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158 ABSTRACTS O F CHEMICAL PAPERS. M in e r a 1 o g i c a1 C h em i s t ry. Mechanical Separation of Minerals. By L. PEBAL (Monatsh. Chem., 3, 723-’725).-In this paper, which is partly a reply to Doelter’s remarks on the same subject (Abstr., 1882, 656, 1173), the author recommends the following modification of his method of moving t,he electromagnet about in water holding the finely pul- verised mineral in suspension. To avoid the formation of lumps, arising from the enclosure of air-bubbles, the fine powder of the mineral is made slowly to absorb water-or alcohol if water will not wet it-from one side only, after which it is treated as followv :-A number of moderate-sized beaker-glasses are filled with distilled water ; the moistened rock-powder is introduced into the first; into this powder is thrust the end of the iron rod surrounded with a coil of wire; and the circuit is closed, while the water is briskly agitated. The electromagnet is then dipped into the second glass ; the circuit is broken ; and t h i s treatment is repeated till the magnet in the firstMIKERALOGICAL CHEMISTRY.159 glass no longer attracts any particles. After all the magnetic pa,rticles have thus been transferred to the sec,ond glass, the process is repeated in exactly the same manner with the second and third glass, then with the third and fourth, and so on till the magnetised bar no longer leaves any residue in the last glass but one. The contents of the last glass are then collected on one filter, and those of all the others on a secoud filter.With a moderate amount of care in carrying out this process, it is easy to avoid loss of substance. One point, however, must not be overlooked, namely, the behaviour of solid diamagnetic bodies in diamagnetic liquids, whereby, if the diamagnetism of the liquid is stronger than that of the solid body, repulsion becomes converted into attraction. 8. w. Application of a Solution of Potassium and Mercury Iodides to Mineralogical and Petrographical Researches. By V. GOLD- SCHMIDT (Jalub. $. Min., 12181, 1, Beil. Bd., 179--238).-1t is to be regretted that the subject of the separation of the constituents of a rock has been neglected of late, in consequence of the success which has attended microscopic investigation, as there are cases in which the latter method cannot be relied on. The separation may be effected chemically or mechanically ; in the latter case advantage is taken of thedifference in the sp.gr. of the substances. I n 1877 Church (" On a Test of Sp. Gr.," illin. LWxg., 1877) proposed to separate the con- stituents of a rock according to their sp. gr. by the help of an aqueous solution of the iodides of potassium and merccry. The paper gives a t some length an accouiit of J. Thoulet's researches on the same subject (Bull. SOC. i l l i ~ , 1879, No. 1). On investigating the subject further, t'he author decided to employ a solution in which the weight of potassium iodide present is to the mercury iodide as 1 is to 1.239; and this solution has a sp. gr. of 3.196, so that fluorspar floats in i t ; while the solutions of T'hoiilet and Church gave as the maximum sp.gr. 2-77 and 3.01 respectively. The maximum density is, however, not constant. It depends on the moisture of the atmosphere and on the temperature. In summer the maximum was 3.196, whilst in winter it was only 3.17. The difficulties which attend this simple method of separation of the rock constituents according to the sp. gr. are due to the variation in the sp. gr. of the predominating mineral ; the close combination of the constituents ; the smallness of the grains ; the great similarity, or, in some cases, identity of sp. gr. of different minerals occurring together, such as quartz and oligoclase; the tendency of the lighter grains when they are in great excess to bring the heavier with them to the top ; and the 1iabilit)y of the solution to change by evaporation or by taking up water.In considering this method, the question arises : Is the value of the sp. gr. constant enough for the mineral to be determined by it, and if a separation is effected between narrow limits of weight, can it with certainty be asserted that the mineral sought for has been separated? I n order to answer the question practically, the author submitted the felspar-group to the strictest inqestigation, and came t o the conclusion that, with fresh material Theoretically it is so.160 ABSTRACTS 01' CHEMICAL PAPERS. and perfect separation, the determination of the sp. gr. gives an exact conclusion as to the nature of the felspar. The apparatus used for the separation of the rock-constituents pro- posed by Thoulet is described, but the author prefers to effect the separation in small beakers of about 40-50 C.C.capacity, the principal advantage of which is that the parts swimming above can be better manipulated with the glass rod, and, consequently, the heavier grains which are enclosed more easily separated. d number of minerals whose sp. gr. has been exactly determined, are used as indi- cators in the solution. The powdered rock and the indicators are introduced into about 30 C.C. of the concentrated solution and stirred, then allowed to subside, and the lighter parts removed. The success of the separation depends on the skill of the experimenter, on the choice of the indicators, but, above all, on the nature of the substance to be separated. It is evident, then, that Thoulet's opinion that the constituents of a rock can be qualitatively and quantitatively separated, holds good only very rarely, and i t would bo necessary also in most cases to make use of auxiliary methods, such as treating the powder with various reagents or with the magnet.Native Palladium-Gold from Taguaril, Brazil. By W. H. SEAXON (Chem. News, 46, 216).-Sp. gr. = 15.73. B. H. B. Analysis:- All. Pd. Age Fe. 91.36 8.21 trace trace E. W. P. . Alloys of Gold, Silver, &a, found in Grains along with the Native Platinum of Columbia. By W. H. SEAMON (Chem. News, 46, 215) .-Occurring with nat'ive platinum, alloys were found having the following composition :-(Ag + Cu')Au3, (Cu' + Ag),Bu6, (Ag + Hg')zAu8, Ag4AuI0. Analyses we given, together with the donsities ; but the results are not of much value, owing to the smallness of the quantity of material a t hand.E. W. P. On a Bed of Coal discovered in Algiers, and on the Layers of White Sand accompanying the same. By G. P~NARD (COW@ rend., 95, 708--709).-The author states that the results of experi- ments made with the coal of Bou-Saada in Algiers show that, both in respect of the amount of gas yielded and the illuminating power of the latter, it is quite equal to the best English and French coals, The yield of coke varies from 60 to 66 per cent. of the coal used.. The coal is always accompanied by beds of white sand arising from the disintegration of bands of sandy loam. This sand can be used for the manufacture of superior glass. Dopplerite from Aussee.By W. DEMEL (J-onatsh. Chem., 3, 763-769) .-A perfectly homogeneous specimen of this mineral freed from adhering peat and dried a t 100-120", gave by analysis 56.42 and 56-51 per cent. carbon and 5-34-5.20 hydrogen, leading to the formula C,,HI4O,, which requires 56.69 C, 5-52 €I, and 37.79 0. It yielded also 5.1 per cent. ash having the following composition:- E. H. R.MIXERALOGICAL CHEMISTRY. The high percentage of lime seems to show that this base may be present as carbonate, but the percentage of GO2 directly determined was only 0.16 ; and this, together with the smallness of the amounts of SO, and CI, shows clearly that the greater part of the lime must be combined with the organic matter, a conclusim which is confirmed by the behaviour of the mineral with caustic potash.On suspending the dopplerite in water and treating it with strong potash-lye, the mass becomes thick, pasty, and very hot, and the alkali appears to be satu- rated, as it no longer absorbs carbonic acid from the air. On boiling the liquid the dopplerite dissolves, yielding a dark brown-red solution, and from this, after filtration, acids throw down a brown flocculent precipikate which, after thorough washing and drying, becomes shining and brittle, and very much like the original dopplerite. This substance dried at 110” gave 0-73 per cent. ash, and its combustion yielded 56.86-56-99 per cent. C and 4-90-4.97 K, leading to the formula C,,H,,O,, which contains 2 at. hydrogen less than that of the original dopplerite. The alkaline solution of dopplerite gives with calcium salts a brown precipitate containing calciiim, which when dried forms a blackish- brown mms like dry dopplerite; it contains about 2-71 per cent.CaC03, and, deducting this, the composition of the salt is found to agree very nearly with the formula C2&,Ca0,,, thereby affording further evidence that. the snbstance isolated from dopplerite in the manner above described has the composition C,,H,,O,. Dopplerite fused with potassium hydroxide is converted into proto- catechuic acid (m. p. 199--201”), together with resinous and dark- coloured products containing more than 70 per cent. carbon. Ulmin (prepared from cane-sugar) also gave, on fusion with potash, protocatechuic acid, together with black amorphous masses very rich in carbon. From the similarity of the compounds above described to humus- substances in general, and from the mode of occurrence of dopplerite in peat-beds, this mineral may be regarded as the calcium salt of one or several acids beIonging to the series of humus-substances.H. W. New Sulphide received as Tetrahedrite from Great Eastern Mine, Colorado. By W. T. PAGE (Chem. News, 46, 215).--Steel- grey metallic lustre ; structure crystalline but indefinite, brittle. Hardness = 4: sp. gr. = 4-89, Composition:- Silicious s. Sb. Cu. Zu. Fe. Pb. residue. 26.88 34.47 23.20 7.14 1.38 1.19 5.86 = 100.12 This corresponds to- {jCu’aS + g(Cu”,Zn,Fe,Pb)S)Sb2S3,162 ABSTRACTS OF CHEMICAL PBPERS. This mineral might be considered as a distinct species of stylotypite, but it is better to class it as a variety of bonrnonite.E. W. P. Martite of the Cerro de Mercado, or Iron Mountain of Durango, Mexico, and certain Iron Ores of Sinaloa. By B. SILLIMAN (Am. J. Xci. [3], 23, 375--379).-This remarldJle hill exposes masses of the ore all over its surface; they appear to be derived from one or more immense beds of specular iron standing nearly vertical; the fragments form a talus on the slopes of the mountain and conceal the underlying porphyry. There is nothing to show that it is a pseudomorph of pyrites. An average sample con- tained- Fe,04. Peso3. Mn,O,. TeOz. CaO. 2 07 77.57 0.11 0.71 5.u5 0.36 0.21 3.04 1-76 1.98 - MgO. SOy. PZO,. SO2. HZO, &c. Al,O,. I n the ores from Sinaloa there still remains in the martite about one- third of the original magnetite. H.€3. New Locality for Hayesine. By N. H. DARTON (Am. J. S C ~ . [3], 23, 458-459).-This very rare mineral occurs with datholite and calcite in the traprock of Bergen Hill. Slender acicular crystals grouped on the calcite crystals ; they are probably a decomposition- product of datholite ; the rock is soft, and permeable to water. CaO. B203 HzO. Found .. .. .. .. .. .. .. 18.39 46.10 35.46 = 99.95. H. B. Occurrence and Composition of some American Varieties (1.) The specimen was appnrently homogeneous. Sp. gr. = 520- 5-25 ; locality, Pelton's Quarry, Portland, Conn. (2.j Picked grains from the monazite sand from gold washing in the Brindletown dis- trict, Burke co., N. Carolina; sp. gr. = 5.10. (3.) A specimen, also apparently pure, from Yale College.of Monazite. By s. L. YENFIELD (Am. J. Sci. [2], 24, 250-255).- P,O,. Ce203. (La,Di) aO,. Th02. SiO,. Ignition. (1.) 28.18 33.54 28.33 8-25 1.67 0.37 = 100.34 (2.) 29.28 31.38 30.88 6.49 1.4G 0.20 = 99.63 (3.) 26.12 29.83 26.66 14.23 2.85 0.67 = 100.42 These numbers are in most cases the mean of two or three deter- minations. The ratios (Ce,La,Di),03 : P,O, are 1 : 1-06, 1 : 1.08, and 1 : 1 . O i ; those of Tho, to SiO, 1 : 0.90, 1 : 092, and 1 : 0.88 respectively. The varying amounts of Tho, and SO,, and their chemical difference from the cerite metals, made it probable that the thorium silicate exists as an impurity ; this was proved by microscopic examination,MINERALOGICAL CHEMISTRY. 163 the mechanically mixed thorite being distinguished by its darker colour and easy decomposition by acids.The thoria was separated by sodium thiosulphate ; the remaining oxides were heated with dilute sulphuric and oxalic acid, and the evolved carbonic anhydride collected in potash bulbs. The joint atomic weight of the oxides obtained from the Portland specimen was 140.1, which number was also used to calcdate the results of the other analyses. H. B. Colourless Mimetite from the Richmond Mine, Nevada. By F. A. MASSIE (Chem. News, 46, 215).-Slender acicular hexagonal prisms, colourlesa, transparent, and with adamantine lustre. Hard- ness = 3 ; sp. gr. 6.92, easily fusible. As205. p 2 0 5 . PbO. PbCI,. 23-41 trace 68.21 8-69 = 100.31 agreeing with the known formula PbC12,3Pb3AszOs. Notes on some N. Carolina Minerals. By W. E. HIDDEN (Am.J. Xci. [3], 24, 372--377).-1n Alexander Co., emerald and beryl crystals, on which the rare forms 3P% and 4P$ are largely developed, are occasionally found. The supposed ceschynite from Ray's Mine, Pancey Go., is columbite. Uraninite from Mitchell Co. has sp. gr. = 8-97-9.22, and hence is not, entirely free from alteration. E'uxenite from Wiseman's mica mine has been reanalysed by .T. W. Mallett; titanic acid is absent; it is therefore probably altered aamarskite, with which it is intimately associated. Composition :- E. W. P. Fe~gzcsoizite from Burke Co. has also been analysed by Mallett. Nb205. TafO,. SnOa,W03. Y,O,, &c. C203. Di205,La203. 43.78 4-08 0.76 57-21 0.66 3.49 u2°3' FeO. CaO. H,O. 5-81 1.81 0.65 1.62 = 99.87. AZZan,ite has recently been found at two new localities, viz., Alex- ander Co.with the above-mentioned emerald crystals, and Wiseman's mica mine, Mitchell Co.; in both cases the crystals are well developed. SiOz. Al,03. Y203. Ce,03. Fe20,. FeO. MgO. CaO. H20. 39.03 14.33 8.20 1.53 7-10 5 22 4.29 17.47 2.78 = 99.95 H. B. Composition of Two Specimens of Jade. By C. L. ALLEN (Chern. News, 46, 216).-The first specimen came from the Karakash Valley, on the borders of Turkestan; it is of a pale green colour, translucent; hardness = 6.5 ; sp. gr. = 2.98, and contains- Si02. A1,03. FeO. MpO. CaO. NazO. K20. HzO. 57.35 1.03 1.22 22.73 13-40 0.25 0.23 2.69 = 98.9164 ABSTRACTS OF CHEMICAL PAPERS. The other specimen came from Hokotika, New Zealand, and is sub- translucent, with hardness = 6 ; sp.gr. 3.026. Coniposition :- Si02. A1203. FeO. MgO. CaO. Na20. K20. H20. 56.34 1.60 4.86 20.23 13.51 0.27 0.31 3-57‘ = 100.69 These specimens therefore represent the nephrite variety of amphi- bole, and the first analysis corresponds to (&Mg + -&Ca)SiO,, whilst the second corresponds to (+Mg + +Ca)Si03. By W. H. SEAMOX (Chem. News, 46, 215).-Crystals flat, well defined, imbedded in soft kaolin, pitch-black, submetallic lustre ; brownish-grey streak ; imperfect conchoTdal fracture; hardness = 6 ; sp. gr. 3.15. Corn- position :- E. W. P. Analysis of a Mineral allied to Orthite. Si02. Al,03. Y203. Ce403. Pe&. FeO. MgO. CaO. H2O. 39.03 1433 8.20 1.53 7-10 5.22 4.29 17.47 2*?8 = 99-95 Distribution of elements + &M” + &M”)Si04. E. W. P. Communications from the U.S. Geological Survey, Rocky Mountains Division. 1. Minerals, mainly Zeolites, occurring in the Basalt of Table Mountain, near Golden, Colorado. By W. CROSS and W. T. HILLEBRAND (Am. J. Sci. [3], 23, 452-458, and 24, 129--138).-Lencite does not occur. The formation of the mountain is due to two protecting sheets of lava, an upper and a lower one, of 115 feet in tliickness. I n the cavit’ies of the upper portion of the lower sheet (felspar basalt) are many beautifully crystallised zeolites, associated with calcite and arragonite. The zeolites are often found together ; the following have been determined, viz., analcite, ap Iphyllite, chnbasite, mesolite, natrolite, stilbite, and thomsonite. Chabasite is apparently the oldest zeolite, as it generally lines the cavities, and the other zeolites are formed upon it.Thomsolzite-Crystals, thin reciangulnr blades, grouped together in various ways ; where calcite crystals are not covered by chabasite, thomsonite never fails to coat them. Toward the close of the zeolitic formation, a second generation of thomsonite, and sometimes also of chabasite, was. deposited. SiO,. 8120,. CaO. N%O. H20. I. 40-68 30.12 11.92 4.44 12.86 = 100.02 11. 43.66 29.52 10.90 4.92 12.28 = 100.01 - - - - 111. 41-60 IV. 40.88 - - - I is of the older growth, and I1 of the newer. No. I was most carefully freed from any chabasite. No. I1 contained a comparatively few crystals of mesolite, and their comptek removal was impossible. I11 is of the of the thin blades, and the microscope showed the presence of irregular rounded isotropic particles imbedded in the outer parts of the crystals.No. IV was from some very fine cryshls, containing but a very few of these rounded particles. The silica isMINERhLOGlCAL CHE3IISTRT. 165 higher than that allowed by the generally accepted formula; the oxygen ratios being- RO : Al,O, : SiO, : H20. I. ................ 1 : 3.09 : 4-76 : 2.51 11. ................ 1 : 3.10 : 5.17 : 2.48 Accepted formula.. .. 1 : 3.00 : 4.00 : 2.50 ArLaZcite follows thomsonite in time of deposition. Form 202 and also +O, which is very characteristic for this locality. The double refraction was very regular. A second generation of small and clear crystals upon apophyllite was observed. Analcite is often found alone in the cavities ; natrolite is almost invariably deposited on analcite.ApophyZlite, form mP.P. Crystals large and rough, or small and smooth ; the terminal edges of the pyramid are slightly furrowed. Sections parallel t o OP exhibit between crossed Nicols a square dark centre, whose sides are parallel to the traces of the prism faces, and from whose corners dark lines proceed to the margin ; the appearance must be caused by internal tensions. The composition is quite normal. Si02. A1,03 Fe20,. CaO. K20. Na2O. H2O. F1. 0 for FlJ 51.89 1.54 0.13 24.51 3-81 0.59 16.52 1.70 -0.72 = 99.97 Much of the apophyllite is altered to a white pearly subst,ance con- tainihg much silica, alumina, and water. Calcite has been deposited in three stages--firstly, wine-yellow crystals, preceding chabasite and deposited directly on the basalt ; secondly, colourless or only slightly yellow; and lastly, aragonite as a snow-white incrustation, mostly on chabasite, sometimes on apophyllite and thomsonite.MesoZite is the last mineral deposited; it, occurs in groups of exceedingly delicate needles, too small to recognise any crystalline form. Si02. Al,03. CaO. Na20. S,O. 46.14 26.88 8.77 6.19 12.17 = 100.15. 46.02 26.87 - - 12.17 - I 12.13 46.33 - This corresponds very nearly with 1 mol. of natrolite substance plus 2 mols. scolecite substance, i e . , Naumann's formula. A second series of zeolites differing in time and manner and also in composition, are found as semi-stratified deposits in the bottoms of many cavities, forming a kind of flow. The sandstone-like substance is crystalline, granular, and yellow, or white in colour, and in one large cavity this consisted entirely of laumontite, as was shown by optical and chemical examination-((a), white crystals ; j b ) , yellow crystals :- Si02.Al,O,. Fe203. CaO. NazO. &O. HaO. (a.) .. 51.74 21.65 0.95 11.95 O * l Y 0.35 13.30 = 100.13. (b.) . . 52.84 21.62 - 11.41 0.48 0.42 13 32 = 1O(j$g. The low amount of water is due to only some of the grains being clear, others being turbid ; laumontite easily loses some of' its water. I n other cases a mixture of laumontite and stilbite grains was present, often accompanied by reddish spherules of thomsonite, as shown by analysis; this mineral is also similarly deposited alone on166 ABSTRACTS OF CHEMICAL PAPERS. the lower lava sheet.I n many cases, fissures filled with these three minerals have been found leading into cavities also containing them ; they were certainly deposited previously Do the other zeolites, whose crystals are aitached to the walls of the cavities, or to this older deposit. H. B. Garnet and Cordierite in the Trachytes of Hungary. By J. SZAB~ (Jahrb. f. X n . , 1881, 1, Beil. Bd., 302--326).-Red garnet has oftsn been found in the trachytes of Hungary, and the researches of Szab6 prove that the garnet represents a type of trachyte which is characterised by its associated minerals, as well as by its relative age and the manner of its origin. He also found that the Hungarian tra- chytes very frequently contain cordierite. The garnet is almost always red. The grains are usually so large that they can be distin- guished with the naked eye.The predominating form of the crystals is an ikostetrahedron, with subordinate rhombic dodecahedron. It fuses easily before the blowpipe, thus indicating the almandine variety. The minerals accompanying it are felspar, amphibole, biotite, magne- tite, and cordierite. The latter bas previously been found in the trachytes of Spain and Tuscany, but was first discorered in the Hun- garian trachytes by Vogelsang, having formerly been mistaken either for quartz or for felspar. The cordierite has a violet-blue colour, and resembles amethyst-coloured quartz. It gave on analysis- SiO,. Fe,O, and 8120,. MgO. CaO. Total. 56.85 28.76 11.84 1-06 98.51 per cent. The remainder is probably soda. It is dichroic.and scratches quartz. It is associated with an orthoclase rich in soda, also with biotite, amphibole, and almandine. The author employs a new method of distinguishing cordierite for petrographic purposes. The dichroism alone is not su5cient, as it is not distinctly marked in light-coloured varieties, and although the mineral is harder than quartz, the difference in this respect is too small to afford any serviceable distinction : for these reasons chemical tests are to be preferred. Before the blowpipe it shows the presence of soda by faintly colouring the flame. The amount of soda is so slight, that it would in a chemical analysis be regarded merely as a trace ; but it is here of the greatest importance, since it serves, together with the fact of its being slightly fusible, to distinguish the mineral from quartz.Garnet is not found in the trachytes of Servia, of Auvergne, or of the Rhine district. It bas, however, been found in the trachytes of the Rocky Mountains (United States Geol. Exploration of the 40th Parallel. The trachyte family may be classed according to the felspar preaent, as follows :-(a) orthoclase trachyte ; ( b ) oligoclase trachyte; ( c ) labra- dorite trachyte ; (d) anorthite trachyte. Most of the Hungarian tra- chytes are biotite trachytes, in which the predominating felspar is labradorite, but andesine (oligoclase) also occurs subordinately : hence it can be seen that the garnet indicates the presence of a lime-soda C. King, 1877, p. 561).MINERALOGICAL CHEMISTRY. 167 felspar, and therefore, if garnet is found in a Hungarian trachyte the latter may be considered a biotite-labradorite trachyte, or, in other words, a garnet trachyte.Cordierite occurs under quite different conditions ; it is not bound to any particular felspar ; it may be found or be wanting, in any of the types of trachyte mentioned above. The presence of cordierite is of importance, as it indicates with certainty that the trachyte has under- gone metamorphism. B. H. B. The Lugano Eruptive District. By TOYOKITSI HARADA ( J u h ~ b . f. Hin,., 1882, 2, Beil. Bd., 1-48).--The paper gives a topographical and geological review, and a petrographical description. of the Lugano eruptive rocks. 1. The Black Porphyry.-This is an intermediate rock, with an exclusively felspathic ground-mass.The minerals which compose it, according to the relative age in which they separated oiit, are the fol- lowing :-Zircon, titanite, apatite, magnetite, biotite, hornblende, plagioclase, ort,hoclase, quartz, and lastly, the various products of decomposition, especially kaolin, mica, chlorite, atid epidote. The plagioclase is proved to be oligoclnse, with a sp. gr. of 2.65. An exact determination of the sp. gr. of the black porphyry itself cannot be expected, on account of its state of decomposition. The compara- tively undecomposed rock had a sp. gr. of 2.672-2-675. The chemical analysis of the rock gave the following result :- Si02. Al,O,. Fe,O,. UaO. MgO. :K20. Na20. GO2. H2O. 59.44 17.26 7.35 3.47 3.60 3.28 3-23 0.62 2.22 =lOO*87 The black porphyry may be regarded as a quartz porphyrite, the structure of which varies between that of quartz diorite and quartz f elsoph yrite.2. The Red Porphyry.-This is widely different from the black porphyry ; it is very acid, and has a magma rich in recent quartz. The four essential constituents are biotite, plagioclase, orthoclase, and quartz, and besides these zircon, npatite, and magnetite occur. The latter are always found enclosed in the other minerals, especially in the biotite. Kaolin, potash mica, epidote, ferric hydrate, calcite, quartz, chalcedony, pyrites, and chlorite appear as secondary constituents. The order in which the minerals separated out from the magma is the following:- 1. Zircon and apatite. 2. Magnetite. 3. Biotite. 4. Oligoclase, 5. Orthoclase. 6. Quartz. The chemical analyses of the red porphyry gave the following results :- Si02.Al,O,. Fe203. FeO. MnO. CaO. MgO. I. 72.32 13-37 0.57 2.34 - 1.88 3.57 11. 73-71 12.20 2.42 1-55 trace 0.40 3.63 I. 2.30 2.76 0.68 = 99.79 11. 2.28 1.83 1.69 = 99.71 K,O. Na,O. H20. The sp. gr. is 2.59.168 ABSTRACTS OF CHEMICAL PAPERS. Tourmaline is to be regarded as a secondary constituent both of the red and black porphyries. 3. The Tzcfccs.-These originate from the comminution of the red porphyry, as is shown by the fact that fragments of the latter are found in its deepest beds, and that the red porphyry and the, tufa beds exhibit perfect conformability. B. H. B. Sericite Rocks occurring in Ore Deposits. By A. v. GRODDECK (Jalzrb, f. Min., 1882, Beil. Bd., [ii], 72--138).-The “ white rock ” of Holzappel, on the Lahn, Wellmich and Werlau, on the Rhine, the slate bed of Mitterberg, in the Salzburg Alps, and the white slate of Agordo, in the Venetian A l p , which up to the present time have been described as talc slates, are sericite rocks.The analyses of the sericite gave the following result :- Phosphoric SiO,. Al,O,. PeO. MgOp CaO. K20. N,O. H20. acid. 45.58 36.76 1.13 0.85 0.03 9.29 1.36 5.16 trace = 100.16 Sp. gr. 2.87-2.88. The analpis thus corresponds pretty exactly with the formula of potash mica, H2(KNa) Als(Si04),, which confirms Laspeyre’s theory that sericite is not a distinct mineral, but a crypto- crystalline potash mica,. A part of the “ white rock ” contains pseudomorphs after felspar, augite, magnetite, and titanic iron ore, and is hence a n altered erup- tive rock, probably a diabase.In the white rock of Wellmich large crystals of apatite are enclosed, which are without doubt of secondary origiii. The sericite rocks of Mitterberg and Agordo are very probably metamorphic rocks from normal clay slates, or Greywack6 slates. An exact knowledge of these rocks seems suitable for opening up new points of view for several most important questions regarding ore deposits, as it is highly probable that the sericite rocks described always occur with ore-deposits where there is conformability between the deposit and the strata of the surrounding rocks. The ore-deposits of Holzappel, Wellmich, Werlau, and Mitterberg are doubtless veins resembling interstratified beds. It had long been doubtful whether the Salzburg and Tyrol copper ore deposits of Mitterberg, &c., were true beds or lodes resembling beds, but the general opinion now is that all the occurrences belong to the group of lodes resembling beds.These seem to be always accompanied by sericite rocks. The Agordo deposit resembles in a remarkable degree that of Mitterberg; it is therefore very probable that it is also a bed-like lode. The white slates of Agordo correspond, according to v. Cotta, with the rock at Fahlun, in Sweden, so it is very possible that the latter a h o belongs to the sericite rocks. Although sericite rocks occur with such typical bed-like lodes as those of Holzappel and Mitterberg, they are entirely absent in the case of typical stratified pyrites deposits, as the beds of Goslar, Schmollnitz, and Meggen.It has long been a moot question whether ore deposits, which are conformably interstratified in sedimentary rocks, must be considered asMINERALOGIICAL CHEMISTRY. 169 beds, or lodes resembling beds. To settle this question, the character of the surrounding rock has never yet been taken into account, but the author is of the opinion that if the sericite rocks are truly the original surrounding rock altered by the formation of a mineral vein, they can only occur in the presence of mineral veins, and their absence must confirm the opinion as to the bedded nature of the deposit. B. H. B. Basalt Rocks containing Hornblende. By H. SOMMERLAD (Jahd. f. Min., 1882, Beil. Bd. [ii], 139--185).-The hornblende basalts, charac- terised macroscopically by their richness in porphyritic amphibole crystals, contain microscopically as essential constituents, plngioclase, augite, hornblende, magnetite, and olivine. In the Rhon rocks, nepheline occurs, although never in distinct crystals, and is of no special importance for the composition of the rock, as the chemical analysis also proves.The hornblende basalts form a subdivision of the felspar basalts. When nepheline is present in greater quantity, they pass into basa- nites ; in the absence of plagioclase, and with predominence of a glass basis they approach the limburgites. The most interesting constituent, the hornblende, frequently shows remarkable peculiarities of structure. Rounded crystals are specially characteristic of it. It was without doubt an original ingredient of the rock, which has separated very early out of the magma.The hornblende basalts of the Rhon-moun- tains, where they seem to be most widely distributed, never form high peaks. They are of older origin than the basalts, which are free from hornblende, as can at least be proved in the case of the Rho, and the Vogelsberg. The chemical composition indicates that the hornblende basalts are tolerably basic, owing to their richness in magnetite, hornblende, and augite. The percentage of silica scarcely rises above 44 ; that of soda varies between 2-57 and 3.25; thus it may be seen that it is not greater than in other felspar bssalts, and this proves that the nephe- line does not play a special part in the hornblende basalts. The per- centage of potash varies between 1.36 and 1.54.Only a few varieties from the Rhon gelatinise weakly with hydrochloric acid, with separa- tion of little cubes of sodium chloride. The rocks from Beuelberg, near Kircheip, and from Naurod, near Viesbaden, contain hornblende and augite, but no felspar can be found microscopically in them as an essential constituent, and they contain large amounts of olivine; they belong to the group of the tertiary picrite porphyries. B. H. B. Examination of certain Meteorites. By W. PLIGHT (Proc. Roy. Xoc., 33, 343-347).-1. The Bruce meteorite, found a t Cranbourne, near Melbourne, is shown by the author to consist entirely of metallic minerals ; the iron contains no combined carbon, from 7-9 per cent. nickel, some cobalt, silicon, and copper.On the surface were metallic plates of a flexible minera.1 of composition Fe&, which the author proposes to name Edmondsite. Among other minerals present were rhabdite, Fe4Ni,P, a brittle coarse powder, proba,bly identical with a schreibersite of formula (Fe,Ni),P, brass-coloured oblique crystale of A glassy basis is rarely met with. VOL. XLIV. n170 ABSTRACTS OF CHEMICAL PAPERS. composition Fe9Ni2B2, and square, black metallic prisms of composition Fe,Ni,P, together with triolite and graphite ; the occluded gases amounted to 3.59 times the volume of the iron, and consisted of- co,. co. H. CHI. N. 0.12 31-88 45.79 4.5.5 17.66 11. The Rowton siderite fell on April 24th, 1876, a t Rowton, near Wellington, Salop. It is covered with a thin black crust of the mag- netic oxide; some fragments of the block were found on analysis to contain- Fe.Ni co. cu. 91.145 8.582 0-371 trace thus closely resembling the iron of Nevagolla, in India,. gas was 6.38 times the volume of the iron, and consisted of- The occluded coil. H. co. N. 5.155 77.778 7.345 9.722 111. The Middlesborough siderite fell at Middlesborough on March 14th, 1881 ; it is in the form of a low pyramid, slightly scolloped, the summit and side being deeply grooved and polished. It contained 9.379 per cent. of nickel iron, containing iron, 76.99 ; nickel, 21.32 ; cobalt, 1.69 per cent ; the remaining constituents consist of a soluble silicate identical with olivine, and an insoluble silicate, bronzite. V. H. V. Deposits of Manganese on the Surfaces of Rocks.By BOUS- SINGAULT (Compt. rend., 95, 368-373).-The author has found manganese in the magnesia prepared from sea-water by Schloesing’s process. Dieulafait has detected manganese in considerable quantity i i t the ashes of marine plants, and the “ Challenger ” expedition dredged up, from the bottom of the deep sea, nodules containing a large proportion of manganese dioxide. There can, therefore, be no doubt that manganese is present in sea-water. The manganese found in such large quantity on the sea bottom by the “Challenger” is apparently of volcanic origin, for it was always found where pumice stone was present. The nodules have an oolitic appearance, and frequently consist of concentric layers of manganese dioxide surrounding a nucleus of red clay, but they show no trace of organic structure.Buclianan regards the nodules as due to the intervention of animal substances, which reduce the sulphates in the sea-water to sulphides. Gurube1 supposes that the manganese is derived from submarine springs which rise in volcanic districts, and contain manganese car- boilate in solution. The manganese carbonate is deposited, and is osidised by the oxygen dissolved in the water. This explanation is very similar to that which the author has advanced to account lor the deposits of manganese dioxide on the surface of rocks on the banks of the Orinoco and in other localities (Abstr., 1882, 1270). C. H. B.MIXERALOGICAL CHEMISTRY. lil The Orchard Alum Spring. By J. C. THRESH (Pharnt. J. Trans. [ 3],13,36l).-This spring, which issues from an old coal mine near the summit of Axe Edge, in the Peak country, has long been valued as it vermifuge, but it is not adapted as a tonic, owing to the amount of aluminium sulphate present.The water has a decided red tint, which varies according to the wetness of the season; it is acid in reaction, b u t contains no free acid. When heated to 66" it becomes opaque, basic ferric sulpbate separating, but the deposit redissolves as evapora- tion proceeds; the water is colourless if the deposit is allowed to settle. The sp. gr. = 1*00351, and the composition per gallon is as follows :- Fe,3S04 .............. 174.426 grains. Fe,Os ................ 6.275 ,, A123S04 .............. 72.908 ,, CaS04 ................ 14.381 ,, FeSOl ................ 1.596 ,, NazSOa ................0.537 ,, MgSO,.. .............. 21.055 ,, KzSO, ................ 0.822 ,, AlPOa ................ 0.456 ,, KC1 .................. 0.282 ,, NH,Cl ................ 0-125 ,, SiO,.. ................ 5.776 ,, KNO, ................ 0.170 ,, 298.809 ,, The source of the spring is above the millstone grit, which is over- The author proceeds to show theoretically laid by aluminous shale. the formation of ferric sulphate from the ferric sulphide in the shale. E. W. P. Analysis of Waters accompanying Petroleum and of those Ejected by Mud Volcanoes. By A. POTILITZIN (Jour. Russ. Chem. Soc., 1882, 300-310).-The author has analysed waters of the above kind from the Caucasian and Caspian petroleum district. The waters have an alkaline reaction, and contain large quantities of sodium chloride, besides sodium bromide and iodide, the latter in such quan- tities as have never been found before in any mineral water, viz., 0*098-0*118 gram NaI in 1000 grama.The author found also con- siderable quantities of a free organic acid belonging to the fatty series, most probably capric acid. He regards the above petroleum wells as a new source of iodine. B. B.158 ABSTRACTS O F CHEMICAL PAPERS.M in e r a 1 o g i c a1 C h em i s t ry.Mechanical Separation of Minerals. By L. PEBAL (Monatsh.Chem., 3, 723-’725).-In this paper, which is partly a reply toDoelter’s remarks on the same subject (Abstr., 1882, 656, 1173),the author recommends the following modification of his method ofmoving t,he electromagnet about in water holding the finely pul-verised mineral in suspension.To avoid the formation of lumps,arising from the enclosure of air-bubbles, the fine powder of themineral is made slowly to absorb water-or alcohol if water will notwet it-from one side only, after which it is treated as followv :-Anumber of moderate-sized beaker-glasses are filled with distilled water ;the moistened rock-powder is introduced into the first; into thispowder is thrust the end of the iron rod surrounded with a coil ofwire; and the circuit is closed, while the water is briskly agitated.The electromagnet is then dipped into the second glass ; the circuit isbroken ; and t h i s treatment is repeated till the magnet in the firsMIKERALOGICAL CHEMISTRY. 159glass no longer attracts any particles. After all the magnetic pa,rticleshave thus been transferred to the sec,ond glass, the process is repeatedin exactly the same manner with the second and third glass, then withthe third and fourth, and so on till the magnetised bar no longerleaves any residue in the last glass but one.The contents of the lastglass are then collected on one filter, and those of all the others on asecoud filter. With a moderate amount of care in carrying out thisprocess, it is easy to avoid loss of substance. One point, however,must not be overlooked, namely, the behaviour of solid diamagneticbodies in diamagnetic liquids, whereby, if the diamagnetism of theliquid is stronger than that of the solid body, repulsion becomesconverted into attraction.8. w.Application of a Solution of Potassium and Mercury Iodidesto Mineralogical and Petrographical Researches. By V. GOLD-SCHMIDT (Jalub. $. Min., 12181, 1, Beil. Bd., 179--238).-1t is to beregretted that the subject of the separation of the constituents of arock has been neglected of late, in consequence of the success whichhas attended microscopic investigation, as there are cases in which thelatter method cannot be relied on. The separation may be effectedchemically or mechanically ; in the latter case advantage is taken ofthedifference in the sp. gr. of the substances. I n 1877 Church (" Ona Test of Sp. Gr.," illin. LWxg., 1877) proposed to separate the con-stituents of a rock according to their sp. gr. by the help of an aqueoussolution of the iodides of potassium and merccry.The paper givesa t some length an accouiit of J. Thoulet's researches on the samesubject (Bull. SOC. i l l i ~ , 1879, No. 1).On investigating the subject further, t'he author decided to employa solution in which the weight of potassium iodide present is to themercury iodide as 1 is to 1.239; and this solution has a sp. gr. of3.196, so that fluorspar floats in i t ; while the solutions of T'hoiiletand Church gave as the maximum sp. gr. 2-77 and 3.01 respectively.The maximum density is, however, not constant. It depends on themoisture of the atmosphere and on the temperature. In summer themaximum was 3.196, whilst in winter it was only 3.17.The difficulties which attend this simple method of separation ofthe rock constituents according to the sp.gr. are due to the variationin the sp. gr. of the predominating mineral ; the close combination ofthe constituents ; the smallness of the grains ; the great similarity, or,in some cases, identity of sp. gr. of different minerals occurringtogether, such as quartz and oligoclase; the tendency of the lightergrains when they are in great excess to bring the heavier with themto the top ; and the 1iabilit)y of the solution to change by evaporationor by taking up water.In considering this method, the question arises : Is the value of thesp. gr. constant enough for the mineral to be determined by it, andif a separation is effected between narrow limits of weight, can itwith certainty be asserted that the mineral sought for has beenseparated? I n order to answer the questionpractically, the author submitted the felspar-group to the strictestinqestigation, and came t o the conclusion that, with fresh materialTheoretically it is so160 ABSTRACTS 01' CHEMICAL PAPERS.and perfect separation, the determination of the sp.gr. gives an exactconclusion as to the nature of the felspar.The apparatus used for the separation of the rock-constituents pro-posed by Thoulet is described, but the author prefers to effect theseparation in small beakers of about 40-50 C.C. capacity, theprincipal advantage of which is that the parts swimming above canbe better manipulated with the glass rod, and, consequently, the heaviergrains which are enclosed more easily separated.d number ofminerals whose sp. gr. has been exactly determined, are used as indi-cators in the solution. The powdered rock and the indicators areintroduced into about 30 C.C. of the concentrated solution and stirred,then allowed to subside, and the lighter parts removed. The successof the separation depends on the skill of the experimenter, on thechoice of the indicators, but, above all, on the nature of the substanceto be separated.It is evident, then, that Thoulet's opinion that the constituents of arock can be qualitatively and quantitatively separated, holds good onlyvery rarely, and i t would bo necessary also in most cases to make useof auxiliary methods, such as treating the powder with variousreagents or with the magnet.Native Palladium-Gold from Taguaril, Brazil.By W. H.SEAXON (Chem. News, 46, 216).-Sp. gr. = 15.73.B. H. B.Analysis:-All. Pd. Age Fe.91.36 8.21 trace trace E. W. P.. Alloys of Gold, Silver, &a, found in Grains along with theNative Platinum of Columbia. By W. H. SEAMON (Chem. News,46, 215) .-Occurring with nat'ive platinum, alloys were found havingthe following composition :-(Ag + Cu')Au3, (Cu' + Ag),Bu6, (Ag +Hg')zAu8, Ag4AuI0. Analyses we given, together with the donsities ;but the results are not of much value, owing to the smallness of thequantity of material a t hand. E. W. P.On a Bed of Coal discovered in Algiers, and on the Layersof White Sand accompanying the same. By G. P~NARD (COW@rend., 95, 708--709).-The author states that the results of experi-ments made with the coal of Bou-Saada in Algiers show that, both inrespect of the amount of gas yielded and the illuminating power ofthe latter, it is quite equal to the best English and French coals, Theyield of coke varies from 60 to 66 per cent.of the coal used..The coal is always accompanied by beds of white sand arising fromthe disintegration of bands of sandy loam. This sand can be used forthe manufacture of superior glass.Dopplerite from Aussee. By W. DEMEL (J-onatsh. Chem., 3,763-769) .-A perfectly homogeneous specimen of this mineral freedfrom adhering peat and dried a t 100-120", gave by analysis 56.42 and56-51 per cent. carbon and 5-34-5.20 hydrogen, leading to the formulaC,,HI4O,, which requires 56.69 C, 5-52 €I, and 37.79 0.It yieldedalso 5.1 per cent. ash having the following composition:-E. H. RMIXERALOGICAL CHEMISTRY.The high percentage of lime seems to show that this base may bepresent as carbonate, but the percentage of GO2 directly determinedwas only 0.16 ; and this, together with the smallness of the amountsof SO, and CI, shows clearly that the greater part of the lime must becombined with the organic matter, a conclusim which is confirmed bythe behaviour of the mineral with caustic potash. On suspending thedopplerite in water and treating it with strong potash-lye, the massbecomes thick, pasty, and very hot, and the alkali appears to be satu-rated, as it no longer absorbs carbonic acid from the air. On boilingthe liquid the dopplerite dissolves, yielding a dark brown-red solution,and from this, after filtration, acids throw down a brown flocculentprecipikate which, after thorough washing and drying, becomes shiningand brittle, and very much like the original dopplerite.This substancedried at 110” gave 0-73 per cent. ash, and its combustion yielded56.86-56-99 per cent. C and 4-90-4.97 K, leading to the formulaC,,H,,O,, which contains 2 at. hydrogen less than that of the originaldopplerite.The alkaline solution of dopplerite gives with calcium salts a brownprecipitate containing calciiim, which when dried forms a blackish-brown mms like dry dopplerite; it contains about 2-71 per cent.CaC03, and, deducting this, the composition of the salt is found toagree very nearly with the formula C2&,Ca0,,, thereby affordingfurther evidence that.the snbstance isolated from dopplerite in themanner above described has the composition C,,H,,O,.Dopplerite fused with potassium hydroxide is converted into proto-catechuic acid (m. p. 199--201”), together with resinous and dark-coloured products containing more than 70 per cent. carbon.Ulmin (prepared from cane-sugar) also gave, on fusion with potash,protocatechuic acid, together with black amorphous masses very richin carbon.From the similarity of the compounds above described to humus-substances in general, and from the mode of occurrence of doppleritein peat-beds, this mineral may be regarded as the calcium salt of oneor several acids beIonging to the series of humus-substances.H.W.New Sulphide received as Tetrahedrite from Great EasternMine, Colorado. By W. T. PAGE (Chem. News, 46, 215).--Steel-grey metallic lustre ; structure crystalline but indefinite, brittle.Hardness = 4: sp. gr. = 4-89, Composition:-Silicious s. Sb. Cu. Zu. Fe. Pb. residue.26.88 34.47 23.20 7.14 1.38 1.19 5.86 = 100.12This corresponds to-{jCu’aS + g(Cu”,Zn,Fe,Pb)S)Sb2S3162 ABSTRACTS OF CHEMICAL PBPERS.This mineral might be considered as a distinct species of stylotypite,but it is better to class it as a variety of bonrnonite.E. W. P.Martite of the Cerro de Mercado, or Iron Mountain ofDurango, Mexico, and certain Iron Ores of Sinaloa. By B.SILLIMAN (Am. J. Xci. [3], 23, 375--379).-This remarldJle hillexposes masses of the ore all over its surface; they appear to bederived from one or more immense beds of specular iron standingnearly vertical; the fragments form a talus on the slopes of themountain and conceal the underlying porphyry.There is nothing toshow that it is a pseudomorph of pyrites. An average sample con-tained-Fe,04. Peso3. Mn,O,. TeOz. CaO.2 07 77.57 0.11 0.71 5.u50.36 0.21 3.04 1-76 1.98 -MgO. SOy. PZO,. SO2. HZO, &c. Al,O,.I n the ores from Sinaloa there still remains in the martite about one-third of the original magnetite. H. €3.New Locality for Hayesine. By N. H. DARTON (Am. J. S C ~ .[3], 23, 458-459).-This very rare mineral occurs with datholiteand calcite in the traprock of Bergen Hill. Slender acicular crystalsgrouped on the calcite crystals ; they are probably a decomposition-product of datholite ; the rock is soft, and permeable to water.CaO.B203 HzO.Found .. .. .. .. .. .. .. 18.39 46.10 35.46 = 99.95.H. B.Occurrence and Composition of some American Varieties(1.) The specimen was appnrently homogeneous. Sp. gr. = 520-5-25 ; locality, Pelton's Quarry, Portland, Conn. (2.j Picked grainsfrom the monazite sand from gold washing in the Brindletown dis-trict, Burke co., N. Carolina; sp. gr. = 5.10. (3.) A specimen, alsoapparently pure, from Yale College.of Monazite. By s. L. YENFIELD (Am. J. Sci. [2], 24, 250-255).-P,O,. Ce203. (La,Di) aO,. Th02. SiO,. Ignition.(1.) 28.18 33.54 28.33 8-25 1.67 0.37 = 100.34(2.) 29.28 31.38 30.88 6.49 1.4G 0.20 = 99.63(3.) 26.12 29.83 26.66 14.23 2.85 0.67 = 100.42These numbers are in most cases the mean of two or three deter-minations.The ratios (Ce,La,Di),03 : P,O, are 1 : 1-06, 1 : 1.08, and 1 : 1 .O i ;those of Tho, to SiO, 1 : 0.90, 1 : 092, and 1 : 0.88 respectively.The varying amounts of Tho, and SO,, and their chemical differencefrom the cerite metals, made it probable that the thorium silicateexists as an impurity ; this was proved by microscopic examinationMINERALOGICAL CHEMISTRY. 163the mechanically mixed thorite being distinguished by its darkercolour and easy decomposition by acids.The thoria was separated by sodium thiosulphate ; the remainingoxides were heated with dilute sulphuric and oxalic acid, and theevolved carbonic anhydride collected in potash bulbs. The jointatomic weight of the oxides obtained from the Portland specimen was140.1, which number was also used to calcdate the results of theother analyses. H.B.Colourless Mimetite from the Richmond Mine, Nevada.By F. A. MASSIE (Chem. News, 46, 215).-Slender acicular hexagonalprisms, colourlesa, transparent, and with adamantine lustre. Hard-ness = 3 ; sp. gr. 6.92, easily fusible.As205. p 2 0 5 . PbO. PbCI,.23-41 trace 68.21 8-69 = 100.31agreeing with the known formula PbC12,3Pb3AszOs.Notes on some N. Carolina Minerals. By W. E. HIDDEN(Am. J. Xci. [3], 24, 372--377).-1n Alexander Co., emerald andberyl crystals, on which the rare forms 3P% and 4P$ are largelydeveloped, are occasionally found.The supposed ceschynite from Ray's Mine, Pancey Go., is columbite.Uraninite from Mitchell Co.has sp. gr. = 8-97-9.22, and hence isnot, entirely free from alteration.E'uxenite from Wiseman's mica mine has been reanalysed by .T. W.Mallett; titanic acid is absent; it is therefore probably alteredaamarskite, with which it is intimately associated.Composition :-E. W. P.Fe~gzcsoizite from Burke Co. has also been analysed by Mallett.Nb205. TafO,. SnOa,W03. Y,O,, &c. C203. Di205,La203.43.78 4-08 0.76 57-21 0.66 3.49u2°3' FeO. CaO. H,O.5-81 1.81 0.65 1.62 = 99.87.AZZan,ite has recently been found at two new localities, viz., Alex-ander Co. with the above-mentioned emerald crystals, and Wiseman'smica mine, Mitchell Co.; in both cases the crystals are welldeveloped.SiOz.Al,03. Y203. Ce,03. Fe20,. FeO. MgO. CaO. H20.39.03 14.33 8.20 1.53 7-10 5 22 4.29 17.47 2.78 = 99.95H. B.Composition of Two Specimens of Jade. By C. L. ALLEN(Chern. News, 46, 216).-The first specimen came from the KarakashValley, on the borders of Turkestan; it is of a pale green colour,translucent; hardness = 6.5 ; sp. gr. = 2.98, and contains-Si02. A1,03. FeO. MpO. CaO. NazO. K20. HzO.57.35 1.03 1.22 22.73 13-40 0.25 0.23 2.69 = 98.164 ABSTRACTS OF CHEMICAL PAPERS.The other specimen came from Hokotika, New Zealand, and is sub-translucent, with hardness = 6 ; sp. gr. 3.026. Coniposition :-Si02. A1203. FeO. MgO. CaO. Na20. K20. H20.56.34 1.60 4.86 20.23 13.51 0.27 0.31 3-57‘ = 100.69These specimens therefore represent the nephrite variety of amphi-bole, and the first analysis corresponds to (&Mg + -&Ca)SiO,,whilst the second corresponds to (+Mg + +Ca)Si03.By W.H. SEAMOX(Chem. News, 46, 215).-Crystals flat, well defined, imbedded insoft kaolin, pitch-black, submetallic lustre ; brownish-grey streak ;imperfect conchoTdal fracture; hardness = 6 ; sp. gr. 3.15. Corn-position :-E. W. P.Analysis of a Mineral allied to Orthite.Si02. Al,03. Y203. Ce403. Pe&. FeO. MgO. CaO. H2O.39.03 1433 8.20 1.53 7-10 5.22 4.29 17.47 2*?8 = 99-95Distribution of elements + &M” + &M”)Si04.E. W. P.Communications from the U. S. Geological Survey, RockyMountains Division. 1. Minerals, mainly Zeolites, occurringin the Basalt of Table Mountain, near Golden, Colorado.ByW. CROSS and W. T. HILLEBRAND (Am. J. Sci. [3], 23, 452-458,and 24, 129--138).-Lencite does not occur. The formation ofthe mountain is due to two protecting sheets of lava, an upper and alower one, of 115 feet in tliickness. I n the cavit’ies of the upperportion of the lower sheet (felspar basalt) are many beautifullycrystallised zeolites, associated with calcite and arragonite. Thezeolites are often found together ; the following have been determined,viz., analcite, ap Iphyllite, chnbasite, mesolite, natrolite, stilbite, andthomsonite. Chabasite is apparently the oldest zeolite, as it generallylines the cavities, and the other zeolites are formed upon it.Thomsolzite-Crystals, thin reciangulnr blades, grouped together invarious ways ; where calcite crystals are not covered by chabasite,thomsonite never fails to coat them.Toward the close of the zeoliticformation, a second generation of thomsonite, and sometimes also ofchabasite, was. deposited.SiO,. 8120,. CaO. N%O. H20.I. 40-68 30.12 11.92 4.44 12.86 = 100.0211. 43.66 29.52 10.90 4.92 12.28 = 100.01- - - - 111. 41-60IV. 40.88 - - -I is of the older growth, and I1 of the newer. No. I was mostcarefully freed from any chabasite. No. I1 contained a comparativelyfew crystals of mesolite, and their comptek removal was impossible.I11 is of the of the thin blades, and the microscope showed thepresence of irregular rounded isotropic particles imbedded in theouter parts of the crystals. No. IV was from some very fine cryshls,containing but a very few of these rounded particles. The silica iMINERhLOGlCAL CHE3IISTRT.165higher than that allowed by the generally accepted formula; theoxygen ratios being-RO : Al,O, : SiO, : H20.I. ................ 1 : 3.09 : 4-76 : 2.5111. ................ 1 : 3.10 : 5.17 : 2.48Accepted formula.. .. 1 : 3.00 : 4.00 : 2.50ArLaZcite follows thomsonite in time of deposition. Form 202 andalso +O, which is very characteristic for this locality. The doublerefraction was very regular. A second generation of small and clearcrystals upon apophyllite was observed. Analcite is often found alonein the cavities ; natrolite is almost invariably deposited on analcite.ApophyZlite, form mP.P. Crystals large and rough, or small andsmooth ; the terminal edges of the pyramid are slightly furrowed.Sections parallel t o OP exhibit between crossed Nicols a square darkcentre, whose sides are parallel to the traces of the prism faces, andfrom whose corners dark lines proceed to the margin ; the appearancemust be caused by internal tensions.The composition is quite normal.Si02. A1,03 Fe20,. CaO. K20. Na2O. H2O. F1. 0 for FlJ51.89 1.54 0.13 24.51 3-81 0.59 16.52 1.70 -0.72 = 99.97Much of the apophyllite is altered to a white pearly subst,ance con-tainihg much silica, alumina, and water. Calcite has been depositedin three stages--firstly, wine-yellow crystals, preceding chabasite anddeposited directly on the basalt ; secondly, colourless or only slightlyyellow; and lastly, aragonite as a snow-white incrustation, mostly onchabasite, sometimes on apophyllite and thomsonite.MesoZite is the last mineral deposited; it, occurs in groups ofexceedingly delicate needles, too small to recognise any crystallineform.Si02. Al,03.CaO. Na20. S,O.46.14 26.88 8.77 6.19 12.17 = 100.15.46.02 26.87 - - 12.17- I 12.13 46.33 -This corresponds very nearly with 1 mol. of natrolite substance plus2 mols. scolecite substance, i e . , Naumann's formula.A second series of zeolites differing in time and manner and also incomposition, are found as semi-stratified deposits in the bottoms ofmany cavities, forming a kind of flow. The sandstone-like substance iscrystalline, granular, and yellow, or white in colour, and in one largecavity this consisted entirely of laumontite, as was shown by opticaland chemical examination-((a), white crystals ; j b ) , yellow crystals :-Si02.Al,O,. Fe203. CaO. NazO. &O. HaO.(a.) .. 51.74 21.65 0.95 11.95 O * l Y 0.35 13.30 = 100.13.(b.) . . 52.84 21.62 - 11.41 0.48 0.42 13 32 = 1O(j$g.The low amount of water is due to only some of the grains beingclear, others being turbid ; laumontite easily loses some of' its water.I n other cases a mixture of laumontite and stilbite grains waspresent, often accompanied by reddish spherules of thomsonite, asshown by analysis; this mineral is also similarly deposited alone o166 ABSTRACTS OF CHEMICAL PAPERS.the lower lava sheet. I n many cases, fissures filled with these threeminerals have been found leading into cavities also containing them ;they were certainly deposited previously Do the other zeolites, whosecrystals are aitached to the walls of the cavities, or to this olderdeposit.H. B.Garnet and Cordierite in the Trachytes of Hungary. ByJ. SZAB~ (Jahrb. f. X n . , 1881, 1, Beil. Bd., 302--326).-Red garnethas oftsn been found in the trachytes of Hungary, and the researchesof Szab6 prove that the garnet represents a type of trachyte which ischaracterised by its associated minerals, as well as by its relative ageand the manner of its origin. He also found that the Hungarian tra-chytes very frequently contain cordierite. The garnet is almostalways red. The grains are usually so large that they can be distin-guished with the naked eye.The predominating form of the crystalsis an ikostetrahedron, with subordinate rhombic dodecahedron. Itfuses easily before the blowpipe, thus indicating the almandine variety.The minerals accompanying it are felspar, amphibole, biotite, magne-tite, and cordierite. The latter bas previously been found in thetrachytes of Spain and Tuscany, but was first discorered in the Hun-garian trachytes by Vogelsang, having formerly been mistaken eitherfor quartz or for felspar. The cordierite has a violet-blue colour, andresembles amethyst-coloured quartz. It gave on analysis-SiO,. Fe,O, and 8120,. MgO. CaO. Total.56.85 28.76 11.84 1-06 98.51 per cent.The remainder is probably soda. It is dichroic. and scratches quartz.It is associated with an orthoclase rich in soda, also with biotite,amphibole, and almandine.The author employs a new method of distinguishing cordierite forpetrographic purposes.The dichroism alone is not su5cient, as it isnot distinctly marked in light-coloured varieties, and although themineral is harder than quartz, the difference in this respect is toosmall to afford any serviceable distinction : for these reasons chemicaltests are to be preferred. Before the blowpipe it shows the presenceof soda by faintly colouring the flame. The amount of soda is soslight, that it would in a chemical analysis be regarded merely as atrace ; but it is here of the greatest importance, since it serves, togetherwith the fact of its being slightly fusible, to distinguish the mineralfrom quartz.Garnet is not found in the trachytes of Servia, of Auvergne, or ofthe Rhine district.It bas, however, been found in the trachytes ofthe Rocky Mountains (United States Geol. Exploration of the 40thParallel.The trachyte family may be classed according to the felspar preaent,as follows :-(a) orthoclase trachyte ; ( b ) oligoclase trachyte; ( c ) labra-dorite trachyte ; (d) anorthite trachyte. Most of the Hungarian tra-chytes are biotite trachytes, in which the predominating felspar islabradorite, but andesine (oligoclase) also occurs subordinately : henceit can be seen that the garnet indicates the presence of a lime-sodaC. King, 1877, p. 561)MINERALOGICAL CHEMISTRY. 167felspar, and therefore, if garnet is found in a Hungarian trachytethe latter may be considered a biotite-labradorite trachyte, or, in otherwords, a garnet trachyte.Cordierite occurs under quite different conditions ; it is not bound toany particular felspar ; it may be found or be wanting, in any of thetypes of trachyte mentioned above.The presence of cordierite is ofimportance, as it indicates with certainty that the trachyte has under-gone metamorphism. B. H. B.The Lugano Eruptive District. By TOYOKITSI HARADA ( J u h ~ b . f.Hin,., 1882, 2, Beil. Bd., 1-48).--The paper gives a topographical andgeological review, and a petrographical description. of the Luganoeruptive rocks.1. The Black Porphyry.-This is an intermediate rock, with anexclusively felspathic ground-mass. The minerals which compose it,according to the relative age in which they separated oiit, are the fol-lowing :-Zircon, titanite, apatite, magnetite, biotite, hornblende,plagioclase, ort,hoclase, quartz, and lastly, the various products ofdecomposition, especially kaolin, mica, chlorite, atid epidote. Theplagioclase is proved to be oligoclnse, with a sp.gr. of 2.65. Anexact determination of the sp. gr. of the black porphyry itself cannotbe expected, on account of its state of decomposition. The compara-tively undecomposed rock had a sp. gr. of 2.672-2-675. The chemicalanalysis of the rock gave the following result :-Si02. Al,O,. Fe,O,. UaO. MgO. :K20. Na20. GO2. H2O.59.44 17.26 7.35 3.47 3.60 3.28 3-23 0.62 2.22 =lOO*87The black porphyry may be regarded as a quartz porphyrite, thestructure of which varies between that of quartz diorite and quartzf elsoph yrite.2.The Red Porphyry.-This is widely different from the blackporphyry ; it is very acid, and has a magma rich in recent quartz. Thefour essential constituents are biotite, plagioclase, orthoclase, and quartz,and besides these zircon, npatite, and magnetite occur. The latter arealways found enclosed in the other minerals, especially in the biotite.Kaolin, potash mica, epidote, ferric hydrate, calcite, quartz, chalcedony,pyrites, and chlorite appear as secondary constituents. The order inwhich the minerals separated out from the magma is the following:-1. Zircon and apatite. 2. Magnetite. 3. Biotite. 4. Oligoclase,5. Orthoclase. 6.Quartz.The chemical analyses of the red porphyry gave the followingresults :-Si02. Al,O,. Fe203. FeO. MnO. CaO. MgO.I. 72.32 13-37 0.57 2.34 - 1.88 3.5711. 73-71 12.20 2.42 1-55 trace 0.40 3.63I. 2.30 2.76 0.68 = 99.7911. 2.28 1.83 1.69 = 99.71K,O. Na,O. H20.The sp. gr. is 2.59168 ABSTRACTS OF CHEMICAL PAPERS.Tourmaline is to be regarded as a secondary constituent both of thered and black porphyries.3. The Tzcfccs.-These originate from the comminution of the redporphyry, as is shown by the fact that fragments of the latter arefound in its deepest beds, and that the red porphyry and the, tufabeds exhibit perfect conformability. B. H. B.Sericite Rocks occurring in Ore Deposits. By A. v. GRODDECK(Jalzrb, f. Min., 1882, Beil.Bd., [ii], 72--138).-The “ white rock ” ofHolzappel, on the Lahn, Wellmich and Werlau, on the Rhine, the slatebed of Mitterberg, in the Salzburg Alps, and the white slate ofAgordo, in the Venetian A l p , which up to the present time havebeen described as talc slates, are sericite rocks.The analyses of the sericite gave the following result :-PhosphoricSiO,. Al,O,. PeO. MgOp CaO. K20. N,O. H20. acid.45.58 36.76 1.13 0.85 0.03 9.29 1.36 5.16 trace = 100.16Sp. gr. 2.87-2.88. The analpis thus corresponds pretty exactlywith the formula of potash mica, H2(KNa) Als(Si04),, which confirmsLaspeyre’s theory that sericite is not a distinct mineral, but a crypto-crystalline potash mica,.A part of the “ white rock ” contains pseudomorphs after felspar,augite, magnetite, and titanic iron ore, and is hence a n altered erup-tive rock, probably a diabase.In the white rock of Wellmich largecrystals of apatite are enclosed, which are without doubt of secondaryorigiii.The sericite rocks of Mitterberg and Agordo are very probablymetamorphic rocks from normal clay slates, or Greywack6 slates.An exact knowledge of these rocks seems suitable for opening upnew points of view for several most important questions regarding oredeposits, as it is highly probable that the sericite rocks describedalways occur with ore-deposits where there is conformability betweenthe deposit and the strata of the surrounding rocks. The ore-depositsof Holzappel, Wellmich, Werlau, and Mitterberg are doubtless veinsresembling interstratified beds.It had long been doubtful whetherthe Salzburg and Tyrol copper ore deposits of Mitterberg, &c., weretrue beds or lodes resembling beds, but the general opinion now isthat all the occurrences belong to the group of lodes resembling beds.These seem to be always accompanied by sericite rocks. The Agordodeposit resembles in a remarkable degree that of Mitterberg; it istherefore very probable that it is also a bed-like lode. The whiteslates of Agordo correspond, according to v. Cotta, with the rock atFahlun, in Sweden, so it is very possible that the latter a h o belongsto the sericite rocks. Although sericite rocks occur with such typicalbed-like lodes as those of Holzappel and Mitterberg, they are entirelyabsent in the case of typical stratified pyrites deposits, as the beds ofGoslar, Schmollnitz, and Meggen.It has long been a moot question whether ore deposits, which areconformably interstratified in sedimentary rocks, must be considered aMINERALOGIICAL CHEMISTRY. 169beds, or lodes resembling beds.To settle this question, the characterof the surrounding rock has never yet been taken into account, but theauthor is of the opinion that if the sericite rocks are truly the originalsurrounding rock altered by the formation of a mineral vein, they canonly occur in the presence of mineral veins, and their absence mustconfirm the opinion as to the bedded nature of the deposit.B. H. B.Basalt Rocks containing Hornblende. By H. SOMMERLAD (Jahd.f. Min., 1882, Beil.Bd. [ii], 139--185).-The hornblende basalts, charac-terised macroscopically by their richness in porphyritic amphibolecrystals, contain microscopically as essential constituents, plngioclase,augite, hornblende, magnetite, and olivine. In the Rhon rocks,nepheline occurs, although never in distinct crystals, and is of nospecial importance for the composition of the rock, as the chemicalanalysis also proves.The hornblende basalts form a subdivision of the felspar basalts.When nepheline is present in greater quantity, they pass into basa-nites ; in the absence of plagioclase, and with predominence of a glassbasis they approach the limburgites. The most interesting constituent,the hornblende, frequently shows remarkable peculiarities of structure.Rounded crystals are specially characteristic of it.It was withoutdoubt an original ingredient of the rock, which has separated veryearly out of the magma. The hornblende basalts of the Rhon-moun-tains, where they seem to be most widely distributed, never form highpeaks. They are of older origin than the basalts, which are free fromhornblende, as can at least be proved in the case of the Rho, and theVogelsberg.The chemical composition indicates that the hornblende basalts aretolerably basic, owing to their richness in magnetite, hornblende, andaugite. The percentage of silica scarcely rises above 44 ; that of sodavaries between 2-57 and 3.25; thus it may be seen that it is notgreater than in other felspar bssalts, and this proves that the nephe-line does not play a special part in the hornblende basalts.The per-centage of potash varies between 1.36 and 1.54. Only a few varietiesfrom the Rhon gelatinise weakly with hydrochloric acid, with separa-tion of little cubes of sodium chloride.The rocks from Beuelberg, near Kircheip, and from Naurod, nearViesbaden, contain hornblende and augite, but no felspar can be foundmicroscopically in them as an essential constituent, and they containlarge amounts of olivine; they belong to the group of the tertiarypicrite porphyries. B. H. B.Examination of certain Meteorites. By W. PLIGHT (Proc. Roy.Xoc., 33, 343-347).-1. The Bruce meteorite, found a t Cranbourne,near Melbourne, is shown by the author to consist entirely of metallicminerals ; the iron contains no combined carbon, from 7-9 per cent.nickel, some cobalt, silicon, and copper.On the surface were metallicplates of a flexible minera.1 of composition Fe&, which the authorproposes to name Edmondsite. Among other minerals present wererhabdite, Fe4Ni,P, a brittle coarse powder, proba,bly identical witha schreibersite of formula (Fe,Ni),P, brass-coloured oblique crystale ofA glassy basis is rarely met with.VOL. XLIV. 170 ABSTRACTS OF CHEMICAL PAPERS.composition Fe9Ni2B2, and square, black metallic prisms of compositionFe,Ni,P, together with triolite and graphite ; the occluded gasesamounted to 3.59 times the volume of the iron, and consisted of-co,. co. H. CHI. N.0.12 31-88 45.79 4.5.5 17.6611.The Rowton siderite fell on April 24th, 1876, a t Rowton, nearWellington, Salop. It is covered with a thin black crust of the mag-netic oxide; some fragments of the block were found on analysis tocontain-Fe. Ni co. cu.91.145 8.582 0-371 tracethus closely resembling the iron of Nevagolla, in India,.gas was 6.38 times the volume of the iron, and consisted of-The occludedcoil. H. co. N.5.155 77.778 7.345 9.722111. The Middlesborough siderite fell at Middlesborough on March14th, 1881 ; it is in the form of a low pyramid, slightly scolloped, thesummit and side being deeply grooved and polished. It contained9.379 per cent. of nickel iron, containing iron, 76.99 ; nickel, 21.32 ;cobalt, 1.69 per cent ; the remaining constituents consist of a solublesilicate identical with olivine, and an insoluble silicate, bronzite.V.H. V.Deposits of Manganese on the Surfaces of Rocks. By BOUS-SINGAULT (Compt. rend., 95, 368-373).-The author has foundmanganese in the magnesia prepared from sea-water by Schloesing’sprocess. Dieulafait has detected manganese in considerable quantityi i t the ashes of marine plants, and the “ Challenger ” expedition dredgedup, from the bottom of the deep sea, nodules containing a largeproportion of manganese dioxide. There can, therefore, be no doubtthat manganese is present in sea-water. The manganese found insuch large quantity on the sea bottom by the “Challenger” is apparentlyof volcanic origin, for it was always found where pumice stone waspresent. The nodules have an oolitic appearance, and frequentlyconsist of concentric layers of manganese dioxide surrounding anucleus of red clay, but they show no trace of organic structure.Buclianan regards the nodules as due to the intervention of animalsubstances, which reduce the sulphates in the sea-water to sulphides.Gurube1 supposes that the manganese is derived from submarinesprings which rise in volcanic districts, and contain manganese car-boilate in solution. The manganese carbonate is deposited, and isosidised by the oxygen dissolved in the water. This explanation isvery similar to that which the author has advanced to account lor thedeposits of manganese dioxide on the surface of rocks on the banksof the Orinoco and in other localities (Abstr., 1882, 1270).C. H. BMIXERALOGICAL CHEMISTRY. lilThe Orchard Alum Spring. By J. C. THRESH (Pharnt. J. Trans.[ 3],13,36l).-This spring, which issues from an old coal mine near thesummit of Axe Edge, in the Peak country, has long been valued as itvermifuge, but it is not adapted as a tonic, owing to the amount ofaluminium sulphate present. The water has a decided red tint, whichvaries according to the wetness of the season; it is acid in reaction,b u t contains no free acid. When heated to 66" it becomes opaque,basic ferric sulpbate separating, but the deposit redissolves as evapora-tion proceeds; the water is colourless if the deposit is allowed tosettle. The sp. gr. = 1*00351, and the composition per gallon is asfollows :-Fe,3S04 .............. 174.426 grains.Fe,Os ................ 6.275 ,,A123S04 .............. 72.908 ,,CaS04 ................ 14.381 ,,FeSOl ................ 1.596 ,,NazSOa ................ 0.537 ,,MgSO,.. .............. 21.055 ,,KzSO, ................ 0.822 ,,AlPOa ................ 0.456 ,,KC1 .................. 0.282 ,,NH,Cl ................ 0-125 ,,SiO,.. ................ 5.776 ,,KNO, ................ 0.170 ,,298.809 ,,The source of the spring is above the millstone grit, which is over-The author proceeds to show theoretically laid by aluminous shale.the formation of ferric sulphate from the ferric sulphide in the shale.E. W. P.Analysis of Waters accompanying Petroleum and of thoseEjected by Mud Volcanoes. By A. POTILITZIN (Jour. Russ. Chem.Soc., 1882, 300-310).-The author has analysed waters of the abovekind from the Caucasian and Caspian petroleum district. The watershave an alkaline reaction, and contain large quantities of sodiumchloride, besides sodium bromide and iodide, the latter in such quan-tities as have never been found before in any mineral water, viz.,0*098-0*118 gram NaI in 1000 grama. The author found also con-siderable quantities of a free organic acid belonging to the fatty series,most probably capric acid. He regards the above petroleum wellsas a new source of iodine. B. B

ISSN:0368-1769    

DOI:10.1039/CA8834400158

出版商:RSC    

年代:1883

数据来源: RSC

摘要:

172 ABSTRACTS OF CHEMICAL bAPERS.Organic Chemistry.Action of Hydrocarbons of the Acetylene Series on Mer-curic Salts. By M. G. KUTCHEROFF (Jour. Russ. Chem. Xoc., 1882,326-327) .-On shaking aqueous solutions of mercuric salts withallylene, white, dense, and sometimes crystalline precipitates of thegeneral formula mHgX,,nHgO,p ( C3H4HgO) separate out. The coeffi-cients m, IZ, and p are different for different salts, e.g., for HgCl,:nz = 3, n = 1, p = 2 ; for Hg(C2E,O2), : m = rt = 1, p = 2 ; forHgSO, : m = 1, IZ = 2, p = 3. The formation of the precipitatesfrom the acetate, sulphate, and chloride takes place as easily as thereaction between allylene and an ammoniacal solution of cuprous orsilver salts, both reactions being equally delicate. A solution of mer-curic bromide gives a slight precipitate, but mercuric iodide in wateror in potassium iodide gives no precipitate.The precipitates areinsoluble in water, easily soluble in acids, acetone being set free at thesame time. The author regardsthese compounds as combinations of basic salts of mercury withacetone, the two hydrogen-atoms of which are replaced by one atomof mercury. A solution of mercuric iodide in potassium iodide andhydroxide, however, absorbs allylene with formation of a crystallineprecipitate ; this is soluble in acids with separation of aZZyZeize.The author explains the hydrntion of hydrocarbons of the acetyleneseries by means of mercuric salts, already announced by him in a,former paper, by the formation of t,he above intermediate compounds.They do not explode when heated.B.B.Transformation of Propyl Bromide into Isopropyl Bromideunder the Influence of Heat. By L. ARONSTEIN (Rec. Tmv. Chim.,1, 13&142).-The author has already shown (Abstr., 1882, 567)that normal propyl bromide, CH,Me.CH,Br or PpBr, heated insealed tubes a t ZSO", is converted into isopropyl bromide, CHMe,Bror PrpBr.Supposing then, in accordance with the received theory of dissocia-tion, that the number of molecules dissociated remains constant a t agiven temperature, the recomposition of dissociated molecules and thedissociation of pre-existing molecules going on simultaneously at thesame rate, the author was led to expect that normalpropyl bromide, ifexposed for a suEcient time to the temperature of dissociation, might becompletely converted into isopropyl bromide. Experiment, however, doesnot confirm this expectation, bnt shows, on the other hand, that afterpropyl bromide has been exposed to the temperature of dissociationfor 20 hours, further heating does not increase the quantity of iso-propyl bromide formed, the transformation not being complete even ifthe heating be continued for 100 hours.This result, which appears at first sight to be a t variance with thefundamental principles of the theory of dissociation, may, according tORGANIC CHEMISTRY rn 173the author, be reconciled with that theoryin two ways, viz.:-(l.) Bysupposing that the propylene and hydrobromic acid resulting from thedecomposition of the propyl bromide recombine partly as PraBr andpartly as PrpBr.If this be the case, PraBr heated in sealed tubesshould be partly converted into PraBr. Such, however, is not thecase : for the author finds that PrSBr may be heated in sealed tubes a t280" for a week with scarcely any alteration, nearly the whole after-wards distilling over at 59-62" (b. p. of PflBr), and only a fewdrops of dark-coloured high-boiling liquid remaining in the retort,probably consisting of hydrobromides of polymeric propylenes.(2.) Another cause capable of preventing the complete transforma-tion of PraBr into PrpBr may, in the author's opinion, be found in thepressure to which the liquid in the sealed tubes is subjected. It isknown indeed that dissociation is retarded by increased pressure, andthe author finds, by determination of the vapour-densities of the pro-ducts obtained by the action of heat on the two propyl bromides, tlhatat any given temperature, PrpBr decomposes more quickly than PraBr :consequently, as the proportion of PrpBr in the mixture becomesgreater, so also will there be an increase in the number of moleculesresolved in a given time into C,H, and HBr, the pressure exerted onthe yet undecomposed molecules, increasing in proportion there to ;and this increase of pressure will retard the decomposition of thenormal prop-yl bromide, and consequently prevent its complete con-version into the isopropyl compound.Similar results have been obtained by Eltekoff .(Ber., 8, 1144 ; 0.J.,1876, 541), with regard to the conversion of'isobutyl bromide intotertiary butyl bromide.Attempts to convert other propyl compounds into isopropyl com-pounds by heating in sealed tubes were ansuccessfnl. Propyl chloride,propyl alcohol, and propyl acetate, heated for several days above 300",showed no sign of alteration; and the same was the case with thedibromide of ethylene (? propylene).oc-Monochlorallylic Alcohol and its Derivatives.By L.HENRY (Compt. rend., 95, 849--851).-On boiling the compoundCH2 : CCl.CH,Cl (b. p. 95") with a dilute solution of potassiumcarbonate for some hours in a wide flask with reflux condenser, thechloride gmdually disappears ; and on distilling the product the alcohol,CH2 CCI. CH2.0H, comes over in the first portions of the distillate,and may be completelF separated from the water by means of potas-sium carbonate.It forms a perfectly limpid colourless liquid, havinga faint sniell. I t s sp. gr. a t 19" is 1.164, and it boils unaltered at 136"under a pressure of 763 mm. It dissolves easily in water, but lesseasily than allylic alcohol. The ethereal acetate, CH, : CCl.CH&,produced by t%e action of acetic chloride, boils a t 145". The bromide,CH, : CCl.CH2Br, formed by the action of phosphorus tribromide,boils a t 121". The corresponding thiocyanate obtained by the actionof the chloride on potassium thiocyanate, boils a t 180-181" withoutdecomposition. When freshly distilled, it is colourless, and recallsexactly the odour of oil of mustard, but after a time it becomes brown.By the action of ammonia upon it, monochiorothiosinnamine isH.W174 ABSTRACTS OF CHEMICAL PAPERS.obtained, melting a t 90-91". A mixture of concentrated nitric andsulphuric acids, well cooled, converts the alcohol into the compounda-Monochlorallylic alcohol dissolves easily in sulphuric acid withdevelopment of heat, and hydrochloric acid is evolved. Distilled witha large quantity of water, the liquid yields a product having all theproperties of pyruvic alcohol, CH,.CO.CH,.O 8.The author draws attention to the grcat difference in physiologicalproperties between the compound above described and /3-monochlor-allylic alcohol, described by Van Romburgh (Bull. SOC. Chim., 36,557), the latter being intensely caustic.CH, : CHCl.CH,.NOs.E.H. R.Ethylene Oxide. By BERTHELOT (Bull. SOC. Chirn., 39, 488-491).-The basic properties of ethylene oxide, as evidenced by itsready combination with hydrochloric acid, have been pointed out byWurtz; this reaction the author has made the subject of a thermo-chemical study.The equation C2H40 + HC1 = C2H5C10 develops heat = + 36.0cal., a number comparable in value to C2H4 + HCl = C2H,C1 = + 38 cal., although in the first case a compound analogous to thehydrate and alcoholates of hydrochloric acid is a t first formed, whilstno such intermediate product is possible with ethylene. But thevalues for the combination of ethylene oxide and ammonia with hydro-chloric acid are approximately equal: for NH, + HCl = NH,C1 = + 42.5,if the heat of solidification of ethylene chlorhpdrin be taken intoaccount; and further, C2H402 (very dilute) + HCl (very dilute) =C2H,C10 (dissolved) = + 12.4, a value equal to the heat of combus-tion of ammonia or potash with hydrochloric acid under the sameconditions.Attention is also drawn to the fact that ethylene oxide com-bines with hydrochloric acid in the presence of a large quantityof water with evolution of a considerable amount of heat ; thisphenomenon explains the reaction between ethylene oxide and themetallic chlorides observed by Wurtz; f o r in the presence of watera certain quantity of hydrochloric acid is formed, and an equilibriumis established dependent upon the heat of formation of the metallicchloride and oxychloride, and the degree of dissociation of the hydrateand the oxychloride in presence of water.Ethylene oxide, doubtless, combines with the other haldid acids, butthis is not the case with the organic acids, for dilute acetic acid isnot appreciably neutralised by the oxide even a'fter the lapse of manyhours. V.H. V.Strobometric Determination of the Rate of Inversion ofCane-sugar, and Transition of the Birotation of Milk-sugarinto its Normal Rotation. By F. URECH (Bey., 15, 2130-2133).--In continuation of his former work on this subject (Abstr., 1881,242), the author finds that although the ultimate result of the inver-sion is unaffected by the concentration of the solution, strength of acidused, or temperature, the rate of inversion varies very greatly undeORGANIC CHEMISTRY.175variations of these conditions. The volume of the solution remainingconst,ant, increase in the percentage of acid present decreases the timerequired for the inversion. The percentage of acid to water beingconstant, increase of volume decreases the time, but percentage of acidto sugar being constant, increase of volume ( i e . , dilution with water)increases the time. Increase of temperature shortens the time of re-action. I n the case of sugar of milk, the rate of transition of thebirotation to the normal seems independent of the proportion of waterto sugar. An addition of a small quantity of hydrochloric acidquickens the action a t first, but does not shorten the total'time ofreaction. When 3 grams of sugar of milk were dissolved in 50 C.C.of hydrochloric acid of sp.gr. 1.155, the rotation was a t once reducedfrom 10" 6' to 6", but after two hours had returned to 10". (See alsoSchmoger, Ber., 13, 1927.) L. T. T.Anhydrous Grape-sugar from Aqueous Solution. By 0..Transformation of Arnides into Amines. By BAUBIGNY(Compt. rend., 95, 646--648).-When a primary or secondary amineis heated with an ethereal salt(, an amide is formed and the alcohol ofthe ethereal salt is set free. Ethylamine and methyl acetate, forexample, yield ethylscetamide and methyl alcohol. Under certainconditions, these amides combine with water, reproducing the originalsalt. The author finds that when the amides are heated a t a tempe-rature higher than that necessary for their formation, they combinewith alcohol, forming the original salt, in which, however, the amineis replaced by a substituted amine derived from the alcohol employed.Acetamide, heated with ethyl alcohol, yields ethylamine acetate ; andethylacetamide, under the same conditions, yields diethylamine acetate.The reaction has been observed with methyl, ethyl, and amyl alcohols,wit'h alcohols of the benzene series, and with acetic, valeric, and benzoicacids.The nmide and the compound amine can be formed in suc-cessive stages of the same operation by heating first at a low, then ata high temperature. When ammonium benzoate is heated withethyl alcohol, or when ammonia in dcoholic solution is heated withethyl benzoate, benzamide is first formed, with elimination of water,and then after some hours' heating a t a higher temperature, ethyl-amine benzoate is formed by the action of the amide on the alcohol.With a mixture of aniline, glacial acetic acid, and methyl alcohol,phenylacetamide and water are first formed, then methylaniline andacetic acid, the salt formed by their union being very unstable.Tliischange can be repeated so as to produce successively, for example,ethylamine benzoa,te, diethylamine benzoate, and triethylamine ben-zoate. The final product contains either the tertiary arnine alone or amixture of different amines, according to the proportion of alcoholemployed. Ammoniums are not formed, and in this respect the reac-tion differs from the action of the amines on alcoholic chlorides, &c.It is worthy of note, that no aniline is formed by the action ofacetamide on phenol, even after heating a t 300" for eight hours.Itis possible that the cyanides derived from the arnides by loss of waterHEME (Ber., 15, 2349-2350) .-A question of priority176 ABSTRACTS OF CHEMICAL PAPERS.will combine with alcohol in a similar manner. A large series of newcompounds would thus be formed.Action of Anhydrous Aluminium Chloride on Acetone. ByE. LOUISE (Compt. rend., 95, 602-603).-1f acetone is gently heatedand aluminium chloride added in successive portions, the mixture,after about 20 hours, is converted into a blackish solid and liquid.This product, when distilled in steam, yields a yellow liquid, amountingto about 35-40 per cent.of the acetone used. It consists of conden-sation-products from acetone, mixed with unstable chlorine-derivativesof the same products. When treated with potash and distilled, ityields a more volatile portion, consisting mainly of mobile colourlessmesityl oxide CsHIlloO, (b. p. 128-130", vapour-density found, 3.51,calculated, 3*39), and a less volatile portion, which conOains crystal-lisable phorone, C,H,,O (m. p. 28", b. p. 195-196", rapour-densityfound, 4.51, calculated, 4-77), mixed with higher condensation-pro-ducts which will not crystallise.The double chloride of aluminium and sodium acts on acetone i n asimilar manner. C. H. B.Action of Nitric Acid on Fatty Acids containing theIsopropyl-group. By J. BREDT (Ber., 15, 2318-23%5). -Whenisovaleric acid is acted on by nitric acid, a mixture of methylmalicacid [identical with the nzethoxysuccinic acid described by Demarqay(Cowpt.rend., 82, 1337) and Morris (this Journal, 1860, 6)], and8-nitrovaleric acid is produced. The two acids are easily separated byrecrystnllisation, the nitro-acid being much less soluble than methyl-malic acid. P-nitroisovaleric acid crystallises in glistening platesbelonging to the monoclinic system, a : b : c = 1.8346 : 1 : 1.7442 p =87" 28'. On reduction with tin and hydrochloric acid, p-aniido-isovaleric acid is obtained. It is identical with the acid described byHeintz (Anizalen, 198, 42). Nitroisovaleric acid is decomposed bystrong nitric acid, yielding dinitrcisopropane (m. p. 50", b. p. 187"),which has been describcd by Meyer and Locher (ibid., 180, 147).This hydrocarbon is also obtained as a bye-product of the action ofnitric acid on ipovaleric acid from valerian root.Under similar treat-ment, isovaleric acid from fermentation amyl alcohol yields methyl-malic acid, nitroisovaleric acid, and dinitroisopropane.Solidification of Different Mixtures of Naphthalene andStearic Acid. By H. COTJRTONNE (Compt. rend., 95, 922-924).-The results of Heintz and of Gottlieb on the melting points of mixturesof fatty acids are borne out by mixtures of bodies widely differing intheir chemical properties, such as st'earic acid and naphthalene.Commercial stearic acid was used ; the results are, therefore, onlyrelative: but if it be admitted that a definite compound is formed(m.p. 47") by melting 100 parts stearic acid with 40 parts naphtha-lene*, by a simple calculation the solidifying points of the three firstmixtures given in the following table may be found. These numbersare given in the fourth column :-* These numbers were taken a5 approaching most nearly the relation betweenthe molecular weights of the two bodies.C. H. B.W. C. WStearic acid.100.07,779 99 ,>797,73 9977,9 ,9 , 0.0ORGANIC CHEMISTRY. 177Point of solidification.Naphthalene. Found. Calculated.0.007.501.5.0022.5040.0045.0050.007 i b O90.00135.002 70.00ld&OO56.00 -53.50 53.8051-50 519050.00 50.2047.00 -47.50 48.0047.60 --&'60 -- 58.5066-0073.00---$00 -The solidifying point of the last four mixtures is not constant.What reaction takes place between these two bodies? Whether acompound analogous to that of stearic acid with glucose or those ofnaphthalene with di- and tri-nitrophenol is formed, will form thesubject of further research.Conversion of Acetonechloroform into HydroxyisobutyrieAcid. By C.WTLLGERODT (Ber., 15, 2305-2308).-Acetonechloro-form, OH.CMe2.CC13, is decomposed by water a t 180", forming hydro-chloric and hydroxyisobutyric acids, CMe2( OH) .COOH.5. T. 0's.w. c. w.Bye-products in the Preparation of Acetonechloroform. ByC. WILLGERODT (Ber., 15, 2308-2313).-On acidifying the residueobtained in the preparation of acetonechloroform, an oily liquid isliberated (b.p. 192-212°), which contains acetonaloxyisobutyric acid,COOH. CMe,. 0. CMe2. 0. CMe2. COOH. This acid probably owes itsformation to the action of potash on a mixture of acetonechloroformand diacetonechloroform, potassium acetonate and acetoneoxyisobuty-rate being formed in the first instmce. Two molecules of the lattersalt lose a molecule of water, and form potassium acetonaloxyiso-Halogen Substitution-compounds of Ethyl Acetoacetate.By M. CONRAD (Ber., 15, 2133--2134).-1n reference to the denial byDuisberg (Abstr., 1882, 1192) of the existence of ethyl dibromacetatedibromide described by the author (Anualeu, 186, 232), he is inclinedto look upon this body as identical with the tetrabromacetoaceticether, CGH6Br403, obtained by Duisberg, instead of C6H8Br,o3,Br,, asoriginally proposed by himself.By E.LIPPMANN (Ber., 15, 2142--2144).-The author upholds the correct-ness of his ethyl acetoacetate dibromide, C6Hlo03Br, ( JVie77,.Alcad.butyrate. w. c. w.L. T. T.The Addition of Bromine to Ethyl Acetoacetate7 78 ABSTRACTS OF CHEMICAL PAPERS.Eer., 1868, 58 [2], 310), the existence of which is denied by Duisberg(Ahstr., 1882, 1192). This dibromide is very unstable, and he believesDuisberg's preparation, which was kept 14 days before analysis, to bea decomposition-product formed according to the equation C6H1008Br2= C6H,BrO3 + HBr. L. 9'. T.Decomposition of Tertiary Amy1 Acetate by Heat. By N.%$ENSCHUrKIN (Cornpi. rend., 95, 648--651).-The author has pre-viously found (Abstr., 1881, 36) that the etherification of acetic acidand tertiary amyl alcohol takes place very slowly and only to a verylimited extent. He has therefore investigated the dissociation oftertiary amyl acetate a t 155" by the method described in a formerpaper.During the first 20 hours, the rate of decomposition is veryslow; it then rapidly increases and attains a maximum after 48hours ; then again decreases until, after 92 hours, the decompositionalmost ceases. The decomposition, C6H,,.C2H302 = CsHlo + C2H402,is limited by the inverse change, C5H,,, + C2H402 = C,HI,.C,H,02 ;but the effect of this inverse change is very slight, for the limit ofdeconiposition a t +53" is as high as 97.42 per cent. The limit ofetherificntion of acetic acid and tertiary amyl alcohol at the sametemperature was previously found (Zoc. cit.) t o be 2.53 per cent.Therate of decomposition is materially affected by the temperature. At100" there is n o decomposition; at 125" it is only perceptible aftersome days' continuous heating, and even at 140" it is extremely slow.The higher the temperature, the more quickly does decompositioncommence, and the greater is its rapidity in all phases ; but underthe most favourable conditions decomposition is not perceptible untilafter two hours' heating ; and whatever the temperature, the rate ofdecomposition is a t first very slow, then increases and attains amaximum, then decreases until the limit of decomposition is reached.The author was unable to ascertain definitely whether the limitdepends on the temperature; at 145" it was found to be 96.59 percent., at 155" 97.42 per cent.C. H. B.Action of Ammonium Cyanate on Glyoxal. By N. LJURAVIN(Jour. Russ. Chew. the., 1882, 281-291).-The author describes ex-periments by which he proves that the compound obtained in the abovereaction, and formerly regarded by him as diamidosuccinic acid, is inreality glgcocine ; but up to the present time he has not been able toascertain the course of the reaction. B. B.Series of Salts containing Chromium and Urea. By W. T.SELL (Yroc. Roy. Soc., 33, 267-274).-When urea is moistened withchromium oxychloride, there is considerable development of heat, andon treating the product with water a green crystalline powder isobtained ; this compound is insoluble in alcohol and ether and dissolvesin hot water with decomposition, another salt separating out in olive-green needles ; this latter body is a dichromate of a base containingurea and chromium, and has the compositioORGANIC CHEMISTRY.179it is sparingly soluble in cold, more freely i n hot, water ; its aqueoussolution gives crystalline precipitates with platinum chloride andpotassium ferrocyanide. The platinochloride,crystallises in green silky needles, sparingly soluble in cold water ;the chloride, ( CONzH4) lzCrzC16,6H20, obtained by decomposing thedichromate with lead chloride and water, crystallises in slender silkyneedles, sparingly soluble in cold, readily soluble in hot water. Itsaqueous solution is precipitated by potassium diohromate and ferro-cyanide and by platinum chloride.The suZphnte,(coNzH,)izC~.( S04)3,10H,0,obtained from the chloride by the action of silver sulphate, crystallisesin dark-green prisms ; the nitrate, (COY2H,)12CrZ(N03)6, also presentsa similar form. The formation of a hydroxide was suspected, but itwas not obtained in a state sufficiently pure for analysis.V. H. V.Synthesis of Uric Acid. By J. HORBACZEWSKI (Monatsh. Chew.,3, 796) .-Pure glycocine (from hippuric acid) was finely pulverisedand mixed with ten times its weight of pure urea prepared fromammonium cyanate, and the mixture was heated in a small flask placedin a metal bath at 200-230" till, the liquid, at first colourless andtransparent, became brownish-yellow and turbid. The melt when coldwas dissolved in potash, and the solution, after supersaturation withsal-ammoniac, was precipitated with a mixture of' ammoniacal silverfiolution and magnesia-mixture.The resulting precipitate was wellwashed with ammoniscal water and decomposed with potassium sul-phide, the liquid filtered from silver sulphide, and the filtrate, afteracidulation with hydrochloric acid, was concentrated on the water-Lath, whereby u r i c a c i d was separated. The crude product tbnsobtained was redissolved in potash-lye, and the above-described processtwice repeated, whereby ultimately a yellowish crystalline powder wasobtained exhibiting the composition, physical properties, and all theyeactions of uric: acid.H. W.Crystallographic Examination of a-p-Dinitroparaxyleneand of the Dinitroparaxylene which melts at 93". By F. BARNER(Bey., 15, 2302--2305).-l'he crystals melting a t 99*5", which Jannaschand Stiinkel (Abstr., 1880, 808) obtained on crystallising a mixture ofa- and 6-dinitroparaxylenes from glacial acetic acid, or preferablyfrom benzene, belong to the rhombic system and exhibit -sphenoidalhemihedry. The ratio of t'he axes a : b : c is 0.69649 : 1 : 1.06850.Dinitroparaxylene (m. p. 93") is deposited from a solution in benzenein lustrous prisms belonging to the monoclinic system, a : b : c =0.869502 : 1 : 0.63818 ; B = 81" 14' 52". w. c. w.Benzyleneorthotolylamine and Methylphenanthridine. BgA. ETARD (Compt. rend., 95, 730--732).-When orthotoluidine andbenzaldehyde are mixed in molecular proportions, heat is evolved,water is separated, and a substance is produced which boils at 314180 ABSTRACTS OF CHEMICAL PAPERS.(uncorr.).Analysis and determination of vaponr-density lead to theformula C,&Me.N CHPh. Water, especially a t loo", decomposes thissubstance into orthotoluidine and benzaldehyde. Concentrated hydro-chloric and nitric acids give rise t o the products of the action of theseacids on orthotoluidine and benzaldehyde respectively. When ben-zyleneorthotolylamine is allowed t o fall drop by drop into an iron tubeat, a bright red heat, two simultaneous decompositions result. One ofthese is represented by the equation C6.E14Me.N CH.C& = C6H5Xe + C,H:,.CN; the other consists in the removal of 2 atoms of hydro-gen from the original substance and the Formation of a new bodywhich the author terms metl~~~Ae.nanthridin,e.C6H41fe.N C6H,Me.N11 = % + I I1 - CJ&,.CH CsH, - CHThe new substance bears the same relation to methylphenanthrenethat pyridine does to benzene.To isolate the new base, the mixedproduct is steam-distilled, by which means the toluene and benzonitrileare removed, and the residue is distilled. The substance is easilypurified, by cr.ystallisation from ether, when it melts a t 170" and boilsabove 360". It is insoluble in water, slightly soluble in alcohol, verysoluble in ether. Aqueous hydrochloric acid does not dissolve it, but inalcoholic solution a hydrochloride is obtained which gives a crystalliuedouble salt with platinic chloride.The author has obtained similarresults with ortho- and para-toluidine and other aldehydes.E. H. B.Azoxylene. By N. SAMONOFF .(,Tour. Russ. Chem. SOC , 1882, 327-328) .-On adding a mixture of potassium hydroxide and ferrocyanideto xylidine sulphate (b. p. 198--210"), an orange precipitate separatesout a t first, and later on resinous compounds are formed: the pre-cipitate is separated from the liquid, dissolved in alcohol, and treatedwith chlorine in order to destroy the resinous bodies. Dark-red crys-tals separate from the solution, which after purification by repeatedcrystallisation melt a t 128". This compound is identical with theazoxylene which Werigo obtained in 1864 by reducing the unsym-metrical nitroparaxylene with sodium-amalgam.The author proposesto examine the axoxylenes. B. B.Klinger's Method of Preparing Azoxybenzene. Note by N.MOLTCHANOFFSKY (Jour. Russ. Chem. Soc.; 1882, 350).-On repeatingKlinger's method for obtaining azoxybenzene, the author could notget more than 32 per cent. of the theoretical yield, though Klingerwould seem to have got a yield of 100 per cent. (48 grams from 60grams of nitrobenzene) ; moreover the preparation obtained by theabove method was far from. being pure. The author recommendstherefore the use of his own method (Abstr., 1882, 965), the yield ofwhich is over 87 per cent. of the theoretical.By P. GRIESS (Ber., 15, 2183-2201).-Thisis the first of two papers in which the author intends summarisingB.B.Diazo-compoundsORGl ANIC CHEMISTRY. 181the results of several years' work on this subject. I n the presentnotice he details the results of the action of paradiazobenzenesulphonicacid (parabenzene-diazine sulphite), C6H4<-N,- so, >, on various primaryamido-compounds,When molecular proportions of paradiazoben~enesulphonic acid andaniline hydrochloride are heated together in aqueous solution for about24 hours, the product is found to consist of diazobenzene hydrochloride,sulphanilic acid, and a new compound, which the author namesarnidoazobenzenesu&honic acid. The reactions probably take placeaccording to the two equations-(i.) C,H,SO,N, + C,H,.NH,Cl = C6H4( s03H).N,.C6H~.NH, + HCI,(ii.) C,H,SO,N, + NH3PhC1 = Ph.N,Cl + C6H4(S03H).NH2.When free aniline WBS used instead of the hydrochloride, the diazo-benzene hydrochloride formed in the above reaction was replaced bydiazoamidobenzene.Azonmidobenzeneszclpphonic acid,C,R,(SO3H).N,.CsH4.NHz [SOsH : Nz : NHZ = 4 : 1 : 41,is precipitated from it solution of its ammonium salt in glitteringyellowish-white microscopic needles, which are almost insoluble inwater, alcohol, ether, and chloroform.When heated, it carbonisesand gives off SO,. Reduced wit'h tin and hydrochloric acid, it splitsup into sulphanilic acid and paraphenylenediamine. The barium salt,( C12H,,N3.S03)2Ba + 6H,O, crystallises in reddish-yellow needles,sparingly soluble in water.Diazoazobenzeneszl.l~onic acid (azobenzenediazine sulphite),-SO&C6H4<Nz.is obtained when azoamidobenzenesulphonic acid suspended in wateris treated for some time with nitrous acid.It forms pale yellowmicroscopic needles, almost insoluble in the usual neutral solvents.It is dissolved by potash, and reprecipitated unchanged by mineralacids. It has scarcely any taste, and decomposes with explosiveviolence st high temperatures. If boiled for some time with water, itis converted into p henolazobenzeneparasulphonic acid,C6H,(S03H).N2.NCsHa(OH) [N : S03H = 1 : 41,already described by the author (Abstr., 1879, 315). Heated withdilute alcohol, an aeobenzenesulphonic acid, C6H4( S0,H) .N,. C,H,,is produced identical with that previously obtained by the author(AnmaZen, 154, 208) by the action of fuming sulphuric acid onazobenzene.Azoa.naidohenzemed isulphonic acid, C6H, ( S 03H).N2. CsH3( S 0,H).NH,,is produced on heating azoamidobenzenesnlphonic acid with fourtimes its weight of fuming aulphuric acid at 100" until water nolonger causes a precipitate. This acid crystallises in glisteningviolet-coloured needles, easily soluble in boiling, sparingly so in col182 ABSTRACTS OF CHEMICAL PAPERS.water, but easily soluble in alcohol, from which it is reprecipitated byether; on exposure to the air, it effloresces to a brown powder. Itdyes silk and wool a fine yellow. Reduced with tin and hydrochloricacid, it splits up into snlphnnilic acid and an acid crystallising inwhite needles, which the author believes to be diamidobenzenesulphonicacid.Barium axoamidobenxenedisulphonnte, CI2H7N2(NH2)( SO,),Ba +7$H20, is easily soluble in boiling water, and on cooling, crystallisesout in reddish-yellow needles.D~azoazobe?azen~edis?~~p~~oni~ acid is obtained from the foregoing acid bythe action of nitrous acid, and is precipitated from its alcoholicsolution by ether in dirty yellow needlep, which carbonise easily whenheated. An azobeiizenedisuzphonic acid, S03H.C6H,.N,.C6H,.S03H, isformed on heating i t with alcohol.The author finds that the above-mentioned azoamido-mono- anddi-sulphonic acids are identical with those prepared according toGrader’s patent by heating azoamidobenzene with 3 to 5 times i t sbulk of fuming sulphixric acid. The author also states that theprocess for preparing azoamidobenzenemonosulphonic acid patentedby Grassler was described by himself as carly as 1876, and that, more-over, this process is valueless from a technical point of view.Action of Paradiazobewenesulphonic Acid on.the Isomeric Toluidines.-The general reactions (taking the chlorides as examples) are-(i.) C,H,SO,N, + C,H,.NH,Cl = C,H,(so,H).N,.C,H,.NH, + HCZ,(ii.) C6H,SOsN2 + C7H7.NHsCl = C7H7.N2.C1 + C6&(S03H).NH2.With orthotoluidine, the reaction takes place principally according to(ii), orthodiazotoluene chloride and sulphanilic acid being the chiefproducts. With metatoluidine, reaction (i) plays the principal part,azo-o-amidotoluene-p-benzenesulphonic acid forming the greatler partof the product. With paratoluidine, reaction (ii) alone takes place,no trace of azo-p-amidotoluene-p-benzenesulphonic acid having beenfound.The author notes here the incorrectness of the generallyreceived idea that in hydrated and amidated benzenes the pura-com-pounds are incapable of reacting with diazo-compounds to formazo-compounds, because t,he hydrogen-atom in the para-position to theOH o r KH2 group is always the one acted on: parahydroxg-benzoic acid and paradiazobenzenesnlphonic acid, for instance, com-bine to form azo-p-snlphobenzene-p- hydroxybenzoic acid,CsH4( SOsH) .N,.C,H,( OH) .COOH,in which [SO,H : N = 4 : 11 and [OH : COOH = 1 : 41. This acidcrystallises in pale yellow needles, easily soluble in boiling, sparinglyin cold water, and very much resembling the corresponding azo-acidobtained from salicylic acid.Par{ I diazobenzenesul~honicl acid combines very readily with z- and6 - n a p h t h y lamine to form azoamidonap hth ale.nebenze~zeszL1~lzoriic acid, nosecondary reactions taking place, as in the case of the toluidines andaniline.Azo-a-amidonayhthaleneparabel7zenesz~on~c acid (Ber., 12, 224)forms a potassium salt crystallising with 3H20, and a barium saltalso with 3H20OROANlC CHEMISTRY.183Azo- fI-amidona,p ht ha1 eneparabenzenemlp honic acid,CsH,(S03H).N~.CloH6.NH, [SOsH : N = 4 : 11 and [N : NH, = 1 : 21,prepared by acting on @-naphthylamine hydrochloride with para-diazobenzenesnlphonic acid, is obtained in yellowish-red needles orgroups of needles, slightly soluble in boiling water. It is very solublein alcohol, thus differing from its isomeride. It carbonises easily,giving off napht hylamine.The potassium salt crystallises in yellowish-red flakes with iQH,O.Both these acids split up under the action of tin and hydrochloricacid into the corresponding diamidonaphthalenes and sulphaiiilic acid.Diamidonucphthalene from the a-acid crystallises in white needles orsmall prisms, which quickly turn green, especially if moist. It iseasily soluble in alcohol, ether, and chloroform, sparingly in boilingwater ; its aqueous solution decomposes quickly. It has an extremelyburning taste, producing on the tongue soreness lasting for days. Itmelts at 120" to a brown oil having an odour similar to that ofquinone. Ferric chloride produces a-naphthaquinone in a hydro-chloric acid solution of this body. The hydrochloride crystallises i nwhite glistening flakes, easily soluble in hot water, almost insoluble inhydrochloric acid.This diamidonaphthalene is almost certainlyidentical with that obtained by Perkin (this Journal, 18, 181) fromazo-a-amidonaphthalene, and that which Liebermann and Dittlerprepared (Anna7ert, 183, 239) from a-amidonitronaphthalene.Diamidoitapl~thalene from the B-acid is equally soluble with itsisomeride in alcohol, ether, and chloroform, more sparingly so in hotwater, from which it separates in white rhombic plates (m. p. 95")having a silvery lustre, soon turfiing to grey. Ferric chloride pro-duces change of colour in its solution, but no quinone or other crys-talline body could be detected.The chloride is easily soluble i nwater, and is reprecipitated by hydrochloric acid. The authorassigns to the first mentioned diamidonaphthalene (from the a-acid,as also Perkin's, and Liebermann and Dittler's), the formulaC,,H,(NH,), [NH,:NH2=1 : 41, and that from the &acid [NH,: NH,=1 : 21, and to Aiguar's ( B e y . , 7, 307) a-diamidonaphthalene (m. p.lSS0), [NH, : NH, = 1 : 4'1, and to the same investigators P-diamide(m. p. 66O) LNH, : NH, = 1 : 1'1.With the isomeric amidonaphthalenesulphonic acids, paradiazobenzene-sulphonic acid forms compounds analogous to those with the isomericnaph thylamines.Axo-a- amiclosulphonaph thal en e-p- beiazeiiesulp honk acid,NH2.aCloH6( SOAH) .N,.C,H,( S0,H) ,(the only one of these compounds which the author has investigated indetail), is easily soluble in alcohol and water, insoluble in ether, andcolours silk and wool yellow.n'ith barium it forms an acid salt,( C,,H,,~,S2O6),Bft + 8Hz0, very sparingly soluble in boiling water,and a neutral salt, (C16HllN3S,0,)Ba + 7+H20, easily soluble in boil-ing water. Treated with tin and hydrochloric acid, dianaidoiiaplttha-1ene.culpt~onic and sulphanilic acids are produced.When paradiazobenzenesulphonic acid acts on either of the isomeri184 ABSTRACTS OF CHEMICAL PAPERS.diamidobenzenes, nitrogen is evolved, and a brown gummy massresults. If orthodiainidobeizzen'e chloyide be used instead of the free base,small quantities of sui'phanilic acid and axinzidobenxene, C H ' I 'NH,are produced ideiitical with that which Ladenburg obtained by actingon orthodiamidobenzene with nitric acid.8-Dianzidobenzoic acid, [COOH : NH, : NH, = 1 : 3 : 51, combinesdirectly with the diazo-acid to form nzo-p-s~clphobenzene-8-dianaiduben-zoic acid, C6&( s0,H) .N2.C6H,(PU'H,)2.COOH. This acid is sparinglysoluble in water, alcohol, and ether, and decomposes very easily, evenon boiling with water.Treated with tin and hydrochloric acid,it gives sulphanilic acid and a new triamidobenzoic acid,This acid crystallises from hot water in colourless compact crystals,very sparingly soluble in a,lcohol, insoluble in ether, and having abitter taste. On attempting to distil it, it almost entirely carbonises,but a small quantity of a base distils over, which may he triamido-benzene.Sulphuric acid gives a salt, C7H9N302,H2SOd. Taking intoaccount the origin of this acid, and that the only other knowntriamidobenzoic acid (Sdkowsky, Awnalen, 163, 12) has the formula[COOH : NH, : NH, : NH, = 1 : 3 : 4 : 51, the formula given abovemust be the correct one. From this it would appear that the azo-acidmust have the formula-N4\N/C,H,(NHz),COOH [COOH : E€Xz : NH, : NH, = 1 : 2 : 3 : 51.C,H,(SOsH).N : N.CsH2(NHz),COOH [COOH : N : NH, : NH? =1 : 2 : 3 : 51. L. T. T.Azylines. By E. LIPPMANN and F. FLEISNEB (Bey., 15,2136-2142).-The authors give the name of azylines to a series of bodies obtainedby the action of nitric oxide on tertiary bases of the aromatic series,and containing the tetrad-group =N-N=.They intend also to trywhether similar bodies can be obtained from secondary amines, andfrom amines belonging to the fatty series.These bodies are obtained by passing nitric oxide into a solution of atertiary amine in alcohol or benzene, whereupon carbonic acid is freelygiven off, and red crystals are deposited. They are insoluble in water,soluble in hydrochloric acid with reddish-purple, in acetic acid withemerald-green coloration. They crystallise from alcohol and benzene inbell-formed red crystals. Their fusing point descends as the molecularweight ascends (except the propyl compound, which melts lower thanthe butyl and amyl bodies). With the chlorides of platinum, gold, zinc,cobalt, &c., they form double salts.By the action of stannous chloride,or of phosphorus and hydriodic acid, unstable hydrogenised bodiesare produced, which, however, yield crystallisable platinochlorides.Mineral acids decompose the azylines, splitting off ammonia. Picricacid gives sparingly soluble cry8talline salts. Bromine and iodinereadily yield substitution-products. The haloyd ethers combine withthem at 100". Nitrous acid produces nitroso-compounds, givingLiebermann's colour reaction with phenol and sulphuric acid. Thefollowing equation expresses the reaction in the case of dimethylORGANIC CHEMISTRY. 185aniline, 2C,€I,,N + N202 = 2Hz0 + Cl6H18N4. The authors believethe general constitutional formula to be R2N.C6H3 : N.N : C6H3.PU'R2.Dimet l ~ y Znwilineaz y line, C 16H18N4, first obtained by Frankland(Awnden, 99,342) fuses a t 266".By careful oxidation with potassiumpermanganate in the cold, it yields carbonic and oxalic acids. This,according to Wallach and Claissen's researches (Ber., 8, l237), tendsto show the correctness of the above formula. The picrate,~16H,,N4,C6H,(N0,),0H + EtOH, forms green need+, which containalcohol of crystallisation.DiethyZan,iZineuzyZino, C2,H2,N4, forms red needles melting a t I '70°,deliquescent in chloroform, and sparingly soluble in cold alcohol. Thepicrate, C20H26N4, [ 2C6H2(N03),.0H], crystallises in yellow needles,sparingly soluble in alcohol and ether.The crystals belongto the rhombic sy+em-(a : b : c = 1 : 0.629 : O913), their principalfaces being mP, mPm, Pcm.Dipropylaniline boils a t 240-242", and forms a yellow crystallineplatinochloride, which is decomposed by water.Dibuty lanilineazy line, C28H42Na, crystallises in needles, and fuses at158".Diamylaniliizeazyli~2e, C32H50N4, fuses a t 1 15".It decomposes at 100".Di~ro~Z/lanilin,enzl/line, C24H34N4, fuses at 90".L.T. T.Phenylenethiocarbamides. By E. LELLMANN (Ber. , 15, 2146-2147).-Orthodiamidohenzene thiocyanate, formed by evaporating anaqueous solution of orthodiamidobenzene hydrochloride with ammo-nium thiocyanate, is further heated in an air-bath a t 120-130", andt,he dry residue extracted with water ; orthopke~iylen.ethiocarbamide,C,H,N,S, remains undissolved. This body is easily soluble in alcohol,sparingly so in water, and crystallises in violet plates.It melts a tabout 280", but becomes brown a t 260": Metadismidobenzene givesa similar body which, with the corresponding para-compound, isnow under investigation. The author proposes the constitutionalformula C6H4<NH>CS for these bodies. L. T. T. XHFormation of Phenylxanthogenamide. By E. BAMBERGER (Ber.,15, 2164-2166).-1n a previous paper (Abstr., 1882, 394) the authordescribed some crystalline bodies obtained b,y heating phenylthio-carbimide with various acid amides in alcoholic solution. He nowfinds that in all cases the body formed is Pl~erL?JZxniatlioge?za~r~ide, andthat the character of the acid amide has no influence on the reaction.L. T. T.Aromatic Isophosphines. By A. M ICHAELIS and L. GLEICHMANN(Ber., 15, 1961--1964).-1n the course of the investigation of themixed aromatic phosphines, the authors endeavoured to obtain thecorresponding phosphonium iodides without the use of the zinc alkyls,by heating together alkyl iodides, phosphenyl chloride, and metalliczinc, and obtained good results.On substituting benzyl chloride forthe alkyl iodides, however, a new class of bodies, the isoplmsphines,were obtained.Isobsiizy~~heny~hospTLilze is prepared by gently warming a mixtureVOL. XLIV. 186 ABSTRACTS OF CHEMICAL PAPERS.of 2 parts benzyl chloride and 1 part phosphenyl chloride, with grann-lated zinc in a vessel provided with a reflux condenser; a violentreaction takes place, and is complet'ed without further heating. Theexcess of benzyl chloride is then decanted, the residual zinc compounddecomposed by soda, and the isophosphine purified by solution inalcohol, precipitation by water, and crystallisation from glacial aceticacid, from which it separates in long, fine, interlaced needles (m.p.70-71"), of the formula Cl3HI3P or C25H24P2. Its properties render itimprobable that it is an crdinary secondary phosphine. It does notunite with the alkyl iodides, nor is it changed by heating with them andzinc oxide in sealed tubes. It unites with acetic anhydride, forming anunstable compound, completely resolved into its components by longexposure to air or by heating at 60-70". It dissolves in benzyl chloride,but is not further affected by it even on heating a t 200" for 15 hours.Strong oxidising agents convert it into benzoic and phosphoric acids ;on heating it with soda-lime, phosphoric acid, benzene, and toluene,are formed ; nascent hydrogen does not act on it.In an atmosphereof chlorine, isobenzylphenylphosphine liquefies to a viscous yellowmass, from which, after treatment with soda t'o remove the chlorinetaken up, an oxide, ClsH13P0 or C&&?P,O, (m. p. 154-355") isobtained, crystallising from acetic acid or alcohol in long, colourless,matted needles. It is insoluble in alkalis, and is similarly indifferentto reagents. Isobenzylphenylphosphine would appear to be closelyrelated to the dibenzylphosphine, CI4Hl5P, obtained by Hofmann(Bey., 5,100) by heating together benzyvl chloride, phosphonium iodide,and zinc oxide.Isotoly lbenzylphosp7Lins is prepared in a manner similar to isobenzyl-phenylphosphine, and closely resembles it in properties ; it crystahlises in light, colourless, felted needles (m.p. 187") of the formulaC,H,,P 01: C27H28P2. A. J. G.Phenylarsine Sulphides. By C. SCHULTE (Bey., 15, 1955-1960) .--Phanylamine monosulphide, AsPhS, is obtained by the actionof sulphuretted hydrogen on phenylarsine oxide or chloride ; it crys-tallises in fine white needles, is sparingly soluble in benzene, alcohol,and ether, readily soluble in hot benzene and in carbon bisulphide.Nitric acid oxidises it to phenglarsenic acid. It is but slightly solublein ammonia, but dissolves in hot soda, and is reprecipitated by hydro-chloric acid. It is sparingly soluble in ammonium monosulphide orsulphydrate, but dissolves readily in the yellow sulphide ; addition ofan acid to the solution precipitates phenylarsine sesquisulphide.Themonosulphide melts at 152" to a yellow liquid, and on dry distillationin a stream of carbonic anhydride, yields arsenic sulphide and tri-phenylarsine. By the action of mercury-ethyl, it is converted intophenyldiethylarsine and mercury sulpl-iide.PlleTzylamine sesguisulphide, AsPh&, is best prepared by the actionof hydrogen sulphide on an ammoniacal solution of phenylarsenic acid,and subsequent precipitation with hydrochloric acid. When crgstal-lised from benzene, it forms pale yellow transparent prisms, readilysolukle in henzene and carbon bisulphide, moderately in boiling glacialacetic acid, sparingly soluble in hot alcohol and ether.It melts aORUANIC CHEMISTRY. 187130" t o a clear liquid, and decomposes: a t higher temperatures. Nitricacid converts it into phenylarsenic acid. It is nearly insoluble inammonia, sparingly soluble in soda, but dissolves readily in yellowammonium sulphide.Bisodiurn phenylsulpharsenate, AsPhS ( SNa),,6H20, is obtained bydissolving phenylarsine mono- or sesqui-sulphide in sodium sulphidecontaining excess of snlphur ; on evaporation and addition of absolutealcohol to the thick liquid, it separates in slender needles. It is readilysoluble in water, sparingly i n alcohol. A. J. G.Arsenobenzene, Arsenonaphthalene, and Phenylcacodyl.By A. MICHAELIS and C. SCHULTE (Ber., 15, 1952--1955).-1n addi-tion to the method previously given (Abstr., 1881, 722), arsenoben-zene can be prepared by the reduction of monophenylarsenic acid.Itreacts readily with sulphur, yielding the phenylarsine sulphides (pre-ceding Abstract). If fused with excess of sulphur, it gives arsenicsulphide and phenyl sulphide. When heated with mercury ethyl insealed tubes a t 150", it gives mercury and diethylphenylamine.Attempts to reduce arsenobenzene to phenylarsine, AsPhH,, have sofar failed, as when heated with alcoholic ammonium sulphide it yieldsbenzene, arsenic sulphide, and metallic arsenic, whilst hydriodic acidhas no action in the cold, and on heating, gives benzene, arsenic iodide,and metallic arsenic.Arsenonaphthalene, ( C10H7)2A~2, is obtained by the reduction ofnaphthylarsineoxide as a powder composed of slender yellow needles(m.p. 221") ; it is sparingly soluble in alcohol, benzene, carbon bisul-phide and chloroform, insoluble in water and in ether. It unites withchlorine, forming naphthylarsine chloride ; with sulphur, formingnaphthylarsine sulphide ; and is oxidised by nitric acid to naphthyl-arsenic acid. On dry distillation, it decomposes, with formation ofnaphthalene aud arsenic, and separation of much carbonaceous matter.PlLerbyZcacodyZ, As,Ph4, as obtained b7 the reduction of diphenyl-arsine oxide with phosphorous acid, forms a white crystalline massmelting a t 135", and soluble in alcohol, less readily in ether. Itquickly oxidises in the air, forming diphenylarsenic anhydride. Withchlorine it forms diphenylarsine trichloride, AsPh2C13.It yieldsarsenic and triphenylarsine on dry distillation.Reduction of Orthonitrobenzaldehyde. By P. FRIEDLANDERand R. HENRIQUES (Ber., 15, 2105-2110).-Rudolph (Ber., 13, 310)CHobtained a base, C,H,/ 11 , by the reduction of orthonitrobenzalde-hyde (obtained by the nitration of benzaldehyde, and containing themeta-compound). The authors have repeated and extended theseexperiments, employing pure orthonitrobemaldehyde, obtained fromethyl nitrocinnamate (Abstr., 1882, 840). They are unable to confirmRudolph's results, having obtained a body CiH,NO.If soda solution in excess be added to the product of the action oftin and acetic acid on orthonitrobenzaldehyde, 2nd the whole distilledwith steam, scarcely anything passes over, but anthranilic acid isA.J. G.'N0 ,188 ABSTRACTS OF CHEMICAL PAPERS.found in the residue. If, however, the acid mixture is neutralisedwith sodium carbonate and distilled with steam, an oil is obtained ofthe formula C7H5N0, which the authors propose to call an,tlzrrlnil.Anthranil is a colourless mobile liquid, slightly soluble in hot water,easily so in t'he nsual solvents. It does not solidify a t - 18" C., hasan odour resembling that of benzaldehyde, and of the vegetable bases,and is easily volatile with steam. Exposed to air and light, it becomesbrown and resinous. It begins to boil at 210-215", but decomposesa t the same time. Anthranil has feeble basic properties, dissolvingeasily in concentrated mineral acids, but is reprecipitated on addingwater.Its salts and double salts are very unstable, the only com-pound obtained being C7H5N0,HgC1, ; this compound fuses a t 174",and is readily decomposable. Dilute soda dissolves anthranil slowlyin the cold, quickly on heating; ammonia requires a temperature of120°, and water has scarcely any action at 130". In these reactionsmihraniZz'c acid is produced : C7H,N0 + H,O = NH,.C6HI.COOH.Boiled with acetic anhydride and mixed with H20, it gives acetyhn-fhrariilic acid, C,H,NO&. These reactions render it probable thatanthranil is an internal anhydride of anthranilic acid, having one of, co .C.OHthe two following formuh : C6H4< 1 or C6H/ 11 . No halogen-,N H 'Nmethyl-.or nitroso-substitution-compounds could be obtained. Fur-ther reducing action gave an amorphous compound, probably a con-densed amidobenzaldehyde ; also, small quantities of amidobeozyla1 co hol .With zinc and hydrochloric acid in alcoholic solution, an amorphoussubstance was obtained, which dissolved in hydrochloric acid, but waspartly reprecipitated by water, entirely by sodirim acetate. It bearsgreat resemblance to the amorphous meta- and para-amidobenzalde-hyde, and is probably a corresponding condensed orthamidobenzalde-hyde. This body is undergoing further investigation. L. T. T.Metahydroxybenzaldehyde and some of its Derivatives. ByF. TIEMANX and R. LUDWIG ( B e y . , 15, 2043-2059) .-Metahydroxy-benzaldehyde has been obtained by Sandemann (Bey., 14, 969) bypartial reduction of meta hydroxybenzoic acid with sodium-amalgam.It is best obtained, however, from metamidobenzaldehyde by thediazo-reaction.For this purpose metanitrobenzaldehyde. prepared bythe method of Priedlander and Henriques (Rer., 14, 2802), is mixedwith exactly the necessary quantity of zinc chloride and hydrochloricacid, and after the reaction is finished a solution of potassium nitriteis added, the mixtiire being kept cold. A double salt,, ha,ving thecomposition ( COH.C6H,.N2.C1),,SnClJ, then separates, and this on beingdecomposed with water easily gives metahydroxybenzaldehyde. Thelatter crjstallises in white needles, nielting a t 104". It yields metahy-droxybenzoic acid on fusion with potash.The potassium compoundsuspended in ether and heated with acetic anhydride, yields theacetyl-derivative, an oil boiling at 263". Metahydroxybenzaldehyde,when boiled for some hours with excess of acetic anhydride, yields acompound, CH(O&)2.C6&0&, melting a t 76"ORGANIC CHEMISTRY. 189MethyZmeta7i~droxybenxalde72yde is a liquid boiling a t 230".Acetonietttcounzaric acid is prepared by heating a mixture of meiiahy-droxy benzaldehyde, anhydrous sodium acetate, and acetic anhydride.It crystallises from water in white needles melting at 151". Onheating it with solution of potash, it yields nzetncoumaric acid, whichcrystallises from hot water in white prisms melting a t 191". Thisacid can also be obtained by the diazo-reaction from metamidocin-namic acid.On treatment with sodium-amalgam, it is reduced toI( ydrometucoumaric acid, which crystdlises in long needles, melting a t111".Net?t,ylmetacoumaric acid melts at 115", and rnethylhydrometacou-maric acid a t 51".Xiitration of Metahydrox?Ibenzaldehyde. - When this aldehyde iswarmed with 10 parts of nitric acid (sp. gr. 1.1), and the productpoured into water, a yellow crystalline mass separates out, which ispartly soluble in benzene and chloroform. After being recrystallisedfrom water, the portion insoluble in benzene melts at 166", and istermed by the author p-nitrornetahydroxybenzaldehyde. The portionsoluble in benzene is separated by a mixture of benzene and lightpetroleum into two bodies, the less soluble melting at 138", termed theycompound, and the other, melting a t 128", the a-compound.Theseare all mononitro-derivatives, and easily yield methyl ethers.Nitration of &!ethylmetah ydroxyBenza1dehyde.-On nitrating this com-pound under different conditions, a mixture of two isomeric dinitro-compounds is always obtained. These may be separated by boilingwater, in which the &compound (m. p. 15t5") is almost insoluble, thea-compound (m. p. 110") being easily soluble.Comtitution of the Niiti.o-derivatiives.--Four mononitro-derivatives ofmetahydroxybenzaldehyde are theoretically possible, in which the NO,-group occupies respectively the two ortho-, the para-, and the meta-position with reference to the hydroxyl. According to the knownlaws of suhstitution i n phenol-like bodies, the authors think it probablethat the three nitro-derivatives prepared by them are those in whichthe N02-group occupies the three former positions.In this case themethyl ethers should, by reduction and the diazo-reaction, yieldrespectively p-metamethoxysalicylaldehyde (Ber., 14, 2022), vanillin,and a- me tame thoxg salicylaldehy de. Now, the so-called y -compoundyields by this treatment a body smelling like vanillin, and the authorstherefore ascribe to it the constitution CsH3( COH) (O&Ie)(NO,)[l : 3 : 41. The @-compound yields, however, a body which does notagree in its properties with either of the metamethoxysalicylaldehydes,and therefore the authors think that it probably has the constitutionC6H3( COH) (OMe) (NO,) [1 : 3 : 51.The a-compound does not yieldany well-defined product.New Derivatives of Salicylaldehyde. By H. VOSWIBCKE L(Bey., 15, 2021-20~7).-ieiemann and Reimer have shown (Bey., 9,1268 ; 10, 1562) that, by the chloroform reaction, salicylic acid yieldsboth para- and ortho-aldehydosalicylic acids, but parahydroxybenzoicacid only one product, namely, orthoaldehydosalicylic acid. Applyingthe same reaction t o salicylic and parahydroxybenzaldehydes, the authorE. H. RI90 ABSTRACTS OF CHEMICAL PAPERS.has obtained analogous results. In the former case two bodies areformed, the one easily, the other sparingly, soluble in light petroleum.The former, a-hyclroxyisophthalaldehyde,CJ&(OH)(COH)z [OH: COH : COH = 1 : 2 : 61,crystallises from water in tufts of needles melting a t 88", the latter,6-hydroxyisophthabldehyde, c6H5(oH) (COH), [OH : COH : COH =1 : 2 : 41, in long needles melting a t 108".When parahydroxybenz-aldehyde is used, only one "bdy is formed, namely, the a-compound.The constitution of these dialdehydes is determined by fusing themwith potash, whereby they are converted into hydroayisop hthalic acid.Attempts to form bodies containing a third COH-group provedfruitless.MethyZsotZicyEaZdehyde.-The author finds that the reaction betweenthe sodium compound of salicylaldehyde and metbyl iodide is com-pleted by digestion on the water-bath. By removing every trace ofsalicylaldehyde, the methyl-derivative is obtained in prisms meltinga t 3 , 5 O .SaZicyZaldehyde cyan.hyd&z, C6H4(0Me)[ CH(OH).CN] [l : 21.Thiscompound is easily obtained by the action of potassic cyanide andhydrochloric acid on salicylaldehyde dissolved in ether. It separatesfrom benzene in colourless transparent crystals melting at 71".Attempts to obtain the corresponding amide were unsuccessful, andorthomethoxyrnanddic acid was obtained only as a syrup in an impurecondition. By the action of the equivalent quantity of a 10 per cent.solution of ammonia in closed vessels a t 60-70", the compound(OMe.C6H,.CH.CN)2N2H, is produced. It melts when freshly pre-pared at 123", but soon alters on exposure to air.Nitri 1 e of or t h ome t hox yp h eny 1 p h en am ido acetic acid,C6H4(OMe)[CH(NHPh).CN [I : 21.This body is easily obtained by the action of aniline on t-he cyanhydrinof methylsalicylaldehyde.It forms colourless six-sided tables meltingat 61".Nitromethy ZsaZicy ZaZde hyde, C,H, (NOz) (OXle) . C0H.-The author hasprepared this compound by dissolving the aldehyde in fuming nitricacid, and recipitating by water. It forms fine white needles meltlingst 88". !$he author is engaged in investigating its constitutionBy R. WEGSCHEIDER (Monatsh. Ohem., 3, 89-795).This compound is formed, together with others, by the action of dilutehydrochloric acid on opianic acid. When these two substances areheated together in a sealed tube a t 160-170", a mixture of dark andnearly colourless crystals is obtained, together with a reddish-yellowliquid ; and on filtering, boiling the crystals with water, and filteringagain, a black mass remains undissolved, and the light red filtrate, boiledwith animal charcoal and evaporated, yields crystals of isovanillin. Onfurther evaporation, a small quantity of unaltered opianic acid separatesout, and the last fraction gives with ferric chloride a green colonr,probably due to the formation of a trace of protocatechuic aldehyde.Jsovanillin recrystallised from water forms anhydrous prismsE.H. R,IsovanillinORGAN10 CHEMISTRY. 191having a vitreous lustre, softening a t 115", melting at 116-117".These crystals are monoclinic, having the axial ratio a : b : c =0.6370 : 1 : 0.9228; /3 = 95.9. Observed faces mP&, OP, 2P&,mP, + P. Habit, tabular by predominance of the clinopinacoid.Face of cleavage PA.Isovaniilin is not much more soluble in caustic soda than in water,but dissolves easily in ammonia and still more in potash-lye, formingyellow solutions. From concentrated alkaline solutions, it is precipi-tated by acids.Strong sulphuric acid colours it yellow, then yel-lowish-red, and slowly dissolves it, both at ordinary temperatures anda t 100" ; on raising the temperature to the boiling point of the acid, ablood-red colour is produced. The aqueous solution is neutral, andgives no reaction with ferric chloride or lead acetate. It reducesammoniacal silver nitrate very slightly in the cold, more abundantlyat boiling heat.Isovanillin is inodorous in the cold, but when heated, and especiallywhen its aqueous solution is boiled, it emits a pleasant odour like thatof vanilla, or fennel, or anise-oil.When heated on platinum-foil, itgives off a stronger odour like that of vanilla, and still more like thatof burning opianic acid.It decomposes slightly when sublimed, and volatilises to a smallextent when its aqueous solution is distilled. Like vanillin, it formssoluble compounds with alkaline bisulphites, and niay be separatedfrom solution in ether by agitation with strong solution of sodiumhydrogen sulphite.If the achion of hydrochloric acid on opianic acid be carried beyondthe point a t which isovanillin is formed, the product subsequentlyobtained is protocatechuic aldehyde, a result which, when viewed inconnection with the fact that isovanillin must differ in constitutionfrom vanillin, shows that the former must be represented by theformula C,H,(COH)(OH)(OMe) [l : 3 : 41.I n the formation of isovanillin from opianic acid, as well as in thatof methylnoropinnic acid from opianic acid, and of methylnorhemi-pinic acid from hemipinic acid, it appears that whenever a singlemethyl-group is detached from hemipinic or opianic acid, the meth-oxyl-group attacked is always that which stands in the ortho-positionrelatively to the carboxyl.H. W.Preparation of the Three Isomeric Nitracetophenones. ByH. GEVEKOHT ( B e y . , 15, 2084-2086).-By acting on ethylic sodace-toacetate with the three isomeric nitrobenzoic chlorides (Ber., 12, 351),the three corresponding ethylic nitrobenzacetoacetates are produced,and these on saponification yield the three nitracetophenones.Themeta- and para-nitracetophenones thus produced agree exactly withthose obtained in other ways. The ortho-compound is now for thefirst time obtained pure. It is a pale yellow oil, which can be distilledin a vacuum, and does not solidify a t -20". It is easily reduced bytin and hydrochloric acid to the corresponding amido-compound,which is a pale yellow oil possessing basic properties, and capable ofbeing distilled unchanged in a vacuum. E. H, R192 ABSTRACTS OF CHEMICAL PAPERS.Action of Cyanogen Chloride on Amido-Acids. By J. TRAUEE(Rer., 15,2110-2122).-The author hoped in this way t o obtain cyan-amido-acids, none of which have hitherto been known in the free state.Cyanogen chloride acts but very slightly on an aqueous solutior ofalanine, producing small quantities of lacturamic acid.When a streamof cyanogen chloride is passed through fusing sarcosine, water isevolved, and methylhydanto'in is produced, as also an anhydride,formed by the abstraction of one molecule of water from two mole-cules of sarcosine. Sarcosine-anhydride, C6H,,N2O,, crystallises inhexagonal colourless plates, melting a t 143-146" : it is easily solublein water, alcohol, and ether : it has a bitter taste, and is reconvertedinto sarcosine by dilute hydrochloric acid. This anhydride differsfrom sarcosine in giving no crystalline compound with zinc chloride,and by its double platinochloride, ( C6H12N203)2,H2PtC16, containing nowater of crystallisation.Cyanogen chloride acts very readily on an alcoholic shution ofmetamidobenzoic acid, and if the prodnct of the reaction is a t oncepoured into a large quantity of water, metacyanamidobenzoic acid isproduced-a secondary reaction sets in very quickly if the alcoholicsolution is allowed to stand before dilution.Meta,cya.1Larnidobenzoic ucid, CN.NH.C&f,.COOH, crystallises in flatwhite rounded needles, containing mol.HZ0 : it is almost insolublein cold, moderately soluble in boiling water: very soluble in boilingalcohol, ether, and chloroform, sparingly so in benzene. Cyannmido-benzoic acid begins to decompose a t 140", but does not fuse below 200",when gas is evolved. Its taste is decidedly acid, and it decomposescarbonates. When heated a t 140" with solution of barium hydroxide,it is decomposed into amidobenzoic acid, ammonia, and carbonic anhy-dride.Boiling it with water causes no decomposition, and evenstrong soda solutiou is slow in its action. Acids decompose it muchmore readily. Most of its salts are easily soluble, but the lead saltforms a white flocculent precipitate, soluble in excess of lead acetateand in boiling water. Ferric chloride produces a pale yellow amor-phous precipitate ; silver nitrate a white gelatinous one insoluble incold water, soluble in ammonia: it is a mixture of the salt,CN.NH.C6H,.COOAg, with small and varying quantities ofNAg(CN) .CsH,. COOAg.A brown amorphous copper salt was also obtained. This productionof a brown copper salt appears to be a common property of the cyan-amides, and serves to distinguish cyanamidobenzoic acid rrom all otherknown derivatives of metamidobenzoic acid.Heated alone, metacyanamidobenzoic acid decomposes slowly at140", quickly at 210-220", evolving cyanic acid freely, and leaving awhite amorphous product insoluble in water, alcohol, ether, and hydro-chloric acid, but easily soluble in concentrated sulphuric acid, fromwhich it is reprecipitated on dilution with water.Analyses show thecomposition of this body to be a mixture of bodies of the general for-mula ntC8H6N202 - nCNOH. This decomposition appears to beanalogous to that observed by Rassler (J. pr. Chern., 16,125) in the caseof ethyl cyanocnrbamate. A siniilar mixed product is obtained by thORGANIC CHEMISTRY.193action of cyanogen chloride on fusing metamidobenzoic acid, but hereCO(NH.C6H'4.COOH)z is also amongst the products of the reacttion.With dilute hydrochloric acid, a similar reaction takes place, as inthe case of cyanocarbamic acid compounds, metuzcl-amidobenxoic ucidbeing formed.Hydrogen sul phide is absorbed very slowly by metacyanamidoben-zoic acid, but with ammonium siilphide a rapid and quantitativereaction takes place, thiouramidoberizoic acid, identical with thatobtained by Arzruni (this Journal, 24, 570), being produced.Tlziouranzii.lobeizzoic acid crystallises in groups of needles melting a t187", and at the same time evolving ammonia and hydrogen sulphide,and leaving products free from sulphur.Several of the salts of metacyanamidobenzoic acid decomposeslowly in contact with boiling water.A concentrated solution ofbarium cyanamidobenzoate heated for several days on the water-bath,gives off ammonia and Ieaves the barium salt of an acid correspondingtolerably closely with the formula C21H17N50,. It is easily soluble inether, alcohol, and water, and gives insoluble zinc, lead, copper, andmercury salts.No addition-product of ammonia could be obtained from cyanamido-benzoic acid. -By digesting it with aniline, PhenzJlbenxocreatisze,NHP h. CNH .NH . CGH,. C 0 OH,is produced. Phenylbeiazocreatine is nearly insoluble in ether andalcohol, easily soluble in boiling water, from which it crystallises incompact groups. It fuses with decomposition at 165" ; i t forms com-pounds both with acids and with alkalis, and gives a yellowish-redpiatinochloride.When cyanamidobenzoic acid is heated with acetamide, it gives abody, C30H'29N506, only soluble in fuming nitric and concentrated sul-phuric acids.The reaction is not analogous to that of acetamide andphenylcyanamide studied by Berger (Abstr., 1881, 810).Paracyaiianzidopheny ltrcetic acid is produced by the action of cya-nogen chloride on an alcoholic solution of paramidophenylacetic acid.It crystallises in colourless glittering plates, very easily soluble inwater, ether, and alcohol, and fusing with decomposition a t 134". Itis a strong acid, and gives a brown copper salt which, like that ofmetacyanamidobenzoic acid, quickly blackens in contact with water.The brown salt differs from that of the meta-acid in being very solublein alcohol.Paracyanamidophenylacetic acid is very unstable, decomposing evenwhen recrystallised.Evaporated with a very small quantity of hydro-cliloric acid, it is converted into par~-.urnrnidopheiaylrr,catii: acid.Pnra-urainiclophe?Lylacetic acid crystallises in compact groups con-taining It is easily solublein alcohol and ether, tolerably so in water. It fuses with decomposi-tion a t 174". With the alkalis and alkaline earths it forms solublesalts ; with copper, lead, zinc, and mercury insoluble. Ferric chloridegives a chnract eristic yellowish-red precipitate.Cyanogen chloride has no action on tyrosine or hippuric acid inalcoholic solution.L. T. T.mol. H,O, which are given up a t 110"194 ABSTRACTS OF CHEMICAL PAPERS.Contributions to the Knowledge of Meta-uramidobenzoicAcid and Carbamido-dibenzoic Acid. By J. TRAUBE (Ber., 16,2122-2129) .-This investigation was undertaken in order to clear upthe divergent statements of Griess (Bey., 2, 147) and Menschutkin(AnnaZen, 153,85) on this subject. The author substantially confirmsMenschutkin's remarks on uramidobenzoic acid, and believes Griess'spreparation not to have been perfectly pure. Crystallised urarnido-bezoic acid, NH2.CO.NH.C,H4.COOH, cont'ains 1 mol. HzO ; theanhydrous acid is soluble in 139 parts of 96 per cent. alcohol ; and in786 parts of ether.Urtcmidobenzoic acid decomposes a t 200", producing a body to whichMenschutkin gave the formula C6H4< NG. c0 >, and Griess, CO N HCO (NH.C,H+ COOH),.The author finds that Griess's formula is the correct one.composition would be represented by the equation-This de-2 (NHZ. CO.NH. C6H4. COOH) = CO (NH. C6H4. COOH), + CO (NH2)pH e has also obtained this body according to the two equations-(;.) NH2.C0.NH.C6H4.COOH + NHz.C6H4.COOH =(ii.) 2(NHz.C6H,COOH) + CO(XH,)z=Co(NH.C6H4.COOH)z+ 2NH3.The latter equation explains a t once the bad yield of uramidobenzoicacid by Griess's method of fusing together equal molecules of ureaand amidobenzoic acid. The author therefore recommends Mens-chutkin's method of preparing this acid by the action of potassiumcyanate on aqueous amidobenzoic acid hydrochloride.The yield isnearly quantitative, and the acid nearly pure. L. T. T.CO(NH.C6&.COOH), + NEB, andDiamidocumic Acid. By E. T m P x m N (Bey., 15, 2144-2146).-By the reduction of dinitrocumic acid (Monatsh., 1, 822), the authorobtained diamidocumic n.cid, C6HzPr~(NH2)2.COOH, crystallising fromether in yellowish plates melting at 192". Crystallised from water itcontains 1 mol. HzO, which is given off a t 100". The silver salt,CloH,,N,O,Ag + HzO, is slightly soluble in water, and decomposesreadily. Diamidocumic acid hydrochloride, C10H14N20z,HC1 + H,O,crystallises in pale brown prisms, soluble in water, but reprecipitatedon the addition of hydrochloric acid. No hydroxy-acid could be ob-trtined by the action of nitric oxide. L. T. T.Constitution of the Halogen Cinnamic Acids.By J. PL~CHL(Ber., 15, 1945--1946).-The position of the bromine-atom in theside-chain of the two bromocinnamic acids has never been determinedwith certainty. Glaser (AnnaZen, 143, 330) termed the acid meltinga t 131" the a-acid, and that melting a t 12Q" the P-acid, but did notdetermine their constitution. W iLh the chlorocinnamic acids (JutzORGAXIC CHEMISTRY. 195Abst'r., 1882, 1073) the acid of highest melting point (142") was alsotermed the a-acid.The author has endeavoured to settle the question by synthesisingan acid of the formala Ph.CH CCLCOOH, and has effected this byheating a mixture of sodium monochloracetate, acetic anhydride, andbenzaldehyde, when an acid melting a t 14.2' and agreeing in all itsother properties with Jutz's a-chlorocinnamic acid, was obtained.(p-C hlorocinnamic acid, unlike /I-bromocinnamic acid, does notchange into the a-acid even by repeated distillation, so that molecularinterchange was not likely to have occurred at the low bemperature[100-110"] of the reaction.) The supposition of Barisch (Abstr.,1880, 43) that the acid of 6-position had the highest melting point isthus shown to be erroneous.A. J. G.Hydrocinnamic and Cinnamic Acids. By S. GABRIEL (Bey.,15, 2291--2301).-Metanitroparamidohydrocinnamic acid (m. p. 145")is converted into diamidolzydrocinrLamic acid by reduction with tin andhydrochloric acid. The hydrochloride of the new acid, althoughfreely soluble in water, is sparingly soluble in strong hydrocliloric,acid.Dinmidohydrocinnamic acid is deposited from a hot aqueoussolution in transparent crystals containing 1 mol. HzO, which isexpelled at 100". The anhydrous acid (m. p. 143") is freely soluble inglacial acetic acid and in hot alcohol.Bromncetoparamidohyd.rocimamic acid is deposited in colourlessneedles (m. p. 160°), when bromine-water is added to a wamn solutionof paracetnrnidohydrocinnarnic acid. The crystals are soluble inether, warm alcohol, benzene, and acetic acid. The acetic group isexpelled from this compound by strong boiling hydrochloric wid, thehydrochloride of bromamidohydrocinnamic acid being formed. Thefree acid, obtained by the cautious addition of ammonia to the hydro-chloride, melts at 104.5". On adding sodium nitrite to an alcoholicsolution of the hydrochloride, diazonmido hromhydroci~~namio acid,( C6H,Br.C,H,. COOH),N,H, is deposited in brown-coloured needle-shaped crystals. It is decomposed by hydrochloric acid, yieldingnzetc~bi.o.unh~dr.ocinnai.nic a,cid, C,H,Br.C2H4.COOH. This acid is depo-sited from an acetic acid solution in glistening prisms (m. p. 75"),soluble in alcohol, ether, benzene, chloroform, carbon bisulphide, andhot water.The nitrocinnamic acids can be converted into bromocinnamic acids,by acting on the nitro-acid with freshly precipitated ferrous oxide,which reduces it to the amido-acid. From the amido-acid, the diazo-compound is prepared, and this is converted into the bromocinnamicacid by the action of hydrobromic acid.O?.thol,romocinnallzic acid crystnllises in needles or scales (m.p. 2127,soluble in hot alcohol, acetic acid, and ether. When treated withhydriodic acid and phosphorus, it yields orthobromhydrocinnamicacid melting at 98". Tbis acid is soluble in ether, alcohol, benzene,acetic acid, and chloroform. Metabromocinnnmic acid forms pale-yellow needles, melting a t 178", and soluble in ether, alcohol, aceticacid, and also in hot benzene, chloroform, or carbon bisulphide. Parn-bro~noc'i~~~~Un.~ic acid also crystallises in needles of a, pale-yellow colour196 ABSTRACTS OF CHEMICAL PAPERS.which melt about 252'.acid deconiposes at loo", apparently yielding paracoumaric acid.An aqueous solution of paradiazocinnamicw. c. w,Derivatives of Cinnamic Acid.By E. ERLENMEYER ( B e y . , 15,2159--2160).--From the results of the further study of this subject,the author draws the following conclusions :-(1.) PherLy Zdicli loro-pyopionic acid prepared by the action of hydrochloric acid on Glaser'sphenylchlorolactic acid, is identical with that formed by the additionof chlorine to cinnamic acid. (2.) The phen~lchZorobrorr?,oprop~o~i~acid, obtained by the action of hydrobromic acid on Glaser~s phenyl-chlorolactic acid, is isomeric but not identical with that obtained byacting on phenylbromolactic acid with hydrochloric acid. Whenboiled with water, the former gives chlorostyrol, the latter bromostyrol.(3.) The phenylbromolactic acid, prepared by the addition of hypo-bronious acid to cicnamic acid, is identical with that produced byboiling phenyldibromopropionic acid with water.(4.) The halogen-cirinamic (phettyl-halogen-ucrylic) acids of higher fusing point containthe halogen in the a-position, those of lower fusing point in the@position. L. T. T.Orthamidophenyipropiolic Acid and its Derivatives. ByA. BAEYER and F. BLOEM (Bet-., 15, 2147--2155).-Ortl~nmido~henyl-popiolic acid, NH2.C6Hi.C i C.COOH, has been obtained by the authorsby reducing orthonitrophen ylpropiolic acid with ammonia and ferrousaulphnte. It crystallises in pde-yellow microscopic needles, almostinsoluble in water, chloroform, and light petroleum ; sparingly solublein ether, rather more so in cold alcohol. Boiling alcohol dissolves itfreely, but it does not separate out on cooling, or on the addition ofwater.Heated to 125-130", it decomposes with stormy evolution ofcarbonic anhydride, leaving a resinous residue, from which traces oforthamidop'tienylacetylene are extracted by acids. If boiled withwater, i t is decomposed, orthamidoacetophenone passing over with thesteam. When boiled with potash, the acid gives a characteristic redcolour on the addition of hydrochloric acid; excess of hydrochloricacid destroys this colour, but it is reproduced on adding alkali. Thepotassium, sodium, and ammonium salts are very soluble, t8he bariumsalt less so. The yellowish-white insoluble silver salt decomposeswhen exposed to the light and air, and explodes on heating. Theethyl salt crystallises in yellow needles, melting at 55".Boiled with dilute hydrochloric acid, amidophenylprbpiolic acidgives y-c~iZo?~ocarbostyl.iZ, C,H,NOCl, crystallisirig in colourless needles,melting a t 246", and subliming a t a higher temperature.I n a similarway, ~ - ~ r o ~ ~ ~ o c a r h o s t y r i ~ Z , colourless needles melting at 266", andyiodocarbostyril, melting a t 27S0, can be obtained ; both sublimeunchanged. It being pioobable from the investigations of Friedianderand Ostermaier (Ber., 15, 332) that carbostyril is a-hydroxyquinoline,the authors acted on the chloro-derivative with phosphoric chloride,and succeeded in obtaining a dichloroquinoline, C9 H,NC12, insoluble inwater, easily soluble in alcohol, ether, benzene, and chloroform, anORGANIC CHEMISTRY. 197melting a t 67".12, 1320), m.p. 104".This is different from that obtained by Baeyer (Ber.,This has probably the formulaY PCH : CCl I. C&<. - - CCl>UThe new body would therefore be represented by the formulaY Paand would be an a-@-dichloroquinoline. The ychlorocarbostyrildescribed above would then necessarily have the formulaY PCC1: CH-"%<N: C(OH)>'aThus, on the addition of hydrochloric acid to amidophenylpropiolicacid, the chlorine goes to the carbon-atom nearest the benzene-nucleus.Heated at 145" with concentrated su1phur.i~ acid and the resultingproduct mixed wifh water, amidophenylpropiolic acid yields hydroxy-cnrbostyril, C,H,NO,, crystallising in colonrless needles, which sublimeabove 320" without previous fusion.It differs from the isomericamidopropiolic acid in subliming without fusing, and in its silver saltnot exploding when heated. Treated with phosphoric chloride, ityields the same dichloroquinoline as chlorcarbostyril. Thc OH-grouphas, therefore, like the chlorine-atom, become attached to the carbon-atom next the benzene-nucleus, and the formula must beC(0H) : CH'GH4<N C(oH)-->'When it is heated with sulphuric acid a t 200-220", hydromycarbostyril-s d p hoizic acid, C9H7NO5S7 is produced, easily soluble in boiling water,sparingly so in cold.Of the three related acids, orthnnzidoli1jC~roci.nnamic acid, ortkamido-cinnamic acid, and ortlzamidopher~yl~~opiolic acid, the first forms aninternal anhydride spontaneously, the second only with difficulty, andthe third, so far as a t present known, not a t all.When the sidenuclei dose to a ring, this is always accompanied by the addition ofHC1, HBr, HI, or H(OH), to the unsaturated pair of carbon-atonis.When distilled with water, orthamidophenylpropiolic acid givesamidoacetophenone accompanied by traces of amidophenylacetylene. I nthis reaction, however, by far the greater part of the acidresinifies. Abetter way of preparing this body is from amidophenylacetylene, byFriedel and Balsohn's process (Ber., 14, 364).01-tharniL~oacetophenon e, NH2.C6H4.CO&fe, is a thick light-yellow oilof basic properties. It distils almost without decomposition between242' and 252", and is very stable. The sulphate and hydrochloride aresoluble in alcohol and water, and crystallise from the latter in prisms.Its barium and silver salts are soluble198 ABSTRACTS OF CHEiMICAL PAPERS.It forms a platinochloride.Acetylorthoamidoacetophmone is producedby the action of acetic anhydride on amidoacetophenone. It formscolourless needles melting at 76".By F. TIEMANN and R.KRAAZ (Ber., 15, 2070-2072).-The authors describe the followingcompounds, which are prepared by the usual methods, and present nopeculiarities :-Hydrohomoferulic acid, M. p.Methylic methylhomoferulate,Met hylhomoferulic acid,Methox yhy drohomof erulic acid ,L. T. T.Derivatives of Homoferulic Acid.CsH,(CH2.CMeH.COOH)(OMe).0H.. ............ 114-115"C6H,( CH : CMe.COOMe) (OMe)z .............. 65--66C,H,(CH : CMe.COOH)(OMe)2 ................140-141C6H3(CH2.CMeH.COOH)(OMe)2 ................ 58-59E. H. R.Phenylphenamidoacetic Acid and its Arnide and Nitrile.By F. TIEMANN and K. PIEST (Ber., 15, 2028-2034).-By heatingtogether in a closed vessel for two hours a t 100" a mixt,ure of equalmolecular weights of benzaldehyde-cyanhydrin and aniline dissolvedin alcohol, and adding water to the product, a crystalline precipitateis obtained, which has the composition NHPh.CHPh.CN, and isformed according to the following equation :-CHPh(0H) .CN +NH,Ph = NHPh.CHPh.CN + HzO. It crjstallises from dilutealcohol in slender white needles, melting a t 85". This substance hasalready been prepared by Cech by the action of hydrogen cyanide onthe compound NPh: CHPh.The authors find that the latter bodxmelts a t 48-49', and not a t 42" as stated by Cech, and they have pre-pared the above-mentioned nitrile by Cech's method. Heated byitself, it gives off hydrogen cyanide, and forms a polymericle ofNPh : CHPh. When heated with concentrated or dilute hydrochloricacid, it splits up into aniline and beiizaldehyde, whilst wit>h causticpotash it yields aniline and mandelic acid ; when dissolved in concen-trated sulphuric acid, however, and allowed to stand two days andthen gently heated, it yields the amide NHPh.CHPh.CONH,, whichis a crystalline substance, easily soluble in alcohol, ether, aid concen-trated acids. On further heating with dilute hydrochloric acid, ityields the acid NHPh.OHPh.COOH, melting at 173-175°. Thissubstance combines with both acids and bases, and if heated quickly,yields aniline, resinous product,s, and a small quantity of benzyl-phenylamine. When the compound NHPh.CHPh.CN is treated withbromine in alcoholic solution, a dibromo-derivative is obtained, havingthe formula CsH3Br2.NH.CHPh.CN (m. p.92"), which, on beingwarmed with concentrated sulphuric acid, splits up into benzaldehydeand dibromaniline, CsH,(NH2)Br.Br. [l : 2 : 41. By heating the bodyNHPh.CHPh.CN with sulphur, the authors obtain a compoundCPhH \C6H4, to which they give the name benzenylorthamido-phenylmercaptan.NE. H. R,'SORGANIC CHEMISTRY. 199a-Phenamidoisobutyric Acid and its Amide and Nitrile. ByF. TIEMANN (Rer., 15, 2039--2043).-The author has applied thereaction described in the foregoing abstracts to acetonecyanhydrin,and has obtained the following compounds which are analogous inevery respect to those previously described :-3T.p.NHPh.CMe,.CN .................... 93-94'N€€Ph.CMe2CONH2 ................ 3 37NHPh.CMe,.COOH .................. 186185E. H. R.Nitriles of a-Phenamido-, a-Paratoluamido-, and a,-Ortho-toluamidopropionic Acids and the corresponding Amides andNitriles. By F. TIEMANN and R. STEPHAN (Bey., 15, 2034-2039).-By methods precisely analogous to those described in the previousabstract, but using acetaldehyde-cyanhydrin and para- and ortho-toluidine, as well as aniline, the authors have obtained the followingcompounds :-M. p.Acetaldehyde- (NHPh) .CBMe.CN.......... 92"cyanhydrin, (NHPh).CHMe.CONHz ...... 140- 141'and aniline. { (NHPh).CRMe.COOH ...... 162"Acetaldehyde- (NHC7H7) .CHMe.CN ........ 81-82'cyanhydrin, and (NHC7H7).CHMe.CONH, .... 145'paratolnidine. I (NHC7H7).CHMe.COOH .... 152"Acetaldehyde- (NHC7H7).CHMe.CN ........ 72-73'cyanhydrin, and (NHC7H7).CHMe.CONH2 .... 125"athotoluidine. (NHC7H,) .CHMe.COOH ..... -E. H. R. {Constitution of Esculetin. By F. TIEMANN and W. WILT, (Bey.,15, 2072-2084) .-Coumarin, umbelliferone, and aesculetin are repre-sented respectively by the following formulze :-C9H60,, C,H,Os,C,H,O,. Since umbelIiferone has been shown by Tiemann and Reimer(Ber., 12, 993) to be a hydroxycoumarin, it is obvious that aesculetinmay be represented as a dihydroxycoumarin.When the hydrogen ofthe hydroxyl in umbelliferone is replaced by methyl, the ether thusproduced shows all the properties of coumarin; the authors havetherefore endeavoured to show that by replacing 2 atoms of hydrogenin zsculetin by methyl, a body is produced behaving exactly as cou-marin. By the usual process the authors obtain a mixture of mono-and di-methplaesculetin, easily separable by ammonia, in which thelatter is insoluble. Monolmethyl~sczLIet~~~ melts a t 184". Dimethyl-mcdetirz crjstallises in shining white needles melting a t 144". Di-methylaescnletin, methylumbelliferone, and coumarin behave in anexactly similar manner towards reagents, solutions of potassium hy-droxide for example. Further, all three exhibit fluorescence.Theseresemblances point to a similarity in constitution.The authors ha,ve endeavoured t o obtain further evidence on thispoint. Perkin has shown that by the action of methyl iodide onsodium coumarin in presence of methyl alcohol isomeric ethers maybe obtained according to the conditions of experiment; and he ha200 ABSTRACTS OF CHEMICAL PAPERS.also obtained these two isomeric ethe'rs and the corresponding acidsby other methods (this Journal, 39, 409). The authors have repeatedPerkin's work, and fully confirm it, and they have further shown thatby oxidation of both a- and P-orthocoumaric acids (Perkin, Zoc. cit.)one and the same methyl-salicylic acid is formed. They have appliedthese reactions t o methylumbelliferone and aesculetin.Methy Zic dinzethoz?/7cn?beZtate, CsH3( CH : CH.COOMe) (OMe) (OMe)r l : 2 : 41, produced by the usual process from methylumbelliferone,forms shining white needles melting a t 87".No isomeric ether coiddbe obtained, although the temperature used did not exceed 100" (thatused by Perkin) ; but the authors think it not impossible that an etheranalogous to that of a-methylorthocoumaric acid may be produced,but, being much less stable than the latter, is transformed at once intoits isomeride.CH.COOH)(OMe), [l : 2 : 43,is prepared by saponification of the ether and melts at, 184". Onoxidation it yields the acid CsH,(COOH)(ORiZe)2 [l : 2 : 41.Mefh!/Z tl.iruzetiiox2J~!sc21.Zeafe7 C6H2(CH CH.COOMe)(OMe),, pre-pared from dimethylaesculetin in the same manner 8s the correspond-ing compound from methylumbelliferone, forms very pale - yellowglistening prisms melting a t 109".On saponification, i t yields thecorresponding acid, which melts at 168". Prom want of material theoxidation-products of the latter could not be determined.These researches show that methylumbelliferone and dimethyl-Esculetin give exactlv analogous results, when their sodium-compoundsare treated with methyl iodide in methyl alcohol solution, and hencethere can be little doubt that mxxletin is a dihydroxycoumarin. Theauthors hope to determine from which trihydroxybenzene zesculetin isderived. E. H. R.Dirnethoxyunzbellic acid, C6H3(CHConstitution of Eugenol. By F. T r m m N and R. KRAAZ (Ber.,15, 2059--20iO).-Some time since Tiemann and Nagai (Ber., 10,201) showed that by oxidation of acetoeugenol under certain condi-tions, acet - a - homovanillic acid, CsH3(CH2.COOH)(OMeO&)[l : 3 : 41, is obtained; and Erlenmeyer concluded (Bey., 10, 630)from these experiments that the C3H5-group in eugenol has the con-stitution -CH2.CH : CH,.The authors have endeavoured to deter-mine this point.Propiohomoferzdic Acid.-By the action of sodium propionate andpropionic anhydride on vanillin a n acid is obtained melting at 128-129", to which the authors ascribe the formulaC,H,(CH : CMe.COOH)(OMe)(OC3H50) [l : 3 : 41.They discuss the changes which take place in Perkin's reaction, andcome t o the conclusion that in the formation of the honiologues ofcinnamic acid condensation takes place between benzaldehgde and theanhydrides of the higher fatty acids, which are either already presentor are formed bg the action of acetic anhydride on the sodium salts ofthose acids, and the following equations represent what takes place :-C,H,.COH + C€I,R.COO.CO.CH,R = C,H5.CH : CR.CO.O.CO.CH,Rand C,H,.CH : C&CO.O.CO.CH,R + H,O = C,H,.CH CR.COOORGANIC CHEMISTRY.201+ CH,R.COOH. Since the homologues of cinnamic acid formed inthis way, and also the hydro-acids derived from t,hem by addition of2 atoms of hydrogen, behave exactly as cinnamic and hydrocinnaniicacids (e.g., in the formation of the so-called inner anhydrides fromtheir orthamido- and orthhydroxyl-derivatives), they must be repre-sented as produced by substitution in the side-chain, of cinnamic acid.HomoferuZic acid, C6H3(CH : CMe.COOH)(OMe)(OH) [l : 3 : 41,is formed by saponification of the last-described compound.It crys-tallises in tables melting a t 167-168". By distilling it with lime abody is obtained which is isomeric with eugenol, and termed isoeugend.It boils a t 258-262", the boiling point of eugenol being 247-249".The two substances are further distinguished by their benzoyl-deriva-tives, which differ widely in melting point. From the formation ofisoeugenol it follows that its formula isC,H,(CH CHMe)(OMe)(OH) [l : 3 : 41,and therefore the formula C6H3(CH2.CH CH2)(OMe)(OH) mustbe assigned to eugenol. The authors are endeavouring to synthesiseit by the action of ally1 chloride, &c., on guaiacol in presence ofaluminium chloride.E. H. It.Isatin. By A. BAEYER and S. @CONOMIDES (Bar., 15, 2093-2103) .-The authors have prepared ethers of isatin and bromisatin,and studied their properties.B'thers of Isatin.-By acting on isatin-silver with methyl iodide,using certain precautions (for an account of which reference must bemade to the original paper), methylisatin cam be obtained in largerhombic prisms of a blood-red colour. This body dissolves slowly indilute potash, and acids precipitate unaltered isat>in from the solution.I t undergoes change spontaneously with the greatest read-iness, and isconverted into a yellow body of much higher melting point, 219"(methylisatin melts a t 100-101"). If care be not used in the pre-paration of the methyl ether, the yellow body, which the authorsterm methyZisatozd, is obtained instead : the latter gives numbers onanalysis agreeing with a formula intermediate between that of isatinand methylisatin, C,H,NO, + CgHTN02 = C17H,2N20a.It dissolvesin boiling soda solution, and acids precipitate isatin therefrom.Ethers of Bronzisntin.--The ethers of bromisatin show less tendencyto form isato'id compounds. MetlqZbromisatin forms blood-red needlesmelting a t 147". It changes spontaueously into nLethyZbrornisatozd,m. p. 230-231".Etlzylbronzisatin, is similar to the methyl-compound, and melts a t107-109". An alcoholic solution of the former, treated with a smallquantity of potash, becomes reddish-violet, and on addition of morepotash yellow, with formation of potassium bromisatate.Hencepotassium Eromisatin is first formed and then converted into thebromisatate. Ethylbromisatoi'd is best obtained by allowing a solu-tion of the ether in acetic anhydride to stand for some days. It behaveswith boiling potash like the ether. AcetyZbromisafin melts a t 170-172", and on treatment with dilute potash, forms a yellow solution,from which acids precipitate acetylbromisatic acid, melting at 178-P VOL. XIItV202 ABSTRACTS OF CHEMICAL PAPERS.180". Isobutylbronzisato~d melts a t 210". To account for the forma-tion of these isatoid compounds, the authors suppose that moisturecauses a partial saponification, and condensation then takes place.Ethers of Dibromisatin.-These differ from the ethers of isatin andbromisatin in not forming isato'id compounds.The authors preparedibromisatin by heating on the water-bath a saturated solution ofbromisatin in glacial acetic acid, with twice the quantity of brominenecessary to produce dibromisatin. Since the melting point of dibrom-isatin (250') is 5' lower than that of brornisatin, the second bromine-atom probably takes the ortho-position with reference to the nitrogen,the first bromine-atom having taken the para-position. Ethyldibrom-isatin melts at 87-49". Treated in the cold with a 5 per cent. solu-tion of potassium hydroxide, it forms a blue-violet powder, which isthe potassium-derivative, but this soon becomes changed, withoutgoing into solution, into potassium dibrornisatate.From the latter acidsseparate dibronzisatic acid, which changes in a few days into dibrom-isatin. Ethyl dibrornisatate crystallises in yellow tables, me1 ting a t10.5".The authors discuss the formula of isatin considered in the light, ofthese new facts. Acetylisatin, on treatment with potash, yields potas-sium acetylisatate. Ethylisatin, under the same conditions, yieldsfirst potassium isatin and then poiassium isatate. It follows that theacetyl does not take up the same position as the ethyl, and that thelatter must be attached to oxygen, whilst the former is directlyattached to nitrogen. Only one constitution can be assigned toacetylisatin, viz. : c6&<-Nkc->. The most probable formula for co co/CGH4-isatin is N, >GO.This method of representing it explains'C (OH) .~easily its formation and also the fact that isatin chloride is red andenters extremely readily into reaction.The relation between ethylisatin or its bromine substitution-pro-ducts and isatin chloride is further shown by the fact that the former,like the latter, yields indigo or substituted indigos. That isatin doesnot behave in a similar manner, shows that the formation of indigodepends on an alteration of the hydroxyl-group.It follows from the above that the true ncetylisatin, that namely inwhich the hydroxylic hydrogen is replaced by isatin, has not yet beenprep are d .Finally, the authors call attention to the great similarity betweenthe formation of isatin, as represented by the new formula, and thatof carbostyril, which Friedlander and Weinberg (this vol., p.204)have shown to be hydroayquinoZine, and not an imido-compound ashitherto supposed. The authors propose the name lactam for bodiesformed like acetylisatin, and Zactim for those formed like isatin.E. H. R.Metanitrodiphenylmethane. By P. BECKER (Bey., 15, 2090-2993).-The author has obtained this body as a brownish liquid byagitating a mixture of metanitrobenzyl alcohol (prepared according tORGIAXIC CHEMISTRY. 203R. Meyer's method, Ber., 14, 2394) and benzene, with a large excessof concentrated sulphuric acid, keeping t'he mixture well cooled.iMetndiizitrodibenzylbe?zzene is produced at the same time, and is a whitecrystalline substance melting at 165 '. By nitration, metanitrodiphenyl-methane yields a dinitro-compound melting a t 94", and isomeric withthose described by Staedel.~~eturnidocl~henyzniethane, obtained byreduction of the corresponding nitro- body with tin and hydrochloricacid, is a crystalline base melting at 46". On oxidation with chromicmixture, metanitrodiphenylmethane yields meta~itrobewophenone, abright yellow crystalline body melting at 92".Amarine. By A. C ~ a u s (Be?.., 15, 2326--2336).-It has beenpreviously pointed out by the author (Ber., 13, 1418) that a mixtureof hydrodimethy lamarine, methyl chloride, and hydromethylbenzyl-nmarine is produced by the action of benzyl chloride on a boiling alco-I tolic solution of dimethylamarine, 2C,1H16Me,N2 + C7H7C1 + %H,O= C21H18Me( C7H7)N20 + CzlH18Me2N20.1\iIeC1.H~clrornetlLylbenz?lLanzariiie, (CZ1Hl8Me) C7H7N20, is deposited from an:ilcoholic solutlion in colourless crystals (m.p. 20s0), which dissolvefreely in chloroform, but are insoluble in water. The hydrochlorideforms colourless transparent crystals which melt, with loss of water,a t 102". The p l n t i n o -ahZoride, (C2,H2sN20)2,H2PtC16 + 2B20, is deposited from a warmalcoholic solution in orange-coloured needles. The anhydrous saltmelts a t 168".H~droclimethylanzarine methyl chloride is a crystalline salt (m. p. ISS"),freely soluble in water, alcohol, and chloroform, but insoluble in ether.The aqueous solution is not acted on by ammonia, but on treatmentwith potash or silver oxide, it yields I~ydrotrimethy l a ~ a r i n e ,E.H. R.The dried salt, C2,H&,O,HC1, melts a t 205".This base crystdises in transparent prisms (m. p. 158"), soluble inether, alcohol, and chloroform. The hydrochloride (m. p. 204") isinsoluble in chloroform and sparingly soluble iu water. On addingammonia to the aqueous solution, the free base is precipitated. Theplatinocldoride, (C21H17Me3N20)2,HnPtCls . + 2H20, obtained as ayellow precipitate, soluble in alcohol, melts at 195". The platino-chloride of hydrodimethylamarine methyl chloride only contains 1 mol.H,O. It is a bright yellow powder, melting at 244", and soluble inalcohol, and in water containing a small quantity of acid.Dibenzylamarine does not combine with alcoholic chlorides, bro-mides, or iodides. When ethyl iodide acts on dibenzylamarine, amixture of hydriodide of dibenzylamarine and its di-iodide is pro-duced.The hydriodide, CZ1Hl6( CT E17),N,,HI, forms colourless plates,iusoluble in water. The di-iodide, Cz,H16(C7H7)2N0,HI,12, is depositedfrom an alcoholic solution in golden needles.Dibenzylamarine is not oxidised by chromic acid, but on treatmentwith dilute nitric acid (sp. gr. 1.13) it yields benzoic and paranitro-benzoic acids, and also two intermediate products, viz., a body crystal-lising in yellow needles melting a t 142", and a substance depositedfrom alcohol in pale yellow prisms melting at 95".P 204 ABSTRACTS OF CHEMICAL PAPERS.Dimethylamarine may be represented by the formulaNMe : CPhPhCy I .'-NMe.CHPh w. c. w.Constitution of Carbostyril and Hydrocarbostyril.By P.FRIEDLANDER and A. WENBERG (Bey., 15, 2103).-By the action of aconcentrated solution of zinc chloride on ethyl orthamidocinnamate,an ethylcarbostyril is obtained identical with that produced directlyfrom carbostyril o r chloroquinoline. It follows, therefore, that ethyl-carbostyril contains an ethoxyl-group ; and carbostyril must be re-garded as a hydroce?/quinoline.I n a similar manner the authors obtain an ether of hydrocarbo-styril which is easily saponified by dilute acids (Bey., 15, 1421). Rutwhen hydrocarbostyril is heated with potassium hydroxide and ethyliodide in the usual way, an ethylhydrocarbostyril is obtained, whichremains unaltered even when heated with concentrated sulphuric acida t 150".The same body is obtained by heating ethylorthamidocin-namic acid with sodium-ama,lgam, ethylorthamidohydrocinnamic acidbeing thereby produced, which, on acidifying its alkaline solution,becomes converted into ethylhydrocarbostyril. The stable form ofethylhydrocarbostyril is therefore represented by Figure I, whileFigure I1 indicates the constitution of its isomeride-C H CH,CH N.EtI.CH CH,CH /\'/\ CH,C H \ I ,)I c\/ COEtCH NIT.E. H. R.New Compounds from Coal-tar: CL- 6- +yrocresoles. ByH. SCHWARZ (Monatsh. Chew., 3, '726-744).-These compounds wereprepared from a buttery distillate occurriiig amongst the last productsof the rectification of carbolic acid in a tar-distillery at Angern nearVienna. The buttery mass, on rectification, began to boil a t 180",the boiling point often remaining stationary for a while a t 207", andthen slowly rising to 225".A small quantity passed over between225" and 265" ; more at 265-320", the distillate then beginning tosolidify. Between 320" and 330", a copious light yellow distillate wasobtained, which quickly solidified ; a t 330-350" the distillate wasdark yellow, and above 350", brown-yellow and softer. Finally,charcoal remained in the retort. On dissolving the crude distillate inglacial acetic acid a t the boiling heat', and then heating it with zinc-dust, it becomes much lighter in colour, and if then distilled, yields acolourless product, which only gradually becomes coloured.On heating the oily non-solidifying portion of the product withpotash-ley, filtering from neutral oil, saturating the filtrate with hydro-chloric acid, and distilling it with steam, ccllecting the oil whichsinks to the bottom of the distillate, drying it with calcium chloridORGANIC CHEMISTRY.205and rectifying, there passes over an acid oil, the chief part of whichhas the composition (77.34 per cent. carbon and 7-45 hydrogen) andboiling point (193-195") of meta-cresol.Preparation of Pure Pyrocl-esole (a, p, and y).-The solid productsof the distillation just described, as well as the press-cakes obtainedon the large scale, and the buttery mass expressed therefrom, werefound-after being subjected to a series of purifying processes by solu-tion, especially a t boiling heat, in benzene, light petroleum, carbonsulphide, chloroform, ether, and alcohol-to crystallise on cooling insilvery laminz, which, after one more crystallisation, appeared to bepure enough for analysis.Nevertheless these apparently pure pro-diicts exhibited very considerable differences of melting point andsolidifying point, the latter-which admitted of more exact determi-nation than the former-varying from 85" to 195"; and by washingwith cold alcohol, boiling first with dilute and then with continuallystronger alcohol, extraction with light petroleum and with ether in apercolator, &c., a number of isomeric bodies were obtained exhibitingdifferent degrees of solubility. No separation could be effected bydifference of boiling point.The bodies of lowest melting point were also the most soluble, butthe differences of solubility were not great enough to effect thedefinite separation of more than the products of highest and lowestmelting point.The former were most readily separated by repeatedcrystallisation from boiling benzene, whereby, from the original press-cake solidifying a t 127", products were obtained solidifying a t 147",l57", l69", 181", and finally at 195", this last product crystallising iiilarge laminz having a silvery and satiny lustre, and dissolving with-out colour in benzene. The substance cqstallised from this solutionexhibited the same solidifying point, as did also that which was ob-tained from the mother-liquor by distilling off the benzene. It ip,moreover, eminently sublimable, so much so indeed that it canscarcely be me1 ted in an open vessel, the greater part subliming beforeit fuses.When quickly heated in a test-tube, it fills the tube withwhite coherent flocks, so that its boiling point cannot be determined.Dissolved in glacial acetic acid and oxidised by chromic acid, it yieldsa product crystallising in splendid needles. The other derivatives ofthis substance (to be described further on) are distinguished by greattendency to crystallise, relatively high melting point, and sparingsolubility.At) the other end of the series is a substance which crystallises con-stantly at 104-105". It may be separated by concentrating themother-liquors, and is likewise obtained from the greasy mass whichruns out on hot-pressing in the manufacturing process. It may befreed from colouring matter by treaking it in the melted state with hotglacial acetic acid and zinc-dust.This substance is much more solublethan that which solidifies at 195" ; it is not sublimable ; its derivativesare less crystallisable ; and its oxidation-product melts under hotwater.A third substance has also been separated, less well-defined than thetwo above mentioned. From a press-cake solidifying a t 127-128",the author, by repeated treatment with alcohol, ether, and benzene206 ABSTRACTS OF CHEMICAL PAPERS.obtained the bodies solidifying a t 195" and 104", but did not succeedin resolving the mass completely into these two compounds ; and hesupposes that it contained also a third substance solidifying a t 124",crystallising in smaller laminae, and intermediate in solubility betweenthe two former.All these three substances were found by analysis to have the sameelementary constitution, viz.:-C. H. 0.84.87 t o 85-24 6.61 to 6-84 7.97 t o 8.48agreeing most nearly with the formula C,4H130, which requires85.28 C, 6.64 H, and 8.08 0, An uneven number of hydrogen-atomsbeing however inadmissible, the author assigns to these isomericbodies the double formula CzsH,,02 (which is confirmed by some ofthe substitution-derivatives), and designates them as pyrocresoles,supposing them to be produced from cresol by elimination of waterand hydrogen as shown by the equation, 4C7H,0 = CzeHzsO, + 2H20 + H2. They are distinguished as a, melting a t 195, /3 a t 124", '1 at104".They may perhaps be regarded as ditolyl-ditolylene dioxides,PPROCR~ESOLE OXIDES, Cz8Hz2O4, are obtained by treating the threepyrocresoles either with nitric acid of sp. gr. 1.40, or with a mixture ofpotassium dichromate and sulphuric acid, or with chromic anhydridein glacial acetic acid, the action being represented by the equationC2,H2,OZ + o4 = 2H20 + C2,Hz20e. The a-compound, which is espe-cially fine, may be precipitated from its solution in glacial acetic acidby water, in groups of needles, and when washed, dried, and recrys-tallised from boiling alcohol, forms beautiful somewhat yellowishneedles, becoming somewhat darker on exposure to light. It solidifiesat 168", ie., 27" lower than a-pyrocresole, and is more soluble than thelatter in alcohol, &c.It distils unaltered, but shows little tendency tosublime.The 6- and y-oxides solidify a t much lower temperatures than thea-compound ; they are also more soluble, and show less tendency tocry st allise.Oapitro-products, Cz~H,B(NOZ)i04, are produced, with evolution ofnitrous fumes, by treating the three oxides with a mixture of 1 vol.NOSH and 2 vols. S04H2, and separate as light yellow, more or lesscrystalline bodies, the separation being completed by addition of water.The washed and dried products melt when heated in test-tubes, anddetonate at higher temperatures, leaving a large quantity of pulveru-lent charcoal. The a-nitro-compound crystallises from hot nitroben-zene or from glacial acetic acid in light yellow laminae ; from strongnitric acid on cooling and dilution, in nearly white laminm and needles.The ymodification is much more soluble in boiling acetic acid, andseparates on cooling in yellow grains and nodules.The ,%compoundcrystallises from a mixture of nitric and acetic acids in yellow lamine.The analyses of these bodies show that they have not yet been ob-tained quite pure.Amdo-conzpozcitds appear to be formed by the action of tin andC7H,.C,H,.O.O.C7H,. C7H7ORGANIC CHEMISTRY. 207hydrochloric acid on the nitro-products, but they have not yet beenisolated.BRoMTNE-COMPOUNDS.-~hen a solution of a-, 6-, or ypyrocresole inslacial acetic acid is treated with excess of bromine, likewise dissolvedin glacial acetic acid, a reddish-yellow crystalline precipitate is formed,which after draining, washing with glacial acetic acid, and drying onearthenware plates over quicklime or potassium hydiaoxide, remainsnearly unaltered. Part of the bromine contained in it is, however,very loosely combined, and may be removed by drying a t loo", or bywashing with alcohol, or best by boiling with water, a white substancethen remaining, which may be crystallised from boiling alcohol orglacial acetic acid.Of the bromine-compounds thus formed, the a-product is the leastsoluble.On adding 6Br to 1 mol. a-pgrocresole, beautiful lamin% arethrown down, which contain only traces of free bromine, and may berendered nearly colourless by treatment wit'h a small quantity ofalcohol.The yproduct obtained in like manner is best purified byrecrystallisation from boiling alcohol. When on the other hand alarger quantity of bromine is added to y-pyrocresole, torrents ofhydrogen bromide are evolved, yellowish granular crusts separate out,and water throws down a yellowish compound, which melts even a tthe heat of boiling water. The analysis of the reddish-yellow a-COIN-pound thus obtained gave as a mean result, 32.62 per cent. C, 2.30 H,60.32 Br, and 4.76 0, agreeing approximately with either of the threeformula?, C,,H?,Br,04, C28H21Br803, and C2SH21Br802, the first agreeingbest with the quantity of bromine found by experiment, the thirdbetter with the carbon. The equation C28H260z + lOBr= 2BrH +C28H2aBrROZ, is in accordance with the experiment in which 1 mol.pyrocresole was acted upon with 10 at.Br, of which only a smallquantity remained free.By distilling the reddish-yellow a-componnd with water, 62-62 pel.cent. of white residue was obtained, together with 94.1 0 to 12.55 per cent.hydrogen bromide, and 18.66 to 24-11 per cent. free bromine. The whiteresidue exhibited a constant composition agreeing with the formula oftribromopyrocresole, CzeH23Br302, its quantity agreeing closelywith the calculated amount, viz., 61 per cent. The reddish-yellowbody is its p e r b r om i d e, and is converted into tribromopyrocresoleby loss of HBr + Br. A similar perbromide is obtained from -/-pyro-cresole, but has not yet been examined. 6-pyrocresole does notappear to yield a bromine-compound.To obtain pure fribro?120~Zlrocrnsv7e, it is sufficient to treat the solu-tion of 1 mol.a- or y-pyrocresole in glacial acetic acid with only 6 at.bromine, according to the equation C,,H,,O, + 6Br = SBrH +C,8H2,13r302 ; the solution on cooling deposits the tribromo-compoundin thin rhombic laminae, which may be washed with water and recrjs-tallised from alcohol.y-Pyrocresole treated a t the boiling heat with a slight excess ofbromine, yielded also another compound in yellow crusts, a furtherquantity of which was separated on dilution with water. This com-pound, not yet fully examined, melts under boiling water, whereasa-tribromopgrocresole solidifies a t 200", and the y-compound at 183"208 ABSTRACTS OF CHEMICAL PAPERS.On attempting to brominate pyrocresole oxide by treating its solu-tion in glacial acetic acid with bromine, fine reddish-yellow needleswere obtained, which turned white when exposed to light over solidpotash, and when boiled with water quickly turned white, with for-mation of hydrobromic acid and evolution of bromine.The residualsubstance dissolved readily in warm alcohol, and crystallised there-from in slender white needles, having the composition of p y r o c r e s o 1 ed i ox i d e, Cr5Hz20s.SULPHOKIC CORIPOUNDS.--~~- and y- Pyrocresole unite somewhat ener-getically with sulphuric acid, forming a red-brown syrup, which,however, on dilution with water, deposits nothing but the unalteredpyrocresole. The same solution saturated with carbonate and hydr-oxide of barium, then filtered and evaporated, yielded only in the caseof a-pyrocresole, a salt which crystallised from the hot liquid inneedles, giving by analysis 25.05 and 24-95 per cent.Ba, and 11.57 S,the formula of barium pyrocresole-tetrasulphonate requiring 27-84Ba and 13.08 S. The salt was perhaps mixed wit,h di- or tri-sulpho-nate. A sodium salt was likewise prepared containing 16.11 percent. S, 10.33 Na, and 4.84 H20, the formula C2,H2,Na&Ol4 + 2H20,requiring 14.92 S, 10.72 Na, and 4.19 H,O.The solution obtained by treating a-pyrocresole oxide with sulphuricacid, deposited on dilution with water nothing but the unaltered oxide,and the filtcred liquid treated with barium carbonate took up scarcelyany traces of baryta.No sulphonic acid had therefore been formed.H. W.a- and t-Dichloronaphthalenes. By 0. WIDMAN (Bey., 15,2160-2163).-In the hope of explaining the anomaly that the a- and @-di-cizZororzn~llthuZent,s both give the same dichloronaphthalene tetrachloride,which, when oxidjsed with nitric acid, gives the same die hlorophthalicacid as that obtsined from B-dichlornaphthalene (BUZZ. SOC. C'him., 28,S O S ) , the author has submitted a-dicl~lororznpl~thalene (obtained byacting on the pure tetrachloride witJh potash) to careful purification.The author has succeeded in separating from this a-compound a smaJlquantity of c-dichloronaphthalene fusing at 120", and identical withthat obtained by Leeds and Everhardt (Amer. Che??z.Xoc., 1880, 2,205), by acting on naphthalene tetrachloride with moist silver oxide a t200". No trace of 6-dichloronaphthalene could be obtained. a-Dichloro-nuphthalene fuses a t 38" (formerly the fusing point was given as 35-3G"), and gives, by V. Meyer's method, the vapour-density 7.02 (theory6*69), showing that it could contain no double-compound. Nevertheless,on treating this perfectly pure a-dichloronaphthalene with chlorine,(3-dichloronaphthalene tetrachloride is produced. This point, there-fore, is still obscure.The author declines to allow as valid the arguments put forward byClaus in favour of his proposed new formula for naphthalene.L. T. T.p-Dinaphthol. By H. WALDER (Bey., 15, 2166--2118).-Theauthor has investigated many new derivatives of Pdirra1~htlzoZ.Thep-dinaphthol used was prepared by oxidisiiig (I-naphthol in etherealsolution with anhydrous ferric chloride. On distillation, 6-dinaphthoORQANIC CHEMISTRY. 209decomposes, /I)-naphthol and some P-dinaphthol distilling over, and acarbonaceous resiciue being left in the retort.P-Ditlaphthol piicrute, C,H,,O2,2[ CsH,( N 0,)3.0H], melts at 174", andis soluble in alcohol and benzene. a-Dinaphthyl is produced when B-di-naphthol is heated with zinc-dust. a-Dinapl ithyl, heated with picricacid dissolved in benzene, yields a crystalline body melting at 143" ;i t crystallises from benzene in reddish-brown needles. By heating6-dinaphthol with zinc chloride at 27U", the author obtained a P-di-naphthalene oxide, which appears to be isomeric and not identicalwith that obtained by Dianin from @-naphthol and phosphoric anhy-dride.The oxide is soluble in the usual solvents: melts a t 157", andgives a picric acid compound, C20H,20,2[ C,H,(NO,),.O HI, melting a t135". On heating P-dinaphthol with zinc ammonium chloride a t 320-330" for 60 hours, a substance was obtained melting at 159", and havingthe formula CzOHION. The author looks upon this body as dincxyhthy-Zenanzide, I ,NH, or N K < ~ ~ ~ ~ > N H . It is soluble in the usualsolvents and yields rhombic crystals. It dissolves in concentratedsulphuric acid with blood-red coloration. With picric acid it gives acompound, C,oH,,N,C,H,(NO,),.oH, melting a t 217". Heated withexcess of acetic anhydride, it forms an acetyl-compound, I \N&,crystallising in greyish-white needles melting a t 144".Substitutingzinc aniline chloride for zinc ammonium chloride, a dincyldhy Zem-yhenylanzine, I \NPh, or PhN< ~ ~ ~ ~ ~ ~ > N P h , is obtained, solublein benzene, ether, acetone, alcohol, and acetic acid, but not in dilutemineral acids. Sulphuric acid dissolves it with violet coloration. Itciystallises in white needles melting a t 144". This amine also yieldsa picric acid compound, ~ 2 , ~ l ~ ~ , ~ ~ ~ , ~ 2 ( ~ o , ) , . ~ I melting a t 169".Acetic chloride attacks dinaphthylenamine, but not the tertiarydinaph t hylenephenylamine.By T. ZINCICE andF. BRAUWS ( B e y . , 15, 1969-1972).-A continuation of the authors'researches on this subject (Abstr., 1880, 48 ; 18~1, 595, 915 ; 1882,735, 967).The ethers of a-naphthoquinonetoluide can be preparedfrom the silver salt by heating an alcoholic solution of the sodium saltwith alcoholic bromides or iodides.The methyl ether, C1,Hl2NO2Me, crjstallises from alcohol in finered crystals melting a t 150". The ethyl ether, C1,H,,lr'02Et, formslarge red crystals melting a t 135-137".C lo&\G"H6c lOH6C,OH/GOH,ClOH/L. T. T.Action of Amines on Quinone. Part VI.The isopopyl ether,C17H1211YIO@Pr,melts a t 137-139". These ethers, when boiled with acetic acid,yield ditoluide ; they are saponified by hot concentrated sulphuric acidwith formation of /3-naphthoquinonetoluide. Bg the long continuedaction of hydrochloric acid, hydroxynaphthaquinones are formed210 ABSTRACTS OF CHEMICAL PAPERS.Nitric acid dissolves the ethers ; and on adding water precipitates areformed; in the case of the ethyl ether, a yellow crystallisable sub-stance (m.p. 17'7-179") being obtained.Nitrous acid acts on /!I-naphthoquinonetoluide, and in presence ofacetic acid and alcohol, gives a substance of the formula C,,H,,N4o6,crystallising from glacial acetic acid in small red needles, and appear-ing to be a nitroso-compound. It unites with alcohol, forming a whitecrystalliue compound, which is decomposed by heat, the alcohol beingdriven off. On reduction, best by means of pot,assiuifi bisulphite, a deepblue compound, C,4H26N,04, is formed ; this forms red salts with acids,which are only stable in alcoholic solution ; with alkalis it yields finegreen salts, insoluble in alcoho2 with acetic anhydride it yields atet,.acet~Z-derivative, C3,H2,N,(OAc)4, forming yellow crystals, meltingat 190-191".On oxidation, the blue compound is converted into ayellowish-red substance, C3,H22Na04 (m. p. 260-265"), crystallisingfrom acetic acid in needles; reducing agents reconvert it into theblue compound. By the action of soda on the nitroso-compounda yellow crystalline body (m. p. 224") is obtained ; it is not attackedby the strongest oxidising agents ; potassium bisulphite gives anunstable white reduction-product which readily reoxidises. Chromicacid converts the nitroso-compound into a body crystallising fromalcohol in small yellow needles melting a t 212-214".Lapachic Acid.By E. PAT ERN^ (Gazzetta, 12, 33'7-392).-Thisacid is extracted from the ground lapacho wood by boiling it with adilute solution of sodium carbonate : the solution acquires a blood-redcolour, and when cold is filtered and neutralised with hydrochloricacid ; an abundant yellow precipitate of lapachic acid is then formed,amounting to about 8 per cent. of the original weight of the wood.Jn order to purify the crude product, it is crystallised snccessivelyfrom ether and from benzene, in which the resinous matters areinsoluble ; it then forms small well-defined monoclinic prisms of a finecanary-yellow colour, and very soluble in boiling alcohol, from whichit separates in thin plates. It melts a t 138", and a t a higher tempera-ture decomposes, leaving an abundant carbonaceous residue.Lapachicacid, C15H140?r is easily soluble in solutions of the alkaline hydroxidesand carbonates, giving bright red solutions.Cl5HI3NaO3 + 5H20,separates from concentrated solutions as a radiated crystalline mass ofdeep red colour, which after a time loses its crystalliue structure andbecomes almost black. It melts in its water of crystallisation at aboutSOo. Potassium Zapachate, CI5Hl3KO3, closely resembles the sodium-compound in appearance. Arnmo.lzium Zapachate, Cl5HI3O3.NH4, crys-tallises in large brick-red needles, which lose ammonia quickly onexposure to the air, leaving a residue of pure lapachic acid. SilverZapachccte, C15H17Ag03, calcium Zapachate, (C15H1J03)2C~ + H20, andstrontium Zapachate, (C,,H1,03),Sr + lgH,O, are obtained from theaiiimonium salt, by precipitation, as red amorphous powders.TheA. J. G.Xodium ZapachateORGANIC CHEMISTRY. 211barium salt, (C15H1303)2Ra + 7H,O, very sparingly soluble in cold,but more so in hot water, crystallises in long slender blood-redneedles. The lead compound forms an orange-red precipitate. Theaniline and toluidine salts were also prepared ; they are orange-yellowcrystalline compounds melting a t 121-122" and 129.5-130' respec-t ively .Action of Byornine on Lapachic Acid.-On mixing bromine (3.3grams), diluted with acetic acid with a solution of lapachic acid(50 grams), in the same solvent, a yellowish-brown solution is ob-tained, which yields an abundant orange-yello w precipitate whenpoured into a large quantity of water.The monobromolapachic acid,Cl5HI3BrO3, thus obtained is easily purified by washing it with etherand crjstallising from boiling alcohol ; it separates in large lustrousplates of an orange-red colour, melting at 139-140". It has none ofthe characters of an acid, being quite insoluble in cold potash solution,and although alcoholic potash dissolves it, it is precipitated unchangedon diluting with water and adding hydrochloric acid. It dissolves innitric or sulphuric acid a t the ordinary temperature, and is precipi-tated unaltered on adding water to the solution. When boiled withnitric acid, however, it is gradually decomposed, bromine is given off,and the solution leaves phthalic acid on evaporation.Acetyl-derivatives.-Lapachic acid is not altered by boiling withacetic chloride or anhydride under the ordinary atmospheric pressure,but on heating it with theanhydride at 150" for three hours, a mou-ucetic-derivative, Cl5HI3O3Ac, is formed ; this may, however, be preparedmore conveniently by heating a mixture of lapachic acid (2 parts),sodium acetate (2 parts), and acetic anhydride ( 5 parts), the liquidrapidly assumes a wine-red colour which passes into yellowish-brown,and finally becomes green ; as soon, however, as the mixture begiiisto assume a green tinge, the reaction is stopped by adding water ; thisthrows down a yellowish-brown oil which soon solidifies to a crystal-line mass, the yield being almost the theoretical.It is easily purifiedby recrystallisation from alcohol, when it forms lustrous sulphur-coloured prisms, insoluble in water, but very soluble in ether ; it meltsa t 82-83'. When heated with acetic anhydride in closed tubes, ityields a green resinous compound. It is not acted on by water at120", but is easily decomposed by alcoholic ammoniaf in the cold withformation of ammonium acetate and lnpachate. With bromine, i tyields monobrornolapachic acid, and with nitric acid a n acetomonon itro-lapachic acid, CI5Hl2(NO,) O,.& ; this crystallises in orange-red plateswhich melt a t about 166-168", but undergo decomposition a t thesame time. If the mixture of acetic anhydride, sodium acetate, andlapachic acid above mentioned, instead of being heated until it com-mences to turn green, is boiled for about 15 minutes, it no longercontains a trace of monacetolapachic acid, but another compoundwhich is precipitated as a brownish-green oil on adding water to theproduct ; this becomes crystalline after some time, and is thenpowdered, washed with ether to remove a greenish resin, and finallypurified by recrystallisation from alcohol or from dilute acetic acid.I t forms dirty-white needles or minute prisms melting at 131-132",andvery sparingly soluble in ether or cold alcohol.Although th21 2 ABSTRACTS OF CHEMICAL PAPERS.analytical results correspond very closely with the formula of biaceto-lapachic acid, yet, as it has not been found possible to reconvert itinto lapachic, acid, it is highly improbable that it is the biaceto-deriva-tive.It is not altered by heating it with water at 150", neither doesit dissolve in solutions of the alkaline carbonates or of their hydrox-ides ; it is decomposed, however, by alcoholic potash, which dissolvesit with brownish-yellow colour, and on diluting the s o l u h n withwater, and adding an acid, a new compound is obtained as a brownish-yellow precipitate. This is very soluble in alcohol, ether, and ben-zene, but may be crystallised from dilute alcohol, when it forms small,silky, flat needles of orange colour, melting a t 140-141". The authort'hinks it probable that these two compounds have the formulm I andI1 respectively :-The action of nitric acid on the acetic-derivative seems to give riseto two nitro-substitution-compounds, one of which crystallises in redneedles melting a t 147-148", whilst the other, less soluble in ether,forms yellow needles melting a t a somewhat higher temperature.When lapachic acid is oxidised by potassium permanganate, i tyields oxalic acid i n small quantity; with ordinary nitric acid ofsp.gr. 1-38 it yields phthalic acid in abundance, exceeding 75 percent. of the lapachic acid taken.On distillation with zinc-dust, lapachic acid yields naphthalene anda hydrocarbon boiling a t about 250", and melting a t a lower tempera-ture than naphthalene, probably a homologue of the latter; of thegaseous products, the portion absorbed by bromine gave two bromides,one isobutylene bromide, CMe2Br.CH2Br, the other derived apparentlyfrom a hydrocarbon containing c6.Action of Reduciwg Agents.-As the general conduct of lapachic acidand the fact that it yields naphthalene on distillation with zinc-dust,indicate that it is a hydroxyquinone derived from some homologue ofnaphthalene, it was of importance to examine the effect of reducingagents.The acid when dissolved with excess of an alkaline hydroxideand treated with zinc-dust, is acted on immediately, the intense redcolour of the solut.ion becoming pale yellow ; the hydrolapachic acidformed, however, is oxiclised so readily that it was found to be impos-sible to obtain it in a state sufficiently pure for analysis. It is solublein boiling water, aildl crystallises in colourless needles melting a t about100".An energetic reaction takes place on heating lapachic acid with redphosphorus and concentrated hydriodic acid, and when it is completethe mixture separates into two layers, the lower of which is an oilyhydrocarbon boiling a t 304 - 306".It combines with trinitrophenol,forming a compound which crystallises from boiling alcohol in largeorange-red needles rnelting a t 140-141". From analyses of the picricacid compound, the hydrocarbon would seem to be an arnylnaphthulene,Action of Concentrated Acids.-Lapschic acid (1 part) dissolved inconcentrated sulphuric acid (4 parts) in the cold gives a solution o€,CIOH7.CjHllORGANIC CHEMISTRY. 213the colour of bromine, and this, when poured into a large quantity ofwater, deposits an orange-yellow flocculent substance, which may bepurified by crystallisation from alcohol.This new compound is Zapa-cone, C15H,103, isomeric or polymeric with lapachic acid. It formsmagnificent flattened needles melting a t 155-156", of orange-redcolour and silky lustre. It is insoluble in water, easily soluble inbenzene and alcohol, but less so in cold alcohol or ether. It dissolvesalso in concentrated sulphuric, nitric, and hydrochloric acids, and isprecipitated unaltered on addition of water ; it also dissolves in potashwhen heated. In like manner when lapachic acid is dissolved in wellcooled concentyated nitric asid of sp. gr. 1.49, it is converted intolapacone, but a small quantity of another substance, more soluble inether and cold alcohol, is formed at the same time ; this crystallisesfrom alcohol in canary-yellow needles melting at 116-117". It doesnot contain nitrogen, and on analysis gave numbers nearly the same asthose obtained with lapachic acid.Lapacone is energetically acted on by asetic anhydride and sodiumacetate ; on heating the mixture, it becomes green and brilliant platesmake their appearance in the liquid ; the addition of water now throwsdown a dark green precipitate, which is washed with ether to removea green resin, leaving the new compound in magnificent plates ofmetallic lustre with blue iridescence, bronze-red by reflected andgolden-yellow by transmitted light ; when pressed under a glass rodon paper they give an indigo-blue spot with coppery lustre like indigo.There is the greatest difficulty in purifying this substance, as it isalmost insoluble in the usual solvents ; it may, however, be recrystal-lised from a large quantity of boiling acetic anhydride.It is alsoslightly soluble in carbon bisulphide, yielding a beautiful blue solution,but on evaporation it is deposited in the amorphous state. It is notaltered by boiling potash solution. Sulphuric acid dissolves it, b u t itis not reprecipitated on adding water ; nitric acid dissolves it with redcolour, but the product has not been examined. This substance isalso formed by the action of acetic anhydride and sodium acetate onmonohromolapachic acid.These results incline the author to believe that it is an anhydride ofapacone, admitting-what is highly probable-that lapacone is anolymeride, CBoHas06, of lapachic acid, analogous to the compound,btained by Stenhouse and Groves from p-naphthaquinone, I n this*ase it would hare the formula C30H2605.The author then proceeds to discuss the identity of lapachic acidwith tniguic acid and groenhartin, pointing out that these three sub-stances are obtained from varieties of the same species, although notfrom the same plant; the properties of lapachic acid and also itsmelting point agree closely with those given by Arnoudon for taiguicacid; there is, however, a great difference in the amount of carbon,lapachic acid containing 74.5 per cent., whilst Arnoudon gives 70.9for taiguic acid ; it should be noted, however, that he does not con-sider the formula as absolutely settled.As regards groenhartin, theanalyses given by Stein agree very closely with those of lapachic acid ;Stein, however, says that he obtained an unstable bromo-derivativecontaining 37 per cent. bromine, whilst monobromolapachic acid con214 AESTRACTS OF CHEMICAL PAPERS.txins but) 25, and no definite dibrcimo-derivative could be obtained. Theauthor suspects that the product analysed by Stein was not pure, butcontained a resinous substance richer in bromine, the formation ofwhich he hfmself has observed. It seems highly pyobable that thesethree substances are identical, and it is very desirable that Arnoudonand Stein should study taiguic acid and groenhartin so as to definitelysettle this point. I n an appendix, the author states that he hasexamined the acid obtained from a fragment of the very same pieceof wood employed by Arnoudon, and finds it to be identical withlapachic acid.Coizstitz~tion of Lapachic Acid.-The results of the analyses oflapachic acid and its substitntion-products, and especially of thesilver salt, closely agree with the formula Cl5H14O3, whilst its chemicalcharacter and the action of reducing agents prove distinctly that it isa hydroxyquinone derived from naphthalene of the formulaThe results obtained by the distillation of lapachic acid with zinc-dust,and the nature of the bromide obtained from the gaseous hydrocarbonevolved, indicate that the side chain C5Hg has the constitution-CH CH.CHMe,.The author assigns valid reasons for believing that in monobromo-lnpachic acid the bromine takes the place of the hydrogen in theOH-group, and that its formula is C15H13(02)".0Br, and that theacetate is C15E113(0?)''.0AC.Finally, he discusses the formula oflapacone, and considers it highly probable that it isA New Monochlorocamphor. By P. CAZENEUVE ( C ~ m p t .i ' e d . , 94, 1530--1532).-When dry chlorine is passed into a mixtureof camphor (760 grams) and absolute alcohol (230 grams), there isdevelopment of heat and the camphor dissolves. On cooling theproduct to about 15"' it becomes a pasty mass of crystals, which, afterbeing collected, washed with water, and crystallised from alcohol,forms long colourless needles of monoch Zorocanzphor, CloHl5ClO. Ithas an odour resembling that of camphor, is sparingly soluble inwater, but easily in ether and benzene.It softens at 75", melts a t83-84", and distils almost without decomposition a t 244-247'. It is:&o easily volatile in the vapour of water. Its specific rotatorypower [a]j = +- go', is grea,ter than that of camphor, or of the di-chloro-derivative. It is not decomposed by an alcoholic solution of silvernitrate or by alcoholic potash, differing greatly in this respect fromWheeler's monochlorocamphor (Bull. SOC. Chirn., 10, 289), w-hichmelts at 95", and is readily decomposed when heated.Contributions to the History of the Isomerism of theDibromocamphors. By T. SWARTS (Ber., 15, 2135--2136).-Byheating a-dibromocamp7~or for six hours a t 120" in a se:alecl tube, inC.E. GORGANIC CHEMISTRY. 215which hydrobromic acid was being evolved from a mixture of phos-phorus bromide and syrupy phosphoric acid, the author has convertedi t into p-dibromocawphor. Hydrochloric acid does not produce thechange.a-Dibromocampkor fornis a liquid compound with chloral hydrat.e ;P-dibromocamphor has no action. The bromine-atoms in the a-bodyappear very immobile ; one a t least of those in the P-body is easilyreplaced, producing, with silver acetate, silver bromide and a crystallineacetic compound.The author believes tribromocamphor t’o partake of the constitutionof the two di-bromocamphors. Treated with nascent hydrogen inalkaline solution, it gives an oil resembling turpentine, boiling at 258-260”.Heated with fuming nitric acid, it gives a nitro-body meltingat 1 7 5 O . L. T. T.Action of Nitric Acid on Oxycamphor from B-Dibromo-camphor. By J. KACHLEB and 3’. V. SPITZER (Ber., 15, 2336-2337).-Oxycamphor (b. p. 259”), obtained by the action of sodiumamalgam on an alcoholic solution of @-dibromocamphor, forms a crys-talline barium salt, Ba(C,oH,,O,),. When treated with nitric acid,oxycamphor yields a mixtiire of oxalic acid and nitroxycamphor,CloH,,NO4. This substance crystallises in colourless needles (m. p.CEnocyanin. By E. J. MAUMENB (Compt. rend., 95, 924).-mnocyanin, the colouring-matter of black grapes and red wines, is ofcolourless origin, and becomes blue through oxidation, and probablyhydration, which may be shown by placing a green grape picked froma bunch which is just beginning to turnred, in a vacuum of 1 to 2 mm.over boiled sulphuric acid for three or four days, or sufficient timeto allow of the grape becoming hard and dry.The colour becomesvellow, but 011 admitting air, moisture and oxygen are rapidlykbsorbed, the colour changing to blue-black at the same time.ByJ. F. EYKMAN (Pharm. J. Tra72s. 131, 13, 365-367).-The aqueousextract of the leaves of this plantl, which has long been consideredas poisonous in Japan, contains a glucoside, “asebotoxin.” It is atransparent brittle col ourless substance, melting at 120”, and containsC = 60.48, H = 7.405, 0 = 32.115 per cent. ; it is only slightly solublein cold water, but easily in ethyl and amyl alcohol, cliloroform, &c.The aqueous solutions are unaffected by ferric, mercuric, or goldchloride, or by lead acetate ; but they reduce alkaline copper solutions,The fatal dose for rabbits by hypodermic injection is 3 mgrms.for eachkilogram of the animal ; the symptoms are detailed.Asebotoxin exhibits some fine colour-reactions, which are of im-portance toxicologically. If an alcoholic solution of the substanceis poured into a watch-glass and strong hydrochloric acid added, amagnificent blue colonr is gradually developed, and, a t the same time,a peculiar odour resembling that of Spircti?a uZmaria. On evaporatingtlie blue solution on a water-bath, a fine violet-red tint derelops itself170”), which dissolve freely in hot alcohol. w. c. w.I;. T. 0’s.The Poisonous Constituent of Andromeda Japonica216 AB.3TRACTS OF CHEMICAL PAPERS.a t the edge of the liquid.If the blue solution be left to itself, it) turnsafter some time to reddish-grey, and the liquid becomes turbid fromthe separation of a bluish-grey substance. Concentrated sulphuricacid dissolves asebotoxin with a red colour, which after some time be-comes fine rose-red, while the liquid is rendered turbid from the sepa-ration of a bluish-grey substance. If asebotoxin is boiled withdiluted hydrochloric acid, the liquid assumes a fine rose-red colour,and a brown resinous substance separates. The same effect is pro-duced by diluted sulphuric acid.Constituents of the Leaves of Fraxinus Excelsior. By w.GINTL and P. REINITZER (&!oncrfsh.Cheoz., 3, 745-762). - Theaqueous decoction of the leaves of the ash-tree contains, as chief con-stituents, calcium malate and a tannin, designated fraxitannic acidby the authors, together with smaller quantities of mannitol andinosol, and still smaller qnantities of quercitrin, dextrose, gummymatter, and free malic scid. To separate the fraxitannic acid, theaqueous extract was precipitated by normal lead acetate, and the pre-cipitlate, after being quickly washed with cold water, was treated twoor three times a t boiling heat with acetic acid of about 10 per cent.,which dissolved nearly all the tannate of lead, leaving undissolved thegreater part of the malate, together with other bodies. The resultingstill impure acetic solution of the lead tannate was then precipitatedby ammonia in nine separate fractions, of which the third, fourth, andfifth yielded the purest tannic acid, whereas the first and second con-tained also oxidised products, which, however, being less soluble inacetic acid than the pure lead tunnate, could be separated by treatingthe precipitates with quantities of acetic acid not sufficient to dissolvethe whole.The resulting solutions were then precipitated by ammo-nia, and the precipitates, as well as those previously obtained, werewashed as quickly as possible by decantation with cold water, and de-composed by hydrogen sulphide ; the solutions thus obtained werefiltered into a flask previously filled with carbonic anhydride; thefiltrates were freed from hydrogen sulphide by a stream of the samegas ; and the solutions thus purified were evaporated to dryness in avacuum over sulphuric acid.The first and second fractions thusobtained were but very slightly hygroscopic, and easily pulverisable ;the third, fourth, and fifth also only slightly hygroscopic; whereas thesixth, which contained considerable quantities of malic acid, and theseventh, eighth, and ninth, were very hygroscopic, and formed syrupystrongly acid masses, the first two containing-togzther with smallquantities of tannic acid-a moderate quantity of malic acid, a littleinosol, a gummy substance, and a somewhat considerable quantity ofamorphous silica, whilst the ninth fraction was destitute of tannicacid, contained only small quantities of malic acid and mannitol, andconsisted mainly of the gummy substance just mentioned.The first five fractions were next digested with absolute alcohol inclosed flasks, filled with carbonic anhydride and kept in the dark,\vhereby the greater part of the tannic acid was dissolved to a yellowliquid, leaving only a small quantity of a blackish-brown substance,easily soluble in water.The united alcoholic filtrates were then freedE. W. PORGANIC CHEMISTRT. 217from the greater part of the alcohol by distillation in a stream of car-bonic anhydride ; the residue was treated with water, which dissolvedit all with the exception of a very small quantity of substance, pro-bably an anhydride, formed by the prolonged boiling with alcohol ;and lastly, the filtrate was evaporated to dryness.The substancesthus obtained from the five fractions agreed so closely in composition,solubility, and reactions, that they may, without hesitation, be regardedas one and the same chemical compound.This compound, frnxitan??ic acid, is an amorphous, yellow- brown,shining, brittle mass, yielding a golden-yellow powder, which, onexposure to moist air, gradually deliquesces to a yellow-brown shiningtenacious mass. It dissolves in water, yielding, according to thedegree of concentration, a golden-yellow to brown-red liquid, whichhas a rough, bitter taste, and reddens litmus slightly ; alcohol, aceticacid, and ethyl acetate dissolve it readily, but it is quite insoluble inbenzene, chloroform, and anhydrous ether, slightly soluble in ethercontnining wat.er.The moderately concentrated aqueous solution isprecipitated by sulphuric and hydrochloric acids, yielding a light-yellow precipitate, soluble in excess of the acids and on warming, andreappearing as the liquid cools. From its aqueous solution, unlessvery dilute, it is completely precipitated, like other tannins, on satu-ration with common salt. The aqueous solution is not precipitated bytartar emetic, but with normal lead acetate it gives a fine golden-yellowprecipitate, easily soluble in acetic acid, becoming brown-green onexposure to the air, and at the same time less soluble in acetic acid.Ferric chloride imparts a fine dark-green colour to the aqueous andalcoholic solutions of the acid, forming a precipitate a t the same time,the colour changing to blood-red on addition of an alkaline hydroxide,normal carbonate, or acid carbonate, these colours becoming dingy onexposure to the air.A small quantity of the tannin solution added toan alkaline cupric solution, throws down cuprous oxide on warming ;with mercuric chloride, i t forms a slight precipitate of calomel.Heated with dilute acids or with barjta-water, it does not yieldglucose ; with the latter reagent, it appears to yield protocatechuic acid.Fraxitannic acid dried in avacuum at ordinary temperature has thecomposition CI3Hl6O7, and when heated a t 100" in a stream of carbonicanhydride, it gives off water and is converted into an anhydride,C,,H,,O,, = 2Cl3Hl6O7 - HzO, which is nearly insoluble in cold, andonly slightly soluble in hot water.The acid, if heated on the water-bath with acetic anhydride, isconverted into an acetyl-derivative, C17H& = C13H14(UAc)205, form-ing an amorphous yellowish mass, which gradually softens whenheated to loo", and melts at a slightly higher temperature; theliquid, after cooling, appears transparent with amber-yellow colour inthin layers, dark brown in thicker layers.It becomes very stronglyelectric on trituration. Its melting point is not determinable, as itpasses into the liquid state by very slow degrees.The corresponding benzoy I-dekuative, CZ~HZJO, = C,,HIa( O B Z ) ~ ~ ~ ,is prepared by heating the taniiic acid with fused benzoic anhydridefor several hours in a paraffin-bath a t about 130" ; exhausting the masswhich solidifies on cooling with ether, which leaves the whole of the4 VOL.XLJV218 ABSTRACTS OF CHEMICAL PAPERS.benzoyl-derivative undissolved, then dissolving the residue in alcohol,and either evaporating on the water-bath, whereby a dark-brownresidue is obtained yielding a light-brown powder, or precipitating thealcoholic solution with water, adding calcium chloride, and heating theliquid to cause the precipitate to settle down. The benzogl-compoundis thus obtained as a light-brown powder insoluble in water and inether, but soluble in alcohol. It becomes electric by friction, thoughnot so strongly as the acetyl-compound. Its alcoholic solution givesno coloration with ferric chloride.On dropping bromine or fuming nitric acid into a well-cooled solu-tion of acetylfraxitaiinic acid in glacial acetic acid, or, better, in aceticanhydride, then precipitating with water, washing the precipitate withcold water, and drying it in a vacuum over sulphuric acid, a lightorange-yellow powder is obtained, which dissolves very sparingly inwater or in ether, easily and with brown-red colour in alcohol.Thenitro-compound, heated on platinum-foil, suddenly takes fire with slightdetonation.The bromncety 71-compound has the composition C3dH37Br301e + 2H,Oor C,,H2,(Kc0)4Br30,0 + 2H2O.The constitut'ion of this body shows that fraxitannic acid containsfour hydroxyl-groups, and that its molecular formula is the double ofthat above given, viz., C2,H,& = C26H28( oH),Olo.The acid, treated with manganese dioxide and sulphuric acid, givesoff a strong odour of quinone.When heated in a stream of carbonicanhydride it liquefies a t 120°, then becomes viscid and frothy, once morefluid a t 180°, and between 220" and 260" yields a small quantity ofyellowish-green oil, giving with ferric chloride a, fine green colour,probably due to admixed catechol.The insoluble residue left in small quantity in the purification offraxitannic acid with absolute alcohol (p. 216), is a shining, brown-black, easily friable, non-hygroscopic substance, which dissolves inwater to a yellowish-brown liquid, giving with lead acetate a brown-green precipitate, similar in colour to lead fraxitannate which has beenexposed to the air.Dried in a vacuum, it has the compositionCl,H1608; after drying a t loo", C2,H,0,, = 2C,,H1,08 - H,O. Ittherefore bears to fraxitannic acid the relation of an ordinary acid toits aldehyde.Another body is formed when a neutral or very slightly alkalinesolution of fraxitannic acid is repeatedly evaporated on the water-bath in an open vessel, and remains, on drenching the residue withwater, as a soft adhesive brown mass running together in a cake at thebottom. This substance, after being dried in a vacuum, forms a brownbrittIe resinous mass having the aspect of catechu. It is very slightlysoluble in cold, somewhat more in hot water, and separates on coolingas a milky cloud, which gradually aggregates to a brown glutinousmass.For purification, it was dissolved in alcohol of 96 per cent.which left a residue, and separated by water into two portions, theportion thereby precipitated being treated with absolute alcohol toremove a small quantity of matter insoluble therein. When thuspurified, it formed a brown powder perfectly soluble in absolute, and innot too much diluted alcohol, also in strong acetic acid and in ethyORGANIC CHEMISTRY. 219acetate, but insoluble in water, ether, and benzene. Boiling waterdissolves it in small quantity, and deposits it on cooling as a yellowishprecipitate. It dissolves readily in alkalis with deep-yellow colourand a faint odour of' tea. The alcoholic solution reacts with ferricchloride and an alkaline cnpric solution, just like fraxitannic acid.This compound forms an acetyl- and a benzoyl-derivative, and is con-verted by fusion with potash into a substance which gives the reactionof protocatechuic acid with ferric chloride. Dried a t 100" in astream of carbonic anhydride, it gives by analysis mimbers agreeingwith the formula C,H803.It appears, however, to be formed by sepa-ration of COz and H,O from several molecules of fraxitannic acid, asshown by the equation-5CisH1607 - (2CO2 + 4HZO) = C63H72027 = 9C7H803,Its benzoy Z-derivative, ClO5H9,O3, = C6&f66i%O,,, is a light-brown powderinsoluble in water, alcohol, and ether, soluble in chloroform ; it beginsto blacken, without fusing, a t 120".Volatile Oil of Ash-leaves.-In preparing the aqueous decoction ofthe leaves, a pleasant smell of tea is given off, due to a very smallquantity of a volatile oil, which may be separated by distilling the freshleaves with water, shaking the aqueous distillate with pure ether,evaporating off the ether, dissolving the residue in alcohol, mixingthe alcoholic solution with solution of common salt, separating the oilylayer which rises to the surface, and rectifying it over calcium chloride.The oil thus rectified forms a colourless liquid having a strong andvery pleasant odour like that of syringa flowers.It boils at 1 7 5 O , andgives by analysis numbers leading to the formula C1oHzoOz. It probablybelongs to the class of terpenes, but has the formula of anhydrousterpin, although it is liquid. H. W.Euxanthic Acid. By A.SBIEGEL (Bey., 15, 1964--1969).--Eu-xanthic acid has long been known as a conjugated compound, but thenature of the substance into which, together with euxanthone, it isresolved by the action of acids, has never yet been clearly ascertained.The author employed the action of 2 per cent. sulphuric acid in sealedtubes, and then found the product to be euxanthone and the anhy-dride of glycuronic acid. The identity of this latter with the glycuronicanhydride of Schmiedeberg and Meyer (Jahd. Chem., 1879, 986)was proved by a comparison of the crystallographic forms and chemicalreactions of the two preparations. The author considers that thesubstance described by Erdmann as hamathionic acid was in reality asulphate of glycuronic acid, the analysis given by Erdmann of a basiclead salt agreeing much better with the formula of the latter thanwith that assigned by him to hamathionic acid.I n conclusion theauthor thinks that some light is thrown on the source of purree bythese results ; the view that it is a dried sediment from camels or ele-phants' urine has lately met with disbelief, but as conjugated glycu-ronic acids have lately been obtained several times from the urine ofanimals subjected to feeding experiments, it seems reasonable to con-clude that euxanthic acid may have a similar origin. A. 2. G.9 280 ABSTRACTS OF CHEMICAL PAPERS.Hydrates of Pyridic Bases derived from Cinchonine. By W.0. DE CONINCK (Rec. Trau. Chim., 1,132). -The author finds that B-col-lidine (b. p. 195-196") and P-lutidine (b.p. 165-166"), left for twomonths over a basin of water covered with a bell-jar, take up quanti-ties of water, agreeing with the formulae C8H11N,H20 and C7$€9N,H20 ;he does not, however, regard the products thus obtained as well-defined hydrates. H. W.Conine. By C. SCHOTTEN (Ber., 15, 1947--1951).-The onlyoxidation-product of conine a t present known is normal butyric acid.As substances of pronounced acid or basic properties are frequentlyunsuitable for directl oxidation, the author first converted conine intoits urethane, a completely neutral body.Conylurethane, C8H16N.COOEt, is best prepared by the action of ethylchlorocarbonate on conine in presence of aqueous potash. It is acolourless liquid (b. p. 245") of agreeable ethereal odour, and is lighterthan water.It is not decom-posed by boiling with concentrated potash or with hydrochloric acid,nor is i t decomposed when heated with aqueous ammonia in sealedtubes at 200". Hydrochloric acid in sealed tubes a t 100" decomposesit into conine, carbonic anhydride, and ethyl chloride. On distillationwith phosphoric acid, it yields, amongst other products, a hydrocarbonwhich is probably conylene. By the action of well-cooled nitric acidon conylurethane, a monobasic acid of the formula C,H140,.COOEt isobtained as a nearly colourless heavy oil of well-marked acid proper-ties. On heating this acid with hydrochloric acid in sealed tubes at loo", the COOEt-group is eliminated (as ethyl chloride and carbonicanhydride), and on evaporating the solution, large crystals areobtained OC a body having the formula C,Hl,02N,HCl.This body isreadily soluble in water, has no poisonous properties, and gives aplatinochloride crystallising in needles or prisms. The author regardsit as the hydrochloride of an amido- or imido-acid, but he has notsucceeded in isolating the acid.It is insoluble in water and in acids.A. J. G.Conhydrine. By A. W. HOFMANN (Ber., 15, 2313--2316).-Whenconhydrine, CBH17N0, is acted on by dehydrating agents, e.g., phosphoricanhydride or concentrated hydrochloric acid, conine is not produced asstated by Wertheim (AnnuZen, 127,75), but an oily liquid is obtainedwhich consists of a mixture of different compounds. W. C. W.Compounds of the Creatinine-group. By E.DUVILLIER(Compt. rend., 9 5, 456-459) .-Methyl amido- a-butyrocyamicline oroc-hzctyric-creatinie, C,Hl,N,O, is obtained by the prolonged action ofcyana'mide in concentrated and slightly animoniacal aqueous solutionon methylamido-a-butyric acid. The substances are mixed in theproportion of equal molecules, and after about one month lamellarcrystals begin to separate out, and continue to form for about fourmonths. At the end of this time, the crystals are removed and abouthalf the original quantity of cyanamide is added to the mother-liquor.A further crop of cryshals is thus obt.ained. The crystals dissolve inboiling alcohol, and separate mt on cooling in slender silky needleORGANIC CHEBIlSTRT. 221composed of small rectangular plates.The creatinine is not formedby the dehydrating action of the alcohol on the original crystals, €orthe latter contain no water of crystallisation and have sensibly thesame composition as the purifiedproduct. This is the first instance ofthe formation of a creatinine without the intermediate formation ofthe corresponding creatine.Methylamido-isoualerocyamidi?ze or Isovaleric Creatinine, C,H13N30, isobtained in a similar manner by the action of cyanamide on methyl-amido-isovaleric acid. It forms slender needles, readily soluble inboiling alcohol.The formida of these compounds are -Methylamido-a-butyrocyamidine. Meth ylamido-isoralerocyamidine.NMe.CH. CHMezNH:C/ I Y or .,e*7HEt \-NH.CONH:CNH : C N.C0.CII,NH(Me).CH2.Me N H : C:N.C0.CH(NHMe).CHMe2according as the view of Strecker and Erlenmeyer, or that of Kolbe,on the constitution of creatine and creatinine is accepted.\-NH.COC.H. B.Morphine. By E. v. GERICHTEN and H. SCHROTTER ,(Bey., 15,2179--2183).-The object of this investigation was‘ to examine thenature of the two non-nitrogenous bodies C15H1002 and C15H9Br02,which the authors obtained from codeine and monobromocodeine(Abstr., 1882, 1112). Their insolubility in dilute alkalis pointed totheir still containing the methoxyl-group present in codeine. Anattempt to split off methyl from the compound C15H1oO2 by heatingwith hydrochloric acid, was unsuccessful. Codethy line, Cl9H,,NO3,treated by Hofmann’s reaction (Abstr., 1882, 921), yielded a non-nitrogenous body, C16H1202, homologous with the above-cited codeinederivative.Both these bodies yield phenanthrene-leaving no doubtof the presence of a methoxyl-group-when heated with zinc-dust,and may therefore probably be considered as phenanthrene deriva-tives. The following table shows the relationship of these compoundsto the morphine alkalo’ids :222 ABSTRACTS OF CHEMICAL PAPERS.Non-nitro-genous derira-tive.~Alkaloid.productbetween non-nitrogenousderivativeMorphine . . . . . . . .Codehe (mor-phine mono-methylether) .Bromocode'ine , . . .Codethyline (mor-phine mono-ethyl ether) . .I CI4H,BrO.OMem. p. 121-122"C14HTO. OE tFormula.Hypotheticalintermediateand phenan-threne.I1 CI4H7O.OH.*Phenan-threne.The authors consider this hypothetical intermediate product to haveeither the formula (i) O< l6 '>C2H2 or (ii) 1 / C z O , and takinginto account the ease with which it is reduced by zinc-dust, they con-sider (ii) as the more probable.The non-nitrogenous derivatives ofcodeine and codethyline would then have the formula C6H'>c20(where R = Me and Et respectively).The non-nitrogenous derivative C,,H,O.OEt, obtained from codethy-line, is insoluble in water, but soluble in ether, alcohol, and acetic acid.It crystallises well, melts a t 59", and distils almost without decom-position. On heating it in sealed tubes with +he calculated quantityof hydriodic or hydrochloric acid, ethyl iodide or chloride is pro-duced, together with a resinous mass, from which a very small quan-tity of a body crystallising in white needles was extracted, insufficientfor investigation. C,,H1,02 is sohzble in strong snlphuric acid to ayellow liquid having a green fluorescence, and is reprecipitated un-changed on adding water.A nitro-derivative was obtained. C,,H,,O,is oxidised by chromic acid, and is easily reduced to phenanthrene byheating it with zinc-dusk.Cinchonine. By H. WEIDHL and K. HAZARA (Monatsh,. Chem., 3,770--T88). -Cinchonine oxidised with chromic acid yields, as chiefproducts, cinchoninic acid and an acid brownish syrup, together withsmall quantities of carbonic and formic acids.The syrupy liquid freed from cinchoninic acid and other substancesby a series of processes for which the original paper must be con-sulted, dried up in the exsiccator to a soft gummy mass, which showed* Cl,H802 and C14H,0 have not yet been obtained.CH C6H4\CsH3 C6H4L.T. TORGANIC CHEMISTRY. 223no tendency tto crystallise, even after standing for a year. Its aqueoussolution decomposes carbonates a t boiling heat, yielding deliquescentuncrystallisable salts. When neutralised with an alkali, it does notprecipitate metallic salts. Heated with oxidising agents, it does notyield either cinchoninic or pyridine-tricarboxylic acid, whence theauthors infer that the syrupy liquid obtained by the oxidation of cin-chonine does not contain any portion of that half of the cinchoninemolecule which yields cinchoninic acid.The syrupy liquid treated for a day with nitric acid yielded a smallquantity of nitl.o72ydrozyquirLoZi?te, C,H,(NO,) (OH) N, a compoundwhich unites both with bases and with acids, the salts which it formswith the latter being however very unstable. I t s platinochloride,(CgH6N,03,HC1),PtC14, forms monoclinic crystals, in which a : b : c =0.9705 : 1 : 0.8806 ; /3 = 96" 20' 4".Optic axes nearly perpendicularto the base. Observed faces mP6, OP, mP, +P, and -P.When the residue left on evaporating the syrup over the water-bath is distilled with zinc-dust, a light-yellow oil passes over, andafterwards a brown viscid distillate, containing-together with ammo-nium carbonate, pyrroline, and bodies related thereto-the tlhree fol-lowing bases :-Pyridine, C,H,N. Ethyl-pyridine, C7HgN.Quinoline, C9H7N.b. p. 120". b. p. 161-164" b. p. 233-237"These bases are formed from that half of the cinchonine-moleculewhich is converted by oxidation into the syrupy product, and theirformation shows that cinchonine must contain two hydiwgenised quino-line-nuclei-a conclusion strengthened by the fact that tetrahydro-cinchoninic acid, as shown by Weidel (C. ,J., Abstr., 1882, 531), yieldsby oxidation, not cinchoninic acid, but a syrupy mass, which as theauthors find by preliminary experiments, also yields by distillation overzinc-dust, bases of the pyridine series, respecting which they promisea further communication. H. W.Strychnine Sulphate. By LEXTREIT (J. Pharm. Chim. [ 5 ] , 6,259-266) .-Regnault assigned to strychnine sulphate the formuIaC2,H,J?,02.H,SO~ 4- 7H,O, which was adopted by the Codex of 1866,but subsequent researches by Schabus, Des Cloizeaux, and Rnmrnels-berg, who have described preparations containing from 5 to 6.5 mols.ofH20, hare failed to confirm this formula. Although a great numberof samples used in pharmacy were analysed, not one satisfied the aboveformula.To determine what hydrates exist, and the conditions under whichthey form, the following research was undertaken :-When a neutral and saturated aqueous solution of strychnine sul-phate is allowed to crystallise between 109" and 95", a salt of the com-position C2,H2,N20, + H,SOa + 5H20 separates out, biit if the tem-perature sinks below 95" some crystals containing 6 mols. H20 areformed.When crystallised from alcohol it always crystallises with5 mols. H20. To prepare this compound, 10 parts of strychnine and1.27 parts sulphuric acid are mixed in a flask, and 50 parts stron224 ABSTRACTS OF CHEMICAL PAPERS.alcohol added and gently warmed. When Bolution is complete, themixture is left to cool, and the salt crystallises; a further crop ofcrystals may be obtained from the mother-liquors. If dilute alcohol isused, the crystals are very bulky, but its strength must not beless than 50", otherwise square tables containing 6H,O will be formed.The salt crystallises in slender needles from aqueous solutions, andfrom alcoholic in clinorhombic prisms identical with those describedby Des Cloizeaux (Arm. n/li.fleraZ., 1858,14,389), containing 6H20, andby Rammelsberg containing 5H20.The hydrate, (C2,H2,NZO,),H2S0~ + 6Hz0, is obtained in longslender needles when a hot concentrated solution of the neutral sul-phate is cooled between 95-50' ; below 50" tabular crystals separateout. 10 parts of strychnine are dissolved in a mixture of 1.27 partssulphuric acid and 35 parts water, the solution boiled, and allowed tocrystallise a t 70" ; above 70" a mixture of this and the previous salt isobtained. This salt crystallises i n octohedrons, which confirms the re-sults of Rammelsberg (Ber., 1882). Des Cloizeaux (Compt. rend., 44,909) also obtained a salt crystallising in octohedrons, but found it tocontain 6.5 H,O. The crystals do not alter when exposed to the air,but slowly lose their water of crystallisation over sulphuric acid, andquickly at 100". The anhydrous crystals reabsorb a portion only ofthe water they have lost.The salt containing 7H20, described by Regnault, is shown by theauthor from the analytical data of the former not to agree with theformula ascribed to it.The acid suZphate, C21Hz2N,02H,SOa + 2Hz0, is prepared by treat-ing 1 mol. of strychnine with 1 mol. of sulphuric acid, and crystal-lising either from alcohol or water. It forms short needles whencrystallised a t a high temperature, but when slowly formed a t lowtemperatures they may be obtained several centimeters long. Theirform could not be determined. L. T. 07s.Preparation of Lupinine Hydrochloride from Lupinine Resi-dues. By G. BAUMERT (Bar., 15, 1951--1952).-1n the preparation ofpure lupinine, a large amount of mother-liquors are obtained from thefrequent recrystallisations ; these contain considerable quantities oflupinine, whose cry stallisation is prevented by the impurities present..The mother-liquors, after removal of ether, are shaken with an equalvolume of cold water, and the emulsion heated for a few minutes onthe water-bath, when it separates into two layers, the upper consistingof water containing lupinine in suspension. On cooling, the turbidityvanishes and the lupinine dissolves. The aqueous layer is poured off,and the residue treated several times with water in the same manner.The aqueous extracts are then neutralised with hydrochloric acid,evaporated, dissolved repeatedly in absolute alcohol, and evaporated toremove water, freed from a black syrup by pressure between filter-paper, and finally crystallised from absolute alcohol, when pure lupi-nine hydrochloride is obtained.Putrid Fermentation, and the Alkaloi'ds produced by it.By A. GAUTIER and A. ~ T A R D (Compt. rend., 94, 1598--1601).--TlieA. J. G ORGANIC CHEMISTRY. 225authors consider that the apparently complex phenomena of putridfermentation may be explained by regarding putrefaction as a breakingup by hydration of the complex albumino'id molecule into the simplenuclei which enter into its composition. As in the results Schiitzen-berger obtained with barium hydroxide, so by the action of thebacteria, the albuminold molecule splits up first into two principal parts ;one of these is relatively stable, giving rise to the glucoprotelns andleucines to which Schiitzenberger attributes the formula C,H2,-4N2O2,whilst the other is unstable, and decomposes rapidly, with formation ofammonia, carbonic anhydride, and formic, acetic, and oxalic acids.But whilst Schutzenberger's method is incapable of hydrating theamides formed,-the leucines and leuceines,-bacteria slowly changethem into ammoniacal saIts, and also by the hydration of the crystallinebody, CnHzsN20s, produced abundantly in the putrefaction of fish.Putrefaction being essentially a process of hydration, i t followsthat the aromatic derivatives and the bases formed during the fer-mentation pre-exist as nuclei in the albumino'id molecule. In orderto obtain the bases, the liquid products of pctrefaction of the skateare acidulated with sulphuric acid and evaporated in a vacuum,whereby indole, phenol, and other volatile products are removed ; theresidue is then treated with baryta and chloroform, which dissolves thebases. After purification, they are colourless oily liquids having allthe characters of the bases described by Selmi. They have an odourlike that of the carbylamines, recalling that of hawthorn and hydro-collidine, resinify rapidly, and give the reactions of the ptomalnes.The hydrochlorides crystallise well, and yield sparingly soluble crys-tall ine plat inoc hlorides.By fractionation, two bases were isolated, one having the formulaof parvoline, C9H13K, and yielding a platinochloride which becomesrose-coloured on exposure to the air, the other an oil boiling a t about110". The latter gives a hydrochloride crystallising in slender needlesof bitter taste. The platinochloride is pale-yellow, and sparinglysoluble ; the aurochloride is very unstable. Although the analyticalresults agree better with the formula CeHIIN, the author assigns tothis base the formula C8H13N, as the boiling point, viscosity, andgeneral properties so very closely resemble those of Cahours andatard's hydrocollidine, with which he believes it to be isomeric.From these considerations, the occurrence of indole and of pyridicand of hydropyridic bases amongst the products derived from albu-minoids by putrefactive hydration, the authors feel compelled toadmit the existence of the homologous series C,H,N and C5H,N inthe radicles of the proteid molecule.By M. J. KJELDAHL (Bied. Centr., 1882, ?9l).-Tern-perature has different effects on the action of invertin from surfaceand from bottom yeast. Bottom yeast acts best on saccharose a t 52-53", whilst surface yeast is most energetic a t 56". The action of theinvertin also increases with the concentration until a certain limit(20 per cent.) is attained.At the commencemeut, the action is proportional to the t8ime ofaction, and also the amount of invertin, so long as not more thallC. E. G.Invertin226 ABSTRACTS OF CHEMICAL PAPERS.40 per cent. of the whole sugar originally present has been converked.Alkalis and rnercizry salts cause the action t o cease, whilst acids aidit at starting. On laevulose, dextrose, maltose, dextrin, and inulin,invertin has no effect. E. W. P

ISSN:0368-1769    

DOI:10.1039/CA8834400172

出版商:RSC    

年代:1883

数据来源: RSC

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226 ABSTRACTS OF CHEMICAL PAPERS.P h y s i ol o g i c a1 Chemistry.Spontaneous Fermentation of Animal Matters. By A.BI~CHAMP (Conzpt. rend., 94, 1533--1536).--The results already pub-lished by the author and others show that alcohol is produced inthe spontaneous fermentation of animal matters, such as eggs, liver,horse-flesh, &c., thus raising the question as to whether alcohol is notproduced in the tissues of the human organism itself; this has beenanswered in the affirmative, alcohol having been found in the uriiie ofa subject who had abstained from taking alcoholic drinks, in freshlydrawn milk, and in the muscles of animals recently killed.The only histological elements in the organism which persist afterdeath being the microzymas, it is natural to regard them as the orga-nised ferments, producing alcohol, acetic acid, &c.; moreover, the pre-sence of alcohol in the tissues indicates one of the causes of the dis-appearance of sugar. The fermentable matter which is the first todisappear after death is glucose or glycogen, and this change is causedby the microzymas from which the bacteria are evolved, since theynever attack the albumino'id matters until after the sugars have beencompletely destroyed, and it is then only under certain conditions,with free access of oxygen, that the animal matter is finally resolvedinto carbonic anhydride, water, and nitrogen, or nitrogenous com-pounds.The author concludes by affirming that the microzymas are theactive chemical and physiological agents, whereby the transforma-tions in the organism are effected both when living and after death.C.E. G.Effect of Food on Sheep of Different Breeds. By El. WEISKE,G. KENNEPOHL, and B. SCHULZE (Bied. Centr., 1882, 743-745).-1tis a well-known fad; that the same quantity and quality of food givento sheep of different breeds does not produce like effects. To provethis fact experimentally, a sheep of the Rambouillet breed and aSouthdown-merino were fed with like food. The digestive coefficientsfor each constituent of the food was found to be almost identical.Comparison of the amount of nitrogen retained by the two sheepshowed that the Rambouillet sheep, which is well known as a bad'' doer," retained the largest quantity, and this is probably due to thegreat amount of wool which grew.So far these experiments show nogreat difference between the races. A further set of experimentswill be made to determine whether the difference lies in the laying onof fat, &c. E. W. PPHYSIOLOGICAL CHENISTRT. 227Artificial and Natural Digestion of Nitrogenous Matter.By T. PF‘EIFFER (Bied. Centr., 1882, 739--743).-Stutzer (Abstr.,1239) divides protejid matter into albuminojids (digestible) and nncle’in(indigestible), and considers that by means of artificial digestion aquantitative separation of the two can be accomplished. The author,however, judging from experiments on sheep, considers that Stutzer’sconclusions are incorrect, as nucle‘in does not pass through the systemunaltered, and he finds that the nnclejiii nitrogen excreted is 25-30per cent.less than that given in the food.Excretion of Nitrogen from the Skin. By J. B. POWER (Proc.Roy. Xoc., 33, 354-360).-The results obtained by various experi-menters on the excretion of nitrogen in the sweat have proved contra-dictory ; Berzelius, Favre, Funke and others, have found nitrogen,whilst Voit, Ranke, and Parkes have denied its exist,ence. The authortakes exception to Funke’s method of procedure, which presupposesan equality of secretive power, and identity of chemical compositionof the sweat from the arm with that excreted from the rest of thebody. The author by a suitable apparatus and a method whereby thesweat from the whole of the body is collected, finds, as a mean of 25experiments, that 0.038 gram of nitrogen existing in some soluble formis excreted per hour.Healthy subjects were operated on, and alsopatients suffering from Brights’s disease, catarrh, gout, acute rheuma-tism, and nephritis.Several determinations were made of the quantities of nitrogen pre-sent in some insoluble form, e.g., epithelium, and also of the sodiumchloride in the sweat; the proportion of the latter to the nitrogenis about 10 : 1. The author concludes that the cutaneous excretion ofnitrogen is so small, that it can never replace the renal excretion toany appreciable extent.Milking of Cows Twice or Thrice Daily. By ERLENXEYER(Bied. CeiLtr., 1882, 785).-The amount of milk is depend-ent on theactivity of the milk glands, as well as on the fodder supplied.Mid-day milk is the richest in fat,, morning milk the poorest, because alonger timehaving elapsed since the evening milking, a greater quantityof milk is formed. Experimental data are given in support of thesestatements. E. W. P.E. W. P.V. H. V.Nitrites in Human Saliva. By R. N. MUSGRAVE (Chem. News,46, 21 7) .-By means of sulphanilic acid followed by naphthylaminehydrochloride, nitrites were detected in the saliva of numerous per-sons, the quantity varying between 0.4-2.0 parts nitrogen per mil-lion; the amount varied for the same person a t different times, forexample, the amount present before breakfast was 0.0, after breakfast(10-11 A.M.) 2.2, and between 1 and 2 P.M., 1.3 parts per million.E. W. P.Cause of the Evolution of Oxygen from Hydrogen Peroxideby Fibrin; Influence of Hydrocyanic Acid in Preventing theActivity of Fibrin.By A. B~CHAMP (Compt. rend., 95, 925-926).Thenard believes that fibrin decomposes hydrogen peroxide in a man228 ABSTRACTS OF CHEMICAL PAPERS.ner similar to silver and platinum ; he ascertained that oxygen wasnot absorbed, neither was carbonic anhydride evolved ; and from theconditions of his experiments, he concludes that the fibrin does notlose weight, and sufEers no modification. The liberation of oxygenfrom hydrogen dioxide by the red colouring matter of blood and byhaematosin has been shown by the author to be accompanied withoxidation, and a change in the bodies themselves. The author is ofopinion that Thenard was misled in his conclusions by the amount ofoxygen absorbed, and the loss of weight being too small to be mea-sured. The author shows that this property soon ceases, and with itthat of rendering starch soluble.30 grams of fibrin were treated three times with 60 C.C. of hydrogenperoxide (containing 10.5 C.C.oxygen per c.c.) free from acid. Thefirst time, oxygen was rapidly evolved, the second time more slowly,and the third time after 24 honrs no more gas was evolved. Afterascertaining that the solution contained excess of hydrogen peroxide,the experiment was stopped. From 180 C.C. of hydrogen peroxide1600 C.C. of oxygen were evolved by 30 grams fibrin in 48 hours. Thesolutions were separated from the fibrin which was finally pressed, andevaporated at about 90" ; the residue dried at 100" amounted to 0.2gram, of which 0.16 gram was organic matter.The fibrin remain-ing did not decompose hydrogen dioxide nor render starch solubleeven after remaining in contact with it eight days, whilst fibrinfrom the same source previous to treatment with hydrogen peroxiderendered starch-paste fluid in six hours. Moreover, it gave rise to nobacteria.The stoppage of the action of fibrin on hydrogen peroxide byhydrocyanic acid is thought to be due to the oxidation of the acid,since if sufficient hydrogen peroxide is present, the action is resumedafter a certain time. L. T. 0's.Lupine Sickness in Sheep. By HARMUTH and others ( X e d .Centr., 1882, 746-749). -Harmuth attributes an attack of lupinesickness which occurred to one of his flocks to dirt, &c., which wasblown by a high wind and settled on the crop, whilst another cropwhich was not thus afiected, produced no evil effects on sheep.Cream of tartar and sulphur readily cured the flock. It is quite pos-sible that the dirt and sand thus taken in did do some harm, butArnold refers tolie sickness to fungus. Arnold and Kuhn considerthat in lupines there is a substance, ictrogen, which becomes more in-soluble as the plant ages, so that if the crop be exposed to rain,ictrogen is more or less removed according to the age of the plant,but this ictrogen under the action of a ferment produces the poisonouscompound. E. W. P

ISSN:0368-1769    

DOI:10.1039/CA8834400226

出版商:RSC    

年代:1883

数据来源: RSC

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VEGETABLE PHYSIOLOGY AND AGRICULTURE. 229Chemistry of Vegetable Physiology and Agriculture.A New Milk Ferment. By E. KERN ( B i d Centr., 1882, '789).-In the Caucasus " kephir," a thick acid drink, which on keepingchanges into coumiss, is prepared from sweet milk by adding to i tmasses of a ferment ; the ferment consists of yeast and schizomycetescells, and these last seem t o be allied to Bacillus, and have been namedDispora caucasica; drying has no effect on the activity of this fer-ment, and the dispora growing threadwise retains its life thoughdried hard as a stone. E. W. P.Reduction of Sulphates by Living Organisms. By A. ~ T A R Dand L. OLIVIER (Compt. rend., 95, 846--849).-1n the protoplasm ofthe cells of certain a l p , such as Beggiatoa, dark granules are foundsoluble in ether, chloroform, and especially in carbon bisulphide.These granules disappear when the algae are placed in water free fromsnlphates, but on the contrary are formed when the organisms inquestion are cultivated in liquids rich in calcium sulphate.Hencethe authors conclude that these granules consist of sulphur. Thesealgae flourish extremely well in liquids containing, in addition to sul-phates, traces of selenium. At least three distinct kinds of algaepossess the power of reducing sulphates and disengaging sulphuret tedhydrogen. Most authors in treating of mineral waters state that theorganic matter exists in, soZution in the liquid, and becomes insolublein contact with the air. The authors' experiments have led them tothink that living organisms exercise an influence on the salinematters present in water, which could not be suspected, except bythe light of the above experiments, and they think that sufficientnotice of these facts is not taken in works on medicine.E.H. €3,.Reduction of Nitrates in the Soil. By D ~ H ~ R A I N and MAQUENNE(Compt. rend., 95, 691--693).--The reduction of nitrates takes placeonly in arable soils containing a considerable proportion of organicmatter, and only when the atmosphere surrounding the soil is entirelyfree from oxygen. The proportion of gas evolved is influenced to a,greater extent by the amount of organic matter present than by theamount of nitrate, but even when the proportion of organic matter islarge, its volume never corresponds with the volume of gas in thenitrate.The gas given off consists of carbonic anhydride andnitrogen, but under certain special conditions nitrous oxide is evolved.In one experiment with 300 grams of garden earth containing 3~ gramsof potassium nitrate, the nitrous oxide amounted to 11.75 per cent. ofthe volume of gas evolved : aiid with 300 grams of earth and 10 gramsof nitrate, it amounted to 9.35 per cent.Reduction of Nitrates in Arable Soil. By D ~ H ~ R A I N andMAQUENNE (Corn@. rend., 95, 732-734 and 85&-856).-SchloesingC. H. B230 ABSTRACTS O F CHEMICAL PAPERS.and Muntz have shown that soil capable of producing nitrates losesthat property if heated to loo", or if treated with chloroform, but thatsoil rendered inactive by heat regains its activity if mixed with alittle fresh active soil.The authors, following exactly the methodsdescribed by Pasteur, have shown that the same effects are producedby similar treatment on soils capable of educing nitrates. The fer-ment capable of effecting the reduction of nitrates seems t o be in-capable of living in oxygen, since in no case did the authors find anya,ction when oxygen was present. Since Schloesing has found thatnitrification takes place, although with less energy, in an atmospherepoor in oxygen, whereas the converse action never takes place but inthe complete absence of that gas, it seems highly improbable thatreduction commonly happens in arable soils ; but it is very likely thatin many instances the loss of nitrogen observed is due to the forma-tion of nitrates and their subsequent removal by drainage-water.When soil capable of reducing nitrates in the absence of air isadded t o a 1 per cent.solution of sugar mixed with a small quantityof nitre, and the whole placed in a flask completely filled with theliquid and kept a t about 35", fermentation commences and gas isevolved, consisting of a mixture of carbonic anhydride, nitrous oxide,and nitrogen, and in some cases hydrogen. The composition of thegas varies with the energy of the fermentation. When hydrogen isevolved, the water from the flask smells of butyric acid. This led theauthors to suspect the presence of the butyric ferment of Pasteur,described by Van Tieghem under the name B a d l u s amyZobacter, andlarge numbers of these organisms weye detected by microscopic ex-amination. Hence the authors attribute the reduction of nitrates tothe action of this organism.E. H. R.Fermentation of Nitrates. By GAYON and DUPETIT (Compt.rend., 95, 644!-646).-1f sewage-water is mixed with 0.02 gramof potassium nitrate per litre and some decomposed urine is added, thenitrate gradually disappears and the liquid becomes full of micro-scopic organisms. By successive cultivations, 0.1 and even 0.2 gramof potassium nitrate per litre can be reduced, but the reaction ceases a tthis limit. With fowl-broth neutralised with dilute potash, however,5 per cent. potassium nitrate can be completely decomposed, and10 per cent. partially.The denitrification is effected by the organismswhich are developed ; for if the liquid is sterilised by heat, or is mixedwith chloroform or copper snlphate, the liquid remains clear and thenitrate is not altered. The temperature most favourable to the deve-lopment of these organisms lies between 35" and 40°, and the presenceof organic matter is essential. Sugar, ordinary alcohol, and especiallypropyl alcohol, give the best resulis. Phenol and salicylic acid, addedin quantities even greater than those which are usually antiseptic, donot prevent fermentation, but, like other forms of organic matter, aredecomposed together with the nitrate. In the process of fermentation,a large proportion of nitrogen is given off as gas, the remainderforming ammonia, and perhaps nitrogen-compounds derived from theorganic matter ; the oxygen is converted into carbonic anhydride,which remains in solution in the form of neutral or acid carbonateVEGETABLE PHYSIOLOGY AXD AGRICULTURE.231The organic matters cause the products of the fermentation of thenitrate to enter into new combinations. Sodium, ammonium, andcalcium nitrate ferment in the same manner as the potassium salt.C. H. B.Absorption of Metallic Oxides by Plants. By F. C. PHILLIPS(Chenz. iV7ews, 46, 224-226). - Freytag has always upheld thatplants absorb oxides which are unnecessary for their growth, andpoisonous ; and as others have combatted this statement, the authorgrew several plants in soils to which had been added various oxides.Ageratums placed in soil containing 0.5 per cent. white lead maturedand produced flowers ; their roots mere abundaiit, but the leaves wereyellowish ; lead was absorbed into the plant.Geraniums in soil con-taining 0.5 per cent. zinc carbonate grew normally, but containedzinc. Achyrsnthes in soil containing 0.5 per cent. copper carbonategrew at first normally, but the leaves soon darkened and the rootsdied ; their ash contained copper in small quantities. Coleas in soilcontaining 0.5 per cent. calcium arsenate soon languished and died intwo weeks. In another series, coleas growing in soil to which had beenadded 0.25 per cent. calcium arsenate, never matured, and the rootsperished ; only traces of arsenic were discovered in the ash. Althoughzinc was found in considerable quantities in the ashes of pansiesgrowing in soil containing 0.5 per cent.zinc carbonate, yet the plantsappeared healthy. The conclusions drawn from the experiments are-that plants niay absorb small quantities of lead, copper, zinc, andarsenic ; zinc and lead may enter into the tissues without causing anydisturbance in the formation of the plant ; compounds of copper andarsenic exert a distinctly poisonous effect. E. W. P.Composition of the Banana a t Different Stages of Maturity.By L. RICCIA~~DI (Conzpt. rend., 95, 393-395).-The pulp has the.following composition :-Green. Ripe.Water (driven off at 110") .... 70.92 66.78Cellulose .................. 0.36 0.1 7Starch .................... 12.06 tracesTannin ....................6.53 0-94F a t . . ...................... 0.21 0.58Inverted sugar .............. 0.08 20.07Cane-sugar ................ 1-34? 4.50Pro te'id substances .......... 3 a04 4.9'2Ash.. ...................... 1.04 0.95Other substances ............ 4.42 1.69100*00 100~00The ash freed from carbon and carbonic anhydride contains-Si02. SO3. P,O,. c1. Fe,O,. CaO. MgO.5.77 3-06 23.18 traces traces 6.13 9.79Na,O. &O.6-79 45.23 = 999232 ABSTRAOTS OF CmMICAL PAPERS.The green fruit contains abont 12 per cent. of starch, which dis-appears in the ripe fruit. The sugar in the fruit which ripens on theplant is almost entirely cane-sugar, but that in fruit cut and ripenedby exposure to air consists of about 80 per cent. invert sugar and20 per cent.cane-sugar; the organic acids and tannin in the greenf r u i t disappear in the ripe fruit. The pulp of the fruit allowed to stagon the vine until t,he rind becomes almost black contains no ethylalcohol. It is evident, therefore, that the carbonic anhydride given offby the banana in the third stage of its maturity is not produced byalcoholic fermentation. Neither can it be derived from the destructionof the tannin, since the latter has almost entirely disappeared in theripe fruit. The evolution of carbonic anhydride is possibly the resultof true eremacausis. C. H. B.Oxalic Acid in Potatoes and in Malt. By M. SIEWERT(Lmndw. Versuchs.-Stat., 28, 263-270) .-An incrustation found inthe worm of an apparatus used for cooling the sweet wort, on beinganalysed, proved to be crystallised calcium oxalate ; the mash usuallyemployed consisting of potatoes and malt.In order to decide thequestion of the origin of this incrustation, samples were taken of thesweet uncooled, and the fermented wort, of the slime deposited fromthe mash, and of fresh potatoes and malt, and investigated withregard t'o their percentage of osnlic acid.It was found unnecessary to filter the wort hot, as no oxalate sepn-rated on cooling. One litre of the cold filtered sweet wort contained0.077 gram oxalic acid; the total amount in one litre of unfilteredwort being 0.134 gram, or 0.059 per cent. of the total acids. Thefermented mash contained 0.155 gram oxalic acid per litre, or 0.189per cent.of total solids ; whilst in the deposit was found 0.1 96 gramper litre, or 0.4 per cent. of dry substance.The amount of oxalic acid in potatoes was determined by boilingthe pulp with sodium carbonate, precipitating the filtrate with calciumchloride and excess of acetic acid; the decomposition with soda andreprecipitation with calcium chloride being repeated until a tolerablypure product was obtained. The first sample of potatoes analysedcontained 0.017 per cent., and the second 0.057 per cent. of acid.This was, however, not sufficient to account for the whole of theoxalic acid in the mash, and the malt used was therefore investigated.I n this case, the starch was first made soluble by heating with tartaricacid a t 145"; but this process was found to be attended by a con-siderable decomposition of oxalic acid.The starch was thereforeconverted into sugar by heating the malt for some time a t 62", andthe oxalic acid then determined in the usual manner. The malt wasfound to contain only 0*0015 per cent., and germinated grain 0.064 percent. oxalic acid. J. K. C.Average Amount of CaffeYne in the Guarana of Commerceas compared with that in the Seeds, &c. By J. H. FEEMSTER(Pharm. J. Trans. [3], 13, 363).-From several samples of guaranaseeds, 5.08 per cent. caffei'ne was obtained. Using this as a basisof comparison with five samples of guarana, it was found thaVEGETABLE PHYSIOLOGY AND AGRICULTURE. 2x3their average percentage amounted to 4.32. The best method of ex-tracting the caffe'ine was found to be Greene's (Chenz.J., 1877, 2,627). The best menstruum for the extraction was a solution con-taining 8 parts of alcohol, 4 of glycerol, made up with water to 20parts. Dilute alcoholic extracts have a tendency to form a deposit.E. W. P.Researches on the Causes of Clover Sickness. By V.KUTZLEB (Bled. Centr., 1882, 728--735).-As the result of the exami-nation of a special district affected with clover sickness, the authorcomes to the conclusion that this condition is due to want of potashin the soil, especially the want of soluble salts of potassium in thesubsoil. The theory that clover sickness is due to decaying vegetablematter is incorrect', as is also that put forward by Linde, who attributesall to the presence of Pleospora herbarum; the reduction in the yield ofclover may in part be due to the presence of parasites, such as Pezizaclborioides, or Ty lenchzcs devastntrix, or T.havensteinii; bur, in the case3when these parasites were found, the general appearances did notresemble those presented by clover sickness. A form of Phacidiicmmed;ccrgir,is has been found on clover; but as it is also to be foundon other allied plants which do not suffer, the disease cannot beattributed to this parasite. E. W. P.On Phylloxera. By P. DE LAFITTE and others (Bied. Centr., 1882,761).-Lafitte does not approve of V. Mayet's method of treatinginfected vineyards (Abstr., 1881, 1069). According to Boiteau, thewinged insect was not produced in such great numbers as usual,owing to the dryness of July, August, and September, 1881; con-sequently, he concluded that winter eggs would be fewer in number,its also the galls in 1882.These conclusions have now bgen found tobe correct. Pellicot and Jaubert recommend ferrous sulphate asdestructive to phylloxera. Yannuccini considers that the natural andartificial moisture of sandy soils, together with the character of thevines themselves, is the only cause of the power of resisting thedisease possessed by certain vines growing in such soils.E. W. P.Cure for Potato Disease. By J. L. JENSEN (Bied. Centr., 1882,755-759).-1t is recommended that, after the disease has attacked theleaves, the soil should be well ridged up, forming a ridge steepenough to induce the rain to run into the furrows ; it should also bemade so that the haulms should be bent over the furrow.All thisis proposed so that the disease spores which fall of€ the leaf may notbe washed down hy rain into the soil and so attack the tubers. It isbest not to lift the potatoes until 2-3 weeks have elapsed after thefull ripening, as it appears that the germs retain vitality up to thatdate. E. W. P.Atmospheric Nitrification. Ry A. MUNTZ and E. AUBIN (Compt.Tend., 95, 919--921).-The authors have examined six samples ofrain, three of mist, and four of snow a t the summit of the Pic du Midifor the presence of nitrates, but, with two exceptions, they failed toVOL. XThIV. 234 ABSTRACTS Of!’ CHENICAL PAPERS.detect any ; in these two cases the amount present was somewhat lessthan 0.1 mgrnm.per 10 litres. I n the exa’mination, 10 litres were used,and the rain gauge was of sufficient size to allow of that amount of waterbeing collected in so short a time as to exclude the idea of the reductionof nitrates.* The results are a t variance with those of Barral, BenceJones, and Boussingnult, who, with rare exceptions, always foundnitrates present in rain, the experiments of Boussingault giving amean of 0.5 mgram. per litre.This absence of nitrates at an altitude of nearly 3000 meters wouldlead to the conclusion that the formation of nitrates in the atmosphereduring thunderstorms takes place in regions below that height.Observations have shown that 184 thunderstorms have been observedfrom the Pic du Midi from August, 1873, t o August, 1882, with an inter-ruption from September, 1872, to June, 1874.Of these, ’only 23 tookplace a t altitudes above 2300 meters. No observation is recordedof a storm taking place a t a greater height than the summit of the Pic.It may therefore be concluded that in the Pyrenean region the violentelectric disturbances which give rise to storms do not take place a t analtitude of 3000 meters, and therefore the formation of nitrates undertheir influence takes place in lower regions.Although these results are isolated, yet their concordance may leadto the following generalisation. Atmospheric nitrification is pro-duced in the lower regions of the atmosphere in the zone between thelevels of the earth and sea and the mean height of the clouds.Theammonium nitrate is in a state of powder, and does not rise to anygreat height. The observations confirm the opinion of Boussingaultthat the ammonium nitrate is not in a state of tension in the atmo-sphere, otherwise it would diffuse itself uniformly throughout thedifferent atmospheric strata in a manner similar to the carbonicanhydride and ammonia. This absence of powdered nitrates a tgreat altitudes accounts for the transparency of the atmosphere inthem, and shows that the mountain vegetation and mountain soils canderive the nitrogenous matters which hthey contain only from theatmospheric ammonia. L. T. 0’s.Hailstorms and their Origin. By RINICEER and D~SSEKEL (Bied.Ceiztr., 1882, 721).-The transformation of a thunderstorm into ahailstorm is caused by local peculiarities ; the direction of these stormsis from S.W., W., and N.W., and the fall of hail occurs only whenafter a succession of hot days thunder-clouds pass first over barrenand thinly-wooded high land, and then, meeting with contrary or side-winds, are brought to rest over well-wooded and warm valleys.Hail-storms are never produced from thunderstorms which have passedover high-lying fir woods, for then the electricity has been sufficientlyabstracted to prevent the formation of hailstones. The size of thestones is proportional to ihe height from which they fall, high locali-ties receiving only small stones ; stones of the size of hazel-nuts fall* During the evaporation of the water, access of air was prevented, thus avoid-ing contamination by the nitrtltes contained in the products of conibustion ofthe source of heat, a source of enor pointed out by Schonbein, and subsequently byWaringtonVEGETABLE PHYSIOLOGY AND AGRICULTURE.235from a height of 100 m., while those as large as walnuts have fallenthrough a distance of 200 m. Storms descending into villages fromthe ridges of high mountains are the most severe. From all theobservations made it is clear that by planting the higher mountainousregions witb trees, the greater niimber of hailstorms which wouldotherwise occur may be prevented.Dossekel in another district of Switzerland comes independently tothe same conclusion as those mentioned above. E. W. P.Cultivation of various Crops.By J. FITTEOGEN and others(Bied. Centr., 1882, 745-752) .-Fittbogen, comparing the cropsobtained by sowing Hallett's Pedigree, Sheriffs Square-head, and NewZealand White Wheat, finds that Square-head produces the best yieldin all respects, and that the amount of nutrient's in all three sorts isthe same. Oppenau grew three sorts of roots, and found that Cham-pion Yellow Globe gave the highest yield and with the narrowestnutrient ratio. Hoffmann obtained a yield of prickly comfrey of1200-3000 crn. per morgen, cutting it twice in the first year, but4-5 times during each of the succeeding 20 years; it should bemixed withchaff, &c., as owing to its roughness it is a t first some-what distasteful to animals. E. W. P.Soja Bean.By E. KINCH (Bied. Centr., 1882, 753--755).-Anumber of analyses of the bean from various sources are given: 10per cent. of the carbohydrates are analogous to mellitose, and of thealbumino'ids 1 per cent. is as peptone, and 1-2 per cent,. as amides;the high percentage of albumino'ids (37.8 per cent. in the Japanese)places this bean above all other leguminoss-in fact the compositionin this respect approximates to that of meat; moreover, the strawsurpasses in value that of wheat and lentils and also hay as regardsnitrogen. Tables of the composition of various Japanese foods madefrom soja are also given, as well as of the ash-constituents of the beanand straw. E. w. p'.Chemical Studies on the White Sugar-beet of Silesia, ByH. LEPLAY (Compt.rend., 95, 760-763 ; 851--854).-These paperscontain the results obtained by the analyses of the roots, stalks, andleaves of the beet in different stages of its growth, and the author givesan account, first, of the amounts of organic salts of potassium andcalcium, taken as a whole, in different parts of the plant a t differentstages of vegetation ; secondly, of the quantities of these salts in thesoluble state in the juice, and in the insoluble state in the tissues;and, finally, of the condition of that portion of these salts which isfound in the insoluble state in the tissues. The author discusses alsoto some extent the eEect of different soils on the amounts of potassiumand calcium to be found in the plant.In continuation of his researches on tlhis subject', the a<uthorhasanalysed the roots, leaves, and stalks of the beet, with especial referencet o the richness of the roots in sugar.The quantity of sugar foundappears to be closely connected with the quantity of calcium in theform of organic insoluble salts in all parts of the plant during growth.r 236 ABSTRACTS OF CHEMICAL PAPERS.Whenever the richness in sugar decreases, the quantity of organic in-soluble calcium salts diminishes in all parts of the plant. Thesecalcium salts have also an important influence i n diminishing the rateof decrease of richness with increase of volume of the root.The decrease of richness of the root under the influence of increaseof volume and weight corresponds to a decrease in the quantity ofcalcium carbonate in the immediate neighbourhood of the root.The means of diminishing the exhaustion of the soil and conse-quently the influence of that exhaustion on the richness of the root,consists in multiplying the points of contact of the rootlets with thesoil by increasing the number of roots to a given surface of soil-thatis, by growing the roots more closely together.This correspondswith the well-kr:own fact that the yield of sugar is very much in-creased when the plants are grown close together. E. H. R.Influence Exerted by the Weight of Potato ffSets.” ByTOBISCH (Bied. Cefatr., 1882, 759) .-To the advantage gained by usingheavy sets there is a limit beyond which the increase of yield is lessthan the weight of the sets employed; moreover, the number ofdiseased tubers increases with increased size of the sets.E.W. P.Amount of Gluten in Wheat. By STUMPF (Bied. Centr., 1882,786) .-The best German and American summer wheats contain24 per cent. of gluten ; South Russian, 45 per cent. ; Californiao andAustralian 23-24 per cent. Russian wheat is mixed with starchyEnglish wheat, and sold under the name of “Mixed Danzig Wheat.”Albuminoid and Non-albuminoid Nitrogen Compounds ofcertain Vegetables. By C. BOHMER (Landw. Versuchs.-Stat., 28,247-262) .-The vegetables examined. were those ordinarily used f o rhuman food; they were grown in the garden of the ExperimentalStation a t Munster, and cut and dried when fit for use. The sampleswere analysed with regard to total nitrogen, fibre, ash, &c.: theamount of total nitrogen varied from 1.9 in carrots, to 5.57 per cent.in broad beans, but ranged in all cases, except the former, between4 and 5.5 per cent.: the percentage of water varied from 4.3 in thetruffle to 96 in asparagus.I n splitting up the nitrogenous bodies into their various groups, themethod of Stutzer was employed, together with precipitation by leadhydroxide, and the method by difference. Concordant results wereobtained by all three methods. The ammonia was determined bymeans of milk of lime, as recommended by Schloesing and modified bySchulze and Emmerling, and estimated as platinochloride. To sepa-rate and determine the quantities of amido-acids and acid amides, thealbumino’ids were precipitated with cupric hydroxide, and the filtratewas concentrated and divided into three equal parts, the Erst of whichwas treated a t once with hypobromite, and the second after two hours’boiling with hydrochloric acid and neutralisation : the difference ofthe two gave the nitrogen of the carboxyl-groups, i.e., of the amido-acid amides.The third portion, after being boiled first with hydro-chloric acid and then with potash to drire off ammonia, was used forE. W. PVEGETABLE PHYSIOLOGY AND AGRICULTURE. 237tbe determination of the pure amido-acids by means of nitrous acid,the nitric oxide formed being absorbed by a strong solution of per-manganate.As the following table shows, t,he above determinations do notexhaust the total quantity of nitrogen present ; the remainder wasfound not to belong, in any considerable quantity, to the peptone-group, but must be classed under the heading of peptosd bodies, sub-stances which have a position intermediate between peptones and thecrjstalline final decomposition-products of albumin.The appended table gives the percentages in the dried substance :-Totalnitrogen.Spinach ..........4.56Peas ............ 4.69Beans.. .......... 5-57Asparagus ........ 4.13Lettuce .......... 4*@5Carrot.. .......... 1.91Turnip-cabbage.. .. 4.64Cauliflower ...... 5.11French beans.. .... 4.32Mushrooms ....... 4-68Truffles .......... 4.50N asalbumi-noids.3.513.564-393.332.971.572.052-602.673-34!3.63N asNH3.0.0210.0200.013?0.0240.0060.0180.0170-0100.0110.008N as amido-acidamide.0.1230.0520.0270.1550.0130.15 10.1040-0610,0920-072N asamido-acid.0.0630.3610.0590.15%0.1420.2310.5660.4420.4160.202_-J. K.C.Fertility of a Soil as Dependent on the Action of Worms.By N. HESSCN (Bied. Centr., 1882, 723-727).-A portion of thispaper is devoted to a short account of the work of others on theaction of worms in the soil ; the analyses of " worm earth" as com-pared with that of ordinary soil are given, and from these analysesit is evident that the composition of worm earth is not far removedfrom that of ordinary leaf mould. That the ordinary earthworm(Lumbricus tsrrestris) eats earth is undoubted, but it does so only forthe purposes of forming its burrow, whilst for the purposes ofnourishment it feeds on decayed vegetable matter.By its variedactions the worm canses an even distribution of natural manurialmatter through the soil ; by removing leaves and other loose particlesfrom the wind the decay of matter is rendered more rapid, decayedmatter is distributed through the soil, and the subsoil is renderedmore open for the roots of plants. The worms as a rule live in theupper soil, descending only during very cold weather. The passagesleft by worms are of importance to rootlets, for there they always findmoisture and an atmosphere rich in carbonic anhydride, and evenduring winter there is always moisture to be found in these passages,for moisture rising from below and unable to pass away from thesurface owing t o its frozen condition, is condensed like dew on therootlets.E. W. P.Effect on the Fertility of the Soil produced by Coveringit with Farmyard Manure. By E. WOLLNY (Bied. Centr., 1882238 ABSTRACTS OF CHEMICAL PAPERS.735-738) .-A not unimportant effect produced by spreading dungon a field is that the soil is kept warmer in winter and cooler insummer, and this action is intensified by a larger amount of enclosedair, as in the case of straw, which shelters the ground more than well-rotted dung. Again, this covering of manure lowers the evaporationof water, which results in a higher percentage of moisture in thesoil, and a consequent increase in the amount of drainage-water.These actions are not always of use, so much depending on thecharacter of the soil.Clover, sainfoin, and lucerne are all benefitedby shelter, and are enabled to start growing earlier in the spring.But if a soil, such as clay, is highly retentive of moisture, then thequantity of water retained is too great, and the crops suffer in con-sequence. Further, close heavy soils which are benefited by frost,whereby they are lightened, remain heavy, and if the field is on ahill-side, and soaked with water, heavy rains will wash awayall nourishment. The covering of manure raises the percentage ofdrainage-water running from light soils, and thus there is a loss of plantfood ; but on soils of medium texture this method of applicationcannot be too strongly recommended, and no loss of ammonia willoccur, except perhaps during the very hottest weather.E.W. P.Manuring Sugar-beet with Dung. By BESELER (Bied. Centr.,1882, 784).-Sheep-dung must not be applied alone, for the high per-centage of nitrogen and potash is detrimental t o the quality of thesugar-beet. Cow-dung must be applied in the late summer or autumn,and allowed to lie some time before ploughing in ; thus tlhe roots ob-tain the nitrates in the early stage of growth, f o r if nitrates areapplied in the later stage the yield of sugar is reduced.E. W. P.Manuring Alpine Meadows. By M. MARCKER ( B i d Ce)Ltr.,1882, 783).-Meadows in the Alps are generally manured with liquidmanure, farmyard manure mixed with water, also with superphos-phate.In East Switzerland, no potash is added to the superphos-phate, but in Western Switzerland, where the soil is more chalky,potash is added. The result of such manuring is that the hay crop isat least three weeks earlier than on the unmanured meadows ; a secondcrop may also be taken. Observations have shown that the presenceof chalk is necessary for the satisfactory action of potash, and that theatmospheric ammonia absorbed by the salts of potash is converted intonitrates by the agency of the lime, whilst nitrification does not occurwhen lime is absent. These facts account for the unsatisfactoryresults obtained when potash is added to nnmarled sandy soils.E. W. P.Employment of Peat as Litter. By A. LENNB (Bied. Centr.,1882, 785).-The following is the analysis of horse manure whenpeat was used as litter instead of straw. The use of the latter is themore expensive of the twoANALYTICAL CHEJIISTRT. 239In 1000 parts. Peat manure. Straw manure.PZO5 ........ 2.23 1-18K,O ........ 4.57 4.50N .......... 6.06 3-90H20 ........ 705.81 750.00E. W. P.Transformation of Blood into a, Solid and InodorousManure by Means of a new Ferric Snlphate. By P. DELA-CHARLONNT (Compt. rend., 95, 841-843) .-The author states that byuse of an acid ferric sulphate having the compositionFe203,4S0,,12H20,instead of the neutral sulphate as usually employed, a coagulum isobtained from the blood at the ordinary temperature, which loses halfits water by simple drainage, whilst the remaining water can beexpelled to a great extent by hydraulic pressure. Great expense isthus saved, as far less evaporation is necessary. The sulphate in ques-tion can easily be obtained by oxidising ferrous sulphate with nitricacid, sufficient sulphuric acid having been added to make up thequantity required for an acid sulphate of the above composition. Onconcentrating the solution sufficiently, the salt crystallises out.E. H. R

ISSN:0368-1769    

DOI:10.1039/CA8834400229

出版商:RSC    

年代:1883

数据来源: RSC

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ANALYTICAL CHEJIISTRT.An a1 y t i c a 1 C h e m i s t r y.239Use of Diphenylamine and Aniline in Qualitative Analysis.By C. LAAR (Ber., 15, 2086--2090).-The author recommends di-phenylamine in preference to aniline as a qualitative reagent fordetecting (more especially) chloric acid. A solution of the base inconcentrated sulphuric acid gives with dilute chloric acid a beautifulblue coloration. The author finds, however, that other oxidising agentsgive a similar colour.Sauer’s Method of Estimating Sulphur, and some Modifi-cations of it. By W. G. MIXTER (Chem. hTews, 46, 217).-Sauer’smethod of burning tlie compound in oxygen and oxidising the sulphu-rous anhydride by bromine is liable to error, by reason of the uncon-densed fumes of aulphuric acid which are lost ; these may, however,be retained, and the amount estimated, by passing the mixed gases intoa large empty flask, when the fumes remain at the bottom and slowlycondense.A hydrochloric acid solution of bromine is found to be nobetter than bromine-water as an oxidiser, and as there is a consider-able loss of bromine if the mixed gases pass through saturated bro-mine-water, an ordinary two-bulb U-tube with a constriction at oneend of the horizontal part just below the bulb is used. By usingthis apparatus a minimum of bromine is lost, and a constant supplyof it is preserved for the purposes of oxidation.E. H. R.E. W. P240 ABSTRBCTS OF CHEMICAL PAPERS.Testing for Barium or Sulphuric Acid. By S. PICKERING(Chem. News, 46, 223).-The smallest qnantity of barium which canhe detected is 1 part Ba in 833,000 parts H,O; the reaction is notrendered more delicate by the use of alkaline ammonium sulphate.The light should fall vertically, there being a black background,allowing the light to fall on a portion only of the liquid.Estimation of Sulphuric Acid in Presence of Alkaline Chlo-rides.By B. SCHULZE (Landw. Versuchs-Stat., 28,161-165) .-Theinfluence of nitrates on the precipitation of barium sulphate hasalready been studied by Fresenius, and he recommends warming theignited precipitate with hydrochloric acid and washing with hotwater. After filtration, the filtrate is evaporated to dryness to sepa-rate dissolved barium sulphate, the latter added to the rest of theprecipitate, and the whole weighed.By this means, the nitrates areremoved, but he does not enter into the question as to whether chlo-rides are also to be found in the precipit'ate. I n the estimation ofsulpbur in organic substances by fusion with potash and saltpetre,excess of alkaline salts is always present : when they are in the form ofnitrates, the precipitated barium sulphate will have to be purified by theabove method ; the author, however, prefers to convert the nitrates intochlorides by heating to dryness with hydrochloric acid. Upon re-dissolv-ing and filtering, the sulphuric acid is precipitated by a little bariumchloride, and the precipitate after filtration ignited alone, and finallywith sulphuric acid, and weighed in the usual manner.A precipitateobtained this way was treated with a few drops of hydrochloric acid,and then with boiling water, and filtered. The fillrate showed quite astrong sulphuric acid reaction with barium chloride, which could onlyhave arisen from the presence of alkaline sulphates in the precipitate,and was of course due originally to the co-precipitation of alkalinechlorides. In general, about 3 per cent. of the original precipitatewas removed in this manner. To ascertain whether barium sulphatewas also removed in any quantity by this process, so as to necessitjatethe evaporation of the wash-water, as in Fresenius's method, furtherportions were treated two or threc times with hydrochloric acid, andthe change of weight in each case noted. The loss by the second andthird treatment was however found to be so small that it could beneglected ; but one treatment with acid seems to be essential in allcases where excess of alkaline chlorides is present.Estimation of Phosphoric Acid as Magnesium Pyrophos-phate. By T.S. GLADDING (Chem. News, 46, 213).-The processesa t present in use for the estimation of phosphoric acid as magnesiumphosphate are not suEciently accurate, as an error of even 0.1 percent. in the amount of phosphoric acid can affect the value of a cargoof phosphate t o the amount of several pounds. Various modificationsof the usual magnesium process have been tried, and it has beenfound that the following is the best to employ :-To the solution of phosphate 75 C.C. in volume and strongly ammo-niacal, add magnesia mixture from a burette at the rate of one drop persecond, stirring meanwhile ; after the addition of the magnesia, addE.W. P.J. K. CAXALTTICAL CHEJIISTRT. 24125 C.C. of strong ammonia, leave the whole a t rest for three hours,and wash the precipitate with strong ammonia water (1 : 3), the im-portant point being the gradual addition of the magnesia mixture. Theerrors then range from 0.05 per cent. without previous precipitation asmolybdate to 0.1 per cent. with previous precipitation as molybdate.E. W. P.Estimation of Phosphoric Acid. By L. MAYER and E. v.SCHNID (Bied. Cent?-., 1852, 7841).-The solution of any superphos-phate is made according to the usual method, and is then freed fromsilica ; to 50 C.C.of this solution, 5 C.C. ammonia is added until apermanent precipitate is formed, and then 50 C.C. of a solution of ammo-nium citrate (1 : l), 25 C.C. of the usual magnesia mixture, and 100 C.C.concentrated ammonia solution are to be added. The mixture is to bethoroughly stirred every ten minutes, and after three hours filtered,the precipitate washed with ammonia water (1 : 3) and ignited. Thepresence of much alumina and lime is detrimental to the results, butthe addition of 10-15 C.C. strong ammonium chloride solution counter-acts the influence of the alumina ; to remove the lime, the imperfectlywashed precipitate is to be dissolved in a little dilute hydrochloricacid, and reprecipitated by 30 C.C. citrate, a few drops of magnesiamixture, and 60 C.C.ammonia solution. E. W. P.Analysis of Potassium Thiocarbonate. By GUYOT-DANNECY( J . Pha~m. [ 5 ] , 6, 336-337).-A flask of two litres capacity contain-ing 100 grams zinc chloride dissolved in a litre of water is fittedwith a doubly perforated cork. In one perforation, a funnel tube isinserted which passes to within 1 cm. of the bottom, whilst in theother a tube bent a t right angles is inserted, and by its means theiiask is connected with a condenser, to which is attached a receiverimmersed in ice. The flask is heated to 60" in a water-bath, and thepotassium thiocarbonate added in small quantities a t a time ; a briskeffervescence takes place with evolution of carbon bisulphide, alleffervescence is allowed to cease before a fresh quantity of the thio-carbonate is added.When all the thiocarbonate is added, the distilla-tion is continued until all the carbon bisulphide has passed over to thereceiver. From its weight the quantity of thiocarhonate present isobtained: the weight of the zinc sulphide gives the proportion ofother substances.Instead of using SL water-bath for heating the flask, the authorprefers to suspend the flask by means of a cord over a flame, wherebyi t is sheltered from the chance of breakage, and allows the flask to begently shaken without disturbing the apparatus, and thus to preventbumping. L. T. 0's.Normal Solutions for the Volumetric Estimation of Iron.By B. BRITTON (C'hem. Centr., 1882, 733).-The author has examinedn number of specimens of iron, such as are generally used f o rstandardising, and found them much more impure than is generallysupposed.The average percente,ge of iron found in a number ofpianoforte wires was 98-76. The purest sample of bar iron fro242 ABSTRACTS OF CHEMICAL PAPERS.Norway and Sweden contained, however, 99*6 per cent. iron.salts were found to be still less trustworthy than metallic iron.Sources of Error in Estimating Iron in Ores by the StannousChloride Method. By K. F. FOHR (Dirtgl. polyt. J., 246, 236).-According to the author very appreciable quantities of ferric chlorideare volatilised and lost whilst an iron ore is being heated with hydro-chloric acid, especially when the operation is conducted in an openvessel. I n the case of some ores, this source of error is, however,counterbalanced by another error, due to the presence of manganesedioxide.In this case, the liberated chlorine remains to a slight extentin solution, and may therefore make up for the loss of ferric chloride.By W. DIEHL (DingZ.polyt. J., 246, 196--200).-The author has made direct comparisonsbetween Bunsen’s method of distilling the peroxide with hydrochloricacid, passing the liberated chlorine into solution of potassium iodide,&c., and Mohr’s modification, according to which the peroxide isdigested with the hydrochloric acid and potassium iodide. He hasalso tried the effect of substituting other acids for hydrochloric acid.The substances experimented with are potassium dichromate, the twooxides of manganese, Mu,O, and Mn02, and lead dioxide.His resultsshow that the more simple method of Mohr can be relied on, andthat in some cases other acids can be employed in place of hydro-chloric acid. The same results are obtained with potassium dichro-mate, whether hydrochloric or oxalic acid is used, but with theoxides of manganese the latter acid cannot be employed. Acetic acidcan be used in the case of manganese dioxide, and with advantagealso in that of lead dioxide. The author also finds that the pesenceof iron does not interfere in estimating the available oxygen in pyro-lusite by this method.By A.LEDEBUHR (Chem. Centr., 1882, 733) .-This method depends on theconversion of manganese into permanganate, and is recommended byGoetz for the estimation of that metal in iron and steel.He dissolves0.2 gram of the iron to be tested in nitric acid, and dilutes with dis-tilled water to 100 c . ~ . To 10 c . ~ . of this solution 2 c . ~ . of nitric acidare added, the mixture heated to boiling, and then well shaken withan excess of lead dioxide. After again warming, the liquid is allowedto cool and is filtered through asbestos into a burette. Potassiumpermanganate solution of known strength is poured into a similarburette, and water added until the same tint is obtained as in the firstburette. The strength of the solution is calculated from the amountof dilution necessary.Haswell’s Method for the Volumetric Estimation of Mercury.By H. v. J~~PTKER (Chem. Cenhr., 188.2, 727).-To a solution contain-ing mercuric chloride, standard solution of ferrous sulphate, acidulatedwith sulphuric acid, is added in excess.The solution is then madestrongly alkaline with potash, and afterwards acidulated with a con-IronA. K. M.A. K. M.Volumetric Estimation of Peroxides.A. I(. M.A Colour-method for the Estimation of Manganese.A. K. MANALYTICAL CHEMISTRY. 243siderable excess of hydrochloric acid. On well shaking, the precipi-tate of mercurous chloride becomes quite white. The excess of ferroussalt in the solution is next oxidised by standard permanganatJe, andon then adding a few drops of stannic chloride solution and a furtherquantity of permanganate, the mercurous chloride becomes convertedinto mercuric chloride, the disappearance of the precipitate indicatingthe completion of the reaction.Each molecule of permanganate,added after oxidation of the excess of ferrous sulphate, correspondswith I atom of mercury.Separation of Silver from Alloys. By SOLTHIEN (Arch. Plznrm.[3], 20, 201).-The author simplifies the process published by him inthis Journal, 1880. The alloy is dissolved in the minimum quantityof crude nitric acid, and then decomposed by a strong excess of ammo-nia; in this liquid placed in cylinders is suspended strips of copper,A. K. M.upon which the silver will be deposited. E. w. P.Use of Oxalic Acid as a Test for Arsenites in Alkaline Salts.By C. PATROUILLARD (Phnrm. J. Trans. [ 3 ] , 13, 362).-An answer toa paper in this Journal by Naylor and Braithwaite, who aflirmedthat, contrary to the statement of the author, oxalic acid does notreduce arsenic acid.The author repeats his statement made in 1874,that oxalic acid does reduce arsenic acid in combination, and the morecompletely the more neutral the combination. In the original paperthe uncombined acid was not referred to. E. w. P.Detection of Iodoform, Naphthol, and Chloroform in theFluids and Organs of the Animal Body. By S. L u s r r G a r E N(Monutsh. Chem., 3, 715--722) .-Iodoform and naphthol being nowused, as well as chloroform, in medical practice, it becomes a matterof importance to be able to detect them in animal fluids and organs.1. Iodqform-The recognition of this substance by its saff ron-likesmell, and its peculiar crystallisation in six-rayed stellate groups,being often greatly hindered by the presence of other compoundsoccurring in animal liquids, the author directs attention to a newreaction not open to this objection.When iodoform is added by smallquantities to a solution of phenol (20 grams) and sodium hydroxide(40 grams) in 70 C.C. water, heated on the water-bath or to 120" in aparaffin-bath, it quickly dissolves and colours the liquid red ; and ifthe heating be continued till about 60 g. iodoform have been dis-solved-which takes several days at the heat of the water-bath, o r ashorter time in the paraffin-bath, and the solution be then acidulatedwith hydrochloric acid and distilled with steam-the excess of phenolwill pass over, probably together with salicylic and parabenzoicaldehydes, while in the flask there will remain a resin, soft and black-brown while warm, brittle and red-brown after cooling.This resindissolves easily in alcohol, with yellowish, and in alkalis with a finecrimson colour, which disappears on adding a slight excess of acid,b u t reappears on neutralisation ; the alkaline solution is coloureddark-red by potassiixrn ferrocyanide. The product of the above reac-tion, like that resulting from the action of an alkaline phenate onchloroform, doubtless consists of rosolic acid and allied bodies. T244 ABSTRACTS OF CE[ENICAL PAPERS.exhibit the reaction on a small scale, an alkali phenate is placed a t thebottom of a short test-tube, in very small quantity only, because thebrown colour which these salts acquire when heated, would maskany slight red coloration that might afterwards be developed. Analcoholic solution (1-3 drops) of iodoform is then added, and themixture is cautiously heated over a small flame ; whereupon, after afew seconds, there appears a t the bottom of the tube a red deposit,which dissolves with crimson colour in a few drops of dilute alcohol.To detect iodoform in urine by this reaction, the liquid is distilledwith steam till about 50 C.C. has passed over, and the distillate, mixedwith a small quantity of potash-ley, is shaken with ether in a tap-funnel; the ethereal extract is evaporated to dryness; the residuetreated with absolute alcohol ; and the alcoholic solution tested withphenol as above.For detection in blood, the liquid, diluted with 2 vols.water, ismade alkaline and distilled with steam, and the distillate is treated inthe manner just described, excepting that the ethereal extract sepa-rated from the aqueous alkaline solution is mixed with a little sulphuricacid to neutralise any amines that may have passed over in the dis-tillation. The smallest quantity of iodoform that can thus be detectedin blood is 4-5 mgrms.I n the reaction above described, the phenol may be replaced byresorcinol, but not by quinol or catechol.2. NcxpiLthoZ.-When chloroform is added to a solution of a- or/3-naphthol in strong potash-ley, and the liquid is heated to about 50°,a fine Prussian-blue colour is developed, changing, in contact with theair, into blue-green, green, green-brown, and finally brown.Thesame reaction is produced by crystals of chloral hydrate, which, inpresence of the alkali, is converted into formic acid and chloroform.To detect naphthol in urine by this reactlion, the liquid is acidulatedwith hydrochloric acid and distilled with steam till about half haspassed over ; the distillate is shaken with ether ; the ether evaporated ;and the residue, dissolved in potash, is tested for naphthol as above.As, however, the alkaline solution is always brownish, the colour pro-duced on adding the chloroform inclines more or less to green. Theresidue in tLe retort may also be tested for naphthol in a similarrnanner; but as its ether solution is always strongly coloured, it isnecessary to evaporate this solution to dryness, dissolve the residue inalcohol, decolorise with animal charcoal, warm, filter, evaporate thefiltrate to dryness, and test the residue as above.3.C?kwojbrn~.-This compound may be detected in animal fluidsexactly in the manner just described, with addition of naphtholinstead of chloroform to the alkaline solution. H. W.Reducing Power of Grape-sugar for Alkaline Copper Solu-tions. By P. ALLIHN (Chenz. Celntr., 1882, 731).-Soxhlet and othershave shown that the power of grape-sugar to reduce Fehling’scopper solution is not constant, but varies under different conditions.The author has examined the methcd described by Degener (Abstr.,1882, lo$), but finds it open to the same objection as Fehling’smethod.A. K. 31ANhLY TICAL CHEMISTRY. 245Amount of Extract in Wines (Tyrolese). By E. MACH andC. PORTELE (Bied. Cemtr., 1882,773-775).-1n thin sour wines, 0.1 percent. sugar is perceptible by the taste, and in some cases as little as0.05 per cent. can be detected. The factors influencing the per-centage of extractive matter are many : continued dryness lowersextract and acidity ; old wines are poorer in extract than new ; as thequality of a red wine rises so does the percentage of extract, reachingeven higher than 4 per cent. The lowest observed (but there may belower) percentage of extract in pure white wine was 1.42 per cent. ;in red, 1.76 per cent.Rapid Method of Estimating Salicylic Acid in Wines, Bcc.By A. R E M o N r (Comyt.rend., 95, 786-788).-The author prepares asolution of salicylic acid to serve as a standard of comparison. 50 C.C.of a liquid analogous to that to be tested are taken, and into it isintroduced the maximum amount of salicylic acid allowed by law. Thisis then shaken several times with 50 C.C. of ether, and the whole leftat rest for a time. 25 C.C. of the ethereal solution are then taken andevaporated a t a temperature below its boiling point in the presence of10 C.C. of water, so that the latter dissolves the salicylic acid from theether as it volatilises. The 10 C.C. of water are then made up to25 c.c., and the liquid thus prepared is used as a standard of com-parison.I n testing a wine, for example, 10 C.C. are treated with 10 C.C.of ether. 5 C.C.of the ethereal solution are then evaporated, asdescribed above, with 1 C.C. of water, which is then made up to 5 C.C.This is placed with the wash-water in a glass vessel of 30 C.C. capacityand of 15 mrn. internal diameter, the standard liquid being placed inan exactly similar vessel. A solution of ferric chloride, containing10 grams to the litre, is then added drop by drop to both vessels, untilthe colour no longer deepens (three or four drops usually suffice).The comparison of the depth of tint is sufficient to decide whetherthe liquid tested contains more or less salicylic acid than the standard.It is always advisable to take as a standard of comparison a liquidsimilar to that to be tested. The method is applicable, without modi-fication, to fruits and syrups.E.W. P.E. H. R.Occurrence of Myronic Acid and Estimation of the Cor-responding Mustard Oil in the Seeds of Crucifer= and inOil-cakes. By V. DIRCKS (Landw. Vessuchs.-Xtat., 28, 179-200) .-The amount of mustard oil is determined by oxidation with alkalinesolution of permanganate, and precipitation with barium chloride.Test experiments were made with mustard oil, which was in somecases directly oxidised, and in others distilled into the oxidising solu-tion. I n the former method, a weighed quantity of oil was introducedinto a thick flask with excess of alkaline permanganate solution, theflask sealed up, thoroughly shaken, and heated for some time on awater-bath, until the green colour had disappeared, and it was againred. It was then opened, the contents evaporated to dryness, andtaken up with hydrochloric acid, again evaporated, dissolved, and pre-cipitated hot with barium chloride.Comparative experiments wit846 ABSTRACTS OF CHEMICAL PAPERS.nitric acid as oxidising agent were fairly satisfactory. In the dis-tillation method the oil was weighed out into a tubulated retort con-nected with a condensing apparatus and receiver with a doubly-boredcork, into the other bore of which a Will-Varrentrapp nitrogen appa-ratus bent a t right angles was passed, connected a t its other end withanother of the same, and the whole apparatus communicated with anair-pump. The receiver and nitrogen bulbs were filled with perman-ganate solution, and after the oil was distilled over, were treated asbefore.Experiments showed that the sulphur determinatiops wererather too low; and this the author thinks is due to the excess ofalkaline chlorides present, in which, as some test experiments shorn,barium sulphate is slightly soluble, 0,025 gramKC1 and 0.1 75 gramNaClrepresenting about 5.5 mgrms. BaS04.The mustard oil was determined by this method in cake and seedsof black mnstard and rape, and in the seeds of Xinapis arvensis. Thefinely-powdered substance was mixed with ten times its weight ofwater, and allowed to stand nine hours a,t 50°, this being necessaryto allow of the easy distillation of the oil. It was then steam-distilled, a current of air being drawn through at the same time toensure thorough mixture, the sulphuric acid being estimated asbefore.By observing these precautions, constant and trustworthyresults may be obtained. The thorough stirring of the contents of theretort, is absolutely essential to expel the whole of the oil, and this isbest done by a tube stopped up a t the end and perforated with smallholes, so that the current of air is well divided in passing through theliquid. The amount of fat present and the relative quantities of sub-stance and water do not seem to have any effect. The followingpercentage quantities of mustard oil were found : Black mustard seed-cake, 1.39; rape seed from 0.018 to 0.037; rape seed cake, 0.020 to0.109 ;. yellow mustard seed cake, 0.018 ; tarnip seed, 0.038 ; seeds of,Sz’rzapw aruensis, 0.006.In the case of rape seed cake, the quantity ofoil decreases apparently with the age of the cake. Whether this isdue to a decomposition of the myrosin or of the ferment, the author isstill engaged in determining. As the seeds of the wild plant Sinapsisaruensis are used f o r adulterating rape seed, and as the former containscarcely any mustard oil, the amount of the latter in rape seed may bealmost taken as a standard of purity, if it should be found that theamount of oil does not greatly vary in samples from different localities.By R. ENMERICH (Bied. Centr., 1882,762) .-Emmerich has compared the gravimetric estimation of milk fatwith the processes of Soxhlet, Hoppe- Seyler, and Feser. Soxhlet’sand Hoppe-Seyler’s method gives a difference of 0-0.4 per cent.,whilst the error of Feser’s optical method is on the average 0.25 perJ.K. C.Estimation of Milk Fat.cent. too high. E. w. P.Analysis of Butter. By A. v. BASTELAER (Client. Centr., 1882,731).-A weighed quantity of butter is heated at 100-120°, the lossin weight indicating the amount of water present. The fat is thenextract,ed by means of benzene, and its amount found on weighing thedried residue. This is finally ignited, the loss indicating the casejin, anANALYTICAL CHEMISTRY. 247the ash the sodium chloride. The presence of oleomargarine can bedetected by its odour when butter is heated to drive off the water, andalso by the high percentage of case’in due to the admixture of milk.A. K. M.By J. MUNIER (Chew.Centr., 1882, 730).-Theauthor has examined a number of different sorts of butter in eachmonth from October, 1880, to February, 1882. He adopted Reichert’smodification of Hehner’s method, and found that the proportion ofvolatile acids differed from time to time. It was lowest betweenOctober and January, increased from February to August, and after-wards again diminished. The author concludes, therefore, that inreporting upon a sample of butter it will be necessary to make allow-ance for the time of year at which the butter was made.By D. GSBEL (Bied.Centr., 1882, 766).-This instrument resembles a hydrometer, thezero of the instrument being that point to which it sinks when floatingin butter heated by the vapour from boiling water ; the other degreesare supposed to indicate the percentages of added fats; the resultsobtained by its use are very untrustworthy, for in one case it indi-cated 20 per cent.of foreign fats present in perfectly pure butter,moreover, a very slight variation in the temperature greatly affects thereadings. E. W. P.Butter Testing.A. K. M.Margarimeter of Leune and Harbulet.Albumin from Urine, coagulated by Nitric Acid and solublein Alcohol. By L. GARNIER (J. Pharnz. [ 5 ] , 6, 339--340).-In ex-amining for albumin the urine of persons t o whom turpentine andbalsams have been administered, it has been shown that nitric acidprecipitates resins soluble in alcohol simultaneously with the albumin.In two cases of nephritis, the urine treated by Heller’s process gaveprecipitates soluble in alcohol, although the pa.tients had not takenturpentine or balsams.The reactions of the urines are as follows:The albumin is coagulated by boiling alcohol, nitric acid, trinitro-phenol, and gives a red colour with Millon’s reagent, but the precipi-tate with nitric acid is soluble in alcohol. It is necessary, therefore,to avoid confounding such precipitates with resinous matters.L. T. 0’s.Estimation of Humus in Soils. By G. Lo~~s(Lundw. Versuchs-Stat., 28, 229-245).-0f the three methods usually employed forthe estimation of humus, namely, loss on ignition, oxidation withchromic acid, and combustion with cupric oxide, the intermediate oneis usually preferred, as being both rapid and safe. Lateia investigations,however, by Warington and Peake (this Journal, p.617) have shownthat lower results are obtained by oxidation with chromic acid thanby ordinary combustion ; the author was able to put this t’o the testin n long series of experiments. In employing the chromic acidmethod, the proportions given by Wolff were strictly followed out,and the carbonic anhydride was absorbed in a Pettenkofer’s appa-ratus. For combustion, the weighed quantity of soil was treated witha dilute solution of phosphoric acid, and dried over a water-bath: itwas then powdered, mixed with cupric oxide, and transferred t o a248 ABSTRACTS O F CHEMICAL PAPERS.combustion-tube open a t both ends, The products of cornhiistionwere first passed through a Fresenius’ drying tube, with moist wad-ding at the top, which was found quite sufficient f u r absorbing anyoxides of nitrogen which might be formed : the carbonic anhydridebeing absorbed by a Pettenkofer apparatus. Samples of 40 differentsoils were analysed by both methods, as well as by loss on igni-tion, and the conclusions of Warington and Peake were confirnicd ;oxidation by chromic acid giving on the average only 84 per cent. ofthe carbonic anhydride yielded by combustion, the extreme limitsheing 96 and 64 per cent.I n nearly all the experiments, the estimation of humus by loss oniqnition gave results very much too high, the only exceptions being inthe cases of moor and certain sandy soils.The deficit in carbon exhibited by the chromic acid method isattributable to two causes : either there are certain compounds in soilnot attacked by chromic acid, or else the whole of their carbon cannotbe converted into its ultimate oxidation-product. Experiments weretherefore made with certain substances, of which presumably theliunius is compounded, such as fibre, roots, &c. ; the fibre was foundto be fully oxidised, but not the roots; humic acid yielded 91 percent. of its carbon by this method, but in this case the formation of3 per cent. of acetic acid was observed, as well as the production of ahigher carbon acid. In the insoluble residue also, a, small proportionof unattacked carbon was found, which probably had existed in theform of brown coal. J. K. C

ISSN:0368-1769    

DOI:10.1039/CA8834400239

出版商:RSC    

年代:1883

数据来源: RSC

摘要:

248 ABSTRACTS O F CHEMICAL PAPERS.T e c h n i c a1 C h em i s t r y.Absorption and Utilisation of the Sulphurous Anhydridecontained in Furnace Gases. (BinyZ. poZyt. J., 246, 228-236.)-According to Hasenclever, sulphurous anhydride and the vapours ofsulphuric acid can be removed from a mixture of gases by sulphuricacid. Precht recommends cooling the gases to about 100°, and thenpassing them over moistened magnesium hydroxide previously mixedwith 1 to 2 per cent. coal. The product consisting principally ofmagnesium sulphite is then heated, and the evolved sulphurous auhy-dride is used for the manufacture of sulphuric acid. The addition ofthe coal is to help the decomposition of a small quantity of sulphatewhich is formed on igniting the sulphite. Aluminium hydroxide can besubstituted f o r magnesium hydroxide, but works more slowly.Schnabelemploys zinc oxide and basic zinc carbonate for absorbing sulphurousanhydride. The zinc oxide must be kept continually moistened withwater to prevent its becoming coated with a layer of sulphite. As inPrecht’s method, coal must be mixed with the zinc oxide, so that aftera time the latter becomes contaminated with a very appreciableamourit of ash. In order to remove this, the mixture is again exposeTECHNICAL CHEMISTRY. 249to furnace gases and the resulting zinc sulphite separated from theash by solution in water. The solution is used instead of water formoistening the zinc oxide in the next operation. Fleitmann passesthe furnace gases together with air through a furnace containing amixture of oxide of iron and coal ; ferrous sulphide being produced bythe reducing action of the latter.According to Kosmann's method, the gases are submitted to theaction of steam and water, by which a part of the sulphurousanhydride becomes oxidised and converted into sulphuric acid.Theremaining sulphurous anhydride is then decomposed by a solution ofhydrogen calcium sulphide, thus :-5 S 0 , + 2H2CaS2 + 2H20 = 7s + 2CaS04,2H20.A. I(. M.Antiseptics. By A. MAYER (Ried. Celztr., 1882, 777).-Stuttgart" preservative salt " consists of a mixture of 2 parts boric acid and 3 ofsodium chloride. " Septon," to preserve cheese from mould, &c., isonly a mixture of equal parts of acetic acid and water. " Glacialin saltmixture " and " glacialin rose-extract " are both mixtures of boric acidwith borax, the second mixture being intended t o preserve meatwithout altering its colour.By R.KOCH (Chew. Centr., 1882, 509-51 2) .-The mode of action of individual disinfectants has not been sufficientlyinvestigated, because of our incomplete knowledge of the infectioiismatter. An e$icierLt disinfectant ought, in the author's opinion, to killall living organisms and render all germs innoxious within twenty-fourhours. To test a disinfectant thoroughly, its action must be tried on .all disease-producing matter, and under conditions exactly similar tothose in which it is used in practice. Thus a disinfectant which doesnot kill fungi would be of no use in contagious skin diseases, whilstone which did not destroy bacteria would be inefficient in diseasescaused by these organisms.The author has investigated the action ofdisinfectants on bacteria. I n these experiments, he has taken greatcare in the cultivation of bacteria, selecting those which are seldomfound in the air. Experiments on the development of bacteria weremade on solid nutritious substances. The chief points observed are-1. If all the organisms are killed. For this it is sufficient to note theaction on the most persistent, viz., the bacilli spores. 2. The facilitywith which t,lie development, of micro-organisms in favourable nutri-tive solutions is prevented.Curbolic acid is almost without action on spores of Anthrax bacilli,e.g., the bacilli spores retained their vitality after being five days in a2 per cent.solution, and in another experiment 15 days in a 1 percent. It is, however, destructive to the living micro-organism, for1 gram of pure carbolic acid can completely prevent the developmentof Anthrax bacilli in 850 C.C. of a nutritive solution, and even shows amarked effect in 1250 grams. Its action on ofher bacteria is lessmarked. Carbolic acid in the form of vapour does not affect thegerminating power of bacilli spores at the ordinary temperature, evenafter being in contact with them 14 months; but a t 55", in half anhour many of the spores are destroyed, in three hours scarcely anyE. W. P.Disinfectants.VOL. XLIV. 250 ABSTRACTS OF CHEMICAL PAPERS.germinating power is discernible, whilst after five or six hours theirdestruction is complete.Raising the temperature does not increasethe activity. Carbolic acid vapour can only be conveniently used forsmall objects.The above results are obtained with aqueous solutions of carbolicacid. Solutions in oil or alcohol do not show any antiseptic proper-ties ; t'his is also the case with other disinfectants, e.g., salicylic acid,thymol, &c., except when they are used with substances containingwater, such as flesh, &c., when some of the disinfectant becomes active.SuZphurous acid, either alone or mixed with water or steam, does notdisinfect dry objects. Tf, on the other hand, the object is firstmoistened with sulphurous acid and then treated, brisk action isobserved ; it does not, however, destroy all germs.Its disinfectingaction is thus uncertain, and is not to be depended on.Amongst many others, zinc chloride and gZycero2 are proved to bewithout effect. In fact the only efective disiilfectants (see above)besides chlorine, brornh~e, and iodine, are corrosive sublimate, osmic acid,and potassizm perrnanganate. The last-mentioned only acts in strongsolutions ( 5 per cent.). Bromine and osmic acid are too expensive.Corrosive sublimate is Fery poisonous ; its action, however, is so veryquick that i t could be used for solid substances, which could then bewashed well with water.Szcbstances efective i n checking the germination of spores are corrosivesublimate, some essential oils, thymol, and amyl alcohol.Effect of the Presence of Sheet Zinc in Boilers, and aMethod for Preventing Explosions.By TRAVE (COW,@ rend., 95,522-524).-When sheet zinc is placed in iron boilers, galvanic actionis set up, and the water is slowly but continually decomposed, Theoxide of zinc which is formed neutralises the fatty acids in the feedwater, producing zinc soaps, which surround the boiler tubes andprevent the adherence of salts deposited by evaporation. The con-tinuous evolution of hydrogen might be expected to assist ebullitionand prevent superheating of the water. Since, however, it sometimesseems to fail in producing this effect, the author proposes to inject intothe water in the boiler a stream of air or a non-oxidising gas, such ascarbonic anhydride, in order to keep up ebullition and prevent super-heating, which is undoubtedly the cause of many boiler explosions.C. H.B.By P. GUYOT (Compt.r e i d . , 95, 693-695).-The crystallised portions of the alunite fromthe Tolfa Mines contain as much as 32 per cent. of the base, but theaverage composition of the mineral is-D. A. L.Industrial Value of Crude Alunite.A1203. SO,. K20. R20. Fe. SiO,.27.60 29.74 7.55 11.20 1.20 22.71 = 100.00When the mineral is gradually broken up, the fine powder is richerin alumina and potash than the coarser fragments. In the followingtable of analyses the numbers indicate the degree of fineness, thefinest powder having the highest number :TECHNICAL CHEMISTRY. 251First crushing.7 rI-h-1.2. 3.Calcination .......... 23.00 37.60 41.00 per cent.C r d e mineral.Alumina ............ 17.81 25.40 31.00 ,,Potassium sulphate .... 8.40 12.30 15.30 ,,Calcined mineral.Alumina ............ 23.13 40.70 44.90 ,,Potassium sulphat,e. ... 10.91 19.50 22.17 ,,Second crushing.r---------- 7 I. 11. 111. IV.Calcination. ..... 22.40 24.40 33.90 34-60 ,,Crude mineral.Alumina ........ 17.80 23.67 31.7.5 32.29 ,,Pota,ssium sulphate 8-51 11.95 15.31 15.40 ),Calcined mineral.Alumina ........ 22-93 31-31 48.04 49.40 ),Potassium sulphate 10.92 15-92 23.16 23.56 ,,Gutzkoff's Process for the Separation of Gold in California.( Chein. Ceiitr., 1882, 508--509.)-The principal materials for separa-tion are-1. Gold bar, containing 2 parts gold and 3 parts silver;this is granulated before being dissolved.2. Silver plates with 2 to10 per cent. of gold. 3. Silver plates mixed with copper ; before dis-solving, fine silver is added to these to reduce the percentage ofcopper to 12 to 8.The alloys a-te treated with boiling sulphuric acid in coveredvessels of cast iron (containing 2 to 4 per cent. of phosphorus, so asto better resist the action of the acid), capable of holding a charge of100 to 150 kilos. of alloy. The pots being partially filled with acid(the acid reservoirs are so arranged that the pots can be easily filled)and boiled, the charge is put i n ; after 15 minutes the necessaryadditional quantity of acid is added, and the whole boiled for three tofour hours. The hot liquid is then syphoned off by means of a vacuumarrangement into shallow iron tanks, capable of holding five charges,in which there is sulphuric acid of 58" B. in the proportion of 0.5 c.m.for every 100 kilos.of alloy a t 110" C. ; here the liquid remains atthis temperature until clear. The gold remains behind in the pots ;there is also some deposited along with graphite and lead sulphate inthe tanks. The hot clear liquid containing silver, copper, and ironsulphates is run into vessels and cooled to 30-40" by means of acurrent of water, when silver sulphate crystallises out ; the copper sul-phate is syphoned back into the tank. The silver sulphate crystalswhen drained are ladled into wooden vats lined with lead, having aC. H. B252 ABSTRACTS OF CHEMICAL PAPERS.false bottom with a tap underneath.A hot saturated neutral solutionof ferrous sulphate is poured over the crystals, and ultimately runout by the tap. The copper sulphate is dissolved first ; the liquid istherefore blue ; the silver sulphate is then reduced, the liquid becomingbrown, and at the end of the operation it is green; the reductionoccupies 3-4 hours. The liquids are separated ; the brown one holdsin solution 24 per cent. of silver ; the (green) ferric solution is treatedwith scrap iron, and is returned to the ferroiis sulphate store tank.The gases and vapours given off during the dissolving are condensedin leaden chambers, towers, and shafts. A figure is necessary for anefficient and clear description of the apparatus employed.D. A.L.Deplastering of Wines. By BLAREX (J. Pharrn. C l ~ i ~ 7 . [ 5 ] , 6,26?--870) .-The author confirms the opinions of Calles (Abstr., 1882,1336) on the deplastering of wines, maintaining that from a hygienicpoint of view the deplastering is more injurious than the plastering-(1) owing to the use of poisonous barium salts, and (2) because in thedecomposition of the potassium sulphate by the barium chloride thepotassium chloride is irij urious. L. T. 0’8.Application of Strontium Chloride in Purifying Syrups.By G. KOTTMAN (Dingl. polyb. J., 245, 395).--The juice obtained bydiffusion or pressure is treated with calcium chloride until the acidsforming insoluble calcium salts have been precipitated. The filtrateis then saturated with lime and again filtered.To the solution asuEcient quantity of strontium chloride is added, when a furtherseparation of acids in the form of insoluble stroiltiurn compounds iseffected. The author recommends to precipitate with calcium chloridein the first place, add strontium chloride after removing the calciumprecipitate, and finally saturate the mixture with lime. Strontiumcliloride may be employed also for the purification of syrups.D. B.Recovery of Sugar from Molasses by means of StrontiumHydroxide. By C. SCHEIRLER (Ding. poZyt. J., 245, 430-453,455-469, and 506-508) .-The author has recently patented an im-proved process for the recovery of sugar from molasses by means ofstrontium hydroxide, according to which molasses is diluted withwater, the degree of dilution depending on the composition and thepercentage of sugar contained in the solutions, and mixed with stron-tium hydroxide in the proportion of 3 mols.to 1 of sugar. The solu-tion is then heated, and the strontium saccharate separated in the formof a heavy sandy precipitate. By diffusing this through warm waterit splits up into a less basic saccharate and strontium hydroxide. Thefiltrate from the saccharate precipitate contains only from 0.3 to 0.8per cent. of sugar. The composition of the saccharate is representedby the following formula : C12H22011,2Sr0,xH20. On throwing i tinto water it suffers the following decomposition :-3C12H32011,2Sr0,~H20 = 4H2Sr02,8H20 + 3C12]EX,201~,2sr0 +(x-9)&0TECHNICAL CHEMISTRY.253The paper, which is of considerable length, gives full particularsrelating to the entire method of working, and describes in detail thepreparation of the strontium hydroxide. D. B.Preparation of Brown and White Cellulose. (Dingl. poZyt. J.,245, 520.)-According to Rasch and Kirchner, the steamed blocks ofwood are broken up into pieces of the size of a pea by means of achopping machine ; they are then crushed between rollers, and thefibres disintegrated in a centrifugal rag-engine. The product thusobtained is used for the preparation of pasteboard and coarse kinds ofpaper. D. B.Preparation of the Homologues of Phenol, Naphthol, andResorcinol. (DingZ. polyt. J., 246, 201 .)-Equivalent quantities ofa phenol and an alcohol are heated with zinc chloride until twolayers form, and the oil is then rectified.The reaction takes placethus :-C6H5.0H + Et.OH = C6H4Et.0H + H,O.A. K. M.Becker's Creaming Process. By W. FLEISCHMANN and R.SACHTLEBEN (Ried. Centr., 1882, 770).--The authors find that nospecial advantage is gained by employing the above process, as theamount of cream removed is no greater than that obtained by theolder methods, and moreover it is uncertain and of long duration.One advantage is, however, gained-that the coagulum formed bythe rennet is not in thick lumps, but in fine flocks, which is the moredigestible form of case'in. E. W. P.Jakobsen's Testing-churn. By W. FLEISCHMANN and R. SACHTLE-BEN (Bied. Centr., 1882, 763).-The results obtained by the use ofthis apparatus (ibid., 1876, 400, and 1877, 224) are not trustworthy,a s the percentage of butter yielded falls with the weight of milk ex-perimented on, and the greatest yield is obtained by the more rapidrotation of the apparatus.Sour milk gave the most trustworthyresults. E. W. P.On Creaming. By D. GABEL (Bied. Centr., 1882, 626).-Theauthor adheres to his opinion, previously expressed, that it is quiteunnecessary to cool milk before creaming. E. W. P.Preservation of Milk, &c. By BARFF and others (Bied. Centr.,1882, 627--630).-Barff preserves milk, &c., by the addition of asolution of boroglyceride in water (1 : 20-60). Le Bon employs acalcium and sodium compound of boroglyceride. Mayer and Portelefind that salicylic acid must not be added to milk or butter, as it im-parts an unpleasant taste.To preserve milk for transport, A. Meyerkeeps it at 50" by steam f o r three hours, introducing sodium benzoate(0% gram per litre), or half as much boric acid with or without sodiumchloride. He believes the benzoate to be harmless, but cannot say as5.254 ABSTRACTS OF CHEMICAL PAPERS.much for the boric acid, which, however, only costs a sixth as muchas the benzoate. E. W. P.Preservation of Milk. By B. DIETZELL (Bied. Centr., 1882, 789).-The method proposed is almost identical with that proposed byScherff (Abstr., 1882, 1016). E. W. P.Preservation of Milk. By BUSSE (Bied. Centr., 1882, 789).-Toevery litre of milk 1-2 teaspoonfuls of hydrogen peroxide is to beadded.Butter made from milk containing hydrogen peroxide remainsfor a long time without becoming rancid. E. W. P.Preserved Milk, 6 % ~ . By W. FLETSCHMANN (Bied. Centr., 1882,771-773).-1n this report from the Experimental Station in Raden,the composition of milk is reported as follows :-Morning. Evening. Mid-day.Dry matter . . . . 11.332-12.852 11.203-12.694 11.376-12.557Fat.. .. . . . . . . . . 2.816- 4.015 2.276- 3.858 2.820- 3.790The composit3ion of two samples of Swiss condensed milk withoutadded sugar, but with added benzoic acid, was :-Water, 52.315 ; fat,13.090 ; albumin, 12.130 ; lactose, 17.434 ; ash, 2.788 ; benzoic acid,1.740. Loss, 0.503.Comparisons of estimation of milk by the gravimetric process withthose obtained by the use of Soxhlet’s method and the lactobutyro-meter (Schmoger’s modification) yielded good results, but Mittelstra~s’optical method gave results varying between +0*37 and -0.26.Pepsin causes caseiin to separate more rapidly from milk than whenrennet is used, but there is no perceptible difference in the appearanceof the curds thus formed.E. W. P.On Milk. By M. SCHRODT and others ( B k d . Centr., 1882, 625).-Schrodt finds that the addition of saltpetre to milk which tastes ofturnips does not remove that unpleasantness, as has been stated.LBz6 placed milk in contact with several odorous gases, which com-municated their t,aste to the milk ; ammonia rendered milk gelatinousand thick. It occasionally happens that butter during churningappears as a flocculent coagulum.H. Schultze’s analyses show that itconsists of 12 per cent. water, 11 per cent. case’in, and 75 per cent. fat ;the cause is probably the presence of excess of acid in the cream, dueto carelessness, &c. E. W. P.Preservation of Butter. By W. HAGEMANN (Landzo. Versuch.9.-Stat., 28, 201--227).-The peculiar smell and taste of rancid butteris generally assumed to be due to the presence of free butyric acid, ofwhich only a very small quantity is required to give fresh buttersimilar properties to those of rancid. I n approaching t>he question asto the origin of the free acid, two theories present themselves : eitherit arises from a butyric fermentation a t the expense of the lactose orglycerol, o r else is the product of chemical changes, and is set freefrom certain glycerides in the butter.I n carrying out experimentTECHNICAL CHEMISTRY. 255suggested by the former of these views, bacteria were obtained froma mass of cane-sugar undergoing butyric fernlentation ; these wereintroduced into quantities of pure butter fat which had been washedand freed from water, salts, and lactose: nutriment was added in theform of lactose, and ammonium and other salts necessary for the growthof the cells. The conditions of experiment were varied greatly, butin no instance was the fat turned rancid, even after standing manyweeks : and the addition of a small quantity of rancid to fresh butterdid not appear to accelerate the process. Analysis also showed thatthe quantity of glycerol in fresh and rancid butter was as nearly aspossible the same, hence the presence of free acid could not arise froma decomposition of the glycerol.Froin these facts the author con-cludes that the rancidity of butter is not due to butyric fermentation.In testing the reaction of fresh and rancid butter with litmus-paper,it was noticed that the former gave reddish spots in all cases when thecream from which it was prepared had become sour owing to lacticfermentation of the milk-sugar : rancid butter, however, gave in allcases a most powerful reaction. About half a per cent. of undecom-posed lactose is contained in fresh butter, and its fermentation appearsto proceed further as the butter becomes rancid : the question thensuggested itself whether this rancidity was not actually due indirectlyto the lactic acid formed, and the action of this on fresh butter wastherefore studied.Experiments made at the close of autumn showedihat fresh butter when mixed with lactic acid becomes rancid veryquickly, and at a temperature too low for the growth of bacteria.Pure butter fat was dissolved in ether, a few drops of lactic acid wereadded, and the whole allowed to stand over night : the ether was thendriven off a t a low temperature, and the residual fat proved to bestrongly rancid. In order rightly to comprehend these results, the actionof lactic acid onmono- and tri-butyrin was studied ; and it was foundt'hat butyric acid was in every case set free, as shown by its smell andreaction with litmus-paper : the amount varying with the tempera-ture, and being greater with tri- than mono-butyrin; these resultsindicate that the rancidity of butter is due to the formation of lacticacid by a process of fermentation from the milk-sugar contained inthe butter.The liability of butter to become rancid might be prevented eitherby removing the glycerides of the volatile acids, by creaming milkfresh from the cow with the addition of a small quantity of causticsoda, or by removing the milk-sugar itself; but at present no success-ful practical methods of performing either separation have beendescribed : washing with water gives a tolerably stable product, but,if pushed too far, the aroma is lost. The ferment which acts on thelactose appears to be organic, and not a chemical ferment such asdiastase, myrosin, &c., as its activity is entirely restrained by chloro-form ; the amount also of acid formed does not vary with the quantityof the ferment, and increases instead of diminishing the longer theferment remains in the lactose solution.This behaviour can only bedue to the presence of some organised bodies which increase in num-bers as the fermentation proceeds, the amount of acid increasing inlike proportion. J. K. c'256 ABSTRACTS OF CHEMICAL PAPERS.Cheese, Oleomargarin-cheese, &c. By P. VIETH and others(Bied. Centr., 1882, 764).-The following is the composition ofspurious American cheeses made from grease and oleomargarin :-Grease. Oleomargarin.Water .......... 38.26 37.99F a t .. ............ 21-07 23-70Casein, &c. ...... 35.55 34.65Ash.. ............ 5-12 3.6G100.00 100.00Insoluble fatty acids 90.46 91.82Butter fat ........ 63.00 46.00--The extracted fat contained-Foreign fat ...... 37-00 54.00Schmoger reports that some cheeses made from milk that has passedthrough a centrifugal machine become blue throughout the wholemass. G5bel has noticed the same appearance, and attributes it tounclean vessels which retain some organisms to which the productionof the blue colour is due. E. W. P.Injurious Action of a Cupriferous Oil used in Turkey-redDyeing. By E. SCHAAL (Dingl. yolyt. J., 245, 516).--Tn dyeingvegetable fibres with alizarin, the yarn is subjccted to a preliminarymordanting process, consisting in treating it with soda or soluble glass,drying, and bringing it into a bath of Turkey-rcd oil (huile toulr~a?ite),potash-ley, and sheep’s dung.After drying, the yarn showed anumber of places full of holes. On examination, it was found that thedestruction was due to the presence of copper in the oil, the iron tankused for storing the warm oil being fitted with a gun-metal cock.When this was replaced by an iron stopcock these appearances wereno longer visible. D. B.Fixation of certain Artificial Colouring Matters by meansof Metallic Mordants. By 31. H. KOECHLIN (Chem. News, 46, 179).-A long list of colouring matters is given which have been fixed byaluminium, magnesium, calcium, and chromium acetates, or a mixtureof these. It is frequently necessary to use a mixture in order that theoolour produced shall be “fast,” and compound mordants have agreater resisting power as regards acids and alkalis, and are thereforesuitable for colours which are either acid or alkaline.A short historicalaccount of the introduchion of compound mordants is also given.E. W. P.Preparation of Aluminium Thiocyanate. (Din$. poZyt. J.,245, 306.)-Lauber and Haussman obtain aluminium thiocyanate inthe following manner :-In the preparation of thiocyanates by meansof carbon bisulphide and sulphuretted hydrogen, there is obtained inthe first place a ley containing ammonium thiocpanate and sulphuretteTECHNICAL CHEMISTRY. 257hydrogen ; if aftel- driving off the latter, the ley is decomposed in suit-able vessels by a definite quantity of lime, a solution of calcium thio-cyanate is obtained, which is free from iron, and sufficiently pure forthe manufacture of aluminium thiocyanate.The latter is prepared asfollows:-5 k. aluminium sulphate are dissolved in 5 1. boiling water,250 g. chalk added, then 11.5 1. calcium thiocyanate solution of 20" B.The mixture is stirred well, allowed to settle, filtered, and the clearsolution used. D. B.Application of Baeyer's Artificial Indigo. By H. SCBMID(DimgZ. polyt. J., 245, 302-305) .-Orthonitrophenylpropiolic acidis brought into commerce in the form of a yellow paste containing25 per cent. dry matter. A weak reducing agent, when allowed to actin an alkaline solution a t a temperature of 31", develops the blue, andfixes it on the fibre.The receipt originally given by the Baden Anilineand Soda Works consists of 40 g. propiolic acid in the form of paste,10 g. finely pulverised borax, 70 g. starch thickening, to which 15 g.sodium xanthate are added immediately before the printing. After beingprinted, the goods are dried and hung in a warm place. The rapiditywith which the colour is developed difters in accordance with the degreeof heat. A passage through Mather and Platt's continuous fixingmachines suffices to produce the blue, whilst if hung in the cold,48 hours' time is necessary to effect the same result. I n order toremove the unpleasant smell resembling mercaptan accompanying theprinting colour, the pieces are treated with a boiling solution of 10 g.sodium carbonate per litre, and soaped a t 30-40". For the produc-tion of lighter shades, a thickening is used containing 100 g.sodium xanthate.The quantity of borax is calculated to form theneutral sodium salt of orthonitrophenylpropiolic acid ; in its place anequivalent amount of sodium carbonate or acetate may be used, whilstthe starch thickening may be replaced by gum tragacanth; bnrntstarch and gum Senegal weaken the colour, although borax coagulat,esthe former. At a price of 44s. per kilo. of propiolic acid in 25 percent. paste, 1 kilo. of indigo blue fixed on the cloth costs 70.4s., itbeing assumed that the conversion into blue is theoretical. Sodiumxanthate acts at a low temperature without steaming, in fact the latteris injurious.It is obtained by the action of sulphuretted hydrogen onalcoholic soda-ley, and forms a yellow crystalline powder. Its prin-cipal products of decomposition are carbonic anhydride, alcohol, andsulphuretted hydrogen. The nitrophenylpropiolic acid is thereforeexposed to this weak reducing action, which is frequently used forreducing aromatic nitro-compounds in alcoholic or alcoholic ammo-niacal solutions by means of sulphuretted hydrogen. The authorfinds that when thiocarbamide is used a higher temperature is needful,which has the advantage that the printing colour keeps better, besidesbeing free from smell. The printing colour prepared with sodiumxanthate is decomposed in a very short time, hence it is necessary toadd the xanthate immediately before printing, or the cloth may beprepared with it, in which case it is padded in a solution containingfrom 100-300 g.sodium xanthate. The blue obtained from the pro-piolic acid gives brighter colours than tlhe blue dyed with natura258 ABSTRACTS OF CHENICAL PAPERS.indigo, and resists rubbing and soaping better. It can be printed inconjunction with aniline-black and all colours which are developed bymeans of oxidation. Owing to its reducing action, sodium xanthatemay be used as resist for aniline-black. The acid contained in theblack liberates xanthic acid, which readily decomposes into alcoholand carbon bisulphide. The author used this reaction to reserveindigo-blue under aniline-black. Sodium xanthate forms a yellowprecipitate with copper salts, so that it is possible to produce a greencolour.By adding an excess of sodium xanthate to the propiolicacid blue, and passing the goods through a solution of copper after fulldevelopment of the blue, a bluish-greenis obtained, owing to the mix-ture of the yellow with the blue. The yellow produced with copperxanthate withstands acids and dilute alkalis, whilst the green resistssoapiug extremely well. D. B.Chemical Theory of Gunpowder. By H. DEBUS (PTOC. Roy.SOC., 33, 361--370).-The author a t the outset draws attention to thefact that notwithstanding the antiquity of the use of gunpowder, notheory has hitherto been propounded by which the quantities of thechief products of combustion can be calculated from the known com-position of a given weight of gunpowder, or of the amount of heatgenerated during its rnetamorpbosis.The potassium nitrate, charcoal, and sulphur are transformedduring the combustion into potassium carbonate, sulphate, bisulphide,and t hiocyanate, carbonic oxide and anhydride, nitrogen, hydrogensulphide, methane, ammonia, hydrogen, and water.Of these sub-stances, the hydrogen and its compounds, together with potassiumthiocyanate amounting to about 2 per cent. of the original weight ofthe powder, are merely secondary products, and not direct results of theexplosion of the powder ; potassium thiosulphate has also been found,but is formed from the sulphide during the analysis by Bunseii andSchischkoE’s metthod. With regard to the remaining products, theauthor proposes to solve the following problems (1) to determine thereactions which cause their formation and the order in which theysucceed one another, and to represent the complete combustion of gun-powder by one equation ; (2) to calculate from the known compositionof a given weight of powder the volume of the gases, the amount ofheat generated, and the relative energies of powders of different com-position.The experiments of Noble and Abel (Phil. Trans., 1875,137) haveshown that the proportions of the several constituents of the solidresidue are dependent upon accidental variations of the conditions ofthe explosion, and therefore any attempt to express by a single equa-tion the metamorphosis in question would be apt to convey anerroneous idea, and would lead to no important elucidation of thetheory of the explosion of gunpowder.But the author shows thatthe differences in the composition of samples of powder of the samenature, together with the inevitable errors attached to the analyticaloperation, are quite sufficient to explain bhe variations in the propor-tions of the product of combustion. For instance, lst, a portion ofthe potassium bisulphide is partly converted into the sulphate anTECHNICAL CHEI1.IIS'rRY. 259thiosulphate, and thus the qnantities of these salts vary in differentexperiments ; Znd, the potassium bisulphide gives up readily a portionof the sulphur to the steel of the vessel in which the explosion iseffected, and the quantity of ferrous sulphide so produced is dependentupon the conditions of the explosions.If the sources of error be taken into consideration, the explosion ofpowders in a confined space may be expressed with some degree ofaccuracy by the equation 16KN03 + 21c + 5 s = 5KzC03 + K2S04 + 2K2Sz + 13c02 + 3CO + 8H20, whereas the composition of t,hepowder calculated from the mean results of the analyses of Noble andAbel can be represented by the symbols 16K:N03 + 21.18C +6-633.The author by the light of the results obtained by Karolyi and thoseof Noble and Abel has been enabled to develop a theory of the explosionof gunpower competent to explain tile observations of former experi-menters, and in harmony with the thermochemical relations of thereacting substances.According to this theory, gunpowders whichdiffer considerably in their composition are transformed during thefirst stage according to the equation-1OKNOs + 8C + 3s = 2KzC03 + 3KZSOd + GCO, + 5Nz (I),but as carbonic oxide is produced, the following equation more nearlyrepresents the natiire of the change :-16KN03 + 13C + 5 s = 3KZC03 + ~ K Z S O ~ 4- 9coz + co + 8Nz (2).The oxygen contained in the potassium carbonate and sulphate, andthe carbonic anhydride in equation (1) stand in the ratio 1 : 2 : 2,whereas the heat developed by the formation of the potassium car-bonate to the sulphate and carbonic anhydride in equation (2) standin the relation 1 : 2.05 : 1.04.But, as a rule, gunpowder contains more carbon and sulphur than isrequired by the equations ahove, so that, in the second stage of the explo-sion, the carbon reacts on the potassium sulphate, and the sulphur onthe carbonate, thus : 4KZS04 + 7C = 2K$03 + 2K2S2 + 5c0, and4KzC03 + 75 = KZso4 + 3K2S2 + 4C02, while some of the freecarbon reduces carbonic anhydride to carbonic oxide.These latterreactions are endothermic, are not of an explosive nature, and inpractice are seldom complete.If z, y, o be positive numbers, and u represents the molecules of car-bonic oxide formed by the complete combustion of a given weight ofpowder, we have the following general equation as representing thecomplete combustion of gunpowder: xKN03 + yC + zS 1 T%(4z +2 - 162 - 4u)(K2CO3) + &(20x - 16y + 42 + ~u)(K,SO,) +::(- 10% + 8y + 122 - 4a)(K2S2) + &(- 4% + 2Oy + 162 --24a)(C02) + aCO + $xNz.The correctness of the equation is provedby the agreement of the calculated numbers with those observed byBunsen and Schischkoff, Noble and Abel, and others. But if in thisequation x = 16 and CL = 0 (and this latter value does not materiallyaffect the main result), we obtain 16KN03 + yC + ZS = &(64 + 8~- 16~)(R2C03) + &(320 - 1 6 ~ + 4z)(Kc,SO4) + &(- 160 + 8y +122)(K2S2) + -&(- 64 + 2 0 ~ + 16~)(COz) + 8Nz260 ABSTRACTS OF CHEMICAL PAPERS.If the coefficients of the potassium carbonate, sulphate, and bisul-phide be taken as 0, the equation ( a ) 64 + 8y - 162 = 0, and (p)320 - 16y + 42 = 0, and (-I) - 160 + 8y + 122 = 0, representthree sides of a triangle, of which the two sides represented by equa-tions (a) and (y) intersect a t points y = 8 and z = 8, and these valuesintroduced into the equation above give 16KN0, + 8C + 8s =8K2S04 + 8C0, + 8N2, and finally the two sides represented byequations (6) and ( p i ) intersect in points y = 24 and z = 16, hence16KNO3 + 24C + 16s = 8KZSz + 24CO2 + 8Nz.Again, if V represent the volume of gas evolved by the combustionof a powder containing 16 mols. KN03, y atoms of carbon and z atomsof sulphur, and W the units of heat developed, then, on the assumption"?{ + 16'? and W = 1000[1827*154 -14that a = 0, V =16.925~ - 8.788~1.Thus the volume of gw becomes greater, andamount of heat lass when ?/ and /?: are increased, and vice versci ; quan-t'ities of KN02, C, and S, represente; by the symbols 16KN03 +8C + 8 S , produce the greatest amount of heah and the smallestvolume of gas, while those corresponding to 16KN0, + 24C + 1 6 sproduce the largest volume of gas and the smallest amount of heat.The products of the equations for V and W divided by 2 x 1000 == 10440.88 - 1 2 . 0 9 ~ ~ + 1208.39~~ - 1 5 . 9 5 ~ ~ + 993.8672 -5.02222 = E, which may be taken as the relative energies of powderof different composition. The difference of the values for E is verysmall if the powders contain from 21-24 at'oms of carbon, and from8-16 atoms of snlphur for every 16 mols. of potassium nitrate.Equal weights of the mixtures 16KN0, + 22C + 8s and lGKNO, + 24C + 1ES give for E the values 16.84 and 16.95 respectively. Iftherefore a powder is required which shall possess nearly the greatestamount of energy, and a t the same time contain the smallest amountof sulphur and carbon compatible with this condition, theory points t oa mixture, 16KN03 + 22C + 85, whereas the gunpowders of mostnations fluctuate about 1GKN03 + 21.2C + 6.8s.The author finally draws attention to the advantage of the geome-trical demonstration above for illustrating the qualitative nature, andthe quantitative relations of the products of combustion, the volumesof the gases, and the amount of heat developed.Cause of the Acid Reaction Exhibited by some Kinds ofPaper. By HAERLING (Din& polyt. J., 246, 195).-It has beenstated by Feichtinger (Abstr., 1882, 1339) that paper sized with resinexhibits an acid reaction, which he attributes to the presence of freesulphuric acid. According to the author, the acid reaction is not dueto free acid, but to the presence of aluminium sulphate, which is usedfor fixing the size.2000V. H. V.A. I(. M

ISSN:0368-1769    

DOI:10.1039/CA8834400248

出版商:RSC    

年代:1883

数据来源: RSC

摘要:

261General and Physical Chemistry.The Light emitted by Comets. By BERTHELOT (Ann. Chim.Phys. [ 5 ] , 27, 232-233) .-Arguing from the presence of hydrogen,carbon, and nitrogen detected by Huggins in the spectra (correspond-ing to those given by acetylene and hydrocyanic acid) of the lightemitted by comets, the author suggests electrical disturbance as amore probable cause of luminosity than combustion.Telluric Rays and the Spectrum of Water Vapour. ByJ. JANSSEN (Compt. rend., 95, 885-890) .-An historical summary.Spectra of Carbon and its Compounds. By 0. D. LIVEINGand J. DEWAR (Proc. Roy. Xoc., 34, 123--130).-The authors, informer experiments, have traced a fluted band spectrum, which occurswhen carbon poles transmit the arc or spark current in air to thecompound cyanogen (Abstr., 1882, 252-253).The present paperis a continuation of the investigations, which have received freshinterest from the discovery by Huggins of cyanogen bands in thecomet of 1881.The arc discbarge between graphite poles in carbonic anhydrideshows the cyanogen triple set beginning about X 4380, with traces ofthe fluted bands at 4218 and 3883 ; if the carbonic anhydride is dis-placed by air, the triple set is weakened, whilst the fluted series isstrengthened. The spark discharge in carbonic anhydride does notshow the cyanogen series ; but it appears when the discharge is takenin nitrogen. With the arc discharge in hydrogen, the triple set iswell marked, while the series at 4218 disappears, bat the hydrocarbon-group at 4310 comes out strong.When the pressure in differentgases was rednced to 1 inch, the arc in air showed the hydrocarbonset, the cyanogen series, and the nitrogen series near H. But in carbonicanhydride, the triple set alone was strongly marked : in hydrogen, thetriple set disappears, but the hydrocarbon-group comes out strong.The authors give a list of carbon arc-lines from X 2434.8 to X 2881.1,when a continuous Siemens current is used; these seem t o provethat carbon-vapour of a low tension exists in the arc discharge, whichwould account for the combination of carbon with hydrogen ornitrogen under these conditions.When the spectrum of a magnified image of the electric arc isexamined, all the more refrangible cyanogen-groups are seen near thepositive pole, together with a series of channellings in the red; thecyanogen-group is also visible at the negative pole.But if puffs ofair or carbonic anhydride are passed into the arc, the hydrocarbonlines amre produced; the same result obtains if one of the poles ismoistened.The De Meritens arc in water shows the hydrocarbon spectrumalone, but if a little nitrobenzene in glycerol be substituted the cyanogentriplet about 4380 appears.L. T. T.VOL. XLIV. 2 62 ABSTRACTS OF CHEMICAL PAPERS.The authors have repeated their experiments with vacuum tubes,using those of capillary glass; the tubes containing benzene or asolution of naphthalene in benzene, show no trace of the cyanogenspectrum, until, after continued use, there is a leak or crack a t thapoint where the platinum is sealed into the glass.In observations by the eye of flames of coal-gas which had passedthrough ammonia, no cyanogen spectrum could be observed ; similarly,hydrogen mixed with carbonic anhydride and ammonia gave noresult, but cyanogen can be detected if the ammonia is mixed withchloroform and other carbon compounds.As a result of their experiments, the authors consider that hydro-cyanic acid can always be separated from reducing flames, in whichthe free carbon or dense hydrocarbon vapours favour its formation.In photographs taken by means of a quartz and calcspar train, theauthors could detect in a flame of coal-gas well supplied with oxygenonly the hydrocarbon-groups ; but if the coal-gas is passed throughammonia, photographs reveal the characteristic cyanogen-groups atX 3803 and X 4218. Spectrum analysis can then detect the presenceof cyanogen under widely different conditions.I n photographs of theultra-violet spectrum of a cyanogen flame fed with oxygen, the authorssucceeded in detecting the carbon line 2478.3, which proves thatcarbon-vapour does exist in flames of cyanogen, although to a smallerextent than in the arc discharge. V. H. V.The Ultra-violet Spectra of Elements. By G. D. LIVETNG andJ. DEWAR (Proc. Roy. SOL, 34, 122-123) .---E’rom photographs takenwith a Rutherford grating, the authors have determined the wave-lengths of 91 of the principal lines in the spark spectrum of ironbetween X 2948, the termination of Cornu’s map of the solar spectrum,and X 2327 ; and 14 of the strongest lines of the spark spectrum ofcopper up to X 2135.With these lines as lines of reference, they havededuced the wave-lengths of 584 more lines in the arc and sparkspectra of iron within those limits.The authors have further mapped out the ultra-violet lines of thearc spectra of sodium, lithium, barium, strontium, calcium, zinc,mercury, gold, thallium, aluminium, lead, tin, antimony, bismuth, andcarbon. They consider that in several cases harmonic relationshipsexist similar to those noticed in the visible lines of the spectra of thealkalis and magnesium. V. H. V.An Arrangement of the Electric Arc for the Study ofRadiation of Vapours. By G. D. LIVEING and J. DEWAR ( P ~ o c .Roy.Xoc., 34, 119--122).-The authors have constructed a form ofapparatus suitable for a study of the reversal of metallic lines; itconsists of a block of lime, perforated by two holes in planes a t rightangles to one another, and through which pass the carbon rods con-nected with a Siemens dynamo-machine. One of these rods isperforated, and observations are made by projecting with a lens theliglit issuing from the tube on the slit of the spectroscope. By intro-ducing a small rod of carbon into the perforation from the furtheGENERAL AND PHYSICAL CHEMISTRY. 263end, a luminous background can be obtained, and as the walls of thetube are hotter than the metallic vapours, the metallic lines arereversed; an alteration of the position of the carbon rod causes thelines to disappear, reappear, or show reversal.Using commercialcarbons, the first lines seen were the potassium lines h 4044-6, nextthe two aluminium lines between H; and I(, then the manganese tripleabout X 4034, a calcium line X 4226, then the calcium lines near 31,the iron line M, and then gradually many conspicuous lines between0 and h. I n the higher region, the continuous spectrum extendsbeyond the solar spectrum. The cdcirtm lines H and K were oftenabsent, and not even brought out reversed when calcium or itschloride was introduced into the tube. The lithium lines X 4603 andX 4131 are relatively difficult of reversal. If ammonia is passed intothe tube, most of the lines attributed to cyanogen by the authors appear.As it is known that ammonia reacts on carbon at a white heat toproduce ammonium cyanide and hydrogen, the appearance of thecyanogen lines offers an independent confirmation of the aathor’sviews.The two indium lines X 4101 and X 4509 are always reversed ;tin gives flutings in Che highly refrangible portions of the spectrum,and silver gives a fluted spectrum in the blue. Cdciurn chloridegives six or seven bands between L and M ; these are sometimesbright and sometimes reversed.Reversal of Metallic Lines in Over-exposed Photographs ofSpectra. By W. N. HARTLEY (Proc. Roy. SOC., 34, 84-86).-Theauthor has made a series of comparative experiments in order toascertain the exact period of exposure of the sensitive plate to therays, in order to bring out the most characteristic lines, without thediffused rays of the air spectrum.Over-exposure causes strong linesto be reversed without materially altering the appearance of the restof the spectrum ; this is particularly the case with lines of the metal’smagnesium, aluminium, and indium : thus in two over-exposedphotographs the magnesium triplet b’ between K and L became aquadruple group by reason of the most refrangible line being splitinto two by a reversal. The author considers that the method ofcomparative exposures should be employed to confirm the accuracy ofobservations based entirely on photographic representations of spectsa.By W. N. HARTLBY(Proc. Roy. Xoc., 34, 81-94)--The author has made an experimentalcomparison of the spectra of various compounds in solution with, thoseof the elements they contain.In order to eliminate lines foreign to thesubstances examined, the arc spectrum between graphite poles waschosen, as producing about 12 insignificant lines due to carbon,and about 66 easily recopisable lines and bands due t~ air. Oncomparing the spectra of solutions of salts with those from metallicelectrodes, it was found that the same lines, with the same graphiccharacter, were produced in both cases, but their continuity wasaltered. Thus discontinuous but long lines, or, in certain cases, evenshort, lines, appear as long lines in the solution-spectra. Zinc offersan excgptional instance of this variation, for the pure metal exhibits aV. H. V.V. H. V.Researches on Spectrum Photography.t 264 ABSTRACTS OF CHEMICAL PAPERS.series of short lines or dots, which are absent from photographs of thespectra from its solutions.Certain discontinuous lines in the spectrumof iridium become continuous when moistened with calcium chloridesolution.The author considers that only the method of solution is availablefor the estimation of the relative proportions of the constituents of analloy or mineral ; for most alloys are not homogeneous, whereas thecomposition of a solution represents throughout the composition ofthe mass dissolved.Experiments were made in order to examine the sensitiveness ofthe spectrum reaction under various conditions, as the nature of theelement, time of exposure, and intensity of the spark ; it was foundthat .&, per cent.of calcium, silver, copper, and dm per cent. ofmanganese, were recognisable quantities.Atomic Refraction of Sulphur. By R. NASINI ( B e y . , 15, 28782892).-The author, at the outset, alludes to the dependence of theatomic refraction of an element on the nature of its combination withother elements, which has been established by the researches ofBriihl. As the specific refraction of only a few sulphur compoundshas been determined, the author has made a minute examination ofseveral organic and inorganic compounds, in order to ascertain whetherthe atomic refraction of sulphur varies with its valency.The refractive indices were determined for the hydrogen lines a, P,and y, and the sodium line D, and the specific refraction calculated-1 ne-1 , according to the empirical formula L, and the formula --d (12' + 2 j d 'on the basis of these formulse, the index of refraction A for a ray ofinfinite wave-length is calculated by the aid of Cauchy's dispersionformula (ph = A + -+h- + .. .). The sp. gr. of the liquid usedwas taken at 20", and reduced t o that of water at 4".V. H. V.B Cx2 4The following table embodies the author's results :-Substance.Ethyl mercaptan, EtSH.. , , . . . . , .Ethyl sulphide, Et2S .. . . . . . . , . . .Ethyl bisulphide, Et,S, . . , . . . , . . .Isobiityl mercaptan, C,H,SH . . . .Isoamyl eulphide, (C,H,,)25 , . . . . ,Carbon bisulphide, CS2 . . . . . . , . . .Ethyl ethylsulphonate, Et.SO,Et . .Sulphuric acid... . . . 8 8 . a . . . . . . .Sulphuric anhydride . . . . . . . , , . .a? 2:--0.893070.836760 992670 *835730 '843141 -2634d2,'L.1 '14517d y .d2,O.1 '82731 -9365Pa--1 -427691 * 43961.503061-4.35751 44.9661 '618471 .a17331 -426591 -4077PD1 *430551 -442331 -506331 -438591 '452381 '62037--1 -419591 -429221 *4@9651 *437881 '449291 -516041 -445471 '458891 *652681 -42421 -433531 - 4148GENERAL AND PHYSICAL CHEMISTRY. 2 65Substance.---------Ethyl mercaptan, EtSH, .............Isobutyl mercaptan, C4H99H ........Isoamyl sulphide, (C,H,,),S ..........Carbon bisulphide, CS2 ..............Ethyl ethylsulphonate, Et.SO,Et ......Sulphuric anhydride ................Ethjl sulphide, Et2S ................Ethyl bisulphide, Et&& ..............Sulphuric acid.. ....................UY1 '44451 -455221.524071 -45111 *464471 -675151 -425951 *a3745 -A.1 0418051 -427861 40671 *423821 -438131 -58641 -410651 -418261 -39922--B.0 -349790 *523620 904310.514560'496%1 '160980.288960 *362020.36924From the values obtained for the line a in the above table, togetherwith a few others obtained by Wiedemann, the author has calculatedthe atomic refraction r, and r,, x4 and ra, for the line a, and deducedfrom the constant A, according to the old and new formulse.Theresults are contained in the table below :-Substance.Ethyl mercaptan ........Ethyl sulphide ..........Ethyl bisulphide ........Isobutyl mercaptan ......Isoam yl mercaptan........Isoamyl sulphide .... , ...Diethyl monothiocarbonateDiethyl dithiocarbonate , .Mean ......Carbon bisulphide ........Diet hyl t hiocarbonat e,CS(0Et)z ............Mean ......12-1a -.r.ra .13-814.2814.4113-931414.2-14-1015.61P-15.61TA.13.4313.6313-713-3113.3413.4'713.65.13.7813-5315.20--18-9815.09--ra.7.8887-827-847-74%A'7.647.727.687.537.537-467-8 97.78From this table it is evident that the atomic refraction of sulphurvaries according as it is combined with two different groupings, by oneaffinity each, or with both of its affinities to one carbon-atom ; and further,the values for ror and r, are concordant among themselves, and standin relation to one another, similar to that existing between the valuesfor ra and xa.As far as regards the other sulphur compounds examined,the values €or the atomic refraction of sulphur are in accordance withone another, but differ in a, most marked way from the values above ;they vary according to the hypothesis adopted to express their con-stitution, i.e., whether the oxygen-atom is combined with the sulphur-atom by one or two bands2G6 ABSTRACTS OF CHEMICAL PAPERS.Atom.refraction.n-1r A *7'(Et.S.O.D.O.Etl. ... 8.910H.S.O.O.OH .. 9.01Diatomic snlphur ... ............ 8.10O<,>O..,.. S 8.37 .... L.[ Et.[.O.Et ...... 8.33TetmtQmicsulphur ' ti ..OH.S.O.OH,. .... 84.3I 0 : S : O ........ 6.94010 : S<J ......... 7.79 iEtEtOH....... 7-75Hexatomic snlphnr . . ...... 7-85nn"- 1(n2+2)d.TA .5.253-24,-6.375.824-594.514.914.593.793.78These variations in the atomic refractmion of sulphur may arise fromone of two caixses, i.e., alteration of valency, or the direct combina,tionof sulphur with oxygen instead of carbon ; a further examination ofother sulphur compounds alone mu decide the question, and theauthor proposes to carry on researches for this purpose.V. H. V.Electric Discharge in Rarefied Gases. By E. GOLDSTEIN(PhiZ. Mag. [5 3, 14, 366--387).-The author has previously shownthat the electricaldischarge in rarefied gases cannot be effected by theactual projection of gas particles, and for the same reasons it cannot bepropagated by particles torn off from the tube, electrodes, &c.A systemof pores in an insulator, or a single aperture of relatively smalldiameter, sends out rays with properties precisely similar t o thosefrom st metailic knthode. It is known also that at sufficiently highexhaustions the positive light has the property of rectilinear propaqa-tion and the power of exciting phosphorescence, and hence it woulGENERAL AND PHYSICAL CHEMISTRY. 267not be reasonable to adopt an explanation of the kathode light, theprinciple of which is not applicable to the positive light.If two wires, a and b, are inserted in the end of a cylindrical tube,parallel with its axis, and both are made kathodes of the same dis-charge, each repels those rays from the other which pass near it, thusproducing two sharply defined surfaces, one of which receives no raysfrom a , whilst the other receives no rays from b.If one of theelectrodes is platinum, it is found that that part of the tube on whichno rays from the platinum kathode fall, is just as thickly coveredwith a deposit of platinum as is any other part of the tube. In otherwords, the rays of the kathode light are deflected, whilst the particlesprojected from the electrode are not deflected. I t follows, therefore,that, contrary to the usual supposition, recently defended by Gintl andby Puluj, the two cannot be essentially connected. The objectionsto the supposition that the discharge is effected through the mediumof particles torn from the electrodes, apply equally well in the case ofparticles torn from the walls of the tube.Since the discharge cannot be explained by the motion of ponder-able particles, it follows that it must be a process which takes place inthe free ether.Hittorf found that the resistance of the positive light decreases asthe exhaustion increases, and that changes in the form and magnitudeof the anode are without influence.He also concluded that the resist-ance of the kathode light, and a t the surface of the kathode, increasesas the exhaustion increases, and hence the resistance to the dischwgea t very high exhaustions is exerted at the surface of the kathode aridin the space filled by the kathode light.The author finds, however,that the resistance of the kathode light at very low pressures becomescomparatirely small with respect to the total resistance to the dis-charge. Hence it appears that the resistance a t very low pressures isexerted entirely a t the surface of the kathode. The experiments onthis point were made with a spark micrometer, included in a secondcircuit connecting the electrodes of the discharge tube. It was foundthat the discharge did not pass exclusively through the tube up to acertain distance between the balls of the micrometer, and then with acertain small decrease in this distance exclusively through the airspace between the balls ; hut that there are certain positions in whichthe spark sometimes takes one path, sometimes the other, and the oncpath the less frequently, the closer the approach to the point a t whichthe other alone is taken.This phenomenon did not affect the accuracy ofthe measurements. If the micrometer is included in the branch circuitof tubes which transmit the discharge a t both make and break, it isfound that if the distance between the balls of the micrometer isgradually diminished, a point is reached a t which the current at breakcompletely leaves the tube and passes only across the air space betweenthe balls, whilst the current a t make continues to pass through thetube with undiminished luminosity. This phenomenon may dependon different maximum tension of the current on making and breakingcontact. From these experiments, it is evident that when the dischargetakes place in gases, the division of the current cannot be calculatedby means of Ohm’s law.If two similar tubes are placed side by side268 ABSTRACTS OF CHEMICAL PAPERS.opposite to each other, in the same induced current, then at a certainpressure the current does not divide itself between the two tubes inaay definite ratio to the resistance of the tubes, but passes exclusivelythrough one of them, leaving the other entirely dark. These observa-tions will slightly, but not materially, affect the accuracy of someresults given in the author’s book on a “New Form of ElectricalRepulsion.”By means of a vacuum tube of special form, in which the anodewas placed close and parallel to the plane of a kathode of largesurface, and in which the length of the tube could be altered by slid-ing an enclosed closely-fitting glass cylinder, the author was able, atvery low pressures, to increase the expan&on of the kathode light inthe ratio 1 : 30, without causing the resistance to vary as much as1 : 1.05; hence the resistance of the kathode light is a vanishingquantity in comparison with the resistance at the surface of thekathode.I t is also evident that the resistance of the gas in the dis-charge tube becomes less as the quantity of gas decreases, and itfollows that the tube would have the greatest conductivity when thewhole of the gas is removed and the tube is filled only withfree ether, which the author regards as the true medium of the dis-charge.The motion of the ether cannot be regarded as progressive,but is best regarded as radiant. Every particle of ether in a pencilof negative light assumes that form of motion which is excited at thepoint of origin of the pencil.Experiments with a tube filled partly with nitrogen and partly withsodium vapour, show that the positive light can be displaced withoutany corresponding displacement of the gas itself, and experiments withtwo tubes connected by a capillary tube furnished with a stop-cock,show that when the discharge is powerfully deflected by a magnetagainst the side of one tube, the stop-cock being open, there was noactual transport of gas from one tube to the other, or, rather, that thedifference in pressure caused by such transport, if it did take place,was less than 0.01 mm.of mercury, a difference which could have beenrecognised by alteration in the distance between two consecutivestrize. It has been argued in opposition to the theory that the etheris the vehicle of the discharge, that if such were the case all gaseswould give the same spectrum, which is contrary to fact. But theether itself has not the power of emitting light. The luminosity ofgas subjected to an electric discharge depends on the molecules of thegas having a form and period of oscillation necessary for the emissionof visible rays. The phenomena of phosphorescence and fluorescenceshow that molecules of matter can take up invisible vibrations of freeether, and thus become luminous. The author considers that the dis-charge takes place in free ether, but is itself non-lnminous.Themotion of the ether is, however, communicated to the molecules of gasin the tube, and these then vibrate according to their particular struc-ture and conditions of elasticity, and in their turn communicate tothe ether transverse vibrations which produce the sensation of ligh 1;.In fact, the luminosity of gases traversed by the electric discharge isa phenomenon closely analogous to resonance. It differs fromfluorescence and phosphoreseence in that, in both these cases, thQENERAL AND PHYSICAL CHEMISTRY. 269vibrations of the ether are transferred to the atoms or molecules ofmatter, and back again to the ether, without changing their characteras transverse vibrations, whilst in the luminous discharge a motion ofthe ether, which does not consist of transverse vibrations, is convertedinto such vibrations.Moreover, a temperature-condition is alwaysassociated with phosphorescence, which does not obtain in thecase of the luminous discharge in gases. The assumption that avacuum conducts electricity is of the highest importance in cosmicalphysics. The author considers that certain terrestrial electric andmagnetic phenomena may be due to currents of electricity radiatedfrom the sun through interplanetary space. Experiments show thatthere is no limit to the expansion of the kathode light, and that itatreams out into space without reference to the position of the anode.It is therefore not necessary to assume that the earth is one pole ofthe solar current, for discharges, both poles of which were on the sun,might produce negative rays radiating from the sun into space.11.Two processes are essential to the production of an electric dia-charge: a change in the condition of the ether preceding the dis-charge, which produces a certain condition of unstable equilibrium inthe arrangement of its parts (this condition may be called the tensionof the etaher) and the restoration of shble eqnilibrium, Le., the dis-charge itself. The tension preceding the discharge is not equallygreat at all cross sections of the discharge-tube, even when the tube isof eqiial section throughout ; in certain parts of the tube it may evenbe zero: it has either finite or maximum values a t the surfaces of themetal poles, and a t those points which appear as points of issue of theseparate positive layers or of secondary negative pencils.The so-called ether-envelopes surrounding the atoms or molecules of a gasundoubtedly play an important part in the emission of liglit producedby the discharge, but their exact function cannot a t present be deter-mined. The forces which are exerted by the particles of matter inthe production of the ether-envelopes tend to produce an arrangementof the ether different from that produced by the electrical forces alone,and consequently the more gas molecules in a given space, the greaterwill be the electrical forces necessary to bring about that arrange-ment of the ether which must precede discharge : hence the resistanceof the space in which the discharge takes place is less the more com-pletely the gas is removed.The author cannot accept Wiedemann’sview that the ether-envelopes are the real medium of discharge. Ifthe envelopes suffer deformation without the free ether taking part inthe discharge, then there must be a pure distance-action between theenvelopes.From the results of the following experiments, the author concludesthat the direction of the negative current from the kathode is thedirection in which the electric discharge is propagated in the kathodelight and also in the negative pencils and in the positive stratifications.If a solid body is placed in the path of a pencil of kathode light,, orof secondary negative light, the shadow is cast on that side farthestaway from the kathode, and the shadows formed in the phosphorescentsurfaces excited by the positive light exhibik similar behaviour.Theproperties of secondary negative rays, even for a considerable dis270 ABSTRACTS OF CHENICAL PAPERS.tance, correspond with the conditions which exist a t that boundary afthe negative rays which is nearest the kathode. With higher andhigher degrees of exhaustion, the pencils radiate continually more andmore from the mouth of a narrow tube opening into a wider tube, aphenomenon which would not occur if the pencil had its origin in thewider tube and was propagated from it into the narrower tube. If asufficiently weak magnet is allowed to act on the eiid of a longkathode pencil remote from the kathode, only the end of the pencil isaffected by the magnet, the rest of the pencil remaining unaltered. If,however, the magnet is brought close t o the kathode, so as to act onthe rays nearest the kathode, then the whole of the pencil is deflectedeven to its furthest point, although the distance of the latter from themagnet is so great that the magnet could not produce any directeffect.Precisely similar phenomena are exhibited by secondary nega-tive pencils, and also by the rays of separate positive stratifications.It is evident, therefore, that in each separate stratification the dis-charge is propagated from the bounding surface on the kathode side tothe bounding surface on the side nearest the anode. The usualphenomena of deflection may be explained in a similaT manner.111. It is necessary to distinguish between the velocity and directionof the discharge of a peneil of electrical rays and the velocity anddirection with which the tension preceding the discharge is propagated.A11 the observed phenomena indicate that the tension is pmpagated inthe direction of the negative current; the tension of se,para,te posi-tive stratifications is developed in the same order of time as that inwhich they follow one another in space from the kathode to the anode.The position and character of separate complete stratifica+ions, espe-cially the position af the points from which the separate dischargesformed by the stratifications issae, depend, not on the conditions .of theanode, but on the position and character of the kathode.With highexhaustion and a sufficiently powerf p31 and regular indudion current,stratitications ean be obtained which are perfectly stationary and equalin thickness to the diameter of the tube. In a tube arranged so thatthe electrodes can be moved along the axis of the tube, any motion ofthe anode produces no displacemeiit of the stratification. The layerspassed over by the anode as i t approaches the kahhode disappear oneby one as if absorbed by the anode. If the anode is moved awayfromthe kathode, all the previously existing layers retain their originalpositions, and new layers appear in the space left by the anode, eachnew layer after its formation being perfectlly independent of any sub-sequent motion of the anode in the 6ame direction.If, however, thekathode is moved towards the anode all the layers in the tube move atonce through exactly .the same distance and exactly in the same direc-tion as the kathsde moves. As &he distance between the electrodes isdiminished, the number of layers possible is diminished also, and eachlayer disappears as soon as it is pushed up against the anode. If thekathode is moved away from the anode, all the layers follow thekathode and new layers appear in the space left between the last layerand the anode, each layer after its formation following the motion ofthe kathode. The interval between every two layers in a tube ispracticaZZy the same, so that at a given deusity of gas and intensity oOELNERAL AND PHI'SICAL CHEJIISTRY.271discharge we may speak simply of the strat9cation i92tervnl. Thenumber of layers in a tube is evidently the quotient of the length ofthe column by the stratification intewal. When, as frequently. hap-pens, this quotient is not, a whole number, it is found that the layernearest the kathode is at the same distance from i t for every distancebetween the two electrodes, whilst the incomplete layer is in contactwith the anode and shortens or lengthens in proportion to the excessof the quotient above a whole number. Moreover, consecutive layersin a column of positive ]light may show distinct differences in colouralthough of the same form and magnitude, a phenomenon especiallymarked in the case of hydrogen. The colour of each layer dependsentirely on its position with respect to the kathode, aud not at all onits relation to the anode.Further, variations in the size of the anodehave no effect on the position of the layers, but a variation in the sizeof the kathode changes the position of all the pmitive layers. Otherconditions being the same, the smaller the kathode the greater thedistance between the ksthode and the fimt positive layer ; the intervalsbetween the successive positive layers are not altered.I t must not be assumed, however, that the conditions of tension anddischarge of the whole stratified column are determined by the kathode,or the physical conditions at the kathode. The position and proper-ties of each layer depend mainly, if not entirely, on the position andproperties of the layer preceding it on the side next the kathode.Theinfluence of the bthode on the entire stratified column is thereforeonly indirect. The conditions at the kathode determine the propertiesof the kathode light ; this determines the position and ,properties ofthe first positive layer ; this the position, &c., of 'the second layer, andso on. This view is based on the results of experiments with secondarynegative light. A cylindrical tube provided with a movable kathode,K, and fixed anode, A, contained a closely-fikting short glass tube, R,with a small aperture, x,, which oould be moved along the larger tube ;the small aperture, x, acting as a secondary negative pole.Any move-ment of K affected all the layers between K and %, but had no effecton the layers between 2 and A. If K remains stationary while x ismoved, the movement affects all the layers between 2 and A, just as ifx were a metallic kathode. Then, too, .the colours between K and zdepend on the position of K, whilst those between a: and A dependonly on the position of x;, and are independent of K. The magnitudeof the secondary pole affects all the layers between it and the anode,just as t'he magnitude of the kathode affects all the layers between itand the secondary pole. With a -tube containing two secondary nega-tive poles it was found that the position of each layer depends on theposition and character of that secondary negative pole or pencil ofsecondary negative light which is nearest to i h on the side towards thekathode.As a matter of fact, the interval between two consecutive layers ina simple cylindrical tube diminishes slightly from the kathode to theanode.If a secondary pole is introduced, the distances diminish fromthe kathode up to this secondary pole, then the distance suddenlyincreases, and a new series of diminishing intervals is commenced.With infinitely small changes in the section when the secondary nega2 72 ABSTRACTS OF CHEMICAL PAPERS.tive pencil passes ink0 a positive layer, the distance between any twolayers depends on the properties of that component of the pair whichis nearest the kathode. The conditions existing at the point of originof each layer always influence the layer following next to it on theside of the anode, but have no effect on the preceding layer on theside of the kathode.The conditions of formation of the nth layerstand to the properties of the (n + 1) layer in the relation of causet o effect. In other words, the propagation of electrical tension or theproduction of separate layers, is effected in the direction from thekathode to the anode. C. H. B.The Leclanchk Cell, and the Reactions of Manganese Oxideswith Ammonium Chloride. By E. DIVERS (Chem. News, 46, 259-2GO).-Longi doubts Priwoznik’s statement that zinc acts on ammo-nium chloride and forms zinco-diammonium chloride, Zn(NH3C1)2 ;the author has, however, obtained this same substance, and describesits properties; in solution it probably exists as a double salt withammonium chloride, for when the liquid is heated, much ammoniaappears and a double chloride of zinc and ammonium is formed.Thezinco-diammonium chloride is decompmed by water into a, solublesalt, (ClH4N)2,Zn(NH,J31),, and an insoluble compound, H0.Zn.NH3C1,which latter is probably the same a’s that found by Davis, and towhich he assigned the formula Zn(OH)2,NHiCl.Manganese dioxide is not affected by digestion with ammoniumchloride ; the monoxide, however, is attacked, a portion passing intosolution accompanied by evolution of ammonia and the formation of alight - coloured body, presumably manganous hy droxy chlor ide, HOMn C1,as treatment with water gives rise to the formation of mangnnonshydroxide.Intermediate oxides are also attacked in a similar manner.Zinco. diammonium chloride, in presence of ammonium chloride, actsgradually on hydrogeu manganite, MG%H2O4, manganese passing intosolution, and zinc being precipitated as manganite, but this action doesnot occur with native manganite. Solid manganese dioxide is attackedby zinc in presence of ammonium chloride, both zinc and manganesegoing into solution, whilst ammonia is set free. From these observedfacts, a theory of the action of the Leclanchh cell is deduced.Primary action-Mn204 + 2HNH3C1 + Zn = Mn20aHz + (NH3C1)2Zn.This zinc compound remains in solution until the liquid is saturated,and then crystallises out in the usual manner.Secondary reaction causing plarisatim-MnzOa + Zn(NH,C1)2 + Zn -- Nn204Zn + (NH3C1),Zn.The zinc manganite thus formed coats over the manganic oxide, pro-tecting it from the action of the ammonium chloride.Secondary reaction causing depolarisation-Mn204Zn + 4NHaC1 = MnOz + 2H20 + MnC12 + Zn(NH3C1), +tLNH,GENERAL AND PHY SICmhL CHEMISTRY. 273From tliis equation we see that the manganese dioxide becomes activeagain, but as this action is slower than that which occurs.duringpolarisation, it is necessary to leave the cell uncircuited for a time ink d e r that it may recover its full power after being used.E. W. P.Currents Produced by Fused Nitrates in Contact with In-candescent Carbon. By BRARD (Cow@. rend., 95, 890-892).-Becquerel has shown that when incandescent gas-carbon is plungedinbo a bath of a fused nitrate, a powerful current is produced whichpasses from the bath to the carbon in the exterior circuit.The authorfinds that this takes place with all forms of carbon. The currentrapidly becomes weaker, in consequence of the deposition on thesurface of the carbon of a very compact strongly adhering crust ofsalts which protects the carbon from the action of the nitrate. Thefused nitrates become very fluid, and acquire the property of moisten-ing for a considerable distance the surfaces of heated bodies withwhich they are brought into contact. In consequence of this propertyit is not necessary to plunge the ignited end of the carbon into thefused nitpate, buf the cool end may be placed in the bath, and theother end then made incandescent.If a capsule, containing somegrains of fused nitrate, is left for a few minutes on the surface ofglowing eoals, a current is produced which flows from the bath to thecoals in the exterior circuit, and remains sensibly constant in intensityso long as the coals continue t o glow or any nitrate remains in thecapsule. I n this experiment the fused nitrate creeps over the edge ofthe vessel and flows down the outside on to the hot coals on whichthe capsule rests. The gradual flow of the thin layer of fused nitrateproduces regular chemical action, and thus the current remainssensibly constant. The current passes through the fire the more easilythe higher the tempemture. When a metallic capsule containing thefused salts is suspended freely above an active fire, a current stillpasses from the nitrate to the exterior of the capsule.These currentsare more feeble than those obtained by the preceding methods, but theymay be increased by surrounding the outside of the capsule with alayer of black-lead and encasing the whole in metallic gauze, Thebest effect is obtained by covering the outside of the capsule with alayer of asbestos-paper, covering the *latter with black-lead, and thenputting on the coarse metallic gauze. The metallic gauze forms thenegative pole of the element, and the capsule the positive pole. Acouple of this kind heated over a Bunsen flame gives a remarkablyconstant current of 6 to 7 milliampBres. It is important t o place thecapsule just in the point of the flame where the number of incan-descent carbon pai*ticles is greatest, for it i R these incandescentparticles which, coming in contact with the fused nitrate absorbed bythe asbestos, produce the current : the constancy of the current is dueto the fact that with a properly regulated lamp the temperature andthe proportion of carbonaceous products remain practically constantfor a long time.The nitrates which melt at about 200" are verystable, and only decompose at about 1000" or 1200". Up to this pointthey not only do not attack the vessels in which they aro containe274 ABSTRACTS OF CHEMICAL PAPERS.but, on the contrary, appear to prevent or to retard considerably theoxidising action of the fire. C. H. B.Determination of High Temperatures.(Chem. Centr. [3], 13,666-667.) -Gold and platinum alloys are recommended for this pur-pose. The alloy used is made into balls of l to 2 grams ; these arehammered out to plates about the size of sixpenny-pieces, bent in theform of an arch, and placed in rows in eupels, which are then arrangedin the furnace so that they can be seen through a peep-hole. Thetemperature is reckoned from the melting pointi, which may vary fromthe melting point of silver to that of steel (nearly). The same alloymay be used over and over agsin. D. A. L.Specific Heat and Heat of Transformation of Silver Iodide,and its Alloys with Cuprous and Lead Iodides. BY H. BELLATIand R. ROMANESE (Proc. Roy. XOC., 34, 104--105).-The authors havemade a, series of calorimetric investigations on these substances, theexpression a,nd contraction of which Rodwell has studied (Abstr., 1881,495, 465)- and 89 are the temperatures betweenwhich the structural change occurs, c the mean specific heat betweent and T for temperatures below 81, c1 the mean specific heat for tem-peratures above 02, and X the heat absorbed by unit weight of thesubstance in consequence of modification of structure :-I n the table belowFormula ofsubstance.el. 8,. c. c1- A.AgI.. . . . . . . 6.25CuJ, + 2AgI 95 228 095882 + (from 16 to 89) 0.058 8.31CuzIz + 4AgI 180 282 0.056526 + 0.000041 (T + t ) 0.0702 7-95Cu212 + 3AgI 194 280 0.059624 + 0.G00028 (T + t ) 0.0726 7.74Cu21, -+ 2AgI 221 298 0 061035 + 0.0000295 (T + t ) - 7.88Cu21, + AgI.256 324 0.063099 + 0.000026 (T + t ) .- 8-67YbI, + AgI. 118 144 0.47458 + 0.000026(T + t ) 0.0567 2.556142 156.5 0.054389 + O*OOOO3Z (T + t ) 0.0577V. H. V.Direct Determination of the Heat of Combination ofCertain Gases. By F. W. RUBE (Rec. Trau. Chim., 1, 158-166).-Ammonium Carbonate.-Lecher ( Wien. Akad. Ber., October, 18 78)determined by an indirect method the heat of combination of car-bonic anhydride and ammonia, and obtained the numbers 38,817 and36,642 heat-units (gram-degrees) ; mean 37,700. The differencebetween these numbers being rather wide, the author has endeavouredto obtain a more exact result by direct combination of the gases,bringing them together in a modified form of Bunsen's calorimeter.The mean value found for the heat evolved when 44 g.CO, and 34 g.NH, unite to form 78 g. ammonium carbamate, (NH,),C02 orNH,.CO.ONH,, was 39,300 units. Thomsen by an indirect methodfound 42,500, and Berthelot 38,100.Ammonium Chloride.-The heat of combination of NH, and HC1has been determined indirectly by Thomsen, by Berthelot, and byPavre and Silbermann, with the following results :GESERSL ASD PHl-SICAL CHEMISTRY. 275Thomsen. Berthelot . Favre and Silbermaun.41,899 42,70 0 43,24 GFavre and Silbermann by an indirect method obtained the number39,970, but regard this result as less exact than that found indi-rectly. The author of the present paFer obtained by the methodabove indicated the value 44,460.Lead Iodide. By BERTHELOT (Compt. reizd., 95, 952-955).-If lead iodide is dissolved in a hot concentrated aqueous solution ofpotassium iodide, the liquid on cooling deposits a pale-yellow crys-talline salt, of the composition PbI,,2KI,2H20.At a lower tempera-ture, or by the gradual evaporation of the mother-liquor in the cold,long pale-yellow needles are obtained, of the compositionThese salts combine together, forming intermediate compounds. Theheat of formation of these double salts was determined by treatingthem with a large quantity of' water. The following results wereobtained :-2KI,Pb12 + 2H20 liquid = 2KI,PbIz,2H20, crystnllised. + 4.62 cal.,, solid = ,, .. + 1.76 ,,2KI ? PbI, + 2H20 solid = 2&,PbI2,iH2O ,, . . + 2-58 ,,2KI + Pb12 = 2KI,Pb12 anhydrous ), + 0.84 ,,4KI,3Pb12 + 6H20 liquid = 4KI,3Pb12,6H20 ,, .. + 12.36 ,,,, solid = ), . . + 3.8 ,,4KI; 3Pb12 + 6H,O solid = 4KI,3Pbii,GH20 ,, . . + 2.8 ),4KI + 3PbI2 = 4KI,3PbI2 ,, . . - 1.0 ,,H. W.4K1,3PbI2,6H20.Develops.The formation of the first salt is exothermic in both the hydratedand anhydrous condition, whereas the formation of the second salt isexothermic in the hydrated condition only.A cold saturated solution of lead iodide yields an immediate pre-cipitate on addition of a few drops of a dilute solution of potassiumiodide or hydriodic acid. Solution of lead bromide, on the otherhand, is precipitated by hydrobromic acid, but not by soluble bro-mides, and solution of lead chloride is precipitated by hydrochloricacid, but not by soluble chlorides.By BERTBELOT (BUZZ.XOC. Chim., 39, 484-487) .-The following heat determinations of ethylene oxide weremade by the author:-Heat of combustion, C2H,0 + 0, = 2C02 +2H20 (liquid) = 307.5 cal. a t constant volume, 308.4 a t constantpressure ; heai; of vaporisation, 6.1 cal. ; heat of solution, 1.5 cal. ;heat of form2tion from its elements, C2 (diamond) + H4 + 0 =C2H40 (gas) = 17.7 cal; heat of formation from ethylene, C2H4 +0 = CzH40 (gas) = 33 cal. This last number is practically thehalf of the heat of formation of aldehyde from the same constituents,which may account for the fact that the formation of ethylene oxidedirectly from ethylene has not been observed, aldehyde being formedin preference.C. H. B.Ethylene Oxide276 ABSTRACTS OF CHEMICAL PAPERS.From the data of the heat of solution of glycol, the followingnumber is deduced:-C2H40 (liquid + H20 (liquid) = C,Hi,O,(liquid) = 19.1, a result comparable with the heat of hydration ofsulphur trioxide (20.4 cal.) and barium oxide (1'7% cal.).On heating ethylene oxide to redness the volume is doubled, withformation of carbonic oxide and marsh-gas, C2H40 = CO + CH4, a,reaction which disengages 26.4 cal.A very volatile liquid, probablyaldehyde, is formed as an intermediate product.The author draws attention to the differences of the heat of forma-tion of gaseous aldehyde and ethylene oxide, for C2 (diamond) +I n forming gaseous ethylene oxide evolves 17.7 cal.Thus ethylene oxide has a greater potential ener,gy than aldehyde,which explains its ready polymerisation and direct combination withwater and acids.The conversion of ethylene oxide into aldehydedisengages 32.8 cal., this isomeric change being accompanied with aloss of energy. Inasmuch as glycol on dehydration with zinc chloridefurnishes not ethylene oxide, but aldehyde, conclusions as to theconstitution of compounds drawn from their products of dehydrationby zinc chloride must not be accepted as final without an appeal tothe thermochemistry of the compounds in question.(Bey., 15, 2460--2464).-The author has made a series of determina-tions of the critical temperatures and boiling points of the alkylsalts of the C,H2,O2 series, the results of which are embodied in thefollowing table. In the first column are the several boiling points, t ;in the second the difference of boiling point (t - t,) of two consecutivesalts; in the third the critical t,emperature, T ; in the fourth thedifference of critical temperature, T - TI, of two consecutive salts ; inthe fifth the difference between the boiling point and critical tern-perat ure.Ha + 0 = C2H4O7 9 ,, aldehyde evolves .. . . 50.1 ,,V. H. V.Critical Temperatures of Alkyl Salts. By B. PAWLEWSKIEthereal salt. (t). (t-t,). (T). (T-TJ. ( T - t ) .Ethyl formate . . . . . . . . 55.7 - 238.6 - 182.9Propyl formate . . . . . . . . 85.1 29.4 267.4 28.8 182.3Isoamyl formate . . . . . . 121-8 36.7 304.6 37.2 182.8Methyl acetate . . . . . . . . 57.1 - 239.8 - 182.7Ethyl acetate.. . . . . .. .. 75.0 17.9 256.5 16.7 181.5Propyl acetate .. . . . . . . 100.3 25.3 282.4 25.9 182.1Normal butyl acetate . . 123.7 23.4 305.9 23.5 182.2Isobutyl acetate.. . . . . . . 114.6 - 295.8 - 181.2Methyl propionate.. . . . . 80.0 - 262.7 - 182.7Ethyl propionate . . . . . . 98.5 18.5 280.6 17.9 182.1Propyl propionate. . . . . . 122.3 23% 304.8 24.8 182.5Isobutyl propionate . . . . 135.8 - 318.7 - 182.9Ethyl bntyrate . . . . . . . . 121.7 - 304.3 - 182.6Propyl butyrate.. . . . . . . 144.3 22.5 326.6 22.3 182.GENERAL AND PHYSICAL CHEMISTRY. 277Ethereal salt. ( t ) . (t-tJ. (T). (T-Ti). (T-t).Methyl isobutyrate . . . . 91.7 - 273.6 - 181.7Ethyl isobutyrate . . . . . . 108.6 16.9 290.4 16.8 181.8Propyl isobtyrate . . . . . . 133.4 24.8 316.0 25.6 182.6The following relations are rendered evident by the tabulatedresults :-(1.) The difference between the boiling point and the critical tem-perature is a constant = 182.3.(2.) Alkyl salts of the same formula and analogous structurehave approximately the same critical temperature.(3.) The difference between the critical temperatures of two con-secutive alkyl salts is equal to the difference between their boilingpoints.(4.) The difference between the critical temperatures of two saltsof the same acid and alcohol-radicals (alkyls) is equal to the differencebetween their boiling points.The author considers that the determination of the critical tem-perature can be used as a control for the boiling point.V.H. V.Critical Point of Mixed Gases. By G.ANSDELL (Proc. Roy.Soc., 34, 113--119).-The author, in continuation of his researcheson the physical constants of liquid acetylene and hydrochloric acid(Abstr., 1882, 266), has investigated the behaviour of two gases inpresence of one another as regards the alteration of the critical point.Carbonic anhydride and hydrochloric acid were chosen as offeringexamples of gases which are easily prepared, and whose criticalpoints are accurately known; and further the results are probablynot modified by their mutual decomposition or by the formation of anaddition compound. The author used a Cailletet pump and the samemethod of experiment which he adopted in his former researches. Thecritical point of the mixture was determined, and then the tensions ofthe saturated vapour at different temperatures, together with the frac-tional volume to which the gas was reduced at the point of liquefac-tion, and also the relation between the liquid and gaseous volumes a tdifferent heights in the Cailletet tube.Some of the results areappended below.Temp. ofmixed gases.P. c. of C 0 2 inmixture 17.18 { 37-5Critical point ( 47.227I 46Temp. ofPressure. mixed gases. Pressure.2 7.84 28.8640.6654.22'70.28 mixture 19.37 67.3676.23 82-26P. c. of CO, in92.21 Critical point r 0 33.17 32-72 I 16.3 50.09 rl:*5 50.73P. c . of CO, in I 25.4 63.98 P. c. of CO, in I 26.6 63.31mixture 25-48 34 77.02 mixture 45.6'7 1 35 76-6443.2 90.03 I 37.6 79.14Critical point 45.1 - Critical point 1.38 81.35VOL.XLIV. I Q278 ABSTRACTS OF CHEMICAL PAPERS.Pawlewski, from his experiments on the ethers and alcohols, arrivesa t the result that the critical point of mixed bodies is directly pro-portional to the percentage composition of the mixture when theco-ordinate origin of temperature taken is that of the body having thelowest critical point. He infers that the same rule would hold goodin the case of liquid substances which are gaseous a t ordinary tem-peratures; but as the physical constants of liquefied gases are soexaggerated as regards their compression and expansion, and as thevariation of their critical points is materially affected by traces ofimpuriby, it would appear probable that mixtures of such liquefiedgases would not follow Pawlewski’s rule.This view is confirmed bythe results of the author’s experiments. V. H. V.Law of Freezing of Solvents. By F. M. RAOULT (Compt. rend.,95, 1030--1033).-1f A represents the reduction of freezing pointcaused by the solution of 1 gram of the substance in 100 grams ofthe solvent, M the molecular weight of the dissolved substance(anhydrous), and T the molecular reduction of freezing point, i.e.,the reduction caused by the solution of a gram-molecule in 100grams of liquid, then, if the solution is dilute,MA = T.The author has examined solutions of a large number of inorganicand organic bodies in water, benzene, nitrobenzene, ethylene dibro-mide, formic acid, and acetic acid, all of which, with the exception ofwater, contract on solidification.Acetic Acid.-All organic and many inorganic bodies produce amolecular reduction of freezing point between 36 and 40, generallyabout 39.Certain inorganic compounds, sulphuric and hydrochloricacid, calcium nitrate, and magnesium acetate produce a molecularreduction of about 19, nearly half the ordinary number.Formic acid behaves in a similar manner; the normal molecularreduction is 28, the abnormal 14.Benzene.-Almost all organic compounds and all non-metallicchlorides produce a molecular reduction between 47 and 51, mean49. Methyl and ethyl alcohols, formic, acetic, valeric, and benzoicacids, produce a mean reduction of 25, or half the normal reduction.Nitrobemewe and ethylene dibromide behave in a similar manner,the mean molecular reductions with the first-named being 68 and 34,and with the second 117 and 58.The different reductions are pro-duced by the same compounds as in the case of benzene.The majority of ‘theinorganic acids, alkaline bases, salts of the alkalis and alkalineearths prodme a molecular reduction between 33 and 43. Bariumand strontium chlorides give about 50. With the greater numberof more than 60 inorgaiiic substances the reduction is about 37.On the other hand, magnesium sulphate, metaphosphoric acid,hydrogen sulphide, and all organic bodies without exception give amuch more constant moIecular reduction, lying between 17 and 20,mean 18-5. Here, as in the other cases, one reduction is just doublethe other.Water.-The results are not so concordantGENERAL AND PHYSICAL CHEMISTRY.279Prom the results of experiments with more than 200 compoundsdissolved in these six different liquids, the author draws the followingconclusions :-All bodies when dissolved in a liquid compound which can solidify,lower its freezing point. In all liquids, the molecular reduction ofthe freezing point due to different compounds approaches two values,invariable for each liquid, and of which one is double the other. Thegreater value is most frequently met with, and is the normal mole-cular reduction; the lower value is the abnormal reduction. Thislower value corresponds with those cases in which the molecules ofthe dissolved substance are united in pairs.The normal molecular reduction of freezing point varies with thenature of the liquid, but if each of the molecular reductions is dividedby the molecular weight of the particular solvent, which reducesthe results to the case of a molecule of the subdance dissolved in100 mols.of the solvent ; the quotients, except in the case of water,are practically the same.Water .-. . 37 : 18 = 2.050 Benzene . .. . . .. . 49 : 78 = 0.628Formic acid 28 : 46 = 0.608 70.5: 123 = 0.600Acetic acid. 39 : 60 = 0.650 Ethylene dibromide 117 : 188 = 0.623Water obeys the general law if it is assumed that the physical mole-cule, a t least near the freezing point, is composed of three chemicalmolecules, for 37 : 18 x 3 = 0 685. It follows that a molecule of anycompound whatever, when dissolved in 100 mols. of any liquid what-ever of a different nature, lowers the freezing point of the liquid by aquantity which is almost constant, and which is about 0.62.This lawis general if i6 is admitted that physical molecules may be composedof two, or in rare cases of three, chemical molecules.Report to the R. Accademia dei Lincei on a Memoir byR. Schiff "On the Molecular Volumes of Liquids." By P.BLASERNA and S. CANNIZZARO (Gazzetta, 12, 488-494) .-A theoreticalpaper, not admitting of abstraction.Passage of Alcoholic Liquids through Porous Vessels. ByH. GAL (Compt. rend., 95, 844--846).-The author has studied thealteration in composition of aqueous alcohol when placed in bladdersunder different conditions. It is generally taught that alcohol placedin bladders becomes stronger with lapse of time, but the author showsthat this is not always true.When the bladders are exposed t o acomparatively high temperature and dry atmosphere, the alcoholincreases regularly in strength, but when placed i i t an atmospheresaturated with moistnre and at low temperatures, the liquid losesstrength regularly. The author thinks that those who have previouslystudied this subject have assigned too much importance t u the parttaken by the nzenibrar~e used, and have not taken sufficient account ofthe effect of the surrounding atmosphere.Nitrobenzene . . . -C. H. B.E. H. R.Lecture Experiments. Ry A. TV. HOFMANN (Ber., 15, 2656-2677).-A continuation of experiments previously described.'26 280 ABSTRACTS OF CHEMICAL PAPERS.Electrolysis of Hydrochloric Acid-The acid is decomposed in theclosed limb of a U-tube, and the liberated chlorine is absorbed by asolution of potassium iodide, which is admitted through the open endof the second limb, the volume of the gas being reduced to one-half.To show that by the union of chlorine with hydrogen no change ofvolume takes place, a glass bulb containing the mixed gases is intro-duced into a large wide-mouthed globe containing dry air.The gaseonsmixture is exploded by means of the magnesiam light, the pressure inthe globe before and after explosion being indicated by a manometer.For showing that the weight of a body is increased by combustion,magnesium or phosphorus is burned in a globe, the globe and metalbeing weighed before the experiment, and the globe together with theproduct of com bustion after the experiment.To show that carbonic anhydride has the same volume as the oxygenit contains, a glass globe fitted with a mercury safety tube is filledwith oxygen.A piece of glowing carbon is then introduced, and theopening immediately closed. After the combustisn of the carbon, theglobe is allowed to cool, when the mercury regains its original level.Combustion of Oxygen in Eydrogen.-The hydrogen is passed upwardsinto a glass globe, and the jet supplying the oxygen is introducedfrom above, both ends being closed by corks, through which the supplytubes pass. I n this way the cracking of the globe is avoided whichso frequently kook place when, as in the older form of the experiment,the hydrogen was allowed to burn below it in contact with the air.To show that aqueous vapour is lighter than air, water is boiled in aflask, the vapour being made to pass through a horizontal tube, inconnection with which are two vertical tubes, one directed upwards,and the other downwards.The &earn escapes by the upper tube, anda t the end of the horizontal tube, but does not escape by the lower tube.Relative Volumes of Water in the Liquid and Gaseous State.-A rapidcurrent of steam is passed through a globe connected above and belowwith narrow glass tubes. When full of vapour the upper end is closed,and the lower end dipped under mercury. The latter rises and fillsthe globe, while the condensed water is forced into the capillary tube.Maximum Density of Water.-Ixa a glass tube containing distilledwater a colonred glass float is placed, the density of which is such thatthe body just floats when the temperature of the water is 4".Thetube is sealed, so that when once adjusted it cannot get out of order.Becompositioa, of Water by Xodiunz.--By placing the sodium on theend of a long packing needle, and introducing it quickly into thewater under the inverted gas jar, the explosions which sometimesoccur when gauze is used, are avoided.Alternate Decomposition and Reproduction of Water.-A U-tube,closed at one end, is arranged with wires for passing the electricspark, and lower down with electrodes for decomposing water. Thelower part of the U-tube contains mercury, and above this in the closedlimb is acidulated water. A cork is inserted in the open end, andmercury is run out below, so as to diminish the pressure in the tube.The decomposition of the water is then started by the current, and asSoon as the evolved gases surround the upper wires, they are caused tocombine again by the passage of the electric sparkINORGANIC; CHEMISTRY. 281Volumetric AnaIpis of Ammonia.-One limb (which can be closedat both ends by stopcocks) of a U-tube is filled with chlorine.Ammonia solution is poured into the other limb, and about 10 C.C.admitted into the chlorine. The tube is well shaken, and the excessof ammonia replaced by dilute sulphuric acid, which is then admittedinto the closed limb. The liquid rises until the volume of the gas(nitrogen) is seen to have diminished to one-third of the originalchlorine.To1 umetric Relation of Ammonia to the Nitrogen it contains.--Theapparatus described in the last experiment is filled with dry a,mmonia:On shaking with a solution of bromine in dilute soda, lhe nitrogen isset free, and occupies half the original volume of the ammonia.For showing quantitatively the production. of nclphu& acid, theauthor employs a U-tube, one limb of which is provided at its upperextremity with a three-way stopcock, the other limb being open. Afterfilling the tube with mercury, nitric oxide (40 c.c.), sulphurous anhy-dride (60 c.c.), and dry oxygen (30 c.c.) are introduced. On finallyadmitting steam, the temporary formation of the characteristic whitecrystals may be observed. At the end of the experiment nearly theoriginal volume of the nitric oxide remains, whilst the mlphuric acidforms a layer above the mercury.Demonstration of &long and Petit's La.w.-The apparatus employedconsists of two similar thermometers, the bulbs of which are doublecylinders of glass, so that there is a hollow space in the centre of eachbulb, into which the metal experimented with can be inserted. I n con-ducting an experiment, the two metals whose specific heats are to becompared are heated to a given temperature, and quickly droppedinto the cavities of the two thermometers.The equivalent weights of lead and zinc can be shown by suspendinga weighed cylinder of zinc in a solution of lead acetate, and comparingthe weight of the precipitated lead with that lost by the zinc.Leidenfrost's Experiment Reversed-A platinum flask is maintainedat a white heat by a current of oxygen and hydrogen passing into it.It is then made to dip under water, when the platiuum will continuet o glow for some secor ils. A. I(. M

ISSN:0368-1769    

DOI:10.1039/CA8834400261

出版商:RSC    

年代:1883

数据来源: RSC

摘要:

INORGANIC; CHEMISTRY.I n o r g a n i c Chemistry.281Oxygen prepared from Potassium Chlorate. By A. WAGNER(Zeits. Anal. Chem., 21, 507-5lO).-It is well known t'hat oxygenprepared from potassium chlorate frequently contains appreciabletraces of chlorine, The author finds that whilst the absolutely puresalt yields pure oxygen, the commercial salt never does, owing totraces of organic matter present in it. Carbonic anhydride decom-poses even pure chlorate, with formation of chlorine. 0, H282 ABSTRACTS OLr CHEMICAL PAPERS.Formation of Ozone and Hydrogen Peroxide. By S. KAPPEL!Arch. Pharw. [3], 20, 574--577).-The author, having previouslyexperimented on the nitrification of ammonia in presence of metals(p. ZSS), made experiments of a similar kind with fixed alkalis andcopper in the presence of air, thinking that the nitrogen of the airwould be oxidised to nitrous acid ; he was, however, unsuccessful asregards the end sought.The test papers which he suspended in theflasks certainly became blue, but were immediately decolorised, andthe fluid, on the termination of the experiment, gave no nitrous reaction.The results indicate the simultaneous production of ozone andhydrogen peroxide ; the latter probably decomposes the former, whichis again formed, and a continuous process of the kind appears to goon. The fluid, if tested with potassium dichromate and sulphuricacid and shaken wi6h ether, does not show the hydrogen peroxide re-action, but if left for a long time in an open flask, or if a current of air ispassed through it to remove the ozone, the reaction is easily obtained.Activity of Oxygen.By M. TEAUBE (Ber., 15, 2421-2443).-Acontinuation of the author’s researches (Abstr., 1882, 795).PABT 1.-In this paper the author criticises the theory of Hoppe-Seyler, which supposes the dependence of the life functions of animalorganisms on a process of fermentation whereby hydrogen is evolved,and the oxygen molecule separated into its constituent atoms, theseat the moment of liberation assuming the active character of ozone, andeffecting the oxidation processes necessary for the continuation of‘ life.According to the author, this theory fails both on phpiological andchemical grounds, for in the first place the evolution of hydrogen hasonly been observed in the alimentary canal, where fermentationprocesses are undoubtedly effected by bacteria : further, if the fermen-tation and life processes were identical, then those organs of the body,such as the blood and muscles, on which the function of life is depen-dent, would soon after death show an evolution of hydrogen (in theabsence of oxygen) ; but this is directly contradicted by the researchesof Broech (Annalen, 115, 78) and hhose of the author, for freshmuscle does not reduce dilute nitric acid.Again fermentationbacteria convert nitrogenous into ammoniacal compounds, but theaiiimal organs in the absence of such bacteria effect no such change.Secoudly, Hoppe-Seyler based the chemical part of this theory onexperiments which showed that petroleum shaken up with sodium inthe presence of air absorbed oxygen with formation of volatile acids.Hoppe-Seyler did not however examine whether this result was notdue to the inevitable moisture of the air; and the experiments ofFudakowski, Schonbein, and others have shown that a, number oforganic Compounds, as benzene, ether, turpentine, gradually darken inthe air with absorption of oxygen, without the intervention of sodiumor of active hydrogen a t the moment of its liberation.Such experimentscannot serve as examples of the conversion of oxygen into ozone bynascent hydrogen. The author made some experiments directly bearingon the point. Dilute sulphuric acid and zinc were shaken up withair, but no ozone could be detected even by indigo snlphahe. Again,zinc and concentrated ammonia solution, or a mixture of ammonia andJ. 3’INORQANIC CHEMISTRY.283soda, shaken up with air, caused no conversion of oxygen into ozone,for the ammonia was not converted into nitrous or nitric acids; there-fore nascent hydrogen cannot separate from the oxygen molecuIe activeatoms, which combine together to form ozone. Further, nascent hydro-gen cannot form hydrogen peroxide with oxygen in the presence ofwater ; for although zinc and dilute sulphuric acid shaken up with aircause a formation of hydrogen peroxide, yet this must be attributedsolely to the water present in the sulphuric acid, for if concentratedacid be used, no hydrogen peroxide is formed, and nascent hydrogeuby itself reduces hydrogen peroxide.Schonbein observed that various metals, which with dilute acidsdo not cause the formation of hydrogen peroxide, possess this pro-perty when amalgamated with mercury ; this the author explains bysupposing that the amalgams of these metals have a more feeblereducing action than the metals themselves, and so do not destroy themolecules of the hydrogen peroxide.This view receives support fromthe fact that the evolution of hFdrogen from zinc and sulphuric acidis considerably modified by the amalgamation of the metal.Again, Hoppe-Seyler attributes the oxidising action of hydrogenpalladium in presence of water and oxygen to the liberated ornascent hydrogen, but he completely overlooks the formation ofhydrogen peroxide, which is produced according to the equation-The presence of water is necessary for this change, for palladiumhydrogen shaken up with ether in the air, forms no hydrogen peroxide,but its presence becomes manifest directly a little water is added.Substituting palladium hydrogen for zinc, the author repeated theexperiments described in his former paper (vide supra), and with thesame results.Palladium-hydrogen must then be classed among thosesubstances, which like zinc, lead, pyrogallol, &c. (which the authorproposes t80 name autoxidisab Ze), possess the property of attractingoxygen, so as to combine with the hydrogen of water to form hydrogenperoxide. I n conclusion, the author remarks that this property ofsuch substances is neither identical nor intimately associated with themore rare property possessed by some substances of rendering oxygenactive by converting it into ozone.PART II.-The author, to examine his theory that h-jdrogen peroxideis not oxidised water but reduced oxygen, has studied the electroiysivof acidulated water, the platinum electrodes being separated by acylinder of some porous material.No hydrogen peroxide is formedat the positive pole, but only at the negative pole, when the oxygenliberated from the opposite pole can come in contact with the hydrogen.It is thus probable that the hydrogen peroxide is formed by the directcombinutioii of the nascent hydrogen with the oxygen molecule, thus :H + H + 0, = H202; in this case, hydrogen peroxide differs in itschemical character from the peroxides of the heavy metals, which areformed by oxidation processes a t the positive pole.The quantity oflijdrogen peroxide is increased when the electrodes are OF palladium284 ABSTRACTS OF CHEMICAL PAPERS.but decreased with electrodes of mercury, silver, gold, and the heavymetals, and it is nil when the negative pole is of carbon. As a generalresult, it is found that those metals which, with dilute sulphuricacid and air readily form hydrogen peroxide, form this substancethe less readily when they are made the electrodes for the decomposi-tion of water. Conversely those metals, which form no hydrogenperoxide in presence of acid and air, but which possess the pro-perty of retaining hydrogen like palladium, form hydrogen peroxide inthe larger quantities during the electrolysis of water; but if thepalladium-hydrogen is made the negative electrode, the hydrogen iscompletely burnt to water: 2Pd2H + 0 = 4Pd + H,O.Thus the formation of hydrogen peroxide is not caused by activeoxygen, as hitherto believed, but is prevented by it.V. H. V.Ozone in Presence of Platinum-black. By E. MULDER andH. G. L. VAN DER MEULEN (Rec. Tmv. Chim., 1, 167-172).-By pass-ing ozonised oxygen over platinum-black at the ordinary temperature,the authors have obtained results from which, they say, it appearshighly probable that the ozone is thereby converted into ordinaryoxygen ; and they regard this result as the first known instance of thetransformation of an element into an allotropic modification under theinfluence of another element, without the occurrence of chemicalaction between the two.For the theoretical speculations as to themanner in which this transformation may be supposed to take place,we must refer to the original. H. W.Variations of the Amount of Oxygen in the Atmosphere.By C. A. VOGLER ( C h m . Centr. [3], 13, 556--558).-The authormakes some remarks in support of his theory against the a.ttack on itby Morley. Both agree as to the fact that the atmosphere varies incomposition vertically and not latitudinally, and therefore that thevariation in the quantity of oxygen is due to vertical air-currents.Morley is of opinion that the air which sinks down when the barometeris high is poor in oxygen, and would thus lower the amount of thatelement ; and that when the barometer is low, the lower layers of airare rich in oxygeu.The author thinks that when the barometer islow the air is well mixed by currents, and that therefore there is nodifference in the amount of oxygen found above or below a certainpoint ; and that when the barometer is high, the air, being in a stateof rest, resolves itself into bands according to Dalton’s law, whichwould cause a greater quantity of oxygen to be found in the lowerbands. He urges this by arguments and calculations. Finally, hewelcomes the idea of analysing air from various places under similarcircumstances, for it will settle the point whether the variation in thequantity of oxygen in the atmosphere is really a regular phenomenonor simply local.D. A. L.Carbonic Anhydride in the Atmosphere. By E. H. COOK(Phil. Mag. [ 5 ] , 14,387-395).-Taking the polar diameter of the earthas 7899 miles, the equatorial diameter as 7925.5 miles, and the heighINOROANIO CHEMISTRY. 285of the homogeneous atmosphere as 26,214 feet (nearly 5 miles), thecubical content of the homogeneous atmosphere is found to be591,647,337 cubic miles, or in round numbers 592,000,000 cubicmiles. If the average amount of carbonic anhydride in the atmosphereis traken as 4 vols. in 10,000, the total volume of the carbonic anhy-dride is 236,800 cubic miles, and the total weight 4287 billions ofpounds, or 1,913,685,908,480,000 kilos. These numbers differ con-siderably from those given by Dumas and Boussingault, and fromthat given in Roscoe and Schorlemmer’s chemistry. The first of theseis nearly 40 per cent.and the second about 33 per cent. too high.Recent investigations, however, show that the proportion of carbonicanhydride in the atmosphere is not, so high as 4 vols. in 10,000. Ifthe mean of these (Fittbogen arid Hasselbarth, 3.4 vols. in 10,000,Farsky 3.4 vols., and Reiset 2.942 vols.) is taken, the total weight ofthe carbonic anhydride is nearly 1545 billions of kilograms. Theaverage amount of coal raised annually in the world during the lastthree years is about 280,0d0,000 tons. Assuming that this con-tains 75 per cent. of carbon, 10 per cent. of which is thrown awaywith the ash, 182,000,000 tons of carbon are annually converted intocarbonic anhydride, which gives a daily production of 1,800,000 tons,or nearly 1,800,000,000 kilos.Assuming that one-third more isproduced by the combustion of wood, peat, oil, &c., the total dailyproduction by combustion is 2,400,000,000 kilos. The present popu-lation of the world is about 1,500,000,000, and each individualproduces on an average a kilogram of carbonic anhydride in24 hours. Assuming that twice as much carbonic anhydride isproduced by the respiration of lower animals as by that of man, thetotal amount produced by respiration is 4,500,000,000 kilos. perday. The amount produced by the decay of animal and vegetablematter may be taken as equal to that produced by the respiration ofman, and the amount sent into the air from subterranean sources maybe fairly assumed to be five times as great as the total amount derivedfrom all the other sources together.This gives about 40,000,000,000kilos. per day. Adding all these quantities together, it is found thatthe total amount of carbonic anhydride daily added to the atmosphereis at least 50,000,000,000 kilos., from which it follows that if nocompensating influences were a t work the proportion of carbonicanhydride would be doubled in about 100 years,The causes which remove carbonic anhydride from the air arefixation of carbon by plants, removal of the anhydride by zoophytes,and absorption of the anhydride by inorganic chemical action. Inthe first case alone is oxygen returned to the atmosphere ; in the othertwo cases the carbonic anhydride is absorbed as a whole.The totalarea of the land-surface of the globe is 57,600,000 square miles(Saunders). Of this 8,200,000 square miles are in arctic and antarcticregions, thus leaving 49,400,000 square miles on which vegetationmight flourish. A considerable portion of this area is, however,occupied by barren mountains, cities, and rivers. Estimating thetotal area of leaf-surface as 50 per cent. of the area of plant-bearingland, it follows that 24,700,000 square miles or 63,973,000,000,000square meters of leaf-surface are engaged in the work of removin286 ABSTRACTS OF GI-IEMICAL PAPERS.carbonic anhydride. Since each square meter of leaf-surface decom-poses about 1 litre of carbonic anhydride per hour, it follows that63,973,000,000,000 litres of the gas are decomposed every hour.Taking into account the fact that snnlight on the average lasts onlyten hours each day, and allowing 25 per cent.for diminution of theaction in winter, the average amount of carbonic anhydride de-composed per daly is 479,000,000,000 kilolitres, or more than900,000,000,000 kilos. A considerable proportion of the carbonthus removed is, however, returned to the air when the leaves decom-pose in the autumn, and allowance must, also be made for the factthat some plants give off carbonic anhydride in the dark. Onthis point, however, there are no data on which to base any calcu-lation, aiid the evolution of carbonic anhydride by the nocturnalrespiration of plank may be mucli greater than is usually supposed.From the numbers given it would appear t h a t the vegetable life on theglobe is of itsclf sufficient to maintain the purity of the atmosphere.This conclusion is, however, based on incomplete data.The removal of carbonic anhydride from sea-water by low forms ofanimal life takes place 'on a gigantic scale, but the carbonic anhydridethus removed exists in the sea and not in fhe atmosphere, and a verylarge proportion .of it must be derived from submarine volcaniceruptions.In all probability the influence of this action is felt onlyafter many years, and so far as the atmosphere is concerned, it cannotbe compared to plant life in poiiit of activity. Large quantities ofcarbonic anhydride are removed by inorganic chemical changes, as, forexample, in the conversion of orthoclase into kaolin (Sterry Hunt.,Am.J. Xci., May 1580), but any estimate of the rate of this action isimpossible.'i'hese calcnlahions seem t o show that the causes which removecarbonic anhydride from the air are more powerful than those whichadd this gas to the air. Its proportion must therefore be graduallydecreasing, but there are no trnstwortlhy data on which to base anyconclusions on this point. As to the source of the enormous quantitiesof carbonic anhydride already fixed in fhe form of limestone, we haveno knowledge. Either ant one time the akmosphere surrounding theearth must have been much richer i n carbonic anhydride than it is a tpresent, or, as Sterry Hunt supposes, there must be a universalatmosphere similar to our own from which the carbonic anhydridenow fixed in the .earth's crust has been derived.C. H. B.Nitrification in Presence of Copper and other Metals. ByS. KAPPEL (Arch. Phawn. [ 3 ] , 26, 567--573).--The author wasaccustomed to show his pupils, as a class experiment, the productionof nitric reactions when ammonia was left in contact with metalliccopper. Some flasks used in his experiments were left with theircontents, corked, for about a year; on examination he then foundthat the fluid had lost its ammoriiacal smell, and contained bothnitrites and nitrates, and induced loy this observation he made theexperiments reported in the present paper :-1. A quantity of copper cuttings were placed in a flavk connectedwith a drjing apparatus--a bulb tube containing copper oxide, and aINORQANIC CHEMISTRE'.287aspirator-the flask was placed on a sand-bath, and air drawn throughthe arrangement for 14 days, a t the end of which time the fluid gavestrong reactions of nitrites and nitrates, and the copper oxide was notreduced; a second experiment exactly similar, except that it wasmade in the cold, gave the reactions plainly, but not so strongly.2. Copper clippings and ammonia were placed in a flask throughwhich carbonic acid was passed, and when as nearly as possible freefrom atmospheric air, .the mouth was closed by fusion. After sixhours the fluid became intensely blue ; i t then gradually waned, andbecame colourless. When the flask was opened, nitrites and nitrateswere distinctly present.3. The arrangement in this experiment was similar to the last, butthe fluid was heated to 60-70" during the process; the reactionswere similar but sharper.Other experiments were made in which a current of hydrogen waspassed through the arrangement during the process.The resultswere variable and inconclusive.Similar experiments mere made with iron and zinc, and it wasfound that in all cases nitrification took place, but not with as muchactivity ; possibly, the author says, the nascent, hydrogen had a reducingeffect on the nitrites at the moment of their farmation, a continuousprocess of oxidation and reduction proceeding simultaneously. Theauthor's opinion is that the presence of air is necessary t o thisprocess of nitrification, and that although it proceeds in the cold, it isfacilitated by heat, and he thinks metals other than those mentionedare capable of producing similar results.Conversion of Tricalcium Phosphate into Chlorine Com-pounds of Phosphorus.By J. RIBAN (Conzpyt. +end., 95, 1160-1163; and BUZZ. Xoc. Chim., 39, 14).-When chlorine is passedover a mixture of tricalcium phosphate and carbon, or whenchlorine and carbonic oxide are passed over tricnlcium phosphatealone heated to incipient redness, a small qumtity of calciumchloride and metaphosphate is formed, but no further changetakes place. If, however, a mixture of chlorine and carbonic oxideis passed over an intimate mixiure of calcium phosphate and carbon(e.g., bone-black), heated in a glass tube to 330-340" in an oil-bath, phosphorus oxychloride, calcium chloride, and carbonic anhy-dride are produced.After some time, the calcium chloride formedinterferes with the reaction, but if it is removed by washing, thephosphate can be completely decomposed. The carbon plays nochemical part in the reaction, and is found practically unalteredat the end of the experiment. It is essential to the produc-tion of the reaction, and probably acts by condensing the gases inits pores. The reaction takes place in two stages, thus : (1) Ca,P20,+2C0 + 2C1, = CaP20G + 2C0, + 2CaC12, and (2) CaP,06 + 4CO +4c1, = 2POC13 + 4C0, + CaCI,. The reaction takes place slowly at180", and proceeds rapidly between 330" and 340".When carbonicoxide and chlorine are passed over bone-black at this temperature, nophosphorus oxychloride is a t first obtained, the gases being used upin converting the phosphate into metaphosphate, which is afterwardsJ. F288 ABSTRACTS OF CHEXICAL PAPERS.decomposed in accordance with the second equation. The phosphorusoxychloride thus obtained is almost pure,When phosphorus oxychloride is passed O V ~ T a long column of woodcharcoal heated to redness in a glass tube, phosphorus trichloride isformed, and carbonic oxide, or a mixture of carbonic oxide andcarbonic anhydride, according to the length and temperature of thecolumn of carbon, is given off.This method of reduction by means of a mixture of chlorine andcarbonic oxide in presence of carbon, will donbtless prove valuable inmany other cases.It answers very well for the production ofaluminium chloride from alumina, the change taking place easily a tthe temperature of an oil-bath. It may also serve for the productionof phosphorus oxychloride from calcium phosphate on it large scale.C. H. B.Volume-weight of Sulphuric Acid. By A. &BERTEL ( J . pr.Chem. [S 3, 26, 246-249).-1f concentrated sulphuric acid is boileddown to about half its volume, the residue contains 80.40 per cent.SOs = 98.50 per cent. HzSOa : sp- gr. a.t 0" (compared with water a t O*)= 1,857. If the same acid is distilled until acid of consGant composi-tion passes over, and the last portions of this are collected, they havethe composition 80-54 of SO, = 98.66 per cent.H2SOa, and are of sp. gr.1.8575 at 0". If these acids are mixed with dry or fuming sulphuricacid, a fall in the volume-weight takes place until the cQmposition ofnormal hydrogen sulphate, H2SOa, is reached. On the other hand,by the addition of anhydride, the volume-weight increases again, asseen from following table :-Percentage ) CorreBpond-( Parts.of SO,. ingmth H2SOk80.40 98-5080-54 98.668 1.00 99.2581.10 99.3581.63 100.0081.86 100.2882.10 100.5782-55 101.1382.97 101.64Volume -weightat 0".1-8 5 701,85751.85581.85501.85401.85481-85771.86401-8722The acid obtained by distillation with constant composition is themost concentrated, and has the highest sp. gr. The liquid normal acidundergoes dissociation even at 0".The tables of the volume-weights and composition of sulphuric acidedited by Bineau, Kolb, and Otto, show a continual increase insp.gr. D. A. L.Argentous Oxide. By W. PILLITZ (Zeitsch. Anal. Chem., 21, 496-506) .-In continuation of his investigation (ibid., 21, 27), theauthor has examined the precipitates obtained by the action of alka-line solutions of antimony triohloride, stannous oxide, or stannouschloride on silver nitrate. The product obtained by means of theantimony solution was proved to consist of a mixture of disodioINORUANIC CHEMISTRY. 259dihydric pyroantimonate (NaeK,Sb,O7 + 6H,O), metallic antimony,metallic silver, and silver chloride, whilst the alkaline tin solutionsfurnished a mixture of metallic silver and stannic acid.The pre-cipitates were quite free from asgentous oxide. 0. H.Aluminates and Basic Haloid Salts of Barium: Notes onBarium Hydroxide and Haloid Salts. By E. BECKMAN (J. pr.Chew., 26, 385-421) .-This paper, the first instalment of theresearch, gives a description of the barium aluminates.Action of Bwyta-water on Al.uminiu,m Compozcn,ds.--The result ofthis action is the production of a soluble aluminate having the com-position Alz,03,Ba0,Aq, and if the solution of this compound is digestedwith excess of aluminium hydroxide, an insoluble aluminate is formed.The result of mixing baryta-water with aluminum chloride is a preci-pitate of aluminiinm hydroxide, but a small percentage of barium isfound in the precipitate, and this is probably due to the formation ofbarium carbonate.The solvent action of baryta-water on metallicaluminium cannst be stated with certainty, as only metal having asmall percentage of silica was obtainable, but a t the ordinary tempera-ture aluminium hydroxide was formed as insoluble cryskalline powder,whilst Ba0,A1,03 was present in solution. At high temperaturesaluminium foil is attackd by water, but not readily, whilst wireremains unaltered ; but w&h baryta-water under like circumstances,a, solution of monobarium aluminate is formed. It appears then thatbarium forms definite compounds with aluminium, and the authorcarefully describes the method of preparation, the analytical re-mlts, &c., and shows that A1,03,Ba0,6H20 ; Al,O3,2BaO,5Hz0, andA1,O3,3Ba0,11H20, exist.The dibarium aluminate is prepared byboiling together the requisite quantities of baryta-water and freshlyprepared aluminium hydroxide, filtering while hot, and then boilingthe filtrate ; when this liquid is reduced to eight times the amount ofcompound present, oolourless crystals begin to be deposited, and canbe washed with hot water; these have the composition of dibarinmaluminate; the crystals are well formed, asymmetrical with anaxial proportion of 0.8545 : 1: 0*98SS, and amongst other faces, havethe following as principal : mPm, mPm, OP, 2'P2. Dibaiium alumi-m t e is a tasteless powder scarcely soluble in cold water, and is pre-cipitated from its solutions by alcohol ; when heated, the crystalsdecrepitate, slowly losing water, but not their form, and do not fuseat the highest temperatuzw; as regards the crystalline water, some islost, up to 125" ; at 1-53", 2 mols.H,O are slowly lost, and a third moreslowly still ; a rise of temperature to 250" removes a further quantity,but the whole of the fourth mol. is not got rid of below 300", and thelast or 5th mol. only a t a red heat. It is probable that this lastmol. is retained by the barium hydroxide, because in the case ofthe tribarium aluminate a mol. of water corresponding to each mol. ofBaO is firmly retained up to the last. When dibarium aluminateis heated in a cnrrent of dry gas, the water is rapidlj and suddenlyremoved, and when it is fused with acid potassium chromate, theremoval is irregular ; this is exactly opposite to what occurs in thecase of barium hydroxide under like conditions290 ABSTRACTS OF CHEMICAL PAPERS.A crystalline precipitate consisting of aluminium and bariumhydroxides, is produced when carbonic anhydride is passed into a solu-tion of the dibarium aluminate, and baryta-water removes thealumina from this precipitate; but if the gas be passed into the boilingsolution, short acicular crystals are formed, and baryta-water removesonly alumina from this a t a high temperature.Dry carbonicanhydride does not act on cold solid dibarium aluminate, but if thiscompound is ignited, then every mol. absorbs 1 mol. CO,.2Clovobariunt Aluminate.-The solution of this compound is obtainedby boiling the result of the last-mentioned reaction with water ; thesolution is stable, but if much concentrated deposits the dibariumcompound.The solid compound is prepared (1) by precipitation from the last-named solution by means of alcohol ; (2) by allowing the solution ofthe monobarium aluminate, whose percentage of alumina correspondswith that' of a concentrated dibariorn aluminate solution (1 = €9 toform spontaneously a granular non-crystalline deposit ; (3) the di-barium solution will also deposit crystals of the monobarium compound,and will decompose the more rapidly the more concentrated the solu-tion.All the preparations of this compound are loose white tastelesspowders, but slightly soluble in cold water, and hy boiling with waterform an opaque alkaline liquid.No alteration in appearance is notice-able when this compound is heated, although it loses crystalline water.When heated a t 110", nearly 3 mols. H,O remain, analogous tothose present in dibarium aluminate; of these, 1 mol. is removed a t130", another a t 220°, the last remaining until a red heat is reached:heated with acid potassium chromate, all the water passes away a tonce. Carbonic anhjdride causes all barium and alnmina to be pre-cipitated as needles from hot solutions, but the dry monobariumaluminate only absorbs this gas if an excess of the barium oxide ispresent.T?-ibaxium AZicn.tinate.-W hen 1 part of dibarium aluminate is boiledin 30 parts of water with 10 parts of barium hydroxide, the solutionfiltered hot, and Concentrated to 28 parts, colourless crystals of the tri-barium compound are deposited ; if the concentration is effected over alamp, there will be 7'4 mols.HzO present, but when an oil-bath is em-ployed, 11 mols. are found. This substance may also be prepared bymixing hot dibarium aluminate solution with barium hydroxide dis-solved in its own water of crystallisation. The crystals are opaque andbrittle, taste alkaline, and dissolve in 15 parts boiling water ; this solu-tion decomposes when boiled, the dibarium compound being formed.The first mol. of water of crystallisation is lost by heating a t 115",5 mols. are lost at 165", and 6 mols. a t 255", the remaining 1$ mol.making up the whole 7+ inols., is only lost at a red heat.Fusedpotassium dichromate removes that amount of water corresponding toits own temperature, 2 mols. remaining even after complete fusion.Microscopic needles containing barium and aluminium are separatedfrom hot solutions by carbonic anhydride, but the gas is onlyabsorbedby the solid a t incipient redness, every molecule absorbing 2 mols.GOz. Oxygen is not absorbed by this compound. E. W. I?INORGANIC CHEXISTRY 291Beryllium Hydroxides. By J. hl. v. BEMMELEX (J. pr.Chew. [2], 26, 227--246).-From previous researches the authorconcluded that those hydroxides which separate from their solu-tions in a colloid form, such as those of silicon, iron, &c., never havea constant composition, and are scarcely ever homogeneous. He,however, thinks it probable that under certain conditions they oughtto be obtained as chemical compounds, and remain constant withiii awide range of changes of temperature.For illustration of this hypo-thesis the hydroxides of beryllium seemed well adapted. Of thesethe author has distinguished two, a, granular, and P, gelatinous. Thep-hydroxide is precipitated by ammonia from pure beryllium sulphate,it is washed out of contact with the air with cold water, dried in astream of air free from carbonic anhydride and powdered ; its constitu-tion is then represented by: Be0,1*61( H20),0*025(C02). When washedand dried in the air, its constitution is Be0,2*63( H20),0*05(COz).To prepare the a-hydroaide, the solution of the &hydroxide insulphuric acid is precipitated with potash and redissolved byexcess of the precipitant; it is then diluted with much water andboiled. The granular deposit of the hydroxide is washed wikh boilitig-hot water, excluding air; it forms a fine white powder, is free fromcarbonic anhydride, and has the constitution BeO,H,O, which remainsconstant up t o ZOO"; dissociation now commences and reaches amaxinium a t 215", and after two hours' heating at 215-220", theoxide loses half a mol.H20, whilst after ten hours' heatingBe0,0*18H20 reniaius ; the last &th mol. HzO is only entirely drivenoff a t a strong red heat. From air saturated with moisture, thea-hydrate will absorb as much as $--+ mol. H,O, which, however, isgiven off again in the ordinary air. mol. H,O a t 200"'its constitution is definitely changed, for although i t absorbs 1 mol.ofwater from moist air at 15", it gives it up again in dry air. Heatedat 280", the water is reduced to 0.13 mol., now again it absorbs 1 mol.H20, but gives it up only till the residue is reduced to 0-18 mol.After being heated to redness, it behaves in the same way ; but a strongred heat changes it altogether; it then loses all power of absorbingwater, and is only soluble in boiling sulphuric acid.The p-hydroxide is a fine powder; a t the ordinary temperature itabsorbs a considerable amount of water from moist air, even when ithas been previously heated at 100". It has no constant composition.When heated it'gradually and constantly loses weight (water) ; between150 and 180°, the compound Be0,R20 is attained, and remains constantbetween 180 and 200" ; above this temperature a t about 215" it under-goes changes similar to the a-hydroxide.When tested with regard tothe power of absorbing salts from aqueous solutions, the P-hydroxideshows this property, the a- does not. Comparative experiments withhydrated magnesium oxide confirm the results of previous investiga-tors (Ditte and Rose); it retains the composition Mg0,H20 evenwhen heated above 350", and does not even undergo molecular changebelow this temperature ; it loses water of hydration between 350" andred heat. The author comes to the conclusiort that beryllium a-hydr-oxide resembles those of magnesinm and calcium, whilst beryllium&hydroxide resembles those of aluminium: &c.After losin292 ABSTRACTS 03' CHEMICAL PAPERS.Thus the former can be represented by a definite and simple formula,and is constant within a certain range of changes of temperature, butsmaller than that of magnesia.The changes which the P-compoundundergoes during heating are similar to those observed by Berthelot inferric hydroxide, for he found that from the time it was precipitated,it constantly changed molecularly, and a t no period could be repre-sented by a simple formula. The author considers this peculiarity ofthe gelatinous hydroxide to be due to the fact that it is a mixture ofhydroxides, which behave differently a t the same temperature, that is,that each one requires a different temperature to convert it into thelower hydroxide or anhydride.This view is supported by some observa-tions which the author has made on the hydroxide freshly precipitatedfrom aluminium chloride by ammonia. 1. After boiling for 24 hourswith water it has the composition A1203,1.6H20. 2. Washed for sometime with cold water it is A1203,1 *9H,O. 3. Precipitated from dilutedsolution and quickly washed with water it is A1203,2*6H,0. 4. Afterhalf a year in contact with water it is Al203,3.lH20. The last-mentionedis quite constant between 1.5 and loo", and even above. Nos. 1,2, and 3are mixtures of this with a lower hydroxide. D. A. L.Atomic Weight of Yttrium. By P. T. CLEVE (Corn@. rend., 95,1225--1226).-The determinations of the atomic weight of yttriummade in 1872 are inexact, since no precautions were taken to sepa-rate terbium, which at that time was not definitely known to exist.By fractional precipitation with oxalic acid, the author has obtainedfrom 3 to 4 grams of yttria with a, constant molecular weight.Themean of twelve determinations of the amount of yttria in the snlphateprepared from this pure oxide is 48.503 f 0.00029 per cent. It fol-lows, therefore, that the atomic weight of yttrium is 89-02 if 0 = 16and S = 32, or 88.9 0.027 if 0 = 15.9633 and S = 31.984. Pureyttria is perfectly white, the yellow colour which it sometimeshas being due to the presence of very small quantities of terbia.Lecture Experiments illustrating the Combination of Zincwith Sulphur. By H. SCHWARZ ( B e y . , 15, 2505--2508).-Afte~alluding to the common method of illustrating chemical combinationby heating flowers of sulphur with copper or iron filings, the authorsuggests the following experiment.Two parts of zinc-dust and onep a r t flowers of sulphur are intimately and carefully mixed ; on apply-ing a light the mixture ignites and burns with n green flame, and thezinc sulphide is deposited on surrounding objects; the mixture canalso be ignited by percussion, and in an explosion apparatus the authorfound that the detonating power of the mixture was about an eighthof that of blasting powder.The author explains the fact that sulphur does not mix directlywith molten zinc, as a form of Leidenfrost's phenomenon, as thesulphur vapour prevents the metal coming in contact with the moltensulphur ; or perhaps a thin layer of zinc oxide or sulphide is formedbetween the sulphur and the metal.If carbon bidphide vapour, either by itself or mixed with hydrogensulphide, be passed over heated zinc-dust, zinc sulphide is formed withC.H. BINORGANIC CEEMISTRY. 293formation of methane and hydrogen. Similarly, if carbon bisulphideand ammonia is led over zinc-dust, ammonium cyanide is formedaccording to the reaction CS2 + 2NH3 + 2Zn= ZZnS + NE[I,.CN + H2.The author also calls attention to the use of zinc-dust for removingsulphur from compounds, and adduces as examples the decompositionof thiocarbanilide into aniline and phenylnitrile fCS.NHPh, + Zn =ZnS + NH,Ph -k PhCN], of thiocarboparatoluidide into paratoluidineand tolylnitrile, and the conversion of allylthiocarbimide inio allyl-nitrile. V.H. V.Separation of Gallium. By L. DE BOISBAUDRAN (Compt. rend.,95, 1192-1194 and 1332-1334 ; see also this vol., p. 21, and Abstr.,1882, pp. 897 and 1323).--From Bbmuth.-(1.) The moderately acidsolution of the chlorides is saturated with hydrogen sulphide; theprecipitated bismuth snlphide is free from gallium. (2.) The bismuthis reduced by means of zinc, or much better, by finely divided copper ina slightly acid solution a t a gentle heat. (3.) The gallium is pre-cipitated by means of potassium ferrocyanide in a solution containingone-third its volume of strong hydrochloric acid : contrary to thegeneral statement, the precipitate produced by potassium ferrocFanidein solutions of bismuth chloride is soluble even in dilute hydrochloricacid. Bismuth and gallium cannot be separated by means of potas-sium hydroxide, since the alkaline solution retains notable quantitiesof bismuth.From Copper,-(l.) The copper is precipitated in an acid solutionbyy.means of hydrogen sulphide ; the precipitate is washed withacidulated water containing hydrogen sulphide. (2.) The copper isprecipitated with excess of potassium hydroxide, and the liquid boiledfor some minutes. (3.) The copper is precipitated by metallic zincor, much better, by electrolysis. (4.) The solution is made stronglyalkaline with ammonia, and boiled for some time. If much copper ispresent, the precipitate must be redissolved, and the operation repeatedseveral times.The liquid should contain a moderate quantity ofammonium chloride. All four methods are good, but the first ispreferable where it can be applied.l + ~ m .Mewu,ry.-(l.) The solution is strongly acidified with hydro-chloric acid and saturated with hydrogen sulphide. This method israpid and exact, and is to be st;rongly recommended. (2.) The mercuryis reduced by zinc or, better,, by copper. (3.) The gallium is precipi-tated as ferrocyanide in presence of it considerable quantity of freehydrochloric acid, and the precipita'te is washed with dilute hydro-chloric acid. Mercury cannot be separated from gsllium by means ofpotassium hydroxide, as contrary to the usual statement, the alka-line liquid retains notable quantities of mercury.The precipitatedmercuric oxide is, however, free from gallium.F T O ~ XiZver.-The silver is precipitated by a slight excess of hydro-chloric acid in presence of a considerable quantity of nitric acid, or thesilver is precipitated by hydrogen sulphide in a moderately acid(hydrochloric or nitric) solution.From Goid.-(1.) The distinctIy acid solution is saturated withhydrogen sulphide. (2.) The gold is reduced by sulphurous acid, andVOL. XLIV. 294 ABSTRACTS OF CHEMICAL PAPERS.the precipitated metal washed with water containing a little hydro-chloric acid. (3.) The solution is made distinctly acid with hydro-chloric acid, and the go4d reduced by finely divided copper a t theordinary temperature, or at a gentle heat.From Pallndi~cm.-(l.) The solution is strongly acidified withhydrochloric acid, submitted t o long treatment, with hydrogen snl-phide, and then heated at 70" for two hours.The solution should besomewhat concentrated, and the greater part of the free acid shouldbe expelled by evaporation before the last treatment with hydrogensulphide. (2.) The palladium is reduced by copper in a distinctlyacid solution a t 80°, the precipitated metal never containing morethan an insignificant trace of gallium. If zinc is used instead ofcopper the precipitated palladium obstinately retains notable quanti-ties of gallium. Precipitation of the palladium as potassium palladio-chloride is inexact, since the double chloride is slightly soluble inalcohol, and the precipitate retains distinct traces of gallium.From PZatinzLm.-The only exact method is to saturate the dis-tinctly acid solution with hydrogen sulphide, heat to 70", and continuethe passage of hydrogen sulphide for several hours.The wash- wateris mixed with the filtrate, evaporated to expel the greater part of theacid, and again treated with hydrogen sulphide. An approximateseparation is effected by adding ammonium chloride to the solutionmade distinctly acid with hydrochloric acid, and mixed with alcohol.The precipitate appears to be free from gallium, but the liquidcontains small quantities of platinum. Platinum is reduced withgreat difficulty by copper, even in R hot solution. 'It is completelyprecipitated by zinc, but the metal retains gallium even more obsti-nzttely than does palladium. C.H. B.Ey A. DITTE(Ann. Chim Phys. [ 5 ] , 28, 145--182).-When a solution of stannouschloride is treated with potassium or sodium hydroxide, stannoushydroxide separates as a compact precipitate, which may be easilywashed by decantation as long as an excess of the alkaline chlorideformed in the reaction is present. When the washing approachescompleteness, however, the solution becomes turbid, and the precipi-tate needs days to settle. The author haa made a careful investi-gation of the behaviour of stannous hydroxide and stannous chloridein the presence of various reagents. From the results of these experi-ments, he draws the following conclusions :--(i.) Stannous hydroxide is transformed into the crystalline anhydrousoxide by traces of any acid which is capable of forming a stannoussalt, decomposable by boiling water into free acid and oxide.(ii.) Thesame change takes place in the presence of salts (such as stannouschloride, ammonium chloride, &c.) which are partially decomposed bywater, with liberation of small quantities of an acid coming underhead (i). (iii.) This conversion of the hydroxide into the oxide is noteffected by acids forming stable stannous salts (such as nitric acid),nor by those (such as sulphuric acid) giving stable basic salts in thepresence of water. (iv.) Potassium and sodium hjdroxides act onstannous hydroxide both in the cold and on heating, but the reactionStannous Oxide and some of its CompoundsINORGANIC CHENISTRT.295is complicated, and the resulting product varies according to the con-centration and temperature of the solution. According to circum-stances, an alkaline stannate, a mixture of this latter with stannousoxide, or a mixture of the stannate with metallic tin, may be obtained.(v.) Contrary to the statements nsually given in text-books, ammonia,not only does not cause the dehydration of the hydroxide, but preventsit taking place : the author shows that if the anhydrous oxide isformed, it is only after the ammonia has been expelled by boiling, andthat if care be taken to replace this, and the solution be kept alkaline, nodehydration will take place, however long the boiling may be continued.(vi.) Anhydrous stannous oxide may be obtained in several slightlymodified forms, but these modifications are not definite enough to betermed alIotropic.(vii.) At a red heat, stannous oxide partially decom-poses into stannic oxide and tin, the former uniting with unchangedstannous oxide to form Sn304. (viii.) The salts of silver, psllladium,and platinum form with fitannous salts, stannates or meta-stannates,according to tbe relative proportions of the two reagents. From thedecided colours of these compounds, they are very good tests for dis-tinguishing stannous from stannic salts.A Higher Oxide of Titanium. By A. WELLER (Bw., 15, 2,599-26OO).-A higher oxide of titanium, probably TiO,, is produced whenfreshly precipitated titanic hydroxide is treated with hydrogen per-oxide or when ammonia is added to a solution of titanic acid and hydro-gen peroxide.This oxide has a yellow colour. It is decomposed by heat,yielding oxygen, water, and titanic oxide. It dissolves in strong acids,forming a reddish-yellow solution, from which the oxide is reprecipi-tated by alkalis ; if an excess of alkali is used, titanic oxide is throwndown. On heating the hydrochloric acid solution, chlorine is evolved. w. c. w.By H. SCHULZE(J. pr. Chem., 25, 431-452).-1t is well known that sulphurettedhydrogen does not precipitate, or only partially precipitates, a pureaqueous solution of arsenious anhydride. The author has experi-mented on this fact, and concludes that the water contains arsenioussulphide in solution. In one experiment, he dissolved 10 grams ofpure arsenious anhydride in 1 litre, and passed sulphuretted hydrogeninto the solution, which became yellow and turbid, forming very thingolden-yellow flakes on the surface, which, on agitation, were throwndown and sank to the bottom in a flocculent state.The rsmainingsolution was slightly turbid and of a reddish-yellow tint. This tur-bidity could not, however, be removed by filtration, and on examina-tion under the microscope no traces of solid matters could be detected,the solution being clear and yellow. When the solution was renderedturbid by addition of an acid or salt insufficient to produce completeprecipitation, solid particles in a yellow menstruum were seen underthe microscope. The solution moreover was not turbid when viewedby transmitted light (e.g., in thin layers between parallel plates ofglass), but only in reflected light, an effect which the author attributesto fluorescence.Carbonic anhydride was passed through the abovesolution to remove excess of sulphuretted hydrogen, and the arsenicL. T. T.Arsenious Sulphide in Aqueous Solution.0 296 ABSTRACTS OF CHEMICAL PAPERS.and sulphur were determined in a portion, and found to be in theratio of As2 : Ss. This solution of arsenious sulphide is a colloid, andcannot he dialysed, although any added arsenious anhydride can bereadily removed from it by dialysis. On evaporetion to dryness, anamount of arsenious sulphide remains proportional to the amount ofarsenious anhydride taken, this solid sulphide being no longer solublein water.There is a limit to the strength of the solutions of arsenious sul-phide prepared by passing sulphuretted hydrogen through aqueoussolutions of arsenious anhydride on account of the sparing solubilityof the latter, but by passing sulphuretted hydrogen and then dissolv-ing fresh arsenious anhydride and so on, the author succeeded inobtaining a 37-46 per cent.solution of As,S3 (1 pt. As$, in 1.67 pts.water) ; it was like an intensely yellow milk, but perfectly transparentunder the microscope. The stronger solutions deposit a small quan-tity of solid matter on prolonged standing ; the dilute solutions aremore permanent, a solution of 1 in 500 being quite unchanged afterstanding for three months.Dilute solutions of arsenious sulphide prepared from stronger solu-tions by dilution are more turbid than dilute solutions of the samestrength prepared directly, and have a yellow rather than a reddish-yellow tint,.These solutions are only very slightly influenced by high tempera-tures; but finely divided animal and vegetable charcoal, acids, andsoluble salts have the power of precipitating the solid sulphide. Inthe case of soluble salts, it is found that there is a certain state of diln-tion for each salt, at which it ceases to precipitate, and further theprecipitating power of the various salts depends on the metals, acdonly slightly on the acids in those salts.The salts of the alkalis havethe least precipitating power ; the ferric, chromic, and aluminiumsalts the greatest.The author infers that we have to deal with a colloidal modifica-tion of arsenious sulphide comparable with the colloYdal ferric andaluminium hydroxides, soluble silicic acid, and soluble albumin.Formation of Crystallised Uranates in the Dry Way.By A.DITTE (Compt. rend., 95, 988-991) .-If uranoso-uranic oxide, U308,is fused with sodium chloride in a platinum crucible, the bottom of whichis kept considerably hotter than the upper portions, a ring is formedround the sides of the crucible a t the surface of the fused mass, con-sisting of a mixture of sodium chloride and brilliant greenish-yellowplate8 of sodium uranate, Na,U,O,, insoluble in water, but easily solu-ble in dilute acids. If the heating is continued after the removalof the first ring, a second ring is obtained, smaller than the first, butsoon the fused mass ceases to yield a crystalline deposit no matter howlong the fusion may be continued.The mass is allowed to cool, andthe sodium chloride removed by washing, when a dcep green crystal-line residue is left, which dissolves partially in dilute hydrochloric andsnlphuric acids, leaving a black crystalline residue of uranous oxide.The portion soluble in acids consists of crystals of the intermediateoxide, Uz05. When the sodium chloride is heated with the uranoso-F. L. TINORQANIC CHEMISTRY. 297uranic oxide, the latter is decomposed into oxygen which ufiites withthe uranic oxide, forming sodium uranate, and into uranous oxide,part of which combines w i t h uranic oxide forming the intermediateoxide, U03,U02, whilst the remainder crystallises.The chlorine ofthe sodium chloride is liberated, but a t high temperatures, attacksneither the uranium oxides nor the platinum of the crucible.If the sodium chloride is mixed with a little sodium carbonate thesame products are obtained; but if the chloride and carboriate arein about equal proportions, sodium uranate is the sole product. If theuranoso-uranic oxide is fused with pure sodium chloride, and sodiunichlorate is added in small portions so that the crucible is always filledwith an atmosphere of oxygen, the uranium is entirely, althoughslowly, converted into crystalline uranate. If the uranium oxide ismixed with sodium chlorate, decomposition is accompanied by defla-gration, and the uranium oxide is almost instantly converted intoamorphous sodium uranate. The reaction is moderated by thepresence of sodium carbonate, but the product is the same.Theamorphous uranate can be obtained in crystals by fusing it withsodium chloride.Any of the alkaline urnnates can be obtained in greenish-yellowplates, insoluble in water, and infusible at a bright red heat, by any ofthese three general methods. Sodium uranate is more readily formedthan the corresponding potassium salt. If the green uranium oxide isfused with sodium and potassium chlorides mixed in equivalent pro-portions, the crystals deposited are almost pure sodium uranate. Thepotassium, rubidium, lithium, and maguesium uranates have beenobtained in crystals by these methods.When uranoso-uranic oxide is fused in the same way witb calcium,barium, and strontium chlorides, the corresponding uranates areobtained, CaU,07, BaU,O,, SrU,07.If the uranium oxide is heatedwith the chlorat,es of the alkaline earths, it is entirely converted intoamorphous uranates, but the latter, when fused with sodium chloride,yield a ring very slowly, and the greenish-yellow plates thus ob-tained have the composition respectively CaU40,2, BaU,O,,, SrU,O ,?.The strontium salts crystallise more slowly than tjhose of calcium,whilst those of barium, on the other hand, form very rapidly. Theseuranates form greenish-yellow plates, insoluble in water, but solublein dilute acids.If heated for some time to bright redness, they acquirea deeper colour, and become less soluble in dilute acids.C. H. B.Nitrososulphides and Nitrosocyanides. By 0. PAVEL (Ber., 15,26OO-2606) .--Yotussium ferrtrnit.1.ososzLZ~hide, K2Fe8 (NO) 14S6, is bestobtained by adding 40U C.C. of potassium sulphide, prepared from44 grams potash, to a boiling solution of 35 grams of sodium nitrite in400 C.C. water. After t,he addition of a few drops of dilute sulphuricacid, 159 grams of ferrous sulphake dissolved in 1200 C.C. water areslowly poured into the hot mixture. The liquid is heated in a water-bath for about half an hour, unt.il a deposit begins to settle on thesides of the flask. It is then quickly filtered, and dilute potash isadded to the filtrate.After 48 hours potassium ferronitrososulphid298 ABSTRACTS OF CHEMICAL PAPERS.crystallises out. It is purified by recrystallisation from water at 70°,containing a small quantity of potassium hydroxide. The potassiumand ammonium salts contain 2 mols. H20. The ammonium salt is lesssoluble tjhan the potassium salt, and the rubidium salt is less solublethan the ammonium salt. The caesium compound is insoluble incold water, and sparingly soluble in alcohol and ether. The easilysoluble sodium, lithium, magnesium, calcium, and barium salts areunstable. T1Fep(N0),S3 + H20 is sparingly soluble. The salt obtainedby the action of ferroiis sulphate on a mixture of sodium thiocarbonateand sodium nitrite, is sodio-ferrous nitrosulphide, and not ferrousnitrosothiocarbonate, Fe4S (NO)&SZ, as stated by 0.Low. Thesenitresosulphides are decomposed by heat in presence of air, withformation of ammonium sulphate, ferrous sulphide, and other pro-ducts; if air is excluded, no ammoniuin aulphate is produced. Thefree acid, Fe4(N0)7SaH, is precipitated Ly dilute sulphuric acid froman aqueous solution of the sodium salt. It is an amorphous unstablecompound, insoluble in water, alcohol, and ether, but soluble in chloro-form and carbon bisulphide. Sodium ferronitrososulphide is com-pletely decompo,sed by hot strong sulphuric acid, by silver oxide orsulphate, by hydrochloric acid, and by iodine?.A second series of nitrososulphides is obtained by treating the pre-ceding salts with a warm dilute solution of potash.These salts arennstable ; they are, with the exception of the iron compound, insolublein ether, chloroform, and carbon bisulphide. They are decomposedby potassium ferricyanide, which does not attack the first class ofnitrososulphides. The composition of the potassium and sodium saltsis represented by the formulz-K,Fe,(NO)& + 4H20 and Na2FeZ(NO),S2 + SH20.Ethyl f e r r o n i t r o s o s u l ~ ~ i d e , EtBFcz(N0)pS2, prepared by the action ofethyl iodide on an alcoholic solution of the potassium salt, forms largemonoclinic ciytnls melting a t 78". The dark glistening crystals diu-solve freely in ether, chloroform, benzene, ethyl iodide, and carbonbisulphide. This compound is not attacked by potash or by sulphuricor hydrochloric acids, but it is completely decomposed by nitric acid.The author considers that the formation of sodium nitro-prusside, i.e.,sodium nitrosoferricyanide, by the action of nitric acid on sodiumferrocyanide, takes place in the following stages :-Artificial Production of Iridosmin. By H. DEBRAY (Conzpt.Tend., 95, 8iS--SSO>.--if iridium is fused with iron pyrites a t a hightemperature a regulus is obtained, which, when trea.ted with dilutehydrochloric acid, leaves a residue of crystallised iridium, mixed witha light black amorphous sulphide easily soluble in dilute nitric acid.The iridium retains from 1 to 2 per cent. of iron, and crystallises inoctohedrons, a1 though some flattened crystals have the appearance ofregular hexahedrons. Osmium behaves in a precisely similar manner,but the crystals obtained retaiu no sensible traces of iron, and have alMINERALOGICAL CHEMISTRY. 299the characteristics of the metal obtained by the action of hydrochloricacid on alloys of osmium with zinc or tin.When a mixture of one part amorphous osmium with 1, 2, or3 parts amorphous iridium, is fused with a large excess of iron pyrites,and the fused mass treated successively with hydrochloric and nitricacids, a crystalline residue is obtained, which consifits of regularoctoliedrons mixed with hexagonal plates, closely resembling certainnatural varieties of iridosmin. The crystals have not the compositionof the mixture from which they are prepared, owing to the partialconversion of the metals into sulphides; the relative proportion ofosmium and iridium does not depend on the relative quantities of thetwo metals employed, but varies with the temperature to which themixture is heated. Three specimens obtained had the following com-position :-1. 2. 3.Iridium ...... 50 59 62.5Osmium ...... 50 41 37.5100 100 100.0-- -- --In appearance and properties, these alloys are identical with thenatural iridosmin. Since osmium and iridium are isomorphous, andcan crystallise together in all proportions, it is possible that naturaliridosmin may be a true isomorphous mixture belonging to theregular system, notwithstanding the hexagonal appearance of some ofthe crystals. The composition of natural iridosmin is, however, muchmore complex than that of the artificial crystals. C . H. B

ISSN:0368-1769    

DOI:10.1039/CA8834400281

出版商:RSC    

年代:1883

数据来源: RSC

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MINERALOGICAL CHEMISTRY. M i n e r a l o g i c a l Chemistry. 299 Analysis of the Coal of the Muaraze. By P. GUYOT (J. Pharm. [5], 6, 474--473).-This is a short paper, containing an account of thin beds of coal found in the valley of the River Muaraze, a tributary of the Zambesi. The volatile matter varies in different specimens from 20 to 22 per cent., and the coke from about 50 to 55 per cent. E. H. R. The Thorite of Arendal. By L. F. NILSON (Compt. rend., 95, 784-7886).-Nordenskiold found, near Arendal, in 1876, a crystalline silicate containing 50 per cent. of oxide of thorium, and 10 per cent. of uranous oxide. He regards the mineral as a variety of thorite. Later, the same mineral was discovered a t Hitter0 (Norway) by Lindstrom, and at Champlain (U.S.A.) by Collier, who called it uranot ho rite.The mineral is interesting as containing urannus oxide. Zimmer- man has shown that uranous oxide has the formula UOz, and the oxide of thorium having probably the formula Thoz, it is to be presumed that the two oxides are capable of replacing one another in thorite in300 ABSTRACTS OF CHENICAL PAPERS. variable proportions. The molecular volumes of the oxides in question confirm this hypothesis. The author has obtained pure sulphate of thorium by a new and simple method. He finds that by saturating 5 parts of water at 0” with 1 part of crude anhydrous sulphate and then warming to 20’, thorium sulphate is precipitated as a heavy white crystalline powder, amounting to two-thirds of the sulphate dissolved. The precipitate is washed with cold water, the mother-liquors are evaporated to dryness, and the product is subjected to the same treatment.Proceeding in this way a solution is finally obtained which, saturated a t zero, precipitates nothing more when warmed to 20”. The solution contains principally thorium sulphate, and gives, with potassium sulphate, insoluble double sulphates, while certain double sulphates remain iu solution. The insoluble double sulphates contain thorium, cerium, and didymium, whilst the others include all the metals contained in the old “ erbia,” and are characterised by their absorption-bands. In examining the earths precipitated as double sulphates, the author has observed the following peculiarity :-The anhydrous sulphates of the earths, from which the didymium has been separated by repeated partial decom- position of the nitrates, are of a yellow colour.Their solution is also yellow, but is decolorised by sulphurous anhydride. When the decolorised solution is evaporated, and the excess of sulphuric acid expelled, the sulphates reassume the yellow colour, and this can be repeated as often as desired. The author finds that a mixture of pure thorium sulphate and cerozcs sulphate behaves in the same manner. The yellow colour indicates the presence of ceric sulphate. Hence the author concludes that the presence of thorium oxide determines the conversion of the cerous into ceric sulphate by means of the excess of sulphuric acid. The author finds that four precipitations of thorium sulphate, in the manner described above, are su5cient to obtain it in a perfectly pure state.E. H. R. Study of “Longrain and Measure of the Foliation in Schistose Rocks by Means of their Thermic Properties. By E. JAENETTAZ (Compt. rend., 95, 996-999).-The law that heat is conducted more easily along the pIane of foliation than along the perpendicular direction, holds good in all cases. By means of experiments made in the manner previously desci-ibed (Compt. rend., 78 and Sl), the author has constructed the isothermal surfaces characteristic of schistose rocks. The isothermal surface of these rocks is an ellipsoid, the three principal sections of which are the plane of foliation, containing the major and the minor axes, and two others perpendicular to this and to one another, the one containing the major and the minor axes, the other the mean and the minor axes.Some- times the two axes in the plane of foliation are equal, in which case the el’lipsoid is a figure of revolution. In slate quarries the workmen split up the rock into slabs, by taking advantage of the ease with which it cleaves in the plane of foliation, or, as the author terms it, Jcirst cleavage, and then cut these up into smaller slabs along a somewhat more difficult plane of cleavage, whichMINERALOGICAL CHEMISTRY. 30 1 is locally termed the “longrain,” “long,” or “fil,” and which the author terms second cleavage. By experiments on a large number of schistose rocks from different localities and of different composition, it is found that the intersection of these two planes is parallel with the major axis of the ellipsoid, and the plane of foliation is perpendicular to the least axis.In other words, the major axis of the isothermal surface is parallel with the Zonqrahz or second cleavage, and the minor axis is perpendicular to the plane of foliation or first cleavage. The author has applied this method to the contorted schistoso beds in the lias in the neighbourhood of La Paute and VBnosc. The following table shows the percentages of calcium carbonate and clay in these beds, with the ratio of the axes of the isothermal surface on sections perpendicular to the plane of foliation. Calcium carbonate. Ciay. Ratio of axm. La Paut6 .......... 90 10 1-07 ,, .......... 65 35 1-30 ,, .......... 50 50 1-42 VBnosc .......... 25 75 2.00 C. H. B. Lithium, Strontium, and Boric Acid, in the Mineral Waters of Contrexeville and Schinznach (Switzerland).By DIEULA- FAiT (Con~pt. rend., 95, 999--1001).-The author’s previous researches have led to the conclusion that the salts existing in different strata have been derived directly or indirectly from the evaporation of ancient seas. He also concludes that mineral waters derive their saline matter from the salt-bearing strata of the permiari, triassic, and tertiary formations, this saline matter itself being derived from ancient seas. If this conclusion is correct, all the substances which existedin these seas should be found in the mineral waters. Amongst the most characteristic are lithium, strontium, and boric acid, and it follows from the author’s investigations of sea water that these sub- stances should exist in mineral waters in relatively considerable pro- portions.The lithium spectrum ought to be obtained with tihe residue left by the evaporation of 1 c.c., or often even from a, single drop, the strontium spectrum with the residue from 5 c.c., and the boric acid reaction with the residue from not more than 190 C.C. Water of Cor~ti-exeuiZZe.-Litliiurn exists in relatively considerable proportion, and the strontium spectrum is obtained distinctly with the residue from 5 C.C. Deboul failed to find strontium in this water, because he looked for it in the precipitate produced by boiling, on the assumption that the strontium is present as bicarbonate, whereas it really exists as sulphate. PV uter of Schinzriach.-This water derives its saline matter from the trias.Contrary to the statement of Grandeau, lithium can be detected in a single drop, strontium in 4 c.c., and boric acid in 25 C.C. of this water. These two waters are therefore not exceptions t o the author’s law, but, OLL the contrary, afford further proof of its accuracy. C. H. B.302 ABSTRACTS OF CHEMICAL PAPERS. Presence of Arsenic in the Waters of Bareges. By M. SCHLAGDENHAUFFEN (J. Pharnz. [ 5 ] , 6, 4i5-480).-Tha author has detected arsenic in these waters from the different springs. The quantities vary from 0.000016 to 0.00022 gram per litre. The source of the metsl is the rock through which the water runs. The residue on evaporation yields only part of its arsenic to -hydrochloric acid : hence the author concludes that the metal is partly present as a sulpharsenate which is converted by the acid into insoluble sulphide.Origin of Arsenic and Lithium in Waters containing Calcium Sulphate. By 31. SCELAGDENHAUFFEN (J. Phnrm. [C;], 6, 457-463).-The author has established the presence of arsenic in the mineral waters of Schinznach and Baden in Switzerland. According to Orfila and Walchner, the arsenic is present in all similar mineral waters in combination with iron, but it is shown in this paper that the quantity of arsenic bears no relation to the proportion of iron, and that the former is often present when the latter is entirely absent. Hence the arsenic probably exists in these waters i,n combination with calcium. The origin of arsenic is without doubt the sulphide of that element contained in mads associated with the gypsum, from which it is dissolved by waters charged with calcium carbonate, being first converted into sulpharsenate and finally into arsenate of calcium.The author shows that ihese marls also contain lithium, and that this metal can easily be detected by the spectroscope in these mineral wat em. E. H. R. E. H. R. Glairin or Baregin. By N. JOLY (Compt. rend., 95, 1194- 1195).-The glairirz or baregirt found in almost all the hot sul- phuretted waters of the Pyrenees, is a very complex substance, con- sisting of the remains of animal and regetable matter, together with various inorganic substances, such as crystals of sulphur, iron pyrites, silica, &c. The nitrogenous organic matter which esists in solution in these waters is apparently derived from the ultimate decomposition of the various animal and vegetable organisms which live in the waters.The complex glairin of Luchon is derived almost entirely from the decomposition of the dead bodies of nnzs, cyclops, iw&soria), and sulfuyairia. The author has been able actually to watch the gradual formation of glairin from the decomposition of these organisms. There can be no doubt that true glairin is an animal product. C. H. B.MINERALOGICAL CHEMISTRY.M i n e r a l o g i c a l Chemistry.299Analysis of the Coal of the Muaraze. By P. GUYOT (J.Pharm. [5], 6, 474--473).-This is a short paper, containing anaccount of thin beds of coal found in the valley of the River Muaraze,a tributary of the Zambesi. The volatile matter varies in differentspecimens from 20 to 22 per cent., and the coke from about 50 to 55per cent.E. H. R.The Thorite of Arendal. By L. F. NILSON (Compt. rend., 95,784-7886).-Nordenskiold found, near Arendal, in 1876, a crystallinesilicate containing 50 per cent. of oxide of thorium, and 10 per cent.of uranous oxide. He regards the mineral as a variety of thorite.Later, the same mineral was discovered a t Hitter0 (Norway) byLindstrom, and at Champlain (U.S.A.) by Collier, who called ituranot ho rite.The mineral is interesting as containing urannus oxide. Zimmer-man has shown that uranous oxide has the formula UOz, and the oxideof thorium having probably the formula Thoz, it is to be presumedthat the two oxides are capable of replacing one another in thorite i300 ABSTRACTS OF CHENICAL PAPERS.variable proportions. The molecular volumes of the oxides in questionconfirm this hypothesis.The author has obtained pure sulphate of thorium by a new andsimple method. He finds that by saturating 5 parts of water at 0”with 1 part of crude anhydrous sulphate and then warming to 20’,thorium sulphate is precipitated as a heavy white crystalline powder,amounting to two-thirds of the sulphate dissolved. The precipitate iswashed with cold water, the mother-liquors are evaporated to dryness,and the product is subjected to the same treatment.Proceeding in thisway a solution is finally obtained which, saturated a t zero, precipitatesnothing more when warmed to 20”. The solution contains principallythorium sulphate, and gives, with potassium sulphate, insoluble doublesulphates, while certain double sulphates remain iu solution.Theinsoluble double sulphates contain thorium, cerium, and didymium,whilst the others include all the metals contained in the old “ erbia,”and are characterised by their absorption-bands. In examining theearths precipitated as double sulphates, the author has observed thefollowing peculiarity :-The anhydrous sulphates of the earths, fromwhich the didymium has been separated by repeated partial decom-position of the nitrates, are of a yellow colour. Their solution is alsoyellow, but is decolorised by sulphurous anhydride. When thedecolorised solution is evaporated, and the excess of sulphuric acidexpelled, the sulphates reassume the yellow colour, and this can berepeated as often as desired.The author finds that a mixture of purethorium sulphate and cerozcs sulphate behaves in the same manner.The yellow colour indicates the presence of ceric sulphate. Hence theauthor concludes that the presence of thorium oxide determines theconversion of the cerous into ceric sulphate by means of the excess ofsulphuric acid.The author finds that four precipitations of thorium sulphate, in themanner described above, are su5cient to obtain it in a perfectly purestate. E. H. R.Study of “Longrain and Measure of the Foliation inSchistose Rocks by Means of their Thermic Properties.By E. JAENETTAZ (Compt. rend., 95, 996-999).-The law thatheat is conducted more easily along the pIane of foliation than alongthe perpendicular direction, holds good in all cases. By meansof experiments made in the manner previously desci-ibed (Compt.rend., 78 and Sl), the author has constructed the isothermal surfacescharacteristic of schistose rocks.The isothermal surface of theserocks is an ellipsoid, the three principal sections of which are the planeof foliation, containing the major and the minor axes, and two othersperpendicular to this and to one another, the one containing the majorand the minor axes, the other the mean and the minor axes. Some-times the two axes in the plane of foliation are equal, in which casethe el’lipsoid is a figure of revolution.In slate quarries the workmen split up the rock into slabs, by takingadvantage of the ease with which it cleaves in the plane of foliation,or, as the author terms it, Jcirst cleavage, and then cut these up intosmaller slabs along a somewhat more difficult plane of cleavage, whicMINERALOGICAL CHEMISTRY.30 1is locally termed the “longrain,” “long,” or “fil,” and which theauthor terms second cleavage. By experiments on a large number ofschistose rocks from different localities and of different composition,it is found that the intersection of these two planes is parallel with themajor axis of the ellipsoid, and the plane of foliation is perpendicularto the least axis. In other words, the major axis of the isothermalsurface is parallel with the Zonqrahz or second cleavage, and the minoraxis is perpendicular to the plane of foliation or first cleavage.Theauthor has applied this method to the contorted schistoso beds in thelias in the neighbourhood of La Paute and VBnosc. The followingtable shows the percentages of calcium carbonate and clay in thesebeds, with the ratio of the axes of the isothermal surface on sectionsperpendicular to the plane of foliation.Calciumcarbonate. Ciay. Ratio of axm.La Paut6 .......... 90 10 1-07,, .......... 65 35 1-30,, .......... 50 50 1-42VBnosc .......... 25 75 2.00C. H. B.Lithium, Strontium, and Boric Acid, in the Mineral Watersof Contrexeville and Schinznach (Switzerland). By DIEULA-FAiT (Con~pt. rend., 95, 999--1001).-The author’s previous researcheshave led to the conclusion that the salts existing in different stratahave been derived directly or indirectly from the evaporation ofancient seas.He also concludes that mineral waters derive theirsaline matter from the salt-bearing strata of the permiari, triassic,and tertiary formations, this saline matter itself being derived fromancient seas. If this conclusion is correct, all the substances whichexistedin these seas should be found in the mineral waters. Amongstthe most characteristic are lithium, strontium, and boric acid, and itfollows from the author’s investigations of sea water that these sub-stances should exist in mineral waters in relatively considerable pro-portions. The lithium spectrum ought to be obtained with tihe residueleft by the evaporation of 1 c.c., or often even from a, single drop, thestrontium spectrum with the residue from 5 c.c., and the boric acidreaction with the residue from not more than 190 C.C.Water of Cor~ti-exeuiZZe.-Litliiurn exists in relatively considerableproportion, and the strontium spectrum is obtained distinctly withthe residue from 5 C.C.Deboul failed to find strontium in this water,because he looked for it in the precipitate produced by boiling, on theassumption that the strontium is present as bicarbonate, whereas itreally exists as sulphate.PV uter of Schinzriach.-This water derives its saline matter fromthe trias. Contrary to the statement of Grandeau, lithium can bedetected in a single drop, strontium in 4 c.c., and boric acid in 25 C.C.of this water.These two waters are therefore not exceptions t o the author’s law,but, OLL the contrary, afford further proof of its accuracy.C.H. B302 ABSTRACTS OF CHEMICAL PAPERS.Presence of Arsenic in the Waters of Bareges. By M.SCHLAGDENHAUFFEN (J. Pharnz. [ 5 ] , 6, 4i5-480).-Tha author hasdetected arsenic in these waters from the different springs. Thequantities vary from 0.000016 to 0.00022 gram per litre. The sourceof the metsl is the rock through which the water runs. The residueon evaporation yields only part of its arsenic to -hydrochloric acid :hence the author concludes that the metal is partly present as asulpharsenate which is converted by the acid into insoluble sulphide.Origin of Arsenic and Lithium in Waters containingCalcium Sulphate. By 31.SCELAGDENHAUFFEN (J. Phnrm. [C;], 6,457-463).-The author has established the presence of arsenic in themineral waters of Schinznach and Baden in Switzerland. Accordingto Orfila and Walchner, the arsenic is present in all similar mineralwaters in combination with iron, but it is shown in this paper that thequantity of arsenic bears no relation to the proportion of iron, andthat the former is often present when the latter is entirely absent.Hence the arsenic probably exists in these waters i,n combination withcalcium. The origin of arsenic is without doubt the sulphide of thatelement contained in mads associated with the gypsum, from which itis dissolved by waters charged with calcium carbonate, being firstconverted into sulpharsenate and finally into arsenate of calcium.The author shows that ihese marls also contain lithium, and thatthis metal can easily be detected by the spectroscope in these mineralwat em. E. H. R.E. H. R.Glairin or Baregin. By N. JOLY (Compt. rend., 95, 1194-1195).-The glairirz or baregirt found in almost all the hot sul-phuretted waters of the Pyrenees, is a very complex substance, con-sisting of the remains of animal and regetable matter, together withvarious inorganic substances, such as crystals of sulphur, iron pyrites,silica, &c. The nitrogenous organic matter which esists in solutionin these waters is apparently derived from the ultimate decompositionof the various animal and vegetable organisms which live in the waters.The complex glairin of Luchon is derived almost entirely from thedecomposition of the dead bodies of nnzs, cyclops, iw&soria), andsulfuyairia. The author has been able actually to watch the gradualformation of glairin from the decomposition of these organisms.There can be no doubt that true glairin is an animal product.C. H. B

ISSN:0368-1769    

DOI:10.1039/CA8834400299

出版商:RSC    

年代:1883

数据来源: RSC

摘要:

302 ABSTRACTS O F CHEMICAL PAPERS.0 r g a n i c C h e m is t ry.Relation between Boiling Points and Specific Volumes. By W. STAEDEL (Ber., 16, 2559--2572).-An examination of the chlori-nated derivatives of ethane shows that the boiling point (under thenormal pressure) is raised 56-22" when one atom of hydrogen isreplaced by chlorine in the group CH,, e.g., CH3.CHC12 (b. p. 57*7')ORGANIC CHEJIISTRY. 303and CH,Cl.CHCl, (b. p. 113.7"). The introduction of a secondchlorine-atom into the methyl group raises the boiling point 31.3", e.g.,CH2C1.CCl3 boils at 130*5", and CHC1,.CC13 boils atr 161.7'. The con-version of the group CHC1, into CC1, raises the boiling point 16.04".The specific volume of these compounds at their boiling points isincreased 14.2 by the introduction of the first chlorine-atom in themethyl group, 16.37 for the second, and 19.16 for the introduction ofthe third chlorine-atom, Hence it appears that an atom of chlorineConversion of Organic Chlorides into Iodides by means ofCalcium Iodide.By P. v. ROMBURGH (Rec. Tmv. G'hhi., 1,151-153).-The transformation of organic chlorides into iodides cannot con-veniently be effected by heating them with potassium iodide, as theaction is too slow; aluminium iodide, on the other hand, acts toorapidly. Hydrogen iodide can be used only a t ordinary temperatures,since at higher temperatures it acts as a reducing agent. Calciumiodide, on the other hand, appears to be available in all cases, andeffects the conversion more rapidly than potassium iodide, inasmuchas the difference between the heats of formation of chloride andiodide of calcium is greater than that which is found to exist in thecase of any of the other metals except aluminium.-AZZyZ chloride,heated with calcium iodide in a sealed tube at 100" for six hours, iscompleiely converted into ally1 iodide (b.p. 100-101" ; sp. gr. 1.846a t 15").--A?nyl chZoride (b. p. lie"), heated with CaI, for 24 hours a t100", is almost wholly converted into iodide (b. p. 147" ; sp. gr. 1.499at 15").--Etlylene clrZoYide, heated with CaI, at 100" for three hours,yields a sniall quantity of a crystalline body, melting a t 82", sublimingwithout alteratioii, decomposed a t a stronger heat with separation ofiodine vapour, and in fact exhibiting all the characters of ethyleneiodide.-Benxyi chloride similarly treated at loo", yielded a red-brownliquid, which was decolorised by washing first with water, then withaqueous potash ; and on distilling the coIourIess liquid thus obtained,the t.emperature soon rose above the boiling point of benzyl chloride,and at 215" decomposition took place, with separation of iodine-vapour,the greater part of the product solidifying a t the same time.Inanother experiment white crystals were obtained, melting a t the heatof the hand. These characters, together with the irritating odour ofthe product, pointed to the presence of beneyl iodide, but the authorintends to examine it further.Decomposition of Cyanogen. By BERTHELOT (Conzpt. rend., 95,9 5 5 4 5 6 ) .-Cyanogen decomposes with explosion under the influenceof a discharge of mercury fulminate. This effect is due to the hightemperature developed by the destruction of the first layers of cyanogenby the detonation, the conditions being favourable to the productionand propagation of an explosive wave.On the other hand the gas i sbut slowly decomposed when passed through a red hot tube. Per-fectly dry cyanogen is completely decomposed into nitrogen andcarbon after about three hours by the continuous passage of inductionsparks. I n presence of the least trace of moisture small quantitiesot' hydrocyanic acid rand acetylene are formed. Decompositiou undercan possess different specific volumes. w. c. w.H. W304 ABSTRACTS OF CHEMICAL PAPERS.these conditions remains slow, and has no explosive characteristics.The gas is very rapidly decomposed by the electric arc, the carbonbeing partly deposited in a flocciilent condition round the negativepole.It would appear that decomposition under these conditionsapproaches the point ant which it becomes explosive. In presence ofhydrogen or a hydrogen compound, some hydrocynnic acid is formed.C. H. B.Properties of Normal Cyrxlnic Acid. By E. MULDER (Bec. Tmv.Chiin., 1, 191-222) .-From the experiments detailed in this paper,and from previous researches, the author draws the following conclu-sions :--1. The existence of normal cyanic acid as potassium salt,CN.O.K, appears to be impossible under ordinary circumsta1ices.-2. Cyanetholine (corps de M.Cloez) is conveniently prepared by theaction of cyanogen bromide on absolutely auhydrous alcohol (easilyobtained by decomposition of a solution of sodium ethylate in ordinaryabsolute alcohol).-3. By the action of cyanogen bromide dissolved inether upon sodium ethylate in presence of alcohol and ether, and sub-sequent filtration and evaporation of the volatile parts of the filtrate, acrude product is obtained, which dissolves for the most part in water,leaving a small residue of cyanetholine, and appears to consist chieflyof a(CN.0Et,C2H,0).--The wash-water treated with ether yieldsurethane, formed according to the equation CN.OEt + H20 =NH,.COOEt. This water likewise contains normal ethyl cyanurate,arid a very small quantity of ethyl monamidoyanurate, and perhapsalso ethyl diamidocyanurate.It is remarkable that cyanogen bromide,acting on sodium ethylahe in presence of alcohol and ether, gives riset o normal ethyl cyanurate, evcn in presence of water, to theamount of5H,O to EtONa, a result which seems to imply the existence ofEtONa in alcoholic solution, in presence of a relatively large quan-tity of water, much larger, indeed, than that which would be neces-sary to decompose EtONa into Et.OH and Na0H.-4. Cyanetholine,after drying for some time in the exsiccator, gives by analysis num-bers agreeing pretty nearly with the formula CN.OEt; it probablyalways contains small qiiantities of ethjlic monamidocyanurate anddiarnidocyanur&e.-5. This body, after remaining at rest for sometime, gradually deposits crystals, consisting chiefly of normal ethylcyanurate, sometimes in well-formed prisms. The crystals depositedfrom aqueous solution a t low temperatures contain a large proportionof crystal-water, which is given off with efflorescence at 6".Thiscompound melts at about 29", remaining liquid for somc hours, and thensolidifying. Normal ethyl cyaniirate may be distilled under diminishedpressure, without being converted int'o isocyanurate. It is vefyslightly soluble iii water, and its saturated or nearly saturated solu-tion becomes thickly clouded when heated nearly to the melting pointof the compound.-6. Normal ethyl cyanurate is soluble in bromine,and on evaportting the exces8 of bromine a t a sufficiently low tempera-ture, there remains an orange-red compound, apparently consisting ofSCNOEt,GI(r, which undergoes dissociation.The same is the casewith an addition-product, which separates in yellow needles on addingbromine-water to an aqueons solution of ethyl cyanurate. Neitherisocyanuric acid, nor its methylic or ethylic ether, forms an additionORGANIC CHEMISTRY. 305product with bromine, so that the formation of such a product may beregarded as a reaction characteristic of the normal cyanurates.-7. Cyanetholine is very slightly soluble in water ; its solution becomesvery tuiibid when heated, and in presence of bromine-water behavesfor the most part like that of normal ethyl cyanmate. Ethyl isocyan-urate, on the contrary, differs from cyanetholine in its behaviour withbromine-water ; the same is the case also with the aqueous solutionsof these bodies at low temperatures.--8. Ammonia-gas passed throughthe alcohol-etheric filtrate of the preparation does not appear to formeither cyanamide or dicyanamide, which might be expected to form inpresence of N i C.OEt, if cyaiiamide were regarded as the amide ofnormal cyanic acid, N i C.NH,.Cyanamide, moreover, does not com-bine either with bromine or with cyanogen, whence it is probably aderivative of isocyanic acid, its constitutional formula being thak ofcarbodiimide, HN : C NH. H. W.A Reaction of the Compounds of Normal Cyanuric Acid andCyanetholine (corps de M. Cloez). By E. MOLDER ( R e c . Truw.Chim., 1, 41).-The compounds of normal cyanuric acid (the free acidis not known) and cyanetholine (isomeric with ethyl cyanate) formaddition-products with bromine, whereby they may readily be distin-guished from isocyanuric acid and its compounds, which do not formsuch addition-products.For example, an aqueous solution of normalethyl cyanurate forms with bromine-water a crystalline addition-product (CN),O,Et,,Br,, very soluble in water, which is not the caseeither with ethyl isocyanurate or with isocyanuric acid. Hence theauthor infers that the two isomeric acids may probably ,be representedby the following formulae :-N=C.OH HN-COI IH0.C NI1 IIN-C.OHI 1I IOC NHHN-CONormal cyanuric acid. Isocyanuric acid.H. W.Ethyl Peroxide. By BERTHELOT (Ann. Clrim. Phys.[ 5 ] , 27, 229-232j.--v. Babo noticed (Annulen, Suppl. 2, 165) that ozone acts onether, and states that hydrogen peroxide is produced. Berthelotfinds that this is the case only when the ether employed is wet. I f dryether is evaporated by passing a dry current of ozonised oxygen overits surface, a small quantity of a dense syrupy liquid is left. Thisliquid is miscible with water, does not solidify when cooled to -40°,and when subjected to heat, explodes violently as soon as a smallportion has distilled oFer. It acts as an oxidising agent in a mannersimilar to hydrogen peroxide, and gives up 10-11 per cent. cjf oxygenwhen treated in the cold with permanganic or chromic acids. Theauthor ascribes the formula (C2H5)403 to this body, and gives it thename of ethyl ptmxide.Second Anhydride of Mannitol.By A. FAGCOXBIER ( C o ~ p t .rend., 95, 991-993).-When mannitol is subjected to dry distillationL. T. T306 ABSTRACTS OF CHEMICAL PAPERSin a vacuum, it yields a brownish-yellow liquid mixed with empyren-matic substances. The liquid is filtered through a moistened filterand distilled. Thefraction which passes over between 160" and 190" under a pressure of0.03 m., consists partly of the second anhydride of mannitol, CsHloO,.When freshly distilled, this compound is a colourless syrup which, ifperfectly pure, forms bulky crystals melting at 87", and apparentlybelonging to the monoclinic system. It boils without decompositionat 176" under a pressure of 0.03 m., and with partial decompositionat 274' under ordinary pressure.It is very soluble in water andalcohol, biit insoluble in ether, and possesses in a high degree the pro-perties of remaining in superfusion, and of forming supersaturatedsolutions.This second anhydride of mannitol does not combine directly witheither cold or hot water, and is not affected by nascent hydrogen. Itis not attacked by bromine in the cold; but if the two bodies areheated together alone or in presence of water, hydrobromic acid isgiven off, and black resinous products are formed, but cannot be dis-tilled. When boiled for eight hours with three times its weight ofacetic anhydride, the mannitol anhydride yields a diacetic derivative,CsHs~&ce, an almost colourless viscid liquid, which is not altered bythe prolonged action of acetic anhydride ; it boils at 197-198" undera pressure of 28 mm.The mannitol anhydride is not attacked by phosphorus oxychloride,but with phosphorus pentachloride it yields a dichlorhydric derivative,C6HS02C12, which forms hexagonal lamellae, very soluble in ether,somewhat soluble in alcohol and benzene, insoluble in water.It meltsat 49", boils at 143" under a pressure of 43 mm., and can be distilledin the vapour of water. Not more than two atoms of chlorine can beintroduced into the molecule by the action of phosphorus pentachlo-ride. When heated in sealed tubes at 120" for four hours with ethyliodide and concentrated potash, the anhydride yields a moriethylderivative, C,H,O,Et, a colourless somewhat mobile liquid, soluble inwater, alcohol, and ether: it boils at 165" under a pressure of 17 mm.Prom these facts it is evident that the second anhydride of mannitolis a saturated compound containiiig two alcoholic hydroxyl-groups,and that there are no double bonds between the carbon-atoms.Itsformula is therefore CsH802(OH)2. The primary, secondary, ortertiary character of the hydroxyl-groups, and the function of thetwo other oxygen-atoms, has yet to be established.Influence of Mass and Time on the Inversion of Sugar. ByF. URECH (Bey., 15, 2457--246O).-The author has observed that theinversion of cane-sugar in the case of a mixture of 16.35 grams cane-sugar and 11.40 grams hydrochloric acid in 100 C.C. water, is anexothermic reaction.Therefore, as the velocity increases with the temperature, no con-stant can be deduced from the lnws of mass action, but only approxi-mate values for short intervals of time.In the fjrst half of the reaction more heat is evolved than in thesecond, during which smaller quantities of cane-sugar enter into theIt begins to boil at 60" under ordinary pressure.C.H. BORGANIC CHEMISTRY* 307reaction. The author has, notwithstanding the experimental difficul-ties, made a series of observations on the velocity of the reaction bythe polariscope and by a titration method with Fehling's solution.The experimental tube of the polariscope wa,s kept cool by a currentof water; and in the titration method quantities of the inversionmixture were taken out, at given intervals of time, run into excess ofalkali to stop the reaction, and then titrated.From the results obtained by these two methods, the author con-cludes that generally in equal intervals of time, equal quantities ofcane-sugar disappear, while the hydrochloric acid plus water increasesin direct proportion to the decrease of cane-sngar. Large quantitiesof hydrochloric acid and water invert more quickly than smaller quan-tities of the same concentration.V. H. V.Formula of Starch. By T. PFEIFFER, B. Torams, and F. SALO-MON (Bied. Centr., 1882, 775-777) .-Sachsse and Nageli attribute tostarch the formula C36H62031 + 5H20 = 6CoH1206, and ground t,his for-mula on the amount of sugar obtained by the action of acid. Pfeifferand Tollens, however, consider that the formula should be C24H490,0, orC24H4,021, deducing this from the composition of the sodium andpotassium compounds, which contain 3.44 per cent.Na and 5.25 percent. K ; they also think that inulin and dextrin should be repre-sented by C12H20010 or CllH.22011, and that the molecules of starch andinulin are not of the same size. Salomon repeated Sachsse's experi-ments, and proceeding further claims zC6HI0O5 as the formula whichmore closely represents the composition of starch, for he obtained111 per cent. dextrin from starch. Combining these two formulae assuggested by Pfeiffer, Tollens, and Salomon, it appears that we mustadopt 4C6H1005. E. W. P.Action of Triethylamine on Symmetrical Trichlorhydriaand on the Two Dichloropropylenes.By E. REBOUL (Compt.rend., 95,993-996) .-When trichlorhydrin is heated with three vols.triethylamine in sealed tubes for some hours at loo", the productbecomes almost entirely solid on cooling ; no gas is given off. Thecontents of the tube are dissolved in water and evaporated on a water-bath in order to expel all unaltered triethylamine.The syrupy mass thus obtained is a mixture of triethylamine hydro-chloride and the two isomeric chlorides, a-chlorallyltriethylammo-nium chloride, CINEt3.CH2.CCl : CH2, and 6-chlorallyltriethylammo-nium chloride, ClNEt3.CHC1.CH : CH,.The triethylamine hydrochloride may be separated from the mixtureby means of boiling alcohol, from which it separates in silky needleson cooling, If platinum tetrachloride is added in slight excess to anaqueous solution of the mixture, an abundant precipitate is formed,readily soluble on warming. The solution on cooling depositsa-chloralZyltriethylammonizlm platinoch Zoride in nodular groups oflong thin orange-red needles, only slightly soluble in cold water.On further concentration and cooling, the orange-red needles aresucceeded by orange-yellow cryst'ak (not needles) of /3-chloraZZyltri-ethylammonium platinochlorde, more soluble in cold water than i308 ABSTRACTS OF CHEMICAL PAPERS.the first compound.On further concentration the mother-liquoryields triethylamineplatinochloride.When triethylamine acts on trichlorhy drin, it first removes hydro-chloric acid, producing a mixture of the two isomeric dichloropropy-lenes, which then unite with the excess of triethylamine, forming thecompounds just described.If triethylamine is heated with an excess of trichlorhydrin, theproduct is a mixture of the two isomeric dichloropropylenes.a-Di-chloropropylene, CH, CC1.CH2C1 (b. p. 94") attacks triethylaminein the cold ; the action proceeds rapidly a t 190", and after some hoursthe whole mass becomes solid. No gas is given off, and the productconsists of a-chlorallyl triethplammonium, without any of the p-com-pound, and with only slight traces of triethylamine hydrochloride.When the mixture of the two dicbloropropylenes obtained by the actionof potash on trichlorhydrin is heated with triethylamine, it yields amixture of the two ammoniums already described, with mere traces oftriethylamine hydrochloride.It is evident that symmetrical trichlorhydrin does not simply fixtwo molecules of triethylamine, as would be supposed from the exist-ence of two CH,Cl groups, but loses hydrochloric acid, the chlorine ofwhich is derived partly from a CH2C1 group, and partly from themiddle group, CHC1.The two isomeric dichloropropylenes thusproduced obey the same law as the chlorine derivatives of the primarymonhydric alcohols, and simply fix triethylamine. The two hetram-monium hydrochlorides thus formed are! easily decomposed by freshlyprecipitated silver oxide, and yield the corresponding ammoniumhydroxides, which precipitate calcium hydroxide from a solution ofcalcium chloride. C. H. B.Glyoxaline and its Homologues.By B. RADZISZEWSKI (Bsr., 15,2706--2708).-1n a previous communication (Abstr., 1882, 1064) theauthor expressed his opinion that glyoxaline has a constitutionC H : Nanalogous to that assigned by him to lophine, viz., ICH : PU" '\CH2,basing this formula, on the synthesis of glyoxaline by the action ofammonia on glyoxal and formaldehyde, just as lophine is formed frombenzil, benzaldehyde, and ammonia. Its solubility in alkalis and itspassive behaviour to nascent hydrogen again suggest an analogy tolophine. Against Wyss's formula, the author urges its neutral be-haviour towards the acid chlorides and anhydrides, and also the factthat it forms no nitroso-derivative. In order to further test the cor-rectness of his views, the author has substituted other aldehydes forformaldehyde in the above-mentioned reaction, and has succeeded inobtaining homologues of glyoxaline.With acetaldehyde he obtained a body melting at 137", and boilingat 266-5268'. It crystallises in needles which readily dissolve inwater, alcohol, and boiling benzene.It is represented by the formula,C4H6N2, and is in fact identical with Wallach and Schulze's paroxal-methyline ( B e y . , 14, 426). With bromine it forms the compoundCdHBBr3N2 (m. p. 258"). The properties of paroxalmethyline shoORGANIC CHEMISTRY. 309that i t is a true homologue of glyoxaline, and from its synthesis fromglyoxal, &c., the author assigns to it the constitution-CH:NC H : N A. K. M.1 )CHM~.Decomposition of Tertiary Amy1 Acetate by Heat.By N.MENSCHUTKIN (Ber., 15, 2512-2518).-Tertiary amyl acetate, pre-pared by the action of acetic anhydride on ethyl dimethyl cnrbinol, isslowly decomposed by heat at 125", according to theequation-GH3( CjHii) 0 2 = CsHIo + CzH402.In six days 2.06 per cent. of the acetate is decomposed. At a highertemperature decomposition proceeds more rapidly. At 155' signs ofdecomposition make their appearance two hours after the commence-ment of the experiment.The rate of decomDosition is at first slow, it then accelerates untilit reaches a maxim& point, when it gradnally diminishes to zero. w. c. w.Tetrasubstituted Propionic Acids. By €I, R. HILL and C. F.MARERY (Anaer. Chem. J., 4, 263--27.2).-Tetrnbromopropionic acid,C3H,Br402, is easily prepared by adding the calculated quantity ofbromine to a solution of tribromopropionic acid in chloroform a tordinary temperatures, and gradually separates in large well-definedprisms, the yield being about 90 p.c. of the theoretical amount. Thecrystals are triclinic, having the axial ratio a : b : c = 1.507 : 1 : 0-934,and angle a b = 94" 50'; ac = 104" 28'; bc = 74" 20'. Observedforms wP&, mP&, OP, Ps, wP'. The acid melts at 125-126';dissolves very readily in alcohol or ether, readily also in hot chloro-form, carbon bisulphide, and benzene, and separates in crystals on cool-ing ; it is sparingly soluble in light petroleum. Under water i t meltsa t a very low temperature to a colourless oil, which dissolves freelyon heating.The silver salt, C3HBr402Ag, separates on adding silver nitrate toa solution of the acid in dilute alcohol in clusters of needles, thequantity of which may be increased by cautious addition of ammonia.It is extremely unstable, yielding silver bromide when warmed, andblackening rapidly on exposure to light.( C3HBr402)2Ba,2H20,obtained by saturation, separates on spontaneous evaporation in groupsof flattened needles, which give off their crystal-water over sulphuricacid.The calcium saZt, (C,HBr402),Ca, prepared in like manner, crys-tallises in anhydrous needles.The barium salt in aqueous solution is resolved by heat into bariumbromide, carbonic anhydride, and tribromethylene : ( C,HBr40,)2 Ba =BaRr, + 2C0, + 2C,HBr3.The acid heated with alcoholic potashis resolved into hydrobromic acid and tribromacrylic acid, C3HBr302,melting at 118" (Abstr., 1881, 1125).a-Dichlorodibromopro~iolzic acid, C,H2C1,Br,02, is prepared by heat-ing dichloracrylic acid (m. p. 85-86') with 1 mol. bromine for severalhours at looo, and may be purified by pressing it between paper andThe barium salt,VOL. XLIV. 310 ABSTRACTS OF CHEMICAL PAPERS.crystallising it, first from carbon bisnlphide and finally from chloro-form. It crystallises in well-fGrmed triclinic crystals, exhibiting thefaces mP&, mP&, OP, P+, P:G, ,PI&, ,Pi*; frequently also mP:and m:P. Angles ab = 91"; ac =70" 31Q'; bc = 108" 52'.The silver salt, C3HC1,Br,O2Ag, is obtained by precipitation inflattened jagged needles, easily decomposed by heat.The hurium salt,(C,HCl,Br,0,)2Ba, obtained by neutralisation, crystallises in longbranching anhydrous needles. It is decomposed by heat, yieldingproducts similar to those obtained from the tetrabromopropionate.~-DichZorodibromopropionic Acid.-Chlorine gas passed into dibrom-acrylic acid in ordinary daylight is slowly taken up, and dichlorodi-bromopropionic acid is formed, but so contaminated with oily productsthat its purification is somewhat difficult. If, however, the action bemade to take place in direct sunshine at loo", i t goes on rapidly, andthe process may be stopped when the melted acid becomes solid, fromseparating crystals of the addition-product. This product purified bycrystallisation, first from carbon bisulphide and then from chloroform,forms oblique prisms melting a t 118-120", easily soluble in water,alcohol, and ether, somewhat less easily in carbon bisulphide, chloro-form, and benzene.The solution in carbon bisulphide deposits well-defined monoclinic crystals having the axes a : b : c = 2.393 : 1 : 1.731,and the angle CIC = 46" 9'. Observed faces wP2, COP, + P, + $PG.The silver suZt of this acid is precipitated in short t.hick pointed prismson adding silver nitrate to the aqueous acid ; it is easily decomposed byheat. The barium saZt, (C3HBr,Cl,f)2)zBa + 2H20, is obtained byneutralisation, and crystallises by slow evaporation in long radiatingneedles, very soluble in cold water.Axes a : 71 : c = 1.02 : 1 : 1.052.H.W.Constitution of the Substituted Acrylic and PropionicAcids. By H. B. HILL (Amer. Chem. J., 4, 273-276).--a-Mono-bromacrylic acid can be made from a- and from &-dibromopro-pionic acid, and must therefore have the structure CH, : CBr.COOH ;the tribromopropionic acid made from it by addition of bromine willhave the corresponding form, CH2Br. CBr,.COOH, and the dibrom-acrylic acid obtained from the latter will be represented by theformula CHBr CBr.COOH. The dibromacrylic acid of Fittig andPetri, which, as shown by Mabery and Hill, can be made frombromopmpiolic acid, must have the form CBr, : CH.COOH, and theacids made in like manner, containing two halogens, will be repre-sented by the corresponding formulae-CBrI : CH.COOH and CBrCl : CH.COOH.The tribromopropionic acid melting a t 118" must be represented bythe formula CHBr,.CHBr.COOH, and tetrabromopropionic acid byCHBr> CBr,.c1 OOH. H. W.Crystalline Form of Tribromacrylic Acid. By W. H. MEL-VILLE (Amer. Chem. J., 4, 277).-This acid forms monoclinic crystalsexhibiting the forms mP&, cmP, +P&, - P s , %Pfi, the last threORGANIC, CHEMISTRY. 3 11however occurring but rarely. a : b : c = 0.502 : 1 : 0.559 ; AngleAddition of Hypochlorous Acid to p-Crotonic Acid. By P.MELIKOFF (Bey., 12, 2586-2588) .--p-Crotonic acid unites directlywith hypochlorous acid, forming chloroxybutyric acid. On treatingan alcoholic solution of chloroxybutyric acid with alcoholic potash,potassium chloride is deposited, and potassium butylglycidate remainsin solution; the excess of potash is precipitated by a current ofcarbonic acid, and ether added t o the filtrate, when potassium butyl-glycidate is deposited in oily drops.ButyZgZycidic acid, C4H603, is a mobile liquid forming viscous salts.It combines with hydrochloric acid, yielding ehloroxybutyric acid,C1H7C103, which crystallises in prisms melting at 98", and forms azinc salt crystallising in rhombic plates containing 1 mol.HzO. Butyl-glycidic acid also unites direetly with water, forming butylglycericacid, which has been described by Hanriot (An?&. Chirn. Phys. [ 5 ) , 17,ac = 64" 29$. H. w.104). w. c. w.Ethyl Acetoacetate, By A. E. Mammws and W. R. HODGKINSON(Bey., 15, 2679) .-By the action of potassium cyanide on monochlor-acetone, Me.CO.CH,CI, the corresponding cyanide Me.CO.CH,.CN isobtained, and on decomposing this with hydrochloric acid, it yields ethylacetoace tate.A. I(. M.Preparation of Methyl Chlorocarbonate. By A. KLEPL(J. pr. Chem., 26, 447).-1n preparing the chlorocarbonate by passingchlorocarbonic oxide into methyl alcohol in the ordinary way, a con-siderable quantity of methyl carbonate is formed at the same time,and can only be separated with di6culty. This may be avoided bydiluting the alcohol with ready-formed methyl chlorocarbanate, andemploying chlorocarbonic oxide free from chlorine ; for this purposethe gas is first passed over a mixture of metallic antimony with frag-ments of glass, kept at a temperature of 100" to absorb the freechlorine, and then into a mixture of methyl chlorocarbonate with lessthan one-third of its bulk of methyl alcohol surrounded by ice-coldwater. As soon as the chlorocarbonic oxide is no longer perceptiblyabsorbed, a fresh quantity of methyl alcohol is added, and the opera-tion repeated, taking care that the alcohol added always bears aboutthe aame ratio to the chlorocarbonate already formed.Whensuccessive additions of alcohol have brought up the total quantity ofliquid to about 150 c.c., the operation is stopped, the product washedwith water at 0", dried over calcium chloride, and distilled ; almostthe whole passes over between '70" and 72", and one or two fraction-ations with it Linnemann's tube, render it perfectly pure (b.p. 71-71.5"). The same process may be employed with advantage in thepreparation of ethyl chlorocarbonate.Action of Chloroform on Sodium Ethylmalonate. By M.COKRAD and M. GUTHZEIT (Ber., 15, 2841-2844) .-Oppenheim andPfaff have observed that by the action of chloroform and otherC. E. G.Y 312 ABSTRACTS OF CHEMICAL PAPERS.chlorine derivatives of methane on sodium acetoacetate, the ethyl saltof hydroxynvitic acid is formed ; a reaction which they explain by theintermediate formation of an ethyl salt of an unsaturated acid offormula C6H604, thus :-2(CH&.COOEt) + CHC13= 3HCl +COOEt.CZ : CH.CH%.COOEt.The authors have studied a simiIar reaction in the case of sodiumethylmalonate, and obtained in the first place a sodium compound,C15H2008Na, crystallising in glistening prisms, whose aqueous solutiongives crystalline precipi tates with the chlorides of the alkaline earthsand the acetates of the heavy metals, and a violet coloration withferric chloride.On decomposing the sodium compound with hydro-chloric acid, a substance of the formula C,,H2208 is found. It is acolourless oil (b. p. 270-280", sp. gr. 1.131) which gives off carbonicanhydride when heated with hydrochloric acid, and is converted intoa crystalline acid (m. p. 133") of composition C5H604, which theauthors propose to name g h f o n i c acid, in that it yields glutaric acidon hydrogenation. The changes described above may be explained bythe following reactions:-2CNa2(COOEt)2 + CHCl, = (COOEt),CNa.CH : C(COOEt), +3NaC1and (COOEt),CH.CH : C(COOEt), + 4H,O =COOH.CHZ.CH CH.COOH + 2C0, + 4EtOH.V.H. V.Action of Sodium Ethylate on the Sodium Salt of SymmetricDibromosuccinic Acid. By E. MULDER and G. HAMBURGER (Rec.Trav. Chim., 1, 54-53) .-Sodium dibromosuccinate (1 g.), treatedwith absolute alcohol containing in solution 0.2875 g. sodium, i.e.,with four times the quantity required by t.he following equation, yieldsa gelatinous mass ; and on treatiog this mass with a small quantity ofwater, filtering, and mixing the filtrate with alcohol, a gelatinous pre-cipitate is obtained, which when washed with alcohol to remove sodiumbromide, and dried under a bell-jar, forms a bulky hygroscopic massconsisting of sodium monobromethylmalate, C6&Br05N%, formedaccording to the equation-C 0 ONa.CEKBr COONa.CHBrC 0 ONa. CHBr COONa.CHOEt.The formation of this compound in presence of an excess of sodiumshows that the second bromine-atom in the dibromosuccinate is diE-cult to replace; but by acting on the lsromethylmalate with sodiumethylate, the authors hope to obtain the sodium salt of diethyltartaricI i- EtONa = NaBr +acid, CsH140s = C,H4Et206. H. w.Derivatives of Citraconic Acid. By G. L. CIAXICIAN and M.DENNSTEDT (Gazsefta, 12,500-502) .-Gottlieb (Awnden, 77, 274), byevaporating to dryness a mixture of citraconic acid with excess ofammonia, and heating the residue to 180", obtained an amorphouORGANlC CHEMISTRY. 313resinous mass, which he regarded as citraconimide ; and the authorsof the present paper, by exactly following Gottlieb's directions, haveobtained an amorphous mass of similar character; but on heating thissubstance to a higher temperature, they find that it gives off largequantities of ammonia, together with a yellow oily distillate solidify-ing on cooling to a mass of crystals ; and a t a still higher temperaturea small quantity of a brown oil which does not solidify, and whosevapour exhibits the characteristic reaction of pyrroline with a dealshaving moistened with hydrochloric acid ; finally there remains inthe retort a quaotity of shining friable charcoal.The crystalline body above-mentioned may be freed from adheringoil by pressure between paper, and further purified by repeated crys-tallisation from boiling water with addition of animal charcoal, thesolution on cooling depositing groups of splendid colourless needleswhich give by analysis 53.90 per cent.carbon, 4.72 hydrogen, and12.92 nitrogen, agreeing very nearly with the formula of citraconi-mide, C5H5N02, which requires 54.05 C, 4.50 H, and 12.61 N. Thisbody melts a t 109-110", is volatile and sublimable, slightly solublein cold, freely in hot water and alcohol, sparingly in ether. It has aneutral reaction, and gives with ammoniacal silver nitrate a compoundsparingly soluble in water. Heated with phosphorus pentachloride a t1O5-1lO0, it yields a dark brown liquid, which dissolves partially inwater, forming a solution from which ether extracts a chlorinatedbody melting at 144-145" and subliming in colourless leaflets.This and other derivatives of citraconimide will form the subject of afuture communication. H.W.Acetylenedicarboxylic Acid. By E. BAUDROWSKI (Ber., 15, 2694-2698) .-Anhydrous acetylenedicarboxylic acid crystallises fromether in well-formed fonr-sided plates, melting with decomposition a t175". Dimethylacetylenedicarboxylate, C404Me2, is a colourless liquid(b. p. 195-198') of aromatic but pungent odour.Chlorofumaric acid, CIH3C104, obtained by the action of lrydro.chloric acid on acetylenedicarboxylic acid, melts a t 178". It dissolvesvery readily in water, alcohol, and ether, and crystadlises in microscopicneedles. Hydrogen potassium chlorofumarate, CaH2C104K, crystal-lises in sparingly soluble prisms.The silver salt, C4HC104Ag, + H20,forms a white crystalline precipitate, and the lead salt, C4HC104Pb +2H20, a flocculent precipitate which, however, soon becomes crystal-line. Prom the properties of chlorofumaric acid, the author considersit as identical with the acid obtained by Perkin and Duppa by theaction of phosphorus pentachloride on tartaric acid (Annalen, 115,105). Caius's acid, obtained by the action of hypochlorous acid onbenzene (AnmaZen, 142, 139), appears, however, to be an isomeride.Bromof umaric acid, prepared by dissolving acetylenedicarboxylic acidin fuming hydrobromic acid, agrees in all its properties with the aciddescribed by Kekul6 and Fittig (AnnnZen, 195, 63). Iodofumaricacid obtained by the action of hydriodic on acetylenedicarboxylic acid,is readily soluble in water, alcohol, and ether.It melts at 182--184".The hydrogen potassium salt, CIH,IKOa, forms small well-formedcrystals, sparinglj soluble in water. The lead salt, CJHIObPb 314 ABSTRACTS OF CHEMICAL PAPERS.2H20, and the silver salt, CaHI04Ag2, are precipitated amorphous,but soon become crystalline.By E. BAuDRoWsKr (Bey., 15, 2698-2704).-The potassium salt of propargylic acid has been previously describedby the author (Ber., 13, 2340). To prepare the free acid, C3H202, a,solution of hydrogen potassium acetylenedicarboxylate is treatedwith dilute sulphuric acid and shaken with ether. After standing forsome hours, the ethereal extract is separated, dried, and evaporatedon a, water-bath. On distillin the residue, the principal fractionsobtained are one at 100-125 , which after repeated fractioningyields ethyl propargylate boiling a t 117-119*, and another a t125-154".The greater part of this fraction distils a t 140-145",b u t as it decomposes a t the same time, a constant boiling point cannotbe obtained. Analysis showed this body to be propargylic acid. Theresidue in the flask became partly solid on cooling, apparently fromseparation of anhydrous acetylenedicarboxylic acid. Propargylic acidis a colourless liquid, which solidifies a t about 4", forming long silkycrystals which melt a t 6". It is soluble in water, alcohol, ether, andchloroform. Its odour resembles that of acetic acid, but is morepowerful. The salts of mercury, silver, and platinum are readilyreduced by this acid.With the alkalis and alkaline earths, it formssalts very readily soluble in water. On reduction it yields propionicacid, and by the action of the halogen acids substituted acrylic acids.Bromine converts it into dibromacrylic acid melting a t 85-86".Derivatives of Barbituric Acid. By M. CONRAD and M. GUTH-ZEIT (Bey., 15, 2844-2850).-The author alludes to the interestattached to the chemistry oE barbituric acid as the central point of thealloxan group, and the starting point for the synthesis of uric acid.I n the course of preparation of barbituric acid from malonic acid,carbamide, and phosphorus oxychloride, the authors obtained as nbye-product a golden powder of empirical formula C3H3N02. As thissubstance gives dibromobarbituric acid by the action of bromine, it ismost probably acetobarbituric acid, formed according to the equa-tion-A.K. M.PrOpargyliC Acid.8A. K. M.Et7yZbarbituric acid, OC<NH.co NH.CO >CHEt, prepared from ethyl-malonic acid, carbamide, and phosphorus oxychloride, crystallises invitreous prisms melting a t 190" ; with bromine it forms a white crystal-line rnonobrom-derivative. Benztjlbarhituric acid from benzylmalonicacid forms prismatic crystals (m. p. 206") soluble in hot water. Theresearches of the authors and others have established that one hydro-gen-atom is replaceable by metals, the halogens and the nitrosylgroup. I n the present paper the silver salt is described. It isobtained as a reddish flocculent precipitate by the addition of silveORGANIC CHEMISTRT.315nitrate to the acid ammonium barbiturate. Dimethylbarbituric acid,prepared by heating silver barbiturate with methyl iodide, wasobtained as a red precipitate. The corresponding diethyl compoundis a crystalline compound melting at 182".On mixing an aqueous solution of barbituric acid with potassiumnitrite and adding silver nitrate, the silver salt of purpuric acid isformed. Benzylpurpuric acid, obtained by the action of benzyl chlo-ride on this silver salt, forms glistening crystals (m. p. 226"). Onsaponifying benzylpurpuric acid, benzylnitromalonic acid is obtained,which shows that the benzyl group (and therefore the silver-atom) isdirectly combined to a carbon-atom, thus-V.H, V.Extraction of Asparagine from Liquids. By E. SCHULZE(Be7-. , 15, 2855-2856) .-The author proposes to separate asparaginef'rom plant-extracts by precipitation with mercuric nitrate, and de-composition of the white precipitate by sulphuretted hydrogen. Thismethod is useful when the presence of soluble carbohydrates pre-vents the cry stallisation of the asparagine.V. H. V.Benzene from Various Sources. By V. MEYER (Bey., 16,2893-2894) .-Baeyer has shown that benzene and isatin combine,when shaken with concentrated sulphuric acid, to form. the deep-blue indophenine (CsH,NO, + 2cSH3;, = H20 + C2,HI5NO). In thepresent communication the author points out that the purest benzene(b. p. 78.8") from coal-tar oil undergoes this reaetion, whereas ben-zene of the same boiling point prepared from benzoic acid remainsunaltered.The same result obtains whatever be the source of thebenzoic acid, but if the purest benzene from cod-tar be heated forten hours with concentrated sulphuric acid, and the unattacked por-tion separated and purified, the benzene so obtained (b. p. 78.8") willnot react with isatin. This difference in property the author con-siders to be due to a minute impurity in the benzene from coal-tar,which assish the reaction, or of an impurity i n the benzene frombenzoic acid, which prevents the reaction, or finally the presence oftwo modifications of benzene in the liquid obtained from coal-tar.V. H. V.Trinitro-derivatives of Benzene and Toluene. By P. HEPP(AnnuZen, 215, 34P-375).--To prepare trinitrobenzene, metadinitro-benzene (4 parts) is dissolved in a mixture of concentrated nitricacid (12 parts) and pyrosulphuric acid (30 parts); the mixture isthen heated for two days at 80" and two days at 120" ; the resultingproduct is poured into water, filtered, washed with water and withdilute sodium carbonate solution, and then crystallised from alcohol.The first crystallisation consists nearly exclusively of trinitrobenzene,which caa be obtained quite pure by a single recrystallisation fromwater. The trinitrobenzene remaining in the alcoholic mother-liqnoris best recovered by precipitation with aniline and decomposition o316 ABSTRACTS OF CHEMICAL PAPERS.the resultling compound with dilute hydrochloric acid.The yield isabout 50 per cent. of the dinitrobenzene employed.Trinitrobenzene crystallises from warm alcohol in silky plates orneedles ; by slow evaporation of the cold saturated solution, smallrhombic tables are obtained, giving the axial relations a_: b : c =0.954 : 1 : 0,733, and showing_combinaticns of P, mPm, mPm, mP,and, seldom and very small, 2P2 and wP2. It melts a t 121-122",can be sublimed in small quantities by careful heating, explodeswhen quickly heated, and does not distlil with water vapour.By the action of ammonium sulphide on trinitrobenzene, only avery small quantity of a dinitraniline (?) was obtained, which resinifiedon attempting to purify it. With tin and hydrochloric acid thedouble salt C6H3(NIIz),(HC1),,SnC1, is obtained in brilliant whitecrystals.By removing the tin with snlphuretted hydrogen, thetriamidobenzene hydrochloride may be obtained as a white crystallinemass. It does not give a blue coloration with ferric chloride, whilstthe triamidophenol of Heintzel and the triamidobenzene prepared frompicric acid (which should be identical with that from trinitrobenzene)both yield a deep-blue colour with this rea.gent.On oxidation with potassium ferricyanide in weak alkaline solution,trinitrobenzene yields picric acid, the reaction occurring with greatreadiness. In order to ascertain what influence the accumulation ofNO, groups had in accelerating oxidation, the author investigated theaction of the same oxidising mixture on di- and mono-nitrobenzene.With metadinitrobenzene the reaction was very slow ; after one hour'sboiling, the greater part of the metadinitrobenzene was unaltered ;the products of oxidation.were p-dinitrophenol and a small quantityof a-dinitrophenol. Mononitrobenzene was not attacked by thisoxidising mixture.Addition-prodtccts of Trinitrobenaene and Aromatic Amines.-Triizitro-benzene-aniZin,e, C6H3(NO2),NHzPh, is precipifated on adding anilineto an alcoholic solution of trinitrobenzene. It crystallises in longbrilliant orange-red needles which melt at 123-124". It is resolvedinto its constituents on long exposure to air, or by treatment withdilute acids. Trinitrobenzene-dimethy Zuniline, CsH3( N02)3,NMe2Ph, crys-tallises in dark-violet needles melting a t 106-108".Compounds werealso prepared with ortho- and para-toluidine, both crystallising in longred needles, and forming violet-black granules with metaphenylenediamine.Picramide, on reduction with tin and hydrochloric acid, gave thehydrochloride C6H2(NH2,HC1)3.0H, crystallising in brilliant whiteneedles. The corresponding sulphate was obtained by the addition ofsulphuric acid to an alcoholic solution of the hydrochloride. Picramidealso unites with amines (Mertens, Abstr., 1878, 725). The anilinecompound (m. p. 123-125') forms dark-red crystals, the dimethyl-nniline compound (m. p. 139-1 41.) brilliant dark-blue crystals.Picryl chloride reacts with potassium iodide in alcoholic solution,giving a substance cr.ystallising in golden-yellow needles (m.p. 164"),decomposed by potash into potassium iodide and potassium picrate,and is therefore tri~itro-iodobenxeii~.By the nitration of paradinitrobeiizene, 1 : 2 : 4 trinitrobenzenORGANlC CHEMISTRY. 317should be obtained ; but all attempts to separate it from the unaltereddinitro-body were unsuccessful. Its presence was, however, conclu-sively proved by the formation from the product of the reaction ofa-dinitraniline [ I : 2 : 41 by treabment with alcoholic ammonia, ofdinitrodiphenylamine (m. p. 153") by boiling in alcoholic solution withaniline, and of a-dinitrophenol by boiling with dilute soda solution.TR~NITROTOLUENES. - Two trinitrotoluenes have been described,a-trinitrotoluene by Wilbrand (AiznnZen, 133, 178) and Tiemann(Ber., 3, 217 and 213), and ytrinitrotoluene, prepared from y-nitro-toluene by Beilstein and Knhlberg (AnnuZen, 155, 26).The author'sresearches add a third, 6- trinitrotoluene.a- TrinitrotoZuene, CGH2Me (NOz)3, closely resembles trinitrobenzene.It crystallises in the rhombic sys&em,_rc : b : c = 0.7586 : 1 : 0.597,and shows the faces mP, wPm, wP2, Pw. It unites with amines,and these compounds may be prepared in a manner similar to thoseof trinitrobenzene, which they closely resemble. a- Trindti-otoZuene-aniline crystallises in long brilliant red needles melting a t 83-84",The dimethylaniline compound forms violet needles.ty- Trinitroto Zuene is obtained by the nitration of metanitrotoluene.It crystallises in six-sided yellow rbombic tables ; axial _relatips,u : b : c = 0.9373 : 1 : 0.6724; observed forms, mPw, P, wP2, 2Pm,OP. It is sparingly soluble in cold alcohol, moderately soluble in hotaicohol or hot glacial acetic acid, readily soluble in ether, benzene,and acetone.Itdoes not yield simple additive products with aromatic amines.y Dinitrotoluidine, C6H,Me( N02)2.NH2, is prepared by the action ofconcentrated alcoholic ammonia on y-trinitrotoluene. It crystallisesin small, hard, well-formed, golden-yellow crystals, apparently of therhombic system. It melts a t 192-193", and is sparingly soluble innearly all solvents, dissolving most readily in acetone.y-l).ilzitrotoZ~lphe122/Zamine, C6€I,Me(NOz),.NHPh, is obtained by theaction of aniline on a hot alcoholic solution of y-trinitrotoluene.Itcrys tallises in orange-colonred needles (m. p. l42'), sparingly solublein alcohol.p-TrinitrotoZuene is formed, together with ty-trinitrotoluene, by thenitration of metanitrotoluene. It is obtained in less quantity than the7-body, from which it can be separated by its greater solubility. Itcrystallises in colourless thick prisms of the triclinic systcm ; axialrelatiocs, a : 5 : c =- 0.665_7 : 1 : 0.6228 ; observed faces, mP', w'P,Pm', 'P'w, 'Pp, P, mPm, OP. It is sparingly soluble in coldalcohol, moderately in hot alcohol and glacial acetic acid, readilysoluble in ether, benzene, and acetone ; with ammonia and aniline itbehaves like ytrinitrotoluene.P-Dinitrotohidine, GH2M e(NOZ),.NHz, is prepared by heating&trinitrotoluene with alcoholic ammonia for four or five hours insealed tubes at 100".It crystallises in short golden-yellow needlesmelting at 94", and is more readily soluble than the correspondingy -derivative. A. J. G.The last solvent yields the best formed crystals.Addition-products of the Nitro-derivatives with Hydro-By P. HEPP (Annalen, 215, 375-380).-Trinitrobenxene- carbons318 ABSTRACTS OF CHEMICAL PAPERS.benzene, C6H3(N02) ,,CfiH,.-Trinitrobenzene is readily soluble in ben-zene, crystals of it deliquescing rapidly in benzene vapour; thesesolutions, on slow evaporation in the cold, yield hard, compact, bril-liant, well-formed crystals of the new compound. They only retaintheir brilliancy whilst preserved in an atmosphere of benzene vapour,and are completely resolved into their components by a few hours'exposure to air.Tri~titroben,zene-nnphthaZene, CfiH3( N02)3,CloH8, separates on mixingcold saturated solutions of trinitrobenzene and naphthalene ; it crystal-lises in long white needleg which melt at 152", and can only berecrystallised from alcohol containing naphthalene. Anthracene andtrinitrobenzene yield a red additive compound.a- Trznitrotoluerte-nap hthalene, C6H2Me(N02)3,CloH8, crystallises inneedles (m.p. 97-98") closely resembling the trinitrobenzene com-pound. TrinifrotoZuene-anthracene crystallises from benzene in redneedles. A benzene-compound could not be obtained.p-Trinitrotoluene-naphthalene crystallises in yellowish-white needleswhich melt at 100". v- Ti.initrotoluene-nu~hthalelze forms fine yellowish-white needles melting at 88-89".Metadinitrobenzene-naphthalene, C6H4(N02)2,C10H8, prepared by mix-ing solutions of its components in benzene, crystallises in longthick prismatic needles meltinq at 52-53".Paradinitrobenzene-naph-thalene forms long white needles melting a t 118-119", and i,s distin-guished from the last by its ready solubility in alcohol.Didrotoluene-naphthalene, C6H3( N02)2Me,CloH,, closely resemblesthe metadinitrobenzene-compound, and melts at 60-61".Paradiethylbenzene. By H. ASCHENBRANDT (Annalen, 216,211-223) .-This compound is best prepared by mixing dibromobenzene(25 g.) with ethyl iodide (50 g.), sodium (15 g.), and benzene (20 g.),and leaving the mixture t o itself for about a day and a half, by whichtime the reaction comes to an end.15 g. ethyl iodide are then added,whereupon further action takes place, and the decomposition is com-pleted by adding 10 g. more, and heating the mixture in a paraffin-bathfor two or three hours at about 150". The product still containssmall quantities of bromine-compounds, from which it may be freedby boiling it in a reftax apparatus with 3 or 4 grams of sodium cutup into small pieces, 150 g. p-dibromobenzene thus treated yielded15 to 16 grams of pure p-diethylbenzene boiling at 181-182".p-Dieth!ylbenzeneswlphonic acid, C,H,Et,.SO,H.-The author, by heat-ing 5 8. diethylbenzene with 20 g. fuming sulphuric acid on the waher-bath, neutralising with lead carbonate, and decomposing the resultinglead salt with hydrogen sulphide, obtained this sulphonic acid as abrown rather viscid liquid which could not be brought to crystnlliseeven by prolonged exposure to freezing mixtures.Fitt.ig and Konig(Annalen, 144, 277), on the other hand, describe the same acid ascrystallising in colourless deliquescent lamina.The salts of this acid are, for the most part, easily soluble in water,and (excepting the alkali-salts) are prepared by heating the acid withthe corresponding carbonates. The 71ariurn salt, ( CloH,,S03)2Ba,4E20,separates by rapid crystallisation in brilliant nacreoug laminse ; byA. J. (3OROANIC OHEMISTRY. 319slower crystallisation in fine roseites of crystals ; it is but sparinglysoluble in alcohol. The strontium salt (+ 4H20) separates from ahighly concentrated solution in large shining laminae ; by slower crys-tallisation iu very fine compact monoclinic crystals.The calcium saZt (+ 3H20) crystallises iu small laminae, more soluble than either ofthe preceding salts. The magnesium salt, (CloH,3S03)2Mg, is lesssoluble than the salts of the alkaline earths, and separates from dilutesolution in fine prismatic crystals. The nickel salt (+ 5H20) is butsparingly soluble, and separates from a concentrated solution in finegreen lamina The cobalt salt (+ 5H20) crystallises from dilutesolutions in cruciform groups of ned tablets, which, when cautiouslyheated on platinum foil, change to a splendid blue, and melt to a deepblue liquid.Mercuric i3aZts.-On boiling the acid with mercuric oxide and con-centrating the solution, shining yellow crusts separate, probably con-sisting of a basic salt, whilst the mother-liquor yields the normalsalt, ( C,oH13S03)2Hg, in small lamin=, which, when once separatedno longer dissolve in water.The potassium salt,obtained by precipitating t.he barium salt with potassium sulphate, isvery soluble in water, and crystallises therefrom in large nacreouslamine, or by slower separation in thick tablets. The sodium salt,ClOH13Sa3Na,prepared in like manner from the strowtiwn sult, is somewhat lesssoluble than the potassium salt, m d crystallises in large lamin=. Theammonium salt is extremely soluble in water, and erystallises in flatwell-defined plates. The silver salt, CloH,,S03Ag, obfained by heatingthe acid with silver oxide, is even more soluble than the potassiumsalt, and separates from concentrated solntions in beautiful shiningtablets, which decompose ou exposure to the air, with blackening andseparation of silver oxide.p - Et h y l benzoic acid, C'J3,E t .CO OH, is obtained by heating p-di-ethyl-benzene with dilute nitric acid, and may be purified by steam-distillingthe product which separates on cooling, then converting it intothe sodium salt, decomposing the latter with hydrochloric acid, anddigesting the precipitate with tin and hydrochloric acid to removetraces of a nitro-acid. The acid thus prepared is identical with thatwhich Fittig and Konig obtained from a mixture of 0- andp-diethyl-benzene, and crystallises from hot aqueous solution in bright shininglamine ; it melts at 112-113", and sublimes in laminae.The residue ofthe steam-distillation above mentioned consists of a mixture of mono-and dinitro-ethylbenzoic acids, together with terephthalic and nitro-terephthalic acids.p-Ethylbenzoic acid is easily soluble in ether, alcohol, benzene, andchloroform, and separates from these solutions in rhombic tablets andprisms. The calcium salt, (C9H902)2Ca + 3H20, obtained by pro-longed boiling of the acid with calcium carbonate in a, flask withupright condensing tube, is slightly soluble in cold water, and crystal-lises in colou-rless needles. The barium salt (+ 2H20) obtained b320 ABSTRACTS OF CHEMICAL PAPERS.gentle boiling of the acid with barium carbonate, forms thin nacreouslaminze, easily soluble in water.The stronhhm salt, prepared in likemanner, is very soluble, and crystallises in small laminae.Nitro-p-ethylbenzoic acid, C,H,Et(NO,).COOH, is obtained by dis-solving y-ethylbenzoic acid in cooled fuming nitric acid, and pour-ing the resulting solution into cold water, as a, crystalline precipit-rtewhich may be purified by filtering, washing, znd recrystallisation fromboiling water, and then separates in long shining needles, which turnyellow when exposed to light, and on keeping split up into smallneedle-shaped fragments. It melts a t 155-156", dissolves readily inalcohol, ether, benzene, and chloroform, and separates therefrom inneedles or prisms. Its b a r i u m salt, [ CgH,(N02)02],Ba, crystallises intufts of needles only slightly soluble in water.The calcium saZt(+ 2H,O) is sparingly soluble, and crystallises in broad tnfts ofneedles. The strontium salt (+ 4H20) is also sparingly soluble, andforms small, shining, faintly yellowish laminae. The sodium salt,crystallises in shining laminze, very soluble in water. The potassiumsalt, CgH,(N02)K + HzO, is much more soluble than the sodium salt,aad separates from a highly concentrated solution in long silkyneedles.p - Bromethylbenzene, C6H4Et.Br, was once obtained, in conse-quence of using an insnfficient quantity of sod-ium for the preparationof pdiethylbenzene from p-dibromobenzene by the process abovedescribed (p. 318), in the form of it heavy liquid, boiling after carefulfractionation at 204".It remains quite colourless on keeping, refractslight very strongly, has a, strong smell of anise, and does not solidify infreezing mixtures. H. W.Camphor-cymene, and the So-called Second Sulphonic Acidof Paracymene. By P. SPICA (Gazzetla, 12, 482-488) .-The state-ments respecting the sulphonic acids obtained from camphor-cymenedo not quite agree (see Abstr., 1880, 878, 890 ; 1881, 174, 594, 602 ;1882,196). Paternb, in preparing the barium salt of ordinary campho-cymenesulphonic acid, obtained also a small quantity of a less solubZesaZt, which crystallised in white scales containing 1 or 13 mols. water.Subsequently Patern6 and Spica Obtained, together with the ordinarybarium cymenesulphonate, a more soZubZe salt containing 12.02 p.c.crystal- water.Jacobsen obtained from " isocymene " two sulphonicacids, the barium salt of one of which, containing 12 p.c. water, wasregarded by Paternb and Spica as identical wit;h the more soluble saltwhich they obtained from camphor-cymene. Claus also obtained fromparacyniene two sulphonic acids, one yielding a barium salt moresolub Ze than ordinary barium cymenesnlphonxte, and containiug3 mols. H,O like the ordinary salt. The sulphonic acid from thissalt melted at 130-131", and yielded a lead salt containing 3H,O,and a calcium salt containing 2Hz0, like the ordinary calcium sul-phonate ; also sodium, potassium, and copper salts crystallising with1 mol. H,O. To throw further light on the constitution of theseacids, the author has made experiments upon a large quantity oORGANIC CHEMISTRY.321cymene prepared by the action of sulphur and red phosphorus oncamphor, carefully purified, and boiling a t 17.5-178". This was con-verted into sulphonic acids ; these acids into barium salts ; the bariumsalt containing 1 mol. HzO was converted into a sodium ,salt; andfrom this latter, by heating it in sealed tubes a t 190-200" withstrong hydrochloric acid, the corresponding. hydrocarbon was obtained.The examination of this hydrocarbon and its products of oxidation-details respecting which the author will communicate in a subsequentpaper-showed clearly that the hydrocarbon in question consisted ofmeta-cymene. Hence it appears that when cymene is prepared fromcamphor by the action of sulphur and red phosphorus, the paracymenewhich forms the chief product is accompanied by metacymene ; andthat the mono-hydrated barium cymenesulphonate prepared fromcamphor-cymene, is derived, not from para- but from nzetn-cymene.H. W.1 4Paradipropylbenzene, C,,H,, = PrQ.C6H,.Pp. By H. KORNER(Annulen, 216, 223-232) .-This hydrocarbon, obtained by the actionof sodium and propyl bromide on p-dibromobenzene, is a colourlessstrongly refracting liquid, having an aromatic odour like that ofsassafras oil, and not solidifying in freezing mixtures, It floats onwater, boils at 218-220", volatilises with aqueous vapour, and burnswith a very smoky flame.p-Dil3rol)yZbenze?aesu~~onic acid, CI2H1,SO3 = C6H3(C3H7),. S03H, isobtained by gently heating the hydrocarbon with a quantity of fumingsulphuric acid Rufficient to form a compound soluble in water.Ondiluting the solution with water, supersaturating with lead carbonate,precipitating the lead from the filtered solution with hydrogensulphide, evaporating the filtrate on the water-bath, and then leavingit to evaporate in the exsiccator, the siilphonic acid is obtained inthin colourless needles having a nacreous lustre ; they absorb waterrapidly from the air, and soon deliquesce. The lead saZt,obtained as above, crystallises in concentric groups of silky needles.The barium salt (+ &H20) forms slender colourless needles whichslowly give off their water in the exsiccator, and may be heated to180" without decomposition.The culciunz salt (+ 9HzO) crystal-lises in large, colourless, highly lustrous, orthorhombic prisms, termi-nated by two dome-faces. On exposure to the air it effloresces, andquickly loses its lustre. The sodium salt, C6H3(C3H7),.SO3Na + 4H,O,forms colourless very soluble laminae.Dinitro-p-d~rop~zbenzene, CI2Hl6( NO,), = C6H2PrZa(N02) ,.-Whenp-dipropylbenzene is added, with stirring, to cooled fuming nitric acid,and the resulting solution is poured into cold water, two nitro-com-pounds separate, both volatilising with steam, one solid a t ordinarytemperatures, the other liquid. The quantity of the liquid compoundwas too small for analysis ; the solid body, after washing with water,repeated pressure between bibulous paper, drying, and several recrys-talllsations from alcohol, exhibited the composition of dinitrodipropyl-benzene.The crystal8 of this nitro-compound are large, colourless322 ABSTRACTS OF CHEMICAL PAPERS.nacreous, rectangular tablets, usually with truncated sumrnih. Itmelts at 65", volatilises with aqueous vapour, turns yellow in the air,and dissolves wit'h yellow colonr in alcohol.Dibronzo-p-dipropy Zbeazerte, CsHzPrzaBr2, is prepared by droppingthe hydrocarbon into excess of bromine, and removing hydrobromicacid and excess of bromine by agitation with potash-lye, whereupon itseparates in white flocks which may be purified by washing withwater, pressing, drying, and solution in alcohol, from which the com-pound separates in shining needles or rectangular plates melting a tabout 48".p-Propy Zbenzoic acid, CloHIzO2 = C6HiPra.COOH, is prepared byboilingp-dipropylbenzene with a mixture of 1 vol.nitric acid (sp. gr.1-3), and 3 vols. water, and separates, after some hours' boiling, inloose masses of crystals. To purify it, the product is diluted with3 vols. water, and distilled, with renewal of the water which passesover ; the distillate, after saturation with sodium carbonate, is dis-tilled with steam to remove any unaltered nitro-dipropylbenzene ; theresidue of the distillation is then evaporated over the water-bath to asmall bulk ; the propylbenzoic acid, somewhat contaminated withnitro-acid, is precipitated with hydrochloric acid ; and the precipitate,after being dried and pressed, is treated with tin and hydrochloricacid to remove the last traces of nitro-acid, and again distilled in astream of aqueous vapour.p-Propylbenzoic acid crystallises from boiling water in small bril-liant, six-sided, monoclinic prisms.It is insoluble in cold, and onlyslightly soluble in boiling water, but dissolves readily in alcohol, ether,benzene, chloroform, and carbon bisulphide, and separates from thesesolvents in long broad needles resembling benzoic acid. It sublimesundecomposed, volatilises readily with steam, and melts a t 140".Bayiuin propy Zbensoate, (C,H,.CsH.i.C00)2Ba + 2Hz0, obtained bysaturating the acid with barium carbonate, crgstallises in large colourlesslaminae or tablets having a satiny lustre, and less soluble than benzoateor ethylbenzoate of barium.The calcium saZt (+ 3HzO) forms moss-like groups of fine satiny needles, more soluble than the barium salt.The strontium salt (2$,HzO) forms colourless shining laminae, some-what sparingly soluble in water. The Zead salt (2HzO) forms drusesof slender needles, nearly insoluble in cold, and only slightly solublein boiling water.Prom the preceding facts, it appears that the p-yropylbenzoic acidprepared by oxidation of p-dipropylbenzene is identical with thatwbic h Paternb and Spica obtained from isopropyl-propylbenzene(Abstr., 1880, 296). By this coincidence, the constitution of thelatter acid is established, supposing that the reaction by which itwas foPmed was not attended with any molecular transformation ofnormal propyl intLo isopropyl.Nitro-~-pro~yZbenzoic acid, CsH3PP(NOz) .GOOH, separates in yellowflocks on adding propylbenzoic acid to fuming nitric acid, and pour-ing the acid solution into a large quantity of water.It is very solu-ble in alcohol, ether, chloroform, and benzene, and crystallises fromalcohol in large, broad, colourless needles. It is nearly insoluble incold water, but meltsin hot water to small oily drops, then dissolves iORGANIC CHEMISTRY. 323moderate quantity, and crystallises on cooling in small, colourless,shining needles. The barium salt, [ C,Hlo(N02) .COOI2Ba,4H2O, crys-tallises i n colourless rectangular plates, sparingly soluble in cold,easily in hot water. The strontium salt (5H20) is sparingly soluble incold water, and crystallises in tufts of colourless needles.By E.LOUISE (Compt. rend., 95,1163-1164).-120 grams of mesitylene are mixed with 80 grams benzylchloride, heated at loo", and aluminium chloride gradually addeduntil evolution of hydrochloric acid ceases. The black product isgradually added to water, and the yellow liquid which separates out isdistilled. When the fraction boiling between 295" and 305" is purifiedit yields B liquid which boils at 300-303". This new hydrocarbon,benzyZ-mesity Zene, C6H2Me3.C7H7, forms a white crystalline mass witha slightly yellow tinge, easily soluble in benzene, Iight petroIeum,alcohol, ether, acetic acid, acetone, &c., from which it separates insmall white needles. Benzyl-mesitylene melts at 31", and will remainin a superfused condition for several days, even if cooled repeatedly to- 25".When benzyl-mesitylene is dissolved in warm alcoholsaturated with yicric acid in the cold, the liquid deposits on coolingsmall citron-yellow needles, probably analogous in composition to thecompounds of hydrocarbons with picric acid described by Bert helot.C. H. B.The History of the Metanitrils. By W. STAEDEL (Ber., 15,2864-2865) .-A purely controversial paper.Oxalic Acid Derivatives of Metanitro-paratoluidine and3-4 Diamidotoluene. By 0. HIR'SBERG (Ber., 15, 2690-2694).-On heating metanitro-paratoluidine with oxalic acid a t 110-130", thetwo bodies, oxalylnitrotoluidide, C202(NH.C6H3Me.N02>,, and nitro-tolyloxamic acid, COOH.CO.NH.C6H3Me.NO2 + H20, are formed.The former has been described by Rudolph (AnnuZen, 209, 3'71).Thelatter crystallises from dilute alcohol in yellowish-red plates, whichlose their water of crystallisation at 100". I t s ethyl-derivative(m. p. 127-1%3") splits up when boiled with alkalis, yielding nitro-toluidine, oxalic acid, and alcohol. The sodium salt, CgH7N20,Na +H20, and the barium salt, C18H14N4010Ba + 3H20, both crystallise inyellow needles. The amido-compound, c2Oz(NH.C6H31S/Ie.NH,),, ob-tained on reducing osalylnitrotoluide, crystallises in small colourlessneedles. Heated to 130°, it loses one mol. H20, ayd the compoundC16H16N40 is formed. At 300" a second mol. water is given off, withformation of the anhydro-base-€€. W.A New Hydrocarbon.which in its properties closely resembles the diamido-compound.Onreducing nitrotolyloxamic acid, water is eliminated and the body2C9HJT202 + H20 is produced ; this is feebly acid and readily soluble inalcohol, sparingly in water, from which it crystallises in colourlessneedles, melting above 300" with slight decomposition. Its salts ar324 ABSTRACTS OF CHEMICAL PAPERS,decomposed by carbonic anhydride. The author suggests threeformuh for this body, viz. :-NH NH.CO'NH.CO'I. C6H3Me( ,)C.COOH, 11. C6R3Me' IIII. C6HaM.e YH-T0 " : C.OH'but from its feebly acid properties he considers the last formula asthe most probable.By A. W. HOFMANN (Bey., 15, 2895-2897)--The author a t the outset alludes to the industrial applicationof the method devised by Martius and himself for the introduction ofthe methyl-group into a phenyl residue (Ber., 4,742).I n the presentpaper, the author describes a cumidine obtained by the action ofmethyl alcohol on xylidine hydrochloride. Tlris base agrees inchemical and physical properties (m. p. 62", b. p. 234') with a cumidineobtained by Schafer from pseudocumene. By the methylation ofcumidine, mono- and di-methyl cnmidine are formed together with thetetralcoholic ammonium iodide. MonornethyZcumidine, C9H,,.WHMe,melts a t 44", and boils a t 2.37"; its platinochloride crystallises inheedles. Dimethylcumidin e, C9HllNMe2, is a fragrant oil boiling a t222" ; the methiodide, C9HllNMe3, crystallises in prisms. Thesecompounds when heated yield the last member of the series ofmethylated anilines, viz., pentamethyl-aniline, C6Me6.NH2, the pro-perties of which the author proposes to study.V. H. V.By E. LELLMANN(Ber., 15, 2839-2840) .-The researches of Hubner and Ladenburghave established various differences in the chemical behaviour of thethree isomeric phenylenediamines. I n the present communication theauthor shows that under similar conditions the dithiocyanates ofthese compounds undergo a dissimilar decomposition, for the ortho-compound gives orthophenglenethiocarbamide, but the meta- andpara-compounds give the corresponding dithiocarbamides. Ortho-phenylenethiocarbamide crystallises in glistening leaflets (m. p. 290°),having an intensely bitter taste. JIetaphenylenedithiocnrbanaide crys-tallises from alkaline solutions in microscopic leaflets melting a t 215".Parapheny Zeitedithiocadaride crystallises from aqueous ammonia insmall colourless needles (m.p. 218"), sparingly soluble in alcohol.A. K. M.Crystalline Cumidine.The Three Isomeric Phenylenediamines.V. H. V.Substitution-products of Azobenzene. By H. JANOVSKY (Bey.,15, 2575-2579) .-Azohelzzen,emonosulphonic acid, formed by the actionof fuming sulphuric acid on azobenzene a t 130", yields aniline andamidobenzeneparasulphonic acid on reduction with iron and hydro-chloric acid. When azobenzene is treated a t 150" with Nordhausenacid containing 25 per cent. SOs, a mixture of three acids is obtained.On diluting the acid liquid with water, the mixture of the a- anORGANIC CHENISTRY.325,@-disulphonic acids solidifies to a crystalline mass. They can beseparated by fractional crystdlisation of the free acids or of theirbarium salts.a-Azobenxenedisulphonic acid, S0,H.CGH4.N:N.C,H4.S03H [4 : 1 : 1 : 41,crystallises in ruby-coloured needles containing 3 mols. H,O. It isidentical with the acid obtained from [l : 41 benzenenitrosulphonicacid. The p-disuZpphonic acid [3 : 1 : 1 : 31 forms yellow plates,which are freely soluble in water. It,s salts are more soluble thanthose of the a-acid. On reduction with tin and hydrochloric acid, the@-acid yields amidobenzenemetasulphonic acid. The third acid, foundin small quantities in the mother-liquor of the a- and P-acids, yieldsaniline and amidobenzenedisulphonic acid on reduction.Its formula,is probably Ph.N2.C6H3(SO3)2 [I : 2 : 41.Two mononitro-derivatives are obtained by treating azobenzene-parasulphonic acid with nitric acid (sp. gr. 1.41). The or-acid,C6H4(NO2) .N2. C6H4.S0,H, resembles azobenzenesulphonic acid inappearance. It crystallises in golden scales belonging to the rhombicsystem. The crystals are sparingly soluble in water, but dissolvefreely in dilute nitric acid. OnPeduction, it yields an amidosulphonic acid which crystallises in paleyellow monoclinic plates. The potassium salt formrs rhombic plates.P-nitrazobenzenesulphonic acid, CeH4(NO2).Nz.C6H,.SO3H [3 : 1 : 1 : 41,is very deliquescent. Its salts have a yellow colour. Dinitmzobenzene-parasulphom'c acid, prepared by the action of nitric acid (sp.gr. 1.45)on azo benzenesulphonic acid, crystallises in microscopic needles. Thepotassium salt explodes on heating. A trinitro-acid is formed whennitric acid (sp. gr. 1.5) is employed. Its salts are very explosive.The salts of this acid are colourless.w. c. w.Formation of Anilides. By G. TOBIAS (Ber., 15, 2666-2876).-This paper consists of a series of observations on the conditionsattending the formation of the anilides. The author has confirmedthe results of Willm and Girard as regards the formation and pro-perties of the formyl-derivatives of diphenylamine ; he finds furtherthat ethylaniline reacts with formic acid, but the resultant anilidecannot be obtained in the pure state. Attention is also drawn t o thefact that fwmic acid acts more readily than acetic acid t o form theanilide.Thus 15.7 per cent. formic acid heated with the equivalentquantity of aniline for four hours gave 79 per cent. of the theoreticalyield of the anilide, but 15 per cent. acetic acid under the same con-ditions gave only 18 per cent. after 36 hours.The author also criticises the observations of Menschutkin on thedecomposition of acetanilide by water containing a trace of aceticacid ; he considers that the change is effected by the acetic acid, andis inclined to maintain the view that pure ncetanilide is unaffected bypure water, and that the same result would hold good with puref ormanilide. V. H. V.Formanilide and its Hornologues. By G. TOBIAS (Ber., 15,2M3-2452) .-T he author has made a series of experiments to provethat aniline reacts more completely and more rapidly with formic thanwith acetic acid ta form the aailide.Thus, under similar conditions,VOL. XLIV. 32 6 ABSTRACTS OF CHEMICAL PAPERS.90 per cent. of the theoretical quantity of the formanilide, bnt only35 per cent. of the acetanilide was obtained. Traces of mineral acidsand the presence of large quantities of water exert a material influenceon the preparation of the formanilide. When 1 mol. anhydrousformic acid acts on 1 mol. aniline, the reaction limit reaches 98 percent. of the theoretical quantity.PormorthotoZuide, H.CONH.C6H4Me, from orthotoluidine andformic acid, crystallises in white glistening leaflets melting at 58' ;formoparatoluide, from paratoluidine, crystallises in compact crystals,melting at 52" ; a-nal3htlLylf@r~Lamide, from a-naphthylamine, crys-tallises in white silky needles, melting at 138.5" ; P-naphthyl forma-mide, from P-naphthylamine, crystallises in glistening leaflets, meltingat 128".By the action of metaphenylenediamine on formic acid, a,substance was obtained in refractive crystals melting at 155", solublein hot water and alcohol, and giving no reaction with the nitrites ofthe alkali-metals unless previously heated with hydrochloric acid.The substance in question was probably clif ormy lrnetaph eny 1 enedinmin e,although the results of t h e analyses showed that it was not quite pure.On passing dry hydrochloric acid through formanilide, methenyl-diphenyldiamine was obtained (a result in accordance with the re-searches of Hofmann and others), with considerable evolution ofcarbonic oxide.Methenyldiphenyldiamine easily reverts t o its twocomponents, aniline and formanilide. The sodium salts of formortho-and para-toluide crystallise in glistening leaflets, which rapidly absorbDecomposition of Acetanilide by Water. By N. MBNSCHUTKIN(Ber.; 15, 2502 - 2505). - After some remarks on the generalconcordance of his quantitative results with L. Meyer's quali-tative experiments on the decomposition of acetanilide with water(this vol., p. 56), the author takes exception to the observation thatacetanilide is not decomposed by water. Although, when pure wateris heated with acetanilide, no reaction occurs even after an interval of150 hours, yet if a trace (d5) of acetic acid is added, a differentresult is obtained ; about 19.75 per cent.of the acetanilide being de-composed when a mixture of 1 mol. acetanilide with 1.103 mols. ofwater is heated for some hours. Experiments were also made todetermine the effect on the limit of the reaction, caused by alteringthe proportion of water, and the following were the results :-carbonic anhydride from the air. v. B. v.Proportion ofacetanilide to water.1 : 0.871 : 0.881 : 0.9Limit of reaction.86.50 per cent.84-41 ,,81.31 ,,These experiments show that acetanilide is decomposed by water,and that the reactions between aniline and acetic acid on the one hand,and acetanilide and water on the other, are reversible according to theconditions of the experiment.The author further shows that anincrease in the proportion of acetic acid is favourable to the productionof the acetanilide--a result which is in accordance with the observatioORGANIC CHEMISTRT. 32 7of Berthelot, that an increase of acetic acid favours its etherificationby alcohol. V. H. V.Aromatic Arsenic- and Antimony-compounds. By A. MICHAELISand A. REESE (Ber., 15, 2876--2877).-The authors show that tri-phenylarsine is best prepared by the action of sodium on a mixture ofarsenic trichloride, monobromobenzene, and ether. On filtration andevaporation of the ethereal solution, the compound separates out as asolid mass, which can be readily purified by crystallisation fromalcohol. By a similar process the corresponding antimony-compoundmay be obtained in the form of golden leaflets melting a t 48", solublein ether and benzene, insoluble in water and hydrochloric acid.If thesodium is not in excess, crystalline bromo- and chloro-addition products,SbPh,Br, and SbPh,Cl?, are formed, but cannot be separated from thefree stibine. The author suggests the above process for the prepa-ration of the aromatic silicon, boron, and metallic derivatives.V. H. V.New Nitro-derivatives of Phenol. By R. HENRIQU~S (AnnaZen,215, 321--344).-So far no isomerides of picric acid have been ob-tained ; Bantlin (this Journal, 1875, 640) stated that he had preparedisopicric acid by boiling the dinitrophenols obtained from metnnitro-phenol with nitric acid ; but he found later (this Journal, 1877, ii, 475)that the substance was trinitroresorcinol (styphnic acid).The authorhas re-investigated this reaction, and succeeded in obtaining two newtrinitrophenols.y-Dinitrophenol is dissolved in three times its weight of concen-trated nitric acid in the cold, and the solution, after standing for 36 to48 hours, is poured into water, when an oily mixture separates ; thefree nitric acid is neutralised with ammonia, and the nitrophenols areextracted with ether. The ethereal solution is evaporated to dryness andtreated with steam to remove unaltered dinitrophenol ; the residue isdissolved in water, treated with barium carbonate, and evaporated todryness ; and the barium derivatives are treated with absolute alcohol.The residue then consists of barium styphnate, together with a smallquantity of the barium salt of a tetranitrodihydroxybenzene (see later).The alcoholic solution contains the barium salts of B- and y-trinitzo-phenol, which can be separated by fractional crystallisation. Theyield of the trinitrophenols is only about one-sixth of the dinitro-phenol employed.Bantlin concluded that y- dinitrophenol had the constitution[OH : NO, : NOz = 1 : 3 : 51.As this, however, is in contradiction to it,qready conversion into trinitroresorcinol, in which the two OH-groupsare known to be in the meta-position, the author has re-investigatedthe question. y-Dinitrophenol was heated for st short time at 100" withmethyl iodide and methyl alcohol, when the aniso'il of melting point 96"was obtained.This was heated with alcoholic ammonia a t 200-210" ; the resulting dinitraniline, on treatment with ethyl nitrite, gavea readily sublimable mass of m. p. 170". (Paradinitrobenzene meltsat 171-172", whilst metadinitrobenzene, which should have beenformed according to Bantlin's hypothesis, melts at goo.) From this,it is evident that the constitution of ydinitrophenol would be[l : 3 : 61 (OE in 1).2 328 ABSTRACTS OF CHEMICAL PAPERS,The nitration of e-dinitrophenol [l : 2 : 31 is best effected by addingit to well-cooled nitric acid, and, after two or three hours, pouringinto water, the subsequent treatrnent being similar to that giveu forthe y-compound.8-Dinitrophenol [l : 3 : 41 yields on nitration trinitroresorcinol,6-trinitrophcnol, and possibly another trinitrophenol in small quantity,as after the treatment, with ammonia, the aqueous solution was foundt o contaiu a dinitramidophenol, apparently not derived from p-trinitro-phenol.The new trinitrophenols closely resemble picric acid ; they have abitter taste, readily decompose carbonates, detonate on heating, yieldexplosive salts, and give crystalline compounds with some hydrocarbons.p-TrinitrophenoZ, C6Hz(N0z)3.0H (m.p. 96" uncorr.), being derivedfrom both 6- and y-dinitrophenols, must have the constitution[l : 3 : 4 : 61 (OH in 1). It crystallises in white satiny needles or plates,is very readily soluble in alcohol, ether, and benzene, moderatelysoluble in hot water, sparingly in cold water and dilute acids.Thebnriuna derivative, [C6H2(N02)30]2Ba + 4&0, crystallises in reddish-brown prisms, and only completely loses its water on long heatinga t 150" ; it is moderately soluble in water and alcohol. The potassiumderivative forms anhydrous, brilliant, clear- red crystals of violet reflex ;it is sparingly soluble in water, nearly insoluble in alcohol. Solu-tions of the salts of ,&trinitrophenol give a yellow precipitate with leadsalts, which can be obtained crystallised in needles, and a reddish-brown flocculent precipitate with silver salts. On gently heating i twith nitric acid, p-trinitrophenol is converted into trinitroresorcinol.Naphthalene unites with 6-trinitrophenol, giving a compound of theformula C,,,H,,C6H2(NO)3.OH ; it crystallises in yellow needles, whichmelt a t 72-73", and are readily soluble in alcohol.Phenanthrenedoes not yield a similar compound.iy-Trinitrophenol is obtained from y- and a-dinitrophenol, and there-fore has the constitution [l : 2 : 3 : 61. It crystallises in whiteneedles (m. p. 11 7-118"), behaves towards solvents like p-trinitro-phenol, and is also converted into trinitroresorcinol on oxidation withnitric acid. The barium derivative, [ C6H2(NOZ),O],Ba, crystallises inclear brown to golden-yellow scales, frequently united in rosettes ; it isnot very soluble in water or alcohol. (In the preparation of ytrinitro-phenol from e-dinitrophenol, barium salts were obtained in smallquantity, crystallising with 1 and 3 mols. H,O, but all attempts toprepare such hydrates from the anhydrous barium salt were unsuc-cessful.) The potassium salt crystallises in deep-red anhydrousneedles, readily soluble in water with red colour, nearly insoluble inalcohol ; the aqueous solution dyes wool and silk of an orange colour.Solutions of 7-trinitrophenol salts give a dark-yellow precipitate withlead salts ; a reddish-brown flocculent precipitate with silver salts, andno precipitate with copper or mercuric salts.With naphthalene, acompound of the formula C~oH8,C6Hz(N02)3.0H is obtained in golden-yellow needles, which melt a t 100".p- Dinitroamidophenol, C6H2 (NO,) 2 (N R,) .OH, isomeric with picramicacid, is obtained, as previously described, by treating the trinitro-pheuols from 6-dinitrophenol with aqueous ammonia ; it crystallises inIt yields trinitroresorcinol and y-trinitrophenolORGANIC CHT3MfSTRY.32 9brilliant red needles, melting a t 2@2", and subliming readily. It isnearly insoluble in ether, water, and mineral acids, sparingly solublein absolute alcohol, but dissolves readily in solutions of alkalis oralkaline earths with formation of salts. The yotnssiiznt derivative crys-tallises in clear yellow needles, readily soluble in water; it explodesfeebly on heating.Tetranitrodihy~roxybenzelze, C6(N0,),(OH)2, obtained in small quan-tity in the nitration of ydinitrophenol, crystallises in yellowish orcolourless needles, which melt a t 166", and are readily soluble in alcoholand ether, sparingly in water.The barium derivative, C,( N0,)40,Ba +GH,O, crystallises in golden-yellow silky needles ; when anhydrous, itacquires a cherry-red colour. It is sparingly soluble in water, inso-luble in alcohol.The constitution of styphnic acid is also settled by these experiments.It has long been known to be a resorcinol derivative, and beingformed by the oxidation of both 6- and ytrinitrophenol, it must havethe constitution [OH : NO, : OH : NOz : NOz = 1 : 2 : 3 : 4 : 51.Conversion of Tolylenediamine into an Amidocresol andv-Orcinol. By 0. WALLACH (Ber., 15, 2831-2835).-1u order todetermine the constitution of the monacetotolyleiiodiamine alreadydescribed by the author, with a view of deciding between theformule ~H2.C6H3Me.NH~ [Me : NH, : N H L = 1 : 2 : 41 or[Me : N H Z : NH, = 1 : 2 : 41, the author convertedit into an arnido-cresol, and compared it with the amidocresol obtained by Knechtfrom nitrotoluidine (Abstr., 1882, 728).By the action of nitrous agdon monacetotol ylcnediamine, an acetamidocresol, OH.C6H3Me.NIIAc,is formed; it crystallises in large leaflets (m. p. 224)', sparinglysoluble in cold water, soluble in alcohol. When the acetamidocresylis boiled with hydrochloric acid, it is converted into amidocresolchloride, which crystallises in 1 eaflets, soluble in water and alcohol.The free amidocresol is obtained by precipitating an aqueous solutionof the hydrochloride with potassium hydrogen carbonate ; it forinsneedles melting a t 15So, sparingly soluble in cold water, Thisamidocresol is not identical, but isomeric with the amidocresol ob-tained by Knecht from nitrotoluidine, which has the constitution[Me : NO,: OH = 1 : 2 : 41 ; it is therefore a derivative of ortho-cresol, and has the constitution [Me: OH: NO, = 1 : 2 : 41. Theauthor has re-examined the former amidocresol, and finds that itshydrochloride gives no colour reaction with ammonia as described byKnecht ; it crystallises in leaflets melting at 138", sparingly solublein cold water.The amidocresol melting a t 159" is converted by the diazo reactioninto y-orcinol, C,H,Me(OH), [Me : OH : OH = 1 : 2 : 41, identical withthe cresorcinol of Knecht.V. H. V.A. J. G.Synthesis of Indole from Cuminol. By 0. WIDMAN (Ber., 15,2547--2553).-Nitrocumic acid can be prepared by the action ofa glacial acetic acid solution of chromic acid on nitrocuminol.Whenan alkaline solution of this acid is treated with a concentrated solu-tion of potassium permanganate, it is converted into nitrohydroxy330 ABSTRACTS OF CHEMICAL PAPERS.propylbenzoic acid, CMe2(OH) .C6H,(N0,) .COOH, which is obtainedas a crystalline precipitate on acidifying the cold solution with hydro-chloric acid. A good yield of nitro~Lydroa~p?.ol)ylbenzoic acid can alsobe obtained by the direct action of potassium permangaiiate on nitro-cuminol. This acid is deposited from a hot aqueous solution in colour-less needles melting at 190", freely soluble in alcohol and ether.The ammoninm salt crystallises in needles, and the d v e r salt inrhombic prisms or plates.The ethylic salt forms rhombic plates,melting a t 96". It is freely soluble in the usual solvents, with theexception of light petroleum. It is decomposed by warm hydrochloricacid, forming nitropropenylbenzoic acid. Sodiz~m a z o a ~ p ~ o ~ y Zbenzoate,(C1,HloN03Na)2 + 10H20, is obtained by the action of sodium amalgamon an aqueous solution of nitrohydroxj-propylbenxoic acid, in rect-angular plates, exhibiting a brilliant red colour. The free acid crystal-lises in yellow plates, iusoluble in alcohol, ether, and benzene. It isnot decomposed by hot hydrochloric acid.Nitr~~ropeny Zberizoic acid, C,,H,N04, prepared by boiling nitro-hydroxypropylbenzoic acid with hydrochloric acid (sp. gr. l + l O ) ,crystallises in colourless needles (m.p. 154"), which dissolve freely inalcohol and ether, but are sparingly soluble in water. The ammoniumand silver salts of this acid crystallise in needles. The methyl andethyl salts are uncrystallisable oils.On distillation with lime, nitropropenylbenzoic acid yields indole,CloH9N04 + CaO = C,H7N + CaC03 + H20 + CO. W. C. W.Brorninated Derivatives of Toluquinone. By F. CAWZONERIand P. SPICA (Gazzettu, 12, 469-475) .-TribI.omotoluyzLinone,C7H3Br302 = C6MeBr302,is obtained, as chief product, on agitating toluquinone, in presence ofa little water, wiih a quantity of bromine rather more than sufficientto form the monobromo-derivative, the liquid becoming warm andyielding as it cools a brown viscid mass, from which alcohol removesa resinous portion, leaving undissolved a yellow crystalline substanceobtainable by repeated crystallisation from alcohol in broad golden-yellow lamina which melt with slight blackening at 223".The sub-stance thus prepared has nearly the composition of tribromotol u-quinone, but contains only 66.06 to 66-52 per cent. bromine, whereasthe formula of that compound requires 66.85 per cent., the deficiencybeing due to the presence of less highly brominated compoundsformed a t the same time and very difficnlt to separate. The puretribromo-derivative may however be obtained by oxidising tribromo-toluquinol (next page) with ferric chloride, in which case it separatesin rather smaller lamina having the same crystalline form, a brightgolden-yellow colour, and melting a t 235-236".It is insoluble inwater, but very freely soluble in ether and in benzene, very sparinglyin cold alcohol ; it dissolves with partial resinification in potash, alsoin sulphuric acid, from which it is precipitated by water.The same tribromotoluquinone is also formed by the action of sul-phuric acid, manganese dioxide, and potassium bromide on commercialcresol, and lastly, together with a more highly brominated compoundORGANIC CHEMISTRP. 331by subjecting cresol to the simultaneous action of bromine and iodine.Being thus obtained by three different processes, it may be regardedas the one of the three possible tribromotoluquinones, which is mosteasy of formation.With regard to its constitution, it may be observed that the tolu-quinone from which it was prepared, having been formed from ortho-toluidine, must have the constitution C6.Me.0.H.H.0.H, and thereforeits tribromo-derivative must be represented by the formula-C6.Me.0.Br.Br.0.Br ;and this view is in accordance with its formation from commercialcresol which, although it contains the three isomeric cresols, is capableof yielding only one tribromotoluquinone, inasmuch as para-cresolcannot furnish a quinone at all, and ortho- and meta-cresol mustnecessarily yield the same tribromotoluquinone.TribromotoZuquinoZ, C,H,Br,(OH), = C6MeBr3(OH),, is formed bythe prolonged action of sulphurous anhydride on tribromotoluquinonesuspended in water, the colour of the substance changing from yellowto white. On filtering and treating the residue with cold alcohol,the tribromoquinol dissolves, the solution when mixed with waterdepositing a flocculent precipitate, which when purified by successivecry stallisation from water and from alcohol, yields the tribromotolu-quinol in white or faintly reddish needles melting a t 201-202".Thesame product is obtained by reducing tribromotoluquinone with tinand hydrochloric acid. Its alcoholic solution, treated with excess offerric chloride, yields a precipitate of tribromotoluquinone.The anilide of tribromotoluquinone,appears to be formed, together with other anilides, on boiling analcoholic solution of the tribromoquinone with excess of aniline, theproduct separating on cooling in black shining crystals, infusible andnearly insoluble in alcohol.Dibromotoluquinone, C6HMeBr202.-The alcohol which had beenused for washing the tribromoquinone yielded on fractional evaporationan additional quantity of the latter, together with products of lowermelting point mixed with resinous matter ; and the remaining mother-liquor, when filtered and left a t rest, deposited yellow crystals (m.p.about loo3) which, after repeated crystallisation from dilute aceticacid, yielded, as the constituerit most soluble in that liquid, yellowcrystals melting a t 85", and having the composition of dibromotolu-quinone ; the same substance, mixed with traces of the tribromo-quinone, is also found in the alcohol which has been used for crystal-lising the latter, and separates in small quantity on adding water,The same products were obtsined by the use of ether instead of alcohol,the proportion of dibromotoluquinone thereby produced being howeversomewhat larger.H. W.Orthamidobenzaldehyde. By P. FRIEDLAENDER (Rer., 15, 2572-2575).-Orthamidobenzaldehyde is best prepared from anthranii,which is obtained from crude nitrobenzaldehyde by the process pre332 ABSTRACTS OF CHEMICAL PAPERS.viously described by the author (Ber., 15, 2105). A mixture of pureanthranil, ferrous sulphate, and ammonia is gently heated until theodour of anthranil is no longer perceptible. On distillation in a cur-rent of steam, orthamidobenzaldehyde is found in the distillate inshining scales melting a t 39". The crystals are freely soluble in alcohol,ether, benzene, and chloroform.Amidobenzaldehyde forms a crys-talline compound with mercaric chloride and with hydrogen sodiumsulphite. Acetorthamidobenzsldehyde crystallises in long needlesmelting at '71'. When this compound is heated with acetic anhydrideand sodium acetate, carbostyril is produced. Attempts to prepare saltsof amidobenzaldehyde were unsuccessful.Quinoline is produced on warming a mixture of this aldehyde withacetaldehyde and soda solution.The ready conversion of anthranil into amidobenzaldehyde is in cofavour of the view that the constitution of anthranil is c6H4<JE.w. c. w.Bromacetophenone. By R. M~HT~AU (Ber., 15,2464-2466).-Aftera description of the numerous difficulties which attend the formation ofbromacetophenone by dropping bromine into a solution of acetophenonein carbon bisulphide, the author proposes the substitution of aceticacid for the carbon bisulphide, as being a better solvent of the waterand hydrobromic acid formed in the reaction.Adopting this change,the author, in a, test experiment, obtained 80 per cent. of the theo-retical quantity of brornacetophenone.Action of Brornacetophenone on Phenol. By R. MOHLAU(Ber., 15, 2497-2500) .-The intoduction of the benzoyl-group intothe molecule of methyl bromide, and the readiness with which theresultant bromacetophenone reacts with the primary amine, points tobromacetophenone as possessing the character of an acid bromide. I norder to examine this hypothesis, the author has studied the action ofphenol on bromacetophenone, and finds that no action occurs unlessthe hydrogen of the phenol is previously replaced by a metal, whenacetophenone phenyl ether, COPh.CH,.OPh, is produced.This sub-stance crystallises in colourless prisms, melting at, 72", soluble inalcohol, and decomposed by fusion with potash into phenol andphenylmethyl ketone.V. H. V.Acetophenone parunitropltenyl ether,COP~.CH~.O.C~HB,.RO~ [0 : NO2 = 1 : 41,formed by the action of sodium paranitrophenol and bromaceto-phenone, crystallises in golden prisms melting at 144", sparinglysoluble in alcohol, insoluble in water, decomposed by molten alkaliinto paranitrophenol and phenyl-methyl ketone. Orthonitrophenoldoes not undergo a similar reaction. These results show that brom-acetophenone possesses the character rather of an alcoholic than of anacid bromide.V. H. V.Acetophenoneanilide. By R. MOHLAU (Ber., 15, 2466-2480 ;compare Abstracts, 1881, 262).-The hydrochloride of acetophenonORGANIC CHEMISTRP. 333anilide, COPh.CH,.NRPh,HCI, is obtained by passing hydrochloricacid into an ethereal solution of the anilide ; it forms glistening pris-matic crystals, decomposible by water into its constituents. Thehydrobromide forms polysynthetic prisms.Acetylacatopheizoneanilide, C OPh.CH,.NPhZ, crystallises in rhombicprisms melting a t 126", insoluble in water, spa8ringly soln ble in-alcoholand ether, Benzol~lbromacetophenoi~en~nili~e, COPh.CH,.NPhBz, crys-tallises in glistening prisms melting at 145", insoluble in water, solublein alcohol and ether.The product of the action of nitrous acid on acetophenoneanilideis dependent on the conditions of the reaction ; in presence of alcoholnit~oacetophenoneanil~~e is formed ; in presence of glacial acetic acid,nitrosoacetopl~e~zonenitranilide. Nitrosoacetophenoneanilide crptallisesin golden prismatic needles melting at 73", insoluble in water, easilysoluble in alcohol, ether, &c.; soluble in potash, with formationof a red colour.It readily gives Liebermsnn's reaction for nitroso-compounds. Nitrosoacetophenonenitranilide crystallises in glisteningleaflets, insoluble in water, easily soluble in ether ; soluble in potashwith a red colour. On boiling an alcoholic solution of this compoundwith concentrated hydrochloric acid, it is converted into acetoFheizone-nitmnilide, COPh.C~:,.NH.C,H,.NO,, which forms glistening goldenneedles, melting a t 167" ; it can readily be reconverted into the nitroso-derivatives by nitrous acid.On oxidation it yields benzoic acid, andon reduction acetophenone and paraphenylenediamine ; these resultsshow that the nitro-group is in the anilide radical, and that the nitro-group is in the para-position to the imido-group.By the action of fuming nitric acid on acetophenoneanilide, a d i n i t r o -deriuntive, COPh.CH2.NH.C,H,~N0,),, is obtained, which crystallisesin golden prisms, melting a t 171" ; on Oxidation it yields benzoic acid,and on reduction, acetophenone and Will's triamidobenzene[NH,: NH2: NH2 = 1: 2:4],and therefore the constitution of the acetophenonedinitranilide is[NH : NO2 : NO2 = 1 : 2 : 41.Oxidation of Durene by Chromic Acid.-DinitrodurylicAcid. By R.GISSMANN (Annalen, 216, 200-2ll>.-W hen durencb,C6H2Mel [1 : 2 : 4 : Sj, is subjected to the action of chromic acidor other powerful oxidising agents, only one of its methyl-groups isconverted into a carboxyl-group, the greater part of the substancebeing completely broken up, The oxidation is best effected by treatingdureno with the calculated quantity of chromic acid, both dissolved inglacial acid. On pouring the resulting green liquid into water, partof the oxidised product separates as a white flocculent precipitate, anda further quantity may be obtained by precipitating the chromium fronithe hot filtered liquid with caustic soda, filtering again, and super-saturating with hydrochloric acid.The product thus obtained isdurylic acid, CIOH,,O, = C6H2Me.COOH [formerly called cumylic acid].It dissolves very sparingly i n cold, more readily in hot water, fromwhich it crystallises in needles ; with moderate facility in alcohol, ether,and benzene, and separates from the latter in long thick transparentV. H. IT334 ABSTRACTS OF CIIEMICAL PAPERS.strongly refracting prisms ; it sublimes between watch-glasses in longneedles, volatilises completely with aqueous vapour, and melts at150".Jannasch (Zeits. f. Chew., 6 , 449), by oxidising durene with dilutenitric acid, obtained, in addition to durylic (cuiuylic) acid, a bibasicacid, CGH2Me2(COOH)2, which he called cumidic acid.The oxidationof durene by chromic acid in acetic acid solution does not appear toyield a bibasic, or any more highly basic acid.Dinitro-dwylic acid, CMe3(N02)2.COOH, is obtained by graduallyadding durylic acid (1 pt.) to strong nitric acid (10 pts.), in which itdissolves immediately, with copious evolution of red vapours. Onpouring the cooled solution into water, a flocculent precipitate sepa-rates ; and on distilling this with steam, there passes over, togetherwith unaltered durylic acid, a small quantity of a yellowish low-meltingcompound, insoluble in alkalis, which the author regards as probablyconsisting of nitrotrimethylbenzene, formed by exchange of one ofthe carboxyl-groups for a nitro-group.The non-volatile part of the product separates on cooling as a finelydivided precipitate; and on boiling this with water and poundedcalcspar, a calcium salt is obtained, which, when purified by recrystal-lisation and treated with hydrochloric acid, yields d i n i t r o d u r y l i ca c i d as a yellowish powder, melting a t 205", slightly soluble in cold,more readily in hot water, and always separating therefrom as anamorphous deposit.It dissolves very readily in ether, chloroform,and benzene, but does not separate from either of these solvents incharacteristic crystals. On dissolving it in alcohol, adding j u s t suffi-cient water to produce turbidity, and boiling the liquid till it becomesclear again, this clear solution yields large transparent prisms, whichbefore redissolving melt to a transparent oil.The same compoundwas once obtained in very well-defined prisms from a solution of thedinitro-acid in alcoholic ether. The crystals quickly become cloudywhen dried in the air, and when left over sulphuric acid they entirelylose their crystalline form, and are reconverted into dinitrodurylicacid. They probably consist of an unstable compound of this acidwith alcohol of cry stallisation. Their formation affords a ready meansof obtaining the acid in great purity.Calcium diriitrodziry Zate, [CGMe,(N02).COO]Ca,3H20, obtained byneutralisation, crystallises from a highly concentrated solution inradiate groups of shining needles, easily soluble in hot, sparingly incold water.It explodes violently when heated on platinum foil.The bari2~nt salt forms slender silky peach-blossom-coloured needles,likewise containing 3&0, and dissolving in water with moderatefacility.Mmobromodurene, CsHBrMe4, is formed, together with the dibromo-compound, on gradually adding bromine (2 mols.) to durene (1 mol.),both dissolved in glacial acetic acid ; and on pouring t'he contents ofthe flask, which are nearly coloui*less after 12 hours' action, into aconsiderable quantity of cold water, a white flocculent precipitate isobtained, consisting of a mixture of mono- and di-bromodurene, easilyseparable by distillation with steam, the monobromo-compound pass-ing over much more readily than the other, The solution of the disORQANIC CHENISTRY.335tillate in boiling alcohol yields monobromodurene in thin shininglaminz, which after several recrystallisations melt a t 61", while themother-liquor deposits a small quantity of another bromine-compoundin needles melting a t 199". This latter, which is obtained in largerquantity by repeated crystallisation of the residue of the distillate,bears considerable resemblance in external aspect to monobromopseuclo-cumene.Bromodurene, obtained as abot-e, crystallises in thin nacreous laminze,sparingly soluble in cold, readily in hot alcohol, also in ether andbenzene. It isthe fourth crystalline monobromo-derivative of a benzene-homologue,the previously known members of the series being parabromotoluene(m. p. 28.so), bromoparaxylene ( 9-1Oo), and bromopseudocumene(73"). H.W.It volatilises with aqueous vapour, and melts at 61".Protocatechutannic Acid and Anhydrides of AromaticHydroxycarboxylic Acids. By H. SCH~FF (Ber., 15, 2588-2592).When a mixture of phosphorus oxychloride and parahydroxybenzoicacid is gently warmed a t a temperature n o t exceeding 5OU, tetraparozy-benzoid, C2sHls09, is produced. I t is a white insoluble powder, whichis decomposed by heat without melting. Under similar treatmentmetahydroxybenzoic acid yields dimetoaybenzoid, CI4Hl0O5, and octo-metoxybenzoid, C6sH,0,,. The former compound melts between 130"and 133", and is soluble in hot alcohol; t'he latter is an amorphouspowder melting at 160-165", insoluble in alcohol, but freely solublein chloroform.These condensation-products do not give a colorationwith ferric chloride.When ether is added to an aqueous solution of protocatechuic acid,which has been boiled for some hours with arsenic acid, the liquidseparates into three layers, and on evaporating the middle layer,diprotocntechuic acid, C14H1007 remains as a hygroscopic vitreous mass,soluble in water and alcohol. This compound produces a green colora-tion in a solution of ferric chloride, but it resembles tannin in itsother reactions. ~etra~?.otocatechutai~nic acid, C,8H180,, obtained bythe action of phosphorus oxychloride on an ethereal solution of proto-catechuic acid, dissolves slowly in water. It gives a green colorationwith ferric chloride, and bright red with alkalis.KlnteZZagic acid, C,JT,,O,, is formed yhen a mixture of dry arsenicand protocatechuic acids is heated a t 160".It dissolves in nitric acid,yielding an orange-coloured liquid. Gallanaide, C~HTNO, + 1dH20,prepared by the action of ammonia on digallic acid, forms large colour-less crystals. Gallanilide is deposited as a crystalline mass whendigallic acid is dissolved in aniline. w. c. w.Allyloxybenzoic Acids. By S. SCICHILONE (Gazzetta, 12, 449-454).-The methylic and ethylic salts of these acids are prepared bya reacbion analogous to that which yields the corresponding alkylsalts of methoxybenzoic acid and its homologues, viz., by heating themethylic or ethylic salts of the three hydroxybenzoic acids in sealedtubes with molecular proportions of ally1 iodide and potassiu336 ABSTRACTS OF CHEMICAL PAPERS.hydroxide in alcoholic solution, methylic allylsalicylate, for example,by heating methyl salicylate (Gaultheria oil) with allyl iodide andalcoholic potash for nine hours at 120", the reaction being representedby the equation C6Hd(OH).COOMe + C,HJ + KOH = H,O +KI + CsH4(0C3H5).COOMe.Methylic allylealicylate thus prepared, and purified by treatmentwith water, drying with calcium chloride, and repeated fractional dis-tillation, is a colourless or faintly yellow liquid, having a fragrantaromatic odour, and boiling at 245".By saponifying it with excess ofaqueous potash, and treating the product with excess of hydrochloricacid, a l l y l s a l i c y l i c acid, C6H4(OC3H,).COOH, is obtained as amass of transparent needles, which after purification by repeated urys-tallisation, melt at 113".This acid crystallises well from very weakspirit, but from stronger alcohol it separates as an oily liquid, andretains that form even on evaporating the solvent, or leaving it in avacuum. It may however be made to crystdlise readily by dissolvingit in alcohol, even at ordinary temperature, and quickly diluting thesolution with a large quantity of water, whereupon the liquid becomesmilky, but recovers its transparency after a few hours, and then yieldsvery beautiful needles of allylsalicylic acid. The author has inseveral instances found this method of crystallisation very useful forpurifying substances, which, in presence of foreign matters, tend toassume an oily consistence.Allylsalicylic acid is tasteless and inodorous, very soluble in alcohol,ether, benzene, and chloroform, moderately soluble in water.I t s silversalt, C6H4(OC3H5) .COOAg, is crystalline.Para-aZZy Zoaybenzoic acid, C6Hd(OC,R,) .COOH.-The ethylic saltof this acid, prepared from ethyl p-hydroxybenzoate, allyl iodide, andalcoholic potash, and purified by distillation, boils at 260", condensest o a dense, transpareut, nearly colourless liquid, having an odoursomewhat like that of acrolein, but not so repulsive, and solidifies oncooling to a mass of colourless transparent needles, melting a t 1.09".The acid obtained from it by saponification cry stallises in transparentlaminae, melts at 123", dissolves very easily in alcohol, ether, benzene,and chloroform, slightly also in water.Metn-,,~ZlyozyZberzzoic acid, C,H,( OC,H,) .COOH.-The ethylic saltof this acid, prepared like that of the para-cornpound, passes over, afterfractional distillation between 283" and 285", as a heavy fragrant oil,which after '15 or 16 hours solidifies to a crystalline mass.By theaction of potash it is converted into meta-allyloxybenzoic acid, whichcrystallises in colourless laminae, soluble in alcohol and ether, slightlysoluble in water, melting a t 118".(Ber., 15, 2705) .-On dissolving ethyl propiolate in sulphuric acidand pouring the solution upon ice, an oil separates rhich is ethylbenzoylacetate.1 21 21 41 3H. W.Benzoylacetic Acid (Preliminary Notice). By A.BAEYERThe reaction may be thus expressed :-CPh i C.COOEt + H20 = COPh.CHz.COOEtORGANIC CHEMISTRY. 337The free acid is crystalline, and is obtained by the saponification ofits ethxl derivative. A. I(. M.Synthesis of some Acids Analogous in Constitution to Hip-puric Acid. By T. CURTIUS (J.pr. Chem. [2], 26,145-208).-Kolbeconsidered that hippuric acid might be regarded as “ amidaceto-benzoic acid,” but as it has been prepared synthetically by Dessaignesfi,om glycocine and benzoic acid, and by Jasukowitsch from nionochlor-acetic acid and benznmide, it is now generally looked upon as‘‘ benzoylamidacetic acid.”Kolbe, however, is of opinion that this benzoylamidacetic acid isisomeric and not identical with the natural hippuric acid, and theauthor has undertaken the present research with the object of settlingthis point.The crude natural hippuric acid is readily puri6ed bytreating the boiling solution with chlorine until it smells distinctly ofthat gas and the colour becomes pale yellow. On cooling, the hippuricacid deposited is recrystallised with aid of animal charcoal, whereby itis obtained quite pure.To prepare pure glycocine, hippuric acid is decomposed by boilingi t for 12 hours with four times its weight of strong sulphuric acid(1 of acid to 2 of water), and after 24 hours the benzoic acid is filteredoff, and the benzoic acid still in solution is removed by agitation withether. The solution of glycocine sulphate thus obtained is neutralisedwith barium hydroxide or with chalk, filtered, and the excess of bariumremoved from the solution by carbonic anhydride (or the calcium byoxalic acid).On evaporation glycocine is deposited in beautiful crystals,generally short monoclinic prisms ; the form of crystallisation, how-ever, is greatly affected by the presence of inorganic matter ; thus a,trace of soda produces rhombohedrons, and with atrace of baryta, thecrystals are long. Amidacetic acid has a, sp. gr. 1.1607, turns browna t 228”, and melts a t 232-236” with evolution of gas, and becomespurple coloured: it does not polarise. Its basic are mcre prominentthan its acid properties. It does not combine with barium, sodium,or thallium hydroxides (strong bases capable of attacking the amido-group), to form salts.With zinc oxide, however, it forms two salts,(NH2.CH2.C0O),Zn + 8 2 0 , and (NH,.CH,COO),Zn +CH,(NH2) COOH.The solution of the former deposits zinc oxide on adding water orO n boiling, the latter salt being left in solution. In the same waySodium carbonate precipitates zinc carbonate readily from the firstsalt, but not from the second. Sulphuretted hydrogen precipitatesboth salts. Silver amidacetate :-A concentrated solution (containing100 grams) of amidoacetic acid is poured on 38 grams of freshly pre-cipitated silver oxide ; the whole is well stirred and heated nearly toboiling, filtered, and the filtrate allowed to cool in the dark, whencrystals of the salt are deposited; the unused silver oxide is againtreated with the mother-liquor, and so on until all the oxide alongwith 38 grams more is taken up.The crystals are generally smalltransparent prisms, but sometimes form large tablets : they soon be338 ABSTRACTS OF CHEMICAL PAPERS.come grey and opaque on exposure to light. This salt is not hygro-scopic, does not contain water of crystallisation, and does not decom-pose below 100'.Action of Benzoic Chloride o n Ainidacetic Acid.-When silver amid-acetate or free amidacetic acid is heated with benzoic chloride, alarge quantity of resinous matter and benzoic acid are obtained, butvery little of the desired compound, as the silver salt or acid decom-poses below the boiling point of the benzoic chloride.On diluting the mixture with benzene, however, reaction soon setsin with deposition of silver chloride : the whole is kept gently boilinguntil hydrochloric acid commences to come off.The benzene is thendistilled off, and the residue after being washed with ether to removebenzoic acid, is extracted with 30 per cent. alcohol. The alcoholicextract is concentrated, neutralised with soda, acidified with stronghydrochloric acid, and the crystals formed are purified with the aid ofanim a1 charcoal .The crystalline product is a mixture of three acids, (a) contain-ing one, ( B ) containing two, and ('y) containing three atoms ofnitrogen.1. The a-acid, synthetical hippuric acid, is identical with the hippuricacid from the urine of Graminivora. It is sepamted from the mixedproduct by extraction with chloroform, in which the other acids arepractically insoluble. If the silver amidacetate and benzoic chlorideare mixed according to the equation, AgC,H,O,N + C7H,0Cl =C9H9N03, then only small quantities of the P- and y-acids are ob-tained; if, however, 2 equivalents of silver amidacetate are mixedwith 1 equivalent of benzoic chloride, and the 2nd equivalent of thelatter added afterwards, then the chief products are the a- and y-acids. The mixed product is treated with absolute alcohol, in whichthe ry-acid is almost insoluble.The a-acid is nearly d l separated fromthe alcoholic extract by chloroform, and finally, the @-acid is puri-fied by fractional crystallisation from absolute alcohol ; 1st fractioncontains a- and B-acids, 2nd pure p, 3rd ,B and y.When the aqueous solution of the P-acid is cooled slowly, it is de-posited in small transparent colourless rhombic tablets, with satinlustre, greasy to the touch; when, however, the solution is cooledquickly it forms tufts of sharp-pointed microscopic needles.It meltsat 206*5", and at this temperature decomposes and becomes red. It isinsoluble in cold ether, chloroform, benzene, and carbon bisulphide.It is sparingly soluble in cold absolute alcohol, somewhat more SOwhen hot. Ammonia dis-solves it immediately, forming a salt. Cold mineral acids have noaction on the 6-acid, but when boiled with them it is decomposed into1 mol. benzoic acid and 2 mols. amidacetic acid, taking up 2 mols.water-hippuric acid under similar circumstances produces 1 mol.benzoic acid and 1 mol.amidacetic acid, taking up 1 mol. H,O. If,however, the decomposition with warm acid be conducted very care-fully, avoiding excess of acid, then the P-acid takes up only 1 mol.H,O, and breaks up into 1 mol. hippuric acid and 1 mol. amidaceticacid. From these decompositions, coupled with its method of forma-tion, the author concludes that this acid is analogous to hippnric acid,It is very soluble in 30 per cent. alcoholORGANIC CHEMISTRY. 339NHE.CH,.COOH, being amidacetic acid in which one of the hydro-gens is replaced by the radical of hippuric acid, " hippuryl,NHE. CH,.CO,"It is therefore called hippuramidacetic acid,NHE.CH,.CONH.CH,.COOH.With alkalis i t behaves in a similar manner: in the cold, salts areformed, and the acid can be reprecipitated unaltered, but they aredecomposed when warmed, with formation of hippuric acid andglycocine, and finally of benzoic acid and glycocine.It has no basicproperties, but is a strong monobasic acid ; it does not dissolve met,al-lic zinc with evolution of hydrogen, but forms crystalline solublesalts with most of the metals. Silver hippury lamidacetate,c 11HllN204 Ag,forms nodular groups of microscopic needles, insoluble in cold, solublein hot water and in ammoniacal liquids. In the moist state it isblackened by light, but when dry it is not perceptibly coloured, and isperfectly stable at 105". The thallium salt, CllH~lNz04Tl, crystallisesin small hexagonal monosymmetrical tablets. The barium salt,(CllHllN204),Ba + 5H20 (?), can be obtained in four-sided leaflets, orin fine hair-like needles, easily soluble in cold water and ordinaryalcohol, sparingly in absolute alcohol.(CiiHiiN20J2CU 4- ~ ~ H z O ,forms brilliant transparent dark-blue rhombic prisms terminating ateach end in short pyramids. It loses its water of crystallisation at 110",becoming bright green.The zinc sult crystallises in drusy groups ofsmall transparent needles or tablets, with 1+H20, which are driven offat lloo.E t h y l hippuranzidacefate, CI0HllN2O2.COOEt, prepared either by theaction of dry hydrochloric acid gas on a solution of hippuramidaceticacid in absolute alcohol, or by the action of ethyl iodide on the silversalt suspended in absolute alcohol. I t crystallises from ether intransparent tablets, from water in large white needles with satin-likelustre, melting a t 117" (ethyl hippurate melts at 60.5").It is moder-at8ely soluble in cold chloroform and cold watcr, and easily in cold abso-lute alcohol spirit, and in boiling chloroform and ether and in warmwater. Ethyl hippurate is insoluble in cold water, and very easilysoluble in ether ; this difference can be used to advantage in separat-ing hippuric and hippuramidacetic acid. On warming it with aqueousammonia, ethyl hippuramidacetate is dissolved, and a somewhatviolent reaction takes place resulting in the formation of hippurylg lyco 1 lamide, C10HllN202.CONH2, which crystallises in transparentsharp-edged leaflets melting at 202" (hippuramide melts at 183" j,easily soluble in warm absolute alcohol and hot water, sparingly inether and cold water, and insoluble in chloroform and benzene.Hippry lglycollarnide hydrochloride crystnllises in yellow quadrangularleaflets ; i t is resolved into its components by the action of water.Itdoes not form a platinochloride. Monochlorobenzoic acid is formedThe copper satt340 ABSTRACTS OF CHEMICAL PAPERS.by the action of chlorine on hippuramidacetic acid. The */-acid,C10H12Ny04, is deposited from boiling water in brilliant semi-trans-parent films, which under a powerful microscope are seen to consist ofstellate groups of needles ; when it is dried a t loo", it turns yellow.Heated a t 230", it becomes gradually brown, and at a little above240" it, melts with complete decomposition.It is almost insoluble incold water and absolute alcohol, and quite so in other solvents. Itis more soluble in 30 per cent. spirit, in ammonia, alka,lis, andconcentrated mineral acids. On heating it with soda, ammonia it3evolved.This (y) acid is decomposed on heating it with hydrochloric acidin sealed tubes. The products are a nitrogenous substance, C9H9N03,and benzoicand amidacetic acids. A. quantitative experiment showedthe radical Bz to be contained only once in the molecule of the y-acid.With dilute Fehling's solution it gives rise to a carmine coloration,with strong solution a purple-violet. With phenol and sodium hypo-chlorite it is coloured dark green-blue, whilst hippuramidaceticacid is coloured very sliglitly greenish-yellow, and hippuric acid is notcoloured a t all.This acid has a strongly acid reaction, but does notform simple salts. The silver salt forms a white precipitate soluble inammonia, from which it is deposited in small transparent irregulargranules. The author suggests the probable isomerism of this 7-acidwith Griess's uramidobippuric acid. D. A. L.Triphenyl Orthoformate. By P. TIEMANN (Bey., 15, 2685-2687) .-On heating an alkaline solution of phenol with chloroform,and extracting with ether, a neutral oil is obtained which becomescrystalline after purification. It is triphenyl formate, CH(OPh),. Itcrystallises in long white needles (m. p. 71.5") which are insoluble inwater, but soliible in ether, chloroform, boiling alcohol, and hot ben-zene, less soluble in light petroleum.It decomposes when distilled a tthe ordinary pressure, but passes over unchanged under a pressure of50-55 mm. Acids readily decompose it into phenol and formic acid,but alkalis do not affect it. A. I(. M.Tribasic Nitrophenyl Orthoformate. By A. WEDDIGE (J. pr.Chern., 26, 44$-446).-The action of the alkali salts of ortho- andpara-nitrophenol on chloroform results in the formation of a nitro-derivative of the tribasic pheayl orthoformate. This substance,CH(0.C6H4.NOz)3, is produced by heating 2 mols. chloroform with 3mols. potassium nitrophenol and 4 to 6 parts of alcohol a t 140-150"for 10 hours. After purification by crystallisation from alcohol, itforms white needles, which melt at 182".They are not decomposedby boiling pot8ash or soda, but are destroyed by distillation. Theethereal salt prepared in a similar way from para-nitrophenol meltsat 232". Reduction by tin and hydrochloric acid produces a crystal-line base, CH(0.C6H,.NH,)3.It will be interesting to see whether this compound yields a dyeunder the influence of oxidising agents in it manner analogous totriamidotriphenylmethane, CH(CJL.NH&. E. W. PORGANIC CHEMISTRY. 341Paradichlorazobenzene-monosulphonic Acid. By A. CALM(Bey., 15, 2558--2559).-The following salts of paradichlorazoben-zene-monosulphonate (Bar., 13, 1183) have been prepared : -The potassium salt, C6H,C1.N2.C6H,C1.S0,K, forms glistening orange-coloured plates, soluble in alcohol and in hot water.The silversalt, C12H,Cl,N2. S03Ag, a pale-orange amorphous precipitate. Thebarium salt, (C12H7C12N2.S03)2Ba, and the lead salt are obtained ascrystalline precipitates soluble in hot water. The caZcium salt,(C12H,ClzN2.S03)zCa, forms lustrous golden scales. The sulpho-chZoride, C,H,C1.N2.C6H,Cl.S02C~, is deposited from an etherealsolution in orange-coloured needles melting at 161".Preparation of Indigo-blue from Orthonitrobenzaldehyde.By A. BAEYER and V. DRBWSEN (Bey., 15, 28p56-2864).-Ry theaction of alkalis on a solution of orthonitrobenzaldeliyde in acetone, acondensation-product is formed, a dilute solution OE which yieldsindigo if acted on by excess of alkali. This intermediate product isorthonitro-/I-phenyllactyl methyl ketone.It crystallisea in mono-clinic prisms (m. p. 68"), soluble in ether and alcohol, insoluble inpetroleum. On boiling its aqueous solution, it decomposes with forma-tion of indigo. This substance is a direct addition-product of nitro-benzaldehyde and acetone, and probably stands in the same relationto orthonitrocinnamyl ketone that aldol does tlo crotonrtldehyde.Its formation may be expressed thus :-N02.C6H4.CH0 + (CH3),C0= NO2.C6H4.CH(OH).CH2.COMe. On boiling one part of this con-densation-product with acetic anhydride, orthonitrocinnarnyl methylketone is formed. thus :-N02.C6H,.CH(OH).CH2.COMe = H2O + N02.C6H*.CH : CH.COMe.This ketone crystallises in long flat needles melting at 58", soluble inether and alcohol, insoluble in petroleum ; it is identical with one ofthe nitro-compounds obtained by the direct nitration of cinnamylmethyl ketone ; and the identity is further established by the forma-tion of indigo from both under similar conditions. In order toobtain indigo from orthonitro-p-phenyllactyl methyl ketone, soda isadded to its aqueous solution, and the precipitated indigo washedwith alcohol and water.The indigo so obtained is perfectly free fromindirubin ; the change may be represented thus :-W. C. W.2CloH,iNOa = C'isHloNzOz + 2CzH402 + 2H2O.If aldehyde be substituted for acetone, a similar condensation-product is formed, which with excess of alkali yields indigo. Thissubstance is probably analogous to aldol, and is the alcohol of ortho-nitro-0-phenyllactic acid, No2.c6H,.cH(oH) .CH2.CH2.0H.It crys-tallises in needles melting a t 108"; it is converted by silver oxideinto an acid (probably orthonitro-p-phenyllactic acid), which crystal-lises in monoclinic prisms, melting a t 127".On saturating a solution of orthonitrobenzaldehyde in pyrotartaricacid with hydrochloric acid, orthonitrocinnamyl formic acid,is obtained in the crystalline form (m. p. l3So), soluble in alcohol andether. Its barium salt crjstallises in leaflets. OrthonitrocinnamylNOpC6Ha.CH : CH.COOH,VOL. XLIV, 2 342 ABSTRACTS OF CHEMICAL PAPERS.formic acid is easily decomposed by alkalis, with formation of indigoand oxalic acid. V. H. V.Diphenyldiisoindole. By R. MOHLAU (Rer., 15, 2480-2490).-If bromacetophenone is added gradually to boiling aniline, a violentreaction occurs, and from the crude prodnct diphenyldiisoindole isobtained, This substance, C28H32N2, is derived from the condensationof 2 mols.of acetophenone anilide and loss of 2 mols. of water, a,change which may be represented thus ;--NPhPhC CH2 (NHP h . CH2. COP h) = I I + 2H20.HC CPhNPhIt offers the first example of a nitrogen-atom combined with threedifferent hydrocarbon radicals, belonging to the class of substanceswhich the author proposes to call paranitriles.Diphenyldiisoindole crystallises in colonrless glistening scales (m. p.18l0, b. p. over 360"), soluble in alcohol and ether, insoluble in water.It shows some points of resemblance to dimethylaniline in forming a,blue-green colouring matter when heated with benzotrichloride andzinc chloride, and in giving azo-dyes.The picrate crystallises in vermillion-coloured prisms melting at12P, easily soluble in alcohol, ether, and benzene.The nitroso-derivative, C2sH20N,(N0)2 crystallises in rhombic leaflets melting at244". It combines directly with mineral acids to form salts, ofwhich the hydrochloride, C2,H2,N2(N0),,2HC1, crystallises in prisms,the nitrate, C2eH2,N,(NO)a,2HN03, in needles. The nitroso-derivativedoes not give Liebermann's reaction. From the analogy of nitroso-diphenyldiisoindole to nitrosodimethylaniline in forming azo colouringmatters, the author suggests for it the following formula :-NPhPhC a CNO I INOC CPhX h V. H. V.Azo- Colouring Substances from Diphenyldiisoindole. ByR.M~HLAU (Ber., 15, 2490-2497).-Diphenyld~soindolazotribromben-zene hydrochloride, c~,H2,N6Br6,2HC1, prepared from diphenyldiiso-indole and tribromodiazobenzene hydrochloride, crystallises in finegolden needles, insoluble in water and alcohol. On wa.rming it withsodium carbonate, the corresponding base is obtained, which crystal-lises in orange-golden prisms melting at 150". Its alcoholic solutionabsorbs all the rays from the green to the violet.D~he?zyZdii.roindoZazodibromo~henoZ, CdOH26N6Br402.-The hydrochlo-ride of this base is obtained by heating an alcoholic solution ofdiphenyldiisoindole and paradiazodibromophenol with hydrochloricacid. It cryfitallises in glistening olive-colonred prisms, insoluble inwater, and decomposed by alkalis with formation of the free azo-colonrORGANIC CHEMISTRP.343ing substance, which crystallises in golden-green prisms melting at 198".An aqueous solution of its scdium salt dyes wools of an orange, andsilk of a yellow colour, and absorbs all lines of the green, beginningfrom E, and all the blue and violet rays. As the paradiazodibrorno-phenol is convertible into the [6 : 1 : 21 dibromophenol, the diphenyl-diisoindolazodibromophenol can be represented by the formula( CsH4.N2.C6H,Br2.0H),(N,C,) H2Ph2, in which the nitrogen-atomsand the phenyl-groups are in the para-position to each other, and[Br : OH : Br = 6 : 1 : 21.Uipheny ldiisoirzdolazobenzene-suI;r,honic acid, C40H30N6S206, from di-isoindole and diazosulphanilic acid, crystallises in red-brown metallicglistening scales.I t s sodium salt forms golden leaflets, its silver saltvermillion-red prisms. On reduction, the acid is converted intodiphenyldiisoindole-sulphanilic acid, together with a basic substancecrystallising in colourless prisms, but which was not obtained in asuficiently large quantity for a minute examination. V. H. V.Derivatives of Diphenyl. By E. LELLMANN (Bey., 15, 2837-2838) .-Mononitrodibronzodipheny Z, C6H4Br. C6H3Br,N0,.--The authoralludes to the difficulty experienced in introducing one nitro-groupinto Fittig's dibromodiphenyl (m. p. 164"), for either no nitro-derivative is formed or else a dinitro-compound. In order to obtaina mononitro-compound the dibromodiphenyl is dissolved in acetic acid,and an equal volume of nitric acid of sp.gr. 1.52 added. After purifi-cation by alcohol, the compound is obtained as a golden crystallinemass melting at 127", easily soluble in alcohol and benzene.Trinitrodibl.omod~p~eny Z, NO,. C,H,Br. C6H,Br (NO,),, obtained bydissolving dibromodiphenyl in fuming nitric acid, crystallises in smallcolourless needles melting at 177", sparingly soluble in alcohol, easilysoluble in benzene.Dibenzoyldiumidodibrom~~h~yl, (C6H,Br.NH&),, is formed by theaction of benzoic chloride on the corresponding diamidodibromo-phenyl. V. H. V.A Case of Physical Isomerism. By E. LELLMANN (Ber., 15,2835-2837) .-The dibenzoyldiamidodibromophenyl mentioned in thepreceding abstract crystallises in colourless needles, which melt at 195";but if the melting-point tube be suddenly taken out of the hot bath,the contents solidify as a glassy mass, which melts a t 99", solidifies incrystals at 125-130°, and finally melts again at 195".This series ofchanges can be repeated frequently. If the substance of lower melt-ing point be dissolved in alcohol, the modification of high meltingpoint crystallises out. The former could be obtained only as avitreous mass, whilst the latter formed distinct crystals.Nitro-derivatives of Naphthalene. By V. MERZ and W. WEITH(Ber., 15, 2708-2731).-By the action of fuming nitric acid onbromonaphthalene, two isomeric bromodinitronaphthalenes are fornied.One of these, called by the author a-bromodinitronaphthalene, meltsat 170.5", and the other, 6-bromodinitronaphthalene, a t 143".Theformer crystallises from benzene in groups of slender ueedles, and theV. H. V.2 r c 344 ABSTRACTS OF CHEMICAL PAPERS.latter in plates (from benzene) or needles (from alcohol). Both dis-solve readily in alcohol, benzene, and glaciai acetic acid. Boiling withsoda-solution does not decompose them. To obtttin more highlynitrated compounds, the dinitro-derivatives are treated with a mix-ture of fuming nitric and concentrated sulphuric acids, when thea-derivative yields bromotetranitronaphthalene, melting a t 189-189*.5", and the /I-derivative a tetranitro-compound melting a t 245".On dissolving a-bromotetranitronaphthalene in sodic carbonate solu-tion, and then acidulating, tetranitronaphthol (m.p. 180") is precipi-tated. It forms coloured metallic derivatives, which crpstallise well.They explode slightly on heating. The sodium salt!, CloH3(N0,)4.0Na + 2H,O, crystallises in reddish-yeliow scales, the potassium salt,CloH3(NOz)4.0K + l$HzO, in dark-red prisms. The barium salt,[ CloH3(N02)40],Ra + 3H20, forms yellowish-red crystalline flocks,the calcium salt, [ Cl,H3(N0,)40]2Ca + 2H20, yellowish-red needles,and the silver salt, C,oH3(N02),.0Ag + 3H20, dark-coloured needles.By the action of aniline and ammonia on a-bromotetranitronaphtha-lene, tetranitroiiaphthylphenylamine, CloH3(NOz)4.NHPh, melting a t162*5", and tetranitronaphthylamiiie, Cl,H3(N0z)4.NH2, melting a t194", are produced.From p-bromotetranitronaphthalene the corresponding tetranitro-naphthol could not be obtained pure.P-Tetranitronaphthylpheiiyl-amine (m. p. 253"), and B-tetranitronaphthylamine (m. p. 202") were,however, prepared. When oxidised with dilute nitric acid, botha- and p- bromodinitronaph thalene yield ordinary a-mononitrophthalicacid melting a t 212". By the oxidation of a-bromotetranitronaph-thalene, a dinitrophthalic acid (m. p. 227") is obtained, which byreduction and subsequent distillation with soda-lime yields meta-liiamidobenzene. p-Bromotetranitronaphthalene yields a dinitropht ha-dc acid (m. p. ZOO0), from which para-diamidobenzene may be obtained,The formula for the two dinitrophthalic acids are thereforeNO,: COOH:COOH:NOr] = (a) [l : 2 : 3 : 51 and (p) [l : 2 : 3 : 41.From the oxidation-products, it is evident that both in the dinitro-and tetranitro- bromonaphthalenes the nitro-groups are equally dividedbetween the two benzene nuclei.The fact that both bromodinitro-naphthalenes yield a-nitrophthalic acid shows that in both dinitro-derivatives one nitro-gronp must have the position l', and since ithas been ascertained that in hromomononitroph thalene (from bronio-naphthalene) the bromine and the nitro-group are in the 1 : 4 positionto one another, it is highly probable that the two dinitro-compoundsare represented by the following formula :-[NOz : Br : NO2 = 1 : 1 : 4and 4' : 1 : 41.Picrates of a- and &Naphthol. By C. MARCHETTI (Gazzetta, 12,502-504). - These compounds are prepared by dissolving thenaphthol in a small quantity of 85 per cent.alcohol, and the picricacid in a quantity of the same alcohol sufficient to form a solutionsaturated a t ordinary temperature, pouring the boiling picric acidsolution into that of the naphthol, then agitating, and cooling. Theliquid then deposits very slender crystals, which are to be collected onA. I(. MORGANIC CHEMISTRP. 345a suction-filter and dried in a vacuum. The filtered liquid when con-centrated and cooled yields a second crop of crystals, and others maybe obtained in like manner.The crystals thus obtained gave by analysis 51-45 and 51.36 percent. carbon, 3.07 and 3.35 hydrogen, agreeing nearly with the formulaof naphthol picrate, C6H2(N02)3.0H,CloH7.0H, which requires 51.47 Cand 295 H.a- Naphthol picrate crystallises from alcoholic solution on rapidcooling in slender orange-yellow needles, and by slow cooling inlarger needles of an orange-red colour.It melts at 189-190" to anopaque dark-red liquid ; dissolves very freely in alcohol and ether, andcrystallises readily therefrom ; sparingly in cold chloroform, some-what more readily at higher temperatures, and crystallises out oncooling. It is but very slightly soluble in carbon bisulphide, and inwater either cold or boiling. It is decomposed by ammonia, theliquid on distillation with steam yielding the a-naphthol in the freestate.6-NaphthoZ picrate crystallises in thin silky orange-yellow needlesof somewhat lighter colour than the a-compound, and melts at 155'to a dark-red limpid liquid.It is very soluble in alcohol, ether, aridchloroform, less soluble in carbon bisulphide, nearly insoluble in cold,sparingly soluble in hot water. Ammonia decomposes it, separating the@-naphthol, which may be obtained in the crystalline form by heatingthe solution and then leaving it to cool.Derivatives of Naphthalene Hexhydride. By A. AGRESTINI(Gazzettn, 12, 495 -499). -With the view of preparing Graebe'snaphthalene tetrahydride (17, J., 1873, lOOS), the author heated in asealed tube at 235", for 73 hours, 10 g. naphthalene, 3 g. red phos-phorus, and 98 g. hydriodic acid (b. p. 12'7"). On decolorising theresulting liquid with acid sodium sulphite, neutralising with sodiumcarbonate, and distilling with steam, then treating the distillate withether, drying it with calcium chloride, and again distilling, an oil wasobtained lighter than water; and on boiling this oil for some timewith pellets of sodinm, distilling, and treating the distillate withpicric acid, a crystalline precipitate was formed consisting of naphtha-lene picrate.The oil separated from this precipitate was then dis-tilled in a current of steam, dried with calcium chloride and withsodium, and subjected to fractional distlillation, the greater part of itpassing over at 195-196" under a pressure of 773.9 nim. Theanalysis of this distillate gave, as a mean result, 89.53 p.c. carbon and10.57 hydrogen, agreeing closely with the formula CloH14 or CloH,,H6,which requires 89.55 C and 10.45 H.The chief product obtained by the process above described is there-fore naphthalene hexhydride.It is a colourless, fragrant liquid,lighter than water, and boiling at 204-205". It does not combinewith picric acid. It is probably identical with the hydrocarbon CloH14(b. p. 195-200"), which was obtained in like manner, together withothers, by Wreden and Znatowicz (Annalen, 187, 164).Naphtha leneh exh y drosu lp honk Acids, C l0Hl2 ( S03H)2.-Two isomericacids, having this composition, are obtained by the action of fumingH. W346 ABSTRACTS OF CHEMICAL PAPERS.sulphuric acid on naphthalene hexhydride, and may be separated bydilut,ing the product with water, neutralising with lead Carbonate,filtering it a t the boiling heat, precipitating the lead with hydrogensulphide, neutralising the filtrate exactly with potassium carbonate,evaporating to dryness, completing the desiccation of the potassiumsalt thus obtained in a, vacuum, then pulverising and treating it withboiling alcohol.I n this way two potassium salts are obtained, onesoluble in alcohol, the other insoluble, but both having the composi-tion of potassium naphthalene hexhydrobisulphonate, C,oH,z(SO,K)z.The crystals of the former are anhydrous ; those of the latter con-taining 1Q mol. H,O, and are soluble in water. Both these salts,when fused with potassium hydroxide, yield small quantities ofa phenolic substance, shown by its melting point to consist ofa-naphthol.Action of Bromine on. Naphthalene Hexhydride.-On treating thishydrocarbon with bromine in molecular proportions, added by successive quantities, a violent action takes place, accompanied by evolutionof hydrogen bromide, and a nearly colourless liquid is obtainedheavier than water, and decomposing when distilled.After purifica-tion with sodium carbonate, solution in ether, &c., it gave by analysis37.41 p.c. C, 4.48 H, and 38.01 Br, agreeing nearly with the formulaC,,H,Br, which is that of monobromonclylzthalene dihydride.E. W.Some Ethereal Oils. By BEILSTEIN and E. WIEGAND (Ber., 15,2854--2855).--0il of Erecthidis consists of a terpene, C,,H,, (b. p.175", sp. gr. 0.838 a t l8.5"), which absorbs a molecule of hydrochloricacid without the separation of a crystalline compound. The portionof the oil which boils above 200" also consists of a terpene.Oil of Erigeron canadense consists of a terpene (b.p. 176", sp. gr.0.8464) ; it absorbs 2 mols. of hydrochloric acid to form a solid di-hydrochlmide melting a t 4 7 4 8 " .Oil of Majorzcm.--'l'he portion of lower boiling point consists of aterpene (b. p. 178",.sp. gr, 8.463) which absorbs 1 mol. of hydrochloricacid, without forming a compound. The portion boiling from 200-220" contains a sesquiterpene hydrate, C,5Hz,,H2O, which from itsbehaviour towards sodium is shown to contain no hydroxyl-group. v. H. v.Ledum Camphor. By F. HJELT and U. COLLAN (Bey., 15,2500-2501).--In the year 1831, Grasvmann obtained from the wild marshrosemary (Ledurn palustre), a volatile oil, which solidifies on exposuret o form the so-called ledum camphor.The substance has since beenexamined by Trapp, who assigned to it a formula, Cz8H4s0, arid byIvanoff, who deduced the formula C5B80z. The author distilled theoil with water, and obtained the camphor in acicular needles meltingat 101", and from his analyses deduces the formula G,,H,,O,. In itschemical relationship ledum camphor shows no resemblance to theother camphors. V. H. V.Note.-Wright (this Journal, 1815, 1038) assigns to ledum camphorthe formula CzoH3,0.--V. 33. VORGANIC CHEMISTRY, 347Glueosides. By H. SCHIFF (CTazzetta, 12, 460-469).-Arbutim.-The variations in the amount of crystal-water and in meltingpoint (142-145", 162-168', and 187") observed in commercialarbutin are attributed by the author to the presence of methyl-arbutin(Abstr., 1881, 610). This latter compound has been preparedby Michael (Abstr., 1882, 174) by the action of acetochlorhydrose onthe potassium-derivative of methyl-quinol, according to the equa-tion :-0 : CH0.(CH.0G)4.CHT,Cl + R0.C6H4.0Me + 4EtOHAcetochlorhydrose. Potassium-methyl-quinol.= KC1 + 4 E t O z + 0 CH.(CHB.0H)4.CH20.CsH4.0MeMethyl- arb utin .When thus obtained it melts at 168-169", i.e., at about the tem-perature observed by Strecker and others for the melting point ofarbutin, whereas the methyl-arbutin prepared by the author's method,vix., by the action of methyl iodide and potassium hydroxide onarbutin dissolved in methyl alcohol, melts at 175-176".The twoproducts differ also in their amount of crystal-water, the crystalsobtained by Michael's process having the composition 2C13H14017 +H20, while those obtained by the author's method contain C13H11O17 + H20.The smaller amount of water found by Michael was perhapsdue to partial dehydration. Methyl-arbutin may also be obtained inanhydrous crystals, e.g., from concentrated solutions containing potas-sium iodide. Supersaturated solutions sometimes also deposit mam-mellated groups of anhydrous crystals. Methyl-arbutin is moderatelysoluble in cold, freely in boiling water, and in alcohol, sparingly inether, more freely in a mixture of alcohol and ether; its solutionsgive no colour with ferric chloride.The lower melting point (168') observed for arbutin by Streckerand others, and by the author in certain fractions, may perhaps beattributed t o the preseuce of methyl-arbutin, and may be regarded asan additional instance of the fact that a mixture may melt a t a tem-perature lower than the melting point of either of its constituents.Constitution of HeZick-W hen hot saturated solutions of helicin( 5 pts.) and urea (2 pts.) are mixed together, and the mixture isevaporated in an open vessel, there remains a dense colourless syrup,which, when left in the exsiccator over sulphuric acid, leaves a nearlycolourless gummy mass, gradually changing to a white crystallinepowder, which is but slightly soluble in absolute alcohol, and may befreed thereby from uncombined helicin and urea.This compounddissolves in a large quantity of boiling water, and separates on coolingin the form of a very white crystalline powder consisting of gluco-sa 1 i c y 1-c a r ba m i d e, (NH,.CONH),CH.C6H4.0.C6H,,O,. It is dis-tinguished from its components by being hygroscopic and very solublei n water.It deliquesces in alcohol of 99 P.c., dissolves readily inalcohol of 95 pc., and is not precipitated by absolute alcohol evenfrom highly concentrated aqueous solutions. The aqueous solutionhas a bitter taste, and is not precipitated by nitric acid, but gives a348 ABSTRACTS OF CEIEMICAL PAPERS.white flocculent precipitate with mercuric nitrate. The compoundmelts at a high temperature, giving off ammonia, becoming coloured,and apparently decomposing in a very complex manner.Gluc o s o s a l i c y 1 - t h i o c a r b a mi d e,(NH,.CS.NH)&H.C6H,.O.C6H,1,prepared by heating together the alcoholic solutions of 1 pt.thiocar-bamide and 2 pts. crystallised helicin, is also a very white crystallinepowder, even more hygroscopic than the carbamide.The compounds just described afford additional proof of the alde-hydic nature of helicin, which is, moreover, confirmed by its powerof combining with organic bases, as with aniline and toluidine. Withtolylene-diamine it forms ghcosalicy lic tolylenedimmine,C6H3Me : (N CH.C6Hd.O.C6H50,)2,which separates in deep orange-coloured crystalline groups when 5 pts.helicin and 2 pts. tolylenediamine are dissolved together in a smallquantity of hot water. Like most derivatives of metatoluidine, thissubstance exhibits a strong tendency to form deep-coloured corn-poonds.Its dilute aqueous solution exhibits a decided red-greenfluorescence. The crystals contain water, which they lose in theexsiccator, being thereby converted into a vitreous mass, which maybe recrystallised from warm water. It dissolves b u t slightly in coldwater, easily and with red colour in dilute hydrochloric acid.Helicin unites readily with hydrocyanic acid, and yields withPerkin’s reagent a mixture of well-crystallised compounds, which,however, the author has not yet succeeded in separating.Anhydrous helicin does not absorb dry ammonia-gas, but dissolvesreadily in concentrated alcoholic ammonia, forming a solution whichhas only the faintest ammoniacal odour, showing that the ammoniahas really entered into combination, though the compound formed hasbut little stability, and gives off ammonia, even at ordinary tempera-tures.It is probably an additive aldehydic combination,C6H,,O5.O,. C,K,.CH( OH) .NH2,which, however, is not converted into the corresponding hydrosalicyl-amide under conditions similar to those which give rise to the forma-tion of salicylaldehyde.The paper concludes with theoretical speculations as t o the consti-tntion of helicin. H. W.Poisonous Principle of Andromeda Japonica. By J. F.EIJKNAN (Rec. Trav. Clkm., 1, 224-226).-By exhausting with waterthe fresh leaves of this plant, well known in Japan for their poisonousproperties, agitating the concentrated and filtered solution withchloroform, and mixing the chloroform with light petroleum, a pre-cipitate is obtained which may be dissolved in ether containingalcohol, and extracted therefrom by agitation with water ; onevaporating the aqueous solution thus obtained, the poisonous princi-ple remains in the form of a transparent, colourless, brittle uncrystal-lisable substance, which the author has not been able to resolve intomore definite constituents6RU ANIC CHEMISTRY.349This substance, which the author designates as Asebotoxin, is freefrom nitrogen, leaves no ash when burnt, and gave, as the mean offour analyses, 60.48 p.c. C, 7.40 H, and 32.11 0. It softens at loo",and melts at 120". It is more soluble in hot than in cold water, anddissolves readily in chloroform, common alcobol, and amyl alcohol ;also in acetic acid and in ammonia, and to a smaller amount in causticpotash and soda; in all cases without decomposition.It is butslightly soluble in pure ether, and nearly insoluble in benzene, lightpetroleum, and carbon bisulphide. The aqueous solution is neutral, andis not precipitated or changed in any way by ferric chloride, cupricsulphate, mercuric chloride, auric chloride, silver nitrate, or normallead acetate, but gives a flocculent precipitate with the basicacetate. From an alkaline cupric solution it throws down a smallquantity of cuprous hydroxide, but the precipitation is more abundantif the asehotoxin be previously heated with hydrochloric acid, and thefiltered liquid added to the cuprous solution.Asebotoxin moistenedwith hydrochloric acid acquires a splendid blue colour, changing tored-violet at the heat of the water-bath, Strong sulphuric acid dis-solves it with red colour, changing after a while to rose-pink, a bluish-grey substance separating a t the same time.Asebotaxin exhibits the characters of a glucoside, and is extremelypoisonous, a fatal dose for a rabbit by subcutaneous injection being3 mg. per kilogram of bodily weight.The poisonous principle of Andromeda japonica has been examinedwith similar results by P. C. Plugge, who calls it Andromedotoxin, andclaims priority over Eijkrnan.Haematoxylin and Haematei'n. By E. ERDMANN and G. SCHULZ(Annalen, 216, 232-240) .-The authors' experiments confirm theformula of haematoxylin, C16H1406, deduced by Gerhardt from theanalyses of 0.L. Erdmnnn, Hesse, and o t h e z Acetyl-hsmatoxylinhas the composition Ca6HZ4011 = c,6H9&06 [Ac. calc. = 42 per cent.;exp. = 41.74 to 42-67].The authors also confirm the formula C16H,,0s assigned to hsmate'in(the product obtained by exposing an ammoniacal solution of haemat-oxylin to the air) by 0. L. Erdmsnn, and by Hummel and Perkin(Trans., 1882, 367), of whose experiments, however, they takeno notice.By sulphurous acid, and more readily by hydrogen sodium sulphite,ha3mate'in is converted into a colourless liquid, which, however, con.-sists no'; of haematoxylin, but of an addition-product, that obtainedwith the free acid being partially decomposed by boiling, whereas theproduct obtained with the acid sodium salt is decomposed onlywhen heated with an acid, yielding.haemate'in, which when thusprepared, cannot be reconverted, by any mode of treatment, intohematoxylin. A similar result is obtained by reducing haemate'inwith tin and hydrochloric acid.Reim (Bey., 4, 331; 0. J., 1871, 541) by treating hsmatoxylinwith strong nitric acid, obtained an oxidation-product, regarded byhim as identical with Erdmann's haemateh, but really isomeric there-with, inasmuch as it crptallises in brown-red needles much moreH. W350 ABSTRACTS OF CHEMICAL PAPERS,soluble in boiling water than haemate'in, and differs from the latter inmany other characters, especially in its behaviour to sulphurous acid,by which it is immediately reduced to hzematoxylin, whereasErdmann's hzematein is not reduced by similar treatment.Lastly,Reim's oxidation-product is converted by boiling with acetic chloridein a reflnx apparatus into an acetyl-derivative, less soluble in alcoholthan pentacetylhaematoxylin, and crystallising therefrom in sphericalgroups of small white needles, melting with partial decomposition a t216-219'. No such acetyl-derivative can be obtained from Erdmann'shsmatei'n.Attempts to split up haematoxylin and hzemate'in into similar mole-cules have not hitherto yielded very definite results. Hzematoxylinreduced by hydriodic acid (b. p. 127") yields a t first a, red body, notobtainable in definite form, and afterwards, when heated therewith insealed tubes, a mixture of hydrocarbons, a small portion of whichvolatilises with steam, while the rest forms zt black mass soluble inbenzene.By heating haematoxylin with strong ammonia a t about M O O , anitrogenous body is obtained, which has the properties of an amido-p hen o 1, and separates on addition of acids as a light red precipitatesoluble in excess of the acid.The authors confirm the observation made by R.Meyer, thathzeniatoxylin by dry distillation yields a mixture of resorcin oland pyrogallol. The two bodies may be separated by prolongedboiling with benzene, which dissolves pyrogallol more readily thanresorcinol.Hzematoxylin yields f o r m i c a c i d when fused with potassiumhydroxide. H. W.Compounds of the Pyrroline Series. By G. L. CTAMICTAN and M.DENNSTEDT (Ber., 15,2759-2585).-'retroluret~~~e, Et0.CO.N : CoH4,prepared by the action of ethyl chlorocarbonate (diluted with anhy-drous ether) on potassium pyrroline, is a colourless oily liquid boilingat 180". It is almost insoluble in water, and is resinified by contactwith hydrochloric acid.By boiling with alkalis it is converted intoethyl alcohol, pyrroline, and an alkaline carbonate. On treatment withammonia a t 11V, tetrolurethane yields tetrolcarbamide, NH,.CO.N : C4H4.This substance crystallises in colourless plates (m. p. 167"), which canbe sublimed without decomposition. Tetrolurethane is decomposedby ammonia at 130", sqlitting up into alcohol, pyrrol, and urea.Allyijqrroline, C4H4 . NC,H,, obtained by warming potassium pyrrolwith a mixture of ally1 bromide and anhydrous ether, is a colourlessoil, which boils at 105" under a pressure of 48 mm., but decomposeswhen distilled under the ordinary atmospheric pressure.On exposureto the air, it acquires a brown colour, and is partially converted intoresin. It is almost insoluble in water, and gives a white precipitatewith mercuric chloride.TetriodopyrroZine, CJ,HN, is best prepared by cautiously pouring anethereal solution of iodine into a flask containing 100 C.C. of anhydrousether and 10 grams of potassium-pyrroline. The iodine is added until apermanent coloration is produced, but a large excess of iodine must bORGANIC CHEMISTRT. 351avoided. After removing the ether fkom the mixture by distillation,the residue is exhausted with boiling alcohol to separate the potassiumiodide from the iodopyrroline ; the alcoholic solution is treated withanimal charcoal, and poured into water ; and the precipitated productis further purified by solution in alcohol, reprecipitation by water, andrecrystallisation from alcohol.Tetriodopyrroline forms long prismssoluble in ether, acetic acid, and in hot alcohol. The crystals decom-pose without melting between 140" and 150". With silver nitrate, theiralcoholic solution gives a white precipitate which rapidly blackens.Tetriodopyrroline is insoluble in an aqueous solution of potash, butdissolves readily in alcoholic potash. On evaporating the alcohol, awhite crystalline compound remains, which is soluble in water.W.C. W.Substitution-derivatives of Quinoline. By P. FRIEDLANDERand A. WEINBRRQ (Bsr., 15, 2679--2685).-The readiness with whichthe chlorine in a-chloroquinoline can be replaced by hydroxyl andother radicals has been already shown by Friedlander and Ostermaier(Abstr., 1882, 732). The authors find that in the case of 6- andy-chloroquinoline the substitution takes place with much greaterdifficulty, and that the replacement. of hydroxyl by chlorine inhydroxy-quinolines by means of phosphorus pentachloride takes placereadily only in the case of the a-compound. From these results it isinferred that the readiness of the substitution depends on the factthat the cai-bon-atom on which the substitution takes place is directlyunited with nitrogen./iI-chlorocarbostyril, C,H,NOCl, obtained byheating dichloroquinoline with dilute hydrochloric acid a t 120", isfound to be isomeric with the compound obtained by Baeyer andBloem from orthamidophenylpropiolic acid (Bey., 15, 2147), althoiighboth melt at nearly the same temperature, viz., 242O and 246". The@-compound differs from Baeyer's in yielding (with phosphoruspentachloride) a dichloroquinoline melting a t 104". On melting(3-chlorocarbostyril with potash, 6-hydroxycarbostyril melting above300' is obtained ; it is soluble in concentrated hydrochloric acid, andcrystallises from it in slender colourless needles. With alkalis itforms stable salts.By the action of bromine-vapours on the ethyl-derivative ofcarbostyril in the cold, an unstable addition-product is formed,which readily gives off bromine and hydrobromic acid, yieldingamongst other products the ethyl-derivative of monobromocarbo-styril.On heating this with hydrochloric acid, ybromocarbostyrilis produced, identical with the body obtained by Baeyer and Bloerufrom orthamidophenylpropiolic acid (Ber., 15, 2149). By the actionof fused potash the corresponding hydroxy-compound is produced,accompaiiied, however, by small quantities of indole, and by allisomeric hydroxycarbostyril. The latter is separated from yhydroxy-carbostyril by means of hot alcohol. It forms white concentricallygrouped needles melting at 189". From the acid properties of thisbody, and from the readiness with which one hydroxyl-group can bereplaced by chlorine, &c., it is assumed that one hydroxyl-group ispresent in the benzene-ring.In this case the body may be termedhydroxyquinophenol. The body, CgH6C1N0 (m. p. 180°), obtaine352 ABSTRACTS OF CHEMICAL PAPERS.from it by the action of phosphorus pentachloride, possesses propertiessimilar to those of hydroxyquinophenol.Cyanethine and Bases derived from it. By E. v. MEYER ( J . pr.Chern. [el, 26, 337--366).-The author has already shown in a pre-vious paper (Abstr., 1881, 54) that cyanethine probably contains anamido-group, which is easily replaced by hydroxyl on treatment withhydrochloric acid. The hydroxyl is further replaced by chlorine bythe action of phosphorus pentachloride. These bodies may all beregarded as derivatives of the base cyanconiine which has been alreadyprepared.Cynnco?ziine, CgHI4N2.-In the perfectly pure state this base is acolourless oil of about 0.93 sp.gr., and boils a t 204-205". Withmercuric chloride it yields a sparingly soluble double salt, which,dried over sulphuric acid, has the composition HgClz,C9H14N2 + +H20.Simple salts of cyanconiine have not yet been obtained. On heating itwith ethyl iodide at ItiO', reaction takes place, and an ethyhjanconiineis produced, which, however, has not been obtained in the free stlate.By treating the product of the reaction, after purification, withplatinic chloride, a platinochloride, ( C,Hl3EtN2),,HZPtC1,, is obtained.Acetic chloride acts violently on cyanconiine, and a crystalline bodyis produced, which appears to be formed by the combination of equalmolecules of the base and the chloride.Bromine-water added to anaqueous solution of the base causes the separation of an oil which soonbecomes crystalline. This is an unstable polybromide, which, onstanding in the air, gives off some of its bromine. The crystallineresidue on treatment with ammonia yields byonzocyanconiine as itsparingly so111 blt. oil.Chlorocyanconiine (Zoc. cit.), when treated with zinc and hydro-chloric acid, yields a double salt. of a base containing more hydrogenthan cyanconiine. This salt has the formula2; nCI,, C 18H30N4, 2HC1,A. K. M.and yields cyancolriine on oxidation. The base C18K30N4 has not beenisolated.Action of Nitrous Acid o n Cyanethine.-When gaseous nitrous acid ispassed into a solution of cyanethine in glacial acetic acid, the follow-ing reaction takes place: C9H,,N,.NHz + NO.OH = N, + H,O +CgHl3N2,0H.The luyhvxycyanconiine thus produced is idectical withthat prepared in other ways.By the action of the iodides of the alcoholic radicles a t 160" substi-tuted cyanethines are obtained.Methylcyanethine melts at 74", and boils between 257-258". Itdissolves easily in water, forming a strongly alkaline solution, whichabsorbs carbonic anhydride from the air. It expels ammonia from itssalts, and forms double salts with mercuric chloride, silver nitrate, &c.Heated with hydrochloric acid in a sealed tube at 180", it yieldsn?et/zyZamine and the hydroxy-base above mentioned. Hence methyl-cyanethine is probably represented by the formula CgHl,Nz.NHMe.It undergoes no alteration when treated with nitrous acid as abovedescribedORGANIC CHEMISTRY.353Etlqlcyanetl&ze forms hard crystals melting a t 45". It boils a t259-261", and closely resembles the methyl-derivative.By the action of methyl iodide, ethyl iodide, and ethylene bromide a t150" on hydroxycyanconiine, derivatives of the latter are obtained.2l.lethyl-hydroxycyancoiziine, CgHI3MeN2O, forms snow-white needlesmelting a t 76.5". It dissolves in water, form-ing a slightly alkaline solution, which is intensely bitter and onlyslightly poisonous. Its platinochloride crystallises in yellow rhornbicprisms. It also forms a characteristic double salt with mercuricchloride. The base is insoluble in alkalis, in this respect differingwidely from the parent base.Etliy I-hydroxycyanconiine closely resembles the meth yl-derivative.It melts at 43" and boils a t 267-268".It is isomeric with theethoxycyanconiine formerly described (prepared by the action of alcoholicpotash on chlorocyanconiine), inasmuch as the latter splits up intoethyl chloride and the hydroxy-base when treated with hydrochloricacid, whilst the former remains unchanged.Ethylene-h?ydroxcyuri,coniine melts at 153.5", and is very sparinglysoluble in water, wherein it differs widely from the methyl and ethyl-derivatives.By digesting a mixture of hydyoqcyancoiine with alcoholic potashand ethyl iodide, the chief product is the ethyl hydroxy-base, but asmall quantity of ethoxy-base seems to be also formed.The authorconcludes from these experiments that the hydroxycyanconiine andits silver and ethyl-derivatives must be formulated respectively asC,H12N (NH).OH, C9HI2N(NAg).OH, and CgHl3N(NNe) .OH.Action of Bromine o n Cyanethirre,-50 grams of cyanethine is dis-solved in from five to six times its weight of dilute sulphuric acid,and 90 grams of bromine added in small portions at a time, the wholebeing warmed and shaken in a strong closed flask. A yellow oil sepa-rates, which is extracted with ether. The acid solution containsammonia, propionic acid, and rnonobrornocyanethine as hydrobromide.Bromocyanethine, precipitated by ammonia from the solution of itshydrobromide, crystallises from alcohol, in which it is easily soluble,in crystals resembling those of cyanethine.It melts at 152-153".Nascent hydrogen converts it into cyanethine, and nitrous acid intorvLonobronzohydrozycy~ncoiine. The latter forms delicate needles, melt-ing a t 172". It gives an unstable silver derivative on addition of' silvernitrate and a few drops of ammonia.Itdissolves in potash, and the yellow solution contains (besides potas-sium bromide) the potassium salts of a fatty acid (probably propionic),of isocrdipic acid, and of an acid containing nitrogen. The oil, whentreated with twice its volume of concentrated ammonia and allowedto remain for a time, yields beautiful crystals of the amide of a butylene-dicarboxylic acid, C:,H8(CONH2),. From 30 grams of cyanethine about2-3 grams of the body are obtained.On saponification with mode-rately dilute sulphnric acid, it yields the corresponding acid. Itmelts at 192", and is identical with the P-butylenedicarboxylic acidwhich Otto and Beckurts obtained from a-dichloropropionic acid, and isin all probability d i r n e t h y h c c i n i c acid, COOH.CHMe. CHNe.COOH.It boils at 275-276".The oil extracted with ether is a mixture of several substances354 ABSTRACTS OF CHEMICAL PAPERS.Be11 aviour of Hydroxycyanconiine with Bromine and Potassium Hy-dyoaide.-The action of bromine alone on hydroxycyanconiine is exactlysimilar to its action on cyanethine. The same yellow oil is produced,and the same products are found in the acid solution. But whenpotash is used in addition, the result is different, a colourless solutionbeing obtained, and this, when distilled by itself, yields, besidesammonia, a body which, on oxidation with chromic mixture, yieldsaldehyde and propionic and acetic acids.Fused potash decomposes hydroxycyanconiine completely, giving offammonia, whilst the " melt " contains the salts of propionic and aceticacids and potassium cyanide.The anbhor concludes the paper with some remarks on the constitu-tioli of cyanethine.The experiments described seem to warrant theconclusion that the body contains both an amido- and an imido-group,and the formation of di??dhyZsucci&c acid points to the presence ofthe group <CHMe.C-* cHMe*c- Hence the author formulates cyanethine asfollows :-C,H,,N, = C6HSNMe,(NH) (NH2). E.33. R.Specific Rotatory Power of Salts of Nicotine. By P.SCHWEBEL (Ber., 15, 2850--2853).-The author has made a series ofobservations on the specific rotatory power of dilute solutions of saltsof nicotine. The values for the rotatory power [a]= of the hydro-chloride CloHI4N2,HC1 in aqueous solution, varied from + 14.44 to20.02 (L = 100.15) according to the concentra.tion, and agree withthose calculated from the formula [a]= = 51.5 -7931q + 0*004238p2.The values for the acetate varied from + 1.667 to + 4.083, inaccordance with the formula [a]= = 49.68 -0.68199~ + 0.002542p2,for the neutral sulphate from + 1.483 to + 14.717, according to theformula [a]= = 19.97powers of nicotine andNicotine9 799 9It is to be observed- 0.05911q. The molecular.specific iotatorythe above salts, are given in the table below :-.................... -261.71hydrochloride. ....... + 10243acetate .............. + 110.29sulphate ............ + 83.43that whereas the free base is laevorotatory, itssalts are dextrorotatory, and these values for the molecular rotkorypower bear no relation to one another.Caffeine, Theobromine, Xanthine, and Guanine, By E.FISCHER (AwnaZen, 215, 253--320).-Derivntives of C'rtfeine. ChZoro-cafeine, C8H9N402C1, first obtained by Rochleder (Jahrb., 1850, 435),is best prepared by the action of dry chlorine on powdered caffeine,the reaction being assisted towards its close by heating to 75-80' ;it can also be prepared by the action of phosphoric pentachloride oncaffeine. It forms white crystals melting at 188", sparingly soluble incold water and ether, more readily in boiling water and hot alcohol.It is reconverted into caffeine by the action of nascent hydrogen.V.H. VORGANIC CHENISTRT. 355Bromorufeine (Abstr., 1881, Sl4), when heated with alcoholic am-monia for 6 to 8 hours a t 130", is converted into unzidoc(rffelne,C,H,N,02.NH, ; this crystallises in slender needles, melts at above360", and can be sublimed. It is sparingly soluble in water andalcohol, more readily in hot acetic acid. Notwithstanding the entryof the amido-group, it has less basic power than caffeine. It is alsoformed in small quantity by the action of potassium cyanide in dilutealcoholic solution on bromocaffeine.Bromocaff eine, when bolled withaqueous potash, does not yield hydroxycaffeine ; with alcoholic potashit yields ethozycnfeine, C,H,N,O,.OE t, crystallising in colourless needles,which melt at 140' and distil a t a higher temperature with b u t littledecomposition. It has feeble basic properties. If heated with hydro-chloric acid it is resolved into ethyl chloride and hydroayccc$eine (Zoc.cit.) ; this melts a t above 345", and sublimes in considerable quantitya t the same temperature; it yields unstable salts with bases. TheSOdiunz salt, C8H,N403Na + 3H20, crystallises in slender interlacedneedles. The barium saZt, (CsH,N4Q3),Ba + 3H,O, forms gronps ofvery fine prisms ; both salts are very soluble in water. The silver saZtis obtained in slender needles by mixing ammoniacal solutions ofhydroxycaffeine and a silver salt, and boiling to expel ammonia ; it isinsoluble in water ; by heating it with ethyl iodide it is converted intoethoxycaff eine.Hydroxycaffeine, when heated with phosphoruspentachloride and oxychloride, is converted into chlorocaffeine.Oxidising agents react readily with hydroxycaff eine ; concentratednitric acid destroys it even in the cold ; chlorine or bromine, accordingto circumstances, gives either dimethylalloxan with small quantities ofapocnff eine, or in concentrated hydrochloric solution in the cold, yieldsno alloxan, but a mixture of apo- and hypo-caffeine ; in both cases anadditive-compound of the halogen and hydroxycaffeine seems to befirst formed, and then decomposed by the water present.A compoundof this kind is obtained by the action of bromine on dry caffeine, butit is too unstable to purify ; as, however, i t yields diethoxyhydroxy-caffeine when treated with alcohol, it would appear to be a dibromide,C8H,N40,(OH)Br,.Diethozyhydroxyc~ff~ine, C8H,N40,( OH) (OEt),, is best prepared bythe action of bromine on an alcoholic solution of hydroxycaffeine,cooled by a freezing mixture of ice and salt : the yield is nearly quanti-tative. It. crystallises in trislinic prisms, showing combinations ofmPy, mpm, OP mP', and 'Pm, mostly developed in tables parallelto mPm ; the properties of this substance and of the correspondingmethoxy-compound, hare been already described (Zoc.cit.).AZZocafeine, C8H9N305, is obtained as a bye-product in the pre-paration of diethoxyhydroxycaffeine ; it forms a sandy powder, meltsat 198", is nearly insoluble in water, and sparingly soluble even inboiling alcohol ; it is slowly dissolved by boiling with concentratedhydrochloric acid, and on evaporation is decomposed into readilysoluble products.Ayocaffeine, C7HTN3O5, is formed together with hypocaffeine (Abstr.,1881, 614; 1882, 217) by the action of hot hydrochloric acid on di-ethoxycaffeine. It crystallises in monoclinic prisms, having the axialrelations a : b : c = 0.8025 : 1 : 0.6976 ; melts at 147-148", and i356 ABSTRACTS OF CHEMICAL PAPERS.decomposed on further heating; it is readily soluble in hot water,alcohol, and chloroform, sparingly soluble in cold water, benzene, andcarbon bisulphide.Cafuric w i d , C6H9N301, is obtained together with carbonic anhy-dride by boiling apocaffeiiie with water; the statement that hypo-caffeine is formed a t the same time (Abstr., 1882, 217) is found to beerroneous, and was due to the presence of hypocaffeine in the apo-caffeine employed (cf.Maly and Hinteregger, ibid., 632). By theaction of hydriodic acid. caifuric acid is converted into hydrocafuricacid, C6HgN303, crystallising in cohurless prisms, melting between240" and 248", and resoiidifying at 235" ; it is readily soluble in hotwater. On boiling it with baryta-water, methylamine is formed,together with the barium salt of an acid (methylhydantoincarboxylicacid ?), stable in alkaline solution, but yielding methylhydantoin whenthe barium is precipitated by carbonic anhydride.Hypocafeine, C6H,N303 (m.p. 182'), is not derived from the decom-position of apocaffeine as previously stated (Abstr., 1881, 614), but isformed at the same time and apparently independently of the latter inthe decomposition of diethoxyhydroxycaff eine by hydrochloric acid.It can be distilled in great part unchanged, and is readily soluble inhot water and alcohol, sparingly in cold water. The barium salt,( C6HFN3OJ2Ba, crystallises in slender white needles, the silver salt,C6H3N,o,Ag or C18H,9N909Ag2, in aggregates of plates. On boiling itwith baryta-water, hypocaff eine is converted into caffoline (Abstr.,1882, 217, 628).When caff oline is boiled with acetic anhydride, carbonic anhydrideand acety Zacecaff'eine, C6Hl0N3O&, are formed ; this crystallises inmonoclinic forms, showing the combinations mPm, OP, mP, Pco,%Pa.It melts a t 106-107", is readily soluble in water, alcohol,chloroform, and benzene, sparingly in ether. On treatment withhydrochloric acid, acecaff eine hydrochloride is obtained as a crystallinemass, readily soluble in water, and yielding the free base on treatmentwith silver oxide.Acecufeine, C6HllN3O2, crystallises in prismatic or tabular forms ofthe rhombic system, having the axial relations a :_h : c = 0.6707 : 1 :1.2245, and_ showing the combination mP: OP, Pa, and, less fre-quently, mPm. It melts at 110-112", distils without decomposition,and is readily soluble in water and alcohol.On oxidation withchromic acid, it yields a substance closely resembling cholestrophane.By the action of chlorine a chloro-derivative is obtained, crystal-lising in colourless needles. When heated with baryta-water, am-monia, methylamine, and dimethylcarbamide are formed.THEOBRONINE.-BY the action of chlorine on theobromine, mono-methylalloxan and methylcarbaraide are obtained. Bromotheobromine,C,H,N,O,Br, is prepared in a manner similar to bromocaffeine, andforms a white crystalline powder, sparingly soluble in hot water,nearly insoluble in the cold ; like theobromine, it possesses acid pro-perties, and dissolves readily in aqueous solutions of alkalis, but onlysparingly in ammonia. The potassium salt is nearly insoluble inalcohol, and does not yield an ethoxy-compound on long boiling withalcoholic potash.The silver salt is obtained as a crystalline preORGANIC CHEMISTRY. 35 7cipitate by mixing ammonincal solutions of bromotheobromine andsilver nitrate. On heating this silver salt with ethyl iodide, bromethyi-theobromine is obtained ; it closely resembles bromocaffeine. By theaction of alcoholic potash, it yields ethosyeth?lZtheobromin~, crystallisingin needles (rn. p. 155"). Hydrox?yetkyZtheobromine, C,H,EtN,O,.OH,is obtained on boiling the ethoxy-compound with hydrochloric acid ; itclosely resembles hydroxycaff eine in appearance ; treated with bromineand alcohol it is converted into diethozykyclroxyethyZtheobrolni?ze (m. p.152"), which is much more readily soluble in alcohol than the corre-sponding caff eine-compound, arid is decomposed by evaporation withhydrochloric acid into methylamine and upoethy ltheobromine. Thislast, on being boiled with water, gives a substance which, by itsbehaviour with basic lead acetate, is undoubtedly a homologue of caf-furic acid.HyPoetliyZthsobromin,e, C,H9N,0s, is obtained, together with the apo-compound, by the action of chlcrine on a solution of hydroxyethyl-theobromine cooled to -10".It forms colourless crystals melting at142", and closely resembles hypocaffeine; it is sparingly soluble incold, readily in hot water, and can be distilled unchanged. The authorconsiders that these results show that the same methylamine-group issplit off in the formation of apo- and hypo-compounds, from bothcaffeine and theobromine.XANTHINE.--From the resemblance which xanthine bears to caffeineand theobromine, Strecker (Artnnlen, 118, 72) considered that thethree bases formed a homologous series, but was unsuccessful in hisattempts to methylate xnnthine.Xanthine is best prepared from guanine as follows :-lo grams ofguanine is dissolved in a mixture of 20 grams concentrated sulphuricacid and 150 grams water, heated to boiling, and after cooling to70-80", a solution of 8 grams of sodium nitrite is added, the mixturebeing well stirred.The yield is nearly quantitative, the xanthine isonly of a pale orange colour, and is free from Strecker's nitro-body.By the action of hydrochloric acid and potassic chlorate xanthineis convert,ed into alloxan and urea.On heating the lead salt of xanthine with la times its weight ofmethyl iodide in closed tubes for 12 hours at loo", a yellow maps isobtained, from which, by boiling with water, treatment with hydrogensulphide, and evaporation with ammonia, a crystalline powder isobtained, possessing all the properties of theobromine.To remove alldoubt as to its identity with natural theobromine, it was convertedinto caffeine by Strecker's method ; the melting point of the sampleso prepared agreed perfectly with that of natural careine.Corlstitution of Cafeine and its Derivatives.-The following are theprincipal facts to be considered in assigning a formula to caffeine :-1. Its decomposition by chlorine into dimethylalloxan and monomethyl-carbnmide. 2.The presence of a single hydrogen-atom other thanthose contained in the three methy 1-groups, and capable of replacementby chlorine, bromine, or the amido- or hydroxyl-groups. 3. The directunion with a molecule of bromine, showing a double carbon linking.4. The conversion of caffeine by addition of oxygen and successiveVOL. XTJV. 2 358 ABSTRACTS OF CHEMICAL PAPERS.elimination of methylamine and carbonic anhydride, into caff uric acid,a substance easily resolved into mesoxalic acid, methylamine, andmethylcarbamide. 5. The ready formation of methylhydantoin fromhydrocaffuric acid, showing the presence in the latter of the groupC.NMeI \ (6.) It has already been shown (Abstr., 1882, 628) thatcaffoline has the constitution I \CO.From these con-siderations caffeine and its homologues are best represented by thefor muls -C,N/CO*0H.CH.NMeNHMe.C = N'MeN-CH MeN-CH HN-CHI IOC CNH.1 IIOC C.NMeI IIOC C.NMeCaffeine. Theobromine. Xanthine.The following formulse are assigned by the author to the moreimportant caffeine-derivatives.COOH COOH COOHICOO. C-NMeIHC-EMeIH0.C-NMe ' \co MeN--C=N/ I I 'co NHMe.C=N/ ' NHMe.C=N/Caffurio acid. Hydrocaffuric acid. Apocaffeine.COO. C H--NMeI I \co MeN----C=N-/Bypocaffeine. A. J. G.Some Derivatives of Morphine. By E. GRIMAUX (Ann. Chim.Phys. [ 5 ] , 27, 273--288).-The substance of Part 1 of this paper hasalready been abstracted (Abstr., 1881, 829) from the Comptes rendus.PART 11.--By acting on the sodium compound of moi-phine withethyl iodide, athy Zmorphine, Cl7Hl8NO3Et, is obtained.This body ishomologous with codeine, itself an ether of morphine, and the authortherefore proposes the generic name codeznes for this class of bodies.Code'ine proper would then be codomethy l i n e , the body under discussion,codethyline, &c. Codethyline crystallises with 1 mol. H,O in plates,soluble in boiling water, alcohol, and ether. At 83" it fuses t o a clearliquid, which solidifies on cooling to a transparent vitreous mass.Heated for scme time at loo", it turns brown, and after cooling fnses at55-60'. Its hydrochloride crystallises in groups of needles. Sulphuricacid does not colour it. Heated to 2C" with sulphuric acid and ferricchloride, it gives a blne coloor, a reaction apparently common to allethers of this class, and not, as Hesse suggested, confined to codeinORGANIC CHEMISTRY. 359proper. Dried in the air at the ordinary temperature, codethyline hasthe formula C19H23N03,H20, but loses mol. of H,O in a vacuum.This seems to support Wright and Matthiessen's double Eormula.Heated with methyl iodide, it forms the addition-productwhich, if treated with silver oxide, yields a tertiary base fnsing a t132", and giving with sulphuric acid the same reaction as metho-codejine. Other halogen compounds, such as the alcoholic iodides,epichlorhydrin, ally1 bromide, benzyl chloride, chlorometh yl acetate,ethylene bromide, &c., give similar compounds with the sodium saltof morphine.Ethy lene-dimorphine, or Dicodethine, ( C,,H,,N03).2C,H4, crystallises insmall colourless needles, insoluble in ether, soluble in alcohol. Onheating, it decomposes below 200°, without fusion. Heated to 20" wit11sulphuric acid and ferric chloride, it gives a blue coloration. Itshydrochloride crystallises in small colourless prisms, easily soluble inwater. With chloromethyl acetate, oxacety lcodezne, or morphine-glycollic acid, CliH,,N03.CH:,.G0 is produced. This body, obtainedas a deliquescent gummy substance, drying up in a vacuum to anamorphous mass, is very unstable, and decomposes on being boiledwith water.When codeine methiodide is treated with silver oxide, it yields acompound which seems to be an ammonium base. On evaporatingthe product in a vacuum on a brine-bath, an oil is deposited,partially crystallising on complete evaporation. From this residueether extracts a substance of the formula C19H27N03, crystallising inbright plates, and having all the properties of a tertiary base; itappears to be formed by the dehydration of methylcodeine hydroxide,and to be analogous to some bodies obtained by Claus from the cin-chona alkaloids. Methocodezne fuses a t 118.5", and soon turns brownif kept a t this temperature. Codethyline methiodide, if treated withsilver oxide, yields a base analogous to methocode'ine, but melting at132".With aldehydes, morphine yields compounds similar t o thoseobt,ained by Baeyer with the phenols. If morphine is treated withmethylal or chloromethyl acetate, it forms a cornpound apparentlyof the formula CH2(Cl7H,,NO3),. The ethers of morphine formsimilar compounds. Benzaldehyde appears to act in like manner.L. T. T.Specific Rotatory Power of Apocinchonine and Hydro-chlorapocinchonine under the Influence of Acids. By A. C.OUDEMANS, Jun. (Rec. Trav. Chim., 1, 173--185).--This paper givesthe results of a large number of observations leading to the conclusionthat, in regard to variation in specific rotatory power under the influenceof acids, the two bases above mentioned conform to the laws alreadydemonstrated with regard to the four hiacid cinchona-bases (p. 81).The statement of Hesse that the specific rotatory power of hydro-chlorapocinchonine is the same in its basic as in its neutral salts, isregarded by the author as destitute of foundation. H. W.2 b 360 ABSTRACTS OF CHEMICAL PAPERS.Behaviour of Conglutin from Lupines towards Saline Solu-tions. By H. RITTHAUSEN (J.pr. Chenz., 26,422-44@).-1n a prelimi-nary communication (Abstr., 1881, 1160) it was stated that crude aswell as purified conglutin from lupine seeds was almost entirely solubleinn 5 per cent. solution of sodium chloride, and a portion remaininguudissolved proved the presence of two sorts of proteids present. Itwas also shown that on adding water to the saline solution, a portionof this proteid was Precipitated, whilst from the mother-liquor coppersulphate separated another portion ; the proportions in which thesesubstances were present were also different, the more nitrogenousbeing present in larger proportion in the soluble part, the less nitro-genous in the insoluble. The present communication deals more fullywith observations made. The results are, that lupines contain largequantities of albumino'id matter relatively poor in carbon, but rich innitrogen, the composition being, C 50.16, H 7.03, N 18.67, S 1.07,0 23.07, corresponding with the formula (C4,H7,N ,,O,,),S. This albu-mino'id matter is soluble a t the ordinary temperature in a 5 per. cent.sodium chloride solution, and by the addition of 4-5 times thevolume of water, is reprecipitated to the extent of 80-90 per cent. It islikewise soluble in water containing a little potassium hydroxidewithout decomposition, and is precipitated by acetic or hydrochloricacids. I n the sodium chloride mother-liquor, a substance remainsdissolved, which is precipitated by salts of copper, and is soluble insolutions of iime or potash. The body heretofore named conglutin istlivided by sodium chloride solutions into a soluble and an insolublesubstance, the latter being however dissolved by potash -solution, andconsisting of legumin originally present, and not of a prodpct of decom-position; otherwise the formation of ammonia, &c., in presence ofpotash would have been noticed. The composition of the substances,one precipitated by addition of water to the salt solution, the otherseparated from the mother-liquors by potash or copper salts, appears tobe identical, and the properties possessed are those of glutin, and forthis substance the author retains the name conglutin. Conglutin ispresent in larger quantities than legumin, from which it may beeasily separated by treatment with potassium hydroxide, additioB ofhydrochloric acid, purification by alcohol, treatment of the dried pre-cipitate with salt solution, which dissolves the conglutin. The aboveis true for the seeds of the blue o r yellow lupines, although thealbumino'id in the blue contains rather less sulphnr. E. W. P.Albuminoids in Peach Kernels and Sesame Cake. By H.RITTHAUSEN (J. pr. Chem., 26, 440-444) .-Peach kernels, whentreated with a 5 per cent. solution of sodium chloride, yie.ld up nearlyall their albumino'id matter, but this substance is reprecipitated onlyby the addition of acids ; in composition it resembles conglutin andthe albuminoid in hazel-nuts acd almonds, but is most probablycombined with potash, seeing that it is precipitated only by acids,and not by the addition of small quantities of water t o its solution.Y'reatment of these kernels with sodium chloride causes the pro-duction of a larger amount of hydrocyanic acid than water alone.In a specimen of sesame cake the author found that the albuminoiPHYSIOLOGICAL CHEJIISTRP. 361contained 2.36 per cent. S (see PJliiger's Archiv., 21, 92-96) ; a laterexamination proves that this excess of sulphur is due not to the albu-~iiino'id, but to calcium sulphate occurring in the ash of the prepara-t,ion. E. W. P

ISSN:0368-1769    

DOI:10.1039/CA8834400302

出版商:RSC    

年代:1883

数据来源: RSC