摘要:

MINERALOGICAL CHEMISTRY. Mineral o g i c a1 C h e m i s t ry. 115 Metamorphic Graphite : Strata containing Garnet from the Ural Mountains. By A. KARPINSKY (Chem. Ceritr., 1887, 891-822; from Bull. Akad. X t . Petersb., 31, 484--495).-0n the banks of the Bagarjak, on the eastern side of the Ural Mountains, a peculiar in- stance occurs of strata of graphite in limestone, thus indicating a remarkable nonconformability of the strata of the carboniferous period. In the limestone are found crinoides, in the sandstone are crystals of hornblende and quartz, together with orthoclase and plagioclase, whilst in the neighbouring village of Fadina are the usual fossils of the carboniferous period, such as stigmaria a i d lepidodendron. The presence of small specimens of garnet in the graphite containing strata of limestone is peculiar, An analysis of specimens gave the following results :- Si02.AI2O3. FeO. MnO. CaO. MgO. Sp. gr. 37.12 %1*31 8.82 25.83 5.72 0.94 4.065 from which the formula 3Mn3Si,Ol2 ( CU,M~)~AI,S i3012, Fe'e,A12Si,0,2 is deduced. The crystals were formed from twelve rhombic faces, whose apices converge in the centre of the crystal, and whose bases were of rhombic form. V. H. V. Mineral Wax. By G. DOLLFUS and S. MEUNIER (Compt. rend., 105,823-824).-The mineral was obtained from Sloboda Rungorska, near Kolomea, in Austrian Galicia. It occurs in petroliferous strata formed of compact non-aqueous and non-fossiliferous bluish-grey rnarls. It has a fibrous structure with a golden-yellow lustre, some samples strongly resembling crocidolite, whilst others resemble colophony.Boiling water does not dissolve it, and does not remove any chlorides. When placed in ether, it first becomes white and then dissolves, and if the solution is concentrated, it deposits long, colourless, monoclinic needles, ahic h act strongly on polarised light. It imparts a yellow colour to carbon bisulphide, which gradually dissolves a considerable quantity. It is less soluble in alcohol, from which i t crystallises in nacreous, white plates. The mineral has the composition C,H,, distils without residue, and burns with a very luminous flame. Artificial Deposition of Calcite Crystals on Spicules of a, By W. J. SOLLAS (Proc. R. Dublin SOC., 5, 73).-After It melts at above 80" ; sp. gr. 0%. C. H. R. Sponge. i 2116 ABSTRACTS OF CHEMICAL PAPERS.having been left to stand for sorhe days in water containing an excess of calcium carbonate, some acerate and triradiate spicules of a calci- sponge were found to have become incrusted with crystals of calcite. The optic axes of the calcite forming ai spicule, and the crystals de- posited on it, are similarly orientated. The crystals are deposited only on those regions which show the greatest liability to solution (compare Sollas, ibid., 4, 385). B. H. B. Howlite. By S. L. PENFIELD and E. S. SPERRY (Anter. J. Sci., 34, 220-!222).--The specimen examined was obtained from the gypsum quarries at Windsor, Nova Scotia. It consisted of an egg-shaped nodule, one inch a,nd a half in diameter, composed of microscopic flattened prisms usually broken at the ends, but occasionally terminated by two dome faces.Analysis of the air-dry powder gave the follow- ing results :- Si02. B,O,. CaO. N%O. KzO. bHZ0. SO3. Total. 14.70 42.69 28.20 0.51 0.12 11-97 2.01 100.20 The mineral is thus a very acid silico-borate, having the formula H5Ca2B5Si014. In the above analysis the boric anhydride wag deter- mined by the method suggested by F. A. Gooch (Abstr., 1887, 299), a method that was found to give most satisfactory results. By I,. BOURGEOIS (Compt. rend., 105, 1072-1074).-Amorphous strontium and lead sulphates heated in sealed tubes at 150" with hydrochloric acid diluted with twice its volume of water are converted into crystals of celestine and anglesite respectively. Strontium sulphate is heated with an excess of acid.Lead sulphate on the other hand is employed in large excess, and the lead chloride which is formed is removed by treatment first with cold and then with boiling water. B. H, B. Celestine and Anglesite by Senarmont's Process. C. H. B. Mursinskite. By N. v. KOKSCRAROFF (Chem. Centr., 1887, 817, from BuZl. Acad. St. Petersb., 31, 450-464).-This new mineral forms inclusions in topaz and is extremely scarce, sufficient material not yet having been obtained for an analysis, although it was first noticed 32 years ago. It crystallises in the tetragonal system in forms derived from a tetragonal pyramid; axial ratios a : b : b = 0.56641 : 1 : 1 ; colour wine to honey-yellow ; hardness 5-6 ; sp. gr. = 4.149 (?). Occurrence of Harmotome in Wicklow. By J. JOLY (PTOC.R. Dublin SOC., 5, 165--168).-The mineral described occurs im- planted on a quartz matrix in the Lugannre lode, which traverses the granite of Glendnlough in Co. Wicklow. The results of measure- ments of the crystals are in accord with those recorded by Dana, although the appearance of the crystals digers from that usually assigned to harrnotome, one set of the prism faces being reduced to minute dimensions. The sp. gr. of the mineral is 2.46, and its hard- ness is 4.5. It A. J. G. Before the blowpipe, it fuses without intumescence.MINERALOGICAL CHEMISTRY. 117 does not gelatinise with, but is deconlposed by, hydrochloric acid. These tests confirm its identity with harmotome. No occurrence of any zeolite in Wicklow has hitherto been recorded. Beryl and Iolite of Glencullen.By J. JOLY (Proc. R. Dublin SOC., 5, 48-72).--The minerals described occur in the granite of Glencullen, Go. Dublin. The beryl crystals occur in veins and bunches, and present three types : normal crystals, radiating crystals, and altered crystals. The normal beryl is of a pale apple-green colour, semitransparent to translucent. It has a sp. gr. of 2.722. Interpenetration by orthoclase is common in these crystals. The second type is remarkable in habit. The crystals radiate in a striking manner, the groups being all more or less fan-like in section. It was found by experiment, that a temperature of 357" is suEcient to decolorise both green and yellow beryls in a very short time, whether in contact with air or not. With long-continued heating the tem- peratlire of alteration is possibly below 250".The greater proportion of the total number of beryl crystals coming from Glencullen belong t o the third type. The author's observations show that these crystals were primarily composed entirely of beryl, subjected t o reaction with a potash felspar in a state of hot solution. They were partially re- placed, the result being a variable mixture of felspar and beryl, pseudomorphous after beryl. The felspar thus mixed with the beryl is orthoclase containing iolite, a mineral as a rule foreign to Irish rocks. The minute crystals developed through the felspar, and absent from the portions of the sections composed of beryl, appear in two forms: a wide polygonal form and a rectangular elongatled form. The crystals are transparent, with uncertain dichroism.They have a pale blue colonr, a vitreous lustre, a sp. gr. of 2.56, and a hardness of about 7. On fusion, the mineral loses transparency. These characteristics clearly indicate that the small crystals are iolite. Analysis of an impure specimen gave the following results :- B. H. B. The fusibility is about that of iolite. SiO,. A1203. FeO. MgO. CaO. MnO. HzO. Total. 56.7 20.7 13.9 4.2 trace. trace 2.0 97.5 The formula deduced from this imperfect analysis is- 10SiOz,2 (A1203,Fe0) ,MgO,H,O. Studies in the Mica-group. By F W. CLARKE (Amer. ,T. Xci., 34, 1&-137) .-1. Muscovite from Alexander Co., North Carolina.- This mica (Analysis I) occurs at Stony Point with dolomite, iron pyrites, and rutile. All these minerals are dusted over with a dark- green chloritic coating (Analysis II), which appears to be a member *)f the obscure hisingerite group.A microscopical examination of the mica showed that the angle of the optic axes, measured in oil in a plane perpendicular to the plane of symmetry, is 3.5". 8 i 0 2 . 50,. A1203. Fe,O,. MgO. Na20. K20. F. Ignition. Total. B. H. B. I. 45.40 1-10 33.66 2.36 1.86 1.41 8.33 0.69 5-46 100.27 11. 31.16 - 8.06 35.86 5.43 - - - 20.50 101.01118 ABSTRACTS OF CHEMICAL PAPERS. 2. Lepidomelane from Baltimore and Maine.-These minerals gave H20. SiO,. A120,. Fe203. FeO. MnO. CaO. on analysis the following results :- 111. 4.48 35.78 16-39 14.55 11.02 1.08 - IV. 4.67 32.35 17.47 24-22 13-11 1.02 0.89 MgO. K20. Na20. Total. 111. 8-67 7.76 0-56 100-29 IV.- 0.70 6-40 100.83 111. Baltimore ; formula R’,&”3R”’pSi5022. IV. Litchfield, Maine ; formula R’6R”””’6Si5024. These two micas and the so-called annite of Rockport (Abstr., 1887, 347), which has the formula R’6“’4R”‘2Si502q are built up on the same fundamental plan, and exhibit a new and highly suggestive order of variation. All the monoxide bases being united, the follow- ing general formuh are obtained :- Rochport. . . . . . . . Baltimore . . . . . . . Litchfield . . . . . . . R’,4R”2(Si04)a. Rr12(A10)zR”‘2( SiO,),. R’~o(A10)4R”’2(Si04)5. 3. Iron-biotite from Auburn, Maine.-In its ratios, this mica is not simple. Its formula may be approximately written- R‘i 1 (A1 0 ) ,812 ( Si 0,) 5 , with Rll = H&FeZ4. It seems to be a compound intermediate between the Litchfield and Baltimore micas, with R“’ nearly all aluminium, 4.Iron-mica from mar Pike’s Peak.-This specimen was a bronzy- black mica, the entire core of which was made up of a soft rotten material evidently derived from the original mica. Analyses of the broad black margin of mica (V) and of the centre (TI) gave the fol- lowing results :- H20. Si02. A1203. Fe203. FeO. MnO. CaO. MgO. V. 4-54 34.21 16.53 20.15 14.17 0.91 0.48 1-34 VI. 7-82 34.63 17.95 31.25 3-01 0.34 0.81 1.08 N%O. K20. F. Total. V. 1.43 6.50 0.08 100.34 VI. 0.89 1.96 0.54 100.28 B. H. B. Crocidolite from Cumberland, Rhode Island. By A. H. CHESTER and F. I. CAIENS (Arne?. J. Sci., 34, 108--1ll).-At Beacon Pole Hill, near the well-known mineral locality, Diamond Hill, Cum- berland, Rhode Island, crocidolite occurs usually disseminated in fine particles through felspar, but often in larger, radiated nodules.Its colour is usually a dark, bluish-grey. Analysis gave the following results :-MINERALOGICAL CHEMISTRY. 119 Si02. Fe,03. FeO. CaO. MgO. N%O. HzO. Total. I. 52.13 15.93 21-25 - 0.22 6.26 3.95 99.74 11. 51.03 17.88 21.19 - 0.09 6.41 364 100.24" 111. 52.11 20.26 16-51 0.75 1.88 5.79 3.53 100.83 I and I1 crocidolite from Cumherland : sp. gr. 3.2 ; I11 is a new analysis of crocidolite from the Orange River, South Africa. The empirical formula suggested for crocidolite is FeaN~HIFeaSi,0z7, or 3Fe0,N~0,2H,0,Fe20,,9Si02. The authors regard crocidolite as one of the well-authenticated mineral species, and cannot agree with the conclusions of Dolter and of Kenngott (Abstr., 1886, 128), that cro- cidolite is merely a fibrous variety of arfvedsonite.The mineral, named abriachanite by Hedcile ( W m . Mag., 3, 61), and the crocidolite from the Vosges Mountains, analysed by Delesse, are shown to be essentially the same substance-a magnesian variety of crocidoli t e. B. H. B. Nature and Formation of Glauconite. By C. W. v. GUMBEL (Chew,. Centr., 1687, 813-814, from Ber. Manch. Akad., 1886, 418- 449).--The author has examined specimens of glauconite from dif- ferent geological formations, and established their identity ; speci- mens of this mineral from tlhe coast of New Jersey are more particularly examined, analysis of which gave the following resiilts :- SiOP AI2O8. Fe20,. PeO. CrtO. MpO. K20. N%O. H20. 46.9 4-06 27-09 3.6 0.2 0.7 6.16 1.28 9.25 There were present, in addition, traces of organic substances, man- ganese, phosphoric acid, and sulphuric acid.The author combats the view of Ehrenberg as to the suspected connection between the remnants of' foraminifere and glauconite : it seems more probable that glauconite has been intussuscepted between the shells of the foraminifer=. The condition of formation was probably a shallow sea, in the muddy deposits of which organisms were included, and in their decomposition gave off hydrocarbons, carbonic acid, and hydrogen sulphide. At the surface of the bubbles of gas minerill substances-such as lime, silicic acid, and, in some cases, glauconite separated, which subsequently increased by intussusception. I n the femiferous earths of Kressenberg, the nuclei of brown oxide, which is probably a metamorphic product of glauconite, has penetrated into the shells of conchylae and echinodermata.Black Marble of Kilkenny. By W. N. HARTLEY ( P ~ o c . R. Dubkim Xoc., 5, 486--488).-At the quarries from which this well-known marble is procured, the author noticed that the weathered surfaces of the rock exhibit a yellow-ochreous colour. This might be caused by the colour of the freshly-hewn marble being due to the presence of ferrous sulphide or of ferrous carbonate which, in presence of carbonic acid and air, become dissolved and oxidised. Fractured surfaces smelt of h3;drogen sulphide, due to the existence of calcium hydro- f This total is given as 9994 in the original. V. H. V.120 ABSTRACTS OF CHEMICAL PAPERS.~ 3'38 1 4.4 2 -3 3 *33 1.66 1 2.087 7.5 4.7 sulphide in the rock. results :- Analysis of the marble gave the following 44-03 59.60 54-37 46.7 C 0 2 . CaO. FeO. CuO. MgO. SiO,. H20. C. S. Total. 40.41 55.36 0.34 0.05 0.24 1.U 0.60 1.48 0.01 99-95 B. H. B. Analyses of Calcareous Rocks and Pozzuolana from Tevere. By VKRRI and TROTTARELLI (Gazzetta, 17, 385-390).-1n this paper, a series of analyses are set forth of calcareous rocks from the Tevere basin ; typical specimens from the several geological periods are selected. References are also given to former memoirs in the Reale Accadrrnia dei Lincei and the Bzdl. SOC. Geol. Amongst others the following analyses of specimens of pozzuolana are of particular iiiterest :- 2.8 2-11 6'63 3 -31 Red pozzuolana ................Grey pozzuolana from Attighano . Grey pozzuolana from Orte.. .... Maroon pozzuolana from Lerni . . 30 * 31 30 '3 6.04 13.61 9 *61 6.7 24.56 20.57 1 '82 0.77'5 0-16 9 '23 Red pozzuola.na ................ Greg pGzzuoluna from Attighano . Grey pozzuolana from Orte ...... Maroon pozzuolana from Lerni.. . 3 -4.6 3.69 1 '63 3.26 V. H. V. Serpentine of the Onondaga Salt-group at Syracuse. By G. H. WILLIAMS (Amer. J. Sci., 34, 137--145).-The eruptive nature of the nintrix of the serpentine (peridotite) of Syracuse, New Pork, is prored from its structure, and from the inclusion of fragments of the adjacent limestone, in' opposition to T. S. Hunt's theory of the aqueous origin of serpentine. Pyrope and ilmenite were not detected in the Syracuse serpentine.Chrome-iron ore and perovskite, however, are present, as was shown by a.n analysis of 0.0165 p a m of the filtrate obtaiiied by digesting the finely-powdered rock for a long time in concentrated hydrochloric acid under pressure, and by treating the residue with strong sulphuric acid. The analysis gave- Ti02. CaO. FeO. Total. 34-54 12-18 54.54 101.20 B. H. B.MINERALOGICAL CHEMISTRY. 121 Peperite of the Puy de la Piquette. By F. GONNARD (Compt. rend., 105, 886-888).-The “ Wacke” of the Puy de la Piquette was described by Lecoq and Bouillet as a bluish peperite of sp. gr. 2-6 to 2.3, which effervesces with an acid, and melts before the blow- pipe to a brownish-black enamel. It contains fragments of basalt, highly cellular black scoria, small crystals of hornblende, calcareous nodules and crystals of mesotype, with masses of carbonised wood, the latter being covered with fibrolamellar crystals of mesotype.The calcareous nodules enclose mesotype in crystals and crystalline masses. Apophyllite in nacreous, white, partially translucent crystals of the form m(110), p(OOl), a’(lOl), also occurs in the calcareous nodules, but not in the peperite itself. It occurs in small druses, and also asso- ciated with mesotype in radiating bundles, the character of which shows that the apophyllite is a later formation than the mesotype. Annlcime is also present in the peperite, but not in the calcareous nodules. There are also small crystals of felspar round which, in many cases, the analcime has accumulated, and crystals of green diallage accompanied by mica.C. H. B. An Iron of doubtful Origin. Bay R. B. RIGGS (Amer. J. Sci., 34, 60). -This iron was found on a farm in Jefferson County, Tennessee, in a region full of small iron furnaces, whence have come a numberof pseudo-meteorites. The iron is characterised by extreme hardness ; its weight is 640 grams, and its sp. gr. 7-61. Analysis gave the fol- lowing results :- Fe. Ni. Co. Cu. As. Mn. Mg. P. 88-27 0-76 0.19 0.03 trace 6.73 0.14 1.80 Si. Graphite. C. Total. 0.15 0.86 1-46 100.39 Treated with nitric acid, the polished surfaces developed fine mark- ings not unlike Widmanstatten figures. B. H. B. New Meteoric Iron. By R. B. RIGGS (Amer. J. Sci., 34, 59).- This meteorite was found in a collection of minerals made by the late Colonel J.J. Abert. It weighed 456 grams, and in cross-section measured 50 by 37 mm. Fe. Xi. Co. P. 5. Graphite. C. Total. Sp. gr. 92-04 7.00 0.68 0.08 0.01 0.03 0.02 99.86 7.89 Analysis gave the following results :- In composition, therefore, it is similar to the Nelson County me- teorite. B. H. B. Aerolite from Rensselaer Co., New York. By S. C. H. BAILEY (Awzer. J. Xci., 34, 60-62).-1n 1863 a stone of unusual appearance was found on the bank of the Tomhannock Creek in Rensselaer Co. I n 1884 it was recognised as an asrolite. It weighed 1.5 kilos., with an average diameter of 10 cm. In its general aspect, upon a cut122 ABSTRACTS OF CHEMICAL PAPERS. surface, it resembles the Seres, Macedonia stone. For many years this aBrolite seems to have been exposed to the action of the atmo- sphere and of the soil without showing any deterioration. An analysis of the metallic portion of the stone gave 13-02 per cent. of metallic iron, and 3.06 per cent.of nickel. The composition of the stony portion has not yet been determined. B. H. B. Deposition of Scorodite from Arsenical Waters in the Yel- lowstone Park. By A. HAGUE (Amer. J. Xci., 34, 171-175).- Scorodite, although a comparatively rare mineral, is found at a num- ber of localities in the Yellowstone Park as an incrustation deposited from the water of hot springs and geysers. The best occurrence is at the Joseph's Coat Springs on Broad Creek, east of the Grand Caiion, in the form a brilliant green deposit upon the sinter. Fre- quently the cavities in the Rinter are filled with scorodite, and occa- sionally it forms nodular masses half an inch in diameter.Analysis (I) of the mineral shows a nearly pure scorodite. Other localities are Chrome Springs, and one or two places in Norris Basin. At the Constant Geyser in Norris Basin, a specimen of scorodite was analysed (11) ; it contained a large quantity of silica. Scorodite, as deposited from these thermal waters, is evidently a very unstable minerd. It slowly undergoes oxidation, leaving an ochreous material containing varying amounts of arsenic acid. SiOz ................. so3 .................. coz .................. B,03 ................ As203 ................ c1 ................... Br ................... HzS.. ................ O(basic) .............. Fe ................... A1 ................... Ca ...................K .................... Na ................... Li.. .................. Am .................. HCl.. ................ Mg .................. Totals ............ Analysis 111. Grams per kilogram of water. -- 0 -4685 0 -0923 0 *0155 0 *03 17 0 *0018 0 -574.0 trace nil 0 -0185 trace 0 -0048 0 *(I146 0.0018 0'!)745 0 *3190 0 '0030 0 -0012 0 *0008 1 '6220 -- Per cent. of total ma- terial in solution. -- 28 *88 5 -69 0.95 1 -95 0 *11 35 *39 - - 1 -14 0.29 0.90 0 *I1 4 -60 19 -67 0 -19 0 -08 0.05 100 -00 - -- Analysis IV. Grams per kilogram. 0 -3828 0 -0152 0 * 0894 0.0148 0 so021 0 -4391 0 9034 0 .om2 0'0419 trace 0 -0009 0 -0015 0 *0006 0 -0267 0 *3666 0 *(I056 0 '0000 - -- 1 *3908 Per cent. of total ma- terial in s o h tion. 27 '52 1 '09 6 -48 1 '07 0 '15 31 '57 0 -25 0.01 3 '02 0.06 0 '11 0 -04 1 -92 26 '36 0 '40 - - - 100~00ORGANIC CBEMISTRT.123 8i02. A120,. Fe203. As205. H20. Total. I. trace - 3494 48.79 16-27 100.00 11. 49.83 4-74 18.00 17.37 10-62 100.56 Ananalysis of the water from the Constant Geyser is given (111). Its temperature was 198" F. ; reaction slightly acid; sp. gr. 1*0011. For the purpose of comparison, an analysis (IV) is given of the water from the Old Faithful Geyser in the Upper Geyser Basin. Its reac- tion is alkaline, and sp. gr. 1.00096. In analysis IV traces of manganese, caesium," and rubidium were observed. B. H. B.MINERALOGICAL CHEMISTRY.Mineral o g i c a1 C h e m i s t ry.115Metamorphic Graphite : Strata containing Garnet from theUral Mountains.By A. KARPINSKY (Chem. Ceritr., 1887, 891-822;from Bull. Akad. X t . Petersb., 31, 484--495).-0n the banks of theBagarjak, on the eastern side of the Ural Mountains, a peculiar in-stance occurs of strata of graphite in limestone, thus indicating aremarkable nonconformability of the strata of the carboniferousperiod. In the limestone are found crinoides, in the sandstone arecrystals of hornblende and quartz, together with orthoclase andplagioclase, whilst in the neighbouring village of Fadina are theusual fossils of the carboniferous period, such as stigmaria a i dlepidodendron. The presence of small specimens of garnet in thegraphite containing strata of limestone is peculiar, An analysis ofspecimens gave the following results :-Si02.AI2O3. FeO. MnO. CaO. MgO. Sp. gr.37.12 %1*31 8.82 25.83 5.72 0.94 4.065from which the formula 3Mn3Si,Ol2 ( CU,M~)~AI,S i3012, Fe'e,A12Si,0,2 isdeduced. The crystals were formed from twelve rhombic faces,whose apices converge in the centre of the crystal, and whose baseswere of rhombic form. V. H. V.Mineral Wax. By G. DOLLFUS and S. MEUNIER (Compt. rend.,105,823-824).-The mineral was obtained from Sloboda Rungorska,near Kolomea, in Austrian Galicia. It occurs in petroliferous strataformed of compact non-aqueous and non-fossiliferous bluish-greyrnarls. It has a fibrous structure with a golden-yellow lustre, somesamples strongly resembling crocidolite, whilst others resemblecolophony. Boiling water doesnot dissolve it, and does not remove any chlorides.When placed inether, it first becomes white and then dissolves, and if the solution isconcentrated, it deposits long, colourless, monoclinic needles, ahic hact strongly on polarised light. It imparts a yellow colour to carbonbisulphide, which gradually dissolves a considerable quantity. It isless soluble in alcohol, from which i t crystallises in nacreous, whiteplates. The mineral has the composition C,H,, distils without residue,and burns with a very luminous flame.Artificial Deposition of Calcite Crystals on Spicules of a,By W. J. SOLLAS (Proc. R. Dublin SOC., 5, 73).-AfterIt melts at above 80" ; sp. gr. 0%.C. H. R.Sponge.i 116 ABSTRACTS OF CHEMICAL PAPERS.having been left to stand for sorhe days in water containing an excessof calcium carbonate, some acerate and triradiate spicules of a calci-sponge were found to have become incrusted with crystals of calcite.The optic axes of the calcite forming ai spicule, and the crystals de-posited on it, are similarly orientated.The crystals are depositedonly on those regions which show the greatest liability to solution(compare Sollas, ibid., 4, 385). B. H. B.Howlite. By S. L. PENFIELD and E. S. SPERRY (Anter. J. Sci., 34,220-!222).--The specimen examined was obtained from the gypsumquarries at Windsor, Nova Scotia. It consisted of an egg-shapednodule, one inch a,nd a half in diameter, composed of microscopicflattened prisms usually broken at the ends, but occasionally terminatedby two dome faces. Analysis of the air-dry powder gave the follow-ing results :-Si02.B,O,. CaO. N%O. KzO. bHZ0. SO3. Total.14.70 42.69 28.20 0.51 0.12 11-97 2.01 100.20The mineral is thus a very acid silico-borate, having the formulaH5Ca2B5Si014. In the above analysis the boric anhydride wag deter-mined by the method suggested by F. A. Gooch (Abstr., 1887, 299),a method that was found to give most satisfactory results.By I,.BOURGEOIS (Compt. rend., 105, 1072-1074).-Amorphous strontiumand lead sulphates heated in sealed tubes at 150" with hydrochloricacid diluted with twice its volume of water are converted into crystalsof celestine and anglesite respectively. Strontium sulphate is heatedwith an excess of acid. Lead sulphate on the other hand is employedin large excess, and the lead chloride which is formed is removed bytreatment first with cold and then with boiling water.B.H, B.Celestine and Anglesite by Senarmont's Process.C. H. B.Mursinskite. By N. v. KOKSCRAROFF (Chem. Centr., 1887, 817,from BuZl. Acad. St. Petersb., 31, 450-464).-This new mineralforms inclusions in topaz and is extremely scarce, sufficient materialnot yet having been obtained for an analysis, although it was firstnoticed 32 years ago. It crystallises in the tetragonal system informs derived from a tetragonal pyramid; axial ratios a : b : b =0.56641 : 1 : 1 ; colour wine to honey-yellow ; hardness 5-6 ; sp.gr. = 4.149 (?).Occurrence of Harmotome in Wicklow. By J. JOLY (PTOC.R. Dublin SOC., 5, 165--168).-The mineral described occurs im-planted on a quartz matrix in the Lugannre lode, which traverses thegranite of Glendnlough in Co.Wicklow. The results of measure-ments of the crystals are in accord with those recorded by Dana,although the appearance of the crystals digers from that usuallyassigned to harrnotome, one set of the prism faces being reduced tominute dimensions. The sp. gr. of the mineral is 2.46, and its hard-ness is 4.5. ItA. J. G.Before the blowpipe, it fuses without intumescenceMINERALOGICAL CHEMISTRY. 117does not gelatinise with, but is deconlposed by, hydrochloric acid.These tests confirm its identity with harmotome. No occurrence ofany zeolite in Wicklow has hitherto been recorded.Beryl and Iolite of Glencullen. By J. JOLY (Proc.R. DublinSOC., 5, 48-72).--The minerals described occur in the granite ofGlencullen, Go. Dublin. The beryl crystals occur in veins andbunches, and present three types : normal crystals, radiating crystals,and altered crystals. The normal beryl is of a pale apple-greencolour, semitransparent to translucent. It has a sp. gr. of 2.722.Interpenetration by orthoclase is common in these crystals. Thesecond type is remarkable in habit. The crystals radiate in a strikingmanner, the groups being all more or less fan-like in section. It wasfound by experiment, that a temperature of 357" is suEcient todecolorise both green and yellow beryls in a very short time, whetherin contact with air or not. With long-continued heating the tem-peratlire of alteration is possibly below 250".The greater proportionof the total number of beryl crystals coming from Glencullen belongt o the third type. The author's observations show that these crystalswere primarily composed entirely of beryl, subjected t o reaction witha potash felspar in a state of hot solution. They were partially re-placed, the result being a variable mixture of felspar and beryl,pseudomorphous after beryl. The felspar thus mixed with the berylis orthoclase containing iolite, a mineral as a rule foreign to Irish rocks.The minute crystals developed through the felspar, and absentfrom the portions of the sections composed of beryl, appear in twoforms: a wide polygonal form and a rectangular elongatled form.The crystals are transparent, with uncertain dichroism.They havea pale blue colonr, a vitreous lustre, a sp. gr. of 2.56, and a hardnessof about 7. On fusion, themineral loses transparency. These characteristics clearly indicatethat the small crystals are iolite. Analysis of an impure specimengave the following results :-B. H. B.The fusibility is about that of iolite.SiO,. A1203. FeO. MgO. CaO. MnO. HzO. Total.56.7 20.7 13.9 4.2 trace. trace 2.0 97.5The formula deduced from this imperfect analysis is-10SiOz,2 (A1203,Fe0) ,MgO,H,O.Studies in the Mica-group. By F W. CLARKE (Amer. ,T. Xci.,34, 1&-137) .-1. Muscovite from Alexander Co., North Carolina.-This mica (Analysis I) occurs at Stony Point with dolomite, ironpyrites, and rutile. All these minerals are dusted over with a dark-green chloritic coating (Analysis II), which appears to be a member*)f the obscure hisingerite group.A microscopical examination of themica showed that the angle of the optic axes, measured in oil in aplane perpendicular to the plane of symmetry, is 3.5".8 i 0 2 . 50,. A1203. Fe,O,. MgO. Na20. K20. F. Ignition. Total.B. H. B.I. 45.40 1-10 33.66 2.36 1.86 1.41 8.33 0.69 5-46 100.2711. 31.16 - 8.06 35.86 5.43 - - - 20.50 101.0118 ABSTRACTS OF CHEMICAL PAPERS.2. Lepidomelane from Baltimore and Maine.-These minerals gaveH20. SiO,. A120,. Fe203. FeO. MnO. CaO.on analysis the following results :-111. 4.48 35.78 16-39 14.55 11.02 1.08 -IV. 4.67 32.35 17.47 24-22 13-11 1.02 0.89MgO. K20. Na20. Total.111. 8-67 7.76 0-56 100-29IV.- 0.70 6-40 100.83111. Baltimore ; formula R’,&”3R”’pSi5022. IV. Litchfield, Maine ;formula R’6R”””’6Si5024.These two micas and the so-called annite of Rockport (Abstr.,1887, 347), which has the formula R’6“’4R”‘2Si502q are built up onthe same fundamental plan, and exhibit a new and highly suggestiveorder of variation. All the monoxide bases being united, the follow-ing general formuh are obtained :-Rochport. . . . . . . .Baltimore . . . . . . .Litchfield . . . . . . .R’,4R”2(Si04)a.Rr12(A10)zR”‘2( SiO,),.R’~o(A10)4R”’2(Si04)5.3. Iron-biotite from Auburn, Maine.-In its ratios, this mica is notsimple. Its formula may be approximately written-R‘i 1 (A1 0 ) ,812 ( Si 0,) 5 ,with Rll = H&FeZ4. It seems to be a compound intermediatebetween the Litchfield and Baltimore micas, with R“’ nearly allaluminium,4.Iron-mica from mar Pike’s Peak.-This specimen was a bronzy-black mica, the entire core of which was made up of a soft rottenmaterial evidently derived from the original mica. Analyses of thebroad black margin of mica (V) and of the centre (TI) gave the fol-lowing results :-H20. Si02. A1203. Fe203. FeO. MnO. CaO. MgO.V. 4-54 34.21 16.53 20.15 14.17 0.91 0.48 1-34VI. 7-82 34.63 17.95 31.25 3-01 0.34 0.81 1.08N%O. K20. F. Total.V. 1.43 6.50 0.08 100.34VI. 0.89 1.96 0.54 100.28 B. H. B.Crocidolite from Cumberland, Rhode Island. By A. H.CHESTER and F. I. CAIENS (Arne?. J. Sci., 34, 108--1ll).-At BeaconPole Hill, near the well-known mineral locality, Diamond Hill, Cum-berland, Rhode Island, crocidolite occurs usually disseminated in fineparticles through felspar, but often in larger, radiated nodules.Itscolour is usually a dark, bluish-grey. Analysis gave the followingresults :MINERALOGICAL CHEMISTRY. 119Si02. Fe,03. FeO. CaO. MgO. N%O. HzO. Total.I. 52.13 15.93 21-25 - 0.22 6.26 3.95 99.7411. 51.03 17.88 21.19 - 0.09 6.41 364 100.24"111. 52.11 20.26 16-51 0.75 1.88 5.79 3.53 100.83I and I1 crocidolite from Cumherland : sp. gr. 3.2 ; I11 is a newanalysis of crocidolite from the Orange River, South Africa. Theempirical formula suggested for crocidolite is FeaN~HIFeaSi,0z7, or3Fe0,N~0,2H,0,Fe20,,9Si02. The authors regard crocidolite as oneof the well-authenticated mineral species, and cannot agree with theconclusions of Dolter and of Kenngott (Abstr., 1886, 128), that cro-cidolite is merely a fibrous variety of arfvedsonite.The mineral, named abriachanite by Hedcile ( W m .Mag., 3, 61), andthe crocidolite from the Vosges Mountains, analysed by Delesse, areshown to be essentially the same substance-a magnesian variety ofcrocidoli t e. B. H. B.Nature and Formation of Glauconite. By C. W. v. GUMBEL(Chew,. Centr., 1687, 813-814, from Ber. Manch. Akad., 1886, 418-449).--The author has examined specimens of glauconite from dif-ferent geological formations, and established their identity ; speci-mens of this mineral from tlhe coast of New Jersey are moreparticularly examined, analysis of which gave the following resiilts :-SiOP AI2O8.Fe20,. PeO. CrtO. MpO. K20. N%O. H20.46.9 4-06 27-09 3.6 0.2 0.7 6.16 1.28 9.25There were present, in addition, traces of organic substances, man-ganese, phosphoric acid, and sulphuric acid. The author combatsthe view of Ehrenberg as to the suspected connection between theremnants of' foraminifere and glauconite : it seems more probablethat glauconite has been intussuscepted between the shells of theforaminifer=. The condition of formation was probably a shallowsea, in the muddy deposits of which organisms were included, andin their decomposition gave off hydrocarbons, carbonic acid, andhydrogen sulphide. At the surface of the bubbles of gas minerillsubstances-such as lime, silicic acid, and, in some cases, glauconiteseparated, which subsequently increased by intussusception. I n thefemiferous earths of Kressenberg, the nuclei of brown oxide, whichis probably a metamorphic product of glauconite, has penetrated intothe shells of conchylae and echinodermata.Black Marble of Kilkenny.By W. N. HARTLEY ( P ~ o c . R. DubkimXoc., 5, 486--488).-At the quarries from which this well-knownmarble is procured, the author noticed that the weathered surfaces ofthe rock exhibit a yellow-ochreous colour. This might be caused bythe colour of the freshly-hewn marble being due to the presence offerrous sulphide or of ferrous carbonate which, in presence of carbonicacid and air, become dissolved and oxidised. Fractured surfacessmelt of h3;drogen sulphide, due to the existence of calcium hydro-f This total is given as 9994 in the original.V.H. V120 ABSTRACTS OF CHEMICAL PAPERS.~ 3'38 1 4.42 -3 3 *331.66 1 2.0877.5 4.7sulphide in the rock.results :-Analysis of the marble gave the following44-0359.6054-3746.7C 0 2 . CaO. FeO. CuO. MgO. SiO,. H20. C. S. Total.40.41 55.36 0.34 0.05 0.24 1.U 0.60 1.48 0.01 99-95B. H. B.Analyses of Calcareous Rocks and Pozzuolana from Tevere.By VKRRI and TROTTARELLI (Gazzetta, 17, 385-390).-1n this paper,a series of analyses are set forth of calcareous rocks from the Teverebasin ; typical specimens from the several geological periods areselected. References are also given to former memoirs in the RealeAccadrrnia dei Lincei and the Bzdl. SOC. Geol.Amongst others the following analyses of specimens of pozzuolanaare of particular iiiterest :-2.82-116'633 -31Red pozzuolana ................Grey pozzuolana from Attighano .Grey pozzuolana from Orte......Maroon pozzuolana from Lerni . .30 * 3130 '36.0413.619 *616.724.5620.571 '820.77'50-169 '23Red pozzuola.na ................Greg pGzzuoluna from Attighano .Grey pozzuolana from Orte ......Maroon pozzuolana from Lerni.. .3 -4.63.691 '633.26V. H. V.Serpentine of the Onondaga Salt-group at Syracuse. By G.H. WILLIAMS (Amer. J. Sci., 34, 137--145).-The eruptive nature ofthe nintrix of the serpentine (peridotite) of Syracuse, New Pork, isprored from its structure, and from the inclusion of fragments of theadjacent limestone, in' opposition to T.S. Hunt's theory of the aqueousorigin of serpentine. Pyrope and ilmenite were not detected in theSyracuse serpentine. Chrome-iron ore and perovskite, however, arepresent, as was shown by a.n analysis of 0.0165 p a m of the filtrateobtaiiied by digesting the finely-powdered rock for a long time inconcentrated hydrochloric acid under pressure, and by treating theresidue with strong sulphuric acid. The analysis gave-Ti02. CaO. FeO. Total.34-54 12-18 54.54 101.20B. H. BMINERALOGICAL CHEMISTRY. 121Peperite of the Puy de la Piquette. By F. GONNARD (Compt.rend., 105, 886-888).-The “ Wacke” of the Puy de la Piquettewas described by Lecoq and Bouillet as a bluish peperite of sp. gr.2-6 to 2.3, which effervesces with an acid, and melts before the blow-pipe to a brownish-black enamel.It contains fragments of basalt,highly cellular black scoria, small crystals of hornblende, calcareousnodules and crystals of mesotype, with masses of carbonised wood,the latter being covered with fibrolamellar crystals of mesotype. Thecalcareous nodules enclose mesotype in crystals and crystallinemasses.Apophyllite in nacreous, white, partially translucent crystals of theform m(110), p(OOl), a’(lOl), also occurs in the calcareous nodules,but not in the peperite itself. It occurs in small druses, and also asso-ciated with mesotype in radiating bundles, the character of whichshows that the apophyllite is a later formation than the mesotype.Annlcime is also present in the peperite, but not in the calcareousnodules.There are also small crystals of felspar round which, inmany cases, the analcime has accumulated, and crystals of greendiallage accompanied by mica. C. H. B.An Iron of doubtful Origin. Bay R. B. RIGGS (Amer. J. Sci., 34,60). -This iron was found on a farm in Jefferson County, Tennessee,in a region full of small iron furnaces, whence have come a numberofpseudo-meteorites. The iron is characterised by extreme hardness ;its weight is 640 grams, and its sp. gr. 7-61. Analysis gave the fol-lowing results :-Fe. Ni. Co. Cu. As. Mn. Mg. P.88-27 0-76 0.19 0.03 trace 6.73 0.14 1.80Si. Graphite. C. Total.0.15 0.86 1-46 100.39Treated with nitric acid, the polished surfaces developed fine mark-ings not unlike Widmanstatten figures.B. H. B.New Meteoric Iron. By R. B. RIGGS (Amer. J. Sci., 34, 59).-This meteorite was found in a collection of minerals made by the lateColonel J. J. Abert. It weighed 456 grams, and in cross-sectionmeasured 50 by 37 mm.Fe. Xi. Co. P. 5. Graphite. C. Total. Sp. gr.92-04 7.00 0.68 0.08 0.01 0.03 0.02 99.86 7.89Analysis gave the following results :-In composition, therefore, it is similar to the Nelson County me-teorite. B. H. B.Aerolite from Rensselaer Co., New York. By S. C. H. BAILEY(Awzer. J. Xci., 34, 60-62).-1n 1863 a stone of unusual appearancewas found on the bank of the Tomhannock Creek in Rensselaer Co.I n 1884 it was recognised as an asrolite. It weighed 1.5 kilos., withan average diameter of 10 cm.In its general aspect, upon a cu122 ABSTRACTS OF CHEMICAL PAPERS.surface, it resembles the Seres, Macedonia stone. For many yearsthis aBrolite seems to have been exposed to the action of the atmo-sphere and of the soil without showing any deterioration. Ananalysis of the metallic portion of the stone gave 13-02 per cent. ofmetallic iron, and 3.06 per cent. of nickel. The composition of thestony portion has not yet been determined. B. H. B.Deposition of Scorodite from Arsenical Waters in the Yel-lowstone Park. By A. HAGUE (Amer. J. Xci., 34, 171-175).-Scorodite, although a comparatively rare mineral, is found at a num-ber of localities in the Yellowstone Park as an incrustation depositedfrom the water of hot springs and geysers. The best occurrence isat the Joseph's Coat Springs on Broad Creek, east of the GrandCaiion, in the form a brilliant green deposit upon the sinter.Fre-quently the cavities in the Rinter are filled with scorodite, and occa-sionally it forms nodular masses half an inch in diameter. Analysis(I) of the mineral shows a nearly pure scorodite.Other localities are Chrome Springs, and one or two places inNorris Basin. At the Constant Geyser in Norris Basin, a specimenof scorodite was analysed (11) ; it contained a large quantity of silica.Scorodite, as deposited from these thermal waters, is evidently a veryunstable minerd. It slowly undergoes oxidation, leaving an ochreousmaterial containing varying amounts of arsenic acid.SiOz .................so3 ..................coz ..................B,03 ................As203 ................c1 ...................Br ...................HzS.. ................O(basic) ..............Fe ...................A1 ...................Ca ...................K ....................Na ...................Li.. ..................Am ..................HCl.. ................Mg ..................Totals ............Analysis 111.Grams perkilogram ofwater.--0 -46850 -09230 *01550 *03 170 *00180 -574.0tracenil0 -0185trace0 -00480 *(I1460.00180'!)7450 *31900 '00300 -00120 *00081 '6220--Per cent. oftotal ma-terial insolution.--28 *885 -690.951 -950 *1135 *39 - -1 -140.290.900 *I14 -6019 -670 -190 -080.05100 -00---Analysis IV.Grams perkilogram.0 -38280 -01520 * 08940.01480 so0210 -43910 90340 .om20'0419trace0 -00090 -00150 *00060 -02670 *36660 *(I0560 '0000- --1 *3908Per cent. oftotal ma-terial ins o h tion.27 '521 '096 -481 '070 '1531 '570 -250.013 '020.060 '110 -041 -9226 '360 '40---100~0ORGANIC CBEMISTRT. 1238i02. A120,. Fe203. As205. H20. Total.I. trace - 3494 48.79 16-27 100.0011. 49.83 4-74 18.00 17.37 10-62 100.56Ananalysis of the water from the Constant Geyser is given (111).Its temperature was 198" F. ; reaction slightly acid; sp. gr. 1*0011.For the purpose of comparison, an analysis (IV) is given of the waterfrom the Old Faithful Geyser in the Upper Geyser Basin. Its reac-tion is alkaline, and sp. gr. 1.00096.In analysis IV traces of manganese, caesium," and rubidium wereobserved. B. H. B

ISSN:0368-1769    

DOI:10.1039/CA8885400115

出版商:RSC    

年代:1888

数据来源: RSC

摘要:

ORGANIC CBEMISTRT. 123 Organic Chemistry. Action of Chlorine on Amylene. By J. KONDAKOFF (Chem. Centr., 1887, 979, from J. Russ. Chem. SOC., 1887, 337)-In the course of investigations on the action of chlorine on isomeric amylenes, the author obtained from the modification insoluble in sulphuric acid, an unsaturated chloro-derivative, C,H,Cl, in addition to the dichloropen- tane C5HloC12. From the former, two aIcohoIs are obtainable, one a primary, boiling at 141”, and on oxidation yielding a caproic acid, the other a secondary alcohol, boiling a t 117”, and yielding a ketone of boiling point 101 -103”, probably methyl propyl ketoue. The primary alcohol is a P-ethyl ally1 alcohol, CH,Me*CHCH*CH,*OH ; the second- ary alcohol differs both from methyl isopropenyl carbinol and ethyl vinylcarbinol, and probably has the constitution CHMe: CH-CHMe-OH. Action of Hypochlorous Acid on the Hydrocarbon C,H,,.By S . A. PBIBYTEK (Chem.. Centr., 1887, 978, from J. Russ. Chem. SOC., 1887,338) .-The hydrocarbon CH2 CMe*CH2*CH2*CMe : CH,, obtained by Sesukoff from sodium and chlorisobutylene when treated with hypochlorous acid, yields a chlorhydrin, C8H14( OH),Cl,, from which the dioxide CsH& can be obtained. The latter gives with water a tetratomic alcohol, octyEerythro2, C,H,4(OH)4. By R. VARET (Compt. rend., 105, 1070-1072) .-Pure zinc cyanide is dissolved to saturation in aqueous ammonia at a gentle heat and a, current of ammonia gas is passed into the liquid, which is filtered when saturated with the cyanide, again treated with ammonia gas, and allowed to cool.A crystalline precipitate forms, but redissolves when gently heated, and separates on cooling in large, transparent, prismatic crystals of the composition ZnCy2,BNH3 + H20. This compound loses ammonia and water when exposed t o the air, and becomes white and opaque. It is very soluble in aqueous or alcoholic ammonia, and if freshly prepared, is also soluble in water with slight decomposition, but if it has been prepared for some time, it is immediately decomposed by water. It i s slowly decomposed by sodium hydroxide in the cold. When heated V. H. V. V. H. V. Ammonio-zinc Cyanides. * “ Calcium ” in the original.”124 ABSTRACTS OF CHEMICAL PAPERS. in a current of ammonia gas, it loses water, but no compound richer in ammonia is formed.When zinc cyanide is dissolved to saturation in alcohol, treated with a current of ammonia gas, and the liquid allowed to evaporate spon t)aneously, the compound ZnCy2,2NH3 is obtained in transparent crystals, which lose ammonia rapidly when exposed to the air and become opaque, and are very soluble in aqueous or alcoholic am- monia. The same compound is obtained by passing ammonia gas over gently heated zinc cyanide. Zinc cyanide forms only one com- pound with ammonia, and not a series of compounds like the chloride and bromide. C. H. B. Methyl Mercaptan and some of its Derivatives. By J. OBERMEYER (Ber., 20, 2918--2928).-Methyl thioacetate is prepared by the action of lead methyl mercaptide on a slight excess of cooled acetic chloride; it boils at 95-96' (not 62-68', Cahours, Compt.rend., 80, 1317, and 81, 1163). The substance described by Cahours (Zoc. cit.) is probably a mixture of the ether with methyl iodide, acetic acid, and hydrobromic acid. M etlyZ thiopropionate, C,H8S0, prepared from propionic chloride, is a colourless liquid of repulsive odour, boiling a t 119-120". Methyl thinbutyrate, C5HloS0, is a light oil having an odour resem- bling that of butyric acid ; i t boils at 140-144". MethyZ a-thi?benzoate, C8HeS0, boils a t 231-232". Methy Zz'sopropyZ sulphide, SMePr, is prepared by dissolving sodium in isopropyl mercaptan diluted with absolute ether, and the mixture, contJained in a reflux apparatus, is treated with methyl iodide in small portions; it is then heated for 15 minutes in a water-bath and filtered.The heavy oil which separates from the solution when kept over night, is removed, and the ethereal solution evaporated and frac- tionally distilled. MethyE anzyZ suZphide, SMe*C5HI1, ie prepared by the action of methyl iodide on ainyl mercaptide ; it boils at 136-138". Isoamyl disulphide is also formed. Methyl aZZyZ sdphide, SMe*C3H6, is formed when 25 grams of lead methyl mercaptide is heated with allyl bromide and ether a t 100". It is a clear liquid of a very penetrating odour, boiling a t 91-93'. When allyl tribromide is heated with an excess of lead methyl mercaptide and ether at lOC)", a compound, probably of the formula SMe*C31-lqBr, is obtained. It could not be purified, as it decomposes at 120-130". Methy 1 benxyl sdphide, SMe*C7H7, is obtained by heating lead methyl mercaptide, and benzyl chloride a t 100".It is a clear liquid of :in odoiir resembling horse-radish, and boils at 195-198'. Methyl pher~yZ sdphide, SMe-Ph, prepared from lead thiophenol and methyl iodide, forms a clear liquid boiling at 187-188". Dimethyl thioresorcino2, C6H4(SMe)2, is an oily liquid of a disagree- able odour boiling a t 278'. Methyl diphenyl sulphide, SMe*CI2H9, is obtained from lead thio- diphenyl ; it crystallises from alcohol in flakes of very slender needles, melting at 107-108". It boils tit 93-95".ORGANIC CHEMISTRY. 125 Dimethyl diphenyl disulphide, CI4Hl4S2, is prepared by heating the lead mercaptide of diphenylthiohydrate with methyl iodide. It crystallises from alcohol in lustrous bright-yellow plates melting a t 185-186".N. H. M. Brandy from a Wine from Charente Inferieure. BYE. C. MORIN (Compt. rend., 105, 1019--1022).-The composition of the brandy in 100 litres is as follows :-Aldehyde, traces ; ethyl alcohol, 50837 grams ; normal propyl alcohol, 27.17 ; isobutyl alcohol, 6.52 ; amyl alcohol, 190.21 ; furfuraldehyde and bases, 2.19 ; fragrant oil, 7-61 ; acetic and butyric acids, traces ; isobutylenic glycol, 2-19 ; glycerol, 4.38. There is no normal butyl alcohol, and ainyl alcohol constitutes five-sixths of the higher alcohols, The fragrant oil is one of the con- stituents to which the wine owes its bouquet. (Compare Abstr., 1887, 714 and 746.) C. H. B. Production of Normal Amy1 Alcohol by the Fermentation of Glycerol by Bacillus Butylicus. By E. C. MORIN (Con2pt.rend., 105, 816-818) .-When glycerol undergoes fermentation by BLicJZus bzctyEicus under the conditions determined by Fitz, 4 per cent. of the alcohols formed is normal amyl alcohol, boiling at 137-138" ; refrac- tive index at 13.5" for D = 1.414. It is worthy of note that all the alcohols produced by B. b?&yZicus are normal. C. H. B. Action of Zinc Methyl on Valeraldehyde. By J. KUVSINOFF (Chem. Centr., 1887, 987-988, from J. Buss. Chem. SOC., 1887, 204). Methyl isobutyZ carbinol is produced when zinc methyl is added to well-cooled valeraldehyde, and the product of the action decomposed with ice-water. It is a light, mobile liquid, boiling at 130°, sp. gr. 0.8271 at 0" ; its acetate boils at 147", sp. gr. = 0.8805 at 0" ; its ketone boils at 116- 116.5", and on oxidation yields isopropylacetic, isobutyric, acetic, and formic acids, and is therefore identical with methyl isobutyl ketone. V.H. V. Action of Zinc Isoamyl and Zinc Isobutyl on Aldehyde, By E. SOKOLOFF (Chew,. Centr., 1887, 988, from J. Russ. Chem. Soc., 1887, 197--204).-When zinc isoamyl is added to aldehyde, kept cool, and the resultant product decomposed with ice-water and distilled, methyl isoamyl carbinol is obtained besides isopropylethylene, and e thy I and isoamyl alcohols. The first yields an acetate boiling at 166-168", and a ketoite boiling a t 143-145", which yields on oxidation isopropyl- acetic acid. Zinc isobutyl when treated in like manner yields iso- butyl and ethyl alcohols. V. H. V. Methyl Isopropenyl Carbinol. By J. KONDAKOFF (Chem.Centr., 1887, 981, from J. Russ. Chem. SOL, 1887, 336).-When treated with a 6 per cent. hydrochloric acid solution, methyl isopropenyl carbin01 is converted into the isomeric trimethylethylene glycol. The readiness with which this change is effected is dependeut on the126 ABSTRACTS OF CHEMICAL PAPERS. atomic arrangement; this has also been observed in the case of unsaturated acids. V. H. V. Iodide of Starch. By H. B. STOCKS (Chem. News, 56, 212- 213).-The author takes exception to the four points set forth by I?. Mylius (Abstr., 1887, 568), and makes the following remarks on each point. (1.) He states that iodide of starch is producd by the action of solutions of pure iodine, or of the vapour of iodine, on moist starch. (2.) That a limited amount of chlorine produces the blue colour in mixtures of hydriodic acid, or of an iodide, with starch ; but that excess of chlorine destroys the colour, probably by the formation , of a colourless chlorine compound of starch and iodine chloride. (3.) Silver nitrate does decolorise the iodide by removing the iodine as silver iodide, t.he colour being reproduced on the addition of either iodine or hydriodic acid ; the action in the latter case may, however, be assumed to be due to iodine set free by the nitric acid liberated from the silver nitrate. (4.) Aqueous solutions of iodine do produce the blue colour with starch. Water is necessary for the production of iodide of starch ; there- fore solutions of iodine in absolute alcohol do not colour dry starch blue.The blue iodide is destroyed by heat, the iodine being, in open vessels, partially volatilised, partially converted into hydriodic acid ; in closed vessels, on the other hand, it is entirely converted into hydriodic acid.This decomposition is quick or slow according as the qnantity of iodine is smaller or greater. By adding iodine to it solution decolorised in this manner, the blue colour is again formed, and this decolorisation and recolorisation may be frequently repeated with the same starch. Exposure to sunlight also decolorises iodide of starch. Iodide of starch is not affected by alcohol, ether, benzene, or carbon bisulphide ; in fact, iodine may be removed from its solutions in the last two solvents by means of starch-paste. Iodide of starch disfiolves to a certain extent in water, and is pre- cipitated from the solution by absolute alcohol, by dilute hydro- chloric, sulphuric, and nitric acids, by strong hydrochloric acid, and by salts which do not react with it, such as sodium chloride.Strong nitric and strong sulphuric acid decompose it. Starch solutions are not precipitated by dilute acids like the solution of the iodide. D. A. L. Constituents of Rice-starch. By L. SOSTEGNI (Chem. Celztr., 1887, 896, from, Stud. d i Chim. Agr. di Pisa, 6, 48--68).-The results quoted of the amount of dextrose obtained by the saccharification of starch accord with those of Salamon. In the course of the prepara- tion of starch cellulose by Schulze's method, a fat melting at 47- 48" was extracted ; the crude fatty acids obtained therefrom melt at 50-51" ; the proportion of fat found was 1.5 to 20 per cent.csf the cellulose. The portion of residue, insoluble in ether, obtained in the saccharificntion of starch, differs from cellulose by its solubility in a 2 per cent. solution of potash, and its partial decomposition when warmed. From its solut.ion, acetic acid precipitates an amorphous substance, turning brown in the air, soluble in Schweizer's reagent when moist, but not when dry; it is decomposed when boiled withORGANIC CHEMISTRY. 1 2 1 hydrochloric acid, The author regards starch cellulose as a mixture of cellulose with the derivatives of the latter aubstance or a modi- fication of granulose. Lichenin. By M. H~NIG and S. SCHUBERT (Monatsh., 8, 452- 465) .-As there was considerable doubt whether the carbohydrate from Iceland moss (Cetruria islandica) was a single substance or a, mixture of two or more, the authors have reinvestigated it.The dried and sorted moss was treated repeatedly with a 1 to 2 per cent. solution of K2C03. A pale-green mass quite free from the original bitter taste was thus obtained. This was then boiled for some time with water and filtered through linen. The filtrate on cooling deposited a gelatinous precipitate, which separated better when the solution was frozen. The liquid still contained some of this gelatinous substance, together with an easily soluble starch. The gelatinous precipitate, for which the authors propose to utilise the name Zichenin, previously used for the whole extract, is very sparingly soluble in cold water, but dissolves in boiling water to an opalescent solution, which is at once cleared by the addition of a little potash.The greater part is pre- cipitated from its solutions on cooling, or on the addition of alcohol. It is not colonred by iodine. When heated with dilute sulphuric acid, it very readily yields a crystalline dextrose, which gives a, rotation [ a]j = +55.52", and closely resembles, if it is not identical with, ordinary dextrose. The intermediate dextrin-compounds are tasteless and non- rotatory. The above-mentioned soluble carbohydrate, for which the authors propose the name Zichelz-starch, could not be obtained free from lichenin. It is strongly rotating, the rotation increasing the freer the starch is from lichenin. It is easily soluble in water, but is thrown down 8s a flocculent precipitate by alcohol.The highest rotation obtained was [a]j.= +102.82". It is coloured blue by iodine. Diastase converts it readily into a dextrin showing rotation [a]j = 162.44". Lichenin is not affected by diastase. Lichen-starch, therefore, appears to be a soluble, unorganised modification of ordinary starch. L. T. T. V. H. V. Reactions of Chloral. By 0. REBUFFAT (Qazzetta, 17, 406-409). -Chloral and sodium acetate, in presence of acetic anhydride, do not react in accordance with Perkin's reaction; the change is for the most part more profound, leading to the destrnction of the molecule of chloral. Sodium acetate at a low temperature combines directly in equimolecular proportions with sodium acetate to form it compound, C2CI3HO,C2H3O2Na, which is white and minutely crystalline ; it is decomposed by water and by alcohol to form chloral alcoholate. Experiments were also made with the anhydrides of other fatky acids, but without success.V. H. V. Trithioacetaldehydes. By W. MARCKWALD (Bey., 20, 281 7- 2818 ; compare Abstr., 1886, 864).-yTrithioacetaldehyde, when mixed with four times its weight of ethyl iodide and allowed to remain in a closed vessel for some weeks, suddenly undergoes conversion into a crystalline mass of the &derivative. This change is not due to128 ABSTRACTS OF CHEMICAL PAPERS. the presence of free iodine in the ethyl iodide, since the change does not take place when an ethereal solution of the y-aldehyde contailling a, small quantity of iodine is similarly treated.w. P. w. Metallic Derivatives of Acetylacetone. By A. COMBES (Compt. rend., 105, 868-871).-The author has previously shown that acetyl- acetone has the constitution CH,Ac.COMe, and that the hydrogen of the Cf-Tz-group is readily displaced by chlorine or by sodium. Acetylacetone and its homologues act on metallic salts like true acids, and yield a new series of crystalline compounds of the general formula M(C5H7O2),, in which M is a metal with a valency n. The sodium and potassium derivatives form white, hexagonal prisms belonging to the rhombic system, and are most readily obtained by adding the required quantity of sodium or potassium ethoxide to an alcobolic solution of acetylacetone. They are somewhat soluble in absolute alcohol, but are insoluble in ether.The magnesium salt is obtained by mixing acetylacetone with an excess of magnesium carbonate. There is rapid effervescence, and the filtered liquid when evaporated in a vacuum, deposits transparent, colourless, hexagonal prisms belonging to the rhombic system, which are anhydrous when dried at 125". The aluminium compound is formed in the preparation of acetylacetone, and is also obtained by the action of the latter compound on a slightly acid solution of aluminium chloride. It is insoluble in water, somewhat soluble in alcohol, but less soluble in ether. When the solution is concentrated, it deposits nacreous crystals of the same form as the preceding com- pound, but they are readily decomposed by heat. The copper salt is obtained in pale blue needles of the same form, when a somewhat concentrated solution of cupric acetate is mixed with a warm saturated aqueous solution of acetylacetone. The compound is insoluble in water, and in moderately dilute solutions the precipitation of the copper is complete.Larger crystals are formed when a dilute solution of cupric chloride is added to a boiling solution of acetylacetone. The crystals are anhydrous when dried at 125". Ferric chloride and acetylacetone yield a dark-red solution, the formation of which may be used as a test for the ketone, and when this is extracted with ether the red compound is dissolved. When the ether evaporates, the iron salt is deposited in bright-red crystals, similar in form to those of the ammonium salt. The lead salt is formed by the action of lead carbonate on the ketone, is soluble in water, and resembles the magnesium compound in its crystalline form.The sodium and potassium salts are, however, decomposed by hot water, with formation of acetone and an alkaline acetate, and the aluminum and iron compounds are not decomposed by ammonia in alcoholic solution. The sodium salt and methyl iodide yield a new derivative, meth?/E- mtylacetcme, boiling at 165", which has acid properties Rimilar to those of the original cornpound. It seems, in fact., that the group -cO.CHZ.CO- has the properties which characterise the group COOH, Acetylacetone behaves in fact like a monobasic acid.ORGANIC CHEMISTRY. 129 except that the two hydrogen-atoms cannot act successively. Salts of the type C,H,02M, in which M is a bivalent metal, have not yet been obtained, but the homologues of acetylacetone form salts of the type (C,H,RO,),M, in which R is an alkyl radicle, and M is a metal of valency n.By J. VOLHARD (Annalen, 241, 141--163).-Very good yields of a-brominated acids may be obtained by a slight modification of Hell's process (Abstr., 1831, 711). The action of the bromine and phosphorus on the acid, or preferably the crude anhydride, is carried OD in a flask provided with a reflux con- denser, instead of in sealed tubes. The bromine and the other ingre- dients must be free from moisture. The bromide is slowly dropped int.0 boiling water, in order t o convert it into the monobrominated acairl. The following compounds were prepared : a-monobromosuccink acid forms four-sided prisms, and melts at 159".The ethyl salt boils :It 15O-l6O0 under 50 mm. pressure, and tlhe methyl salt at 132-13c;" under 30 mm. pressure. a-Monobromosuccinic acid is decomposed by boiling with water, yielding furnark acid. a-BromopropiorLic& acid forms prismatic crystals melting at 24.5", and z-brornisovaleric acid melts at 40°, and distils at 230" with slight decomposition. C. H. B. Preparation of a-Bromo-acids. w. c. w. Ethereal Salts of Aldehydo-acids. By W. WISLICENUS (BPT,, 20, 2930--2934).-When a mixture of ethyl acetate and ethyl formate is added by drops to twice the amount of ether in which sodium is placed, and the product decomposed by dilute sulphuric acid, an oil is obtained which gives an intense blue-violet coloor with ferric chloride, and reacts with phenylhydrazine.The compound is probably ethyl formyZacetate, COHGH2*COOEt. It could not be purified; when kept in a desiccator, crystals of ethyl trimesate melting at 133", separate. The yield of the latter is better than that obtained by Piutti's method (Abstr., 1887, 491). Ethyl pheizylfornz ylacetafe, COH*CHYh*COOEt, is prepared by sus- pending dry sodium ethoxide in absolute ether (3 parts), adding a mixture of ethyl phenylacetate and etliyl formate, and keeping the whole for several days in a closed vessel. The product is shaken with water, being kept cold with ice, and the aqueous solution is treated with sulphuric acid and extracted with ether. The ethereal extract is washed, with soda, filtered, and freed from ether in a vacuum, The residue, consisting of a crystalline substance and an oil, is filtered, and the oil distilled in a vacuum.If boils at 144-143" under 16 mm. pressure, When boiled with dilute aqueous soda, i t is &corn- posed into phenylacetic and formic acids ; the free acid could not be obtained. The alcoholic solution of the ethereal salt gives a very intense blue-violet coloration with ferric chloride. It reacts readily with phenylhydrazine, with formation of the compound this cryatallises in plates melting at 195-196", and is soluble in alkali, sparingly soluble in ether. BOL. LTV. k130 ABSTRACTS OF CHEMICAL PAPERS. The crystalline compound obtained in the preparation of ethyl phenylformylacetate is readily purified by crystallisation from ether ; i t has the same composition as ethyl phenylforniylacetate ; it gives no colour reaction with ferric chloride.The liquid isomeride chanps slowly a t the ordinary temperature into the crystalline compound, but the change is immediate at the melting point of the crystals, 69-71'. The crystalline compound is also decomposed by alkali into formic and phenylacetic acids. Ethyl rnethy Iformylncetate, COH.CHMe*COOEt, is a colourless oil, of agreeable odour, and boils a t 160-162" ; it gives an intense red- violet coloration with ferric chloride, and yields a pyrazoline-deriva- tive with phenylhydrazine. The above ethereal salts are derivatives of the half-aldehyde of maIonic acid which v. Pechmnnn assumed (Ber., 17, 936) to exist as an intermediate product in the synthesis of cumalinic acid.N. H. M. Conversion of Benzene-derivatives into Fatty Cornnounds by the Action of Chlorine in Alkaline Sol&ion. -By A. HANTZSCH (Ber., 20, 2780-2795).-When phenol (at most 50 grams) is dissolved in a moderate excess of aqueous soda (sp. gr. = 1-12>, and the solution, after dilution with 2 to 3 times its volume of water, is treated at 0" with chlorine, the colour changes through green to brown, and a liquid or semi-solid brown mass separates; this dissolves on the addition of more alkali, but, subsequently the solution slowly deposits a grey or black powder insoluble in alkali, and finally by alternating the addition of chlorine and alkali a point is reached, indicated by the dull-yellow colour of the solution, beyond which chlorination must not be carried.After precipitation of trichloro- phenol by hydrochloric acid, a compound, tvichlorodihydroxyarnenyl- carboxyzic acid, CaH5CI304, is extracted by ether from this solution, and is obtained by caut'ious evaporation of the ether as an oil, which is best purified by heating it with aqueous ammonia, recrystallising the ammonium salt, decomposing this with sulphuric acid, extracting with ether, and repeatedly recrptallising from water. The acid crystallises in slender, white needles, which are anhydrous, and melt at 1'76-177" with complete decomposition ; once, however, large, efflorescent, seemingly monoclinic crystals containing 4 mols. H,O were obtained. It has a sour and yet distinctly sweet taste, is unaltered by exposure to the air, dissolves readily in water, alcohol, and ether, and when boiled in aqueous solution decomposes with evolution of hydrogen chloride.Under the conditions given, the yield of the acid was 50 per cent. The acid is monobasic, and the ammonium salt, CsH4CI3O4-NH, + 2Hz0, is the most characteristic compound ; this crystallises in lustrous, rhombic prisms, has a neutral resction and very sweet taste, is sparingly soluble in water with partial decomposition, and is not rendered anhydrous by exposure over sulphuric acid or by heating; it decomposes at 123". The remaining salts are readily soluhle with the exception of the mercurous salt, which crptallises in stellate gronps of needles, and is converted into a dense, white, microcrystalline powder by heating with water. Concentrated alcoholic potash completely decomposes the acid withORGANIC CHEMISTRY.131 the formation of chloride and carbonate. The methyl salt, CsH4C1304Me crystallises in needles, melts at 126", and is insoluble in water. The acid does not form derivatives with hydroxylamine and phenyl- hydrazine, but yields with acetic anhydride a diacetyl-derivative, C,H,Cl,04Ac2, which crystallises best from acetic acid, melts a t 188- 192" with complete decomposition, and is insoluble in cold water. When the acid, or better its ammonium salt, is treated with zinc- dust and ammonia, or preferably with sodium-amalgam, and the product after acidification is extracted with ether, dichlorodiliydroxy- 17 menyZcarBozyEic acid, C,E,CI,(OH),*COOH, is obtained. This very closely resembles the trichloro-acid, and melts at 176-177"; it differs from it, however, by readily crystallising in large, lustrous prisms, by yielding an ammonium salt which does not crystallise well and melts a t 185", and by forming an acetyl-derivative melting at 132- 134".Concentrated aqueous soda converts the acid into a sodium d t , C6H,~O4Na2 + 6H20, crystallising in canary-yellow needles. The corresponding acid could not be isolated, but salts were prepared, and these, with the exception of the copper salt which is green, am yellow. The sodium salt gives with ferric chloride a brownish-yellow precipitate, which dissolves in excess of the reagent to a dark- green solution. The salt is unst~ble and decomposes on heating with water, the solution becoming alkaline, whilst mineral acids, even in the cold, destroy its colour, and convert ih, with the evolution of carbonic anhydride, into a white, microcrystalline acid of the com- position C,H,CIO,.This subst'ance is very unstable; it melts at 96- 97" with complete decomposition into a carbonaceous mass, and is sparingly soluble in water, soluble in alcohol and ether, yielding solu- tions from which, with the exceptiou of the last, the compound cannot again be obtained by crystallisation. The salts are intensely coloured ; the sodium salt, C,H4CIOzNa + 3H20, which can also be obtained from dichlorodihydroxyamenylcarboxylic acid by heating with con- centratpd aqueous soda at loo", is readily soluble in water, very sparingly soluble in excess of aqueous soda, and crystallises in scales. With regard to the constitution of these derivakives.the formula, CH,Cl*C( OH):CCl*C( 0H):CClCOOH is ascribed to the cornpound C6H5C1304, termed trichlorodi hydroxynmenylcarboxylic acid. In sup- port of this view, it is urged that, together with the acid, the symmetrical trichlorophenol [OH : C1: C1: C1= 1 : 2 : 4 : 61 is always obtained, and that the acid can be readily prepared from this trichloro- phenol under conditions similar to those employed in the case of phenol, 10 grams of trichlorophenol yielding 7 grams of the ammonium salt of the acid. It is probable, therefore, that the further action of chlorine in a1 kaline solution causes the beti mne-ring in trichlorophenol to break at the point 1 : 2 or 1 : 6. To dichlorodihydroxyamenyl- cerboxylic acid is assigned the constitution CH,Cl*C( OH>:CCl.C(OH):CH.COOH.The compound c6H,c104 derived from it is the carboxylic acid of the compound G5H,C1O2, which despite its acid character is not a true acid, since it does not yield an ethyl salt either by treatment in alcoholic solution with hydrogen chloride, or by the action of ethyl 362132 ABSTRACTS OF OHEMICAL PAPERS. iodide on its sodium salt. With bromine, it does not form additive but only substitution derivatives ; ammoniacal silver nitrate and cuprous chloride are not precipitated by it, and its sodium salt, when treated with phenylhydrazine acetate, yields an amorphous pheqyl- hydrazide, whose composition approximates to that required by the formula CsH,C1(N2PhH),. The formula CHC1'Co>CHCOOH and <co CHCI*CO CH2>CH,, <CO-CH2 - are ascribed to the two compounds, which are termed chloro- dibeto~erLtamethylenecarboxylic acid and chlorodiketopentamethyEene respectively, and the analogy between these and derivatives of tbe similarly cons titu ted dike tohexame t hylene- derivatives is pointed out in the paper.It has not been found possible as yet to displace the remaining chlorine-atom in chlorodiketopentamethylene, but it is possible to simultaneously withdraw all the chlorine from trichlorodihydroxy- amenylycarboxylic acid. When the acid, or preferably its ammonium salt, is treat,ed with a considerable excess of concentrated baryta- water, and heated t o about 60°, barium diliydrox yd~~eto~entumethyle?Le- cnrbosylccte, C6&06B% + 4H20, separates as a bright-yellow powder, insoluble in water.This salt effervesces on the addition of acetic acid, and is converted into the barium salt of dihydroxydiketopenta- metltylene, C,H404Ba + 3iH20, which very closely resembles the pre- ceding salt. Dihydroxydiketopentamethylene could not be prepared i n the pure state ; i t is obtained as a yellow oil from the barium salt by treating i t with hydrochloric acid and extracting with ether, and shows at first it tendency to crystallise, but very rapidly decomposes. It dissolves readily in water, reduces silver nitrate, and yields a com- pound with phenylhydraxine. The formulae are =signed to dihydroxydiketopentamethylene end its carboxylic acid respectively. Trichlorophloroglucinol on treatment with bargta yields neither the bricbloro-acid nor any of its decomposition products, whilst phloroglucinol and the t h r e e dihydroxybenzenes, when treated in a, similar manner to phenol, do not yield crystalline ammonium salts, but only acid syrups, which on reduction with zinc-dust and ammonia give monochloracetic acid in large quantitty, but no dichlorodihpdroxy- amenylcarboxylic acid.Bromine, under precisely similar conditions to the above, does not a& on phenol further than to produce tribrornophenol. Derivatives of Isosuccinic Acid. By G. KORNER and A. MENOZZI (Gazzetta, 17, 425441).-1n continuation of a former paper on a-amido-isosuccinic mid, or a-isoaspartic acid (Abstr., 1887, 80 L), the salts are more fully described. The sodium salt, C,H6N04N4 crys- tallises either in needles with 1 mol. H20 from concentrated solutions, or ia prisms with 4 mols.H,O in large, transparent prisms. The potas- w. P. w.ORQANTC CHEMISTRY. 133 sium salt is anhydrous. The calcium, magnesium, zinc, cadmium, lead, copper, and silver salts are described, as also the compounds it forms with hydrochloric and nitric acids. The methyl salt, formed from methyl iodide and the silver salt, crystallises in white needles ; when the potassium salt is heated with methyl iodide, the betazne potassio- iodide, C4H,NMe3O4KII,iH,0, is produced ; it is rery hygroscopic, and forms an atwochloride, C4H5NMe3C104,AuC13, a yellow, insoluble pre- cipitate. Amido-a-isosuccinamic acid, or a-isoasparagin e, NH,*CMe( CONHJGOOH, obtained by heating the neutral amide with aqueous ammonia in sealed tubes, forms crystals with hexagonal base, more solubie in cold than in hot water ; it forms a copper salt, (C4H7NZO3),Cu, crystallising in small tables.Amido-a-isosuccinamide, N H2*CMe (CONH,),, obtained by heating pyruvic and hydrocyanic acids, and treating the resultant product with alcoholic ammonia, crystallises in tables with a rhombic base, sparingly soluble in cold, readily in hot water. When boiled with barium or potassium hydroxides it gives for each molecule two mole- cules of ammonia; it is decomposed only to a slight extent by magnesia. Its hydrochloride, sulphate, and nitrate cryatallise in prisms, and are very soluble in water. V. H. V., Oxidation of Copaiba, Balsam. By S. LEVY and P. ENGL~DER (AvLnaZen, 242, 189--214).-The most important facts contained in this paper have already a.ppeared in this Journal (Abstr., 1886, 250).The unsymmetrical dimethylsuccinic acid obtained by the oxidation of copaiba balsam is identical with the acid described by Barnstein ( t h i s vol., p. 135). The acid forms triclinic crystals [ a : b : c = 2.0294 : 1 : 1.1909 ; a = 118" 36', p = 95" 16', 7 = 101"). 'l'he barium salt, C6H,04Ba -t 2$H,O, is monoclinic [a : b : c = 1.6006 : 1 : 1.709 ; = 97" 26'1. The salts of calcium, C6H804Ca + H,O, and ammonium, c6 H804(NH,), and C6H9U4*N H p , are crystalline. The nornid sodium salt, C6H6OlNa2 + llHzO, forms silky prisms, and the acid Lalt, C,H90,Na + 3+H20, monoclinic prisms, a : b : c = 1.83653 : 1 : 4.18006 ; /3 = 90" 43'. The anhydride of dimethylsuccinic acid melts at 29". It unites with phen y 1 hydrazine, forming dime thy lsucciny lphen y 1 hy drazine, a corn- pound crystallising in monoclinic plates [a : b : c = 1.05521 : 1 : 0.82996; p = 99" .57'].The h i d e of dimethylsuccinic acid melts a t 106". w. c. w. It melts a t 131-132". Dibromosebacic Acid and some of its Derivatives. By A, CLAUS and T. STEINKAULER (Ber., 20, 2882-2889) .--Dibromosebacic acid, C,,H,,Br,O,, is prepared by heating sebacic acid and bromine (2h rnols.) at 160-170" for about three hours. The oily product solidifies after some hours to a crystalline mass which is freed from adherent oil by suction on porous plates. It crystallises from water i n long, feathery needlea melting at 115" (uncorr.), and is readily soluble in134 ABSTRACTS OF CHEMICAL PAPERS.alcohol, ether, chloroforrii, and benzene, sparingly soluble in boiling water. Prolonged boiling with water decomposes the acid and its salts with elimination of hydrobromic acid. Snlphuric acid dissolves it unchanged. The sodiwn salt, CloHl4BrzO4Na?, is a heavy white, crystalline substance, very readily soluble in water, from which i t crystallises with 3 mols. H20. The hydrogen potassium salt is almo~t insoluble in cold water; the barium (with 2 mols. H,O), cakiunc (with 2 mols. H20), lead, silver, copper, and ammonium salts were also prepared. The methyl salt crystallises in small, lustrous, rhombo- hedric plates melting at 50" ,(uricorr.) ; the ethyl salt is a thin oil. Hydroxysebaceic acid, C,oH,,05, is prepared by boiling sodium di- bromosebate with water, .evaporatiug to dryness on a water-bath, digesting over sulphuric acid, and extracting with absolute alcohol.The filtrate is neutralised with alcoholic soda. The sodium salt so obtained is converted into the insoluble lead salt which is then decom- posed with hydrogen sdphide. The acid is readily soluble in hot water and in cold alcohol, from which it Reparates in small crystalline grains melting at 143" (uncorr.) ; i t is very sparingly soluble in ether, in- soluble in benzene and chloroform. The sodium salt, CIOH1105Na2, forms a white, sandy powder very readily soluble in water. Dikydroxysebucic acid, C1OHIBO6, is obtained by boiling an aqueous solution of dibromosebacic acid with freshly precipitated silver oxide ; the product is filtered, treated with hydrogen sulphide, and evaporated to a syrup ; this becomes crystalline when kept over snlphuric acid.It is very readily soluble in water, alcohol, and glacial acetic acid, sparingly soluble in ether, insoluble in benzene and chloroform ; it melts a t 130" (uncorr.) and is decomposed a t a higher temperature. I t is optically inactive. The sodium salt, CloH~B06Na2, is very soluble in water. N. H. M. Constitution of Levulinic and Malei'c Acids. By A. MrCHAEL (Amer. Chem. J., 9, 364--372).-The reactions trought forward by Anschiitz (Abstr., 1687, 916) in favour of the new constitutional formula suggested by Iloser for rnalei'c and levulinic acids are ex- amined. It is shown that by assumiug certain reactions for ketones or for aldehydes similar in kind to those already known, the syntheses and tran,sformations of these two acids and also of several others such as their acetyl-derivatives, mucobromic acid, the dibromo- succinic acids, &c., are quite as easily explained by the old formulae as by the new ones of Roser.H. I?. Butenyltricarboxylic and Ethylsuccinic Acids. By G. POLKO Awnalen, 24 2, 113-1.26) .-kA7thy1 butetr y l tricarboxy late, is prepared by adding 48 grams of ethyl malonate to a warm solution of 6.9 grams of sodium in 77 grams of alcohol ; 48.5 grams of ethyl a-bromobutyrate is added to the product. It is a pale-yellow liquid boiling between 271" and 281". Its sp. gr. is 1.065 compared with water at 17". The free acid is soluble in water, alcohol, ether, and acetone. The It melts at 119", and begins to decompose at 124".ORQANIO CHEMISTRY.135 barium salt, Bn3(C7H70,)2, and silver salt, Ag3C7H70s + 1+H20, are amorphous. The normal calcium salt, Ca3(C5H706)2, is very hygro- scopic. The acid salts, CaHa(C7H706)2 and CaH:(C7H7O6) + 2iHz0, are crystalline and insoluble i n alcohol. The zinc, strontium, and potassium salts are amorphous. E t h y Zsuccinic a,cid, COOH*CHEt*CH,*COOH, is prepared by dis- tilling butenyltricarboxylic acid. It is also formed in the saponifica- tion of ethyl butenjltzicarboxylate. It melts a t 97" and is identical with the a-ethylsuccinic acid described by Huggenberg (Abstr., 1878, 782). In addition to the salts described by Huggenberg, the crystalline strontium salt and the methyl salt were prepared. The latter boils at 202-205". The anhydride remains liquid a t -19".Its sp. gr. a t 34O is 1.165. The amide melts a t 214" with decomposi- tion. It is insoluble in cold water and in alcohol. w. c. w. Isobutenyltricarboxylic Acid and Unsymmetrical Dimethyl- succinic Acid. By F. BARNSTETN (Annulen, 242, 126-140).- E t h y l isobiLten,yltricail.boxy h i e , COOEtCMe,.CH( COOEt,)?, is pre- pared by the action of ethyl a-bromisobutyrate on ethyl sodiornalonate in alcoholic solution. It boils at 272--275", and its sp. gr. is 1.064 compared with water a t 17". The free acid is difficult to obtain i n the crystalline state. It is soluble in water, alcohol, ether, and acetone. On boiling the aqueous solution, carbonic anhydride is evolved. The acid melts a t 120" with decomposition, yielding un- symmetrical diniethylsuccinic acid.The sodium, magnesium, barium and silver salts of isobutenyltricarboxylic acid are amorphous. The potassium sait, K3C7H70, + 2H20, forms efflorescent prisms. The calcium salts, Ca3(C7H70& + 9Hz0 and Ca(CiH,06)2 + 'LH20, are crystalline. Unsymmetrical dill i eth y Zsuccinic acid, C 0 OH*CMe2*CH,*C 0 0 H, melts at 139", and is freely soluble in alcohol, ether, acetone, and in hot wat4er. The normal salts of the heavy metals and alkaline earths are, as a rule, very sparingly soluble in water. The noymal potassium salt is amorphous and deliquescent ; the acid salt, C6B904K + 5H20, crystallises in plates which effloresce on exposnre t o the air. The normal barium salt, C6H804Ha + 2H20, is crystalline; the acid salt is also crystalline, and readily soluble in water. The cadmium salt, C6H,0aCd + 6HzO, and the lead salt, C6H80aPb 4- H20, are crystalline, and dissolve with difficulty in water.DimethyZsuccinyZ chloride, CGH802Cl,, boils at 200-202". Diethyl dimethylsuccinate boils st 213-215". Its sp. gr. at 17" is 1.0134 compared with water a t the same temperature. The dimethyl salt boils a t 200" ; sp. gi;. 1.0568 at 16". Dimethybuccinic m- hydride boil8 at 215". Thiophen-derivatives cannot be obtained by the action of pbosphorus sulphide on unsymmetrical dimethylsuccinic acid. w. c. w. It forms acid and normal salts. Furfuran Derivatives. By W. MARCKWALD (Bey., 20, 2811- 2817; compare Abstr., 1876, ii, 444).-Furfuracrylic acid is best ob- tained by heating furfuraldehyde (1 part), sodium acetate (2 parts), and acetic anhydride (2 parts) at '250" for 11 hours ; the yield amouuts13G ABSTRACTS OF CHEMICAL PAPERS.to more than 80 per cent. of that theoretically possible. The ammo- nium salt of its reduction-product, f urfuropropionic acid, is converted i l l to fuyfuropropionamide, C6H70*CONH2, by heating for several hours in a closed tube at 220" ; this crystallises in white needles, melts at 98", distils a t 270" withont decomposition, is soluble in water, alcohol, ether, and benzene, sparingly soluble in light petroleum, and on treat- ment with bromine and aqueous potash does not yield the correspond- ing arnine, since the furfuran nucleus alone is attacked. When fur- furacrylic acid (1 part) is heated with 95 per cent. alcohol (3.5 parts) and saturated with hydrogen chloride, the ethyl salt of a bibasic acid, C.=,H80(COOEt)2, is obtained as an oil which distils a t 286" ; this is heavier than and insoluble in water, soluble in alcohol and ether in all proportions, and has a pleasant, aromatic odour and a very bitlter taste ; the yield amounts t o more than 80 per cent.of that theoretically pos- sible. When saponified, it yields the corresponding acid, C5Hlo05, which crystallises from water in large, colourless, transparent, thin prisms, melts a t 138", or with partial decomposition a t about 110" when heated for some time in an open vessel, and has a very bitter taste. On dis- tillation, it is converted into oily decomposition-products of partly acid and partly neutral character. The barium, calcium, zinc, and copper saltq were prepared ; the silver salt, C,H805Ag2, forms microscopic needles.Since the ethyl salt yields a phenyZhydranide, CIIH,,Oa : N*NHPh, the author ascribes to the acid the formula COOH*CH,*CH,*CO*CH2*CH2*COOH, and adduces the following evidence in its support; the acid is not reduced by sodium amalgam, does not form an additive compound with bromine, and on oxidation with dilute nitric acid is converted into succinic acid (the yield amounting to more than 40 per cent. of tbe acid employed), and a liquid fatty acid (? acetic or propionic acid). The acid is not acted on when heated a t 200" with hydriodic acid saturated a t 0", whilst addition of amorphous phosphorus leads to experimental difficulties which have not yet been surmoimtled. w. P. w.Action of Nitric Acid on Symmetrical Trichlorobenzene. By C. L. JACKSON and J. F. WING (Amer. Chem. J., 9, 348-355).-1n proving the constitution of benzenetrisulphonic acid (this vol., p. 152), it was found that with fuming nitric acid, symmetrical trichlorobenzene did not yield a mononitro-derivative melting af 68" (Beilstein and Kurbatow, Annnlen, 192, 233), but the dinitro-derivative melting at 130". I f sulphuric acid was used a t the same time, the trinitro- derivative was obtained. Whether a mono-, di-, OP tri-nitro-compound is obtained depends not only on the temperature and presence or absence of sulphuric acid, but also to a very considerable extent, on the purity of the acid employed, an acid of sp. gr. 1.51, free from nitrogen peroxide, being more effective than one of sp.gr. 1.534 con- taining much nitrogen peroxide. Trichlorobenzene (1 : 3 : 5) is best formed by the chlorination of di-ORGANIC CHEMISTRY. 137 chlormiline prepared by Witt's method (this Journal, 1876, i, 264). Tr~~F,lo1^odii~itrobenzene, C6EC13 (NO,),, is produced at the ordinary temperature by the action of nitric acid of sp. gr. 1.505 on trichloro- benzene. It crystallises from alcobol in white prisms melting at 129.5". The mononitro-compound is readily obtained by boiling with nitric acid of sp. gr. 1-46. TricltZorotrirLirrohe?zzene, C6Cl,( NOJ3? is prepared by using a mixture of fuming sulphuric acid and nitric acid of sp. gr. 1.505. It crystallises from alcohol in nearly white needles melting at 187". Action of Sulphuric Acid on Bromodurene.By 0. JACOBSEN (Rer., 20, 2837-2840) .-When bromodurene is treated with eight times ita weight of sulphuric acid a t the ordinary temperature, and the mixture allowed to remain for 10 to 12 days, a thick brown liquid is obtained, which, on the addition of ice and subsequently of water, yields a residue consisting chiefly of dibrornodurene, together with hexamethylbenzene and unaltered bromodurene. The aqueous solution was free from halogenated sulphonic acids, but contained at least three sulphonic acids, one of which on hydrolysis yields prehnit- ene, whilst the other two yield pseudocumene. From these results, the author concludes that sulphuric acid acts in this case as a bromine- carrier, converting the bromodurene into dibrornodurene and d urene (compare Neumann, Abstr., 1887, 573), the latter of which in the presence of sulphuric acid yields psendocumene, prehnitene, and hexamethylbenzene in the manner already described by him (Abstr., 1887, 660).Dibrornodurene, under similar conditions, is not acted on by sul- pliuric acid. Probably sulphuric acid acts as a bromine-carrier when in its presence bromobenzene and paradibromobenzene are converted into di bromobenzenesulphonic acid and a mixtare of tetra- and hex+ bromobenzene respectively, as observed by Herzig (Abstr., 1882, 46). The author has also found that dibromometaxylene, [Me : Me : Br : Br = 1 : 3 : 4 : 61, when treated with chlorosulphonic acid, yields the chloride of its sulphonic acid together with a considerable quantity of tetrabromometnxylene, although but a small quantity of the latter results when the same dibromometaxylene is heated with sulphuric acid at 240°, an isomeric liquid dibromometaxylene being the chief Aniline Salts.By A. DITTE (Compt. rend., 105, 813-816).- Aniline rnoZytdutP, 2NH2Ph,3Mo0,,5B,O, forms hard, brilliant, trans- parent, prismatic crystals, which lose water when gently heated, and decompose at a higher temperature. It is obtained by mixing a warm concentrated solution of ammonium molybdate with excess of a con- cent'rated solution of aniline hydrochloride. Oily drops separate and rapidly change to a crystalline precipitate, and when t h i s is dissolved in hot water and the solution cooled, the salt crystalliaes in radiating groups. An dine tungstnte, ZNH,P h ,4Wo03,3H,0, analogous to ammonium metatnngstate, forms long, brilliant, transparent needles, which lose H.B. product in this cme. w. P. w.138 ABSTRACTS OF CHEMICAL PAPERS. water when gently heated, and at a higher temperature burn with a smoky flame leaving a residue of tungstic anhydride. When am- monium tungstate is mixed with a boiling solution of aniline hydro- chloride, no reaction takes place, but if aniline is added, a portion of i t dissolves, and when the still acid liquid is concentrated and cooled, the aniline tungstate crystallises. Three aniline vanadates can be obtained. Warm solutions of am- monium vanadate and aniline hydrochloride yield a red liquid, acid to litmus; when this is cooled, i t deposits yellow needles of the com- position NH,Ph,V,0,,4 H,O, which darken on exposure to light, and a t 100" lose water and become green with a metallic lustre, At a higher temperature, the snit blackens and decomposes.If a small quantity of aniline is added to the mixed solutions in the experiment just described, and the black precipitate which forms filtered off, a reddish-brown liquid is obtained, which after some hours deposits bril- liant, reddish-brown needles of the composition 4PhNHz,3Vz0,,18H,0. They lose water when heated, and decompose at a higher temperature. If aniline is added gradually in small quantities with constant agitation to a cold concentrated solution of equal equivalents of aniline hydrochloride and ammonium vanadate, small yellow crystals separate. The solution is diluted until these crystals dissolve, and aniline is added until it no longer dissolves.The liquid is then concen- trated over sulphuric acid, when the compound 2NH,Ph,VZO5,2H,O crystallises in large pale-yellow plakes mixed with reddish-brown crystals of the preceding compound. A n i l i n e iodate, NH2Ph,21a05, is obtained by mixing a cold almost saturated solution of' ammonium iodate with an excess of aniline hydrochloride. It forms brilliant, white, nacreous plates, which alter when exposed to light, but may be kept in the dark a t a low tempera- ture. When gradually heated, it at first seems to undergo no altern- tion, but below a red heat it detonates very violently. If ammonium cliiodate is used instead of the normal salt, decomposition of the salt begins a t the moment of its formation.A n i l i n e chlorccte is obtained in needles by mixing cold concentrated solutions of sodium chlorate and aniline hydrochloride. It is very unstable, and decomposes rampidly even in the dark a t 0". At. the ordinary temperature, it quickly becomes black, and detonates violently at about 20". Aniline boi-ate, NH,Ph,'LB,O3,4H2O, analogous to ammonium biborate, is obtained by mixing the ammonium salt with aniline hydrochloride, or more easily by adding aniline to a boiling saturated solution of boric acid, in which it is readily soluble. The filtered liquid when cooled first deposits unaltered aniline, and then unctuous, transparent, white lamellae, which lose water when heated, then in- tumesce and give off alkaline vapours,and finally take fire at a higher temperature.C. H. B. Homologues of Aniline and their Separation on a Large Scale. By 0. N. WITT (Chern. h d . , 10, 8--23j.-In the present communicatien, the author, ai'ter detailing the progress made in the manufacture of pure benzene, to1 uene, and xylene, since 1880, refersORGANIC CHE3l'ISTRY. 139 to the processes of separating the homologues of aniline on a com- mercial scale. The two nitrotoluenes are best isolated by freezing out part of the para-compound, and separating part of the ortho- derivatives by fractional distillation with steam. The medium por- tion is then reduced, and the toluidines thus obtained are subjbcted to a separation process, based on the fact that on treating a mixture of ortho- and para- toluidine with sulphuric acid insufficient in quantity to saturate both isomerides, the para-compound is first attacked.Hence on subjecting such mixtures to distillation, aided by the introduction of steam, a distillate rich in orthotoluidine is obtained. The latter may then be further purified by repeating the above treat- ment. The residual paratolnidine sulphate is neutralised with caustic soda or lime, and the base separated by distillation and re- crystallisation. The separation of para- and meta-xylidine may be effected by sulphonating both isomerides ; metaxylidinesulphonic acid is insoluble, whilst the acid from the para-componud is freely soluble, but yields an almost insoluble sodium salt, from which the base may be obtained by distillation with addition of a small amount of linie. To isoIate the base from the meta-acid, the latter is heated at 160- 180" uuder pressure with five times its weight of hydrochloric acid. The acid mixture is then saturated with soda or lime, and subjected to distillation with steam.D. B. Butylenic Bases : Characteristics of E thylenic Diamines. By A. COLSON ( C o n y t . rend., 105, 1014-1016).-10 grams of iso- butyiene bromide, boiling at i47-149", was heated to boiling for 10 minutes with 40 C.C. of aniline, the excess of aniline expelled by distillation in a vacuum, and the aniline hydrochloride removed by treatment with water. The residue was then dissolved in warm hydrobromic acid, and the crystals which separated on cooling were purified by washing with hydro bromic acid. Diphenylbutyienediamine hydrobromide, C4H8(C,H6N),,2HBr, is thus obtained in white crystals, which melt at 122" with decomposition.I t dissolves in five times its weight of boiling water, and 10 times its weight of cold water with partial decomposition, which is prevented if hydrobromic acid is present. It is about twice as soluble in alcohol as in water, but is not soluble in ether. The hydrobromide is decomposed completely by alkaline hydroxides with liberation of the base as a colourless oil, insoluble in water, but soluble in alcohol, ether, and chloroform. It has a bitter burning taste, and is coloured brown by nitric acid ; its sp. gr. is about 1.0. With hydrochloric acid it yields a hydrochloride crystailising in white nodules, which become blue when exposed to air, melt at 98", and dissolve in 10 times their weight of cold water with some.decomposition. With acetic acid, the base forms a viscous acetate which is soluble in water, and seems to be uncrystallisable. The aqueous solution of the base has no action on any indicator, and the alcoholic solution has no action on phthaleins, but decolorises methyl - orange. In this respect, it resembles ethylenediphenyl- diamine and ethyleneditolyldiamine, and hence i t would seem that secondary aromatic diamines containing ethylene a m distinguislied from primary amines such as aniline and toluidine, by the fact that140 ABSTRAOTS OF OHEMIOAL PAPERS. they are very feebly bmic, and do not act on phthaleins, but decolorise methyl-orange. The basic properties decrease as the molecular weight increases. When diphenylb~t~ylenediamine hydrobromide is treated with sodium nitrite at 0" it yields a nitroso-derivative in the form of a yellow precipitate which melts a t 90".C. H. B. Azopseudocumene. By V. POSP~CHOFF (Chem. Centr., 1887, 858 -859, from J. Buss. Chem. Xoc., 1887, 113-118).-Nitropseudo- cumene when reduced with sodium amalgam, yields azopseudocuni ene, N,( C6H3MeJ2, which forms yellowish crystals melting at 1'13-1 74", and may be sublimed without decomposition. It is sparingly soluble in alcohol, more readily in ether and benzene ; i t dissolves in concen- tratod sulphuric acid, but is reprecipitated on dilution. The corresponding hydrazo- derivative is obtained by reducing nit ropseudocumene with zinc-foil ; it melts at 124-125", and is readily oxidised in the air to the azo-derivative.In both cases, cumidine is obtained as a bye-product. V. H. V. Formation of Aniline Dyes by the Oxidation of Aromatic Amines. By J. BARZILOFFSEY (Chem. Cenfr., 1867, 855-657, from J. RIMS. Chena. Xoc., 1887, 132-149) .-By the oxidation of aromatic amines, azo-compounds and polycmines are formed ; by changing certain conditions, basic products are formed which play an important, part in the aniline dye industry. Jn order to throw some light on the nature of the chemical changes involved, the products of the oxi- dation of paratoluidine were investigated. The principal compounds formed are parazotoluene and azotolyl, C,,H,,N,, the latter of which may also be obtained from hydroparazotoluene by heating its alcoholic solution with concentrated liydrochloric acid, as also by the Oxidation of toluidine.The formahion of azotolyl by the oxidation of paratoluidine is explained thus : two atoms of hydrogen are removed from two molecules of toluidine with production of hydrnzotoluene, of which one part is converted into azotoluene by further oxidation, whilst the other part is transformed into the isomeric tolidine, which passes by oxidation into azotolyl. Azotolyl when heated with an alcoholic solution of ammonium snlphite is readily transformed into the corresponding hydro-derivs tiue, which differs from its analogues in readily combining with acids, and being separable on addition of alkalis. The hydrochloride, (C,H,,HCI) + l$HO, is colourless in the pure state, but when damp is readily oxidised to a compound, pararosotoluidine, which is also obtained by oxidation of a, dilute solution of paratoluidine witJh large excess of chromic acid, and subsequent addition of soda to the resultant product.V. H. V.ORGANIC CHEMISTRY, 131 Formation of Dyes by means of Hydrogen Peroxide. Bg C. WURSTER (Ber., 20,2934-2940).-Ammonia is added t o an emulsion of phenol and water so that a part of the phenol remains undissolved ; a solution of sodium carbonate and an equal volume of hydrogen peroxide are added, and the whole diluted with water. The mixture is well shaken, a crystal of a hydroxylarnine salt added, and the whole again shaken ; a bright-blue and then a deep-blue coloration is pro- duced which in a day or two changes to glseen. The dye which is extracted with ether is shown to be phenolqainonimide.Hydrogen peroxide is found in the sap of many plants ; it is also produced by micro-organisms, especially by the non-pathogenic. All the monatomic phenols of the benzene series examined, in which the para-position to the hydroxyl-group is free, gave quinone-imides with hydrogen peroxide and ammonia. Hydroxy-acids also yield dyes. Lacmo'id is formed when an arnmoniacal solution of resorcinol is boiled with a little hydrogen peroxide. If sodium carbonate is added to a mixture of resorcinol and quinone, a deep-green solution is obtained which, when shaken with air becomes yellow, then reddish-yellow and brownish-red ; when air is removed, the green colour is regenerated. A similar change of colour is observed in many leaves, especially those of Berberis which contain a considerable amount of hydrogen peroxide.Pyrocatechol, orcinol, and some plant constituents, such AS phlo- ridzin, also give dyes with hydrogen peroxide. Formation of Safranines. By P. BARBIER and L. VIGNON (COW@. rend., 105, 939--941).-1t has been shown that phenosafranine is formed by oxidising a mixture of paraphenylene diamine (1 mol.) and aniline (2 mols.), and it is known that amidoazobenzene yields paraphenylenedinmine on reduction. It therefore seemed probable that the action of nitrobenzene or amidoazobenzene in presence of some reducing agent evolving hydrogen, should yield phenosafranine, and this supposition is confirmed by experiment. Amidoazobenzene hydrochloride (1 mol.) is mixed with iron and hydrochloric acid in sufficient quantity t o yield one molecular propor- tion (H,) of hydrogen, and sufficient nitrobenzene to form a paste, and heated at 188" for three hours.The product is diluted with water, and treated with a current of steam to remove unchanged aniline; the aqueous solution is then mixed with ammonia, filtered, and the safranine precipitated by adding sodium chloride. The phenosafra- nine which separates is purified by repeated precipitation by means of salt and recrystallisation from hot water. Amidoazotoluene likewise yields a safranine when heated with nitrobenzene, and hence it seems that this constitutes a general reaction for the preparation of safranines. Nitro-derivatives of Oxanilide. By W. G. MIXTER and F. 0. WaurHm (Awzer. Chew. J., 9, 355--361).-Hnebner and Rudolph's work on paradinitro-oxmilide is confirmed.Tdranitrooxanilide, C,0a[NH*C&X3(NO~),jr [NH : (NO,)% = 1 : 2 : 41, is formed by the N. H. M. C. H. B.142 ARSTRACTS OF CHEMICAL PAPERS. action of red fuming nitric acid on oxanilide; it melts at 300°, is hut slightly soluble, and is eaqilp saponified bv weak potash. Hexa- nitro-oxan.iZide, C202[NH.C&L(N02)3]2 [NH : (NO,), = 1 : 2 : 4: 61,is ob- tained when a mixture of fEming nitric acid and strong sulphuric acid is employed ; it is the highest substitution product obtainable. It melts at 300", its best solvent is glacial acetic acid. When heated with sulphuric acid at 200", it yields a trinitraniline melting at 188", which is the melting point of the only known trinitraniline, NH,: (NO,), = 1 : 2 : 4 : 6.In alkaline solutions, it dissolves with formation of trinitrophenyloxanilide, trinitro phenol, and trinitraniline. Trilziti-ophelzZ/Zoxa~zide, NH,*CO*CO*NH*C,H, (NO,) 3, crystallises in white fibres, and melts with decomposition a t 255-260". It has strongly marked acid characters. The potassium and ammonium salts are described. H. B. Nitro-derivatives of Dibromoxanilide. By W. G. MIXTER and C. P. WILLCOX (Arner. Chem. J., 9,361-364).-Dinitrodibromoa?nnilide, C,0z(NH-C,H,Br.N02)2 [NE : NO2 : Br = 1 : 2 : 43, is obtained by the action of strong nitric acid on paradibromoxanilide. It is yellow, melts at 288", and when saponified yields orthonitroparabromaniline, melting at 111.4". Tetranitrodihromoza~nilide, C202[ NH*C6H2 (N02),Br J2, is obtained with some difficulty by using red fuming nitric acid.It is white, melts at 285-287", and does not yield dinitrobromaniline when saponified. H. B. Compounds of Alloxan with Aromatic Amines. By G. PELLIZZARI (G'azzatta, 17, 409-425) .-Alloxan combines directly with the aromatic aniines to form additive products from which, however, the base cannot be recovered as such. Thus when a concentrated boil- ing aqueous solution of alloxan is agitated with a-naphthylamine, and the solution cooled, a compound of the formula C,,H,,N,O, separates C4H2N20 + CloH7NH2 = Cl~HllN304. This compound, a-nccphthyZ- arnine-aZZoxan, ciystallises in transparent, colourless needles, insoluble in water, acids, aqueous ammonia, bct Boluble in ether, benzene, and chloroform ; i t is coloured greenish by concentrated sulphuric acid.When heated with alkalirj, it, dissolves, yielding ammonia and the potassium salt of an acid, CI~HION~O,; on acidification, the acid separates in long, glistening needles, insoluble in ether, benzene, and chloroform, but very soluble in alcohol. At 110", it loses the elements of a molecule of water, but takes it up again on recrystallisation from aqueous alcohol. PNaphthylamine apparently does not combine with a1 loxan. Aniline combines with alloxan to form pheny Zarnine-aZZoxam, C,,HgN304 = CpH,N204 + PhNH2, which crystallises in scales, decomposing at 248". It forms a hydro- chZoride, C10HgN304,HC1, which crystallises in transparent needlea, and a silver salt, CloHsAgN304, a white, insoluble powder. Like the naphthyl-derivative, it yields an acid, C9H8N303, when boiled withORGANIC CHEMISTRY.143 alkalis, thus : This acid crystallises in colourless needles which decompose a t 180" without fusion ; i t is soluble in alkalis and their carbonates ; its silver salt,, CgH,AgN,03, is a white crystalline precipitate. On dry distillation, phenylamine-alloxan yields parafol uidine. MetA?/ZphenyZu}iiine-aZZ~xan, Cll H,,N30, = C4HzNz04 + NHPhMe, crystallises in white scales soluble in alcohol, moderately soluble in boiling water ; its hydrochloride, CllHllN304,HC1, forms colourless prisms. Uimeth?/Z~ihenyZamine-aZZoxan, C1,H,,N3O3 + HzO, crystallises in colour- less needles, sparingly soluble in water, and decomposing at 230". Its hydrochEoride crystallises i n transparent needles, the nitrate in lozenge- shaped crystals, the ozaZate in quadrangular tables ; the silver salt is a white precipitate.This compound, like the preceding, is decom- posed by alkalis with formation of an acid. To these derivatives, of which that of aniline is selected as a typical example, the author ascribes either the formula CloH9N304 + HZO = CgH&N,O, + NH, + CO,. or COOH*NHCO*C(CONHz) C,H,*NHz, of which the latter illus- trates a t once the basic and acid character, as also its decomposition by alkalis to form an acid, C9H8N203, by elimination of ammonia and carbonic anhydride, thus : COOH*NH.CO(CONH2) : C,H,-NH, + H20 = COOH.C(CONH2) On the other hand, the combination of the benzene nucleus with another grouping by two of its carbon-atoms is unusual. The other formula illustrates the formation of paratoluidine by the dry distillation of the aniline compound, whilst the production of the acid compound is explained as a result of two successive reactions, in the first of which a carboxylic acid is formed which subsequently gives oEa molecule of water to produce an imide, thus : CO<NH.co NH.co>C(OH)mC6H4*NH, + 2Hz0 = COOE*C(OH)(CONH2)*C,H,*NH2 + CO, + NH,, and (ii) COOH*C(OH)(CONH2).CJ&*NH4 - OHz = C,H,*NH, + NH3 + COs.NH<::> c (OH)GH.NH,. If the latter formula be correct, then the above compounds might be considered as derivatives of dialuric acid or tartrony 1 carbamide. Benzylidenephthalide and Isobenzalphthalide. By . 8. GABRIEL (Ber., 20, 2863--868).-Benzylidenephthalide crystalhses in small, monoclinic forms ; a : b : c = 1.9005 : 1 : 2.3830 ; p = 76" 2-5'.Benzylphthalimidine (Abstr., 1885, 902, 1229) is readily obtained by adding a mixture of benzalphthalimidine (12 grams) and amorphous phosphorus (6 grams) to 36 C.C. of boiling hydriodic acid (b. p. = l27'), and subsequently heating for 45 minutes in a reflux apparatns. The yield amounts to 80 per cent. of that theoretically possible. When treated with phosphorus oxychloyide, V. H. V.144 ABSTRACTS OF CHEMICAL PAPERS. and heated on a water-bath until hydrogen chloride ceases to be evolved, a product is obtained which, after extraction with water, solution in alcohol, and precipitation with ammonia, crystallises from benzene in orange- or cinnabar-red, slender needles of the composition CIBHIIN.This compound is soluble in chloroform, but only very sparingly in alcohol, has feeble basic properties, arid forms unstable purple salts which are soluble in alcohol, and could not be amalysed with the exception of the picrnte, C,H2,N50,, a salt crystallising in cantharides-green prisms appearing reddish-violet by transmitted light,. Phthalimidine also yields with phosphorus oxychloride a black powder having a bronze lustre; this is insoluble in all ordinary reagents and dissolves in sulphuric acid with a dark blue colour. When isobenzalphthalide is heated with methylamine and alcohol f o r nine hours a t lOO", it is converted into P-desoxybenzoilzca~box~Z- methylamide, C0Ph.C Hz*CaH,*CO-NMeH ; this crpstallises from ben- zene in snow-white, matted needles, melts at 14-14Ao, and when heated a t 200" is converted into its constituents.Nitrobenxylidenephthalide, on reduction with hydriodic acid and amorphous phosphorus, yields in addition to isobenzalphthalide a white powder ; this cryst'allises from acetic acid in colourless, cornpact needles, begins to sinter at 240", melts at 255-25i0, and dissolves in aqueous soda, or potash yielding yellow crystals of the corresponding salt. The crystals have the composition CI5H,,NOa. When the compound (1 gram) is heated with methyl alcohol (10 c.c.), potassium hydroxide (1.7 gram) and methyl iodide (3 grams) a t 100" for one hour, two compounds are obtained of the composition C15HION02Me ; one of these crystallises out on cooling in colourless, compact crystals, which begin to sinter nt 200", melt at 235-5237", and are sparingly soluble in alcohol, insoluble in alkalis, whilst the second remains in the mother-liquor and crystallises from alcohol in long, colourless needles melting at 119-121".Since the compound is not a lactone, its constitution is probably expressed by one of the C(0H) : CPh CO. CHPh two formd= C6&< CO--BH> or COB,< CO-NH>. w. P. w. Beneyl-derivatives. By S. GABRIEL and H. HENDESS (Rer., 20, 2869- 28 72) .-MetanitrobsiLzzJZ~h~haZ~m ide, NOz*C6H4*CHz*N : C,H,O,, is formed when an intimate mixture of metanitrobenzyl chloride (1-7 gram) and potassium phthalimide (2 grams) is heated at 120° for about one hour. It crystallises in slender needles, melts at 155", and is soluble in acetic acid and alcohol, sparingly soluble in water.When heated with fuming hgdroohloric acid at 200" for two hours, it i s converted into a mixture of phthalic acid and nietunitrobenzy Zaminne hydrochloride ; the latter crystallises in needles. Metanitrobenzyl- m i n e yields an acetyl-derivative, C&N202Ac, cryatallising in needles whicb melt at 91 O , and a pZcct&aochZoride, (C7H,N202),,HzPtC1,, crystallising in rhombic scales, whilst reduction with tin a,nd hydrochloric acid converts it into metamidobenzy lamine ; this dmolvea in water, has e atrongly alkaline reaction, and formORGANIC CHEMISTRY. 145 picrate crgstallising in sparingly soluble scales and a plafiinochloride, C,H,(NH2),,H2PtC1,, cryshlhing in yellow scales. BenzaZtetrach Zwcvphthulide, CHPh : C<c,;i>CO, is obtained when tetrachlorophthalic anhydride (10 parts) is heated with phenylacetic acid ( 5 parts) and sodium acetate ($ part).I t crystallises in slender, yellow needles, melts above 360", and 1s practically insoluble in acetic acid and hot alcohol, more soluble in hot benzene and nitrobenzene. On treatment with sodiiim hydroxide, it is converted into a-tetrachloro- desoz y benzo~nort hocarbox y Zic which crystallises in colourless needles, melts at 175", dissolves readily in alcohol, ether and benzene, and yields a barium salt, (C,,H7C1403)zBa, crystallising in pale rose-coloured needles. Dichlorophthalic anhydride, when similarly treated, yields benzaltli- chlorophthalide, CHPh C<C6HzC12>C0, which crystallises in small, brownish-yellow needles, melts at 2 loo, dissolves readily in benzene, and by the action of alkalis is converted into oc-dichlorodesoxybenzo~~~ - orthocarboxlylic acid, C15H10C1203, crystallising in colourless needles acid, CHzP h* C 0.c& 14.c 0 0 H, -0- melting at 117". w. P. w. Resazo'in and Resorufin. By E. EHRLICH (Mowatsh., 8, 425- 428) .-Bruiiner and Kraemer (Abstr., 1884,1333) proposed to drop the prefix di- from the names diazoresorcinol and diazoresorufin, but the author and Benedikt, contending that these compounds are no more azo- than diazo-derivatives, suggest re-naming them resuaozn and resorwjin. Resazojin when dissolved in potash and oxidised with hydrogen peroxide yields hydroryresazoln, C18H12N207. This substance crystal- lises in almost colourless needles or scales which decompose before fusion, yielding a slight crystalline sublimate and leaving a carbon- aceous residue.It is sparingly soluble in alcohol, soluble in glacial acetic and hydrochloric acids. Alkalis dissolve it with a reddish- yellow coloration. When reduced with zinc and sulphuric acid or ammonia, it yields a derivative of the formula C,,H,,NZO7, crystallising in needles. These oxidation-derivatives confirm the correctness of Weselsky and Benedikt's formula Cl,H12N,0s for resazo'in, but are not in keep- ing with Brunner and Kraemer's formula C12H9N04 (Eoc. c i f . ) . L. T. T. Three Isomeric Tritolylstibines. By A. MICHAELIS and U. GENZKEN (Annnlen, 242,164--188).-The preparation of the tritolgl- ptibines has been previously described by the authors(Abstr., 1884,1135).Paratritolylstibine forms hexagonal rhombohedra [a : c = 1 : 1.58071. Its sp. gr. a t 15.6' is 1.35448 (water at 4" = 1). It melts at 127- 128" and dissolves freely in chloroform. It forms additive chlorine, bromine, and iodine compounds which have already been described (hc. cit.). On the addition of a cold alcoholic solution of mercuric chloride to pal-atritolylstibine dissolved in alcohol and ether, tritolyl- stibinemercuric chloride is precipitated, (CrHACH3)3Sb,HgClz, but if hot VOL. LIV. I146 ABSTRACTS OF CHEMICAL PAPERS. solutious are mixed, paratolylmercuric chloride, C6H4Me.HgC1, is obtained. Orthotritoly Zstibine, Sb( C6H4Me),, melts at 79-40", and dissolves freely in chloroform, benzene, ether, and light petroleum. Orfho- tolylmercuric chloride, c6H4Me*HgC1, is obtained as a crystalline powder on mixing ethereal solutions of mercuriq chloride and mercury ditolyl.It melts a t 145-i46". Orthotritolylmercuric chlor-iile is freely soluble in chloroform and is deposited from alcohol in silky plates. Unlike the para-compound, the alcoholic solution is not decomposed on boiling, yielding tolylrnercuric chloride. I n the preparation of orthotritolylstibine, needle-shaped crystals melting a t 112" are obtained. The compound (probably orthopara- tritolylstibine) is freely soluble in chloroform, benzene, ether, and light petroleum. With mercuric chloride, it yields a crystalline com- pound which melts at 164" with decomposition. The alcoholic solution is not decomposed on boiling. Orthotritolylstibine chloride, (C6H4*CH3),SbC1,, melts at 178-179", the bromide melts a t 209-210", and the iodide a t 174--175'.The oaide melts a t 220" and dissolves freely in acids. MetatritoZyZstibine melts at 67-68' and dissolves freely in ether, benzene, chloroform, and acetic acid. I t s sp. gr. at 15.7" is 1.3957 compared with water a t 4". The additive compound with mercuric chloride melts with decomposition a t 140". The alcoholic solution is decomposed by boiling, yielding metatolylmercuric chloride, C6H4Me*HgCl (m. p. 159-16d"). Hetatrito Zy Zstib lne chloride melts a t 137-138". It is very soluble in benzene, ether, and chloroforni. The bromide has been previously described (loc. cit.). The iotlide melts at 138-139" and dissolves freely in chloroform, benzene, ether, and alcohol.The oxide is sparingly soluble in alkalis, alcohol, benzene, chloroform, and ether. OH*Sb( C6H4Me),*OAc, is crystallirie and melts a t 142-143". Metatritolylstibine swlpllide, SbS(C6H4D/Ie),, is obtained as a crystalline compound by the action of hydrogen sulphide on a solution of tritolylstibine chloride in alco1:olio ammonia. It melts a t 162-163" and dissolves in chloroform arid benzene. Chlorine, bromine, or iodine converts the sulphide (in solution in chloroform) into the corresponding chloride, bromide, or iodide. w. c. w. The basic acetate, Decomposition of Isonitroso-compounds. By H. v. PECHMANN (Ber., 20, 2904-2906 ; compare Abstr., 1887, 1103).--BenzoyZ- fornzaldeh yde hydrate, COPh*CH(OH),, is obtained as follows : nitroso- acetophenone is dissolved in a strong solution of hydrogen sodium sulphite, and thedouble compound so obtained boiled with 10 parts of 30 per cent.snlphuric acid ; on cooling, the whole solidifies to a mass of white needles, which are dissolved out in ether and recrystal- lised from water. It forms lustrous, colourless needles, which melt ah 73' and give off water a t a higher temperature. The anhydrous Lrldehyde boils at above 142" under 125 mm. pressure. The hydrate has a peculiar penetrating odour, dissolves readily in the usualORGANIC CHEMISTRY. 147 solvents, reduces ammoniacal silver solution, and is converted into inandelic acid by alkalis. When the dilute aqueous solution is treated with some drops of ammonia, flakes separate which form spkieres on adding acid. Phenyltoluquinoxaline (Hinsberg, AnnnZen, 23 7, 370) is formed when an aqueous aldehyde solution is warmed with toluylenediamine siilphate and sodium acetate, and crystallises in colourless needles melting at 155".Negative Nature of Organic Radicles. By V. MEYER (Ber., 20, 2944-2952) .-It was shown previously that desoxybenzoyn and benzyl cyanide, when treated with sodium ethoxide and an alkyl iodide, yield derivatives in which one hydrogen-atom of the me- thylene-group is replaced by an alkyl radicie, whilst ethyl phenyl- acetate does not react under similar conditions (Abstr., 1887, 572), This reaction has now been extended to a large number of aromatic compounds containing carbonyl- and methylene-groups, and it is found that the hydrogen of the methylene-group is displaceable by an nikyl radicle only in compounds precisely analogous in constitution to desoxybenzoh and benzyl cyanide.Under these conditions, the amides CH,Ph*CO.NEt, and CH,Ph*CO*NPh,, the phenylpropionitrile, CH,Ph*CH,*CH,*CN, the nitrile of cinnamic acid, CHPh CH-CN, and methyl diphenylacetate, CHPh*,CO@Me, do not yield alkyl- derivatives ; aceto- and butyro-nitrile are unattacked ; whilst dibenz y 1 ketone, C H,Ph*C 0 C H,Ph, paraphen y lenediace tonitril e, CN*CH,-C,H,*CH,.CN, and derivatives of the type COR-CH,.R', containing complex aromatic radicles (naphthyl, phenanthryl, $c.) readily form alkyl-compounds. The sulphone, SO,Ph*CH,Ph, a compound which crystallises well and volatilises without decomposi- tion, does not reaoij with sodium ethoxide and alkyI iodides.Di- and tri-phenylmethane also do not yield alkyl-derivatives when similarly treated, whilst beautiful, violet-coloured compounds are formed by the action of sodium ethoxide on the nitro-derivatives of these hydrocarbons. Further investigation has shown thaf under no condition can more than one hydrogen-atom of the methylene-group present in desoxybeneoyn be displaced by an alkyl radicle. Nor is it possible t o effect a substitution of an alkyl radicle for the remaining hydrogen- atom of the methylene-group in benzojin, COPh*CHPh*OH, or its acetyl-derivative, COPh*CHPh*OAc. Diphenylacetonitrile, C HP h,*CN, a well- charac terised crystalline compound , how ever, is readily acted on by sodium ethoxide and halojid alkyl-derivatives. The substitution of methyl in the phenyl-group of benzyl cyanide does not seem to interfere with the production of alkyl-derivatives, since the three isomeric methylbenzyl cyanides, C6H,Me.CH2*CN, react with sodium ethoxide and benzyl chloride just as readily as benzyl cyanide itself, although the yield of the product C6H4Me-CH(C7H,)*CN is not quite the same in each case.Like nitroethane and ethyl acetoacetate, desoxybenzoin and benzyl cyanide combine with nitrous acid, diazobenzene, &c. The diazo- derivatives have little stability and are difficult of isolation; the N. H. M. 7 0148 ABSTRACTS OF CHEMICAL PAPERS. isonitroso-compounds, CO*Ph*CPh NoOK and CN-CPh : NOOH, can readily be obtained ; the: latter crystallises well and is distinctly acid in character. w. P. w.Derivatives of Dimethyl-2-Resorcylic Acid. By H. MEYER (Monatsh., 8, 429-438). -MethyE diinethyl-oc-).esorcylate, CGH,( OMe),*COOMe, crystallises in prisms, melts at 81", boils a t 298", and sublimes in white needles. Methyl m onomet 21 y E-a-resorc y late, 0 H *C6H, (OMe) *C 0 ()Me, which is also formed during the methylation of dimethyl-a-resorcylic acid, forms an oil boiling with partial decomposition a t 315". Nitro- dimethyE-a:-resorcyZic acid, N02.C,H2(0Me),*COOH, may be formed either by heating the solid acid with nitric acid, or by adding nitric acid to an acetic acid solution of the acid. It crystallises in yellow needles or prisms, is sparingly soluble in water, easily in alcohol and glacial acetic acid, and melts at 225", subliming at a higher temperature.It forms well-marked salts, of which those of the alkalis are easily, the others sparingly, soluble in water. On reduction, it yields amidodimethy 1-a-resorc y Zic acid, NHz.CGHz (OMe),. CO 0 H, which crys- tallises in hexagonal plates, easily soluble in alcohol, sparingly in water, and melting with decomposition at 182". Its hydrochloride and stannochZoride crystallise in needles. The silver and copper salts are very sparingly soluble in water. The amido-acid does not yield a quinoline-derivative, and consequently the amido- (respectively nitro-) group is probably in the para-position to the carboxyl-group. When calcium dimet'hyl-a-resorcylate is subjected to dry distillation, dimethylresorcinol distils over. The residue contains calcium car. bonate, a resinous compound (probably an etheric-derivative of res- orcinol), and the calcium salt of an acid which the author has not yet isolated. This acid melts at about 222", gives a violet coloration with ferric chloride, and is therefore an ortho-hydroxy acid.L. T. T. Action of Phthalic Anhydride on Amido-acids. By L. REESE (Annalem, 242, 1-22) .-Drechsel has shown (Abstr., 1883, 1126 j that phthnlylamidoacetic acid is formed by the action of phthalic anhydride on glycocine, and he has described the properties of the acid and of several of its salts. The sodium salt is very soluble in water, but it is precipitated on the addition of alcohol to the solution. The precipitate has the composition CloH6N0,Na + HzO. The am- monium salt, CloH6W0,NH4, is prepared by adding alcoholic ammonia to an alcoholic solution of the acid ; it melts at 205" with decomposi- tion.The salt is very soluble in water ; the aqueous solution loses ammonia on evaporation. When a cold solution of copper sulphate is added to the sodium saltl, rhombic prisms or plates of a pale blue colour are depnsited having the composition ( C,,H6N04),Cu + 3H,O, but on mixing hot solutions the anhydrous salt is deposited in six-sided plates. When the copper salt is cautiously heated, phthalirnide and benzoic acid sublime. The silver salt, CloH6N0&, is deposited from hot aqueous solutions in prisms. By the action of ethyl iodide onORGANIC CHEMISTRY. 149 t8his salt, the et'hylic salt, ~,H,NO,Et, is obtained. It crystallises in needles, dissolves freely in ether, chloroform, and hot alcohol, melts at 104-105", and distils at a temperature above 300" without decom- position.Salts of glycocinephthaloic acid are formed by neutralising hot aqueous solutions of the alkalis or alkaline earths with phthalylamido- acetic acid, and evaporating the solution. The sodium salt is amor- phous. It is precipitated as a gelatinous mass on the addition of alcohol to the concentrated aqueous solution. The potassium salt is deliquescent, and crystallises in needles ; the barium salt forms rhombic plates. The copper salt is deposited in needle-shaped crys- tals on the addition of the sodium salt to a solution of copper sulphate. The crystalline silver salt is soluble in hot water. P h t l ~ a t y t a ~ ~ d o c a ~ o ~ c acid, C,,H,,NO,, is prepared by fusing a mix- ture of phthalic anhydride and leucine.The pure acid crystallises in needles, melts at 115-116", and is soluble in alcohol and ether ; on the addibion of water to the alcoholic solution, the acid is deposited in the form of a n oily liquid. The alcoholic solution is Iavogyrate. On dry distillation, optically inactive phthalylamidocaproic acid is formed. The inactive acid can be recrystallised from hot alcohol and ether. It melts in boiling water, and the solution on cooling deposits a few crystals. The acti-re acid forms a crystalline platodiammonium salt, Pt(NH,*NH,~15H,,NOa)z + 3Hz0, insoluble in alcohol. The in- active acid forms a similar compound containing 3Q mols. HzO, which is less soluble in cold water than the salt of the optically active acid, The copper salt is amorphous.It is soluble in alcohol, and is decomposed by heat, yielding butylp hthalimide. The phthalylamidocaproic acids are converted by the action of alkalis into leucinphthaloic acids, and finally into leucine and phthalic acid. The sodium salt of the optically active leucinephthaloic acid is amorphous, and is deposited as a gelatinous mass on the addition of alcohol to the aqueous solutiou. The potassium salt, K2Cl4HI5NO5, is crystalline and freely soluble in water. The barium salt is crystalline and sparingly soluble. The platodiammonium salt forms rhombic plates freely soluble in water, sparingly soluble in alcohol, and in- soluble in ether. The amorphous copper salt dissolves freely in alcohol. The free acid, COOH*C6Ha*CO*NH*CH( COOH).CH,Pr(l., is soluble in alcohol and ether.It is decomposed by boiling water, yield- ing phthalic acid and leucine. It melts at 130-132", and splits u p into water and phtlhalyIamidocaproic acid (active), The potassium salt of inactive leucinephthaloic acid is deposited in crystals on the addition of alcohol to the aqueous solution. The silver salt is amor- phous. The free acid melts at 152-153", splitting up into inactive phtlhalyly lamidocaproic acid and water. It closely resembles the Action of Phthalyl Dichloride on Ethyl Sodiomalonate. By J. WISLICENJS (Artnalert, 242, 23-93) .-By the action of phthalyl dichloride (1 mol.) on ethyl sodiomalonate (2 mols.) mixed with ether, 8 mixture of ethyl phthalylmalonate, dimalonate and phthaloxyldi- It is quickly saponified by boiling water.optically active acid in its properties. w. c. w.I50 ABSTRACTS OF CHEMICAL PAPERS. malonate is obtained. The crude product is treated with water, and the ethereal solution evaporated. An oily liquid remains which deposits crystals of ethyl phthalylmalonate. I n the course of a few days, ethyl phthnloxyldimalonate is also depositcd. On distilling the uncrystallisable mother-liquor in a, current of stearn, ethyl malonate volatilises ; the non-volatile oil consists of ethyl phthalyldimalonate. After it has been purified by washing with a solution of sodium car- bonate, it solidifies, forming a crystalline mass. Ethyl phthalylmalonata, C I5Hl4O6, is deposited from ether in tri- clinic prisms. The crystals are highly refractive.The ethereal salt dissolves in 14 times its weight of ether at 9", and in 1.7 times its weight of ether at 35". It is more soluble in alcohol. It melts a t 74*5", and on cooling the fused mass, the solidification proceeds from certain points in a peculiar and characteristic manner. Ethy 1 phthalox y ldimalonate, Cz2Hz409, is deposited from ether in needles and from alcohol in prisms. I t requires 184 parts by weight of ether a t 9", and 174 parts of absolute alcohol a t 14" for solution. It is dissolved by alkalis with an intense yellow coloration. The sub- stance melts a t 116.5" if the temperature is slowly raised, and a t 106" if it i s quickly heated. In the latter case, it soon solidifies and melts again a t 116.5". Ethyl phthalyZdimaZonate, C,,H2,OI,,, is deposited from hot alcohol in prisms melting at 48.3".Ethyl phthalylmalonate is decomposed by alkalis, yielding ethyl alcohol, and phthalic and maloiiic acids. It also splits up on boiling with water into ethyl malonate and phthalic acid. When reduced with zinc-dust and acetic acid, it unites with foiir atoms of hydrogen, forming diethyl hydrogen benxylmaloncarboxylate, It is freely soluble in alcohol and ether. COOH*CsH*.CHz*CR( COOEt)2. The formation of this monobasic acid is incompatible with the sym- metrical formula for ethyl phthalylmalonate. The new compound i8 very soluble in alcohol and ether, but it requires 2230 times its weight of water at 17" for solution. It melts at S6". The sodium salt is deliquescent and is precipitated by ether from its alcoholic solution.The silver salt, C15H17ag06, is soluble in hot water and is crystalline. On treatment with ethyl iodide, i t yields triethyl benzylmaloncarboxyl- ate, a colourlcas liquid boiling a t 2EiO" under 45 mm. pressure. Dipotassium ethy E benzy Imalon carboxylnte, C,H, (COOK) 2*C OOE t, is formed when a solution of the potassium salt of diethylbenzylmafon- carboxylic acid is left in contact. with potassium hydroxide for one hour at the ordinary temperature, but benxylmalonorthocarboxylic acid, COOH*C6H4.i_l'2H3,(COOH)2, is produced if the salt is boiled with an excess of alkali and &hen acidified, This acid is soluble in hot water. It begins to decompose at 170", and at 180" it is completely converted into carbonic anhydride and the hydrocinnamorthocarboxylic acid described by Gabriel and Michael (Abstr., 1878, 426).Phtlidy Zdiarnide, C8HAN202, is deposited in crystals when alcoholic ammonia is added to a solution of ethyl phthalylmalonate in absolute alcohol. Itl is insoluble in the usual solvents, and by boiling with water or by heating at 210" is decomposed, yielding phthalylimide.ORGANIC CHEMISTRY. 151 Sodium ethoxide acts on ethyl phthalylmalonate, forming ethyl p ht hnly loxethy bodiomalonate, C 0 <32> C (OE t) .CNa( COOE t) 2. The sodium atom is easily displaced by hydrogen, yielding ethyl phthalyloxyetliylmalonate, a substance which is easily decomposed by warm alkalis, yielding ethyl alcohol, phthalic and malonic acids. Et h y Z phtF,aZyZoxyethylethylmalo~~ate, CO <cf:> C (OEt) CEt*(COOEt),, is formed by the action of ethyl iodide on the preceding sodium com- pound.It is saponified by alcoholic potash at the ordinary tempera- ture, but the product ,splits up into alcohol and the potlassium salt, C13H9K307. On the addition of hydrochloric acid to a solution of the potassium salt, benzoylorthocarboxethylmalonic acid is liberated, but it spontaneously decomposes into phthalic and malonic acids. An oily liquid which behaves in a similar manner is obtained when an acid is added to the solution of ethyl phthalylmalonate in alkalis. It is probable that the sodium compound of ethyl phthalylhydroxy- mnloiiate is formed in the first instance, and that it IS converted into ethyl phthalylhydroxymalonate, which at the ordinary temperature bplits up into phthalic anhydride and ethyl malonate.At loo", ethyl itionochloracetate converts the ethyl phthalyloxyethylsodiomalollnte iuto trhe ethyl phthalylethylethenyltricarboxylate. On hydrolysis, this acid yields benzoylorthocarboxethezlyltricarboxylic acid, which is decomposed by water, yielding ethenyltricarboxylic and phthalic acids. E thy1 ph thaloxydimalonate uiiites with potassium hydroxide, form- ing orange-coloured crystals of the composition Cz2Hz5K0,,. A yellow sodium compound, C22H21Na2010, is produced by the action of an ethereal solution of ethyl phthrtlyldimalonnte on ethyl sodiomalonate. The sodium is displaced by ethyl on treatment with ethyl iodide, and the product is decomposed by alkalis into alcohol, ethylrnalonic and phthalic acids. The yellow substance is probably a mixture of the two isomerides, CO<~f~>C[CNa(COOEt)2]z and CsH4[ CO*CNa(COOEt)z]2.By the action of acetic anhydride, phthalic anhydride, or phthalic chloride on the yellow sodium compound, ethyl phehaloxyldimalonate is formed, but glacial acetic acid decomposes the substance with the formatiou of ethyl malonate and ethylphthalylmalonate, together with small quantities of ethyl phthalyldimalonate. Hot water also decomposes the sodium compound, yielding ethyl phthalyldimalonate (from the unsymmetrical compound), and ethyl malonate and sodium phthalate from the symmetrical isomeride. It is decomposed by bromine into ethyl phthalylmalonate and ethyl dibromomalonnte, C22H2,Na20,0 + 2Br2 = 2NaBr + C15H1406 + CBr,(COOEt),. Ethyl phthaloxyldimalonate unites with four atoms of nascent hydrogen, forming a neutral oil of the composition C2,H,0,.Ethyl phthaloxyl- dimdonate is probably an unsymmetrical compound, having the consti- n Tr tution represented by the formula C O < c ; $ & - - >C: C(COOEt),.152 ABSTRACTS OF CHEMICAL PAPERS. Ethyl phthalyldimalonate dissolves in alkalis, forming an orange- coloured liquid. If the solution is heated at 100" for some hours, the colour disappears; on the addition of an acid, a tribasic acid, COOH~C6Ha.C(CH2*COOH)2~OH, is liberated, which at once splits up into water and phthalyldiacetic acid, CO<?f:>C(CH2*COOH)2. A yellow potassium compound, C2,H,K2010 + 2H20, is precipitated on the addition of ether to the orange-coloured solution of ethyl phthalyldimalonate in alcoholic poiash.It is reconverted into ethyl phthalyldimalonate by the action of acids. If phthalic chloride is added to a mixture of ether and et.hy1 sodio- malonate at the ordinary temperature, the chief 'product of the re- action is ethyl phthalylmalonate, but if half the chloride is slowly added to the warm mixture, and the product heated for some time before the remainder of the phthalic chloride itJ added, the chief pro- duct is ethyl phthaloxyldimalonate, a small quantity of ethyl phthalyl- dimalonate is also formed. By reversing the process, and adding the mixt,ure of ether and ethyl sodium malonate to the phthalic chloride, a large yield of ethyl phthalylmalonate is obtained, together with halt' the weight of phthalyldimalonate, aud &th of phthaloxyldimalonate.Phthalic anhvdride acts on eth vl sodium malonate. forming sodium Y phthalate, edyl phthalylmalona'te and ethyl rnalonate. w. c. w. Benzenetrisulphonic Acid. By C. L. JACESON and J. F. WING (Amer. Chem. J., 9,325-347, Compare Abstr., l886,623).--Senhofer prepared benzenet risulphonic acid by heating benzene with phos- phoric anhydride and fuming sulphuric acid ; the auth0r.s in prepar- ing potassium benzeneparadisulphonate also obtained benzen etrisu 1.- phonic acid; and its formation was proved to be due, during a second heating of the ingredients, to the Rction of potassium sulphate previously formed ; a similar action possibly takes place in Claesson's method (heating a potassium sulphonate with sulpburyl chloride), and Neville and Winther's method (heating the acid sulphates of the amines) , The potassium sulphate can be replaced by ailver sulphate, and very imperfectly by alumiiiium sulphnte, but not by zinc sulphate, and it therefore acts not as a dehydrating agent, but as a carrier of sulphuric acid.Yotcrssiuwt benzenetrisulphonate, C6H3(S03K)3 + 3H20 [= 1 : 3 : 51, is easily prepared by heating 15 grams of potassium benzenemetadisul- phonate with 18 grams of strong sulphuric acid, until the mass begins to get pasty, when it is dissolved in water and converted into the potassium salt by the usual methods ; the yield amounts to 44 per rent. The preparation may be made from benzene itself, but the product is more difficult to purify owing to the formation of para- disulphonic compounds.The salt forms monoclinic plates or needles : /3 = 68" 38&' ; a : b = 1 : 3.10 ; 35-46 parts of the anhydrous salt are dissolved by 100 of water at 20". Attempts to brominate or nitrate the acid were unsuccessful. Benzenetrisu~phmic chloride, C,H,(SO,CI),, is prepared by the usual methods; it melts at 184." and soon after sublimes slowly ; i t is slowly decomposed by boiling water,ORGANIC CHEMISTRY. 153 and is best recrystallised from chloroform. Ethyl benzenetrisulphonate, C,H,(SO,Et),, is readily obtained from the silver salt and ethyl iodide ; other methods are not suitable. It melts at 147", but is decomposed by long heating at lower temperatures. It crystallises readily from benzene, and is insoluble in water ; it is decomposed by boiling with absolute alcohol, the free acid and ethyl ether being formed.Benzene- trisuZphortarnide, CsH,( S02NH2),, is formed from the chloride by the action of aqueous ammonia. It may be crystallised from water or alcohol, and. melts at 310-315". The following salts are described, C,H,( SO,NHAg),, C,H,(SO,NHHgOH),, and [ C,H,( SOZNH),],Hg, both formed with difficulty, and [CaH,(S03)3]2[ CU(NH~)~]~. Attempts to prepare the imide were not altogether successful. Benzenetrisulpho- benzo!yZamide, C,H,( SO,NHBZ)~, is obtained by acting with benzoic chloride on the sulphonamide at temperatures not above 140". It is purified by crystallisation from alcohol, but shows no definite melting point, owing to its ready decomposition. It dissolves easily in alkalis, and forms salts such as C6H3(S02NNaBz),, and [C6H3(S02NBz),]Ba3 + 12H,O, both being uncrystallisable.When the benzoylamide is treated with phosphorus pentachloride, the substance CsH3( SOZN : CClPh), is formed, which by warming with aniline is converted into the corn- pound CsH3(S0,N : CPh*NHPh),, melting at 193", and best crystal- lised from alcohol. Benze/~etrisuZphaniZide, C0H3( SO,NHPh),, formed by the action of aniline on the sulphochloride ; it crystallises well from alcohol, and melts at 837". The constitution of the benzenetrisulphonic acid here described is ascertained by fusion of the potassium salt with potitssiiim cyanide and saponifying the nitrile formed, when the only product is trimesic acid ; moreover, when the sulphochloride is heated with phosphorus penta- chloride at 200", it is converted into the symmetrical trichlorbenzene, hence [(SOSH)I = 1 : 3 : 51.Sulphonefluorescein. By I. REMSEN and C. W. HAYES (Amer. Chem. J., 9, 372--379).-1t has been previously shown (Abstr., 1885, 539), that when resorcinol is heated with orthosulphobenzoic acid, it yields a highly fluorescent substance. This is now shown to be one oE a new class of compounds, the sulphonphthaleins. Sulphonjhorescdn, 0 < C,H,(OH) CeH3(0H)>C<~eN4>S02 0- + 2H,O, is ob- tained when orthosulphobenzoiu acid is fused with resorcinol at 175- 185" until the inass becomes pasty. The mass is crystallised from water, and the crystals washed with ether ; they are pale straw-yellow, and probably monoclinic. It shows a feeble green fluorescence, much stronger in alkaline solution, is very soluble in water and alcohol, but dissolves only slowly in ether.It does not melt without decomposi- tion. It has decided acid reactions, differing from fluorescein i n that it decomposes carbonates. The barium, (C19H1307S)2Ba, and calcium salts are described, as also a crystalline acetyl-derivative. When treated with bromine in acetic acid solution, it yields a dibromide, ClgH'loBraOsS, and with sulphuric acid it yields an intensely fluorescent a. B.154 ABSTRACTS OF CHEMICAL PAPERS. acid. oxidises in the air. H. B. Nascent hydrogen reduces it to a colourless substance that re* Diphthalic Acid. By C. GRAEBE and P. JTJILLARD (Annulen, 242, 214+257).-Pure diphthalic acid is a colourless substance which melts at 270-272". The methyl salt, CI6HBo6Me2, obtained by the action of methyl iodide on silver diphthalate, crystallises in plates of a lemon colonr.The ethyl salt form8 lemon- col oured needles, and melts at 1.54-1 55". When hydrogen chloride is passed into warm ethyl alcohol containing diphthalic acid in solu- tion and suspension, colourless plates are deposited of the composition CI,H1408. The compound melts at 174", and dissolves in alcohol, et.her, and chloroform. If methyl alcohol is substituted for ethyl alcohol in the previous experiment, a crystalline compound is obtained which melts a t 275". After recrystcallisation from phenol, it seems to have the composition CleH1406. These substances are decomposed by hydrocliloric acid a t 150°, yielding diphthalic acid and methyl or ethyl chloride.At 180", hydroxylamine hydrochloride acts on diphthalic acid in presence of alcohol, forming a compound of the composition Cl6Hl8N2O4. This substance is also formed by heating a t 100" in sealed tubes a mixture of hydroxylamine hydrochloride, alcohol, and diphthalic anhydride, but if the operation is carried on in an open vessel an ethereal salt is produced. The first compound crystallises in slender needles, melts at 285-286", and dissolves in phenol. The lactone of benzhydroltricarboxylic acid is obtained by dissolv- ing diphthalic acid in a 4 per cent. solution of sodium hydroxide, and heating the solution a t 110-115" for three minutes. When cold, the product is acidified with hydrocl.11oi.i~ acid and the lactone is precipitated. It is soluble in choroform and in alcohol.On boiling the alcoholic solution, carbonic anhydride escapes, and the laotoiie of benzhydroldicarboxylic acid is formed. On reduction with phosphorus and hydriodic acid a t 1 70°, the lactone of benzhydroltricarboxylic acid is converted into di~F,enylmeth~netricarboxylic acid, It melts at 191-192". C OOH*CH( C6H4.C OOH),. This acid is soluble in hot water and crystallises with 1 mol. H20. It begins to decompose at its melting point, 218-220", and nt 250- 270" it is comylelely converted into a red compound, CIGHBO1, which melts a t 260". This red substance is also formed by dissolving the acid in warm sulphuric acid and pouring the solution into water. Benzhydroldicarhoxylic acid, OH*CH(C,H,*COOH),, is formed by heating diphthnlic acid with a 50 per cent.solution of potassium hydroxide at 125-130" for five minutes. The lactonic acid, dissolves freely in alcohol, ether, and chloroform ; it melts at 203'. On oxidation, the alkaline solution yields benzophenonedicarboxylic acid, and the acid solution when treated with chromic acid yields the dilactone of the above acid. On reduction with hydriodic acid andORGANIC CKEMISTRF. 155 phosphorus, diphenylmethanedicarboxylic and dihydroanthracene- carboxylic acids are obtained. If the lactone is sublimed, the sublimate melts a t 171°, and has the same composition as the lactone. The potassium and barium salts (C15H1005Ra + HzO) of benz- hydroldicarboxylic acid are amorphous. The ammonium salt of the lactone is crystalline. The following salts of the lactone are insoluble in water: (C15H90a)2Ba+ 2&H,O, (CI5HgOJ2Cu+ 3H20, and C15H,0Jg.The methyl salt melts nt 154-155", and the ethyl salt at 99.5". The nmide, C15H903*NH2, crystallises in needles, and melts at 158-160". The lactone unites with phenylhydrazine, forming the crystalline compound CZ1H,,NaO3. It also forms a crystalline dinitro-derivative, C15H80,(N0z)2, melting between 270" and 280". The ethyl sdt, C15H,01(N02)2Et, melts a t 146-148". Benzo~heiLonedicarboxEIZ1:c acid, (20 (C,H,-COOH),, is soluble in alcohol, ether, and acetic acid. It melts between 150" and 155", losing a molecule of water, and forming the dilactone. The potas- sium' and ammonium salts cryatallise in needles, and are freely soluble ill water. The copper salt is insoluble, and the silver salt sparingly soluble.The barium salt, C15H,05Ba + 5H20, forms prisms, which dissolve freely in hot, and sparingly in cold water. Anthraquinone is'formed when the anhydrous barium salt is strongly heated. The methyl salt, C,H805Me2, melts at 85-86', and the ethyl salt at 73- 74". The dilactone of benzophenonedicarboxylic acid, C <ff:> GO>,, is obtained in crystals when strong hydrochloric acid is added to a con- centrated alcoholic solution of benzophenonedicarboxylic acid. It is soluble in benzene, chloroform, hot acetic acid, and hot alcohol. When reduced with zinc-dust and acetic acid, it is converted into the lactone of benzhydroldicarboxylic acid, and when reduced with hydriodic acid and phosphorus at 1 70°, it yields diphenylmethanedicarboxylic acid and a small quantity of dihydroanthracenecarboxylic: acid.At 200", if much phosphorus is used, the chief product is methyl- anthracene hexahydride. Fuming snlphuric acid converts the dilactone into anthraquinonesulphonic acid. The imide of benzo- phenonedicarboxylic acid is obtained on heating the ammonium salt of the acid, or by the action of ammonia on the dilactone ; it forms colourless crystals, and melts at 951-252". It is converted into the di-iwhide, C15Hlo0zN2, by treatment with alcoholic ammonia a t 140" ; this is soluble in acetic acid, hot water, and hot alcohol. It crystallises in prisms, and melts a t 284-286". The acetoxime of benzophenonedicarboxylic acid forms colourless crystals, and melts at 213-214". When the dilactone is treated with dilute alcohol and hydroxylamine hydrochloride at a gentle heat, the ethyl salt of the acetoxime is obtained ; it melts at 146-149".Phenylhydrazine unites with benzophenonedicarboxylic acid, form- ing a crystalline compound of the composition C2,Hle05N2, which melts at 155", aAd loses 2 mols. H,O, yielding the compound C21H1404N2. This substance can also be prepared by slowly adding (156 ABSTRAOTS OF CHEMICAL PAPERS. phenylhydrazine to a warm alcoholic solution of the dilacbne. It melts at 230°, and is soluble in hot alcohol. Diphenylmethanedicarboxy Z ~ c acid, CH2(C6H4*C00H),, melts at '254.5", and at 280" yields n sublimate which consists of a mixture of anthraquinone and unaltered acid. The acid is soluble in alcohol and ether. It is oxidised by potassium permanganate to benzophenone- dicarboxylic acid.Strong sulphuric acid at 100" converts it into a-nnthranolcarboxylic acid. The barium salt, C15HloOaBa + 6Hz0, is crystalline. The methyl salt, ClsHlo04Me2, is very soluble in alcohol, and nielts at 43-44". a-Anthrai~oZc~,rbozyZic acid dissolves freely in alcohol and ether, and melts at 252-253" ; when oxidised, it yields anthraquinone- carboxylic acid melting at 286". a-Dihydroawthracenecarboxylic acid, ~6~,<,H2>~6H,~cooH, CH2 crystallises in yellow prisms, and is soluble in alcohol and ether. It melts at PO9", and on oxidation with potas- sium permanganate yields the anthraquinonecarboxlic acid which nielts at 288". a-Methylanthmcene ftexahydride crystallises in plates, and dissolves freely in alcohol, ether, and chloroform.On oxidation with a mixture of chromic and acetic acids, it yields a-methyl- anthraquinone, crystallising in yellow needles, .and melting at 153- 154". w. c. w. Auramines. By W. FEHRMANN (Bey., 20, 2844-2862).- Com- mercial auramine is the hydrochloride of a base obtained by the action of ammonium chloride on tetramethyldiamidobenzophenone ; the author, however, gives to the base itself the name auramine. Tetramethyldiamidobenzophenone (this Journ., 1876, ii, 298) crptallises in silvery-white scales, melts at 172-172*5", and is in- soluble in water, very sparingly soluble in ether, soluble in alcohol and benzene. The hydrochloride, C17H20N,0,2HCl, crystallises from alcohol in small, white, radially-grouped prisms, and decomposes in aqueous solu- tion with separation of the base ; theplatinochluride, Cl,H2,N20,H2PtCl6, is a granular, yellow precipitate, sparingly soluble in water and alcohol ; the picrate, C,,H,,N,O,C,H, (N02)J*OR, crystallises from alcohol in small, purple-red, radially-grouped prisms, melts at 156- 157", and is very sparingly soluble in hot water, soluble in alcohol. Burainime hydroeldoride (commercial auramine), C17H,,N3,HC1 + H20, is prepared by heating equal parts of tetramethyldiamidobenzo- phenone, ammonium chloride, and zinc chloride at 150-160" until the melt is almost completely soluble in water.It crystallises from water (at 60-70"), in beautiful, yellow scales, decomposes at 263--280", without previous fusion, and is spariiigly soluble in cold water, soluble in alcohol.Dilute mineral acids readily con- vert it into tetramethyldiamidobenxophenone even in the cold, and the same change is effected by boiling the aqueous solution. Cotton prepared with tannin is tinged a pure yellow by the dye, and the colour is little affected by acids. Auramine, NH : C(C6'Hp*NMe2)2, crystmllises from alcohol by spontaneous evaporation in citron-yellow scales, and is insoluble in water and ether, soluble in alcohol; the plat iuochloride, ( C,7HE,,N,),,H2PtCl,, separates from mixed aqueousORGANIC CHEMISTRY. 15'7 solutions of the constituents as a yellow, granular precipitate, in- soluble in water, and sparingly soluble in alcohol; if, however, alcoholic solutions are employed, the chief product is the platino- chloride of tetramethyldiamido benzophenone ; the picrate, crystallises in slender, yellow scales, melts at 230--236*, and is inso- luble in cold water, sparingly soluble in cold alcohol; the oxalate, (C,,H?1N3)2,H2CZ04, crystallises in small, orange-yellow needles, melts a t 193-194", with the evolution of gas, and is sparingly soluble in water, soluble in warm alcohol.Phenylauramine hydrochloride, CP3H,,N3,HC1, is formed when aur- amine hydrochloride is heated with aniline at 175-180" until ammonia ceases to be evolved, or when tetramethyldiamidobenzo- phenone is heated with aniline hydrochloride. It is a reddish, crystalline mass, which dissolves in water and alcohol, and graduaily in aqueous solution, or more rapidly on treatment with mineral acids, decomposes into tetramethyldiamidobenzophenone and aniline.Phenylaurcrmine, NPh : C( c6H,*NMez)2, crystallises from alcohol i n small. greyish-yellow, radially-grouped needles, decomposes at SO" into a solid and a liquid substance, and is insoluble in water and ether, soluble in alcohol ; the pZcLtinochZoride, (C,H2,N3)2,H2PtC16, and picrate, C23H,,N3,CsH2(NOz)3.0H, are flocculent and dissolve in alcohol. l'ol.t/Zaurarnine hydroch loride, obtained by heating auramine hydro- chloride with paratoluidine a t 160°, resembies the phenyl-derivative in its properties ; the platinochloride, ( C2,H27N3)2,H2PtC&, forms red flocks, soluble in alcohol. c 17H21N3, csH2 (No&* OH, To 1% y leneauranaine, C6H3Me <:E> C( C6H4*N&h2) 2, is formed when auramine hydrochloride is heated with metaparat.oluylenediamine at 160°, and the resulting hydrochloride is treat'ed with ammonia.It crystallises from alcohol in small, brown scales, and in dilute acetic acid solution dyes cotton prepared with tannin a reddish-brown. In acetic acid solution, or more rapidly on treatment with dilute mineral acids, it is decomposed into tetramethy ldiamidobenzophenone. The hydrochloride crystallises in very slender, small, brown needles, and decomposes very readily ; the platinochloride, CZ4H2*N4, H,PtCIs, and the picrate, ~ , ~ z , ~ , , ~ ~ 6 ~ , ( ~ ~ z ) , ~ ~ , are soluble in alcohol. manner from ethylenediamine, crystallises from alcohol in yellowish scales, is insoluble in wat.er, soluble in alcohol, and decomposes into tetramethyidiamidobenzophenone in acetic acid solution, or on treat- ment with mineral acidR.It dyes cotton prepared with tannin yellow with a shade of red. The hydrochloride forms yellow needles, and is very unstable ; the plutinochloride, C',gH26N4,H2PtC16, and picrate, C19H26KN4, 2 C6&( NO,) 3*0 H, were also prepared. If the auramines, instead of being heated with water, are dissolved in warm alcohol, and treated with hydrogen sulphide, a n analogous decomposition occurs with the production ot' ammonia or the cor- responding amine and tetramethyldiamidothiobenzophenone. The158 ABSTRACTS OF OHEMICAL PAPERS. latter crystallises in small, dark-red, flattened needles, and melts at about 164", although by repeated crystallisation the melting poiiit slowly rises, owing apparently to slight decomposition.When warmed with mineral acids, or when heated with water a t 110-120", it is decom- posed into hpdrogen sulphide and tetramethyldiamidobenzophenono. The platiiLochloride, C17H20N2S,H2PtC16 (compare Abstr., 188i, 81(i), forms violet-black flocks, insoluble in water and ether, sparingly soluble in alcohol, but readily soluble in excess of hydrochloric acid to a purple- red solution, which readily decomposes with the separation of platinum sulphide. On treatment with carbon bisulphide in the cold, auramine is converted into a mixture of tetramethyldiamidothiobenzophenone and thiocyanic acid, whilst phenylauramine, when heated at 150" for five hours with carbon bisulphide, yields the thioketone and phenyl thiocarbimide. w. P. w. Auramine. By C . GRAEBE (Chmz.Centr., 1887, 951, from MO7Lit. Sci., 1887, 601).-Auramine, first obtained by Kern and Caro, is pre- pared by heating tetramethy ldiamidobenzophenone with ammoni urn and zinc chlorides. The free base is colourless, the hydrochloride, which has been introduced into commerce, forms golden-yellow leaf- lets, sparingly soluble in cold, readily in hot water. V. H. V. p-Naphthaquinone. By T. ZTNCKE (Ber., 20, 2890-2895 ; com- pare Abstr., 1887, 53).~Tr~chlorodiketohydronaphthale1~e h i d m t e , C6H*<cEcl->CC12 + 2H20, is prepared by passing chlorine into co*co glacial acetic acid containing p-naphthaquinone, filtering, and keeping the solution for two days in a closed vessel ; water is then added, and the trichloride, which separates in thin, white needles, is crystallised from alcohol or glacial acetic acid.It forms large, lustrous, well- formed crystals, probably monoclinic, which melt at 112" with sepa- ration of water ; a t 180", it becomes red and gives off hydrogefi chloride. The anhydrous substance forms a tough, yellowish mass, which separates from benzene in highly coloured crystals melting a t 128". When warmed with methylamine in alcoholic solution, the cornpour& C6H4<C( CO*C(OH) NMe>>CC1 separates in intensely red scales of a metallic lustre, melting at 200". Two other compounds, melting at 237" and 160" respectively, are formed. Tricldoret hy Zen epheql eneg lycollic acid , is formed when the trichloride is dissolved in dilute aqueous soda, and separates as an oil on adding an acid. The methyE salt crystallises in colourless, lustrous, monoclinic crystals melting at 150".The acetyl- derivative crystallises in small needles which melt at 114-116". Phenylenetrichlorathylene ketone, CHC1< gg:>CO, is prepared by oxidisivg the above hydroxy-acid with dilute chromic acid, and sepa-ORGANIC CHE SIISTRT. 159 rates as an oil, which gradually solidifies. I t crystnllises from alcohol in thick pointed needles, having a peculiar odour resembling that of benzophenone; it is readily soluble, melts a t 58-59', and distils slowly with steam. OrthodichZoroiiin?/Zberzzoic acid, C2HC12-C6H4*COOH, is obtained by dissolving the trichloroketone in an alkali and adding acid. It crys- tallises from dilute alcohol in long, slender needles melting at 120- 121". It is reduced by sodium amalgam to orthoethylbenzoic acid melting at 68".The methyZ salt crystallises in thick needles which melt at 47". N. H. M. Hydro-derivatives of Aromatic Bases. By E. BAMBERGER (Ber., 20,2915-29 17).-p- Tetral~ydronapl~th~ilamine, CIOH11*NH2, pre- pared by the reduction of p-naphthylamine with sodium, is a very strong base, capable of displacing ammonia from its salts. It forms stable, crystalline salts with carbonic anhydride, and by carbon bisul- phide is converted with explosive violence into tetrahydronapht,hyl- amine tetrahydronaphthylsulphocarbamate. The isomeric a- derim- tive is a feeble base, which does not react alkaline or yield a carbonate. It reacts like a normal amine with nitrous acid. It is suggested that the hydro-derivatives of the aromatic bases are related to bases of the camphor-group, and that tetrahydro- p-naphthylamine and Leuckart and Bach's bornylamine (Abstr., 188 7, 376) are similarly constituted.N. H. &I. Orthamidazo- and Hydrazimido-cornpour, ds. By T. ZIKCB E and A. T. LAWSON (Ber., 20, 2896-2903 ; compare Abstr., 1886,795, and 1887,731) .-Benzeneszo-P-naphthylamine is a much feebler base than orthamidazotuluene ; the salts are readily decomposed by alcohol and water. The hydrochZoride crystallises in yellowish needles ; the sdphate, NHz.CloH6.N2Ph,HzS04, forms brownish-yellow needles. The diazochbride is prepared by dissolving 1 part of the am-compouqd in 15 parts of hot glacial acetic acid and adding 3 parts of strong hydro- chloric acid ; cold nitrous acid i s then passed through, and the whole kept until a clear, dark-red solution is obtained.The platinochloride, ( N2 C 1 C ,,H,*N,P h) ,Pt C 14, forms small, yellow , sparingly soluble needles. The diazosulphate is less soluble than the chloride ; the p e r - bromide, NZBr3*C,,H6.N,Ph, forms small, red needles. When the soh- tion of the diazochloride in acetic acid is diluted with water, nitrogen is evolved, and benzeneazo-&naphthol is formed. When the well- cooled acetic acid solution of the diazochloride is treated with stannous chloride, heated on a water-bath, and filtered, the diazohydride, N2H*CloH6.NzPh, is obtained ; this crystallises from benzene or alcohol in colourless, lustrous needles, melting a t 204-205". The acetyZ-deri- uative, NzAc*CloH,*N2Ph. crystallises from alcohol in lustrous needles which melt at 137-139". p-Anzidazonaphthalene hydrochlomkie, C,,H,*N2*C,,H,~NH2,HC1, forms small, brownish-yellow needles ; the sulphate crystallises in brovvnish- yellow needles. The diaxochloride is decomposed by water, with forrna- tion of /3-hydraxyazonaphthalene (Nietzki and Goll, Abstr., 1886,714) and evolution of nitrogen. The diaxohydride, N2H*C10H6-N2*C10H7,160 ABSTRACTS OF CHEMICAL PAPERS. crystallises in white needles melting at 202-204, is readily soluble in hot alcohol and hot glacial acetic acid, sparingly soluble in benzene.N. H. 11. Sulphonation of Acetonaphthalide. By M. LANGE (Rer., 20, 8940-2941.) .-a-Acetonaphthalide is sulphonated by adding it i r i fine powder to fuming sulphuric acid containing 20 per cent.of anhy- dride. The sulphonic acid is unstable, and loses the acetyl-group when boiled with alkalis or acids. a-Naphthy laminesulphonic acid is obtained by treating the solution of acetonaphthalidesulphonic acid in sulphuric acid with twice the bulk of water. It crystallises in needles much more soluble than naphthionic acid ; the salts are also much more soluble than those of the naphthionic acid. The solution shows a green fluorescence. The benzylidene compound crystdlises in long needles. When the acid is diazotised and boiled with alcohol, a naphthalenesulphonic acid is formed, which yields a-naphthol when fused with potash. By A. WEINBERG (Ber., 20, 2905-2Yll).-~-Naphthalenedisulphonic acid is converted by the action of soda into a new /3-naphtholsulphonic acid.This, when heated with ammonia, is converted into (3-naphthylaminesulphonic acid, from which P-naphthalenemonosulphonic acid was obtained by means of the diazo-compound. Assuming that P-naphthalenedisa 1- phonic acid has the constitution [2 : 3'1, the constitution of a-naph- thalenedisulphonic acid would be [2 : 2'1. pp-Naphtholsulphonic acid, [ 2 : 2'J (known as naphtholsulphonic acid I?.), is prepared by heating sodium naphthalenedisnlphonate (1GO grams), soda (30 grams), and water (300 c.c.), for 12 hours at 250". The product is recrystallised and converted into the barium ~ a l t ; the free acid is recrystallised from strong hydrochloric acid, from which it separates in needles which melt, when dried, at 89". It is readily soluble in water and alcohol, insoluble in ether and ben- zene.When the sodium salt is heated with phosphorus pentachloride (3 parts) at l65", chloronaphthol phosphate melting at 215" is formed as chief product, together with a naphthalene dichloride, which crys- tallises €rom methyl alcohol in rhombic plates which melt at 114". Sodium rtaphtholsulphonate crystallises with 2& mols. H,O in large plates ; the potassium salt with 1 mol. H20 forms rhombic crystals. Both salts are readily soluble in water. The magnesium salt crystal- lises in plates with 54 mols. H,O ; the barium salt is sparingly soluble, but more soluble than the barium salt of Schaeffer's P-naphtholsul- phonic acid. Nitrous acid converts the sulphonic acid into a nitroso- compound; the sodium salt crystallises with 2 mols.H,O in golden needles. Naphthylaminesnlphonic acid [2 : 2'1 (F.), is obtained by the action of ammonia on the naphtholsulphonic acid ; it dissolves in 850 parts of boiling water. The barium salt with 5 mols. H20 crys- tallises in well-formed needles ; the magnesium salt crystallises with 5$ mols. H20. Bayer and Duisberg's P-naphthylamine-6-sulphonic acid (Abstr., 1887, 732) is not identical with the acid [2 : 2'3, but is a mixture. N. H. M. dC-Naphthalenedisulphonic Acid.ORGANIC CHEMISTRY, 161 ~-Naphthol-6-disulphonic acid, prepared from 2 : 2' naphtholsnl- phonic acid, yields with diazobenzene a crystalline orange dye, and with a-diazonaphthalene a Bordeaux, which crystallises in violet plates. The sodizcm saEt is readily soluble in water, from which it is precipitated by alcohol as B yellow powder; the barium salt with 2g mols.H,O crystallises in prisms soluble in 180 parts of boiling wat,er. The solutions of the salts show a green fluorescence. Derivatives of Dinaphthyl. By P. JULIUS (Chem.. Ind., 10, 97 -99).-The author has modified Dianin's method of preparing a- and p-dina,pht,hol. He proposes to treat an aqueous solution of sodium iiaphthoxide with a mixture of ferric chloride and hydrochloric acid, whereby the naphthol, which separates in a finely-divided state, is oxidised into dinaphthol as soon as it is brought into contact with ferric chloride. The following reaction occurs :--LLCloH7*OH + Fe2C1, = C,H,2(OH)2 + Fe2C14 + 2HCL In practice it is necessary to use 2 mols. of hydrochloric acid to 1 mol.of ferric chloride. a-Di- napAthoE thus prepared forms a white, crystalline powder melting at 296-299". p-DienaphthoE forms pale-yellow, glistening needles melt- ing at 217". The yields of a- and 6-dinaphtbols are 70 to 75 and 85 to 95 per cent. respectively as compared with theory. On treating /?-dinaphthol with sulphuric acid, and saturahg the resulting sul- phonic acid with barium carbonate, the barium salt of P-dinaphthol- disulphonie acid, C,HIo( OH),( SO&Ba + 6H20, separates, whilst the filtrate contains the barium salt of ~-da'nirphtho~tetmsz~~phonic acid, &He( OH) ~ S 0 3 ) a B ~ . C20H,(N02)2(0H)2fS03H)2 + 3H20, is obtained by treating the barium salt of the disulphonic acid with nitric acid. It crystallises from alcohol in yellow, silky needles.p-Dinaphthol does not combine with diazo-compounds ; a-dinaphthol, however, does so readily, giving rise to a series of dyes. Diamidopyrene. By R. JAHODA (Monatsh., 8,449-451) .-The hydrochloride of this base is obtained by the reduction of dinitro- pyrene (Goldsohmiedt, Abstr., 1881, 206) ; it forms white needles. Di- amidopyrene, C16H8(NH2)2, is very unstable in the €ree state, resinifying very rapidly. The sulphute forms a white substance, insoluble in water and alcohol, and decomposes when heated. N. H. M. Dinitro-p- diii apht holdidphonic acid, D. B. L. T. T. Diterebenthyl. By A. RENARD (Gonipt. rend., 105, 865-868) .- The resin oils obtained by the destructive distillation of colophony consist mainly of a hydrocarbon which boils above 309", and can be isolated by successive washings with sodium hydroxide solution, and then with water, followed by fractionation. The liquid thus obtained bas the composition CZ0Hm, and boils at 343-346" ; sp.gr. at 18" = 0.9688; vapour-density 9.6; rotatory power for [ a ] ~ = + 59"; refractive index 1.53. It seems to be diterebenthyl, formed by the condensa- tion of 2 molecules of terebenthene with elimination of H20. When exposed to air in thin layers for five days, it absorbs about one-tenth of its weight of oxygen and forms a varnish. Chromic anhydride in vcjT.4. LIV. 413162 ABSTRACTS OF OHEMICAL PAPERS. boiling acetic acid oxidises the hydrocarbon to carbonic oxide and carbonic anhydride. Potassium permanganate in aqueous solution converts it into carbonic anhydride and formic, acetic, and propionic acids. When the hydrocarbon is poured gradnally into well-cooled, fuming nitric acid, there is no evolution of gases, and on adding water a tri- nitro-derivative, C20H27(NO2)3, separates out.When dried in a vacuum, i t forms a yellow powder soluble in alcohol and et,her. If the ethereal solution of the hydrocai-bon is treated with a current of hydrogen chlo- ride, the compound 2C20Hm,HCI is obtained. Bromine acts violentlg, but in solution in carbon bisulphide it yields the dibromide C20H30Br2, aud when the carbon bisulphide evaporates, the bromine- derivative decomposes with evolution of hydrogen bromide. The direct action of bromine on the hydrocarbon i n presence of water yields the hexabromo-derivative C2nH24Br6, a dark- brown, amorphous solid, which melts below 100",and is soluble in a(lcoho1 and ether.Ordinary concentrated sulphuric acid converts diterebenthyl into a sulphoiiic acid, which is isolated by agitating with water and light petroleum. The liquid separates into three layers, the lower of which is dilute sulphuric acid, the middIe the sulphonic acid, and the upper layer a solation of the unalt'ered hydrocarbon in the light yetro- leum, which does not dissolve the Rulphonic acid. A certain quantity of a new hydrocarbon is formed, which is not attacked by acids. The sulphonic acid is converted into the ammonium salt, which is pre- cipitated by adding sodium chloride to the solution. The sulphonic acid, C2,,He9.SO3H, is obtained by decomposing the ammonium salt with sulphuric acid and extracting with benzene.It is a dark-brown mass, soluble in water, alcohol, ether, and benzene, but insoluble in light petroleum. Its solutions are highly fluorescent, and are brown by transmitted light, green by reflected light. It decomposes carbo- nates of the alkalis and alkaline earths. The free acid is precipitated from its aqneous solution by sodium chloride, sulphuric acid, sodium sulphate, arid calcium chloride. The ammonium salt is soluble in water, forming fluorescent solu- hons. The barium, calcinm, copper, and lead salts, which can be obtained by double decomposition, are all insoluble in water. They all dissolve in alcohol, ether, and benzene, and burn with a smoky flame. C. €3 B. Bitter Principle of Calamus Root. By H. THOMS (An?/,aZtva, 942, 257-260).-The author states that the reason Geuther (Ahstr., 1887, 972) failed t o obtain acorine and acoretine from calamus root is because he did not use the original process descrihed by the author (Abstr., 1886, 895), and consequently obtained different results.w. c. w. Bitter Principle of Calamus Root. By A. GEUTHER (Annulen, 242, 260-264).-A reply to the above. Cubebin. By C. POMERANZ (Hwmtsh., 8,466-470).-The author is investigating this compound from Piyer mbebu, the formula of which was proved by Weidel to be C10H1003. Attempts to eliminateORGANIC CHEMISTRY. 3 63 possible alkyl-groups by the action of hydrogen chloride or iodide proved unavailing, as the substance always carbonised. When osidised with permanganate, it yielded piperonylic acid, CsHc04.When treatled with acetic anhydride, no aceto-derivative is furmed, but an ether, (C,,H,,O,),C), which crystallises in needles, is soluble in alcohol, and melts a t 78". From these results, the author concludes that cuhebb (i) is a deri- vative of a methylene ether of pTrocatecho1; (ii) contains a side-chain, C3H50, yielding carboxyl on oxidation ; and (iii) contains this side- chain in the same position relatively to the two etheric oxygen-atoms as the carboxyl in protocatechuic acid stands to the two hgdroxyls. 1;. T. T. Brominated Quinolines. By A. CLAUS and V. TORNI-ER (Bey., 20, 2872-2882). - yBromoquinoline (Claus and Collischonn, Abstr., 1887, 158) boils at 274-276" (uncorr. ; not 273-274"), solidifies when cooled to below 0" and melts a t 12-13'.The oxalate crystallises in stellate groups of prisms, me1 tirig a t 107" (uncorr.). The picrate forms a loose, bright yellow precipitate, consisting of slender needles ; i t melts at 190". The ethobromide, C,NH,Br,EtBr, is obtained by heating the base with ethyl bromide and absolute alcohol at 100" for some hours; it separates on cooling in lemon-coloured needles with 2 mols. EtOH, and melts at 216" (uncorr.). y B r o a o - pwinoline dibromide hydrobromide is obtained when bromine is added to a, solution of ybromoquinoline hydrobromide in chloroform, as a cinnabar-coloured mass of crystals, melting a t 76" with decomposi- tion; it was not analysed, When the hydrobromide is heated at about 'LOO", ai new dibronzopinoZine is obtained, together with its hydrobromide. The new base crystallises from alcohol in colourless, lustrous needles, which melt at 166" (nncorr.).Parabromoquinoline is best purified by boiling with chromic acid. It is an almost colourless liquid which boils at 178" (uncorr.), solidifies when cooled to below O", and melts at 18-19" (uncorr.) When oxidised with potassium permanganate, i t yields only quinolinic acid [ (GOOH), = 2 : 31. The hydrobromide forms colourless needlcs, which soon become red, and melt at about 256'. The hydrochloride (with 1 mol. H,O) melts at 213" (uncnrr.). The nitrate forms needles melting a t 182"; the swlphate crystnllises (with 1 mol, H,O) in small plates melting when dry a t 176" ; the chromate forms small, yellow needles melting at 1 i Y ; the oxalate, melting ah 62", the picrate, melting at 216-217", and the ethohrorkde, melting at 230' (uncorr.), are also described.P a r a b r m q u i n o l i n e dibroinide hydrobronzide is a very unstable, orange-red substance, which melts a t 70°, and when heated at 200" yields dibromoquinoline, melting a t 125-126" (Ida Coste, Ber., 14, 925 ; Claus and Kiittner, Abstr,, 1887, 278). Orthobron7oquinoZi.ne, prepared from ortbobromaniline and purified by chromic acid, forms a colourless oil boiling a t 300-304" (uncorr.). The hydrochZoride, C9NE6Br,HC1 + H20, melts with decomposition at 166" ; the platinochloride crystallises from alcohol in small, bright yellow needles ; the nitrate melts at 90" ; the dichromate begins to decompose at loo", and melts a t 168". Orthobrmnoquinoline dibromide hydrobromide form% om tge-red m 2164 ABSTRACTS OF OaEMICAL PAPERS.crystals, melting at 90' with decomposition; when heated a t ZOO", a new dibromoquinolins is formed, which sublimes in colourless, lustrous needles melting at 90" (uncorr.). Metabromaniline yields a mixture of two isomeric metabromo- quinolines which are best separated by means of the nitrates. Metnbrowaopuinolin,e, C9NH6Br, is an almost colourless oil, which boils a t 280" (uncorr.), and does not solidify at -4". The hydyo- chZoride (with 1 rnol. H,O) is readily soluble in water, and melts a t 2'25" with decomposition ; the platinochloride is a yellow, very spar- ingly soluble substance ; the nitrate is readily soluble in water, and melts at 165" (uncorr.) ; the dichronzate forms reddish-yellow needles, melting a t 190" with previous decomposition ; the ethobromide me1 ts at 290" (uncorr.). Metn bromoquinoline dibromide hydrobromide is an orange-red crystalline substance, melting a t 107" (uncorr.) ; when heated a,t 200", it yields a dibromoquinoline which crystallises in prisms melting at 119" (uncorr.).Anabromoquinoline is crystalline, melts at 32" and boils at 290" (pncorr.). The hydrochloride (with 1 mol. H,O) forms small branched crygtals, very readily soluble in water ; it melts a t 213". The nitrate is much more sparingly soluble in water than its isomeride, and separates in concentricdly-grouped needles melting at 199" (nncorr.) . The ethobromide crystallises from alcohol in coloarless, lustrous needles melting a t ' L l 4 O . Anabromoquinoline dibrontide hydrobroqnide forms light yellow crystals, which melt a t 106-107" (uncorr.) with decomposition ; when heated a t 200", dibromoqui.noZine, melting a t 108" (uncorr.), is obtained.This crystallises in small, colourless needles, N. H. M. Ethyl Hydroxyquinoline Carbonate. By E. LIPPMANK (Monatsh,, 8, 439-441). -When ethyl chloroformate and hydroxyqainoline axe heated together, ethy 1 hydroaypzlinoline carbonate, CgNH,*O*COOEt, is formed. This crystallises in prisms, is soluble in boiling alcohol, chloroform, and etber, melts at 105", and gives no coloration with ferrous sulphate or ferric chloride. The platinochloride, crystallises in orange needles. This ethyl salt when heated with caustic soda yields alcohol, hydroxyquinoline, and sodium carbonate ; with strong hydrochloric acid at 140", it yields ethyl chloride, carbonic anhydride, and hydroxy- quinoline.It is thuv a carbonate and not a carboxylic acid, and i8 not converted into the latter even by heating at 'LOO". Pyrenoline. By R. JAHODA (Monatsh., 8, 442-448) .-Amido- pyrene hydrochloride (Abstr., 1881, 206) was treated by Skraup's reaction with glycerol and sulphuric acid, when pyrenoline, ClgNHll, was formed. This substance forms yellow scales soluble in boiling alcohol, and a dilute solution shows a strong green fluorescence. I t is also soluble in benzene, ether, and chloroform. It melts at 152-153". The hydrochloride forms orange, microscopic needles melting at 270" ; the sulphate pale red, hygroscopic needles melting a t 246"; the L. T. T.ORGANIO CHEMISTRY.165 PZatinocfiZoride a red precipitate, still solid at 290" ; the methiodide dark red, microscopic needles melting at 212", and soluble in alcohol ; and the picrate yellow, microscopic needles, which decompose at 260'. The latter compound is well suited for the purification of the base. When oxidised with permanganate, an acid is formed, but has no+ yet been isolated. Action of Sulphuric Acid on Morphine and Bibasic Acids. By P. CHASTAINB and E. BAIBIZLOT (Compt. rend., 105, 941-943, 3 012--1014).-When morphine is dissolved in excess of dilute sul- phurjc acid, and the solution evaporated until white fumes are given off, sulphomorphide, a substance of Tariable composition which gives brown products with alkalis, is formed. If, however, morphine is heated with concentrated sulphurio acid at 120°, diluted with water, treated with alkalis for a very short time and then neutralised,. it yields a slightly soluble compound of the composition CIaHI7NOa. It always contains some sulphur in the form of sulphuryl, which is removed by strong alkalis, the compound being decomposed at the same time.If morphine, 1 part, oxalic acid, 2 parts, and sulphuric acid, 1.5 part, are heated together at 115-120" for some hours, cooled and mixed with a large excess of water, a yellowish-white compound of the composition C,Hl,NOa or C,HsN,O, is obtained. Malonic acid under similar conditions yields the compound C30HmN2010, and suc- cinic acid the compound CaH43N2012.. These compounds differ by 2CH20. They are white, non-crystallisable substances which beeome greenish when exposed to air and light.They are insoluble in most neutral solvents, but are slightly soluble in cold water, more soluble in hot water. They behave like palyhydric phenols, and when mixed with alkalis oxidise on exposure to the air, forming red solutions. When these solutions are acidified, they deposit a deep blue flocculent precipitate soluble in ether, forming a violet-red solution, and in chloroform forming a blue solution, both of which deposit blue erys- tals of the composition C,,H2,N20a on evaporation. The same compound, morphine-blue, is obtained with all three of the acids above-mentioned. At loo", it contains 1 mol. H20, which is expelled at 120-125". Each of the products from the bibasic acids absorbs 2 mols.of oxygen in alkaline solution, and forms 1 mol. of morphine-blue. This compound crystallises in slightly oblique prisms with a square base, which are red by transmitted light and blue by reflected light. They have no action on polarised light and melt to a blue liquid at a very high temperature. They are insolnble in water, slightly soluble in alcohol, and very soluble in ether, forming a solu- tion which is red by transmitted light, and violet-red by reflected light. It also dissolves in chloroform, and alkalis remove the compound from both the ethereal and the chloroform solution, forming blue solutions. The compound in fact combines with alkalis to form salts which are somewhat stable when exposed to air. L. T. T. C. H. B. Cinchonamine. By C. FRIEDEL (Compt.rend., 105, 985-987). -The crystals examimd were obtained by Arnaud by gradually cool-166 ABSTRACTS OF CHEMICAL PAPERS. ing an alcoholic solution. They formed hexagonal prisms terminated by rhombohedra1 faces, the faces of the prisms being tangent to the edges of the rhombohedron. Sometimes the latter is modified by other faces. Optical examination shows, however, that the rhonibo - hedral form is only apparent, and the crystals really consist of three rhombic sections mncled along the faces m, and the faces which seem tro be those of the fundamental rhombohedron are really the faces a'. The fundamental form is a rhombic prism, i n which mm = GO", and 6 : h = 1.6157. The other angles were found to be a'm = 4 7 O 39'; n'p = 51' 4' (calc.), e4a' = 42" 21' (calc.), e4p = 31" 45' (calc.), LL'X = 53" 29' (cnlc.53" 25') xp = 68" 10' (calc.) ; xm = 36" 42'. There is no outward sign of the structure, the faces eh and x being perfectly united, b u t the macles are not always regular, especially in the larger crystals. The crptals do not become unaxial at a higher tempera- t ure C. H. F. I n two adjacent sections of the macle, a'a' = 84" 42'. Alkaloid from Solsnurrr Gmdiflora. By D. FBMRE ( Q o T H ~ ~ . w i d . , 105,1074-1076).-The so-called " Wolf Fruit " of Brazil is the fruit of Solanam grandijlora, var. pulverulentem. Exteznally it is green, but the sarcocarp is white, somewhat thick, and has a bitter and disagreeable taste. It was treated with water and calcium hydroxide, evaporated to dryness on the water-bath, and the residue extracted with absolute alcohol and the solution filtered.The liquid was then concentrated to a small bulk, resinous matter being removed as it separated. After cooling, the semi-solid residue was treated with dilute hydrochloric acid, which dissolved the alkaloid but left the resinous matter undissolved. The acid solution was decolorised by animal charcoal, precipitated with ammonia, and the precipitate washed with water and dried over sulphuric acid. The a1kaloYd thus obtained is a white subRtance with a, very bitter taste, insoluble in water but soluble in alkalis and dilute acids. When heated with potassium hydroxide, it gives off ammonia, and its solution gives the usual reactions for alkaloids. With platinum tetrachloride, it gives a yellaw precipitate ; mercuric potassium iodide, a yellow precipitat,e; tannin, a turbidity ; ammonia, a white precipi- tate ; concentrated sulphuric acid, an egg-yellow coionr changing to red ; with sulphuric acid and manganese dioxide, a yeIlow colour becoming first green .and then sio.let; concentrated nitric acid, a purplish-red colour.The molecular weight as determined by means of the platinum compound is 236.4. It is an energetic poison, and the fruit itself kills sheep which eat it, hence its name. C. H. B. The author proposes to call this alkalo'id grandiflorilze. Trigonelline. By E. JAHNS (Bey., 20,2840-2843) .-Trigonelline (Abstr., 1886, SS), when heated at 120" with an aqueous solution of barium hydroxide saturated at the boiling point, yields the whole of its nitrogen as methylamine, and when heated with excess of hydro- chloric acid (sp.gr. = 1.2) at 260-270" is converted into nicotinic acid and a combustible gas burning with a green flame, probablyORGANIC CHEMISTRY. 167 methyl chloride. On these grounds, trigonelline is regarded as iden- tical with the methylbetaiue of nicotinic acid, and a comparison of the properties of the two substances shows this to be the case. Alkaloi'ds extracted from the Bark of the Xanthoxylon Senegalense. By GIACOSA and MONARI (Cazzetta, 17, 362-367).- On extracting the bark of t4he Xanthoxylom senegatense (ai-lar-root) with petroleum, an oil is obtained, from which a crystalline substance separates ; t h i s contains no nitrogen, and when purified has a white micaceous appearance, melts at 120-125", and gives a purple-red coloration with chloroform and sulphuric acid.It is probably a pseudocholesterin, but sufficient material waa not at hand for a more complete investigation. The bark, after treatment with petroleum, gives on prolonged boiling with alcohol a brownish extxact, from which, on addition of alkali, a yellowish solid is obtained. This consists of two alkaloi'ds, one of which is amorphous and insoluble in hot water, the other crystalline and soluble. The former was not further examined ; the latter forms a hydrochtoride, crystallising in minute needles or prisms, boluble in cold water, and of intensely bitter taste. The nitrate crystallises in needles melting a t 215-220" ; the platinochloride forms sparingly soluble yellowish prisms.The insoluble alkaloid produces muscular irritatioii with coagulation of myosin, and physiological disturbances analogous to those observed with veratrine. The compounds were not analysed. By A. CLERMONT (Compt. rend., 105, 1022-1023).-20 grams of chopped meat is mixed with 30 grams of water and 0.5 gram of sulphuric acid, and heated in sealed tubes at 180" for six hours. The products are gases and a slightly brown liquid, which is easily filtered. When evaporated to dryness, ammo- niacal vapours are given off, and the residue dissolves readily in water. The solution is not affected by boiling, nor by hydrochloric, nitric, or acetic acids, but it is precipitated by 4 vols. a.lcoho1 of. 90", or by tannin, mercuric chloride, or platinic chloride. 41 grams of peptone are obtained from 20 grams of fresh meat.When heated with water without any acid, the meat is converted into sptonin, which is readily converted into peptone by pepsin at 35" in a slightly acid solution. C. H. B. w. P. w. V. H. V. Formation of Peptone. Mucin of the Submaxillary Gland. By 0. HAMMARSTEN (Zeit. physiol. Chem. 12, 163- 195) .-Obolensky (P'uger's Archiv, 4, 336) and Landwehr (Zeit. physiol. Clzem., 5, 371) have both made analyses of submaxillary mucin, but their method of preparing the rnucin was faulty. In the present research, the following method was first employed : the glands were extracted with water, the extract filtered, and freed from microscopic elements by centrifugalising ; acetic acid was used to precipitate the mucin from this solution ; the precipitate had a stringy character. Attempts were then made to wash t h i s pre- cipitate free from proteids by water acidified with acetic acid, the precipitate being repeatedly well kneaded with the aciditied water ; thia was found to be exceedingly di6culi. The mucin was redis-168 ABSTRAUTS OF CHE-WCAL P-4PERS.solved in faintly alkaline water, and reprecipitated by acetic acid several times, but there was always the same difficulty in freeing it from proteids. This was found to be due t o the presence in the gland extract of a prote'id which is precipitable by acetic acid, and which is with difficulty soluble in excess of that reagent. It belongs to the class of protei'ds to which the name nucleo-albumin has been given. The older method of extracting the mucin from the glands with a weak alkali was not used, because it was found that sub- maxillary mucin is readily decomposed by this treatment.The nucleo- albumin contains 17 per cent. of nitrogen ; and it was admixture with this substance that gave in Landwehr's analyses the somewhat higher percentage of nitrogen than was found subsequently in the present research. The new method ultimately adopted for the preparation of the mucin was as follows : the clear watery extract was acidified with hydrochloric acid until the percentage of the latter reached 0.1- 0-15 ; the mucin which was first precipitated was redissolved when the acid present reached the percentage mentioned. The mixture was then diluted with three to five times its bulk of distilled water ; by this means the mucin was precipitated, and the nucleo-albumin remained in solution.This process was repeated several times, until ulti- mately the mucin was obtained pure. Repeated precipitation and re-solution by this method does not alter the physical properties of the precipitate, which occurs in sticky, yellowish strings, nor does it alter its chemical properties or its elementary composition. This is in contrast with what occurs with dilute alkalis ; a 0.1 per cent. solu- tion o€ sodium hydroxide, or saturated or half saturated lime-water dissolves the mucin ; but when precipitated by acetic acid its stringy character is lost, and the precipitate is flocculent ; ammonia is given off in small quantities, and the percentage of nitrogen in the pre- cipitate increases, the precipitate probably consisting of acid albu- min.The mucin prepared in the manner described was washed with water by decantation ; when free from acid, it becomes white in colour, but becomes again brownish-yellow on the addition of acetic acid ; it was then washed with alcohol and ether, and dried. Elementary analysis of seven preparations gave the following average results in per- centages :-(3, 48.84 ; H, 6.8 ; N, 12.38 ; S, 0.843 ; ash, 035. Previous statements as to the absence of sulphur in mucin appear to be incorrect. The extremely small quantity of phosphorus found might have been contained in the ash. The percentage composition corresponds closely with that obtained by Loebisch (Abstr., 1886, 166), for tendon mucin. Mucin prepared in this way was found to be acid in reaction ; thib cannot be from union with the acid during its preparation, as the quantity of chlorine found by analysis was so excessively small ; but mucin is probably itself of the nature of an acid.A neutral solution of niucin in 8 per cent. sodium chloride soliltion does not coagulate on heating, and even after adding acetic acid it only becomes slightly cloudy. Alcohol precipitates mucin from a neutra'l solution ; the precipitate is soluble in water, unless sodium chloride is present, in which case the precipitate is very insoluble. Mineral acids in small quantities pre-ORGANIC CHEMISTRY. 169 cipitate mucin, and the precipitate is soluble in excess. Cop,per sulphate and ferric chloride, mercuric chloride, lead acetate, potassium dichromate, and potassium alum, all give slimy, gelatinous precipi- tates.Potassio-mercuric iodide gives no precipitate. Saturation with magnesium sulphate or sodium chloride precipitates muuin ; Millon’s, Adamkiewicz’s, and the xanthoproteic reactions are all given by mucin. By heating with dilute mineral acids, a reducing substance is obtained. Potassium ferrocjanide gives no precipitate, or only a cloudiness in a solution of mucin in dilute hydrochloric acid. A sodium chloride solution can be pretty strongly acidified by acetic acid before precipitation occurs ; and potassium ferrocyariide added to such a mixture produces no precipitate. Tannic acid in small qnantities causes the liquid to become slimy and thick, and in excess causes pre- cipitation. Of the varieties of mucin hitherto described, this approaches nearest to tendon mucin, but it differs from that in its solubility in dilute hydrochloric acid, and its behaviour to weak alkalis.W. D. H. The Mucin of Bile. By L. PATJEULL (Zeit. phgsiol. Chem., 12, 196--210).--Landwehr (Zeit. pliysiol. Chem., 8, 114) was the first to point out that the slimy substance in bile is not true mucin; he considered it to be a mixture of globulin with bile salts. An exa- mination of his analytical results shows that there is Rome difficulty in accepting this view; for instance, the percentage of nitrogen i n bile-mucin is 13.8 ; in paraglobulin, 15.85 ; and in glycocholic acid 2 . 5 ; there must therefore be 15.4 per cent. of glycocholic acid in the mixture called bile-mucin. The percentage of carbon on this calculation ought to be 55.01, but it is only 53.09.More- over, although Landwehr states that a mixture of Aodium glyco- oholate with serum-globulin has the physical characters of bile- mucin, it was found in this research that a mixture of globulin with bile deprived of its so-called mucin did not produce the cha- racteristic sliminess of normal bile. The usual method of preparing mucin is not applicable to bile, as the bile-much is slightly soluble in excess of acetic acid. By dialysis, the mucin can be readily freed from bile salts, but not so readily from bile pigment ; moreover, putrefaction is apt to e~isue when dialysis is prolonged. The method ultimately adopted was to precipitate the mucin with five times its volume of absolute alcohol ; the precipitate was collected and freed from alcohol by centrifugnlising, redissolved in water, and again precipitated by alcohol.By thus quickly removing the alcohol, the mucin was not rendered insoluble. The properties of a 0.23 per cent. solution of this so-called mucin were as follows :- After the addition of a trace of acetic acid, which caused no precipitation a t the ordinary temperature, it coagulated on heating, like a proteid solution. More acetic acid caused precipitation without heat, and the precipitate dissolved in excess although with some difficulty ; this acetic acid solution was precipitated by potassium ferrocyanide, potassio-mercuric iodide, mercuric chloride, and tannic acid. Hydro- chloric acid in very small quantities caused a flocculent precipitate, On heating a neutral solution, it coagulated on boiling.170 ABSTRACTS OF CHEMICAL PAPERS.which dissolved easily in excess. Copper sulpha te, ferric chloride, potassio-mercuric iodide, lead acetate, and potash alum gave abun- dant precipitates when added to a neutral solution. Saturation with sodium chloride or magnesium sulphate gave precipitates ; the solu- tion also gave the xanthoproteic, Millon’s, and Adamkiewicz’s reaction. A solution of the mucin in hydrochloric acid (0.3 per cent.) gave no precipitate when digested for some fime a t 40’ ; but if pepsin were first added, a flocculent precipitate formed, as in solutions of nucleo. albumins. Prolonged heating with dilute mineral acids yielded no reducing substance.The following are the results of elementary analysis :-C, 50.89 ; H, 6.735 ; N, 16.14 ; and S, 1.66 per cent. The so-called mucin of bile is regarded, not as trnemncin, nor as a mixture of globulin with bile salts, but as a nucleo-albumin. Small qmntities of true mncin derived from the walla of the gall-bladder appear to be also present i n certain cases. W. D. H.ORGANIC CBEMISTRT. 123Organic Chemistry.Action of Chlorine on Amylene. By J. KONDAKOFF (Chem. Centr.,1887, 979, from J. Russ. Chem. SOC., 1887, 337)-In the course ofinvestigations on the action of chlorine on isomeric amylenes, theauthor obtained from the modification insoluble in sulphuric acid, anunsaturated chloro-derivative, C,H,Cl, in addition to the dichloropen-tane C5HloC12.From the former, two aIcohoIs are obtainable, one aprimary, boiling at 141”, and on oxidation yielding a caproic acid, theother a secondary alcohol, boiling a t 117”, and yielding a ketone ofboiling point 101 -103”, probably methyl propyl ketoue. The primaryalcohol is a P-ethyl ally1 alcohol, CH,Me*CHCH*CH,*OH ; the second-ary alcohol differs both from methyl isopropenyl carbinol and ethylvinylcarbinol, and probably has the constitution CHMe: CH-CHMe-OH.Action of Hypochlorous Acid on the Hydrocarbon C,H,,.By S . A. PBIBYTEK (Chem.. Centr., 1887, 978, from J. Russ. Chem. SOC.,1887,338) .-The hydrocarbon CH2 CMe*CH2*CH2*CMe : CH,, obtainedby Sesukoff from sodium and chlorisobutylene when treated withhypochlorous acid, yields a chlorhydrin, C8H14( OH),Cl,, from whichthe dioxide CsH& can be obtained.The latter gives with water atetratomic alcohol, octyEerythro2, C,H,4(OH)4.By R. VARET (Compt. rend., 105,1070-1072) .-Pure zinc cyanide is dissolved to saturation in aqueousammonia at a gentle heat and a, current of ammonia gas is passedinto the liquid, which is filtered when saturated with the cyanide,again treated with ammonia gas, and allowed to cool. A crystallineprecipitate forms, but redissolves when gently heated, and separateson cooling in large, transparent, prismatic crystals of the compositionZnCy2,BNH3 + H20. This compound loses ammonia and waterwhen exposed t o the air, and becomes white and opaque. It is verysoluble in aqueous or alcoholic ammonia, and if freshly prepared, isalso soluble in water with slight decomposition, but if it has beenprepared for some time, it is immediately decomposed by water.Iti s slowly decomposed by sodium hydroxide in the cold. When heatedV. H. V.V. H. V.Ammonio-zinc Cyanides.* “ Calcium ” in the original.124 ABSTRACTS OF CHEMICAL PAPERS.in a current of ammonia gas, it loses water, but no compound richerin ammonia is formed.When zinc cyanide is dissolved to saturation in alcohol, treatedwith a current of ammonia gas, and the liquid allowed to evaporatespon t)aneously, the compound ZnCy2,2NH3 is obtained in transparentcrystals, which lose ammonia rapidly when exposed to the air andbecome opaque, and are very soluble in aqueous or alcoholic am-monia.The same compound is obtained by passing ammonia gasover gently heated zinc cyanide. Zinc cyanide forms only one com-pound with ammonia, and not a series of compounds like the chlorideand bromide. C. H. B.Methyl Mercaptan and some of its Derivatives. By J.OBERMEYER (Ber., 20, 2918--2928).-Methyl thioacetate is preparedby the action of lead methyl mercaptide on a slight excess of cooledacetic chloride; it boils at 95-96' (not 62-68', Cahours, Compt.rend., 80, 1317, and 81, 1163). The substance described by Cahours(Zoc. cit.) is probably a mixture of the ether with methyl iodide, aceticacid, and hydrobromic acid.M etlyZ thiopropionate, C,H8S0, prepared from propionic chloride, isa colourless liquid of repulsive odour, boiling a t 119-120".Methyl thinbutyrate, C5HloS0, is a light oil having an odour resem-bling that of butyric acid ; i t boils at 140-144".MethyZ a-thi?benzoate, C8HeS0, boils a t 231-232".Methy Zz'sopropyZ sulphide, SMePr, is prepared by dissolving sodiumin isopropyl mercaptan diluted with absolute ether, and the mixture,contJained in a reflux apparatus, is treated with methyl iodide insmall portions; it is then heated for 15 minutes in a water-bath andfiltered.The heavy oil which separates from the solution when keptover night, is removed, and the ethereal solution evaporated and frac-tionally distilled.MethyE anzyZ suZphide, SMe*C5HI1, ie prepared by the action of methyliodide on ainyl mercaptide ; it boils at 136-138". Isoamyl disulphideis also formed.Methyl aZZyZ sdphide, SMe*C3H6, is formed when 25 grams of leadmethyl mercaptide is heated with allyl bromide and ether a t 100".It is a clear liquid of a very penetrating odour, boiling a t 91-93'.When allyl tribromide is heated with an excess of lead methylmercaptide and ether at lOC)", a compound, probably of the formulaSMe*C31-lqBr, is obtained.It could not be purified, as it decomposes at120-130".Methy 1 benxyl sdphide, SMe*C7H7, is obtained by heating leadmethyl mercaptide, and benzyl chloride a t 100". It is a clear liquidof :in odoiir resembling horse-radish, and boils at 195-198'.Methyl pher~yZ sdphide, SMe-Ph, prepared from lead thiophenoland methyl iodide, forms a clear liquid boiling at 187-188".Dimethyl thioresorcino2, C6H4(SMe)2, is an oily liquid of a disagree-able odour boiling a t 278'.Methyl diphenyl sulphide, SMe*CI2H9, is obtained from lead thio-diphenyl ; it crystallises from alcohol in flakes of very slender needles,melting at 107-108".It boils tit 93-95"ORGANIC CHEMISTRY.125Dimethyl diphenyl disulphide, CI4Hl4S2, is prepared by heating thelead mercaptide of diphenylthiohydrate with methyl iodide. Itcrystallises from alcohol in lustrous bright-yellow plates melting a t185-186". N. H. M.Brandy from a Wine from Charente Inferieure. BYE. C. MORIN(Compt. rend., 105, 1019--1022).-The composition of the brandy in100 litres is as follows :-Aldehyde, traces ; ethyl alcohol, 50837grams ; normal propyl alcohol, 27.17 ; isobutyl alcohol, 6.52 ; amylalcohol, 190.21 ; furfuraldehyde and bases, 2.19 ; fragrant oil, 7-61 ;acetic and butyric acids, traces ; isobutylenic glycol, 2-19 ; glycerol,4.38.There is no normal butyl alcohol, and ainyl alcohol constitutesfive-sixths of the higher alcohols, The fragrant oil is one of the con-stituents to which the wine owes its bouquet. (Compare Abstr., 1887,714 and 746.) C. H. B.Production of Normal Amy1 Alcohol by the Fermentationof Glycerol by Bacillus Butylicus. By E. C. MORIN (Con2pt. rend.,105, 816-818) .-When glycerol undergoes fermentation by BLicJZusbzctyEicus under the conditions determined by Fitz, 4 per cent. of thealcohols formed is normal amyl alcohol, boiling at 137-138" ; refrac-tive index at 13.5" for D = 1.414.It is worthy of note that all the alcohols produced by B.b?&yZicusare normal. C. H. B.Action of Zinc Methyl on Valeraldehyde. By J. KUVSINOFF(Chem. Centr., 1887, 987-988, from J. Buss. Chem. SOC., 1887, 204).Methyl isobutyZ carbinol is produced when zinc methyl is added towell-cooled valeraldehyde, and the product of the action decomposedwith ice-water. It is a light, mobile liquid, boiling at 130°, sp. gr.0.8271 at 0" ; its acetate boils at 147", sp. gr. = 0.8805 at 0" ; its ketoneboils at 116- 116.5", and on oxidation yields isopropylacetic, isobutyric,acetic, and formic acids, and is therefore identical with methylisobutyl ketone. V. H. V.Action of Zinc Isoamyl and Zinc Isobutyl on Aldehyde, ByE. SOKOLOFF (Chew,. Centr., 1887, 988, from J. Russ. Chem. Soc., 1887,197--204).-When zinc isoamyl is added to aldehyde, kept cool, andthe resultant product decomposed with ice-water and distilled, methylisoamyl carbinol is obtained besides isopropylethylene, and e thy I andisoamyl alcohols.The first yields an acetate boiling at 166-168", anda ketoite boiling a t 143-145", which yields on oxidation isopropyl-acetic acid. Zinc isobutyl when treated in like manner yields iso-butyl and ethyl alcohols. V. H. V.Methyl Isopropenyl Carbinol. By J. KONDAKOFF (Chem. Centr.,1887, 981, from J. Russ. Chem. SOL, 1887, 336).-When treatedwith a 6 per cent. hydrochloric acid solution, methyl isopropenylcarbin01 is converted into the isomeric trimethylethylene glycol. Thereadiness with which this change is effected is dependeut on th126 ABSTRACTS OF CHEMICAL PAPERS.atomic arrangement; this has also been observed in the case ofunsaturated acids.V. H. V.Iodide of Starch. By H. B. STOCKS (Chem. News, 56, 212-213).-The author takes exception to the four points set forth byI?. Mylius (Abstr., 1887, 568), and makes the following remarks on eachpoint. (1.) He states that iodide of starch is producd by the actionof solutions of pure iodine, or of the vapour of iodine, on moiststarch. (2.) That a limited amount of chlorine produces the bluecolour in mixtures of hydriodic acid, or of an iodide, with starch ; butthat excess of chlorine destroys the colour, probably by the formation ,of a colourless chlorine compound of starch and iodine chloride.(3.) Silver nitrate does decolorise the iodide by removing the iodineas silver iodide, t.he colour being reproduced on the addition of eitheriodine or hydriodic acid ; the action in the latter case may, however,be assumed to be due to iodine set free by the nitric acid liberatedfrom the silver nitrate.(4.) Aqueous solutions of iodine do producethe blue colour with starch.Water is necessary for the production of iodide of starch ; there-fore solutions of iodine in absolute alcohol do not colour dry starchblue. The blue iodide is destroyed by heat, the iodine being, in openvessels, partially volatilised, partially converted into hydriodic acid ;in closed vessels, on the other hand, it is entirely converted intohydriodic acid. This decomposition is quick or slow according asthe qnantity of iodine is smaller or greater.By adding iodine to itsolution decolorised in this manner, the blue colour is again formed,and this decolorisation and recolorisation may be frequently repeatedwith the same starch. Exposure to sunlight also decolorises iodide ofstarch. Iodide of starch is not affected by alcohol, ether, benzene, orcarbon bisulphide ; in fact, iodine may be removed from its solutionsin the last two solvents by means of starch-paste.Iodide of starch disfiolves to a certain extent in water, and is pre-cipitated from the solution by absolute alcohol, by dilute hydro-chloric, sulphuric, and nitric acids, by strong hydrochloric acid, andby salts which do not react with it, such as sodium chloride. Strongnitric and strong sulphuric acid decompose it.Starch solutions arenot precipitated by dilute acids like the solution of the iodide.D. A. L.Constituents of Rice-starch. By L. SOSTEGNI (Chem. Celztr.,1887, 896, from, Stud. d i Chim. Agr. di Pisa, 6, 48--68).-The resultsquoted of the amount of dextrose obtained by the saccharification ofstarch accord with those of Salamon. In the course of the prepara-tion of starch cellulose by Schulze's method, a fat melting at 47-48" was extracted ; the crude fatty acids obtained therefrom melt at50-51" ; the proportion of fat found was 1.5 to 20 per cent. csf thecellulose. The portion of residue, insoluble in ether, obtained in thesaccharificntion of starch, differs from cellulose by its solubility in a2 per cent.solution of potash, and its partial decomposition whenwarmed. From its solut.ion, acetic acid precipitates an amorphoussubstance, turning brown in the air, soluble in Schweizer's reagentwhen moist, but not when dry; it is decomposed when boiled witORGANIC CHEMISTRY. 1 2 1hydrochloric acid, The author regards starch cellulose as a mixtureof cellulose with the derivatives of the latter aubstance or a modi-fication of granulose.Lichenin. By M. H~NIG and S. SCHUBERT (Monatsh., 8, 452-465) .-As there was considerable doubt whether the carbohydratefrom Iceland moss (Cetruria islandica) was a single substance or a,mixture of two or more, the authors have reinvestigated it. The driedand sorted moss was treated repeatedly with a 1 to 2 per cent.solutionof K2C03. A pale-green mass quite free from the original bittertaste was thus obtained. This was then boiled for some time withwater and filtered through linen. The filtrate on cooling depositeda gelatinous precipitate, which separated better when the solution wasfrozen. The liquid still contained some of this gelatinous substance,together with an easily soluble starch. The gelatinous precipitate, forwhich the authors propose to utilise the name Zichenin, previouslyused for the whole extract, is very sparingly soluble in cold water,but dissolves in boiling water to an opalescent solution, which is atonce cleared by the addition of a little potash. The greater part is pre-cipitated from its solutions on cooling, or on the addition of alcohol.Itis not colonred by iodine. When heated with dilute sulphuric acid, itvery readily yields a crystalline dextrose, which gives a, rotation [ a]j =+55.52", and closely resembles, if it is not identical with, ordinarydextrose. The intermediate dextrin-compounds are tasteless and non-rotatory. The above-mentioned soluble carbohydrate, for which theauthors propose the name Zichelz-starch, could not be obtained freefrom lichenin. It is strongly rotating, the rotation increasing thefreer the starch is from lichenin. It is easily soluble in water, but isthrown down 8s a flocculent precipitate by alcohol. The highestrotation obtained was [a]j.= +102.82". It is coloured blue byiodine. Diastase converts it readily into a dextrin showing rotation[a]j = 162.44".Lichenin is not affected by diastase. Lichen-starch,therefore, appears to be a soluble, unorganised modification of ordinarystarch. L. T. T.V. H. V.Reactions of Chloral. By 0. REBUFFAT (Qazzetta, 17, 406-409).-Chloral and sodium acetate, in presence of acetic anhydride, do notreact in accordance with Perkin's reaction; the change is for themost part more profound, leading to the destrnction of the molecule ofchloral. Sodium acetate at a low temperature combines directlyin equimolecular proportions with sodium acetate to form it compound,C2CI3HO,C2H3O2Na, which is white and minutely crystalline ; it isdecomposed by water and by alcohol to form chloral alcoholate.Experiments were also made with the anhydrides of other fatky acids,but without success.V. H. V.Trithioacetaldehydes. By W. MARCKWALD (Bey., 20, 281 7-2818 ; compare Abstr., 1886, 864).-yTrithioacetaldehyde, whenmixed with four times its weight of ethyl iodide and allowed to remainin a closed vessel for some weeks, suddenly undergoes conversion intoa crystalline mass of the &derivative. This change is not due t128 ABSTRACTS OF CHEMICAL PAPERS.the presence of free iodine in the ethyl iodide, since the change doesnot take place when an ethereal solution of the y-aldehyde contaillinga, small quantity of iodine is similarly treated. w. P. w.Metallic Derivatives of Acetylacetone. By A. COMBES (Compt.rend., 105, 868-871).-The author has previously shown that acetyl-acetone has the constitution CH,Ac.COMe, and that the hydrogenof the Cf-Tz-group is readily displaced by chlorine or by sodium.Acetylacetone and its homologues act on metallic salts like trueacids, and yield a new series of crystalline compounds of the generalformula M(C5H7O2),, in which M is a metal with a valency n.Thesodium and potassium derivatives form white, hexagonal prismsbelonging to the rhombic system, and are most readily obtained byadding the required quantity of sodium or potassium ethoxide to analcobolic solution of acetylacetone. They are somewhat soluble inabsolute alcohol, but are insoluble in ether.The magnesium salt is obtained by mixing acetylacetone with anexcess of magnesium carbonate. There is rapid effervescence, andthe filtered liquid when evaporated in a vacuum, deposits transparent,colourless, hexagonal prisms belonging to the rhombic system, whichare anhydrous when dried at 125".The aluminium compound isformed in the preparation of acetylacetone, and is also obtained bythe action of the latter compound on a slightly acid solution ofaluminium chloride. It is insoluble in water, somewhat soluble inalcohol, but less soluble in ether. When the solution is concentrated,it deposits nacreous crystals of the same form as the preceding com-pound, but they are readily decomposed by heat.The copper salt is obtained in pale blue needles of the same form,when a somewhat concentrated solution of cupric acetate is mixedwith a warm saturated aqueous solution of acetylacetone. Thecompound is insoluble in water, and in moderately dilute solutionsthe precipitation of the copper is complete. Larger crystals areformed when a dilute solution of cupric chloride is added to a boilingsolution of acetylacetone.The crystals are anhydrous when dried at125".Ferric chloride and acetylacetone yield a dark-red solution, theformation of which may be used as a test for the ketone, and whenthis is extracted with ether the red compound is dissolved. Whenthe ether evaporates, the iron salt is deposited in bright-red crystals,similar in form to those of the ammonium salt.The lead salt is formed by the action of lead carbonate on theketone, is soluble in water, and resembles the magnesium compoundin its crystalline form.The sodiumand potassium salts are, however, decomposed by hot water, withformation of acetone and an alkaline acetate, and the aluminum andiron compounds are not decomposed by ammonia in alcoholic solution.The sodium salt and methyl iodide yield a new derivative, meth?/E-mtylacetcme, boiling at 165", which has acid properties Rimilar tothose of the original cornpound.It seems, in fact., that the group-cO.CHZ.CO- has the properties which characterise the group COOH,Acetylacetone behaves in fact like a monobasic acidORGANIC CHEMISTRY. 129except that the two hydrogen-atoms cannot act successively. Saltsof the type C,H,02M, in which M is a bivalent metal, have not yetbeen obtained, but the homologues of acetylacetone form salts of thetype (C,H,RO,),M, in which R is an alkyl radicle, and M is a metalof valency n.By J.VOLHARD (Annalen, 241,141--163).-Very good yields of a-brominated acids may be obtainedby a slight modification of Hell's process (Abstr., 1831, 711). Theaction of the bromine and phosphorus on the acid, or preferably thecrude anhydride, is carried OD in a flask provided with a reflux con-denser, instead of in sealed tubes. The bromine and the other ingre-dients must be free from moisture. The bromide is slowly dropped int.0boiling water, in order t o convert it into the monobrominated acairl.The following compounds were prepared : a-monobromosuccink acidforms four-sided prisms, and melts at 159". The ethyl salt boils :It15O-l6O0 under 50 mm. pressure, and tlhe methyl salt at 132-13c;"under 30 mm.pressure. a-Monobromosuccinic acid is decomposed byboiling with water, yielding furnark acid. a-BromopropiorLic& acidforms prismatic crystals melting at 24.5", and z-brornisovaleric acidmelts at 40°, and distils at 230" with slight decomposition.C. H. B.Preparation of a-Bromo-acids.w. c. w.Ethereal Salts of Aldehydo-acids. By W. WISLICENUS (BPT,,20, 2930--2934).-When a mixture of ethyl acetate and ethylformate is added by drops to twice the amount of ether in whichsodium is placed, and the product decomposed by dilute sulphuricacid, an oil is obtained which gives an intense blue-violet coloor withferric chloride, and reacts with phenylhydrazine. The compound isprobably ethyl formyZacetate, COHGH2*COOEt. It could not bepurified; when kept in a desiccator, crystals of ethyl trimesatemelting at 133", separate.The yield of the latter is better than thatobtained by Piutti's method (Abstr., 1887, 491).Ethyl pheizylfornz ylacetafe, COH*CHYh*COOEt, is prepared by sus-pending dry sodium ethoxide in absolute ether (3 parts), adding amixture of ethyl phenylacetate and etliyl formate, and keeping thewhole for several days in a closed vessel. The product is shaken withwater, being kept cold with ice, and the aqueous solution is treatedwith sulphuric acid and extracted with ether. The ethereal extract iswashed, with soda, filtered, and freed from ether in a vacuum, Theresidue, consisting of a crystalline substance and an oil, is filtered,and the oil distilled in a vacuum.If boils at 144-143" under16 mm. pressure, When boiled with dilute aqueous soda, i t is &corn-posed into phenylacetic and formic acids ; the free acid could not beobtained. The alcoholic solution of the ethereal salt gives a veryintense blue-violet coloration with ferric chloride. It reacts readilywith phenylhydrazine, with formation of the compoundthis cryatallises in plates melting at 195-196", and is soluble inalkali, sparingly soluble in ether.BOL. LTV. 130 ABSTRACTS OF CHEMICAL PAPERS.The crystalline compound obtained in the preparation of ethylphenylformylacetate is readily purified by crystallisation from ether ; i thas the same composition as ethyl phenylforniylacetate ; it gives nocolour reaction with ferric chloride.The liquid isomeride chanpsslowly a t the ordinary temperature into the crystalline compound, butthe change is immediate at the melting point of the crystals, 69-71'.The crystalline compound is also decomposed by alkali into formicand phenylacetic acids.Ethyl rnethy Iformylncetate, COH.CHMe*COOEt, is a colourless oil,of agreeable odour, and boils a t 160-162" ; it gives an intense red-violet coloration with ferric chloride, and yields a pyrazoline-deriva-tive with phenylhydrazine.The above ethereal salts are derivatives of the half-aldehyde ofmaIonic acid which v. Pechmnnn assumed (Ber., 17, 936) to exist asan intermediate product in the synthesis of cumalinic acid.N. H. M.Conversion of Benzene-derivatives into Fatty Cornnoundsby the Action of Chlorine in Alkaline Sol&ion.-By A.HANTZSCH (Ber., 20, 2780-2795).-When phenol (at most 50 grams)is dissolved in a moderate excess of aqueous soda (sp. gr. = 1-12>, andthe solution, after dilution with 2 to 3 times its volume of water, istreated at 0" with chlorine, the colour changes through green to brown,and a liquid or semi-solid brown mass separates; this dissolves onthe addition of more alkali, but, subsequently the solution slowlydeposits a grey or black powder insoluble in alkali, and finally byalternating the addition of chlorine and alkali a point is reached,indicated by the dull-yellow colour of the solution, beyond whichchlorination must not be carried. After precipitation of trichloro-phenol by hydrochloric acid, a compound, tvichlorodihydroxyarnenyl-carboxyzic acid, CaH5CI304, is extracted by ether from this solution,and is obtained by caut'ious evaporation of the ether as an oil, whichis best purified by heating it with aqueous ammonia, recrystallisingthe ammonium salt, decomposing this with sulphuric acid, extractingwith ether, and repeatedly recrptallising from water.The acidcrystallises in slender, white needles, which are anhydrous, and meltat 1'76-177" with complete decomposition ; once, however, large,efflorescent, seemingly monoclinic crystals containing 4 mols. H,Owere obtained. It has a sour and yet distinctly sweet taste, isunaltered by exposure to the air, dissolves readily in water, alcohol,and ether, and when boiled in aqueous solution decomposes withevolution of hydrogen chloride.Under the conditions given, theyield of the acid was 50 per cent. The acid is monobasic, and theammonium salt, CsH4CI3O4-NH, + 2Hz0, is the most characteristiccompound ; this crystallises in lustrous, rhombic prisms, has a neutralresction and very sweet taste, is sparingly soluble in water withpartial decomposition, and is not rendered anhydrous by exposure oversulphuric acid or by heating; it decomposes at 123". The remainingsalts are readily soluhle with the exception of the mercurous salt,which crptallises in stellate gronps of needles, and is converted intoa dense, white, microcrystalline powder by heating with water.Concentrated alcoholic potash completely decomposes the acid witORGANIC CHEMISTRY. 131the formation of chloride and carbonate.The methyl salt, CsH4C1304Mecrystallises in needles, melts at 126", and is insoluble in water. Theacid does not form derivatives with hydroxylamine and phenyl-hydrazine, but yields with acetic anhydride a diacetyl-derivative,C,H,Cl,04Ac2, which crystallises best from acetic acid, melts a t 188-192" with complete decomposition, and is insoluble in cold water.When the acid, or better its ammonium salt, is treated with zinc-dust and ammonia, or preferably with sodium-amalgam, and theproduct after acidification is extracted with ether, dichlorodiliydroxy-17 menyZcarBozyEic acid, C,E,CI,(OH),*COOH, is obtained. This veryclosely resembles the trichloro-acid, and melts at 176-177"; it differsfrom it, however, by readily crystallising in large, lustrous prisms,by yielding an ammonium salt which does not crystallise well andmelts a t 185", and by forming an acetyl-derivative melting at 132-134".Concentrated aqueous soda converts the acid into a sodiumd t , C6H,~O4Na2 + 6H20, crystallising in canary-yellow needles.The corresponding acid could not be isolated, but salts were prepared,and these, with the exception of the copper salt which is green, amyellow. The sodium salt gives with ferric chloride a brownish-yellowprecipitate, which dissolves in excess of the reagent to a dark-green solution. The salt is unst~ble and decomposes on heatingwith water, the solution becoming alkaline, whilst mineral acids, evenin the cold, destroy its colour, and convert ih, with the evolution ofcarbonic anhydride, into a white, microcrystalline acid of the com-position C,H,CIO,.This subst'ance is very unstable; it melts at 96-97" with complete decomposition into a carbonaceous mass, and issparingly soluble in water, soluble in alcohol and ether, yielding solu-tions from which, with the exceptiou of the last, the compound cannotagain be obtained by crystallisation. The salts are intensely coloured ;the sodium salt, C,H4CIOzNa + 3H20, which can also be obtainedfrom dichlorodihydroxyamenylcarboxylic acid by heating with con-centratpd aqueous soda at loo", is readily soluble in water, verysparingly soluble in excess of aqueous soda, and crystallises in scales.With regard to the constitution of these derivakives.the formula,CH,Cl*C( OH):CCl*C( 0H):CClCOOH is ascribed to the cornpoundC6H5C1304, termed trichlorodi hydroxynmenylcarboxylic acid. In sup-port of this view, it is urged that, together with the acid, thesymmetrical trichlorophenol [OH : C1: C1: C1= 1 : 2 : 4 : 61 is alwaysobtained, and that the acid can be readily prepared from this trichloro-phenol under conditions similar to those employed in the case ofphenol, 10 grams of trichlorophenol yielding 7 grams of the ammoniumsalt of the acid. It is probable, therefore, that the further action ofchlorine in a1 kaline solution causes the beti mne-ring in trichlorophenolto break at the point 1 : 2 or 1 : 6. To dichlorodihydroxyamenyl-cerboxylic acid is assigned the constitutionCH,Cl*C( OH>:CCl.C(OH):CH.COOH.The compound c6H,c104 derived from it is the carboxylic acid of thecompound G5H,C1O2, which despite its acid character is not a trueacid, since it does not yield an ethyl salt either by treatment inalcoholic solution with hydrogen chloride, or by the action of ethyl36132 ABSTRACTS OF OHEMICAL PAPERS.iodide on its sodium salt.With bromine, it does not form additivebut only substitution derivatives ; ammoniacal silver nitrate andcuprous chloride are not precipitated by it, and its sodium salt, whentreated with phenylhydrazine acetate, yields an amorphous pheqyl-hydrazide, whose composition approximates to that required by theformula CsH,C1(N2PhH),. The formulaCHC1'Co>CHCOOH and <co CHCI*CO CH2>CH,,<CO-CH2 -are ascribed to the two compounds, which are termed chloro-dibeto~erLtamethylenecarboxylic acid and chlorodiketopentamethyEenerespectively, and the analogy between these and derivatives of tbesimilarly cons titu ted dike tohexame t hylene- derivatives is pointed outin the paper.It has not been found possible as yet to displace the remainingchlorine-atom in chlorodiketopentamethylene, but it is possible tosimultaneously withdraw all the chlorine from trichlorodihydroxy-amenylycarboxylic acid.When the acid, or preferably its ammoniumsalt, is treat,ed with a considerable excess of concentrated baryta-water, and heated t o about 60°, barium diliydrox yd~~eto~entumethyle?Le-cnrbosylccte, C6&06B% + 4H20, separates as a bright-yellow powder,insoluble in water.This salt effervesces on the addition of aceticacid, and is converted into the barium salt of dihydroxydiketopenta-metltylene, C,H404Ba + 3iH20, which very closely resembles the pre-ceding salt. Dihydroxydiketopentamethylene could not be preparedi n the pure state ; i t is obtained as a yellow oil from the barium saltby treating i t with hydrochloric acid and extracting with ether, andshows at first it tendency to crystallise, but very rapidly decomposes.It dissolves readily in water, reduces silver nitrate, and yields a com-pound with phenylhydraxine. The formulaeare =signed to dihydroxydiketopentamethylene end its carboxylic acidrespectively.Trichlorophloroglucinol on treatment with bargta yields neitherthe bricbloro-acid nor any of its decomposition products, whilstphloroglucinol and the t h r e e dihydroxybenzenes, when treated in a,similar manner to phenol, do not yield crystalline ammonium salts,but only acid syrups, which on reduction with zinc-dust and ammoniagive monochloracetic acid in large quantitty, but no dichlorodihpdroxy-amenylcarboxylic acid.Bromine, under precisely similar conditions to the above, does nota& on phenol further than to produce tribrornophenol.Derivatives of Isosuccinic Acid.By G. KORNER and A.MENOZZI (Gazzetta, 17, 425441).-1n continuation of a former paperon a-amido-isosuccinic mid, or a-isoaspartic acid (Abstr., 1887, 80 L),the salts are more fully described. The sodium salt, C,H6N04N4 crys-tallises either in needles with 1 mol.H20 from concentrated solutions,or ia prisms with 4 mols. H,O in large, transparent prisms. The potas-w. P. wORQANTC CHEMISTRY. 133sium salt is anhydrous. The calcium, magnesium, zinc, cadmium, lead,copper, and silver salts are described, as also the compounds it formswith hydrochloric and nitric acids. The methyl salt, formed frommethyl iodide and the silver salt, crystallises in white needles ; whenthe potassium salt is heated with methyl iodide, the betazne potassio-iodide, C4H,NMe3O4KII,iH,0, is produced ; it is rery hygroscopic, andforms an atwochloride, C4H5NMe3C104,AuC13, a yellow, insoluble pre-cipitate.Amido-a-isosuccinamic acid, or a-isoasparagin e,NH,*CMe( CONHJGOOH,obtained by heating the neutral amide with aqueous ammonia insealed tubes, forms crystals with hexagonal base, more solubie in coldthan in hot water ; it forms a copper salt, (C4H7NZO3),Cu, crystallisingin small tables.Amido-a-isosuccinamide, N H2*CMe (CONH,),, obtained by heatingpyruvic and hydrocyanic acids, and treating the resultant productwith alcoholic ammonia, crystallises in tables with a rhombic base,sparingly soluble in cold, readily in hot water.When boiled withbarium or potassium hydroxides it gives for each molecule two mole-cules of ammonia; it is decomposed only to a slight extent bymagnesia. Its hydrochloride, sulphate, and nitrate cryatallise in prisms,and are very soluble in water. V. H. V.,Oxidation of Copaiba, Balsam. By S.LEVY and P. ENGL~DER(AvLnaZen, 242, 189--214).-The most important facts contained inthis paper have already a.ppeared in this Journal (Abstr., 1886, 250).The unsymmetrical dimethylsuccinic acid obtained by the oxidationof copaiba balsam is identical with the acid described by Barnstein( t h i s vol., p. 135). The acid forms triclinic crystals [ a : b : c =2.0294 : 1 : 1.1909 ; a = 118" 36', p = 95" 16', 7 = 101"). 'l'he bariumsalt, C6H,04Ba -t 2$H,O, is monoclinic [a : b : c = 1.6006 : 1 : 1.709 ;= 97" 26'1. The salts of calcium, C6H804Ca + H,O, and ammonium, c6 H804(NH,), and C6H9U4*N H p , are crystalline. The nornid sodiumsalt, C6H6OlNa2 + llHzO, forms silky prisms, and the acid Lalt,C,H90,Na + 3+H20, monoclinic prisms,a : b : c = 1.83653 : 1 : 4.18006 ; /3 = 90" 43'.The anhydride of dimethylsuccinic acid melts at 29".It unites withphen y 1 hydrazine, forming dime thy lsucciny lphen y 1 hy drazine, a corn-pound crystallising in monoclinic plates [a : b : c = 1.05521 : 1 : 0.82996;p = 99" .57']. The h i d e of dimethylsuccinicacid melts a t 106". w. c. w. It melts a t 131-132".Dibromosebacic Acid and some of its Derivatives. By A,CLAUS and T. STEINKAULER (Ber., 20, 2882-2889) .--Dibromosebacicacid, C,,H,,Br,O,, is prepared by heating sebacic acid and bromine (2hrnols.) at 160-170" for about three hours. The oily product solidifiesafter some hours to a crystalline mass which is freed from adherentoil by suction on porous plates. It crystallises from water i n long,feathery needlea melting at 115" (uncorr.), and is readily soluble i134 ABSTRACTS OF CHEMICAL PAPERS.alcohol, ether, chloroforrii, and benzene, sparingly soluble in boilingwater.Prolonged boiling with water decomposes the acid and itssalts with elimination of hydrobromic acid. Snlphuric acid dissolvesit unchanged. The sodiwn salt, CloHl4BrzO4Na?, is a heavy white,crystalline substance, very readily soluble in water, from which i tcrystallises with 3 mols. H20. The hydrogen potassium salt is almo~tinsoluble in cold water; the barium (with 2 mols. H,O), cakiunc(with 2 mols. H20), lead, silver, copper, and ammonium salts were alsoprepared. The methyl salt crystallises in small, lustrous, rhombo-hedric plates melting at 50" ,(uricorr.) ; the ethyl salt is a thin oil.Hydroxysebaceic acid, C,oH,,05, is prepared by boiling sodium di-bromosebate with water, .evaporatiug to dryness on a water-bath,digesting over sulphuric acid, and extracting with absolute alcohol.The filtrate is neutralised with alcoholic soda.The sodium salt soobtained is converted into the insoluble lead salt which is then decom-posed with hydrogen sdphide. The acid is readily soluble in hot waterand in cold alcohol, from which it Reparates in small crystalline grainsmelting at 143" (uncorr.) ; i t is very sparingly soluble in ether, in-soluble in benzene and chloroform. The sodium salt, CIOH1105Na2,forms a white, sandy powder very readily soluble in water.Dikydroxysebucic acid, C1OHIBO6, is obtained by boiling an aqueoussolution of dibromosebacic acid with freshly precipitated silver oxide ;the product is filtered, treated with hydrogen sulphide, and evaporatedto a syrup ; this becomes crystalline when kept over snlphuric acid.It is very readily soluble in water, alcohol, and glacial acetic acid,sparingly soluble in ether, insoluble in benzene and chloroform ; itmelts a t 130" (uncorr.) and is decomposed a t a higher temperature.I tis optically inactive. The sodium salt, CloH~B06Na2, is very soluble inwater. N. H. M.Constitution of Levulinic and Malei'c Acids. By A. MrCHAEL(Amer. Chem. J., 9, 364--372).-The reactions trought forward byAnschiitz (Abstr., 1687, 916) in favour of the new constitutionalformula suggested by Iloser for rnalei'c and levulinic acids are ex-amined.It is shown that by assumiug certain reactions for ketonesor for aldehydes similar in kind to those already known, thesyntheses and tran,sformations of these two acids and also of severalothers such as their acetyl-derivatives, mucobromic acid, the dibromo-succinic acids, &c., are quite as easily explained by the old formulaeas by the new ones of Roser. H. I?.Butenyltricarboxylic and Ethylsuccinic Acids. By G. POLKOAwnalen, 24 2, 113-1.26) .-kA7thy1 butetr y l tricarboxy late,is prepared by adding 48 grams of ethyl malonate to a warm solutionof 6.9 grams of sodium in 77 grams of alcohol ; 48.5 grams of ethyla-bromobutyrate is added to the product. It is a pale-yellow liquidboiling between 271" and 281". Its sp. gr. is 1.065 compared withwater at 17".The free acid is soluble in water, alcohol, ether, andacetone. The It melts at 119", and begins to decompose at 124"ORQANIO CHEMISTRY. 135barium salt, Bn3(C7H70,)2, and silver salt, Ag3C7H70s + 1+H20, areamorphous. The normal calcium salt, Ca3(C5H706)2, is very hygro-scopic. The acid salts, CaHa(C7H706)2 and CaH:(C7H7O6) + 2iHz0,are crystalline and insoluble i n alcohol. The zinc, strontium, andpotassium salts are amorphous.E t h y Zsuccinic a,cid, COOH*CHEt*CH,*COOH, is prepared by dis-tilling butenyltricarboxylic acid. It is also formed in the saponifica-tion of ethyl butenjltzicarboxylate. It melts a t 97" and is identicalwith the a-ethylsuccinic acid described by Huggenberg (Abstr.,1878, 782). In addition to the salts described by Huggenberg, thecrystalline strontium salt and the methyl salt were prepared.Thelatter boils at 202-205". The anhydride remains liquid a t -19".Its sp. gr. a t 34O is 1.165. The amide melts a t 214" with decomposi-tion. It is insoluble in cold water and in alcohol. w. c. w.Isobutenyltricarboxylic Acid and Unsymmetrical Dimethyl-succinic Acid. By F. BARNSTETN (Annulen, 242, 126-140).-E t h y l isobiLten,yltricail.boxy h i e , COOEtCMe,.CH( COOEt,)?, is pre-pared by the action of ethyl a-bromisobutyrate on ethyl sodiornalonatein alcoholic solution. It boils at 272--275", and its sp. gr. is 1.064compared with water a t 17". The free acid is difficult to obtain i nthe crystalline state. It is soluble in water, alcohol, ether, andacetone.On boiling the aqueous solution, carbonic anhydride isevolved. The acid melts a t 120" with decomposition, yielding un-symmetrical diniethylsuccinic acid. The sodium, magnesium, bariumand silver salts of isobutenyltricarboxylic acid are amorphous. Thepotassium sait, K3C7H70, + 2H20, forms efflorescent prisms. Thecalcium salts, Ca3(C7H70& + 9Hz0 and Ca(CiH,06)2 + 'LH20, arecrystalline.Unsymmetrical dill i eth y Zsuccinic acid, C 0 OH*CMe2*CH,*C 0 0 H,melts at 139", and is freely soluble in alcohol, ether, acetone, and inhot wat4er. The normal salts of theheavy metals and alkaline earths are, as a rule, very sparingly solublein water. The noymal potassium salt is amorphous and deliquescent ;the acid salt, C6B904K + 5H20, crystallises in plates which effloresceon exposnre t o the air.The normal barium salt, C6H804Ha + 2H20,is crystalline; the acid salt is also crystalline, and readily soluble inwater. The cadmium salt, C6H,0aCd + 6HzO, and the lead salt,C6H80aPb 4- H20, are crystalline, and dissolve with difficulty inwater. DimethyZsuccinyZ chloride, CGH802Cl,, boils at 200-202".Diethyl dimethylsuccinate boils st 213-215". Its sp. gr. at 17" is1.0134 compared with water a t the same temperature. The dimethylsalt boils a t 200" ; sp. gi;. 1.0568 at 16". Dimethybuccinic m-hydride boil8 at 215". Thiophen-derivatives cannot be obtained bythe action of pbosphorus sulphide on unsymmetrical dimethylsuccinicacid. w. c. w.It forms acid and normal salts.Furfuran Derivatives.By W. MARCKWALD (Bey., 20, 2811-2817; compare Abstr., 1876, ii, 444).-Furfuracrylic acid is best ob-tained by heating furfuraldehyde (1 part), sodium acetate (2 parts),and acetic anhydride (2 parts) at '250" for 11 hours ; the yield amouut13G ABSTRACTS OF CHEMICAL PAPERS.to more than 80 per cent. of that theoretically possible. The ammo-nium salt of its reduction-product, f urfuropropionic acid, is convertedi l l to fuyfuropropionamide, C6H70*CONH2, by heating for several hoursin a closed tube at 220" ; this crystallises in white needles, melts at98", distils a t 270" withont decomposition, is soluble in water, alcohol,ether, and benzene, sparingly soluble in light petroleum, and on treat-ment with bromine and aqueous potash does not yield the correspond-ing arnine, since the furfuran nucleus alone is attacked. When fur-furacrylic acid (1 part) is heated with 95 per cent.alcohol (3.5 parts)and saturated with hydrogen chloride, the ethyl salt of a bibasic acid,C.=,H80(COOEt)2, is obtained as an oil which distils a t 286" ; this isheavier than and insoluble in water, soluble in alcohol and ether in allproportions, and has a pleasant, aromatic odour and a very bitlter taste ;the yield amounts t o more than 80 per cent. of that theoretically pos-sible. When saponified, it yields the corresponding acid, C5Hlo05, whichcrystallises from water in large, colourless, transparent, thin prisms,melts a t 138", or with partial decomposition a t about 110" when heatedfor some time in an open vessel, and has a very bitter taste.On dis-tillation, it is converted into oily decomposition-products of partly acidand partly neutral character. The barium, calcium, zinc, and coppersaltq were prepared ; the silver salt, C,H805Ag2, forms microscopicneedles. Since the ethyl salt yields a phenyZhydranide,CIIH,,Oa : N*NHPh,the author ascribes to the acid the formulaCOOH*CH,*CH,*CO*CH2*CH2*COOH,and adduces the following evidence in its support; the acid is notreduced by sodium amalgam, does not form an additive compoundwith bromine, and on oxidation with dilute nitric acid is convertedinto succinic acid (the yield amounting to more than 40 per cent. oftbe acid employed), and a liquid fatty acid (? acetic or propionicacid).The acid is not acted on when heated a t 200" with hydriodicacid saturated a t 0", whilst addition of amorphous phosphorus leadsto experimental difficulties which have not yet been surmoimtled. w. P. w.Action of Nitric Acid on Symmetrical Trichlorobenzene. ByC. L. JACKSON and J. F. WING (Amer. Chem. J., 9, 348-355).-1nproving the constitution of benzenetrisulphonic acid (this vol., p. 152),it was found that with fuming nitric acid, symmetrical trichlorobenzenedid not yield a mononitro-derivative melting af 68" (Beilstein andKurbatow, Annnlen, 192, 233), but the dinitro-derivative melting at130". I f sulphuric acid was used a t the same time, the trinitro-derivative was obtained. Whether a mono-, di-, OP tri-nitro-compoundis obtained depends not only on the temperature and presence orabsence of sulphuric acid, but also to a very considerable extent, onthe purity of the acid employed, an acid of sp.gr. 1.51, free fromnitrogen peroxide, being more effective than one of sp. gr. 1.534 con-taining much nitrogen peroxide.Trichlorobenzene (1 : 3 : 5) is best formed by the chlorination of diORGANIC CHEMISTRY. 137chlormiline prepared by Witt's method (this Journal, 1876, i, 264).Tr~~F,lo1^odii~itrobenzene, C6EC13 (NO,),, is produced at the ordinarytemperature by the action of nitric acid of sp. gr. 1.505 on trichloro-benzene. It crystallises from alcobol in white prisms melting at129.5". The mononitro-compound is readily obtained by boilingwith nitric acid of sp. gr. 1-46. TricltZorotrirLirrohe?zzene, C6Cl,( NOJ3?is prepared by using a mixture of fuming sulphuric acid and nitricacid of sp. gr.1.505. It crystallises from alcohol in nearly whiteneedles melting at 187".Action of Sulphuric Acid on Bromodurene. By 0. JACOBSEN(Rer., 20, 2837-2840) .-When bromodurene is treated with eighttimes ita weight of sulphuric acid a t the ordinary temperature, andthe mixture allowed to remain for 10 to 12 days, a thick brownliquid is obtained, which, on the addition of ice and subsequently ofwater, yields a residue consisting chiefly of dibrornodurene, togetherwith hexamethylbenzene and unaltered bromodurene. The aqueoussolution was free from halogenated sulphonic acids, but contained atleast three sulphonic acids, one of which on hydrolysis yields prehnit-ene, whilst the other two yield pseudocumene.From these results, theauthor concludes that sulphuric acid acts in this case as a bromine-carrier, converting the bromodurene into dibrornodurene and d urene(compare Neumann, Abstr., 1887, 573), the latter of which in thepresence of sulphuric acid yields psendocumene, prehnitene, andhexamethylbenzene in the manner already described by him (Abstr.,1887, 660).Dibrornodurene, under similar conditions, is not acted on by sul-pliuric acid.Probably sulphuric acid acts as a bromine-carrier when in itspresence bromobenzene and paradibromobenzene are converted intodi bromobenzenesulphonic acid and a mixtare of tetra- and hex+bromobenzene respectively, as observed by Herzig (Abstr., 1882, 46).The author has also found that dibromometaxylene, [Me : Me : Br : Br= 1 : 3 : 4 : 61, when treated with chlorosulphonic acid, yields thechloride of its sulphonic acid together with a considerable quantity oftetrabromometnxylene, although but a small quantity of the latterresults when the same dibromometaxylene is heated with sulphuricacid at 240°, an isomeric liquid dibromometaxylene being the chiefAniline Salts.By A. DITTE (Compt. rend., 105, 813-816).-Aniline rnoZytdutP, 2NH2Ph,3Mo0,,5B,O, forms hard, brilliant, trans-parent, prismatic crystals, which lose water when gently heated, anddecompose at a higher temperature. It is obtained by mixing a warmconcentrated solution of ammonium molybdate with excess of a con-cent'rated solution of aniline hydrochloride.Oily drops separate andrapidly change to a crystalline precipitate, and when t h i s is dissolvedin hot water and the solution cooled, the salt crystalliaes in radiatinggroups.An dine tungstnte, ZNH,P h ,4Wo03,3H,0, analogous to ammoniummetatnngstate, forms long, brilliant, transparent needles, which loseH. B.product in this cme. w. P. w138 ABSTRACTS OF CHEMICAL PAPERS.water when gently heated, and at a higher temperature burn with asmoky flame leaving a residue of tungstic anhydride. When am-monium tungstate is mixed with a boiling solution of aniline hydro-chloride, no reaction takes place, but if aniline is added, a portion of i tdissolves, and when the still acid liquid is concentrated and cooled,the aniline tungstate crystallises.Three aniline vanadates can be obtained.Warm solutions of am-monium vanadate and aniline hydrochloride yield a red liquid, acid tolitmus; when this is cooled, i t deposits yellow needles of the com-position NH,Ph,V,0,,4 H,O, which darken on exposure to light, anda t 100" lose water and become green with a metallic lustre, At ahigher temperature, the snit blackens and decomposes. If a smallquantity of aniline is added to the mixed solutions in the experimentjust described, and the black precipitate which forms filtered off, areddish-brown liquid is obtained, which after some hours deposits bril-liant, reddish-brown needles of the composition 4PhNHz,3Vz0,,18H,0.They lose water when heated, and decompose at a higher temperature.If aniline is added gradually in small quantities with constantagitation to a cold concentrated solution of equal equivalents ofaniline hydrochloride and ammonium vanadate, small yellow crystalsseparate. The solution is diluted until these crystals dissolve, andaniline is added until it no longer dissolves.The liquid is then concen-trated over sulphuric acid, when the compound 2NH,Ph,VZO5,2H,Ocrystallises in large pale-yellow plakes mixed with reddish-browncrystals of the preceding compound.A n i l i n e iodate, NH2Ph,21a05, is obtained by mixing a cold almostsaturated solution of' ammonium iodate with an excess of anilinehydrochloride. It forms brilliant, white, nacreous plates, which alterwhen exposed to light, but may be kept in the dark a t a low tempera-ture.When gradually heated, it at first seems to undergo no altern-tion, but below a red heat it detonates very violently. If ammoniumcliiodate is used instead of the normal salt, decomposition of the saltbegins a t the moment of its formation.A n i l i n e chlorccte is obtained in needles by mixing cold concentratedsolutions of sodium chlorate and aniline hydrochloride. It is veryunstable, and decomposes rampidly even in the dark a t 0". At. theordinary temperature, it quickly becomes black, and detonates violentlyat about 20".Aniline boi-ate, NH,Ph,'LB,O3,4H2O, analogous to ammoniumbiborate, is obtained by mixing the ammonium salt with anilinehydrochloride, or more easily by adding aniline to a boiling saturatedsolution of boric acid, in which it is readily soluble.The filteredliquid when cooled first deposits unaltered aniline, and then unctuous,transparent, white lamellae, which lose water when heated, then in-tumesce and give off alkaline vapours,and finally take fire at a highertemperature. C. H. B.Homologues of Aniline and their Separation on a LargeScale. By 0. N. WITT (Chern. h d . , 10, 8--23j.-In the presentcommunicatien, the author, ai'ter detailing the progress made in themanufacture of pure benzene, to1 uene, and xylene, since 1880, referORGANIC CHE3l'ISTRY. 139to the processes of separating the homologues of aniline on a com-mercial scale. The two nitrotoluenes are best isolated by freezingout part of the para-compound, and separating part of the ortho-derivatives by fractional distillation with steam.The medium por-tion is then reduced, and the toluidines thus obtained are subjbcted toa separation process, based on the fact that on treating a mixture ofortho- and para- toluidine with sulphuric acid insufficient in quantityto saturate both isomerides, the para-compound is first attacked.Hence on subjecting such mixtures to distillation, aided by theintroduction of steam, a distillate rich in orthotoluidine is obtained.The latter may then be further purified by repeating the above treat-ment. The residual paratolnidine sulphate is neutralised withcaustic soda or lime, and the base separated by distillation and re-crystallisation. The separation of para- and meta-xylidine may beeffected by sulphonating both isomerides ; metaxylidinesulphonic acidis insoluble, whilst the acid from the para-componud is freely soluble,but yields an almost insoluble sodium salt, from which the base maybe obtained by distillation with addition of a small amount of linie.To isoIate the base from the meta-acid, the latter is heated at 160-180" uuder pressure with five times its weight of hydrochloric acid.The acid mixture is then saturated with soda or lime, and subjectedto distillation with steam.D. B.Butylenic Bases : Characteristics of E thylenic Diamines.By A. COLSON ( C o n y t . rend., 105, 1014-1016).-10 grams of iso-butyiene bromide, boiling at i47-149", was heated to boiling for10 minutes with 40 C.C.of aniline, the excess of aniline expelled bydistillation in a vacuum, and the aniline hydrochloride removed bytreatment with water. The residue was then dissolved in warmhydrobromic acid, and the crystals which separated on cooling werepurified by washing with hydro bromic acid. Diphenylbutyienediaminehydrobromide, C4H8(C,H6N),,2HBr, is thus obtained in white crystals,which melt at 122" with decomposition. I t dissolves in five times itsweight of boiling water, and 10 times its weight of cold water withpartial decomposition, which is prevented if hydrobromic acid ispresent. It is about twice as soluble in alcohol as in water, butis not soluble in ether. The hydrobromide is decomposed completelyby alkaline hydroxides with liberation of the base as a colourless oil,insoluble in water, but soluble in alcohol, ether, and chloroform.Ithas a bitter burning taste, and is coloured brown by nitric acid ; itssp. gr. is about 1.0. With hydrochloric acid it yields a hydrochloridecrystailising in white nodules, which become blue when exposed toair, melt at 98", and dissolve in 10 times their weight of cold waterwith some. decomposition. With acetic acid, the base forms a viscousacetate which is soluble in water, and seems to be uncrystallisable.The aqueous solution of the base has no action on any indicator,and the alcoholic solution has no action on phthaleins, but decolorisesmethyl - orange. In this respect, it resembles ethylenediphenyl-diamine and ethyleneditolyldiamine, and hence i t would seem thatsecondary aromatic diamines containing ethylene a m distinguisliedfrom primary amines such as aniline and toluidine, by the fact tha140 ABSTRAOTS OF OHEMIOAL PAPERS.they are very feebly bmic, and do not act on phthaleins, but decolorisemethyl-orange. The basic properties decrease as the molecular weightincreases.When diphenylb~t~ylenediamine hydrobromide is treated withsodium nitrite at 0" it yields a nitroso-derivative in the form of ayellow precipitate which melts a t 90".C. H. B.Azopseudocumene. By V. POSP~CHOFF (Chem. Centr., 1887, 858-859, from J. Buss. Chem. Xoc., 1887, 113-118).-Nitropseudo-cumene when reduced with sodium amalgam, yields azopseudocuni ene,N,( C6H3MeJ2, which forms yellowish crystals melting at 1'13-1 74",and may be sublimed without decomposition. It is sparingly solublein alcohol, more readily in ether and benzene ; i t dissolves in concen-tratod sulphuric acid, but is reprecipitated on dilution.The corresponding hydrazo- derivative is obtained by reducingnit ropseudocumene with zinc-foil ; it melts at 124-125", and is readilyoxidised in the air to the azo-derivative.In both cases, cumidine isobtained as a bye-product. V. H. V.Formation of Aniline Dyes by the Oxidation of AromaticAmines. By J. BARZILOFFSEY (Chem. Cenfr., 1867, 855-657, fromJ. RIMS. Chena. Xoc., 1887, 132-149) .-By the oxidation of aromaticamines, azo-compounds and polycmines are formed ; by changingcertain conditions, basic products are formed which play an important,part in the aniline dye industry.Jn order to throw some light onthe nature of the chemical changes involved, the products of the oxi-dation of paratoluidine were investigated. The principal compoundsformed are parazotoluene and azotolyl, C,,H,,N,, the latter of whichmay also be obtained from hydroparazotoluene by heating itsalcoholic solution with concentrated liydrochloric acid, as also by theOxidation of toluidine. The formahion of azotolyl by the oxidation ofparatoluidine is explained thus : two atoms of hydrogen are removedfrom two molecules of toluidine with production of hydrnzotoluene, ofwhich one part is converted into azotoluene by further oxidation, whilstthe other part is transformed into the isomeric tolidine, which passesby oxidation into azotolyl.Azotolyl when heated with an alcoholic solution of ammoniumsnlphite is readily transformed into the corresponding hydro-derivstiue, which differs from its analogues in readily combining with acids,and being separable on addition of alkalis.The hydrochloride,(C,H,,HCI) + l$HO, is colourless in the pure state, but when dampis readily oxidised to a compound, pararosotoluidine,which is also obtained by oxidation of a, dilute solution of paratoluidinewitJh large excess of chromic acid, and subsequent addition of soda tothe resultant product. V. H. VORGANIC CHEMISTRY, 131Formation of Dyes by means of Hydrogen Peroxide. Bg C.WURSTER (Ber., 20,2934-2940).-Ammonia is added t o an emulsion ofphenol and water so that a part of the phenol remains undissolved ;a solution of sodium carbonate and an equal volume of hydrogenperoxide are added, and the whole diluted with water.The mixtureis well shaken, a crystal of a hydroxylarnine salt added, and the wholeagain shaken ; a bright-blue and then a deep-blue coloration is pro-duced which in a day or two changes to glseen. The dye which isextracted with ether is shown to be phenolqainonimide.Hydrogen peroxide is found in the sap of many plants ; it is alsoproduced by micro-organisms, especially by the non-pathogenic.All the monatomic phenols of the benzene series examined, in whichthe para-position to the hydroxyl-group is free, gave quinone-imideswith hydrogen peroxide and ammonia. Hydroxy-acids also yielddyes.Lacmo'id is formed when an arnmoniacal solution of resorcinolis boiled with a little hydrogen peroxide.If sodium carbonate is added to a mixture of resorcinol andquinone, a deep-green solution is obtained which, when shaken withair becomes yellow, then reddish-yellow and brownish-red ; when airis removed, the green colour is regenerated.A similar change ofcolour is observed in many leaves, especially those of Berberis whichcontain a considerable amount of hydrogen peroxide.Pyrocatechol, orcinol, and some plant constituents, such AS phlo-ridzin, also give dyes with hydrogen peroxide.Formation of Safranines. By P. BARBIER and L. VIGNON (COW@.rend., 105, 939--941).-1t has been shown that phenosafranine isformed by oxidising a mixture of paraphenylene diamine (1 mol.)and aniline (2 mols.), and it is known that amidoazobenzene yieldsparaphenylenedinmine on reduction.It therefore seemed probablethat the action of nitrobenzene or amidoazobenzene in presence of somereducing agent evolving hydrogen, should yield phenosafranine, andthis supposition is confirmed by experiment.Amidoazobenzene hydrochloride (1 mol.) is mixed with iron andhydrochloric acid in sufficient quantity t o yield one molecular propor-tion (H,) of hydrogen, and sufficient nitrobenzene to form a paste,and heated at 188" for three hours. The product is diluted with water,and treated with a current of steam to remove unchanged aniline;the aqueous solution is then mixed with ammonia, filtered, and thesafranine precipitated by adding sodium chloride.The phenosafra-nine which separates is purified by repeated precipitation by meansof salt and recrystallisation from hot water.Amidoazotoluene likewise yields a safranine when heated withnitrobenzene, and hence it seems that this constitutes a generalreaction for the preparation of safranines.Nitro-derivatives of Oxanilide. By W. G. MIXTER and F. 0.WaurHm (Awzer. Chew. J., 9, 355--361).-Hnebner and Rudolph'swork on paradinitro-oxmilide is confirmed. Tdranitrooxanilide,C,0a[NH*C&X3(NO~),jr [NH : (NO,)% = 1 : 2 : 41, is formed by theN. H. M.C. H. B142 ARSTRACTS OF CHEMICAL PAPERS.action of red fuming nitric acid on oxanilide; it melts at 300°, ishut slightly soluble, and is eaqilp saponified bv weak potash. Hexa-nitro-oxan.iZide, C202[NH.C&L(N02)3]2 [NH : (NO,), = 1 : 2 : 4: 61,is ob-tained when a mixture of fEming nitric acid and strong sulphuricacid is employed ; it is the highest substitution product obtainable.It melts at 300", its best solvent is glacial acetic acid.When heatedwith sulphuric acid at 200", it yields a trinitraniline melting at188", which is the melting point of the only known trinitraniline,NH,: (NO,), = 1 : 2 : 4 : 6. In alkaline solutions, it dissolves withformation of trinitrophenyloxanilide, trinitro phenol, and trinitraniline.Trilziti-ophelzZ/Zoxa~zide, NH,*CO*CO*NH*C,H, (NO,) 3, crystallises inwhite fibres, and melts with decomposition a t 255-260". It hasstrongly marked acid characters. The potassium and ammoniumsalts are described.H. B.Nitro-derivatives of Dibromoxanilide. By W. G. MIXTER andC. P. WILLCOX (Arner. Chem. J., 9,361-364).-Dinitrodibromoa?nnilide,C,0z(NH-C,H,Br.N02)2 [NE : NO2 : Br = 1 : 2 : 43, is obtained bythe action of strong nitric acid on paradibromoxanilide. It is yellow,melts at 288", and when saponified yields orthonitroparabromaniline,melting at 111.4".Tetranitrodihromoza~nilide, C202[ NH*C6H2 (N02),Br J2, is obtainedwith some difficulty by using red fuming nitric acid. It is white,melts at 285-287", and does not yield dinitrobromaniline whensaponified. H. B.Compounds of Alloxan with Aromatic Amines. By G.PELLIZZARI (G'azzatta, 17, 409-425) .-Alloxan combines directly withthe aromatic aniines to form additive products from which, however,the base cannot be recovered as such.Thus when a concentrated boil-ing aqueous solution of alloxan is agitated with a-naphthylamine, andthe solution cooled, a compound of the formula C,,H,,N,O, separatesC4H2N20 + CloH7NH2 = Cl~HllN304. This compound, a-nccphthyZ-arnine-aZZoxan, ciystallises in transparent, colourless needles, insolublein water, acids, aqueous ammonia, bct Boluble in ether, benzene, andchloroform ; i t is coloured greenish by concentrated sulphuric acid.When heated with alkalirj, it, dissolves, yielding ammonia and thepotassium salt of an acid, CI~HION~O,; on acidification, the acidseparates in long, glistening needles, insoluble in ether, benzene, andchloroform, but very soluble in alcohol.At 110", it loses the elementsof a molecule of water, but takes it up again on recrystallisation fromaqueous alcohol. PNaphthylamine apparently does not combine witha1 loxan.Aniline combines with alloxan to form pheny Zarnine-aZZoxam,C,,HgN304 = CpH,N204 + PhNH2,which crystallises in scales, decomposing at 248". It forms a hydro-chZoride, C10HgN304,HC1, which crystallises in transparent needlea,and a silver salt, CloHsAgN304, a white, insoluble powder. Like thenaphthyl-derivative, it yields an acid, C9H8N303, when boiled witORGANIC CHEMISTRY. 143alkalis, thus : Thisacid crystallises in colourless needles which decompose a t 180" withoutfusion ; i t is soluble in alkalis and their carbonates ; its silver salt,,CgH,AgN,03, is a white crystalline precipitate.On dry distillation,phenylamine-alloxan yields parafol uidine.MetA?/ZphenyZu}iiine-aZZ~xan, Cll H,,N30, = C4HzNz04 + NHPhMe,crystallises in white scales soluble in alcohol, moderately solublein boiling water ; its hydrochloride, CllHllN304,HC1, forms colourlessprisms.Uimeth?/Z~ihenyZamine-aZZoxan, C1,H,,N3O3 + HzO, crystallises in colour-less needles, sparingly soluble in water, and decomposing at 230". ItshydrochEoride crystallises i n transparent needles, the nitrate in lozenge-shaped crystals, the ozaZate in quadrangular tables ; the silver salt isa white precipitate. This compound, like the preceding, is decom-posed by alkalis with formation of an acid.To these derivatives, of which that of aniline is selected as a typicalexample, the author ascribes either the formulaCloH9N304 + HZO = CgH&N,O, + NH, + CO,.or COOH*NHCO*C(CONHz) C,H,*NHz, of which the latter illus-trates a t once the basic and acid character, as also its decompositionby alkalis to form an acid, C9H8N203, by elimination of ammonia andcarbonic anhydride, thus : COOH*NH.CO(CONH2) : C,H,-NH, +H20 = COOH.C(CONH2) On the otherhand, the combination of the benzene nucleus with another groupingby two of its carbon-atoms is unusual.The other formula illustratesthe formation of paratoluidine by the dry distillation of the anilinecompound, whilst the production of the acid compound is explained asa result of two successive reactions, in the first of which a carboxylicacid is formed which subsequently gives oEa molecule of water toproduce an imide, thus : CO<NH.co NH.co>C(OH)mC6H4*NH, + 2Hz0 =COOE*C(OH)(CONH2)*C,H,*NH2 + CO, + NH,, and(ii) COOH*C(OH)(CONH2).CJ&*NH4 - OHz =C,H,*NH, + NH3 + COs.NH<::> c (OH)GH.NH,.If the latter formula be correct, then the above compounds might beconsidered as derivatives of dialuric acid or tartrony 1 carbamide.Benzylidenephthalide and Isobenzalphthalide.By . 8.GABRIEL (Ber., 20, 2863--868).-Benzylidenephthalide crystalhsesin small, monoclinic forms ; a : b : c = 1.9005 : 1 : 2.3830 ; p =76" 2-5'.Benzylphthalimidine (Abstr., 1885, 902, 1229) is readily obtainedby adding a mixture of benzalphthalimidine (12 grams) andamorphous phosphorus (6 grams) to 36 C.C. of boiling hydriodicacid (b.p. = l27'), and subsequently heating for 45 minutesin a reflux apparatns. The yield amounts to 80 per cent. of thattheoretically possible. When treated with phosphorus oxychloyide,V. H. V144 ABSTRACTS OF CHEMICAL PAPERS.and heated on a water-bath until hydrogen chloride ceases to beevolved, a product is obtained which, after extraction with water,solution in alcohol, and precipitation with ammonia, crystallises frombenzene in orange- or cinnabar-red, slender needles of the compositionCIBHIIN. This compound is soluble in chloroform, but only verysparingly in alcohol, has feeble basic properties, arid forms unstablepurple salts which are soluble in alcohol, and could not be amalysedwith the exception of the picrnte, C,H2,N50,, a salt crystallising incantharides-green prisms appearing reddish-violet by transmittedlight,.Phthalimidine also yields with phosphorus oxychloride ablack powder having a bronze lustre; this is insoluble in allordinary reagents and dissolves in sulphuric acid with a dark bluecolour.When isobenzalphthalide is heated with methylamine and alcoholf o r nine hours a t lOO", it is converted into P-desoxybenzoilzca~box~Z-methylamide, C0Ph.C Hz*CaH,*CO-NMeH ; this crpstallises from ben-zene in snow-white, matted needles, melts at 14-14Ao, and whenheated a t 200" is converted into its constituents.Nitrobenxylidenephthalide, on reduction with hydriodic acid andamorphous phosphorus, yields in addition to isobenzalphthalide awhite powder ; this cryst'allises from acetic acid in colourless, cornpactneedles, begins to sinter at 240", melts at 255-25i0, and dissolvesin aqueous soda, or potash yielding yellow crystals of thecorresponding salt.The crystals have the composition CI5H,,NOa.When the compound (1 gram) is heated with methyl alcohol (10 c.c.),potassium hydroxide (1.7 gram) and methyl iodide (3 grams) a t100" for one hour, two compounds are obtained of the compositionC15HION02Me ; one of these crystallises out on cooling in colourless,compact crystals, which begin to sinter nt 200", melt at 235-5237",and are sparingly soluble in alcohol, insoluble in alkalis, whilst thesecond remains in the mother-liquor and crystallises from alcohol inlong, colourless needles melting at 119-121". Since the compoundis not a lactone, its constitution is probably expressed by one of theC(0H) : CPh CO.CHPhtwo formd= C6&< CO--BH> or COB,< CO-NH>.w. P. w.Beneyl-derivatives. By S. GABRIEL and H. HENDESS (Rer., 20,2869- 28 72) .-MetanitrobsiLzzJZ~h~haZ~m ide, NOz*C6H4*CHz*N : C,H,O,,is formed when an intimate mixture of metanitrobenzyl chloride(1-7 gram) and potassium phthalimide (2 grams) is heated at 120°for about one hour. It crystallises in slender needles, melts at 155",and is soluble in acetic acid and alcohol, sparingly soluble in water.When heated with fuming hgdroohloric acid at 200" for two hours, iti s converted into a mixture of phthalic acid and nietunitrobenzy Zaminnehydrochloride ; the latter crystallises in needles. Metanitrobenzyl-m i n e yields an acetyl-derivative, C&N202Ac, cryatallising inneedles whicb melt at 91 O , and a pZcct&aochZoride, (C7H,N202),,HzPtC1,,crystallising in rhombic scales, whilst reduction with tin a,ndhydrochloric acid converts it into metamidobenzy lamine ; thisdmolvea in water, has e atrongly alkaline reaction, and forORGANIC CHEMISTRY.145picrate crgstallising in sparingly soluble scales and a plafiinochloride,C,H,(NH2),,H2PtC1,, cryshlhing in yellow scales.BenzaZtetrach Zwcvphthulide, CHPh : C<c,;i>CO, is obtained whentetrachlorophthalic anhydride (10 parts) is heated with phenylaceticacid ( 5 parts) and sodium acetate ($ part). I t crystallises in slender,yellow needles, melts above 360", and 1s practically insoluble in aceticacid and hot alcohol, more soluble in hot benzene and nitrobenzene.On treatment with sodiiim hydroxide, it is converted into a-tetrachloro-desoz y benzo~nort hocarbox y Zic whichcrystallises in colourless needles, melts at 175", dissolves readily inalcohol, ether and benzene, and yields a barium salt, (C,,H7C1403)zBa,crystallising in pale rose-coloured needles.Dichlorophthalic anhydride, when similarly treated, yields benzaltli-chlorophthalide, CHPh C<C6HzC12>C0, which crystallises in small,brownish-yellow needles, melts at 2 loo, dissolves readily in benzene,and by the action of alkalis is converted into oc-dichlorodesoxybenzo~~~ -orthocarboxlylic acid, C15H10C1203, crystallising in colourless needlesacid, CHzP h* C 0. c& 14.c 0 0 H,-0-melting at 117".w. P. w.Resazo'in and Resorufin. By E. EHRLICH (Mowatsh., 8, 425-428) .-Bruiiner and Kraemer (Abstr., 1884,1333) proposed to dropthe prefix di- from the names diazoresorcinol and diazoresorufin, butthe author and Benedikt, contending that these compounds are nomore azo- than diazo-derivatives, suggest re-naming them resuaozn andresorwjin.Resazojin when dissolved in potash and oxidised with hydrogenperoxide yields hydroryresazoln, C18H12N207. This substance crystal-lises in almost colourless needles or scales which decompose beforefusion, yielding a slight crystalline sublimate and leaving a carbon-aceous residue. It is sparingly soluble in alcohol, soluble in glacialacetic and hydrochloric acids.Alkalis dissolve it with a reddish-yellow coloration. When reduced with zinc and sulphuric acid orammonia, it yields a derivative of the formula C,,H,,NZO7, crystallisingin needles.These oxidation-derivatives confirm the correctness of Weselskyand Benedikt's formula Cl,H12N,0s for resazo'in, but are not in keep-ing with Brunner and Kraemer's formula C12H9N04 (Eoc. c i f . ) .L. T. T.Three Isomeric Tritolylstibines. By A. MICHAELIS and U.GENZKEN (Annnlen, 242,164--188).-The preparation of the tritolgl-ptibines has been previously described by the authors(Abstr., 1884,1135).Paratritolylstibine forms hexagonal rhombohedra [a : c = 1 : 1.58071.Its sp. gr. a t 15.6' is 1.35448 (water at 4" = 1). It melts at 127-128" and dissolves freely in chloroform.It forms additive chlorine,bromine, and iodine compounds which have already been described(hc. cit.). On the addition of a cold alcoholic solution of mercuricchloride to pal-atritolylstibine dissolved in alcohol and ether, tritolyl-stibinemercuric chloride is precipitated, (CrHACH3)3Sb,HgClz, but if hotVOL. LIV. 146 ABSTRACTS OF CHEMICAL PAPERS.solutious are mixed, paratolylmercuric chloride, C6H4Me.HgC1, isobtained.Orthotritoly Zstibine, Sb( C6H4Me),, melts at 79-40", and dissolvesfreely in chloroform, benzene, ether, and light petroleum. Orfho-tolylmercuric chloride, c6H4Me*HgC1, is obtained as a crystallinepowder on mixing ethereal solutions of mercuriq chloride andmercury ditolyl. It melts a t 145-i46".Orthotritolylmercuric chlor-iileis freely soluble in chloroform and is deposited from alcohol in silkyplates. Unlike the para-compound, the alcoholic solution is notdecomposed on boiling, yielding tolylrnercuric chloride.I n the preparation of orthotritolylstibine, needle-shaped crystalsmelting a t 112" are obtained. The compound (probably orthopara-tritolylstibine) is freely soluble in chloroform, benzene, ether, andlight petroleum. With mercuric chloride, it yields a crystalline com-pound which melts at 164" with decomposition. The alcoholicsolution is not decomposed on boiling.Orthotritolylstibine chloride, (C6H4*CH3),SbC1,, melts at 178-179",the bromide melts a t 209-210", and the iodide a t 174--175'. Theoaide melts a t 220" and dissolves freely in acids.MetatritoZyZstibine melts at 67-68' and dissolves freely in ether,benzene, chloroform, and acetic acid. I t s sp.gr. at 15.7" is 1.3957compared with water a t 4". The additive compound with mercuricchloride melts with decomposition a t 140". The alcoholic solutionis decomposed by boiling, yielding metatolylmercuric chloride,C6H4Me*HgCl (m. p. 159-16d"). Hetatrito Zy Zstib lne chloride meltsa t 137-138". It is very soluble in benzene, ether, and chloroforni.The bromide has been previously described (loc. cit.). The iotlidemelts at 138-139" and dissolves freely in chloroform, benzene, ether,and alcohol. The oxide is sparingly soluble in alkalis, alcohol,benzene, chloroform, and ether.OH*Sb( C6H4Me),*OAc,is crystallirie and melts a t 142-143".Metatritolylstibine swlpllide,SbS(C6H4D/Ie),, is obtained as a crystalline compound by the action ofhydrogen sulphide on a solution of tritolylstibine chloride in alco1:olioammonia. It melts a t 162-163" and dissolves in chloroform aridbenzene. Chlorine, bromine, or iodine converts the sulphide (insolution in chloroform) into the corresponding chloride, bromide,or iodide. w. c. w.The basic acetate,Decomposition of Isonitroso-compounds. By H. v. PECHMANN(Ber., 20, 2904-2906 ; compare Abstr., 1887, 1103).--BenzoyZ-fornzaldeh yde hydrate, COPh*CH(OH),, is obtained as follows : nitroso-acetophenone is dissolved in a strong solution of hydrogen sodiumsulphite, and thedouble compound so obtained boiled with 10 partsof 30 per cent.snlphuric acid ; on cooling, the whole solidifies to amass of white needles, which are dissolved out in ether and recrystal-lised from water. It forms lustrous, colourless needles, which melt ah73' and give off water a t a higher temperature. The anhydrousLrldehyde boils at above 142" under 125 mm. pressure. The hydratehas a peculiar penetrating odour, dissolves readily in the usuaORGANIC CHEMISTRY. 147solvents, reduces ammoniacal silver solution, and is converted intoinandelic acid by alkalis. When the dilute aqueous solution istreated with some drops of ammonia, flakes separate which formspkieres on adding acid.Phenyltoluquinoxaline (Hinsberg, AnnnZen, 23 7, 370) is formedwhen an aqueous aldehyde solution is warmed with toluylenediaminesiilphate and sodium acetate, and crystallises in colourless needlesmelting at 155".Negative Nature of Organic Radicles.By V. MEYER (Ber.,20, 2944-2952) .-It was shown previously that desoxybenzoyn andbenzyl cyanide, when treated with sodium ethoxide and an alkyliodide, yield derivatives in which one hydrogen-atom of the me-thylene-group is replaced by an alkyl radicie, whilst ethyl phenyl-acetate does not react under similar conditions (Abstr., 1887, 572),This reaction has now been extended to a large number of aromaticcompounds containing carbonyl- and methylene-groups, and it isfound that the hydrogen of the methylene-group is displaceable by annikyl radicle only in compounds precisely analogous in constitution todesoxybenzoh and benzyl cyanide.Under these conditions, the amidesCH,Ph*CO.NEt, and CH,Ph*CO*NPh,, the phenylpropionitrile,CH,Ph*CH,*CH,*CN, the nitrile of cinnamic acid, CHPh CH-CN,and methyl diphenylacetate, CHPh*,CO@Me, do not yield alkyl-derivatives ; aceto- and butyro-nitrile are unattacked ; whilstdibenz y 1 ketone, C H,Ph*C 0 C H,Ph, paraphen y lenediace tonitril e,CN*CH,-C,H,*CH,.CN, and derivatives of the type COR-CH,.R',containing complex aromatic radicles (naphthyl, phenanthryl, $c.)readily form alkyl-compounds. The sulphone, SO,Ph*CH,Ph, acompound which crystallises well and volatilises without decomposi-tion, does not reaoij with sodium ethoxide and alkyI iodides.Di- and tri-phenylmethane also do not yield alkyl-derivatives whensimilarly treated, whilst beautiful, violet-coloured compounds areformed by the action of sodium ethoxide on the nitro-derivativesof these hydrocarbons.Further investigation has shown thaf under no condition canmore than one hydrogen-atom of the methylene-group presentin desoxybeneoyn be displaced by an alkyl radicle. Nor is it possiblet o effect a substitution of an alkyl radicle for the remaining hydrogen-atom of the methylene-group in benzojin, COPh*CHPh*OH, orits acetyl-derivative, COPh*CHPh*OAc.Diphenylacetonitrile,C HP h,*CN, a well- charac terised crystalline compound , how ever,is readily acted on by sodium ethoxide and halojid alkyl-derivatives.The substitution of methyl in the phenyl-group of benzyl cyanidedoes not seem to interfere with the production of alkyl-derivatives,since the three isomeric methylbenzyl cyanides, C6H,Me.CH2*CN,react with sodium ethoxide and benzyl chloride just as readilyas benzyl cyanide itself, although the yield of the productC6H4Me-CH(C7H,)*CN is not quite the same in each case.Like nitroethane and ethyl acetoacetate, desoxybenzoin and benzylcyanide combine with nitrous acid, diazobenzene, &c.The diazo-derivatives have little stability and are difficult of isolation; theN. H. M.7 148 ABSTRACTS OF CHEMICAL PAPERS.isonitroso-compounds, CO*Ph*CPh NoOK and CN-CPh : NOOH, canreadily be obtained ; the: latter crystallises well and is distinctly acidin character. w. P. w.Derivatives of Dimethyl-2-Resorcylic Acid. By H. MEYER(Monatsh., 8, 429-438).-MethyE diinethyl-oc-).esorcylate,CGH,( OMe),*COOMe,crystallises in prisms, melts at 81", boils a t 298", and sublimes in whiteneedles. Methyl m onomet 21 y E-a-resorc y late, 0 H *C6H, (OMe) *C 0 ()Me,which is also formed during the methylation of dimethyl-a-resorcylicacid, forms an oil boiling with partial decomposition a t 315". Nitro-dimethyE-a:-resorcyZic acid, N02.C,H2(0Me),*COOH, may be formedeither by heating the solid acid with nitric acid, or by adding nitric acidto an acetic acid solution of the acid. It crystallises in yellow needlesor prisms, is sparingly soluble in water, easily in alcohol and glacialacetic acid, and melts at 225", subliming at a higher temperature.It forms well-marked salts, of which those of the alkalis are easily,the others sparingly, soluble in water.On reduction, it yieldsamidodimethy 1-a-resorc y Zic acid, NHz.CGHz (OMe),. CO 0 H, which crys-tallises in hexagonal plates, easily soluble in alcohol, sparingly inwater, and melting with decomposition at 182". Its hydrochlorideand stannochZoride crystallise in needles. The silver and copper saltsare very sparingly soluble in water. The amido-acid does not yield aquinoline-derivative, and consequently the amido- (respectively nitro-)group is probably in the para-position to the carboxyl-group.When calcium dimet'hyl-a-resorcylate is subjected to dry distillation,dimethylresorcinol distils over. The residue contains calcium car.bonate, a resinous compound (probably an etheric-derivative of res-orcinol), and the calcium salt of an acid which the author has notyet isolated.This acid melts at about 222", gives a violet colorationwith ferric chloride, and is therefore an ortho-hydroxy acid.L. T. T.Action of Phthalic Anhydride on Amido-acids. By L. REESE(Annalem, 242, 1-22) .-Drechsel has shown (Abstr., 1883, 1126 jthat phthnlylamidoacetic acid is formed by the action of phthalicanhydride on glycocine, and he has described the properties of theacid and of several of its salts. The sodium salt is very soluble inwater, but it is precipitated on the addition of alcohol to the solution.The precipitate has the composition CloH6N0,Na + HzO. The am-monium salt, CloH6W0,NH4, is prepared by adding alcoholic ammoniato an alcoholic solution of the acid ; it melts at 205" with decomposi-tion.The salt is very soluble in water ; the aqueous solution losesammonia on evaporation. When a cold solution of copper sulphateis added to the sodium saltl, rhombic prisms or plates of a pale bluecolour are depnsited having the composition ( C,,H6N04),Cu + 3H,O,but on mixing hot solutions the anhydrous salt is deposited in six-sidedplates. When the copper salt is cautiously heated, phthalirnide andbenzoic acid sublime. The silver salt, CloH6N0&, is deposited fromhot aqueous solutions in prisms. By the action of ethyl iodide oORGANIC CHEMISTRY. 149t8his salt, the et'hylic salt, ~,H,NO,Et, is obtained. It crystallises inneedles, dissolves freely in ether, chloroform, and hot alcohol, meltsat 104-105", and distils at a temperature above 300" without decom-position.Salts of glycocinephthaloic acid are formed by neutralising hotaqueous solutions of the alkalis or alkaline earths with phthalylamido-acetic acid, and evaporating the solution.The sodium salt is amor-phous. It is precipitated as a gelatinous mass on the addition ofalcohol to the concentrated aqueous solution. The potassium salt isdeliquescent, and crystallises in needles ; the barium salt formsrhombic plates. The copper salt is deposited in needle-shaped crys-tals on the addition of the sodium salt to a solution of coppersulphate. The crystalline silver salt is soluble in hot water.P h t l ~ a t y t a ~ ~ d o c a ~ o ~ c acid, C,,H,,NO,, is prepared by fusing a mix-ture of phthalic anhydride and leucine.The pure acid crystallises inneedles, melts at 115-116", and is soluble in alcohol and ether ; onthe addibion of water to the alcoholic solution, the acid is depositedin the form of a n oily liquid. The alcoholic solution is Iavogyrate.On dry distillation, optically inactive phthalylamidocaproic acid isformed. The inactive acid can be recrystallised from hot alcohol andether. It melts in boiling water, and the solution on cooling depositsa few crystals. The acti-re acid forms a crystalline platodiammoniumsalt, Pt(NH,*NH,~15H,,NOa)z + 3Hz0, insoluble in alcohol. The in-active acid forms a similar compound containing 3Q mols. HzO, whichis less soluble in cold water than the salt of the optically active acid,The copper salt is amorphous.It is soluble in alcohol, and isdecomposed by heat, yielding butylp hthalimide.The phthalylamidocaproic acids are converted by the action ofalkalis into leucinphthaloic acids, and finally into leucine and phthalicacid.The sodium salt of the optically active leucinephthaloic acid isamorphous, and is deposited as a gelatinous mass on the addition ofalcohol to the aqueous solutiou. The potassium salt, K2Cl4HI5NO5, iscrystalline and freely soluble in water. The barium salt is crystallineand sparingly soluble. The platodiammonium salt forms rhombicplates freely soluble in water, sparingly soluble in alcohol, and in-soluble in ether. The amorphous copper salt dissolves freely inalcohol. The free acid, COOH*C6Ha*CO*NH*CH( COOH).CH,Pr(l., issoluble in alcohol and ether. It is decomposed by boiling water, yield-ing phthalic acid and leucine.It melts at 130-132", and splits u pinto water and phtlhalyIamidocaproic acid (active), The potassiumsalt of inactive leucinephthaloic acid is deposited in crystals on theaddition of alcohol to the aqueous solution. The silver salt is amor-phous. The free acid melts at 152-153", splitting up into inactivephtlhalyly lamidocaproic acid and water. It closely resembles theAction of Phthalyl Dichloride on Ethyl Sodiomalonate. ByJ. WISLICENJS (Artnalert, 242, 23-93) .-By the action of phthalyldichloride (1 mol.) on ethyl sodiomalonate (2 mols.) mixed with ether,8 mixture of ethyl phthalylmalonate, dimalonate and phthaloxyldi-It is quickly saponified by boiling water.optically active acid in its properties.w. c. wI50 ABSTRACTS OF CHEMICAL PAPERS.malonate is obtained. The crude product is treated with water, andthe ethereal solution evaporated. An oily liquid remains whichdeposits crystals of ethyl phthalylmalonate. I n the course of a fewdays, ethyl phthnloxyldimalonate is also depositcd. On distilling theuncrystallisable mother-liquor in a, current of stearn, ethyl malonatevolatilises ; the non-volatile oil consists of ethyl phthalyldimalonate.After it has been purified by washing with a solution of sodium car-bonate, it solidifies, forming a crystalline mass.Ethyl phthalylmalonata, C I5Hl4O6, is deposited from ether in tri-clinic prisms.The crystals are highly refractive. The ethereal saltdissolves in 14 times its weight of ether at 9", and in 1.7 times itsweight of ether at 35". It is more soluble in alcohol. It melts a t74*5", and on cooling the fused mass, the solidification proceeds fromcertain points in a peculiar and characteristic manner.Ethy 1 phthalox y ldimalonate, Cz2Hz409, is deposited from ether inneedles and from alcohol in prisms. I t requires 184 parts by weightof ether a t 9", and 174 parts of absolute alcohol a t 14" for solution.It is dissolved by alkalis with an intense yellow coloration. The sub-stance melts a t 116.5" if the temperature is slowly raised, and a t 106"if it i s quickly heated. In the latter case, it soon solidifies and meltsagain a t 116.5".Ethyl phthalyZdimaZonate, C,,H2,OI,,, is deposited from hot alcoholin prisms melting at 48.3".Ethyl phthalylmalonate is decomposed by alkalis, yielding ethylalcohol, and phthalic and maloiiic acids.It also splits up on boilingwith water into ethyl malonate and phthalic acid. When reducedwith zinc-dust and acetic acid, it unites with foiir atoms of hydrogen,forming diethyl hydrogen benxylmaloncarboxylate,It is freely soluble in alcohol and ether.COOH*CsH*.CHz*CR( COOEt)2.The formation of this monobasic acid is incompatible with the sym-metrical formula for ethyl phthalylmalonate. The new compound i8very soluble in alcohol and ether, but it requires 2230 times its weightof water at 17" for solution. It melts at S6". The sodium salt isdeliquescent and is precipitated by ether from its alcoholic solution.The silver salt, C15H17ag06, is soluble in hot water and is crystalline.On treatment with ethyl iodide, i t yields triethyl benzylmaloncarboxyl-ate, a colourlcas liquid boiling a t 2EiO" under 45 mm.pressure.Dipotassium ethy E benzy Imalon carboxylnte, C,H, (COOK) 2*C OOE t, isformed when a solution of the potassium salt of diethylbenzylmafon-carboxylic acid is left in contact. with potassium hydroxide for onehour at the ordinary temperature, but benxylmalonorthocarboxylic acid,COOH*C6H4.i_l'2H3,(COOH)2, is produced if the salt is boiled with anexcess of alkali and &hen acidified, This acid is soluble in hot water.It begins to decompose at 170", and at 180" it is completely convertedinto carbonic anhydride and the hydrocinnamorthocarboxylic aciddescribed by Gabriel and Michael (Abstr., 1878, 426).Phtlidy Zdiarnide, C8HAN202, is deposited in crystals when alcoholicammonia is added to a solution of ethyl phthalylmalonate in absolutealcohol.Itl is insoluble in the usual solvents, and by boiling withwater or by heating at 210" is decomposed, yielding phthalylimideORGANIC CHEMISTRY. 151Sodium ethoxide acts on ethyl phthalylmalonate, forming ethylp ht hnly loxethy bodiomalonate, C 0 <32> C (OE t) .CNa( COOE t) 2.The sodium atom is easily displaced by hydrogen, yielding ethylphthalyloxyetliylmalonate, a substance which is easily decomposed bywarm alkalis, yielding ethyl alcohol, phthalic and malonic acids.Et h y ZphtF,aZyZoxyethylethylmalo~~ate, CO <cf:> C (OEt) CEt*(COOEt),, isformed by the action of ethyl iodide on the preceding sodium com-pound. It is saponified by alcoholic potash at the ordinary tempera-ture, but the product ,splits up into alcohol and the potlassium salt,C13H9K307. On the addition of hydrochloric acid to a solution of thepotassium salt, benzoylorthocarboxethylmalonic acid is liberated, butit spontaneously decomposes into phthalic and malonic acids. Anoily liquid which behaves in a similar manner is obtained when anacid is added to the solution of ethyl phthalylmalonate in alkalis. Itis probable that the sodium compound of ethyl phthalylhydroxy-mnloiiate is formed in the first instance, and that it IS converted intoethyl phthalylhydroxymalonate, which at the ordinary temperaturebplits up into phthalic anhydride and ethyl malonate.At loo", ethylitionochloracetate converts the ethyl phthalyloxyethylsodiomalollnteiuto trhe ethyl phthalylethylethenyltricarboxylate. On hydrolysis,this acid yields benzoylorthocarboxethezlyltricarboxylic acid, which isdecomposed by water, yielding ethenyltricarboxylic and phthalicacids.E thy1 ph thaloxydimalonate uiiites with potassium hydroxide, form-ing orange-coloured crystals of the composition Cz2Hz5K0,,. A yellowsodium compound, C22H21Na2010, is produced by the action of anethereal solution of ethyl phthrtlyldimalonnte on ethyl sodiomalonate.The sodium is displaced by ethyl on treatment with ethyl iodide, andthe product is decomposed by alkalis into alcohol, ethylrnalonic andphthalic acids.The yellow substance is probably a mixture of thetwo isomerides,CO<~f~>C[CNa(COOEt)2]z and CsH4[ CO*CNa(COOEt)z]2.By the action of acetic anhydride, phthalic anhydride, or phthalicchloride on the yellow sodium compound, ethyl phehaloxyldimalonateis formed, but glacial acetic acid decomposes the substance with theformatiou of ethyl malonate and ethylphthalylmalonate, togetherwith small quantities of ethyl phthalyldimalonate. Hot water alsodecomposes the sodium compound, yielding ethyl phthalyldimalonate(from the unsymmetrical compound), and ethyl malonate and sodiumphthalate from the symmetrical isomeride. It is decomposed bybromine into ethyl phthalylmalonate and ethyl dibromomalonnte,C22H2,Na20,0 + 2Br2 = 2NaBr + C15H1406 + CBr,(COOEt),.Ethylphthaloxyldimalonate unites with four atoms of nascent hydrogen,forming a neutral oil of the composition C2,H,0,. Ethyl phthaloxyl-dimdonate is probably an unsymmetrical compound, having the consti-n Trtution represented by the formula C O < c ; $ & - - >C: C(COOEt),152 ABSTRACTS OF CHEMICAL PAPERS.Ethyl phthalyldimalonate dissolves in alkalis, forming an orange-coloured liquid. If the solution is heated at 100" for some hours,the colour disappears; on the addition of an acid, a tribasic acid,COOH~C6Ha.C(CH2*COOH)2~OH, is liberated, which at once splits upinto water and phthalyldiacetic acid, CO<?f:>C(CH2*COOH)2.A yellow potassium compound, C2,H,K2010 + 2H20, is precipitatedon the addition of ether to the orange-coloured solution of ethylphthalyldimalonate in alcoholic poiash.It is reconverted into ethylphthalyldimalonate by the action of acids.If phthalic chloride is added to a mixture of ether and et.hy1 sodio-malonate at the ordinary temperature, the chief 'product of the re-action is ethyl phthalylmalonate, but if half the chloride is slowlyadded to the warm mixture, and the product heated for some timebefore the remainder of the phthalic chloride itJ added, the chief pro-duct is ethyl phthaloxyldimalonate, a small quantity of ethyl phthalyl-dimalonate is also formed. By reversing the process, and adding themixt,ure of ether and ethyl sodium malonate to the phthalic chloride,a large yield of ethyl phthalylmalonate is obtained, together with halt'the weight of phthalyldimalonate, aud &th of phthaloxyldimalonate.Phthalic anhvdride acts on eth vl sodium malonate.forming sodium Y phthalate, edyl phthalylmalona'te and ethyl rnalonate. w. c. w.Benzenetrisulphonic Acid. By C. L. JACESON and J. F. WING(Amer. Chem. J., 9,325-347, Compare Abstr., l886,623).--Senhoferprepared benzenet risulphonic acid by heating benzene with phos-phoric anhydride and fuming sulphuric acid ; the auth0r.s in prepar-ing potassium benzeneparadisulphonate also obtained benzen etrisu 1.-phonic acid; and its formation was proved to be due, during asecond heating of the ingredients, to the Rction of potassium sulphatepreviously formed ; a similar action possibly takes place in Claesson'smethod (heating a potassium sulphonate with sulpburyl chloride), andNeville and Winther's method (heating the acid sulphates of theamines) , The potassium sulphate can be replaced by ailver sulphate,and very imperfectly by alumiiiium sulphnte, but not by zinc sulphate,and it therefore acts not as a dehydrating agent, but as a carrier ofsulphuric acid.Yotcrssiuwt benzenetrisulphonate, C6H3(S03K)3 + 3H20 [= 1 : 3 : 51,is easily prepared by heating 15 grams of potassium benzenemetadisul-phonate with 18 grams of strong sulphuric acid, until the mass beginsto get pasty, when it is dissolved in water and converted into thepotassium salt by the usual methods ; the yield amounts to 44 perrent. The preparation may be made from benzene itself, but theproduct is more difficult to purify owing to the formation of para-disulphonic compounds.The salt forms monoclinic plates or needles :/3 = 68" 38&' ; a : b = 1 : 3.10 ; 35-46 parts of the anhydrous saltare dissolved by 100 of water at 20". Attempts to brominate ornitrate the acid were unsuccessful. Benzenetrisu~phmic chloride,C,H,(SO,CI),, is prepared by the usual methods; it melts at 184." andsoon after sublimes slowly ; i t is slowly decomposed by boiling waterORGANIC CHEMISTRY. 153and is best recrystallised from chloroform. Ethyl benzenetrisulphonate,C,H,(SO,Et),, is readily obtained from the silver salt and ethyl iodide ;other methods are not suitable. It melts at 147", but is decomposedby long heating at lower temperatures.It crystallises readily frombenzene, and is insoluble in water ; it is decomposed by boiling withabsolute alcohol, the free acid and ethyl ether being formed. Benzene-trisuZphortarnide, CsH,( S02NH2),, is formed from the chloride by theaction of aqueous ammonia. It may be crystallised from water oralcohol, and. melts at 310-315". The following salts are described,C,H,( SO,NHAg),, C,H,(SO,NHHgOH),, and [ C,H,( SOZNH),],Hg,both formed with difficulty, and [CaH,(S03)3]2[ CU(NH~)~]~. Attemptsto prepare the imide were not altogether successful. Benzenetrisulpho-benzo!yZamide, C,H,( SO,NHBZ)~, is obtained by acting with benzoicchloride on the sulphonamide at temperatures not above 140".It ispurified by crystallisation from alcohol, but shows no definite meltingpoint, owing to its ready decomposition. It dissolves easily in alkalis,and forms salts such as C6H3(S02NNaBz),, and [C6H3(S02NBz),]Ba3 +12H,O, both being uncrystallisable. When the benzoylamide istreated with phosphorus pentachloride, the substanceCsH3( SOZN : CClPh),is formed, which by warming with aniline is converted into the corn-pound CsH3(S0,N : CPh*NHPh),, melting at 193", and best crystal-lised from alcohol. Benze/~etrisuZphaniZide, C0H3( SO,NHPh),, formedby the action of aniline on the sulphochloride ; it crystallises well fromalcohol, and melts at 837".The constitution of the benzenetrisulphonic acid here described isascertained by fusion of the potassium salt with potitssiiim cyanide andsaponifying the nitrile formed, when the only product is trimesic acid ;moreover, when the sulphochloride is heated with phosphorus penta-chloride at 200", it is converted into the symmetrical trichlorbenzene,hence [(SOSH)I = 1 : 3 : 51.Sulphonefluorescein.By I. REMSEN and C. W. HAYES (Amer.Chem. J., 9, 372--379).-1t has been previously shown (Abstr., 1885,539), that when resorcinol is heated with orthosulphobenzoic acid, ityields a highly fluorescent substance. This is now shown to be oneoE a new class of compounds, the sulphonphthaleins.Sulphonjhorescdn, 0 < C,H,(OH) CeH3(0H)>C<~eN4>S02 0- + 2H,O, is ob-tained when orthosulphobenzoiu acid is fused with resorcinol at 175-185" until the inass becomes pasty.The mass is crystallised fromwater, and the crystals washed with ether ; they are pale straw-yellow,and probably monoclinic. It shows a feeble green fluorescence, muchstronger in alkaline solution, is very soluble in water and alcohol, butdissolves only slowly in ether. It does not melt without decomposi-tion. It has decided acid reactions, differing from fluorescein i n thatit decomposes carbonates. The barium, (C19H1307S)2Ba, and calciumsalts are described, as also a crystalline acetyl-derivative. Whentreated with bromine in acetic acid solution, it yields a dibromide,ClgH'loBraOsS, and with sulphuric acid it yields an intensely fluorescenta. B154 ABSTRACTS OF CHEMICAL PAPERS.acid.oxidises in the air. H. B.Nascent hydrogen reduces it to a colourless substance that re*Diphthalic Acid.By C. GRAEBE and P. JTJILLARD (Annulen, 242,214+257).-Pure diphthalic acid is a colourless substance whichmelts at 270-272". The methyl salt, CI6HBo6Me2, obtained by theaction of methyl iodide on silver diphthalate, crystallises in plates ofa lemon colonr. The ethyl salt form8 lemon-col oured needles, and melts at 1.54-1 55". When hydrogen chlorideis passed into warm ethyl alcohol containing diphthalic acid in solu-tion and suspension, colourless plates are deposited of the compositionCI,H1408. The compound melts at 174", and dissolves in alcohol,et.her, and chloroform. If methyl alcohol is substituted for ethylalcohol in the previous experiment, a crystalline compound is obtainedwhich melts a t 275".After recrystcallisation from phenol, it seems tohave the composition CleH1406. These substances are decomposed byhydrocliloric acid a t 150°, yielding diphthalic acid and methyl orethyl chloride.At 180", hydroxylamine hydrochloride acts on diphthalic acid inpresence of alcohol, forming a compound of the composition Cl6Hl8N2O4.This substance is also formed by heating a t 100" in sealed tubes amixture of hydroxylamine hydrochloride, alcohol, and diphthalicanhydride, but if the operation is carried on in an open vessel anethereal salt is produced. The first compound crystallises in slenderneedles, melts at 285-286", and dissolves in phenol.The lactone of benzhydroltricarboxylic acid is obtained by dissolv-ing diphthalic acid in a 4 per cent.solution of sodium hydroxide, andheating the solution a t 110-115" for three minutes. When cold,the product is acidified with hydrocl.11oi.i~ acid and the lactone isprecipitated. It is soluble in choroform and in alcohol. On boilingthe alcoholic solution, carbonic anhydride escapes, and the laotoiie ofbenzhydroldicarboxylic acid is formed. On reduction with phosphorusand hydriodic acid a t 1 70°, the lactone of benzhydroltricarboxylic acidis converted into di~F,enylmeth~netricarboxylic acid,It melts at 191-192".C OOH*CH( C6H4.C OOH),.This acid is soluble in hot water and crystallises with 1 mol. H20.It begins to decompose at its melting point, 218-220", and nt 250-270" it is comylelely converted into a red compound, CIGHBO1, whichmelts a t 260".This red substance is also formed by dissolving theacid in warm sulphuric acid and pouring the solution into water.Benzhydroldicarhoxylic acid, OH*CH(C,H,*COOH),, is formed byheating diphthnlic acid with a 50 per cent. solution of potassiumhydroxide at 125-130" for five minutes. The lactonic acid,dissolves freely in alcohol, ether, and chloroform ; it melts at 203'.On oxidation, the alkaline solution yields benzophenonedicarboxylicacid, and the acid solution when treated with chromic acid yields thedilactone of the above acid. On reduction with hydriodic acid anORGANIC CKEMISTRF. 155phosphorus, diphenylmethanedicarboxylic and dihydroanthracene-carboxylic acids are obtained.If the lactone is sublimed, the sublimate melts a t 171°, and has thesame composition as the lactone.The potassium and barium salts (C15H1005Ra + HzO) of benz-hydroldicarboxylic acid are amorphous.The ammonium salt of thelactone is crystalline. The following salts of the lactone are insolublein water: (C15H90a)2Ba+ 2&H,O, (CI5HgOJ2Cu+ 3H20, and C15H,0Jg.The methyl salt melts nt 154-155", and the ethyl salt at 99.5". Thenmide, C15H903*NH2, crystallises in needles, and melts at 158-160".The lactone unites with phenylhydrazine, forming the crystallinecompound CZ1H,,NaO3. It also forms a crystalline dinitro-derivative,C15H80,(N0z)2, melting between 270" and 280". The ethyl sdt,C15H,01(N02)2Et, melts a t 146-148".Benzo~heiLonedicarboxEIZ1:c acid, (20 (C,H,-COOH),, is soluble inalcohol, ether, and acetic acid.It melts between 150" and 155",losing a molecule of water, and forming the dilactone. The potas-sium' and ammonium salts cryatallise in needles, and are freely solubleill water. The copper salt is insoluble, and the silver salt sparinglysoluble. The barium salt, C15H,05Ba + 5H20, forms prisms, whichdissolve freely in hot, and sparingly in cold water. Anthraquinoneis'formed when the anhydrous barium salt is strongly heated. Themethyl salt, C,H805Me2, melts at 85-86', and the ethyl salt at73- 74".The dilactone of benzophenonedicarboxylic acid, C <ff:> GO>,, isobtained in crystals when strong hydrochloric acid is added to a con-centrated alcoholic solution of benzophenonedicarboxylic acid.It issoluble in benzene, chloroform, hot acetic acid, and hot alcohol. Whenreduced with zinc-dust and acetic acid, it is converted into the lactoneof benzhydroldicarboxylic acid, and when reduced with hydriodicacid and phosphorus at 1 70°, it yields diphenylmethanedicarboxylicacid and a small quantity of dihydroanthracenecarboxylic: acid. At200", if much phosphorus is used, the chief product is methyl-anthracene hexahydride. Fuming snlphuric acid converts thedilactone into anthraquinonesulphonic acid. The imide of benzo-phenonedicarboxylic acid is obtained on heating the ammonium saltof the acid, or by the action of ammonia on the dilactone ; it formscolourless crystals, and melts at 951-252". It is converted into thedi-iwhide, C15Hlo0zN2, by treatment with alcoholic ammonia a t 140" ;this is soluble in acetic acid, hot water, and hot alcohol.Itcrystallises in prisms, and melts a t 284-286". The acetoxime ofbenzophenonedicarboxylic acid forms colourless crystals, and meltsat 213-214". When the dilactone is treated with dilute alcohol andhydroxylamine hydrochloride at a gentle heat, the ethyl salt of theacetoxime is obtained ; it melts at 146-149".Phenylhydrazine unites with benzophenonedicarboxylic acid, form-ing a crystalline compound of the composition C2,Hle05N2, whichmelts at 155", aAd loses 2 mols. H,O, yielding the compoundC21H1404N2. This substance can also be prepared by slowly adding156 ABSTRAOTS OF CHEMICAL PAPERS.phenylhydrazine to a warm alcoholic solution of the dilacbne.Itmelts at 230°, and is soluble in hot alcohol.Diphenylmethanedicarboxy Z ~ c acid, CH2(C6H4*C00H),, melts at'254.5", and at 280" yields n sublimate which consists of a mixtureof anthraquinone and unaltered acid. The acid is soluble in alcoholand ether. It is oxidised by potassium permanganate to benzophenone-dicarboxylic acid. Strong sulphuric acid at 100" converts it intoa-nnthranolcarboxylic acid. The barium salt, C15HloOaBa + 6Hz0, iscrystalline. The methyl salt, ClsHlo04Me2, is very soluble in alcohol,and nielts at 43-44".a-Anthrai~oZc~,rbozyZic acid dissolves freely in alcohol and ether,and melts at 252-253" ; when oxidised, it yields anthraquinone-carboxylic acid melting at 286". a-Dihydroawthracenecarboxylic acid,~6~,<,H2>~6H,~cooH, CH2 crystallises in yellow prisms, and is solublein alcohol and ether.It melts at PO9", and on oxidation with potas-sium permanganate yields the anthraquinonecarboxlic acid whichnielts at 288". a-Methylanthmcene ftexahydride crystallises in plates,and dissolves freely in alcohol, ether, and chloroform. On oxidationwith a mixture of chromic and acetic acids, it yields a-methyl-anthraquinone, crystallising in yellow needles, .and melting at 153-154". w. c. w.Auramines. By W. FEHRMANN (Bey., 20, 2844-2862).- Com-mercial auramine is the hydrochloride of a base obtained by theaction of ammonium chloride on tetramethyldiamidobenzophenone ;the author, however, gives to the base itself the name auramine.Tetramethyldiamidobenzophenone (this Journ., 1876, ii, 298)crptallises in silvery-white scales, melts at 172-172*5", and is in-soluble in water, very sparingly soluble in ether, soluble in alcohol andbenzene. The hydrochloride, C17H20N,0,2HCl, crystallises from alcohol insmall, white, radially-grouped prisms, and decomposes in aqueous solu-tion with separation of the base ; theplatinochluride, Cl,H2,N20,H2PtCl6,is a granular, yellow precipitate, sparingly soluble in water andalcohol ; the picrate, C,,H,,N,O,C,H, (N02)J*OR, crystallises fromalcohol in small, purple-red, radially-grouped prisms, melts at 156-157", and is very sparingly soluble in hot water, soluble in alcohol.Burainime hydroeldoride (commercial auramine), C17H,,N3,HC1 +H20, is prepared by heating equal parts of tetramethyldiamidobenzo-phenone, ammonium chloride, and zinc chloride at 150-160" untilthe melt is almost completely soluble in water.It crystallisesfrom water (at 60-70"), in beautiful, yellow scales, decomposesat 263--280", without previous fusion, and is spariiigly soluble incold water, soluble in alcohol. Dilute mineral acids readily con-vert it into tetramethyldiamidobenxophenone even in the cold,and the same change is effected by boiling the aqueous solution.Cotton prepared with tannin is tinged a pure yellow by the dye, andthe colour is little affected by acids. Auramine, NH : C(C6'Hp*NMe2)2,crystmllises from alcohol by spontaneous evaporation in citron-yellowscales, and is insoluble in water and ether, soluble in alcohol; theplat iuochloride, ( C,7HE,,N,),,H2PtCl,, separates from mixed aqueouORGANIC CHEMISTRY.15'7solutions of the constituents as a yellow, granular precipitate, in-soluble in water, and sparingly soluble in alcohol; if, however,alcoholic solutions are employed, the chief product is the platino-chloride of tetramethyldiamido benzophenone ; the picrate,crystallises in slender, yellow scales, melts at 230--236*, and is inso-luble in cold water, sparingly soluble in cold alcohol; the oxalate,(C,,H?1N3)2,H2CZ04, crystallises in small, orange-yellow needles, meltsa t 193-194", with the evolution of gas, and is sparingly soluble inwater, soluble in warm alcohol.Phenylauramine hydrochloride, CP3H,,N3,HC1, is formed when aur-amine hydrochloride is heated with aniline at 175-180" untilammonia ceases to be evolved, or when tetramethyldiamidobenzo-phenone is heated with aniline hydrochloride.It is a reddish,crystalline mass, which dissolves in water and alcohol, and graduailyin aqueous solution, or more rapidly on treatment with mineralacids, decomposes into tetramethyldiamidobenzophenone and aniline.Phenylaurcrmine, NPh : C( c6H,*NMez)2, crystallises from alcohol i nsmall. greyish-yellow, radially-grouped needles, decomposes at SO"into a solid and a liquid substance, and is insoluble in water and ether,soluble in alcohol ; the pZcLtinochZoride, (C,H2,N3)2,H2PtC16, and picrate,C23H,,N3,CsH2(NOz)3.0H, are flocculent and dissolve in alcohol.l'ol.t/Zaurarnine hydroch loride, obtained by heating auramine hydro-chloride with paratoluidine a t 160°, resembies the phenyl-derivativein its properties ; the platinochloride, ( C2,H27N3)2,H2PtC&, forms redflocks, soluble in alcohol.c 17H21N3, csH2 (No&* OH,To 1% y leneauranaine, C6H3Me <:E> C( C6H4*N&h2) 2, is formed whenauramine hydrochloride is heated with metaparat.oluylenediamine at160°, and the resulting hydrochloride is treat'ed with ammonia.Itcrystallises from alcohol in small, brown scales, and in dilute aceticacid solution dyes cotton prepared with tannin a reddish-brown. Inacetic acid solution, or more rapidly on treatment with dilutemineral acids, it is decomposed into tetramethy ldiamidobenzophenone.The hydrochloride crystallises in very slender, small, brown needles,and decomposes very readily ; the platinochloride, CZ4H2*N4, H,PtCIs,and the picrate, ~ , ~ z , ~ , , ~ ~ 6 ~ , ( ~ ~ z ) , ~ ~ , are soluble in alcohol.manner from ethylenediamine, crystallises from alcohol in yellowishscales, is insoluble in wat.er, soluble in alcohol, and decomposes intotetramethyidiamidobenzophenone in acetic acid solution, or on treat-ment with mineral acidR.It dyes cotton prepared with tannin yellowwith a shade of red. The hydrochloride forms yellow needles, and isvery unstable ; the plutinochloride, C',gH26N4,H2PtC16, and picrate,C19H26KN4, 2 C6&( NO,) 3*0 H, were also prepared.If the auramines, instead of being heated with water, are dissolvedin warm alcohol, and treated with hydrogen sulphide, a n analogousdecomposition occurs with the production ot' ammonia or the cor-responding amine and tetramethyldiamidothiobenzophenone.Th158 ABSTRACTS OF OHEMICAL PAPERS.latter crystallises in small, dark-red, flattened needles, and melts atabout 164", although by repeated crystallisation the melting poiiitslowly rises, owing apparently to slight decomposition. When warmedwith mineral acids, or when heated with water a t 110-120", it is decom-posed into hpdrogen sulphide and tetramethyldiamidobenzophenono.The platiiLochloride, C17H20N2S,H2PtC16 (compare Abstr., 188i, 81(i),forms violet-black flocks, insoluble in water and ether, sparingly solublein alcohol, but readily soluble in excess of hydrochloric acid to a purple-red solution, which readily decomposes with the separation of platinumsulphide.On treatment with carbon bisulphide in the cold, auramine isconverted into a mixture of tetramethyldiamidothiobenzophenoneand thiocyanic acid, whilst phenylauramine, when heated at 150"for five hours with carbon bisulphide, yields the thioketone andphenyl thiocarbimide.w. P. w.Auramine. By C . GRAEBE (Chmz. Centr., 1887, 951, from MO7Lit.Sci., 1887, 601).-Auramine, first obtained by Kern and Caro, is pre-pared by heating tetramethy ldiamidobenzophenone with ammoni urnand zinc chlorides. The free base is colourless, the hydrochloride,which has been introduced into commerce, forms golden-yellow leaf-lets, sparingly soluble in cold, readily in hot water. V. H. V.p-Naphthaquinone.By T. ZTNCKE (Ber., 20, 2890-2895 ; com-pare Abstr., 1887, 53).~Tr~chlorodiketohydronaphthale1~e h i d m t e ,C6H*<cEcl->CC12 + 2H20, is prepared by passing chlorine into co*coglacial acetic acid containing p-naphthaquinone, filtering, and keepingthe solution for two days in a closed vessel ; water is then added, andthe trichloride, which separates in thin, white needles, is crystallisedfrom alcohol or glacial acetic acid. It forms large, lustrous, well-formed crystals, probably monoclinic, which melt at 112" with sepa-ration of water ; a t 180", it becomes red and gives off hydrogefi chloride.The anhydrous substance forms a tough, yellowish mass, whichseparates from benzene in highly coloured crystals melting a t 128".When warmed with methylamine in alcoholic solution, the cornpour&C6H4<C( CO*C(OH) NMe>>CC1 separates in intensely red scales of a metalliclustre, melting at 200".Two other compounds, melting at 237" and160" respectively, are formed.Tricldoret hy Zen epheql eneg lycollic acid ,is formed when the trichloride is dissolved in dilute aqueous soda,and separates as an oil on adding an acid. The methyE salt crystallises incolourless, lustrous, monoclinic crystals melting at 150". The acetyl-derivative crystallises in small needles which melt at 114-116".Phenylenetrichlorathylene ketone, CHC1< gg:>CO, is prepared byoxidisivg the above hydroxy-acid with dilute chromic acid, and sepaORGANIC CHE SIISTRT. 159rates as an oil, which gradually solidifies.I t crystnllises from alcoholin thick pointed needles, having a peculiar odour resembling that ofbenzophenone; it is readily soluble, melts a t 58-59', and distilsslowly with steam.OrthodichZoroiiin?/Zberzzoic acid, C2HC12-C6H4*COOH, is obtained bydissolving the trichloroketone in an alkali and adding acid. It crys-tallises from dilute alcohol in long, slender needles melting at 120-121". It is reduced by sodium amalgam to orthoethylbenzoic acidmelting at 68". The methyZ salt crystallises in thick needles whichmelt at 47". N. H. M.Hydro-derivatives of Aromatic Bases. By E. BAMBERGER(Ber., 20,2915-29 17).-p- Tetral~ydronapl~th~ilamine, CIOH11*NH2, pre-pared by the reduction of p-naphthylamine with sodium, is a verystrong base, capable of displacing ammonia from its salts.It formsstable, crystalline salts with carbonic anhydride, and by carbon bisul-phide is converted with explosive violence into tetrahydronapht,hyl-amine tetrahydronaphthylsulphocarbamate. The isomeric a- derim-tive is a feeble base, which does not react alkaline or yield a carbonate.It reacts like a normal amine with nitrous acid.It is suggested that the hydro-derivatives of the aromatic basesare related to bases of the camphor-group, and that tetrahydro-p-naphthylamine and Leuckart and Bach's bornylamine (Abstr., 188 7,376) are similarly constituted. N. H. &I.Orthamidazo- and Hydrazimido-cornpour, ds. By T. ZIKCB Eand A. T. LAWSON (Ber., 20, 2896-2903 ; compare Abstr., 1886,795,and 1887,731) .-Benzeneszo-P-naphthylamine is a much feebler basethan orthamidazotuluene ; the salts are readily decomposed by alcoholand water.The hydrochZoride crystallises in yellowish needles ; thesdphate, NHz.CloH6.N2Ph,HzS04, forms brownish-yellow needles. Thediazochbride is prepared by dissolving 1 part of the am-compouqd in15 parts of hot glacial acetic acid and adding 3 parts of strong hydro-chloric acid ; cold nitrous acid i s then passed through, and the wholekept until a clear, dark-red solution is obtained. The platinochloride,( N2 C 1 C ,,H,*N,P h) ,Pt C 14, forms small, yellow , sparingly solubleneedles. The diazosulphate is less soluble than the chloride ; the p e r -bromide, NZBr3*C,,H6.N,Ph, forms small, red needles. When the soh-tion of the diazochloride in acetic acid is diluted with water, nitrogenis evolved, and benzeneazo-&naphthol is formed.When the well-cooled acetic acid solution of the diazochloride is treated with stannouschloride, heated on a water-bath, and filtered, the diazohydride,N2H*CloH6.NzPh, is obtained ; this crystallises from benzene or alcoholin colourless, lustrous needles, melting a t 204-205". The acetyZ-deri-uative, NzAc*CloH,*N2Ph. crystallises from alcohol in lustrous needleswhich melt at 137-139".p-Anzidazonaphthalene hydrochlomkie, C,,H,*N2*C,,H,~NH2,HC1, formssmall, brownish-yellow needles ; the sulphate crystallises in brovvnish-yellow needles. The diaxochloride is decomposed by water, with forrna-tion of /3-hydraxyazonaphthalene (Nietzki and Goll, Abstr., 1886,714)and evolution of nitrogen.The diaxohydride, N2H*C10H6-N2*C10H7160 ABSTRACTS OF CHEMICAL PAPERS.crystallises in white needles melting at 202-204, is readily soluble inhot alcohol and hot glacial acetic acid, sparingly soluble in benzene.N. H. 11.Sulphonation of Acetonaphthalide. By M. LANGE (Rer., 20,8940-2941.) .-a-Acetonaphthalide is sulphonated by adding it i r ifine powder to fuming sulphuric acid containing 20 per cent. of anhy-dride. The sulphonic acid is unstable, and loses the acetyl-groupwhen boiled with alkalis or acids.a-Naphthy laminesulphonic acid is obtained by treating the solutionof acetonaphthalidesulphonic acid in sulphuric acid with twice thebulk of water. It crystallises in needles much more soluble thannaphthionic acid ; the salts are also much more soluble than those ofthe naphthionic acid.The solution shows a green fluorescence. Thebenzylidene compound crystdlises in long needles. When the acid isdiazotised and boiled with alcohol, a naphthalenesulphonic acid isformed, which yields a-naphthol when fused with potash.By A. WEINBERG (Ber., 20,2905-2Yll).-~-Naphthalenedisulphonic acid is converted by theaction of soda into a new /3-naphtholsulphonic acid. This, whenheated with ammonia, is converted into (3-naphthylaminesulphonicacid, from which P-naphthalenemonosulphonic acid was obtained bymeans of the diazo-compound. Assuming that P-naphthalenedisa 1-phonic acid has the constitution [2 : 3'1, the constitution of a-naph-thalenedisulphonic acid would be [2 : 2'1.pp-Naphtholsulphonic acid, [ 2 : 2'J (known as naphtholsulphonicacid I?.), is prepared by heating sodium naphthalenedisnlphonate(1GO grams), soda (30 grams), and water (300 c.c.), for 12 hours at250".The product is recrystallised and converted into the barium~ a l t ; the free acid is recrystallised from strong hydrochloric acid,from which it separates in needles which melt, when dried, at 89". Itis readily soluble in water and alcohol, insoluble in ether and ben-zene. When the sodium salt is heated with phosphorus pentachloride(3 parts) at l65", chloronaphthol phosphate melting at 215" is formedas chief product, together with a naphthalene dichloride, which crys-tallises €rom methyl alcohol in rhombic plates which melt at 114".Sodium rtaphtholsulphonate crystallises with 2& mols.H,O in largeplates ; the potassium salt with 1 mol. H20 forms rhombic crystals.Both salts are readily soluble in water. The magnesium salt crystal-lises in plates with 54 mols. H,O ; the barium salt is sparingly soluble,but more soluble than the barium salt of Schaeffer's P-naphtholsul-phonic acid. Nitrous acid converts the sulphonic acid into a nitroso-compound; the sodium salt crystallises with 2 mols. H,O in goldenneedles.Naphthylaminesnlphonic acid [2 : 2'1 (F.), is obtained by theaction of ammonia on the naphtholsulphonic acid ; it dissolves in850 parts of boiling water. The barium salt with 5 mols. H20 crys-tallises in well-formed needles ; the magnesium salt crystallises with5$ mols.H20.Bayer and Duisberg's P-naphthylamine-6-sulphonic acid (Abstr.,1887, 732) is not identical with the acid [2 : 2'3, but is a mixture.N. H. M.dC-Naphthalenedisulphonic AcidORGANIC CHEMISTRY, 161~-Naphthol-6-disulphonic acid, prepared from 2 : 2' naphtholsnl-phonic acid, yields with diazobenzene a crystalline orange dye, andwith a-diazonaphthalene a Bordeaux, which crystallises in violetplates. The sodizcm saEt is readily soluble in water, from which it isprecipitated by alcohol as B yellow powder; the barium salt with2g mols. H,O crystallises in prisms soluble in 180 parts of boilingwat,er. The solutions of the salts show a green fluorescence.Derivatives of Dinaphthyl. By P. JULIUS (Chem.. Ind., 10, 97-99).-The author has modified Dianin's method of preparing a- andp-dina,pht,hol. He proposes to treat an aqueous solution of sodiumiiaphthoxide with a mixture of ferric chloride and hydrochloric acid,whereby the naphthol, which separates in a finely-divided state, isoxidised into dinaphthol as soon as it is brought into contact withferric chloride.The following reaction occurs :--LLCloH7*OH + Fe2C1,= C,H,2(OH)2 + Fe2C14 + 2HCL In practice it is necessary touse 2 mols. of hydrochloric acid to 1 mol. of ferric chloride. a-Di-napAthoE thus prepared forms a white, crystalline powder melting at296-299". p-DienaphthoE forms pale-yellow, glistening needles melt-ing at 217". The yields of a- and 6-dinaphtbols are 70 to 75 and 85 to95 per cent.respectively as compared with theory. On treating/?-dinaphthol with sulphuric acid, and saturahg the resulting sul-phonic acid with barium carbonate, the barium salt of P-dinaphthol-disulphonie acid, C,HIo( OH),( SO&Ba + 6H20, separates, whilst thefiltrate contains the barium salt of ~-da'nirphtho~tetmsz~~phonic acid,&He( OH) ~ S 0 3 ) a B ~ .C20H,(N02)2(0H)2fS03H)2 + 3H20,is obtained by treating the barium salt of the disulphonic acid withnitric acid. It crystallises from alcohol in yellow, silky needles.p-Dinaphthol does not combine with diazo-compounds ; a-dinaphthol,however, does so readily, giving rise to a series of dyes.Diamidopyrene. By R. JAHODA (Monatsh., 8,449-451) .-Thehydrochloride of this base is obtained by the reduction of dinitro-pyrene (Goldsohmiedt, Abstr., 1881, 206) ; it forms white needles.Di-amidopyrene, C16H8(NH2)2, is very unstable in the €ree state, resinifyingvery rapidly. The sulphute forms a white substance, insoluble inwater and alcohol, and decomposes when heated.N. H. M.Dinitro-p- diii apht holdidphonic acid,D. B.L. T. T.Diterebenthyl. By A. RENARD (Gonipt. rend., 105, 865-868) .-The resin oils obtained by the destructive distillation of colophonyconsist mainly of a hydrocarbon which boils above 309", and can beisolated by successive washings with sodium hydroxide solution, andthen with water, followed by fractionation. The liquid thus obtainedbas the composition CZ0Hm, and boils at 343-346" ; sp. gr. at 18" =0.9688; vapour-density 9.6; rotatory power for [ a ] ~ = + 59"; refractiveindex 1.53.It seems to be diterebenthyl, formed by the condensa-tion of 2 molecules of terebenthene with elimination of H20. Whenexposed to air in thin layers for five days, it absorbs about one-tenthof its weight of oxygen and forms a varnish. Chromic anhydride invcjT.4. LIV. 41162 ABSTRACTS OF OHEMICAL PAPERS.boiling acetic acid oxidises the hydrocarbon to carbonic oxide andcarbonic anhydride. Potassium permanganate in aqueous solutionconverts it into carbonic anhydride and formic, acetic, and propionicacids.When the hydrocarbon is poured gradnally into well-cooled, fumingnitric acid, there is no evolution of gases, and on adding water a tri-nitro-derivative, C20H27(NO2)3, separates out.When dried in a vacuum,i t forms a yellow powder soluble in alcohol and et,her. If the etherealsolution of the hydrocai-bon is treated with a current of hydrogen chlo-ride, the compound 2C20Hm,HCI is obtained. Bromine acts violentlg,but in solution in carbon bisulphide it yields the dibromideC20H30Br2, aud when the carbon bisulphide evaporates, the bromine-derivative decomposes with evolution of hydrogen bromide. Thedirect action of bromine on the hydrocarbon i n presence of wateryields the hexabromo-derivative C2nH24Br6, a dark- brown, amorphoussolid, which melts below 100",and is soluble in a(lcoho1 and ether.Ordinary concentrated sulphuric acid converts diterebenthyl into asulphoiiic acid, which is isolated by agitating with water and lightpetroleum.The liquid separates into three layers, the lower ofwhich is dilute sulphuric acid, the middIe the sulphonic acid, and theupper layer a solation of the unalt'ered hydrocarbon in the light yetro-leum, which does not dissolve the Rulphonic acid. A certain quantityof a new hydrocarbon is formed, which is not attacked by acids. Thesulphonic acid is converted into the ammonium salt, which is pre-cipitated by adding sodium chloride to the solution. The sulphonicacid, C2,,He9.SO3H, is obtained by decomposing the ammonium saltwith sulphuric acid and extracting with benzene. It is a dark-brownmass, soluble in water, alcohol, ether, and benzene, but insoluble inlight petroleum. Its solutions are highly fluorescent, and are brownby transmitted light, green by reflected light. It decomposes carbo-nates of the alkalis and alkaline earths.The free acid is precipitatedfrom its aqneous solution by sodium chloride, sulphuric acid, sodiumsulphate, arid calcium chloride.The ammonium salt is soluble in water, forming fluorescent solu-hons. The barium, calcinm, copper, and lead salts, which can beobtained by double decomposition, are all insoluble in water. Theyall dissolve in alcohol, ether, and benzene, and burn with a smokyflame. C. €3 B.Bitter Principle of Calamus Root. By H. THOMS (An?/,aZtva,942, 257-260).-The author states that the reason Geuther (Ahstr.,1887, 972) failed t o obtain acorine and acoretine from calamus root isbecause he did not use the original process descrihed by the author(Abstr., 1886, 895), and consequently obtained different results.w. c. w.Bitter Principle of Calamus Root. By A. GEUTHER (Annulen,242, 260-264).-A reply to the above.Cubebin. By C. POMERANZ (Hwmtsh., 8,466-470).-The authoris investigating this compound from Piyer mbebu, the formula ofwhich was proved by Weidel to be C10H1003. Attempts to eliminatORGANIC CHEMISTRY. 3 63possible alkyl-groups by the action of hydrogen chloride or iodideproved unavailing, as the substance always carbonised. When osidisedwith permanganate, it yielded piperonylic acid, CsHc04. When treatledwith acetic anhydride, no aceto-derivative is furmed, but an ether,(C,,H,,O,),C), which crystallises in needles, is soluble in alcohol, andmelts a t 78".From these results, the author concludes that cuhebb (i) is a deri-vative of a methylene ether of pTrocatecho1; (ii) contains a side-chain,C3H50, yielding carboxyl on oxidation ; and (iii) contains this side-chain in the same position relatively to the two etheric oxygen-atomsas the carboxyl in protocatechuic acid stands to the two hgdroxyls.1;.T. T.Brominated Quinolines. By A. CLAUS and V. TORNI-ER (Bey., 20,2872-2882). - yBromoquinoline (Claus and Collischonn, Abstr.,1887, 158) boils at 274-276" (uncorr. ; not 273-274"), solidifieswhen cooled to below 0" and melts a t 12-13'. The oxalatecrystallises in stellate groups of prisms, me1 tirig a t 107" (uncorr.).The picrate forms a loose, bright yellow precipitate, consisting ofslender needles ; i t melts at 190".The ethobromide, C,NH,Br,EtBr, isobtained by heating the base with ethyl bromide and absolute alcoholat 100" for some hours; it separates on cooling in lemon-colouredneedles with 2 mols. EtOH, and melts at 216" (uncorr.). y B r o a o -pwinoline dibromide hydrobromide is obtained when bromine is addedto a, solution of ybromoquinoline hydrobromide in chloroform, as acinnabar-coloured mass of crystals, melting a t 76" with decomposi-tion; it was not analysed, When the hydrobromide is heated atabout 'LOO", ai new dibronzopinoZine is obtained, together with itshydrobromide. The new base crystallises from alcohol in colourless,lustrous needles, which melt at 166" (nncorr.).Parabromoquinoline is best purified by boiling with chromic acid.It is an almost colourless liquid which boils at 178" (uncorr.),solidifies when cooled to below O", and melts at 18-19" (uncorr.)When oxidised with potassium permanganate, i t yields only quinolinicacid [ (GOOH), = 2 : 31.The hydrobromide forms colourless needlcs,which soon become red, and melt at about 256'. The hydrochloride(with 1 mol. H,O) melts at 213" (uncnrr.). The nitrate forms needlesmelting a t 182"; the swlphate crystnllises (with 1 mol, H,O) in smallplates melting when dry a t 176" ; the chromate forms small, yellowneedles melting at 1 i Y ; the oxalate, melting ah 62", the picrate,melting at 216-217", and the ethohrorkde, melting at 230' (uncorr.),are also described. P a r a b r m q u i n o l i n e dibroinide hydrobronzide is avery unstable, orange-red substance, which melts a t 70°, and whenheated at 200" yields dibromoquinoline, melting a t 125-126" (IdaCoste, Ber., 14, 925 ; Claus and Kiittner, Abstr,, 1887, 278).Orthobron7oquinoZi.ne, prepared from ortbobromaniline and purifiedby chromic acid, forms a colourless oil boiling a t 300-304" (uncorr.).The hydrochZoride, C9NE6Br,HC1 + H20, melts with decompositionat 166" ; the platinochloride crystallises from alcohol in small, brightyellow needles ; the nitrate melts at 90" ; the dichromate begins todecompose at loo", and melts a t 168".Orthobrmnoquinoline dibromide hydrobromide form% om tge-redm 164 ABSTRACTS OF OaEMICAL PAPERS.crystals, melting at 90' with decomposition; when heated a t ZOO", anew dibromoquinolins is formed, which sublimes in colourless, lustrousneedles melting at 90" (uncorr.).Metabromaniline yields a mixture of two isomeric metabromo-quinolines which are best separated by means of the nitrates.Metnbrowaopuinolin,e, C9NH6Br, is an almost colourless oil, whichboils a t 280" (uncorr.), and does not solidify at -4".The hydyo-chZoride (with 1 rnol. H,O) is readily soluble in water, and melts a t2'25" with decomposition ; the platinochloride is a yellow, very spar-ingly soluble substance ; the nitrate is readily soluble in water, andmelts at 165" (uncorr.) ; the dichronzate forms reddish-yellow needles,melting a t 190" with previous decomposition ; the ethobromide me1 tsat 290" (uncorr.). Metn bromoquinoline dibromide hydrobromide is anorange-red crystalline substance, melting a t 107" (uncorr.) ; whenheated a,t 200", it yields a dibromoquinoline which crystallises in prismsmelting at 119" (uncorr.).Anabromoquinoline is crystalline, melts at 32" and boils at 290"(pncorr.).The hydrochloride (with 1 mol. H,O) forms small branchedcrygtals, very readily soluble in water ; it melts a t 213". The nitrateis much more sparingly soluble in water than its isomeride, andseparates in concentricdly-grouped needles melting at 199" (nncorr.) .The ethobromide crystallises from alcohol in coloarless, lustrousneedles melting a t ' L l 4 O . Anabromoquinoline dibrontide hydrobroqnideforms light yellow crystals, which melt a t 106-107" (uncorr.) withdecomposition ; when heated a t 200", dibromoqui.noZine, melting a t108" (uncorr.), is obtained.This crystallises in small, colourlessneedles, N. H. M.Ethyl Hydroxyquinoline Carbonate. By E. LIPPMANK (Monatsh,,8, 439-441). -When ethyl chloroformate and hydroxyqainolineaxe heated together, ethy 1 hydroaypzlinoline carbonate, CgNH,*O*COOEt,is formed. This crystallises in prisms, is soluble in boiling alcohol,chloroform, and etber, melts at 105", and gives no coloration withferrous sulphate or ferric chloride. The platinochloride,crystallises in orange needles.This ethyl salt when heated with caustic soda yields alcohol,hydroxyquinoline, and sodium carbonate ; with strong hydrochloricacid at 140", it yields ethyl chloride, carbonic anhydride, and hydroxy-quinoline.It is thuv a carbonate and not a carboxylic acid, and i8 notconverted into the latter even by heating at 'LOO".Pyrenoline. By R. JAHODA (Monatsh., 8, 442-448) .-Amido-pyrene hydrochloride (Abstr., 1881, 206) was treated by Skraup'sreaction with glycerol and sulphuric acid, when pyrenoline, ClgNHll,was formed. This substance forms yellow scales soluble in boilingalcohol, and a dilute solution shows a strong green fluorescence. I t isalso soluble in benzene, ether, and chloroform. It melts at 152-153".The hydrochloride forms orange, microscopic needles melting at 270" ;the sulphate pale red, hygroscopic needles melting a t 246"; theL. T. TORGANIO CHEMISTRY. 165PZatinocfiZoride a red precipitate, still solid at 290" ; the methiodidedark red, microscopic needles melting at 212", and soluble in alcohol ;and the picrate yellow, microscopic needles, which decompose at 260'.The latter compound is well suited for the purification of the base.When oxidised with permanganate, an acid is formed, but has no+yet been isolated.Action of Sulphuric Acid on Morphine and Bibasic Acids.By P.CHASTAINB and E. BAIBIZLOT (Compt. rend., 105, 941-943,3 012--1014).-When morphine is dissolved in excess of dilute sul-phurjc acid, and the solution evaporated until white fumes are givenoff, sulphomorphide, a substance of Tariable composition which givesbrown products with alkalis, is formed. If, however, morphine isheated with concentrated sulphurio acid at 120°, diluted with water,treated with alkalis for a very short time and then neutralised,.ityields a slightly soluble compound of the composition CIaHI7NOa. Italways contains some sulphur in the form of sulphuryl, which isremoved by strong alkalis, the compound being decomposed at thesame time.If morphine, 1 part, oxalic acid, 2 parts, and sulphuric acid, 1.5part, are heated together at 115-120" for some hours, cooled andmixed with a large excess of water, a yellowish-white compound ofthe composition C,Hl,NOa or C,HsN,O, is obtained. Malonic acidunder similar conditions yields the compound C30HmN2010, and suc-cinic acid the compound CaH43N2012.. These compounds differ by2CH20. They are white, non-crystallisable substances which beeomegreenish when exposed to air and light.They are insoluble in mostneutral solvents, but are slightly soluble in cold water, more solublein hot water. They behave like palyhydric phenols, and when mixedwith alkalis oxidise on exposure to the air, forming red solutions.When these solutions are acidified, they deposit a deep blue flocculentprecipitate soluble in ether, forming a violet-red solution, and inchloroform forming a blue solution, both of which deposit blue erys-tals of the composition C,,H2,N20a on evaporation.The same compound, morphine-blue, is obtained with all three of theacids above-mentioned. At loo", it contains 1 mol. H20, which isexpelled at 120-125". Each of the products from the bibasic acidsabsorbs 2 mols. of oxygen in alkaline solution, and forms 1 mol.ofmorphine-blue. This compound crystallises in slightly oblique prismswith a square base, which are red by transmitted light and blue byreflected light. They have no action on polarised light and melt to ablue liquid at a very high temperature. They are insolnble in water,slightly soluble in alcohol, and very soluble in ether, forming a solu-tion which is red by transmitted light, and violet-red by reflected light.It also dissolves in chloroform, and alkalis remove the compoundfrom both the ethereal and the chloroform solution, forming bluesolutions. The compound in fact combines with alkalis to form saltswhich are somewhat stable when exposed to air.L. T. T.C. H. B.Cinchonamine. By C. FRIEDEL (Compt. rend., 105, 985-987).-The crystals examimd were obtained by Arnaud by gradually cool166 ABSTRACTS OF CHEMICAL PAPERS.ing an alcoholic solution.They formed hexagonal prisms terminatedby rhombohedra1 faces, the faces of the prisms being tangent to theedges of the rhombohedron. Sometimes the latter is modified byother faces. Optical examination shows, however, that the rhonibo -hedral form is only apparent, and the crystals really consist of threerhombic sections mncled along the faces m, and the faces which seemtro be those of the fundamental rhombohedron are really the faces a'.The fundamental form is a rhombic prism, i n which mm = GO", and6 : h = 1.6157. The other angles were found to be a'm = 4 7 O 39';n'p = 51' 4' (calc.), e4a' = 42" 21' (calc.), e4p = 31" 45' (calc.),LL'X = 53" 29' (cnlc.53" 25') xp = 68" 10' (calc.) ; xm = 36" 42'.There is nooutward sign of the structure, the faces eh and x being perfectlyunited, b u t the macles are not always regular, especially in the largercrystals. The crptals do not become unaxial at a higher tempera-t ure C. H. F.I n two adjacent sections of the macle, a'a' = 84" 42'.Alkaloid from Solsnurrr Gmdiflora. By D. FBMRE ( Q o T H ~ ~ .w i d . , 105,1074-1076).-The so-called " Wolf Fruit " of Brazil is thefruit of Solanam grandijlora, var. pulverulentem. Exteznally it isgreen, but the sarcocarp is white, somewhat thick, and has a bitterand disagreeable taste. It was treated with water and calciumhydroxide, evaporated to dryness on the water-bath, and the residueextracted with absolute alcohol and the solution filtered.The liquidwas then concentrated to a small bulk, resinous matter being removedas it separated. After cooling, the semi-solid residue was treatedwith dilute hydrochloric acid, which dissolved the alkaloid but leftthe resinous matter undissolved. The acid solution was decolorisedby animal charcoal, precipitated with ammonia, and the precipitatewashed with water and dried over sulphuric acid.The a1kaloYd thus obtained is a white subRtance with a, very bittertaste, insoluble in water but soluble in alkalis and dilute acids.When heated with potassium hydroxide, it gives off ammonia, and itssolution gives the usual reactions for alkaloids. With platinumtetrachloride, it gives a yellaw precipitate ; mercuric potassium iodide,a yellow precipitat,e; tannin, a turbidity ; ammonia, a white precipi-tate ; concentrated sulphuric acid, an egg-yellow coionr changing tored ; with sulphuric acid and manganese dioxide, a yeIlow colourbecoming first green .and then sio.let; concentrated nitric acid, apurplish-red colour.The molecular weight as determined by meansof the platinum compound is 236.4.It is anenergetic poison, and the fruit itself kills sheep which eat it, henceits name. C. H. B.The author proposes to call this alkalo'id grandiflorilze.Trigonelline. By E. JAHNS (Bey., 20,2840-2843) .-Trigonelline(Abstr., 1886, SS), when heated at 120" with an aqueous solution ofbarium hydroxide saturated at the boiling point, yields the whole ofits nitrogen as methylamine, and when heated with excess of hydro-chloric acid (sp. gr.= 1.2) at 260-270" is converted into nicotinicacid and a combustible gas burning with a green flame, probablORGANIC CHEMISTRY. 167methyl chloride. On these grounds, trigonelline is regarded as iden-tical with the methylbetaiue of nicotinic acid, and a comparison ofthe properties of the two substances shows this to be the case.Alkaloi'ds extracted from the Bark of the XanthoxylonSenegalense. By GIACOSA and MONARI (Cazzetta, 17, 362-367).-On extracting the bark of t4he Xanthoxylom senegatense (ai-lar-root)with petroleum, an oil is obtained, from which a crystalline substanceseparates ; t h i s contains no nitrogen, and when purified has a whitemicaceous appearance, melts at 120-125", and gives a purple-redcoloration with chloroform and sulphuric acid. It is probably apseudocholesterin, but sufficient material waa not at hand for a morecomplete investigation. The bark, after treatment with petroleum,gives on prolonged boiling with alcohol a brownish extxact, fromwhich, on addition of alkali, a yellowish solid is obtained. Thisconsists of two alkaloi'ds, one of which is amorphous and insoluble inhot water, the other crystalline and soluble. The former was notfurther examined ; the latter forms a hydrochtoride, crystallising inminute needles or prisms, boluble in cold water, and of intensely bittertaste. The nitrate crystallises in needles melting a t 215-220" ; theplatinochloride forms sparingly soluble yellowish prisms. The insolublealkaloid produces muscular irritatioii with coagulation of myosin, andphysiological disturbances analogous to those observed with veratrine.The compounds were not analysed.By A. CLERMONT (Compt. rend., 105,1022-1023).-20 grams of chopped meat is mixed with 30 gramsof water and 0.5 gram of sulphuric acid, and heated in sealed tubesat 180" for six hours. The products are gases and a slightly brownliquid, which is easily filtered. When evaporated to dryness, ammo-niacal vapours are given off, and the residue dissolves readily in water.The solution is not affected by boiling, nor by hydrochloric, nitric, oracetic acids, but it is precipitated by 4 vols. a.lcoho1 of. 90", or bytannin, mercuric chloride, or platinic chloride. 41 grams of peptoneare obtained from 20 grams of fresh meat. When heated with waterwithout any acid, the meat is converted into sptonin, which isreadily converted into peptone by pepsin at 35" in a slightly acidsolution. C. H. B.w. P. w.V. H. V.Formation of Peptone.Mucin of the Submaxillary Gland. By 0. HAMMARSTEN (Zeit.physiol. Chem. 12, 163- 195) .-Obolensky (P'uger's Archiv, 4, 336)and Landwehr (Zeit. physiol. Clzem., 5, 371) have both made analysesof submaxillary mucin, but their method of preparing the rnucin wasfaulty. In the present research, the following method was firstemployed : the glands were extracted with water, the extract filtered,and freed from microscopic elements by centrifugalising ; acetic acidwas used to precipitate the mucin from this solution ; the precipitatehad a stringy character. Attempts were then made to wash t h i s pre-cipitate free from proteids by water acidified with acetic acid, theprecipitate being repeatedly well kneaded with the aciditied water ;thia was found to be exceedingly di6culi. The mucin was redis168 ABSTRAUTS OF CHE-WCAL P-4PERS.solved in faintly alkaline water, and reprecipitated by acetic acidseveral times, but there was always the same difficulty in freeing itfrom proteids. This was found to be due t o the presence in thegland extract of a prote'id which is precipitable by acetic acid, andwhich is with difficulty soluble in excess of that reagent. It belongsto the class of protei'ds to which the name nucleo-albumin has beengiven. The older method of extracting the mucin from the glandswith a weak alkali was not used, because it was found that sub-maxillary mucin is readily decomposed by this treatment. The nucleo-albumin contains 17 per cent. of nitrogen ; and it was admixture withthis substance that gave in Landwehr's analyses the somewhat higherpercentage of nitrogen than was found subsequently in the presentresearch. The new method ultimately adopted for the preparation ofthe mucin was as follows : the clear watery extract was acidified withhydrochloric acid until the percentage of the latter reached 0.1-0-15 ; the mucin which was first precipitated was redissolved whenthe acid present reached the percentage mentioned. The mixture wasthen diluted with three to five times its bulk of distilled water ; by thismeans the mucin was precipitated, and the nucleo-albumin remainedin solution. This process was repeated several times, until ulti-mately the mucin was obtained pure. Repeated precipitation andre-solution by this method does not alter the physical properties ofthe precipitate, which occurs in sticky, yellowish strings, nor does italter its chemical properties or its elementary composition. This isin contrast with what occurs with dilute alkalis ; a 0.1 per cent. solu-tion o€ sodium hydroxide, or saturated or half saturated lime-waterdissolves the mucin ; but when precipitated by acetic acid its stringycharacter is lost, and the precipitate is flocculent ; ammonia is givenoff in small quantities, and the percentage of nitrogen in the pre-cipitate increases, the precipitate probably consisting of acid albu-min.The mucin prepared in the manner described was washed with waterby decantation ; when free from acid, it becomes white in colour, butbecomes again brownish-yellow on the addition of acetic acid ; it wasthen washed with alcohol and ether, and dried. Elementary analysisof seven preparations gave the following average results in per-centages :-(3, 48.84 ; H, 6.8 ; N, 12.38 ; S, 0.843 ; ash, 035. Previousstatements as to the absence of sulphur in mucin appear to be incorrect.The extremely small quantity of phosphorus found might have beencontained in the ash. The percentage composition correspondsclosely with that obtained by Loebisch (Abstr., 1886, 166), for tendonmucin. Mucin prepared in this way was found to be acid in reaction ;thib cannot be from union with the acid during its preparation, as thequantity of chlorine found by analysis was so excessively small ; butmucin is probably itself of the nature of an acid. A neutral solutionof niucin in 8 per cent. sodium chloride soliltion does not coagulateon heating, and even after adding acetic acid it only becomes slightlycloudy.Alcohol precipitates mucin from a neutra'l solution ; the precipitate issoluble in water, unless sodium chloride is present, in which case theprecipitate is very insoluble. Mineral acids in small quantities preORGANIC CHEMISTRY. 169cipitate mucin, and the precipitate is soluble in excess. Cop,persulphate and ferric chloride, mercuric chloride, lead acetate, potassiumdichromate, and potassium alum, all give slimy, gelatinous precipi-tates. Potassio-mercuric iodide gives no precipitate. Saturation withmagnesium sulphate or sodium chloride precipitates muuin ; Millon’s,Adamkiewicz’s, and the xanthoproteic reactions are all given bymucin. By heating with dilute mineral acids, a reducing substance isobtained. Potassium ferrocjanide gives no precipitate, or only acloudiness in a solution of mucin in dilute hydrochloric acid. Asodium chloride solution can be pretty strongly acidified by acetic acidbefore precipitation occurs ; and potassium ferrocyariide added to sucha mixture produces no precipitate. Tannic acid in small qnantitiescauses the liquid to become slimy and thick, and in excess causes pre-cipitation. Of the varieties of mucin hitherto described, thisapproaches nearest to tendon mucin, but it differs from that in itssolubility in dilute hydrochloric acid, and its behaviour to weakalkalis. W. D. H.The Mucin of Bile. By L. PATJEULL (Zeit. phgsiol. Chem., 12,196--210).--Landwehr (Zeit. pliysiol. Chem., 8, 114) was the firstto point out that the slimy substance in bile is not true mucin; heconsidered it to be a mixture of globulin with bile salts. An exa-mination of his analytical results shows that there is Rome difficultyin accepting this view; for instance, the percentage of nitrogeni n bile-mucin is 13.8 ; in paraglobulin, 15.85 ; and in glycocholicacid 2 . 5 ; there must therefore be 15.4 per cent. of glycocholicacid in the mixture called bile-mucin. The percentage of carbonon this calculation ought to be 55.01, but it is only 53.09. More-over, although Landwehr states that a mixture of Aodium glyco-oholate with serum-globulin has the physical characters of bile-mucin, it was found in this research that a mixture of globulin withbile deprived of its so-called mucin did not produce the cha-racteristic sliminess of normal bile. The usual method of preparingmucin is not applicable to bile, as the bile-much is slightly soluble inexcess of acetic acid. By dialysis, the mucin can be readily freed frombile salts, but not so readily from bile pigment ; moreover, putrefactionis apt to e~isue when dialysis is prolonged. The method ultimatelyadopted was to precipitate the mucin with five times its volume ofabsolute alcohol ; the precipitate was collected and freed from alcoholby centrifugnlising, redissolved in water, and again precipitated byalcohol. By thus quickly removing the alcohol, the mucin was notrendered insoluble. The properties of a 0.23 per cent. solution of thisso-called mucin were as follows :-After theaddition of a trace of acetic acid, which caused no precipitation a tthe ordinary temperature, it coagulated on heating, like a proteidsolution. More acetic acid caused precipitation without heat, and theprecipitate dissolved in excess although with some difficulty ; thisacetic acid solution was precipitated by potassium ferrocyanide,potassio-mercuric iodide, mercuric chloride, and tannic acid. Hydro-chloric acid in very small quantities caused a flocculent precipitate,On heating a neutral solution, it coagulated on boiling170 ABSTRACTS OF CHEMICAL PAPERS.which dissolved easily in excess. Copper sulpha te, ferric chloride,potassio-mercuric iodide, lead acetate, and potash alum gave abun-dant precipitates when added to a neutral solution. Saturation withsodium chloride or magnesium sulphate gave precipitates ; the solu-tion also gave the xanthoproteic, Millon’s, and Adamkiewicz’s reaction.A solution of the mucin in hydrochloric acid (0.3 per cent.) gaveno precipitate when digested for some fime a t 40’ ; but if pepsin werefirst added, a flocculent precipitate formed, as in solutions of nucleo.albumins. Prolonged heating with dilute mineral acids yielded noreducing substance.The following are the results of elementary analysis :-C, 50.89 ;H, 6.735 ; N, 16.14 ; and S, 1.66 per cent.The so-called mucin of bile is regarded, not as trnemncin, nor as amixture of globulin with bile salts, but as a nucleo-albumin. Smallqmntities of true mncin derived from the walla of the gall-bladderappear to be also present i n certain cases. W. D. H

ISSN:0368-1769    

DOI:10.1039/CA8885400123

出版商:RSC    

年代:1888

数据来源: RSC

摘要:

170 ABSTRACTS OF CHEMICAL PAPERS. P h y s i o l o g i c a l Chemistry. Relation of Carbohydrates in Food to Digestive Ferments. By A. STUTZER and A. ISBERT (Zeit. physiol. Chern., 12, 72-94),-- The question of the artificial digestion of carbohydrates is taken up from the same point of view as that of prote'ids (Abstr., 1887, 361, 388, 1229) ; namely, can quantitative estimations be obtained of the digestible and indigestible portions of carbohydrates by the succes- sive treatment of the fodder with the various diastatic ferments ? It is already well known that certain carbohydrates, such as starch and sugar, are more digestible than certain others, such as cellulose, which is not attacked by the digestive juices, but only by putrefac- tive agents. Standard solutions of ptyalin (from pig's salivary glands) of malt diastase, of pepsin, and of pancreatin were prepared; the t w o last being the same as those used in previous experiments.Pt.yalin acts best at 40°, diastase at 60" ; qancreatic fluid acts on starch better in a neutral than an alkaline fluid: not at all in an acid one. Clover- hay, wheat-meal, and white bread were the kinds of food used ; and tables are given of the protejid, fat, carbohydrate, ash, and water in each of these. Fat was in all cases first removed by extracting with ether. 2 grams of the food was used in each experiment,; this was boiled with 100 C.C. of water, and when cool the ferment solution was added ; 200 C.C. of the ptyalin solution with which it was kept at 37-40' for two hours: or 25 C.C. of the solution of diastase for the same length of time a t 60-65".The residue was then filtered off through asbestos, and exposed to the action of 400 C.C. of the peptic fluid; it WRS again freed from digestive fluids by filtration before being exposed for three hours to the action of the pancreaticPHYSIOLOGICAL CHEMISTRY. 171 ferment at 37-40'. The weight of the final residue (minus ash, the carbonic anhydride being driven off by nitric acid) gave the un- digested organic substance ( a ) ; the nitrogen in this was estimated, multiplied by 6.25, and the product gives t'he undigested proteyd ( b ) ; the difference between ( a ) and ( b ) gives the undigested carbohydrate. The 3rd series of analyses are those in which the food was sub- jected either to the action of ptyalin or diastase, and to the subse- quent action in most cases of pepsin.Full details in tabalar form are given of these and the following analyses; and the following cou- clusions are drawn :- (1.) A feebly alkaline solution of ptyalin acts better t,han a neutral, and this better again than a feebly acid one. (2.) For substances which are rich in digestible carbohydrates, like wheat-meal, the optimum of digestion with a neutral ptyalin solution (which was the one usually employed) was obtained when 100 C.C. of the solution was present to every gram of the food. Wheri food, such as hay, in which the digestible carbohydrates was small in quantity was used, half this amount sufficed. (3.) 25 C.C. of the diastase solution was suflicient. (4,) Ptyalin alone worked better than diastase, but when followed (5.) Neutral ptyalin solution dissolves some amount of prote'id.The second series of analyses was one in which the pancreatic fluid alone acted. 100 C.C. of the neutral fluid gave the optimum of diges- tion on the carbohydrates, but the action was not so great as with ptyalin or diastase alone. Alkaline pancreatic fluid acts best on proteids. The third series were experiments in which the action of ptyalin or diastase was followed by that of the neatral pancreatic fluid : the best results being obtained when ptyalin was first used. The additional action of the pancreas is, however, very small. The fourth series were experiments in which the action of either ptyalin or diastase was followed by that of both pepsin and pancreatic ferment ; but the optimum was the same whether ptyalin or diastase was used.Although the pancreatic juice by itself acts on amyloids best when neutral, .yet, after the action of the other ferments, the best resnlts are obtained when it is feebly alkaline. It is not, however, believed tliat these results are comparable with what is obtained in natural digestion, because The bacteria which occur in the intestines and which act so energetically on carbohydrates, are left out of account. It is possible, however, that the method of arti- ficial digestion may furnish us with- a means of estimating cellulose quantitatively. W. D. H. Changes in Carbohydrates in the Alimentary Canal. By J. SEEQEN (P'iiger's Archiv, 40, 38-48) .-Cane-sugar and starch are the carbohydrates most used as food ; the former is inverted in the stomach (Hoppe-Seyler) ; the latter is converted into erythrodextrin in the stomach, and sugar is formed from it in the intestine by the action of the pancreatic and, according to some, of the intestinal jnice also.Nasse named the sugar 80 formed ptyalose; v. Mering and by the action of pepsin they gave identical results.172 ABSTRACTS OF CHEMICAL PAPERS. Mnscnlns showed that this is identical with maltose. On the other hand, the sugar present in the blood and that which leaves the liver is dextrose. Tbe present research is devoted to a reinvestigation of these points. Animals were fed for some days on cane-sugar, and then killed ; the contents of stomach and intestines were examined, and the following conclusions drawn : the stomach inverts sugar ; besides cane-sugar, a certain quantity of redncing sugar was also found.The small intestine contained no cane-sugar ; after boiling the contents with hydrochloric acid, the amount of sugar remained the same ; the sugar present is therefore invert sugar ; 24 hours after death, no sugar is found in the stomach, and only traces in the intestine, the sugar having been changed into lactic acid. In the portal blood, a certain quantity of reducing sugar is found, but after boiling with acid there was no increase in reduction, showing that cane-sugar is not absorbed as such, or if it is, in such small quantities as not to be recognisable by this method ; the latter is probably the more correct statement, as cane-sugar is sometimes found in the urine.Tn experiments in which starch (starch-meal, potatoea, and rice) was used, it was found $hat erythrodextrin was present in the stomach, but only traces of sugar which might have been formed by the saliva, The small intestine also contains dextrin, probably achroodextrin, and a reducing sugar ; on boiling the contents of the small intestine with acid, the reducing power is increased ; this is due to the conver- sion of dextrin into sugar; if the dextrin is first precipitated by alcohol, and the residue treated with acid, there is no increase in the reducing power ; the sugar is therefore grape-sugar. It is possible that starcb is converted into maltose by the pancreatic secretion, and then by the further action of the intestinal juice iiito dextrose (Brown and Heron, Abstr., 1880, 903).Absorption takes place so rapidly that only small amounts of the products of digestion are obtainable. In the portal blood, dextrose was found, and in one instance dextrin also. W. D. H. From what Material does the Liver form Sugar 6, By J. SEEGEN (I'ffliiyer's Archiv, 40,48--64).-The liver continues to form sugar after removal from the body; in fact, as long as its cells retain vitality and the quantity formed is not in proportion to the glycogen lost (Seegen and Kratschmer, Abstr., 1882, 540). By researches of three kinds, (2) using various materials, for instance, peptones as food ; (2) injecting these substances into the blood; and (3) placing the excised liver in contact with them, it was shown fhat peptone was one substance from which the liver forms sugar. The blood in the hepatic vein contains twice as much sugar as the portal vein, whether the food contains carbohydrate ur not; fat and prote'id seem to be the substances from which the liver normalJy forms sugar.The sugar formed from glycogen by diastatic ferments is maltose, whereas that found in the blood leaving the liver is dextrose. Chittenden and Lambert (Studies from Lab. Physiol. Chem., Yale U&., 1885) obtained results which showed that although the total carbohydrates are increased by peptone, the sugar is increased butPHYSIOLOGICAL CHEMISTRY. 173 little ; they adhere to the view generally held that the sugar is formed from glycogen. They also speak of the sugar which leaves the liver as a mixture of maltose and dextrose.A large amount of the present paper is devoted to a criticism of the methods and results of Chittenden and Lambert. W. D. H. Fate of Lecithin in the Body. By K. HASERROEK (Zeit. physiol. Chem., 12, 148--162).-Bokay (Zeit. physiol. Clzsm., 1, 157) showed that the pancreatic juice splits lecithin into a fatty (oleic, palmitic, or stearic) acid, choline or neurine, and glycero-phosphoric acid. The question which is investigated in the present research was what happens to these three products of decomposition. The fatty acid doubtless behaves like fatty acids from adipose tissue, being partly saponified and separated from the body as calcium compounds, partlg absorbed and further oxidised in the body to form carbonic anhydride and water.Choline, as has been shown by Brieger’s work on ptomaines, is a type of poisonous alkaloids obtained by the putrefac- tion of organic substances. It is perhaps here also obtained from lecithin, which has a wide distribution in the animal kingdom. Putrefaction has an important part to play in the alimentary canal. The process of putrefaction in both neurine and glycero-phosphoric acid outside the body was studied according to Hoppe-Seyler’s method and with the apparatus used by him (Zeit. physiol. Ch.em., 1, 561). A mixture of choline hydrochloride, sewer-mud, calcium carbonate and water was kept at the ordinary temperature, and the gases which came off in large quantities were collected and analysed. They were found to consist of carbonic anhydride 18 to 20, and methane 80 to 82 per cent.After two months, when all evolution of gas had ceased, the liquid residue was examined microscopically, zoogloea colonies being found. Some was injected hypodermically in a rabbit but without ill results. On analysis it was fonnd to coiitain large quantities of ammonia, and traces of first substitution products ; of higher substitution basic products such as trimethylamine there was none. If a similar decomposition occurs in the intestine, it may be concluded that carbonic anhydride, methane, and ammonia are formed from choline there. This gives us a fresh source of methane in the intestine ; Hoppe-Seyler and Tappenier. (Abstr., 1887, 1131) have shown that cellulose is one source ; and Hoppe-Seyler (Abstr., 1887, 1135) has shown that acetates form another.Choline, more- over, is not an unimportant source of marsh-gas, as lecithin is largely contained in eggs, meat, and in leguminous and other seeds, On subjecting glycero-phosphoric acid to similar treatment, it was not found to yield any gases, or only minute quantities such as probably came from the mud used. The conclusion is therefore drawn that the acid is absorbed as such. This coincides with the observation of Sotnischewsky (Zeit. physioE. Chem., 4, 215). who found it unaltered in the urine. W. D. H. Relative Nutritive Value of Fat and Carbohydrate. By 0. KELLNER (Zed. physiol. Chem., 12, 113--115).-By feeding a horse on starch and linseed oil respectively, and calculating the work done, it174 ABSTRACTS OF CHEMICAL PAPERS.was fonnd that the energy of one part of fat is equal to that of 2.6 parts of starch. W. D. H. Feeding with Earth-nut and Palm Cake. By M. SCHRODT (Bied. Centr., 1887, 624-626) .-The animals employed were cows, and they were fed with palm-nnt cake containing 15 per cent. albu- minoids, whilst in the other periods of feeding they received earth- nut cake, which contained three times that quantity. Earth-nut cake cann3t be replaced by a similar quantity of palm cske without a loss of milk, fat, and dry matter,; and cotton cake produces the best results of all known cakes. Change of Chemical Composition of Muscle by Fatigue. By A. MONARI (Gazzetta, 17,367-385).-1n this paper a further account is given of the variation of the chemical composition of muscle induced by fatigue.Full-grown dogs were killed after repose and after protracted exercise, and their muscles separated and worked up by well-known methods. The relation of creat#ine to creatinine was determined in each case and the results are set forth in extensive tablm. The main conclusions arrived at are that (i) the proportion both of creatine and crentinine is increased by fatigue ; (ii) in certain cnndi- tions of labour, the proportion of creatinine can exceed that of the creatine by one-half ; (iii) in some cases the quantity of creatine in the wearied muscle is less than that present in the muscle in a state of repose, but then a greater proportion of creatine is formed owinq to the triinsforrnation of the one into the other ; (iv) that the creatinine is produced by transformation of the creatine ; (v) xanthocrentinine is also produced, and in a proportion about one-tenth of the creatinine.Ry A. MONARI (Gazzetfct, 17, 360--362).-1n this paper in addition to the pre- vious observations (Abstr., 1887,615) an analysis is given of the com- pound of xanthocreatinine with zinc chloride, which points t o a formula (C,H,,N,02,),,ZnC12. This substance cannot however be completely separated from the similar compound with creatine. V. H. V. Scatoxylsulphuric Acid and Scatole Pigment. By B. MESTER (Zeit. ylysiol. Chem., 12,130-144).-Brieger (Zeit. p h ysiol. Chem., 4, 414) showed that scatole when administered to animals leaves the body in the urine as an ethereal hydrogen sulphate, and the chromo- gen of a red pigment is often also observed ; this occnrs also in human urine.J. Otto (PJEuger’s Archiu, 33, 614) obtained this pigment from the urine of a diabetic patient in considerable quantity, and showed by its reactions and analysis that it consisted of scatoxyl potassium sulphate. In the present experiments, scatole was prepared synthetically by E. Fischer’s method (Abstr., 1886, SOS), and i t was given in doses of 6 grams daily to a dog; it was afterwards found advisable to reduce this to half, as so large a dose caused sickness occasionally but never diarrhoea. Observations were made on the relations of the normal sulphates and the ethereal hydrogen sulphates, but the variations were within normal limits. The E. W. P. V. H. V. Formation of Xanthocreatinine in the Organism.PHYSIOLOQICATi CHEMISTRY.3 75 urine passed dnring three weeks was collected, and G. Hoppe- Seyler’s method (Zeit. physiol. Chem., 7, 423) for the separation of salts of indoxylsulphuric acid was adopted for the preparation of scatoxyl potassium sulphnte, but unsuccessfully, either none of the salt or the merest traces being obtained. The pigment oannot therefore be a compound of scatoxylsulphuric acid, but the chromogen is of an unknown nature. The urine used contained abundance of the pigment, which was formed by adding hydrochloric acid to an alcoholic, ethereal, or watery extract of the evaporated urine. The urine also reduced alkaline copper hydroxide solutions, and was lzevorota,tory. A series of observations were made on the daily relations of ordinary sulphates to ethereal hydrogen sulphates, ctnd the quantity of pigment present in the urine during the admini- stration of scatole.Of 12 grains given during seven days, not more than one-fifth was passed as seatoxylsulphuric acid. There is a slight increase of ethereal hydrogen sulphates produced i n the urine by giving scatole, and the normal sulphates are slightly diminished. After prolonged feeding on scatole, however, the ethereal hydrogen snlphates are diminished in the urine, this may be due to scatole being an antiseptic ; moreover the quantity of pigment varies without any fixed relation to the amount of these compounds. The pigment is apparently an Oxidation product of the chromogen, as its formatioil i s prevented by the simultaneous action of reducing agents like nascent hydrogen.Elementary analyses are not concordant, but the author considers that they approach to what would be attained from scatoxyl itself; he considers that the pigment is an oxidation product of scatoxyl with a simultaneous condensation of two molecules. It is amorphous ; on heating it loses 10 per cent. of water. A solution of the chromogen at first colourless becomes dark-violet and later brown on exposure to air. It dissolves in hydrochloric and sulphuric acids with a red, and in alkalis with a yellow colour. It is soluble in alcohol, amyl alcohol, ether and chloroform, but not in water. It is apparently unaltered by ammoniacal fermentation. The r e d t of giving scatole as food thus differs considerably from what follows the administration of indole.The property of the urine in rotating polarised light to the left may indicate that the chromogen is a compound of glycuronic acid analogous to indoxylglycuronic acid. This pigment is perhaps the same as the pigment described in normal human urine under various names-urorubin, urorosei‘n, uroerythrin, purpnrin, &c. The effects of administering phenylhydrazinepyruvic acid to animals with their food shows that it is a powerful poison, producing blood i n trhe urine among other symptoms. By H. A. LANDWEHR (PJliiger’s Archiv, 40, 21- 37).-Animal gum (Abstr., lSS7,26) is present in greater abundance in foetal life than i n extra-uterine life; it is present in the Whar- tonian jelly, it is in excess in the connective tissues, and the chondro- genous tissue (cartilage) which precedes the long bones appears t o Acertain part of the scatole is found unchanged in the feces.W. D. H. Animal Gum.176 ABSTRACTS OF CHEMICAL PAPERS. consist of collagen combined with animal gum ; the latter compound is replaced by calcareous salts in adult bone. In some animals, as the frog, the gum is derived from the muciuo'id envelope of the eggs ; in mammals, from the uterine glands, which are enormously developed during pregnancy. Pathological conditions of the female generative organs are often associated with excess of mucin or other compounds which yield gum ; such as ovarian cysts, which contain metalbumin (pseudomucin) : goitrous colldid cysts do not yield gum. Myo- mdema, a disease first described by Gull and Ord in women, is asso- ciated with iucrease of mucin in the cutaneous tissues (Charles, Med-Chirurg. Trans., 71, 57), and may, perhaps, be associated with disease of the genital organs.Chlorosis is a form of anaemia which seems limited to women at about the age of puberty. The adminis- tration of iron in this disease causes great increase in the hEmoglobin of the blood; Hamburger, among others, has shown, however, that little or no proportion of the medicinal preparations of iron is absorbed from the alimentary canal, but iron is absorbed only in the form of organic compounds, such as are formed in the processes of plant life. Moreover, the quantity of iron is only 3 grams in the whole body, and this quantity is taken many times over during treatment, Bunge explains (Abstr., 1885, 574) the usefulness of iron in this affection by its forming iron sulphide in the intestines, removing the excess of sulphur in this way from the body ; in chlorosis due to excessive fermentat'ion processes in the alimentary canal, large quantities of hydrogen sulphide are formed, which destroy the organic com- pounds of iron that form haPmoglobin (hmmatogen); the adminis- tration of iron prevents this destruction of the hamatogen.The limitation of chlorosis to the female sex, and to the time of puberty, leads the author to doubt this explanation. He regards the disease as one produced by excessive development at this period of the sub- stances containing gum necessary for the nourisbment of the embryo, and which acts injuriously on the haemoglobin molecule ; iron pre- cipitates the gum in the alimentary canal as a jelly-like coagnlum (as i t does vegetable gum), and thus excess of gum leaves the body with the faxes.The hypothesis formerly advanced as to the function of the gum in the stomach requires to be modified as follows :-In the lumen of the gastric glands which is filled with mucus, a ferment is produced by stimulation, which forms lactic acid from the gum of the mucus, and this by acting on sodium chloride produces free hydrochloric acid and sodium lactate ; the former is poured into the stomach, the latter is absorbed from the glands. During digestion, the amount of sarco- lactic acid in the blood is increased from 0.02 to 0.1 per cent. (Drechsel). In phosphorus poisoning, this acid is found in the urine, and also excess in the gast.ric juice (Cahn, Abstr., 1886, 1053) ; the intestinal mucus in these cases remains neutral.In the intestine, the function of animal gum seems to be to aid the emulsion, and also the absorption of fats ; pancreatic juice is not neces- sary for this purpose ; -parotid saliva, which although it contains no mucin, contains free animal gum, will emulsify fats. Thierfelden (Pfliiger's Archiw, 32, 619) found that in the mammaryPHYSIOLOGICAL CHEMISTRY. 177 glands milk-sugar is formed by a fermentation process, at the body temperature from a mother-substance which is not glycogen. This substance is animal gum ; a watery decoction of rabbit’s milk-glands was freed from proteid by heat, from milk-sugar by two days’ dialysis; it mas then evaporated to a small bulk, saturated with sodilim sulphate, and filtered.The filtrate contained anirnal gum, and gave the characteristic blue flocculi with copper hydroxide. Pro- bably in the same way that starch is hydrated to form sugar in the intestines, and in the liver again dehydrated to form glycogen, so milk-sugar undergoes similar changes, which after being inverted into galactose in the alimentary canal is absorbed, and then dehydrated in the body, and stored as animal gum. If this is so, chlorotic people should take no carbohydrate food. In flesh feeders, it is probable that gum, like glycogen, is formed from prote’id. Quantitative investigations on animal gum are at present impos- sible. The conversion of the gum, C S H ~ L , into gummose, CSH1206, R reducing substance, is slow and incomplete. It is, morever, pre- cipitated at least partially by the precipitants of proteids, neutral salts, alcohol, copper sulphate, ferric chloride: &c. [Note by Abstractor.-Myxoedema has been since found to be present in men nearly as often as in women; no constant relation has been found to exist between disease of the generative organs and myxmdema ; moreover, subsequent analyses have not confirmed Charles’s statement as to tbe high percentage of mucin in the cuta- neous tissues.] W.D. H. Animal Dextran. By L. LIEBERMANN (P’liiger’s Archiv, 40, 454--$59).-The Schizoneura Zartugivosa is a gall-producing louse which attacks elms. In the interior of the gall are found masses of a secretion from the animal’s body which are a t first clear drops, hut when the galls dry up in the autumn, it consists of dirt,y-brown, irregular masses.The properties of this substance were investigated as follows :-The masses were finely divided, and boiled with distilled water ; the resulting greenish-brown cloudy solution was decolorised to a great extent by animal charcoal, and filtered; it was acidified with hydrochloric acid, and precipitated with 96 per cent. alcohol. The precipitate was washed with alcohol, dried over sulphuric acid, and analysed; the substance contained no nitrogen, and the per- centage composition corresponds very closely with the formula C,H,,O,. Its specific rotation is [a]= = +156*7. This substance has the physical appearance of gum, is soluble with difljculty in cold, more easily in boiling water; it is insoluble in alcohol and ether, and neutral in reaction.On burning it, it gives out a smell like that of burning paper. With potash and copper sulphate, a greenish-blue, jelly-like coagulum is formed soluble in hydrochloric acid ; from this acid solution, t>he gum is precipitated by alcohol. In the watery solution, lead acetate gives no precipitate, if alcohol is present, however, as well, it gives a pre- cipitate ; iodine gives no colour ; picric acid and potash also give no reaction. On heating for a long time with dilute sulphuric acid, a It does not reduce copper or bismuth salts. VOL. LIT. n178 ABSTRACTS OF CHEMICAL PAPERS. substance which reduces copper oxide is formed ; it differs from all known gums by its high rotatory power ; it seems not to be identical with Landwehr’s animal gum, and the name animal dextran (comtmre .L Scheibler, Wagner’s Jahr&er.,. 1875, 790) is suggested for it. W. D. H. Nephridia and Liver of Patella Vulgata. By A. B. GRIFFITHS (Proc. Roy. Soc., 42, 392-394) .-The nephridia were dissected from the bodies of a large number of fresh limpets, and the secretions of the left nephridia examined separately from those of the right nephridia. Chemically, the secretions on the two sides were found to be identical ; the clear liquid was first treated with hot dilute sodium hydroxide, and then hydrochloric acid added, and rhombic crystals obtained. which gave the murexide test; crystals of uric acid were obtained bv evaporating the secretion to dryness ; the residue was taken up with absolute alcohol, filtered, dissolved in hot water ; on adding excess of acetic acid to this, and allowing the mixture to stand seven hours, crystals of uric acid were obtained.The liver of patella was found to possess the functions of a true pancreas, like the “ Cephalopod liver.’’ The secretion converts starch into glucose, it produces ail emulsion with fats, and a soluble ferment extracted from the cells of the gland converts fibrin into leucine and tyrosine. The secretion con- tains proteyds, leucine, and tyrosine, but no biliary acids. Glycogen also could not be detected in either the organ or its secretion. W. D. H. Absence of Uric Acid and Alkaline Reaction in the Urine of Carnivore By G. SANARELLI (Chem. Centr., 1887,804-805 ; j y o m Ann.Chim. Farm., 1887, 273--285).-The reaction of urine from t w o young foxes was found to be strongly alkaline, both after a flesh and after a mixed diet ; uric acid was absent and hippuric acid initially present was replaced by benzoic acid. Ammoniacal fermentation quickly set in, although the urine did not coutain an abnormally large quantity of bacteria even for acid urine. Albumin, sugar and haematin were absent. With a flesh diet, the alkalinity increased, but with ft bread diet it decreased and changed suddenly into an acid reaction, although both uric and hippuric acids were absent. The alkalinity was ascertained by means of litmus and not by phenolphthale‘in. V. H. V. Presence of Hydrogen Sulphide in Urine. By F. MijLr,ER (ohem. Celztr., 1887, 807 ; from Bed.klin. Wochenschr., 24, $05--408 and 436-437) .-The formation of hydrogen sulphide in urine from fermentation (hydrothionuria) is doubtless conditioned by micro- organisms. It is here shown that its formation is due neither to albumin nor cystin, nor potassium thiocyanate, nor yet to the presence of snlphates. On adding a solution of hydrogen sulphide to normal urine, it is quickly oxidised into water and sulphur, even in absence of air, thus showing that0 in cases of hydrothionuria the urine must have lost this oxidising property. On the ot,her hand, if hy- drogen sulphide is added to urine from which the hydrogen sulphide reaction originally present has disappeared, its presence could be detected for a considerable time ; this proves that the bacteria con-PHYSIOLOGICAL CHEMISTRY.I79 sumed all the available oxygeu, and thus the oxidation of the hydro- gen sulphide could not ensue. Ethereal Hydrogen Sulphates in Morbid Urines. By G. HOPPE-SEYLER (Zeit. physioZ. Chem., 12, 1-32j .-Tables are given of the amounts of sulphuric acid combined as sulphates (a) and that com- bined as ethereal hydrogen sulphates ; (71) and the ratio a : b i n the urine of patients suffering from a variety of diseases. The details of the chief cases are also given. The general results obtained may, however, be summarised as follows :-Deficient or increased absorp- tion of the normal products of digestion, as in peritonitis, tubercular diseases of the intestine, &c., leads to an increase of ethereal hydrogen sulphates in the urine, as the normal products of digestion undergo putrefactive changes, and these putrefactive products are absorbed from the intestine.In typhoid fever, there is no such increase. Simple constipation also causes no change. Diseases of the stomach in which the food lies in the stomach a long time and then undergoes fermentative changes, alwap lead to increase of the ethereal hydrogen sulphates. Putrefactive changes outside the alimentary canal, putrid cystitis, putrid abscesses, peritonitis putrida, &c., have the same result ; and the result is proportional to the severity of the putrefaction, in- creased by the retention and diminished by the discharge of putrid matter as, for instance, on opening the abscess, The quantity of the ethereal hydrogen sulphates may, however, be unaltered, if at the same time other products of putrefaction are increased. Such a relation is seen between indoxyl and scatoxyl.In normal human urine, scatoxyl predominates over indoxyl ; in peritonitis, the reverse the case. W. D. H. V. H. V. Determination of Urea and Total Nitrogen excreted hourly in Urine. By E. GLEY and C. RICHET (Cowpt. rend. SOC. Bid. [8], 4, 3 7 7 4 8 5 ) .-Hourly determinations of the quantity of urine and the percentage of urea, extractives and total nitrogen contained therein have been made by the authors for four consecutive days. The following are the conclusions :- 1. The greatest elimination of water takes place about one hour after a meal; the greatest elimination of urea three to four hours after. 2. The excretion of water and nitrogen is much less during the night than during the day.3. With the same diet!, two persons of different body-weight ex- crete almost the same amount of nitrogen. 4. The ratio between the excretion of urea, extractives and total nitrogen remains almost constant throughout the 24 hours. 5. The ratio of nitrogen as urea to total nitrogen is about 4 to 5. J. P. L. A New Pathological Colouring Matter from Urine. By W. LEUBE (Zeit. anaZ. Chem., 26, 672).-The urine in a case of osteo- malacia tamed black in the air. Ether took up the colouring matter with red-violet colour, and on evaporation left it as a resinous mass, soluble for the most part in water, and wholly in ether, benzene, % 2180 ABSTRACTS OF CHEIUCAL PAPERS. chloroform, and alcohol.Alkalis removcd the colouring matter from its ethereal solution, becoming first brown-red and then yellow. Strong hydrochloric acid dissolved the colouring matter unchanged ; the colom disappeared on heating. Zinc-dust decolorised the solution ; the eolour returned on exposure to air. No characteristic absorption- speckrum could be seen. Urinary Pigments. By L. v. UDR~NSZKY (Zeit. physio2. Chem., 12, 33-63).-1n continuation of this research (see AFstr., 1887, 1135), the first question investigated was what constituent or constituents of normal urine yield these products. Hoppe-Seyler states that hurnous substances, when heated with potash, yield pyrocatech uic acid, volatile fatty soids, and a non-nitrogenous acid, which are the same products as those derived from the pigment.It was found that the non-iiit,rogenous residue from the humous substances prepared from normal urine, from diabetic urine, or from a mixture of urea and dextrose, has the same composition. The conclusion is drawn that, the dark colour which occurs in urine on treating it with mineral acids is due to a formation of such substances. They are formed by the decomposition of the reducing substance of normal urine, and their quantity stands in a canstant relation to the reducing power of the urine. By boiling the urine for a t least 18 hours with hydrochloric acid, the complete separation of the humous substances is brought about, and the urinc loses i2ts reducing power. The indoxyl compounds in the urine have probably only a very small influence in the formation of these sub- stances. Humous substances containing nitrogen can be formed from carbohydrates in the presence of nascent ammonia.As Thudi- chum first remarked, there can no longer be any doubt that Proust’s fallow resin, Scharling’s omichmyl oxide, Heller’s nrrhodine, Schunck’s indirubin, Scherer’s pigment from urinc, Harley’s uro- barnatin, and Marcet’s immediate principle, are different expressioirs for one and the same mixture of substances, namely, of some of the products of decomposition by acids or ferments, under the influence of air or heat of the normal yellow pigment of the urine. The uropithin, uromelamin, and omicholic acid of Thudichum, Heller’s 11 roph =in, and several others can now be put into the same category ; i t is also possible to go a step further and say that the mother-substance of these artificially prepared pigments is the reducing substance of urine, and the normal yellow colour of urine is due to the change of carbohydrates into humous substances which has commenced iuside the body.The dark colour of the mine of hcrbivora (horses) depends on the presence of some constituent of the hay ; the colour itself is due to a humous substance formed from this material in the fodder. The dark colour of the urine after the administration of carbolic acid (carboluria) is also due to a similar substance. M. J. s. W. D. H. Ferments in Human Faeces and in the Contentsof Cysts. By R. V. JAKSCH (Reit. physiol. Chem., 12, 116--129).-The contents of abdominal cysts and ascitic fluid have a diastatic action ; the blood aud other tissues and fluids of the body have also been described asPHPSIOLOGICAL CEIXMISTRY.181 having a similar action. The presence of such a ferment in the contents of pancreahic cysts cannot therefore be considered diagnostic. The faces of children were examined for a similar ferment, and in 30 cases of various diseases, i t was found that the faxes themselves, as well as a glycerol extract of them, had a marked diastatic action on starch in most cases. Sugar was tesbed for by Trommer’s, Nylander’s, Rubner’s, and the phenylhydrazine tests, and abundance was Found in 25 cases. I n three cases only a small amount of sugar was formed; these were cases of pneumonia: rickets, and acute nephritis respectively ; in two cases only (chronic intestinal catarrh and general atrophy respectively) did the ferment appear to be absent.Whether this ferment is derived from the pancreas, or is due to the action of micro-organisms, or is the result of the presence of certain protei‘ds (Seegeu and Kratschmer having shown that egg-albumin, serum-albumin, and case’in have an amylolytic action, PfEiiger’s Archiu, 14, 593)’ is uncertain. Possibly all these factors come into account. A second series of experiments similarly conducted proved the presence of R ferment, which, with one exception, was soluble in glycerol, and which had the power of inverting cane-sugar. This ferment may be derived from the intestinal juice (0. Loew, P$iiger’s A ~ c h i v , 27, 203 ; Pavy, Maly’s Juhresber., 14, 294). The action is certainly not due to the action of acids in the faxes, as it is present in alkaline faxes also.Both these ferments are present in healthy faeces, and in adults as well as in children. Their absence in cases of disease may be found to be of diagnostic value; but this question, as well as that of the influence of these ferments on food introduced per rectum, must be left until more is known about them. The presence of ferments shows probably that some action more important than the mere absorption of water goes on in the large intestine. W. D. H. Hemoglobin Crystals in Septic Diseases. By C. J, BOND (Lancet, 2, 1887, 509-511, 557-560).-1f normal human blood is drawn from the finger, placed on a slide, and covered with a cover- glass, no crystallisation of the haemoglobin occurs.If, however, a drop of putrid serum is added, crystallisation occurs in 24 to 48 hours. The blood drawn from the finger of patients suffering from septic poisoning has the same tendency to crystallise without the addition of any serum. In pyaemia, the effect is not so marked ; in the blood from the red patches of erysipelas there is the same tendency for crystallisation to occur after removal from the body, whereas this does not occur in blood drawn from other parts of the body ; in cancrum oris, which is an emphatically infective process, the same phenomenon is observed ; whereas in the common zymotic diseases the blood behaves normally. The presence of sugar in the blood in diabetes, or the nitrogenous subst,anceR in uramia, 01’ the supposed lactic acid in rheumatism, or the bile salts in jaundice, is also not sufficient in itself to cause the crystalline tendency.I n Addison’s disease and in leucocythaemia, the crystalline tendency is well marked, whereas in ordinary anaemia, and often in pernicious antemia, it is absent. In leucocythamia the change is evidently connected with the presence of excess of white182 ABSTRACTS OF CHEMICAL PAPERS. corpuscles, or some product of their decomposition ; cancer cells, and the cells of other rapidly growing tumours, act. similarly to leucocytcbs in this particular. It is found that in 10 or 12 hours after death in persons who have died from accident, the crystalline tendency is present in the blood removed from the heart, and absent in that removed from the limbs ; this is probably because the blood in the heart is within easy reach of the septic gases formed in the intes- tines.The larger domestic animals resemble man in the matter 'of crystallisation of hsemoglobin ; but in the seemingly healthy mouse crystallisation occurs readily in the unaltered blood ; in the cat there is a similar but not so well marked a tendency, especially in blood drawn from the splenic vein, The occurrence of this tendency in man under the conditions described above, especially in septic diseases, is supposed to be due to the formation or presence of some ferment produced, either by the growth of bacterial organisms, or as in leucocythsemia, by the dis- integration of animal cells; the stages in the change which this ferment works being first a deoxidising action on the hsemoglobin, then its exndation into the serum, and lastly crjstallisation.W. D. H. Physiological and Therapeutical Action of Hyoscine Hydro- chloride, By E. GLEY and P. RQNDEAU (Compt. rend. SUC. Bid. [8], 4, 56-57, and 163-164) .-Hyoscine hydrochloride and hydro- bromide are rapid, powerful, and unirritat ing mydriatics, acting more rapidly and for a more prolonged period than atropine. One drop of a 1 per cent. solution produces the maximum dilatation and para- Jysis of accommodation in 8 to 10 minutes. In the rabbit and dog, the pupil of the other eye is affected, dilata- tion and temporary paralysis of accommodation occurring. This is not the case in man, so far as the authors' oibservations go. I f the cervical sympathetic of a rabbit i s seyered on the same side as the eye treated with the mydriatic, further dilzLtation of the pupil takes place on stimulating the proximal end of the nerve.The hydro- chloride exercises the same effect as atropine on the inhibitory nerves of the heart, and diminishes or even snppre.sses tbe secretion of saliva, excitation of the chocda tympani with even sfrong currents being without effect on the submaxillary gland,. Both the hjdrochloride and the hydrobromide act as powerful sedatives. J. P. L. Sodium Benzenesulphinate as an Antiseptic for Wounds, By E. HECKEL (Cornpt. rend., 105, 896--898).-This compound is readily obtained by dissolving benzoic acid in a concentrated solution of sodium sulphite. It is very soluble in water at the ordinary teni- perature, and has no injurious effects even in somewhat large doses.It may be applied in the form of a solution containing from 4 to 5 grams per litre. It is more efficient than phenol, and ranks with mercuric salts and iodoform, without having the poisonous properties of the former or the dkagreeable smell of the latter. C. H. B.PHYSIOLOaIChL CHEMISTRY. 183 Naphthol as an Antiseptic Medicine. By C. BOUCHARD (Compt. rend., 105, 702-707) .-+-Naphthol has already been used for external application, but has not been administered internally on account of its supposed high toxic power. From its comparative in- solubility, however, it. is a valuable antiseptic for deep wounds and fbr internal adniinistration ; 1000 C.C. of water dissolve 0.2 gram ; 1000 C.C.of water containing 0.1 per cent. alcohol dissolve 0.33 gram ; 1000 C.C. containing 5 per cent. alcohol dissolve 1.0 grsm ; 1000 C.C. containing 30 per cent. alcohol dissolve 2.0 grams. 0.33 gram of &naphthol in 1000 C.C. of the usual cultivation liquids prevents the development of 11 species of bacteria, including hhose of anthrax, chicken cholera, and pneumonia, and a weak cultivation of the typhoid bacillus: it also retards the development of the bacillus of tuberculosis. It pre- vents the fermentation of urine, and the production of putrefaction by frecal matter. Putrefying organic substances mixed with p-naphthol in the proportion of 0.2 gram per litre cease to putrefy, and soon lose their fcetidity. In order to compare P-naphthol with other antiseptics, the author determined t,he quant,ity required to prevent the development of the bacillus which produces pyocyanine.0.4 gram of @-naphthol per litre was required, and mercuric iodide was found to have six times the antiseptic power, phenol only one-sixth, creosot>e one-fourth. Mer- curic iodide is, however, a violent poison, whilst P-naphthol may be introduced into the stomach of a rabbit in quantities not exceeding 3.8 grams per kilo. without producing death. Mercuric iodide has 250 times the toxic power. The fatal dose for a man of 65 kilos. wou!d therefore be more than 259 gra.ms, and it is only slightly more poisonous when injected subcutaneously. The poisonous action of B-naphthol is not observed with doses not exceeding 1.1 gram per kilo. per diem ; the injurious effects previously observed must have been largely due to the mode of administration.The following table shows th-e iornparative efficiency of the less seytics :- An tiseptic. Iodoform .......... 1.27 Iodol .............. 2.75 Naphthalene ........ 1.51 p-Naphthol ......... 0.40 poisonous insolubl; anti- Doses per kilo. f---”-- 7 Toxic. Daily toxic. 0.50 0.05 2.1 7 1.24 3.40 1-00 3-80 1-10 C. H. B. Localisation of Barium in the Organism arter Chronic Poisoning with a Barium Salt. By G. LINOSSIER (Conapt. rend. SOC. Biol. [S], 4, 122--123).-Neumann has recently shown in the case of rabbits, that after repeated injections of fhe insoluble sulphate into the veins, barium. is to be found in the liver, kidneys, spleen, and spinal cord, but not in the muscles, thymus, and brain.As the insolubility of the sulphate precludes the question of chronic poieoning, the author has made a similar series of experiments with barium carbonate, prolonging the chronic poisoning for a period of 30 daya. He finds on analysis that all organs contain some barium,184 ABSTRACTS OF CHEMICAL PAPERS. but that it is present in very variable proportions. Lungs, muscles, and particularly the heart yield only traces, liver rather more, kid- neys, brain, and spinal cord still more, and lastly bones a considerable quantity, as much as 0.56 in 1000 parts of bone ash. Action of Acetanilide and Dihydroxynaphthalene on Blood. By R. L~PINE (Compt. ?-end. Xoc. Bid. [8], 4, 517-519) .-Both wet- anilide and dihydroxynaphthalene wheii administered as drugs pro- duce after continued use a marked ansmic condition of the pahnt,.The number of red corpuscles rapidly diminishes, and methmmoglobin is produced. J. P. L. J. P. L. Saffron Substitutes. By T. WEYL (Ber., 20, 2835-2836).- Commercial dinitrocresol is employed as a yellow colouring matter for bntter, margarine, vermicelli, and confectionery. The author finds that it is poisonous, and that when introduced i n aqueous solution into the stomach of rabbits in doses of 0.25 gram per kilo. it causes convulsions, paralysis of the pupil, and great difficulty in bileathing, death ensuing from suffocation in from 20 t o 30 minutes. Martius- yellow and the " butter-yellow " prepared by Griess from dimethyl- aniline and diazotised aniline are not poisonous. w.P. w.170 ABSTRACTS OF CHEMICAL PAPERS.P h y s i o l o g i c a l Chemistry.Relation of Carbohydrates in Food to Digestive Ferments.By A. STUTZER and A. ISBERT (Zeit. physiol. Chern., 12, 72-94),--The question of the artificial digestion of carbohydrates is taken upfrom the same point of view as that of prote'ids (Abstr., 1887, 361,388, 1229) ; namely, can quantitative estimations be obtained of thedigestible and indigestible portions of carbohydrates by the succes-sive treatment of the fodder with the various diastatic ferments ? Itis already well known that certain carbohydrates, such as starch andsugar, are more digestible than certain others, such as cellulose,which is not attacked by the digestive juices, but only by putrefac-tive agents.Standard solutions of ptyalin (from pig's salivary glands) of maltdiastase, of pepsin, and of pancreatin were prepared; the t w o lastbeing the same as those used in previous experiments.Pt.yalin actsbest at 40°, diastase at 60" ; qancreatic fluid acts on starch better ina neutral than an alkaline fluid: not at all in an acid one. Clover-hay, wheat-meal, and white bread were the kinds of food used ; andtables are given of the protejid, fat, carbohydrate, ash, and water ineach of these. Fat was in all cases first removed by extracting withether. 2 grams of the food was used in each experiment,; this wasboiled with 100 C.C. of water, and when cool the ferment solution wasadded ; 200 C.C. of the ptyalin solution with which it was kept at37-40' for two hours: or 25 C.C.of the solution of diastase forthe same length of time a t 60-65". The residue was then filteredoff through asbestos, and exposed to the action of 400 C.C. of thepeptic fluid; it WRS again freed from digestive fluids by filtrationbefore being exposed for three hours to the action of the pancreatiPHYSIOLOGICAL CHEMISTRY. 171ferment at 37-40'. The weight of the final residue (minus ash,the carbonic anhydride being driven off by nitric acid) gave the un-digested organic substance ( a ) ; the nitrogen in this was estimated,multiplied by 6.25, and the product gives t'he undigested proteyd ( b ) ;the difference between ( a ) and ( b ) gives the undigested carbohydrate.The 3rd series of analyses are those in which the food was sub-jected either to the action of ptyalin or diastase, and to the subse-quent action in most cases of pepsin.Full details in tabalar form aregiven of these and the following analyses; and the following cou-clusions are drawn :-(1.) A feebly alkaline solution of ptyalin acts better t,han aneutral, and this better again than a feebly acid one.(2.) For substances which are rich in digestible carbohydrates,like wheat-meal, the optimum of digestion with a neutral ptyalinsolution (which was the one usually employed) was obtained when100 C.C. of the solution was present to every gram of the food. Wherifood, such as hay, in which the digestible carbohydrates was small inquantity was used, half this amount sufficed.(3.) 25 C.C.of the diastase solution was suflicient.(4,) Ptyalin alone worked better than diastase, but when followed(5.) Neutral ptyalin solution dissolves some amount of prote'id.The second series of analyses was one in which the pancreatic fluidalone acted. 100 C.C. of the neutral fluid gave the optimum of diges-tion on the carbohydrates, but the action was not so great as withptyalin or diastase alone. Alkaline pancreatic fluid acts best onproteids.The third series were experiments in which the action of ptyalin ordiastase was followed by that of the neatral pancreatic fluid : the bestresults being obtained when ptyalin was first used. The additionalaction of the pancreas is, however, very small.The fourth series were experiments in which the action of eitherptyalin or diastase was followed by that of both pepsin and pancreaticferment ; but the optimum was the same whether ptyalin or diastasewas used.Although the pancreatic juice by itself acts on amyloidsbest when neutral, .yet, after the action of the other ferments, thebest resnlts are obtained when it is feebly alkaline.It is not, however, believed tliat these results are comparable withwhat is obtained in natural digestion, because The bacteria which occurin the intestines and which act so energetically on carbohydrates, areleft out of account. It is possible, however, that the method of arti-ficial digestion may furnish us with- a means of estimating cellulosequantitatively. W. D. H.Changes in Carbohydrates in the Alimentary Canal.By J.SEEQEN (P'iiger's Archiv, 40, 38-48) .-Cane-sugar and starch arethe carbohydrates most used as food ; the former is inverted in thestomach (Hoppe-Seyler) ; the latter is converted into erythrodextrinin the stomach, and sugar is formed from it in the intestine by theaction of the pancreatic and, according to some, of the intestinal jnicealso. Nasse named the sugar 80 formed ptyalose; v. Mering andby the action of pepsin they gave identical results172 ABSTRACTS OF CHEMICAL PAPERS.Mnscnlns showed that this is identical with maltose. On the otherhand, the sugar present in the blood and that which leaves the liver isdextrose.Tbe present research is devoted to a reinvestigation of thesepoints. Animals were fed for some days on cane-sugar, and thenkilled ; the contents of stomach and intestines were examined, and thefollowing conclusions drawn : the stomach inverts sugar ; besidescane-sugar, a certain quantity of redncing sugar was also found.Thesmall intestine contained no cane-sugar ; after boiling the contentswith hydrochloric acid, the amount of sugar remained the same ; thesugar present is therefore invert sugar ; 24 hours after death, no sugaris found in the stomach, and only traces in the intestine, the sugarhaving been changed into lactic acid. In the portal blood, a certainquantity of reducing sugar is found, but after boiling with acid therewas no increase in reduction, showing that cane-sugar is not absorbedas such, or if it is, in such small quantities as not to be recognisableby this method ; the latter is probably the more correct statement, ascane-sugar is sometimes found in the urine.Tn experiments in which starch (starch-meal, potatoea, and rice) wasused, it was found $hat erythrodextrin was present in the stomach, butonly traces of sugar which might have been formed by the saliva,The small intestine also contains dextrin, probably achroodextrin,and a reducing sugar ; on boiling the contents of the small intestinewith acid, the reducing power is increased ; this is due to the conver-sion of dextrin into sugar; if the dextrin is first precipitated byalcohol, and the residue treated with acid, there is no increase in thereducing power ; the sugar is therefore grape-sugar. It is possiblethat starcb is converted into maltose by the pancreatic secretion, andthen by the further action of the intestinal juice iiito dextrose (Brownand Heron, Abstr., 1880, 903).Absorption takes place so rapidlythat only small amounts of the products of digestion are obtainable.In the portal blood, dextrose was found, and in one instance dextrinalso. W. D. H.From what Material does the Liver form Sugar 6, By J. SEEGEN(I'ffliiyer's Archiv, 40,48--64).-The liver continues to form sugar afterremoval from the body; in fact, as long as its cells retain vitalityand the quantity formed is not in proportion to the glycogen lost(Seegen and Kratschmer, Abstr., 1882, 540). By researches of threekinds, (2) using various materials, for instance, peptones as food ;(2) injecting these substances into the blood; and (3) placing theexcised liver in contact with them, it was shown fhat peptone wasone substance from which the liver forms sugar.The blood in thehepatic vein contains twice as much sugar as the portal vein, whetherthe food contains carbohydrate ur not; fat and prote'id seem to bethe substances from which the liver normalJy forms sugar. The sugarformed from glycogen by diastatic ferments is maltose, whereas thatfound in the blood leaving the liver is dextrose.Chittenden and Lambert (Studies from Lab. Physiol. Chem., YaleU&., 1885) obtained results which showed that although the totalcarbohydrates are increased by peptone, the sugar is increased buPHYSIOLOGICAL CHEMISTRY. 173little ; they adhere to the view generally held that the sugar is formedfrom glycogen. They also speak of the sugar which leaves theliver as a mixture of maltose and dextrose.A large amount of thepresent paper is devoted to a criticism of the methods and resultsof Chittenden and Lambert. W. D. H.Fate of Lecithin in the Body. By K. HASERROEK (Zeit. physiol.Chem., 12, 148--162).-Bokay (Zeit. physiol. Clzsm., 1, 157) showedthat the pancreatic juice splits lecithin into a fatty (oleic, palmitic, orstearic) acid, choline or neurine, and glycero-phosphoric acid. Thequestion which is investigated in the present research was whathappens to these three products of decomposition. The fatty aciddoubtless behaves like fatty acids from adipose tissue, being partlysaponified and separated from the body as calcium compounds, partlgabsorbed and further oxidised in the body to form carbonic anhydrideand water.Choline, as has been shown by Brieger’s work onptomaines, is a type of poisonous alkaloids obtained by the putrefac-tion of organic substances. It is perhaps here also obtained fromlecithin, which has a wide distribution in the animal kingdom.Putrefaction has an important part to play in the alimentary canal.The process of putrefaction in both neurine and glycero-phosphoricacid outside the body was studied according to Hoppe-Seyler’smethod and with the apparatus used by him (Zeit. physiol. Ch.em., 1,561). A mixture of choline hydrochloride, sewer-mud, calciumcarbonate and water was kept at the ordinary temperature, and thegases which came off in large quantities were collected and analysed.They were found to consist of carbonic anhydride 18 to 20, andmethane 80 to 82 per cent.After two months, when all evolution ofgas had ceased, the liquid residue was examined microscopically,zoogloea colonies being found. Some was injected hypodermically ina rabbit but without ill results. On analysis it was fonnd to coiitainlarge quantities of ammonia, and traces of first substitution products ;of higher substitution basic products such as trimethylamine therewas none. If a similar decomposition occurs in the intestine, it maybe concluded that carbonic anhydride, methane, and ammonia areformed from choline there. This gives us a fresh source of methanein the intestine ; Hoppe-Seyler and Tappenier.(Abstr., 1887, 1131)have shown that cellulose is one source ; and Hoppe-Seyler (Abstr.,1887, 1135) has shown that acetates form another. Choline, more-over, is not an unimportant source of marsh-gas, as lecithin islargely contained in eggs, meat, and in leguminous and other seeds,On subjecting glycero-phosphoric acid to similar treatment, it wasnot found to yield any gases, or only minute quantities such asprobably came from the mud used. The conclusion is thereforedrawn that the acid is absorbed as such. This coincides with theobservation of Sotnischewsky (Zeit. physioE. Chem., 4, 215). whofound it unaltered in the urine. W. D. H.Relative Nutritive Value of Fat and Carbohydrate. By 0.KELLNER (Zed.physiol. Chem., 12, 113--115).-By feeding a horse onstarch and linseed oil respectively, and calculating the work done, i174 ABSTRACTS OF CHEMICAL PAPERS.was fonnd that the energy of one part of fat is equal to that of 2.6 partsof starch. W. D. H.Feeding with Earth-nut and Palm Cake. By M. SCHRODT(Bied. Centr., 1887, 624-626) .-The animals employed were cows,and they were fed with palm-nnt cake containing 15 per cent. albu-minoids, whilst in the other periods of feeding they received earth-nut cake, which contained three times that quantity.Earth-nut cake cann3t be replaced by a similar quantity of palmcske without a loss of milk, fat, and dry matter,; and cotton cakeproduces the best results of all known cakes.Change of Chemical Composition of Muscle by Fatigue.ByA. MONARI (Gazzetta, 17,367-385).-1n this paper a further accountis given of the variation of the chemical composition of muscleinduced by fatigue. Full-grown dogs were killed after repose andafter protracted exercise, and their muscles separated and worked upby well-known methods. The relation of creat#ine to creatinine wasdetermined in each case and the results are set forth in extensive tablm.The main conclusions arrived at are that (i) the proportion both ofcreatine and crentinine is increased by fatigue ; (ii) in certain cnndi-tions of labour, the proportion of creatinine can exceed that of thecreatine by one-half ; (iii) in some cases the quantity of creatine inthe wearied muscle is less than that present in the muscle in a state ofrepose, but then a greater proportion of creatine is formed owinq tothe triinsforrnation of the one into the other ; (iv) that the creatinine isproduced by transformation of the creatine ; (v) xanthocrentinine isalso produced, and in a proportion about one-tenth of the creatinine.Ry A.MONARI (Gazzetfct, 17, 360--362).-1n this paper in addition to the pre-vious observations (Abstr., 1887,615) an analysis is given of the com-pound of xanthocreatinine with zinc chloride, which points t o a formula(C,H,,N,02,),,ZnC12. This substance cannot however be completelyseparated from the similar compound with creatine.V. H. V.Scatoxylsulphuric Acid and Scatole Pigment. By B. MESTER(Zeit. ylysiol. Chem., 12,130-144).-Brieger (Zeit.p h ysiol. Chem., 4,414) showed that scatole when administered to animals leaves thebody in the urine as an ethereal hydrogen sulphate, and the chromo-gen of a red pigment is often also observed ; this occnrs also inhuman urine. J. Otto (PJEuger’s Archiu, 33, 614) obtained thispigment from the urine of a diabetic patient in considerable quantity,and showed by its reactions and analysis that it consisted of scatoxylpotassium sulphate. In the present experiments, scatole was preparedsynthetically by E. Fischer’s method (Abstr., 1886, SOS), and i t wasgiven in doses of 6 grams daily to a dog; it was afterwards foundadvisable to reduce this to half, as so large a dose caused sicknessoccasionally but never diarrhoea. Observations were made on therelations of the normal sulphates and the ethereal hydrogensulphates, but the variations were within normal limits.TheE. W. P.V. H. V.Formation of Xanthocreatinine in the OrganismPHYSIOLOQICATi CHEMISTRY. 3 75urine passed dnring three weeks was collected, and G. Hoppe-Seyler’s method (Zeit. physiol. Chem., 7, 423) for the separationof salts of indoxylsulphuric acid was adopted for the preparationof scatoxyl potassium sulphnte, but unsuccessfully, either noneof the salt or the merest traces being obtained. The pigmentoannot therefore be a compound of scatoxylsulphuric acid, but thechromogen is of an unknown nature. The urine used containedabundance of the pigment, which was formed by adding hydrochloricacid to an alcoholic, ethereal, or watery extract of the evaporatedurine. The urine also reduced alkaline copper hydroxide solutions,and was lzevorota,tory.A series of observations were made on thedaily relations of ordinary sulphates to ethereal hydrogen sulphates,ctnd the quantity of pigment present in the urine during the admini-stration of scatole. Of 12 grains given during seven days, not morethan one-fifth was passed as seatoxylsulphuric acid. There is aslight increase of ethereal hydrogen sulphates produced i n the urineby giving scatole, and the normal sulphates are slightly diminished.After prolonged feeding on scatole, however, the ethereal hydrogensnlphates are diminished in the urine, this may be due to scatole beingan antiseptic ; moreover the quantity of pigment varies without anyfixed relation to the amount of these compounds.The pigment isapparently an Oxidation product of the chromogen, as its formatioil i sprevented by the simultaneous action of reducing agents like nascenthydrogen.Elementary analyses are not concordant, but the author considersthat they approach to what would be attained from scatoxyl itself; heconsiders that the pigment is an oxidation product of scatoxyl with asimultaneous condensation of two molecules. It is amorphous ; onheating it loses 10 per cent. of water. A solution of the chromogenat first colourless becomes dark-violet and later brown on exposure toair. It dissolves in hydrochloric and sulphuric acids with a red, andin alkalis with a yellow colour.It is soluble in alcohol, amyl alcohol,ether and chloroform, but not in water. It is apparently unaltered byammoniacal fermentation.Ther e d t of giving scatole as food thus differs considerably from whatfollows the administration of indole. The property of the urine inrotating polarised light to the left may indicate that the chromogen isa compound of glycuronic acid analogous to indoxylglycuronic acid.This pigment is perhaps the same as the pigment described innormal human urine under various names-urorubin, urorosei‘n,uroerythrin, purpnrin, &c.The effects of administering phenylhydrazinepyruvic acid to animalswith their food shows that it is a powerful poison, producing blood i ntrhe urine among other symptoms.By H.A. LANDWEHR (PJliiger’s Archiv, 40, 21-37).-Animal gum (Abstr., lSS7,26) is present in greater abundancein foetal life than i n extra-uterine life; it is present in the Whar-tonian jelly, it is in excess in the connective tissues, and the chondro-genous tissue (cartilage) which precedes the long bones appears t oAcertain part of the scatole is found unchanged in the feces.W. D. H.Animal Gum176 ABSTRACTS OF CHEMICAL PAPERS.consist of collagen combined with animal gum ; the latter compoundis replaced by calcareous salts in adult bone. In some animals, as thefrog, the gum is derived from the muciuo'id envelope of the eggs ; inmammals, from the uterine glands, which are enormously developedduring pregnancy. Pathological conditions of the female generativeorgans are often associated with excess of mucin or other compoundswhich yield gum ; such as ovarian cysts, which contain metalbumin(pseudomucin) : goitrous colldid cysts do not yield gum.Myo-mdema, a disease first described by Gull and Ord in women, is asso-ciated with iucrease of mucin in the cutaneous tissues (Charles,Med-Chirurg. Trans., 71, 57), and may, perhaps, be associated withdisease of the genital organs. Chlorosis is a form of anaemia whichseems limited to women at about the age of puberty. The adminis-tration of iron in this disease causes great increase in the hEmoglobinof the blood; Hamburger, among others, has shown, however, thatlittle or no proportion of the medicinal preparations of iron is absorbedfrom the alimentary canal, but iron is absorbed only in the form oforganic compounds, such as are formed in the processes of plant life.Moreover, the quantity of iron is only 3 grams in the whole body, andthis quantity is taken many times over during treatment, Bungeexplains (Abstr., 1885, 574) the usefulness of iron in this affection byits forming iron sulphide in the intestines, removing the excessof sulphur in this way from the body ; in chlorosis due to excessivefermentat'ion processes in the alimentary canal, large quantitiesof hydrogen sulphide are formed, which destroy the organic com-pounds of iron that form haPmoglobin (hmmatogen); the adminis-tration of iron prevents this destruction of the hamatogen.Thelimitation of chlorosis to the female sex, and to the time of puberty,leads the author to doubt this explanation.He regards the diseaseas one produced by excessive development at this period of the sub-stances containing gum necessary for the nourisbment of the embryo,and which acts injuriously on the haemoglobin molecule ; iron pre-cipitates the gum in the alimentary canal as a jelly-like coagnlum(as i t does vegetable gum), and thus excess of gum leaves the bodywith the faxes.The hypothesis formerly advanced as to the function of the gum inthe stomach requires to be modified as follows :-In the lumen of thegastric glands which is filled with mucus, a ferment is produced bystimulation, which forms lactic acid from the gum of the mucus, andthis by acting on sodium chloride produces free hydrochloric acidand sodium lactate ; the former is poured into the stomach, the latteris absorbed from the glands.During digestion, the amount of sarco-lactic acid in the blood is increased from 0.02 to 0.1 per cent.(Drechsel). In phosphorus poisoning, this acid is found in the urine,and also excess in the gast.ric juice (Cahn, Abstr., 1886, 1053) ; theintestinal mucus in these cases remains neutral.In the intestine, the function of animal gum seems to be to aid theemulsion, and also the absorption of fats ; pancreatic juice is not neces-sary for this purpose ; -parotid saliva, which although it contains nomucin, contains free animal gum, will emulsify fats.Thierfelden (Pfliiger's Archiw, 32, 619) found that in the mammarPHYSIOLOGICAL CHEMISTRY.177glands milk-sugar is formed by a fermentation process, at the bodytemperature from a mother-substance which is not glycogen. Thissubstance is animal gum ; a watery decoction of rabbit’s milk-glandswas freed from proteid by heat, from milk-sugar by two days’dialysis; it mas then evaporated to a small bulk, saturated withsodilim sulphate, and filtered. The filtrate contained anirnal gum,and gave the characteristic blue flocculi with copper hydroxide. Pro-bably in the same way that starch is hydrated to form sugar in theintestines, and in the liver again dehydrated to form glycogen, somilk-sugar undergoes similar changes, which after being inverted intogalactose in the alimentary canal is absorbed, and then dehydrated inthe body, and stored as animal gum. If this is so, chlorotic peopleshould take no carbohydrate food.In flesh feeders, it is probable thatgum, like glycogen, is formed from prote’id.Quantitative investigations on animal gum are at present impos-sible. The conversion of the gum, C S H ~ L , into gummose, CSH1206,R reducing substance, is slow and incomplete. It is, morever, pre-cipitated at least partially by the precipitants of proteids, neutralsalts, alcohol, copper sulphate, ferric chloride: &c.[Note by Abstractor.-Myxoedema has been since found to bepresent in men nearly as often as in women; no constant relationhas been found to exist between disease of the generative organs andmyxmdema ; moreover, subsequent analyses have not confirmedCharles’s statement as to tbe high percentage of mucin in the cuta-neous tissues.]W.D. H.Animal Dextran. By L. LIEBERMANN (P’liiger’s Archiv, 40,454--$59).-The Schizoneura Zartugivosa is a gall-producing lousewhich attacks elms. In the interior of the gall are found masses ofa secretion from the animal’s body which are a t first clear drops, hutwhen the galls dry up in the autumn, it consists of dirt,y-brown,irregular masses. The properties of this substance were investigatedas follows :-The masses were finely divided, and boiled with distilledwater ; the resulting greenish-brown cloudy solution was decolorisedto a great extent by animal charcoal, and filtered; it was acidifiedwith hydrochloric acid, and precipitated with 96 per cent.alcohol.The precipitate was washed with alcohol, dried over sulphuric acid,and analysed; the substance contained no nitrogen, and the per-centage composition corresponds very closely with the formula C,H,,O,.Its specific rotation is [a]= = +156*7. This substance has thephysical appearance of gum, is soluble with difljculty in cold, moreeasily in boiling water; it is insoluble in alcohol and ether, andneutral in reaction. On burning it, it gives out a smell like that ofburning paper. Withpotash and copper sulphate, a greenish-blue, jelly-like coagulum isformed soluble in hydrochloric acid ; from this acid solution, t>he gumis precipitated by alcohol. In the watery solution, lead acetate givesno precipitate, if alcohol is present, however, as well, it gives a pre-cipitate ; iodine gives no colour ; picric acid and potash also give noreaction.On heating for a long time with dilute sulphuric acid, aIt does not reduce copper or bismuth salts.VOL. LIT. 178 ABSTRACTS OF CHEMICAL PAPERS.substance which reduces copper oxide is formed ; it differs from allknown gums by its high rotatory power ; it seems not to be identicalwith Landwehr’s animal gum, and the name animal dextran (comtmre . L Scheibler, Wagner’s Jahr&er.,. 1875, 790) is suggested for it.W. D. H.Nephridia and Liver of Patella Vulgata. By A. B. GRIFFITHS(Proc. Roy. Soc., 42, 392-394) .-The nephridia were dissected fromthe bodies of a large number of fresh limpets, and the secretions of theleft nephridia examined separately from those of the right nephridia.Chemically, the secretions on the two sides were found to be identical ;the clear liquid was first treated with hot dilute sodium hydroxide, andthen hydrochloric acid added, and rhombic crystals obtained.whichgave the murexide test; crystals of uric acid were obtained bvevaporating the secretion to dryness ; the residue was taken up withabsolute alcohol, filtered, dissolved in hot water ; on adding excess ofacetic acid to this, and allowing the mixture to stand seven hours,crystals of uric acid were obtained. The liver of patella was foundto possess the functions of a true pancreas, like the “ Cephalopodliver.’’ The secretion converts starch into glucose, it produces ailemulsion with fats, and a soluble ferment extracted from the cells ofthe gland converts fibrin into leucine and tyrosine.The secretion con-tains proteyds, leucine, and tyrosine, but no biliary acids. Glycogenalso could not be detected in either the organ or its secretion.W. D. H.Absence of Uric Acid and Alkaline Reaction in the Urine ofCarnivore By G. SANARELLI (Chem. Centr., 1887,804-805 ; j y o mAnn. Chim. Farm., 1887, 273--285).-The reaction of urine fromt w o young foxes was found to be strongly alkaline, both after a fleshand after a mixed diet ; uric acid was absent and hippuric acid initiallypresent was replaced by benzoic acid. Ammoniacal fermentationquickly set in, although the urine did not coutain an abnormally largequantity of bacteria even for acid urine.Albumin, sugar and haematinwere absent. With a flesh diet, the alkalinity increased, but with ftbread diet it decreased and changed suddenly into an acid reaction,although both uric and hippuric acids were absent. The alkalinitywas ascertained by means of litmus and not by phenolphthale‘in.V. H. V.Presence of Hydrogen Sulphide in Urine. By F. MijLr,ER(ohem. Celztr., 1887, 807 ; from Bed. klin. Wochenschr., 24, $05--408and 436-437) .-The formation of hydrogen sulphide in urine fromfermentation (hydrothionuria) is doubtless conditioned by micro-organisms. It is here shown that its formation is due neither toalbumin nor cystin, nor potassium thiocyanate, nor yet to the presenceof snlphates. On adding a solution of hydrogen sulphide tonormal urine, it is quickly oxidised into water and sulphur, even inabsence of air, thus showing that0 in cases of hydrothionuria the urinemust have lost this oxidising property.On the ot,her hand, if hy-drogen sulphide is added to urine from which the hydrogen sulphidereaction originally present has disappeared, its presence could bedetected for a considerable time ; this proves that the bacteria conPHYSIOLOGICAL CHEMISTRY. I79sumed all the available oxygeu, and thus the oxidation of the hydro-gen sulphide could not ensue.Ethereal Hydrogen Sulphates in Morbid Urines. By G.HOPPE-SEYLER (Zeit. physioZ. Chem., 12, 1-32j .-Tables are given ofthe amounts of sulphuric acid combined as sulphates (a) and that com-bined as ethereal hydrogen sulphates ; (71) and the ratio a : b i n theurine of patients suffering from a variety of diseases. The details ofthe chief cases are also given.The general results obtained may,however, be summarised as follows :-Deficient or increased absorp-tion of the normal products of digestion, as in peritonitis, tuberculardiseases of the intestine, &c., leads to an increase of ethereal hydrogensulphates in the urine, as the normal products of digestion undergoputrefactive changes, and these putrefactive products are absorbedfrom the intestine. In typhoid fever, there is no such increase.Simple constipation also causes no change. Diseases of the stomachin which the food lies in the stomach a long time and then undergoesfermentative changes, alwap lead to increase of the ethereal hydrogensulphates.Putrefactive changes outside the alimentary canal, putridcystitis, putrid abscesses, peritonitis putrida, &c., have the same result ;and the result is proportional to the severity of the putrefaction, in-creased by the retention and diminished by the discharge of putridmatter as, for instance, on opening the abscess, The quantity of theethereal hydrogen sulphates may, however, be unaltered, if at thesame time other products of putrefaction are increased. Such arelation is seen between indoxyl and scatoxyl. In normal humanurine, scatoxyl predominates over indoxyl ; in peritonitis, the reversethe case. W. D. H.V. H. V.Determination of Urea and Total Nitrogen excreted hourlyin Urine.By E. GLEY and C. RICHET (Cowpt. rend. SOC. Bid. [8],4, 3 7 7 4 8 5 ) .-Hourly determinations of the quantity of urine andthe percentage of urea, extractives and total nitrogen containedtherein have been made by the authors for four consecutive days. Thefollowing are the conclusions :-1. The greatest elimination of water takes place about one hourafter a meal; the greatest elimination of urea three to four hoursafter.2. The excretion of water and nitrogen is much less during thenight than during the day.3. With the same diet!, two persons of different body-weight ex-crete almost the same amount of nitrogen.4. The ratio between the excretion of urea, extractives and totalnitrogen remains almost constant throughout the 24 hours.5. The ratio of nitrogen as urea to total nitrogen is about 4 to 5.J.P. L.A New Pathological Colouring Matter from Urine. By W.LEUBE (Zeit. anaZ. Chem., 26, 672).-The urine in a case of osteo-malacia tamed black in the air. Ether took up the colouring matterwith red-violet colour, and on evaporation left it as a resinous mass,soluble for the most part in water, and wholly in ether, benzene,% 180 ABSTRACTS OF CHEIUCAL PAPERS.chloroform, and alcohol. Alkalis removcd the colouring matter fromits ethereal solution, becoming first brown-red and then yellow. Stronghydrochloric acid dissolved the colouring matter unchanged ; thecolom disappeared on heating. Zinc-dust decolorised the solution ;the eolour returned on exposure to air. No characteristic absorption-speckrum could be seen.Urinary Pigments.By L. v. UDR~NSZKY (Zeit. physio2. Chem., 12,33-63).-1n continuation of this research (see AFstr., 1887, 1135),the first question investigated was what constituent or constituents ofnormal urine yield these products. Hoppe-Seyler states that hurnoussubstances, when heated with potash, yield pyrocatech uic acid, volatilefatty soids, and a non-nitrogenous acid, which are the same products asthose derived from the pigment. It was found that the non-iiit,rogenousresidue from the humous substances prepared from normal urine,from diabetic urine, or from a mixture of urea and dextrose, has thesame composition. The conclusion is drawn that, the dark colourwhich occurs in urine on treating it with mineral acids is due to aformation of such substances. They are formed by the decompositionof the reducing substance of normal urine, and their quantity standsin a canstant relation to the reducing power of the urine.By boilingthe urine for a t least 18 hours with hydrochloric acid, the completeseparation of the humous substances is brought about, and the urincloses i2ts reducing power. The indoxyl compounds in the urine haveprobably only a very small influence in the formation of these sub-stances. Humous substances containing nitrogen can be formedfrom carbohydrates in the presence of nascent ammonia. As Thudi-chum first remarked, there can no longer be any doubt that Proust’sfallow resin, Scharling’s omichmyl oxide, Heller’s nrrhodine,Schunck’s indirubin, Scherer’s pigment from urinc, Harley’s uro-barnatin, and Marcet’s immediate principle, are different expressioirsfor one and the same mixture of substances, namely, of some of theproducts of decomposition by acids or ferments, under the influence ofair or heat of the normal yellow pigment of the urine.The uropithin,uromelamin, and omicholic acid of Thudichum, Heller’s 11 roph =in,and several others can now be put into the same category ; i t is alsopossible to go a step further and say that the mother-substanceof these artificially prepared pigments is the reducing substance ofurine, and the normal yellow colour of urine is due to the change ofcarbohydrates into humous substances which has commenced iusidethe body.The dark colour of the mine of hcrbivora (horses) depends on thepresence of some constituent of the hay ; the colour itself is due to ahumous substance formed from this material in the fodder.The dark colour of the urine after the administration of carbolicacid (carboluria) is also due to a similar substance.M.J. s.W. D. H.Ferments in Human Faeces and in the Contentsof Cysts.By R. V. JAKSCH (Reit. physiol. Chem., 12, 116--129).-The contentsof abdominal cysts and ascitic fluid have a diastatic action ; the bloodaud other tissues and fluids of the body have also been described aPHPSIOLOGICAL CEIXMISTRY. 181having a similar action. The presence of such a ferment in thecontents of pancreahic cysts cannot therefore be considered diagnostic.The faces of children were examined for a similar ferment, and in30 cases of various diseases, i t was found that the faxes themselves,as well as a glycerol extract of them, had a marked diastatic actionon starch in most cases. Sugar was tesbed for by Trommer’s,Nylander’s, Rubner’s, and the phenylhydrazine tests, and abundancewas Found in 25 cases.I n three cases only a small amount of sugarwas formed; these were cases of pneumonia: rickets, and acutenephritis respectively ; in two cases only (chronic intestinal catarrhand general atrophy respectively) did the ferment appear to be absent.Whether this ferment is derived from the pancreas, or is due to theaction of micro-organisms, or is the result of the presence of certainprotei‘ds (Seegeu and Kratschmer having shown that egg-albumin,serum-albumin, and case’in have an amylolytic action, PfEiiger’s Archiu,14, 593)’ is uncertain.Possibly all these factors come into account.A second series of experiments similarly conducted proved the presenceof R ferment, which, with one exception, was soluble in glycerol, andwhich had the power of inverting cane-sugar. This ferment maybe derived from the intestinal juice (0. Loew, P$iiger’s A ~ c h i v , 27,203 ; Pavy, Maly’s Juhresber., 14, 294). The action is certainly notdue to the action of acids in the faxes, as it is present in alkalinefaxes also.Both these ferments are present in healthy faeces, and in adults aswell as in children. Their absence in cases of disease may be foundto be of diagnostic value; but this question, as well as that of theinfluence of these ferments on food introduced per rectum, must beleft until more is known about them. The presence of ferments showsprobably that some action more important than the mere absorption ofwater goes on in the large intestine.W. D. H.Hemoglobin Crystals in Septic Diseases. By C. J, BOND(Lancet, 2, 1887, 509-511, 557-560).-1f normal human blood isdrawn from the finger, placed on a slide, and covered with a cover-glass, no crystallisation of the haemoglobin occurs. If, however, a dropof putrid serum is added, crystallisation occurs in 24 to 48 hours. Theblood drawn from the finger of patients suffering from septic poisoninghas the same tendency to crystallise without the addition of any serum.In pyaemia, the effect is not so marked ; in the blood from the redpatches of erysipelas there is the same tendency for crystallisation tooccur after removal from the body, whereas this does not occur inblood drawn from other parts of the body ; in cancrum oris, which isan emphatically infective process, the same phenomenon is observed ;whereas in the common zymotic diseases the blood behaves normally.The presence of sugar in the blood in diabetes, or the nitrogenoussubst,anceR in uramia, 01’ the supposed lactic acid in rheumatism,or the bile salts in jaundice, is also not sufficient in itself to cause thecrystalline tendency.I n Addison’s disease and in leucocythaemia,the crystalline tendency is well marked, whereas in ordinary anaemia,and often in pernicious antemia, it is absent.In leucocythamia thechange is evidently connected with the presence of excess of whit182 ABSTRACTS OF CHEMICAL PAPERS.corpuscles, or some product of their decomposition ; cancer cells, andthe cells of other rapidly growing tumours, act. similarly to leucocytcbsin this particular. It is found that in 10 or 12 hours after death inpersons who have died from accident, the crystalline tendency ispresent in the blood removed from the heart, and absent in thatremoved from the limbs ; this is probably because the blood in theheart is within easy reach of the septic gases formed in the intes-tines.The larger domestic animals resemble man in the matter 'ofcrystallisation of hsemoglobin ; but in the seemingly healthy mousecrystallisation occurs readily in the unaltered blood ; in the cat thereis a similar but not so well marked a tendency, especially in blooddrawn from the splenic vein,The occurrence of this tendency in man under the conditionsdescribed above, especially in septic diseases, is supposed to be due tothe formation or presence of some ferment produced, either by thegrowth of bacterial organisms, or as in leucocythsemia, by the dis-integration of animal cells; the stages in the change which thisferment works being first a deoxidising action on the hsemoglobin,then its exndation into the serum, and lastly crjstallisation.W.D. H.Physiological and Therapeutical Action of Hyoscine Hydro-chloride, By E. GLEY and P.RQNDEAU (Compt. rend. SUC. Bid. [8],4, 56-57, and 163-164) .-Hyoscine hydrochloride and hydro-bromide are rapid, powerful, and unirritat ing mydriatics, acting morerapidly and for a more prolonged period than atropine. One drop ofa 1 per cent. solution produces the maximum dilatation and para-Jysis of accommodation in 8 to 10 minutes.In the rabbit and dog, the pupil of the other eye is affected, dilata-tion and temporary paralysis of accommodation occurring. This isnot the case in man, so far as the authors' oibservations go.I f the cervical sympathetic of a rabbit i s seyered on the same sideas the eye treated with the mydriatic, further dilzLtation of the pupiltakes place on stimulating the proximal end of the nerve. The hydro-chloride exercises the same effect as atropine on the inhibitory nervesof the heart, and diminishes or even snppre.sses tbe secretion of saliva,excitation of the chocda tympani with even sfrong currents beingwithout effect on the submaxillary gland,.Both the hjdrochloride and the hydrobromide act as powerfulsedatives.J. P. L.Sodium Benzenesulphinate as an Antiseptic for Wounds,By E. HECKEL (Cornpt. rend., 105, 896--898).-This compound isreadily obtained by dissolving benzoic acid in a concentrated solutionof sodium sulphite. It is very soluble in water at the ordinary teni-perature, and has no injurious effects even in somewhat large doses.It may be applied in the form of a solution containing from 4 to5 grams per litre. It is more efficient than phenol, and ranks withmercuric salts and iodoform, without having the poisonous propertiesof the former or the dkagreeable smell of the latter.C. H. BPHYSIOLOaIChL CHEMISTRY. 183Naphthol as an Antiseptic Medicine. By C. BOUCHARD(Compt. rend., 105, 702-707) .-+-Naphthol has already been usedfor external application, but has not been administered internally onaccount of its supposed high toxic power. From its comparative in-solubility, however, it. is a valuable antiseptic for deep wounds and fbrinternal adniinistration ; 1000 C.C. of water dissolve 0.2 gram ; 1000 C.C.of water containing 0.1 per cent. alcohol dissolve 0.33 gram ; 1000 C.C.containing 5 per cent. alcohol dissolve 1.0 grsm ; 1000 C.C. containing30 per cent. alcohol dissolve 2.0 grams. 0.33 gram of &naphthol in1000 C.C. of the usual cultivation liquids prevents the development of11 species of bacteria, including hhose of anthrax, chicken cholera,and pneumonia, and a weak cultivation of the typhoid bacillus: italso retards the development of the bacillus of tuberculosis. It pre-vents the fermentation of urine, and the production of putrefaction byfrecal matter. Putrefying organic substances mixed with p-naphtholin the proportion of 0.2 gram per litre cease to putrefy, and soon losetheir fcetidity.In order to compare P-naphthol with other antiseptics, the authordetermined t,he quant,ity required to prevent the development of thebacillus which produces pyocyanine. 0.4 gram of @-naphthol per litrewas required, and mercuric iodide was found to have six times theantiseptic power, phenol only one-sixth, creosot>e one-fourth. Mer-curic iodide is, however, a violent poison, whilst P-naphthol may beintroduced into the stomach of a rabbit in quantities not exceeding3.8 grams per kilo. without producing death. Mercuric iodide has250 times the toxic power. The fatal dose for a man of 65 kilos.wou!d therefore be more than 259 gra.ms, and it is only slightly morepoisonous when injected subcutaneously. The poisonous action ofB-naphthol is not observed with doses not exceeding 1.1 gram perkilo. per diem ; the injurious effects previously observed must havebeen largely due to the mode of administration. The following tableshows th-e iornparative efficiency of the lessseytics :-An tiseptic.Iodoform .......... 1.27Iodol .............. 2.75Naphthalene ........ 1.51p-Naphthol ......... 0.40poisonous insolubl; anti-Doses per kilo.f---”-- 7Toxic. Daily toxic.0.50 0.052.1 7 1.243.40 1-003-80 1-10C. H. B.Localisation of Barium in the Organism arter ChronicPoisoning with a Barium Salt. By G. LINOSSIER (Conapt. rend.SOC. Biol. [S], 4, 122--123).-Neumann has recently shown in thecase of rabbits, that after repeated injections of fhe insoluble sulphateinto the veins, barium. is to be found in the liver, kidneys, spleen, andspinal cord, but not in the muscles, thymus, and brain.As the insolubility of the sulphate precludes the question of chronicpoieoning, the author has made a similar series of experiments withbarium carbonate, prolonging the chronic poisoning for a period of30 daya. He finds on analysis that all organs contain some barium184 ABSTRACTS OF CHEMICAL PAPERS.but that it is present in very variable proportions. Lungs, muscles,and particularly the heart yield only traces, liver rather more, kid-neys, brain, and spinal cord still more, and lastly bones a considerablequantity, as much as 0.56 in 1000 parts of bone ash.Action of Acetanilide and Dihydroxynaphthalene on Blood.By R. L~PINE (Compt. ?-end. Xoc. Bid. [8], 4, 517-519) .-Both wet-anilide and dihydroxynaphthalene wheii administered as drugs pro-duce after continued use a marked ansmic condition of the pahnt,.The number of red corpuscles rapidly diminishes, and methmmoglobinis produced. J. P. L.J. P. L.Saffron Substitutes. By T. WEYL (Ber., 20, 2835-2836).-Commercial dinitrocresol is employed as a yellow colouring matter forbntter, margarine, vermicelli, and confectionery. The author findsthat it is poisonous, and that when introduced i n aqueous solutioninto the stomach of rabbits in doses of 0.25 gram per kilo. it causesconvulsions, paralysis of the pupil, and great difficulty in bileathing,death ensuing from suffocation in from 20 t o 30 minutes. Martius-yellow and the " butter-yellow " prepared by Griess from dimethyl-aniline and diazotised aniline are not poisonous. w. P. w

ISSN:0368-1769    

DOI:10.1039/CA8885400170

出版商:RSC    

年代:1888

数据来源: RSC

摘要:

184 ABSTRACTS OF CHEMICAL PAPERS. Chemistry of Vegetable Physiology and Agriculture. Studies on Pure Yeast. By C. AMTHOR (Zeit. physiol. Cl~em., 12, 64- 71) .-The paper consists of comparative observations on the fermentative activity on wort of eight different kinds of yeast ob- tained from various German breweries. Observations were made on the amount of alcohol, extractives, specific gravity, glycei.ol, nitrogen, and reducing substances (reckoned as maltose). The colour intensity was also observed by Stammer's colorimeter. The wort contained 10.8 of maltose ; after fermentation, the sum total of sugar (that reckoned as alcohol + the maltose in the beer) was 11-34. In reality the increase was greater, as dextrin and malto- dexfrin are reckoned in the above as maltose. The increase is doubt- less due to the conversion of dextrin into maltose.W. D. H. Influence of the Age of Yeast on Alcoholic Fermentation. By P. REGNARD (Ccrrnpt. rend. SOC. Biol. [ 8 ] , 4,442-444).-The in- ff uence on alcoholic fermentation exercised by the protoplasmic metamorphosis which occurs in the yeast cell when i t is maintained under circurnstances of complete starvation is represented graphi- cally by the method introduced by the author in 1882. The characteristic fermentation which yeast normally produces is lost after three days' complete starvation at a temperature of 25" to 30" J. P. L.VEGETABLE PHYSIOLOQY AND AGRICULTURE. '1 85 The Development of Free Nitrogen in Putrefaction and Nitrification. By 0. KELLNER and T. YOSHII (Zeit. physiol.Chem., 12, 95-111).-1n the first experiments, beans, milk, and fish meal were allowed to putrefy, 20 to 50 grams of each being mixed with 10 C.C. of putrid urine and 33 C.O. of water, a small quantity of gypsum being also added. The quantity of nitrogen present before and after putrefaction was practically the same; no formation of nitrates took place. I n a second series of experiments with ( a ) aspa- ragine and ( b ) beans, earth was added, and also small quantities of rnonocslcium phosphate, precipitated tricalcium phosphate, and mag- nesium sulphate, for the favourable development of organised fer- ments (Warington, Trans., 1834, 637) ; no nitrification occurred, however, even after five months, and nitrogen estimations gave the same results as in the first experiments. There is thus no loss of nitrogen during putrefaction.Dietzell in experiments similar to those of Ehrenberg (Abstr., 1887, 746) in the presence of oxjgen, obtained different results. In the experiments made by the latter the putrefaction lasted six weeks, and there was no free nitrogen formed, whilst in those of the former, in which the experiments lasted 12 months, there was a loss of 15 per cent. of the nitrogen, that is to say, although putrefaction pure and simple does not cause the disengagement of gaseous nitrogen, certain processes of a secondary nature may perbaps do so. It may be due to the oxidation of ammonia by atmospheric oxygen. This could, however, not take place if organic substances are present which have a, stronger affinity for oxygen; or it may be due to similar oxidation brought about by the action of nitrifying organisms, or by the action of free nitric acid on nitrogenous organic compounds; or it may be due to the reduction of nitrates and nitrites by organic substances, or, lastly, to a spontaneous decomposition of ammonium nitrate in dilute solutions. I n a third series of experiments, in which the earth used con- tained the nitrifying ferment, it was found that a loss of 9 to 10 per cent.of nitrogen acconipanied the nitrification process ; in which out of the possible ways enumerated above this takes place no definite statement can be made. Diluted sterilised solutions of ammonium nitrate do not appear to decompose spontaneously, but most pro- bably the loss of nitrogen is due to a reaction between nitrites and organic nitrogenous compounds.When nitrification begins, the reaction of the urine, at first acid, becomes alkaline, and later neutral ; this then remains unaltered. It appears possible that it is in the deeper layers of the mixture, or where the earth is specially rich in humus, that a portion of the nitrates or nitrites is rednced. W. D. H. Formation of Nitrogen during Putrefaction. By A. EHREN- REKG (Zeit. physiol. Chem., 12, 145--147).-A few further experi- ments illustrating the formation of methane and carbonic anhydride in putrefaction are detailed (Abstr., 1887, 746). W. D. H. Dependence of Assimilation of Green Cells on their Respi- ration of Oxygen; the part of the Plant in which Oxygen186 ABSTRACTS OF CHEMICAL PAPERS, formed in Assimilation is produced. By N.PR~XGSHEIM ( B e y . Akad. Ber., 1887, 763-777 ; compare Abstr., 1886, 64'2).-The end cells of the leaves of Chara fraqilis were enclosed in a microscopic gas- chamber, through which a mixture of hydrogen and carbonic anhy- dride (containing 1 to 5 per cent. of the latter) was passed. When light is excluded, the rotation gradually becomes less and less until at last (in 2 to 10 hours) the plasma is quite still. The cells, if not kept too long in this state, otherwise retain their original appearance, the chlorophyll apparatus remaining normal. On admitting oxygen, the rotation of the plasma again commences, unless the cells have been kept too long without oxygen after the protoplasm has ceased to rotate. If the cells are kept without oxygen just so long that the plasma still shows a slight movement, they will be found to have lost the power of assimilating, and when exposed to light, will no longer g i v e off oxygen.When the cells of Chara are exposed to light in a stream of hydrogen and carbonic anhydride, rotation of the plasma and evolution of oxygen cease after some time; in most cases the evolution of oxygen ceases before the rotation. The presence of the smallest amount of oxygen is sufficient (even after the rotation of the plasma has ceased for some time) to bring about movement and assimilation. These results make it probable that in the decomposition of car- bonic anhydride in plants no oxygen is formed, but that a compound is produced which decomposes a t the outermost surface of the cells with evolution of oxygen.The decomposition of carbonic anhydride and the evolution of oxygen do not occur together, but are distinct processes both as to time and place. Green and other tissues and plants in dying give off oxygen in the dark ; the evolution of oxygen often continues for hours after the plant has died. Assimilation and Respiration of Plants. By U. KREUSLER (Bied. Centr., 1887, 669-68 l).--In this continuation of former experiments (Bied. Centr., 1881, 110) are given the details of experiments made with shoots of the same kind of plant, Pldadelphus qraiidajlorus, a t different stages of growth, the temperature of observation being 15" and 25". At a temperature of 25", a strong and marked decrease in assimilative power accompanies increasing age of the leaf; a t 15" a maximum of assimilative power is noticed in the youngest leaves, This power reaches its minimum at the period of blossom, and agaiii rises in the oldest leaves ; so that between the assimilative power in the youngest and in the oldest leaves, there does not exist much difference.A table showing the amount of water absorbed at the different temperatures is also given. I n the second portion of this paper, amongst many statements concerning the absorption and exha- lation of carbonic anhydride at different temperatures, it is recorded that the range of temperature in which exhalation occurs is from 0- 50°, and that it is greatest a t the highest temperature, the maximum appearing to be a t 46.4". Assimilation seems to take place a t a lower temperature than exhalation, and it is active at 50" ; but the curve representing the relation of assimilation to temperature daes not N.H. $1.VEGETABLE PEIYSIOLOGY AND AGRICULTURE. 187 agree with that representing exhalation at various temperatures. In the case of the bramble, the maximum intensity of exhalation occurs at about 466", whilst that of assimilation is found at 25". For further statements and arguments, reference must be made to the original. E. W. P. Physiological Signification of Tannin in Vegetable Tissues. By 11. WES'I'ERMA~ER (Ber. Akad. Ber., 1887, 127--143).-The amount of tannin in living cells free from and containing chlorophyll increases with the amount of light to which the cells are exposed. Experiments made with Quercus pedunculata showed that tjhe tannin migrates from the leaves downwards through the bark and the pith.It is uncertain whether starch and tannin migrate side by side without changing, or whether the starch migrates in the form of tannin. In examiniug the leaves of Ruinez patentia and Rheum rhaponticunz, st substance was found which showed the starch reaction with iodine and the tannin reaction with ferric chloride and with potassium dichromate. The colour produced in the starch reaction is a bright- blue, sometimes greenish, and sometimes deep sky-blue. The sub- stance was found in large amount in the autumn leaves of Rheum rliayonticum. N. H. M. The Hop and its Constituents. By HAYDUCK (Bied. Centr., 1887, 694-698) .-Hops have no influence on alcoholic fermentation, but they retard, even if they do not wholly prevent, lactic fermen- tation, and this applies also t o the butyric and other forms of like change, excepting the acetous, which is unaffected.Lerner and Bungener have shown that there exists in hops a white, crystallint: compound, which they termed " hop-bitter acid." This acid, OIL oxidation, forms a soft resinous matter, slightly soluble in water; besides the acid, a hard resin seems to exist in large quantities, and the authors have now discovered a third, soft resin. The method whereby it may be obtained is as follows :-The hops are first exhausted with ether, and after evaporation of the ether, the residue is treated with alcohol, which leaves a white wax undissolved ; solution of lead acetate is then added to the alcoholic solution, when a yellow preci- pitate is produced, consisting of the soft resin in combination with lead.In the filtrate from this precipitate, the two other resins are found, the one soft and soluble in light, petroleum, the other hard, iusolcible in light petroleum, but soluble in alcohol and ether; the former is identical with that which is an oxidation-product of hop- bitter acid. All three seem to be feeble acids, and have no definite solixbility in water, but the solution of the soft resins are intensely and disagreeably bitter ; whilst that of the hard resin is slightly and agreeably bitter. As regards the suppression of lactic fermentation, although the hard resin has no effect, this property belongs to the soft resins.A resinous coating sometimes forms in the wort in brewing, and it has been generally ascribed to resin, but this view is now shown to be incorrect, as this coating contains only 4 6 per cent. of resin soluble in ether, whilst nitrogenous matter was present to the extent of 13 per cent. of nitrogen. E. W. P.188 ABSTRACTS OF CHEMICAL PAPERS. Compounds extracted from Anagyris Fcetida. By N. REALI (G'nzzetta, 17, 325--329).-The seeds of the Anagyris fcetida, on ex- traction with ether, yield a fatty oil, two resinous substances, and also a citron-vellow compound not further examined but probably a glucoside. From an alcoholic extract, glucose, sacchsrose, and st yellow substance are obtained, together with a compound having all the characteristics of an alkaloyd, and called ArLagyrine. One of the above resinous substances which the author calls ann- gyric mid forms a lead salt, by means of which the acid can be isolated.It contains carbon, hydrogen and oxygen, but the analyses given are not very concordant. The oil is not desiccative, sp. gr. = 0.924 a t 17" ; on treatment with sulphuric and nitric acid, it acquires a blood-red colour. The oil yields a mixture of fatty acids on saponi- fication. Anagyrine occurs as an amorphous mass of bitter taste, soluble in water, alcohol, ether, and benzene ; it has an alkaline re- action and forms salts with acids. It gives all the reactions of alkalo'idu, such as precipitates with solutions of phosphomolybdic acid, potassium bismutho-iodide, and potassium mercuro-iodide. It is unaltered at ordinary temperature by sulphuric acid, but when warmed it evolves a musk-like odour.The platinochloride is an amorphous, yellow powder, the analysis of which pointed to a formula, CIIH3,N0, for anagyrine. The Freezing of Ciders. By G. LECHARTIER (Compt. rend., 105, 723-726).-The cider was cooled at -18" to -20" until nearly completely frozen, and the liquid portioc was drawn off. The mother- liquor was denser and more highly coloured than the liquid obtained by melting the ice, which in the end yielded almost pure water. The mother-liquors were kept in a cellar for some months, and at the end of that time had a very fine colour and flavour. Addition of sugar t o the must merely increases the proportion of alcohol, but concentra- tion by freezing concentrates all the soluble substances from the apples.Concentration should not be carried beyond a certain point or a disagreeable flavour is developed, and for a similar reason only ciders of good oyiginal quality are suitable for this treatment. Even when the cider is kept a t -18' for 12 hours, the ferment is not killed, although fermentation is retarded. By F. MENGARINI (Gazzetta, l7,441450).-Blaserna and Carpene have previously made experiments on the effects produced on wine by the action of an electric current ; these have shown that various oxidation product8 are formed, and the wine is artificially matured. In this paper, some further experiments on this subject are described, in which a current o f 3.99 amp8res per hour was passed for various periods of time through a sample of Italian wine ; analyses were made of the wine without a.nd with passage of the current and the results compared.The platinum electrodes were found to be corered with albuminous substances, blackened by oxidation ; there was also a considerable deposit of these substances. The proportion of alcohol was diminished partly by the slight concomitant formation of acetic acid, partly also V. H. V. C. H. B. Effects of an Electric Current on Wine.WOETABLE PHYSIOLOGY AND AGRICULTURE. 189 by evaporation, and partly also by its destruction by a more profound oxidation. There wa.s also imparted to the wine a perfume similar to that acquired by maturing ; this increased by prolongation of the current. The passage of the current also assists its future preserva- tion.The colouring matters are affected, but the author would not for the present draw any conclusions from his experiments. If by passage of an electric current the wine could be sterilised, so as to effect the complete IBemoval of Bacterium aceti, this process would be of considerable technical importance. V. H. V. Manuring Barley. By v. LIEBENBERG (Bied. Centr., 1887, 649- 651).-The experiments were conducted at 12 st.ations, and tbe manures employed were (1) Chili saltpetre, (2) Chili saltpetre and soluble phosphate, and (3) Chili saltpetre, soluble phosphate and potas- sium sulphate. The spring of the year (1886) was dry, whilst June and July were wet. There were three failures ; of the remaining nine stations, the nitrogen showed itself active in producing corn and straw at seven stations, whilst an influence on the straw only was manifested at two.In two cases, potash increased the corn and straw, whilst in one it acted on the straw only ; the phosphate in five cases affected the corn and straw, and in one the straw only. It seems then that nitrogen is available for barley in all localities, whilst phosphates or potash are less PO. Manuring Oats. By v. LIEBENBERG (Ried. Certtr., 1887, 651- 653).-The experiments were conducted on the same principle and in the same manner as those on barley manuring. Nitrogen, and nitro- gen combined with phosphate yielded an increase, but there is an uncertainty as to the gain produced by potash. Phosphates influence oats more than barley, because the former is slower and later in coming to maturity.E. W. P. E. W. P. Comparative Experiments with Oats manured with Basic Slag on Moorlands. By BAESSLEH, (Bied. Cem!r., 1887, 653-655). -The soil on which the experiments were conducted contained 69 per cent. organic matter, 2.7 N, 0.29 P205, and 13.66 per cent. ash. Kainite, basic slag, and superphosphates were used. Neither the super nor the slag produced any decided effects ; kainite increased the yield of straw, but a general increase was remarked when the phos- phates in either form were combined with kainite. The action of the slag was only 42 per cent. of that of the superphosphate, but this difierenca is compensated for by the lower price of the slag. E. W. P. Manuring Winter Wheat and Winter Rye. By V. LIEBEN- BERG (Bied.Centr., 1887, 656-658).-Tbe manures were the same as those employed in the author's experiment8 on oats and barley. No decided nor especial advantage was remarked in the crop of wheat thus manured. As regards the rye, nitrogen alone produced no effect, but when combined with phosphates or kainite there was a very decided increase. The author accounts for the absence of effect190 ABSTRACTS OF CHEMICAL PAPERS. from the uRe of nitrogen by the fact that the a n d had previously Manuring of Vines. By J. MORITZ and P. SEUCKER (Bied. Cent?-., 1887, 604-609).-The experiments were instituted to determine if artificial manures could not be used for vines instead of the expensive farmyard manure. The manures were those usually employed, namely, ammonia superphofiphates and potash compounds, and peat.The analyses of the must as well as its total quantity show that fa8rm- yard manure can be replaced by other manures; mineral manureg seem to prerent the usual premature ripening, and consequently rotting, of some of the berries on the vines, whilst farmyard manure induces an extra growth of weeds. These experiments have been carried on for nine years, and are still being continued. Condition of Potassium in Soils, Plants, and Moulds. By BERTHELOT and ANDRF: (C'ompt. rend., 105, 833-840 ; 91 1-914)- I kilo. of the dried earth contained 23.5 grams organic carbon, 1.66 gram nitrogen at the beginning of the season and 1.73 gram. and the end, and 8-92 grams of potassium. The only methods available for the estimation of the total potassium are those in which the soil is completely decomposed by ammonium fluoride, calcium carbonate, or barium hydroxide.Water percolating through the soil removed only 0.0029 gram of potassium per kilo., but if the soil was treated with successive quan- tities of water the amount dissolved increased to 0.143 gram per kilo. Heating the soil to dull redness had little effect on the solubility of the potassium. Ethyl acetate and ammonia have practically no effect on the solubi- lity, but water containing 2 per cent. of sugar or acetamide dissolves more potassium compound than pure water. Water saturated with carbonic anhrdride dissolved 0.198 gram per litre ; water containing 2 per cent. of acetic acid dissolved 0.290 gram per litre ; water with 2 per cent. of hydrochloric acid 0.404 gram; water with 2 per cent.nitric acid 0.296 gram. These results afford no definite evidence either as to the forms in which the potassium exists in the soil or as to the proportion assimilable by plants. Concentrated hydrochloric and nitric acids at a higher temperature dissolve considerably more potassium, the exact quantity depending on the temperature and time of action. The whole of t*he potassium, however, is never removed. Calcination of the soil increases the proportion of the potassium soluble in acids, probably in consequence of some alteration of the silicates. It is not possible to draw any sharp line of demarcation between the potassium which is soluble or insoluble, assimilable or non- assimilable. In order to obtain similar information respecting the potassium present in living plants, Mercurialis annua was selected as an example.The dried plant contained per kilo. 19.35 grams of nitrogen and 27.87 grams of potassium oxide, and left 125 grams of ash. When treated with 10 times its weight of water for 24 hours, received farmyard manure. E. w. P. E. W. P.VEGETABLE PHYSIOLOGY AND AGRICULTURE. 191 18-92 gra,ms of potasaium per kilo., or two-thirds of the total amount, was dissolved. Hydrochloric acid of 2 to 3 per cent. dissolved 84-58 grams of potassium in 24 hours, or 5.66 grams more than water. The remaining 3.29 grams was present in some form insoluble in dilute acids. A sample of vegetable mould which was examined in a similar waj7 contained 32.4 per cent. of water and lost 45.9 per cent.when calcined in presence of air. The dried mould contained per kilo. 95.8 grams of organic cnrhon ; 14.5 grams combined carbonic anhydride ; 8.6 grams of nitrogen; and 11.65 grams of potassinm. 2-96 grams or one- quarter of the potassium was soluble in water; 5.84 grams was soluble in hydrochloric acid of 2 per cent., but even after incineration the quantity of potassium insoluble in acids was 2-14 grams per kilo. The proportion soluble in water was considerably less after incinera- tion, owing doubtless to the action of the silicates on the potassium carbonate. It is erident that the mould does not retain the whole of the potas- sium present in the .original plant, a considerable proportion being removed by rain during the process of decay. The proportion remain- ing is, however, still much more considerable than in the soil, and mould is a truly complementary manure intermediate in its character between the organic and inorganic manures.Best Time for Ploughing Yellow Lupines under. By BAESSLER (Bied. Ceiz.fr., 1887, 615-618) .-The periods into which the growth of the yellow lupine which was to be used as “green manure ” was divided, were (1) full bloom of main stem, (2) commencement of podding of the same, (3) full bloom of side shoots, (4) full ripeness of the pods of main stern. It was found that the plants should be ploughed under in the fourth period, for then they mould give to the morgen N 140.3 kilos., R20 53.96, and P205 25.7, when 253,440 plants are allowed per morgen ; at tbis period, the nitrogen and phos- phoric acid are three times and the potash twice that found in the plant in the period of bloom. Analysis of Rubbish-heaps employed to Improve Soils.By A. MAPER ( B i d . Centr., 1887, 577--578).-The rubbish-heaps arc found at places of refuge which were frequented in times of flooding before Holland was protected by dykes; they consist largely of animaland vegetable remains. The analysis of one sample must heye suffice: Organic matter, 6.0 per cent. ; total nitrogen, 0.14; easily soluble nitrogen, 0.02 ; phosphoric acid, 0.78 ; potash, 0.34 ; calcium carbonate, 1.1. The material is richer in plant food than the various “ muds ” used for amelioration of poor land ; i n the former, the lowest quantity of phosphoric acid is higher than the highest percentage in the latter; the same may be said for potash and nitrogen, but the muds contain more calcium carbonate.C. H. B. E. W. P. E. W P.184 ABSTRACTS OF CHEMICAL PAPERS.Chemistry of Vegetable Physiology and Agriculture.Studies on Pure Yeast. By C. AMTHOR (Zeit. physiol. Cl~em.,12, 64- 71) .-The paper consists of comparative observations on thefermentative activity on wort of eight different kinds of yeast ob-tained from various German breweries. Observations were made onthe amount of alcohol, extractives, specific gravity, glycei.ol, nitrogen,and reducing substances (reckoned as maltose). The colour intensitywas also observed by Stammer's colorimeter.The wort contained 10.8 of maltose ; after fermentation, the sumtotal of sugar (that reckoned as alcohol + the maltose in the beer)was 11-34.In reality the increase was greater, as dextrin and malto-dexfrin are reckoned in the above as maltose. The increase is doubt-less due to the conversion of dextrin into maltose. W. D. H.Influence of the Age of Yeast on Alcoholic Fermentation.By P. REGNARD (Ccrrnpt. rend. SOC. Biol. [ 8 ] , 4,442-444).-The in-ff uence on alcoholic fermentation exercised by the protoplasmicmetamorphosis which occurs in the yeast cell when i t is maintainedunder circurnstances of complete starvation is represented graphi-cally by the method introduced by the author in 1882.The characteristic fermentation which yeast normally produces islost after three days' complete starvation at a temperature of 25" to30" J.P. LVEGETABLE PHYSIOLOQY AND AGRICULTURE. '1 85The Development of Free Nitrogen in Putrefaction andNitrification. By 0. KELLNER and T. YOSHII (Zeit. physiol. Chem.,12, 95-111).-1n the first experiments, beans, milk, and fish mealwere allowed to putrefy, 20 to 50 grams of each being mixed with10 C.C. of putrid urine and 33 C.O. of water, a small quantity ofgypsum being also added. The quantity of nitrogen present beforeand after putrefaction was practically the same; no formation ofnitrates took place. I n a second series of experiments with ( a ) aspa-ragine and ( b ) beans, earth was added, and also small quantities ofrnonocslcium phosphate, precipitated tricalcium phosphate, and mag-nesium sulphate, for the favourable development of organised fer-ments (Warington, Trans., 1834, 637) ; no nitrification occurred,however, even after five months, and nitrogen estimations gave thesame results as in the first experiments.There is thus no loss ofnitrogen during putrefaction. Dietzell in experiments similar tothose of Ehrenberg (Abstr., 1887, 746) in the presence of oxjgen,obtained different results. In the experiments made by the latterthe putrefaction lasted six weeks, and there was no free nitrogenformed, whilst in those of the former, in which the experiments lasted12 months, there was a loss of 15 per cent. of the nitrogen, that isto say, although putrefaction pure and simple does not cause thedisengagement of gaseous nitrogen, certain processes of a secondarynature may perbaps do so.It may be due to the oxidation ofammonia by atmospheric oxygen. This could, however, not takeplace if organic substances are present which have a, strongeraffinity for oxygen; or it may be due to similar oxidation broughtabout by the action of nitrifying organisms, or by the action offree nitric acid on nitrogenous organic compounds; or it may bedue to the reduction of nitrates and nitrites by organic substances,or, lastly, to a spontaneous decomposition of ammonium nitrate indilute solutions.I n a third series of experiments, in which the earth used con-tained the nitrifying ferment, it was found that a loss of 9 to 10per cent. of nitrogen acconipanied the nitrification process ; in whichout of the possible ways enumerated above this takes place no definitestatement can be made.Diluted sterilised solutions of ammoniumnitrate do not appear to decompose spontaneously, but most pro-bably the loss of nitrogen is due to a reaction between nitritesand organic nitrogenous compounds. When nitrification begins, thereaction of the urine, at first acid, becomes alkaline, and later neutral ;this then remains unaltered. It appears possible that it is in thedeeper layers of the mixture, or where the earth is specially richin humus, that a portion of the nitrates or nitrites is rednced.W. D. H.Formation of Nitrogen during Putrefaction. By A. EHREN-REKG (Zeit. physiol. Chem., 12, 145--147).-A few further experi-ments illustrating the formation of methane and carbonic anhydridein putrefaction are detailed (Abstr., 1887, 746).W. D. H.Dependence of Assimilation of Green Cells on their Respi-ration of Oxygen; the part of the Plant in which Oxyge186 ABSTRACTS OF CHEMICAL PAPERS,formed in Assimilation is produced. By N. PR~XGSHEIM ( B e y .Akad. Ber., 1887, 763-777 ; compare Abstr., 1886, 64'2).-The endcells of the leaves of Chara fraqilis were enclosed in a microscopic gas-chamber, through which a mixture of hydrogen and carbonic anhy-dride (containing 1 to 5 per cent. of the latter) was passed. Whenlight is excluded, the rotation gradually becomes less and less until atlast (in 2 to 10 hours) the plasma is quite still. The cells, if not kepttoo long in this state, otherwise retain their original appearance, thechlorophyll apparatus remaining normal.On admitting oxygen, therotation of the plasma again commences, unless the cells have been kepttoo long without oxygen after the protoplasm has ceased to rotate. Ifthe cells are kept without oxygen just so long that the plasma stillshows a slight movement, they will be found to have lost the powerof assimilating, and when exposed to light, will no longer g i v e offoxygen.When the cells of Chara are exposed to light in a stream ofhydrogen and carbonic anhydride, rotation of the plasma and evolutionof oxygen cease after some time; in most cases the evolution ofoxygen ceases before the rotation. The presence of the smallestamount of oxygen is sufficient (even after the rotation of the plasmahas ceased for some time) to bring about movement and assimilation.These results make it probable that in the decomposition of car-bonic anhydride in plants no oxygen is formed, but that a compound isproduced which decomposes a t the outermost surface of the cells withevolution of oxygen.The decomposition of carbonic anhydride and the evolution ofoxygen do not occur together, but are distinct processes both as totime and place.Green and other tissues and plants in dying give offoxygen in the dark ; the evolution of oxygen often continues for hoursafter the plant has died.Assimilation and Respiration of Plants. By U. KREUSLER (Bied.Centr., 1887, 669-68 l).--In this continuation of former experiments(Bied. Centr., 1881, 110) are given the details of experiments madewith shoots of the same kind of plant, Pldadelphus qraiidajlorus, a tdifferent stages of growth, the temperature of observation being 15"and 25".At a temperature of 25", a strong and marked decrease inassimilative power accompanies increasing age of the leaf; a t 15" amaximum of assimilative power is noticed in the youngest leaves,This power reaches its minimum at the period of blossom, and agaiiirises in the oldest leaves ; so that between the assimilative power inthe youngest and in the oldest leaves, there does not exist muchdifference. A table showing the amount of water absorbed at thedifferent temperatures is also given. I n the second portion of thispaper, amongst many statements concerning the absorption and exha-lation of carbonic anhydride at different temperatures, it is recordedthat the range of temperature in which exhalation occurs is from 0-50°, and that it is greatest a t the highest temperature, the maximumappearing to be a t 46.4".Assimilation seems to take place a t a lowertemperature than exhalation, and it is active at 50" ; but the curverepresenting the relation of assimilation to temperature daes notN. H. $1VEGETABLE PEIYSIOLOGY AND AGRICULTURE. 187agree with that representing exhalation at various temperatures. Inthe case of the bramble, the maximum intensity of exhalation occursat about 466", whilst that of assimilation is found at 25". Forfurther statements and arguments, reference must be made to theoriginal. E. W. P.Physiological Signification of Tannin in Vegetable Tissues.By 11.WES'I'ERMA~ER (Ber. Akad. Ber., 1887, 127--143).-The amountof tannin in living cells free from and containing chlorophyll increaseswith the amount of light to which the cells are exposed. Experimentsmade with Quercus pedunculata showed that tjhe tannin migrates fromthe leaves downwards through the bark and the pith. It is uncertainwhether starch and tannin migrate side by side without changing, orwhether the starch migrates in the form of tannin.In examiniug the leaves of Ruinez patentia and Rheum rhaponticunz,st substance was found which showed the starch reaction with iodineand the tannin reaction with ferric chloride and with potassiumdichromate. The colour produced in the starch reaction is a bright-blue, sometimes greenish, and sometimes deep sky-blue.The sub-stance was found in large amount in the autumn leaves of Rheumrliayonticum. N. H. M.The Hop and its Constituents. By HAYDUCK (Bied. Centr.,1887, 694-698) .-Hops have no influence on alcoholic fermentation,but they retard, even if they do not wholly prevent, lactic fermen-tation, and this applies also t o the butyric and other forms of likechange, excepting the acetous, which is unaffected. Lerner andBungener have shown that there exists in hops a white, crystallint:compound, which they termed " hop-bitter acid." This acid, OILoxidation, forms a soft resinous matter, slightly soluble in water;besides the acid, a hard resin seems to exist in large quantities, andthe authors have now discovered a third, soft resin.The methodwhereby it may be obtained is as follows :-The hops are first exhaustedwith ether, and after evaporation of the ether, the residue is treatedwith alcohol, which leaves a white wax undissolved ; solution of leadacetate is then added to the alcoholic solution, when a yellow preci-pitate is produced, consisting of the soft resin in combination withlead. In the filtrate from this precipitate, the two other resins arefound, the one soft and soluble in light, petroleum, the other hard,iusolcible in light petroleum, but soluble in alcohol and ether; theformer is identical with that which is an oxidation-product of hop-bitter acid. All three seem to be feeble acids, and have no definitesolixbility in water, but the solution of the soft resins are intenselyand disagreeably bitter ; whilst that of the hard resin is slightly andagreeably bitter.As regards the suppression of lactic fermentation,although the hard resin has no effect, this property belongs to the softresins. A resinous coating sometimes forms in the wort in brewing,and it has been generally ascribed to resin, but this view is now shownto be incorrect, as this coating contains only 4 6 per cent. of resinsoluble in ether, whilst nitrogenous matter was present to the extentof 13 per cent. of nitrogen. E. W. P188 ABSTRACTS OF CHEMICAL PAPERS.Compounds extracted from Anagyris Fcetida. By N. REALI(G'nzzetta, 17, 325--329).-The seeds of the Anagyris fcetida, on ex-traction with ether, yield a fatty oil, two resinous substances, andalso a citron-vellow compound not further examined but probably aglucoside.From an alcoholic extract, glucose, sacchsrose, and styellow substance are obtained, together with a compound having allthe characteristics of an alkaloyd, and called ArLagyrine.One of the above resinous substances which the author calls ann-gyric mid forms a lead salt, by means of which the acid can beisolated. It contains carbon, hydrogen and oxygen, but the analysesgiven are not very concordant. The oil is not desiccative, sp. gr. =0.924 a t 17" ; on treatment with sulphuric and nitric acid, it acquiresa blood-red colour. The oil yields a mixture of fatty acids on saponi-fication. Anagyrine occurs as an amorphous mass of bitter taste,soluble in water, alcohol, ether, and benzene ; it has an alkaline re-action and forms salts with acids. It gives all the reactions ofalkalo'idu, such as precipitates with solutions of phosphomolybdicacid, potassium bismutho-iodide, and potassium mercuro-iodide. Itis unaltered at ordinary temperature by sulphuric acid, but whenwarmed it evolves a musk-like odour.The platinochloride is anamorphous, yellow powder, the analysis of which pointed to a formula,CIIH3,N0, for anagyrine.The Freezing of Ciders. By G. LECHARTIER (Compt. rend., 105,723-726).-The cider was cooled at -18" to -20" until nearlycompletely frozen, and the liquid portioc was drawn off. The mother-liquor was denser and more highly coloured than the liquid obtainedby melting the ice, which in the end yielded almost pure water.Themother-liquors were kept in a cellar for some months, and at the endof that time had a very fine colour and flavour. Addition of sugar t othe must merely increases the proportion of alcohol, but concentra-tion by freezing concentrates all the soluble substances from theapples. Concentration should not be carried beyond a certain pointor a disagreeable flavour is developed, and for a similar reason onlyciders of good oyiginal quality are suitable for this treatment. Evenwhen the cider is kept a t -18' for 12 hours, the ferment is not killed,although fermentation is retarded.By F. MENGARINI(Gazzetta, l7,441450).-Blaserna and Carpene have previously madeexperiments on the effects produced on wine by the action of anelectric current ; these have shown that various oxidation product8are formed, and the wine is artificially matured.In this paper, somefurther experiments on this subject are described, in which a currento f 3.99 amp8res per hour was passed for various periods of timethrough a sample of Italian wine ; analyses were made of the winewithout a.nd with passage of the current and the results compared.The platinum electrodes were found to be corered with albuminoussubstances, blackened by oxidation ; there was also a considerabledeposit of these substances. The proportion of alcohol was diminishedpartly by the slight concomitant formation of acetic acid, partly alsoV. H.V.C. H. B.Effects of an Electric Current on WineWOETABLE PHYSIOLOGY AND AGRICULTURE. 189by evaporation, and partly also by its destruction by a more profoundoxidation. There wa.s also imparted to the wine a perfume similarto that acquired by maturing ; this increased by prolongation of thecurrent. The passage of the current also assists its future preserva-tion. The colouring matters are affected, but the author would notfor the present draw any conclusions from his experiments. If bypassage of an electric current the wine could be sterilised, so as toeffect the complete IBemoval of Bacterium aceti, this process would beof considerable technical importance. V. H. V.Manuring Barley. By v. LIEBENBERG (Bied. Centr., 1887, 649-651).-The experiments were conducted at 12 st.ations, and tbemanures employed were (1) Chili saltpetre, (2) Chili saltpetre andsoluble phosphate, and (3) Chili saltpetre, soluble phosphate and potas-sium sulphate.The spring of the year (1886) was dry, whilst Juneand July were wet. There were three failures ; of the remaining ninestations, the nitrogen showed itself active in producing corn and strawat seven stations, whilst an influence on the straw only was manifestedat two. In two cases, potash increased the corn and straw, whilst inone it acted on the straw only ; the phosphate in five cases affectedthe corn and straw, and in one the straw only. It seems then thatnitrogen is available for barley in all localities, whilst phosphates orpotash are less PO.Manuring Oats.By v. LIEBENBERG (Ried. Certtr., 1887, 651-653).-The experiments were conducted on the same principle and inthe same manner as those on barley manuring. Nitrogen, and nitro-gen combined with phosphate yielded an increase, but there is anuncertainty as to the gain produced by potash. Phosphates influenceoats more than barley, because the former is slower and later incoming to maturity.E. W. P.E. W. P.Comparative Experiments with Oats manured with BasicSlag on Moorlands. By BAESSLEH, (Bied. Cem!r., 1887, 653-655).-The soil on which the experiments were conducted contained 69per cent. organic matter, 2.7 N, 0.29 P205, and 13.66 per cent. ash.Kainite, basic slag, and superphosphates were used. Neither the supernor the slag produced any decided effects ; kainite increased theyield of straw, but a general increase was remarked when the phos-phates in either form were combined with kainite.The action of theslag was only 42 per cent. of that of the superphosphate, but thisdifierenca is compensated for by the lower price of the slag.E. W. P.Manuring Winter Wheat and Winter Rye. By V. LIEBEN-BERG (Bied. Centr., 1887, 656-658).-Tbe manures were the same asthose employed in the author's experiment8 on oats and barley. Nodecided nor especial advantage was remarked in the crop of wheatthus manured. As regards the rye, nitrogen alone produced noeffect, but when combined with phosphates or kainite there was avery decided increase. The author accounts for the absence of effec190 ABSTRACTS OF CHEMICAL PAPERS.from the uRe of nitrogen by the fact that the a n d had previouslyManuring of Vines.By J. MORITZ and P. SEUCKER (Bied. Cent?-.,1887, 604-609).-The experiments were instituted to determine ifartificial manures could not be used for vines instead of the expensivefarmyard manure. The manures were those usually employed,namely, ammonia superphofiphates and potash compounds, and peat.The analyses of the must as well as its total quantity show that fa8rm-yard manure can be replaced by other manures; mineral manuregseem to prerent the usual premature ripening, and consequentlyrotting, of some of the berries on the vines, whilst farmyard manureinduces an extra growth of weeds. These experiments have beencarried on for nine years, and are still being continued.Condition of Potassium in Soils, Plants, and Moulds.ByBERTHELOT and ANDRF: (C'ompt. rend., 105, 833-840 ; 91 1-914)-I kilo. of the dried earth contained 23.5 grams organic carbon,1.66 gram nitrogen at the beginning of the season and 1.73 gram.and the end, and 8-92 grams of potassium. The only methods availablefor the estimation of the total potassium are those in which the soilis completely decomposed by ammonium fluoride, calcium carbonate,or barium hydroxide.Water percolating through the soil removed only 0.0029 gram ofpotassium per kilo., but if the soil was treated with successive quan-tities of water the amount dissolved increased to 0.143 gram per kilo.Heating the soil to dull redness had little effect on the solubility ofthe potassium.Ethyl acetate and ammonia have practically no effect on the solubi-lity, but water containing 2 per cent.of sugar or acetamide dissolvesmore potassium compound than pure water. Water saturated withcarbonic anhrdride dissolved 0.198 gram per litre ; water containing2 per cent. of acetic acid dissolved 0.290 gram per litre ; water with2 per cent. of hydrochloric acid 0.404 gram; water with 2 per cent.nitric acid 0.296 gram. These results afford no definite evidenceeither as to the forms in which the potassium exists in the soil or asto the proportion assimilable by plants.Concentrated hydrochloric and nitric acids at a higher temperaturedissolve considerably more potassium, the exact quantity dependingon the temperature and time of action. The whole of t*he potassium,however, is never removed.Calcination of the soil increases theproportion of the potassium soluble in acids, probably in consequenceof some alteration of the silicates.It is not possible to draw any sharp line of demarcation betweenthe potassium which is soluble or insoluble, assimilable or non-assimilable.In order to obtain similar information respecting the potassiumpresent in living plants, Mercurialis annua was selected as an example.The dried plant contained per kilo. 19.35 grams of nitrogen and27.87 grams of potassium oxide, and left 125 grams of ash.When treated with 10 times its weight of water for 24 hours,received farmyard manure. E.w. P.E. W. PVEGETABLE PHYSIOLOGY AND AGRICULTURE. 19118-92 gra,ms of potasaium per kilo., or two-thirds of the total amount,was dissolved. Hydrochloric acid of 2 to 3 per cent. dissolved 84-58grams of potassium in 24 hours, or 5.66 grams more than water.The remaining 3.29 grams was present in some form insoluble indilute acids.A sample of vegetable mould which was examined in a similar waj7contained 32.4 per cent. of water and lost 45.9 per cent. when calcinedin presence of air. The dried mould contained per kilo. 95.8 grams oforganic cnrhon ; 14.5 grams combined carbonic anhydride ; 8.6 gramsof nitrogen; and 11.65 grams of potassinm. 2-96 grams or one-quarter of the potassium was soluble in water; 5.84 grams wassoluble in hydrochloric acid of 2 per cent., but even after incinerationthe quantity of potassium insoluble in acids was 2-14 grams per kilo.The proportion soluble in water was considerably less after incinera-tion, owing doubtless to the action of the silicates on the potassiumcarbonate.It is erident that the mould does not retain the whole of the potas-sium present in the .original plant, a considerable proportion beingremoved by rain during the process of decay. The proportion remain-ing is, however, still much more considerable than in the soil, and mouldis a truly complementary manure intermediate in its character betweenthe organic and inorganic manures.Best Time for Ploughing Yellow Lupines under. By BAESSLER(Bied. Ceiz.fr., 1887, 615-618) .-The periods into which the growthof the yellow lupine which was to be used as “green manure ” wasdivided, were (1) full bloom of main stem, (2) commencement ofpodding of the same, (3) full bloom of side shoots, (4) full ripenessof the pods of main stern. It was found that the plants should beploughed under in the fourth period, for then they mould give tothe morgen N 140.3 kilos., R20 53.96, and P205 25.7, when 253,440plants are allowed per morgen ; at tbis period, the nitrogen and phos-phoric acid are three times and the potash twice that found in theplant in the period of bloom.Analysis of Rubbish-heaps employed to Improve Soils. ByA. MAPER ( B i d . Centr., 1887, 577--578).-The rubbish-heaps arcfound at places of refuge which were frequented in times of floodingbefore Holland was protected by dykes; they consist largely ofanimaland vegetable remains. The analysis of one sample must heyesuffice: Organic matter, 6.0 per cent. ; total nitrogen, 0.14; easilysoluble nitrogen, 0.02 ; phosphoric acid, 0.78 ; potash, 0.34 ; calciumcarbonate, 1.1. The material is richer in plant food than thevarious “ muds ” used for amelioration of poor land ; i n the former,the lowest quantity of phosphoric acid is higher than the highestpercentage in the latter; the same may be said for potash andnitrogen, but the muds contain more calcium carbonate.C. H. B.E. W. P.E. W P

ISSN:0368-1769    

DOI:10.1039/CA8885400184

出版商:RSC    

年代:1888

数据来源: RSC

摘要:

192 ABSTRACTS OF CHEMICAL PAPERS. Analytical Chemistry. Support for Funnels while Drying. By V. MEURER (Zeit. anal. Chem., 26, 624).-Two horizontal, parallel bars of glass tube are support,ed by pieces of glass rod, which have their ends bent npwards till they nearly meet, and thrust into the ends of the tubes which are bent downwards at right angles. A small hook of glass rod prevents the bars from springing apart under the weight of thc funnels which rest between them. M. J. S. Moisture remaining in a Gas after drying by Phosphoric Anhydride. By E. W. MORLHY (Amer. J. Sci., 34, 199-204).- The method employed for determining the amount of aqneous vaponr left in a gas after drying with phosphoric anhydride, consists in drying the gas with that snbstance, and then passing it through a weighed apparatus in which the gas is first slightly moistened, then niuch expanded, and, lastly, again dried by phosphoric anhydride.The decrease in weight of the apparatus is then due to the moisture left by phosphoric anhydridein that volume by which the gas passing out of the apparatus exceeds the gas entering it. In this way, it was found that the moist’ure left unabsorbed may be roughly estimated at a fourth of a milligram in 10,000 litres of gas. (For the result with sulphuric acid see Abstr., 1886, 278.) Hygienic Air Analysis. By K. S O N D ~ (Zeit. anal. Chem., 26, 5 9 2 4 9 8 ) .-The apparatus is essentially that of Pettersson (Abstr., 1887, 999 ; also 179 and 180), but with the inlet tnbe so arranged as to draw the sample of air for analysis from a pipette in which it has been collected, thus avoiding the necessity of performing the analysis in the locality from which the air is taken.The carbonic anhydride only is determined, the gases being saturated with moisture before each measurement, Results agreeing closely among themselves and fairly with determinations by Pettenkofer’s method have been obtained with an apparatus containing only 18 C.C. of air. Estimation of Sulphurous Acid by Standard Iodine Solution. By J. VOLHARD (Annalen, 242,93--113).-The drawback to BunseIi’s voliimetric method, involving the use of standard iodine solution and dilute sulphurous acid, is the fact that the acid solution will notl be completely oxidised if it contains more than 0.04 per cent. of SO,. The incomplete oxidation of the sulphurous acid in stronger solutions is generally attributed to the action of the sulphuric acid on the hydr- iodic acid :-H,S04 + 2HI = 1, + H2S03 + H20.The author finds that the true explanation is, that sulphurous acid is decomposed by a strong solution of hydriodic acid, yielding sulphur and iodine ; the iodine at once oxidises sulphurous acid t o sulphuric acid and is itself converted into hydriodic acid ; this secondary a d o n may be avoided by adding the moderately dilute sulphnrous acid to the standard iodine solution. w. c. w. B. H. B. M. J. S.ANALYTICAL CHEMISTRY. 193 Rapid Method of Determining the Total Acidity in Flue Gases from Vitriol Chambers, adapted for the use of Workmen. By W. YOUNGER (J. Soc. Clzem. Ind., 6, 347--348).-The author re- commeiids the use of Hurter's apparatus, which is described in detail in Wanklyn's book on " Gas Analysis.'' The method being intended only for the use of foremen, to serve as a guide in the working of chambers, no pretensions are made to any great degree of accuracy.The most useful property of the apparatus is that it indicates how far the combustion is carried on, what fuel is used, and how much is wasted. Soda-lime Method for Determining Nitrogen. By W. 0. ATWATER and C. D. WOODS (Ampr. Chem. J., 9, 311--324).-The soda-lime is prepared by slaking 23 kilos. of lime in an iron kettle with a solution of 1 kilo. of sodium hydroxide, evaporating, and heating to fusion. It is ground whilst warm, and divided into two portions by sieves of 2 mm. and 2 mm.Tbis soda-lime is, on the whole, pre- ferable t o a more fusible one containing more soda, the complete de- composition of the substance being effected by the large surface presenied by the coarse soda-lime with which the front part of the tube is filled. The same results are obtained whether the lime con- tains much or little soda, or even none, the ammonia probably being produced by the action of saperheated ateam. Combustions with sugar are not to be recommended for testing the purity of soda-lime, as even when recrystallised from alcohol i t appears to contain a trace of nitrogen ; stearic acid or oxslic acid is to be preferred. For the filling of the absorption-bulb, it is convenient to have a little thistle funnel blown on the end of the exit tube.If the tubes are well and closely packed with granular soda-lime, so as t o leave no considerable open channel, and if a sufficiency of powdered soda-lime be well mixed with the substance, short tubes, 30 cm. long, may be used ; cochineal is used as indicator. When using the absolute method for the determination of nitrogen, a, small correction should be made for the residual air and for the vapour-tension of the potash solution, namely, when ah sp. gr. 1.36, 4 mm. at 9.5" and 6.5 mm. at 14.5". Although the results obtained by the two methods are almost the same, the soda-lime method is not quite so exact, but is much simpler, and sufficient for most purposes if the above precautions are observed. Determination of Nitrogen by Kjeldahl's Method. BY L. LENZ (Zeit.m a l . Chem., 26, 590--592).-To ascertain whether the addition of permanganate is invariably necessary, comparative deter- minations were made on 11 nitrogenous substances, containing from 1.4 to 14 per cent. of nitrogen. In every case, the use of permanga- nate gave the higher result, the difference varying from 0-28 to 16 per cent. of the whole. The permanganate cannot, therefore, in any case be safely dispensed with. By KRATSCHMER (Zeit. nnaZ. Chem., 26, 608--610).-A simple apparatus for Schlo- sing's method. A flask of 150 C.C. capacity is fitted with a caout- D. B. H. B. M. J. S. Apparatus for Nitric Acid Determination. VOL. LIT. 0194 ABSTRACTS OF CHEMICAL PAPERS. chouc stopper, through which pass the tube of a separator bulb with a good stopcock and a long (3 to 4 dcm.) delivery tube bent downwards at an acute angle and turned up at the end.The nitrate solution is boiled in the flask (the delivery tube dipping into the mercury trough) until every trace of air is expelled. The stop- cock is then closed, a boiling hot mixture of ferrous chloride and hydrochloric acid is poured into the bulb, and the lamp is removed. As soon as the mercury begins to rise in the delivery tube, the ferrous solution is allowed to flow in, the lamp is replaced, and the nitric oxide boiled out as usual. A little of the ferrous solution should re- main in the bulb to act as a seal. M. J. S. Determination of Phosphoric Acid. By A. ISBERT and A. STUTZER (Zeit. anal. Chem., 26, 583-587).-The method based on the determination of the ammonia in the phosphomolybdate pre- cipitate (Abstr., 1887, 526) is confirmed.A further simplification consists in washing the yellow precipitate with cold water instead of with ammonium nitrate solution. The compound of silicic acid with ammonia and molybdic acid is soluble in pure water although insoluble in ammonium nitrate. On the other hand, the phosphomolybdate re- quires 10,000 parts of cold water for it,s solution. The removal of silica by evaporation may therefore be omitted. The precipitate is allowed to subside completely at 70°, and filtered off after cooling. It is thrown with it8 filter into a flask, and distilled with soda into standard acid, which is then titrated back with baryta, using corallin as indicator. One part of nitrogen in the precipitate corresponds with 1.654 parts of phosphoric anhydride.Test analyses with known quantities of phosphate, with and without silicic acid, and com- parative assays of phosphatic manures by the above and the gravi- metric process, show that for commercial purposes the method is sufficiently accurate. M. J. S. New Methods of Estimating Arsenic in Pyrites. By J. CLARK (J. Soa. Chem. Iiad., 6, 352-355).-Preci23itation Process.- Three grams of the finely powdered pyrites is mixed in a platinum crucible with four times its weight of calcined magnesia and soda, and the mixture heated for about 10 minutes over a moderately low .Bunsen flame. The contentls of the crucible are then extracted with boiling water and filtered. The filtrate, which should be green in colour owing to the presence of iron, is acidified with hydrochloric acid, and the solution, which is now nearly colourless, is boiled for ft few minutes, when the arsenic sulphide will separate along with sulphur.To ensure complete precipitation of the arsenic, it is always advisable to saturate the solution with hydrogen sulphide. The precipitate is then thrown on to a filter, washed, dissolved with ammonia, and the solution evaporated to dryness on a water-bath. The residue is treated with nitric acid and the arsenic in the solu- tion either estimated as magnesium ammonium arsenate, or precipi- tated as silver arsenate, and the arsenic calculated from the silver as determined volumetricall~ by Volhard’s process, or gravimet~ically by cupellation, as recommended by Richter.ANALYTICAL CHEMISTRY.195 DistiZEictioa Process.-dbout 1.7 gram of the finely pulverised pyrites is introduced into a platinum criicible with six times the weight of the above mixture, and heated for an hour over a low Bunsen flame. The contents of the crucible are transferred to a flask, moistened with water, and dissolved in strong hydrochloric acid. The flask, which is fitted with a funnel tube, having the end drawn to a point and dipping under the liquid, is then connected with a small glass condenser, to the end of which a straight calcium chloride tube is attached, and by means of the funnel tube a considerable excess of cuprous chloride dissolved in strong hydrochloric acid is introduced. The contents are then slowly distilled into water for an hour, when a fresh quantity of hydrochloric acid is introduced, and the distillation continued for + hour.The whole of the arsenic will now be found in the receiver, but it is always advisable to add a little more hydrochloric acid, change the receiver, and test the distillate. The arsenic is then precipitated as sulphide, or it is titrated with iodine in the usual way. D. B. Estimation of Silicon in Iron and Steel. By J. J. MORGAN (Chem. News, 56, 221).-The author criticises Turner’s statements (Abstr., 1887, 1140), and states that silica may be obtained free from iron and phosphorus in the following manner :-The solution obtained by dissolving iron in aqua regia is evaporated to a thick syrupy con- sistence, treated with hydrochloric acid, and the precipitated silica well washed with dilute hydrochloric acid and water, when it is found to be free from both iron and phosphorus.Estimation of Silicon in Iron and Steel. By T. TURNER (Chem. News, 56, 244--245).-A reply to Morgan (preceding Abstract). Whilst the process described above will give fairly accu- rate results with iron containing under 1 per cent. of phosphorus and about 1 per cent. of silicon, this is not the case with commoner irons oontaining 2 per cent. of phosphorus and 3 to 4 per cent. of silicon. Indirect Determination of Alkalis in Presence of Lithium. By I(. KRAUT (Zeii. and. Chem., 26, 604405).--The metals are weighed as nit,rates, ;md the nitric anhydride then expelled by fusion with silica. Chlorides are converted into nitrates by treatment with silver nitrate.Phosphates are dissolved in a little nitric acid, about an equivalent quantity of silver nitrate is added, and then freshly pre- cipitated silver oxide to neutrality. The excess of silver in either case is removed from the filtrate by hydrocyanic acid. This method is not applicable to sulphates, since barium sulphate cannot be freed M. J. s. Determination of Ammonia in Commercial Products. By 3. M. MILEE (J. Soc. Chem. Ind., 6, 423).-Some time ago a German committee recommended the liberation of the ammonia from phos- phates, manures, and other commercial products, by boiling with magnesia instead of alkaline hydroxides, and absorption in a measured D. A. L. The calculation is made in the usual manner. from lithium salts by washing.196 ABSTRACTS OF CHEMICAL PAPERS.excess of standard sulphuric acid. One great advantage of this modification is that the contents of the distilling flask boil quite quietly, and can be brought nearly to dryness without spirting if the gas flame is properly regulated. The author has used this method for some time with very satisfactory results. I t is necessary, however, to observe the following precautions :-(1) The steam containing the ammonia should be thoroughly condensed as it passes over. (2) The end of the condenser tube should not dip beneath the surface of the sulphuric acid in the bulb flask. (3) I n order to ensure complete absorption of the ammonia, a small U-tube containing a little of the standard acid should be attached to the exit tube of the flask. Assay of Silver containing Small Quantities of Bismuth.Estimation of Mercury in Urine. By L. BRASSE (Corn@. rend. Xoc. Bid. [8], 4, 297-300) .-Simple electrolysis is insufficient, inasmuch as certain organic matters are deposited along with the mercury on the electrode. To obviate this error, the author treats 100 C.C. of urine with 10 C.C. of hydrochloric acid, places in the mix- ture a small coil of thin sheet brass 1 cm. broad by about 50 cm. long, and allows the interaction to go on for a day. The coil is then removed, washed with alcohol and ether, dried, transferred to a porcelain crucible and heated. The mercury vapour is condensed on a concave cover of gold kept cool by distilled water. The difference between the weight of the dried cover before and after heating gives Estimation of Iron in Chars.By R. DAVTDSON (J. SOC. Chem. Id., 6, 421).-Having tested the accuracy of the stannous chloride process for the estimation of iron in the case of substances such as animal charcoal, containing only from 0.1 to 1.0 per cent. of ferric oxide, the author confidently recommends it in preference to either the " permanganate " or " dichromate " process. Determination of Ferrous Oxide in Insoluble Silicates. By A. H. CHESTER and F. I. CAIRNS (Amer. J. Sci., 34, 113--116).-1n their examination of t'he crocidolite from Rhode Island, the authors determined the ferrous oxide by means of ammonium fluoride. Half a gram of the pulverised mineral is placed in a large platinum crucible over a water-bath, and a slow stream of carbonic anhydride is carried into it.When the air is expelled, a few drops of concentrated sul- phnric acid is added, then Rome ammonium fluoride. Similar addi- tions are made from time to time until the mineral is completely decomposed. The contents of the crucible are then emptied into a beaker containing cold water. The solution is diluted, and the iron D. R. By J. SCULLY (see p. 108). the amount of mercury. J. P. L. D. B. determined by mGaw of potsesium permanganate in the usual manner. B. H. B. Estimation of Titanic Oxide. By L. LEVY (Cornpt. rend., 105, 754-756) .-The author has investigated the conditions necessary to ensure accuracy when using the ordinary method of fusing withANALYTICAL CHEMISTRY. 197 potassium hydrogen snlphate, extracting with water, and precipitating the titanic oxide by prolonged boiling.The solution should contain 0.5 per cent. of free sulphuric acid : if less, the precipitate is impure ; if more, precipitation is incomplete. The presence of zinc in the solution is without influence on the result, provided the proportion of free acid is 0.5 per cent., and the same is true of copper, magnesium, and aluminium, but in presence of ferric sulphate the result is always too high. The best method of procedure is as follows :-The fused mass is mixed with suficient sulphuric acid to convert the whole of the potassium into the hydrogen sulphate, solution being thus greatly accelerated, and the liquid is then carefully neutralised with potassium hydroxide, free sulphuric acid added t o the extent of 0.5 per cent., and the solution boiled for six hours.C. H. B. Determination of Antimony. By F. MUCK (Zeit. anaZ. Chem., 26, 600-602) .-The precipitate of trisulphide is dried by suction until it can be detached from the filter. The filter is washed with warm ammonium sulphide in which much free sulphur has been dis- solved, this polysulphide having a far greater solvent action than the monosulphide. The solution is evaporated in a porcelain crucible. A convenient way of doing this is to support the crucible on a glass triangle in a deep glass basin containing a little sulphuric acid, and covered closely with a glass plate. On gently heating the basin on a bed of asbestos, tthe liquid evaporates rapidly without spitting. The detached precipitate is then added and the whole dried.The free sulphur is removed by treatment with a mixture of carbon bisulphide and chloroform, and the antimony sulphide is converted into tetroxide for weighing. M. J. S. Delicate Test for Bismuth. By F. B. Srrom (J. Soc. Chem. I d , 6, 416).-This test depends on the fact that a strong solution of potassium iodide produces a bright yellow colour when added to it very dilute solntion of bismuth sulphate containing only a small quantity of free sulpuric acid. 1 part of bismuth oxide in 1,000,000 parbs will show a distinct coloration. Very small quantities of bis- muth may also be estimated colorimetrically by meaus of this test. D. B. Detection of Nitrates in Well Water. By 0. BINDER ( Z e d . anal. Chern., 26, 605--606).-The method depending on the reduction to nitrit,e by zinc, and testing with potassium iodide and starch, fails if too mnch zinc is used.A trace of zinc powder shaken with the liquid answers better than compact zinc. M. J. S. Water Analysis. By 0. BINDER (Zeit. aizal. Chem., 26, 607).- Liquids, such as natural waters, evaporated over a free gas flame, become contaminated with sulphuric acid from the products of com- bustion. M. J. S. Elementary Analysis of Highly Volatile Organic Liquids. By G. KASSNER (Zeit. anal Chem., 26, 588-590) .-The combustion 0 2198 ABSTRACTS OF CHEMICAL PAPERS. tube is prolonged at the posterior end beyond the furnace, and is bent upwards at an angle of about 45". A plug of asbestos is placed at the bend. The bulb containing the liquid is introduced at this end, and rests against the asbestos plug with its capillary tube pointing upwards.The bulb having been cooled before breaking the point of the capillary tube, can be introduced without the escape of any of the liquid, and the gradual expulsion of the contents can be watched and regulated, since the va,porised liquid condenses in the capillary tube, and is driven out in the form of minute drops. These are immediately evaporated and swept forward by the current of oxygen passed through the tube. The more volatile the liquid, the longer and narrower should be the capillary tube. The portion of the combustion tube which is to be heated is filled with platinised asbestos (see Kopfer, ibid., 17,l). For substances which burn with difficulty, how- ever, cupric oxide cannot be dispensed with. For arresting halogens, a plug is employed prepared by shaking chopped asbestos with finely divided, reduced silver.A stream of hydrogen (free from arsenic or antimony) passed through the hot tube regenerates the metallic silver after it has absorbed a halogen. M. J. S. The Stalagmometer. By J. TRAUBE (Ber., 20, %24-2835).- Applications of the stalagmometer (this vol., p. 91) to the estimation of alcohol in wine, beer, and liqueurs, and of acetic acid and alcohol in vinegar. Tables are given for use at temperatures between 10" and 30" for alcohol, and 11" and 29" €or acetic acid, €or percentages up to 10 per cent. by weight of the pure substance in each case. w. P. w. Recognition of Pyrogallol. By G. KLIEBAHN (Zeit;. anal. Chem., 26, 641) .-Pyrogallol when fused with ammonium oxalate yields am- monium rufigallate, which dissolves in water with red colour, and gives the following characteristic reactions :-Potassium ferricysbnide and potassium dichromate, a dark-brown precipitate insoluble in alcohol. B'erric chloride, no black coloration.A few drops of acetic acid, then potassium cyanide and mercurous nitrate, a black precipitate. Sodium nitroprusside a.nd platinic chloride, no precipitate or change of colour. Potash, a change to brown, but not to black. M. J. S. Estimation of Grape-sugar in Urine by Robert's Method. By V. BUDDE (P'iiger's Archiv, 40, 137-172) .-The fermentation method of determining the amount of sugar in diabetic urine consists in multiplying the difference in specific gravity before and after re- moval of the sugar by fermentation, by a, constant factor found by control titration experiments in which the percentage so found was divided by the difference in the specific gravities.Worm-Muller has stated (ibid., 37, 479-510) that this factor is constant, namely, 230. This paper is devoted to showing mathematically that from its very nature this factor is a variable one, increasing as the percentage o€ sugar diminishes. W. D. H.ANALYTICAL CHEJIISTRY. 199 Examination of Wort and Starch. By E. W. T. JOX’ES (AnnZyst, 12, 16:J- 168) .-The methods eixiployed are essentially those described by O’Sullivan (this Journal, 1876, ii, 130). An analysis is given of a wort which gave [a]j3.89 = 116.5, and R = 50.8 (Trans., 1879, 606). The same wort analysed in the Inland Revenue Laboratory gave the values [a] = 120, and K = 57.2, on which numbers a charge of the addition of 1.6 per cent.of glucose was based. The suggestion is made that the higher value of K may have been obtained by the use of Fchling’s solution volumetrically in the presence of dextrin. On keeping this wort for four months (after adding salicylic acid). the rotatory power diminished, whilst the cupric reducing power increased. Some of the same malt, mashed in the laboratory for three hours at 57-60’, gave [a] = 113.6, K = 51.85, from which it would appear that with some malts the limits recognised by the Inland Revenue chemists ( [ a ] not less than 120, and K not over 51) may be exceeded. The method of analysing starch differs from that of O’Sullivan (Trans., 1884, 9) only in the omission of the washings with ether, alcohol, and warm water before gelatinising, and in controlling the results of the optical method by a subsequent hydrolysis with acid, and a determination by Fehling’s solution.Estimation of Small Quantities of Lactic Acid. By W. WINDISCH (Chem. Centr., 1887, 826, from Wocherzschr. f. Braueri, 13, 214).-In order to estimate small quantities of lactic acid, the sub- stance to be examined is heated with chromic acid, whereby the lactic acid is decomposed into formic acid and aldehyde. The mixed vapours are passed into Nessler solution, in which, in presence of an aldehyde, lead salts give a yellowish-red precipitate, or with smaller quantities, a yellowish opalescence. In order to examine roots by this process, they are first extracted with ether, which dissolves out all acid substances, V.H. V. 31. J. S. New Method of Examining Butter. By T. T. P. B. WARREN (Clzen~. News, 56, 222, 231, 243--244).-Five grams of butter is placed in a tared tube, plugged with asbestos, and is extracted with carbon bisulphide. The fats are weighed, dissolved in carbon bisul- phide, and well mixed with a solution of equal volumes of yellow sulphur chloride and carbon bisulphide ; the latter is evaporated, and the thickened mass redissolved in carbon bisulphide, any insoluble residue indicating the presence of vegetable oils. The filter tube is dried and weighed ; then by successive weighings after washing, first with water, then with ammonia, the dry matter, soluble substances, casein, &c., are determined.The sulphur chloride treatment applied to other fatty mixtures, such as lard, oil, or oleomargarin, will detect the admixture of any vegetable oil, rosin, rosin oil, or petroleum. After a few hours’ contact with sulphur chloride, butter becomes brownish, commercial olein thickens and turns black, and animal ole’in assumes a very dark colour, but all dissolve in carbon b i d - phide, whereas vegetable oiIs do not. Inasmuch as animal oils them- selves dissolve vegetable oils, a small qmntity of the latter might200 ABSTRACTS OF CHEMICAL PAPERS. escape detection in presence of a large quantity of the former; to avoid thilj it is suggested to add to the butter or other fatty mixture sufficient tested cotton-seed oil to supersaturate the animal fats ; then by treatment with sulphur chloride and subsequent washing with carbon bisulphide, the animal fats are removed, and the vegetable oils remain insoluble.Any excess residue over that due to the cotton- seed oil added is derived from vegetable oil present in the butter; this is, however, only approximately quantitative. Water must be absent when using sulphur chloride. Other precautions are noted, and some remarks are advanced on the character of tho reaction of sulphur chloride on fats, and of the products formed in the reaction. Attention is drawn t o the high percentage of case'in in some samples of country butter, probably indicating the use of this substance as an adulterant. D. A. L. The Reichert-Meissl Process for the Estimation of Butter Fat.By R. WOLLNY (Bied. Cent?-., 1887, 699-703).-Errors fre- quently arise in the results obtained by working this process, the results being generally too high. This the author ascribes to the pre- sence of carbonates in the potash used for saponification. A loss may also occur from the fact that distillation with sulphuric acid in pre- sence of alcohol will produce ethereal salts of butyric and other acids, consequently the results may be too low. If tohe following precautions are taken, the results will be accurate. Instead of potassium hydroxide, a 50 per cent. sodium hydroxide solution is to be used, and allowed to settle before putting aside. Admission of carbonic anhydride t o the saponifying solution must be avoided, and for this purpose the saponification must be conducted in a vessel to which a reflux con- denser is attached, and the distillation of the alcohol should be effected without opening the apparatus.A closed T-tube is inserted between the flask and condenser, whereby, after distillation, water and acid can he added. As regards the process itself, 5 grams of t,he molten and filtered fat is accurately weighed into a 300 C.C. flask (length of neck 7 to 8 cm.), 2 C.C. of 50 per cent. sodium hydroxide solution, which has been preserved from all contact with carbonic anhydride, and 10 C.C. alcohol (96 vol. per cent.) are introduced into the flask, and after connection with the reflux condenser the flask is heated in the water-bath for hour; the alcchol is distilled off, and the heat continued for at least 6 hour, 100 C.C.distilled water is then added, and the mixture further heated for & hour, until the soap is dissolved. The clear solution is now to be decomposed whilst hot by 40 C.C. of sulphuric acid (30-35 C.C. = 2 C.C. of the soda solution), and a small piece of pumice should also be introduced. Distillation must be continued until 110 C.C. of the liquid has been collected, the distillate well mixed, and of it 100 C.C. filtered 08 and titrated with decinormstl baryta, phenolphthalein being used as indicator. The figure thus obtained is to be multiplied by 1.1, and from the product are to be deducted such figures as are obtained from a preliminary blank experiment. The deduction to be made should not exceed 0.33. E. W. P.ANALYTICAL CHEMISTRY. 201 Examination of Cod-liver Oil and Vegetable Oils.By E. SALKOWSKI (Zeit. ana2. Chew., 26, 557--582).-The determination of the temperature of solidification is of little assistance, since un- doubtedly genuine specimens show widely different solidifying points. Moreover, cod-liver oil solidifies with extreme slowness, even at tem- peratures far below its freezing point, and an admixture of 20 per cent. of rape-seed, linseed, or cotton-seed oil, with an oil of low freezing point is not revealed a t a temperature (0" C.) at which other genuine oils solidify. The presence of palm oil, palm kernel oil, or cocoa-nut oil may, however, be suspected if solidification occurs in 15 to 30 minutes a t 0". Treated by Reichert's process, cod-liver oil gives a very small quan- tity of volatile acid.Linseed, rape-seed, cotton-seed, and palm oils give a slightly higher yield, but not sufficiently diiferent to enable this method to detect an admixture. When cod-liver oil is saponified and the dilute solution of the soap shaken with ether, cholesterin is extracted, together wit@h a yellow substance, which seems to belong to the lipochrome series (Kuhne, Untersuch. physiol. Inst. Heidelberg, 1882). This substance gives an indigo-blue colour with strong sulphuric acid, whilst cholesterin and also the cod-liver oil itself give violet. The fatty acids from the soap solution freed from cholesterin, when dissolved in chloroform and mixed with sulphuric acid, give a dark brown-red colour, with dirty- green fluorescence. If after pouring off the chloroform some of the acid is added to glacial acetic acid, the mixture slowly acquires a fine red-violet colour, with dirty-green fluorescence.The only vegetable oils which in choloform solution are coloured blue by sulphuric acid are palm oil and cotton-seed oil. All the vegetable oils (except palm oil), when treated as above for the extraction of cholesterin, yielded a substance which was identified with the phytosterin of Hesse. This may be dist'inguished from cholesterin by its appearance under the microscope. A hot alcoholic solution of choles terin solidifies 011 cooling to a mass of thin, rhonibic plates, frequently showing re- entering angles; the substance obtained from the vegetable oils forms stellate or fascicnlate groups of thick needles, or on slow cooling gives elongated six-sided plates.The products from all the vegetable oils melted at 132-134" (Hesse's phytosterin at 132-135"). Choles- terin from genuine cod-liver oil melts a t 146" ; the product from an oil adulterated with 20 per cent. of rape, linseed, or cotton-seed oil melted at 139-140", and showed the needles of phytosterin, toge- ther with the plates of cholesterin. Most of the specimens of cod-liver oil examined contained very litlle free fatty acid (0.24 to 0.69 per cent. calculated as oleic acid ; one specimen, however, showed 6.5 per cent.). Since many vegetable oils give numbers lying within these limits, this character is of no service ior their detection. M. J. S. Titration of Urea with Mercuric Nitrate. By E. PFL~GER (Pfliiger's Archiv, 40, 533-586) .-After some critical remarks on von Rantenberg's and Pfeiff er's modifications of Liebig's method of estimating urea, a series of 28 experiments is detailed, in which202 ABSTRACTS OF CHEMICAL PAPERS.the amount of nitrogen in urine was estimated first by Kjeldahl’s method, and secondly by Rautenberg’s mercurial solution. In some cases, the results by the latter were higher, in othem lower than by Kjeldahl’s method, and taking Kjeldahl’s method as one which gives accurate results, it is calculated that the average error of Rautenberg’s method is 0.7 per cent. On the average, out, of 100 pavts of the nitrogen in urine, 13 are combined i n substances other than urea. Rautenberg’s method does not give the amount of urea, but the total nitrogen.W. D. H. Fractional Reduction of Ortho- and Para-nitrotoluene and Quantitative Analysis of Ortho- and Para-toluidine. By T. MINIATI, H. BOOTH, and J. B. COHEN (J. SOC. Chem. I d , 6, 418-420). -From a series of experiments on the reduction of ortho- and para- nitrotoluene, it seem8 that both nitro-compounds are acted on conour- ren tly . Before commencing their analytical work, tJhe authors thought it desirable to determine whether the reduction could be so regulated that approximately the same quantities of nitrotoluene could be reduced with w given quantity of the reducing agent ; it was found that with care this could be readily accomplished. The separation and isolation of the nitrotoluene and toluidine is effected in the following manner :-After reduction, the acid solution obtained is distilled with steam, and the uuattacked nitrotoluene driven over, the toluidine remaining behind.The toluidine solution is freed from tin by treatment with hydrogen sulphide and filtered. The filtrate is made alkaline and distilled with steam, when the toluidine distils over. Both distillates are extracted with ether, the ether is distilled off and the residues dried and weighed. The first gives the weight of nitrotoluene, t,he second that of the toluidine. Having the respective weights, an analysis of the one or the other and determination of the quantity of‘ ortho- and para-compound present therein, suEces to find exactly how the reduction has gone. Having made unsuccessful attempts to analyse the resulting nitro-compound, the authors tried various methods for the quantitative estimation of ortho- and para- toluidine.The only process they found practicable was to add excess of oxalic acid solution, bring the precipitate on to a filter-paper, wash three or four times with ether, and weigh on a watch-glass. Any residue remaining in the precipitating vessel and in the filter- paper was dissolved in water and titrated with decinormal potash solution. With paratoluidine, it was found that precipitation was not complete unless the mixture was allowed to remain 1% hours. With pure orthotoluitl ine, there is no immediate precipitation, biit in 12 hours from 4 to 5 per cent. of the ortho-compound crystallises out ; hence in performing the analysis the error due to the precipitation of the ortho-compound must be allowed for if the golution remains 12 hours, or the error due to incomplete precipitation of the para- compound must be allowed for if the precipitate is filtered imme- diately.The better plan would therefore be to obtain an approximn- tion of the amount of para-compound present in one determination,ANALYTICAL CHEMISTRY. 203 and then run in just sufficient oxalic acid solution t o precipitate this quantity, and wait for 12 hours. D. B. Estimation of Small Quantities of Paratoluidine in Ortho- toluidine. By C. HAEUSSERMANN (Chem. Ind., 10, 55-56).-0f the methods recommended for the estimation of para- and ortho-toluidine the process based on the titration of the para-compound with oxalic acid in an ethereal solution has been mostly adopted.It is not, however, wholly free from error, owing to the fact that t,he amount of ether to be used is frequently insufficient to completely dissolve the '' ortho-oxalate " produced by the reaction. The author suggests the following method :-A solution containing 88 grams of crystallised oxalic acid in 750 C.C. of water and 43 C.C. of hydrochloric acid of 22' B. is heated in a porcelain basin to 70-75', and treated with 10 grams of the toluidine under examination. When the preci- pitate which separates has been entirely redissolved, the mixture is allowed to cool gradually to 30-35" nntil the oxalate shows signs of cryshallisation on the surface of the solution. It is then filtered through cotton and the residue washed with a few drops of water. The precipitate forms small, colourless scales having a dull appear- ance.The filtrate on standing deposits a further portion of crystals whi& are mJJecked on a qmrahe filier md wa,sned Tbj,, oppmiim is repeated until crystals are obtained having a lustrous appearance. These consist of the pure '' ortho-oxalate," and are readily distin- guished from the crystals of the para-compound. The crystalline fractions are then treated with a solution of sodium carbonate and subjected separately to distillation. The solidifying point of the distilled bases is determined by cooling a fraction of each distillate with ice. If the oil solidifies by merely agitating it, the crystals are collected on a tared filter, and after drying over sodium hydroxide weighed as paratoluidine. If, however, the addition of a few crystah of pure paratoluidine is required to induce solidification, only one-half of the mass is calciilated as paratoluidine. If, on the other hand, it is impossible to solidify the base obtained from the distillation of the first crystalline fraction, orthotoluidine only is present in the sample under examination.With good toluidines, it generally suffices to collect and distil two fractions, in which case the base from the second cryst,zllisation mostly constitutes a perfectly liquid oil. This method being inapplicable to mixtures containing more than 10 per cent. of paratoluidine, it is suggested to dilute such mixtures by the addition of pure orthotoluidine. D. B. Volumetric Determination of Alkaloids by Mayer's Reagent. By F.S. HERETH (Zeit. a n d Chem., 26, 647)-To avoid the errors introduced by the use of filters and the irregular addition of the reagent (potassio-mercuric iodide), several equal portions of the solu- tion to be titrnted should be mixed a t once with quantities of the reagent differing from one another by 0.1 c.c., and ranging from somewhat below the amount indicated by a rough preliminary test to an equal distance above. After settling for at least eight hours in204 ABSTRACTS OF CHEMICAL PAPERS. closed test-tube, part of the clear upper liquor can be poured off a i d tested by a drop of the reagent. The extract is prepared for titration by acidifying and gently warming t o drive off alcohol. If any pre- cipitate separates it is filtered off and washed with dilute acid.The liquid should finally contain about 1 per cent. of free sulphuric acid. M. J. S. Tanret's Reaction for Albumin, Peptone, and Alkaloi'ds in Urine. By L. BRASSE (Compt. rend. Hoe. BioZ. [S], 4, 369-370).- Albumin, peptone, and alkaloids are precipitated from urine in the cold by Tanret's reagent, potassium mercury iodide. On heating, the peptone and a1 kalojidd precipitate dissolves, leaving the albumin insoluble. The alkalo'idal precipitate can be easily separated from the peptone precipitate by reason of its solubility in ether. No insoluble combinations are formed with any of the ordinary constituents of urine, such as creatine, creatinine, xanthine, or hypo - xanthine, but bile salts give rise to a precipitate insoluble, like albumin, in both cold and hot solutions. This precipitate, however, can be cliff erent'inted from the ordinary albumin precipitate inasmuch as it is soluble in ether.J. P. L. Haematoscopic Study of Blood. By A. H~NOCQUE (Conzpt. rend. ,S"oc. Bid. [8], 4, 383--284).-The chief advantage in the use of the haemahscope (Abstr., 1887, 312), for the spectroscopic examin- ation of blood is the possibility of examining the blood undiluted. J. P. L.192 ABSTRACTS OF CHEMICAL PAPERS.Analytical Chemistry.Support for Funnels while Drying. By V. MEURER (Zeit.anal. Chem., 26, 624).-Two horizontal, parallel bars of glass tubeare support,ed by pieces of glass rod, which have their ends bentnpwards till they nearly meet, and thrust into the ends of the tubeswhich are bent downwards at right angles.A small hook of glassrod prevents the bars from springing apart under the weight of thcfunnels which rest between them. M. J. S.Moisture remaining in a Gas after drying by PhosphoricAnhydride. By E. W. MORLHY (Amer. J. Sci., 34, 199-204).-The method employed for determining the amount of aqneous vaponrleft in a gas after drying with phosphoric anhydride, consists in dryingthe gas with that snbstance, and then passing it through a weighedapparatus in which the gas is first slightly moistened, then niuchexpanded, and, lastly, again dried by phosphoric anhydride. Thedecrease in weight of the apparatus is then due to the moisture leftby phosphoric anhydridein that volume by which the gas passing outof the apparatus exceeds the gas entering it.In this way, it wasfound that the moist’ure left unabsorbed may be roughly estimated ata fourth of a milligram in 10,000 litres of gas. (For the result withsulphuric acid see Abstr., 1886, 278.)Hygienic Air Analysis. By K. S O N D ~ (Zeit. anal. Chem., 26,5 9 2 4 9 8 ) .-The apparatus is essentially that of Pettersson (Abstr.,1887, 999 ; also 179 and 180), but with the inlet tnbe so arranged as todraw the sample of air for analysis from a pipette in which it hasbeen collected, thus avoiding the necessity of performing the analysisin the locality from which the air is taken. The carbonic anhydrideonly is determined, the gases being saturated with moisture beforeeach measurement, Results agreeing closely among themselves andfairly with determinations by Pettenkofer’s method have been obtainedwith an apparatus containing only 18 C.C.of air.Estimation of Sulphurous Acid by Standard Iodine Solution.By J. VOLHARD (Annalen, 242,93--113).-The drawback to BunseIi’svoliimetric method, involving the use of standard iodine solution anddilute sulphurous acid, is the fact that the acid solution will notl becompletely oxidised if it contains more than 0.04 per cent. of SO,.The incomplete oxidation of the sulphurous acid in stronger solutions isgenerally attributed to the action of the sulphuric acid on the hydr-iodic acid :-H,S04 + 2HI = 1, + H2S03 + H20. The author findsthat the true explanation is, that sulphurous acid is decomposed bya strong solution of hydriodic acid, yielding sulphur and iodine ; theiodine at once oxidises sulphurous acid t o sulphuric acid and is itselfconverted into hydriodic acid ; this secondary a d o n may be avoidedby adding the moderately dilute sulphnrous acid to the standardiodine solution.w. c. w.B. H. B.M. J. SANALYTICAL CHEMISTRY. 193Rapid Method of Determining the Total Acidity in FlueGases from Vitriol Chambers, adapted for the use of Workmen.By W. YOUNGER (J. Soc. Clzem. Ind., 6, 347--348).-The author re-commeiids the use of Hurter's apparatus, which is described in detailin Wanklyn's book on " Gas Analysis.'' The method being intendedonly for the use of foremen, to serve as a guide in the working ofchambers, no pretensions are made to any great degree of accuracy.The most useful property of the apparatus is that it indicates how farthe combustion is carried on, what fuel is used, and how much is wasted.Soda-lime Method for Determining Nitrogen.By W. 0.ATWATER and C. D. WOODS (Ampr. Chem. J., 9, 311--324).-Thesoda-lime is prepared by slaking 23 kilos. of lime in an iron kettlewith a solution of 1 kilo. of sodium hydroxide, evaporating, and heatingto fusion. It is ground whilst warm, and divided into two portionsby sieves of 2 mm. and 2 mm. Tbis soda-lime is, on the whole, pre-ferable t o a more fusible one containing more soda, the complete de-composition of the substance being effected by the large surfacepresenied by the coarse soda-lime with which the front part of thetube is filled. The same results are obtained whether the lime con-tains much or little soda, or even none, the ammonia probably beingproduced by the action of saperheated ateam.Combustions withsugar are not to be recommended for testing the purity of soda-lime,as even when recrystallised from alcohol i t appears to contain a trace ofnitrogen ; stearic acid or oxslic acid is to be preferred. For the fillingof the absorption-bulb, it is convenient to have a little thistle funnelblown on the end of the exit tube. If the tubes are well and closelypacked with granular soda-lime, so as t o leave no considerable openchannel, and if a sufficiency of powdered soda-lime be well mixed withthe substance, short tubes, 30 cm. long, may be used ; cochineal is usedas indicator.When using the absolute method for the determination of nitrogen,a, small correction should be made for the residual air and for thevapour-tension of the potash solution, namely, when ah sp.gr. 1.36,4 mm. at 9.5" and 6.5 mm. at 14.5".Although the results obtained by the two methods are almost thesame, the soda-lime method is not quite so exact, but is much simpler,and sufficient for most purposes if the above precautions are observed.Determination of Nitrogen by Kjeldahl's Method. BY L.LENZ (Zeit. m a l . Chem., 26, 590--592).-To ascertain whether theaddition of permanganate is invariably necessary, comparative deter-minations were made on 11 nitrogenous substances, containing from1.4 to 14 per cent. of nitrogen. In every case, the use of permanga-nate gave the higher result, the difference varying from 0-28 to 16 percent.of the whole. The permanganate cannot, therefore, in any casebe safely dispensed with.By KRATSCHMER(Zeit. nnaZ. Chem., 26, 608--610).-A simple apparatus for Schlo-sing's method. A flask of 150 C.C. capacity is fitted with a caout-D. B.H. B.M. J. S.Apparatus for Nitric Acid Determination.VOL. LIT. 194 ABSTRACTS OF CHEMICAL PAPERS.chouc stopper, through which pass the tube of a separator bulbwith a good stopcock and a long (3 to 4 dcm.) delivery tube bentdownwards at an acute angle and turned up at the end. The nitratesolution is boiled in the flask (the delivery tube dipping into themercury trough) until every trace of air is expelled. The stop-cock is then closed, a boiling hot mixture of ferrous chloride andhydrochloric acid is poured into the bulb, and the lamp is removed.As soon as the mercury begins to rise in the delivery tube, the ferroussolution is allowed to flow in, the lamp is replaced, and the nitricoxide boiled out as usual.A little of the ferrous solution should re-main in the bulb to act as a seal. M. J. S.Determination of Phosphoric Acid. By A. ISBERT andA. STUTZER (Zeit. anal. Chem., 26, 583-587).-The method basedon the determination of the ammonia in the phosphomolybdate pre-cipitate (Abstr., 1887, 526) is confirmed. A further simplificationconsists in washing the yellow precipitate with cold water instead ofwith ammonium nitrate solution. The compound of silicic acid withammonia and molybdic acid is soluble in pure water although insolublein ammonium nitrate.On the other hand, the phosphomolybdate re-quires 10,000 parts of cold water for it,s solution. The removal ofsilica by evaporation may therefore be omitted. The precipitate isallowed to subside completely at 70°, and filtered off after cooling. Itis thrown with it8 filter into a flask, and distilled with soda intostandard acid, which is then titrated back with baryta, using corallinas indicator. One part of nitrogen in the precipitate corresponds with1.654 parts of phosphoric anhydride. Test analyses with knownquantities of phosphate, with and without silicic acid, and com-parative assays of phosphatic manures by the above and the gravi-metric process, show that for commercial purposes the method issufficiently accurate.M. J. S.New Methods of Estimating Arsenic in Pyrites. By J.CLARK (J. Soa. Chem. Iiad., 6, 352-355).-Preci23itation Process.-Three grams of the finely powdered pyrites is mixed in a platinumcrucible with four times its weight of calcined magnesia and soda,and the mixture heated for about 10 minutes over a moderately low.Bunsen flame. The contentls of the crucible are then extracted withboiling water and filtered. The filtrate, which should be green incolour owing to the presence of iron, is acidified with hydrochloricacid, and the solution, which is now nearly colourless, is boiled for ftfew minutes, when the arsenic sulphide will separate along withsulphur.To ensure complete precipitation of the arsenic, it isalways advisable to saturate the solution with hydrogen sulphide.The precipitate is then thrown on to a filter, washed, dissolved withammonia, and the solution evaporated to dryness on a water-bath.The residue is treated with nitric acid and the arsenic in the solu-tion either estimated as magnesium ammonium arsenate, or precipi-tated as silver arsenate, and the arsenic calculated from the silveras determined volumetricall~ by Volhard’s process, or gravimet~icallyby cupellation, as recommended by RichterANALYTICAL CHEMISTRY. 195DistiZEictioa Process.-dbout 1.7 gram of the finely pulverisedpyrites is introduced into a platinum criicible with six times theweight of the above mixture, and heated for an hour over a lowBunsen flame.The contents of the crucible are transferred to aflask, moistened with water, and dissolved in strong hydrochloric acid.The flask, which is fitted with a funnel tube, having the end drawnto a point and dipping under the liquid, is then connected with asmall glass condenser, to the end of which a straight calcium chloridetube is attached, and by means of the funnel tube a considerableexcess of cuprous chloride dissolved in strong hydrochloric acid isintroduced. The contents are then slowly distilled into water for anhour, when a fresh quantity of hydrochloric acid is introduced, andthe distillation continued for + hour. The whole of the arsenic willnow be found in the receiver, but it is always advisable to add a littlemore hydrochloric acid, change the receiver, and test the distillate.The arsenic is then precipitated as sulphide, or it is titrated withiodine in the usual way.D. B.Estimation of Silicon in Iron and Steel. By J. J. MORGAN(Chem. News, 56, 221).-The author criticises Turner’s statements(Abstr., 1887, 1140), and states that silica may be obtained free fromiron and phosphorus in the following manner :-The solution obtainedby dissolving iron in aqua regia is evaporated to a thick syrupy con-sistence, treated with hydrochloric acid, and the precipitated silicawell washed with dilute hydrochloric acid and water, when it is foundto be free from both iron and phosphorus.Estimation of Silicon in Iron and Steel. By T. TURNER(Chem.News, 56, 244--245).-A reply to Morgan (precedingAbstract). Whilst the process described above will give fairly accu-rate results with iron containing under 1 per cent. of phosphorus andabout 1 per cent. of silicon, this is not the case with commoner ironsoontaining 2 per cent. of phosphorus and 3 to 4 per cent. of silicon.Indirect Determination of Alkalis in Presence of Lithium.By I(. KRAUT (Zeii. and. Chem., 26, 604405).--The metals areweighed as nit,rates, ;md the nitric anhydride then expelled by fusionwith silica.Chlorides are converted into nitrates by treatment with silvernitrate. Phosphates are dissolved in a little nitric acid, about anequivalent quantity of silver nitrate is added, and then freshly pre-cipitated silver oxide to neutrality.The excess of silver in eithercase is removed from the filtrate by hydrocyanic acid. This methodis not applicable to sulphates, since barium sulphate cannot be freedM. J. s.Determination of Ammonia in Commercial Products. By 3.M. MILEE (J. Soc. Chem. Ind., 6, 423).-Some time ago a Germancommittee recommended the liberation of the ammonia from phos-phates, manures, and other commercial products, by boiling withmagnesia instead of alkaline hydroxides, and absorption in a measuredD. A. L.The calculation is made in the usual manner.from lithium salts by washing196 ABSTRACTS OF CHEMICAL PAPERS.excess of standard sulphuric acid. One great advantage of thismodification is that the contents of the distilling flask boil quitequietly, and can be brought nearly to dryness without spirting if thegas flame is properly regulated.The author has used this methodfor some time with very satisfactory results. I t is necessary, however,to observe the following precautions :-(1) The steam containing theammonia should be thoroughly condensed as it passes over. (2) Theend of the condenser tube should not dip beneath the surface of thesulphuric acid in the bulb flask. (3) I n order to ensure completeabsorption of the ammonia, a small U-tube containing a little of thestandard acid should be attached to the exit tube of the flask.Assay of Silver containing Small Quantities of Bismuth.Estimation of Mercury in Urine. By L. BRASSE (Corn@. rend.Xoc. Bid. [8], 4, 297-300) .-Simple electrolysis is insufficient,inasmuch as certain organic matters are deposited along with themercury on the electrode.To obviate this error, the author treats100 C.C. of urine with 10 C.C. of hydrochloric acid, places in the mix-ture a small coil of thin sheet brass 1 cm. broad by about 50 cm.long, and allows the interaction to go on for a day. The coil is thenremoved, washed with alcohol and ether, dried, transferred to aporcelain crucible and heated. The mercury vapour is condensed ona concave cover of gold kept cool by distilled water. The differencebetween the weight of the dried cover before and after heating givesEstimation of Iron in Chars. By R. DAVTDSON (J. SOC. Chem.Id., 6, 421).-Having tested the accuracy of the stannous chlorideprocess for the estimation of iron in the case of substances such asanimal charcoal, containing only from 0.1 to 1.0 per cent.of ferricoxide, the author confidently recommends it in preference to eitherthe " permanganate " or " dichromate " process.Determination of Ferrous Oxide in Insoluble Silicates. ByA. H. CHESTER and F. I. CAIRNS (Amer. J. Sci., 34, 113--116).-1ntheir examination of t'he crocidolite from Rhode Island, the authorsdetermined the ferrous oxide by means of ammonium fluoride. Halfa gram of the pulverised mineral is placed in a large platinum crucibleover a water-bath, and a slow stream of carbonic anhydride is carriedinto it. When the air is expelled, a few drops of concentrated sul-phnric acid is added, then Rome ammonium fluoride. Similar addi-tions are made from time to time until the mineral is completelydecomposed. The contents of the crucible are then emptied into abeaker containing cold water.The solution is diluted, and the ironD. R.By J. SCULLY (see p. 108).the amount of mercury. J. P. L.D. B.determined by mGaw of potsesium permanganate in the usual manner.B. H. B.Estimation of Titanic Oxide. By L. LEVY (Cornpt. rend., 105,754-756) .-The author has investigated the conditions necessary toensure accuracy when using the ordinary method of fusing witANALYTICAL CHEMISTRY. 197potassium hydrogen snlphate, extracting with water, and precipitatingthe titanic oxide by prolonged boiling. The solution should contain0.5 per cent. of free sulphuric acid : if less, the precipitate is impure ;if more, precipitation is incomplete.The presence of zinc in thesolution is without influence on the result, provided the proportion offree acid is 0.5 per cent., and the same is true of copper, magnesium,and aluminium, but in presence of ferric sulphate the result is alwaystoo high.The best method of procedure is as follows :-The fused mass ismixed with suficient sulphuric acid to convert the whole of thepotassium into the hydrogen sulphate, solution being thus greatlyaccelerated, and the liquid is then carefully neutralised with potassiumhydroxide, free sulphuric acid added t o the extent of 0.5 per cent.,and the solution boiled for six hours. C. H. B.Determination of Antimony. By F. MUCK (Zeit. anaZ.Chem.,26, 600-602) .-The precipitate of trisulphide is dried by suctionuntil it can be detached from the filter. The filter is washed withwarm ammonium sulphide in which much free sulphur has been dis-solved, this polysulphide having a far greater solvent action thanthe monosulphide. The solution is evaporated in a porcelain crucible.A convenient way of doing this is to support the crucible on a glasstriangle in a deep glass basin containing a little sulphuric acid, andcovered closely with a glass plate. On gently heating the basin on abed of asbestos, tthe liquid evaporates rapidly without spitting. Thedetached precipitate is then added and the whole dried. The freesulphur is removed by treatment with a mixture of carbon bisulphideand chloroform, and the antimony sulphide is converted into tetroxidefor weighing.M. J. S.Delicate Test for Bismuth. By F. B. Srrom (J. Soc. Chem. I d ,6, 416).-This test depends on the fact that a strong solution ofpotassium iodide produces a bright yellow colour when added to itvery dilute solntion of bismuth sulphate containing only a smallquantity of free sulpuric acid. 1 part of bismuth oxide in 1,000,000parbs will show a distinct coloration. Very small quantities of bis-muth may also be estimated colorimetrically by meaus of this test.D. B.Detection of Nitrates in Well Water. By 0. BINDER ( Z e d .anal. Chern., 26, 605--606).-The method depending on the reductionto nitrit,e by zinc, and testing with potassium iodide and starch, failsif too mnch zinc is used.A trace of zinc powder shaken with theliquid answers better than compact zinc. M. J. S.Water Analysis. By 0. BINDER (Zeit. aizal. Chem., 26, 607).-Liquids, such as natural waters, evaporated over a free gas flame,become contaminated with sulphuric acid from the products of com-bustion. M. J. S.Elementary Analysis of Highly Volatile Organic Liquids.By G. KASSNER (Zeit. anal Chem., 26, 588-590) .-The combustion0 198 ABSTRACTS OF CHEMICAL PAPERS.tube is prolonged at the posterior end beyond the furnace, and is bentupwards at an angle of about 45". A plug of asbestos is placed atthe bend. The bulb containing the liquid is introduced at this end,and rests against the asbestos plug with its capillary tube pointingupwards.The bulb having been cooled before breaking the point ofthe capillary tube, can be introduced without the escape of any of theliquid, and the gradual expulsion of the contents can be watched andregulated, since the va,porised liquid condenses in the capillary tube,and is driven out in the form of minute drops. These are immediatelyevaporated and swept forward by the current of oxygen passedthrough the tube. The more volatile the liquid, the longer andnarrower should be the capillary tube. The portion of the combustiontube which is to be heated is filled with platinised asbestos (seeKopfer, ibid., 17,l). For substances which burn with difficulty, how-ever, cupric oxide cannot be dispensed with. For arresting halogens,a plug is employed prepared by shaking chopped asbestos with finelydivided, reduced silver.A stream of hydrogen (free from arsenic orantimony) passed through the hot tube regenerates the metallic silverafter it has absorbed a halogen. M. J. S.The Stalagmometer. By J. TRAUBE (Ber., 20, %24-2835).-Applications of the stalagmometer (this vol., p. 91) to the estimationof alcohol in wine, beer, and liqueurs, and of acetic acid and alcoholin vinegar. Tables are given for use at temperatures between 10" and30" for alcohol, and 11" and 29" €or acetic acid, €or percentages up to10 per cent. by weight of the pure substance in each case. w. P. w.Recognition of Pyrogallol. By G. KLIEBAHN (Zeit;. anal. Chem.,26, 641) .-Pyrogallol when fused with ammonium oxalate yields am-monium rufigallate, which dissolves in water with red colour, and givesthe following characteristic reactions :-Potassium ferricysbnide andpotassium dichromate, a dark-brown precipitate insoluble in alcohol.B'erric chloride, no black coloration.A few drops of acetic acid, thenpotassium cyanide and mercurous nitrate, a black precipitate.Sodium nitroprusside a.nd platinic chloride, no precipitate or changeof colour. Potash, a change to brown, but not to black.M. J. S.Estimation of Grape-sugar in Urine by Robert's Method.By V. BUDDE (P'iiger's Archiv, 40, 137-172) .-The fermentationmethod of determining the amount of sugar in diabetic urine consistsin multiplying the difference in specific gravity before and after re-moval of the sugar by fermentation, by a, constant factor found bycontrol titration experiments in which the percentage so found wasdivided by the difference in the specific gravities.Worm-Muller hasstated (ibid., 37, 479-510) that this factor is constant, namely, 230.This paper is devoted to showing mathematically that from its verynature this factor is a variable one, increasing as the percentage o€sugar diminishes. W. D. HANALYTICAL CHEJIISTRY. 199Examination of Wort and Starch. By E. W. T. JOX’ES (AnnZyst,12, 16:J- 168) .-The methods eixiployed are essentially those describedby O’Sullivan (this Journal, 1876, ii, 130). An analysis is given ofa wort which gave [a]j3.89 = 116.5, and R = 50.8 (Trans., 1879,606). The same wort analysed in the Inland Revenue Laboratorygave the values [a] = 120, and K = 57.2, on which numbers a chargeof the addition of 1.6 per cent.of glucose was based. The suggestionis made that the higher value of K may have been obtained by theuse of Fchling’s solution volumetrically in the presence of dextrin.On keeping this wort for four months (after adding salicylic acid).the rotatory power diminished, whilst the cupric reducing powerincreased. Some of the same malt, mashed in the laboratory forthree hours at 57-60’, gave [a] = 113.6, K = 51.85, from which itwould appear that with some malts the limits recognised by theInland Revenue chemists ( [ a ] not less than 120, and K not over 51)may be exceeded.The method of analysing starch differs from that of O’Sullivan(Trans., 1884, 9) only in the omission of the washings with ether,alcohol, and warm water before gelatinising, and in controlling theresults of the optical method by a subsequent hydrolysis with acid,and a determination by Fehling’s solution.Estimation of Small Quantities of Lactic Acid.By W.WINDISCH (Chem. Centr., 1887, 826, from Wocherzschr. f. Braueri, 13,214).-In order to estimate small quantities of lactic acid, the sub-stance to be examined is heated with chromic acid, whereby thelactic acid is decomposed into formic acid and aldehyde. The mixedvapours are passed into Nessler solution, in which, in presence of analdehyde, lead salts give a yellowish-red precipitate, or with smallerquantities, a yellowish opalescence. In order to examine roots by thisprocess, they are first extracted with ether, which dissolves out allacid substances, V.H. V.31. J. S.New Method of Examining Butter. By T. T. P. B. WARREN(Clzen~. News, 56, 222, 231, 243--244).-Five grams of butter isplaced in a tared tube, plugged with asbestos, and is extracted withcarbon bisulphide. The fats are weighed, dissolved in carbon bisul-phide, and well mixed with a solution of equal volumes of yellowsulphur chloride and carbon bisulphide ; the latter is evaporated, andthe thickened mass redissolved in carbon bisulphide, any insolubleresidue indicating the presence of vegetable oils. The filter tube isdried and weighed ; then by successive weighings after washing, firstwith water, then with ammonia, the dry matter, soluble substances,casein, &c., are determined.The sulphur chloride treatment appliedto other fatty mixtures, such as lard, oil, or oleomargarin, will detectthe admixture of any vegetable oil, rosin, rosin oil, or petroleum.After a few hours’ contact with sulphur chloride, butter becomesbrownish, commercial olein thickens and turns black, and animalole’in assumes a very dark colour, but all dissolve in carbon b i d -phide, whereas vegetable oiIs do not. Inasmuch as animal oils them-selves dissolve vegetable oils, a small qmntity of the latter migh200 ABSTRACTS OF CHEMICAL PAPERS.escape detection in presence of a large quantity of the former; toavoid thilj it is suggested to add to the butter or other fatty mixturesufficient tested cotton-seed oil to supersaturate the animal fats ; thenby treatment with sulphur chloride and subsequent washing withcarbon bisulphide, the animal fats are removed, and the vegetable oilsremain insoluble.Any excess residue over that due to the cotton-seed oil added is derived from vegetable oil present in the butter;this is, however, only approximately quantitative. Water must beabsent when using sulphur chloride. Other precautions are noted,and some remarks are advanced on the character of tho reaction ofsulphur chloride on fats, and of the products formed in the reaction.Attention is drawn t o the high percentage of case'in in some samplesof country butter, probably indicating the use of this substance asan adulterant. D. A. L.The Reichert-Meissl Process for the Estimation of ButterFat.By R. WOLLNY (Bied. Cent?-., 1887, 699-703).-Errors fre-quently arise in the results obtained by working this process, theresults being generally too high. This the author ascribes to the pre-sence of carbonates in the potash used for saponification. A loss mayalso occur from the fact that distillation with sulphuric acid in pre-sence of alcohol will produce ethereal salts of butyric and other acids,consequently the results may be too low. If tohe following precautionsare taken, the results will be accurate. Instead of potassium hydroxide,a 50 per cent. sodium hydroxide solution is to be used, and allowed tosettle before putting aside. Admission of carbonic anhydride t o thesaponifying solution must be avoided, and for this purpose thesaponification must be conducted in a vessel to which a reflux con-denser is attached, and the distillation of the alcohol should be effectedwithout opening the apparatus.A closed T-tube is inserted betweenthe flask and condenser, whereby, after distillation, water and acid canhe added. As regards the process itself, 5 grams of t,he molten andfiltered fat is accurately weighed into a 300 C.C. flask (length of neck7 to 8 cm.), 2 C.C. of 50 per cent. sodium hydroxide solution, whichhas been preserved from all contact with carbonic anhydride, and10 C.C. alcohol (96 vol. per cent.) are introduced into the flask, andafter connection with the reflux condenser the flask is heated in thewater-bath for hour; the alcchol is distilled off, and the heatcontinued for at least 6 hour, 100 C.C.distilled water is then added,and the mixture further heated for & hour, until the soap is dissolved.The clear solution is now to be decomposed whilst hot by 40 C.C. ofsulphuric acid (30-35 C.C. = 2 C.C. of the soda solution), and a smallpiece of pumice should also be introduced. Distillation must becontinued until 110 C.C. of the liquid has been collected, the distillatewell mixed, and of it 100 C.C. filtered 08 and titrated with decinormstlbaryta, phenolphthalein being used as indicator. The figure thusobtained is to be multiplied by 1.1, and from the product are to bededucted such figures as are obtained from a preliminary blankexperiment. The deduction to be made should not exceed 0.33.E. W.PANALYTICAL CHEMISTRY. 201Examination of Cod-liver Oil and Vegetable Oils. By E.SALKOWSKI (Zeit. ana2. Chew., 26, 557--582).-The determination ofthe temperature of solidification is of little assistance, since un-doubtedly genuine specimens show widely different solidifying points.Moreover, cod-liver oil solidifies with extreme slowness, even at tem-peratures far below its freezing point, and an admixture of 20 percent. of rape-seed, linseed, or cotton-seed oil, with an oil of low freezingpoint is not revealed a t a temperature (0" C.) at which other genuineoils solidify. The presence of palm oil, palm kernel oil, or cocoa-nut oilmay, however, be suspected if solidification occurs in 15 to 30 minutesa t 0".Treated by Reichert's process, cod-liver oil gives a very small quan-tity of volatile acid.Linseed, rape-seed, cotton-seed, and palm oilsgive a slightly higher yield, but not sufficiently diiferent to enable thismethod to detect an admixture.When cod-liver oil is saponified and the dilute solution of the soapshaken with ether, cholesterin is extracted, together wit@h a yellowsubstance, which seems to belong to the lipochrome series (Kuhne,Untersuch. physiol. Inst. Heidelberg, 1882). This substance gives anindigo-blue colour with strong sulphuric acid, whilst cholesterin andalso the cod-liver oil itself give violet. The fatty acids from the soapsolution freed from cholesterin, when dissolved in chloroform andmixed with sulphuric acid, give a dark brown-red colour, with dirty-green fluorescence.If after pouring off the chloroform some of theacid is added to glacial acetic acid, the mixture slowly acquires a finered-violet colour, with dirty-green fluorescence. The only vegetableoils which in choloform solution are coloured blue by sulphuric acidare palm oil and cotton-seed oil. All the vegetable oils (except palmoil), when treated as above for the extraction of cholesterin, yielded asubstance which was identified with the phytosterin of Hesse. Thismay be dist'inguished from cholesterin by its appearance under themicroscope. A hot alcoholic solution of choles terin solidifies 011cooling to a mass of thin, rhonibic plates, frequently showing re-entering angles; the substance obtained from the vegetable oils formsstellate or fascicnlate groups of thick needles, or on slow coolinggives elongated six-sided plates.The products from all the vegetableoils melted at 132-134" (Hesse's phytosterin at 132-135"). Choles-terin from genuine cod-liver oil melts a t 146" ; the product from anoil adulterated with 20 per cent. of rape, linseed, or cotton-seedoil melted at 139-140", and showed the needles of phytosterin, toge-ther with the plates of cholesterin.Most of the specimens of cod-liver oil examined contained very litllefree fatty acid (0.24 to 0.69 per cent. calculated as oleic acid ; onespecimen, however, showed 6.5 per cent.). Since many vegetable oilsgive numbers lying within these limits, this character is of no serviceior their detection.M. J. S.Titration of Urea with Mercuric Nitrate. By E. PFL~GER(Pfliiger's Archiv, 40, 533-586) .-After some critical remarks onvon Rantenberg's and Pfeiff er's modifications of Liebig's method ofestimating urea, a series of 28 experiments is detailed, in whic202 ABSTRACTS OF CHEMICAL PAPERS.the amount of nitrogen in urine was estimated first by Kjeldahl’smethod, and secondly by Rautenberg’s mercurial solution. In somecases, the results by the latter were higher, in othem lower than byKjeldahl’s method, and taking Kjeldahl’s method as one which givesaccurate results, it is calculated that the average error of Rautenberg’smethod is 0.7 per cent. On the average, out, of 100 pavts of thenitrogen in urine, 13 are combined i n substances other than urea.Rautenberg’s method does not give the amount of urea, but the totalnitrogen.W. D. H.Fractional Reduction of Ortho- and Para-nitrotoluene andQuantitative Analysis of Ortho- and Para-toluidine. By T.MINIATI, H. BOOTH, and J. B. COHEN (J. SOC. Chem. I d , 6, 418-420).-From a series of experiments on the reduction of ortho- and para-nitrotoluene, it seem8 that both nitro-compounds are acted on conour-ren tly .Before commencing their analytical work, tJhe authors thought itdesirable to determine whether the reduction could be so regulatedthat approximately the same quantities of nitrotoluene could bereduced with w given quantity of the reducing agent ; it was foundthat with care this could be readily accomplished.The separationand isolation of the nitrotoluene and toluidine is effected in thefollowing manner :-After reduction, the acid solution obtained isdistilled with steam, and the uuattacked nitrotoluene driven over,the toluidine remaining behind. The toluidine solution is freed fromtin by treatment with hydrogen sulphide and filtered. The filtrate ismade alkaline and distilled with steam, when the toluidine distilsover. Both distillates are extracted with ether, the ether is distilledoff and the residues dried and weighed. The first gives the weight ofnitrotoluene, t,he second that of the toluidine. Having the respectiveweights, an analysis of the one or the other and determination of thequantity of‘ ortho- and para-compound present therein, suEces tofind exactly how the reduction has gone.Having made unsuccessfulattempts to analyse the resulting nitro-compound, the authors triedvarious methods for the quantitative estimation of ortho- and para-toluidine. The only process they found practicable was to add excessof oxalic acid solution, bring the precipitate on to a filter-paper,wash three or four times with ether, and weigh on a watch-glass.Any residue remaining in the precipitating vessel and in the filter-paper was dissolved in water and titrated with decinormal potashsolution. With paratoluidine, it was found that precipitation was notcomplete unless the mixture was allowed to remain 1% hours.With pure orthotoluitl ine, there is no immediate precipitation, biit in12 hours from 4 to 5 per cent.of the ortho-compound crystallises out ;hence in performing the analysis the error due to the precipitation ofthe ortho-compound must be allowed for if the golution remains12 hours, or the error due to incomplete precipitation of the para-compound must be allowed for if the precipitate is filtered imme-diately. The better plan would therefore be to obtain an approximn-tion of the amount of para-compound present in one determinationANALYTICAL CHEMISTRY. 203and then run in just sufficient oxalic acid solution t o precipitate thisquantity, and wait for 12 hours. D. B.Estimation of Small Quantities of Paratoluidine in Ortho-toluidine. By C. HAEUSSERMANN (Chem. Ind., 10, 55-56).-0f themethods recommended for the estimation of para- and ortho-toluidinethe process based on the titration of the para-compound with oxalicacid in an ethereal solution has been mostly adopted.It is not,however, wholly free from error, owing to the fact that t,he amount ofether to be used is frequently insufficient to completely dissolve the'' ortho-oxalate " produced by the reaction. The author suggests thefollowing method :-A solution containing 88 grams of crystallisedoxalic acid in 750 C.C. of water and 43 C.C. of hydrochloric acid of22' B. is heated in a porcelain basin to 70-75', and treated with10 grams of the toluidine under examination. When the preci-pitate which separates has been entirely redissolved, the mixture isallowed to cool gradually to 30-35" nntil the oxalate shows signs ofcryshallisation on the surface of the solution.It is then filteredthrough cotton and the residue washed with a few drops of water.The precipitate forms small, colourless scales having a dull appear-ance. The filtrate on standing deposits a further portion of crystalswhi& are mJJecked on a qmrahe filier md wa,sned Tbj,, oppmiimis repeated until crystals are obtained having a lustrous appearance.These consist of the pure '' ortho-oxalate," and are readily distin-guished from the crystals of the para-compound. The crystallinefractions are then treated with a solution of sodium carbonate andsubjected separately to distillation. The solidifying point of thedistilled bases is determined by cooling a fraction of each distillatewith ice. If the oil solidifies by merely agitating it, the crystals arecollected on a tared filter, and after drying over sodium hydroxideweighed as paratoluidine. If, however, the addition of a few crystahof pure paratoluidine is required to induce solidification, only one-halfof the mass is calciilated as paratoluidine. If, on the other hand, it isimpossible to solidify the base obtained from the distillation of thefirst crystalline fraction, orthotoluidine only is present in the sampleunder examination. With good toluidines, it generally suffices tocollect and distil two fractions, in which case the base from the secondcryst,zllisation mostly constitutes a perfectly liquid oil. This methodbeing inapplicable to mixtures containing more than 10 per cent. ofparatoluidine, it is suggested to dilute such mixtures by the additionof pure orthotoluidine. D. B.Volumetric Determination of Alkaloids by Mayer's Reagent.By F. S. HERETH (Zeit. a n d Chem., 26, 647)-To avoid the errorsintroduced by the use of filters and the irregular addition of thereagent (potassio-mercuric iodide), several equal portions of the solu-tion to be titrnted should be mixed a t once with quantities of thereagent differing from one another by 0.1 c.c., and ranging fromsomewhat below the amount indicated by a rough preliminary test toan equal distance above. After settling for at least eight hours i204 ABSTRACTS OF CHEMICAL PAPERS.closed test-tube, part of the clear upper liquor can be poured off a i dtested by a drop of the reagent. The extract is prepared for titrationby acidifying and gently warming t o drive off alcohol. If any pre-cipitate separates it is filtered off and washed with dilute acid. Theliquid should finally contain about 1 per cent. of free sulphuric acid.M. J. S.Tanret's Reaction for Albumin, Peptone, and Alkaloi'ds inUrine. By L. BRASSE (Compt. rend. Hoe. BioZ. [S], 4, 369-370).-Albumin, peptone, and alkaloids are precipitated from urine in thecold by Tanret's reagent, potassium mercury iodide. On heating,the peptone and a1 kalojidd precipitate dissolves, leaving the albumininsoluble. The alkalo'idal precipitate can be easily separated fromthe peptone precipitate by reason of its solubility in ether.No insoluble combinations are formed with any of the ordinaryconstituents of urine, such as creatine, creatinine, xanthine, or hypo -xanthine, but bile salts give rise to a precipitate insoluble, likealbumin, in both cold and hot solutions. This precipitate, however,can be cliff erent'inted from the ordinary albumin precipitate inasmuchas it is soluble in ether. J. P. L.Haematoscopic Study of Blood. By A. H~NOCQUE (Conzpt.rend. ,S"oc. Bid. [8], 4, 383--284).-The chief advantage in the useof the haemahscope (Abstr., 1887, 312), for the spectroscopic examin-ation of blood is the possibility of examining the blood undiluted.J. P. L

ISSN:0368-1769    

DOI:10.1039/CA8885400192

出版商:RSC    

年代:1888

数据来源: RSC

摘要:

205 General and Physical Chemistry, Chemical Action of Light on an Explosive Mixture of Chlo- rine and Hydrogen. 'By E. PRINGSHEIM (Ann. Phys. Chem. [2], 32, 384-428).-Bunsen and Roscoe (Ann. Phys. Chem., 96, 373 ; 100,43, 481; 101, 235; 108, 193; 117, 529) propounded the question- " Whether in photochemical combination an amount of work is done for which an equivalent of luminous energy disappears, o r whether the action effected by the chemical rays is merely started by the light without the expenditure of a sensible amount of luminous energy." They endeavoured to solve this problem in the case of hydrogen and chlorine, by comparing the quantity of light absorbed by the mixture with that absorbed by dry chlorine, or as they call it, the opt,ical extinction in chlorine. They assomed that this optical extinction would be of the same amount in the mixture, and therefore concluded that the considerable additional extinction observed in the mixture was due to the transformation of luminous energy into heat energy during the chemical action.The author objects to thiq reasoning, that the light absorbed in chlorine alone is itself trnns- formed into heat, thereby raising the temperature of the gas, whilst in the case of the mixture, the luminous energy may very probably be transformed directly intg chemical energy. In support of this view, he adduces Bunsen and Roscoe's observation that the action of light was considerable when the range of temperature was from 18" to 26". The luminous energy, indeed, may either increase the molecular motion directly and the atomic motion indirectly, or vice tiers$, G r more probably hoth processes may go on simultaneously.From the kinetic theory of gases, the introduction of energy by conduction of heat mnst increase the molecular velocities, which are of rt very irre- gular character. Now it is found that the absorption of light is a function of the wave-length,. and i t therefore seems qrobable that, the chemical action of light consists in the direct transfer of energy to the atoms, whose motions consist of vibrations of definite periods, and is therefore the direct cause of dissociation. When in equilibrium, there is a definite relation between the atomic and the molecular energy OF a gas, and if this is disturbed by the absorption of light, there will be a change in the number of molecular impacts, and before A fresh state of equilibrium is attained, the direct increase in the atomic energ7 may be more or less expended ; in the present case in effecting chemical change ; in other cases, in producing fluorescence, phosphorescence, or electrical phenomena.The assumption, therefore, that what Bunsen and Roscoe call the optically absorbed light simply increases the temperature, and that the additional absorption due to the presence of hydrogen increases the chemical absorption, is not justifiable. If the light absorbed by the chlorine molecules in the mixture produces chemical action, this, as shown later, will probably P TOL. LIT.206 ABSTRACTS OF CHEMICAL PAPERS. consist i n the formation of intermediate unstable products whose coefficient of absorption of light differs from that of the mixture of chlorine and hvdrogen, so that “ chemical extinction” must be regarded as the consequenco rather than the cause of the chemical change.The existence of chemical extinction is therefore no criterion as to whether transformation of luminous into chemical energy takes place, SO that Bunsen and Roscoe’s method is incapable of solving the question proposed by them, but a result obtained in another portion of their researches, namely, that the chemical action is proportional to the intensity of the light, although not so applied by them, seems to give tshe required solution; for if the action of the light were simply to disturb a state of unstable equilibrium, the quantity of hydrogen chloride formed would be independent of the initial impulse.It must, hherefore, be assumed that a definite absorption of luminous energy will take place for every molecule of hydrogen chloride formed, but it does not follow that more light must be absorbed than with the chlorine alone, The determination of the cause of the increase of the extinction- coefficient, which may be due merely to a change in the condition of the mixture, leads to an investigation of the pliysical and chemical phenomena which accompany the formation of hydrogen chloride, and therefore to the consideration of “ Photochemical Induction.” Burmen and Roscoe found that when light falls on a freshly prepared mixture, or on one which has been for a time in darkness after previous exposure to light,, there is a t first no appreciable formation of hydrogen chloride ; after a certain interval, a, slight action begins, gradually increases to a maximum, and then remains constantly proportional to the time.The act of overcoming the resistance here indicated and bringing the gas into a state of readiness for combination, tlhey call chemical induction, and when due to the action of light, photo- chemical induction. They found the duration of the seemingly in- active interval to increase with the thickness of gas traversed by the light, and to decrease with increasing intensity of light more rapidly than the intensity increases. Both of these results are confirmed by the author, who further finds that the rate of formation of hydrogeii chloride depends only on the intensity, and not on the wave-length of the light, from which he concludes that the inductive action is pro- bably a chemical one.By instantaneous exposure to a stronger source of light, he finds that the gas undergoes a momentary expan- Rion proportional to the intensity of the light, which is evidently not due to the heat of formation of hydrogen chloride, from the rapidity with which it appears and disappears, and also because it is found to be independent of previous induction and of the amount of hydrogen chloride formed. Neither can it, for the former reason, be due to the heat which Budde (Ann. Phys. Chem., 144, 213) has shown to be produced by the absorption of light by chlorine. He therefore concludes that some intermediate product is formed, that the expansion is due to momentary dissociation, and that the quantity formed is proportional to the int’ensity of the light.It does n o t seem reasonable to suppose that this may consist of molecules of H2Cl and C1 or HCI, and H ; the author therefore seeks for the cause inGENERAL AND PHYSICAL CHEJlISTRT. 207 the presence of water-vapour (the gas being in contact with water during the experiments), in accordance with the influence known to be ex- cited by water-vapour on other explosive mixtures, and in confirma- tion of this he finds that when a solution of hydrogen chlorida is substituted for the water, and the gas dried as completely n s possible, much less hydrogen chloride is formed by the action of light of given intensity, and with the feeble light used in the earlier experiments, no action at all takes place.The author assumes the action t o take place in two stages, for example : - (1.) H2 + C12 + HzO = C1,O + 2H2; (2.) C120 + BH2 = 2HC1 + H20; or some similar action, the exact nature of which may be determined by chemical analysis. He supposes the action to be Homewhat as fol- lows :-The intermediate substance is first formed, the process con- tinuing until a certain proportion of the gas is transformed. Mass actions then come into play between chlorine, hydrogen, water and the intermediate product, and hydrogen chloride begi,ns to be formed. The second stage of induction now begins. The amount of the inter- mediate product increases more rapidly than it is used up in forming hydrogen chloride, which is therefore formed a t an increasing rate, until the intermediate product is destroyed as fast as it is produced, introducing the third stage, in which the formation of hydrogen chloride is proportional to the time.When removed from the action of light, the quantity of intermediate product will soon fall below the minimum required for the production of hydrogen chloride, and the remainder will break np again into hydrogen, chlorine, and water. This gradual decomposition of the intermediate product into its original coiistituents will go on even during induction, which explains why, with diminishing intensity of light, the duration of induction increases more rapidly than the intensity diminishes, for since the nature of the change undergone by the intermediate product depends on its actual amount, therefore the less the intensity the greater will be the ratio of the amount destroyed to that newly formed in each moment.G. W. T’. Anomalous Dispersion produced by Glowing Vapours. By A. WINKELMANN (Ann. Phys. Chem. [2], 32, 439--442).-Kundt (Ann. Phys. Chem. [a], 10, 231) discovered the anomalous dispersion produced by sodium vapour. The method he used was to allow a ray of light to pass through the conical flame of a Bunsen burner coloured with sodium vapour, so as to be refracted by the flame, which acted like a prism wit!L its refractiug angle horizontal and upwards, and then through a vertiral prism, by which means he obtained crossed spectra which showed the anomalous dispersion. In the hope of making the action stronger, Kundt attempted, but without success, t o reduce the flame to a prismatic form by the use of glass or mica plates.The author has succeeded in doing this by using as the burner a tube of triangular section and provided with an air-blast. p Y208 ABSTRACTS OF CHEMICAL PAPERS. On the top of the tube is placed a double thickness of wire-gauze, and on that again a triangular support smaller than the section of the burner, made of iron wire, which carries an iron cup of the same dimensions as the support, in which the sodium is placed. With this apparatus Rundt’s phenomenon was exhibited very clearly, and it was also obtained, although less distinctly, with potas- sium. Lithium and thallium chlorides were also tried but with negative results ; this the author attributes to the insufficient density of -the vapour.G. W. T. Components of the Rare Earths yielding Absorption-spectra. By G. KR%S and L. F. NILSON (Ber., 20, 3067--3072).-A reply to G. H. Bailey (this vol., p. 1)’ in which the authors maintain the cor- rectness of their views on the components of the rare earths (Abstr., 1887, 890). Components of the Rare Earths yielding Absorption-spectra. By G. H. BAILEY (Ber., 20, 3325--3327).-A rejoinder to the pre- ceding Abstract. Theory of Researches on Contact-electricity. By F. EXNER (Ann. Phys. Chenz. [2], 32, 515--520).-The author’s recent re- searches in support of his denial of contact-electrification (Ann. Phys. Chem. [2], 32, 53) were founded on his experimental result, that if an insulated conductor is connected with an electrometer, and the latter then disconnected from the earth, and if the capacity of the con- ductor is then altered, the electrometer will remain unaffected, whilst according to the contact-theory there should be a flow of electricity.The present note is a reply to objections which Hallwachs (ibid., 64) has advanced against the author’s conclusions. In reply to these objections he states that- (1.) The potential of the grating of oxidised iron which surrounded the apparatus differed by less than 0.05 of a, Daniel1 from that of the walls of the room, which would justify his neglecting it; moreover, from (4), its potential, whatever its value, would be without influence on the results. (2.) The capacity of the conductor was measured inside the grating, and not outside as assumed by Hdlwachs.(3.) He is justified in neglecting the change of capacity in the quadrants during the movement of the needle, since for the maximum deflection to be expected the error so arising would not exceed 1 per cent., and as no deflection was observed, the objection is entirely irrele- vallt. (4.) The potentials would aatnrally be understood to refer to that of the grating as zero, without an express statement to that effect; moreover, the author shows by a simple mathematical proof that the result is independent of the absolute values of the potential, the essence of his method consisting in eliminating the influence of the grating by comparative observations on different metals. The dif- ference of deflections which should hare been obtained accordiiig toGENERAL AND PHYSICAL CHEMISTRY.209 the coiltact-theory would have amounted to from 10 to 15 scale-divi- Bions, and would therefore be easily observed. (5.) To eliminate the possibility that t’he absence of a deflection might be due to unknown external effects, a Daniell’s cell was intro- duced into the insulated system, and the deflection obtained was found to agree closely with the value predicted theoretically. (6.) The author claims that he has proved that no change is pro- duced when the grating is brought into contact with a conductor con- sisting of a different metal. Such a change is required by the contact- theory, but the author has not attempted to determine whether it would be required by the chemical theory, nor, as far as he is aware, has the question been considered by others.Resolution of the Electromotive Forces’of Galvanic Elements into their Differences of Potential. By J. MOSER (Monatsh., 8, 508--509.)--Examples are given in this paper of the resolution of the electromotive forces of certain galvanic combinations, and determinn- tion of each of the components at the electrolytic surface. The sum of these several components is shown t o be equal to the total electro- motive force of the cell. The method of “drop electrodes,” as applied by the author to exclude the electromotive force of contact metals, is used, a method based upon an observation of Helmholtz, that if a n insulated mass of mercury, dropping quickly, is in contact with an electrolyte at the dropping point, there is no difference of potential between the mercury and the electrolyte.Thus the total electromotive force of the combination Zn I dilute ZnC1, [ concentrated ZnClz I Zn = 0.15 volt. The values of the electromotive force a t the three surfaces v, J; and c, were found by the drop electrode method to be- G. W. T. 21 = 1.1 volt c = 0.98 andf = 0.27 f + c = 0.95. Now 1.1 - 0.95 = 0.15, or the value found for the total electro- Again taking the Daniell’s cell as another example- motive force. total electromotive force = 232 - 40 Zn I ZnS04 I CuSO4 Zn I ZnSO1 c u I G U S 0 4 = 40 a value agreeing with that obtained by direct observation. A similar agreement between the sum of the differences of potential and the total electromotive force in the Lakimer-Clark’s cell is also noticed.V. H. V. Property of the Alkalis of increasing the E.M.F. of Zinc. By J. H. KOOSEN (Ann. Phys. Chent. [Z), 32, 508-515).-Grove, Joule, Poggendorff, and others have observed the increased E.M.F. obtained by substituting aqueous potash or soda for the dilute acid in n cell. The author states that according to his researches the alkali, say potassium hydroxide, has a four-fold action: (1) it breaks up210 ABSTRACTS OF CHEMICAL PAPERS. into potassium and oxygen ; (2) potassium replaces zinc in its elec- trical action, for instance, in a Daniell’s cell potassium sulphate is formed in place of zinc sulphate, as the copper is deposited ; (3) the zinc is oxidised by the oxygen of the potash; (4) the resulting zinc oxide is dissolved by the aqueous potash.(1) Diminishes the E.M.F., whilst (2) and (3) increase i t ; (4j may possibly slightly increase it, but it would be desirable to have positive evidence on this point. If the external resistance of a cell is very great, almost the whole heat of combination will be developed in the external circuit.. Let the E.M.F. of a Daniell’s cell be taken as the unit of E.M.F., and let the unit of heat be the amount generated in a Daniell’s cell by the decomposition of n grams of zinc, where n is the atomic weight of that metal. Then from Thomsen’s determinations, the E.M.F. of a Daniell’s cell is given by the equation ZnS0,(248) - CuSOa(198) = 50 = 1 Daniell; and with potash substituted for dilute sulphuric acid, K,S04(337) + 2ZnOH20(166) - 2KH0(232) - CuS04(198) = 73 = 1.46 Daniell.For the author’s zinc-bromine-platinum cell, ZnBr2(91) = 1.82 Daniell. The results thus thoretically obtained in the case of these and a few other simple cells considered by the author agree closely with experimental determinations. The heat of combustion of zinc oxide and potassium is not taken into account, as it is certainly not more than 2 per cent. of that due to the decomposition of zinc in a Daniell’s cell, and according t o Favre and Silbermann it would seem that th’s chemical action is merely local, and does not contribute to the electrical energy. Practically the author finds that a Daniell’s cell with a solution of potassium hydroxide is very satisfactory for giving continuous currents through a high resistance, and sodium hydroxide gives still better results, as sodium sulphate, being more soluble, does not so readily crystallise on the porous cell.I t is very important to prevent interdiffusion of the fluids as far as possible, and for this purpose the author uses a double porous cell, having the intermediate space filled with a solution of potassium and sodium sulphates respectively, with a small admixture of sulphuric acid to diminish the resistance. Cells of this kind have been kept joined up through a resistance of 20 or 30 ohms for weeks together without any perceptible diminution in the E.R.I.F. The alkaline solution must not be too dilute or the zinc will soon become coated with oxide. The author stmates that his zinc-bromine-platinum cell is still better for giving a continuous current through a high resistance.It re- quires no porous cell, has a high E.M.E., and has been kept in con- tinuous action for months withont any change in the E.M.F., in fa(+ until one or other of the elements was completely decomposed. The only precaution necessary is to cover the bromine with a layer of petroleum, which completely prevents all evaporation and smell. G. W. T. Electrolytic Formation of Hydrogen Peroxide at the Anode. By M. TRAUBE (Ber., 20, 3345--3351).-From the results of previousGENERAL AND PHYSICAL CHEJIISTHY. 211 cxperirnents (Abstr., 1885, 1108), i t was concluded that hydrogen peroxide is formed by the union of molecular oxygen with hydrogen. Richarz, on the other hand (this vol., p. 11). maint'ains that that hydrogen peroxide is produced by the oxidation of water.When 1 per cent. sulphuric acid is electrolysed in presence of alcohol or hydrogen peroxide a t the anode, these are rapidly oxidised. I n the electrolysis of a 1 per cent. solutionof chrome alum, not a trace of ozone is formed, and chromic acid appears at the anode. When lead is used as anode in the electrolysis of 1 per cent. sulphuric acid, i t becomes covered with lead peroxide. These experiments point to the presence of free oxygen-atoms which only unite to passive mole- cules when there is nothing to oxidise, and a.lso show that water is not oxidised by oxygen-atoms. I n the electrolysis of sulphuric acid, it is suggested tliatl persulphriric acid is formed by the action of nascent oxygen, and that this decomposes into sulphuric acid (2 mols.) and hydrogen peroxide ( 1 mol.).As further proof in favour of the constitution previously ascribed t o hydrogen peroxide (Abstr., 1886, 660), it is mentioned that the poroxides of hydrogen, of the alkalis and alkaline earths, of zinc, cadmium, and copper, have quite different chemical properties from those of lead, silver, manganese, and nickel, &c. Only those of the first group yield hydrogen peroxide when trea,ted with acids. The peroxides of the second group can all be prepared by oxidising the oxides or hydroxides in alkaline solution. The peroxides of the first group possess powerful reducing properties, whilst those of the second group are indifferent to oxidising agents. Hence it, is concluded that the peroxides OF the two groups are differently constituted, and that hydrogen peroxides cannot have the formula HO-OH.The con- stitution represented by the formula H*O : 0.H is considered to be the only one possible. N. H. M. Electrolytic Conductivity of Halogen-compounds. By W. HAMPE (Ckem. Zeit., 11, 816; 846-847 ; 904-905; 93.1f-935 ; 1109- 1110 ; 1158).-Pure dry sa1t.s fused in hard glass tubes or porcelain crucibles, o r dissolved in dry ether or absolute alcohol, weTe submitted to a current from eight large Buusen chromic acid cells, platinum electrodes being used when the conditions of experiment permitted. The following salts proved good electrolytes i n a state of fusion:- A11 6he haloid salts of lidhiurn, sodium, potassium, rubidium, and cmium, beryllium chloride, magnesium chloride and bromide, stron- tium and calcium chlorides and bromides (part of the liberated metals combining with the silica of tlie glass or porcelain), barium chloride, lanthanum, didymium, and cerium chlorides (this confirms Hillebrand and Norton's experience), indium chloride, thallous and cuprous chlorides (thallic and cupric chlorides decompose when fused), tantalum chloride, and thorium chloride, although the latter is not suitable for electrolysis, as the melting and boiling points are near together I n concentrated alcoholic solutions, cupric chloride behaves as aii electrolyte.Gold chloride in carbon bisulphide is a non-conductor ; when mixed with ether a pasty mass forms, and the supernatant212 ABSTRACTS OF CHEMICAL PAPERS. liquid gradually deposits gold ; this liquid conducts slightly, and after 15 minutes the negative pole becomes gilded.Aqueous solutions of gold chloride owe t'heir electrolytic conductivity to the presence of hydrochloric acid. Zinc and cadmium iodides, bromides, and chlorides are good electrolytes when fused, but their conductivity ceases on solidi- fication. I n concentrated solutions, these salts conduct well, in weak solutions badly; in absolute alcohol all, but only zinc chloride and bromide dissolve iu ether and conduct well, whilst the other salts dis- solve in ether and conduct only sparingly or not at all. Fused mer- curic chloride, bromide, and iodide are feeble electrolytes, especially the first; in solution in ether, none conduct, owing probably to sparing solubility ; in absolute alcohol, they conduct slightly ; better when the solution is hot than when it is cold.Mercurous chloride fused in closed glass vessels proved electrolytic. Aqueous solutions of mercuric chloride conduct badly at first, with deposition of mercury and mercurous chloride, and evolution of oxygen and chlorine ; sub- sequently mercury only is deposited, and the electrolysis proceeds at a quicker rate ; i n this case the current in the first instance produces electrolytes (hydrochloric acid for instance), and when these are present in abundance the process goes well. Fused gallous chloride is a very good conductor, globules of metal Reparate at the negative pole, but the chlorine a t the positive pole corn- bines with the gallous chloride to form gallic chloride ; the latter is iiot such a good conductor as gallous chloride, no metal separates, evidently owing to its entering into combination with the gallic ahloride to form gallous chloride.S tannic chloride does not conduct; when electrolysed in aqueous solution the hydrochloric acid only con- duct,s, the tin being set free by the hydrogen (Hittorf hag stated the contrary). Fused stannous chloride on the other hand is an excellent electrolytic conductor, the current continues to pass even on cooling a3 long as the mass remains soft, but ceases to flow when the chloride iii solid. Fused lead chloride, broniide, and iodide conduct very well with vigorous decompositiori, and, unlike the other salts examined, metallic, Wiedermann regarded it as electrolytic ; the author confirms the latter view.At ordinary temperatures, no current passes through the cold fused lead salts; it is first observed to flow at 110" throuph the chloride, at 115" through the bromide, and a t 159" through the iodide, the conductivity then increases as the temperature rises, in the manner usual with electrolytes. The trihaloyd compounds of antimony in a fused state behaye as feeble electrolytes, the tri-iodide Iieing the best; but in carbon bisulphide solutions they do not con- duct electricity. Vanadium tetra- and tri-chlorides do not conduct, but when decomposed with water the solutions electrolyse, but in lieither case is the metal deposited. The following aye non-con- ductors :-Fusea aluminium chloride or bromide (Buff's statement to -the contrary is probably based on experimerits with impure chloride), boron chloride, titanium and silicon tetrachlorides and bromides, vanadyl chloride, niobium pentachloride, all the haloid compounds of phosphorus, arsenic trichloride, and antimony pentachloride.Yttrium and zirconium chlorides sublime without melting, and when +Jiitq Z~mi!U~~i" a h a wJ,:rt,; BL% cbarw?iu&fi+u Wfi C-ddUciPfiGENERAL AND PHYSICAL CHEMISTRY. 213 +he former is dissolved in water it conduct,s on account of the hydro- chloric acid, but no metal is deposited ; the latter is a non-conductor ; titanium hexa- and di-chlorides are infusible solids, so do not come under consideration, D. A. L. Molecular Heats of Gases. By H. LE CHATELIER (BUZZ. HOG. Chim., 48, 122--124).-The fact that the curves of the specific heats of carbonic anhydride and water vapour converge to a point below zero, leads to the supposition that molecular heats of all gases tend to hhe same limit as the temperature approaches absolute zero.The author has compared the specific heats, calculated on this assumption, with the actual determinations of Wiedemann. The specific heats can be represented by the expression C = 6-8 + r ~ [ 3 7 3 + t ] , a being a constant which depends on the nature of the gas and has a higher value the more complex the molecule. The numbers calculated by this equation differ from the actual numbers by quantities less than the experimental errors. A similar agreement is found between the numbers for carbonic anhydride at high temperatures deduced from khis equation and the actual numbers obtained by the author and Mallard. C.H. B. Influence of Small Amounts of Impurities on the Vapour- tension of Liquids. By G. TAMMAN ( A ~ L Phys. Chena. [Pj, 32, 683--699).--The increase in the vapour-tension of a liquid observed by Wiillner and Grotrian (Ann. Phys. Chew,. [2], 11, 545), when the space occupied by its vapour in the manometer has been decreased by compression, and attributed by them t o a dependence of the tension on the amount of liquid in contact with the vapour, is shown to be caused and brought about by traces of impurity in the liquid. These traces are often so exceedingly small as not to be recognisable by the urdidary tests. But the vapour, if containing this impurity, consists of a mixture of two substances one of which is more volatile than the other, so that compression causing a greater condensation of the less 3-olatile, causes a rise in the vapour-tension, and expansion has just the opposite eeect.A difference is therefore observed between the tension measured after compression and after expansion. This diffe- rence is reduced in magnitude by purifica.tion of the liquid used, but could not in any case be entirely eliminated, although an approxima- tion to a constqnt tension was reached in the case of water. A measurement of the vapour-tension, once after compression and once after expansion, will give a, rough measure of the purity of the sub- stance used. Experiments are given with water, ether, carbon bisulphide, benzene, methyl and ethyl alcohols, chloroform and acetic acid.H. C. Dissociation of Crystallised Lead Acetate and Sodium Thiosulphate. By W. M~LLER-ERZBACH (Ber., 20, 2974-%81) .- Two series of experiments were made with lead acetate. In the first series, large crystals of the commercial salt were employed in the state of powder, and with it the relative tension was 0.27 to 0.38 at temperatures varying between 12.5" and 21.8" ; whilst in the second series, in which214 ABSTRACTS OF CHEIlICdL PAPER.S. small crystals OF the pure salt were used, the relative tension was 0.32 to 0.39 a t 149-24*3"; the valiie of tl - t2, which the author assumes to be a measure of the attraction between the aalt and its water of crystallisation (compare Abstr., 1887, 628), decreasing with +,he rise of temperature.A partially dehydrated specimen of the salt containing about 8 mol. H,O, when placed in a moist atmosphere until water equal in amount to 3 mols. had been absorbed, showed a higher and less constant relative tension, the highest value being 0.485 a t 21.5". Wit,h sodium thiosulphate, Na2S2O3 + 5H,O, two series of experi- ments were also made, and in the first eeries 3 mols. H,O were lost with a relative tension = 0.33 to 0.36 a t 29*1-32.9", and a, further 1-4 mol. with a relative tension = 0.17 to 0.22 a t 31-7--34-2", the remainder of the water being given off with a relative tension = 0.047 to 0.053 a t 50.6-52.7". The second series of experiments showed that, 3 mols. were lost with a relative tension = 0.26 to 028 at 18*3-21*6", that a fnrther 1.4 mol. was lost with a relative tension = 0-G8 to 0.12 at 15.9-22.1", and that the tension became imper- ceptible when the salt contained 0.6 mol.H20. The partially dehy- drated salt, containing 2 mols. H,O, exposed in a moist atmosphere until i t contained 4.75 mols. H20, lost 2.55 mols. with a relative tension = 0.29 to 0.31 a t 23.6-25.9", and the salt with 2 mols. H,O, obtained in like manner from the salt + 0.49 mol. H20, lost approximately 1.5 mol. with a relative tension = 0.10 to 0.19 at 5.3-16.1". It was found, however, that when sodium thiosulphate was heat,ed to drive off the water of crystallisation rapidly and then exposed to moist air until 4.9 mols. H,O had been taken up, it lost the whole of the water with a relative tension = 0.21 to 0.32 a t 15.8-30.6. W.P. W. Relation between the Compressibility of a Solution and the Compressibilities of its Constituent Parts. By F. RRAUN (Ann. Phys. Chem. [Z], 32, 504-5508).-Rontgen and Schneider (this vol., p. 22) have given for the compressibility of rock-salt the value 5 x 10-6, which does not agree with the author's previous determina- tion (Abstr., 1887, 436), which gave 1.4 x 10-6 This result was ohtained by comparatively rough methods, but the author points out that it agrees very closely with the value 1.6 x 10-6, deduced from Voigt's determination (Ann. Phys. Ohem. h'rgbd., 7, 214) of its two coetiicients of elasticity. Rontgen and Schneider assume that if y be the compressibility of a solution containing per unit volume a volume V' of water, and V" of salt, and if y' be the compressibility of water and y" that of the salt;, then (1) Now if n be the number of molecules in a solution containing a percentage p of salt of molecular weight m, then (2) n = 10~p/m(100--p). They then take a constant a such t h a t (3) n = aV"/V', and eliminating V' and V" from equations (1) and ( 3 ) , they obtain the equation (y - $)(n + a ) = (r' - $')a, which they write (y - b)(n + a ) = (1 - b)a, where TJ is the appa- rent compressibility of the solution, and b that of the salt. If K be the cubic conipressibility of glass, ( 5 ) y = (-1 - ~ ) / ( y ' - K ) , and = y'V' + y V " .GENERAL AND PHYSTCAL CHEMISTRY.215 I, = (v” - K)/(V - K ) . They determined 12 and y for five different concentrated solutions of sodium chloride. Two of these results they used to determine a and b by means of (4).They then found that by snbstitution in (4) the relations obtained between n and y agreed well with the experimental determinations. Assuming the formula to hold good when n becomes infinite, y will in that case be equal to b, and determining y” from ( 5 ) , they obtained values Farying from 4.7 x 10-6 to 4-8 x 10-6, which agreed well with the value 5 x 10-6 determined directly for the solid salt. In a previous memoir, fhe author found t’hnt: (i j does not; agree with experiment, if for example -1’ were given, y” would have to be negative to give the correct value of 7. If, therefore, the compressibility of a solution is equal to the sum of the compressibilities of its constituents, the compressibility of the water of the solution must be diminished by the presence of the salt, and this is shown to be the case by Rijntgen and Schneider’s recent results.The other discrepancy the author traces to these observers having determined the value of a from two equations of the form (4), the observations then show that u and b are constants, PO that if the value of V“ calculated from (3) be substituted in (l), this equahion will naturally agree with experi- ment, since it is merely another form of (4). The value of a can, however, be obtained directly from (2) and (3), and the value thus obtained is about five times as great as before, and (1) will only bold good for this value of a, for then only does the ratio V”/V express the actual conditions. With this value of a, b is no longer found to be a constant.The author gives a numerical example, i n which Rontgen and Schneider’s value of a leads to an impossible result. He observes that as this correction does not alter the form of (4), all conclusions drawn simply from the form of this equation will still hold good. G. W. T. Dilatation and Compressibility of Liquids. By E. H. ANAGAT (Compt. rend., 105, 1120--1122).-l’he author has determined the expansion and compressibility between 0” and 50°, and 1 atmosphere and 3000 atmospheres, of water, of ether, of methyl, ethyl, propyl and ally1 alcohols, of ethyl chloride, bromide and iodide, of carbon bi- sulphide and of phosphorous chloride. I n all cases, except that of water, the coefficient of expansion dimin- ishes with increased pressure, but the rate of diminution decreases as the pressure rises, although it remains distinct eren a t 3000 atmospheres.The increase in the coefficient of expansion due to a rise of tempera- ture, likewise diminishes under increased pressure. The coefficient of expansion of ether under a pressure of 3000 atmospheres is only one- third of its value a t normal pressure, and when this liquid is compared with carbon bisulphide, i t is found that whilst under normal pressure t.he ether is much the more expansible of the two, under 2500 atmo- spheres the coefficients are identical, and under 3000 atmospheres the coefficient for carbon bisulphide is higher than that for ether. Under very high pressures, the perturbations which are observed i n the case of water, and which are due to the existence of a point, of maximum density, gradually disappear, and under 3000 atmospheres216 ABSTRACTS OF CHEMICAL PAPERS, the law of expansion of water agrees with that of other liquids (compare Abstr., 1887, 695).Compressibility of an Aqueous Solution of Ethylamine. By F. ISAMBERT (Co?npi. rend., 105,1173-1175).-The coefbcient of com- pressibility of ethylamine between 5" a n d 7" and from 8 to 4.5 atmos. is 0.000120, a value which approximates to that for ether at O", and is much higher than that for water. The compressibility of an aqueous solution of ethylairline is much lower than the value calcu- lated on the assumption that the two liquids are simply mixed, and i t decreases as the proportion of water increases. Ethylamine in fact behaves like ammonia, and this result confirms the author's conclu- sion that solutions of the amrrioniacal bases behave like true chemical compounds more or less dissociated i n presence of excess of water.The view that a compound is formed is supported by the contraction which takes place, and t,he development of heat, which as in the case of ammonia is equal to the heat of volatilisation of the amine. C. H. €3. C. H. B. Oxygen Carriers. By L. MEPER (Bey., 20, 3058-3061).- Experiments were made with various metallic salts with a view to determine their power of expediting the oxidation of sulphurous acid. The oxygen and sulphnrous acid were passed, for four hours, at as uniform a rate as possible, through the solution of known con- centration contained in a flask heated on a water-bath.The amount of sulphuric acid was then determined. The most active salt was manganous sulphate, of which 2.404 grams (JlinSO, + 5H20) was dissolved in 290 C.C. of water ; this solution in four honrs gave six times as much sulphuric acid as the salt contained. Manganous chloride is also very active ; copper sulphate. gives less sulphuric acid. After copper salts, the salts of iron and cobalt are the most active, the chlorides being more so than the sulphates. The salts of nickel, zinc, cadmi um, and magnesium produce less sulphuric acid, whilst dilute solutions of thallium and potassium salphates and free sulphuric acid produce none at all (compare Kessler, Am2. Phys. Ckem., 1863, 119, 218). N. H. M. Explosive Decomposition of Picric Acid and other Nitro- derivatives.By BERTHELOT (Contpt. rend., 105, 1159-1162).- When picric acid is heated in a capsule, it melts and gives off inflam- mable vapours, which burn with a smoky flame, but it does not ex- plode. A small quantity when heated in a closed tube can be sublimed without decomposition. If, however, the picric acid is thrown into a vessel previously strongly heated, the quantity of the solid being so small that the temperature is not materially reduced, then it decom- poses with detonation accompanied by a vivid flash of light. When the quantity of picric acid introduced is sufficient to somewhat cool the bottom of the vessel, detonation does not take place at once, but the acid is partially volatilised, and a somewhat less violent explosion follows.If t.he quantity is still larger, the acid decomposes, but them is no explosion. Similar results were obtained with mono- and di-GESERAL AND PHYSICAL CHEMISTRY. 217 nitrobenzene, and mono-, di-, and tri-nitronaphthalene. The tendency to detonate increases with the number of NO, groups. If the heat developed by combustion is carried awa,y with sufEcient rapidity, there is no deflagration or detonation, but if the heat accumulates the temperature may rise sufficiently high to prodace detonation. The heating of only a small part of the containing vessel to a high tem- perature may produce an explosive wave, which may then propagato itself through the whole mass, and thus produce an explosion. Nitro-derivatives may decompose in several different ways. C.H. B. Relative Size of the Molecules, calculated from the Elec- tric Conductivity of Salt Solutions. By G. JAGER (Honatsh., 8, 498--507).-1n this paper, an attempt is made to determine the rela- tive diameters of some of the elementary molecules and atomic group- ings, adopting as a basis for the calculations the results obtained by Kohlrausch in hi8 investigations on the electric conductivity in aqneous solutions of certain metallic hydroxides and salts. If, in such an aqueous solution, a cylindrical section is taken o€ unit dimensions, them are contained therein rn electrochemical molecules ; taking, then, the electromotive force in the direction of the axis as unity, the kathion will be propelled in the one direction with velocity U, and the anion with velocity V in the other.If B is the quantity of positive or negative electricity with which each molecule is endowed, then the coefficient of conductivity 1c = (u $- v)m where EU = u and e V = v, and the specific molecular conductivity X = u + v. But according to Hittorf v / u + ZI = n, in which n is the number of molecules passing in unit time through unit space. Hence 21 = (1 - rt)X and 21 = pzX. If the molecules of the ions pass with a certain velocity, they meet in unit time a certain number of other molecules of a different kind passing in the opposite direction ; there- fore they require a certain amount of energy to overcome the neces- sary resistance which is proportional to their rate of passage. If for the sake of simplicity the molecules are assumed to be spheres, and the solution is so dilute that there is no interaction between the mole- cules of the dissolved substance ; also if a molecule of radius r passes in a certain direction whilst the environment consists of molecules of radius p , and the number of molecules in unit volume is a, then T + p = R if the forces are resolved in two directions. The result ia the same if the radius of the moving molecule is R, whilst the mole- cules in the environment are reduced to a mathematical point.Now (1) 2r = CJR? = CJ(r + p)', in which C is a constant obtained by integration, while for another molecule (2) D' = C/(f + P ) ~ ; dividing (1) by (2) wju' = (r' + p)'/'(r + ,Q)~, from which T = (r' + p ) d v ' / v - p. To solve this equation the values for the relative velocities have been determined by Kohlrausch, whilst to find T' and p the diameters o€ the molecules of water and chlorine calculated by 0.Meyer are used. The vdues are for water d = 96 x for chlorine 6 = 44 x 10-9 ceiitimetres, while U for water = 49. Hence the diameter of a given molecule is-218 ABSTRACTS OF CHEMICAL PAPERS. expressed in 10-0 centimetres. The following rcsultn are given for the relative diametem of the elementary molecules and of certain atomic groupings arranged in order of magnitude. H. $H2. I. Br. (CN). C1. I(. (NIT,). (NO,). (c103). 15 32 91 91 95 96 97 99 100 111 +Kp *(so4). Ag- $(NH4)2- i(CO3). 9Agz. F. $Ba. 111 111 111 117 119 129 132 135 138 ~ C U . gSr. ?&a. BMg. (C-H302). SNa,. *SO4.+ Li. 3Zn. 138 141 148 160 160 165 165 170 175 *ME.* +Zn.* gCu.* &Li.+ 218 239 239 251 The values marked thus * were determined by the electric con- ductivity of magnesium, copper, and zinc sulphate.It mill be seen that the relative size of the molecules is most rariable, that of lithium, for example, being more than 16 times greater than that of hydrogen, both being expressed in linear dimen- sions. It is further to be noticed that the diameters of the double molecules of the elements, as for instance hydrogen, is greater than that of twice the single molecule, but this result would be a necessary consequence of the union of two spheres of equal volume. The elements belonging to the same family in MendelBeffs scheme, Fiuch as chlorine, bromine, iodine, or barium, strontium, and calcium, come close together in the table.If a substance is in the solid or liquid state, the number of niolecules in unit volume is directly proportional to the volume of the molecule ; multiplying this number by the molecular weight, values should be obtained proportional to the specific gravities of the elements in question, or conversely similar proportional numbers should be obtained by dividing the molecular weight by the molecular volume. However, this relation does not alwajs hold good, except in the case of certain chemically allied elements. Hence it follows that different molecules consist of ultimate particles differently arranged. V. H. V. Representation of Atoms in Space. By W. LOSSEN (Bey., 20, 3306-3310).-1f atoms be considered as material points, the tetra- hedron employed in the Vaa’t Hoe- Le Be1 hypothesis to represent the compound C(RlR2R3R4) niay be replaced by the straight lines joining the points a t the solid angles where the radicles are assumed to be situated with a point in the centre representing the carbon- atom.The attractive forces by which the radicles IL,R,R3R4 are held 1 y the carbon-atom must then act in the directions of these straight lines, the said directions being solely dependent on the positions of the atoms in space. A combination of t w o carbon-atoms is thenINORGANIC CHEMISTRY. 219 effected by an attraction acting along and represented by the straight line joining them. By such a representation, however, a double union would be in no way distinguishable from a single one, both deing denoted by a straight line joining the carbon-atonis.The author considers this to indicate R weak point in the Van’t Hoff - Le Be1 hypothesis, and one requiring explanation. He also concludes that a polyvalent atom cannot be represented as a point in space, but that various portions of such an atom having different affinities must be d is t i i i guis hed. H. C.205General and Physical Chemistry,Chemical Action of Light on an Explosive Mixture of Chlo-rine and Hydrogen. 'By E. PRINGSHEIM (Ann. Phys. Chem. [2], 32,384-428).-Bunsen and Roscoe (Ann. Phys. Chem., 96, 373 ; 100,43,481; 101, 235; 108, 193; 117, 529) propounded the question-" Whether in photochemical combination an amount of work is donefor which an equivalent of luminous energy disappears, o r whetherthe action effected by the chemical rays is merely started by thelight without the expenditure of a sensible amount of luminousenergy." They endeavoured to solve this problem in the case ofhydrogen and chlorine, by comparing the quantity of light absorbedby the mixture with that absorbed by dry chlorine, or as they call it,the opt,ical extinction in chlorine.They assomed that this opticalextinction would be of the same amount in the mixture, and thereforeconcluded that the considerable additional extinction observed in themixture was due to the transformation of luminous energy into heatenergy during the chemical action. The author objects to thiqreasoning, that the light absorbed in chlorine alone is itself trnns-formed into heat, thereby raising the temperature of the gas, whilstin the case of the mixture, the luminous energy may very probably betransformed directly intg chemical energy. In support of this view,he adduces Bunsen and Roscoe's observation that the action of lightwas considerable when the range of temperature was from 18" to26".The luminous energy, indeed, may either increase the molecularmotion directly and the atomic motion indirectly, or vice tiers$, G rmore probably hoth processes may go on simultaneously.From thekinetic theory of gases, the introduction of energy by conduction ofheat mnst increase the molecular velocities, which are of rt very irre-gular character. Now it is found that the absorption of light is afunction of the wave-length,.and i t therefore seems qrobable that, thechemical action of light consists in the direct transfer of energy tothe atoms, whose motions consist of vibrations of definite periods, andis therefore the direct cause of dissociation. When in equilibrium,there is a definite relation between the atomic and the molecularenergy OF a gas, and if this is disturbed by the absorption of light,there will be a change in the number of molecular impacts, and beforeA fresh state of equilibrium is attained, the direct increase in theatomic energ7 may be more or less expended ; in the present case ineffecting chemical change ; in other cases, in producing fluorescence,phosphorescence, or electrical phenomena. The assumption, therefore,that what Bunsen and Roscoe call the optically absorbed light simplyincreases the temperature, and that the additional absorption due tothe presence of hydrogen increases the chemical absorption, is notjustifiable.If the light absorbed by the chlorine molecules in themixture produces chemical action, this, as shown later, will probablyP TOL. LIT206 ABSTRACTS OF CHEMICAL PAPERS.consist i n the formation of intermediate unstable products whosecoefficient of absorption of light differs from that of the mixture ofchlorine and hvdrogen, so that “ chemical extinction” must beregarded as the consequenco rather than the cause of the chemicalchange. The existence of chemical extinction is therefore no criterionas to whether transformation of luminous into chemical energy takesplace, SO that Bunsen and Roscoe’s method is incapable of solving thequestion proposed by them, but a result obtained in another portionof their researches, namely, that the chemical action is proportionalto the intensity of the light, although not so applied by them, seemsto give tshe required solution; for if the action of the light weresimply to disturb a state of unstable equilibrium, the quantity ofhydrogen chloride formed would be independent of the initial impulse.It must, hherefore, be assumed that a definite absorption of luminousenergy will take place for every molecule of hydrogen chloride formed,but it does not follow that more light must be absorbed than with thechlorine alone,The determination of the cause of the increase of the extinction-coefficient, which may be due merely to a change in the condition ofthe mixture, leads to an investigation of the pliysical and chemicalphenomena which accompany the formation of hydrogen chloride, andtherefore to the consideration of “ Photochemical Induction.” Burmenand Roscoe found that when light falls on a freshly prepared mixture,or on one which has been for a time in darkness after previousexposure to light,, there is a t first no appreciable formation of hydrogenchloride ; after a certain interval, a, slight action begins, graduallyincreases to a maximum, and then remains constantly proportional tothe time. The act of overcoming the resistance here indicatedand bringing the gas into a state of readiness for combination, tlheycall chemical induction, and when due to the action of light, photo-chemical induction.They found the duration of the seemingly in-active interval to increase with the thickness of gas traversed by thelight, and to decrease with increasing intensity of light more rapidlythan the intensity increases. Both of these results are confirmed bythe author, who further finds that the rate of formation of hydrogeiichloride depends only on the intensity, and not on the wave-length ofthe light, from which he concludes that the inductive action is pro-bably a chemical one. By instantaneous exposure to a strongersource of light, he finds that the gas undergoes a momentary expan-Rion proportional to the intensity of the light, which is evidently notdue to the heat of formation of hydrogen chloride, from the rapiditywith which it appears and disappears, and also because it is found tobe independent of previous induction and of the amount of hydrogenchloride formed.Neither can it, for the former reason, be due to theheat which Budde (Ann. Phys. Chem., 144, 213) has shown to beproduced by the absorption of light by chlorine.He therefore concludes that some intermediate product is formed,that the expansion is due to momentary dissociation, and that thequantity formed is proportional to the int’ensity of the light. It doesn o t seem reasonable to suppose that this may consist of molecules ofH2Cl and C1 or HCI, and H ; the author therefore seeks for the cause iGENERAL AND PHYSICAL CHEJlISTRT.207the presence of water-vapour (the gas being in contact with water duringthe experiments), in accordance with the influence known to be ex-cited by water-vapour on other explosive mixtures, and in confirma-tion of this he finds that when a solution of hydrogen chlorida issubstituted for the water, and the gas dried as completely n s possible,much less hydrogen chloride is formed by the action of light of givenintensity, and with the feeble light used in the earlier experiments, noaction at all takes place.The author assumes the action t o take place in two stages, forexample : -(1.) H2 + C12 + HzO = C1,O + 2H2;(2.) C120 + BH2 = 2HC1 + H20;or some similar action, the exact nature of which may be determinedby chemical analysis.He supposes the action to be Homewhat as fol-lows :-The intermediate substance is first formed, the process con-tinuing until a certain proportion of the gas is transformed. Massactions then come into play between chlorine, hydrogen, water andthe intermediate product, and hydrogen chloride begi,ns to be formed.The second stage of induction now begins. The amount of the inter-mediate product increases more rapidly than it is used up in forminghydrogen chloride, which is therefore formed a t an increasing rate,until the intermediate product is destroyed as fast as it is produced,introducing the third stage, in which the formation of hydrogenchloride is proportional to the time. When removed from the actionof light, the quantity of intermediate product will soon fall below theminimum required for the production of hydrogen chloride, and theremainder will break np again into hydrogen, chlorine, and water.This gradual decomposition of the intermediate product into itsoriginal coiistituents will go on even during induction, which explainswhy, with diminishing intensity of light, the duration of inductionincreases more rapidly than the intensity diminishes, for since thenature of the change undergone by the intermediate product dependson its actual amount, therefore the less the intensity the greater willbe the ratio of the amount destroyed to that newly formed in eachmoment.G. W. T’.Anomalous Dispersion produced by Glowing Vapours. ByA. WINKELMANN (Ann. Phys. Chem. [2], 32, 439--442).-Kundt(Ann.Phys. Chem. [a], 10, 231) discovered the anomalous dispersionproduced by sodium vapour. The method he used was to allow a rayof light to pass through the conical flame of a Bunsen burner colouredwith sodium vapour, so as to be refracted by the flame, which actedlike a prism wit!L its refractiug angle horizontal and upwards, andthen through a vertiral prism, by which means he obtained crossedspectra which showed the anomalous dispersion. In the hope ofmaking the action stronger, Kundt attempted, but without success, t oreduce the flame to a prismatic form by the use of glass or micaplates. The author has succeeded in doing this by using as theburner a tube of triangular section and provided with an air-blast.p 208 ABSTRACTS OF CHEMICAL PAPERS.On the top of the tube is placed a double thickness of wire-gauze,and on that again a triangular support smaller than the section of theburner, made of iron wire, which carries an iron cup of the samedimensions as the support, in which the sodium is placed.With this apparatus Rundt’s phenomenon was exhibited veryclearly, and it was also obtained, although less distinctly, with potas-sium.Lithium and thallium chlorides were also tried but withnegative results ; this the author attributes to the insufficient densityof -the vapour. G. W. T.Components of the Rare Earths yielding Absorption-spectra.By G. KR%S and L. F. NILSON (Ber., 20, 3067--3072).-A reply toG. H. Bailey (this vol., p. 1)’ in which the authors maintain the cor-rectness of their views on the components of the rare earths (Abstr.,1887, 890).Components of the Rare Earths yielding Absorption-spectra.By G.H. BAILEY (Ber., 20, 3325--3327).-A rejoinder to the pre-ceding Abstract.Theory of Researches on Contact-electricity. By F. EXNER(Ann. Phys. Chenz. [2], 32, 515--520).-The author’s recent re-searches in support of his denial of contact-electrification (Ann. Phys.Chem. [2], 32, 53) were founded on his experimental result, that if aninsulated conductor is connected with an electrometer, and the latterthen disconnected from the earth, and if the capacity of the con-ductor is then altered, the electrometer will remain unaffected, whilstaccording to the contact-theory there should be a flow of electricity.The present note is a reply to objections which Hallwachs (ibid.,64) has advanced against the author’s conclusions.In reply to these objections he states that-(1.) The potential of the grating of oxidised iron which surroundedthe apparatus differed by less than 0.05 of a, Daniel1 from that of thewalls of the room, which would justify his neglecting it; moreover,from (4), its potential, whatever its value, would be without influenceon the results.(2.) The capacity of the conductor was measured inside the grating,and not outside as assumed by Hdlwachs.(3.) He is justified in neglecting the change of capacity in thequadrants during the movement of the needle, since for the maximumdeflection to be expected the error so arising would not exceed 1 percent., and as no deflection was observed, the objection is entirely irrele-vallt.(4.) The potentials would aatnrally be understood to refer to thatof the grating as zero, without an express statement to that effect;moreover, the author shows by a simple mathematical proof that theresult is independent of the absolute values of the potential, theessence of his method consisting in eliminating the influence of thegrating by comparative observations on different metals.The dif-ference of deflections which should hare been obtained accordiiig tGENERAL AND PHYSICAL CHEMISTRY. 209the coiltact-theory would have amounted to from 10 to 15 scale-divi-Bions, and would therefore be easily observed.(5.) To eliminate the possibility that t’he absence of a deflectionmight be due to unknown external effects, a Daniell’s cell was intro-duced into the insulated system, and the deflection obtained was foundto agree closely with the value predicted theoretically.(6.) The author claims that he has proved that no change is pro-duced when the grating is brought into contact with a conductor con-sisting of a different metal.Such a change is required by the contact-theory, but the author has not attempted to determine whether itwould be required by the chemical theory, nor, as far as he is aware,has the question been considered by others.Resolution of the Electromotive Forces’of Galvanic Elementsinto their Differences of Potential. By J. MOSER (Monatsh., 8,508--509.)--Examples are given in this paper of the resolution of theelectromotive forces of certain galvanic combinations, and determinn-tion of each of the components at the electrolytic surface.The sumof these several components is shown t o be equal to the total electro-motive force of the cell. The method of “drop electrodes,” as appliedby the author to exclude the electromotive force of contact metals, isused, a method based upon an observation of Helmholtz, that if a ninsulated mass of mercury, dropping quickly, is in contact with anelectrolyte at the dropping point, there is no difference of potentialbetween the mercury and the electrolyte.Thus the total electromotive force of the combination Zn I diluteZnC1, [ concentrated ZnClz I Zn = 0.15 volt. The values of theelectromotive force a t the three surfaces v, J; and c, were found bythe drop electrode method to be-G. W.T.21 = 1.1 voltc = 0.98 andf = 0.27f + c = 0.95.Now 1.1 - 0.95 = 0.15, or the value found for the total electro-Again taking the Daniell’s cell as another example-motive force.total electromotive force = 232 - 40 Zn I ZnS04 I CuSO4Zn I ZnSO1c u I G U S 0 4 = 40a value agreeing with that obtained by direct observation. A similaragreement between the sum of the differences of potential and thetotal electromotive force in the Lakimer-Clark’s cell is also noticed.V. H. V.Property of the Alkalis of increasing the E.M.F. of Zinc.By J. H. KOOSEN (Ann. Phys. Chent. [Z), 32, 508-515).-Grove,Joule, Poggendorff, and others have observed the increased E.M.F.obtained by substituting aqueous potash or soda for the dilute acid inn cell.The author states that according to his researches the alkali,say potassium hydroxide, has a four-fold action: (1) it breaks u210 ABSTRACTS OF CHEMICAL PAPERS.into potassium and oxygen ; (2) potassium replaces zinc in its elec-trical action, for instance, in a Daniell’s cell potassium sulphate isformed in place of zinc sulphate, as the copper is deposited ; (3) thezinc is oxidised by the oxygen of the potash; (4) the resultingzinc oxide is dissolved by the aqueous potash. (1) Diminishes theE.M.F., whilst (2) and (3) increase i t ; (4j may possibly slightlyincrease it, but it would be desirable to have positive evidence on thispoint.If the external resistance of a cell is very great, almost the wholeheat of combination will be developed in the external circuit..Letthe E.M.F. of a Daniell’s cell be taken as the unit of E.M.F., and letthe unit of heat be the amount generated in a Daniell’s cell by thedecomposition of n grams of zinc, where n is the atomic weight ofthat metal. Then from Thomsen’s determinations, the E.M.F. of aDaniell’s cell is given by the equation ZnS0,(248) - CuSOa(198) =50 = 1 Daniell; and with potash substituted for dilute sulphuricacid, K,S04(337) + 2ZnOH20(166) - 2KH0(232) - CuS04(198) =73 = 1.46 Daniell. For the author’s zinc-bromine-platinum cell,ZnBr2(91) = 1.82 Daniell.The results thus thoretically obtained in the case of these and afew other simple cells considered by the author agree closely withexperimental determinations.The heat of combustion of zinc oxideand potassium is not taken into account, as it is certainly not morethan 2 per cent. of that due to the decomposition of zinc in a Daniell’scell, and according t o Favre and Silbermann it would seem that th’schemical action is merely local, and does not contribute to theelectrical energy. Practically the author finds that a Daniell’s cellwith a solution of potassium hydroxide is very satisfactory for givingcontinuous currents through a high resistance, and sodium hydroxidegives still better results, as sodium sulphate, being more soluble, doesnot so readily crystallise on the porous cell.I t is very important to prevent interdiffusion of the fluids as far aspossible, and for this purpose the author uses a double porous cell,having the intermediate space filled with a solution of potassium andsodium sulphates respectively, with a small admixture of sulphuricacid to diminish the resistance.Cells of this kind have been keptjoined up through a resistance of 20 or 30 ohms for weeks togetherwithout any perceptible diminution in the E.R.I.F. The alkalinesolution must not be too dilute or the zinc will soon become coatedwith oxide.The author stmates that his zinc-bromine-platinum cell is still betterfor giving a continuous current through a high resistance. It re-quires no porous cell, has a high E.M.E., and has been kept in con-tinuous action for months withont any change in the E.M.F., in fa(+until one or other of the elements was completely decomposed.Theonly precaution necessary is to cover the bromine with a layer ofpetroleum, which completely prevents all evaporation and smell.G. W. T.Electrolytic Formation of Hydrogen Peroxide at the Anode.By M. TRAUBE (Ber., 20, 3345--3351).-From the results of previouGENERAL AND PHYSICAL CHEJIISTHY. 211cxperirnents (Abstr., 1885, 1108), i t was concluded that hydrogenperoxide is formed by the union of molecular oxygen with hydrogen.Richarz, on the other hand (this vol., p. 11). maint'ains that thathydrogen peroxide is produced by the oxidation of water.When 1 per cent. sulphuric acid is electrolysed in presence ofalcohol or hydrogen peroxide a t the anode, these are rapidly oxidised.I n the electrolysis of a 1 per cent.solutionof chrome alum, not a traceof ozone is formed, and chromic acid appears at the anode. Whenlead is used as anode in the electrolysis of 1 per cent. sulphuric acid,i t becomes covered with lead peroxide. These experiments point tothe presence of free oxygen-atoms which only unite to passive mole-cules when there is nothing to oxidise, and a.lso show that water isnot oxidised by oxygen-atoms. I n the electrolysis of sulphuric acid,it is suggested tliatl persulphriric acid is formed by the action ofnascent oxygen, and that this decomposes into sulphuric acid (2 mols.)and hydrogen peroxide ( 1 mol.).As further proof in favour of the constitution previously ascribedt o hydrogen peroxide (Abstr., 1886, 660), it is mentioned that theporoxides of hydrogen, of the alkalis and alkaline earths, of zinc,cadmium, and copper, have quite different chemical properties fromthose of lead, silver, manganese, and nickel, &c.Only those of thefirst group yield hydrogen peroxide when trea,ted with acids. Theperoxides of the second group can all be prepared by oxidising theoxides or hydroxides in alkaline solution. The peroxides of the firstgroup possess powerful reducing properties, whilst those of the secondgroup are indifferent to oxidising agents. Hence it, is concluded thatthe peroxides OF the two groups are differently constituted, and thathydrogen peroxides cannot have the formula HO-OH. The con-stitution represented by the formula H*O : 0.H is considered to bethe only one possible.N. H. M.Electrolytic Conductivity of Halogen-compounds. By W.HAMPE (Ckem. Zeit., 11, 816; 846-847 ; 904-905; 93.1f-935 ; 1109-1110 ; 1158).-Pure dry sa1t.s fused in hard glass tubes or porcelaincrucibles, o r dissolved in dry ether or absolute alcohol, weTe submittedto a current from eight large Buusen chromic acid cells, platinumelectrodes being used when the conditions of experiment permitted.The following salts proved good electrolytes i n a state of fusion:-A11 6he haloid salts of lidhiurn, sodium, potassium, rubidium, andcmium, beryllium chloride, magnesium chloride and bromide, stron-tium and calcium chlorides and bromides (part of the liberated metalscombining with the silica of tlie glass or porcelain), barium chloride,lanthanum, didymium, and cerium chlorides (this confirms Hillebrandand Norton's experience), indium chloride, thallous and cuprouschlorides (thallic and cupric chlorides decompose when fused), tantalumchloride, and thorium chloride, although the latter is not suitablefor electrolysis, as the melting and boiling points are near togetherI n concentrated alcoholic solutions, cupric chloride behaves as aiielectrolyte. Gold chloride in carbon bisulphide is a non-conductor ;when mixed with ether a pasty mass forms, and the supernatan212 ABSTRACTS OF CHEMICAL PAPERS.liquid gradually deposits gold ; this liquid conducts slightly, and after15 minutes the negative pole becomes gilded.Aqueous solutions ofgold chloride owe t'heir electrolytic conductivity to the presence ofhydrochloric acid. Zinc and cadmium iodides, bromides, and chloridesare good electrolytes when fused, but their conductivity ceases on solidi-fication.I n concentrated solutions, these salts conduct well, in weaksolutions badly; in absolute alcohol all, but only zinc chloride andbromide dissolve iu ether and conduct well, whilst the other salts dis-solve in ether and conduct only sparingly or not at all. Fused mer-curic chloride, bromide, and iodide are feeble electrolytes, especiallythe first; in solution in ether, none conduct, owing probably tosparing solubility ; in absolute alcohol, they conduct slightly ; betterwhen the solution is hot than when it is cold.Mercurous chloridefused in closed glass vessels proved electrolytic. Aqueous solutionsof mercuric chloride conduct badly at first, with deposition of mercuryand mercurous chloride, and evolution of oxygen and chlorine ; sub-sequently mercury only is deposited, and the electrolysis proceeds ata quicker rate ; i n this case the current in the first instance produceselectrolytes (hydrochloric acid for instance), and when these arepresent in abundance the process goes well.Fused gallous chloride is a very good conductor, globules of metalReparate at the negative pole, but the chlorine a t the positive pole corn-bines with the gallous chloride to form gallic chloride ; the latter isiiot such a good conductor as gallous chloride, no metal separates,evidently owing to its entering into combination with the gallicahloride to form gallous chloride.S tannic chloride does not conduct;when electrolysed in aqueous solution the hydrochloric acid only con-duct,s, the tin being set free by the hydrogen (Hittorf hag stated thecontrary). Fused stannous chloride on the other hand is an excellentelectrolytic conductor, the current continues to pass even on coolinga3 long as the mass remains soft, but ceases to flow when the chlorideiii solid. Fused lead chloride, broniide, and iodide conduct very wellwith vigorous decompositiori, and, unlike the other salts examined,metallic, Wiedermann regarded it as electrolytic ; the author confirmsthe latter view. At ordinary temperatures, no current passes throughthe cold fused lead salts; it is first observed to flow at 110" throuphthe chloride, at 115" through the bromide, and a t 159" through theiodide, the conductivity then increases as the temperature rises, inthe manner usual with electrolytes.The trihaloyd compounds ofantimony in a fused state behaye as feeble electrolytes, the tri-iodideIieing the best; but in carbon bisulphide solutions they do not con-duct electricity. Vanadium tetra- and tri-chlorides do not conduct,but when decomposed with water the solutions electrolyse, but inlieither case is the metal deposited. The following aye non-con-ductors :-Fusea aluminium chloride or bromide (Buff's statement to-the contrary is probably based on experimerits with impure chloride),boron chloride, titanium and silicon tetrachlorides and bromides,vanadyl chloride, niobium pentachloride, all the haloid compoundsof phosphorus, arsenic trichloride, and antimony pentachloride.Yttrium and zirconium chlorides sublime without melting, and when+Jiitq Z~mi!U~~i" a h a wJ,:rt,; BL% cbarw?iu&fi+u Wfi C-ddUciPfGENERAL AND PHYSICAL CHEMISTRY. 213+he former is dissolved in water it conduct,s on account of the hydro-chloric acid, but no metal is deposited ; the latter is a non-conductor ;titanium hexa- and di-chlorides are infusible solids, so do not comeunder consideration, D.A. L.Molecular Heats of Gases. By H. LE CHATELIER (BUZZ. HOG.Chim., 48, 122--124).-The fact that the curves of the specific heatsof carbonic anhydride and water vapour converge to a point belowzero, leads to the supposition that molecular heats of all gases tend tohhe same limit as the temperature approaches absolute zero.Theauthor has compared the specific heats, calculated on this assumption,with the actual determinations of Wiedemann. The specific heats canbe represented by the expression C = 6-8 + r ~ [ 3 7 3 + t ] , a being aconstant which depends on the nature of the gas and has a highervalue the more complex the molecule. The numbers calculated bythis equation differ from the actual numbers by quantities less thanthe experimental errors. A similar agreement is found between thenumbers for carbonic anhydride at high temperatures deduced fromkhis equation and the actual numbers obtained by the author andMallard.C. H. B.Influence of Small Amounts of Impurities on the Vapour-tension of Liquids. By G. TAMMAN ( A ~ L Phys. Chena. [Pj, 32,683--699).--The increase in the vapour-tension of a liquid observedby Wiillner and Grotrian (Ann. Phys. Chew,. [2], 11, 545), when thespace occupied by its vapour in the manometer has been decreased bycompression, and attributed by them t o a dependence of the tensionon the amount of liquid in contact with the vapour, is shown to becaused and brought about by traces of impurity in the liquid. Thesetraces are often so exceedingly small as not to be recognisable by theurdidary tests. But the vapour, if containing this impurity, consistsof a mixture of two substances one of which is more volatile than theother, so that compression causing a greater condensation of the less3-olatile, causes a rise in the vapour-tension, and expansion has justthe opposite eeect.A difference is therefore observed between thetension measured after compression and after expansion. This diffe-rence is reduced in magnitude by purifica.tion of the liquid used, butcould not in any case be entirely eliminated, although an approxima-tion to a constqnt tension was reached in the case of water. Ameasurement of the vapour-tension, once after compression and onceafter expansion, will give a, rough measure of the purity of the sub-stance used. Experiments are given with water, ether, carbonbisulphide, benzene, methyl and ethyl alcohols, chloroform and aceticacid. H.C.Dissociation of Crystallised Lead Acetate and SodiumThiosulphate. By W. M~LLER-ERZBACH (Ber., 20, 2974-%81) .-Two series of experiments were made with lead acetate. In the firstseries, large crystals of the commercial salt were employed in the state ofpowder, and with it the relative tension was 0.27 to 0.38 at temperaturesvarying between 12.5" and 21.8" ; whilst in the second series, in whic214 ABSTRACTS OF CHEIlICdL PAPER.S.small crystals OF the pure salt were used, the relative tension was0.32 to 0.39 a t 149-24*3"; the valiie of tl - t2, which the authorassumes to be a measure of the attraction between the aalt and itswater of crystallisation (compare Abstr., 1887, 628), decreasing with+,he rise of temperature. A partially dehydrated specimen of thesalt containing about 8 mol.H,O, when placed in a moist atmosphereuntil water equal in amount to 3 mols. had been absorbed, showeda higher and less constant relative tension, the highest value being0.485 a t 21.5".Wit,h sodium thiosulphate, Na2S2O3 + 5H,O, two series of experi-ments were also made, and in the first eeries 3 mols. H,O were lostwith a relative tension = 0.33 to 0.36 a t 29*1-32.9", and a, further1-4 mol. with a relative tension = 0.17 to 0.22 a t 31-7--34-2", theremainder of the water being given off with a relative tension =0.047 to 0.053 a t 50.6-52.7". The second series of experimentsshowed that, 3 mols. were lost with a relative tension = 0.26 to 028 at18*3-21*6", that a fnrther 1.4 mol.was lost with a relative tension= 0-G8 to 0.12 at 15.9-22.1", and that the tension became imper-ceptible when the salt contained 0.6 mol. H20. The partially dehy-drated salt, containing 2 mols. H,O, exposed in a moist atmosphereuntil i t contained 4.75 mols. H20, lost 2.55 mols. with a relative tension= 0.29 to 0.31 a t 23.6-25.9", and the salt with 2 mols. H,O, obtainedin like manner from the salt + 0.49 mol. H20, lost approximately1.5 mol. with a relative tension = 0.10 to 0.19 at 5.3-16.1". It wasfound, however, that when sodium thiosulphate was heat,ed to driveoff the water of crystallisation rapidly and then exposed to moist airuntil 4.9 mols. H,O had been taken up, it lost the whole of the waterwith a relative tension = 0.21 to 0.32 a t 15.8-30.6.W. P. W.Relation between the Compressibility of a Solution and theCompressibilities of its Constituent Parts. By F. RRAUN (Ann.Phys. Chem. [Z], 32, 504-5508).-Rontgen and Schneider (this vol.,p. 22) have given for the compressibility of rock-salt the value5 x 10-6, which does not agree with the author's previous determina-tion (Abstr., 1887, 436), which gave 1.4 x 10-6 This result wasohtained by comparatively rough methods, but the author points outthat it agrees very closely with the value 1.6 x 10-6, deduced fromVoigt's determination (Ann. Phys. Ohem. h'rgbd., 7, 214) of its twocoetiicients of elasticity.Rontgen and Schneider assume that if y be the compressibility of asolution containing per unit volume a volume V' of water, and V" ofsalt, and if y' be the compressibility of water and y" that of the salt;,then (1) Now if n be the number of molecules ina solution containing a percentage p of salt of molecular weight m,then (2) n = 10~p/m(100--p).They then take a constant a sucht h a t (3) n = aV"/V', and eliminating V' and V" from equations (1)and ( 3 ) , they obtain the equation (y - $)(n + a ) = (r' - $')a,which they write (y - b)(n + a ) = (1 - b)a, where TJ is the appa-rent compressibility of the solution, and b that of the salt. If K bethe cubic conipressibility of glass, ( 5 ) y = (-1 - ~ ) / ( y ' - K ) , and= y'V' + y V " GENERAL AND PHYSTCAL CHEMISTRY. 215I, = (v” - K)/(V - K ) . They determined 12 and y for five differentconcentrated solutions of sodium chloride.Two of these results theyused to determine a and b by means of (4). They then found that bysnbstitution in (4) the relations obtained between n and y agreed wellwith the experimental determinations. Assuming the formula to holdgood when n becomes infinite, y will in that case be equal to b, anddetermining y” from ( 5 ) , they obtained values Farying from 4.7 x10-6 to 4-8 x 10-6, which agreed well with the value 5 x 10-6determined directly for the solid salt.In a previous memoir, fhe author found t’hnt: (i j does not; agree withexperiment, if for example -1’ were given, y” would have to be negativeto give the correct value of 7. If, therefore, the compressibility of asolution is equal to the sum of the compressibilities of its constituents,the compressibility of the water of the solution must be diminishedby the presence of the salt, and this is shown to be the case byRijntgen and Schneider’s recent results.The other discrepancy theauthor traces to these observers having determined the value of afrom two equations of the form (4), the observations then show thatu and b are constants, PO that if the value of V“ calculated from (3)be substituted in (l), this equahion will naturally agree with experi-ment, since it is merely another form of (4). The value of a can,however, be obtained directly from (2) and (3), and the value thusobtained is about five times as great as before, and (1) will only boldgood for this value of a, for then only does the ratio V”/V expressthe actual conditions.With this value of a, b is no longer found tobe a constant. The author gives a numerical example, i n whichRontgen and Schneider’s value of a leads to an impossible result.He observes that as this correction does not alter the form of (4), allconclusions drawn simply from the form of this equation will stillhold good. G. W. T.Dilatation and Compressibility of Liquids. By E. H. ANAGAT(Compt. rend., 105, 1120--1122).-l’he author has determined theexpansion and compressibility between 0” and 50°, and 1 atmosphereand 3000 atmospheres, of water, of ether, of methyl, ethyl, propyl andally1 alcohols, of ethyl chloride, bromide and iodide, of carbon bi-sulphide and of phosphorous chloride.I n all cases, except that of water, the coefficient of expansion dimin-ishes with increased pressure, but the rate of diminution decreases as thepressure rises, although it remains distinct eren a t 3000 atmospheres.The increase in the coefficient of expansion due to a rise of tempera-ture, likewise diminishes under increased pressure.The coefficient ofexpansion of ether under a pressure of 3000 atmospheres is only one-third of its value a t normal pressure, and when this liquid is comparedwith carbon bisulphide, i t is found that whilst under normal pressuret.he ether is much the more expansible of the two, under 2500 atmo-spheres the coefficients are identical, and under 3000 atmospheres thecoefficient for carbon bisulphide is higher than that for ether.Under very high pressures, the perturbations which are observed i nthe case of water, and which are due to the existence of a point, ofmaximum density, gradually disappear, and under 3000 atmosphere216 ABSTRACTS OF CHEMICAL PAPERS,the law of expansion of water agrees with that of other liquids(compare Abstr., 1887, 695).Compressibility of an Aqueous Solution of Ethylamine.ByF. ISAMBERT (Co?npi. rend., 105,1173-1175).-The coefbcient of com-pressibility of ethylamine between 5" a n d 7" and from 8 to 4.5 atmos.is 0.000120, a value which approximates to that for ether at O", andis much higher than that for water. The compressibility of anaqueous solution of ethylairline is much lower than the value calcu-lated on the assumption that the two liquids are simply mixed, and i tdecreases as the proportion of water increases.Ethylamine in factbehaves like ammonia, and this result confirms the author's conclu-sion that solutions of the amrrioniacal bases behave like true chemicalcompounds more or less dissociated i n presence of excess of water.The view that a compound is formed is supported by the contractionwhich takes place, and t,he development of heat, which as in the caseof ammonia is equal to the heat of volatilisation of the amine.C. H. €3.C. H. B.Oxygen Carriers. By L. MEPER (Bey., 20, 3058-3061).-Experiments were made with various metallic salts with a view todetermine their power of expediting the oxidation of sulphurousacid. The oxygen and sulphnrous acid were passed, for four hours,at as uniform a rate as possible, through the solution of known con-centration contained in a flask heated on a water-bath.The amountof sulphuric acid was then determined.The most active salt was manganous sulphate, of which 2.404 grams(JlinSO, + 5H20) was dissolved in 290 C.C. of water ; this solution infour honrs gave six times as much sulphuric acid as the salt contained.Manganous chloride is also very active ; copper sulphate. gives lesssulphuric acid. After copper salts, the salts of iron and cobalt arethe most active, the chlorides being more so than the sulphates. Thesalts of nickel, zinc, cadmi um, and magnesium produce less sulphuricacid, whilst dilute solutions of thallium and potassium salphates andfree sulphuric acid produce none at all (compare Kessler, Am2.Phys.Ckem., 1863, 119, 218). N. H. M.Explosive Decomposition of Picric Acid and other Nitro-derivatives. By BERTHELOT (Contpt. rend., 105, 1159-1162).-When picric acid is heated in a capsule, it melts and gives off inflam-mable vapours, which burn with a smoky flame, but it does not ex-plode. A small quantity when heated in a closed tube can be sublimedwithout decomposition. If, however, the picric acid is thrown into avessel previously strongly heated, the quantity of the solid being sosmall that the temperature is not materially reduced, then it decom-poses with detonation accompanied by a vivid flash of light. Whenthe quantity of picric acid introduced is sufficient to somewhat coolthe bottom of the vessel, detonation does not take place at once, butthe acid is partially volatilised, and a somewhat less violent explosionfollows.If t.he quantity is still larger, the acid decomposes, but themis no explosion. Similar results were obtained with mono- and diGESERAL AND PHYSICAL CHEMISTRY. 217nitrobenzene, and mono-, di-, and tri-nitronaphthalene. The tendencyto detonate increases with the number of NO, groups.If theheat developed by combustion is carried awa,y with sufEcient rapidity,there is no deflagration or detonation, but if the heat accumulates thetemperature may rise sufficiently high to prodace detonation. Theheating of only a small part of the containing vessel to a high tem-perature may produce an explosive wave, which may then propagatoitself through the whole mass, and thus produce an explosion.Nitro-derivatives may decompose in several different ways.C.H. B.Relative Size of the Molecules, calculated from the Elec-tric Conductivity of Salt Solutions. By G. JAGER (Honatsh., 8,498--507).-1n this paper, an attempt is made to determine the rela-tive diameters of some of the elementary molecules and atomic group-ings, adopting as a basis for the calculations the results obtained byKohlrausch in hi8 investigations on the electric conductivity inaqneous solutions of certain metallic hydroxides and salts.If, in such an aqueous solution, a cylindrical section is taken o€ unitdimensions, them are contained therein rn electrochemical molecules ;taking, then, the electromotive force in the direction of the axis asunity, the kathion will be propelled in the one direction with velocityU, and the anion with velocity V in the other.If B is the quantityof positive or negative electricity with which each molecule isendowed, then the coefficient of conductivity 1c = (u $- v)m whereEU = u and e V = v, and the specific molecular conductivity X =u + v. But according to Hittorf v / u + ZI = n, in which n is thenumber of molecules passing in unit time through unit space. Hence21 = (1 - rt)X and 21 = pzX. If the molecules of the ions pass with acertain velocity, they meet in unit time a certain number of othermolecules of a different kind passing in the opposite direction ; there-fore they require a certain amount of energy to overcome the neces-sary resistance which is proportional to their rate of passage.If forthe sake of simplicity the molecules are assumed to be spheres, andthe solution is so dilute that there is no interaction between the mole-cules of the dissolved substance ; also if a molecule of radius r passes ina certain direction whilst the environment consists of molecules ofradius p , and the number of molecules in unit volume is a, thenT + p = R if the forces are resolved in two directions. The result iathe same if the radius of the moving molecule is R, whilst the mole-cules in the environment are reduced to a mathematical point.Now (1) 2r = CJR? = CJ(r + p)', in which C is a constant obtainedby integration, while for another molecule (2) D' = C/(f + P ) ~ ;dividing (1) by (2) wju' = (r' + p)'/'(r + ,Q)~, from which T =(r' + p ) d v ' / v - p. To solve this equation the values for the relativevelocities have been determined by Kohlrausch, whilst to find T' and pthe diameters o€ the molecules of water and chlorine calculated by0. Meyer are used. The vdues are for water d = 96 x forchlorine 6 = 44 x 10-9 ceiitimetres, while U for water = 49. Hencethe diameter of a given molecule is218 ABSTRACTS OF CHEMICAL PAPERS.expressed in 10-0 centimetres. The following rcsultn are given forthe relative diametem of the elementary molecules and of certainatomic groupings arranged in order of magnitude.H. $H2. I. Br. (CN). C1. I(. (NIT,). (NO,). (c103).15 32 91 91 95 96 97 99 100 111+Kp *(so4). Ag- $(NH4)2- i(CO3). 9Agz. F. $Ba.111 111 111 117 119 129 132 135 138~ C U . gSr. ?&a. BMg. (C-H302). SNa,. *SO4.+ Li. 3Zn.138 141 148 160 160 165 165 170 175*ME.* +Zn.* gCu.* &Li.+218 239 239 251The values marked thus * were determined by the electric con-ductivity of magnesium, copper, and zinc sulphate.It mill be seen that the relative size of the molecules is mostrariable, that of lithium, for example, being more than 16 timesgreater than that of hydrogen, both being expressed in linear dimen-sions. It is further to be noticed that the diameters of the doublemolecules of the elements, as for instance hydrogen, is greater thanthat of twice the single molecule, but this result would be a necessaryconsequence of the union of two spheres of equal volume.The elements belonging to the same family in MendelBeffs scheme,Fiuch as chlorine, bromine, iodine, or barium, strontium, and calcium,come close together in the table. If a substance is in the solidor liquid state, the number of niolecules in unit volume is directlyproportional to the volume of the molecule ; multiplying this numberby the molecular weight, values should be obtained proportional to thespecific gravities of the elements in question, or conversely similarproportional numbers should be obtained by dividing the molecularweight by the molecular volume. However, this relation does notalwajs hold good, except in the case of certain chemically alliedelements. Hence it follows that different molecules consist of ultimateparticles differently arranged. V. H. V.Representation of Atoms in Space. By W. LOSSEN (Bey., 20,3306-3310).-1f atoms be considered as material points, the tetra-hedron employed in the Vaa’t Hoe- Le Be1 hypothesis to representthe compound C(RlR2R3R4) niay be replaced by the straight linesjoining the points a t the solid angles where the radicles are assumedto be situated with a point in the centre representing the carbon-atom. The attractive forces by which the radicles IL,R,R3R4 are held1 y the carbon-atom must then act in the directions of these straightlines, the said directions being solely dependent on the positions ofthe atoms in space. A combination of t w o carbon-atoms is theINORGANIC CHEMISTRY. 219effected by an attraction acting along and represented by the straightline joining them. By such a representation, however, a doubleunion would be in no way distinguishable from a single one, bothdeing denoted by a straight line joining the carbon-atonis. Theauthor considers this to indicate R weak point in the Van’t Hoff - Le Be1hypothesis, and one requiring explanation. He also concludes that apolyvalent atom cannot be represented as a point in space, but thatvarious portions of such an atom having different affinities must bed is t i i i guis hed. H. C

ISSN:0368-1769    

DOI:10.1039/CA8885400205

出版商:RSC    

年代:1888

数据来源: RSC

摘要:

INORGANIC CHEMISTRY. 219 I n o r g a n i c Chemistry. Preparation of Hydrogen Iodide. By L. MEYER (Ber., 20, 3381--3383).-100 parts of iodine contained in a retort are moistened with about 10 parts of water. The retort is then fitted with a funnel closed with a glass rod, containing 5 parts of amorphous phosphorus mixed with 10 parts of water. One drop of water containing pbos- phorus is let into the retort; more phosphorus is slowly added, after which large amounts may be added. The mixing is completed in a quarter of an hour. I f more than a drop is added a t first, the action cannot be controlled, and will generally result in a violent explosion. No heating is necessary. The iodine carried over by the hydrogen iodide is nearly all deposited in the neck of the retort, which is inclined upwards.By using 100 grams of iodine, 5 grams of phosphorus, and 25 C.C. of water, 95 grams of hydrogen iodide (of which 37.5 grams were obtained by- distillation) were obtained, instead of 1C0.8 grams. With 20 grams of water 98.1 grams were obtained (74.4 grams as gas and 23.7 grams by distillation), N. H. M. Products and Rate of Decomposition of the Salts of the Halogen Oxy-acids by Heat. By A. POTILITZIN (Chem. Centr., 1887, 1218, from J. Russ. Chem. Soc., 1887, 339-357).-Between 330" and 400°, barium chlornte decomposes entirely according to the equation 2Ba(ClO,), = BaC1, + Ba(C104), + 40. Between 400" and 470", barium chloride and oxygen are the only products. The rate of the decomposition rises with the temperature up to 400", whilst if the temperature remains constant, the decomposition rises a t first, and then gradually falls again, ahhough it is not complete.According to the author, barium chlorate decomposes to some extent before it melts, Barium perchlorate crystallises with 3 mols. HzO, whereas Marignac gives the formula Ba(C10& + 4H,O; also, contrary to Narignac's statement, it is not hygroscopic. It loses 2 mols. H,O by remaining over sulphuric acid, and the third molecule is expelled at 100". Barium bromate becomes anhydrous at 170°, the crystals turning220 ABSTRACTS OF CEEMICAL PAPERS. slightly yellow, without, however, losing their crystalline form or lustre. Decomposition begins at 260", and at 300" bromine i8 evolved. The decomposition becomes complete without tho salt melting.The author draws the conclusion that the bromate is changed into two isomeric salts, namely BrV0,90M (the original salt), and MBr"fi03, and that these, therefore, decompose at different rates. He could not find any perbromate in the product of decomposition. J. W. L. Mutual Displacement of the Halogens in their Compounds with Oxygen. By A. POTILITZTN (Chern. Centr., 1887, 1218-1219 ; from J, Russ. Chem. SOC., 1887, 358--364).-The author believes that these reactions are much more complex than is usually supposed. By the action of chlorine on a solution of sodium bromat,e in the dark, he obtained a mixture of sodium chloride and bromide, and byomir, and chloric acids together with free bromine. He finds that chlorine acts in the same way on potassium bromate and on barium bromate ; experiments were also made on the dry salts, when the same products seemed to be formed.Bromine was also found to act on the chlorates in the same way, although much less energetically. These reaction8 tske place much more readily in a sealed tube. Iodine and the iodates were also included in the serie8 of experiments wit,h similar results. J. W. L. Preparation of Hydrogen Sulphide Free from Arsenic, By C. WINKLER (Zeit. and. Chem., 27, 26--27).-Barinm sulphate (powdered barytes) is mixed with 25 per cent. of ground coal and 20 per cent. of common salt. The damped mixture is rammed into a clay crucible, which after drying and closing with a luted cover is heated for several hours at an incipient white heat. The product, ig in hard compact masses which dissolve completely in dilute hydro- chloric acid with a steady evolution of hydrogen snlphide. Selenites.By BOULZOUREANO (BUZZ. Soc. Chim., 48, 209-210).- Solutions of metallic salts were mixed with sodium selenite and the resulting precipitates were heated in sealed tubes at 200" with very dilute selenious acid. Ferric selenite forms small, golden-yellow prisms which separate in radiating groups. Another method consists in treating a metallic carbonate with dilute selenious acid, mixing the solution with its own volume of water, and heating in sealed tubes at 200". This was employed for the pre- paration of the cobalt, nickel, manganese, and cadmium salts. Cobalt selenite forms transparent, violet prisms, nickel selenite forms large, short, green prisms arranged in radiating groups.If the original solution is mixed with sodium selenite, yellow crystals are obtained. Manganese selenite crystallises in short, pale-red prisms or in slender, brown needles if heated beyond 230'. The cadmium salt forms long, colourless, transparent prisms, or much shorter yellow crystals if heated at about 200". Zinc seems to form a selenite crystallising in prisms. The liquid obtained by the second method was allowed to evaporate qontaneously at the ordinary temperature or in a vacuum. Cryshls 31. J. S.INOROAKIC CHEMISTRY. 221 are obtained in t.he case of cobalt and manganese. The latter yields a pink-colonred crust and the former deep violet crystals. Cupric carbonate, when treated with a warm solution of selenious acid, yields a blue precipitate of the normal selenite, and if this is heated to boiling, it is converted into green, microscopic prisms.The solii tion is bluish-green, and on cooling deposits large, green crystals, If the normal selenite is heated in sealed tubes with the carbonate and water, it yields well-defined, greenish-yellow, prismatic crystals. Sodiiim selenite and zinc sulphate in sealed tubes yield white, trans- parent crystals. C, H. B. Preparation of Hydrogen Arsenide. By A. CAVAZZI (Ohem. Centr., 1887, 1097, from Remd. Am. Bologna, 1886-87, 85-86).- The action of zinc on an acid solution of arsenious acid produces a gas containing 70 per cent. by volume of hydrogen arsenide. Sodium amalgam containing not more than 4 grams of sodium in 50 C.C. of mercury, by its action on a concentrated solution of arsenious acid, pra- duces a gas containing 86 per cent.by volume of hydrogen arsenide, A gas containing a large qnantity of arsenic may be prepared by the action of aluminium on a somewhat dilute alkaline solution of pot'assiurn arsenite, whilst a solution of arsenic disulphide in potash, when subjected to the action of aluminium, evolves a gas quite free from arsenic. J. W. b. Action of Hydrogen Arsenide on Arsenious Acid. By D. TIVOL~ (Chem. Centr., 1887, 1097, from Rend. Acc, BoZogna, 188647, 98) .-The reactions of hydrogen arsenide on arsenious acid dissolved in hydrochloric and sulphuric acid respectively are expressed by the equations :-2dsH, + 2AsC1, = 6HC1 + As4 and 3(As02)S0, + H,S04 + 6AsH3 = 3As4 + 4K2S04 + 68,O.The precipitation of the arsenic does not take place in neutral solutions, whereas in the hydrochloric acid solution it is complete, and in the sulphuric acid solution almost so. J. w. L. Lowest Compounds of Silver. By 0. v. D. PFORDTEN (Bey., 20, 3.375-3382 ; compare Abstr., 1887, 699).-According to Stas, silver is oxidised i n the cold in presence of water containing dissolved air and acidified with hydrochloric, sulphuric, or acetio acid, &c. Experiments made by the author show that when a solution contain- in? potassium perrnanganate and sulphuric acid is boiled in a current of carbonic anhydride it is not capable of dissolving finely divided silver; on admitting air to the solution, silver dissolves and the permanganate becomes decolorised.This accounts for the resuIt previously obtained (Zoc. cit.) when silver was boiled with dilute sulphiiric acid and treated with a drop of permanganste solution ; the solution being free from air, the permanganate did not decolorise. In presence of air, the reaction is very slow, and in the titzation of the argentous oxide with permanganate, none of the silver formed is dissolved (compare Priedheim, Abstr., 1887, 1079). With regard to Friedheim's supposition (Zoc. cit.) that the argentous oxide is a mixture of silver and argentic oxide or organic matter, it is VOL. LIV. ¶222 ABSTRACTS OF CHEMICAL PAPERS. mentioned that the preparation previoixsly described contained no carbon and dissolved in nitric acid without leaving a residue ; when shaken f o r 12 hours with mercury, it underwent, no change in properties or appearance. It is therefore maintained that the substance cannot be metallic silver.The examination of the substance will be continued. N. H. M. Behaviour of Basic Slag with Water charged with Carbonic Anhydride. By M. A. v. REIS (Chem. Zeit., 11, 933-934; 981- 982) .-In these experiments, which are a continuation of those pre- viously made by him (Abstr., 1886, 663), the author has included nine samples of slag from different sources ; two samples of precipitated slag ; one sample each of di-, tri-, snd t,etra-calcium phosphate (the last synthetically prepared), also bones, bone-ash, arid phosphorite. Ten grams of the finely powdered phosphate supported on a platinum cone covered with asbestos in a funnel, were treated with water saturated with carbonic anhydride percolating at the rate of 1 litre in three hours.One slag W A S treated with 50 litres of carbonic anhydride solution ; each litre of the first 10 litres of percolate was examined separately, but subseqnent81y examinations were made at definite intervals. Silica and phosphoric acid pass through in nearly constant quantities in proportions approximating to their relative amounts in the original slag up to the 25th like, after which their solubility rapidly decreases ; lime, however, continues t o dissolve even in the 50th litre. Although the various changes take place simultaneously at first, the free lime is most readily attacked, then the calcium silicate and phosphate, and finally the other compounds of calcium (probably ferrite or manganate).The exhausted slag amounted t o 30.07 of the original ; its composi- tion (I), and that of the original slag (11), is as follows :- Si02. P,05. CaO. MgO. MnO. FeO. Fe,03. I. 2.30 2.25 14.7 6.65 9-09 18.41 35.90 11. 7.67 16.32 47-98 2-47 4.18 8.90 7.41 Loss on A1,0,. Insoluble. ignition. I. 5.52 2.25 3.10 11. - 0-47 - The slight solubility of the magnesia is noteworthy. The other phosphates and slags were treated each with 10 litres of carbonic anhydride water, and the percolates were examined in two lots of 5 litres each. Full numerical details are given, from which the follow- ing table is taken, showing the relative solubility of the phosphoric acid, silica, and lime in the various phosphates examined; the figures are percetitages of the amount of each constituent in the original substmces :-INORUANLC CHEMISTRY.223 Si02. PZO,. Slags .............. 86.1-27-4 48.1-229 Tetracalcium phosphate - 42.1 Hones .............. - 28-5 Precipitated slags. ... 7.7-22.7 22.0-33-0 Dicalcium phosphate. . - 16.8 Tricalcium ,, . . - 12.5 Bone ash.. .......... - 5.5 Phosphorite ......... - 3.1 CaO. 57.5-34.4 53.0 28 -9 30.1-58.5 16.8 13.6 5.9 3.8 The slags varied considerably amongst themselves owing to their different origin and constitution, but along with the tetracalcium phos- phake they proved more soluble than the other forms of phosphate ; the comparatively high solubility of bone phosphoric acid is due to the organic matter present. It is interesting to note that in experiments with the tetracalcium phosphate after the removal of any excess of lime in the first 5 litres or so, the phosphoric acid and lime wash out in the inolecule ratio lP,O,: 4Ca0, tending to show that this really is a com- pound of that composition, for had it been a mixture of lime and tri- phosphate, the lime would have continued to wash out irregularly.In a similar manner, the existence of tetracalcium phosphate in basic slag is illustrated. The author concludes that he has now set a.side v. Maltzahn’s adverse criticism of his previous work, and upset any views as to the comparative insolubility of basic slag phosphates. Tetrabasic Calcium Phosphate and the Basicity of the Sili- cate in Basic Cinder. By G. HILGENSTOCK (Chern. Centr., 1887, 1097-1098, from Stahl zc.Eisen, 7 , 557-560).-The author bas succeeded in preparing tetrabasic calcium phosphate by fusing together calcium phosphate or phosphoric acid with lime, using fluorspar as a flux. The author points out further that since calcium triphosphate is reduced by metallic iron when fused, it can only be the tetrabasic phosphate which is contained in the basic slag, and that the difference in crystalline form of this phosphate may be accounted for in some- what the same way as in the formation of the various modifications of antinionious oxide, valentinite and senarmontite. Observations seem to show that as the flux cools, the rhombic plates are first formed, next the hexagonal needles, and finally the monosymmetrical crystals. In conclusion, the author endeavours to prove that the silica can only be present in the form CaSi03.D. A. L. J. W. L. Behaviour with the usual Solvents of the Soluble Phosphoric Acid in Superphosphates, which have remained some time in Bulk. By A. BEYER (Chern. Centr., 1687,1115, from Rep. anal. Chem., 7,327-330) .-In making a series of determinations to compare Peter- mann’s and Wagner’s methods for the estimahion of the phosphoric acid soluble in ammonium citrate, the author found that not only was the percentage of phosphoric acid soluble in waker reduced by long standing in heaps, but also that soluble in ammouiurn citrahe solution as estimated by Wagner’s method, The alteration in the percentage g f L224 ABSTRACTS OF CHEMICAL PAPERS. of phosplioric acid as estimated by Petermann’s method, was lees noticeable.In superphosphates containing but little ferric oxide and alumina, the differences between the results obtained by the two methods were not very great, but even a t the end of eight, days an appreciable loss of soluble phosphoric acid as determined by Wagner’s method was observed, which quantity mas not so great where con- siderable quantities of acid had been employed. Petermann’s method does not show so great a change in the soluble character of the phos- phoric acid in superphosphates after a time. If the superphosphates contain considerable quantities of ferric oxide and alumina, the results as obtained by the two methods vary almost directly after manufac- ture, which differences increase the longer the superphosphates are kept. Here also the results obtained with Petermann’s method remain almost constant, whilst the percentage as determined by Wagner’s method, as also the phosphoric acid soluble in water, decreases.Cadmium Sulphide and the various Cadmium Pigments of Commerce. By G. BBUCHNER (Chew,. Zeit., 11, 1087-1089 ; 1107- 1109).-The author finds that all the forms of cadmium sulphide have the same percentage composition represented by the formula CdS, but that two modifications exist, one lemon-yellow, the simple CdS, the other a polymeride of it, and of a vermilion colour. The variety of colour in different preparations of cadmium sulphide is due to the mixture of these two modifications in varying proportions, and not to the small quautity of soluble cadmium salt retained by the sulphide during its precipitation, as has been suggested. The yellow variety is readily polymerised into the red variety by dilute acids, alkalis, &c., especially when in the nascent state, hence on precipitating solutions of cadmium salts with hydrogen sulphide, at first the yellow sulphide forms, but, as the liberated acid comes into action, the red sulphide is precipitated, and if the solution is acid beforehand, little or no yellow sulphide is produced.The red variety passes through the yellow stage when dissolved in acids. Sodium sulphide produces the yellow sulphide in dilute solutions of a cadmium salt, a reddish precipitate in strong solutions, and a brick-red one in boiling solutions. Polysulphides of potassium or ammonium precipitate the yellow cadmium sulphide mixed with varying quantities of finely divided sulphur, which can be extracted by carbon bisulphide.It is note- worthy that pure (red or yellow) cadmium sulphide is quite stable in light, whereas this mixture of sulphide and s u l p h r oxidises rapidly in light (not in darkness), becoming dirty white, especially after it is ground with linseed oil. Cadmium hydroxide also assumes two forms : the simple one pre- pared by adding sodium hydroxide to solutions of cadmium salts gives rise to the yellow sulphide with sodium sulphide, &c. ; the polymeric one is formed when cadmium solutions are poured into solutions of sodium hydroxide or when they are precipitated hot ; this hydroxide produces the red sulphide, with an intermediate &cadmium sulph- hydroxide, Cd,S(OH)2, of a fiiie red colour, but too unstable for a pigment ; the author considers this association of red colour with the fwo cadmium atoms in a single molecule, supports his view of the J.W L.INORGANIC CHEMISTRS. 225 ---- Ammonia .............. polymeric character of the red sulphide. When heated carefully, the yellow and red sulphides undergo a series of changes of colour through which they pass on cooling in the reverse order, both returning to yellow, the red sulphide having suffered molecular disarrangement during the heating. When heated out of direct contact with the air they neither sublime nor oxidise beyond just the surface. The author finally goes into the question of cadmium pigments, finds zinc com- pounds the most ordinary adulterants, and gives various tests hy which a good pigment for oil painting may be recognised.Action of Water on Lead. By M. MELLER (J. pr. Chem. [2], 36, 317--340).-A sample of water from the Ocker was distilled. The amounts of dissolved gases and of ammonia were determined in the first, middle, and last fractions, and the behaviour of the different fractions with lend observed. The water before distillation contained 0.00015 per cent. of ammonia. D. A. L. First fraction. Middle fraction. Last fraction. -__-__------ 0.00115 p. c. 0'0001 p. c. O~OOOo8 p. c. Total volume ........... 2 -04 vol. p. c. 1 -196 vol. p. c. Cwbonic anhydride.. .... 1 -159 ), 0-178 ,: Oxygen ................ 0 -269 ,, 0-316 ,: Nitrogen (diff.) ......... 0 -612 ,, 0-70.2 ,, 0.77 vol, p. c. 0.025 ,, 0'232 ,, 0.513 ,, I------ ----- $--- Dissolved $,ses reduced to 0" and 760 mm.pressure. First fraction. Middle fraction. Laat fraction. In this case also the first fraction' showed scarcely any action on lead, after remaining in contact with it for 24 hours. The middle and last fractions attacked it with considerable energy. The protecting influence of the first fractions must be considered as due to their con- Total volume ........... Carbonic anhydride. ..... Oxpgcn ................ Nitrogen (diff.) ........ 2 -661 vol. p. c. 1 -31.2 vol. p. c. 1.047 vol. p. c. 2.030 ), 0'228 ,, 0.069 ,, 0 -198 ,i 0.358 ,, 0.341 ,, 0 -433 ,, 0-738 ,, 0-637 ,,226 ABSTRACTS OF CHEMICAL PAPERS. taining a, relatively large quantity of carbonic anhydride. Distilled water, which was vigorously boiled f o r some time and quickly cooled in contact with air, was found to contain 0-04 per cent.of its volume of carbonic anhydride, 0.236 per cent. of its volume of oxygen, and 0.514 per cent. of its volume of nitrogen. The rapid absorption of these p s e s explains the behaviour of water so treated towards lead. Distilled water, quite free from carbonic anhydride but containing oxygen, scarcely acts on lead, but on exposure to the air the liquid becomes cloudy, owing to the formation of a white precipitate. Samples of water containing different amounts of carbonic anhydride, but an invariable quantity of oxygen, behave very differently with lead. I n one case, when the oxygen present was 0.35 per cent. of tile volume of the liquid, and saturated solution of carbonic anhydride was added until the water contained 0.14 per cent. of its volume, the lead was appreciably attacked.On increasing the carbonic anhydride to 0.6 vol. per cent., the athack became remarkably energetic. With 1 vol. per cent. the action was considerably weaker, and when the carbonic anhydride was increased to 1.5 vol. per cent. the lead was no longer visibly corroded. Water containing 2,2.5, and 3 vols. per cent. of carbonic anhydride was equally inactive. Water containing car- bonic anhydride but no oxygen is practically without action on lead, when atmospheric air is excluded. When strips of lead are immersetl for eight days in pure distilled water, recently boiled and cooled out of contact witb the air, they do not become tarnished.Before filtra- tion, however, but not after, the water gives a considerable reaction with hydrogen sulphide. Pure water evidently attacks lead with formation of an oxide. Ordinary distilled water in which strips oE lead were placed, and from which the air was excluded, contained a maximum quantity of lead a t the end of three days, after which the lead was by degrees thrown out of solution. This is explained by supposing that water containing carbonic anhydride and oxygen in contact with lead forms lead carbonate, which dissolves in t h e excess of the gas; but as more lead oxide is formed, this carbonic aphydride is absorbed, and all the lead falls out of solution as lead carbonate. Distilled water, free from carbonic anhydride, to which minute quantities of ammonia have been added, attacks lead, but is without action on it if carbonic anhydride is present. Lime water, through which a current of air, perfectly free from car- bonic anhydride, was passed, a t first slowly dissolved lead, but this was soon again thrown out of solution in the form of minute crystals.The solution attained a maximum after 13 hours, and then decreased. Sodium hydroxide solution behaved in a similar way. I n the absence of oxygen, neither lime-water nor sodium hydroxide solution attacked lead. Lead tubing, buried in mortar, and kept in a dry room for a year suffered no change, but when the mortar was occasionally moistened with pure water, corrosion rapidly took place. When soapy water or an alkaline solution of lime was used instead of pure water, the decomposition-products consisted to some extent of red lead.Ordinary distilled water, to which a small quantity of sodium carbonate was added, dissolved no lead, but the metal became slowlyINORGANIC CHEJIISTRY. 227 corered with a white, compact coating. When the water contained oxygen but no carbonic anhydride, lead was found in solution after a, few hours. A trace of sodium hydrogen carbonate added to distilled water completely prevented the dissolution of lead, and the metal hecame covered Kith a protecting crust. Waters containing lead in solution were found to be freed from it by adding sodium carbonate. Pure lead carbonate is soluble in water containing carbonic anhydride ; it, is reprecipitsted by boiling the solution or by adding hydrogen sodium carbonate to it.Evidently lead forms an acid carbonate, which is soluble in water but possesses little stability. Hydrogen cal- cium carbonate acts in precisely the same way as hydrogen sodiunr carbonate. Polished strips of lead immersed in a saturated solution of pure calcium sulphate, containing oxygen, become covered with a hard white coating, but no lead goes into solution. In the absence of oxygen, the metal remains perfectly bright. On placing lead covered with the white crust formed by long immersion in a solution of calcic sulphate, in pure distilled water, no lead went into solution except when a considerable quantity of carbonic anhydride was present. When a trace of hydrogen calcium carbonate was added to the solution, in no case was any lead dissolved.The coating is in all probability a basic sulphate of lead. The presence of minute quantities of chlorides, nitrates, organic matter, and ammonia in water, did not influence its behaviour towards lead. This seems to depend on the presence of oxygen and carbonic anhydride. Water containing much organic matter, and rich in car- bonic anhydride, rapidly corrodes lead, but polished surfaces of the metal remain perfectly bright when immersed in pure solutions of organic compounds, such as starch aud sugar, provided no carbonic anhydride is present. Colloidal Copper Sulphide. By W. SPRING and G. DE BOECK (BUZZ. Soc. Chim., 48, 165-170) .-An aqueous solution of copper sulphide can be obtained by precipitating any copper salt by hydrogen snlphide and washing by decantation with dilute sulphuric acid.As the impurities are removed, the copper sulphide becomes soluble and forms a dark-coloured solution with a slight greenish fluorescence. A purer product is obtained by precipitating with ammonium s d - phide. The solution contains hydrogen sulphide and may possibly contain copper hydrosulphide. The former may be expelled by a short ebullition without any notable precipitation of copper taking place. Analysis of the liquid shows that the copper and sulphur are in the ratio required by the formula GUS, and hence the solution contains no copper hydrosulphide. Examination with the spectro- scope shows that the solution is a true solution and not simply a turbid liquid. It absorbs half the red, the violet, and half the blue in the spectrum of a lamp flame.The copper sulphide is precipitated from this solution by the addition of various salts, a lkt of which is given i n the paper, but the power of precipitation bears no simple relation to the molecular weight 01- molecular volume of the salt. The valency of the metal, howevei., G. T. MI.228 ABSTRACTS OF CHEMICAL PAPERS. exerts considerable influence. Alum, chrome alum, and aluminium sulphate, precipitate it when added in very small quantities, and the precipitating power of salts of dyad metals is about 10 times as great as that of salts of sodium and potassium. Schulze has made similar observations in the case of antimony sul- phide, but the copper sulphide is more readily precipitated thah the antimony compound. C.H. B. Stability of Mercuric Chloride Solutions. By V. MEYER (Ber., 20, 29'70-2974 ; comp. Abstr., 1887, 774).-Further experi- ments have shown that the solutions of mercuric chloride in the hard Gottingen water, even when preserved in hermeticnlly sealed flasks with or without the addition of common salt, gradually deposit mer- curic oxychloride, but less rapidly than when kept in vessels exposed to the air ; atmospheric dust, however, does not seem to influence the rate of decomposition in any very marked way. If the solution of mercuric chloride in ordinary water, instead of being exposed to diffused daylight, is kept in the dark in well-stoppered flasks, it is found that practically no decomposition occurs, even after two months in solutions made with Gottingen water, pond water, and a well water charged with organic impurity, to which no addition of salt has been made ; the very small amount of decomposition which actually occurs being attributed to the unavoidable exposure to diffused day- light during the repeated examination of the solutions.w. P. w. Action of Alumina and Kaolin on Calcium Chloride. By A. GORGEU (Bull. SOC. Chim., 48, 51--52).-Calcium chloride mixed with alumina, kaolin, o r ordinary day, and fused a t a cherry-red heat in presence of moist air, yields crystalline products soluble in dilute acids. With alumina, the crystals are distinct, colourless, mono-refractive, modified tetrahedra. They are anhydrous at 120", have the composition 6A1,O3,10CaO,CaCl,, and are slowly decom- posed by boiling water. Kaolin alone, or mixed with silica, seems to produce various crystalline compounds, including mono-refractive crystals resembling calcium garnet, but these could not be isolated.After prolonged fusion, the product was treated with dilute hydro- chloric acid and a solution of sugar. In this way modified tetrahedra of the composition 3Si0,,3Al,0,,16Ca0,2CaCl,. were obtained. It would seem that calcium garnet is first formed, and afterwards con- verted into the chlorosilicate. Calcium garnet, in fact, when fused with calcium chloride and oxide, yields modified tet'rahedra similar to those just described. Soluble Manganese Oxide. By W. SPRING and G . DE BOECK (Bull. SOC. C'him., 48, 170--178).-This manganese oxide is obt-ained by acting on potassium permanganate with sodium thiosulphate, and thoroughly washing the precipitate with water.As Boon as all the potassium has been removed, a brown solution is obtained, from which the oxide is precipitated on the addition of any salt (comp. Gorgeu, Ann. C'him. Phys. [S], 63, 155). Amlysis of the product obtained by C. H. B.INORGANIC CHEMISTRY. 229 evaporation of the brown solution shows that it has the composition 4(MnO,,H,O) ,Mn304. .The portion of the original precipitate which is insoluble in water has the composition MnsOI3,4H20, or 3Mn02, Mn304, Mn203, 4H20. The colloidal manganese oxide is precipitated by salts more readily than collojidal copper sulphide, and the valency of the metals in the salts has the same influence in both cases. The manganese solution can be kept for a long time in sealed tubes, but if filtered through paper the manganese is completely precipitated.By A. JOLLES (Chem. Zeit., 11, 1394- 1395).-In a previous communication, it is stated that the following equation : KzMn04 + C2H60 = KZMnO3 + C2H40 + HzO, represents the oxidation which takes place in the author's test for certain impurities in chloroform (Abstr., 1887, 866). This statement has been cont.ested. I t is now shown that both aldehyde and the manga- nite KzMn03 are produced, but in excess of alcohol the latter soon decomposes ; when, however, the substances are taken in equivalent quantities, the manganite can be separated and dried over sulphuric acid. It is a yellowisb-brown substance; is decomposed by dilute nitric and sulphuric acids, yielding manganese dioxide and hydrated dioxide and potassium uitrate or sulphate.It oxidises sulphurous acid to sulphuric acid, which in the nascent state forms manganese sulphate. Boiled with oxalic or tartaric acid, the manganite dissolves with evolution of carbonic anhydride. On exposure to a current of superheated steam and air, it is partially converted into manganate (compare Rousseau, Abstr., 1887, 552, 892). Manganese Compounds. By B. FRANKE ( J . p r . Chem. [Z], 36, 451-468 ; compare Abstr., 1887,893, 1016) .-By heating 8 grams of potassium permanganate with 1OU C.C. of strong sulphuric acid at 300", and allowing it to cool, a brown crystalline salt, Mnz03,4S03,5H20, is formed. When this is treated with water, it is decomposed into equimolecular quantities of mangnnous sulphate and the hydrated oxide H2Mn03; the salt is probably Mn2(S0&,H2SOd + 4H20.Manganic sulphate, Mn,(804)3, is obtained when the above salt is heated more strongly with sulphuric acid, in green crystals, decom- posed by water in the same way as the acid salt, showing that the atoms of manganese are of different valency. The salt may therefore be regarded as the manganous salt of an acid, Mni'SO~(O~SOz*OH)2, analogous to the manganous manganese chloride (Abstr., 1881, 893). Mnz( S04)3,K2SOa, is obtained in red-brown crystals by carefully heat- ing 8 grams of potassium permanganate with the mother-liquor from the above acid salt; water decomposes it in a manner similar to the other salts. Steel-grey, metallic-looking crystals of H2Mn20~ are obtained when either of the foregoing compounds is thrown into very weak aqueous soda ; sulphuric acid decomposes it into manganous sulphate and manganous acid, MnO(OH)2, which is thus obtained pure as a brown powder ; this points to the formula Mn<O>Mn(OH)a.C. H. B. Potassium Manganite. D. A. L. 0230 ABSTRACTS OF CREMICAL PAPERS. The brown colour of the solution of manganese dioxide in strong hydrochloric acid is caused by the presence of manganous acid. A. G. B. Permanganates. By T. KLOBB (BUZZ. SOC. Chim., 48, 240-244). -The author has previously prepared certain permanganates by adding potassium permanganate to ammonincal solutions of certain metallic salts (Abstr., 1886, 983). He has now obtained similar derivatives from luteocobalt chloride in a similar way.Luteocobal tic pe rmangan ate, Go2( MnO ,) 6, 1 2NH3, is obtained by mixing warm concentrated solutions of luteocobalt chloride (1 mol.) and potassium permanganate (12 mols.) It separates in the form of a precipitate mixed with a salt which crystallises in hexagonal plates, and is formed in greater proportion when the permanganate is not in excess. The latter can be removed by treatment with cold water, and the luteocobaltic permariganate is recrystaliised from water a t 60". It then forms very brilliant, black tetahedra., only slightly soluble in cold water, but more soluble in hot water with partial decomposition. When heated, it detonates, and it also explodes when struck. With hydrochloric acid, it yields manganous chloride and luteocobaltic chloride.Luteocobaltic chloroper~~~angar2.ate, (Coz,12NH,)Cl,,2Mn0,, is pre- pared by mixing a solution of luteocobaltic chloride (8 mols.) with a solution of luteocobaltic permanganate (1 mol.), filtering rapidly, and allowing t o cool. It separates in small, black lamellae with the form of a regular hexagon, red or brown by transmitted light. It is very unstable, and is decomposed by water with removal of the chloride, but dissolves without decomposition in a solution of luteo- cobaltic chloride. When heated rapidly, it detonates, but it does not explode on percussion. Luteocobaltic bromopermanganate is analogous to the chloroper- manganate, rind is prepared in a similar way, or more simply, by mixing warm solutions of potassium permanganate (3 mols.) and luteocobaltic bromide (1 mol.), and allowing them to remain.It forms brilliazit, hexagonal lamells, which are much more stable than the chlorine-derivative, and are not decomposed by boiling water. The salt which is obtained in the preparation of lnteocobaltic per- manganate, and which crystallises in hexagonal lamells, is also obtained by mixing cold concentrated solutions of luteocobaltic chloride (1 rnol.) and potassium permanganate (3 mols.), when it separates slowly in violet hexagonal lamells of the composition ( Co2,12NH3) Cl2,2ICC1,4MnOa, very soluble in water with partial de- composition in to its constituents. When heated, it behaves like the preceding salts. It may be regarded as a compound of luteocobaltic permanganate and luteocobaltic chloride with potassium chloride.It can also be formed by dissolving luteocobaltic chloropermanganate in potassium chloride solution, o r by the action of luteocobaltic per- manganate on a large excess of potassium chloride. C. H. B. Electrolytic Extraction of Antimony. By W. BORCHERS (Chem, Zeit., 11, 1021--1022).-The author has based a process for the extraction of antimony (from all its combinations soluble in sodiumMINERALOGICAL CHEMISTRY. 231 sulphide solution) on the electrolytic method of Classen and Ludwig (Abstr., 1885, 932) for the estimation of that metal. The ore is extracted with sodium sulphide solution, using 3 mols. Na2S for every mol. Sh,S,. The concentrated extract is mixed with 3 per cent. of sodium chloride to increase its conductivity, and electro- lysed.According to the intensity of the current, the metal is deposited as a powder or in shining scales. To prevent deposition of sulphur, the relation of 1 atom of available Na for every atom of oxidisable sulphur must, be maintained, but as t h e mixture Sb,S3 + Na,S + 2NaHO is too unstable, the above proportions are used; too much sodium sulphide is to be avoided as i t increases the resistance of the liquid. The common salt is easily crystallised from the electrolysed solo- tions, and the sulphur recovered as sodium thiosulphate without much difficulty. D. A. L. By G. v. KNORRE and P. OLSPHFWSKY (Ber., 20, 3043--3052).-Attempts were made to prepare Fremy ' s potassium antimoniate, K4Sb,07 ( J . pr. Chein., 45, 209), but without success ; it is concluded that that salt does not exist, and thatFremy's compound is a mixture of potassium antimoniate and potash.Potassium antirnoniate, K,Sb,Oc, contains 5 mols. H,O when air- dried, and is a, white granular salt. 100 parts of water at 20" dissolve 2.81 parts of anhydrous salt. Rp.. gr. of saturated solution at 18" = 1.0263. A table is given showing the loss of weight it under- goes at various temperatures ; at 330" it contains rather more than 1 mol. H20, and the author assumes that 1 mol. H,O is chemically combined, and that the formula of the air-dry salt is K,E2Sb,O7 + 4H20. When the hot aqueous solution is evaporated, a gummy salt remains ; when this is dried at loo", it has the composition expressed by the formula, K,Sb206 + 3H,O. Potassium antimoniate was also prepared by the methods of Rrunner (DinrgZ.polyt. J., 159, 356) and tteynoso (Annalen, 80,272) ; details of preparation and results are given (compare Abstr., 188& 1184). N. H. M. Antimoniates.INORGANIC CHEMISTRY. 219I n o r g a n i c Chemistry.Preparation of Hydrogen Iodide. By L. MEYER (Ber., 20,3381--3383).-100 parts of iodine contained in a retort are moistenedwith about 10 parts of water. The retort is then fitted with a funnelclosed with a glass rod, containing 5 parts of amorphous phosphorusmixed with 10 parts of water. One drop of water containing pbos-phorus is let into the retort; more phosphorus is slowly added,after which large amounts may be added. The mixing is completedin a quarter of an hour. I f more than a drop is added a t first, theaction cannot be controlled, and will generally result in a violentexplosion.No heating is necessary. The iodine carried over by thehydrogen iodide is nearly all deposited in the neck of the retort,which is inclined upwards.By using 100 grams of iodine, 5 grams of phosphorus, and 25 C.C.of water, 95 grams of hydrogen iodide (of which 37.5 grams wereobtained by- distillation) were obtained, instead of 1C0.8 grams.With 20 grams of water 98.1 grams were obtained (74.4 grams as gasand 23.7 grams by distillation), N. H. M.Products and Rate of Decomposition of the Salts of theHalogen Oxy-acids by Heat. By A. POTILITZIN (Chem. Centr., 1887,1218, from J. Russ. Chem. Soc., 1887, 339-357).-Between 330" and400°, barium chlornte decomposes entirely according to the equation2Ba(ClO,), = BaC1, + Ba(C104), + 40.Between 400" and 470",barium chloride and oxygen are the only products. The rate of thedecomposition rises with the temperature up to 400", whilst if thetemperature remains constant, the decomposition rises a t first, andthen gradually falls again, ahhough it is not complete. According tothe author, barium chlorate decomposes to some extent before itmelts, Barium perchlorate crystallises with 3 mols. HzO, whereasMarignac gives the formula Ba(C10& + 4H,O; also, contrary toNarignac's statement, it is not hygroscopic. It loses 2 mols. H,O byremaining over sulphuric acid, and the third molecule is expelled at100".Barium bromate becomes anhydrous at 170°, the crystals turnin220 ABSTRACTS OF CEEMICAL PAPERS.slightly yellow, without, however, losing their crystalline form orlustre.Decomposition begins at 260", and at 300" bromine i8 evolved.The decomposition becomes complete without tho salt melting. Theauthor draws the conclusion that the bromate is changed into twoisomeric salts, namely BrV0,90M (the original salt), and MBr"fi03,and that these, therefore, decompose at different rates. He could notfind any perbromate in the product of decomposition. J. W. L.Mutual Displacement of the Halogens in their Compoundswith Oxygen. By A. POTILITZTN (Chern. Centr., 1887, 1218-1219 ;from J, Russ. Chem. SOC., 1887, 358--364).-The author believes thatthese reactions are much more complex than is usually supposed.By the action of chlorine on a solution of sodium bromat,e in the dark,he obtained a mixture of sodium chloride and bromide, and byomir,and chloric acids together with free bromine.He finds that chlorineacts in the same way on potassium bromate and on barium bromate ;experiments were also made on the dry salts, when the same productsseemed to be formed. Bromine was also found to act on the chloratesin the same way, although much less energetically. These reaction8tske place much more readily in a sealed tube. Iodine and theiodates were also included in the serie8 of experiments wit,h similarresults. J. W. L.Preparation of Hydrogen Sulphide Free from Arsenic, ByC. WINKLER (Zeit. and. Chem., 27, 26--27).-Barinm sulphate(powdered barytes) is mixed with 25 per cent.of ground coal and 20per cent. of common salt. The damped mixture is rammed into aclay crucible, which after drying and closing with a luted cover isheated for several hours at an incipient white heat. The product, igin hard compact masses which dissolve completely in dilute hydro-chloric acid with a steady evolution of hydrogen snlphide.Selenites. By BOULZOUREANO (BUZZ. Soc. Chim., 48, 209-210).-Solutions of metallic salts were mixed with sodium selenite and theresulting precipitates were heated in sealed tubes at 200" with verydilute selenious acid. Ferric selenite forms small, golden-yellowprisms which separate in radiating groups.Another method consists in treating a metallic carbonate withdilute selenious acid, mixing the solution with its own volume of water,and heating in sealed tubes at 200".This was employed for the pre-paration of the cobalt, nickel, manganese, and cadmium salts.Cobalt selenite forms transparent, violet prisms, nickel seleniteforms large, short, green prisms arranged in radiating groups. Ifthe original solution is mixed with sodium selenite, yellow crystals areobtained. Manganese selenite crystallises in short, pale-red prismsor in slender, brown needles if heated beyond 230'. The cadmiumsalt forms long, colourless, transparent prisms, or much shorter yellowcrystals if heated at about 200". Zinc seems to form a selenitecrystallising in prisms.The liquid obtained by the second method was allowed to evaporateqontaneously at the ordinary temperature or in a vacuum.Cryshls31. J. SINOROAKIC CHEMISTRY. 221are obtained in t.he case of cobalt and manganese. The latter yieldsa pink-colonred crust and the former deep violet crystals.Cupric carbonate, when treated with a warm solution of seleniousacid, yields a blue precipitate of the normal selenite, and if this isheated to boiling, it is converted into green, microscopic prisms. Thesolii tion is bluish-green, and on cooling deposits large, green crystals,If the normal selenite is heated in sealed tubes with the carbonateand water, it yields well-defined, greenish-yellow, prismatic crystals.Sodiiim selenite and zinc sulphate in sealed tubes yield white, trans-parent crystals. C, H. B.Preparation of Hydrogen Arsenide.By A. CAVAZZI (Ohem.Centr., 1887, 1097, from Remd. Am. Bologna, 1886-87, 85-86).-The action of zinc on an acid solution of arsenious acid produces a gascontaining 70 per cent. by volume of hydrogen arsenide. Sodiumamalgam containing not more than 4 grams of sodium in 50 C.C. ofmercury, by its action on a concentrated solution of arsenious acid, pra-duces a gas containing 86 per cent. by volume of hydrogen arsenide,A gas containing a large qnantity of arsenic may be prepared by theaction of aluminium on a somewhat dilute alkaline solution ofpot'assiurn arsenite, whilst a solution of arsenic disulphide in potash,when subjected to the action of aluminium, evolves a gas quite freefrom arsenic. J. W. b.Action of Hydrogen Arsenide on Arsenious Acid.By D.TIVOL~ (Chem. Centr., 1887, 1097, from Rend. Acc, BoZogna, 188647,98) .-The reactions of hydrogen arsenide on arsenious acid dissolvedin hydrochloric and sulphuric acid respectively are expressed by theequations :-2dsH, + 2AsC1, = 6HC1 + As4 and 3(As02)S0, +H,S04 + 6AsH3 = 3As4 + 4K2S04 + 68,O. The precipitation ofthe arsenic does not take place in neutral solutions, whereas in thehydrochloric acid solution it is complete, and in the sulphuric acidsolution almost so. J. w. L.Lowest Compounds of Silver. By 0. v. D. PFORDTEN (Bey.,20, 3.375-3382 ; compare Abstr., 1887, 699).-According to Stas,silver is oxidised i n the cold in presence of water containing dissolvedair and acidified with hydrochloric, sulphuric, or acetio acid, &c.Experiments made by the author show that when a solution contain-in? potassium perrnanganate and sulphuric acid is boiled in a currentof carbonic anhydride it is not capable of dissolving finely dividedsilver; on admitting air to the solution, silver dissolves and thepermanganate becomes decolorised. This accounts for the resuItpreviously obtained (Zoc.cit.) when silver was boiled with dilutesulphiiric acid and treated with a drop of permanganste solution ; thesolution being free from air, the permanganate did not decolorise. Inpresence of air, the reaction is very slow, and in the titzation of theargentous oxide with permanganate, none of the silver formed isdissolved (compare Priedheim, Abstr., 1887, 1079).With regard to Friedheim's supposition (Zoc.cit.) that the argentousoxide is a mixture of silver and argentic oxide or organic matter, it isVOL. LIV. 222 ABSTRACTS OF CHEMICAL PAPERS.mentioned that the preparation previoixsly described contained nocarbon and dissolved in nitric acid without leaving a residue ; whenshaken f o r 12 hours with mercury, it underwent, no change in propertiesor appearance. It is therefore maintained that the substance cannotbe metallic silver. The examination of the substance will becontinued. N. H. M.Behaviour of Basic Slag with Water charged with CarbonicAnhydride. By M. A. v. REIS (Chem. Zeit., 11, 933-934; 981-982) .-In these experiments, which are a continuation of those pre-viously made by him (Abstr., 1886, 663), the author has included ninesamples of slag from different sources ; two samples of precipitatedslag ; one sample each of di-, tri-, snd t,etra-calcium phosphate (thelast synthetically prepared), also bones, bone-ash, arid phosphorite.Tengrams of the finely powdered phosphate supported on a platinum conecovered with asbestos in a funnel, were treated with water saturatedwith carbonic anhydride percolating at the rate of 1 litre in three hours.One slag W A S treated with 50 litres of carbonic anhydride solution ;each litre of the first 10 litres of percolate was examined separately,but subseqnent81y examinations were made at definite intervals.Silica and phosphoric acid pass through in nearly constant quantitiesin proportions approximating to their relative amounts in the originalslag up to the 25th like, after which their solubility rapidly decreases ;lime, however, continues t o dissolve even in the 50th litre.Althoughthe various changes take place simultaneously at first, the free lime ismost readily attacked, then the calcium silicate and phosphate, andfinally the other compounds of calcium (probably ferrite or manganate).The exhausted slag amounted t o 30.07 of the original ; its composi-tion (I), and that of the original slag (11), is as follows :-Si02. P,05. CaO. MgO. MnO. FeO. Fe,03.I. 2.30 2.25 14.7 6.65 9-09 18.41 35.9011. 7.67 16.32 47-98 2-47 4.18 8.90 7.41Loss onA1,0,. Insoluble. ignition.I. 5.52 2.25 3.1011. - 0-47 -The slight solubility of the magnesia is noteworthy.The otherphosphates and slags were treated each with 10 litres of carbonicanhydride water, and the percolates were examined in two lots of5 litres each. Full numerical details are given, from which the follow-ing table is taken, showing the relative solubility of the phosphoricacid, silica, and lime in the various phosphates examined; the figuresare percetitages of the amount of each constituent in the originalsubstmces :INORUANLC CHEMISTRY. 223Si02. PZO,.Slags .............. 86.1-27-4 48.1-229Tetracalcium phosphate - 42.1Hones .............. - 28-5Precipitated slags. ... 7.7-22.7 22.0-33-0Dicalcium phosphate. . - 16.8Tricalcium ,, . . - 12.5Bone ash.. .......... - 5.5Phosphorite ......... - 3.1CaO.57.5-34.453.028 -930.1-58.516.813.65.93.8The slags varied considerably amongst themselves owing to theirdifferent origin and constitution, but along with the tetracalcium phos-phake they proved more soluble than the other forms of phosphate ; thecomparatively high solubility of bone phosphoric acid is due to theorganic matter present.It is interesting to note that in experimentswith the tetracalcium phosphate after the removal of any excess of limein the first 5 litres or so, the phosphoric acid and lime wash out in theinolecule ratio lP,O,: 4Ca0, tending to show that this really is a com-pound of that composition, for had it been a mixture of lime and tri-phosphate, the lime would have continued to wash out irregularly.In a similar manner, the existence of tetracalcium phosphate in basicslag is illustrated.The author concludes that he has now set a.side v.Maltzahn’sadverse criticism of his previous work, and upset any views as to thecomparative insolubility of basic slag phosphates.Tetrabasic Calcium Phosphate and the Basicity of the Sili-cate in Basic Cinder. By G. HILGENSTOCK (Chern. Centr., 1887,1097-1098, from Stahl zc. Eisen, 7 , 557-560).-The author bassucceeded in preparing tetrabasic calcium phosphate by fusing togethercalcium phosphate or phosphoric acid with lime, using fluorspar as aflux. The author points out further that since calcium triphosphate isreduced by metallic iron when fused, it can only be the tetrabasicphosphate which is contained in the basic slag, and that the differencein crystalline form of this phosphate may be accounted for in some-what the same way as in the formation of the various modifications ofantinionious oxide, valentinite and senarmontite. Observationsseem to show that as the flux cools, the rhombic plates are first formed,next the hexagonal needles, and finally the monosymmetrical crystals.In conclusion, the author endeavours to prove that the silica can onlybe present in the form CaSi03.D.A. L.J. W. L.Behaviour with the usual Solvents of the Soluble PhosphoricAcid in Superphosphates, which have remained some time inBulk. By A. BEYER (Chern. Centr., 1687,1115, from Rep. anal. Chem.,7,327-330) .-In making a series of determinations to compare Peter-mann’s and Wagner’s methods for the estimahion of the phosphoricacid soluble in ammonium citrate, the author found that not only wasthe percentage of phosphoric acid soluble in waker reduced by longstanding in heaps, but also that soluble in ammouiurn citrahe solutionas estimated by Wagner’s method, The alteration in the percentageg f 224 ABSTRACTS OF CHEMICAL PAPERS.of phosplioric acid as estimated by Petermann’s method, was leesnoticeable.In superphosphates containing but little ferric oxide andalumina, the differences between the results obtained by the twomethods were not very great, but even a t the end of eight, days anappreciable loss of soluble phosphoric acid as determined by Wagner’smethod was observed, which quantity mas not so great where con-siderable quantities of acid had been employed.Petermann’s methoddoes not show so great a change in the soluble character of the phos-phoric acid in superphosphates after a time. If the superphosphatescontain considerable quantities of ferric oxide and alumina, the resultsas obtained by the two methods vary almost directly after manufac-ture, which differences increase the longer the superphosphates are kept.Here also the results obtained with Petermann’s method remainalmost constant, whilst the percentage as determined by Wagner’smethod, as also the phosphoric acid soluble in water, decreases.Cadmium Sulphide and the various Cadmium Pigments ofCommerce. By G. BBUCHNER (Chew,. Zeit., 11, 1087-1089 ; 1107-1109).-The author finds that all the forms of cadmium sulphidehave the same percentage composition represented by the formulaCdS, but that two modifications exist, one lemon-yellow, the simpleCdS, the other a polymeride of it, and of a vermilion colour.Thevariety of colour in different preparations of cadmium sulphide is dueto the mixture of these two modifications in varying proportions, andnot to the small quautity of soluble cadmium salt retained by thesulphide during its precipitation, as has been suggested. The yellowvariety is readily polymerised into the red variety by dilute acids,alkalis, &c., especially when in the nascent state, hence on precipitatingsolutions of cadmium salts with hydrogen sulphide, at first the yellowsulphide forms, but, as the liberated acid comes into action, the redsulphide is precipitated, and if the solution is acid beforehand, littleor no yellow sulphide is produced.The red variety passes throughthe yellow stage when dissolved in acids. Sodium sulphide producesthe yellow sulphide in dilute solutions of a cadmium salt, a reddishprecipitate in strong solutions, and a brick-red one in boiling solutions.Polysulphides of potassium or ammonium precipitate the yellowcadmium sulphide mixed with varying quantities of finely dividedsulphur, which can be extracted by carbon bisulphide. It is note-worthy that pure (red or yellow) cadmium sulphide is quite stable inlight, whereas this mixture of sulphide and s u l p h r oxidises rapidly inlight (not in darkness), becoming dirty white, especially after it isground with linseed oil.Cadmium hydroxide also assumes two forms : the simple one pre-pared by adding sodium hydroxide to solutions of cadmium salts givesrise to the yellow sulphide with sodium sulphide, &c.; the polymericone is formed when cadmium solutions are poured into solutions ofsodium hydroxide or when they are precipitated hot ; this hydroxideproduces the red sulphide, with an intermediate &cadmium sulph-hydroxide, Cd,S(OH)2, of a fiiie red colour, but too unstable for apigment ; the author considers this association of red colour with thefwo cadmium atoms in a single molecule, supports his view of theJ. W LINORGANIC CHEMISTRS. 225----Ammonia ..............polymeric character of the red sulphide. When heated carefully, theyellow and red sulphides undergo a series of changes of colour throughwhich they pass on cooling in the reverse order, both returning toyellow, the red sulphide having suffered molecular disarrangementduring the heating. When heated out of direct contact with the airthey neither sublime nor oxidise beyond just the surface.The authorfinally goes into the question of cadmium pigments, finds zinc com-pounds the most ordinary adulterants, and gives various tests hywhich a good pigment for oil painting may be recognised.Action of Water on Lead. By M. MELLER (J. pr. Chem. [2],36, 317--340).-A sample of water from the Ocker was distilled.The amounts of dissolved gases and of ammonia were determined inthe first, middle, and last fractions, and the behaviour of the differentfractions with lend observed.The water before distillation contained0.00015 per cent. of ammonia.D. A. L.First fraction. Middle fraction. Last fraction.-__-__------0.00115 p. c. 0'0001 p. c. O~OOOo8 p. c.Total volume ........... 2 -04 vol. p. c. 1 -196 vol. p. c.Cwbonic anhydride.. .... 1 -159 ), 0-178 ,:Oxygen ................ 0 -269 ,, 0-316 ,:Nitrogen (diff.) ......... 0 -612 ,, 0-70.2 ,,0.77 vol, p. c.0.025 ,,0'232 ,,0.513 ,,I------ ----- $---Dissolved $,ses reduced to 0" and 760 mm. pressure.First fraction. Middle fraction. Laat fraction.In this case also the first fraction' showed scarcely any action onlead, after remaining in contact with it for 24 hours. The middle andlast fractions attacked it with considerable energy.The protectinginfluence of the first fractions must be considered as due to their con-Total volume ...........Carbonic anhydride. .....Oxpgcn ................Nitrogen (diff.) ........2 -661 vol. p. c. 1 -31.2 vol. p. c. 1.047 vol. p. c.2.030 ), 0'228 ,, 0.069 ,,0 -198 ,i 0.358 ,, 0.341 ,,0 -433 ,, 0-738 ,, 0-637 ,226 ABSTRACTS OF CHEMICAL PAPERS.taining a, relatively large quantity of carbonic anhydride. Distilledwater, which was vigorously boiled f o r some time and quickly cooledin contact with air, was found to contain 0-04 per cent. of its volume ofcarbonic anhydride, 0.236 per cent. of its volume of oxygen, and 0.514per cent. of its volume of nitrogen. The rapid absorption of these p s e sexplains the behaviour of water so treated towards lead.Distilledwater, quite free from carbonic anhydride but containing oxygen,scarcely acts on lead, but on exposure to the air the liquid becomescloudy, owing to the formation of a white precipitate.Samples of water containing different amounts of carbonic anhydride,but an invariable quantity of oxygen, behave very differently with lead.I n one case, when the oxygen present was 0.35 per cent. of tile volumeof the liquid, and saturated solution of carbonic anhydride was addeduntil the water contained 0.14 per cent. of its volume, the lead wasappreciably attacked. On increasing the carbonic anhydride to0.6 vol. per cent., the athack became remarkably energetic. With1 vol. per cent.the action was considerably weaker, and when thecarbonic anhydride was increased to 1.5 vol. per cent. the lead was nolonger visibly corroded. Water containing 2,2.5, and 3 vols. per cent.of carbonic anhydride was equally inactive. Water containing car-bonic anhydride but no oxygen is practically without action on lead,when atmospheric air is excluded. When strips of lead are immersetlfor eight days in pure distilled water, recently boiled and cooled outof contact witb the air, they do not become tarnished. Before filtra-tion, however, but not after, the water gives a considerable reactionwith hydrogen sulphide. Pure water evidently attacks lead withformation of an oxide. Ordinary distilled water in which strips oElead were placed, and from which the air was excluded, contained amaximum quantity of lead a t the end of three days, after which thelead was by degrees thrown out of solution.This is explained bysupposing that water containing carbonic anhydride and oxygenin contact with lead forms lead carbonate, which dissolves in t h eexcess of the gas; but as more lead oxide is formed, this carbonicaphydride is absorbed, and all the lead falls out of solution as leadcarbonate. Distilled water, free from carbonic anhydride, to whichminute quantities of ammonia have been added, attacks lead, but iswithout action on it if carbonic anhydride is present.Lime water, through which a current of air, perfectly free from car-bonic anhydride, was passed, a t first slowly dissolved lead, but thiswas soon again thrown out of solution in the form of minute crystals.The solution attained a maximum after 13 hours, and then decreased.Sodium hydroxide solution behaved in a similar way. I n the absenceof oxygen, neither lime-water nor sodium hydroxide solution attackedlead.Lead tubing, buried in mortar, and kept in a dry room for ayear suffered no change, but when the mortar was occasionallymoistened with pure water, corrosion rapidly took place. Whensoapy water or an alkaline solution of lime was used instead of purewater, the decomposition-products consisted to some extent of redlead.Ordinary distilled water, to which a small quantity of sodiumcarbonate was added, dissolved no lead, but the metal became slowlINORGANIC CHEJIISTRY.227corered with a white, compact coating. When the water containedoxygen but no carbonic anhydride, lead was found in solution after a,few hours. A trace of sodium hydrogen carbonate added to distilledwater completely prevented the dissolution of lead, and the metalhecame covered Kith a protecting crust. Waters containing lead insolution were found to be freed from it by adding sodium carbonate.Pure lead carbonate is soluble in water containing carbonic anhydride ;it, is reprecipitsted by boiling the solution or by adding hydrogensodium carbonate to it. Evidently lead forms an acid carbonate,which is soluble in water but possesses little stability. Hydrogen cal-cium carbonate acts in precisely the same way as hydrogen sodiunrcarbonate.Polished strips of lead immersed in a saturated solution of purecalcium sulphate, containing oxygen, become covered with a hardwhite coating, but no lead goes into solution.In the absence ofoxygen, the metal remains perfectly bright. On placing lead coveredwith the white crust formed by long immersion in a solution of calcicsulphate, in pure distilled water, no lead went into solution exceptwhen a considerable quantity of carbonic anhydride was present.When a trace of hydrogen calcium carbonate was added to the solution,in no case was any lead dissolved. The coating is in all probability abasic sulphate of lead.The presence of minute quantities of chlorides, nitrates, organicmatter, and ammonia in water, did not influence its behaviour towardslead.This seems to depend on the presence of oxygen and carbonicanhydride. Water containing much organic matter, and rich in car-bonic anhydride, rapidly corrodes lead, but polished surfaces of themetal remain perfectly bright when immersed in pure solutions oforganic compounds, such as starch aud sugar, provided no carbonicanhydride is present.Colloidal Copper Sulphide. By W. SPRING and G. DE BOECK(BUZZ. Soc. Chim., 48, 165-170) .-An aqueous solution of coppersulphide can be obtained by precipitating any copper salt by hydrogensnlphide and washing by decantation with dilute sulphuric acid. Asthe impurities are removed, the copper sulphide becomes soluble andforms a dark-coloured solution with a slight greenish fluorescence.A purer product is obtained by precipitating with ammonium s d -phide.The solution contains hydrogen sulphide and may possiblycontain copper hydrosulphide. The former may be expelled by ashort ebullition without any notable precipitation of copper takingplace. Analysis of the liquid shows that the copper and sulphur arein the ratio required by the formula GUS, and hence the solutioncontains no copper hydrosulphide. Examination with the spectro-scope shows that the solution is a true solution and not simply aturbid liquid. It absorbs half the red, the violet, and half the blue inthe spectrum of a lamp flame.The copper sulphide is precipitated from this solution by the additionof various salts, a lkt of which is given i n the paper, but the power ofprecipitation bears no simple relation to the molecular weight 01-molecular volume of the salt.The valency of the metal, howevei.,G. T. MI228 ABSTRACTS OF CHEMICAL PAPERS.exerts considerable influence. Alum, chrome alum, and aluminiumsulphate, precipitate it when added in very small quantities, and theprecipitating power of salts of dyad metals is about 10 times as greatas that of salts of sodium and potassium.Schulze has made similar observations in the case of antimony sul-phide, but the copper sulphide is more readily precipitated thah theantimony compound. C. H. B.Stability of Mercuric Chloride Solutions. By V. MEYER(Ber., 20, 29'70-2974 ; comp. Abstr., 1887, 774).-Further experi-ments have shown that the solutions of mercuric chloride in the hardGottingen water, even when preserved in hermeticnlly sealed flaskswith or without the addition of common salt, gradually deposit mer-curic oxychloride, but less rapidly than when kept in vessels exposedto the air ; atmospheric dust, however, does not seem to influence therate of decomposition in any very marked way.If the solution ofmercuric chloride in ordinary water, instead of being exposed todiffused daylight, is kept in the dark in well-stoppered flasks, it isfound that practically no decomposition occurs, even after two monthsin solutions made with Gottingen water, pond water, and a wellwater charged with organic impurity, to which no addition of salt hasbeen made ; the very small amount of decomposition which actuallyoccurs being attributed to the unavoidable exposure to diffused day-light during the repeated examination of the solutions.w. P. w.Action of Alumina and Kaolin on Calcium Chloride.By A. GORGEU (Bull. SOC. Chim., 48, 51--52).-Calcium chloridemixed with alumina, kaolin, o r ordinary day, and fused a t a cherry-redheat in presence of moist air, yields crystalline products soluble indilute acids. With alumina, the crystals are distinct, colourless,mono-refractive, modified tetrahedra. They are anhydrous at 120",have the composition 6A1,O3,10CaO,CaCl,, and are slowly decom-posed by boiling water. Kaolin alone, or mixed with silica, seems toproduce various crystalline compounds, including mono-refractivecrystals resembling calcium garnet, but these could not be isolated.After prolonged fusion, the product was treated with dilute hydro-chloric acid and a solution of sugar.In this way modified tetrahedraof the composition 3Si0,,3Al,0,,16Ca0,2CaCl,. were obtained. Itwould seem that calcium garnet is first formed, and afterwards con-verted into the chlorosilicate. Calcium garnet, in fact, when fusedwith calcium chloride and oxide, yields modified tet'rahedra similar tothose just described.Soluble Manganese Oxide. By W. SPRING and G . DE BOECK(Bull. SOC. C'him., 48, 170--178).-This manganese oxide is obt-ainedby acting on potassium permanganate with sodium thiosulphate, andthoroughly washing the precipitate with water. As Boon as all thepotassium has been removed, a brown solution is obtained, from whichthe oxide is precipitated on the addition of any salt (comp.Gorgeu,Ann. C'him. Phys. [S], 63, 155). Amlysis of the product obtained byC. H. BINORGANIC CHEMISTRY. 229evaporation of the brown solution shows that it has the composition4(MnO,,H,O) ,Mn304..The portion of the original precipitate which is insoluble in waterhas the composition MnsOI3,4H20, or 3Mn02, Mn304, Mn203, 4H20.The colloidal manganese oxide is precipitated by salts more readilythan collojidal copper sulphide, and the valency of the metals in thesalts has the same influence in both cases. The manganese solutioncan be kept for a long time in sealed tubes, but if filtered throughpaper the manganese is completely precipitated.By A. JOLLES (Chem.Zeit., 11, 1394-1395).-In a previous communication, it is stated that the followingequation : KzMn04 + C2H60 = KZMnO3 + C2H40 + HzO, representsthe oxidation which takes place in the author's test for certainimpurities in chloroform (Abstr., 1887, 866). This statement hasbeen cont.ested. I t is now shown that both aldehyde and the manga-nite KzMn03 are produced, but in excess of alcohol the latter soondecomposes ; when, however, the substances are taken in equivalentquantities, the manganite can be separated and dried over sulphuricacid. It is a yellowisb-brown substance; is decomposed by dilutenitric and sulphuric acids, yielding manganese dioxide and hydrateddioxide and potassium uitrate or sulphate. It oxidises sulphurousacid to sulphuric acid, which in the nascent state forms manganesesulphate. Boiled with oxalic or tartaric acid, the manganite dissolveswith evolution of carbonic anhydride.On exposure to a current ofsuperheated steam and air, it is partially converted into manganate(compare Rousseau, Abstr., 1887, 552, 892).Manganese Compounds. By B. FRANKE ( J . p r . Chem. [Z], 36,451-468 ; compare Abstr., 1887,893, 1016) .-By heating 8 grams ofpotassium permanganate with 1OU C.C. of strong sulphuric acid at 300",and allowing it to cool, a brown crystalline salt, Mnz03,4S03,5H20,is formed. When this is treated with water, it is decomposed intoequimolecular quantities of mangnnous sulphate and the hydratedoxide H2Mn03; the salt is probably Mn2(S0&,H2SOd + 4H20.Manganic sulphate, Mn,(804)3, is obtained when the above salt isheated more strongly with sulphuric acid, in green crystals, decom-posed by water in the same way as the acid salt, showing that theatoms of manganese are of different valency.The salt may thereforebe regarded as the manganous salt of an acid, Mni'SO~(O~SOz*OH)2,analogous to the manganous manganese chloride (Abstr., 1881, 893).Mnz( S04)3,K2SOa, is obtained in red-brown crystals by carefully heat-ing 8 grams of potassium permanganate with the mother-liquor fromthe above acid salt; water decomposes it in a manner similar to theother salts.Steel-grey, metallic-looking crystals of H2Mn20~ are obtained wheneither of the foregoing compounds is thrown into very weak aqueoussoda ; sulphuric acid decomposes it into manganous sulphate andmanganous acid, MnO(OH)2, which is thus obtained pure as a brownpowder ; this points to the formula Mn<O>Mn(OH)a.C.H. B.Potassium Manganite.D. A. L.230 ABSTRACTS OF CREMICAL PAPERS.The brown colour of the solution of manganese dioxide in stronghydrochloric acid is caused by the presence of manganous acid.A. G. B.Permanganates. By T. KLOBB (BUZZ. SOC. Chim., 48, 240-244).-The author has previously prepared certain permanganates byadding potassium permanganate to ammonincal solutions of certainmetallic salts (Abstr., 1886, 983). He has now obtained similarderivatives from luteocobalt chloride in a similar way.Luteocobal tic pe rmangan ate, Go2( MnO ,) 6, 1 2NH3, is obtained bymixing warm concentrated solutions of luteocobalt chloride (1 mol.)and potassium permanganate (12 mols.) It separates in the form ofa precipitate mixed with a salt which crystallises in hexagonal plates,and is formed in greater proportion when the permanganate is not inexcess.The latter can be removed by treatment with cold water,and the luteocobaltic permariganate is recrystaliised from water a t60". It then forms very brilliant, black tetahedra., only slightlysoluble in cold water, but more soluble in hot water with partialdecomposition. When heated, it detonates, and it also explodes whenstruck. With hydrochloric acid, it yields manganous chloride andluteocobaltic chloride.Luteocobaltic chloroper~~~angar2.ate, (Coz,12NH,)Cl,,2Mn0,, is pre-pared by mixing a solution of luteocobaltic chloride (8 mols.) with asolution of luteocobaltic permanganate (1 mol.), filtering rapidly,and allowing t o cool.It separates in small, black lamellae with theform of a regular hexagon, red or brown by transmitted light. It isvery unstable, and is decomposed by water with removal of thechloride, but dissolves without decomposition in a solution of luteo-cobaltic chloride. When heated rapidly, it detonates, but it does notexplode on percussion.Luteocobaltic bromopermanganate is analogous to the chloroper-manganate, rind is prepared in a similar way, or more simply, bymixing warm solutions of potassium permanganate (3 mols.) andluteocobaltic bromide (1 mol.), and allowing them to remain. It formsbrilliazit, hexagonal lamells, which are much more stable than thechlorine-derivative, and are not decomposed by boiling water.The salt which is obtained in the preparation of lnteocobaltic per-manganate, and which crystallises in hexagonal lamells, is alsoobtained by mixing cold concentrated solutions of luteocobalticchloride (1 rnol.) and potassium permanganate (3 mols.), when itseparates slowly in violet hexagonal lamells of the composition( Co2,12NH3) Cl2,2ICC1,4MnOa, very soluble in water with partial de-composition in to its constituents. When heated, it behaves like thepreceding salts. It may be regarded as a compound of luteocobalticpermanganate and luteocobaltic chloride with potassium chloride.It can also be formed by dissolving luteocobaltic chloropermanganatein potassium chloride solution, o r by the action of luteocobaltic per-manganate on a large excess of potassium chloride. C. H. B.Electrolytic Extraction of Antimony. By W. BORCHERS (Chem,Zeit., 11, 1021--1022).-The author has based a process for theextraction of antimony (from all its combinations soluble in sodiuMINERALOGICAL CHEMISTRY. 231sulphide solution) on the electrolytic method of Classen and Ludwig(Abstr., 1885, 932) for the estimation of that metal.The ore is extracted with sodium sulphide solution, using 3 mols.Na2S for every mol. Sh,S,. The concentrated extract is mixed with3 per cent. of sodium chloride to increase its conductivity, and electro-lysed. According to the intensity of the current, the metal is depositedas a powder or in shining scales. To prevent deposition of sulphur, therelation of 1 atom of available Na for every atom of oxidisable sulphurmust, be maintained, but as t h e mixture Sb,S3 + Na,S + 2NaHOis too unstable, the above proportions are used; too much sodiumsulphide is to be avoided as i t increases the resistance of the liquid.The common salt is easily crystallised from the electrolysed solo-tions, and the sulphur recovered as sodium thiosulphate without muchdifficulty. D. A. L.By G. v. KNORRE and P. OLSPHFWSKY (Ber., 20,3043--3052).-Attempts were made to prepare Fremy ' s potassiumantimoniate, K4Sb,07 ( J . pr. Chein., 45, 209), but without success ; itis concluded that that salt does not exist, and thatFremy's compoundis a mixture of potassium antimoniate and potash.Potassium antirnoniate, K,Sb,Oc, contains 5 mols. H,O when air-dried, and is a, white granular salt. 100 parts of water at 20" dissolve2.81 parts of anhydrous salt. Rp.. gr. of saturated solution at18" = 1.0263. A table is given showing the loss of weight it under-goes at various temperatures ; at 330" it contains rather more than1 mol. H20, and the author assumes that 1 mol. H,O is chemicallycombined, and that the formula of the air-dry salt is K,E2Sb,O7 +4H20. When the hot aqueous solution is evaporated, a gummy saltremains ; when this is dried at loo", it has the composition expressedby the formula, K,Sb206 + 3H,O.Potassium antimoniate was also prepared by the methods ofRrunner (DinrgZ. polyt. J., 159, 356) and tteynoso (Annalen, 80,272) ;details of preparation and results are given (compare Abstr., 188&1184). N. H. M.Antimoniates

ISSN:0368-1769    

DOI:10.1039/CA8885400219

出版商:RSC    

年代:1888

数据来源: RSC

摘要:

MINERALOGICAL CHEMISTRY. M i n e r a 1 o g i c a 1 C h e m i s try. 231 Arksutite from Ivigtut in Greenland. By A. E. NORDENSKIOLD (Zed. Eryst. Min., 13, 400-401, from GYeol. FGren. Porhandl., 8, 172-175).-A specimen of arksutite mas separated according to Thoulet’s method, and gave three different substances : an optically isotropic mineral having a sp. gr. of 3.12 (fluorspar) ; a mineral lighter than 2.99 (possibly thomsenolite) ; and a birefractive sub- stance of sp. gr. = 2.994, and giving on analysis the following results :- A1 . Ca. Mg. Na . F. Total. 17-28 0.22 0-05 24.72 57.16 99-43232 ABSTRACTS OF CKEMICAL PAPERS. corresponding with the formula 5NaF + 3A1,F3. The composition of arksutite is thus perfectly in accord with that of the chiolite of Brandl. From the optical properties of the two minerals, there can be no doubt that they are identical.Mineralogical Notes. By G. FL~NK (Zeit. Kmpt. Mia., 13, 401- 408, from Bihany till K. Su. vet. akad. handl., 12, Afd. 2).-The author gives the resiilts of a crystallographical and chemical investigation of the following minerals :--1. Cobalt-glance from Nordmarken ; 2. Cosalite from Nordrnarken ; 3. Pyrochroite from Nordmarken ; 4. Magnetite from Norduiarken ; 5. Manganomagnetite from Lkng- ban; 6. Berzeliite from the same locality; 7. Monimolite from Pajsberg; 8. Xenotime from Hittero, Norway; 9. Apatite from Nordmarken; 10. Lizvrite from Thyrill, Iceland ; 11. Epidote from Nordmai-ken (28 new planes) ; 12. Epidote from Morkhult; 13. Manganese-vesuvian from Pajsberg ; 14.Orthoclase from the kraf3ite of Krafla, Iceland; 15. Titanite from the Fredriksberg Mine, Nord- marken. The author also describes a new mineral, 7iarstigite, from Pajsberg, named after the mine in which it WAS discovered. The min_eral 1relongsJo the- rhombic system, and exhibits the forms OOP, mPm, km, wP2, =Pa, P2. No cleavage was observed. The mineral is colourless, and has a vitreous lustre. Analysis gave the following results :- B. H. B. a : b : L: = 0.7141 : 1 : 1.01495. SiOp. Al,O,. CaO. MnO. MgO. KzO. Na,O. HzO. Total. 38.94 10.61 29.23 12.81 3.27 0.35 0.71 3.97 99.89 B. H. B. Manganese and Uranium Oxides. By C. RAMMELSBERG (Zeit. Kiyst. Mi?&., 13, 418-419, from Ber. Akad. Ber., 1885, 97).-The author finds that both arti ticial Mn,O, and crystallised hausmannite, when boiled with concentrated nitric acid, or treated with dilute sul phuric acid, split up into 2Mn0, which dissolves, and insoluble MnO,.Crystallised manganite is not decomposed by sulphuric acid in the same way. Powdered braunite undergoes decomposition, although not completely. Hausmannite should therefore be regarded as having the composition 2Mn0,Mn02, whilst the formula of braunite is MnO, (Mn, Si) 0,. The author gives the following new analysis of pitchblende from Joacbimstha1:- TTO* UOz. PbO. FeO. CaO. SiOz. Total. 42.87 40.50 3.25 3-78 3.00 6.60 100*00 The general formula of pitchblende is R0,R02 = (U02,Pb,Fe,Ca)0,(U,Si)02 ; the formula of the varieties containing thorium is (UOz,Pb,Fe,Ca) O,(U,Th) 02. The oxides, Y20a, Erz03, Ce20s, which occur in Beveral varieties of pitchblende, appear to be isomorphically mixed with the compoundMINERALOGICAL CHEMISTRY.233 R0,R02. which crystallises in a similar manner. The latter is thus analogous in constitution to braunite, B. H. B. Minerals from Carinthia. By A. BRUNLECHNER (Zeit. K ~ y s t . Min., 13, 391-392, from Jnhrb. nat. hist. Landesmuseums in Karnthen, 17, l--.j).-Among the Carinthian minerals described by the author are the following :-Greenockite from Raibl, as a lemon-yellow coat- ing on slate; garnet from Lamprechtsberg in the Lavanthal, as orange crystals enclosing copper pyrites ; tourmaline from the same locality, in short, dark-brown crystals ; zoisite from Stanziwurdikopf, preen in columnar crystals in mica schist. Analyses are given of two srwcimens of siderite : I.Translucent crystals, with plane faces, from Wolch ; 11. Yellowish-white crystals, with curved faces, from Lolling :- FeC0,. MnC03. NgCO,. CaC0,. Impurities. Total. I. 95-10 2.11 2.19 trace 0.59 99.99 11. 94.97 trace 3.22 1.78 0.25 100.22 In addition to other factors, the proportion of calcium, even in small quantities, appears to influence the crystal form of iron_ carbun- ate. B. H. B. Martinite from the West Indies. By J. H. KLOOS (Jahr6.f. Min., 1888, i, Ref., 41, from Xammlg. geol. Reichsmuseums, Leiden).- Martinite is a new calcium phosphate pseudomorphous after gypsum, fi*om the phosphorite beds of the Island of Curapo. The pseudo- morphs occur in lenticular crystals, having the fomn of gypsum (-P, -Pm, mym). The crystals are colourless and transparent. Their sp.gr. is 2.892 to 2.896. Analysis gave the following results :- P!A CaO. Loss on ignition. Total. 47.87 47.63 5-46 100.96 Fluorine is absent. The results of the analysis are in accord with the empirical formula 10Ca0, 4P3O5,3H20. By G. CESARO (Zed. K ~ y s t . Min., 13, 421-422, from Ann. SOC. gebl. BeZg., 12, 173).-The mineral from VisB, to which the name destin&te has been assigned, appears to be a variety of diadochite. An almost white and very pure specimen gave on analysis the following results :- B. H. B. Diadochite from Vise. Fe203. P205. SO,. H20. Hygroscopic H,O. C. Total. 3'7.60 16.76 18-85 25.35 0.30 1.40 100.26 The mineral on microscopic examination was found to belong t o the monoclinic system. B. H. B. Mineral from Krerns in Austria.By E. DRASCHE (Juh~7,. f. Myn., 1888, i, Ref., 29-30, from Vwh. geoZ. Beiclisanst., 19, 81).-!Ihe234 ABSTRACTS OF CHEMICAL PAPERS. author gives an analysis of a mineral, erroneously supposed to be bauxite, which is found in considerable quantities in terbedded in crystalline schists. The mineral is of a white t o yellowish-brown colour. For the analysis, pure white specimens were selected. The results were as follows :- SiO,. Al,03. CaO. K20. Na,O. SO,. P20,. H 2 0 a t 100'. 1.30 38.00 0.75 3.75 4.54 38.85 0.88 0 45 The remainder consists of water and organic substance. B. H. B. Manganotantalite from the Ural. By A. ARZRUNI (Juhrh. f. Min., 1888, i, Ref., 18, from Trams. Imp. Rws. Min. Soc.).-The crys- tal described was found in the Bakakin gold washings in the Sanarka Cistrict, in the sou_th of-the Ural.It exhibits the planes ~ P w , mPw, O P , @03, ~ P w , P2, 4P2. It is semi-metallic and nearly black. In very thin layers the colour is orange to ruby-red. Sp. gr. = 7.37. Analyses gave the following results :- Ta20,. Nb,O,. Sn02 + WO,. FeO. MnO. CaO. Ignition. Total. 79.81 4.47 0.67 1.17 13.88 0.17 0.16 100.33 These results correspond with the formula llMnTaOs + FeNbO,. This miiieral, of which as yet only one crystal has been foiind, is the member of the tantalite group richest in manganese and tantalum. B. H. B. Kainosite, a new Mineral from Hitterii, in Norway. By A. E. NORDENSKIOLD (Zeit. Kryst. M k . , 13, 399-400, from GeoZ. 2sliiren. ForhandZ., 8, 143-1 46) .-In consequence of the unusual composition of this new mineral, the author has termed it kainosite from ~ a s v d ~ (strange).It consists of a calcium yttrium silicate. mixed with a carbonate and water. The only specimen found is a portion of a liexagonal prism. The optical examination, however, shows that it belongs, not to the hexagonal, but to the rhombic or to the mono- clinic system. The mineral is semi-transparent, yellowish-brown, and birefractive. Its hardness is 5.5, and sp. gr. 3.413. Analysis gave the following results :- SiO,. Y,03 + Er20* CaO. MgO. FeO. Nk0. CO,. H20. Total. 34.63 37.67 15-95 0.03 0.26 0.40 5.90 5.26 100.10 corresponding with the formula 4Si0,,CO2,Y2O,(Er2O3),2CaO ,2H20. B. H. B. Chemical Nature of Eudialite. By C. RAHMELSBEEG (Juh.1-b. f. Mii~., 1887, ii, Ref., 449-451, from Sitzber.E. Preuss. Aknd. Wiss., 24, 441-461).-The author has analysed specimens of this rare silico-zirconate from the principal localities at which it is found. The results of his analyseg were as follows :-MISERALOGICAL CHEMISTRY. 235 C1. SiO,. I. 1.53 49.84 11. 1.57 48.88 111. 1-70 46.68 IV. 1,441 46.84 Na20. I. 13.32 11. 8.80 111. 11.24 TV. 10.70 ZrO. 14.0 1 15.17 15.43 16.09 K20. 0.75 1.24 0.42 0.50 Ce20,. FeO. 2.35 5.96 4.07 7% - 7.32 5.19 5.92 H2O. 1.24 2-50 0.90 1.77 MnO. CaO. 0.64 10-77 0-52 10.63 2-82 11.76 1-50 1 a . a Sp. gr. 2.928 2.908 3.081 3.000 I. Eudialite from 'Kangerdluarsuk, Greenland ; II. From Brevig, Norway ; 111. Prom Sigter.5, Norway ; 1V. From Aro, Norway. The formula given by the author for the eudialite of Greenland and of Brevig is NaC1,2R'6R''3( Si,Zr)10026, and for the eudialite of Sigtero and Aro is NaC1,R'1zR''g(Si,Zr)25065.B. H. B. Zeolites from Chili. By L. DARAPSKY (Jahrb. f. Nin., 1888, i, Mem., 65--67).-The author has subjected various zeolites, from the mineralogical collection of the National Museum of Santiago, to chemical examination. The analytical results were as follows :- SiO2. A1203. CaO. N%O. H,O. K20. Fe203. Total. I. 52.67 19.80 11.25 - 16.29 - - 100.01 11. 54.60 - 29.52 1.06 15.03 -- - 100.21 IrI. 47-69 25-45 14-05 - 13.25 - - 100.44 IV. 4&i$ 25.99 9-11 5.23 16.41 - - 92-48 V. 45.15 26.53 11-86 2-24 13.81 0.45 - 100.04 VI. 43-37 24.27 21.74 0.96 5.28 - 4.44 100.26 I. Hypostilbite from altered amygdaloydal porphyry at the Hacienda La Quinta at Curic6 ; formula, 2Ca0,2AlzO3,9SiOz,5HZO.11. Okenite from the Rio Pntagan ; formula, 9Ca0,3SiOz,3Hz0. This appears to be identical with the zeolite from Greenland termed bordite by Dufrenoy. 111. Scolenite, accompanying the okenite ; sp. gr. 2.1 5 ; formula, CaO,A1,O3,3SiO2.3H2O. IV. Typical mesolite from the Desert of Atacama. V. A dense form of the same mineral coating the weathered rock of the Rodaito Mines in the Province of Coquimbo. VI. Prehnite, in green globular masses, from the Rodaito Mines, associated with calcice crystals, and containing small, black scales or wires of natural amalgam (Ag3gHg). B. H. B. Manganese-bearing Idocrase from Sweden. By L. J. IGEL- STROM (Jahrb, f. Min., 1887, ii, Ref., 453, from Bull. SOC. franp. min., 9, %Z -24) .--The mineral occurs with mangauese-garnet, manganese- epidote, and manganese-silicate in limestone at the Jakobsberg manganese mine in Wermland.The crystals exhibit the forms UP, WP, 03Po0, P. In thick plates, the colour is black ; in powder, dark- violet. In thin sections, the mineral is highly pleochroic, having an amethyst and orange colour. In chemical composition it is character-236 ABSTRACTS OF CHEMICAL PAPERS. ised by a remarkably high percentage of manganese, copper, and lead, as is shown by the following analytical results :- Si02. A1203. FeO. MnO. CuO. PbO. CaO. MgO. Total. 38.07 13-88 5-08 4 7 2 2.16 1.80 25-60 5.07 938.38 B. H. B. Beryl from Madagascar. By A. DAMOUR (Jahrb. f. M A , 1888, i, Ref., 9, from Bull. SOC. frnnp. min., 9, 153--154).-The crystal described was found with tourmaline, quartz, and triphane at Fara- fatrana, on the east coast of Madagascar.I t is characterised by its pink coloar. Its composition is as follows :- SiO,. A1203. BeO. FeO. MnO. CaO. Ignition. Total. Sp. gr. 66.56 18.66 12.47 0.09 0.21 0.06 2.30 100.35 2.72 B. H. B. So-called Soda Granites. By A. GERHARD (Jnh~b. f. Mi%., 1887, ii, Mem., 267--275).-Althongh in the analyses of most granites, the percentage of potash exceeds that of soda, yet certain granites are known in which the opposite is the case. Attention was first drawn to such granites in 1856 by Halighton, who termed them soda-granites. The author has made a series of careful analyses. of typical examples of these rocks, and finds that in the granites of Baveno, both the red and the white varieties, and in those of Bejby in Sweden, the soda is not, as stated by former observers, in excess of the potash.These rocks, consequently, should no longer be regarded as soda-p-anites. I n the granite of Ulferud, in Sweden, the author finds 74.77 per cent. of silica, 2.65 per cent. of potash, and 4.40 per cent. of soda, thus con- firming the results obtained by Hummel arid Erdmann. This rock is thus a true soda-granite. In addition to microcline, ortboclase, quartz, muscovite, biotite, zircon, and apatite, i t contains a plagioclase-felspar, which gave on anelysis the following resnlts :- Si02. A1203. CaO. K20. N+O. Total. Sp. p. 67.99 19.23 1-84 1.25 9.69 100*00 2.63 and must therefore be regarded as an almost pure albite. B.H. B. Albite in Norwegian Pegmatites. By A. LACROIX ( J d ~ b . f. Min., 1887, ii, Ref., 455, from Bull. SOC. franq. mi%., 9, 131-134).- The albite in tjhe pegmatite veins of Moss, Hittera, and Ytterhy is always emylanted on microcline, and is accompanied by quartz, calcite, and a mica differing from the muscovite of the rock." The crystals are poorly developed, the predominating form being mPm. Bands of albite contained in the microcline appear to be younger than that mineral. An analysis of the albite of Garta near Arendal gave the following results :- SiO,. A1203. Na,O. E20. Total. Sp. gr. 68.40 19.89 10-69 0.90 99.88 2.601 B. H. B. Griqualandite. B,v B. R. BROUGH (Chern. News, 56, 244).-The author shows that the analysis of the supposed new mineral describedMINERALOGICAL CHEMISTRY.237 hy Hepburn (Abstr., 1887, 709) as griqualmdite, corresponds more closely with the simple formula H,0,Be203,4Si02, than with the more complicated formula given. The pewfitage compositions demanded by the two formulae are- SiO,.. Fe20,. H20. H2Fe,Si,0 12. , . . . . . . . . 5 7.42 38.28 4.30 H,,Fe,Si,O,, . . . . . . . . 56.80 37.87 5.33 The formula IEz0,Fe203,4SiOz for griqualand’ite is analogous to that of crociddite, aegirine, and arfvcdsonite, Na20,Fe203,4Si02. Griqua- landite must therefore be regarded as a crocidolihe in which hydrogen is substituted for sodium. I t is not a pseudomorph after crocidolite, but rather a fibrous hornblende or uralite resulting from the alteration of that mineral. B. H. B. NTineral Veins, By Ii“. SANDBERGER (Zeit.Rryst. Min., 13, 409- 417).-This memoir is an abstract of the second volume of the author’s treatise on mineral veins, in which he brings fopward further evidence in support of the lateral secretion theory of the genesis of mineral veins. This theory assumes that water percolating through the country-rock has, by the aid of carbonic acid and other natural solvents, dissolved out of i t a11 the minerals now forming the consti- tuents of mheral veins. The gveater portion of the volume is occupied by a discassion of the genesis of mineral, veins in crystalline and stratified rocks. In discussing the tin-ore veins in lithionite-gpanite, the author applies the term protolithionite to a dark lithium mica found in the manite masses of Cornwall, the Erzgebirge, and the Fichtelgebirge.I n this mica, as much as 0.22 pel cent. of tin oxide has been detected. The deposition of the tin ore, of zinnwaldite, and of turmaline in fissures in the granite is due to the decomposition of this mica. Prosopite is formed by the action of dissolved calcium carbonate on topaz. The fluorine derived from the mica, explains the presence of fluorspar in the veins. Tin has also been detected in the potassium- mica of Villeder in Morbihm, and consequently the author regards the tin-ore veins of that district as formed by lateral secretion, whilst he regards the tin ore in the pegmatite of Finbo, in the beds of Pitkaranta and Breitenbruun, as primitive. At Marienberg in Saxony, tin-ore veins occur in gneiss. In their formation by being dissolved out of the mica in the country-rock, the constituents, silica and tin oxide, least soluble in alkaline carbonates, were deposited first ; then followed arsenic and copper; then cobalt and nickel ores, barytes (derived from the orthoclase of the country-rock) ; and lastly calcite and silver ores.In tbe mica of the mica- schist of Ehrenfriedersdorf, which is traversed by tin-ore veins, tin, arsenic, and fluorine have been detected. Lastly, small quantities of tin have been discovered in the phyllites of various districts. Iu those of Eibenstock and Johanngeorgenstadt, boron has also been found. This discovery enables the formation of interstratified turma- line-schist in these phyllites to be explained. The tin-ore deposits in Secondary mica is absent.VOL. LIV. 1-238 ABSTRACTS OF CHEMICAL PAPERS. limestone at Campiglia were undoubtedly derived from an eruptire rock in the vicinity. The Freiberg gneiss is extremely rich in mica, and in this mineral the majority of the metals occurring in the veins of that district have been detected. The barytes, however, appears to have been derived from the felspar of the country-rock. The metals contained in eruptive rocks of recent age, for instance, in the basalt of Strieth and in the phonolite of Hohenkrahen, segregate in fissures as mag- netic or iron pyrites o r as hydrated ferric oxide. The ore veins of Transylvania and of America are thought by the author to have heen formed in a similar manner by leaching out of the andesites, &c. I n the micas of Hnngarian rocks, all the metals occurring in the mineral veins are found, whilst fluorine is absent'.This is in accord with the known rare occurrence of fluorspar in those veins. The barytes is derived from the anorthic felspar of the country-rocks. At the Cornstock lode, the lateral secretion theory has been confirmed by the dscovery of the precious metals in the ftugite of the country- rock. The mineral veins of Caracoles in Jurassic limestone have been derived from the adjacent quartz-trachyte. The metals in this rock are contained for the most part in the hornblende, whilst in the felspar is contained a considerable proportion of barium, which appears in the veins as barytes. B. H. B. Composition of the Meteorite of Saint-Denis-Westrem. By C. KL~MENT (Jcchrb. .f. Min., 1888, i, Ref., 45, from Bull.mas. roy. hist. nat. BeZg., 4, 273-282).-The anal3 sis of the meteorite from Saint- Denis-Westrem in East Flanders, gave the following results :- SiO,. A1203. Cr203. FeO. CaO. MgO. Na20. 40.20 2.54 O%O 16.22 2-00 25.08 0.99 Fe. Ni. co. S. Total. 10.37 1.24 0.12 2.12 101.78 From these results, the author calculates the following mineralo- gical composition :-Chrome-iron, ( PeCr204), 1.33 ; iron sulphide, ( Fe7S8), 5*:37 ; nickel-iron, 8.48 ; bronzite, 26.18 ; olivine, 46.41. The remaining 14.01 per cent., which consist,s of- SiO,. Al,03. CaO. MgO. NaaO. 7-88 2-54 2.00 0-60 0.99 may perhaps be plagioclase (maskelynite). B. H. B. Mineral Springs in the Peninsula of Methana. By A. K. DAMRERGIS (Brr., 20, 3328-3330).-The sulphur springs of Methanw rise on the coast on the east side of the Chelona range near the village of Wromolimni, a t about the sea, level.The temperature OE the vater-which rises in more than 24 springs forming t>hree separate groups-varies from 26.4" to 31" ; the specific gravity of the water varies from 1.02865 to 1.02882. The watcr, when examined under theMINERALOGICAL CHEMISTRY. 239 1. 0 -1343 0.0228 0 -0313 0~0000 0 -0388 0 -0276 0.0008 0 -0449 0 *0840 0 -0065 - - 0*032,4 microscope, was found to contain the bacteria Beggiutou nivea, often found in sulphurous wa.ters. The water from the various springs showed almost identical composition. The analysis of water from one of the springs gave in parts per 10,000 :--NaCl, 297.630 ; KCI, 6.960 ; MgCl,, 36.948 ; MgBr2, 0.584 ; CaS04, 21.357 ; MgS04, 18.486 ; CaCO,, 4.600; MgCO,, 2,250; Fe,O,, 0.038; A1303, 0.019; Si02, 0.485 ; organic matter, 0.042 ; total solids, 389.399.GO2 as bicarbon- ate, 3.200; CO, free, 7.218 ; SH,, 0.109 ; total mineral constituents, 399.926. Besides this the water contained traces of ammonia, nitric acid, phosphoric acid, iodine, and fluorine. L. T. T. 2. --- 0 -1902 0.07M 0 -0170 0 '0010 0 -0167 0 -0063 0'0106 0 -0179 0 -1295 0.0250 - - 0 0200 Analyses of Water from Artesian Wells. By C . KLEMENT (Jahrb. f. Min., 1888, i, Ref., 71-72, from Bull. mus. roy. hist. nat. Belg., 3, 1- 97).-The wells investigated are in Brussels or its immediate vicinity. The bore-holes struck water, below a bed of clay, in fissured chalk underlain by rocks of Silurian age.The following are the depths and temperatures of the water :-1. Hospital St. Pierre, Rue Haute, Brussels, 94.5 m., 15.2" ; 2. Distillery, St. Gilles, 65.62 m., 1;11.8" ; 3. Candle factory, Cureghem, 73 m., 12.5"; 4. Godin foundry, Laekm. '106.9 m., 12.5"; 5. St. Sauveur baths, Brussels, 75 m., 12.8"; 6. Boeck brewery, Koekelberg, 115.5 rn., 12.0" ; 7. Brewery, Anderlecht, 95 m., 12.2" ; 8. Starch manufactory, Machelen, 82 m., 12.5" The analyses were conducted in accordance with Bunsen's method wihh the following resulh :- 3. -- 0 -0852 0 '0425 - 0 -0020 - 0.0286 0.0174 0 -4618 0.0433 0-0257 0 * 0173 0 -0398 0 -0274 -- CaC03 ...... MgC03 ...... Na2C0, ..... K2NO3.. ..... I(2SOj. ...... Ca904 ...... MgO12 ....... Nat'l ....... KCl.. ....... SiOz ........ Org. subs..... C02 free ..... 00, ......... 4. 0 -1084 0 *0593 0 *0569 0 -0021 0 -0256 - - 0 -0490 0-0175 0*0300 0 '0178 0 '1024 0 '0074 - 5. 0.1811 0 *0976 0 *0606 0.0016 0 '0174 - - 0 '0020 0 '0230 0 '0320 0 '0135 0 -1659 0 -0143 - - 6. 0 -0679 0-0362 0 '0653 0 -0014 0 -0263 - - 0 -1980 0 -0177 0 '0302 0-0160 0 -0759 0 -0032 - 7. --. 0 -0998 0 * 0492 0 '0140 0 *0008 0 *0374 I - 0.44i09 0 '0093 0.0258 0.0245 0 '0755 0 -0045 8. -_ 0.1295 0-0686 0 *0'726 trace 0 -0263 - - 0 *0102 0.0233 0 *0:302 0.0115 0.1231 0 -0084 - B. H. B.MINERALOGICAL CHEMISTRY.M i n e r a 1 o g i c a 1 C h e m i s try.231Arksutite from Ivigtut in Greenland. By A. E. NORDENSKIOLD(Zed. Eryst. Min., 13, 400-401, from GYeol. FGren. Porhandl., 8,172-175).-A specimen of arksutite mas separated according toThoulet’s method, and gave three different substances : an opticallyisotropic mineral having a sp.gr. of 3.12 (fluorspar) ; a minerallighter than 2.99 (possibly thomsenolite) ; and a birefractive sub-stance of sp. gr. = 2.994, and giving on analysis the followingresults :-A1 . Ca. Mg. Na . F. Total.17-28 0.22 0-05 24.72 57.16 99-4232 ABSTRACTS OF CKEMICAL PAPERS.corresponding with the formula 5NaF + 3A1,F3. The composition ofarksutite is thus perfectly in accord with that of the chiolite of Brandl.From the optical properties of the two minerals, there can be no doubtthat they are identical.Mineralogical Notes. By G. FL~NK (Zeit. Kmpt. Mia., 13, 401-408, from Bihany till K. Su. vet. akad. handl., 12, Afd. 2).-The authorgives the resiilts of a crystallographical and chemical investigationof the following minerals :--1.Cobalt-glance from Nordmarken ;2. Cosalite from Nordrnarken ; 3. Pyrochroite from Nordmarken ;4. Magnetite from Norduiarken ; 5. Manganomagnetite from Lkng-ban; 6. Berzeliite from the same locality; 7. Monimolite fromPajsberg; 8. Xenotime from Hittero, Norway; 9. Apatite fromNordmarken; 10. Lizvrite from Thyrill, Iceland ; 11. Epidote fromNordmai-ken (28 new planes) ; 12. Epidote from Morkhult; 13.Manganese-vesuvian from Pajsberg ; 14. Orthoclase from the kraf3iteof Krafla, Iceland; 15. Titanite from the Fredriksberg Mine, Nord-marken.The author also describes a new mineral, 7iarstigite, from Pajsberg,named after the mine in which it WAS discovered.The min_eral1relongsJo the- rhombic system, and exhibits the forms OOP, mPm,km, wP2, =Pa, P2. No cleavagewas observed. The mineral is colourless, and has a vitreous lustre.Analysis gave the following results :-B. H. B.a : b : L: = 0.7141 : 1 : 1.01495.SiOp. Al,O,. CaO. MnO. MgO. KzO. Na,O. HzO. Total.38.94 10.61 29.23 12.81 3.27 0.35 0.71 3.97 99.89B. H. B.Manganese and Uranium Oxides. By C. RAMMELSBERG (Zeit.Kiyst. Mi?&., 13, 418-419, from Ber. Akad. Ber., 1885, 97).-Theauthor finds that both arti ticial Mn,O, and crystallised hausmannite,when boiled with concentrated nitric acid, or treated with dilutesul phuric acid, split up into 2Mn0, which dissolves, and insolubleMnO,. Crystallised manganite is not decomposed by sulphuric acidin the same way.Powdered braunite undergoes decomposition,although not completely. Hausmannite should therefore be regardedas having the composition 2Mn0,Mn02, whilst the formula of brauniteis MnO, (Mn, Si) 0,.The author gives the following new analysis of pitchblende fromJoacbimstha1:-TTO* UOz. PbO. FeO. CaO. SiOz. Total.42.87 40.50 3.25 3-78 3.00 6.60 100*00The general formula of pitchblende isR0,R02 = (U02,Pb,Fe,Ca)0,(U,Si)02 ;the formula of the varieties containing thorium is(UOz,Pb,Fe,Ca) O,(U,Th) 02.The oxides, Y20a, Erz03, Ce20s, which occur in Beveral varieties ofpitchblende, appear to be isomorphically mixed with the compounMINERALOGICAL CHEMISTRY. 233R0,R02.which crystallises in a similar manner.The latter is thus analogous in constitution to braunite,B. H.B.Minerals from Carinthia. By A. BRUNLECHNER (Zeit. K ~ y s t .Min., 13, 391-392, from Jnhrb. nat. hist. Landesmuseums in Karnthen,17, l--.j).-Among the Carinthian minerals described by the authorare the following :-Greenockite from Raibl, as a lemon-yellow coat-ing on slate; garnet from Lamprechtsberg in the Lavanthal, asorange crystals enclosing copper pyrites ; tourmaline from the samelocality, in short, dark-brown crystals ; zoisite from Stanziwurdikopf,preen in columnar crystals in mica schist. Analyses are given of twosrwcimens of siderite : I. Translucent crystals, with plane faces, fromWolch ; 11. Yellowish-white crystals, with curved faces, fromLolling :-FeC0,. MnC03. NgCO,.CaC0,. Impurities. Total.I. 95-10 2.11 2.19 trace 0.59 99.9911. 94.97 trace 3.22 1.78 0.25 100.22In addition to other factors, the proportion of calcium, even insmall quantities, appears to influence the crystal form of iron_ carbun-ate. B. H. B.Martinite from the West Indies. By J. H. KLOOS (Jahr6.f.Min., 1888, i, Ref., 41, from Xammlg. geol. Reichsmuseums, Leiden).-Martinite is a new calcium phosphate pseudomorphous after gypsum,fi*om the phosphorite beds of the Island of Curapo. The pseudo-morphs occur in lenticular crystals, having the fomn of gypsum(-P, -Pm, mym). The crystals are colourless and transparent.Their sp. gr. is 2.892 to 2.896. Analysis gave the followingresults :-P!A CaO. Loss on ignition. Total.47.87 47.63 5-46 100.96Fluorine is absent.The results of the analysis are in accord withthe empirical formula 10Ca0, 4P3O5,3H20.By G. CESARO (Zed. K ~ y s t . Min., 13,421-422, from Ann. SOC. gebl. BeZg., 12, 173).-The mineral fromVisB, to which the name destin&te has been assigned, appears to be avariety of diadochite. An almost white and very pure specimen gaveon analysis the following results :-B. H. B.Diadochite from Vise.Fe203. P205. SO,. H20. Hygroscopic H,O. C. Total.3'7.60 16.76 18-85 25.35 0.30 1.40 100.26The mineral on microscopic examination was found to belong t othe monoclinic system. B. H. B.Mineral from Krerns in Austria. By E. DRASCHE (Juh~7,. f.Myn., 1888, i, Ref., 29-30, from Vwh. geoZ. Beiclisanst., 19, 81).-!Ih234 ABSTRACTS OF CHEMICAL PAPERS.author gives an analysis of a mineral, erroneously supposed to bebauxite, which is found in considerable quantities in terbedded incrystalline schists.The mineral is of a white t o yellowish-browncolour. For the analysis, pure white specimens were selected. Theresults were as follows :-SiO,. Al,03. CaO. K20. Na,O. SO,. P20,. H 2 0 a t 100'.1.30 38.00 0.75 3.75 4.54 38.85 0.88 0 45The remainder consists of water and organic substance.B. H. B.Manganotantalite from the Ural. By A. ARZRUNI (Juhrh. f.Min., 1888, i, Ref., 18, from Trams. Imp. Rws. Min. Soc.).-The crys-tal described was found in the Bakakin gold washings in theSanarka Cistrict, in the sou_th of-the Ural. It exhibits the planes~ P w , mPw, O P , @03, ~ P w , P2, 4P2.It is semi-metallic andnearly black. In very thin layers the colour is orange to ruby-red.Sp. gr. = 7.37. Analyses gave the following results :-Ta20,. Nb,O,. Sn02 + WO,. FeO. MnO. CaO. Ignition. Total.79.81 4.47 0.67 1.17 13.88 0.17 0.16 100.33These results correspond with the formula llMnTaOs + FeNbO,.This miiieral, of which as yet only one crystal has been foiind, is themember of the tantalite group richest in manganese and tantalum.B. H. B.Kainosite, a new Mineral from Hitterii, in Norway. By A.E. NORDENSKIOLD (Zeit. Kryst. M k . , 13, 399-400, from GeoZ. 2sliiren.ForhandZ., 8, 143-1 46) .-In consequence of the unusual compositionof this new mineral, the author has termed it kainosite from ~ a s v d ~(strange). It consists of a calcium yttrium silicate.mixed with acarbonate and water. The only specimen found is a portion of aliexagonal prism. The optical examination, however, shows that itbelongs, not to the hexagonal, but to the rhombic or to the mono-clinic system. The mineral is semi-transparent, yellowish-brown, andbirefractive. Its hardness is 5.5, and sp. gr. 3.413. Analysis gavethe following results :-SiO,. Y,03 + Er20* CaO. MgO. FeO. Nk0. CO,. H20. Total.34.63 37.67 15-95 0.03 0.26 0.40 5.90 5.26 100.10corresponding with the formula 4Si0,,CO2,Y2O,(Er2O3),2CaO ,2H20.B. H. B.Chemical Nature of Eudialite. By C. RAHMELSBEEG (Juh.1-b. f.Mii~., 1887, ii, Ref., 449-451, from Sitzber. E. Preuss. Aknd. Wiss.,24, 441-461).-The author has analysed specimens of this raresilico-zirconate from the principal localities at which it is found.Theresults of his analyseg were as follows :MISERALOGICAL CHEMISTRY. 235C1. SiO,.I. 1.53 49.8411. 1.57 48.88111. 1-70 46.68IV. 1,441 46.84Na20.I. 13.3211. 8.80111. 11.24TV. 10.70ZrO.14.0 115.1715.4316.09K20.0.751.240.420.50Ce20,. FeO.2.35 5.964.07 7%- 7.325.19 5.92H2O.1.242-500.901.77MnO. CaO.0.64 10-770-52 10.632-82 11.761-50 1 a . aSp. gr.2.9282.9083.0813.000I. Eudialite from 'Kangerdluarsuk, Greenland ; II. From Brevig,Norway ; 111. Prom Sigter.5, Norway ; 1V. From Aro, Norway. Theformula given by the author for the eudialite of Greenland and ofBrevig is NaC1,2R'6R''3( Si,Zr)10026, and for the eudialite of Sigteroand Aro is NaC1,R'1zR''g(Si,Zr)25065.B. H. B.Zeolites from Chili. By L. DARAPSKY (Jahrb. f. Nin., 1888, i,Mem., 65--67).-The author has subjected various zeolites, from themineralogical collection of the National Museum of Santiago, tochemical examination. The analytical results were as follows :-SiO2. A1203. CaO. N%O. H,O. K20. Fe203. Total.I. 52.67 19.80 11.25 - 16.29 - - 100.0111. 54.60 - 29.52 1.06 15.03 -- - 100.21IrI. 47-69 25-45 14-05 - 13.25 - - 100.44IV. 4&i$ 25.99 9-11 5.23 16.41 - - 92-48V. 45.15 26.53 11-86 2-24 13.81 0.45 - 100.04VI. 43-37 24.27 21.74 0.96 5.28 - 4.44 100.26I. Hypostilbite from altered amygdaloydal porphyry at theHacienda La Quinta at Curic6 ; formula, 2Ca0,2AlzO3,9SiOz,5HZO.11.Okenite from the Rio Pntagan ; formula, 9Ca0,3SiOz,3Hz0. Thisappears to be identical with the zeolite from Greenland termedbordite by Dufrenoy. 111. Scolenite, accompanying the okenite ;sp. gr. 2.1 5 ; formula, CaO,A1,O3,3SiO2.3H2O. IV. Typical mesolitefrom the Desert of Atacama. V. A dense form of the same mineralcoating the weathered rock of the Rodaito Mines in the Province ofCoquimbo. VI. Prehnite, in green globular masses, from the RodaitoMines, associated with calcice crystals, and containing small, blackscales or wires of natural amalgam (Ag3gHg). B. H. B.Manganese-bearing Idocrase from Sweden. By L. J. IGEL-STROM (Jahrb, f. Min., 1887, ii, Ref., 453, from Bull. SOC. franp. min.,9, %Z -24) .--The mineral occurs with mangauese-garnet, manganese-epidote, and manganese-silicate in limestone at the Jakobsbergmanganese mine in Wermland.The crystals exhibit the forms UP,WP, 03Po0, P. In thick plates, the colour is black ; in powder, dark-violet. In thin sections, the mineral is highly pleochroic, having anamethyst and orange colour. In chemical composition it is character236 ABSTRACTS OF CHEMICAL PAPERS.ised by a remarkably high percentage of manganese, copper, andlead, as is shown by the following analytical results :-Si02. A1203. FeO. MnO. CuO. PbO. CaO. MgO. Total.38.07 13-88 5-08 4 7 2 2.16 1.80 25-60 5.07 938.38B. H. B.Beryl from Madagascar. By A. DAMOUR (Jahrb. f. M A , 1888,i, Ref., 9, from Bull. SOC. frnnp. min., 9, 153--154).-The crystaldescribed was found with tourmaline, quartz, and triphane at Fara-fatrana, on the east coast of Madagascar.I t is characterised by itspink coloar. Its composition is as follows :-SiO,. A1203. BeO. FeO. MnO. CaO. Ignition. Total. Sp. gr.66.56 18.66 12.47 0.09 0.21 0.06 2.30 100.35 2.72B. H. B.So-called Soda Granites. By A. GERHARD (Jnh~b. f. Mi%., 1887,ii, Mem., 267--275).-Althongh in the analyses of most granites, thepercentage of potash exceeds that of soda, yet certain granites areknown in which the opposite is the case. Attention was first drawnto such granites in 1856 by Halighton, who termed them soda-granites.The author has made a series of careful analyses. of typical examplesof these rocks, and finds that in the granites of Baveno, both the redand the white varieties, and in those of Bejby in Sweden, the soda isnot, as stated by former observers, in excess of the potash. Theserocks, consequently, should no longer be regarded as soda-p-anites.I n the granite of Ulferud, in Sweden, the author finds 74.77 per cent.of silica, 2.65 per cent.of potash, and 4.40 per cent. of soda, thus con-firming the results obtained by Hummel arid Erdmann. This rock isthus a true soda-granite. In addition to microcline, ortboclase, quartz,muscovite, biotite, zircon, and apatite, i t contains a plagioclase-felspar,which gave on anelysis the following resnlts :-Si02. A1203. CaO. K20. N+O. Total. Sp. p.67.99 19.23 1-84 1.25 9.69 100*00 2.63and must therefore be regarded as an almost pure albite.B. H. B.Albite in Norwegian Pegmatites.By A. LACROIX ( J d ~ b . f.Min., 1887, ii, Ref., 455, from Bull. SOC. franq. mi%., 9, 131-134).-The albite in tjhe pegmatite veins of Moss, Hittera, and Ytterhy isalways emylanted on microcline, and is accompanied by quartz, calcite,and a mica differing from the muscovite of the rock." The crystalsare poorly developed, the predominating form being mPm. Bands ofalbite contained in the microcline appear to be younger than thatmineral. An analysis of the albite of Garta near Arendal gave thefollowing results :-SiO,. A1203. Na,O. E20. Total. Sp. gr.68.40 19.89 10-69 0.90 99.88 2.601B. H. B.Griqualandite. B,v B. R. BROUGH (Chern. News, 56, 244).-Theauthor shows that the analysis of the supposed new mineral describeMINERALOGICAL CHEMISTRY.237hy Hepburn (Abstr., 1887, 709) as griqualmdite, corresponds moreclosely with the simple formula H,0,Be203,4Si02, than with the morecomplicated formula given. The pewfitage compositions demandedby the two formulae are-SiO,.. Fe20,. H20.H2Fe,Si,0 12. , . . . . . . . . 5 7.42 38.28 4.30H,,Fe,Si,O,, . . . . . . . . 56.80 37.87 5.33The formula IEz0,Fe203,4SiOz for griqualand’ite is analogous to thatof crociddite, aegirine, and arfvcdsonite, Na20,Fe203,4Si02. Griqua-landite must therefore be regarded as a crocidolihe in which hydrogenis substituted for sodium. I t is not a pseudomorph after crocidolite,but rather a fibrous hornblende or uralite resulting from the alterationof that mineral. B. H. B.NTineral Veins, By Ii“.SANDBERGER (Zeit. Rryst. Min., 13, 409-417).-This memoir is an abstract of the second volume of theauthor’s treatise on mineral veins, in which he brings fopward furtherevidence in support of the lateral secretion theory of the genesis ofmineral veins. This theory assumes that water percolating throughthe country-rock has, by the aid of carbonic acid and other naturalsolvents, dissolved out of i t a11 the minerals now forming the consti-tuents of mheral veins. The gveater portion of the volume isoccupied by a discassion of the genesis of mineral, veins in crystallineand stratified rocks.In discussing the tin-ore veins in lithionite-gpanite, the authorapplies the term protolithionite to a dark lithium mica found in themanite masses of Cornwall, the Erzgebirge, and the Fichtelgebirge.I n this mica, as much as 0.22 pel cent.of tin oxide has been detected.The deposition of the tin ore, of zinnwaldite, and of turmaline infissures in the granite is due to the decomposition of this mica.Prosopite is formed by the action of dissolved calcium carbonate ontopaz. The fluorine derived from the mica, explains the presence offluorspar in the veins. Tin has also been detected in the potassium-mica of Villeder in Morbihm, and consequently the author regardsthe tin-ore veins of that district as formed by lateral secretion, whilsthe regards the tin ore in the pegmatite of Finbo, in the beds ofPitkaranta and Breitenbruun, as primitive. At Marienberg in Saxony,tin-ore veins occur in gneiss. In their formation by being dissolvedout of the mica in the country-rock, the constituents, silica and tinoxide, least soluble in alkaline carbonates, were deposited first ; thenfollowed arsenic and copper; then cobalt and nickel ores, barytes(derived from the orthoclase of the country-rock) ; and lastly calciteand silver ores.In tbe mica of the mica-schist of Ehrenfriedersdorf, which is traversed by tin-ore veins, tin,arsenic, and fluorine have been detected. Lastly, small quantities oftin have been discovered in the phyllites of various districts. Iuthose of Eibenstock and Johanngeorgenstadt, boron has also beenfound. This discovery enables the formation of interstratified turma-line-schist in these phyllites to be explained.The tin-ore deposits inSecondary mica is absent.VOL. LIV. 1238 ABSTRACTS OF CHEMICAL PAPERS.limestone at Campiglia were undoubtedly derived from an eruptirerock in the vicinity.The Freiberg gneiss is extremely rich in mica, and in this mineralthe majority of the metals occurring in the veins of that district havebeen detected. The barytes, however, appears to have been derivedfrom the felspar of the country-rock. The metals contained ineruptive rocks of recent age, for instance, in the basalt of Striethand in the phonolite of Hohenkrahen, segregate in fissures as mag-netic or iron pyrites o r as hydrated ferric oxide. The ore veins ofTransylvania and of America are thought by the author to haveheen formed in a similar manner by leaching out of the andesites, &c.I n the micas of Hnngarian rocks, all the metals occurring in themineral veins are found, whilst fluorine is absent'.This is in accordwith the known rare occurrence of fluorspar in those veins. Thebarytes is derived from the anorthic felspar of the country-rocks. Atthe Cornstock lode, the lateral secretion theory has been confirmed bythe dscovery of the precious metals in the ftugite of the country-rock. The mineral veins of Caracoles in Jurassic limestone havebeen derived from the adjacent quartz-trachyte. The metals in thisrock are contained for the most part in the hornblende, whilst in thefelspar is contained a considerable proportion of barium, which appearsin the veins as barytes. B. H. B.Composition of the Meteorite of Saint-Denis-Westrem. ByC.KL~MENT (Jcchrb. .f. Min., 1888, i, Ref., 45, from Bull. mas. roy. hist.nat. BeZg., 4, 273-282).-The anal3 sis of the meteorite from Saint-Denis-Westrem in East Flanders, gave the following results :-SiO,. A1203. Cr203. FeO. CaO. MgO. Na20.40.20 2.54 O%O 16.22 2-00 25.08 0.99Fe. Ni. co. S. Total.10.37 1.24 0.12 2.12 101.78From these results, the author calculates the following mineralo-gical composition :-Chrome-iron, ( PeCr204), 1.33 ; iron sulphide,( Fe7S8), 5*:37 ; nickel-iron, 8.48 ; bronzite, 26.18 ; olivine, 46.41. Theremaining 14.01 per cent., which consist,s of-SiO,. Al,03. CaO. MgO. NaaO.7-88 2-54 2.00 0-60 0.99may perhaps be plagioclase (maskelynite). B. H. B.Mineral Springs in the Peninsula of Methana.By A. K.DAMRERGIS (Brr., 20, 3328-3330).-The sulphur springs of Methanwrise on the coast on the east side of the Chelona range near thevillage of Wromolimni, a t about the sea, level. The temperature OEthe vater-which rises in more than 24 springs forming t>hree separategroups-varies from 26.4" to 31" ; the specific gravity of the watervaries from 1.02865 to 1.02882. The watcr, when examined under thMINERALOGICAL CHEMISTRY. 2391.0 -13430.02280 -03130~00000 -03880 -02760.00080 -04490 *08400 -0065--0*032,4microscope, was found to contain the bacteria Beggiutou nivea, oftenfound in sulphurous wa.ters. The water from the various springsshowed almost identical composition. The analysis of water from oneof the springs gave in parts per 10,000 :--NaCl, 297.630 ; KCI, 6.960 ;MgCl,, 36.948 ; MgBr2, 0.584 ; CaS04, 21.357 ; MgS04, 18.486 ;CaCO,, 4.600; MgCO,, 2,250; Fe,O,, 0.038; A1303, 0.019; Si02,0.485 ; organic matter, 0.042 ; total solids, 389.399. GO2 as bicarbon-ate, 3.200; CO, free, 7.218 ; SH,, 0.109 ; total mineral constituents,399.926. Besides this the water contained traces of ammonia, nitricacid, phosphoric acid, iodine, and fluorine. L. T. T.2.---0 -19020.07M0 -01700 '00100 -01670 -00630'01060 -01790 -12950.0250- -0 0200Analyses of Water from Artesian Wells. By C . KLEMENT(Jahrb. f. Min., 1888, i, Ref., 71-72, from Bull. mus. roy. hist. nat. Belg.,3, 1- 97).-The wells investigated are in Brussels or its immediatevicinity. The bore-holes struck water, below a bed of clay, in fissuredchalk underlain by rocks of Silurian age. The following are the depthsand temperatures of the water :-1. Hospital St. Pierre, Rue Haute,Brussels, 94.5 m., 15.2" ; 2. Distillery, St. Gilles, 65.62 m., 1;11.8" ; 3.Candle factory, Cureghem, 73 m., 12.5"; 4. Godin foundry, Laekm.'106.9 m., 12.5"; 5. St. Sauveur baths, Brussels, 75 m., 12.8"; 6.Boeck brewery, Koekelberg, 115.5 rn., 12.0" ; 7. Brewery, Anderlecht,95 m., 12.2" ; 8. Starch manufactory, Machelen, 82 m., 12.5" Theanalyses were conducted in accordance with Bunsen's method wihhthe following resulh :-3.--0 -08520 '0425 -0 -0020 -0.02860.01740 -46180.04330-02570 * 01730 -03980 -0274--CaC03 ......MgC03 ......Na2C0, .....K2NO3.. .....I(2SOj. ......Ca904 ......MgO12 .......Nat'l .......KCl.. .......SiOz ........Org. subs. ....C02 free ..... 00, .........4.0 -10840 *05930 *05690 -00210 -0256--0 -04900-01750*03000 '01780 '10240 '0074-5.0.18110 *09760 *06060.00160 '0174 --0 '00200 '02300 '03200 '01350 -16590 -0143 --6.0 -06790-03620 '06530 -00140 -0263 --0 -19800 -01770 '03020-01600 -07590 -0032 -7.--.0 -09980 * 04920 '01400 *00080 *0374I -0.44i090 '00930.02580.02450 '07550 -00458.-_0.12950-06860 *0'726trace0 -0263 --0 *01020.02330 *0:3020.01150.12310 -0084 -B. H. B

ISSN:0368-1769    

DOI:10.1039/CA8885400231

出版商:RSC    

年代:1888

数据来源: RSC

摘要:

240 ABSTRACTS OF CHEMICAL PAPERS. Organic Chemistry. Preparation of Trirnethylene. By G. GUSTAVSON (J. pr. Chem. [ 2J 36 300-303).-Trirnethylene may he prepared by heating trimethylene bromide with zinc-dust and aqueous alcohol or water ; 1 litre of the gas is thus obtained from 10 grams of bromide and from this qnmtity of the gas 7.2 gmms of dry crude trimethylene bromide (or 4.57 grams iodide) can be again produced showing that this method of preparation gives good results. When trimethylene is passed into concentcrated sulphuric acid liquid hydrocarbons are formed on the surface of the acid and the solution after diluting yields normal props1 alcohol on distillation. F. S. IC. Conversion of Trimethylene Bromide into Propylene Bromide. By G. GUSTATSOX (J. pr. Chem. [ a ] 36 303-304).- When trimethylene bromide and aluminium bromide are placed together in a sealed tube a t the ordinary temperature the former undergoes intermolecular change and propylene 6romide is formed.F. S . I(. Ethylpropylacetylene. By A. BOHAL (Bull. SOC. Chim. 48,216- 219) .-Butyrone (106 grams) is gradually mixed with phosphorus pentachloride (200 grams) and when the action has ceased a furhher quantity of butyrone is added and the reaction is completed by heating. The liquid is then cooled and poured on ice and the chlo- rine-derivative separated and heated with alcoholic potash in sealed tubes a t 130-150" for 20 hours. The product is treated with water and dried over calcium chloride. The ethylpro pylncetylene thus obtained is a liquid which boils at 105-106" and has an odour of acetylene ; sp.gr. at 0" = 0.760. It does not combine with cnprous chloride but with mercuric chloride a white precipitate is formed after some time and when this precipitate is dissolved in dilute hydrochloric acid an odour of butyrone can be perceived. Bromine acts on it with great energy yielding a liquid of higher sp. gr. than water. When treated with about twice its own weight of concentrated sulphuric acid a t 0" the hydrocarbon yields a red-Pirown solution which becomes colourless when mixed with ice. The sole product of hydrolysis is butyrone. The removal of 2 mols. of hydrogen chloride from dichlorobutyrone may yield diethylallylene or the corresponding hydrocarbon with a closed chain but the fact that this hydrocarbon forms a compound with mercuric chloride and is readily hydrolysed combined with the absence of tertiary carbon united with the carbon which is in union with the chlorine render it most probable that this hydrocarbon is ethylpropylacetylene CEt i CPr. C.H. B.ORGANIC CHEMISTRY. 241 Hydrolysis of Diallyl. By A. BBHAL (BuZZ. SOC. Chim. 48 43-51).-Diallyl is added drop by drop with contiiiual agitation to ordinary concentrated sulphuric acid cooled by ice. The acid becomes red but the colour disappears when the acid is diluted by ice which is added in sufficient quantity to reduce the temperature and the product is then neutralised with an alkali or an alkaline earth preferably the former. The liquid is then distilled and the snper- natant layer separated. In all cases the sulphonic acid C6Hll*SO3H.is obtained. The barium calcium and potassium salts are very soluble in water and crystallise with difficulty. The supernatant layer of the distillate boils at 93" and is soluble in 1.3 parts of water at the ordinary temperature. It does not combine with sodium hydrogen sulphite even after prolonged contact has no action on hydroxylamine and does not reduce ammoniacal silver nitrate in alcoholic or aqueous solution. It dissolves in hydrochloric acid with development of heat but no combination takes place ; wheu heated with this acid in sealed tubes at 143-150" it yields dichlor- hydrin bciling at 170-180". It does not precipitate magnesium chloride solutions and when treated with phosphorus pentachloride a considerable quantity of hydrogen chloride is evolved but no definite products could be isolated.Bromine is absorbed with great energy but the product readily decomposes and cannot be distilled even i n a vacuum. In one case the liquid was treated with excess of bromine and then washed with water; when the water was added there was considerable development of heat and the liquid separated into two layers. The lower layer was hexylene bromide probably correspond- ing with pseudohexylene glycol. The upper aqueous liquid readily reduced ammoniacal silver nitrate and when neutralised and distilled yielded a small quantity of a liquid having the properties of an alde- hyde. The original liquid heated with water a t 150-180" yields no When hexyl pseudoglycol is mixed with concentrated snlphuric acid at Oo it yields a product identical with that obtained by the action of the acid on diallyl.The hydrolysis of diallyl under the influence of sulphuric acid yields a compound formed by the dehydration of isohexyl glycol identical with the hexglene pseudoxide obtained by Wurtz by the action of silver oxide on diallyl dihvdriodide. The oxide thus ob- glycol. tained differs from ordinary "glycol" by its inaptitude to combine with wa,ter and has the constitution <cH;.CaMe>O. Its forma- CH-G BMe tion is due to the fact that the two alcoholic groups from which the oxide is derived are separated by two atoms of carbon ; and the two ethylene-groups do not act independently but have been linked together by the atom of oxygen formirig an oxide more stable than the glycol.Moreover the hydroxyl-groups in pseudohexyl glycol are in the 01 position and hence readily form an anhydride. The other products of the hydrolysis are a sulphoriic acid and polymerides of diallyl. C. H. B.242 ABSTRACTS OF CHEMICAL PAPERS. Pyrrolylene Tetrabromide. By G. CIAMICIAN (Ber. 20 3061- 3064) .-The author considers the explanation given by Grimaux and CloSz (Abstr. 1887 789) to be improbable. Hydrocyanic Acid and Cyanogen Iodide. By E. V. MEYER (J. pr. Chern. [2] 36 292-5399). The author confirms Millon's statement that small quantities of hydrocyanic acid prevent the reduction of iodic acid by formic acid and finds that the hydrocyanic acid causes the iodic acid to assume a passive state since even when all the former acid has been expelled from the solution by boiling a certain time elapses before the iodine begins to separate.On the other hand hydrocyanic acid does not prevent but only checks the reduction of iodic acid by sulphurous acid and a considerable quantity of the latter must be added before the separation of iodine com- mences. Hydrocyanic acid has no influence on the reduction of iodic acid by hydriodic acid. When a solution of iodine is added to hydrocyanic acid cyanogen iodide and hydriodic acid are formed up t o a certain point after which the iodine is no longer acted on. These two products have a great tendency to reproduce hydrocyanic acid and iodine but an excess of hydrocyanic acid prevents this in- verse change taking place. Numerous experiments were made to find how much iodine must be added to a constant quantity of hydro- cyanic acid in varying quantities of water before free iodine is present in the solution and the tabulated results show that the amount of iodine used increases with dilution and with the temperature.Cyanogen iodide is completely decomposed by hydriodic acid and snl- phurous acid and these reactions may be employed for the estimation of cyanogen iodide volumetrically. Hydrogen sulphide stannous chloride and other reducing agents act in like manner but towards oxidising agents cyanogen iodide is as stable as iodic acid. Oxidation of the Azulmic Matter obtained by the Electro- lysis of Ammonia with Carbon Electrodes. Bg A. MILLOT (BUZZ. SOC. Chim. 48 238-240) .-The composition of the black residue obtained by evaporating the liquid after electrolysis (Abstr.1886 979) then extracting with alcohol and finally with water is-C 35.5 ; H 2-0 ; N 36.3 ; 0 26.2. It is not readily oxidised by sodium hypo- chlorite. 10 grams of the residue was dissolved in water and ammonia the ammonia expelled by heating on the water-bath and the gelatinous residue mixed with 50 C.C. of hydrogen peroxide capable of giving 3000 C.C. of oxygen. The mixture was heated on the water-bath for 10 or 12 hours and filtered. On cooling ammelide is deposited and on further concentration a second quantity of this compound is obtained The mother-liquor is evaporated t o dryness and extracted with alcohol which when concentrated deposits crystals of cyanuric acid. The last extracts yield nacreous plates or rhombo'idal prisms of the hydrated acid resembling the modification which Liebig termed cjanilic acid.When this is dissolved in sulphuric acid and pre- cipitated by adding water it separates in the ordinary form. That portion of the products of oxidation which is insoluble in F. S. K.ORGANIC CHEMISTRY. 213 alcohol consists of ammonium sulphate the sulphuric acid having been present as an impurity in the hydrogen peroxide. Sulphuranes. By I3. RRADN (Bey. 20 2967-2970) .-When ethyl snlphurane EtS*C,H,.S.C,H is heated for many hours with excess of ethyl iodide at 100" and the product exlracted with water a crystalline compound is obtained which is either diethylvinyl- sulphurane or triethylsulphine iodide whilst the portion insoluble in water yields ethylene bisulphide on fractional distillation.The diethyl-derivative of ethylene mercaptan Et*S*C,H,*S.Et when treated with ethvl iodide in like manner. is converted into a C. H. B. mixture of triethylsulpkne iodide and ethjlene disulphide. w. P. w. Propane-derivatives. By C. m T ~ ~ ~ ~ ~ r ; ~ ~ ~ (Bull. Xoc. Ghim. 48 108-112).-The product of the action of bromine on excess of propyl alcohol contains an alcohol which boils constantly at 87' but has all the other properties of propyl alcohol. After dehydration by means of potassium carbonate it boils at' 92". It is evident that a hydrate of primary propyl alcohol does actually exist. Propyl mercaptan and propyl sulphide boil at 67-68" and 141.5- 142.5" respectively under a pressure of 772 mm. Cshours's number 130-135* for the boiling point of propyl sulphide was doubtless due to the presence of impurities one of which was most probably the mercaptan formed in consequence of the partial decomposition of the potassium sulphide into hydrosulphide during the preparation of the d.erivative.This decomposition becomes much more marked with the higher members in the series. Orthopropylsulphonic acid is obtained by the action of nitric acid o€ sp. gr. 13 on propyl mercaptan. The reactiou is violent and the first products are nitrogen oxides and a red oil probably ethyl thioet hylsulphonate which gradually dissolves as the effervescence ceases. Orthopropyl oayswlphide is obtained by the action of nitric acid of sp. gr. 1.2 on propyl sulphide. I t forms long colourlesq and odonrless needles which melt at 14.5-15" cannot be distilled with- out decomposition and dissolve in water alcohol and ether.It burns with a brilliant flame and is easily reduced by ferrous chloride or by nascent hydrogen. When a solution of the oxysulphide and calcium uitrate is concentrated i t yields a fibrocrystalline compound 4[2SOPr2,Ca(N03),] + Ca(NO& which melts at SO" and shows the phenomena of supersaturation and superfusion in a very marked manner. To obtain diortlzopropyl sulphone it is necessary to use a warm con- centrat,ed solution of potassium permanganate as the oxidising agent. 'l'he sulphone crystallises i u beautiful transparent scales soluble in water but more soluble in alcohol and ether. It cannot be distilled without decomposition otherwise than in a current of steam.-~ono~ropylphos~hol-lc acid is contained in the dense viscous residue obtained in the preparation of prDpy1 chloride by the action of phos- phorus pentachloride on propyl alcohol. This residue also contains an244 ABSTRACTS OF CHENICAL PAPERS. acid which yields a barium salt of the composition PO(OPr)O,Ba anhydrous a t looo and soluble in cold water from which it separates on boiling and an ethereal salt PO(OPr)3 which is most soluble in water at 70-80" dissolves in alcohol and ether and cannot be distilled without decomposition even in a vacuum. By A. REFORMATSKY ( J . pr. Chem. [el 36 340-347).-Diethyl methyl carbinol CMeEt,-OH is prepared by the action of zinc on a mixture of diethyl ketone (100 grams,) and methyl iodide (495 grams) and subsequent treatment witah water.It is a colourless mobile liquid having a pleasant smell resembling trimethyl carbinol boils a t 122-123" and has the sp. gr. 0.8237 at 20° 0.8194 a t 25" 0.8179 at 30° and 0.8143 35" (water at 0" = 1). The acetate is a colourless liquid boiling at 148" (coi-r.). The iodide boils a t 140-144" and is parhly decomposed on distillation. When oxidised with chromic mixture diethyl methyl carbinol yields acetic acid as the sole product Bromination of Ally1 Alcohol. By I. FIXK (Nonatsh. 8 561- 562).-By bromination of ally1 alcohol in absence of water a dibrom- hydrin is formed almost in the theoretical proportions as observed by Markownikoff and v Tollens. In the presence of water there is formed in addition a monobromhydrin C3H,Br02 boiling a t 138" a t a pressure of 17 mm.; it is shown to be of this constitution by its con- version into glycerol and triacetin. Diisobutenyl Oxide. By S. PRZYBYTEK (Rer. 20 3239-3246). -The methods of preparation of the following substances have already been given (this vol. p. 123). The dichlorliydrin C,H,4C1,(OH)z is a thick viscid pale-yellow liquid of faint odour and burning taste. Diisobutenyl oxide <-02> CH CMe*CHz*CHz*CMe<~~~> is it colourless mobiIe liquid of agreeable odour and burning taste ; it is heavier than water and boils a t 170-180" under 125 mm. pressure. As was to be expected from their respective constitutions it combines with water with greater slowness and difficulty than does erythrene dioxide. Octylerythrol C8H,,(OH)4 is a thick and very viscid liquid of bitter taste readily soluble in water and alcohol but insoluble in ether.It can be formed directly from the chlorhydrin by heating with potash and a large excess of water. Action of Hydrogen Chloride on Glycerol. By A. FAUCONNIER and J. SANSOX (BUZZ. Soc. Chim. 48,2s6-%8).-Dry hydrogen chloride was pasbed into glycerol for five days in an apparatus provided with a reflux condenser. The fraction of the product boiling below 80" contains hydrochloric acid and water together with a small quantity of an oily substance precipitated by water; the fraction 80-12O0 contains the two dichlorhydrins in quantity equal to half the weight of the glycerol ; the fraction 120-150" contains glyceryl monochlor- hydrin and substances which crystallise in the receiver.The pro- ducts boiling above 150" have not yet been examined. C. H. B. Synthesis of Diethyl Methyl Carbinol. G. T M. V. H. V. A. J. G.ORGANIC CHEMISTRY. 245 The crystalline solid in the last fraction amounts to 0.75 per cent. of the glycerol used. It crystallises from alcohol in white needles which have the same composition as epichlorhydrin and melt at 109-110". The substance is probably a polymeriae of epichlorhydrin ; it dissolves readily in cold benzene ether carbon bisulphide and chloroform is somewhat soluble in alcohol especially on heating and dissolves slowly in boiling water from which it crystallises in very lorig needles. C. H. B. Sugar-Tike Nature 01 Formose. 39 0. LOEW '(BeT. 20 Y~SY- 3043).-A solution of formose (10 grams) in I litre of water is boiled in a reflux apparatus and the whole extracted with chloroform ; the residue obtained by evaporating the chloroform is treated with alcohol aniline and a little hydrochloric acid when an intense red coloration is prodnced showing the presence of furfuraldehyde. When formose is digested with 1 per cent.sulphuric acid on a water-bath more fur- furaldehyde is obtained than from other sugars. Formose has all the following characteristics of sugar :-(1) Sweet taste; (2) strong reducing power; (3) ready decomposition by dilute alkali ; (4) formation of saccharic acid by the action of lime ; (5) power of combination with hydrogen and hydrogen cyanide and formation of an osazone ; (6) formation of humous substances by acids ; (7) formation of furfuraldehyde by dilute acid ; (8) capability of fermentation.The author concludes with a criticism of Wehmer's paper on the carbohydrate nature of formose (this vol. p. 40). N. H. M. Erythrene Dioxide. By S. PRZYBYTEK (Ber. 20 3234-3239). -Erythrene dioxide when treztted with bromine in tubes immersed in cold water is gradually converted into a citron-pellow crystalline dibromide which is insoluble in water alcohol and chloroform and readily decomposes with evolution of hydrogen bromide. A polymeride of the dioxide is obtained in very small quantities by lieatring the dioxide at 110-130" (below its boiling point = 137") a better yield being obtained at 140-150" but the best yield is obtained when sealed tubes containing powdered anhydrous sodium sulphate just moistened with the dioxide are heated at 110-120" for 10 days.In all cases the polymerisation is very incomplete. It is an amorphous colourless substance devoid of taste and odour and insoluble in water alcohol ether benzene and chloroform. It can although with diffi- culty be converted into erythrol and its derivatives. Uihydroxyerythren.edisuZphonic acid C,H,(OH),( SO,H) is obtained when erythrene dioxide is shaken with a slight excess of concentrated aqueous hydrogen sodium sulphite and the sodium salt formed decom- posed with oxalic acid. It forms a deliquescent mass of felted needles and is very unstable charring when gently heated and yielding sulphurous anhydride when its aqueous solution is heated at 50". Its salts on the contrary are very stable.Inosite. Ry LORIN (BUZZ. SOC. Chim. 48 235-237).-Thc author showed 10 years ago from its behaviour with oxalic acid that inosite 1s a polyhydric alcohol (Abstr. 1878 398). A. J. G. G. H. B.246 ABSTRACTS OF UHEMICAL PAPERS. Carbohydrates. By b. G. EKSTRAND and C. J. JOHANSON (Ber. 20 3310-3317).-The authors have obtained a new carbohydrate from the haulm of the Phleum pratenss. The hanlm is thickened ah its lower end to a bulb and in the autumn this bulb increases in size and becomes filled with ft concentrated solution of a carbohydrate to which the authors give the name graminin. This substance is a powder resembling starch of the formula 6C6Hl0O + HzO and fuses with decomposition at 215". It is soluble in water and in caustic potash insoluble in alcohol. From its aqueous solutions baryta-water throws down a precipitate which redissolves in excess of the precipi- tant.It does not give a blue coloration with iodine it reduces silver nitrate but not Fehling's solution. Under the microscope graminin eho ws spheroidal granules which are sometimes concentrically striated on the addition of water a part dissolves but the larger part remains in the form of half-spheres which show radial stria. The authors hAve also obtained graminin from the rhizome of Baldingern urzmdina,cea but in this case a part of the carbohydrate occurs in a less soluble modification. This latter modification shows decided cruciform or semi- circular striae in polarised light. Graminin also seems to be present in the rhizomes of Calamagnostis ngrostis and of Teisetum hierochloa.This carbohydrate seems closely related to inulin and irisin as is apparent from the following comparison of their properties :- Solubility in 100 Rotatory parts H20 a t power. Melting ordinary temp. [.ID. point. sol. variety.. 3.29 parts - 48-12" 215" . . 1.79 - 49.27 205 Graminin { insol Irisin ................ 3.26 ) - 52.34 160 Inulin ................ 0.96 - 34.53 160 From Draccena australis the author has obtained a carbohydrate 6CsH,,O5 + H,O which very closely resembles triticin from Triticuin repens. It diflers however from the latter in its rotatory power which is [a]= = -36*61" whilst that for triticin is [a]= = -41.07". By M. HONIG and S. SCHUBERT (Monatsh. 8 529-560). -Braconnot Berzelius and Payen have observed the formation of certain dextrins and saccharine substances when inulin is heated ; whilst Dragendorff has described intermediate products between inulin and lsevulose formed by heating innlin with water under pres- sure.In this paper a long account is given of experiments on the saccharification of inulin effected either by heating inulin in glycerol or with dilute mineral acids the specific rotatory and cupric oxide reducing powers of the various intermediate products are also set forth in a series of tables. The principal results obtained are as fol- lows :-( 1.) The intermediate products obtained by heating inulin with diluh mineral acids so far as they are directly comparable seem to be identical with the products obtained by heating inulin by itself. (2.) These dextrin-like substances differ from one another by their specific rotatory power as also by their solubility in water and alcohol and their precipitability by barium .hydrate. At a lower L.T. T. Inulin.ORGANIC CHEMISTRY. 217 temperature the substances formed more nearly resemble inulin as regards their sparing solubility whilst a t a higher temperature at first certain products metinulin and indoid are produced which are readily soluble in wat'er and not precipitated by barium hydrate. After a more profound change the substance formed shows succes- sively a slight laevorotatory then no rotalory power and finally a dextrorotatory power. The specific rotatory power varies from [a]j = -41.5 that of inulin t o [a]j = +30*68 that of the final dextrin. (3.) The substances without specific rotatory power are not identical with laevuloses.(4.) The saccharification of inulin is effected rapidly by dilute acids reaching its maximum in 15 to 30 minutes according t o the concentration ; laevulose and the above- mentioned dextrins are simultaneously produced. The authors have also succeeded in obtaining laevulose in crystals sufficiently well developed for measurement by i'reqiientlp recrystal- lising the crude crystalline l~evulose from absolute alcohol the crystallisation in each case being induced by dropping in a solid crystal ; a similar product was also obtained by the sacehsrification of inulin. Laevulose crystallises in the rhombic system individual crys- tals being of the prismatic and combined crystals of the octohedral type.The axial ratio is a b :-% = 0.80067 1 0.90674 whilst 110 110 = 77" 22' and 011 011 = 84" 24'. The crystals are slightly biaxial resembling as regards their action on polarised light certain mixtures of sodium-ammonium and potassium-sodium tar- trates. The specific rotatory power of an aqueous Eolution of the pure laerulose was [a]j = -89.74 L = 200 mm. c = 3.6555 ; t = 22". This value when calculated by means of the factor 1.129 gives for [a] the value -87.84". Analyses are also given of the pure product which prove that the formula C6H,,06 expresses the composition of laevulose. V. H. V. Fermentation of Glyceraldehyde. By E. GRIMAUX (Compt. rend. 105 1175-1177).-By oxidising glycerol by means of platinum-black the author had previously obtained a liquid which seemed t o contain glyceraldehyde although the latter could not be isolated (Abstr.1887 695). When this product is distilled in a vacuum with dilute hydrochloric acid its rotatory power is con- siderably reduced and a gummy residue is left which is soluble in absolute alcohol. The residue therefore contains no dextrin and since dextrose is converted into dextrin under these conditions i t follows that the product of the action of platinum-black on glycerol contamins no dextrose. With phenylhydraziiie it yields a compound identical with the hydrazine-derivative obtained by Fischer and Tafel from the products of the oxidation of glycerol by nitric acid. The author oxidised glycerol by Fischer and Tafel's process neutralised with potassium hydroxide extracted with alcohol and evaporated the solution to dryness in a vacuum.The product thus obtained has very little reducing power but if boiled with very dilute snlphuric acid it recovers its reducing power and after neutralisation it ferments readily in coctact with yeast. Glyceraldehyde is not eonverted into glucose by treatment with hydrochloric acid.248 ABSTRACTS OF CHEMICAL PAPERS. This is the first instance of the synthetical formation of a sugar which undergoes alcoholic fermentation. It is evident that the pro- perty of fermenting. in this manner is not confined to carbohydrates containing Cs and C12. C. H. B. Decomposition of Nitrosoketones. By H. V. PECHMANN (Ber. 20 3213-3214 ; compare this vol. p. 146).-When boiled with dilute snlph uric acid fatty nitroketones are converted into hydroxylamine and diketones.When the liquid obtained by treating an alkaline solution of ethyl methylacetoacetate with sodium nitrite and sulphuric acid is dist.illed with much sulphuric acid a yellow distillate contain- ing diacetyl is obtained. N. H. M. Action of Zinc Ethide and Zinc Iodoethide on Dipropyl- ketone. By P. MENSCHIKOFF (J. pr. Chem [g] 36 347-352).- Both zinc athide and zinc iodoethide form condensation-products with dipropyl ketone but only the compound of the iodoethide yields a tertiary alcohol on treatment with water. G. T. &I. Diacetyl and its Homologues. By H. v. PECHMANN (Ber. 20. 3162-3164) .-By successive treatment with sodium hydrogen sul- phite and dilute acids the homologues of nitrosoacetone are converted into a-diketones (homologues of diacetyl) ammonia and sulphuric acid being also produced.From nitrosomethylacetone diucety Z is obtained COMe*CMe:NOH + H,SO = COMe*CMe:NSO,H + H,O = COMe-COMe + NH4HYOr. It is a yellowish-green oil which boils without decomposition at 87-88' and does not solidify when placed in a freezing mixture of ice and salt; its odour resembles that of acetone and its vapour is the colonr of chlorine ; it dissolves in 4 parts of water a t 15" forming a yellow solution and is miscible with ordinary solvents. I t is decom- posed by alkalis or hot alkaline carbonates forms a colourlesa crystal- line substance with ammonia and with phenylhydrazine yields two liydrazides melting a t 133" and 242" respectively. With aniline it forms a crystalline product ; with orthodiamines liquid quinoxalines are produced and it combines readily with alkaline hydrogen sul- phites.When reduced in acid solution it is converted into a benzoiu which reduces Fehling's solution instantly at the ordinary temperature. Since in its physical properties diacetyl differs so considerably from @yoxal the latter compound must be considered as a polymeric di- formyl diacetyl however resembles itis higher homologues di butyl and diisovaleryF1. F. S. K. Chlorinated Methyl Formates. By W. HENTSCHEL (J. pr. Chem. [2] 36 305-317 ; compare Abstr. 1887 1027 1099).-Trichloro- methyl chloroformate COCl.OCCl is obtained among other products of &he chlorination of methyl chloroformate. When heated at 300° it decomposes into twice its volume of carbonyl chloride a t a dull- red heat it yields carbonic anhydride and carbon tetrachloride whilst in presence of aluminium chloride it is rapidly and completelyORGANIC CHEMISTRY.249 resolved into these substances giving almost a theoretical yield of carbon tetrachloride. Both dry and aqueous ammonia convert it into carbamide but contrary to the statement of Cahours no trichlor- acetamide is formed. If aniline is used instead of ammouia diphenyl- carbamide is formed which on further treatment'wi th trichtoromethyl chloroformate yields phenyl isocyanate. Trichloromethyl chloro- formate does not react with benzene when heated in closed tubes at 150° but if the substances are brought together in presence or aluminium chloride triphenylchloromethane is produced.With alcohol and phenol trichloromethyl chloroformate yields trichloro- methyl carbonate OMe.COOCCl and phenyl chloroformate COCl-OPh respectively whilst it is practically without action on unsaturated hydrocarbons such as ethylene and amylene when heated with them in sealed tubes. G. 'r. M. Chlorinated Methyl Formates. By W. HENTSCHEL (J. pr. Ch,em. [ 2],36,468-48O).-Trichlormethyl dictilorformate C,H,CI,O (Abstr. 1887,1028) is not formed by heating together methyl chloro- formate and perchloromethyl formate. By the action of aluminium chloride the formate is split up into carbonic anhydride methylene chloride and chloroform pointing to the formula CH,Cl.OCCl 0 CC1.0.CH2C1 rather than to OMe-C,0,CI,*O-CC13 where chlormethane and tetra- chloromethane should be the products.By distilling the formate (1 mol.) with anhydrous sodium acetamhe ( 5 mols.) acetic acid acetic anhydride niethylene diacetate and carbonic oxide and anhydride are obtained ; if a smaller proportion of sodium acetate is used acetic chloride and methylene diacetate are formed. The action of aluminium chloride on the formate dissolved jn benzene yieids di- and tri-phenylmethane. Aniline acts on the formate producing a crystalline substance C4H,C1:,0,(NHPh) of unpleasant odour melting at 45". By the action of sodium phenoxide on the formate a phenyl ether corresponding with this anilide was obtained. On chlorinating methyl chloroformate a heavy oil either C,H,Cl,O or C,H,Cl,O boiling at NO" is obtained. Its vnpour-density could not be ascertained. A.G. B. Action of Triethylamine on a-Bromobutyric Acid. By E. DUVILLIER (Bull. SOC. Chinz. 48 3-6).-When a solution oE a-bromobutyric acid (1 mol.) is added to a saturated aqueous solution of triethylamine (2-3 mols.) there is some development of heat and the liquid separates into two layers the upper of which is un- altered triet,hylamine. The mixture is heated to complete the reac- tion and the excess of triethylamine distilled off. The products are triethylamine hydrobromide and a-hydroxybutgric acid the latter being soluble in ether. The barium salt of this acid is allnost in- soluble in alcohol. The zinc salt crystallises with 2 mols. H,O jn small nodules which lose their water at 110". It is almost insoluble250 ABSTRACTS OF CHEMICAL PAPERS.in alcohol. No beta'ine is formed in this reaction and hence the behaviour of triethylamine is analogous to that of potassium barium or silver hydroxide. When the dry substances are mixed in the same proportions there is likewise some development of heat and the reaction is completed by heating in closed vessels. The products are a-hydroxybutyric acid traces of crotonic acid and tetrethglammonium bromide. C. H. B. Solubility of Salts of Isovale ric Methylethylacetic and Isobutyric Acids. By L. SEDL~TZKY (iionatsh. 8 563-576) .-In this paper determinations are given of the solubility of various salts of isovaleric methylethylacetic and isobutyric acids by the method of heating and cooling described by Rmpenstmnch ; from these deter- minations formulm are deduced and the calculated results in each case are compared with those found.These formulae are given below :- Silver isovalerate S = 0.1774 + 0.003349 ( t - 0.2) + Calcium isoralerate S = 18.429 + 0-10514 ( t - 0.2) - Calcium isobutyrate S = 20.3833 + 0.08061 ( t - 1) + Silver methylethylaceta.te S = 1-1116 + 0.0002978 (t - 1) + Calcium methylethylacetate S = '289822 + 0.33186 (t - 0.6) Barium methylethylacetate could not be obtained in ft crystalline Tbe curves of solubility in terms of degrees are given in it 0*000006528 ( t - 0*2)2. 0~001091 (t - 0.2)*. 0.0006522 (t - l)2. 0~0002105 (t - 1y. + 0.004417 ( t - O.t;),. form. series of diagrams. V. H. V. Oxidation of Palmitic Acid. By M. GR~GER ( M o w u ~ s ~ . 8 484 -497).-An account is given of experiments on the oxidation of palmitic acid with alkaline permanganate under varions conditions of concentration.The principal products formed are acids of the oxalic series namrly oxalic succinic and adipic ; acids of the acetic series namely acetic butyric caproic and probably caprylic; and acids of the lactic series namely hydroxyvaleric and dihydroxypalmitic acids. Other conditions remaining the same acids of lower molecular weight are produced with greater concentration of the oxidising solution aitd acids of higher molecular weight with more dilute solutions. The conditions of each experiment the product3 obtained and the methode by which they were s'eparxted; are discussed in detail in the paper. V. H. V. Mixed Acid Anhydrides. By W. AUTENRIETH (Bw. 20 3187- 3191).-The general method for preparing the mixed anhydrides consists in heating the acid with two or three times the calculated amount of acetic anhydride in a reflux apparatus for $ to Q an hour.The product is treated with sodium carbonate to remove excess ofORGANIC CHEMISTRT. 251 acet;c anhydride as well as the acetic acid; the anhydride separates as an oil from the alkaline liquid. Acetocuproic anhydride CsHi,,O*OAc is a colourless liquid which is lighter than water and boils at 165-175". Acefovaleric anhydride CsH,O*OAc resembles the above compound ; it boils at 147-160". Aceto-p-thioethylcrotonic aiihydride SEt*CMe:CH*CO-OAc is a thick yellowish-brown oil heavier than water which when exposed to air gradually decomposes with separation of crystals of thioethyl- crotonic acid.It gives a dark-red coloration with sulphuric acid but does not show the dark-green coloration characteristic of tho thioethylcrotonic acids when treated with isatin and sulphuric acid. Nitric acid acts violently on it. Acetobenzoic anhydride COPh-OAc (Gerhardt Annulen. 87 85) is readily obtained by boiling benzoic acid with acetic anhydride. When treated with ammonia it is converted with development of heat into benzamide and ammonium acetate. VuZeryZph#iylhydrazide NHPh*NH*C,H,O prepared by mixing acetovaleric anhydride with phenylhydrazine crystallises in yellowish- white pIates melting at 101"; it dissolves readily in alcohol ether and chloroform sparingly in light petroleum. Capronyl phenylhydruzide NHPh*NH*C6Hl,0 crystallises from light petroleum in white needles melting at 116-117" (compare Abstr.1887 797). N. H. BI. Oxidation-products of the a-Hydroxy acids of the Fatty Series. By V. ARISTOFF and N. DEMJANOFF (Chew,. Centr. 1887 1157 from J . Russ. Chem. Soc. 1887 257-271).-The authors studied the intermediate products which are obtained by oxidising the ethereal salts of the a-hydroxy-acids on the assumption that the ethereal salts of the ketonic acids formed by that reaction oughf to show a greater stability than the ketonic acids themselves. Potassium permanganate was used as the oxidising agent. Ethyl lactate in sulphuric acid solution gave ethyl pyruvate. Ethyl hydroxybutyrate gave about 15 per cent. of the theoretical yield of ethyl propionyl- formate CH,,*CH2*C0.C0,C2H,. It is thus shown that in oxidising the a-hydroxy-acids a-ketonic acids are formed as intermediate products.J. W. L. Lactones and Lactonie Acids. By R. FITTTG (Bar. 20 3174- 3185).-When the lactonic acids CHX<fg&:o:!!> obtained by the union of aldehydes wikh succinic acid are boiled a part distils un- changed but the greater portion decomposes yielding a8 chief products the monobasic unsaturated acids CHX:CH.CH,.COOH together with the lactones CHX< CH*CH o,co-> and a small quantity of the anhy- dride of the bibasic acids COOH-CHX*CH,.COOH (?). Prop y Zpamconic acid CHPr <-o. o. H,- > prepared from but yral- dehyde and succinic acid crystailises well and melts at 2'35". It CH(CO0H)252 ABSTRACTS OF CHEblICAL PAPERS. readily yields heptyleiiic m i d C7H1202 boiling a t 224-226" and hepto- This boils at 232-237" without change and behaves quite similarly to the other lactones.The abnormal behaviour observed by Kiliani (loc. cit.) was probably due to impurity. lactone (Kiliani Abstr. 1886 687) CHPr<&6>CH2. CH CH(CO0H) T r i c h l o r o m e t 7 i y ~ a r a c o ~ ~ c (mid CCI,*CH< -O.CO.CH,->~ ObtainedbS treating cblord with sodium succinate and acetic anhydride,mel ts a t 97" and is sparingly soluble. When treated with an excess of haryta-water it is converted into the barium salt of iso-citric acid. The lnt8ter has therefhe the constitution COOH~CH(OH)*CH(COOH)*CH2-COOH ; it could not be isolated as the nqueous'solution when evaporated yields the lactonic acid COOHCH< - cH,.co,o->. This is crystalline dis- CII (CO OH) solves i n water in all proportions and gives salts of isocitric acid when treated with bases.Phen!ilisohomoparaconic acid C,,H,,Oa is obtained together with phenylhomopnraconic acid (Abstr. 1883,473) by the action of benzal- dehyde on methjlsuccinic acid; it melts at 129.5". The two acids react similarly and when distilled yield phenyl butylenes unsaturated acids CI1H,,O and methylnaphthols CloH6Me*OR. The methyl- naphthol from methylhomoparaconic acid has pro0ably the constitu- tion [Me OH = 3 41 ; it forms yellow needles melting at 89". The naphthol from the iso-acid is colonrlesa rneTts a t 92" and is more stable ; the constitution [Me OH = 2 41 is ascribed to it. Both compounds give with bleaching powder a green precipitate which a fterwards becomes yellow.When distilled orer heated zinc-dust they both yield P-methylnaphthalene ; this melt,s at 37-~3$" (not :-32.5" Schulze Abstr. 1884 1184) and has an odour resembling that of naphthalene. When the tetrabromo-derivative of ethyl ketipate (Fittig and Daimler Abstr. 1887,361) is treated with ammonia alcohol oxamide (1 mol.) and dibromacetamide (2 niols.) are formed. The conqtitu- tion of ketipntic acid is therefore COOH*CH2~CO*CO~CH,~COOH. The reaction is similar to that observed by Hantzsch and Zeckendorf in the case of ethyl tetrachlorodiketoadipate (Abstr. 1887 727) which can be prepared by the action of chlorine on ethyl ketipate. Dimethyldiketone (DiacetyZ) COMe*COMe is obtained by distilling ketipic acid. I t forms a pnre yellow liquid boiling a t 87-89' rather soluble in water miscible with alcohol and ether.It has an odour resembling tha5 of quinone and yields a very unstable compound with sulphurous anhydride. The phenylhydraxine compound C,,H,,N crystallises in splendid slightly yellow needles which melt a t '236" with decomposition ; it is sparingly soluble in ether less Roluble in alcohol The dioxinze C4H8N202 is obtained as a white crystalline precipitate when a dilute solution of the diketone is treated with free hydroxylamine ; a very small amount of the diketone can be detectpd by means of this reaction. The dioxime is very stable and melts without decomposition at 234" (compare v. Pechmann t,his vol. p. 24%). N . H. 31.ORGANIC UHE,I11IS'rRY. 253 Action of Ammonia on Ethyl Acetoacetate and ita Deriva- tives.By M. CONRAD and W. EPSTEIN (Ber. 20 3052-3058).- Met y l ' anzidoacetoncatate " N H,* C Me CH- C 0 OMe is prepared by passing ammonia throngh a cooled mixture of methyl acetoacetate with ether (2 parts) in presence of powdered ammonium nitrate. It crystallises in lustrous colourless prisms a centimetre long melts at 85" and sublimes unchanged. MethyZ " arnidoethy Zacetoacetccte," NH,*CMe:CEt.COOMe is pre- pared by treating 11.6 grams of methyl acetoacetate with 2.3 grams of sodium and 25 grams of methyl alcohol and adding ethyl iodide ; the whole is afterwards heated on a water-bath ; the methyl ethyl- acetoacetate so ohtained boils at 186-188". This is treated with ammonia and the c q s talline product crystallised from alcohol.It melts a t 36-37". Ethyl '' amidometh yzacetoacetate," NH,-CMe:CMe.COOEt is pre- pared by the action of sodium in the form of' wire on ethyl p-amido- crotonate (m. p. 37") dissolved in ether the sodium compound being then warmed with methyl iodide. It is a white crystalline substance readily soluble in ether alcohol and light petroleum ; it melts at 52 ' sublimes readily and has a sharp odour and taste. Boiling hydro- chloric acid decomposes i t very readily into ammonium chloride and ethyl methylacetoacetate. E thy1 " amidoethy lacetoacetate," NH,*CMe:CEt*COOEt is formed by the action of ammonia on ethyl et~liylacetoacetate ; it was prepared by Geuther. Ammonia has no action on ethyl diethylacetoacetate ; ethyl '' amido- acetoacetate " is therefore probably ethyl amidocrotonate and not an imidobutyrate (compare Kuckert Ber.18 618). Ethyl diuhloro- acetoacetate (cooled with ice) is decomposed by ammonia into ethyl- dichloracetate and acetamide. Methyl p-a,midoethyZc?.otonate NH,CMe:CMe*COOMe melts at 58-59". Eth y 11 NH,.CMe:C (CO 0 E t)- CH,-C 0 OE t crystallises in white lustrous prisms melting at 72" (compare Brandes Jen. Zeitsch. 3 35). It forms white plates nielting a t 60". " am idoacetosuccinrr te " N. H. M. Action of Aqueous Ammonia on Alkylated Alkyl Acetoace- tates and of Alcohols on the Carboxylic Alkyl-group in Aceto- acetates. By T. PETERS (Ber. 20 3318-3314).-Brandes ( J m . Zeitsck. 3 35 and Z e d . fGr. Chenz. 1866,437) described the formation of two compounds (&H,,OaN and C5H,0,N by the action of aqueous ammonia on methyl ethylacetoacetate. Conrad and Epstein (preceding Abstr.).employing gaseous ammonia only obtained the compoiind C,H,,O,N or methyl amidoethylcrotonate NH,-CMe CEt-COOMe. The author has repeated Brandes' experiments and besides C7H,,0,N olhained ethylacetoacetarnide CH3*CO*CHEt.CONH2 (m. p. W). This is undoubtedly the cotnpoa nd described by Brandes as C,H,O,N and probably obtained by him in an impure state. Ethylic methyl- isobutyl- and isoainyl-acetoacetates similarly yielded metlhyl- isolmtvl- aud isoamyl-acetoacetamides melting respectively at 73" 85" and 12io whilst if Brandes' supposition is correct that in his experi nent,s the VOL. LIV. S254 ABSTRACTS OF CHEMICAL PAPERS. substituted ethyl-group was eliminated the above three compounds must have yielded amides which were identical.In preparing methyl ethylacetoacetate the author found that if ethyl alcohol was eniployed as the solvent the larger quantity of the methyl salt was converted into tlhe ethyl sdt. Making further experi- ments he found that isobutyl or isoamyl salts could be readily obtained by the action of the respective alcohol on the et'hyl salts the action taking place especially easily in the presence of a small quantity of sodium. He was similarly able to convert ethyl ethylacetoacetate into the methyl salt in the presence of sodiiim but the action was less complete than when replacing a lower by a higher alkyl-group. By C. A. BISCHOFF (Bey. 20 2988 -2992) .-The author in conjrinction with Voit has saponified ethyl a-/3-dimethylethenyltricarboxylate on the large scale and has confirmed the results previously obtained by him in conjunction with Rach (Abstr.1885,885). I11 addition a second acid is also formed which melts a t E O " and is identical with the readily soluble butane- dicarboxylic acid (Abstr. 1887 45) and the product of change from the sparingly soluble dimethylsuccinic acid of high melting points. Voit has also succeeded in converting the two isomeric dimethyl- succinic acids into pyrocinchonic acid. Two symmetrical diethylsuccinic acids are obtained by saponifying either ethyl dietbylacetylenetetracarboxylate or the compound CEt(COOEt),.CHEt.COOEt ; one of the acids is sparingly soluble melts a t 189" and can be converted into the second which is readily soluble and melts at 127-128".These acids are probably identical with Hell and Muhlhauser's isosuberic acids (Abstr. 1880 542). Experiments are in progress with the object of splitting info t w o optically active compounds the optically inactive didhylsuccinic Symmetrical Diethylsuccinic Acids. By E. HJELT (Bey. 20 L. T. 1'. Isomeric Dialkylsuccinic Acids. acid corresponding with racemic acid. w. P. w. 3078-3080) .-Symmetrical diethylsuccinic acid COOH-CHEt*CHEt*COOH is prepared by the action of ethyl a-bromobutyrate on ethyl malonate and sodium ethoxide. The ethyl ethylbutenyl tricarboxylate so obtained which boils at 280-282" is saponified and the acid (m. p. 147") heated at 150". The residue is then crystallised from hot water when two acids of the same composition are obtained ; the one melts at 189-190° and is identical with that prepared by Otto by reducing xeronic acid (Annulen 239 279) and gives an ethyl salt boiling a t 233" which is identical with that obtained by Hell(Rer. 6 30) by the astion of silver on ethyl a-iodohutyrate.The second acid melts at 127". When the acid melting a t 1@9-190" is heated it is converted into an anhydride which boils at about 240"; when this ie boiled with water it yields the acid melting a t 127". 100 parts of water a t 23" dissolve 0.61 part of the acid of higher melting point and about 2.4 parts of t.he lower melting acid. The two acids differ also in crystalline form (compare Otto and Rossing this vol. p. 45). N. H. M.ORQANIC CHEMISTRY. 255 Action of Ammonia on Alkyl Salts of Fatty Acids.By S. RUHEUANN (Rer. 20 3366-3371 ; compare Trans. 1887 403).- Phenylhgdrazine reacts with ethyl diacetjltartrate acetylphenylhjdr- azine being formed. When ethyl diacetyltartaric acid is treated with ammonia tartramide C,H,N204 is formed. I n similar manner mucamide is obtained from ethyl tetracetylmucate. Ethyl aconitate boils a t 174-175’ under about 22 mm. pressure. When left in contact with aqueous ammonia for 2 to 3 days it is con- verted into citrazinamide (loc. cit.) . When bromine is added to a solution of citrazinamide in strong hydrochloric acid the com,pound C,H3Br,N20 separates as a yellow crystalline precipitate. This is stable when dry but decomposes slowly in presence of moisture ; hot water decomposes it with evolu- tion of carbonic anhydride.It dissolves very readily in ammonia and in aqueous potash. The corresponding chZoro-derivative C,H:,CI,N,O resembles the bromine compound b u t is more stable; it can be crystallised from water but the solution decomposes wben boiled for some time. Both halogen-derivatives react with aniline orthotolu- idine and piperidine. N. H. It. Apparatus for Distilling Zinc Methyl and Zinc Ethyl. By A. KAULFUSS (Ber. 20 3104-3105).-The apparatus of which a sketch is given is so constructed that the distillation can be conducted in an atmosphere of carbonic anhydride. N. H. M. Disulphones R”R’,(SO,) and R”2(S02)2 By R. OTTO and R. C. CASANOVA (J. p r . Chem. [el 36 433-452 ; compare Abstr. 1885 261 and 537).-Ethylenediethyldi.sulphane C2H4( SO fit) is prepared by heating an alcoholic solut,ion of sodium ethylsulphinate (2 mols.) with ethylene dibromide (1 mol.) ; or by heating an alcoholic solution of sodium ethylenedisnlphinate (1 mol.) with ethgl bromide (2 mols.).The identity of the products of these two reactions tends to show that the sulphur in these sulphinic acids is hexavalent. The snlphone crptallises in colourless needles and melts a t 136 -137”. Nascent hydrogen in alkaline solution convcrf s it into sodium ethylsulphinate and alcohol. When heated with aqueous potassium hydroxide it yields a thick oil which with benzoic chloride gives ethylsulphone- ethyl benzoate SO,Et*CH,-CH,-OBz melting at 118” ; the correspond- i n g alcohol could not be isolated. Etl~ylenedimet1,y I d i s u l ~ h o n e C,H,(SO,Me) is formed when methyl bromide is substituted for ethyl bromide in the above reaction ; i t crystallises in pearly scales melts at 190” and is soluble in hot water.Ethyle?zedipropyldisu,lp.phone C2H4( SO,Pr) forms crystals with a peady lnstxe melting at 155”. DiethyZenedisulp12one C,H,< !:> C2H4 prepared by the action of sodium ethylenedisulphinate on ethylene dibromide is identical with the oxidation product of diethylene disulphide. Metaphenylenedieth y Idisidphone (&HA( SO,E t)2 prepared by the s 2256 ABSTRACTS OF CHEMICAL PAPERS action of potassium benzenedisulphinate on ethyl bromide forms colourless tables melting a t 142". PhenyZelze-etiLyZenedisuZ~~one C6H4< so4>CpH4 obtained by heat- ing ethylene dibromide with potassium metabenzenedisulphinnte forms very small crystals insoluble in most solvents.so A. G. B. Synthetical Researches on and Constitution of Uric Acid. By J. HORRACZEWSKI (Molzatsh. 8 Fi84-593).-The author has shown that uric acid may be synthetically produced from trichlorolactamide and carbamide ; it is also formed although in smaller quantity from tricblorolactic acid as also from amidoacetic acid and carloamide. This last change doubtless depends on the intermediate formation of a glycocine-carbamide which react's with the carbamide to form u r i c acid water and ammonia. thus COOHCH,*NH2,NHz*CONH2 + 2CO<g$ = CO' I( I + 2H,O + 3NH3. Similarly methyl- nric acid may be obtained from sarcosine and carbamide as also from inethylhydantoin and biuret or amyl allophanate.The formation of uric acid from trichlorolactic acid shows that uric acid is an ureide of acrylic acid whilst the formation of methyluric acid from methyl- hydantoh shows that it is a hydanto'in cyanate. The relation of uric acid to lactic acid is of especial physiological importance a8 Minkowski has shown that on removal of the liver from geese con- siderable quantities of ammonia and lactic acid occur in the urine whilst the proportion of uric acid is diminished. It has further been shown by Kan6ra and the author that in the human organism the proportion of uric acid is increased by doses of glycerol. On the other hand the synthesis of uric acid from amidoacetic acid is of interest as v. Knierem has proved that in the organism of birds amidoacetic acid (glycocine) is converted into uric acid and expelled a8 siich in the urine ; the same phenomenon has also been observed to a less degree in the human organism since the glycocine is for the most part converted in to carbamide.NH- C-C 0 *N H 2 \NH.C-NH-CO V. H. V. Furfuracrylic Acid. By H. B. HILL (Ber. 20 3359) -Bromine acts on furfuracrylic acid with formation of a crystalline compound C7H5Br305 which is decomposed by water into dibron2of~rSuretlzy2ene and carbonic anhydride. From the dibromo-compound monobromo- furfuracrylic acid crystallising in long needles and dibromofurFur- acrjlic acid can be readily prepared. (Compare Markwald t h i s vol. p. 135.) N. a. M. Thiazole Compounds. By A. HANTZSCH and J. H. WEHER ( B e y . 20 3118-3132 and 3336-3337).-Thiazole is the name .. given to the isomeric compounds <cG N * CH>S CH and <cH CH :mcE>S N ; m simple thiazole-derivative is known but by the condensation ofORGANIC CHEMISTRY. 257 certair ortho-benzene-derivatives benzene-thiazoles are formed ; for instance hydroxyphenylthiocyanate gives the compound and all thiocyanic compounds of ketonic or aldehydic nature in which the carbonyl radicle is in the ortho-position to the thiocyanic group are in their stable .form thiazole-derivatives the atomic complex CO:CH-S.CN changing into <g::>C*OH. The term meso-deriva- tive is suggested for all compounds in which the hydroxyl-group is displaced. From thiocyanacetone Tscherniac and Norton (Abstr. 1883 568) obtained a peculiar base thiocyanopropiniine to which they gave the formula NH CMe*CH,*SCN ; this substance is how- ever meso-amidomethylthiazole < CMe cH >S ; by neither of Hofmann's reactions can it be proved that this compound is a primary amine and with nitrous acid it yields only resinous products but from its behaviour towards methyl iodide only two hydrogen-atoms can be in combination with nitrogen ; the study of its acetyl-deriva- tives and of thiocyanacetone prove the above formula to be correct.Methy lamidomethy lthiaxo le hydriodidcr C,NS H4*NHMe HI is the principal product of the action of mefhyl iodide on thiocyanopropimine ; i t crystallises with 1 mol. H,O and when treated with potash yields methylamidoniethylthiazole ; this base is a white very deliquescent crystalline substance not very readily soluble in ether.It has a strongly alkaline reaction and reacts mare readily with methyl iodide than the origiiial base an abnormal ammonium iodide CloK14S2N31 and diniethylamidomethy Ithimole hydriodide heing formed. The latter crystallises in large transparent plates with 1 mol. H,O and melts at 54" the anhydrous substance melting at 155" ; with potash it yields diinpthylamidonzeth ylthiazole which is a crystalline compound and melts a t 96". Trimethylamidometh ylthiazolium iodide C4NSH4-NMe31 is obtained on heating the dimethyl base in sealed tubes with methyl iodide ; it is a white solid which melts at 85" and is not decomposed when boiled with potash. Ace tg lm e t ?i y lamid omet h y It hiazo le CaN S H4.NMeAc is produced by acting on the monomethyl base with acetic anhydride ; it crystallises in white needles with 6 mols. H,O and melts a t 50" the anhydrous compound however melts at 113".The existence of this derivative and the fact that a diacetyl-derivative cannot be obtained from this com- pound is strong evidence in favour of the formula suggested and that th iocyanopropimine is m eso-amidometh yl thi azole. The ace tyl-deriva- tjive of amidomethylthiazole forms salts with alkaline hydroxides the sodium salt C6H,NaN2S0 + 8H,O is obtained by warming it with concentrated soda. The formation of this compound and the non- formation of a salt in the case of the monomethylacetyl-derivative are further proofs in favour of the author's formula as is also the behaviour of dimethylamidomethylthiazole towards bromine ; when this last-named compound is treated with bromine-water only one hydrogen-atom is displaced.The bromo-derivative CsH,BrN2S N C(NH,j258 ABSTRACTS OF OHEMICAL PAPERS. crystallises from alcohol and melts a t 114". Amidomethylthiazole and methylamidomethylthiazole are completely destroyed by bromine. Since thiocyanacetone yields mesoamidomethylthiazole when treated with ammonia it must be represented by the formula N C(0H) < CMe CH >S and not by COMeGB,.SCN that given to it by Tscherniac and Norton (Zoc. cit.). It was obtained by their method in crystalline needles melting a t 98" ; with phenylhydrazine acetate hydroxylamine and sodium hydrogen splphite it does not react like a ketone but with phosphorous pentachloride it acts like a phenol. The hydroxyl-group reacts very readily and can be displaced by amines ; by the action of aniline anilidomethylthiazole CaNSH4NHPh is obtained; it crystallises from alcohol and melts at 117".Para- toluiclomet~.ylthiazole melts a t 125" ; with metaphylenediamine the compound C,H,(NHC,NSH& melting a t 152" is obtained. By the action of metallic thiocyanates on ethyl monochloraceto- acetate ethyl hydr~llmet,hylthiazoleccLrboxylate < -N '(OH)- CMel C(CO*OEt?S' is formed a molecular change taking place similar to that occurring in the formation of hydroxymethylthiazole ; this ethereal salt melts a t 128" and judging from its behaviour towards phenylhydrazine does not contain a ketone-group. A compound CII&IlS05N,S which melts at 142" is also formed in this reaction.F. S. K. Bromobenzenes. By A. J. LEROY (BUZZ. SOC. Chin%. 48 210- 216).-Benzene 450 grams and aluminium chloride 25 grams are mixed in a large flask and the calculated quantity of bromine is added gradually care being taken to keep the benzene in large excess. The product is treated with dilute hydrochloric acid separated and dried. I n this way monobromobenzene is obtained almost free from the di- derivative. Dibromobenzene is obtained in tt similar manner using benzene 240 grams bromine 960 grams and aluminium chloride 30 grams. When treated with water crystals of paradibromobenzene melting a t 89" are obtained together with .a small quantity of tbe tri-deriva- tive which can be separated by fractionation. The liquid product is mainly dibromobenzene which boils a t 219" and does not solidify at -2O" mixed with some of the monobromo-derivative.The mixture is cooled to remove the para-derivative and then treated with fuming sulphuric acid and ordinary sulphuric acid in which the liquid readily dissolves. The product is treated with water to separate the para- derivative and the liquid is distilled in a current of steam when metadibromobenzene boiling at 200" is obtained the yield being equal to about 16 per cent. of the bromine taken. The action of chlorine on benzene in presence of iodine yields the orttho- and para- derivatives. With aluminium chloride no other derivative is obtained. I t would seem therefore that in the reactions in presence of alum- inium chloride there is a tendency to the formation of para- and meta-deri vatives.Paradibromobenzene when treated with methyl chloride in presence of aluminium chloride is mainly converted into carbonaceous pro-ORGANIC CHEMISTRY. 259 duct8s ; the liquid products besides monobromobenzene meta- and paradi-bromobenzene contain two tribromobenzenes melting at 44" and 119.6" respectively and yielding nitro-derivatives which melt at 93-5" and 125" respectively. It would seem that the aluminium chloride first reduces the para- dibromobenzene to the monobromo-derivative part of the bromine becoming free and acting on the mono-derivative with formation of the meta-di-derivative. At the same time another portion of the liberated bromine forms tri-derivatives. These results are analogous t,o those obtained by Friedel and Crafts by the action of aluminium chloride on dichlorobenzene.C. H. B. Action of Sulphuric Acid on Chlorobenzenes. By ISTRATI (BzdZ. Xoc. Chim. 48 35-41) .-300 grams of pentachlorobenzene was heated with 2000 C.C. of Nordhausen acid for seven to eight hours per day during 13 days. Hydrogen chloride sulphurous anhydride and some water were given o$. A t the end of 15 days the acid was decanted off a fresh quantity added and the heating continued 15 days longer. No carbonisatmion took place but a deep maroon- culoured substance gradually separated. The acid was neutralised by barium carbonate but no sulphonic acid was obtained. The maroon-coloured substance after being washed with water dis- solved completely and rapidly in sodium or potassium hydroxide solu- tion forming a deep red liquid and when this was filtered and acidified with hydrochloric or sulphuric acid the substance was reprecipitated.When dried a t 60" it contracts and becomes dark green with a metallic lustre. It is insoluble in boiling water which removes traces of a colourless crystalline substance but it is soluble in concentrated alcohol very slightly soluble in ether chloroform or carbon bisulphide quite insoluble in benzene. The alcoholic solution which is cherry-red by transmitted light and yellowish-green by reflected light and has very great tinctorial power deposits no solid on cooling hence it seems probable t,hat a compound is formed. The substance will not crystal- lise from alcohol and is not fusible. When heated to redness it burns and leaves r? residue of carbon which is only combustible at a very high temperature.It contains 36.83 per cent. of chlorine and is free from sulphur. The potassium salt is deep brown with a metallic lustre and is readily soluble in water forming a deep red non-dichroic solution. The barium iron tin mercury aluminium magnesium cadmium nickel and other salts are obtained by double decomposi- tion. They are all pale or deep red and are insoluble in water with the exception of the silver salt which blackens rapidly and of the mercuric salt which separates slowly from the solution. The com- pound seems to have a phenolic function and the author proposes to call it &'rancein. Francein is readily attacked and dissolved by cold fuming nitric acid. When heated in sealed tubes a t 150" to 180" for six hours large colourless crystals separate.Francein can also be obtained by the action of ordinary Concentrated sulphuric acid and in this case another substance of the same composition as francein but much more soluble is also formed a t the same time.2 cio ABSTRACTS OF CHEMICAL PAPERS. Tetrachlorbenzene (200 c.c.) when heated to boiling with concen- trated sulphuric acid (1200 c.c.) €or 105 hours is completely dissolved with evolution of water hydrogen chloride and large quantities of sulphurous anhydride. No sulphonic acid is. formed but the chief product is a colonring matter which retains a volatile substance; this sublimes a t loo" crystallises in slender needles and has an odour resembling that of benzoic acid. This substance is removed by treat- ment with boiling water when a reddish-brown solid is left easily ~oluble in alkalis.A considerable portion is soluble in boiling water and especially in alcohol forming a solution which is pale-brown by transmitted light and dull-preen by reflected light. The more soluble portion contains 33.12 per cent. of chlorine ; the portion insoluble in water contains 38-72 per cent. I n the preparation of trichlorobenzenesulphonic acid when the snl- phuric acid is diluted with water i t yields tt red prodnct insoluble in water but easily soluble in alcohol ; this is infusible and very dark- coloured with a metallic lustre. The formation of hydrogen chloride and sulphurous anhydride in these reactions is of special interest. It is probable that under the influence of the sulphuric acid which plays the part of an oxidising agent part of the chlorine leaves the benzene nucleus the sulphiiric acid being reduced.This action which is quite secondary with the lower chlorobenzenes becomes the dominant reaction with the higher derivatives. In the case of the trichloro-derivative both reactions are well marked. When pentachloronit~robenzene is heated with concenti-abed sul- phnric acid water and hydrochloric acid are given off in large quan- tities but very little sulphurous anhydride is liberated. On diluting with water a crimson precipitate forms. This substance is not soluble in alkalis but dissolves in warm alcohol from which it separates on cooling. A dilute alcoholic solution is golden-yellow by reflected light and pale-red by transmitted light.By ISTRATI ( RI& S'OC. Chim. 84 41-43) .-Paradichlorethylbenzene when boiled with concen trntecl sulphuric acid and fuming nitric acid for 50 hours fresh nitric acid being added each day .yields a solid crystalline product completely ~olnble in the warm acids from which i t is precipitated by adding water. This nitro-derivative is readily soluble in a mixture of alcohol one part and ether two parts. When treated with boiling water the compound C6H2Cl,Et*N02 is dissolved and is deposited on cooling. It is very soluble in alcohol and ether and crystallises in lamella melting at 175". Its solution is feebly acid and is not precipitated by lead salts and is not oxidised by potassium permanganate in the cold. Perri c chloride gives an abun clan t yellowish- w hite precipitate.The portion less soluble in water has the cornpositmion C6C1,Et(N0,) and is easily soluble in alcohol ether and benzene. It forms small hard crystals which melt at about 195' with partial decomposition. The alcoholic solution mixed with an aqueous solution of ferric chloride yields a slight precipitate after some time. 100 grams of the compound CsH2C12Et.NO2 was boiled for 12 hours C. H. B. NitrochTorethylbenzenes.ORQSNIC CHEMISTRY. 261 with 500 C.C. of fuming nitric acid and then with a mixture of fuming nitric and sulphuric acids. The product consists of two isomerides which can be separated by treatment with warm alcohol. The loss soluble compound forms hard white crystals which dissolve in ether and melt at 82".The more soluble compound has a strong aromatic odour and forms crystals melting at 150". These compounds contain 24 per cent.. of chlorine. Orthocyanotoluene. By S. GABRIEL and B. WEHE (Ber. 20 3197-3199) .-OrthocytrnobenzaZ chloride CN*C6H,*CHCl3 is prepared by boiling the oil obtained in tbe preparation of orthocyanobenzyl chloride (Abstr. 1887 1035) whilst chlorine is being passed through. It boils at 260". When heated with fuming hydrochloric acid a t 170" orthophthaIdehydic acid melting at 97" is formed. Strong sulphuric acid converts it into diphthalide ether (m. p. 221"). Ort hocy an obenzotr ichloride C No C,H,* C C 13 is o btnin ed bay the f n rt h e r action of chlorine on the oil from cyanobenzene chloride and crystal- lises from alcohol i n monoclinic crystals of a vitreous lustre ; a b c = 1.5464 1 1.1056; /3 = 73" 53'.It melts a t 94-95' and boils a t about 280". N. H. 21. C. H. B. Action of Nitric Acid on Pentamethylbenzene. By 11. GCTTSCHALK (Rer. 20 3286-3288).-When oxidised with dilute nitric acid pentamethylbenzene yields tetramPthyZbenzenecarEoxyZic acid C6HMe4*COOH [COOH Me4 = 1 2 3 4 31. This acid crys- tallises from alcohol in colourless needles and melts at 165". Its bariuni salt crystallises in anhydroug scales or in tiiftlv of needles (CllH1302)zBn + 2Hz0. When the barium salt is heated with lime it yields prehiiitene. Small quantities of polybasic acids were also formed but were not examined. When dissolved in cold fiuning nitric acid pentamethylbenzene yields dinitroprehnitene. The author believes that the reaction is analogous to that noticed by Jaoobsen (Abstr.1886 694) when durene is treated with fuming sulphuric acid but he has not been able to isolate bexamethylben~ene from t8he products of tbe reaction. Nitropentamethylbenzene C,Mej.NO2 is obtained by the slow action of bromine vapour on a mixture of pentamethylbenzene and silver nitrate at ordinary temperatures. It crystallises from alcohol in long ueedles melting a t 202". L. T. 1'. Phenylacetylene and Dipher. yldiacetylene. By A. F. HOLLE- MAN (Ber. 20 3080-3082).-Phenylncetylene is prepared by boiling monohromocinnamene with alcoholic potash. The bromocinnameno was obtained from ethylbenzene by the method of Friedel and Bahlson (Bull. Soc. Chim. 35 55). Diphenyldiacetylene is prepared by the method of v. Baeyer and Landsberg (Ber.15 57) ; it melts at 88" (not !No Glaser Annnlen 154 151). Bromine (4 mols.) acts on diphenyldiacetylene (1 mol.) with formation of a tetrabromide melting at 173" and a compoiind melting a t 149-153"; analyses of the latter point to the formula C,,HioBrz*C,~HloBr4. N. H. M.262 ABSTRACTS OF CHEMICAL PAPERS. Iodophenols. By E. NOLTING and T. SnwxER (Btr. 20 3018- 3023 ; compare this Journal 1874 259 ; Zeit.fur Chew. [el 4 322).- Orthiodophenol remains practically colourless after two years' exposure to the air and light. When treated with nitric acid iodine is set €ree but chloriodophenol is formed if chlorine is passed through its solu- tion in carbon klisulphide. When fused with potassium hydroxide orthiodophenol yields catechol free from resorcinol even at tempe- ratures above 250".Metiodophenol is formed by the usual reactions from metiodonitro- benzene and metamidophenol ; it is necessary to diazotise metiodaniline in an excess of acid otherwise a compound is obtained which crystallises in red needles melts a t 145" and is powibly diiodoxyazo- benzene C6H41gN2*C6H31*OH. Metiodophenol crystallises from light petroleum in white needles melting a t 3Y0 or sublimes in small snow- white needles meltiiig a t 40'. It is readily soluble in the usual solvents does not liberat'e iodine when treated with chlorine or fuming nitric acid even when boiled with the latter and on fusion with potassium hydroxide yields resorcinol free from catechol. Pariodophenol is readily obtained from paramidophenol.It forms long needles melts a t 93-94" yields iodine when treated with nitric acid b u t not with chlorine and on fusion with potassium hjdroxide at higher temperatures yields resorcinol instead of quinol. To explain the formation in fusions with potash or soda of resorcinol from ortho- and pnra-derivatives and gf catechol from meta-deriva- tives without assuming the occuiBrence of intramolecular change Nolting recalling the fact that fused alkalis sometimes act as oxiciising and sometimes as reducing agents suggests that both these actions occur during f asion ; 1 3 brornophenol for example being first oxidised to 1 2 3 dihydroxybromobenzene which is then reduced to catechol. w. P. w. Solid Orthiodophenol from Iod b e and Sodium Phenoxide.By C. SCHALL (Ber. 20 3362-3364).-When the orthiodophenol obtained by the action of iodine on sodium phenoxide (Abstr. 1883 1109) is kept for some months crystals separate melting a t 4L-43". These dissolre sparingly in hot water and separate as an oil which crystallises when a crystal is added. An iodine determination and the vapour-density show that the substance is pure orthiodophenol. The crystals are at first lustrous and trans- parent but become slightly red when exposed to air ; they are doubly refractive and are probably monoclinic (cornpare Neumann AnnaEen 211 67). N. H. &I. It then melts at 29-40". Occurrence of Catechol in Raw Beet-sugar. By E. 0. V. LIPPSIANN (Ber. 20,3298-3:501).-The author has examined a samp:e of raw beet-sugar which showed a strong reducing action on Pehling's solution but from its mode of manufacture could not contain invert- sugar.An ethereal extract yielded small quantities of catechol and of an acid C9HlOOa which showed most of the properties of catechol and yielded that substance when heated. The author cannot tell whether these substances were derived from the beetroot or wereORGANIC CHEMISTRY. 2G3 formed by the decomposition of part of the carbohydrates during the process of manufacture. Catechol reduces Fehling’s solution but not Soldaini’s solution and the author therefore advises the use of the latter in preference to Pehling’s solution in sugar testing. L. T. T. Hydroxyquinones. By R. NIETZKI and 3‘. KEHRMANN (Rer. 20 3150-3158) .-The authors try to prove experimentally that the formula of tetrahydroxyquinone is C6(OH),OZ [O 0 = 1 41 and that of rhodizonic acid C6(OH),O4 [OH OH = 3 61.By mixing an aqueous solution of tetrahydroxyquinone with a salt of orthotoluyl- enediamine and adding sodium acetate a green crystalline sub- stance is precipitated. This dissolves in alkalis and dilute mineral acids ; when dried a t increased temperatures it turns brown and is ultimately converted into the mine of rhodizonic acid ; when oxidised it yields diquinoylazine C604:N,C7 H,. From its marked basic pro- perties it was thought that only one nitrogen-atom had entered into reaction and that its formula was c6( OH),O:NC,H,NH aiialysis showed however that its true composition was C,,H,,N,O and t w o formulae N- N C6(OH)/ I ‘C7H6 [N N = 1 21 or C60(OH)3<NH >C7H6 ‘N’ [N NH 0 = 1 2 41 are suggested.Now if tetrahydroxyquinone is an orthoqninone it would react with diamines even when the hydro- gen of the hydroxyl-group is displaced ; but with tetrabenzoyltetrahy- droxyquinone no reaction takes place. By heating tetrahydroxy- quinorie with acetic chloride a yellow crystalline diaeetyZ-derivative Gg08(OA~)L(OH)1 is obtained ; it melts a t 205” is soluble in alcohol and ether but less readily in water; it acts like a bibasic acid and with orthotoluylenediamine yields a compound very similar to that obtained from tetrahydroxybenzene ; it is moreover in ita whole behaviour very similar to chloranilic acid and has therefore the con- stitution [(OH) (OAC)~ = 2 5 3 61. From these results i t follows thatl tetrahydroxyqninone is a paraquinone and that the second o€ the above formulae shows the constitution of the compound formed with orthotoluylenediamine.By S. v. KOSTANECKI (Ber. 20 3133- 3137).-As paraquinon-oximes are obtained by acting on monhydric phenol-derivatives with nitrous acid it is usually accepted that when more than one isonitroso-group enters into a polyhydric phenol each takes up the para-position with respect to a hydroxyl-group. The symmetrical formula C6H20,(NOH) [ 0 (NOH) = 1 3 5 61 has therefore been given to dinitrosoresorcinol and its correctness is the subject of this research. Resorcinol and orcinol give dinitroso-compounds when heated with only one molecule of nitrous acid but from bet.orcino1 C‘6H,Me,(OH)2 [Me = 1 4 3 51 amono-derivative only is obtained even with an excess of nitrous acid and this abnormal behaviour can only be explained by the supposition that the methyl F.S. K. Dinitrosocresorcinol.264 ABSTRACTS OF CHEMICAL PAPERS. radicle occupies the pmition which would be taken u p by the second isonitroso-group. The formula of dinitroso-orcinol is therefore C6HMe(NOH),o2 [Me (NOH) 0 = 1 2 4 3 51 and of dini- trosoresorcinol C6H,(NOH),0 [(NOH) 0 = 1 :? 2 41. These formulm are supported by the behaviour of cresorcinol C6H,Me( OH) [Me (OH) = 1 2 41 towards nitrous acid a dinitroso-derivative being produced. Since in cresorcinol there is only one para-position free it is probable that the symmetrical formula for dinitrosoresorcinol is wrong.DiiLitrosocresorcinol was obtained in the form of it pale- green substance which crystallises with 1 mol. H,O. When heated in a capillary tube above 160° it explodes ; i t is sparingly soluble in water a,nd alcohol insoluble in ether chloroform and benzene. Nitric acid oxidises i t to dinitrocresorcinol CsHMe(NOz)a(OH)2 which cryatalliaes in long yellow needles and melts a t 90" it is sparingly soluble in cold more readily in hot water readily soluble in ether or alcohol; it imparts a bright-yellow colonr to animal fibres. It is probable that dinitrosocresorcinol has the formula C6H02(NOH)JLe [O (NOH) Me = 1 3 2 4 61 that dinitrosoresorcinol has an analogous constitution namely [ 0 (NOH)2 = 1 3 2 41. and F. S. I(. Action of Nitrous Acid on Anethoi'l.By P. TOENNIES (Ber. 20 2982 - 2987).-The compound of anethoil and nitrous acid OMe-C6H4.C3H5( N203) (Abstr. 1879 35 517) as already described (Abstr. 1881 167) when heated with alcohol or aqueous potash yields an isomeric crystalline product' which dissolves readily in alkalis but is precipitated by acids from the solution with the 105s of the elements of a molecule of water in the form of a well- crystallised compound OMe.C6H,*C<NpOp>. This substance by the action of alcoholic potash is converted into an isomeric com- pound which readily yields methoxycyanobenzene OMe*C6H4*CN when heated with hydrochloric acid. The compound of anethoil and nitrous acid in addition forms an acetate CMe OMe.C6H~*C(NOAc).CIeH(oN~) when treated with acebic chloride and on these grounds is now regarded by the author as an isonitroso-derivative of the formula OMe*C6H4.CI(N-OH)*CMeH(ONO). The acetate cannot be distilled in a vacuum without undergoing decomposition into acetic acid and the nitrosoketone OMe-CaH,*C(N.OH)*COMe which forms an oil readily crystallising in yellow needles.This compound is easily decomposed by boiling hydrochloric acid yielding hydroxylamine and the diketone OMe*C6H4.CO*CO&fe which can also be obtained by treating the compound of anethoil and nitrous acid with hydrochloric acid in the cold ; i t is a yellow oil and reacts with phenylhydrazine to form the beautifully crystalline dihydrazide OMe* C6H4' C ( N2HP h) CMe*N,HPh. The isonitrosoketone is obtained also when the compound of anetho'ilORGANIC CHEMISTRY.265 and nitrous acid is treated with alcoholic potash and the product after the evolution of nitrous oxide has ceased is dissolved in water and precipitated by hydrochloric acid. On reducbion it is converted into two compounds one of which is the base Okfe-C6]E-T4*CHAc*NH2 and the second is the ketone OMe*C6H~*CH2Ac derived from this by loss of ammonia. This ketone is an oil of pleasant odour boils at 264" and yields an oily compound with phenylhydrazine. The ketonic base also forms a condensation compound with phenyl- hydrazine and is converted into the acetate OMe*C6H&HAc.NHAc by the action of acetic anhydride whilst its solution in hydrochloric acid if treated with aqueous potash yields a condensation compound OMe*C6H4*CH<gM>&T> CH*C,H,*OMe.This tertiary base does not react with acetic acid or nit,rous acid but forms with methyl iodide a t 100" a beautifully crystalline hydriodide of a mono- methylated base ; on heating this it is readily converted into methyl iodide and the original base but forms with aqueous soda a scarlet- red powder yielding well-crystallised salts with hydrochloric acid and platinic chloride. The addition product of cinnamene and nitrous acid C,H3Ph(N,0,) exhi bits properties very similar to those of the anethoil compounds. By reduction it yields a base CzH3Ph(OH)*NH2 and on treatment with sulphuric acid is converted into phenylnitroethylene with the evolution of nitrous oxide. When the cinnamene additive compound is treated with aniline nitrous oxide is also evolved and a new base probably of the formula NHPh*CH(O€€).CPh NOH is obtained ; this is decomposed by hydrochloric acid into benzaldehyde benzo- nitrile and aniline.A similar reaction also occurs when ammonia and methylamine are employed instead of aniline and in this respect the cinnsmene compound differs from the anethoF1-derivative since the latter when treated in like mmner with ammonia and methylamine yields with evdlution of nitrous oxide the diketone OMe* C6H4* c0.c 0 Me as chief product only small quantities of the bases OMe*C6H4*C( NOH)*CHNe*NH and OMe*C6H4*c (NOH)*CHMe*NHMe being obtained. The research w. P. w. By A. HNOP (Her. 20 335'2 -3353). When phosphorous pentasulphide is heated with aiiiline a t a temperature not exceeding 150° and the product is steam-distilled and crystallised from alcohol the compound PS*C,,H,,N3 is obtained in monoclinic crystals melting at 153" ; the reaction is accompanied by a violent evolution of hydrogen sul- phide.Chcvrier (Zeit. fiir Chem. 1868 569) by the action of phosphorus sulphochloride on aniline obtained an amorphous compound melting at 75' of the same percentage composition as that described above. N. H. Me is being contin lied. Action of Phosphorous Pentasulphide on Aniline.266 ABSTRACTS OJ!' CHEMICAL PAPERS. Sandmeyer's Reaction. Substitution of Cyanogen for the Amido-group. By F. AHRENS (Beg-. 20 2952-2958).-The three isomeric amidophenols when diazotised and heated with Sandmeyer's solution of potassium cyanide and copper sulphate (Abstr. 1885 149) aye readily converted into the corresponding cyannophenols (com- pare next Abstract).To obtain a good yield of orthocyanophenol it is necessary to separate the diazochloride of orthamidophenol before treatment by Sandmeyer's method but this step can be omitted in the other two cases. Orthanisidine can in like manner be con- verted into cyananisoil. Paramidoa cetophenone on similar freatm ent yields cyanncetophe- none CN-C6N4*COMe. This crystallises. in white needles melts at 60- 61'. is insoluble in water but readily soluble in alcohol and ether and on hydrolysis is converted into Meyer's acetylbenzoic acid (m. p. = ZOOo). The ozime CN*C6H4*CMe:NOH crystallises in wbite scales melting a t 160'. Paramidohenzophenone under like conditions forms a cyanobenzoph enone CN.C6H4* C 0 Ph crys tallisin g in y ellowish-whit e grznules melting at 107-108" and this on hydrolysis yields para- benzoylbenzoic acid.The oxinie CN.C,H,*CPh:NOE crystallises in white scales and melts at 176". When paramidodimethylaiiiline is similarly treated and the product extracted with ether an oil is obtained which cbuld not he purified but probably consists of dimethylamidobenzonitrile CN*C,H,*NMe since. on hydrolysis with alcoholic potash i t yields an acid identical with Michler's paradimethylamidohenzoic acid. The author has not succeeded in converting sulphanilic acid into Otthocyanophenol. By V. MEYER (Ber. 20 3289) .-Repeating Ahrens' experiments on the effect' of Sandmeyer's reaction on amido- phenol the author entirely failed to get the cyanophenol described by Ahrens (preceding Abstract) b u t obtained salicouitrile (Tiemann this.vol.p. 276). Derivatives of Paramidoisobutylbenzene. By C. GELZER (Ber. 20,3253-3259) .-Nitracety lamidoisobuty lbenzene is obtained on nitrating acetylarnidoisobutylbenz~ne at 0" ; it crystal- lises in slender,-yellow needles and melts a t 250-252O with some decomposition. When reduced an anhydro-base seems to be formed. NitramidoisobutyZbeizzene C4H,-C,H,(NCi,)*NH prepared by the action of cold alcoholic potash on the acetyl-compound crystallises in yellowish-red short needles or plates melts at 106.5" is only sparingly soluble in h o t water readily in alcohol benzene and ether. The salts are rery soluble and are not characteristic. DiamidoisobutyEbenzene C4Hg*C6H3(NH2) obtained by the reduction of the preceding compound crystallises in micaceous colourless scales or tables melts at 97*5" distils a t 280-282" and is sparingly soluble in cold readily soluble in hot water and in alcohol ether and benzene.The hyhochZoride C,H,,N2,2HC1 forms lubtrous white cyaiiobenzenesulphonic acid by this reaction. w. P. w. L. T. T. CaHg*CsH,( NO,).NHAc,ORGANIC CHEMISTRY. 267 plates ; the picrate crystallises in slender yellow needles ; the oxalate forms thin white plates. Like other orthodiamines it forms compounds with phenanthraquinone and benzil. P~enanthraisoZ,utylphenazine I 11 I \C6H3*C4H prepared by adding the diamido-base to a solution of phenan thraquinone in glacial acetic acid crystallises in pale-yellow interlaced needIes melts at 146-5" and is very sparingly soluble in hot water or cold alcohol readily in ether or benzene. It is not decomposed when boiled with hydro- chloric acid.With concentrated sulphuric acid it gives a charac- teristic cherry-red coloration. c6H.a.c.N C6H4* GO:." C Ph C *N. BeltziZoisoZ,2Lty123henazine I 11 I \c6H3*c4H forms nearly white C P 11 C *N' slender needles melts at 144") is insoluble in water moderately soluble in alcohol and readi1y.h benzene ether and carbon bi- sulphide. It has very feeble basic powers but a hydrochloride ( C24H22N2)2,HCl is described ; i t forms a greenish crystalline powder and is decomposed when dissolved. Condensation of Chloral Hydrate with Tertiary Aromatic Amines. By 0. KK~~FLER and P. BOESSNECK (Rer. 20 3193-3195). -The compound CCI,GH(OH).C6H4*NMe2 (Abstr.1886 458) is best prepared by treating a solution of 200 grams of chloral hydrate i n 300 grams of dimethylaniline with 110 grams of powdered zinc chloride. After some weeks the viscous mass becomes crystalline. The base is then converted into the hydrochloride. The yield is 82 per cent. of the theoretrical. The sulphate crystallises in cubes more soluble than the hydrochloride. A. J. G. Paradimethy lamidobenz y lidene-phsny lhydraxine NMe2*C6H4*CH:N2HPh crystallises in needles melting a t 148". in yellowish-brown plates melting a t 144". Paradimeihylnmidobenzaldoxime NMe2*C6H4-CH:N*OH crystallises N. H. M Action of Aromatic Diamines on Sugar. By P. GRIESS and G. HARROW (Be7-. 20 3111-31 IS> .-Ar~bino-ortl~odianzidobenzene C6H4<NH >C5H,0a is obtained by mixing aqueous solutions of orthodjamidobenzene (1 mol.) and arabinose (2 mols.). The whole is evaporated nearly to dryness water being added as it evaporates until the amount of crystals no longer increases.It crystallises from boil- ing water in small white needles which melt with decomposition at 235" ; it is sparingly soluble i n boiling water less soluble in alcohol and almost insoluble in ether. It has a slightly bitter taste does not reduce Pehling's solution and is dextrorotatory. Aqueous potash dissolves it readily. Boiling concentrated hydrochloric acid and boiling aqueous potash have no action on it. The hydrochdoride crys- tallises from water in which it is readily soluble in globular groups NH2 68 ABSTRACTS Otc' CHEJIICAL PAPERS.of very small plates. It is sparingly soluble in dilute hydrochloric acid. The I~ydrobromide resembles the hydrochloride. The formation of arabinodiamidobenzene is similar to that of gluco-orthodiamido- benzene (Ahstr. 2887 930) assuming arabinose to have the formula C,Hl0O5 (Kiliani Abstr. 1887 465). 81.abir~ornc!t~~aradiam idof o Zueize C6H3Me <hH > C5H804 prepared similarly to the componnd above described crys tallises in small white needles having n slightly bitter taste. It melts at 238" and is more sparingly soluble than the orthodiamidobenzene-derivative to which it is in other respects very similar. Ara bino- 7- dii1712 idobenzo ic acid c 00 H*C6H3< NH> C,H804 + 2H20 crystallises in needles melting with decomposition at. 235". It is sparingly soluble in boiling water less soluble in alcohol.It is dextrorotatory reddens litmus and does not reduce Fehling's solution. The barium salt is a white amorphous substance ; the silver salt. forms a white sandy powder. The hydroc7doride crystallises from dilute hydrochloric acid in small white needles ; it is decomposed by water . Galacfo-orthodia-i~o~enselze C6H4<NH > c6H,005 rese rribles t be mabino- derivative in physical and chemical properties. It me1 ts a t 246" wit4 decpmposition. The 7Lydror:hZoride with 14 mol. H,O. and the hydrobmmi~e.crysta11ise in needles and are very readily soluble in water sparingly soluble in hydrochloric acid. Galacto-y-dianzidohenxoic acid COOH*CJ13<NH> C6HI0O5 + H20 It completely resembles the corresponding YH NH NH NH crystallises in needles.arabino-acid. N. H. M. Decomposition of Diazo-compounds. By I. REMSEN and W. R. ORNDORFF (Amer. Chem. J. 9 387-399).-Pure and dry diazobenxene nitrate was decomposed by warming it with ten times its weight of absolute alcohol. The several products obtained calculated on the weight of nitrate taken were phenetoil 16 per cent. orthonitrophenol 7 per cent. diriitrophenol 3.5 per cent. benzene 1.8 per cent. and considerable quantities of tarry matter from which nothing definite could be separated ; no aldehyde was observed. Griess had previously not,iced the production of nitrophenols and attributed them to his not having used absoluts alcohol but that this explanation is not correct is shown by the above and by the fact that dry diazobenzene nitrate when heated with dry toluene yields 20 to 24 per cent.of orthonitrophenol but no dinitrophenol. Using 50 per cent. alcohol for the decompmition the quantities of nitrophevols formed are increased whilst the yield of phenetoi'l and especiaIly of henzene is decreased. Using dry diazobenzene sulpl-mte and absolute alcohol SO per cent. of phenetoi'l and 1.5 per cent. of benzene were obtained and using toluene in place of the alcohol para1)henol- siilphonic acid is formed. The last decomposition namely elimina- tion of nitrogen and rearrangement of the constituents of the mole-ORGANIC CHEMTSThT. 269 cule corresponds with that undergone by the nitrate :-C6Hb-N2*O*N02 = C,H,(OH)-NO + N2. Phenetoil boils a t 170" and when treated with fuming nitric acid yields dinitrophenol (m.p. 86-87'). This is very nearly t h e melting point of dinitrobenzene (89*9O) and hence the misstatement that benzene is the principal product of the decom- position of diazobenzene with alcohol. When orthodiazotoluene sulphate is heated with absolute alcohol the principal product is orthocresyl ethyl ether (30 per cent.) ; neither toluene nor aldehyde could be detected. With the para-compound the decomposition is quite different 18 per cent. of toluene and 11 per. cent. of paracres71 ethyl ether being obtained as well as aldehyde. Metadiazotoluene sulphate and absolute alcohol yield neither aldehyde nor toluene but rnetacresyl e t h j l ether is formed (55 per cent. reckoned on the metatoluidine employed). The metatoluidine was prepared from paratoliiidine by nitrating the acetyl-derivative eliminat,ing the amido-group and reducing the metanitrotoluene.In this case i t is to be noticed that the diazo-group is readily displaced by hydrogen a yield of 68.7 per cent. being obtained. The authors conclude that the presence of a paraffin residue in the para-position relatively to the diazo-group is favourable to the displace- inent of' the diazo-group by hydrogen. Wroblewski from st stud7 of the three ohlorotoluidines concludes that in the decomposition of the diazo-compounds by alcohol the normal reaction (production of the hydrocarbon) suffers a change due to the influence of the-halogen when it occupies the para-position relatively to some Dther substitu- ting group. This conclusion is contradicted by the author's experi- ments.Of the nine recorded cases of mono-substituted amido-benzene compounds that undergo Griess' reaction eight contain the two groups in the para-position. An examination of the 80 or 90 cases in which two or more groups are present besides the amido-group and in which the diazo-group is displaceable by hydrogen also shows that in nearly all cases the amido-group is in the para-position with respect to some other group. H. B. Diphenylpara-azophenylene. By E. v. BANDROWSKI (Monatsh. 8 475-48S).-In a former paper (Ahstr. 1886 1023) the author rjhowed that the product of the oxidation of diphenylamine in alkaline - NPh solution is a diphenylpara-azophenylene C,H,< Nph>' a view con- firmed by its ready hydrogenation into a leuco-product ; the latter seems to be identical with Calm's diphenylparaphenylenediamine. To confirm this view this substance was prepared according to Calm's directions from quinol and aniline heated with a mixture of zinc and calcium chlorides in a eealed tube at 200-210".Thus prepared the melting point of the compound was found to be 132-135" instead of 152" as assigned to it by Calm. The same melting point was found for the substance Cl8HI6N2 prepared by the author's method ; hence there can be no doubt as to the identity of the two compounds in question. This identity was further confirmed by the conversion of the diphenylparaphenylenediamine prepared by eit)her method into the oxidation product of diphenylarnine CleHl*Nz which was effected VOL. LTV. t270 ABSTRACTS OF CHEMICAL PAPERS.either directly by moderate oxidation with hydrogen peroxide or indi- rectly by decomposit.ion of the dinitroso-derivative in hot alcoholic solution. This dinitroso-derivative formed by passing nitrous fumes into a cold alcoholic solution of diphenylpar~phenylenediamine forms yellow glistening crystals melting at 120" with decomposition. It gives an intense red coloration with sulphur and nitric acid and is converted by hydrogenation with zinc-dust and acetic acid into diphenylpara-azophenylene and on boiling with alcohol into diphenyl- para-azophenylene and nitric oxide. On bromination in chloroform solution diphenylpara-azopbenylene gives a hromo-derivative C,H8Br6N2 or C18HIOBrRN2. This forms aciculrtr crystals melting at 243".T t dissolves in nitric acid with production of a dirty-green colour. On dilution a reddish precipitate of a dinitro-derivative is obtained but this probably con- sists of two isomeric substances. V. H. V. Substitution in Azo-compounds. By E. Niirmw (Bey. 20 2992-2998) .-Amidoazobenzene yields several crystalline compounds when nitrated none of which however are identical with 1 4 o r 1 3 C,H,(NO,)*N N*C6H4-NHa. The nitro-group seems to enter the amidated group since aniline was obtained by the reduction of the compound. When phenylazodimethylaniline (dimethylamidoazobenzene) is dis- solved in concentrated sulphuric acid (66" B.) nitrated in a freezing mixture with A mixture of 50 per cent. nitric acid (1 part) and sulphuric acid (2 parts) and the product poured into water a nitro- derivative PhN N-C6H,(N02)-NMe2 is obtained which crystallises in black needles with a greenish iridescence and melts a t 198" ; it is insoluble in water sparingly soluble in alcohol and ether readily soluble in benzene.It is a feeble base and on reduction yields aniline and anot'her basc probably dimethyltriamidobenzene. An isomeric nitro-derivative N02*C6H4.N2.~~H4*NMe2 is also formed identical with that prepared by Meldola (Trans. 1884 107). This crystallises ir needles melts a t 225-226" and is sparingly soluble in alcohol ether and benzene. On reduction with ammonium sulphide it yields amido- dimethglamidoazobenzene melting at 186-187" and with tin and hydrochloric acid it is converted into paraphenylenediamine and dime thylparaphenylenediamine.When pnratolylazodimethylaniline is nitrated in like manner it ~ yields a nitro-derivative C6H4Me.N,.C6H4(Pu'Of).NMe which crystal- lises in long bright red needles melts at 181" and is sparingly soluble in alcohol and etther readily soluble in benzene. It is a feeble base and on reduction is converted into paratoluidine and a readily decomposable 'base. The isomeric bases C6H,Me(N02).N,.C6H4.NMe2 [Me NO N = 4 2 I] cx-ystallising in brownish-red scales melting at 159-160" and l>fe NO N2 = 4 3 11 crystallising in red prisms melting at 114G-147" were prepared for purposes of comparison.ORGANIC CHEMISTRY. 271 If phenylazodimethy laniline is sulphonated with 100 per cent. sul- phuric acid at loo" a sulphonic acid s03H*CaH*.Nz*C6H40NMe2 is formed identical with that obtained by Miihlau (Abstr.1884 1149). ParatolylazodimethylaniIine can be sulphonated by dissolving it in 100 per cent. sulphuric acid and heating at 100" with sulphuric acid containing 66 per cent. of sulphuric anhydride; the resulting sulphonic acid S03H.CsH3Me.Nz*~sH4*NMez crystallises in violet prisms and is soluble in hot water and alcohol yielding like its salts red-coloured solutions. On reduction it is converted into dimethyl- psrnphenylenediamine and metamidoparatoluenesulphonic acid. These experiments were made in conjunction with T. Bhumann. When phen ylazophenol (oxyazobenzene) is nitrated under the above conditions the witro-derivative NOZ*C~H~.N~*C~H~.OH forms the chief product. This crystallises in reddish-brown needles melts at 211" and is identical with that obtained from phenol and diazotised paranitraniline.The isomeric nitro-derivatiTres [NO N2 = 1 21 crystallising in orange-yellow needles melting at 126" and [NOz Nz = 1 31 ci-ystallising in red needles melting at 155-157" were also prepared for purposes of comparison. A dinitro-derivative is also formed during the nitration and constitutes the chief product if twice the quantity of nitric acid is employed. It crystallises in orange-red needles melts at 200° and is identical with the compound obtained from diazotised 1 2 4 dinitraniline and phenol. These experiments were made in conjunction with T. Stricker. w. P. w. Diazoamido-compounds. By E. No~nma and F. BIXDER (Bey. 20 3004-3018) .-The authors have prepared the diazoamido-com- pounds from paratoluidine and diazohenzene chloride and from aniline and diazoparatolyl chloride and have submitted each to the following reactions comparing the products throughout :-( 1.) Reduction at 0" in alcoholic solution with tin and bydrochloric acid products aniline paratohidine phenylhydrazine an d paratolylhydrazine.(2.) Bromination in benzene solution in the cold products diazo- paratoluene bromide and tribromaniline. (3.) Digestion with a mix- ture of aniline (2 parts) and aniline hydrochloride (Q part) at 60" until nitrogen was no longer evolved when a sample was treated with dilute sulphuric acid products amidoazobenzene and paratoluidine. (4.) Digestion in like manner with dimethylaniline products para- tolylnzodimethylaniline and aniline.(5.) Digestion with excess of phenol and some sodium hydroxide at 60" until nitrogen was no longer evolved when a sample was treated with dilute sulphuric acid products phenylazophenol (hydroxyazobenzene) and paratoluidine. The quantity of phenol employed seems to influence the nature of the product (compare Abstr. 1887 664). (6.) Digestion with excess of dilute sulphuric acid (1 to 10) products aniline paratoluidine phenol and paracresol. (7.) Ethylation of the compounds and decomposition of the products by treat>ment with dilute sulphurio t 22 i d ABSTRACTS OF CHEMICAL PAPEkF. acid products ethylaniline ethylparatoluidine phenol and para- cresol. I n experiments (3) and- (5) the compounds act as if each liad the constitution PhN N*NH*C7H7 in experiments (2) and (4) as if each had the constitotion C7H,.N:N-NHPh whilst from experiments (1) and (6) both formulte must be ascribed to each of the compounds? and i n experiment (7) each compound must have con- tained both isomerides unless in this experiment a third isomeride has been formed 2s Meldola has been led to conclude is tile case when diazoamidometani%roparaliitrobenzene is ethylated (Trans.1887 110 443). In all these experiments no difference could be detected between the two compounds in the course of the reactions or in the nature or relative quantities of the decomposition products and hence Griess' conclusion that they are identical is confirmed. The compounds formed by the action of diazoparatolyl chloride on ethy laniline and of diazo'benzene chloride on ethylparatoluidine are isomeric.Para~aazotobylethyZnrzilide C7H7N N-NPhEt is an oil which cannot be crystallised and yields paratolylhydrazine and ethylaniline on treatment with nascent hydrogen paracresol and ethylaniline on di- g,>stion with dilute aulphuric acid and paratolylazophenol and ethylani- line on digestion with phenol. Diazo benzene-et hy Zpa yatoluide on the contrary forms red crystals melk a t 38-39" and yields phenylhydrazine and ethylparaboluidine on reduction with nascent hydrogen phenol and ethylparatoluidine on digestion with dilute sul- phuric acid and phenylaaophend and ethylparatoluidine on.digest,ion with phenol. The compounds formed by the action of diazobenzene chloride on parabromaniline and of pambromodiazobenzene chloride on aniline are identical and yield parabromaniline and phenol on digestion with dilute sulphuric acid a result.pointing to the formula PhN N.N%€*C6H4Br.Diazobenzene chloride reach with P-nqhthylamine to form an amido-a,zo-compound ; a ctiazo-nmrifo-compound however is formed by the action of diazo-,B-nnyhthyl chloride on aniline. This crystallises in bright yellow needles melts at 150' with decomposition and yields aniline B-naph thylamine phenol and @naphthol on digestion with dilute sulphuric acid amido-am benzene and ,B-naphthylamine on digestion with aniline and phenylazophenol and ,B-naphthylamine on digestion with excess of phenol the two last results pointing to the formula PhN N*NH*CloH7 which does not accord with its method of formation. The diazo-amido-compound obtained by the action of diazo-3-naphthyl chloride on aniline yields on digestion with dilute sulphuric acid a mixture of aniline or-naphthylamine phenol and a-naphthol.The diazo-aniido-compound foymed by the action of diazoparanitrobenzenc chloride on aniline crystallises in yellow silky needles. melts a t 148" and yields phenol aiid paranitraniline on digestion with dilute sul- Diazobenzcne chloride does not react with paranitraniline.ORGANIC CHE3IlYTRT. 273 phuric acid diazobenzene bromide and bromoparanitraniline on hromination phenylazophenol and paranitranihe on digestion with excess of phenol and paranitraniline aniline amido-azobenzen e and pariinitramido-azobenzene the last in very small quantit>y on diges- tion with aniline. Diazobenzenepiperide PhN N-N C5Hlo obtained by the action of diazobenzene chloride on piperidine and sodium acetate in molcculay proportion yields phenol and piperidine on digestion with dilute sulphnric acid and phenylhydraziine and piperidine on reduction with nascent hydrogen.Diarobenxenetetrahydr~~.~i?aolide PhN N*N C9Hlo obtained in like manner is a yellow oil and yields phenol and tetrahydroquinoline when boiled with dilute sulphuric acid. Diaxobenzenemethylaizilide PhN N-NMePh d s o obtained in like manner is a yellow oil which gradually changes especiaily if Braces of acid are present into the amido-azo-compound and yields phenol and methylaniline when boiled with dilute sulphuric acid and phenylhjdrazine and methylaniline on reduction with nasoent hydrogen. The compound formed by the reduction of paranitmdiaeobeneene chloride on methylaniline is para- n~ts.o~~~enyZazornethijlunill;r~e C6H4( N02)NI N.C6H4*NHMe which ci-ys- tallises in red needles melting at 134".Gasteger has prepared the following -Diazop~rnto71/Zethyl~~a~~- toluide C7HiN N*NEt*C,H a yellow oil yielding paracresol and ethylparatoluidine with dilute sdphuric acidr; diaxom,etanitrobensene- ethylparatoZihide. C6H4(NO2) N N-NEh*C7H which crystallises in yellow needles melts a t 53" and yields metanitrophenol and ethyl- paratoluidine when boiled with dilute sulphnric acid ; dianoyuranitro- Etenxe~Le-ethtlZ~arato~i~ide C6H4(N0,)N N.NEt.C7Hi which crystal- lises in yellow needles melts a t 114-115" and yields paranitrophenol and ethylparatoluidine when boiled with dilute sulphuric acid.TV. P. w. Constitution of Azimido-compounds. By E. NOLTING and A. ABT (Bey. 20 m9-3003) .-Hitherto Gciess' formula R' 'NH (Abstr. 1883 56) for the azimido-compounds has been more gener- ally adopted than the alternative formula R<- N>N proposed by Kekulk and by Idadenburg (Rer. 9 219); the authors however bring forward the following evidence in supFort of the latter and in addition point out that the formation of acetylazimidotoluene from ncetylorthotoluylenediamine (Abstr. 1886 874) admits of easy expla- nation on this theory without assuming an intramolecular change which is necessary if Griess' formula is employed. When pure ethyltoluylenediamine hydrochloride [NEtH NH Me = 1 2 41 in concentrated aqueous solution is treated a t 0" with sodium nitrite in molecular proportion et?r~ZazimidotolzLene C6H,Me N,*Et is obtained ; this cryshallises from alcohol in colourless needles melts a t 147" and is insoluble in water and alkalis but soluble in the ordinary organic solvents.The hydrochloride is N \A/ NH2 74 ABSTRACTS OF CHEMICAL PAPERS. decomposed by wat,er ; the platinfochloride ( C9H12Ns),,H2PtC16 crys- tallises in yellow needles. Azimidotolnene (Ladenburg ;bid.) prepared in like manner from pure orthotolnylenediamine hydrochloride has not only basic but feebly acid properties since it dissolves in alkalis and can be repre- cipitated frcm the aolution by carbonic anhydride. The sodiunz- compound C7H6NaN3 crystallises from benzene in white flocks con- sisting of small needles and in solution is only stable in the presence of excess of alkali.When ethylnted azimidotoluene yields a com- pound identica,l with the ethylazimidotoluene just described and inasmuch as two isomeric ethyl-derivatives are theoretically possible (assuming Ladenburg's formula) the authors hold that in this case i t is the amido-group in the meta-positicn relatively to the methyl which is converted into the azo-group when orthotoluylenediamine is diazo- tised. On fusion with potassium hydroxide azimidotoluene is con- rerted into amidocresol with the evolution of ammonia. In a footnote the authors state ethylnitrotoluidine (Gattermann Abstr. 1885 975) can be obtained by nitrating ethylacetotoluide in 4 parts of sulphnric acid and subsequently saponifying; if larger quantities (20 parts) of sulphuric acid are employed appreciable quantities of the meta-derivative are also formed.w. P. w. Action of Phenylhydrazine on Members of the Carbamide Series. By S. SKINNER nnd S. RUHEMANN (Ber. 20 3372-3374).- When biuret is heated over a small flame with a slight excess of phenylhydrazine ammonia is evolved and Pinner's phenylurazole (Abstr. 1887. 1042) is formed to which the authors ascribe the con- . ' CO*NH stitution NH< CO,Nph>. Diphewylcarbazide GO (NHaNHPh) is prepared by heating urethane (1 mol.) with phenylhydraxine (2 mols.) for some hours until the evolution of ammonia ceases. It melts at 151" is readily soluble in alcohol sparingly soluble in hot water insoluble in ether. Phen?lZsemithiocarbazide NH,*CS*NH*NHIPh formed by the action of phenylhydrazine on monophenylthiocarbamide crystallises in white needles melting a t 190° readily soluble in hot alcohol insoluble in water.Ammonia nitrogen benzene arid aniline are formed in the reaction. N. H. M. Dyes which can be Fixed by Mordants. By S. V. KOSTANECKI (Ber. 20 3146-3149).-Very little is known of the connection existing between the constitution of organic colouring matters arid their tinc torial properties or what determines whether certain acid colouring matters can be fixed by a mordant or not. Experiments were made which seem to show that nitrosophenols can be fixed by a mordant only when they are ortho-quinoneoximes and that other phenol colours can do so only when they contain two hydroxyl radicles in the ortho-position.All the dyes which are derived from gallic acid for instance anthragdlol gallei'n coerulejin galloflsvin,ORGANIC CHEXISTRY. 275 and gallocyanin owe their tinctorial value to the presence of the ortho-hydroxyl-groups (see also this vol. p. 292). F. S. I(. Products of the Action of Nitric Acid on Aeetophenone. By A. 3'. HOLLEMANN (Ber. 20 3359-3362).-Eighty grams of fuming iiitric acid (sp. gr. 1.4) is added t o 10 grams of acetoyhenone and the whole heated at 30-40" ; the liquid separates into two layers of which the upper one becomes crystalline after one to two days. The crystJals are washed with water and extracted with boiling ether. A sparingly soluble nitrogenous substance melting at 177-179" remains undissolved The ethereal solution yields cry stab of a compound c(,N2O2(C0Ph) melting at 87" ; it is readily soluble in alcohol and ether insoluble in water.When treated with potash or sulphuric wid it yields benzoic acid. It is reduced by zinc-dust and acetic acid to diphenylethylene diketone melting at 143" (not 140"). The com- pound contains no hydroxyl-group and can be boiled with acetic chloride for a day without change (compare Rec. Trav. China. 6 60). Methyl Duryl Ketone from Asymmetrical and Symmetrical Durene. By A. CLAUS and C. FOECKING (Ber. 20 3097-3104).- 'Ihe durenes are best prepared as follows :-A mixture of 100 grams of mesitylene (or pseudocumene) and 140 grams of methyl iodide is added to 100 grams of aluminium chloride covered with carbon bisul- phide and the whole heated on a water-bath for five days.The product is treated with water steam distilled and th4 distillate fractionally distilled. The three durenes are separated from one a110 ther by freezing. Unsymmetrical duryl methyl ketone C6HMe4-COMe [Me4 COMe = 2 3 4 G I] is prepared in the usual mauner by means of alum- inium chloride and forms a colourless strongly refractive liquid of a peculiar odour boiling a t 253-255" (uncorr.) ; it is readily soluble in the usual solvents except water. It distils without decomposition with superheated steam. The phenylhydrazine compound forms lnstrous yellowish. matted needles which decompose at 215" without previous fusion. The lLydroxylarnine-derivati,ue crystallises in smnll plates melting at 148". When the ketone is reduced with elm-dust and alcoholic potash the carbinol CsHMea*CHMe*OH is obtained ; it is a pale-yellow liquid and boils at above 300".2 3 4 6 Tetranzethylphenylglyoxylic acld C6HMe4.CO*COOH is formed when the ketone ia oxidised with potassium permauganafe in dilute aqueous solution in the cold. It is a bright yellow oil readily soluble in alcohol and ether sparingly soluble in water When kept in a freezing mixture for months it solidifies. Boiling water decomposes it. The sodium salt (with 5 mols. H20) the potas- sium and barium (with 5 mols. H,O) calcium (with 3 mols. H,O) and other salts were prepared. 2 3 4 6 Tetrametl~ylrr~andelic acid C6HMe4-CH(OH)*COOH is prepared by reducing the glyoxglic acid with sodium-amalgam. It orystallises in short colourless transparent lustrous prisms melting at 156" ; it dissolves readily in alcohol and ether sparingly in water.The sodium (with 1i mol. H20j and potassium salts are very readily N. H. M.27G ABSTRACTS OF CHEJliCAL PAPERS. soluble in water ; the calcium salt (with 8 mols. H,O) crystallises in tufts of needles ; the barium salt (with 3 mols. H,O) forms aniall crystals readily soluble in water. Xymmetriral duryl methyl ketone C6HMe4.COMe [Me4 COMe = 2 3 5 6 13 crystallises in white lustrous plates melts a t 63" (uncorr.) boils a t 251" (uncorr.) and distils with steam. The hydr- mine-derivative forms small lustrous crystals which a t 225" decompose without melting. The curbinol crystallises in white plates which melt a t 72". Symmetrical d u r y l g l y o ~ y l i c acid crystallises in small white lustrous scales which melt a t 124" (uncorr.) ; it is readily soluble except in water and cannot be distilled.The alkali salts are very readily soluble; the potassium with 5 mols. H,O the calcium with 9 mols. H20 the barium with 3 mols. H20 and the silver stclts are described. 2 3 5 6 Tetranzethylmandelic acid C,HMe,*CH(OH)-COOH melts a t 146" (uncorr.) dissolves readily in alcohol ether benzene &c. The alkali salts are very readily soluble and can scarcely be obiained crystalline; the barium salt with 2 mols. H20 and the calcitm. salt with 8 mols. H,O were prepared ; the latter crystallises in small slender needles. 2 3 4 6 Teti-umethyZ~~r2xo.i~ acid C6HMe4-COOH and the 2 3 5 6 acid are obtained by oxidising the corresponding duryvl methyl ketones with warm permanganste solution.The former is a thick oil whilst the latter crystallisea in plates of a Bilvery lustre melting a t 109" (uncorr.). N. 8. M. Nitrile of Salicylic Acid. By F. TIEMANN (Bey. 20 3082- 3084).-XalicyZic acid nitrile is prepared from the aldoxime of salicaldehyde or by distilling the thiamide of salicylic acid. It melts at W dissolves readily in alcohol and ether rather sparingly in water behaves towards alkalis like a phenol and gives a reddish- violet coloration with ferric chloride ; under diminished pressure it distils almost without decomposition and can be readily converted into salicylic acid. The compound prepared by Grimaux (Bull. 8oc. Chirn. 13 25) by fusing salicylamide with phosphoric anhydride which melts a t 195" is therefore not the normal nitrile of salicylic acid (compare also Ahrens this vol.p. 266). N. H. 11. Condensation-products from p-Anilido-acids. By A. REISSERT (Be+. 20 3105-3110).-P-Bnilido-acrylic add NHPh.C,H,*COOK is obtained by boiling the mixture of anilidomnle'ic-anilide and anilidomalei'c acid (formed from aniline and dibromoeuccinic acid Tiemann and Reissert Abstr. 1886 551 ; Michael Abstr. 1886 698 ; and Reissert Abstr. 1886 791) with aqueous potash. The product is precipitated with acetic acid dissolved in absolute alcohol and converted into the sodium salt. It melts with partial decomposition a t 194" dissolves readily with alcohol and acetone and is almost insoluble in water benzene and chloroform. The sodizcm salt with 2k mols.H,O crysdallises in white plates of a silky lustre ; the ethyl salt melts at 143-144".CO*CH ~I-~etodihydroquinoline C6H4<NHmc H> is formed when p-anilido- acrylic acid is dissolved in concentrated sulphuric acid or when tbe acid is heated for a short time a t '200'. The product is several times dissolved in acetone and precipitated with water and is then crjstnllised from alcohol from which it separates in gold-coloured plates melting a t 255". When distilled a small amount is obtained colourless. It is very sparingly soluble in the usual solvents and is almost insoluble in acids and alkalis. When distilled over heated zinc-dust quirioline is formed. N. H. M. Formation of Anilic Acids from Anhydrides of Bibasic Acids. By R. A;"r.scaU~z (Ber.20,8214-3816).-Eumaranilic acid COOH CH CH*CO*NHPh identical with that prepared from malein- itnil is formed when ma!eic anhydride dissolved in ether is mixed with aniline. Mesaconanilic acid prepared from citraconic anhydride melts a t 152-15:3" and is identical with the product which separates when an aqueous solution of moilaniline citraconate is kept. The anilic acid from itaconic anhydride melts a t 151-151*5" ; it is not identical with the acids obtained by Gottlieb and by Michael by hesting itaconic acid with aniline and by boiling an aqueous solution of monanilino itaconate. N. H. M. Hydrazocumic Acid. By N. MOIXANOFFSKI (Chenz. Celztr. 1887 1168 from J. l h s s . Cl/,enz. Soc. 1887 295-297) .-Nitrocurnic acid was reduced in alkaline solution by an excess of sodium amalgam and the reduction products (mostly the azo- and hydrazo-acids) pre- cipitated by adding hydrochloric acid. They were separated by cry stallisation from alcohol the hydrazo-acid being much less soluble in this medium.Hydyazocuuzic acid forms coloiirless needles very stable when dry but in solution slowiy changing into the azo-acid nearly insoluble in cold alcohol more readily soluble in hot alcohol still more readily in hot methyl alcohol insoluble in ether. Bitric acid reach with it in the same way as with the azo-acid. When heated with concentrated hydrochloric acid in sealed tubes a t 100-115" it partly dissolves with a violet colour. Prom the solution ;I white crystalline substance separates after some time which is easily soluble in alcohol dilute hydrochloric and nitric acids and in concentrated sulphuric acid.Salts of the azo-acids crybtallise out from the solution of the hydrazo-acids in alkalis and these effloresce when exposed to the air. Synthesis of Phenoxycoumarin. By A. OGLIALORO (Cherrz. Cewtr. 1887 1164 from Rend. Ace. Sc. NapoLi [2! 1 90-91).-The ituthor has already shown that phenylcoumarin is formed by the itction of sodium a-toluylate on salicaldehyde and acetic anhydride (Abstr. 1880 164)) and phenoxyuinnamic acid by the action of sodium phenylglycolate on benzaldehyde and acetic anhydride (Abstr. 1881 276). By heating acetic anhydride (100 grams) salicyl- aldehyde (25 grams) and sodium phenylglycolate (40 grams) for eight The sodium salt contains 1.2 mols. H,O. J. W. L278 ABSTRACTS OF CHENICAL PAPERS.hours at 150-160" phenoxycou.marin Cl5HI0Oj is formed. I t crystal- lises in small yellow prisms mqlts at 113' (uncorr.) is nearly insoluble in cold very sparingly soluble in hot water more readily in alcohol sparingly in ether and light petroleum very readily in chloro- form and benzene. An alkaline extract from the crude product of the reaction when acidified gave a brown precipitate that crystallised slowly. From this an acid crystallisiog in yellow needles and melting at 175" with decomposition could be separated but has not yet been fully investigated. J. W. L. Derivatives of E thy1 Quinoneparadicarboxylate. By A. HANTZSCH and A. ZECKENDORF (Ber. 20,2796-2801). -The compound C12H&1206 obtained by the hydrogenation of ethyl dichloroqninone- dicarboxylate (Abstr.1887,727)) wad shown by Lahman as quoted by the autbors (Her. 20 1313) to exiat in two forms. The first of these crptallises in colourless radially grouped needles destitute of fluorescence and melts at 123" to a green liquid ; the second formed from the preceding by rapid cooling of the fused substance crystal- lises in greenish-yellow dichroic tables which are stable at the ordinary temperature but are very readily transformed by gentle heating into the original colourless needles. The former represents the stable modification and is regarded as ethyl dichloroquinoldicarb- tmyhte C6(OH),C12(COOEt)2 whilst the latter is the labile form and is regarded as ethyl d ichloroquiiionedihlldrodicarboxylate CsH2C1,02( COOEt),. I n the case of the compound CI2H,,Os from which the compound G12H12C1206 is derived by chlorination and hydrogenation the order is reversed ethyl quinonedihydrodicnrboxylate the coloured compound being the stable and ethyl quinoldicarboxglate which is colourless the labile form (ibid.).It is now shown that tohe dichloro-acid come- spondiug with these salts also exists in two modifications-one coloured and the other colourless. When colourless ethyl dichloroquinoldicarboxylate is treated in the cold with concentrated aqueous fioda a greenish- yellow sodium salt is obtained In aqueous solution this also is greenish-yellow and yields the unaltered ethyl salt on treatment with hydrochloric acid. If however the alkaline solution is saponified on a water-bath evapo- rated nearly to dryuess and the sparingly soluble residue dissolved in water and acidified a pale yellow solution is obtained which by rapid evaporation yields dichloroquinonedihydrodicarboxylic acid C6H2t%02( COOH) + 2H20 in the form of greenish-yellow needles.These are stable in the air but effloresce on exposure over sulphuric acid yielding dichEoroquin.oZ- dicurbozylic acid; the stable form is a white anhydrous powder which on heating carboniseg without fusion or change of colour is sparingly soluble in alcohol and ether almost insoluble in water and pames into the labile form only by heating with aqueous soda and acidifying the solution since it does not directly combine with the elements of water.ORGANIC OHEXISTRY. 2179 Hihherto compounds of this type have been known to react.as if they possessed only one of the two formuh ascribed to them. Arr examination of ethyl tetrahydroxytereph t halate (dbstr. 1886 1028) shows however that it sometimes reacts as if i t were this compound and a t others as if it had the composition of the yellow stable ethyl dihydroxyquinonedihydrodicarboxylate C6H2( OH),02( COOEt),. Thus when heated with acetic anhydride it is converted into :t tetracetyl-derivative C6(OAc),(C00&) a white microcrystalline powder melting a t 202". If however the yellow salt is dissolved in concentrated aqueous ammonia and treated with hydroxylamine it yields the dioxirne of ethyl dihydroxyquinonedihydrodicarboxylate C6H2(OR)2(NOH)2(COOEt)2 as a yellow powder melting a t 156-15i" without decomposition and soluble in alkalis and ammonia.The very similar yellow stable ethyl quinonedihydrodicarboxylate on the contrary does not react with hydroxylamine under the conditions just stated but yields a colourless diucetyl-derivative of ethyl di- hydroxyterephthalate when heated with acetic anhydride. Moreover the compound C6H2o4( CoOE t ) 2 (Abstr. 1886 358) reacts as if it were ethyl dihydroxyquinonedicarboxylate since it yields with hydroxylamine the dzoxinze C,(OH),(NOH),(COOEt) ; this is a yellow powder which melts a t 160" with decomposition and is very sparingly soluble in alcohol and ether soluble in hot chloroform and acetic acid. When ethyl succinosuccinate is treated with bromine in molecular proportion and particularly when the bromination proceeds rapidly a compound which crystaliises in yellow needles is present in the mother-liquor from ethyl q uinonedil~ydrodicarboxylate. This is a hydrate of ethyl quinonedihydrodicarboxylate C1.'H1406 + 2H,O.It melts a t 113" and is slowly converted into the anhydrous cornpound by recrystallisation or more rapidly by boiling its alcoholic solution. I n its fluorescence colour reactions with ferric chloride &c. it re- sembles the anhjdrous salt but diffew from it by yielding on treat- ment with hydroxylamine in ammoniacal solution ethyl quinoltetru- hydrodicwboxylate C,( OH)2&(COOEt)2 a yellow crystalline substance Preparation of Orthosulphobenzoic Acid. Rp N. R. BRACKETT and C. W. HAYES (Amer. Ckem. J. 9 399-496).-The preparation of orthotoluenesulphonic acid from paranitrotoluene by the diazo- reaction is not satisfactory as the greater portion is converted into an ethoxy-compound. Haller's method (decomposition of the hydr- azine compound by copper sulphate) is much better.Hycirazine orth.otoZuer~esu~honic acid N2~3*C6H31Vle*S03'~ prepared by the usual methods ciystallises in scales is soluble in hot water and has acid properties. With copper sulphate it decomposes readily but the ortho- toluenesulphonic acid is not easily purified and is not readily oxidised by potassium permanganate except in alkaline solution ; moreover the yield of the benzoic acid is not satisfactory. Again sodium ortho- toluenesulphonate as prepared above does not give a good yield of orthotoluenesnlphonamide and this last when oxidised gives a fair yield of the sulphinide but little of orthosulphobemoic acid.melting at 128". w. P. w.280 ABSTRACTS OF CHENI JAL PAPERS. The best aiid quickest method of preparing this compound is that of' Noyes (Abstr. 1886 604) by the action of chlorvsulphonic acid on toluene; a mixture of the partt- and ortho-compounds is obtained which is best converted by ammonium carbonate into the toluene- sulphonamides ; by treatment with potassium permanganate the para- coinpound is oxidised to parasul phobenzoic acid and is precipitated by addition of dilute hydrochloric acid whilst from the filtrate strong hydrochloric acid throws down the orthobenzoic sulphinide. This rnay then be converted into orthosulphobenzoic acid by evaporating with hydrochloric acid; the residue is extracted with water from which the substance separates in large rhonibic crystals; a b c = 0.5507 J 1 0.8121.H. B. Paramido-orthosulphobenzoic Acid. By W. A. HEDRICK (Amer. Chem. J. 9 410-418).-P~aranitro-orthotoluenesulphonic acid is oxidised by potassium permanganate in alkaline solution and tjhe para- nitro-orthosulphobenzoic acid precipitated from the filtered and concell- trated solution by hydrochloric acid. The reduction of the nitro-group is effected by ammonia and sulphiiretted hydrogen ; the yield of the pure amido-acid amounts to one-half the weight of the nitrotoluene used. The following salts are described [ COOH-C,H3(NHz)-S03],Bn + 5Hz0 ; C7H5NS0,Ha + H,O ; C7H,NS05Pb ; and CiH5NSO58gz. The silver salt when boiled with methyl iodide and then with water and calcium carbonate yields A compound N&h3~'C6H3<Coo>c~ SOd- whilst ethyl iodide and barium carbonate yield a neutral salt [ CO OEt.C,H (NH,) * S 03]?Ba.The free amido-acid has no basic properties and no acetyl or benzoyl compound could be obtained from it. Paradiaxo-orthosulpla~ben~oic acid COOH c6H3<z&> is best ob- tained by passing nitrous anhydride into a solution of the acid barium salt containing Rome of the same salt in suspension; it Reparates in white crystals. It may be converted into a well-crystallised hydrazine-compound in the usual way. The diazo-compound when boiled with water yields hydroxysuZpphobenzoic acid of which the follow- ing salts are described:- [ COOH.C,B3(OH).S03]LBa ( C7113SOa),Ba3 and C,H,SO,Ca + 5H,O ; the last salt crystallises in the tr&hic pystern; n b c = 0.9567 1 1.0121 ; observed faces cmPq mPw cmP and OP.H. B. Metacresolsulphonic Acids. By A. CLAUS and J. KRAUSS (Ber. 20 3O89-3095) .-1CZetac~esolya~asuIlphonic acid OH*C,H3Me*SO3H [OH Me SO,H = 1 3 41 is obtained by heating sulphuric acid and cresol (equal weights) at 100-120" for some hours. The reaction also takes place at the ordinary temperature but requires three or four days. It ciytallises from dilute sulphuric acid in colourless plates (with 2 mols. HzO)ORGXSIC CHENISTRT. 281 melting a t 75" (uncorr.) and from concentrated sulphuric acid in large colourless plates (with 14 mol. H?O) which melt a t 95-96" (uncorr.). The anhydrous acid melts at l l s " and dissolves verv readily in water alcohol ether and benzene.The potassium salt (with 2$ mols. H,O) forms stellate groups of small crystals of a fatty lustre readily solnble in water; the sodium and Zead salts are also r~arlilj- soluble in water. The copper salt (with 3 mols. € 3 3 0 ) crystallises in h f t s of lustrous pale-yellow prisms rat her readily soluble in water. The sulphochloride C,H,O-SO,CI forms a thin honey-coloured syrup. The sulpJionanaYde is readily soluble in alcohol and ether ; i t does not cr.ystallise. When a dilute solution of the sulphonic acid is heated with chromic acid toluquinone is formed. ~~eetacresoZdisulpJ72onic acid is prepared by heating metacresol with sulphuric acid (4 to 6 parts) a t 120-140" for some hours and forms an oily liquid readily soluble in water and alcohol soluble in ether and benzene.The potassium saZt crystallises wit'h 3 mols. H,O in colourless plates of a fatty lustre ; the barium salt (with f mol. HJ)) is very readily soluble; the Zead salt is a readily soluble slightly lustrous crystalline powder. The copper salt is extremely soluble. The disulphochloride is a thick honey-coloured liquid. The disulphon- amide is also a syrup. Metac~esoltrisulphonic acid is formed when the cresol is heated with fuming sulphuric acid and phosphorus pentoxide at 180". The barium salt is very readily soluble in water. N. H. M. Orthocresolsulphonic Acids. By E. HANTKE (Ror. 20 3209- 3213).-When orthocresol is heated with sulphuric acid for five to six hours on a water-bath Enqelhardt and Latschinoff's sulplionic acid (Zeitsch.f. Chem. 1869 621) is formed. The potassium sslt crystal- lises with + mol. H,O. 'The acid has the constitution- [Me:OH:SOsH = 1 2 4 ] . The same acid is formed together with Neville and Winther's sul- phonic acid [Me OH S03H = 1 2 51 (Bey. 13 1946) when orthocresol is treated with sulphuric mid in the cold. The 1 2 5 acid forms deliquescent needles. N. H. M. Synthesis of Anhydrides of Aromatic Sulphinic Acids. By R. Owo and A. MILCH (Rer. 20 3337-3338).-1n a previous paper (Abstr. 1885 1231) Otto and Rossing showed that when an alkyl chlorocarbonate is allowed to act on an alkaline sulphinate an aikJl sulphinate and carbonic anhydride are formed. The authors now find that a similar reaction takes place when carbonic oxychloride is substituted for the chlorocarbonate.Phosgene gas and sodium benzene- sulphinate yield carbonic anhydride sodium carbonate and benzene- sulyhinic ailhydride (C,&SO),O. This conipound is soluble in ether b u t is decomposed immediately by water and alcohol forming the acid or the ethyl salt respectively. L. T. T.282 Al3STRACTS OF CHEMICAL PAPERS. Sulphoneketones. By R. and W. OTTO (J. pr. Chem. [2] 36 401-432).-Phenylsulphon~cetone behaves as a ketone forming with sodium hydrogen snlphite colourless tabular crystals of a double salt ; with hydroxylamine mono- or tri-clinic needles of phenylsul- phonacetozime 0H.N CMe*CH2-S0,Ph melting a t 147-148" ; with ammonia tabular crystals of phenylsulphonacetonamine NH CMe*CH2SOzPh*Me melting a t 110-11 1". With phenylhydrazine it yields pale-yellow needles melting a t 129" of formula N2HPh CMe*CH2*SOZPh and with thiophenol it forms needles of phenylsulphonacetone mercnptole CMe( SPh),*CH2*S02Ph melting at 103-104".When oxidised it vields acetic acid benzenesulphonic acid and carbonic anhydride. When reduced by hydrogen in an acid solution phenyl mercaptan and isopropyl alcohol are formed ; in an alkaline solution benzenesulphinic acid and isopropyl alcohol. With bromine it yields phenylsuZphone- bromacetona crystallising in colourless silky needles soluble in hot alcohol and melting at 96" and pheny lsulphonedibromacetone also in colourless needles me1 ting a t 113-1 14". With potassium hydmxide it yields potassium acetate and methylphenylsulphone. 1)iphenylsulphonacetone has the symmetrical constitution CO(CH,-S&ph')2 for yt is conveheh by potas&um hydroxide into potassium phenylsulphonscetnte and methylphenylsulphone.Di- phenylsulphonacetoxime 0H.N C( CH2*S0,Ph) obtained by heating the above compound with hydroxylamine hydrochloride crystallises in rectangular tables melting izt 1.76-137". The phenylhydrazine compound forms yellow needles melting at 171". With thiophenol diphenylsulphone rnercaptart is formed as a fine lustrous crystalline powder insoluble in water melting a t 190-191". A briphenylsulphone-derivative was not obtained by acting on phenyldibromacetone with sodium benzenesulphinate. Parato1 y Zsu Zphonacetone COMe CH,. S02*C7 H forms long silky needles soluble in alcohol benzene and chloroform and melts at $1" The bromo-derivative GH,Br*C0.CB,*S0,.C7H7 cryshallises in needles or rectangular plates melts at i29-13Oo and is sparingly soluble in hot water Diparatoly lsulpkonaeetone CO ( CH2* S 0,.C7H7) forms white rhombic tables melting a t 152" ssluble in hot glacial acetic acid and in chloroform. Paratdylsnlphonephenylsulphonacetone C7H,*S0,*CH2*CO*CH,*S02Ph prepared by the action of paratolylsulphonebromacetone on sodium benzenesulphinate crystallises in rhombic plates and melts a t 112". Calcium phenylsulphonacetate crystallises with 24 mols. H,O in small needles the lead salt with 2 mols. H 2 0 ; the silver salt when heated yields methylphenylsulphone and not diphenylsulphonacetone as was expected. A. G. B. Ethereal Salts of Benzoic Sulphinide. By R. N. BRACRETT co (Amer.Chem. J. 9 406-410).-The methyl salt C6H,< SO,>NMe,ORGANIC CHEMISTRY. 283 is obtained from methyl iodide and the potassium or silver salt. It crystallises from alcohol or hot water in flat needles melting a t 131- 132". The ethyl salt C7H4S03NEt melting at 96-97" (Fahlberg and List give 93-94") is prepared in like manner; at the same time some ethyl orthosulphamine benzoate is formed. The propyl salt melts a t 60-70". When benzoic sulphinide is treated with phosphorus pentachloride and methyl alcohol added in the cold a crystalline substance is pre- cipitated probably c"~"<~-,i >NH ; when this is boiled with methyl alcohol it dissolves and the solution on cooling yields first crystals of an acid melting above 330" and then crystals melting at so 2 C ( OMe)2 123-125" ; the latter is the dimethyl ether C6H4< so ->PIT= of Remsen and Palmer and when boiled with water and barium carbonate yields the barium salt of benzoic sulphinide. H.B. Aromatic Lead Compoupds. By A. POLIS (Bey. 20 3331- 3336).-The author has obtained lead tetraphenyl (Abstr. 1887 572) in measurable crystals. These crystals are colourless prisms belong- ing to the tetragonal system; axial ratio a c = 1 0.3808. The corresponding tin compound gives a c = 1 0.38935. Silicon tetraphenyl gives a c = 1 0.43969. The three compounds are isomorphous the valne of the principle axis decreasing with the increase of atomic weight of the grouping element. Lead diphemy2 dichZoride PbPh2CI2 is formed by the action of chlorine on ft carbon bisulphide solution of lead tetraphenyl or from the nitrate (Zoc.eit.) by precipitation with potassium chloride. It is a white powder insoluble in alcohol and ether sparingly soluble in chloroform benzene and carbon bisulphide. The oxide PbPh20 obtained by the act'ion of soda on an aqueous solution of the nitrate is a white powder which does not fuse without decomposition. It does not seem to form a hydroxide but is strongly basic i n character and dissolves in acids t o form salts. The acetute PbPh2(OAc) + 2H20 forms long colourless needles ; the formate PbPhz(CHO2) + H20 colouriess needles ; the basic cyaqide PbPh,Cy*OH a white powder ; the thiocyannte PbPh,( CNS) and the phosphate (PbPh,),P208 white flocculent pre- cipitates ; the basic carbonate (PbPh2*OH)&03 a white powder and the chromate PbPh2CrOd a yellow precipitate which when crystal- lised from a mixture of alcohol and benzene yields yellowish crystals.L. T. T Methylketole. By E. FISCHER (Annulen 242 372-383) .- Many of the compounds mentioned in this paper have been previously described by the author (Abstr. 1887 265). Benzylidenemethylketole CHPh(C9H8N) begins to melt at 242" and melts completely at 246-247'. In the crystalline state this substance is sparingly soluble in the ordinary solvents with the exception of acetone. The amor- phous precipitate which is formed when water is added to the solution i n acetone is fkeely soluble in ether and alcohol but it soon changes to284 ABSTRACTS OF CHEMICAL PAPERS. the less soluble form. On oxidation dimethylrosindole is producecl (Abstr.1887 588). Metanitrobemaldehyde and methylketole readily unite form inq ni~tanitrobei~z!llidel.!emeth?ll7cefo7e. This substance is soluble in acctone melts a t ?63" arid yields a red colouring matter on oxidation. Whrn rcduced with zinc-dust and ammonia it is converted into mefamido- benz~/Zitbr)enzeth?/lketoZe NH2.C6H,-CH(C9H8N),. This base is soluble in ether alcohol and benzene. The preparation of efh~~lidenemetliyl- I,-eto7e CHMe(C,H,N) from paraldehyde zinc chloride and methyl- ketole has already been described (Abstr. 1887 265). It melts a t lYl" and boils with slight decomposition. It is freely soluble in alcohol ether and acetone. Bg acting on methylketole and phthalic anhydride with zinc chlo- ride a t loo" a compound of the composition C17H,,N0 is obtained.It forms colourlesa prisms and dissolves in hot alcohol and acetic acid. The acid melts above moo and completely decomposes a t a higher temperature. The author. is of opinion that the acid may have the formula C9H,N-COGsH4-COOH. In the presence of zinc chloride 1'-methylindole and phthalic an- hydride unite to form phthalylmethylindole C26H,oN,0,. The new compound crystallises in prisms melts a t 300" and dissolves in hot acetone. w. c. w. Azo- and Amido-derivatives of Methylketole. By P. WAGNER (Annalen 242 383-388) .-The preparation of methplketoleazo- benzene C8H,N(Me)N,Ph has been already described (Abstr. 1887 265). On reducing the alcoholic solution with t'in and hydrochloric acid aniline and amidomethyl ketole are foitmed.The ketoIe crystJallises in plates and melts a t 112-113". It is soluble in alcohol ether chloroform and light petroleum. The liydrochloritle crystallises in prisms which turn pink on exposure to the air. When reduced with zinc-dust and hydrochloric acid amidomethylketole yields first methylketole and then hydromethylketole. On oxidation with ferric chloride amido- nietliylketole yields a mixture of two compounds one of which is very solutde in alcohol. The other is less soluble in alcohol crystallises in plates and has the empirical formula CgH7N0. It melts a t 22.5" with partial decomposition. When dry hydrogen iodide is passed into an ethereal solution of methylketole an amorphous precipitate ( C9H9N,HI) is produced. The compound is decomposed by water into its two components.Derivatives of p-Naphthindole. By A. STECHE (Annalen 242 367-3'1) .-p-hiayhtli ylhydrazinelevulii~ic acid is deposited as a crystalline precipitate on the addition of water to an alcoholic solution of levulinic acid and p-naphthylhydrazine in their molecular propor- tions. At 170" the acid is converted into the an7ydride. This substance melts a t 119" and is deposited from hot alcohol in needle- shaped cr-y stals. Et h y l nup hth y lhy drazilze7evulin ate is formed by the direct union of ethyl levidinate with /3-naphthylhydrazine. It is crystalline and melts at 129-130". It is converted into methgi-/3- The compound is soluble in alcohol ether and benzene. w. c. w.ORGANIC CHENISTRY. 285 NH naphthindolacetic acid C,,H,<CMe>C*COOH by the action of zinc chloride a t 130-135'.This acid is freely soluble in alcohol ether acetone and acetic acid. The silver salt is decomposed by boiling in water forming a metallic mirror. The acid decomposes at 210" yielding carbonic anhydride and ~ i m e t h y 1-P-ra~jhthindole CI,NH,Mee [Me = 2" 3"]. The latter com- pound melts a t 126" and dissolves freely in alcohol and acetic acid. It yields a dark-red picrate and a crystalline nitrosamine and gives a characteristic blue coloration with acetic acid and ferric chloride. On reduction with zinc-dust and hydrochloric acid hydrodimethyz-P- naphthindoze is produced. This base is an oily liquid which turns red on oxidation. The platinochloride is crystalline and is decom- posed by boiling water. w. c. w.Hydroxydiphenyl Bases. By A. WEINBERG (Ber. 20 3171- 31 78) .-ianzidohydroxydi~h~n~lsu~ho?iic crcid OH-C,,H,(NH,),.SO,H [OH NH SOsH NH = 3 4 6 4'1 is prepmed by reducing with stannous chloride a t a temperature not exceeding 30" 300 grams of sodium benzene-azopamphenolsulphom i e dissolved in 500 C.C. of water. Aftor 12 hours the product is treated with hydrogen sulphide filtered and evaporated to a small bulk ; the hydrochloride of the sulphonic acid separates in large clear crystals. The free sulphonic acid crystallises in needles from water which dissolves it readily. D i a m i d o h y d r o x ~ d i p h e r ~ l C,,H,(NH,),*OH [= 4' 4 33 is formed when diamidohydroxydiphenylsulphonic acid hydrochloride is heated with water at 180". It crjstallises in colourle~s plates melting at 185" and is almost insoluble in water readily soluble in dilute caustic alkali solutions.The alkaline solutions oxidise quickly when expostbd to air. Diamidolzydrox~phen~ZtoZ~lsu~ho~i i c acid 0H.C 12H5Me ( NH2),*S O,H [NH Me OH NH S03H = 4' 3' 3 4 61 is prepared from the dye obtained from ortliotoluidine and paraphenolsulphonic acic . It crptallises in colourless needles which decompose when heated. It dissolves sparingly in water readily in acids and alkalis. Diamidohydmayphenylfolyl NH,-CcH3Me.C6H,(NH,)*OH prepared by heating the sulphonic acid with water a t 180° crystallises from water in lustrous plates melting a t 177" ; it dissolves readily in dilute aqueous potash sparingly in ether and benzene. The sulpliate is almost insoluble in water more soluble in dilute acid.Diamido-~thorydi~henylsu~honic acid C12H16N2S01 is obtained by reducing sodium benzene-azophenetoilsulphonate. It crystallises in needles sparingly solubie in cold water. The hydrochloride (with 2 niols. H,O) is readily soluhle. Diamido-ethoxydiphenyl Cl4HlZO(NH2) is prepared by heating the above snlphonic acid with water a t 170" for 8 to 10 hours; i t forms flat lustrous needles which melt a t 134-135" dissolves sparingly in water ether and benzene readily in alcohol. When heated with h.ydrochloric acid diamidohydroxydiphenyl (m. p. 185") is formed. The hydrochloride is very readily soluble. VOL. LIT. ZG286 ABSTRACTS OF CHEIIIICAL PAPERS. The suZphate crystallises in prisms sparingly soluble in water readily in hydrochloric acid.Diamido-etho~pheny ItolzJlszL~holzic acid is sparingly soluble in water. The hydrochloride forms large prismatic crystals (with 4 mols. H,O). The barium saZt (with 8 mols. H,O) crystallises in concentrically grouped needles. ~inmido-etAozy~henyZtoZ?;ll C,,H,,N,O cryRtallises from water in flat needles melting a t 117.5"; it is sparingly soluble in water cold alcohol ether and benzene. When saponified it yields diamido- hydroxyphenyltolyl melting a t 177". Diwmido- ethoxy n aph t7zyZph ew y 1 NH2.C6B,*C ,,H5 ( OE t ) *NH2 [NH CIZHI2NO = 1 4; C,H,.NH OEt NH = 1 3 41 is prepared by dissolving benzene-azo-P-naphthol in the equivdent amount of alcoholic potash adding ethyl bromide and boiling the whole for 24 hours under a slight pressure When cold it is filf ered and evaporated down when the benzene-azo-P-naphthyl- ethyl oxide remains as a dark-red oil.This is reduced with stannous chloride. The diamide melts a t 72" dissolves readily in alcohol ether and benzene ; the alcoholic solution shows a greenish-blue the ether and benzene solutions a violet fluorescence. The normal sulphnte is sparingly soluble in water ; the hydroc7doride crystallises in needles of a silky lustre. N. H. M. Dinitrobenzidine. By E. v. BANDROWSKI (Monatsh. 8,471-474). -By the hydrolysis of dinitr~dipht~halylparabenzidine with sulphuric acid at 130" two di.nitrobenzidines are produced together with phthalic acid. One modification less soluble in ammonia forms long needles melting a t 21@-221" and decomposing when heated with explosion.The more soluble modification forms saffron-yellow needles melting a t 196-197" ; it is also distinguished from its isomeride by its greater solubility in aicohol and dilute acids. A dinitrobenzidine has pre- viously been described by Strakosch who obtained it by the nitration of acetylbenzidine ; this has been shown by Brunner and Witt to be an ortho-derivative. From its method of formation it would seem that this compound is identical with the isomeride melting at 218- 221" described above although Strakosch assigns a melting point of over 300" to the substance. However the identity of the two sub- stances is confirmed by the formation from both of them of the same tet ramidodiphen yl. V. H. V. Bases produced by Nascent Formaldehyde. By J. TR~GER (J.pr. Chem. [2] 36 225-245).-A crystalline monacid base pro- bably CH,( CH:N-C6H4Me)2 is produced by the action of nascent formaldehyde on paratoluidine ; it melts at 134" dissolves in alcohol ether &c. but is insoluble in water; it forms a crystalline hydro- chloride sulphate platinochloride and picrate. When treated with nitrous acid carbonic anhydride and nitric oxide are evolved and a compound having the formula C,,HlSN4O2 is formed ; this substance dissolves in acetic acid but is insoluble in alcohol ether water andORCIASIC CHEMISTRY. 287 concentrated hydrochloric acid ; it melts at 260-264" with decompo- sition gives Liebermann's reaction and also the nitric acid reaction with ferrous sulphate. A very similar product is obtained when the base is treated with nitric acid nitrogen dioxide and carbonic anhydride being evolved ; with acetic anhydride it yields a very stable compound Cc2H4,Na0,. Nascent formaldehyde and dimethylaniline yield tetramethyldi- amidodiphenylmethrtne from which a crystalline picrate and nitro- derivative CH2[ C6H(NOZ),.NMe2 J2 were prepared.Tetramethy ldiamidodipheny Zethane C2H4*( C6H4*NMez)z is produced TV hen dimethylaniline and carbon bisulphide are treated in alcoholic solution with zinc-dust and concentrated hydrochloric acid; it is a colourless crystalline compound melts at 8 7" dissolves in ordinary solvents but is insoluble in water; combines with methyl iodide forms a crystalline picrate (melting at 190') and platinochloride and with nitric acid yields dinitronitrosodimet hylaniline N0.C6H2(N02)2*NMe2.F. S. K. Condensation Products from Paratoluidine and Paranitro- benzaldehyde. By A. BISCHLER (Ber. 20 3302-3306).-When paranitrobenzaldehyde paratoluidine and concentrated hydrochloric acid are heated together in alcoholic solution a-paranitrophen?y ldi- pararnidotolylmethane N02*C6Ha.CH( C6H3Me-NH2)2 is formed. Crys- t'allised from benzene this substance forms white needles of the formula 3C,,H,,N,O2 + C6Hs which lose their benzene at '110-120" and melt at 170-172". It is but sparingly soluble in alcohol and ether easily in boiling benzene. Its salts crystallise with difficulty ibnd are decomposed by water. The platinochloride C21H2,N3o2,H2PtCl6 forms yellow crystals soluble in boiling alcohol. When however pnranitrobenzaldehyde and paratoluidine are heated with strong sulphuric acid an isomeric compound P-yaranitro- phenyldiparamidotolylmethane is formed.It crystnllises in yellow scales melting at 126-127" and is easily soluble in cold benzene and boiling alcohol or ether. I t also is but a feeble base but its salts are more easily crystallisable than those of the a-compound. The hydro- chloride forms yellow needles the p7atinochZoride yellow scales. The author believes the isomerism of these two compounds to be due to the benzaldehyde nucleus displacing ortho-hydrogen atoms in the toluidine in the a-case meta-atoms in the p- (sulphuric acid) condensation. L. T. T. Compounds of Ketones with Dimethylaniline and Diethyl- aniline. By 0. DOBNER and G. PETSCHOW (Annalen 242 333- 348). -The formation of tetrame thyldiamidodiphenylpropane by the action of zinc chloride on acetone (1 mol.) and dimethylaniline (2 mols.) has been already described by Dobner (Abstr.1879 787). By a similar reaction tetreth~lldiamidodiphe~~yl~~G~ane CMe2(C6H4-NEt2) has been prepared from diethylaniline and acetone. The base forms silky needles and melts a t 76". It is soluble in ether carbon bisulphide benzene and light petroleum. The salts are very 111. 2288 ABSTRACTS OF CEEMICAL PAPERS. soluble and crystallise with difficulty. The hydriodide C2sHsNz 2H1 forms pale-yellow plates freely soluble in alcohol and in hot water. Tetramethyldiamidotriphenylmethane is the chief product of the action of zinc chloride on acetophenone and dimethylaniline. Tetra- metliyldiamidodiphenylmethane and triphenylbenzene are also formed.Tetramefhyl~~am~dotr~7~enylethane CMePh( C6H4.N&fe2) is a pale- yellow oil which gradually acquires a dark-red colour on exposure to the air. It boils above 360" with part,ial decomposition; under reduced pressure it may be distilled without undergoing any change. It is non-volatile in steam and dissolves freely in ether benzene light petroleum and wwm alcohol. The salts are very soluble in water and do not crydallise. It yields amorphous precipitates with the chlorides of gold platinum and mercury. An acetic acid solution of the base turns blue on the addition of lead or manganese peroxide. Benzoplienon e and dime thylaniline yield dim ethylamid o tri ph enyl- methane. Methyl hexyl ketone and dimethylaniline yield tetramethyl- diamidodiphenylmethane and a liquid base CI4Hz3N which is probably a hexyldimethylaniline. The chief product of the action of zinc chloride on diethyl ketone and dimethylaniline is tetramethy ldiamido- B y C.-0 LLYANN (J. pr. Chem. [ 2 ] 36 246-272).-Diamido-derivatives of Iriphenylmethane are produced by the action of benzaldehyde on a mixture of a suitable aromatic base a i d its hydrochloride. Aniline yields diamidotri- pheny1rnet)hane ; orthotoludine gives dia~idorthotoZylphenylmethane a white microcrystalline powder whose melting point could not be determined. Paratoluidine yields diamidopa~ratolylphenylmethane which crystal- lises from a mixture of benzene and light petroleum with + mol. c6H6 in concentric groups of yellow needles and melts at 185- 186" ; it is a.diacid amiae and forms a liydrochloride picmte $c. The colourless crystalline acetyl-derivative C2,H,,(NHAc) melts at 217-218" ; the beruoy Z-derivative C21Ht8(NHBz)2 melts a t 196". By means of the diazo-reaction diamidoparatolylphenylmethane can be conrerted into the di-iodo-derivative C21H1812 crystallising in brownish-red prisms and melting at 167-168". When distilled with zinc-dust it yields paratoluidine and methylacridine and therefore probably has the constitution CHPh(C6H,Me*NH,) [Me CH NH = 1 3 41 ; from its formation by the above method and as it can also be obtained by Mazzara's and by 0. Fischer's methods it follows that it is not necessary that the para-position with respect to the amido-group shoul d be free in order to synthesise amidotriphenyl- methane-deriratives.I n the preparation of the para-compound a substance of the formula cZlH16N2 is also formed; it crystallises in long nearly colou .less needles melts a t 177-176" and gives an orange-yellow crysta,Il ine platinochloride. diphen ylmethane. w. c. w. Derivatives oT Wq5henS;lrneChane. F. S. K.ORGANIC CHEMISTRY. 289 Tetramethyldiamidothiobenzophenone. By 0. BAITHER (Ber. 20 3289-3298).-The author is inclined to think that this sub- stance which he previouslg described (Abstr. 1887 SlS) is really a thioketone and identical with the compound obtained by Fehrmann (this vol. p. 156) from auramine. He believes the differences of properties and melting points are due to want of purity and difficulty in exactly determining the melting point.He now gives the melting point as 193-194.. When the ketone is heated with benzoic chloride in carbon bi- sulphide solution a dic?~Zoro-derivative CC12(C6H4*NMe2)2 is formed which is soluble in alcohol and glacial acetic acids sparingly so in benzene and chloroform and when heated decomposes. With water it yields Michler s kekone CO(CsH4*NMe2)2 and is probably the compound prepared from the latter. in the manufacture of auramine colouring matters. With benzoic chloride,. the thioketone forms an additive derivative CS( C6H4*NMe2)n,COPhCl. This subsbance is crystalline and melts below 200° but was not obtained quite pure. It is soluble in acetic acid and in benzene. Alcohol and chloroform also dissolve it but a t the same time decompose it i n b its two constituents.Acetic chloride yields a similar derivative CS( C6H4.NMe,)2,COMeCl which is crystalline and begins to decompose at 160". It is soluble in alcohol acetic acid chloroform and benzene. When the thioketone is heated with acetic anhydride and sodium acetate it yields a compomnd CssH46N40~S of which the constitution is probably s[C(C,H,*NMe,),*oAc],. It forms a green powder which begins to decompose at 120". When heated with aniline the thiokehone appears to yield chiefly Michler's ketone b u t with aniline hydrochloride it yields phenyl- auramine. The author found the melting point of the latter to be 170-1 71". Phenylhydrazine appears to convert the thioketone into the corresponding oxy- (Michler's) ketone. In his previous communication the author described the product of the action of nitric acid on the thioketone as trinitrodimethylaniline.He now finds however that it is the same compound Go[ C6H2(NOz)z.NMe*N02]2 obtained from Michler's ketone. With hy droxylamine this compound yields van Romburgh's compound' COrC6Hz(N02)2.NHMe]2. It is pro- bable that an oxime is first formed and is subsequently decomposed. L. T. T. Ring-formation with Elimination of Hydrogen Bromide or Nitrous Acid. By E. LELLMANN and 0. SCHMIDT (Ber. 2 0 3 1 5 6 3157) .-When P-naphthyltlmine is treated with glycerol orthonitro- phenol and sulphuric acid it yields P-naphthaquinoline in which the condensation has occurred at the 1 2 position ; it was thought that by starting from a-bromo-P-naphthylamine in which the 1 position is occupied the condensation would occur at the 2 3 positions. a-Bromo-P-naphthylamine [Br NH,=1 21 was obtained by brominat- ing P-acetonaphthalide ; i t was then treatled with glycerol orthonitro- phenol and eulphuric acid and the product of the reaction crystallised290 ABSTRACTS OF OEEMlCAL PAPERS.from light petroleum ; it melted at 93.5" and on examination it was found that p-naphthaquinoline had been formed with elimination of hydrogen bromide. a-Nitro-6-naphthylamine when treated in a similar manner yields the same compound with elimination of nitrous acid. The conclusion drawn is that the 6'-carbon-atom is far less prone to ring-formation than the a-carbon-atom. The nitrophenol takes no part in the reaction the result being the same whether it is present o r not.I?. S. K. Isomeric Naphthylaminesulphonic Acids. By G. SCHULTZ (Rer. 20. 3158-3162).-Bayer and Duisberg (this vol. p. 732) have stated that when P-naphthylamine is sulphonated a mixture of sulpho-acids is obtained from which a hitherto unknown P-naphthyl- amine-b~iionosulphonic acid can be isolated ; this compound yields a /jl-naphthol-3-sulphonlc acid which is identical with Casella and Co.'s naphtholsulphonic acid F ; conversely by heating this acid with am- monia Bayer and Duisberg obtained a compound identical with P-naphthylamine-6-sulphonic acid. Weinherg and Lange (this vol. p. 160) throw doubt on the identity of the acid which they themselves obtained from naphtholsulphonic acid F and that prepared by Bayer and Duisberg from p-naphthylamine. The author concludes that Weinberg obtained an impure product only and gives proofs of the identity of the acids in question.F. S . K. Intramolecular Migration in p-Naphthylaminesulphonic Acids. By A. WEINBERG (Bey. 20,3353-3355).-When /3-napthyl- amine-a- and ysulphonic acids are added to sulphuric acid (3 parts) previously heated at 160" and the whole kept at this teni- perature for 1$ hours they both yield as chief product the 2 2' acid together with the 2 3' acid. The same product is formed by sulpho- nating p-naphthylamine sulphate. It is possible that Bayer and Duis- berg's &acid (Abstr. 1887 732) really consisted of this mixtpre. (Compare Schnltz preceding Abstract.) N. H. M. Conversion of BTaphthylarninesulphonic Acid into Dichloro- naphthalene. By H.ERDMANN (Bey. 20,3185-3187) .-When Witt's naphthdenedisulphonic acid (Abstr. 1886 554) is diazotised the product warmed with phosphorus pentachloride and then distilled dichloronaphthalene [ 1 4'1 melting at 107" is obtained together with some a-monochloronaphthalene. The yield of dichloronaphthalene is 30 to 40 per cent. of the theoretical. N. Ef. M. Action of Bromine on Diamido-a-naphthol. By T. ZINCKE and C. GERLAND (Ber. 20 3216-3231 ; compare Abstr. 1887 838). -When bromine acts on bromamido-a-naphthaquinonimide or bromo- hydroxynaphthaquinonimide the main products are the tribromide C,H,Br3N03 and the dibromide C,H,Br,O ; the latter meIts at 176" which is rather higher than the figure given by Kronfeld. I n the second case a small quantity of a third bromide melting at 130" is also formed.ORGANIC CHEMISTRT.291 By t,he bromination of bromamidonaphthaquinone or of bromo- hydroxynaphthaquinone four brominated compounds are obtained of which three are formed in very small quantity. Two of these are not yet worked out the other is identified as the dibromide CgH4Br202. The main product is a dibromo-compound C10H6Br201 dibromotriketo- hydronaphthalene hydrate C6H4< Br2,> ; this crystallises in matted needles melts at 114-115" with decomposition is readily soluble in alcohol chloroform and benzene less Yeadily in light petro- leuin and is soluble in alkalis with yellow coloration. It is readily converted into bromoxy-a-naphthaquinone and hypobromous acid either when heated alone or when boiled with benzene toluene dilute alcohol or dilute acetic acid.When boiled with water carbonic anhydride is evolved and a- mixture of bromoxynaphthaquinone and the dibromide C9H4Br20 separates. When dissolved in ethyl or methyl alcohol and treated with hydrogen chloride chlorohydroxy-a- naphthaquinorie is formed. When boiled with aqueous potash it yields a monobromo-compound crystallising i n small nearly colour- less plates andneedles and melting at 118-119" and probably of the constitution C6H4<- CO->CBr or C6H4< CO>CHBr probably due CO*C(OH) C(0H) co to the decomposition of an acid C,3H4<-c0.cBr2-> C (OH) (COOH) first formed and for whose existence some evidence is adduced. coac(0H)2> co-cc12 The corresponding dichloro-compound C6H,< pared in similar manner crystallises in thick white needles melts at 105" without decomposition and is far more stable than the dibromo- compound.When treated with alkalis i t is converted into a crystal- line compound melting at 128-129" and if the alkaline solution is oxidised small lustrous plates melting at 124-125". The authors regard - C(OH)(COOH) GCi,> these substances as having the formulae C,H,<cQ and c6H4<co> CO cClz respectively. A chlorobromo-compound CloH6C1BrO4 was also prepwed ; it is less stable than the dichloro-compound crystallises in white needles melts at 104-105" and when oxidised in alkaline solution yields plates of a substance melting at 141". When the dibromide C9H,Br204 is treated with aqpeous soda it yields bromoform phthalic acid and the monobromo-compound C,H,BrO2 described above.A. J. G . Synthesis of Anthracoumarins from Cinnamic and '1G1 eta- hydroxybe37zoic Acids. By s. v. KOSTANECKI (Ber. 20 3137- 3145). \V l i t 3 1 1 a mixture of cinnamic acid and metahydroxybenzoic acid or nvly hydroxy-derivative of the latter is heated with concen- trated sulphuric acid condensation products are formed. From metahydroxybenzoic acid anthracozcmarin ClsHs03 is ob- tained as a yellow crystalline compound melting at 260" ; it dissolves readily in hot glacial acetic acid benzene concentrated sulphuric acid,292 ADSTRACTS OP CHEMICAL PAPERS. and hot baryta-water sparingly in alcohol; with boiling alkalis it forms a yellow solution of green fluorescence which probably contains a salt of the corresponding coumaric acid.It is not dissolved by alkalis in the cold whilst the compounds obtained from dihydroxy- benzoic or gallic acid are readily soluble. This fact shows that the hydroxyl-group has taken part in the con- densation and from the great similarity between these compounds and anthraqninone-derivatives the constitution of anthracoumarin is ,/G9*CD*Dt probably C /C6H3. c6H4.co- In like manner metahydrozyanthracoumariiz CI6H8O4 is obtained from symmetrical dihydroxybenzoic acid. By sublimation or crystal- lisation from acetic acid yellow needles are formed which melt at 325' and are only sparingly soluble in any ordinary solvent ; they dissolre however in alkalis and sulphuric acid. When boiled with baryta- water the coumarin-ring is probably split an insoluble barium salt being precipitated. The yellow crystalline monacetyZ-der.ivatire C16H704Ac melts a t 25.5".Orthodihydroxyanthracoumarin Cl6H8Oa has already been obtained by Jacobsen and Julius (this vol. p. 56) who gave to it the name " styrogaliol ;" this compound and also its diacetyl-derivative were prepared the latter melts a t 260" and its formation lends support to the constitution assigned to the anthracoumarins. Orthodihydroxy- anthracoumarin can be fixed bv a mordant. a fact which is in accord- ance with a theory put forwardy by the author (see this vol. p. 274). I?. S. I(. Purpurogallin. By S. C. HOOKER (Ber. 20 3259-3260).-Tht! author recommends the following method of preparing purpurogallin -20 grams of pyrogallol is dissolved in 330 C.C.of cold water and treated with a solution of 87 grams of potassium ferricynnide in 330 C.C. of water. Gas is evolved the solution loses its deep red colour a,nd purpurogallin separates ; in about 6 hour the oxidation is complete. The yield is 13 to 14 per cent. of the pyrogsllol employed. Purpurogallin is formed in the oxidation of an aqueous solution of gallic acid by sodium nitrite. Purpurogallin dissolved i n sulphuric acid gives an intense but fugitive violet coloration when a trace of nitrous acid or a nitrite is added. The reaction is very characteristic and delicate. A. J. G. Hydrogenation of Aromatic Hydrocarbons. By E. BAMRERGER and W. LODTER (Ber. 20 3073-3078).-The hydrocarbons are boiled with amyl alcohol and sodium the whole poured into water and the upper layer dried with sodium carbonate and distilled.The yield varies with different hydrocarbons from 50 to 80 per cent. of the theoretical. Tetrahydroretene C18H22 .forms a clear viscous oil which when kept from air remains liquid ; in open vessels it solidifies probably becom- inc oxidised to retene. Tetyahydro-acenaphthene CI2H14 is a clear colourless viscous oil of It boils at 280" under 50 mm. pyessure.ORGANIC CHICBUSTRY. 293 a slightly aromatic odour boiling at 249.5" (corr.) under 719 mm. pressure. Tetrahydyodiphenyl C12H14 is a clear colourless viscous oil having a slight odour of diphenyl. It boils at 244.8" under 716 mm. pressure. Dihydronaphthalene dihydroanthracene (m. p. 108*5') and tetra- liydrophenanthrene were also prepared. Sulphocamphylic Acid.By A. DAMSKY (Ber. 20 2959-2967). -When ammonium sulphocamphylate is distilled with ammonium chloride a yellowish- brown oil of peculiar tnrpentine-like odour is obtained which on fractionation can be separated into two portions one boiling at 108-110" and the second at 195-196". k'hese were separately examined. The fraction boiling at 108-110" is a coIourless mobile liquid having the odour of the crude product and a sp. gr. = 0.7949 at 11.5". I t has the composition CeH14 and is a non-aromatic hydrocarbon possibly identical with that obtained by Moitessier by distilling copper camphorate (Jahresb. 1866 410). On treatment with concen- trated nitric acid it is violently attacked and completely resinified but when dissolved in acetic acid and treated with an acetic acid solution of nitric acid no action occurs.Oxidation with chromic acid mixture does not convert it into an aromatic acid and with per- manganate it jields only oily fatty acids; whilst contrary to the behaviour of aromatic hydrocarbons it does not form an acid amide on treatment with amidoformic chloride. Bromine reacts with it readily yielding an unstable crystalline compound CsH12Br2 and subsequently liquid higher snbstitution-products whilst the unstable crystalline additive-compounds C8H14,HC1 and C8Hlr,HBr are formed when it is treated with hydrogen chloride and hydrogen bromide respectively. The fraction boiling at 195-196" under,poes slight decomposition at each distillation and is a colourlese liquid having an odour similar to that of the lower fraction.I t has probably the composition CloH140 and forms oily compounds with hydroxylamine hydro- chloride and phenylhydrazine hydrochloride ; the oaime having pro- bably the formula CloH14 NmOH. When potassium sulphocamphylate is fused with twice its weight of potassium hydroxide and the melt extracted with ether a brown resinous mass is obtained which on distillation in a vacuum yields a pal e-yellow readily crystallisable oil. The crystals have the compo- sition C9HI2O2 are readily soluble in alcohol and ether very sparingly soluble in hot water and melt at 99". The compound although pre- pared by Kachler's method (Abstr. 1874 154) and having the same composition differs from the substance prepared by him in its lower melting paint and marked acid character. The silver salt CgHl1O2Ag is soluble in hot water; the calcium salt (CgH1102)2Ca + 2H20 forms yellowish crystals soluble in hot water ; the barium salt (C9H1,02)2Ba + 2H20 is crystalline and soluble in hot water ; the methyl salt was also prepared and is crystalline.Treated with bromine the acid yields a cryatalline compound with the evolution of N. H. M.294 ABSTRACTS OF CHEMICAL PAPERS. hydrogen bromide and it is not reduced by the action of sodium amdgam. When distilled with soda-lime i t yields R yellow oil which on rectification forms a colourless mobile liquid of the com- position C,Hl boiling at 133-1%" and polymerisink on exposure to the air. w. P. w. Action of Sulphuric Acid on Terebenthene. By J. Bou- CHARDAT and J. LAFONT (Compt. rend. 105 1177 - 1179). - The product of the gradual action of 467 grams of Rulphuric acid on 9340 grams of French terebenthene boiling at 155-15i" (rotator-y power -33.2") was distilled in a current of steam ; 79 grams of sul- phuric acid remained in the free state the rest having formed a compound 2C10H16,H2SO~ which is almost though not quite fixed.This compound could not be isolated from the colophene with which it is mixed. Jt is a neutral substance and does not combine with potassinm hydroxide. Alcoholic potash is without action in the cold but at 150" decomposition takes place with formation of volatile pro- ducts and the compound C,oH16,S02K(K which crystallises from its aqueous solution in thin lamellse. The portion of the original product which distils with steam con- sists mainly of the unaltered hydrocarbon without any camphene.The fraction boiling at 175-180" has the composition CI0Hl6 oxidises very readily and is somewhat lighter than the original terebenthene. It absorbs hydrogen chloride readily yielding a liquid product and when the latter is distilled in a vacuum it yields cymene and ter- pilene hydrochloride CloHI6,ZHCl melting at 48". The rotatory power of the corresponding terpilene is only one-fifth or one-sixth That of another terpilene obtained from tohe same terebenthene by a diffrrent method. The fraction boiling below 165" was treated successively four times with sulphuric acid always with a similar result but the fraction boiling at 157" which gradually became smaller and smaller in quantity diminished in rotatory power and after a fifth treatment was converted into an easily solidified camphene.This camphene is formed by the decomposition of the small quantity of the sulphur compound which distil6 over with the water. This fraction in fact aIways contains a small quantity of free sulphuric acid. Wben the original product which is not volatile in steam is heated at 200-250" an energetic reaction takes place water sul- phurous anhydride and sulphur being produced. The liquid products contain a slightly active lsevogyrale compound boiling at lX" cymene terpilene and dextrogyrate camphenols. By A. VESTERBERG (Ber. 20 3248-3253).-1n a previous paper (Abstr. 1886 1038) the author showed that the mother-liquor from the preparation of dextropimaric acid contained p-pimarjc acid.From the very vigorous lsevorotatory power of this acid the name laevopimaric acid is now given to i t ; its separation and purification were attended with great difficulty. Leuopimaric acid C20H3002 isomeric with dextropimnric acid crystallises in the 1-hombic system ; axial ratios a b c = 0.81042 1 0.61407 ; ob- C. H. B. Pimaric Acids.ORGANIC CHEMISTRY. 295 served faces wP ~ P w P/2 2Pm OP. It melts between 140" and 150" and is insoluble in water readily soluble in all the other usual solvents its solubility being greater than that of the dextro-acid. One part of the acid dissolves in 10.8 parts of 98 per cent. alcohol at 15". A solution of 3.174 parts of I~vopimaric acid in 100 C.C. of alcohol has a laevorotatory power = -272". It forms readily crys- tallisable salts of which the sodium ammonium and lead salts are described.The author considers it very probable that Calliot's pyromaric acid (this Journal 1874 457) is a mixture of dextro- and hvo-pimaric acids. A. J. G. Action of Phenylhydrazine on Santonin. By C. GRAM (Chern. Centr. 1887 1163-1164; from Rend. R. ACC. Lincei [4] 3 521-522).-When a solution of aantonin (10 grams) is heated with phenylhydrazine (10 grams) in acetic acid solution (sp. gr. 1-06) a yellow hydrazide ClaH,,02*N2HPh separates which melts at 220" and is not decomposed by acids. Hydrochloric acid dissolves it in the cold with a reddish-yellow colour; on heating a scarlet preci- pitate is formed. Lakmoid and Litmin. By W. N. HARTLEY (Proc. R. Dublin XOC. 5 159).-.Lakmoi'd (Abstr.1885 148) is soluble in strong alcohol insoluble in water. A solution in 50 per cent. alcohol retains its colour with but slight alteration for several months. Litmin is insoluble in strong alcohol but soluble in spirit of 50 per cent. ; the solution was bleached after a time although not exposed to bright light. The photographic spectra of the two substances did not differ markedly. From these results it follows that the two substances are not identical. LakmoYd is a better reagent than litmin. New Brazilin-derivative. By C. SCHALT and C. DRALLE (Ber. 20 3365-3366) .- Tetran,ethyZbraxitezn Cl6N1,,O5Me4 is prepared by mixing 2.7 grams of brazilin with 0.8 gram of sodium (each dissolved in alcohol); 8 grams of methyl iodide is then added and the whole warmed on a water-bath until the colour changes to a yellowish-brown. The greater portion of the alcohol is distilled off and the rest evapo- rated on a water-bath.It is washed with water dissolved in ether and washed with dilute aqueous soda. It forms a brittle transparent amber-coloured mass which becomes crystalline when ether is poured over it. When crystallised from alcohol it is obtained in colourless crystals melting at 138-139". The compound has the properties of a phenol alkyl ether; it does not change when exposed to air and yields an additive product with ammonia. Metaritroquinoline. By A. CLAUS and A. STIEBEL (Ber. 20 3095-3097).-ilfetanitropuinoZine C9NH,*NO2 is prepared from 10 grams of nitraniline 2.6 grams of picric acid 14 g r a m s of glycerol and 14 grams of sulphuric acid.The mixture is afterwards boiled for some hours. The product after being freed from resin is treated with light petroleum to remove the phenanthroline which is also formed in The hydrazine compound yields a platinochloride. J. W. L. A. J. G. N. H. M.296 ABSTRACTS OF CEEMTCAL PAPERS. the reaction and recrystallised from alcohol or water. It forms long thin colourless needles melting a t 131 5" (uncorr.). The hydro- chloride crystallises in long yellowish-white needles melts at 225" with evolution of gas and decomposes in contact with water. The nitrate crystallises in long flat needles of a satiny lustre not very readily soluble in water. The platinochloride forms large amber- coloured prismatic crystals. Metamidoquinoline C,NH,*NH pre- pared by reducing the nitro-compound with stannous chloride forms long hair-like yellowish needles which melt at 186" (uncorr.) ; it is readily soluble in ether chloroform &c.When heated i t yields a sublimate of splendid red needles. It does not distil with steam. (Compare Abstr. 2887 810). N. H. 31. Constitution of Quinoline-derivatives. By J. FREYDL (Monatsh,. 8 580-583) .-The so-called p-amidoquinoline on conversion into the corresponding diazochloride and treatment of the same with potassium cyanide yields a cyanoquinoline identical with the meta.. cyanoquinoline of Bedall and Fischer. On hydrolysis this nitrile yields a quinolinecarboxylic acid identical with that obtained from an amidobenzoic acid by Skraup's reaction. The amidoquinoline is also converted by the diazo-reaction into a chloroquinoline identical with the compound obtained by La Costae (Abstr.1886 159) from rnetachlortlniline by Skraup's reaction. Then in the above group the substituted groupings are in the 2 position as derived from the 1 3 benzenoid derivatives. V. H. V. Sulphonation of Quinoline. By G. v. GEORGIEVICS (Monatsh. 8 577-579) .-By the sulphonation of quinoline with Nordhausen acid La Coste as also Bednll and 0. Fischer obtained a mixture of the 1 2 and 1 3 quinoliuesulphonic acids the proportion of each which is formed being dependent on the conditions of the experiment. It is here shown that if the sulphonation is effected with ordinary sulphuric acid the 1 4 sulphonic acid is produced a result confirmed by the conversion of the acid into the corresponding nitrile and carboxylic acid.V. H. V. Quinoline. By E. LELLMANN and (3. LANGE (Bey. 20,3084!-3089 ; compare Abstr. 188 7 737) .-Calcium parabromobenzenesulphonate crystallises is well-formed monoclinic crystals with 2 mols. H20 a b c = 0.5872 1 0.5168; p = 85" 14' 42" (compare Goslich this Journal 1876 i 929). Parabromometamidobenzenesulphonic acid crystallises in well-formed prisms with 1 mol. H,O (not 14 mol. H,O Goslich Zoc. cit.). Orthobromoqzcinoline-anaszLkpho~ic acid C9NH5Br-SOsH [Br SOsH = 1 41 is prepared by heating 5 grams of parabromometamidobenzene- sulphonic acid 6 to 7 grams of orthonitrophenol 20 grams of glycerol and 25 to 27 grams of sulphuric acid in a reflux apparatus a t 155- 160" for six hours.The product is treated with water stenm-distilled treated with baryta filtered and the filtrate boiled with animal char- coal. By precipitating the barium as exactly as possible with sul- phuric acid and carefully evaporating the fihate the sulphonic acidORGANIC CHEMISTRY. 297 is obtained in small lustrous plates with 1 mol. H,O. The calcium salt with 6i mols. H20 crystallises in long needles readily soluble in water. Tetrah ydro~.uinoline-aitasu~honic acid C9NH,*SOSH + H,O is formed when 5 grams of bromoquinolinesulphonic acid is heated on a water- bath with concentrated hydrochloric acid and tin. It crystallises from dilute solutions in rhombic crystals ; a b c == 0.5041 1 0.7511 and from concentrated solutions is monoclinic crystals ; a b G = 0.4855 1 0.5298 ; p = 55" 10'.When treated with oxidising agents it shows the reactions characteristic of tetrahydroquinoline-derivatives. The quinolinesulphonic acid previously prepared (Zoc. cit.) from metamidohenzenesulphonic acid also yields a tetrahydroquinoline- sulphonic acid which completely resembles that just described. N. H. M. p-Quinolinedisulphonic Acid. By W. LA COSTE and F. VALEUR (Bey. 20 3199-3201) .-/3-Quinolinedisulphonic acid prepared by heating the pure barium salt with the necessary amount of sulphuric acid crystallises in slender white needles readily soluble in water insoluble in alcohol ether benzene and chloroform. (Compare Abstr. 1887 379.) The barium salt is obtained by treating the potassium salt with barium acetate. The potassium salt (with 1 mol.H,O) is insoluble in alcohol readily soluble in boiling water. When this salt is fused with 3 parts of potash at 160" potassium P-hydroxy- quinoliiiesulphonate is formed. p-H~droxyquinolines.rL~honic acid crystallises in yellow lustrous plates melting a t 270-275" ; it dissolves readily in hot water sparingly in alcohol and still less in chloroform and carbon bisulphide. p- Dihydroxyqaiinoline CsNH,( OH) is prepared in a manner similar to the a-compound (Abstr. 1886 629) except that the temperature is only raised to 250-255". It crystallises in slightly brown needles readily soluble in ether alcohol benzene chloroform and carboil bisulphide insoluble in water. It melts a t 68" and sublimes a t a higher temperature in slender white needles. The salts are stable but difficult to crystalhe. (Compare also Abstr.1887 973.) N. H. M. Tetrahydroquinaldine. By M. MOLLER (AnnaZen 242 313- 321) .-Tetraby droquinaldine has already been described by Jackson (Abstr. 1881 742) and by Dobner and Miller (Abstr. 1884 183). The nitronitroso-compound NO,.C,oNH,,.NO crystallises in golden plates and melts a t 152". Methylhydroquinaldine CloHI2NMe has been prepared by Dobner and Millei. (Zoc. cit.). It can also be prepared by the action of tin and hydrochloric acid on quinaldine methiodide. Methy Ihydroquinuldine methiodide,CloNH,,Me,MeI crystallises in needles melts at 205" and dissolves freely in water and in hot alcohol. Freshly precipitated silver oxide converts it into the ammonium base CloNH,,Me,MeOH a crystalline hygroscopic compound.The auro- chloride crystallises in lemon-coloured needles and the dichromate in six-sided plates. The plstinochloride forms brick-red crystals soIuble in hot water. The base is decomposed by heat yielding methyl alcohol and methy ltetrahydroquinaldine298 ABSTRACTS OF CHEMICAL PAPERS. Ethy ZtetrahydroquinaZdine CloNH12Et is a colourless liquid boiling at 256". The platinochloride and methiodide are crystalline. The latter melts at 187" and dissolves in water but is not acted on by a solution of potassium hydroxide. w. c. w. Quinaldine Alkyl Iodides. By M. MOLLER (AsmaZen 242,300- 312) .-Quinaldine methiodide and methylquinaldinium hydroxide have been previously described by Dobner (Abstr. 1884 l84) and by Bernthsen and Hess (Abstr. 1885 558) respectively.I n addition to the salts prepared by Bernthsen and Hess the ammonium base yields an aurochloride CloHgNMeCl,AuCI and a dichromate crystallising in lemon-coloured needles. The dichromate detonates a t 90". Ethylquinaldinium hydroxide on exposure to the air changes into a carmine-coloured resin. The platinochloride ( CloNHgEt)2PtCI is deposited from hot water in ruby prisms. The aurochloride CloNHgE t C~,AUCI~ forms golden needles. The dichromate detonates at 100". Quirznldine- propiodide forms greenish-yellow prisms soluble in water and in hot alcohol. It melts at 166-167". The ammonium base is amorphous. It is soluble in alcohol and ether. The platinochloride aurochloride and dichromate are crystalline. Quirzaldine butiodide is prepared by heating quinaldine with isobutyl iodide at 115" in niolecule pro- portion.It crystallises in plates and melts at 172". The amyl iodide requires a temperature of 140-145" for its formation. It is crystalline soluble in water and hot alcohol and melts at 175". 0rthometh.ylyuin.aldine methiodide is deposited from alcohol in yellow needles and melts at; 221". The ammonium base is tolerably st.able and does not change rapidly on exposure t,o the air. The platinochloride dichromate and aurochloride are crystalline. The base is decomposed by heat yielding orthomethylquinaldine. Ortho- methylquinaldine ethiodide is deposited from alcohol in yellow needles and melts at 228". The ammonium base is a stable oily liquid and it forms crystalline platino- and auro-chlorides. Paramethylquinaldine unites with methyl iodide at the ordinary temperature. The compound melts at 236-237" and dissolves freely in water.The ammonium base is unstable. The platino- chloride dichromate and aurochloride crystallise in needles. w. c. w. Conversion of Indoles into Hydroquinolines. By E. FISCHER and A. STECHE (Annalen 242 348-366) .-In previous communicn- tions (Abatr. 1887 588 and 976) the authors have described the conversion of methylketale into dimethyldihydroq uinoline and di- methyltetrahydroquinoline which are derivatives of P-methylquino- line. In the preparation of dimethyldihydroquinoline a monomethyl- dihydroquinoliue is formed as a bye-product. Dihydroethyldimethyl- quinoline and ethylmethylketole have already been described by the authors (loc. cit.).ORGANIC CHEXISTdT.299 Et~ylmeth2/Idihydroquilzoline [Et Me = 1' 3 7 prepared by the action of methyl iodide on ethylmethylketole and methyl alcohol at 120" is a colourless oil which turns pink on exposure to the air. It boils at 254-255" and forms salts which are freely soluble in alcohol and water. With ferric and platinic chlorides it yields crystalline precipitates. Tr.imethyZdihydroquinoZine CgNH,Me3 [l' 3' 4'1 boils at 244". The hydriodide crystallises in long prisms. The sulphate is precipi- tated from its alcoholic solution in crystalline scales on the addition of ether. The dimethyldihydro-p-naphthaquinoline previously described by the authors (Zoc. cit.) is an imide base. The hydriodide and platino- chloride are sparingly soluble in alcohol and in water.The methiodides of the quinolines and dihydroquinolines are easily decomposed by alkalis but the methiodides of the tetrahydro- quinolines are not attacked. Dihydroquinolines containing methylene in the indole-ring turn red The platinochloride is decomposed by boiling water. on exposure to the air. w. 0. w. a-Alkylcinchonic Acids and a-Alkylquinolines. By 0. DOBNER (AlznaZen 242 265-29@).-The preparation of the a-alky! - cinchonic acids and the properties of some of these compounds have already been described by the author (Abstr. 1387 ,504). In the preparation of a-isopropylcinchonic acid a neutral substance of the composition C19H,,N,0 is obtained as a bye-product. I t is insoluble in alkalis. a-Isopropylcinchonic acid CgNH,PrW300H [ 2' 4'1 crystallises with 1+ mols.H,O. The hydrochloride CuH13N0,,H C1 forms colourless plates freely soluble in water. The platinochloride which is abnormal (C,3H13N0,,HCl),,PtC14 + H20 and the auro- chloride ( C13H13N02)2,HA~C14 are crystalline. a-IsopropyIquino- line picrate is deposited from alcoholic solutions in yellow plates. .It melts at 150". The platinochloride crystallises with 2 mols. H,O. A neutral substance of t,he composition C,,H,,N,O is formed by the action of aniline on an ethereal solution of pyruvic acid and isovalei= aldehyde. It crystallises from alcohol in silky needles and melts at 160". If a warm alcoholic solution is substituted for the ethereal solution a-isobutylcinchonic acid is produced. The acid crystallises with 19 mols. H,O. The hydrochloride ClaH15N0,,HC1 + H,O crystallises in colourless plates and dissolves freely in water.The plahinochloride ( C,,Hl5NO,),,H,PtC1 is also crystalline. a-Isobutyl- quinoline picrate crystallises in plates soluble in alcohol. It melts 161'. On mixing together cold ahoholic or ethereal solutions of fur.. furaldehyde pyruvic acid and aniline a neutral substance ol the composition C,,H,,N,O is formed but with warm alcoholic solu- t,ions a-furfurcinchonic acid ( C4H,0C,NH5)-COOH is produced. This acid crystallises in greenish-yellow needles. It melts with decomposition between 210" and 215" and dissolves freely in alcohol ether benzene and in hot water. The silver lead and copper salts are sparingly soluble in water. The hydrochloride nitrate and300 ABSTRACTS OF CHEMICAL PAPERS.sulphate are freely soluble. The platinochl oride ( C,4H,N0,),,B2PtCl and the aurochloride ( Cl4HSNO3),,AuCI3 crgstallise in needles. a-Furfurpinoline is obtained by heating furfurcinchonic acid st 300'. It crystallises in thick needles and dissolves in alcohol ether and benzene. The platino- chloride ( c,3HgNO)2,H2PtC16 + 2H,O and the aurochloride It melts at 92" and boils above 300". Cl3HgNO ,HAu Clc crystallise in needles and dissolve in hot water. forms orange-red needles. decomposes at 100". The dichromnte The dry salt The picrate melts at 186" and is deposited from w. c. w. It is soluble in hot wateii. hot alcohol in large yellow plates. a-Phenylcinchonic Acid and its Homologues. By 0. D~BNER and M. GIESEKE (Anna7ern 242 290-300).-0n mixing together ethereal solutions of aniline pyruvic acid and benzaldehyde a com- pound of the cornposition C,,H,,N,O is obtained in the form of a crys- talline mass insoluble in acids alkalis and water.It melts at 225" and dissolves freely in ether benzene acetic acid and light petroleum. Strong acids and hot alkalis decompose the compound yielding aniline and resinous products. The preparation and properties of a-phenylcinchonic acid have been previously described by the authors (Abstr. 1887. 504). The silver lead copper and zinc salts were obtained in the form of amorphoiis precipitates. A compound of the composition C24H2zNz0 is deposited in crgstals on mixing ethereal solutions of paratolnidine pyruvic acid and benz- aldehyde. It melts at 204-205" and is insoluble in acids and alkalis.If warm alcoholic solutions are used only a small quantity of this compound is formed the chief product being paramethyz-a- phenylcinchonic acid C9NH4MePh*COOH [Me Ph COOH = 3 2' 4'1. This acid is deposited from alcohol in yellow needles. It melts at 228" and is soluble in alcohol and ether. The platinochloride forms golden needles. On distillation with soda-lime paramethyl- phenylcinchonic acid yields paramethyl-2-phenylquinoline. Ortho- methyl-a-yhenylcinchonic acid [I 2' 4'1 melts at 245" and is freely ~oluble in ether and hot alcohol. The silver salt C,HI2NO,Ag.+ F,O crystallises from hot water in needles. On distillation with lime the acid yields orthomethy7-2-phenylquinoline. The base hoils w. c. w. above 360" and melt's at 49-50".Parabenzoylquinaldine and Paradiquinaldine. By E. HTNZ (Annden 242 321-329). -Paraldehyde acts on parabenzoylnni- line dissolved in hydrochloric acid forming parabenzoylqllLina7dil?e C9NH5MeBz and several bye-products. The new base melts at 67-68",ORQANIC CHEMISTRY. 301 boils above W O O and dissolves freely in hot water alcohol ether benzene chloroform and light petroleum. The platinochloride ci*ystallises in needles and is sparingly soluble in water. The anhy- drous salt melts at 108-110". The dichromate also crystallises in needles. UiqwinaZdine is prepared by the action of paraldehyde on benzidine dissolved in hydrochloric acid. The yield is poor. Djquinaldine C20H16Nz me1 ts at 206-207" and dissolves in alcohol benzene chloroform and acetone. It boils with siight decomposition above 360".The platinochloride CzoH16~2,H2PtC16 + 2H20 is sparingly soluble in hot water. The nitrate C20H,6N2,2HN03 cry stallises in needles and is soluble in water. Quinolina By E. BAMBERGPR (Ber. 20 3338-3344).-Quinoliwe- phenacyl bromide COPh*CHz*CSNH7Br is prepared by mixing equal mol. weights of quinoline and bromacetophenone dissolved in ether or in benzene ; it separates in tufts of white needles. The yield is quanti- tative. It dissolves readily in alcohol and water sparingly in ether and benzene begins to decompose at 115-1 18" and melts at about 165". The xincochloride crystallises from water in small thick strongly refractive prisms ; the nitrate crystallises in clear strongly refractive prisms of a vitreous lustre which are generally bent.The phpio- logical action of the nitrate on mice frogs and cats is described ; it resembles that of curare. When a qninolinephenacyl salt is treated with alkalis the ammonium base is obtained Cogether with a scarlet dye ; the base forms white flakes readily soluble in ether. Form y 1 henacy lait thraihi lic acid CC) 0 H*C6H4*N( CH,*C@ Ph) C OH is formed when 16 grams of potassium permanganate disgolved in 600 C.C. of water is gradually added to a cooled solution of 10 grams of quinolinephenacyl bromide in 1200 C.C. of water ; after 12 hours the colourless liquid is filtered the manganese peroxide extracted several times with boiling water and the collected filtrates from 50 grams of the phenacyl bromide evaporated down to 2 to 2.5 litres. It is then made acid left for 24 hours in a cool place and the crystals thus obtained are recrystallised from much water.I t crystallises from dilute alcohol in white plates of a satiny lustre melting at 184" readily soluble in alcohol less in hot water. Benzoic acid is formed as the chief product of the reaction. When the acid is boiled with dilute sulphuric acid formic acid is obtained. Pyridinephenacy Z bromide C,8HH,Br*CHz*C0 Ph prepared from pyri- dine and bromacetophenone crystallises from a mixture of ether and alcohol in slender lustrous strongly refractive prisms. The chromate crystallises from water in lustrous orange-coioured prisms ; the zinco- chloride separates from its hot aqueous solution in lustrous rhombic plates. When the bromide is treated with aqueous soda it is decom- posed into pyridine and benzoic aoid.The methiodide melts at 220". %'he dichromate is cr-ystalline. w. c. w. N. H. M. VOL. IJV. X302 AllSTltXCTS OF CHEMICAL PAPERS. Acetic Tripiperide. By J. Busz and A. KEKUL~ (Rer. 20 3246-3248).-0rtho-amides corresponding with the ortho-salts formed by acetic and other acids have not yet been prepared. Experiments made with primary amiiies and with secondary amines of the type NHR' have failed to yield such conipounds but with secondary amines of tlie type NHR" o€ which piperidine is an example success was attained. Acetic tripiperide CMe( C6NHl0) is obtained by heating acetic tri- chloride (a-trichloroethane) for 4 to 5 hours in a reflux apparatus. It boils at 133-134" under 15 mm. or 261-263" under ordinary pressure.It is very stable yjelding but slight quantities of acetic acid when boiled for days witli water or dilute acetic acid. The hydrochloride is crystalline and insoluble in ether ; the platinochloride crystallises in golden-yellow plates. Chloroform acts very slowly on piperidine yielding a base boiling a t 9 8 O which seems to be orthqformic piperide CH( C,NH,,),,H,O. Benzotric'riloride reacts readily with piperidine but whether a benzoic tripiperidide is formed is not yet established. A. J. G. Oxidation Products of Papaverine. B J G. G o r m c H m E D T (Mo?aafsh. 8 510-528) .-In continuation of former experiments on the oxidation of papaverine by potassium permanganate (Abstr. 1886 479) the author has more fully examined dimethoxycinchonic acid and other products formed.Papaverine hydrochloride yields oxalic hemipinic and veratric acids which are contained in the filtrate from the reduced manganese peroxide ; on treatment of this last with sul- phurous acid and extrstction of the residue with hydrochloric acid papaveraldine hydrochloride and dimethoxycinchonic acid are obtained together with a substance of the formula C,,H,NO,. This last named I~ernipinisoimide to distinguish it from the isomeric hemipini- mide obtained by Liebermann by the action of hydroxylamine on opianic acid forms small white needles melting above 300"; it dissolves only on prolonged heating with alkali but is a t t'he same time decom- posed into ammonia and hemipinic acid. It is also distinguished from hemipinimicle by the unstable character of its potassium-derivative.The formula of this substance is discussed but without satisfactory conclusions. Dinz ethoz y cinchonic acid CgNH4(0Me) 2-C 0 0 H crys tallises with 2H,O in sinall needles ; it melts a t 205" with violent evolution of car- bonic anhydride and formation of dimethoxyquinolino ; it gives a brownish-red turbidity with ferric chloride but no reaction with ferrous sulphate. Solutions of its salts give gelatinous precipitates with barium calcium copper and silver salts. The hydrochloride crystallises with 2 mols H20 in glistening needles and theplatino- chloride ifi groups of yellow needles. By hydriodic acid the dimethoxy- acid is converted into dihydroxycin,chonic acid C9NH4(OH),*COOH which is an amorphous powder melting a t 221" with violent evolution of gas.It gives a violet coloration with ferric chloride and a reddish- yellow with ferrous sulphate. Its salts are all of a yellow aolonr thus resembling those of hydroxycinchonic acid obtained by Weidel from the corresponding sulphonic acid.ORGANIC CHEJIISTRY. 303 nirvLet?2oxyg2LinoZine C9NE,(OMe) obtained by heating the di- methoxycinclionic acid as also from pRpaveraldine when it is heated with alkali forms a hydrochloride crystallising with 3H,O a picrate crystallising in citron-yellow needles and a ckronzute in small orange- yellow rhombic crystals. This dimethoxyquinoline from papaverine is isomeric with that obtained from veratric acid ; a list is given of the points of difference between the salts of' these two bases.It is probable that in the methoxyqninolim from veratric acid the methoxy-groups are in the position 1 2 but in thah from papaverine the groups are in the positions 2 3 ; the aukhor proposes to. confirm this view by further experiments. V. H. V. Adenine. By A . KOSSEL (Ber. 28 3356-3358 ; compare Abstr. 1886 556) .-Adenine nitrate C5H5N5,HN03 + iH,O crystallises in stellate groups of needles; the dry salt dissolves in 110.6 parts of water. The hydrochZoride (with + md. H,O) forms transparent mono- clinic crystals a 8 c = 2.0794 1 1.8127; @ = 61" 40' ; the anhy- drous salt dissolves in 41.9 parts of water. The pZatinochloride ( C5H,N6),,H,PtCl crystallises from its dilute solution in needles ; when a concentrated solution is boiled long the salt C,H5N5,HCl,PtCL separates as a bright yellow powder.The silver c07npownd C5H4N5Ag is obtained4 as an amorphous powder by adding an amrnoniacal silver solution to a hot ammoniacal solution of adenine ; with a large excess of silver solution the c o n y o u i d C5H5N5,Ae0 is formed. The acetyl- derivative C5H,N5Ac crystallises in small white plates readily soluble in hot water and alcobol soluble in dilute acids and alkalis ; it does not melt at 860". The banxoyZ-derivative C5H,N5Bz fomns long thin lustrons needles melting a+ 234-23.5" readily soluble in hat alcohol soluble in dilute acids and m zmmonia. Adenine is very &able towards acids alkalis and oxidising agents but is readily reduced by zinc and hydrochlo~ic acid behaving like h ypoxanthine. N. H. M. Ptomaines and Leucsma'ines.By A. GAGTTIER (BUZZ. XOC. Chinz. 48 6-23).-A summary of our present knowledge concerning ptomahes giving an account of the results obtained by the author Brieger and others whose papers have from time to time appeared in Abstracts i n this Journal (see Abstracts 1881 100 224; 1882 1115 ; 1884 89 188; 1885 676; 1886 634; also BUZZ. de Z'Acad de Med. 1886). C. H. B. Empirical Formula of Cholic Acid. By P. LATSCHINOFF (Ber. 20 3274-3283),-Mylius has lately (Abstr. 1887 982) upheld Strecker's formula C2,H,,05 for choiic acid against this formula C~SH& proposed by the author. The latter has therefore carefully re-examined this acid and its drrivatives with the result of confirming the formula C,,H4,05. He has been unable to obtain the acid perfectly anhydrous.Cholic acid crystailises in two forms (i) in tetrahydric $ 2304 ABSTRACTS OF CHEMICAL PAPERS. cryst'als and (ii) in prismatic crystals. The first obtained bv crystal- lisation from alcohol acetone ether (of which it requires 510 parts a t 18" for solution) isobutyl alcohol or ethyl acetate has the formula CZ5H,,O5 + $H,O. It only loses this water of crystallisation a t or above 145" and partial decomposition always takes place simultane- ously. Fusion ultimately results at 160-180". The prismatic crystals obtained by the precipitation of an acetic solution of the acid with water have the formula C25Hd?05 + H20. They lose 2 mol. H,O a t 120" but the remaining t is only lost a t or above 145". The author believes -Mylius to have taken the not fully dehydrated acid as anhy- drous When this acid is dissolt-ed inpheno1,it forms white prisms which give analytical results agreeing with the formula C25H,205 + $H20 + %C,B,O.It seems that the last trace of water is very firmly united to the cholic acid and that when crystallised from other media with which i t unites the acid only takes up the complemmtary quantity of the medium. Thug the crystals from an alcoholic solution had the formula c&&05 + + pC2H,0. Attempts to obtain mineral salts of the acid showed that here also a similar state of things existed. The salts all contained an excess of the base that excess being as in the case of the water of crystallisa- tion about one-eigti th of an equivalent. With aniline and toluidine however cholic acid yields well-defined crystalline salts which give iiumbers agreeing with those required by theory.Aniline choZafe C~H&,NH2Ph forms needles melting at 140" ; wetatoluidine choZate needles melting at 140-180". Action of Sodium Chloride in Dissolving Fibrin. By .J. R. GREEN (J. PhysioZ. 8 37.2-377).-When fibrin is extracted with a 5 or 10 per cent. solution of sodium chloride a prote'id goes into solution ; on renewing this sollition daily removing that added on the previous d.ty it is found that in 32 to 35 days the whole of the fibrin is dis- solved. In all these experiments there was perkct freedom from putrefaction. When dissolved in this way the fibrin is decomposed with the formation of two globulins one of which coagulates at 56" is soluble in 1 per cent.sodium chloride solution is readily converted into syntonin and alkali-albumin and is not precipitated by weak acid; the other is insoluble in 1 per cent. sodium chloride solution hut soluble in a 10 per cent. solution ; i t coagulates on heating a t 59- MI" is readily converted into alkali-albumin but not into syntonin the ncid added for the latter purpose precipitating it and in suspension it is not acted on. In sDme of its reactions the former substance mcals the behaviom of fibrinogen but neither corresponds with fibrin- ogen cr serum globulin and the latter cannot be made to re-form fibrin. W. D. H. L. T. T. Haematoporphyrin. By C. A. MACMUNN (J. PhhysioZ. 8 384- 389).-A brownish pigment is scattered over several superficial portions of the mollusc Xolecurtus strigillatus.On microscopical examination i t is found that ill the foot especially the pigment is sitnat,ed a t the border of the cells so that the boundaries between them are marked much in the same way that endothelium cells arePHYSIOLOGICAL CHEMISTRY. 305 demonstrated by the use of sil-rer nitrate. Granules in the cells contain the same pigment. Spectroscopic examination shows that the pigment is haematoporphyrin ; this is identical with Moseley’s pols- perythrin (Quart. J. Mic. Science 17 1 ) ; the bands are identical with those seen in the pigment from the dorsal streak of the earthworm ; a list of 12 other invertebrates in which the same pigment has been found is given. In many of these there is no hemoglobin present but the universal distribution of the histohaematins and the fact that these yield some of the decomposition products of hBmoglobin fully explain the occasional appearance of a hemoglobin-deriva,tire in invertebrate animals (see Abstr.1886 638). W. D. H.240 ABSTRACTS OF CHEMICAL PAPERS.Organic Chemistry.Preparation of Trirnethylene. By G. GUSTAVSON (J. pr. Chem.[ 2J 36 300-303).-Trirnethylene may he prepared by heatingtrimethylene bromide with zinc-dust and aqueous alcohol or water ;1 litre of the gas is thus obtained from 10 grams of bromide and fromthis qnmtity of the gas 7.2 gmms of dry crude trimethylene bromide(or 4.57 grams iodide) can be again produced showing that thismethod of preparation gives good results.When trimethylene is passed into concentcrated sulphuric acid liquidhydrocarbons are formed on the surface of the acid and the solution,after diluting yields normal props1 alcohol on distillation.F.S. IC.Conversion of Trimethylene Bromide into PropyleneBromide. By G. GUSTATSOX (J. pr. Chem. [ a ] 36 303-304).-When trimethylene bromide and aluminium bromide are placedtogether in a sealed tube a t the ordinary temperature the formerundergoes intermolecular change and propylene 6romide is formed.F. S . I(.Ethylpropylacetylene. By A. BOHAL (Bull. SOC. Chim. 48,216-219) .-Butyrone (106 grams) is gradually mixed with phosphoruspentachloride (200 grams) and when the action has ceased a furhherquantity of butyrone is added and the reaction is completed byheating. The liquid is then cooled and poured on ice and the chlo-rine-derivative separated and heated with alcoholic potash in sealedtubes a t 130-150" for 20 hours.The product is treated withwater and dried over calcium chloride. The ethylpro pylncetylenethus obtained is a liquid which boils at 105-106" and has an odourof acetylene ; sp. gr. at 0" = 0.760.It does not combine with cnprous chloride but with mercuricchloride a white precipitate is formed after some time and when thisprecipitate is dissolved in dilute hydrochloric acid an odour ofbutyrone can be perceived.Bromine acts on it with great energy yielding a liquid of highersp. gr. than water. When treated with about twice its own weight ofconcentrated sulphuric acid a t 0" the hydrocarbon yields a red-Pirownsolution which becomes colourless when mixed with ice.The soleproduct of hydrolysis is butyrone.The removal of 2 mols. of hydrogen chloride from dichlorobutyronemay yield diethylallylene or the corresponding hydrocarbon with aclosed chain but the fact that this hydrocarbon forms a compoundwith mercuric chloride and is readily hydrolysed combined with theabsence of tertiary carbon united with the carbon which is in unionwith the chlorine render it most probable that this hydrocarbon isethylpropylacetylene CEt i CPr. C. H. BORGANIC CHEMISTRY. 241Hydrolysis of Diallyl. By A. BBHAL (BuZZ. SOC. Chim. 48,43-51).-Diallyl is added drop by drop with contiiiual agitationto ordinary concentrated sulphuric acid cooled by ice. The acidbecomes red but the colour disappears when the acid is diluted byice which is added in sufficient quantity to reduce the temperature,and the product is then neutralised with an alkali or an alkaline earth,preferably the former.The liquid is then distilled and the snper-natant layer separated. In all cases the sulphonic acid C6Hll*SO3H.is obtained. The barium calcium and potassium salts are very solublein water and crystallise with difficulty.The supernatant layer of the distillate boils at 93" and is soluble in1.3 parts of water at the ordinary temperature. It does not combinewith sodium hydrogen sulphite even after prolonged contact has noaction on hydroxylamine and does not reduce ammoniacal silvernitrate in alcoholic or aqueous solution. It dissolves in hydrochloricacid with development of heat but no combination takes place ; wheuheated with this acid in sealed tubes at 143-150" it yields dichlor-hydrin bciling at 170-180".It does not precipitate magnesiumchloride solutions and when treated with phosphorus pentachloride aconsiderable quantity of hydrogen chloride is evolved but no definiteproducts could be isolated. Bromine is absorbed with great energy,but the product readily decomposes and cannot be distilled even i n avacuum. In one case the liquid was treated with excess of bromineand then washed with water; when the water was added there wasconsiderable development of heat and the liquid separated into twolayers. The lower layer was hexylene bromide probably correspond-ing with pseudohexylene glycol.The upper aqueous liquid readilyreduced ammoniacal silver nitrate and when neutralised and distilledyielded a small quantity of a liquid having the properties of an alde-hyde.The original liquid heated with water a t 150-180" yields noWhen hexyl pseudoglycol is mixed with concentrated snlphuricacid at Oo it yields a product identical with that obtained by the actionof the acid on diallyl.The hydrolysis of diallyl under the influence of sulphuric acidyields a compound formed by the dehydration of isohexyl glycol,identical with the hexglene pseudoxide obtained by Wurtz by theaction of silver oxide on diallyl dihvdriodide. The oxide thus ob-glycol.tained differs from ordinary "glycol" by its inaptitude to combinewith wa,ter and has the constitution <cH;.CaMe>O.Its forma- CH-G BMetion is due to the fact that the two alcoholic groups from which theoxide is derived are separated by two atoms of carbon ; and the twoethylene-groups do not act independently but have been linkedtogether by the atom of oxygen formirig an oxide more stable thanthe glycol. Moreover the hydroxyl-groups in pseudohexyl glycolare in the 01 position and hence readily form an anhydride.The other products of the hydrolysis are a sulphoriic acid andpolymerides of diallyl. C. H. B242 ABSTRACTS OF CHEMICAL PAPERS.Pyrrolylene Tetrabromide. By G. CIAMICIAN (Ber. 20 3061-3064) .-The author considers the explanation given by Grimauxand CloSz (Abstr. 1887 789) to be improbable.Hydrocyanic Acid and Cyanogen Iodide.By E. V. MEYER(J. pr. Chern. [2] 36 292-5399). The author confirms Millon'sstatement that small quantities of hydrocyanic acid prevent thereduction of iodic acid by formic acid and finds that the hydrocyanicacid causes the iodic acid to assume a passive state since even whenall the former acid has been expelled from the solution by boiling acertain time elapses before the iodine begins to separate. On theother hand hydrocyanic acid does not prevent but only checks thereduction of iodic acid by sulphurous acid and a considerable quantityof the latter must be added before the separation of iodine com-mences. Hydrocyanic acid has no influence on the reduction of iodicacid by hydriodic acid. When a solution of iodine is added tohydrocyanic acid cyanogen iodide and hydriodic acid are formed upt o a certain point after which the iodine is no longer acted on.These two products have a great tendency to reproduce hydrocyanicacid and iodine but an excess of hydrocyanic acid prevents this in-verse change taking place.Numerous experiments were made tofind how much iodine must be added to a constant quantity of hydro-cyanic acid in varying quantities of water before free iodine is presentin the solution and the tabulated results show that the amount ofiodine used increases with dilution and with the temperature.Cyanogen iodide is completely decomposed by hydriodic acid and snl-phurous acid and these reactions may be employed for the estimationof cyanogen iodide volumetrically.Hydrogen sulphide stannouschloride and other reducing agents act in like manner but towardsoxidising agents cyanogen iodide is as stable as iodic acid.Oxidation of the Azulmic Matter obtained by the Electro-lysis of Ammonia with Carbon Electrodes. Bg A. MILLOT (BUZZ.SOC. Chim. 48 238-240) .-The composition of the black residueobtained by evaporating the liquid after electrolysis (Abstr. 1886,979) then extracting with alcohol and finally with water is-C 35.5 ;H 2-0 ; N 36.3 ; 0 26.2. It is not readily oxidised by sodium hypo-chlorite.10 grams of the residue was dissolved in water and ammonia theammonia expelled by heating on the water-bath and the gelatinousresidue mixed with 50 C.C. of hydrogen peroxide capable of giving3000 C.C.of oxygen. The mixture was heated on the water-bath for10 or 12 hours and filtered. On cooling ammelide is deposited and onfurther concentration a second quantity of this compound is obtained,The mother-liquor is evaporated t o dryness and extracted withalcohol which when concentrated deposits crystals of cyanuric acid.The last extracts yield nacreous plates or rhombo'idal prisms of thehydrated acid resembling the modification which Liebig termedcjanilic acid. When this is dissolved in sulphuric acid and pre-cipitated by adding water it separates in the ordinary form.That portion of the products of oxidation which is insoluble inF. S. KORGANIC CHEMISTRY. 213alcohol consists of ammonium sulphate the sulphuric acid having beenpresent as an impurity in the hydrogen peroxide.Sulphuranes.By I3. RRADN (Bey. 20 2967-2970) .-Whenethyl snlphurane EtS*C,H,.S.C,H is heated for many hours withexcess of ethyl iodide at 100" and the product exlracted with water,a crystalline compound is obtained which is either diethylvinyl-sulphurane or triethylsulphine iodide whilst the portion insolublein water yields ethylene bisulphide on fractional distillation.The diethyl-derivative of ethylene mercaptan Et*S*C,H,*S.Et,when treated with ethvl iodide in like manner. is converted into aC. H. B.mixture of triethylsulpkne iodide and ethjlene disulphide. w. P. w.Propane-derivatives. By C. m T ~ ~ ~ ~ ~ r ; ~ ~ ~ (Bull. Xoc. Ghim. 48,108-112).-The product of the action of bromine on excess of propylalcohol contains an alcohol which boils constantly at 87' but has allthe other properties of propyl alcohol.After dehydration by meansof potassium carbonate it boils at' 92". It is evident that a hydrate ofprimary propyl alcohol does actually exist.Propyl mercaptan and propyl sulphide boil at 67-68" and 141.5-142.5" respectively under a pressure of 772 mm. Cshours's number,130-135* for the boiling point of propyl sulphide was doubtless dueto the presence of impurities one of which was most probably themercaptan formed in consequence of the partial decomposition of thepotassium sulphide into hydrosulphide during the preparation of thed.erivative. This decomposition becomes much more marked with thehigher members in the series.Orthopropylsulphonic acid is obtained by the action of nitric acido€ sp.gr. 13 on propyl mercaptan. The reactiou is violent and thefirst products are nitrogen oxides and a red oil probably ethylthioet hylsulphonate which gradually dissolves as the effervescenceceases.Orthopropyl oayswlphide is obtained by the action of nitric acidof sp. gr. 1.2 on propyl sulphide. I t forms long colourlesq andodonrless needles which melt at 14.5-15" cannot be distilled with-out decomposition and dissolve in water alcohol and ether. It burnswith a brilliant flame and is easily reduced by ferrous chloride or bynascent hydrogen. When a solution of the oxysulphide and calciumuitrate is concentrated i t yields a fibrocrystalline compound,4[2SOPr2,Ca(N03),] + Ca(NO&,which melts at SO" and shows the phenomena of supersaturation andsuperfusion in a very marked manner.To obtain diortlzopropyl sulphone it is necessary to use a warm con-centrat,ed solution of potassium permanganate as the oxidising agent.'l'he sulphone crystallises i u beautiful transparent scales soluble inwater but more soluble in alcohol and ether.It cannot be distilledwithout decomposition otherwise than in a current of steam.-~ono~ropylphos~hol-lc acid is contained in the dense viscous residueobtained in the preparation of prDpy1 chloride by the action of phos-phorus pentachloride on propyl alcohol. This residue also contains a244 ABSTRACTS OF CHENICAL PAPERS.acid which yields a barium salt of the composition PO(OPr)O,Ba,anhydrous a t looo and soluble in cold water from which it separateson boiling and an ethereal salt PO(OPr)3 which is most soluble inwater at 70-80" dissolves in alcohol and ether and cannot be distilledwithout decomposition even in a vacuum.By A.REFORMATSKY( J . pr. Chem. [el 36 340-347).-Diethyl methyl carbinol,CMeEt,-OH is prepared by the action of zinc on a mixture of diethylketone (100 grams,) and methyl iodide (495 grams) and subsequenttreatment witah water. It is a colourless mobile liquid having apleasant smell resembling trimethyl carbinol boils a t 122-123" andhas the sp. gr. 0.8237 at 20° 0.8194 a t 25" 0.8179 at 30° and 0.814335" (water at 0" = 1). The acetate is a colourless liquid boiling at148" (coi-r.). The iodide boils a t 140-144" and is parhly decomposedon distillation. When oxidised with chromic mixture diethyl methylcarbinol yields acetic acid as the sole product,Bromination of Ally1 Alcohol.By I. FIXK (Nonatsh. 8 561-562).-By bromination of ally1 alcohol in absence of water a dibrom-hydrin is formed almost in the theoretical proportions as observed byMarkownikoff and v Tollens. In the presence of water there is formedin addition a monobromhydrin C3H,Br02 boiling a t 138" a t apressure of 17 mm. ; it is shown to be of this constitution by its con-version into glycerol and triacetin.Diisobutenyl Oxide. By S. PRZYBYTEK (Rer. 20 3239-3246).-The methods of preparation of the following substances have alreadybeen given (this vol. p. 123). The dichlorliydrin C,H,4C1,(OH)z isa thick viscid pale-yellow liquid of faint odour and burning taste.Diisobutenyl oxide <-02> CH CMe*CHz*CHz*CMe<~~~> is itcolourless mobiIe liquid of agreeable odour and burning taste ; it isheavier than water and boils a t 170-180" under 125 mm. pressure.As was to be expected from their respective constitutions it combineswith water with greater slowness and difficulty than does erythrenedioxide.Octylerythrol C8H,,(OH)4 is a thick and very viscid liquid ofbitter taste readily soluble in water and alcohol but insoluble inether.It can be formed directly from the chlorhydrin by heatingwith potash and a large excess of water.Action of Hydrogen Chloride on Glycerol. By A. FAUCONNIERand J. SANSOX (BUZZ. Soc. Chim. 48,2s6-%8).-Dry hydrogen chloridewas pasbed into glycerol for five days in an apparatus provided witha reflux condenser.The fraction of the product boiling below 80"contains hydrochloric acid and water together with a small quantityof an oily substance precipitated by water; the fraction 80-12O0contains the two dichlorhydrins in quantity equal to half the weightof the glycerol ; the fraction 120-150" contains glyceryl monochlor-hydrin and substances which crystallise in the receiver. The pro-ducts boiling above 150" have not yet been examined.C. H. B.Synthesis of Diethyl Methyl Carbinol.G. T M.V. H. V.A. J. GORGANIC CHEMISTRY. 245The crystalline solid in the last fraction amounts to 0.75 per cent.of the glycerol used. It crystallises from alcohol in white needles,which have the same composition as epichlorhydrin and melt at109-110".The substance is probably a polymeriae of epichlorhydrin ;it dissolves readily in cold benzene ether carbon bisulphide andchloroform is somewhat soluble in alcohol especially on heating anddissolves slowly in boiling water from which it crystallises in verylorig needles. C. H. B.Sugar-Tike Nature 01 Formose. 39 0. LOEW '(BeT. 20 Y~SY-3043).-A solution of formose (10 grams) in I litre of water is boiledin a reflux apparatus and the whole extracted with chloroform ; theresidue obtained by evaporating the chloroform is treated with alcohol,aniline and a little hydrochloric acid when an intense red colorationis prodnced showing the presence of furfuraldehyde.When formoseis digested with 1 per cent. sulphuric acid on a water-bath more fur-furaldehyde is obtained than from other sugars.Formose has all the following characteristics of sugar :-(1) Sweettaste; (2) strong reducing power; (3) ready decomposition bydilute alkali ; (4) formation of saccharic acid by the action of lime ;(5) power of combination with hydrogen and hydrogen cyanide andformation of an osazone ; (6) formation of humous substances by acids ;(7) formation of furfuraldehyde by dilute acid ; (8) capability offermentation. The author concludes with a criticism of Wehmer'spaper on the carbohydrate nature of formose (this vol. p. 40).N. H. M.Erythrene Dioxide. By S. PRZYBYTEK (Ber. 20 3234-3239).-Erythrene dioxide when treztted with bromine in tubes immersedin cold water is gradually converted into a citron-pellow crystallinedibromide which is insoluble in water alcohol and chloroform andreadily decomposes with evolution of hydrogen bromide.A polymeride of the dioxide is obtained in very small quantities bylieatring the dioxide at 110-130" (below its boiling point = 137") abetter yield being obtained at 140-150" but the best yield is obtainedwhen sealed tubes containing powdered anhydrous sodium sulphatejust moistened with the dioxide are heated at 110-120" for 10 days.In all cases the polymerisation is very incomplete.It is an amorphous,colourless substance devoid of taste and odour and insoluble in water,alcohol ether benzene and chloroform. It can although with diffi-culty be converted into erythrol and its derivatives.Uihydroxyerythren.edisuZphonic acid C,H,(OH),( SO,H) is obtainedwhen erythrene dioxide is shaken with a slight excess of concentratedaqueous hydrogen sodium sulphite and the sodium salt formed decom-posed with oxalic acid.It forms a deliquescent mass of felted needles,and is very unstable charring when gently heated and yieldingsulphurous anhydride when its aqueous solution is heated at 50". Itssalts on the contrary are very stable.Inosite. Ry LORIN (BUZZ. SOC. Chim. 48 235-237).-Thc authorshowed 10 years ago from its behaviour with oxalic acid that inosite1s a polyhydric alcohol (Abstr. 1878 398).A. J. G.G. H. B246 ABSTRACTS OF UHEMICAL PAPERS.Carbohydrates. By b. G.EKSTRAND and C. J. JOHANSON (Ber. 20,3310-3317).-The authors have obtained a new carbohydrate fromthe haulm of the Phleum pratenss. The hanlm is thickened ah itslower end to a bulb and in the autumn this bulb increases in size andbecomes filled with ft concentrated solution of a carbohydrate towhich the authors give the name graminin. This substance is apowder resembling starch of the formula 6C6Hl0O + HzO and fuseswith decomposition at 215". It is soluble in water and in causticpotash insoluble in alcohol. From its aqueous solutions baryta-waterthrows down a precipitate which redissolves in excess of the precipi-tant. It does not give a blue coloration with iodine it reduces silvernitrate but not Fehling's solution. Under the microscope graminineho ws spheroidal granules which are sometimes concentrically striated :on the addition of water a part dissolves but the larger part remains inthe form of half-spheres which show radial stria.The authors hAvealso obtained graminin from the rhizome of Baldingern urzmdina,cea,but in this case a part of the carbohydrate occurs in a less solublemodification. This latter modification shows decided cruciform or semi-circular striae in polarised light. Graminin also seems to be present inthe rhizomes of Calamagnostis ngrostis and of Teisetum hierochloa.This carbohydrate seems closely related to inulin and irisin as isapparent from the following comparison of their properties :-Solubility in 100 Rotatoryparts H20 a t power. Meltingordinary temp.[.ID. point.sol. variety.. 3.29 parts - 48-12" 215" . . 1.79 - 49.27 205 Graminin { insol,Irisin ................ 3.26 ) - 52.34 160Inulin ................ 0.96 - 34.53 160From Draccena australis the author has obtained a carbohydrate,6CsH,,O5 + H,O which very closely resembles triticin from Triticuinrepens. It diflers however from the latter in its rotatory power,which is [a]= = -36*61" whilst that for triticin is [a]= = -41.07".By M. HONIG and S. SCHUBERT (Monatsh. 8 529-560).-Braconnot Berzelius and Payen have observed the formation ofcertain dextrins and saccharine substances when inulin is heated ;whilst Dragendorff has described intermediate products betweeninulin and lsevulose formed by heating innlin with water under pres-sure.In this paper a long account is given of experiments on thesaccharification of inulin effected either by heating inulin in glycerolor with dilute mineral acids the specific rotatory and cupric oxidereducing powers of the various intermediate products are also setforth in a series of tables. The principal results obtained are as fol-lows :-( 1.) The intermediate products obtained by heating inulinwith diluh mineral acids so far as they are directly comparable seemto be identical with the products obtained by heating inulin byitself. (2.) These dextrin-like substances differ from one another bytheir specific rotatory power as also by their solubility in water andalcohol and their precipitability by barium .hydrate. At a lowerL.T. T.InulinORGANIC CHEMISTRY. 217temperature the substances formed more nearly resemble inulin asregards their sparing solubility whilst a t a higher temperature atfirst certain products metinulin and indoid are produced whichare readily soluble in wat'er and not precipitated by barium hydrate.After a more profound change the substance formed shows succes-sively a slight laevorotatory then no rotalory power and finallya dextrorotatory power. The specific rotatory power varies from[a]j = -41.5 that of inulin t o [a]j = +30*68 that of the finaldextrin. (3.) The substances without specific rotatory power arenot identical with laevuloses. (4.) The saccharification of inulin iseffected rapidly by dilute acids reaching its maximum in 15 to 30minutes according t o the concentration ; laevulose and the above-mentioned dextrins are simultaneously produced.The authors have also succeeded in obtaining laevulose in crystalssufficiently well developed for measurement by i'reqiientlp recrystal-lising the crude crystalline l~evulose from absolute alcohol thecrystallisation in each case being induced by dropping in a solidcrystal ; a similar product was also obtained by the sacehsrification ofinulin.Laevulose crystallises in the rhombic system individual crys-tals being of the prismatic and combined crystals of the octohedraltype. The axial ratio is a b :-% = 0.80067 1 0.90674 whilst110 110 = 77" 22' and 011 011 = 84" 24'. The crystals areslightly biaxial resembling as regards their action on polarised light,certain mixtures of sodium-ammonium and potassium-sodium tar-trates.The specific rotatory power of an aqueous Eolution of the purelaerulose was [a]j = -89.74 L = 200 mm. c = 3.6555 ; t = 22".This value when calculated by means of the factor 1.129 gives for [a],,the value -87.84". Analyses are also given of the pure product,which prove that the formula C6H,,06 expresses the composition oflaevulose. V. H. V.Fermentation of Glyceraldehyde. By E. GRIMAUX (Compt.rend. 105 1175-1177).-By oxidising glycerol by means ofplatinum-black the author had previously obtained a liquid whichseemed t o contain glyceraldehyde although the latter could not beisolated (Abstr. 1887 695). When this product is distilled in avacuum with dilute hydrochloric acid its rotatory power is con-siderably reduced and a gummy residue is left which is soluble inabsolute alcohol.The residue therefore contains no dextrin andsince dextrose is converted into dextrin under these conditions i tfollows that the product of the action of platinum-black on glycerolcontamins no dextrose. With phenylhydraziiie it yields a compoundidentical with the hydrazine-derivative obtained by Fischer and Tafelfrom the products of the oxidation of glycerol by nitric acid. Theauthor oxidised glycerol by Fischer and Tafel's process neutralisedwith potassium hydroxide extracted with alcohol and evaporated thesolution to dryness in a vacuum. The product thus obtained has verylittle reducing power but if boiled with very dilute snlphuric acid itrecovers its reducing power and after neutralisation it fermentsreadily in coctact with yeast. Glyceraldehyde is not eonverted intoglucose by treatment with hydrochloric acid248 ABSTRACTS OF CHEMICAL PAPERS.This is the first instance of the synthetical formation of a sugarwhich undergoes alcoholic fermentation.It is evident that the pro-perty of fermenting. in this manner is not confined to carbohydratescontaining Cs and C12. C. H. B.Decomposition of Nitrosoketones. By H. V. PECHMANN (Ber.,20 3213-3214 ; compare this vol. p. 146).-When boiled with dilutesnlph uric acid fatty nitroketones are converted into hydroxylamineand diketones. When the liquid obtained by treating an alkalinesolution of ethyl methylacetoacetate with sodium nitrite and sulphuricacid is dist.illed with much sulphuric acid a yellow distillate contain-ing diacetyl is obtained.N. H. M.Action of Zinc Ethide and Zinc Iodoethide on Dipropyl-ketone. By P. MENSCHIKOFF (J. pr. Chem [g] 36 347-352).-Both zinc athide and zinc iodoethide form condensation-products withdipropyl ketone but only the compound of the iodoethide yields atertiary alcohol on treatment with water. G. T. &I.Diacetyl and its Homologues. By H. v. PECHMANN (Ber. 20.3162-3164) .-By successive treatment with sodium hydrogen sul-phite and dilute acids the homologues of nitrosoacetone are convertedinto a-diketones (homologues of diacetyl) ammonia and sulphuricacid being also produced. From nitrosomethylacetone diucety Z isobtained COMe*CMe:NOH + H,SO = COMe*CMe:NSO,H + H,O =COMe-COMe + NH4HYOr.It is a yellowish-green oil which boils without decomposition at87-88' and does not solidify when placed in a freezing mixture ofice and salt; its odour resembles that of acetone and its vapour is thecolonr of chlorine ; it dissolves in 4 parts of water a t 15" forming ayellow solution and is miscible with ordinary solvents.I t is decom-posed by alkalis or hot alkaline carbonates forms a colourlesa crystal-line substance with ammonia and with phenylhydrazine yields twoliydrazides melting a t 133" and 242" respectively. With aniline itforms a crystalline product ; with orthodiamines liquid quinoxalinesare produced and it combines readily with alkaline hydrogen sul-phites.When reduced in acid solution it is converted into a benzoiuwhich reduces Fehling's solution instantly at the ordinary temperature.Since in its physical properties diacetyl differs so considerably from@yoxal the latter compound must be considered as a polymeric di-formyl diacetyl however resembles itis higher homologues di butyland diisovaleryF1. F. S. K.Chlorinated Methyl Formates. By W. HENTSCHEL (J. pr. Chem.[2] 36 305-317 ; compare Abstr. 1887 1027 1099).-Trichloro-methyl chloroformate COCl.OCCl is obtained among other productsof &he chlorination of methyl chloroformate. When heated at 300°,it decomposes into twice its volume of carbonyl chloride a t a dull-red heat it yields carbonic anhydride and carbon tetrachloride whilstin presence of aluminium chloride it is rapidly and completelORGANIC CHEMISTRY.249resolved into these substances giving almost a theoretical yield ofcarbon tetrachloride. Both dry and aqueous ammonia convert it intocarbamide but contrary to the statement of Cahours no trichlor-acetamide is formed. If aniline is used instead of ammouia diphenyl-carbamide is formed which on further treatment'wi th trichtoromethylchloroformate yields phenyl isocyanate. Trichloromethyl chloro-formate does not react with benzene when heated in closed tubes at150° but if the substances are brought together in presence oraluminium chloride triphenylchloromethane is produced. Withalcohol and phenol trichloromethyl chloroformate yields trichloro-methyl carbonate OMe.COOCCl and phenyl chloroformate,COCl-OPh respectively whilst it is practically without action onunsaturated hydrocarbons such as ethylene and amylene when heatedwith them in sealed tubes.G. 'r. M.Chlorinated Methyl Formates. By W. HENTSCHEL (J. pr.Ch,em. [ 2],36,468-48O).-Trichlormethyl dictilorformate C,H,CI,O,(Abstr. 1887,1028) is not formed by heating together methyl chloro-formate and perchloromethyl formate. By the action of aluminiumchloride the formate is split up into carbonic anhydride methylenechloride and chloroform pointing to the formulaCH,Cl.OCCl 0 CC1.0.CH2C1,rather than to OMe-C,0,CI,*O-CC13 where chlormethane and tetra-chloromethane should be the products.By distilling the formate (1 mol.) with anhydrous sodium acetamhe( 5 mols.) acetic acid acetic anhydride niethylene diacetate andcarbonic oxide and anhydride are obtained ; if a smaller proportionof sodium acetate is used acetic chloride and methylene diacetate areformed.The action of aluminium chloride on the formate dissolvedjn benzene yieids di- and tri-phenylmethane. Aniline acts on theformate producing a crystalline substance C4H,C1:,0,(NHPh) ofunpleasant odour melting at 45". By the action of sodium phenoxideon the formate a phenyl ether corresponding with this anilide wasobtained.On chlorinating methyl chloroformate a heavy oil either C,H,Cl,O,or C,H,Cl,O boiling at NO" is obtained. Its vnpour-density couldnot be ascertained. A. G. B.Action of Triethylamine on a-Bromobutyric Acid.By E.DUVILLIER (Bull. SOC. Chinz. 48 3-6).-When a solution oEa-bromobutyric acid (1 mol.) is added to a saturated aqueous solutionof triethylamine (2-3 mols.) there is some development of heat,and the liquid separates into two layers the upper of which is un-altered triet,hylamine. The mixture is heated to complete the reac-tion and the excess of triethylamine distilled off. The products aretriethylamine hydrobromide and a-hydroxybutgric acid the latterbeing soluble in ether. The barium salt of this acid is allnost in-soluble in alcohol. The zinc salt crystallises with 2 mols. H,O jnsmall nodules which lose their water at 110". It is almost insolubl250 ABSTRACTS OF CHEMICAL PAPERS.in alcohol. No beta'ine is formed in this reaction and hence thebehaviour of triethylamine is analogous to that of potassium,barium or silver hydroxide.When the dry substances are mixed in the same proportions thereis likewise some development of heat and the reaction is completedby heating in closed vessels. The products are a-hydroxybutyricacid traces of crotonic acid and tetrethglammonium bromide.C.H. B.Solubility of Salts of Isovale ric Methylethylacetic andIsobutyric Acids. By L. SEDL~TZKY (iionatsh. 8 563-576) .-Inthis paper determinations are given of the solubility of various salts ofisovaleric methylethylacetic and isobutyric acids by the method ofheating and cooling described by Rmpenstmnch ; from these deter-minations formulm are deduced and the calculated results in each caseare compared with those found.These formulae are given below :-Silver isovalerate S = 0.1774 + 0.003349 ( t - 0.2) +Calcium isoralerate S = 18.429 + 0-10514 ( t - 0.2) -Calcium isobutyrate S = 20.3833 + 0.08061 ( t - 1) +Silver methylethylaceta.te S = 1-1116 + 0.0002978 (t - 1) +Calcium methylethylacetate S = '289822 + 0.33186 (t - 0.6)Barium methylethylacetate could not be obtained in ft crystallineTbe curves of solubility in terms of degrees are given in it0*000006528 ( t - 0*2)2.0~001091 (t - 0.2)*.0.0006522 (t - l)2.0~0002105 (t - 1y.+ 0.004417 ( t - O.t;),.form.series of diagrams. V. H. V.Oxidation of Palmitic Acid. By M. GR~GER ( M o w u ~ s ~ . 8 484-497).-An account is given of experiments on the oxidation ofpalmitic acid with alkaline permanganate under varions conditions ofconcentration.The principal products formed are acids of the oxalicseries namrly oxalic succinic and adipic ; acids of the acetic series,namely acetic butyric caproic and probably caprylic; and acids of thelactic series namely hydroxyvaleric and dihydroxypalmitic acids. Otherconditions remaining the same acids of lower molecular weight areproduced with greater concentration of the oxidising solution aitdacids of higher molecular weight with more dilute solutions. Theconditions of each experiment the product3 obtained and the methodeby which they were s'eparxted; are discussed in detail in the paper.V. H. V.Mixed Acid Anhydrides. By W. AUTENRIETH (Bw. 20 3187-3191).-The general method for preparing the mixed anhydridesconsists in heating the acid with two or three times the calculatedamount of acetic anhydride in a reflux apparatus for $ to Q an hour.The product is treated with sodium carbonate to remove excess oORGANIC CHEMISTRT.251acet;c anhydride as well as the acetic acid; the anhydride separatesas an oil from the alkaline liquid.Acetocuproic anhydride CsHi,,O*OAc is a colourless liquid whichis lighter than water and boils at 165-175".Acefovaleric anhydride CsH,O*OAc resembles the above compound ;it boils at 147-160".Aceto-p-thioethylcrotonic aiihydride SEt*CMe:CH*CO-OAc is a thickyellowish-brown oil heavier than water which when exposed toair gradually decomposes with separation of crystals of thioethyl-crotonic acid.It gives a dark-red coloration with sulphuric acid,but does not show the dark-green coloration characteristic of thothioethylcrotonic acids when treated with isatin and sulphuric acid.Nitric acid acts violently on it.Acetobenzoic anhydride COPh-OAc (Gerhardt Annulen. 87 85),is readily obtained by boiling benzoic acid with acetic anhydride.When treated with ammonia it is converted with development ofheat into benzamide and ammonium acetate.VuZeryZph#iylhydrazide NHPh*NH*C,H,O prepared by mixingacetovaleric anhydride with phenylhydrazine crystallises in yellowish-white pIates melting at 101"; it dissolves readily in alcohol ether,and chloroform sparingly in light petroleum.Capronyl phenylhydruzide NHPh*NH*C6Hl,0 crystallises from lightpetroleum in white needles melting at 116-117" (compare Abstr.,1887 797).N. H. BI.Oxidation-products of the a-Hydroxy acids of the FattySeries. By V. ARISTOFF and N. DEMJANOFF (Chew,. Centr. 1887,1157 from J . Russ. Chem. Soc. 1887 257-271).-The authorsstudied the intermediate products which are obtained by oxidisingthe ethereal salts of the a-hydroxy-acids on the assumption that theethereal salts of the ketonic acids formed by that reaction oughf toshow a greater stability than the ketonic acids themselves. Potassiumpermanganate was used as the oxidising agent. Ethyl lactate insulphuric acid solution gave ethyl pyruvate. Ethyl hydroxybutyrategave about 15 per cent. of the theoretical yield of ethyl propionyl-formate CH,,*CH2*C0.C0,C2H,. It is thus shown that in oxidising thea-hydroxy-acids a-ketonic acids are formed as intermediate products.J.W. L.Lactones and Lactonie Acids. By R. FITTTG (Bar. 20 3174-3185).-When the lactonic acids CHX<fg&:o:!!> obtained bythe union of aldehydes wikh succinic acid are boiled a part distils un-changed but the greater portion decomposes yielding a8 chief products,the monobasic unsaturated acids CHX:CH.CH,.COOH togetherwith the lactones CHX< CH*CH o,co-> and a small quantity of the anhy-dride of the bibasic acids COOH-CHX*CH,.COOH (?).Prop y Zpamconic acid CHPr <-o. o. H,- > prepared from but yral-dehyde and succinic acid crystailises well and melts at 2'35". ItCH(CO0H252 ABSTRACTS OF CHEblICAL PAPERS.readily yields heptyleiiic m i d C7H1202 boiling a t 224-226" and hepto-This boilsat 232-237" without change and behaves quite similarly to the otherlactones. The abnormal behaviour observed by Kiliani (loc.cit.) wasprobably due to impurity.lactone (Kiliani Abstr. 1886 687) CHPr<&6>CH2. CHCH(CO0H)T r i c h l o r o m e t 7 i y ~ a r a c o ~ ~ c (mid CCI,*CH< -O.CO.CH,->~ ObtainedbStreating cblord with sodium succinate and acetic anhydride,mel ts a t 97",and is sparingly soluble. When treated with an excess of haryta-water,it is converted into the barium salt of iso-citric acid. The lnt8ter hastherefhe the constitution COOH~CH(OH)*CH(COOH)*CH2-COOH ;it could not be isolated as the nqueous'solution when evaporated yieldsthe lactonic acid COOHCH< - cH,.co,o->.This is crystalline dis- CII (CO OH)solves i n water in all proportions and gives salts of isocitric acidwhen treated with bases.Phen!ilisohomoparaconic acid C,,H,,Oa is obtained together withphenylhomopnraconic acid (Abstr. 1883,473) by the action of benzal-dehyde on methjlsuccinic acid; it melts at 129.5". The two acidsreact similarly and when distilled yield phenyl butylenes unsaturatedacids CI1H,,O and methylnaphthols CloH6Me*OR. The methyl-naphthol from methylhomoparaconic acid has pro0ably the constitu-tion [Me OH = 3 41 ; it forms yellow needles melting at 89". Thenaphthol from the iso-acid is colonrlesa rneTts a t 92" and is morestable ; the constitution [Me OH = 2 41 is ascribed to it.Bothcompounds give with bleaching powder a green precipitate whicha fterwards becomes yellow. When distilled orer heated zinc-dust,they both yield P-methylnaphthalene ; this melt,s at 37-~3$" (not:-32.5" Schulze Abstr. 1884 1184) and has an odour resembling thatof naphthalene.When the tetrabromo-derivative of ethyl ketipate (Fittig andDaimler Abstr. 1887,361) is treated with ammonia alcohol oxamide(1 mol.) and dibromacetamide (2 niols.) are formed. The conqtitu-tion of ketipntic acid is therefore COOH*CH2~CO*CO~CH,~COOH.The reaction is similar to that observed by Hantzsch and Zeckendorfin the case of ethyl tetrachlorodiketoadipate (Abstr. 1887 727),which can be prepared by the action of chlorine on ethyl ketipate.Dimethyldiketone (DiacetyZ) COMe*COMe is obtained by distillingketipic acid.I t forms a pnre yellow liquid boiling a t 87-89' rathersoluble in water miscible with alcohol and ether. It has an odourresembling tha5 of quinone and yields a very unstable compoundwith sulphurous anhydride. The phenylhydraxine compound C,,H,,N,,crystallises in splendid slightly yellow needles which melt a t '236"with decomposition ; it is sparingly soluble in ether less Roluble inalcohol The dioxinze C4H8N202 is obtained as a white crystallineprecipitate when a dilute solution of the diketone is treated with freehydroxylamine ; a very small amount of the diketone can be detectpdby means of this reaction. The dioxime is very stable and meltswithout decomposition at 234" (compare v. Pechmann t,his vol.,p.24%). N . H. 31ORGANIC UHE,I11IS'rRY. 253Action of Ammonia on Ethyl Acetoacetate and ita Deriva-tives. By M. CONRAD and W. EPSTEIN (Ber. 20 3052-3058).-Met y l ' anzidoacetoncatate " N H,* C Me CH- C 0 OMe is prepared bypassing ammonia throngh a cooled mixture of methyl acetoacetatewith ether (2 parts) in presence of powdered ammonium nitrate. Itcrystallises in lustrous colourless prisms a centimetre long melts at85" and sublimes unchanged.MethyZ " arnidoethy Zacetoacetccte," NH,*CMe:CEt.COOMe is pre-pared by treating 11.6 grams of methyl acetoacetate with 2.3 gramsof sodium and 25 grams of methyl alcohol and adding ethyl iodide ;the whole is afterwards heated on a water-bath ; the methyl ethyl-acetoacetate so ohtained boils at 186-188".This is treated withammonia and the c q s talline product crystallised from alcohol. Itmelts a t 36-37".Ethyl '' amidometh yzacetoacetate," NH,-CMe:CMe.COOEt is pre-pared by the action of sodium in the form of' wire on ethyl p-amido-crotonate (m. p. 37") dissolved in ether the sodium compound beingthen warmed with methyl iodide. It is a white crystalline substancereadily soluble in ether alcohol and light petroleum ; it melts at 52 ',sublimes readily and has a sharp odour and taste. Boiling hydro-chloric acid decomposes i t very readily into ammonium chloride andethyl methylacetoacetate.E thy1 " amidoethy lacetoacetate," NH,*CMe:CEt*COOEt is formedby the action of ammonia on ethyl et~liylacetoacetate ; it was preparedby Geuther.Ammonia has no action on ethyl diethylacetoacetate ; ethyl '' amido-acetoacetate " is therefore probably ethyl amidocrotonate and not animidobutyrate (compare Kuckert Ber.18 618). Ethyl diuhloro-acetoacetate (cooled with ice) is decomposed by ammonia into ethyl-dichloracetate and acetamide.Methyl p-a,midoethyZc?.otonate NH,CMe:CMe*COOMe melts at58-59".Eth y 11 NH,.CMe:C (CO 0 E t)- CH,-C 0 OE t ,crystallises in white lustrous prisms melting at 72" (compare Brandes,Jen. Zeitsch. 3 35).It forms white plates nielting a t 60"." am idoacetosuccinrr te "N. H. M.Action of Aqueous Ammonia on Alkylated Alkyl Acetoace-tates and of Alcohols on the Carboxylic Alkyl-group in Aceto-acetates. By T. PETERS (Ber. 20 3318-3314).-Brandes ( J m .Zeitsck.3 35 and Z e d . fGr. Chenz. 1866,437) described the formationof two compounds (&H,,OaN and C5H,0,N by the action of aqueousammonia on methyl ethylacetoacetate. Conrad and Epstein (precedingAbstr.). employing gaseous ammonia only obtained the compoiindC,H,,O,N or methyl amidoethylcrotonate NH,-CMe CEt-COOMe.The author has repeated Brandes' experiments and besides C7H,,0,N,olhained ethylacetoacetarnide CH3*CO*CHEt.CONH2 (m. p. W).This is undoubtedly the cotnpoa nd described by Brandes as C,H,O,N,and probably obtained by him in an impure state. Ethylic methyl-,isobutyl- and isoainyl-acetoacetates similarly yielded metlhyl- isolmtvl-,aud isoamyl-acetoacetamides melting respectively at 73" 85" and 12io,whilst if Brandes' supposition is correct that in his experi nent,s theVOL. LIV.254 ABSTRACTS OF CHEMICAL PAPERS.substituted ethyl-group was eliminated the above three compoundsmust have yielded amides which were identical.In preparing methyl ethylacetoacetate the author found that ifethyl alcohol was eniployed as the solvent the larger quantity of themethyl salt was converted into tlhe ethyl sdt. Making further experi-ments he found that isobutyl or isoamyl salts could be readily obtainedby the action of the respective alcohol on the et'hyl salts the actiontaking place especially easily in the presence of a small quantity ofsodium. He was similarly able to convert ethyl ethylacetoacetate intothe methyl salt in the presence of sodiiim but the action was lesscomplete than when replacing a lower by a higher alkyl-group.By C.A. BISCHOFF (Bey. 20,2988 -2992) .-The author in conjrinction with Voit has saponifiedethyl a-/3-dimethylethenyltricarboxylate on the large scale and hasconfirmed the results previously obtained by him in conjunction withRach (Abstr. 1885,885). I11 addition a second acid is also formedwhich melts a t E O " and is identical with the readily soluble butane-dicarboxylic acid (Abstr. 1887 45) and the product of change fromthe sparingly soluble dimethylsuccinic acid of high melting points.Voit has also succeeded in converting the two isomeric dimethyl-succinic acids into pyrocinchonic acid.Two symmetrical diethylsuccinic acids are obtained by saponifyingeither ethyl dietbylacetylenetetracarboxylate or the compoundCEt(COOEt),.CHEt.COOEt ; one of the acids is sparingly soluble,melts a t 189" and can be converted into the second which isreadily soluble and melts at 127-128".These acids are probablyidentical with Hell and Muhlhauser's isosuberic acids (Abstr. 1880,542). Experiments are in progress with the object of splitting infot w o optically active compounds the optically inactive didhylsuccinicSymmetrical Diethylsuccinic Acids. By E. HJELT (Bey. 20,L. T. 1'.Isomeric Dialkylsuccinic Acids.acid corresponding with racemic acid. w. P. w.3078-3080) .-Symmetrical diethylsuccinic acid,COOH-CHEt*CHEt*COOH,is prepared by the action of ethyl a-bromobutyrate on ethyl malonateand sodium ethoxide. The ethyl ethylbutenyl tricarboxylate soobtained which boils at 280-282" is saponified and the acid(m. p.147") heated at 150". The residue is then crystallised from hotwater when two acids of the same composition are obtained ; the onemelts at 189-190° and is identical with that prepared by Otto byreducing xeronic acid (Annulen 239 279) and gives an ethyl saltboiling a t 233" which is identical with that obtained by Hell(Rer. 6,30) by the astion of silver on ethyl a-iodohutyrate. The second acidmelts at 127". When the acid melting a t 1@9-190" is heated it isconverted into an anhydride which boils at about 240"; when this ieboiled with water it yields the acid melting a t 127". 100 parts ofwater a t 23" dissolve 0.61 part of the acid of higher melting point andabout 2.4 parts of t.he lower melting acid.The two acids differ alsoin crystalline form (compare Otto and Rossing this vol. p. 45).N. H. MORQANIC CHEMISTRY. 255Action of Ammonia on Alkyl Salts of Fatty Acids. By S.RUHEUANN (Rer. 20 3366-3371 ; compare Trans. 1887 403).-Phenylhgdrazine reacts with ethyl diacetjltartrate acetylphenylhjdr-azine being formed. When ethyl diacetyltartaric acid is treated withammonia tartramide C,H,N204 is formed. I n similar manner,mucamide is obtained from ethyl tetracetylmucate.Ethyl aconitate boils a t 174-175’ under about 22 mm. pressure.When left in contact with aqueous ammonia for 2 to 3 days it is con-verted into citrazinamide (loc. cit.) .When bromine is added to a solution of citrazinamide in stronghydrochloric acid the com,pound C,H3Br,N20 separates as a yellowcrystalline precipitate. This is stable when dry but decomposesslowly in presence of moisture ; hot water decomposes it with evolu-tion of carbonic anhydride.It dissolves very readily in ammonia andin aqueous potash. The corresponding chZoro-derivative C,H:,CI,N,O,,resembles the bromine compound b u t is more stable; it can becrystallised from water but the solution decomposes wben boiled forsome time. Both halogen-derivatives react with aniline orthotolu-idine and piperidine. N. H. It.Apparatus for Distilling Zinc Methyl and Zinc Ethyl. ByA. KAULFUSS (Ber. 20 3104-3105).-The apparatus of which asketch is given is so constructed that the distillation can be conductedin an atmosphere of carbonic anhydride.N. H. M.Disulphones R”R’,(SO,) and R”2(S02)2 By R. OTTO and R.C. CASANOVA (J. p r . Chem. [el 36 433-452 ; compare Abstr. 1885,261 and 537).-Ethylenediethyldi.sulphane C2H4( SO fit) is preparedby heating an alcoholic solut,ion of sodium ethylsulphinate (2 mols.)with ethylene dibromide (1 mol.) ; or by heating an alcoholic solutionof sodium ethylenedisnlphinate (1 mol.) with ethgl bromide (2 mols.).The identity of the products of these two reactions tends to show thatthe sulphur in these sulphinic acids is hexavalent. The snlphonecrptallises in colourless needles and melts a t 136 -137”. Nascenthydrogen in alkaline solution convcrf s it into sodium ethylsulphinateand alcohol. When heated with aqueous potassium hydroxide ityields a thick oil which with benzoic chloride gives ethylsulphone-ethyl benzoate SO,Et*CH,-CH,-OBz melting at 118” ; the correspond-i n g alcohol could not be isolated.Etl~ylenedimet1,y I d i s u l ~ h o n e C,H,(SO,Me) is formed when methylbromide is substituted for ethyl bromide in the above reaction ; i tcrystallises in pearly scales melts at 190” and is soluble in hotwater.Ethyle?zedipropyldisu,lp.phone C2H4( SO,Pr) forms crystals with apeady lnstxe melting at 155”.DiethyZenedisulp12one C,H,< !:> C2H4 prepared by the action ofsodium ethylenedisulphinate on ethylene dibromide is identical withthe oxidation product of diethylene disulphide.Metaphenylenedieth y Idisidphone (&HA( SO,E t)2 prepared by thes 256 ABSTRACTS OF CHEMICAL PAPERS,action of potassium benzenedisulphinate on ethyl bromide formscolourless tables melting a t 142".PhenyZelze-etiLyZenedisuZ~~one C6H4< so4>CpH4 obtained by heat-ing ethylene dibromide with potassium metabenzenedisulphinnte,forms very small crystals insoluble in most solvents.so,A.G. B.Synthetical Researches on and Constitution of Uric Acid.By J. HORRACZEWSKI (Molzatsh. 8 Fi84-593).-The author has shownthat uric acid may be synthetically produced from trichlorolactamideand carbamide ; it is also formed although in smaller quantity fromtricblorolactic acid as also from amidoacetic acid and carloamide. Thislast change doubtless depends on the intermediate formation of aglycocine-carbamide which react's with the carbamide to form u r i cacid water and ammonia.thus COOHCH,*NH2,NHz*CONH2 +2CO<g$ = CO' I( I + 2H,O + 3NH3. Similarly methyl-nric acid may be obtained from sarcosine and carbamide as also frominethylhydantoin and biuret or amyl allophanate. The formation ofuric acid from trichlorolactic acid shows that uric acid is an ureideof acrylic acid whilst the formation of methyluric acid from methyl-hydantoh shows that it is a hydanto'in cyanate. The relation ofuric acid to lactic acid is of especial physiological importance a8Minkowski has shown that on removal of the liver from geese con-siderable quantities of ammonia and lactic acid occur in the urine,whilst the proportion of uric acid is diminished. It has further beenshown by Kan6ra and the author that in the human organism theproportion of uric acid is increased by doses of glycerol.On theother hand the synthesis of uric acid from amidoacetic acid is ofinterest as v. Knierem has proved that in the organism of birdsamidoacetic acid (glycocine) is converted into uric acid and expelleda8 siich in the urine ; the same phenomenon has also been observed,to a less degree in the human organism since the glycocine is for themost part converted in to carbamide.NH- C-C 0 *N H2 \NH.C-NH-COV. H. V.Furfuracrylic Acid. By H. B. HILL (Ber. 20 3359) -Bromineacts on furfuracrylic acid with formation of a crystalline compound,C7H5Br305 which is decomposed by water into dibron2of~rSuretlzy2eneand carbonic anhydride. From the dibromo-compound monobromo-furfuracrylic acid crystallising in long needles and dibromofurFur-acrjlic acid can be readily prepared. (Compare Markwald t h i s vol.,p.135.) N. a. M.Thiazole Compounds. By A. HANTZSCH and J. H. WEHER( B e y . 20 3118-3132 and 3336-3337).-Thiazole is the name . .given to the isomeric compounds <cG N * CH>S CH and <cH CH :mcE>S N ;m simple thiazole-derivative is known but by the condensation oORGANIC CHEMISTRY. 257certair ortho-benzene-derivatives benzene-thiazoles are formed ; forinstance hydroxyphenylthiocyanate gives the compoundand all thiocyanic compounds of ketonic or aldehydic nature in whichthe carbonyl radicle is in the ortho-position to the thiocyanic groupare in their stable .form thiazole-derivatives the atomic complex,CO:CH-S.CN changing into <g::>C*OH.The term meso-deriva-tive is suggested for all compounds in which the hydroxyl-group isdisplaced. From thiocyanacetone Tscherniac and Norton (Abstr.,1883 568) obtained a peculiar base thiocyanopropiniine to whichthey gave the formula NH CMe*CH,*SCN ; this substance is how-ever meso-amidomethylthiazole < CMe cH >S ; by neither ofHofmann's reactions can it be proved that this compound is a primaryamine and with nitrous acid it yields only resinous products butfrom its behaviour towards methyl iodide only two hydrogen-atomscan be in combination with nitrogen ; the study of its acetyl-deriva-tives and of thiocyanacetone prove the above formula to be correct.Methy lamidomethy lthiaxo le hydriodidcr C,NS H4*NHMe HI is theprincipal product of the action of mefhyl iodide on thiocyanopropimine ;i t crystallises with 1 mol.H,O and when treated with potash yieldsmethylamidoniethylthiazole ; this base is a white very deliquescent,crystalline substance not very readily soluble in ether. It has astrongly alkaline reaction and reacts mare readily with methyl iodidethan the origiiial base an abnormal ammonium iodide CloK14S2N31,and diniethylamidomethy Ithimole hydriodide heing formed. The lattercrystallises in large transparent plates with 1 mol. H,O and melts at54" the anhydrous substance melting at 155" ; with potash it yieldsdiinpthylamidonzeth ylthiazole which is a crystalline compound andmelts a t 96". Trimethylamidometh ylthiazolium iodide C4NSH4-NMe31,is obtained on heating the dimethyl base in sealed tubes with methyliodide ; it is a white solid which melts at 85" and is not decomposedwhen boiled with potash.Ace tg lm e t ?i y lamid omet h y It hiazo le CaN S H4.NMeAc is produced byacting on the monomethyl base with acetic anhydride ; it crystallisesin white needles with 6 mols.H,O and melts a t 50" the anhydrouscompound however melts at 113". The existence of this derivative,and the fact that a diacetyl-derivative cannot be obtained from this com-pound is strong evidence in favour of the formula suggested and thatth iocyanopropimine is m eso-amidometh yl thi azole. The ace tyl-deriva-tjive of amidomethylthiazole forms salts with alkaline hydroxides thesodium salt C6H,NaN2S0 + 8H,O is obtained by warming it withconcentrated soda.The formation of this compound and the non-formation of a salt in the case of the monomethylacetyl-derivative,are further proofs in favour of the author's formula as is also thebehaviour of dimethylamidomethylthiazole towards bromine ; whenthis last-named compound is treated with bromine-water only onehydrogen-atom is displaced. The bromo-derivative CsH,BrN2S,N C(NH,258 ABSTRACTS OF OHEMICAL PAPERS.crystallises from alcohol and melts a t 114". Amidomethylthiazole andmethylamidomethylthiazole are completely destroyed by bromine.Since thiocyanacetone yields mesoamidomethylthiazole whentreated with ammonia it must be represented by the formulaN C(0H) < CMe CH >S and not by COMeGB,.SCN that given to it byTscherniac and Norton (Zoc.cit.). It was obtained by their methodin crystalline needles melting a t 98" ; with phenylhydrazine acetate,hydroxylamine and sodium hydrogen splphite it does not react likea ketone but with phosphorous pentachloride it acts like a phenol.The hydroxyl-group reacts very readily and can be displaced byamines ; by the action of aniline anilidomethylthiazole CaNSH4NHPh,is obtained; it crystallises from alcohol and melts at 117". Para-toluiclomet~.ylthiazole melts a t 125" ; with metaphylenediamine,the compound C,H,(NHC,NSH& melting a t 152" is obtained.By the action of metallic thiocyanates on ethyl monochloraceto-acetate ethyl hydr~llmet,hylthiazoleccLrboxylate < -N '(OH)- CMel C(CO*OEt?S'is formed a molecular change taking place similar to that occurringin the formation of hydroxymethylthiazole ; this ethereal salt melts a t128" and judging from its behaviour towards phenylhydrazine doesnot contain a ketone-group.A compound CII&IlS05N,S which meltsat 142" is also formed in this reaction. F. S. K.Bromobenzenes. By A. J. LEROY (BUZZ. SOC. Chin%. 48 210-216).-Benzene 450 grams and aluminium chloride 25 grams aremixed in a large flask and the calculated quantity of bromine is addedgradually care being taken to keep the benzene in large excess. Theproduct is treated with dilute hydrochloric acid separated and dried.I n this way monobromobenzene is obtained almost free from the di-derivative.Dibromobenzene is obtained in tt similar manner using benzene,240 grams bromine 960 grams and aluminium chloride 30 grams.When treated with water crystals of paradibromobenzene meltinga t 89" are obtained together with .a small quantity of tbe tri-deriva-tive which can be separated by fractionation.The liquid product ismainly dibromobenzene which boils a t 219" and does not solidify at-2O" mixed with some of the monobromo-derivative. The mixture iscooled to remove the para-derivative and then treated with fumingsulphuric acid and ordinary sulphuric acid in which the liquid readilydissolves. The product is treated with water to separate the para-derivative and the liquid is distilled in a current of steam whenmetadibromobenzene boiling at 200" is obtained the yield beingequal to about 16 per cent.of the bromine taken. The action ofchlorine on benzene in presence of iodine yields the orttho- and para-derivatives. With aluminium chloride no other derivative is obtained.I t would seem therefore that in the reactions in presence of alum-inium chloride there is a tendency to the formation of para- andmeta-deri vatives.Paradibromobenzene when treated with methyl chloride in presenceof aluminium chloride is mainly converted into carbonaceous proORGANIC CHEMISTRY. 259duct8s ; the liquid products besides monobromobenzene meta- andparadi-bromobenzene contain two tribromobenzenes melting at 44"and 119.6" respectively and yielding nitro-derivatives which melt at93-5" and 125" respectively.It would seem that the aluminium chloride first reduces the para-dibromobenzene to the monobromo-derivative part of the brominebecoming free and acting on the mono-derivative with formation ofthe meta-di-derivative.At the same time another portion of theliberated bromine forms tri-derivatives. These results are analogoust,o those obtained by Friedel and Crafts by the action of aluminiumchloride on dichlorobenzene. C. H. B.Action of Sulphuric Acid on Chlorobenzenes. By ISTRATI(BzdZ. Xoc. Chim. 48 35-41) .-300 grams of pentachlorobenzenewas heated with 2000 C.C. of Nordhausen acid for seven to eight hoursper day during 13 days. Hydrogen chloride sulphurous anhydride,and some water were given o$. A t the end of 15 days the acid wasdecanted off a fresh quantity added and the heating continued15 days longer.No carbonisatmion took place but a deep maroon-culoured substance gradually separated. The acid was neutralised bybarium carbonate but no sulphonic acid was obtained.The maroon-coloured substance after being washed with water dis-solved completely and rapidly in sodium or potassium hydroxide solu-tion forming a deep red liquid and when this was filtered and acidifiedwith hydrochloric or sulphuric acid the substance was reprecipitated.When dried a t 60" it contracts and becomes dark green with a metalliclustre. It is insoluble in boiling water which removes traces of acolourless crystalline substance but it is soluble in concentrated alcohol,very slightly soluble in ether chloroform or carbon bisulphide quiteinsoluble in benzene.The alcoholic solution which is cherry-red bytransmitted light and yellowish-green by reflected light and has verygreat tinctorial power deposits no solid on cooling hence it seemsprobable t,hat a compound is formed. The substance will not crystal-lise from alcohol and is not fusible. When heated to redness it burnsand leaves r? residue of carbon which is only combustible at a veryhigh temperature. It contains 36.83 per cent. of chlorine and is freefrom sulphur. The potassium salt is deep brown with a metalliclustre and is readily soluble in water forming a deep red non-dichroicsolution. The barium iron tin mercury aluminium magnesium,cadmium nickel and other salts are obtained by double decomposi-tion.They are all pale or deep red and are insoluble in water withthe exception of the silver salt which blackens rapidly and of themercuric salt which separates slowly from the solution. The com-pound seems to have a phenolic function and the author proposes tocall it &'rancein.Francein is readily attacked and dissolved by cold fuming nitricacid. When heated in sealed tubes a t 150" to 180" for six hours,large colourless crystals separate. Francein can also be obtained bythe action of ordinary Concentrated sulphuric acid and in this caseanother substance of the same composition as francein but muchmore soluble is also formed a t the same time2 cio ABSTRACTS OF CHEMICAL PAPERS.Tetrachlorbenzene (200 c.c.) when heated to boiling with concen-trated sulphuric acid (1200 c.c.) €or 105 hours is completely dissolvedwith evolution of water hydrogen chloride and large quantities ofsulphurous anhydride.No sulphonic acid is. formed but the chiefproduct is a colonring matter which retains a volatile substance;this sublimes a t loo" crystallises in slender needles and has an odourresembling that of benzoic acid. This substance is removed by treat-ment with boiling water when a reddish-brown solid is left easily~oluble in alkalis. A considerable portion is soluble in boiling waterand especially in alcohol forming a solution which is pale-brown bytransmitted light and dull-preen by reflected light. The more solubleportion contains 33.12 per cent. of chlorine ; the portion insoluble inwater contains 38-72 per cent.I n the preparation of trichlorobenzenesulphonic acid when the snl-phuric acid is diluted with water i t yields tt red prodnct insoluble inwater but easily soluble in alcohol ; this is infusible and very dark-coloured with a metallic lustre.The formation of hydrogen chloride and sulphurous anhydride inthese reactions is of special interest.It is probable that under theinfluence of the sulphuric acid which plays the part of an oxidisingagent part of the chlorine leaves the benzene nucleus the sulphiiricacid being reduced. This action which is quite secondary with thelower chlorobenzenes becomes the dominant reaction with the higherderivatives. In the case of the trichloro-derivative both reactions arewell marked.When pentachloronit~robenzene is heated with concenti-abed sul-phnric acid water and hydrochloric acid are given off in large quan-tities but very little sulphurous anhydride is liberated. On dilutingwith water a crimson precipitate forms.This substance is notsoluble in alkalis but dissolves in warm alcohol from which itseparates on cooling. A dilute alcoholic solution is golden-yellow byreflected light and pale-red by transmitted light.By ISTRATI ( RI& S'OC. Chim. 84,41-43) .-Paradichlorethylbenzene when boiled with concen trnteclsulphuric acid and fuming nitric acid for 50 hours fresh nitric acidbeing added each day .yields a solid crystalline product completely~olnble in the warm acids from which i t is precipitated by addingwater.This nitro-derivative is readily soluble in a mixture of alcoholone part and ether two parts. When treated with boiling water thecompound C6H2Cl,Et*N02 is dissolved and is deposited on cooling.It is very soluble in alcohol and ether and crystallises in lamella:melting at 175". Its solution is feebly acid and is not precipitated bylead salts and is not oxidised by potassium permanganate in the cold.Perri c chloride gives an abun clan t yellowish- w hite precipitate.The portion less soluble in water has the cornpositmion C6C1,Et(N0,),,and is easily soluble in alcohol ether and benzene. It forms smallhard crystals which melt at about 195' with partial decomposition.The alcoholic solution mixed with an aqueous solution of ferricchloride yields a slight precipitate after some time.100 grams of the compound CsH2C12Et.NO2 was boiled for 12 hoursC.H. B.NitrochTorethylbenzenesORQSNIC CHEMISTRY. 261with 500 C.C. of fuming nitric acid and then with a mixture of fumingnitric and sulphuric acids. The product consists of two isomerideswhich can be separated by treatment with warm alcohol. The losssoluble compound forms hard white crystals which dissolve in etherand melt at 82". The more soluble compound has a strong aromaticodour and forms crystals melting at 150". These compounds contain24 per cent.. of chlorine.Orthocyanotoluene. By S. GABRIEL and B. WEHE (Ber. 20,3197-3199) .-OrthocytrnobenzaZ chloride CN*C6H,*CHCl3 is preparedby boiling the oil obtained in tbe preparation of orthocyanobenzylchloride (Abstr.1887 1035) whilst chlorine is being passed through.It boils at 260". When heated with fuming hydrochloric acid a t 170",orthophthaIdehydic acid melting at 97" is formed. Strong sulphuricacid converts it into diphthalide ether (m. p. 221").Ort hocy an obenzotr ichloride C No C,H,* C C 13 is o btnin ed bay the f n rt h e raction of chlorine on the oil from cyanobenzene chloride and crystal-lises from alcohol i n monoclinic crystals of a vitreous lustre ; a b c =1.5464 1 1.1056; /3 = 73" 53'. It melts a t 94-95' and boils a tabout 280". N. H. 21.C. H. B.Action of Nitric Acid on Pentamethylbenzene. By 11.GCTTSCHALK (Rer. 20 3286-3288).-When oxidised with dilutenitric acid pentamethylbenzene yields tetramPthyZbenzenecarEoxyZicacid C6HMe4*COOH [COOH Me4 = 1 2 3 4 31. This acid crys-tallises from alcohol in colourless needles and melts at 165". Itsbariuni salt crystallises in anhydroug scales or in tiiftlv of needles,(CllH1302)zBn + 2Hz0.When the barium salt is heated with lime,it yields prehiiitene. Small quantities of polybasic acids were alsoformed but were not examined.When dissolved in cold fiuning nitric acid pentamethylbenzeneyields dinitroprehnitene. The author believes that the reaction isanalogous to that noticed by Jaoobsen (Abstr. 1886 694) whendurene is treated with fuming sulphuric acid but he has not been ableto isolate bexamethylben~ene from t8he products of tbe reaction.Nitropentamethylbenzene C,Mej.NO2 is obtained by the slow action ofbromine vapour on a mixture of pentamethylbenzene and silver nitrateat ordinary temperatures.It crystallises from alcohol in long ueedlesmelting a t 202". L. T. 1'.Phenylacetylene and Dipher. yldiacetylene. By A. F. HOLLE-MAN (Ber. 20 3080-3082).-Phenylncetylene is prepared by boilingmonohromocinnamene with alcoholic potash. The bromocinnamenowas obtained from ethylbenzene by the method of Friedel and Bahlson(Bull. Soc. Chim. 35 55).Diphenyldiacetylene is prepared by the method of v. Baeyer andLandsberg (Ber. 15 57) ; it melts at 88" (not !No Glaser Annnlen,154 151). Bromine (4 mols.) acts on diphenyldiacetylene (1 mol.)with formation of a tetrabromide melting at 173" and a compoiindmelting a t 149-153"; analyses of the latter point to the formulaC,,HioBrz*C,~HloBr4.N. H. M262 ABSTRACTS OF CHEMICAL PAPERS.Iodophenols. By E. NOLTING and T. SnwxER (Btr. 20 3018-3023 ; compare this Journal 1874 259 ; Zeit.fur Chew. [el 4 322).-Orthiodophenol remains practically colourless after two years' exposureto the air and light. When treated with nitric acid iodine is set €ree,but chloriodophenol is formed if chlorine is passed through its solu-tion in carbon klisulphide. When fused with potassium hydroxide,orthiodophenol yields catechol free from resorcinol even at tempe-ratures above 250".Metiodophenol is formed by the usual reactions from metiodonitro-benzene and metamidophenol ; it is necessary to diazotise metiodanilinein an excess of acid otherwise a compound is obtained whichcrystallises in red needles melts a t 145" and is powibly diiodoxyazo-benzene C6H41gN2*C6H31*OH.Metiodophenol crystallises from lightpetroleum in white needles melting a t 3Y0 or sublimes in small snow-white needles meltiiig a t 40'. It is readily soluble in the usualsolvents does not liberat'e iodine when treated with chlorine orfuming nitric acid even when boiled with the latter and on fusionwith potassium hydroxide yields resorcinol free from catechol.Pariodophenol is readily obtained from paramidophenol. It formslong needles melts a t 93-94" yields iodine when treated with nitricacid b u t not with chlorine and on fusion with potassium hjdroxideat higher temperatures yields resorcinol instead of quinol.To explain the formation in fusions with potash or soda of resorcinolfrom ortho- and pnra-derivatives and gf catechol from meta-deriva-tives without assuming the occuiBrence of intramolecular change Nolting,recalling the fact that fused alkalis sometimes act as oxiciising andsometimes as reducing agents suggests that both these actions occurduring f asion ; 1 3 brornophenol for example being first oxidised to1 2 3 dihydroxybromobenzene which is then reduced to catechol.w. P. w.Solid Orthiodophenol from Iod b e and Sodium Phenoxide.By C. SCHALL (Ber. 20 3362-3364).-When the orthiodophenolobtained by the action of iodine on sodium phenoxide (Abstr. 1883,1109) is kept for some months crystals separate melting a t 4L-43".These dissolre sparingly in hot water and separate as an oil whichcrystallises when a crystal is added.Aniodine determination and the vapour-density show that the substanceis pure orthiodophenol. The crystals are at first lustrous and trans-parent but become slightly red when exposed to air ; they are doublyrefractive and are probably monoclinic (cornpare Neumann AnnaEen,211 67). N. H. &I.It then melts at 29-40".Occurrence of Catechol in Raw Beet-sugar. By E. 0. V.LIPPSIANN (Ber. 20,3298-3:501).-The author has examined a samp:eof raw beet-sugar which showed a strong reducing action on Pehling'ssolution but from its mode of manufacture could not contain invert-sugar. An ethereal extract yielded small quantities of catechol and ofan acid C9HlOOa which showed most of the properties of catechol,and yielded that substance when heated.The author cannot tellwhether these substances were derived from the beetroot or werORGANIC CHEMISTRY. 2G3formed by the decomposition of part of the carbohydrates during theprocess of manufacture.Catechol reduces Fehling’s solution but not Soldaini’s solution andthe author therefore advises the use of the latter in preference toPehling’s solution in sugar testing. L. T. T.Hydroxyquinones. By R. NIETZKI and 3‘. KEHRMANN (Rer. 20,3150-3158) .-The authors try to prove experimentally that theformula of tetrahydroxyquinone is C6(OH),OZ [O 0 = 1 41 andthat of rhodizonic acid C6(OH),O4 [OH OH = 3 61. By mixingan aqueous solution of tetrahydroxyquinone with a salt of orthotoluyl-enediamine and adding sodium acetate a green crystalline sub-stance is precipitated.This dissolves in alkalis and dilute mineralacids ; when dried a t increased temperatures it turns brown and isultimately converted into the mine of rhodizonic acid ; when oxidisedit yields diquinoylazine C604:N,C7 H,. From its marked basic pro-perties it was thought that only one nitrogen-atom had entered intoreaction and that its formula was c6( OH),O:NC,H,NH aiialysisshowed however that its true composition was C,,H,,N,O and t w oformulae,N- NC6(OH)/ I ‘C7H6 [N N = 1 21 or C60(OH)3<NH >C7H6‘N’[N NH 0 = 1 2 41 are suggested. Now if tetrahydroxyquinoneis an orthoqninone it would react with diamines even when the hydro-gen of the hydroxyl-group is displaced ; but with tetrabenzoyltetrahy-droxyquinone no reaction takes place.By heating tetrahydroxy-quinorie with acetic chloride a yellow crystalline diaeetyZ-derivative,Gg08(OA~)L(OH)1 is obtained ; it melts a t 205” is soluble in alcoholand ether but less readily in water; it acts like a bibasic acid andwith orthotoluylenediamine yields a compound very similar to thatobtained from tetrahydroxybenzene ; it is moreover in ita wholebehaviour very similar to chloranilic acid and has therefore the con-stitution [(OH) (OAC)~ = 2 5 3 61. From these results i tfollows thatl tetrahydroxyqninone is a paraquinone and that thesecond o€ the above formulae shows the constitution of the compoundformed with orthotoluylenediamine.By S.v. KOSTANECKI (Ber. 20 3133-3137).-As paraquinon-oximes are obtained by acting on monhydricphenol-derivatives with nitrous acid it is usually accepted that whenmore than one isonitroso-group enters into a polyhydric phenol eachtakes up the para-position with respect to a hydroxyl-group. Thesymmetrical formula C6H20,(NOH) [ 0 (NOH) = 1 3 5 61 hastherefore been given to dinitrosoresorcinol and its correctness is thesubject of this research.Resorcinol and orcinol give dinitroso-compounds when heatedwith only one molecule of nitrous acid but from bet.orcino1C‘6H,Me,(OH)2 [Me = 1 4 3 51 amono-derivative only isobtained even with an excess of nitrous acid and this abnormalbehaviour can only be explained by the supposition that the methylF.S. K.Dinitrosocresorcinol264 ABSTRACTS OF CHEMICAL PAPERS.radicle occupies the pmition which would be taken u p by the secondisonitroso-group. The formula of dinitroso-orcinol is thereforeC6HMe(NOH),o2 [Me (NOH) 0 = 1 2 4 3 51 and of dini-trosoresorcinol C6H,(NOH),0 [(NOH) 0 = 1 :? 2 41. Theseformulm are supported by the behaviour of cresorcinol C6H,Me( OH),[Me (OH) = 1 2 41 towards nitrous acid a dinitroso-derivativebeing produced. Since in cresorcinol there is only one para-positionfree it is probable that the symmetrical formula for dinitrosoresorcinolis wrong. DiiLitrosocresorcinol was obtained in the form of it pale-green substance which crystallises with 1 mol. H,O. When heatedin a capillary tube above 160° it explodes ; i t is sparingly soluble inwater a,nd alcohol insoluble in ether chloroform and benzene.Nitric acid oxidises i t to dinitrocresorcinol CsHMe(NOz)a(OH)2,which cryatalliaes in long yellow needles and melts a t 90" it issparingly soluble in cold more readily in hot water readily solublein ether or alcohol; it imparts a bright-yellow colonr to animalfibres.It is probable that dinitrosocresorcinol has the formulaC6H02(NOH)JLe [O (NOH) Me = 1 3 2 4 61 thatdinitrosoresorcinol has an analogous constitution namely [ 0 (NOH)2= 1 3 2 41.andF. S. I(.Action of Nitrous Acid on Anethoi'l. By P. TOENNIES (Ber. 20,2982 - 2987).-The compound of anethoil and nitrous acid,OMe-C6H4.C3H5( N203) (Abstr.1879 35 517) as already described(Abstr. 1881 167) when heated with alcohol or aqueous potash,yields an isomeric crystalline product' which dissolves readily inalkalis but is precipitated by acids from the solution with the 105sof the elements of a molecule of water in the form of a well-crystallised compound OMe.C6H,*C<NpOp>. This substance bythe action of alcoholic potash is converted into an isomeric com-pound which readily yields methoxycyanobenzene OMe*C6H4*CN,when heated with hydrochloric acid. The compound of anethoil andnitrous acid in addition forms an acetate,CMeOMe.C6H~*C(NOAc).CIeH(oN~),when treated with acebic chloride and on these grounds is nowregarded by the author as an isonitroso-derivative of the formulaOMe*C6H4.CI(N-OH)*CMeH(ONO).The acetate cannot be distilledin a vacuum without undergoing decomposition into acetic acid andthe nitrosoketone OMe-CaH,*C(N.OH)*COMe which forms an oilreadily crystallising in yellow needles. This compound is easilydecomposed by boiling hydrochloric acid yielding hydroxylamineand the diketone OMe*C6H4.CO*CO&fe which can also be obtained bytreating the compound of anethoil and nitrous acid with hydrochloricacid in the cold ; i t is a yellow oil and reacts with phenylhydrazineto form the beautifully crystalline dihydrazide,OMe* C6H4' C ( N2HP h) CMe*N,HPh.The isonitrosoketone is obtained also when the compound of anetho'iORGANIC CHEMISTRY. 265and nitrous acid is treated with alcoholic potash and the product,after the evolution of nitrous oxide has ceased is dissolved in waterand precipitated by hydrochloric acid.On reducbion it is convertedinto two compounds one of which is the base Okfe-C6]E-T4*CHAc*NH2,and the second is the ketone OMe*C6H~*CH2Ac derived from this byloss of ammonia. This ketone is an oil of pleasant odour boils at264" and yields an oily compound with phenylhydrazine. Theketonic base also forms a condensation compound with phenyl-hydrazine and is converted into the acetate OMe*C6H&HAc.NHAc,by the action of acetic anhydride whilst its solution in hydrochloricacid if treated with aqueous potash yields a condensation compound,OMe*C6H4*CH<gM>&T> CH*C,H,*OMe. This tertiary base doesnot react with acetic acid or nit,rous acid but forms with methyliodide a t 100" a beautifully crystalline hydriodide of a mono-methylated base ; on heating this it is readily converted into methyliodide and the original base but forms with aqueous soda a scarlet-red powder yielding well-crystallised salts with hydrochloric acidand platinic chloride.The addition product of cinnamene and nitrous acid C,H3Ph(N,0,),exhi bits properties very similar to those of the anethoil compounds.By reduction it yields a base CzH3Ph(OH)*NH2 and on treatmentwith sulphuric acid is converted into phenylnitroethylene with theevolution of nitrous oxide.When the cinnamene additive compoundis treated with aniline nitrous oxide is also evolved and a newbase probably of the formula NHPh*CH(O€€).CPh NOH is obtained ;this is decomposed by hydrochloric acid into benzaldehyde benzo-nitrile and aniline.A similar reaction also occurs when ammoniaand methylamine are employed instead of aniline and in this respectthe cinnsmene compound differs from the anethoF1-derivative since thelatter when treated in like mmner with ammonia and methylamineyields with evdlution of nitrous oxide the diketone,OMe* C6H4* c0.c 0 Me,as chief product only small quantities of the basesOMe*C6H4*C( NOH)*CHNe*NH,,and OMe*C6H4*c (NOH)*CHMe*NHMe being obtained. The research w. P. w.By A.HNOP (Her. 20 335'2 -3353). When phosphorous pentasulphide isheated with aiiiline a t a temperature not exceeding 150° and theproduct is steam-distilled and crystallised from alcohol the compoundPS*C,,H,,N3 is obtained in monoclinic crystals melting at 153" ; thereaction is accompanied by a violent evolution of hydrogen sul-phide.Chcvrier (Zeit.fiir Chem. 1868 569) by the action of phosphorussulphochloride on aniline obtained an amorphous compound meltingat 75' of the same percentage composition as that described above.N. H. Meis being contin lied.Action of Phosphorous Pentasulphide on Aniline266 ABSTRACTS OJ!' CHEMICAL PAPERS.Sandmeyer's Reaction. Substitution of Cyanogen for theAmido-group. By F. AHRENS (Beg-. 20 2952-2958).-The threeisomeric amidophenols when diazotised and heated with Sandmeyer'ssolution of potassium cyanide and copper sulphate (Abstr. 1885,149) aye readily converted into the corresponding cyannophenols (com-pare next Abstract).To obtain a good yield of orthocyanophenol,it is necessary to separate the diazochloride of orthamidophenolbefore treatment by Sandmeyer's method but this step can be omittedin the other two cases. Orthanisidine can in like manner be con-verted into cyananisoil.Paramidoa cetophenone on similar freatm ent yields cyanncetophe-none CN-C6N4*COMe. This crystallises. in white needles melts at 60-61'. is insoluble in water but readily soluble in alcohol and ether and onhydrolysis is converted into Meyer's acetylbenzoic acid (m. p. = ZOOo).The ozime CN*C6H4*CMe:NOH crystallises in wbite scales meltinga t 160'. Paramidohenzophenone under like conditions forms acyanobenzoph enone CN.C6H4* C 0 Ph crys tallisin g in y ellowish-whit egrznules melting at 107-108" and this on hydrolysis yields para-benzoylbenzoic acid.The oxinie CN.C,H,*CPh:NOE crystallises inwhite scales and melts at 176".When paramidodimethylaiiiline is similarly treated and the productextracted with ether an oil is obtained which cbuld not he purified,but probably consists of dimethylamidobenzonitrile CN*C,H,*NMe,,since. on hydrolysis with alcoholic potash i t yields an acid identicalwith Michler's paradimethylamidohenzoic acid.The author has not succeeded in converting sulphanilic acid intoOtthocyanophenol. By V. MEYER (Ber. 20 3289) .-RepeatingAhrens' experiments on the effect' of Sandmeyer's reaction on amido-phenol the author entirely failed to get the cyanophenol described byAhrens (preceding Abstract) b u t obtained salicouitrile (Tiemann,this.vol. p.276).Derivatives of Paramidoisobutylbenzene. By C. GELZER(Ber. 20,3253-3259) .-Nitracety lamidoisobuty lbenzene,is obtained on nitrating acetylarnidoisobutylbenz~ne at 0" ; it crystal-lises in slender,-yellow needles and melts a t 250-252O with somedecomposition. When reduced an anhydro-base seems to beformed.NitramidoisobutyZbeizzene C4H,-C,H,(NCi,)*NH prepared by theaction of cold alcoholic potash on the acetyl-compound crystallisesin yellowish-red short needles or plates melts at 106.5" is onlysparingly soluble in h o t water readily in alcohol benzene and ether.The salts are rery soluble and are not characteristic.DiamidoisobutyEbenzene C4Hg*C6H3(NH2) obtained by the reductionof the preceding compound crystallises in micaceous colourless scalesor tables melts at 97*5" distils a t 280-282" and is sparingly solublein cold readily soluble in hot water and in alcohol ether andbenzene.The hyhochZoride C,H,,N2,2HC1 forms lubtrous whitecyaiiobenzenesulphonic acid by this reaction. w. P. w.L. T. T.CaHg*CsH,( NO,).NHAcORGANIC CHEMISTRY. 267plates ; the picrate crystallises in slender yellow needles ; theoxalate forms thin white plates. Like other orthodiamines it formscompounds with phenanthraquinone and benzil.P~enanthraisoZ,utylphenazine I 11 I \C6H3*C4H prepared byadding the diamido-base to a solution of phenan thraquinone in glacialacetic acid crystallises in pale-yellow interlaced needIes melts at146-5" and is very sparingly soluble in hot water or cold alcohol readilyin ether or benzene.It is not decomposed when boiled with hydro-chloric acid. With concentrated sulphuric acid it gives a charac-teristic cherry-red coloration.c6H.a.c.NC6H4* GO:."C Ph C *N.BeltziZoisoZ,2Lty123henazine I 11 I \c6H3*c4H forms nearly white,C P 11 C *N'slender needles melts at 144") is insoluble in water moderatelysoluble in alcohol and readi1y.h benzene ether and carbon bi-sulphide. It has very feeble basic powers but a hydrochloride,( C24H22N2)2,HCl is described ; i t forms a greenish crystalline powder,and is decomposed when dissolved.Condensation of Chloral Hydrate with Tertiary AromaticAmines. By 0. KK~~FLER and P. BOESSNECK (Rer.20 3193-3195).-The compound CCI,GH(OH).C6H4*NMe2 (Abstr. 1886 458) isbest prepared by treating a solution of 200 grams of chloral hydratei n 300 grams of dimethylaniline with 110 grams of powdered zincchloride. After some weeks the viscous mass becomes crystalline.The base is then converted into the hydrochloride. The yield is82 per cent. of the theoretrical. The sulphate crystallises in cubes moresoluble than the hydrochloride.A. J. G.Paradimethy lamidobenz y lidene-phsny lhydraxine,NMe2*C6H4*CH:N2HPh,crystallises in needles melting a t 148".in yellowish-brown plates melting a t 144".Paradimeihylnmidobenzaldoxime NMe2*C6H4-CH:N*OH crystallisesN. H. M,Action of Aromatic Diamines on Sugar. By P. GRIESS andG. HARROW (Be7-.20 3111-31 IS> .-Ar~bino-ortl~odianzidobenzene,C6H4<NH >C5H,0a is obtained by mixing aqueous solutions oforthodjamidobenzene (1 mol.) and arabinose (2 mols.). The whole isevaporated nearly to dryness water being added as it evaporates untilthe amount of crystals no longer increases. It crystallises from boil-ing water in small white needles which melt with decomposition at235" ; it is sparingly soluble i n boiling water less soluble in alcohol,and almost insoluble in ether. It has a slightly bitter taste does notreduce Pehling's solution and is dextrorotatory. Aqueous potashdissolves it readily. Boiling concentrated hydrochloric acid andboiling aqueous potash have no action on it. The hydrochdoride crys-tallises from water in which it is readily soluble in globular groupsN2 68 ABSTRACTS Otc' CHEJIICAL PAPERS.of very small plates.It is sparingly soluble in dilute hydrochloricacid. The I~ydrobromide resembles the hydrochloride. The formationof arabinodiamidobenzene is similar to that of gluco-orthodiamido-benzene (Ahstr. 2887 930) assuming arabinose to have the formulaC,Hl0O5 (Kiliani Abstr. 1887 465). ,81.abir~ornc!t~~aradiam idof o Zueize C6H3Me <hH > C5H804 preparedsimilarly to the componnd above described crys tallises in small,white needles having n slightly bitter taste. It melts at 238" and ismore sparingly soluble than the orthodiamidobenzene-derivative towhich it is in other respects very similar.Ara bino- 7- dii1712 idobenzo ic acid c 00 H*C6H3< NH> C,H804 + 2H20,crystallises in needles melting with decomposition at.235". It issparingly soluble in boiling water less soluble in alcohol. It isdextrorotatory reddens litmus and does not reduce Fehling's solution.The barium salt is a white amorphous substance ; the silver salt.forms a white sandy powder. The hydroc7doride crystallises fromdilute hydrochloric acid in small white needles ; it is decomposed bywater .Galacfo-orthodia-i~o~enselze C6H4<NH > c6H,005 rese rribles t bemabino- derivative in physical and chemical properties. It me1 ts a t246" wit4 decpmposition. The 7Lydror:hZoride with 14 mol. H,O. andthe hydrobmmi~e.crysta11ise in needles and are very readily soluble inwater sparingly soluble in hydrochloric acid.Galacto-y-dianzidohenxoic acid COOH*CJ13<NH> C6HI0O5 + H20,It completely resembles the correspondingYHNHNHNHcrystallises in needles.arabino-acid.N. H. M.Decomposition of Diazo-compounds. By I. REMSEN andW. R. ORNDORFF (Amer. Chem. J. 9 387-399).-Pure and drydiazobenxene nitrate was decomposed by warming it with ten timesits weight of absolute alcohol. The several products obtained,calculated on the weight of nitrate taken were phenetoil 16 per cent.,orthonitrophenol 7 per cent. diriitrophenol 3.5 per cent. benzene1.8 per cent. and considerable quantities of tarry matter from whichnothing definite could be separated ; no aldehyde was observed.Griess had previously not,iced the production of nitrophenols andattributed them to his not having used absoluts alcohol but that thisexplanation is not correct is shown by the above and by the fact thatdry diazobenzene nitrate when heated with dry toluene yields 20 to24 per cent.of orthonitrophenol but no dinitrophenol. Using 50 percent. alcohol for the decompmition the quantities of nitrophevolsformed are increased whilst the yield of phenetoi'l and especiaIly ofhenzene is decreased. Using dry diazobenzene sulpl-mte and absolutealcohol SO per cent. of phenetoi'l and 1.5 per cent. of benzene wereobtained and using toluene in place of the alcohol para1)henol-siilphonic acid is formed. The last decomposition namely elimina-tion of nitrogen and rearrangement of the constituents of the moleORGANIC CHEMTSThT. 269cule corresponds with that undergone by the nitrate :-C6Hb-N2*O*N02= C,H,(OH)-NO + N2. Phenetoil boils a t 170" and when treatedwith fuming nitric acid yields dinitrophenol (m.p. 86-87'). This isvery nearly t h e melting point of dinitrobenzene (89*9O) and hencethe misstatement that benzene is the principal product of the decom-position of diazobenzene with alcohol.When orthodiazotoluene sulphate is heated with absolute alcohol,the principal product is orthocresyl ethyl ether (30 per cent.) ; neithertoluene nor aldehyde could be detected. With the para-compound thedecomposition is quite different 18 per cent. of toluene and 11 per.cent. of paracres71 ethyl ether being obtained as well as aldehyde.Metadiazotoluene sulphate and absolute alcohol yield neither aldehydenor toluene but rnetacresyl e t h j l ether is formed (55 per cent. reckonedon the metatoluidine employed).The metatoluidine was preparedfrom paratoliiidine by nitrating the acetyl-derivative eliminat,ing theamido-group and reducing the metanitrotoluene. In this case i t is tobe noticed that the diazo-group is readily displaced by hydrogen ayield of 68.7 per cent. being obtained.The authors conclude that the presence of a paraffin residue in thepara-position relatively to the diazo-group is favourable to the displace-inent of' the diazo-group by hydrogen. Wroblewski from st stud7 ofthe three ohlorotoluidines concludes that in the decomposition of thediazo-compounds by alcohol the normal reaction (production of thehydrocarbon) suffers a change due to the influence of the-halogenwhen it occupies the para-position relatively to some Dther substitu-ting group.This conclusion is contradicted by the author's experi-ments. Of the nine recorded cases of mono-substituted amido-benzenecompounds that undergo Griess' reaction eight contain the two groupsin the para-position. An examination of the 80 or 90 cases in whichtwo or more groups are present besides the amido-group and inwhich the diazo-group is displaceable by hydrogen also shows that innearly all cases the amido-group is in the para-position with respect tosome other group. H. B.Diphenylpara-azophenylene. By E. v. BANDROWSKI (Monatsh. 8,475-48S).-In a former paper (Ahstr. 1886 1023) the authorrjhowed that the product of the oxidation of diphenylamine in alkaline- NPh solution is a diphenylpara-azophenylene C,H,< Nph>' a view con-firmed by its ready hydrogenation into a leuco-product ; the latterseems to be identical with Calm's diphenylparaphenylenediamine.To confirm this view this substance was prepared according to Calm'sdirections from quinol and aniline heated with a mixture of zinc andcalcium chlorides in a eealed tube at 200-210".Thus prepared themelting point of the compound was found to be 132-135" instead of152" as assigned to it by Calm. The same melting point was foundfor the substance Cl8HI6N2 prepared by the author's method ; hencethere can be no doubt as to the identity of the two compounds inquestion. This identity was further confirmed by the conversion ofthe diphenylparaphenylenediamine prepared by eit)her method intothe oxidation product of diphenylarnine CleHl*Nz which was effectedVOL.LTV. 270 ABSTRACTS OF CHEMICAL PAPERS.either directly by moderate oxidation with hydrogen peroxide or indi-rectly by decomposit.ion of the dinitroso-derivative in hot alcoholicsolution. This dinitroso-derivative formed by passing nitrous fumesinto a cold alcoholic solution of diphenylpar~phenylenediamine formsyellow glistening crystals melting at 120" with decomposition. Itgives an intense red coloration with sulphur and nitric acid and isconverted by hydrogenation with zinc-dust and acetic acid intodiphenylpara-azophenylene and on boiling with alcohol into diphenyl-para-azophenylene and nitric oxide.On bromination in chloroformsolution diphenylpara-azopbenylene gives a hromo-derivative,C,H8Br6N2 or C18HIOBrRN2.This forms aciculrtr crystals melting at 243". T t dissolves in nitricacid with production of a dirty-green colour. On dilution a reddishprecipitate of a dinitro-derivative is obtained but this probably con-sists of two isomeric substances. V. H. V.Substitution in Azo-compounds. By E. Niirmw (Bey. 20,2992-2998) .-Amidoazobenzene yields several crystalline compoundswhen nitrated none of which however are identical with 1 4 o r 1 3C,H,(NO,)*N N*C6H4-NHa. The nitro-group seems to enter theamidated group since aniline was obtained by the reduction of thecompound.When phenylazodimethylaniline (dimethylamidoazobenzene) is dis-solved in concentrated sulphuric acid (66" B.) nitrated in a freezingmixture with A mixture of 50 per cent.nitric acid (1 part) andsulphuric acid (2 parts) and the product poured into water a nitro-derivative PhN N-C6H,(N02)-NMe2 is obtained which crystallisesin black needles with a greenish iridescence and melts a t 198" ; it isinsoluble in water sparingly soluble in alcohol and ether readilysoluble in benzene. It is a feeble base and on reduction yields anilineand anot'her basc probably dimethyltriamidobenzene. An isomericnitro-derivative N02*C6H4.N2.~~H4*NMe2 is also formed identical withthat prepared by Meldola (Trans. 1884 107). This crystallises ir,needles melts a t 225-226" and is sparingly soluble in alcohol ether,and benzene.On reduction with ammonium sulphide it yields amido-dimethglamidoazobenzene melting at 186-187" and with tin andhydrochloric acid it is converted into paraphenylenediamine anddime thylparaphenylenediamine.When pnratolylazodimethylaniline is nitrated in like manner it~ yields a nitro-derivative C6H4Me.N,.C6H4(Pu'Of).NMe which crystal-lises in long bright red needles melts at 181" and is sparingly solublein alcohol and etther readily soluble in benzene. It is a feeble base andon reduction is converted into paratoluidine and a readily decomposable'base. The isomeric bases C6H,Me(N02).N,.C6H4.NMe2[Me NO N = 4 2 I],cx-ystallising in brownish-red scales melting at 159-160" andl>fe NO N2 = 4 3 11 crystallising in red prisms melting at114G-147" were prepared for purposes of comparisonORGANIC CHEMISTRY.271If phenylazodimethy laniline is sulphonated with 100 per cent. sul-phuric acid at loo" a sulphonic acid s03H*CaH*.Nz*C6H40NMe2 isformed identical with that obtained by Miihlau (Abstr. 1884 1149).ParatolylazodimethylaniIine can be sulphonated by dissolving it in100 per cent. sulphuric acid and heating at 100" with sulphuricacid containing 66 per cent. of sulphuric anhydride; the resultingsulphonic acid S03H.CsH3Me.Nz*~sH4*NMez crystallises in violetprisms and is soluble in hot water and alcohol yielding like its salts,red-coloured solutions. On reduction it is converted into dimethyl-psrnphenylenediamine and metamidoparatoluenesulphonic acid. Theseexperiments were made in conjunction with T.Bhumann.When phen ylazophenol (oxyazobenzene) is nitrated under the aboveconditions the witro-derivative NOZ*C~H~.N~*C~H~.OH forms thechief product. This crystallises in reddish-brown needles melts at211" and is identical with that obtained from phenol and diazotisedparanitraniline. The isomeric nitro-derivatiTres [NO N2 = 1 21,crystallising in orange-yellow needles melting at 126" and [NOz Nz= 1 31 ci-ystallising in red needles melting at 155-157" were alsoprepared for purposes of comparison. A dinitro-derivative,is also formed during the nitration and constitutes the chief productif twice the quantity of nitric acid is employed. It crystallises inorange-red needles melts at 200° and is identical with the compoundobtained from diazotised 1 2 4 dinitraniline and phenol.Theseexperiments were made in conjunction with T. Stricker. w. P. w.Diazoamido-compounds. By E. No~nma and F. BIXDER (Bey.,20 3004-3018) .-The authors have prepared the diazoamido-com-pounds from paratoluidine and diazohenzene chloride and from anilineand diazoparatolyl chloride and have submitted each to the followingreactions comparing the products throughout :-( 1.) Reduction at0" in alcoholic solution with tin and bydrochloric acid products,aniline paratohidine phenylhydrazine an d paratolylhydrazine.(2.) Bromination in benzene solution in the cold products diazo-paratoluene bromide and tribromaniline. (3.) Digestion with a mix-ture of aniline (2 parts) and aniline hydrochloride (Q part) at 60"until nitrogen was no longer evolved when a sample was treated withdilute sulphuric acid products amidoazobenzene and paratoluidine.(4.) Digestion in like manner with dimethylaniline products para-tolylnzodimethylaniline and aniline.(5.) Digestion with excess ofphenol and some sodium hydroxide at 60" until nitrogen was nolonger evolved when a sample was treated with dilute sulphuric acid :products phenylazophenol (hydroxyazobenzene) and paratoluidine.The quantity of phenol employed seems to influence the nature of theproduct (compare Abstr. 1887 664). (6.) Digestion with excess ofdilute sulphuric acid (1 to 10) products aniline paratoluidine,phenol and paracresol. (7.) Ethylation of the compounds anddecomposition of the products by treat>ment with dilute sulphuriot 2 i d ABSTRACTS OF CHEMICAL PAPEkF.acid products ethylaniline ethylparatoluidine phenol and para-cresol.I n experiments (3) and- (5) the compounds act as if eachliad the constitution PhN N*NH*C7H7 in experiments (2) and(4) as if each had the constitotion C7H,.N:N-NHPh whilst fromexperiments (1) and (6) both formulte must be ascribed to each of thecompounds? and i n experiment (7) each compound must have con-tained both isomerides unless in this experiment a third isomeridehas been formed 2s Meldola has been led to conclude is tile case whendiazoamidometani%roparaliitrobenzene is ethylated (Trans. 1887 110,443). In all these experiments no difference could be detectedbetween the two compounds in the course of the reactions or in thenature or relative quantities of the decomposition products and henceGriess' conclusion that they are identical is confirmed.The compounds formed by the action of diazoparatolyl chloride onethy laniline and of diazo'benzene chloride on ethylparatoluidine areisomeric.Para~aazotobylethyZnrzilide C7H7N N-NPhEt is an oil whichcannot be crystallised and yields paratolylhydrazine and ethylanilineon treatment with nascent hydrogen paracresol and ethylaniline on di-g,>stion with dilute aulphuric acid and paratolylazophenol and ethylani-line on digestion with phenol. Diazo benzene-et hy Zpa yatoluide,on the contrary forms red crystals melk a t 38-39" and yieldsphenylhydrazine and ethylparaboluidine on reduction with nascenthydrogen phenol and ethylparatoluidine on digestion with dilute sul-phuric acid and phenylaaophend and ethylparatoluidine on.digest,ionwith phenol.The compounds formed by the action of diazobenzene chloride onparabromaniline and of pambromodiazobenzene chloride on aniline areidentical and yield parabromaniline and phenol on digestion withdilute sulphuric acid a result.pointing to the formulaPhN N.N%€*C6H4Br.Diazobenzene chloride reach with P-nqhthylamine to form anamido-a,zo-compound ; a ctiazo-nmrifo-compound however is formed bythe action of diazo-,B-nnyhthyl chloride on aniline.This crystallisesin bright yellow needles melts at 150' with decomposition and yieldsaniline B-naph thylamine phenol and @naphthol on digestion withdilute sulphuric acid amido-am benzene and ,B-naphthylamine ondigestion with aniline and phenylazophenol and ,B-naphthylamine ondigestion with excess of phenol the two last results pointing to theformula PhN N*NH*CloH7 which does not accord with its method offormation.The diazo-amido-compound obtained by the action of diazo-3-naphthylchloride on aniline yields on digestion with dilute sulphuric acid amixture of aniline or-naphthylamine phenol and a-naphthol.Thediazo-aniido-compound foymed by the action of diazoparanitrobenzencchloride on aniline crystallises in yellow silky needles. melts a t 148",and yields phenol aiid paranitraniline on digestion with dilute sul-Diazobenzcne chloride does not react with paranitranilineORGANIC CHE3IlYTRT.273phuric acid diazobenzene bromide and bromoparanitraniline onhromination phenylazophenol and paranitranihe on digestion withexcess of phenol and paranitraniline aniline amido-azobenzen e andpariinitramido-azobenzene the last in very small quantit>y on diges-tion with aniline.Diazobenzenepiperide PhN N-N C5Hlo obtained by the action ofdiazobenzene chloride on piperidine and sodium acetate in molcculayproportion yields phenol and piperidine on digestion with dilutesulphnric acid and phenylhydraziine and piperidine on reduction withnascent hydrogen.Diarobenxenetetrahydr~~.~i?aolide PhN N*N C9Hlo obtained in likemanner is a yellow oil and yields phenol and tetrahydroquinolinewhen boiled with dilute sulphuric acid.Diaxobenzenemethylaizilide,PhN N-NMePh d s o obtained in like manner is a yellow oil whichgradually changes especiaily if Braces of acid are present into theamido-azo-compound and yields phenol and methylaniline when boiledwith dilute sulphuric acid and phenylhjdrazine and methylaniline onreduction with nasoent hydrogen. The compound formed by thereduction of paranitmdiaeobeneene chloride on methylaniline is para-n~ts.o~~~enyZazornethijlunill;r~e C6H4( N02)NI N.C6H4*NHMe which ci-ys-tallises in red needles melting at 134".Gasteger has prepared the following -Diazop~rnto71/Zethyl~~a~~-toluide C7HiN N*NEt*C,H a yellow oil yielding paracresol andethylparatoluidine with dilute sdphuric acidr; diaxom,etanitrobensene-ethylparatoZihide.C6H4(NO2) N N-NEh*C7H which crystallises inyellow needles melts a t 53" and yields metanitrophenol and ethyl-paratoluidine when boiled with dilute sulphnric acid ; dianoyuranitro-Etenxe~Le-ethtlZ~arato~i~ide C6H4(N0,)N N.NEt.C7Hi which crystal-lises in yellow needles melts a t 114-115" and yields paranitrophenoland ethylparatoluidine when boiled with dilute sulphuric acid.TV. P. w.Constitution of Azimido-compounds. By E. NOLTING and A.ABT (Bey. 20 m9-3003) .-Hitherto Gciess' formula R' 'NH(Abstr. 1883 56) for the azimido-compounds has been more gener-ally adopted than the alternative formula R<- N>N proposed byKekulk and by Idadenburg (Rer. 9 219); the authors however,bring forward the following evidence in supFort of the latter and inaddition point out that the formation of acetylazimidotoluene fromncetylorthotoluylenediamine (Abstr.1886 874) admits of easy expla-nation on this theory without assuming an intramolecular change,which is necessary if Griess' formula is employed.When pure ethyltoluylenediamine hydrochloride [NEtH NH Me= 1 2 41 in concentrated aqueous solution is treated a t 0"with sodium nitrite in molecular proportion et?r~ZazimidotolzLene,C6H,Me N,*Et is obtained ; this cryshallises from alcohol incolourless needles melts a t 147" and is insoluble in water and alkalis,but soluble in the ordinary organic solvents. The hydrochloride isN \A/N2 74 ABSTRACTS OF CHEMICAL PAPERS.decomposed by wat,er ; the platinfochloride ( C9H12Ns),,H2PtC16 crys-tallises in yellow needles.Azimidotolnene (Ladenburg ;bid.) prepared in like manner frompure orthotolnylenediamine hydrochloride has not only basic butfeebly acid properties since it dissolves in alkalis and can be repre-cipitated frcm the aolution by carbonic anhydride. The sodiunz-compound C7H6NaN3 crystallises from benzene in white flocks con-sisting of small needles and in solution is only stable in the presenceof excess of alkali.When ethylnted azimidotoluene yields a com-pound identica,l with the ethylazimidotoluene just described andinasmuch as two isomeric ethyl-derivatives are theoretically possible(assuming Ladenburg's formula) the authors hold that in this case i tis the amido-group in the meta-positicn relatively to the methyl whichis converted into the azo-group when orthotoluylenediamine is diazo-tised.On fusion with potassium hydroxide azimidotoluene is con-rerted into amidocresol with the evolution of ammonia.In a footnote the authors state ethylnitrotoluidine (Gattermann,Abstr. 1885 975) can be obtained by nitrating ethylacetotoluide in4 parts of sulphnric acid and subsequently saponifying; if largerquantities (20 parts) of sulphuric acid are employed appreciablequantities of the meta-derivative are also formed. w. P. w.Action of Phenylhydrazine on Members of the CarbamideSeries. By S. SKINNER nnd S. RUHEMANN (Ber. 20 3372-3374).-When biuret is heated over a small flame with a slight excess ofphenylhydrazine ammonia is evolved and Pinner's phenylurazole(Abstr.1887. 1042) is formed to which the authors ascribe the con- .' CO*NH stitution NH< CO,Nph>.Diphewylcarbazide GO (NHaNHPh) is prepared by heating urethane(1 mol.) with phenylhydraxine (2 mols.) for some hours until theevolution of ammonia ceases. It melts at 151" is readily soluble inalcohol sparingly soluble in hot water insoluble in ether.Phen?lZsemithiocarbazide NH,*CS*NH*NHIPh formed by the action ofphenylhydrazine on monophenylthiocarbamide crystallises in whiteneedles melting a t 190° readily soluble in hot alcohol insoluble inwater. Ammonia nitrogen benzene arid aniline are formed in thereaction. N. H. M.Dyes which can be Fixed by Mordants. By S. V. KOSTANECKI(Ber. 20 3146-3149).-Very little is known of the connectionexisting between the constitution of organic colouring matters aridtheir tinc torial properties or what determines whether certain acidcolouring matters can be fixed by a mordant or not.Experimentswere made which seem to show that nitrosophenols can be fixed by a,mordant only when they are ortho-quinoneoximes and that otherphenol colours can do so only when they contain two hydroxylradicles in the ortho-position. All the dyes which are derived fromgallic acid for instance anthragdlol gallei'n coerulejin galloflsvinORGANIC CHEXISTRY. 275and gallocyanin owe their tinctorial value to the presence of theortho-hydroxyl-groups (see also this vol. p. 292). F. S. I(.Products of the Action of Nitric Acid on Aeetophenone. ByA. 3'. HOLLEMANN (Ber.20 3359-3362).-Eighty grams of fumingiiitric acid (sp. gr. 1.4) is added t o 10 grams of acetoyhenone andthe whole heated at 30-40" ; the liquid separates into two layers ofwhich the upper one becomes crystalline after one to two days. ThecrystJals are washed with water and extracted with boiling ether. Asparingly soluble nitrogenous substance melting at 177-179" remainsundissolved The ethereal solution yields cry stab of a compound,c(,N2O2(C0Ph) melting at 87" ; it is readily soluble in alcohol andether insoluble in water. When treated with potash or sulphuricwid it yields benzoic acid. It is reduced by zinc-dust and acetic acidto diphenylethylene diketone melting at 143" (not 140"). The com-pound contains no hydroxyl-group and can be boiled with aceticchloride for a day without change (compare Rec.Trav. China. 6 60).Methyl Duryl Ketone from Asymmetrical and SymmetricalDurene. By A. CLAUS and C. FOECKING (Ber. 20 3097-3104).-'Ihe durenes are best prepared as follows :-A mixture of 100 gramsof mesitylene (or pseudocumene) and 140 grams of methyl iodide isadded to 100 grams of aluminium chloride covered with carbon bisul-phide and the whole heated on a water-bath for five days. Theproduct is treated with water steam distilled and th4 distillatefractionally distilled. The three durenes are separated from onea110 ther by freezing.Unsymmetrical duryl methyl ketone C6HMe4-COMe [Me4 COMe =2 3 4 G I] is prepared in the usual mauner by means of alum-inium chloride and forms a colourless strongly refractive liquid ofa peculiar odour boiling a t 253-255" (uncorr.) ; it is readily solublein the usual solvents except water.It distils without decompositionwith superheated steam. The phenylhydrazine compound formslnstrous yellowish. matted needles which decompose at 215" withoutprevious fusion. The lLydroxylarnine-derivati,ue crystallises in smnllplates melting at 148". When the ketone is reduced with elm-dustand alcoholic potash the carbinol CsHMea*CHMe*OH is obtained ;it is a pale-yellow liquid and boils at above 300".2 3 4 6 Tetranzethylphenylglyoxylic acld C6HMe4.CO*COOH,is formed when the ketone ia oxidised with potassium permauganafein dilute aqueous solution in the cold. It is a bright yellow oil,readily soluble in alcohol and ether sparingly soluble in water,When kept in a freezing mixture for months it solidifies.Boilingwater decomposes it. The sodium salt (with 5 mols. H20) the potas-sium and barium (with 5 mols. H,O) calcium (with 3 mols. H,O) andother salts were prepared.2 3 4 6 Tetrametl~ylrr~andelic acid C6HMe4-CH(OH)*COOH isprepared by reducing the glyoxglic acid with sodium-amalgam. Itorystallises in short colourless transparent lustrous prisms meltingat 156" ; it dissolves readily in alcohol and ether sparingly in water.The sodium (with 1i mol. H20j and potassium salts are very readilyN. H. M27G ABSTRACTS OF CHEJliCAL PAPERS.soluble in water ; the calcium salt (with 8 mols. H,O) crystallises intufts of needles ; the barium salt (with 3 mols.H,O) forms aniallcrystals readily soluble in water.Xymmetriral duryl methyl ketone C6HMe4.COMe [Me4 COMe =2 3 5 6 13 crystallises in white lustrous plates melts a t 63"(uncorr.) boils a t 251" (uncorr.) and distils with steam. The hydr-mine-derivative forms small lustrous crystals which a t 225" decomposewithout melting. The curbinol crystallises in white plates whichmelt a t 72".Symmetrical d u r y l g l y o ~ y l i c acid crystallises in small white lustrousscales which melt a t 124" (uncorr.) ; it is readily soluble except inwater and cannot be distilled. The alkali salts are very readilysoluble; the potassium with 5 mols. H,O the calcium with 9 mols.H20 the barium with 3 mols. H20 and the silver stclts are described.2 3 5 6 Tetranzethylmandelic acid C,HMe,*CH(OH)-COOH,melts a t 146" (uncorr.) dissolves readily in alcohol ether benzene,&c.The alkali salts are very readily soluble and can scarcely beobiained crystalline; the barium salt with 2 mols. H20 and thecalcitm. salt with 8 mols. H,O were prepared ; the latter crystallisesin small slender needles.2 3 4 6 Teti-umethyZ~~r2xo.i~ acid C6HMe4-COOH and the2 3 5 6 acid are obtained by oxidising the corresponding duryvlmethyl ketones with warm permanganste solution. The former is athick oil whilst the latter crystallisea in plates of a Bilvery lustre,melting a t 109" (uncorr.). N. 8. M.Nitrile of Salicylic Acid. By F. TIEMANN (Bey. 20 3082-3084).-XalicyZic acid nitrile is prepared from the aldoxime ofsalicaldehyde or by distilling the thiamide of salicylic acid.Itmelts at W dissolves readily in alcohol and ether rather sparinglyin water behaves towards alkalis like a phenol and gives a reddish-violet coloration with ferric chloride ; under diminished pressure itdistils almost without decomposition and can be readily convertedinto salicylic acid. The compound prepared by Grimaux (Bull. 8oc.Chirn. 13 25) by fusing salicylamide with phosphoric anhydride,which melts a t 195" is therefore not the normal nitrile of salicylicacid (compare also Ahrens this vol. p. 266). N. H. 11.Condensation-products from p-Anilido-acids. By A. REISSERT(Be+. 20 3105-3110).-P-Bnilido-acrylic add NHPh.C,H,*COOK,is obtained by boiling the mixture of anilidomnle'ic-anilide andanilidomalei'c acid (formed from aniline and dibromoeuccinic acid,Tiemann and Reissert Abstr.1886 551 ; Michael Abstr. 1886 698 ;and Reissert Abstr. 1886 791) with aqueous potash. The productis precipitated with acetic acid dissolved in absolute alcohol andconverted into the sodium salt. It melts with partial decompositiona t 194" dissolves readily with alcohol and acetone and is almostinsoluble in water benzene and chloroform. The sodizcm salt with2k mols. H,O crysdallises in white plates of a silky lustre ; the ethylsalt melts at 143-144"CO*CH ~I-~etodihydroquinoline C6H4<NHmc H> is formed when p-anilido-acrylic acid is dissolved in concentrated sulphuric acid or when tbeacid is heated for a short time a t '200'.The product is severaltimes dissolved in acetone and precipitated with water and is thencrjstnllised from alcohol from which it separates in gold-colouredplates melting a t 255". When distilled a small amount is obtainedcolourless. It is very sparingly soluble in the usual solvents and isalmost insoluble in acids and alkalis. When distilled over heatedzinc-dust quirioline is formed. N. H. M.Formation of Anilic Acids from Anhydrides of BibasicAcids. By R. A;"r.scaU~z (Ber. 20,8214-3816).-Eumaranilic acid,COOH CH CH*CO*NHPh identical with that prepared from malein-itnil is formed when ma!eic anhydride dissolved in ether is mixedwith aniline.Mesaconanilic acid prepared from citraconic anhydride melts a t152-15:3" and is identical with the product which separates when anaqueous solution of moilaniline citraconate is kept.The anilic acid from itaconic anhydride melts a t 151-151*5" ; it isnot identical with the acids obtained by Gottlieb and by Michael byhesting itaconic acid with aniline and by boiling an aqueous solutionof monanilino itaconate.N. H. M.Hydrazocumic Acid. By N. MOIXANOFFSKI (Chenz. Celztr. 1887,1168 from J. l h s s . Cl/,enz. Soc. 1887 295-297) .-Nitrocurnic acidwas reduced in alkaline solution by an excess of sodium amalgamand the reduction products (mostly the azo- and hydrazo-acids) pre-cipitated by adding hydrochloric acid. They were separated bycry stallisation from alcohol the hydrazo-acid being much less solublein this medium. Hydyazocuuzic acid forms coloiirless needles verystable when dry but in solution slowiy changing into the azo-acid,nearly insoluble in cold alcohol more readily soluble in hot alcohol,still more readily in hot methyl alcohol insoluble in ether.Bitricacid reach with it in the same way as with the azo-acid. Whenheated with concentrated hydrochloric acid in sealed tubes a t100-115" it partly dissolves with a violet colour. Prom the solution,;I white crystalline substance separates after some time which iseasily soluble in alcohol dilute hydrochloric and nitric acids and inconcentrated sulphuric acid. Salts of the azo-acids crybtallise outfrom the solution of the hydrazo-acids in alkalis and these efflorescewhen exposed to the air.Synthesis of Phenoxycoumarin.By A. OGLIALORO (Cherrz.Cewtr. 1887 1164 from Rend. Ace. Sc. NapoLi [2! 1 90-91).-Theituthor has already shown that phenylcoumarin is formed by theitction of sodium a-toluylate on salicaldehyde and acetic anhydride(Abstr. 1880 164)) and phenoxyuinnamic acid by the action ofsodium phenylglycolate on benzaldehyde and acetic anhydride,(Abstr. 1881 276). By heating acetic anhydride (100 grams) salicyl-aldehyde (25 grams) and sodium phenylglycolate (40 grams) for eightThe sodium salt contains 1.2 mols. H,O.J. W. 278 ABSTRACTS OF CHENICAL PAPERS.hours at 150-160" phenoxycou.marin Cl5HI0Oj is formed. I t crystal-lises in small yellow prisms mqlts at 113' (uncorr.) is nearlyinsoluble in cold very sparingly soluble in hot water more readily inalcohol sparingly in ether and light petroleum very readily in chloro-form and benzene.An alkaline extract from the crude product ofthe reaction when acidified gave a brown precipitate that crystallisedslowly. From this an acid crystallisiog in yellow needles and meltingat 175" with decomposition could be separated but has not yet beenfully investigated. J. W. L.Derivatives of E thy1 Quinoneparadicarboxylate. By A.HANTZSCH and A. ZECKENDORF (Ber. 20,2796-2801). -The compoundC12H&1206 obtained by the hydrogenation of ethyl dichloroqninone-dicarboxylate (Abstr. 1887,727)) wad shown by Lahman as quoted bythe autbors (Her. 20 1313) to exiat in two forms. The first ofthese crptallises in colourless radially grouped needles destitute offluorescence and melts at 123" to a green liquid ; the second formedfrom the preceding by rapid cooling of the fused substance crystal-lises in greenish-yellow dichroic tables which are stable at theordinary temperature but are very readily transformed by gentleheating into the original colourless needles. The former representsthe stable modification and is regarded as ethyl dichloroquinoldicarb-tmyhte C6(OH),C12(COOEt)2 whilst the latter is the labile form and isregarded as ethyl d ichloroquiiionedihlldrodicarboxylate,CsH2C1,02( COOEt),.I n the case of the compound CI2H,,Os from which the compoundG12H12C1206 is derived by chlorination and hydrogenation the order isreversed ethyl quinonedihydrodicnrboxylate the coloured compound,being the stable and ethyl quinoldicarboxglate which is colourless,the labile form (ibid.).It is now shown that tohe dichloro-acid come-spondiug with these salts also exists in two modifications-one colouredand the other colourless.When colourless ethyl dichloroquinoldicarboxylate is treated inthe cold with concentrated aqueous fioda a greenish- yellow sodiumsalt is obtained In aqueous solution this also is greenish-yellow andyields the unaltered ethyl salt on treatment with hydrochloric acid.If however the alkaline solution is saponified on a water-bath evapo-rated nearly to dryuess and the sparingly soluble residue dissolved inwater and acidified a pale yellow solution is obtained which by rapidevaporation yields dichloroquinonedihydrodicarboxylic acid,C6H2t%02( COOH) + 2H20,in the form of greenish-yellow needles.These are stable in the air,but effloresce on exposure over sulphuric acid yielding dichEoroquin.oZ-dicurbozylic acid; the stable form is a white anhydrous powder,which on heating carboniseg without fusion or change of colour issparingly soluble in alcohol and ether almost insoluble in water andpames into the labile form only by heating with aqueous soda andacidifying the solution since it does not directly combine with theelements of waterORGANIC OHEXISTRY. 2179Hihherto compounds of this type have been known to react. as ifthey possessed only one of the two formuh ascribed to them. Arrexamination of ethyl tetrahydroxytereph t halate (dbstr. 1886 1028)shows however that it sometimes reacts as if i t were this compound,and a t others as if it had the composition of the yellow stableethyl dihydroxyquinonedihydrodicarboxylate C6H2( OH),02( COOEt),.Thus when heated with acetic anhydride it is converted into :ttetracetyl-derivative C6(OAc),(C00&) a white microcrystallinepowder melting a t 202".If however the yellow salt is dissolved inconcentrated aqueous ammonia and treated with hydroxylamine ityields the dioxirne of ethyl dihydroxyquinonedihydrodicarboxylate,C6H2(OR)2(NOH)2(COOEt)2 as a yellow powder melting a t 156-15i"without decomposition and soluble in alkalis and ammonia. The verysimilar yellow stable ethyl quinonedihydrodicarboxylate on thecontrary does not react with hydroxylamine under the conditionsjust stated but yields a colourless diucetyl-derivative of ethyl di-hydroxyterephthalate when heated with acetic anhydride.Moreover,the compound C6H2o4( CoOE t ) 2 (Abstr. 1886 358) reacts as if itwere ethyl dihydroxyquinonedicarboxylate since it yields withhydroxylamine the dzoxinze C,(OH),(NOH),(COOEt) ; this is ayellow powder which melts a t 160" with decomposition and is verysparingly soluble in alcohol and ether soluble in hot chloroform andacetic acid.When ethyl succinosuccinate is treated with bromine in molecularproportion and particularly when the bromination proceeds rapidly acompound which crystaliises in yellow needles is present in themother-liquor from ethyl q uinonedil~ydrodicarboxylate. This is ahydrate of ethyl quinonedihydrodicarboxylate C1.'H1406 + 2H,O.Itmelts a t 113" and is slowly converted into the anhydrous cornpoundby recrystallisation or more rapidly by boiling its alcoholic solution.I n its fluorescence colour reactions with ferric chloride &c. it re-sembles the anhjdrous salt but diffew from it by yielding on treat-ment with hydroxylamine in ammoniacal solution ethyl quinoltetru-hydrodicwboxylate C,( OH)2&(COOEt)2 a yellow crystalline substancePreparation of Orthosulphobenzoic Acid. Rp N. R. BRACKETTand C. W. HAYES (Amer. Ckem. J. 9 399-496).-The preparation oforthotoluenesulphonic acid from paranitrotoluene by the diazo-reaction is not satisfactory as the greater portion is converted intoan ethoxy-compound. Haller's method (decomposition of the hydr-azine compound by copper sulphate) is much better.Hycirazineorth.otoZuer~esu~honic acid N2~3*C6H31Vle*S03'~ prepared by the usualmethods ciystallises in scales is soluble in hot water and has acidproperties. With copper sulphate it decomposes readily but the ortho-toluenesulphonic acid is not easily purified and is not readily oxidisedby potassium permanganate except in alkaline solution ; moreover theyield of the benzoic acid is not satisfactory. Again sodium ortho-toluenesulphonate as prepared above does not give a good yield oforthotoluenesnlphonamide and this last when oxidised gives a fairyield of the sulphinide but little of orthosulphobemoic acid.melting at 128". w. P. w280 ABSTRACTS OF CHENI JAL PAPERS.The best aiid quickest method of preparing this compound is thatof' Noyes (Abstr.1886 604) by the action of chlorvsulphonic acid ontoluene; a mixture of the partt- and ortho-compounds is obtainedwhich is best converted by ammonium carbonate into the toluene-sulphonamides ; by treatment with potassium permanganate the para-coinpound is oxidised to parasul phobenzoic acid and is precipitatedby addition of dilute hydrochloric acid whilst from the filtrate stronghydrochloric acid throws down the orthobenzoic sulphinide. Thisrnay then be converted into orthosulphobenzoic acid by evaporatingwith hydrochloric acid; the residue is extracted with water fromwhich the substance separates in large rhonibic crystals; a b c =0.5507 J 1 0.8121.H. B.Paramido-orthosulphobenzoic Acid. By W. A. HEDRICK (Amer.Chem. J. 9 410-418).-P~aranitro-orthotoluenesulphonic acid isoxidised by potassium permanganate in alkaline solution and tjhe para-nitro-orthosulphobenzoic acid precipitated from the filtered and concell-trated solution by hydrochloric acid. The reduction of the nitro-groupis effected by ammonia and sulphiiretted hydrogen ; the yield of thepure amido-acid amounts to one-half the weight of the nitrotolueneused. The following salts are described [ COOH-C,H3(NHz)-S03],Bn +5Hz0 ; C7H5NS0,Ha + H,O ; C7H,NS05Pb ; and CiH5NSO58gz. Thesilver salt when boiled with methyl iodide and then with water andcalcium carbonate yields A compound N&h3~'C6H3<Coo>c~ SOd- whilstethyl iodide and barium carbonate yield a neutral salt,[ CO OEt.C,H (NH,) * S 03]?Ba.The free amido-acid has no basic properties and no acetyl or benzoylcompound could be obtained from it.Paradiaxo-orthosulpla~ben~oic acid COOH c6H3<z&> is best ob-tained by passing nitrous anhydride into a solution of the acid bariumsalt containing Rome of the same salt in suspension; it Reparatesin white crystals.It may be converted into a well-crystallisedhydrazine-compound in the usual way. The diazo-compound whenboiled with water yields hydroxysuZpphobenzoic acid of which the follow-ing salts are described:-[ COOH.C,B3(OH).S03]LBa ( C7113SOa),Ba3 and C,H,SO,Ca + 5H,O ;the last salt crystallises in the tr&hic pystern; n b c =0.9567 1 1.0121 ; observed faces cmPq mPw cmP and OP.H.B.Metacresolsulphonic Acids. By A. CLAUS and J. KRAUSS(Ber. 20 3O89-3095) .-1CZetac~esolya~asuIlphonic acid,OH*C,H3Me*SO3H [OH Me SO,H = 1 3 41,is obtained by heating sulphuric acid and cresol (equal weights) at100-120" for some hours. The reaction also takes place at theordinary temperature but requires three or four days. It ciytallisesfrom dilute sulphuric acid in colourless plates (with 2 mols. HzOORGXSIC CHENISTRT. 281melting a t 75" (uncorr.) and from concentrated sulphuric acid inlarge colourless plates (with 14 mol. H?O) which melt a t 95-96"(uncorr.). The anhydrous acid melts at l l s " and dissolves verv readilyin water alcohol ether and benzene. The potassium salt (with2$ mols. H,O) forms stellate groups of small crystals of a fatty lustrereadily solnble in water; the sodium and Zead salts are also r~arlilj-soluble in water.The copper salt (with 3 mols. € 3 3 0 ) crystallises inh f t s of lustrous pale-yellow prisms rat her readily soluble in water.The sulphochloride C,H,O-SO,CI forms a thin honey-coloured syrup.The sulpJionanaYde is readily soluble in alcohol and ether ; i t does notcr.ystallise. When a dilute solution of the sulphonic acid is heatedwith chromic acid toluquinone is formed.~~eetacresoZdisulpJ72onic acid is prepared by heating metacresol withsulphuric acid (4 to 6 parts) a t 120-140" for some hours and formsan oily liquid readily soluble in water and alcohol soluble in etherand benzene. The potassium saZt crystallises wit'h 3 mols.H,O incolourless plates of a fatty lustre ; the barium salt (with f mol. HJ))is very readily soluble; the Zead salt is a readily soluble slightlylustrous crystalline powder. The copper salt is extremely soluble.The disulphochloride is a thick honey-coloured liquid. The disulphon-amide is also a syrup.Metac~esoltrisulphonic acid is formed when the cresol is heated withfuming sulphuric acid and phosphorus pentoxide at 180". The bariumsalt is very readily soluble in water. N. H. M.Orthocresolsulphonic Acids. By E. HANTKE (Ror. 20 3209-3213).-When orthocresol is heated with sulphuric acid for five to sixhours on a water-bath Enqelhardt and Latschinoff's sulplionic acid(Zeitsch. f. Chem. 1869 621) is formed. The potassium sslt crystal-lises with + mol.H,O. 'The acid has the constitution-[Me:OH:SOsH = 1 2 4 ] .The same acid is formed together with Neville and Winther's sul-phonic acid [Me OH S03H = 1 2 51 (Bey. 13 1946) whenorthocresol is treated with sulphuric mid in the cold. The 1 2 5 acidforms deliquescent needles. N. H. M.Synthesis of Anhydrides of Aromatic Sulphinic Acids. ByR. Owo and A. MILCH (Rer. 20 3337-3338).-1n a previous paper(Abstr. 1885 1231) Otto and Rossing showed that when an alkylchlorocarbonate is allowed to act on an alkaline sulphinate an aikJlsulphinate and carbonic anhydride are formed. The authors now findthat a similar reaction takes place when carbonic oxychloride issubstituted for the chlorocarbonate. Phosgene gas and sodium benzene-sulphinate yield carbonic anhydride sodium carbonate and benzene-sulyhinic ailhydride (C,&SO),O.This conipound is soluble in ether,b u t is decomposed immediately by water and alcohol forming theacid or the ethyl salt respectively. L. T. T282 Al3STRACTS OF CHEMICAL PAPERS.Sulphoneketones. By R. and W. OTTO (J. pr. Chem. [2] 36,401-432).-Phenylsulphon~cetone behaves as a ketone formingwith sodium hydrogen snlphite colourless tabular crystals of a doublesalt ; with hydroxylamine mono- or tri-clinic needles of phenylsul-phonacetozime 0H.N CMe*CH2-S0,Ph melting a t 147-148" ; withammonia tabular crystals of phenylsulphonacetonamine,NH CMe*CH2SOzPh*Me,melting a t 110-11 1". With phenylhydrazine it yields pale-yellowneedles melting a t 129" of formula N2HPh CMe*CH2*SOZPh andwith thiophenol it forms needles of phenylsulphonacetone mercnptole,CMe( SPh),*CH2*S02Ph melting at 103-104".When oxidised itvields acetic acid benzenesulphonic acid and carbonic anhydride.When reduced by hydrogen in an acid solution phenyl mercaptan andisopropyl alcohol are formed ; in an alkaline solution benzenesulphinicacid and isopropyl alcohol. With bromine it yields phenylsuZphone-bromacetona crystallising in colourless silky needles soluble in hotalcohol and melting at 96" and pheny lsulphonedibromacetone also incolourless needles me1 ting a t 113-1 14". With potassium hydmxide,it yields potassium acetate and methylphenylsulphone.1)iphenylsulphonacetone has the symmetrical constitutionCO(CH,-S&ph')2 for yt is conveheh by potas&um hydroxide intopotassium phenylsulphonscetnte and methylphenylsulphone. Di-phenylsulphonacetoxime 0H.N C( CH2*S0,Ph) obtained by heatingthe above compound with hydroxylamine hydrochloride crystallisesin rectangular tables melting izt 1.76-137".The phenylhydrazinecompound forms yellow needles melting at 171". With thiophenol,diphenylsulphone rnercaptart is formed as a fine lustrous crystallinepowder insoluble in water melting a t 190-191".A briphenylsulphone-derivative was not obtained by acting onphenyldibromacetone with sodium benzenesulphinate.Parato1 y Zsu Zphonacetone COMe CH,. S02*C7 H forms long silkyneedles soluble in alcohol benzene and chloroform and melts at $1"The bromo-derivative GH,Br*C0.CB,*S0,.C7H7 cryshallises in needlesor rectangular plates melts at i29-13Oo and is sparingly soluble inhot water,Diparatoly lsulpkonaeetone CO ( CH2* S 0,.C7H7) forms white,rhombic tables melting a t 152" ssluble in hot glacial acetic acid andin chloroform. Paratdylsnlphonephenylsulphonacetone,C7H,*S0,*CH2*CO*CH,*S02Ph,prepared by the action of paratolylsulphonebromacetone on sodiumbenzenesulphinate crystallises in rhombic plates and melts a t 112".Calcium phenylsulphonacetate crystallises with 24 mols. H,O insmall needles the lead salt with 2 mols. H 2 0 ; the silver salt whenheated yields methylphenylsulphone and not diphenylsulphonacetoneas was expected. A. G. B.Ethereal Salts of Benzoic Sulphinide. By R.N. BRACRETT co (Amer. Chem. J. 9 406-410).-The methyl salt C6H,< SO,>NMeORGANIC CHEMISTRY. 283is obtained from methyl iodide and the potassium or silver salt. Itcrystallises from alcohol or hot water in flat needles melting a t 131-132". The ethyl salt C7H4S03NEt melting at 96-97" (Fahlberg andList give 93-94") is prepared in like manner; at the same timesome ethyl orthosulphamine benzoate is formed. The propyl saltmelts a t 60-70".When benzoic sulphinide is treated with phosphorus pentachloride,and methyl alcohol added in the cold a crystalline substance is pre-cipitated probably c"~"<~-,i >NH ; when this is boiled withmethyl alcohol it dissolves and the solution on cooling yields firstcrystals of an acid melting above 330" and then crystals melting atso,2C ( OMe)2123-125" ; the latter is the dimethyl ether C6H4< so ->PIT=,of Remsen and Palmer and when boiled with water and bariumcarbonate yields the barium salt of benzoic sulphinide.H. B.Aromatic Lead Compoupds. By A. POLIS (Bey. 20 3331-3336).-The author has obtained lead tetraphenyl (Abstr. 1887 572)in measurable crystals. These crystals are colourless prisms belong-ing to the tetragonal system; axial ratio a c = 1 0.3808. Thecorresponding tin compound gives a c = 1 0.38935. Silicontetraphenyl gives a c = 1 0.43969. The three compounds areisomorphous the valne of the principle axis decreasing with theincrease of atomic weight of the grouping element. Lead diphemy2dichZoride PbPh2CI2 is formed by the action of chlorine on ft carbonbisulphide solution of lead tetraphenyl or from the nitrate (Zoc.eit.)by precipitation with potassium chloride. It is a white powder,insoluble in alcohol and ether sparingly soluble in chloroform benzene,and carbon bisulphide. The oxide PbPh20 obtained by the act'ion ofsoda on an aqueous solution of the nitrate is a white powder whichdoes not fuse without decomposition. It does not seem to form ahydroxide but is strongly basic i n character and dissolves in acids t oform salts. The acetute PbPh2(OAc) + 2H20 forms long colourlessneedles ; the formate PbPhz(CHO2) + H20 colouriess needles ; thebasic cyaqide PbPh,Cy*OH a white powder ; the thiocyannte,PbPh,( CNS) and the phosphate (PbPh,),P208 white flocculent pre-cipitates ; the basic carbonate (PbPh2*OH)&03 a white powder andthe chromate PbPh2CrOd a yellow precipitate which when crystal-lised from a mixture of alcohol and benzene yields yellowish crystals.L.T. T,Methylketole. By E. FISCHER (Annulen 242 372-383) .-Many of the compounds mentioned in this paper have been previouslydescribed by the author (Abstr. 1887 265). Benzylidenemethylketole,CHPh(C9H8N) begins to melt at 242" and melts completely at246-247'. In the crystalline state this substance is sparingly solublein the ordinary solvents with the exception of acetone. The amor-phous precipitate which is formed when water is added to the solutioni n acetone is fkeely soluble in ether and alcohol but it soon changes t284 ABSTRACTS OF CHEMICAL PAPERS.the less soluble form.On oxidation dimethylrosindole is producecl(Abstr. 1887 588).Metanitrobemaldehyde and methylketole readily unite form inqni~tanitrobei~z!llidel.!emeth?ll7cefo7e. This substance is soluble in acctone,melts a t ?63" arid yields a red colouring matter on oxidation. Whrnrcduced with zinc-dust and ammonia it is converted into mefamido-benz~/Zitbr)enzeth?/lketoZe NH2.C6H,-CH(C9H8N),. This base is solublein ether alcohol and benzene. The preparation of efh~~lidenemetliyl-I,-eto7e CHMe(C,H,N) from paraldehyde zinc chloride and methyl-ketole has already been described (Abstr. 1887 265). It melts a tlYl" and boils with slight decomposition. It is freely soluble inalcohol ether and acetone.Bg acting on methylketole and phthalic anhydride with zinc chlo-ride a t loo" a compound of the composition C17H,,N0 is obtained.It forms colourlesa prisms and dissolves in hot alcohol and acetic acid.The acid melts above moo and completely decomposes a t a highertemperature.The author. is of opinion that the acid may have theformula C9H,N-COGsH4-COOH.In the presence of zinc chloride 1'-methylindole and phthalic an-hydride unite to form phthalylmethylindole C26H,oN,0,. The newcompound crystallises in prisms melts a t 300" and dissolves in hotacetone. w. c. w.Azo- and Amido-derivatives of Methylketole. By P. WAGNER(Annalen 242 383-388) .-The preparation of methplketoleazo-benzene C8H,N(Me)N,Ph has been already described (Abstr. 1887,265). Onreducing the alcoholic solution with t'in and hydrochloric acid anilineand amidomethyl ketole are foitmed. The ketoIe crystJallises in platesand melts a t 112-113".It is soluble in alcohol ether chloroform,and light petroleum. The liydrochloritle crystallises in prisms whichturn pink on exposure to the air. When reduced with zinc-dust andhydrochloric acid amidomethylketole yields first methylketole andthen hydromethylketole. On oxidation with ferric chloride amido-nietliylketole yields a mixture of two compounds one of which is verysolutde in alcohol. The other is less soluble in alcohol crystallises inplates and has the empirical formula CgH7N0. It melts a t 22.5" withpartial decomposition.When dry hydrogen iodide is passed into an ethereal solution ofmethylketole an amorphous precipitate ( C9H9N,HI) is produced.The compound is decomposed by water into its two components.Derivatives of p-Naphthindole.By A. STECHE (Annalen 242,367-3'1) .-p-hiayhtli ylhydrazinelevulii~ic acid is deposited as acrystalline precipitate on the addition of water to an alcoholic solutionof levulinic acid and p-naphthylhydrazine in their molecular propor-tions. At 170" the acid is converted into the an7ydride. Thissubstance melts a t 119" and is deposited from hot alcohol in needle-shaped cr-y stals. Et h y l nup hth y lhy drazilze7evulin ate is formed by thedirect union of ethyl levidinate with /3-naphthylhydrazine. It iscrystalline and melts at 129-130". It is converted into methgi-/3-The compound is soluble in alcohol ether and benzene.w. c.wORGANIC CHENISTRY. 285NH naphthindolacetic acid C,,H,<CMe>C*COOH by the action of zincchloride a t 130-135'. This acid is freely soluble in alcohol ether,acetone and acetic acid. The silver salt is decomposed by boiling inwater forming a metallic mirror.The acid decomposes at 210" yielding carbonic anhydride and~ i m e t h y 1-P-ra~jhthindole CI,NH,Mee [Me = 2" 3"]. The latter com-pound melts a t 126" and dissolves freely in alcohol and acetic acid.It yields a dark-red picrate and a crystalline nitrosamine and gives acharacteristic blue coloration with acetic acid and ferric chloride. Onreduction with zinc-dust and hydrochloric acid hydrodimethyz-P-naphthindoze is produced. This base is an oily liquid which turnsred on oxidation. The platinochloride is crystalline and is decom-posed by boiling water. w.c. w.Hydroxydiphenyl Bases. By A. WEINBERG (Ber. 20 3171-31 78) .-ianzidohydroxydi~h~n~lsu~ho?iic crcid,OH-C,,H,(NH,),.SO,H [OH NH SOsH NH = 3 4 6 4'1,is prepmed by reducing with stannous chloride a t a temperature notexceeding 30" 300 grams of sodium benzene-azopamphenolsulphom i edissolved in 500 C.C. of water. Aftor 12 hours the product is treatedwith hydrogen sulphide filtered and evaporated to a small bulk ; thehydrochloride of the sulphonic acid separates in large clear crystals.The free sulphonic acid crystallises in needles from water whichdissolves it readily.D i a m i d o h y d r o x ~ d i p h e r ~ l C,,H,(NH,),*OH [= 4' 4 33 is formedwhen diamidohydroxydiphenylsulphonic acid hydrochloride is heatedwith water at 180".It crjstallises in colourle~s plates melting at,185" and is almost insoluble in water readily soluble in dilute causticalkali solutions. The alkaline solutions oxidise quickly when expostbdto air.Diamidolzydrox~phen~ZtoZ~lsu~ho~i i c acid 0H.C 12H5Me ( NH2),*S O,H[NH Me OH NH S03H = 4' 3' 3 4 61 is prepared fromthe dye obtained from ortliotoluidine and paraphenolsulphonic acic .It crptallises in colourless needles which decompose when heated.It dissolves sparingly in water readily in acids and alkalis.Diamidohydmayphenylfolyl NH,-CcH3Me.C6H,(NH,)*OH preparedby heating the sulphonic acid with water a t 180° crystallises fromwater in lustrous plates melting a t 177" ; it dissolves readily in diluteaqueous potash sparingly in ether and benzene. The sulpliate isalmost insoluble in water more soluble in dilute acid.Diamido-~thorydi~henylsu~honic acid C12H16N2S01 is obtained byreducing sodium benzene-azophenetoilsulphonate.It crystallises inneedles sparingly solubie in cold water. The hydrochloride (with2 niols. H,O) is readily soluhle.Diamido-ethoxydiphenyl Cl4HlZO(NH2) is prepared by heating theabove snlphonic acid with water a t 170" for 8 to 10 hours; i tforms flat lustrous needles which melt a t 134-135" dissolves sparinglyin water ether and benzene readily in alcohol. When heated withh.ydrochloric acid diamidohydroxydiphenyl (m. p. 185") is formed.The hydrochloride is very readily soluble.VOL.LIT. Z286 ABSTRACTS OF CHEIIIICAL PAPERS.The suZphate crystallises in prisms sparingly soluble in water readilyin hydrochloric acid.Diamido-etho~pheny ItolzJlszL~holzic acid is sparingly soluble in water.The hydrochloride forms large prismatic crystals (with 4 mols. H,O).The barium saZt (with 8 mols. H,O) crystallises in concentricallygrouped needles.~inmido-etAozy~henyZtoZ?;ll C,,H,,N,O cryRtallises from water in flatneedles melting a t 117.5"; it is sparingly soluble in water coldalcohol ether and benzene. When saponified it yields diamido-hydroxyphenyltolyl melting a t 177".Diwmido- ethoxy n aph t7zyZph ew y 1 NH2.C6B,*C ,,H5 ( OE t ) *NH2[NH CIZHI2NO = 1 4; C,H,.NH OEt NH = 1 3 41,is prepared by dissolving benzene-azo-P-naphthol in the equivdentamount of alcoholic potash adding ethyl bromide and boilingthe whole for 24 hours under a slight pressure When cold it isfilf ered and evaporated down when the benzene-azo-P-naphthyl-ethyl oxide remains as a dark-red oil. This is reduced with stannouschloride.The diamide melts a t 72" dissolves readily in alcohol,ether and benzene ; the alcoholic solution shows a greenish-blue theether and benzene solutions a violet fluorescence. The normal sulphnteis sparingly soluble in water ; the hydroc7doride crystallises in needlesof a silky lustre. N. H. M.Dinitrobenzidine. By E. v. BANDROWSKI (Monatsh. 8,471-474).-By the hydrolysis of dinitr~dipht~halylparabenzidine with sulphuricacid at 130" two di.nitrobenzidines are produced together with phthalicacid. One modification less soluble in ammonia forms long needlesmelting a t 21@-221" and decomposing when heated with explosion.The more soluble modification forms saffron-yellow needles melting a t196-197" ; it is also distinguished from its isomeride by its greatersolubility in aicohol and dilute acids. A dinitrobenzidine has pre-viously been described by Strakosch who obtained it by the nitrationof acetylbenzidine ; this has been shown by Brunner and Witt to bean ortho-derivative.From its method of formation it would seemthat this compound is identical with the isomeride melting at 218-221" described above although Strakosch assigns a melting point ofover 300" to the substance.However the identity of the two sub-stances is confirmed by the formation from both of them of the sametet ramidodiphen yl. V. H. V.Bases produced by Nascent Formaldehyde. By J. TR~GER(J. pr. Chem. [2] 36 225-245).-A crystalline monacid base pro-bably CH,( CH:N-C6H4Me)2 is produced by the action of nascentformaldehyde on paratoluidine ; it melts at 134" dissolves in alcohol,ether &c. but is insoluble in water; it forms a crystalline hydro-chloride sulphate platinochloride and picrate. When treated withnitrous acid carbonic anhydride and nitric oxide are evolved and acompound having the formula C,,HlSN4O2 is formed ; this substancedissolves in acetic acid but is insoluble in alcohol ether water anORCIASIC CHEMISTRY. 287concentrated hydrochloric acid ; it melts at 260-264" with decompo-sition gives Liebermann's reaction and also the nitric acid reactionwith ferrous sulphate.A very similar product is obtained whenthe base is treated with nitric acid nitrogen dioxide and carbonicanhydride being evolved ; with acetic anhydride it yields a verystable compound Cc2H4,Na0,.Nascent formaldehyde and dimethylaniline yield tetramethyldi-amidodiphenylmethrtne from which a crystalline picrate and nitro-derivative CH2[ C6H(NOZ),.NMe2 J2 were prepared.Tetramethy ldiamidodipheny Zethane C2H4*( C6H4*NMez)z is producedTV hen dimethylaniline and carbon bisulphide are treated in alcoholicsolution with zinc-dust and concentrated hydrochloric acid; it is acolourless crystalline compound melts at 8 7" dissolves in ordinarysolvents but is insoluble in water; combines with methyl iodide,forms a crystalline picrate (melting at 190') and platinochloride andwith nitric acid yields dinitronitrosodimet hylaniline,N0.C6H2(N02)2*NMe2. F.S. K.Condensation Products from Paratoluidine and Paranitro-benzaldehyde. By A. BISCHLER (Ber. 20 3302-3306).-Whenparanitrobenzaldehyde paratoluidine and concentrated hydrochloricacid are heated together in alcoholic solution a-paranitrophen?y ldi-pararnidotolylmethane N02*C6Ha.CH( C6H3Me-NH2)2 is formed. Crys-t'allised from benzene this substance forms white needles of theformula 3C,,H,,N,O2 + C6Hs which lose their benzene at '110-120"and melt at 170-172". It is but sparingly soluble in alcohol andether easily in boiling benzene.Its salts crystallise with difficulty,ibnd are decomposed by water. The platinochloride C21H2,N3o2,H2PtCl6,forms yellow crystals soluble in boiling alcohol.When however pnranitrobenzaldehyde and paratoluidine areheated with strong sulphuric acid an isomeric compound P-yaranitro-phenyldiparamidotolylmethane is formed. It crystnllises in yellowscales melting at 126-127" and is easily soluble in cold benzene andboiling alcohol or ether. I t also is but a feeble base but its salts aremore easily crystallisable than those of the a-compound. The hydro-chloride forms yellow needles the p7atinochZoride yellow scales.The author believes the isomerism of these two compounds to bedue to the benzaldehyde nucleus displacing ortho-hydrogen atoms inthe toluidine in the a-case meta-atoms in the p- (sulphuric acid)condensation. L.T. T.Compounds of Ketones with Dimethylaniline and Diethyl-aniline. By 0. DOBNER and G. PETSCHOW (Annalen 242 333-348). -The formation of tetrame thyldiamidodiphenylpropane by theaction of zinc chloride on acetone (1 mol.) and dimethylaniline(2 mols.) has been already described by Dobner (Abstr. 1879,787). By a similar reaction tetreth~lldiamidodiphe~~yl~~G~ane,CMe2(C6H4-NEt2) has been prepared from diethylaniline and acetone.The base forms silky needles and melts a t 76". It is soluble in ether,carbon bisulphide benzene and light petroleum. The salts are very111. 288 ABSTRACTS OF CEEMICAL PAPERS.soluble and crystallise with difficulty.The hydriodide C2sHsNz 2H1,forms pale-yellow plates freely soluble in alcohol and in hotwater.Tetramethyldiamidotriphenylmethane is the chief product of theaction of zinc chloride on acetophenone and dimethylaniline. Tetra-metliyldiamidodiphenylmethane and triphenylbenzene are alsoformed.Tetramefhyl~~am~dotr~7~enylethane CMePh( C6H4.N&fe2) is a pale-yellow oil which gradually acquires a dark-red colour on exposure tothe air. It boils above 360" with part,ial decomposition; underreduced pressure it may be distilled without undergoing any change.It is non-volatile in steam and dissolves freely in ether benzene,light petroleum and wwm alcohol. The salts are very soluble inwater and do not crydallise. It yields amorphous precipitates withthe chlorides of gold platinum and mercury.An acetic acid solution of the base turns blue on the addition oflead or manganese peroxide.Benzoplienon e and dime thylaniline yield dim ethylamid o tri ph enyl-methane.Methyl hexyl ketone and dimethylaniline yield tetramethyl-diamidodiphenylmethane and a liquid base CI4Hz3N which is probablya hexyldimethylaniline. The chief product of the action of zincchloride on diethyl ketone and dimethylaniline is tetramethy ldiamido-B y C. -0 LLYANN (J. pr.Chem. [ 2 ] 36 246-272).-Diamido-derivatives of Iriphenylmethaneare produced by the action of benzaldehyde on a mixture of a suitablearomatic base a i d its hydrochloride. Aniline yields diamidotri-pheny1rnet)hane ; orthotoludine gives dia~idorthotoZylphenylmethane,a white microcrystalline powder whose melting point could not bedetermined.Paratoluidine yields diamidopa~ratolylphenylmethane which crystal-lises from a mixture of benzene and light petroleum with + mol.c6H6 in concentric groups of yellow needles and melts at 185-186" ; it is a.diacid amiae and forms a liydrochloride picmte,$c. The colourless crystalline acetyl-derivative C2,H,,(NHAc) meltsat 217-218" ; the beruoy Z-derivative C21Ht8(NHBz)2 melts a t 196".By means of the diazo-reaction diamidoparatolylphenylmethane canbe conrerted into the di-iodo-derivative C21H1812 crystallising inbrownish-red prisms and melting at 167-168". When distilled withzinc-dust it yields paratoluidine and methylacridine and therefore,probably has the constitution CHPh(C6H,Me*NH,) [Me CH NH,= 1 3 41 ; from its formation by the above method and as it canalso be obtained by Mazzara's and by 0.Fischer's methods it followsthat it is not necessary that the para-position with respect to theamido-group shoul d be free in order to synthesise amidotriphenyl-methane-deriratives.I n the preparation of the para-compound a substance of theformula cZlH16N2 is also formed; it crystallises in long nearlycolou .less needles melts a t 177-176" and gives an orange-yellow,crysta,Il ine platinochloride.diphen ylmethane. w. c. w.Derivatives oT Wq5henS;lrneChane.F. S. KORGANIC CHEMISTRY. 289Tetramethyldiamidothiobenzophenone. By 0. BAITHER (Ber.,20 3289-3298).-The author is inclined to think that this sub-stance which he previouslg described (Abstr.1887 SlS) is really athioketone and identical with the compound obtained by Fehrmann(this vol. p. 156) from auramine. He believes the differences ofproperties and melting points are due to want of purity and difficultyin exactly determining the melting point. He now gives the meltingpoint as 193-194..When the ketone is heated with benzoic chloride in carbon bi-sulphide solution a dic?~Zoro-derivative CC12(C6H4*NMe2)2 is formed,which is soluble in alcohol and glacial acetic acids sparingly so inbenzene and chloroform and when heated decomposes. Withwater it yields Michler s kekone CO(CsH4*NMe2)2 and is probably thecompound prepared from the latter. in the manufacture of auraminecolouring matters.With benzoic chloride,.the thioketone forms an additive derivative,CS( C6H4*NMe2)n,COPhCl. This subsbance is crystalline and meltsbelow 200° but was not obtained quite pure. It is soluble in aceticacid and in benzene. Alcohol and chloroform also dissolve it buta t the same time decompose it i n b its two constituents. Aceticchloride yields a similar derivative CS( C6H4.NMe,)2,COMeCl whichis crystalline and begins to decompose at 160". It is soluble inalcohol acetic acid chloroform and benzene.When the thioketone is heated with acetic anhydride and sodiumacetate it yields a compomnd CssH46N40~S of which the constitutionis probably s[C(C,H,*NMe,),*oAc],. It forms a green powder whichbegins to decompose at 120".When heated with aniline the thiokehone appears to yield chieflyMichler's ketone b u t with aniline hydrochloride it yields phenyl-auramine. The author found the melting point of the latter to be170-1 71".Phenylhydrazine appears to convert the thioketone intothe corresponding oxy- (Michler's) ketone.In his previous communication the author described the product ofthe action of nitric acid on the thioketone as trinitrodimethylaniline.He now finds however that it is the same compound,Go[ C6H2(NOz)z.NMe*N02]2,obtained from Michler's ketone. With hy droxylamine this compoundyields van Romburgh's compound' COrC6Hz(N02)2.NHMe]2. It is pro-bable that an oxime is first formed and is subsequently decomposed.L. T. T.Ring-formation with Elimination of Hydrogen Bromide orNitrous Acid.By E. LELLMANN and 0. SCHMIDT (Ber. 2 0 3 1 5 63157) .-When P-naphthyltlmine is treated with glycerol orthonitro-phenol and sulphuric acid it yields P-naphthaquinoline in which thecondensation has occurred at the 1 2 position ; it was thought that,by starting from a-bromo-P-naphthylamine in which the 1 positionis occupied the condensation would occur at the 2 3 positions.a-Bromo-P-naphthylamine [Br NH,=1 21 was obtained by brominat-ing P-acetonaphthalide ; i t was then treatled with glycerol orthonitro-phenol and eulphuric acid and the product of the reaction crystallise290 ABSTRACTS OF OEEMlCAL PAPERS.from light petroleum ; it melted at 93.5" and on examination it wasfound that p-naphthaquinoline had been formed with elimination ofhydrogen bromide.a-Nitro-6-naphthylamine when treated in asimilar manner yields the same compound with elimination of nitrousacid. The conclusion drawn is that the 6'-carbon-atom is far lessprone to ring-formation than the a-carbon-atom. The nitrophenoltakes no part in the reaction the result being the same whether it ispresent o r not. I?. S. K.Isomeric Naphthylaminesulphonic Acids. By G. SCHULTZ(Rer. 20. 3158-3162).-Bayer and Duisberg (this vol. p. 732)have stated that when P-naphthylamine is sulphonated a mixture ofsulpho-acids is obtained from which a hitherto unknown P-naphthyl-amine-b~iionosulphonic acid can be isolated ; this compound yields a/jl-naphthol-3-sulphonlc acid which is identical with Casella and Co.'snaphtholsulphonic acid F ; conversely by heating this acid with am-monia Bayer and Duisberg obtained a compound identical withP-naphthylamine-6-sulphonic acid.Weinherg and Lange (this vol.,p. 160) throw doubt on the identity of the acid which they themselvesobtained from naphtholsulphonic acid F and that prepared byBayer and Duisberg from p-naphthylamine. The author concludesthat Weinberg obtained an impure product only and gives proofs ofthe identity of the acids in question. F. S . K.Intramolecular Migration in p-NaphthylaminesulphonicAcids. By A. WEINBERG (Bey. 20,3353-3355).-When /3-napthyl-amine-a- and ysulphonic acids are added to sulphuric acid (3parts) previously heated at 160" and the whole kept at this teni-perature for 1$ hours they both yield as chief product the 2 2' acidtogether with the 2 3' acid. The same product is formed by sulpho-nating p-naphthylamine sulphate.It is possible that Bayer and Duis-berg's &acid (Abstr. 1887 732) really consisted of this mixtpre.(Compare Schnltz preceding Abstract.) N. H. M.Conversion of BTaphthylarninesulphonic Acid into Dichloro-naphthalene. By H. ERDMANN (Bey. 20,3185-3187) .-When Witt'snaphthdenedisulphonic acid (Abstr. 1886 554) is diazotised theproduct warmed with phosphorus pentachloride and then distilled,dichloronaphthalene [ 1 4'1 melting at 107" is obtained together withsome a-monochloronaphthalene. The yield of dichloronaphthalene is30 to 40 per cent. of the theoretical. N. Ef.M.Action of Bromine on Diamido-a-naphthol. By T. ZINCKEand C. GERLAND (Ber. 20 3216-3231 ; compare Abstr. 1887 838).-When bromine acts on bromamido-a-naphthaquinonimide or bromo-hydroxynaphthaquinonimide the main products are the tribromide,C,H,Br3N03 and the dibromide C,H,Br,O ; the latter meIts at 176",which is rather higher than the figure given by Kronfeld. I n thesecond case a small quantity of a third bromide melting at 130" isalso formedORGANIC CHEMISTRT. 291By t,he bromination of bromamidonaphthaquinone or of bromo-hydroxynaphthaquinone four brominated compounds are obtained ofwhich three are formed in very small quantity. Two of these are notyet worked out the other is identified as the dibromide CgH4Br202.The main product is a dibromo-compound C10H6Br201 dibromotriketo-hydronaphthalene hydrate C6H4< Br2,> ; this crystallises inmatted needles melts at 114-115" with decomposition is readilysoluble in alcohol chloroform and benzene less Yeadily in light petro-leuin and is soluble in alkalis with yellow coloration.It is readilyconverted into bromoxy-a-naphthaquinone and hypobromous acid,either when heated alone or when boiled with benzene toluene dilutealcohol or dilute acetic acid. When boiled with water carbonicanhydride is evolved and a- mixture of bromoxynaphthaquinone andthe dibromide C9H4Br20 separates. When dissolved in ethyl ormethyl alcohol and treated with hydrogen chloride chlorohydroxy-a-naphthaquinorie is formed. When boiled with aqueous potash ityields a monobromo-compound crystallising i n small nearly colour-less plates andneedles and melting at 118-119" and probably of theconstitution C6H4<- CO->CBr or C6H4< CO>CHBr probably dueCO*C(OH)C(0H) coto the decomposition of an acid C,3H4<-c0.cBr2-> C (OH) (COOH) firstformed and for whose existence some evidence is adduced.coac(0H)2> co-cc12 The corresponding dichloro-compound C6H,<pared in similar manner crystallises in thick white needles melts at105" without decomposition and is far more stable than the dibromo-compound.When treated with alkalis i t is converted into a crystal-line compound melting at 128-129" and if the alkaline solution isoxidised small lustrous plates melting at 124-125". The authors regard -C(OH)(COOH)GCi,> these substances as having the formulae C,H,<cQand c6H4<co> CO cClz respectively.A chlorobromo-compound CloH6C1BrO4 was also prepwed ; it isless stable than the dichloro-compound crystallises in white needles,melts at 104-105" and when oxidised in alkaline solution yieldsplates of a substance melting at 141".When the dibromide C9H,Br204 is treated with aqpeous soda ityields bromoform phthalic acid and the monobromo-compoundC,H,BrO2 described above.A. J. G .Synthesis of Anthracoumarins from Cinnamic and '1G1 eta-hydroxybe37zoic Acids. By s. v. KOSTANECKI (Ber. 20 3137-3145). \V l i t 3 1 1 a mixture of cinnamic acid and metahydroxybenzoicacid or nvly hydroxy-derivative of the latter is heated with concen-trated sulphuric acid condensation products are formed.From metahydroxybenzoic acid anthracozcmarin ClsHs03 is ob-tained as a yellow crystalline compound melting at 260" ; it dissolvesreadily in hot glacial acetic acid benzene concentrated sulphuric acid292 ADSTRACTS OP CHEMICAL PAPERS.and hot baryta-water sparingly in alcohol; with boiling alkalis itforms a yellow solution of green fluorescence which probably containsa salt of the corresponding coumaric acid.It is not dissolved byalkalis in the cold whilst the compounds obtained from dihydroxy-benzoic or gallic acid are readily soluble.This fact shows that the hydroxyl-group has taken part in the con-densation and from the great similarity between these compounds andanthraqninone-derivatives the constitution of anthracoumarin is,/G9*CD*Dtprobably C /C6H3.c6H4.co-In like manner metahydrozyanthracoumariiz CI6H8O4 is obtainedfrom symmetrical dihydroxybenzoic acid.By sublimation or crystal-lisation from acetic acid yellow needles are formed which melt at 325'and are only sparingly soluble in any ordinary solvent ; they dissolre,however in alkalis and sulphuric acid. When boiled with baryta-water the coumarin-ring is probably split an insoluble barium saltbeing precipitated. The yellow crystalline monacetyZ-der.ivatire,C16H704Ac melts a t 25.5".Orthodihydroxyanthracoumarin Cl6H8Oa has already been obtainedby Jacobsen and Julius (this vol. p. 56) who gave to it the name" styrogaliol ;" this compound and also its diacetyl-derivative wereprepared the latter melts a t 260" and its formation lends support tothe constitution assigned to the anthracoumarins.Orthodihydroxy-anthracoumarin can be fixed bv a mordant. a fact which is in accord-ance with a theory put forwardy by the author (see this vol. p. 274).I?. S. I(.Purpurogallin. By S. C. HOOKER (Ber. 20 3259-3260).-Tht!author recommends the following method of preparing purpurogallin :-20 grams of pyrogallol is dissolved in 330 C.C. of cold water andtreated with a solution of 87 grams of potassium ferricynnide in330 C.C. of water. Gas is evolved the solution loses its deep redcolour a,nd purpurogallin separates ; in about 6 hour the oxidation iscomplete. The yield is 13 to 14 per cent. of the pyrogsllol employed.Purpurogallin is formed in the oxidation of an aqueous solution ofgallic acid by sodium nitrite.Purpurogallin dissolved i n sulphuric acid gives an intense butfugitive violet coloration when a trace of nitrous acid or a nitrite isadded.The reaction is very characteristic and delicate.A. J. G.Hydrogenation of Aromatic Hydrocarbons. By E. BAMRERGERand W. LODTER (Ber. 20 3073-3078).-The hydrocarbons areboiled with amyl alcohol and sodium the whole poured into water,and the upper layer dried with sodium carbonate and distilled. Theyield varies with different hydrocarbons from 50 to 80 per cent. of thetheoretical.Tetrahydroretene C18H22 .forms a clear viscous oil which when keptfrom air remains liquid ; in open vessels it solidifies probably becom-inc oxidised to retene.Tetyahydro-acenaphthene CI2H14 is a clear colourless viscous oil ofIt boils at 280" under 50 mm.pyessureORGANIC CHICBUSTRY. 293a slightly aromatic odour boiling at 249.5" (corr.) under 719 mm.pressure.Tetrahydyodiphenyl C12H14 is a clear colourless viscous oil havinga slight odour of diphenyl. It boils at 244.8" under 716 mm.pressure.Dihydronaphthalene dihydroanthracene (m. p. 108*5') and tetra-liydrophenanthrene were also prepared.Sulphocamphylic Acid. By A. DAMSKY (Ber. 20 2959-2967).-When ammonium sulphocamphylate is distilled with ammoniumchloride a yellowish- brown oil of peculiar tnrpentine-like odour isobtained which on fractionation can be separated into two portions,one boiling at 108-110" and the second at 195-196".k'hese wereseparately examined.The fraction boiling at 108-110" is a coIourless mobile liquid,having the odour of the crude product and a sp. gr. = 0.7949 at 11.5".I t has the composition CeH14 and is a non-aromatic hydrocarbon,possibly identical with that obtained by Moitessier by distillingcopper camphorate (Jahresb. 1866 410). On treatment with concen-trated nitric acid it is violently attacked and completely resinified,but when dissolved in acetic acid and treated with an acetic acidsolution of nitric acid no action occurs. Oxidation with chromicacid mixture does not convert it into an aromatic acid and with per-manganate it jields only oily fatty acids; whilst contrary to thebehaviour of aromatic hydrocarbons it does not form an acid amideon treatment with amidoformic chloride.Bromine reacts with it,readily yielding an unstable crystalline compound CsH12Br2 andsubsequently liquid higher snbstitution-products whilst the unstable,crystalline additive-compounds C8H14,HC1 and C8Hlr,HBr are formedwhen it is treated with hydrogen chloride and hydrogen bromiderespectively.The fraction boiling at 195-196" under,poes slight decomposition ateach distillation and is a colourlese liquid having an odour similarto that of the lower fraction. I t has probably the compositionCloH140 and forms oily compounds with hydroxylamine hydro-chloride and phenylhydrazine hydrochloride ; the oaime having pro-bably the formula CloH14 NmOH.When potassium sulphocamphylate is fused with twice its weightof potassium hydroxide and the melt extracted with ether a brown,resinous mass is obtained which on distillation in a vacuum yields apal e-yellow readily crystallisable oil.The crystals have the compo-sition C9HI2O2 are readily soluble in alcohol and ether very sparinglysoluble in hot water and melt at 99". The compound although pre-pared by Kachler's method (Abstr. 1874 154) and having thesame composition differs from the substance prepared by him in itslower melting paint and marked acid character. The silver salt,CgHl1O2Ag is soluble in hot water; the calcium salt (CgH1102)2Ca+ 2H20 forms yellowish crystals soluble in hot water ; the bariumsalt (C9H1,02)2Ba + 2H20 is crystalline and soluble in hot water ;the methyl salt was also prepared and is crystalline.Treated withbromine the acid yields a cryatalline compound with the evolution ofN. H. M294 ABSTRACTS OF CHEMICAL PAPERS.hydrogen bromide and it is not reduced by the action of sodiumamdgam. When distilled with soda-lime i t yields R yellow oil,which on rectification forms a colourless mobile liquid of the com-position C,Hl boiling at 133-1%" and polymerisink on exposure tothe air. w. P. w.Action of Sulphuric Acid on Terebenthene. By J. Bou-CHARDAT and J. LAFONT (Compt. rend. 105 1177 - 1179). - Theproduct of the gradual action of 467 grams of Rulphuric acid on9340 grams of French terebenthene boiling at 155-15i" (rotator-ypower -33.2") was distilled in a current of steam ; 79 grams of sul-phuric acid remained in the free state the rest having formed acompound 2C10H16,H2SO~ which is almost though not quite fixed.This compound could not be isolated from the colophene with whichit is mixed.Jt is a neutral substance and does not combine withpotassinm hydroxide. Alcoholic potash is without action in the cold,but at 150" decomposition takes place with formation of volatile pro-ducts and the compound C,oH16,S02K(K which crystallises from itsaqueous solution in thin lamellse.The portion of the original product which distils with steam con-sists mainly of the unaltered hydrocarbon without any camphene.The fraction boiling at 175-180" has the composition CI0Hl6 oxidisesvery readily and is somewhat lighter than the original terebenthene.It absorbs hydrogen chloride readily yielding a liquid product andwhen the latter is distilled in a vacuum it yields cymene and ter-pilene hydrochloride CloHI6,ZHCl melting at 48".The rotatorypower of the corresponding terpilene is only one-fifth or one-sixthThat of another terpilene obtained from tohe same terebenthene by adiffrrent method.The fraction boiling below 165" was treated successively four timeswith sulphuric acid always with a similar result but the fractionboiling at 157" which gradually became smaller and smaller inquantity diminished in rotatory power and after a fifth treatmentwas converted into an easily solidified camphene. This camphene isformed by the decomposition of the small quantity of the sulphurcompound which distil6 over with the water.This fraction in fact,aIways contains a small quantity of free sulphuric acid.Wben the original product which is not volatile in steam isheated at 200-250" an energetic reaction takes place water sul-phurous anhydride and sulphur being produced. The liquid productscontain a slightly active lsevogyrale compound boiling at lX",cymene terpilene and dextrogyrate camphenols.By A. VESTERBERG (Ber. 20 3248-3253).-1na previous paper (Abstr. 1886 1038) the author showed that themother-liquor from the preparation of dextropimaric acid containedp-pimarjc acid. From the very vigorous lsevorotatory power of thisacid the name laevopimaric acid is now given to i t ; its separationand purification were attended with great difficulty.Leuopimaricacid C20H3002 isomeric with dextropimnric acid crystallises in the1-hombic system ; axial ratios a b c = 0.81042 1 0.61407 ; ob-C. H. B.Pimaric AcidsORGANIC CHEMISTRY. 295served faces wP ~ P w P/2 2Pm OP. It melts between 140" and150" and is insoluble in water readily soluble in all the other usualsolvents its solubility being greater than that of the dextro-acid.One part of the acid dissolves in 10.8 parts of 98 per cent. alcohol at 15".A solution of 3.174 parts of I~vopimaric acid in 100 C.C. of alcoholhas a laevorotatory power = -272". It forms readily crys-tallisable salts of which the sodium ammonium and lead salts aredescribed.The author considers it very probable that Calliot's pyromaric acid(this Journal 1874 457) is a mixture of dextro- and hvo-pimaricacids. A.J. G.Action of Phenylhydrazine on Santonin. By C. GRAM(Chern. Centr. 1887 1163-1164; from Rend. R. ACC. Lincei [4] 3,521-522).-When a solution of aantonin (10 grams) is heated withphenylhydrazine (10 grams) in acetic acid solution (sp. gr. 1-06) ayellow hydrazide ClaH,,02*N2HPh separates which melts at 220",and is not decomposed by acids. Hydrochloric acid dissolves it inthe cold with a reddish-yellow colour; on heating a scarlet preci-pitate is formed.Lakmoid and Litmin. By W. N. HARTLEY (Proc. R. Dublin XOC.,5 159).-.Lakmoi'd (Abstr. 1885 148) is soluble in strong alcohol,insoluble in water. A solution in 50 per cent. alcohol retains its colourwith but slight alteration for several months.Litmin is insoluble instrong alcohol but soluble in spirit of 50 per cent. ; the solution wasbleached after a time although not exposed to bright light. Thephotographic spectra of the two substances did not differ markedly.From these results it follows that the two substances are not identical.LakmoYd is a better reagent than litmin.New Brazilin-derivative. By C. SCHALT and C. DRALLE (Ber.,20 3365-3366) .- Tetran,ethyZbraxitezn Cl6N1,,O5Me4 is prepared bymixing 2.7 grams of brazilin with 0.8 gram of sodium (each dissolvedin alcohol); 8 grams of methyl iodide is then added and the wholewarmed on a water-bath until the colour changes to a yellowish-brown.The greater portion of the alcohol is distilled off and the rest evapo-rated on a water-bath.It is washed with water dissolved in ether,and washed with dilute aqueous soda. It forms a brittle transparent,amber-coloured mass which becomes crystalline when ether is pouredover it. When crystallised from alcohol it is obtained in colourlesscrystals melting at 138-139". The compound has the properties ofa phenol alkyl ether; it does not change when exposed to air andyields an additive product with ammonia.Metaritroquinoline. By A. CLAUS and A. STIEBEL (Ber. 20,3095-3097).-ilfetanitropuinoZine C9NH,*NO2 is prepared from 10grams of nitraniline 2.6 grams of picric acid 14 g r a m s of glycerol and14 grams of sulphuric acid. The mixture is afterwards boiled forsome hours. The product after being freed from resin is treated withlight petroleum to remove the phenanthroline which is also formed inThe hydrazine compound yields a platinochloride.J.W. L.A. J. G.N. H. M296 ABSTRACTS OF CEEMTCAL PAPERS.the reaction and recrystallised from alcohol or water. It forms long,thin colourless needles melting a t 131 5" (uncorr.). The hydro-chloride crystallises in long yellowish-white needles melts at 225"with evolution of gas and decomposes in contact with water. Thenitrate crystallises in long flat needles of a satiny lustre not veryreadily soluble in water. The platinochloride forms large amber-coloured prismatic crystals. Metamidoquinoline C,NH,*NH pre-pared by reducing the nitro-compound with stannous chloride formslong hair-like yellowish needles which melt at 186" (uncorr.) ; it isreadily soluble in ether chloroform &c.When heated i t yields asublimate of splendid red needles. It does not distil with steam.(Compare Abstr. 2887 810). N. H. 31.Constitution of Quinoline-derivatives. By J. FREYDL (Monatsh,.,8 580-583) .-The so-called p-amidoquinoline on conversion intothe corresponding diazochloride and treatment of the same withpotassium cyanide yields a cyanoquinoline identical with the meta..cyanoquinoline of Bedall and Fischer. On hydrolysis this nitrileyields a quinolinecarboxylic acid identical with that obtained froman amidobenzoic acid by Skraup's reaction. The amidoquinoline isalso converted by the diazo-reaction into a chloroquinoline identicalwith the compound obtained by La Costae (Abstr. 1886 159) fromrnetachlortlniline by Skraup's reaction.Then in the above group thesubstituted groupings are in the 2 position as derived from the1 3 benzenoid derivatives. V. H. V.Sulphonation of Quinoline. By G. v. GEORGIEVICS (Monatsh. 8,577-579) .-By the sulphonation of quinoline with Nordhausen acid,La Coste as also Bednll and 0. Fischer obtained a mixture of the 1 2and 1 3 quinoliuesulphonic acids the proportion of each which isformed being dependent on the conditions of the experiment. It is hereshown that if the sulphonation is effected with ordinary sulphuricacid the 1 4 sulphonic acid is produced a result confirmed by theconversion of the acid into the corresponding nitrile and carboxylicacid. V.H. V.Quinoline. By E. LELLMANN and (3. LANGE (Bey. 20,3084!-3089 ;compare Abstr. 188 7 737) .-Calcium parabromobenzenesulphonatecrystallises is well-formed monoclinic crystals with 2 mols. H20 :a b c = 0.5872 1 0.5168; p = 85" 14' 42" (compare Goslich,this Journal 1876 i 929). Parabromometamidobenzenesulphonicacid crystallises in well-formed prisms with 1 mol. H,O (not 14 mol.H,O Goslich Zoc. cit.).Orthobromoqzcinoline-anaszLkpho~ic acid C9NH5Br-SOsH [Br SOsH =1 41 is prepared by heating 5 grams of parabromometamidobenzene-sulphonic acid 6 to 7 grams of orthonitrophenol 20 grams of glycerol,and 25 to 27 grams of sulphuric acid in a reflux apparatus a t 155-160" for six hours. The product is treated with water stenm-distilled,treated with baryta filtered and the filtrate boiled with animal char-coal.By precipitating the barium as exactly as possible with sul-phuric acid and carefully evaporating the fihate the sulphonic aciORGANIC CHEMISTRY. 297is obtained in small lustrous plates with 1 mol. H,O. The calciumsalt with 6i mols. H20 crystallises in long needles readily soluble inwater.Tetrah ydro~.uinoline-aitasu~honic acid C9NH,*SOSH + H,O is formedwhen 5 grams of bromoquinolinesulphonic acid is heated on a water-bath with concentrated hydrochloric acid and tin. It crystallises fromdilute solutions in rhombic crystals ; a b c == 0.5041 1 0.7511,and from concentrated solutions is monoclinic crystals ; a b G =0.4855 1 0.5298 ; p = 55" 10'. When treated with oxidising agents,it shows the reactions characteristic of tetrahydroquinoline-derivatives.The quinolinesulphonic acid previously prepared (Zoc.cit.) frommetamidohenzenesulphonic acid also yields a tetrahydroquinoline-sulphonic acid which completely resembles that just described.N. H. M.p-Quinolinedisulphonic Acid. By W. LA COSTE and F. VALEUR(Bey. 20 3199-3201) .-/3-Quinolinedisulphonic acid prepared byheating the pure barium salt with the necessary amount of sulphuricacid crystallises in slender white needles readily soluble in water,insoluble in alcohol ether benzene and chloroform. (CompareAbstr. 1887 379.) The barium salt is obtained by treating thepotassium salt with barium acetate. The potassium salt (with 1 mol.H,O) is insoluble in alcohol readily soluble in boiling water.Whenthis salt is fused with 3 parts of potash at 160" potassium P-hydroxy-quinoliiiesulphonate is formed. p-H~droxyquinolines.rL~honic acidcrystallises in yellow lustrous plates melting a t 270-275" ; it dissolvesreadily in hot water sparingly in alcohol and still less in chloroformand carbon bisulphide.p- Dihydroxyqaiinoline CsNH,( OH) is prepared in a manner similarto the a-compound (Abstr. 1886 629) except that the temperature isonly raised to 250-255". It crystallises in slightly brown needles,readily soluble in ether alcohol benzene chloroform and carboilbisulphide insoluble in water. It melts a t 68" and sublimes a t ahigher temperature in slender white needles. The salts are stable,but difficult to crystalhe.(Compare also Abstr. 1887 973.)N. H. M.Tetrahydroquinaldine. By M. MOLLER (AnnaZen 242 313-321) .-Tetraby droquinaldine has already been described by Jackson(Abstr. 1881 742) and by Dobner and Miller (Abstr. 1884 183).The nitronitroso-compound NO,.C,oNH,,.NO crystallises in goldenplates and melts a t 152". Methylhydroquinaldine CloHI2NMe has beenprepared by Dobner and Millei. (Zoc. cit.). It can also be preparedby the action of tin and hydrochloric acid on quinaldine methiodide.Methy Ihydroquinuldine methiodide,CloNH,,Me,MeI crystallises in needles,melts at 205" and dissolves freely in water and in hot alcohol. Freshlyprecipitated silver oxide converts it into the ammonium base,CloNH,,Me,MeOH a crystalline hygroscopic compound.The auro-chloride crystallises in lemon-coloured needles and the dichromate insix-sided plates. The plstinochloride forms brick-red crystals soIublein hot water. The base is decomposed by heat yielding methyl,alcohol and methy ltetrahydroquinaldin298 ABSTRACTS OF CHEMICAL PAPERS.Ethy ZtetrahydroquinaZdine CloNH12Et is a colourless liquid boilingat 256". The platinochloride and methiodide are crystalline. Thelatter melts at 187" and dissolves in water but is not acted on by asolution of potassium hydroxide. w. c. w.Quinaldine Alkyl Iodides. By M. MOLLER (AsmaZen 242,300-312) .-Quinaldine methiodide and methylquinaldinium hydroxidehave been previously described by Dobner (Abstr. 1884 l84) andby Bernthsen and Hess (Abstr. 1885 558) respectively.I n additionto the salts prepared by Bernthsen and Hess the ammonium baseyields an aurochloride CloHgNMeCl,AuCI and a dichromate,crystallising in lemon-coloured needles. The dichromate detonates a t90". Ethylquinaldinium hydroxide on exposure to the air changes intoa carmine-coloured resin. The platinochloride ( CloNHgEt)2PtCI,,is deposited from hot water in ruby prisms. The aurochloride,CloNHgE t C~,AUCI~,forms golden needles. The dichromate detonates at 100". Quirznldine-propiodide forms greenish-yellow prisms soluble in water and in hotalcohol. It melts at 166-167". The ammonium base is amorphous.It is soluble in alcohol and ether. The platinochloride aurochloride,and dichromate are crystalline. Quirzaldine butiodide is preparedby heating quinaldine with isobutyl iodide at 115" in niolecule pro-portion. It crystallises in plates and melts at 172".The amyliodide requires a temperature of 140-145" for its formation. It iscrystalline soluble in water and hot alcohol and melts at 175".0rthometh.ylyuin.aldine methiodide is deposited from alcohol inyellow needles and melts at; 221". The ammonium base is tolerablyst.able and does not change rapidly on exposure t,o the air. Theplatinochloride dichromate and aurochloride are crystalline. Thebase is decomposed by heat yielding orthomethylquinaldine. Ortho-methylquinaldine ethiodide is deposited from alcohol in yellow needles,and melts at 228". The ammonium base is a stable oily liquid andit forms crystalline platino- and auro-chlorides.Paramethylquinaldine unites with methyl iodide at the ordinarytemperature. The compound melts at 236-237" and dissolvesfreely in water.The ammonium base is unstable. The platino-chloride dichromate and aurochloride crystallise in needles. w. c. w.Conversion of Indoles into Hydroquinolines. By E. FISCHERand A. STECHE (Annalen 242 348-366) .-In previous communicn-tions (Abatr. 1887 588 and 976) the authors have described theconversion of methylketale into dimethyldihydroq uinoline and di-methyltetrahydroquinoline which are derivatives of P-methylquino-line. In the preparation of dimethyldihydroquinoline a monomethyl-dihydroquinoliue is formed as a bye-product. Dihydroethyldimethyl-quinoline and ethylmethylketole have already been described by theauthors (loc.cit.)ORGANIC CHEXISTdT. 299Et~ylmeth2/Idihydroquilzoline [Et Me = 1' 3 7 prepared by theaction of methyl iodide on ethylmethylketole and methyl alcohol at120" is a colourless oil which turns pink on exposure to the air. Itboils at 254-255" and forms salts which are freely soluble in alcoholand water. With ferric and platinic chlorides it yields crystallineprecipitates.Tr.imethyZdihydroquinoZine CgNH,Me3 [l' 3' 4'1 boils at 244".The hydriodide crystallises in long prisms. The sulphate is precipi-tated from its alcoholic solution in crystalline scales on the addition ofether.The dimethyldihydro-p-naphthaquinoline previously described bythe authors (Zoc. cit.) is an imide base. The hydriodide and platino-chloride are sparingly soluble in alcohol and in water.The methiodides of the quinolines and dihydroquinolines are easilydecomposed by alkalis but the methiodides of the tetrahydro-quinolines are not attacked.Dihydroquinolines containing methylene in the indole-ring turn redThe platinochloride is decomposed by boiling water.on exposure to the air.w. 0. w.a-Alkylcinchonic Acids and a-Alkylquinolines. By 0.DOBNER (AlznaZen 242 265-29@).-The preparation of the a-alky! -cinchonic acids and the properties of some of these compounds havealready been described by the author (Abstr. 1387 ,504). In thepreparation of a-isopropylcinchonic acid a neutral substance of thecomposition C19H,,N,0 is obtained as a bye-product. I t is insolublein alkalis.a-Isopropylcinchonic acid CgNH,PrW300H [ 2' 4'1,crystallises with 1+ mols. H,O. The hydrochloride CuH13N0,,H C1,forms colourless plates freely soluble in water. The platinochloride,which is abnormal (C,3H13N0,,HCl),,PtC14 + H20 and the auro-chloride ( C13H13N02)2,HA~C14 are crystalline. a-IsopropyIquino-line picrate is deposited from alcoholic solutions in yellow plates..It melts at 150". The platinochloride crystallises with 2 mols.H,O.A neutral substance of t,he composition C,,H,,N,O is formed by theaction of aniline on an ethereal solution of pyruvic acid and isovalei=aldehyde. It crystallises from alcohol in silky needles and melts at160". If a warm alcoholic solution is substituted for the etherealsolution a-isobutylcinchonic acid is produced.The acid crystalliseswith 19 mols. H,O. The hydrochloride ClaH15N0,,HC1 + H,O,crystallises in colourless plates and dissolves freely in water. Theplahinochloride ( C,,Hl5NO,),,H,PtC1 is also crystalline. a-Isobutyl-quinoline picrate crystallises in plates soluble in alcohol. It melts161'.On mixing together cold ahoholic or ethereal solutions of fur..furaldehyde pyruvic acid and aniline a neutral substance ol thecomposition C,,H,,N,O is formed but with warm alcoholic solu-t,ions a-furfurcinchonic acid ( C4H,0C,NH5)-COOH is produced.This acid crystallises in greenish-yellow needles. It melts withdecomposition between 210" and 215" and dissolves freely in alcohol,ether benzene and in hot water. The silver lead and copper saltsare sparingly soluble in water.The hydrochloride nitrate an300 ABSTRACTS OF CHEMICAL PAPERS.sulphate are freely soluble. The platinochl oride ( C,4H,N0,),,B2PtCl,,and the aurochloride ( Cl4HSNO3),,AuCI3 crgstallise in needles.a-Furfurpinoline is obtained by heating furfurcinchonic acid st300'. It crystallises in thickneedles and dissolves in alcohol ether and benzene. The platino-chloride ( c,3HgNO)2,H2PtC16 + 2H,O and the aurochloride,It melts at 92" and boils above 300".Cl3HgNO ,HAu Clc,crystallise in needles and dissolve in hot water.forms orange-red needles.decomposes at 100".The dichromnteThe dry saltThe picrate melts at 186" and is deposited from w. c. w.It is soluble in hot wateii.hot alcohol in large yellow plates.a-Phenylcinchonic Acid and its Homologues.By 0. D~BNERand M. GIESEKE (Anna7ern 242 290-300).-0n mixing togetherethereal solutions of aniline pyruvic acid and benzaldehyde a com-pound of the cornposition C,,H,,N,O is obtained in the form of a crys-talline mass insoluble in acids alkalis and water. It melts at 225",and dissolves freely in ether benzene acetic acid and light petroleum.Strong acids and hot alkalis decompose the compound yieldinganiline and resinous products.The preparation and properties of a-phenylcinchonic acid havebeen previously described by the authors (Abstr. 1887. 504). Thesilver lead copper and zinc salts were obtained in the form ofamorphoiis precipitates.A compound of the composition C24H2zNz0 is deposited in crgstalson mixing ethereal solutions of paratolnidine pyruvic acid and benz-aldehyde.It melts at 204-205" and is insoluble in acids andalkalis. If warm alcoholic solutions are used only a small quantityof this compound is formed the chief product being paramethyz-a-phenylcinchonic acid,C9NH4MePh*COOH [Me Ph COOH = 3 2' 4'1.This acid is deposited from alcohol in yellow needles. It melts at 228",and is soluble in alcohol and ether. The platinochloride,forms golden needles. On distillation with soda-lime paramethyl-phenylcinchonic acid yields paramethyl-2-phenylquinoline. Ortho-methyl-a-yhenylcinchonic acid [I 2' 4'1 melts at 245" and is freely~oluble in ether and hot alcohol. The silver salt C,HI2NO,Ag.+F,O crystallises from hot water in needles.On distillation withlime the acid yields orthomethy7-2-phenylquinoline. The base hoils w. c. w. above 360" and melt's at 49-50".Parabenzoylquinaldine and Paradiquinaldine. By E. HTNZ(Annden 242 321-329). -Paraldehyde acts on parabenzoylnni-line dissolved in hydrochloric acid forming parabenzoylqllLina7dil?e,C9NH5MeBz and several bye-products. The new base melts at 67-68"ORQANIC CHEMISTRY. 301boils above W O O and dissolves freely in hot water alcohol ether,benzene chloroform and light petroleum. The platinochloride,ci*ystallises in needles and is sparingly soluble in water. The anhy-drous salt melts at 108-110". The dichromate also crystallises inneedles.UiqwinaZdine is prepared by the action of paraldehyde on benzidinedissolved in hydrochloric acid.The yield is poor. Djquinaldine,C20H16Nz me1 ts at 206-207" and dissolves in alcohol benzene,chloroform and acetone. It boils with siight decomposition above360".The platinochloride CzoH16~2,H2PtC16 + 2H20 is sparingly solublein hot water. The nitrate C20H,6N2,2HN03 cry stallises in needles,and is soluble in water.Quinolina By E. BAMBERGPR (Ber. 20 3338-3344).-Quinoliwe-phenacyl bromide COPh*CHz*CSNH7Br is prepared by mixing equalmol. weights of quinoline and bromacetophenone dissolved in ether orin benzene ; it separates in tufts of white needles. The yield is quanti-tative. It dissolves readily in alcohol and water sparingly in etherand benzene begins to decompose at 115-1 18" and melts at about 165".The xincochloride crystallises from water in small thick stronglyrefractive prisms ; the nitrate crystallises in clear strongly refractiveprisms of a vitreous lustre which are generally bent.The phpio-logical action of the nitrate on mice frogs and cats is described ; itresembles that of curare. When a qninolinephenacyl salt is treatedwith alkalis the ammonium base is obtained Cogether with a scarletdye ; the base forms white flakes readily soluble in ether.Form y 1 henacy lait thraihi lic acid CC) 0 H*C6H4*N( CH,*C@ Ph) C OH,is formed when 16 grams of potassium permanganate disgolved in600 C.C. of water is gradually added to a cooled solution of 10 gramsof quinolinephenacyl bromide in 1200 C.C. of water ; after 12 hours thecolourless liquid is filtered the manganese peroxide extracted severaltimes with boiling water and the collected filtrates from 50 grams ofthe phenacyl bromide evaporated down to 2 to 2.5 litres.It is thenmade acid left for 24 hours in a cool place and the crystals thusobtained are recrystallised from much water. I t crystallises fromdilute alcohol in white plates of a satiny lustre melting at 184" readilysoluble in alcohol less in hot water. Benzoic acid is formed as thechief product of the reaction. When the acid is boiled with dilutesulphuric acid formic acid is obtained.Pyridinephenacy Z bromide C,8HH,Br*CHz*C0 Ph prepared from pyri-dine and bromacetophenone crystallises from a mixture of ether andalcohol in slender lustrous strongly refractive prisms. The chromatecrystallises from water in lustrous orange-coioured prisms ; the zinco-chloride separates from its hot aqueous solution in lustrous rhombicplates.When the bromide is treated with aqueous soda it is decom-posed into pyridine and benzoic aoid.The methiodide melts at 220".%'he dichromate is cr-ystalline. w. c. w.N. H. M.VOL. IJV. 302 AllSTltXCTS OF CHEMICAL PAPERS.Acetic Tripiperide. By J. Busz and A. KEKUL~ (Rer. 20,3246-3248).-0rtho-amides corresponding with the ortho-saltsformed by acetic and other acids have not yet been prepared.Experiments made with primary amiiies and with secondary aminesof the type NHR' have failed to yield such conipounds but withsecondary amines of tlie type NHR" o€ which piperidine is an example,success was attained.Acetic tripiperide CMe( C6NHl0) is obtained by heating acetic tri-chloride (a-trichloroethane) for 4 to 5 hours in a reflux apparatus.It boils at 133-134" under 15 mm.or 261-263" under ordinarypressure. It is very stable yjelding but slight quantities of aceticacid when boiled for days witli water or dilute acetic acid. Thehydrochloride is crystalline and insoluble in ether ; the platinochloridecrystallises in golden-yellow plates.Chloroform acts very slowly on piperidine yielding a base boilinga t 9 8 O which seems to be orthqformic piperide CH( C,NH,,),,H,O.Benzotric'riloride reacts readily with piperidine but whether abenzoic tripiperidide is formed is not yet established. A. J. G.Oxidation Products of Papaverine. B J G. G o r m c H m E D T(Mo?aafsh.8 510-528) .-In continuation of former experiments onthe oxidation of papaverine by potassium permanganate (Abstr. 1886,479) the author has more fully examined dimethoxycinchonic acidand other products formed. Papaverine hydrochloride yields oxalic,hemipinic and veratric acids which are contained in the filtrate fromthe reduced manganese peroxide ; on treatment of this last with sul-phurous acid and extrstction of the residue with hydrochloric acid,papaveraldine hydrochloride and dimethoxycinchonic acid are obtained,together with a substance of the formula C,,H,NO,. This last,named I~ernipinisoimide to distinguish it from the isomeric hemipini-mide obtained by Liebermann by the action of hydroxylamine onopianic acid forms small white needles melting above 300"; it dissolvesonly on prolonged heating with alkali but is a t t'he same time decom-posed into ammonia and hemipinic acid. It is also distinguished fromhemipinimicle by the unstable character of its potassium-derivative.The formula of this substance is discussed but without satisfactoryconclusions.Dinz ethoz y cinchonic acid CgNH4(0Me) 2-C 0 0 H crys tallises with2H,O in sinall needles ; it melts a t 205" with violent evolution of car-bonic anhydride and formation of dimethoxyquinolino ; it gives abrownish-red turbidity with ferric chloride but no reaction withferrous sulphate. Solutions of its salts give gelatinous precipitateswith barium calcium copper and silver salts. The hydrochloridecrystallises with 2 mols H20 in glistening needles and theplatino-chloride ifi groups of yellow needles. By hydriodic acid the dimethoxy-acid is converted into dihydroxycin,chonic acid C9NH4(OH),*COOH,which is an amorphous powder melting a t 221" with violent evolutionof gas. It gives a violet coloration with ferric chloride and a reddish-yellow with ferrous sulphate. Its salts are all of a yellow aolonr thusresembling those of hydroxycinchonic acid obtained by Weidel fromthe corresponding sulphonic acidORGANIC CHEJIISTRY. 303nirvLet?2oxyg2LinoZine C9NE,(OMe) obtained by heating the di-methoxycinclionic acid as also from pRpaveraldine when it is heatedwith alkali forms a hydrochloride crystallising with 3H,O a picratecrystallising in citron-yellow needles and a ckronzute in small orange-yellow rhombic crystals.This dimethoxyquinoline from papaverine is isomeric with thatobtained from veratric acid ; a list is given of the points of differencebetween the salts of' these two bases. It is probable that in themethoxyqninolim from veratric acid the methoxy-groups are in theposition 1 2 but in thah from papaverine the groups are in thepositions 2 3 ; the aukhor proposes to. confirm this view by furtherexperiments. V. H. V.Adenine. By A . KOSSEL (Ber. 28 3356-3358 ; compare Abstr.,1886 556) .-Adenine nitrate C5H5N5,HN03 + iH,O crystallises instellate groups of needles; the dry salt dissolves in 110.6 parts ofwater. The hydrochZoride (with + md. H,O) forms transparent mono-clinic crystals a 8 c = 2.0794 1 1.8127; @ = 61" 40' ; the anhy-drous salt dissolves in 41.9 parts of water. The pZatinochloride,( C5H,N6),,H,PtCl crystallises from its dilute solution in needles ;when a concentrated solution is boiled long the salt,C,H5N5,HCl,PtCL,separates as a bright yellow powder. The silver c07npownd C5H4N5Ag,is obtained4 as an amorphous powder by adding an amrnoniacal silversolution to a hot ammoniacal solution of adenine ; with a large excessof silver solution the c o n y o u i d C5H5N5,Ae0 is formed. The acetyl-derivative C5H,N5Ac crystallises in small white plates readily solublein hot water and alcobol soluble in dilute acids and alkalis ; it doesnot melt at 860". The banxoyZ-derivative C5H,N5Bz fomns long thin,lustrons needles melting a+ 234-23.5" readily soluble in hat alcohol,soluble in dilute acids and m zmmonia.Adenine is very &able towards acids alkalis and oxidising agents,but is readily reduced by zinc and hydrochlo~ic acid behaving likeh ypoxanthine. N. H. M.Ptomaines and Leucsma'ines. By A. GAGTTIER (BUZZ. XOC. Chinz.,48 6-23).-A summary of our present knowledge concerningptomahes giving an account of the results obtained by the author,Brieger and others whose papers have from time to time appeared inAbstracts i n this Journal (see Abstracts 1881 100 224; 1882 1115 ;1884 89 188; 1885 676; 1886 634; also BUZZ. de Z'Acad de Med.,1886). C. H. B.Empirical Formula of Cholic Acid. By P. LATSCHINOFF (Ber.,20 3274-3283),-Mylius has lately (Abstr. 1887 982) upheldStrecker's formula C2,H,,05 for choiic acid against this formulaC~SH& proposed by the author. The latter has therefore carefullyre-examined this acid and its drrivatives with the result of confirmingthe formula C,,H4,05. He has been unable to obtain the acid perfectlyanhydrous. Cholic acid crystailises in two forms (i) in tetrahydric$ 304 ABSTRACTS OF CHEMICAL PAPERS.cryst'als and (ii) in prismatic crystals. The first obtained bv crystal-lisation from alcohol acetone ether (of which it requires 510 parts a t18" for solution) isobutyl alcohol or ethyl acetate has the formulaCZ5H,,O5 + $H,O. It only loses this water of crystallisation a t orabove 145" and partial decomposition always takes place simultane-ously. Fusion ultimately results at 160-180". The prismatic crystals,obtained by the precipitation of an acetic solution of the acid withwater have the formula C25Hd?05 + H20. They lose 2 mol. H,O a t120" but the remaining t is only lost a t or above 145". The authorbelieves -Mylius to have taken the not fully dehydrated acid as anhy-drous When this acid is dissolt-ed inpheno1,it forms white prisms whichgive analytical results agreeing with the formula C25H,205 + $H20 +%C,B,O. It seems that the last trace of water is very firmly unitedto the cholic acid and that when crystallised from other media withwhich i t unites the acid only takes up the complemmtary quantityof the medium. Thug the crystals from an alcoholic solution had theformula c&&05 + + pC2H,0.Attempts to obtain mineral salts of the acid showed that here alsoa similar state of things existed. The salts all contained an excessof the base that excess being as in the case of the water of crystallisa-tion about one-eigti th of an equivalent. With aniline and toluidine,however cholic acid yields well-defined crystalline salts which giveiiumbers agreeing with those required by theory. Aniline choZafe,C~H&,NH2Ph forms needles melting at 140" ; wetatoluidine choZateneedles melting at 140-180".Action of Sodium Chloride in Dissolving Fibrin. By .J. R.GREEN (J. PhysioZ. 8 37.2-377).-When fibrin is extracted with a 5or 10 per cent. solution of sodium chloride a prote'id goes into solution ;on renewing this sollition daily removing that added on the previousd.ty it is found that in 32 to 35 days the whole of the fibrin is dis-solved. In all these experiments there was perkct freedom fromputrefaction. When dissolved in this way the fibrin is decomposed,with the formation of two globulins one of which coagulates at 56",is soluble in 1 per cent. sodium chloride solution is readily convertedinto syntonin and alkali-albumin and is not precipitated by weakacid; the other is insoluble in 1 per cent. sodium chloride solution,hut soluble in a 10 per cent. solution ; i t coagulates on heating a t 59-MI" is readily converted into alkali-albumin but not into syntonin thencid added for the latter purpose precipitating it and in suspensionit is not acted on. In sDme of its reactions the former substancemcals the behaviom of fibrinogen but neither corresponds with fibrin-ogen cr serum globulin and the latter cannot be made to re-formfibrin. W. D. H.L. T. T.Haematoporphyrin. By C. A. MACMUNN (J. PhhysioZ. 8 384-389).-A brownish pigment is scattered over several superficialportions of the mollusc Xolecurtus strigillatus. On microscopicalexamination i t is found that ill the foot especially the pigment issitnat,ed a t the border of the cells so that the boundaries betweenthem are marked much in the same way that endothelium cells arPHYSIOLOGICAL CHEMISTRY. 305demonstrated by the use of sil-rer nitrate. Granules in the cellscontain the same pigment. Spectroscopic examination shows thatthe pigment is haematoporphyrin ; this is identical with Moseley’s pols-perythrin (Quart. J. Mic. Science 17 1 ) ; the bands are identical withthose seen in the pigment from the dorsal streak of the earthworm ; alist of 12 other invertebrates in which the same pigment has beenfound is given. In many of these there is no hemoglobin present butthe universal distribution of the histohaematins and the fact thatthese yield some of the decomposition products of hBmoglobin fullyexplain the occasional appearance of a hemoglobin-deriva,tire ininvertebrate animals (see Abstr. 1886 638). W. D. H

ISSN:0368-1769    

DOI:10.1039/CA8885400240

出版商:RSC    

年代:1888

数据来源: RSC

摘要:

PHYSIOLOGICAL CHEMISTRY. P h y s i o l o g i c a1 C h e m i s t r y . 305 Influence of Sleep on the Activity of Respiratory Combus- tion. By L. DE SAINT-MARTIN (Compt: rend., 105, 1124-1128).- Experiments with doves show that, independently of the effect pro- duced by fasting, natural sleep reduces the quantity of carbonic anhydride exhaled by about one-fifth, and reduces the quantity of oxygen absorbed by about one-tenth. Experiments with dogs show that during sleep produced by mor- phine the proportion of carbonic anhydride exhaled falls to one-half the normal amount ; during sleep produced by chloral or chloroform it falls to one-third the normal proportion. When anmthesia by chloroform is sufficiently long continued the blood becomes impoverished in oxygen and is charged with an amount of carbonic anhydride very considerably in excess of the normal propor- tion.In the early stage of insensibility, there is a diminution in the proportion of carbonic anhydride in the blood, but this is due to secondary causes. C. H. B. Coagulation of Fibrin and Intravt#xular Clotting. By F. KRGGER (Zeit. Biol .24, 189--225).-Wooldpidge has shown that the phenomenon of coagulation is brought about by a substance which he calls A fibrinogen, obtainable from peptone plasma by simply cooling, and that the cellular elements which were hitherto considered essen- tial, although they may assist coagulation, are nevertheless of second- ary import. In his Croonian lecture he described coagulation as essentially similar to crystallisation. In plmmai there are three con- stituents concerned in coagulation-A, B, and C fibrinogen.A and B fibrinogen are compounds of lecithin and proteid, and fibrin results from the transference of the lecithin from A Gbrinogen to B fibrino- gen. From this point of view the ferment is of secondary import- ance. Wooldridge further found that a compound of lecithin and prote’id closely allied to the A fibrinogen, which he considers probably the306 ABSTRACTS OF CHEMICAL PAPERS. precursor of A fibrinogen, exists in the testis and thymus gland of the calf, in the fluid of the lymph glands and the stromata of red blood- corpuscles. This compound is capable of causing widespread intra- vascular clotting in the entire absence of any cellular elements. It is with reference t o this last statement that the author joins issue, A large number of experiments have led him to the opposite conclusion, namely, that the corpuscular elements play the chief part in the coagulation, both within and without the body.He corrobo- rates Wooldridge's statement, however, that the stromata of red blood corpuscles produce intravascular clotting. The leucocytes obtained by centrifugalising the fluid of the lymph glands produce intravascular clotting, but the supernatant liquid, the author states, is inert, o r almost so. He considers that any slight action of the fluid may be accounted for by the presence of some leuco- cytes, for he found it impossible to remove them completely, even by centrifugal action. J. P. L. Influence of Calcium Sulphate on the Coagulation of the Blood.By J. R. GREEN (J. PhysioZ., 8, 354--371).-A saline extract of washed blood clot contains fibrin ferment (Bnchanan). Henting.such an extract nearly to the boiling point delays the action of the ferment but does mot destroy it ; the ash was found to contain n definite and fairly constant amount of calcium sulphate. A saturated solution of calcinrn sulyhate was prepared, and on adding 1 C.C. of this to 10 c c. of diluted magnesium sulphate plasma, coagulation set in with great rapidity; a very small amount of the salt (0.001 per cent.) has considerable clotting power ; this increases with the quantity of calcium sulphate used, but not proportionately. In other experiments with peptone or leech extract, in which coagulation was reiarded by cold, the addition of calcium sulphate caused it to take place in some cases very rapidly, in others more slowly. Calcium sulphate cannd be regarded as the fibrin ferment however ; addition of that salt to pericardial fluid or t o a sodium chloride solu- tion of fibrinogen causes no coagulation in those fluids ; but when the ferment is present, addition of salt accelerates the coagulation.The next point investigated was whether it is possible to have coagulation in the absence of calcium sulphate ; peptone-plasma was dialysed for three days into a 0.6 per cent. solution of sodium chloride ; if water had been used outside fhe membrane, the globulins of the plasma would have been precipitated. Dilution of the plasma with saline solutions then caused no clotting, nor did the passing of R stream of carbonic anhydride through the plasma coagulate it as i t does ordinary peptone-plasma,. But on adding a little calcium sulphate to fhe diluted plasma coagulation rapidly set in.In plasma prevented from coagulating by cold, or by admixture with magnesium sulphate, similar experiments were performed, dialysis being carried out at the temperature of 1". After a week's dialysis, dilution caused no coagulation, but after adding calcium sulphate clotting set in, though slowly. It was suggested that the fibrin ferment exists as a zymogen in plasma, and is converted into ferment by the action of calcium snlphate. Horse's blood kept fromPHY SIOLOQICAL OHENISTRY. 307 clotting by cold was precipitated by a large excess of alcohol ; after remaining for some weeks under the spirit, the precipitate was collected, dried, and extracted with a 0.6 per cent.sodium chloride solution ; this was warmed with calcium sulphate for an hour, and then that salt removed by dialysis ; but on diluting plasma or pericardial fluid with this there was no hastening of the coagulation ; that is, there was no evidence of zymogen conversion. Calcium sulphate helps the working of the ferment, but it is not concerned with its liberation. Quantitative experiments on the rela- tion of the amount of fibrin formed to the amount of calcium sulphate added negative the idea that fibrin is a union of fibrin with that salt. Hammarsten (Maly's Jahrsbericht, 4, 135) has shown that cslcirim phosphate is necessary for the proper activity of the rennet ferment.Secretion of the Gall Bladder. By B. BIRCH and H. SPONG (J. PhzpioE., 8, 378--383).-The fluid was obtained from two women in which a fistula remained in each case after the operation of chole- cystotomy had been performed. A celluloid cannula was found to be the best to use, as it did not set up the irritation consequent on the use of metallic ones. About 20 C.C. in the day was collected, but it is supposed that a third or more of the fluid was lost. In both cases the bile channels were completely closed off from the gall bladder, and no biliary constituents were present. The fluid was therefore the secretion of the mucous membrane of the gall bladder, and in both cases i t had identical composition and properties, Both pa,tients were also in excellent health.The fluid was sometimes clear, sometimes fainfly opalescent; it was viscid; its specific gravity varied from 1.011 to 1.012 at 12.5". On microscopic exaniinntion, it was found to contain a few leucocytes. It was always distinctly alkaline, which reaction must be attributed to alkaline sodium phosphate. The following is the approximate quantitative analysis in parts per 1000 :- W. D. H. Water and gases .............. 979.7 Solids ........................ 20.3 A. Organic- ........................ } 12.09 Mucin Protei'd matter, a trace. ......... B. Inorganic- Chlorine. ..................... 3.84 Carbonic anhydride ............ 0.29 Sodium (combined with Cl) ..... 2-50 Soda (combined wit'h GO,) ...... 0.41 Potassium salts and phosphates by difference ..................1.1 7 20.30 The fluid has distinct diastatic properties, which were destroyed by boiling ; the fermentation agent was not definitely separated ; the308 ABSTRACTS OF CHEMICAL PAPERS. Dry substance. 2G.6 18.3 1'7.4 24.6 36-4 21-8 alcoholic precipitate, however, was found to contain it, whilst none remained in the filtrate ; the ferment was also non-diffusible. Some was filtered through a porous cell; the filtrate was inoperative on st'arch, whilst the residue, which evidently represented the mucin that could not get through the filter, was still active. The fluid had no curdling action on milk, and no emuIsion was formed when it was mixed with cod-liver oil. The secretion, moreover, does not readily putrefy, although it was demonstrated by means of experiments with sterilised peptone infusion that it has no active power in restraining putrefac- tion; its apparent immunity from change being due to its poverty in nourishing material.The secretion cannot be regarded as playing any important part in digestion, the small diastatic action it possesses being shared by many fluids in the economy on which it does not confer any special digestive value. Its use is no doubt confined to lubricating the walls of the gall bladder, and it adventitiously adds some mucus to the bile which comes to repose in it. W. D. H. Albu- mino'id. 18.3 16.8 15.8 18.4 21.6 17% Analyses of American Fishes. By W. 0. ATWATER (Amer. Chern. J., 9, 421452).-52 species of American fishes were ex- amined. The methods of analysis are described, and tables are given containing proportion of edible portion and the amounts of nitrogen, proteids, ether extract, and ash of this portion of the fish.The com- position varies very considerably, thus- 7.1 0.25 0.4 5 - 2 13-4 2 . 8 Water. 1 . 3 1.2 1'2 1-1 1.4 1 . 2 Mackerel ................... Haddock ................... Cod ........................ Halibut .................... Salmon ..................... Spent salmon, female ......... 73 -4 81 -7 82.6 75 *4 63 *6 78 - 2 Fat. 1 Ash. I- H. H. Ferments in Normal Urine. By E. STADELMANN (Zeit. Biol., 24, 226--260).-Very divergent opinions have from time to time been expressed with reference to the presence of ferments in normal urine. It may be safely said that all observers are agreed on the constant occurrence of pepsin in normal urine, but the most conflicting evidence is forthcoming as to the presence of trypsin.Griitzner and his pupils, Sahli, Gehrig, and Holortschiner state that trypsin is a constant concomitant of normal urine, and that it is present in regular quantity. Mya and Belfanti state that both pepsin and trypsin are present in normal' and pathological urine, except in cases of acute and chronic nephritis. In opposition to this, Leo denies the occurrence of trypsin in all cases, but admits the presence of pepsin in normal and in most patho- logical cases. In cancer of the stomach and typhoid fever, pepflin, is however, absent.PHTSIOLOGICAI 1 CHEMI STRT. ? 09 In the presmt investigation, a complete survey of the whole subject has beeu undertaken. The occurrence of pepsin is further corrobo- raked, but in no instance has trypsin been found.The author, there- fore, considers with Leo that the apparent digestion of raw fibrin in alkaline urine, in Griitzner’s and other ObEerverS’ experiments, was due to the presence of sepsis which had not been sufficiently guarded against. Raw fibrin does disintegrate in alkaline urine even in the presence of thymol, owing no doubt to the presence of bacteria in the raw fibrin, but in no instance did any digestion or disintegration take place when boiled fibrin was used. As the direct experiments with urine were negative, a large quantity was evaporated nearly to dryness a t 40°, the residue thoroughly exti*acted, and washed with alcohol. The residue, which would contain any trypsin that might be present, was then dissolved in a small quantity of water and tested with regard to its digestive power, but the solution was found to be entirely inert.When proper precautions are taken to enswe the absence of any putrefactive change, the results are always negative. Certain inorganic salts-potassium, sodium, and ammonium siil- phates, and potassium and sodium phosphates-hinder tryptic diges- tion in a marked degree. This is especially the case with the potassium phosphates. J. P. L. Physiological Action of Ethyl Lactate. By P. PEZLACAX’I and G. BERTONI (Chew. Cent?.., 1E87, 1149 ; from Arch. ItaZ. Bid., 7, 201-- 208).-The ethyl salt of fermentation lactic acid, when taken by the mouth in concentrated solutions, causes great irrit.ation of the throat and the first p r t s of the alimentary tract.When subcutaneously injected i t causes no local irritation. A 10 to 15 per cent. solution does not coagulate albumin. It is a liquid, and soluble in all propor- tions in water, alcohol, and ether. Its hypnotic properties are weak, and its physiological action is compared with that of chloral and iodal. When given in doses sufficient to cause deep anmthesia, it causes death by iuterference with the respiration. w. I). 13;. Physiological Action of Trimethylethyloxyarnmonium aT: d Trimethylvinylammonium Hydroxides. By V. CERVELLO (Chem. Centr., 1887, 1150; from Arch. ItaZ. BioZ., 7, 232-233).-0°.01 gram of the hydrochloride of the first base causes in the frog, dilatation of the pupil and increased frequency of respiration; after about two hours the animal returns to its normal condition.To cause complete paralysis, at least 0-05 gram must be given: death then occurs in about three hours. In a rabbit weighing 850 grams, 0-5 gram caused increased secretion of tears, running from the nose, and enlargement of the pupil. Paralysis, which ensues aft,er large doses, is produced like that caused by cumre. Aqneous solutions of trimethylvinylammonium hydroxide (neurine), came the same symptoms, but its action is more powerful. The antagonism between this base and atropine holds only with regard to the heart and glandular system. Atropine will not prevent death after the administration of lethal doses of neurine. Neurine thus The pulse is but little affected.310 ABSTRACTS OF CHEMICAL PAPERS. resembles curare in its physiological action, and muscarin in its antagonism to atropine.W. D. H. Physiological Action of ((Saccharin." By V. ADUCCO and U. Moss0 (Chein. Centr., 1887, 1148-1149 ; from Arch. Ital. Biol., 7, 158-171 ; and 8,22-36).-" Saccharin " (Fahlberg) is but little solu- ble in cold water, but dissolves more easily in hot, and very easily in boiling water. The solution so obtained is strongly acid. On cooling the hot, concentrated aqueous solution, the substance separates in monoclinic (2) needles melting at about 200". It is more easily soluble in ether, and still more so in alcohol: it dissolves easily in water if its solution be continuously and carefully neutralised, but is reprecipitated on addition of hydrochloric acid.Even in large doses, it is harmless to the animal organism. After its administration, the uriiie has a well-marked, sweet taste, and decomposes with much more di6culty ; it contains unaltered saccharin. It causes no alteration in nutrition or metabolism, with the exception that the chlorides of the urine are increased in amount. Saccharin is not excreted by the saliva nor by the milk. Half an hour after its administration by the mouth, +,he urine acquires a very sweet taste, which after doses of 5 grams disappears in 24 hours. 0.16 gram of saccharin weakens the alcoholic fermention of dextrose, as well at 30" as a t 16". A mixture of urine with an equal volume of a 0.32 per cent. solution of Mac- charin does not undergo the ammoniacal fermentation for over seven days, whilst urine mixed with a corresponding amount of salicylic acid ferments in less than that time.Saccharin also prevents putre- faction during pancreatic digestion. A percentage of 0.16 to 0.32 of saccharin hinders but does not prevent gastric digestmion. A per- centage of 0.0064 has no such effect. Benzoic acid in similar amounts has the same effect; salicylic acid a stronger effect. Saccharin hinders the amylol y tic action of saliva, especially in a neutral solution, but not so much as does salicylic acid; benzoic acid, on the other hand, is not so active. As the sweetness of saccharin is 280 times greater than that of cane-sugar, it can be, substituted for the latter in common use. The taste is pleasanter on neutralising and diluting.It can also be used to prevent fermentative changes in the stomach, in the urinary bladder, and for disinfection generally. W. D. H. Physiological Action of Santonin and its Derivatives. By F. COPPOLA (Chem. Centr., 1887, 1206, 1208-1209, 1301-1302 ; from Rend. R. Acc. Lincei [4], 3, 513-521, 573-578).-0ne per cent. solutions of santonin, of photosantonin, and of isophotosantonin in olive oil, at. 38", do not kill the ascarides lumbricoidi of the pig. Whilst, however, the two first-named substances increase the move- ments of the animal and cause convulsions, with isophotosantonin the reverse is the case. The other santonin-derivatives examined re- semble the two first in their action on the worms. It was also found that doses of 1.25 grams of santonin daily administered to the pigdid not kill the worms.The action of santonin 011 worms resembles its action on vertebrate animals. In order to lessen the toxic effects ofPHYSIOLOGICAL CHEMISTRY. 311 the drug on the animal to which it is given i t is advisable to use santoninoxime (Cannizzaro, Rend. B. Acc. Lincei, 1885, 703) which is insoluble in water, easily soluble in oils and fats, but not in crganic acids, nor is it acted on by the gastric juice. The increased activity of the worms leads to increased peristaltic action of the intestine, which thus voids them. In the urine, santoninoxime passes out slowly as santonin ; it is less poisonous than santonin, b u t is equally effica- cious in its action on the pmasites. Experiments were also performed in order to see whether the photo- santonin-derivatives differed in their action from that of santonin, and also to discover if any relation existed between physiological action and the power of solutions of these compounds to rotate the plane of polarised light.Photosantonic acid, C15H2a05, has a narcotic action 011 frogs, doses of 0.02 to 0.03 gram abolishing first voluutary move- ment, then the movements of respiration ; the heart and reflexes are but little affected : doses of 0.04-0*06 gram first diminish, a,nd then abolish reflexes, and stop the heart in diastole. I n vertebrate animals the action is similar, except that the reflexes are not affected. Photo- santonin, C,7H2101, acts in the same way, but on account of its smaller solubiiity the effects are not so marked. Snntonin, CuH,,03, itself, and sodium santonate cause as their chief symptoms convulsions ; it seems then that the action of light is to modify the physiological action of these cornpounds on the nervous system ; the action on the respiratory and circulatory systems is, however, the same.Santonic acid, C15H2004, in doses of 0.03 gram, causes no effect in frogs ; 0.04 to 0.05 gram produces narcosis, abolishes respiratory movements, but does not lessen reflexes. Larger doses affect the reflexes and kill the animal ; if the dose is not lethal, the animal experiences clonic con- vulsions like those produced by santonin, as the narcosis passes off. In a rabbit of 1 kilo. body-weight, doses of 1 to 1.5 gram applied hypodermically have no effect: 2 to 3 grams caused sleep in 4 to 1 hour, and, like santonin, epileptic convulsions.There is no action on the circulation, except with lethal doses, which stop the heart in dia- stoie : atropine does not antagonise this action ; this acid thus pro- duces the effect of santonin combined with that of the photo-com- pounds, both narcosis and convulsions. Santonic and isosantonic acids act like photosantonic acid. Isophotosantonin, C17H2101, is no hypnotic, but easily causes strong convulsions. Isophotosantonic acid, C15H22[4]05, acts similarly, but is weaker. The derivatives of santonin that cause convulsions do so by their action on the medulla, not on the spinal cord. The photo-derivatives contain, like santonin, a closed naphthalene nucleus, and the differences on their constitution are to be found in the side-chains.There was found to be no connec- tion between physiological action and the direction or amount of rota- tion of the plane of polarised light. Physiological Action of Thallin. By G. PrsENfrr (f%em. Centr., 1887, 1149-1150 ; from Amh. ItaZ. Bid., 7, 134--141).-Jaksch (Zeit. KZirL. bled., 8 ) states that thallin is a strong febrifuge, but one which has no influence on the course of the disease. I n the present research i t was found that small doses (0.025-0*075 gram) lower the W. D. H.312 ABSTRACTS OF CHEMICAL PAPERS. temperature of fever patients directly a d considerably, but only for a short time : and as Jaksch states, there is no alteration in the cmrse of the malady which causes the high temperature. The salt used was the sulphate.This salt hinders putrefaction, lowers the blood pres- sure considerably, and leaves the body by the liver and kidneys. Subcutaneous injection is not dangerous. Action of Brucine and Strychnine. By T. J. MAYS (J. Ph?ysiot., 8, 391--403).-1t was found that in the frog the physiological effects of poisoning by strychnine and brucine respectively differ as fol- lows :-(1.) Brucine pi-imarilp affects tho posterior, whilst, strychnine affects the anterior extremities. (2.) Convulsions appear very early in strychnine, and not at all or very late in brucine poisoning. (!.) Convulsions invariably develop before death occurs in strychnine poisoning, whilst death often occurs in brucine poisoning without a trace of spasm. (4.) Rrucine diminishes sensibility when locally applied, whilst strychnine does not,.(5.) The local anaesthetic effect of brucine appears to bear a direct relationship t o its degree of freedom from strychnine. W. D. H. W. D. H. Physiological Action of Caffeine. By F. COPPOLA (Chem. Centr., 1887, 1209-1210 ; from Ann. Chim. IFarm., 8, 10-38).- From the result of numerous experiments on both cold- and warm- blooded animals the following conclusions are drawn :-Gaff e'ine does not belong to the same pharmacological group as digitalin, because it acbs on the heart and the nerve-centres, whilst digitalin and the glucosides derived from i t are characterised by their exclusive action on the heart. Both strengthen the heart's action by stimulation of the muscular tissue of that organ, but they act differently on the frequency of t6he beat. The chief difference is, however, that caffe'ine causes dilatation and digitalin contraction of the blood-vessels.In many cases of cardiac degeneration where digitalis is useless caffeine does much good. The dilatation of the vessels produced by caffei'ne renders it a, valuable drug in cases of cerebral anmmia and consequent headache due to contraction of the cerebral vessels ; though whether this drug would be useful in migraine it is impossible at present. to say. I W. D. H. Physiological Action of CocaYne. By C. SIGHICELLI (Chem. Centr., 1887, 1150 ; from Arch. Itat. Biol., 7, 128-133) .-Coca'ine causes complete paralysis of the muscles of the eyeball, and indeed of all small striped muscles. On dropping about 1 c c. of a 2 per cent.solution of the hydrochloride into the eye, the above takes place in about 10 minutes. It causes widening of the pupil and paralysis of the iris. It has the same action on the smooth muscles of the intes- tine. W. D. H.PHYSIOLOGICAL CHEMISTRY.P h y s i o l o g i c a1 C h e m i s t r y .305Influence of Sleep on the Activity of Respiratory Combus-tion. By L. DE SAINT-MARTIN (Compt: rend., 105, 1124-1128).-Experiments with doves show that, independently of the effect pro-duced by fasting, natural sleep reduces the quantity of carbonicanhydride exhaled by about one-fifth, and reduces the quantity ofoxygen absorbed by about one-tenth.Experiments with dogs show that during sleep produced by mor-phine the proportion of carbonic anhydride exhaled falls to one-halfthe normal amount ; during sleep produced by chloral or chloroformit falls to one-third the normal proportion.When anmthesia by chloroform is sufficiently long continued theblood becomes impoverished in oxygen and is charged with an amount ofcarbonic anhydride very considerably in excess of the normal propor-tion. In the early stage of insensibility, there is a diminution in theproportion of carbonic anhydride in the blood, but this is due tosecondary causes.C. H. B.Coagulation of Fibrin and Intravt#xular Clotting. By F.KRGGER (Zeit. Biol .24, 189--225).-Wooldpidge has shown that thephenomenon of coagulation is brought about by a substance which hecalls A fibrinogen, obtainable from peptone plasma by simply cooling,and that the cellular elements which were hitherto considered essen-tial, although they may assist coagulation, are nevertheless of second-ary import.In his Croonian lecture he described coagulation asessentially similar to crystallisation. In plmmai there are three con-stituents concerned in coagulation-A, B, and C fibrinogen. A and Bfibrinogen are compounds of lecithin and proteid, and fibrin resultsfrom the transference of the lecithin from A Gbrinogen to B fibrino-gen. From this point of view the ferment is of secondary import-ance.Wooldridge further found that a compound of lecithin and prote’idclosely allied to the A fibrinogen, which he considers probably th306 ABSTRACTS OF CHEMICAL PAPERS.precursor of A fibrinogen, exists in the testis and thymus gland of thecalf, in the fluid of the lymph glands and the stromata of red blood-corpuscles.This compound is capable of causing widespread intra-vascular clotting in the entire absence of any cellular elements.It is with reference t o this last statement that the author joinsissue, A large number of experiments have led him to the oppositeconclusion, namely, that the corpuscular elements play the chief partin the coagulation, both within and without the body. He corrobo-rates Wooldridge's statement, however, that the stromata of redblood corpuscles produce intravascular clotting.The leucocytes obtained by centrifugalising the fluid of the lymphglands produce intravascular clotting, but the supernatant liquid, theauthor states, is inert, o r almost so.He considers that any slightaction of the fluid may be accounted for by the presence of some leuco-cytes, for he found it impossible to remove them completely, even bycentrifugal action. J. P. L.Influence of Calcium Sulphate on the Coagulation of theBlood. By J. R. GREEN (J. PhysioZ., 8, 354--371).-A salineextract of washed blood clot contains fibrin ferment (Bnchanan).Henting.such an extract nearly to the boiling point delays the actionof the ferment but does mot destroy it ; the ash was found to contain ndefinite and fairly constant amount of calcium sulphate. A saturatedsolution of calcinrn sulyhate was prepared, and on adding 1 C.C. of thisto 10 c c. of diluted magnesium sulphate plasma, coagulation set inwith great rapidity; a very small amount of the salt (0.001 per cent.)has considerable clotting power ; this increases with the quantity ofcalcium sulphate used, but not proportionately.In other experimentswith peptone or leech extract, in which coagulation was reiarded bycold, the addition of calcium sulphate caused it to take place in somecases very rapidly, in others more slowly.Calcium sulphate cannd be regarded as the fibrin ferment however ;addition of that salt to pericardial fluid or t o a sodium chloride solu-tion of fibrinogen causes no coagulation in those fluids ; but when theferment is present, addition of salt accelerates the coagulation.The next point investigated was whether it is possible to havecoagulation in the absence of calcium sulphate ; peptone-plasma wasdialysed for three days into a 0.6 per cent.solution of sodiumchloride ; if water had been used outside fhe membrane, the globulinsof the plasma would have been precipitated. Dilution of the plasmawith saline solutions then caused no clotting, nor did the passing of Rstream of carbonic anhydride through the plasma coagulate it as i tdoes ordinary peptone-plasma,. But on adding a little calciumsulphate to fhe diluted plasma coagulation rapidly set in.In plasma prevented from coagulating by cold, or by admixturewith magnesium sulphate, similar experiments were performed,dialysis being carried out at the temperature of 1". After a week'sdialysis, dilution caused no coagulation, but after adding calciumsulphate clotting set in, though slowly.It was suggested that thefibrin ferment exists as a zymogen in plasma, and is converted intoferment by the action of calcium snlphate. Horse's blood kept froPHY SIOLOQICAL OHENISTRY. 307clotting by cold was precipitated by a large excess of alcohol ; afterremaining for some weeks under the spirit, the precipitate was collected,dried, and extracted with a 0.6 per cent. sodium chloride solution ; thiswas warmed with calcium sulphate for an hour, and then that saltremoved by dialysis ; but on diluting plasma or pericardial fluid withthis there was no hastening of the coagulation ; that is, there was noevidence of zymogen conversion.Calcium sulphate helps the working of the ferment, but it is notconcerned with its liberation.Quantitative experiments on the rela-tion of the amount of fibrin formed to the amount of calcium sulphateadded negative the idea that fibrin is a union of fibrin with that salt.Hammarsten (Maly's Jahrsbericht, 4, 135) has shown that cslcirimphosphate is necessary for the proper activity of the rennet ferment.Secretion of the Gall Bladder. By B. BIRCH and H. SPONG(J. PhzpioE., 8, 378--383).-The fluid was obtained from two womenin which a fistula remained in each case after the operation of chole-cystotomy had been performed. A celluloid cannula was found to bethe best to use, as it did not set up the irritation consequent on theuse of metallic ones. About 20 C.C. in the day was collected, but it issupposed that a third or more of the fluid was lost.In both cases thebile channels were completely closed off from the gall bladder, and nobiliary constituents were present. The fluid was therefore thesecretion of the mucous membrane of the gall bladder, and in bothcases i t had identical composition and properties, Both pa,tients werealso in excellent health. The fluid was sometimes clear, sometimesfainfly opalescent; it was viscid; its specific gravity varied from1.011 to 1.012 at 12.5". On microscopic exaniinntion, it was found tocontain a few leucocytes. It was always distinctly alkaline, whichreaction must be attributed to alkaline sodium phosphate. Thefollowing is the approximate quantitative analysis in parts per1000 :-W. D. H.Water and gases ..............979.7Solids ........................ 20.3A. Organic-........................ } 12.09 MucinProtei'd matter, a trace. .........B. Inorganic-Chlorine. ..................... 3.84Carbonic anhydride ............ 0.29Sodium (combined with Cl) ..... 2-50Soda (combined wit'h GO,) ...... 0.41Potassium salts and phosphates bydifference .................. 1.1 720.30The fluid has distinct diastatic properties, which were destroyed byboiling ; the fermentation agent was not definitely separated ; th308 ABSTRACTS OF CHEMICAL PAPERS.Drysubstance.2G.618.31'7.424.636-421-8alcoholic precipitate, however, was found to contain it, whilst noneremained in the filtrate ; the ferment was also non-diffusible. Somewas filtered through a porous cell; the filtrate was inoperative onst'arch, whilst the residue, which evidently represented the mucin thatcould not get through the filter, was still active.The fluid had nocurdling action on milk, and no emuIsion was formed when it was mixedwith cod-liver oil. The secretion, moreover, does not readily putrefy,although it was demonstrated by means of experiments with sterilisedpeptone infusion that it has no active power in restraining putrefac-tion; its apparent immunity from change being due to its povertyin nourishing material. The secretion cannot be regarded as playingany important part in digestion, the small diastatic action it possessesbeing shared by many fluids in the economy on which it does notconfer any special digestive value.Its use is no doubt confined tolubricating the walls of the gall bladder, and it adventitiously addssome mucus to the bile which comes to repose in it. W. D. H.Albu-mino'id.18.316.815.818.421.617%Analyses of American Fishes. By W. 0. ATWATER (Amer.Chern. J., 9, 421452).-52 species of American fishes were ex-amined. The methods of analysis are described, and tables are givencontaining proportion of edible portion and the amounts of nitrogen,proteids, ether extract, and ash of this portion of the fish. The com-position varies very considerably, thus-7.10.250.45 - 213-42 . 8Water.1 . 31.21'21-11.41 . 2Mackerel ...................Haddock ...................Cod ........................Halibut ....................Salmon .....................Spent salmon, female .........73 -481 -782.675 *463 *678 - 2Fat.1 Ash.I-H. H.Ferments in Normal Urine. By E. STADELMANN (Zeit. Biol., 24,226--260).-Very divergent opinions have from time to time beenexpressed with reference to the presence of ferments in normal urine.It may be safely said that all observers are agreed on the constantoccurrence of pepsin in normal urine, but the most conflictingevidence is forthcoming as to the presence of trypsin.Griitzner and his pupils, Sahli, Gehrig, and Holortschiner state thattrypsin is a constant concomitant of normal urine, and that it ispresent in regular quantity. Mya and Belfanti state that both pepsinand trypsin are present in normal' and pathological urine, except incases of acute and chronic nephritis.In opposition to this, Leo denies the occurrence of trypsin in allcases, but admits the presence of pepsin in normal and in most patho-logical cases.In cancer of the stomach and typhoid fever, pepflin, ishowever, absentPHTSIOLOGICAI 1 CHEMI STRT. ? 09In the presmt investigation, a complete survey of the whole subjecthas beeu undertaken. The occurrence of pepsin is further corrobo-raked, but in no instance has trypsin been found. The author, there-fore, considers with Leo that the apparent digestion of raw fibrin inalkaline urine, in Griitzner’s and other ObEerverS’ experiments, wasdue to the presence of sepsis which had not been sufficiently guardedagainst.Raw fibrin does disintegrate in alkaline urine even in thepresence of thymol, owing no doubt to the presence of bacteria in theraw fibrin, but in no instance did any digestion or disintegration takeplace when boiled fibrin was used. As the direct experiments withurine were negative, a large quantity was evaporated nearly to drynessa t 40°, the residue thoroughly exti*acted, and washed with alcohol.The residue, which would contain any trypsin that might be present,was then dissolved in a small quantity of water and tested withregard to its digestive power, but the solution was found to be entirelyinert. When proper precautions are taken to enswe the absence ofany putrefactive change, the results are always negative.Certain inorganic salts-potassium, sodium, and ammonium siil-phates, and potassium and sodium phosphates-hinder tryptic diges-tion in a marked degree.This is especially the case with thepotassium phosphates. J. P. L.Physiological Action of Ethyl Lactate. By P. PEZLACAX’I andG. BERTONI (Chew. Cent?.., 1E87, 1149 ; from Arch. ItaZ. Bid., 7, 201--208).-The ethyl salt of fermentation lactic acid, when taken by themouth in concentrated solutions, causes great irrit.ation of the throatand the first p r t s of the alimentary tract. When subcutaneouslyinjected i t causes no local irritation. A 10 to 15 per cent. solutiondoes not coagulate albumin. It is a liquid, and soluble in all propor-tions in water, alcohol, and ether. Its hypnotic properties are weak,and its physiological action is compared with that of chloral and iodal.When given in doses sufficient to cause deep anmthesia, it causesdeath by iuterference with the respiration.w. I). 13;.Physiological Action of Trimethylethyloxyarnmonium aT: dTrimethylvinylammonium Hydroxides. By V. CERVELLO (Chem.Centr., 1887, 1150; from Arch. ItaZ. BioZ., 7, 232-233).-0°.01 gramof the hydrochloride of the first base causes in the frog, dilatation ofthe pupil and increased frequency of respiration; after about twohours the animal returns to its normal condition. To cause completeparalysis, at least 0-05 gram must be given: death then occurs inabout three hours. In a rabbitweighing 850 grams, 0-5 gram caused increased secretion of tears,running from the nose, and enlargement of the pupil.Paralysis,which ensues aft,er large doses, is produced like that caused by cumre.Aqneous solutions of trimethylvinylammonium hydroxide (neurine),came the same symptoms, but its action is more powerful. Theantagonism between this base and atropine holds only with regard tothe heart and glandular system. Atropine will not prevent deathafter the administration of lethal doses of neurine. Neurine thusThe pulse is but little affected310 ABSTRACTS OF CHEMICAL PAPERS.resembles curare in its physiological action, and muscarin in itsantagonism to atropine. W. D. H.Physiological Action of ((Saccharin." By V. ADUCCO and U.Moss0 (Chein. Centr., 1887, 1148-1149 ; from Arch. Ital. Biol., 7,158-171 ; and 8,22-36).-" Saccharin " (Fahlberg) is but little solu-ble in cold water, but dissolves more easily in hot, and very easily inboiling water.The solution so obtained is strongly acid. On coolingthe hot, concentrated aqueous solution, the substance separates inmonoclinic (2) needles melting at about 200". It is more easilysoluble in ether, and still more so in alcohol: it dissolves easily inwater if its solution be continuously and carefully neutralised, but isreprecipitated on addition of hydrochloric acid. Even in large doses,it is harmless to the animal organism. After its administration, theuriiie has a well-marked, sweet taste, and decomposes with much moredi6culty ; it contains unaltered saccharin. It causes no alteration innutrition or metabolism, with the exception that the chlorides of theurine are increased in amount.Saccharin is not excreted by thesaliva nor by the milk. Half an hour after its administration by themouth, +,he urine acquires a very sweet taste, which after doses of5 grams disappears in 24 hours. 0.16 gram of saccharin weakens thealcoholic fermention of dextrose, as well at 30" as a t 16". A mixtureof urine with an equal volume of a 0.32 per cent. solution of Mac-charin does not undergo the ammoniacal fermentation for over sevendays, whilst urine mixed with a corresponding amount of salicylicacid ferments in less than that time. Saccharin also prevents putre-faction during pancreatic digestion. A percentage of 0.16 to 0.32 ofsaccharin hinders but does not prevent gastric digestmion.A per-centage of 0.0064 has no such effect. Benzoic acid in similar amountshas the same effect; salicylic acid a stronger effect. Saccharinhinders the amylol y tic action of saliva, especially in a neutral solution,but not so much as does salicylic acid; benzoic acid, on the otherhand, is not so active. As the sweetness of saccharin is 280 timesgreater than that of cane-sugar, it can be, substituted for the latter incommon use. The taste is pleasanter on neutralising and diluting.It can also be used to prevent fermentative changes in the stomach,in the urinary bladder, and for disinfection generally.W. D. H.Physiological Action of Santonin and its Derivatives. ByF. COPPOLA (Chem. Centr., 1887, 1206, 1208-1209, 1301-1302 ; fromRend.R. Acc. Lincei [4], 3, 513-521, 573-578).-0ne per cent.solutions of santonin, of photosantonin, and of isophotosantonin inolive oil, at. 38", do not kill the ascarides lumbricoidi of the pig.Whilst, however, the two first-named substances increase the move-ments of the animal and cause convulsions, with isophotosantonin thereverse is the case. The other santonin-derivatives examined re-semble the two first in their action on the worms. It was also foundthat doses of 1.25 grams of santonin daily administered to the pigdidnot kill the worms. The action of santonin 011 worms resembles itsaction on vertebrate animals. In order to lessen the toxic effects oPHYSIOLOGICAL CHEMISTRY. 311the drug on the animal to which it is given i t is advisable to usesantoninoxime (Cannizzaro, Rend.B. Acc. Lincei, 1885, 703) which isinsoluble in water, easily soluble in oils and fats, but not in crganicacids, nor is it acted on by the gastric juice. The increased activityof the worms leads to increased peristaltic action of the intestine,which thus voids them. In the urine, santoninoxime passes out slowlyas santonin ; it is less poisonous than santonin, b u t is equally effica-cious in its action on the pmasites.Experiments were also performed in order to see whether the photo-santonin-derivatives differed in their action from that of santonin, andalso to discover if any relation existed between physiological actionand the power of solutions of these compounds to rotate the plane ofpolarised light.Photosantonic acid, C15H2a05, has a narcotic action 011frogs, doses of 0.02 to 0.03 gram abolishing first voluutary move-ment, then the movements of respiration ; the heart and reflexes arebut little affected : doses of 0.04-0*06 gram first diminish, a,nd thenabolish reflexes, and stop the heart in diastole. I n vertebrate animalsthe action is similar, except that the reflexes are not affected. Photo-santonin, C,7H2101, acts in the same way, but on account of its smallersolubiiity the effects are not so marked. Snntonin, CuH,,03, itself,and sodium santonate cause as their chief symptoms convulsions ; itseems then that the action of light is to modify the physiologicalaction of these cornpounds on the nervous system ; the action on therespiratory and circulatory systems is, however, the same.Santonicacid, C15H2004, in doses of 0.03 gram, causes no effect in frogs ; 0.04 to0.05 gram produces narcosis, abolishes respiratory movements, butdoes not lessen reflexes. Larger doses affect the reflexes and kill theanimal ; if the dose is not lethal, the animal experiences clonic con-vulsions like those produced by santonin, as the narcosis passes off.In a rabbit of 1 kilo. body-weight, doses of 1 to 1.5 gram appliedhypodermically have no effect: 2 to 3 grams caused sleep in 4 to 1hour, and, like santonin, epileptic convulsions. There is no action onthe circulation, except with lethal doses, which stop the heart in dia-stoie : atropine does not antagonise this action ; this acid thus pro-duces the effect of santonin combined with that of the photo-com-pounds, both narcosis and convulsions.Santonic and isosantonicacids act like photosantonic acid. Isophotosantonin, C17H2101, isno hypnotic, but easily causes strong convulsions. Isophotosantonicacid, C15H22[4]05, acts similarly, but is weaker. The derivatives ofsantonin that cause convulsions do so by their action on the medulla,not on the spinal cord. The photo-derivatives contain, like santonin,a closed naphthalene nucleus, and the differences on their constitutionare to be found in the side-chains. There was found to be no connec-tion between physiological action and the direction or amount of rota-tion of the plane of polarised light.Physiological Action of Thallin.By G. PrsENfrr (f%em. Centr.,1887, 1149-1150 ; from Amh. ItaZ. Bid., 7, 134--141).-Jaksch(Zeit. KZirL. bled., 8 ) states that thallin is a strong febrifuge, but onewhich has no influence on the course of the disease. I n the presentresearch i t was found that small doses (0.025-0*075 gram) lower theW. D. H312 ABSTRACTS OF CHEMICAL PAPERS.temperature of fever patients directly a d considerably, but only fora short time : and as Jaksch states, there is no alteration in the cmrseof the malady which causes the high temperature. The salt used wasthe sulphate. This salt hinders putrefaction, lowers the blood pres-sure considerably, and leaves the body by the liver and kidneys.Subcutaneous injection is not dangerous.Action of Brucine and Strychnine. By T. J. MAYS (J. Ph?ysiot.,8, 391--403).-1t was found that in the frog the physiological effectsof poisoning by strychnine and brucine respectively differ as fol-lows :-(1.) Brucine pi-imarilp affects tho posterior, whilst, strychnineaffects the anterior extremities. (2.) Convulsions appear very earlyin strychnine, and not at all or very late in brucine poisoning. (!.)Convulsions invariably develop before death occurs in strychninepoisoning, whilst death often occurs in brucine poisoning without atrace of spasm. (4.) Rrucine diminishes sensibility when locallyapplied, whilst strychnine does not,. (5.) The local anaesthetic effectof brucine appears to bear a direct relationship t o its degree offreedom from strychnine.W. D. H.W. D. H.Physiological Action of Caffeine. By F. COPPOLA (Chem.Centr., 1887, 1209-1210 ; from Ann. Chim. IFarm., 8, 10-38).-From the result of numerous experiments on both cold- and warm-blooded animals the following conclusions are drawn :-Gaff e'ine doesnot belong to the same pharmacological group as digitalin, becauseit acbs on the heart and the nerve-centres, whilst digitalin and theglucosides derived from i t are characterised by their exclusive actionon the heart. Both strengthen the heart's action by stimulation ofthe muscular tissue of that organ, but they act differently on thefrequency of t6he beat. The chief difference is, however, that caffe'inecauses dilatation and digitalin contraction of the blood-vessels. Inmany cases of cardiac degeneration where digitalis is useless caffeinedoes much good.The dilatation of the vessels produced by caffei'ne renders it a,valuable drug in cases of cerebral anmmia and consequent headachedue to contraction of the cerebral vessels ; though whether this drugwould be useful in migraine it is impossible at present. to say. IW. D. H.Physiological Action of CocaYne. By C. SIGHICELLI (Chem.Centr., 1887, 1150 ; from Arch. Itat. Biol., 7, 128-133) .-Coca'inecauses complete paralysis of the muscles of the eyeball, and indeed ofall small striped muscles. On dropping about 1 c c. of a 2 per cent.solution of the hydrochloride into the eye, the above takes place inabout 10 minutes. It causes widening of the pupil and paralysis ofthe iris. It has the same action on the smooth muscles of the intes-tine. W. D. H

ISSN:0368-1769    

DOI:10.1039/CA8885400305

出版商:RSC    

年代:1888

数据来源: RSC