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126 ABSTRACTS OF CHEMICAL PAPERS. Emplectite from RBzbanya. By J. -4. KRENBER (Juhrb. f. &fin., 1885, 2, Ref., 263-264).-The mineral from Rbzbhnya, described by Peters as bismuthine, is emplectite. An analysis gave the following results :- S. Te. Bi. Cu. Ag. Pb. Fe. Total. 18.61 0.16 63.20 16.84 0.20 1.14 0.11 100.26 corresponding with the formula Cua8,BiaSa. shown by the author to be wollastonite. The accompanying mineral, described by Peters as tremolite, is B. H. B. Zircon and Titanium Minerals. By H. TH~~RACH (Jahrb. f. Min., 1885, 2, Ref., 396-401) .-In conducting an investigation of the rocks of the Spessart, and their alteration products, the author found zircon and titanium minerals in many of the rocks. He has since extended his researches to the rocks of other districts, and the results of his investigations may be summarised as follows :- Microscopic zircon is rarely absent in the ArchEan and sedimentary rocks. It also occurs in very many eruptive rocks.Its wide distri- bution in basalts and dolerites was hitherto unknown. Rutile is also contained in almost all ArchEau and sedimentary rocks, and in the de'bris from granites, porphyries, diabases, basalts, and dolerites. Microscopic annstase is widely distributed in decomposed crystalline and sedimentary rocks, and, in these, occurs principally in two types, one formed by the primary pyramid and the basal plane, and developed in a tabular or pyramidal manner; whilst the other is formed by an obtuse pyramid of the second order and the basal plane, pyesenting crystals of a lenticular character.Microscopic brookite is distributed in the same way as anatnse, and appears in thin or thick tablets with the rnacrodi3gonals predominaJing, and "showing the subordinate planes mP, Y2, 2Pm, OP, &P, iPm, and WPW. Anatase and brookite never occur in unaltered crystalline rocks, but only when the rock weathers. In the sedimentary rocks, they are partially of recent formation, partially derived from secondary deposits. Pseudo-brookite occurs in the alkered basalt and phonolite of the Kreuzberg, and has been formed during the weathering of the rock. Of a,ll the minerals occurring in the sedimentary rocks, staurolite deserves special attention as evidence of the derivation of these rocks from the various ArchEan rocks. (Compare Sandberger, this vol., p.24.) B. H. B. Minerals from Switzerland. By G. SELIGMANN (Jahrb. f. Mi.., 1885, 2, Ref., 240--242).-The author describes the following minei:als :-Brookite from the Maderana Thal ; milarite and turnerite from the Strim Glacier; danburite crystals from the Scopi; topaz, resuvian and diopside from the P i z Rondadura; iron glance and phenacite from the Rachi Thal. A new occurrence of iron glance, OR, mP2, mP, $P2, R, r i t h adularia, calcite, and quartz, occasionally in very fine twin crystals, is described, from the Gorpibaoh, a tributary of the Rh6ne. B. €1. B.MINERALOGICAL CHEMISTRY. 127 Richellite. By G. CESBRO (Jahrb. f. K n . , 1885, 2, Ref., 260).- The results of the analyses are : (I) for compact richellite; (11) for laminated richellite :- Hygroscopic H,O.HzO. HF. P,O,. Fe,O,. CaO. Also,. Total. I. 6-90 25.64 1.22 27.23 29.63 6-18 2-82 99.62 11. 9.47 23.63 0-96 25549 29.67 7.19 3-64 100.05 corresponding with the formula : 4Fe,(PO,), + Fez03,2H% + 36H20. Richellite is amorphous. (comp. Abstr., 1884, 1102). It is found in the neighbourhood of Vise B. H. B. Optical Properties of Berzeliite. By BERTRAKD (Jahrb. f. Min., 1885, 2, Ref., 246-247).-The author has determined the optical properties of the Ferzeliite, recently discovered by Igelstriim (this vol., p. 25) in Nordmark. An examination of the Lingban berzeliite conducted a t the same time showed that the two minerals differ considerably. The berzeliite from Lhgban, which occurs in large fragments, exhibits, on the same specimen, points with single and double refraction ; but the double refraction is indistinct, and in con- vergent light the interference figures cannot be detected.The berzeliite from Nordmark, which occurs almost without exception in round grains wit,hout crystal planes, always exhibits distinct double refraction of a very constant character. It is biaxial: 2E = 140". The bisectrix is positive ; p is less than v. As also no dispersion of t'he axes of elasticity was observed, the author is inclined to regard the Nordmark berzeliite as belonging to the rhombic system. B. H. R. Beryl from Amelia, Co., Virginia. By R. W. BAKER (Amer. Chem. J., 7, 175--176).-The sample from Amelia Court House was transparent and of a rich honey-yellow colour; there were many microscopical fluid cavities.Analysis gave- SiO,. Al,O,. Fe,O,. BeO. CaO. Na,O. H,O. 65.24 17.05 2-20 12.64 0.57 0.68 2.70 = 101.08. constituents of beryl. H. B. The author holds that both water and alkalis are probably normal Allanite from Nelson Co., Virginia. By C. MEMMINGER (Amer. Chem. J., 7, 177--178).-The mineral occurs in rounded masses, covered with a thin yellowish-white coating. Lustre resinous ; hard- ness 6 ; sp. gr. 3.59. SiO,. SnO,. A1,0,. Ce,O,. Di,O,. L%O,. FezO,. FeO. CaO. 30.04 0.17 16.10 11.61 5.39 4.11 5-06 9.89 13.02 1.11 0.28 0.02 2.56 = 99.36 Analysis gave :- MgO. N%O. K20. HsO. H. B.128 ABSTRACTS OF CHEMICAL PAPERS. A Decomposition Product of Allanite : a Variety of Kaolinite from Nelson Go., Virginia. By E. P. VALEN'I'INE.-This brown, soft substance is produced by the weathering of the allanite described in the preceding Abstract.Analyses gave- SiO,. A1203. Fe,03. Ce203. La203. Di203. MgO. K20. I. 18.66 23.28 34.48 1.30 3.27' 0.65 C.29 0.20 TI. 21.37 20.66 12.24 21.90 - - - -- Na,O. BeO. HzO. I. 0.43 - 17.16 = 99.72 11. - 1.95 21.37 = 99.49 H. B. Hornblende from St. Lawrence Co., New York. By G. IT. WILLIAMS (Jahrb. f. illin., 1685, 2, Mem., 175--176).-The author has made a series of crystallographic observations on the green horn- blende (pargasite) occurring a t East 'Russel, St. Lawrence Co. The results are of interest on account'of the discovery of two new planes : mP3 and mP?. The following, forms were observed on several crystals: PA, m ~ f , m ~ i , W P ~ , m ~ , WP?, W P ~ , m ~ e . B. H. B. Amphibole-Anthophyllite from Baltimore.I3y G. H. WILLIAMS fJtchrb. f. &Fir&., 1885, 2, Mem., 176-177):The author describes an interestling occurrence of amphibole-anthophyllite, near Baltimore, which is perfectly similar to that described by Des Cloizeaux from Greenland and Norway. An analysis shows that the mineral is a typical anthophyllite ; and from the optical examination there can be no doubt that it belongs to the monoclinic system. Krokydolite and Arfvedsonite. By A. RENNGOTT (Jahrb. f. Min., 1885, 2, Mern., 163-167) .-From a comparison of the published analyses of krokydolite and afvedsonite, the author concludes that krokydolite must be regarded as a fibrous rariety of arfvedsonite. An analysis of the krokydolite associated with nrfvedsonite in the zircon-syenite of Stavern in South Norway, would be of great value towards determining the relation between the two minerals.B. H. B. B. H. B. Alteration of Labradorite intb an Albite and a Zeolitic Mineral. By KLOOS (Jahrb. f. Min., 1885, 2, Ref., 412-413).- I n a rock from the Black Forest, consisting of plagioclase (labradorite), diallage, and hornblende, the author observed a gradual transition of the unaltered labradorite (Analysis 1) into EL dull, milk-white, opaque mass, which was found under the microscope to consist of' two minerals, a striated felspar and a finely granular mineral. The second mineral WRS soluble in dilute hydrochloric acid. 11 and 111 are analyses of the mixture, IV and V the plagioclase, and V the soluble, finely granular rniueral.MIn’ERALOCIICAL CHEMISTRY.129 SO,. A1,0,. CaO. MgO. N,O. KzO. HzO. I. 51.53 31.41 13.00 -- 3.49 0.57 - 11. 61.64 22.47 4-98 - 8.03 0.60 3.19 In. 58-02 24-00 7-4s 0.25 6.43 0.44 3-11 IV. 64.87 21.54 2.28 - 8.78 1*:33 - V. 68.61 20.36 1.55 - 8.88 0.58 - VI. 42.73 27.55 16.40 - 0.83 0.10 12.39 The newly formed plngioclase represents a mixture of 1 mol. nnorthite and 8 mols. albite (IV), or 1 mol. anorthite and 10 mols. albite (V). The second mineral appears to be a zeolite with the molecular proportion of Na,O : CaO : A1,03 : SiO, : HzO = 1 : 21 : 19 : 51 : 49. This constitution is approximately that of scolezite. B. H. B. Alteration-pseudomorphs of Scapolite after Garnet. By A. CATHREIN (Jalzrb. f. Min., 1885, 2, 251).-Near the Castle of Achen- rain, the author found an altered garnet contained in a fragment of amphibolite.The microscopic examination, the measurements of a pyramid 3P3, and the chemical analysis, indicate that the specimen is an alteration-product which resembles many scapolites, notably passauite. The analysis, it is true, was incomplete, as soda, potash, and chlorine were estimated by difference. The comparison of the analytical results with the theoretical composition of a mixture of 45 per cent. meionite silicate and 55 per cent. marialite silicate is fairly satisfactory, and the other observations clearly indicate that the white mineral surrounding the garnet-interior is scnpolite. Epidote and labradorite appear as bye-products of the alteratiok. B. H. B. The Branchville Mica. By C. RAMMELSBERQ ( h h r b .f. Min., 1885, 2, Mem., 225-22S).-G. vom R,ath presented the author with a large specimen of mica from Branchville, Connecticut. The specimen consists of grey, translucent mica (I), traversed in the middle by a broad layer of dark-brown mica (11). Analysis gave the following results :- F. SiO,. A1,0,. Fe203. FeO. K20. Na20. I. 0.93 44.19 32.69 4.75 3.90 8-00 0-59 11. 2-43 40.14 23-43 7.65 11-87 9-64 1.13 Li20. H20. Total. Sp. gr. I. 0.21 3.85 99.11 2.898 TI. 1-18 2.64 100.11 3.030 Both micas appear to be new varieties of pure iron mica, their formulw being- I. R’,,FeZk7Si,,056. 11. R’,Be2J&Si90s. B. H. B. Chloritoid containing Manganese. By E. PRosr (Jahrb. f. VOL. L. k ,Min., 1885, 2, Ref., 259).-This mineral, the salmite of Dnmont,130 ABSTkACTS OF CHEMICAL PAPERS.occurs in the quartz veins which traverse the phyllnde snlmien of Vielsalm. It forms irregular masses with a finely granular texture, and greyish-green colour. The mineral fuses with diEculty to a black enamel, and is imperfectly soluble in hydrochloric acid. H. = 5 to 6 ; sp. gr. 3-38, The analysis gave the following results :- Quartz. SiO,. A1203. Fe203. PeO. MnO. COO. MgO. 15-06 19.14 33.66 3.38 13.05 7-14! 0.04 1.79 CaO. H20. Total. 0.30 6-32 99.88 This corresponds with the formula- B. H. B. Chlorite from Albemarle Co., Virginia. By M. BIND (Anzer. Chem. J., 7, 181).--Olive-green, pearly scales ; hardness 2.5 ; sp. gr. 3.05. Under the microscope, a small amount of hydrated ferric oxide is seen between the lamina Analysis gave- SiO,. Al,O,. %e20,.FeO. MnO. CaO. MgO. H20. 23.52 22-35 1-92 28.78 0.32 0.39 10.70 11.28 = 99.35 Some Ill-determined Minerals. By HEDDLE (Bin. Hug., 5, 26-31 ; Jahrb. f. Min., 1885, 2, Ref., 260-262).-The followiiig substances are described as ill-determined or doubtful species :- PZynthite.-From Quiraing in Skye. It occurs in layers 1 to 2 inches thick in amy gdaloid. Colonr deep red, lustre greasy, sometimes earthy and dull. It falls to pieces in water, and may thus be dis- tinguished from the accompanying massive mesolite. Its composition was found to be as follows :- H. B. SiO,. A120,. Pe203. FeO. MnO. CaO. H20. Total. 29.54 19-02 28.01 3.25 0.84 2-23 17.39 100.28 A t 100" it loses 6.687 per cent. of moisture. At the Storr, in Skye, it occurs in a repeated series of beds.Ui;gite.-The mineral, for which the name uigite is proposed, was found at Uig, 16 miles north of Portree, in Skye, with faroelite and analcime. It occurs indistinctly crystallised in small nests in the amygdaloid. In general appearance, it is intermediate between faroelite and gyrolite. Sp. gr. 2.284. Analyses gave the following results :- It, is evidently merely bole. SiO,. A1203. CaO. ?Ja20. H20. Total. I. 46.32 21.35 16.36 4.69 12.21 100.93 11. 45.98 21-93 16-15 4-68 11.25 99.99 Uigite is thus either a mixture of faroelite and gyrolite, or a simple Ferrite.-This mineral the author shows to be an alteration-product mineral. of either augite or olivine.NINERALOOlCAL CHEMISTRY. 151 Craigtonite is the name given by the a,uthor to a substance occuibring as a thin coating which adheres to red granite at Craigton, Aberdeen- shire.Its colour is blue-black. The substance was dissolved off the granite by dilute hydrochloric acid, and gave on analysis the following results :- Al,O,. Fe,O,. MnO. MgO. K,O. Na@. Total. 32.20 38.30 7.46 16-61 4.74 0.68 9999 Ellonite is the ad interim name given to a pale, dull, unctuous powder which occurs in small nests in gneiss at Ellon in Aberdeen- shire. Tile associated minerals were orthoclase and lepidomelane. Analysis gave- SiO,. A1,0,. Fe203. Fe3. MnO. CaO. MgO. 62-00 3.05 1.67 1.46 0.69 1-29 15.61 K@. Ka,O. H,O. Total. 0% 0.79 11.70 99.89 At 100" it loses 6.365 per cent. of water. The powder may possibly be of the nature of ciniolite or sepiolite. Fibrous Bisilicate from Nelson Co, Virginia.By L. G. PATTERSON (Anzer. Chenz. J., 7, 180) -- Wedge-shaped, fibrous, massive olive-green to dark-green layers, interpenetrating epidote rocks. Hardness 4 ; sp. gi;. 3.153. Microscopically examined, it appears quite fresh. Analysis gave- B. H. B. SiO,. AI,O,. Fe20,. FeO. MnO. CaO. MgO. K,O. 51.00 3.05 4-35 12.83 0.60 11.20 14.24 0.27 Na,O. H20. 0.73 2.00 = 100.27 H. B. Trachytes of the Eperies-Tokay Mountains. By S. ROTH (Jalzrb. f. Min., 1885, 2, Bef., 280--281).-The eruptive rocks of the northern portion of the Eperies-Tokay mountains are described partly as amphibole-trachytes, partly as augite-trachytes, and are divided into four geographical groups. The composition and structure of the amphibole-trachytes are normal ; plagioclase (andesine and oligoclase) , brown opaque or transparent, green crystals of hornblende, augite, magnetite, and apatite being constituents. Three analyses of amphibole-trachjte are given: I, from the Fintaer Straz; 11, from the valley south of Krivi and Jaror; 111, from the road leading to Klauzura.The augite-trachytes correspond in composition and structure with t,he normal augite-andesites. Two analyses are given : IV, from the Sosujfaluer mountain; V, from Uubnik. To this type belongs the mother-rock of the Dubnik opals. k 2132 ABSTRACTS OF CHEXllCAL PAPERS. 55-80 5'22 t,raoe 10-80 20.00 --- Si02 ................ CaO.. .............. MgO ............... FepO,. ............... K,O ............ A1203.. ............. Na& .............. P20, ............... H,O.. .............---- 58-20 4 *50 trace 8 *60 21-40 _ _ _ _ ~ ~ I. -- 60 *70 1 *92 1.20 '9.20 I9 *70 4 *53 2.40 'trace 0.99 -- 60 -17 3 -55 trace 10.20 17.40 4.64 4.20 0 -43 trace -- 59-80 4 -30 trace 7'10 18 -30 3.50 4 '47 1 -85 trace -- IT. 1 v. Totals .............. 1 100.64 1 100.59 1 99.32 1 100.60 1 100.34 B. H. B. Application of Thermochemistry to Geology : Zinc. By DIEULAFAIT (Comp't. rend., 101, 842-845) .-It irj well known that the carbonate and sulphide are 'by far the most dbundant naturally occurring compounds af zinc. Zinc carbonate is formed from the monoxide with development of heat, and no oxide higher than the monoxide is known; hence, when the zinc has been converted into carbonate it is in its state of most stable equilibrium, and the car- bonate does not undergo oxidation like the corresponding compounds of iron and manganese.Natural deposits of zinc carbonate are almost always associated with dolomitic rocks. Many metals, including zinc, which are now found in the form of carbonates, originally existed as sulphides. The zinc sulphide has been oxidised to the soluble sulphate, and this in course of time has been brought into contact with water holding in solution either calcium or magnesium carbonate, or both. Con- sideration of the following thermochemical data- ZnO-+ SO, develops 11.7 cal. CaO+COz ,, 9.9 ?, CaO+SO, ,, 15.8 ,, 21.5 ,, 21.3 ,, ZnO + CO, develops 5-5 cal. --_- - ZnO + SO3 develops 11.7 ,, ZnO+ GO2 develops 5.5 ,, M@+COz 7 3 9.0 3, MgO+SO, ,, 15.6 ,, - -- 20.7 ,, 21.1 ,, shows that with zinc sulphate and calcium carbonate the first system corresponds with the greatest development of heat, and hence will be formed in preference, or, in other words, the zinc will remain as sulphate ; but in the case of zinc sulphate and magnesium carbonate the second system has the greatest heat of formation, and con- sequently the zinc sulphate will be converted into carbonate with simultaneous formation of magnesium sulphate.The salts of zinc art. isomorphous with the corresponding salts of magnesium, and unite with them to form double compounds, hence when magnesium car-NlNERXLOGICAL CIIENISTRY. 133 bonate is deposited, any zinc carbonate existing in the same solution will also separate out. This conclusion agrees with the results of the author’s previous researches on the formation of zinciferous dolomites i n ancient seas. The various natural forms of zinc carbonabe may be grouped under three heads, namely, that associaked with and disseminated throughout dolomitic rocks, which is the most abundant form ; that existing in beds and strings contemporaneous with the rocks in which they are found ; and that which is found in fissures and caverns.in dolomitic rocks, and has been extracted from these rocks by some agency similar to that which has caused the formation of the deposits of calcium phospha,te in the south-east of France. Most probably all the zino carbonah now found, originally existed in solution in water together with the oonstituents of dolomite, and i t is therefore contemporaneous with the dolomitic rocks in which it occurs.The isolation of the zinc carbonate in masses is the result of subsequent secondary changes. The Meteoric Iron of Santa Rosa, Colombia, 1810. By A, v. LASA4ULX (Jahrb.f. Min., 1885, 2, Ref., 269--270).-The author has examined a fragment of the meteoric iron from Santa Rosa in Colombia, which Stiibel himself broke off from the large, block that lies in the market place of Santa Rosa. It, is stated by Boussingault to have been found in 1810 at Tocavita. The block is, according to Stiibel, 0.7 metre long, 0.6 broad, and 0.5 high, and weighs 75 kilos. The analysis gave 91-48 per cent. of iron and 8.20 per cent. of nickel, with some cobalt, 0.38 silicates, and traces of copper, aarbon, phos- phorus, and schreibersite, This analysis agrees with. the analyses of the RasgatB iron, so the meteorites of Santa Rosa and RasgatA evidently fell at the same time.Olivine and colourless splinters of another silicate were observed, but the colourless grains. stated by Wohler to occur in the RasgatA iron, were absent. C. H. B. B. H. B. The Bingera Meteorite.. By A. LIVERSIDGE (J. R. XOC. New South Wales, 16, 35-36; Juhrh f. &tin., 1865, 2, Ref., 271).-The meteorite, a meteoric iron, was found by some gold-miners at Bingern. It is pear-shaped, 2 inches long, and 1; inch thick a t the thicker end, inch at the thinner. !The total weight is 240.735 grams, the sp. gr. being 7.834 to 7.849. The surface is covened with a, black, fused skin of magnetic oxide of iron. The skin is hard, brittle, and laminated. In places it is marked with sharply defined cracks, clearly the outlines of the Widmanstattian figures. The mass has well-marked palarity, the thin end being the south4eeking pole.. On analysis, the following results were obtained :- C.Insol. in HC1. Fe. . Ni. Go. B. Total. 0.137 0.553 93762 4.391 0.668 0.195 99-iOS B. Ix. B. Meteorites in the Public Collections of Mexico. By .G. VOM RATH (Jahrb. f. >!fin.., 1885, 2, Ref., 270).--The following meteorites are described :--From the National Museum : an iron mass a134 ABSTRACTS OF CHEMICAL PAPERS. cubic foot in size from Xiquipilco, Toluca Valley, which has remained unaltered, whilst similar irons in Enrope exfoliate ; an iron meteorite of nearly the same siee from the Hacienda Cacaria, 42 kilometres north of Durango ; a meteorite, 421 lbs.in weight, from Yanhuitlan, Oaxaca, with 6-21 per cent. of nickel and 0.27 per cent. cobalt. From the XchooE of Mines: a chondrite which fell 33 kilometres east of Dolores Hidalgo, Guanaxnato, and an iron meteorite from Santa Rosa, in the east of Coahuila. ,From the Guanaxuato College: a maqnificent,, crystalline-granular chondrite, 399 grams in weight, which fell on June 11, 1878, -between 11 and 12 A.M., at La Charca, 8 kilometres from Irapuata. The Deniliquin or Barratta Meteorite. By A. LIVERSTDGE ( J . R. SOC. New Xouth Wales, 16, 31-34; Jcrlzrb. f. Min., 1885, 2, Ref., 270-271).-A preliminary notice of this meteorite was pub- lished in 1872. It is a siderolite, and eonsists of varions silicates and nickeliferous iron. Externally it is covered with a blackish, fused skin, the external portions to the depth of an inch being distinctly laminated.The strudure is chondritic, most of the grains varying i n size from ilK to # inch in diameter. Under the microscope they are seen to have an imperfectly crystalline structure. The meteorite is essentially a mixture of enstatite and a mineral resembling olivine, with small quantities #of other .silicates. The percentage of nickel- iron amounts to 3.93. The sp. gr. of the laminated cruet is 3.382, and that of the interior 3.Fi03; the sp. gr. of the whole mass, weighing 145 lbs., was found to be 3.387. After prolonged digestion in con- centrated hydrochloric acid, 47.47 per cent. of the meteorite dissolved. The analysis gave the following results :- B. H. B.Si02. Cu. Fe. Fe,O,. A1,03. Ni. MnO. CaO. MgO. 40.28 0.18 1496 3-93 1-84 %*22 0-73 1-40 23.73 K,O. Na,O. S. P. Cr,Co, C. 0. 1-02 0.99 2.29 0.61 traces [3*78] The analysis af the metallic portion, separated by means of a fine sieve, gave the following results :- Si02. Fe. Ni. co. P. 0. S. 6.61 79.85 7.34 0.43 024 5.21 trace A second portion from a different part of the meteorite gave- Fe. Ni + Co. S O 2 . Total. 91-25 2 - 2 0 1-55 100*00 Daubr6e provisionally dlasses *this meteorite with those of Tadjera, Orvinio, and Koursk. B. €3. B. Proportion of Bromine in Sea-water. Ry E. BEIGLUKD (Ber., 18, 2888--2890).-Former determinations of the relative pro- portion of bromine to chlorine in sea-water are very variable. By nieans of an improred method for the estimation of bromine in theORGAXIC CHEXISTRP. 135 presence of chlorine, the author has made a series of determinations of milligrams of bromine to 100 grams of chlorine, and of the propor- tion of chlorine in grams per litre in sea-water from various sources.The mean results are approximately equal to those obtained by Dittmar (Report of Voyage of " Challenger "), namely, 340 mgrms. of bromine to 100 gmms chlorine, and 19.5 grams chlorine per litre. V. H. V.ORGAXIC CHEXISTRP. 135 presence of chlorine, the author has made a series of determinations of milligrams of bromine to 100 grams of chlorine, and of the propor- tion of chlorine in grams per litre in sea-water from various sources. The mean results are approximately equal to those obtained by Dittmar (Report of Voyage of " Challenger "), namely, 340 mgrms.of bromine to 100 gmms chlorine, and 19.5 grams chlorine per litre. V. H. V. MISERALOGICAL CHEMISTRY. M i n e r a 1 o g i c a 1 C h e m i s t ry. 125 Occurrence of Millerite in St.. Louis. By V. LEOKHARD (Jahrb. f. MirL., 1885, 2, Ref., 403).-Millerite occurs in large quanti- ties in St. Louis, in cavities 1 inch to 1 foot in diameter, in car- boniEerous limestone. In these cavities, the following minerals occur :-Calcite, dolomite, fluorspar, blende, millerite, anhydrite, gypsum, heavy-spar, strontianite, and pyrites. The latter minerals are formed later than the millerite. The millerite occurs in various forms : long, thin needles being the purest. These crystals are 6 inches long, 0.03 to 0.05 mm. thick, very elastic, with metallic lustre, and brass-yellow colour.They are hexagonal prisms with rhombohedra1 termination. The analjses gaw on an average 64.45 per cent. of nickel, and 35.55 pel. cent. of sulphur, with some iron (0-8 to 2.65 per cent.). The sp. gr. of the mineral is 5.028. B. H. B.126 ABSTRACTS OF CHEMICAL PAPERS. Emplectite from RBzbanya. By J. -4. KRENBER (Juhrb. f. &fin., 1885, 2, Ref., 263-264).-The mineral from Rbzbhnya, described by Peters as bismuthine, is emplectite. An analysis gave the following results :- S. Te. Bi. Cu. Ag. Pb. Fe. Total. 18.61 0.16 63.20 16.84 0.20 1.14 0.11 100.26 corresponding with the formula Cua8,BiaSa. shown by the author to be wollastonite. The accompanying mineral, described by Peters as tremolite, is B.H. B. Zircon and Titanium Minerals. By H. TH~~RACH (Jahrb. f. Min., 1885, 2, Ref., 396-401) .-In conducting an investigation of the rocks of the Spessart, and their alteration products, the author found zircon and titanium minerals in many of the rocks. He has since extended his researches to the rocks of other districts, and the results of his investigations may be summarised as follows :- Microscopic zircon is rarely absent in the ArchEan and sedimentary rocks. It also occurs in very many eruptive rocks. Its wide distri- bution in basalts and dolerites was hitherto unknown. Rutile is also contained in almost all ArchEau and sedimentary rocks, and in the de'bris from granites, porphyries, diabases, basalts, and dolerites. Microscopic annstase is widely distributed in decomposed crystalline and sedimentary rocks, and, in these, occurs principally in two types, one formed by the primary pyramid and the basal plane, and developed in a tabular or pyramidal manner; whilst the other is formed by an obtuse pyramid of the second order and the basal plane, pyesenting crystals of a lenticular character.Microscopic brookite is distributed in the same way as anatnse, and appears in thin or thick tablets with the rnacrodi3gonals predominaJing, and "showing the subordinate planes mP, Y2, 2Pm, OP, &P, iPm, and WPW. Anatase and brookite never occur in unaltered crystalline rocks, but only when the rock weathers. In the sedimentary rocks, they are partially of recent formation, partially derived from secondary deposits. Pseudo-brookite occurs in the alkered basalt and phonolite of the Kreuzberg, and has been formed during the weathering of the rock.Of a,ll the minerals occurring in the sedimentary rocks, staurolite deserves special attention as evidence of the derivation of these rocks from the various ArchEan rocks. (Compare Sandberger, this vol., p. 24.) B. H. B. Minerals from Switzerland. By G. SELIGMANN (Jahrb. f. Mi.., 1885, 2, Ref., 240--242).-The author describes the following minei:als :-Brookite from the Maderana Thal ; milarite and turnerite from the Strim Glacier; danburite crystals from the Scopi; topaz, resuvian and diopside from the P i z Rondadura; iron glance and phenacite from the Rachi Thal. A new occurrence of iron glance, OR, mP2, mP, $P2, R, r i t h adularia, calcite, and quartz, occasionally in very fine twin crystals, is described, from the Gorpibaoh, a tributary of the Rh6ne.B. €1. B.MINERALOGICAL CHEMISTRY. 127 Richellite. By G. CESBRO (Jahrb. f. K n . , 1885, 2, Ref., 260).- The results of the analyses are : (I) for compact richellite; (11) for laminated richellite :- Hygroscopic H,O. HzO. HF. P,O,. Fe,O,. CaO. Also,. Total. I. 6-90 25.64 1.22 27.23 29.63 6-18 2-82 99.62 11. 9.47 23.63 0-96 25549 29.67 7.19 3-64 100.05 corresponding with the formula : 4Fe,(PO,), + Fez03,2H% + 36H20. Richellite is amorphous. (comp. Abstr., 1884, 1102). It is found in the neighbourhood of Vise B. H. B. Optical Properties of Berzeliite. By BERTRAKD (Jahrb. f. Min., 1885, 2, Ref., 246-247).-The author has determined the optical properties of the Ferzeliite, recently discovered by Igelstriim (this vol., p.25) in Nordmark. An examination of the Lingban berzeliite conducted a t the same time showed that the two minerals differ considerably. The berzeliite from Lhgban, which occurs in large fragments, exhibits, on the same specimen, points with single and double refraction ; but the double refraction is indistinct, and in con- vergent light the interference figures cannot be detected. The berzeliite from Nordmark, which occurs almost without exception in round grains wit,hout crystal planes, always exhibits distinct double refraction of a very constant character. It is biaxial: 2E = 140". The bisectrix is positive ; p is less than v. As also no dispersion of t'he axes of elasticity was observed, the author is inclined to regard the Nordmark berzeliite as belonging to the rhombic system.B. H. R. Beryl from Amelia, Co., Virginia. By R. W. BAKER (Amer. Chem. J., 7, 175--176).-The sample from Amelia Court House was transparent and of a rich honey-yellow colour; there were many microscopical fluid cavities. Analysis gave- SiO,. Al,O,. Fe,O,. BeO. CaO. Na,O. H,O. 65.24 17.05 2-20 12.64 0.57 0.68 2.70 = 101.08. constituents of beryl. H. B. The author holds that both water and alkalis are probably normal Allanite from Nelson Co., Virginia. By C. MEMMINGER (Amer. Chem. J., 7, 177--178).-The mineral occurs in rounded masses, covered with a thin yellowish-white coating. Lustre resinous ; hard- ness 6 ; sp. gr. 3.59. SiO,. SnO,. A1,0,. Ce,O,. Di,O,. L%O,. FezO,.FeO. CaO. 30.04 0.17 16.10 11.61 5.39 4.11 5-06 9.89 13.02 1.11 0.28 0.02 2.56 = 99.36 Analysis gave :- MgO. N%O. K20. HsO. H. B.128 ABSTRACTS OF CHEMICAL PAPERS. A Decomposition Product of Allanite : a Variety of Kaolinite from Nelson Go., Virginia. By E. P. VALEN'I'INE.-This brown, soft substance is produced by the weathering of the allanite described in the preceding Abstract. Analyses gave- SiO,. A1203. Fe,03. Ce203. La203. Di203. MgO. K20. I. 18.66 23.28 34.48 1.30 3.27' 0.65 C.29 0.20 TI. 21.37 20.66 12.24 21.90 - - - -- Na,O. BeO. HzO. I. 0.43 - 17.16 = 99.72 11. - 1.95 21.37 = 99.49 H. B. Hornblende from St. Lawrence Co., New York. By G. IT. WILLIAMS (Jahrb. f. illin., 1685, 2, Mem., 175--176).-The author has made a series of crystallographic observations on the green horn- blende (pargasite) occurring a t East 'Russel, St.Lawrence Co. The results are of interest on account'of the discovery of two new planes : mP3 and mP?. The following, forms were observed on several crystals: PA, m ~ f , m ~ i , W P ~ , m ~ , WP?, W P ~ , m ~ e . B. H. B. Amphibole-Anthophyllite from Baltimore. I3y G. H. WILLIAMS fJtchrb. f. &Fir&., 1885, 2, Mem., 176-177):The author describes an interestling occurrence of amphibole-anthophyllite, near Baltimore, which is perfectly similar to that described by Des Cloizeaux from Greenland and Norway. An analysis shows that the mineral is a typical anthophyllite ; and from the optical examination there can be no doubt that it belongs to the monoclinic system. Krokydolite and Arfvedsonite.By A. RENNGOTT (Jahrb. f. Min., 1885, 2, Mern., 163-167) .-From a comparison of the published analyses of krokydolite and afvedsonite, the author concludes that krokydolite must be regarded as a fibrous rariety of arfvedsonite. An analysis of the krokydolite associated with nrfvedsonite in the zircon-syenite of Stavern in South Norway, would be of great value towards determining the relation between the two minerals. B. H. B. B. H. B. Alteration of Labradorite intb an Albite and a Zeolitic Mineral. By KLOOS (Jahrb. f. Min., 1885, 2, Ref., 412-413).- I n a rock from the Black Forest, consisting of plagioclase (labradorite), diallage, and hornblende, the author observed a gradual transition of the unaltered labradorite (Analysis 1) into EL dull, milk-white, opaque mass, which was found under the microscope to consist of' two minerals, a striated felspar and a finely granular mineral.The second mineral WRS soluble in dilute hydrochloric acid. 11 and 111 are analyses of the mixture, IV and V the plagioclase, and V the soluble, finely granular rniueral.MIn’ERALOCIICAL CHEMISTRY. 129 SO,. A1,0,. CaO. MgO. N,O. KzO. HzO. I. 51.53 31.41 13.00 -- 3.49 0.57 - 11. 61.64 22.47 4-98 - 8.03 0.60 3.19 In. 58-02 24-00 7-4s 0.25 6.43 0.44 3-11 IV. 64.87 21.54 2.28 - 8.78 1*:33 - V. 68.61 20.36 1.55 - 8.88 0.58 - VI. 42.73 27.55 16.40 - 0.83 0.10 12.39 The newly formed plngioclase represents a mixture of 1 mol. nnorthite and 8 mols. albite (IV), or 1 mol. anorthite and 10 mols. albite (V). The second mineral appears to be a zeolite with the molecular proportion of Na,O : CaO : A1,03 : SiO, : HzO = 1 : 21 : 19 : 51 : 49.This constitution is approximately that of scolezite. B. H. B. Alteration-pseudomorphs of Scapolite after Garnet. By A. CATHREIN (Jalzrb. f. Min., 1885, 2, 251).-Near the Castle of Achen- rain, the author found an altered garnet contained in a fragment of amphibolite. The microscopic examination, the measurements of a pyramid 3P3, and the chemical analysis, indicate that the specimen is an alteration-product which resembles many scapolites, notably passauite. The analysis, it is true, was incomplete, as soda, potash, and chlorine were estimated by difference. The comparison of the analytical results with the theoretical composition of a mixture of 45 per cent. meionite silicate and 55 per cent.marialite silicate is fairly satisfactory, and the other observations clearly indicate that the white mineral surrounding the garnet-interior is scnpolite. Epidote and labradorite appear as bye-products of the alteratiok. B. H. B. The Branchville Mica. By C. RAMMELSBERQ ( h h r b . f. Min., 1885, 2, Mem., 225-22S).-G. vom R,ath presented the author with a large specimen of mica from Branchville, Connecticut. The specimen consists of grey, translucent mica (I), traversed in the middle by a broad layer of dark-brown mica (11). Analysis gave the following results :- F. SiO,. A1,0,. Fe203. FeO. K20. Na20. I. 0.93 44.19 32.69 4.75 3.90 8-00 0-59 11. 2-43 40.14 23-43 7.65 11-87 9-64 1.13 Li20. H20. Total. Sp. gr. I. 0.21 3.85 99.11 2.898 TI.1-18 2.64 100.11 3.030 Both micas appear to be new varieties of pure iron mica, their formulw being- I. R’,,FeZk7Si,,056. 11. R’,Be2J&Si90s. B. H. B. Chloritoid containing Manganese. By E. PRosr (Jahrb. f. VOL. L. k ,Min., 1885, 2, Ref., 259).-This mineral, the salmite of Dnmont,130 ABSTkACTS OF CHEMICAL PAPERS. occurs in the quartz veins which traverse the phyllnde snlmien of Vielsalm. It forms irregular masses with a finely granular texture, and greyish-green colour. The mineral fuses with diEculty to a black enamel, and is imperfectly soluble in hydrochloric acid. H. = 5 to 6 ; sp. gr. 3-38, The analysis gave the following results :- Quartz. SiO,. A1203. Fe203. PeO. MnO. COO. MgO. 15-06 19.14 33.66 3.38 13.05 7-14! 0.04 1.79 CaO. H20. Total. 0.30 6-32 99.88 This corresponds with the formula- B.H. B. Chlorite from Albemarle Co., Virginia. By M. BIND (Anzer. Chem. J., 7, 181).--Olive-green, pearly scales ; hardness 2.5 ; sp. gr. 3.05. Under the microscope, a small amount of hydrated ferric oxide is seen between the lamina Analysis gave- SiO,. Al,O,. %e20,. FeO. MnO. CaO. MgO. H20. 23.52 22-35 1-92 28.78 0.32 0.39 10.70 11.28 = 99.35 Some Ill-determined Minerals. By HEDDLE (Bin. Hug., 5, 26-31 ; Jahrb. f. Min., 1885, 2, Ref., 260-262).-The followiiig substances are described as ill-determined or doubtful species :- PZynthite.-From Quiraing in Skye. It occurs in layers 1 to 2 inches thick in amy gdaloid. Colonr deep red, lustre greasy, sometimes earthy and dull. It falls to pieces in water, and may thus be dis- tinguished from the accompanying massive mesolite.Its composition was found to be as follows :- H. B. SiO,. A120,. Pe203. FeO. MnO. CaO. H20. Total. 29.54 19-02 28.01 3.25 0.84 2-23 17.39 100.28 A t 100" it loses 6.687 per cent. of moisture. At the Storr, in Skye, it occurs in a repeated series of beds. Ui;gite.-The mineral, for which the name uigite is proposed, was found at Uig, 16 miles north of Portree, in Skye, with faroelite and analcime. It occurs indistinctly crystallised in small nests in the amygdaloid. In general appearance, it is intermediate between faroelite and gyrolite. Sp. gr. 2.284. Analyses gave the following results :- It, is evidently merely bole. SiO,. A1203. CaO. ?Ja20. H20. Total. I. 46.32 21.35 16.36 4.69 12.21 100.93 11. 45.98 21-93 16-15 4-68 11.25 99.99 Uigite is thus either a mixture of faroelite and gyrolite, or a simple Ferrite.-This mineral the author shows to be an alteration-product mineral.of either augite or olivine.NINERALOOlCAL CHEMISTRY. 151 Craigtonite is the name given by the a,uthor to a substance occuibring as a thin coating which adheres to red granite at Craigton, Aberdeen- shire. Its colour is blue-black. The substance was dissolved off the granite by dilute hydrochloric acid, and gave on analysis the following results :- Al,O,. Fe,O,. MnO. MgO. K,O. Na@. Total. 32.20 38.30 7.46 16-61 4.74 0.68 9999 Ellonite is the ad interim name given to a pale, dull, unctuous powder which occurs in small nests in gneiss at Ellon in Aberdeen- shire. Tile associated minerals were orthoclase and lepidomelane.Analysis gave- SiO,. A1,0,. Fe203. Fe3. MnO. CaO. MgO. 62-00 3.05 1.67 1.46 0.69 1-29 15.61 K@. Ka,O. H,O. Total. 0% 0.79 11.70 99.89 At 100" it loses 6.365 per cent. of water. The powder may possibly be of the nature of ciniolite or sepiolite. Fibrous Bisilicate from Nelson Co, Virginia. By L. G. PATTERSON (Anzer. Chenz. J., 7, 180) -- Wedge-shaped, fibrous, massive olive-green to dark-green layers, interpenetrating epidote rocks. Hardness 4 ; sp. gi;. 3.153. Microscopically examined, it appears quite fresh. Analysis gave- B. H. B. SiO,. AI,O,. Fe20,. FeO. MnO. CaO. MgO. K,O. 51.00 3.05 4-35 12.83 0.60 11.20 14.24 0.27 Na,O. H20. 0.73 2.00 = 100.27 H. B. Trachytes of the Eperies-Tokay Mountains. By S. ROTH (Jalzrb. f. Min., 1885, 2, Bef., 280--281).-The eruptive rocks of the northern portion of the Eperies-Tokay mountains are described partly as amphibole-trachytes, partly as augite-trachytes, and are divided into four geographical groups.The composition and structure of the amphibole-trachytes are normal ; plagioclase (andesine and oligoclase) , brown opaque or transparent, green crystals of hornblende, augite, magnetite, and apatite being constituents. Three analyses of amphibole-trachjte are given: I, from the Fintaer Straz; 11, from the valley south of Krivi and Jaror; 111, from the road leading to Klauzura. The augite-trachytes correspond in composition and structure with t,he normal augite-andesites. Two analyses are given : IV, from the Sosujfaluer mountain; V, from Uubnik. To this type belongs the mother-rock of the Dubnik opals.k 2132 ABSTRACTS OF CHEXllCAL PAPERS. 55-80 5'22 t,raoe 10-80 20.00 --- Si02 ................ CaO.. .............. MgO ............... FepO,. ............... K,O ............ A1203.. ............. Na& .............. P20, ............... H,O.. ............. ---- 58-20 4 *50 trace 8 *60 21-40 _ _ _ _ ~ ~ I. -- 60 *70 1 *92 1.20 '9.20 I9 *70 4 *53 2.40 'trace 0.99 -- 60 -17 3 -55 trace 10.20 17.40 4.64 4.20 0 -43 trace -- 59-80 4 -30 trace 7'10 18 -30 3.50 4 '47 1 -85 trace -- IT. 1 v. Totals .............. 1 100.64 1 100.59 1 99.32 1 100.60 1 100.34 B. H. B. Application of Thermochemistry to Geology : Zinc. By DIEULAFAIT (Comp't. rend., 101, 842-845) .-It irj well known that the carbonate and sulphide are 'by far the most dbundant naturally occurring compounds af zinc.Zinc carbonate is formed from the monoxide with development of heat, and no oxide higher than the monoxide is known; hence, when the zinc has been converted into carbonate it is in its state of most stable equilibrium, and the car- bonate does not undergo oxidation like the corresponding compounds of iron and manganese. Natural deposits of zinc carbonate are almost always associated with dolomitic rocks. Many metals, including zinc, which are now found in the form of carbonates, originally existed as sulphides. The zinc sulphide has been oxidised to the soluble sulphate, and this in course of time has been brought into contact with water holding in solution either calcium or magnesium carbonate, or both.Con- sideration of the following thermochemical data- ZnO-+ SO, develops 11.7 cal. CaO+COz ,, 9.9 ?, CaO+SO, ,, 15.8 ,, 21.5 ,, 21.3 ,, ZnO + CO, develops 5-5 cal. --_- - ZnO + SO3 develops 11.7 ,, ZnO+ GO2 develops 5.5 ,, M@+COz 7 3 9.0 3, MgO+SO, ,, 15.6 ,, - -- 20.7 ,, 21.1 ,, shows that with zinc sulphate and calcium carbonate the first system corresponds with the greatest development of heat, and hence will be formed in preference, or, in other words, the zinc will remain as sulphate ; but in the case of zinc sulphate and magnesium carbonate the second system has the greatest heat of formation, and con- sequently the zinc sulphate will be converted into carbonate with simultaneous formation of magnesium sulphate. The salts of zinc art. isomorphous with the corresponding salts of magnesium, and unite with them to form double compounds, hence when magnesium car-NlNERXLOGICAL CIIENISTRY.133 bonate is deposited, any zinc carbonate existing in the same solution will also separate out. This conclusion agrees with the results of the author’s previous researches on the formation of zinciferous dolomites i n ancient seas. The various natural forms of zinc carbonabe may be grouped under three heads, namely, that associaked with and disseminated throughout dolomitic rocks, which is the most abundant form ; that existing in beds and strings contemporaneous with the rocks in which they are found ; and that which is found in fissures and caverns. in dolomitic rocks, and has been extracted from these rocks by some agency similar to that which has caused the formation of the deposits of calcium phospha,te in the south-east of France.Most probably all the zino carbonah now found, originally existed in solution in water together with the oonstituents of dolomite, and i t is therefore contemporaneous with the dolomitic rocks in which it occurs. The isolation of the zinc carbonate in masses is the result of subsequent secondary changes. The Meteoric Iron of Santa Rosa, Colombia, 1810. By A, v. LASA4ULX (Jahrb.f. Min., 1885, 2, Ref., 269--270).-The author has examined a fragment of the meteoric iron from Santa Rosa in Colombia, which Stiibel himself broke off from the large, block that lies in the market place of Santa Rosa. It, is stated by Boussingault to have been found in 1810 at Tocavita.The block is, according to Stiibel, 0.7 metre long, 0.6 broad, and 0.5 high, and weighs 75 kilos. The analysis gave 91-48 per cent. of iron and 8.20 per cent. of nickel, with some cobalt, 0.38 silicates, and traces of copper, aarbon, phos- phorus, and schreibersite, This analysis agrees with. the analyses of the RasgatB iron, so the meteorites of Santa Rosa and RasgatA evidently fell at the same time. Olivine and colourless splinters of another silicate were observed, but the colourless grains. stated by Wohler to occur in the RasgatA iron, were absent. C. H. B. B. H. B. The Bingera Meteorite.. By A. LIVERSIDGE (J. R. XOC. New South Wales, 16, 35-36; Juhrh f. &tin., 1865, 2, Ref., 271).-The meteorite, a meteoric iron, was found by some gold-miners at Bingern.It is pear-shaped, 2 inches long, and 1; inch thick a t the thicker end, inch at the thinner. !The total weight is 240.735 grams, the sp. gr. being 7.834 to 7.849. The surface is covened with a, black, fused skin of magnetic oxide of iron. The skin is hard, brittle, and laminated. In places it is marked with sharply defined cracks, clearly the outlines of the Widmanstattian figures. The mass has well-marked palarity, the thin end being the south4eeking pole.. On analysis, the following results were obtained :- C. Insol. in HC1. Fe. . Ni. Go. B. Total. 0.137 0.553 93762 4.391 0.668 0.195 99-iOS B. Ix. B. Meteorites in the Public Collections of Mexico. By .G. VOM RATH (Jahrb. f. >!fin.., 1885, 2, Ref., 270).--The following meteorites are described :--From the National Museum : an iron mass a134 ABSTRACTS OF CHEMICAL PAPERS.cubic foot in size from Xiquipilco, Toluca Valley, which has remained unaltered, whilst similar irons in Enrope exfoliate ; an iron meteorite of nearly the same siee from the Hacienda Cacaria, 42 kilometres north of Durango ; a meteorite, 421 lbs. in weight, from Yanhuitlan, Oaxaca, with 6-21 per cent. of nickel and 0.27 per cent. cobalt. From the XchooE of Mines: a chondrite which fell 33 kilometres east of Dolores Hidalgo, Guanaxnato, and an iron meteorite from Santa Rosa, in the east of Coahuila. ,From the Guanaxuato College: a maqnificent,, crystalline-granular chondrite, 399 grams in weight, which fell on June 11, 1878, -between 11 and 12 A.M., at La Charca, 8 kilometres from Irapuata.The Deniliquin or Barratta Meteorite. By A. LIVERSTDGE ( J . R. SOC. New Xouth Wales, 16, 31-34; Jcrlzrb. f. Min., 1885, 2, Ref., 270-271).-A preliminary notice of this meteorite was pub- lished in 1872. It is a siderolite, and eonsists of varions silicates and nickeliferous iron. Externally it is covered with a blackish, fused skin, the external portions to the depth of an inch being distinctly laminated. The strudure is chondritic, most of the grains varying i n size from ilK to # inch in diameter. Under the microscope they are seen to have an imperfectly crystalline structure. The meteorite is essentially a mixture of enstatite and a mineral resembling olivine, with small quantities #of other .silicates. The percentage of nickel- iron amounts to 3.93.The sp. gr. of the laminated cruet is 3.382, and that of the interior 3.Fi03; the sp. gr. of the whole mass, weighing 145 lbs., was found to be 3.387. After prolonged digestion in con- centrated hydrochloric acid, 47.47 per cent. of the meteorite dissolved. The analysis gave the following results :- B. H. B. Si02. Cu. Fe. Fe,O,. A1,03. Ni. MnO. CaO. MgO. 40.28 0.18 1496 3-93 1-84 %*22 0-73 1-40 23.73 K,O. Na,O. S. P. Cr,Co, C. 0. 1-02 0.99 2.29 0.61 traces [3*78] The analysis af the metallic portion, separated by means of a fine sieve, gave the following results :- Si02. Fe. Ni. co. P. 0. S. 6.61 79.85 7.34 0.43 024 5.21 trace A second portion from a different part of the meteorite gave- Fe. Ni + Co. S O 2 . Total. 91-25 2 - 2 0 1-55 100*00 Daubr6e provisionally dlasses *this meteorite with those of Tadjera, Orvinio, and Koursk.B. €3. B. Proportion of Bromine in Sea-water. Ry E. BEIGLUKD (Ber., 18, 2888--2890).-Former determinations of the relative pro- portion of bromine to chlorine in sea-water are very variable. By nieans of an improred method for the estimation of bromine in theORGAXIC CHEXISTRP. 135 presence of chlorine, the author has made a series of determinations of milligrams of bromine to 100 grams of chlorine, and of the propor- tion of chlorine in grams per litre in sea-water from various sources. The mean results are approximately equal to those obtained by Dittmar (Report of Voyage of " Challenger "), namely, 340 mgrms. of bromine to 100 gmms chlorine, and 19.5 grams chlorine per litre. V. H. V.MISERALOGICAL CHEMISTRY.M i n e r a 1 o g i c a 1 C h e m i s t ry.125Occurrence of Millerite in St..Louis. By V. LEOKHARD(Jahrb. f. MirL., 1885, 2, Ref., 403).-Millerite occurs in large quanti-ties in St. Louis, in cavities 1 inch to 1 foot in diameter, in car-boniEerous limestone. In these cavities, the following mineralsoccur :-Calcite, dolomite, fluorspar, blende, millerite, anhydrite,gypsum, heavy-spar, strontianite, and pyrites. The latter mineralsare formed later than the millerite.The millerite occurs in various forms : long, thin needles being thepurest. These crystals are 6 inches long, 0.03 to 0.05 mm. thick, veryelastic, with metallic lustre, and brass-yellow colour. They arehexagonal prisms with rhombohedra1 termination.The analjses gawon an average 64.45 per cent. of nickel, and 35.55 pel. cent. of sulphur,with some iron (0-8 to 2.65 per cent.). The sp. gr. of the mineralis 5.028. B. H. B126 ABSTRACTS OF CHEMICAL PAPERS.Emplectite from RBzbanya. By J. -4. KRENBER (Juhrb. f. &fin.,1885, 2, Ref., 263-264).-The mineral from Rbzbhnya, described byPeters as bismuthine, is emplectite. An analysis gave the followingresults :-S. Te. Bi. Cu. Ag. Pb. Fe. Total.18.61 0.16 63.20 16.84 0.20 1.14 0.11 100.26corresponding with the formula Cua8,BiaSa.shown by the author to be wollastonite.The accompanying mineral, described by Peters as tremolite, isB. H. B.Zircon and Titanium Minerals. By H. TH~~RACH (Jahrb. f.Min., 1885, 2, Ref., 396-401) .-In conducting an investigation ofthe rocks of the Spessart, and their alteration products, the authorfound zircon and titanium minerals in many of the rocks.He hassince extended his researches to the rocks of other districts, and theresults of his investigations may be summarised as follows :-Microscopic zircon is rarely absent in the ArchEan and sedimentaryrocks. It also occurs in very many eruptive rocks. Its wide distri-bution in basalts and dolerites was hitherto unknown. Rutile is alsocontained in almost all ArchEau and sedimentary rocks, and in thede'bris from granites, porphyries, diabases, basalts, and dolerites.Microscopic annstase is widely distributed in decomposed crystallineand sedimentary rocks, and, in these, occurs principally in two types,one formed by the primary pyramid and the basal plane, and developedin a tabular or pyramidal manner; whilst the other is formed by anobtuse pyramid of the second order and the basal plane, pyesentingcrystals of a lenticular character.Microscopic brookite is distributedin the same way as anatnse, and appears in thin or thick tablets withthe rnacrodi3gonals predominaJing, and "showing the subordinateplanes mP, Y2, 2Pm, OP, &P, iPm, and WPW. Anatase and brookitenever occur in unaltered crystalline rocks, but only when the rockweathers. In the sedimentary rocks, they are partially of recentformation, partially derived from secondary deposits. Pseudo-brookiteoccurs in the alkered basalt and phonolite of the Kreuzberg, and hasbeen formed during the weathering of the rock.Of a,ll the mineralsoccurring in the sedimentary rocks, staurolite deserves specialattention as evidence of the derivation of these rocks from thevarious ArchEan rocks. (Compare Sandberger, this vol., p. 24.)B. H. B.Minerals from Switzerland. By G. SELIGMANN (Jahrb. f. Mi..,1885, 2, Ref., 240--242).-The author describes the followingminei:als :-Brookite from the Maderana Thal ; milarite and turneritefrom the Strim Glacier; danburite crystals from the Scopi; topaz,resuvian and diopside from the P i z Rondadura; iron glance andphenacite from the Rachi Thal. A new occurrence of iron glance,OR, mP2, mP, $P2, R, r i t h adularia, calcite, and quartz, occasionallyin very fine twin crystals, is described, from the Gorpibaoh, a tributaryof the Rh6ne.B. €1. BMINERALOGICAL CHEMISTRY. 127Richellite. By G. CESBRO (Jahrb. f. K n . , 1885, 2, Ref., 260).-The results of the analyses are : (I) for compact richellite; (11) forlaminated richellite :-HygroscopicH,O. HzO. HF. P,O,. Fe,O,. CaO. Also,. Total.I. 6-90 25.64 1.22 27.23 29.63 6-18 2-82 99.6211. 9.47 23.63 0-96 25549 29.67 7.19 3-64 100.05corresponding with the formula :4Fe,(PO,), + Fez03,2H% + 36H20.Richellite is amorphous.(comp. Abstr., 1884, 1102).It is found in the neighbourhood of ViseB. H. B.Optical Properties of Berzeliite. By BERTRAKD (Jahrb. f. Min.,1885, 2, Ref., 246-247).-The author has determined the opticalproperties of the Ferzeliite, recently discovered by Igelstriim (thisvol., p.25) in Nordmark. An examination of the Lingban berzeliiteconducted a t the same time showed that the two minerals differconsiderably. The berzeliite from Lhgban, which occurs in largefragments, exhibits, on the same specimen, points with single anddouble refraction ; but the double refraction is indistinct, and in con-vergent light the interference figures cannot be detected. Theberzeliite from Nordmark, which occurs almost without exception inround grains wit,hout crystal planes, always exhibits distinct doublerefraction of a very constant character. It is biaxial: 2E = 140".The bisectrix is positive ; p is less than v. As also no dispersion oft'he axes of elasticity was observed, the author is inclined to regardthe Nordmark berzeliite as belonging to the rhombic system.B.H. R.Beryl from Amelia, Co., Virginia. By R. W. BAKER (Amer.Chem. J., 7, 175--176).-The sample from Amelia Court House wastransparent and of a rich honey-yellow colour; there were manymicroscopical fluid cavities. Analysis gave-SiO,. Al,O,. Fe,O,. BeO. CaO. Na,O. H,O.65.24 17.05 2-20 12.64 0.57 0.68 2.70 = 101.08.constituents of beryl. H. B.The author holds that both water and alkalis are probably normalAllanite from Nelson Co., Virginia. By C. MEMMINGER (Amer.Chem. J., 7, 177--178).-The mineral occurs in rounded masses,covered with a thin yellowish-white coating. Lustre resinous ; hard-ness 6 ; sp. gr. 3.59.SiO,. SnO,. A1,0,. Ce,O,. Di,O,. L%O,. FezO,. FeO. CaO.30.04 0.17 16.10 11.61 5.39 4.11 5-06 9.89 13.021.11 0.28 0.02 2.56 = 99.36Analysis gave :-MgO. N%O.K20. HsO.H. B128 ABSTRACTS OF CHEMICAL PAPERS.A Decomposition Product of Allanite : a Variety of Kaolinitefrom Nelson Go., Virginia. By E. P. VALEN'I'INE.-This brown,soft substance is produced by the weathering of the allanite describedin the preceding Abstract. Analyses gave-SiO,. A1203. Fe,03. Ce203. La203. Di203. MgO. K20.I. 18.66 23.28 34.48 1.30 3.27' 0.65 C.29 0.20TI. 21.37 20.66 12.24 21.90 - - - --Na,O. BeO. HzO.I. 0.43 - 17.16 = 99.7211. - 1.95 21.37 = 99.49 H. B.Hornblende from St. Lawrence Co., New York. By G. IT.WILLIAMS (Jahrb. f. illin., 1685, 2, Mem., 175--176).-The authorhas made a series of crystallographic observations on the green horn-blende (pargasite) occurring a t East 'Russel, St.Lawrence Co. Theresults are of interest on account'of the discovery of two new planes :mP3 and mP?. The following, forms were observed on severalcrystals: PA, m ~ f , m ~ i , W P ~ , m ~ , WP?, W P ~ , m ~ e .B. H. B.Amphibole-Anthophyllite from Baltimore. I3y G. H. WILLIAMSfJtchrb. f. &Fir&., 1885, 2, Mem., 176-177):The author describes aninterestling occurrence of amphibole-anthophyllite, near Baltimore,which is perfectly similar to that described by Des Cloizeaux fromGreenland and Norway. An analysis shows that the mineral is atypical anthophyllite ; and from the optical examination there can beno doubt that it belongs to the monoclinic system.Krokydolite and Arfvedsonite. By A.RENNGOTT (Jahrb. f. Min.,1885, 2, Mern., 163-167) .-From a comparison of the publishedanalyses of krokydolite and afvedsonite, the author concludes thatkrokydolite must be regarded as a fibrous rariety of arfvedsonite.An analysis of the krokydolite associated with nrfvedsonite in thezircon-syenite of Stavern in South Norway, would be of great valuetowards determining the relation between the two minerals.B. H. B.B. H. B.Alteration of Labradorite intb an Albite and a ZeoliticMineral. By KLOOS (Jahrb. f. Min., 1885, 2, Ref., 412-413).-I n a rock from the Black Forest, consisting of plagioclase (labradorite),diallage, and hornblende, the author observed a gradual transition ofthe unaltered labradorite (Analysis 1) into EL dull, milk-white, opaquemass, which was found under the microscope to consist of' twominerals, a striated felspar and a finely granular mineral.The secondmineral WRS soluble in dilute hydrochloric acid. 11 and 111 areanalyses of the mixture, IV and V the plagioclase, and V thesoluble, finely granular rniueralMIn’ERALOCIICAL CHEMISTRY. 129SO,. A1,0,. CaO. MgO. N,O. KzO. HzO.I. 51.53 31.41 13.00 -- 3.49 0.57 -11. 61.64 22.47 4-98 - 8.03 0.60 3.19In. 58-02 24-00 7-4s 0.25 6.43 0.44 3-11IV. 64.87 21.54 2.28 - 8.78 1*:33 -V. 68.61 20.36 1.55 - 8.88 0.58 -VI. 42.73 27.55 16.40 - 0.83 0.10 12.39The newly formed plngioclase represents a mixture of 1 mol.nnorthite and 8 mols. albite (IV), or 1 mol. anorthite and 10 mols.albite (V). The second mineral appears to be a zeolite with themolecular proportion ofNa,O : CaO : A1,03 : SiO, : HzO = 1 : 21 : 19 : 51 : 49.This constitution is approximately that of scolezite.B. H. B.Alteration-pseudomorphs of Scapolite after Garnet. By A.CATHREIN (Jalzrb. f. Min., 1885, 2, 251).-Near the Castle of Achen-rain, the author found an altered garnet contained in a fragment ofamphibolite. The microscopic examination, the measurements of apyramid 3P3, and the chemical analysis, indicate that the specimenis an alteration-product which resembles many scapolites, notablypassauite. The analysis, it is true, was incomplete, as soda, potash,and chlorine were estimated by difference. The comparison of theanalytical results with the theoretical composition of a mixture of45 per cent.meionite silicate and 55 per cent. marialite silicate isfairly satisfactory, and the other observations clearly indicate thatthe white mineral surrounding the garnet-interior is scnpolite.Epidote and labradorite appear as bye-products of the alteratiok.B. H. B.The Branchville Mica. By C. RAMMELSBERQ ( h h r b . f. Min.,1885, 2, Mem., 225-22S).-G. vom R,ath presented the author witha large specimen of mica from Branchville, Connecticut. Thespecimen consists of grey, translucent mica (I), traversed in themiddle by a broad layer of dark-brown mica (11). Analysis gave thefollowing results :-F. SiO,. A1,0,. Fe203. FeO. K20. Na20.I. 0.93 44.19 32.69 4.75 3.90 8-00 0-5911. 2-43 40.14 23-43 7.65 11-87 9-64 1.13Li20. H20.Total. Sp. gr.I. 0.21 3.85 99.11 2.898TI. 1-18 2.64 100.11 3.030Both micas appear to be new varieties of pure iron mica, theirformulw being-I. R’,,FeZk7Si,,056.11. R’,Be2J&Si90s. B. H. B.Chloritoid containing Manganese. By E. PRosr (Jahrb. f.VOL. L. k,Min., 1885, 2, Ref., 259).-This mineral, the salmite of Dnmont130 ABSTkACTS OF CHEMICAL PAPERS.occurs in the quartz veins which traverse the phyllnde snlmien ofVielsalm. It forms irregular masses with a finely granular texture,and greyish-green colour. The mineralfuses with diEculty to a black enamel, and is imperfectly soluble inhydrochloric acid.H. = 5 to 6 ; sp. gr. 3-38,The analysis gave the following results :-Quartz. SiO,. A1203. Fe203. PeO. MnO. COO. MgO.15-06 19.14 33.66 3.38 13.05 7-14! 0.04 1.79CaO.H20. Total.0.30 6-32 99.88This corresponds with the formula-B. H. B.Chlorite from Albemarle Co., Virginia. By M. BIND (Anzer.Chem. J., 7, 181).--Olive-green, pearly scales ; hardness 2.5 ; sp. gr.3.05. Under the microscope, a small amount of hydrated ferric oxideis seen between the lamina Analysis gave-SiO,. Al,O,. %e20,. FeO. MnO. CaO. MgO. H20.23.52 22-35 1-92 28.78 0.32 0.39 10.70 11.28 = 99.35Some Ill-determined Minerals. By HEDDLE (Bin. Hug., 5,26-31 ; Jahrb. f. Min., 1885, 2, Ref., 260-262).-The followiiigsubstances are described as ill-determined or doubtful species :-PZynthite.-From Quiraing in Skye. It occurs in layers 1 to 2inches thick in amy gdaloid. Colonr deep red, lustre greasy, sometimesearthy and dull.It falls to pieces in water, and may thus be dis-tinguished from the accompanying massive mesolite. Its compositionwas found to be as follows :-H. B.SiO,. A120,. Pe203. FeO. MnO. CaO. H20. Total.29.54 19-02 28.01 3.25 0.84 2-23 17.39 100.28A t 100" it loses 6.687 per cent. of moisture. At the Storr, in Skye,it occurs in a repeated series of beds.Ui;gite.-The mineral, for which the name uigite is proposed, wasfound at Uig, 16 miles north of Portree, in Skye, with faroelite andanalcime. It occurs indistinctly crystallised in small nests in theamygdaloid. In general appearance, it is intermediate betweenfaroelite and gyrolite. Sp. gr. 2.284. Analyses gave the followingresults :-It, is evidently merely bole.SiO,.A1203. CaO. ?Ja20. H20. Total.I. 46.32 21.35 16.36 4.69 12.21 100.9311. 45.98 21-93 16-15 4-68 11.25 99.99Uigite is thus either a mixture of faroelite and gyrolite, or a simpleFerrite.-This mineral the author shows to be an alteration-productmineral.of either augite or olivineNINERALOOlCAL CHEMISTRY. 151Craigtonite is the name given by the a,uthor to a substance occuibringas a thin coating which adheres to red granite at Craigton, Aberdeen-shire. Its colour is blue-black. The substance was dissolved off thegranite by dilute hydrochloric acid, and gave on analysis the followingresults :-Al,O,. Fe,O,. MnO. MgO. K,O. Na@. Total.32.20 38.30 7.46 16-61 4.74 0.68 9999Ellonite is the ad interim name given to a pale, dull, unctuouspowder which occurs in small nests in gneiss at Ellon in Aberdeen-shire. Tile associated minerals were orthoclase and lepidomelane.Analysis gave-SiO,. A1,0,.Fe203. Fe3. MnO. CaO. MgO.62-00 3.05 1.67 1.46 0.69 1-29 15.61K@. Ka,O. H,O. Total.0% 0.79 11.70 99.89At 100" it loses 6.365 per cent. of water. The powder may possiblybe of the nature of ciniolite or sepiolite.Fibrous Bisilicate from Nelson Co, Virginia. By L. G.PATTERSON (Anzer. Chenz. J., 7, 180) -- Wedge-shaped, fibrous, massiveolive-green to dark-green layers, interpenetrating epidote rocks.Hardness 4 ; sp. gi;. 3.153. Microscopically examined, it appearsquite fresh. Analysis gave-B. H. B.SiO,. AI,O,. Fe20,. FeO. MnO. CaO. MgO. K,O.51.00 3.05 4-35 12.83 0.60 11.20 14.24 0.27Na,O. H20.0.73 2.00 = 100.27 H.B.Trachytes of the Eperies-Tokay Mountains. By S. ROTH(Jalzrb. f. Min., 1885, 2, Bef., 280--281).-The eruptive rocks of thenorthern portion of the Eperies-Tokay mountains are described partlyas amphibole-trachytes, partly as augite-trachytes, and are dividedinto four geographical groups. The composition and structure of theamphibole-trachytes are normal ; plagioclase (andesine and oligoclase) ,brown opaque or transparent, green crystals of hornblende, augite,magnetite, and apatite being constituents. Three analyses ofamphibole-trachjte are given: I, from the Fintaer Straz; 11, fromthe valley south of Krivi and Jaror; 111, from the road leading toKlauzura.The augite-trachytes correspond in composition and structure witht,he normal augite-andesites.Two analyses are given : IV, from theSosujfaluer mountain; V, from Uubnik. To this type belongs themother-rock of the Dubnik opals.k 132 ABSTRACTS OF CHEXllCAL PAPERS.55-805'22t,raoe10-8020.00---Si02 ................CaO.. ..............MgO ...............FepO,. ...............K,O ............ A1203.. .............Na& ..............P20, ...............H,O.. ............. ----58-204 *50trace8 *6021-40_ _ _ _ ~ ~I.--60 *701 *921.20'9.20I9 *704 *532.40'trace0.99--60 -173 -55trace10.2017.404.644.200 -43trace--59-804 -30trace7'1018 -303.504 '471 -85trace--IT. 1 v.Totals .............. 1 100.64 1 100.59 1 99.32 1 100.60 1 100.34B.H. B.Application of Thermochemistry to Geology : Zinc. ByDIEULAFAIT (Comp't. rend., 101, 842-845) .-It irj well known that thecarbonate and sulphide are 'by far the most dbundant naturallyoccurring compounds af zinc. Zinc carbonate is formed from themonoxide with development of heat, and no oxide higher than themonoxide is known; hence, when the zinc has been converted intocarbonate it is in its state of most stable equilibrium, and the car-bonate does not undergo oxidation like the corresponding compoundsof iron and manganese.Natural deposits of zinc carbonate are almost always associatedwith dolomitic rocks. Many metals, including zinc, which are nowfound in the form of carbonates, originally existed as sulphides. Thezinc sulphide has been oxidised to the soluble sulphate, and this incourse of time has been brought into contact with water holdingin solution either calcium or magnesium carbonate, or both.Con-sideration of the following thermochemical data-ZnO-+ SO, develops 11.7 cal.CaO+COz ,, 9.9 ?, CaO+SO, ,, 15.8 ,,21.5 ,, 21.3 ,,ZnO + CO, develops 5-5 cal.--_- -ZnO + SO3 develops 11.7 ,, ZnO+ GO2 develops 5.5 ,,M@+COz 7 3 9.0 3, MgO+SO, ,, 15.6 ,, - --20.7 ,, 21.1 ,,shows that with zinc sulphate and calcium carbonate the first systemcorresponds with the greatest development of heat, and hence will beformed in preference, or, in other words, the zinc will remain assulphate ; but in the case of zinc sulphate and magnesium carbonatethe second system has the greatest heat of formation, and con-sequently the zinc sulphate will be converted into carbonate withsimultaneous formation of magnesium sulphate.The salts of zinc art.isomorphous with the corresponding salts of magnesium, and unitewith them to form double compounds, hence when magnesium carNlNERXLOGICAL CIIENISTRY. 133bonate is deposited, any zinc carbonate existing in the same solutionwill also separate out. This conclusion agrees with the results of theauthor’s previous researches on the formation of zinciferous dolomitesi n ancient seas.The various natural forms of zinc carbonabe may be grouped underthree heads, namely, that associaked with and disseminated throughoutdolomitic rocks, which is the most abundant form ; that existing inbeds and strings contemporaneous with the rocks in which they arefound ; and that which is found in fissures and caverns.in dolomiticrocks, and has been extracted from these rocks by some agency similarto that which has caused the formation of the deposits of calciumphospha,te in the south-east of France.Most probably all the zino carbonah now found, originally existedin solution in water together with the oonstituents of dolomite, andi t is therefore contemporaneous with the dolomitic rocks in which itoccurs. The isolation of the zinc carbonate in masses is the result ofsubsequent secondary changes.The Meteoric Iron of Santa Rosa, Colombia, 1810. ByA, v. LASA4ULX (Jahrb.f. Min., 1885, 2, Ref., 269--270).-The authorhas examined a fragment of the meteoric iron from Santa Rosa inColombia, which Stiibel himself broke off from the large, block thatlies in the market place of Santa Rosa.It, is stated by Boussingaultto have been found in 1810 at Tocavita. The block is, according toStiibel, 0.7 metre long, 0.6 broad, and 0.5 high, and weighs 75 kilos.The analysis gave 91-48 per cent. of iron and 8.20 per cent. of nickel,with some cobalt, 0.38 silicates, and traces of copper, aarbon, phos-phorus, and schreibersite, This analysis agrees with. the analysesof the RasgatB iron, so the meteorites of Santa Rosa and RasgatAevidently fell at the same time. Olivine and colourless splinters ofanother silicate were observed, but the colourless grains. stated byWohler to occur in the RasgatA iron, were absent.C. H.B.B. H. B.The Bingera Meteorite.. By A. LIVERSIDGE (J. R. XOC. NewSouth Wales, 16, 35-36; Juhrh f. &tin., 1865, 2, Ref., 271).-Themeteorite, a meteoric iron, was found by some gold-miners at Bingern.It is pear-shaped, 2 inches long, and 1; inch thick a t the thicker end,inch at the thinner. !The total weight is 240.735 grams, the sp. gr.being 7.834 to 7.849. The surface is covened with a, black, fused skinof magnetic oxide of iron. The skin is hard, brittle, and laminated.In places it is marked with sharply defined cracks, clearly the outlinesof the Widmanstattian figures. The mass has well-marked palarity,the thin end being the south4eeking pole.. On analysis, the followingresults were obtained :-C.Insol. in HC1. Fe. . Ni. Go. B. Total.0.137 0.553 93762 4.391 0.668 0.195 99-iOSB. Ix. B.Meteorites in the Public Collections of Mexico. By .G.VOM RATH (Jahrb. f. >!fin.., 1885, 2, Ref., 270).--The followingmeteorites are described :--From the National Museum : an iron mass 134 ABSTRACTS OF CHEMICAL PAPERS.cubic foot in size from Xiquipilco, Toluca Valley, which has remainedunaltered, whilst similar irons in Enrope exfoliate ; an iron meteoriteof nearly the same siee from the Hacienda Cacaria, 42 kilometresnorth of Durango ; a meteorite, 421 lbs. in weight, from Yanhuitlan,Oaxaca, with 6-21 per cent. of nickel and 0.27 per cent. cobalt.From the XchooE of Mines: a chondrite which fell 33 kilometres eastof Dolores Hidalgo, Guanaxnato, and an iron meteorite from SantaRosa, in the east of Coahuila. ,From the Guanaxuato College: amaqnificent,, crystalline-granular chondrite, 399 grams in weight,which fell on June 11, 1878, -between 11 and 12 A.M., at La Charca,8 kilometres from Irapuata.The Deniliquin or Barratta Meteorite. By A. LIVERSTDGE( J . R. SOC. New Xouth Wales, 16, 31-34; Jcrlzrb. f. Min., 1885, 2,Ref., 270-271).-A preliminary notice of this meteorite was pub-lished in 1872. It is a siderolite, and eonsists of varions silicates andnickeliferous iron. Externally it is covered with a blackish, fusedskin, the external portions to the depth of an inch being distinctlylaminated. The strudure is chondritic, most of the grains varyingi n size from ilK to # inch in diameter. Under the microscope they areseen to have an imperfectly crystalline structure. The meteorite isessentially a mixture of enstatite and a mineral resembling olivine,with small quantities #of other .silicates. The percentage of nickel-iron amounts to 3.93. The sp. gr. of the laminated cruet is 3.382, andthat of the interior 3.Fi03; the sp. gr. of the whole mass, weighing145 lbs., was found to be 3.387. After prolonged digestion in con-centrated hydrochloric acid, 47.47 per cent. of the meteorite dissolved.The analysis gave the following results :-B. H. B.Si02. Cu. Fe. Fe,O,. A1,03. Ni. MnO. CaO. MgO.40.28 0.18 1496 3-93 1-84 %*22 0-73 1-40 23.73K,O. Na,O. S. P. Cr,Co, C. 0.1-02 0.99 2.29 0.61 traces [3*78]The analysis af the metallic portion, separated by means of a finesieve, gave the following results :-Si02. Fe. Ni. co. P. 0. S.6.61 79.85 7.34 0.43 024 5.21 traceA second portion from a different part of the meteorite gave-Fe. Ni + Co. S O 2 . Total.91-25 2 - 2 0 1-55 100*00Daubr6e provisionally dlasses *this meteorite with those of Tadjera,Orvinio, and Koursk. B. €3. B.Proportion of Bromine in Sea-water. Ry E. BEIGLUKD(Ber., 18, 2888--2890).-Former determinations of the relative pro-portion of bromine to chlorine in sea-water are very variable. Bynieans of an improred method for the estimation of bromine in thORGAXIC CHEXISTRP. 135presence of chlorine, the author has made a series of determinationsof milligrams of bromine to 100 grams of chlorine, and of the propor-tion of chlorine in grams per litre in sea-water from various sources.The mean results are approximately equal to those obtained byDittmar (Report of Voyage of " Challenger "), namely, 340 mgrms.of bromine to 100 gmms chlorine, and 19.5 grams chlorine perlitre. V. H. V

ISSN:0368-1769    

DOI:10.1039/CA8865000125

出版商:RSC    

年代:1886

数据来源: RSC

摘要:

ORGAXIC CHEXISTRP. B. p. CHZCIZ.. .... 40-41" COCl, ...... 8" CH,*CHCl2.. .. 60 135 B. p. CO(OEtj, ...... 126 CHz(0Me)2 ..... 42" CH,*CH(AcO), . 169 Organic Chemistry. Volatility of Mixed Derivatives. By L. HENRY (Compt. r e d . , 101, 816--818).-The boiling points of mixed derivatives of the type = CXX', which contain equivalent radicles X and X' of malogous functions are the means of the boiling points of the corresponding simple derivatives, CXz and CXf2. The following kable contains examples selected from the large number given by the author. B. p. CH2C1,. ........ 41.0" CO(OMe), ..... 91.0 CH,*CH(OMe), 64.0 CHzBr*CHCl2 . . 187-138" CHCI, ........ 61.2 CH,*CHC12. ... 60.0 B. p. CH,Br,.. ...... 98.0" OHClBr, ...... 1233-125" CO(OEt),. ..... 126" CH,*CHBrz .... 110 CHs*CH(OEt)z.. 104 CHzBr-CHBr2... 186-187" B. p. CH,ClBr ............... 68-69" CHC1,Br ............... 91-92 OMeCOOEt ........... 109" CH3*CHCIBr ....... : .. 843-85" OEt-CHMe-OMe ....... 85" CHzBr*CHCIBr ......... 162-163"136 ABSTRACTS OF CHEMICAL PAPERS. Analogous relations are observed in the case of mixed polycarbon derivatives, XC . . . CX' in which the two radicles are combined with different atoms of carbon. C. H. B. Formation of Propylene from Glycerol. By A. CLAUS (Bar., 18, 2931 ; compare Abstr., 1882, 1038).-The yield of propylene is satisfactory only when a large amount of glycerol (1 kilo.) is distilled as quickly as possible with twice its weight of zinc-dust. West- phal has shown (I72aUg. Diss., Freibnrg, 1877), that acraldehyde, alljl alcohol, and two condensation products, CsHl,O and C12H,,02, boil- ing a t 140" and 200" respectively, are formed in the reaction.Both. condensation compounds when oxidised yield propionic acid and carbonic anhydride. N. H. 31. Action of Chlorine on Trimethylethylene. By N. KONDAKOFP ( J . R ~ S . Chem. Soc., 1885,. 290-319) .-Trimethylethylene may be prepared either by the action of dilute sulphuric acid on tertiary amyI alcohol, or by treating tertiary amyl iodide with alcoholic potash ; as the amylene obtained by the first method contains as a rule an admixture of asynimetrical methglethylethglene, the author used the latter mcthod in most of his experiments, Tertiary amyl iodide distils almost entirely at 124-125", net at 127-129" as stated by other investigators.The amylene obtained from this iodide was converted into bromide, and fhe latter heated with lead oxide and water in a sealed tube : methyl isopropyl ketone was formed and not an aldehyde, as would have been the case were methylethylethylene present (Eltekoff, Abstr., 1883, 566), When a current of chlorine gas is passed into trimethylethylene (the temperature being either - No or + 20°, or finally + 38', the boiling point of the hydrocarbon), it was observed that up to a certain Roint only absorption of the gas takes place, but in a short time this ceases, and hydrogen chloride is evolved until the end of the operation. The products of the reactioir differ slightly according to the temperature. In the cold, high boil- ing products (160-180") m e formed along with more volatile com- pounds ; a t the ordinary temperature, the whole of the product distils below 135" ; the compounds obtained a t 38" all pass over below 110".The chlorinated product more espeoially investigated was obtained a t the ordinary temperature. Seven fractions were obtained on distilla- tion : the first consisted chiefly of unchanged triniethylethylene, the last did not coritain any unsaturated compounds. The intermediate fractioiis strongly decolorise bromine and contain No. 3 (the main portion boiling between 90-95"), 64, No. 4, 67, and No. 5, 60 per cent. of C,H,Cl. When treated with water, the fractions 2, 3, and 4 were entirely dissolved, 5 and 6 dissolved partly, leaving an oil free from unsaturated compounds. The aqueous solution contains, in addition to tertiary amyl alcohol, an unsaturated alcohol, COHi00, boiling a t 115-117"; sp.gr. a t 0" = 0.8571 and a t 20.5" = 0.8419. This unites readily with bromine, reacts with phosphorus penta- chloride, and yields a crystalline sodium-derivative. The bromide and acetate were prepared, the latter boiling at 130-131". The data for the etherification of the alcohol, proved it t o be a secondaryORGAXIC CHEJfISTRY. 7 37 alcohol. By the action of dilute acids at 100" it is transformed into methyl isopropyl ketone. It is therefore methyl isopropenyl carbinol, CH, : CMe-CHMe-OH, the chlorinated compound obtained from trimethylethylene having an analogous structure. The fraction of the chlorine-derivatives boiling a t 133-135" contains the chloride C5Hl0ClLZ, a heavy oil, which is also left when the portions 5 and 6 of the distillate are treated with water.A. T. Fulminic Acid. By L. SCHOLVIEN (J. pr. Chew,. [Z], 32, 461- 489).-A continuation of Carstanjen and Ehrenberg's work on the fulminates (Abstr., 1882, 816). When dilute sulphnric acid (1 : 5 ) acts on sodium fulminate and the mixture is kept well cooled, a yellow liquid is obtained, which o a treatment with ether yields an ethereal solution of fulminic acid. This solution is very un- stable, and t'he fulminic acid is rapidly converted into two isomeric acids, isocyanuric acid and isocyanilic acid. The presence of free fulminic acid in the ethereal solution was proved by separating it very rapidly from the mother-liquor,. and shaking it w i t h an aqueous silver solution, when a white precipitate of silver fulminate separated immediately ; if the ethereal solution was allowed t o remain for ten minutes and then shaken with the silver solution, red silver isocjanurate separated and imcyanilic acid remained in solution.Xsocynizuric acid gives coloured Salk containing one, two, and three equivalents o€ metal ; when evaporated with hydrochloric acid it yields hydroxylamine; with potash, ammonia is given off. The pure acid, C,N303H3 + 3Hz0, forms a white, crystalline powder, melting a t 81", and exploding with great violence a t 106". When kept for a long time i t is converted into an isomeric acid, p-isoful- minzwic acid; this crystallises in small needles of vitreous lustre, when anhydrous melts at 196" with decomposition, and is not acted on by hydrochloric acid.Isocyanilic acid, HCNO, crystallises in. white lustrous needles ; when heated it decomposes without previous fusion; it forms unstable salts, and is not acted on by hydrochloric acid. Boiled with potash i t yields an acid, isomeric with Stideler and Strecker's " Uroxanic acid " ; this forms a dark violet potassium salt. When thiocarbamide is acted on by mercury fulminate, a mixture of thiocarbamide, mercury thiocyanate, carbonic anhydride, mercury sulphide and carbamide is formed. G. H. M. Decomposition of Butylene and Amylene Hydrate by Heat. By WOLKOFF and BOCGAIEFF (J. Russ. Chem. Soc., 1885, 276).- Rutylene hydra,te (secondary but,yl alcohol) when heated in sealed tubes at 240-250" for 8-16 hours is not decomposed, but if the least quantity of a hydmcid (hydriodic acid or even methyl iodide) be added, decomposition takes place a t 220°, and pseudobutylene is formed after the lapse of only five to six hours.Similar observations were made with dimethyl ethyl carbinol and methyl isopropyl carbinol and some other alcohols ; tertiary alcohols suffer this decomposition135 ABSTRACTS OF CHEMICAL PAPERS. most easily, primary alcohol with much more difficulty ; normal alcohols have not yet been studied in this direction. A . T. Preparation of Hexyl Glycerol. By P. ORLOFF (J. Russ. Chem. SOC., 1835, Abstr., 146) .-Hexylglycernl previously obtained by the author from dibromhydrin is best prepared by the action of diluted aqueous potash on the monochlorhydrin, the latter being formed by addition of hypochlorous acid to dimethyl allyl csrbinol. The iodhydrin is obtained by the action of mercuric oxide and iodine on dimethyl allyl carbinol in the presence of aster.The glycerol itself,'when treated with filming hydriodic wid and phosphorus, yields, besides a small amount of a crystalline compound not yet examined, an iodide distilling a t 140-150", and converted by alcoholic potash into a hexylene identical with Jawein's (Abstr., 1878, 961). A. T. Decomposition of Galactose and Arabinae by Dilute Acids. By M. CONRAD and M. GUTHZEIT (Bey-., 18, 290%-2907).--The following results were !obtained by heating 10.5 grams of galactose, 59 grams of water, and 4.87-4.N grams of hydrochlopic acid for Humic Undtered Acetopropionic Formic substances. galactose.acid. acid. 1-60 8-60 2.84 1.05 1 . i 7 3.05 2.85 1.10 1'; hoUPfi:- On replacing hydrochloric by sulphuric acid of the same concen- tration, the quantity df the decomposition produd obtained was considerably less. A specimen of arabinose from marc of beet-sugar melted a t 358- 160"; its specific rotatory power f o r a 10 pep cent. sdlution mas found to be [a]= = 104"; on heating 10.5 grams with hydrochloric acid under the same conditions as above, there were obtained 4.3 grams of humic subshances, 0.42 gram of formic, and 1.2% gram of aceto- propionic acid. These results tend to show that galactose and arabinose are not identical. V. H. V. Raanose or Melitose from Molasses, Cotton-seeds, and Eucalyptus Manna. By P. RISCHBIET and B. TOLLENS (Ber.. 18, 2611- 2616).-From a consideration of the properties and reactions of this substance, and especially from the composition of the sodium- derivative and the amount of mucic acid formed on oxidation, the authors conclude that it is best represented by the formula C36H640,2 + 108,O.When boiled for some time with acids, a sugar cry stallising in six-sided tables (probably galactose) is obtained. A comparison of melitose, from the manna of Eucalypfu.~ viminalis, with raffinose shows the two substances to be identical ; the name melitose is therefore preferable. Action of Oxymethylene on Amines. By S. KOLOTOFF ( J . RUSS. Chem. Soc., 1885, 229-251). - It, is known that oxymethylene reacting with ammonia forms hexamet.hylenamine ; the author has A. J. #.ORGANIC CHEMISTRY. 139 studied the reaction with mono-, di-, and tri-ethylamine and aniline. Ethylmethylanainiize, C3H7N, obtained from oxymethglene and ethyl- amine, is a colourless, alkaline liquid, boiling a t 205-208".The vapour-density dehermination and the analysis of the platinochloride show that the molecule of the compound is not polymeric, one molecule of each of the constituents entering into reaction. A solution of the base in hpdrocliloric acid, on remaining in a vacuum, is decomposed into ethylamine and oxymethylene. With diethylamine, a similar compound, CH2N2Et4, was obtained as a bright colourless liquid boiling a t 16G-169", and having a well- detined basic character. Triethylamine, ib8 was expected, does not react with oxymethylene ; thus in the reaction of axymethylene wikh amines, the oxygen of the former combines wifh all the amidic hydrogen of the amine-group, forming water, whilst the two remaining radicles, uniting, form basic compounds.Aniline reacts very reacEly with oxymethylene, the mixture a t once solidifying to a basic com- pound, which melts at 137-138"~with decomposition, and forms a solid substance which does not melt even a t 'LC)O", the temperature of its decomposition. Heated with water at loo", phenylmethylenamine splits up into aniline and oxymethylene. According to the author the molecule of the compound corresponds not with the simplest,, but with a higher, probably dodbled, formula. Imines. By A. I~ADENBURG (Bey., 18, 2956-2961 ; comp. Abstr., 1883, 910).-Pentarnethylenediamine is prepared by adding sodium as quickly as possible to a solution of trime ethylene cyanide in boiling dcohol ; the product is poured into water, and the alcohol (distilled off.A trace of ammonia is evolved, and a small quantity of piperidine goes over with the aJcoho1. The pentam&hylenediamine' is then distilled with superheated steam, the distillate treated with a slight excess of dilute hydrochloric acid, and evaporated $to dryness. The free base is obtained by dissolving theiresidue in a little water, adding potash and extracting with ether. The yield of base is 80 per cent. of the weight of cyanide employed. iIt is a colourless, syrupy liquid boiling a t 175-L78". When expnsed to air, it fumes and absorbs water and carbonic anhydride. It dissolvessparingly in ether, readily in alcohol and watar.The acetyl-derivative, CaH,o(NHAc)2, is a crgstal- line substance ; it boils above 360". The formation of piperidine in the reaction is fresh evidence in support of the formula ascribed to it, and also explains i d s relation to h i - and penta-methylene-com- pounds : piperidine is penta~aetli;lllpnimine. l h e author thinks i t probable that all cyanides may kbe converted ink0 amido-compounds by the method above desmibed. Ricuhyba nuts, from U y r i s t i c a qiqicilzalis or M. bicuhyba, give the following results on proximate analysis :- A. T. N. H. M. Bicuhyba Fa& By R. NOE8DLIKUER (Bey., 18, 2617-2623).-1-20 ABSTRACTS OF CHK1\IlCAL PAPERS. Water ........................ 8.86 Ash.. ........................ 4.50 Pat ..........................17.74 Crude fibre.. .................. 30.62 Prote'ids ...................... 1 7 f a Non-nitrogenous extractives.. ... 20.66 The results of the examination of the fat are very similar to those obtained by Reimer and Will (Abstr., 1885, 1197) with the fat of the f r u i t of 31. Xuritiamensis ; it consists mainly of trimyristin and triolein with small quantities of resin and free myristic acid, and very slight amounts. of ethereal oils, volatile acids, and of a non- saponifiable oil. A. J. G. p-Dimethacrylic Acid. By D, OUST.INOFF ( J . BUSS. Chem. SOC., 1885, 439-448). - 13-Diethylenelactic acid, obtained by oxidising ally1 dimethyl carbinol, was distilled with dilute sulphuric acid (comp. Schirokoff, Abstr:, 1880, 382). The dimethacrylic acid formed was purified by converting it into the zinc salt, decomposing this and crystallising the acid from water; it melts a t 69.5-70'.The sodium, calcium, barium,. zinc,. copper, lead, and silver. salts were examined as well as the dibromide, melting at 105--106" and resolidi- fjing a t 76". The author gives a comparative table of the principal salts and dibromides of dimethacrylic.acid, GMe2 : CH-COOH, and of its isomerides, angelic, methgrlcrotonic, and allylacetic acids. A m n. I. Oxidation of Oleic and Elaidic Acidsl wibh Potassium Per- manganate i n Alkaline Solution. By A. SAYTZEFF ( J . Rtuss. C'hent. Xoc., 1885, 41i-433).-01eic acid when treated with potassium permanganate in the presence of an excess of potash, yields dilzydr- oxystearic acid, C,,H,3(0.H)2*C!OOH, a crptalline acid insoluble in water, easily soluble in boiling, but sparingly in cold alcohol, and in hot ettier.It melts after repeated purification a t 136*5", and solidifies again a t 122-119'. When heated in a sealed tube a t 120-130" with hydriodic acid, or by the action of phosphorus tri-iodide and water, it is converted into liquid iodostearic acid, the latter by reduction with zinc and hydrochloric acid yielding ordinary stearic acid. Iodo- stearic acid and silver oxide give hydiaoxystearic acid, melting a t 83*5-85*5", and solidifying a t 68-63". The dihydroxy-acid is identical with the isodihydroxystearic acid of Overbeck (Aniaalev, 140, 72) ; the description of the properties of the acid given by Overbeck is inaccurate. Dihydroxysteatk acid, when distilled under a pressure of 100 - 150 mm., yields a crystalline acid, melting a t 77-79", and resolidi- fying at 69-66" ; the analyt'icsl results approximate to the formula CleH,O,; it would, therefore, seem to be formed by elimination of 1 mol.H,O from dihydroxystearic acid. The oxidation of elaidic acid under the above conditions yields an acid of the same composition as dihydroxystearic acid, but entirely differing from it in its properties ; i t melts a t 99-loo", resolidifiefi a tORGASIC CHEMISTRY. 1 d l 86-85', and is much more soluble in ether and in ahohol. The small amount of material did not admit of fiirther study. Oleic acid when treated with potassium permanganate alone seems to yield azelaic acid, although this could not be obtained in a state of purity from the products of the reaction. A.T. Lactic Acid from Levulose. By V. SOROKINE ( J . Euss. Chem. Soc., 1885, :368--369).-Amongst the products of the action of bases (caustic soda and baryta) upon levulose, the author finds lactic acid; it seems, therefore, that the formation of lactic acid from glucose by the aotion of bases is a reaction characteristic of all the substances of this group, similarly to the formation of levulinic acid under the influence of acids. Experiments are being made in order to determine the quantity of lactic acid formed in this reaction under varied conditions. A. T. Action of Ammonia on Succinirnide. By ROUBTZOPF (J. Rztss. Ckem. Soc., 1885, 277-278).-When amrnonia is passed over powdered succinimide placed in glass tubes and cooled to - 10' or - 20", the tubes being then sealed and heated to 100-200", succin- amide is formed.At the ordinary temperature ammonia is not taken lip, and the amide is not formed. A . T. Ethyl Diacetofumarate. By 3'. JUST (Ber., 18, 2636-2637).- By the action of sodium ethoxide on a solution of ethyl diaceto- succinate and precipitation with ether, the compound C 0 OE t.CNaAc*CNaAc.C 0 OE t is obtained as a whit'e powder. solution of iodine yields ethyl diacetofumarate, This when treat,ed with an ethereal COOEt-CAc : CAc*COOEt, as a colourless oil which solidifies to long, silky needles, melting at 95-5-96'. Non-volatile Product of the Oxidation of the Hydrocarbon C,,H,. By A. ALBITZKY and V. NIKOLSKY (J. Russ. Chem. Xoc., 1885, 435-439) .-Amongst the products of the oxidation with chromic mixtures, of the hydrocarbon C12H2, from ally1 dimethyl carbinol, a, syrupy acid, not volatilising with steam, has been obtained (Abstr., 1883,1074).The authors have made analyses of its barium, calcium, and ethyl salts; although the results best a p e with the formula C10H1606, it is more probably C,,H1,06, the latter formula being more in accordance with the structure of the hydrocarbon C1,H2,. I t a reaction with phenjlhydrazine is being studied. A. J. G. A. T. Action of Ammonia on Parabanic Acid. By MISS ROUDINSKAI.~ ( J . Russ. Chem. Soc., 1885, 278-279) .-Ammonium parabanate when heated in a sealed tube a t above 160", is to a large extent converted into oxaluramide; a t 100" the salt is decomposed, but scai~ely any amide is formed.Thc same amicle is obtained by passing142 ABS'lXACTS OF CHEMICAL PAPERS. ammonia over parnbauic acid a t 130" ; a t lower temperatures ammonium parabanate is formed. From a few experiments, it apueara that the formation of oxaluramide from ammonium parahanat e (probably con- sisting in a decomposition of the salt into ammonia and parabanic acid, and subsequent formation of amide) is not only influenced by temperature, but also by the pressure of the gaseous product of the decomposition. A. T. By S. DOROSHEMKO ( J . Russ. Chem. Soc., 1885, 285-290) .-The presence of aromatic hydrocarbons in Caucasian petroleum has been shown by Markownikoff and Oglobline (Abstr., 1883, 564), who found hydrocarbons belongiug to the higher isologous series in fractions of petroleum boiling between 150-210" and above 270".It is, therefore, highly probable tlint the lower homologues of the benzene series might be present in the portions of petroleum hydrocarbons boiling below 150'. The material for the present, investigation con- sisted (1) of portions of Bibi-Aibat petroleum boiling at 105-115" and 115-125", and (2) of a mixture of the products of purification of Balakhani petroleum boiling below loo", and of Bibi-Aibat oil boiling a t 100-120"- The hydrocarbons were converted into sulphonic acids by treatment with sulphuric acid, and these distilled with calcium hydroxide. The amount of oil thus obtained did not exceed 10 per cent. of the sulphonic acids; the hydrocarbons were subjected t80 fractional distillation, and fractions boiling a t 75-95', 95-1 lo", 110-120", 1 2 0 - M O O , 130-135, 135-141" were collected.I n the first portion benzene was shown to be present by its separation in crystals on cooling the oil to - 30" ; in the higher boiling distillates, the presence of toluene also was shown. The portion boiling at 75-110" was nitrated in the cold, and the nitro-products, which had a decided smell of nitrobenzene, reduced with tiu and hydrochloric acid, when aniline and tolaidine were formed. Toluene is also contained in tht? fraction 110-120". The portions boiling between 1.30" and 141" contain isoxylene. During the dry distillation of the sulphonic acids with calcium hydroxide, a crystalline substance melting at 192.5- 194", was deposited in the condenser, and was also obtained on cool- ing the hydrocarbons boiling above 140".Its quantity was too small for analjsia, and the author only points out its resemblance to methy lenediphenyleiie obtained by Carnelley on passing a mixture of toluene and benzene vapours through a red-hot tube (Trans., 1880, 710). A. T. Aromatic Hydrocarbons in Caucasian Petroleum. Oxidation of Benzene-derivatives with Potassium Ferri- cyanide. By W. A. NOYES (Avner. Chem. J., 7 , 145-149 ; comp. Abstr., 1884,299) .-Orthobromotoluene when oxidised with an alkaline ferricy anidc, yields orthobromobenzoic acid, but oxidation occurs only to a very slight extent, less than 0.5 per cent. being formed during three or four hours. Paratoluenesulphonamide yields 55 per cent. of the corresponding parasulphaminebenzoic acid ; the barium salt, (C7H,S04N)2Ba + 5H,O, separates in crystal!iue tufts from a cold solution, whilst fromORGANIC CHEMISTRY.143 a hot soliltion it separates with 2H20 in small scales ; this salt has been described by Remsen as crystallising with only 1 mol. H,O. H. B. Oxidation of Metanitrotoluene. By W. A. NOYES and W. E. MOSES ( A m e r . Chem. J., 7, 149-1533 comp. Abstr., 1884, 299).- When metanitrotoluene is oxidised with alkaline ferricyanide, not more than 5 per cent. of metanitrobenzoic acid was obtained, whilst the para- and ortho-nitrotoluenes yield 70 to 75 per cent. of the corresponding acids ; it would, therefore, seem probable that an alka- line ferricyanide solution can be used to oxidise a methyl-group standing in the ortho-position to a nitro-group without attackinq a methy I-group in the meta-position.By E. HJELT (Ber., 18, 2879-2881). -If chlorine is passed into ortbo-xylene until the gain in weight corresponds with the replacement of 4 atoms of hydrogen by chlorine, a crystalline mass saturat)ed with an oil is produced. On distillation, a liquid and a crystalline solid are obtained; the latter is a tetra- chloride. It melts a t 89" and boils a t 273-274", is insoluble in water, readily soluble in ether ; it crystallises in the triclinic system with axial ratio a : b : c = 0.972 : 1 : 0.741. I n order to determine whether the chlorine-atoms are disposed symmetricallg or unsym- metrically, the compound was heated with water in a sealed tube a t 200-210" : phthalide was obtained in large quantities, a result which would point to the latter hypothesis; but inasmuch as the phthalide was always accompanied, especially at the lower tempera- ture, by an oil having aldehydic properties, the author is inclined to regard the substance as having the formula C6H1(CHCl,),.H. B. Ortho-xylenyl Chloride. V. H. V. Reaction of Aluminium Chloride with Hydroxyl Com- pounds. By A. CLAUS and H. MERCKLIN (Ber., 18, 2932-2936).- Dichlorhydrin-alu.minium chloride, A12C14( 0*C3H5C1,),, is obtained by the action of aluminium chloride on dichlorhydrin dissolved in carbon bisulphide. Trip h enol- alumi?aium chloride, A12C13( 0 Ph) 3, is prepared by adding alnmiiiiuni chloride in small quantities to a solution of phenol i u boiling carbon bisulphide ; it forms a yellow powder readily soluble in boiling carbon bisulphide.Resol.cino1-akl.minium chloride, Al2C1, : CsHaO,, forms a thick reddish- brown liquid, which gradually becomes solid when kept over sulphuric acid ; it dissolves readily in hot carbon bisulphide. All these corn- pounds decompose violently when brought into contact with water. Symmetrical triphenylpropane, C3H5€'h3, is prepared from trichlor- or tribrom-hydrin and forms a thick, yellow liquid which distils without decomposition only under diminished pressure. D ipheng 1- propane is formed at the same time. Pseudocumenol and Pseudocumidine. By I(. AUWERS (Bey., 18,2655-2663).-By the action of bromoform and aqueous alkalis on pseudocumenol, a compound, CLoHr4Brz0, is obtained, which melts It is a crystalline, hygroscopic substance.N. H. M.144 ABSTRACTS OF CHEMICAL PAPERS. at 105", and resembles the chlorine compound described in the author's previous communication (Abstr., 2885, 380) in all respects save in its ready decomposition by alcoholic potash, by which the chlorine compound is not affected a t 100". By the action of iodoform on pseudocumenol, only a very small quantity of an iodo-compound is formed. Similar products cannot be obtained from phenol, triphenyl orthoformate being formed. Dibromopseudocumenyl methyl: ether, c6Br2Me3*OMe[2 : 5 : 1 : 3 : 4 : 6 J, is obtained by brominating pseudocuinenyl methyl ether a t the ordinary temperature, o r by methylating dibromopseudocummol. It crystallises in white needles of vitreous lustre, melts at 96", is in- soluble in water, readily soluble in alcohol and acetic acid, very readily soluble in ether, chloroform, and benzene, and is only slightly attacked when heated with hydrochloric acid a t 170".Metnnityopseudocumenoi, OH-C6HMe3*NO2 [Me3 : NO, : OH = 1 : 3 : 4 : 2 : 61, is prepared 'by evaporating an alcoholic solution of its nitrate (Zoc. cit.) .to a syrup and then distilling with steam, and is also obtained by adding concentrated hydrochloric acid to an alcoholic solution of the nitrate, and allowing the mixture to remain for some time. It. crystxllises i n long, reddish-yellow needles or prisms of fatty lustre, melts a t 48", and is moderately soluble in hot water, readily in the other usual solvents. The nitrate of this substance is also formed when pseudocumenyl methyl ether is nitrated.2Cletanitro- pseudocumen yl methyl ether, NO,-C6HMe3-OMe, is prepared by methyl- ating metanitrocumenol : it crystallises in large prisms and rhombic tables, melts a t 4 1 4 2 " , and is very readily soluble in the ordinary solvents except water. The following corrections are made in the melting points previously given (Zoc. cit.) : dinitropseudocumenol melts a t 112", dipseudocumenol a t 173", and dipseudocumenyl methyl ether a t 126". Dibromodipseudocumenol, ClrrHrOBr202, crystallises in small, lustrous crystals, and melts a t 186-187". Dipseudocumidine, when pure, melts a t 68" and boils a t 234" ; aceto- pseudocumide melts a t 164" and boils a t above 360" ; orthonitraceto- pseudocumide melh a t 202--204". Diizitracetopseudocun.lide, C6Me3(N02)1*NHAc [l : 3 : 4 : 2 : 5 : 61, melts at 280", sublimes unchanged, and is insoluble in water, and sparingly soluble in otber solvents.If this is heated with concentrated sulphuric acid for a few minutes at loo", and a, large quantity of water is then added, dinitropseudocumidine, C6Me3(N02)2*NH2, is preci- pitated. This crystallises in long, lustrous, orange-yellow needles, melts at 183", and has but very feeble basic properties. When reduced with tin and hydrochloric acid, it yields t'he hydrochloride of a base whose composition could not be ascertained with certainty. The hydrochloride crystallises in plates or prisms, the free base forms silky needles. Aiizidopseudocumy lenetheny lamidine, NH2*C6%fe3<NH>CMe, is pre- pared by reducing dinitracetopseudocumide with tin and hydrochloric acid.It crystallises with 2 mole. H,O in pale-yellow prisms or stellate --NORGANIC CHEMISTRP. 145 groups of plates, softens at 215", and melts a t 215-218". The hydro- chloride, CllH15N3,2HCl + Aq, crystallises in slender, white needles ; it monohydrochloride, Cl1H1JYB,HCL + 2H3,0, crystallises in slender, white prisms ; the platinochloride, Cl,H,,N3,H2PtC16, forms stellate groups of slender, oi-ange-red prisms. Action of Acetone on Aniline. By C. BEYER (J. pr. Chem. [Z], 30, 489-491).-An answer to Engler and Riehm regarding priority. Remarks on the Preceding Answer." By E. v. MEYER (J. pr. A. J. G. Chem. [a], 30,491). Consecutive Xylidines. 2905) .-A controversial paper. By E. WROBLEWSKI (Ber., 18, 2904- Commercial Xylidine.By W. STAEDEL and 0. HOLZ (Ber., 18, 2919--2924).-Commercial xylidine consists of two isomeric modifi- cations : the one a metaxylidine [Me : Me : NH, = 1 : 3 : 41 ; the other a paraxylidine. The former boils a t 212", and its acetyl- derivative at 130"; its corresponding xylenol is not, as Jacobsen described, a liquid, bat a solid crystallising in needles which melt at 28O, sparingly soluble in water, the aqueous solution giving a blue coloration with ferric chloride. On oxidation with chromic acid, the paraxylidine yields a quinone. The corresponding quinol forms a dibenzoyl-derivative, CGH2Mez( OBz),, crystallising in glistening needles which melt at 160". The diethyl- derivative, C6H2Me(OEt)2, forms glistening white leaflets melting a t 106".V. H. V. Simple Method of Preparing Azo-derivatives. By 0. N. WITT (Ber., 18, 2912-2913).-After alluding t o the various difficulties incidental to the methods of preparation hitherto proposed for the azo-derivatives, the following simple process is suggested. A quantity of stannous chloride equivalent t.0 that of the nitro- compound, is poured into an excess of soda, and the solution formed is heated with the nitro-compound a t the temperature of the water- bath. The process is suitably modified according to the nature and stability of the compound which it is required to reduce. Usually the azo-salt crystallises out on cooling, but if this does not, occur, then the stannous oxide is precipit,ated by a current of carbonic anhydride, the liquid filtered and evaporated, and the azo-derivative finally separated from the potassium carbonate by aqueous alcohol.V. H. V. Azo-compounds with Mixed and Substituted Radicles and their Derivatives. By T. KANOKNIKOFF (J. Russ. Chem. SOC., 1885, 369--371).-1n manner similar to the formation of hydroxyazobenzene from diazobenzene and phenol, new azo-compounds were obtained from orthoanisidine and metacresol, from orthoanisidine and ortho- cresol, and from orthonitranisoil by reducing them with sodium amalgam. The first, OMe*C6H4.N2*C6H3Me*0H, melts a t 161", the second a t 68", and the third at 103". The reduction of these isomeric VOL. L. I146 ABSTRACTS OF CHEMICAL PAPERS. compounds with stannous chloride and hydrochloric acid yields sub- stances corresponding with benzidine and diphenylene.The chief aim of further investigation will be the study of Skraup's reaction with the compounds containing amido-groups. Thus far, on heating me ta- cresolorthoanisod and azorthoanisoil with glycerol-sulphuric acid and nitrophenol, compounds of basic character are obtained which form well crystallised salts. A. T. Derivatives of Dicyanphenylhydrazine. By J. A. BLADIN (Ber., 18, 2907'-2912).-By the action of nitrous acid on dicyan- phenylhydrazine, a compound, C8H5N5, is obtained (Abstr., 1885, 980) t o which the formula N<Nph>c.CN is now ascribed, This, wben saponified, yields the corresponding carbozglic acid, N-N crystallising with 1 mol. H,O in colourless needles; when dried it melts a t 137-138", and is decomposed with evolution of carbonic anhydride a t 150". Its potassium salt forms glistening leaflets, copper salt, bluish-green rhombic tables, silcer and lead salt';, sparingly soluble crystalline precipitates. The nzethyl salt, CN4Ph*COOMe, crystallises in glistening leaflets melting a t 116", soluble in alcohol and ether, sparingly soluble in water; the ethyl salt forms colourless needles melting a t 74".Hydrogen peroxide converts the nitrile, PhCN,.CN, into the corresponding amide, CN,Ph*CONH2, which crystallises in colourless prisms melting a t 168", sparingly soluble in water, alcohol, and ether. On heating the carboxylic acid, an oil is obtained of the composition C,N,P4 = N<hph>CH ; it is heavier than and insoluble in water, readily soluble in alcohol and ether, is readily decomposed on distilla- tion, and has feebly basic properties, dissolving in concentrated acids, and yielding a, platinochloride in the form of golden leaflets.YON V. H. V. Indophenol and Indoaniline. By R. MOHLAIJ (Bw., 18, 2913- 2918).-The researches of Caro, Nietski and others, have shown that the simultaneous oxidation of paradiamines or amidophenols on the one hand, and of phenols and amines on the other, yields a number of dyes belonging to the safranine, or indophenol and indoaniline groups. In this paper phenol- and &-naphthol- blues and their deriva- tives are more particularly studied. Phenol-blue, CIJHIINPO, is best prepared by heating the double chloride of zinc and dimethylphenylene-green with soda solution (sp.. gr. = 1.4) ; a flocculent blue precipitate separates out, which on boiling with a 10 per cent.grape-sugar solution, evolves dimethyl- amine and dissolves to form a red liquid. On filtration and exposure of the liquid to the air, the phenol-blue separates out in glistening, prismatic crystals. The reaction is explained thus :-ORGANIC CHEMISTRY. 147 N*C,H4*NMe, N*C,H,*NMe, CSH,' I + NaOH = NaCI + C,H/ 1 'KMe2C1 'NMe2.0H I n the above operation,.if a larger proportion of soda solution is used, and the liquid is boiled before the addition of the grape-sugar, quinonephenolimide, <C"H">N*C6H,*OH, -0- is produced by a similar reaction; the same change is also effected by boiling phenol-blue with soda. a-ilTaphthol-bZue, c,HI,,N20, is prepared by reducing nitroso- dimethylaniline hydrochloride with zinc-dust, and adding the product to an equimoleculur poportion of mnaphthylaaine hydrochloride dissolved in 500 parts of water.It forms bluish-violet, hard crystals. Para- and Ortha-nitroxanilic Acids and their Reduction. By 0. ASCHAN (Ber., 18; 2936-2940) .-Paranitroxanilic acid, C,H6N,05, is obtained, together with a small quantity of the ortho- derivative, by the action of fuming nitric acid on oxanilic acid. It crptallises from water in long, pale yellow needles, containing 1 mol. H20. The potassium and sodirum salts are sparingly soluble in cold water; the ammonium salt dissolves readily in alcohol. When paranitroxanilic acid is reduced, it yields parapheny lenediamine. Orthonitroxamilic acid is best prepared by heating orthonitraniline with anhydrous oxalic acid for 40 minutes a t 130-140" ; the product is then washed with a little water and recrystallised from water.The acid separates in long, gold-coloured needles, melting a t 112". It is readily soluble in hot water, alcohol, and glacial acetic acid. The alkali salts are sparingly soluble in cold water and alcohol, and crystallise in yellow, lustrous needles. The barium and silver sa2ts form colourless needles almost insoluble in water. The acid has already been obtained by v. Herff (Anden, 209,367), who described it as " ethyl oxorthonitranilate." Tin and hydrochloric acid act on the acid with formation of dihydr~x~ethe.lzylphe?z?llenediami~ze, CsH,N,O,. This crystallises in long, slender needles with a glassy lustre melting a t 280" ; it is sparingly soluble in water, alcohol, and ether, insoluble in benzene, &c. It dissolves in alkali, with formation of unstable salts which are deconiposed by carbonic anhydride.A similar compound was obtained by Hinsberg (Abstr., 1883, 323) from meta- nitroparoxaltoluidic acid. N. H. M. V. H. V. It melts at 210". Isomeric Malontoluidic Acids. By L. R~~GHEIMER and R. HOFFMANN (Be?.., 18, 2971-29 75) .-Malonparatoluidic acid has already been described (Abstr., 1884, 1023). The calcium salt (with 44 mols. H,O) forms long, slerider needles; the barium salt (wit'h 5 mols. H,O) forms lustrous prisms. The silver, copper (with 2 mols. H,O), and zinc salts are also described. The ethyl sult 1 2148 ABSTRACTS OF CHEMICAL PAPERS. crystallises from alcohol in large, well formed, rhombic crystals, a : b : c = 0.9320 : 1 : ? Malonorthotoluidic acid, C,H,Me*NH*C0.CH2.COOH, is prepared in a manner similar to the para-acid (Zoc. cit.).It is readily soluble in water and alcohol, from which it crystallises in long, colourless needles; these become reddish when exposed to air. It melts a t 138-143" with evolution of carbonic anhydride. The calcium salt (with 3 mols. H,O) forms groups of small needles rather readily soluble in water; the barium salt (with 1 mol. H20) crystallises in broad needles, very readily soluble in water; the copper salt (with 2 mols. H20) crystallises in well-formed, lustrous,. greenish-blue prisms. The ethyl saZt forms long, narrow prisms melting a t 73-74'. Malonnaetatoluidic acid, C,H4Me*NH*CO*CH2*COOH, forms large, lustrous plates which melt at, 99-101", and decompose only when heated to a still higher temperature.Reaction of Benzaldehyde with Azobenzene. By T. BARZILOVSKY ( J . Russ. Chem. Soc., 1885, 366-368) .-When azo- benzene and benzaldehyde are heated with zinc chloride, a greenish- grey powder (m. p. 339") is obtained and found to be identical with Schiff's benzilidene-benzidine (Abstr., 1878, 668). In the absence of zinc chloride, the reaction gives a different result ; when heated in a sealed tube during three to four hours a t 200", the two compounds yield a dark brown, crystalline mass, which after purification forms white, glistening, nacreous plates, melting at 164", easily soluble in alcohol and benzene, sparingly in ether, and very slightly in light petroleum. Its composition seems to indicate that it is a product of the direct union of benzaldehyde with azobenzene, CI2H,,N2( C7HsO),.A further investigation of the compound will be made, as well as of the products which may be obtained from azo- benzene and the three isomeric nitrobenzaldehydes, and from azo- benzene and azotoluene and some saturated aldehydes. Action of Alkyl Iodides on Amido-acids. By A. M~CHAEL and J. F. WING (Amer. Chem. J., 7, 195--199).-Paramidobenzoic acid was dissolved in methyl alcohol, and an excess of caustic potash and methyl iodide (3 mols.) added, with addition of more potash from time to time. After removal of the methyl alcohol, the addition of acetic acid precipitated dimethylamidobenzoic acid ; from the concentrated filtrate, hydriodic acid precipitated the hydriodide of the beta'ine, C,H,<CG.O> ; the free base, its hydriodide and its platinochloride, are described.When ethyl iodide acts on paramidobenzoic acid in presence of ethyl alcohol, only ethyl diethylamidobenzoate is formed ; no trace of a betaine could be detected. Ally1 iodide in alcoholic solution did not yield the corresponding betaine, but only diallylparamidobenzoic acid melting a t 127" ; the corresponding ally1 salt was not formed. The three iodides therefore show a gradual variation in their action. N. H. M. A. T. NMe3 H. B.ORGAXIC CHEMISTRY. 149 Mononitro-derivatives of Par- and Met-acetamidobenzoic Acids and their Products of Reduction. By A. KAISER (Ber., 18, 2942-2 9 5 2) .-Met anitrop Bra cet amid ob enzoic acid, COOHCsH,(NOZ)*NHAc [COOH : NO2 : NHAc = 1 : 3 : 41, is prepared by nitrating paracetamidobenzoic acid a t a temperature below LO", and subsequent purification of the product by means of its barium salt.It forms yellow plates melting a t 220-221", readily soluble in boiling alcohol, glacial acetic acid, and acetone, very sparingly soluble in cold water. Warm dilute hjdrochloric acid saponifies it easily. The barium salt (with 64 mols. HzO) forms yellow plates readily soluble in hot water; the caZcium salt cry+ tallises with 2 mols. H,O in sparingly soluble, yellow needles. When a solution of the a,cid in glacial acetic acid is treated with tin ,meta~~nranh~d,racetodiamidobenzoic acid, COOHG6H,<~H>CMe, N is formed. This compound crystallises with 1 mot.H20 (which it loses a t looo), and melts with decomposition a t 301-302"; it dissolves readily in boiling glacial acetic acid, less readily in hot alcohol, and is almost insoluble in ether, acetone, benzene, and chloroform. When heated above 160°, it gives off carbonic anhydride and yields anhydracet'diamidobenzene. The hydrochlo?-ide forms slender, white needles, very readily soluble in cold water ; the platinochloride (with 2 mols. H,Oj crystallises in gold-coloured needles. The potassium salt forms colourless, microscopic needles. Paranitrometacetariidobenzoic acid, [COOH : NOz : NHAc = 1 : 4 : 31, is obtained in a manner similar to the metanitro-derivative, and forms deep yellow plates which melt a t 205-206"; it is readily soluble in boiling alcohol, glacial acetic acid, and acetone. The barium salt crystallises with 7 mols.H20, in long, slender, yellow needles ; the calcium saZt, with 7Q mols. HzO, forms nodular groups of yellow needles; both dissolve readily in boiling water. When saponified, the acid yields paranitrometacetamidobenzoic acid, melting at 298". Ethyl yaranitrometanzidobenxoate ci*ystdlises in long, red needles melting at 139", very readily soluble in ether, alcohol, acetone, &c. When paranitrometacetamidobenzoic acid is reduced, an anhydro-compound is formed identical with that obtained from metanitroparacetamidobenzoic acid. Consecutive orthonitrometaceta~nnidobenxoic acid was found in the mother-liquor obtained in the purification of paranitrometacetamido- beneoic acid ; it forms colourless needles readily soluble in alcohol, glacial acetic acid, &c., and melts with decomposition at 240-241".The barium (with 1 mol. H20) and calcium (with 6 mols. H20) salts are described. When saponified with baryta, it yields consecutive orthonitrometarnidobcnzoic acid melting at 156-157". Action of Benzanilidoimide Chloride on Ethyl Sodo- malonate. By F. Jusr (Bey., 18,2623-2631>.-By this reaction about equal parts of ethyl mono- and di-anilbenzeny1mnlonate are formed. N. H. M.150 ABSTRACTS OF CHEMICAL PAPERS. Ethyl anilobenzenylmaloozate, NPh : CPh*CH(Cr)OEt),, is obtained from the product of the reaction, by diluting it with water, extracting with ether, evaporating the ethereal solution, and crystallising the residue from alcohol.I t forms large, hard, monoclinic or triclinic crystals, which are strongly refractive, and show a blue fluorescence ; i t melts a t 75", and is insoluble in water, readily soluble in alcohol and ether. When heated with dilute hydrochloric acid in sealed tubes a t 120°, it is converted into acetophenone, ethyl chloride, aniline hydrochloride, and carbonic anhydride. Ethyl dianiZbenzenylmaZonate, C(CPh NPh),(COOEt),, is con- tained together with ethjl malonate in the motheu-liquor of the preceding compound; it can also be prepared by the action of sodium and benzanilidoimide 6hloride on the mono-compound. It crystallises in stellate groups of pldfes, and melts at 160". When heated with ditute hydrochloric acid in sealed tubes at 150", i t yields beiizoic and acetic acids, ethyl chloride, aniline hydrochloride, and carbonic anhydride. Ethyl ani/be?zzenylethyZmalonate, .NPh : CPh*CEt(COOEt),, is obtained by the successive action of sodium and af benzanilidoimide chloride on ethylic ethylmalonate, as a colourless oil, which cannot be crystallised or distilled unaltered.Benzanilide is formed by the action of aniline on the product of the reaction of beneoic chloride with ethyl sodomalonate. Arnidotoluenedisulphonic.?,Acid. By H. HASSE (Anmlelz, 230, A. J. G. 28 6-298) .-Ort h amido toluen emetasulphonic acid, NH2*C6HjMe-E103H [Me : NH, : SOiH = 1 : 2 : 51, NH,GH,Me(S03H), [Me : NH, : SO,H : SO,H = 1 : 2 : 3 : 51, by the action of fuming sulphnric acid a t l50-l7O0, or of chloro- sulphonic acid at 160". The disulphonic acid crystallises with 16 mols.H20 i n colourless needles, which are soluble in alcohol and in water The normal barium salt, C7H7N(S0,),Ba + 3H20, crystallises in the triclinic system. It is freely soldble in water, but is precipitated from the solution by alcohol. The acid salt, ( SO3H.C7H7X*S03),Ra + 39&O, forms microscopic needles soluble in water, but insoluble in alcohol. The potassium salt, C7H,N(SO9K), + 2H20, crystallises in monoclinic plates. The sodium salt forms tabular crystals containing 6 mols. HfO. The calciwn salt, C7H,N(SO3)?Ca + 5H20, forms l u n g plates soluble in water, but not in alcohol. The normal lead salt, C&t,N(SO,),Pb + 2H@, crystallises in cololrrless prisms. It is less soluble in water than the potassium salt. {HSCi*&H,N*SO,),Pb + 6iW20 forms quadratic prisms.It is more soluble in water than the normal salt. The disulphonic acid decomposes a t 240", yielding amidotolnene- sulphonic and sulphuric acids. The diazo-compound is crystalline. The salts af amidotolnenedisulphanic acid are converted into diazo- tolnenedisulphanates by the action of nitrous acid. The pofassiwn salt crj stnllises in anhqdrous, jellow prisms. The barium salt, is converted into am.idot~~uenedisulphonic acid,ORGANIC CHEMISTRY. 151 [C7H,N2(S03)2]2Ba + 4H20, is deposited from its aqueous solution on the addition of alcohol, in microscopic plates. The lead salt forms yellow, anhydrous plates. CresoZdisulphonic acid is obtained in needles or plates by boiling an aqueous solution of the diazo-compound. It is freely soluble in water and alcohol.The potassium salt, OH*C7H5(S03K)z + 14H20, and barium salt, OH*C7H5( SO,)?Ra + 3iH20, crystallise in needles. Diazotoluenedisulphonic acid is decomposed by boiling with absolute alcohol, yielding ethoxytoluenedisulphonic acid. It is also decom- posed by hydrobromic acid, forming bromotoluenedisulphonic acid. The potassiunz salt, C,H5Br(S03K)z + 4H20, crystallises in plates, and the barium salt, C711,Br( SO,)?Ba + lQHzO, in long, colourless needles, sparingly soluble in water. The chloride melts a t 90°, and the amide at 237". Tbe bromiiie in the acid is replaced by hjdrogen on treat- ment with sodium amalgam, but a better yield of toluenedisulphonic acid, C,H3Me(S03H), [Me : S03H : SO,H = 1 : 3 : 51, is obtained by the action of hydriodic acid on potassium diazotoluenedisulphonate.Toliienedisulphonic acid.is an oily liquid. The ammonium and potas- sium salts are crystalline; the latter is insoluble in alcohol. The chloride, C7H6( S02Cl),, is deposited from ether in colourless prisms melting a t 132". The amide forms sparingly soluble plates, which melt at 230. Attempts to prepare amidotoluenetrisulphonic acid were unsnc- cessful. w. c. w. Two Dislllphonic Acids of Paratoltzidine. By L. RICHTER (Annalen, 230, 313-333) .-Paramidotoluenedisdphonic acid, NH2*CsH2Me(S03H)2 + 2H20, can be prepared by the action of 'fuming sdlphuric acid or of chloro- sulphonic acid on paramidotoluenemetasulphonic acid. It forms B crystalline mass soluble in water, less soluble in alcohol. The normal barium salt, NHi*C7H5(S03),3a + 3HZQ crystallises in rhombic plates soluble in hot water, but insoluble in alcohol.The acid barium d t , ( S03H*C7H7N*S03)Ba + 3Hzo, crystallises in needles. It dis- solves freely in hot -A atfer. Potassium amidotoluenedisulphonate, NH2.C7H5(SO3K), + 2H20, is deposited in pointed prisms from an aqueous solution on the cautious addition of alcohol. The normal lead salt forms anhydrous, silky needles, soluble in water. The acid lead salt forms white needles. It is less soluble than the normal salt. Paramido toluenedisulphonic acid is decomposed by heat at 200", or by the action of water a t 140°, into sulphuric and paramidotoluene- metasulphonic acids. The diazo-compound of the disuiphonic acid is exceedingly soluble in water, but is neither dissolved nor decomposed by alcohol.The potassiuni, barium, and lead salts of this acid are anhydrous. They are decomposed by boiling with water, yielding salts of paracresoldisulphonic acid. The free acid forms needle-shaped crystals, which are freely soluble in water and alcohol. Barium paracresoZdisuZphonate, OH*C7H,( SO)zBa + 4H20, crystallises in flat needles, soluble in water. The potassium salt, which crystallises in152 ABSTRACTS OF CHEMlCAL PAPERS. plates, and the lead salt>, OHG7H,(S0,),Pb + 3H,O, are precipitated from their aqueous solutions by alcohol. The dinitroparacreso 2 obtained from the amidodisulphonic acid crystallises in lemon-coloured needles. It melts a t 82*5", and dissolves freely in alcohol, sparingly in water. The potassium, barium, and silver salts are crystalline. Barium and potassium parabromotoluenedisulphonates, C7H,Br(S03)zBa + 6H20, and C7H5Br(S03K), + H20, The su1phoni.c chZoride forms thick prisms melting a t 133".form sjlky needles soluble in water. It is freely soluble in ether. On cooling its hot aqueous solution, the amide is deposited in colourless prisms soluble in hot water and in alcohol. It melts above 240". Pariodotoluenedisulplaonic acid, C,H,I( SO,H),, forms needle-shaped crystals freely soluble in alcohol and water. The barium salt, C,H51(S03)&a + 6H,O, and the potas.sium salt, C7K61(S03K)z + 2H20, ai-e soluble in water, but insoluble in alcohol. The sulphonic chloride forms quadratic prisms. It melts at 143", but if it is allowed to solidify and is then reheated, it melts at 126".The amide melts a t 130-132", and is soluble in alcohol. The toZuen,edisulphonic acid, C7H6( SO,H),, obtained by the action of sodium amalgam on an aqueous solution of potassium iodo- toluenedisulphonate, is identical with the acid described by Hakansson, (Ber., 5, 1084). Hy drazinet oluenedisu lphonic acid, N2H3* C7H5( S 03H)2, is a crystal I ine compound dissolving freely in alcohol and in water. The acid barium salt crystallises in plates containing 2& mols. H,O. 11. ParamidotoZuenedisulphonic mid, NH2*CGH2Me( S03H), + 2$H20, forms silky needles freely soluble in water, less soluble in alcohol. The normal barium salt crystallises in plates containing 1 mol. H,O. It is sparingly soluble in water. The acid barium salt crystallises with 1+ or 4 mol.H,O. Thepdassium salt contains 2 mols. H20. It is freelv soluble in water, but insoluble in alcohol. The free acid decomp&es at 290", yielding paramido-orthosulphonic and snlpbnric acids. w. c. w. Nitrotoluidiqesulphonie Acid. By G. FOTH (AnnitZen, 230, N0,~CsH,~~e(NH2)*SOaH [Me : NO, : NH, : SO,H = 1 : 2 : 4 : 51, is obtained by the action of chlorosulphonic acid on nitrotoluidine at 160". The crude product is dissolved in ammonia, and the free acid liberated from the ammonium salt by the addit'ion of hydrochloric acid. The pure acid is deposited from its aqueous solution in pale- yellow needles which darken on exposure to the air. It is sparingly soluble in alcohol and in cold water. Potassium nitrotoluidinesulphoaate, C,H,N202*S03K + H,O, crystallises in needles or prisms of an orange colour, and the ammonium salt in golden needles or prisms.Both salts are sparingly soluble in cold water. The barium salt, (C,H7N202*S03)2Ba + 4H20, forms yellowish-red prisms. The lend 298-313) .-The best yield of nitrotoluidinesulphonic acid,ORGANIC CHEXISTRE'. 153 and silver salts are also sparingly snluble in cold water ; the former crystal!ises in red needles, and the latter in glistening white prisms. The diazo-compound, NOz*CsHzMe<& SOa- : N>, is prepared by adding dilute sulphuric acid to a solution of potassium nitrite and nitro- toluidine sulphonate. It is converted into nitrotoluenesulphonic acid by the action of absolute alcohol a t 100". ~itrotoluenesulphonic acid, N0z.C6H,Me.S03H [Me : NO2 : S03H = 1 : 2 : 51, and its salts are very soluble in water, and crystallise with difficulty.The potassium salt forms thick prisms of a reddish-yellow hue. The sulphoiiic chloride is deposited from ether in thick prisms melting a t 50". It is freely soluble in ether and in glacial acetic acid. The arnide forms glistening needle-shaped crystals, which are freely soluble in alcohol. J t melts a t 133.5". When reduced with ammonium sulphide, nitrotoluenesulphonic acid yields a toZuidiiaesuZp h o n k acid, NH2.c6H3~$e*So3H [Me : NH, : S0,H = 1 : 2 : 51, which appears to be identical with the acid described by Page1 (this Journal, 1875,897), and by Nevile and Winther (Trans., 1880, 626). Iodotoluidinesulphonic acid, NH2*C7H,I*SO3H, prepared by the action of hydriodic acid on the diazo-compound of nitrotoluidinesulphonic acid, crystallises in needles.The barium salt crystallises in rhombic plates which are freely soluble in water. ToluylenediarninesuIlp7~onic acid, CsHZMe(NHz),~SO,H [l : 2 : 4 : 51, is obtained by the action of stannous chloride on nitrotoluidinesulphonic acid. It is a crystalline substance, and unites with acids as well as with bases, forming crystalline compounds : for example, The barium salt contains 54 mols. HzO. ~0zoC6HzMe(NzH3)~S03H [Me : NOz : N2H3 : S03H = 1 : 2 : 4 : 51, crystallises in quadratic plates. prisms containing 4 mols. H,O. It is sparingly soluble in water. C,H~(XHZ)~*SO3H,HCl + HZO ; C7Hs(NHz)z*SO3K + HZO. Nitrotoly lhydraxinesulphonic acid, The barium salt forms long, yellow It is freely soluble in hot water, but Orthamidometaxylenesulphonic Acid.By J. SARTIG (AnnuZen., 230,333-345).-The author confirms Jacobsen's statements (Abstr., 1883, 593) regarding orthamidometaxylenesulphonic acid and its salts, with the exception that he finds that the barium salt contains 2 mols. H20, whilst Jacobsen found only 1 mol. H,O. The diazo- compound crystallises in microscopic rhombic plates. It is decom- posed by hydrohromic acid, yielding a bromo-xylenesulphonic acid, C6HzMezBr*S0,H [Me : Me : Br : S03H : 1 : 3 : 6 : 41, which has been described by Wedding (Ber., 11, 1062). By decomposing the diazo- compound with water, xylenolsulphonic acid, only sparingly soluble in cold. w. c. w. OH*C6H,Me*S03H [Me : Me : OH : S03H = 1 : 3 : 6 : 41, is obtained i n needle-shaped crystals which are freely soluble in water and alcohol.The aqueous solution gives a violet coloration with154 ABSTRACTS OF CHEXICAL PAPERS. ferric chloride, which turns green on the addition of alcohol. The buwium, (OH*C,H,*SO,),Ba + HZO, and lead, (OH.C8H,S03)2Pb + 2H20, salts crystallising in needles, and the anhydrous potassium salt crystal- lising in rhombic plates, are easily soluble in water. Absolute alcohol decomposes the diazo-compound. forming erhoxy-xylenesulplzonic acid, OEt.C6HzMe2*S03H [Me : Me : OEt : SOjH = 1 : 3 : 6 : 41. Thisacid crystallises in microscopic, rhombic plates, which are freely soluble in alcohol and in water. The b a ~ i u m salt contains 3 mols. HzO ; it is soluble in water and in alcohol. Nitra71aido-x2lZe9teulphonic acid, NHi*C,HMeZ(NOz)-SO3H, prepared by the action of a mixture of stronq nitric and srilphuric acids on rtmidoxylenesulphonic acid, crystallises in colourless needles.It is sparingly soluble in water and in alcohol. 'The potassium and barium salts crystallise in rhombic plates containing l+ mols. H20. They dis- solve freely in water; the barium salt is but sparingly soluble in alcohol. Lpad niiro-xylidiTzesupho1Late, NH,( C,IE4,S03),Pb + HzO, forms silky needles soluble in water. The diazo-compound crystallises in quadratic plates. It is decomposed by boiling water, yielding nitro-zylenol- sulphoriic acid. This acid is freely soluble in water and alcohol. The barium and lead salts crystallise with 3 rnols. H,O. They are more soluble in water than in alcohol.Rromonitro-xyZe?aesulphonic acid, N0z*C6H&fe,Br*S0,H, crystalhe8 in rhombic plates, which dissolve freely in alcohol and water. The barium salt, (N02*C,H,3~S03)2Ba + 3+H2Q, forms needle-shaped crystals soluble in hot water and in alcohol. The potassium salt contains 1 mol. HLO. It forms yellow prisms, and resembles the barium salt in-solubility. Thepotusiium and barium salts of the ethoxy- nitrosulphonic acid are &woluble in alcohol, but, soluble in warm water. Diumido-xylen,esuZphonic acid, C6H~e,(NHz)i*S03H, obtained by the action of tin and hydrochloric acid on nitramido-xylenesulphonic acid, crystallises in prisms. It is soluble in water, but insoluble in alcohol, and forms crystalline compounds with acids and with bases. The barium salt crystallises in microscopic, rliombic plates, the potassium and lend salts in prisms.Ths first contains 36 mols. HzO, the potassium salt 1 mol. H,O, and the lead salt is anhydrous. w. c. w. Condensation Products o€ Isatin. By A. BAEYER and M. J. TJAZARUS (Ber., 18, 2637--2648).-Fresh analyses of indophenine and its dibrom-derivative lead to the formulw C12H7N 0s and C1,H5BrzNOS for these compounds. Whilst benzene does not seem to unite with isatin, toluene reacts readily with it in presence of sulphuric acid. Toluisatin, so obtained, crystallises in lustrous, colourless needles, melts at 200-201", is readily soluble in alcohol, ether, and benzene, sparingly i n light petroleum, insoluble in water, acids, and alkalis. The acetyl- derivative, CZrH2,NO2, crystallises in thin, colouriess needles, melts a tORQANIC CHEMISTRY.155 142-143", and yields toluisatin when boiled with alkalis. The ethyl- derivative, C,4H23N0,, pFepared by 'heating to1 uisatin with sodium ethoxide and ethyl -iodide, or by the condensation of dhylpseudo- isatin with toluene, crystallises 'in nearly colourless plates, and melts a t 108'. From these results, it, follows that toluisatin must be regarded as a pseudoisatin-derivative, and that in the condensation of isatin vith toluene a conversion of is&in into pseudo-isatin must have occurred. Tolubrornisatin, C22H1,BrN0, prepared from toluene and bromisatin, crystallises in colourless needles, and melts at 235" ; the acetyl-derivative ci-ystallisea in needles, and melts a t 156". Phenolisatin, NH<~~$>C(C6H4*OH)z, is prepared by dissolving isatin in an excess of phenol and adding sulphuric acid, with constant agitation, until the colour of the isatin 'has disappeared.It cqstal- lises in slender, white needles, melts at 220", is practio~~lly insoluble in water, sparingly solnble in benzene and chloroform, readily in ether and in alkalis. When potassium femicyanide is added to an alkaline solution, a deep reddish-violet coloration is produced. The acetyl-derivative, C22H17N04, orystallises in colourless needlw, and melts at 185". Anidisatin, C2,Hl,NQ,, is obtained by eondensation from a mixture of anisoil with excess of isatin. It crystallises in colourlew needles, melts a t 65", is soluble in most solvents, butinot in alkalis. Dimethy Znnilinisatin, XH<-%f:> ( C,&NMe2),, is prepared by heating isatin with an excess of dimethylaniline and zinc chloride on the watesbath fur .5-6 hours.It mystallises in colourleSfi, lustrous, well-formed prisms, melts a t 234O, is insoluble in water and alkalis, sparinglysoluble in ether, alcohol, and light petroleum, readily soluble in dilute acids. When oxidised, it yields a product that seems to be identical with Figcher and Schmidb's ortbamidabenzaldehyde- green (Abstr., 1884, 1315). Simultaneous~Oxidation and Reduction by Means of Hydro- cyanic Acid. By A. MICHAEL and G. M. PALMER (Anler. Chem. J., 7, 189--194).-Benzil, when treated with alcoholic potassium cyanide and concentrated hydrochloric acid is converted almost quantitatively into benznld ehyde and ethyl benzoate.Strong aqueous hydrocyanic acid at 200" effects (the same change. Benzoquinone, when treated with alcoholic potassium cyanide and hydrochloric acid is converted into benzoquinol, and an oily liquid not fully examined, but probably ethylbenzoquinol. Benzo'in is converted into benzaldehyde and ethyl benzoate. Benzaldehyde when heated at 200" with alcohol and hydrocyanic acid yields benmic acid and ethyl beneoate, probably also benzyl alcohol. The work is being continued. H. B. Nitronaphthoic Acids. By A. G. EKSTRAND (Ber., 18, 2881- 2%7).-A discussion of the constitution of the nitronaphthoic acids obtained by the nitration of a-naphthoic acid, and melting at 215" and 239" respectively (Abstr., 1885, 548). Both acids are converted intoo dinitronaphthalenes, the former yielding the p-, the latter the A.J. G.156 ABSTRACTS OF CHESIICAL PAPERS. a-compound. As the a-dinitronaphthalene yields mononitrophthdic acid [NOz: COOH : COOH = 1 : 2 : 31 on oxidation, t'he N02-qroups 8s also the NOz- and COOH-groups in the nitronaphthoic acid are in the positions 1 : 4'; then in the p-dinitronaphthane and its cor- responding nitronaphthoic acid, the groups will be in the position 1 : 1'. The nitro-acid melting a t 239' can be converted into a chloro- naphthoic acid melting a t 245", which on nitration yields a nitro- chloronaphthoic acid, melting a t 225" and crystallising in prismatic needles; its ethyl salt crystallisea in tables melting a t 125". On NH reduction, the acid is converted into an anhydride, CI,H3C1< co>, crystallising in yellow needles, and melting a t 270".The ready formation of this anhydride points to the contiguity of the a-positions By A. CLAUS and M. KNYRIM (Ber., 18, 2924-2930) .-This acid is formed when a-naphthol dis- solved in glacial acetic acid is sulphonated a t a temperature below 75". It forms long, slender, deliquescent needles, melting at 90" (uncorr.). A dilute solution of the acid decomposes when boiled, with separation of a-naphthol. The sodium salt forms white, lustrous plates readily soluble in water ; the potussium salt crystallises in colour- less needles, also readily soluble in water. The barium and lead saZts (each with 1 mol. H,O) were prepared. When the sodium salt is treated with phosphorus pentachloride in presence of chloroform, dichloronaphthol, C,,H,Cl,O [OH : C1 : C1 = 1 : 2 : 31, is formed ; this compound sublimes in white needles, melting a t 101" (uncorr.), and is readily soluble in chloroform, alcohol, ether, benzene, &c.The sodizrm and barium salts are readily soluble. Phosphorus penta- chloride acts on dichloronapht8hol at 140°, yielding trichZorona~htk,aZens [Cl, = 1 : 2 : 31 melting a t go", and probably identical with that obtained by Faust and Saame (this Journal, 1872, 64), and that of Atterberg (this Journal, 1876 [ii], 51 6). When dichloronaphthol is heated with dilute nitric acid a t 200", it yields phthalic acid. Chromic anhydride converts it into dichloronaphthsquinone, LO : G12 : 0 = 1 : 2 : 3 : 41. N. H. M. By J. BREDT (Ber., 18, 2989-2990).- Camphoronic acid has the formula C9H,,0,, and not C6HL004, that ascribed to it by Rudzinski (Inaug. Diss., Wiirzburg, 1879).When slowly distilled it loses water and carbonic anhydride, yielding iso- butyric acid, and the anhydride of a new acid, C6H,,O4(?), melting at 135". The caZcium salt, C,H,,OICa + 2+H20, and the siher salt, CiHloOdAg2, were prepared. Note.-The formulse of the new acid and its salts are given as printed in the original. Fluorescent Constituent of Atropa Belladonna. By H. PASCHKIS (Arch. Phurrn. [3], 23, 541-543).-10 kilos. of ripe belladonna berries were extracted with strong alcohol, the solution evaporated to diyess, the residue taken up with hot water, and the acid liquid thus obtained, agitated with chloroform. The residue of the nitro- aud carboxyl-groups respectively. v.8. v. a-Naphthol-p-sulphonic Acid. Camphoronic Acid. N. H. M.ORGAXIC C'HEJIISTRY 157 obtained on evaporation of the chloroform extract was recrystallised from hot concentrated alcohol, from 40 per cent. alcohol, and finally from water. When pure, the substance crystallises in yellowish-white, slender needles, seemingly rhombic pyramids ; it melts at 197-198". I t dissolves sparingly in cold water and in ether, more easily in hot wat,er, chloroform, arid in concentrated alcohol, and very easily in hot alcohol, ethyl acetate, acetic acid, and alkalis. Amy1 alcohol and benzene extract it from its aqueous solution. The aqueous solution reacts faintly acid ; the aqueous, alkaline, and especially the ammo- niacal and alcoholic solutions, show a splendid blue fluorescence.The fluorescence disappears on adding acids, but alkalis cause its re- appearance. The sulphuric acid solution when nearly neut<ralised with arnmonia shows a fine purple-violet colour by reflected light, but is colourless by transmitted light. The aqueous solution gives a beautiful blue precipitate with gold chloride, and a green oue with iron chloride ; alkaline copper solution and ammoniacal silver nitrate solution are reduced on warming. In slightly concentrated nitric acid, the substance dissolves with a yellow colour, which becomes blood-red on the addition of ammonia (reaction of mculin according to Sonnenschein). The substance seems to be identical with scopo- letin, obtained by Eijkman from ScopoZia japonica (Abstr., 1884, 404).The yield is only about 0.001 per cent. A New Nitrogenous Constituent of Plants. By E. SCHULZE and 3:. BOSSHAHD (Zeit. ph,z/sioZ. Chem., 10, 80--89).-The authors give the name vernine to this substance, and prepare it as follows; the young plants are dried, and extracted with hot water ; the extract is precipitated by lead acetate, and then by mercuric chloride. The precipitate produced by the latter reagent is collected, washed with cold water, and treated with hydrogen sulphide, the filtrate is neutra- lised with ammonia, and concentrated in a water-bath. On cooling, a jelly-like amorphous substance and asparagine crystals appear, these are collected, and the amorphous substance dissolved in hot water ; on cooling this solution, crystals of vernine form. Vernine may be also separated from asparagine by fractional crys tallisation, vernine crystallisirig first. It crystallises in long, thin prisms of the formula C,H,,N,Os + 3Hz0 ; gives precipitates with silver nitrate, mercuric chloride, phosphotungstic acid, and with copper acetatre.It does not dissolve cupric oxide; it is slightly soluble in dilute hydro- chloric and dilute nitric acids. On evaporating the nitric acid soliition to dryness and adding ammonia, the residue is turned reddish- yellow. The silver compound has the formula CI6H,&g,N,O8. Guanine is formed amongst other products when vernine is heated with hydrochloric acid. Vernine occurs in Vicia sativa, Tr{foZium pratense, ergot of rye, Medicago sativa, Piims siluestris, &c. ; the quantity present in ergot being 0.1 per cent., in vetch 0.05 per cent.of the dried plant. Action of Phosphorus Pentachloride on Santonin. By B. PAWLEWSKI (Ber., 18, 2900--2901).--If equal inolecular proportions of santonin and phosphorus pentachloride are heated together, and the J. T. W. D. H.158 ABSTRACTS OF CHEMICAL PAPERS. crude product crystallised from ether, a m onoehZoro-der.ivatirrp, C,,H,,C102, is obtained in the form of small crystals melting at 125‘, readily soluble in benzene, sparingly soluble in alcohol. If two molecules of phosphorus- pentachloride are. used, a dichloro-derivative is formed ; this can best be mptallised from a mixture of benzene and petroleum. It is a pale yellow substance, melting at 182”, insoluble in water, sparingly soluble in alcohol.Thus the two hydroxyl groupings, in santonin are successively replaced by chlorine, but it appars probable thatt these groups are difterent in function. V. H. V. Reactions of Iodine, Chlorrde with AlkaloYds. By A. D~TTMAR (Ber., 18, 1612--1622).-When yuinoline is treated with iodine chloride, quinoli.ne-chZor,~od~de,. C,H,NICI, is obtained as a yellow precipitate ; this is acted on by ammonia, yielding a dark green com- pound, C9H7NH2T, which when warmed with alcohol decomposes with evolution of nitrogen and ammonia, and formation of quinoline and of a compound, C9H7PU’12. It is therefore probably a molecular compound. This characteristic yellow precipitate, giving t,he ammonia reaction above described, is obtained by the action of iodine chloride on all sub- stances containing pyridine nuclei, with the exception of a few quino- line-derivatives.Several chloriodides are described. Substitution in the pyridine-ring does not prevent the reaction from takihg place, but influences the results ; f o r instance,.qztinaldine chloriodide reacts with ammonia only when warmed. Hydroxyquinolines, hydroxylated in the benzene-ring, reach differently with iodine chloride ; the products do not react with ammonia. The author expects, with the help of this difference of behaviour, to be able to determine the presence or absence of substitution in oertain directions in the alkalo’ids. The reactions of the alkaloids with iodine chloride are described, All alkalo‘ids which react with iodine chloride and yield the charac- teristic bright yellow precipitate which gives the ammonia reaction, contain one or more pyridine nuclei, the number of the latter, corresponding, as a rule, with the number of halogen-groups in the product.N. H. M. Method for Determining Positions in the Pyridine Series. By A. LADENBURG (Bey., 18, 2967--2969).-The fact that cincho- meronic acid, when heated, yields two monocarboxylic acids (nicotic and isonicotic acids) excludes the constitution az’ and pp’. The position aB, as belonging to quinolinic acid which when heated yields nicotic acid, is excluded, as is also the position ap’. The only positions which now remain are ay and &, from which it follows tliat either nicotic or isonicotic acid has the carboxyl in the y-position ; nicotic acid must, however, have the carboxyl-group in the Z- or P-position, as it can be obtained from quinolinic acid : hence isonicotic acid has the constitution, [N : COOH = 1 : 41.When cinchomeronic acid is reduced, cinchonic acid is formed ; this, when distilled yields pyrocinchoiiic anhydride, the acid corre- sponding with which can be obtained from a-dichloropropionic acid, and must therefore contain adjacent carboxyl-groups. I n nico tic acid,ORGANIC CHEMISTRY. 159 the carboxyl must therefore have the &position, and in picolinic acid the only other position : namely, the a-position. Ethylpyridine and Ethylpiperidine. By A. LADENBURG (Bw., 18, 2961-2967 ; compare Abstr., 1885, 992).-The product obtained by heating pyridiiie ethiodide a t 290" yields three bases: a-ethyl- pyridine, ty-ethylpyridine, and a-y-diet8hylpyridine.The platinochloride melts at 168-1'70", and dissolves readily in water ; the h.ydrochZoride melts a t about 110'. When oxidised, the base yields picolinic acid, and a small quantity of isonicotic acid (from the yderivative present as impurity). Yhe base when reduced yields a-ethylpiperidine, which was previously prepared (Abstr., 1884, 1054) but described as 7-ethylpiperidine. The platinochloride melts at 178". y - E t h y l p p i d i n e boils a t 164-166". Sp. gr. = 0.9592 at 0"; 0.9358 a t 20". It is sparingly soluble in water, and has an offensive odour. Its reaotions resemble those of the a-compound. The ylatinochloride crystallises in well-formed plates melting a t 208" The gold salt forms gold-coloured, lustrous prisms, which melt a t 138".When oxidised the base yields only isonicotic acid. When reduced, a base, C7H15N, is formed, which boils at 156-158" ; this is sparingly soluble in water, and has a dis- agreeable odour resembling that of piperidine. Sp. gr. = 0.8759 a t 0". The platinochloride forms yellow plates sparingly soluble in cold water ; it melts at 173-174". a-.l-DiethyZpyridine, C9HI3N, is formed only in small quantities ; it boils at 187-188", has an unpleasant odour, and is sparingly soluble in water. N. H. M. a - E i h y l p y r i d i n e forms the chief pmduct ; it boils a t 150". The picrate melts a t 163". The gold salt melts a t 105". When oxidised it yields a-ylutidioic acid. N. 8. M. Metachloroquinoline. By W. LA COSTE (Ber., 18,2940-2942). -The author has found that the metachloroquinoline previously examined by him (Abstr., 1885, '792) is a mixture of chloroquinoline melting a t 31-32", and metachloroquinoline, which is a liquid a t the ordinary temperature and boils a t about 257". The dichromate of the solid derivative forms long, slender, bright yellow needles which melt with decomposition a t 165" ; metachloroquinoline dichromate crystal- lises in nodular-groups of very small needles melting a t 109".The solid base is acted on by nitric acid with formation of a compound previously described as a-nitro-metachloroquinoline (compare Abstr., 1884, 1196) ; metachloroquinoline, when nitrated, yields p-nitrometa- chloroquinoline. N. H. M. Toluquinolines Substituted in the Pyridine-ring. By I,. R~GHEIMER and R.HOFFMANN (Her., 18, 2979-2989) .--.-P-y- Trichloroparat oluquinoline (me thy1 trichloroquinoline) ( Abstr . , 1884, 1023) can also be prepared by the action of phosphoric chloride on paratoluidine mnlonate dissolved in dry benzene ; the product is treated with water and with soda, and distilled with steam. BecJides t~~lu;lorotoluquinoiine, dichloracetoparatolnide is obtained ; the two substances are separated by means of concentrated hydrochloric acid.1 GO ABSTRACTS OF CEEMICAL PAPERS. Trichlorotoluquinoline is a feeble base readily soluble in strong acids, but is precipitated by adding water. p-y-DiclaZoroparatolucarbo~tyril, CloH,NC1,O [Me : C1, = 3 : 3' : 4'1, is obtained by heating trichlorotoluquinoline with dilute hydrochloric acid for five hours a t 180"; it forms slender needles insoluble in water, sparingly soluble in alcohol and ether, and melts at 290-292", becoming brown a t the same time.It has both feeble acid and basic properties. The potassium salt forms lustrous plates which are decomposed by water. When a solution of the base in sulphuric acid is sahrated with nitrous acid, being kept cold all the while, and the product poured into water, 9-7- d ich lorodinitroparatol ucarbostyril, C,oH,NCl,(N02)2, is foimed. This crystallises from alcohol in long, lemon-coloured needles which melt at 186". Monoc h 1 orodiet hox y p arat o lug uin o line, C,NH,MeCl(OEt), [OEt : OEt = 2' : 3' or 4'J, is prepared by heating trichlorotoluquinoline with a solution of sodium in anhydrous alcohol for two hours a t loo", and then for four hours at 130"; the product is filtered and washed with water.It forms long, colourless needles melting a t 70*5-71*5". Dichloroh ydroxyort hotoluqui?zo line, C9NH3MeClz*OH [Me : C1, : OH = 1 : 2' : 3' : 41, is obtained by the action of phosphoric chloride on hydrogen orthotoluidine malonate, and forms microscopic needles which me1 t a t 245" ; it is sparingly soluble in water, alcohol, and glacial acetic acid. It dissolves in dilute, but more readily in concentrated acids ; it also dissolves in carbonates. When heated with phosphoric chloride for 1$ hours at 125", it yields 2' : 3' : 4' trichlorortl~otoluquinoline, C,NH,Cl,Me, which resembles in appearance trichloroquinoline and trichloroparatoluquinoline ; it melts at 111-112*5". It dissolves readily in concentrated hydrochloric acid, and is precipitated by the addition of water.Dilute hydrochloric acid acts on it a t 180" with for mation of dichl ororthotolucarbost~ril, CSNH,MeC1,*OH [Me : C1, : OH = 1 : 3' : 4' : 2'1. This compound melts at 287-288", and when strongly heated, sublimes ; it is insoluble in water, sparingly soluble in boiling alcohol, but dissolves readily in alcoholic potash. H y droxychlororthotolucarbostyril, CSNH3MeC1(OH), [Me : C1 : (OH), = 1 : 3' : 2' : 4'1, is formed when 4' : 2' : 3' hydroxydichlororthotoluquinoline is heated with dilute hydrochloric acid for five hours a t 160". It crystallises in lustrous plates melting a t 276-277", and is readily soluble in glacial acetic acid, in ammonia, and in alkaline carbonates.It is insoluble in water, and sparingly soluble in alcohol. Dichloracetortl~otoluide, CcH4Me*NH*CO*CHCI,, prepared from orthotohidine malonate, crystallises in needles, which are very readily soluble in alcohol and ether, sparingly soluble in light petroleum. It dissolves slowly in dilute soda. When warmed with caustic alkali, itORG-4INIC CHEMISTRY. 161 decomposes, giving off an odour of isonitriles. Phosphoric chloride acts 011 it with formation of a mixture of cii- and tri-chlorinated quinolines. DichZoracetometatoZuide, C,H,Me*NH*CO*CHCI,, forms slender, colourless plates with silky lustre, melting a t 98-100". It is decom- posed when warmed with alkaline carbonates, and yields an oil having the powerful odour of isonitriles. N. H. M. Formation of Quinoline-derivatives by the Action of Phos- phoric Chloride on the Malonates of Primary Aromatic Bases.Ry L. R~~GHEIMER (Ber., 18, 2975--2978).-A discussion of the theoretical bearings of the results described by the author in other papers (Abstr., 1884, 1050, and preceding Abstract). Formation of Quinolines from Meta-substituted Amines. By L. MEYER ( R e r . , 18, 2902--2903).-This paper is a preliminary notice regarding the production from paraxylidene sulphate of a dimethylquinoline boiling a t 265" under 736 mm. pressure and of sp. gr. 1.070 a t 21". It is converted into a methylquinolinecar- boxylic acid by nitric acid. This acid, when heated, loses carbonic anhydride, and yields a methylquinoline, possibly identical with that obtained from metatoluidine. V. H.V. Synthesis in the Quinoline, Series. By F. JUST (Ber., 18, 2632--2635).-When ethyl anilbenzenylmalonate; PhN : CPh.CH(COOEt), (this ~ o l . , p. 149), is heated a t 150°, it is decomposed into ethyl alco- hol and eth y 1 p h e n y lhydroz y lq uino linecnrbmy 1 ate, OH*CgNH,Ph-COOEt [Ph : COOEt : OH = 2' : 3' : 4'1 ; it is colourless, crystalline, and melts a t 2623 The f r e e acid is obtained by heating the ethyl salt with hydrochlorib auid at 120", and melts a t 232"; on further heating, it is convertedrinto a hydroxy- quinoline which, when distilled with zinc-dust, yields the known n-phenylquinoline [Ph = 2'1, thus confirming the oonstitution de- duced from the method of formation. The author intends to apply this method to the preparation of substituted quinolines, preparing in the first place substituted anilbenzenylmalonates by t b e action of ethyl sodomalonate or its substitu tion-derivatives on substituted benzanilimide chlorides, and thus obtaining quinoline-derivatives of known structure.A. J. G. Reduction of Nicotine. By A. LIEBRECHT (Be7*., 18, 2969- 2970) .-Dipiperic%yZ, C,oH,,N,, is obtained by reducing nicotine in alcoholic solution with sodium. The platinochloride forms dark red crystals which melt a t 202" ; the hydroch Zoride, aurocldoride, and picrate are described. D i n i t r o s o d ~ ~ i ~ e r i d y l , N0.C,NH,*C,NH9*N0, is pre- pared by the action of sodium nitrite on the base. N . H. M. By A. KRAKAU ( J . Russ. Chem. SOC., 1885, 356--366).-A mixture of cinchonine Action of Caustic Alkalis on Cinchonine.VOL. L. m162 ABSTRACTS OF CHEMICAL PAPERS. and pure soda was heated in a flask and, as soon as the t'emperature had reached 170-190", a current of superheated steam passed through the apparatus, the reaction being conducted generally at 195-210". A yellowish, optically active oil distils over with the steam. This product, a mixtare of different substances, was redis- tilled with steam, when an optically inactive oil passed over, whilst a viscous heavy oil remained, which contained some cinchonine, but not enough to account for the optical activity of the original pro- duct, and another substance not yet fully investigated. The inactive oil, on being redistilled, passed over between 240" and 265" ; its alco- holic solution was treated with alcoholic sulphuric acid, when crystal- lisation at once took place.The pink crystals, separated from the brownish-red mother-liquor, after being boiled with absolute alcohol and repeatedly crystallised from acetic acid, melt at 228-229" ; they are insoluble in ether, chloroform, and benzene, easily soluble in water, and were found to be almost pure lepidine bisulphate. The pink substance becomes colourless by treatmetit with animal charcoal, the melting point remaining unchanged. In the brown mother- liquor, quinoline bisulphate (m. p. 163.5-164.5 ") was found. The bases lepidine and quinoline, and some of their salts, were pre- pared from the bisulphates. As the former was obtained in a state of greater purity than by any other investigator, a more detailed descrip- tion of it is given : it is an oil distilling at 205.5" (bar.746.7 mm.), of sp. gr. 1.0995 a t 0" and 1.0862 a t + 20" ; the author prepared the dichromate (begins to decompose at 136-138"), the picrate melting a t 212-21 3", the platinochloride, and the aurochloride melting at The optically active oil formed in the reaction simultaneously with lepidine and quinoline (resembling cinchonine in its properties) seems to be produced in the early stages of thereaction of caustic alkalis on cinchonine ; indeed, if the reaction is carefully conducted without the use of superheated steam, the oil is found in the product without any lepidine or quinoline having been formed. The investigation of the oil is continued. I n another paper (p. 282) the author states that by the action of caustic alkalis on cinchonidine, quinoline, lepidine, and a dextrorotat0r.y viscous oil are formed.From quinine and quinidine he has obtained an amorphous optically active substance and two optically inactive bases, one of which is easily converted into a hydrate melting at 52". By A. MICHAEL (Amel.. Chern. J., 7, 182--1f33).-The best results were obtained by heating 6 grams of cmstic soda, 6 grams of cinchonine, and 60 C.C. of absolute alcohol a t 130-135" for 8-10 hours; no gaseous products were formed. The contents of the tubes were freed from alcohol, a large quantiLy of water added, and the whole extracted with ether. The ethereal extract when evaporated and distilled with steam yielded a very small qua.ntity of volatile bases, about 1 per cent.of the cinchonine employed. The bases not volatilised by steam amounted to over 80 per cent. of the cinchonine employed; thcy could not be separated by distillation, but fractional precipitation 188490". A. T. Decomposition of Cinchonine by Sodium Ethoxide.ORGANIC CHEXISTRY. 163 with platinum chloride showed that the material was almost perfectly Lomogeneous. The free base, C2,,Hz6N2, is a heavy, reddish-yellow, viscous oil ; the salts are, so far as examined, amorphous, except the platinochloride, C20H26N2,H2P t Cl,. The aqueous alkaline solution, left aft,er extraction with ether, contains formic acid. The reaction is thereFore probably expressed by the equation C19H2,N20 + EtONa = C,,H,,N,Et + HCOONa ; whence cinchonine would be an amide of the base CIEH2?NZ, and of formic acid; the volatile bases obtained by other experimenters, are decomposition products of the base here described.H. B. Artificial Preparation of Cocaine and its Homologues. By W. MERCK (Bey., 18, 2952-2955 ; compare Abstr., 1885, l.249).- Cccaine can be prepared by heating anhydrous ecgonine with benzoic anhydride and methyl iodide for 10 hours a t 100"; the product ir poured into water, purified by extraction with ether and filtration through animal charcoal, and the base is liberated by means of sodium carbonate ; +#he yield is small. C o c e t h y h e , C18H23NOi, is prepared by heatina benzoylecgonine with ethyl iodide and alcohol for eight hours at 103. It crystallis(*s from alcohol in splendid prisms with vitreous lustre, melting a t 108-109".The platinochloride forms bright yellow rhotnbic plates ; it resembles cocaine platinochloride, but is more crystalline. Like cocaiiie, the base is an anzesthetic. N. H. M. Lupanine, an AlkaloYd from the Seed of the Blue Lupine. By &I. HAGEN (AnnaZen, 230, 367-384).--The seeds of the blue 1 upine, Lupinus arhgustifolius, contain a liquid a1 kalo'id, lzcpanine, CI5H2,N2O, but do not contain either of the alkalo'ids Inpinine, C21Hao~,Oz, or lupinidine, CRHliN, which Baumert (Abstr , 1881, 831 ; 1882, 229, 873; 1883, 100, 224) found in Lupinus luteus. The alkalo'id is extracted from the seed by Liebscher's process (Bey. landw. Institut zu Halle, Heft 11). Lupanine is a thick, non-crystallisable syrup, possessing a bitter taste and a strongly alkaline reaction.l t has a pale-yellow colour, and exhibits a green fluorescence. Lupanine attacks the skin, and fumes in the presence of hydrochloric acid. It is precipitated from its salts b y soda and potash, but liberates ammonia from its compounds. The alkaloid is sparingly soluble in water and alcohol, but is freely soluble in ether, chloroform, and light petroleum. The liquid does not boil a t 290" under a pressure of 130 mm. The 7~ydriodide, C,,H,N,O,HI + l$H,O, forms large, monoclinic crystals, which are sparingly soluble in water and alcohol. The hydrochloride, C,,H,,N,O,€€Cl + 2H20, appears to crystnllise in the quadratic system. It is a hygro- scopic salt, soluble in water and alcohol, but insoluble in ether; it melts a t 127". The thiocyanate, Cl5H2,N,O,HSCN + +K,O, forms transparent crystals, soluble in hot alcohol.The sulphate and oxalate do not crystallise. The platinochloride, C,,H2,N,O,H2PtCl6 + 3+H20, is not m 2164 ABSTRACTS OF CHEEhIICAL PAPERS. distinctly crystalline ; it is sparingly soluble in cold water and cold alcohol, and is insoluble in ether. Tlie aurochloride forms silky, golden needles, insoluble in water, alcohol, and ether. Lupanine unites with methyl iodide to form the methiodide, which is decomposed by moist oxide of silver, yielding the hydroxide, CI5H,,N20,MeOH. This base exists as- a colaurless syrup. It unites with acids, forming tx series of mystallina salts. Like lupanine, it forms an acid platinochloride, CI,H2,N,0,MeHPtC1, + H20. The nurochZoride forms triclinic needle-shaped crystals, soluble in hot water.w. c. w. Alkalo'ids in Old Flour.. By BALLAXD ( J . Pharm. [ 5 ] , 11, 341- 342).-Flour kept in sacks for some time, shows traces of the presence of alknla'ids, arvd later the quantity formed becomes more and more appreciable. The flour is extracted with ether ; the solu- tion thus obtained gives on evaporation a fatty residue which is acid, especially in th'e case of very old flour ; its odour is disagreeable and penetrating, and its tast'e is very acrid. The presence of alka- loids in an aqueous extract of the residue can readily be detected by means of suitable reagent$. Flour112 to 18 months old gives sensible amounts. The extract administered t o sparrows kills them after several hours, whilst fresh flour gives no such results.J. T. New Method of Separating Globulins from Albumins. By V. M~CHAILOFF ( J . Russ. Chem, SOC., 1885, 348--354).-1n a former communication (Abstr., 1885, 69) a method of preparing pure albumin was described, which consists in precipitating filtered white of egg with ammonium sulphate and dialysing the precipitated albu- mino'id matter, after dissolving it in water. Tlie present paper is a description of the separation of the diserent albumino'id bodies con- tained in the serum of blood. A convenient volume of serum (20- .50 c.c.) is saturated with solid ammonium sulphate until the whole of the albumino'id matter is precipitated. The precipitate is thoroughly washed with saturated ammonium sulphate solution, to free it from other mineral salts, dissolved in the smallest possible volume of water, and placed in a dialyser.After 2-3 days' dialysing, water is added to the solution, which is then filtered. The whole of the globulins remain on the filter, whilst the albumin passes into the filtrate. On sahrating this with magnesium sulpllate at 30°, not the slightest precipitate is formed. The author considers that globulin and albumin originally form a complex group in the serum, which, after eliniination of the mineral salts, is split up by the action of an excess of water. It is noticed that on concentrating the dialysed mixture of serum, globulin, and albumin a t low temperatures (70- 75"), the globulin precipitate disappears as soon as a certain degree of concentration is reached. The existence of a compound of albumin and globulin in the serum is the more probable, as the reaction of albumin is acid (Zoc.cit.). As regards the globulins, or at least sub- 8tances closely related t o them, some data established by DanilevskyORGANIC CHEMISTRY. 165 (Cenfr. Med. Wiss., 1880, 51) seem to point to their alkaline cha- racter. A. T. The Haemoglobin Molecule, By 0. ZINOFFSKY (Zeit. physiol. Chem., 10, 16-34) .-Former analyses of hmmoglobin have shown that the molecule contains at least 600 atoms of carbon. This is a minimal number reckoned on the basis that only one atom of iron is present. Sulphur i8 also it constituent of hemoglobin, but previous determinations of the amount present show very contradictory results : hence the .supposition. first advanced by Lehmann, that the crjstallised substance hemoglobin is not a chemical unit, but consists of haematin, which I contains iron, mechanically mixed with a crys- tallised proteid.A seeming confirmatiola of t h i s theory has been recently advanced by Struve (Zeit. p a c t . Chew,., lM4), who found that by means of alcoholic ammonia, hsmatin could be extracted from tlie crystals, leaving them colourless. The author, however, shows that the conflicting results as to the ,quantity of sulphur present are due to bad methods of preparation of hernoglobin, and that hzemoglobin is, after all., a chemical unit. The method of preparation is a s follows :-The red corpuscles are collected from defibrizrated horse's blood, mixed with three times their volume of distilled water, the mixtwe warmed to 35", anci the hzemoglobin thm dissolved.The colourless stromata of the corpuscles lloat in the liquid, but are too small to be .separated by filtration. They are, therefore, dissolved by adding a smadl quantity of ammo- nia or ether. If ammonia is used, it must be afterwards neutralised by dilute hydrochloric acid. Cry stallisation of the hzemoglobin is brought about, by the addition to the liquid of a quarter of its volume of alcohol, the mixture being kppt a t 0" for 48 hours. The crystals form abundantly, are filtered off, washed with 75 per cent. alcohol a t O", redissolved in water at 35", and purified by repeated recrys- tallisation. By this method three preparations of pure haemoglo bin were made and submitted to analysis, and the ratio of iron to sulphur atoms found to be as 1 : 2.The formula deduced for hzemoglobin is C712H,,,N2,,S,Fe02~. The author further oonsidets that as decom- position-products of hzemoglobin, one molecule of hematin with 34 atoms of carbon, and two molecules of proteid (globulin), each with one atom of sulphur and 339 of carbon, are formed. He, how- ever, thinks it probable that each molecule of prote'id contains four atoms of sulphur and 1356 of carbon (that is, granting that peptones are decompositiou-products of prote'id, and that each molecule of peptone probably contains two atoms of sulphur united in different ways). W. D. H. Action of Ammonia on Hsmin. By M. SHALF~EFF ( J . Russ. Chent. SOC., 1885, 203-204). - Hamin crystals, when treated with an alcoholic solution of ammonia, become colourless, without losing their crystalline form or undergoing any change in volume ; the ammoniacal solution deposits brown, translucent, globular aggre- gates of needles. These crystals show double refraction in a higher degree than haemin crystals, whilst the colourless crystals have en-166 ABSTRACTS OF CHEMICAL PAPERS. tirely lost this property.of hEmin, heeminostromine, the colouring matter, haeminic acid, The author term., the colourless constituent A. T. By W. F. LOERISCH (Zeit. physiol. Chem., 10, 40--79).-The most important recent work on mucin is that of Landwehr (ibid., 6, 7 , 8, 9). Previously it was known that much mas an albumino’id, soluble in dilute alkalis, precipitable by ac3tic acid, and that after heating with dilute sulphuric acid, a reducing substance of unknown nature is formed.The author holds that a prote’id and a carbohydrate are the products of decomposition of mucin, and that mucin is not merely a mechanical mixture of two such substances, as Landwehr supposes, but probably a glucoside. He prepares mucin by precipitating a lime- water extract of the tendons with acetic acid. After 24 hours, the length of time the lime-water and the tendons are in contact does not cause more much to be dissolved, nor does the temperature of the lime-water make any difference. Boiling causes mucin t o be no longer precipitable by acetic acid; 1 to 5 per cent. acetic acid is the best strengt’h of acid to use, weaker acid causing only a cloudiness, not a precipitate. Unlike Landwehr’s mucin (from saliva and snails), tendon-mucin is not chanqed into coagulated prote’id by boiling or by remaining under alcohol.The amount of mucin may be estimated not only by weighing the dried acetic acid precipitate, but by the decrease of alkalinity of an alkaline solution employed to dissolve it, mucin having an acid reac- tion. The author’s formula for mucin is C1,H2JV3,S08,,. By heating with dilute sulphuric acid, it yields a carbohydrate of the formula C,,H,,O,,; by still further heating, a reducing sugar, C61y1206, is obtained; this differs from Landwehr’s “ animal gum” in forming a clear solutiou with water ; a prote’id is also formed. On Mucin obtained from Tendons of the Ox. W. D. H.ORGAXIC CHEXISTRP.B. p.CHZCIZ.. .... 40-41"COCl, ...... 8"CH,*CHCl2.. .. 60135B.p.CO(OEtj, ...... 126CHz(0Me)2 ..... 42"CH,*CH(AcO), . 169Organic Chemistry.Volatility of Mixed Derivatives. By L. HENRY (Compt. r e d . ,101, 816--818).-The boiling points of mixed derivatives of the type= CXX', which contain equivalent radicles X and X' of malogousfunctions are the means of the boiling points of the correspondingsimple derivatives, CXz and CXf2. The following kable containsexamples selected from the large number given by the author.B. p.CH2C1,. ........ 41.0"CO(OMe), ..... 91.0CH,*CH(OMe), 64.0CHzBr*CHCl2 . . 187-138"CHCI, ........ 61.2CH,*CHC12. ... 60.0B. p.CH,Br,.. ...... 98.0"OHClBr, ...... 1233-125"CO(OEt),. ..... 126"CH,*CHBrz .... 110CHs*CH(OEt)z.. 104CHzBr-CHBr2.. . 186-187"B.p.CH,ClBr ............... 68-69"CHC1,Br ............... 91-92OMeCOOEt ........... 109"CH3*CHCIBr ....... : .. 843-85"OEt-CHMe-OMe ....... 85"CHzBr*CHCIBr ......... 162-163136 ABSTRACTS OF CHEMICAL PAPERS.Analogous relations are observed in the case of mixed polycarbonderivatives, XC . . . CX' in which the two radicles are combinedwith different atoms of carbon. C. H. B.Formation of Propylene from Glycerol. By A. CLAUS (Bar.,18, 2931 ; compare Abstr., 1882, 1038).-The yield of propylene issatisfactory only when a large amount of glycerol (1 kilo.) is distilledas quickly as possible with twice its weight of zinc-dust. West-phal has shown (I72aUg. Diss., Freibnrg, 1877), that acraldehyde, alljlalcohol, and two condensation products, CsHl,O and C12H,,02, boil-ing a t 140" and 200" respectively, are formed in the reaction.Both.condensation compounds when oxidised yield propionic acid andcarbonic anhydride. N. H. 31.Action of Chlorine on Trimethylethylene. By N. KONDAKOFP( J . R ~ S . Chem. Soc., 1885,. 290-319) .-Trimethylethylene may beprepared either by the action of dilute sulphuric acid on tertiaryamyI alcohol, or by treating tertiary amyl iodide with alcoholic potash ;as the amylene obtained by the first method contains as a rule anadmixture of asynimetrical methglethylethglene, the author used thelatter mcthod in most of his experiments, Tertiary amyl iodidedistils almost entirely at 124-125", net at 127-129" as stated byother investigators. The amylene obtained from this iodide wasconverted into bromide, and fhe latter heated with lead oxide andwater in a sealed tube : methyl isopropyl ketone was formed and notan aldehyde, as would have been the case were methylethylethylenepresent (Eltekoff, Abstr., 1883, 566), When a current of chlorine gasis passed into trimethylethylene (the temperature being either - Noor + 20°, or finally + 38', the boiling point of the hydrocarbon), itwas observed that up to a certain Roint only absorption of the gastakes place, but in a short time this ceases, and hydrogen chloride isevolved until the end of the operation. The products of the reactioirdiffer slightly according to the temperature. In the cold, high boil-ing products (160-180") m e formed along with more volatile com-pounds ; a t the ordinary temperature, the whole of the product distilsbelow 135" ; the compounds obtained a t 38" all pass over below 110".The chlorinated product more espeoially investigated was obtained a tthe ordinary temperature.Seven fractions were obtained on distilla-tion : the first consisted chiefly of unchanged triniethylethylene, thelast did not coritain any unsaturated compounds. The intermediatefractioiis strongly decolorise bromine and contain No. 3 (the mainportion boiling between 90-95"), 64, No. 4, 67, and No. 5, 60per cent. of C,H,Cl. When treated with water, the fractions 2, 3, and4 were entirely dissolved, 5 and 6 dissolved partly, leaving an oil freefrom unsaturated compounds. The aqueous solution contains, inaddition to tertiary amyl alcohol, an unsaturated alcohol, COHi00,boiling a t 115-117"; sp.gr. a t 0" = 0.8571 and a t 20.5" = 0.8419.This unites readily with bromine, reacts with phosphorus penta-chloride, and yields a crystalline sodium-derivative. The bromideand acetate were prepared, the latter boiling at 130-131". Thedata for the etherification of the alcohol, proved it t o be a secondarORGAXIC CHEJfISTRY. 7 37alcohol. By the action of dilute acids at 100" it is transformed intomethyl isopropyl ketone. It is therefore methyl isopropenyl carbinol,CH, : CMe-CHMe-OH, the chlorinated compound obtained fromtrimethylethylene having an analogous structure. The fraction ofthe chlorine-derivatives boiling a t 133-135" contains the chlorideC5Hl0ClLZ, a heavy oil, which is also left when the portions 5 and 6 ofthe distillate are treated with water.A. T.Fulminic Acid. By L. SCHOLVIEN (J. pr. Chew,. [Z], 32, 461-489).-A continuation of Carstanjen and Ehrenberg's work on thefulminates (Abstr., 1882, 816). When dilute sulphnric acid (1 : 5 )acts on sodium fulminate and the mixture is kept well cooled,a yellow liquid is obtained, which o a treatment with ether yieldsan ethereal solution of fulminic acid. This solution is very un-stable, and t'he fulminic acid is rapidly converted into two isomericacids, isocyanuric acid and isocyanilic acid. The presence of freefulminic acid in the ethereal solution was proved by separating itvery rapidly from the mother-liquor,. and shaking it w i t h anaqueous silver solution, when a white precipitate of silver fulminateseparated immediately ; if the ethereal solution was allowed t oremain for ten minutes and then shaken with the silver solution,red silver isocjanurate separated and imcyanilic acid remained insolution.Xsocynizuric acid gives coloured Salk containing one, two, andthree equivalents o€ metal ; when evaporated with hydrochloric acidit yields hydroxylamine; with potash, ammonia is given off. Thepure acid, C,N303H3 + 3Hz0, forms a white, crystalline powder,melting a t 81", and exploding with great violence a t 106".Whenkept for a long time i t is converted into an isomeric acid, p-isoful-minzwic acid; this crystallises in small needles of vitreous lustre, whenanhydrous melts at 196" with decomposition, and is not acted on byhydrochloric acid.Isocyanilic acid, HCNO, crystallises in.white lustrous needles ; whenheated it decomposes without previous fusion; it forms unstable salts,and is not acted on by hydrochloric acid. Boiled with potash i tyields an acid, isomeric with Stideler and Strecker's " Uroxanicacid " ; this forms a dark violet potassium salt.When thiocarbamide is acted on by mercury fulminate, a mixtureof thiocarbamide, mercury thiocyanate, carbonic anhydride, mercurysulphide and carbamide is formed. G. H. M.Decomposition of Butylene and Amylene Hydrate by Heat.By WOLKOFF and BOCGAIEFF (J. Russ. Chem. Soc., 1885, 276).-Rutylene hydra,te (secondary but,yl alcohol) when heated in sealedtubes at 240-250" for 8-16 hours is not decomposed, but if the leastquantity of a hydmcid (hydriodic acid or even methyl iodide) beadded, decomposition takes place a t 220°, and pseudobutylene isformed after the lapse of only five to six hours.Similar observationswere made with dimethyl ethyl carbinol and methyl isopropyl carbinoland some other alcohols ; tertiary alcohols suffer this decompositio135 ABSTRACTS OF CHEMICAL PAPERS.most easily, primary alcohol with much more difficulty ; normalalcohols have not yet been studied in this direction. A . T.Preparation of Hexyl Glycerol. By P. ORLOFF (J. Russ. Chem.SOC., 1835, Abstr., 146) .-Hexylglycernl previously obtained by theauthor from dibromhydrin is best prepared by the action of dilutedaqueous potash on the monochlorhydrin, the latter being formed byaddition of hypochlorous acid to dimethyl allyl csrbinol.The iodhydrinis obtained by the action of mercuric oxide and iodine on dimethylallyl carbinol in the presence of aster. The glycerol itself,'when treatedwith filming hydriodic wid and phosphorus, yields, besides a smallamount of a crystalline compound not yet examined, an iodidedistilling a t 140-150", and converted by alcoholic potash into ahexylene identical with Jawein's (Abstr., 1878, 961). A. T.Decomposition of Galactose and Arabinae by Dilute Acids.By M. CONRAD and M. GUTHZEIT (Bey-., 18, 290%-2907).--Thefollowing results were !obtained by heating 10.5 grams of galactose,59 grams of water, and 4.87-4.N grams of hydrochlopic acid forHumic Undtered Acetopropionic Formicsubstances.galactose. acid. acid.1-60 8-60 2.84 1.051 . i 7 3.05 2.85 1.101'; hoUPfi:-On replacing hydrochloric by sulphuric acid of the same concen-tration, the quantity df the decomposition produd obtained wasconsiderably less.A specimen of arabinose from marc of beet-sugar melted a t 358-160"; its specific rotatory power f o r a 10 pep cent. sdlution mas foundto be [a]= = 104"; on heating 10.5 grams with hydrochloric acidunder the same conditions as above, there were obtained 4.3 gramsof humic subshances, 0.42 gram of formic, and 1.2% gram of aceto-propionic acid. These results tend to show that galactose andarabinose are not identical. V. H. V.Raanose or Melitose from Molasses, Cotton-seeds, andEucalyptus Manna.By P. RISCHBIET and B. TOLLENS (Ber.. 18,2611- 2616).-From a consideration of the properties and reactionsof this substance, and especially from the composition of the sodium-derivative and the amount of mucic acid formed on oxidation, theauthors conclude that it is best represented by the formulaC36H640,2 + 108,O. When boiled for some time with acids, a sugarcry stallising in six-sided tables (probably galactose) is obtained. Acomparison of melitose, from the manna of Eucalypfu.~ viminalis, withraffinose shows the two substances to be identical ; the name melitoseis therefore preferable.Action of Oxymethylene on Amines. By S. KOLOTOFF ( J . RUSS.Chem. Soc., 1885, 229-251). - It, is known that oxymethylenereacting with ammonia forms hexamet.hylenamine ; the author hasA.J. #ORGANIC CHEMISTRY. 139studied the reaction with mono-, di-, and tri-ethylamine and aniline.Ethylmethylanainiize, C3H7N, obtained from oxymethglene and ethyl-amine, is a colourless, alkaline liquid, boiling a t 205-208". Thevapour-density dehermination and the analysis of the platinochlorideshow that the molecule of the compound is not polymeric, onemolecule of each of the constituents entering into reaction. Asolution of the base in hpdrocliloric acid, on remaining in avacuum, is decomposed into ethylamine and oxymethylene.With diethylamine, a similar compound, CH2N2Et4, was obtained asa bright colourless liquid boiling a t 16G-169", and having a well-detined basic character.Triethylamine, ib8 was expected, does notreact with oxymethylene ; thus in the reaction of axymethylene wikhamines, the oxygen of the former combines wifh all the amidichydrogen of the amine-group, forming water, whilst the two remainingradicles, uniting, form basic compounds. Aniline reacts very reacElywith oxymethylene, the mixture a t once solidifying to a basic com-pound, which melts at 137-138"~with decomposition, and forms asolid substance which does not melt even a t 'LC)O", the temperature ofits decomposition. Heated with water at loo", phenylmethylenaminesplits up into aniline and oxymethylene. According to the author themolecule of the compound corresponds not with the simplest,, but witha higher, probably dodbled, formula.Imines.By A. I~ADENBURG (Bey., 18, 2956-2961 ; comp. Abstr.,1883, 910).-Pentarnethylenediamine is prepared by adding sodiumas quickly as possible to a solution of trime ethylene cyanide in boilingdcohol ; the product is poured into water, and the alcohol (distilledoff. A trace of ammonia is evolved, and a small quantity of piperidinegoes over with the aJcoho1. The pentam&hylenediamine' is thendistilled with superheated steam, the distillate treated with a slightexcess of dilute hydrochloric acid, and evaporated $to dryness. Thefree base is obtained by dissolving theiresidue in a little water, addingpotash and extracting with ether. The yield of base is 80 per cent.of the weight of cyanide employed. iIt is a colourless, syrupy liquidboiling a t 175-L78".When expnsed to air, it fumes and absorbswater and carbonic anhydride. It dissolvessparingly in ether, readilyin alcohol and watar. The acetyl-derivative, CaH,o(NHAc)2, is a crgstal-line substance ; it boils above 360". The formation of piperidine inthe reaction is fresh evidence in support of the formula ascribed toit, and also explains i d s relation to h i - and penta-methylene-com-pounds : piperidine is penta~aetli;lllpnimine. l h e author thinks i tprobable that all cyanides may kbe converted ink0 amido-compoundsby the method above desmibed.Ricuhyba nuts, from U y r i s t i c a qiqicilzalis or M. bicuhyba, give thefollowing results on proximate analysis :-A. T.N. H. M.Bicuhyba Fa& By R. NOE8DLIKUER (Bey., 18, 2617-2623).1-20 ABSTRACTS OF CHK1\IlCAL PAPERS.Water ........................ 8.86Ash.......................... 4.50Pat .......................... 17.74Crude fibre.. .................. 30.62Prote'ids ...................... 1 7 f aNon-nitrogenous extractives.. ... 20.66The results of the examination of the fat are very similar tothose obtained by Reimer and Will (Abstr., 1885, 1197) with thefat of the f r u i t of 31. Xuritiamensis ; it consists mainly of trimyristinand triolein with small quantities of resin and free myristic acid, andvery slight amounts. of ethereal oils, volatile acids, and of a non-saponifiable oil. A. J. G.p-Dimethacrylic Acid. By D, OUST.INOFF ( J . BUSS. Chem. SOC.,1885, 439-448). - 13-Diethylenelactic acid, obtained by oxidisingally1 dimethyl carbinol, was distilled with dilute sulphuric acid(comp. Schirokoff, Abstr:, 1880, 382).The dimethacrylic acidformed was purified by converting it into the zinc salt, decomposingthis and crystallising the acid from water; it melts a t 69.5-70'.The sodium, calcium, barium,. zinc,. copper, lead, and silver. salts wereexamined as well as the dibromide, melting at 105--106" and resolidi-fjing a t 76". The author gives a comparative table of the principalsalts and dibromides of dimethacrylic.acid, GMe2 : CH-COOH, and ofits isomerides, angelic, methgrlcrotonic, and allylacetic acids.A m n. I.Oxidation of Oleic and Elaidic Acidsl wibh Potassium Per-manganate i n Alkaline Solution. By A. SAYTZEFF ( J . Rtuss. C'hent.Xoc., 1885, 41i-433).-01eic acid when treated with potassiumpermanganate in the presence of an excess of potash, yields dilzydr-oxystearic acid, C,,H,3(0.H)2*C!OOH, a crptalline acid insoluble inwater, easily soluble in boiling, but sparingly in cold alcohol, and inhot ettier.It melts after repeated purification a t 136*5", and solidifiesagain a t 122-119'. When heated in a sealed tube a t 120-130" withhydriodic acid, or by the action of phosphorus tri-iodide and water,it is converted into liquid iodostearic acid, the latter by reductionwith zinc and hydrochloric acid yielding ordinary stearic acid. Iodo-stearic acid and silver oxide give hydiaoxystearic acid, melting a t83*5-85*5", and solidifying a t 68-63". The dihydroxy-acid isidentical with the isodihydroxystearic acid of Overbeck (Aniaalev,140, 72) ; the description of the properties of the acid given byOverbeck is inaccurate.Dihydroxysteatk acid, when distilled under a pressure of 100 -150 mm., yields a crystalline acid, melting a t 77-79", and resolidi-fying at 69-66" ; the analyt'icsl results approximate to the formulaCleH,O,; it would, therefore, seem to be formed by elimination of1 mol.H,O from dihydroxystearic acid.The oxidation of elaidic acid under the above conditions yields anacid of the same composition as dihydroxystearic acid, but entirelydiffering from it in its properties ; i t melts a t 99-loo", resolidifiefi a ORGASIC CHEMISTRY. 1 d l86-85', and is much more soluble in ether and in ahohol. The smallamount of material did not admit of fiirther study.Oleic acid when treated with potassium permanganate alone seemsto yield azelaic acid, although this could not be obtained in a stateof purity from the products of the reaction.A. T.Lactic Acid from Levulose. By V. SOROKINE ( J . Euss. Chem.Soc., 1885, :368--369).-Amongst the products of the action ofbases (caustic soda and baryta) upon levulose, the author finds lacticacid; it seems, therefore, that the formation of lactic acid fromglucose by the aotion of bases is a reaction characteristic of all thesubstances of this group, similarly to the formation of levulinic acidunder the influence of acids. Experiments are being made in orderto determine the quantity of lactic acid formed in this reaction undervaried conditions. A.T.Action of Ammonia on Succinirnide. By ROUBTZOPF (J.Rztss. Ckem. Soc., 1885, 277-278).-When amrnonia is passed overpowdered succinimide placed in glass tubes and cooled to - 10' or- 20", the tubes being then sealed and heated to 100-200", succin-amide is formed. At the ordinary temperature ammonia is not takenlip, and the amide is not formed. A . T.Ethyl Diacetofumarate. By 3'. JUST (Ber., 18, 2636-2637).-By the action of sodium ethoxide on a solution of ethyl diaceto-succinate and precipitation with ether, the compoundC 0 OE t.CNaAc*CNaAc.C 0 OE tis obtained as a whit'e powder.solution of iodine yields ethyl diacetofumarate,This when treat,ed with an etherealCOOEt-CAc : CAc*COOEt,as a colourless oil which solidifies to long, silky needles, melting at95-5-96'.Non-volatile Product of the Oxidation of the HydrocarbonC,,H,.By A. ALBITZKY and V. NIKOLSKY (J. Russ. Chem. Xoc., 1885,435-439) .-Amongst the products of the oxidation with chromicmixtures, of the hydrocarbon C12H2, from ally1 dimethyl carbinol, a,syrupy acid, not volatilising with steam, has been obtained (Abstr.,1883,1074). The authors have made analyses of its barium, calcium,and ethyl salts; although the results best a p e with the formulaC10H1606, it is more probably C,,H1,06, the latter formula being morein accordance with the structure of the hydrocarbon C1,H2,.I t a reaction with phenjlhydrazine is being studied.A. J. G.A. T.Action of Ammonia on Parabanic Acid.By MISS ROUDINSKAI.~( J . Russ. Chem. Soc., 1885, 278-279) .-Ammonium parabanatewhen heated in a sealed tube a t above 160", is to a large extentconverted into oxaluramide; a t 100" the salt is decomposed, butscai~ely any amide is formed. Thc same amicle is obtained by passin142 ABS'lXACTS OF CHEMICAL PAPERS.ammonia over parnbauic acid a t 130" ; a t lower temperatures ammoniumparabanate is formed. From a few experiments, it apueara that theformation of oxaluramide from ammonium parahanat e (probably con-sisting in a decomposition of the salt into ammonia and parabanicacid, and subsequent formation of amide) is not only influenced bytemperature, but also by the pressure of the gaseous product of thedecomposition. A. T.By S.DOROSHEMKO ( J .Russ. Chem. Soc., 1885, 285-290) .-The presenceof aromatic hydrocarbons in Caucasian petroleum has been shownby Markownikoff and Oglobline (Abstr., 1883, 564), who foundhydrocarbons belongiug to the higher isologous series in fractionsof petroleum boiling between 150-210" and above 270". It is,therefore, highly probable tlint the lower homologues of the benzeneseries might be present in the portions of petroleum hydrocarbonsboiling below 150'. The material for the present, investigation con-sisted (1) of portions of Bibi-Aibat petroleum boiling at 105-115"and 115-125", and (2) of a mixture of the products of purificationof Balakhani petroleum boiling below loo", and of Bibi-Aibat oilboiling a t 100-120"- The hydrocarbons were converted into sulphonicacids by treatment with sulphuric acid, and these distilled with calciumhydroxide.The amount of oil thus obtained did not exceed 10 percent. of the sulphonic acids; the hydrocarbons were subjected t80fractional distillation, and fractions boiling a t 75-95', 95-1 lo",110-120", 1 2 0 - M O O , 130-135, 135-141" were collected. I n thefirst portion benzene was shown to be present by its separation incrystals on cooling the oil to - 30" ; in the higher boiling distillates,the presence of toluene also was shown. The portion boiling at 75-110"was nitrated in the cold, and the nitro-products, which had a decidedsmell of nitrobenzene, reduced with tiu and hydrochloric acid, whenaniline and tolaidine were formed. Toluene is also contained in tht?fraction 110-120".The portions boiling between 1.30" and 141"contain isoxylene. During the dry distillation of the sulphonic acidswith calcium hydroxide, a crystalline substance melting at 192.5-194", was deposited in the condenser, and was also obtained on cool-ing the hydrocarbons boiling above 140". Its quantity was too smallfor analjsia, and the author only points out its resemblance tomethy lenediphenyleiie obtained by Carnelley on passing a mixtureof toluene and benzene vapours through a red-hot tube (Trans.,1880, 710). A. T.Aromatic Hydrocarbons in Caucasian Petroleum.Oxidation of Benzene-derivatives with Potassium Ferri-cyanide. By W. A. NOYES (Avner. Chem. J., 7 , 145-149 ; comp.Abstr., 1884,299) .-Orthobromotoluene when oxidised with an alkalineferricy anidc, yields orthobromobenzoic acid, but oxidation occurs onlyto a very slight extent, less than 0.5 per cent.being formed duringthree or four hours.Paratoluenesulphonamide yields 55 per cent. of the correspondingparasulphaminebenzoic acid ; the barium salt, (C7H,S04N)2Ba +5H,O, separates in crystal!iue tufts from a cold solution, whilst froORGANIC CHEMISTRY. 143a hot soliltion it separates with 2H20 in small scales ; this salt hasbeen described by Remsen as crystallising with only 1 mol. H,O.H. B.Oxidation of Metanitrotoluene. By W. A. NOYES and W. E.MOSES ( A m e r . Chem. J., 7, 149-1533 comp. Abstr., 1884, 299).-When metanitrotoluene is oxidised with alkaline ferricyanide, notmore than 5 per cent.of metanitrobenzoic acid was obtained, whilstthe para- and ortho-nitrotoluenes yield 70 to 75 per cent. of thecorresponding acids ; it would, therefore, seem probable that an alka-line ferricyanide solution can be used to oxidise a methyl-groupstanding in the ortho-position to a nitro-group without attackinq amethy I-group in the meta-position.By E. HJELT (Ber., 18, 2879-2881).-If chlorine is passed into ortbo-xylene until the gain in weightcorresponds with the replacement of 4 atoms of hydrogen by chlorine,a crystalline mass saturat)ed with an oil is produced. On distillation,a liquid and a crystalline solid are obtained; the latter is a tetra-chloride. It melts a t 89" and boils a t 273-274", is insoluble inwater, readily soluble in ether ; it crystallises in the triclinic systemwith axial ratio a : b : c = 0.972 : 1 : 0.741.I n order to determinewhether the chlorine-atoms are disposed symmetricallg or unsym-metrically, the compound was heated with water in a sealed tube a t200-210" : phthalide was obtained in large quantities, a resultwhich would point to the latter hypothesis; but inasmuch as thephthalide was always accompanied, especially at the lower tempera-ture, by an oil having aldehydic properties, the author is inclined toregard the substance as having the formula C6H1(CHCl,),.H. B.Ortho-xylenyl Chloride.V. H. V.Reaction of Aluminium Chloride with Hydroxyl Com-pounds. By A. CLAUS and H. MERCKLIN (Ber., 18, 2932-2936).-Dichlorhydrin-alu.minium chloride, A12C14( 0*C3H5C1,),, is obtained bythe action of aluminium chloride on dichlorhydrin dissolved incarbon bisulphide.Trip h enol- alumi?aium chloride, A12C13( 0 Ph) 3, is prepared by addingalnmiiiiuni chloride in small quantities to a solution of phenol i uboiling carbon bisulphide ; it forms a yellow powder readily solublein boiling carbon bisulphide.Resol.cino1-akl.minium chloride, Al2C1, : CsHaO,, forms a thick reddish-brown liquid, which gradually becomes solid when kept over sulphuricacid ; it dissolves readily in hot carbon bisulphide. All these corn-pounds decompose violently when brought into contact with water.Symmetrical triphenylpropane, C3H5€'h3, is prepared from trichlor-or tribrom-hydrin and forms a thick, yellow liquid which distilswithout decomposition only under diminished pressure.D ipheng 1-propane is formed at the same time.Pseudocumenol and Pseudocumidine. By I(. AUWERS (Bey.,18,2655-2663).-By the action of bromoform and aqueous alkalison pseudocumenol, a compound, CLoHr4Brz0, is obtained, which meltsIt is a crystalline, hygroscopic substance.N. H. M144 ABSTRACTS OF CHEMICAL PAPERS.at 105", and resembles the chlorine compound described in the author'sprevious communication (Abstr., 2885, 380) in all respects save inits ready decomposition by alcoholic potash, by which the chlorinecompound is not affected a t 100". By the action of iodoform onpseudocumenol, only a very small quantity of an iodo-compound isformed. Similar products cannot be obtained from phenol, triphenylorthoformate being formed.Dibromopseudocumenyl methyl: ether, c6Br2Me3*OMe[2 : 5 : 1 : 3 : 4 : 6 J,is obtained by brominating pseudocuinenyl methyl ether a t theordinary temperature, o r by methylating dibromopseudocummol.Itcrystallises in white needles of vitreous lustre, melts at 96", is in-soluble in water, readily soluble in alcohol and acetic acid, veryreadily soluble in ether, chloroform, and benzene, and is only slightlyattacked when heated with hydrochloric acid a t 170".Metnnityopseudocumenoi, OH-C6HMe3*NO2 [Me3 : NO, : OH =1 : 3 : 4 : 2 : 61, is prepared 'by evaporating an alcoholic solution ofits nitrate (Zoc. cit.) .to a syrup and then distilling with steam, and isalso obtained by adding concentrated hydrochloric acid to an alcoholicsolution of the nitrate, and allowing the mixture to remain for sometime.It. crystxllises i n long, reddish-yellow needles or prisms offatty lustre, melts a t 48", and is moderately soluble in hot water,readily in the other usual solvents. The nitrate of this substance isalso formed when pseudocumenyl methyl ether is nitrated. 2Cletanitro-pseudocumen yl methyl ether, NO,-C6HMe3-OMe, is prepared by methyl-ating metanitrocumenol : it crystallises in large prisms and rhombictables, melts a t 4 1 4 2 " , and is very readily soluble in the ordinarysolvents except water. The following corrections are made in themelting points previously given (Zoc. cit.) : dinitropseudocumenol meltsa t 112", dipseudocumenol a t 173", and dipseudocumenyl methyl ethera t 126".Dibromodipseudocumenol, ClrrHrOBr202, crystallises in small, lustrouscrystals, and melts a t 186-187".Dipseudocumidine, when pure, melts a t 68" and boils a t 234" ; aceto-pseudocumide melts a t 164" and boils a t above 360" ; orthonitraceto-pseudocumide melh a t 202--204".Diizitracetopseudocun.lide,C6Me3(N02)1*NHAc [l : 3 : 4 : 2 : 5 : 61,melts at 280", sublimes unchanged, and is insoluble in water, andsparingly soluble in otber solvents. If this is heated with concentratedsulphuric acid for a few minutes at loo", and a, large quantity ofwater is then added, dinitropseudocumidine, C6Me3(N02)2*NH2, is preci-pitated. This crystallises in long, lustrous, orange-yellow needles,melts at 183", and has but very feeble basic properties.When reducedwith tin and hydrochloric acid, it yields t'he hydrochloride of a basewhose composition could not be ascertained with certainty. Thehydrochloride crystallises in plates or prisms, the free base formssilky needles.Aiizidopseudocumy lenetheny lamidine, NH2*C6%fe3<NH>CMe, is pre-pared by reducing dinitracetopseudocumide with tin and hydrochloricacid. It crystallises with 2 mole. H,O in pale-yellow prisms or stellate--ORGANIC CHEMISTRP. 145groups of plates, softens at 215", and melts a t 215-218". The hydro-chloride, CllH15N3,2HCl + Aq, crystallises in slender, white needles ;it monohydrochloride, Cl1H1JYB,HCL + 2H3,0, crystallises in slender,white prisms ; the platinochloride, Cl,H,,N3,H2PtC16, forms stellategroups of slender, oi-ange-red prisms.Action of Acetone on Aniline.By C. BEYER (J. pr. Chem. [Z],30, 489-491).-An answer to Engler and Riehm regarding priority.Remarks on the Preceding Answer." By E. v. MEYER (J. pr.A. J. G.Chem. [a], 30,491).Consecutive Xylidines.2905) .-A controversial paper.By E. WROBLEWSKI (Ber., 18, 2904-Commercial Xylidine. By W. STAEDEL and 0. HOLZ (Ber., 18,2919--2924).-Commercial xylidine consists of two isomeric modifi-cations : the one a metaxylidine [Me : Me : NH, = 1 : 3 : 41 ; theother a paraxylidine. The former boils a t 212", and its acetyl-derivative at 130"; its corresponding xylenol is not, as Jacobsendescribed, a liquid, bat a solid crystallising in needles which melt at28O, sparingly soluble in water, the aqueous solution giving a bluecoloration with ferric chloride.On oxidation with chromic acid, the paraxylidine yields a quinone.The corresponding quinol forms a dibenzoyl-derivative, CGH2Mez( OBz),,crystallising in glistening needles which melt at 160". The diethyl-derivative, C6H2Me(OEt)2, forms glistening white leaflets melting a t106".V. H. V.Simple Method of Preparing Azo-derivatives. By 0. N.WITT (Ber., 18, 2912-2913).-After alluding t o the variousdifficulties incidental to the methods of preparation hitherto proposedfor the azo-derivatives, the following simple process is suggested.A quantity of stannous chloride equivalent t.0 that of the nitro-compound, is poured into an excess of soda, and the solution formedis heated with the nitro-compound a t the temperature of the water-bath.The process is suitably modified according to the nature andstability of the compound which it is required to reduce. Usually theazo-salt crystallises out on cooling, but if this does not, occur, then thestannous oxide is precipit,ated by a current of carbonic anhydride, theliquid filtered and evaporated, and the azo-derivative finally separatedfrom the potassium carbonate by aqueous alcohol. V. H. V.Azo-compounds with Mixed and Substituted Radicles andtheir Derivatives. By T. KANOKNIKOFF (J. Russ. Chem. SOC., 1885,369--371).-1n manner similar to the formation of hydroxyazobenzenefrom diazobenzene and phenol, new azo-compounds were obtainedfrom orthoanisidine and metacresol, from orthoanisidine and ortho-cresol, and from orthonitranisoil by reducing them with sodiumamalgam.The first, OMe*C6H4.N2*C6H3Me*0H, melts a t 161", thesecond a t 68", and the third at 103". The reduction of these isomericVOL. L. 146 ABSTRACTS OF CHEMICAL PAPERS.compounds with stannous chloride and hydrochloric acid yields sub-stances corresponding with benzidine and diphenylene. The chief aimof further investigation will be the study of Skraup's reaction withthe compounds containing amido-groups. Thus far, on heating me ta-cresolorthoanisod and azorthoanisoil with glycerol-sulphuric acid andnitrophenol, compounds of basic character are obtained which formwell crystallised salts. A. T.Derivatives of Dicyanphenylhydrazine. By J.A. BLADIN(Ber., 18, 2907'-2912).-By the action of nitrous acid on dicyan-phenylhydrazine, a compound, C8H5N5, is obtained (Abstr., 1885,980) t o which the formula N<Nph>c.CN is now ascribed, This,wben saponified, yields the corresponding carbozglic acid,N-Ncrystallising with 1 mol. H,O in colourless needles; when dried itmelts a t 137-138", and is decomposed with evolution of carbonicanhydride a t 150". Its potassium salt forms glistening leaflets, coppersalt, bluish-green rhombic tables, silcer and lead salt';, sparingly solublecrystalline precipitates. The nzethyl salt, CN4Ph*COOMe, crystallisesin glistening leaflets melting a t 116", soluble in alcohol and ether,sparingly soluble in water; the ethyl salt forms colourless needlesmelting a t 74".Hydrogen peroxide converts the nitrile, PhCN,.CN, into thecorresponding amide, CN,Ph*CONH2, which crystallises in colourlessprisms melting a t 168", sparingly soluble in water, alcohol, and ether.On heating the carboxylic acid, an oil is obtained of the compositionC,N,P4 = N<hph>CH ; it is heavier than and insoluble in water,readily soluble in alcohol and ether, is readily decomposed on distilla-tion, and has feebly basic properties, dissolving in concentrated acids,and yielding a, platinochloride in the form of golden leaflets.YONV.H. V.Indophenol and Indoaniline. By R. MOHLAIJ (Bw., 18, 2913-2918).-The researches of Caro, Nietski and others, have shown thatthe simultaneous oxidation of paradiamines or amidophenols on theone hand, and of phenols and amines on the other, yields a numberof dyes belonging to the safranine, or indophenol and indoanilinegroups.In this paper phenol- and &-naphthol- blues and their deriva-tives are more particularly studied.Phenol-blue, CIJHIINPO, is best prepared by heating the doublechloride of zinc and dimethylphenylene-green with soda solution(sp.. gr. = 1.4) ; a flocculent blue precipitate separates out, which onboiling with a 10 per cent. grape-sugar solution, evolves dimethyl-amine and dissolves to form a red liquid. On filtration and exposureof the liquid to the air, the phenol-blue separates out in glistening,prismatic crystals. The reaction is explained thus :ORGANIC CHEMISTRY. 147N*C,H4*NMe, N*C,H,*NMe,CSH,' I + NaOH = NaCI + C,H/ 1'KMe2C1 'NMe2.0HI n the above operation,.if a larger proportion of soda solution isused, and the liquid is boiled before the addition of the grape-sugar,quinonephenolimide, <C"H">N*C6H,*OH, -0- is produced by a similarreaction; the same change is also effected by boiling phenol-bluewith soda.a-ilTaphthol-bZue, c,HI,,N20, is prepared by reducing nitroso-dimethylaniline hydrochloride with zinc-dust, and adding the productto an equimoleculur poportion of mnaphthylaaine hydrochloridedissolved in 500 parts of water.It forms bluish-violet, hard crystals.Para- and Ortha-nitroxanilic Acids and their Reduction.By 0. ASCHAN (Ber., 18; 2936-2940) .-Paranitroxanilic acid,C,H6N,05, is obtained, together with a small quantity of the ortho-derivative, by the action of fuming nitric acid on oxanilic acid.It crptallises from water in long, pale yellow needles, containing1 mol.H20. The potassium and sodirum salts aresparingly soluble in cold water; the ammonium salt dissolvesreadily in alcohol. When paranitroxanilic acid is reduced, it yieldsparapheny lenediamine.Orthonitroxamilic acid is best prepared by heating orthonitranilinewith anhydrous oxalic acid for 40 minutes a t 130-140" ; the productis then washed with a little water and recrystallised from water. Theacid separates in long, gold-coloured needles, melting a t 112". It isreadily soluble in hot water, alcohol, and glacial acetic acid. Thealkali salts are sparingly soluble in cold water and alcohol, andcrystallise in yellow, lustrous needles.The barium and silver sa2tsform colourless needles almost insoluble in water. The acid hasalready been obtained by v. Herff (Anden, 209,367), who described itas " ethyl oxorthonitranilate." Tin and hydrochloric acid act on theacid with formation of dihydr~x~ethe.lzylphe?z?llenediami~ze, CsH,N,O,.This crystallises in long, slender needles with a glassy lustre meltinga t 280" ; it is sparingly soluble in water, alcohol, and ether, insolublein benzene, &c. It dissolves in alkali, with formation of unstablesalts which are deconiposed by carbonic anhydride. A similarcompound was obtained by Hinsberg (Abstr., 1883, 323) from meta-nitroparoxaltoluidic acid. N. H. M.V. H. V.It melts at 210".Isomeric Malontoluidic Acids. By L.R~~GHEIMER and R.HOFFMANN (Be?.., 18, 2971-29 75) .-Malonparatoluidic acid hasalready been described (Abstr., 1884, 1023). The calcium salt (with44 mols. H,O) forms long, slerider needles; the barium salt (wit'h5 mols. H,O) forms lustrous prisms. The silver, copper (with2 mols. H,O), and zinc salts are also described. The ethyl sult1 148 ABSTRACTS OF CHEMICAL PAPERS.crystallises from alcohol in large, well formed, rhombic crystals,a : b : c = 0.9320 : 1 : ?Malonorthotoluidic acid, C,H,Me*NH*C0.CH2.COOH, is prepared ina manner similar to the para-acid (Zoc. cit.). It is readily soluble inwater and alcohol, from which it crystallises in long, colourlessneedles; these become reddish when exposed to air.It melts a t138-143" with evolution of carbonic anhydride. The calcium salt(with 3 mols. H,O) forms groups of small needles rather readilysoluble in water; the barium salt (with 1 mol. H20) crystallises inbroad needles, very readily soluble in water; the copper salt (with2 mols. H20) crystallises in well-formed, lustrous,. greenish-blueprisms. The ethyl saZt forms long, narrow prisms melting a t 73-74'.Malonnaetatoluidic acid, C,H4Me*NH*CO*CH2*COOH, forms large,lustrous plates which melt at, 99-101", and decompose only whenheated to a still higher temperature.Reaction of Benzaldehyde with Azobenzene. By T.BARZILOVSKY ( J . Russ. Chem. Soc., 1885, 366-368) .-When azo-benzene and benzaldehyde are heated with zinc chloride, a greenish-grey powder (m.p. 339") is obtained and found to be identicalwith Schiff's benzilidene-benzidine (Abstr., 1878, 668). In theabsence of zinc chloride, the reaction gives a different result ; whenheated in a sealed tube during three to four hours a t 200", thetwo compounds yield a dark brown, crystalline mass, which afterpurification forms white, glistening, nacreous plates, melting at 164",easily soluble in alcohol and benzene, sparingly in ether, and veryslightly in light petroleum. Its composition seems to indicate thatit is a product of the direct union of benzaldehyde with azobenzene,CI2H,,N2( C7HsO),. A further investigation of the compound will bemade, as well as of the products which may be obtained from azo-benzene and the three isomeric nitrobenzaldehydes, and from azo-benzene and azotoluene and some saturated aldehydes.Action of Alkyl Iodides on Amido-acids. By A.M~CHAEL andJ. F. WING (Amer. Chem. J., 7, 195--199).-Paramidobenzoic acidwas dissolved in methyl alcohol, and an excess of caustic potash andmethyl iodide (3 mols.) added, with addition of more potash from timeto time. After removal of the methyl alcohol, the addition of aceticacid precipitated dimethylamidobenzoic acid ; from the concentratedfiltrate, hydriodic acid precipitated the hydriodide of the beta'ine,C,H,<CG.O> ; the free base, its hydriodide and its platinochloride,are described. When ethyl iodide acts on paramidobenzoic acidin presence of ethyl alcohol, only ethyl diethylamidobenzoate isformed ; no trace of a betaine could be detected.Ally1 iodide inalcoholic solution did not yield the corresponding betaine, but onlydiallylparamidobenzoic acid melting a t 127" ; the corresponding ally1salt was not formed. The three iodides therefore show a gradualvariation in their action.N. H. M.A. T.NMe3H. BORGAXIC CHEMISTRY. 149Mononitro-derivatives of Par- and Met-acetamidobenzoicAcids and their Products of Reduction. By A. KAISER (Ber.,18, 2942-2 9 5 2) .-Met anitrop Bra cet amid ob enzoic acid,COOHCsH,(NOZ)*NHAc [COOH : NO2 : NHAc = 1 : 3 : 41,is prepared by nitrating paracetamidobenzoic acid a t a temperaturebelow LO", and subsequent purification of the product by means of itsbarium salt. It forms yellow plates melting a t 220-221", readilysoluble in boiling alcohol, glacial acetic acid, and acetone, verysparingly soluble in cold water.Warm dilute hjdrochloric acidsaponifies it easily. The barium salt (with 64 mols. HzO) formsyellow plates readily soluble in hot water; the caZcium salt cry+tallises with 2 mols. H,O in sparingly soluble, yellow needles.When a solution of the a,cid in glacial acetic acid is treated with tin,meta~~nranh~d,racetodiamidobenzoic acid, COOHG6H,<~H>CMe, N isformed. This compound crystallises with 1 mot. H20 (which it losesa t looo), and melts with decomposition a t 301-302"; it dissolvesreadily in boiling glacial acetic acid, less readily in hot alcohol, and isalmost insoluble in ether, acetone, benzene, and chloroform.Whenheated above 160°, it gives off carbonic anhydride and yieldsanhydracet'diamidobenzene. The hydrochlo?-ide forms slender, whiteneedles, very readily soluble in cold water ; the platinochloride(with 2 mols. H,Oj crystallises in gold-coloured needles. Thepotassium salt forms colourless, microscopic needles.Paranitrometacetariidobenzoic acid,[COOH : NOz : NHAc = 1 : 4 : 31,is obtained in a manner similar to the metanitro-derivative, andforms deep yellow plates which melt a t 205-206"; it is readilysoluble in boiling alcohol, glacial acetic acid, and acetone. Thebarium salt crystallises with 7 mols. H20, in long, slender, yellowneedles ; the calcium saZt, with 7Q mols. HzO, forms nodular groupsof yellow needles; both dissolve readily in boiling water. Whensaponified, the acid yields paranitrometacetamidobenzoic acid, meltingat 298".Ethyl yaranitrometanzidobenxoate ci*ystdlises in long, redneedles melting at 139", very readily soluble in ether, alcohol,acetone, &c. When paranitrometacetamidobenzoic acid is reduced,an anhydro-compound is formed identical with that obtained frommetanitroparacetamidobenzoic acid.Consecutive orthonitrometaceta~nnidobenxoic acid was found in themother-liquor obtained in the purification of paranitrometacetamido-beneoic acid ; it forms colourless needles readily soluble in alcohol,glacial acetic acid, &c., and melts with decomposition at 240-241".The barium (with 1 mol. H20) and calcium (with 6 mols. H20) saltsare described. When saponified with baryta, it yields consecutiveorthonitrometarnidobcnzoic acid melting at 156-157".Action of Benzanilidoimide Chloride on Ethyl Sodo-malonate.By F. Jusr (Bey., 18,2623-2631>.-By this reaction aboutequal parts of ethyl mono- and di-anilbenzeny1mnlonate are formed.N. H. M150 ABSTRACTS OF CHEMICAL PAPERS.Ethyl anilobenzenylmaloozate, NPh : CPh*CH(Cr)OEt),, is obtainedfrom the product of the reaction, by diluting it with water, extractingwith ether, evaporating the ethereal solution, and crystallising theresidue from alcohol. I t forms large, hard, monoclinic or tricliniccrystals, which are strongly refractive, and show a blue fluorescence ;i t melts a t 75", and is insoluble in water, readily soluble in alcoholand ether. When heated with dilute hydrochloric acid in sealed tubesa t 120°, it is converted into acetophenone, ethyl chloride, anilinehydrochloride, and carbonic anhydride.Ethyl dianiZbenzenylmaZonate, C(CPh NPh),(COOEt),, is con-tained together with ethjl malonate in the motheu-liquor of thepreceding compound; it can also be prepared by the action ofsodium and benzanilidoimide 6hloride on the mono-compound.Itcrystallises in stellate groups of pldfes, and melts at 160". Whenheated with ditute hydrochloric acid in sealed tubes at 150", i t yieldsbeiizoic and acetic acids, ethyl chloride, aniline hydrochloride, andcarbonic anhydride.Ethyl ani/be?zzenylethyZmalonate, .NPh : CPh*CEt(COOEt),, isobtained by the successive action of sodium and af benzanilidoimidechloride on ethylic ethylmalonate, as a colourless oil, which cannot becrystallised or distilled unaltered.Benzanilide is formed by the action of aniline on the product of thereaction of beneoic chloride with ethyl sodomalonate.Arnidotoluenedisulphonic.?,Acid. By H.HASSE (Anmlelz, 230,A. J. G.28 6-298) .-Ort h amido toluen emetasulphonic acid,NH2*C6HjMe-E103H [Me : NH, : SOiH = 1 : 2 : 51,NH,GH,Me(S03H), [Me : NH, : SO,H : SO,H = 1 : 2 : 3 : 51,by the action of fuming sulphnric acid a t l50-l7O0, or of chloro-sulphonic acid at 160". The disulphonic acid crystallises with 16 mols.H20 i n colourless needles, which are soluble in alcohol and in waterThe normal barium salt, C7H7N(S0,),Ba + 3H20, crystallises in thetriclinic system.It is freely soldble in water, but is precipitated fromthe solution by alcohol. The acid salt, ( SO3H.C7H7X*S03),Ra + 39&O,forms microscopic needles soluble in water, but insoluble in alcohol.The potassium salt, C7H,N(SO9K), + 2H20, crystallises in monoclinicplates. The sodium salt forms tabular crystals containing 6 mols.HfO. The calciwn salt, C7H,N(SO3)?Ca + 5H20, forms l u n g platessoluble in water, but not in alcohol. The normal lead salt,C&t,N(SO,),Pb + 2H@, crystallises in cololrrless prisms. It is lesssoluble in water than the potassium salt. {HSCi*&H,N*SO,),Pb +6iW20 forms quadratic prisms. It is more soluble in water than thenormal salt.The disulphonic acid decomposes a t 240", yielding amidotolnene-sulphonic and sulphuric acids.The diazo-compound is crystalline.The salts af amidotolnenedisulphanic acid are converted into diazo-tolnenedisulphanates by the action of nitrous acid. The pofassiwnsalt crj stnllises in anhqdrous, jellow prisms. The barium salt,is converted into am.idot~~uenedisulphonic acidORGANIC CHEMISTRY. 151[C7H,N2(S03)2]2Ba + 4H20, is deposited from its aqueous solution onthe addition of alcohol, in microscopic plates. The lead salt formsyellow, anhydrous plates.CresoZdisulphonic acid is obtained in needles or plates by boiling anaqueous solution of the diazo-compound. It is freely soluble in waterand alcohol. The potassium salt, OH*C7H5(S03K)z + 14H20, andbarium salt, OH*C7H5( SO,)?Ra + 3iH20, crystallise in needles.Diazotoluenedisulphonic acid is decomposed by boiling with absolutealcohol, yielding ethoxytoluenedisulphonic acid.It is also decom-posed by hydrobromic acid, forming bromotoluenedisulphonic acid.The potassiunz salt, C,H5Br(S03K)z + 4H20, crystallises in plates, andthe barium salt, C711,Br( SO,)?Ba + lQHzO, in long, colourless needles,sparingly soluble in water. The chloride melts a t 90°, and the amideat 237". Tbe bromiiie in the acid is replaced by hjdrogen on treat-ment with sodium amalgam, but a better yield of toluenedisulphonicacid, C,H3Me(S03H), [Me : S03H : SO,H = 1 : 3 : 51, is obtained bythe action of hydriodic acid on potassium diazotoluenedisulphonate.Toliienedisulphonic acid.is an oily liquid. The ammonium and potas-sium salts are crystalline; the latter is insoluble in alcohol.Thechloride, C7H6( S02Cl),, is deposited from ether in colourless prismsmelting a t 132". The amide forms sparingly soluble plates, whichmelt at 230.Attempts to prepare amidotoluenetrisulphonic acid were unsnc-cessful. w. c. w.Two Dislllphonic Acids of Paratoltzidine. By L. RICHTER(Annalen, 230, 313-333) .-Paramidotoluenedisdphonic acid,NH2*CsH2Me(S03H)2 + 2H20,can be prepared by the action of 'fuming sdlphuric acid or of chloro-sulphonic acid on paramidotoluenemetasulphonic acid. It forms Bcrystalline mass soluble in water, less soluble in alcohol. The normalbarium salt, NHi*C7H5(S03),3a + 3HZQ crystallises in rhombicplates soluble in hot water, but insoluble in alcohol. The acid bariumd t , ( S03H*C7H7N*S03)Ba + 3Hzo, crystallises in needles.It dis-solves freely in hot -A atfer. Potassium amidotoluenedisulphonate,NH2.C7H5(SO3K), + 2H20, is deposited in pointed prisms from anaqueous solution on the cautious addition of alcohol. The normal leadsalt forms anhydrous, silky needles, soluble in water. The acid leadsalt forms white needles. It is less soluble than the normal salt.Paramido toluenedisulphonic acid is decomposed by heat at 200", orby the action of water a t 140°, into sulphuric and paramidotoluene-metasulphonic acids. The diazo-compound of the disuiphonic acid isexceedingly soluble in water, but is neither dissolved nor decomposedby alcohol. The potassiuni, barium, and lead salts of this acid areanhydrous. They are decomposed by boiling with water, yieldingsalts of paracresoldisulphonic acid.The free acid forms needle-shapedcrystals, which are freely soluble in water and alcohol. BariumparacresoZdisuZphonate, OH*C7H,( SO)zBa + 4H20, crystallises in flatneedles, soluble in water. The potassium salt, which crystallises i152 ABSTRACTS OF CHEMlCAL PAPERS.plates, and the lead salt>, OHG7H,(S0,),Pb + 3H,O, are precipitatedfrom their aqueous solutions by alcohol.The dinitroparacreso 2 obtained from the amidodisulphonic acidcrystallises in lemon-coloured needles. It melts a t 82*5", and dissolvesfreely in alcohol, sparingly in water. The potassium, barium, andsilver salts are crystalline.Barium and potassium parabromotoluenedisulphonates,C7H,Br(S03)zBa + 6H20, and C7H5Br(S03K), + H20,The su1phoni.c chZoride forms thick prisms melting a t 133".form sjlky needles soluble in water.It isfreely soluble in ether.On cooling its hot aqueous solution, theamide is deposited in colourless prisms soluble in hot water and inalcohol. It melts above 240".Pariodotoluenedisulplaonic acid, C,H,I( SO,H),, forms needle-shapedcrystals freely soluble in alcohol and water. The barium salt,C,H51(S03)&a + 6H,O, and the potas.sium salt, C7K61(S03K)z + 2H20,ai-e soluble in water, but insoluble in alcohol. The sulphonic chlorideforms quadratic prisms. It melts at 143", but if it is allowed tosolidify and is then reheated, it melts at 126". The amide melts a t130-132", and is soluble in alcohol.The toZuen,edisulphonic acid, C7H6( SO,H),, obtained by the actionof sodium amalgam on an aqueous solution of potassium iodo-toluenedisulphonate, is identical with the acid described by Hakansson,(Ber., 5, 1084).Hy drazinet oluenedisu lphonic acid, N2H3* C7H5( S 03H)2, is a crystal I inecompound dissolving freely in alcohol and in water. The acid bariumsalt crystallises in plates containing 2& mols.H,O.11. ParamidotoZuenedisulphonic mid, NH2*CGH2Me( S03H), + 2$H20,forms silky needles freely soluble in water, less soluble in alcohol.The normal barium salt crystallises in plates containing 1 mol. H,O.It is sparingly soluble in water. The acid barium salt crystalliseswith 1+ or 4 mol. H,O. Thepdassium salt contains 2 mols. H20. Itis freelv soluble in water, but insoluble in alcohol. The free aciddecomp&es at 290", yielding paramido-orthosulphonic and snlpbnricacids.w. c. w.Nitrotoluidiqesulphonie Acid. By G. FOTH (AnnitZen, 230,N0,~CsH,~~e(NH2)*SOaH [Me : NO, : NH, : SO,H = 1 : 2 : 4 : 51,is obtained by the action of chlorosulphonic acid on nitrotoluidine at160". The crude product is dissolved in ammonia, and the free acidliberated from the ammonium salt by the addit'ion of hydrochloricacid. The pure acid is deposited from its aqueous solution in pale-yellow needles which darken on exposure to the air. It is sparinglysoluble in alcohol and in cold water. Potassium nitrotoluidinesulphoaate,C,H,N202*S03K + H,O, crystallises in needles or prisms of an orangecolour, and the ammonium salt in golden needles or prisms.Both salts are sparingly soluble in cold water.The barium salt,(C,H7N202*S03)2Ba + 4H20, forms yellowish-red prisms. The lend298-313) .-The best yield of nitrotoluidinesulphonic acidORGANIC CHEXISTRE'. 153and silver salts are also sparingly snluble in cold water ; the formercrystal!ises in red needles, and the latter in glistening white prisms.The diazo-compound, NOz*CsHzMe<& SOa- : N>, is prepared by addingdilute sulphuric acid to a solution of potassium nitrite and nitro-toluidine sulphonate. It is converted into nitrotoluenesulphonic acidby the action of absolute alcohol a t 100".~itrotoluenesulphonic acid, N0z.C6H,Me.S03H [Me : NO2 : S03H =1 : 2 : 51, and its salts are very soluble in water, and crystallise withdifficulty.The potassium salt forms thick prisms of a reddish-yellowhue. The sulphoiiic chloride is deposited from ether in thick prismsmelting a t 50". It is freely soluble in ether and in glacial acetic acid.The arnide forms glistening needle-shaped crystals, which are freelysoluble in alcohol. J t melts a t 133.5". When reduced with ammoniumsulphide, nitrotoluenesulphonic acid yields a toZuidiiaesuZp h o n k acid,NH2.c6H3~$e*So3H [Me : NH, : S0,H = 1 : 2 : 51, which appears tobe identical with the acid described by Page1 (this Journal, 1875,897),and by Nevile and Winther (Trans., 1880, 626).Iodotoluidinesulphonic acid, NH2*C7H,I*SO3H, prepared by the actionof hydriodic acid on the diazo-compound of nitrotoluidinesulphonicacid, crystallises in needles.Thebarium salt crystallises in rhombic plates which are freely soluble inwater.ToluylenediarninesuIlp7~onic acid, CsHZMe(NHz),~SO,H [l : 2 : 4 : 51,is obtained by the action of stannous chloride on nitrotoluidinesulphonicacid. It is a crystalline substance, and unites with acids as well aswith bases, forming crystalline compounds : for example,The barium salt contains 54 mols. HzO.~0zoC6HzMe(NzH3)~S03H [Me : NOz : N2H3 : S03H = 1 : 2 : 4 : 51,crystallises in quadratic plates.prisms containing 4 mols. H,O.It is sparingly soluble in water.C,H~(XHZ)~*SO3H,HCl + HZO ; C7Hs(NHz)z*SO3K + HZO.Nitrotoly lhydraxinesulphonic acid,The barium salt forms long, yellowIt is freely soluble in hot water, butOrthamidometaxylenesulphonic Acid.By J. SARTIG (AnnuZen.,230,333-345).-The author confirms Jacobsen's statements (Abstr.,1883, 593) regarding orthamidometaxylenesulphonic acid and itssalts, with the exception that he finds that the barium salt contains2 mols. H20, whilst Jacobsen found only 1 mol. H,O. The diazo-compound crystallises in microscopic rhombic plates. It is decom-posed by hydrohromic acid, yielding a bromo-xylenesulphonic acid,C6HzMezBr*S0,H [Me : Me : Br : S03H : 1 : 3 : 6 : 41, which has beendescribed by Wedding (Ber., 11, 1062). By decomposing the diazo-compound with water, xylenolsulphonic acid,only sparingly soluble in cold. w. c. w.OH*C6H,Me*S03H [Me : Me : OH : S03H = 1 : 3 : 6 : 41,is obtained i n needle-shaped crystals which are freely soluble in waterand alcohol.The aqueous solution gives a violet coloration wit154 ABSTRACTS OF CHEXICAL PAPERS.ferric chloride, which turns green on the addition of alcohol. Thebuwium, (OH*C,H,*SO,),Ba + HZO, and lead, (OH.C8H,S03)2Pb + 2H20,salts crystallising in needles, and the anhydrous potassium salt crystal-lising in rhombic plates, are easily soluble in water. Absolute alcoholdecomposes the diazo-compound. forming erhoxy-xylenesulplzonic acid,OEt.C6HzMe2*S03H [Me : Me : OEt : SOjH = 1 : 3 : 6 : 41. Thisacidcrystallises in microscopic, rhombic plates, which are freely soluble inalcohol and in water. The b a ~ i u m salt contains 3 mols. HzO ; it issoluble in water and in alcohol.Nitra71aido-x2lZe9teulphonic acid, NHi*C,HMeZ(NOz)-SO3H, preparedby the action of a mixture of stronq nitric and srilphuric acids onrtmidoxylenesulphonic acid, crystallises in colourless needles.It issparingly soluble in water and in alcohol. 'The potassium and bariumsalts crystallise in rhombic plates containing l+ mols. H20. They dis-solve freely in water; the barium salt is but sparingly soluble in alcohol.Lpad niiro-xylidiTzesupho1Late, NH,( C,IE4,S03),Pb + HzO, forms silkyneedles soluble in water. The diazo-compound crystallises in quadraticplates. It is decomposed by boiling water, yielding nitro-zylenol-sulphoriic acid. This acid is freely soluble in water and alcohol. Thebarium and lead salts crystallise with 3 rnols. H,O. They are moresoluble in water than in alcohol.Rromonitro-xyZe?aesulphonic acid, N0z*C6H&fe,Br*S0,H, crystalhe8in rhombic plates, which dissolve freely in alcohol and water.Thebarium salt, (N02*C,H,3~S03)2Ba + 3+H2Q, forms needle-shapedcrystals soluble in hot water and in alcohol. The potassium saltcontains 1 mol. HLO. It forms yellow prisms, and resembles thebarium salt in-solubility. Thepotusiium and barium salts of the ethoxy-nitrosulphonic acid are &woluble in alcohol, but, soluble in warmwater.Diumido-xylen,esuZphonic acid, C6H~e,(NHz)i*S03H, obtained by theaction of tin and hydrochloric acid on nitramido-xylenesulphonic acid,crystallises in prisms. It is soluble in water, but insoluble in alcohol,and forms crystalline compounds with acids and with bases. Thebarium salt crystallises in microscopic, rliombic plates, the potassiumand lend salts in prisms. Ths first contains 36 mols.HzO, thepotassium salt 1 mol. H,O, and the lead salt is anhydrous. w. c. w.Condensation Products o€ Isatin. By A. BAEYER and M. J.TJAZARUS (Ber., 18, 2637--2648).-Fresh analyses of indophenine andits dibrom-derivative lead to the formulw C12H7N 0s and C1,H5BrzNOSfor these compounds.Whilst benzene does not seem to unite with isatin, toluene reactsreadily with it in presence of sulphuric acid. Toluisatin,so obtained, crystallises in lustrous, colourless needles, melts at200-201", is readily soluble in alcohol, ether, and benzene, sparinglyi n light petroleum, insoluble in water, acids, and alkalis. The acetyl-derivative, CZrH2,NO2, crystallises in thin, colouriess needles, melts a ORQANIC CHEMISTRY.155142-143", and yields toluisatin when boiled with alkalis. The ethyl-derivative, C,4H23N0,, pFepared by 'heating to1 uisatin with sodiumethoxide and ethyl -iodide, or by the condensation of dhylpseudo-isatin with toluene, crystallises 'in nearly colourless plates, and meltsa t 108'. From these results, it, follows that toluisatin must beregarded as a pseudoisatin-derivative, and that in the condensation ofisatin vith toluene a conversion of is&in into pseudo-isatin musthave occurred. Tolubrornisatin, C22H1,BrN0, prepared from tolueneand bromisatin, crystallises in colourless needles, and melts at 235" ;the acetyl-derivative ci-ystallisea in needles, and melts a t 156".Phenolisatin, NH<~~$>C(C6H4*OH)z, is prepared by dissolvingisatin in an excess of phenol and adding sulphuric acid, with constantagitation, until the colour of the isatin 'has disappeared.It cqstal-lises in slender, white needles, melts at 220", is practio~~lly insolublein water, sparingly solnble in benzene and chloroform, readily inether and in alkalis. When potassium femicyanide is added to analkaline solution, a deep reddish-violet coloration is produced. Theacetyl-derivative, C22H17N04, orystallises in colourless needlw, andmelts at 185".Anidisatin, C2,Hl,NQ,, is obtained by eondensation from a mixtureof anisoil with excess of isatin. It crystallises in colourlew needles,melts a t 65", is soluble in most solvents, butinot in alkalis.Dimethy Znnilinisatin, XH<-%f:> ( C,&NMe2),, is prepared byheating isatin with an excess of dimethylaniline and zinc chlorideon the watesbath fur .5-6 hours.It mystallises in colourleSfi,lustrous, well-formed prisms, melts a t 234O, is insoluble in water andalkalis, sparinglysoluble in ether, alcohol, and light petroleum, readilysoluble in dilute acids. When oxidised, it yields a product that seemsto be identical with Figcher and Schmidb's ortbamidabenzaldehyde-green (Abstr., 1884, 1315).Simultaneous~Oxidation and Reduction by Means of Hydro-cyanic Acid. By A. MICHAEL and G. M. PALMER (Anler. Chem. J., 7,189--194).-Benzil, when treated with alcoholic potassium cyanide andconcentrated hydrochloric acid is converted almost quantitatively intobenznld ehyde and ethyl benzoate.Strong aqueous hydrocyanic acidat 200" effects (the same change. Benzoquinone, when treated withalcoholic potassium cyanide and hydrochloric acid is converted intobenzoquinol, and an oily liquid not fully examined, but probablyethylbenzoquinol. Benzo'in is converted into benzaldehyde andethyl benzoate. Benzaldehyde when heated at 200" with alcohol andhydrocyanic acid yields benmic acid and ethyl beneoate, probably alsobenzyl alcohol. The work is being continued. H. B.Nitronaphthoic Acids. By A. G. EKSTRAND (Ber., 18, 2881-2%7).-A discussion of the constitution of the nitronaphthoic acidsobtained by the nitration of a-naphthoic acid, and melting at 215"and 239" respectively (Abstr., 1885, 548). Both acids are convertedintoo dinitronaphthalenes, the former yielding the p-, the latter theA.J. G156 ABSTRACTS OF CHESIICAL PAPERS.a-compound. As the a-dinitronaphthalene yields mononitrophthdicacid [NOz: COOH : COOH = 1 : 2 : 31 on oxidation, t'he N02-qroups8s also the NOz- and COOH-groups in the nitronaphthoic acidare in the positions 1 : 4'; then in the p-dinitronaphthane and its cor-responding nitronaphthoic acid, the groups will be in the position 1 : 1'.The nitro-acid melting a t 239' can be converted into a chloro-naphthoic acid melting a t 245", which on nitration yields a nitro-chloronaphthoic acid, melting a t 225" and crystallising in prismaticneedles; its ethyl salt crystallisea in tables melting a t 125". OnNH reduction, the acid is converted into an anhydride, CI,H3C1< co>,crystallising in yellow needles, and melting a t 270".The readyformation of this anhydride points to the contiguity of the a-positionsBy A. CLAUS and M. KNYRIM(Ber., 18, 2924-2930) .-This acid is formed when a-naphthol dis-solved in glacial acetic acid is sulphonated a t a temperature below75". It forms long, slender, deliquescent needles, melting at 90"(uncorr.). A dilute solution of the acid decomposes when boiled,with separation of a-naphthol. The sodium salt forms white, lustrousplates readily soluble in water ; the potussium salt crystallises in colour-less needles, also readily soluble in water. The barium and lead saZts(each with 1 mol. H,O) were prepared. When the sodium salt istreated with phosphorus pentachloride in presence of chloroform,dichloronaphthol, C,,H,Cl,O [OH : C1 : C1 = 1 : 2 : 31, is formed ; thiscompound sublimes in white needles, melting a t 101" (uncorr.), and isreadily soluble in chloroform, alcohol, ether, benzene, &c. Thesodizrm and barium salts are readily soluble.Phosphorus penta-chloride acts on dichloronapht8hol at 140°, yielding trichZorona~htk,aZens[Cl, = 1 : 2 : 31 melting a t go", and probably identical with thatobtained by Faust and Saame (this Journal, 1872, 64), and that ofAtterberg (this Journal, 1876 [ii], 51 6). When dichloronaphthol isheated with dilute nitric acid a t 200", it yields phthalic acid. Chromicanhydride converts it into dichloronaphthsquinone, LO : G12 : 0 =1 : 2 : 3 : 41.N. H. M.By J. BREDT (Ber., 18, 2989-2990).-Camphoronic acid has the formula C9H,,0,, and not C6HL004, thatascribed to it by Rudzinski (Inaug. Diss., Wiirzburg, 1879). Whenslowly distilled it loses water and carbonic anhydride, yielding iso-butyric acid, and the anhydride of a new acid, C6H,,O4(?), meltingat 135". The caZcium salt, C,H,,OICa + 2+H20, and the siher salt,CiHloOdAg2, were prepared.Note.-The formulse of the new acid and its salts are given asprinted in the original.Fluorescent Constituent of Atropa Belladonna. By H.PASCHKIS (Arch. Phurrn. [3], 23, 541-543).-10 kilos. of ripebelladonna berries were extracted with strong alcohol, the solutionevaporated to diyess, the residue taken up with hot water, and theacid liquid thus obtained, agitated with chloroform.The residueof the nitro- aud carboxyl-groups respectively. v. 8. v.a-Naphthol-p-sulphonic Acid.Camphoronic Acid.N. H. MORGAXIC C'HEJIISTRY 157obtained on evaporation of the chloroform extract was recrystallisedfrom hot concentrated alcohol, from 40 per cent. alcohol, and finallyfrom water. When pure, the substance crystallises in yellowish-white,slender needles, seemingly rhombic pyramids ; it melts at 197-198".I t dissolves sparingly in cold water and in ether, more easily in hotwat,er, chloroform, arid in concentrated alcohol, and very easily in hotalcohol, ethyl acetate, acetic acid, and alkalis. Amy1 alcohol andbenzene extract it from its aqueous solution. The aqueous solutionreacts faintly acid ; the aqueous, alkaline, and especially the ammo-niacal and alcoholic solutions, show a splendid blue fluorescence.Thefluorescence disappears on adding acids, but alkalis cause its re-appearance. The sulphuric acid solution when nearly neut<ralised witharnmonia shows a fine purple-violet colour by reflected light, but iscolourless by transmitted light. The aqueous solution gives abeautiful blue precipitate with gold chloride, and a green oue withiron chloride ; alkaline copper solution and ammoniacal silver nitratesolution are reduced on warming. In slightly concentrated nitricacid, the substance dissolves with a yellow colour, which becomesblood-red on the addition of ammonia (reaction of mculin accordingto Sonnenschein). The substance seems to be identical with scopo-letin, obtained by Eijkman from ScopoZia japonica (Abstr., 1884, 404).The yield is only about 0.001 per cent.A New Nitrogenous Constituent of Plants.By E. SCHULZE and3:. BOSSHAHD (Zeit. ph,z/sioZ. Chem., 10, 80--89).-The authors givethe name vernine to this substance, and prepare it as follows; theyoung plants are dried, and extracted with hot water ; the extractis precipitated by lead acetate, and then by mercuric chloride. Theprecipitate produced by the latter reagent is collected, washed withcold water, and treated with hydrogen sulphide, the filtrate is neutra-lised with ammonia, and concentrated in a water-bath. On cooling,a jelly-like amorphous substance and asparagine crystals appear,these are collected, and the amorphous substance dissolved in hotwater ; on cooling this solution, crystals of vernine form.Verninemay be also separated from asparagine by fractional crys tallisation,vernine crystallisirig first. It crystallises in long, thin prisms of theformula C,H,,N,Os + 3Hz0 ; gives precipitates with silver nitrate,mercuric chloride, phosphotungstic acid, and with copper acetatre. Itdoes not dissolve cupric oxide; it is slightly soluble in dilute hydro-chloric and dilute nitric acids. On evaporating the nitric acidsoliition to dryness and adding ammonia, the residue is turned reddish-yellow. The silver compound has the formula CI6H,&g,N,O8.Guanine is formed amongst other products when vernine is heatedwith hydrochloric acid. Vernine occurs in Vicia sativa, Tr{foZiumpratense, ergot of rye, Medicago sativa, Piims siluestris, &c.; thequantity present in ergot being 0.1 per cent., in vetch 0.05 per cent.of the dried plant.Action of Phosphorus Pentachloride on Santonin. By B.PAWLEWSKI (Ber., 18, 2900--2901).--If equal inolecular proportionsof santonin and phosphorus pentachloride are heated together, and theJ. T.W. D. H158 ABSTRACTS OF CHEMICAL PAPERS.crude product crystallised from ether, a m onoehZoro-der.ivatirrp,C,,H,,C102, is obtained in the form of small crystals melting at 125‘,readily soluble in benzene, sparingly soluble in alcohol.If two molecules of phosphorus- pentachloride are. used, adichloro-derivative is formed ; this can best be mptallised from amixture of benzene and petroleum.It is a pale yellow substance,melting at 182”, insoluble in water, sparingly soluble in alcohol.Thus the two hydroxyl groupings, in santonin are successivelyreplaced by chlorine, but it appars probable thatt these groups aredifterent in function. V. H. V.Reactions of Iodine, Chlorrde with AlkaloYds. By A. D~TTMAR(Ber., 18, 1612--1622).-When yuinoline is treated with iodinechloride, quinoli.ne-chZor,~od~de,. C,H,NICI, is obtained as a yellowprecipitate ; this is acted on by ammonia, yielding a dark green com-pound, C9H7NH2T, which when warmed with alcohol decomposes withevolution of nitrogen and ammonia, and formation of quinoline and ofa compound, C9H7PU’12. It is therefore probably a molecular compound.This characteristic yellow precipitate, giving t,he ammonia reactionabove described, is obtained by the action of iodine chloride on all sub-stances containing pyridine nuclei, with the exception of a few quino-line-derivatives.Several chloriodides are described. Substitution inthe pyridine-ring does not prevent the reaction from takihg place, butinfluences the results ; f o r instance,.qztinaldine chloriodide reacts withammonia only when warmed. Hydroxyquinolines, hydroxylated inthe benzene-ring, reach differently with iodine chloride ; the productsdo not react with ammonia. The author expects, with the help of thisdifference of behaviour, to be able to determine the presence orabsence of substitution in oertain directions in the alkalo’ids.The reactions of the alkaloids with iodine chloride are described,All alkalo‘ids which react with iodine chloride and yield the charac-teristic bright yellow precipitate which gives the ammonia reaction,contain one or more pyridine nuclei, the number of the latter,corresponding, as a rule, with the number of halogen-groups in theproduct.N. H. M.Method for Determining Positions in the Pyridine Series.By A. LADENBURG (Bey., 18, 2967--2969).-The fact that cincho-meronic acid, when heated, yields two monocarboxylic acids (nicoticand isonicotic acids) excludes the constitution az’ and pp’. Theposition aB, as belonging to quinolinic acid which when heated yieldsnicotic acid, is excluded, as is also the position ap’. The only positionswhich now remain are ay and &, from which it follows tliat eithernicotic or isonicotic acid has the carboxyl in the y-position ; nicoticacid must, however, have the carboxyl-group in the Z- or P-position,as it can be obtained from quinolinic acid : hence isonicotic acid hasthe constitution, [N : COOH = 1 : 41.When cinchomeronic acid is reduced, cinchonic acid is formed ;this, when distilled yields pyrocinchoiiic anhydride, the acid corre-sponding with which can be obtained from a-dichloropropionic acid,and must therefore contain adjacent carboxyl-groups. I n nico tic acidORGANIC CHEMISTRY.159the carboxyl must therefore have the &position, and in picolinic acidthe only other position : namely, the a-position.Ethylpyridine and Ethylpiperidine.By A. LADENBURG (Bw.,18, 2961-2967 ; compare Abstr., 1885, 992).-The product obtainedby heating pyridiiie ethiodide a t 290" yields three bases: a-ethyl-pyridine, ty-ethylpyridine, and a-y-diet8hylpyridine.Theplatinochloride melts at 168-1'70", and dissolves readily in water ; theh.ydrochZoride melts a t about 110'. When oxidised, the base yieldspicolinic acid, and a small quantity of isonicotic acid (from theyderivative present as impurity). Yhe base when reduced yieldsa-ethylpiperidine, which was previously prepared (Abstr., 1884, 1054)but described as 7-ethylpiperidine. The platinochloride melts at 178".y - E t h y l p p i d i n e boils a t 164-166". Sp. gr. = 0.9592 at 0";0.9358 a t 20". It is sparingly soluble in water, and has an offensiveodour.Its reaotions resemble those of the a-compound. Theylatinochloride crystallises in well-formed plates melting a t 208"The gold salt forms gold-coloured, lustrous prisms, which melt a t138". When oxidised the base yieldsonly isonicotic acid. When reduced, a base, C7H15N, is formed, whichboils at 156-158" ; this is sparingly soluble in water, and has a dis-agreeable odour resembling that of piperidine. Sp. gr. = 0.8759a t 0". The platinochloride forms yellow plates sparingly soluble in coldwater ; it melts at 173-174".a-.l-DiethyZpyridine, C9HI3N, is formed only in small quantities ; itboils at 187-188", has an unpleasant odour, and is sparingly solublein water.N. H. M.a - E i h y l p y r i d i n e forms the chief pmduct ; it boils a t 150".The picrate melts a t 163".The gold salt melts a t 105".When oxidised it yields a-ylutidioic acid.N.8. M.Metachloroquinoline. By W. LA COSTE (Ber., 18,2940-2942).-The author has found that the metachloroquinoline previouslyexamined by him (Abstr., 1885, '792) is a mixture of chloroquinolinemelting a t 31-32", and metachloroquinoline, which is a liquid a t theordinary temperature and boils a t about 257". The dichromate of thesolid derivative forms long, slender, bright yellow needles which meltwith decomposition a t 165" ; metachloroquinoline dichromate crystal-lises in nodular-groups of very small needles melting a t 109". Thesolid base is acted on by nitric acid with formation of a compoundpreviously described as a-nitro-metachloroquinoline (compare Abstr.,1884, 1196) ; metachloroquinoline, when nitrated, yields p-nitrometa-chloroquinoline. N.H. M.Toluquinolines Substituted in the Pyridine-ring. By I,.R~GHEIMER and R. HOFFMANN (Her., 18, 2979-2989) .--.-P-y-Trichloroparat oluquinoline (me thy1 trichloroquinoline) ( Abstr . , 1884,1023) can also be prepared by the action of phosphoric chloride onparatoluidine mnlonate dissolved in dry benzene ; the product istreated with water and with soda, and distilled with steam. BecJidest~~lu;lorotoluquinoiine, dichloracetoparatolnide is obtained ; the twosubstances are separated by means of concentrated hydrochloric acid1 GO ABSTRACTS OF CEEMICAL PAPERS.Trichlorotoluquinoline is a feeble base readily soluble in strong acids,but is precipitated by adding water.p-y-DiclaZoroparatolucarbo~tyril, CloH,NC1,O [Me : C1, = 3 : 3' : 4'1,is obtained by heating trichlorotoluquinoline with dilute hydrochloricacid for five hours a t 180"; it forms slender needles insoluble inwater, sparingly soluble in alcohol and ether, and melts at 290-292",becoming brown a t the same time.It has both feeble acid and basicproperties. The potassium salt forms lustrous plates which aredecomposed by water. When a solution of the base in sulphuric acidis sahrated with nitrous acid, being kept cold all the while, and theproduct poured into water, 9-7- d ich lorodinitroparatol ucarbostyril,C,oH,NCl,(N02)2, is foimed. This crystallises from alcohol in long,lemon-coloured needles which melt at 186".Monoc h 1 orodiet hox y p arat o lug uin o line,C,NH,MeCl(OEt), [OEt : OEt = 2' : 3' or 4'J,is prepared by heating trichlorotoluquinoline with a solution ofsodium in anhydrous alcohol for two hours a t loo", and then for fourhours at 130"; the product is filtered and washed with water.Itforms long, colourless needles melting a t 70*5-71*5".Dichloroh ydroxyort hotoluqui?zo line,C9NH3MeClz*OH [Me : C1, : OH = 1 : 2' : 3' : 41,is obtained by the action of phosphoric chloride on hydrogenorthotoluidine malonate, and forms microscopic needles which me1 t a t245" ; it is sparingly soluble in water, alcohol, and glacial acetic acid.It dissolves in dilute, but more readily in concentrated acids ; it alsodissolves in carbonates.When heated with phosphoric chloride for1$ hours at 125", it yields 2' : 3' : 4' trichlorortl~otoluquinoline,C,NH,Cl,Me, which resembles in appearance trichloroquinoline andtrichloroparatoluquinoline ; it melts at 111-112*5". It dissolvesreadily in concentrated hydrochloric acid, and is precipitated by theaddition of water. Dilute hydrochloric acid acts on it a t 180" withfor mation of dichl ororthotolucarbost~ril,CSNH,MeC1,*OH [Me : C1, : OH = 1 : 3' : 4' : 2'1.This compound melts at 287-288", and when strongly heated,sublimes ; it is insoluble in water, sparingly soluble in boiling alcohol,but dissolves readily in alcoholic potash.H y droxychlororthotolucarbostyril,CSNH3MeC1(OH), [Me : C1 : (OH), = 1 : 3' : 2' : 4'1,is formed when 4' : 2' : 3' hydroxydichlororthotoluquinoline is heatedwith dilute hydrochloric acid for five hours a t 160".It crystallises inlustrous plates melting a t 276-277", and is readily soluble in glacialacetic acid, in ammonia, and in alkaline carbonates. It is insoluble inwater, and sparingly soluble in alcohol.Dichloracetortl~otoluide, CcH4Me*NH*CO*CHCI,, prepared fromorthotohidine malonate, crystallises in needles, which are very readilysoluble in alcohol and ether, sparingly soluble in light petroleum. Itdissolves slowly in dilute soda. When warmed with caustic alkali, iORG-4INIC CHEMISTRY. 161decomposes, giving off an odour of isonitriles. Phosphoric chloride acts011 it with formation of a mixture of cii- and tri-chlorinated quinolines.DichZoracetometatoZuide, C,H,Me*NH*CO*CHCI,, forms slender,colourless plates with silky lustre, melting a t 98-100".It is decom-posed when warmed with alkaline carbonates, and yields an oil havingthe powerful odour of isonitriles. N. H. M.Formation of Quinoline-derivatives by the Action of Phos-phoric Chloride on the Malonates of Primary Aromatic Bases.Ry L. R~~GHEIMER (Ber., 18, 2975--2978).-A discussion of thetheoretical bearings of the results described by the author in otherpapers (Abstr., 1884, 1050, and preceding Abstract).Formation of Quinolines from Meta-substituted Amines.By L. MEYER ( R e r . , 18, 2902--2903).-This paper is a preliminarynotice regarding the production from paraxylidene sulphate of adimethylquinoline boiling a t 265" under 736 mm.pressure and ofsp. gr. 1.070 a t 21". It is converted into a methylquinolinecar-boxylic acid by nitric acid. This acid, when heated, loses carbonicanhydride, and yields a methylquinoline, possibly identical with thatobtained from metatoluidine. V. H. V.Synthesis in the Quinoline, Series. By F. JUST (Ber., 18,2632--2635).-When ethyl anilbenzenylmalonate;PhN : CPh.CH(COOEt),(this ~ o l . , p. 149), is heated a t 150°, it is decomposed into ethyl alco-hol and eth y 1 p h e n y lhydroz y lq uino linecnrbmy 1 ate,OH*CgNH,Ph-COOEt [Ph : COOEt : OH = 2' : 3' : 4'1 ;it is colourless, crystalline, and melts a t 2623 The f r e e acid isobtained by heating the ethyl salt with hydrochlorib auid at 120", andmelts a t 232"; on further heating, it is convertedrinto a hydroxy-quinoline which, when distilled with zinc-dust, yields the knownn-phenylquinoline [Ph = 2'1, thus confirming the oonstitution de-duced from the method of formation.The author intends to applythis method to the preparation of substituted quinolines, preparing inthe first place substituted anilbenzenylmalonates by t b e action ofethyl sodomalonate or its substitu tion-derivatives on substitutedbenzanilimide chlorides, and thus obtaining quinoline-derivatives ofknown structure. A. J. G.Reduction of Nicotine. By A. LIEBRECHT (Be7*., 18, 2969-2970) .-Dipiperic%yZ, C,oH,,N,, is obtained by reducing nicotine inalcoholic solution with sodium. The platinochloride forms dark redcrystals which melt a t 202" ; the hydroch Zoride, aurocldoride, and picrateare described.D i n i t r o s o d ~ ~ i ~ e r i d y l , N0.C,NH,*C,NH9*N0, is pre-pared by the action of sodium nitrite on the base. N . H. M.By A. KRAKAU( J . Russ. Chem. SOC., 1885, 356--366).-A mixture of cinchonineAction of Caustic Alkalis on Cinchonine.VOL. L. 162 ABSTRACTS OF CHEMICAL PAPERS.and pure soda was heated in a flask and, as soon as the t'emperaturehad reached 170-190", a current of superheated steam passedthrough the apparatus, the reaction being conducted generally at195-210". A yellowish, optically active oil distils over with thesteam. This product, a mixtare of different substances, was redis-tilled with steam, when an optically inactive oil passed over, whilsta viscous heavy oil remained, which contained some cinchonine,but not enough to account for the optical activity of the original pro-duct, and another substance not yet fully investigated.The inactiveoil, on being redistilled, passed over between 240" and 265" ; its alco-holic solution was treated with alcoholic sulphuric acid, when crystal-lisation at once took place. The pink crystals, separated from thebrownish-red mother-liquor, after being boiled with absolute alcoholand repeatedly crystallised from acetic acid, melt at 228-229" ; theyare insoluble in ether, chloroform, and benzene, easily soluble inwater, and were found to be almost pure lepidine bisulphate. Thepink substance becomes colourless by treatmetit with animal charcoal,the melting point remaining unchanged.In the brown mother-liquor, quinoline bisulphate (m. p. 163.5-164.5 ") was found.The bases lepidine and quinoline, and some of their salts, were pre-pared from the bisulphates. As the former was obtained in a state ofgreater purity than by any other investigator, a more detailed descrip-tion of it is given : it is an oil distilling at 205.5" (bar. 746.7 mm.),of sp. gr. 1.0995 a t 0" and 1.0862 a t + 20" ; the author prepared thedichromate (begins to decompose at 136-138"), the picrate meltinga t 212-21 3", the platinochloride, and the aurochloride melting atThe optically active oil formed in the reaction simultaneously withlepidine and quinoline (resembling cinchonine in its properties) seemsto be produced in the early stages of thereaction of caustic alkalis oncinchonine ; indeed, if the reaction is carefully conducted without theuse of superheated steam, the oil is found in the product withoutany lepidine or quinoline having been formed.The investigation ofthe oil is continued.I n another paper (p. 282) the author states that by the action ofcaustic alkalis on cinchonidine, quinoline, lepidine, and a dextrorotat0r.yviscous oil are formed. From quinine and quinidine he has obtainedan amorphous optically active substance and two optically inactivebases, one of which is easily converted into a hydrate melting at 52".By A.MICHAEL (Amel.. Chern. J., 7, 182--1f33).-The best results wereobtained by heating 6 grams of cmstic soda, 6 grams of cinchonine,and 60 C.C.of absolute alcohol a t 130-135" for 8-10 hours; nogaseous products were formed. The contents of the tubes were freedfrom alcohol, a large quantiLy of water added, and the whole extractedwith ether. The ethereal extract when evaporated and distilled withsteam yielded a very small qua.ntity of volatile bases, about 1 per cent.of the cinchonine employed. The bases not volatilised by steamamounted to over 80 per cent. of the cinchonine employed; thcycould not be separated by distillation, but fractional precipitation188490".A. T.Decomposition of Cinchonine by Sodium EthoxideORGANIC CHEXISTRY. 163with platinum chloride showed that the material was almost perfectlyLomogeneous. The free base, C2,,Hz6N2, is a heavy, reddish-yellow,viscous oil ; the salts are, so far as examined, amorphous, except theplatinochloride, C20H26N2,H2P t Cl,.The aqueous alkaline solution, leftaft,er extraction with ether, contains formic acid. The reaction isthereFore probably expressed by the equation C19H2,N20 + EtONa =C,,H,,N,Et + HCOONa ; whence cinchonine would be an amide ofthe base CIEH2?NZ, and of formic acid; the volatile bases obtainedby other experimenters, are decomposition products of the base heredescribed. H. B.Artificial Preparation of Cocaine and its Homologues. ByW. MERCK (Bey., 18, 2952-2955 ; compare Abstr., 1885, l.249).-Cccaine can be prepared by heating anhydrous ecgonine with benzoicanhydride and methyl iodide for 10 hours a t 100"; the product irpoured into water, purified by extraction with ether and filtrationthrough animal charcoal, and the base is liberated by means ofsodium carbonate ; +#he yield is small.C o c e t h y h e , C18H23NOi, is prepared by heatina benzoylecgoninewith ethyl iodide and alcohol for eight hours at 103.It crystallis(*sfrom alcohol in splendid prisms with vitreous lustre, melting a t108-109". The platinochloride forms bright yellow rhotnbic plates ;it resembles cocaine platinochloride, but is more crystalline. Likecocaiiie, the base is an anzesthetic. N. H. M.Lupanine, an AlkaloYd from the Seed of the Blue Lupine.By &I. HAGEN (AnnaZen, 230, 367-384).--The seeds of the blue1 upine, Lupinus arhgustifolius, contain a liquid a1 kalo'id, lzcpanine,CI5H2,N2O, but do not contain either of the alkalo'ids Inpinine,C21Hao~,Oz,or lupinidine, CRHliN, which Baumert (Abstr , 1881, 831 ; 1882, 229,873; 1883, 100, 224) found in Lupinus luteus.The alkalo'id isextracted from the seed by Liebscher's process (Bey. landw. Institutzu Halle, Heft 11).Lupanine is a thick, non-crystallisable syrup, possessing a bittertaste and a strongly alkaline reaction. l t has a pale-yellow colour, andexhibits a green fluorescence. Lupanine attacks the skin, and fumesin the presence of hydrochloric acid. It is precipitated from its saltsb y soda and potash, but liberates ammonia from its compounds. Thealkaloid is sparingly soluble in water and alcohol, but is freely solublein ether, chloroform, and light petroleum. The liquid does not boila t 290" under a pressure of 130 mm.The 7~ydriodide, C,,H,N,O,HI + l$H,O, forms large, monoclinic crystals, which are sparinglysoluble in water and alcohol. The hydrochloride, C,,H,,N,O,€€Cl +2H20, appears to crystnllise in the quadratic system. It is a hygro-scopic salt, soluble in water and alcohol, but insoluble in ether; itmelts a t 127".The thiocyanate, Cl5H2,N,O,HSCN + +K,O, forms transparentcrystals, soluble in hot alcohol. The sulphate and oxalate do notcrystallise. The platinochloride, C,,H2,N,O,H2PtCl6 + 3+H20, is notm 164 ABSTRACTS OF CHEEhIICAL PAPERS.distinctly crystalline ; it is sparingly soluble in cold water and coldalcohol, and is insoluble in ether. Tlie aurochloride forms silky,golden needles, insoluble in water, alcohol, and ether.Lupanine unites with methyl iodide to form the methiodide,which is decomposed by moist oxide of silver, yielding the hydroxide,CI5H,,N20,MeOH. This base exists as- a colaurless syrup.It uniteswith acids, forming tx series of mystallina salts. Like lupanine, itforms an acid platinochloride, CI,H2,N,0,MeHPtC1, + H20. ThenurochZoride forms triclinic needle-shaped crystals, soluble in hotwater. w. c. w.Alkalo'ids in Old Flour.. By BALLAXD ( J . Pharm. [ 5 ] , 11, 341-342).-Flour kept in sacks for some time, shows traces of thepresence of alknla'ids, arvd later the quantity formed becomes moreand more appreciable. The flour is extracted with ether ; the solu-tion thus obtained gives on evaporation a fatty residue which isacid, especially in th'e case of very old flour ; its odour is disagreeableand penetrating, and its tast'e is very acrid. The presence of alka-loids in an aqueous extract of the residue can readily be detected bymeans of suitable reagent$. Flour112 to 18 months old gives sensibleamounts. The extract administered t o sparrows kills them afterseveral hours, whilst fresh flour gives no such results. J. T.New Method of Separating Globulins from Albumins.By V. M~CHAILOFF ( J . Russ. Chem, SOC., 1885, 348--354).-1n aformer communication (Abstr., 1885, 69) a method of preparing purealbumin was described, which consists in precipitating filtered whiteof egg with ammonium sulphate and dialysing the precipitated albu-mino'id matter, after dissolving it in water. Tlie present paper is adescription of the separation of the diserent albumino'id bodies con-tained in the serum of blood. A convenient volume of serum (20-.50 c.c.) is saturated with solid ammonium sulphate until the whole ofthe albumino'id matter is precipitated. The precipitate is thoroughlywashed with saturated ammonium sulphate solution, to free it fromother mineral salts, dissolved in the smallest possible volume of water,and placed in a dialyser. After 2-3 days' dialysing, water isadded to the solution, which is then filtered. The whole of theglobulins remain on the filter, whilst the albumin passes into thefiltrate. On sahrating this with magnesium sulpllate at 30°, not theslightest precipitate is formed. The author considers that globulinand albumin originally form a complex group in the serum, which,after eliniination of the mineral salts, is split up by the action of anexcess of water. It is noticed that on concentrating the dialysedmixture of serum, globulin, and albumin a t low temperatures (70-75"), the globulin precipitate disappears as soon as a certain degreeof concentration is reached. The existence of a compound of albuminand globulin in the serum is the more probable, as the reaction ofalbumin is acid (Zoc. cit.). As regards the globulins, or at least sub-8tances closely related t o them, some data established by DanilevskORGANIC CHEMISTRY. 165(Cenfr. Med. Wiss., 1880, 51) seem to point to their alkaline cha-racter. A. T.The Haemoglobin Molecule, By 0. ZINOFFSKY (Zeit. physiol.Chem., 10, 16-34) .-Former analyses of hmmoglobin have shownthat the molecule contains at least 600 atoms of carbon. This is aminimal number reckoned on the basis that only one atom of iron ispresent. Sulphur i8 also it constituent of hemoglobin, but previousdeterminations of the amount present show very contradictoryresults : hence the .supposition. first advanced by Lehmann, that thecrjstallised substance hemoglobin is not a chemical unit, but consistsof haematin, which I contains iron, mechanically mixed with a crys-tallised proteid. A seeming confirmatiola of t h i s theory has beenrecently advanced by Struve (Zeit. p a c t . Chew,., lM4), who foundthat by means of alcoholic ammonia, hsmatin could be extractedfrom tlie crystals, leaving them colourless. The author, however,shows that the conflicting results as to the ,quantity of sulphur presentare due to bad methods of preparation of hernoglobin, and thathzemoglobin is, after all., a chemical unit.The method of preparation is a s follows :-The red corpuscles arecollected from defibrizrated horse's blood, mixed with three timestheir volume of distilled water, the mixtwe warmed to 35", anci thehzemoglobin thm dissolved. The colourless stromata of the corpuscleslloat in the liquid, but are too small to be .separated by filtration.They are, therefore, dissolved by adding a smadl quantity of ammo-nia or ether. If ammonia is used, it must be afterwards neutralisedby dilute hydrochloric acid. Cry stallisation of the hzemoglobin isbrought about, by the addition to the liquid of a quarter of its volumeof alcohol, the mixture being kppt a t 0" for 48 hours. The crystalsform abundantly, are filtered off, washed with 75 per cent. alcohol a tO", redissolved in water at 35", and purified by repeated recrys-tallisation. By this method three preparations of pure haemoglo binwere made and submitted to analysis, and the ratio of iron to sulphuratoms found to be as 1 : 2. The formula deduced for hzemoglobin isC712H,,,N2,,S,Fe02~. The author further oonsidets that as decom-position-products of hzemoglobin, one molecule of hematin with34 atoms of carbon, and two molecules of proteid (globulin), eachwith one atom of sulphur and 339 of carbon, are formed. He, how-ever, thinks it probable that each molecule of prote'id contains fouratoms of sulphur and 1356 of carbon (that is, granting that peptonesare decompositiou-products of prote'id, and that each molecule ofpeptone probably contains two atoms of sulphur united in differentways). W. D. H.Action of Ammonia on Hsmin. By M. SHALF~EFF ( J . Russ.Chent. SOC., 1885, 203-204). - Hamin crystals, when treatedwith an alcoholic solution of ammonia, become colourless, withoutlosing their crystalline form or undergoing any change in volume ;the ammoniacal solution deposits brown, translucent, globular aggre-gates of needles. These crystals show double refraction in a higherdegree than haemin crystals, whilst the colourless crystals have en166 ABSTRACTS OF CHEMICAL PAPERS.tirely lost this property.of hEmin, heeminostromine, the colouring matter, haeminic acid,The author term., the colourless constituentA. T.By W. F.LOERISCH (Zeit. physiol. Chem., 10, 40--79).-The most importantrecent work on mucin is that of Landwehr (ibid., 6, 7 , 8, 9).Previously it was known that much mas an albumino’id, soluble indilute alkalis, precipitable by ac3tic acid, and that after heating withdilute sulphuric acid, a reducing substance of unknown nature isformed. The author holds that a prote’id and a carbohydrate are theproducts of decomposition of mucin, and that mucin is not merely amechanical mixture of two such substances, as Landwehr supposes, butprobably a glucoside. He prepares mucin by precipitating a lime-water extract of the tendons with acetic acid. After 24 hours, thelength of time the lime-water and the tendons are in contact does notcause more much to be dissolved, nor does the temperature of thelime-water make any difference. Boiling causes mucin t o be no longerprecipitable by acetic acid; 1 to 5 per cent. acetic acid is the beststrengt’h of acid to use, weaker acid causing only a cloudiness, not aprecipitate. Unlike Landwehr’s mucin (from saliva and snails),tendon-mucin is not chanqed into coagulated prote’id by boiling orby remaining under alcohol.The amount of mucin may be estimated not only by weighing thedried acetic acid precipitate, but by the decrease of alkalinity of analkaline solution employed to dissolve it, mucin having an acid reac-tion. The author’s formula for mucin is C1,H2JV3,S08,,. By heatingwith dilute sulphuric acid, it yields a carbohydrate of the formulaC,,H,,O,,; by still further heating, a reducing sugar, C61y1206, isobtained; this differs from Landwehr’s “ animal gum” in forming aclear solutiou with water ; a prote’id is also formed.On Mucin obtained from Tendons of the Ox.W. D. H

ISSN:0368-1769    

DOI:10.1039/CA8865000135

出版商:RSC    

年代:1886

数据来源: RSC

摘要:

166 ABSTRACTS OF CHEMICAL PAPERS. P h y s i o l o g i c a l C h e m i s t r y . Occurrence of Peptdne in Hen’s Eggs during Incubation. By W. FISCHEL (Zeit. physiol. Chem., 10, 11--IS).-The author had observed that the occurrence of peptone in the urine of puerperal women is a constant physiological phenomenon. He accounted for this (Archiw. Gyncik., 24,425) by supposing that peptones are formed in the tissues of the embryo during development, that excess of this diffuses into the maternal blood, and thence appears in the urine. Confirmation of this theory was obtained by examining the embryonic tissues and yolk of developing eggs. I n all, 42 specimens were examined, the period of incubation varying from the second to the nineteenth day. In eight cases,.peptones were found both in the embryonic tissues and in the yolk, in one embryo as much as 54 mrgms.being present. Peptones were never found before the fifteenth day, and in some cases not even after that date. The author hopes toPHYSIOLOGICAL CHEAIISTRS. 167 continue his investigation of the subject with a larger supplv of material. W. D. H. Occurrence of Peptones in Fibromata of the Uterus. By W. F~SCHEL (Zeit. physio2. Chew,., 10, 14--15).-Although peptone is not a normal constituent of the uterus, yet it occurs in those over- growths of the uterine muscular walls known as fibromata or myo- mata. On examining one of these turnours, abundant evidence of peptones was found in the watery extract after the precipitation of the other proteids. This would seem to be contained in the tumour itself, not in the contents of its blood-vessels and lymphatics, which were abundant,, because in a similar tumour, the blood and lymph were examined and peptones shown to be absent, although it was present in the muscular tissue of this tumour, as in the one first described.W. D. H. Relations of the Phosphates in Urine. By A. OTT (Zeit. physioZ. Chem., 10, 1-lo).-The acid reaction of urine is now known to be due to an excess of acid over normal phosphates. The author gives a serics of analyses showing the relative quantities of phosphoric acid present in the urine combined in the form of acid and normal phosphates. Huppert’s method of analysis was used. The urine was collected daily at 10 P.M., 8 A.M., and 2 P.M. Meals were taken after each collection of urine ; dinner and supper consisting of meat and vegetables, breakfast of coffee and bread.The average of the analyses shows that the ratio of P,05 combined as normal phosphate to that combined as acid phosphate WBS as follows :-Evening urine (2 P.M. to 10 P.M.j as 91 : 100, night urine (10 P.M. to 8 A.M.) 56 : 100, morning urine (8 A.M. to 2 P.M.) 58 : 100, or for the total urine for 24 hours as 69 : 100. The large amount of normal phosphates present in the evening’s urine illustrates the previously known fact of the relation between the food taken and the phosphates in the urine. Erlenmeyer (Ber., 9, 1839) has shown that acid calcium phosphate is soluble in 700 parts of water. But that the urine is able to hold more than this in solution is accounted fop by the presence of othw salts in it, for it is known that i f aeid calcium phosphate and calcium chloride be mixed in equivalent t quantities, a solution can be obtained in which the phosphate is dissolved in only 342 parts of water.Similarly it is shown that the normal phosphate is more soluble in urine than in water, salts such) rn potassium phosphate and sodium chloride aiding its solution. By heating the aqueous solution of both phosphates, they are pre- cipitated, the acid phosphate being changed into the normal phosphate, whilst phosphoric acid passes into solution. But in normal urine no such precipitate, or only a very slight one occurs. This is accounted for again by the presence of other salts, especially magnesium phos- phate, potassium phosphate, and sodium phosphate.This can be shown experimentally with the individual salts, and normal urine contains such proportions of these salts as to prevent precipitation by heat. W. D. H.168 ABSTRACTS OF CHERlICAL PAPERS. Fat,. per cent. 2 '3 6 .6 3.7 Composition of the Milk of Shorthorns and other Cows and Goats. By P. VIETH (Bled. Centr., 1885, 603--606).-The following results were obtained by Volcker in 1881--t?4, when examining the milk of several cows :- Shorthorns. Cream in creamome- ters. per cent. 3 16 9 ---- -- Minimum . . . Maximum . . , Average , . . . weeks. 1 31 10 Lacta- Daily Dry tion. I yield. 1 gr' 1 matter. kilos. per cent. 4.990 1.02'70 10.9 25.473 1.0360 15.1 1'7.663 1-0315 12.6 - 8.051 1-0300 23 18-377 1.0370 8 13.851 1.0327 'Jerseys .12.3 14.8 13.5 3.0 5-6 4.1 Minimum.. . Maximum . . . Average , , . . 7 20 12 - 74 -14 11.340 1-0288 11.6 2.6 2 21.880 1.0360 14.9 5 *6 1'7 16-183 1.0324 13.5 4-2 11 Querns ey s. 2 12 6 Minimum .. , Maximum .. Average., . . . 16.556 1.0316 9 -9 27-329 1'0360 14.2 21'793 1.0330 12.0 2 1*@300 28 I 168:;g 1 1.0340 1 iz't 15 11'244 1-0319 13.9 1.9 4.4 3.1 I I I I I 6 14 9 A yrshires. Average .. . . Minimum . . . Maximum . . . Average . . . . 16 1.767 I 1.0829 1 14.1 4.9 1 - Minimum . , . Maximum .. Average , . . . , Goats. The author has during three years examined the milk of 300 short- horns, and finds the following yearly average :-VEGETABLE PHYSIOLOGY AND AQRICULTURE. 169 -~ ~ 1881. 1882. 1883. Speci6c gravity ............... 1 *0326 1 -0330 1 * 0328 Dry matter, per cent........... 13.0 13.1 13.0 FLtt,per cent .................. 1 3.8 1 3.8 1 3 . 7 E. W. P. Hypnotic Properties of Phenyl Methyl Ketone. By D. BEAU- METZ and G. BARDET (Coypi. yend.,.lOl, 960-961).-Phenyl methyl ketone bas powerful hypnotic properties, and in this respect surpasses chloral and paraldehyde. When administered together with a little glycerol in gelatin capsules, in doses of 0.05 to 0.15 gram, it produces profound sleep, followed by no evil after-effects, except that the breath is disagreeable in consequence of the elimination of the ketone by the lungs. If the ketone is injected under the skin 0-f the guinea-pig in doses of 0.5 to 1 gram, it produces R remarkable hypnotic torpor, and this gradually passes into a state of coma which ends in death in five or six hours.C. H. B. Poisonous Product of the Culture of Comma Bacillus. By W. NICATI and RIETSCH (J. Pharrn. [ 5 ] , 11, 292-296).-The authors have already shown the poisonous effect of comma bacillus cultures when injected into the veins of dogs (Abstr., 1885,180). In the present paper they show that a product obtained by Stas' method from these cultures is also poisonous. As contradictory or negative results have been previously published, the authors seek to ascertain if this poison is constantly or only accidentally formed. J. T. 166 ABSTRACTS OF CHEMICAL PAPERS. P h y s i o l o g i c a l C h e m i s t r y . Occurrence of Peptdne in Hen’s Eggs during Incubation. By W. FISCHEL (Zeit. physiol. Chem., 10, 11--IS).-The author had observed that the occurrence of peptone in the urine of puerperal women is a constant physiological phenomenon.He accounted for this (Archiw. Gyncik., 24,425) by supposing that peptones are formed in the tissues of the embryo during development, that excess of this diffuses into the maternal blood, and thence appears in the urine. Confirmation of this theory was obtained by examining the embryonic tissues and yolk of developing eggs. I n all, 42 specimens were examined, the period of incubation varying from the second to the nineteenth day. In eight cases,.peptones were found both in the embryonic tissues and in the yolk, in one embryo as much as 54 mrgms. being present. Peptones were never found before the fifteenth day, and in some cases not even after that date. The author hopes toPHYSIOLOGICAL CHEAIISTRS.167 continue his investigation of the subject with a larger supplv of material. W. D. H. Occurrence of Peptones in Fibromata of the Uterus. By W. F~SCHEL (Zeit. physio2. Chew,., 10, 14--15).-Although peptone is not a normal constituent of the uterus, yet it occurs in those over- growths of the uterine muscular walls known as fibromata or myo- mata. On examining one of these turnours, abundant evidence of peptones was found in the watery extract after the precipitation of the other proteids. This would seem to be contained in the tumour itself, not in the contents of its blood-vessels and lymphatics, which were abundant,, because in a similar tumour, the blood and lymph were examined and peptones shown to be absent, although it was present in the muscular tissue of this tumour, as in the one first described.W. D. H. Relations of the Phosphates in Urine. By A. OTT (Zeit. physioZ. Chem., 10, 1-lo).-The acid reaction of urine is now known to be due to an excess of acid over normal phosphates. The author gives a serics of analyses showing the relative quantities of phosphoric acid present in the urine combined in the form of acid and normal phosphates. Huppert’s method of analysis was used. The urine was collected daily at 10 P.M., 8 A.M., and 2 P.M. Meals were taken after each collection of urine ; dinner and supper consisting of meat and vegetables, breakfast of coffee and bread. The average of the analyses shows that the ratio of P,05 combined as normal phosphate to that combined as acid phosphate WBS as follows :-Evening urine (2 P.M.to 10 P.M.j as 91 : 100, night urine (10 P.M. to 8 A.M.) 56 : 100, morning urine (8 A.M. to 2 P.M.) 58 : 100, or for the total urine for 24 hours as 69 : 100. The large amount of normal phosphates present in the evening’s urine illustrates the previously known fact of the relation between the food taken and the phosphates in the urine. Erlenmeyer (Ber., 9, 1839) has shown that acid calcium phosphate is soluble in 700 parts of water. But that the urine is able to hold more than this in solution is accounted fop by the presence of othw salts in it, for it is known that i f aeid calcium phosphate and calcium chloride be mixed in equivalent t quantities, a solution can be obtained in which the phosphate is dissolved in only 342 parts of water.Similarly it is shown that the normal phosphate is more soluble in urine than in water, salts such) rn potassium phosphate and sodium chloride aiding its solution. By heating the aqueous solution of both phosphates, they are pre- cipitated, the acid phosphate being changed into the normal phosphate, whilst phosphoric acid passes into solution. But in normal urine no such precipitate, or only a very slight one occurs. This is accounted for again by the presence of other salts, especially magnesium phos- phate, potassium phosphate, and sodium phosphate. This can be shown experimentally with the individual salts, and normal urine contains such proportions of these salts as to prevent precipitation by heat. W. D. H.168 ABSTRACTS OF CHERlICAL PAPERS.Fat,. per cent. 2 '3 6 .6 3.7 Composition of the Milk of Shorthorns and other Cows and Goats. By P. VIETH (Bled. Centr., 1885, 603--606).-The following results were obtained by Volcker in 1881--t?4, when examining the milk of several cows :- Shorthorns. Cream in creamome- ters. per cent. 3 16 9 ---- -- Minimum . . . Maximum . . , Average , . . . weeks. 1 31 10 Lacta- Daily Dry tion. I yield. 1 gr' 1 matter. kilos. per cent. 4.990 1.02'70 10.9 25.473 1.0360 15.1 1'7.663 1-0315 12.6 - 8.051 1-0300 23 18-377 1.0370 8 13.851 1.0327 'Jerseys . 12.3 14.8 13.5 3.0 5-6 4.1 Minimum.. . Maximum . . . Average , , . . 7 20 12 - 74 -14 11.340 1-0288 11.6 2.6 2 21.880 1.0360 14.9 5 *6 1'7 16-183 1.0324 13.5 4-2 11 Querns ey s. 2 12 6 Minimum .. , Maximum ..Average., . . . 16.556 1.0316 9 -9 27-329 1'0360 14.2 21'793 1.0330 12.0 2 1*@300 28 I 168:;g 1 1.0340 1 iz't 15 11'244 1-0319 13.9 1.9 4.4 3.1 I I I I I 6 14 9 A yrshires. Average .. . . Minimum . . . Maximum . . . Average . . . . 16 1.767 I 1.0829 1 14.1 4.9 1 - Minimum . , . Maximum .. Average , . . . , Goats. The author has during three years examined the milk of 300 short- horns, and finds the following yearly average :-VEGETABLE PHYSIOLOGY AND AQRICULTURE. 169 -~ ~ 1881. 1882. 1883. Speci6c gravity ............... 1 *0326 1 -0330 1 * 0328 Dry matter, per cent.. ......... 13.0 13.1 13.0 FLtt,per cent .................. 1 3.8 1 3.8 1 3 . 7 E. W. P. Hypnotic Properties of Phenyl Methyl Ketone. By D. BEAU- METZ and G. BARDET (Coypi. yend.,.lOl, 960-961).-Phenyl methyl ketone bas powerful hypnotic properties, and in this respect surpasses chloral and paraldehyde.When administered together with a little glycerol in gelatin capsules, in doses of 0.05 to 0.15 gram, it produces profound sleep, followed by no evil after-effects, except that the breath is disagreeable in consequence of the elimination of the ketone by the lungs. If the ketone is injected under the skin 0-f the guinea-pig in doses of 0.5 to 1 gram, it produces R remarkable hypnotic torpor, and this gradually passes into a state of coma which ends in death in five or six hours. C. H. B. Poisonous Product of the Culture of Comma Bacillus. By W. NICATI and RIETSCH (J. Pharrn. [ 5 ] , 11, 292-296).-The authors have already shown the poisonous effect of comma bacillus cultures when injected into the veins of dogs (Abstr., 1885,180).In the present paper they show that a product obtained by Stas' method from these cultures is also poisonous. As contradictory or negative results have been previously published, the authors seek to ascertain if this poison is constantly or only accidentally formed. J. T.166 ABSTRACTS OF CHEMICAL PAPERS.P h y s i o l o g i c a l C h e m i s t r y .Occurrence of Peptdne in Hen’s Eggs during Incubation.By W. FISCHEL (Zeit. physiol. Chem., 10, 11--IS).-The author hadobserved that the occurrence of peptone in the urine of puerperalwomen is a constant physiological phenomenon. He accounted forthis (Archiw. Gyncik., 24,425) by supposing that peptones are formedin the tissues of the embryo during development, that excess of thisdiffuses into the maternal blood, and thence appears in the urine.Confirmation of this theory was obtained by examining the embryonictissues and yolk of developing eggs.I n all, 42 specimens wereexamined, the period of incubation varying from the second to thenineteenth day. In eight cases,.peptones were found both in theembryonic tissues and in the yolk, in one embryo as much as 54 mrgms.being present. Peptones were never found before the fifteenth day,and in some cases not even after that date. The author hopes tPHYSIOLOGICAL CHEAIISTRS. 167continue his investigation of the subject with a larger supplv ofmaterial. W. D. H.Occurrence of Peptones in Fibromata of the Uterus.ByW. F~SCHEL (Zeit. physio2. Chew,., 10, 14--15).-Although peptone isnot a normal constituent of the uterus, yet it occurs in those over-growths of the uterine muscular walls known as fibromata or myo-mata. On examining one of these turnours, abundant evidence ofpeptones was found in the watery extract after the precipitation ofthe other proteids. This would seem to be contained in the tumouritself, not in the contents of its blood-vessels and lymphatics, whichwere abundant,, because in a similar tumour, the blood and lymph wereexamined and peptones shown to be absent, although it was present inthe muscular tissue of this tumour, as in the one first described.W. D. H.Relations of the Phosphates in Urine. By A. OTT (Zeit.physioZ. Chem., 10, 1-lo).-The acid reaction of urine is now knownto be due to an excess of acid over normal phosphates.The authorgives a serics of analyses showing the relative quantities of phosphoricacid present in the urine combined in the form of acid and normalphosphates. Huppert’s method of analysis was used. The urinewas collected daily at 10 P.M., 8 A.M., and 2 P.M. Meals were takenafter each collection of urine ; dinner and supper consisting of meatand vegetables, breakfast of coffee and bread. The average of theanalyses shows that the ratio of P,05 combined as normal phosphateto that combined as acid phosphate WBS as follows :-Evening urine(2 P.M. to 10 P.M.j as 91 : 100, night urine (10 P.M. to 8 A.M.) 56 : 100,morning urine (8 A.M. to 2 P.M.) 58 : 100, or for the total urine for24 hours as 69 : 100.The large amount of normal phosphates present in the evening’surine illustrates the previously known fact of the relation betweenthe food taken and the phosphates in the urine.Erlenmeyer (Ber., 9, 1839) has shown that acid calcium phosphateis soluble in 700 parts of water.But that the urine is able to holdmore than this in solution is accounted fop by the presence of othwsalts in it, for it is known that i f aeid calcium phosphate andcalcium chloride be mixed in equivalent t quantities, a solution can beobtained in which the phosphate is dissolved in only 342 parts ofwater. Similarly it is shown that the normal phosphate is moresoluble in urine than in water, salts such) rn potassium phosphateand sodium chloride aiding its solution.By heating the aqueous solution of both phosphates, they are pre-cipitated, the acid phosphate being changed into the normal phosphate,whilst phosphoric acid passes into solution.But in normal urine nosuch precipitate, or only a very slight one occurs. This is accountedfor again by the presence of other salts, especially magnesium phos-phate, potassium phosphate, and sodium phosphate. This can beshown experimentally with the individual salts, and normal urinecontains such proportions of these salts as to prevent precipitation byheat. W. D. H168 ABSTRACTS OF CHERlICAL PAPERS.Fat,.per cent.2 '36 .63.7Composition of the Milk of Shorthorns and other Cows andGoats. By P. VIETH (Bled.Centr., 1885, 603--606).-The followingresults were obtained by Volcker in 1881--t?4, when examining themilk of several cows :-Shorthorns.Cream increamome-ters.per cent.3169---- --Minimum . . .Maximum . . ,Average , . . .weeks.13110Lacta- Daily Drytion. I yield. 1 gr' 1 matter.kilos. per cent.4.990 1.02'70 10.925.473 1.0360 15.11'7.663 1-0315 12.6- 8.051 1-030023 18-377 1.03708 13.851 1.0327'Jerseys .12.314.813.53.05-64.1Minimum.. .Maximum . . .Average , , . .72012-74-1411.340 1-0288 11.6 2.6 221.880 1.0360 14.9 5 *6 1'716-183 1.0324 13.5 4-2 11Querns ey s.2126Minimum .. ,Maximum ..Average., . . .16.556 1.0316 9 -927-329 1'0360 14.221'793 1.0330 12.02 1*@30028 I 168:;g 1 1.0340 1 iz't15 11'244 1-0319 13.91.94.43.1I I I I I6149A yrshires.Average ... .Minimum . . .Maximum . . .Average . . . .16 1.767 I 1.0829 1 14.1 4.9 1 -Minimum . , .Maximum ..Average , . . .,Goats.The author has during three years examined the milk of 300 short-horns, and finds the following yearly average :VEGETABLE PHYSIOLOGY AND AQRICULTURE. 169-~ ~1881. 1882. 1883.Speci6c gravity ............... 1 *0326 1 -0330 1 * 0328Dry matter, per cent.. ......... 13.0 13.1 13.0FLtt,per cent .................. 1 3.8 1 3.8 1 3 . 7E. W. P.Hypnotic Properties of Phenyl Methyl Ketone. By D. BEAU-METZ and G. BARDET (Coypi. yend.,.lOl, 960-961).-Phenyl methylketone bas powerful hypnotic properties, and in this respect surpasseschloral and paraldehyde. When administered together with a littleglycerol in gelatin capsules, in doses of 0.05 to 0.15 gram, it producesprofound sleep, followed by no evil after-effects, except that the breathis disagreeable in consequence of the elimination of the ketone by thelungs.If the ketone is injected under the skin 0-f the guinea-pig in dosesof 0.5 to 1 gram, it produces R remarkable hypnotic torpor, and thisgradually passes into a state of coma which ends in death in five orsix hours. C. H. B.Poisonous Product of the Culture of Comma Bacillus. ByW. NICATI and RIETSCH (J. Pharrn. [ 5 ] , 11, 292-296).-The authorshave already shown the poisonous effect of comma bacillus cultureswhen injected into the veins of dogs (Abstr., 1885,180). In the presentpaper they show that a product obtained by Stas' method from thesecultures is also poisonous. As contradictory or negative results havebeen previously published, the authors seek to ascertain if this poisonis constantly or only accidentally formed. J. T

ISSN:0368-1769    

DOI:10.1039/CA8865000166

出版商:RSC    

年代:1886

数据来源: RSC

摘要:

VEGETABLE PHYSIOLOGY AND AQRICULTURE. 169 Chemistry of Vegetable Physiology and Agriculture. Composition and Fermentation of Invert Sugar. By E. BOURQIJELOT (Comnpt. rend., 101,958-960).-A reply to Maurnen6 and to Leplay. The author shows that Leplay’s results really support his own conclusions. C. H. B. Inverting Ferment of Cane-sugar. By A. LADUREAU (Ann, Agronm., 11, 404408) .--Certain saccharometer tubes containing solutions of cane-sugar to be examined optically, were found to gradually lose their rotatory power on being allowed to remain for some hours. At the end of two or three days the whole of the cane-sugar was found to be converted into invert sugar. Subacetate of lead, far from hindering this inversion, appears to favour it. The ferment appeared to be attached to the tubes used, for when these were washed with hydrochloric acid, phenol, or salicylic acid, no inversion occurred.170 ABSTRACTS OF CHEMICAL PAPERS.Neither did it occur in solutions of sugar kept in glass vessels. The author explains by means of this fact the otherwise unaccountable deteriorat5on of the sugar (accompanied by inversion) which occurred in a sugar refinery under his own observation. J. 111. H. 31. Zymotic Properties of Certain Virus. By S. ARLOING (Compt. rend., 101, 819-821) .-Bacillus awthrax and Micrococcus septicus puerperalis from an old cultivation, produce no distinct fermentation, but Jf. septicus puerperdis from recent cultivations, and especially the anasrobic virus of gangrenous septicemia, and emphysematous anthrax in beef, cause rapid fermentations in solutions of glucose, lactose, saccharose, and mnnnitol, and act even still more energetically on solutions of starch, dextrin, and inulin.Hydrogen and carbonic anhydride are evolved in varying proportions, and the solutions, which become more or less acid, contain glucose. The deposlts formed during fei*mentation are capable of producing the same change in fresh solutions. The recently dried virus from septicemia and anthrax produce similar results, but if they have been dry for a long time, or if their pathogenic activity has been lessened by the action of heat, they lose their zymotic action without losing their injurious properties. It would seem, therefore, that the pathogenic properties of these micro- organisms are partially distinct from their zymotic properties ; the latter djkappear first, and seem to reside in the mycelium itself, and not in the spores.The analogy between virulent micro-organisms and ferments can no longer be doubted. Intramolecular Respiration. By PFEFFER (Ann. Agronom ., 11, 486-432).-Some experimentally observed values of the ratio between intramolecular and normal respiration (;) are as follows:-Bean, 0.994, 1.094, 0.829, 1.197 ; wheat, 0.490 ; whike mustard, 0.1 77, 0.181 ; turnip. 0*24!3 ; hemp, 0.339 ; sunflower, 0.354 ; lupine, 0*244-d1 the foregoing ratios refer to the young plants. In the fruits of Heracleum, before maturity, the ratio was 0.416 ; young branch of Abies excelsa, 0,077; flowering stem of Orobnnche ranzosa, 0.321 ; spadix of Arum maculatm, 0.615 ; branch of Ligustrum vidgure, 0.816 ; Luctarius piperatus, 0.31 6 ; Hydnum rqandum, 0.256 ; Cantharellus cib(iriu.9, 0.666 ; beer yeast cultivated with milk-sugar, 0.310. The remainder of the paper is devoted to a discussion of the theories which have heen advanced as to the nature of normal and intramolecular respira- tion, and their relations to each other.Pfeffer holds provisionally that the same cause produces intramolecular or normal respiration according as the plant is or is not deprived of oxygeii. C. H. B. J. M. H. M. Respiration of Leaves in the Dark. By DEHERAIN and MAQUENNE (Compt. rend., 101, 887-889) .-These experiments were undertaken with a view to establish the authors' previous conclusion (Abstr., 1885, 927) that leaves retain part of the carbonic anhydride hyhich they produce, and that consequently an analysis of the airVEGETABLE PHYSIOLOGY AKD AGRLCULTURE'.1 7 1 surrounding the leaves gives no accurate information regarding the i.atio between the oxygen absorbed and the carbonic anhydride pro- duced. A known quail tity of the leaves of Euonoii ymus japonica was placed in a known volume of pure air, and after some time the air surrounding the leaves was analysed, and then by making the mcuum complete, the air retained by the leaves was also extracted, and the second quantity of gas analysed. The first result gives the apparent ratio COz : 0 ; the second and first together give the real ratio. The difference between the two values depends on the ratio of the volume of the leaves to the volume of the space in which they are confined, and if the leaves occupy more than one-tenth of the space, the difference becomes considerable.The authors also find that if the leaves are placed in an atmosphere of carbonic anhydride in the dark, they rapidly absorb a considerable quantity of this gas. Germinative Power of Seeds after Exclusion of Air and Drying at High Temperatures. By W~LHELM (Bied. Cenfr., 1885, 611--613).-When seeds were dried at 50-60" and kept in hermeti- cally sealed vessels, it was thought that they retained their germinative power most effectively. The author has carried on his experiments in the same directioii on the same sample of seed for six years. For the sake of comparison, some seed was kept, in bags, so as to preserve it from dust; another sample was hermetically sealed up, and both samples exposed to the ordinary temperature ; two other samples were exposed for two hours, the one to a temperature of 50", the other t o 75".The seeds were winter wheat, rye, oats, and linseed. The results: exclusion from the air enables the seed to retain its germinative power longer than when air has free access to i t ; this is especially the case with rye. Two hours' heating to 50", whereby some water is removed, is very effective for the preservation of the seed. After exposure to higher temperatures than 50", seeds, at least the cereals, germinate more slowly than if only exposed to a lower temperature. Seeds which have been artificially dried, when subse- quently moistened, absorb more water than they would otherwise have done ; and old seeds, as a rule, germinate more slowly than new seeds, especially if they have been exposed to the air.Absorption of the Non-alimentary Substances by Plants. By KNOP (Ann. Agronom., 11, 418-419 ; from Bot. Centr., 22, 35).- Maize plants were grown in nutrient solutions containing 2 grams per litre of the followiiig mixture of salts :-4 parts calcium nitrate, 1 part potassium nitrate, 1 part potassium phosphate, and 2 parts crgstallised magnesium sulphate. One solution was neutral, the other was acidified by the addition of 0.07455 gram free phosphoric acid. The phosphates of most metals are soluble in t.he acid solution, and were added to it in a freshly precipitated stat'e, mixed with phosphate of iron. Tlie author's previous .researches have shown that iodine and bromine, in small quantities, are not more injurious tha2n chlorine, but that in larger doses iodine is the most injurious, C.H. B. E. W. P.172 ABSTRACTS OF CHEXICXL PAPERS. then bromine, and chlorine least. Also that zinc, boric acid, cobalt, copper, silver phosphate, and gold chloride are poisonous ; but strontium, barium, and manganese are absorbed without injury. The researches reported in the present *paper gave the following results : Ammonium vanadate (50 mgrms. per litre) is poisonous a t the end of two days. Roots coloured white by the lower oxides of vanadium soon cease to grow, but as soon bs all the salt is absorbed the plants become healthy again. Holy bdic acid acts in the same way. Phospho- tungstic acid in doses of 0*05-0.1 gram is very poisonous.Tellurous acid, being scarcely soluble in the nutrient solution, is not absorbed. Telluric acid (0*05-0*1 gram, per litre) is without action ; whilst selenious and selenic acids are very poisonous. Arsenious acid is very poisonous, but potassium arsenate given in 0.05 gram dose to plants of maize with 10 to 15 leaves, did not hinder normal growth and fructification, nor kill a Volvox globator or a mauld. Cadmium and thallium are poisonous. Lead phosphate feebly retarded the general development of the plant without disorgariising the various iunctions. Bismuth resembles lead in this respect,. Oxalic, humic, malic, tartaric, citric, benzoic, and succinic acids are without influence when very dilute. Potassium ferrocyanide rapidly remedies chlorosis ; in 0.1 gram dose it simply arrests the growth of the plant, which nevertheless remains green and healthy until autumn.Hydroxyl- amine hydrochloride, in the, proportion of O.5.gram per litre, is very poisonous ; so are mellitic acid and ammonium mellitate in doses of 1 gram. It is doubtful whether nickel and bismuth are absorbed, since they cannot be found in the plant. Chromium and uranium oxides are not absorbed because of their. insolubility. The following substances act fatally on the roots, whether or not they are really absorbed : silver oxide, gold chloride, platinum chloride, x-anadic, molybdic, and phosphotungstic acids, thallium oxide, selenious and selenic acids, boric and chromic acids. By A. F A w N T z I N and S.PRZIBYTEK (J. Russ. Chena. SOC., 1885, 371--372).-0n drying the pollen of Pinus silvestri's a t 200-105" it loses 6.;9 per cent. in weight ; the dried substance gives 3.30 per cent. of ash containing- E20. Na,O. CaO. MgO. Fe203,Al,03. MnO. P205. SO3. C1. 35.25 3-62 0.88 7-00 5.30 trace 29-86 14.83 0.99 nitrogen by Kjeldahl's method = 2.40 per cent. ; if the whole of t b i s nitrogen be calculated in the form of albumino'id matter (which obviously is only approximately correct), the quantity of the latter in the pollen is 15 per cent. (compare Von Planta, this vol., p. 91). J. M. H. M. Ash of the Pollen of Pinus Silvestris. A. T. Glycyrrhizin in Myrrhis Odorata. By SCHROEDER (Arch. Pharm. [3], 23, 621-622).-Guignet has remarked the presence of glycyrrhizin in plants not belonging to the Papilionaceae; this in- duced the author to examine Myrrhis odorata both by Robiquet's method and that of Guignet.The latter (treatment with acetic acid, then with alcohol, and after concentration, separation by means ofVEGETABLE PHYSIOLOGY AND AGRICULTURE. 17:; water, &c.) gave unsatisfactory results. The plant was treated with aqueous ammonia, sulpliuric acid added t o the filtrate, the precipitate evaporated to dr.yness with barium carbonate, treated with alcohol, and the filtrat,e evaporated. Repeated attempts were made to obtain a crystallised product, but without success. The reactions of gly- cyrrhizin were obtained. J. T. Nitrogenous Constituents of Pumpkin Sprouts. Ry E. SCHULZE (J. pr. Chem. [2], 32, 433--461).-1n continuation of his work on this subject (compare Abstr., 1880, .180), the author describes in full detail the methods by which he isolated or recognised the follow- ing substances :-Glutamine, asparagine, tyrosine, lencine, vernine, members of the xanthine-group (probably as decomposition products of nucle’in), ammoilium salts, and nihrates.Most of these substances occur in both axial organs and cotyledons ; but asparacine and ver- nine were found only in the cotyledons, ghtamine in the axial orgalis only. A. J. G. BV E. HECKEL and F. SCHLAGDEN- HAUFFEN (Compt. rend., 101, 955-957) .-This root, contrary to the statement of Bourdon, contains no alkaloPd. The colouring principle, which is also the therapeutic agent, was isolated by precipitating the extract of the root with basic lead acet&te, decomposing the precipi- tate with hydrogen sulphide, and evaporating the red solution to dryness after filtering.The residue is a greenish-brown substance, completely soluble in alcohol, acetone, and methyl alcohol, less soluble i n chloroform and ether, and only slightly soluble in cold water, b u t completely soluble in boiling water. The greater part sublimes unchanged when heated, but a small portion is carbonised. This substance, to which the aut’hor gives tlic name danain, has the compo- sition Cl4HI4O5, and splits ITP into half its own weight of glilcose, and a resinous amorphous compound, danafdin, which probably has the coinposition C2,Hz,06. C. H. B. Root of Danais Fragrans. Composition of Spurrey (Spergula Arvensis), Spurrey Seed, and Spurrey Silage.By J. 31. H. MUNRO (FieZd, 1885, 386--38i). -Spurrey, recently recommended as a suitable crop for growing on barren sands with a view bo ensiling, has the following composition, the specimen analysed being cut on June 12th, partly in flower and partly in seed. The air-dried spurrey, or hay, contained in 100 parts :-Water, 20.79 ; insoluble ash, 5.33 ; soluble ash, 4.77 ; crude fibre, 23.82 ; oil (light petroleum extract), 3.80 ; resin, &c., soluble in ether, 1.47 ; true albumino’ids, 8-75 ; starch, digestible fibre, amides, &c., 41.22. The total nitrogen was 1.82 per cent., and the albuminoid nitrogen 1.40 per cent ; 77 per cent. of the total nitrogen was thus albumino‘id. Silage was made on a small scale (in a glass vessel) from a portion of the same sample, and its analysis, compared with that of the fresh herbage, is exhibited Water, 81.43 ; dry substance, 18-57.the following tables :-174 ABSTRACTS OF CHEMlOAL PAPERS. Fresh Fresh herbage. silage. Water ......................... Ash, insoluble in water ........... Ash, soluble in water ............ Crude fibre ..................... Ether extract.. ................. Albumino'ids ................... Volatile acid, reckoned as acetic.. . Fixed acid reckoned as lactic.. .... St,arch, digestible fibre, soluble carbohydrates,* amides, and other non- albumino'id nitro- genous substances ........... 81-43 1.12 0.99 4-96 1.09 1-82 - - 8.59 77-23 0.88 0.98 5.75 1.78 0-76 0.06 0.94 11.62 Total nit,rogen .................. 0.378 0.334 Albumindid nitrogen ............ I 0.291 I 0.122 +Non-albumino'id nitrogen........ Nitrogen soluble in water ........ - 0.087 0.262 0-289 Percentage composi- ;ion of dry substance of Herbage. - 6.03 5-34 26-70 5-90 9 '81 - - 46*22 100'01, 2.04 1-57 0.4'7 - Silage. - 3.86 4.30 25-25 7 *82 3.34 0.26 4-13 51.04 100*00 1.68 0.54 1.14 1.2'7 The loss of mineral matter is apparent only, and is caused by adven- titious sand in the samples. The crude fibre and the fat appear to undergo no alteration. Two-thirds of the albuminoyds are lost during the fermentation i n the silo ; some of their nitrogen is absolutely lost (as nitrogen gas), but most of it exists in the silage as ammonia, amides, &c. As bearing on this point, an experiment made in 1883 on the fermentation of the nitrogen of gelatin, first with ammonia, and afterwards with nitric acid, under the influence of soil-ferments, is recorded in this paper..The total loss of weight suffered by the spurrey during its conversion into ensilage did not exceed 8.4 per cent. of the dry substance. The starch contained in the seeds of the spurrey herbage was found unaltered in the fresh silage, but the sour silage could not be dried in a steam oven without total conversion of this starch into carbohydrates, giving no iodine reaction. A slight loss of nitrogen, and of non-nitrogenous matter, a considerable trans- formation of albuminojids into less valuable substances, and a develop- ment of free acid a t the expense of a little sugary or starchy material, probably sum up all the important changes brought about in the manufacture of good silage.Some specimens of silage will keep well on exposure to the air, others become mouldy, others ra,pidly putrefy : the causes of the differences are a t present unknown, but probably depend on the proportions of water and free acid. The lower layers of silage contains more, the upper layers less water than the original herba,ge. Spurrey seed contains in 100 parts :-Water, 11.48; ash, 2.58;VEGETABLE PHYSIOLOGY AND AGRICULTURE. 175 crude fibre, 13.93 ; oil (light petroleum extract), 8-52 ; resin, soluble in ether, insoluble in alcohol. 2.24; other substances extracted by ether, 1.44 ; albumino'ids, 10.13 ; starch, digestible fibre, &c., 49.68. The nitrogen is almost entirely albuminoi'd, and amounts to 1.62 per cent.The black testa of the seed contains a siibstnnce with a peacock- blue fluorescence, similar to the peonio$uorescin, discovered by Dragendorff in the testa of peony seeds. This substance is insoluble in water and light petroleum, soluble ;P ether and alcohol. To extract it, the crushed seeds are exhausted first with light petroleum to free them from oil, and then with alcohol. The alcoholic solution is evaporated to dryness, and the residue boiled with water (which dissolves out tannin and other substances amounting to 5 per cent. of the seed). The residue insoluble in water is an olive-green powder, whose alcoholic or ethereal solution exhibits fluorescence of increased brilliancy, but this fluorescence disappears after some days, the solu- tions becoming dark-brown.This solution gives a peculiar taste and odour to spurrey seed. Absorption of Free Nitrogen from the Atmosphere by Argillaceous Soils. By BERTHELOT (Compt. rend., 101, 775-784). -Four different kinds of soil, namely, two samples of yellow argil- laceous sand, white clay, and crude kaolin were placed in open cylin- drical pots of glazed earthenware aud left, for many months in a closed apartment, freshly plastered, well lighted, dry, and free from any effluvia. Samples for analysis were taken from the various pots a t intervals. In all four cases, the amount of combined nitrogen in- creased continually and very considerably, whilst nitrification remained stationary, and the proportion of ammonia, always small, was either constant or tended to decrease.The same soils were placed in glazed porcelain pots perforated at the bottom, and the pots were supported on a table in a meadow a t a height of 0.7 m. from the ground. The pots were protected from vertical rain by a roof, whilst the air could circulate freely round them, and they were exposed to the action of oblique rain. During the latter part of the experiment, the soils were watered with dis- tilled water on account of the extreme dryness of the weather. A similar series of pots was exposed, without any protection from the weather, on the top of a tower 29 m. above the soil of a meadow, I n both series the result was the same as in the first series ; the amount of combined nitrogen continually increased. The amount of nitro yen in the rain which fell during the latter experiments was estimated by collecting the rain in st hygrometer with a known collecting surface and determining the amount of ammonia.The atmospheric ammonia was estimated by placing it vessel containing dilute acid by the side of the pots containing the soils. The amount of nitrogen derived from nitrogen compounds in the atmosphere was much less than the amount of nitrogen absorbcd by the soils, and it follows from this result that the absorption of nitrogen by these soils is independent of the combined nitrogen in the air, or, in other words, free nitrogen is absorbed. J. M. H. M.176 ABSTRACTS OF CHEMICAL PAPERS. Yellow argillaaeoue-sand, I.. .. 0'0910 0 *11'79 I 0.0983 I - >, 3 ) ,, I1 ....I 0.1119 ' 0.1639 0.1295 1 0.1396 White clay.................. 0'0210 0.0407 0.0353 I 0.0557 Crude kaolin ................ 0.1065 0.1144 I 0.1497' I 1 - 1 i I n a fourth series of experiments, 1 kilo. of each soil was placed in a flask of 4 litres capacity, moistened with water, and the flasks stop- pered and placed in diffused light or in the dark, as the case might be. I n all the soils employed, the amount of combined nitrogen con- tinually increased, the absorption taking place somewhat more rapidly in the light than in the dark. The amounts of nitrates and ammonia remained constant or diminished. It was found, however, that if the soils were sterilised by heating a t 100" for two hours, and only filtered air was allowed to enter the flasks, or even i f the sterilised soil was freely exposed in a closed apartment, no increase in the amount of nitrogen was observed.From these results it follows that argillaceous soils have the power of absorbing free nitrogen from the air, the absorption taking place under the influence of living organisms. This absorption is perfect,ly distinct from nitrification. It does not take place in winter, but proceeds most rapidly when vegetation is most active. The following table gives the amount. of nitrogen absorbed by 1 kilo. of the different soils during six months; that is, from April to October, 1885 r- 0.1289 0'1503 0.0494 0'1236 The absolute weight of nitrogen absorbed was 0*02-0*04 gram per kilo., or, calculating from the surface exposed in the pots, 26-32 kilos. per hectare. This last number is, however, too low, since absorption is not confined to the surface, but extends to a considerable depth. C.H. B. Changes occurring during and the Action of Water in Irriga- tion. By J. KONIG and C. BOHMER ( B i d Ceittr., 1885, 577-594).- The researches, of which mention was made (Abstr., 1882, 655), have hxm continued in the South of France on fields cultivated under a six-course sjstem. It was found that with the same absolute amount of water flowing, the evaporat'ion from equal surfaces was the same. Water, when present in small quant,ities, was more thoroughly ex- hausted of its constituents than when much was present; that is, the absolute quantity of materials removed by like surfaces was in all cases alike. Poor soils abstract more mineral matter from water than rich; consequently, water cannot be so frequently used on poor as on fertile land.The manuring action, or the cession of minerals to the soil, is not absolutely dependent on the absorptive capacity of the soil, hut the plants themselves absorb a considerable part, the quautity varying with their energy of growth. This manuring action is by no means the chief advantage which the soil gains, forTWETABLE PHYSIOLOGY AND AGRICULTURE. 177 the water remores 8ome uselcss material and reduces the acidity in its passage through. The quantity of manure which water brings can be easily replaced by artificial manures, but the neutralisation of the acid must be accomplished by ploughing, &c. The last result is accomplished by irrigating according to Vincent’s system (simple surface or gravitation), but this requires plenty of water and natural subsoil drainage, by which a t least 100 litres per hectare a second can flow away.If the supply of water is wanting, when only 10.70 litres are available, then the oxidising action must be assisted hy drainage ; in such a case Petersen’s valvular drainage system may be employed with great advantage. With plenty of fall, with 20- 30 litres a t disposal, Abel’s system is best. Effect of Various Manures on the Ash of Tobacco. By W. El. JORDAN (Bied. Centr., 1885,598-600) .-In order that tobacco, when prepared for smoking purposes, shall burn well, it must contain but little chlorides J consequently, all manures containing chlorides must be carefully avoided. Tobacco also requires much potash ; therefore, the sulphate and carbonate (potashes) should be employed.The analyses show that the absolute quantity of ash is not much altered, but that the constituents of that ash vary very considerably according to the manure. E. W. P. E. W. P. Analysis of Tobacco Leaves and Stems. By E. H. JENKINS (Died. CerLtr., 1885, 623--627).--The results stated in this article are similar to t8hose in the previous Abstract. There appears to be no relationship between the capability for burning and the percentage of potassium carbonate in the plant. Efs SIR J. B. LAWES and J. H. GILBERT (Jour. Roy. Agri. Xoc. Etbg., 42 (1885) [2], 590- 611).-The authors revise the table, originally issued 25 years ago, containing their estimates of the manurial value of one ton of various farm foods, after deducting that portion of the manurial constituents of each food which may be supposed, in the case of a fattening animal, to appear as increase of live-weight.The cdcu- lations are made on the same principles as the former ones, and the alterations are due in some measure to the adoption of average per- centage compositions based on more recent analyses, but chiefly to the alteration in the price of ammonia, which is now valued a t 6d. per lb. instead of 8d. ; phosphoric acid and potash are now valued at 3d. and a i d . per lb. as against 2 i d . and 2d. per lb. respectively. Whereas in the former table the manurial value of a t’on of linseed cake consumed by a fattening animal appeared as S4 12s. 6d., it is now estimated to be S 3 28s.6d.; that of a ton of maize is reduced from $1 11s. to $1 5s. Id. Of the Woburn experiments, in which “ the manure from cattle foods of such widely different manure value as decorticated cotton-cake and maize have shown very little difference in the crops to which they were applied,” the authors remark that “ the result was doubtless due to tlie condition of the land being, in both cases, high enough to yield approximately maximum crops.” E. W. P. Valuation of Unexhausted Manures. VOL. L. n178 ABSTRAOTS OF CHEMICAL PAPERS. Tn addition to the revised table of original manurial value of the different foods after consumption by fattening animals, the authors now attempt an estimate of the compensation value or unexhausted manurial value of the same foods, after they have been used for a series of years by the outgoing tenant, and he has realised a certain portion of the manure value in his increased crops.In the case of all the foods except hays and straws, one-half of the original manurial value of the purchased food used during the last year of the outgoing tenmt’s possession is to be deducted, and the remainder is the unexhausted manurial value. The unexhausted value of foods used the year before is one-third less than this; and one- third is deducted from the remainder for every additional year up to the eighth year before quitting. I n the case of hays and straws, the constituents of which more slowly become available to crops, two-thirds of the original manurial value is deducted for the last Sear, and only one-fifth from year to year for each preceding year up to the eighth. For the many circumstances which must be taken into account in attempting to utilise the authors’ tables, the original paper must, be consulted; the principle, however, on which emphasis i q laid, is the substitution of manurial value for cost of purchased foods as the basis of valuations.J. M. H. M. VEGETABLE PHYSIOLOGY AND AQRICULTURE. 169 Chemistry of Vegetable Physiology and Agriculture. Composition and Fermentation of Invert Sugar. By E. BOURQIJELOT (Comnpt. rend., 101,958-960).-A reply to Maurnen6 and to Leplay. The author shows that Leplay’s results really support his own conclusions. C. H. B. Inverting Ferment of Cane-sugar. By A. LADUREAU (Ann, Agronm., 11, 404408) .--Certain saccharometer tubes containing solutions of cane-sugar to be examined optically, were found to gradually lose their rotatory power on being allowed to remain for some hours.At the end of two or three days the whole of the cane-sugar was found to be converted into invert sugar. Subacetate of lead, far from hindering this inversion, appears to favour it. The ferment appeared to be attached to the tubes used, for when these were washed with hydrochloric acid, phenol, or salicylic acid, no inversion occurred.170 ABSTRACTS OF CHEMICAL PAPERS. Neither did it occur in solutions of sugar kept in glass vessels. The author explains by means of this fact the otherwise unaccountable deteriorat5on of the sugar (accompanied by inversion) which occurred in a sugar refinery under his own observation.J. 111. H. 31. Zymotic Properties of Certain Virus. By S. ARLOING (Compt. rend., 101, 819-821) .-Bacillus awthrax and Micrococcus septicus puerperalis from an old cultivation, produce no distinct fermentation, but Jf. septicus puerperdis from recent cultivations, and especially the anasrobic virus of gangrenous septicemia, and emphysematous anthrax in beef, cause rapid fermentations in solutions of glucose, lactose, saccharose, and mnnnitol, and act even still more energetically on solutions of starch, dextrin, and inulin. Hydrogen and carbonic anhydride are evolved in varying proportions, and the solutions, which become more or less acid, contain glucose. The deposlts formed during fei*mentation are capable of producing the same change in fresh solutions.The recently dried virus from septicemia and anthrax produce similar results, but if they have been dry for a long time, or if their pathogenic activity has been lessened by the action of heat, they lose their zymotic action without losing their injurious properties. It would seem, therefore, that the pathogenic properties of these micro- organisms are partially distinct from their zymotic properties ; the latter djkappear first, and seem to reside in the mycelium itself, and not in the spores. The analogy between virulent micro-organisms and ferments can no longer be doubted. Intramolecular Respiration. By PFEFFER (Ann. Agronom ., 11, 486-432).-Some experimentally observed values of the ratio between intramolecular and normal respiration (;) are as follows:-Bean, 0.994, 1.094, 0.829, 1.197 ; wheat, 0.490 ; whike mustard, 0.1 77, 0.181 ; turnip.0*24!3 ; hemp, 0.339 ; sunflower, 0.354 ; lupine, 0*244-d1 the foregoing ratios refer to the young plants. In the fruits of Heracleum, before maturity, the ratio was 0.416 ; young branch of Abies excelsa, 0,077; flowering stem of Orobnnche ranzosa, 0.321 ; spadix of Arum maculatm, 0.615 ; branch of Ligustrum vidgure, 0.816 ; Luctarius piperatus, 0.31 6 ; Hydnum rqandum, 0.256 ; Cantharellus cib(iriu.9, 0.666 ; beer yeast cultivated with milk-sugar, 0.310. The remainder of the paper is devoted to a discussion of the theories which have heen advanced as to the nature of normal and intramolecular respira- tion, and their relations to each other. Pfeffer holds provisionally that the same cause produces intramolecular or normal respiration according as the plant is or is not deprived of oxygeii.C. H. B. J. M. H. M. Respiration of Leaves in the Dark. By DEHERAIN and MAQUENNE (Compt. rend., 101, 887-889) .-These experiments were undertaken with a view to establish the authors' previous conclusion (Abstr., 1885, 927) that leaves retain part of the carbonic anhydride hyhich they produce, and that consequently an analysis of the airVEGETABLE PHYSIOLOGY AKD AGRLCULTURE'. 1 7 1 surrounding the leaves gives no accurate information regarding the i.atio between the oxygen absorbed and the carbonic anhydride pro- duced. A known quail tity of the leaves of Euonoii ymus japonica was placed in a known volume of pure air, and after some time the air surrounding the leaves was analysed, and then by making the mcuum complete, the air retained by the leaves was also extracted, and the second quantity of gas analysed. The first result gives the apparent ratio COz : 0 ; the second and first together give the real ratio.The difference between the two values depends on the ratio of the volume of the leaves to the volume of the space in which they are confined, and if the leaves occupy more than one-tenth of the space, the difference becomes considerable. The authors also find that if the leaves are placed in an atmosphere of carbonic anhydride in the dark, they rapidly absorb a considerable quantity of this gas. Germinative Power of Seeds after Exclusion of Air and Drying at High Temperatures.By W~LHELM (Bied. Cenfr., 1885, 611--613).-When seeds were dried at 50-60" and kept in hermeti- cally sealed vessels, it was thought that they retained their germinative power most effectively. The author has carried on his experiments in the same directioii on the same sample of seed for six years. For the sake of comparison, some seed was kept, in bags, so as to preserve it from dust; another sample was hermetically sealed up, and both samples exposed to the ordinary temperature ; two other samples were exposed for two hours, the one to a temperature of 50", the other t o 75". The seeds were winter wheat, rye, oats, and linseed. The results: exclusion from the air enables the seed to retain its germinative power longer than when air has free access to i t ; this is especially the case with rye.Two hours' heating to 50", whereby some water is removed, is very effective for the preservation of the seed. After exposure to higher temperatures than 50", seeds, at least the cereals, germinate more slowly than if only exposed to a lower temperature. Seeds which have been artificially dried, when subse- quently moistened, absorb more water than they would otherwise have done ; and old seeds, as a rule, germinate more slowly than new seeds, especially if they have been exposed to the air. Absorption of the Non-alimentary Substances by Plants. By KNOP (Ann. Agronom., 11, 418-419 ; from Bot. Centr., 22, 35).- Maize plants were grown in nutrient solutions containing 2 grams per litre of the followiiig mixture of salts :-4 parts calcium nitrate, 1 part potassium nitrate, 1 part potassium phosphate, and 2 parts crgstallised magnesium sulphate.One solution was neutral, the other was acidified by the addition of 0.07455 gram free phosphoric acid. The phosphates of most metals are soluble in t.he acid solution, and were added to it in a freshly precipitated stat'e, mixed with phosphate of iron. Tlie author's previous .researches have shown that iodine and bromine, in small quantities, are not more injurious tha2n chlorine, but that in larger doses iodine is the most injurious, C. H. B. E. W. P.172 ABSTRACTS OF CHEXICXL PAPERS. then bromine, and chlorine least. Also that zinc, boric acid, cobalt, copper, silver phosphate, and gold chloride are poisonous ; but strontium, barium, and manganese are absorbed without injury.The researches reported in the present *paper gave the following results : Ammonium vanadate (50 mgrms. per litre) is poisonous a t the end of two days. Roots coloured white by the lower oxides of vanadium soon cease to grow, but as soon bs all the salt is absorbed the plants become healthy again. Holy bdic acid acts in the same way. Phospho- tungstic acid in doses of 0*05-0.1 gram is very poisonous. Tellurous acid, being scarcely soluble in the nutrient solution, is not absorbed. Telluric acid (0*05-0*1 gram, per litre) is without action ; whilst selenious and selenic acids are very poisonous. Arsenious acid is very poisonous, but potassium arsenate given in 0.05 gram dose to plants of maize with 10 to 15 leaves, did not hinder normal growth and fructification, nor kill a Volvox globator or a mauld.Cadmium and thallium are poisonous. Lead phosphate feebly retarded the general development of the plant without disorgariising the various iunctions. Bismuth resembles lead in this respect,. Oxalic, humic, malic, tartaric, citric, benzoic, and succinic acids are without influence when very dilute. Potassium ferrocyanide rapidly remedies chlorosis ; in 0.1 gram dose it simply arrests the growth of the plant, which nevertheless remains green and healthy until autumn. Hydroxyl- amine hydrochloride, in the, proportion of O.5.gram per litre, is very poisonous ; so are mellitic acid and ammonium mellitate in doses of 1 gram. It is doubtful whether nickel and bismuth are absorbed, since they cannot be found in the plant.Chromium and uranium oxides are not absorbed because of their. insolubility. The following substances act fatally on the roots, whether or not they are really absorbed : silver oxide, gold chloride, platinum chloride, x-anadic, molybdic, and phosphotungstic acids, thallium oxide, selenious and selenic acids, boric and chromic acids. By A. F A w N T z I N and S. PRZIBYTEK (J. Russ. Chena. SOC., 1885, 371--372).-0n drying the pollen of Pinus silvestri's a t 200-105" it loses 6.;9 per cent. in weight ; the dried substance gives 3.30 per cent. of ash containing- E20. Na,O. CaO. MgO. Fe203,Al,03. MnO. P205. SO3. C1. 35.25 3-62 0.88 7-00 5.30 trace 29-86 14.83 0.99 nitrogen by Kjeldahl's method = 2.40 per cent. ; if the whole of t b i s nitrogen be calculated in the form of albumino'id matter (which obviously is only approximately correct), the quantity of the latter in the pollen is 15 per cent. (compare Von Planta, this vol., p.91). J. M. H. M. Ash of the Pollen of Pinus Silvestris. A. T. Glycyrrhizin in Myrrhis Odorata. By SCHROEDER (Arch. Pharm. [3], 23, 621-622).-Guignet has remarked the presence of glycyrrhizin in plants not belonging to the Papilionaceae; this in- duced the author to examine Myrrhis odorata both by Robiquet's method and that of Guignet. The latter (treatment with acetic acid, then with alcohol, and after concentration, separation by means ofVEGETABLE PHYSIOLOGY AND AGRICULTURE. 17:; water, &c.) gave unsatisfactory results. The plant was treated with aqueous ammonia, sulpliuric acid added t o the filtrate, the precipitate evaporated to dr.yness with barium carbonate, treated with alcohol, and the filtrat,e evaporated.Repeated attempts were made to obtain a crystallised product, but without success. The reactions of gly- cyrrhizin were obtained. J. T. Nitrogenous Constituents of Pumpkin Sprouts. Ry E. SCHULZE (J. pr. Chem. [2], 32, 433--461).-1n continuation of his work on this subject (compare Abstr., 1880, .180), the author describes in full detail the methods by which he isolated or recognised the follow- ing substances :-Glutamine, asparagine, tyrosine, lencine, vernine, members of the xanthine-group (probably as decomposition products of nucle’in), ammoilium salts, and nihrates. Most of these substances occur in both axial organs and cotyledons ; but asparacine and ver- nine were found only in the cotyledons, ghtamine in the axial orgalis only.A. J. G. BV E. HECKEL and F. SCHLAGDEN- HAUFFEN (Compt. rend., 101, 955-957) .-This root, contrary to the statement of Bourdon, contains no alkaloPd. The colouring principle, which is also the therapeutic agent, was isolated by precipitating the extract of the root with basic lead acet&te, decomposing the precipi- tate with hydrogen sulphide, and evaporating the red solution to dryness after filtering. The residue is a greenish-brown substance, completely soluble in alcohol, acetone, and methyl alcohol, less soluble i n chloroform and ether, and only slightly soluble in cold water, b u t completely soluble in boiling water. The greater part sublimes unchanged when heated, but a small portion is carbonised.This substance, to which the aut’hor gives tlic name danain, has the compo- sition Cl4HI4O5, and splits ITP into half its own weight of glilcose, and a resinous amorphous compound, danafdin, which probably has the coinposition C2,Hz,06. C. H. B. Root of Danais Fragrans. Composition of Spurrey (Spergula Arvensis), Spurrey Seed, and Spurrey Silage. By J. 31. H. MUNRO (FieZd, 1885, 386--38i). -Spurrey, recently recommended as a suitable crop for growing on barren sands with a view bo ensiling, has the following composition, the specimen analysed being cut on June 12th, partly in flower and partly in seed. The air-dried spurrey, or hay, contained in 100 parts :-Water, 20.79 ; insoluble ash, 5.33 ; soluble ash, 4.77 ; crude fibre, 23.82 ; oil (light petroleum extract), 3.80 ; resin, &c., soluble in ether, 1.47 ; true albumino’ids, 8-75 ; starch, digestible fibre, amides, &c., 41.22.The total nitrogen was 1.82 per cent., and the albuminoid nitrogen 1.40 per cent ; 77 per cent. of the total nitrogen was thus albumino‘id. Silage was made on a small scale (in a glass vessel) from a portion of the same sample, and its analysis, compared with that of the fresh herbage, is exhibited Water, 81.43 ; dry substance, 18-57. the following tables :-174 ABSTRACTS OF CHEMlOAL PAPERS. Fresh Fresh herbage. silage. Water ......................... Ash, insoluble in water ........... Ash, soluble in water ............ Crude fibre ..................... Ether extract................... Albumino'ids ................... Volatile acid, reckoned as acetic.. . Fixed acid reckoned as lactic.. .... St,arch, digestible fibre, soluble carbohydrates,* amides, and other non- albumino'id nitro- genous substances ........... 81-43 1.12 0.99 4-96 1.09 1-82 - - 8.59 77-23 0.88 0.98 5.75 1.78 0-76 0.06 0.94 11.62 Total nit,rogen .................. 0.378 0.334 Albumindid nitrogen ............ I 0.291 I 0.122 +Non-albumino'id nitrogen. ....... Nitrogen soluble in water ........ - 0.087 0.262 0-289 Percentage composi- ;ion of dry substance of Herbage. - 6.03 5-34 26-70 5-90 9 '81 - - 46*22 100'01, 2.04 1-57 0.4'7 - Silage. - 3.86 4.30 25-25 7 *82 3.34 0.26 4-13 51.04 100*00 1.68 0.54 1.14 1.2'7 The loss of mineral matter is apparent only, and is caused by adven- titious sand in the samples.The crude fibre and the fat appear to undergo no alteration. Two-thirds of the albuminoyds are lost during the fermentation i n the silo ; some of their nitrogen is absolutely lost (as nitrogen gas), but most of it exists in the silage as ammonia, amides, &c. As bearing on this point, an experiment made in 1883 on the fermentation of the nitrogen of gelatin, first with ammonia, and afterwards with nitric acid, under the influence of soil-ferments, is recorded in this paper.. The total loss of weight suffered by the spurrey during its conversion into ensilage did not exceed 8.4 per cent. of the dry substance. The starch contained in the seeds of the spurrey herbage was found unaltered in the fresh silage, but the sour silage could not be dried in a steam oven without total conversion of this starch into carbohydrates, giving no iodine reaction.A slight loss of nitrogen, and of non-nitrogenous matter, a considerable trans- formation of albuminojids into less valuable substances, and a develop- ment of free acid a t the expense of a little sugary or starchy material, probably sum up all the important changes brought about in the manufacture of good silage. Some specimens of silage will keep well on exposure to the air, others become mouldy, others ra,pidly putrefy : the causes of the differences are a t present unknown, but probably depend on the proportions of water and free acid. The lower layers of silage contains more, the upper layers less water than the original herba,ge.Spurrey seed contains in 100 parts :-Water, 11.48; ash, 2.58;VEGETABLE PHYSIOLOGY AND AGRICULTURE. 175 crude fibre, 13.93 ; oil (light petroleum extract), 8-52 ; resin, soluble in ether, insoluble in alcohol. 2.24; other substances extracted by ether, 1.44 ; albumino'ids, 10.13 ; starch, digestible fibre, &c., 49.68. The nitrogen is almost entirely albuminoi'd, and amounts to 1.62 per cent. The black testa of the seed contains a siibstnnce with a peacock- blue fluorescence, similar to the peonio$uorescin, discovered by Dragendorff in the testa of peony seeds. This substance is insoluble in water and light petroleum, soluble ;P ether and alcohol. To extract it, the crushed seeds are exhausted first with light petroleum to free them from oil, and then with alcohol.The alcoholic solution is evaporated to dryness, and the residue boiled with water (which dissolves out tannin and other substances amounting to 5 per cent. of the seed). The residue insoluble in water is an olive-green powder, whose alcoholic or ethereal solution exhibits fluorescence of increased brilliancy, but this fluorescence disappears after some days, the solu- tions becoming dark-brown. This solution gives a peculiar taste and odour to spurrey seed. Absorption of Free Nitrogen from the Atmosphere by Argillaceous Soils. By BERTHELOT (Compt. rend., 101, 775-784). -Four different kinds of soil, namely, two samples of yellow argil- laceous sand, white clay, and crude kaolin were placed in open cylin- drical pots of glazed earthenware aud left, for many months in a closed apartment, freshly plastered, well lighted, dry, and free from any effluvia.Samples for analysis were taken from the various pots a t intervals. In all four cases, the amount of combined nitrogen in- creased continually and very considerably, whilst nitrification remained stationary, and the proportion of ammonia, always small, was either constant or tended to decrease. The same soils were placed in glazed porcelain pots perforated at the bottom, and the pots were supported on a table in a meadow a t a height of 0.7 m. from the ground. The pots were protected from vertical rain by a roof, whilst the air could circulate freely round them, and they were exposed to the action of oblique rain. During the latter part of the experiment, the soils were watered with dis- tilled water on account of the extreme dryness of the weather.A similar series of pots was exposed, without any protection from the weather, on the top of a tower 29 m. above the soil of a meadow, I n both series the result was the same as in the first series ; the amount of combined nitrogen continually increased. The amount of nitro yen in the rain which fell during the latter experiments was estimated by collecting the rain in st hygrometer with a known collecting surface and determining the amount of ammonia. The atmospheric ammonia was estimated by placing it vessel containing dilute acid by the side of the pots containing the soils. The amount of nitrogen derived from nitrogen compounds in the atmosphere was much less than the amount of nitrogen absorbcd by the soils, and it follows from this result that the absorption of nitrogen by these soils is independent of the combined nitrogen in the air, or, in other words, free nitrogen is absorbed.J. M. H. M.176 ABSTRACTS OF CHEMICAL PAPERS. Yellow argillaaeoue-sand, I.. .. 0'0910 0 *11'79 I 0.0983 I - >, 3 ) ,, I1 ....I 0.1119 ' 0.1639 0.1295 1 0.1396 White clay.. ................ 0'0210 0.0407 0.0353 I 0.0557 Crude kaolin ................ 0.1065 0.1144 I 0.1497' I 1 - 1 i I n a fourth series of experiments, 1 kilo. of each soil was placed in a flask of 4 litres capacity, moistened with water, and the flasks stop- pered and placed in diffused light or in the dark, as the case might be. I n all the soils employed, the amount of combined nitrogen con- tinually increased, the absorption taking place somewhat more rapidly in the light than in the dark.The amounts of nitrates and ammonia remained constant or diminished. It was found, however, that if the soils were sterilised by heating a t 100" for two hours, and only filtered air was allowed to enter the flasks, or even i f the sterilised soil was freely exposed in a closed apartment, no increase in the amount of nitrogen was observed. From these results it follows that argillaceous soils have the power of absorbing free nitrogen from the air, the absorption taking place under the influence of living organisms. This absorption is perfect,ly distinct from nitrification. It does not take place in winter, but proceeds most rapidly when vegetation is most active.The following table gives the amount. of nitrogen absorbed by 1 kilo. of the different soils during six months; that is, from April to October, 1885 r- 0.1289 0'1503 0.0494 0'1236 The absolute weight of nitrogen absorbed was 0*02-0*04 gram per kilo., or, calculating from the surface exposed in the pots, 26-32 kilos. per hectare. This last number is, however, too low, since absorption is not confined to the surface, but extends to a considerable depth. C. H. B. Changes occurring during and the Action of Water in Irriga- tion. By J. KONIG and C. BOHMER ( B i d Ceittr., 1885, 577-594).- The researches, of which mention was made (Abstr., 1882, 655), have hxm continued in the South of France on fields cultivated under a six-course sjstem.It was found that with the same absolute amount of water flowing, the evaporat'ion from equal surfaces was the same. Water, when present in small quant,ities, was more thoroughly ex- hausted of its constituents than when much was present; that is, the absolute quantity of materials removed by like surfaces was in all cases alike. Poor soils abstract more mineral matter from water than rich; consequently, water cannot be so frequently used on poor as on fertile land. The manuring action, or the cession of minerals to the soil, is not absolutely dependent on the absorptive capacity of the soil, hut the plants themselves absorb a considerable part, the quautity varying with their energy of growth. This manuring action is by no means the chief advantage which the soil gains, forTWETABLE PHYSIOLOGY AND AGRICULTURE.177 the water remores 8ome uselcss material and reduces the acidity in its passage through. The quantity of manure which water brings can be easily replaced by artificial manures, but the neutralisation of the acid must be accomplished by ploughing, &c. The last result is accomplished by irrigating according to Vincent’s system (simple surface or gravitation), but this requires plenty of water and natural subsoil drainage, by which a t least 100 litres per hectare a second can flow away. If the supply of water is wanting, when only 10.70 litres are available, then the oxidising action must be assisted hy drainage ; in such a case Petersen’s valvular drainage system may be employed with great advantage.With plenty of fall, with 20- 30 litres a t disposal, Abel’s system is best. Effect of Various Manures on the Ash of Tobacco. By W. El. JORDAN (Bied. Centr., 1885,598-600) .-In order that tobacco, when prepared for smoking purposes, shall burn well, it must contain but little chlorides J consequently, all manures containing chlorides must be carefully avoided. Tobacco also requires much potash ; therefore, the sulphate and carbonate (potashes) should be employed. The analyses show that the absolute quantity of ash is not much altered, but that the constituents of that ash vary very considerably according to the manure. E. W. P. E. W. P. Analysis of Tobacco Leaves and Stems. By E. H. JENKINS (Died. CerLtr., 1885, 623--627).--The results stated in this article are similar to t8hose in the previous Abstract.There appears to be no relationship between the capability for burning and the percentage of potassium carbonate in the plant. Efs SIR J. B. LAWES and J. H. GILBERT (Jour. Roy. Agri. Xoc. Etbg., 42 (1885) [2], 590- 611).-The authors revise the table, originally issued 25 years ago, containing their estimates of the manurial value of one ton of various farm foods, after deducting that portion of the manurial constituents of each food which may be supposed, in the case of a fattening animal, to appear as increase of live-weight. The cdcu- lations are made on the same principles as the former ones, and the alterations are due in some measure to the adoption of average per- centage compositions based on more recent analyses, but chiefly to the alteration in the price of ammonia, which is now valued a t 6d.per lb. instead of 8d. ; phosphoric acid and potash are now valued at 3d. and a i d . per lb. as against 2 i d . and 2d. per lb. respectively. Whereas in the former table the manurial value of a t’on of linseed cake consumed by a fattening animal appeared as S4 12s. 6d., it is now estimated to be S 3 28s. 6d.; that of a ton of maize is reduced from $1 11s. to $1 5s. Id. Of the Woburn experiments, in which “ the manure from cattle foods of such widely different manure value as decorticated cotton-cake and maize have shown very little difference in the crops to which they were applied,” the authors remark that “ the result was doubtless due to tlie condition of the land being, in both cases, high enough to yield approximately maximum crops.” E.W. P. Valuation of Unexhausted Manures. VOL. L. n178 ABSTRAOTS OF CHEMICAL PAPERS. Tn addition to the revised table of original manurial value of the different foods after consumption by fattening animals, the authors now attempt an estimate of the compensation value or unexhausted manurial value of the same foods, after they have been used for a series of years by the outgoing tenant, and he has realised a certain portion of the manure value in his increased crops. In the case of all the foods except hays and straws, one-half of the original manurial value of the purchased food used during the last year of the outgoing tenmt’s possession is to be deducted, and the remainder is the unexhausted manurial value.The unexhausted value of foods used the year before is one-third less than this; and one- third is deducted from the remainder for every additional year up to the eighth year before quitting. I n the case of hays and straws, the constituents of which more slowly become available to crops, two-thirds of the original manurial value is deducted for the last Sear, and only one-fifth from year to year for each preceding year up to the eighth. For the many circumstances which must be taken into account in attempting to utilise the authors’ tables, the original paper must, be consulted; the principle, however, on which emphasis i q laid, is the substitution of manurial value for cost of purchased foods as the basis of valuations. J. M. H. M.VEGETABLE PHYSIOLOGY AND AQRICULTURE.169Chemistry of Vegetable Physiology and Agriculture.Composition and Fermentation of Invert Sugar. By E.BOURQIJELOT (Comnpt. rend., 101,958-960).-A reply to Maurnen6 andto Leplay. The author shows that Leplay’s results really support hisown conclusions. C. H. B.Inverting Ferment of Cane-sugar. By A. LADUREAU (Ann,Agronm., 11, 404408) .--Certain saccharometer tubes containingsolutions of cane-sugar to be examined optically, were found to graduallylose their rotatory power on being allowed to remain for some hours.At the end of two or three days the whole of the cane-sugar wasfound to be converted into invert sugar. Subacetate of lead, far fromhindering this inversion, appears to favour it. The ferment appearedto be attached to the tubes used, for when these were washed withhydrochloric acid, phenol, or salicylic acid, no inversion occurred170 ABSTRACTS OF CHEMICAL PAPERS.Neither did it occur in solutions of sugar kept in glass vessels. Theauthor explains by means of this fact the otherwise unaccountabledeteriorat5on of the sugar (accompanied by inversion) which occurredin a sugar refinery under his own observation.J. 111. H. 31.Zymotic Properties of Certain Virus. By S. ARLOING (Compt.rend., 101, 819-821) .-Bacillus awthrax and Micrococcus septicuspuerperalis from an old cultivation, produce no distinct fermentation,but Jf. septicus puerperdis from recent cultivations, and especially theanasrobic virus of gangrenous septicemia, and emphysematous anthraxin beef, cause rapid fermentations in solutions of glucose, lactose,saccharose, and mnnnitol, and act even still more energetically onsolutions of starch, dextrin, and inulin.Hydrogen and carbonicanhydride are evolved in varying proportions, and the solutions,which become more or less acid, contain glucose. The deposltsformed during fei*mentation are capable of producing the samechange in fresh solutions.The recently dried virus from septicemia and anthrax producesimilar results, but if they have been dry for a long time, or if theirpathogenic activity has been lessened by the action of heat, they losetheir zymotic action without losing their injurious properties. Itwould seem, therefore, that the pathogenic properties of these micro-organisms are partially distinct from their zymotic properties ; thelatter djkappear first, and seem to reside in the mycelium itself, andnot in the spores.The analogy between virulent micro-organisms and ferments canno longer be doubted.Intramolecular Respiration.By PFEFFER (Ann. Agronom ., 11,486-432).-Some experimentally observed values of the ratio betweenintramolecular and normal respiration (;) are as follows:-Bean,0.994, 1.094, 0.829, 1.197 ; wheat, 0.490 ; whike mustard, 0.1 77, 0.181 ;turnip. 0*24!3 ; hemp, 0.339 ; sunflower, 0.354 ; lupine, 0*244-d1 theforegoing ratios refer to the young plants. In the fruits of Heracleum,before maturity, the ratio was 0.416 ; young branch of Abies excelsa,0,077; flowering stem of Orobnnche ranzosa, 0.321 ; spadix of Arummaculatm, 0.615 ; branch of Ligustrum vidgure, 0.816 ; Luctariuspiperatus, 0.31 6 ; Hydnum rqandum, 0.256 ; Cantharellus cib(iriu.9,0.666 ; beer yeast cultivated with milk-sugar, 0.310.The remainderof the paper is devoted to a discussion of the theories which haveheen advanced as to the nature of normal and intramolecular respira-tion, and their relations to each other. Pfeffer holds provisionallythat the same cause produces intramolecular or normal respirationaccording as the plant is or is not deprived of oxygeii.C. H. B.J. M. H. M.Respiration of Leaves in the Dark. By DEHERAIN andMAQUENNE (Compt. rend., 101, 887-889) .-These experiments wereundertaken with a view to establish the authors' previous conclusion(Abstr., 1885, 927) that leaves retain part of the carbonic anhydridehyhich they produce, and that consequently an analysis of the aiVEGETABLE PHYSIOLOGY AKD AGRLCULTURE'. 1 7 1surrounding the leaves gives no accurate information regarding thei.atio between the oxygen absorbed and the carbonic anhydride pro-duced.A known quail tity of the leaves of Euonoii ymus japonica wasplaced in a known volume of pure air, and after some time the airsurrounding the leaves was analysed, and then by making the mcuumcomplete, the air retained by the leaves was also extracted, and thesecond quantity of gas analysed. The first result gives the apparentratio COz : 0 ; the second and first together give the real ratio. Thedifference between the two values depends on the ratio of thevolume of the leaves to the volume of the space in which they areconfined, and if the leaves occupy more than one-tenth of the space,the difference becomes considerable.The authors also find that if the leaves are placed in an atmosphereof carbonic anhydride in the dark, they rapidly absorb a considerablequantity of this gas.Germinative Power of Seeds after Exclusion of Air andDrying at High Temperatures.By W~LHELM (Bied. Cenfr., 1885,611--613).-When seeds were dried at 50-60" and kept in hermeti-cally sealed vessels, it was thought that they retained their germinativepower most effectively. The author has carried on his experimentsin the same directioii on the same sample of seed for six years. Forthe sake of comparison, some seed was kept, in bags, so as to preserveit from dust; another sample was hermetically sealed up, and bothsamples exposed to the ordinary temperature ; two other sampleswere exposed for two hours, the one to a temperature of 50", theother t o 75". The seeds were winter wheat, rye, oats, and linseed.The results: exclusion from the air enables the seed to retain itsgerminative power longer than when air has free access to i t ; this isespecially the case with rye.Two hours' heating to 50", wherebysome water is removed, is very effective for the preservation of theseed. After exposure to higher temperatures than 50", seeds, at leastthe cereals, germinate more slowly than if only exposed to a lowertemperature. Seeds which have been artificially dried, when subse-quently moistened, absorb more water than they would otherwisehave done ; and old seeds, as a rule, germinate more slowly than newseeds, especially if they have been exposed to the air.Absorption of the Non-alimentary Substances by Plants.By KNOP (Ann.Agronom., 11, 418-419 ; from Bot. Centr., 22, 35).-Maize plants were grown in nutrient solutions containing 2 grams perlitre of the followiiig mixture of salts :-4 parts calcium nitrate,1 part potassium nitrate, 1 part potassium phosphate, and 2 partscrgstallised magnesium sulphate. One solution was neutral, theother was acidified by the addition of 0.07455 gram free phosphoricacid.The phosphates of most metals are soluble in t.he acid solution,and were added to it in a freshly precipitated stat'e, mixed withphosphate of iron.Tlie author's previous .researches have shownthat iodine and bromine, in small quantities, are not more injurioustha2n chlorine, but that in larger doses iodine is the most injurious,C. H. B.E. W. P172 ABSTRACTS OF CHEXICXL PAPERS.then bromine, and chlorine least. Also that zinc, boric acid, cobalt,copper, silver phosphate, and gold chloride are poisonous ; butstrontium, barium, and manganese are absorbed without injury. Theresearches reported in the present *paper gave the following results :Ammonium vanadate (50 mgrms. per litre) is poisonous a t the end oftwo days. Roots coloured white by the lower oxides of vanadiumsoon cease to grow, but as soon bs all the salt is absorbed the plantsbecome healthy again.Holy bdic acid acts in the same way. Phospho-tungstic acid in doses of 0*05-0.1 gram is very poisonous. Tellurousacid, being scarcely soluble in the nutrient solution, is not absorbed.Telluric acid (0*05-0*1 gram, per litre) is without action ; whilstselenious and selenic acids are very poisonous. Arsenious acid isvery poisonous, but potassium arsenate given in 0.05 gram dose toplants of maize with 10 to 15 leaves, did not hinder normal growthand fructification, nor kill a Volvox globator or a mauld. Cadmiumand thallium are poisonous. Lead phosphate feebly retarded thegeneral development of the plant without disorgariising the variousiunctions. Bismuth resembles lead in this respect,. Oxalic, humic,malic, tartaric, citric, benzoic, and succinic acids are without influencewhen very dilute.Potassium ferrocyanide rapidly remedies chlorosis ;in 0.1 gram dose it simply arrests the growth of the plant, whichnevertheless remains green and healthy until autumn. Hydroxyl-amine hydrochloride, in the, proportion of O.5.gram per litre, is verypoisonous ; so are mellitic acid and ammonium mellitate in doses of1 gram. It is doubtful whether nickel and bismuth are absorbed,since they cannot be found in the plant. Chromium and uraniumoxides are not absorbed because of their. insolubility. The followingsubstances act fatally on the roots, whether or not they are reallyabsorbed : silver oxide, gold chloride, platinum chloride, x-anadic,molybdic, and phosphotungstic acids, thallium oxide, selenious andselenic acids, boric and chromic acids.By A.F A w N T z I N andS. PRZIBYTEK (J. Russ. Chena. SOC., 1885, 371--372).-0n drying thepollen of Pinus silvestri's a t 200-105" it loses 6.;9 per cent. in weight ;the dried substance gives 3.30 per cent. of ash containing-E20. Na,O. CaO. MgO. Fe203,Al,03. MnO. P205. SO3. C1.35.25 3-62 0.88 7-00 5.30 trace 29-86 14.83 0.99nitrogen by Kjeldahl's method = 2.40 per cent. ; if the whole of t b i snitrogen be calculated in the form of albumino'id matter (whichobviously is only approximately correct), the quantity of the latter inthe pollen is 15 per cent. (compare Von Planta, this vol., p. 91).J. M. H. M.Ash of the Pollen of Pinus Silvestris.A. T.Glycyrrhizin in Myrrhis Odorata.By SCHROEDER (Arch.Pharm. [3], 23, 621-622).-Guignet has remarked the presence ofglycyrrhizin in plants not belonging to the Papilionaceae; this in-duced the author to examine Myrrhis odorata both by Robiquet'smethod and that of Guignet. The latter (treatment with acetic acid,then with alcohol, and after concentration, separation by means oVEGETABLE PHYSIOLOGY AND AGRICULTURE. 17:;water, &c.) gave unsatisfactory results. The plant was treated withaqueous ammonia, sulpliuric acid added t o the filtrate, the precipitateevaporated to dr.yness with barium carbonate, treated with alcohol,and the filtrat,e evaporated. Repeated attempts were made to obtaina crystallised product, but without success. The reactions of gly-cyrrhizin were obtained.J. T.Nitrogenous Constituents of Pumpkin Sprouts. Ry E. SCHULZE(J. pr. Chem. [2], 32, 433--461).-1n continuation of his work onthis subject (compare Abstr., 1880, .180), the author describes in fulldetail the methods by which he isolated or recognised the follow-ing substances :-Glutamine, asparagine, tyrosine, lencine, vernine,members of the xanthine-group (probably as decomposition productsof nucle’in), ammoilium salts, and nihrates. Most of these substancesoccur in both axial organs and cotyledons ; but asparacine and ver-nine were found only in the cotyledons, ghtamine in the axial orgalisonly. A. J. G.BV E. HECKEL and F. SCHLAGDEN-HAUFFEN (Compt. rend., 101, 955-957) .-This root, contrary to thestatement of Bourdon, contains no alkaloPd.The colouring principle,which is also the therapeutic agent, was isolated by precipitating theextract of the root with basic lead acet&te, decomposing the precipi-tate with hydrogen sulphide, and evaporating the red solution todryness after filtering. The residue is a greenish-brown substance,completely soluble in alcohol, acetone, and methyl alcohol, less solublei n chloroform and ether, and only slightly soluble in cold water, b u tcompletely soluble in boiling water. The greater part sublimesunchanged when heated, but a small portion is carbonised. Thissubstance, to which the aut’hor gives tlic name danain, has the compo-sition Cl4HI4O5, and splits ITP into half its own weight of glilcose, anda resinous amorphous compound, danafdin, which probably has thecoinposition C2,Hz,06.C. H. B.Root of Danais Fragrans.Composition of Spurrey (Spergula Arvensis), Spurrey Seed,and Spurrey Silage. By J. 31. H. MUNRO (FieZd, 1885, 386--38i).-Spurrey, recently recommended as a suitable crop for growing onbarren sands with a view bo ensiling, has the following composition,the specimen analysed being cut on June 12th, partly in flower andpartly in seed. The air-driedspurrey, or hay, contained in 100 parts :-Water, 20.79 ; insolubleash, 5.33 ; soluble ash, 4.77 ; crude fibre, 23.82 ; oil (light petroleumextract), 3.80 ; resin, &c., soluble in ether, 1.47 ; true albumino’ids,8-75 ; starch, digestible fibre, amides, &c., 41.22. The total nitrogenwas 1.82 per cent., and the albuminoid nitrogen 1.40 per cent ; 77 percent.of the total nitrogen was thus albumino‘id. Silage was madeon a small scale (in a glass vessel) from a portion of the same sample,and its analysis, compared with that of the fresh herbage, is exhibitedWater, 81.43 ; dry substance, 18-57.the following tables :174 ABSTRACTS OF CHEMlOAL PAPERS.Fresh Freshherbage. silage.Water .........................Ash, insoluble in water ...........Ash, soluble in water ............Crude fibre .....................Ether extract.. .................Albumino'ids ...................Volatile acid, reckoned as acetic.. .Fixed acid reckoned as lactic.. ....St,arch, digestible fibre, solublecarbohydrates,* amides, andother non- albumino'id nitro-genous substances ...........81-431.120.994-961.091-82--8.5977-230.880.985.751.780-760.060.9411.62Total nit,rogen .................. 0.378 0.334Albumindid nitrogen ............I 0.291 I 0.122+Non-albumino'id nitrogen. .......Nitrogen soluble in water ........ -0.0870.2620-289Percentage composi-;ion of dry substance ofHerbage.-6.035-3426-705-909 '81 --46*22100'01,2.041-570.4'7 -Silage.-3.864.3025-257 *823.340.264-1351.04100*001.680.541.141.2'7The loss of mineral matter is apparent only, and is caused by adven-titious sand in the samples. The crude fibre and the fat appear toundergo no alteration. Two-thirds of the albuminoyds are lost duringthe fermentation i n the silo ; some of their nitrogen is absolutely lost(as nitrogen gas), but most of it exists in the silage as ammonia,amides, &c.As bearing on this point, an experiment made in 1883on the fermentation of the nitrogen of gelatin, first with ammonia,and afterwards with nitric acid, under the influence of soil-ferments,is recorded in this paper.. The total loss of weight suffered by thespurrey during its conversion into ensilage did not exceed 8.4 percent. of the dry substance. The starch contained in the seeds of thespurrey herbage was found unaltered in the fresh silage, but the soursilage could not be dried in a steam oven without total conversion ofthis starch into carbohydrates, giving no iodine reaction.A slightloss of nitrogen, and of non-nitrogenous matter, a considerable trans-formation of albuminojids into less valuable substances, and a develop-ment of free acid a t the expense of a little sugary or starchy material,probably sum up all the important changes brought about in themanufacture of good silage. Some specimens of silage will keep wellon exposure to the air, others become mouldy, others ra,pidly putrefy :the causes of the differences are a t present unknown, but probablydepend on the proportions of water and free acid. The lower layersof silage contains more, the upper layers less water than the originalherba,ge.Spurrey seed contains in 100 parts :-Water, 11.48; ash, 2.58VEGETABLE PHYSIOLOGY AND AGRICULTURE.175crude fibre, 13.93 ; oil (light petroleum extract), 8-52 ; resin, solublein ether, insoluble in alcohol. 2.24; other substances extracted byether, 1.44 ; albumino'ids, 10.13 ; starch, digestible fibre, &c., 49.68.The nitrogen is almost entirely albuminoi'd, and amounts to 1.62 percent.The black testa of the seed contains a siibstnnce with a peacock-blue fluorescence, similar to the peonio$uorescin, discovered byDragendorff in the testa of peony seeds. This substance is insolublein water and light petroleum, soluble ;P ether and alcohol. Toextract it, the crushed seeds are exhausted first with light petroleumto free them from oil, and then with alcohol. The alcoholic solutionis evaporated to dryness, and the residue boiled with water (whichdissolves out tannin and other substances amounting to 5 per cent.ofthe seed). The residue insoluble in water is an olive-green powder,whose alcoholic or ethereal solution exhibits fluorescence of increasedbrilliancy, but this fluorescence disappears after some days, the solu-tions becoming dark-brown. This solution gives a peculiar taste andodour to spurrey seed.Absorption of Free Nitrogen from the Atmosphere byArgillaceous Soils. By BERTHELOT (Compt. rend., 101, 775-784).-Four different kinds of soil, namely, two samples of yellow argil-laceous sand, white clay, and crude kaolin were placed in open cylin-drical pots of glazed earthenware aud left, for many months in aclosed apartment, freshly plastered, well lighted, dry, and free fromany effluvia.Samples for analysis were taken from the various potsa t intervals. In all four cases, the amount of combined nitrogen in-creased continually and very considerably, whilst nitrification remainedstationary, and the proportion of ammonia, always small, was eitherconstant or tended to decrease.The same soils were placed in glazed porcelain pots perforated atthe bottom, and the pots were supported on a table in a meadow a t aheight of 0.7 m. from the ground. The pots were protected fromvertical rain by a roof, whilst the air could circulate freely roundthem, and they were exposed to the action of oblique rain. Duringthe latter part of the experiment, the soils were watered with dis-tilled water on account of the extreme dryness of the weather.Asimilar series of pots was exposed, without any protection from theweather, on the top of a tower 29 m. above the soil of a meadow, I nboth series the result was the same as in the first series ; the amountof combined nitrogen continually increased. The amount of nitro yenin the rain which fell during the latter experiments was estimated bycollecting the rain in st hygrometer with a known collecting surfaceand determining the amount of ammonia. The atmospheric ammoniawas estimated by placing it vessel containing dilute acid by the sideof the pots containing the soils. The amount of nitrogen derivedfrom nitrogen compounds in the atmosphere was much less than theamount of nitrogen absorbcd by the soils, and it follows from thisresult that the absorption of nitrogen by these soils is independent ofthe combined nitrogen in the air, or, in other words, free nitrogen isabsorbed.J. M.H. M176 ABSTRACTS OF CHEMICAL PAPERS.Yellow argillaaeoue-sand, I.. .. 0'0910 0 *11'79 I 0.0983 I ->, 3 ) ,, I1 ....I 0.1119 ' 0.1639 0.1295 1 0.1396White clay.. ................ 0'0210 0.0407 0.0353 I 0.0557Crude kaolin ................ 0.1065 0.1144 I 0.1497' I 1 - 1 iI n a fourth series of experiments, 1 kilo. of each soil was placed ina flask of 4 litres capacity, moistened with water, and the flasks stop-pered and placed in diffused light or in the dark, as the case mightbe. I n all the soils employed, the amount of combined nitrogen con-tinually increased, the absorption taking place somewhat more rapidlyin the light than in the dark.The amounts of nitrates and ammoniaremained constant or diminished.It was found, however, that if the soils were sterilised by heatinga t 100" for two hours, and only filtered air was allowed to enter theflasks, or even i f the sterilised soil was freely exposed in a closedapartment, no increase in the amount of nitrogen was observed.From these results it follows that argillaceous soils have the powerof absorbing free nitrogen from the air, the absorption taking placeunder the influence of living organisms. This absorption is perfect,lydistinct from nitrification. It does not take place in winter, butproceeds most rapidly when vegetation is most active.The following table gives the amount. of nitrogen absorbed by1 kilo.of the different soils during six months; that is, from Aprilto October, 1885 r-0.12890'15030.04940'1236The absolute weight of nitrogen absorbed was 0*02-0*04 gram perkilo., or, calculating from the surface exposed in the pots, 26-32 kilos.per hectare. This last number is, however, too low, since absorptionis not confined to the surface, but extends to a considerable depth.C. H. B.Changes occurring during and the Action of Water in Irriga-tion. By J. KONIG and C. BOHMER ( B i d Ceittr., 1885, 577-594).-The researches, of which mention was made (Abstr., 1882, 655), havehxm continued in the South of France on fields cultivated under asix-course sjstem. It was found that with the same absolute amountof water flowing, the evaporat'ion from equal surfaces was the same.Water, when present in small quant,ities, was more thoroughly ex-hausted of its constituents than when much was present; that is, theabsolute quantity of materials removed by like surfaces was in allcases alike.Poor soils abstract more mineral matter from waterthan rich; consequently, water cannot be so frequently used onpoor as on fertile land. The manuring action, or the cession ofminerals to the soil, is not absolutely dependent on the absorptivecapacity of the soil, hut the plants themselves absorb a considerablepart, the quautity varying with their energy of growth. This manuringaction is by no means the chief advantage which the soil gains, foTWETABLE PHYSIOLOGY AND AGRICULTURE.177the water remores 8ome uselcss material and reduces the acidity inits passage through. The quantity of manure which water bringscan be easily replaced by artificial manures, but the neutralisation ofthe acid must be accomplished by ploughing, &c. The last result isaccomplished by irrigating according to Vincent’s system (simplesurface or gravitation), but this requires plenty of water and naturalsubsoil drainage, by which a t least 100 litres per hectare a secondcan flow away. If the supply of water is wanting, when only10.70 litres are available, then the oxidising action must be assistedhy drainage ; in such a case Petersen’s valvular drainage system maybe employed with great advantage. With plenty of fall, with 20-30 litres a t disposal, Abel’s system is best.Effect of Various Manures on the Ash of Tobacco.By W.El. JORDAN (Bied. Centr., 1885,598-600) .-In order that tobacco, whenprepared for smoking purposes, shall burn well, it must contain butlittle chlorides J consequently, all manures containing chlorides mustbe carefully avoided. Tobacco also requires much potash ; therefore,the sulphate and carbonate (potashes) should be employed. Theanalyses show that the absolute quantity of ash is not much altered,but that the constituents of that ash vary very considerably accordingto the manure. E. W. P.E. W. P.Analysis of Tobacco Leaves and Stems. By E. H. JENKINS(Died. CerLtr., 1885, 623--627).--The results stated in this article aresimilar to t8hose in the previous Abstract. There appears to be norelationship between the capability for burning and the percentage ofpotassium carbonate in the plant.Efs SIR J. B. LAWESand J. H. GILBERT (Jour. Roy. Agri. Xoc. Etbg., 42 (1885) [2], 590-611).-The authors revise the table, originally issued 25 years ago,containing their estimates of the manurial value of one ton ofvarious farm foods, after deducting that portion of the manurialconstituents of each food which may be supposed, in the case of afattening animal, to appear as increase of live-weight. The cdcu-lations are made on the same principles as the former ones, and thealterations are due in some measure to the adoption of average per-centage compositions based on more recent analyses, but chiefly tothe alteration in the price of ammonia, which is now valued a t 6d.per lb. instead of 8d. ; phosphoric acid and potash are now valued at3d. and a i d . per lb. as against 2 i d . and 2d. per lb. respectively.Whereas in the former table the manurial value of a t’on of linseedcake consumed by a fattening animal appeared as S4 12s. 6d., it isnow estimated to be S 3 28s. 6d.; that of a ton of maize is reducedfrom $1 11s. to $1 5s. Id. Of the Woburn experiments, in which“ the manure from cattle foods of such widely different manure valueas decorticated cotton-cake and maize have shown very little differencein the crops to which they were applied,” the authors remark that“ the result was doubtless due to tlie condition of the land being, inboth cases, high enough to yield approximately maximum crops.”E. W. P.Valuation of Unexhausted Manures.VOL. L. 178 ABSTRAOTS OF CHEMICAL PAPERS.Tn addition to the revised table of original manurial value of thedifferent foods after consumption by fattening animals, the authorsnow attempt an estimate of the compensation value or unexhaustedmanurial value of the same foods, after they have been used for aseries of years by the outgoing tenant, and he has realised a certainportion of the manure value in his increased crops.In the case of all the foods except hays and straws, one-half of theoriginal manurial value of the purchased food used during the lastyear of the outgoing tenmt’s possession is to be deducted, and theremainder is the unexhausted manurial value. The unexhausted valueof foods used the year before is one-third less than this; and one-third is deducted from the remainder for every additional year up tothe eighth year before quitting. I n the case of hays and straws,the constituents of which more slowly become available to crops,two-thirds of the original manurial value is deducted for the lastSear, and only one-fifth from year to year for each preceding year upto the eighth. For the many circumstances which must be takeninto account in attempting to utilise the authors’ tables, the originalpaper must, be consulted; the principle, however, on which emphasisi q laid, is the substitution of manurial value for cost of purchasedfoods as the basis of valuations. J. M. H. M

ISSN:0368-1769    

DOI:10.1039/CA8865000169

出版商:RSC    

年代:1886

数据来源: RSC

摘要:

178 ABSTRAOTS OF CHEMICAL PAPERS. A n a1 y t i c a 1 Chemistry. Apparatus for Operations in a Vacuum. By N. V. KLOBUKOW Zeit. anal. Chew., 24, 395-399) .-A convenient arrangement for performing filtrations, washings, evaporations, &c., in a vacuum, or an atmosphere of carbonic anhydride, &c. Estimation of Lithium by Spectrum Analysis. By B. K. HOFMANN (Bey., 18, 2897-2898) .-A question of priority. Volumetric Estimation of Chlorine. By E. BOHLIQ (Zeit. and. Chew., 24, 408).-This met'hod, which depends on the insolubility of silver oxalate in neutral solutions and its immediate conversion into silver chloride in contact with soluble chlorides, is conducted as follows:-The liquid to be examined is boiled with magnesiiim car- bonate, and filtered, ail aliquot part of the clear solution is shaken up with dry silver oxalate, allowed to remain €or a time, and again filtered ; the filtrate is then treated with sulphuric acid, and titrated with deciiiormal permanganate solution, (1 C.C.= 0.007 gram of chlorine), a correction being made for the solubility of the silver oxalate. The author has employed the method for the estimation of chlorine in water. When organic matter is present, the oxalic acid is first, precipitated as the calcium salt, washed, and then titrated aa before. A. P.ANALYTICAL CHEJIlSTRY. 179 Detection of Chlorides in the Presence of Bromides and Iodides. By L. L. DE KONINCK (Zeit. anal. Chem., 24, 376-379).- Slight excess of silver nitrate is added to the solution, the precipitate collected, well washed, and digested with ammonium carbonate, which partially dissolves out any silver chloride present; on adding potassium bromide to the clear solution obtained, a distinct precipitate of silver bromide is formed if chlorides are present ; a slight cloudiness is how- ever always observed, and must therefore be neglected. If iodates are present, the silver precipitate must, be treated with sulphurous acid, before proceeding with the examination.In the presence of cyanides, the silver precipitate must be heated sufficiently to destroy a11 the cyanogen, and then reduced with zinc or cadmium and dilute sulphuric acid, and the liquid examined as above. Sulphur corn- pounds do not affect the process. Kjeldahl’s Method of Estimating Nitrogen. By T. PPEZFFER and F. LEHYANN (Zeit.aiial. Clzenz., 24, 388-4393) .-The hydrogen given off from the zinc employed to prevent bumping in this process, carries over some of the alkali into the standard acid, causing an error of from 2.5 to 5-0 rngrms. of nitrogen ; this may be avoided by introducing a short wide tube containing glass beads, above the dis- tillation flask. In blank experiments performed with this modified apparatus, theoretical results were obtained. A. P. A. P. Detection of Nitric Acid by Means of Pyrogalld. By CURT- MAX (Arch. Pharm. [3J, 23, 711).-A little pyrogallol is dissolved in the water to be tested (less than 1 mgrm. to 1 c.c.) ; and 10 to 1 2 drops of concentrated sulphuric acid are dropped down the side of the test- tube, so as to form two laFers. At the surface of contact, a brown or yellow coloration appears if nitric acid is present.0.1 mgrm. of nitric acid in 1 litre of potable water can thns be clearly detected. Estimation of Carbonic Anhydride. By KKATSCHMER (&it. anal. Chem., 24, 409) .-A modification of Fresenius’ absorption apparatus. Estimation of Potassium C hlorate in Organic Mixtures. Bey SCHACK and SCHWARZ (Arch. Pharm. [3], 23,396).-Schack treats urine by completely precipitating with lead acetate, removing the excess of lead by hydrogen sulphide, and excess of the latter by boiling. The amouut of chlorate is then deduced from the difference in the amount of chloride in the filtrate before and after ignition. The same process serves to estimate potassium chlorate in broth, but it fails in the case of strongly decomposed blood.Schwarz proceeds as follows with urine :-A measured volume is boiled to coagulat,e albumin, made up to the original volume with water, and filtered. A portion is placed in a well-stoppered glass flask, some potassium iodide is added, aud then hydrochloric acid to strongly acidify the liquid. After digestion on the steam-bath for about 15 minutes, the separated iodine is titrated with sodium thiosulphate, using zinc-iodine-starch solution as indicator. In the J. T.180 ABSTRACTS OF CHEMICAL PAPERS. case of the contents of a stomach, blood, &c., after dilution a dialgser is employed. The solut,ion obtained is concentrated, and treated as in the case of urine. J. T. Volumetric Estimation of the Alkaline Earths, and of Com- bined Sulphuric Acid.By 0. KNOFLER (Annalen, 230,345-367). -Calcium, strontium, and barium may be estimated by a modification of the process described in Mohr’s Lehrbuch der I’itrirmethode. Sufficient hydrochloric acid is added to the substance to produce a faintly acid reaction, and the solution is boiled to expel carbonic acid. A mixture of phenolphthaleh and methgl-orange (1 gram of each dis- solved in 250 c . ~ . of alcohol) is used as the indicator. One-fifth normal sodium carbonate solution is now added until a pale rose coloration’is produced. Another cubic centimetne of the sodium carbonate solution is added, and the mixture is filtered through a wet filter-paper. The precipitate is washed once with water, and the excess of alkali in the filtrate determined by means of + normal solution of hydrochloric acid.The volume of sodium carbona,te solution, less the volume of acid, gives the amount of alkaline earth, normal barium chloride solution is required. The solution of the subst’ance is acidified by the addition of + normal acid, and boiled. Sufficient + normal sodium carbonate solution is added to produce a distinctly alkaline reaction. The barium cshloride solution is next added until the alkaline reaction disappears ; an additional cubic centimetre is added, and the mixture boiled. The sodium carbonate is now added, and the analysis finished as in the determination of the alkaline earths. w. c. w. In the volumetric estimation of combined sulphuric acid, a Estimation of Tin in Har3head. By R. FRESENIUS and E. HINTZ (Zeit.a.na1.. Chem., 24,. 412-414).-3 grams of the finely- powdered sample are heated with aqua regia, the solution diluted and filtered, and the residue washed with water containing ammonium nitrate. The acid solutian is made alkaline with soda, and digested with excess of. sodinm sulphide solution, the black precipitate formed, is collected on a filtec and repeatedly extracted with further quantities of sodium sulphide solution ; the residue is fused with liver of sulphur, extracted with water, and the filtered solution added to the alkaline sodium sulphide filtrate and washings ; the whole is then acidified with hydrochloric acid, and the precipitated sulphides of tin, arsenic, antimony, tungsten, and molybdenum, thus obtained are treated with a solution of bromine in hydrochloric acid, whereby t,he greater part of the tungsten is removed as insoluble tungstic anhydride.The acid solution is evaporated to a small bulk with potassium chloride (to pre- vent loss of tin chloride by evaporation) any further deposit of tungstic anhydride being filtered off, and the tin is precipitated from the solution by ammonium nitrate, and purified from tungsten and molybdenum by repeated fusion with potassium cyanide. The metallic tin thus obtained, together with a small amount obtained in a similar manner from the precipitated tangstic anhydride, is again fused with liver of sulphur, extracted with water, filtered and acidified with sulphuricAYALYTICAL CHEMISTRY. IS1 acid; the precipitated sulphide is collected and ignited in a poi*- t-elain boat in A current of hydrogen, to remove sulphur and arsenic.The insoluble residue from this melt is heated in air, fused with potassium cyanide, and the small amount of tin obtained added to the main quantity, dried at loo”, and weighed. This tin still contains traces of silica, antimony, and arsenic, which are estimated by dis- solving the tin in hydrochloric acid, and passing the gases given off through a silver solution, the insoluble matter and the antimony and arsenic found being deducted from the total. A. P. New Reaction of Titanic Acid. By R. FRESENITX (Zeit. and. Chem., 24, 410-4159 .-When a solution of hyposulphurous acid is added to a solution of titanic anhydride in sulphuric or hydrochloric acid, an intense red coloration is produced which gradually changes to yellow and finally disappears, reappearing, however, on the addition of a further quantity of the reagent.Ether does not take up the colour from the solution. The reaction can be made use of only when other oxides or acids yielding coloured solutions on reduction are absent. Sulphurous and dithionic acids do not yield the reaction. A, P. Analysis of Native Platinum. By T. WILM (Bey., 18, 2536- 2551) .-A lengOhy criticism of methods employed or suggested for the analysis of platinum ore. It appears that all the methods are inaccurate to a greater o r less extent, the errors being mostly due to the different behavionr of these substances when mixed, to that which they exhibit when alone, and to the great energy with which many of the insoluble compounds, when precipitated, carry other substances dowii with them. No satisfactory method for this analysis is indicated.A. J. G. Analysis of Gaseous Halogenated Hydrocarbons. By K. SEUBERT (Bey., 18, 26444655) .-The author has experimented on the eudiometric analysis of some gaseous fluoro-, chloro-, and bromo- paraffins, and finds that by explosion wit,h slight excess of oxygen under reduced pressure, they all yield carbonic anhydride and water ; in the case of the fluorine compounds, hydrogen fluoride is also formed ; the chlorine compounds yield hydrogen chloride and a small quantity of chlorine, whilst the bromine compounds give bromine and a little hydrobromic acid. I n the case of the chlorine and bromine corn- pounds, therefore, the results are not very accurate.A. J. G. Testing Peru Balsam. By A. ANDRBE (Arch. Pharm. [3], 22, 561-576) .-The author discusses various proposed methods as far as concerns tolu-balsam, benzo’in, and storax : the first two are detected with certainty by Hager’s light petroleum process, when an increased resinous residue is obtained, with a corresponding diminution in the cinname’in (benzyl cinnamate). The amount of acid in the cinname’in will show whether tolu-balsam or benzoin is the adulterant. Storax can be detected by Schlickum’s ether-ammonia test, in which the ether layer gelatinises. Fluckiger’s test with lime is very good for the tc 2lS2 ARSTRXCTS O F CHEMICAL PAPERS. detection of such adulterants as form compounds with the lime on rubbing up in the cold, but it does not detect tolu-balsam.J. T. Examination of Argol and Wine-lees. By F. KLEIN (Zeit. anal. Chem., 24, 379--388).-The total acidity is estimated in the usual manner. The total tartaric acid is estimated by Warington and Grosjean’s method (this Journ., 1875, 97.3, and Trans., 1879, 341). The hydrogen potassium tartrate present is estimated by a modification of that process. A convenient amount of the sample is treated with hot wat8er, filtered, and the solution and washings evaporated t o about 40 C.C. 5 grams of potassium chloride are then added, the solution well shaken, and further treated as in Warington’s process. From these results, the acid compounds other than hydrogen potassium tartrate, the calcium tartrate, and the hydrogen potassium tartrate present, may be calculated. The presence of calcium tartrate and hydrogen potassium phosphate does not affect the accuracy of the process.A. P. Adulteration of Olive Oil. By A. AUDOI-NAUD (Compt. rend., 101, 752-753).-2 C.C. of oil is placed in a tube 150 Dim. long and 15 mm. diameter, graduated in c.c., mixed wiih 0.1 gram of powdered potassium dichromate, agitated for a short time, then mixed with sufficient nitrosulphuric acid to increase the volume to 4 c.c., and again agitated. The liquid becomes brownish-red, and after the lapse of two minutes sufficient ether is added to increase the volume to 5 c.c., and the liquids are mixed by agitation. The liquid if left at rest tends to separate into two layers, but in a few minutes there is rapid effervescence, nitrogen oxides are given off, and the oil swims on the surface of the liquid with a peculiar colour.With pure olive oil, the colour of the upper layer is green; but with any oil containing not less than 5 per cent,. of oil of sesame, earth-nut, cotton-seed, or poppy, the colour varies from yellowish- green to yellow, or even reddish-yellow. The colour is more easily observed if 4--5 C.C. of water is added. C. H. B. Reagent for Alkaloids. By A. LUCHINI (Adz. Pl~arm. [3], 23, 684) .-The author suggests the use of a s o h tion of potassium dichro- mate in concentrated sulphuric acid. He has compared it with Wenzell’s solution with satisfactory results ; the latter solution, as is known, consists of potassium perlnanganate dissolved in 200 parts of sulphuric acid. The two solutions together render unnecessary the use of the so-called general reagents for alkaloids.1-2 drops of the reagent are added to 1 C.C. of the alkaloid or glucoside solution, and observations are finished after 24 hours. J. T. Examination of Commercial Quinine Sulphate. By !v. KOPPESCHAAR ( Z e d . anal. Ckem., 24, 362-376) .--The examination of commercial quinine sulphate is confined to the determination of the amounts of quinine and cinchonidine, as unless the sample has been adulterated, no other alkaloids should be present. The method of separation of these alkaloids by means of ether is practically worth-AXALTTIC AL CHEMIYTR Y. l S 3 less, as cinchonidine forms a compound alkaloid with quinine, which is readily soluble in ether. I n practised hands, the herapathite method yields very good results; but the most accurate method of determination is by a modification of Oudeman's process (A~znalez, 182, 67) ; the alkaloi'ds are converted into their tartrates, dried a t 12.5-130", and the specific rotatory power of the anhydrous salts determined.By using the anhydrous instead of the crystallised salt, errors are avoided due to variation in the amount of water of c r p tallisation present occurring from the formation of salts of a double alkaloid. The percentage of quinine and cinchonine present may then be calculated by the formula 220.072 + 137.67 (100 - z> = 100 [a],,, in which 220.07 and 137.67 are the respective specific rota- tory powers of anhydrous quinine and cinchonidine tartrates. Cinchonidine sulphate and quinine cinchonidine sulphate crystallise with 6 mols.H,O, whilst quinine sulphate seems to crystallise with 8 mols. H,O ; the contradictory determinations of the water of crys- tallisation present in quinine sulphate, amre probably due to the samples being indefinite mixtures of these salts. The author strongly I ecommends the introduction of acid quinine sulphate into commerce, as this sulphate may be readily purified from cinchonidine by recrys- tallisation. A. P. Detection of Colouring Matters in Wine and Confectionery. By F. STROHMER (Bied. Centr., 1885, 648) .-To detect oxyazo-colour- ing matters, a sample of the liquid or an alcoholic extract of the solid is evaporated to one-half, so that nearly all the alcohol is dispersed. Pure wool is then boiled for 10 to 20 minutes in the liquid ; the results will be as follows :-Ponceau R, dark-red ; Ponceau RR, light- red ; Bordeaux B, bluish Bordeaux red ; Bordeaux R: reddish Bor- deaux red ; Crocein scarlet, violet-red ; Bieberich scarlet, violet-red.If the dyed wool is dried and bhen moisbened with concentrated s u l - phuric acid, the first two will be fiery-red, the next three deel) indigo-blue, whilst the last will assume a dark-green colour. Punk red wine dyes wool a dirty brownish-red, which, under the influence of the acid, is changed to a dirty brown, E. W. P. An Albumin Reaction. By D. AXENFELD (Arch. Phawn. [3], 23, 71 5).-Many organic substances reduce gold chloride with the pro- duction of bluish, violet, or brown precipitates of gold; albumin, however, behaves differently in a solution acidified with formic acid.I f to such a solntion, some drops of a solution of gold chloride (1 : 1000) are added, gas bubbles appear on the walls of the vessel, the solution becomes rose-red ; on further addition, purple-red, then bluish, and finally dark-blue ; whilst on still further addition a blue flocculent precipitate appears, and the supernatant fluid becomes colourless. 1 gram of albumin solution containing 1 part per million with one drop of formic acid, gives with one drop of gold chloride solution a rose-red colour, with two drops a, clear red, and with a third drop a blue colour. All albuminous compounds give these reactions. Gum solution gives a beautiful purple-red colour, but this becomes a splendid orange-yellow on adding potash or soda.The1 s i ABSTRACTS OF @HEJIICAL PAPERS. presence of other substances such as sodium chloride, uric acid, urea, and grape-sugar does not, interfere with the reaction, but more acid and more gold solution are required. Formation of Iodohaemin as a Method for Detecting Blood Stains. By BUFALIXI (Arch. Pharm. [3], 23, 682).-The author prefers the formation of iodohaemin t o Teichmann’s method. The blood, or the aqueous extract of blood stains, is treated with a drop of iodine tincture and very little acetic acid, a, drop of the liquid isrplaced on a slide, and whilst this is repeatedly passed through a flame 8-10 drops of acetic acid are gradually added. In this way, crystals of iodohzemin can be obtained with absolute certainty in 1-2 minutes.J. T. J. T. 178 ABSTRAOTS OF CHEMICAL PAPERS. A n a1 y t i c a 1 Chemistry. Apparatus for Operations in a Vacuum. By N. V. KLOBUKOW Zeit. anal. Chew., 24, 395-399) .-A convenient arrangement for performing filtrations, washings, evaporations, &c., in a vacuum, or an atmosphere of carbonic anhydride, &c. Estimation of Lithium by Spectrum Analysis. By B. K. HOFMANN (Bey., 18, 2897-2898) .-A question of priority. Volumetric Estimation of Chlorine. By E. BOHLIQ (Zeit. and. Chew., 24, 408).-This met'hod, which depends on the insolubility of silver oxalate in neutral solutions and its immediate conversion into silver chloride in contact with soluble chlorides, is conducted as follows:-The liquid to be examined is boiled with magnesiiim car- bonate, and filtered, ail aliquot part of the clear solution is shaken up with dry silver oxalate, allowed to remain €or a time, and again filtered ; the filtrate is then treated with sulphuric acid, and titrated with deciiiormal permanganate solution, (1 C.C.= 0.007 gram of chlorine), a correction being made for the solubility of the silver oxalate. The author has employed the method for the estimation of chlorine in water. When organic matter is present, the oxalic acid is first, precipitated as the calcium salt, washed, and then titrated aa before. A. P.ANALYTICAL CHEJIlSTRY. 179 Detection of Chlorides in the Presence of Bromides and Iodides. By L. L. DE KONINCK (Zeit. anal. Chem., 24, 376-379).- Slight excess of silver nitrate is added to the solution, the precipitate collected, well washed, and digested with ammonium carbonate, which partially dissolves out any silver chloride present; on adding potassium bromide to the clear solution obtained, a distinct precipitate of silver bromide is formed if chlorides are present ; a slight cloudiness is how- ever always observed, and must therefore be neglected.If iodates are present, the silver precipitate must, be treated with sulphurous acid, before proceeding with the examination. In the presence of cyanides, the silver precipitate must be heated sufficiently to destroy a11 the cyanogen, and then reduced with zinc or cadmium and dilute sulphuric acid, and the liquid examined as above. Sulphur corn- pounds do not affect the process. Kjeldahl’s Method of Estimating Nitrogen.By T. PPEZFFER and F. LEHYANN (Zeit. aiial. Clzenz., 24, 388-4393) .-The hydrogen given off from the zinc employed to prevent bumping in this process, carries over some of the alkali into the standard acid, causing an error of from 2.5 to 5-0 rngrms. of nitrogen ; this may be avoided by introducing a short wide tube containing glass beads, above the dis- tillation flask. In blank experiments performed with this modified apparatus, theoretical results were obtained. A. P. A. P. Detection of Nitric Acid by Means of Pyrogalld. By CURT- MAX (Arch. Pharm. [3J, 23, 711).-A little pyrogallol is dissolved in the water to be tested (less than 1 mgrm. to 1 c.c.) ; and 10 to 1 2 drops of concentrated sulphuric acid are dropped down the side of the test- tube, so as to form two laFers. At the surface of contact, a brown or yellow coloration appears if nitric acid is present.0.1 mgrm. of nitric acid in 1 litre of potable water can thns be clearly detected. Estimation of Carbonic Anhydride. By KKATSCHMER (&it. anal. Chem., 24, 409) .-A modification of Fresenius’ absorption apparatus. Estimation of Potassium C hlorate in Organic Mixtures. Bey SCHACK and SCHWARZ (Arch. Pharm. [3], 23,396).-Schack treats urine by completely precipitating with lead acetate, removing the excess of lead by hydrogen sulphide, and excess of the latter by boiling. The amouut of chlorate is then deduced from the difference in the amount of chloride in the filtrate before and after ignition. The same process serves to estimate potassium chlorate in broth, but it fails in the case of strongly decomposed blood.Schwarz proceeds as follows with urine :-A measured volume is boiled to coagulat,e albumin, made up to the original volume with water, and filtered. A portion is placed in a well-stoppered glass flask, some potassium iodide is added, aud then hydrochloric acid to strongly acidify the liquid. After digestion on the steam-bath for about 15 minutes, the separated iodine is titrated with sodium thiosulphate, using zinc-iodine-starch solution as indicator. In the J. T.180 ABSTRACTS OF CHEMICAL PAPERS. case of the contents of a stomach, blood, &c., after dilution a dialgser is employed. The solut,ion obtained is concentrated, and treated as in the case of urine. J. T. Volumetric Estimation of the Alkaline Earths, and of Com- bined Sulphuric Acid.By 0. KNOFLER (Annalen, 230,345-367). -Calcium, strontium, and barium may be estimated by a modification of the process described in Mohr’s Lehrbuch der I’itrirmethode. Sufficient hydrochloric acid is added to the substance to produce a faintly acid reaction, and the solution is boiled to expel carbonic acid. A mixture of phenolphthaleh and methgl-orange (1 gram of each dis- solved in 250 c . ~ . of alcohol) is used as the indicator. One-fifth normal sodium carbonate solution is now added until a pale rose coloration’is produced. Another cubic centimetne of the sodium carbonate solution is added, and the mixture is filtered through a wet filter-paper. The precipitate is washed once with water, and the excess of alkali in the filtrate determined by means of + normal solution of hydrochloric acid.The volume of sodium carbona,te solution, less the volume of acid, gives the amount of alkaline earth, normal barium chloride solution is required. The solution of the subst’ance is acidified by the addition of + normal acid, and boiled. Sufficient + normal sodium carbonate solution is added to produce a distinctly alkaline reaction. The barium cshloride solution is next added until the alkaline reaction disappears ; an additional cubic centimetre is added, and the mixture boiled. The sodium carbonate is now added, and the analysis finished as in the determination of the alkaline earths. w. c. w. In the volumetric estimation of combined sulphuric acid, a Estimation of Tin in Har3head.By R. FRESENIUS and E. HINTZ (Zeit. a.na1.. Chem., 24,. 412-414).-3 grams of the finely- powdered sample are heated with aqua regia, the solution diluted and filtered, and the residue washed with water containing ammonium nitrate. The acid solutian is made alkaline with soda, and digested with excess of. sodinm sulphide solution, the black precipitate formed, is collected on a filtec and repeatedly extracted with further quantities of sodium sulphide solution ; the residue is fused with liver of sulphur, extracted with water, and the filtered solution added to the alkaline sodium sulphide filtrate and washings ; the whole is then acidified with hydrochloric acid, and the precipitated sulphides of tin, arsenic, antimony, tungsten, and molybdenum, thus obtained are treated with a solution of bromine in hydrochloric acid, whereby t,he greater part of the tungsten is removed as insoluble tungstic anhydride.The acid solution is evaporated to a small bulk with potassium chloride (to pre- vent loss of tin chloride by evaporation) any further deposit of tungstic anhydride being filtered off, and the tin is precipitated from the solution by ammonium nitrate, and purified from tungsten and molybdenum by repeated fusion with potassium cyanide. The metallic tin thus obtained, together with a small amount obtained in a similar manner from the precipitated tangstic anhydride, is again fused with liver of sulphur, extracted with water, filtered and acidified with sulphuricAYALYTICAL CHEMISTRY. IS1 acid; the precipitated sulphide is collected and ignited in a poi*- t-elain boat in A current of hydrogen, to remove sulphur and arsenic.The insoluble residue from this melt is heated in air, fused with potassium cyanide, and the small amount of tin obtained added to the main quantity, dried at loo”, and weighed. This tin still contains traces of silica, antimony, and arsenic, which are estimated by dis- solving the tin in hydrochloric acid, and passing the gases given off through a silver solution, the insoluble matter and the antimony and arsenic found being deducted from the total. A. P. New Reaction of Titanic Acid. By R. FRESENITX (Zeit. and. Chem., 24, 410-4159 .-When a solution of hyposulphurous acid is added to a solution of titanic anhydride in sulphuric or hydrochloric acid, an intense red coloration is produced which gradually changes to yellow and finally disappears, reappearing, however, on the addition of a further quantity of the reagent.Ether does not take up the colour from the solution. The reaction can be made use of only when other oxides or acids yielding coloured solutions on reduction are absent. Sulphurous and dithionic acids do not yield the reaction. A, P. Analysis of Native Platinum. By T. WILM (Bey., 18, 2536- 2551) .-A lengOhy criticism of methods employed or suggested for the analysis of platinum ore. It appears that all the methods are inaccurate to a greater o r less extent, the errors being mostly due to the different behavionr of these substances when mixed, to that which they exhibit when alone, and to the great energy with which many of the insoluble compounds, when precipitated, carry other substances dowii with them.No satisfactory method for this analysis is indicated. A. J. G. Analysis of Gaseous Halogenated Hydrocarbons. By K. SEUBERT (Bey., 18, 26444655) .-The author has experimented on the eudiometric analysis of some gaseous fluoro-, chloro-, and bromo- paraffins, and finds that by explosion wit,h slight excess of oxygen under reduced pressure, they all yield carbonic anhydride and water ; in the case of the fluorine compounds, hydrogen fluoride is also formed ; the chlorine compounds yield hydrogen chloride and a small quantity of chlorine, whilst the bromine compounds give bromine and a little hydrobromic acid. I n the case of the chlorine and bromine corn- pounds, therefore, the results are not very accurate.A. J. G. Testing Peru Balsam. By A. ANDRBE (Arch. Pharm. [3], 22, 561-576) .-The author discusses various proposed methods as far as concerns tolu-balsam, benzo’in, and storax : the first two are detected with certainty by Hager’s light petroleum process, when an increased resinous residue is obtained, with a corresponding diminution in the cinname’in (benzyl cinnamate). The amount of acid in the cinname’in will show whether tolu-balsam or benzoin is the adulterant. Storax can be detected by Schlickum’s ether-ammonia test, in which the ether layer gelatinises. Fluckiger’s test with lime is very good for the tc 2lS2 ARSTRXCTS O F CHEMICAL PAPERS. detection of such adulterants as form compounds with the lime on rubbing up in the cold, but it does not detect tolu-balsam.J. T. Examination of Argol and Wine-lees. By F. KLEIN (Zeit. anal. Chem., 24, 379--388).-The total acidity is estimated in the usual manner. The total tartaric acid is estimated by Warington and Grosjean’s method (this Journ., 1875, 97.3, and Trans., 1879, 341). The hydrogen potassium tartrate present is estimated by a modification of that process. A convenient amount of the sample is treated with hot wat8er, filtered, and the solution and washings evaporated t o about 40 C.C. 5 grams of potassium chloride are then added, the solution well shaken, and further treated as in Warington’s process. From these results, the acid compounds other than hydrogen potassium tartrate, the calcium tartrate, and the hydrogen potassium tartrate present, may be calculated.The presence of calcium tartrate and hydrogen potassium phosphate does not affect the accuracy of the process. A. P. Adulteration of Olive Oil. By A. AUDOI-NAUD (Compt. rend., 101, 752-753).-2 C.C. of oil is placed in a tube 150 Dim. long and 15 mm. diameter, graduated in c.c., mixed wiih 0.1 gram of powdered potassium dichromate, agitated for a short time, then mixed with sufficient nitrosulphuric acid to increase the volume to 4 c.c., and again agitated. The liquid becomes brownish-red, and after the lapse of two minutes sufficient ether is added to increase the volume to 5 c.c., and the liquids are mixed by agitation. The liquid if left at rest tends to separate into two layers, but in a few minutes there is rapid effervescence, nitrogen oxides are given off, and the oil swims on the surface of the liquid with a peculiar colour.With pure olive oil, the colour of the upper layer is green; but with any oil containing not less than 5 per cent,. of oil of sesame, earth-nut, cotton-seed, or poppy, the colour varies from yellowish- green to yellow, or even reddish-yellow. The colour is more easily observed if 4--5 C.C. of water is added. C. H. B. Reagent for Alkaloids. By A. LUCHINI (Adz. Pl~arm. [3], 23, 684) .-The author suggests the use of a s o h tion of potassium dichro- mate in concentrated sulphuric acid. He has compared it with Wenzell’s solution with satisfactory results ; the latter solution, as is known, consists of potassium perlnanganate dissolved in 200 parts of sulphuric acid. The two solutions together render unnecessary the use of the so-called general reagents for alkaloids.1-2 drops of the reagent are added to 1 C.C. of the alkaloid or glucoside solution, and observations are finished after 24 hours. J. T. Examination of Commercial Quinine Sulphate. By !v. KOPPESCHAAR ( Z e d . anal. Ckem., 24, 362-376) .--The examination of commercial quinine sulphate is confined to the determination of the amounts of quinine and cinchonidine, as unless the sample has been adulterated, no other alkaloids should be present. The method of separation of these alkaloids by means of ether is practically worth-AXALTTIC AL CHEMIYTR Y. l S 3 less, as cinchonidine forms a compound alkaloid with quinine, which is readily soluble in ether.I n practised hands, the herapathite method yields very good results; but the most accurate method of determination is by a modification of Oudeman's process (A~znalez, 182, 67) ; the alkaloi'ds are converted into their tartrates, dried a t 12.5-130", and the specific rotatory power of the anhydrous salts determined. By using the anhydrous instead of the crystallised salt, errors are avoided due to variation in the amount of water of c r p tallisation present occurring from the formation of salts of a double alkaloid. The percentage of quinine and cinchonine present may then be calculated by the formula 220.072 + 137.67 (100 - z> = 100 [a],,, in which 220.07 and 137.67 are the respective specific rota- tory powers of anhydrous quinine and cinchonidine tartrates.Cinchonidine sulphate and quinine cinchonidine sulphate crystallise with 6 mols. H,O, whilst quinine sulphate seems to crystallise with 8 mols. H,O ; the contradictory determinations of the water of crys- tallisation present in quinine sulphate, amre probably due to the samples being indefinite mixtures of these salts. The author strongly I ecommends the introduction of acid quinine sulphate into commerce, as this sulphate may be readily purified from cinchonidine by recrys- tallisation. A. P. Detection of Colouring Matters in Wine and Confectionery. By F. STROHMER (Bied. Centr., 1885, 648) .-To detect oxyazo-colour- ing matters, a sample of the liquid or an alcoholic extract of the solid is evaporated to one-half, so that nearly all the alcohol is dispersed.Pure wool is then boiled for 10 to 20 minutes in the liquid ; the results will be as follows :-Ponceau R, dark-red ; Ponceau RR, light- red ; Bordeaux B, bluish Bordeaux red ; Bordeaux R: reddish Bor- deaux red ; Crocein scarlet, violet-red ; Bieberich scarlet, violet-red. If the dyed wool is dried and bhen moisbened with concentrated s u l - phuric acid, the first two will be fiery-red, the next three deel) indigo-blue, whilst the last will assume a dark-green colour. Punk red wine dyes wool a dirty brownish-red, which, under the influence of the acid, is changed to a dirty brown, E. W. P. An Albumin Reaction. By D. AXENFELD (Arch. Phawn. [3], 23, 71 5).-Many organic substances reduce gold chloride with the pro- duction of bluish, violet, or brown precipitates of gold; albumin, however, behaves differently in a solution acidified with formic acid.I f to such a solntion, some drops of a solution of gold chloride (1 : 1000) are added, gas bubbles appear on the walls of the vessel, the solution becomes rose-red ; on further addition, purple-red, then bluish, and finally dark-blue ; whilst on still further addition a blue flocculent precipitate appears, and the supernatant fluid becomes colourless. 1 gram of albumin solution containing 1 part per million with one drop of formic acid, gives with one drop of gold chloride solution a rose-red colour, with two drops a, clear red, and with a third drop a blue colour. All albuminous compounds give these reactions. Gum solution gives a beautiful purple-red colour, but this becomes a splendid orange-yellow on adding potash or soda.The1 s i ABSTRACTS OF @HEJIICAL PAPERS. presence of other substances such as sodium chloride, uric acid, urea, and grape-sugar does not, interfere with the reaction, but more acid and more gold solution are required. Formation of Iodohaemin as a Method for Detecting Blood Stains. By BUFALIXI (Arch. Pharm. [3], 23, 682).-The author prefers the formation of iodohaemin t o Teichmann’s method. The blood, or the aqueous extract of blood stains, is treated with a drop of iodine tincture and very little acetic acid, a, drop of the liquid isrplaced on a slide, and whilst this is repeatedly passed through a flame 8-10 drops of acetic acid are gradually added. In this way, crystals of iodohzemin can be obtained with absolute certainty in 1-2 minutes.J. T. J. T.178 ABSTRAOTS OF CHEMICAL PAPERS.A n a1 y t i c a 1 Chemistry.Apparatus for Operations in a Vacuum. By N. V. KLOBUKOWZeit. anal. Chew., 24, 395-399) .-A convenient arrangement forperforming filtrations, washings, evaporations, &c., in a vacuum, oran atmosphere of carbonic anhydride, &c.Estimation of Lithium by Spectrum Analysis. By B. K.HOFMANN (Bey., 18, 2897-2898) .-A question of priority.Volumetric Estimation of Chlorine. By E. BOHLIQ (Zeit. and.Chew., 24, 408).-This met'hod, which depends on the insolubilityof silver oxalate in neutral solutions and its immediate conversioninto silver chloride in contact with soluble chlorides, is conducted asfollows:-The liquid to be examined is boiled with magnesiiim car-bonate, and filtered, ail aliquot part of the clear solution is shaken upwith dry silver oxalate, allowed to remain €or a time, and againfiltered ; the filtrate is then treated with sulphuric acid, and titratedwith deciiiormal permanganate solution, (1 C.C.= 0.007 gram ofchlorine), a correction being made for the solubility of the silveroxalate. The author has employed the method for the estimation ofchlorine in water. When organic matter is present, the oxalic acidis first, precipitated as the calcium salt, washed, and then titrated aabefore. A. PANALYTICAL CHEJIlSTRY. 179Detection of Chlorides in the Presence of Bromides andIodides. By L. L. DE KONINCK (Zeit. anal. Chem., 24, 376-379).-Slight excess of silver nitrate is added to the solution, the precipitatecollected, well washed, and digested with ammonium carbonate, whichpartially dissolves out any silver chloride present; on adding potassiumbromide to the clear solution obtained, a distinct precipitate of silverbromide is formed if chlorides are present ; a slight cloudiness is how-ever always observed, and must therefore be neglected.If iodatesare present, the silver precipitate must, be treated with sulphurousacid, before proceeding with the examination. In the presence ofcyanides, the silver precipitate must be heated sufficiently to destroya11 the cyanogen, and then reduced with zinc or cadmium and dilutesulphuric acid, and the liquid examined as above. Sulphur corn-pounds do not affect the process.Kjeldahl’s Method of Estimating Nitrogen.By T. PPEZFFERand F. LEHYANN (Zeit. aiial. Clzenz., 24, 388-4393) .-The hydrogengiven off from the zinc employed to prevent bumping in this process,carries over some of the alkali into the standard acid, causing anerror of from 2.5 to 5-0 rngrms. of nitrogen ; this may be avoided byintroducing a short wide tube containing glass beads, above the dis-tillation flask. In blank experiments performed with this modifiedapparatus, theoretical results were obtained.A. P.A. P.Detection of Nitric Acid by Means of Pyrogalld. By CURT-MAX (Arch. Pharm. [3J, 23, 711).-A little pyrogallol is dissolved inthe water to be tested (less than 1 mgrm. to 1 c.c.) ; and 10 to 1 2 dropsof concentrated sulphuric acid are dropped down the side of the test-tube, so as to form two laFers.At the surface of contact, a brown oryellow coloration appears if nitric acid is present. 0.1 mgrm. of nitricacid in 1 litre of potable water can thns be clearly detected.Estimation of Carbonic Anhydride. By KKATSCHMER (&it.anal. Chem., 24, 409) .-A modification of Fresenius’ absorptionapparatus.Estimation of Potassium C hlorate in Organic Mixtures.Bey SCHACK and SCHWARZ (Arch. Pharm. [3], 23,396).-Schack treatsurine by completely precipitating with lead acetate, removing theexcess of lead by hydrogen sulphide, and excess of the latter byboiling. The amouut of chlorate is then deduced from the differencein the amount of chloride in the filtrate before and after ignition.Thesame process serves to estimate potassium chlorate in broth, but itfails in the case of strongly decomposed blood.Schwarz proceeds as follows with urine :-A measured volume isboiled to coagulat,e albumin, made up to the original volume withwater, and filtered. A portion is placed in a well-stoppered glassflask, some potassium iodide is added, aud then hydrochloric acid tostrongly acidify the liquid. After digestion on the steam-bath forabout 15 minutes, the separated iodine is titrated with sodiumthiosulphate, using zinc-iodine-starch solution as indicator. In theJ. T180 ABSTRACTS OF CHEMICAL PAPERS.case of the contents of a stomach, blood, &c., after dilution a dialgseris employed. The solut,ion obtained is concentrated, and treated asin the case of urine.J. T.Volumetric Estimation of the Alkaline Earths, and of Com-bined Sulphuric Acid. By 0. KNOFLER (Annalen, 230,345-367).-Calcium, strontium, and barium may be estimated by a modificationof the process described in Mohr’s Lehrbuch der I’itrirmethode.Sufficient hydrochloric acid is added to the substance to produce afaintly acid reaction, and the solution is boiled to expel carbonic acid.A mixture of phenolphthaleh and methgl-orange (1 gram of each dis-solved in 250 c . ~ . of alcohol) is used as the indicator. One-fifth normalsodium carbonate solution is now added until a pale rose coloration’isproduced. Another cubic centimetne of the sodium carbonate solutionis added, and the mixture is filtered through a wet filter-paper. Theprecipitate is washed once with water, and the excess of alkali in thefiltrate determined by means of + normal solution of hydrochloricacid. The volume of sodium carbona,te solution, less the volume ofacid, gives the amount of alkaline earth,normalbarium chloride solution is required. The solution of the subst’anceis acidified by the addition of + normal acid, and boiled.Sufficient + normal sodium carbonate solution is added to produce a distinctlyalkaline reaction. The barium cshloride solution is next added untilthe alkaline reaction disappears ; an additional cubic centimetre isadded, and the mixture boiled. The sodium carbonate is now added,and the analysis finished as in the determination of the alkalineearths.w. c. w.In the volumetric estimation of combined sulphuric acid, aEstimation of Tin in Har3head. By R. FRESENIUS and E.HINTZ (Zeit. a.na1.. Chem., 24,. 412-414).-3 grams of the finely-powdered sample are heated with aqua regia, the solution diluted andfiltered, and the residue washed with water containing ammoniumnitrate. The acid solutian is made alkaline with soda, and digestedwith excess of. sodinm sulphide solution, the black precipitate formed,is collected on a filtec and repeatedly extracted with further quantitiesof sodium sulphide solution ; the residue is fused with liver of sulphur,extracted with water, and the filtered solution added to the alkalinesodium sulphide filtrate and washings ; the whole is then acidified withhydrochloric acid, and the precipitated sulphides of tin, arsenic,antimony, tungsten, and molybdenum, thus obtained are treated witha solution of bromine in hydrochloric acid, whereby t,he greater partof the tungsten is removed as insoluble tungstic anhydride. The acidsolution is evaporated to a small bulk with potassium chloride (to pre-vent loss of tin chloride by evaporation) any further deposit of tungsticanhydride being filtered off, and the tin is precipitated from the solutionby ammonium nitrate, and purified from tungsten and molybdenumby repeated fusion with potassium cyanide.The metallic tin thusobtained, together with a small amount obtained in a similar mannerfrom the precipitated tangstic anhydride, is again fused with liver ofsulphur, extracted with water, filtered and acidified with sulphuriAYALYTICAL CHEMISTRY.IS1acid; the precipitated sulphide is collected and ignited in a poi*-t-elain boat in A current of hydrogen, to remove sulphur and arsenic.The insoluble residue from this melt is heated in air, fused withpotassium cyanide, and the small amount of tin obtained added to themain quantity, dried at loo”, and weighed. This tin still containstraces of silica, antimony, and arsenic, which are estimated by dis-solving the tin in hydrochloric acid, and passing the gases given offthrough a silver solution, the insoluble matter and the antimony andarsenic found being deducted from the total. A. P.New Reaction of Titanic Acid. By R. FRESENITX (Zeit.and.Chem., 24, 410-4159 .-When a solution of hyposulphurous acid isadded to a solution of titanic anhydride in sulphuric or hydrochloricacid, an intense red coloration is produced which gradually changes toyellow and finally disappears, reappearing, however, on the additionof a further quantity of the reagent. Ether does not take up thecolour from the solution. The reaction can be made use of only whenother oxides or acids yielding coloured solutions on reduction areabsent. Sulphurous and dithionic acids do not yield the reaction.A, P.Analysis of Native Platinum. By T. WILM (Bey., 18, 2536-2551) .-A lengOhy criticism of methods employed or suggested forthe analysis of platinum ore. It appears that all the methods areinaccurate to a greater o r less extent, the errors being mostly due tothe different behavionr of these substances when mixed, to that whichthey exhibit when alone, and to the great energy with which many ofthe insoluble compounds, when precipitated, carry other substancesdowii with them.No satisfactory method for this analysis is indicated.A. J. G.Analysis of Gaseous Halogenated Hydrocarbons. By K.SEUBERT (Bey., 18, 26444655) .-The author has experimented onthe eudiometric analysis of some gaseous fluoro-, chloro-, and bromo-paraffins, and finds that by explosion wit,h slight excess of oxygenunder reduced pressure, they all yield carbonic anhydride and water ;in the case of the fluorine compounds, hydrogen fluoride is also formed ;the chlorine compounds yield hydrogen chloride and a small quantityof chlorine, whilst the bromine compounds give bromine and a littlehydrobromic acid.I n the case of the chlorine and bromine corn-pounds, therefore, the results are not very accurate. A. J. G.Testing Peru Balsam. By A. ANDRBE (Arch. Pharm. [3], 22,561-576) .-The author discusses various proposed methods as far asconcerns tolu-balsam, benzo’in, and storax : the first two are detectedwith certainty by Hager’s light petroleum process, when an increasedresinous residue is obtained, with a corresponding diminution in thecinname’in (benzyl cinnamate). The amount of acid in the cinname’inwill show whether tolu-balsam or benzoin is the adulterant. Storaxcan be detected by Schlickum’s ether-ammonia test, in which the etherlayer gelatinises.Fluckiger’s test with lime is very good for thetc lS2 ARSTRXCTS O F CHEMICAL PAPERS.detection of such adulterants as form compounds with the lime onrubbing up in the cold, but it does not detect tolu-balsam.J. T.Examination of Argol and Wine-lees. By F. KLEIN (Zeit.anal. Chem., 24, 379--388).-The total acidity is estimated in theusual manner. The total tartaric acid is estimated by Waringtonand Grosjean’s method (this Journ., 1875, 97.3, and Trans., 1879, 341).The hydrogen potassium tartrate present is estimated by a modificationof that process. A convenient amount of the sample is treated withhot wat8er, filtered, and the solution and washings evaporated t o about40 C.C. 5 grams of potassium chloride are then added, the solutionwell shaken, and further treated as in Warington’s process. Fromthese results, the acid compounds other than hydrogen potassiumtartrate, the calcium tartrate, and the hydrogen potassium tartratepresent, may be calculated.The presence of calcium tartrate andhydrogen potassium phosphate does not affect the accuracy of theprocess. A. P.Adulteration of Olive Oil. By A. AUDOI-NAUD (Compt. rend., 101,752-753).-2 C.C. of oil is placed in a tube 150 Dim. long and 15 mm.diameter, graduated in c.c., mixed wiih 0.1 gram of powderedpotassium dichromate, agitated for a short time, then mixed withsufficient nitrosulphuric acid to increase the volume to 4 c.c., andagain agitated. The liquid becomes brownish-red, and after the lapseof two minutes sufficient ether is added to increase the volume to5 c.c., and the liquids are mixed by agitation.The liquid if left atrest tends to separate into two layers, but in a few minutes there israpid effervescence, nitrogen oxides are given off, and the oil swimson the surface of the liquid with a peculiar colour.With pure olive oil, the colour of the upper layer is green; butwith any oil containing not less than 5 per cent,. of oil of sesame,earth-nut, cotton-seed, or poppy, the colour varies from yellowish-green to yellow, or even reddish-yellow. The colour is more easilyobserved if 4--5 C.C. of water is added. C. H. B.Reagent for Alkaloids. By A. LUCHINI (Adz. Pl~arm. [3], 23,684) .-The author suggests the use of a s o h tion of potassium dichro-mate in concentrated sulphuric acid.He has compared it withWenzell’s solution with satisfactory results ; the latter solution, as isknown, consists of potassium perlnanganate dissolved in 200 parts ofsulphuric acid. The two solutions together render unnecessary theuse of the so-called general reagents for alkaloids. 1-2 drops of thereagent are added to 1 C.C. of the alkaloid or glucoside solution, andobservations are finished after 24 hours. J. T.Examination of Commercial Quinine Sulphate. By !v. KOPPESCHAAR ( Z e d . anal. Ckem., 24, 362-376) .--The examinationof commercial quinine sulphate is confined to the determination ofthe amounts of quinine and cinchonidine, as unless the sample hasbeen adulterated, no other alkaloids should be present.The methodof separation of these alkaloids by means of ether is practically worthAXALTTIC AL CHEMIYTR Y. l S 3less, as cinchonidine forms a compound alkaloid with quinine, whichis readily soluble in ether. I n practised hands, the herapathitemethod yields very good results; but the most accurate method ofdetermination is by a modification of Oudeman's process (A~znalez,182, 67) ; the alkaloi'ds are converted into their tartrates, dried a t12.5-130", and the specific rotatory power of the anhydrous saltsdetermined. By using the anhydrous instead of the crystallised salt,errors are avoided due to variation in the amount of water of c r ptallisation present occurring from the formation of salts of a doublealkaloid.The percentage of quinine and cinchonine present maythen be calculated by the formula 220.072 + 137.67 (100 - z> =100 [a],,, in which 220.07 and 137.67 are the respective specific rota-tory powers of anhydrous quinine and cinchonidine tartrates.Cinchonidine sulphate and quinine cinchonidine sulphate crystallisewith 6 mols. H,O, whilst quinine sulphate seems to crystallise with8 mols. H,O ; the contradictory determinations of the water of crys-tallisation present in quinine sulphate, amre probably due to thesamples being indefinite mixtures of these salts. The author stronglyI ecommends the introduction of acid quinine sulphate into commerce,as this sulphate may be readily purified from cinchonidine by recrys-tallisation. A. P.Detection of Colouring Matters in Wine and Confectionery.By F. STROHMER (Bied. Centr., 1885, 648) .-To detect oxyazo-colour-ing matters, a sample of the liquid or an alcoholic extract of the solidis evaporated to one-half, so that nearly all the alcohol is dispersed.Pure wool is then boiled for 10 to 20 minutes in the liquid ; theresults will be as follows :-Ponceau R, dark-red ; Ponceau RR, light-red ; Bordeaux B, bluish Bordeaux red ; Bordeaux R: reddish Bor-deaux red ; Crocein scarlet, violet-red ; Bieberich scarlet, violet-red.If the dyed wool is dried and bhen moisbened with concentrated s u l -phuric acid, the first two will be fiery-red, the next three deel)indigo-blue, whilst the last will assume a dark-green colour. Punkred wine dyes wool a dirty brownish-red, which, under the influence ofthe acid, is changed to a dirty brown, E. W. P.An Albumin Reaction. By D. AXENFELD (Arch. Phawn. [3], 23,71 5).-Many organic substances reduce gold chloride with the pro-duction of bluish, violet, or brown precipitates of gold; albumin,however, behaves differently in a solution acidified with formic acid.I f to such a solntion, some drops of a solution of gold chloride(1 : 1000) are added, gas bubbles appear on the walls of the vessel,the solution becomes rose-red ; on further addition, purple-red, thenbluish, and finally dark-blue ; whilst on still further addition a blueflocculent precipitate appears, and the supernatant fluid becomescolourless. 1 gram of albumin solution containing 1 part per millionwith one drop of formic acid, gives with one drop of gold chloridesolution a rose-red colour, with two drops a, clear red, and with athird drop a blue colour. All albuminous compounds give thesereactions. Gum solution gives a beautiful purple-red colour, but thisbecomes a splendid orange-yellow on adding potash or soda. Th1 s i ABSTRACTS OF @HEJIICAL PAPERS.presence of other substances such as sodium chloride, uric acid, urea,and grape-sugar does not, interfere with the reaction, but more acidand more gold solution are required.Formation of Iodohaemin as a Method for Detecting BloodStains. By BUFALIXI (Arch. Pharm. [3], 23, 682).-The authorprefers the formation of iodohaemin t o Teichmann’s method. Theblood, or the aqueous extract of blood stains, is treated with a drop ofiodine tincture and very little acetic acid, a, drop of the liquid isrplacedon a slide, and whilst this is repeatedly passed through a flame 8-10drops of acetic acid are gradually added. In this way, crystals ofiodohzemin can be obtained with absolute certainty in 1-2 minutes.J. T.J. T

ISSN:0368-1769    

DOI:10.1039/CA8865000178

出版商:RSC    

年代:1886

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1 s i ABSTRACTS OF @HEJIICAL PAPERS. T e c h n i c a1 C h e m i s t r y . Preparation of Hydrogen. By F. HEMBERT and HENRY (Compt. rend., 101, 797).-Superheated steam is projected in fine jets on incandescent coke, and the mixture of equal volumes of hydrogen and carbonic oxide which is thus obtained is led into a second retort con- taining some refractory material so arranged that the gases pass over a very large heated surface, Steam heated to the point. of dissocia- tion is driven into this second retort, and the steam and carbonic oxide react on one another with production of carbonic anhydride and hydrogen, decomposition being facililated by contact with the large extent of heated surface. About 3200 cubic metres of hydr,ogen are obtained per ton of coke, and the cost is about 0.015 franc per cubic metre, C.H. B. Apparatus for the Preparation of Carbonic Anhydride. (Dingl. polyt. J., 258, 181--182.)-A deEription of apparatus for preparing carbonic anhydride for technical purposes. Action of Chlorates on Met,allic Evaporating Pans. By G. LUNGE (J. SOC. Chew,. Ind., 4, %?).-In order to determine the action of chlorate liquors on boiling-down pans, short pieces of cast- iron, wrought-iron, and lead tubing were separately immersed for seven hours in boiling solutions (I) of pure potassium chlorate containing 6.03 per cent. by weight, (11) of potassium chlorate containing 25 per cent., and (111) of calcium chlorate and calcium chloride obtained as usual by passing chlorine through milk of lime, and boiling to expel free chlorine and hypochlorite.The following results reduced to 1 square metre of surface were obtained:-TECHKICXL CHEMISTRY. 185 --- Metal osidised. .. .. .. KC103 decomposed.. . Lead. I Cast -iron. Wrought-iron. I I. j 11. i 111. I. 1 11. 1 111. 1 I. 1 11. 1 111. _ _ _ - - - ~ grms.'grms. grms. grms.1 grms. grms. grms. grms. F'"; I 1 11~2524~59ti5'0080~104~~90 95.0064.30151.12437 40 12.2626.90'92.65 21~9649~94~103*55'12~76 29.811 86.31 Power of Certain Salts to Decompose Tribasic Calcium Sac- charate. By P. DEGENER (Chem. Cei~tr., 1883, 605).-The author has on a former occasion expressed the opinion that a portion of the loss of sugar in the separation as lime sacchnrate is due t o the decomposition of t'his compound by salts of the alkali metals. Experi- ments with sodium butyrate, potassium sulphate, potassium oxalate, and citrate, show that these compounds have no such action.P. P. B. Fermentation of Bread. By A. GIRARD (Compt. rend., 101, 601 -603).--The author has examined the gas contained in dough at various stages of preparation, and finds that i t consists mainly of carbonic anhydride mixed with the air originally contained in the flour. In some cases, part of the oxygen ha,s been absorbed, most probably in consequence of the secondary formation of acetic acid. When the dough is distilled with water, the distillate contains alcohol186 ABSI'HAOTS OF CHENICAL PIPERS. Free alkali. 0.99- trace 1' 41-0.3 in quantity amounting to 3.15 c.c., or 2.5 gram, per kilo. of paste. The same results were obtained whether the dough was mixed with leaven or with yeast, and it is evident therefore that what is termed the '' rising " of the dough is the result of alcoholic fermentation.C. H. B. Formation of Basic Salts in the Saponification of Fats and Oils. By &I. DECHAN and T. M-~BEN (Pharm. J. Truns. [3], 15, 1025 -1C)27).-Expcriments are described which show that a soap wili combine with more alkali than is required by the fatty acids present to form normal salts. The experiments prove that these fatty acids combine with varying propoitions of alkalis, and from certain theo- retical considerations, the authors conclude that basic salts are formed. This fact would go far to explain the great variations which soaps show in the amount of alkali they contain ; and as these basic salts would be decomposed by water, producing free alkali and salts of the fatty acids, their presence in a soap would elucidate the liberation of free alkali when alcoholic solutions of some soaps me treated with water.Moreover, the soaps containing the largest excess of combined alkali above that required to form the Iaormal salts, have the strongest detergent powers, whilst those containing more normal proportions of fats and alkali have low cleansing properties, but am well suited for fulling or milling purposes. These facts are of great importance, as liberation of alkali during the dyeing of both silk aud wool is very injurious. In the analysis of ten samples of hard and two of soft soap, the extreme variations per cent. of the alkalinity in relation to the acidity assumed to be oleic were as follows :- Corn bin ed alkali in excess.----- 3 * 17-0 -03 2' 60-0 *31 I I Combined 1 Fat* 1 alkali. Hard.. 68*0-24.8 9.3-6.45 &ft . . . 63 -0-41 * 0 11 1-9 *4 Total excess of alkali. --- 4 '16-0.26 4.01-0*61 D. A. L. Preparation of Canarine. By H. 0. MILLER (Dingl. poZyt. J., 257, 431) .-This substance is prepared in the following manner :-3 kilos. of potassium thiocyanate dissolved in 6 litres of hot water, are treated with 300 grams of potassium chlorate and 2.4 kilos. of hydrochloric acid. After the reaction is ended, the mass is cooled, the remaining 1.2 kilos. of potassium chlorate and 3.6 kilos. of hydrochloric acid are then added gradually. The orange precipitate thus obtained is washed with hot water, pressed, and dried.It is then puritied by solution in potash, filtration, and addition of alcohol to the filtrate, when the potassium compound is thrown down in the form of a reddish-orange crjstalline precipitate. This is collected on a filter, washed, pressed, and dried. It is now dissolved in water, and the solution treated with hydrochloric acid, a brown precipitate ofTEC HKICAL CHEMISTKT. 187 canarine being obtained, which is filtered off, washed, and dried. Canarine, C6NC02H2S5, is insoluble in water, alcohol, and acids. It dissolves in concentrated sulphuric acid with evolution of sulphurous anhydride, and decomposes alkaline carbonates and earths, forming salts of the formula C6N40zM2H2S5, whose aqueous solutions impart t,o cotton-colours varying from orange to maize-yellow, and resisting the action of light and extreme soaping.D. B. Preparation of a Brown Azo-dye. (Dingl. poZ,yt. J., 257, 435). -According to R process patented by P. Monnett and Co., a brown dye is obtained by the action of metaphenyleuecliamine on diazotised plienylenediamine. D. B. Producing Sulpho-colouring Matters by Electrolysis. Bg EWER and PICK (Dingl. polyt. J., 258, 42).-When two plates of platinum are immersed in a solution of paramidodimet~hyl- aniline in dilute sulphuric acid, and the solution is saturated with hydrogen sulphide, the liquid round the positive plate (anode) assumes a blue colour, whilst hydrogen is liberated a t the cathode. The blue colour soon disappears, and a grey film is deposited on the plate. When this coating is removed, the blue colour is again developed, so that if the plate is kept clean by constant brushing, a point is soon reached a t which the whole of the hydrogen sulphide disappears from the solution, and t h e latter assumes a permanent blue colour.The solution at this stage consists mainly of niethylene- white. As the electrolytic operation proceeds, the colour of the solu- tion becomes deeper and deeper, until the conversion is completed. New Blue for Printing. By E. ULLRICR (DingLpolyt. J., 257, 379) .-Tndulines have recently been brought into commerce in the form of a paste by the Farbwerke, vorrnals Meister Lztcius und Briining. When fixed with tannin, these dyes resist the action of light and soap better than the other basic colour derivatives. On decomposing the tannate formed on the fibre by prolonged boiling with caustic soda, the colour remains unaltered.The goods may then be boiled in coin- paratively strong mineral acids without detriment to the dye. This treatment appears to add brightness to the colour, from which it is inferred that salts of mineral acids give better results than tannates. Finding that the solubility in alcohol could not be applied to the fixing of this dye, a subetance was sought for which would act as a solvent during the dyeing process, and thus effect the combination of the colour with tannin. Acetic acid, although at first used, was soon abandoned owing t o its great volatility. Lactic acid gave better results, the high price, however, prevented its general application. Brandt then found that ethyl- or methyl-tartaric acid could be employed with advantage as a substitnte for acetic acid.These acids are prepared on a commercial scale by Goldenberg, Gernmont, aiid Co. D. B. D. B. Bleaching Vegetable Fibres. By J. B. THOMPSON and J. P. RICK- YANN (Dingl. polyt. J., 257, 484).-It is proposed to treat vegetable158 ABSTRACTS OF CHEMICAL PAPERS. fibres with aluminium hydroxide and sodium carbonate, or kaolin and caustic soda. After five to six hours' digestion at a boiling tempera- ture, the goods are rinsed and bleached with chloride of lime, in conjunction with carbonic anhydride. D. B. Bleaching Vegetable Substances with Chloride of Lime. By G. LUNGE (Di??gl. polyt. J., 257, 387).-In order to augment the action of solutions of bleaching powder the author recommends the addition of small quantities of acetic or formic acid.I n the case of acetic acid, hypochlorons acid and calcium acetate are first produced. In the bleaching process, the former gives up its oxygen, forming hydrochloric acid, which simultaneously acts on the calcium acetate, calcium chloride being obtained and acetic acid liberated. The latter is then allowed to act"on fresh portions of bleaching powder. D. B. Bleaching and Dyeing Bone and Ivory. By R. KAYSER (Diiigl. polyt. J., 257, 436).--The bleaching is effected by means of hydrogen peroxide. "'he goods to be treated are cleaned with benzene or ether, and placed in a bath of equal parts of hydrogen peroxide and water. l ' h e dyeing is carried out in the following manner. Having cleaned the goods as before, they are immersed in a solution containinp 10 grams of hydrochloric acid in 1 litre of water for two minutes, after which they are taken out and washed.For red, 10 grams of magemtam rubine are dissolved in 3 litres of water, and treated with 100 grams of .acetic aeid. The gonds are then placed into this solution a t a temperature of 30". After half-an-hour's digestion they are taken out and washed, and dried a t a gentJe heat. The following solutions may be used under similar conditions :-For. red : 5 grams of eosin, erythrosin, eosin-scarlet, phloxine, " rose Bengale," or " erythrine dissolved in 1 litre of water and treated with 2 grams of tartaric acid. For violet: 5 granis methyl-violet 01- dahlia, dissolved in 1 litre of water and 3 grams of tartaric acid.For blue: two grams of methylene-blue 01- navy-blue. For green: 3 grams of new Victoria p e e n or brilliant green, dissolved in two litres of water and 100 grams acetic acid. For yellow: 8 grams of naphthol-pellow S., or fast yellow, dissolved in 2 litres of water and 300 paitis of acetic acid. For black : 3 0 grams of soluble nigrosin dissolved in 2 litres of water and treated with 300 grams OF acetic acid. D. B. Improved Gum Solution. (Cham Centr., 1885, 418.)-Two grams of crystallised aluminium sulphate dissolved in 20 grams water is added to 250 grams strong gum arabic solution (2 grams in 5 grams water). Ordinary solutions of gum arabic, however concen- trated, fail in their adhesive power in many cases, such as the joiiiing together of wood, glass, or porcelain ; prepared, however, according to the above receipt, the solution meets all requirements.J. I(. C. 1 s i ABSTRACTS OF @HEJIICAL PAPERS. T e c h n i c a1 C h e m i s t r y . Preparation of Hydrogen. By F. HEMBERT and HENRY (Compt. rend., 101, 797).-Superheated steam is projected in fine jets on incandescent coke, and the mixture of equal volumes of hydrogen and carbonic oxide which is thus obtained is led into a second retort con- taining some refractory material so arranged that the gases pass over a very large heated surface, Steam heated to the point. of dissocia- tion is driven into this second retort, and the steam and carbonic oxide react on one another with production of carbonic anhydride and hydrogen, decomposition being facililated by contact with the large extent of heated surface.About 3200 cubic metres of hydr,ogen are obtained per ton of coke, and the cost is about 0.015 franc per cubic metre, C. H. B. Apparatus for the Preparation of Carbonic Anhydride. (Dingl. polyt. J., 258, 181--182.)-A deEription of apparatus for preparing carbonic anhydride for technical purposes. Action of Chlorates on Met,allic Evaporating Pans. By G. LUNGE (J. SOC. Chew,. Ind., 4, %?).-In order to determine the action of chlorate liquors on boiling-down pans, short pieces of cast- iron, wrought-iron, and lead tubing were separately immersed for seven hours in boiling solutions (I) of pure potassium chlorate containing 6.03 per cent. by weight, (11) of potassium chlorate containing 25 per cent., and (111) of calcium chlorate and calcium chloride obtained as usual by passing chlorine through milk of lime, and boiling to expel free chlorine and hypochlorite.The following results reduced to 1 square metre of surface were obtained:-TECHKICXL CHEMISTRY. 185 --- Metal osidised. .. .. .. KC103 decomposed.. . Lead. I Cast -iron. Wrought-iron. I I. j 11. i 111. I. 1 11. 1 111. 1 I. 1 11. 1 111. _ _ _ - - - ~ grms.'grms. grms. grms.1 grms. grms. grms. grms. F'"; I 1 11~2524~59ti5'0080~104~~90 95.0064.30151.12437 40 12.2626.90'92.65 21~9649~94~103*55'12~76 29.811 86.31 Power of Certain Salts to Decompose Tribasic Calcium Sac- charate. By P. DEGENER (Chem. Cei~tr., 1883, 605).-The author has on a former occasion expressed the opinion that a portion of the loss of sugar in the separation as lime sacchnrate is due t o the decomposition of t'his compound by salts of the alkali metals.Experi- ments with sodium butyrate, potassium sulphate, potassium oxalate, and citrate, show that these compounds have no such action. P. P. B. Fermentation of Bread. By A. GIRARD (Compt. rend., 101, 601 -603).--The author has examined the gas contained in dough at various stages of preparation, and finds that i t consists mainly of carbonic anhydride mixed with the air originally contained in the flour. In some cases, part of the oxygen ha,s been absorbed, most probably in consequence of the secondary formation of acetic acid. When the dough is distilled with water, the distillate contains alcohol186 ABSI'HAOTS OF CHENICAL PIPERS.Free alkali. 0.99- trace 1' 41-0.3 in quantity amounting to 3.15 c.c., or 2.5 gram, per kilo. of paste. The same results were obtained whether the dough was mixed with leaven or with yeast, and it is evident therefore that what is termed the '' rising " of the dough is the result of alcoholic fermentation. C. H. B. Formation of Basic Salts in the Saponification of Fats and Oils. By &I. DECHAN and T. M-~BEN (Pharm. J. Truns. [3], 15, 1025 -1C)27).-Expcriments are described which show that a soap wili combine with more alkali than is required by the fatty acids present to form normal salts. The experiments prove that these fatty acids combine with varying propoitions of alkalis, and from certain theo- retical considerations, the authors conclude that basic salts are formed.This fact would go far to explain the great variations which soaps show in the amount of alkali they contain ; and as these basic salts would be decomposed by water, producing free alkali and salts of the fatty acids, their presence in a soap would elucidate the liberation of free alkali when alcoholic solutions of some soaps me treated with water. Moreover, the soaps containing the largest excess of combined alkali above that required to form the Iaormal salts, have the strongest detergent powers, whilst those containing more normal proportions of fats and alkali have low cleansing properties, but am well suited for fulling or milling purposes. These facts are of great importance, as liberation of alkali during the dyeing of both silk aud wool is very injurious.In the analysis of ten samples of hard and two of soft soap, the extreme variations per cent. of the alkalinity in relation to the acidity assumed to be oleic were as follows :- Corn bin ed alkali in excess. ----- 3 * 17-0 -03 2' 60-0 *31 I I Combined 1 Fat* 1 alkali. Hard.. 68*0-24.8 9.3-6.45 &ft . . . 63 -0-41 * 0 11 1-9 *4 Total excess of alkali. --- 4 '16-0.26 4.01-0*61 D. A. L. Preparation of Canarine. By H. 0. MILLER (Dingl. poZyt. J., 257, 431) .-This substance is prepared in the following manner :-3 kilos. of potassium thiocyanate dissolved in 6 litres of hot water, are treated with 300 grams of potassium chlorate and 2.4 kilos. of hydrochloric acid. After the reaction is ended, the mass is cooled, the remaining 1.2 kilos. of potassium chlorate and 3.6 kilos.of hydrochloric acid are then added gradually. The orange precipitate thus obtained is washed with hot water, pressed, and dried. It is then puritied by solution in potash, filtration, and addition of alcohol to the filtrate, when the potassium compound is thrown down in the form of a reddish-orange crjstalline precipitate. This is collected on a filter, washed, pressed, and dried. It is now dissolved in water, and the solution treated with hydrochloric acid, a brown precipitate ofTEC HKICAL CHEMISTKT. 187 canarine being obtained, which is filtered off, washed, and dried. Canarine, C6NC02H2S5, is insoluble in water, alcohol, and acids. It dissolves in concentrated sulphuric acid with evolution of sulphurous anhydride, and decomposes alkaline carbonates and earths, forming salts of the formula C6N40zM2H2S5, whose aqueous solutions impart t,o cotton-colours varying from orange to maize-yellow, and resisting the action of light and extreme soaping.D. B. Preparation of a Brown Azo-dye. (Dingl. poZ,yt. J., 257, 435). -According to R process patented by P. Monnett and Co., a brown dye is obtained by the action of metaphenyleuecliamine on diazotised plienylenediamine. D. B. Producing Sulpho-colouring Matters by Electrolysis. Bg EWER and PICK (Dingl. polyt. J., 258, 42).-When two plates of platinum are immersed in a solution of paramidodimet~hyl- aniline in dilute sulphuric acid, and the solution is saturated with hydrogen sulphide, the liquid round the positive plate (anode) assumes a blue colour, whilst hydrogen is liberated a t the cathode.The blue colour soon disappears, and a grey film is deposited on the plate. When this coating is removed, the blue colour is again developed, so that if the plate is kept clean by constant brushing, a point is soon reached a t which the whole of the hydrogen sulphide disappears from the solution, and t h e latter assumes a permanent blue colour. The solution at this stage consists mainly of niethylene- white. As the electrolytic operation proceeds, the colour of the solu- tion becomes deeper and deeper, until the conversion is completed. New Blue for Printing. By E. ULLRICR (DingLpolyt. J., 257, 379) .-Tndulines have recently been brought into commerce in the form of a paste by the Farbwerke, vorrnals Meister Lztcius und Briining.When fixed with tannin, these dyes resist the action of light and soap better than the other basic colour derivatives. On decomposing the tannate formed on the fibre by prolonged boiling with caustic soda, the colour remains unaltered. The goods may then be boiled in coin- paratively strong mineral acids without detriment to the dye. This treatment appears to add brightness to the colour, from which it is inferred that salts of mineral acids give better results than tannates. Finding that the solubility in alcohol could not be applied to the fixing of this dye, a subetance was sought for which would act as a solvent during the dyeing process, and thus effect the combination of the colour with tannin. Acetic acid, although at first used, was soon abandoned owing t o its great volatility.Lactic acid gave better results, the high price, however, prevented its general application. Brandt then found that ethyl- or methyl-tartaric acid could be employed with advantage as a substitnte for acetic acid. These acids are prepared on a commercial scale by Goldenberg, Gernmont, aiid Co. D. B. D. B. Bleaching Vegetable Fibres. By J. B. THOMPSON and J. P. RICK- YANN (Dingl. polyt. J., 257, 484).-It is proposed to treat vegetable158 ABSTRACTS OF CHEMICAL PAPERS. fibres with aluminium hydroxide and sodium carbonate, or kaolin and caustic soda. After five to six hours' digestion at a boiling tempera- ture, the goods are rinsed and bleached with chloride of lime, in conjunction with carbonic anhydride. D. B. Bleaching Vegetable Substances with Chloride of Lime.By G. LUNGE (Di??gl. polyt. J., 257, 387).-In order to augment the action of solutions of bleaching powder the author recommends the addition of small quantities of acetic or formic acid. I n the case of acetic acid, hypochlorons acid and calcium acetate are first produced. In the bleaching process, the former gives up its oxygen, forming hydrochloric acid, which simultaneously acts on the calcium acetate, calcium chloride being obtained and acetic acid liberated. The latter is then allowed to act"on fresh portions of bleaching powder. D. B. Bleaching and Dyeing Bone and Ivory. By R. KAYSER (Diiigl. polyt. J., 257, 436).--The bleaching is effected by means of hydrogen peroxide. "'he goods to be treated are cleaned with benzene or ether, and placed in a bath of equal parts of hydrogen peroxide and water.l ' h e dyeing is carried out in the following manner. Having cleaned the goods as before, they are immersed in a solution containinp 10 grams of hydrochloric acid in 1 litre of water for two minutes, after which they are taken out and washed. For red, 10 grams of magemtam rubine are dissolved in 3 litres of water, and treated with 100 grams of .acetic aeid. The gonds are then placed into this solution a t a temperature of 30". After half-an-hour's digestion they are taken out and washed, and dried a t a gentJe heat. The following solutions may be used under similar conditions :-For. red : 5 grams of eosin, erythrosin, eosin-scarlet, phloxine, " rose Bengale," or " erythrine dissolved in 1 litre of water and treated with 2 grams of tartaric acid.For violet: 5 granis methyl-violet 01- dahlia, dissolved in 1 litre of water and 3 grams of tartaric acid. For blue: two grams of methylene-blue 01- navy-blue. For green: 3 grams of new Victoria p e e n or brilliant green, dissolved in two litres of water and 100 grams acetic acid. For yellow: 8 grams of naphthol-pellow S., or fast yellow, dissolved in 2 litres of water and 300 paitis of acetic acid. For black : 3 0 grams of soluble nigrosin dissolved in 2 litres of water and treated with 300 grams OF acetic acid. D. B. Improved Gum Solution. (Cham Centr., 1885, 418.)-Two grams of crystallised aluminium sulphate dissolved in 20 grams water is added to 250 grams strong gum arabic solution (2 grams in 5 grams water).Ordinary solutions of gum arabic, however concen- trated, fail in their adhesive power in many cases, such as the joiiiing together of wood, glass, or porcelain ; prepared, however, according to the above receipt, the solution meets all requirements. J. I(. C.1 s i ABSTRACTS OF @HEJIICAL PAPERS.T e c h n i c a1 C h e m i s t r y .Preparation of Hydrogen. By F. HEMBERT and HENRY (Compt.rend., 101, 797).-Superheated steam is projected in fine jets onincandescent coke, and the mixture of equal volumes of hydrogen andcarbonic oxide which is thus obtained is led into a second retort con-taining some refractory material so arranged that the gases pass overa very large heated surface, Steam heated to the point. of dissocia-tion is driven into this second retort, and the steam and carbonicoxide react on one another with production of carbonic anhydride andhydrogen, decomposition being facililated by contact with the largeextent of heated surface.About 3200 cubic metres of hydr,ogen are obtained per ton of coke,and the cost is about 0.015 franc per cubic metre, C. H.B.Apparatus for the Preparation of Carbonic Anhydride.(Dingl. polyt. J., 258, 181--182.)-A deEription of apparatus forpreparing carbonic anhydride for technical purposes.Action of Chlorates on Met,allic Evaporating Pans. By G.LUNGE (J. SOC. Chew,. Ind., 4, %?).-In order to determine theaction of chlorate liquors on boiling-down pans, short pieces of cast-iron, wrought-iron, and lead tubing were separately immersed for sevenhours in boiling solutions (I) of pure potassium chlorate containing6.03 per cent.by weight, (11) of potassium chlorate containing 25 percent., and (111) of calcium chlorate and calcium chloride obtained asusual by passing chlorine through milk of lime, and boiling to expelfree chlorine and hypochlorite. The following results reduced to1 square metre of surface were obtained:TECHKICXL CHEMISTRY. 185---Metal osidised. .. .. ..KC103 decomposed.. .Lead. I Cast -iron. Wrought-iron. II. j 11. i 111. I. 1 11. 1 111. 1 I. 1 11. 1 111._ _ _ - - - ~grms.'grms. grms. grms.1 grms. grms. grms. grms. F'";I 111~2524~59ti5'0080~104~~90 95.0064.30151.12437 4012.2626.90'92.65 21~9649~94~103*55'12~76 29.811 86.31Power of Certain Salts to Decompose Tribasic Calcium Sac-charate. By P.DEGENER (Chem. Cei~tr., 1883, 605).-The authorhas on a former occasion expressed the opinion that a portion of theloss of sugar in the separation as lime sacchnrate is due t o thedecomposition of t'his compound by salts of the alkali metals. Experi-ments with sodium butyrate, potassium sulphate, potassium oxalate,and citrate, show that these compounds have no such action.P. P. B.Fermentation of Bread. By A. GIRARD (Compt. rend., 101, 601-603).--The author has examined the gas contained in dough atvarious stages of preparation, and finds that i t consists mainly ofcarbonic anhydride mixed with the air originally contained in theflour. In some cases, part of the oxygen ha,s been absorbed, mostprobably in consequence of the secondary formation of acetic acid.When the dough is distilled with water, the distillate contains alcoho186 ABSI'HAOTS OF CHENICAL PIPERS.Free alkali.0.99- trace1' 41-0.3in quantity amounting to 3.15 c.c., or 2.5 gram, per kilo.of paste.The same results were obtained whether the dough was mixed withleaven or with yeast, and it is evident therefore that what is termedthe '' rising " of the dough is the result of alcoholic fermentation.C. H. B.Formation of Basic Salts in the Saponification of Fats andOils. By &I. DECHAN and T. M-~BEN (Pharm. J. Truns. [3], 15, 1025-1C)27).-Expcriments are described which show that a soap wilicombine with more alkali than is required by the fatty acids presentto form normal salts.The experiments prove that these fatty acidscombine with varying propoitions of alkalis, and from certain theo-retical considerations, the authors conclude that basic salts are formed.This fact would go far to explain the great variations which soapsshow in the amount of alkali they contain ; and as these basic saltswould be decomposed by water, producing free alkali and salts of thefatty acids, their presence in a soap would elucidate the liberation offree alkali when alcoholic solutions of some soaps me treated withwater.Moreover, the soaps containing the largest excess of combinedalkali above that required to form the Iaormal salts, have the strongestdetergent powers, whilst those containing more normal proportionsof fats and alkali have low cleansing properties, but am well suited forfulling or milling purposes.These facts are of great importance, asliberation of alkali during the dyeing of both silk aud wool is veryinjurious. In the analysis of ten samples of hard and two of soft soap,the extreme variations per cent. of the alkalinity in relation to theacidity assumed to be oleic were as follows :-Corn bin edalkali inexcess.-----3 * 17-0 -032' 60-0 *31I ICombined 1 Fat* 1 alkali.Hard.. 68*0-24.8 9.3-6.45&ft . . . 63 -0-41 * 0 11 1-9 *4Totalexcess ofalkali.---4 '16-0.264.01-0*61D. A. L.Preparation of Canarine. By H. 0. MILLER (Dingl. poZyt. J., 257,431) .-This substance is prepared in the following manner :-3 kilos.of potassium thiocyanate dissolved in 6 litres of hot water, are treatedwith 300 grams of potassium chlorate and 2.4 kilos.of hydrochloricacid. After the reaction is ended, the mass is cooled, the remaining1.2 kilos. of potassium chlorate and 3.6 kilos. of hydrochloric acid arethen added gradually. The orange precipitate thus obtained iswashed with hot water, pressed, and dried. It is then puritied bysolution in potash, filtration, and addition of alcohol to the filtrate,when the potassium compound is thrown down in the form of areddish-orange crjstalline precipitate. This is collected on a filter,washed, pressed, and dried. It is now dissolved in water, and thesolution treated with hydrochloric acid, a brown precipitate oTEC HKICAL CHEMISTKT. 187canarine being obtained, which is filtered off, washed, and dried.Canarine, C6NC02H2S5, is insoluble in water, alcohol, and acids.Itdissolves in concentrated sulphuric acid with evolution of sulphurousanhydride, and decomposes alkaline carbonates and earths, formingsalts of the formula C6N40zM2H2S5, whose aqueous solutions impartt,o cotton-colours varying from orange to maize-yellow, and resistingthe action of light and extreme soaping. D. B.Preparation of a Brown Azo-dye. (Dingl. poZ,yt. J., 257, 435).-According to R process patented by P. Monnett and Co., a browndye is obtained by the action of metaphenyleuecliamine on diazotisedplienylenediamine. D. B.Producing Sulpho-colouring Matters by Electrolysis. BgEWER and PICK (Dingl.polyt. J., 258, 42).-When two platesof platinum are immersed in a solution of paramidodimet~hyl-aniline in dilute sulphuric acid, and the solution is saturated withhydrogen sulphide, the liquid round the positive plate (anode)assumes a blue colour, whilst hydrogen is liberated a t the cathode.The blue colour soon disappears, and a grey film is deposited on theplate. When this coating is removed, the blue colour is againdeveloped, so that if the plate is kept clean by constant brushing, apoint is soon reached a t which the whole of the hydrogen sulphidedisappears from the solution, and t h e latter assumes a permanentblue colour. The solution at this stage consists mainly of niethylene-white. As the electrolytic operation proceeds, the colour of the solu-tion becomes deeper and deeper, until the conversion is completed.New Blue for Printing.By E. ULLRICR (DingLpolyt. J., 257,379) .-Tndulines have recently been brought into commerce in theform of a paste by the Farbwerke, vorrnals Meister Lztcius und Briining.When fixed with tannin, these dyes resist the action of light and soapbetter than the other basic colour derivatives. On decomposing thetannate formed on the fibre by prolonged boiling with caustic soda,the colour remains unaltered. The goods may then be boiled in coin-paratively strong mineral acids without detriment to the dye. Thistreatment appears to add brightness to the colour, from which it isinferred that salts of mineral acids give better results than tannates.Finding that the solubility in alcohol could not be applied to thefixing of this dye, a subetance was sought for which would act as asolvent during the dyeing process, and thus effect the combination ofthe colour with tannin.Acetic acid, although at first used, was soonabandoned owing t o its great volatility. Lactic acid gave betterresults, the high price, however, prevented its general application.Brandt then found that ethyl- or methyl-tartaric acid could beemployed with advantage as a substitnte for acetic acid. Theseacids are prepared on a commercial scale by Goldenberg, Gernmont,aiid Co. D. B.D. B.Bleaching Vegetable Fibres. By J. B. THOMPSON and J. P. RICK-YANN (Dingl. polyt. J., 257, 484).-It is proposed to treat vegetabl158 ABSTRACTS OF CHEMICAL PAPERS.fibres with aluminium hydroxide and sodium carbonate, or kaolin andcaustic soda.After five to six hours' digestion at a boiling tempera-ture, the goods are rinsed and bleached with chloride of lime, inconjunction with carbonic anhydride. D. B.Bleaching Vegetable Substances with Chloride of Lime. ByG. LUNGE (Di??gl. polyt. J., 257, 387).-In order to augment theaction of solutions of bleaching powder the author recommends theaddition of small quantities of acetic or formic acid. I n the case ofacetic acid, hypochlorons acid and calcium acetate are first produced.In the bleaching process, the former gives up its oxygen, forminghydrochloric acid, which simultaneously acts on the calcium acetate,calcium chloride being obtained and acetic acid liberated.The latteris then allowed to act"on fresh portions of bleaching powder.D. B.Bleaching and Dyeing Bone and Ivory. By R. KAYSER(Diiigl. polyt. J., 257, 436).--The bleaching is effected by means ofhydrogen peroxide. "'he goods to be treated are cleaned withbenzene or ether, and placed in a bath of equal parts of hydrogenperoxide and water. l ' h e dyeing is carried out in the followingmanner. Having cleaned the goods as before, they are immersed ina solution containinp 10 grams of hydrochloric acid in 1 litre of waterfor two minutes, after which they are taken out and washed. Forred, 10 grams of magemtam rubine are dissolved in 3 litres of water,and treated with 100 grams of .acetic aeid. The gonds are thenplaced into this solution a t a temperature of 30". After half-an-hour'sdigestion they are taken out and washed, and dried a t a gentJe heat.The following solutions may be used under similar conditions :-For.red : 5 grams of eosin, erythrosin, eosin-scarlet, phloxine, " roseBengale," or " erythrine dissolved in 1 litre of water and treatedwith 2 grams of tartaric acid. For violet: 5 granis methyl-violet01- dahlia, dissolved in 1 litre of water and 3 grams of tartaric acid.For blue: two grams of methylene-blue 01- navy-blue. For green:3 grams of new Victoria p e e n or brilliant green, dissolved in twolitres of water and 100 grams acetic acid. For yellow: 8 grams ofnaphthol-pellow S., or fast yellow, dissolved in 2 litres of water and300 paitis of acetic acid. For black : 3 0 grams of soluble nigrosindissolved in 2 litres of water and treated with 300 grams OF aceticacid. D. B.Improved Gum Solution. (Cham Centr., 1885, 418.)-Twograms of crystallised aluminium sulphate dissolved in 20 grams wateris added to 250 grams strong gum arabic solution (2 grams in5 grams water). Ordinary solutions of gum arabic, however concen-trated, fail in their adhesive power in many cases, such as the joiiiingtogether of wood, glass, or porcelain ; prepared, however, accordingto the above receipt, the solution meets all requirements.J. I(. C

ISSN:0368-1769    

DOI:10.1039/CA8865000184

出版商:RSC    

年代:1886

数据来源: RSC

摘要:

189 General a n d Physical Chemistry. AbEorption-spectrum of Oxygen. By N. EGOROFF (Compt. 7-end., 101: 1143--1145).-The author gives a summary of previous observations on t'he absorption-spectrum of the terrestrial atmosphere and of oxlgen, and reports the results of some recent experiments. The absorption-spectrum of a layer of the atmosphere 3 kilos. in breadth, observed a t St. Petersburg, showed the groups A, a, and 13, but the group a was absent. The absorption-spectrum of a column of oxygen 60 metres in length, under a pressure of 6 atmos., showed distinctly the group A and the preliminary line and the seven doublets of the group I3. It is evident therefore that all the lines in the groups A, B, and a in the absorption-spectrum of the terrestrial atmosphere are due to oxygen.By H. DESLANDRES (Compt. rend., 101, 1256-1260) .-The band-spectrum of nitrogen consists of three distinct groups. The first, which is entirely visible, extends from A7000 to about X5000 ; the second, which is partly visible and partly in the ultra-riolet, extends from about A5000 to X2800, whilst the third is wholly in the ultra-violet, and extends from X3000 to X2000. The second group is the most intense, and those bands of it which are visible are almost equal in intensity, but in the ultra-violet portion some are very intense whilst others are very weak. The two strongest bands in this group a t 35i9 arid 3372 are characteristic of nitrogen, and can often be seen when all the other bands are invisible. The third group is less intense than the second, but has the same general appearance and shows the same succession of maxima and minima ; it contains two very strong bands a t 248U and 2371 respectively.If the nitrogen is perfectly free from oxygen, and the gas and the vacuum tube are completely dried by means of sodinm, the third group of bends entirely disappears. It follows thererore that this group is due to an oxide of nitrogen. At the same time the first group showed no appreciable alteration, whilst the second group was distinctly stronger. The tube was not entirely free from hydrogen. If oxygen was allowed to enter the tube and was dried by means of sodium, the three groups were observed with their normal intensities. The second group is probably due to a compound of nitrogen and hydrogen (ammonia), whilst the first group seems to be due to nitrogen alone, or to some other compound of nitrogen and hjdrogen.C. H. 13. Band-spectrum of Nitrogen. C. H. B. Relation between the Absorption and the Phosphorescence of Uranium Compounds. By H. BECQUEREL (Compt. rend., 101, 125'2-1256) .-The majority of the uranic compounds are phospho- rescent, and the emitted light gives a spectrum which consists of seven or eight bands or groups of bands regularly distributed between C and F, the positioo and appearance of the bauds depending on the VOL. L. 0190 ABSTRACTS OF CHEMICAL PAPERS. particular compound. The same compounds gave an nbForption- spectrum of bands or groups of bands, which in position and appearance do not coincide with, but seem to be a repetition of, the spectrum of phosphorescence. The wave-lengths of all the bands in each spectrum are connected by the following law: the inverse differences of the wave-lengths, 01’ the difference in the number of vibrations in unit time, is sensibly constant in passing from one group to another, and the value of this difference varies but slightly for the different uranic compounds.Each absorption-band corresponds with a group of radiations which excite phosphorescence, and the corresponding band in the spectrum of phosphorescence is of lower refrangibility. There are however always one or two bands common to both spectra, showing that in these regions the phosphorescent substance emits waves of the same length a s those by which i t was excited. The less refrangible portion of the absorption-spectrum of uranium compounds seems to terminate between F and 6.Uranous compounds show no appreciable phosphorescence, but give a remarkable discontinuous spectrum extending from P to a consider- able distance into the infra-red. The spectra given by the solid salts are different from those of their aqueous solutions. The absorption- bands of the urnnous compounds follow with remarkable regularity the law of distribution of bands in the spectrum of phosphorescence of the uranic compounds, but without having the same relative intensities. C. H. B. Spectroscope for Furnaces and for the Bessemer Process. By C. V. ZENGER (Compt. rend., 101, 1005).-Description of the arrangement of spectrcscopic apparatus for the study of flames from various processes.Electromotive Force of the Currents yielded by Metallic Couples in Simple Saline Solutions. By B. C. DAMIEN (Ann. chin^. Phys. [GI, 6, 289--313).-From a large number of determina- tions of the E.M.F. of the currents yielded by zinc-copper and lead- platinum couples in various simple saline solutions, the author finds that the E.M.F. as a rule decreases with the time the couple is immersed. In the case, however, of the zinc-copper couple in solutions of the chlorides, the E.M.F. at first slowly increases. The E.M.F. of the current yielded hy a zinc-copper couple i n a solution of magnesium sulphate is very constant, scarcely varying 0.01 7 1-olt during 12 months, and is not appreciably affected by changes either of the strength of the solution o r of temperature.By introdncizig an exterior resistance of 20,000 ohms, the current becomes practically invariable, even when the couple is kept in circuit; the author proposes to employ this couple for the generation of currents of standard strength. The zinc-copper couple yields currents whose E.M.F. is almost identical for members of any class of salts containing a given acid, but va.ries greatly with a change of acids ; amalgamation of the zinc slightly increases the E.M.F. a t first, but it decreases more rapidly than is the case when unamalgamated zinc is employed. The current obtained from a platinum and amalgamated zinc coupleGEKERAL AND PHYSICAL CHEXIISTHT. 191 in dilute sulphuric acid has its maximum E.M.F. when its solution contains 30 per cent. of acid.A. P. Electrical Conductivity of Carbon Compounds. By A. BARTOLI (Gazzetta, 15, 392-397, and 397-399, 400--403).-1n these 1)apers the general results are given of the examination of the electric conductivity of liquid carbon compounds, especially those containing iiitrogen. To avoid the effects of polarisation, the determinations were made in U tubes, which were heated to a constant temperature. The arnides and anilides and compounds derived from them by the substitution of hydrogen in the acid radicles by the halogens, give indications of conductivity, as also the amines, anilines, and the pyridine bases. The nitro-compounds are conductors, and the sub- stitution of hydrogen by the NOz group increases the conductivity. All liquid carbon compounds, whether in the pure state, or mixed or dissolved, show an increase of conductivity with rise of temperature, thus differing from metallic conductors. A remarkable exception to this generalisation is dieth.ylamine, the conductivity of which decrehqes with the temperatnre.Thus experi- ments are quoted to show that the relative conductivities a t 10" and 56" are as 10.79 : 4.4. The conductivity of propylaimine, allylamine, and amylamine between 0" and 50" is invariable. In a former memoir, the author has shown that the electric con- ductivity of most solid carbon compounds diminishes very considerably a t the immediate point of solidification, whilst in others this change, although still considerable, is more gradual. In this paper examples are given of the latter case, such as benzamide, phenol, and para- toluidine, and one, paranitrotoluene, of the former.Thus the rela- tive conductivities of this last substance, which melts a t 54", are a t 56" and a t 50' in the ratio of 10 : 1 respectively. In conclusion, the author expresses his belief that the more regular gradation in the diminution of the conductivity is dne not to retained traces of impurities, but to *he actual nature or physical aggregation of the substances themselves. V. H. V. Electrical Conductivity of Mixtures of Organic Com- pounds. By A. BARTOLI (Gazzeth, 15, 410--417).-The author has noticed that, although generally the electric conductivity of carbon compounds diminishes almost to zero a t or about their points of solidification, yet certain mixtures and solutions of these compounds show an increase of conductivity a t temperatures below that of the solidifying point, and a subsequent, decrease to zero at a lower 1 emperature.This phenomenon is not noticeable in mixtures of natural origin, such as the oils, wax, balsams, and resins, but only in artificially prepared mixtures and solutions, such as naphthalene with one of its derivatives? naphthalene or paraffin with phenol, phthalic or benzoic anhydride and the acids of the acetic series. As regards its explanation there are t w o possible cases to be considered, lst, that of a mechanical mixture, such as paraffin in amyl alcohol I n this paper, tables are given illustrating this phenomenon. 0 2192 ABSTRACTS OF CREMLCAL PAPERS. or acetic acid; Znd, that of the mutual solution of the two com- ponents, such as naphthalene in one of its derivatives. In the former case, the interdigused liquid would have a constant conductivity independent of the temperature up to the point of it8s own solidification. A simple caseaof the latter is the solution of a small quantity of a conductorln an insulator ; such a material shows two points of soliaification, the one near to that of the moreabundant constituent, the other immediately below. Between these two points there is a sufficient amount of condncting Iiquid interposed bettween the solid particles, to admit of Ithe passage of the current ; but this gradually diminislies with decrease of temperature.This explanat ion is not however valid for Compounds such as phenol and benzamide, which possess R ceiltain amount of conductivity a t temperatures far below that of their solidification.V. H. V. Heat of Combustion of Compounds of %he Fatty Series. Bg LGGGCIX[K-~ '( Compt. rend., 901, 1061-1064). Heat of combustion. r------- - 1 gram. 1 gram-molecule. Paraldehyde.. ......... e+. .. 6160.4 cal. 813172.8 cal. Normal propionic acid ...... 4957.8 ,) 3668i7.2 ,, Aldol ...................... 6214.3 ,, 546858.4 ,, 9, ,, anhydride . . 5'746.8 ,, 747084,O ,, From these results it follows thst- 3C,H,O = 'C,H,,O, develops + 26827 cd. and CGHI003 + HZO = 2C3H602 ,) + 13330 ,, The conversion oi€ acetic anhydride into acetic acia develops 13060 cal. The aldol employed in*fhese experimerlts was burnt as soon after preparation as possible. From the results obtained, it follows that the conversion of 2 mols.aldehyde into aldol develops + 1.3142 cal. Aldol is isomeric with isobutyric acid, but they have a different chemical function, and th'e difference between their heats of com- bustion, 290i9 cal., is much greater than the differences found in the case of isomerides of the same function. C. H. B. Heats of Cbmbustionaf Ethereal 'Salts uf Fdtty Acids. By LOUGUININE (Conq~t. rend., 101, 1154-,1156). Heat of combustion. r-----L--- 7 'I giam. 1 gram-molec.de. E t h y1 lactate. ......... 5 5.5 9.4 656000.9 E thy1 but y rnt e ........ Ethyl isobut,grate.. .... 7290.7 845721.2 Ethyl citrate. . . . . . . . . 5289.0 1459708.0 851254.4 7 3 38 -4 Yroni these results the htats of combustion of the acids have beenGESERAL ASD PHYSICAL CI-IEJIIS PRY.19a calculated according to Berthelot's law, that, the heat of combustion. of the acid is equal to tliat. of the ethereal salt, minm the sum of the heat of combustion of the alcohol radicle and the prodnct of the number of molecules of alcohol into 2000 cal. The heats of formation of tlie acids are the differences between their heats of combustion and the sum of the heats of comb.ustion of their constituenhs. Heat of Heat of combustion. formation. 1 gram-molecule. 1 gram-molecule. Lactic acid.. ........ 329509 166451 Citric acid. ......... 4802f19 274991 Rutyric acid.. ...... 534764 - Isobutyric acid . . , , . . 519261 - The heat of combustion of normal propionic acid is 366877, and it follows that the replacement of H by OH with formation of lactic acid causes a diminution of 3.7368 cal.in the heat of combustion- The coilversion of mrmal propyl aIcohol into normal propyl glycol diminishes the lieat of combustion by 49142 cal., and the correspond- ing value in the case of the iso-derivatives is 4'2014 cal. The conver- sion of normal prop91 glycol into glycerol is accompanied by a decrease of 38716 cal. ia the heat of combustion, The author's value for the heat of combustion of normal butyric acid is considerably higher than that given by Favre and Silbermann (496940 cal.). The heats of combustion of the normal and iso- derivatives are practically identical. A direct determination of tile lieat of combustion of isobutyric acid gave the number 517796 cal. C. H. B. Do the Static and the Dynamic Methods of Measuring Vapour-tensions give Different Results ? By G.W. A. KAHLBAUJI (Be)-., 18, 3146-3153).-A reply to Ramsay and Young (compare this vol., p. 5). Alcohol and Mixtures of Alcohol with Water. By G.. T. GERLACK (Zed. anal. Chern., 24, 487-533).-The author reviews the principal investigations which have been made of the physical properties of alcohol and its mixtures with water. Following a suggestion of Ilges, he shows that the following expression serves to connect the composition, specific heat, and boiling point of an alcohol water mixture :- a~ s x S + (100 - a)ZOO" luo w boiling point of the mixture, where a is the percentage of alcohol, W the specific heat of the mixture, s and s the specific heat and boiling point of absoluie alcohol: the expression does not appear to be a general one, as it does not hold good for mixtures of sulphuric acid and watzr.The following law appears, however, to connect the boiling point with the relative proportions in a mixhiire of two volatile substances. If to an invariable quantity of the constituent of higher boiliug194 ABSTRACTS OP’ CHEMICAL PAPERS. point vmying quantities of the other constituent are added, the amount of the latter divided by the resulting deprcssion of the boiling point gives a series of numbers having constant differences f o r equal incre- ments of the more volatile substance. Moreover, the difference bet’weeii each of the numbers of this series, and the corresponding one obtained by using as divisor the whole difference between the boiling points of the two constituents, is sensibly constant for a wide range, although, naturally, as the proportion of either constituent approaches infinity, the difference must fall to zero.Alteration of pressure affects the amount of t,ho differences, but not their constancy. Mixtures of alcohol with water, glycerol with water, sulphuric acid with water, and alcohol w i t h ether are found to follow this law ; but i t is obviously only applicable to mixtures whose boiling points lie between those of their constituents, and this is by no means alwajs the case. The Law of Density Numbers. By J. A. GROSHANS (Phil. i&g. [ 5 ] , 20, 19-29 and l91--203 ; also Bec. Truv. Chi/r~., 4, 236-1162). -In these papers, the lam of d e n s i t y n ( ~ m b e r s is enunciated and applied to ithe elemenks and their compounds in different states of physical aggregation, such as gases, liquids a t their boiling points, and crystalline solids, whether Iiydrated, anhydrous, or in solution.Various relations are also indicated between these density numbers and the atomic weights, the specific gravities of solids and liquids, specific volumes, and the absolute boiling points. Briefly expressed the lsw is as follows z-‘~ The specijc gravities of substances a1.e proportio?ial t o t h e density numbers.” Thus, to take a simple example i n tlie case of two comparable compounds containing carbon, hydrogen, and oxygen only, of formdm CI,H,O, and C,,H,O,,, let n and n‘ be the sum of p , q, r, andp’, q’, T’ respectively, then if their specific gravities be d and d’, then- M.J. S. d - n n n’ - - -- or - = - = k a constant. d’ n’ d d’ These density numbers are simple integers; to each element is assigned only one such number, although two or more elements may have t h e same number. The following table contains some of the better ascertained nurubers for the elements :- R 1 Li 2 B 3 F 4 M g 5 C a 7 A s 8 Cr 9 N i l 1 C 1 B e 2 N 3 N a 4 K 5 Se 8 Mn 9 Co 11 0 1 S 2 P 3 A 1 4 F e 9 Cu 11 Si 4 Br 9 Zn 11 Ce 4 Sr l;? Sn 14 Ag 1f Ba 19 Hg 26 Pb 29 S b 13 Te 14 Cd 16 I 14 Pt 16 T h e various applications and relations alluded to above of these (i.) lielation fo Atontic Weights.-In some few cases, pairs of ele- numbers will be discussed seriatim.GESERAL AND PHYSICAL CHENISTRT. 195 rnents, whose atomic weights differ by a constant quantity, show a similar constant difference between their density numbers ; in other cases these numbers show a periodic variation with the atomic weights analogous to fhat observed in other physical constants. (ii.) Application to Hydrated Crystalline Salts.-If I3 represent the sum of the density numbers of the elements contained in the salt, d its specific gravity, then B/d=lc, a constant for all salts with similar formulse, and containing the same number of molecules of water of crystallisation.Thus, referring to the above table, i t is seen that for the salt CaCI,,GH,O, B = 7 + 2 x 4 + 6 x 3 = 33, d = 1 %54, B/d = k = 19.95, and this constant holds good for other hexahydrated metallic chlorides, as also for the hexahydrated nitrates of nickel and zinc.So also for the double sulphates and selenatesl of ammonium and the metals of the magnesium series, the values for k are 28.7 and 29.5 respectively, which become 23.5 and 24 when the ammonium is replaced by poiassinm. I n a series of tables, similar results are given for simple hydrated sulphates, the double silico-, stanno-, and zircono- fluorides, and the plaiirio- and palladio-chlorides. (iii.) Relation to Alisolvte Boiling Poirtts aad Vapour-densities at that Point.--If the boiling point of a compound be so and D, the vapour- density at that point under standard conditions of pressure, then ‘1’ = 273 + so ; with these factors the laws of Avogadro and Gay-Lussac may be expressed thus: 2 = - x 3T, in which M and M‘ are the molecular weights of the two compared compounds.But from the hence - = k a constant, or if the law of densit,y numbers 4 =- compound contain carbon, hydrogen, and oxygen only, then - - k, llil in which n is the sum of the number of atoms (cf. supra). Thus, in the case of water, this constant equals 62.2 = constant equally holds good for other conipounds derived from water by the replacement of hydrogen by hydrocarbon and acidic groupings, and containing 10 atoms of hydrogen. Similarly other series of compounds, isologous as rcgai ds the numbers of hydrogen-atoms contained therein, have similar constants. (iv.) Relation between the Values cy the Constant T x n/M.-(i.) These constants form a series of algebraic numbers ; (ii) in an homologoi~s series the constants increase with increase of molecular weiyht ; (iii) corresponding members of different homologous series, such as the ethers, ethereal salts of the acetic and oxalic acid series, and henzene, have the same constant.The numbers forming these series can be calculated according to the empirical formula T x n/M = 27.8dK whilst in other cases the formula becomes T x n/M = 28.7 Jm + y, in which y is some sma!2 integer, whilst m represents the number of CH2 groupings contained in the compound plns 1. Thus, the value for m for ethyl ether, CaH,,O, is 4 + 1 = 5 ; for benzene, C&, is 3 + 1 = 4; for hexane, C6H14 = 7. (v.) Drtemtinution of Absolute Boiling Points.-It is obvious from T’ 11’ TB 31 D, €3’’ T x n - (273+ and this 18156 ABSTRACT8 OF CHEMICAL PAPERS. the above that it' the values for m or m + y he known for any series of compounds, then the absolute or actual boiling points can be calculated according to the formula T = 273 + 8 =M 27.8 J M Thus, to take the example of benzene, T = 273 + 8 = - X 27.8~'' o r s = 88.4 (85 observed). The degree of accordance between the calculated and observed boiling points is illustrated by the following table, which is selected out of many given in the original papers.n 78 12 Boiling point Naphthylamine, C,,H,N. , . . . . 298.5" Phenylamine, CsH7N . . . . . . . . 184.1 Nitronaphthalene, CloH702N. . 305.4 Nitrobenzene, C6H8N02 . . . . . . 204.9 Methyl nttphthyl ether, CI,H,,O 255.3 Methyl phenyl ether, c&o.. 146.6 Diphenyl, C12Hlo. . . . . . . . . . . . 241.9 Compoimd. calculated. Boiling point observed.300" 184 304 205 258 152 243-243 Conversely from the observed boiling points the values for x in the above formula can be determined, as also the density numbers of other elements ; tables are given illustrative of this point. Relatiow to Spec@ Volurrtes.-As the specific volume of a liquid a t its boiling point so is expressed by the formula vS =-- in applying the law of density numbers t o these volumes, the constant v,n/M analogous to Tn/M is obtained. From the data of Kopp, Pierre, and others the values for the constants in some few series are calculated, although the data are a t present too few to admit of any discussion on the relations between the constants. I n conclusion, particular cases are discussed of certain isomeric substances, such as the crotonic acids, CaHs02, and compounds of the same or nearly equal molecular weight, acrid f o r which the valae for n or B is the same, but whose boiling point and specific volumes are widely different, such as bromine and iodine monochloride, sulphur dichloride, SzClz, and sulphur oxychloride, SO,Cl,.I n such cases it is observed that the values for z differ to an equal degree from some siniple integer; thus this law points to a previously observed but incompletely understood disturbing influence. M ds V. H. V. Numerical Laws of Chemical Equilibrium. By H. LE CHATELIER ( Compt. rend., 101, 1005-1OOS) .-A preliminary inves- tigation of a general equation representing chemical change, in which the magnitude of the change is expressed as a function of the con- centration (that is, the quantity of the reacting substances in unit volume), the temperature, and the electrical conditions. In gaseocs systeins, the coefficient of the proportional variation in the conden- sation of each substance taking part in the reaction, is equal to the mechanical energy gained by the syst~rn during an infinitely small transformation as a result of the disappearance of the particularGENEfIAL AND PHYSICAL CHEJIISTRY.197 substance. calorific energy gained under the same condit>ions. determination of the coefficients presents much greater difficulties. The coefficient relattve to the temperature is equal to the The same formula should apply also to liquid systems, but the C. H. B. Cryoscopy as a means of Determining Molecular Weights. By F.M. RAOT~LT (Compt. rend., 101, 1056--1058).--Tlie author's experiments have shown that the molecnlnr reduction of the freezing point of one and the same solvent is practically constant for all sub- stances belonging to the same type. Conversely, if the mean co- efficient of reduction for several trj-pes are known, a deteimination of the coefficients of reduction of a given substance will serve to indicate which of two alternative moleciilar weights is correct. Amongst organic compounds, if water is the solvent, and the sub- stance is neither a true salt nor an ammonium, the molecular weight - 19 M is given by the formula M = - where A is, the obserred coefficient A of reduction; if acetic acid is the solvent, the formula becomes $1 = -; if benzene is the solvent and the compound is neither an 39 A alcohol, nor a phenol, nor an acid, the formula is M = 49 - The same A ' formulze hold good for anhydrous inorganic chlorides, such as AsCI:?, YCl,, &c., which are soluble in benzene or acetic acid.The molecu1a.r weighh of acids, bases, and salts can be determined in a similar manner, the proper constant being introduced into the formula in each case. If E is the weight of a normal alkaline salt which contains one equiva- lent of metal, and A its coefIicient of reduction of the freezing point of water, then A x E = 35 if the acid is monobasic, 20 if it is dibasic, and 15 if it, is tribasic or tehbasic. Similarly, the atomicity of a metal can be determined. I f E repre- sents that weight of the nitrate which contains one equivalent of acid, then A X E = 35 if the metal of the nitrate is monatomic, 22.5 if i t is diatomic, and A x E < 22.5 if it is plyatomic. The same formula hold good in the case of the chlorides.The same method serves to determine the basicity of an acid. C . H. B. Physical Molecular Equivalents. By F. GUTHRIE (Chem. News, 52, 232-233) .--Many instances are adduced illustrating combina- tions of matter in which the mass ratios, although definite and con- stant, are apparently unconnected with molecular mass ratios. Such, for example, are the cryohydrates: thus sodium chloride forms NnC1 + 10HzO, but potassium sulphate cr-yohydrate is K2SOa + 114*2H,O, whilst potassium nitrate yields KNO, + 44*6H,O. The sub-cryohydrates are, on the other hand, true molecular combinations.I n all )ys, when the metals are mixed in the proportions giving the lowest fusion points, they are never in atomic ratios ; this also holds good with regard to the mass and molecular ratios of salt alloys. The varying solubility of salts in water of different temperatures is198 ABSTRACTS OF CKERIICAL PAPERS. referred to. Moreover, attention is drawn to the admixture of liquids with the production of heat, and subsequent contraction (chemical combination), or with cooling followed by a gain in volume (the antithesis of chemical combination) ; in the latter case, the maximum effect is produced a t a certain niolecular weight ratio (the ratio OF maximum niolecular repulsion), which, in the case of carbon bi- snlphide and chloroform, is 1 : 1, and in the ca,se of carbon bisulphide and alcohol is 2 : 1 ; such mixtures have abnormally high vapour- tensions.In a mixture of carbonic anhydride and hydrogen, the joint volume is measurably greater than the sum of the volumes of the two gases alone. D. A. L. Molecular Weights of Liquids and Solids (Evidence De- ducible from the Study of Salts). By S. U. PICKENING (Chem. News, 52, 239-240, 251--353).-1n this paper the author critioises the literature connected with the so-called molecular compounds such as hydrated salts, basic salts, double salts, and with the numerous experiments on hydration, dehydration, vapouy-tensions, dilatation, boiling points and densities of solutions, and calorimetric cxperi- ments niade with such compounds. After carefully considering and sifting the evidence deducible from all these, and from the numerous expximeiits made by the author himself, he concludes “that, although in a few isolated cases the molecular weight would appear to be greater than the analytical results necessitate, still, in a vast majority of cases we have no grounds for multiplying these weight,s, and have, indeed, a considerable mass of evidence in favour of adhering to the simplest possible formulae,” but admi ts thaf although the smallest particles may be simple chemically, there is no reason why they “ may not agglomerate and act in uaison as regards certain physical forces,” and hence “ t h e molecule of the cheniist is not necessarily identical with the molecule of the physicist.” (Compare Guthrie, preceding Abstract). D.A. L. Apparatus to Extract Solutions with Liquids. By G. NEC- MANN (Eer., 18,3061-3064) .-An apparatus is described for extracting an aqueous solution with ether. Ether is boiled in a Bask, from which the vapour passes nearly to the bottom of the vessel containing the liquid to be extracted ; when the ether which rises to the surface of the liquid reaches a certain height, it syphons itself back into the distilling- flask. A second apparatus is also described. The author recommends the use of corks which have been brushed over with chromo-gelatin (prepared by adding 1 part of ammonium dichromate to a filtered solution of 4 parts of gelatin in 52 parts of boiling water), and then exposed to the light. Corks thus treated are attacked with difficulty by solvents.N. H. M. 189 General a n d Physical Chemistry. AbEorption-spectrum of Oxygen. By N. EGOROFF (Compt. 7-end., 101: 1143--1145).-The author gives a summary of previous observations on t'he absorption-spectrum of the terrestrial atmosphere and of oxlgen, and reports the results of some recent experiments. The absorption-spectrum of a layer of the atmosphere 3 kilos. in breadth, observed a t St. Petersburg, showed the groups A, a, and 13, but the group a was absent. The absorption-spectrum of a column of oxygen 60 metres in length, under a pressure of 6 atmos., showed distinctly the group A and the preliminary line and the seven doublets of the group I3. It is evident therefore that all the lines in the groups A, B, and a in the absorption-spectrum of the terrestrial atmosphere are due to oxygen.By H. DESLANDRES (Compt. rend., 101, 1256-1260) .-The band-spectrum of nitrogen consists of three distinct groups. The first, which is entirely visible, extends from A7000 to about X5000 ; the second, which is partly visible and partly in the ultra-riolet, extends from about A5000 to X2800, whilst the third is wholly in the ultra-violet, and extends from X3000 to X2000. The second group is the most intense, and those bands of it which are visible are almost equal in intensity, but in the ultra-violet portion some are very intense whilst others are very weak. The two strongest bands in this group a t 35i9 arid 3372 are characteristic of nitrogen, and can often be seen when all the other bands are invisible. The third group is less intense than the second, but has the same general appearance and shows the same succession of maxima and minima ; it contains two very strong bands a t 248U and 2371 respectively. If the nitrogen is perfectly free from oxygen, and the gas and the vacuum tube are completely dried by means of sodinm, the third group of bends entirely disappears.It follows thererore that this group is due to an oxide of nitrogen. At the same time the first group showed no appreciable alteration, whilst the second group was distinctly stronger. The tube was not entirely free from hydrogen. If oxygen was allowed to enter the tube and was dried by means of sodium, the three groups were observed with their normal intensities. The second group is probably due to a compound of nitrogen and hydrogen (ammonia), whilst the first group seems to be due to nitrogen alone, or to some other compound of nitrogen and hjdrogen.C. H. 13. Band-spectrum of Nitrogen. C. H. B. Relation between the Absorption and the Phosphorescence of Uranium Compounds. By H. BECQUEREL (Compt. rend., 101, 125'2-1256) .-The majority of the uranic compounds are phospho- rescent, and the emitted light gives a spectrum which consists of seven or eight bands or groups of bands regularly distributed between C and F, the positioo and appearance of the bauds depending on the VOL. L. 0190 ABSTRACTS OF CHEMICAL PAPERS. particular compound. The same compounds gave an nbForption- spectrum of bands or groups of bands, which in position and appearance do not coincide with, but seem to be a repetition of, the spectrum of phosphorescence.The wave-lengths of all the bands in each spectrum are connected by the following law: the inverse differences of the wave-lengths, 01’ the difference in the number of vibrations in unit time, is sensibly constant in passing from one group to another, and the value of this difference varies but slightly for the different uranic compounds. Each absorption-band corresponds with a group of radiations which excite phosphorescence, and the corresponding band in the spectrum of phosphorescence is of lower refrangibility. There are however always one or two bands common to both spectra, showing that in these regions the phosphorescent substance emits waves of the same length a s those by which i t was excited.The less refrangible portion of the absorption-spectrum of uranium compounds seems to terminate between F and 6. Uranous compounds show no appreciable phosphorescence, but give a remarkable discontinuous spectrum extending from P to a consider- able distance into the infra-red. The spectra given by the solid salts are different from those of their aqueous solutions. The absorption- bands of the urnnous compounds follow with remarkable regularity the law of distribution of bands in the spectrum of phosphorescence of the uranic compounds, but without having the same relative intensities. C. H. B. Spectroscope for Furnaces and for the Bessemer Process. By C. V. ZENGER (Compt. rend., 101, 1005).-Description of the arrangement of spectrcscopic apparatus for the study of flames from various processes.Electromotive Force of the Currents yielded by Metallic Couples in Simple Saline Solutions. By B. C. DAMIEN (Ann. chin^. Phys. [GI, 6, 289--313).-From a large number of determina- tions of the E.M.F. of the currents yielded by zinc-copper and lead- platinum couples in various simple saline solutions, the author finds that the E.M.F. as a rule decreases with the time the couple is immersed. In the case, however, of the zinc-copper couple in solutions of the chlorides, the E.M.F. at first slowly increases. The E.M.F. of the current yielded hy a zinc-copper couple i n a solution of magnesium sulphate is very constant, scarcely varying 0.01 7 1-olt during 12 months, and is not appreciably affected by changes either of the strength of the solution o r of temperature.By introdncizig an exterior resistance of 20,000 ohms, the current becomes practically invariable, even when the couple is kept in circuit; the author proposes to employ this couple for the generation of currents of standard strength. The zinc-copper couple yields currents whose E.M.F. is almost identical for members of any class of salts containing a given acid, but va.ries greatly with a change of acids ; amalgamation of the zinc slightly increases the E.M.F. a t first, but it decreases more rapidly than is the case when unamalgamated zinc is employed. The current obtained from a platinum and amalgamated zinc coupleGEKERAL AND PHYSICAL CHEXIISTHT. 191 in dilute sulphuric acid has its maximum E.M.F. when its solution contains 30 per cent.of acid. A. P. Electrical Conductivity of Carbon Compounds. By A. BARTOLI (Gazzetta, 15, 392-397, and 397-399, 400--403).-1n these 1)apers the general results are given of the examination of the electric conductivity of liquid carbon compounds, especially those containing iiitrogen. To avoid the effects of polarisation, the determinations were made in U tubes, which were heated to a constant temperature. The arnides and anilides and compounds derived from them by the substitution of hydrogen in the acid radicles by the halogens, give indications of conductivity, as also the amines, anilines, and the pyridine bases. The nitro-compounds are conductors, and the sub- stitution of hydrogen by the NOz group increases the conductivity. All liquid carbon compounds, whether in the pure state, or mixed or dissolved, show an increase of conductivity with rise of temperature, thus differing from metallic conductors.A remarkable exception to this generalisation is dieth.ylamine, the conductivity of which decrehqes with the temperatnre. Thus experi- ments are quoted to show that the relative conductivities a t 10" and 56" are as 10.79 : 4.4. The conductivity of propylaimine, allylamine, and amylamine between 0" and 50" is invariable. In a former memoir, the author has shown that the electric con- ductivity of most solid carbon compounds diminishes very considerably a t the immediate point of solidification, whilst in others this change, although still considerable, is more gradual. In this paper examples are given of the latter case, such as benzamide, phenol, and para- toluidine, and one, paranitrotoluene, of the former.Thus the rela- tive conductivities of this last substance, which melts a t 54", are a t 56" and a t 50' in the ratio of 10 : 1 respectively. In conclusion, the author expresses his belief that the more regular gradation in the diminution of the conductivity is dne not to retained traces of impurities, but to *he actual nature or physical aggregation of the substances themselves. V. H. V. Electrical Conductivity of Mixtures of Organic Com- pounds. By A. BARTOLI (Gazzeth, 15, 410--417).-The author has noticed that, although generally the electric conductivity of carbon compounds diminishes almost to zero a t or about their points of solidification, yet certain mixtures and solutions of these compounds show an increase of conductivity a t temperatures below that of the solidifying point, and a subsequent, decrease to zero at a lower 1 emperature.This phenomenon is not noticeable in mixtures of natural origin, such as the oils, wax, balsams, and resins, but only in artificially prepared mixtures and solutions, such as naphthalene with one of its derivatives? naphthalene or paraffin with phenol, phthalic or benzoic anhydride and the acids of the acetic series. As regards its explanation there are t w o possible cases to be considered, lst, that of a mechanical mixture, such as paraffin in amyl alcohol I n this paper, tables are given illustrating this phenomenon. 0 2192 ABSTRACTS OF CREMLCAL PAPERS. or acetic acid; Znd, that of the mutual solution of the two com- ponents, such as naphthalene in one of its derivatives.In the former case, the interdigused liquid would have a constant conductivity independent of the temperature up to the point of it8s own solidification. A simple caseaof the latter is the solution of a small quantity of a conductorln an insulator ; such a material shows two points of soliaification, the one near to that of the moreabundant constituent, the other immediately below. Between these two points there is a sufficient amount of condncting Iiquid interposed bettween the solid particles, to admit of Ithe passage of the current ; but this gradually diminislies with decrease of temperature. This explanat ion is not however valid for Compounds such as phenol and benzamide, which possess R ceiltain amount of conductivity a t temperatures far below that of their solidification.V. H. V. Heat of Combustion of Compounds of %he Fatty Series. Bg LGGGCIX[K-~ '( Compt. rend., 901, 1061-1064). Heat of combustion. r------- - 1 gram. 1 gram-molecule. Paraldehyde.. ......... e+. .. 6160.4 cal. 813172.8 cal. Normal propionic acid ...... 4957.8 ,) 3668i7.2 ,, Aldol ...................... 6214.3 ,, 546858.4 ,, 9, ,, anhydride . . 5'746.8 ,, 747084,O ,, From these results it follows thst- 3C,H,O = 'C,H,,O, develops + 26827 cd. and CGHI003 + HZO = 2C3H602 ,) + 13330 ,, The conversion oi€ acetic anhydride into acetic acia develops 13060 cal. The aldol employed in*fhese experimerlts was burnt as soon after preparation as possible.From the results obtained, it follows that the conversion of 2 mols. aldehyde into aldol develops + 1.3142 cal. Aldol is isomeric with isobutyric acid, but they have a different chemical function, and th'e difference between their heats of com- bustion, 290i9 cal., is much greater than the differences found in the case of isomerides of the same function. C. H. B. Heats of Cbmbustionaf Ethereal 'Salts uf Fdtty Acids. By LOUGUININE (Conq~t. rend., 101, 1154-,1156). Heat of combustion. r-----L--- 7 'I giam. 1 gram-molec.de. E t h y1 lactate. ......... 5 5.5 9.4 656000.9 E thy1 but y rnt e ........ Ethyl isobut,grate.. .... 7290.7 845721.2 Ethyl citrate. . . . . . . . . 5289.0 1459708.0 851254.4 7 3 38 -4 Yroni these results the htats of combustion of the acids have beenGESERAL ASD PHYSICAL CI-IEJIIS PRY.19a calculated according to Berthelot's law, that, the heat of combustion. of the acid is equal to tliat. of the ethereal salt, minm the sum of the heat of combustion of the alcohol radicle and the prodnct of the number of molecules of alcohol into 2000 cal. The heats of formation of tlie acids are the differences between their heats of combustion and the sum of the heats of comb.ustion of their constituenhs. Heat of Heat of combustion. formation. 1 gram-molecule. 1 gram-molecule. Lactic acid.. ........ 329509 166451 Citric acid. ......... 4802f19 274991 Rutyric acid.. ...... 534764 - Isobutyric acid . . , , . . 519261 - The heat of combustion of normal propionic acid is 366877, and it follows that the replacement of H by OH with formation of lactic acid causes a diminution of 3.7368 cal.in the heat of combustion- The coilversion of mrmal propyl aIcohol into normal propyl glycol diminishes the lieat of combustion by 49142 cal., and the correspond- ing value in the case of the iso-derivatives is 4'2014 cal. The conver- sion of normal prop91 glycol into glycerol is accompanied by a decrease of 38716 cal. ia the heat of combustion, The author's value for the heat of combustion of normal butyric acid is considerably higher than that given by Favre and Silbermann (496940 cal.). The heats of combustion of the normal and iso- derivatives are practically identical. A direct determination of tile lieat of combustion of isobutyric acid gave the number 517796 cal. C. H. B. Do the Static and the Dynamic Methods of Measuring Vapour-tensions give Different Results ? By G.W. A. KAHLBAUJI (Be)-., 18, 3146-3153).-A reply to Ramsay and Young (compare this vol., p. 5). Alcohol and Mixtures of Alcohol with Water. By G.. T. GERLACK (Zed. anal. Chern., 24, 487-533).-The author reviews the principal investigations which have been made of the physical properties of alcohol and its mixtures with water. Following a suggestion of Ilges, he shows that the following expression serves to connect the composition, specific heat, and boiling point of an alcohol water mixture :- a~ s x S + (100 - a)ZOO" luo w boiling point of the mixture, where a is the percentage of alcohol, W the specific heat of the mixture, s and s the specific heat and boiling point of absoluie alcohol: the expression does not appear to be a general one, as it does not hold good for mixtures of sulphuric acid and watzr. The following law appears, however, to connect the boiling point with the relative proportions in a mixhiire of two volatile substances.If to an invariable quantity of the constituent of higher boiliug194 ABSTRACTS OP’ CHEMICAL PAPERS. point vmying quantities of the other constituent are added, the amount of the latter divided by the resulting deprcssion of the boiling point gives a series of numbers having constant differences f o r equal incre- ments of the more volatile substance. Moreover, the difference bet’weeii each of the numbers of this series, and the corresponding one obtained by using as divisor the whole difference between the boiling points of the two constituents, is sensibly constant for a wide range, although, naturally, as the proportion of either constituent approaches infinity, the difference must fall to zero.Alteration of pressure affects the amount of t,ho differences, but not their constancy. Mixtures of alcohol with water, glycerol with water, sulphuric acid with water, and alcohol w i t h ether are found to follow this law ; but i t is obviously only applicable to mixtures whose boiling points lie between those of their constituents, and this is by no means alwajs the case. The Law of Density Numbers. By J. A. GROSHANS (Phil. i&g. [ 5 ] , 20, 19-29 and l91--203 ; also Bec. Truv. Chi/r~., 4, 236-1162). -In these papers, the lam of d e n s i t y n ( ~ m b e r s is enunciated and applied to ithe elemenks and their compounds in different states of physical aggregation, such as gases, liquids a t their boiling points, and crystalline solids, whether Iiydrated, anhydrous, or in solution. Various relations are also indicated between these density numbers and the atomic weights, the specific gravities of solids and liquids, specific volumes, and the absolute boiling points.Briefly expressed the lsw is as follows z-‘~ The specijc gravities of substances a1.e proportio?ial t o t h e density numbers.” Thus, to take a simple example i n tlie case of two comparable compounds containing carbon, hydrogen, and oxygen only, of formdm CI,H,O, and C,,H,O,,, let n and n‘ be the sum of p , q, r, andp’, q’, T’ respectively, then if their specific gravities be d and d’, then- M.J. S. d - n n n’ - - -- or - = - = k a constant. d’ n’ d d’ These density numbers are simple integers; to each element is assigned only one such number, although two or more elements may have t h e same number. The following table contains some of the better ascertained nurubers for the elements :- R 1 Li 2 B 3 F 4 M g 5 C a 7 A s 8 Cr 9 N i l 1 C 1 B e 2 N 3 N a 4 K 5 Se 8 Mn 9 Co 11 0 1 S 2 P 3 A 1 4 F e 9 Cu 11 Si 4 Br 9 Zn 11 Ce 4 Sr l;? Sn 14 Ag 1f Ba 19 Hg 26 Pb 29 S b 13 Te 14 Cd 16 I 14 Pt 16 T h e various applications and relations alluded to above of these (i.) lielation fo Atontic Weights.-In some few cases, pairs of ele- numbers will be discussed seriatim.GESERAL AND PHYSICAL CHENISTRT. 195 rnents, whose atomic weights differ by a constant quantity, show a similar constant difference between their density numbers ; in other cases these numbers show a periodic variation with the atomic weights analogous to fhat observed in other physical constants.(ii.) Application to Hydrated Crystalline Salts.-If I3 represent the sum of the density numbers of the elements contained in the salt, d its specific gravity, then B/d=lc, a constant for all salts with similar formulse, and containing the same number of molecules of water of crystallisation. Thus, referring to the above table, i t is seen that for the salt CaCI,,GH,O, B = 7 + 2 x 4 + 6 x 3 = 33, d = 1 %54, B/d = k = 19.95, and this constant holds good for other hexahydrated metallic chlorides, as also for the hexahydrated nitrates of nickel and zinc.So also for the double sulphates and selenatesl of ammonium and the metals of the magnesium series, the values for k are 28.7 and 29.5 respectively, which become 23.5 and 24 when the ammonium is replaced by poiassinm. I n a series of tables, similar results are given for simple hydrated sulphates, the double silico-, stanno-, and zircono- fluorides, and the plaiirio- and palladio-chlorides. (iii.) Relation to Alisolvte Boiling Poirtts aad Vapour-densities at that Point.--If the boiling point of a compound be so and D, the vapour- density at that point under standard conditions of pressure, then ‘1’ = 273 + so ; with these factors the laws of Avogadro and Gay-Lussac may be expressed thus: 2 = - x 3T, in which M and M‘ are the molecular weights of the two compared compounds.But from the hence - = k a constant, or if the law of densit,y numbers 4 =- compound contain carbon, hydrogen, and oxygen only, then - - k, llil in which n is the sum of the number of atoms (cf. supra). Thus, in the case of water, this constant equals 62.2 = constant equally holds good for other conipounds derived from water by the replacement of hydrogen by hydrocarbon and acidic groupings, and containing 10 atoms of hydrogen. Similarly other series of compounds, isologous as rcgai ds the numbers of hydrogen-atoms contained therein, have similar constants. (iv.) Relation between the Values cy the Constant T x n/M.-(i.) These constants form a series of algebraic numbers ; (ii) in an homologoi~s series the constants increase with increase of molecular weiyht ; (iii) corresponding members of different homologous series, such as the ethers, ethereal salts of the acetic and oxalic acid series, and henzene, have the same constant.The numbers forming these series can be calculated according to the empirical formula T x n/M = 27.8dK whilst in other cases the formula becomes T x n/M = 28.7 Jm + y, in which y is some sma!2 integer, whilst m represents the number of CH2 groupings contained in the compound plns 1. Thus, the value for m for ethyl ether, CaH,,O, is 4 + 1 = 5 ; for benzene, C&, is 3 + 1 = 4; for hexane, C6H14 = 7. (v.) Drtemtinution of Absolute Boiling Points.-It is obvious from T’ 11’ TB 31 D, €3’’ T x n - (273+ and this 18156 ABSTRACT8 OF CHEMICAL PAPERS.the above that it' the values for m or m + y he known for any series of compounds, then the absolute or actual boiling points can be calculated according to the formula T = 273 + 8 =M 27.8 J M Thus, to take the example of benzene, T = 273 + 8 = - X 27.8~'' o r s = 88.4 (85 observed). The degree of accordance between the calculated and observed boiling points is illustrated by the following table, which is selected out of many given in the original papers. n 78 12 Boiling point Naphthylamine, C,,H,N. , . . . . 298.5" Phenylamine, CsH7N . . . . . . . . 184.1 Nitronaphthalene, CloH702N. . 305.4 Nitrobenzene, C6H8N02 . . . . . . 204.9 Methyl nttphthyl ether, CI,H,,O 255.3 Methyl phenyl ether, c&o.. 146.6 Diphenyl, C12Hlo. . . . . . . . . . . . 241.9 Compoimd. calculated.Boiling point observed. 300" 184 304 205 258 152 243-243 Conversely from the observed boiling points the values for x in the above formula can be determined, as also the density numbers of other elements ; tables are given illustrative of this point. Relatiow to Spec@ Volurrtes.-As the specific volume of a liquid a t its boiling point so is expressed by the formula vS =-- in applying the law of density numbers t o these volumes, the constant v,n/M analogous to Tn/M is obtained. From the data of Kopp, Pierre, and others the values for the constants in some few series are calculated, although the data are a t present too few to admit of any discussion on the relations between the constants. I n conclusion, particular cases are discussed of certain isomeric substances, such as the crotonic acids, CaHs02, and compounds of the same or nearly equal molecular weight, acrid f o r which the valae for n or B is the same, but whose boiling point and specific volumes are widely different, such as bromine and iodine monochloride, sulphur dichloride, SzClz, and sulphur oxychloride, SO,Cl,.I n such cases it is observed that the values for z differ to an equal degree from some siniple integer; thus this law points to a previously observed but incompletely understood disturbing influence. M ds V. H. V. Numerical Laws of Chemical Equilibrium. By H. LE CHATELIER ( Compt. rend., 101, 1005-1OOS) .-A preliminary inves- tigation of a general equation representing chemical change, in which the magnitude of the change is expressed as a function of the con- centration (that is, the quantity of the reacting substances in unit volume), the temperature, and the electrical conditions.In gaseocs systeins, the coefficient of the proportional variation in the conden- sation of each substance taking part in the reaction, is equal to the mechanical energy gained by the syst~rn during an infinitely small transformation as a result of the disappearance of the particularGENEfIAL AND PHYSICAL CHEJIISTRY. 197 substance. calorific energy gained under the same condit>ions. determination of the coefficients presents much greater difficulties. The coefficient relattve to the temperature is equal to the The same formula should apply also to liquid systems, but the C. H. B. Cryoscopy as a means of Determining Molecular Weights.By F. M. RAOT~LT (Compt. rend., 101, 1056--1058).--Tlie author's experiments have shown that the molecnlnr reduction of the freezing point of one and the same solvent is practically constant for all sub- stances belonging to the same type. Conversely, if the mean co- efficient of reduction for several trj-pes are known, a deteimination of the coefficients of reduction of a given substance will serve to indicate which of two alternative moleciilar weights is correct. Amongst organic compounds, if water is the solvent, and the sub- stance is neither a true salt nor an ammonium, the molecular weight - 19 M is given by the formula M = - where A is, the obserred coefficient A of reduction; if acetic acid is the solvent, the formula becomes $1 = -; if benzene is the solvent and the compound is neither an 39 A alcohol, nor a phenol, nor an acid, the formula is M = 49 - The same A ' formulze hold good for anhydrous inorganic chlorides, such as AsCI:?, YCl,, &c., which are soluble in benzene or acetic acid.The molecu1a.r weighh of acids, bases, and salts can be determined in a similar manner, the proper constant being introduced into the formula in each case. If E is the weight of a normal alkaline salt which contains one equiva- lent of metal, and A its coefIicient of reduction of the freezing point of water, then A x E = 35 if the acid is monobasic, 20 if it is dibasic, and 15 if it, is tribasic or tehbasic. Similarly, the atomicity of a metal can be determined. I f E repre- sents that weight of the nitrate which contains one equivalent of acid, then A X E = 35 if the metal of the nitrate is monatomic, 22.5 if i t is diatomic, and A x E < 22.5 if it is plyatomic.The same formula hold good in the case of the chlorides. The same method serves to determine the basicity of an acid. C . H. B. Physical Molecular Equivalents. By F. GUTHRIE (Chem. News, 52, 232-233) .--Many instances are adduced illustrating combina- tions of matter in which the mass ratios, although definite and con- stant, are apparently unconnected with molecular mass ratios. Such, for example, are the cryohydrates: thus sodium chloride forms NnC1 + 10HzO, but potassium sulphate cr-yohydrate is K2SOa + 114*2H,O, whilst potassium nitrate yields KNO, + 44*6H,O. The sub-cryohydrates are, on the other hand, true molecular combinations.I n all )ys, when the metals are mixed in the proportions giving the lowest fusion points, they are never in atomic ratios ; this also holds good with regard to the mass and molecular ratios of salt alloys. The varying solubility of salts in water of different temperatures is198 ABSTRACTS OF CKERIICAL PAPERS. referred to. Moreover, attention is drawn to the admixture of liquids with the production of heat, and subsequent contraction (chemical combination), or with cooling followed by a gain in volume (the antithesis of chemical combination) ; in the latter case, the maximum effect is produced a t a certain niolecular weight ratio (the ratio OF maximum niolecular repulsion), which, in the case of carbon bi- snlphide and chloroform, is 1 : 1, and in the ca,se of carbon bisulphide and alcohol is 2 : 1 ; such mixtures have abnormally high vapour- tensions.In a mixture of carbonic anhydride and hydrogen, the joint volume is measurably greater than the sum of the volumes of the two gases alone. D. A. L. Molecular Weights of Liquids and Solids (Evidence De- ducible from the Study of Salts). By S. U. PICKENING (Chem. News, 52, 239-240, 251--353).-1n this paper the author critioises the literature connected with the so-called molecular compounds such as hydrated salts, basic salts, double salts, and with the numerous experiments on hydration, dehydration, vapouy-tensions, dilatation, boiling points and densities of solutions, and calorimetric cxperi- ments niade with such compounds.After carefully considering and sifting the evidence deducible from all these, and from the numerous expximeiits made by the author himself, he concludes “that, although in a few isolated cases the molecular weight would appear to be greater than the analytical results necessitate, still, in a vast majority of cases we have no grounds for multiplying these weight,s, and have, indeed, a considerable mass of evidence in favour of adhering to the simplest possible formulae,” but admi ts thaf although the smallest particles may be simple chemically, there is no reason why they “ may not agglomerate and act in uaison as regards certain physical forces,” and hence “ t h e molecule of the cheniist is not necessarily identical with the molecule of the physicist.” (Compare Guthrie, preceding Abstract). D.A. L. Apparatus to Extract Solutions with Liquids. By G. NEC- MANN (Eer., 18,3061-3064) .-An apparatus is described for extracting an aqueous solution with ether. Ether is boiled in a Bask, from which the vapour passes nearly to the bottom of the vessel containing the liquid to be extracted ; when the ether which rises to the surface of the liquid reaches a certain height, it syphons itself back into the distilling- flask. A second apparatus is also described. The author recommends the use of corks which have been brushed over with chromo-gelatin (prepared by adding 1 part of ammonium dichromate to a filtered solution of 4 parts of gelatin in 52 parts of boiling water), and then exposed to the light. Corks thus treated are attacked with difficulty by solvents. N.H. M.189General a n d Physical Chemistry.AbEorption-spectrum of Oxygen. By N. EGOROFF (Compt.7-end., 101: 1143--1145).-The author gives a summary of previousobservations on t'he absorption-spectrum of the terrestrial atmosphereand of oxlgen, and reports the results of some recent experiments.The absorption-spectrum of a layer of the atmosphere 3 kilos. inbreadth, observed a t St. Petersburg, showed the groups A, a, and 13,but the group a was absent. The absorption-spectrum of a columnof oxygen 60 metres in length, under a pressure of 6 atmos., showeddistinctly the group A and the preliminary line and the seven doubletsof the group I3. It is evident therefore that all the lines in the groupsA, B, and a in the absorption-spectrum of the terrestrial atmosphereare due to oxygen.By H.DESLANDRES (Compt. rend.,101, 1256-1260) .-The band-spectrum of nitrogen consists of threedistinct groups. The first, which is entirely visible, extends fromA7000 to about X5000 ; the second, which is partly visible and partlyin the ultra-riolet, extends from about A5000 to X2800, whilst the thirdis wholly in the ultra-violet, and extends from X3000 to X2000. Thesecond group is the most intense, and those bands of it which arevisible are almost equal in intensity, but in the ultra-violet portionsome are very intense whilst others are very weak. The two strongestbands in this group a t 35i9 arid 3372 are characteristic of nitrogen,and can often be seen when all the other bands are invisible.Thethird group is less intense than the second, but has the same generalappearance and shows the same succession of maxima and minima ;it contains two very strong bands a t 248U and 2371 respectively.If the nitrogen is perfectly free from oxygen, and the gas and thevacuum tube are completely dried by means of sodinm, the thirdgroup of bends entirely disappears. It follows thererore that thisgroup is due to an oxide of nitrogen. At the same time the firstgroup showed no appreciable alteration, whilst the second group wasdistinctly stronger. The tube was not entirely free from hydrogen.If oxygen was allowed to enter the tube and was dried by means ofsodium, the three groups were observed with their normal intensities.The second group is probably due to a compound of nitrogen andhydrogen (ammonia), whilst the first group seems to be due to nitrogenalone, or to some other compound of nitrogen and hjdrogen.C. H.13.Band-spectrum of Nitrogen.C. H. B.Relation between the Absorption and the Phosphorescenceof Uranium Compounds. By H. BECQUEREL (Compt. rend., 101,125'2-1256) .-The majority of the uranic compounds are phospho-rescent, and the emitted light gives a spectrum which consists ofseven or eight bands or groups of bands regularly distributed betweenC and F, the positioo and appearance of the bauds depending on theVOL. L. 190 ABSTRACTS OF CHEMICAL PAPERS.particular compound. The same compounds gave an nbForption-spectrum of bands or groups of bands, which in position and appearancedo not coincide with, but seem to be a repetition of, the spectrum ofphosphorescence. The wave-lengths of all the bands in each spectrumare connected by the following law: the inverse differences of thewave-lengths, 01’ the difference in the number of vibrations in unittime, is sensibly constant in passing from one group to another, andthe value of this difference varies but slightly for the different uraniccompounds.Each absorption-band corresponds with a group ofradiations which excite phosphorescence, and the corresponding bandin the spectrum of phosphorescence is of lower refrangibility. Thereare however always one or two bands common to both spectra, showingthat in these regions the phosphorescent substance emits waves of thesame length a s those by which i t was excited.The less refrangibleportion of the absorption-spectrum of uranium compounds seems toterminate between F and 6.Uranous compounds show no appreciable phosphorescence, but givea remarkable discontinuous spectrum extending from P to a consider-able distance into the infra-red. The spectra given by the solid saltsare different from those of their aqueous solutions. The absorption-bands of the urnnous compounds follow with remarkable regularitythe law of distribution of bands in the spectrum of phosphorescenceof the uranic compounds, but without having the same relativeintensities. C. H. B.Spectroscope for Furnaces and for the Bessemer Process.By C. V. ZENGER (Compt.rend., 101, 1005).-Description of thearrangement of spectrcscopic apparatus for the study of flames fromvarious processes.Electromotive Force of the Currents yielded by MetallicCouples in Simple Saline Solutions. By B. C. DAMIEN (Ann.chin^. Phys. [GI, 6, 289--313).-From a large number of determina-tions of the E.M.F. of the currents yielded by zinc-copper and lead-platinum couples in various simple saline solutions, the author findsthat the E.M.F. as a rule decreases with the time the couple isimmersed. In the case, however, of the zinc-copper couple in solutionsof the chlorides, the E.M.F. at first slowly increases. The E.M.F. ofthe current yielded hy a zinc-copper couple i n a solution of magnesiumsulphate is very constant, scarcely varying 0.01 7 1-olt during12 months, and is not appreciably affected by changes either of thestrength of the solution o r of temperature.By introdncizig anexterior resistance of 20,000 ohms, the current becomes practicallyinvariable, even when the couple is kept in circuit; the authorproposes to employ this couple for the generation of currents ofstandard strength. The zinc-copper couple yields currents whoseE.M.F. is almost identical for members of any class of salts containinga given acid, but va.ries greatly with a change of acids ; amalgamationof the zinc slightly increases the E.M.F. a t first, but it decreases morerapidly than is the case when unamalgamated zinc is employed.The current obtained from a platinum and amalgamated zinc couplGEKERAL AND PHYSICAL CHEXIISTHT.191in dilute sulphuric acid has its maximum E.M.F. when its solutioncontains 30 per cent. of acid. A. P.Electrical Conductivity of Carbon Compounds. By A.BARTOLI (Gazzetta, 15, 392-397, and 397-399, 400--403).-1n these1)apers the general results are given of the examination of the electricconductivity of liquid carbon compounds, especially those containingiiitrogen. To avoid the effects of polarisation, the determinationswere made in U tubes, which were heated to a constant temperature.The arnides and anilides and compounds derived from them by thesubstitution of hydrogen in the acid radicles by the halogens, giveindications of conductivity, as also the amines, anilines, and thepyridine bases. The nitro-compounds are conductors, and the sub-stitution of hydrogen by the NOz group increases the conductivity.All liquid carbon compounds, whether in the pure state, or mixed ordissolved, show an increase of conductivity with rise of temperature,thus differing from metallic conductors.A remarkable exception to this generalisation is dieth.ylamine, theconductivity of which decrehqes with the temperatnre.Thus experi-ments are quoted to show that the relative conductivities a t 10" and56" are as 10.79 : 4.4. The conductivity of propylaimine, allylamine,and amylamine between 0" and 50" is invariable.In a former memoir, the author has shown that the electric con-ductivity of most solid carbon compounds diminishes very considerablya t the immediate point of solidification, whilst in others this change,although still considerable, is more gradual. In this paper examplesare given of the latter case, such as benzamide, phenol, and para-toluidine, and one, paranitrotoluene, of the former.Thus the rela-tive conductivities of this last substance, which melts a t 54", are a t56" and a t 50' in the ratio of 10 : 1 respectively. In conclusion,the author expresses his belief that the more regular gradation inthe diminution of the conductivity is dne not to retained traces ofimpurities, but to *he actual nature or physical aggregation of thesubstances themselves. V. H. V.Electrical Conductivity of Mixtures of Organic Com-pounds. By A. BARTOLI (Gazzeth, 15, 410--417).-The author hasnoticed that, although generally the electric conductivity of carboncompounds diminishes almost to zero a t or about their points ofsolidification, yet certain mixtures and solutions of these compoundsshow an increase of conductivity a t temperatures below that of thesolidifying point, and a subsequent, decrease to zero at a lower1 emperature. This phenomenon is not noticeable in mixtures ofnatural origin, such as the oils, wax, balsams, and resins, but only inartificially prepared mixtures and solutions, such as naphthalene withone of its derivatives? naphthalene or paraffin with phenol, phthalic orbenzoic anhydride and the acids of the acetic series.Asregards its explanation there are t w o possible cases to be considered,lst, that of a mechanical mixture, such as paraffin in amyl alcoholI n this paper, tables are given illustrating this phenomenon.0 192 ABSTRACTS OF CREMLCAL PAPERS.or acetic acid; Znd, that of the mutual solution of the two com-ponents, such as naphthalene in one of its derivatives.In the former case, the interdigused liquid would have a constantconductivity independent of the temperature up to the point of it8sown solidification. A simple caseaof the latter is the solution of asmall quantity of a conductorln an insulator ; such a material showstwo points of soliaification, the one near to that of the moreabundantconstituent, the other immediately below. Between these two pointsthere is a sufficient amount of condncting Iiquid interposed bettweenthe solid particles, to admit of Ithe passage of the current ; but thisgradually diminislies with decrease of temperature.This explanat ionis not however valid for Compounds such as phenol and benzamide,which possess R ceiltain amount of conductivity a t temperatures farbelow that of their solidification. V. H. V.Heat of Combustion of Compounds of %he Fatty Series. BgLGGGCIX[K-~ '( Compt. rend., 901, 1061-1064).Heat of combustion.r------- - 1 gram. 1 gram-molecule.Paraldehyde.. ......... e+. .. 6160.4 cal. 813172.8 cal.Normal propionic acid ...... 4957.8 ,) 3668i7.2 ,,Aldol ...................... 6214.3 ,, 546858.4 ,, 9, ,, anhydride . . 5'746.8 ,, 747084,O ,,From these results it follows thst-3C,H,O = 'C,H,,O, develops + 26827 cd.and CGHI003 + HZO = 2C3H602 ,) + 13330 ,,The conversion oi€ acetic anhydride into acetic acia develops13060 cal.The aldol employed in*fhese experimerlts was burnt as soon afterpreparation as possible.From the results obtained, it follows thatthe conversion of 2 mols. aldehyde into aldol develops + 1.3142 cal.Aldol is isomeric with isobutyric acid, but they have a differentchemical function, and th'e difference between their heats of com-bustion, 290i9 cal., is much greater than the differences found inthe case of isomerides of the same function. C. H. B.Heats of Cbmbustionaf Ethereal 'Salts uf Fdtty Acids. ByLOUGUININE (Conq~t. rend., 101, 1154-,1156).Heat of combustion.r-----L--- 7'I giam. 1 gram-molec.de.E t h y1 lactate. ......... 5 5.5 9.4 656000.9E thy1 but y rnt e ........Ethyl isobut,grate...... 7290.7 845721.2Ethyl citrate. . . . . . . . . 5289.0 1459708.0851254.4 7 3 38 -4Yroni these results the htats of combustion of the acids have beeGESERAL ASD PHYSICAL CI-IEJIIS PRY. 19acalculated according to Berthelot's law, that, the heat of combustion. ofthe acid is equal to tliat. of the ethereal salt, minm the sum of the heatof combustion of the alcohol radicle and the prodnct of the number ofmolecules of alcohol into 2000 cal. The heats of formation of tlieacids are the differences between their heats of combustion and thesum of the heats of comb.ustion of their constituenhs.Heat of Heat ofcombustion. formation.1 gram-molecule. 1 gram-molecule.Lactic acid.. ........ 329509 166451Citric acid.......... 4802f19 274991Rutyric acid.. ...... 534764 -Isobutyric acid . . , , . . 519261 -The heat of combustion of normal propionic acid is 366877, andit follows that the replacement of H by OH with formation of lacticacid causes a diminution of 3.7368 cal. in the heat of combustion-The coilversion of mrmal propyl aIcohol into normal propyl glycoldiminishes the lieat of combustion by 49142 cal., and the correspond-ing value in the case of the iso-derivatives is 4'2014 cal. The conver-sion of normal prop91 glycol into glycerol is accompanied by a decreaseof 38716 cal. ia the heat of combustion,The author's value for the heat of combustion of normal butyricacid is considerably higher than that given by Favre and Silbermann(496940 cal.).The heats of combustion of the normal and iso-derivatives are practically identical. A direct determination of tilelieat of combustion of isobutyric acid gave the number 517796 cal.C. H. B.Do the Static and the Dynamic Methods of MeasuringVapour-tensions give Different Results ? By G. W. A. KAHLBAUJI(Be)-., 18, 3146-3153).-A reply to Ramsay and Young (comparethis vol., p. 5).Alcohol and Mixtures of Alcohol with Water. By G.. T.GERLACK (Zed. anal. Chern., 24, 487-533).-The author reviewsthe principal investigations which have been made of the physicalproperties of alcohol and its mixtures with water. Following asuggestion of Ilges, he shows that the following expression serves toconnect the composition, specific heat, and boiling point of an alcoholwater mixture :-a~ s x S + (100 - a)ZOO"luo w boiling point of the mixture,where a is the percentage of alcohol, W the specific heat of themixture, s and s the specific heat and boiling point of absoluiealcohol: the expression does not appear to be a general one, as itdoes not hold good for mixtures of sulphuric acid and watzr.The following law appears, however, to connect the boiling pointwith the relative proportions in a mixhiire of two volatile substances.If to an invariable quantity of the constituent of higher boiliu194 ABSTRACTS OP’ CHEMICAL PAPERS.point vmying quantities of the other constituent are added, the amountof the latter divided by the resulting deprcssion of the boiling pointgives a series of numbers having constant differences f o r equal incre-ments of the more volatile substance.Moreover, the difference bet’weeiieach of the numbers of this series, and the corresponding one obtainedby using as divisor the whole difference between the boiling points ofthe two constituents, is sensibly constant for a wide range, although,naturally, as the proportion of either constituent approaches infinity,the difference must fall to zero. Alteration of pressure affects theamount of t,ho differences, but not their constancy. Mixtures ofalcohol with water, glycerol with water, sulphuric acid with water,and alcohol w i t h ether are found to follow this law ; but i t is obviouslyonly applicable to mixtures whose boiling points lie between those oftheir constituents, and this is by no means alwajs the case.The Law of Density Numbers. By J.A. GROSHANS (Phil. i&g.[ 5 ] , 20, 19-29 and l91--203 ; also Bec. Truv. Chi/r~., 4, 236-1162).-In these papers, the lam of d e n s i t y n ( ~ m b e r s is enunciated andapplied to ithe elemenks and their compounds in different states ofphysical aggregation, such as gases, liquids a t their boiling points,and crystalline solids, whether Iiydrated, anhydrous, or in solution.Various relations are also indicated between these density numbersand the atomic weights, the specific gravities of solids and liquids,specific volumes, and the absolute boiling points.Briefly expressed the lsw is as follows z-‘~ The specijc gravities ofsubstances a1.e proportio?ial t o t h e density numbers.”Thus, to take a simple example i n tlie case of two comparablecompounds containing carbon, hydrogen, and oxygen only, of formdmCI,H,O, and C,,H,O,,, let n and n‘ be the sum of p , q, r, andp’, q’, T’respectively, then if their specific gravities be d and d’, then-M.J. S.d - n n n’ - - -- or - = - = k a constant.d’ n’ d d’These density numbers are simple integers; to each element isassigned only one such number, although two or more elements mayhave t h e same number. The following table contains some of thebetter ascertained nurubers for the elements :-R 1 Li 2 B 3 F 4 M g 5 C a 7 A s 8 Cr 9 N i l 1C 1 B e 2 N 3 N a 4 K 5 Se 8 Mn 9 Co 110 1 S 2 P 3 A 1 4 F e 9 Cu 11Si 4 Br 9 Zn 11Ce 4Sr l;? Sn 14 Ag 1f Ba 19 Hg 26 Pb 29S b 13 Te 14 Cd 16I 14 Pt 16T h e various applications and relations alluded to above of these(i.) lielation fo Atontic Weights.-In some few cases, pairs of ele-numbers will be discussed seriatimGESERAL AND PHYSICAL CHENISTRT.195rnents, whose atomic weights differ by a constant quantity, show asimilar constant difference between their density numbers ; in othercases these numbers show a periodic variation with the atomic weightsanalogous to fhat observed in other physical constants.(ii.) Application to Hydrated Crystalline Salts.-If I3 represent thesum of the density numbers of the elements contained in the salt, dits specific gravity, then B/d=lc, a constant for all salts with similarformulse, and containing the same number of molecules of water ofcrystallisation.Thus, referring to the above table, i t is seen that forthe salt CaCI,,GH,O, B = 7 + 2 x 4 + 6 x 3 = 33, d = 1 %54, B/d = k= 19.95, and this constant holds good for other hexahydrated metallicchlorides, as also for the hexahydrated nitrates of nickel and zinc.So also for the double sulphates and selenatesl of ammonium and themetals of the magnesium series, the values for k are 28.7 and 29.5respectively, which become 23.5 and 24 when the ammonium isreplaced by poiassinm. I n a series of tables, similar results are givenfor simple hydrated sulphates, the double silico-, stanno-, and zircono-fluorides, and the plaiirio- and palladio-chlorides.(iii.) Relation to Alisolvte Boiling Poirtts aad Vapour-densities at thatPoint.--If the boiling point of a compound be so and D, the vapour-density at that point under standard conditions of pressure, then‘1’ = 273 + so ; with these factors the laws of Avogadro and Gay-Lussacmay be expressed thus: 2 = - x 3T, in which M and M‘ are themolecular weights of the two compared compounds. But from thehence - = k a constant, or if the law of densit,y numbers 4 =-compound contain carbon, hydrogen, and oxygen only, then - - k,llilin which n is the sum of the number of atoms (cf.supra). Thus, inthe case of water, this constant equals 62.2 =constant equally holds good for other conipounds derived from waterby the replacement of hydrogen by hydrocarbon and acidic groupings,and containing 10 atoms of hydrogen.Similarly other series ofcompounds, isologous as rcgai ds the numbers of hydrogen-atomscontained therein, have similar constants.(iv.) Relation between the Values cy the Constant T x n/M.-(i.) Theseconstants form a series of algebraic numbers ; (ii) in an homologoi~sseries the constants increase with increase of molecular weiyht ;(iii) corresponding members of different homologous series, such asthe ethers, ethereal salts of the acetic and oxalic acid series, andhenzene, have the same constant. The numbers forming these seriescan be calculated according to the empirical formula T x n/M =27.8dK whilst in other cases the formula becomes T x n/M =28.7 Jm + y, in which y is some sma!2 integer, whilst m representsthe number of CH2 groupings contained in the compound plns 1.Thus, the value for m for ethyl ether, CaH,,O, is 4 + 1 = 5 ; forbenzene, C&, is 3 + 1 = 4; for hexane, C6H14 = 7.(v.) Drtemtinution of Absolute Boiling Points.-It is obvious fromT’11’TB31 D, €3’’T x n -(273+ and this1156 ABSTRACT8 OF CHEMICAL PAPERS.the above that it' the values for m or m + y he known for any seriesof compounds, then the absolute or actual boiling points can becalculated according to the formula T = 273 + 8 =M 27.8 J M Thus,to take the example of benzene, T = 273 + 8 = - X 27.8~'' o rs = 88.4 (85 observed).The degree of accordance between thecalculated and observed boiling points is illustrated by the followingtable, which is selected out of many given in the original papers.n7812Boiling pointNaphthylamine, C,,H,N., . . . . 298.5"Phenylamine, CsH7N . . . . . . . . 184.1Nitronaphthalene, CloH702N. . 305.4Nitrobenzene, C6H8N02 . . . . . . 204.9Methyl nttphthyl ether, CI,H,,O 255.3Methyl phenyl ether, c&o.. 146.6Diphenyl, C12Hlo. . . . . . . . . . . . 241.9Compoimd. calculated.Boiling pointobserved.300"184304205258152243-243Conversely from the observed boiling points the values for x in theabove formula can be determined, as also the density numbers ofother elements ; tables are given illustrative of this point.Relatiow to Spec@ Volurrtes.-As the specific volume of a liquid a tits boiling point so is expressed by the formula vS =-- in applyingthe law of density numbers t o these volumes, the constant v,n/Manalogous to Tn/M is obtained.From the data of Kopp, Pierre, andothers the values for the constants in some few series are calculated,although the data are a t present too few to admit of any discussion onthe relations between the constants.I n conclusion, particular cases are discussed of certain isomericsubstances, such as the crotonic acids, CaHs02, and compounds of thesame or nearly equal molecular weight, acrid f o r which the valae forn or B is the same, but whose boiling point and specific volumes arewidely different, such as bromine and iodine monochloride, sulphurdichloride, SzClz, and sulphur oxychloride, SO,Cl,. I n such cases it isobserved that the values for z differ to an equal degree from somesiniple integer; thus this law points to a previously observed butincompletely understood disturbing influence.MdsV.H. V.Numerical Laws of Chemical Equilibrium. By H. LECHATELIER ( Compt. rend., 101, 1005-1OOS) .-A preliminary inves-tigation of a general equation representing chemical change, in whichthe magnitude of the change is expressed as a function of the con-centration (that is, the quantity of the reacting substances in unitvolume), the temperature, and the electrical conditions. In gaseocssysteins, the coefficient of the proportional variation in the conden-sation of each substance taking part in the reaction, is equal to themechanical energy gained by the syst~rn during an infinitely smalltransformation as a result of the disappearance of the particulaGENEfIAL AND PHYSICAL CHEJIISTRY. 197substance.calorific energy gained under the same condit>ions.determination of the coefficients presents much greater difficulties.The coefficient relattve to the temperature is equal to theThe same formula should apply also to liquid systems, but theC.H. B.Cryoscopy as a means of Determining Molecular Weights.By F. M. RAOT~LT (Compt. rend., 101, 1056--1058).--Tlie author'sexperiments have shown that the molecnlnr reduction of the freezingpoint of one and the same solvent is practically constant for all sub-stances belonging to the same type. Conversely, if the mean co-efficient of reduction for several trj-pes are known, a deteimination ofthe coefficients of reduction of a given substance will serve to indicatewhich of two alternative moleciilar weights is correct.Amongst organic compounds, if water is the solvent, and the sub-stance is neither a true salt nor an ammonium, the molecular weight -19 M is given by the formula M = - where A is, the obserred coefficientAof reduction; if acetic acid is the solvent, the formula becomes$1 = -; if benzene is the solvent and the compound is neither an 39Aalcohol, nor a phenol, nor an acid, the formula is M = 49 - The sameA 'formulze hold good for anhydrous inorganic chlorides, such as AsCI:?,YCl,, &c., which are soluble in benzene or acetic acid.The molecu1a.rweighh of acids, bases, and salts can be determined in a similarmanner, the proper constant being introduced into the formula ineach case.IfE is the weight of a normal alkaline salt which contains one equiva-lent of metal, and A its coefIicient of reduction of the freezing pointof water, then A x E = 35 if the acid is monobasic, 20 if it isdibasic, and 15 if it, is tribasic or tehbasic.Similarly, the atomicity of a metal can be determined.I f E repre-sents that weight of the nitrate which contains one equivalent of acid,then A X E = 35 if the metal of the nitrate is monatomic, 22.5 if i tis diatomic, and A x E < 22.5 if it is plyatomic. The sameformula hold good in the case of the chlorides.The same method serves to determine the basicity of an acid.C . H. B.Physical Molecular Equivalents. By F. GUTHRIE (Chem. News,52, 232-233) .--Many instances are adduced illustrating combina-tions of matter in which the mass ratios, although definite and con-stant, are apparently unconnected with molecular mass ratios. Such,for example, are the cryohydrates: thus sodium chloride formsNnC1 + 10HzO, but potassium sulphate cr-yohydrate is K2SOa +114*2H,O, whilst potassium nitrate yields KNO, + 44*6H,O. Thesub-cryohydrates are, on the other hand, true molecular combinations.I n all )ys, when the metals are mixed in the proportions giving thelowest fusion points, they are never in atomic ratios ; this also holdsgood with regard to the mass and molecular ratios of salt alloys. Thevarying solubility of salts in water of different temperatures i198 ABSTRACTS OF CKERIICAL PAPERS.referred to. Moreover, attention is drawn to the admixture of liquidswith the production of heat, and subsequent contraction (chemicalcombination), or with cooling followed by a gain in volume (theantithesis of chemical combination) ; in the latter case, the maximumeffect is produced a t a certain niolecular weight ratio (the ratio OFmaximum niolecular repulsion), which, in the case of carbon bi-snlphide and chloroform, is 1 : 1, and in the ca,se of carbon bisulphideand alcohol is 2 : 1 ; such mixtures have abnormally high vapour-tensions. In a mixture of carbonic anhydride and hydrogen, the jointvolume is measurably greater than the sum of the volumes of the twogases alone. D. A. L.Molecular Weights of Liquids and Solids (Evidence De-ducible from the Study of Salts). By S. U. PICKENING (Chem.News, 52, 239-240, 251--353).-1n this paper the author critioisesthe literature connected with the so-called molecular compounds suchas hydrated salts, basic salts, double salts, and with the numerousexperiments on hydration, dehydration, vapouy-tensions, dilatation,boiling points and densities of solutions, and calorimetric cxperi-ments niade with such compounds. After carefully considering andsifting the evidence deducible from all these, and from the numerousexpximeiits made by the author himself, he concludes “that, althoughin a few isolated cases the molecular weight would appear to begreater than the analytical results necessitate, still, in a vast majorityof cases we have no grounds for multiplying these weight,s, and have,indeed, a considerable mass of evidence in favour of adhering to thesimplest possible formulae,” but admi ts thaf although the smallestparticles may be simple chemically, there is no reason why they“ may not agglomerate and act in uaison as regards certain physicalforces,” and hence “ t h e molecule of the cheniist is not necessarilyidentical with the molecule of the physicist.” (Compare Guthrie,preceding Abstract). D. A. L.Apparatus to Extract Solutions with Liquids. By G. NEC-MANN (Eer., 18,3061-3064) .-An apparatus is described for extractingan aqueous solution with ether. Ether is boiled in a Bask, from whichthe vapour passes nearly to the bottom of the vessel containing theliquid to be extracted ; when the ether which rises to the surface of theliquid reaches a certain height, it syphons itself back into the distilling-flask. A second apparatus is also described. The author recommendsthe use of corks which have been brushed over with chromo-gelatin(prepared by adding 1 part of ammonium dichromate to a filteredsolution of 4 parts of gelatin in 52 parts of boiling water), and thenexposed to the light. Corks thus treated are attacked with difficultyby solvents. N. H. M

ISSN:0368-1769    

DOI:10.1039/CA8865000189

出版商:RSC    

年代:1886

数据来源: RSC

摘要:

LYORGASIC CIIEJIISTRT. 199 I n o r g a n i c Chemistrr Influence of Moisture on the Oxidation of Hydrogen. By W. M~~LLER-ERZBACH (L'er., 18,5239-3240) .-The author has already shown (An%. Phys. C'hem., 136, 53) that ferric oxide requires a higher temperature for reduction in nearly dry hydrogen, than in moist hydrogen. When hematite is heated in sealed tubes witli calcium chloride and hjdrogen for 7, 17, and 37 hours respectively, me-half, one-third, and one-eighth of the hydrogen remained. This is explained by the gradual decrease of the amount of moisfure in the tube, and the consequent retarding of the reduction. N. H. M. Percentage of Oxygen in the Air. By U. KREUSLER (Bied. Centr., 1885, 649--654~).-Having passed in review the labours of others, and especially those of v.Jolly, and having made numerous analyses of the air himself, the author comes to the conclusion that the statement that the cornpsihion of the atmosphere is constant remains unshaken, or a t least, that the variation is of the very smallest kind. E. W. P. Percentage of Sulphurous Anhydride in Aqueous Solutions of Various Specific Gravities and its Determination therein. By W . B. GILES and A . SCHEARER ( J . Soc. Chem. Ind., 4, 303-305). In a previous communication (ibid., 3, 197), the authors gave an account of an accurate and rapid method of estimating the percentage of sulphurous anhydride when in combination with bases. They found it necessary to add the sulphite to the iodine solution, and not the iodine to the sulphite; and instead of diluting with water down io the percentage of 0.05 per cent.of SO2, as recommended by Bunsen, better results were obtained by placing the weighed solid or liquid substance int.0 an excess of decinormal iodine solution without the use of water. In t'he present paper, it is shown that the same method gives accurate results when applied to the estimation of the anhydride itself. The amount of sulphurous anhydride in its solutions of rarying specific gravities was then determined, and is compared in the accompanying table with the figures given by Gautier and Wagner. From a large number of experiments, the authors have deduced the following simple law of the ratio between any given per- centage of sulphurous anhydride in an aqueous solution at 15.4" and 7(;0 mm. and its sp. gr. " The percentage of SO, multiplied by 5 gives the sp.gr. of the solution over and above 1000."200 ABSTRACTS OF CHEMICAL PAPERS. Percentage of SO, in Solutions of carious Specilfic Gyavities. Giles and Schearer. Gautier and Wagner. T--L-- r--L- Sp. gr. a t 15.Zi”. SO,. sp. gr. sop 1*005l 0.9.) 1.0028 0.5 1.0102 2.05 1.0056 1.0 1.0148 2-87 1.0113 2.0 1 * 02 04 4.04 1.0221 4.0 I 9252 4.99 10275 5.0 1.0297 5.89 1- 0:3 28 6.0 1*0:%53 7.01 1.0397 7.0 1.0399 8.O8 1.0426 8.0 1.0438 8.683 1.0 t74 9.0 1,0492 9-80 1.0520 10.0 1.0541 10.75 - - I -3 D. R. Prepmation of Nitric Oxide- By H. KAEMMERER (Bey., 18, 3064--3066).-A Toulff’s bottle, fitted with a Sunnel and delivery tube, is filled loosely with strips of copper, and then one-third with a cold saturated solution of sodium nitrate.Strong sulphriric is added more or less quickly according to. the amount of gas required. The evolution of gas is very regular, and may be kept up for hours. N. H. M. Action of Hydrogen Phosphide on Solutions of Metallic Salts. By P. KULISCH (Annulem, 231, 327? and Chem. Cent?.., 1885, 805-806).-The author’s results disagree i,n general with Winkler’s i iivestigat ions (Ann- Ph y s . Ch em., 111, 443). Hydrogen phosphide when passed through solutions of salts of the light metals, remains unchanged ; the white precipitate, formed in some cases, consists simply of finely divided phosphorus carried over mechanically. Winkler’s assumption that hydrogen phosphide does not reduce ammonium molybdate is incorrect, for although solutions of that salt free from acid are scarcely affected by the gas, yet free moljbdic acid, especially when warmed, is reduced with formation of the intense blue compound of molybdic acid with molybdenum oxide; t h i s reaction serves for the detection of traces of the gas.Solut.ions of salts of the heavy metals when treabed with the gas undergo partial or total reduction, or a phosphide is formed ; generally both reactions go on togethe]., as in the case of copper sulphate, silver, cobalt, and nickel salts. Lead and cadmium salts furnish precipitates containing excess of metal, which cannot be separated from the phosphide ; these mixed precipitates show a marked tendency to deposit in a mirror-like form. The properties of the phosphides obtained differ very much; when treated with strong acids they are decomposed, and, with the exception of cadmium phospliide.yield non-spontaneously inflammable gas. As LZ rule the action of the hydrogen phosphide is very sldw. H. P. W. Hypophosphoric Acid. BV A. JOLT (Co~npt. rend., 101, 10%- 10 j l and 1148-115 I).-Phosphorus partly immersed in water isISORGANlC CHEMISTRY. 201 allowred to oxidise slowly in a confined space of air at the ordinary temperature, the acid liquid heated to boiling, mixed with sodium carbonate until neutral to metlhrl-orange, concentrated and allowed to cool. The salt which separates is washed with cold watcr and recr-j-s- tallised from boiling water, when it forms large crystals identical with those of sodium hypophosphxte, Na,H2P,O6 + 6H,O, described by Salzer. It loses 6Hz0 at 110", and at a red heat is converted into sodium metaphosphate with evolution of hydrogen.Its solution gives with silver nitrate a white precipitate, which dissolves in warm dilute acid, from which AgrP,O, crgstallises on cooliag. Hypophosphoric acid resembles phosphoric and pbosphoroua acids in its behaviour towards methyl-orange and phenolphthalein, but differe from them in that it shows an intermediate state of saturation corre- sponding with the formation of a sesquisalt. When a solution of monosodium hypophosphate is mixed with a solution of an equivalent quantity 6f barium chloride, a gelatinous precipitate is formed, and the solution, which was previously neiitral to Orange No. 3, becomes acid to this indicator. Titration with&an- dard alkali shows that half an equivalent of acid is liberated, and the precipitate is therefore dibarium hypophosphate.If the precipitate is left in contact with the liquid, it is gradually converted into crystals of monobarium hypophosphate-the conversion being accelerated by agitation and by heating to 50" OF 60". If the original solutions are mixed at loo", the gelatinous precipitate almost immediately changes into a granular precipitate of the same composition, which is only 17er.y slowly attacked by the liberated acid. Moiiobariam hypophosphate is almost insoluble in water. 'It loses 2HZO (10.8 per cent.) at 140°, and a t a somewhat higher temperature gives off hydrogen which 'burns with a green flame. This salt can also be obtained in the following manner. & portion of tbe aqueous solution of the products of the slow combustion of phosphorus is titrated and the remainder is heated to boiling and mixed with sufficient barium carbonate to neutralise one-fourth of the total acid.When the liquid Is allowed to cool monobarium hypophosphate crystallkes out and is yurilfied by washing with cold water until the washings no longer reduce silver nitrate, and is then recrystalIised from very dilute boiling nitrie acid. In order to prepare the acid, the monobarium salt is mixed with an equivalent quantity of sulphuric acid diluted with its own weight of water. After standing for two or three days, the solution is evapo- rated in a vacuum over some hygroscopic substance, and when the composition of the liquid approaches Pz04,6H20, it deposits bulky, rectangular tables which probably belong to the rhombic sjstem.These crystals have the composition P2o4,4H20, are deliquescent, and dissolve rapidly in a small quantity of water. With silver nitrate, the solution gives a white precipikate which does not blacken on boiling and is soluble in warm dilute nitric acid (1 : 1). C. H. B. Preparation of Phosphoric Acid. By G. A. ZIEGELER (Dingl. polyt. J,, 258, 239).--Yhosphoric acid can be prepared from phos- phorus and the quantity of nitric acid theoretically required by202 ABSTRACTS OF CHENICAL PAPERS. adding a small amount of iodine to the mixture. For 100 grams of phosphorus 0.3 to 0.6 gram iodine is used. By A. JOLLY (Compt. rend., 101, 1262--1'264).-The hydrate As,05,4H10 lis deposited in long, trans- parent prisms from a solution of the same composition if the latter is agitated or is exposed to winter temperature.If the solution is more dilufe, a crystal of As205,4H20 or of the isomorphous P205,4H20 must be added to produce crystallisation. A solntion having the composi- tion As,05 + 5H20 may be cooled to - 50" and violently agitated, without solidification taking place. The crystaIs of As2Q5,4Hz0 melt a t 3.5.5-36", are very deliquescent, and dissolve rapidly in a small quantity of water with reduction of temperature. Heat of ~olntion fit 13" in 100H,O = -2.8 cal., in 300 H,O = -2-6 cal., in 900 H,O = = -2.0 cal. It follows from these niim- bers and the heats of solntion of the other hydrates as determined by Thomsen, that- As205 solid + 2H20 solid develops + 1.90 cal.As205 ,: + 31120 7f + 2-6 ,, D. B. Hydmtes of Arsenic Acid. Heat of fusion -7.4 cal. ASd05 ,, + 4HZO r* -t 2-8 ,, combination with the last molecule of water develops only f0.2. The heats of hydration are much lower than in the case of phosphoric acid. The crystals of the hydrate As2O5,4H,O effforesce rapidIy in a drg Vacuum, and form R white powder of the composition 2As20,,3H,0. The same product is obtained by heating the hydrate, Asz05,3H20, a t 100" until it ceases to lose weight. This sesquihydrate is onIy very slightly hygroscopic, but dissolves rapidly in water with development of -heat. Heat of solution a t 14" = +5*52, and therefore 2As,05 solid $-3H20 solid, deveIops +2*20 cal. Tt follows from this result t'iat combinatioil with the first molecule of water deveIops more heat than combination with the second. T;SThen the hydrate As,Q5,4Hz0 is melted in a closed vessel and allowed to remain in snperfusion at the ordinary temperature, i t gradually deposits crystals of the hydrate As2O5,3H20.The hgdrate AszO5,3H20, whether obtained a t the ordinary tempera- ture or by Kopp's method a t loo", does not cause the solidification of superfused P2O5,3H2O, and it would seem, therefore, that the tri- hydrates, unlike the tetrahydrntes, are not isomorphous. This change is exothermic, and develops + 5-8 ml. C. H. B. Oxidation of Various Forms of Carbon. By A. BARTOLI and G. PAPASOGLI (Gazzetta, 15, 446--457).-1n this paper, an account is given of experiments on the oxidation by alkaline hypochlorites of natural and artificial foyms of carbon, such as various species of lignites and fossil carbon, wood and animal charcoal, soot and lamp- b'ack.As a general result it is shown that those forms of carbon which contain one or more per cent. of hydrogen are completely oxidised hy alkaline hypochlorites with formation of carbonic anhydride, oxalic and mellitic acids, together with other less-defined substances. TheISORGANIC CHEXISTRY. 203 various forms of carbon are separable into four distinct classes : lst, those mentioned above, oxidised by alkaline hypochlorites ; 2nd, those unaltered by hypochlorites but transformed into soluble products by potassium chlorate and nitric acid, such as retort carbon ; 3rd, those transformed by the latter reagent into the various forms of graphite ; and, 4th, the diamond unalkered by any of the above reagents.V. H. V. Characteristic Equation of Carbonic Anhydride. By E. SARRAU ( Compt. rend., 101, 1145--1148).-The characteristic eqna- tion of carbonic anhydride being put into the form RT p=------- "J --a (v + p y the constants have 0.001150; and p' = from the results of the values K = 0.016551; E = 1.00285; a = 0.000703 ; the two last values being calcuIated Cailletet and Haut,efeuilIe's experiments on the density of liquid carbonic anhydride under varying conditions. The values calculated by means of these constants agree very closely with Cailletet and Hautefeuille's numbers, and also agree fairly well with the results of Andrews and Amagat's experiments on the gas. By means of these coefficients and Clausius' tables, the following numbers have been calculated :-P = tension of the saturated vapour of carbonic anhydride a t the temperature t ; S and = respectively the specific volumes of the vapour and of the liquid under the pressure P, calculated to the normal volume of the gas; A = the density of the liquid :- P.. s . . 0-00568 0.01422 0.02706 045216 0-1079.5 fi . . 0*00428 0.00251 0.00208 0*00183 0.00167 A . . 0.461 0.785 0.9 50 1 9 7 G 1.1 78 The numbers await experimental verification. At t'he lemperature of solidification, -57", the calculated value of P is 6-15 atmos., and of A 1.209. t .. 30" 10" -10" - 30" - 50" 73-49 atmos. 46.12 atmos. 27.02 atmos. 14.49 atmos. 6-91 atrnos. The actual tension measured by Faradsy was 5.3 atmos.C. H. B. Limits of the Conversion of Sodium Carbonate into Sodium Hydroxide by Lime. By G. LUNGE and J. SCHMID (Ber., 18, 3286 -3289).-According to Mitscherlich (Lehrb. d. Chemie, 2, 15) 1 part of potassium carbonate is only completely causticised by lime in presence of 50 parts of water. Parnell and Simpson (Engl. Pat. No. 4144, Nov. 7, 1877) proposed operating with more concentrated solutions of sodium carbonate under pressure. Experiments made by t,he authors with solutions of pure carbonate of different strengths show khat the highest percentages (99.4 and 99.3) are obtained by using a 2 per cent. sohtion of sodium carbonate. The employment of pressure has no material influence on the result; i t is probable that a thorough stirring assists the reaction.N. H. M.2 04 Al3STRAC;TS OF CHBXIICAL PA) ERP. A New Ammonium Magnesium Phosphate. BY A. GAWA- LOVSKZ ( C h e ~ Centr., 1885, 72l).-€'recipita,ted ammonium mazne- sium phosphate is dissolved to saturation in acetic acid : the solution after a time deposits well-formed crystals having the composition Rfgs(NH&)z( PO,), + 24E20. C. F. C. Some Properties of Zinc. By L. L'H~TE (Compt. rend., 101, 1 I53).-Perfectly pure zinc was obtained by mixing precipitated zinc oxide with calcined lamp-black and distilling the mixture per descerz- sum. The pure metal does not decompose water at lOO", and is not attacked by dilute sulphuric acid. If the pure zinc is melted in a crucible and stirred with an iron rod, i t takes up 0.03-0.05 per cent. of the iron, and the impure zinc thus obtained decomposes boiling water and dissolves in dilute sul- phuric acid.The presence of very small quantities of antimony or arsenic have the same effect on the properties of zinc. All commer- cial samples of the metal decompose water a t 100". The author recommends the use of zinc containing a small quantity of iron in Marsh's process in order to insure a regular erolution of gas. C. H. B. Action of Zinc-dust on Zinc Hydroxide. By G. WIL1,IAMS (Chern. News, 52, 301).-In mnnection with the evolution of hydro- gen from strongly heated zinc-dust (compare this vol., p. 15), it is now shown that zinc-dust which, when heated alone, yielded about 50 times its volume of hydrogen, when mixed with equal weights of zinc hydroxide and then heated to redness, gave off a6 much as 535 times its volume of hydrogen. D.A. L. Action of Nitric Acid on Mercuric Iodide. By K. KRAUT (Bet-., 18, 3461-3462).-As it appears that, the observations of Liebig and .other chemists regarding the reaction between mercuric iodide and nitric acid were incorrect, the author has examined this point. Mercuric iodide when boiled with nitric acid of sp. gr. 1.5, is converted into the iodate Hg(IO:$), ; the same result is obtained with acid of sp. gr. 1.4, although a small quantity of nitrate enters into solution ; with acid of sp. gr. 1.3, white, micaceons leaflets of a com- pound, HgI,Hg(NO,), separate, and finally, with acid of sp. gr. 1.2, red crystals of unaltered iodide are obtained together with white crystals of the preceding compound.Aluminium Sulphate. By A. GAWALOVSKI (Chem. Cenfr., 188.5, iSl).-Perfect crystals of this salt are obtained by dissolving the freshly precipitated hydroxide to satuvation i n sulphuric acid and nllowing the solution to remain for several months, The octahedra c. F. c. V. H. V. have the composition A123SOd + 17H,O. Preparation of Vanadyl Chloride. By L. L'H~TE (Compt. Tend., 101, 1151--1152).-Vanadinit,e occurs in somewhat large quantity at San Luis Potosi, in Mexico. A sample of the mineral from this district had the composition-INORGANIC CHEMISTRY. 205 SiO, + A20,. CaO. FezO,. MnO. CuO. PbO. A@,. V&. Loss. In order to separate t,he vanadium, the powdered mineral is mixed with four times its weight of lamp-black, made into a paste with oil, and calcined.The calcined product is then heated in an oil-bath in a current of dry chlorine, care being taken to prevent the temperat'ure exceeding 300". Pure vanadyl trichloride begins to distil a t 210", and if the temperature is raised to 300" the whole of the vanadium in the mineral is converted into this compound. 13.20 5.48 3-08 1.57 10.01 43.08 0.46 14.42 8.70 C. H. B. Complex Inorganic Acids. By W. GIBBS (Amer. Chem. J., 7, 209-238) .-Phosp hovanndates.-Phosphoric and vanadic anhydrides unite to form well-defined complex inorganic acids strictly comparable with those containing phosphoric and molybdic or tungstic nnhydr- ides (compare Abstr., 1884, 161, 560, 713 ; and 1882, 469, 702). The salts are crystalline, and have a yellow or orange colour; they are frequently decomposed by a large quantity of water, and are generally formed by treating a mixed solution of a vanadate and a phosphate with an acid.P,O,,V,O,, (NH,),O + HzO, briglit yellow; granular crystals ; P205,V205,2 AgzO + 5H20, granular, yellow crystals ; 4Pz05,GV,0,3K,0 + 21HT0, yellow, granular masses ; 7PZO5,6V2O5 + 37Hz0, distinctly crystalline masses ; P205,20\Tzo, + 59H20, granular ruby or garnet- red crystals ; Pz05,2V205,(NH4)z0 + 7Hzo, a lemon-yellow crystalline salt. A rseniovalzadates.-These compounds generally resemble the pre- ceding salts. The compound 5As205,8V205 + 2 i H z 0 , a crystalline orange salt, is described ; a second preparation had a different com- position, namely, 7As,0,,6V205 + ?H20 (compare Abstr., 1884, 1266). Phosphovanadicovanadates are formed by adding a solution of vanadium dioxide, VO,, in hydrochloric acid to a mixed solution of a vanadate and phosphate; they are well crystallised, dark green salts ; 2P,0,,V0,,18V,0,,7(NH4),0 + 50Hzo dissolves in water to a deep red solution ; 5PzO5,VO2,4VZ0,,4Na20 + 37H,O, green, crystal- line scales, insoluble in water ; 1 BP20~,1.LV02,6Vz05,51(10 + 40Hz0, deep green crystals, appearing almost black ; green, crystalline salt ; 14Pz05,16VO~,6V~O~,7(N HJ2O + 6SH20, intensely deep green crystals : 10Pz05,1 1V02,5V205,(NH4),0 + 41H,O, lighter green in colour.A rsew iovanadicovanadates, 1 2AsZO5, 12V02,6 V205, 5 (NH4),0 + 7 H,O, very dark green, almost black, crystalline salt ; olive-green in colour. Varzadicovauadates are obtained by adding an acid solution of vanadium dioxide to a vanadate; they are generally dark green (compare Trans., 1886, 30).The salt 4Vz05,2V02,(NH,)I0 $- 8&O is described. The following compounds are described :- 12Pz05,14VOz,GVz05,7K~O + 52H20, 9As,05, 9V02, 8VZO5,4 (NH,) 2 0 + 1 lH20, VOL. L. - 'U206 ABSTRACTS OF CHEMICAL PAPERS. The probable existence of ranadium componnds corresponding with the phosphorosotungstates and hypophosphotungstates is indicated ; and as t'here are ortho-, pyro-, and various meta-phosphotungstates, so there ought to exist corresponding vanadium compounds. It is saggested that the various double chlorides (such as VOCl,,PtCI,, &c.) are the chlorides of double oxides capable of forming complex acids: and that the ortho-, pyro-, and meta-vanadates, tungststes, &c., are only particular members of a homologous series.From the re- semblance of tbe phospho-vanadates, -tungstates, and -molybdates, it appears that MOO.?, W03, and V,O,*O, are chemically equivalent. The description of two new sodio-ammonium tungstates is appended, namely, 3Naz0,4(NH4)20,16W03 + 18Hz0 and Na,0,4(NH4),0,12WO3 + 14H20 ; both form small shining scales. H. B. LYORGASIC CIIEJIISTRT. 199 I n o r g a n i c Chemistrr Influence of Moisture on the Oxidation of Hydrogen. By W. M~~LLER-ERZBACH (L'er., 18,5239-3240) .-The author has already shown (An%. Phys. C'hem., 136, 53) that ferric oxide requires a higher temperature for reduction in nearly dry hydrogen, than in moist hydrogen. When hematite is heated in sealed tubes witli calcium chloride and hjdrogen for 7, 17, and 37 hours respectively, me-half, one-third, and one-eighth of the hydrogen remained.This is explained by the gradual decrease of the amount of moisfure in the tube, and the consequent retarding of the reduction. N. H. M. Percentage of Oxygen in the Air. By U. KREUSLER (Bied. Centr., 1885, 649--654~).-Having passed in review the labours of others, and especially those of v. Jolly, and having made numerous analyses of the air himself, the author comes to the conclusion that the statement that the cornpsihion of the atmosphere is constant remains unshaken, or a t least, that the variation is of the very smallest kind. E. W. P. Percentage of Sulphurous Anhydride in Aqueous Solutions of Various Specific Gravities and its Determination therein.By W . B. GILES and A . SCHEARER ( J . Soc. Chem. Ind., 4, 303-305). In a previous communication (ibid., 3, 197), the authors gave an account of an accurate and rapid method of estimating the percentage of sulphurous anhydride when in combination with bases. They found it necessary to add the sulphite to the iodine solution, and not the iodine to the sulphite; and instead of diluting with water down io the percentage of 0.05 per cent. of SO2, as recommended by Bunsen, better results were obtained by placing the weighed solid or liquid substance int.0 an excess of decinormal iodine solution without the use of water. In t'he present paper, it is shown that the same method gives accurate results when applied to the estimation of the anhydride itself.The amount of sulphurous anhydride in its solutions of rarying specific gravities was then determined, and is compared in the accompanying table with the figures given by Gautier and Wagner. From a large number of experiments, the authors have deduced the following simple law of the ratio between any given per- centage of sulphurous anhydride in an aqueous solution at 15.4" and 7(;0 mm. and its sp. gr. " The percentage of SO, multiplied by 5 gives the sp. gr. of the solution over and above 1000."200 ABSTRACTS OF CHEMICAL PAPERS. Percentage of SO, in Solutions of carious Specilfic Gyavities. Giles and Schearer. Gautier and Wagner. T--L-- r--L- Sp. gr. a t 15.Zi”. SO,. sp. gr. sop 1*005l 0.9.) 1.0028 0.5 1.0102 2.05 1.0056 1.0 1.0148 2-87 1.0113 2.0 1 * 02 04 4.04 1.0221 4.0 I 9252 4.99 10275 5.0 1.0297 5.89 1- 0:3 28 6.0 1*0:%53 7.01 1.0397 7.0 1.0399 8.O8 1.0426 8.0 1.0438 8.683 1.0 t74 9.0 1,0492 9-80 1.0520 10.0 1.0541 10.75 - - I -3 D.R. Prepmation of Nitric Oxide- By H. KAEMMERER (Bey., 18, 3064--3066).-A Toulff’s bottle, fitted with a Sunnel and delivery tube, is filled loosely with strips of copper, and then one-third with a cold saturated solution of sodium nitrate. Strong sulphriric is added more or less quickly according to. the amount of gas required. The evolution of gas is very regular, and may be kept up for hours. N. H. M. Action of Hydrogen Phosphide on Solutions of Metallic Salts. By P. KULISCH (Annulem, 231, 327? and Chem. Cent?.., 1885, 805-806).-The author’s results disagree i,n general with Winkler’s i iivestigat ions (Ann- Ph y s . Ch em., 111, 443).Hydrogen phosphide when passed through solutions of salts of the light metals, remains unchanged ; the white precipitate, formed in some cases, consists simply of finely divided phosphorus carried over mechanically. Winkler’s assumption that hydrogen phosphide does not reduce ammonium molybdate is incorrect, for although solutions of that salt free from acid are scarcely affected by the gas, yet free moljbdic acid, especially when warmed, is reduced with formation of the intense blue compound of molybdic acid with molybdenum oxide; t h i s reaction serves for the detection of traces of the gas. Solut.ions of salts of the heavy metals when treabed with the gas undergo partial or total reduction, or a phosphide is formed ; generally both reactions go on togethe]., as in the case of copper sulphate, silver, cobalt, and nickel salts. Lead and cadmium salts furnish precipitates containing excess of metal, which cannot be separated from the phosphide ; these mixed precipitates show a marked tendency to deposit in a mirror-like form.The properties of the phosphides obtained differ very much; when treated with strong acids they are decomposed, and, with the exception of cadmium phospliide. yield non-spontaneously inflammable gas. As LZ rule the action of the hydrogen phosphide is very sldw. H. P. W. Hypophosphoric Acid. BV A. JOLT (Co~npt. rend., 101, 10%- 10 j l and 1148-115 I).-Phosphorus partly immersed in water isISORGANlC CHEMISTRY. 201 allowred to oxidise slowly in a confined space of air at the ordinary temperature, the acid liquid heated to boiling, mixed with sodium carbonate until neutral to metlhrl-orange, concentrated and allowed to cool.The salt which separates is washed with cold watcr and recr-j-s- tallised from boiling water, when it forms large crystals identical with those of sodium hypophosphxte, Na,H2P,O6 + 6H,O, described by Salzer. It loses 6Hz0 at 110", and at a red heat is converted into sodium metaphosphate with evolution of hydrogen. Its solution gives with silver nitrate a white precipitate, which dissolves in warm dilute acid, from which AgrP,O, crgstallises on cooliag. Hypophosphoric acid resembles phosphoric and pbosphoroua acids in its behaviour towards methyl-orange and phenolphthalein, but differe from them in that it shows an intermediate state of saturation corre- sponding with the formation of a sesquisalt.When a solution of monosodium hypophosphate is mixed with a solution of an equivalent quantity 6f barium chloride, a gelatinous precipitate is formed, and the solution, which was previously neiitral to Orange No. 3, becomes acid to this indicator. Titration with&an- dard alkali shows that half an equivalent of acid is liberated, and the precipitate is therefore dibarium hypophosphate. If the precipitate is left in contact with the liquid, it is gradually converted into crystals of monobarium hypophosphate-the conversion being accelerated by agitation and by heating to 50" OF 60". If the original solutions are mixed at loo", the gelatinous precipitate almost immediately changes into a granular precipitate of the same composition, which is only 17er.y slowly attacked by the liberated acid.Moiiobariam hypophosphate is almost insoluble in water. 'It loses 2HZO (10.8 per cent.) at 140°, and a t a somewhat higher temperature gives off hydrogen which 'burns with a green flame. This salt can also be obtained in the following manner. & portion of tbe aqueous solution of the products of the slow combustion of phosphorus is titrated and the remainder is heated to boiling and mixed with sufficient barium carbonate to neutralise one-fourth of the total acid. When the liquid Is allowed to cool monobarium hypophosphate crystallkes out and is yurilfied by washing with cold water until the washings no longer reduce silver nitrate, and is then recrystalIised from very dilute boiling nitrie acid.In order to prepare the acid, the monobarium salt is mixed with an equivalent quantity of sulphuric acid diluted with its own weight of water. After standing for two or three days, the solution is evapo- rated in a vacuum over some hygroscopic substance, and when the composition of the liquid approaches Pz04,6H20, it deposits bulky, rectangular tables which probably belong to the rhombic sjstem. These crystals have the composition P2o4,4H20, are deliquescent, and dissolve rapidly in a small quantity of water. With silver nitrate, the solution gives a white precipikate which does not blacken on boiling and is soluble in warm dilute nitric acid (1 : 1). C. H. B. Preparation of Phosphoric Acid.By G. A. ZIEGELER (Dingl. polyt. J,, 258, 239).--Yhosphoric acid can be prepared from phos- phorus and the quantity of nitric acid theoretically required by202 ABSTRACTS OF CHENICAL PAPERS. adding a small amount of iodine to the mixture. For 100 grams of phosphorus 0.3 to 0.6 gram iodine is used. By A. JOLLY (Compt. rend., 101, 1262--1'264).-The hydrate As,05,4H10 lis deposited in long, trans- parent prisms from a solution of the same composition if the latter is agitated or is exposed to winter temperature. If the solution is more dilufe, a crystal of As205,4H20 or of the isomorphous P205,4H20 must be added to produce crystallisation. A solntion having the composi- tion As,05 + 5H20 may be cooled to - 50" and violently agitated, without solidification taking place.The crystaIs of As2Q5,4Hz0 melt a t 3.5.5-36", are very deliquescent, and dissolve rapidly in a small quantity of water with reduction of temperature. Heat of ~olntion fit 13" in 100H,O = -2.8 cal., in 300 H,O = -2-6 cal., in 900 H,O = = -2.0 cal. It follows from these niim- bers and the heats of solntion of the other hydrates as determined by Thomsen, that- As205 solid + 2H20 solid develops + 1.90 cal. As205 ,: + 31120 7f + 2-6 ,, D. B. Hydmtes of Arsenic Acid. Heat of fusion -7.4 cal. ASd05 ,, + 4HZO r* -t 2-8 ,, combination with the last molecule of water develops only f0.2. The heats of hydration are much lower than in the case of phosphoric acid. The crystals of the hydrate As2O5,4H,O effforesce rapidIy in a drg Vacuum, and form R white powder of the composition 2As20,,3H,0.The same product is obtained by heating the hydrate, Asz05,3H20, a t 100" until it ceases to lose weight. This sesquihydrate is onIy very slightly hygroscopic, but dissolves rapidly in water with development of -heat. Heat of solution a t 14" = +5*52, and therefore 2As,05 solid $-3H20 solid, deveIops +2*20 cal. Tt follows from this result t'iat combinatioil with the first molecule of water deveIops more heat than combination with the second. T;SThen the hydrate As,Q5,4Hz0 is melted in a closed vessel and allowed to remain in snperfusion at the ordinary temperature, i t gradually deposits crystals of the hydrate As2O5,3H20. The hgdrate AszO5,3H20, whether obtained a t the ordinary tempera- ture or by Kopp's method a t loo", does not cause the solidification of superfused P2O5,3H2O, and it would seem, therefore, that the tri- hydrates, unlike the tetrahydrntes, are not isomorphous.This change is exothermic, and develops + 5-8 ml. C. H. B. Oxidation of Various Forms of Carbon. By A. BARTOLI and G. PAPASOGLI (Gazzetta, 15, 446--457).-1n this paper, an account is given of experiments on the oxidation by alkaline hypochlorites of natural and artificial foyms of carbon, such as various species of lignites and fossil carbon, wood and animal charcoal, soot and lamp- b'ack. As a general result it is shown that those forms of carbon which contain one or more per cent. of hydrogen are completely oxidised hy alkaline hypochlorites with formation of carbonic anhydride, oxalic and mellitic acids, together with other less-defined substances.TheISORGANIC CHEXISTRY. 203 various forms of carbon are separable into four distinct classes : lst, those mentioned above, oxidised by alkaline hypochlorites ; 2nd, those unaltered by hypochlorites but transformed into soluble products by potassium chlorate and nitric acid, such as retort carbon ; 3rd, those transformed by the latter reagent into the various forms of graphite ; and, 4th, the diamond unalkered by any of the above reagents. V. H. V. Characteristic Equation of Carbonic Anhydride. By E. SARRAU ( Compt. rend., 101, 1145--1148).-The characteristic eqna- tion of carbonic anhydride being put into the form RT p=------- "J --a (v + p y the constants have 0.001150; and p' = from the results of the values K = 0.016551; E = 1.00285; a = 0.000703 ; the two last values being calcuIated Cailletet and Haut,efeuilIe's experiments on the density of liquid carbonic anhydride under varying conditions. The values calculated by means of these constants agree very closely with Cailletet and Hautefeuille's numbers, and also agree fairly well with the results of Andrews and Amagat's experiments on the gas.By means of these coefficients and Clausius' tables, the following numbers have been calculated :-P = tension of the saturated vapour of carbonic anhydride a t the temperature t ; S and = respectively the specific volumes of the vapour and of the liquid under the pressure P, calculated to the normal volume of the gas; A = the density of the liquid :- P. . s . .0-00568 0.01422 0.02706 045216 0-1079.5 fi . . 0*00428 0.00251 0.00208 0*00183 0.00167 A . . 0.461 0.785 0.9 50 1 9 7 G 1.1 78 The numbers await experimental verification. At t'he lemperature of solidification, -57", the calculated value of P is 6-15 atmos., and of A 1.209. t .. 30" 10" -10" - 30" - 50" 73-49 atmos. 46.12 atmos. 27.02 atmos. 14.49 atmos. 6-91 atrnos. The actual tension measured by Faradsy was 5.3 atmos. C. H. B. Limits of the Conversion of Sodium Carbonate into Sodium Hydroxide by Lime. By G. LUNGE and J. SCHMID (Ber., 18, 3286 -3289).-According to Mitscherlich (Lehrb. d. Chemie, 2, 15) 1 part of potassium carbonate is only completely causticised by lime in presence of 50 parts of water. Parnell and Simpson (Engl. Pat. No. 4144, Nov. 7, 1877) proposed operating with more concentrated solutions of sodium carbonate under pressure.Experiments made by t,he authors with solutions of pure carbonate of different strengths show khat the highest percentages (99.4 and 99.3) are obtained by using a 2 per cent. sohtion of sodium carbonate. The employment of pressure has no material influence on the result; i t is probable that a thorough stirring assists the reaction. N. H. M.2 04 Al3STRAC;TS OF CHBXIICAL PA) ERP. A New Ammonium Magnesium Phosphate. BY A. GAWA- LOVSKZ ( C h e ~ Centr., 1885, 72l).-€'recipita,ted ammonium mazne- sium phosphate is dissolved to saturation in acetic acid : the solution after a time deposits well-formed crystals having the composition Rfgs(NH&)z( PO,), + 24E20. C. F. C. Some Properties of Zinc.By L. L'H~TE (Compt. rend., 101, 1 I53).-Perfectly pure zinc was obtained by mixing precipitated zinc oxide with calcined lamp-black and distilling the mixture per descerz- sum. The pure metal does not decompose water at lOO", and is not attacked by dilute sulphuric acid. If the pure zinc is melted in a crucible and stirred with an iron rod, i t takes up 0.03-0.05 per cent. of the iron, and the impure zinc thus obtained decomposes boiling water and dissolves in dilute sul- phuric acid. The presence of very small quantities of antimony or arsenic have the same effect on the properties of zinc. All commer- cial samples of the metal decompose water a t 100". The author recommends the use of zinc containing a small quantity of iron in Marsh's process in order to insure a regular erolution of gas.C. H. B. Action of Zinc-dust on Zinc Hydroxide. By G. WIL1,IAMS (Chern. News, 52, 301).-In mnnection with the evolution of hydro- gen from strongly heated zinc-dust (compare this vol., p. 15), it is now shown that zinc-dust which, when heated alone, yielded about 50 times its volume of hydrogen, when mixed with equal weights of zinc hydroxide and then heated to redness, gave off a6 much as 535 times its volume of hydrogen. D. A. L. Action of Nitric Acid on Mercuric Iodide. By K. KRAUT (Bet-., 18, 3461-3462).-As it appears that, the observations of Liebig and .other chemists regarding the reaction between mercuric iodide and nitric acid were incorrect, the author has examined this point. Mercuric iodide when boiled with nitric acid of sp.gr. 1.5, is converted into the iodate Hg(IO:$), ; the same result is obtained with acid of sp. gr. 1.4, although a small quantity of nitrate enters into solution ; with acid of sp. gr. 1.3, white, micaceons leaflets of a com- pound, HgI,Hg(NO,), separate, and finally, with acid of sp. gr. 1.2, red crystals of unaltered iodide are obtained together with white crystals of the preceding compound. Aluminium Sulphate. By A. GAWALOVSKI (Chem. Cenfr., 188.5, iSl).-Perfect crystals of this salt are obtained by dissolving the freshly precipitated hydroxide to satuvation i n sulphuric acid and nllowing the solution to remain for several months, The octahedra c. F. c. V. H. V. have the composition A123SOd + 17H,O. Preparation of Vanadyl Chloride. By L.L'H~TE (Compt. Tend., 101, 1151--1152).-Vanadinit,e occurs in somewhat large quantity at San Luis Potosi, in Mexico. A sample of the mineral from this district had the composition-INORGANIC CHEMISTRY. 205 SiO, + A20,. CaO. FezO,. MnO. CuO. PbO. A@,. V&. Loss. In order to separate t,he vanadium, the powdered mineral is mixed with four times its weight of lamp-black, made into a paste with oil, and calcined. The calcined product is then heated in an oil-bath in a current of dry chlorine, care being taken to prevent the temperat'ure exceeding 300". Pure vanadyl trichloride begins to distil a t 210", and if the temperature is raised to 300" the whole of the vanadium in the mineral is converted into this compound. 13.20 5.48 3-08 1.57 10.01 43.08 0.46 14.42 8.70 C.H. B. Complex Inorganic Acids. By W. GIBBS (Amer. Chem. J., 7, 209-238) .-Phosp hovanndates.-Phosphoric and vanadic anhydrides unite to form well-defined complex inorganic acids strictly comparable with those containing phosphoric and molybdic or tungstic nnhydr- ides (compare Abstr., 1884, 161, 560, 713 ; and 1882, 469, 702). The salts are crystalline, and have a yellow or orange colour; they are frequently decomposed by a large quantity of water, and are generally formed by treating a mixed solution of a vanadate and a phosphate with an acid. P,O,,V,O,, (NH,),O + HzO, briglit yellow; granular crystals ; P205,V205,2 AgzO + 5H20, granular, yellow crystals ; 4Pz05,GV,0,3K,0 + 21HT0, yellow, granular masses ; 7PZO5,6V2O5 + 37Hz0, distinctly crystalline masses ; P205,20\Tzo, + 59H20, granular ruby or garnet- red crystals ; Pz05,2V205,(NH4)z0 + 7Hzo, a lemon-yellow crystalline salt.A rseniovalzadates.-These compounds generally resemble the pre- ceding salts. The compound 5As205,8V205 + 2 i H z 0 , a crystalline orange salt, is described ; a second preparation had a different com- position, namely, 7As,0,,6V205 + ?H20 (compare Abstr., 1884, 1266). Phosphovanadicovanadates are formed by adding a solution of vanadium dioxide, VO,, in hydrochloric acid to a mixed solution of a vanadate and phosphate; they are well crystallised, dark green salts ; 2P,0,,V0,,18V,0,,7(NH4),0 + 50Hzo dissolves in water to a deep red solution ; 5PzO5,VO2,4VZ0,,4Na20 + 37H,O, green, crystal- line scales, insoluble in water ; 1 BP20~,1.LV02,6Vz05,51(10 + 40Hz0, deep green crystals, appearing almost black ; green, crystalline salt ; 14Pz05,16VO~,6V~O~,7(N HJ2O + 6SH20, intensely deep green crystals : 10Pz05,1 1V02,5V205,(NH4),0 + 41H,O, lighter green in colour.A rsew iovanadicovanadates, 1 2AsZO5, 12V02,6 V205, 5 (NH4),0 + 7 H,O, very dark green, almost black, crystalline salt ; olive-green in colour. Varzadicovauadates are obtained by adding an acid solution of vanadium dioxide to a vanadate; they are generally dark green (compare Trans., 1886, 30). The salt 4Vz05,2V02,(NH,)I0 $- 8&O is described. The following compounds are described :- 12Pz05,14VOz,GVz05,7K~O + 52H20, 9As,05, 9V02, 8VZO5,4 (NH,) 2 0 + 1 lH20, VOL. L. - 'U206 ABSTRACTS OF CHEMICAL PAPERS. The probable existence of ranadium componnds corresponding with the phosphorosotungstates and hypophosphotungstates is indicated ; and as t'here are ortho-, pyro-, and various meta-phosphotungstates, so there ought to exist corresponding vanadium compounds.It is saggested that the various double chlorides (such as VOCl,,PtCI,, &c.) are the chlorides of double oxides capable of forming complex acids: and that the ortho-, pyro-, and meta-vanadates, tungststes, &c., are only particular members of a homologous series. From the re- semblance of tbe phospho-vanadates, -tungstates, and -molybdates, it appears that MOO.?, W03, and V,O,*O, are chemically equivalent. The description of two new sodio-ammonium tungstates is appended, namely, 3Naz0,4(NH4)20,16W03 + 18Hz0 and Na,0,4(NH4),0,12WO3 + 14H20 ; both form small shining scales.H. B.LYORGASIC CIIEJIISTRT. 199I n o r g a n i c ChemistrrInfluence of Moisture on the Oxidation of Hydrogen. ByW. M~~LLER-ERZBACH (L'er., 18,5239-3240) .-The author has alreadyshown (An%. Phys. C'hem., 136, 53) that ferric oxide requires ahigher temperature for reduction in nearly dry hydrogen, than inmoist hydrogen. When hematite is heated in sealed tubes witlicalcium chloride and hjdrogen for 7, 17, and 37 hours respectively,me-half, one-third, and one-eighth of the hydrogen remained. Thisis explained by the gradual decrease of the amount of moisfure in thetube, and the consequent retarding of the reduction. N. H. M.Percentage of Oxygen in the Air. By U. KREUSLER (Bied.Centr., 1885, 649--654~).-Having passed in review the labours ofothers, and especially those of v.Jolly, and having made numerousanalyses of the air himself, the author comes to the conclusion thatthe statement that the cornpsihion of the atmosphere is constantremains unshaken, or a t least, that the variation is of the very smallestkind. E. W. P.Percentage of Sulphurous Anhydride in Aqueous Solutionsof Various Specific Gravities and its Determination therein.By W . B. GILES and A . SCHEARER ( J . Soc. Chem. Ind., 4, 303-305).In a previous communication (ibid., 3, 197), the authors gave anaccount of an accurate and rapid method of estimating the percentageof sulphurous anhydride when in combination with bases. Theyfound it necessary to add the sulphite to the iodine solution, andnot the iodine to the sulphite; and instead of diluting with waterdown io the percentage of 0.05 per cent.of SO2, as recommended byBunsen, better results were obtained by placing the weighed solid orliquid substance int.0 an excess of decinormal iodine solution without theuse of water. In t'he present paper, it is shown that the same methodgives accurate results when applied to the estimation of the anhydrideitself. The amount of sulphurous anhydride in its solutions ofrarying specific gravities was then determined, and is compared inthe accompanying table with the figures given by Gautier andWagner. From a large number of experiments, the authors havededuced the following simple law of the ratio between any given per-centage of sulphurous anhydride in an aqueous solution at 15.4" and7(;0 mm.and its sp. gr. " The percentage of SO, multiplied by 5gives the sp. gr. of the solution over and above 1000.200 ABSTRACTS OF CHEMICAL PAPERS.Percentage of SO, in Solutions of carious Specilfic Gyavities.Giles and Schearer. Gautier and Wagner.T--L-- r--L-Sp. gr. a t 15.Zi”. SO,. sp. gr. sop1*005l 0.9.) 1.0028 0.51.0102 2.05 1.0056 1.01.0148 2-87 1.0113 2.01 * 02 04 4.04 1.0221 4.0I 9252 4.99 10275 5.01.0297 5.89 1- 0:3 28 6.01*0:%53 7.01 1.0397 7.01.0399 8.O8 1.0426 8.01.0438 8.683 1.0 t74 9.01,0492 9-80 1.0520 10.01.0541 10.75 - -I -3D. R.Prepmation of Nitric Oxide- By H. KAEMMERER (Bey., 18,3064--3066).-A Toulff’s bottle, fitted with a Sunnel and deliverytube, is filled loosely with strips of copper, and then one-third with acold saturated solution of sodium nitrate.Strong sulphriric is addedmore or less quickly according to. the amount of gas required. Theevolution of gas is very regular, and may be kept up for hours.N. H. M.Action of Hydrogen Phosphide on Solutions of MetallicSalts. By P. KULISCH (Annulem, 231, 327? and Chem. Cent?.., 1885,805-806).-The author’s results disagree i,n general with Winkler’si iivestigat ions (Ann- Ph y s . Ch em., 111, 443). Hydrogen phosphidewhen passed through solutions of salts of the light metals, remainsunchanged ; the white precipitate, formed in some cases, consistssimply of finely divided phosphorus carried over mechanically.Winkler’s assumption that hydrogen phosphide does not reduceammonium molybdate is incorrect, for although solutions of thatsalt free from acid are scarcely affected by the gas, yet freemoljbdic acid, especially when warmed, is reduced with formationof the intense blue compound of molybdic acid with molybdenumoxide; t h i s reaction serves for the detection of traces of the gas.Solut.ions of salts of the heavy metals when treabed with the gasundergo partial or total reduction, or a phosphide is formed ;generally both reactions go on togethe]., as in the case of coppersulphate, silver, cobalt, and nickel salts. Lead and cadmium saltsfurnish precipitates containing excess of metal, which cannot beseparated from the phosphide ; these mixed precipitates show amarked tendency to deposit in a mirror-like form.The propertiesof the phosphides obtained differ very much; when treated withstrong acids they are decomposed, and, with the exception ofcadmium phospliide. yield non-spontaneously inflammable gas. As LZrule the action of the hydrogen phosphide is very sldw.H. P. W.Hypophosphoric Acid. BV A. JOLT (Co~npt. rend., 101, 10%-10 j l and 1148-115 I).-Phosphorus partly immersed in water iISORGANlC CHEMISTRY. 201allowred to oxidise slowly in a confined space of air at the ordinarytemperature, the acid liquid heated to boiling, mixed with sodiumcarbonate until neutral to metlhrl-orange, concentrated and allowed tocool. The salt which separates is washed with cold watcr and recr-j-s-tallised from boiling water, when it forms large crystals identical withthose of sodium hypophosphxte, Na,H2P,O6 + 6H,O, described bySalzer.It loses 6Hz0 at 110", and at a red heat is converted intosodium metaphosphate with evolution of hydrogen. Its solution giveswith silver nitrate a white precipitate, which dissolves in warm diluteacid, from which AgrP,O, crgstallises on cooliag.Hypophosphoric acid resembles phosphoric and pbosphoroua acids inits behaviour towards methyl-orange and phenolphthalein, but differefrom them in that it shows an intermediate state of saturation corre-sponding with the formation of a sesquisalt.When a solution of monosodium hypophosphate is mixed with asolution of an equivalent quantity 6f barium chloride, a gelatinousprecipitate is formed, and the solution, which was previously neiitralto Orange No.3, becomes acid to this indicator. Titration with&an-dard alkali shows that half an equivalent of acid is liberated, and theprecipitate is therefore dibarium hypophosphate. If the precipitateis left in contact with the liquid, it is gradually converted into crystalsof monobarium hypophosphate-the conversion being accelerated byagitation and by heating to 50" OF 60". If the original solutions aremixed at loo", the gelatinous precipitate almost immediately changesinto a granular precipitate of the same composition, which is only 17er.yslowly attacked by the liberated acid. Moiiobariam hypophosphate isalmost insoluble in water. 'It loses 2HZO (10.8 per cent.) at 140°, anda t a somewhat higher temperature gives off hydrogen which 'burnswith a green flame.This salt can also be obtained in the followingmanner. & portion of tbe aqueous solution of the products of theslow combustion of phosphorus is titrated and the remainder is heatedto boiling and mixed with sufficient barium carbonate to neutraliseone-fourth of the total acid. When the liquid Is allowed to coolmonobarium hypophosphate crystallkes out and is yurilfied by washingwith cold water until the washings no longer reduce silver nitrate, andis then recrystalIised from very dilute boiling nitrie acid.In order to prepare the acid, the monobarium salt is mixed with anequivalent quantity of sulphuric acid diluted with its own weight ofwater.After standing for two or three days, the solution is evapo-rated in a vacuum over some hygroscopic substance, and when thecomposition of the liquid approaches Pz04,6H20, it deposits bulky,rectangular tables which probably belong to the rhombic sjstem.These crystals have the composition P2o4,4H20, are deliquescent, anddissolve rapidly in a small quantity of water. With silver nitrate,the solution gives a white precipikate which does not blacken onboiling and is soluble in warm dilute nitric acid (1 : 1).C. H. B.Preparation of Phosphoric Acid. By G. A. ZIEGELER (Dingl.polyt. J,, 258, 239).--Yhosphoric acid can be prepared from phos-phorus and the quantity of nitric acid theoretically required b202 ABSTRACTS OF CHENICAL PAPERS.adding a small amount of iodine to the mixture.For 100 grams ofphosphorus 0.3 to 0.6 gram iodine is used.By A. JOLLY (Compt. rend., 101,1262--1'264).-The hydrate As,05,4H10 lis deposited in long, trans-parent prisms from a solution of the same composition if the latter isagitated or is exposed to winter temperature. If the solution is moredilufe, a crystal of As205,4H20 or of the isomorphous P205,4H20 mustbe added to produce crystallisation. A solntion having the composi-tion As,05 + 5H20 may be cooled to - 50" and violently agitated,without solidification taking place. The crystaIs of As2Q5,4Hz0 melta t 3.5.5-36", are very deliquescent, and dissolve rapidly in a smallquantity of water with reduction of temperature. Heat of ~olntionfit 13" in 100H,O = -2.8 cal., in 300 H,O = -2-6 cal., in 900 H,O == -2.0 cal.It follows from these niim-bers and the heats of solntion of the other hydrates as determined byThomsen, that-As205 solid + 2H20 solid develops + 1.90 cal.As205 ,: + 31120 7f + 2-6 ,,D. B.Hydmtes of Arsenic Acid.Heat of fusion -7.4 cal.ASd05 ,, + 4HZO r* -t 2-8 ,,combination with the last molecule of water develops only f0.2. Theheats of hydration are much lower than in the case of phosphoricacid.The crystals of the hydrate As2O5,4H,O effforesce rapidIy in a drgVacuum, and form R white powder of the composition 2As20,,3H,0.The same product is obtained by heating the hydrate, Asz05,3H20, a t100" until it ceases to lose weight. This sesquihydrate is onIy veryslightly hygroscopic, but dissolves rapidly in water with developmentof -heat.Heat of solution a t 14" = +5*52, and therefore 2As,05solid $-3H20 solid, deveIops +2*20 cal. Tt follows from this resultt'iat combinatioil with the first molecule of water deveIops more heatthan combination with the second. T;SThen the hydrate As,Q5,4Hz0 ismelted in a closed vessel and allowed to remain in snperfusion at theordinary temperature, i t gradually deposits crystals of the hydrateAs2O5,3H20.The hgdrate AszO5,3H20, whether obtained a t the ordinary tempera-ture or by Kopp's method a t loo", does not cause the solidification ofsuperfused P2O5,3H2O, and it would seem, therefore, that the tri-hydrates, unlike the tetrahydrntes, are not isomorphous.This change is exothermic, and develops + 5-8 ml.C.H. B.Oxidation of Various Forms of Carbon. By A. BARTOLI andG. PAPASOGLI (Gazzetta, 15, 446--457).-1n this paper, an account isgiven of experiments on the oxidation by alkaline hypochlorites ofnatural and artificial foyms of carbon, such as various species oflignites and fossil carbon, wood and animal charcoal, soot and lamp-b'ack. As a general result it is shown that those forms of carbon whichcontain one or more per cent. of hydrogen are completely oxidised hyalkaline hypochlorites with formation of carbonic anhydride, oxalicand mellitic acids, together with other less-defined substances. ThISORGANIC CHEXISTRY. 203various forms of carbon are separable into four distinct classes : lst,those mentioned above, oxidised by alkaline hypochlorites ; 2nd, thoseunaltered by hypochlorites but transformed into soluble products bypotassium chlorate and nitric acid, such as retort carbon ; 3rd, thosetransformed by the latter reagent into the various forms of graphite ;and, 4th, the diamond unalkered by any of the above reagents.V.H. V.Characteristic Equation of Carbonic Anhydride. By E.SARRAU ( Compt. rend., 101, 1145--1148).-The characteristic eqna-tion of carbonic anhydride being put into the formRTp=------- "J --a (v + p ythe constants have0.001150; and p' =from the results ofthe values K = 0.016551; E = 1.00285; a =0.000703 ; the two last values being calcuIatedCailletet and Haut,efeuilIe's experiments on thedensity of liquid carbonic anhydride under varying conditions.Thevalues calculated by means of these constants agree very closely withCailletet and Hautefeuille's numbers, and also agree fairly well withthe results of Andrews and Amagat's experiments on the gas.By means of these coefficients and Clausius' tables, the followingnumbers have been calculated :-P = tension of the saturated vapourof carbonic anhydride a t the temperature t ; S and = respectivelythe specific volumes of the vapour and of the liquid under the pressureP, calculated to the normal volume of the gas; A = the density ofthe liquid :-P. .s . . 0-00568 0.01422 0.02706 045216 0-1079.5fi . . 0*00428 0.00251 0.00208 0*00183 0.00167A . . 0.461 0.785 0.9 50 1 9 7 G 1.1 78The numbers await experimental verification.At t'he lemperature ofsolidification, -57", the calculated value of P is 6-15 atmos., and ofA 1.209.t .. 30" 10" -10" - 30" - 50"73-49 atmos. 46.12 atmos. 27.02 atmos. 14.49 atmos. 6-91 atrnos.The actual tension measured by Faradsy was 5.3 atmos.C. H. B.Limits of the Conversion of Sodium Carbonate into SodiumHydroxide by Lime. By G. LUNGE and J. SCHMID (Ber., 18, 3286-3289).-According to Mitscherlich (Lehrb. d. Chemie, 2, 15) 1 partof potassium carbonate is only completely causticised by lime inpresence of 50 parts of water. Parnell and Simpson (Engl. Pat.No. 4144, Nov. 7, 1877) proposed operating with more concentratedsolutions of sodium carbonate under pressure. Experiments made byt,he authors with solutions of pure carbonate of different strengthsshow khat the highest percentages (99.4 and 99.3) are obtained byusing a 2 per cent.sohtion of sodium carbonate. The employmentof pressure has no material influence on the result; i t is probablethat a thorough stirring assists the reaction. N. H. M2 04 Al3STRAC;TS OF CHBXIICAL PA) ERP.A New Ammonium Magnesium Phosphate. BY A. GAWA-LOVSKZ ( C h e ~ Centr., 1885, 72l).-€'recipita,ted ammonium mazne-sium phosphate is dissolved to saturation in acetic acid : the solutionafter a time deposits well-formed crystals having the compositionRfgs(NH&)z( PO,), + 24E20. C. F. C.Some Properties of Zinc. By L. L'H~TE (Compt. rend., 101,1 I53).-Perfectly pure zinc was obtained by mixing precipitated zincoxide with calcined lamp-black and distilling the mixture per descerz-sum.The pure metal does not decompose water at lOO", and is notattacked by dilute sulphuric acid.If the pure zinc is melted in a crucible and stirred with an ironrod, i t takes up 0.03-0.05 per cent. of the iron, and the impure zincthus obtained decomposes boiling water and dissolves in dilute sul-phuric acid. The presence of very small quantities of antimony orarsenic have the same effect on the properties of zinc. All commer-cial samples of the metal decompose water a t 100".The author recommends the use of zinc containing a small quantityof iron in Marsh's process in order to insure a regular erolution ofgas. C. H. B.Action of Zinc-dust on Zinc Hydroxide. By G. WIL1,IAMS(Chern.News, 52, 301).-In mnnection with the evolution of hydro-gen from strongly heated zinc-dust (compare this vol., p. 15), it isnow shown that zinc-dust which, when heated alone, yielded about50 times its volume of hydrogen, when mixed with equal weights ofzinc hydroxide and then heated to redness, gave off a6 much as 535times its volume of hydrogen. D. A. L.Action of Nitric Acid on Mercuric Iodide. By K. KRAUT(Bet-., 18, 3461-3462).-As it appears that, the observations ofLiebig and .other chemists regarding the reaction between mercuriciodide and nitric acid were incorrect, the author has examined thispoint. Mercuric iodide when boiled with nitric acid of sp. gr. 1.5, isconverted into the iodate Hg(IO:$), ; the same result is obtained withacid of sp.gr. 1.4, although a small quantity of nitrate enters intosolution ; with acid of sp. gr. 1.3, white, micaceons leaflets of a com-pound, HgI,Hg(NO,), separate, and finally, with acid of sp. gr. 1.2,red crystals of unaltered iodide are obtained together with whitecrystals of the preceding compound.Aluminium Sulphate. By A. GAWALOVSKI (Chem. Cenfr., 188.5,iSl).-Perfect crystals of this salt are obtained by dissolving thefreshly precipitated hydroxide to satuvation i n sulphuric acid andnllowing the solution to remain for several months, The octahedra c. F. c.V. H. V.have the composition A123SOd + 17H,O.Preparation of Vanadyl Chloride. By L. L'H~TE (Compt.Tend., 101, 1151--1152).-Vanadinit,e occurs in somewhat largequantity at San Luis Potosi, in Mexico.A sample of the mineralfrom this district had the compositionINORGANIC CHEMISTRY. 205SiO, + A20,. CaO. FezO,. MnO. CuO. PbO. A@,. V&. Loss.In order to separate t,he vanadium, the powdered mineral is mixedwith four times its weight of lamp-black, made into a paste with oil,and calcined. The calcined product is then heated in an oil-bath ina current of dry chlorine, care being taken to prevent the temperat'ureexceeding 300". Pure vanadyl trichloride begins to distil a t 210",and if the temperature is raised to 300" the whole of the vanadium inthe mineral is converted into this compound.13.20 5.48 3-08 1.57 10.01 43.08 0.46 14.42 8.70C. H. B.Complex Inorganic Acids. By W. GIBBS (Amer. Chem. J., 7,209-238) .-Phosp hovanndates.-Phosphoric and vanadic anhydridesunite to form well-defined complex inorganic acids strictly comparablewith those containing phosphoric and molybdic or tungstic nnhydr-ides (compare Abstr., 1884, 161, 560, 713 ; and 1882, 469, 702).Thesalts are crystalline, and have a yellow or orange colour; they arefrequently decomposed by a large quantity of water, and are generallyformed by treating a mixed solution of a vanadate and a phosphatewith an acid.P,O,,V,O,, (NH,),O + HzO, briglit yellow; granular crystals ;P205,V205,2 AgzO + 5H20, granular, yellow crystals ; 4Pz05,GV,0,3K,0 + 21HT0, yellow, granular masses ; 7PZO5,6V2O5 + 37Hz0, distinctlycrystalline masses ; P205,20\Tzo, + 59H20, granular ruby or garnet-red crystals ; Pz05,2V205,(NH4)z0 + 7Hzo, a lemon-yellow crystallinesalt.A rseniovalzadates.-These compounds generally resemble the pre-ceding salts. The compound 5As205,8V205 + 2 i H z 0 , a crystallineorange salt, is described ; a second preparation had a different com-position, namely, 7As,0,,6V205 + ?H20 (compare Abstr., 1884,1266).Phosphovanadicovanadates are formed by adding a solution ofvanadium dioxide, VO,, in hydrochloric acid to a mixed solution ofa vanadate and phosphate; they are well crystallised, dark greensalts ; 2P,0,,V0,,18V,0,,7(NH4),0 + 50Hzo dissolves in water to adeep red solution ; 5PzO5,VO2,4VZ0,,4Na20 + 37H,O, green, crystal-line scales, insoluble in water ; 1 BP20~,1.LV02,6Vz05,51(10 + 40Hz0,deep green crystals, appearing almost black ;green, crystalline salt ; 14Pz05,16VO~,6V~O~,7(N HJ2O + 6SH20,intensely deep green crystals : 10Pz05,1 1V02,5V205,(NH4),0 + 41H,O,lighter green in colour.A rsew iovanadicovanadates, 1 2AsZO5, 12V02,6 V205, 5 (NH4),0 + 7 H,O,very dark green, almost black, crystalline salt ;olive-green in colour.Varzadicovauadates are obtained by adding an acid solution ofvanadium dioxide to a vanadate; they are generally dark green(compare Trans., 1886, 30). The salt 4Vz05,2V02,(NH,)I0 $- 8&Ois described.The following compounds are described :-12Pz05,14VOz,GVz05,7K~O + 52H20,9As,05, 9V02, 8VZO5,4 (NH,) 2 0 + 1 lH20,VOL. L. - '206 ABSTRACTS OF CHEMICAL PAPERS.The probable existence of ranadium componnds corresponding withthe phosphorosotungstates and hypophosphotungstates is indicated ;and as t'here are ortho-, pyro-, and various meta-phosphotungstates,so there ought to exist corresponding vanadium compounds. It issaggested that the various double chlorides (such as VOCl,,PtCI,, &c.)are the chlorides of double oxides capable of forming complex acids:and that the ortho-, pyro-, and meta-vanadates, tungststes, &c., areonly particular members of a homologous series. From the re-semblance of tbe phospho-vanadates, -tungstates, and -molybdates,it appears that MOO.?, W03, and V,O,*O, are chemically equivalent.The description of two new sodio-ammonium tungstates is appended,namely, 3Naz0,4(NH4)20,16W03 + 18Hz0 andNa,0,4(NH4),0,12WO3 + 14H20 ;both form small shining scales. H. B

ISSN:0368-1769    

DOI:10.1039/CA8865000199

出版商:RSC    

年代:1886

数据来源: RSC

摘要:

206 ABSTRACTS OF CHEMICAL PAPERS. M i n e r a 1 o g i c a 1 C h em i s t r y. Native Arsenic of Valtellina. By D. BTZZARI and G . CAMPANI (Gazzetta, 15, 349-351).-In this paper is described the first speci- men of native arsenic in Italy, found on the mountain of Corns dei Darden, near the Passo del Gatto in the Valtelline. The following analytical results were obtained :- Arsenic .......................... 89.57 Antimony ........................ 8.27 Sulphur, calcium, lead, silica, &c. .... 2.16 It occurred in steel-grey, compact masses, of sp. gr. at 27” = 5.777, hardness 4 ; it resembled the native arsenic of Marienberg. V. H. V. Doubly Refracting Crystals of Sodium Chloride and Potas- sium Chloride. By A. BEF SAUDE (Zeit. Kyst. Mirt., 10, 642- 643) .-Doubly refracting crystals of sodium chloride are obtained if the crystallisation is accelerated by change of temperature, or if a gelatinous substance is added to the solution, or if the solubility is decreased by the addition of alcohol.The doubly refracting crystals of sodium or potassium chloride are much less clear than the ordinary crystals ; the clouding being caused by numerous rectangular tabular flu id- i ncl u signs. A mixture of sodium and potassium chlorides, slowly evaporated, gave crystals exhibiting double refraction. These crystals were quite free from inclusions. In the same way, according to Brauns (Zeit. ICryst. Mi%., 10, 110), in the case of the alums, an isomorphous mix- ture causes optical anomalies. B. H. B.MINERALOGICAL CHEMISTRY. 207 Zinc-blende. By F.BECKE (Zeit. Kryst. Min., 11, 54-58j.- Boiling dilute hydrochloric acid, after two to three minutes' action, produces etched figures on the crystalline faces of zinc-blende. They are trisymmetrical on the planos of the tetrahedron, and appear as depressed trilateral pyramids. Supported by the results obtained by thus etching zinc-blende with hydrochloric acid, the author compares the crystals from different localities, giving, in conclusion, a table of the 35 forms hitherto found to occur on zinc-blende crystals. B. H. B. Parallel Growth of Tetrahedrite and Zinc-blende. By F. BECKE (Zeit. Kryst. Jfin., 11, 53-54).-At Kapnik, on compact brown blende and tetrahedrite, yellowish-brown partially transparent crystals of blende occur. On the blende ci*ystals are planted nume- rous tetrahedrite crystals, mostly less than 2 mm.in size. They are younger than the blende, and not a product of its alteration. Tetra- hedrite and blende are aspociated according to this law : the principal axes are parallel, the first tetrahedron of the tetrahedrite is parallel to the second tetrahedron of the blende. B. H. B. So-called Nepaulite. By F. B. MALLET (Rec. Geol. Surv. In&, 1885).-The name nepaulite was given by Piddington to a mineral from Khatmandu which he considered to be essentially a carbonat,e of bismuth, copper, and iron. The author has re-examined the mineral, and finds that on analysis it gives- 5. Sb. As. cu. Age Pb. Fe. '21.12 25.17 1-32 38.69 trace 0.3 5-33 Zn. CaC03. MgCO,. Insoluble. 2-44 1.07 0.13 0-68 It woiild therefore seem to be a partially altered tetrahedrite.Artificial Production of Sulphides. By C. DOELTER (Zeit. Kryst. Min., 11, 29-41).-Iron Pyrites.-The repetition of the syn- thetical experiments of Durocher and Rammelsberg, in which iron chloride or iron glance was acted on by hjdrogen sulphide a t a red heat, showed that a temperature of 200" is sufficient. The experiment was successful when ferric oxide was employed instead of iron glance or metallic iron, but failed with iron carbonate and ferrous sulphate. I n the latter case, troilite appears to be formed. The crystal form of artificial pyrites is usually the cube or the combination of cube and octahedron. I n order to show the action of water containing hydrogen sulphide on iron oxides, iron glance, magnetic oxide, and lastly siderite were treated with aqueous hydrogen sulphide in a closed tube for 72 hours at 90".The best result was obtained with siderite, minute crystals of pyrites being formed. These crystals contained 46.07 per cent. of iron and 53.13 per cent.. of sulphur. The results of the three experi- ments showed that ferric oxide, iron carbonate, and magnetic oxide may easily pass over into pyrites by the action of aqueous hydrogen P 220s ABSTRACTS OF CHEMICAL PAPERS. sulphide in a short time with an inconsiderable increase of tem- perature. Narcasite.--By mixing ferrous sulphate with a little carbon and heating to a red heat in a stream of hydrogen sulphide, marcasite was not formed. The same neqative result was obtained by reducing iron carbonate with sulphuretted hydrogen, and hy decomposing ferrous sulphate with illuminating gas.In all three cases iron pyrites or troilite was formed. Hauerite and Manganese-Z,lende.-If hydrogen sidphide is allowed to act on various manganese compounds, manganese-blende, MnS, is formed. To obtain hauerite, the sulphur must conseq3ently be in excess. The author mixed sulphur with the manganese compound, and warmed the mass in a stream of hydrogen sulphide. The results with braunite, manganese chloride, and potassium permanganate were unsuccessful, manganese-blende being formed. With a mixture of pj roluaite and sulphur, hauerite was ohtained. Galena.-The author's experiments show that galena can easily be formed in nature by the action of hydrogen sulphide on solutions of lead carbonate, or lead chloride. Galena was produced at the ordinary temperature by exposing lead chloride to the action of hydrogen sulphide and some sodium hydrogen carbonate for five months.Cinnabar.-The occurrence of mercury ores shows that they must apparently, in many cases, have been formed by the action of hydrogen sulphide a t a low temperature. This is confirmed by a simple experi- ment; mercury heated in a water-bath a t 70" to 90" for six days in a tube filled with hydrogen sulphide, forms small, red crystals of cinnabar. C'ovelline and Copper Glance.-Copper oxide treated with hydrogen sulphide at, a temperature oE 200" gives a very characteristic crystalline aggregate of covelline. At a higher temperature (250 t o 400") copper g!ance is formed.Cuprous oxide treated with hydrogen sulphide gives copper glance. According to Durocher, this is also obtained at a red heat from copper chloride. Copper Pyrites.--The author obtained small crystals of copper pyrites by the action of hydrogen sulphide on a mixture of 2CuO + Fe,03, slightly heated in a glass tube. Copper pyrites is also formed by treating copper carbonate and ferric sulphate with sulphuretted hydrogen water in a closed tube for three days. Romite.-By the action of sulphuretted hydrogen on a mixture of Cu20, CuO, and FezOs, bornite is obtained at a low temperature, 100" to 200". The compound CugFe4S1,,, which contains less copper and more iron than the normal bornite (CuS,Cu2S,FeS), was obtained from a mixture of 2Fe203,3Cu20,3Cu0. I n other experiments, a mixture rich in iron, Cu2S,2CuS,4FeS, and a mixture rich in copper, were obtained.The experiments seem to prove that bornite differs from copper pyrites in requiring both CuS and Cu2S. The ratio of the two to FeS is not absolutely fixed; and CuS and Cu,S need not be present in equal quantities. Bournonite is obtained by the action of hydrogen sulphide on the corresponding chlorine and oxygen compounds of lead, copper, aiid antimony, a t a, low heat.MINERALOGICAL CHEMISTRY. 209 J I i a r g y ~ i t ~ was obtained by heating a mixture of antimony and silver chlorides, corresponding with the piaoportion Ag : Sb = 1 : 1, in a glass tube through which a strong stream of hydrogen sulphide passed. Jamesnnite was obtained by the action of hydrogen snlphide on a mixture of antimony or antimony oxide and lead chloride a t a tempe- rature of 200" to 400".B. H. B. Massive Safflorite. By L. W. MCCAT (Arner. J. Rci., 29, 369- 374).-In a previous paper (Abstr., 1884, 1098) the author showed that the rhom hic modification of speiskobalt, described by Sandberger as spathiopyrite, is identical with the safflorite of Breithaupt. Sand- berger (Abstr., 1884, 40.5), admitting the existence of the crystalline safflorite, objected to the use of the term to cover the massive varieties, and doubted the accuracy of the statement that speiskobalt and safflorite appear together, the former above the latter. The author has thereEore examined some specimens of speiskobalt from the Freiberg collection, exhibiting the occurrence of smaltine and massive safflorite together.An analysis of a specimen of the grey cobalt arsenir-le, called by the Schneeberg miners XchZackenkobdt, gave the following results :- As. S. Co. Ni. Fe. Cu. Bi. Insoluble. Total. 65.52 0.90 18.36 absent 9.40 0.62 trace 1.30 100.10 This analysis agrees in a curious way with v. Kobell's analysis of E;se?&dmZtkies (safflorite) from Schneeberg ; the quantity of cobalt shown in the author's analysis being identical with the quantity of iron in v. Kobell's, and vice versci. The author is consequently inclined to believe that v. Kobe11 made a mistake in writing down his figures. The specific gravity, 7.167, together with the results of the analysis, prove that the heavy grey Schlackenkobalt is massive safflorite, and the accompanying tin-white smaltine demonstrates conclusively that safflorite and smaltine occur together.B. H. B. The Crystal Forms of the Andreasberg Calcite. By F. SANSONI (Zeit. K v y s t . Min., 10, 545--600).-This paper, the first part of a monograph on calcite, treats of the crystal forms of the Andrens- berg calcite. The nut,hor has examined 2b00 specimens in various public and private collections, and has measured i22 crystals. He finds that the number of forms occurring on Sndreasberg calcite amounts to 131, a.nd that 359 combinations of these forms have, up to the present time, been met with. B. H. B. Determination of the Refractive Indices of Boracite. By. E. MALLARD (Zeit. K r y s t . Min., 10, 631-6:32) .--For the determination of the refractive indices, t,he author employed the measurement of the relative retardation experienced by two principal vibrations running perpendicularly to a crystal plate ; t,he measurements being made by means of a Babinet compensator.I n sections of boracite parallel to the dodecahedron planes, the portions perpendicular to the negative210 ABSTRACTS OF CHEMICAL PAPERS. bisectrix gave nb - n, = 0.00597. This observation combined with Des Cloizeaux's measurement of the axial angle V = 41" 47' gives nb - mu = 0.00477; from which is deduced n, - nu = 0.01074. Combining these data with the mean refractive index (nb = 1.66'7) determined by Des Cloizeaux, the t h e e principal indices are found to be : n, = 1.6622 ; nb = 1.6670; n, = 1.6730. B. H. R. Formation of Beds of Sodium Nitrate.By A. M ~ T Z (Corn@ rend., 101, 1265-1267) .-The author's previous observations and experiments (Cornpt. rend., 85, 1020 ; 100, 1136 ; 101, 65, 248, and 1136 ; see Abstr., 1884, et seg.), lead to the following conclusions. The nitric acid is derived from organic matter by oxidation under the influence of a nitrifying ferment ; sea-water, or the mother-liquor of brackish marshes, has come in contact with the organic matter during nitrification ; the sodium nitrate has been produced by the action of sodium chloride on the calcium nitrate originally formed ; the sodium nitrate has not been formed ,in its present position, but has been removed from its place of origin, and afterwards concentrated in the beds in which it is now found. C. H. B. Mimetesite, containing Lime, from Puy-de-Ddme.By A. DANOUR (Zeit. KrysC. Nin., 10, 627).-Smail botryo'idal masses of a greyish colour, from the Villevieille mine a t Pontgibaut, gave on an a1 y sis- As205. P20,. PbO. CaO. C1. Pb. Total. Sp. gr. 19.65 3.44 63.25 3.46 2.57 7.49 99-86 6.65 This corresponds with the formula (Pb,Ca),C1[(As,P)O4I3. B. H. B. Pectolite fro- Alaska. By H. FISCHER (Zeit. & y t . Nin., 10, 614).-An analysis of pectolite from Port Barrow gave the following results :- Si02. CaO. MgO. Na,O. A1,0,. H2O. Total. Sp. gr. 53.94 32-21 1.43 8.57 0.58 409 100.82 2.873 Colour, pale apple-green ; compact ; easily fusible. B. H. B. New Locality for Nephrite in Asia. By A. B. MEYER (Zeit. Kr-yst. Min., 10, 612).-A dark green mineral brought from Yunan by Anderson, is, according to Arzruni, typical nephrite.Analysis gave- SiO,. A120,. FeO. CaO. MgO. H20. Total. 36-58 0.92 4.12 12-92 21.65 3.25 99.44 The author suggests that Yunan o r Barma is a hitherto unknown locality for Chinese nephrite. Optical Properties of Albite. By A. DES CLOIZEAUX (Zeit. Tiryst. nlrin ., 10, 6 2 8 4 3 1 ) .-Although albite has, of all felspars, the most constant composition, its optical properties vary according l o B. H. B.MINERALOGICAL CHEMISTRY. 211 the homogeneity of the crystals, the number and disposition of the twin lamelh and the manner of its occurrence. Regarding the pro- perties of the crystals from the crystalline schists and in dolomitic limestones as normal, the following may be given :-The plane of the optic axes is always perpendicular to a plane which bevels the acute edge OP, mPm, and with OP forms hhe angle S = 78" to 79".Double refractive posit'ive. The first bisectrix is almost perpendicular t o the edge OP, mPm ; 2H, = 80" t o 85" red ; dispersion p less than u ; BH, = 1 0 4 O to 106" ; plates perpendicular to the second bisectrix exhibit crossed dispersion with more or less distinct inclined dis- persion. Normal results of this kind were given by transparent crystids from the Tyrol, Modane, Dauphin&, greyish-white crystals from Arentlal, large white crystals from Karabinsk in the Ural, olatite from Snarum, small crystals from Calvados, red masses from Piedmont, white masses from the Mer de Glace a t Chamauni, red masses from Mineral Hill, Pennsylvania, peristerite from Perth in Canada, yellow aggregates from Morongoze, and small white masses from S.Marcel and Piedmont. Variations from the normal optical characters were shown hy the following varieties of albite :-Moonstone from Mineral Hi1 1, greyish- green masses from Moriah, New York, peristerite from Bathurst aud Burgess in Canada, partly kaolinised masses from St. Viacenz in Styria, white aggregates from Hammerfest, pericline from the Tyrol, reddish-grey masses from Arendal ; tscherrnakite from Bamle, Mid- dletown in Connecticut, Irigny, Eureka in Victoria. The position of the optic axes is uncertain in the varieties from Crique Boulanger in French Guiana, and from Miask. B. H. B. Andesine from Arddche. By A. DAMOUR (&it. R~pt. 2cz;L'1~., 10, 646 ) .--8 in all, trans par en t, colourless fragments, with dis tine t s tr I a tio n, from a volcanic tuff of the Coirons, near Rochesauve in the depart- ment of Ardbche, gave on analysis the following results :- Si02.AlZO:,. CaO. Na,O. K20. Total. Sp. gr. 58.71 25.43 9.05 5.45 0.78 99.48 2.68 I n the same tuff the following minerals mere also found : octahedra Analysis of Labradorite from the Krakatoa Ashes. By A. of magnetite, yellow titanite, augite, and apatite. SAUER (Zeit. Kryst. Min., 11, 59).--The results were as follows :- B. H. B. SiO,. A.l,O,. CaO. NQO. K20. Total. 51.03 28.37 10.74 8-74! 1-11 99-99 B. H. B. Analysis of Enstatite and Labradorite from the Enstatite- Porphyrite of the Cheviot Hills. By J. PETERSEN (Zeit. K ~ y s t . &!it&., 11, 69--70).-The results of the analyses were as follows : - SiO,.Al,O,. PeO. MgO. CaO. H20. K20. Na,O. Total. I. 52.53 3-38 9.89 26 66 6.19 0.26 - - 98.91 11. 56.04 29-48 - 0.05 l'J.09 - 0.57 6.41 102.64212 ABSTRACTS OF CHEMICAL PAPERS. I, enstatite, sp. gr. 3.331 ; 11, labradorite, sp. gr. 2.666. B. H. B. Analyses of Diallage, Labradorite, Aragonite, and Picrolite. By H. TRAUBE (Zeit. Kryst. Mirz., 11, 60-61).-Diallage (I), and labradorite (11), from the gabbro of the Buchberg, Lower Silesia, gave on analysis the following results :- Si02. A1,03. FeO. FezO,. MnO. CaO. MgO. I. 51-23 1-21 11.57 - 1.26 17.07 16.11 11. 52.08 27.56 - 1.65 - 12.23 0.60 HZO. K,O. Na,O. Total. Sp. gr. I. 1.31 - - 99.76 3-18 11. - 4-82 0.80 99-74 2.71 Aragonite (111) from the magnesite of the Wachberg, near Baum- garten, Lower Silesia, and globular radiated aragonite (IV) with included magnesium carbonante, from the same locality, gave on analysis- co,.CaO. MgO. Total. Sp. gr. IV. 45.73 44.87 9-36 99.96 2.94 111. 44.14 55.33 0.44 99.91 2.91 Picrolite from Endersdorf, Lower Silesia, gave- V. 43.46 2-25 1.26 40.98 trace 12.25 100.20 2.65 B. H. B. SiOz. FeO. A1,03. MgO. CaO. H,O. Total. 8p. gr. corresponding with the formula H,Mg,Si,O, + H20. Hyalophane from Jakobsberg in Wermland, Sweden. By L. J. IGELSTROM (Zeit. Kryst. Min., 10, 632) .-The author has analjsed a greenish-blue compact felspar, which occurs with hausmannite and manganese-epidote in the limestone of the Jakobsberg mine. The results were as follows :- SiO,. &03. BaO. MgO. MnO. K,O + N%O. Total. 53.53 23.33 7.30 3.23 t'race 11-71 99-10 B.H. B. Analysis of Felspar, Augite, and Mica. By G. LINCK (Zeit. R~yst. Mi%., 11, 63-66) .-Analyses of minerals from the minette of Weiier, near Weissenberg, gave the following results :- Si02. TiO,. Al,O,. Fe,O,. FeO. MgO. CaO. KZO. I. 57.13 - 17.29 2.39 - 1.96 1.59 7-83 Ir. 48-23 - 5.28 4-83 3-01 15-84 19.85 0.52 111. 36.61 3-16 15.26 5.11 8.32 16.81 2.71 7.00 Na,O. P. H,O. Total. I. 2.57 - 1.00 101.78 11. 0.67 - 0.45 100.68 111. trace 0.20 4.9-5 100.13 I, felspar (sp. gr. 2.633) ; 11, augite ; 111, mica. B. H. B.MINERALOGICAL CHEMISTR P. 213 Topaz from Stoneham, Maine. By F. W. CLARKE and J. S. DILLER (Amer. J. Xci., 29, 378-384).-C. M. Bradbury (Abstr., 1884, 67) published an analysis of the Stoneham topaz, showing it to be unlike any topaz hitherto known.The peculiar interest attaching to his results made a new analysis desirable. Some apparently altered topaz has now been found, the crystals of which, having the un- changed mineral a t the centre, are transformed on the surface into a dark-purple soft substance. Between the purple zone and the topaz was a greenish intermediate layer. Damourite was intimately associ- ated with the topaz in all the specimens examined. The results of the analyses may be tabulated as follows :- I, unaltered topaz (sp. gr. 3.51, H. 8) ; 11, greenish layer (sp. gr. 3.42, H. 7) ; 111, purple zone (sp. gr. 2.82, H. 3) ; IT, massive damour- ite ; V, foliated damourite :- Si02 ............... F .................. K20 ............... Na,O ............... FeO ................MnO ............... CaO.. .............. MgO ............... Totals ...... Deduct 0 ..... 8 1 2 0 3 . . ............ H20.. .............. Totals ...... I. -- 31 -92 57-38 16 -99 0 *20 0.15 1.33 - - - - -- 107 -97 7 -16 100.81 --- 11. 35 *15 53 -18 12 a3 0 '90 1 -52 1 -28 - 1 *32 0 -17 106 -4Q 5 -42 -i 100 *98 111. 44 -52 46 -19 0 -40 3 -74 2 -30 2 -82 0 -21 0 *30 0.14 100 *62 0.16 - -- 100 46 IV. 45 *19 33.32 4 -48 11-06 1-57 4 -25 0 *58 trace 0 *36 100 -81 V. -- 45.34 33 *96 4 -78 10 -73 1.49 3.96 0.51 0.22 0 -10 1.01.09 - --- The topaz is thus ovdinary topaz, with none of the anomalous character indicated by Bradbury. The analyses point to a progressive change from topaz to damourite, the fluorine and some alumina being gradually eliminated. This change was probably brought ambout by the kaolinisation of adjacent felspathic material.The results of a crystallographic and microscopic examination were even more conclusive than the analyses in showing that the altered topaz is essentially damourite. The fluorine washed out from the topaz in the form of alkaline fluorides, enters into new combinations, represeuted a t the locality hy fluorite, herderite, triplite, and apatite. Rubellan. By M. U. HOLLRCNG (Zeit. Kryst. Min., 11, 53).-The author has investigated the occurrence of rubellan in the basalt tuffs of Schima and Kostenblatt, in the nepheline dolerite of the Loban Mountain, and in the basalt lava of the Laacher See. He arrives at the conclusion that rubellan is not homogeneous, but is an alteration- product. He also states that two different minerals go by the name B.H. B.2 14 ABSTRACTS OF CHENICAL PAPERS. of rubellan. omitted from the mica series. on analysis the following results :- He therefore proposes t'hat the name rubellan should be Rubellan from three different specimens from the Laacher See gave F. Si02. TiO,. Al,O,. Fe203 FeO. MgO. Ia. -- 36-25 0.88 14-88 28.04 3.24 11.18 Ib. - 35.90 0.6.5 1Fi.34 27.69 3.24 11.31 TIu. 1-32 36-99 0.61 18-17 22-19 1.81 11.75 I I b . - 36.97 0.80 17.94 22-81 1.50 11.97 IIIa. 1.19 36.63 1.08 17.11 25.85 1-19 11.78 1IIb. - 37.09 1.24 17.02 25.96 1.19 11.53 K20. Na,O. HPO. Total. Ia. 1.87 1-25 3.29 100.88 I b . 1.59 1.38 3-31 100.41 IIa. 1.66 1.58 3.59 99.67 I I b . 1.60 1-42 3.61 98.62 Illa. 1.88 0.39 4-51 10 1 * 59 IIIb. 2.01 0.38 4.66 101.08 The sp.gr. cf I1 was 2.81 to 2.86, and of 111, 2.50. B. H. B. Blue Tourmaline from Chapey. By A. MICHEL-L~VY (Zeit. Kryst. Min., 10, 649).-In the pegmatite veins in the gneiss of Cliapey, near iliarmagne (Sadne-et-Loire), small strings of a blue substance occur, composed of minute fragments embedded in clay. This blue mineral is uniaxial, and gives a difference of the refractive indices oc - "J = 0.0234, 5t difference which corresponds with tour- maline only. This view is supported by the pleochroysm and sp. gr. of the subsbance. B. H. B. Analyses of Plagioelase and Olivine from Chili. By H. Zr TGENSPECK (Zeit. Kyst. Min., 11, 69).-Plagioclase (I) and olivine (LI), from the basalt of the Volcano Yake, gave on analysis the fol- lowing results :- Si02. A1,0,.Fe2@,. FeO. CaO. MgO. K20. NaZO. I. 46.03 32.41 1.78 - 13.78 0.28 0.73 4.43 - 24.83 - 37.62 - - 11. :38*47 - Ignition. Total. Sp. gr. I. 0.48 99-94 3.14 11. - 100.98 3.48 B. E. B. Artificial Preparation of Rhodonite. By L. BOURGEOIS (Zeit. Kryst. &!in., 10, 626-627).-By fusing MnOz (1 mol.) and SiO, (1 mol.) for a short time, an aggregate of prisms of rhodonite is ob- tained. A mixture of MnO, (2 mols.) and SiO, (1 mol.) gives rhombic plates of tephroite, with small pyramids of hausmannite surrounded by a crystalline aggregate of rhodonite. An intermediate mixture of MnO, and SiO, gives a perfectly crystalline mass consistingORGANIC CHEMISTRY. 215 of large rhombic plates of tephroite, hausmannite, and rhodonite filling the space between the crystals. By employing MnC12, haus- mannite and tephroite are obtained with very fine crystals of rhodonite 0.5 mm.long. These crystals have exactly the composition repre- sented by the formula MnSiO,. The planes observed and the optical properties are exactly the same as those of the natural ciystnls. B. H. B. Deposit from the Spring at Chabetout. By F. THABUIS (Covipt. r e d . , 101, 1163--1164).--The spring at Chabetout, Puy- de- Dame, issues from a compact rock formed of mica schist and goeiss, impregnated with crystals of iron pyrites, and containing traces of arsenical pyrites. The deposit from this water is ochreous and unctuous, and contains micsceous plates and golden-yellow plates. It has the following percentage composition after drying in the air :- CaO.MgO. Alkalis. matter. mica, &c. H20. c 0 2 . 2234 0.276 0.406 9.400 2.087 22.900 1-820 As205. P20,. SiO,. Fe20,. Mn,O,. A1,0,. 0.230 0.145 11.137 49.410 0.305 0.900 Organic Sand, The deposit, contairs lithium. The association of arsenic acid with phosphoric acid is unusual ; the former exists as basic ferric arsenate, the latter as calcium phosphate. C. H. B. 206 ABSTRACTS OF CHEMICAL PAPERS. M i n e r a 1 o g i c a 1 C h em i s t r y. Native Arsenic of Valtellina. By D. BTZZARI and G . CAMPANI (Gazzetta, 15, 349-351).-In this paper is described the first speci- men of native arsenic in Italy, found on the mountain of Corns dei Darden, near the Passo del Gatto in the Valtelline. The following analytical results were obtained :- Arsenic ..........................89.57 Antimony ........................ 8.27 Sulphur, calcium, lead, silica, &c. .... 2.16 It occurred in steel-grey, compact masses, of sp. gr. at 27” = 5.777, hardness 4 ; it resembled the native arsenic of Marienberg. V. H. V. Doubly Refracting Crystals of Sodium Chloride and Potas- sium Chloride. By A. BEF SAUDE (Zeit. Kyst. Mirt., 10, 642- 643) .-Doubly refracting crystals of sodium chloride are obtained if the crystallisation is accelerated by change of temperature, or if a gelatinous substance is added to the solution, or if the solubility is decreased by the addition of alcohol. The doubly refracting crystals of sodium or potassium chloride are much less clear than the ordinary crystals ; the clouding being caused by numerous rectangular tabular flu id- i ncl u signs. A mixture of sodium and potassium chlorides, slowly evaporated, gave crystals exhibiting double refraction.These crystals were quite free from inclusions. In the same way, according to Brauns (Zeit. ICryst. Mi%., 10, 110), in the case of the alums, an isomorphous mix- ture causes optical anomalies. B. H. B.MINERALOGICAL CHEMISTRY. 207 Zinc-blende. By F. BECKE (Zeit. Kryst. Min., 11, 54-58j.- Boiling dilute hydrochloric acid, after two to three minutes' action, produces etched figures on the crystalline faces of zinc-blende. They are trisymmetrical on the planos of the tetrahedron, and appear as depressed trilateral pyramids. Supported by the results obtained by thus etching zinc-blende with hydrochloric acid, the author compares the crystals from different localities, giving, in conclusion, a table of the 35 forms hitherto found to occur on zinc-blende crystals.B. H. B. Parallel Growth of Tetrahedrite and Zinc-blende. By F. BECKE (Zeit. Kryst. Jfin., 11, 53-54).-At Kapnik, on compact brown blende and tetrahedrite, yellowish-brown partially transparent crystals of blende occur. On the blende ci*ystals are planted nume- rous tetrahedrite crystals, mostly less than 2 mm. in size. They are younger than the blende, and not a product of its alteration. Tetra- hedrite and blende are aspociated according to this law : the principal axes are parallel, the first tetrahedron of the tetrahedrite is parallel to the second tetrahedron of the blende. B. H. B. So-called Nepaulite.By F. B. MALLET (Rec. Geol. Surv. In&, 1885).-The name nepaulite was given by Piddington to a mineral from Khatmandu which he considered to be essentially a carbonat,e of bismuth, copper, and iron. The author has re-examined the mineral, and finds that on analysis it gives- 5. Sb. As. cu. Age Pb. Fe. '21.12 25.17 1-32 38.69 trace 0.3 5-33 Zn. CaC03. MgCO,. Insoluble. 2-44 1.07 0.13 0-68 It woiild therefore seem to be a partially altered tetrahedrite. Artificial Production of Sulphides. By C. DOELTER (Zeit. Kryst. Min., 11, 29-41).-Iron Pyrites.-The repetition of the syn- thetical experiments of Durocher and Rammelsberg, in which iron chloride or iron glance was acted on by hjdrogen sulphide a t a red heat, showed that a temperature of 200" is sufficient. The experiment was successful when ferric oxide was employed instead of iron glance or metallic iron, but failed with iron carbonate and ferrous sulphate.I n the latter case, troilite appears to be formed. The crystal form of artificial pyrites is usually the cube or the combination of cube and octahedron. I n order to show the action of water containing hydrogen sulphide on iron oxides, iron glance, magnetic oxide, and lastly siderite were treated with aqueous hydrogen sulphide in a closed tube for 72 hours at 90". The best result was obtained with siderite, minute crystals of pyrites being formed. These crystals contained 46.07 per cent. of iron and 53.13 per cent.. of sulphur. The results of the three experi- ments showed that ferric oxide, iron carbonate, and magnetic oxide may easily pass over into pyrites by the action of aqueous hydrogen P 220s ABSTRACTS OF CHEMICAL PAPERS.sulphide in a short time with an inconsiderable increase of tem- perature. Narcasite.--By mixing ferrous sulphate with a little carbon and heating to a red heat in a stream of hydrogen sulphide, marcasite was not formed. The same neqative result was obtained by reducing iron carbonate with sulphuretted hydrogen, and hy decomposing ferrous sulphate with illuminating gas. In all three cases iron pyrites or troilite was formed. Hauerite and Manganese-Z,lende.-If hydrogen sidphide is allowed to act on various manganese compounds, manganese-blende, MnS, is formed. To obtain hauerite, the sulphur must conseq3ently be in excess. The author mixed sulphur with the manganese compound, and warmed the mass in a stream of hydrogen sulphide.The results with braunite, manganese chloride, and potassium permanganate were unsuccessful, manganese-blende being formed. With a mixture of pj roluaite and sulphur, hauerite was ohtained. Galena.-The author's experiments show that galena can easily be formed in nature by the action of hydrogen sulphide on solutions of lead carbonate, or lead chloride. Galena was produced at the ordinary temperature by exposing lead chloride to the action of hydrogen sulphide and some sodium hydrogen carbonate for five months. Cinnabar.-The occurrence of mercury ores shows that they must apparently, in many cases, have been formed by the action of hydrogen sulphide a t a low temperature.This is confirmed by a simple experi- ment; mercury heated in a water-bath a t 70" to 90" for six days in a tube filled with hydrogen sulphide, forms small, red crystals of cinnabar. C'ovelline and Copper Glance.-Copper oxide treated with hydrogen sulphide at, a temperature oE 200" gives a very characteristic crystalline aggregate of covelline. At a higher temperature (250 t o 400") copper g!ance is formed. Cuprous oxide treated with hydrogen sulphide gives copper glance. According to Durocher, this is also obtained at a red heat from copper chloride. Copper Pyrites.--The author obtained small crystals of copper pyrites by the action of hydrogen sulphide on a mixture of 2CuO + Fe,03, slightly heated in a glass tube. Copper pyrites is also formed by treating copper carbonate and ferric sulphate with sulphuretted hydrogen water in a closed tube for three days. Romite.-By the action of sulphuretted hydrogen on a mixture of Cu20, CuO, and FezOs, bornite is obtained at a low temperature, 100" to 200".The compound CugFe4S1,,, which contains less copper and more iron than the normal bornite (CuS,Cu2S,FeS), was obtained from a mixture of 2Fe203,3Cu20,3Cu0. I n other experiments, a mixture rich in iron, Cu2S,2CuS,4FeS, and a mixture rich in copper, were obtained. The experiments seem to prove that bornite differs from copper pyrites in requiring both CuS and Cu2S. The ratio of the two to FeS is not absolutely fixed; and CuS and Cu,S need not be present in equal quantities. Bournonite is obtained by the action of hydrogen sulphide on the corresponding chlorine and oxygen compounds of lead, copper, aiid antimony, a t a, low heat.MINERALOGICAL CHEMISTRY.209 J I i a r g y ~ i t ~ was obtained by heating a mixture of antimony and silver chlorides, corresponding with the piaoportion Ag : Sb = 1 : 1, in a glass tube through which a strong stream of hydrogen sulphide passed. Jamesnnite was obtained by the action of hydrogen snlphide on a mixture of antimony or antimony oxide and lead chloride a t a tempe- rature of 200" to 400". B. H. B. Massive Safflorite. By L. W. MCCAT (Arner. J. Rci., 29, 369- 374).-In a previous paper (Abstr., 1884, 1098) the author showed that the rhom hic modification of speiskobalt, described by Sandberger as spathiopyrite, is identical with the safflorite of Breithaupt.Sand- berger (Abstr., 1884, 40.5), admitting the existence of the crystalline safflorite, objected to the use of the term to cover the massive varieties, and doubted the accuracy of the statement that speiskobalt and safflorite appear together, the former above the latter. The author has thereEore examined some specimens of speiskobalt from the Freiberg collection, exhibiting the occurrence of smaltine and massive safflorite together. An analysis of a specimen of the grey cobalt arsenir-le, called by the Schneeberg miners XchZackenkobdt, gave the following results :- As. S. Co. Ni. Fe. Cu. Bi. Insoluble. Total. 65.52 0.90 18.36 absent 9.40 0.62 trace 1.30 100.10 This analysis agrees in a curious way with v. Kobell's analysis of E;se?&dmZtkies (safflorite) from Schneeberg ; the quantity of cobalt shown in the author's analysis being identical with the quantity of iron in v.Kobell's, and vice versci. The author is consequently inclined to believe that v. Kobe11 made a mistake in writing down his figures. The specific gravity, 7.167, together with the results of the analysis, prove that the heavy grey Schlackenkobalt is massive safflorite, and the accompanying tin-white smaltine demonstrates conclusively that safflorite and smaltine occur together. B. H. B. The Crystal Forms of the Andreasberg Calcite. By F. SANSONI (Zeit. K v y s t . Min., 10, 545--600).-This paper, the first part of a monograph on calcite, treats of the crystal forms of the Andrens- berg calcite. The nut,hor has examined 2b00 specimens in various public and private collections, and has measured i22 crystals.He finds that the number of forms occurring on Sndreasberg calcite amounts to 131, a.nd that 359 combinations of these forms have, up to the present time, been met with. B. H. B. Determination of the Refractive Indices of Boracite. By. E. MALLARD (Zeit. K r y s t . Min., 10, 631-6:32) .--For the determination of the refractive indices, t,he author employed the measurement of the relative retardation experienced by two principal vibrations running perpendicularly to a crystal plate ; t,he measurements being made by means of a Babinet compensator. I n sections of boracite parallel to the dodecahedron planes, the portions perpendicular to the negative210 ABSTRACTS OF CHEMICAL PAPERS.bisectrix gave nb - n, = 0.00597. This observation combined with Des Cloizeaux's measurement of the axial angle V = 41" 47' gives nb - mu = 0.00477; from which is deduced n, - nu = 0.01074. Combining these data with the mean refractive index (nb = 1.66'7) determined by Des Cloizeaux, the t h e e principal indices are found to be : n, = 1.6622 ; nb = 1.6670; n, = 1.6730. B. H. R. Formation of Beds of Sodium Nitrate. By A. M ~ T Z (Corn@ rend., 101, 1265-1267) .-The author's previous observations and experiments (Cornpt. rend., 85, 1020 ; 100, 1136 ; 101, 65, 248, and 1136 ; see Abstr., 1884, et seg.), lead to the following conclusions. The nitric acid is derived from organic matter by oxidation under the influence of a nitrifying ferment ; sea-water, or the mother-liquor of brackish marshes, has come in contact with the organic matter during nitrification ; the sodium nitrate has been produced by the action of sodium chloride on the calcium nitrate originally formed ; the sodium nitrate has not been formed ,in its present position, but has been removed from its place of origin, and afterwards concentrated in the beds in which it is now found.C. H. B. Mimetesite, containing Lime, from Puy-de-Ddme. By A. DANOUR (Zeit. KrysC. Nin., 10, 627).-Smail botryo'idal masses of a greyish colour, from the Villevieille mine a t Pontgibaut, gave on an a1 y sis- As205. P20,. PbO. CaO. C1. Pb. Total. Sp. gr. 19.65 3.44 63.25 3.46 2.57 7.49 99-86 6.65 This corresponds with the formula (Pb,Ca),C1[(As,P)O4I3. B. H. B. Pectolite fro- Alaska. By H.FISCHER (Zeit. & y t . Nin., 10, 614).-An analysis of pectolite from Port Barrow gave the following results :- Si02. CaO. MgO. Na,O. A1,0,. H2O. Total. Sp. gr. 53.94 32-21 1.43 8.57 0.58 409 100.82 2.873 Colour, pale apple-green ; compact ; easily fusible. B. H. B. New Locality for Nephrite in Asia. By A. B. MEYER (Zeit. Kr-yst. Min., 10, 612).-A dark green mineral brought from Yunan by Anderson, is, according to Arzruni, typical nephrite. Analysis gave- SiO,. A120,. FeO. CaO. MgO. H20. Total. 36-58 0.92 4.12 12-92 21.65 3.25 99.44 The author suggests that Yunan o r Barma is a hitherto unknown locality for Chinese nephrite. Optical Properties of Albite. By A. DES CLOIZEAUX (Zeit. Tiryst. nlrin ., 10, 6 2 8 4 3 1 ) .-Although albite has, of all felspars, the most constant composition, its optical properties vary according l o B.H. B.MINERALOGICAL CHEMISTRY. 211 the homogeneity of the crystals, the number and disposition of the twin lamelh and the manner of its occurrence. Regarding the pro- perties of the crystals from the crystalline schists and in dolomitic limestones as normal, the following may be given :-The plane of the optic axes is always perpendicular to a plane which bevels the acute edge OP, mPm, and with OP forms hhe angle S = 78" to 79". Double refractive posit'ive. The first bisectrix is almost perpendicular t o the edge OP, mPm ; 2H, = 80" t o 85" red ; dispersion p less than u ; BH, = 1 0 4 O to 106" ; plates perpendicular to the second bisectrix exhibit crossed dispersion with more or less distinct inclined dis- persion.Normal results of this kind were given by transparent crystids from the Tyrol, Modane, Dauphin&, greyish-white crystals from Arentlal, large white crystals from Karabinsk in the Ural, olatite from Snarum, small crystals from Calvados, red masses from Piedmont, white masses from the Mer de Glace a t Chamauni, red masses from Mineral Hill, Pennsylvania, peristerite from Perth in Canada, yellow aggregates from Morongoze, and small white masses from S. Marcel and Piedmont. Variations from the normal optical characters were shown hy the following varieties of albite :-Moonstone from Mineral Hi1 1, greyish- green masses from Moriah, New York, peristerite from Bathurst aud Burgess in Canada, partly kaolinised masses from St. Viacenz in Styria, white aggregates from Hammerfest, pericline from the Tyrol, reddish-grey masses from Arendal ; tscherrnakite from Bamle, Mid- dletown in Connecticut, Irigny, Eureka in Victoria.The position of the optic axes is uncertain in the varieties from Crique Boulanger in French Guiana, and from Miask. B. H. B. Andesine from Arddche. By A. DAMOUR (&it. R~pt. 2cz;L'1~., 10, 646 ) .--8 in all, trans par en t, colourless fragments, with dis tine t s tr I a tio n, from a volcanic tuff of the Coirons, near Rochesauve in the depart- ment of Ardbche, gave on analysis the following results :- Si02. AlZO:,. CaO. Na,O. K20. Total. Sp. gr. 58.71 25.43 9.05 5.45 0.78 99.48 2.68 I n the same tuff the following minerals mere also found : octahedra Analysis of Labradorite from the Krakatoa Ashes. By A.of magnetite, yellow titanite, augite, and apatite. SAUER (Zeit. Kryst. Min., 11, 59).--The results were as follows :- B. H. B. SiO,. A.l,O,. CaO. NQO. K20. Total. 51.03 28.37 10.74 8-74! 1-11 99-99 B. H. B. Analysis of Enstatite and Labradorite from the Enstatite- Porphyrite of the Cheviot Hills. By J. PETERSEN (Zeit. K ~ y s t . &!it&., 11, 69--70).-The results of the analyses were as follows : - SiO,. Al,O,. PeO. MgO. CaO. H20. K20. Na,O. Total. I. 52.53 3-38 9.89 26 66 6.19 0.26 - - 98.91 11. 56.04 29-48 - 0.05 l'J.09 - 0.57 6.41 102.64212 ABSTRACTS OF CHEMICAL PAPERS. I, enstatite, sp. gr. 3.331 ; 11, labradorite, sp. gr. 2.666. B. H. B. Analyses of Diallage, Labradorite, Aragonite, and Picrolite. By H. TRAUBE (Zeit.Kryst. Mirz., 11, 60-61).-Diallage (I), and labradorite (11), from the gabbro of the Buchberg, Lower Silesia, gave on analysis the following results :- Si02. A1,03. FeO. FezO,. MnO. CaO. MgO. I. 51-23 1-21 11.57 - 1.26 17.07 16.11 11. 52.08 27.56 - 1.65 - 12.23 0.60 HZO. K,O. Na,O. Total. Sp. gr. I. 1.31 - - 99.76 3-18 11. - 4-82 0.80 99-74 2.71 Aragonite (111) from the magnesite of the Wachberg, near Baum- garten, Lower Silesia, and globular radiated aragonite (IV) with included magnesium carbonante, from the same locality, gave on analysis- co,. CaO. MgO. Total. Sp. gr. IV. 45.73 44.87 9-36 99.96 2.94 111. 44.14 55.33 0.44 99.91 2.91 Picrolite from Endersdorf, Lower Silesia, gave- V. 43.46 2-25 1.26 40.98 trace 12.25 100.20 2.65 B. H. B. SiOz. FeO. A1,03.MgO. CaO. H,O. Total. 8p. gr. corresponding with the formula H,Mg,Si,O, + H20. Hyalophane from Jakobsberg in Wermland, Sweden. By L. J. IGELSTROM (Zeit. Kryst. Min., 10, 632) .-The author has analjsed a greenish-blue compact felspar, which occurs with hausmannite and manganese-epidote in the limestone of the Jakobsberg mine. The results were as follows :- SiO,. &03. BaO. MgO. MnO. K,O + N%O. Total. 53.53 23.33 7.30 3.23 t'race 11-71 99-10 B. H. B. Analysis of Felspar, Augite, and Mica. By G. LINCK (Zeit. R~yst. Mi%., 11, 63-66) .-Analyses of minerals from the minette of Weiier, near Weissenberg, gave the following results :- Si02. TiO,. Al,O,. Fe,O,. FeO. MgO. CaO. KZO. I. 57.13 - 17.29 2.39 - 1.96 1.59 7-83 Ir. 48-23 - 5.28 4-83 3-01 15-84 19.85 0.52 111. 36.61 3-16 15.26 5.11 8.32 16.81 2.71 7.00 Na,O. P.H,O. Total. I. 2.57 - 1.00 101.78 11. 0.67 - 0.45 100.68 111. trace 0.20 4.9-5 100.13 I, felspar (sp. gr. 2.633) ; 11, augite ; 111, mica. B. H. B.MINERALOGICAL CHEMISTR P. 213 Topaz from Stoneham, Maine. By F. W. CLARKE and J. S. DILLER (Amer. J. Xci., 29, 378-384).-C. M. Bradbury (Abstr., 1884, 67) published an analysis of the Stoneham topaz, showing it to be unlike any topaz hitherto known. The peculiar interest attaching to his results made a new analysis desirable. Some apparently altered topaz has now been found, the crystals of which, having the un- changed mineral a t the centre, are transformed on the surface into a dark-purple soft substance. Between the purple zone and the topaz was a greenish intermediate layer.Damourite was intimately associ- ated with the topaz in all the specimens examined. The results of the analyses may be tabulated as follows :- I, unaltered topaz (sp. gr. 3.51, H. 8) ; 11, greenish layer (sp. gr. 3.42, H. 7) ; 111, purple zone (sp. gr. 2.82, H. 3) ; IT, massive damour- ite ; V, foliated damourite :- Si02 ............... F .................. K20 ............... Na,O ............... FeO ................ MnO ............... CaO.. .............. MgO ............... Totals ...... Deduct 0 ..... 8 1 2 0 3 . . ............ H20.. .............. Totals ...... I. -- 31 -92 57-38 16 -99 0 *20 0.15 1.33 - - - - -- 107 -97 7 -16 100.81 --- 11. 35 *15 53 -18 12 a3 0 '90 1 -52 1 -28 - 1 *32 0 -17 106 -4Q 5 -42 -i 100 *98 111. 44 -52 46 -19 0 -40 3 -74 2 -30 2 -82 0 -21 0 *30 0.14 100 *62 0.16 - -- 100 46 IV.45 *19 33.32 4 -48 11-06 1-57 4 -25 0 *58 trace 0 *36 100 -81 V. -- 45.34 33 *96 4 -78 10 -73 1.49 3.96 0.51 0.22 0 -10 1.01.09 - --- The topaz is thus ovdinary topaz, with none of the anomalous character indicated by Bradbury. The analyses point to a progressive change from topaz to damourite, the fluorine and some alumina being gradually eliminated. This change was probably brought ambout by the kaolinisation of adjacent felspathic material. The results of a crystallographic and microscopic examination were even more conclusive than the analyses in showing that the altered topaz is essentially damourite. The fluorine washed out from the topaz in the form of alkaline fluorides, enters into new combinations, represeuted a t the locality hy fluorite, herderite, triplite, and apatite.Rubellan. By M. U. HOLLRCNG (Zeit. Kryst. Min., 11, 53).-The author has investigated the occurrence of rubellan in the basalt tuffs of Schima and Kostenblatt, in the nepheline dolerite of the Loban Mountain, and in the basalt lava of the Laacher See. He arrives at the conclusion that rubellan is not homogeneous, but is an alteration- product. He also states that two different minerals go by the name B. H. B.2 14 ABSTRACTS OF CHENICAL PAPERS. of rubellan. omitted from the mica series. on analysis the following results :- He therefore proposes t'hat the name rubellan should be Rubellan from three different specimens from the Laacher See gave F. Si02. TiO,. Al,O,. Fe203 FeO.MgO. Ia. -- 36-25 0.88 14-88 28.04 3.24 11.18 Ib. - 35.90 0.6.5 1Fi.34 27.69 3.24 11.31 TIu. 1-32 36-99 0.61 18-17 22-19 1.81 11.75 I I b . - 36.97 0.80 17.94 22-81 1.50 11.97 IIIa. 1.19 36.63 1.08 17.11 25.85 1-19 11.78 1IIb. - 37.09 1.24 17.02 25.96 1.19 11.53 K20. Na,O. HPO. Total. Ia. 1.87 1-25 3.29 100.88 I b . 1.59 1.38 3-31 100.41 IIa. 1.66 1.58 3.59 99.67 I I b . 1.60 1-42 3.61 98.62 Illa. 1.88 0.39 4-51 10 1 * 59 IIIb. 2.01 0.38 4.66 101.08 The sp. gr. cf I1 was 2.81 to 2.86, and of 111, 2.50. B. H. B. Blue Tourmaline from Chapey. By A. MICHEL-L~VY (Zeit. Kryst. Min., 10, 649).-In the pegmatite veins in the gneiss of Cliapey, near iliarmagne (Sadne-et-Loire), small strings of a blue substance occur, composed of minute fragments embedded in clay. This blue mineral is uniaxial, and gives a difference of the refractive indices oc - "J = 0.0234, 5t difference which corresponds with tour- maline only.This view is supported by the pleochroysm and sp. gr. of the subsbance. B. H. B. Analyses of Plagioelase and Olivine from Chili. By H. Zr TGENSPECK (Zeit. Kyst. Min., 11, 69).-Plagioclase (I) and olivine (LI), from the basalt of the Volcano Yake, gave on analysis the fol- lowing results :- Si02. A1,0,. Fe2@,. FeO. CaO. MgO. K20. NaZO. I. 46.03 32.41 1.78 - 13.78 0.28 0.73 4.43 - 24.83 - 37.62 - - 11. :38*47 - Ignition. Total. Sp. gr. I. 0.48 99-94 3.14 11. - 100.98 3.48 B. E. B. Artificial Preparation of Rhodonite. By L. BOURGEOIS (Zeit. Kryst. &!in., 10, 626-627).-By fusing MnOz (1 mol.) and SiO, (1 mol.) for a short time, an aggregate of prisms of rhodonite is ob- tained.A mixture of MnO, (2 mols.) and SiO, (1 mol.) gives rhombic plates of tephroite, with small pyramids of hausmannite surrounded by a crystalline aggregate of rhodonite. An intermediate mixture of MnO, and SiO, gives a perfectly crystalline mass consistingORGANIC CHEMISTRY. 215 of large rhombic plates of tephroite, hausmannite, and rhodonite filling the space between the crystals. By employing MnC12, haus- mannite and tephroite are obtained with very fine crystals of rhodonite 0.5 mm. long. These crystals have exactly the composition repre- sented by the formula MnSiO,. The planes observed and the optical properties are exactly the same as those of the natural ciystnls. B. H. B. Deposit from the Spring at Chabetout. By F.THABUIS (Covipt. r e d . , 101, 1163--1164).--The spring at Chabetout, Puy- de- Dame, issues from a compact rock formed of mica schist and goeiss, impregnated with crystals of iron pyrites, and containing traces of arsenical pyrites. The deposit from this water is ochreous and unctuous, and contains micsceous plates and golden-yellow plates. It has the following percentage composition after drying in the air :- CaO. MgO. Alkalis. matter. mica, &c. H20. c 0 2 . 2234 0.276 0.406 9.400 2.087 22.900 1-820 As205. P20,. SiO,. Fe20,. Mn,O,. A1,0,. 0.230 0.145 11.137 49.410 0.305 0.900 Organic Sand, The deposit, contairs lithium. The association of arsenic acid with phosphoric acid is unusual ; the former exists as basic ferric arsenate, the latter as calcium phosphate. C.H. B.206 ABSTRACTS OF CHEMICAL PAPERS.M i n e r a 1 o g i c a 1 C h em i s t r y.Native Arsenic of Valtellina. By D. BTZZARI and G . CAMPANI(Gazzetta, 15, 349-351).-In this paper is described the first speci-men of native arsenic in Italy, found on the mountain of Corns deiDarden, near the Passo del Gatto in the Valtelline. The followinganalytical results were obtained :-Arsenic .......................... 89.57Antimony ........................ 8.27Sulphur, calcium, lead, silica, &c. .... 2.16It occurred in steel-grey, compact masses, of sp. gr. at 27” = 5.777,hardness 4 ; it resembled the native arsenic of Marienberg.V. H. V.Doubly Refracting Crystals of Sodium Chloride and Potas-sium Chloride. By A.BEF SAUDE (Zeit. Kyst. Mirt., 10, 642-643) .-Doubly refracting crystals of sodium chloride are obtained ifthe crystallisation is accelerated by change of temperature, or if agelatinous substance is added to the solution, or if the solubility isdecreased by the addition of alcohol. The doubly refracting crystalsof sodium or potassium chloride are much less clear than the ordinarycrystals ; the clouding being caused by numerous rectangular tabularflu id- i ncl u signs.A mixture of sodium and potassium chlorides, slowly evaporated,gave crystals exhibiting double refraction. These crystals were quitefree from inclusions. In the same way, according to Brauns (Zeit.ICryst. Mi%., 10, 110), in the case of the alums, an isomorphous mix-ture causes optical anomalies.B. H. BMINERALOGICAL CHEMISTRY. 207Zinc-blende. By F. BECKE (Zeit. Kryst. Min., 11, 54-58j.-Boiling dilute hydrochloric acid, after two to three minutes' action,produces etched figures on the crystalline faces of zinc-blende. Theyare trisymmetrical on the planos of the tetrahedron, and appear asdepressed trilateral pyramids. Supported by the results obtained bythus etching zinc-blende with hydrochloric acid, the author comparesthe crystals from different localities, giving, in conclusion, a table ofthe 35 forms hitherto found to occur on zinc-blende crystals.B. H. B.Parallel Growth of Tetrahedrite and Zinc-blende. By F.BECKE (Zeit. Kryst. Jfin., 11, 53-54).-At Kapnik, on compactbrown blende and tetrahedrite, yellowish-brown partially transparentcrystals of blende occur.On the blende ci*ystals are planted nume-rous tetrahedrite crystals, mostly less than 2 mm. in size. They areyounger than the blende, and not a product of its alteration. Tetra-hedrite and blende are aspociated according to this law : the principalaxes are parallel, the first tetrahedron of the tetrahedrite is parallel tothe second tetrahedron of the blende. B. H. B.So-called Nepaulite. By F. B. MALLET (Rec. Geol. Surv. In&,1885).-The name nepaulite was given by Piddington to a mineralfrom Khatmandu which he considered to be essentially a carbonat,e ofbismuth, copper, and iron. The author has re-examined the mineral,and finds that on analysis it gives-5. Sb. As. cu. Age Pb. Fe.'21.12 25.17 1-32 38.69 trace 0.3 5-33Zn.CaC03. MgCO,. Insoluble.2-44 1.07 0.13 0-68It woiild therefore seem to be a partially altered tetrahedrite.Artificial Production of Sulphides. By C. DOELTER (Zeit.Kryst. Min., 11, 29-41).-Iron Pyrites.-The repetition of the syn-thetical experiments of Durocher and Rammelsberg, in which ironchloride or iron glance was acted on by hjdrogen sulphide a t a redheat, showed that a temperature of 200" is sufficient. The experimentwas successful when ferric oxide was employed instead of iron glanceor metallic iron, but failed with iron carbonate and ferrous sulphate.I n the latter case, troilite appears to be formed. The crystal form ofartificial pyrites is usually the cube or the combination of cube andoctahedron.I n order to show the action of water containing hydrogen sulphideon iron oxides, iron glance, magnetic oxide, and lastly siderite weretreated with aqueous hydrogen sulphide in a closed tube for 72 hoursat 90".The best result was obtained with siderite, minute crystalsof pyrites being formed. These crystals contained 46.07 per cent. ofiron and 53.13 per cent.. of sulphur. The results of the three experi-ments showed that ferric oxide, iron carbonate, and magnetic oxidemay easily pass over into pyrites by the action of aqueous hydrogenP 20s ABSTRACTS OF CHEMICAL PAPERS.sulphide in a short time with an inconsiderable increase of tem-perature.Narcasite.--By mixing ferrous sulphate with a little carbon andheating to a red heat in a stream of hydrogen sulphide, marcasitewas not formed. The same neqative result was obtained by reducingiron carbonate with sulphuretted hydrogen, and hy decomposingferrous sulphate with illuminating gas.In all three cases ironpyrites or troilite was formed.Hauerite and Manganese-Z,lende.-If hydrogen sidphide is allowed toact on various manganese compounds, manganese-blende, MnS, isformed. To obtain hauerite, the sulphur must conseq3ently be inexcess. The author mixed sulphur with the manganese compound,and warmed the mass in a stream of hydrogen sulphide. The resultswith braunite, manganese chloride, and potassium permanganate wereunsuccessful, manganese-blende being formed. With a mixture ofpj roluaite and sulphur, hauerite was ohtained.Galena.-The author's experiments show that galena can easily beformed in nature by the action of hydrogen sulphide on solutions oflead carbonate, or lead chloride.Galena was produced at the ordinarytemperature by exposing lead chloride to the action of hydrogensulphide and some sodium hydrogen carbonate for five months.Cinnabar.-The occurrence of mercury ores shows that they mustapparently, in many cases, have been formed by the action of hydrogensulphide a t a low temperature. This is confirmed by a simple experi-ment; mercury heated in a water-bath a t 70" to 90" for six days in atube filled with hydrogen sulphide, forms small, red crystals ofcinnabar.C'ovelline and Copper Glance.-Copper oxide treated with hydrogensulphide at, a temperature oE 200" gives a very characteristic crystallineaggregate of covelline.At a higher temperature (250 t o 400") copperg!ance is formed. Cuprous oxide treated with hydrogen sulphidegives copper glance. According to Durocher, this is also obtained ata red heat from copper chloride.Copper Pyrites.--The author obtained small crystals of copperpyrites by the action of hydrogen sulphide on a mixture of 2CuO +Fe,03, slightly heated in a glass tube. Copper pyrites is also formedby treating copper carbonate and ferric sulphate with sulphurettedhydrogen water in a closed tube for three days.Romite.-By the action of sulphuretted hydrogen on a mixture ofCu20, CuO, and FezOs, bornite is obtained at a low temperature,100" to 200". The compound CugFe4S1,,, which contains less copperand more iron than the normal bornite (CuS,Cu2S,FeS), was obtainedfrom a mixture of 2Fe203,3Cu20,3Cu0.I n other experiments, amixture rich in iron, Cu2S,2CuS,4FeS, and a mixture rich incopper, were obtained. The experiments seem to prove that bornitediffers from copper pyrites in requiring both CuS and Cu2S. Theratio of the two to FeS is not absolutely fixed; and CuS and Cu,Sneed not be present in equal quantities.Bournonite is obtained by the action of hydrogen sulphide on thecorresponding chlorine and oxygen compounds of lead, copper, aiidantimony, a t a, low heatMINERALOGICAL CHEMISTRY. 209J I i a r g y ~ i t ~ was obtained by heating a mixture of antimony andsilver chlorides, corresponding with the piaoportion Ag : Sb = 1 : 1,in a glass tube through which a strong stream of hydrogen sulphidepassed.Jamesnnite was obtained by the action of hydrogen snlphide on amixture of antimony or antimony oxide and lead chloride a t a tempe-rature of 200" to 400".B. H. B.Massive Safflorite. By L. W. MCCAT (Arner. J. Rci., 29, 369-374).-In a previous paper (Abstr., 1884, 1098) the author showedthat the rhom hic modification of speiskobalt, described by Sandbergeras spathiopyrite, is identical with the safflorite of Breithaupt. Sand-berger (Abstr., 1884, 40.5), admitting the existence of the crystallinesafflorite, objected to the use of the term to cover the massivevarieties, and doubted the accuracy of the statement that speiskobaltand safflorite appear together, the former above the latter.The authorhas thereEore examined some specimens of speiskobalt from theFreiberg collection, exhibiting the occurrence of smaltine and massivesafflorite together. An analysis of a specimen of the grey cobaltarsenir-le, called by the Schneeberg miners XchZackenkobdt, gave thefollowing results :-As. S. Co. Ni. Fe. Cu. Bi. Insoluble. Total.65.52 0.90 18.36 absent 9.40 0.62 trace 1.30 100.10This analysis agrees in a curious way with v. Kobell's analysis ofE;se?&dmZtkies (safflorite) from Schneeberg ; the quantity of cobaltshown in the author's analysis being identical with the quantity ofiron in v. Kobell's, and vice versci. The author is consequently inclinedto believe that v. Kobe11 made a mistake in writing down his figures.The specific gravity, 7.167, together with the results of the analysis,prove that the heavy grey Schlackenkobalt is massive safflorite, andthe accompanying tin-white smaltine demonstrates conclusively thatsafflorite and smaltine occur together.B. H. B.The Crystal Forms of the Andreasberg Calcite. By F.SANSONI (Zeit. K v y s t . Min., 10, 545--600).-This paper, the first partof a monograph on calcite, treats of the crystal forms of the Andrens-berg calcite. The nut,hor has examined 2b00 specimens in variouspublic and private collections, and has measured i22 crystals. Hefinds that the number of forms occurring on Sndreasberg calciteamounts to 131, a.nd that 359 combinations of these forms have, upto the present time, been met with. B.H. B.Determination of the Refractive Indices of Boracite. By. E.MALLARD (Zeit. K r y s t . Min., 10, 631-6:32) .--For the determinationof the refractive indices, t,he author employed the measurement of therelative retardation experienced by two principal vibrations runningperpendicularly to a crystal plate ; t,he measurements being made bymeans of a Babinet compensator. I n sections of boracite parallel tothe dodecahedron planes, the portions perpendicular to the negativ210 ABSTRACTS OF CHEMICAL PAPERS.bisectrix gave nb - n, = 0.00597. This observation combined withDes Cloizeaux's measurement of the axial angle V = 41" 47' givesnb - mu = 0.00477; from which is deduced n, - nu = 0.01074.Combining these data with the mean refractive index (nb = 1.66'7)determined by Des Cloizeaux, the t h e e principal indices are found tobe : n, = 1.6622 ; nb = 1.6670; n, = 1.6730.B. H. R.Formation of Beds of Sodium Nitrate. By A. M ~ T Z (Corn@rend., 101, 1265-1267) .-The author's previous observations andexperiments (Cornpt. rend., 85, 1020 ; 100, 1136 ; 101, 65, 248, and1136 ; see Abstr., 1884, et seg.), lead to the following conclusions.The nitric acid is derived from organic matter by oxidation under theinfluence of a nitrifying ferment ; sea-water, or the mother-liquor ofbrackish marshes, has come in contact with the organic matter duringnitrification ; the sodium nitrate has been produced by the action ofsodium chloride on the calcium nitrate originally formed ; the sodiumnitrate has not been formed ,in its present position, but has beenremoved from its place of origin, and afterwards concentrated in thebeds in which it is now found.C. H. B.Mimetesite, containing Lime, from Puy-de-Ddme. By A.DANOUR (Zeit. KrysC. Nin., 10, 627).-Smail botryo'idal masses of agreyish colour, from the Villevieille mine a t Pontgibaut, gave onan a1 y sis-As205. P20,. PbO. CaO. C1. Pb. Total. Sp. gr.19.65 3.44 63.25 3.46 2.57 7.49 99-86 6.65This corresponds with the formula (Pb,Ca),C1[(As,P)O4I3.B. H. B.Pectolite fro- Alaska. By H. FISCHER (Zeit. & y t . Nin., 10,614).-An analysis of pectolite from Port Barrow gave the followingresults :-Si02. CaO. MgO. Na,O. A1,0,. H2O. Total. Sp. gr.53.94 32-21 1.43 8.57 0.58 409 100.82 2.873Colour, pale apple-green ; compact ; easily fusible.B. H. B.New Locality for Nephrite in Asia. By A. B. MEYER (Zeit.Kr-yst. Min., 10, 612).-A dark green mineral brought from Yunanby Anderson, is, according to Arzruni, typical nephrite. Analysisgave-SiO,. A120,. FeO. CaO. MgO. H20. Total.36-58 0.92 4.12 12-92 21.65 3.25 99.44The author suggests that Yunan o r Barma is a hitherto unknownlocality for Chinese nephrite.Optical Properties of Albite. By A. DES CLOIZEAUX (Zeit.Tiryst. nlrin ., 10, 6 2 8 4 3 1 ) .-Although albite has, of all felspars, themost constant composition, its optical properties vary according l oB. H. BMINERALOGICAL CHEMISTRY. 211the homogeneity of the crystals, the number and disposition of thetwin lamelh and the manner of its occurrence. Regarding the pro-perties of the crystals from the crystalline schists and in dolomiticlimestones as normal, the following may be given :-The plane of theoptic axes is always perpendicular to a plane which bevels the acuteedge OP, mPm, and with OP forms hhe angle S = 78" to 79".Double refractive posit'ive. The first bisectrix is almost perpendiculart o the edge OP, mPm ; 2H, = 80" t o 85" red ; dispersion p less thanu ; BH, = 1 0 4 O to 106" ; plates perpendicular to the second bisectrixexhibit crossed dispersion with more or less distinct inclined dis-persion.Normal results of this kind were given by transparentcrystids from the Tyrol, Modane, Dauphin&, greyish-white crystalsfrom Arentlal, large white crystals from Karabinsk in the Ural,olatite from Snarum, small crystals from Calvados, red masses fromPiedmont, white masses from the Mer de Glace a t Chamauni, redmasses from Mineral Hill, Pennsylvania, peristerite from Perth inCanada, yellow aggregates from Morongoze, and small white massesfrom S.Marcel and Piedmont.Variations from the normal optical characters were shown hy thefollowing varieties of albite :-Moonstone from Mineral Hi1 1, greyish-green masses from Moriah, New York, peristerite from Bathurst audBurgess in Canada, partly kaolinised masses from St. Viacenz inStyria, white aggregates from Hammerfest, pericline from the Tyrol,reddish-grey masses from Arendal ; tscherrnakite from Bamle, Mid-dletown in Connecticut, Irigny, Eureka in Victoria.The position of the optic axes is uncertain in the varieties fromCrique Boulanger in French Guiana, and from Miask.B.H. B.Andesine from Arddche. By A. DAMOUR (&it. R~pt. 2cz;L'1~., 10,646 ) .--8 in all, trans par en t, colourless fragments, with dis tine t s tr I a tio n,from a volcanic tuff of the Coirons, near Rochesauve in the depart-ment of Ardbche, gave on analysis the following results :-Si02. AlZO:,. CaO. Na,O. K20. Total. Sp. gr.58.71 25.43 9.05 5.45 0.78 99.48 2.68I n the same tuff the following minerals mere also found : octahedraAnalysis of Labradorite from the Krakatoa Ashes. By A.of magnetite, yellow titanite, augite, and apatite.SAUER (Zeit. Kryst. Min., 11, 59).--The results were as follows :-B.H. B.SiO,. A.l,O,. CaO. NQO. K20. Total.51.03 28.37 10.74 8-74! 1-11 99-99B. H. B.Analysis of Enstatite and Labradorite from the Enstatite-Porphyrite of the Cheviot Hills. By J. PETERSEN (Zeit. K ~ y s t .&!it&., 11, 69--70).-The results of the analyses were as follows : -SiO,. Al,O,. PeO. MgO. CaO. H20. K20. Na,O. Total.I. 52.53 3-38 9.89 26 66 6.19 0.26 - - 98.9111. 56.04 29-48 - 0.05 l'J.09 - 0.57 6.41 102.6212 ABSTRACTS OF CHEMICAL PAPERS.I, enstatite, sp. gr. 3.331 ; 11, labradorite, sp. gr. 2.666.B. H. B.Analyses of Diallage, Labradorite, Aragonite, and Picrolite.By H. TRAUBE (Zeit. Kryst. Mirz., 11, 60-61).-Diallage (I), andlabradorite (11), from the gabbro of the Buchberg, Lower Silesia,gave on analysis the following results :-Si02.A1,03. FeO. FezO,. MnO. CaO. MgO.I. 51-23 1-21 11.57 - 1.26 17.07 16.1111. 52.08 27.56 - 1.65 - 12.23 0.60HZO. K,O. Na,O. Total. Sp. gr.I. 1.31 - - 99.76 3-1811. - 4-82 0.80 99-74 2.71Aragonite (111) from the magnesite of the Wachberg, near Baum-garten, Lower Silesia, and globular radiated aragonite (IV) withincluded magnesium carbonante, from the same locality, gave onanalysis- co,. CaO. MgO. Total. Sp. gr.IV. 45.73 44.87 9-36 99.96 2.94111. 44.14 55.33 0.44 99.91 2.91Picrolite from Endersdorf, Lower Silesia, gave-V. 43.46 2-25 1.26 40.98 trace 12.25 100.20 2.65B. H. B.SiOz. FeO. A1,03. MgO. CaO. H,O. Total. 8p. gr.corresponding with the formula H,Mg,Si,O, + H20.Hyalophane from Jakobsberg in Wermland, Sweden. By L.J.IGELSTROM (Zeit. Kryst. Min., 10, 632) .-The author has analjseda greenish-blue compact felspar, which occurs with hausmannite andmanganese-epidote in the limestone of the Jakobsberg mine. Theresults were as follows :-SiO,. &03. BaO. MgO. MnO. K,O + N%O. Total.53.53 23.33 7.30 3.23 t'race 11-71 99-10B. H. B.Analysis of Felspar, Augite, and Mica. By G. LINCK (Zeit.R~yst. Mi%., 11, 63-66) .-Analyses of minerals from the minette ofWeiier, near Weissenberg, gave the following results :-Si02. TiO,. Al,O,. Fe,O,. FeO. MgO. CaO. KZO.I. 57.13 - 17.29 2.39 - 1.96 1.59 7-83Ir. 48-23 - 5.28 4-83 3-01 15-84 19.85 0.52111. 36.61 3-16 15.26 5.11 8.32 16.81 2.71 7.00Na,O. P. H,O. Total.I. 2.57 - 1.00 101.7811. 0.67 - 0.45 100.68111. trace 0.20 4.9-5 100.13I, felspar (sp.gr. 2.633) ; 11, augite ; 111, mica. B. H. BMINERALOGICAL CHEMISTR P. 213Topaz from Stoneham, Maine. By F. W. CLARKE and J. S.DILLER (Amer. J. Xci., 29, 378-384).-C. M. Bradbury (Abstr.,1884, 67) published an analysis of the Stoneham topaz, showing it tobe unlike any topaz hitherto known. The peculiar interest attachingto his results made a new analysis desirable. Some apparently alteredtopaz has now been found, the crystals of which, having the un-changed mineral a t the centre, are transformed on the surface into adark-purple soft substance. Between the purple zone and the topazwas a greenish intermediate layer. Damourite was intimately associ-ated with the topaz in all the specimens examined.The results ofthe analyses may be tabulated as follows :-I, unaltered topaz (sp. gr. 3.51, H. 8) ; 11, greenish layer (sp. gr.3.42, H. 7) ; 111, purple zone (sp. gr. 2.82, H. 3) ; IT, massive damour-ite ; V, foliated damourite :-Si02 ...............F ..................K20 ...............Na,O ...............FeO ................MnO ...............CaO.. ..............MgO ...............Totals ......Deduct 0 .....8 1 2 0 3 . . ............H20.. ..............Totals ......I.--31 -9257-3816 -990 *200.151.33------107 -977 -16100.81---11.35 *1553 -1812 a30 '901 -521 -28 -1 *320 -17106 -4Q5 -42-i100 *98111.44 -5246 -190 -403 -742 -302 -820 -210 *300.14100 *620.16---100 46IV.45 *1933.324 -4811-061-574 -250 *58trace0 *36100 -81V.--45.3433 *964 -7810 -731.493.960.510.220 -101.01.09----The topaz is thus ovdinary topaz, with none of the anomalouscharacter indicated by Bradbury.The analyses point to a progressivechange from topaz to damourite, the fluorine and some alumina beinggradually eliminated. This change was probably brought ambout bythe kaolinisation of adjacent felspathic material.The results of a crystallographic and microscopic examination wereeven more conclusive than the analyses in showing that the alteredtopaz is essentially damourite.The fluorine washed out from the topaz in the form of alkalinefluorides, enters into new combinations, represeuted a t the locality hyfluorite, herderite, triplite, and apatite.Rubellan.By M. U. HOLLRCNG (Zeit. Kryst. Min., 11, 53).-Theauthor has investigated the occurrence of rubellan in the basalt tuffsof Schima and Kostenblatt, in the nepheline dolerite of the LobanMountain, and in the basalt lava of the Laacher See. He arrives atthe conclusion that rubellan is not homogeneous, but is an alteration-product. He also states that two different minerals go by the nameB. H. B2 14 ABSTRACTS OF CHENICAL PAPERS.of rubellan.omitted from the mica series.on analysis the following results :-He therefore proposes t'hat the name rubellan should beRubellan from three different specimens from the Laacher See gaveF. Si02. TiO,. Al,O,. Fe203 FeO. MgO.Ia. -- 36-25 0.88 14-88 28.04 3.24 11.18Ib. - 35.90 0.6.5 1Fi.34 27.69 3.24 11.31TIu. 1-32 36-99 0.61 18-17 22-19 1.81 11.75I I b . - 36.97 0.80 17.94 22-81 1.50 11.97IIIa. 1.19 36.63 1.08 17.11 25.85 1-19 11.781IIb. - 37.09 1.24 17.02 25.96 1.19 11.53K20. Na,O. HPO. Total.Ia. 1.87 1-25 3.29 100.88I b . 1.59 1.38 3-31 100.41IIa. 1.66 1.58 3.59 99.67I I b . 1.60 1-42 3.61 98.62Illa. 1.88 0.39 4-51 10 1 * 59IIIb. 2.01 0.38 4.66 101.08The sp. gr. cf I1 was 2.81 to 2.86, and of 111, 2.50. B. H. B.Blue Tourmaline from Chapey. By A. MICHEL-L~VY (Zeit.Kryst. Min., 10, 649).-In the pegmatite veins in the gneiss ofCliapey, near iliarmagne (Sadne-et-Loire), small strings of a bluesubstance occur, composed of minute fragments embedded in clay.This blue mineral is uniaxial, and gives a difference of the refractiveindices oc - "J = 0.0234, 5t difference which corresponds with tour-maline only. This view is supported by the pleochroysm and sp. gr.of the subsbance. B. H. B.Analyses of Plagioelase and Olivine from Chili. By H.Zr TGENSPECK (Zeit. Kyst. Min., 11, 69).-Plagioclase (I) and olivine(LI), from the basalt of the Volcano Yake, gave on analysis the fol-lowing results :-Si02. A1,0,. Fe2@,. FeO. CaO. MgO. K20. NaZO.I. 46.03 32.41 1.78 - 13.78 0.28 0.73 4.43- 24.83 - 37.62 - - 11. :38*47 -Ignition. Total. Sp. gr.I. 0.48 99-94 3.1411. - 100.98 3.48 B. E. B.Artificial Preparation of Rhodonite. By L. BOURGEOIS (Zeit.Kryst. &!in., 10, 626-627).-By fusing MnOz (1 mol.) and SiO,(1 mol.) for a short time, an aggregate of prisms of rhodonite is ob-tained. A mixture of MnO, (2 mols.) and SiO, (1 mol.) givesrhombic plates of tephroite, with small pyramids of hausmannitesurrounded by a crystalline aggregate of rhodonite. An intermediatemixture of MnO, and SiO, gives a perfectly crystalline mass consistinORGANIC CHEMISTRY. 215of large rhombic plates of tephroite, hausmannite, and rhodonitefilling the space between the crystals. By employing MnC12, haus-mannite and tephroite are obtained with very fine crystals of rhodonite0.5 mm. long. These crystals have exactly the composition repre-sented by the formula MnSiO,. The planes observed and the opticalproperties are exactly the same as those of the natural ciystnls.B. H. B.Deposit from the Spring at Chabetout. By F. THABUIS(Covipt. r e d . , 101, 1163--1164).--The spring at Chabetout, Puy- de-Dame, issues from a compact rock formed of mica schist and goeiss,impregnated with crystals of iron pyrites, and containing traces ofarsenical pyrites. The deposit from this water is ochreous andunctuous, and contains micsceous plates and golden-yellow plates.It has the following percentage composition after drying in theair :-CaO. MgO. Alkalis. matter. mica, &c. H20. c 0 2 .2234 0.276 0.406 9.400 2.087 22.900 1-820As205. P20,. SiO,. Fe20,. Mn,O,. A1,0,.0.230 0.145 11.137 49.410 0.305 0.900Organic Sand,The deposit, contairs lithium. The association of arsenic acid withphosphoric acid is unusual ; the former exists as basic ferric arsenate,the latter as calcium phosphate. C. H. B

ISSN:0368-1769    

DOI:10.1039/CA8865000206

出版商:RSC    

年代:1886

数据来源: RSC

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ORGANIC CHEMISTRY. 215 O r g a n i c C h e m i s t r y . Physical Properties of Paraffins from Pennsylvanian Petro- leum. By A. BARTOLI and E. STRACCIATI (Gazzetta 15 417-446.)- I n this paper a number of determinations are given of the coefficients of expansion capillarity and friction the specific volumes and specific heats indices of refraction and specific inductive powers of the paraffins from C,H to Cl6HS obtained from Pecnsylvanian petroleum. These physical constants with the exception of the specific volnmes increase regularly with increase of molecular weight ; the specific heat is practically constant for all the hydrocarhons and the specific inductive powers are in accordance with the laws of Maxwell. Normal and Primary Monochlorobutyl-derivatives. By L. HENRY (Conipt.Tend. 101 1158-1161).-The author has prepared a number of derivatives from chlorobromopropane CH,Cl.CH,.CH,Br by taking advantage of the different reaction aptitudes of the groups CHI,C1 and CH2Br. r-ChZoroButyrorlitrile CH,Cl.CH,.CH,.CN is a colourless mobile liquid with a faint disagreeable odour and a piquant taste. I t is insoluble in water but easily soluble in alcohol and i n ether; it boils without decomposition at 195-197" under ordinary pressure; sp. gr. at 10" compared with water at the same V. H. V.216 ABSTRACTS OF CHEMICAL PAPERS. temperature = 1 -1620. I t dissolves in concentrated hydrochloric acid with slight development of heat and if the solution is heated in saaled tubes the corresponding acid i q obtained. 7- Ch lorohutyric acid CH2C1*CH,*CHz*COOH is a thick viscous colourless liquid with a feeble butyric odour and a burning taste ; sp.gr. at 10" = 1.2498. It is feebly corrosive and is only slightly soluble in water but dis- solves easily in alcohol and ether. When cooled in a mixture of sodiutn sulphate and hydrochloric acid it crystallises in large thin perfectly transparent lamellae which melt arid resolidify at 1@-10*5". 7- Chlorobutyric acid does not distil without decomposition under ordinary pressure ; hydrochloric acid is given off abundantly at 180-185" and at 200" butyrolactone,< cH~2.coz>0 distils over. This is a verr convenient method of preparing butyrolactone ; the product boils a t 200-201" ; sp. gr. a t 10" = 1.1205. The methyl and ethyl salts of ychlorobutyric acid were prepared by dissolving the nitrile in the respective alcohols saturating the solution with hydrochloric acid and heating for some time.They are colourless liquids with an agreeable odour somewhat resembling that of menthol and a sharp piquant taste. They are insoluble in water and react very slowly with aqueous ammonia at the ordinary tempe- rature. Methyl y-chlorobutyrute boils at 173-174" under a pressure of 758 mm. ; sp. gr. a t 10" = 1.1894. Ethyl y-chlorobutyrate boils a t 183-184" under the same pressure ; sp. gr. a t 10" = 1.1221. Normal primary chlorobutyric chloride CH,Cl.CH,*CH,*COCl easily obtained by the action of phosphorus trichloride on the acid is a colourless liquid with a disagreeable suffocating odour ; sp. gr. at 10' = 1.2679. It boils a t 173-174" under a pressure of 750 mm.that is a t prac- tically the same temperature as methyl ychlorobutyrate and in this respect it follows the law which connects the boiling points of the methyl salts and of the acid chlorides in the biityric series. h/-Chloi-o- butgric chloride has the general properties of the acid chlorides. r- Chlorobutyramzde ~H~C1~CHz.C:H,~CONHz obtained by the action 01 animonia on the methyl salt or the acid chloride is a solid com- pound which melts a t 88-90" and cannot be distilled. It is only slightly soluble in water but dissolves easily in hot alcohol from which it crystallises in needles. By J. PONOMAREIFF (Ber. 18 3261-3275 ; compare Abstr. 1882 937).-A polymeride of cyanogen bromide C3N3Br3 is obtained by the action of dry hydrogen bromide on cyanogen bromide dissolved in absolute ether.It resembles solid cyanogen chloride in its properties. When heated a t 140-150" with acetic anhydride it decomposes into cyanuric acid and acetic bromide. Sodium ethoxide and methoxide act on it readily with formation of normal ethyl and methyl cyanurate respectively. Phosphorus pentachloride acts on ethyl cyanurate in the same way as on the methyl salt with formation of solid cyanogen chloride. Ammonia at 170-180" converts ethyl cyanurate into melamine and ammeline Diethylcyarturic acid C,N,(OEt),*OH isomeric with Limpricht and CH *CH C. H. B. Constitution of Cyanuric Acid.OROASIC CHEMISTRY. 21 7 Habich's diethylcyanuric acid is obtained by the action of baryta on normal ethyl cyanurate.It forms a crystalline powder sparingly soluble in alcohol and cold water. The barium saZt (with 3 mols. H,O) crystallises in plates ; it separates from a dilute aqueous solution in small needles with 12 mols H,O. The lead and sih-er saZts were pre- pared. Ethyl iodide acts on the lead salt with formation of normal ethyl cyanurate. When potassium ethyl sulphate is heated with sodium cyanurate a t 160" ethyl isocyanurate is formed (compare this vol. p. 42). Ethyl iodide acts on mono- and di-potassium cyanurate with formation of diethyl cyanurate melting a t 17:3" identical with Limpricht's com- pound (AnnuZen 109 112). By the action of methyl iodide on silver cyanurate a.t lOU" methyl isocpanurate and a small quantity of normal methyl cyanurate were obtained. In presence of an excess of the iodide the reaction takes place at the ordinary temperature ; the yield of normal cyanurate is then much larger.Acetic chloride acts on silver cynnurate with rise of temperature and formation of acetic anhydride and triacetyl cyanurate C3N303Ac3. This compound melts at 170" with partial decomposition ; i t is insolu- ble in ether sparingly soluble in chloroform. When warmed with water it decomposes into acetic and cyanuric acids. These results show that cyanuric acid belongs to the same series as the normal and alkyl salts of cyanuric acid ; that is to say it contains three hydroxyl-groups united with the group C3N3. N. H. M. Additive Products of Cyanogen Compounds Constitution of Dicyandiamide and Melamine. By B. RATHKE (Ber. 18 3102-3112).- Dicyandiamide reacts readily with thiocyanic acid with formation of thionmmeline. On the assumption that dicyan- diamine has the constitution NH,*CI(NH)*NH.CN (compare Bamberger Abstr. 1883 logo) the author ascribes to thioammeline the formula NH< c(NH).NH>CS. Melariurenic acid obtained by the action of carbonic anhydride on dicyandiamide would have an analogous con- stitution. This is contrary to the opinion expressed by Hofmann (this vol. p. 41). The author does not think however that it will be possible to find single formulae which will account for all reactions of these compounds and recommends the use of Hofmann's formule (Zoc. cit.) together with his own. C (NH) *NH N. H. M. Preparation of Alkyl Bisulphides. By E. COURANT and V v. RICHTER (Ber.18 3i7!3-3180).-It was thought probable that the action of sulphuryl chloride on mercaptnn might lead to the formation of ethyl dithiosulphate SO,(SEt) but' the reaction takes a different course and yields ethyl hisulphide. This gives a better method for the formation of the bisulphides than those previously employed. Ethereal Salts of Nitrous Acid. By G. BERTONI (Gazzettu 15 351-360 and 361-370).-Ethyiene Nitrite ON*O*CIH,*CH,OKO.- The co:npound of the empirical formula C2H4N204 first prepared by A. J. G.215 ABSTRACTS OLr CHEMICAL PAPERS. Serrienow (Zeit. Chern. 1864 lag) is regarded by some as nitro- ethylene by others as the ethylene salt of nitrous acid. The latter view is however incorrect as the true ethereal salt prepared by the general process previously described by the author differs from Semenom's compound. The process consists in distilling glyceryl trinitrite with ethylene glycol the compound passing over at 90-105" ; it is redistilled in a current of carbonic anhydride.It is a mobile yellow liquid boiling a t 96-98" sp. gr. a t 0" = 1.2156 insoluble in watm soluble in methyl and ethyl alcohols ether chloroform and glycerol. When inspired it produces vertigo and paralysis of the respiratory system. On exposure to air it is gradually converted into oxalic acid. It gives a violet coloration with con- centrated sulphuric acid and when distilled with methyl alcohol it is converted into ethylene glvcol and methyl nitrite. Tertiary bzLtyZ nitrite CaH9*0.N0 is prepared in a manner similar to the ethylene compound from tertiary butyl alcohol and glyceryl trinitrite.It is a yellow mobile liquid boiling at 63" sp. gr. a t 0" = 0.8914 sparingly soluble in water soluble in alcohol ether and chloroform. It is rapidly decomposed by acids with evolution of nitrous fumes. The tertiary butyl nitrite obtained with its isomeric nitro-com- pound described by Tschermak as boiling a t 67-68" was probably contaminated with its isorneride. Ally 1 Nitrite C,H,-O*NO.-Prepared as above from equimolecular proportions of glyceryl trinitrite and allyl alcohol the two liquids being mixed in a vessel kept cool ; the mixture is then quickly dis- tilled the portions passing over a t 50" being retained. This fraction is then dried over lime and distilled in a water-bath below lOO" inasmuch as a t this temperature it is completely decomposed with explosive violence. It is a mobile liquid boiling a t 44" ; sp.gr. a t 0" = 0.9546 insoluble in water soluble in methyl alcohol and decom- posing into methyl nitrite and allyl alcohol. It is rapidly decomposed by mineral acids and when heated it evolves nitrous fumes arid acraldehyde is formed. On prolonged contact with water i t is slowly destroyed forming a white crystalline mass which is rapidly resinified. 8-Hexyleneglycol and its Oxide. By A. Lim (Ber. 18 3275- 3286 ).-Ethylic bromo~ropylaaetoacetnte V. H. V. CH,Br*CH,.C H,* CHAc* C 0 OE t is prepared by adding a solution of 6 grams of sodium in 60 grams of absolute alcohol to 32 grams ethyl acetoacetate ; the product is then added to 80 grams trimethylene bromide.The alcohol is distilled off the residue treated with water and shaken with dilute potash (to dissolve out unchanged ethyl acetoacetate) and then dried. It is insoluble in water but soluble in alcohol. When boiled with 5 per cent. hydrochloric acid it decomposes into bromobutyl methyl ketone alcohol aud carbonic anhydride. Alcoholic ammonia converts it into ethylic trimethyieneacetoacetate (Ber. 16 208). Normal acetobutyl alcoholic COMe*CH,*CH,*CH2*CH2-OH is obtained by boiling 50 grams of ethyl bromopropylacetoacetate with 50 gramsORGASIC CHEXISTRT. 219 of water and 20 grams of hydrochloric acid (sp. gr. = 1.1) until the evolution of carbonic anhydride ceases. When cold the solution is separated from an oil (consisting of bromine compounds) partially distilled and then supersaturated with potassium carboilate.The acetobntyl alcohol separates as an oil and is dried with potassium carbonate and over sulphuric acid to remove ethyl alcohol. It is very readily soluble in water alcohol and ether ; it. boils a t 154-15.5" under 718 mm. pressure with slight decomposition ; sp. gr. = 1.0143 at 0". Sulphuric acid and potassium dichromate oxidise it to acetobutyric acid. Broinobutyl methyl ketone COMe*CH,.CH,*CH,-CH,Br is obtained by distilling acetobutyl alcohol with five times the amount of strong hydrobromic acid. It is a colourless oil of agreeable odour sparingly soluble in water readily in alcohol and ether. It boils a t 214-216" (under 718 mm. pressure). Alcoholic ammonia acts on it with formation of ammonium bromide and a base having the odour of piperidine.8-HexyZene gZycoZ OH.CHMe*CH,*CH,*CH,*CH20H is formed by the action of sodium amalgam on acetobutyl alcohol. It is a thick colour- less liquid readily soluble in alcohol less soluble in ether. It boils a t 234-235" under 710 mm. pressure sp. gr. a t 0" = 0.9809. When heated with fuming hydrochloric acid a t loo' it is converted into the corresponding monochlorhydrin. This is almost insoluble in water and has an agreeable odonr. 8-Hexylene ozide <UH,-CHMc CH,-CH,*CH >0 is prepared by heating 10 grams of 8-hexylene glycol with 20 grams of sulphuric acid and 10 grams of water for one hour at 100". The product is diluted with water and distilled ; the distillate is then dried by means of potassium carbonate and redistilled. It is a colourless liquid having a strong odonr resembling when dilute that of ethyl ether.It boils at 103-104" (under 720 mm. pressure). It is sparingly soluble in water readily in ether and alcohol. Water a t 225-230" and ammonia a t 200" have no action on it. Hydrochloric acid (sp. gr. 1.1) a t 100" converts it into the monoch Zorh y drin C HMe C1- C H,.C H,*CH,-C H,*OH mentioned above ; prolonged heating with fuming hydrochloric acid converts it into hexylene dichloride which can also be obtained from the glycol. The low boiling point of 8-besylene oxide and its behaviour towards dilute hydrochloric acid support the constitutional formula ascribed to it. The eliminat'ion of water from 8-hexylene glycol does not there- fore take place in the same way as in the case of the &-glycols which yield unsaturated alcohols.Cyanhydrin of Levulose. By H. KILIANI (Re)-. 18 3G66- 3072).-Levulose was prepared by boiling 50 grams of inulin with 150 grams of water and 10 C.C. of dilute sulphuric acid for eight hours. The acid was then precipitated by baryta the filtrate eva- porated and mixed with 5-6 vols. of alcohol. In 24 hours a volu- minous brown substance separated. The filtrate was evaporated to a syrup and then shaken up with strong hydrocynnic acid which con- verted the levulose into the cyanhydrin C7H,06N. This is readily It has an odour resembling that of camphor. N. H. M.220 ABSTRACTS OF CHEMICAL PAPERS. soluble in water insoluble in alcohol and ether. When heated it softens between l00-105" and becomes strongly coloured. Fuming hydrochloric acid converts it a t the ordinary temperatnre into an acid which could only be obtained as a syrup.This when boiled with concentrated hydriodic acid and amorphous phosphorus yields a hepto- Zactowe C7HI2O2 which boils a t 220" ; it does not solidify in a freezing mixture. When the lactone is heated with hydriodic acid and amor- phous phosphorus a t 180" it yields an acid boiling a t 209.6" which could not be got to solidify and therefore is not normal heptylic acid. The culcizcrn salt (with 5-6 mols. H,O) crystallises in long needles. The results do not agree with the description of calcium methybutyl- acetate given by Hecht and the acid is probably ethylpropylacetic acid. The formation of this acid would point t o the constitution OH*C€I,~CH(OH)*CH(OH)~CO~CH(OH)-CH2~OH for levulose.The Succession of the Rate of Retrogressive Birotation of some Saccharoses and Glucoses with regard to their Con stitu- tional Formulz and the Extent of Affinity. By F. URECH (Rer. 18 3047-3060).-Milk-sugar is not changed by oxalic acid. When 9.34 grams of milk-sugar are dissolved in 11.83 grams hydrochloric acid and kept for 28 day3 a t lo" the milk-sugar was recovered un- changed. Saccharose under the same conditions is completely inverted in nine hours. When three times the quantity of hydro- chloric acid is used the milk-sugar is slowly inverted. According to Meissl maltose occupies a position between that of milk-sugar and saccbarose with regard to its invertibility. Solutions of alkalis act more quickly on maltose than on milk-sugar and more quickly cn milk-sugar than on yaccharose.This indifferent behaviour of sacclia- rose may be accounted for by assuming that the relations of the glu- cose radicles to one another are different in sacchnrose ; for instance that the glucoses are joined by an oxygen-atom to form an ether. Alkali Eolutions act on lactose more slowly than on dextrose and on dextrose more slowly than on levuiose ; a table with the results of experiments is given (compare Abstr. 1884 1112). The author has already (ioc. cit.) shown that dextrose reduces alka- line copper solution more slowly than levulose ; further experiments show that the action of lactose is still slower. Fehling's solution decomposes maltose more quickly than milk-sugar ; saccharose is decomposed slowly a t a higher temperature.The results of comparative experiments made with lactose and dextrose show taliat the retrogressive birotation of the latter takes pkce rather more quickly than in the case of lactose. Composition and Properties of Raffinose. By H. PELLET and L. BIARD (Chem. Centr. 1885 47 878-87Y).-The authors confirm Loiseau's investigations. A crystalline raffinose containing 15.1 per cent. of water was obtained. The rotatory power of inverted raffinose was found to be +66.7 (sugar = 100). Scheibler gives it as +67*1. It remains to be decided whether raffinose exists ready-formed in beetroot or is formed during the treatrnent of the sap. From the action of acetic acid on raffinose and from other considerations the N.H. M. N. H. M.ORGANIC CHEMISTRT. 221 authors conclude it to be a compound of crystallisable sugar with dextrin or some similar substance and a certain amount of water. H. P. W. Source of Raffinose (Melitose) in the Products of the Manu- facture of Sugar. By E. 0. v. LTPPRZANN (Ber. 18,3087-3090).- Ra,6nose was obtained directly from beetroot sap bg the method employed by Scheibler for the separation of railinose frorri molasses (Abstr. 1885 962). The presence of raffinose partly accounts for the high polarisation of beetroot sap. The author does not hold Degener’s view that the formation of dextrorotatory sugar in beetroot beginning to decompose is due to tlie action of maltose-especially as it has not been shown t h a t the latter exists in the sap of beetroot.N. H. M. Researches on Rice-starch. By 2. SOSTEGNI (Gazzetta 15 376-384) .-On account of the discordant observations as to the amount of dextrose obtained from starch by the action of acids on it tliis point is examined in the case of pure specimens of rice-starch. The ratio between the quantities of starch and dextrose was found to be 93.2 100 a result in accordance with the recent researches of Salomon ( J . pr. Chem. 25,348 and 26,342). I n order to trace out the cause of the discrepancies the author has examined the insoluble i.esidue obtained in the course of the degradation of the starch molecule by unorpaniscd ferments or by 1 per cent. h=j-drochloric wid. Ether extracted from tlie product a mixture of fatty acids containing a pro- portion of carbon less than that required for palmitic or oleic acid.‘l’he ratio between the amido-cellulose thus purified and the dextrose obtained was found to be as 98.7 100 a result which is still low owing t o the formation of other products of decomposition by the action of the acid used. V. H. V. Maltodextrin. By A. HERZFELD (Ber. 18 3469-3470) .-This paper contains a short explanation of a few points of difference between the observations of Brown and Morris on maltodextrin (Trans. 1885 560) and those of the author (Abstr. 1880 866). The former state that this compound does not undergo fermentation by Ntrcclmrornyces cerevisice of the high fermentat’ion type until it is forther hydrated whereas the author found that it is readily and completely fermented by pressed yeast.This discrepancy arises from the difference. of species of yeast used. Indeed Brown a i d Morris themselves show that nialtodextrin is fermented by the slow action of certain forms of saccharomyces such as 8. ellipticus and 8. pastorianus of the bottom fermentation type (comp. supra 570). The author also ~ l l o w s that his former specimens of maltodextrin were not altogether fyee from maltose and on a recent repetition of his work he is able to confirm Brown and Morris’ data as to the composition and specific rotatory power of their rnaltodextrin. v. H. V. Action of Chlorine on Anhydrous Chloral. By H. GAUTIER (Compf. rend. 101 1161-1162).-Sixty grams O E chloral was placed i n a flask of 10 litzes capacity which was then filled with chlorine VOL.L. 9222 ADSTkACTS OF CHE3lICAL PAPERP. gas. No change takes place in the dark even after 15 da,ys but in diffused light a reaction proceede slowly and in direct sunlight the colour of the chlorine completely disappears in two or three hours. The products are hydrogen chloride carbonic chloride and carbon tetrachloride ; the reaction being represented by the equation (cornp. Beilstein Hnndbuch p. 760). Preparation of Trichloracetic Acid. By A. CLERMONT (Ann. Chim. Phys. [6] 6 135-139) .-One equivalent of chloral hydrate is melted at 50-55" one equivalent of fuming nitric acid added and the source of heat then removed; in a few minutes nitrous vnpours are given off; the action ceases almost entirely in an hour's time. The liquid is then heated in a tubulated retort at 123" to 195" whereby the whole of the nitric acid is removed ; above 195" trichlor- acetic acid distils as a colourless liquid which solidifies on cooling.Trichloracetic acid exists in a state of superfusion at 52*2' its normal point of solidification being 55.0". Acetic acid ntny be readily repro- duced from trichloracetic acid by heating equal volumes of saturated aqueous solutions of trichloracetic and fuming hy driodic acids in a sealed tube a t 100" for 12 hours the resulting liquid is exactly iieutralised with potash evaporated to dryness and the solid mass heated sufficiently to decompose any trichloracetic acid present ; the potassium acetate may then be extracted with absolute alcohol. Action of Nitrous Acid on Sulphonediacetic Acid. By J.31. LOVI~N (Bey. 18 3241-3242) .-When 1 mol. sulphonedincetic acid (hbst,r. 1885 241) is gradually added to a well-cooled mode- rately concentrated solution of 2 mols. sodium nitrite gas consisting mainly of carbonic anhydride is evolved and the solution is found to contain sulphuric acid and a considerable amount of hydrocyanic acid. This reaction may be explained on the assumption that pri- mary diisonitrososulphonediacetic acid is first formed and that this simultaneously decomposes into carbonic anhydride sulphuric and lr ydrocyanic acids. Higher homologues of sulphonediacetic acid would yield nitriles or products of their decomposition in addition to carbonic anhydride and sulphuric acid. Action of Acid Chlorides on Inorganic Compounds. By B. LACHOWICZ (Be?-.18 2950-2996 ; comp. Abstr. 1884 990).-Pro- pionic and euccinic chlorides act on dry lead nitrate with slight rise of temperature and formation of propionic and succinic anhydrides respectively nitrogen peroxide and oxygen being evolved. Analogous reactions take place between the Chlorides of organic acids and all normal anhydrous nitrates of Iiea\?y metals. All metallic carbon- ates appear to react with the acid chlorides with evolution of carbonic anhjdride and formation of a salt of the organic acid ; a trace of the anhydride i s also formed. With the oxides of heavy metals t8he reaction is much more vigorous ; tlie chief' product is the salt of the organic acid (comp. Abstr. 1878 108). C. H. B. A. P. N. H. M. N. H. M.ORGANIC CHEMISTRY. 223 Fat of the Fruit of Vateria Indica.By F. P. HORNEL and J. F. WOLFBAUER (Chenz. Certtr. 1885 762)-There have lately been brought into commerce under the name of butter beans some peculiar fatty seeds which are now identified as those of Vateria i n d i c a a tree from which considerable quantities of vegetable tallow (Piney tallow Malabar tallow) is derived. The air-dried seeds contain 49.2 per cent. of a greenish-yellow solid fat which bleaches rapidly on exposure to light and has a peculiar agreeable balsamic odour. The fat is readily saponified and yields a mixture of fatty acids melting at -56.6" and resolidifying a t ,54*8". This mixture consists of oleic acid with solid fatty acids which melt at 63.8" and constitute about 60 per cent. of the vegetable tallow. A. J.G. Synthesis of Ethyl Acetoacetate and Phloroglucinol. By A. BAEYER (Bey. 18 3454-3460).-As a preliminary point the author reopens the discussion between Frankland Duppa and Wislicenus on the one hand and Geuther on the other regarding the constitution of ethylic sodacet oacetate namely whether the sodium is combined directly with the carbon or indirectly by means of the oxygen. Against the latter view is the ready replacement of the metal by other groupings which are then undoubtedly directly associated with the carbon. Xecondly there arises the difficulty of representing the con- stitution of ethylic sodomalonate whereby it would be necessai-y to assume that the stable COOEt grouping undergoes an extraordinary transformation leading to the production of a cqmpound of formula COOEt-CH C(ONa).OEt.ThirdZy the analogy drawn by Geuther as to the formation of ethylic sodacetoacetate with that of pinacone from acetone by the action of sodium through the inter- vention of a compound ONa*CMe,*CMe,*ONa fails inasmuch a s i t has been observed that whereas sodium has no action on ethyl succinate yet sodium ethylate free from alcohol converts it readily into ethyl succinosnccinate. Further the observations of Purdie on the action of sodium ethoxide on ethyl fumarate are rationally explained by the intermediate formation of ekhylic sodethoxpsncci- nate and its subsequent decomposition in the presence of alcohoi with re-formation of sodium ethoxide and production of ethyl ethoxys uc- cinate (Trans. 1881 3 4 ; 1885 855) ; such an explanation is in complete accordance with the commonly received view of the con- stitution of ethylic sodacetoacetate.On applying these facts to the initial action of sodium on ethyl acetate it follows that the original hypothesis of Frankland and Duppa regarding the inter- mediate formation of a compound ethylic sodacetate CH,Na*COOEt is possibly correct. By the action of 1 atom of sodium on 2 mols. of ethyl malonate a t a temperature of 110" a substance of the composi- tion C,H,O is obtained crystallising in needles which melt a t 104". It is insoluble in water sparingly soluble in alcohol readily soluble in ether and chloroform with pale-green fluorescence. It is analogous in its reactions to ethyl succinosnccinnte yet is much more stable ; its constitution is thus probably similar and it is doubtless derived from 3 mols.of ethjl mnlonate the carbon-atoms being associated i n a ring formula. It may thus be regarded as methyl phloroglucinoliri- q 2224 ABSTRACTS OF CHEMICAL PAPERS. carboxylate C6(OH)J( COOEt) and this hypothesis is supported by the formation of phloroglucinol from it by fusion with potash. Incidentally this synthesis of phloroglucinol rizises the question whether its composition is correctly represented by its generally CH2.CO received formula and not by the formula CO< CH,.CO>CH2; in support of the latter it is mentioned that hydroxylamine reacts with phloroglucinol to form a crystalline compound melting a t 128". It is proposed to make this point a subject of further investigabion. V. H.V. Ethenylglycollic Acid. By C. A. LOBRY DE BRUYN (Rec. Tmv. Cl~irn. 4 221-235) .-Amaldehyde combines directly with hydro- cyanio acid to form the nitrile of ethenylglycollic acid which distils a t 110" under a pressure of 85 mm. ; sp. gr. a t 15" = 1.05; it is soluble i n alcohol and ether but its preparation in a state of purity presents considerable difficulty. On saponification with hydrochloric acid the nitrile is converted into ethenrylglycollic acid CH CH*CH(OH)*COOH which may be purified by means of its zinc salt. The acid is a syrupy liquid solidifiying in a vacuum after some time forming a crystalline mass of the consistency of camphor. 1t.s zinc salt crystallises with 3H20 its potassium salt is a gummy hygroscopic mass and the copper salt a greenish-blue indistinctly crystalline powder very soluble in water sparingly soluble in alcohol. The acid as also its salts readily take up bromine a molecule of the acid combining with a molecule of bromine ; but the acid so far as it was examined was probably not a dibromerytliic acid.V. H. V. Ry HANRIOT (Compt. rend. 101 1156-1158).-The acids were distilled in contact with a large excess of quicklime. Pyrogenic Decomposition of Organic Acids. Succinic acid yields ethane C,H604 = 2C0 + C&. A d l p i c acid yields butane C6H,0a = 2C02 + CpH:,. Glycollic acid under these conditions decomposes onlyaf a red heat and yields methane (2 1-01s.) and hydrogen (1 vol.) and small quan- tities of liquid products which are free from methyl alcohol. The decomposition seems to be very complicated. This reaction renders it possible to pass from glucose to alcohol without the inter- vention of an alcoholic ferment.Pyruvic acid yields only a very small quantity of aldehyde the remainder being in all probability decomposed in contact with the lime. C . H. B. Lactic acid yields alcohol CsH60d = C02 + C2H60. Vinaconic Acid. By R. FITTIG and R. MARBURG (Bw. 18 2413-3414).-1n this notice it is stated that Perkin's observa- tion that vinaconic acid (t rimethg-lenedicarboxylic acid) does not combine with bromine is incorrect' inasmuch as in chlorofurm solu- tion in diffused daylight it yields a dibromo-additive product,ORGANIC CHEllJISTRY. 225 C,H,Br2( COOH)2 in well-defined crystals which melt a t 100-11~1" with incipient decomposition. Pentamethylenedicarboxylic Acid (1,2).By W. H. PERKIN Jun. (Ber. 18 3246-3252).-E5?2yl pentanetetracayboxylate V. H. V. CH( COOE t)2* CH,*CH,* CH,*CH ( CO OE t) 2 is prepared by gradually adding a mixture of 150 grams of eth31 malonate and 76 grams of trimethylene bromide to a cooled solution of 22 grams of sodium in 250 grams of absolute alcohol. I n about an hour water is added and the whole extracted with ether. On distilling off the ether an oil is obtained which is distilled with steam and frac- tioned under diminished pressure. The pure ether forms a very thick colourless oil boiling a t 259-262" (under 100 mm. pressure). When saponified i t yields a brown oily acid (probably pentanetetra- CarboxyZic acid) ; this when heated gives off carbonic anhydride and yields a-pimelic acid.By treating an ethereal solution of pentnnetetracarboxylic acicl (1 mol.) with sodium ethoxide (2 mols.) a sodium compound C1,H,O,Na is formed; and this when treated with bromine and subsequently saponified with alcoholic potash yields pen,tarmethyZ- euetetrtrcarboxylic acid. When this is heated a t 200-220° i t decomposes into carbonic anhydride and p e n t a m e t h y lenedic,m-bozylic acid. This acid CH,' 1 crystallises in nodular masses which melt a t 159-160" ; it is readily soluble in hot water alcohol and ethyl acetate sparingly in ether benzene chloroform and light petroleum. The siZver salt forms a sparingly soluble white precipitate. When the acid is heated for a long time a t 300" it gives off water C H2.CH.C 0 OH 'CH,*CH*C 0 0 H ,CH2*CH*CO and yields the anhydride CH2/ ' 0 .The latter compound \ CH2* AH-C 0' melts at 64-67" is readily soluble in ether benzene chloroform and alcohol more sparingly in light petzoleum and is almost insoluble in carbon bisulphide ; if it is warmed with resorcinol and sulphurjc acid and ammonia is subsequently added it gives the fluoresce'in reaction very splendidly. N. H. M. Constitution of Carbopyrotritartaric Acid. Ey R. F r T ' r t G (Ber. 18 3410-3413).-1n a former paper the author has shown that ethyl acetoacetate reacts with succinie acid to form an acid isomeric with carbopyrotritartaric acid (this vol. p. 47) ; it is pro- posed to name it methroiric acid. n'hen heated a t 200-240° it is decomposed into carbonic anhydride and pyrotritartaric acid. Re- garding t.he constitution of carbopyl.otritartaric acid the author regards its formation from diacetosuccinic acid as analogous t o that of mesitj-l oxide from acetone thus giving the formula- Co<-CH ChIe- >CH*COOH.CH(CO0H)226 ABSTRACTS OF CHEMICAL PAPERS. On comparison with the formula of methronic acid C(CO0H) CMe c o < ~ ~ ~ ~ ~ ( ~ ~ ~ ~ ) > it is seen that both are a-p-dicarboxylic acids in which the carboxylic groupings are in relatively different positions but both acids would yield carbopyrotritartaric acid. V. H. V. Action of Phosphoric Chloride on Alloxan. By G. CIAMICIAN and P. MAGKAGHI (Rer. 18 344$-3446).-Aa a continiiation of ob- servations on the action of phosphorus pentachloride on dichloro- rnalejimide (Abstr. 1884 Ills) the authors have examined the action of the same reagent on alloxan.On heating together alloxan phos- phoric chloride (24 parts) and phosphorus oxychloride (24 parts) at 126-136" tetruchZocrop~?.iniidine C4NzC14 is formed. This sub- stance crystallises in micaceous leaflets melting at 67-68" a n d possessing a penetrating d o u r resembling that of camphor. V. H. V. Thiohydantoin and its Derivatives. By R. ANDREASCH (Monatsh. Chem. 6 821-843). - By digesting the nitrosothiohy- danto'in obtained by Maly (Abstr. 1879 712) with dilute hydrochloric acid in a sealed tube a t 115-120" it is completely decomposed hy- droxylarnine occurring amongst the products of the reaction. It is probable therefore that this compound as also the nitrosothioglycollic acid derived from it are true isonitroso-compounds a view which is supported by the fact that neither subst,ance yields Lieberman's reaction with phenol and sulphuric acid.By the reduction of iso- nitrosothiohydantoh with tin and hydrochloric acid or with hy- driodic acid thiocarbamide and glycocine are formed together with a small quantity of a substance which is separated by means of ether ; this forms a red powder is soluble in water o r alcohol with a brilliant yellow coloration and has an acid reaction ; on the addition of alkalis it acquires a purple-red colour which on acidifying again changes to yellow. Isonitrosot hioglycollic acid when reduced by hydriodic acid yields glycocirie alone sulphur being precipitated. Imidocul.baonine-P-tkiolactic m i d E .€Iz.C ( NH).S*CH2*C Hz*C 0 OH is formed by the action of carbamide on a concentrated aqueous solution of p-iodopropionic acid and not as was expected the corresponding thiohydantoin.This acid crystallises in needles and melts a t 175-1 76" with decomposition ; when digested with aqueous baryta dithiolactic acid and 6-thiolactic acid are formed. When a solution of the latter is mixed with dilute ferric chloride and an alkali is added a brownish- red coloration is produced which becomes more intense on shaking with air but disappears on standing. By oxidising imidocarbamine-6-thio- lactic acid dissolved in strong hydrochloric acid with potassium chlorate at 50-60° carbamide and P-sulphopropionic acid are obtained. The latter forms a strongly acid colonrless syrup. The silver salt forms small scales and is anhydrous ; the barium salt HSOS*CH2*CHz*COOH,ORGANIC CHEMISTRY.227 C3H4BaSO5 + 5H20 is soluble in water and has a neutral reaction. This acid is also formed when broniiiie is added to an aqueous solution of imidocarbamine-B-thiolactic acid. Methylllziohydaiatoi'~k CO<g%:>C NH may be prepared by heating methyl thiocarbamide with chloracetic acid a t 100" ; it forms almost colourless crystals identical in appearance with thiohydantoln but differs from t h i s compound in being soluble in ether and alcohol. By the action of nitrous acid it is converted into isoizitrosomethyZthio- hycladoztz C4H5N,S02 ; this forms a reddish powder which is insoluble in ether but dissolves in alcohol and hot water ; it dissolves readily in aqueous alkalis and on heating with aqueous baryta is converted into the barium salt of isoiiitrosomet h~lthioglycollic acid.A. P. Constitutional Formula of Thiophen. By L. GATTERMANN. A . KAISER and V. MEPEE (Her. 18 3005-3012).-The results of expe- riments made by the authors show-I. That a-thiotolen from coal-tar is a mixture of /3- and y-thiotolen. 31. That there are only two thio- tolenic acids which are chemically different from one another the /Aacid melting a t 126*5" and the yacid which melts at 136". The a-acid melting a t 118" is chemically identical with the &acid; it yields the same bromo-derivative (Abstr. 1885 L206) and the cal- cium salts of both acids yield when distilled the same ketone (coin- pare p. 229). 111. That a-tribromothiotolen melting at 74" is formed by the joint crystallisation of the /3- and V-coinpounds ; when once formed it cannot be resolved into its constituents.These reaults remove the objections to V. Meyer's formula for thiophen (which admits of only two series of mono-derivatives) caused by the apparent existence of three series of derivatives. N. H. M. Monobromothiophen and Ethylthiophen. By E. SCHLEICHER (Ber. 18 3015-3023).-When monobromothiophen (Abstr. 1883 1091) is treated with ethyl bromide and sodium it yields /%ethyl- thiophen. Ethylthiophenic acid C4SH,Et*COOH is prepared by the action of iodine and mercuric oxide on ethylthiophen and subsequent treat- ment of the iodo-ethylthiophen thus formed with ethyl chlorocar- honake and sodium amalgam. It forms colourless lustrous cryst& readily soluble in alcohol and ether and melts at 71".The calciurn salt (with 2+ mols. H,O) forms colourless needles with a silky lustre. 'l'he silver salt fornis a white curdy precipitate. When ethylthiophenic acid is oxidised by potassium permanganate a thiophendiuarboxylic acid (Abstr. 1885 767) is obtained. AcetoethllZthieno?ze C4SH,EtAc is obtained by treating a mixture of 33 grams of ethylthiophen 20 grams of acetic chloride in 160 gramg light petroleum with about 30 grams of aluminium chloride ; it forms an almost colourless liquid having an agreeable odour ; the h y d r o q l - arniae-dtrivative melts a t 110". Nitracetoethylthienone NO,-CISHEtAc forms white lustrous needles melting at 71" readily soluble in boiling water alcohol and ether. When an alcoholic solution is228 ABSTRACTS OF CHENICXL PAPERS.treated with a trace of soda it acquires a splendid purple colour. Acetoethylthiihone when oxidised yields a dicarboxylic acid identical with that obtained from ethylthiophenic acid. Derivatives of Brominated Thiophens. By J. ROSENRERG (Bey. 18 3027-3031 ; compare Abstr. 1885 1051). - Tribromo- thiophen sdphocldoride C4SBr3*S02C1 is prepared by boiling a weighed quantity of the sulphonic anhydride and the necessary amount of phosphoric chloride with phosphorus oxychloride. It crystallises in yellowish-white hard needles melting a t 126". Tribromothiophen- sulphonamide C4SBr3.S02NH2 is obtained from the above compound by the acttion of ammonium carbonate. Tribromoiiitrothiophen C&3Br3*N02 is obtained by the action of fuming nitric acid on tribromothiophen suspended in sulphuric acid.Itt crystallises in matted reddish-yellow needles which melt a t 10V and are readily soluble in ether sparingly in alcohol. When fused tribromothiophen suspended in sulphuric acid is treated with fuming nitric acid dinitrodibromothiophen is formed identical with that already obtained from dibromothiophen The author endeavoured to obtain an isomeric thiophendicarboxylic acid by distilling with potassium cyanide the thiophendisulphonic acid obtained by the sulphonation of dibromothiophen and sub sequent removal of the bromine from the dibromo-disulphonic acid so obtained (this acid being isomeric with that obtained by the direct sulphonation of thiophen) but mere traces of a nitrile were formed.Several substances described by Langer (Ber. 17 1566) were obtained in a state of purity and the following corrections are made :-Dibro- mothiophen sulphochloride C4SHBr2*SO2C1 is a crystalline solid and melts a t 32-33' ; dibromothiophen disulphochloride C4SBr2( SO,Cl) melts a t 219-220'. N. H. 31. It forms white needles. N. H. M. Methylacetathienone. By R. DEMUTH (Ber. 18 302443026). -MethyZucetothie)zone C4SH2Me*COMe is prepared by the action of aluminium chloride on P-thiotolen and acetic chloride dissolved in light petroleum. It forms a pale red oil boiling a t 224" (corr). The hydrox?y Zamine-derivative crystal 1 i ses in small colourless needles melting.Rt 119". Phenylhydrazine and sodium acetate act on methyl- acetothienone with formation of a compound melting at 131".When methylacetothiihone is treated with well-cooled fuming nitric acid a nifro-compound N0,-C4SHMe*COMe melting at 125" i s obtained. When methyliicetothiihone is oxidised i t yields thiophendicarboxylic acid. 7-Methylthiophen behaves like the p-compound when acetylated and yields a ketone boiling a t 216" (cow.). a- and p-Thienone. By L. GATTERMANN (Rer. 18 3012-3015). +-Thienone CO(C&3H3) is prepared by the action of carbonyl chloride on thiophen ; the product is diluted with an equal volume of light petroleum cooled and treated with aluminium chloride. It is readily soluble in warm alcohol crystallises in colourless needles melts at 87-88" and boils a t 326" (iincorr.). The hydrazide crystallisrs in nodules and melts a t 137".@-ThiGnone was also prepared by N. H. M.0 RQANIC CHEMISTRY. 289 distilling calcium P-thiophenate. The same ketone is obtained by the distillation of calcium a-thiophenate. By F. MUHLERT (Ber. 18 3003-3005).- This acid was obtained by oxidising thiotolen (Abstr. 1885 1051). It crystallises from water in colourless needles melting a t 136". The calcium salt (with 9 mol. .H20) forms colourless needles ; the s i h e r salt crystallises in iustrous needles sparingly soluble in water. Concentrated nitric acid acts on ytribromothiotolen with fcrmation of a compound C4SBrll;Ie(N02)2 melting a t 125" ; it crystallises in short yellow prisms. N. H. M. v-Thiophenic Acid. N. H. M. Chlorobenzenes. By ISTRATI (Ann. Chim. Phys. [6] 6 367- 395).-Chlorine acts on benzene in the presence of sunlight form- ing only additive compounds in the first place.When the benzene is saturated in this manner substitution-componnds are formed and possibly all the hydrogen may be thus replaced and hexachloro- benzene hexachloride obtained. By acting on benzene with excess of chlorine in this manner and boiling the products obtained with alcoholic potash in addition to 1 2 4 trichlorobenzene and penta- and hexa-chlorobenzenes the author has obtained 1 3 4 5 tetrachloro- benzene in the pure state in considerable quantity (about 14 per cent. of the crude chlorobenzenes treated). It melts between 28" and 30" remains in a state of superfusion to a little below 20" and boils a t 242-243". A. P. Separation of Mixtures of Hydrocarbons of the Benzene Series.By C. FRIEDEL and J. M. CRAFTS (Compt. rend. 101 1218- 122:3).-The method described in this paper was devised f o r the pur- pose of separating ethylbenzene and the t.hree xylenes which are formed together with other products by the action of aluminium chloride on toluene. It is based upon the fact that dry bromine con- taining I per cent. of iodine converts all the xylenes completely into tetrabromo-derivatives and ethylbenzene into a dibromo-derivative the latter being subsequently converted into pentabromethylbenzent by the action of bromine in presence of aluminium chloride or bromide. Pentabromethylhenzene was obtained by Gustavson but was not described. It crystallises in monoclinic prisms which melt a t 141.5" and can be distilled with considerable decomposition undei- ordinary pressure.Under a pressure of 160 mm. it distils unchanged. Pentnbromethylbenzene is soluble in 11 parts of light petroleum (13. p. 80-90") a t 20" and the dibromo-derivative is miscible with light petroleum in almost all proportions. The tetrabromo-xylenes require about 200 parts of light petroleum for solution ; hence this liquid can be employed to separate the various products. The mixture of hydrocarbons is mixed with about 10 times its weight of bromine containing 1 per cent. of iodine and allowed to remain for 10 hours at the ordinary temperature. The excess of bromine is removed by means of potash aud the dried product ex- hausted with successive portions of light petroleum until the dis- solved matter melts at a higher tempcrature than 240".The petro-230 ABSTRACTS OF CHEJflCAL PAPERS. leuni is concentrated repeatedly until the tetrabromo-xylenes have almost completely crystallised and the quantity remaining in soln- t8ion is calculated from the known solubility of these compounds. The petroleum is expelled from the mother-liquor by evaporation the residue is mixed with four or five times its weight of bromine and aluminium chloride or bromide is added. After some hours the pro- duct is washed with potash crystallised from benzene and weighed a correction being made for the small quantity of admixed tetra- bro mo-x ylenes. About 10 per cent. of ethylbenzene was isolated by this method from the product boiling a t 137" obtained byheating toluene ak 110" for two days with 20 per cent.of aluminium chloride. The analysis can be made with 5 grams of matter or even less. Ethylene and its homologues are formed by the condensation of the methjlene which is liberated in the reaction thus 2C6H5.CH = 2CsH6 + C2H4 and the ethylbeneene is produced by the reaction CsHa + In order to separate the xylenes about 2 grams of the tetrabromo- derivatives are heated in sealed tubes a t 160-1'70" (in the vapour of pseudocumene) with 20 grams of bromine and 20 grams of water. The tetrabromp-derivatives are converted into the theoretical quanti- ties of tlie corresponding tetrabromophthalic acids C6Br4( C.H3) + 6Br2 + 4H20 = C6Br4(COOH)2 + 12HBr. Any destruction of the phthalic acids by further oxidation is indicated by the presence of carbonic anhydride in the tubes.The tetrabromophthalic acids are obtained in exactly the same proportions as the isomeric hydrocarbons i n the mixture taken for analysis and they can be separated by methods which will be described in a subsequent paper. The ortho- acid crystallises in small plates requires 400 parts of water at 15" for complete solution and is easily converted into the anhydride or the imide. The para-derivative crptallises in needles and gives a pre- cipitate with silver solution. The meta-derivative gives no precipitate with silver and is much more soluble than the other two. Chlorinated Ethylbenzenes. By ISTRATI (Ann. Chim. Phys. [6] 6 395-432) .-The higher members of the series of monochlor- ethylbenzenes may be prepared by passing a further amount of ethylene into the mixture of phenyl and aluminium chlorides (Abstr.1885 251). They are all liquids which do not crystallise a t 7" and are soluble in the usual solvents. Parachlorethylbenxeiae boils a t 181-182" and has a sp. gr. of 1.068. By boiling the mixed monochlorethylbenzenes (Zoc. cit.) with sulphuric acid four isomeric sulphonic acids are formed which may be separated by the fractional crystallisation of' their bariiim salts. a. 2(C6H3C1EL-S03),Ba + H20 forms white needles and is very sparingly soluble in water. p. 4(C6H,C1Et.S03)zBa + SH,O forms a white crystalline powder consisting of very small needles. y. (C,H,ClEt.SO,),Ba + H,O forms colourless rhombic plates having a brilliant lustre; and lastly 6. S(C6H,C1Et.S03),Ba + H,O forms white granular or mamellar tufts of acicular crystals and is readily soluble in water.CzH = CgHj'c~H'j. C. H. R.ORGANIC CHEMISTRY. 231 The mixed monochlorodiethylbenzenes C6H3C1Eh2 have a sp. gr. of 1.036 a t O" and boil between 215" and 255" ; by oxidation with chromic acid two chlorophthalic acids are obtained; the a-acid [?C1 (COOH) = 1 3 51 is insoluble in water a t 15" but dissolves readily in boilinq water and most of the ordiiiary solvents and melts at 129-130". When sublimed it readily yields the anhydride which crystallises in needles melts at 114" and is soluble in the usual solvents. The /?-acid is insoluble in boiling water but dissolves in dilute ammonia from which hydrochloric acid precipitates it in amorphous whik flocks ; it is sparingly soluble in hot alcohol from which it crystallises better than its isomeride ; i t dissolves in most of the ordinary solvents melts at 123" sublimes readily a t loo" and distils without decom- position ; it probably has the constitution c6H3c1( COOH)? [?C1 (COOH) = 1 2 51.Besides these acids a third oxidation- product chlorethylbenzene m e t h y l ketone C6HsEtC1*CO&Ie was ob- tained ; i t is insoluble in hot aqueous ammonia but dissolves readily in hot alcohol ; boils between 265-270"; by fusion with potash i t is converted into ethylchloroberraoic acid C,H,ClEt*COOH. This is in- soluble in cold water melts a t 115" and commences to sublime at 100" ; the bayium salt (~6H3CIEt*COO)2Ba forms small crystals insoluble in cold wat,er. The chlorotriethylbenzenes CcH,C1Ets3 boil between 235" and 260" and have a sp.gr. of 1.028 a t I" ; by oxidation with potassium per- manganate an acid was obtained in small quantities. The rnonochlorotetrethy Zbenzenes C6Hc1Et4 boil between 265" and 290" ; the sp. gr. of the liquid a t 0" is 1.022. Monochloropenteth ylbenzene C6C1Et is very difficult to obtain ; it boils between 290" and 295"; the sp. gr. of the liquid at 0" is 1.065. In the preparation of this compound a liquid boiling at 350" was separated; it has a reddish colour; its vapour-density is 8.85 and its sp. gr. at 0" = 1.179 ; it remains liquid at -7" and has the composition C,H,Cl,. A. P. New Method of Chlorination. By A. COLSON and 13. GAL'TIER ( C o m p t . rend. 101 1064-1066).-When 10 C.C. of a xylene are heated with 35 grams of phosphoric chloride in sealed tubes a t about 190" the products are phosphorous chloride hydrogen chloride and a chlorine-derivative. Paraxylene yields tolylene chloride C6H4(CH~C1) ; ortho-xylene yields the chloride corresponding with ortho-xylene glycol and metaxylene the chloride corresponding with metaxylene glycol.If 7 C.C. of toluene is heated in sealed tubes a t 190" with 30 grams of phosphoric chloride i t yields benzyl dichloride CHPhCI,. 5.5 C.C. of paraxylene heated under the same conditions with 4 0 grams of phosphoric chloride yields phosphorus trichloride and a chloride c6H4( CHCI,) which forms transparent crystals melting a t Y 3 O and is soluble in ether light petroleum chloroform benzene and alcohol. When heated with 100 times its own weight of water this chloride is converted into terephthalic aldehyde. Ortho-xylene under the same conditions yields a correspondinq derivative which melts a t 8G0 is more soluble in ether and light232 ABSTRACTS OF CHEIIICAL PAPERS.petroleum than the para-compound and likewise dissolves in benzene chloroform and alcohol. When boiled with 100 times its weight of water it is completely saponified and although the corresponditig aldehyde has not yet been isolated alkalimetric titration of the liquiti after saponification shows t,hnt the chloride has t8he constitution CsH1(CHC12)2 and not C,H,.CCl,*CH,Cl. These results show that phosphoric chloride furnishes a means of introducing a definite amount of chlorine into the homologues of benzene and that the chlorine does not act on the hydrogen of the benzene nucleus until substitution has taken place in the lateral chains.C. H. B. Fractions of Coal-tar Oil Boiling between 170 -210" ; 1 2 4 5 Durene. By K. E. SCHULZE ( B e y . 18 3032-3034).- 1500 C.C. of coal-tar oil boiling between 189 and 200" previously freed from bases and phenols was shaken successively with quantities of sulphuric acid of increasing strength (from 400 C.C. of 66 per cent. acid to 20 C.C. fuming acid containing 50 per cent. sulpliuric anhydride) for 10 minutes and allowed to subside for a quarter of an hour in each case when the acid was drawn off and saponified. A residue of paraffin remained. The last fraction but one yielded symmetrical durene. Other modifications of durene are probably present. These results are contrary to Jacobsen's hypothesis which excludes tlie possibility of the presence of tetramethyl-derivativea of benzene in coal-tar oil.N. H. &I. generally stated that metacresol does not solidify even a t -80" ; it is however here shown that when prepared pure from metatoluidine it can be malde to crytdallise when cooled in a freeziiig mixture to -18" by the addition of minute crystals of phenol which it resembles in crystalline form. Thus obtained it melts a t 3-4". Similar experiments with commercial metacresol were not so suc- cessful although it WRS obtained of a glassy consistlency in a freezing mixture of ether and solid carbonic anhydride. Derivatives of Phloroglucinol. By J . HERZIG (Monatsh. Chem. 6 884-888) .-Tribromophloroglucinol was prepared from pure syn- thetically produced phloroglucinol and also from the querciglucol of Gautier (Abstr.1881 272). As the loss in the preparation of this compound by Hlasiwetz's method is due to the simultaneous presence of bromine and water the following modified process was adopted. Bromine was added gradually and in slight excess to a solutim of phloroglucinol in glacial acetic acid the free bromine removed by heating on the water-bath and the tribromophloroglucinol recrpstal- lised from water the yield was 92-94 per cent. of the phloroglucinol employed. The melting points of the tribromo-compounds produced by this method from pure phloroglucinol and from querciglucol were found to be identical namely 148-150" and further the triacetyl- derivatives CgBr3Ac3 prepared from the tribromo-compounds by the action of acetic anhydride and sodium acetate which crystztilise from alcohol in colourless needles also showed in each case the same Metacresol.By W. SI'AEDEL (Bey. 18 3443-3445)-It is V. H. V.ORGANIC CHEMISTRY. 233 ~uelting point 181-183". The difference therefore observed by GiLutier between phloroglucinol and querciglucol is apparently due to the presence of impurities in the latter. On submitting tribromophloroglucinol to the action of dilute alkalis the whole of the bromine is removed as hydrogen bromide aud on acidifying no precipitate is formed ; the products of this reaction liave not yet been examiiied. Phenylmelamines and their Derivatives Normal Iso and Asymmetric Compounds. By A. W. HOFMANN (Ber. 18 3217- 3234).-Triphen~lmelamine (this vol.p. 41) is best prepared by the action of aniline on cyanuric chloride ; the product is extravted with tlilute hydrochloric acid to remove unclianged aniline and then crystal- lised from alcohol. When heated with hydrochloric acid a t l50" it is decomposed into aniline and cyanuric acid. HemphenyZmela?nine C,N,( S Ph2)3 is obtained by the action of tliphenylnmiiie on cyanuric chloride. I t forms rhombic plates melting above 300' insoluble in alcohol ether chloroform &c. but can be recrystallised from nitrobenzeile. Hydrochloric acid a t 150" converts it into diphenylamine and cFanuric acid. Phenylcyanainide is prepared by heating 15 grams of phenylthio- carbamide 25 prams of potagh 50 grams of' lead acetate and 2 litre of water f o r 10-15 minutes a t 100" ; the solution is then filtered and treated with acetic acid. The amide separates as an oil which solidifies on cooling.It crystallises from water (with 4 mol. HI,O) and melts a t 47" (comp. Abstr. 1879 804; 1880 44) ; a pZatiiiocldoi.ide (CN*NHPh),H,PtCl and a siZrer salt CN-NAgPh were pre- pared ; they differ in composition from those described by Feuerlkin 'rriphenylisomelamine (C N*Ph) ,(NH) is prepared by heating pllenylcj-anamide for one hour a t 100" ; it melts a t 185" (comp. Bey. 3 267). The plutinochloride and auroc7~Zoritle are described. When stirred with cold dilute hydrochloric acid it gradually dissolves with formation of a cornpound of the formula NPh< C(NH)-NPh and much ammonium chloride. This substance when boiled wit11 A.P . (lor. Cit.). CO-NPh>C:NH CO*NPh hydrochloric acid yields a compound NPh<<co~Kph>c NH. This crystallises from alcohol in needles which melt a t 272". cliloride ( C,H,N,o,),]Ei,PtCl was prepared. 150" converts triphen~lisomelamine into triphenyl isocyanurate A platino- Hydrochloric acid a t melting at 275" (comp. Abstr. 1835 774). Asymmetrical trip7~enyZmelamine NPh<C(Ka c(NH)*NPh l-N>C-Y HPh is obtained when a solution of phenylthiocarbamide' in strong alcohol is boiled with freshly precipitated mercury oxide filtered and boiled for a long time in a reflux apparatus. From time to time the alcohol is ciistilled off and the resinous product twated with the cold alcohol. This is repeated until the resin no longer forms a clear solution irl the234 ABSTRACTS OF CHEJIICAL PAPERS.alcohol when an additional hour's boiling suffices to complete tlie reaction. The product is purified by cryst'allisation from chloroform and forms small colourless needIes melting a t 217". It is insoluble ill water but dissolves readily in all acids and is precipitated by the addition of alkali. Theplafinochloride C21H,6N6,H2PtC16 + H,@ forms small nodular very sparingly soluble cryst'als. The aurochloride was also prepared. Hydrochloric acid act,s on it a t loo" with formation of a compound Co*N'h>C*NHPh. The aui-ochloride C2,H,N60,HAuC14 crystallises in groups of plates. When asymmetrical triphenjlmelamine is heated a t 150" with hydro- chl oric acid diphen. y lated ort hoisoc y anuric acid NPh< co-N>C -0 H is formed.It is almost insoluble in water sparingly soluble in ether and alcohol and crystallises from the latter in groups of needles melting a t 261" ; a silver salt C15H10AgNY03 was prepared. Concen- trated hydrochloric acid a t 280" decomposes the acid into aniline ammonia and carbonic anhydride. CO*NPh N. H. M. Toluylenethiocarbimide. By 0. BILLETER and A. STEINER (BY. 18 3292-32993) .-Toluylenedit hiovarbamide was prepared by Lussy 's method (this Jour. 1875 1036) slightly modified. It forms colourless lustrous plates melting a t 206" (uncorr.). Fuming nitric acid at 120" does not act on it. Hydrochloric acid acts on it with formation of a small quantit'y of a crystalline substance probahly toluylenethiocarbimide. l\iCetatoluylenediphenylthiocarbamide separates from a dilute soh tion of tolnylenediamine and phenylthiocarbimide in a mixture of alcohol and ether in small crystals melting a t 163".When boiled with strong hydrochloric acid it decomposes into (1) toluylenediamine and phenylthiocarbimide (2) aniline and metatoh yZei~edithiocu,rbimide (toluyleneisothiocyanate) C7H6(CNSb. The latter compound crystal- lises from light petroleum in colourlcss crystals melting at 56". Its vapour has the characteristic odour of thiocarbimides. The compound described by Lussy (loc. cit.) as toluylenethiocarbimide is probably impure phenylthiocarbimide. Toluylenethiocarbivnide can be more ad vantageonsly prepared by Rathke's method (Annalen 167 218) from toluylenediamine. Crystallography of some Organic Compounds. By E. WICKEL (Zeit.Kryst. &Fin. 11 78-82) .-Crystals of the following compounds were measured Metanitrobenzmesidine C6H,~~e,NHE.C0.C6H,.NOz monosymmetric a b c = 1.6983 1 2.7838 6 = 84" 18'. Sodium metasulphobenzoate SO3Na*C6H4*C@*OH + 2H,O asymmetric a b c = 0.5183 1 1.7144 ac = 95" 43' /3 = 103" 3 3 y = 78" 24'. Benzo- phenone rhombic a b c = 0.8511 1 0.6644. Mononitromesitylene rhombic a b c = 0.5600 1 0.4878. Ethylacetanilide rhombic a b c = 0.8401 1 1.0064. Ethyl anishyclroxamate C,H,@,NEt.OH (Abstr. 1883 462) monosymmetric a b c = 1.3174 1 0.85B3 /j = 86" 5 4 . N. H. M. B. H. Y,.ORGANIC CHEJIISTRT. 235 Crystallographic Examination of some Organic Compounds. By 0. HEINTZE (Zeit. K~ysf. Min. 11 83-88> .-Crystals of the follow- ing compounds mere measured 'rrinitroparaxyleiie C6H&1e,(N0,) monosymmetric a b c = 2.4134 1 1.9194 /3 = 75" 40'.Bariurn isophthalate C & ( ~ o * 0 ) z h -I- 6H20 asymmetric u b c = 0.79354 1 0 61347 a = 92" 39+' /3 = 93" 48$' = 78" 534'. Nitrodiethylmetamidobenzoic acid monosymmetric a b c == 0.89385 1 1.09523 /3 = 74" 57'. Tri me thy lme tachlorop henylamm on; urn C6H4 CIoNMe3Br rhombic a b c = 0.87535 1 0-5:3392. Compound of grape-sngar with sodium chloride 2C6H120s7NaC1 + H20 hexagonal rhombo- hedra] a c = 1 1.7S23. Paratolptrimethylammonium iodide rhombic a b c = 0.71'747 1 3.0549.5. Triethylentritolytriamine N3Et3(C6HIRfe)3 monosymmetric a b c = 0.5816 1 1.0309 /3 = 75" 239'. B. H. B. bromide Action of Acetone on Aniline.By C. EXGLER and P. RIEHM (h'er. 18 3296-3297 ; comp. Abstr. 1885 1246).-A reply to Beyer (this vol. p. 145). Action of Potassium Cyanide on Dinitromethylaniline. By E. L~PPMANN aiid F. FLEISSNER (Monatsh. Chem. 6 807-817).- On slowly adding potassium cyanide (1 mol.) t,o an alcoholic solution of dinitrodimethylaniline (1 mol.) heated a t 50° dimethylaniline and a little ammonia are given off the liquid becomes reddish-brown and after a time blnckish- brown crystals of the potassium-derivative of dinit?-oditizeth!/ lamidophenol separate out. The pure phenol NMe,.C6H,(N0,)*OH prepared from this melts a t 195" is very sparingly soluble in alcohol more readily in chloroform and insoluble i n benzene-; it forms clear yellow triclinic crystals exhibiting the faces 101 101 110 and 110.The yield is about 20 per cent. of the nitro-base employed. By the action of nascent h-j-drogen o r hydrogen sulphide the phenol is converted into an unstable amicio-conipound. The ammonium-derivative forms golden-yellow scales ; it melts at 195". The potassium-dericative crystallises in brilliant orange-red needles is insoluble in alcohol and sparingly soluble in water. The silver-derivatice forms clear red crystals which become brown on ex- posure to light ; it explodes violently when heated to 140° and is fairly soluble in cold water. The baviuin lead and copper derivatives were prepared. On heating diriitrodimethylaniidophenol with dilute potash dimethylamine and the dinitroresorcinol described by Benedikt (Abstr. 1881 1132) are formed. Ortho-xylidines.By 0. JACOBSEN ( B e y . 18 3166-3168).-A reply to Wroblewsky (Ber. 18 2904). Compounds from Diazophenols and 8-Naphthylamine. By 0. SACHS (Ber. 18 3125-3132; compare Abstr. 1885 1238).- When an aqueous solution of ortliodiazophenol is added to a cold alcoholic solutionof P-naphthylamine a compound OH*(& EI4N3H-C1,H A. P.236 ABSTRACTS OF CHESIICAL PAPERS. is formed. This is insoluble in water soluble in alcohol frvm which i t crg-stallises i n slender red needles melting a t 192-19.3". 'I'he acety I-deriontive OH*C6H4N3Ac*C,oHi forms small red needles which melt a t 198". The bensoyl-conzpou?zd OH*C6H,*N,Bz*C1,Hi is prepared by melting together 1 part of the /3-naphthylamine-compound and 2 parts of benzoic anhydride. It crcstallises horn benzene in slender red lustrous needles melting at 163".'l'he compound OH*C6HIN,H*C,H7 is decomposed by hydrochloric acid at 150-160" with liberation of nitrogen and formation of /%naphthylamine and pyrocatechol. Bromine acts ou it yielding dibronio-/3-naphthylamine (described by Lawson loe. tit.) and a brominated pyrocatechol. When reduced with zinc-dust and glacial acetic acid it yields Lawson's x-P-naphthylenediamine. A corresponding compound was prepared by t h e action of paradiazophennl 011 P-naph thylamine. It forms red flat prisms melting at 192-193" and resembles tlie orthophenol-derivative conipletely. The acety2-derizmfive crystallises from glacial acetic acid in red lust,rous needles melting at 21 8". The Fmzoyl-tlerivniive is rcladily soluble in nitrobenzene and crgstallises in bright red lustrous needles ; it melts a t 244".A conapound OMe*C6H4NJH*ClnHi was prepitred by the action of methpl orthodiazophenyl ether on P-naphthylamine. It crystallises from alcohol in dark red monoclinic prisms having a metsllic lustre 2nd melts at 133". I n its behaviour it resembles the two compounds above described. The acetill. derivative forms very lubtrous red needles mclting at 198-199". The beruoyl-derirative crystnllises in groups of dark red lustrous needles which melt a t 152-153'. N. H. M. Ortharnidazo-compounds. By T. ZINCKE (Ber. 18 3142- 3114) .-Orthamidazotoluene when oxidised behaves in the same way as the compouiids from /3-naphthylamine and diazo-sal t s (compare 13. %4) and yields a very stable compound this forms colourless lustraus thin plates readily soluble in hot alcohol glacial acetic acid and beiizeiie; it iiielts at 125 -126".Hot acetic anhydride and cold concentrated sulphuric acid dissolve it unchanged ; nitric acid appears to have no ;iction on it. Assuming the compound to have the constitution given above t h e constitution of orthamidazotolnene would be - C,H,Me<~~>N*c,H,Me. This formula does not however account for the formation of a diazo-compound from orthamidazotoluene and from its disulphonic acid which requires tlie presence of a n amido- group. N. H. M. Sulphonation of Phenylhydrazines. By A. GALLINEK and 17. v. RICHTER ( H e r . 18 31 72-31 78) .-The sulphonation of the llydrazines can bs effect,ed b j slowly adding the hydrazine base toORGANIC CHEMISTRY. 237 concentrated sulphuric acid strong heating being avoided.Sulphonic acids however seem only to be formed when the para-position relatively to the hydraxine-group is unoccupied. The sulphonic acids can also be more readily prepared by the xct'ion of sulphuric acid on the sodium hydrazinesulphonates (X*S2H,*S03Na) obtained as intermediate products in the preparation of the hydrazines by tho reduction of diazo-compounds with sodium sulphite and zinc-dust. Limpricht has recently obtained several of the hydrazinebenzene- sulphonic acids by reducing the corresponding diazo-compounds (Abstr. 1885 1216). Pnrahydrazinebenzenesulphonic acid NzH3*C6H4*S0,H crystallises in flat lustrous needles with f mol. HZO. Strecker stated i t to be anhydrous. The barium lead sodium zinc and ammonium salts are described.Orthohydrazinetoluenesnlphonic acid N,H3-C6H3Me*S03H [Afe NzH3 SO,H = 1 2 ? 51 crystallises in tufts of thin needles. The barium lead sodium and zinc salts are described. In correction to Bosler's statements ( Abstr. 1882,1062) it is meiitioned that orthotolylligdrazine melts a t 59" not at 56" and that the free base crystallises in needles the hydrochloride in colourless four-sided plates. Pnratolylhydrazine when heated Rrit'h sulphuric acid yields not a sulphonic acid but a peculiar basic substance which is precipitated in volnminous yellow flocks on addition of soda to the solution. It is being investigated. I n conclusion the author states that the method of eliminating the hydrazine-group by boiling with a solution of copper sulphate can also be applied to the determination of the nitrogen in these sulphonic acids or i n acid solutions of their salts the nitrogen being completely evolved in the free state.A. J. G. Additive Products of Amarine Silver Mono-substituted Derivatives of Amarine. By A. CLAUS and L. SCHERBEL (Bw. 18 3077-3087 ; comp. Abstr. 1885 1132) .-Amurine silver methiodide CzlH1,AgN2,MeI is prepared by the action of methyl iodide a t the ordinary temperature on amarine silver to which a large quantity of berzene has been added; in 2 or 3 days a greyish-black powder is formed which is washed with benzene and crystallised from chloro- form. It is a white pulverulent substance insoluble in ether readily soluble in chloroform. It melts a t 173" (uncorr.).Amuriiie siluer ethiodide C21H1,AgN2,EtI is obtained in the same way as the above compound and forms a white ponder melting a t 115" (uncorr.). Amarine silcer benzylchloride C2,HIiAgN2,C7H7C1 is formed by the action of benzyl chloride on amarine silver a t 100". It is a white powder which becomes violet on exposure to light ; it melts at 250" (uncoi~.). Atnarine silver propyl iodide forms white microscopic crystals melting a t 140" (uncorr.). M e t h y lamarine (&H17MeN2 is formed in the preparation of the above-mentioned metbiodide. It is a white crystalline substance readily soluble in ether benzene alcohol and chloroform ; i t melts at 184" (uncorr.). Ethylamwine CZ,H,EtN formed in the preparation VOL. L. T238 ABSTRACTS OF CHEMICAL PAPERS.of amarine silver ethiodide crystallises in lustrous whitc plates melting a t 163" (uncorr.) ; it dissolves sparingly in ether readily in alcohol benzene and chloroform. Bromoberizenc acts on asmarine silver with formation of lophine and benzene. IC~oonobenzol/7amari?~e C21H,iBzN2 is obtained by the action of hen- zoyl chloride on amarine silver suspended in benzene a t 100". It forms large clear prisms readily soluble i n benzene alcohol and chloroform and melts a t 180" (niicorr.). Caustic alkali converts it into amarine and benzoic acid. The l~ydrochloride is soluble in hotl alcohol and in chloroform and melts at 802". The plutinochloride fornis a yellow crystalline precipitate readily soluble in alcohol insoluble in ether ; it melts a t 192". The dichron7ate and (rcrvhte are also described.Benzoy l a m a r i n e beuzoylchloride C,H,BzN2,BzCl separates from a solu- tion of its ingredients in benzene as a white crystnlline powder readily soluble in alcohol sparingly in chloroform and light petroleuni. It melts a t 312" (uncorr.). When benzoylamnrine is boiled with alcohol dibenzoylamarine is formed (comp. Abstr. 1883 799). Bm- zoylamarine benzylchloru7e C21H17B~N21C7H,C1 fornis small bright rhombohedra insoluble in ether and benzene sparingly soluble in chloroform. It melts at 351". When boiled with alcoholic potash solution it yields potassium chloride and benz!lIhs,rzo!/Zu,~ul.incl C7H7*CL1H,BzN2. This forms a white powder insoluble in alcohol ether benzene &c. IJewzylarnarine benzo?ylch7oridr C,H,.C21H,N,RzCI is obtained by the action of benzoic chloi-ide on benzylamarine mixed with benzene.It forms long yellowish needles which melt a t 340-350". It is insoluble in ether but dissolves readily in alcohol with decomposition and is thus distinguished from its isomeride. The compound SO formed benzoyl benzy lamarine C21 H (C,H7) BzN is i 1is0l uble in ethcr slcol~ol chloroform and dilute acids. Beiuoylumas.ine methiodide C21H17BzN2RfeI melts at 318" ; i t dis- solves in hot alcohol unchanged. The author considers that the existence of the two compourids benzoyl- amarine benzylchloride and its isorneride benzylamarine benzoyl- chloride excludc Japp's formula for amarine in which both nitrogen- atoms are represented as symmetrical amido-groups. The following formula are suggested for amarine silver and ethylamarine respect- ively :- I t melts a t 318".The ethiodide melts a t 354". N. H. 31. Preparation of Vanillin from the Gum of the Olive Tree. By A. SCHEIDEL ( D i ~ g l . polyt. J. 258 240).-The author obtains this substance by oxidising the gum of the olive tree. Olivil obtained by recryshllising the gum from alcohol or its acetyl-derivative C1B15O5Ac may also be employed. chacteristic reaction of vanillin is the productioii of a bluish-violet D. B. Dehydrodivanillin. By F. TIEMAYN (Der. 18 349.3-3496) .-AORGANIC CHEMISTRY. 239 coloration with ferric chloride ; on heating dehydrodivanilti?c OMe~CGH,(OH)(COH)~C6H2(OH) (COH)*OMe separates from tht! liquid in white needles insoluble iii ordinary menstrua but readily soluble in potash.It is derived from 2 mols. of vanillin by the abstraction of 2 atoms of hydrogen. I t s formation is Etnalogous to that of dithymol from thymol and of cedriret from ethylic dimethylpyrogallol ether by means of the same reaction. De- l~ydrodivanillin when heated with sodium methoxide and methyl iodide is converted into the corresponding dimefli y 1 ether It melts a t 303-304'. c 1,H I ( c 0 H ) 2 ( 0 31 e) 4 which crystallises in white needles melting at 131-138" insoluble in water and alkalis but more soluble than its parent compound in alcohol and ether. Deli yd~od~p~otocatechuic acid C,2H,(OH),(COOH)L obtained from dehydrodivanillin by fusion with potash and subse- quent purification by means of the calcium salt is an amorphous flocculent substance melting a t above 300" ; i t is slightly soluble in water and more soluble in alcohol.With ferric chloride it gives the characteristic colonr reactions of protocatechuic acid with copper sulphate a brownish-red with silver nitrate a brown with lead acetatc a voluminous white and with zinc sulphate a white precipitate. V. H. V. Resacetophenone. By A. MICHAEL and G. 31. P A L b x m (Amer. Cherrz. J. 7 275-277).-Nencki and Sieber (Abstr. 1881 591 arid 811) have given to resacetophenone the constitutional formula C6H3( OH) 2*C 0.C H3 whilst the authors had regarded i t as more probably represented by C,T3,<O>C(OH)*CH3 0 as it forms only a single monacetyl-derivative. By the action of phenylhpdrazine on resacetophenone in alcoholic solution a crystalline substance is formed melting a t 159" and haviug a composition agreeing with the formula C,H3(OH),.CMe N,HPh.Thus it would seem that a carbonyl-group is present although it was found impossible to obtain a diacetyl-derivative even by using acetic anhydride and sodium acetate. Nencki and Sieber were unable t,o obtain a hydroxyacetophenone by the action of zinc chloride on phenol and acetic acid; but by increasing the amount of zinc chloride this substance C,H,(OH)Ac can be prepared; it crystallises in needles melts at log" and is insoluble in water but dissolves in alcohol. H. B. Polythymoquinone. By C. LIEBERMANN and M. ILINSKI (Rer. 18 3193-3201 ; comp. Abstr. 1878 418).-When polythymoquinone is distilled it is reconverted into thymoquinone B small quantity of thymo- quinol being also formed.Thymoquiiione boils a t 332" under 760 mm. pressure not at about 200" as stated by Carstnnjen (this .Tour. 1877. 350). When polytliymoquinone is heated with stannous chloride and 1 . 2240 ABSTRACTS OF CHENICAL PAPERS. hydrochloric acid o r with zinc-dust and ammonia or is distilled with zinc-dust it is converted int,o thymoquinol. Polythymoquinone phenylhydraxide (c6H2MePr<g!&->)a pre- pared by boiling the quinone with phenylhydrazine hydrochloride and alcohol crystallises in lustrous orange microscopic cubes com- mences to decompose a t 243" and melts at 249". Polythymoquinone monoxime (C,H,MePr<N(EH)>) is obtained by dissolving 10 grams of the quinone in 30d c.c of 80 per cent. alcohol adding 10 grams of hydroxylamine hydrochloride and boiling for 2-3 hours.It is a crystalline powder insoluble in water; it blackens a t 240" and melts a t 264" with decomposition; if heated quickly it explodes. Like other quinoximes it shows feebly basic as well as acid properties. When reduced with stannous chloride it yields amidothymol. is prepared by heating the qninone with hydroxylamine hydrochloride soda and absolute alcohol a t 145" for two hours. It is a sparingly soluble heavy white powder melts with decomposition at about 290" and closely resembles the monoxime. When reduced with st'annons chloride and hydrochloric acitl. i t yields paradiamidocymene hydrochloride C6H2MePr( NH,Cl) ; this forms colourless needles and when oxidised yields thymoqui- none. Expeyirnents ape being made on the polymerisation of other qui non 8s.The dioxime (C6H2MePr< A. J. G. Ethyl Benzoylcyanacetate and Cyanacetophenone. By HALLER (Conzpt. rend. 101 1270-1273) .-Ethyl benzoylcyanacetate is obtained by the action of cyanogen chloride on ethyl benzoylacetate. 2.4 grams of sodium is dissolved in 30 grams of absolute alcohol 20 grams of ethyl benzoylacetate is added to the cooled mixture and dry cyanoqen chloride is passed into the liquid until the alkaline reaction disappears. The liquid is then filtered concentrated by evaporation and the residue heated with water and agitated wit>h ether to remove unaltered ethyl benzoylacetate. The aqueous solution is supersaturated with sulphuric acid and repeatedly agitated with ether The ethereal solutions are coricentrated by evaporation and the ethyl benzoylcyanacetate purified by repeated recrystallisation.It forms hard transparent prisms which melt a t 37.5" and are soluble in alcohol ether potassium hydroxide and sodium carbonate. Its alcoholic solution is distinctly acid and gives a red coloration with ferric salts. Like its analogues ethyl benzoylcyanacetate combines with bases and forms salts. The barium salt forms white crystals soluble in alcohol but less soluble in water and not decomposed by boiling ; the calcium salt is very similar. When treated with a saturated solution of hydrochloric acid in absolute alcohol ethyl benzoylcyanacetat,e yields carbonic anhydride ammonium chloride et.hyl acetate and ethyl benzoate. If boiled with a large quantity of water it yields cyanacetophenone the decomposi-ORGANIC CHEMISTRY.2-11 tion being represented by the equation COPh*CH(CN)-COOEt + H,O = CO + C,H,O + COPh.CH,.CN. Cyanacetophenone has a dis- tinctly acid reaction ; it dissolves i n sodium carbonate and seems to form a crystallisable salt. Derivatives of Durylic Acid. By J. U. NEF (Ber. 18 3496- 3499) .-A continuation of the author's investigations of durene (this vol. p. 64). DianiidoduiyZic acid C6Mes(NH?),.COOH,isobtained by the reduction of hhe corresponding dinitro-derivative. It crystallisea in silky needles me1 ts at 221" with decomposition is sparingly soluble in cold water more soluble in hot and in alcohol. When dissolved in hydrochloric acid it is oxidised by ferric chloride into dumquinone- carbozylic acid C802Me3.COOH which crystal lises in tufts of needles soluble in ordinary menstrua ; it decomposes a t 130" with evolution of gas.It gives a yellow amorphous precipitate with lead acetate and a compound wikh phenylhydrazine insoluble in ether. It is the first example of a benzoquinonecarboxglic acid. On reduction with zinc-dust in alkaline solution it is converted into the corresponding quinol or dihydmxyd u ~ y l i c acid C6h!te3( O.K),-COOH which crjstallises in grouped needles melting a t 190)" with decomposition. It is sparingly soluble in cold water but more soluble in hot. The alkaline solutions are of a deep-violet colour ; it is reconverted into the qui- none acid by ferric chloride. Benzallevulinic Acid. By H. ERDMANN (Ber. 18 3441-3443). -BenzalZecuZinic acid CI2Hl2O3 is obtained by heating a mixture of benzaldehyde levulinic acid and sodium acetate ; it forms minute compact crystals which do not however show a very definite melting point (120-125").It dissolves in concentrated sulphuric acid with production of a n intense red coloration ; it is decomposed by concentrated potash with separation of benzaldehyde. When reduced in alkaline solution it forms a 7-hjdroxy-acid decomposed on acidifi- cation into benzylvalerolactone The author ascribes provisionally the formula CHPh C. H. B. V. H. V. C(CH2Ac)*COOH to benzallevulinic acid. V. H. P. Perkin's Reaction. Synthesis of a Sulphur-derivative of Cinnamic Acid. By .J. M. LOVBN (Ber. 18 3242-3245).-A mixture of 15 grams of thiodiglgcollic acid with 20 grams of benz- aldehyde and 40 grams of acetic anhydride was heated with 5 to 10 grams of fused anhydrous sodium acetate for 2 to 1 hour.The product WRS poured into water when a thick brown oil separated which gradually became crystalline. This mas treated with animal charcoal and further purified by means of the sodium salt. The new compound COOH.C( CHPh).S.C( CHPh)*COOH is insoluble in water readily soluble in ether and in hot alcohol and separates from the latter in small pale-yellow crystals which do not melt without decom- position. The sodium sult ClsH,SO4Na + 2&H,O fornis thin plates with a silvery lust're. A bromine-derivative Cl8Hl2Br2SOJ was obtained by the action of bromine a t 100" on a solution of the acid in chloro- form. It is readily soluble in alcohol from wliich it separates in short242 ABSTRACTS OF CHEMICAL PAPERS. yellow prisms very similar in appearance to the original acid only yellower and larger.Introduction of the Carboxyl-group into Phenols. By S. V. KOSTANECKI (Ber. 18 3202-3206).-The author points out that the metbod of directly introducing a carboxyl-group into polyhydric phenols by heating them with aqueous sodium or potassium hydrogen carbonates only succeeds with those phenols containing two hydroxyl- groups in the meta-position relatively to one another. Cresorr,inolcarbo~:1/lic acid C6H,Me( OH)2*COOH is prepared by heating cresorcinol (1 part) with potassium hydrogen carbonate (4 parts) and water (5 to 10 parts) for 15 minutes ; the product of the reaction is then acidified extracted with ether &c.I t crystallises with L no$. H20 in very long thin colourless lustrous prisms melts a t 208" with evolution of carbonic anhydride is readily soluble in ether alcohol and hot wafer and gives a bluish-violet coloration with ferric chloride. [OH COOH 0 H M e = 1 2 3 6 or 1 4 3 61 as the remaining possible constitntion [COOH = 51 has been shown to belong to cresorsellinic acid. Pyrogallol is also readily converted into an acid when heated with potassium hydrogen carbonate ; this proved to be identical with the known pyrogallolcarboxylic acid. Derivatives of Phthalide. By M. HOENIG (Ber. 18 3447- 3450).-When phthalide is heated with fuming nitric acid it yields a N. H. M. The acid must have the constitution A. J. G. mononitro-derivative N02*C6H3<cH2>0 co [CO CH2 NOz = 1 2 41 which crystallises in long colourless needles melting at 141" nearly insoluble in cold water more soluble in hot alcohol and ether.When heated with chromic acid it yields unsymmetrical nitrophthalic acid. When reduced with tin and hvdrochloric acid it is converted into amidophthalide N H z * C H 3 < ~ ~ 9 > 0 [CO C02 NH2 = 1 2 41 which crystallises in short prisms melting a t 178" insoluble in cold water sparingly soluble in alcohol and ether ; its hydrochloride crystal- lises in needles and its platinochloride in minute rhombohedra. Nitrophthalidc when heated with phosphorus and hydriodic acid yields the pnosphate of amidotoluic acid COOH*C6H3Me.NH2,H3P04 from which the free acid is obtained by decomposition with barium carbonate and subsequent addition of sulphuric acid.It crystallises in colourless needles which melt a t I53" and are sparingly soluble in cold moderately soluble in hot water and alcohol ; its copper salt is a green precipitate consisting of minute crystals. Nit~-o-orthoh2Jdroxy- m e t hy Zbenao L'c acid prepared by heating nitrophthalide with alkalis crystallises in minute needles which melt a t 129" ; it is very soluble in ether alcohol and hot water ; its silver salt forms grouped needles. The corresponding amiclo-derivative OH*CH2*CGH3(NH2)*COOH is OH*CH,.C6H3(NO2).COOH [COOH CHZ-OH NO = 1 2 41,ORGANIC CHEMISTRY. 243 best obtained from amidophthalide. When heated wit,h fuming sulphuric acid phthalide yields a sulphonic acid S03H*C6H3<CH,>0 which crystallises in colourless deliquescent needles very soluble in alcohol insoluble in ether and chloroform.Its barium salt crystal- lises in colourless prisms t!he copper salt in large glistening light- blue prisms containing 2 niols. €LO and the sodium salt in hygro- scopic needles. V. H. V. By W. ROSER (Ber. 18 3115-3125).- Ethylenediphthalyl dissolves readily in boiling alkali solution to which alcohol has been added. When acidified the solution yields ethylene- benzoylbenzoic acid melting a t 172". When ethylenebenzoyl- orthocai*boxylic acid is treated with hydrochloric acid it yields ethylenediphthalyl and an anhydride ClsH,05 (a-) already described by Gabriel. The p-anhydride ClsN1205 is formed when the acid is heated a t 100" with hydrochloric acid for 10 hours.It is insoluble in water readily soluble in hot alcohol and crystallises in prisms melting a t 200-202". When boiled with alkali it is converted (like the a- an h j dride) into eth jlenebenzo y lorthocar box y 1 ic acid. The following formula are proposed for the a- and @-anhydride :- co Phthalyl-derivatives. When the double lactone Cl,H904 (Abstr. 1885 267) is boiled i t yields carbonic anhydride and phthazethylidene <c&,o>C c H4 CHMe which crystallises in small lustrous plates and melts at 67-69'. This compound is converted by boiIing with alkali into henzogl- eth2/l~)rthocarbnxyZic ucid COOH.(&H4*C0.Et. This acid was prepared by Gabriel and described by him as propiophenoneort hocarboxylic acid. pi- Pheny 1 butyric-orthocad3oxy lic acid COO H*C~H4*CH,.CH,*CH~*COOH is obtained by the action of hydriodic acid and amorphous phos- phorus on the double lactone (7oc.cif.). It forms small lustrous plates which melt a t 138-139"; i t is sparingly soluble in water readily in alcohol. P-Phthalirnidy~ropionic acid CO< $ z > C CH*CH,*COOH is obtained by the action of aqueous ammonia on the double lactone and subsequent addition of hydrochloric acid to the solution. It is sparingly soluble in water readily in hot alcohol and crystallises in slender slightly yellow needles melting a t 225". Salts are described. CO <%z>C< __ co> isomeric with the compound last described is prepared by evaporating a solution of the double lactone in strong alcoholic ammonia. It forms The barium and silver salts are described.C El,* C H Phtha,limidy~ropiolactone,244 ABSTRACTS O F CHEJIICAL PAPERS. small bright rhoinbic plates which melt with decomposition a t 20.5" ; it dissolves readily in hot water and alcohol. Alkalis dissolve i t readily with formation of salts of a bibasic acid Cl1H,NOa the barium calciuu11c and silver salts are described. The constitution of the acid is probably COOI'I.C,H,.C (NH)*CH,-CH,*COOH. Diphthalsuccinanilide C30H2dN204 is contlainad i n the aniline mot her-liquor i n the preparation of iso-ethylenediphthalyl (loc. cit.). I t is readily soluble in nitrobenzene and aniline sparingly in hot alcohol from which it separates as a white crystalline powder; it melts a t 267" with decomposition. When boiled with glacial acetic acid and hydrochloric acid it yields di23htha1succindehydranilide7 C30H20N202.This is insoluble in water and alcohol sparingly soluble in glacial acetic acid. It melts above 280". Alcoholic solution of pottash acts on it with formation of an acid not further examined. N. H. M. Carbostyril. By E. ERLENMEYER and J. ROSENHEK (Ber. 18 3295).-By the action of a solution of hypochlorous acid obtained by treating a solution of bleaching powder with boric acid (Abstr. 1885 1194) on quinoline carbostyril was obtained together with other pro- ducts. From a hot dilute aqueous solution (about 1 100) carbostyril crystallises with 1 mol. H,O in very thin long threads like asbestos ; from a concentrated solution it separates in anhydrous lustrous prisms. N. H. M. Constitution of the Compounds obtained from p-Naphthyl- amine and Diazo-salts their Behaviour on Oxidation.BJ- T. ZINCKE (Ber. 18 313.L-3141).-1'he fact that these compouiids do not react with nitrous acid makes it improbable that they contain NH,-groups. Oxidation experiments show that they contain two NH-groups. They probably belong to the class of compounds de- scribed by Griess as azimido-compounds. Thus the benzene-deriva- tive (Abstr. 1885 802) would have the constitution- PhN<NH>CloH6 N H or NHPh*N<b NH- H6>. J l O N Benzeneuxi~~~idora~~thalene PhN/ I \C,H6 is obtained by the 'd oxidation of the hydroazimido-compound (from diazobenzene and ,!3-naphthylamine) in acetic acid solution with chromic anhjdride. It forms nodular groups of white slender needles readily soluble in glacial acetic acid sparingly in alcoliol and benzene.It melts at 107-108". Ortho~~~~droxybenzemeazimido?aa~ht7,alene OH*C6H4*N3 C10H6 is pre- pared by the action of lead dioxide on a solution of the hydro-corn- pound in dilute alkali. I t crystallises in white needles having a silky lustre and melts a t 140'. It is insoluble in carbonates but dis- solves readily in hot glacial acetic acid alcohol benzene and aqueous alkalis. Concentrated nitric acid and bromine act on i t with forma- tion of compounds melting respectively a t 21 5-220" and 198-200".ORGANIC CIIEIiIISTRY. 245 Concentrated sulphuric acid dissol~es both compounds above described without change ; reducing agents have no action on them. Paralzyd?.oxybenzenenzimidona~hthale?ze is prepared in manner similar to the ortho-derivative.It crystallises from glacial acetic acid in three forms and melts a t 198-199'. It dissolves readily in acetic anhydride with formation of an acetyl-derivative melting a t 164-165'. N. H. &I. Azonaphthalene and its Derivatives. By R. NIETZKI and 0. GOLL (Ber. 18 3252-3260).-a-Azonaplithalene (Abstr. 1885 545) is best prepared by adding 5 parts of sulphuric acid to a solution of 1 part of amidoazonaphthalene in 100 parts of 95 per cent. alcohol ; the theoretical amount of sodium nitrit,e dissolved in water is then added the mliole boiled for some hours and precipitated with water. The crude product is dissolved in hot aniline and alcohol is added to the solut,ion when steel-blue crystals of azonaphthalene separate as it cools.It dissolves in sulphuric acid yielding a blue solution ; when this is heated a t 183" the colour changes to violet and the solution acquires a splendid brick-red fluorescence. Hydrazonn~,hthuZeize CIOH7*NH*NH*C1OH is obtained by boiling a solution of 16 parts of soda in 160-170 parts of alcohol in which 1 part. of azonaphthalene is suspended and then adding zinc-dust until the solution is decolorised. The product is filtered directly into water coutaining ammonium sulphide. and the precipitate thus formed dried and extracted with benzene. It forms colourless plates melting a t 275" insoluble in water readily soluble in alcohol ether and benzene. Naphthiclin,e NH2*CloHs*CloEifi*NHz is prepared by the action of staniious chloride on a solution of the azo-compound in glacial acetic acid.1 t crystallises from dilute alcohol in lustrous plates resembling benzidine and melts a t 198". The /i ydrocldoride C,oH,N,2HCl forms colourless lustrous plates ; the platinochZoritle crystallises in yellow needles which become greenish when dried ; the sulphate forms lustrous plates. When a svlution of a naphthidine salt is treated w i t h ferric chloride or chromic anhydride it acquires a splendid crimson colour. When warmed with chromic anhydride it yields a-naphthaquinone and phthalic acid. The diacetyl-derivat ive C20HlJN2A~2 melts above 300" and is almost insoluble in the usual solvents. Nitrous acid converts naphthidine into a diazo-comzpoud which yields violet azo-dyes with /j-naphtholsulphonic acids. The pZcrtitLochZoride is described.By converting naphthidine sulphate into the diazo-compound and decotriposing the latter with alcohol a hydro- carbon was obtained melting a t 153.5" ; it is probably identical with Lossen's a-a-dinaph tIiyl. Dinayhtll yline C,H,N2 is formed by treating hydrazonaphthalene with hydrochloric acid. It crystallises from beiizene in colourless plates melting at 273". The salts are readily soluble; when boiled with acids even acetic acid they give up ammonia and yield di- naphthylimide. When oxidised phthalic acid is formed. The diazo- compound yielded a hydrocarbon identical with that obtained fro ru napht hidine. I n the dry state i t is stable.246 ABSTRACTS OF CHEMICAL PAPERS. ninupl2fhyZcarbnxoZe < g::g:>NH is prepared by boiling a strongly acid solution of dinaphthyline hydrochloride.J t forms long colourless needles which melt a t 216". It sublimes without decomposition. It dissolves in sulphuric acid forming a reddish-brown solution which becomes deep green on addition of a trace of nitric acid. The pici-ate forms red needles melting a t 226" ; it is decomposed by ammonia. When a solution of dinaphthylcarbazole in glacial acetic acid is treated with sodium nitrite a nitrosamine is formed which crystallises in small yellow plates melting above 300". Acetic anhydride a t 220" converts dinaphthylcarbazole into an acetyl-derivative. It forms colourless plates which melt above 3CO" ; it is insoluble in benzene. N. H. M. Naphtholazobenzenes. By A. DENARO (Guzzettu 15,405 -409). -Four isomeric naphtholazobenzenes 0H~CI0H6.N2*C6H5 are possible namely two derivable from a- and two from @-naphthol.By frac- t'ional crystallisation from alcohol the two lat ter are separated from the crude product of the action of potassium nitrite on aniline nitrate and P-naphthol; the one forms cherry-red prisms melting at 132" (comp. Margary Abstr. 1885 546) the other is a red crystalline powder melting a t 120". The former yields an acetyl-derivative CI~H~~N,*OAC a s a brown crystalline substance melting a t 95". On reduction with tin and hydrochloric acid aniline hydrochloride and @-amido-P-iiaphthol (NH OH = 2 3) are formed thus proving that the hydroxyl and azo-groupings are in the positions 2 3 respectively. Of the isomeric a-nnphtholnzobenzenes one crystallises in minute red needles melting a t 166" the other is a violet powder melting a t 175".The former yields an acetyl-derivative melting a t 340° and on reduction and subsequent oxidation of the nmido-naphthol formed it yields a-naphthaquinone ; it is therefore a 1 4-derivative. V. H. V. 2 3 Naphtholsulphonic Acid. By A. CLAUS and 0. VOLZ (Bey. 18 3154-3162).-The following salts of this mid are described :-Sodium salts ONa*CloH6*S03Na and OH*C10H6*S03Na normal zinc salt with 2 inol. HzO normal lead salt with 24 mol. H20 basic lead salts CI0H6SO3,2PbO and CloH6SO3,2Pb0,OH2. By the action of phosphoric chloride on the acid a t temperatures below 150° several complex ethereal salts are obtained ; a t temperatures above 150" a chloronaphthol and a dichloronaphthalene are mainly formed.The chZoronaphthoZ CloH6Cl*OH [OH C1 = 2 31 is obtained by recrystallisation or sublimation in slender colourless needles ; it melts a t 101' (uncorr.) and is moderately soluble in hot. water and light petroleum very readily in most other solvents. 2 3 dichZoronaphthalene CloH6CIz crysfnllises in lustrous plates melts a t 61.5" (uncorr.) boils a t 286" and seems to be identical with the 6-dichloronaphthalcne of CGve (Abstr. 1878 676). The oxidation of these substances was attended with great difficulty. With chromic acid under the most favourable conditions aboutORGANIC CHEMISTRY. 247 10 per cent. of a dichloronaphthaquinone was obtained which was found to be the known dichloroquinone [O C1 C1 0 = 1 2 3 41. 0 A dinaphthylena ether C,,H,<O >CloH was obtained by heating either 2 3 dichloronaphthalene or the corresponding chloronaphthol or naphtholsulphonic acid with sodium carbonate and potassium nitrate a t 300". It sublimes in golden-yellow lustrous prismatic needles melts at 229" (uncorr.) and is soluble in chloroform acetic acid ether and alcohol to sulphur-yellow solutions showing a sea- green fluorescence.A. J. G. p-Dichloronaphthaquinone ; Constitution of 6-Dichloronaph- thalene. By A. CLAUS and P. F. MELLER (Ber. 18 3073-3076).- f3-Dichlorona~A,thapuinone CloH4ClzOz is obtained as an intensely yellow powder by the oxidation of e-dichloronaphthalene (Abstr. 1882 734). It melts a t 148-149" (uncorr.) and sublimes unchanged. When boiled with alkalis i t gives up one chlorine-atom and yields /Lhydroxychloronaphthaquinone CI,H4ClO2*OH.This crystallises in slender bright-yellow needles which melt at 203" (uncorr.) ; it is sparingly soluble in water readily in alcohol ether chloroforin? and glacial acetic acid. The alkali derivatives form small red crystals readily soluble in water; the barium and cnlcium derivatives are bright-red and dissolve in much water. The silver copper and Zeatd derivatives are also described. 13 - Chloronaphtlinquinone - anilide C,oH4C102*NHPh is obtained by boiling an alcoholic solution of P-dichloronaphthaquinone with aniline. It forms dark reddish-violet crystals which dissolve sparingly in alcohol readily in glacial acetic acid. It melts a t 155" (uncorr.). /I-Chloronaphthapuinone - ortlio- toZitide melts a t 175" (uncorr.) ; theparatoluida melts at 164" (uncorr.). The formation of p-dichloronaphthaquinone and of a mono- chlorophthalic acid in the oxidation of 6-dichloronaphthalene (7oc.cit.) show that in the latter compound the chlorine-atoms must have t'he P-position and must be on different sides of the naphthalene nucleus. N. El. M. p-Hydroxanthranole. By K. E. SCHULZE (Ber. 18 3036- 3039). - p-HydroxanlhranoZe OH-C -C.OH is obtained by the action of lead peroxide on pure anthracene dissolved in glacial acetic acid. Several precautions described in detail have to be taken owing t o the ease with which the substance is oxidised. It resembles hydroxanthranole in most of its propert,ies but is distinguished by its behaviour towards an alkaline copper solution from which it causes a separation of cuprous oxide ; hydroxanthranole merely decolorises the solution.An ethyl ether C,8H1802 was prepared by boiling ,%hydroxanthranole with ethyl iodide and alcohol for an hour ; it forms transparent amber-coloured crystals. The methy1 ether ci-ystallises in transparent yellow square plates which melt a t 196". The beiizyl ether forms lustrous colourless crystals melting a t 2.20". N. H. M. ,G&\ \C,H4/248 ABSTRACTS OF CHEMICAL PAPERS. Anthrapinacone. By K. E. S c H m z E (Ber. 18 3034-3036).- Aizthrapinacone CH2<c6H'>C(OH)*C( C6H4 O H ) < ~ ~ ~ > C H is pre- pared by acting on anthraqninone with zinc-dust and ammonia and subsequently treating the zinc-dust with hot xylene ; on cooling this yields long white needles of the pinacone which resemble dihydro- anchranole in appearance but is much more sparingly soluble i n alcohol.When heated it melts a t 182" and a t the same time loses water' with formation of diantlzranyl It is very electric. Chlor- and Brom-anthracenecarboxylic Acids Action of Carbonyl Chloride on Phenanthrene. By G. BEHLA (Ber. 18 3169-3171) .-Graebe and Liebermanii have shown (this Journ. 1872 139) that the chloride of one of the three anthracenedi- carboxylic acids is formed when anthracene is heated with carbonyi chloride at 180-200". The author finds that a t higher tempera- tures the known dichloranthracene CC1- /CCI and the 'c6H4 chloride of a monocarboxylic acid are formed. This chZoranthrace?t e- carbozylicacid CCl-C*COOH is also obtained by the action of chlorine on a solution of anthracenecarboxylic acid in chloroform. It is crystalline and melts at 258-259" ; wlieri heated above it,s melting point in sealed tubes i t is resolved into carbonic anhydride and chloranthracene. A bromaiath?.acenecarbvxyZic acid crystallisiiig in needles bas been obtained i n a similar niauner.Carbonyl chloride does not act on phenanthrene a t 200" ; between 250" and 280" a very small quantity of a substance was obtained soluble in soda and crystallising from benzene in needles. C,H4\ ,CsH4\ \C,Hj/ When oxidised it yields anthraquinone. A. J. G. Crystallography of some Camphor-derivatives. By V. V. ZEPHAROVICH (Zeit. Kryst. Min. 11 42-51).-The author gives the results of measurements of crjstals of the following compounds:-Cam- pholic acid CloHla02 monosymmetric a b c = 1.0935 1 1.2810 /3 = 64" 40$'.Nitrohydroxy-camphor Cl,H15(NO~) 02 monosym- metric a b c = 0.7617 1 0.4310 /3 = 89" 184'. Bromonitro- camphor Cl,-,HI4Br(NO2)O rhombic a b c = 0.7390 1 0.4757. Dibromonitro-camphor C1,H,3Br,(N02)0 rhombic a b c = 0.8472 1 0.5684. Anhydrocamphoronic acid CSHl2O5 rhombic a b c = 0.9634 1 0.8170. Camphor-derivative C8HL204 ob- tained by oxidising camphoronic acid rhombic a b c = 0 9877 1 1.1236. Silver salt of C8H120i C8HuAg04 asymmetric a b c = 0.5726 1 0.5737 axial angles u = 92" 3' 34" = 95" 14' 44" = 91" 52' 35". Potassium-derivative of dinitrobrom-ORGANIC CHEMISTRY. 249 methane CKRr(NO,).? asymmetric a = 77" 15' 17" /3 = 117" 3' 51t' '1 = 98" 49' 24". a b c = 0.2345 1 0.6619 B.H. B. The Camphor Group. By W. ROSEK (Bey. 18 3112-311,5).- When camphor is oxidised with nitric acid camphanic acid is formed as well as camphoric acid. E th y Z camp hocn rbozy late C,H 150. C 0 OE t is prepared by passing hydrochloric acid into an alcoholic solution of the acid and forms a cwlourless liquid boiling a t 276" (uncorr.) ; sp. gr. = 1.052 a t 15". The boiling point excludes the possibility of the formula C,H,O ascribed to the acid by Kachler and Spitzer (Abstr. 1852 66). When sodium camphocarboxylate is t'reated with sodium acetate and phenyl- hydrazine hydrochloride a hydmzhre cowpound is formed which crystallises in needles. These results confirm the formula C ,H,9 already ascribed to camphocarboxylic acid and show that it is a ketonic acid.From its instability the acid would be a p-ketonic acid. On the other hand it may be compared with phenylglyoxylic acid which when distilled yields benzaldehyde and carbonic anhydride according to which camphor would be an aldehyde. This would account for the formation of campholenic acid from caniphoroxime as well as from p-dibromo-camphor. Haller's camphor cyanide may be considered as the nitrile of campho- cxrboxylic acid ; hydroxycamphocarboxglic acid appears to have the same relation to camphocarboxylic acid that campholic acid has to camphor. N. H. M. Camphylamine. By H. GOLDSCHMIDT (Ber. 18 3297-3298 ; compare Abstr. 1885 1072). - Camphylamine CloHI9N was pre- viously prepared (loc. cit.) by reducing the anhydride of camphoroxime with zinc and sulphuric acid.An almost theoretical yield is obtained by the actiou of sodium and alcohol on the anhydride It forms a colourless liquid which boils at 1 9 6 1 9 6 " without decomposition. Exposed to the air it solidifies to it wa,xy mass consisting of a com- pound of camphylamine with carbonic anhydride. N. H. M. Gutta-percha from Bassia Parkii. By E. HECKEL and F. SCHLAGDENHAUFFEN (Compt. rend. 101 1069-1071).-Gutta-perchn from Bassia (or Butyrospermurn) Parkii (Conzpt. rend. 100 1239) resembles ordinary gutta-percha in its physical properties. I t is obtained in compact fibrous ma,sses which soften in warm water and become adhesive a t about the boiling point. It becomes electrified as easily as the ordinary va'riety and serves equally well as an insu- lator ; sp. gr.0.976. The gutta-percha from Bassia is however much less soluble in light petroleum terebenthene ether and boiling acetic acid than the ordinary variety hut is almost equally soluble in carbon bisulphide chloroform benzene and boiling alcohol of 95". The proportion of each variety dissolved by the different solvents is given in the following table :-250 ABSTRACTS OF CHEMICAL PAPERS. Carbon bisulphide. Chloroform. Benzene. Ether. Ordinary gutta-percha . . . . . 99.72 98.60 93.20 413.8 Gutta-percha from B. Parkii 97.92 98.28 92.80 20.1 Boiling Light Tere- Boiling alcohol petroleum. benthene. acetic acid. of 95'. Ordinary gutta-percha . . . . . . 34.0 20 19.2 7 Gutta-percha from H. Parkii 18.1 8 12.8 7 When analysed by Payen's method the product from B.Piwlzii yields gutta-percha 91.5 albane 6.0 fluavile 2.5 = 100 and is almost identical in composition with the commercial article. It leaves 1.2 per cent. of ash which contains iron manganese calcium sodium potas- sium lithium silica and sulphuric and carbonic acids. Gutta-percha from B. Parkii is excellently adapted for the produc- tion of casts moulds &c. C. H. B. Oxidation of Copai%a Balsam. By S. LEVY (Bey. 18 3206- 3208). Dimethylsuccinic Acid an Oxidation-product of Copaiba Balsam. By S. LEVY and P. ENGLANDNR (Ber. 18 3209- 3212)-By the distillation of copa'iba balsam two fractions of nearly constant boiling point are obtained of which the one investigated is colourless lsevorotat,ory boils a t 252-254" and has a sp.gr. of 0.8978 atl 24". When oxidised with chromic mixture it gave in addition to acetic acid and other products not yet examined 14 to 2 per cent. of an acid CGHl"04 which proved to be identical with un- symmetrical dimethylsuccinic acid. A Glucoside Allied to Coniferin. By F. TIEMANN (Ber. 18 3481-3493).-As it has been demonstrated tlhat the composition of coniferin is represented by the formula A. J. G. C6H,(C3H4*OH) (OMe)*OC,H,05 [ = 1 3 41 and that it thus belongs to the class of phenol glucosides experiments were made with a view to the synthesis of this glucoside indirectly from glucovanillin. Glucoferulic aldehyde C6H3(C2H2-CHO)(OMe)*OC6H1105 [ = 1 3 41 obtained by heating glucovanillin with acetaldehyde in presence of soda crystallises in needles containing 2 mols.H20 ; it melts at 200 -202' and is readily soluble in hot water alcohol and ether. It does not reduce Fehling's solution and in aqueous solution is lsevorotatory. It shows all the characteristic reactions of the aldehydes giving a red coloration with rosaniline in presence of sulphuric acid and with para- diazohenzenesulphonic acid and sodium amalgam as also in yielding phelzylhydrazine and aldoaime derivatives. The former OMe*CGH3(C2H2*CH N2HPh)*OC6Hl,05 is a golden-yellow powder melting a t 212" insoluble in ether and water readily soluble in alcohol. OMe*CsH3( CzHz*CH N*OH)*0C6HllO5 The latter,ORGANIC CHEMISTRY. 251 crystallises in white needles melting a t 163" sparingly soluble in cold water more soluble in alcohol. Ferulic aZdetiyde OMe*C6H,( C,H,.CHO)*OH is best obtained by the decomposition of the above glucoside with emillsin.It is best although very imperfectly separated from the accompanying vanillin by the difference of solubility of their sodium hydrogen sulphite compounds. I t s melting point 84" is close to that of vanillin 81" ; but its crys- talline form is very different in that it forms needles belonging probably to the monosymmetric system cc b c = 3.014 1 ?. It is sparingly soluble in cold water readily soluble in alcohol and ether. As regards the ready transformation into vanillin ferulic aldehyde resembles coniferyl alcohol. Experiments on the reduction of glucoferulic aldehyde do not seem to have led to any very definite resalts. Glucofemlic m e t h y l ketone OMe.C,H,* ( C2H2*CO&~e)-OC6Hllo5 [ = 1 3 41 prepared from glucovanillin and acetone crystallises in golden-yellow needles containing 2 mols.H 2 0 ; i t melts a t 207" is sparingly soluble in cold water more soluble in hot water and alcohol. I t s aqueous solution is 1zevorotatoi.y. It yields a phenylhydrazine- derivative as a golden precipitate and also a ketoxime. It is decom- posed by emulsin into dextrose and ferulic m e t h y l ketone OMe*C6H,( C2H2*COMe)-OH which forms clear golden needles melting a t 130° soluble in alcohol ether and benzene. V. H. V. Quercetin and its Derivatives. By J. HERZIG (Monafsh. Chem. 863-883).-"t'he author considers that the formula C2J116011 adopted for quercetin is probably incorrect and that almost beyond doubt the so-called quercetin-derivatives (tribrorno-compounds &c.) can no longer be considered as substitution-compounds in which the quercetin nucleus exists in an unaltered state.This view is supported by the fact that the most carefully executed analyses of tribromoquercetin and tribroni-octacetylquercetin give results always differing very much from the theoretical and that both the so-called tribromoquercetin and also quercetiri itself when submitted to the action of excess of bromine in acetic acid are converted into tribrornophloroglucinol instead of yielding a more highly brominated quercetin compound ; warm dilute alkalis act on tribromoquercetin removing the bromine as hydro- hromic acid and forming an uncrystallisable substance a reaction exactly similar to that which takes place with tribromophloroglucinol (compare this vol.p. 232). The last two reactions seem to indicate the presence of a phloroglucinol nucleus in quercetin. By boiling quercetin with dilute alcoholic potash for from 8 to 10 hours phloroglucinol and protoeatechuic acid are obtained as end- products and by oxidising quercetin with potassium chlorate and hydrochloric acid protocatechuic acid is formed i n abundance. The author further points out that a series of estimations of quercetin in a large number of most carefully purified samples of quercitrin coming from various sources have invariably given results from 2 t o S per cent. higher than those of Lieberlnann and Hamburger252 ABSTRACTS O F CHEPllICdL PAPER,S. (Abstr. 1879 945) and of Rigaud (AnnaZsn 90 283).The anthor has net discovered any satisfactory method for the determination of the isorlulcitol and considers it to be still an open question as to whether the products of the decomposition of quercitrin by sulphuric acid consist simply of queiacetin and isodulcitol. The amount of iso- du1cit)ol which he finds varies between 34.7 and 38.6 per cent. Quercitrin is decomposed by the action of dilute acetic acid but is not acted on by hydrogen sulphide. It is converted into an acetyl-derivative by the action of acetic anhydyide and sodium acetate; this is an amor- phous compound which melts below loo" arid is much more readily soluble in alcohol than the acetylquercetin compound. A. P. Rhamnetin. By J. HERZIG (Monatsh. Chem. 6 889-890).-The author considers that rliamnetin is a compound very closely allied to quercetin and that the formula C12H8C) given by Liebermann and Hormann (Abstr.1879 271) should he doubled ; further the acetyl- rhamnetin prepared by these aut hms contains six molecules of acetyl on the double formula and not four as stated by them. By digesting ethyl-rhamnetin with potash in a sealed tube the formation of diethyl- protocatechuic acid and a derivative of phloroglucinol was observed. A. P. The Colouring Matter of Cochineal. By W. WILL and H. LEYMANN (Ber. l8,3180-3193).-The constitution of carminic acid is still practically undetermined those substances of known constitu- tion that have been prepared from it such as niirococcusic acid (tri- nitrocresotic acid [(NO,) Me OH COOH = 2 4 6 1 3 51 o r coccinin ruficoccin and ruficarmin (shown by Liebermann to be anthracene-derivatives) having been obtained by such energetic reac- tions as may have led to considerable modificat'ions in the component groups.The object of the present investigation was to obtain deriva- tives standing in closer relation to the original colouring matter. According to Hlasiwetz and Grabowski (AnnaZen 141 329) carrninic acid is a glucoside and when heated with dilute sulphuric acid is re- solved into a sugar and carmine-red CllH1,07. These statements however require confirmation. When carmine-red is dissolved in aqueous (50 per cent.) acetic acid and the solution boiled with excess of bromine two bromo-corn- pounds are formed of which one a-bromocarmin crystallises on cool- ing whilst the other p-bromocarmin separates in clear yellow flocks on adding water to the filtrate.a- Rromocurmir12 C1,H4Br1O3 after purification crystallises in colour- less needles melts a t 247-2418' with decomposition is insoluble in water sparingly soluble in hot alcohol benzene and glacial acetic acid. It is soluble in the alkaline hydroxides but not in alkaline hydrogen carbonates. U-HudroxzJFromocnrmin Cl0H6Br205 = OH*C,H~Br,O,*COOH is ob- tained by boiling the a-bromo-compouud with strong aqueous potash and is precipitated on acidifyiiig with dilute hydrochloric acid. It forms colourless crystals and melts a t 207-208" withORGXSIC CHEMISTRY. 253 evolution of gas. From its behsvisur when ninthylated it would seem to contain both a hydroxyl and a carboxyl group.The methyl salt OH*CgH4Br,O2.C0O.Me prepared by treating the above com- pound with methyl alcohol and hydrogen chloride is crjstalline and melts a t 192". A dimethyl salt OMe.CgHdBr202*C OOMe is prepared by heating a-hydroxybromocarmin with methyl alcohol methyl iodide and potash ; it is crystalline melts at 185" and when boiled with alcoholic potash and acidified with hydrochloric acid yields the niethoxy-acid OMe~C,H4Br,02*COOH. This forms voluminous ci*.rs- tslline flocks and melts a t 185" is insoluble in water very readily soluble in acids. A t the same time a6 the dimethyl saIt another compound is formed melting a t 150" from which by boiling with potash &c. a crystalline acid melting at 171" is obtained and is still under investigation.When a-hydroxybromocarmin is oxidised with an alkaline solution of potassium permanganate an acid of the formula C9H,Br,04 is obtained together with another substance C,H,Br?O which will be described with the derivatives of P-brornoearmin. The acid C9H6Br,0 forms colourless crystals and melts a t 243-244". The methyl sult OH*C,HdBr204~C00Me forms compact colourless crystals and melts at 201". The dimethyl salt OMeC,HdBr,O*COOMe forms lustrous crystals melts a t 161" and is soluble in alcohol. 0-Bromocarmin could not be crystallised directly from any solvent nor otherwise purified but by boiling it f o r a short time with potash a red powderj potassium salt C,H,Br,O,K i s formed from which by the action of hydrochloric acid an acid cryst;dlising in lustroiis needles and melting a t 232" is obtained.This wid P-hydroxybromo- carmin is distinguished from those previously described by the fact that all its salts are highly coloured ; it has the formula Cl,H5Br304. Attempts ta prepare its rne'thyl-derivatives were unsuccessful. When oxidised in alkaline .solution with dilate potassium permanganate it yields two substances whicqh can be separattd by treatment with water in whieh-one anly is soluble. Dibram~.ydro~i~aeth~lbenzoyldicarboxylic acid c&6&206 = ? C O O H . C 6 B ~ ~ M e ( O ~ ~ ~ C ~ c o o H .the aubshance soluble in water crystallises with 1 mol. H20 in colour- less lustrous prisms melts at 2%" with decomposition and is very madily soluble in most solvents. Several of its salts have been pre- pared. Uibromo7~ydro~ymethyl~hthalic aiihydride co CeHrBr20r = OH*CsMeBrz< co> 0 the second oxidation-product is also obtained as previously mcn- t,ioned by the oxidation of a-hydroxybromocarmin ; it is a crystalline solid melts at 195" is readily soluble in alcohol insoluble in water.It dissolves in alkalis but not in sodium hydrogen carbonate except on long boiling. When digested for 5-6 hours with methyl iodide methyl alcohol and potash it is converted into a methyZ salt of the formula O&Ie*C,lAeBr,( COOMe) which is crystalline melts at 70° VOL. L. P254 ABSTRACTS OF CHEMICAL PAPERS. and is readily soluble in alcohol ether and benzene insoluble in water and in cold alkalis. When saponified with alcoholic potash &c. it gives d i bronzometh 0% ymeih y lp hthalic acid OMe-C6MeBr (C 0 OH) ; this crystallises in slender needles and melts at 100" with loss of water and conversion into the corresponding anhydride co OMe* C6MeBr2 < > 0 a crystalline substance melting a t 144" and giving with sulphuric acid and phenol a similar colour reaction to that obtained with phthalic anhydride.When treated wit'h potash it is reconverted into the acid. As these results point clearly to the contiguous position of t,he carboxyl-groups and as the relative positions of carboxyl to methyl and hydroxyl have already been determined in nitrococcusic acid it follows that the hydroxy-anhydride must have the constitution [Me C20 Br OH Br = 1 2 3 4 5 61. If carmine-red really has the composition CllHI2O7 /3-hydroxybromo- carmin which contains the same number of carbon-atoms must stand in very close relation to i t ; and although not itself a coloured substance yet when dissolved in alkali mixed with stannous chlo- ride and acidified with hydrochloric acid it yields a substance which when exposed to air in ethereal solution absorbs oxygen yielding a coloured liquid of tint similar to that of a cochineal solution which dyes a similar colour and also like a cochineal solution turns violet- red on addition of an alkali.A. J. G Action of Chlorophyll on Carbonic Anhydride when re- moved from Vegetable Cells. By P. REGNARD (COWL@ rend. 101 1293-1295) .-Water containing carbonic anhydride was mixed with Coupier's solution exactly decolorised with sodium hyposulphite the chlorophyll was added and the vessel completely filled was placed in sunlight or in the dark.The decomposition of the carbonic anhy- dride was shown by the solution becoming blue. An entire leaf in sunlight quickly caused a blue coloration. Some tender leaves were triturated with enamel powder treated with water and the solu- tion filtered. The filtrate contained chlorophyll and fragments of cellules but no intact cells. k small quantity readily produced a coloration in the test-solution. Chlorophyll was extracted from other leaves by means of ether or alcohol and cotton-wool was dipped into the filtered solutions and then thoroughly dried in a vacuum at the ordinary temperature. Fragments of this prepared wool were intro- duced into the test-solution and exposed to light; a blue coloration was quickly produced.It follows therefore that chlorophyll has the power of decomposing carbonic anhydride even when not enclosed in a vegetable cell and not in contact with the white protoplasm. The chlorophyll in fact stands in the same relahion to the protoplasm as the haemoglobin in the blood does to the colourless globulin. Lokao or Chinese Green. By R. KAYSER (Bey. 18 3417- 3429).-This dye imported from China is obtained from the bark of various species of buckthorn ; according to the researches of Cloez and C. H. B.ORGAXIC CHEMISTRY. 255 Guignet (this Journal 1872 706) if is in the crude state a lake containing 26 per cent. of mineral matter and from which a compound lokain cz&f3,017 is extracted by ammonia. I n this paper these experiments are repeated but with slightly different results.On exhausting lokao frequently with ammonium carbonate and addiDg 90 per cent. alcohol a deep blue precipitate is obtained ; this is the ammonium salt of Eokaonir acid C42H&7 from which the acid may be obtained by decomposition with oxalic acid. Thus produced it is a pulverulent bluish-black mass of metallic lustre insoluble in water alcohol and ether. Its vtonarnmoniurn salt C42H17027*NHi forms small crystals of bronze-like lustre ; the ~~iammo~2ium salt is of similar appearance; the potassium barium and lead salts are deep blue powders. Soluble compounds of lokaonic acid show a perfect absorp- tion in the red and jellow portions of the spectrum. Lokaonic acid when boiled with dilute acids is decomposed into Zokanic acid (&HJ602 and a carbohydrate Zokaose ?&&1206.The former is a violet crystalline powder insoluble in water dcohol and ether; it gives off a molecule of water a t 120”; its aiizmonium salt C36H3502,NH4 is a dark blue powder soluble in water to form a bluish-violet solution ; the barium and lead salts C36H&”& are iusoluble blaekish-blue poviders. The soluble compounds of the acid show a characteristic absorption in the yellow and yellow-green portions of the spectrum. The decomposition of lokaonic acid is expressed thus C12H,027 = C36H36021 + C,H,O6. Concentrated sulphuric acid convepts lokanic acid into R substance of the composition C36H,01~ = C3,H3,OZ~ + 5Hzo a red-brown powder forming a barium-derivative CB6HUBaO16 whilst potash decomposes it into phloroglucinol and delokayiic acid C15R908 a brown powder ; dilute nitric acid yields nitrophloroglucinol and a brown powder which was not further examined.Lokaose CSH1206 obtained in the filtrate from the insoluble lokaonic acid in the reaction mentioned above forms minute ttcicular crystals and is distinguished from dextrose by its cupric oxide reducing power Rk I= 50 and its optical inactivity. v. H. v. New Constituents of Atropa Belladonna. By H. KUNZ ( 4 d ~ . Pharm. [3] 23 722-735) .-The occurrence of a fluorescent compound in belladonna has been repeatedly noticed. The author has found this compound both in the extract of the root and of the leaves and stalk ; the root extract was acidified until all fluorescence disap- peared and then agitated with ether.The brownish-yellow residue left on evaporation of the ethereal solution consisted of microscopic prisms having an acid reaction. By washing with cold ether a non- cry stallisable bitter mother-liquor was separated which was reserved for further examination. The crystals were purified by repcated treatment with boiling absolute alcohol which finally yielded small clusters of light yellow four-sided highly refractive rhombic prisms. This substance the author names prorisionally chrysatropic acid CI2H1,O5. It melts at 201*5” resolidifies a t 182.6”. When carefully heated the acid sublimes without decomposition but when more strongly heated burns with a luminous flame leaving no residue. It s 22 5 i; ABSTRACTS OB' CHEMICAL PAPERS. is soluble in 70-80 parts of hot water sparingly in cold water and in ether more soluble in alcohol and acetic acid.The concentrated aqueous and alcoholic solutions are pale yellow by transmitted light but by reflected light show a beautiful emerald-green fluorescence ; dilute solutionR give a bluish fluorescence. The crjstals dissolve in alkalis or alkaline carbonate solutions yielding splendid bluish-green fluorescent solutions. An aqneous solution when treated with potassium permanganate gives a green liquid showing strong indigo- blue fluorescence. Ferric chloride gives an emerald-green coloration changing t o cobalt-blue. The lead and copper salts were examined and described. From the formula and reactions of the substance the author infers a near relatioiisliip to hydroxynaphthaquinone.Leucatropic acid C1,H3'LgS is obtained from the bitter mother- liquor previously mentioned ; it crystallises in clusters of microscopic prisms haviEg a satin-like lustre it melts a t i3.8" and rcsolidifies a t 60.2". I t is insoluble in cold. but somewhat soluble in boiling water i t is nearly insoluble in cold but readily soluble in boiling ether and in alcohol. Qualitative examination indicates that the compound belongs to the fatty acid series. The anthor also found about 0.6 per cent. of succinic acid in belladonna extract prepared from the herbaceous part of the plant. J. T. and r-Picolines. By 0. LANGE (Rer. 18 3436-3441J.- a-Picoline is best separated from animal oil by means of its sparingly soluble mercuriochloride ; the process is more practical than that of the fractional crystallisation of the a- and ,G-picoline platinochloride~j proposed by Wkidel.The pure base boils at 129-130" (13$" Weidel) ; its sp. gr. at 0" compared with water at 4" is 0.9656; its platinochloyide Forms small crystals which melt at 178" its mercuyio- c h l o d e leaflets which melt a t 104" ; its aurochloride crystallises in needles melting at 167-168" and its picrate in needles melt- ing at 165"; both these last-named salts are moderately soluble in water. 7-Picoline is best obtained synthetically by Ladeuburg's process from pyridine and methyl iodide. On distilling the product obtained from pyridine methiodide two principal fractions are obtained boiling a t 127-134" and 142-1 50" respectively ; the former consists of 0 - the latter of ypicoline.This base when pure boils a t 144 -145" (corny. Hofmann and Rehrmann Ber. 17 26%) ; its sp. gr. at 0" compared with water at 4" is 0.971. Its salts are more or less sparingly soh ble in water ; the platinochloride is crystalline and melts a t 225-226" ; tbe aurockloride forms leaflets melting a t 205" ; the rnercuriochZoric7e long white needles melting at 136- 138" and the picrate silky needles melting a t 156-157". On oxidation the base is converted into isonicotinic acid. V. H. V. p-Picoline Synthesis of some Hornologues of Pyridine. B.y A. HESEKIEL ( B e r . 18 3091-3LOO) .-P-Picoline prepared from acetamide glycerol and phosphoric anhydride (Abstr. 1885 812) is lzvorotatory ; this cannot he due to the presence of optically active impurities as suggested by Skraup in the case of P-picoline preparedORGANIC CHEMISTRY.257 fi-om coal-oil. The mercuriochloride (C6NH7)2,H2HgCI* crystallises in white needles which melt at 143". The aurochloride forms a volu- minous precipitate sparingly soluble in water ; it melts at 182-184". The picrate crystallises in lustrous needles melting atl 145-146" ; it dissolves readily in water. The zinc salt and the platinochloride are also described. Meth ylethy Zpyridine C,HllN is prepared by heating paraldehyde with 3 parts of acetnmide and 2 parts of phosphoric acid for 16-20 hours at 160". It forms a clear colonrless oil boiling a t 175-179'. The platinochloride cryetallises in beautiful dark orange-coloured plates melting at 180" ; it is probably identical with a platinochloride obtained by Diirkopf from aldehydecollidine (Abstr. 1885 817).The uurochloride melting at 72" and the picrate melting at 157" are described. Parvoline was prepared in a similar way from propaldehyde acet- nmide and phosphoric anhydride. By the action of methyl iodide in P-pipecoline (Abstr. 1885 812) dissolved in methyl alcohol a compound CsH,NI is formed. It is a white crystalline substance melting at 1925". A platinorhloride C,H,N,PtCI was obtained which when heated at 234" becomes black. N. H. M. Constitution of Aldehyde-collidine. By E. DGRKOPF (Ber. 18 3432-3455) .-In this paper it is shown that aldehyde-collidine (comp. Abstr. 188.5 817) is an ethylmethylpyridine as. evidenced by its yielding on moderate oxidation a methylpyridinecarboxylic acid identical with the acid obtained by Hoogeaerff and v.Dorp from methylquinolinic acid and with the homoisonicotinic acid of de Coninck as shown by its physical properties and its conversion on further oxidation into cinchomeronic acid. The constitution of this collidine is thus represented by the formula C,NH,MeEt [Et Me = 3 41 and its hexahydride or copellidine by the formula C,NH,Me,Et ; it must then be identical with the cJlidine obtained from brucine by de Coninck. V. H. V. Identity of Bottinger's Pyridinedicarboxylic Acid with Lutidinic Acid. By E. VOGES (Ber. 18 3162-3165) .-Whilst according to the received theory there can be but two pyridinecarbo- xylic acids which yield r- pyridinemonocarboxylic acid (isonicotinic acid) three such acids have been described.The author has reinvestigated Bottinger's pyridinedicarboxylic acid and finds that it is identical with lutidinic acid. 'Ihere are therefore but t w o pyridinedicarboxylic acids containing one COOH-group in the [ = 3 ] position uamely cinchomeronic acid [2 31 and lutidiniu acid [l 31. Condensation of Cinnamaldehyde with Ammonia and Ethyl Acetoacetate. By W. EPSTEIN (Annalen 231 1-36).- x'shylio benzylidenedihy&rocoll~d~n~d~~arboxylate C2,Hz5O4N is formed by the actim of ethyl acetoacetate and alcoholic ammonia on cinnam- aldehyde. It is a white crystalline substance soluble in ether and iu. A. J. G.258 ABSTRACTS O F CHEMICAL PAPERS. warm alcohol. I t begins to soften a t 146" and melts a t 148-149'. When nitrous acid is passed into an alcoholic solution of this com- pound it is oxidised and converted into ethyl benzylidenecollidinedicar- boxylate C,H2,04N ; this melts a t 39" and is soluble in alcohol and ether.It also dissolves easily in acids forming crystalline salts which are decomposed by water. The pZatimchZoride (C2,H2304N)2,H2PtC16 melts at 195". Benzylidenecollidined~carbo~~li~ acid melts at 218-219' with partial decomposition. The anhydrous acid melts a t 241". It is soluble in alcohol and sparingly soluble in water ether and chloroform. With hydrochloric acid it forms an unstable compound which is decomposed by water. The platinochloride (C,H150J?)2.H2PtC1 crystallises in needles. The acid forms amor- phous metallic salts. When oxidised with potassium permanganate the acid splits up into benzoic acid and a lutidinetricarboxylic acid which is not identical with the acid obtained by Hantzsch (Abstr.1883 85) by the oxidation of collidinedicarboxylic acid. The luti- dinetricarboxylic acid crystallises with 1 mol. H20 in prisms. It is sparingly soluble in the ordinary solvents-560 parts by weight of water a t 8' dissolve 1 part of the acid. It decomposes a t 220" without melting. Hot hydrochloric acid slowly dissolves the acid ; on cooling mono- or tri-clinic crystals of the hydrochloride are deposited. This salt is decomposed by water or alcohol. The neutral salts of the acid are sparingly soluble and generally crystal- lise readily. Ferric chloride produces a red coloration in a solu- tion of t'he ammonium salt. The mercurous salt dissolves in hot water and is deposited from the solution on cooling in microscopic prisms.Benzene and lutidine C5NTvIezH are formed when the mixture of benzoic and lutidinetricarboxylic acids obtained by the oxidation of benzylidenecollidinedicarboxylic acid is heated with quicklime in a current of hydrogen. The properties of the lutidine obtained in t'his way have already been described by the author (Abstr. 1885 815). It is an isomeride of the lutidine which Hantzsch obtained from lntidinetricarboxylic acid (Abstr. 1883 85) and from pseudolutido- styril (Abstr. 1885 397). On oxidation it yields a pyridenedicarbo- xylic acid which closely resemble8 Ramsay's a-pyridinedicarboxylic acid (Abstr. 1879 266) and the isocinchomeronic acid of Weidel and Hertzig (Monatsh.Chem. 1880 5). On distillation in a current of hydrogen picolinic but no nicotinic acid is formed. Picolinic acid is also formed by the action of glacial acetic acid on the acid a t 160'. Hence it appears that the condensation-products of aldehydes with ethyl acetoacetate have the symmetrical constitution CHPh CR*C,NMe,(COOHh C(COOH)*CMe xceC(COOH) CMeyN' w. c. w. Action of the Homologues of Acetaldehyde on Ammonia and Ethyl Acetoacetate. By F. ENGELMANN (Aniznlen 231 37- i 1) .-Ethyl hy droparvo1in.edicarboxy b t e C5NH,Me2E t (C OOEt ) is fcwmed on waiaming a mixture of ethyl acetoacetate propaldehyde,ORGANIC CHEMISTRY. 259 and alcoholic ammonia. It melts a t 110" and closely resembles ethyl hydrocollidinedicarboxylnte in its properties. On oxidation with nitrous acid it loses 2 atoms of hydrogen and is converted into ethyl parvolinedicarboxylate CllHl104NEt,.This compound is a colourless oil insoluble in water. It unites with mineral acids forming hygro- scopic salts. The platinochluride ( C15H2,04N),H2PtC1~ forms red prisms soluble in water less soluble in alcohol. It melts at 139" and begins to decompose a t 185". ParvoZinedicarbo~ylic acid C,NMe,Et (COOK) is obtained from the ethylic salt by saponification with alcoholic potash in closed vessels. Most of the metallic salts of this acid are easily soluble in water. The silver salt is an exception. The free acid is best prepared by the action of sulphuretted hydrogen on the silver salt. It is freely soluble in water and in aicohol and melts a t 289-290" with decomposition.The barium salt C11HIIN04Ba + 3H,O crystallises in plates. The hydrochloride (C1,H,04N),HC1 + H,O forms glistening prisms. Farvuline C5NH2EtMe obtained by heating a mixture of potassium parvolinedicarbosylate anti quicklime is a colourless highly refrac- tive liquid. Its sp. gr. a t 14" is 0916. It boils at 186" and is so!uble in 73 parts of water at 0" but is less soluble in warm water. The aqueous solution yields precipitates with chromic and picric acids melting a t 120" and with solutions of zinc lead mercuric mercurous and silver salts. The platinockloride ( C9H,3N)2,H2PtC16 is soluble in hot water and alcohol. It melts at 210". The dickromate (C,H,3N)2,H,Cr20 begins to blacken at lSO" and melts with decom- position a t ZOO". It is not identical with the a-parvoline of Williams (Jahrb.che??z. 1854 495) and of Thenins (ibid. 1861 502) nor with the P-parvoline of de Coninck (Abstr. 1881 56) nor with the base which Waage obtained from propaldehyde-ammonia ( Abstr. 1884 172). Ethy 1 lqdroisoprop yl-lutidinedicarboxy late C5NH,Me2Pr ( COOEt) prepared by the action of alcoholic ammonia and ethyl acetoacetate on isobutaldehyde crystallises in long prisms melting a t 97". It is soluble in absolute alcohol ether benzene and chloroform insoluble in water and sparingly soluble in alcohol. When oxidised with nitrous acid it yields ethyl Zutidinedic~~,rboxyZat~ C5NHMe2( COOEt),. This substance melts a t 73' and boils at 301-302" without decomposi- tion. On recrystallisation from warm alcohol it is obtained in long prismatic needles which are insoluble in water.Lutidinedicarboxylic acid is obtained as a crystalline precipitate containing 8 mol. H20 on the addition of hydrochloric acid to a solution of the potassium salt. It is soluble in hot water and sparingly soluble in alcohol and ether. The barium salt CgH,04NBa + 2H20 is freely soluble in water; the lea,d salt C9HI,0aNPb + 2H,O crystallises in thick prisms. The 7b~drocliZoride CgH90aN,HC1 + ZH,O forms prisms. A solution of potassium lutidinedicarboxylate yields precipitates with silver mer- cury copper cadmium zinc anti iron salts. The acid is decomposed on distillation with lime yielding a lutidine which is identical with that obtained by Epstein (this vol. p. 257). E t h y l ~ydroisobutyllutidi.lledicarboxylate C4H9*C5NMe2H2(COOEt) is obtained by the action of alcoholic ammonia on valeraldehyde and260 ABSTRACTS OF CHEMICAL PAPERS.ethyl acetoacetate. It is deposited from akohd or light petroleum in long prisms insoluble in water but freely soluble in alcohol ether benzene chloroform and glacial acetic acid. It melts a t 100". When nitrous acid. is passed into the alcoholic solution of this substance it loses 2 atoms of hydrogen forming eayb i.,.obut.~l-lutidinedicarboxylate C4Hg-C,SJMe2( GOOE t),. This compound exists as a colourless thick liquid insolalble in water. It boils without decomposition between 312" and 318". The hydrochloride C17H11'1504N,HC1 forms long needles the platirtuch loride ( C,H2,O4N),H2Pt,Cl6 is freely soluble in water. It melts a t 207-208" with decomposition.By the action of alcoholic potash on diethyl isobutyllutidi~edicnr- boxylate mily one ethyl-group i8 replaced by potash. On decomposing this potassium salt the monethyl salt C4H,*C5NMe2( COOEt)*COOH is obtained in prismatic crystals soluble in alcohol and water. It melts a t 135" and begins to decompose at 230". The mercurous salt is obtained as a white precipitate on the addition of mercurous niimite to a solution of the pokassium salt. On warming the mixture the precipitate dissolves and is deposited on cooling in long needles It is decomposed by water and metallic mercury is precipitated. The barium (C,H,O,N),Ba + 5H20 and culciurii ( 615H2004N)2Ca + 4H20 salts crystallise in plates and are freely soluble i n water. The hydrochloride C15H2,S 04,HCl + 2H20 forms monoclinic prisms soluble in water and in alcohol.The porassium salt is converted into isobut!il-luti~ineilica,.boz2/lic acid by boilirrg with an aqueous solution of potassium hydroxide. The free acid C4H9*C5NMe2(COOH)2 f 2H2O prepared from the mercurous salt crystallises in monochnic prisms. It dissolves in hot water and in warm alcohol. The anhydrous acid melts with decomposition at 273". A solution o€ the potassium iJalt gives precipitates with silver lead zinc cadmium and copper salts and also with concentrated solutions of mercurous and mercuric salts. The bui-ium salt C1,H,O4NBa + 5H20 is freely soluble in water. 'l'he culciurn salt crystallises i n four-sided pyramids containing 3 molu. H20. The hydrochlol*ide C1,H15( COOH),N,HCI is soluble in alcohol and in hydrochloric acid.Isobutyllutidine CaIIg*C5NH2Rh2 is a colourless liquid boiling a t 210-213" and possessing a bitter taste. Its sp. gr. a t 18" is 0.8961 compared with water at the same temperature. It is more soluble in cold than in warm water. The base unites with acids forming very cleliquescent salts. The picrate forms yellow needles which melt a t 114-115". The ylatinochloride is crystalline. It melts a t 208-209". The dichrosnate is soluble iu hot water. It is decomposed by heat w itlioub melting. Condensation products could not be obtained by the action of acraldehyde instead of aldehyde on ammonia and ethyl acetoacetate. Pgridine-derivatives are not obtained when ethyl acetobenzoats is bubstituted fur ethyl acetoacetate in the preceding experiments. No condensatiori product is formed by the action of sulphuric acid Dimethylquinolines. By L.BEHEND (Bey. 18 3165) .-The uirnethj lquinoline from paraxjlidine sulphate described by L. XZJ er on ethyl acetobenzoste. w. c. w.ORGANIC CHEJIISTRY. 261 (this vol. p. 161) has already been described by the author. The base boils a t 264.5-265.5" ; sp. gr. 1.0752 at 4". The platinoclloride (GI ,HllN) (,H2P t Cl crys tnllises in reddish-yellow needles. 1 4 ~~trahydrodimethylguinoline CI1Hl5N7 obtained by reduction with tin and hydrochloric acid boils a t 271" and has an agreeable odour ; the hydrochloride CllHl,N,BCl crystallises in slender needles or transparent six-sided tables. Quinoline-derivatives from Propaldehyde. By K. HARZ (Ber. 18 3384-3401).-Ethylmethylto2uquinoline (ethyldimethyl- quinoliiie) CsLUHiMezEt [Me Et Me = 3 2' 3'1 prepared from paratohidine,.propaldehyde and hydroch!oric wid forms rhombic crystals melting a t 54" and boiling a t 287-288" under a pressure of 720 mm. ; i t is insoluble in water soluble in ether alcohol and ben- zene. Many of its salts are exceedingly soluble in water ; the hydr- iodide crystdlises in colourless needles ; the chromate in red needles ; the picrate in small yellow needles melting at 177"; the pZntim- c h l o d e in orangwred needles containing 2 mols. H20 ; the methiodide with H,O in monoclinic needles melting a t 75-76" ; the ethiodide with 4H20 in agglomerated crystals melting a t 112-114" ; and the etlboplutinochloride with 1H20 in minute glistening crystals.The base forriis a tetruhydro-udditice product C,sHi,M a colourless strongly refractive oil boiling a t 285-286" ; its hydrochloride crystallises in needles ; the platinochlowde i n brown leaflets containing 2H20 ; its uitrosn-derivative C,Hl,N*NO forms a crystalline mass and gives Liebermann's roaction ; its methyl-deriuutive CI3Hl8NMe7 is an oil boiling at 275-280" and forming a platinochloride crystallising with 2H20 in needles. With bromine the base forms an unstable dibromo-additive product decomposed on heating with formation of a dibromo-substitution pro- duct CldH13Br2N crystallising in white needles which melt at 143- 1&" and are insoluble in water but soluble iu ether and hot alcohol. Conceiitrated sulphuric acid yields a monosu1phorLic acid Cl,H,N*S03H crystallking in the rhombic system sparingly soluble in cold more so in hot water ; its barium salt crystallises with 1 rtiol.H,O in inter- laced needles and its lead salt (C'l,H,so,N),Pb,2C,3Hl~N*S0,H + 6H20 in golden needles very soluble in water. On fusing it with alkali the sulphonic acid is converted into the corresponding hydroxyl-derivative ClsHllN*OH which forms colourless needles melting at 45" and boiling a t 312-316". With concentrated sulphuric and nitric acids the base yields a mononitro-~eriuative C13H,N*N0 which crystallises in the triclinic system; it melts at log" and is insoluble in water but readily soluble in chloroform. Its hydyochloride forms dendritic golden crystals arid its plutitbochloride thick reddish-golden crystids containiug 2 mols.I!&. On reduction with stannous chloride there is formed an amid+ derivative C13H14N*NH2 crystallising in prisms or flat needles be- longing to the triclinic system; i t melts at 148-149" and is very boluble in alcohol sparingly soluble in ether and petroleum. A. J. G. ~thyltoluquinoli~~ecarb~xylic acid C9XH4MeEt.COOH jble Et COOH = 3 2' 3'152 62 ABSTRACTS OF CHENICAL PAPERS. obtained by the oxidation of the above bass with chromic acid crystallises with 1 mol. H,O in the triclinic system; it melts at 142- 143" and is soluble in hot water and alcohol; its solutions show a slight acid reaction. Its sodium salt with 3Hz0 and barium salt with 4H20 form interlaced needles ; its copper salt is a crystalline and silver salt an amorphous precipitate.The ethyl salt crystallises in needles ; it is soluble in alcohol and also in water but is saponified by it. On heating a t 150" it gives off carbonic anhydride with formation of ethyltoluquinoliiie CgNH5MeEt [Me E t = 3 2'3 crys- tallising in snow-white needles which melt a t 59-60" and boil a t 270" under a pressure of 718 mm. ; its salts with mineral acids are very soluble in water ; its plntinochloride crystallises in needles its picrate forms minute golden crystals melting a t 244-245". The base is apparently isomeric with the a-ethylmethylquinoline of Kugler. Etl~~lmethyZtoluqilinol~?~,e CgNH4Me2Et [Me Et Me = 2 or 4 2' 3'1 from metatoluidine and propaldehyde crystallises in hexagonal leaflets belonging to the rhombic system. It melts a t 40-41" and boils a t 288-292".Its hydrochloride crystallises in colourless prisms ; the hydroiodide in needles ; the picrate in golden needles melting a t 219-220' ; the platinochloride in minute needles containing 2H20 ; the methiodide with 1H20 in golden needles and the methoplatino- chloride in glistening orange-red needles. Ethylmeth~ltoluqz~ioline C,N&Me2Et [Me Et Me = 1 2' 3'1 from orthotoluidine and propaldehyde forms rnonoclinic cryst'als which melt at 44" and boil at 279-280" under a pressure of 717 mm. Its hydrochloride hydroiodide picrate and methiodide crystallise in needles theplatirwchloride in large leaflets and the methoplatinochloride in glistening orange-red needles. With tin and hydrochloric acid it forms a tetrahydro-additive product CI3HL9N a pale yellow oil boiling a t 274-276" and dissolving in nitric acid with production of an intense coloration ; its hgdrochloride forms colourless crystals spar- ingly soluble in water.V. H. V. Quinoline-derivatives from Normal Butaldehyde. By M. KAHN (Ber. l8,3361-3372).-On the addition of normal butaldehyde (100 grams) to aniline (60 grams) and fuming hydrochloric acid (120 grams) distillation of the product and extraction by ether two principal fractions are obtained boiling a t 230-250" and 280- 300" respectively ; the former consists of butylphenylamine the latter of propylethylquinoline CgNH5EtPP [PF Et = 2' 3'3. The pure base is a colourless liquid boiling a t 291" under 720 mm. pressure resembling quinaldine in odour rapidly darkening on exposure to air insoluble in water but volatile in a current of steam.I t is soluble in alcohol ether and dilute acids. Its hydrochloride crystallises with 2 mols. H,O in triclinic tables the nitrate with 1 mol. H20 in long crystals ; both these salts are best obtained by the gradual addition of ether to their alcoholic solutions ; the suZphate crystallises in tufts of needles the picrate in golden needles or leaflets melting a t 163" in- soluble in cold water sparingly soluble in alcohol; the chromate ( C,H,N),H,Cr207 in orange-) ellow needles ; the platinochloride inORGANIC OHEMlSTRY. 263 yellow needles insoluble in cold soluble in hot water ; the methiodide in golden needles containing 1 mol. HzO ; and methoplatinochloride (C14H.,7N)2,Me2PtCI in orange-yellow dendritic needles.EthyZpuinoZinecarboxylic acid C,NH,Et-COOH [COOH Et = T 3'1 is obtained by the oxidation of the above base with chromic acid. It crystallises in interlaced needles which melt at 148" with evolution of carbonic anhydride ; it is soluble in water crystallising therefrom with + mol. HzO sparingly soluble in ether. I t s pEa,tinochloride forms groups of needles and its picrate golden needleu melting at 153" sparingly soluble in water and alcohol. The copper salt is a bluish- green precipitate consisting of minute needles; the silver salt a white amorphous precipitate. Eth.ylquinoZi.ne C,NH,Et [Et = 3'1 obtained by the dry distilla- tion of the above acid is a colourless highly refractive liquid boiling at 265" under 718 mm. pressure. Its platinochloride crystallises in golden needles and its picrate also in needles which melt a t 163" (comp.Baeyer and Jackson Abstr. 1880 406 and Riedel Abstr. 1883 1152). Numal butylphen ylamine NHPh*C4Hg obtained in the reaction mentioned above is best purified by means of its nitroso-derivative ; it is a colourless oil boiling a t 235" under a pressure of 720 mm. and is volatile in a current of steam. Its hydrochloride and sulph.de crystallise in needles and are very soluble in water. The ?zityoso- derimtive NO*NPh*C4Hg is a golden-yellow liquid insoluble in water and dilute acids soluble in alcohol and ether ; i t gives Liebermann's reaction in a most marked way ; the acetyl-derivative NAcPh*C4H9 is a colourless liquid boiling at 273-275" under a pressure of 718 mm.V. H. V. Quinoline-derivatives from Isovalerafdehyde. By J. SPADY (Ber. 18 33 73-3384) .-Isovaleraldehyde and aniline in presence of hydrochloric acid form isobutylisopropylquinoline and isoamyl- phenylamine (comp. preceding Abstr.) which are best separated by means of their picrates that of the former being insoluble whilst that of the latter is soluble in cold alcohol. Isobuty~~so~ropylqzcinolle C,NH5PrS*C4Hn$ [C4Hg PrS = 2' 3'1 is a liquid boiling at 295-296" under 709 mm. pressure insoluble in water soluble in alcohol ether and benzene. On the addition of nitric acid to the base its nitrate C16H21N,HN03 + HzO separates at first as an oil but ultimately solidifies in acicular crystals ; the add swlphate forms pyramidal crystals belonging to the triclinic system; the hydro- chloride with 1H20 prismatic leaflets belonging to the triclinic system ; the chromate long orange-yellow needles insoluble in cold water and dilute sulphuric acid ; the methiodide golden needles containing 1 mol.H20 soluble in alcohol and hot water; the methoplatino- chloride ( CleH21N)z,Me2PtC1 reddish-golden triclinic prisms spar- ingly soluble in water and dilute hydrochloric acid. hop rop y l g uinol inecar box y lie acid C9NH5PrWOOH [COOH PI? = 2' 3'1 obtained by the oxidation of the above base with chromic acid c r p264 ABSTRACTS OF CHEMICAL PAPERS. t'allises in prismatic leaflets melting at 188-189' with slight de- composition ; its y latinochloride crystallises in orange-yellow prisms ; with silver nitrate it gives a flocculent precipitate of the composition CI3H12,NO2Ag + C13H,7N02,HN03 sparingly soluble in dilute nitric acid and decomposed by water into its components.On distillation with lime the acid is decomposed into qiiinoline and a diquinoline probably identical with that obtained by Japp and Graham (Trans. 1881 174) and by Weidel (-4bstr. 1881,613) ; but when heated above its melting point it is decomposed into carbonic anhATdride and iso- propylquinolirhe C,NH,PJ? [PI? = 3'1 a pale golden liquid boiling at 275-280" under a pressure of 71s mm. and solidifying in a freezing iiiixture to a crystalline mass; it is insoluble in water soluble in alcohol et.her; and benzene. Its hydrochloride and platinochloride crystallise in needles the picrate and chromate in delicate golden needles.Isoamylphewylarnine NHPh.CH2*CH2*C:HMe formed in the above- mentioned reaction i s a colourless oil of pleasant aromatic odour ; i t boils at 242-244" is insoluble in water soluble in alcohol and ether. Its hydruchloride crystallises in prisms its nitroso-derivative is an oil soluble in alcohol. and ether and giving Liebermann's reac- tion ; and its acetyl-derivative a liquid boiling a t 278" under a pres- sure of 720 mm. insoluble in water soluble in alcohol and ether. The base apparently is isomeric with the amylphenylamine obtained by Hofniann from amyl bromide and aniline (AnnaZen 74,153). Quinoline-aldehyde By A. EINHORN (Ber. 18 3465-3468).- I n this paper trichlo?-etl~ylidenepuinaldirze C9H6N*CH CH*CC13 and quinoline-(aldehyde are described which are identical with those obtained by v.Miller and Spady (p. 265) and were prepared by the same methods. The author however ascribes the formula C12HllN03 and not UI2HgNO2 to the acid from the trichloro-derivative. The pZatinochZoride of the aldehyde forms golden transparent crystals containing 2 mols. H20 ; whilst the aldehyde itself is said to melt at. 103-104+" but no analyses are given of this substance. An Aldehyde of the Quinoline Series. By A. EINHORN (Ber. 18 3144-3146).-Trirnethylyuinolinealdehyde CI3Hl,NO + 3H20 is obtained by the actioii of chromyl chloride on crude quinaldine being probably formed from tetramethylquinoline present in the crude substance. It crystallises from water in splendid needles melting at 73-74" ; it easily parts with its water of crystallisation and has then the melting point 101.5". It reacts readily with hydroxylamine and with phenylhydrazine with formation of compounds melting at 203" and 207" respectively.It reduces ammoniacal silver solution and is oxidised a t the same time to an acid which melts a t 224". V. H. V. V. H. V. N. H. M. Quinoline-a-acrylic Acid. By W. v. MILLER and J. SPADY (Ber. 18 3402-3405) .-By the direct reaction of equal molecules of chloral and quinaldine a trichloro-compound C12H8NC13,H20 is formed which crystallises in delicate needles melting at 146145O ; when heated with an aqueous solution of potassium carbonate it yield8ORGANIC CHEMISTRY. 265 pinoZilze-urr?ykic acid C9NH6-CH CHhCOOH [ C,H,*COOH = 2'7 which rrystallises in leaflets melting a t 3 90-195" ; its hydrochloride crystal- liseg in colourless needles the p l a t i n o c h l o d e in prisms and the barium salt in tufts of needles. QuinoZine-aldeh?yde C9PU'H6.COH [COH = 3'1 formed by the oxida- tion of the above acid with potassium perniamganate crystallises in plates belonging to t h e monoclinic system; it melts a t 70-71° is sparingly soluble in water aad petroleum readily soluble in benzene and alcohol.Its aldehydic nature is evidenced by itls ready reduction by silver salts a n d the forma.tion of a phenylhydrazine compound C16H,3N3 crystallising in golden leaflets melting at 195-198'. The authors propose t o extend these researohes to other aldehydes and their derivatives. V. H. V. Paraquinaldine-acrylic Acid. By W. v. MILLER and F. KINKELIN (Bey.18 3234-3239). Paramidocinnamic acid was prepared by the action of 100 grams of 38 per cent. hydrochloric acid and 100 grams of tin on a warm alcoholic solution of 25 grams of ethyl paranitro- cinnamate. The product was freed from tin and evaporated when crystals of the hydrochloride separa6ed. The jield is 75 per cent. of the themetical. Paraguin aldine-acry lie aciil C9NH,MeCH CH-COOH [Me C,H,*COOH = 2' 31 is obtained by heating 50 grams a€ paramidocinnamic acid hydro- chloride with 50 grams of concentrated hydrochioric acid and 40 grams of paraldehyde for two hours a t 100'. The product is diluted with water filtered and evaporated and the hydrochloride so obtained treated with sodium acetate which precipitates the free acid. It forms small needles which melt at 240-250" with decomposition but can be sublimed in part unchanged; iit dissolves sparingly in water and cold alcohol readily in dilute alkali solution.The hydro- chloride (with 1 mol. H,O) crystallises in prisms readily soluble i n water; the nitrate (with 1 mol. H20) forms colourless prisms with vitrems lustre. The plafknochloride (Cl&LllN02)~,H2PtC1 + 2H,O forms thick reddish-yellow prisms. Paroquin~~Zdine-aZdehyde C9N.H51fe-CH0 [Me CHO = 2' 31 is prepared by oxidising the above compound trit,h potassium pernmn- gnnate at 0". It cr,whllises from a mixture of benzene and light petro- leum in yellowish plates melting at ;106",readily soluble in alcobol ether benzene and in acids. The plutiiioohlaride (with 3 mols. H,O) crys- tallises in jorangeeoloured prisms.The phenylhydrazine compound forms gold-coloured p r i s m which melt a t 160". When the alde- hyde is heated for some hours at 150" with an equal quttntityof quinaldine a compmnd C9NH6*CH CH*C,NH,Me is formed. It is a yellow powder almost insoluble in the usual solvents soluble in aniline phenylhydrazine &c. and in strong acetic acid. Derivatives of Isoquinoline. By S. GABRIEL (Ber. 18 3470- 3 180).-Tn continuation of investigations on substances derived from isobenzalphthalide (Abstr. 1885,12;31) t,he author adds further obser- N. H. M.266 ABSTRACTS UP CHEMICAL PAPERS. vations on isobenza~hthaZimid.ine. This substance to which the formula c6&<C(oH) N> is now given in place of -CH*CPh- crystallises in the asymmetric system with axial ratios a b c = 0.8601 1 (?) ; its formation from isobenzalphthalide is analogous t o that of oxynicotinic from cumalinic acid.The presence of a hydroxyl- group in the compound is evidenced by the formation of a compound C,H,NCl from it by the action of phosphorus oxychloride whilst phosphoric chloride yields a dichloro-compound CsH,< c-,ll- >. The latter melts a t 162-163'; the former crystallises in needles melting a t 77-78' ; it is soluble in benaene and ether. On heating the dichloro-compound with amorphous phosphorus (1 part) arid hydriodic acid (8 parts) n monochloro-compound CIBHIONC1 is produced isomeric with the one above mentioned ; it crys- tallises in short glistening pyramids melts at 68-70' and forms a crystalline hydrochloride C15HloNCl,HC1 and a pZatinochZoride crys- tallising in sparingly soluble orange-yellow needles ; to this com- pound the formula C 6 H 4 < g g ! k > is ascribed.If these formulz are correct therefore the constitution of the last-named substance is that of a phenylisoquinoline. The moiiochloro-compound (m. p. 77') when heated with amorphous phosphorus and hydriodic acid is converted into phenylisoquinoline c6H4<cH-N> which crystal- lises in rhombic plates melting at 103-105" ; its hydmckloride forms orange-red pointed needles. On reduction with sodium amalgam both the di- and mono-chloro- derivatives yield tetrahydride of phenylisoquinoline C,H,N which forms glassy crystals ; it melts at 45-48" and is soluble in water and acetic acid. It is probable that phenylisoquinoline is identical with a base formerly obtained by the author by the disbillation of plitha- limide with zinc-dust.V. H. 1'. CC1. CPh -N CH CPh Paraxanthine and Heteroxanthine. By G. SALOMON (Ber. 18 3406-3410) .-As a correction of former observations on paraxan- thine a constituent of human urine (Abstr. 1883 Sol) the author ascribes to it the formula C,H8N,0 namely that of a dimethyl- xanthine isomeric with theobromine instead of the more complex formula C,H',N,O,. Further it is now shown that paraxanthine forms a sparingly soluble precipitate with mercuric chloride provided that the latter be in excess ; this consists of colourless prisms melting with partial decomposition ; it is readily soluble in hot water. Para- xan thine hydrochloride crystallises with difficulty ; it forms an orange- yellow crystalline platinochloride.These extended researches have led to the isolation of another con- stituent of human urine which it is proposed to call heterozanthine. In order to separate this the amorphous residue obtained as a bye-ORG-IX IC CHEMISTRY. 267 product in the preparation of paraxanthine is dissolved in ammonia the solution filtered from the calcium phosphate and oxalate and evaporated down when the heteroxanthine crystallises out. It is best purified by means of the crystalline sodium-derivative obtained by the addition of soda to a solution of the heteroxanthine. The base is a white amorphous granular powder ; it exists in urine it1 the propor- tion of 1 gram in 1000 litres. Its composition is expressed by the formula C6H6N402 corresponding with that of a metbylxanthine.It is differentiated from hypoxanthine xanthine and guanine by the above- mentiol;ed soda reaction and from paraxanthine by its amorphous form its sparing solubility the ready solubility of its hydrochloride in not yielding a precipitate with picric acid in presence of hydrochloric acid and in not emitting the characteristic odour of paraxanthine when heated. It is precipitated by copper acetate phosphotungstic acid and lead acetate in presence of ammonia. Its hydrochloride forms trans- parent crystals arranged in tufts; it gives a minutely crystalline platino- chloride. With mercuric chloride the base yields a greyish-yellow precipitate becoming crystalline after a time ; it contains chlorine and is converted by silver nitrate and ammonia into a silver com- pound.V. H. V. Doundak6 or African Quinine. By E. HECKEL and F. SCHLAG- DENHAUFFEN (Ann. Chim. Phys. [6] 6 313-328). The authors have made careful examinations of this bark from various sources and contrary to the results obtained by Bochefontaine Feris and Marcus find that it contains no alkaloid whatever but that the bitter principle consists of two nitrogenous resino'id yellow colouring matters soluble in alcohol and alkalis one being insoluble and the other soluble in water. The bark also contains a third principle of a brown colour insoluble in water and having no taste; glucose and small quantities of tannin chlorophyll and two fatty substances were also present. A. P. Strychnine-derivatives.By W. F. LOERISCII and P. SCROOP (Monutsh. Chem. 6,844-862) .-iVitrostyychnine N02*C?1H21N202 may be obtained by gra>dually adding 1 part of amhydrous strychnine nitrate t o 10 parts by weight of sulphuric acid the temperature being kept below 20° and the mixture allowed to remain for eight days then poured into 80 paats of water and neutralised with ammonia the nitro-compound thus precipitated is collected and re- crystallised from dilute alcohol ; it forms yellowish plates becomes slightly brown and melts a t 225" and dissolves in the usual solvents. The yield is about 88 per cent. of the strychnine nitrate employed. It is as strongly basic as strychnine and does not give any colour reaction with sulphuric acid and dichromate. N02.C21H21N202,HC1 forms hair-like crystals and is insoluble in cold adcohol. The plutinochloride ( N0,*Ce,H2,Nz02)2,HzPtC16 forms a light yellow granular precipitate and is insoluble in water and alcohol ; on dry distillation it gives a strong quinoline-like odour.The nitrate The hyhchloride,268 ABSTRACTS OF CBEJllChL PhPERS. tas*trnte olrnlate and acetate were also prepared. Solutions of the acetate yield precipitates with the usual alkaloidal reagents. Amido-str?~chiliiLe NH2*CZ1Hz1NZO2 may be prepared by acting on the hydrochloric acid solution of the nitro-compound with tinfoil a t about 20” ; i t forms small coloualess cubical crystals melts a t 275” and boils without decomposition a t about 280” under 5 mm. pressure ; it is insoluble in water and acbs as a diacid-base.I t s salts are con- siderably more soluble in water tban those of strychnine ; on exposure to the air they are ooloured a reddish-violet solutions of the neutr:11 salts yield precipitates with the usual alkaloidal reagents ; by treating the base dissolved in excess of nitric hydrochloric or sulphuric acid with a sol~~tion of potassium dichromate an intense pure blue coloration or in concentrated solutions even a blue precipitate is formed which if the free mineral acids be removed by the addition of sodium acetate will remain unaltered €or a week ; by warming the solution in the presence of acid idi turns violet and finally if the quantity oE free acid is considwable forms a clear yellow solution ; the reaction is as delicate as the dichromate strychnine react#ion.By heating the amido-base with alcobolic potash and chloroform i t yields the characteristic isonitrile odour. The hydrochloride NHZ.C2,H2,N,O,HCL forms long brilliant prisms and is readily soluble in water ; the platinochloride is rather unstable and forms an amorphous yellow precipitate and by dry distillation yields a quino- line-like odour. The nitrate forms octohedra and after a time turns a violet colour. By treating an alcoholic solution of the nitro- strychnine described above with alcoholic potash the potassiurr- derivative of a compound isomeric with the nitro-compound and to which the authors give the name of “xanthostrychnoZ,” is formed ; the free compound crptallises in slender yellow needles is iusoluble in water but dissolves in most of the other umal solv.ents; it yields precipitates with the alkaloYda1 reagents.The platinochloride ( C21H21N,04)2,H,PtCl forms a bright-yellow precipitate ; the nitrate mZphrzte and hydrochloride were also prepared. Although in the above compounds xanthostrychnol acts as a base it also possesses acid or pheuolic properties yielding unstable oompounds with bases. The potassium-derivative forms brilliaat ruby-red needles is decomposed by carbonic acid and is soluble in thm usual solvents ; when heated it explodes slightly; its solution yields precipitates with most of the metallic salts which are however very unstable. By acting on the hydrochloric acid solution of xanthostrychiiol with tinfoil two reduction products are formed which are not yet thoroughly examined.A monob~omstrychn~ne C?1H21BrN202 which differs from that ob- tained by Beckurts (Abstr. 1885 911) may be prepared by treating R sulphuric acid solution of strychnine with bromine the acid solution IS diluted and the base precipitated with ammonia ; it forms colourless needles which dissolve readily in water but are insoluble in alcohol ; its solntion in sulphuric acid yields an indigo-blue coloration on the addition of potassium dichromate ; its salts are more soluble in water t hnn the corresponding strychnine compounds ; the hydrochloride the nitrate and the platinochloride were prepared.ORQSNIC CHEMISTRY. 269 Strychninesulphonic acid CZlHz,N2O2-SO3H may be prepared by slowly adding 1 part of anhydrous strychnine sulphate to 6 parts of fuming sulphuric acid cont,aining 30 per cent.of the anhydride keeping the temperature below 20° and allowing the mixture to remain for a fortlnight. It forms a brittle transparent yellow mass readily soluble in water and alcohol ; i t does not yield any coloration with sulphuric acid and potassium dichromate. The barium ctdciunz potassium sodium and lead salts were prepared they are all soluble in. water. By fusing the acid with sodium hydroxide a new derivative is formed which yields a violet colour with ferric chloride. The authors have repeated the experiments of Beckett and Wright (this Journ. 1874 G 5 ) of Schiitzenberger (Annalen 108 353) and of Shenstone (Trans. 1885 141) but cannot confirm their results. An examination of the pb ysiological action of nine derivatives of strychnine shows that they all possess poisonous properties alihough in a less marked degree than strychnine itself.A. P. Strychninesulphonic Acids. By C. STOEHR (Bey. 18 3429- 3432) .-Strychnine when heated wiih concentrated sulphuric acid at loo" yields a n~onoszdpphonic acid C2~Hz~N2OZ.SO3H a colourless substance very sparingly soluble in water. Its potassium sodium and barium salts are colourless precipitates ; the arnmonI'urn salt is soluble in water but undergoes decomposition when its solution is evaporated. Concentrated sulphuric acid and sulphuric anhydride a t 150" yield a disulphonic acid Cz1H2,NzOz( SO,H) a colourless amorphous substance readily soluble in water sparingly soluble in ether and benzene; its neutral bari.z6m salt crystallises in minute plates the barium hydrogen salt is a pale-yellow amorphous powder.These results are not in exact accordance with the observations of Loebisch and Schoop (preceding Abstract). V. H. V. Piperidine from Pentamethylenediamine. By A. LADENBURG (Bey. 18 3100-3102 comp. this vol. p. 139).-18 grams of penta- methylenediamine hydrochloride were quickly distilled and the product again dist'illed with aqueous potash solution. Much ammonia is formed. The distillate was treated with strong potash solution shaken up several times with ether and the base extracted from the ether with hydrochloric acid. The salt thus obtained was identified as piperidin; hydrochloride ; the yield was 8 grams. N. H. N. Hopeine. (J. P h a ~ n z . [ 5 ] 12 460-462.)-This crystallisable narcotic alkaloid can only be obtained with difficult.y as most varieties of hops do not contain more than traces.I t was first obtained from wild American hops. The investigations of Smith Williamson Myers and Springmuhl show that the pure alkaloid has an energetic action similar to t'hat of morphine. German hops contain only traces of it ; some English varieties have given 0.05 per cent. whilst American wild hops have yielded 0.15 per cent. In the pure form it is obtained as brilliant white needles or as a white crystalline powder soluble VOL. L. t270 ABSTRACTS OF CHEMICAL PAPERS. in 800 parts of water a t 15" and in 50 parts alcohol a t 15"; it crystallises out on cooling the hot alcoholic solution. To extract hopeine hops are digested with a 16 per cent. solution of glucose containing a little acetic acid then boiled for six hours under pres- sure.The liquid is filtered t,hrough carbon and is evaporated until the sugar crystallises. The alkaloi'd is extracted from the residue by means of alcohol and the solution filtered and evaporated. The residue is treated with ether and alkali to separate certain alkaloids present and finally pure hopeine is obtained by repeated crystallisations of its alcoholic solutions. J. T. New Acid Analogous to Cholic Acid. By P. LATSCHINOFF (Ber. 18 3039-3047).-Cholic acid obtained from ox-gall was found to contain a new acid choleic acid C2,H4,0 which was separated from i t by means of the barium salt. The new acid forms large quadratic crystals (with 1; mol. H20) but separates from a concentrated solu- tion in groups of slender needles (anhydrous) ; it is less soluble in water alcohol and ether than cholic acid.The anhydrous acid melts at 185-190'. The barium (with 3 mols. H,O) and the siZver salts were prepared. When choleic acid is oxidised by means of potassium dichromate and sulphuric acid it yields cholanic acid. Cholic acicl treated in the same way yields bilianic acid. The authoii confirms the result of Hammarsten (Abstr. 1881 62.5) who obtained dehydrocholic acid by gently oxidisiiig cholic acid with chromic anhydride in acetic acid solution and repeated the experiment with choleic acid which yielded dehydrocholeic acid C2,H3,0a. This forms irregular plates with a fatty lustre melting a t 182-183". The salts are analogous to those of dehydrocholic acid but are more sparingly soluble.N. H. M. Digestion of Elastin with Pepsin. By J. HORBACZEWSKI (Chew,. Centr. 1885 843) .-Elastin is slowly digested by gastric juice with formation of hemielastin and elastinpeptone ; these substances were obtained pure by dialysis. In aqueous solution hemielastin is precipitated by acetic acid and potassium ferrocyanide whilst elastinpeptone remains unprecipitated. Hemielastin when dried for some time a t 110-120" becomes insolnble and with exception of microscopic structure acquires all the properties of elastin ; elastin- peptone contains more hydrogen and oxygen than elastin. H. P. W. Proteids. By P. SCH~TZENBERGER (Compt. rend. 101 1267- 1270) .-Noncrystallisable leucein obtained by the action of baryta on coagulated albumin only gives analytical results concordant with the formula xCaH,NOz after drying for a long time at 140-150".If dried a t 100-llO" i t retains water of constitution. Leucei'n can be split up into equal equivalents of two compounds. One is a strong ayid proteic acid of the composition CsH14NzO5 which forms a gumm1 noncrystnllisable barium salt insoluble in alcohol of 90". The other gZucoprotez/? C,H,N,04 is a neutral body soluble in water and in cold absolute alcohol. It cry stallises with difficulty in indistinctPHTSIOLOGICAL CHEMISTRY. 271 crystals. These two compounds stand in the relation of an acid and t,he corresponding alcohol and leucei'n dried a.t 1.50" represents the product of their union with liberation of water thus C,H,~N20 + C,H,N,O = H20 + C]6&8N40 or 4C4H,N0,.These facts com- bined with the author's previous researches (Abstr. 1879 542) lead to the conclusion that albumin has the formula C29&,N6010 and that its decomposition by baryta is represented by the equation C2,H4,N,O H,C,O + 2NH3 or one molecule of albumin is formed by the union of 1 mol. leuce'in with 1 mol. each of leuce'in amidovaleric acid and oxalic acid and 2 mols. of ammonia water being eliminated. This view agrees very closely both with the composition of albumin and the proportions of the products obtained by the action of baryta. Leucein when oxidised yieids products which indicat'e that it is closely related to the succinic acid series. + 7HQO = CGHiSN02 + C5HiiNO2 + [C,H,N,O + C~HI~N,O~] + C. H. B.ORGANIC CHEMISTRY.215O r g a n i c C h e m i s t r y .Physical Properties of Paraffins from Pennsylvanian Petro-leum. By A. BARTOLI and E. STRACCIATI (Gazzetta 15 417-446.)-I n this paper a number of determinations are given of the coefficientsof expansion capillarity and friction the specific volumes and specificheats indices of refraction and specific inductive powers of theparaffins from C,H to Cl6HS obtained from Pecnsylvanian petroleum.These physical constants with the exception of the specific volnmes,increase regularly with increase of molecular weight ; the specificheat is practically constant for all the hydrocarhons and the specificinductive powers are in accordance with the laws of Maxwell.Normal and Primary Monochlorobutyl-derivatives. By L.HENRY (Conipt.Tend. 101 1158-1161).-The author has prepared anumber of derivatives from chlorobromopropane CH,Cl.CH,.CH,Br,by taking advantage of the different reaction aptitudes of the groupsCHI,C1 and CH2Br. r-ChZoroButyrorlitrile CH,Cl.CH,.CH,.CN is acolourless mobile liquid with a faint disagreeable odour and apiquant taste. I t is insoluble in water but easily soluble in alcoholand i n ether; it boils without decomposition at 195-197" underordinary pressure; sp. gr. at 10" compared with water at the sameV. H. V216 ABSTRACTS OF CHEMICAL PAPERS.temperature = 1 -1620. I t dissolves in concentrated hydrochloric acidwith slight development of heat and if the solution is heated insaaled tubes the corresponding acid i q obtained.7- Ch lorohutyricacid CH2C1*CH,*CHz*COOH is a thick viscous colourless liquid witha feeble butyric odour and a burning taste ; sp. gr. at 10" = 1.2498.It is feebly corrosive and is only slightly soluble in water but dis-solves easily in alcohol and ether. When cooled in a mixture ofsodiutn sulphate and hydrochloric acid it crystallises in large thin,perfectly transparent lamellae which melt arid resolidify at 1@-10*5".7- Chlorobutyric acid does not distil without decomposition underordinary pressure ; hydrochloric acid is given off abundantly at180-185" and at 200" butyrolactone,< cH~2.coz>0 distils over. Thisis a verr convenient method of preparing butyrolactone ; the productboils a t 200-201" ; sp. gr. a t 10" = 1.1205.The methyl and ethyl salts of ychlorobutyric acid were preparedby dissolving the nitrile in the respective alcohols saturating thesolution with hydrochloric acid and heating for some time.They arecolourless liquids with an agreeable odour somewhat resembling thatof menthol and a sharp piquant taste. They are insoluble in water,and react very slowly with aqueous ammonia at the ordinary tempe-rature. Methyl y-chlorobutyrute boils at 173-174" under a pressureof 758 mm. ; sp. gr. a t 10" = 1.1894. Ethyl y-chlorobutyrate boils a t183-184" under the same pressure ; sp. gr. a t 10" = 1.1221. Normalprimary chlorobutyric chloride CH,Cl.CH,*CH,*COCl easily obtainedby the action of phosphorus trichloride on the acid is a colourlessliquid with a disagreeable suffocating odour ; sp.gr. at 10' = 1.2679.It boils a t 173-174" under a pressure of 750 mm. that is a t prac-tically the same temperature as methyl ychlorobutyrate and in thisrespect it follows the law which connects the boiling points of themethyl salts and of the acid chlorides in the biityric series. h/-Chloi-o-butgric chloride has the general properties of the acid chlorides.r- Chlorobutyramzde ~H~C1~CHz.C:H,~CONHz obtained by the action01 animonia on the methyl salt or the acid chloride is a solid com-pound which melts a t 88-90" and cannot be distilled. It is onlyslightly soluble in water but dissolves easily in hot alcohol fromwhich it crystallises in needles.By J. PONOMAREIFF (Ber. 18,3261-3275 ; compare Abstr. 1882 937).-A polymeride of cyanogenbromide C3N3Br3 is obtained by the action of dry hydrogen bromideon cyanogen bromide dissolved in absolute ether.It resembles solidcyanogen chloride in its properties. When heated a t 140-150" withacetic anhydride it decomposes into cyanuric acid and acetic bromide.Sodium ethoxide and methoxide act on it readily with formation ofnormal ethyl and methyl cyanurate respectively.Phosphorus pentachloride acts on ethyl cyanurate in the same wayas on the methyl salt with formation of solid cyanogen chloride.Ammonia at 170-180" converts ethyl cyanurate into melamine andammelineDiethylcyarturic acid C,N,(OEt),*OH isomeric with Limpricht andCH *CHC. H. B.Constitution of Cyanuric AcidOROASIC CHEMISTRY. 21 7Habich's diethylcyanuric acid is obtained by the action of baryta onnormal ethyl cyanurate.It forms a crystalline powder sparinglysoluble in alcohol and cold water. The barium saZt (with 3 mols. H,O)crystallises in plates ; it separates from a dilute aqueous solution insmall needles with 12 mols H,O. The lead and sih-er saZts were pre-pared. Ethyl iodide acts on the lead salt with formation of normalethyl cyanurate.When potassium ethyl sulphate is heated with sodium cyanurate a t160" ethyl isocyanurate is formed (compare this vol. p. 42). Ethyliodide acts on mono- and di-potassium cyanurate with formation ofdiethyl cyanurate melting a t 17:3" identical with Limpricht's com-pound (AnnuZen 109 112). By the action of methyl iodide on silvercyanurate a.t lOU" methyl isocpanurate and a small quantity ofnormal methyl cyanurate were obtained.In presence of an excessof the iodide the reaction takes place at the ordinary temperature ;the yield of normal cyanurate is then much larger.Acetic chloride acts on silver cynnurate with rise of temperatureand formation of acetic anhydride and triacetyl cyanurate C3N303Ac3.This compound melts at 170" with partial decomposition ; i t is insolu-ble in ether sparingly soluble in chloroform. When warmed withwater it decomposes into acetic and cyanuric acids.These results show that cyanuric acid belongs to the same series asthe normal and alkyl salts of cyanuric acid ; that is to say it containsthree hydroxyl-groups united with the group C3N3. N. H. M.Additive Products of Cyanogen Compounds Constitutionof Dicyandiamide and Melamine.By B. RATHKE (Ber. 18,3102-3112). - Dicyandiamide reacts readily with thiocyanic acidwith formation of thionmmeline. On the assumption that dicyan-diamine has the constitution NH,*CI(NH)*NH.CN (compare Bamberger,Abstr. 1883 logo) the author ascribes to thioammeline the formulaNH< c(NH).NH>CS. Melariurenic acid obtained by the action ofcarbonic anhydride on dicyandiamide would have an analogous con-stitution. This is contrary to the opinion expressed by Hofmann(this vol. p. 41). The author does not think however that it will bepossible to find single formulae which will account for all reactions ofthese compounds and recommends the use of Hofmann's formule(Zoc. cit.) together with his own.C (NH) *NHN.H. M.Preparation of Alkyl Bisulphides. By E. COURANT and V v.RICHTER (Ber. 18 3i7!3-3180).-It was thought probable that theaction of sulphuryl chloride on mercaptnn might lead to the formationof ethyl dithiosulphate SO,(SEt) but' the reaction takes a differentcourse and yields ethyl hisulphide. This gives a better method forthe formation of the bisulphides than those previously employed.Ethereal Salts of Nitrous Acid. By G. BERTONI (Gazzettu 15,351-360 and 361-370).-Ethyiene Nitrite ON*O*CIH,*CH,OKO.-The co:npound of the empirical formula C2H4N204 first prepared byA. J. G215 ABSTRACTS OLr CHEMICAL PAPERS.Serrienow (Zeit. Chern. 1864 lag) is regarded by some as nitro-ethylene by others as the ethylene salt of nitrous acid.The latterview is however incorrect as the true ethereal salt prepared by thegeneral process previously described by the author differs fromSemenom's compound. The process consists in distilling glyceryltrinitrite with ethylene glycol the compound passing over at90-105" ; it is redistilled in a current of carbonic anhydride.It is a mobile yellow liquid boiling a t 96-98" sp. gr. a t 0" =1.2156 insoluble in watm soluble in methyl and ethyl alcohols ether,chloroform and glycerol. When inspired it produces vertigo andparalysis of the respiratory system. On exposure to air it is graduallyconverted into oxalic acid. It gives a violet coloration with con-centrated sulphuric acid and when distilled with methyl alcohol itis converted into ethylene glvcol and methyl nitrite.Tertiary bzLtyZ nitrite CaH9*0.N0 is prepared in a manner similarto the ethylene compound from tertiary butyl alcohol and glyceryltrinitrite.It is a yellow mobile liquid boiling at 63" sp. gr. a t0" = 0.8914 sparingly soluble in water soluble in alcohol ether andchloroform. It is rapidly decomposed by acids with evolution ofnitrous fumes.The tertiary butyl nitrite obtained with its isomeric nitro-com-pound described by Tschermak as boiling a t 67-68" was probablycontaminated with its isorneride.Ally 1 Nitrite C,H,-O*NO.-Prepared as above from equimolecularproportions of glyceryl trinitrite and allyl alcohol the two liquidsbeing mixed in a vessel kept cool ; the mixture is then quickly dis-tilled the portions passing over a t 50" being retained.This fractionis then dried over lime and distilled in a water-bath below lOO",inasmuch as a t this temperature it is completely decomposed withexplosive violence. It is a mobile liquid boiling a t 44" ; sp. gr. a t 0"= 0.9546 insoluble in water soluble in methyl alcohol and decom-posing into methyl nitrite and allyl alcohol. It is rapidly decomposedby mineral acids and when heated it evolves nitrous fumes aridacraldehyde is formed. On prolonged contact with water i t is slowlydestroyed forming a white crystalline mass which is rapidly resinified.8-Hexyleneglycol and its Oxide. By A. Lim (Ber. 18 3275-3286 ).-Ethylic bromo~ropylaaetoacetnte,V. H. V.CH,Br*CH,.C H,* CHAc* C 0 OE t ,is prepared by adding a solution of 6 grams of sodium in 60 grams ofabsolute alcohol to 32 grams ethyl acetoacetate ; the product is thenadded to 80 grams trimethylene bromide.The alcohol is distilled off,the residue treated with water and shaken with dilute potash (todissolve out unchanged ethyl acetoacetate) and then dried. It isinsoluble in water but soluble in alcohol. When boiled with 5 percent. hydrochloric acid it decomposes into bromobutyl methyl ketone,alcohol aud carbonic anhydride. Alcoholic ammonia converts it intoethylic trimethyieneacetoacetate (Ber. 16 208).Normal acetobutyl alcoholic COMe*CH,*CH,*CH2*CH2-OH is obtainedby boiling 50 grams of ethyl bromopropylacetoacetate with 50 gramORGASIC CHEXISTRT. 219of water and 20 grams of hydrochloric acid (sp.gr. = 1.1) until theevolution of carbonic anhydride ceases. When cold the solution isseparated from an oil (consisting of bromine compounds) partiallydistilled and then supersaturated with potassium carboilate. Theacetobntyl alcohol separates as an oil and is dried with potassiumcarbonate and over sulphuric acid to remove ethyl alcohol. It isvery readily soluble in water alcohol and ether ; it. boils a t 154-15.5"under 718 mm. pressure with slight decomposition ; sp. gr. = 1.0143at 0". Sulphuric acidand potassium dichromate oxidise it to acetobutyric acid.Broinobutyl methyl ketone COMe*CH,.CH,*CH,-CH,Br is obtainedby distilling acetobutyl alcohol with five times the amount of stronghydrobromic acid. It is a colourless oil of agreeable odour,sparingly soluble in water readily in alcohol and ether.It boils a t214-216" (under 718 mm. pressure). Alcoholic ammonia acts on itwith formation of ammonium bromide and a base having the odourof piperidine.8-HexyZene gZycoZ OH.CHMe*CH,*CH,*CH,*CH20H is formed by theaction of sodium amalgam on acetobutyl alcohol. It is a thick colour-less liquid readily soluble in alcohol less soluble in ether. It boils a t234-235" under 710 mm. pressure sp. gr. a t 0" = 0.9809. Whenheated with fuming hydrochloric acid a t loo' it is converted into thecorresponding monochlorhydrin. This is almost insoluble in water,and has an agreeable odonr.8-Hexylene ozide <UH,-CHMc CH,-CH,*CH >0 is prepared by heating10 grams of 8-hexylene glycol with 20 grams of sulphuric acid and10 grams of water for one hour at 100".The product is diluted withwater and distilled ; the distillate is then dried by means of potassiumcarbonate and redistilled. It is a colourless liquid having a strong odonr,resembling when dilute that of ethyl ether. It boils at 103-104"(under 720 mm. pressure). It is sparingly soluble in water readilyin ether and alcohol. Water a t 225-230" and ammonia a t 200" haveno action on it. Hydrochloric acid (sp. gr. 1.1) a t 100" converts itinto the monoch Zorh y drin C HMe C1- C H,.C H,*CH,-C H,*OH mentionedabove ; prolonged heating with fuming hydrochloric acid converts itinto hexylene dichloride which can also be obtained from the glycol.The low boiling point of 8-besylene oxide and its behaviour towardsdilute hydrochloric acid support the constitutional formula ascribed toit.The eliminat'ion of water from 8-hexylene glycol does not there-fore take place in the same way as in the case of the &-glycols whichyield unsaturated alcohols.Cyanhydrin of Levulose. By H. KILIANI (Re)-. 18 3G66-3072).-Levulose was prepared by boiling 50 grams of inulin with150 grams of water and 10 C.C. of dilute sulphuric acid for eighthours. The acid was then precipitated by baryta the filtrate eva-porated and mixed with 5-6 vols. of alcohol. In 24 hours a volu-minous brown substance separated. The filtrate was evaporated to asyrup and then shaken up with strong hydrocynnic acid which con-verted the levulose into the cyanhydrin C7H,06N.This is readilyIt has an odour resembling that of camphor.N. H. M220 ABSTRACTS OF CHEMICAL PAPERS.soluble in water insoluble in alcohol and ether. When heated itsoftens between l00-105" and becomes strongly coloured. Fuminghydrochloric acid converts it a t the ordinary temperatnre into an acidwhich could only be obtained as a syrup. This when boiled withconcentrated hydriodic acid and amorphous phosphorus yields a hepto-Zactowe C7HI2O2 which boils a t 220" ; it does not solidify in a freezingmixture. When the lactone is heated with hydriodic acid and amor-phous phosphorus a t 180" it yields an acid boiling a t 209.6" whichcould not be got to solidify and therefore is not normal heptylic acid.The culcizcrn salt (with 5-6 mols.H,O) crystallises in long needles.The results do not agree with the description of calcium methybutyl-acetate given by Hecht and the acid is probably ethylpropylaceticacid. The formation of this acid would point t o the constitutionOH*C€I,~CH(OH)*CH(OH)~CO~CH(OH)-CH2~OH for levulose.The Succession of the Rate of Retrogressive Birotation ofsome Saccharoses and Glucoses with regard to their Con stitu-tional Formulz and the Extent of Affinity. By F. URECH (Rer.,18 3047-3060).-Milk-sugar is not changed by oxalic acid. When9.34 grams of milk-sugar are dissolved in 11.83 grams hydrochloricacid and kept for 28 day3 a t lo" the milk-sugar was recovered un-changed. Saccharose under the same conditions is completelyinverted in nine hours.When three times the quantity of hydro-chloric acid is used the milk-sugar is slowly inverted. According toMeissl maltose occupies a position between that of milk-sugar andsaccbarose with regard to its invertibility. Solutions of alkalis actmore quickly on maltose than on milk-sugar and more quickly cnmilk-sugar than on yaccharose. This indifferent behaviour of sacclia-rose may be accounted for by assuming that the relations of the glu-cose radicles to one another are different in sacchnrose ; for instance,that the glucoses are joined by an oxygen-atom to form an ether.Alkali Eolutions act on lactose more slowly than on dextrose andon dextrose more slowly than on levuiose ; a table with the results ofexperiments is given (compare Abstr.1884 1112).The author has already (ioc. cit.) shown that dextrose reduces alka-line copper solution more slowly than levulose ; further experimentsshow that the action of lactose is still slower. Fehling's solutiondecomposes maltose more quickly than milk-sugar ; saccharose isdecomposed slowly a t a higher temperature.The results of comparative experiments made with lactose anddextrose show taliat the retrogressive birotation of the latter takespkce rather more quickly than in the case of lactose.Composition and Properties of Raffinose. By H. PELLET andL. BIARD (Chem. Centr. 1885 47 878-87Y).-The authors confirmLoiseau's investigations. A crystalline raffinose containing 15.1 percent. of water was obtained. The rotatory power of inverted raffinosewas found to be +66.7 (sugar = 100).Scheibler gives it as +67*1.It remains to be decided whether raffinose exists ready-formed inbeetroot or is formed during the treatrnent of the sap. From theaction of acetic acid on raffinose and from other considerations theN. H. M.N. H. MORGANIC CHEMISTRT. 221authors conclude it to be a compound of crystallisable sugar withdextrin or some similar substance and a certain amount of water.H. P. W.Source of Raffinose (Melitose) in the Products of the Manu-facture of Sugar. By E. 0. v. LTPPRZANN (Ber. 18,3087-3090).-Ra,6nose was obtained directly from beetroot sap bg the methodemployed by Scheibler for the separation of railinose frorri molasses(Abstr. 1885 962). The presence of raffinose partly accounts for thehigh polarisation of beetroot sap.The author does not hold Degener’s view that the formation ofdextrorotatory sugar in beetroot beginning to decompose is due totlie action of maltose-especially as it has not been shown t h a t thelatter exists in the sap of beetroot.N. H. M.Researches on Rice-starch. By 2. SOSTEGNI (Gazzetta 15,376-384) .-On account of the discordant observations as to theamount of dextrose obtained from starch by the action of acids on it,tliis point is examined in the case of pure specimens of rice-starch.The ratio between the quantities of starch and dextrose was foundto be 93.2 100 a result in accordance with the recent researchesof Salomon ( J . pr. Chem. 25,348 and 26,342). I n order to trace outthe cause of the discrepancies the author has examined the insolublei.esidue obtained in the course of the degradation of the starch moleculeby unorpaniscd ferments or by 1 per cent.h=j-drochloric wid. Etherextracted from tlie product a mixture of fatty acids containing a pro-portion of carbon less than that required for palmitic or oleic acid.‘l’he ratio between the amido-cellulose thus purified and the dextroseobtained was found to be as 98.7 100 a result which is still lowowing t o the formation of other products of decomposition by theaction of the acid used. V. H. V.Maltodextrin. By A. HERZFELD (Ber. 18 3469-3470) .-Thispaper contains a short explanation of a few points of differencebetween the observations of Brown and Morris on maltodextrin(Trans. 1885 560) and those of the author (Abstr.1880 866). Theformer state that this compound does not undergo fermentation byNtrcclmrornyces cerevisice of the high fermentat’ion type until it isforther hydrated whereas the author found that it is readily andcompletely fermented by pressed yeast. This discrepancy arises fromthe difference. of species of yeast used. Indeed Brown a i d Morristhemselves show that nialtodextrin is fermented by the slow action ofcertain forms of saccharomyces such as 8. ellipticus and 8. pastorianusof the bottom fermentation type (comp. supra 570). The author also~ l l o w s that his former specimens of maltodextrin were not altogetherfyee from maltose and on a recent repetition of his work he is able toconfirm Brown and Morris’ data as to the composition and specificrotatory power of their rnaltodextrin.v. H. V.Action of Chlorine on Anhydrous Chloral. By H. GAUTIER(Compf. rend. 101 1161-1162).-Sixty grams O E chloral was placedi n a flask of 10 litzes capacity which was then filled with chlorineVOL. L. 222 ADSTkACTS OF CHE3lICAL PAPERP.gas. No change takes place in the dark even after 15 da,ys but indiffused light a reaction proceede slowly and in direct sunlight thecolour of the chlorine completely disappears in two or three hours.The products are hydrogen chloride carbonic chloride and carbontetrachloride ; the reaction being represented by the equation(cornp. Beilstein Hnndbuch p. 760).Preparation of Trichloracetic Acid.By A. CLERMONT (Ann.Chim. Phys. [6] 6 135-139) .-One equivalent of chloral hydrate ismelted at 50-55" one equivalent of fuming nitric acid added,and the source of heat then removed; in a few minutes nitrousvnpours are given off; the action ceases almost entirely in an hour'stime. The liquid is then heated in a tubulated retort at 123" to 195",whereby the whole of the nitric acid is removed ; above 195" trichlor-acetic acid distils as a colourless liquid which solidifies on cooling.Trichloracetic acid exists in a state of superfusion at 52*2' its normalpoint of solidification being 55.0". Acetic acid ntny be readily repro-duced from trichloracetic acid by heating equal volumes of saturatedaqueous solutions of trichloracetic and fuming hy driodic acids in asealed tube a t 100" for 12 hours the resulting liquid is exactlyiieutralised with potash evaporated to dryness and the solid massheated sufficiently to decompose any trichloracetic acid present ; thepotassium acetate may then be extracted with absolute alcohol.Action of Nitrous Acid on Sulphonediacetic Acid.By J.31. LOVI~N (Bey. 18 3241-3242) .-When 1 mol. sulphonedinceticacid (hbst,r. 1885 241) is gradually added to a well-cooled mode-rately concentrated solution of 2 mols. sodium nitrite gas consistingmainly of carbonic anhydride is evolved and the solution is found tocontain sulphuric acid and a considerable amount of hydrocyanicacid. This reaction may be explained on the assumption that pri-mary diisonitrososulphonediacetic acid is first formed and that thissimultaneously decomposes into carbonic anhydride sulphuric andlr ydrocyanic acids.Higher homologues of sulphonediacetic acidwould yield nitriles or products of their decomposition in addition tocarbonic anhydride and sulphuric acid.Action of Acid Chlorides on Inorganic Compounds. By B.LACHOWICZ (Be?-. 18 2950-2996 ; comp. Abstr. 1884 990).-Pro-pionic and euccinic chlorides act on dry lead nitrate with slight riseof temperature and formation of propionic and succinic anhydridesrespectively nitrogen peroxide and oxygen being evolved. Analogousreactions take place between the Chlorides of organic acids and allnormal anhydrous nitrates of Iiea\?y metals. All metallic carbon-ates appear to react with the acid chlorides with evolution ofcarbonic anhjdride and formation of a salt of the organic acid ; atrace of the anhydride i s also formed.With the oxides of heavymetals t8he reaction is much more vigorous ; tlie chief' product is thesalt of the organic acid (comp. Abstr. 1878 108).C. H. B.A. P.N. H. M.N. H. MORGANIC CHEMISTRY. 223Fat of the Fruit of Vateria Indica. By F. P. HORNEL and J.F. WOLFBAUER (Chenz. Certtr. 1885 762)-There have lately beenbrought into commerce under the name of butter beans some peculiarfatty seeds which are now identified as those of Vateria i n d i c a a treefrom which considerable quantities of vegetable tallow (Piney tallow,Malabar tallow) is derived. The air-dried seeds contain 49.2 per cent.of a greenish-yellow solid fat which bleaches rapidly on exposureto light and has a peculiar agreeable balsamic odour.The fatis readily saponified and yields a mixture of fatty acids melting at-56.6" and resolidifying a t ,54*8". This mixture consists of oleic acidwith solid fatty acids which melt at 63.8" and constitute about 60per cent. of the vegetable tallow. A. J. G.Synthesis of Ethyl Acetoacetate and Phloroglucinol. By A.BAEYER (Bey. 18 3454-3460).-As a preliminary point the authorreopens the discussion between Frankland Duppa and Wislicenuson the one hand and Geuther on the other regarding the constitutionof ethylic sodacet oacetate namely whether the sodium is combineddirectly with the carbon or indirectly by means of the oxygen. Againstthe latter view is the ready replacement of the metal by othergroupings which are then undoubtedly directly associated with thecarbon.Xecondly there arises the difficulty of representing the con-stitution of ethylic sodomalonate whereby it would be necessai-y toassume that the stable COOEt grouping undergoes an extraordinarytransformation leading to the production of a cqmpound of formulaCOOEt-CH C(ONa).OEt. ThirdZy the analogy drawn by Geutheras to the formation of ethylic sodacetoacetate with that ofpinacone from acetone by the action of sodium through the inter-vention of a compound ONa*CMe,*CMe,*ONa fails inasmuch a s i thas been observed that whereas sodium has no action on ethylsuccinate yet sodium ethylate free from alcohol converts it readilyinto ethyl succinosnccinate.Further the observations of Purdie onthe action of sodium ethoxide on ethyl fumarate are rationallyexplained by the intermediate formation of ekhylic sodethoxpsncci-nate and its subsequent decomposition in the presence of alcohoi withre-formation of sodium ethoxide and production of ethyl ethoxys uc-cinate (Trans. 1881 3 4 ; 1885 855) ; such an explanation is incomplete accordance with the commonly received view of the con-stitution of ethylic sodacetoacetate. On applying these facts tothe initial action of sodium on ethyl acetate it follows that theoriginal hypothesis of Frankland and Duppa regarding the inter-mediate formation of a compound ethylic sodacetate CH,Na*COOEt,is possibly correct. By the action of 1 atom of sodium on 2 mols.ofethyl malonate a t a temperature of 110" a substance of the composi-tion C,H,O is obtained crystallising in needles which melt a t 104".It is insoluble in water sparingly soluble in alcohol readily solublein ether and chloroform with pale-green fluorescence. It is analogousin its reactions to ethyl succinosnccinnte yet is much more stable ;its constitution is thus probably similar and it is doubtless derivedfrom 3 mols. of ethjl mnlonate the carbon-atoms being associated i na ring formula. It may thus be regarded as methyl phloroglucinoliri-q 224 ABSTRACTS OF CHEMICAL PAPERS.carboxylate C6(OH)J( COOEt) and this hypothesis is supported bythe formation of phloroglucinol from it by fusion with potash.Incidentally this synthesis of phloroglucinol rizises the questionwhether its composition is correctly represented by its generallyCH2.COreceived formula and not by the formula CO< CH,.CO>CH2; insupport of the latter it is mentioned that hydroxylamine reacts withphloroglucinol to form a crystalline compound melting a t 128".It isproposed to make this point a subject of further investigabion.V. H. V.Ethenylglycollic Acid. By C. A. LOBRY DE BRUYN (Rec. Tmv.Cl~irn. 4 221-235) .-Amaldehyde combines directly with hydro-cyanio acid to form the nitrile of ethenylglycollic acid which distilsa t 110" under a pressure of 85 mm. ; sp. gr. a t 15" = 1.05; it issoluble i n alcohol and ether but its preparation in a state of puritypresents considerable difficulty. On saponification with hydrochloricacid the nitrile is converted into ethenrylglycollic acid,CH CH*CH(OH)*COOH,which may be purified by means of its zinc salt.The acid is a syrupyliquid solidifiying in a vacuum after some time forming a crystallinemass of the consistency of camphor. 1t.s zinc salt crystallises with 3H20,its potassium salt is a gummy hygroscopic mass and the copper salta greenish-blue indistinctly crystalline powder very soluble in water,sparingly soluble in alcohol. The acid as also its salts readily takeup bromine a molecule of the acid combining with a molecule ofbromine ; but the acid so far as it was examined was probably not adibromerytliic acid. V. H. V.Ry HANRIOT(Compt. rend. 101 1156-1158).-The acids were distilled in contactwith a large excess of quicklime.Pyrogenic Decomposition of Organic Acids.Succinic acid yields ethane C,H604 = 2C0 + C&.A d l p i c acid yields butane C6H,0a = 2C02 + CpH:,.Glycollic acid under these conditions decomposes onlyaf a red heat,and yields methane (2 1-01s.) and hydrogen (1 vol.) and small quan-tities of liquid products which are free from methyl alcohol.Thedecomposition seems to be very complicated.This reactionrenders it possible to pass from glucose to alcohol without the inter-vention of an alcoholic ferment.Pyruvic acid yields only a very small quantity of aldehyde theremainder being in all probability decomposed in contact with thelime. C . H. B.Lactic acid yields alcohol CsH60d = C02 + C2H60.Vinaconic Acid.By R. FITTIG and R. MARBURG (Bw. 18,2413-3414).-1n this notice it is stated that Perkin's observa-tion that vinaconic acid (t rimethg-lenedicarboxylic acid) does notcombine with bromine is incorrect' inasmuch as in chlorofurm solu-tion in diffused daylight it yields a dibromo-additive productORGANIC CHEllJISTRY. 225C,H,Br2( COOH)2 in well-defined crystals which melt a t 100-11~1"with incipient decomposition.Pentamethylenedicarboxylic Acid (1,2). By W. H. PERKIN Jun.(Ber. 18 3246-3252).-E5?2yl pentanetetracayboxylate,V. H. V.CH( COOE t)2* CH,*CH,* CH,*CH ( CO OE t) 2,is prepared by gradually adding a mixture of 150 grams of eth31malonate and 76 grams of trimethylene bromide to a cooled solution of22 grams of sodium in 250 grams of absolute alcohol.I n about an hourwater is added and the whole extracted with ether. On distilling offthe ether an oil is obtained which is distilled with steam and frac-tioned under diminished pressure. The pure ether forms a very thickcolourless oil boiling a t 259-262" (under 100 mm. pressure).When saponified i t yields a brown oily acid (probably pentanetetra-CarboxyZic acid) ; this when heated gives off carbonic anhydride andyields a-pimelic acid.By treating an ethereal solution of pentnnetetracarboxylic acicl(1 mol.) with sodium ethoxide (2 mols.) a sodium compound,C1,H,O,Na is formed; and this when treated with bromine andsubsequently saponified with alcoholic potash yields pen,tarmethyZ-euetetrtrcarboxylic acid.When this is heated a t 200-220° i tdecomposes into carbonic anhydride and p e n t a m e t h y lenedic,m-bozylicacid. This acid CH,' 1 crystallises in nodular masseswhich melt a t 159-160" ; it is readily soluble in hot water alcohol,and ethyl acetate sparingly in ether benzene chloroform and lightpetroleum. The siZver salt forms a sparingly soluble white precipitate.When the acid is heated for a long time a t 300" it gives off water, C H2.CH.C 0 OH'CH,*CH*C 0 0 H,CH2*CH*CO,and yields the anhydride CH2/ ' 0 . The latter compound\ CH2* AH-C 0'melts at 64-67" is readily soluble in ether benzene chloroform andalcohol more sparingly in light petzoleum and is almost insoluble incarbon bisulphide ; if it is warmed with resorcinol and sulphurjc acid,and ammonia is subsequently added it gives the fluoresce'in reactionvery splendidly.N. H. M.Constitution of Carbopyrotritartaric Acid. Ey R. F r T ' r t G(Ber. 18 3410-3413).-1n a former paper the author has shownthat ethyl acetoacetate reacts with succinie acid to form an acidisomeric with carbopyrotritartaric acid (this vol. p. 47) ; it is pro-posed to name it methroiric acid. n'hen heated a t 200-240° it isdecomposed into carbonic anhydride and pyrotritartaric acid. Re-garding t.he constitution of carbopyl.otritartaric acid the authorregards its formation from diacetosuccinic acid as analogous t o thatof mesitj-l oxide from acetone thus giving the formula-Co<-CH ChIe- >CH*COOH. CH(CO0H226 ABSTRACTS OF CHEMICAL PAPERS.On comparison with the formula of methronic acid,C(CO0H) CMec o < ~ ~ ~ ~ ~ ( ~ ~ ~ ~ ) > ,it is seen that both are a-p-dicarboxylic acids in which the carboxylicgroupings are in relatively different positions but both acids wouldyield carbopyrotritartaric acid. V.H. V.Action of Phosphoric Chloride on Alloxan. By G. CIAMICIANand P. MAGKAGHI (Rer. 18 344$-3446).-Aa a continiiation of ob-servations on the action of phosphorus pentachloride on dichloro-rnalejimide (Abstr. 1884 Ills) the authors have examined the actionof the same reagent on alloxan. On heating together alloxan phos-phoric chloride (24 parts) and phosphorus oxychloride (24 parts)at 126-136" tetruchZocrop~?.iniidine C4NzC14 is formed. This sub-stance crystallises in micaceous leaflets melting at 67-68" a n dpossessing a penetrating d o u r resembling that of camphor.V.H. V.Thiohydantoin and its Derivatives. By R. ANDREASCH(Monatsh. Chem. 6 821-843). - By digesting the nitrosothiohy-danto'in obtained by Maly (Abstr. 1879 712) with dilute hydrochloricacid in a sealed tube a t 115-120" it is completely decomposed hy-droxylarnine occurring amongst the products of the reaction. It isprobable therefore that this compound as also the nitrosothioglycollicacid derived from it are true isonitroso-compounds a view which issupported by the fact that neither subst,ance yields Lieberman'sreaction with phenol and sulphuric acid. By the reduction of iso-nitrosothiohydantoh with tin and hydrochloric acid or with hy-driodic acid thiocarbamide and glycocine are formed together witha small quantity of a substance which is separated by means of ether ;this forms a red powder is soluble in water o r alcohol with a brilliantyellow coloration and has an acid reaction ; on the addition of alkalisit acquires a purple-red colour which on acidifying again changes toyellow.Isonitrosot hioglycollic acid when reduced by hydriodic acidyields glycocirie alone sulphur being precipitated.Imidocul.baonine-P-tkiolactic m i d E .€Iz.C ( NH).S*CH2*C Hz*C 0 OH isformed by the action of carbamide on a concentrated aqueous solutionof p-iodopropionic acid and not as was expected the correspondingthiohydantoin. This acid crystallises in needles and melts a t 175-1 76"with decomposition ; when digested with aqueous baryta dithiolacticacid and 6-thiolactic acid are formed.When a solution of the latter ismixed with dilute ferric chloride and an alkali is added a brownish-red coloration is produced which becomes more intense on shaking withair but disappears on standing. By oxidising imidocarbamine-6-thio-lactic acid dissolved in strong hydrochloric acid with potassiumchlorate at 50-60° carbamide and P-sulphopropionic acid,are obtained. The latter forms a strongly acid colonrless syrup.The silver salt forms small scales and is anhydrous ; the barium salt,HSOS*CH2*CHz*COOHORGANIC CHEMISTRY. 227C3H4BaSO5 + 5H20 is soluble in water and has a neutral reaction.This acid is also formed when broniiiie is added to an aqueous solutionof imidocarbamine-B-thiolactic acid.Methylllziohydaiatoi'~k CO<g%:>C NH may be prepared byheating methyl thiocarbamide with chloracetic acid a t 100" ; it formsalmost colourless crystals identical in appearance with thiohydantoln,but differs from t h i s compound in being soluble in ether and alcohol.By the action of nitrous acid it is converted into isoizitrosomethyZthio-hycladoztz C4H5N,S02 ; this forms a reddish powder which is insolublein ether but dissolves in alcohol and hot water ; it dissolves readily inaqueous alkalis and on heating with aqueous baryta is converted intothe barium salt of isoiiitrosomet h~lthioglycollic acid.A. P.Constitutional Formula of Thiophen. By L. GATTERMANN. A .KAISER and V. MEPEE (Her.18 3005-3012).-The results of expe-riments made by the authors show-I. That a-thiotolen from coal-taris a mixture of /3- and y-thiotolen. 31. That there are only two thio-tolenic acids which are chemically different from one another the/Aacid melting a t 126*5" and the yacid which melts at 136". Thea-acid melting a t 118" is chemically identical with the &acid; ityields the same bromo-derivative (Abstr. 1885 L206) and the cal-cium salts of both acids yield when distilled the same ketone (coin-pare p. 229). 111. That a-tribromothiotolen melting at 74" isformed by the joint crystallisation of the /3- and V-coinpounds ; whenonce formed it cannot be resolved into its constituents.These reaults remove the objections to V. Meyer's formula forthiophen (which admits of only two series of mono-derivatives),caused by the apparent existence of three series of derivatives.N.H. M.Monobromothiophen and Ethylthiophen. By E. SCHLEICHER(Ber. 18 3015-3023).-When monobromothiophen (Abstr. 1883,1091) is treated with ethyl bromide and sodium it yields /%ethyl-thiophen.Ethylthiophenic acid C4SH,Et*COOH is prepared by the action ofiodine and mercuric oxide on ethylthiophen and subsequent treat-ment of the iodo-ethylthiophen thus formed with ethyl chlorocar-honake and sodium amalgam. It forms colourless lustrous cryst&,readily soluble in alcohol and ether and melts at 71". The calciurnsalt (with 2+ mols. H,O) forms colourless needles with a silky lustre.'l'he silver salt fornis a white curdy precipitate. When ethylthiophenicacid is oxidised by potassium permanganate a thiophendiuarboxylicacid (Abstr.1885 767) is obtained.AcetoethllZthieno?ze C4SH,EtAc is obtained by treating a mixtureof 33 grams of ethylthiophen 20 grams of acetic chloride in 160 gramglight petroleum with about 30 grams of aluminium chloride ; it formsan almost colourless liquid having an agreeable odour ; the h y d r o q l -arniae-dtrivative melts a t 110". Nitracetoethylthienone NO,-CISHEtAc,forms white lustrous needles melting at 71" readily soluble inboiling water alcohol and ether. When an alcoholic solution i228 ABSTRACTS OF CHENICXL PAPERS.treated with a trace of soda it acquires a splendid purple colour.Acetoethylthiihone when oxidised yields a dicarboxylic acid identicalwith that obtained from ethylthiophenic acid.Derivatives of Brominated Thiophens.By J. ROSENRERG(Bey. 18 3027-3031 ; compare Abstr. 1885 1051). - Tribromo-thiophen sdphocldoride C4SBr3*S02C1 is prepared by boiling a weighedquantity of the sulphonic anhydride and the necessary amount ofphosphoric chloride with phosphorus oxychloride. It crystallises inyellowish-white hard needles melting a t 126". Tribromothiophen-sulphonamide C4SBr3.S02NH2 is obtained from the above compoundby the acttion of ammonium carbonate.Tribromoiiitrothiophen C&3Br3*N02 is obtained by the action offuming nitric acid on tribromothiophen suspended in sulphuric acid.Itt crystallises in matted reddish-yellow needles which melt a t 10Vand are readily soluble in ether sparingly in alcohol.When fusedtribromothiophen suspended in sulphuric acid is treated with fumingnitric acid dinitrodibromothiophen is formed identical with thatalready obtained from dibromothiophen,The author endeavoured to obtain an isomeric thiophendicarboxylicacid by distilling with potassium cyanide the thiophendisulphonicacid obtained by the sulphonation of dibromothiophen and subsequent removal of the bromine from the dibromo-disulphonic acid soobtained (this acid being isomeric with that obtained by the directsulphonation of thiophen) but mere traces of a nitrile were formed.Several substances described by Langer (Ber. 17 1566) were obtainedin a state of purity and the following corrections are made :-Dibro-mothiophen sulphochloride C4SHBr2*SO2C1 is a crystalline solid andmelts a t 32-33' ; dibromothiophen disulphochloride C4SBr2( SO,Cl),melts a t 219-220'.N.H. 31.It forms white needles.N. H. M.Methylacetathienone. By R. DEMUTH (Ber. 18 302443026).-MethyZucetothie)zone C4SH2Me*COMe is prepared by the action ofaluminium chloride on P-thiotolen and acetic chloride dissolved inlight petroleum. It forms a pale red oil boiling a t 224" (corr).The hydrox?y Zamine-derivative crystal 1 i ses in small colourless needlesmelting.Rt 119". Phenylhydrazine and sodium acetate act on methyl-acetothienone with formation of a compound melting at 131". Whenmethylacetothiihone is treated with well-cooled fuming nitric acid anifro-compound N0,-C4SHMe*COMe melting at 125" i s obtained.When methyliicetothiihone is oxidised i t yields thiophendicarboxylicacid.7-Methylthiophen behaves like the p-compound when acetylatedand yields a ketone boiling a t 216" (cow.).a- and p-Thienone. By L. GATTERMANN (Rer. 18 3012-3015).+-Thienone CO(C&3H3) is prepared by the action of carbonylchloride on thiophen ; the product is diluted with an equal volume oflight petroleum cooled and treated with aluminium chloride. It isreadily soluble in warm alcohol crystallises in colourless needles meltsat 87-88" and boils a t 326" (iincorr.). The hydrazide crystallisrsin nodules and melts a t 137". @-ThiGnone was also prepared byN. H. M0 RQANIC CHEMISTRY. 289distilling calcium P-thiophenate. The same ketone is obtained bythe distillation of calcium a-thiophenate.By F.MUHLERT (Ber. 18 3003-3005).-This acid was obtained by oxidising thiotolen (Abstr. 1885 1051).It crystallises from water in colourless needles melting a t 136". Thecalcium salt (with 9 mol. .H20) forms colourless needles ; the s i h e rsalt crystallises in iustrous needles sparingly soluble in water.Concentrated nitric acid acts on ytribromothiotolen with fcrmationof a compound C4SBrll;Ie(N02)2 melting a t 125" ; it crystallises inshort yellow prisms.N. H. M.v-Thiophenic Acid.N. H. M.Chlorobenzenes. By ISTRATI (Ann. Chim. Phys. [6] 6 367-395).-Chlorine acts on benzene in the presence of sunlight form-ing only additive compounds in the first place. When the benzene issaturated in this manner substitution-componnds are formed andpossibly all the hydrogen may be thus replaced and hexachloro-benzene hexachloride obtained.By acting on benzene with excessof chlorine in this manner and boiling the products obtained withalcoholic potash in addition to 1 2 4 trichlorobenzene and penta- andhexa-chlorobenzenes the author has obtained 1 3 4 5 tetrachloro-benzene in the pure state in considerable quantity (about 14 per cent.of the crude chlorobenzenes treated). It melts between 28" and 30",remains in a state of superfusion to a little below 20" and boils a t242-243". A. P.Separation of Mixtures of Hydrocarbons of the BenzeneSeries. By C. FRIEDEL and J. M. CRAFTS (Compt. rend. 101 1218-122:3).-The method described in this paper was devised f o r the pur-pose of separating ethylbenzene and the t.hree xylenes which areformed together with other products by the action of aluminiumchloride on toluene.It is based upon the fact that dry bromine con-taining I per cent. of iodine converts all the xylenes completely intotetrabromo-derivatives and ethylbenzene into a dibromo-derivative,the latter being subsequently converted into pentabromethylbenzent:by the action of bromine in presence of aluminium chloride orbromide. Pentabromethylhenzene was obtained by Gustavson butwas not described. It crystallises in monoclinic prisms which melt a t141.5" and can be distilled with considerable decomposition undei-ordinary pressure. Under a pressure of 160 mm. it distils unchanged.Pentnbromethylbenzene is soluble in 11 parts of light petroleum (13.p.80-90") a t 20" and the dibromo-derivative is miscible with lightpetroleum in almost all proportions. The tetrabromo-xylenes requireabout 200 parts of light petroleum for solution ; hence this liquid canbe employed to separate the various products.The mixture of hydrocarbons is mixed with about 10 times itsweight of bromine containing 1 per cent. of iodine and allowed toremain for 10 hours at the ordinary temperature. The excess ofbromine is removed by means of potash aud the dried product ex-hausted with successive portions of light petroleum until the dis-solved matter melts at a higher tempcrature than 240". The petro230 ABSTRACTS OF CHEJflCAL PAPERS.leuni is concentrated repeatedly until the tetrabromo-xylenes havealmost completely crystallised and the quantity remaining in soln-t8ion is calculated from the known solubility of these compounds.Thepetroleum is expelled from the mother-liquor by evaporation theresidue is mixed with four or five times its weight of bromine andaluminium chloride or bromide is added. After some hours the pro-duct is washed with potash crystallised from benzene and weighed,a correction being made for the small quantity of admixed tetra-bro mo-x ylenes.About 10 per cent. of ethylbenzene was isolated by this methodfrom the product boiling a t 137" obtained byheating toluene ak 110"for two days with 20 per cent. of aluminium chloride. The analysiscan be made with 5 grams of matter or even less.Ethylene and its homologues are formed by the condensation of themethjlene which is liberated in the reaction thus 2C6H5.CH = 2CsH6 + C2H4 and the ethylbeneene is produced by the reaction CsHa +In order to separate the xylenes about 2 grams of the tetrabromo-derivatives are heated in sealed tubes a t 160-1'70" (in the vapour ofpseudocumene) with 20 grams of bromine and 20 grams of water.The tetrabromp-derivatives are converted into the theoretical quanti-ties of tlie corresponding tetrabromophthalic acids C6Br4( C.H3) + 6Br2 + 4H20 = C6Br4(COOH)2 + 12HBr.Any destruction of thephthalic acids by further oxidation is indicated by the presence ofcarbonic anhydride in the tubes. The tetrabromophthalic acids areobtained in exactly the same proportions as the isomeric hydrocarbonsi n the mixture taken for analysis and they can be separated bymethods which will be described in a subsequent paper.The ortho-acid crystallises in small plates requires 400 parts of water at 15" forcomplete solution and is easily converted into the anhydride or theimide. The para-derivative crptallises in needles and gives a pre-cipitate with silver solution. The meta-derivative gives no precipitatewith silver and is much more soluble than the other two.Chlorinated Ethylbenzenes. By ISTRATI (Ann. Chim. Phys.[6] 6 395-432) .-The higher members of the series of monochlor-ethylbenzenes may be prepared by passing a further amount ofethylene into the mixture of phenyl and aluminium chlorides (Abstr.,1885 251).They are all liquids which do not crystallise a t 7" andare soluble in the usual solvents.Parachlorethylbenxeiae boils a t 181-182" and has a sp. gr. of 1.068.By boiling the mixed monochlorethylbenzenes (Zoc. cit.) with sulphuricacid four isomeric sulphonic acids are formed which may be separatedby the fractional crystallisation of' their bariiim salts.a. 2(C6H3C1EL-S03),Ba + H20 forms white needles and is verysparingly soluble in water. p. 4(C6H,C1Et.S03)zBa + SH,O formsa white crystalline powder consisting of very small needles.y. (C,H,ClEt.SO,),Ba + H,O forms colourless rhombic plates havinga brilliant lustre; and lastly 6. S(C6H,C1Et.S03),Ba + H,O formswhite granular or mamellar tufts of acicular crystals and is readilysoluble in water.CzH = CgHj'c~H'j.C.H. RORGANIC CHEMISTRY. 231The mixed monochlorodiethylbenzenes C6H3C1Eh2 have a sp. gr. of1.036 a t O" and boil between 215" and 255" ; by oxidation with chromicacid two chlorophthalic acids are obtained; the a-acid [?C1 (COOH) =1 3 51 is insoluble in water a t 15" but dissolves readily in boilinqwater and most of the ordiiiary solvents and melts at 129-130".When sublimed it readily yields the anhydride which crystallises inneedles melts at 114" and is soluble in the usual solvents. The/?-acid is insoluble in boiling water but dissolves in dilute ammoniafrom which hydrochloric acid precipitates it in amorphous whikflocks ; it is sparingly soluble in hot alcohol from which it crystallisesbetter than its isomeride ; i t dissolves in most of the ordinary solvents,melts at 123" sublimes readily a t loo" and distils without decom-position ; it probably has the constitution c6H3c1( COOH)?[?C1 (COOH) = 1 2 51.Besides these acids a third oxidation-product chlorethylbenzene m e t h y l ketone C6HsEtC1*CO&Ie was ob-tained ; i t is insoluble in hot aqueous ammonia but dissolves readilyin hot alcohol ; boils between 265-270"; by fusion with potash i t isconverted into ethylchloroberraoic acid C,H,ClEt*COOH. This is in-soluble in cold water melts a t 115" and commences to sublime at100" ; the bayium salt (~6H3CIEt*COO)2Ba forms small crystalsinsoluble in cold wat,er.The chlorotriethylbenzenes CcH,C1Ets3 boil between 235" and 260",and have a sp.gr. of 1.028 a t I" ; by oxidation with potassium per-manganate an acid was obtained in small quantities.The rnonochlorotetrethy Zbenzenes C6Hc1Et4 boil between 265" and290" ; the sp. gr. of the liquid a t 0" is 1.022.Monochloropenteth ylbenzene C6C1Et is very difficult to obtain ;it boils between 290" and 295"; the sp. gr. of the liquid at 0" is1.065. In the preparation of this compound a liquid boiling at 350"was separated; it has a reddish colour; its vapour-density is 8.85,and its sp. gr. at 0" = 1.179 ; it remains liquid at -7" and has thecomposition C,H,Cl,. A. P.New Method of Chlorination. By A. COLSON and 13. GAL'TIER( C o m p t . rend. 101 1064-1066).-When 10 C.C. of a xylene areheated with 35 grams of phosphoric chloride in sealed tubes a t about190" the products are phosphorous chloride hydrogen chloride,and a chlorine-derivative. Paraxylene yields tolylene chloride,C6H4(CH~C1) ; ortho-xylene yields the chloride corresponding withortho-xylene glycol and metaxylene the chloride corresponding withmetaxylene glycol.If 7 C.C.of toluene is heated in sealed tubes a t 190" with 30 gramsof phosphoric chloride i t yields benzyl dichloride CHPhCI,.5.5 C.C. of paraxylene heated under the same conditions with4 0 grams of phosphoric chloride yields phosphorus trichloride and achloride c6H4( CHCI,) which forms transparent crystals melting a tY 3 O and is soluble in ether light petroleum chloroform benzene andalcohol. When heated with 100 times its own weight of water thischloride is converted into terephthalic aldehyde.Ortho-xylene under the same conditions yields a correspondinqderivative which melts a t 8G0 is more soluble in ether and ligh232 ABSTRACTS OF CHEIIICAL PAPERS.petroleum than the para-compound and likewise dissolves in benzene,chloroform and alcohol.When boiled with 100 times its weight ofwater it is completely saponified and although the corresponditigaldehyde has not yet been isolated alkalimetric titration of the liquitiafter saponification shows t,hnt the chloride has t8he constitutionCsH1(CHC12)2 and not C,H,.CCl,*CH,Cl.These results show that phosphoric chloride furnishes a means ofintroducing a definite amount of chlorine into the homologues ofbenzene and that the chlorine does not act on the hydrogen of thebenzene nucleus until substitution has taken place in the lateralchains.C. H. B.Fractions of Coal-tar Oil Boiling between 170 -210" ;1 2 4 5 Durene. By K. E. SCHULZE ( B e y . 18 3032-3034).-1500 C.C. of coal-tar oil boiling between 189 and 200" previously freedfrom bases and phenols was shaken successively with quantities ofsulphuric acid of increasing strength (from 400 C.C. of 66 per cent. acidto 20 C.C. fuming acid containing 50 per cent. sulpliuric anhydride)for 10 minutes and allowed to subside for a quarter of an hour ineach case when the acid was drawn off and saponified. A residue ofparaffin remained. The last fraction but one yielded symmetricaldurene. Other modifications of durene are probably present.Theseresults are contrary to Jacobsen's hypothesis which excludes tliepossibility of the presence of tetramethyl-derivativea of benzene incoal-tar oil. N. H. &I.generally stated that metacresol does not solidify even a t -80" ; it is,however here shown that when prepared pure from metatoluidine itcan be malde to crytdallise when cooled in a freeziiig mixture to -18",by the addition of minute crystals of phenol which it resembles incrystalline form. Thus obtained it melts a t 3-4".Similar experiments with commercial metacresol were not so suc-cessful although it WRS obtained of a glassy consistlency in a freezingmixture of ether and solid carbonic anhydride.Derivatives of Phloroglucinol. By J . HERZIG (Monatsh. Chem.,6 884-888) .-Tribromophloroglucinol was prepared from pure syn-thetically produced phloroglucinol and also from the querciglucol ofGautier (Abstr.1881 272). As the loss in the preparation of thiscompound by Hlasiwetz's method is due to the simultaneous presenceof bromine and water the following modified process was adopted.Bromine was added gradually and in slight excess to a solutim ofphloroglucinol in glacial acetic acid the free bromine removed byheating on the water-bath and the tribromophloroglucinol recrpstal-lised from water the yield was 92-94 per cent. of the phloroglucinolemployed. The melting points of the tribromo-compounds producedby this method from pure phloroglucinol and from querciglucol werefound to be identical namely 148-150" and further the triacetyl-derivatives CgBr3Ac3 prepared from the tribromo-compounds by theaction of acetic anhydride and sodium acetate which crystztilise fromalcohol in colourless needles also showed in each case the sameMetacresol. By W.SI'AEDEL (Bey. 18 3443-3445)-It isV. H. VORGANIC CHEMISTRY. 233~uelting point 181-183". The difference therefore observed byGiLutier between phloroglucinol and querciglucol is apparently due tothe presence of impurities in the latter.On submitting tribromophloroglucinol to the action of dilute alkalis,the whole of the bromine is removed as hydrogen bromide aud onacidifying no precipitate is formed ; the products of this reaction liavenot yet been examiiied.Phenylmelamines and their Derivatives Normal Iso andAsymmetric Compounds.By A. W. HOFMANN (Ber. 18 3217-3234).-Triphen~lmelamine (this vol. p. 41) is best prepared by theaction of aniline on cyanuric chloride ; the product is extravted withtlilute hydrochloric acid to remove unclianged aniline and then crystal-lised from alcohol. When heated with hydrochloric acid a t l50" it isdecomposed into aniline and cyanuric acid.HemphenyZmela?nine C,N,( S Ph2)3 is obtained by the action oftliphenylnmiiie on cyanuric chloride. I t forms rhombic plates meltingabove 300' insoluble in alcohol ether chloroform &c. but can berecrystallised from nitrobenzeile. Hydrochloric acid a t 150" converts itinto diphenylamine and cFanuric acid.Phenylcyanainide is prepared by heating 15 grams of phenylthio-carbamide 25 prams of potagh 50 grams of' lead acetate and 2 litre ofwater f o r 10-15 minutes a t 100" ; the solution is then filtered andtreated with acetic acid.The amide separates as an oil which solidifieson cooling. It crystallises from water (with 4 mol. HI,O) and meltsa t 47" (comp. Abstr. 1879 804; 1880 44) ; a pZatiiiocldoi.ide,(CN*NHPh),H,PtCl and a siZrer salt CN-NAgPh were pre-pared ; they differ in composition from those described by Feuerlkin'rriphenylisomelamine (C N*Ph) ,(NH) is prepared by heatingpllenylcj-anamide for one hour a t 100" ; it melts a t 185" (comp. Bey.,3 267). The plutinochloride and auroc7~Zoritle are described. Whenstirred with cold dilute hydrochloric acid it gradually dissolves withformation of a cornpound of the formula NPh< C(NH)-NPhand much ammonium chloride.This substance when boiled wit11A. P .(lor. Cit.).CO-NPh>C:NH,CO*NPh hydrochloric acid yields a compound NPh<<co~Kph>c NH. Thiscrystallises from alcohol in needles which melt a t 272".cliloride ( C,H,N,o,),]Ei,PtCl was prepared.150" converts triphen~lisomelamine into triphenyl isocyanurate,A platino-Hydrochloric acid a tmelting at 275" (comp. Abstr. 1835 774).Asymmetrical trip7~enyZmelamine NPh<C(Ka c(NH)*NPh l-N>C-Y HPh isobtained when a solution of phenylthiocarbamide' in strong alcohol isboiled with freshly precipitated mercury oxide filtered and boiled fora long time in a reflux apparatus. From time to time the alcoholis ciistilled off and the resinous product twated with the cold alcohol.This is repeated until the resin no longer forms a clear solution irl th234 ABSTRACTS OF CHEJIICAL PAPERS.alcohol when an additional hour's boiling suffices to complete tliereaction.The product is purified by cryst'allisation from chloroform,and forms small colourless needIes melting a t 217". It is insoluble illwater but dissolves readily in all acids and is precipitated by theaddition of alkali. Theplafinochloride C21H,6N6,H2PtC16 + H,@ formssmall nodular very sparingly soluble cryst'als. The aurochloride wasalso prepared. Hydrochloric acid act,s on it a t loo" with formationof a compound Co*N'h>C*NHPh.The aui-ochloride C2,H,N60,HAuC14 crystallises in groups ofplates.When asymmetrical triphenjlmelamine is heated a t 150" with hydro-chl oric acid diphen.y lated ort hoisoc y anuric acid NPh< co-N>C -0 H,is formed. It is almost insoluble in water sparingly soluble in etherand alcohol and crystallises from the latter in groups of needles,melting a t 261" ; a silver salt C15H10AgNY03 was prepared. Concen-trated hydrochloric acid a t 280" decomposes the acid into aniline,ammonia and carbonic anhydride.CO*NPhN. H. M.Toluylenethiocarbimide. By 0. BILLETER and A. STEINER (BY.,18 3292-32993) .-Toluylenedit hiovarbamide was prepared by Lussy 'smethod (this Jour. 1875 1036) slightly modified. It formscolourless lustrous plates melting a t 206" (uncorr.). Fuming nitricacid at 120" does not act on it. Hydrochloric acid acts on it withformation of a small quantit'y of a crystalline substance probahlytoluylenethiocarbimide.l\iCetatoluylenediphenylthiocarbamide separates from a dilute soh,tion of tolnylenediamine and phenylthiocarbimide in a mixture ofalcohol and ether in small crystals melting a t 163".When boiledwith strong hydrochloric acid it decomposes into (1) toluylenediamineand phenylthiocarbimide (2) aniline and metatoh yZei~edithiocu,rbimide(toluyleneisothiocyanate) C7H6(CNSb. The latter compound crystal-lises from light petroleum in colourlcss crystals melting at 56". Itsvapour has the characteristic odour of thiocarbimides.The compound described by Lussy (loc. cit.) as toluylenethiocarbimideis probably impure phenylthiocarbimide. Toluylenethiocarbivnide canbe more ad vantageonsly prepared by Rathke's method (Annalen 167,218) from toluylenediamine.Crystallography of some Organic Compounds.By E. WICKEL(Zeit. Kryst. &Fin. 11 78-82) .-Crystals of the following compoundswere measured Metanitrobenzmesidine C6H,~~e,NHE.C0.C6H,.NOz,monosymmetric a b c = 1.6983 1 2.7838 6 = 84" 18'. Sodiummetasulphobenzoate SO3Na*C6H4*C@*OH + 2H,O asymmetric a b c= 0.5183 1 1.7144 ac = 95" 43' /3 = 103" 3 3 y = 78" 24'. Benzo-phenone rhombic a b c = 0.8511 1 0.6644. Mononitromesitylene,rhombic a b c = 0.5600 1 0.4878. Ethylacetanilide rhombic,a b c = 0.8401 1 1.0064. Ethyl anishyclroxamate C,H,@,NEt.OH(Abstr. 1883 462) monosymmetric a b c = 1.3174 1 0.85B3,/j = 86" 5 4 .N.H. M.B. H. Y,ORGANIC CHEJIISTRT. 235Crystallographic Examination of some Organic Compounds.By 0. HEINTZE (Zeit. K~ysf. Min. 11 83-88> .-Crystals of the follow-ing compounds mere measured 'rrinitroparaxyleiie C6H&1e,(N0,),monosymmetric a b c = 2.4134 1 1.9194 /3 = 75" 40'. Bariurnisophthalate C & ( ~ o * 0 ) z h -I- 6H20 asymmetric,u b c = 0.79354 1 0 61347,a = 92" 39+' /3 = 93" 48$' = 78" 534'. Nitrodiethylmetamidobenzoicacid monosymmetric a b c == 0.89385 1 1.09523 /3 = 74" 57'.Tri me thy lme tachlorop henylamm on; urn C6H4 CIoNMe3Br,rhombic a b c = 0.87535 1 0-5:3392. Compound of grape-sngarwith sodium chloride 2C6H120s7NaC1 + H20 hexagonal rhombo-hedra] a c = 1 1.7S23. Paratolptrimethylammonium iodide,rhombic a b c = 0.71'747 1 3.0549.5.Triethylentritolytriamine,N3Et3(C6HIRfe)3 monosymmetric a b c = 0.5816 1 1.0309 /3 =75" 239'. B. H. B.bromide,Action of Acetone on Aniline. By C. EXGLER and P. RIEHM(h'er. 18 3296-3297 ; comp. Abstr. 1885 1246).-A reply to Beyer(this vol. p. 145).Action of Potassium Cyanide on Dinitromethylaniline.By E. L~PPMANN aiid F. FLEISSNER (Monatsh. Chem. 6 807-817).-On slowly adding potassium cyanide (1 mol.) t,o an alcoholic solutionof dinitrodimethylaniline (1 mol.) heated a t 50° dimethylaniline anda little ammonia are given off the liquid becomes reddish-brown andafter a time blnckish- brown crystals of the potassium-derivativeof dinit?-oditizeth!/ lamidophenol separate out. The pure phenol,NMe,.C6H,(N0,)*OH prepared from this melts a t 195" is verysparingly soluble in alcohol more readily in chloroform and insolublei n benzene-; it forms clear yellow triclinic crystals exhibiting thefaces 101 101 110 and 110. The yield is about 20 per cent.of thenitro-base employed. By the action of nascent h-j-drogen o r hydrogensulphide the phenol is converted into an unstable amicio-conipound.The ammonium-derivative forms golden-yellow scales ; it melts at195". The potassium-dericative crystallises in brilliant orange-redneedles is insoluble in alcohol and sparingly soluble in water. Thesilver-derivatice forms clear red crystals which become brown on ex-posure to light ; it explodes violently when heated to 140° and is fairlysoluble in cold water.The baviuin lead and copper derivatives wereprepared. On heating diriitrodimethylaniidophenol with dilute potash,dimethylamine and the dinitroresorcinol described by Benedikt (Abstr.,1881 1132) are formed.Ortho-xylidines. By 0. JACOBSEN ( B e y . 18 3166-3168).-Areply to Wroblewsky (Ber. 18 2904).Compounds from Diazophenols and 8-Naphthylamine. By0. SACHS (Ber. 18 3125-3132; compare Abstr. 1885 1238).-When an aqueous solution of ortliodiazophenol is added to a coldalcoholic solutionof P-naphthylamine a compound OH*(& EI4N3H-C1,H,A. P236 ABSTRACTS OF CHESIICAL PAPERS.is formed. This is insoluble in water soluble in alcohol frvm whichi t crg-stallises i n slender red needles melting a t 192-19.3". 'I'heacety I-deriontive OH*C6H4N3Ac*C,oHi forms small red needles whichmelt a t 198".The bensoyl-conzpou?zd OH*C6H,*N,Bz*C1,Hi is preparedby melting together 1 part of the /3-naphthylamine-compound and2 parts of benzoic anhydride. It crcstallises horn benzene in slender,red lustrous needles melting at 163".'l'he compound OH*C6HIN,H*C,H7 is decomposed by hydrochloricacid at 150-160" with liberation of nitrogen and formation of/%naphthylamine and pyrocatechol. Bromine acts ou it yieldingdibronio-/3-naphthylamine (described by Lawson loe. tit.) and abrominated pyrocatechol. When reduced with zinc-dust and glacialacetic acid it yields Lawson's x-P-naphthylenediamine.A corresponding compound was prepared by t h e action ofparadiazophennl 011 P-naph thylamine. It forms red flat prismsmelting at 192-193" and resembles tlie orthophenol-derivativeconipletely.The acety2-derizmfive crystallises from glacial acetic acidin red lust,rous needles melting at 21 8". The Fmzoyl-tlerivniive isrcladily soluble in nitrobenzene and crgstallises in bright red lustrousneedles ; it melts a t 244".A conapound OMe*C6H4NJH*ClnHi was prepitred by the action ofmethpl orthodiazophenyl ether on P-naphthylamine. It crystallisesfrom alcohol in dark red monoclinic prisms having a metsllic lustre,2nd melts at 133". I n its behaviour it resembles the two compoundsabove described. The acetill. derivative forms very lubtrous redneedles mclting at 198-199". The beruoyl-derirative crystnllises ingroups of dark red lustrous needles which melt a t 152-153'.N.H. M.Ortharnidazo-compounds. By T. ZINCKE (Ber. 18 3142-3114) .-Orthamidazotoluene when oxidised behaves in the same wayas the compouiids from /3-naphthylamine and diazo-sal t s (compare13. %4) and yields a very stable compound,this forms colourless lustraus thin plates readily soluble inhot alcohol glacial acetic acid and beiizeiie; it iiielts at 125-126". Hot acetic anhydride and cold concentrated sulphuricacid dissolve it unchanged ; nitric acid appears to have no;iction on it. Assuming the compound to have the constitutiongiven above t h e constitution of orthamidazotolnene would be -C,H,Me<~~>N*c,H,Me. This formula does not however accountfor the formation of a diazo-compound from orthamidazotoluene andfrom its disulphonic acid which requires tlie presence of a n amido-group.N. H. M.Sulphonation of Phenylhydrazines. By A. GALLINEK and17. v. RICHTER ( H e r . 18 31 72-31 78) .-The sulphonation of thellydrazines can bs effect,ed b j slowly adding the hydrazine base tORGANIC CHEMISTRY. 237concentrated sulphuric acid strong heating being avoided. Sulphonicacids however seem only to be formed when the para-positionrelatively to the hydraxine-group is unoccupied. The sulphonic acidscan also be more readily prepared by the xct'ion of sulphuric acid onthe sodium hydrazinesulphonates (X*S2H,*S03Na) obtained asintermediate products in the preparation of the hydrazines by thoreduction of diazo-compounds with sodium sulphite and zinc-dust.Limpricht has recently obtained several of the hydrazinebenzene-sulphonic acids by reducing the corresponding diazo-compounds(Abstr. 1885 1216).Pnrahydrazinebenzenesulphonic acid NzH3*C6H4*S0,H crystallisesin flat lustrous needles with f mol.HZO. Strecker stated i t to beanhydrous. The barium lead sodium zinc and ammonium salts aredescribed. Orthohydrazinetoluenesnlphonic acid,N,H3-C6H3Me*S03H [Afe NzH3 SO,H = 1 2 ? 51crystallises in tufts of thin needles. The barium lead sodium andzinc salts are described. In correction to Bosler's statements ( Abstr.,1882,1062) it is meiitioned that orthotolylligdrazine melts a t 59" notat 56" and that the free base crystallises in needles the hydrochloridein colourless four-sided plates.Pnratolylhydrazine when heated Rrit'h sulphuric acid yields not asulphonic acid but a peculiar basic substance which is precipitatedin volnminous yellow flocks on addition of soda to the solution.It isbeing investigated.I n conclusion the author states that the method of eliminating thehydrazine-group by boiling with a solution of copper sulphate canalso be applied to the determination of the nitrogen in these sulphonicacids or i n acid solutions of their salts the nitrogen being completelyevolved in the free state. A. J. G.Additive Products of Amarine Silver Mono-substitutedDerivatives of Amarine. By A. CLAUS and L. SCHERBEL (Bw. 18,3077-3087 ; comp. Abstr. 1885 1132) .-Amurine silver methiodide,CzlH1,AgN2,MeI is prepared by the action of methyl iodide a t theordinary temperature on amarine silver to which a large quantity ofberzene has been added; in 2 or 3 days a greyish-black powder isformed which is washed with benzene and crystallised from chloro-form. It is a white pulverulent substance insoluble in ether readilysoluble in chloroform.It melts a t 173" (uncorr.). Amuriiie siluerethiodide C21H1,AgN2,EtI is obtained in the same way as the abovecompound and forms a white ponder melting a t 115" (uncorr.).Amarine silcer benzylchloride C2,HIiAgN2,C7H7C1 is formed bythe action of benzyl chloride on amarine silver a t 100". It is a whitepowder which becomes violet on exposure to light ; it melts at 250"(uncoi~.). Atnarine silver propyl iodide forms white microscopiccrystals melting a t 140" (uncorr.).M e t h y lamarine (&H17MeN2 is formed in the preparation of theabove-mentioned metbiodide.It is a white crystalline substancereadily soluble in ether benzene alcohol and chloroform ; i t melts at184" (uncorr.). Ethylamwine CZ,H,EtN formed in the preparationVOL. L. 238 ABSTRACTS OF CHEMICAL PAPERS.of amarine silver ethiodide crystallises in lustrous whitc platesmelting a t 163" (uncorr.) ; it dissolves sparingly in ether readily inalcohol benzene and chloroform.Bromoberizenc acts on asmarine silver with formation of lophine andbenzene.IC~oonobenzol/7amari?~e C21H,iBzN2 is obtained by the action of hen-zoyl chloride on amarine silver suspended in benzene a t 100". It formslarge clear prisms readily soluble i n benzene alcohol and chloroform,and melts a t 180" (niicorr.).Caustic alkali converts it into amarineand benzoic acid. The l~ydrochloride is soluble in hotl alcohol and inchloroform and melts at 802". The plutinochloride fornis a yellow,crystalline precipitate readily soluble in alcohol insoluble in ether ; itmelts a t 192". The dichron7ate and (rcrvhte are also described.Benzoy l a m a r i n e beuzoylchloride C,H,BzN2,BzCl separates from a solu-tion of its ingredients in benzene as a white crystnlline powderreadily soluble in alcohol sparingly in chloroform and light petroleuni.It melts a t 312" (uncorr.). When benzoylamnrine is boiled withalcohol dibenzoylamarine is formed (comp. Abstr. 1883 799). Bm-zoylamarine benzylchloru7e C21H17B~N21C7H,C1 fornis small brightrhombohedra insoluble in ether and benzene sparingly soluble inchloroform.It melts at 351". When boiled with alcoholic potashsolution it yields potassium chloride and benz!lIhs,rzo!/Zu,~ul.incl,C7H7*CL1H,BzN2. This forms a white powder insoluble in alcohol,ether benzene &c.IJewzylarnarine benzo?ylch7oridr C,H,.C21H,N,RzCI is obtained bythe action of benzoic chloi-ide on benzylamarine mixed with benzene.It forms long yellowish needles which melt a t 340-350". It isinsoluble in ether but dissolves readily in alcohol with decomposition,and is thus distinguished from its isomeride. The compound SOformed benzoyl benzy lamarine C21 H (C,H7) BzN is i 1is0l uble inethcr slcol~ol chloroform and dilute acids.Beiuoylumas.ine methiodide C21H17BzN2RfeI melts at 318" ; i t dis-solves in hot alcohol unchanged. Theauthor considers that the existence of the two compourids benzoyl-amarine benzylchloride and its isorneride benzylamarine benzoyl-chloride excludc Japp's formula for amarine in which both nitrogen-atoms are represented as symmetrical amido-groups.The followingformula are suggested for amarine silver and ethylamarine respect-ively :-I t melts a t 318".The ethiodide melts a t 354".N. H. 31.Preparation of Vanillin from the Gum of the Olive Tree.By A. SCHEIDEL ( D i ~ g l . polyt. J. 258 240).-The author obtainsthis substance by oxidising the gum of the olive tree. Olivil obtainedby recryshllising the gum from alcohol or its acetyl-derivative,C1B15O5Ac may also be employed.chacteristic reaction of vanillin is the productioii of a bluish-violetD. B.Dehydrodivanillin.By F. TIEMAYN (Der. 18 349.3-3496) .-ORGANIC CHEMISTRY. 239coloration with ferric chloride ; on heating dehydrodivanilti?c,OMe~CGH,(OH)(COH)~C6H2(OH) (COH)*OMe separates from tht!liquid in white needles insoluble iii ordinary menstrua but readilysoluble in potash. It is derived from 2 mols.of vanillin by the abstraction of 2 atoms of hydrogen. I t s formationis Etnalogous to that of dithymol from thymol and of cedriret fromethylic dimethylpyrogallol ether by means of the same reaction. De-l~ydrodivanillin when heated with sodium methoxide and methyliodide is converted into the corresponding dimefli y 1 ether,It melts a t 303-304'.c 1,H I ( c 0 H ) 2 ( 0 31 e) 4 ,which crystallises in white needles melting at 131-138" insoluble inwater and alkalis but more soluble than its parent compound inalcohol and ether.Deli yd~od~p~otocatechuic acid C,2H,(OH),(COOH)L,obtained from dehydrodivanillin by fusion with potash and subse-quent purification by means of the calcium salt is an amorphousflocculent substance melting a t above 300" ; i t is slightly soluble inwater and more soluble in alcohol. With ferric chloride it gives thecharacteristic colonr reactions of protocatechuic acid with coppersulphate a brownish-red with silver nitrate a brown with lead acetatca voluminous white and with zinc sulphate a white precipitate.V. H. V.Resacetophenone. By A. MICHAEL and G.31. P A L b x m (Amer.Cherrz. J. 7 275-277).-Nencki and Sieber (Abstr. 1881 591 arid811) have given to resacetophenone the constitutional formulaC6H3( OH) 2*C 0.C H3,whilst the authors had regarded i t as more probably represented byC,T3,<O>C(OH)*CH3 0 as it forms only a single monacetyl-derivative.By the action of phenylhpdrazine on resacetophenone in alcoholicsolution a crystalline substance is formed melting a t 159" andhaviug a composition agreeing with the formulaC,H3(OH),.CMe N,HPh.Thus it would seem that a carbonyl-group is present although it wasfound impossible to obtain a diacetyl-derivative even by using aceticanhydride and sodium acetate.Nencki and Sieber were unable t,o obtain a hydroxyacetophenoneby the action of zinc chloride on phenol and acetic acid; but byincreasing the amount of zinc chloride this substance C,H,(OH)Ac,can be prepared; it crystallises in needles melts at log" and isinsoluble in water but dissolves in alcohol.H. B.Polythymoquinone. By C. LIEBERMANN and M. ILINSKI (Rer. 18,3193-3201 ; comp. Abstr. 1878 418).-When polythymoquinone isdistilled it is reconverted into thymoquinone B small quantity of thymo-quinol being also formed. Thymoquiiione boils a t 332" under 760 mm.pressure not at about 200" as stated by Carstnnjen (this .Tour. 1877.350). When polytliymoquinone is heated with stannous chloride and1 . 240 ABSTRACTS OF CHENICAL PAPERS.hydrochloric acid o r with zinc-dust and ammonia or is distilled withzinc-dust it is converted int,o thymoquinol.Polythymoquinone phenylhydraxide (c6H2MePr<g!&->)a pre-pared by boiling the quinone with phenylhydrazine hydrochlorideand alcohol crystallises in lustrous orange microscopic cubes com-mences to decompose a t 243" and melts at 249".Polythymoquinone monoxime (C,H,MePr<N(EH)>) is obtainedby dissolving 10 grams of the quinone in 30d c.c of 80 per cent.alcohol adding 10 grams of hydroxylamine hydrochloride and boilingfor 2-3 hours.It is a crystalline powder insoluble in water; itblackens a t 240" and melts a t 264" with decomposition; if heatedquickly it explodes. Like other quinoximes it shows feebly basic aswell as acid properties. When reduced with stannous chloride ityields amidothymol.is prepared by heating theqninone with hydroxylamine hydrochloride soda and absolute alcohola t 145" for two hours.It is a sparingly soluble heavy white powder,melts with decomposition at about 290" and closely resembles themonoxime. When reduced with st'annons chloride and hydrochloricacitl. i t yields paradiamidocymene hydrochloride C6H2MePr( NH,Cl) ;this forms colourless needles and when oxidised yields thymoqui-none.Expeyirnents ape being made on the polymerisation of otherqui non 8s.The dioxime (C6H2MePr<A. J. G.Ethyl Benzoylcyanacetate and Cyanacetophenone. ByHALLER (Conzpt. rend. 101 1270-1273) .-Ethyl benzoylcyanacetateis obtained by the action of cyanogen chloride on ethyl benzoylacetate.2.4 grams of sodium is dissolved in 30 grams of absolute alcohol,20 grams of ethyl benzoylacetate is added to the cooled mixture anddry cyanoqen chloride is passed into the liquid until the alkalinereaction disappears.The liquid is then filtered concentrated byevaporation and the residue heated with water and agitated wit>hether to remove unaltered ethyl benzoylacetate. The aqueous solutionis supersaturated with sulphuric acid and repeatedly agitated withether The ethereal solutions are coricentrated by evaporation andthe ethyl benzoylcyanacetate purified by repeated recrystallisation. Itforms hard transparent prisms which melt a t 37.5" and are soluble inalcohol ether potassium hydroxide and sodium carbonate. Itsalcoholic solution is distinctly acid and gives a red coloration withferric salts.Like its analogues ethyl benzoylcyanacetate combineswith bases and forms salts. The barium salt forms white crystals,soluble in alcohol but less soluble in water and not decomposed byboiling ; the calcium salt is very similar.When treated with a saturated solution of hydrochloric acid inabsolute alcohol ethyl benzoylcyanacetat,e yields carbonic anhydride,ammonium chloride et.hyl acetate and ethyl benzoate. If boiled witha large quantity of water it yields cyanacetophenone the decomposiORGANIC CHEMISTRY. 2-11tion being represented by the equation COPh*CH(CN)-COOEt + H,O= CO + C,H,O + COPh.CH,.CN. Cyanacetophenone has a dis-tinctly acid reaction ; it dissolves i n sodium carbonate and seems toform a crystallisable salt.Derivatives of Durylic Acid.By J. U. NEF (Ber. 18 3496-3499) .-A continuation of the author's investigations of durene (thisvol. p. 64). DianiidoduiyZic acid C6Mes(NH?),.COOH,isobtained by thereduction of hhe corresponding dinitro-derivative. It crystallisea insilky needles me1 ts at 221" with decomposition is sparingly solublein cold water more soluble in hot and in alcohol. When dissolved inhydrochloric acid it is oxidised by ferric chloride into dumquinone-carbozylic acid C802Me3.COOH which crystal lises in tufts of needles,soluble in ordinary menstrua ; it decomposes a t 130" with evolutionof gas. It gives a yellow amorphous precipitate with lead acetate,and a compound wikh phenylhydrazine insoluble in ether. It is thefirst example of a benzoquinonecarboxglic acid.On reduction withzinc-dust in alkaline solution it is converted into the correspondingquinol or dihydmxyd u ~ y l i c acid C6h!te3( O.K),-COOH which crjstallisesin grouped needles melting a t 190)" with decomposition. It issparingly soluble in cold water but more soluble in hot. The alkalinesolutions are of a deep-violet colour ; it is reconverted into the qui-none acid by ferric chloride.Benzallevulinic Acid. By H. ERDMANN (Ber. 18 3441-3443).-BenzalZecuZinic acid CI2Hl2O3 is obtained by heating a mixture ofbenzaldehyde levulinic acid and sodium acetate ; it forms minute,compact crystals which do not however show a very definitemelting point (120-125"). It dissolves in concentrated sulphuricacid with production of a n intense red coloration ; it is decomposed byconcentrated potash with separation of benzaldehyde.When reducedin alkaline solution it forms a 7-hjdroxy-acid decomposed on acidifi-cation into benzylvalerolactone The author ascribes provisionallythe formula CHPhC. H. B.V. H. V.C(CH2Ac)*COOH to benzallevulinic acid.V. H. P.Perkin's Reaction. Synthesis of a Sulphur-derivative ofCinnamic Acid. By .J. M. LOVBN (Ber. 18 3242-3245).-Amixture of 15 grams of thiodiglgcollic acid with 20 grams of benz-aldehyde and 40 grams of acetic anhydride was heated with 5 to 10grams of fused anhydrous sodium acetate for 2 to 1 hour. Theproduct WRS poured into water when a thick brown oil separatedwhich gradually became crystalline. This mas treated with animalcharcoal and further purified by means of the sodium salt.The newcompound COOH.C( CHPh).S.C( CHPh)*COOH is insoluble in water,readily soluble in ether and in hot alcohol and separates from thelatter in small pale-yellow crystals which do not melt without decom-position. The sodium sult ClsH,SO4Na + 2&H,O fornis thin plateswith a silvery lust're. A bromine-derivative Cl8Hl2Br2SOJ was obtainedby the action of bromine a t 100" on a solution of the acid in chloro-form. It is readily soluble in alcohol from wliich it separates in shor242 ABSTRACTS OF CHEMICAL PAPERS.yellow prisms very similar in appearance to the original acid onlyyellower and larger.Introduction of the Carboxyl-group into Phenols. By S. V.KOSTANECKI (Ber. 18 3202-3206).-The author points out that themetbod of directly introducing a carboxyl-group into polyhydricphenols by heating them with aqueous sodium or potassium hydrogencarbonates only succeeds with those phenols containing two hydroxyl-groups in the meta-position relatively to one another.Cresorr,inolcarbo~:1/lic acid C6H,Me( OH)2*COOH is prepared byheating cresorcinol (1 part) with potassium hydrogen carbonate(4 parts) and water (5 to 10 parts) for 15 minutes ; the product ofthe reaction is then acidified extracted with ether &c.I t crystalliseswith L no$. H20 in very long thin colourless lustrous prisms meltsa t 208" with evolution of carbonic anhydride is readily soluble inether alcohol and hot wafer and gives a bluish-violet colorationwith ferric chloride.[OH COOH 0 H M e = 1 2 3 6 or 1 4 3 61,as the remaining possible constitntion [COOH = 51 has been shownto belong to cresorsellinic acid.Pyrogallol is also readily converted into an acid when heated withpotassium hydrogen carbonate ; this proved to be identical with theknown pyrogallolcarboxylic acid.Derivatives of Phthalide.By M. HOENIG (Ber. 18 3447-3450).-When phthalide is heated with fuming nitric acid it yields aN. H. M.The acid must have the constitutionA. J. G.mononitro-derivative N02*C6H3<cH2>0 co [CO CH2 NOz = 1 2 41,which crystallises in long colourless needles melting at 141" nearlyinsoluble in cold water more soluble in hot alcohol and ether. Whenheated with chromic acid it yields unsymmetrical nitrophthalic acid.When reduced with tin and hvdrochloric acid it is converted intoamidophthalide N H z * C H 3 < ~ ~ 9 > 0 [CO C02 NH2 = 1 2 41,which crystallises in short prisms melting a t 178" insoluble in coldwater sparingly soluble in alcohol and ether ; its hydrochloride crystal-lises in needles and its platinochloride in minute rhombohedra.Nitrophthalidc when heated with phosphorus and hydriodic acid,yields the pnosphate of amidotoluic acid COOH*C6H3Me.NH2,H3P04,from which the free acid is obtained by decomposition with bariumcarbonate and subsequent addition of sulphuric acid.It crystallisesin colourless needles which melt a t I53" and are sparingly soluble incold moderately soluble in hot water and alcohol ; its copper salt is agreen precipitate consisting of minute crystals.Nit~-o-orthoh2Jdroxy-m e t hy Zbenao L'c acid,prepared by heating nitrophthalide with alkalis crystallises in minuteneedles which melt a t 129" ; it is very soluble in ether alcohol andhot water ; its silver salt forms grouped needles.The corresponding amiclo-derivative OH*CH2*CGH3(NH2)*COOH isOH*CH,.C6H3(NO2).COOH [COOH CHZ-OH NO = 1 2 41ORGANIC CHEMISTRY. 243best obtained from amidophthalide. When heated wit,h fumingsulphuric acid phthalide yields a sulphonic acid S03H*C6H3<CH,>0,which crystallises in colourless deliquescent needles very soluble inalcohol insoluble in ether and chloroform. Its barium salt crystal-lises in colourless prisms t!he copper salt in large glistening light-blue prisms containing 2 niols.€LO and the sodium salt in hygro-scopic needles. V. H. V.By W. ROSER (Ber. 18 3115-3125).-Ethylenediphthalyl dissolves readily in boiling alkali solution to whichalcohol has been added. When acidified the solution yields ethylene-benzoylbenzoic acid melting a t 172". When ethylenebenzoyl-orthocai*boxylic acid is treated with hydrochloric acid it yieldsethylenediphthalyl and an anhydride ClsH,05 (a-) already describedby Gabriel. The p-anhydride ClsN1205 is formed when the acid isheated a t 100" with hydrochloric acid for 10 hours. It is insolublein water readily soluble in hot alcohol and crystallises in prismsmelting a t 200-202". When boiled with alkali it is converted (likethe a- an h j dride) into eth jlenebenzo y lorthocar box y 1 ic acid.Thefollowing formula are proposed for the a- and @-anhydride :-coPhthalyl-derivatives.When the double lactone Cl,H904 (Abstr. 1885 267) is boiled i tyields carbonic anhydride and phthazethylidene <c&,o>C c H4 CHMe,which crystallises in small lustrous plates and melts at 67-69'.This compound is converted by boiIing with alkali into henzogl-eth2/l~)rthocarbnxyZic ucid COOH.(&H4*C0.Et. This acid was preparedby Gabriel and described by him as propiophenoneort hocarboxylicacid.pi- Pheny 1 butyric-orthocad3oxy lic acid,COO H*C~H4*CH,.CH,*CH~*COOH,is obtained by the action of hydriodic acid and amorphous phos-phorus on the double lactone (7oc. cif.). It forms small lustrousplates which melt a t 138-139"; i t is sparingly soluble in water readilyin alcohol.P-Phthalirnidy~ropionic acid CO< $ z > C CH*CH,*COOH isobtained by the action of aqueous ammonia on the double lactone andsubsequent addition of hydrochloric acid to the solution. It issparingly soluble in water readily in hot alcohol and crystallises inslender slightly yellow needles melting a t 225".Salts are described.CO <%z>C< __ co> isomericwith the compound last described is prepared by evaporating asolution of the double lactone in strong alcoholic ammonia. It formsThe barium and silver salts are described.C El,* C H Phtha,limidy~ropiolactone244 ABSTRACTS O F CHEJIICAL PAPERS.small bright rhoinbic plates which melt with decomposition a t 20.5" ;it dissolves readily in hot water and alcohol.Alkalis dissolve i treadily with formation of salts of a bibasic acid Cl1H,NOa thebarium calciuu11c and silver salts are described. The constitution ofthe acid is probably COOI'I.C,H,.C (NH)*CH,-CH,*COOH.Diphthalsuccinanilide C30H2dN204 is contlainad i n the anilinemot her-liquor i n the preparation of iso-ethylenediphthalyl (loc. cit.).I t is readily soluble in nitrobenzene and aniline sparingly in hotalcohol from which it separates as a white crystalline powder; itmelts a t 267" with decomposition. When boiled with glacial aceticacid and hydrochloric acid it yields di23htha1succindehydranilide7C30H20N202. This is insoluble in water and alcohol sparingly solublein glacial acetic acid.It melts above 280". Alcoholic solution ofpottash acts on it with formation of an acid not further examined.N. H. M.Carbostyril. By E. ERLENMEYER and J. ROSENHEK (Ber. 18,3295).-By the action of a solution of hypochlorous acid obtained bytreating a solution of bleaching powder with boric acid (Abstr. 1885,1194) on quinoline carbostyril was obtained together with other pro-ducts. From a hot dilute aqueous solution (about 1 100) carbostyrilcrystallises with 1 mol. H,O in very thin long threads like asbestos ;from a concentrated solution it separates in anhydrous lustrousprisms. N. H. M.Constitution of the Compounds obtained from p-Naphthyl-amine and Diazo-salts their Behaviour on Oxidation. BJ-T. ZINCKE (Ber. 18 313.L-3141).-1'he fact that these compouiidsdo not react with nitrous acid makes it improbable that they containNH,-groups.Oxidation experiments show that they contain twoNH-groups. They probably belong to the class of compounds de-scribed by Griess as azimido-compounds. Thus the benzene-deriva-tive (Abstr. 1885 802) would have the constitution-PhN<NH>CloH6 N H or NHPh*N<b NH- H6>.J l ONBenzeneuxi~~~idora~~thalene PhN/ I \C,H6 is obtained by the 'doxidation of the hydroazimido-compound (from diazobenzene and,!3-naphthylamine) in acetic acid solution with chromic anhjdride. Itforms nodular groups of white slender needles readily soluble inglacial acetic acid sparingly in alcoliol and benzene. It melts at107-108".Ortho~~~~droxybenzemeazimido?aa~ht7,alene OH*C6H4*N3 C10H6 is pre-pared by the action of lead dioxide on a solution of the hydro-corn-pound in dilute alkali.I t crystallises in white needles having asilky lustre and melts a t 140'. It is insoluble in carbonates but dis-solves readily in hot glacial acetic acid alcohol benzene and aqueousalkalis. Concentrated nitric acid and bromine act on i t with forma-tion of compounds melting respectively a t 21 5-220" and 198-200"ORGANIC CIIEIiIISTRY. 245Concentrated sulphuric acid dissol~es both compounds above describedwithout change ; reducing agents have no action on them.Paralzyd?.oxybenzenenzimidona~hthale?ze is prepared in mannersimilar to the ortho-derivative. It crystallises from glacial aceticacid in three forms and melts a t 198-199'.It dissolves readily inacetic anhydride with formation of an acetyl-derivative melting a t164-165'. N. H. &I.Azonaphthalene and its Derivatives. By R. NIETZKI and 0.GOLL (Ber. 18 3252-3260).-a-Azonaplithalene (Abstr. 1885 545)is best prepared by adding 5 parts of sulphuric acid to a solution of1 part of amidoazonaphthalene in 100 parts of 95 per cent. alcohol ; thetheoretical amount of sodium nitrit,e dissolved in water is then added,the mliole boiled for some hours and precipitated with water. Thecrude product is dissolved in hot aniline and alcohol is added to thesolut,ion when steel-blue crystals of azonaphthalene separate as it cools.It dissolves in sulphuric acid yielding a blue solution ; when this isheated a t 183" the colour changes to violet and the solution acquiresa splendid brick-red fluorescence.Hydrazonn~,hthuZeize CIOH7*NH*NH*C1OH is obtained by boiling asolution of 16 parts of soda in 160-170 parts of alcohol in which1 part. of azonaphthalene is suspended and then adding zinc-dust untilthe solution is decolorised.The product is filtered directly into watercoutaining ammonium sulphide. and the precipitate thus formeddried and extracted with benzene. It forms colourless plates meltinga t 275" insoluble in water readily soluble in alcohol ether andbenzene.Naphthiclin,e NH2*CloHs*CloEifi*NHz is prepared by the action ofstaniious chloride on a solution of the azo-compound in glacial aceticacid. 1 t crystallises from dilute alcohol in lustrous plates resemblingbenzidine and melts a t 198".The /i ydrocldoride C,oH,N,2HCl,forms colourless lustrous plates ; the platinochZoritle crystallises inyellow needles which become greenish when dried ; the sulphateforms lustrous plates. When a svlution of a naphthidine salt istreated w i t h ferric chloride or chromic anhydride it acquires asplendid crimson colour. When warmed with chromic anhydride,it yields a-naphthaquinone and phthalic acid. The diacetyl-derivat ive,C20HlJN2A~2 melts above 300" and is almost insoluble in the usualsolvents. Nitrous acid converts naphthidine into a diazo-comzpoud,which yields violet azo-dyes with /j-naphtholsulphonic acids. ThepZcrtitLochZoride is described. By converting naphthidine sulphate intothe diazo-compound and decotriposing the latter with alcohol a hydro-carbon was obtained melting a t 153.5" ; it is probably identical withLossen's a-a-dinaph tIiyl.Dinayhtll yline C,H,N2 is formed by treating hydrazonaphthalenewith hydrochloric acid. It crystallises from beiizene in colourlessplates melting at 273".The salts are readily soluble; when boiledwith acids even acetic acid they give up ammonia and yield di-naphthylimide. When oxidised phthalic acid is formed. The diazo-compound yielded a hydrocarbon identical with that obtained fro runapht hidine.I n the dry state i t is stable246 ABSTRACTS OF CHEMICAL PAPERS.ninupl2fhyZcarbnxoZe < g::g:>NH is prepared by boiling a stronglyacid solution of dinaphthyline hydrochloride.J t forms long colourlessneedles which melt a t 216". It sublimes without decomposition. Itdissolves in sulphuric acid forming a reddish-brown solution whichbecomes deep green on addition of a trace of nitric acid. The pici-ateforms red needles melting a t 226" ; it is decomposed by ammonia.When a solution of dinaphthylcarbazole in glacial acetic acid is treatedwith sodium nitrite a nitrosamine is formed which crystallises insmall yellow plates melting above 300". Acetic anhydride a t 220"converts dinaphthylcarbazole into an acetyl-derivative. It formscolourless plates which melt above 3CO" ; it is insoluble in benzene.N. H. M.Naphtholazobenzenes. By A. DENARO (Guzzettu 15,405 -409).-Four isomeric naphtholazobenzenes 0H~CI0H6.N2*C6H5 are possible,namely two derivable from a- and two from @-naphthol.By frac-t'ional crystallisation from alcohol the two lat ter are separated fromthe crude product of the action of potassium nitrite on aniline nitrateand P-naphthol; the one forms cherry-red prisms melting at 132"(comp. Margary Abstr. 1885 546) the other is a red crystallinepowder melting a t 120". The former yields an acetyl-derivative,CI~H~~N,*OAC a s a brown crystalline substance melting a t 95".On reduction with tin and hydrochloric acid aniline hydrochlorideand @-amido-P-iiaphthol (NH OH = 2 3) are formed thusproving that the hydroxyl and azo-groupings are in the positions 2 3respectively.Of the isomeric a-nnphtholnzobenzenes one crystallises in minute,red needles melting a t 166" the other is a violet powder melting a t175".The former yields an acetyl-derivative melting a t 340° and onreduction and subsequent oxidation of the nmido-naphthol formed ityields a-naphthaquinone ; it is therefore a 1 4-derivative.V. H. V.2 3 Naphtholsulphonic Acid. By A. CLAUS and 0. VOLZ(Bey. 18 3154-3162).-The following salts of this mid aredescribed :-Sodium salts ONa*CloH6*S03Na and OH*C10H6*S03Na,normal zinc salt with 2 inol. HzO normal lead salt with 24 mol. H20,basic lead salts CI0H6SO3,2PbO and CloH6SO3,2Pb0,OH2. By theaction of phosphoric chloride on the acid a t temperatures below150° several complex ethereal salts are obtained ; a t temperaturesabove 150" a chloronaphthol and a dichloronaphthalene are mainlyformed.The chZoronaphthoZ CloH6Cl*OH [OH C1 = 2 31 is obtainedby recrystallisation or sublimation in slender colourless needles ; itmelts a t 101' (uncorr.) and is moderately soluble in hot. water andlight petroleum very readily in most other solvents.2 3 dichZoronaphthalene CloH6CIz crysfnllises in lustrous plates,melts a t 61.5" (uncorr.) boils a t 286" and seems to be identicalwith the 6-dichloronaphthalcne of CGve (Abstr. 1878 676). Theoxidation of these substances was attended with great difficulty.With chromic acid under the most favourable conditions abouORGANIC CHEMISTRY. 24710 per cent. of a dichloronaphthaquinone was obtained which wasfound to be the known dichloroquinone [O C1 C1 0 = 1 2 3 41.0 A dinaphthylena ether C,,H,<O >CloH was obtained by heatingeither 2 3 dichloronaphthalene or the corresponding chloronaphtholor naphtholsulphonic acid with sodium carbonate and potassiumnitrate a t 300".It sublimes in golden-yellow lustrous prismaticneedles melts at 229" (uncorr.) and is soluble in chloroform aceticacid ether and alcohol to sulphur-yellow solutions showing a sea-green fluorescence. A. J. G.p-Dichloronaphthaquinone ; Constitution of 6-Dichloronaph-thalene. By A. CLAUS and P. F. MELLER (Ber. 18 3073-3076).-f3-Dichlorona~A,thapuinone CloH4ClzOz is obtained as an intenselyyellow powder by the oxidation of e-dichloronaphthalene (Abstr. 1882,734). It melts a t 148-149" (uncorr.) and sublimes unchanged.When boiled with alkalis i t gives up one chlorine-atom and yields/Lhydroxychloronaphthaquinone CI,H4ClO2*OH. This crystallises inslender bright-yellow needles which melt at 203" (uncorr.) ; it issparingly soluble in water readily in alcohol ether chloroforin? andglacial acetic acid.The alkali derivatives form small red crystals,readily soluble in water; the barium and cnlcium derivatives arebright-red and dissolve in much water. The silver copper and Zeatdderivatives are also described. 13 - Chloronaphtlinquinone - anilide,C,oH4C102*NHPh is obtained by boiling an alcoholic solution ofP-dichloronaphthaquinone with aniline. It forms dark reddish-violetcrystals which dissolve sparingly in alcohol readily in glacial aceticacid. It melts a t 155" (uncorr.). /I-Chloronaphthapuinone - ortlio-toZitide melts a t 175" (uncorr.) ; theparatoluida melts at 164" (uncorr.).The formation of p-dichloronaphthaquinone and of a mono-chlorophthalic acid in the oxidation of 6-dichloronaphthalene (7oc.cit.) show that in the latter compound the chlorine-atoms must havet'he P-position and must be on different sides of the naphthalenenucleus.N. El. M.p-Hydroxanthranole. By K. E. SCHULZE (Ber. 18 3036-3039). - p-HydroxanlhranoZe OH-C -C.OH is obtained by theaction of lead peroxide on pure anthracene dissolved in glacial aceticacid. Several precautions described in detail have to be taken,owing t o the ease with which the substance is oxidised. It resembleshydroxanthranole in most of its propert,ies but is distinguished byits behaviour towards an alkaline copper solution from which itcauses a separation of cuprous oxide ; hydroxanthranole merelydecolorises the solution.An ethyl ether C,8H1802 was prepared byboiling ,%hydroxanthranole with ethyl iodide and alcohol for anhour ; it forms transparent amber-coloured crystals. The methy1ether ci-ystallises in transparent yellow square plates which melt a t196". The beiizyl ether forms lustrous colourless crystals melting a t2.20". N. H. M.,G&\\C,H4248 ABSTRACTS OF CHEMICAL PAPERS.Anthrapinacone. By K. E. S c H m z E (Ber. 18 3034-3036).-Aizthrapinacone CH2<c6H'>C(OH)*C( C6H4 O H ) < ~ ~ ~ > C H is pre-pared by acting on anthraqninone with zinc-dust and ammonia andsubsequently treating the zinc-dust with hot xylene ; on cooling thisyields long white needles of the pinacone which resemble dihydro-anchranole in appearance but is much more sparingly soluble i nalcohol.When heated it melts a t 182" and a tthe same time loses water' with formation of diantlzranyl,It is very electric.Chlor- and Brom-anthracenecarboxylic Acids Action ofCarbonyl Chloride on Phenanthrene. By G. BEHLA (Ber. 18,3169-3171) .-Graebe and Liebermanii have shown (this Journ.,1872 139) that the chloride of one of the three anthracenedi-carboxylic acids is formed when anthracene is heated with carbonyichloride at 180-200". The author finds that a t higher tempera-tures the known dichloranthracene CC1- /CCI and the'c6H4chloride of a monocarboxylic acid are formed. This chZoranthrace?t e-carbozylicacid CCl-C*COOH is also obtained by the action ofchlorine on a solution of anthracenecarboxylic acid in chloroform.Itis crystalline and melts at 258-259" ; wlieri heated above it,s meltingpoint in sealed tubes i t is resolved into carbonic anhydride andchloranthracene.A bromaiath?.acenecarbvxyZic acid crystallisiiig in needles bas beenobtained i n a similar niauner.Carbonyl chloride does not act on phenanthrene a t 200" ; between250" and 280" a very small quantity of a substance was obtainedsoluble in soda and crystallising from benzene in needles. C,H4\,CsH4\\C,Hj/When oxidised it yields anthraquinone.A. J. G.Crystallography of some Camphor-derivatives. By V. V.ZEPHAROVICH (Zeit. Kryst. Min. 11 42-51).-The author gives theresults of measurements of crjstals of the following compounds:-Cam-pholic acid CloHla02 monosymmetric a b c = 1.0935 1 1.2810,/3 = 64" 40$'.Nitrohydroxy-camphor Cl,H15(NO~) 02 monosym-metric a b c = 0.7617 1 0.4310 /3 = 89" 184'. Bromonitro-camphor Cl,-,HI4Br(NO2)O rhombic a b c = 0.7390 1 0.4757.Dibromonitro-camphor C1,H,3Br,(N02)0 rhombic a b c =0.8472 1 0.5684. Anhydrocamphoronic acid CSHl2O5 rhombic,a b c = 0.9634 1 0.8170. Camphor-derivative C8HL204 ob-tained by oxidising camphoronic acid rhombic a b c =0 9877 1 1.1236. Silver salt of C8H120i C8HuAg04 asymmetric,a b c = 0.5726 1 0.5737 axial angles u = 92" 3' 34" =95" 14' 44" = 91" 52' 35". Potassium-derivative of dinitrobromORGANIC CHEMISTRY.249methane CKRr(NO,).? asymmetric,a = 77" 15' 17" /3 = 117" 3' 51t' '1 = 98" 49' 24".a b c = 0.2345 1 0.6619,B. H. B.The Camphor Group. By W. ROSEK (Bey. 18 3112-311,5).-When camphor is oxidised with nitric acid camphanic acid is formedas well as camphoric acid.E th y Z camp hocn rbozy late C,H 150. C 0 OE t is prepared by passinghydrochloric acid into an alcoholic solution of the acid and forms acwlourless liquid boiling a t 276" (uncorr.) ; sp. gr. = 1.052 a t 15".The boiling point excludes the possibility of the formula C,H,O,ascribed to the acid by Kachler and Spitzer (Abstr. 1852 66). Whensodium camphocarboxylate is t'reated with sodium acetate and phenyl-hydrazine hydrochloride a hydmzhre cowpound is formed whichcrystallises in needles.These results confirm the formula C ,H,9,already ascribed to camphocarboxylic acid and show that it is a ketonicacid. From its instability the acid would be a p-ketonic acid. Onthe other hand it may be compared with phenylglyoxylic acid,which when distilled yields benzaldehyde and carbonic anhydride,according to which camphor would be an aldehyde. This wouldaccount for the formation of campholenic acid from caniphoroxime aswell as from p-dibromo-camphor.Haller's camphor cyanide may be considered as the nitrile of campho-cxrboxylic acid ; hydroxycamphocarboxglic acid appears to have thesame relation to camphocarboxylic acid that campholic acid has tocamphor. N. H. M.Camphylamine. By H. GOLDSCHMIDT (Ber. 18 3297-3298 ;compare Abstr.1885 1072). - Camphylamine CloHI9N was pre-viously prepared (loc. cit.) by reducing the anhydride of camphoroximewith zinc and sulphuric acid. An almost theoretical yield is obtainedby the actiou of sodium and alcohol on the anhydride It forms acolourless liquid which boils at 1 9 6 1 9 6 " without decomposition.Exposed to the air it solidifies to it wa,xy mass consisting of a com-pound of camphylamine with carbonic anhydride. N. H. M.Gutta-percha from Bassia Parkii. By E. HECKEL and F.SCHLAGDENHAUFFEN (Compt. rend. 101 1069-1071).-Gutta-perchnfrom Bassia (or Butyrospermurn) Parkii (Conzpt. rend. 100 1239)resembles ordinary gutta-percha in its physical properties. I t isobtained in compact fibrous ma,sses which soften in warm water andbecome adhesive a t about the boiling point. It becomes electrifiedas easily as the ordinary va'riety and serves equally well as an insu-lator ; sp.gr. 0.976.The gutta-percha from Bassia is however much less soluble inlight petroleum terebenthene ether and boiling acetic acid than theordinary variety hut is almost equally soluble in carbon bisulphide,chloroform benzene and boiling alcohol of 95".The proportion of each variety dissolved by the different solventsis given in the following table :250 ABSTRACTS OF CHEMICAL PAPERS.Carbonbisulphide. Chloroform. Benzene. Ether.Ordinary gutta-percha . . . . . 99.72 98.60 93.20 413.8Gutta-percha from B. Parkii 97.92 98.28 92.80 20.1BoilingLight Tere- Boiling alcoholpetroleum. benthene.acetic acid. of 95'.Ordinary gutta-percha . . . . . . 34.0 20 19.2 7Gutta-percha from H. Parkii 18.1 8 12.8 7When analysed by Payen's method the product from B. Piwlziiyields gutta-percha 91.5 albane 6.0 fluavile 2.5 = 100 and is almostidentical in composition with the commercial article. It leaves 1.2 percent. of ash which contains iron manganese calcium sodium potas-sium lithium silica and sulphuric and carbonic acids.Gutta-percha from B. Parkii is excellently adapted for the produc-tion of casts moulds &c. C. H. B.Oxidation of Copai%a Balsam. By S. LEVY (Bey. 18 3206-3208). Dimethylsuccinic Acid an Oxidation-product ofCopaiba Balsam. By S. LEVY and P. ENGLANDNR (Ber. 18 3209-3212)-By the distillation of copa'iba balsam two fractions of nearlyconstant boiling point are obtained of which the one investigated iscolourless lsevorotat,ory boils a t 252-254" and has a sp.gr. of0.8978 atl 24". When oxidised with chromic mixture it gave inaddition to acetic acid and other products not yet examined 14 to2 per cent. of an acid CGHl"04 which proved to be identical with un-symmetrical dimethylsuccinic acid.A Glucoside Allied to Coniferin. By F. TIEMANN (Ber. 18,3481-3493).-As it has been demonstrated tlhat the composition ofconiferin is represented by the formulaA. J. G.C6H,(C3H4*OH) (OMe)*OC,H,05 [ = 1 3 41,and that it thus belongs to the class of phenol glucosides experimentswere made with a view to the synthesis of this glucoside indirectlyfrom glucovanillin.Glucoferulic aldehyde C6H3(C2H2-CHO)(OMe)*OC6H1105 [ = 1 3 41,obtained by heating glucovanillin with acetaldehyde in presence ofsoda crystallises in needles containing 2 mols.H20 ; it melts at 200-202' and is readily soluble in hot water alcohol and ether. It doesnot reduce Fehling's solution and in aqueous solution is lsevorotatory.It shows all the characteristic reactions of the aldehydes giving a redcoloration with rosaniline in presence of sulphuric acid and with para-diazohenzenesulphonic acid and sodium amalgam as also in yieldingphelzylhydrazine and aldoaime derivatives. The former,OMe*CGH3(C2H2*CH N2HPh)*OC6Hl,05,is a golden-yellow powder melting a t 212" insoluble in ether andwater readily soluble in alcohol.OMe*CsH3( CzHz*CH N*OH)*0C6HllO5,The latterORGANIC CHEMISTRY.251crystallises in white needles melting a t 163" sparingly soluble in coldwater more soluble in alcohol.Ferulic aZdetiyde OMe*C6H,( C,H,.CHO)*OH is best obtained by thedecomposition of the above glucoside with emillsin. It is best althoughvery imperfectly separated from the accompanying vanillin by thedifference of solubility of their sodium hydrogen sulphite compounds.I t s melting point 84" is close to that of vanillin 81" ; but its crys-talline form is very different in that it forms needles belongingprobably to the monosymmetric system cc b c = 3.014 1 ?. It issparingly soluble in cold water readily soluble in alcohol and ether.As regards the ready transformation into vanillin ferulic aldehyderesembles coniferyl alcohol.Experiments on the reduction of glucoferulic aldehyde do not seemto have led to any very definite resalts.Glucofemlic m e t h y l ketone OMe.C,H,* ( C2H2*CO&~e)-OC6Hllo5[ = 1 3 41 prepared from glucovanillin and acetone crystallises ingolden-yellow needles containing 2 mols.H 2 0 ; i t melts a t 207" issparingly soluble in cold water more soluble in hot water and alcohol.I t s aqueous solution is 1zevorotatoi.y. It yields a phenylhydrazine-derivative as a golden precipitate and also a ketoxime. It is decom-posed by emulsin into dextrose and ferulic m e t h y l ketone,OMe*C6H,( C2H2*COMe)-OH,which forms clear golden needles melting a t 130° soluble in alcohol,ether and benzene. V. H. V.Quercetin and its Derivatives. By J.HERZIG (Monafsh. Chem.,863-883).-"t'he author considers that the formula C2J116011 adoptedfor quercetin is probably incorrect and that almost beyond doubt,the so-called quercetin-derivatives (tribrorno-compounds &c.) can nolonger be considered as substitution-compounds in which the quercetinnucleus exists in an unaltered state. This view is supported by thefact that the most carefully executed analyses of tribromoquercetinand tribroni-octacetylquercetin give results always differing very muchfrom the theoretical and that both the so-called tribromoquercetin andalso quercetiri itself when submitted to the action of excess of brominein acetic acid are converted into tribrornophloroglucinol instead ofyielding a more highly brominated quercetin compound ; warm dilutealkalis act on tribromoquercetin removing the bromine as hydro-hromic acid and forming an uncrystallisable substance a reactionexactly similar to that which takes place with tribromophloroglucinol(compare this vol.p. 232). The last two reactions seem to indicatethe presence of a phloroglucinol nucleus in quercetin.By boiling quercetin with dilute alcoholic potash for from 8 to10 hours phloroglucinol and protoeatechuic acid are obtained as end-products and by oxidising quercetin with potassium chlorate andhydrochloric acid protocatechuic acid is formed i n abundance. Theauthor further points out that a series of estimations of quercetin,in a large number of most carefully purified samples of quercitrincoming from various sources have invariably given results from2 t o S per cent.higher than those of Lieberlnann and Hamburge252 ABSTRACTS O F CHEPllICdL PAPER,S.(Abstr. 1879 945) and of Rigaud (AnnaZsn 90 283). The anthorhas net discovered any satisfactory method for the determination ofthe isorlulcitol and considers it to be still an open question as towhether the products of the decomposition of quercitrin by sulphuricacid consist simply of queiacetin and isodulcitol. The amount of iso-du1cit)ol which he finds varies between 34.7 and 38.6 per cent. Quercitrinis decomposed by the action of dilute acetic acid but is not acted onby hydrogen sulphide. It is converted into an acetyl-derivative bythe action of acetic anhydyide and sodium acetate; this is an amor-phous compound which melts below loo" arid is much more readilysoluble in alcohol than the acetylquercetin compound.A.P.Rhamnetin. By J. HERZIG (Monatsh. Chem. 6 889-890).-Theauthor considers that rliamnetin is a compound very closely allied toquercetin and that the formula C12H8C) given by Liebermann andHormann (Abstr. 1879 271) should he doubled ; further the acetyl-rhamnetin prepared by these aut hms contains six molecules of acetylon the double formula and not four as stated by them. By digestingethyl-rhamnetin with potash in a sealed tube the formation of diethyl-protocatechuic acid and a derivative of phloroglucinol was observed.A. P.The Colouring Matter of Cochineal. By W. WILL and H.LEYMANN (Ber.l8,3180-3193).-The constitution of carminic acidis still practically undetermined those substances of known constitu-tion that have been prepared from it such as niirococcusic acid (tri-nitrocresotic acid [(NO,) Me OH COOH = 2 4 6 1 3 51 o rcoccinin ruficoccin and ruficarmin (shown by Liebermann to beanthracene-derivatives) having been obtained by such energetic reac-tions as may have led to considerable modificat'ions in the componentgroups. The object of the present investigation was to obtain deriva-tives standing in closer relation to the original colouring matter.According to Hlasiwetz and Grabowski (AnnaZen 141 329) carrninicacid is a glucoside and when heated with dilute sulphuric acid is re-solved into a sugar and carmine-red CllH1,07.These statements,however require confirmation.When carmine-red is dissolved in aqueous (50 per cent.) aceticacid and the solution boiled with excess of bromine two bromo-corn-pounds are formed of which one a-bromocarmin crystallises on cool-ing whilst the other p-bromocarmin separates in clear yellow flockson adding water to the filtrate.a- Rromocurmir12 C1,H4Br1O3 after purification crystallises in colour-less needles melts a t 247-2418' with decomposition is insoluble inwater sparingly soluble in hot alcohol benzene and glacial aceticacid. It is soluble in the alkaline hydroxides but not in alkalinehydrogen carbonates.U-HudroxzJFromocnrmin Cl0H6Br205 = OH*C,H~Br,O,*COOH is ob-tained by boiling the a-bromo-compouud with strong aqueouspotash and is precipitated on acidifyiiig with dilute hydrochloricacid.It forms colourless crystals and melts a t 207-208" witORGXSIC CHEMISTRY. 253evolution of gas. From its behsvisur when ninthylated it wouldseem to contain both a hydroxyl and a carboxyl group. The methylsalt OH*CgH4Br,O2.C0O.Me prepared by treating the above com-pound with methyl alcohol and hydrogen chloride is crjstalline andmelts a t 192". A dimethyl salt OMe.CgHdBr202*C OOMe is preparedby heating a-hydroxybromocarmin with methyl alcohol methyliodide and potash ; it is crystalline melts at 185" and when boiledwith alcoholic potash and acidified with hydrochloric acid yields theniethoxy-acid OMe~C,H4Br,02*COOH. This forms voluminous ci*.rs-tslline flocks and melts a t 185" is insoluble in water very readilysoluble in acids.A t the same time a6 the dimethyl saIt anothercompound is formed melting a t 150" from which by boiling withpotash &c. a crystalline acid melting at 171" is obtained and is stillunder investigation.When a-hydroxybromocarmin is oxidised with an alkaline solutionof potassium permanganate an acid of the formula C9H,Br,04 isobtained together with another substance C,H,Br?O which will bedescribed with the derivatives of P-brornoearmin. The acid C9H6Br,0,forms colourless crystals and melts a t 243-244". The methyl sult,OH*C,HdBr204~C00Me forms compact colourless crystals and meltsat 201". The dimethyl salt OMeC,HdBr,O*COOMe forms lustrouscrystals melts a t 161" and is soluble in alcohol.0-Bromocarmin could not be crystallised directly from any solvent,nor otherwise purified but by boiling it f o r a short time with potasha red powderj potassium salt C,H,Br,O,K i s formed from which,by the action of hydrochloric acid an acid cryst;dlising in lustroiisneedles and melting a t 232" is obtained.This wid P-hydroxybromo-carmin is distinguished from those previously described by the factthat all its salts are highly coloured ; it has the formula Cl,H5Br304.Attempts ta prepare its rne'thyl-derivatives were unsuccessful. Whenoxidised in alkaline .solution with dilate potassium permanganate ityields two substances whicqh can be separattd by treatment withwater in whieh-one anly is soluble.Dibram~.ydro~i~aeth~lbenzoyldicarboxylic acid,c&6&206 = ? C O O H .C 6 B ~ ~ M e ( O ~ ~ ~ C ~ c o o H ,.the aubshance soluble in water crystallises with 1 mol. H20 in colour-less lustrous prisms melts at 2%" with decomposition and is verymadily soluble in most solvents. Several of its salts have been pre-pared.Uibromo7~ydro~ymethyl~hthalic aiihydride,co CeHrBr20r = OH*CsMeBrz< co> 0,the second oxidation-product is also obtained as previously mcn-t,ioned by the oxidation of a-hydroxybromocarmin ; it is a crystallinesolid melts at 195" is readily soluble in alcohol insoluble in water.It dissolves in alkalis but not in sodium hydrogen carbonate excepton long boiling. When digested for 5-6 hours with methyl iodide,methyl alcohol and potash it is converted into a methyZ salt of theformula O&Ie*C,lAeBr,( COOMe) which is crystalline melts at 70°,VOL.L. 254 ABSTRACTS OF CHEMICAL PAPERS.and is readily soluble in alcohol ether and benzene insoluble in waterand in cold alkalis. When saponified with alcoholic potash &c. itgives d i bronzometh 0% ymeih y lp hthalic acid OMe-C6MeBr (C 0 OH) ; thiscrystallises in slender needles and melts at 100" with loss of waterand conversion into the corresponding anhydride,co OMe* C6MeBr2 < > 0,a crystalline substance melting a t 144" and giving with sulphuricacid and phenol a similar colour reaction to that obtained with phthalicanhydride. When treated wit'h potash it is reconverted into theacid. As these results point clearly to the contiguous position of t,hecarboxyl-groups and as the relative positions of carboxyl to methyland hydroxyl have already been determined in nitrococcusic acid itfollows that the hydroxy-anhydride must have the constitution[Me C20 Br OH Br = 1 2 3 4 5 61.If carmine-red really has the composition CllHI2O7 /3-hydroxybromo-carmin which contains the same number of carbon-atoms muststand in very close relation to i t ; and although not itself a colouredsubstance yet when dissolved in alkali mixed with stannous chlo-ride and acidified with hydrochloric acid it yields a substance whichwhen exposed to air in ethereal solution absorbs oxygen yielding acoloured liquid of tint similar to that of a cochineal solution whichdyes a similar colour and also like a cochineal solution turns violet-red on addition of an alkali.A. J. G,Action of Chlorophyll on Carbonic Anhydride when re-moved from Vegetable Cells. By P. REGNARD (COWL@ rend. 101,1293-1295) .-Water containing carbonic anhydride was mixed withCoupier's solution exactly decolorised with sodium hyposulphite thechlorophyll was added and the vessel completely filled was placed insunlight or in the dark. The decomposition of the carbonic anhy-dride was shown by the solution becoming blue. An entire leaf insunlight quickly caused a blue coloration. Some tender leaves weretriturated with enamel powder treated with water and the solu-tion filtered. The filtrate contained chlorophyll and fragments ofcellules but no intact cells. k small quantity readily produced acoloration in the test-solution.Chlorophyll was extracted from otherleaves by means of ether or alcohol and cotton-wool was dipped intothe filtered solutions and then thoroughly dried in a vacuum at theordinary temperature. Fragments of this prepared wool were intro-duced into the test-solution and exposed to light; a blue colorationwas quickly produced. It follows therefore that chlorophyll has thepower of decomposing carbonic anhydride even when not enclosed ina vegetable cell and not in contact with the white protoplasm. Thechlorophyll in fact stands in the same relahion to the protoplasm asthe haemoglobin in the blood does to the colourless globulin.Lokao or Chinese Green. By R. KAYSER (Bey. 18 3417-3429).-This dye imported from China is obtained from the bark ofvarious species of buckthorn ; according to the researches of Cloez andC.H. BORGAXIC CHEMISTRY. 255Guignet (this Journal 1872 706) if is in the crude state a lakecontaining 26 per cent. of mineral matter and from which a compoundlokain cz&f3,017 is extracted by ammonia. I n this paper theseexperiments are repeated but with slightly different results. Onexhausting lokao frequently with ammonium carbonate and addiDg90 per cent. alcohol a deep blue precipitate is obtained ; this is theammonium salt of Eokaonir acid C42H&7 from which the acid may beobtained by decomposition with oxalic acid. Thus produced it is apulverulent bluish-black mass of metallic lustre insoluble in water,alcohol and ether.Its vtonarnmoniurn salt C42H17027*NHi formssmall crystals of bronze-like lustre ; the ~~iammo~2ium salt is of similarappearance; the potassium barium and lead salts are deep bluepowders. Soluble compounds of lokaonic acid show a perfect absorp-tion in the red and jellow portions of the spectrum.Lokaonic acid when boiled with dilute acids is decomposed intoZokanic acid (&HJ602 and a carbohydrate Zokaose ?&&1206. Theformer is a violet crystalline powder insoluble in water dcohol andether; it gives off a molecule of water a t 120”; its aiizmonium salt,C36H3502,NH4 is a dark blue powder soluble in water to form abluish-violet solution ; the barium and lead salts C36H&”& areiusoluble blaekish-blue poviders.The soluble compounds of the acid show a characteristic absorptionin the yellow and yellow-green portions of the spectrum.The decomposition of lokaonic acid is expressed thus C12H,027 =C36H36021 + C,H,O6.Concentrated sulphuric acid convepts lokanic acidinto R substance of the composition C36H,01~ = C3,H3,OZ~ + 5Hzo,a red-brown powder forming a barium-derivative CB6HUBaO16,whilst potash decomposes it into phloroglucinol and delokayiic acid,C15R908 a brown powder ; dilute nitric acid yields nitrophloroglucinoland a brown powder which was not further examined.Lokaose CSH1206 obtained in the filtrate from the insolublelokaonic acid in the reaction mentioned above forms minute ttcicularcrystals and is distinguished from dextrose by its cupric oxidereducing power Rk I= 50 and its optical inactivity. v.H. v.New Constituents of Atropa Belladonna. By H. KUNZ ( 4 d ~ .Pharm. [3] 23 722-735) .-The occurrence of a fluorescentcompound in belladonna has been repeatedly noticed. The author hasfound this compound both in the extract of the root and of the leavesand stalk ; the root extract was acidified until all fluorescence disap-peared and then agitated with ether. The brownish-yellow residueleft on evaporation of the ethereal solution consisted of microscopicprisms having an acid reaction. By washing with cold ether a non-cry stallisable bitter mother-liquor was separated which was reservedfor further examination. The crystals were purified by repcatedtreatment with boiling absolute alcohol which finally yielded smallclusters of light yellow four-sided highly refractive rhombic prisms.This substance the author names prorisionally chrysatropic acid,CI2H1,O5.It melts at 201*5” resolidifies a t 182.6”. When carefullyheated the acid sublimes without decomposition but when morestrongly heated burns with a luminous flame leaving no residue. Its 2 5 i; ABSTRACTS OB' CHEMICAL PAPERS.is soluble in 70-80 parts of hot water sparingly in cold water and inether more soluble in alcohol and acetic acid. The concentratedaqueous and alcoholic solutions are pale yellow by transmitted light,but by reflected light show a beautiful emerald-green fluorescence ;dilute solutionR give a bluish fluorescence. The crjstals dissolve inalkalis or alkaline carbonate solutions yielding splendid bluish-greenfluorescent solutions.An aqneous solution when treated withpotassium permanganate gives a green liquid showing strong indigo-blue fluorescence. Ferric chloride gives an emerald-green colorationchanging t o cobalt-blue. The lead and copper salts were examinedand described. From the formula and reactions of the substance theauthor infers a near relatioiisliip to hydroxynaphthaquinone.Leucatropic acid C1,H3'LgS is obtained from the bitter mother-liquor previously mentioned ; it crystallises in clusters of microscopicprisms haviEg a satin-like lustre it melts a t i3.8" and rcsolidifies a t60.2". I t is insoluble in cold. but somewhat soluble in boiling water,i t is nearly insoluble in cold but readily soluble in boiling ether andin alcohol.Qualitative examination indicates that the compoundbelongs to the fatty acid series.The anthor also found about 0.6 per cent. of succinic acid inbelladonna extract prepared from the herbaceous part of the plant.J. T.and r-Picolines. By 0. LANGE (Rer. 18 3436-3441J.-a-Picoline is best separated from animal oil by means of its sparinglysoluble mercuriochloride ; the process is more practical than that ofthe fractional crystallisation of the a- and ,G-picoline platinochloride~jproposed by Wkidel. The pure base boils at 129-130" (13$"Weidel) ; its sp. gr. at 0" compared with water at 4" is 0.9656; itsplatinochloyide Forms small crystals which melt at 178" its mercuyio-c h l o d e leaflets which melt a t 104" ; its aurochloride crystallisesin needles melting at 167-168" and its picrate in needles melt-ing at 165"; both these last-named salts are moderately soluble inwater.7-Picoline is best obtained synthetically by Ladeuburg's processfrom pyridine and methyl iodide.On distilling the product obtainedfrom pyridine methiodide two principal fractions are obtained boilinga t 127-134" and 142-1 50" respectively ; the former consists of0 - the latter of ypicoline. This base when pure boils a t 144-145" (corny. Hofmann and Rehrmann Ber. 17 26%) ; its sp. gr.at 0" compared with water at 4" is 0.971. Its salts are more or lesssparingly soh ble in water ; the platinochloride is crystalline andmelts a t 225-226" ; tbe aurockloride forms leaflets melting a t 205" ;the rnercuriochZoric7e long white needles melting at 136- 138" andthe picrate silky needles melting a t 156-157".On oxidation thebase is converted into isonicotinic acid. V. H. V.p-Picoline Synthesis of some Hornologues of Pyridine. B.yA. HESEKIEL ( B e r . 18 3091-3LOO) .-P-Picoline prepared fromacetamide glycerol and phosphoric anhydride (Abstr. 1885 812) islzvorotatory ; this cannot he due to the presence of optically activeimpurities as suggested by Skraup in the case of P-picoline prepareORGANIC CHEMISTRY. 257fi-om coal-oil. The mercuriochloride (C6NH7)2,H2HgCI* crystallisesin white needles which melt at 143". The aurochloride forms a volu-minous precipitate sparingly soluble in water ; it melts at 182-184".The picrate crystallises in lustrous needles melting atl 145-146" ; itdissolves readily in water.The zinc salt and the platinochlorideare also described.Meth ylethy Zpyridine C,HllN is prepared by heating paraldehydewith 3 parts of acetnmide and 2 parts of phosphoric acid for 16-20hours at 160". It forms a clear colonrless oil boiling a t 175-179'.The platinochloride cryetallises in beautiful dark orange-colouredplates melting at 180" ; it is probably identical with a platinochlorideobtained by Diirkopf from aldehydecollidine (Abstr. 1885 817).The uurochloride melting at 72" and the picrate melting at 157" aredescribed.Parvoline was prepared in a similar way from propaldehyde acet-nmide and phosphoric anhydride.By the action of methyl iodide in P-pipecoline (Abstr.1885 812)dissolved in methyl alcohol a compound CsH,NI is formed. It isa white crystalline substance melting at 1925". A platinorhloride,C,H,N,PtCI was obtained which when heated at 234" becomesblack. N. H. M.Constitution of Aldehyde-collidine. By E. DGRKOPF (Ber. 18,3432-3455) .-In this paper it is shown that aldehyde-collidine(comp. Abstr. 188.5 817) is an ethylmethylpyridine as. evidenced byits yielding on moderate oxidation a methylpyridinecarboxylic acid,identical with the acid obtained by Hoogeaerff and v. Dorp frommethylquinolinic acid and with the homoisonicotinic acid of deConinck as shown by its physical properties and its conversion onfurther oxidation into cinchomeronic acid. The constitution of thiscollidine is thus represented by the formula C,NH,MeEt [Et Me =3 41 and its hexahydride or copellidine by the formula C,NH,Me,Et ;it must then be identical with the cJlidine obtained from brucine byde Coninck.V. H. V.Identity of Bottinger's Pyridinedicarboxylic Acid withLutidinic Acid. By E. VOGES (Ber. 18 3162-3165) .-Whilstaccording to the received theory there can be but two pyridinecarbo-xylic acids which yield r- pyridinemonocarboxylic acid (isonicotinicacid) three such acids have been described. The author hasreinvestigated Bottinger's pyridinedicarboxylic acid and finds thatit is identical with lutidinic acid. 'Ihere are therefore but t w opyridinedicarboxylic acids containing one COOH-group in the[ = 3 ] position uamely cinchomeronic acid [2 31 and lutidiniuacid [l 31.Condensation of Cinnamaldehyde with Ammonia andEthyl Acetoacetate.By W. EPSTEIN (Annalen 231 1-36).-x'shylio benzylidenedihy&rocoll~d~n~d~~arboxylate C2,Hz5O4N is formedby the actim of ethyl acetoacetate and alcoholic ammonia on cinnam-aldehyde. It is a white crystalline substance soluble in ether and iu.A. J. G258 ABSTRACTS O F CHEMICAL PAPERS.warm alcohol. I t begins to soften a t 146" and melts a t 148-149'.When nitrous acid is passed into an alcoholic solution of this com-pound it is oxidised and converted into ethyl benzylidenecollidinedicar-boxylate C,H2,04N ; this melts a t 39" and is soluble in alcohol andether. It also dissolves easily in acids forming crystalline salts whichare decomposed by water.The pZatimchZoride (C2,H2304N)2,H2PtC16,melts at 195". Benzylidenecollidined~carbo~~li~ acid,melts at 218-219' with partial decomposition. The anhydrous acidmelts a t 241". It is soluble in alcohol and sparingly soluble in water,ether and chloroform. With hydrochloric acid it forms an unstablecompound which is decomposed by water. The platinochloride,(C,H150J?)2.H2PtC1 crystallises in needles. The acid forms amor-phous metallic salts. When oxidised with potassium permanganate,the acid splits up into benzoic acid and a lutidinetricarboxylic acidwhich is not identical with the acid obtained by Hantzsch (Abstr.,1883 85) by the oxidation of collidinedicarboxylic acid. The luti-dinetricarboxylic acid crystallises with 1 mol.H20 in prisms. It issparingly soluble in the ordinary solvents-560 parts by weight ofwater a t 8' dissolve 1 part of the acid. It decomposes a t 220"without melting. Hot hydrochloric acid slowly dissolves the acid ;on cooling mono- or tri-clinic crystals of the hydrochloride aredeposited. This salt is decomposed by water or alcohol. Theneutral salts of the acid are sparingly soluble and generally crystal-lise readily. Ferric chloride produces a red coloration in a solu-tion of t'he ammonium salt. The mercurous salt dissolves in hotwater and is deposited from the solution on cooling in microscopicprisms.Benzene and lutidine C5NTvIezH are formed when the mixture ofbenzoic and lutidinetricarboxylic acids obtained by the oxidation ofbenzylidenecollidinedicarboxylic acid is heated with quicklime in acurrent of hydrogen.The properties of the lutidine obtained in t'hisway have already been described by the author (Abstr. 1885 815).It is an isomeride of the lutidine which Hantzsch obtained fromlntidinetricarboxylic acid (Abstr. 1883 85) and from pseudolutido-styril (Abstr. 1885 397). On oxidation it yields a pyridenedicarbo-xylic acid which closely resemble8 Ramsay's a-pyridinedicarboxylicacid (Abstr. 1879 266) and the isocinchomeronic acid of Weideland Hertzig (Monatsh. Chem. 1880 5). On distillation in a current ofhydrogen picolinic but no nicotinic acid is formed. Picolinic acidis also formed by the action of glacial acetic acid on the acid a t 160'.Hence it appears that the condensation-products of aldehydes withethyl acetoacetate have the symmetrical constitutionCHPh CR*C,NMe,(COOHh,C(COOH)*CMexceC(COOH) CMeyN' w.c. w.Action of the Homologues of Acetaldehyde on Ammoniaand Ethyl Acetoacetate. By F. ENGELMANN (Aniznlen 231 37-i 1) .-Ethyl hy droparvo1in.edicarboxy b t e C5NH,Me2E t (C OOEt ) isfcwmed on waiaming a mixture of ethyl acetoacetate propaldehydeORGANIC CHEMISTRY. 259and alcoholic ammonia. It melts a t 110" and closely resembles ethylhydrocollidinedicarboxylnte in its properties. On oxidation withnitrous acid it loses 2 atoms of hydrogen and is converted into ethylparvolinedicarboxylate CllHl104NEt,. This compound is a colourlessoil insoluble in water. It unites with mineral acids forming hygro-scopic salts.The platinochluride ( C15H2,04N),H2PtC1~ forms redprisms soluble in water less soluble in alcohol. It melts at 139" andbegins to decompose a t 185".ParvoZinedicarbo~ylic acid C,NMe,Et (COOK) is obtained from theethylic salt by saponification with alcoholic potash in closed vessels.Most of the metallic salts of this acid are easily soluble in water.The silver salt is an exception. The free acid is best prepared by theaction of sulphuretted hydrogen on the silver salt. It is freely solublein water and in aicohol and melts a t 289-290" with decomposition.The barium salt C11HIIN04Ba + 3H,O crystallises in plates. Thehydrochloride (C1,H,04N),HC1 + H,O forms glistening prisms.Farvuline C5NH2EtMe obtained by heating a mixture of potassiumparvolinedicarbosylate anti quicklime is a colourless highly refrac-tive liquid.Its sp. gr. a t 14" is 0916. It boils at 186" and is so!ublein 73 parts of water at 0" but is less soluble in warm water. Theaqueous solution yields precipitates with chromic and picric acids,melting a t 120" and with solutions of zinc lead mercuric mercurous,and silver salts. The platinockloride ( C9H,3N)2,H2PtC16 is solublein hot water and alcohol. It melts at 210". The dickromate,(C,H,3N)2,H,Cr20 begins to blacken at lSO" and melts with decom-position a t ZOO". It is not identical with the a-parvoline of Williams(Jahrb. che??z. 1854 495) and of Thenins (ibid. 1861 502) nor withthe P-parvoline of de Coninck (Abstr. 1881 56) nor with thebase which Waage obtained from propaldehyde-ammonia ( Abstr.,1884 172).Ethy 1 lqdroisoprop yl-lutidinedicarboxy late C5NH,Me2Pr ( COOEt),prepared by the action of alcoholic ammonia and ethyl acetoacetateon isobutaldehyde crystallises in long prisms melting a t 97".It issoluble in absolute alcohol ether benzene and chloroform insolublein water and sparingly soluble in alcohol. When oxidised withnitrous acid it yields ethyl Zutidinedic~~,rboxyZat~ C5NHMe2( COOEt),.This substance melts a t 73' and boils at 301-302" without decomposi-tion. On recrystallisation from warm alcohol it is obtained in longprismatic needles which are insoluble in water. Lutidinedicarboxylicacid is obtained as a crystalline precipitate containing 8 mol. H20 onthe addition of hydrochloric acid to a solution of the potassium salt.It is soluble in hot water and sparingly soluble in alcohol and ether.The barium salt CgH,04NBa + 2H20 is freely soluble in water;the lea,d salt C9HI,0aNPb + 2H,O crystallises in thick prisms.The7b~drocliZoride CgH90aN,HC1 + ZH,O forms prisms. A solution ofpotassium lutidinedicarboxylate yields precipitates with silver mer-cury copper cadmium zinc anti iron salts. The acid is decomposedon distillation with lime yielding a lutidine which is identical withthat obtained by Epstein (this vol. p. 257).E t h y l ~ydroisobutyllutidi.lledicarboxylate C4H9*C5NMe2H2(COOEt),is obtained by the action of alcoholic ammonia on valeraldehyde an260 ABSTRACTS OF CHEMICAL PAPERS.ethyl acetoacetate.It is deposited from akohd or light petroleum inlong prisms insoluble in water but freely soluble in alcohol ether,benzene chloroform and glacial acetic acid. It melts a t 100". Whennitrous acid. is passed into the alcoholic solution of this substance itloses 2 atoms of hydrogen forming eayb i.,.obut.~l-lutidinedicarboxylate,C4Hg-C,SJMe2( GOOE t),. This compound exists as a colourless thickliquid insolalble in water. It boils without decomposition between312" and 318". The hydrochloride C17H11'1504N,HC1 forms long needles :the platirtuch loride ( C,H2,O4N),H2Pt,Cl6 is freely soluble in water.It melts a t 207-208" with decomposition.By the action of alcoholic potash on diethyl isobutyllutidi~edicnr-boxylate mily one ethyl-group i8 replaced by potash.On decomposingthis potassium salt the monethyl salt C4H,*C5NMe2( COOEt)*COOH,is obtained in prismatic crystals soluble in alcohol and water. Itmelts a t 135" and begins to decompose at 230". The mercurous saltis obtained as a white precipitate on the addition of mercurous niimiteto a solution of the pokassium salt. On warming the mixture theprecipitate dissolves and is deposited on cooling in long needles Itis decomposed by water and metallic mercury is precipitated. Thebarium (C,H,O,N),Ba + 5H20 and culciurii ( 615H2004N)2Ca +4H20 salts crystallise in plates and are freely soluble i n water. Thehydrochloride C15H2,S 04,HCl + 2H20 forms monoclinic prisms,soluble in water and in alcohol. The porassium salt is converted intoisobut!il-luti~ineilica,.boz2/lic acid by boilirrg with an aqueous solution ofpotassium hydroxide.The free acid C4H9*C5NMe2(COOH)2 f 2H2O,prepared from the mercurous salt crystallises in monochnic prisms.It dissolves in hot water and in warm alcohol. The anhydrous acidmelts with decomposition at 273". A solution o€ the potassium iJaltgives precipitates with silver lead zinc cadmium and copper salts,and also with concentrated solutions of mercurous and mercuric salts.The bui-ium salt C1,H,O4NBa + 5H20 is freely soluble in water.'l'he culciurn salt crystallises i n four-sided pyramids containing 3 molu.H20. The hydrochlol*ide C1,H15( COOH),N,HCI is soluble in alcoholand in hydrochloric acid.Isobutyllutidine CaIIg*C5NH2Rh2 is a colourless liquid boiling a t210-213" and possessing a bitter taste.Its sp. gr. a t 18" is 0.8961compared with water at the same temperature. It is more soluble incold than in warm water. The base unites with acids forming verycleliquescent salts. The picrate forms yellow needles which melt a t114-115". The ylatinochloride is crystalline. It melts a t 208-209".The dichrosnate is soluble iu hot water. It is decomposed by heatw itlioub melting.Condensation products could not be obtained by the action ofacraldehyde instead of aldehyde on ammonia and ethyl acetoacetate.Pgridine-derivatives are not obtained when ethyl acetobenzoats isbubstituted fur ethyl acetoacetate in the preceding experiments.No condensatiori product is formed by the action of sulphuric acidDimethylquinolines.By L. BEHEND (Bey. 18 3165) .-Theuirnethj lquinoline from paraxjlidine sulphate described by L. XZJ eron ethyl acetobenzoste. w. c. wORGANIC CHEJIISTRY. 261(this vol. p. 161) has already been described by the author. Thebase boils a t 264.5-265.5" ; sp. gr. 1.0752 at 4". The platinoclloride,(GI ,HllN) (,H2P t Cl crys tnllises in reddish-yellow needles.1 4 ~~trahydrodimethylguinoline CI1Hl5N7 obtained by reductionwith tin and hydrochloric acid boils a t 271" and has an agreeableodour ; the hydrochloride CllHl,N,BCl crystallises in slender needlesor transparent six-sided tables.Quinoline-derivatives from Propaldehyde. By K. HARZ(Ber. 18 3384-3401).-Ethylmethylto2uquinoline (ethyldimethyl-quinoliiie) CsLUHiMezEt [Me Et Me = 3 2' 3'1 prepared fromparatohidine,.propaldehyde and hydroch!oric wid forms rhombiccrystals melting a t 54" and boiling a t 287-288" under a pressure of720 mm. ; i t is insoluble in water soluble in ether alcohol and ben-zene. Many of its salts are exceedingly soluble in water ; the hydr-iodide crystdlises in colourless needles ; the chromate in red needles ;the picrate in small yellow needles melting at 177"; the pZntim-c h l o d e in orangwred needles containing 2 mols. H20 ; the methiodidewith H,O in monoclinic needles melting a t 75-76" ; the ethiodidewith 4H20 in agglomerated crystals melting a t 112-114" ; and theetlboplutinochloride with 1H20 in minute glistening crystals. The baseforriis a tetruhydro-udditice product C,sHi,M a colourless stronglyrefractive oil boiling a t 285-286" ; its hydrochloride crystallises inneedles ; the platinochlowde i n brown leaflets containing 2H20 ; itsuitrosn-derivative C,Hl,N*NO forms a crystalline mass and givesLiebermann's roaction ; its methyl-deriuutive CI3Hl8NMe7 is an oilboiling at 275-280" and forming a platinochloride crystallising with2H20 in needles.With bromine the base forms an unstable dibromo-additive productdecomposed on heating with formation of a dibromo-substitution pro-duct CldH13Br2N crystallising in white needles which melt at 143-1&" and are insoluble in water but soluble iu ether and hot alcohol.Conceiitrated sulphuric acid yields a monosu1phorLic acid Cl,H,N*S03H,crystallking in the rhombic system sparingly soluble in cold more soin hot water ; its barium salt crystallises with 1 rtiol.H,O in inter-laced needles and its lead salt (C'l,H,so,N),Pb,2C,3Hl~N*S0,H + 6H20,in golden needles very soluble in water. On fusing it with alkali thesulphonic acid is converted into the corresponding hydroxyl-derivative,ClsHllN*OH which forms colourless needles melting at 45" andboiling a t 312-316".With concentrated sulphuric and nitric acids the base yields amononitro-~eriuative C13H,N*N0 which crystallises in the triclinicsystem; it melts at log" and is insoluble in water but readily solublein chloroform. Its hydyochloride forms dendritic golden crystals aridits plutitbochloride thick reddish-golden crystids containiug 2 mols.I!&. On reduction with stannous chloride there is formed an amid+derivative C13H14N*NH2 crystallising in prisms or flat needles be-longing to the triclinic system; i t melts at 148-149" and is veryboluble in alcohol sparingly soluble in ether and petroleum.A.J. G.~thyltoluquinoli~~ecarb~xylic acid,C9XH4MeEt.COOH jble Et COOH = 3 2' 3'12 62 ABSTRACTS OF CHENICAL PAPERS.obtained by the oxidation of the above bass with chromic acid,crystallises with 1 mol. H,O in the triclinic system; it melts at 142-143" and is soluble in hot water and alcohol; its solutions show aslight acid reaction. Its sodium salt with 3Hz0 and barium salt with4H20 form interlaced needles ; its copper salt is a crystalline andsilver salt an amorphous precipitate. The ethyl salt crystallises inneedles ; it is soluble in alcohol and also in water but is saponifiedby it.On heating a t 150" it gives off carbonic anhydride withformation of ethyltoluquinoliiie CgNH5MeEt [Me E t = 3 2'3 crys-tallising in snow-white needles which melt a t 59-60" and boil a t270" under a pressure of 718 mm. ; its salts with mineral acids arevery soluble in water ; its plntinochloride crystallises in needles itspicrate forms minute golden crystals melting a t 244-245". The baseis apparently isomeric with the a-ethylmethylquinoline of Kugler.Etl~~lmethyZtoluqilinol~?~,e CgNH4Me2Et [Me Et Me = 2 or 4 2' 3'1,from metatoluidine and propaldehyde crystallises in hexagonalleaflets belonging to the rhombic system. It melts a t 40-41" andboils a t 288-292". Its hydrochloride crystallises in colourless prisms ;the hydroiodide in needles ; the picrate in golden needles melting a t219-220' ; the platinochloride in minute needles containing 2H20 ;the methiodide with 1H20 in golden needles and the methoplatino-chloride in glistening orange-red needles.Ethylmeth~ltoluqz~ioline C,N&Me2Et [Me Et Me = 1 2' 3'1,from orthotoluidine and propaldehyde forms rnonoclinic cryst'als,which melt at 44" and boil at 279-280" under a pressure of 717 mm.Its hydrochloride hydroiodide picrate and methiodide crystallise inneedles theplatirwchloride in large leaflets and the methoplatinochloridein glistening orange-red needles.With tin and hydrochloric acid itforms a tetrahydro-additive product CI3HL9N a pale yellow oil boilinga t 274-276" and dissolving in nitric acid with production of anintense coloration ; its hgdrochloride forms colourless crystals spar-ingly soluble in water.V. H. V.Quinoline-derivatives from Normal Butaldehyde. By M.KAHN (Ber. l8,3361-3372).-On the addition of normal butaldehyde(100 grams) to aniline (60 grams) and fuming hydrochloric acid(120 grams) distillation of the product and extraction by ether,two principal fractions are obtained boiling a t 230-250" and 280-300" respectively ; the former consists of butylphenylamine the latterof propylethylquinoline CgNH5EtPP [PF Et = 2' 3'3. The purebase is a colourless liquid boiling a t 291" under 720 mm. pressure,resembling quinaldine in odour rapidly darkening on exposure to air,insoluble in water but volatile in a current of steam.I t is soluble inalcohol ether and dilute acids. Its hydrochloride crystallises with2 mols. H,O in triclinic tables the nitrate with 1 mol. H20 in longcrystals ; both these salts are best obtained by the gradual addition ofether to their alcoholic solutions ; the suZphate crystallises in tufts ofneedles the picrate in golden needles or leaflets melting a t 163" in-soluble in cold water sparingly soluble in alcohol; the chromate,( C,H,N),H,Cr207 in orange-) ellow needles ; the platinochloride iORGANIC OHEMlSTRY. 263yellow needles insoluble in cold soluble in hot water ; the methiodidein golden needles containing 1 mol. HzO ; and methoplatinochloride(C14H.,7N)2,Me2PtCI in orange-yellow dendritic needles.EthyZpuinoZinecarboxylic acid C,NH,Et-COOH [COOH Et = T 3'1,is obtained by the oxidation of the above base with chromic acid.Itcrystallises in interlaced needles which melt at 148" with evolutionof carbonic anhydride ; it is soluble in water crystallising therefromwith + mol. HzO sparingly soluble in ether. I t s pEa,tinochloride formsgroups of needles and its picrate golden needleu melting at 153",sparingly soluble in water and alcohol. The copper salt is a bluish-green precipitate consisting of minute needles; the silver salt awhite amorphous precipitate.Eth.ylquinoZi.ne C,NH,Et [Et = 3'1 obtained by the dry distilla-tion of the above acid is a colourless highly refractive liquid boilingat 265" under 718 mm.pressure. Its platinochloride crystallises ingolden needles and its picrate also in needles which melt a t 163"(comp. Baeyer and Jackson Abstr. 1880 406 and Riedel Abstr.,1883 1152).Numal butylphen ylamine NHPh*C4Hg obtained in the reactionmentioned above is best purified by means of its nitroso-derivative ;it is a colourless oil boiling a t 235" under a pressure of 720 mm. andis volatile in a current of steam. Its hydrochloride and sulph.decrystallise in needles and are very soluble in water. The ?zityoso-derimtive NO*NPh*C4Hg is a golden-yellow liquid insoluble in waterand dilute acids soluble in alcohol and ether ; i t gives Liebermann'sreaction in a most marked way ; the acetyl-derivative NAcPh*C4H9,is a colourless liquid boiling at 273-275" under a pressure of718 mm. V.H. V.Quinoline-derivatives from Isovalerafdehyde. By J. SPADY(Ber. 18 33 73-3384) .-Isovaleraldehyde and aniline in presenceof hydrochloric acid form isobutylisopropylquinoline and isoamyl-phenylamine (comp. preceding Abstr.) which are best separatedby means of their picrates that of the former being insoluble whilstthat of the latter is soluble in cold alcohol.Isobuty~~so~ropylqzcinolle C,NH5PrS*C4Hn$ [C4Hg PrS = 2' 3'1 is aliquid boiling at 295-296" under 709 mm. pressure insoluble inwater soluble in alcohol ether and benzene. On the addition of nitricacid to the base its nitrate C16H21N,HN03 + HzO separates at first asan oil but ultimately solidifies in acicular crystals ; the add swlphateforms pyramidal crystals belonging to the triclinic system; the hydro-chloride with 1H20 prismatic leaflets belonging to the triclinic system ;the chromate long orange-yellow needles insoluble in cold water anddilute sulphuric acid ; the methiodide golden needles containing1 mol.H20 soluble in alcohol and hot water; the methoplatino-chloride ( CleH21N)z,Me2PtC1 reddish-golden triclinic prisms spar-ingly soluble in water and dilute hydrochloric acid.hop rop y l g uinol inecar box y lie acid,C9NH5PrWOOH [COOH PI? = 2' 3'1,obtained by the oxidation of the above base with chromic acid c r 264 ABSTRACTS OF CHEMICAL PAPERS.t'allises in prismatic leaflets melting at 188-189' with slight de-composition ; its y latinochloride crystallises in orange-yellow prisms ;with silver nitrate it gives a flocculent precipitate of the composition,CI3H12,NO2Ag + C13H,7N02,HN03 sparingly soluble in dilute nitricacid and decomposed by water into its components. On distillationwith lime the acid is decomposed into qiiinoline and a diquinolineprobably identical with that obtained by Japp and Graham (Trans.,1881 174) and by Weidel (-4bstr.1881,613) ; but when heated aboveits melting point it is decomposed into carbonic anhATdride and iso-propylquinolirhe C,NH,PJ? [PI? = 3'1 a pale golden liquid boiling at275-280" under a pressure of 71s mm. and solidifying in a freezingiiiixture to a crystalline mass; it is insoluble in water soluble inalcohol et.her; and benzene. Its hydrochloride and platinochloridecrystallise in needles the picrate and chromate in delicate goldenneedles.Isoamylphewylarnine NHPh.CH2*CH2*C:HMe formed in the above-mentioned reaction i s a colourless oil of pleasant aromatic odour ; i tboils at 242-244" is insoluble in water soluble in alcohol andether.Its hydruchloride crystallises in prisms its nitroso-derivativeis an oil soluble in alcohol. and ether and giving Liebermann's reac-tion ; and its acetyl-derivative a liquid boiling a t 278" under a pres-sure of 720 mm. insoluble in water soluble in alcohol and ether.The base apparently is isomeric with the amylphenylamine obtainedby Hofniann from amyl bromide and aniline (AnnaZen 74,153).Quinoline-aldehyde By A. EINHORN (Ber. 18 3465-3468).-I n this paper trichlo?-etl~ylidenepuinaldirze C9H6N*CH CH*CC13 andquinoline-(aldehyde are described which are identical with thoseobtained by v.Miller and Spady (p. 265) and were prepared by thesame methods. The author however ascribes the formula C12HllN03,and not UI2HgNO2 to the acid from the trichloro-derivative. ThepZatinochZoride of the aldehyde forms golden transparent crystals,containing 2 mols. H20 ; whilst the aldehyde itself is said to melt at.103-104+" but no analyses are given of this substance.An Aldehyde of the Quinoline Series. By A. EINHORN (Ber.,18 3144-3146).-Trirnethylyuinolinealdehyde CI3Hl,NO + 3H20 isobtained by the actioii of chromyl chloride on crude quinaldine beingprobably formed from tetramethylquinoline present in the crudesubstance. It crystallises from water in splendid needles melting at73-74" ; it easily parts with its water of crystallisation and has thenthe melting point 101.5". It reacts readily with hydroxylamine andwith phenylhydrazine with formation of compounds melting at 203"and 207" respectively.It reduces ammoniacal silver solution and isoxidised a t the same time to an acid which melts a t 224".V. H. V.V. H. V.N. H. M.Quinoline-a-acrylic Acid. By W. v. MILLER and J. SPADY (Ber.,18 3402-3405) .-By the direct reaction of equal molecules of chloraland quinaldine a trichloro-compound C12H8NC13,H20 is formed,which crystallises in delicate needles melting at 146145O ; whenheated with an aqueous solution of potassium carbonate it yieldORGANIC CHEMISTRY.265pinoZilze-urr?ykic acid C9NH6-CH CHhCOOH [ C,H,*COOH = 2'7 whichrrystallises in leaflets melting a t 3 90-195" ; its hydrochloride crystal-liseg in colourless needles the p l a t i n o c h l o d e in prisms and the bariumsalt in tufts of needles.QuinoZine-aldeh?yde C9PU'H6.COH [COH = 3'1 formed by the oxida-tion of the above acid with potassium perniamganate crystallises inplates belonging to t h e monoclinic system; it melts a t 70-71° issparingly soluble in water aad petroleum readily soluble in benzeneand alcohol. Its aldehydic nature is evidenced by itls ready reductionby silver salts a n d the forma.tion of a phenylhydrazine compound,C16H,3N3 crystallising in golden leaflets melting at 195-198'. Theauthors propose t o extend these researohes to other aldehydes andtheir derivatives.V. H. V.Paraquinaldine-acrylic Acid. By W. v. MILLER and F. KINKELIN(Bey. 18 3234-3239). Paramidocinnamic acid was prepared by theaction of 100 grams of 38 per cent. hydrochloric acid and 100 gramsof tin on a warm alcoholic solution of 25 grams of ethyl paranitro-cinnamate. The product was freed from tin and evaporated whencrystals of the hydrochloride separa6ed. The jield is 75 per cent. ofthe themetical.Paraguin aldine-acry lie aciil,C9NH,MeCH CH-COOH [Me C,H,*COOH = 2' 31,is obtained by heating 50 grams a€ paramidocinnamic acid hydro-chloride with 50 grams of concentrated hydrochioric acid and 40grams of paraldehyde for two hours a t 100'. The product is dilutedwith water filtered and evaporated and the hydrochloride so obtainedtreated with sodium acetate which precipitates the free acid.Itforms small needles which melt at 240-250" with decomposition,but can be sublimed in part unchanged; iit dissolves sparingly inwater and cold alcohol readily in dilute alkali solution. The hydro-chloride (with 1 mol. H,O) crystallises in prisms readily soluble i nwater; the nitrate (with 1 mol. H20) forms colourless prisms withvitrems lustre. The plafknochloride (Cl&LllN02)~,H2PtC1 + 2H,O,forms thick reddish-yellow prisms.Paroquin~~Zdine-aZdehyde C9N.H51fe-CH0 [Me CHO = 2' 31 isprepared by oxidising the above compound trit,h potassium pernmn-gnnate at 0". It cr,whllises from a mixture of benzene and light petro-leum in yellowish plates melting at ;106",readily soluble in alcobol ether,benzene and in acids.The plutiiioohlaride (with 3 mols. H,O) crys-tallises in jorangeeoloured prisms. The phenylhydrazine compoundforms gold-coloured p r i s m which melt a t 160". When the alde-hyde is heated for some hours at 150" with an equal quttntityofquinaldine a compmnd C9NH6*CH CH*C,NH,Me is formed. It is ayellow powder almost insoluble in the usual solvents soluble inaniline phenylhydrazine &c. and in strong acetic acid.Derivatives of Isoquinoline. By S. GABRIEL (Ber. 18 3470-3 180).-Tn continuation of investigations on substances derived fromisobenzalphthalide (Abstr. 1885,12;31) t,he author adds further obser-N. H. M266 ABSTRACTS UP CHEMICAL PAPERS.vations on isobenza~hthaZimid.ine.This substance to which theformula c6&<C(oH) N> is now given in place of -CH*CPh-crystallises in the asymmetric system with axial ratios a b c =0.8601 1 (?) ; its formation from isobenzalphthalide is analogous t othat of oxynicotinic from cumalinic acid. The presence of a hydroxyl-group in the compound is evidenced by the formation of a compound,C,H,NCl from it by the action of phosphorus oxychloride whilstphosphoric chloride yields a dichloro-compound CsH,< c-,ll- >.The latter melts a t 162-163'; the former crystallises in needlesmelting a t 77-78' ; it is soluble in benaene and ether.On heating the dichloro-compound with amorphous phosphorus(1 part) arid hydriodic acid (8 parts) n monochloro-compound,CIBHIONC1 is produced isomeric with the one above mentioned ; it crys-tallises in short glistening pyramids melts at 68-70' and forms acrystalline hydrochloride C15HloNCl,HC1 and a pZatinochZoride crys-tallising in sparingly soluble orange-yellow needles ; to this com-pound the formula C 6 H 4 < g g ! k > is ascribed.If these formulzare correct therefore the constitution of the last-named substance isthat of a phenylisoquinoline. The moiiochloro-compound (m. p. 77'),when heated with amorphous phosphorus and hydriodic acid isconverted into phenylisoquinoline c6H4<cH-N> which crystal-lises in rhombic plates melting at 103-105" ; its hydmckloride formsorange-red pointed needles.On reduction with sodium amalgam both the di- and mono-chloro-derivatives yield tetrahydride of phenylisoquinoline C,H,N whichforms glassy crystals ; it melts at 45-48" and is soluble in water andacetic acid.It is probable that phenylisoquinoline is identical witha base formerly obtained by the author by the disbillation of plitha-limide with zinc-dust. V. H. 1'.CC1. CPh-NCH CPhParaxanthine and Heteroxanthine. By G. SALOMON (Ber. 18,3406-3410) .-As a correction of former observations on paraxan-thine a constituent of human urine (Abstr. 1883 Sol) the authorascribes to it the formula C,H8N,0 namely that of a dimethyl-xanthine isomeric with theobromine instead of the more complexformula C,H',N,O,. Further it is now shown that paraxanthine formsa sparingly soluble precipitate with mercuric chloride provided thatthe latter be in excess ; this consists of colourless prisms meltingwith partial decomposition ; it is readily soluble in hot water.Para-xan thine hydrochloride crystallises with difficulty ; it forms an orange-yellow crystalline platinochloride.These extended researches have led to the isolation of another con-stituent of human urine which it is proposed to call heterozanthine.In order to separate this the amorphous residue obtained as a byeORG-IX IC CHEMISTRY. 267product in the preparation of paraxanthine is dissolved in ammonia,the solution filtered from the calcium phosphate and oxalate andevaporated down when the heteroxanthine crystallises out. It is bestpurified by means of the crystalline sodium-derivative obtained by theaddition of soda to a solution of the heteroxanthine.The base is awhite amorphous granular powder ; it exists in urine it1 the propor-tion of 1 gram in 1000 litres. Its composition is expressed by theformula C6H6N402 corresponding with that of a metbylxanthine. It isdifferentiated from hypoxanthine xanthine and guanine by the above-mentiol;ed soda reaction and from paraxanthine by its amorphous form,its sparing solubility the ready solubility of its hydrochloride in notyielding a precipitate with picric acid in presence of hydrochloric acid,and in not emitting the characteristic odour of paraxanthine whenheated. It is precipitated by copper acetate phosphotungstic acid andlead acetate in presence of ammonia. Its hydrochloride forms trans-parent crystals arranged in tufts; it gives a minutely crystalline platino-chloride.With mercuric chloride the base yields a greyish-yellowprecipitate becoming crystalline after a time ; it contains chlorine,and is converted by silver nitrate and ammonia into a silver com-pound. V. H. V.Doundak6 or African Quinine. By E. HECKEL and F. SCHLAG-DENHAUFFEN (Ann. Chim. Phys. [6] 6 313-328). The authors havemade careful examinations of this bark from various sources and,contrary to the results obtained by Bochefontaine Feris and Marcus,find that it contains no alkaloid whatever but that the bitter principleconsists of two nitrogenous resino'id yellow colouring matters,soluble in alcohol and alkalis one being insoluble and the othersoluble in water.The bark also contains a third principle of abrown colour insoluble in water and having no taste; glucoseand small quantities of tannin chlorophyll and two fatty substanceswere also present. A. P.Strychnine-derivatives. By W. F. LOERISCII and P. SCROOP(Monutsh. Chem. 6,844-862) .-iVitrostyychnine N02*C?1H21N202 maybe obtained by gra>dually adding 1 part of amhydrous strychninenitrate t o 10 parts by weight of sulphuric acid the temperaturebeing kept below 20° and the mixture allowed to remain for eightdays then poured into 80 paats of water and neutralised withammonia the nitro-compound thus precipitated is collected and re-crystallised from dilute alcohol ; it forms yellowish plates becomesslightly brown and melts a t 225" and dissolves in the usual solvents.The yield is about 88 per cent.of the strychnine nitrate employed.It is as strongly basic as strychnine and does not give any colourreaction with sulphuric acid and dichromate.N02.C21H21N202,HC1forms hair-like crystals and is insoluble in cold adcohol. Theplutinochloride ( N0,*Ce,H2,Nz02)2,HzPtC16 forms a light yellowgranular precipitate and is insoluble in water and alcohol ; on drydistillation it gives a strong quinoline-like odour. The nitrate,The hyhchloride268 ABSTRACTS OF CBEJllChL PhPERS.tas*trnte olrnlate and acetate were also prepared. Solutions of theacetate yield precipitates with the usual alkaloidal reagents.Amido-str?~chiliiLe NH2*CZ1Hz1NZO2 may be prepared by acting on thehydrochloric acid solution of the nitro-compound with tinfoil a tabout 20” ; i t forms small coloualess cubical crystals melts a t 275”,and boils without decomposition a t about 280” under 5 mm.pressure ;it is insoluble in water and acbs as a diacid-base. I t s salts are con-siderably more soluble in water tban those of strychnine ; on exposureto the air they are ooloured a reddish-violet solutions of the neutr:11salts yield precipitates with the usual alkaloidal reagents ; by treatingthe base dissolved in excess of nitric hydrochloric or sulphuric acid,with a sol~~tion of potassium dichromate an intense pure bluecoloration or in concentrated solutions even a blue precipitate isformed which if the free mineral acids be removed by the additionof sodium acetate will remain unaltered €or a week ; by warming thesolution in the presence of acid idi turns violet and finally if thequantity oE free acid is considwable forms a clear yellow solution ;the reaction is as delicate as the dichromate strychnine react#ion.Byheating the amido-base with alcobolic potash and chloroform i tyields the characteristic isonitrile odour. The hydrochlorideNHZ.C2,H2,N,O,HCL forms long brilliant prisms and is readilysoluble in water ; the platinochloride is rather unstable and forms anamorphous yellow precipitate and by dry distillation yields a quino-line-like odour. The nitrate forms octohedra and after a time turnsa violet colour. By treating an alcoholic solution of the nitro-strychnine described above with alcoholic potash the potassiurr-derivative of a compound isomeric with the nitro-compound and towhich the authors give the name of “xanthostrychnoZ,” is formed ;the free compound crptallises in slender yellow needles is iusolublein water but dissolves in most of the other umal solv.ents; it yieldsprecipitates with the alkaloYda1 reagents.The platinochloride( C21H21N,04)2,H,PtCl forms a bright-yellow precipitate ; the nitrate,mZphrzte and hydrochloride were also prepared. Although in the abovecompounds xanthostrychnol acts as a base it also possesses acid orpheuolic properties yielding unstable oompounds with bases. Thepotassium-derivative forms brilliaat ruby-red needles is decomposedby carbonic acid and is soluble in thm usual solvents ; when heated,it explodes slightly; its solution yields precipitates with most of themetallic salts which are however very unstable.By acting onthe hydrochloric acid solution of xanthostrychiiol with tinfoil tworeduction products are formed which are not yet thoroughlyexamined.A monob~omstrychn~ne C?1H21BrN202 which differs from that ob-tained by Beckurts (Abstr. 1885 911) may be prepared by treatingR sulphuric acid solution of strychnine with bromine the acid solutionIS diluted and the base precipitated with ammonia ; it forms colourlessneedles which dissolve readily in water but are insoluble in alcohol ;its solntion in sulphuric acid yields an indigo-blue coloration on theaddition of potassium dichromate ; its salts are more soluble in watert hnn the corresponding strychnine compounds ; the hydrochloride thenitrate and the platinochloride were preparedORQSNIC CHEMISTRY. 269Strychninesulphonic acid CZlHz,N2O2-SO3H may be prepared byslowly adding 1 part of anhydrous strychnine sulphate to 6 partsof fuming sulphuric acid cont,aining 30 per cent. of the anhydride,keeping the temperature below 20° and allowing the mixture toremain for a fortlnight. It forms a brittle transparent yellow mass,readily soluble in water and alcohol ; i t does not yield any colorationwith sulphuric acid and potassium dichromate. The barium ctdciunz,potassium sodium and lead salts were prepared they are all soluble in.water. By fusing the acid with sodium hydroxide a new derivativeis formed which yields a violet colour with ferric chloride. Theauthors have repeated the experiments of Beckett and Wright (thisJourn. 1874 G 5 ) of Schiitzenberger (Annalen 108 353) and ofShenstone (Trans. 1885 141) but cannot confirm their results.An examination of the pb ysiological action of nine derivatives ofstrychnine shows that they all possess poisonous properties alihoughin a less marked degree than strychnine itself. A. P.Strychninesulphonic Acids. By C. STOEHR (Bey. 18 3429-3432) .-Strychnine when heated wiih concentrated sulphuric acid atloo" yields a n~onoszdpphonic acid C2~Hz~N2OZ.SO3H a colourlesssubstance very sparingly soluble in water.Its potassium sodium and barium salts are colourless precipitates ;the arnmonI'urn salt is soluble in water but undergoes decompositionwhen its solution is evaporated.Concentrated sulphuric acid and sulphuric anhydride a t 150"yield a disulphonic acid Cz1H2,NzOz( SO,H) a colourless amorphoussubstance readily soluble in water sparingly soluble in ether andbenzene; its neutral bari.z6m salt crystallises in minute plates thebarium hydrogen salt is a pale-yellow amorphous powder.These results are not in exact accordance with the observations ofLoebisch and Schoop (preceding Abstract). V. H. V.Piperidine from Pentamethylenediamine. By A. LADENBURG(Bey. 18 3100-3102 comp. this vol. p. 139).-18 grams of penta-methylenediamine hydrochloride were quickly distilled and theproduct again dist'illed with aqueous potash solution. Much ammoniais formed. The distillate was treated with strong potash solution,shaken up several times with ether and the base extracted from theether with hydrochloric acid. The salt thus obtained was identifiedas piperidin; hydrochloride ; the yield was 8 grams.N. H. N.Hopeine. (J. P h a ~ n z . [ 5 ] 12 460-462.)-This crystallisablenarcotic alkaloid can only be obtained with difficult.y as most varietiesof hops do not contain more than traces. I t was first obtained fromwild American hops. The investigations of Smith Williamson Myers,and Springmuhl show that the pure alkaloid has an energetic actionsimilar to t'hat of morphine. German hops contain only traces of it ;some English varieties have given 0.05 per cent. whilst American wildhops have yielded 0.15 per cent. In the pure form it is obtained asbrilliant white needles or as a white crystalline powder solubleVOL. L. 270 ABSTRACTS OF CHEMICAL PAPERS.in 800 parts of water a t 15" and in 50 parts alcohol a t 15"; itcrystallises out on cooling the hot alcoholic solution. To extracthopeine hops are digested with a 16 per cent. solution of glucosecontaining a little acetic acid then boiled for six hours under pres-sure. The liquid is filtered t,hrough carbon and is evaporated untilthe sugar crystallises. The alkaloi'd is extracted from the residue bymeans of alcohol and the solution filtered and evaporated. The residueis treated with ether and alkali to separate certain alkaloids present,and finally pure hopeine is obtained by repeated crystallisations of itsalcoholic solutions. J. T.New Acid Analogous to Cholic Acid. By P. LATSCHINOFF(Ber. 18 3039-3047).-Cholic acid obtained from ox-gall was foundto contain a new acid choleic acid C2,H4,0 which was separated fromi t by means of the barium salt. The new acid forms large quadraticcrystals (with 1; mol. H20) but separates from a concentrated solu-tion in groups of slender needles (anhydrous) ; it is less soluble inwater alcohol and ether than cholic acid. The anhydrous acidmelts at 185-190'. The barium (with 3 mols. H,O) and the siZversalts were prepared. When choleic acid is oxidised by means ofpotassium dichromate and sulphuric acid it yields cholanic acid.Cholic acicl treated in the same way yields bilianic acid. The authoiiconfirms the result of Hammarsten (Abstr. 1881 62.5) who obtaineddehydrocholic acid by gently oxidisiiig cholic acid with chromicanhydride in acetic acid solution and repeated the experiment withcholeic acid which yielded dehydrocholeic acid C2,H3,0a. This formsirregular plates with a fatty lustre melting a t 182-183". The saltsare analogous to those of dehydrocholic acid but are more sparinglysoluble. N. H. M.Digestion of Elastin with Pepsin. By J. HORBACZEWSKI (Chew,.Centr. 1885 843) .-Elastin is slowly digested by gastric juice withformation of hemielastin and elastinpeptone ; these substanceswere obtained pure by dialysis. In aqueous solution hemielastinis precipitated by acetic acid and potassium ferrocyanide whilstelastinpeptone remains unprecipitated. Hemielastin when dried forsome time a t 110-120" becomes insolnble and with exception ofmicroscopic structure acquires all the properties of elastin ; elastin-peptone contains more hydrogen and oxygen than elastin.H. P. W.Proteids. By P. SCH~TZENBERGER (Compt. rend. 101 1267-1270) .-Noncrystallisable leucein obtained by the action of baryta oncoagulated albumin only gives analytical results concordant with theformula xCaH,NOz after drying for a long time at 140-150". Ifdried a t 100-llO" i t retains water of constitution. Leucei'n can besplit up into equal equivalents of two compounds. One is a strongayid proteic acid of the composition CsH14NzO5 which forms a gumm1noncrystnllisable barium salt insoluble in alcohol of 90". The other,gZucoprotez/? C,H,N,04 is a neutral body soluble in water and incold absolute alcohol. It cry stallises with difficulty in indistincPHTSIOLOGICAL CHEMISTRY. 271crystals. These two compounds stand in the relation of an acid andt,he corresponding alcohol and leucei'n dried a.t 1.50" represents theproduct of their union with liberation of water thus C,H,~N20 +C,H,N,O = H20 + C]6&8N40 or 4C4H,N0,. These facts com-bined with the author's previous researches (Abstr. 1879 542) leadto the conclusion that albumin has the formula C29&,N6010 and thatits decomposition by baryta is represented by the equation C2,H4,N,O,H,C,O + 2NH3 or one molecule of albumin is formed by the unionof 1 mol. leuce'in with 1 mol. each of leuce'in amidovaleric acid andoxalic acid and 2 mols. of ammonia water being eliminated. Thisview agrees very closely both with the composition of albumin andthe proportions of the products obtained by the action of baryta.Leucein when oxidised yieids products which indicat'e that it isclosely related to the succinic acid series.+ 7HQO = CGHiSN02 + C5HiiNO2 + [C,H,N,O + C~HI~N,O~] +C. H. B

ISSN:0368-1769    

DOI:10.1039/CA8865000215

出版商:RSC    

年代:1886

数据来源: RSC