摘要:

J O U R N A L J. DEWAR, LL.D., F.R.S. WYNDHAM R. DUNSTAN, M. A., F. R.S. C. E. GROVES, F. R. S. A. VERNON HARCOURT, M.A., F.R.S. C. T. HEYCOCE, M.A., F.R.S. OF H. FORSTER MORLEY, M.A., D.Sc. A. SCOTT, D.Sc., F.R.S. T. E. THORPE, LL.D., F.BS. W. A. TILDEN, D.Sc., F.R.S. THE CHEMICAL SOCIETY, ABSTRACTS O F PAPERS ON ORGANIC CHEMISTRY. 0. F. BAKER, Ph. D., B.Sc. C. H. BOTHAMLEY. A. C. CHAPMAN. H. CROMPTON. A. W. CBOSSLEY, M.Sc., Ph. D. W. A. DAVIS. T. EWAN, B.Sc., Ph.D. M. 0. FORSTER, Ph.D., D.Sc. W. D. HALLIBURTON, M.D., B.Sc., A, HARDEN, M.Sc., Ph.D. L M. JONES, B.Sc. L DE KONINGH. 4 . LAPWORTH, D.Sc. T. LEONARD, B.Sc. .i. R. LE SUEUR, B.Sc. F. R. S . A. R. LING. D. A. LOUIS. T. M. LOWRY, D.Sc. N. H. J. MILLER, Ph.D G. T. MORGAN, D.Sc. J. C. PHILIP, M.A., Ph.D. R. H. PICEARD, D.Sc., Ph.D. T. H. POPE. w. J. POPE. E. C. ROSSITER. M. J. SALTER. L. J. SPENCER, M.A. J. J. SUDBOROUQH, Ph.D., D.Sc. J. F. THORPB, Ph.D. E. W, WHEELWRIGHT, B. A., Ph.D. 1899. Vol. LXXVI. Part I. LONDON: GURNEY & JACKSON, 1, PATERNOSTER ROW. 1899.RICHARD CLAY AND SONS, LIMITED LONDON AND BUNOAV

ISSN:0368-1769    

DOI:10.1039/CA89976FP001

出版商:RSC    

年代:1899

数据来源: RSC

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J O U R N A L HORACE T. BROWN, LL. D., F. R.S. J. DEWAR, LL.D., F.R.S. WYKDHAM R. DUNSTAN, M.A., F.R.S. C. E. GROVES, F.R.S. A. VERNON HARCOURT, M.A., F.R.S. C. T. HEYCOCK, M.A., F.R.S. O F R. MELDOLA, F.R.S. H. FORSTER MORLEY, M. A., D. Sc. A. SCOTT, D.Sc., F.R.S. T. E. THORPE, LL.D., F.R.S. W. A. TILDEN, D.Sc.,F.R.S. THE CHEMICAL SOCIETY. C. F. BAKER, Ph.D., KSc. C. H. BOTHAMLEY. A. C. CHAPMAN. H. CROMPTON. A. W. CROSSLEY, M.Sc., Ph.D. w. A. DAVIS. T. EWAN, B.Sc., Ph.D. M. 0. FORSTER, Ph.D., D.Sc. W. D. HALLIBURTON, M.D., B.Sc., A. HARDEN, M.Sc., Ph.D. L. M. JONES, B.Sc. L. DE KONINGH. A. LAPWORTH, D.Sc. N. LEONARD, B.Sc. F.R.S. H. R. r,E SUEUR, B.s~. ABSTRACTS O F PAPERS A. R. LING. D A. LOUIS. T. M. LOWRY, D.Sc. N. H. J. MILLER, Ph.D. G. T. MORGAN, D.Sc. J. C. PHILIP, M.A., Ph.D.R. H. PICKARD, D.Sc., Ph.D. T. H. POPE. W. J. POPE. E. C. ROSSITER. M. J. SALTER. L. J. SPENCER, M.A. J. J. SUDBOROUGH, Ph.D., D.Sc. J. F. THORPE, Ph.D. E. W. WHEELWRIGHT, B.A., Ph.D. 1899. Vol. LXXVI. Part 11. .- LONDON: GURNEY & JACKSON, 1, PATERNOSTER ROW 1899.J O U R N A L HORACE T. BROWN, LL. D., F. R.S. J. DEWAR, LL.D., F.R.S. WYKDHAM R. DUNSTAN, M.A., F.R.S. C. E. GROVES, F.R.S. A. VERNON HARCOURT, M.A., F.R.S. C. T. HEYCOCK, M.A., F.R.S. O F R. MELDOLA, F.R.S. H. FORSTER MORLEY, M. A., D. Sc. A. SCOTT, D.Sc., F.R.S. T. E. THORPE, LL.D., F.R.S. W. A. TILDEN, D.Sc.,F.R.S. THE CHEMICAL SOCIETY. C. F. BAKER, Ph.D., KSc. C. H. BOTHAMLEY. A. C. CHAPMAN. H. CROMPTON. A. W. CROSSLEY, M.Sc., Ph.D. w. A. DAVIS. T. EWAN, B.Sc., Ph.D. M. 0. FORSTER, Ph.D., D.Sc. W. D. HALLIBURTON, M.D., B.Sc., A. HARDEN, M.Sc., Ph.D. L. M. JONES, B.Sc. L. DE KONINGH. A. LAPWORTH, D.Sc. N. LEONARD, B.Sc. F.R.S. H. R. r,E SUEUR, B.s~. ABSTRACTS O F PAPERS A. R. LING. D A. LOUIS. T. M. LOWRY, D.Sc. N. H. J. MILLER, Ph.D. G. T. MORGAN, D.Sc. J. C. PHILIP, M.A., Ph.D. R. H. PICKARD, D.Sc., Ph.D. T. H. POPE. W. J. POPE. E. C. ROSSITER. M. J. SALTER. L. J. SPENCER, M.A. J. J. SUDBOROUGH, Ph.D., D.Sc. J. F. THORPE, Ph.D. E. W. WHEELWRIGHT, B.A., Ph.D. 1899. Vol. LXXVI. Part 11. .- LONDON: GURNEY & JACKSON, 1, PATERNOSTER ROW 1899.

ISSN:0368-1769    

DOI:10.1039/CA89976FP003

出版商:RSC    

年代:1899

数据来源: RSC

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INORGANIC CHEMISTRY. Inorganic Chemistry. Electrolytic Formation of Hydrogen Peroxide. By FRITZ HABER and S. GRINBERG (Zeit. anorg. Chem., 1898, 18, 37--47).-The authors, on repeating their experiments on the electrolysis of hydrochloric acid (A bstr., 1898, ii, 215 and 365),find that there is no formation of hydrogen peroxide, as previously stated. The test which they employed consisted i n shaking the electrolyte with mercury, and then treating with titanic acid. They now find that the small quantity of hydrogen peroxide pre- viously detected is produced by the action of the air and the finely divided mercury during the filtration. Experiments with platinum and gold electrodes show that if hydrogen peroxide is formed, it is destroyed by a secondary reaction, which takes place according to the equation H,02 + 0 = H,O + 0,, and such a small quantity remains undecomposed that it is not possible to detect it.By EMMANUELE PAT ERN^ and UGO ALVISI (Gccxzettcc, 1898, 28, ii, 18--24).-Those metallic oxalates which are sparingly soluble OF insoluble in water are less soluble in hydrofluoric acid than in solutions acidified with hydrochloric or sul- phuric acid. On adding oxalic acid to a hydrogen fluoride solution of cupric fluoride, cupric oxalate, 2CuC204 + H,O, separates, and only traces of copper remain in solution. Although solutions of manganese chloride, nitrate, or sulphate in the corresponding acid are not precipitated by oxalic acid, yet on adding oxalic acid to a hydrogen fluoride solution of manganese fluoride and warming, a granular, white precipitate of manganic oxalate, MnC,O4,2H20, is obtained, and only traces of manganese remain in solution.Oxalic acid does not give a precipitate with mercuric chloride solution, but throws down mercuric oxalate from a solution of mercuric fluoride in hydrofluoric acid. On heating powdered fluorspar with concentrated oxalic acid solution on the water-bath, the fluorine is slowly but wholly eliminated; the same occurs with magnesium fluoride and the fluorides of the cerite earths, yttria, thoria, &c. ; this fact may be applied in the analysis of incandescent gas-lamp mantles. Concentrated tartaric acid solution decomposes fluorspar completely on the water-bath, although more slowly than oxalic acid. Sulphurous anhydride acts on cupric fluoride, depositing Chevreul’s salt of the composition CU,SO,~CUSO, + 2H,O in minute, red crystals ; the precipitation is, however, incomplete.An acid solution of silver fluoride is precipitated by arsenates, chromates, nitrites, platino- chlorides, and sulphurous acid. E. C. R. Reactions of Metallic Fluorides. W. J. P. VOL. LXXVI. ii. 218 ABSTRACTS OF CHEMICAL PAPERS. Reactions of Fluoro- and Fluoroxy-salts. By EMMANUELE PAT ERN^ and UGO ALVISI (Gazxetta, 1898,28, ii, 24--29).-0n treating, with aqueous oxalic acid, solutions of the silicofluoride, fluoroxyuranate, fluoroxytungstate, fluoroxymolybdate and the hydrogen fluoride of potassium, potassium quadroxalate separates and the corresponding fluoro- or fluoroxy-acid remains in solution ; the silicofluorides of cerium, lanthanum, yttrium, &c., behave similarly, all the fluorine being eliminated from the salt.On heating cryolite with concentrated oxalic acid solution on the water-bath, hydrogen fluoride is evolved, the aluminium fluoride being first decomposed and subsequently the sodium fluoride ; similarly, on passing steam over red-hot cryolite, alumina, hydrogen fluoride, and sodium fluoride are first formed, and in a second stage of the reaction the sodium fluoride is attacked by the water vapour. Triplite is also decomposed by heating with oxalic acid solution. Tartaric acid in aqueous solution also decomposes potassium silico- fluoride and cryolite. Ozone. By ALBERT LADENBURG (Bey., 1898, 31, 2508-2513).- Ozonised oxygen is condensed by means of liquid air and then allowed to partially evaporate, by which the residue is rendered much richer in the less readily volatile ozone.This operation is again repeated and the ozone finally allowed to evaporate; in this way, a gas is obtained which contains 86.16 per cent. by weight of ozone, and has a density of 1.3698 as compared with oxygen, the density being calculated from the rate of effusion determined in Schilling’s apparatus. From these data, it follows that the density of piire ozone would be 1-456 as compared with oxygen, whereas the theoretical density is 1.5. Ozone is not so soluble in water as is usually supposed, since at the normal pressure and ordinary temperature, water only absorbs 0.01 volume or 0*00002 part by weight. An attempt was made to determine the boiling point of ozone by con- densing ozonised oxygen, allowing the oxygen to evaporate, and then as- certaining the temperature at which the residual ozone evaporated.The oxygen volatilised at - 186’ leaving 4-5 C.C. of an almost black opaque liquid, The temperature as indicated by the thermometer then rose to - l2So, at which point the apparatus exploded violently, so that this can only be taken as a lower limit. By RUDOLPH JOH. KNOLL (Ber., 1898,31, 2183--2185).-This alleged compound, S,OCl, (Abstr., 1882, 694), is in reality a mixture of sulphur dichloride, thionyl chloride, and sulphuryl chloride, approximately in the proportions, 17SC1, + 2SOC1, + 5,SOC1,. When it is distilled alone (under 50 mm. pressure), the first fraction of the distillate has not quite the same composition as the last.When it is distilled with sulphur, thionyl and sulphuryl chlorides distil over, and finally sulphur chloride, S,Cl,, which must have been formed by the action of the sulphur on the sulphur dichloride present. C. F. B. By VICTOR LENHER (J. Anzer. Chem. Xoc., 1898, 20, 555--579).--Two series of determinations of the atomic weight of selenium were made by analys- W. J. P. A. H. Ogier’s Sulphur Oxychloride. Atomic Weight and Derivatives of Selenium.INORGANIC CHEMISTRY. 19 ing carefully purified silver selenite, Ag,SeO,, and ammonium seleni- bromide, (NH,),SeBrG. The silver employed in preparing the former was purified by Stas’s method and converted into nitrate ; the selenious anhydride was prepared from pure selenium by means of nitric acid, and was purified by repeated sublimation.On dissolving i t in water and adding the purified silver nitrate, a white precipitate of silver selenite was obtained which crystallised from dilute nitric acid in anhydrous plates having a sp. gr. = 5.9297. The analyses were carried out by expelling the selenium completely in the form of dioxide, by passing hydrogen chloride over the salt contained in a porcelain boat, heated in a combustion tube ; the residue of silver chloride was weighed, and was then reduced by purified hydrogen to metallic silver, and the latter weighed. The average of eleven experiments gives as the atomic weight of selenium, calculated from the silver chloride formed, the value 79.329 (0= 16), the probable error being +OmO09 ; exactly the same value was obtained from the weight of reduced silver in eight of these experiments.Attempts to obtain sodium selenite siifficiently pure to serve as a means of determining the atomic weight of selenium failed. Ammonium selenibromide, however, was readily prepared pure by dissolving ammonium bromide (9 parts) in water, adding selenium (4 parts) and a slight excess of bromine until a clear solution was obtained, and heating on the water-bath until the excess of bromine was expelled ; on slow evaporation, crystals of ammonium seleni- bromide separated, which were purified by repeated crystallisation. Special care was taken t o purify the materials used in preparing the salt. The latter was analysed by precipitating the selenium by hydroxyl- amine hydrochloride, according to Keller’s method (Abstr., 1898, ii, 575), and the mean of eight experiments gave a value 79.285 (0= 16) for the atomic weight, with a probable error +,OmO1l.The general mean of all the author’s experiments is 79.314. Double Bromides of 8elenium.-Although potassium and ammonium selenibromides are easily obtained by adding potassium or ammonium bromide to an aqueous solution of selenium tetrabromide (Muthmann and Schafer, Abstr., 1893, ii, 318), the corresponding sodium and lithium salts do not appear to exist. The selenibromides of rubidium, Rb,SeBr,, and casium, Cs2SeBr6, are somewhat less soluble than the corresponding potassium salt, although closely resembling it in crystalline form ; they are best prepared by adding a slight excess of bromine to a solution of the alkali bromide containing in suspension the theoretical amount of selenium, and evaporating on the water-bath until crystals separate.Corresponding organic salts containing selenium can be prepared by adding the hydrobromide of a base, dissolved in alcohol, to analcoholic solution of selenium dioxide in concentrated hydro- bromic acid. They are all decomposed by water, and prolonged digestion with ether extracts selenium tetrabromide. IWethyZamine selenibvomide, (NH,Me),,H,SeBr,, separates from alcohol containing hydrobromic acid in well defined red crystals; ethylarnine seZenibq*onzide, (NH,Et),,H,SeBr,, formsred, hexagonal prisms. Thedinzethylnmine salt, (NHMe,),,H,SeEr,, and the trimethykmine salt, (NMe,),,H,SeBr6, separate from alcohol in redcrystals, whilst tetvethykunanaoizium selen&oi?aide, ( NEt,),SeBr,, forms 2-220 ABSTRACTS OF CHEMICAL PAPERS.flat, hexagonal plates. On adding the hydrobromides of aniline and diphenylamine to an aqueous solution of selenium tetrabromide, no double salt is formed, but the selenium is almost completely precipitated in the free state. Phenylhydrazine and quinoline act similarly ; pyri- dine hydrobromide, however, gives rise to the salt, (C,H,N),,H,SeBr,, which crystallises from alcohol in deep-red leaflets or prisms, but is de- composed by other solvents. The p'peridiw salt, (C,H,,N),,~,SeBr,, which crystallises from alcohol in red plates, closely resembles the pyridine derivative. Existence of Selenium Monoxide (compare Pierce, Abstr., 1898, ii, 403)-In subliming large quantities of pure selenious anhydride, no odour similar to that attributed by Berzelius to selenium monoxide was noticeable. On heating a mixture of equivalent quantities of sele- nium and its dioxide, either in an open vessel, or in a sealed tube, to the boiling temperature of selenium, no interaction took place, and no gaseous product could be detected. Selenium monobromide does not act on dry silver oxide below 20", but at this temperature a violent action takes place, selenious anhydride alone being formed. From these exDeriments.it is concluded that selenium monoxide does not exist (coipare Chabri6, Ann. Chim. Phys., 1890, [vi], 20, 273). W. A. D. NOTE BY ABSTRAGTOR.-NOrriS (Abstr., 1898, i, 510), has already described the salt, (NHMe,),,H,SeBr,, prepared from dimethylamine, and in addition has obtained the salts, 3NHMe2,HBr,SeBr,2SeBr, ; 2(NHMe,,HBr,),SeBr4 ; 2(NHMe2,HBr2),SeBr, ; and 2( NHMe,,HBr,),NHMe,,H Br,SeBr,.Similar salts were also obtained from trimethylamine. Copper Selenarte. Preparation of Selenic Acid. By R E N ~ METZNER (Compt. rend., 1898, 12'7, 54-57).--8 solution of selenious acid was oxidised by a current of chlorine, the reaction being accom- panied by the development of 30 Cal., and the solution of selenic acid thus obtained was neutralised with piwe cupric oxide. On cooling the liquid, after concentration by evaporation, pale blue prisms of copper selenate, CuSeO, + 5H,O, were deposited. Attempts were made to substitute bromine for chlorine in the preparation of the salt, but it was found that the oxidation of the selenious acid was never com- plete. The solubility of copper selenate varies greatly with the temperature; 1 litre of the saturated solution was found to contain 257 grams of the salt at 15", 346 grams at 35", and 435 grams a t 55".A t about 70°, the solution undergoes decomposition, with formation of it green, crystalline deposit which is seen under the microscope to consist of small, monoclinic prisms. This compound was first obtained, but not analysed, by Mitscherlich ; the author's analyses show that i t has the composition 2CuSe04,Cu0 + 5H,O. When crystallised from a solution containing a large excess of selenic acid, copper selenate forms microscopic, transparent, tabular crystals of the composition CuSe04+2H,0.The crystals lose water on exposure to a dry atmosphere, and when dried at 100" only one molecule of water is retained. The heat of formation of copper selenate (18.12 Cal.) was deduced from the heat developed (13.06 Gal.) on precipitating aINORUANIC CHEMISTRY. 21 normal solution of the salt with the equivalent amount of potash. The heat of dissolution is - 2-66 Cal. Selenic acid was obtained in a very pure state by the electrolysis of a saturated solution of copper selenate with a current of 5 amperes a t 2-3 volts. N. L. Decomposition of Nitric Acid by Heat a t Moderate Tempera- tures. By MARCELLIN P. E. BERTHELOT (Compt. rend., 1898, 127, 83--88).--Small quantities of purenitric acid were introduced into tubes previously made vacuous and having a volume about 20 times that of the liquid, and the tubes were then kept in the dark at the ordinary temperature for several weeks ; the nitric acid remained unaltered.When, however, similar tubes are heated a t loo', also in the dark, the nitric acid decomposes into nitric peroxide, oxygen, and water, and the decomposition at first increases with the time, but the rate of increase gradually falls. The decomposition is always incomplete and is limited chiefly by the water produced. Nitric acid of sp. gr. 1.333 undergoes practically no change at looo under similar conditions. The decomposition can scarcely be regarded as reversible, since the oxygen will combine very slowly with any nitrous acid that may be formed by the action of the nitric peroxide on the water.Thedecom- position of nitric acid into nitric peroxide, oxygen, and water at 100' would absorb about - 6.5 Cal. per molecule of acid. The decomposition of nitric anhydride absorbs much less, hence the instability of this compound. On the other hand, the heat of formation of hydrated nitric acid is much higher than that of the anhydrous acid, hence the greater stability of the former. Action of Free Hydrogen on Nitric Acid. By MARCELLIN P. E. BERTHELOT (Compt, rend., 1898,127,27-29).-Sealed tubes containing known quantities of hydrogen and concentrated nitric acid were exposed to direct sunlight for two weeks, kept in the dark during the same period, and heated a t 100' for 1 to 5 hours. I n every case, the original volume of hydrogen employed was recovered on examining the contents of the tubes, even when the experimental conditions had been such that the nitric acid itself was decomposed, with liberation of oxygen.This inactivity of hydrogen towarda nitric acid is in striking contrast with its behaviour with concentrated sulphuric acid, which is acted on at the ordinary temperature with formation of sulphurous acid. The liberation of oxygen from pure nitric acid takes place a t 100' and also, under the influence of light, in the cold ; it does not take place in the dark a t the ordinary temperature. The author's observations N. L. Action of Dilute Nitric, Sulphuric, Hydrochloric and Phos- phoric Acids on Nitrates in the Presence of Ether. By CHARLES TANRET (BztZZ. Soc. Chim., 1897, [iii], 17, 497--503).-It has pre- viously (Abstr., 1897, ii, 255) been shown that the presence of nitrates raises the coefficient partition of dilute nitric acid between ether and water.This property affords a basis for a method of extracting free nitric acid from solutions of nitrates by the aid of ether. C. H. B. on this point will be published hereafter.22 ABSTRACTS OF CHEMICAL PAPERS. The reaction between dilute sulphuric acid and an excess of potassium nitrate is represented as follows : H2S0, + 2KN0, = HNO, + KNO, + KHSO,. If the nitric acid thus formed is removed by ether, then the acid sulphate tends to dissociate under the influence of the water into sulphuric acid and the normal sulphate. The sulphuric acid will then act on a further amount of potassium nitrate according to the above equation, until the whole of the sulphuric acid has been converted into normal sulphate, as if the reaction had taken place according to the equation H,SO, + 2KN0, = K,SO, + 2HN0,.This has been proved experimentally by taking 20 C.C. of water containing 0.20 gram of sulphuric acid, dissolving in this 5 grams of potassium nitrate, and extracting with 200 C.C. of ether, the ex- traction being repeated six times. Hydrochloric acid reacts in the same manner as sulphuric acid. Phosphoric acid reacts according t o the equation H,PO, + KNO, = I’INO, + KH2P0,. Nitric acid acting on normal sulphates gives acid sulphates; the acid sulphate does not sensibly dissociate,. yielding free sulphuric acid. The action between nitric acid and chlorides is not appreciable.J. J. S. Homogeneity of Helium. By WILLIAM RAMSAY and MORRIS W. TRAVERS (PYOC. Boy. Xoc., 1898,52,3 16-324).-The gas was separated into six fractions by diffusion through a piece of pipe stem. Fraction No. 1 was then pumped into the diffusion vessel, one half of it was diffused and transferred to vessel No 1 ; fraction No, 2 was then added, and one-third of the mixture diffused and transferred to vessel No. 1 ; fraction No. 3 was then added, and one half of the whole diffused and transferred to vessel No. 2 ; fraction No, 4 added and one half diffused and transferred to vessel No. 3, and so on. After four such complete fractionations in the case of air, the extreme fractions contained 17-37 and 22.03 per cent. of oxygen respectively. In the case of nitrogen, prepared from solutions of ammonium chloride and sodium nitrite, with some copper sulphate, thirty fractionations produced no alteration in density.Repeated fractionations of samples of helium from samarskite and cleveite resulted in the separation of helium with density 1.98 and refractivity 0.1238 as the lightest fraction, and a very little nearly pure argon as the heaviest fraction. The light fraction was apparently pure helium, as further diffusion did not alter its density. “ It appears, therefore, tbat helium contains no unknown gas, nor is it possible to separate it by diffusion into any two kinds of gas; all that can be said is that most minerals which evolve helium also evolve argon in small quantity.” The authors had hoped to find an element with density = 10 and atomic weight = 20 ; they still regard the existence of such an element as probable, for it would form with He = 4 and A = 40 a triad like F= 19, Cl= 35.5, Mn= 55 and many similar triads occurring in the groups of the periodic table.Conversion of Potassium Iodide and Bromide into Potassium Chloride. By FRIEDRICH W. KUSTER (Zeit. anorg. Chem., 1898, 18, 77 - €32)-Potassium iodide is easily and completely con- C. F. B.INORGANIC CHEMISTRY, 23 verted into potassium chloride by heating it in a porcelain crucible in a current of chlorine, Potassium bromide, on the other hand, cannot be completely converted into chloride by means of a current of dry chorine unless it is heated to such a high temperature that potassium chloride begins to volatilise. I n the presence of water, however, the conversion into chloride is complete at moderate temperatures. The potassium bromide (2.49 grams) is treated in a small Erlenmeyer flask with 1 C.C.of water and a drop of hydrochloric acid and then heated in a brisk current of chlorine. The flask is placed on an asbestos plate with another asbestos plate 2 C.C. below the first and under this a small burner. After 1-14 hours heating below the boiling point, the water is evaporated off and finally the asbestos plate on which the flask rests is heated to redness for a short time, and the operation repeated until a constant weight is obtained. By H. C. HAEN (J. Amer. Chem. Xoc., 1898,20, 621-630).-This is an elaborate investigation as to the best way of accurately determining the sp.gr. of sodium chloride solutions. To be of any real value, the sp. gr. a t 15.08O should be exact to the fourth place of decimals. In this case, if X = the sp. gr., the percentage of sodium chloride will be 60,209,585 - 626,853,lS + 1067,352,66782 - 633,92Xs + 133,333,333S4. A main factor in determining the sp. gr. is the knowledge of the sp. gr. of the air in the balance case, which depends on the pressure, temperature, moisture, and the amount of carbonic anhydride. For further particulars, the original paper should be consulted, the results Action of Sodium Metarsenite on Metallic Salts, By C. REICHARD (Ber., 1898, 31, 2163-2171).-When sodium metarsenite, Na2As204, was added to excess of a solution of a metallic salt, free E. C. R. Speciflc Gravity of Sodium Chloride Solutions. being set forth in a very comprehensive table.L. DE E. Composition. Metallic salt used. Ni(N03)2 Pb(NOa12 ZnSO, SnCI, Properties. Bright green, amorphous powder. Heavy, white powder. Crystallises from ammonia in white needles. Yellowish-white ; decoiriposed by acids and alkalis Amethyst-coloured mass, White substance. Green, amorphous powder. Greenish-white substance, turning rusty in the air. White, turning pink to brown in the air. White mass, turning yellow and decomposing in Yellowish-white mass. Yellowish substance, decomposed by caustic soda with separation of metallic arsenic. daylight. with separation of metallic silver.24 ABSTRACTS OF CHEMICAL PAPERS. acid was always liberated, and the precipitate was in 4 cases (enumerated first in the table) an orthoarsenite, in 2 (the next two) a pyroarsenite, but in no case was it a metarsenite. The substances prepared are described in the table (p.23). Action of Hydrogen on Silver Sulphide. By H. P~LABON (Compt. rend., 1898, 126, 1864-1 866).-Hydrogen acts on silver sulphide in sealed tubes above 250', the proportion of hydrogen sulphide formed at first increasing with the time but eventually becoming con- stant. Conversely, in a tube containing silver and hydrogen sulphide, the quantity of the latter gradually diminishes until it reaches a limit. A t any given temperature above 350°, the limit is the same, whether the initial system contained hydrogen sulphide and silver, or silver sulphide and hydrogen. The ratio, p, of the partial pressure of the hydrogen sulphide to the total pressure of the mixture diminishes as the temperature rises and the curve that representsit as a function of the temperature approaches the axis of the abscissze as the tempera- ture increases.Between 360' and 700°, the curve is identical with a straight line passing through the points p = 0.21, t = 360', and p = 0.16, t = 700". Whatever the initial system, equilibrium is reached more quickly the higher the temperature; at 36O0, about 160 hours is necessary, whilst a t 580° a few moments suffice. At a given temperature, the limit value of p is independent of the physical con- dition of the silver or silver sulphide, and, moreover, is the same if the initial system consisted of silver, hydrogen, and sulphur. The silver liberated from the silver sulphide forms filiform masses only when the temperature is below 580°, and the best specimens are obtained by C.F. B. h e a h g crystallised silver sulphide and hydrogen in sealed tubes a t 440'. C. H. B. Heat of Formation of Lithium Carbide. By ANTOINE GUNTZ (Compt. rend., 1898, 126, 1866--1868).-The action of water on lithium carbide, C,Li,, develops + 37-10 Cal., and hence C, (diamond) + Li, sol. = C,Li, (sol.) develops + 11 93 Gal., a value which is much higher than the corresponding values for sodium or calcium, and explains the formation of lithium carbide under such varied conditions. When the carbide is prepared by the direct action of lithium on carbon, the mixture must be placed in an iron dish in a hard glass tube enclosed in a glazed porcelain tube, and the tubes must be made vacuous, because lithium readily combines with nitrogen.The temperature must not exceed a dull red heat, otherwise the carbide dissociates. Even the diamond is attacked by lithium a t this temperature. The carbide cannot be obtained by heating carbon with lithium carbonate, because the latter volatilises before it dissociates. When the carbide is added to fused lithium chloride, lithium subchloride and carbon are formed, but a t a high temperature the subchloride dissociates into the normal chloride and lithium, and the latter attacks the carbon, and these changes go on until a condition of equilibrium is established. These observations explain why a carbon cathode cannot be used for the isolation of lithium by electrolysis of the fused chloride.C. H. B.INOHGANIC CHEMISTRY, 25 Calcium Hydride. By HENRI MOISSAN (Compt . rend., 1398, 127, 29--34).-Calcium hydride is obtained by heating crystallised calcium (Abstr., 1898, ii, 578), contained in a nickel boat, to dull redness in an atmosphere of dry hydrogen. Comparison of the weight of metal employed with the weight of hydride obtained, and measurement of the volume of hydrogen evolved on treating the substance with water, show that the hydride has the composition CaH,. Obtained as above, calcium hydride forms a white, fused mass of crystalline fracture, which is shown by microscopic examination to consist of slender, transparent plates; it has a sp. gr. = 1.7. When heated to 600' in a vacuum, no appreciable dissociation occurs ; nor is the hydride affected by heating in hydrogen at the melting point of glass.It is decom- posed by the halogens at a dull red heat, with incandescence. When heated to redness in air or oxygen, it burns brilliantly, and sufficient heat is evolved to cause fusion and crystallisation of the calcium oxide formed, Calcium hydride is decomposed by heating in sulphur or phosphorus vapour, but no action was observed with selenium at the melting point of glass, or with nitrogen, silicon, and boron. When heated a t 700-80O0 with finely-divided carbon, calcium hydride is partially decomposed, with production of calcium carbide. Metallic fluorides, sodium chloride, and silver iodide are decomposed when heated with calcium hydride, but potassium iodide is not acted on.Chlorates, perchlorates, bromates, or permanganates, and similar oxidising agents, are reduced with explosive violence. Hydrogen sulphide, nitric oxide, and carbonic anhydride aro also decomposed a t a red heat. Calcium hydride is readily decomposed by water and by dilute acids ; concentrated sulphuric and nitric acids, however, have but little action in the cold. Benzene, turpentine, and alkyl chlorides and iodides, when free from water, are without action on calcium hydride; ethylic alcohol slowly attacks it. The vapour of carbon tetrachloride is decomposed, with incaadescence, a t about 400O. N. L. Solubility of Lime in Water at Different Temperatures. By ALEXANDER HERZFELD (Bied. Centr., 1898, 27, 5 7 1 ; from Oesterr. Zeits. Zuckerind., 1897, 1197).-The amounts of water required to dissolve 1 part of CaO at different temperatures are as follows.15" 20" 25" 30" 35" 40" 45" 50" 55" 60" 65" ?Oo 75" 80" 776 813 848 885 924 962 1004 1044 1108 1158 1244 1330 1410 1482 N. H. J. M. Solubility of Lime in Aqueous Solutions of Sodium and Potassium Chloride. By GODFREY L. CABOT (J. Xoc. Chem. Ind., 1897, 16, 417--419).-Curves are given which shorn that the solu- bility of lime in solutions of either sodium or potassium chloride is a maximum for all temperatures when the solution contains about 60 grams of the salt per litre; it is a minimum at any fixed tem- perature when the solution is saturated, the solubility then being much less than in pure water of the same temperature. A solution of sodium chloride dissolves more lime a t all temperatures and con- centrations than a corresponding solution of potassium chloride.I n26 ABSTRACTS OF CHEMICAL PAPERS, all cases, the maximum solubility of lime in the chloride sotutiofi occurs when the temperature is lowest; with solutions of all concen- trations, the solubility decreases regularly as the temperature increases. W. A. D. Formation and Composition of Bleaching Powder. By HUGO DITZ (Chem. Zeit., 1898, 22, 7--9).-The author regards the formation of bleaching powder as taking place in several stages. The first action of chlorine on the slaked lim; is t o give (Ca0,CaCl~OCl+2H20); further action gives (2CaCl*OC1+ CaO,CaCl*OCl+ 4H20) ; yet fur- ther action, (GCaCl*OCI + CaO,CaCl*OCI + 8H,O). In practice, the reaction seems to stop here; theoretically, it might continue inde- finitely, yielding successive members of the series [(Zn - 2)CaCI*OCl+ CaO,CaCl*OCl+ 2nH,O].Most bleaching powders consist of mixtures of the first three members, (n=O, 1, 2), the formulae of which are given above ; but of the numerous published analyses of blenching powders, some are found to correspond very well with these three; three such analyses are quoted below. n= 0. 12=1. n=2. Found. Calc. Found. Calc. Found. Calc. Total CaO ......... 52.12 51.14 44.12 44.01 41.27 41.14 Available C1 ...... 31.44 32-42 41-05 41.85 44.5 45.64 CaO from CaO,CaCI*OCl ... 27.33 25.57 11*80 11.00 5-40 5.14 It is shown that these views allow of a satisfactory explanation of the reactions of bleaching powder with carbonic anhydride, with sul- phurous anhydride, and with acetic acid, and of its behaviour when heated.It is proposed to perform experiments with a view to testing their truth further. c. I?. B. Decomposition of Barium and Calcium Dihydrogen Phos- phates by Water at 100". By GEORGES VIARD (Compt. Tend., 1898, 127, 178-180). -The monobasic phosphates of the alkaline earths are known to undergopartial decomposition by water at the ordinary temperature, with liberation of phosphoric acid and precipita- tion of a dibasic phosphate. The author has studied the decompo- sition of monobarium and monocalcium phosphates by water at loo", and finds the reaction to be similar to that which occurs in the cold, the quantitative results, however, are different. As the weight of monobasic phosphate which is heated with a constant weight of water increases, the ratio of the total phosphoric acid remaining in solution to the combined phosphoric acid also increases, a t first rapidly and then more slowly, until it becomes sensibly constant.The limiting value of this ratio was found to be 2.8 for the barium, and 2-34 for the calcium, salt; in the cold, the values obtained by Joly were 2.0 and 1 *5 respectively. Analysis shows that the precipitate consists only of the dibasic phosphate, unless a saturated solution has been employed, in which case the precipitate is contaminated with undissolved mono- basic phosphate. It is t o be observed that the precipitated dicalcium phosphate is always anhydrous and insoluble in acetic acid, whereas,IN0 RGANIC CHEMISTRY.27 if the decomposition takes place in the cold, the hydrated phosphate, Ca,H,(PO,), + 4H,O, is formed, which is soluble in acetic acid. The composition of the precipitate being once determined, the ratio R, of the total to the combined phosphoric acid may be calculated from the weight of the precipitate. For, if P is the weight of monobasic phosphate employed, iM its molecular weight, p the weight of dibasic phosphate precipitated, m its molecular weight, and q the molecular weight of phosphoric anhydride, then the weights of the latter contained in P and p are Pq/M and pq/m respectively and N. L. Anhydrous Crystalline Magnesium Sulphide. By A. MOURLOT (Compt. q*end., 1898, 127, 180--183).-Amorphous magnesium sul- phide is best prepared by passing a current of hydrogen sulphide over a mixture of sulphur with magnesium filings contained in a carbon boat, which is placed in a porcelain tube heated in a reverberatory furnace.The sulphide is thus obtained as a white, or slightly grey, mass, which analysis shows to have the composition MgS. Another method of preparation consists in passing hydrogen sulphide over anhydrous magnesium sulphate or oxide heated to about 1200' ; in this, however, the action is much slower. When the amorphous sulphide is heated for a few minutes in the electric furnace, it is converted into a globular mass of crystalline fracture, which is shown by analysis to have the same composition as the amorphous sulphide ; the crystalline sulphide may be also prepared by heating, in the electric furnace, a mixture of magnesium chloride with stannous sulphide in molecular proportion.Attempts to prepare i t by the reduction of magnesium sulphate with carbon gave unsatisfac- tory results. The crystalline magnesium sulphide obtained by the methods described above consists of a mass of cubical crystals of sp. gr. = 1.85, which have no action on polarised light, and exhibit two cleavage planes at right angles to each other. It is not acted on by hydrogen at the highest temperature of a reverberatory furnace, but is decom- posed, with incandescence, by chlorine a t about 300°, with the formation of the chlorides of magnesium and sulphur ; bromine and iodine also decompose it a t a dull red heat. The crystalline sulphide is readily oxidised when heated in oxygen, and also by heating with potassium chlorate, potassium nitrate, lead peroxide, and phosphoric anhydride.It is not reduced by heating at a high temperature with phosphorus, boron, silicon, or iron ; sodium, however, decomposes it. It is readily acted on by steam, with formation of magnesium oxide and hydrogen sulphide ; at the ordinary temperature, however, water acts with great difficulty on the crystalline sulphide, whereas the amorphous sulphide is immediately decomposed. Nitric and sul- phuric acids and gaseous hydrogen fluoride and chloride act on the crystalline sulphide a t the ordinary temperature, whilst hydrogen bromide and iodide react a t a dull red heat. It is also readily attacked by phosphorus trichloride and by chromyl chloride; in the28 ABSTRACTS OF CHEMICAL PAPERS.latter case, a greenish substance is produced, the nature of which is being investigated ; it contains both chromium and sulphur. N. L. Formation of Metallic Sulphides by Mechanical Influences. By L ~ O N FRANCK (Bull. Xoc. Chim., 1897, [iii], 17, 504-506).- Spring has shown that sulphides of magnesium, zinc, iron, copper, &c., may be obtained by subjecting intimate mixtures of the metals and sulphur t o a pressure of 6500 atmospheres (Abstr., 1883, 904; 1884, 959), and it has long been known t h a t mercuric sulphide may be obtained by triturating the metal with sulphur, cuprous sulphide by triturating the metal with sulphur under water, and ferrous sulphide in a similar manner with hot water. The author finds that when a mixture of flowers of sulphur and of magnesium powder is rubbed between two sheets of paper, hydrogen sulphide is evolved.A similar reaction occurs with aluminium powder and sulphur, or even when sheet aluminium is rubbed with flowers of sulphur. By G. URBAIN (Conpt. rend., 1898, 12'7, 107--108).-Further investigations have confirmed the utility of the method of fractionating by means of ethyl-sulphates ; it is especially valuable for resolving a complex mixture into groups to which the other methods of fractionation can be applied much more easily than to the original substance, The constituents of crude yttria do not separate with uniform distinctness; i t is easy, for example, to obtain erbium quite free from holmium, but very difficult t o eliminate erbium from the fractions rich in holmium.By com- bining the ethyl-sulphate method with some of the older methods, the author finds that the crude yttria from monazite sands consists chiefly of yttrium of atomic weight 89, and contains terbium with an atomic weight as high as 151.4, but no element with the atomic weight 100 or 97. By ROBERT M. CAVEN and ALFRED HILL (J. Xoc. Chern. hd., 1897, 16, 29-30. Compare Abstr., 1898, ii, 591).-On adding disodium hydrogen phosphate to a n aqueous solution of aluminium sulphate, no precipitate is formed at first, but on boil- ing for a n hour, the greater part of the aluminium is precipitated as phosphate. An excess of ammonium chloride partially precipitates aluminium phosphate from a solution of the latter in aqueous ammonia or caustic alkalis. Cold, dilute acetic acid dissolves aluminium phos- phate, but, on boiling, the latter is precipitated ; ammonium acetate does not produce a precipitate with the cold solution, nor with a solution of the phosphate in hydrochloric acid to which an excess of acetic acid has been added; if, however, only a small quantity of acetic acid is present in the latter case, ammonium acetate gives rise t o a precipitate of aluminium phosphate.On adding dilute acetic acid and ammonium acetate t o a nearly saturated solution of alumi- nium phosphate in aqueous aluminium sulphate, a precipitate is produced, although none is formed when only a small amount of the phosphate is present ; in the latter case, the addition of a little disodium hydrogen phosphate brings about precipitation. Chromium phosphate is gradually precipitated on boiling a solution J.J. S. Yttrium Earths in Monazite Sands. C. H. B. Metallic Phosphates.INORGANIC CHEMISTRY. 29 containing disodium hydrogen phosphate and chromium sulphate ; it is not as easily soluble in aqueous ammonia as aluminium sulphate, but resembles the latter in being precipitated by ammonium chloride from its solution in caustic potash. Chromium phosphate is readily soluble in acetic a.cid, but is precipitated from neutral solutions by ammonium acetate ; like ferric phosphate, it undergoes hydrolysis when washed with water. Traces of chromium and aluminium may be detected in presence of large quantities of ferric phosphate by fusing the mixed phosphates with potassium hydroxide on platinum foil; on adding ammonium chloride to the aqueous extract, aluminium is precipitated as mixed phosphate and hydroxide, and, on filtering, a yellow solution is ob- tained if chromium is present, becoming green when sulphurous acid is added.Cupric phosphate is somewhat soluble in aqueous cupric chloride and cupric sulphate, and undergoes hydrolysis when washed with water ; on boiling w2th water, it is converted into a basic phosphate, Cu3(P0,),,Cu0,H,0, as stated by Steinscheider (Abstr., 1891, 1423), whilst aqueous potash completely hydrolyses i t to cupric oxide. Bismuth phosphate is somewhat soluble in aqueous bismuth chloride, but is not hydrolysed by boiling water, although completely converted into oxide when boiled with caustic alkalis, Lead phosphate is insoluble in aqueous lead nitrate, and is not changed when boiled with water ; it easily dissolves in boiling caustic potash, but less readily in aqueous ammonia.W. A. D. Influence of Silicon on the Heat of Solution of Coke Cast Irons. By EDWARD D. CAMPBELL and WILLIAM E. HARTMAN (J. Amer. Chem. Xoc. 1898, 20, 690-695).-The object of this research was to determine if any thermochemical evidence could be obtained of a change in the condition in which silicon exists in cast iron, this change being due to differences of the temperature at which the iron is made. The solvent was a solution of ammonium copper chloride in the molecular ratio (NH,C1),CuC12 : 50H20, but with the addition of 0.84 per cent. of free hydrochloric acid. When either from a suffi- ciently high temperature of the blast furnace at the time the iron is made, or from the presence of a moderate amount of silicon, probably about one and four-tenths per cent., the carbon is nearly all in the graphitic or “graphitic temper” form; then the heat evolved by theoxid- ation of the silicon, is proportional to the amount of silicon present. When from a low temperature in the furnace accompanied by low silicon, the carbon is largely in the combined form, then the heat rendered sensible is very much diminished owing to the large amount of heat necessary to decompose the compounds of iron and carbon, or possibly compounds of iron, silicon, and carbon, or of carbon and silicon.As the oxidation of one gram of silicon alone develops 3824 Cal., and the results obtained by dissolving cast irons give a maximum of 3303 Cal., it is evident that the compound of silicon with iron must have avery con- siderable heat of formation.When the percentage of silicon is nearly sufficient to correspond with the empirical formula SiFe,, the compound is insoluble in ammonium copper chloride. H. C.30 ABSTRACTS OF CHEMICAL PAPERS. Constitution and Genesis of Iron Sulphates. By RUDOLF SCHARIZER (Zeit. Eryst. Min., 1898, 30, 209--231).-1n an investiga- tion dealing with the genesis of native iron sulphates, the author has made experiments requiring several years For their completion. In this first paper are given the results of experiments on the loss of water, and oxidation of ferrous sulphate. Over sulphuric acid, ferrous sulphate (FeSO, + 7H20) readily loses three molecules of water, 3H,O more are given off, with partial oxida- tion of the ferrous sulphate, at 60-80°, +H,O is lost at 100-300°, whilst the remainder is only given off on ignition.When exposed to air, it effloresces after a long period of time to the end product FeSO, + H20. The products of oxidation of a ferrous sulphate solution depend on the lapse of time and on the degree of dilution of the solution ; ferric sulphate is also formed [lOFeSO, + 5 0 = Fe,SO, + 3Fe2(S04),], and this by its decomposition [3Fe2(S04), + 8H20 = Fe,SO,, + 8H2S0,] introduces further complications. One gram of ferrous sulphate in 50 C.C. of water gives a permanent ferric sulphate solution ; in more concentrated solutions, soluble basic salts are formed, whilst in more dilute solutions there is free sulphuric acid.L. J. 5. Decomposition of Water by Chromous Salts, and their Use for the Absorption of Oxygen. By MARCELLIN P. E. BERTHELOT (Compt. rend,, 1898, 127, 24--27).-Since the oxidation of chromous chloride, with production of the oxychloride, Cr,Cl,O, is accompanied by the evolution of a larger amount of heat (100.4 Cal.) than is pro- duced in the formation of water from its elements, there should be a tendency to the decomposition of water by chromous chloride. The latter reaction does not take place at the ordinary temperature in the case of pure solutions of chromous salts containing no free acid; above 250°, however, or at the ordinary temperature in presence of traces of free hydrochloric acid, decomposition slowly occurs, and hydrogen is evolved.An explanation of the influence of the hydro- chloric acid in this reaction is suggested by a consideration of the properties of the green and violet modifications of chromic chloride, which are formed from chromous chloride with the evolution of 94.6 Cal. and 113.4 Cal. respectively, The oxychloride formed by the oxidation of the chromous chloride is not converted by the hydro- chloric acid into the green chromic chloride, since this reaction would involve the absorption of 5.8 Cal. ; under the influence of time, how- ever, the formation of the violet modification is rendered possible, with the evolution of 13 Cal., and it is the supplementary energy of this reaction which determines the slow decomposition of the water.It follows from the foregoing observations that an acid solution of chromous chloride should not be employed as an absorbent of oxygen in the exact analysis of gaseous mixtures, or in the purification of any By PETR. GI-. MELIKOFF and L. PISSARJEWSKY (Zeit. ccn.org. Chem., 1898, 18, 59--65).-The authors discuss the results which they have obtained in their researches on the peroxides (Abstr., 1898, ii, 161, 165, 219, 292, 332, 337, and 374). They have gas but hydrogen. N. L. Peroxides.INORGANIC CHEMISTRY, 31 shown that the acid peroxides are capable of forming salts with alkali peroxides. The soluble salts, for example, the sodium and lithium salts of peruranic acid, when treated with aluminium hydroxide, are converted into the free acid and hydrogen peroxide; the insoluble salts, for example, the barium salt of peruranic acid, when treated with carbonic anhydride, behave like barium peroxide, and barium carbonate, hydrogen peroxide, and peruranic acid are formed.Acid peroxides of the type RO, have been obtained from elements belonging to six groups, The stability of the salts which they form with alkali peroxides decreases with the atomic weight of the element which forms the acid peroxide. Those peroxides which are strong acids do not form salts with metallic peroxides, but decompose the latter, with formation of hydrogen peroxide. The authors assign to the peroxy-acids and metallic peroxides a constitution of the type of hydrogen peroxide, HO-OH, since they show a simiIar behaviour towards many reagents. When treated with dilute sulphuric acid, they yield hydrogen peroxide; with con- centrated sulphuric acid, many of them yield ozone.The peroxy- acids are decomposed by water in a similar manner to the metallic peroxides ; thus, sodium perborate is partially [decomposed into sodium metaborate and hydrogen peroxide; they also behave in a manner similar to the metallic peroxides when treated with manganese peroxide, whereby oxygen is rapidly evolved in the case of soluble salts, and slowly in that of insoluble salts. The peroxy-acids very easily oxidise alkalis, converting them into peroxides, for example, in the case of peruranic acid according to the equation 3U0, + 4KOH = 2U0, + (K2O2),UO4 + 2H,O. E. C . R. Permolybdates. By PETR. G. MELTKOFF and L. PISSARJEWSKY (Ber., 1898,31, 2448-2451).-The failure of Muthmann and Nagel (Abstr., 1898, ii, 593) to obtain potassium peroxide permolybdate having the properties described by the authors can osly be due to their failure t o reproduce the necessary experimental conditions, and for this reason the authors repeat their description of the method employed by them.To a solution of potassium permolybdate prepared by PQchard's method (Abstr., 1891, 988) are added aqueous solutions of potash and hydrogen peroxide (3 per cent.) in amounts corresponding with the scheme KMoO, + 3KOH + 4H,O, ; the liquid, which has now become dark red, is mixed with alcohol cooled to - 10' to - 1 2 O , insufficient in amount to precipitate potassium peroxide. The flocculent, red precipitate thus produced is separated by means of a filter cooled by ice and salt, washed with alcohol and ether successively, and finally dried on a cooled tile.The salt thus obtained is ready for analysis, and always possesses the same properties ; it evolves oxygen when dissolved in water a t the ordinary temperature, changing colour simultaneously, and i t is exploded by friction, or by the heat spontaneously developed on exposure to air; it is not hygroscopic as mas the substance obtained by Muthmann and Nagel, and i t is probable that these experimenters were dealing with an impure specimen containing potassium peroxide.32 ABSTRACTS OF CHEMICAL PAPERS. The suggestion made by Muthmann and Nagel, that the foregoing substance contained some hydrogen peroxide, is untenable, as its pro- perties are not sensibly different if excess of hydrogen peroxide be employed in its preparation, and when it is reprecipitated from a solution in alkaline hydrogen peroxide its properties remain unaltered.It is, therefore, a chemical individual. The authors are unable to accept the view that the molybdates can combine with a molecular proportion of oxygen at low temperatures, and believe that there is much evidence to show that the I' per-" acids form salt-like compounds with the metallic peroxides. A. L. Action of Hydrogen on Potassium Paratungstate. By L. A. HALLOPEAU (Comdpt. rend., 1898, 127, 57-58).-When potassium paratungstate is heated to dull redness in a current of hydrogen, a mixture of tungsten dioxide with the blue oxide of tungsten is ob- tained.A t higher temperatures, a compound of the composition K,OIWO, + WO,,WO, is also produced, which crystallises in small, reddish-violet prisms having a coppery lustre. This substance, which appears to be identical with the compounds obtained by Laurent and by Wohler, may be purified by prolonged washing with boiling water, concentrated hydrochloric acid, and potassium carbonate solution. A t a bright red heat, it nndergoes further reduction by hydrogen, with Production of Tungsten Blue by the Reduction of Tungsten in Porcelain Furnaces, By ALBERT GRANGER (Comnpt. rend., 1898, 127, 106--107).-When a mixture of barium and sodium tetra- tungstates, RI',O, WO,, is used as a glaze on porcelain and is heated in a reducing flame at about 1250°, it yields a blue colour varying from pale blue to indigo. The t i n t depends on the proportion of the two salts and the quantity of the glaze used, and can also be modified by adding borax or phosphates.The blue colour is most probably due to the formation of the oxide W,O, in the conditions specified. formation of metallic tungsten. N. L. C. H. B. Lead-antimony, Tin-antimony, Tin-arsenic, and Tin-phos- phorus Alloys. By JOHN E. STEAD (J. SOC. Chem., Ind., 1897, 16, 300-208 and 309).-When alloys of lead and antimony containing from 1-12.66 per cent. of the latter, are melted and allowed to solidify, a perfectly homogeneous product is obtained. On increasing the proportion of antimony, however, crystals of the latter separate in a nearly pure state, and rising to the surface of the cooled product form a layer of a much lighter colour than the subjacent portion.The latter has a composition corresponding with the formula Pb,Sb, and appears to be the eutectic alloy of the two metals; it has a sp. gr.- 10.48, melts at about 247O, and solidifies in ill-defined hexagonal plates. Although all lead-antimony alloys, except the eutectic, have two critical points, one of these always corresponds with the fusing temperature of the compound Pb,Sb. MThen alloys of tin and antimony are melted and cooled, as long as the amount of the latter does not exceed 7.5 per cent., perfectly homogeneous products are obtained. On increasing the amount ofINORGANIC CHEMISTRY. 33 antimony, well-defined crystals separate, which consist of a combination of cubic and octahedral forms.They were isolated from the matrix by dissolving the latter completely in dilute nitric acid (sp. gr. = 1-04) ; thus obtained, they appear to consist of tin antimonide, SnSb, and have a sp. gr. = 6-96 (calc. 7.00). It appears that tin antimonide only crys- tallises from alloys containing an excess of tin; the crycJtaIs are formed best when 75 per cent. of the latter is present. On melting tin antimonide and allowing the mass to cool, cubic crystals are no longer formed in bhe solidifying mass; it appears that, like iron carbide, Fe,C, tin antimonide is decomposed by fusion. On melting alloys of tin and phosphorus containing from 0.04-5 per cent. of the latter, brilliant, white, crystalline plates of tin phos- phide, Sn3P,, separate on cooling; this was isolated by the same process as was used for preparing tin antimonide.It is decomposed when heated in a stream of hydrogen, phosphine being formed, whilst spontaneously inflammable hydrogen phosphide is evolved when any of the tin-phosphorus alloys are acted on by concentrated hydrochloric acid. A crystalline tin arsenic& mas isolated by the author from alloys of arsenic and tin ; it separates from the still molten tin at a temperature of 530°, and apparently has the composition Sn,As,. By H. F. HUNT and L. J. STEELE (J. Xoc. Chem. I t d . , 1896, 15, 849-850).- When aluminium is allowed to stand on mercury covered with a thick film of oxide, although apparently no amalgamation takes place, the aluminium is rapidly converted into its hydroxide. The action is not so rapid when the metal is kept beneath dirty mercury, and is very slight when aluminium is floated on freshly distilled mercury. The hydroxide is formed most rapidly on aluminium which has had its surface amalgamated by the ordinary methods.A Chloriodide of Tin. By C. LENOMAND (J. Pharm., 1898, [vi], 8, 249-253). -Although iodine does not act on anhydrous stannous chloride a t the ordinary temperature, it combines with it, when heated at 100' for several hours, forming tin chloriodide, SnC1,12. This is a mobile, red liquid, which fumes in the air, and has a sp. gr. = 3.287 at 15' ; i t is decomposed by water, and when poured into ether or ethylic, propylic, butylic, or smylic alcohol, gives rise to a crystalline compound. When tin chloriodide (100 grams) is heated, it begins to distil a t 19l0, but the temperature gradually rises to 297'; the residue (55.44 grams) in the flask at this temperature consists of nearly pure stannic iodide, EM,. I f the distillate obtained be redistilled, a further quantity of stannic iodide is left, and still more can be isolated by repeating the process. Ultimately, 67.78 per cent. of stnnnic iodide and 26.82 per cent. of stannic chloride were obtained ; the total result of the decomposition can therefore be expressed by the equation 2SnCl,I, = SnC1, + SnI,. Double Sulphfttes of Antimony and the Alkali Metals. By AUQUST GUTMANN ( A T c ~ . Pham., 1898, SEB, 477-479).-Antimony potassium dphate, KSb( SO,),, prepared by dissolving antimonious oxide W. A. D. Oxidation of Aluminium in Contact with Mercury. W. A. D. W. A. D. VOL. LXXVI. ii 339 ABSTRACTS OF CHEMICAL PAPERS. in a boiling solution of potassium sulphate in concentrated hydro- chloric acid, crystallises in small, six-sided, nacreous leaflets. The corresponding sodium salt forms small, scaly crystals, and the ammonium salt large, glistening leaflets. Action of Heat on the DoubleRhodium-AJkali Nitrites. By ALEXANDRE JOLY and EMILE LEIDI~ (Compt. vend., 1898,27,103-106). -The double nitrites of rhodium with potassium, sodium, and barium begin to decompose at about 360°, but the products a t this temperature are complex and indefinite. If, however, the salts are heated in a vacuum between 440' and incipient redness until evolution of gas ceases, and the products are then treated with water, definite, insoluble, crystalline compounds are obtained. The potassium salt yields the compound K20,6Rh0,, the sodium salt the compound Na,0,8Rh02, and the barium salt the compound BaO,l2RhO,. These compounds are t o be regarded as the salts of hexarhodous acid, octa- rhodous acid and dodecarhodous acid respectively, and the acids are products of the condensation of rhodous acid, H,O,RhO,. The existence of these compounds affords definite evidence of the existence of an oxide, Rho?, with an acidic function; they are analogous to the chromites, cobaltites and manganites obtained by G. Rousseau, and their formation seems to show that the production of salts of peroxides by the action of heat on double nitrites is a property common to many of the metals of the platinum group, A. W. C. C. H, B.

ISSN:0368-1769    

DOI:10.1039/CA8997605017

出版商:RSC    

年代:1899

数据来源: RSC

摘要:

39 ABSTRACTS OF CHEMICAL PAPERS. Mineralogical Chemistry. Cedarite, an Amber-like Resin from Canada. By RICHARD KLEBS (Jahrb. f. Min., 1898, ii, 212; from Jahrb. k, preuss. geol. Landesanst., for 1896, 1--32).-This resin, to which the new name cedarite is given, has been known since 1890 at Cedar Lake, near the mouth of the North Saskatchewan River, and in many other parts of Western Canada. It occurs as isolated grains in wood-bearing, alluvial beds, and appears to have been originally derived from strata of Cretaceous or Tertiary age. The grains, having sometimes the form of drops, are rarely as large as a pea, and never exceed a walnut in size. The resin is clear yellow, but sometimes brown and cloudy. The sp. gr. is that of amber, but the hardness rather less. Analysis gave C.H. S. 0. Ash. Total. 78-15 9-89 0.31 11.20 0.45 100-00 Melting point 340' ; at 390' it decomposes and leaves a residue of 86.8 per cent. of colophony. Succinic acid is absent. It is of much less commercial use than Baltic amber, Other fossil resins are compared with the one here described. [This mineral(formerlycal1ed chemawinite) has already been described, Abstr., 1892,5731. It is only partially soluble in alcohol, ether, acetone, &c. L. J. 8.MINXRALOGICAL CBEMISTRP. 35 Uinfiahite (Gilsonite) Deposits of Utah. By GEORGE H. ELDRIDGE (Jahrb. f. &fin., 1808, ii. Ref. 211 ; from 17th Ama. Rept. 0.27. Geol. Survey, 1896, part i, 909-949).-Uintahite or gilsonite is an asphalt, occurring abundantly in the Uintah mountains ol Utah. It differs from albertite and grahamite in the brown or reddish-brown streak, hardness of 2-24, and sp.gr. of 1*065-1*070. It fills fissures, 1 in. to 18 ft. across, in the Tertiary beds, and has apparently been forced up from below. Analysis by W. C. Day (J. lipanklin Inst., 1895, 140, No. 837) gave, Solid C. H. S. O+N. Ash. Total. Volatile. residue. 88.30 9.96 1.32 [0.32] 0.10 100.00 54.46 43.43 and perhaps also of the naphthalene, series. Day considers it to be a mixture of hydrocarbons of the paraffin, L. J. S. Occurrence of Hydrogen Sulphide in the Natural Gas of Point Abino, Canada; Estimation of Sulphur in Gas Mix- tures. By FRANCIS C. PHILLIPS (J, Amer. Clem. SOC., 1898, 20, 696-705).-The gas escaping from the well a t Point Abino is strongly contaminated with hydrogen sulphide, which may be proved by passing it through solutions of lead acetate or ammoniacal cadmium chloride.The gas, after being passed through lead acetate, gives no precipitate or marked odour when again passed through mercuric chloride, showing the absence of volatile sulphur compounds ; palladium chloride also remains unaffected, In order to estimate the quantity of hydrogen sulphide, the lead sulphide obtained from a definite volume of the gas was oxidised by means of hydrochloric acid and potassium chlorate, and the sulphuric acid formed estimated as barium sulphide. A more convenient way, although requiring a complicated apparatus, was found to be to pass a current of carbonic oxide throiigh a definite volume of the gas, and then to burn the mixed gas in oxygen, the products of combustion being collected in an abForption apparatus containing sodium car- bonate and some bromine.All the sulphur was thus obtained as sulphuric acid, which was then estimated in the usual way, as barium By HJALMAR SJOGREN (Jcclwb. f. Min., 1898, ii, Ref. 209; from Geol. For. Forh., 1897, 19, 106--112).-1n the analysis of the new mineral retzian, a hydrated arsenate of manganese, calcium, &c., a constituent amounting to 10.3 per cent, (0-0082 gram) was previously not identified (Abstr., 1896, ii, 35). This is now stated to be rare earths, most probably yttrium oxides with a molecular weight of about 250. The manganese and calcium, as given in the analysis, may also have contained rare earths. A formula cannot yet be given. The orthorhombic crystals have the parameters, a : b : c : = 0.4414 : 1 : 0.7270.By WILLIAM RAMSAY and MORRIS W. TRAVERS (Prsc. Roy. Xoc., 1898, 62, 325-329).- The mineral examined gave, on analysis (by Miss Aston), sulphste. L. DE K. Composition of Retzian. L. J. 8. Fergusonite, an Endothermic Mineral. 3-236 ABSTRACTS OF CHEMICAL PAPERS. (Nb,l'a)@a. (Y,Er, &c ) 0 . (Ce, &c.)O,. VO,. UO,. TiO,. SiO,. Fe,0,. PbO. CuO. Total. 40-95 31.0Q2 13-87 3.36 3.81 4.56 1-42 1.55 0.16 0.12 100.89 When heated to 500-600°, the mineral suddenly becomes incan- descent, and liberates, per gram of mineral, He, 1-080 C.C. ; H,, 0.078 ; GO,, 0.245 ; N,, 0.027 ; on further heating with potassium hydrogen sulphate, it yields, in addition to CO,, He, 0.733; N,, 0.088; O,, 0.394 C.C.per gram of mineral. The total percentage of helium is 0.0326. The density is 5.619 before, 5-375 after, heating to incan- descence; the mean specific heat of the mineral between Oo and 1 7 ~ 3 ~ is 0,1069. To determine the heat of decomposition, the mineral was heated in a platinum crucible (contained in a calorimeter) by burning under the crucible, in oxygen, a known weight of hydrogen, and noting the additional rise of temperature above that obtained when hydrogen was burned under the empty crucible. The heat of decomposition is +SO9 calories per gram of mineral, and is probably caused by the decomposition of an endothermic compound of helium with some con- stituent of the mineral. Thaumasite from Skottvhg, Sweden. By HELGE BACKSTR~M (Jahrb. f. Mk, 1898, ii, Ref.196; from Geol. liiir. Piirh,, 1897, IS, 307--310).-Thaumasite has recently been found at a new Swedish locality, namely, in the mines of Skottvgng, parish of Ggsinge, Nykoping. It occurs as an aggregate of prismatic crystals between, and later than, crystal aggregates of apophyllite. The hexagonal prisms, are without distinct terminal faces, which are optically uniaxial and negative j o = 1.505, E = 1.468. Analysis gave7 C. F. B. Sp. gr. 1.811-1.875. H,O. CO,. SiO, SO,. CaO. Total. 43.28 7-01 9.68 12-88 27.16 100-01 CaSi0,,CaC0,,CaS04, 15 H,O. This agrees closely with the usual formula, Diopside (Salite) as a Weathering Product in Palaeopicrite from Medenbach (Nassau). By REINHARD BRAUNS (Jahrb. f. Nh., 1898, ii, 79-88).-With a little serpentine and calcite, salite fills crevices in a palaeopicrite at Medenbach, near Herborn ; it is compact to fibrous, and light grey to yellowish-grey. The optical characters are those of diopside, with the extinction angle & : c = 409 Sp.gr. =3-31. The following analysis by Noack gives the formula Ca(Mg,Fe)Si,O,. SiO,. FeO. MnO. A1203. CaO. MgO. Total. 55.56 3-65 trace - 24.51 15.58 99-30 L. J. S. The palaeopicrite is composed of olivine (mostly altered to ser- pentine), augite and plagioclase, with ilmenite and magnetite. Tn the serpentine are small, radiated groups of spear-shaped crystals of salite, which has been derived from the olivine. Kainosite from the KO Mine, Sweden. By HJALMAR SJ~GREN (Jahrb. f. Hin,, 1898, ii, Ref. 202 ; from Geol. F&r. F&h., 1897, 19, 54--60).-0nly one Norwegian crystal of this mineral, kainosite or cenosite, has previously been known.It has now been found in L. J. S.MINERALOGICAL CHEMISTRY. 37 small, isolated crystals associated with clinochlore and apatite in a druse consisting mainly of magnetite and diopside at the KO mine, Nordmark. The crystals, which do not exceed 2 mm. across, are yellowish-brown or dark chestnut-brown ; they are opaque and have a feeble vitreous to greasy lustre, H = 5-6 ; there is no distinct cleavage. The short, prismatic crystals are orthorhombic, with the forms { 1 lo}, (OOl), and {Oll), and others less prominent. The parameters, a : b : c = 0.9517 : 1 : 0.8832, are compared with those of cerite. The mineral is easily soluble in hydrochloric acid with evolution of gas (CO,?).Analysis by R. Mauzelius, on 000666 gram, gave SiO,. Y,O,. Fe,O,. CaO. MgO. Alkalis. H,O. COP Total. Sp. gr. 31.7 35.9 2.9 16-5 1.4 3.6 2.9 [5.1] 100.0 3.38 With the Fe,O, is possibly some BeO, and other elements may be present. Yttrium minerals usually occur in pegmatite veins and in other separations from ancient eruptive rocks; and an occurrence in an ore deposit is remarkable. This composition agrees with that of the Hitter0 mineral. L. J . S. Minerals [Hessonite, &c.] from the Urals. By ALEKSANDR N. russ. min. Ges., 1896, [ ii 3, 34, l-l60).-The new Eugenie-Maximi- lianow mines, 15-20 km. west and north-west of Ekaterinburg, yield the following minerals, many of them as fine crystals : garnet (hesso- nite, &c.), epidote (very abundant), sphene, axinite, clinochlore, microcline, idocrase, beryl, corundum, &c.These are, in nearly all cases, confined to the junction of the orthoclase rocks (granite and syenite), and the amphibole rocks (gneiss, &c.), but they also rarely occur in dolomite at the dolomite-granite contacts. The following analyses are given of hessonite. I. Fine, transparent rhombic-dodeca- hedral crystals, often 3-4 cm. across, light yellow to dark-reddish in colour, from Mt. Pup. 11. Transparent yellowish to orange-red crystals from Mt. Mjedwjeschka. 111. Greyish-yellow crystals from the same locality. Analyses I, I1 by W. Alexheff, I11 by W. Worobi6ff. VON KARNOJITSKY (Zeit. Kryst. Min., 1898,30,311-319 ; from h - h . k. SiO, TiO,. Al,O,. F%O,. CaO. Mn0. MgO. I.39.10 0.50 17.75 6.50 35.77 trace 0.19 11. 38-10 0.78 16-30 10.53 35.00 trace trace 111. 39.3 0.4 17.9 6.3 35.5 1.3 All the crystals of hessonite show optical anomalies, the lighter coloured being the most strongly birefringent, whilst the darker are sometimes almost isotropic. The difference in colour, depending on the amount of iron, is also connected with a difference in optical orientation. L. J. 8. [Mariposite.] By HENRY W. TURNER (Jahrb.f. Him, 1898, ii, Ref. 200 ; from 17th Ann. Rept. 77.8. Geol. Survey, 1896, part i, 678-679 ; and Arner. J. Xci., 1895, 40, 377).-Mariposite was described by Silliman in 1868 as a green, micaceous mineral from the gold-quartz veins of Tuohirnne and Mariposa counties, California. It is abundant38 ABSTRACTS OF CHEMICAL PAPERS. at the Josephine mine, near Beau Valley.Analyses by Hilbbrand gave I for the green, sp. gr.=2*817; and XI for the white, sp. gr. = 2.787. Water is not given off below 300'. In thin sections, both are nearly colourless : they show bright polarisation colours, and give straight, or nearly straight, extinction. SiO,. TiO,. A1,0,. Cr20,. Fe,O,. FeO. CaO. MgO. K20. (Li,Na),O. H,O. I. 55.35 0.18 25.62 0.1s 0.63 0.92 0.07 3.25 9.29 0.12 4.52 11. 56.79 25.29 Nil 1.59 0.07 3-29 8.92 0.17 4.72 No definite formula can be given, and the material appears to be similar to pinite. Marekanite-obsidian from Nicaragua. By JOHANNES PETERSEN (Ja1wb.f. Min., 1898, ii, 156-159).-Marekanite balls from Corinto in Nicaragua are described; they are about the size of hazel-nuts, and black, with vitreous lustre.They are difficult to break with a hammer, but when cut they fly to pieces; in form, they are approximately spheres or truncated pyramids, and the surfaces show concave areas. Under the microscope, fragments of the transparent, colourless glass show flow structure marked out by numerous globu- lites, trichites, and small crystals. These marekanite balls appear to be perlite balls rather than the kernels of perlites, as has been supposed, and a rock coinposed of them may be called a marekanite- obsidian. As shown by the following analysis, the composition is that of a Ziparite magma. - L. J. S. SiO,. Al,O,. FeO. MnO. MgO. CaO. K,O. Na20. H20. Total. 76.68 14.49 1 4 9 trace 0.84: 1.53 1.20 3.92 0.36 100.11 L. J. S. Dyke Rocks from Adamello Mountains. By CARLO RIVA (Jcchrb.f. Min., 1898, ii, Ref. 247; from Atti Xoc. Itccl. Sci. Nat., 1897, 27, 365).-Numerous dyke rocks, mostly intersecting the tonalite, have recently been found in the Adamello Mountains, on the Italian-Tyrol border ; they include diorite-porphyrites, vintlites, malchites, odinites, and aplites. Analysis I is of malchite, with horn- blende and biotite, from the Passo di Campo; 11, of malchite, with augite and biotite, from Lago d'Arno. Both are grey to grey-brown rocks with felspar (andesine-labradorite) and quartz. They are more basic than the surrounding tonalite. SiO,. AI20,. Fe,Os. MgO. CaO. Na,O. K,O. H,O. Total. I. 57.48 16.82 8.49 4.64 5.45 2-63 4-57 0.25 100.33 11. 56.77 20.02 6-40 3-70 5-40 4.01 3.94 0.13 100.36 L. J.S. Analysis of the Mineral Water of Castrocaro. By FAUSTO SESTINI and R. CAMPANI (L'Orosi, 1897,20,43-47).-The results of the analysis of this mineral water are given below in tabular form. The sp. gr. = 1.0312 at 15". Tho total volume of the gases expelled from one litre by boiling is 50.15 c.c., including CO,, 29.94 C.C. ; O,, 4.39 C.C. ; N, (gas unabsorbed by potash or phosphorus), 15.80 c,c,Substance. I Grams per litre. C1 ..................... Br. ..................... I. ....................... SO, .................... SiO, ................... P,O, .................. Substance. 36*8109 0.1382 0,1516 0.5845 0'0219 0'0026 N%O .................. CaO .................... MgO .................. Fe203.. ................ Organic matter.., ... Grams per litre.28 -0284 2'2047 1.2676 0*0014 0,6842 Total solid residue dried a t 180°= 61.7475. A series of monthly analyses made during the year 1891-1892 show that the composition of the water is fairly constant; there is, however, a marked decrease in the amounts of bromine and iodine, more especially the former, in the rainy months of the year. The Sulphur Water of Sandef'jord. By EYVIND B~DTKER (Annalen, 1898, 302, 43-51. Compare Strecker, Annalen, 1855, 95, 177). -The Sandefjord is in the neighbourhoodof Christiania, and opens into the Skager Rack. Water drawn from the spring there is a trans- parent, yellowish liquid having a powerful odour of hydrogen sulphide ; owing to separation of sulphur, it becomes turbid on exposure to the air, but clear again after a long interval.The liquid is neutral, but acquires alkaline properties if kept in glass bottles, black sulphide of iron separating during the change. On July 19, 1893, the temperature of the spring was 10.3O at half-past eleven, identical with that observed by Strecker towards the end of June, 1853 ; if the temperature is raised above this point, carbonic anhydride is liberated. The amount of solid matter dissolved in the water is very variable, and appears to fluctuate between 1.5 and 3 per cent. The quantity of hydrogen sulphide in 1000 C.C. is, on the other hand, fairly constant ; it amounted to 34.26 C.C. in the summer of 1892, and 37.89 C.C. a year later. A complete analysis of the gaseous and solid substances dis- solved in the water is given in the paper, showing that the quantities of carbonic anhydride and hydrogen sulphide have increased by 33 per cent. and 60 per cent. respectively during the last 50 years. The gytje is a peculiar, dark grey mud which collects in sheltered bays along this coast. At Sandefjord the gytje is greasy to the touch, and has the odour of hydrogen sulphide; it is used for mud baths. A specimen, dried at 100°, gave the following results on analysis. SiO,. A1,Op NaC1. KCl. K,SO,. CaO. Ca3P20,. MgO. FeO. 54-43 12.93 5 5 7 0.65 2.11 1.89 0.3'7 1-64 4-88 with organic matter (9.87), and chemically combined water 5.97, making the total 100.31. One thousand parts by weight of the moist sub- stance contained 1-53 and 0.083 parts of ammonia and hydrogen sul- phide respectively. The water in the fjord itself, observed by Strecker to contain only 1-40 per cent. of salts, now contains almost twice this amount. N. L. M. 0. F.

ISSN:0368-1769    

DOI:10.1039/CA8997605034

出版商:RSC    

年代:1899

数据来源: RSC

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40 ABSTRACTS OF CHEMICAL PAPERS. P h y si ol og i cal C h emi s t r y. Composition of Normal Gastric Juice. By ADOLF SCH~LE (Chern. Centr., 1898, i, 347, from Zed. kZin. Med., 33, 543-546),- A case is described in which gastric juice was obtainable free from saliva; it contained some flakes of mucin ; the free hydrochloric acid varied from 0.09-0.2 per cent. ; the sp. gr. = 1.0012. The peptonising power of 3 C.C. was 50-55 per cent. (Hammerschlag’s method) ; the juice did not invert cane-sugar, neither did it give the xanthoproteic reaction, nor the tests for albumoses or peptone. Influence of Organic Foods on Inorganic Metabolism. By ANGELO PUGLIESE (Chem, Cenntr., 1898, i, 266-267; from Du Bois Reymond’s Archiu, 1897, 473-485).-0n the administration of carbo- hydrates and fats to dogs, the excretion of nitrogen and phosphates sinks; gelatin also causes a fall in the phosphates excreted.Sugar and, to a less degree, fat and gelatin, produce a rise in the output of sodium and potassium, the alkaline earths, however, not being affected. The total quantity of urine is lessened by feeding with sugar, but increased by intravenous injection of sugar. Very small quantities of sugar increase the output of nitrogen and phosphates. W. D. H. W. D. H. Oxidation of Acetone and Homologous Fatty Ketones [in the Organism].-By LEO SCHWARZ (Chern. Centr., 1898, i, 264 ; from Arch. exp. Path. Pharrn., 40, 168-1 94).-The separation of acetone is chiefly effected by the lungs. With doses of 0.2 to 1.6 grams per kilo- gram weight of the animal, 1-4 per cent. is found in the urine, and when larger quantities are administered, proportionately greater amounts are thus separated.Since very small quantities of acetone are not completely oxidised in the body, acetone cannot occur as an intermediate product of physiological action, and neither albumin nor carbohydrates yield acetone when oxidised with potassium permangan- ate. The power of oxidising acetone in dogs is not diminished by in- ducing diabetes in them by means of phloridzin, or by extirpation of the pancreas, but the organism is then able to form acetone from aceto- acetic acid, whereas in the healthy animal acetoacetic acid, hydroxy- isobutyric acid, /I-hydroxybutyric acid, and mesityl oxide do not yield acetone. In the healthy organism, however, acetone is formed from acetoxime, and the mixed ketones of the fatty series are partly oxi- dised and partly excreted.Of the ketones examined, diethyl ketone is physiologically the most easily oxidised. Presence of Manganese in Minerals, Plants, and Animals. By P. PICHARD (Compt. rend., 1898,126,18S2-1885).-Manganese seems to be universally diffused in rocks, plants, and animals. The author gives a list of 36 orders of plants, including both phanerogams and cryptogams, in which he has detected this element by the method previously described. J t seems to be concentrated in the leaves and E. W. W.PHYSIOLOGICAJ, CHEMISTRY. 41 other parts of the plant that are in active growth, and especially in the seeds of phanerogams. The proportion of manganese in animals is much smaller than in plants.It is noteworthy that the yolkof an egg contains much more than the white, an egg contains more than flesh, and flesh contains more than bones. C. H. B. By B. MOORE and SWALE VINCENT (Proc. Roy. Xoc., 1898,62, 352-354).- The suprarenal capsules of teleostean fishes resemble, anatomically, the inter-renal body of elasmobranchs, and the cortex of mammalian suprarenals. The chromogen present in the medulla of mammalian suprarenals is absent, and extracts of the teleostean capsules are physiologically inactive. No organ corresponding to the medulla is found in these fishes. Comparative Chemistry of the Suprarenal Capsules. W. D. H. Presence of Organic Chlorine in Normal Urine. By DIOSCORIDE VITALI (L’Orosi, 1897, 20, 114-119 ; 145--153).-The question of the existence in urine of chlorine in various forms of combination is discussed, and an account is given of the experiments which have hitherto been made with a view to distinguishing between the chlorine present as chlorides and that existing in intimate combination with organic substances and incapable of being directly precipitated by silver nitrate.The results obtained by previous observers are criticised in detail, and sundry discrepancies therein are shown to be due to defec- tive methods of analysis. That ‘‘ organic chlorine ” exists in urine to a small, but not insignificant, extent, is demonstrated by the following process, which appears to be free from sources of error. The urine is rendered distinctly acid with pure nitric acid, a slight excess of silver nitrate added, and the liquid filtered from the precipitated silver chloride.The excess of silver in the filtrate is removed by hydrogen sulphide, the liquid filtered, warmed to expel hydrogen sulphide, filtered again, mixed with potassium nitrate and excess of sodium carbonate, evaporated t o dryness in a platinum dish, and incinerated. The residue is extracted with water, and to the filtered solution, after acidification with nitric acid, silver nitrate is added; the precipitate thus obtained is soluble in ammonia, but insoluble in boiling concentrated nitric acid, and does not, therefore, consist of silver cyanide, as has been suggested by some experimenters. Some experiments made with the object of ascertaining the nature of the organic chlorine compounds in urine, showed that they are not extracted from acid or alkaline urine by ether, chloroform, or light petroleum.Phosphorus in Urine. By LEOPOLD JOLLY (Compt. yernd., 1898,127, 11 8-1 19).-Sometimes urine contains phosphorns in a form tbat is not precipitated even by a large excess of ammoniacal magnesium mixture, and this phosphorus has been supposed to exist in an incompletely oxidised form (LBpine and Aubert), or as phosphoglyceric acid. The author finds, however, that the urine of many patients suffering from nervous disorders or diathesia, and even the urine of healthy persons after an excess of food, contains peculiar nitrogen compounds which are not affected by the ordinary reagents for N. L.42 ABSTRACTS OF CHEMICAL PAPERS. albumins and peptones, but are precipitated by tannin and by concen- trated mercuric chloride solution, These nitrogen compounds retain some metallic phosphates in such intimate association that the phosphoric acid in them is not precipitated by magnesium mixture, and the author considers that it is these phosphates, and not phosphoglyceric acid or any incompletely oxidised form of phosphorus, that escapes precipitation by the ordinary method. By WILLIAIII OECHSNER DE CONINCK (Cornpi.rend., 1898, 127,72).-The urine in five cases of rachitis was found to contain chlorides (calculated as sodium chloride ‘I) ranging from 11.22 to 12-14 grams per litre. These results, corresponding with a considerable loss of chlorine, are in accordance with the author’s views as to the nature of the disease.N. L. By HEINRICH ROSIN (Chem. Cent?*., 1898, i, 74-75; from Bedin. KZin. Woch, 34, 1044--1047).-1n a female patient suffering from myelogenic sarcoma of the thoracic skeleton, a proteose resembling in general characters deutero-albumose was present in the urine, Chemistry of Amyloid Degeneration. By N. P. KRAWKOFF (Chem. Centr., 1898, i, 261-262; from Arch. exp. Path. Phwm., 1897, 40, 195--220).-The author describes the occurrence of chondroitin- sulphuric acid in healthy and diseased men and animals. The amyloid substance is prepared from the various organs, the liver, kidneys, and spleen, from which the Glisson’s capsule and the larger vessels have been removed, by treating them in small pieces with cold water and a dilute solution of ammonia.The mass is macerated on a nickel gauze sieve, and washed with dilute ammonia until the filtrate is free from chondroitinsulphuric acid. After washing with water, it is digested for several days with pepsin-hydrochloric acid, the mass then treated with ammonia, in which the greater part dissolves, and the amyloid precipitated with hydrochloric acid. The flocculent precipitate is washed with water, alcohol, and ether. The product contained C, 46.92 ; H, 6.60 ; N, 14.16, and P, 1-16 per cc it. The phosphorus is due to the presence of nucleins which may be removed by treating the freshly-precipitated substance with baryta water. The amyloid gives the reaction with methyl-violet, but the reaction with iodine is dependent on its physical condition. Analyses of four preparations are quoted.The amyloid is insoluble in weak alkalis, and is a com- bination of chondroitinsulphuric acid with an albuminous substance ; by the action of pepsin-hydrochloric acid, the latter is possibly con- verted into an albumose complex. In healthy organisms, the amyloid occurs so sparsely distributed in the walls of arteries, that the colour Pharmacology of Aconitine, Diacetylaconitine, Benzaconine, and Aconine. BY J. THEODORE CASH and WYNDHAM R. DUNSTAN (PYOC. Roy. Xoc., 1898, 62, 338--347).--Action on the Cie.cuZc&on. -Aconitine first stimulates the medullary centres, slowing the heart ; acceleration follows, auricles and ventricles taking up an independent rhythm. Imperfect systole and delirium of the ventricles may C. H. B. Elimination of Chlorides in Rachitis.Proteose in Urine. W. H. D. reactions are not apparent. E. w. w.PHYSIOLOGICAL CHEMlSTRY. 43 follow. If the poisoning is slow, stimulation of the cardiac vagus ceases to produce the usual inhibitory effect. The vaso-motor centre is first stimulated, then depressed. Diacetylaconitine produces in the main the same results, but in a less marked manner. Benzaconine produces a preliminary acceleration of the pulse, and then slowing, with fall of blood pressure, ensues; this is due to the depression of the motor mechanism within the heart. The vaso- motor centre is depressed, Vagus stimulation causes slowing until a late stage of the poisoning is reached. Digitaline is an effective antagonist. Aconine is comparatively harmless. Action, on Res~ircction.-Aconitine first stimulates, then depresses, the respiratory centre and the pulmonary sensory vagal fibres.Diacetylaconitine produces a slighter initial stimulation ; death results from central failure, Benzaconine depresses the ce;l tzes from the first. Respiratory failure is partly produced by act on on motor nerve endings, and causes death without spasm. Aconine slows the respiration, and has a pronounced curare-like action on the motor nerve endings. Actioa on the Nervous 8ystem.-Aconitine produces no distinct narcotic effect, but the depression is secondary to diminution of oxidation processes from cardiac and respiratory failure. There is preliminary stimulation. Sensation is depressed. Respiratory spasm occurs a t death. Diacetylaconitine produces a similar, but less marked, effect. Benzaconine causes a semi-narcotised condition, which is partly Sensory nerves are but little referable to low intracranial pressure. affected. Aconine produces loss of volition in large doses. Action on Oxidation.-Tested with vegetable protoplasm, all reduce oxidation processes, aconitine being the most, and aconine the least, active. All produce a fall of body temperature in the same order of activity , Lethal Doses.-These are stated in fractions of a gram per kilo. of body weight for cat, rabbit, guinea-pig, and frog. The figures for the cat are : Aconitine .............................. O*OUO134 Diacetylaconitine ..................... 0.004 to 0.006 Benzaconine ........................... 0.0245 Aconine ................................. 0.16 to 0.4 General Conclusions.-The introduction of two additional acetyl groups into the molecule of aconitine slightly weakens, but does not materially modify, its action. The removal of the acetyl group so as to form benzaconine almost entirely annuls its characteristic actions. The withdrawal of the benzoyl group (as in aconine) reduces the toxicity still more. In fact, aconine and benzaconino are largely antagonistic to aconitine. IT. D. H.

ISSN:0368-1769    

DOI:10.1039/CA8997605040

出版商:RSC    

年代:1899

数据来源: RSC

摘要:

44 ABSTRACTS OF CHEMICAL PAPERS. Chemistry of Vegetable Physiology and Agriculture. Action of the Sorbose Bacterium on Xylose (Wood-sugar). By GABRIEL RERTRAND (Cornpt. rend., 1898, 127, 124--127).-When the bacterium of sorbose is allowed to grow in a decoction of yeast mixed with xylose, the latter is slowly, but almost completely, con- verted into xylonic acid. C. H. B. Composition of the Mycelium of Mould Fungi. By MARSCHALL ( B e d . Centr., 1898,27,575 ; from Arch. Hyg., 28, 16-29 ; and Chem. Centr., 1897, i, 115).-Anslyses were made of Aspergillus iaiger, Pen& cilliurn glaucum, and Mucor stolonifer before fructification. The average percentage composition of the dry matter was found t o be as follows. Ether Alcohol Nitrog. extract Proteids. extract. extract. Cellulose.Starch. sol. in water. Ash, 38 5.27 14.03 5.03 2-8 28-47 6-37 The fungi occupy, therefore, as regards composition, a position be- tween bacteria and the higher plants. Germination. By F. VICTOR JODIN (Ann. Agrm., 1898, 24, 382-390. Compare Abstr., 1898, ii, 129).-Experiments similar to those previously described were made with dead pea seeds, sterilised and not sterilised. The sterilised seeds remained practically inert, whilst the results obtained with the non-sterilised seeds seemed to indicate very active respiration. On repeating the experiment with live peas, the relation C02/02 was 1-00 with sterilised, and 1.23 with non-sterilised seeds, showing that the activity of live seeds is able to overcome the effect of microbes. Pea seeds, seven years old, the germinative power of which was very much weakened, were covered with water.They did not ger- minate, but underwent a slight change, liberating carbonic anhydride and absorbing oxygen. Cotyledons (of peas), after removal of the rudimentary plant, con- tinued to give off carbonic anhydride, and retained a great part of the chemical energy of the seeds. But the nature of the change was entirely altered. Thus whilst during two successive periods of 5 days the relation, C02/0,, was 1-41 and 0.84 with entire peas which had germinated normally, it was 14.08 and 2.15 in the case of the mutilated peas. Effect of Formaldehyde on the Germination of Sugar Beet Seed. By ANTON STIFT (Bied. Centr., 1898, 2'?, 568; from Outerr. Zeit. Zuckerind., 1898, in).-Beetroot seeds retained, without excep- tion, their power of germinating, after remaining 24 hours in an atmosphere of formaldehyde (compare Windisch, Abstr., 1898, ii, 40).N. H. J. M. N. H. J. M. N. H. J. M,VEQETABLE PHYSIOLOGY AND AGRICULTURE. 45 The Presence of Simple Organic Gompounds in the Vege- table Kingdom. By ADOLF LIEBEN (Monatsh., 1898,19,333-354). -It has previously been shown (Abstr., 1895, ii, 348) that the only product which can be isolated when carbonic anhydride is reduced with nascent hydrogen is formic acid. Experiments have now been undertaken to determine whether grass and the leaves of different trees yield formic acid or other volatile products when mixed with their own weight of acidified water (containing about 0.6 per cent. of sulphuric acid) and then subjected to distillation with steam.The faintly acid distillates were treated with sodium hydrogen carbonate and evaporated to dryness,and the solid residue examined for different acids. In all cases, formic and acetic acids, and a higher fatty acid, probably propionic, were obtained, the amount of acetic acid being greater than that of the other acids, although the amounts were invariably small; for example, from 72 kilos. of grass only 11 grams of the mixed barium salts were obtained. A small quantity of a higher crystalline acid was isolated which was practically insoluble in water, readily soluble in ammonia, fused readily, and gave insoluble lead and silver salts. The neutral volatile products were obtained by distilling with steam and attaching a fractionating column to the flask ; the distillate coming over was examined separately, and then the column was removed, the distillation continued, and the distillate examined for acids. Methylic and ethylic alcohols and a small quantity of oil were the only neutral products isolated, the amount of ethylic alcohol being always greater than that of methylic, and experiments indicated that this alcohol was only obtained after the vegetable tissue had remained for some time in contact with water. I n order to determine whether the acid and neutral products thus obtained were actually present in the leaves, bc., or were obtained by the action of the acidified water on the carbohydrates present in the tissues, the author subjected cane-sugar to an exactly similar treat- ment, and it was found that neither methylic nor ethylic alcohol was formed, but, apparently, when 5 or 10 per cent.sulphuric acid was employed, a small quantity of furfuraldehyde was produced. The volatile acids obtained from different carbohydrates, for example, filter paper, starch, and cane-sugar, were formic acid and a small quantity of a higher solid acid, probably identical with that obtained from leaves. When cane-sugar was mixed with water acidified with tartaric acid and then subjected to distillation with steam, formic acid was the only volatile product isolated, J. J. 8. Physiological Meaning of Phosphoric Acid in the Organism of Sugar Beet. By JULIUS STOKLASA (Bied. Centr., 1898,2'7,537-539 ; from Zeit. Zuckerind. Bohmen, 1897, 403, and Oesterr.Zeit. Zuchrind. 2c. Landw., 1897, 933).-Of the total phosphoric acid in beet seeds, 2-72 is in the form of lecithin. In seedlings six days old (sand-culture), the amount of phosphoric acid as lecithin was 6 per cent. of the total, and after 30 days, 9 per cent. was found in the leaves and stems, and 4.6 per cent. in the roots. In the case of plants grown under ordinary conditions, 6.3 per cent. of the phosphoric acid of the leaves46 ABSTRACTS OF CHEMICAL PAPERS. was present as lecithin after 60 days, but only 5 per cent. in the roots. At the end of the vegetative period, when the outer leaves were yellow, the green leaves contained 0-89, and the yellow leaves only 0.15, per cent. of lecithin. The dry substance of chlorotic beet contained only 0.22 per cent.of lecithin, whilst green leaves contained nearly 1 per cent. in the dry matter. As leaves die off and the chlorophyll is destroyed, the lecithin migrates to the root, where it is stored up, chiefly in the head, presum- ably in anticipation of second year's growth. N. H. J. M. Chlorophyll in a Nostoc grown in the Dark. By ALEXANDRE ~ T A R D and BOUILHAC (Compt. rend., 1898, 127, 119--121).-A Nostoc grown in the dark on a solution of glucose containing certain salts, was found to contain a green chlorophyll, which gave the spectrum charac- teristic of the glaucophylls found in ordinary living leaves, except that the band X548-536 had a much higher relative intensity than usual, being stronger than the band X631-606, although not so strong as the band h690-650.The alcoholic solution was yellowish-green with R distinct red fluorescence. Whether this chlorophyll possesses the ordinary chlorophyllien function was not ascertained. Conditions of Development and the Composition of the Volatile Mustard Oils of the Seeds of the Crucifer=. By GUNNER JORGENSEN (Sied. Centr., 1898, 27, 697-699 ; from Tidsky. f. Pysik. 09 Kemi. Copenhagen, 1898, 3, 91-1 1 l).-The investigation was undertaken in consequence of the poisoning of cattle fed with rape cake. The cakes examined, which were stated to be rape cake, proved in some cases to consist of Brassica napus or B. rapa, in other cases the seeds of Sinapis, Eruca and Erysimum were found. Various Brassiccc seeds, unmixed, were also examined. The cakes which acted corrosively on the digestive organs of the cows, did not show any considerable difference in the amount of mustard oil they produced, The composition of the mustard oils from different sources varied, however, considerably.I n some cases (Xinap's nigra and Bra~ica juncea) the analytical results corresponded with the composi- tion of allylthiocarbamide ; in other cases (Brassica glauca, B. dichotoma h.), the thiosinamine produced was a crotonylthiocarbamide. The permanence of the pungent odour, produced by stirring with water and adding white mustard, was fairly proportional to the amount of '( Indian seeds " in the cakes. Under the conditions of the experi- ments (the substance 5, mustard 1, water 100 grams, were kept at 40" in a closed 250 C.C. flask), the odour of mustard oil could still be detected after from 0-2 hours when no Indian rape was present, after 18-19 hours when the sample consisted mainly of Indian rape, after 26 hours with sarepta, and after 28 hours with black mustard.C. H. B. N. H. J. M. Miorochemical Proof of the Presence of Alkaloids in Medicinal Drugs. By HERMANN BARTII (Arch. Phurm., 1898, 236, 354-367).-The paper contains the results of a number of experiments made on some drugs with the idea of determining in which cells orVEGETABLE PHYSIOLOGY AND AGRICULTURE. 47 Lowest .. Highest. Nean. ... cell-complexes the alkaloids are to be found. I n addition to the ordinary reagents, the following were often found to give good results :-vanadium sulphate, a sulphuric acid solution of cerium sulphate, and selenium sulphate and nitrate.Some reagents, such as iodine, bromine, chlorine, hydrochloric and nitric acids, were employed in the form of vapour, thus permitting the use of a very powerful reagent, without dilution. Such reagents are strong enough to kill the plasma and convert the alkaloid, combined with an organic acid into an easily crystalIisnble salt. Many alkaloids for example, give crystalline substitution or additive products with the halogens, which are, however, easily soluble in water. Such compounds can, in the above manner, be easily detected by the microscope, or a t all events when a polarising microscope is employed, as most of them are doubly refractive. The results, which cannot well be abstracted, lead the author to the belief that the alkaloids are utilised during the germinating and de- velopment of the young plants, which is in agreement with Heckel's views (compare Arch.Phav-m., 1892, 555). Formation of Proteids in Plants by the Reduction of Nitrates. By ALEXANDRE HEBERT (Ann. Ayron., 1898, 24, 41 6-440). -The results of different investigators indicate that in the reduction of nitrates in plants, hydrogen cyanide is formed, and that this action usually takes place in those organs in which chlorophyll is present, and where the production of formaldehyde also predominates. After calling attention to the great combining power, and the facility of forming polymerides, which formaldehyde possesses, and the similar properties of cyanogen derivatives, it is suggested as probable that the two substances combine in the vege- table cells, yielding the more or less complex nitrogen compounds- which form the fundamental products of the hydration of albumin.N. H. J. M. A. W. C. Cereals. Leguminous. Straw, Chaff. Straw, Chaff. In total In total In total In total proteids. proteids. proteids. proteids. -________-____-~- 0 0 0'049 3'49 0.058 5-39 0.078 6'05 0'102 15-74 0.117 13.23 0'203 19.37 0'465 24.49 0'049 7-29 0.085 8-19 0.123 11-74 0'244 12.25 Amount of Nitrogenous Substances other than Proteids in Ripe Straw and Chaff. By PAUL HOLDEFLEISS ( B e d . Centr., 1898, 27, 532-534 ; from Habilitationsschr. Halle ad., 1897).-The total nitrogen, and the pure proteids (by Stutzer's method) were determined in a large number of samples of the straw and chaff of various plants. The following is a summary of the percentage results relating to non-proteids :48 AESTRACTS OF CHEMICAT, PAPERS.Amount of Nicotine in Retail Cigar8 and Tobacco. By HUGO SINNHOLD (Arch. Pharm., 1898, 236, 522-529).-The amount of nico- tine in European cigars, varies from 0.648 to 2.957 per cent. and in Havanna cigars from 0.972 to 2.241 per cent. Cigarette tobaccos con- tain 0.801 to 2.887 per cent., and pipe tobaccos 0.518 to 1.854 per cent. of nicotine. The analytical methods employed were those of Kissling (Zeit. anal. Chern., 21, 6 4 ; 22, 199), and Popovici (Biss. E'rlangen, 1889). A. W. C. The Changes in Sugar when Stored. By LEOPOLD JESSER (Bied. Centr., 1898,27, 701-705; from Oestemn. Zeit. Zuckerind., 1898, 35). Behaviour of Raw Sugar when Stored, By N. RYDLEWSICI (itid., from D. Deut.Zuchrind., 1897,1413, and Oesterr. Zed. Zuchrind., 1897, 1202)-Raw sugar in quantities of 1 cwt., contained in sacks, was buried in sugar. The sacks were taken out from time to time, in order to obtain samples, in which the cane-sugar and the alkalinity were determined. The results agree with those of previous investigators, in showing that the changes which sugar undergoes are not due to the composition of, at any rate, the normal non-sugars present, but to micro-organisms. The change does not progress uniformly. High alkalinity does not prevent the change, but when neutrality is reached reducing sub- stances are produced in such amounts that they can be determined by ordinary methods. In the early stages of decomposition, analysis is unable to decide whether the sugar is likely t o change much or little when stored.As a rule, strongly alkaline sugar can be kept longest. Feebly alkaline sugar, however, is often well able to resist change, especially when sulphurous acid has been employed. N, RYDLEwsKItstored different sugars for 100, 200, and 300 days, and examined them by the usual methods. He concludes that there is no danger as long as the sugar shows an alkaline reaction. The preparation of the sugar, for example, with or without animal charcoal, has no effect if the alkalinity of the sugar amounts to 0-020 or 0.030. N. H. J. M. Production of Humus from Manures. By HARRY SNYDER (Agr. Expt. Stat. Urbiv. Minnesota Bul., 53, 1897, 12-35. Compare Abstr., 1898, ii, 449).-Cow manure, green clover, and meat scraps produce valuable, highly nitrogenous humus, capable of combining with the phosphoric acid and potash of the soil.Sawdust, straw, and carbohydrates produce humus rich in carbon, which has less power to combine with the phosphoric acid and potash of the soil than the more nitrogenous forms of humus. Prolonged cropping produces less nitrogenous and more carbonaceous humus as compared with the humus of uncultivated land. Forest fires may dissipate 75 per cent. of the total nitrogen of the soil, and the practice of burning over new land sometimes causes per- manent injury to the soil. Soils which are deficient in humus are sandy and sandy-loam soils, which have grown maize, potatoes, and small grains without applica- tion of stable manures or without the proper rotation of crops.Prairie soil contains, per acre, about 1500 lbs. of phosphoric acidVEGETABLE PHYSIOLOGY AND AGRICULTURE. 49 and 800 Ibs. of potash combined with humus. After twenty years of cultivation, the amount of phosphoric acid is reduced to about 400 lbs. if the supply of humus is not kept up. Production of Nitrogenous Manure. By JOSEF KONIG (Bied. Centr., 1898, 27, 667-671 ; from Neue Zeit. Riibenxwckerind, 1898, l).-Attention is directed to the powibility of sapplying a great portion of the nitrogen required in Germany for manuring, in the form of ammonium salts from gas-works and coke-furnaces. It is estimated that at least 230,000 tons of ammonium sulphate, contain- ing 46,000 tons of nitrogen, could be produced annually as against 19,600 tons actually produced in 1898.As regards the prevalent idea that nitrogen in the form of ammonia is less valuable than in the form of nitrates, it is pointed out that, whilst for spring manuring nitrates are preferable to ammonium salts (as most plants probably assimilate nitrogen in the form of nitrates), nitrates have the disadvantage that they are liable to give rise to the formation of a crust on the surface of the soil ; they are also unsuited for autumn manuring owing to loss by drainage, and when used in large amounts they injure the quality of the crops. The application of ammonium salts involves, in the case of soils poor in lime, more or less frequent addition of marl, lime, or basic slag ; marl and ammonium salts may be applied simultaneously, but should be at once ploughed in.Experiments have shown the relative values of ammonium sulphate and sodium nitrate to be 90-96 : 100. But when the disadvantages of sodium nitrate are taken into account, both forms of nitrogen may be considered equal. hsimilation of Nitrates, and the Effect of Different Nitrates. By W. SCHNEIDEWIND' (Bied. CeBtr., 1898, 27, 674-676; from J. Landw., 1898, 46, I).-The rssults of experiments with sugar-beet manured with sodium and potassium nitrates respectively, indicated that the sodium salt gave a greater yield OF dry matter and sugar in the roots, whilst the potassium salt produced a greater amount of leaf. The better effect of sodium nitrate is attributed to its greater solubility and diffusibility. In the case of oats manured with various nitrates, the yield of grain was greatest with the magnesium salt; sodium nitrate gave the next largest amount of grain, then calcium, and, lastly, potassium nitrate.Magnesia has zt special r6Ze in the production of grain ; but it is supposed that the better result of sodium as compared with potassium nitrate is due, as in the case of sugar-beet, to the greater solubility of sodium salts, and to the consequent more rapid supply of nitrogen and phosphoric and sulphuric acids to the plant. Straw production was least with magnesium, and greatest with potassium nitrate. The composition of the grain did not vary to any extent, except in the case of the magnesia plants, the grain of which was somewhat richer in magnesia. Most of the magnesia, however, was deposited in the straw.N. H. J. M. N. H. J. M. VOL. LXXVX. ii. 450 ABSTRACTS OF CHEMICAL PAPERS, 50 kilos. P205. It is not supposed that sodium can in any way replace potassium in its functions connected with the migration of starch and sugar, N. H. J. M. Experiments on the Effect of the Phosphoric Acid of Bone Meal. By JULIUS KUHN (Bied. Centr., 1898, 27, 527-530; from Deut. landw. Presse, 1897, 24, Nos. 62 and 63).-Bone meal, being sparingly soluble, is not very effective when applied for crops which occupy the land for short periods. Even the after-effect in such cases is inconsiderable, as, with ordinary soils, the phosphoric acid of bone meal remains, after the harvest, unchanged in the sparingly soluble, tribasic form. The effect is, however, essentially different in the case of crops such as winter wheat, perennial clovers, &c., and the appropriative power of plants such as winter rye is of importance.Pot experiments were made, in which summer rye was grown in poor, sandy soil, without phosphate and with different amounts of various phosphates. The numbers given below show the percentage increase in produce over the unmanured pot. The amounts of phos- phoric acid are given in kilos. per hectare : 100kilos. P,O,. 200kilos. P,O, Superphosphate.. .......... Basic slag., ................. Degelatinised bone meal. Steamed bone meal ....... grain. straw, grain. I straw. I grain. grain. -I--l-- straw. 18 61 64 45 straw. 13 45 50 79 61 - 50 58 34 72 46 - -I- 76 1 58 With heavy soils, and with crops of long vegetative periods, i t is best to employ superphosphate.With good, warm, average soil, both steamed bone meal and superphosphate may be used, whilst super- phosphate alone should be applied to cold loams, or cold sandy loams. In the case of good sandy soil, superphosphate should not be used; both basic slag and steamed bone meal are suitable. There will, perhaps, in future, be more competition between de- gelatinised bones and basic slag for light sandy soils than has hitherto been the case. Observations as to whether the Beneficial Action of Lime on the Soil of the Experiment Station is due to any extent to its Neutralising Action. By HOHER J. WHEELER, GEORGE M. TuCKER,and BURT L. HARTWELL (Ann. Rep. Agr. Expt. Stat. Rho& Island, 1896,9,294-318).-The injizrious effect which invariablyresulted from the continuous application of ammonium sulphate to the soil of the Experiment Station could be overcome by simultaneous application of sufficient potassium carbonate, wood ashes, air-slacked lime, sodium carbonate, or caustic magnesia. Magnesium sulphate gave less satisfactory results, and the same holds, in a mom marked degree, in the case of gypsum as compared with slacked lime. In experiments with N. H. J. M.ANALYTICAL CHEMISTRY. 5 1 potatoes, gypsum failed to produce the beneficial effect observed with calcium carbonate, acetate, and oxalate, slacked lime and wood-ashes. Calcium acetate and oxalate are no doubt converted in the soil into carbonate (compare Schmoeger, Bes., 1879,755). It is concluded that, apart from the beneficial effect, both physical and mannrial, of the above-named substances, they were probably, to a great extent, useful owing to a natural deficiency of bases in the soil and also in correct- ing acidity. Calcium chloride exerted a poisonous action (on potatoes). N. H. J, M.

ISSN:0368-1769    

DOI:10.1039/CA8997605044

出版商:RSC    

年代:1899

数据来源: RSC

摘要:

ANALYTICAL CHEMISTRY. 5 1 Analytical Chemistry. Measurement of Gases. By OTTO BLEIER (Be?*., 1898, 31, 2513).-The author finds the method recently described by him (Abstr., 1898, i, 183) for the absolute measurement of gases has been previously used by Hempel (Verhdlg. Pereins. Befard. Gewery., 1894, 460). A. H. Crystals in Blowpipe Beads. By WILHELM FLORENCE (Jahrb. f. Min., 1898, ii, 102--146),-A systematic account is given of the results obtained on heating various substances in borax and sodium phosphate beads with or without the presence of lead oxide ; numerous figures are given of the crystals characteristic for each element so treated. The method is recommended for the microchemical deter- mination of minerals in the dry way. Use of Ferrous Salts in Alkaline Solution as a Reducing Agent in Volumetric Analysis.By ANDRI~ JOB (Compt. rend., 1898, 127, 59-60).-A solution made by adding an excess of sodium pyrophosphate to a solution of ferrous ammonium sulphate, is recom- mended as an alkaline reducing agent in volumetric analysis. When titrated with iodine or potassium permanganate, an operation which should be carried out in a current of hydrogen, the liquid remains colourless up to the end point, which is extremely sharp. A solution of sodium pyrophosphate readily dissolves ferrous sulphide, and the green solution thus obtained is well adapted for the colorimetric estimation of small quantities of iron, The reaction is stated to be as delicate as that with potassium thiocyanate. The solu- tion to be tested for traces of iron is mixed with a few drops of sodium pyrophosphate solution and one bubble of hydrogen sulphide passed in.N. L. Estimation of Moisture in Invert-sugar. By LEONARD T. THORNE and E. H. JEFFERS (J. Soc. Cliern. Ind., 1898, 17, 114--116).-1n consequence of the difficulty of drying invert-sugar in the ordinary way, it is usual to take the specific gravity (at 60' F.) of a 10 per cent. solution of the sample, and divide the excess of gravity over that of water (taken as 1000) by 0.386. This gives the percentage of dry sugar in the solution and the moisture in the sample is obtained by L. J. 8. 4-252 ABSTRACTS OF CHEMICAL PAPERS. difference. When a notable amount of mineral matter is present this is estimated, the percentage is multiplied by 0.8, and deducted from the original excess gravity before calculating out the dry sugar (Heron).To obtain a direct method of estimating the moisture, the authors have devised an apparatus for drying the sugar a t 65-70' in a slow current of carbonic anhydride at a pressure of 50-80 mm. of mercury. For this purpose, the sugar is weighed on to the end of a coil of paper contained in a test tube (previously dried until constant in weight) and is then distributed over the paper by the addition of a few C.C. of water, with certain precautions. The test tube is then placed in a wider tube which is heated in the vapour of boiling methylated spirit, and whilst kept exhausted as completely as possible by a powerful and constantly working exhaust pump, a very slow current of carbonic anhydride is allowed to pass through the apparatus.The results agree very closely with those deduced from the specific gravity of the solutions provided that the ash is weighed after sulphating and GT deducted before multiplying by 0.8 ; also for invert-sugars, the factor 0.3888 given by Brown, Morris and Millar (Trans., 1857, SO), is employed instead of 0.386, which is the correct factor for saccharose. M. J. S. Use of a Solution of Phloroglucinol-vanillin for the Detec- tion of Halogens in Organic Compounds. By P. N. RAIKOW (Chem. Zeit., 1898, 22, 20--31).-An alcoholic solution of phloro- glucinol-vanillin has been successfully used for the detection of free hydrochloric acid in gastric juice; the author now states that it may be succesefully applied to test for halogens in the products of corn- bustion of organic substances.A porcelain dish is rinsed with some of the reagent and then dried; a little of the substance to be tested is burnt on a platinum wire in a spirit lamp, or, if it is a gas, it is either burnt from a jet, or a current of it is passed through the spirit flame. If the dish coated with the reagent is inverted over the flame, the least trace of halogen acid formed will be indicated By MAURICE LUCAS (J. Pharm., 1898, [vi], 8, 311-312).-By varying the details of t h e silver nitrate method of estimating cuprous oxide in copper, the autbor has determined the conditions which are necessary to give concordant results agreeing with those obtained on reduction by hydrogen. It appears, also, that when cuprous oxide alone is treated, the amount of copper in the residue corresponds with that required by Hampe's equation, and that the action of silver nitrate on mixed cuprous oxide and copper gives the same result as its action on the separate components of the mixture.On immersing a sheet of copper in a neutral solution of copper nitrate, no precipitate containing copper is obtained on filtering. Estimation of Sulphur in Coal. By GEORGE L. HEATH (J. Amr. Chenz. ~Soc., 1898, 20, 630-637).-The author iejects, for technical The safest way is to operate as follows. by the intensely red permanent coloration. L. DE K. Estimation of Oxygen in Copper. W. A. D.h~ALJ?TICA~, CHEMISTRY. 53 purposes, those processes which are based on fusing with an oxidising mixture, as this involves an evaporation in order t o render any silica insoluble.The best method is the one proposed by Eschka, provided that bromine is used as the oxidising agent; the details are as follows. One gram of the powdered coal is intimately mixed with 1 gram of pure light magnesia and half a gram of dry sodium carbonate, and heated in a 100 C.C. platinum dish with the flame of a large spirit lamp, at first very slowly ; the mixture is frequently stirred with a platinum wire, and the whole is finally heated for 15 minutes at a low, red heat. When cold, the contents are transferred t o a beaker, and boiled for 5 minutes with 100 C.C. of water and 15 C.C. of saturated bromine water; the filtrate is finally mixed with a slight excess of hydrochloric acid and then precipitated with barium chloride, with Estimation of Traces of Hydrogen Sulphide in the Air.By KARL B. LEHramN (C’hem. Centr., 1898, i, 139; from Arch. Hyg., 30, 262).-First method-Eight litres of air are drawn through 10 C.C. of N/100 iodine solution, at the rate of 6 litres in 30 minutes, by means of an aspirator, any traces of iodine which may be carried off by the current being caught in a trap containing an N/100 solu- tion of sodium thiosulphate. From the loss in iodine, the amount of hydrogen sulphide is calculated. Second method.-The same volume of air is passed through a glass tube 30 cm. long and 12 mm. wide containing a strip of filter paper 5 cm. long and 2 cm. wide which has been saturated with lead nitrate solution. I f the paper turns pale yellowish-brown, the air contains about 1 *4-2 parts of hydrogen sulphide per million ; if dark brown, the amount will be from 3-5 parts, and if brownish-black, 8 or more Titration of Combined Sulphuric Acid.By MAX REUTER (Chem. Zeit., 1898, 22, 357).-The author has tried Andrew’ process (Amer. Chem. J., 1880, 2, 567), and finds that it gives excellent results if the titration with thiosulphate is made in a liquid containing only 5 C.C. of hydrochloric acid instead of 20; as this necessitates a longer contact with potassium iodide, the beaker should be covered with a watch-glass, and the air kept off by a surface current of carbonic anhydride. The process, as will be remembered, consists in precipitating the sulphnric acid by means of a solution of barium chromate in hydro- chloric acid.The excess of barium chromate is then removed by means of calcium carbonate, and the filtrate which contains an amount of soluble chromate equivalent to the sulphate is acidified with hydro- chloric acid, mixed with potassium iodide, and titrated with sodium Estimation of Nitrogen by the Kjeldahl-Gunning Method. By K. WEDEMEYER (Chem. Zeit., 1898,22,21).-The author has proved by a number of experiments that the addition of potassium sulphate, as recommended by Gunning, to the usual mixture of sulphuric acid, the usual precautions. L. DE K. parts may be present. L. DE I(. thiosulphate. L. DE K.54 ABSTRACTS OF CHEMICAL PAPERS. phosphoric anhydride, and metallic mercury, considerably shortens the time of boiling without in the least interfering with the accuracy of the method.NoTE.-Those who have read Gunning's original Dutch paper know that his chief object was to obviate the addition of potassium perman- ganate, salts of heavy metals, phosphoric anhydride, &c. Detection of Nitrates in Milk by means of Formaldehyde. By E. FRITZMANN (Chem. Centr., 1898, i, 218-219; from Zeit. O$E. Chem., 3, 610--614).--Nitrates, which, if present in milk, are a sure sign of the presence of adulteration with water, may be detected by adding to the milk a small quantity of formaldehyde, such as one drop of a 40 per cent. solution to 250 C.C. of the sample. On adding strong sulphuric acid, which should be chemically pure, a blue ring is obtained, and, on shaking, the liquid turns reddish- or bluish-violet. Too much formaldehyde interferes with the reaction ; if, therefore, the reaction still shows when more of it is added, the amount of nitrates is L.DE K. considerable. L. DE K. Estimation of Phosphoric Acid. By HENRI LASNE (Compt. rend., 1898, 12'7, 62--64).-According to Vignon (Abstr., 1898, ii, 639), the sum of the amounts of phosphoric acid precipitated as ammonium magnesium phosphate from the solutions obtained by treating superphosphate, (1) with water, (2) with ammonium citrate solution, is always considerably less than the amount precipitated from the mixture of the two solutions. The author, in his large experience of superphosphate analysis, has never observed such a discrepancy, and quotes the results of three experiments in support of his opinion of the exactitude of the precipitation of phosphoric acid in presence of ammonium citrate.It is also maintained that ammonium magnesium phosphate is absolutely insoluble in a liquid containing one-third of its volume of ammonia of 22O, and experi- ments are described which show that even as little as a milligram of phosphoric acid in a litre of liquid is aompletely precipitated as the double salt. N. L. Estimation of Phosphoric Acid, By LBO VIGNON (Compt. rend., 1898, 127, 191).-A reply to Lasne (preceding abstract). The author does not dispute the fact that the phosphoric acid soluble in citrate solution may be determined with accuracy directly, but maintains that his method of estimating it by difference offers the combined Estimation of Phosphoric Acid for Physiological Pur- poses.By ALBERT NEUMANN (Chem. Centr., 1898, i, 219-223); from Dzc Bois Reymond's Arch., 1897, 552-553).-The destruction of the organic matter is effected by means of strong sulphnric acid and ammonium nitrate, 1 gram for every C.C. of the acid, the operation being conducted in a Kjeldahl flask and the substance introduced in two or three separate portions. To destroy the organic matter in 25 C.C. of urine, 10 C.C. of acid is required ; for 25 C.C. of milk or 8 grams of fresh meat, 15 C.C. ; and for 5 grams of dry faxes, 20 c,c. of acid is needed. advantages of rapidity and accuracy. N. L.ANALYTICAL CHEMISTRY. 55 The phosphoric acid is then estimated graviine tricdly or, if possible, Method of Preparing a Strictly Neutral Ammonium Citrate Solution. By A. D.COOK (J. A n z e ~ . Chew,, S'oc., 1898, 20, 585-586).-Seven hundred and forty grams of citric acid is placed in a 4-litre measure containing 1900 C.C. of 10 per cent. ammonium hydroxide, the mixture is vigorously stirred until it is all dissolved. and the solution made up to the mark ; after being again well stirred, it is transferred to a large porcelain evaporating dish and allowed to remain overnight; in the morning i t will be found to be perfectly neutral both to corallin and cochineal. It is then Estimation of Citrate Soluble Phosphoric Acid in Bone Meals, Superphosphates, &c. By 0. BOTTCHER (Chew.. Zeit., 1898,22, 201-202).-Five grams of the sample is repeatedly ground up with a solution of ammonium citrate containing free citric acid, and the whole introduced into a Stohmann's half-litre fiask, which is then filled up to themark with the citrate solution a t 17.5".After closing the flask with an indiarubber cork, it is rotated for 30 minutes in a suitable apparatus which turns 30-40 times per minute round its axis. The liquid is then filtered and 50-100 C.C. is used for the estimation of the phosphoric acid either by the molybdic or the magnesia method. Preparation, qf the Citrate XoZutiorn.-One hundred and fifty grams of citric acid is put into a litre flask, dissolved in water, and exactly neutralised with ammonia; 10 grams of citric acid is then added, and the whole is made up to 1 litre. Before use, 1 volume of the By HUGO MASTBAUM (Zeit. anal. Chena., 1898, 37, 581-582).-With reference to the rapid method of igniting magnesium ammonium phosphate described by Schmoger (Abstr., 1898, ii, 455), the author states that even the preliminary drying of the precipitate is unnecessary, but that the wet precipitate, wrapped in its paper filter, may be placed in the platinum crucible and the latter at once exposed to the full flame of a Bunsen burner. The water assumes almost instantly the spheroidal condition, and no loss of precipitate takes place.After 15-20 minutes, the grey residue is moistened with strong nitric acid, which is then carefully evaporated. Exposure t o the blowpipe flame for half a minute completes the ignition. Volumetric Analysis of a Mixture of Alkyl Phosphates with Phosphoric Acid, By JACQUES CAVALIER (Compt. rend., 1898, 127, 60--61).-The composition of a mixture of phosphoric acid with tho two alkyl phosphates, RH,PO, and R2HP0,, where R is methyl, ethyl, or allyl, may be determined volumetrically by a process based on the behaviour of these compounds towards diff erent indicators and on the different solubilities of the barium salts.The dialkyl hydrogen phosphate is acid to methyl-orange and to phenolphthalein, and is rendered neutral to both indicators by combination with one equivalent of alkali. The monalkyl dihydrogen phosphate is neutralised by one by the volumetric uranium process. L. DE K. diluted with water to a sp. gr. = 1.09 at 20'. L. DE K. solution is diluted with 4 volumes of water. L. DE K. Ignition of Magnesium Ammonium Phosphate. M. J. S.56 ABSTRACTS OF CHEMICAL PAPERS. equivalent of alkali if methyl-orange is used as the indicator, and by two equivalents if phenolphthalein is employed ; the barium salt is soluble in water.Phosphoric acid resembles the preceding compound in its behaviour with indicators, but the barium salt, BaHPO,, is insoluble in water. The mixture of the three acids is first titrated with baryta water in the cold, using methyl-orange as indicator, and the liquid is then warmed to about 60° and the titration completed to the end point indicated by phenolphthalein. The first titration gives the sum of the three acids and the second the two polybasic acids, RH,PO, and H,PO,. The liquid is now filtered from the precipitated barium hydrogen phosphate, and both precipitate and filtrate are mixed with excess of standard hydro- chloric acid.The phosphoric acid and the monalkyl dihydrogen phos- phate respectively contained in the two solutions thus obtained are then titrated with baryta water, the volume of alkali required to pass from the end point indicated by methyl-orange to that indicated by phenolphthalein being determined. The sum of the two results should bo equal to that given by the second titration of the original mixture, N. L. By JOHN PATTINSON and HUGH S. PATTINSON (J. XOC. Cl~rn. Ind., 1898, 17, 211-214).- Arsenious sulphide requires for dissolution not more than 400,000 parts of hydrochloric acid of sp, gr. = 1 *17 saturated with hydrogen sulphide. I n the absence of hydrogen sulphide, the solubility is somewhat greater, although still very minute. Lead, cadmium, tin, antimony, and bismuth are not precipitated at all by hydrogen sulphide from acid of this strength, and the separation of arsenic from these metals is quantitatively complete.The precipitate may be washed with a mixture of 5 parts of hydrochloric acid and 2 parts of hydrogen sul- phide solution without loss, and without risk of precipitation of the other metals. If the arsenic be in the form of arsenic acid, it may be reduced by stannous chloride before passing the gas. The arsenious sulphide is best collected on an asbestos (Gooch) filter, After washing with acid, and then completely with water, it may either be weighed, or, if the quantity amounts to only a few centigrams, i t may be heated with 10-15 C.C. of strong sulphuric acid in an uncovered beaker at a temperature at which the acid gives off white fumes.No loss of arsenic is to be feared if chlorides are absent. Hydrogen sulphide is first given off, then sulphurous anhydride j the acid darkens at first but becomes colourless when a11 the sulphurous anhydride is expelled. A clear solution of arsenious acid is thus obtained. The solution is then nearly neutralised with sodium hydroxide, rendered alkaline with excess of sodium hydrogen carbonate, and titrated with iodine. A blank experiment with the same sulphuric acid is desirable, Very accurate results are obtained. Volumetric Estimation of Boric Acid. By VADAM (J. Phrm., 1898, [vi], 8, 109-1ll).-In presence of an excess of mannitol, the quantity of boric acid present in a solution can be determined by adding decinormal caustic soda until an alkaline reaction with phenol- Separation and Estimation of Arsenic, M.J. S.ANALYTICAT, CHEMISTRY. 57 phthalein or litmus is obtained ; the end point of the reaction is more sharply defined than in Barthe’s method, using glycerol (Abstr., 1896, ii, 337). In both cases, however, 1 C.C. of decinormal alkali is equivalent to 0.0062 gram of boric acid. The above method is avail- able for determining boric acid in butter ; 1.5 grams of the latter is extracted with warm water i(20 c.c.), the free fatty acids present neutralised with decinormal caustic soda in presence of litmus, 1-2 grams of mannitol added, and the boric acid determined as above described. W. A. D. Estimation of Potaasium. By JULIUS DIAMANT (Chem. Zed., 1898, 22, 99).-The author, finding a great difficulty in making potassium platinochloride perfectly anhydrous, now proposes the following process.The double salt, which should weigh about 0.5 gram, is dissolved in boiling water in a 500 C.C. flask, and when cold is diluted to the mark, and 1 gram of zinc dust is added; this rapidly decomposes the compound, forming zinc and potassium chlorides. Two hundred and fifty C.C. is then pipetted off and titrated with N/10 silver nitrate; from the chlorine thus found, the amount of potassium chloride may Test for the Presence of Sodium Hydrogen Carbonate in Sodium Carbonate. By MELCHIOR KIJBLI (Arch. Phurm., 1898,236, 321-324).-The test for the presence of sodium hydrogen carbonate in sodium carbonate, as given in the Pharmucop. German., III., and in the Phurmcop.Boss., IV., is not sufficiently delicate, as, according to the author, it mill not show the presence of 2 per cent. of the acid salt, and according to Thummel (Pharm. CentraLH., 1891, 86) as much as 4-5 per cent. may escape detection. The author therefore proposes the following test, which depends on the fact that an aqueous solu- tion of a soluble quinine salt of a certain concentration is not pre- cipitated by normal sodium carbonate, if the latter does not contain more than 2 per cent. of sodium hydrogen carbonate. Ten C.C. of a solution of quinine hydrochloride, containing 0.4 gram of the salt in 100 C.C. water, is added to 10 C.C. of the sodium car- bonate solution (3 grams in 50 C.C. water) ; if there is not more than 2 per cent.of sodium hydrogen carbonate present, no permanent cloudiness is produced. The quinine solution should be preserved from air and light, Estimation of Perchlorate in Chili Saltpetre. By OTTO FOERSTER (Chem. Zeit., 1898, a2, 357).-Ten grams of the sample is mixed with 10 grams of pure dry sodium carbonate and heated in a covered platinum or porcelain dish over the full flame until the fused mass flows quietly; this takes about 10 minutes. When cold, the mass, which can be readily detached from the dish, is dissolved in dilute nitric acid, and the total chlorine titrated by Volhard’s method ; afterallowing for chlorine present in other forms, the difference is Estimation of Lead in Ores. By FR. MOLDENHAUER (Chem. Zeit., 1898, 22, 256-257).-Two grams of the finely powdered ore is boiled be readily calculated.L. DE K. A. W. C. calculated to perchlorate. L. DE I(.5s ABSTRACTS OF CHEMICAL PAPERS. with strong hydrochloric acid until hydrogen sulphide is no longer evolved; if much antimony is present, this may be practically ex- pelled by evaporating to dryness two or three times with strong hydrochloric acid; the addition of a little nitric acid is advisable. The dry residue is now moistened with hydrochloric acid, 100 C.C. of water is added, the liquid boiled to dissolve the lead chloride, and the insoluble matter repeatedly washed with boiling water until quite free from lead ; 300 C.C. generally suffices, The filtrate, heated to redissolve any deposited lead chloride, is nearly neutralised with ammonia, preci- pitated with hydrogen sulphide, and the lead sulphide collected, washed, and digested with ammonium sulphide. It is then treated, together with the paper, with nitric acid, evaporated to dryness, and after being heated to expel any sulphur and organic matter, is con- verted into sulphate by means of sulphuric acid; finally, the sulphate is freed from other metals by washing, dried, and weighed.L. DE I(. Estimation of Traces of Lead in Water. By A. LIEBRICH (Chem. Zeit., 1898, 22, 325)-One, or more, litres of water is con- centrated, acidified with acetic acid, precipitated with hydrogen sul- phide, and the precipitate ignited and converted into sulphate by heating with a drop of sulphuric and nitric acid. The lead sulphate is then dissolved in a few C.C. of 10 per cent.aqueous potash, diluted to 20 c.c., mixed with 2 C.C. of freshly prepared ammonium sulphide, and the tint compared with that given by a standard solution of lead sulphate in aqueous potash containing 1 milligram of lead per c.c., and also diluted to 20 C.C. The experiment is then repeated, using more, or less, of the standard lead. By way of control, the lead sulphide New Volumetric Method for the Estimation of Copper. By RICHARD K. MEADE ( J . Amer. Chm. Xoc,, 1898,20, 610-613)- The solution of the copper ore is evaporated with sulphuric acid, the residue is dissolved in water, the greater part of the free acid neutra- lised with ammonia, and sulphurous acid added in excess ; the copper is then precipitated by adding a slight excess of ammonium thio- cyanate.The precipitate, collected on asbestos, is well washed and then put back into the beaker, where it is heated with aqueous (3 per cent.) potash; the suboxide thus produced is again collected on an asbestos filter, well washed with hot water, and then heated in a beaker with solution of pure ferric sulphate until it is entirely dissolved. The cuprous oxide sets f ree a corresponding equivalent of ferrous oxide, which is then titrated with permanganate, the iron equivalent of the perman- ganate multiplied by 1.125 giving the weight of the copper in the sample. Instead of sulphurous acid, a mixture of equal weights of sodium hydrogen sulphite and potassium thiocyanate may be used to precipi- tate the copper. Ferric chloride may be used instead of ferric sul- phate, but the titration with permanganate is then less safe.The process is not interfered with by the presence of arsenic, antimony, bismuth, or zinc. may be again converted into sulphate and weighed. L. DE K. L. DE K.ANALYTICAL CHEMISTRY. 59 Estimation of Copper in Vegetables. By VICTOR VEUROUI (Chert&. Zeit., 1838, 22, 103--IU4).-This is a controversy with Lehmann on the subject of the occurrence of copper in vegetable substances. The author (Abstr., 1897, ii, 602) has found in the same samples a very much larger amount of copper than Lehmann did, and attributes this to the inaccuracy of the latter’s colorimetric process. The author also expresses his view that the presence of even 0.8 gram of copper per kilogram of wheat does not constitute a danger to health, as the metal is there in the form of a harmless compound.L. DE I(. Estimation of Copper in Vegetable Substances. By KARL B. LEHMANN (Chem. Zeit., 1898, 22, 296--297).-A reply to Vedrodi (preceding abstract). The author cannot understand the great dif- ferences in the amount of copper found by Yedradi and himself in the ash of the same cereals, but he upholds his own views. L. DE I(. Estimation of Cuprous Oxide by Permangante. By ROBERT M. CAVEN and ALFRED HILL (J. Xoc. Chem. Ind., 1897,16, 981-983 ; 17, 124).-Cuprous oxide dissolves completely and rapidly in a mixture of potassium permanganate and sulphuric acid, with formation of cupric sulphate and corresponding reduction of the permanganate. One part of sulphuric acid is diluted with 3 parts of water, and 4 volumes of this acid is added to 1 vol.of standard permanganate. The cuprous oxide, collected and washed on an asbestos filter, is introduced into a measured excess of this mixture, and after stirring for a minute or two the unreduced permanganate is titrated with oxalic acid. Highly satis- factory results are obtained with great rapidity. M. J. S. Quantitative Separation of Metals by Hydroxylamine and Hydraeine. By PAUL JANNASCH (Ber., 1898, 31, 2377-2394).- [With a. D~v~~.]-Mercury may be separated from copper, bismuth, lead, cadmium, arsenic, antimony, or tin, in solutions of their salts, by the employment of an ammoniacal solution of hydroxylamine. A mixture of mercuric chloride and a salt of one of these metals is dissolved in water, or in hydrochloric acid if necessary, tartaric acid, ammonia, and hydroxylamine hydrochloride are added in excess, and the solution heated until the precipitation of mercury is complete; the latter is then collected, redissolved in fuming nitric acid, the solution evaporated to dryness, the residue taken up with hydrochloric acid and water, and the mercury precipitated as sulphide.From the ammoniacal filtrate, the remaining metal may be separated by suitable means, the copper as cuprous thiocyanate, the bismuth, lead, cadmium, antimony, and tin as sulphides, and the arsenic as magnesium ammonium arsenate. The copper, cadmium, bismuth, and tin are finally weighed as oxides, the lead as sulphate or peroxide, and the antimony as sulphide or oxide. [With F. ALFFERs.1-In a similar manner, mercury is separated from molybdenum or tungsten by ammoniacal hydroxylamine in the presence of tartaric or citric acids ; the precipitated metal is treated as described above, whilst from the filtrate the molybdenum is obtained as sulphide and weighed as trioxide.GO ABRTRAC'L'S OF CHEMICAT, PAPERS. r i 1 he separation of mercury from aluminium, chromium, or manganese is effected by the same reducing agent in the presence of oxalic acid ; aluminium and chromium are obtained as oxides, whilst the manganese is precipitated from the ammoniacal filtrate by hydrogen peroxide and weighed as the protosesquioxide. Tartaric or citric acid may be substituted for oxalic acid in the case of these metals, but its use is less convenient.Mercury and cobalt are separated by the addition of ammoniacal hydroxylamine to the slightly acid solution of their salts, the cobalt being precipitated as sulphide in the filtrate from the mercury.Mercury and nickel are similarly separated in the presence of an organic acid such as tartaric or citric. Either of these acids or oxalic acid may be employed in the separation of mercury from uranium by ammoniacal hrdroxylamine, the latter element being determined by evaporating the filtrate to dryness, igniting, and weighing both as U,08 and UO,. [With WILHELM H~InlANN.]-selenium, either in the form of selenious or selenic acid, is separated from sulphuric and phosphoric acids by boiling their solutions with excess of hydroxylamine hydrochloride, the selenium being precipitated and weighed, whilst the sulphuric and phosphoric acids in the filtrate are determined in the usual way. The separation of tellurous or telluric acids from sulphuric or phosphoric acids is effected in the same way.[With M. MULLER.]-A~ ammoniacal solution of hydroxylamine reduces tellurous and telluric acids, causing the complete precipitation of the tellurium, whilst an acid solution of this reagent is without action on these acids ; hydroxylamine may therefore be employed in separat- ing selenium and tellurium. The selenium is completely precipitated when a hydrochloric acid solution of these elements is boiled with hydroxylamine, and the tellurium separates quantitatively when the filtrate is rendered ammoniacal and boiled with more of the reducing agent ; four molecules of hydroxylamine are required for the reduction of one molecule of selenious acid, water and nitrogen being produced at the same time.Tellurium is separated from palladium by distilling an alloy of these elements in a current of bromine, the tellurium bromide is volatilised and received in hydrochloric acid, and the solution reduced with ammoniacal hydroxylamine ; the residue containing the palladium is dissolved in aqua regia, the metal precipitated as sulphide, and finally weighed as PdO, and also in the metallic state. Selenium is most conveniently separated from barium by means of hydroxylamine. Barium selenite dissolved in hydrochloric acid is boiled with excess of the reducing agent, and the selenium is collected and weighed; the barium remains in the filtrate and is estimated as sulphate. [With M.MU~~~~.]-Hydrazine sulphate reduces selenium compounds even more energetically than hydroxylamine and precipitates selenium both from hydrochloric and nitric acid solutions. Tellurium is also precipitated from its hydrochloric acid solution by this reagent but not from the solution in nitric acid ; from a hot ammoniacal solution, hjdrazine precipitates it quantitatively, and theANALYTiCAL CHEMISTRY. 61 reduction of this element from its salts by hydrazine and by hydroxyl. amine is being employed in the determination of its atomic weight. G. T. M. Detection of Cobalt in the Presence of Nickel. By ADAM JAWOROWSKI ( C l ~ m . Cerctr., 1898, i, 144; from Pharm. Zeit. Rus~., 36, 632-634). -The liquid, if containing free acid, is neutralised with sodium carbonate, and solid sodium pyrophosphate is added until the tur- bidity a t first produced has again disappeared ; the liquid, after being poured off from any undissolved pyrophosphate, is, if necessary, diluted with water until nearly colourless, and 6-43 C.C.of this solution is shaken with 1-1 -5 grams of sodium carbonate and 5-8 drops of brom- ine water; if cobalt be present, even in traces, the liquid will be of a By ANDRE JOB (Compt. rend., 1898, 127, 100-103. Compare McConnell and Hanes, Trans., 1897, 584).-It is well known that when hydrogen peroxide or bromine is added to a solution of potassium hydrogen carbonate mixed with a cobalt salt, the pink colour of the solution changes to green, but the composition of the green compound has not hitherto been ascertained. By titration with the special ferrous reagent proposed by the author (this vol., ii, 51), he finds that the ratio of cobalt oxide to active oxygen is 2Co : 0.Hence the green compound is a de- rivative of the oxide Co,O, ; its exact formula is Co2(OH),(HC0,), The oxidation of the cobalt in presence of an alkali followed by the titra- tion of the green compound with the ferrous reagent and iodine affords a rapid and very accurate means of estimating cobalt in presence of iron or nickel. Any excess of hydrogen peroxide soon decomposes or may be expelled by boiling the liquid for a few minutes. The best plan is to add the solution containing the cobalt salt t o a mixed solution of potassium hydrogen carbonate and hydrogen peroxide, heat gently for a few minutes and then titrate.beautiful green when observed in reflected light. L. DE I(. Oxidation of Cobalt Salts in Presence of Alkalis. C. H. B. Analysis of Swedish Magnetic Iron Ores. By TH. WETZKE (Chem. Centr., 1898, i, 144; from Zeit. O$z. Chem., 3, 575-577).- The solution in hydrochloric acid is effected by micro-burners so as to avoid boiling, and the vessel is covered; the iron is finally titrated with permanganate, any sulphurous insoluble residue being examined by Hauffe’s method. Phosphorus is best estimated by the process recommended by Meineke (Abstr., 1897, ii, 157), namely, ignition of the phosphomolybdate precipitate in a Gooch crucible. L . D E I(. Estimation of Tin in Tin Plate. By ROBERT JOB (J SOC. Chem. Ind., 1898, 17, 325-326).-1n a 200 C.C.flask, about 100 C.C. of pure hydrochloric acid of sp. gr. = 1.2 is placed, a piece of marble weighing about 5 grams is dropped in, and the flask is closed with a perforated cork fitted with a Bunsen valve. After about 5 minutes, 4 square inches of the tin plate, from the middle of a sheet, cut into strips, is dropped into the acid, and the flask is heated until the action becomes vigorous. When the plate is nearly dissolved, another fragment of marble is added, and immediately the plate is entirely dissolved, and while62 ABSTRACTS OF CHEMICAL PAPERS. effervescence from the marble still continues, the flask is cooled as rapidly as possible to 0'. I t is then filled to the mark with ice cold water, the contents mixed, and 50 C.C.of the solution titrated with iodine (1 C.C. = 0°00056 gram of tin). A fresh quantity of the iodine solution equal to that required in the first; titration is then placed in a flask, and 50 C.C. of the tin solution delivered into it, keeping the point of the pipette just below the surface; in this way, oxidation by air is completely avoided. A little starch is added and the titration finished with the iodine. Electrolytic Estimation of Tin in Tin Ores. By EDWARD D. CAMPBELL and E. C. CHAMPION (J. Amer. Chem. Soc., 1898, 20, 687--690).-0ne gram of the finely ground ore is fused with 3 grams of sulphur and 3 grams of sodium carbonate in a covered porcelain crucible inserted in a larger one; this is then placed on a triangle and covered with a Hessian crucible, the bottom of which has been removed.After being heated for an hour to a full red heat, it is allowed to cool, the inner crucible is placed in a beaker with water to dissolve the soluble tin compound, and the insoluble portion is again fused with soda and sulphur and the twofiltrates are united. Hydro- chloric acid is now added until all the tin is precipitated, and the liquid is evaporated to about 75 c.c,, mixed with 10 C.C. of hydrochloric acid, and fully oxidised by means of sodium peroxide. After filtering off from any sulphur, ammonia is added to the filtrate until the liquid becomes slightly turbid, and then 50 C.C. of a 10 per cent. solution of ammonium hydrogen oxalate is added, which will cause the solution to become clear, The liquid is now electrolysed during a night with a current N.D.l O O = O * l O amphre with an E. M. F. of 4 volts. This will cause the metal to be completely precipitated as a pure white, firmly adhering coating upon the platinum dish, and after being washed first with warm water, and then with alcohol, it is dried and weighed. The dish, cleaned by dissolving off the tin with hydrochloric acid, is Estimation of Tin in Commercial Antimony. By JOHN PATTINSON AND HUGH S. PATTINSON (J. SOC. Chem. Tzd., 1898, 17, 214--215).-1n this process, advantage is taken of the very sparing solubility of antimony pentasulphate in cold strong sulphuric acid. About 6.5 grams of the pulverised metal is heated with 75 C.C. of sulphuric acid of sp. gr. = 1.83 until completely dissolved, which re- quires about 10 minutes, and then allowed to cool completely, when the greater part of the antimony sulphate crystallises out, whilst the tin, arsenic, copper, iron, and other impurities (except lead) remain in solution, The whole is thrown on an asbestos filter, the precipitate washed several times with sulphuric acid (sp. gr.= 1-83), and the filtrate diluted with 3 times its volume of water, cooled, nearly neutralised with ammonia, and treated with an excess of strongly yellow ammonium sulphide. All the metals except tin, arsenic, and antimony are precipi- tated, and are filtered off and washed with ammonium sulphide. The filtrate is then feebly acidified with dilute sulphuric acid and the sulphides of tin, arsenic, and antimony collected and washed. The precipitate is next boiled with a solution of bromine in strong hydro- M.J. S. washed, dried, and weighed. L. DE I(.ANALYTICAL CH EMISTBY. 63 chloric acid, any sulphur which separates is oxidised by fuming nitric acid, and the united solntions are boiled until free from bromine. The greater part of the acid is now neutralised by ammonia, and the tin is separated from the other metals by Clarke’s oxalic acid process, for which purpose oxalic acid is added to saturation and hydrogen sulphide passed through the hot solution; this throws down the arsenic and antimony, whilst the tin remains in solution. Finally, the filtrate is nearly neutralised with ammonia, an excess of ammonium sulphide added, and the stannic sulphide thrown down by acetic acid. M. J. S . Assay of Telluride Ores, By CHARLES H.FULTON ( J . Amer. Chem. Xoc., 1898, 20, 586--597).-As telluride ores, when assayed for gold and silver, give less accurate results than other auriferous minerals, the author has made a laborious investigation into the cause of this, and has now greatly improved the process. I f the ore is very poor, 1 assay-ton of the powder is mixed with the same amount of dry soda, and half its amount of silica; 1-6 assay- tons of litharge, 10 grams of borax glass, and 2 grams of argol are added, and the whole well mixed and covered with salt. If traces of silver are likely to be present, an extra 0.02 gram of this metal is added, and also 4 iron nails to assist in desulphurising the ore. I n dealing with rich ores, only one-fifth of an assay-ton is used with a t least 2 assay-tons of litharge, 1 assay-ton of soda, and 1 gram of argol.The fire should be moderately hot, and the fusion should last from 40-50 minutes; the lead button obtained should weigh about 20-28 grams, and be, if possible, submitted a t once to cupellation without previous scorification. The traces of gold absorbed by the cupel may be disregarded, but the slag should always be powdered and remelted with another assay- ton of litharge and 2 grams of argol ; the button formed is then also By 9. N. RAIKOW (Chem. Zeit., 1898, 22, 149--150).-Dietze has proposed the following standard tests for the purity of Otto of roses. (1) The sp. gr, a t 1 5 O should not exceed 0.870. (2) The solidification point should not be below 15--20°. (3) The rotatory power observed in a 100 mm.tube at 20° should not exceed -lo 30’. (4) The saponification number should not exceed 9.5-10, and the relation between the acid and ether numbers not be higher than 7. The author having tested the process with two samples of Otto of roses of undoubted genuineness, states that the tests do not safeguard Technical Analysis of Asphaltum and Asphalts. By STEPHEN F. PECKHAM (J. SOC. Chem. Izd., 1898, 17’,438--439).-For technical purposes, a more or less empirical examination is of greater value than a scientific analysis, and it isof primary importance to ascertain what proportion of the mineral is soluble in light petroleum, boiling oil of tur- pentine, and chloroform respectively. If the ‘‘ organic matter not bitumen ” is large in amount, its nature should be ascertained.The cupelled. L. DE K. Examination of Otto of Roses. against an adulteration with oil of geranium. L. DE K.64 ABSTRACTS OF CHEMICAL PAPERS. amount and form of combination of the sulphur is next in importance, then the amount of the nitrogen and, lastly, that of the iron and aluminium. The solvents used should be carefully freed from water. Quantities of the mineral containing about 0.5 gram of bitumen aro weighed into two 11 cm. extracted filters of known weight, placed in stop-cock funnels ; the filters are filled with light petroleum which is allowed to run off slowly until the colour has perceptibly diminished, then the stop-cock i8 kept closed for 15-30 minutes after each addi- tion of solvent and the last digestion should extend to 12 hours.The filters are dried a t 6 6 O and weighed. They are then exhausted with boiling oil of turpentine which is displaced by light petroleum before drying ; the same filters are then exhausted with chloroform. They may next be extracted with 10 per cent. hydrochloric acid which re- moves calcium and magnesium carbonates and calcium sulphate ; and lastly, they are deflagrated with sodium carbonate and potassium nitrate, and the sulphur present as pyrites, silica, iron, and aluminium are estimated in the fused mass. For total sulphur, a fresh portion of the mineral is deflagrated in the sameway. Another portion is dissolved in benzene, the solution washed with dilute (10 per cent.) sulphuric acid, and the acid solution is treated with sodium nitrate when any nitro- genous basic oils present will be recognised by their odour.Another portion is exhausted with chloroform, and the residue extracted with ammonia for peat acids. Free sulphur will be found in the petroleum extract, organic aluminium compounds in the turpentine solution. Nitrogen may be determined by any method. The interpretation of the analytical results is reserved for a later communication. By FREDEBIC WILLIAM RICHARDSON and ADOLF J A F F ~ (J. Soc. Chem. Ind., 1898, 17, 330--333).-The only trustworthy methods for the estimation of glycerol are the dichromate and the acetin methods (Abotr., 1890, 425), and of these the dichrom- ate process is the simpler and more satisfactory. The authors depart slightly from Hehner’s instructions, relying on basic lead acetate for the removal of chlorides as well as of organic impurities, removing the excess of lead by diluto sulphuric acid and filtration before adding the dichromate.They recommend somewhat different proportions, namely, 20-25 C.C. of the glycerol solution, 25 C.C. of dichromate (Hehner’s solution, of 74-86 grams per litre : 1 c.c.=O-Ol gram of glycerol), and 25 C.C. of concentrated sulphuric acid, and find that 20 minutes heating in the water-bath completes the reaction. It is possible to estimate the glycerol in commercial samples by using a table of specific gravities, but i t is necessary to determine the ash and to deduct certain constants from the specific gravity, in order to correct for the organic impurities usually present ; these constants require to be varied for different percentages.Estimation of Phenols in Disinfectants in the Presence of Soap. By WERNER SPALTEHOLZ (Chm. Zed., 1898,22, 58)-The following process is recommended for testing compounds which contain the phenols in the free state; the sample is heated in an iron retort to 200°, and steam is passed through i t until oily drops no longer come over with the distillate. The temperature during the distillation should M. J. S. Estimation of Glycerol. M. J. S.ANALYTICAL CHEMISTRY, 65 not exceed 210°, as otherwise any olein soap which may be present will undergo decomposition ; rosin soap, however, may be heated with- out decomposition to 220". The distillate is shaken with benzene to dissolve the phenols, and the benzene is then agitated with aqueous soda and the phenols precipitated from the alkaline solution by means Estimation of Small Amounts of a-Naphthol in Commercial P-Naphthol.By JOHN PROCHAZKA and H. N. HERMAN (J. Xoc. Chem. Ind., 1897, 16, 894--895).-The method is based on the fact that a-naphthol combines with diazo-compounds more readily than ,&naphthol does, and forms more soluble products. The diazo-compound employed is thatof 1 : 4-naphthylaminesulphonic acid (naphthionic acid) : 27.5 grams of (90 per cent.) sodium naphthionate is dissolved in 185 C.C. of water, 6.2 C.C. of concentrated sulphuric acid is diluted to 186 C.C. and slowly added with stirring, the mixture is cooled below 5", and 7 grams of (98 percent.)sodium nitrite ina 10 per cent. solution is slowlyadded ; the paste obtained in this way is made up t o 750 c,c.The P-naphthol solution is prepared as follows : 1.5 grams of P-naphthol, 200 grams of a 25 per cent, solution of sodium hydroxide, and 140 grams of a 10 per cent. solution of sodium carbonate are heated together until the P-naphthol is dissolved, and the solution is made up to 250 C.C. and cooled below 5" before use. To this P-naphthol solution, 37.5 C.C. of the diazo-solution (being GG of the theoretical amount) is slotvly addedwith stirring. If the P-naphthol solution is pure, the coloiir produced is entirely insoluble; but the presence of less than 10 per cent. of a-naphthol is indicated by a peculiar bluish tint and the production of a coloured supernatant liquid. The amount of a-naphthol can be very fairly estimated by dipping strips of filter paper into this liquid, and comparing the depth of t i n t with that produced by a solution of known composition.By ADOLF LIEBMANN (J. Xoc. Chem. Ind., 1897, 16, 294-296).-Quantities of a-naphthol greater than 0.1 per cent. present in the P-naphthol used for preparing paranitraniline red, are deleterious as regards the colour of the resulting dye. P-Naphthol can readily be freed from a-naphthol by crystallising it from toluene, washing the crystals first with a mixture of toluene and light petroleum, then with the latter alone, steaming, and crystallising the steamed product several times from boiling water. For determining the quantity of a-naphthol in P-naphthol, the following process gives good results even when 0.01 per cent. only of the former is present ; 0.144 gram of the P-naphthol is dissolved in 5 c,c.of absolute alcohol contained in a graduated test-tube, and the solu- tion made up to 15 C.C. with pure toluene ; 0.14 gram of paranitraniline dissolved in 9 C.C. of dilute hydrochloric acid is then cooled and diazo- tised with 1 C.C. of normal sodium nitrite, and 1 C.C. of the diazo-solution added to the tube containing the &naphthol. Water is then added, the toluene solution separated and shaken with 5 C.C. of normal caustic soda, and the colour of the alkaline solution compared with that of the alkaline solution obtained in exactly the same way from P-naphthol containing a known quantity of a-naphthol. The test is based on the fact that the hydroxyazo-derivative obtained from of an acid.L. DE K. M. J. S. Paranitraniline Red. VOL. LXXVI ii. 566 ABSTRACTS OF CHEMICAL PAPERS. a-naphthol and paranitraniline is soluble in alkalis, whereas the corresponding P-naphthol derivative is insoluble. The following method of estimating metanitraniline in paranitr- aniline is available when more than 0.1 per cent. of the former is present. 0.25 gram of the paranitraniline is reduced to paraphenylene- diamine by zinc dust and hydrochloric acid in a flask which permits gas t o escape and yet does not allow air to enter; the colourless solution is then quickly filtered and diluted t o 250 C.C. 0.25 gram of metanitraniline is reduced in the same way, and made up to 250 C.C. Ten C.C. of the paraphenylenediamine solution is then diluted to 50 c.c., and a drop or two of dilute sodium nitrite added ; if the paranitraniline is pure, only a very slight change in colour occurs.If, however, metanitraniline is present, a light brown coloration (Bismarck brown) is produced ; by comparing the latter with that obtained from a known quantity of the standard metaphenylenediamine solution, the amount of metanitraniline can be determined. W. A. D. Estimation of Sugars as Osaeones. By CARL J. LINTNER and KROBER (Ann. Agrron., 1898, 24,448; from Zeit. Bvauwesen, 1896,153). -Twenty C.C. of t h e solution, which should not contain more than 1 per cent, of sugar, is heated for one hour and a half on a water bath with phenylhgdrazine (1 gram) and 50 per cent. acetic acid (1 gram). I n presence of dextrin, the heating must be prolonged to 2 hours, Boiling water (20 c.c ) is then added, and the osazone collected on a tared tilter, dried a t 110' for 3 hours, and weighed, Saccharose, which is not completely inverted by acetic acid, is first inverted with hydrochloric acid ; sodium acetate is then added, and the process continued as described.The method is suitable for dextrose, levulose, and saccharose both alone and in presence of maltose and dextrins; the latter increase the weight of the osazone slightly. Detection and Estimation of Glucose in Diabetic Urine, By A. CARPENI~ (L'Orosi, 1697, 20, 157--160).-A quantity of urine containing not more than 0.2 gram of glucose is, if acid, neutralised with potash or, if alkaline, boiled to expel ammonia, mixed with a slight excess of lead acetate solution, filtered, and the precipitate on the filter washed with water.Five or six grams of glycerol are added to the filtrate and washings, and the liquid is then mixed with six times i t d volume of alcohol of 95-96', filtered again if necessary, and about 10 C.C. of baryta water added. If glucose is present, a precipitate is produced, which may be collected, washed with alcohol of 95-96', and converted into barium sulphate in the usual manner. Each decigram of the sulphate corresponds with 0.0772 gram of glucose. The test analyses given are very satisfactory. The glycerol in this process is added to prevent the precipitation of barium hydroxide by the alcohol. According to the author, the precipitate which glucose forms with baryta has the composition BaC6HIoo6, and not Ba(C6H1,0,),, as By ARTHUR R.LING ( J . Soc. Chem. Ind., 1898, 17, 1 10-lll).-The author gives N. H. J. 11. usually stated. N. L. Clerget's Method of Estimating Saccharose.ANALYTICAL CHEMISTRY. 67 lOOIl 142.66 - 0.58’ results confirmatory of Herzfeld’s well-known formula, S = which is used when K stands for the difference between the readings of the Soleil-Ventzke-Scheibler polariscope, before and after the inversion of 26.048 grams of saccharose per 100 C.C. It is customary t o make the solution after inversion of only half this strength, and t o multiply the observed reading, i, by 2 before deducting it from the original reading. If any quantity other than 13.024 grams of sugar is inverted and diluted to 100 c.c., the formula becomes X= 141.84 + o.05i - 0,5t.Modiflcation of Clerget’s Saccharimetric Process, applicable to After Products, and Molasses. By ARTHUR R. LING and JULIAN L. BAKER (J. Xoc. Chern. Ind., 1898, 17, lll-l14).-The authors recommend the use of invertase (compare O’Sullivan, Trans., 1886, 58; 1891, 46) instead of hydrochloric acid for the inversion of saccharose, on the ground that, in highly impure substances, its hydrolytic action is u o r e likely to be confined to saccharose than that of a mineral acid, and they show by experiments on pure sugar that identical results are obtained with the two inverting reagents. Satisfactory agreement is shown between duplicate determinations made by this process on various dark commercial products, 10011 M. J. 5. M. J.5. Estimation of Sugar in Chocolate. By P. CARLES (J. Phwm., 1898, [vi], 8, 245--257).-The optical method of determining sugar in chocolate is inaccurate, because it neglects to take into account the volume occupied in the solution by dissolved cocoa, and the rotation often caused by the latter. The values obtained by cupric reduction are also high, since, after inversion, substances, other than dextrose, which reduce Fehling’s solution are often present. The following process, however, gives good results : 16.20 grams of the chocolate in thin shavings is heated with 80 C.C. of water during 1+ hours on the water-bath, 2-3 C.C. of a solution of basic lead acetate added, the mixture well shaken, and, after being diluted to 100 C.C. with water, filtered, and the amount of sugar determined by the saccharimeter.I f N denotes the value thus obtained, the true percentage of sugar =0*919 N. W. A. D. By GEORG LEBBIN (Ann. Agron., 1898, 24, 352 ; from Arch. Hyg., 1897, 28, 213).-The finely powdered substance (3 t o 5 grams) is heated t o boiling with 100 C.C. of water, for half an hour, to gelatinise the starch; 20 per cent. hydrogen peroxide (50 c.c.) is then added, and the boiling continued for 20 minutes, during which time 5 per cent. ammonia (15 c.c.) is added, 1 c.c at a time. The mixture is then boiled for 20 minutes longer, filtered through a tared filter, the precipitate washed with boiling water, dried, and weighed ; the weight of the ash is afterwards deducted. In some cases, the nitrogen is determined and the corresponding amount of protein also deducted.Concordant results, obtnined with rye and wheat bran and with wheat grain, are given. Estimation of Cellulose. 5-268 ABSTRACTS OF CHEMICAL PAPERS. Filter paper treated with hydrogen peroxide and ammonia lost 2-72 to 5.65 per cent. Estimation of Crude Fibre in Fodders and Foods, By JOSEF KONIG (Bied. Centr., 1598,2'7, 706-711 ; from Zeits. Unters. NcdiTungs. u. Genussmittel, 1898, 3).-The air-dried substance (3 grams), contained in a dry 500 C.C. porcelain dish, is stirred with nearly 200 C.C. of glycerol (sp. gr.=1*230) containing 30 C.C. of strong sulphuric acid per litre, the rest of the 200 C.C. being used to rinse the glass rod, when done with, into the dish; the dish is then placed in an autoclave and heated for an hour at 137" (3 atmospheres pressure).When cooled to SO-loo", the contents of the dish are diluted with 200-250 C.C. of boiling water, and at once filtered through asbestos; and as soon as the whole of the residue is on the filter, it is washed successively with 300-400 C.C. of boiling water, about 50 C.C. of alcohol (about 93 per cent.), and a warmed mixture of ether and alcohol, until the filtrate is colourless. The filter is dried until the weight is constant, weighed, ignited, and again weighed ; the difference between the two weights is the amount of crude fibre free from ash. Gooch crucibles of 90 C.C. capacity and 35 mm. in diameter at the bottom were employed. An alternative method, not involving the use of an autoclave, is also given. The substance is boiled with glycerol and sulphuric acid (the quantities are as given above) in a reflux apparatus for 1 hour ; when the temperature reaches 120-1 30") the contents generally froth, and the flask has to be shaken a few times.The process is afterwards completed as already described. By the above method, the pentosans are removed either completely or nearly completely (to 6.62 per cent.). Leguminous fodders seem to be freed from pentosans with greater difficulty than gramineous fodders. The method is simpler, as well as more efficacious, than the older ones. Separation and Estimation of Acids of the Saturated Fatty Series. By SIGMUND ~ L Z M A N N ( A ~ L . Pharm., 1898,236,409-441). -The author has prepared and studied the properties of the barium salts of the following acids : formic, acetic, propionic, butyric, iso- butyric, isovaleric, hexoic, octoic, decoic, lauric, myristic, palmitic, stearic, and cerotic.Experiments on the separation of the volatile acids are described, based on the supposition that, if a mixture of the alkali salts of several fatty acids be partially acidified with sulphuric acid and distilled, the acid of highest molecular weight passes over first, and on further acidification, the next lower acid, &c. (compare Wechsler, Abstr., 1894, i, 12, and Crossley, Trans., 1897, 580). Formic and acetic acids cannot be separated in this way, but with the higher members a partial separation is possible. The solubility of the alkali salts of the volatile fatty acids in methylic and ethylic alcohols increases with the molecular weight, whereas amylic alcohol dissolves more sodium propionate than sodium butyrate. The salts of the lower members are not readily soluble in acetone, whereas sodium isovalerate is very soluble, and on cooling N.H. J. M. N. H. J. M.ANALYTICAL CHEMISTRY. 69 the solution no milkiness is caused, but a separation of long, glistening, prismatic needles ; by this means, isovaleric can be separated from propionic, butyric, or hexoic acid. Ethylic palmitate, prepared by heating the acid with a 3 per cent. solution of hydrogen chloride in alcohol (yield 80 per cent. of theory) melts at 24O and boils a t 1S4.5-185-5° a t 10 mm. Ethylic stearate, produced in a similar manner (yield, the same), melts at 33.5’ and boils at 199-201’ at 10 mm. The melting and boiling points of mixtures of these two ethylic salts are given.A. W. C. Sulphuric Acid as a Reagent in the Analysis of Fatty Acids By ERNST TWITCHELL (J. SOC. Chem. Ind., 1897, 16,1002-1004).- The saturated fatty acids (palmitic, stearic, &c.) dissolve in, but are not sulphonated by, concentrated sulphuric acid, even at 100’; on the other hand, oleic acid seems to be quantitatively sulphonated by acid of even S5 per cent., the sulphonated acid thus produced, C,,H,,* OH,* CH(SO,H)*COOH, being practically insoluble in light petroleum, whilst the unattacked fatty acids can be dissolved out by petroleum, if acid not stronger than 85 per cent. has been employed. From 95 per cent. sulphuric acid, petroleum fails to dissolve out stearic and palmitic acids.For the examination of a mixture of saturated and unsaturated fatty acids, about 1 gram is solidified in a thin layer on the bottom of a stoppered conical flask, about 3 C.C. of S5 per cent. sulphuric acid is added, and the flask slightly warmed ; as soon as a clear solution has been obtained, the flask is quickly cooled, 50 C.C. of light petroleum is added, the stopper inserted, and the flask violently shaken. The petroleum extract is then decanted, the flask twice rinsed with 10 C.C. of petroleum, and the united extracts washed with water and evaporated. Lard yielded 42.3 per cent., two samples of cotton-seed oil 32.6 and 23.9 per cent. respectively, of saturated acids, having melting points of 53-53.5’. M. J. S. Estimation of Tartaric Acid. By JOHN MOSZCZEKSKI (J.Xoc. Chem. Ind., 1898, 17, 215--216).-Goldenberg’s (‘ acid method,” which, a t the present time, is almost exclusively employed, does not provide for the separation of iron, aluminium, or the pectinic substances which are present in argols and lees, and which probably interfere greatly with the final titration. The following method excludes these substances, and is shorter than Goldenberg’s. Five grams of the finely pulverised substance is treated with 26 C.C. of 13 per cent. sulphuric acid; this provides a sufficient excess of sulphuric acid for all ordinary materials, a large excess should be avoided. After stirring for a few minutes, the mixture is made up to 250 C.C. with alcohol of at least 90 per cent., well shaken, im- mediately thrown on a ribbed filter, and 200 C.C.of the filtrate measured into a basin ; any long delay a t this stage is objectionable, as there is a risk of ethylic tartrate being formed. An alcoholic solution of potassium acetate is now added as long as it produces a precipitate of potassium hydrogen tartrate; also 5 C.C. of strong potassium chloride solution. After 6 hours, the precipitate is col-70 ABSTRACTS OF CHEMICAL PAPERS. lected on a filter, washed with strong alcohol, and titrated as .usual. A correction of 1.2 C.C. should be made for the bulk of the insoluble matter in the 250 C.C. flask, and 0.320 ( 1 gram or per cent.) of tartaric acid should be added to the result to compensate for the solubility of potassium hydrogen tartrate in alcohol. The method is interfered with by the presence of potassium oxalate, as also is the case with Goldenberg’s ; phosphoric acid also raises the results, apparently to the extent of 1 molecule of tartaric acid for 1 molecule of P,O,.M. J. 8. Estimation of Potassium Hydrogen Tartrate in Wines. By LOUIS MAGNIEB DE LA SOURCE (Chem. Centr., 1898, i, 149; from Rev. Intern. Falszjic., 10, 195--196).-First method.-Ten C.C. of the wine is evaporated over sulphuric acid to dryness, and meanwhile a solution is made by dissolving 1 gram of potassium hydrogen tartrate in 100 C.C. of water containing 10-12 C.C. of alcohol, and adding an excess of pure potassium sulphate; 10 C.C. of the filtrate is then added to the wine residue, so as to dissolve all matters except the cream of tartar and any potassium sulphate which may be present.After washing the insoluble matter with the same liquid, the residue is dissolved in hot water and titrated with standard baryta water. Second method.-One hundred C.C. OE wine is mixed with 1.5 gram of potassium sulphate, and evaporated down to 15 C.C. ; after the lapse of 48 hours, the crystals are collected, washed with the alcoholic liquid already described, and finally titrated with baryta. L. DE I(. Analysis of Raw Materials containing Tartaric Acid. By JOH. SCHAFER (Chem. Zeit., 1898, 22, 255-256 ; 269 ; and 404-405). -The first paper deals with the estimation of tartaric acid in argols, &c. To obtain correct results, Goldenberg’s method, slightly modified, should be used. The original process, which is all but universally adopted, consists in heating the sample with dilute hydrochloric acid, neutralising the filtrate with excess of potassium carbonate, evapo- rating to a small bulk, adding acetic acid and alcohol, and finally titrating the potassium hydrogen tartrate with standard alkali.The author recommends first extracting any fatty matter by means of a mixture of alcohol and ether ; after adding the acetic acid and alcohol, the mixture should not be allowed to stand overnight, but should be at once filtered. I n titrating, feebly red litmus paper should be used as indicator. The second paper is a reply to Eckstein’s criticism (following abstract). L. DE K. Analysis of Raw Materials containing Tartaric Acid. By F. ECHSTEIN (Chem Zeit., 1898, 22, 351-352).-This is a criticism on Schafer’s article (preceding abstract).The chief point of interest is the author’s condemnation of the use of red litmus paper. Violet litmus paper or azolithmin paper should be used when titrating the precipitated potassium hydrogen tartrate with standard soda. The rest of the paper is not adapted for abstraction. L. DE K.ANALYTICAL CHEMISTRY. 71 Test for Uric Acid, and its Volumetric Estimation. By TORQUATO GIULI (Chem. Zeit., 1898, 22, 330-331).-The paper is a preliminary communication on a new test for, and a volumetric estimation of, uric acid ; 10 C.C. of the urine, or a solution of uric acid containing about the same quantity of the acid as occurs in urine, is mixed with 10 C.C. of a 7-5 per cent, solution of ammonium molybdate, and then with 10 C.C. of normal sulphuric acid.After a few minutes, 10 C.C. of normal soda is added, which causes the precipitate to redissolve; in the presence of uric acid, a bluish liquid is obtained. N/100 solution of potassium permanganate is now added, 1 C.C. at a time, until the liquid, which first becomes green and then yellow, changes to a reddish- yellow. This is the end reaction, and if the permanganate has been checked in the same manner with a known quantity of pure uric acid, the amount in the sample is readily calculated. The author admits that urine probably contains matters which also reduce molybdic acid, and thus count as uric acid; the chief consti- tuent of urine, the urea, does not, however, reduce the reagent. 1,. DE K. Estimation of the Iodine Number. By C. ASCHMAN (Chem.Zeit., 1898, 22, 59 ; 71-’72).-This is a modification of Hubl’s process, the fats being measured instead of weighed, and a solution of iodine chloride used instead of the mercurial solution; 30 grams of potassium iodide is dissolved in 100 C.C. of water contained in a flask furnished with a side tube, which serves to carry off the excess of chlorine. Washed chlorine is now passed into the solution until the liberated iodine has redissolved, forming a dark yellow liquid. After being left for 6 hours in a cold place, potassium iodate and iodic acid separate. The clear liquid is then poured off, the crystals are washed four times with water, and the whole is made up to one litre. The solution is further diluted to such an extent that 10 C.C. of it, on adding 10 C.C.of a 20 per cent. solution of potassium iodide, liberates as much iodine as will correspond with 40 C.C. of N/10 sodium thiosul- phate. The fatty solution is made by measuring exactly 10 C.C. of the oil a t 15O, or 10 C.C. of a melted fat at 50°, and dissolving this in exactly 10 C.C. of chloroform. Of this solution, 0.4 C.C. is carefully measured into a 250 C.C. flask, and after adding 10 C.C. of chloroform, 20 C.C. of the iodine chloride is introduced, the mixture is well shaken, and left for 24 hours in the dark with occasional shaking, when it is titrated with thiosulphate in the usual way, after adding 10 C.C. of 20 per cent. solution of potassium iodide. A list of test results is given, the iodine figures being decidedly lower than those obtained by the original Hub1 method. It is claimed, however, that they are more trustworthy and concordant.L. DE I(. The solution will keep unaltered for a year. Detection of Sesame Oil in Butter or Margarines. By PAUL SOLTSIEN (Chem. Centr., 1898, i, 224 ; from Pharm. Zeit., 1897,42,83’7 ; 846)-In applying the furfuraldehyde test to butter or margarine, care should be taken to use a hydrochloric acid of sp. gr. = 1.125, as the stronger acid of sp. gr. = 1.19 causes a distinct red coloration with furfuraldehyde alone, and also with turmeric, which is often used t o72 ABSTRACTS OF CKEMICAL PAPERS. colour butters. Fats containing sesame oil give a permanent, fine red colour when heated on a water bath with stannous chloride; the colour is not discharged by moderately diluting with water.Turmeric also gives a reddish coloration with strong hydrochloric acid or stannous chloride, but the colour is not stable and disappears on Detection of Rape Oil. By A. PALAS (L’Orosi, 1897, 20, 49-50).-Thirty cubic centimetres of a 0.1 per cent. solution of rosaniline are mixed with 20 C.C. of sodium hydrogen sulphite solution of 34O, 200 C.C. of water, and 5 C.C. of sulphuric acid of 65’. The reagent thus obtained, which should be perfectly colourless, is agitated in the cold with an equal volume of the oil to be tested, when a rose tint is developed if rape oil is present. Two per cent. of rape oil can be detected in olive oil by this means. The reaction is not given by other oils, neither is it given by the fatty acids of rape oil itself.adding water. L. D E K . N. L. Apparatus for the Rapid Estimation of Fat in Soap, and of Hehner’s Number. By GIOVANNI POSSETTO (L’Orosi, 1897, 20, 73--76).-The apparatus consists of a flask of about 200 C.C. capacity, into the ground neck of which is fitted a glass tube graduated from 0 to 40 C.C. and closed a t the top with a stopper, I n order to determine the fatty acids in soap, about 1 gram of the sample is introduced into the flask and dissolved in hot water. The solution is then cooled, acidified with dilute sulphuric acid, the graduated tube inserted into the neck of the flask, and sufficient water added to bring the level of the liquid to the zero mark or thereabouts. Ether is now added, and the contents of the apparatus well mixed and allowed to settle ; the volume of the ethereal layer is then read, and an aliquot part of it is pipetted off and evaporated, the residue being afterwards dried and weighed.For the determination of Hehner’s number (percentage of insoluble fatty acids), 1-1.5 grams of the fat or oil is placed in the flask and dis- solved in alcoholic potash, the alcohol being subsequently expelled by evaporation and the residual soap treated as above described. The apparatus is also adapted for the estimation of the amount of Use of Lead Dioxide as a means of Clarifying Urine for Analysis. By A. LOUBIOU ( J . Phawn., 1898, [vi], 8,270-272 ; from Bull. Xoc. Phavm. Bordeaux, July, 1898).-Turbid or fermented urine can be readily clarified by the following method ; to 10 C.C. of it caustic soda is added until the solution becomes alkaline to phenolphthalein, 1.0-1.5 grams of lead dioxide is then added, and the mixture well shakenduring a minute, and filtered.In the clear solution thus obtained, the albumin can be determined by Tanret’s reagent; experiment shows that no albumin is removed by the lead dioxide during clarification. The process described is especially useful in the case of turbid biliary urine which cannot be obtained clear by other met hods. W. A. D. Modification of Morner and Sj oquist’s Method of Estima- ting Urea, By HENRI MOREIGNE (J. Pharm., 1898, [vi], 8, 193-197. Compare Abstr., 1891, 758 and 1561).-The process named oil in paints, and for other purposes. N. L.ANALYTICAL CHEMISTRY. 73 is more rapidly carried out by determining the nitrogen of the urea by means of sodium hypobromite, instead of by Kjeldahl’s method, as originally recommended.After the process has been carried out as usualuntil the addition of magnesia, the solution is evaporated to 8 or 10 c.c., a little distilled water added, and the solution decanted from the magnesia; the latter is washed by decantation, and the washings added to the solution of urea, which is diluted to 50 c.c., and the urea present in 10 c.c., determined by the hypobromite method. The above method gives lower results with urine than are obtained on purifying the latter by basic lead aoetate, before estimating the urea; the difference is due to the ammonium salts not being removed in the latter process. Estimation of Urea in Urine by means of Sodium Hypobro- mite.By HENRI MOREIGNE (J. Pharm., 1898, [vi], 8,197-200, and 241-245).-The results obtained by the ordinary method, using basic lead acetate to purify the urine, are too high, owing probably t o the incomplete removal of ammonium salts (compare preceding abstract) and small quantities of guanine and creatinine. All the substances present in urine, including ammonium salts, which are capable of yielding nitrogen when acted on by sodium hypobromite, are, however, completely precipitated on adding phosphotungstic acid. It is im- portant that the latter should be prepared as follows : 20 grams of sodium tungstate and 2.34 grams of crystallised phosphoric acid are boiled with 100 C.C. of water during 20 minutes, the solution slightly acidified with hydrochloric acid, and, after standing, filtered.To 10 C.C. of the urine, a small quantity of water is added, together with 4 C.C. of hydrochloric acid, and the amount of phosphotungstic acid (15-20 c.c.) necessary for accurate precipitation, and the whole diluted to 50 c.c.; after standing 24 hours, the solution is filtered, and 25 C.C. of the filtrate, rendered slightly alkaline by caustic soda, diluted to 50 C.C. The urea is estimated in 10 C.C. of the solution thus obtained by the hypobromite method. In the case of certain pathological urines, it is advisable to subject the latter to a preliminary precipitation with basic lead acetate. After adding this and diluting the solution to a known volume, it is left for some time, filtered, and the lead precipitated in a n aliquot portion by dilute sulphuric acid ; any excess of the latter is neutralised with caustic soda, the solution acidified with hydrochloric acid, and the lead sulphate allowed to subside.One-half of the total volume is then filtered, precipitated with phosphotungstic acid, and the urea determined as above described. W. A. D. Relation between the Total Nitrogen of Urine and the Nitrogen Present as Urea. By HENRI MOREIGNE (J. Phcmn., 1898, [vi], 8, 293-302).-Although the method of determining the total nitrogen of urine by Kjeldahl’s process, generally adopted, is satis- factory, the methods for determining the nitrogen of the urea are by no means accurate (compare preceding abstract). If, for example, the solution to which sodium hypobromite is added, in the hypobromite method, contains more than 0.5 gram of urea in 100 c.c., an error as W.A. D.74 ABSTRACTS OF CHEMICAL PAPERS. great as 2.5-3 per cent. may arise ; the composition of the solution of hypobromite also exercises great influence on the volume of nitrogen obtained. In the author’s opinion, little value can be attached to the ratio of total nitrogen of urine to urea nitrogen determined by other investigators. W. A. D. Volumetric Estimation of Alkaloids as Higher Periodides. By ALBERT €3. PRESCOTT and HARRY M. GORDIN ( J . Amer. Chem. Xoc., 1898, 20, 706-728). Volumetric Method for the Estimation of the Total Alkaloids in ‘‘ Cortex china succirubr.” By H. EKROOS (Arch. Yhccrm., 1898, 236, 328-334).-The finely powdered bark is extracted with a mixture of chloroform, ether, and aqueous soda for 3 hours, and a certain portion of the clear ethereal solution is then shaken with normal sulphuric acid, the excess of acid being titrated back with decinormal caustic potash solution, using a freshly prepared alcoholic solution of hsemntoxylin as indicator.The end of the reaction is denoted by a pale yellow colour, which, on vigorous shaking, changes to a bluish-violet. The method can also be used for the analysis of quinine extracts. A. W. C. Indigo Testing by Permanganate. By J. GROSSYANN (J. XOC. Chem. Ind., 1S97, 16, 974-975).-1t has been stated by Rawson (J. Xoc. Chem. had., 1885, 489) that, by direct titration with perman- ganate after sulphonation, a fairly approximate idea OF the value of a sampleof indigocan be formed ; the author shows, however, that,although this may be true as regards high class indigoes (Bengal, Java), the method, when applied to low class samples (Kurpahs, Oiides), gives very variable results, which, in some cases, may err to the extent of 34 per cent.Results sufficiently trustworthy for practical purposes are, however, obtained if the sulphindigotic acid is precipitated by sodium chloride, and after washing is dissolved in dilute sulphuric acid and titrated. The instructions given by Rawson (not here reproduced) must be exactly followed, and they should be combined with the author’s dye test, which is not described in this place, See this vol., i, 89. M. J. S. Indigotin and Nitrobenzene. By B. WILLIAM GERLAND (J. SOC. Chem. fnd., 1897, 16, 108-109.Compare Abstr., 1898, ii, 102).- Carefully purified cold nitrobenzene dissolves indigotin very slowly ; on warming, however, a blue solution is obtained, which becomes tinged with red a t 65O, and pure blood-red a t 95’. On cooling, the solution remains red during several hours, but if a glass rod is introduced immediately becomes blue. Owing to the tendency to supersaturation which nitrobenzene solutions of indigotin exhibit, the solubility of the latter a t the boiling point of the solvent could not be accurately determined ; the numbers vary from 0.5-1 gram in 100 C.C. After indigotin has separated from its nitrobenzene solution, 25 C.C. of the filtrate contains only 0.000225 gram of indigotin; in the author’s process of determining indigotin (Zoc. cit.), this amount is quite negligible.The indigotin crystals, before weighing, should beANA1,YTICAL CHEMISTRY. 7.5 extracted on the filter with acid and alcohol, dried, washed with benzene, and digested with concentrated hydrochloric acid ; after boiling with water and with aqueous sodium carbonate, the crystals are finally thoroughly washed with water, dried, and weighed. To determine indigotin in woollen and cotton fabrics? it is best to destroy the fibre by treatment with dilute sulphuric acid, and after filtering, washing, and drying to extract the residue with nitrobenzene. The author has confirmed the accnracy of his method by comparing the results given by the latter with those obtained by the Muller- Bernthsen method ; in addition, accurate results were obtained when known weights of indigotin were suitably adulterated, and then determined by the nitrobenzene method.Detection of Turmeric in Rhubarb Powder, By ADAM JAWOROWSKI (J. Phavm., 1898, [vi], 8, 303-304; from Ann. Chim. Anal., 1898, 102)-If the powder contains turmeric, on agitating it with chloroform (10 c.c.) for several minutes, and filtering, a yellowish-brown solution is obtained with a greenish fluoresc- ence; and on adding light petroleum (50 c.c.), a yellow, flocculent precipitate is formed, although the solution remains yellow and fluorescent. This is now divided into two portions; to the first, sulphuric acid (2-3 c.c.) is added, and to the second, a saturated solution of borax (1-1.5 c.c.). I n presence of turmeric, the former becomes violet, whilst the acid layer, at first bright red, becomes succes- sively reddish-brown and yellow ; the borax solution becomes coloured violet, without, however, any colour-change taking place in the petrol- eum layer. W, A.D. Standard Methods for the Sampling and Analysis of Tan- ning Materials. By HENRY R. PROCTER and J. GORDON PAHKER (J: Xoc. Chem. Ind., 1898, 17, 6--lO).-This communication makes public the resolutions on the above subject adopted by an Inter- national Conference of the Chemists connected with the leather industry, held in London on September 28-30, 1897. The “hide powder” method was adopted for the estimation of tannin. The resolutions came into force on January lst, 1898, and all leather trades’ chemists who are members of the Association have agreed to work by the Conference methods until these are altered at a future Conference. M. J. S. Chemical Method of Ascertaining whether Milk or Cream has been Heated to at least 80”. By V. STORCH (Bied. Centr., 1898, 2’7, 711-714; from 40de Beret. kgl. Vet. LandbohCjskoZes Lab. Zindokon. POTS. Copenhagen, 1898, 1-1 6).-Not only mixed milk, but the milk of single cows during the whole period of lactation, shows a bluish-grey coloration when treated with a drop of dilute hydrogen peroxide and a few drops of a 2 per cent. solution of praphenylene- diamine. The action seems to be rather less in the case of cream and rather greater with butter milk, probably owing to the varying amount of fat globules present. Whey produces a dark violet-brown colour. It is supposed that the blue coloration obtained with milk is the result of a special interaction of the casein and the diphenylenediamine. W. A. D.76 ABSTRACTS OF CHEMICAL PAPERS. Butter milk from sour cream gave the coloration only when the free acid was partly neutralised with lime water. Milk fat globules free from milk serum, and pure casein solutions, gave no coloration. The '' active substance" could not be obtained quite pure. It is especially abundant in the deposit which forms on the inner side of a centrifugal separator. When obtained as free as possible from proteids, the aqueous solution gives the same violet-brown coloration as is obtained with whey, but when added to boiled milk (which gives no coloration with hydrogen peroxide and paraphenylenediamiue) the dark blue colour is at once obtained. Nilk which has been heated to 79-80' may still produce the blue coloration, provided that it is cooled as soon as that temperature is reached. Heating for 2 minutes a t 75" is sufficient to destroy the active substance " if the cooling is slow. As regards the effect of acidity, it was found that, whilst with milk which required 17 C.C. of N/lO alkali to neutralise 100 c.c., the limit of temperature was 79", butter milk which required 90 C.C. of alkali was rendered inactive by heating to 71". The reaction is not without importance in the case of Pasteurisation. It sometimes happens that the whole of the milk has not been heated to 79". Milk heated to 8Z0, mixed with 10 per cent. of milk heated to 7S0, showed the blue coloration distinctly. The presence of 1 per cent. of milk heated at 75" could also be detected. By P. ONFROY (J. Pharm., 1898, [vi], 8, 7-9).-1n presence of 5 per cent. of gelatin, as much as 10 per cent. of water can be added to chocolate without altering the latter's appearance. When a considerable proportion of gelatin is present it can be detected by boiling the chocolate (5 grams) with water (50 c.c.), adding 5 C.C. of 10 per cent. solution of lead acetate, filtering and adding a few drops of a saturated solution of picric acid; the latter produces an immediate, light yellow, amorphous precipitate with solutions containing more than 0.01 per cent. of gelatin. When only a small quantity of gelatin is present in a chocolate, it is ren- dered insoluble by the tannin of the latter, and the following method bas t o be adopted for its detection. After removing the fat from 10 grams of the sample by means of ether, 100 C.C. of warm water is added, then 5-10 C.C. of a 10 per cent. solution of potassium carbonate, and 10 C.C. of 10 per cent. lead acetate; on filtering and carefully neutralising, a solution is obtained which can be tested for gelatin by the ordinary methods. N. H. J. M. Gelatin in Chocolate. W. A. D.

ISSN:0368-1769    

DOI:10.1039/CA8997605051

出版商:RSC    

年代:1899

数据来源: RSC

摘要:

77 General and Physical Chemistry. Magnet-radiometer. By NICOLAE TECLU (J. pr. Chm., 1898, [ ii], 58, 255-260. Compare Abstr., 1893, ii, 401).-The paper contains a detailed description and photograph of the '' magnet-radiometer " designed by the author for use in the diaphonometer previously described by him (Zoc. cit.). The outer portion of the vane of a radiometer is coated with a very thin layer of iron, so that move- ments of the vane can be caused, not only by the action of light rays, but also by the approach of a magnet ; when both forces are applied simultaneously, the position assumed by the vane will be a resultant of the two, and so 3an be applied to the measurement of the intensity of the light falling on the instrument. By FHAN~OIS DUPONT (BUZZ. SOC. China., 1897, [iii], 17, 584)-A much more satisfactory yellow light €or polarimetric observations is obtained when a mixture of sodium chloride and trisodium phosphate, in molecular proportions, is used in place of sodium chloride alone.By DOUGLAS MCINTOSH (J. Physical Chern., 1898, 2, 185--193).-The object of the author in undertaking this research was t o find a convenient standard having an E.M.F. of about 0.5 volt. A cell consisting of zinc, zinc chIoride, lead chloride, and lead, as described by Baille and Fhry, gives good results, and has an E.M.F. of 0.5 at 20' when the specific gravity of the zinc chloride is 1.23. The temperature coefficient is extremely low. A great many cells in which mercuric oxide was used as a depolariser were tried, but none of these were satisfactory, and the use of other oxides as depolarisers gave negative results. Cells of copper, copper sul- phate, mercurous sulphate, and mercury were tried and gave excellent results.The copper sulphate and mercurous sulphate are each taken in the form of a paste. The E.M.F. of this cell decreases with rising temperature, and in the neighbourhood of 1 6 ~ 5 ~ may be calcu- lated by the formula E = 0.3613 + (16.5 - t)0*0006 volt. Cells con- taining Pb, PbCl,, Hg,CI,, Hg were also examined, and gave satisfactory results. The E.M.F. increases with the temperature, and may be calculated approximately between 15' and 21° by the formula B= 0.5382 + ( t - 2l)O~OOOS. Determination of Polarisation. By KARL HEIM (Zeit. Elektl.0- chem., 1898, 4, 527).-In an electrolytic cell of resistance R, with insoluble anode, through which current C is passing with E.M.F. = 3, we have E = p + CR, where p is the polarisation.If a thin sheet of metal be interposed between the electrodes so as to divide the cell completely, without sensibly affecting its resistance, and the current be maintained unchanged, we -have E' = 2p + CR, or p = ,&' - E. In putting the method into practice, the main difficulty is encountered in arranging the cell so that the third electrode may be put in or taken VOL. LXXVI. ii. 6 A. W. C. Yellow Light for the Polarimeter. J, J. S. Normal Elements. H. C.78 ABSTRACTS OF CHEMICAL PAPEKS. out easily, and in such a way that the current shall pass through it, and not round it. A rectangular ebonite cell is provided with platinum electrodes fitting into grooves in the wallg 60 mm.apart. Between these, a third groove, 8 mm. deep and 0.25 mm. wide, receives the third electrode. This depth is sufficient t o prevent undue leakage round the electrode with moderate conductivities and current densities. About half an hour elapses before the polarisation becomes constant. The following are some of the results obtained. A greater depth would be better. Copper sulphate, 16 per cent. a t 14.7-14*95'. Current density ... 0.03 0.06 0.12 0*2 Polarisation ...... 1,591 1.628 1.668 1.695 Silver nitrate, about normal, a t Current density.., 0.015 0.03 0.06 0-12 Polarisation . . . . . . 0.888 0.897 0.903 0.908 0.3 amp./sq. dcm. 1 -71 7 volts. 0-2 0.4 amp./sq. dcm. 0.926 0.935 volt. 15-1 5.5' T.E. Pulverisation of Metal Cathodes During Electrolysis with a Constant Current. By GEORG BREDIG and FXITZ HABER (Bey., 1898, 31,2741-2752. Compare Abstr., 1898, ii, 364).-When a cathode con- sisting of a bright lead plate or wire conveying a current at 24-72 volts is brought into dilute sulphuric acid, a platinum anode being em- ployed, a momentary pulverisation of the lead occurs, and a fine, metallic powder falls through the liquid. This takes place a t isolated spots on the surface of the metal, bright indentations being left with rounded edges. A similar phenomenon takes place in alkaline solutions, but in this case is continuous and much more energetic. The metallic lead thrown down is peculiarly susceptible to chemical change, and can readily be converted into white lead by the simultaneous action of air and carbonic anhydride.The addition of small quantities of a chromate or chromium salt prevents the occurrence of the phenomenon. Mercury, tin, bismuth, thallium, arsenic, antimony, and Rose's metal all show the same phenomenon in alkaline solutions, whereas cadmium, zinc, copper, silver, aluminium, platinum, and palladium do not act in this way. In acid solution, on the other hand, only bismuth and Rose's metal behave in a similar manner to lead. The phenomenon is to be distinguished from the loosening of the surface which occurs with cathodes of platinum, palladium, and lead. I n alkaline solution, it is probably preceded by the formation of an alloy of the metal of the cathode with the alkali metal present, which is then decomposed by the water. This is especially marked in the case of mercury, but no similar action can occur in acid solution.Electrolytic Decomposition of Aqueoufir Solutions. By L. GLASER (Zeit. Elelitrochem., 1898,4, 355, 373, 397, and 424).-The author first repeats the experiments of Smale (Abstr., 1894, ii, 436) on the oxygen- hydrogen gas cell, and confirms his conclusion that the formation of water in this cell takes place in a reversible way a t the E.M.F. of 1-08 volts. He then goes on to determine the E.M.F.'s required to separate the ions contained in various aqueous solutions from their electrical charges. The observations are made by applying any desired A. H.GENERAL AND PHYSICAL CHEMISTRY. 79 E.M.F. from zero upwards to a pair of electrodes immersed in the solution under examination, and noting the current which is thereby caused to pass through the cell.When the E.M.F. is less than that required to produce continuous decomposition, a very small diffusion current is observed. When the decomposition point is reached, the current increases more or less suddenly, so that at each decom- position point a change in the direction of the curve connecting current and E.M.F. is observed. One of the electrodes is made of platinised platinum saturated with atmospheric oxygen, and is very large com- pared with the other ; in this way, its polarisation is rendered practically constant and the changes of direction observed are due to separation of ions at the small electrode. The small electrode being used as cathode, a decided increase of current is found at 1.08 volts with dilute sulphuric acid, and a much less decided change a t the same E.M.F.with solutions of sodium or potassium hydroxide ; the difference is due to the small number of hydrogen ions in the solytions of the bases. I n all cases, a decom- position point is better marked the greater the quantity of the particular ion which is present. When the small electrode was used as anode and the large oxygen electrode as cathode, an exceedingly well marked decomposition point was found a t 0.59 volt with solutions of sodium or potassium hydroxides, and a much less marked decomposition point at 0.6 volt with dilute sulphuric acid. Measured in both cases with reference to the large oxygen electrode, 1-08 volts are therefore required for the continuous separation of hydrogen and 0.59 volt for that of hydroxyl.The sum of these quantities, 1.67 volts, is the frequently observed polarisation in the ordinary electrolysis of dilute aqueous solutions. That visible electrolysis can be produced with 1-08 volts is explained by assuming the separation of 0 ions, the very minute amount of these ions present accounting for the slow course of the decomposition. When a solution of potassium hydroxide is electrolysed, using the small electrode as cathode, two changes of direction are observed in tbe current-E.M.F. curve, The first, at 1.08 volts, corresponds with the separation of the hydrogen ions from their charges, whilst the second corresponds to the separation of potassium ions.The position of the second point varies with the concentration of the potash solu- tions, the following values being found: lON, 1.32 volts; 4N, 1.38 volts; l N , 1.4 volts; +N, 1.45 volts; &N, 1.46 volts. Similar results are obtained with other bases, the values being, 1 normal KOH 1.4 volts 1 ,, NaOH 1.315 ,, 0.0002 ,, Mg(OH), 1.395 ,, 0.02 ,, Ca(OH), 1.33 ,, 0.22 ,, Ba(OH), 1.185 ,, 0.063 ,, Sr(OH), 1.20 ,, The ion separated here is, therefore, hydroxyl. From the latter measurements, it follows that the separation of hydrogen from aqueous solutions is only primary with very small 6-280 ABSTRACTS OF CHEMICAL PAPERS. electromotive forces ; with any ordinary current, the greater part of it is due to secondary action. Thermochemistry of Suberic Acid.By GUSTAVE MASSOL (BUZZ. SOC. Chirn., 1897, [ iii], 17, 745--716).-Suberic acid cryatal- lises in brilliant, white scales melting at 139.5' ; one litre of water at 17" dissolves about 1.8 grams of the acid, the heat of dissolution being - 5.45 Cal. Normal potassium suberate becomes anhydrous at 1 OOO, and dissolves in water with the development of + 0.92 Cal. Potassium hydrogen suberate is only very slightly soluble in cold water ; its heat of dissolution is - 5.36 Cal. at 40'. When a solution of this salt is con- centrated on the water-bath, suberic acid first crystallises out, and then the acid salt, whilst the more soluble normal salt remains in solution, C,H,,O,(solid) + 2KOH(diss.) = C,H,2K,04(diss.) + 17.9 Cal. C,H,,KO,(diss.) + KOH(diss.) = C,H,,K20,(diss.) + I1 -4 Cal.it is calculated that the heats of formation of normal potassium suberate and potassium hydrogen suberate are + 44.76 Cal.and + 25.67 Cal. respectively, all the substances concerned being in the solid state. Thermochemistry of Sebacic Acid. By GUSTAVE MASSOL (Bull. SOC. Chim., 1897, [iii], 17, 746 -747).-Sebacic acid crystal- lises in anhydrous, nacreous scales melting at 129'. One litre of water at 16O dissolves 0.55 gram of the acid, without sensible development of heat. Normal potassium sebate crystallises with one molecule of water, and dissolves in water with the absorption of -1.33 Cal. ; it does not lose water at loo', nor when placed in a vacuum over sulphuric acid, but the anhydrous salt is obtained by heating at 150' in a current of dry hydrogen. Its heat of dissolution is + 1.47 CaI.C,,H,,O,(solid) + 2KOH(diss.) = C,,H1,K,O,(diss.) + 17-68 Cal., it is calculated that the heat of formation of normal potassium sebate is 43.99 Cal., all the substances concerned being in the solid state. Potassium and sodium hydrogen sebates are not sufficiently soluble in water to allow of thermochemical study by the usual methods. T. E. From the heats of neutralisation, N. L, From the heat of neutralisation, N. L. Normal Dibasic Acids of the Oxalic Series. By GUSTAVE MASSOL (Bull. Soc. Chim., 1897, [iii], 17, 747-74S).-The heats of formation of the anhydrous normal potassium salts of some acids of the oxalic series have been found to be as follows : oxalic acid, + 58.97 Cal.; malonic acid, + 48.57 Cal.; succinic acid, + 46.40 Cal.; glutaric acid, + 44.23 Cal.; suberic acid, + 44.76 Cnl. ; sebacic acid, + 43.99 Cal. From these results, it appears that, as the molecular weight of the acid and the distance between the two carboxyl groups increase, the heat of formation of the salt decreases, and ultimately approaches that of two molecules of potassium acetate (43.72 Cal.). The influence of the carboxyl groups on each other decreases rapidly with the intro- duction of intermediary CH,-groups, a fact which is in accordance with the formation of anhydrides from these acids, succinic anhy-GENERAL AND PHYSICAL CHEMISTRY. 81 dride being easily obtained and glutaric anhydride with difficulty, whilst the higher members of the series seem to be incapable of existence.A similar relationship is observed in the production of lactones from acids of the lactic series. Acetaldoxime. By HECTOR. CARVETH (J. Physicul Chem., 1898, 2, 159--167).-The author has repeated Dunstan and Dymond's experiments on the freezing point of acetaldoxime (Trans., 1892, 61, 471 ; 1894, 65, 206), and confirmed them in every detail. All the freezing point phenomena can be accounted for on the assumption of an equilibrium between two modifications in the liquid phase. Although the rate of change of the freezing point of acetaldoxime is a function of the temperature to which the substance is heated, the final equilibrium is independent of the temperature. Heating to 11 4.5' causes the freezing point to drop from 47" t o 1 3 O , and also if the crystals are kept long enough at 20" they will liquefy, and if the liquid is kept for about 10 days and then cooled, the freezing point mill be found to be 13".I n other words, the equilibrium is not displaced by the temperature, and the relative amounts of these two modifications is not a function of the temperature. The liquefaction of the crystals is not accompanied by a measurable change of vapour pressure, and the author regards it as probable that two modifications exist in the vapour. N. L. Sunlight does not produce any visible effect. H. C. Determination of the Speciflc Gravity of Pulverulent Sub- stances. By GUSTAV J. W. BREMER (Rec. Tmv. Chim., 1898, 17, 263--269).-By the following method, more accurate results can be obtained than by using Kopp's volumenometer, and small quantities only of the substance dealt with are necessary; the difficulty of re- moving air bubbles in the ordinary method, using a pyknomefer, is also obviated.A flask (P), having a capacity of from 3-15 c.c., is surrounded by cold water, and is connected to a three-way stop-cock (R) fitted to the top of a manometer tube (a) which is closed below by an ordinary tap, 8, through which it communicates by india- rubber tubing with a pressure tube (C), R enables the flask P to be in connection with the manometer tube alone or with both it and the air simultaneously. The pressure tube is filled with mercury; by raising C, the level of the mercury in a is brought to coincidence, under atmospheric pressure, H, with the upper edge ( p ) of a window in a ring which slides on u near the top.By turning R through 1804 the connection between the flask and the air is broken, and the tube c is then lowered until the level of the mercury in a coincides with the upper edge (q) of the window in a second ring placed near the bottom of a. The difference in level, h, of the mercury in the tubes a and c is measured by a cathetometer. The observations described are then repeated after introducing a weighed amount, w, of the substance taken into the flask P. If h' denote the new difference of level in the tubes a and c, corresponding t o the original h ; H' the atmospheric pressure during the latter part of the experiment, v the volume occupied by the mercury between the levels of the upper edges of the windows p and p, and Q the required82 ABSTRACTS OF CHEMICAL PAPERS.36.40 138-1 35.90 109.8 35-10 75-8 volume of the powder, then x = v . H, as is usual, H=H', 21 -9 46'0 30.20 11.8 34.85 33 -90 32% 32.7 28.10 Acetone. lOs0O 19.91 29.92 40.81 48-67 57-43 60.43 Water. 89.92 80.00 69.67 58.22 48.68 36-64 25.75 Naphthalene. 0-08 0.09 0.4 1 0.97 2.65 5.93 13-82 Teniperature. 65.5" 55.3 45.0 38.0 32.2 28-5 28.2 The effect of a very small quantity of naphthalene on the consolute temperature is very marked, H. C.GENERAL AND PHYSICAL CHEMISTRY, 83 Distribution of Mercuric Chloride between Toluene and Water. By OLIVER W. BROWN (J. Physical CAem., 1598, 2, 51-52). -According to Skinner (Trans., 1892, 61, 342), a fairly constant dis- tribution ratio is obtained when mercuric chloride is added to mixtures of ether and water, Experiments made by the author with toluene and water show that the ratio of the concentrations is not constant in this case, the concentrations in the water phase not increasing quite so rapidly as those in the toluene phase.This would mean, according to the Nernst theory, that there is a slight dissociation in the aqueous solution. H. C. Solubilities of some Sparingly Soluble Liquids in Water. By W. HERZ (Bey., 1898, 31, 2669-2672).-The author has deter- mined the mutual solubility of a number of liquids and water, with the following results. 1000 C.C. of water dissolve 4'20 C.C. of chloroform, forniiiig 1003.9 C.C. ofsolution. carbon bisuhhide, 9 , ), 1'74 2 , ,, 3-41 J , ,, 81-10 Y , ,( 0.82 9 3 ,, 32-84 Y ) ,, 34.81 chloroform dissolve 1-52 carbon bisul- phide dissolve 9'61 light petroleum dissolve 3-35 ether ,, 29.30 benzene ,, 2.11 amylic alcohol dissolve 22-14 aniline ,, 52-22 Lforrniug 1002'08 light petroleum (sp.gr. 0.6646) ,, 1003.41 ether ,, 1071'45 benzene ,, 1000.82 amylic alcohol ,, 1029.92 aniline ,, 1034.81 water ,, 996.2 9 , ,, 1009.61 I , ,, 1006*04 3 , ,, 1032082 1 7 ,, 1001.35 9 5 ,, 1012.82 Y , ,, 1049.55 Indicators. By JOHN WADDELL (J. Physical Chem., 1898, 2, 171-1 84).-According to the dissociation theory, an indicator must be a weak base or a weak acid in which one of the ions has a different colour from that of the undissociated substance, Under these circum- stances, the presence in the solution of a liquid in which the indicator dissociates to a less extent than in water should cause the colour due to the ion to disappear more or less.Nine indicators were, therefore, taken, and tested in presence of alcohol, acetone, ether, benzene, and chloroform. The results obtained were in keeping with the dissocia- tion theory. In alcohol and acetone, the colour of the ion is often perceptible, but this disappears when any one of the other organic solvents is added. It is often possible to predict the acid or basic properties of an indicator from the colour changes on the addition of organic solvents. Methyl-orange and lacmoid act as weak bases ; fluorescein, phenacetolin, and probably corallin are both basic and acid. More satisfactory results were obtained with ammonia and acetic acid than with caustic potash and hydrochloric acid.This the author84 ABSTRACTS OF CHEMICAL PAPERS. regards as due to the dissociation, to some extent, of salts of weak acids and weak bases into the free acid and free base in organic solvents. H. C. By CHARLES A. SOCH (J. Phgsical Chem., 1898, 2, 43-50).-Solubility determinations of the pairs of salts, potassium chloride and potassium nitrate, potassium chloride and sodium chloride, potassium nitrate and sodium chloride, and sodium nitrate and sodium chloride were made at 25O and a t 80' in pure water, and at 25' in 40 per cent. aqueous alcohol. The results are given in the following table, the concentrations being in grams of salt per hundred grams of solvent. Fractional Crystallisation. Aqueous alcohol at 25". Water at 25". KCl ......... 10.06 34.12 ...... 5-29 22.58 1.51 Ratio ......1-90 NaNO, ...... 22.78 43.66 NaCl ........ 10.17 26.58 ....... 2.24 1-64 ...... 13.74 41-14 NaCl ........ 15.78 38.53 Ratio.. ...... 0.87 1.07 NaCl ........ 12.28 29.05 KCI ......... 5.87 17.1 Ratio ........ 2.09 1.70 { KNO, I Water at 80". 40.20 117.5 121.6 0.361 17.62 6.90 39-81 4.1 4 26-5 31.0 168.8 0.855 From the above, it will be seen that the displacement of the equi- librium by the addition of alcohol is in no case as large as the change produced by difference of temperature. A short theoretical treatment of the subject of fractional crystallisation by Bancroft is added. H. C. Absorpt,ion. By JACOSUS M. VAN BEYYELEN (Zeit. army. Chem., 1898, 18: 98--146).-The continuation of the author's research is in accordance with the previous results (Abstr., 1897, ii, 137, and this vol., ii, 12).The elimination of water from the hydrogel, up to a certain point, takes place without the formation of water-free inter- stices, the decrease in volume corresponding with the amount of water evaporated. The greater part of the water evaporates at 15O, with a rapidity little less than that of water itself. As the remaining water evaporates at a steadily increasing vapour pressure, the colloid gradu- ally assumes a solid, glassy condition. The point at which the elimin- ation of water ceases, under a given vapour pressure, varies with the method of formation and age of the colloid, the rapidity of the evaporation, and temperature. In the reabsorption of water by a partially dried colloid, a higher vapour pressure is necessary in order to obtain the same amount of water in the colloid as was present before drying.The absorbing properties of the colloid are decreased by formation in a concentrated silica solution, by prolonged drying, and by time. At a red heat, the absorbing properties are lost. E. C. R.GENERAL AND PHYSICAL CHEMISTRY. 85 General Problem of Chemical Statics. By PIERRE DUHEM (J. Physical Ch,em., 1898, 2, 1-42 and 91--115).--A mathematical paper not suitable for abstracting. H. c. Combination of Gases. By H. H~LIER (Ann. Phys. Chim., 1897, [vii], 10, 521-556).-The author describes the furnace, pyrometer, and gas apparatus employed by him in studying the combination of gaseous mixtures at definite temperatures. Experiments, made on a mixture of hydrogen and oxygen containing the gases in combining proportions, show that a t any given temperature there is a certain limit of combination, and that, after a certain time, continued heating produces no further interaction.This limit is reached in a relatively short time; in the case of oxygen and hydrogen heated to 300', the time required is 17 seconds. The amount of water produced varies with the temperature, at 180' it is only 0.04 per cent., a t 825' i t is 96.1 per cent., and combination takes place explosively at 853' (Abstr., 1896, i, 416). This temperature of explosion is 300' above that indicated by Mallard and Le Chatelier. Van't Hoff defined the tem- perature of explosion as that at which the initial loss of heat due t o conduction, &c., is equal to the heat produced in the same time by the chemical reaction.It may, therefore, be raised considerably by in- creasing the initial loss of heat of the gaseous mixture. Experiments made on the above mixture in the presence of nitrogen, show that the inert gas hinders the combination ; at 491°, the de- crease produced by the addition of 13 volumes of nitrogen is 17.4 per cent. Half the quantity of nitrogen produces aspproximately half this diminution. Excess of oxygen or hydrogen increases the amount of combination, but, volume for volume, excess of oxygen produces greater effect than excess of hydrogen. A mixture of carbonic oxide and oxygen, in combining proportions, begins to react at 195', the amount of combination increases slowly up t o 500°, and more rapidly up to 855O, when it amounts to 65 per cent.The presence of nitrogen diminishes the amount of combination. The inert gas also decreases the velocity of combination; with the normal mixture of carbonic oxide and oxygen at 549O, the limit is reached in 30 seconds; in the presence of l& volumes of nitrogen, the limit is attained only after 70 seconds. An excess of oxygen increases the percentage of combination, ex- cess of carbonic oxide, on the contrary, diminishes the amount of carbonic anhydride produced. The walls of the vessels in which gaseous combination occurs have a marked influence on the results (compare Abstr., 1897, ii, 437, 486, and 548). The combination of hydrogen and oxygen is always complete when the normal mixture is heated for 5 hours in tubes of potash glass, and the water produced is strongly alkaline ; in tubes of lead glass, the combination, carried out under similar conditions, is far less complete, and some of the hydrogen is used up in reducing the lead silicate present.In new silvered tubes, the combination is complete, but on repeating the experiment the amount of water formed, although variable, never indicates complete combination. The presence of water vagour decreases the amount of combination.86 ABSTRACTS OF CREMICAII PAPER3 . This cannot be due to the fact that there is any tendency towards a reverse action. since the effect is well marked a t temperatures far below that a t which steam dissociates . The combination of gases a t any temperature attains a limit.not because the reaction is reversible. but because the presence of the products of combination appears to hinder the completion of the reaction. Report of the Committee of the German Chemical Society on Atomic Weights . By the Members of the Committee : HANS LANDOLT. WILHELM OSTWALD. and KARL SEUBERT (Bey., 1898. 31. 2761-2768).-This report is issued by the committee appointed by the German Chemical Society on December 1. 1897. to consider the question of atomic weights. and to draw up a table of the most pro- bable values of these constants for general use . The members of the committee were unanimous in adopting the two foilowing conclusions . I . The atomic weight of oxygen shall be taken as the standard. and assigned the value 16.000 ; the atomic weights of the other elements to be then calculated from their.directly or indirectly determined. combining proportions with oxygen . I1 . The numbers which may a t present be taken for practical pur- poses to represent the probable atomic weights of the elements are as follows . G . T . M . Aluminium ...... Antimony ......... Argon (2) ......... Arsenic ............ Barium ............ Beryllium ........ Bismuth ............ Boron ............... Bromine ............ Cadmium ......... CEsium ............ Calcium ............ Carbon ............ Cerium ............ Chlorine ............ Chromium ......... Cobalt ............... Copper ............ Erbium (1) ......... Fluorine ............ Gallium ............ Germanium ...... Gold .............. Helium (1) ......... Hydrogen .........Indium ............ Iodine ............... Iridium ............ Iron .................. Lanthanum ...... Lead ............... Lithium ............ Magnesium ......... Manganese ........ Mercury ............ Molybdenum ...... A1 Sb A AS Bil Be Bi B Br Cd cs Ca C Ce c1 Cr co c u Er F Ga Ge All He H In I I r Fe La Pb Li w4 Mn Hg Mo 27.1 120 40 75 137*4 9 '1 208 -5" 11 79.96 112 133 40 12-00 140 35.45 52 '1 59 63-6 166 19 70 72 197'2 4 1-01 114 126.85 193.0 56 -0 138 206'9 7 -03 24-36 55.0 200.3 96 *O Neodymium ( a ) ... Nickel ............... Niobium ............ Nitrogen ............ Osmium ............ Oxygen ............ Palladium ......... Phosphorus ...... Platinum ......... Potassium ......... Praseodymium (2) Rhodium ............ Rubidium ......... Ruthenium .........Samarium ('1) ...... Scandium ......... Selenium ......... Silicon ............ Silver ............... Sodium ............ Strontium ......... Sulphur ............ Tantalum ......... Tellurium ......... Thallium ......... Thorium ............ Tin .................. Titanium ......... Tungsten ......... Uranium ............ Vanadium ......... Ytterbium ......... Yttrium ............ Zinc. ................. Zirconium ......... Nd Ni Nb N os 0 Pd P Pt K Pr Rh Rb Ru Sa s c Se Si Sr S Ta Te T1 Th Sn Ti W iT V Yb Y Zn Zr 2 144 589" 94 14'04 191 16.00 106 31-0 194.8 39-15 140 103.0 85-4 101.7 150 44'1 79.1 28.4 107-93 23-05 87-6 32-06 183 127 204.1 232 118.5" 48'1 184 239-5 51.2 173 89 65'4 90'6INORGANIC CHEM18TR.Y. 87 The numbers in the above table may be regarded as correct t o the last figure given, with the exception of those marked by an asterisk. The atomic weight of nickel is certainly lower than t h a t of cobalt, but the number 58.7 is only correct to k0.2. A like uncertainty holds for bismuth and tin, For hydrogen, the value 1.008 is only certain to 0.001. For practical purposes, the number 1.01 may, therefore, be taken, the error being only about one-fifth per cent. H. C. Gas Generator. By EMIL JAGEI~ (Zeit. cclzgw. Chew., 1898, 961)-The apparatus, of which a drawing is given in the paper, consists essentially of a kind of large wine-glass, but having perfora- tions through the bottom, containing the substance to be acted on and placed at the bottom of a cylindrical glass vessel containing acid. Over it is placed a double bell-jar ; the inner smaller one which plays the part of a diving bell may be lifted up and down by means of a glass rod attached to it. When down, the acid is completely excluded , when up, the acid ascends and acts on the substance. The strength of the gaseous current is regulated by a screw-clamp attached to a piece of india-rubber connected with a side tube belonging to the outer bell- jar. The advantage claimed is that, when out of use, not the slightest evolution of gas takes place, even when the screm-clamp is loosened. L. DE K.

ISSN:0368-1769    

DOI:10.1039/CA8997605077

出版商:RSC    

年代:1899

数据来源: RSC

摘要:

INORGANIC CHEM18TR.Y. Inorganic Chemistry. Quantitative Syntheais of Water, By EDWARD H. KEISER (Amel*. Chem. J., 1898, 20, 733-739. Compare Abstr., 1887, 1078; 1891, 1154).-By the following method, the quantities of hydrogen and oxygen combining to form water can be determined gravimetri- cally without the necessity of gasometric measurement. A light glass cylinder, terminated at the bottom by a narrow tube carrying a glass stopcock, and closed a t the top with a round glass cap with a three- way stopcock, is divided by a slight constriction into two compart- ments, the smailer and lower of which contains purified phosphoric anhydride. After completely exhausting the tube, i t is weighed, and pure spongy palladium, contained in a thin glass tube having a number of small holes near the bottom, is introduced into the larger compartment; the tube is again exhausted and weighed;, pure hydrogen is admitted so as to completely saturate the palladium, and after partially exhausting, the amount of hydrogen absorbed is determined.Pure oxygen is then passed through the apparatus a t such a rate that the water formed is completely absorbed by the anhydride, and the temperature does not rise sensibly. After completely oxidising the hydrogen, the exeess of oxygen is removed by exhausting the apparatus, and the weight of the water formed is determined. In the author’s experiments, the tube used was counterpoised during88 ABSTRACTS OF CHEMICAL PAPERS. all weighings by a duplicate; both the oxygen and hydrogen were prepared electrolytically, and were purified by being passed over heated palladium, and subsequently through tubes of fused caustic potash and phosphoric anhydride.The average of four experiments carried out by this method, ranging from 15.874-15.886, gives 15.880 as the atomic weight of oxygen, W. A. D. Electrolytic Production of Chlorates, Bromates, Iodates, and Hypochlorites. By WILHELY VAUBEL (Chem. Zeit., 1898, 22, 33 l).-The author finds, on employing an electrolytic cell containing a saturated solution of sodium hydrogen carbonate surrounding the anode, and separated by a porous diaphragm from a strong brine solution in contact with the cathode, that the whole of the chlorine migrating into the anodic compartment is oxidised to chlorate, whilst carbonic anhydride and caustic soda are obtained a t the anode and cathode respectively.The temperature is maintained at 60-70° during electrolysis, and a current density of 5-10 amperes per sq. dcm. and an E.M.F. of 4-5 volts are employed, A table showing the yield of chlorate after the expiration of certain ampere-hours is given, and the author compares his results with those of previous investigators, The experimental conditions for the production of potassium chlorate are quite similar, as are also those for the preparation of bromates and iodates. When the above electrolysis is performed at lower temperatures, hypochlorite, and not chlorate, becomes the chief product, but, as in the former experiment, there is no formation of chloride round the anode. G. T. M. Electrolytic Preparation of Perchloric Acid and its Salts.By FRITZ FOERSTER (Zeit. EZektrocliem., 1898, 4, 386) .-Potassium chlorate in neutral or alkaline solution is scarcely reduced by a high cathodic current density when the cathode is made of platinum, lead, copper, zinc, or nickel, but is vigorously reduced when it is of iron and to some extent when i t is of cobalt. I n neutral or acid solutions, chlorates are readily oxidised at the anode to perchlorates. A series of experiments shows that, with high current density, concentrated solutions, and low temperatures, the yield of perchlorate is a very good one. A 50 per cent. solution of sodium chlorate was electrolysed with equal platinum electrodes 1.5 cm. apart and a current density of 8-3 amperes per sq. dcm. The solution was at the ordinary tempera- ture, and 4.5 volts were required.The yield increased from 86 to 98 per cent. of the theoretical amount, falling off only when the greater part of the chlorate was oxidised. With a 5-6 per cent. solution of potassium chlorate and 8 ampbres per sq. dcm. the yield was about 82 per cent., but fell off considerably when about one-half of the chlorate was oxidised. In alkaline solutions, oxidation ia observed at the beginning of the electrolysis, but even with high current densities it soon ceases, so that the direct production of perchlorates from chlorides would appear to be imprac- ticable. T. E.INORGANIC CHEMISTRY. 89 Electrolysis of Solutions of Calcium Chloride. By H. BISCHOFF and FRITZ FOERSTER (Zeit Elektrochem., 1898, 4, 464).- Oettel's statement that a better yield of chlorate is obtained in the electrolysis of calcium chloride than in that of potassium chloride is confirmed.Measurements of the gases evolved during the electrolysis give the percentages of the current employed (a) in the formation of hypochlorite, chlorate, and perchlorate, ( b ) in reducing hypochlorite at the cathode, (c) in decomposing water. When a solution of 74.3 grams of calcium chloride in 500 C.C. of water is electrolysed with 6.7 volts, and current densities of 9.1 amperes per sq. dcm. at the anode and 13 amperes per sq. dcm. a t the cathode, 85.7 to 90.4 per cent. of the current yields oxygen compounds of chlorine, mainly chlorate, 1.4 to 2.9 per cent, reduces hypochlorite, and 7.8 to 12.8 per cent. decom- poses water.With a solution of 100 grams of potassium chloride + 7.5 'grams of potash in 500 C.C. of water, the E.M.F. being 4.8 volts and the current densities the same as before, the corresponding values were 50.9 to 61.9, 12 to 19.9 and 20.8 to 29.6. Both solutions were cooled with ice. A solution of barium chloride gave results very similar to those obtained with potassium chloride, The small reduction observed with calcium chloride is probably due to a layer of calcium hydroxide on the cathode which acts as a diaphragm; the greater part of the calcium hydroxide formed combines with chlorine, but part of i t remains undissolved, free hypochlorous acid existing in the solution and volatilising with the gases evolved. Further experiments show that at 20-25' the best yield of chlorate is obtained from solutions con- taining at least (preferably much more than) 10 per cent.of calcium chloride, and with a current density of 10 amperes per sq. dcm. at the anode and at least double that amount at the cathode; the yield is nearly 90 per cent. The deposit of calcium hydroxide on the cathode considerably increases the E.M.F. required ; at 50°, however, 4.55 volts suffice, and the yield is but slightly reduced (80 to 87 per cent.). Determinations of oxygen in admixture with hydrogen should not be made in the phosphorus pipette, but by means of copper in presence of a solution of ammonia. T. E. Density and Molecular Weight of Ozone. By ALBERT LADENBURG (Ber., 1898, 31, 2830-2831. Compare this vol., ii, 18).- The calculation of the amount of ozone present in the gas employed in the experiments previously described was based on the assumption that 253.06 parts of iodine are liberated by 48 parts of ozone.Since the object of the experiment was t o determine the molecular weight of ozone, the author has recalculated the results on the simpler assump- tion that 1 molecule of iodine is set free by 1 molecule of ozone. He thus finds that the gas employed contained 84.4 per cent. by weight of ozone, and that the density of ozone is 1.469. Colour of Sulphur Vapour. By J. LEWIS HOWE and S. G. HAMNER (J. Anzev. Chem. Xoc., 1898, 20, 757-759).-The authors, after referring to the varying statements with regard to the colour of sulphur vapour, describe experiments which show that this colour varies with the temperature, being orange-yellow just above the boiling point of sulphur, becoming rapidly darker with rise of temperature A.H.90 ABSTRACTS OF CHEMICAL PAPERS. until it becomes deep red comparable to the red of ferric thiocyanate ; this red colour is most intense at about 500". Above this temperature, the colour becomes lighter until at 634O, the limit of temperature at which observationa were made, the colour is straw-yellow. G.. W. P. H. The Change in Sulphur by Heat. By FRIEDRICH W. KUSTER (Zeit. cmorg. Chem., 1898, 18, 365-370).-The author has determined the amount of insoluble sulphur which is formed on heating sulphur at known temperatures for a known time. The sulphur, pTeviously crystaIlised from carbon bisulphide, is sealed up in a vacuum in a glass tube, and, after heating, the insoluble portion is determined by ex- traction with carbon bisulphide (so-called insoluble sulphur is slightly soluble in carbon bisulphide).When heated at 141.7", about 5.2 per cent. of insoluble sulphur is formed, the amount formed being independent of the time ; after 1 hour, this amount is approximately the same as after 16 hours. When heated at 1 8 3 O , the amount of insoluble sulphur is also independent of the time, and also apparently of the temperature, since about 6 per cent. of insoluble sulphur was obtained. When heated at 448" for 15 minutes and then gradually cooled, 1.8 to 3.3 per cent. of insoluble sulphur is formed ; when, how- ever, the molten sulphur is suddenly cooled by plunging into cold water, 30.9 to 34.2 per cent.of insoluble is obtained. The formation of the insoluble modification and the converse formation of soluble sulphur take place, therefore, with extreme rapidity, so that the amount of insoluble sulphur which is present after crystallisation is not dependent on the temperature and time of the heating, but on the rate of the crystallisation and the temperature at which it takes place. Therefore, different samples of sulphur which have been heated for different times above the melting point after remaining some time at a lower temperature (loo'), are practically identical as regards the concentration of the insoluble modification, from which it follows that the difference observed in the velocity of solidification, &c., must be assigned to some other cause than the different concentration of the insoluble modification (Abstr., 1897, ii, 439).A sample of insoluble sulphur which has been kept for 5 months, when treated with carbon bisulphide, gives the same percentage of soluble matter as when freshly prepared. On evaporating the solution, the sulphur separates in solid drops which show no signs of crystal- lisation under the microscope, but give evidence of crystallisation when subjected to polarised light. This sulphur is not completely soluble in carbon bisulphide, so that the '' insoluble " modification, when dissolved, is not completely converted into the soluble modification. The author concludes that the soluble and insoluble modifications have different molecules in solution, that they are not only physical isomerides, but chemical isomerides, having a relation to each other similar to that of ozone to oxygen.By THEODOR CURTIUS and JOHANNES Rrssonl (J. pa. Clbem., 1598, [ii], 58, 261-309. Compare Abstr., 1891, 57 ; 1892, 1 l2).-The azoimide, HN,, was obtained in aqueous solution by dis- tilling with dilute sulphuric acid either the ammonium salt (Abstr., E. C. It. Azoimide.INORGANIC CHEMISTRY. 91 1892, 113) or the lead salt precipitatied from the mother liquor of that salt; excess of acid should be avoided, especially in the latter case. Azoimide is decompoeed but very slowly when boiled with dilute hydrochloric acid ; most of the nitrogen is liberated as the gas ; a little ammonia is formed, but neither hydroxylamine nor hydrazine. In aqueous solution at the ordinary temperature, azoimide is very stable; such loss of strength as does occur is due t o volatilisation.The metallic salts (azoimides, azides, or nitrides) were prepared (1) by precipitation, in the case of AgN,, HgN,, Pb(N,),, TlN,, and Cu(N,),; (2) by dissolving the metal in the dilute acid of 16-17 per cent. strength (applicable in the case of Zn, Fe, Cd, and Mn, but the solutions are decomposed on evaporation, basic azoimides or even the hydroxides of the metal being formed and azoimide given off); (3) by dissolving the freshly precipitated hydroxide or carbonate of the metal in the aqueous acid and evaporating the solution; (4) by double decomposition of the sulphate of the metal with barium azoimide and evaporation of the filtered solution.In the analysis of the salts, the nitrogen was sometimes determined by combustion, the substance being mixed with plenty of powdered lead chromate in a long porcelain boat, but more often by distillation with dilute sul- phuric acid, the azoimide evolved being collected in excess of N/10 potassium hydroxide, of which the excess was estimated with N/10 hydrochloric acid, phenolphthalein serving as the indicator ; in the residue from the distillation, the metal was determined. Crystallographically the azoimides of potassium, rubidium, and thallium appear to form an isomorphous tetragonal group, those of barium, calcium (and stron- tium?) an isomorphous rhombic one; in all cases, the double re- fraction is very marked. As regards solubility in water a t 16O, the azoimides of Na, I(, Rb, Cs, NH, arrange themselves, as compared with the corresponding halogen salts, in the order of increasing solubility F, C1, N,, Br, I (which is also that of increasing formula-weight), those of Ba, Ca, Sr, Li, T1 in the order F, N,, C1, Br, I. When the azoimides of the alkali and alkaline earth metals are heated in a small capillary tube closed a t one end (melting point tube), azoimide is evolved, and the metal is left (in this way, small quantities of Cs, Rb, Ba, Sr, Ca may be prepared) ; none of them are very explosive, only lithium and the alkaline earth azoimides exploding at comparatively Iow temperatures, and only thallium azoimide when hammered ; in aqueous solution, they attack glass, although the acid itself has no such action; in aqueous solution, they are stable, but the'solution has often an alkaline reaction.The azoimides of the heavy metals are often very ex- plosive, perhaps most of all the potassium-platinum derivative, which explodes spontaneously with frightful violence, even in aqueous solution. No azoimide has been found as yet to crystallise with water. Ammonium azoimidg NH,*N,, melts and decomposes violently at 160" ; very volatile ; the vapour density at 100' in Hofmann apparatus gave themolecular weight = 29.3; 30.3 (calculated 60), so that complete dissociation must have taken place ; the spectrum resembles that of am- monium chloride, showing the hydrogen lines and the red-yellow part of the nitrogen spectrum ; crystals apparently rhombic. Hydrazine92 ABSTRACTS OF CHEMICAL PAPERS, azoimide, N2H59N3, begins to melt at 65', and decomposes energetically at 108'.Lithium axoimide, LiN, : crystals anisotropic ; deliquescent ; explodes between 115' and 298'. Sodium azoimide, NaN3 : crystals apparently hexagonal ; unchanged a t 350'. Potassium axoimide, KN, : crystals tetragonal ( a : c = 1 : 0.5810) ; melts and decomposes above 350'. Rubidium azoimide, RbN, : the best crystallised of the salts examined ; crystals tetragonal [a : c = 1 : 0.57851 ; slightly hygro- scopic ; melts at 330-340'. Casium axoirnide, CsN,, crystalline, deliquescent ; melts at 310-318'. Thallium azoimide, TIN, : crystals, tetragonal [a : c = 1 : 0*5SS] ; explodes when struck, also when heated strongly, but is unchanged a t 340'. Calcium axoimide, Ca(N3)2 : crystals rhombic [a : b : c = 0.320'7 : 1 : 0.8815 ( P ) ] ; hygroscopic ; explodes at 144-156'.Strontium azoimide, Sr(NJ2 : crystalline ; hygroscopic ; decomposes violently at 194-196O. Barium axoimide, Ba( N3)2: crystals rhombic [a : b :c = 0-3424 : 1 : 0.84611; hardly hygroscopic ; decomposes violently at 2 1'7-221". Magnesium and beryllium axoimides are readily decomposed by hot water. Basic zinc uxoimide, N,*Zn*OH (a) ; crystals ill-defined, anisotropic. Basic manganese axoimide, N,mMn*OH. Cadmium axoimide, Cd (N3)2 : yellow, biaxial crystals ; forms with pyridine a colourless, crystalline compound, Cd(N,),,SC,NH,. Cupric axoimide, Cu(N,),, from copper sulphate and sodium azoimide, but also by dissolving copper in the aqueous acid ; dark brown and crystalline ; insoluble in water ; very explosive.Aluminium forms no azoimide ; from a solution of the sulphate, sodium azoimide precipitates the hydroxide. Chromium azoimide is formed in solution by dissolving chromium hydroxide in aqueous azoimide ; it decomposes on evaporating the solution, the residue containing only 2N, per 3Cr. Ferrous sulphate gives a colourless solution with cold aqueous azoimide ; on boiling, a yellow solid is precipitated. The solution turns red when shaken in the air; a deep red solution is also obtained when solutions of ferric chloride and azoimide are mixed ; this becomes colourless slowly in t-he cold, rapidly wheu boiled, all the iron being precipitated. Tin is precipitated from a solution of stannous chloride by sodium azoimide, and the precipitate is, in part at any rate, an azoimide.Basic nickel axoirnide, N,*Ni*OH, with some Ni(N3)2(?), from nickel carbonate and aqueous azoimide : green, crystalline; explodes a t 247-271'. Basic cobalt axoimide, N,*Co*OH, with some CO(N,)~ : violet and possibly amorphous ; potassium cobaltoaxoimide, KN,,Co(N;),, precipitated when strong solutions of the two azoimides are mixed, is bright blue (gives a pink solution) and crystalline, and explodes at 225' ; the ammonium analogue, (NH4)Nq(CoN,),, is similar in appearance and properties. An analogous bright green nickel com- pound, KN,,Ni (NJ2(P), also crystalline and explosive, was obtained. By mixing strong solutions of platinochloric acid and potassium azoimide, or aurochloric acid and sodium azoimide, solutions were obtained from which, in the first case, a brownish-red, in the second an orange crystalline, residue, extremely explosive in both cases, remained on evaporation (potassium platinoazoimide and sodium auroazoimide 9).C. P. B.INORCIANIC CHEMISTRY 3 93 Metaphosphimic Acids. 111. By HENRY N. STOKES (Amer. Chew. J., 1898, 20, 740-760 and Zeit. Anorg. Chem., IS, 36-58. Compare Abstr., 1897, ii, 28 and 94).-Although penta- and hexa-phosphonitrilic chlorides (Abstr., 1898, ii, 70), on hydrolysis give rise to the corre- sponding pen ta- and hexa-metaphosphimic acids, from heptaphospho- nitrilic chloride the acid (H,PNO,), + H20 is obtained. The salts of all three new acids differ from those of tri- and tetra-metaphosphimic acid in being amorphous; hence, in many cases, they cannot be obtained satisfactorily pure, Pentametaphosphimic acid, N H PO( OH) *.NH * PO(OH)>NH, PO(OH)<NH.PO(OH).NR.PO(OH) is best prepared by shaking pentaphosphonitrilic chloride (4 parts), dissolved in ether free from alcohol (20 parts), with a solution of sodium hydroxide (5 parts) in water (20 parts) during 60 hours.On adding alcohol, the pentasodium salt, P5N501,H5Na5 + 2H,O, is precipi- tated as a thick syrup, which is mashed repeatedly with 60 per cent. alcohol, dissolved in water, reprecipitated by alcohol and again washed until free from sodium chloride; it is then freed from water by stirring several hours with frequently renewed absolute alcohol. Thus prepared, it is a white, sandy powder, which retains 2H20 after dryingat loo', and dissolves in water with developmentof heat, the solution having an alkaline reaction. When dissolved in 80 per cent.acetic acid, i t is converted into the tetrasodium salt, P5N50,,H6Na4 + 2H20 ; the latter is precipitated on adding alcohol and resembles the pentasodium sdt, but has a neutral reaction, On adding a magnesium salt to an aqueous solution of sodium pentametaphosphimate strongly acidified with acetic acid, the mclgnesium salt, P5N50,,H6Mg2 + 5H#, is preci- pitated ; on dissolving tbis in dilute nitric acid, adding ammonia until a precipitate just forms, and filtering, a solution containing the salt (P,N,0,,H9)2Mg is obtained. The silver salt, P5N501,H,Ag5, precipi- tated by adding the calculated quantities of nitric acid and silver nitrate to II solution of the tetrasodium salt, is a white powder, which is not affected by light or by heating a t 100'; it is decomposed, how- ever, by cold caustic alkalis.Salts containing more than five atoms of silver can be obtained, which are yellow in colour. When silver nitrate is added to an ammoniacal solution of sodium pentametaphos- phimate, a yellow, amorphous salt, P5N5011H3Ag9, is obtained, which i g probably a derivative of amidotetrimidopentaphosphoric acid, OH *PO( NH2)* [NH*PO(OH) J3*NH* PO(OH),. Somewhat impure pen ta- metaphosphimic acid separates as a gelatinous precipitate on adding alcohol to the filtrate obtained after decomposing its silver salt with hydrogen sul phide . When sodium pentametaphosphimate is heated during 8 hours with dilute acetic acid, it is decomposed into a mixture of the sodium salts of tetrametaphosphimic acid (Abstr., 1897, ii, 94), tri-imidotetra- phosphoric di-imidotriphosphoric and orthophosphoric acids, together with other substances.The first of these acids is completely precipi- tated during the reaction as a sparingly soluble acid sodium salt, in spindle-shaped crystals. On concentrating the filtrate, and adding sodium acetate, sodium tri-imidotetraphosphate, probably P4N,01,H5Na,, crystallises out in small rhombic or hexagonal plates ; on dissolving in VOL. LXXVI. ii. 794 ABSTRACTS OF CHEMICAL PAPERS. water and adding silver nitrate, the silver salt, P,N,O,,H, Ag,, separates as an amorphous precipitate which becomes crystalline on washing with water. Sodium ILexameta~hosp~~i~~~~~te, Y,N,O1,HGNa, + 2H,O, prepared from hexaphosphonitrilic chloride, closely resembles sodium pentameta- phosphimate.No definite magnesium salt could be obtained, but the silver salt, P6N60,,H6Ag6, separates on adding the calculated quantity of nitric acid and silver nitrate to a solution of the sodium salt ; i t forms a white, gelatinous precipitate, and is decomposed by cold caustic patash. I n presence of ammonia, a yellow silver salt is pre- cipitated. Free hexametaphosphimic acid cannot be obtained, as on decomposing its silver salt suspended in water by hydrogen sulphide, filtering, and adding alcohol, no precipitate separates ; on attempting to evaporate, decomposition occurs, and a gum-like residue is obtained. On heating sodium hexametaphosphimate with dilute acetic acid, 30 per cent.of the theoretical quantity of tetrametaphosphimic acid is obtained. When the hydrolysis of heptaphosphonifrilic chloride is effected by sodium hydroxide as in the cam of pestaphosphonitrilic chloride, amidoheximidoheptaphosphoric acid, OH*PO(NH,)* [NHePO(OH) J6*NH*PO(OH),, is formed j the sodium salt, P7N70,,H,.57Na7.43 + 2H,O, and the silver salt, P7N70,bH9Ag7, were analysed. Attempts to prepare amides by acting on ethereal solutions of tetra- and penta-phosphonitrilic chloride with aqueous ammonia gave amorphous substances of indefinite composition. In discussing his results, the author points out that tetrametaphos- phimic acid is by far the most stable of the metaphosphimic acids. To explain this, and the formation of tetraphosphimic acid from the penta- and hexa-acids by hydrolysis, a hypothesis as t o the stability of the acid rings is put forward, which is similar to von Baeyer’s tension theory of carbon rings. By ALBERT L&VY and H.HENRIET (Compt. rend., 1898, 127,353-355).--When air that has been completely freed from carbonic anhydride by passing it over potassium hydroxide is allowed to remain for 2 hours in contact with potassium hydroxide solution, a further quantity of carbonic anhy- dride is formed (compare Abstr., 1898, ii, 573). I f the potassium hydroxide solution contains 7 grams per litre, all the carbonic anhydride existing as such in the air is completely absorbed in 10 minutes, and all the organic matter in the air in the form of gas or vapour is com- pletely oxidised in 2 hours.Experiments were made during July, 1898, in which the carbonic anhydride absorbed by the potassium hydroxide was determined after it had been in contact with the air in large flasks for 10 minutes and 2 hours respectively. The difference was often from 3 to 6 litres per 100 cubic metres of air, but sometimes was as high as 11 or 12 litres, and in one exceptional instance it reached 56 litres. It is obvious that this difference gives useful information as to the quantity of gaseous organic matter present in the air. I n all cases, thedifference observed W. A. D. Atmospheric Carbonic Anhydride.INORGANIC CHEMISTRY, 95 in the manner indicated is somewhat less than its true value, because even in 10 minutes the organic matter is appreciably oxidised in presence of the alkali.C. JI. B. The Various Theories relating to the Constitution of the Arnrnonio-metallic Salts. By FRITZ REITZENSTE~ N (Zed. anopg. Chem., 1898, 18, 152--210).-An historical review of the theories that have been put forward on this subject. By LOUIS KAHLENBERCI and AZARIAH T. LINCOLN (J. Physical Chem., 1898, 2, 77-90).-The conclusion arrived at by Kohlrausch (Abstr., 1893, ii, 166) that in solutions of sodium silicates these salts are hydrolytically decomposed into sodium hydroxide and colloidial silicic acid, has been confirmed by investigating the freezing points of such solutions. The freezing points and the electrical conductivity of solutions of the silicates of potassium, lithium, rubidium, and cesium show that these salts are also decomposed by water into colloidal silicic acid and the hydroxide of the alkali metal.The silicates of the alkalis all show an analogous behaviour when dissolved in water. The same solution is obtained whether a silicate is dissolved in water, or whether solu- tions of caustic alkali and colloidal silicic acid in proper propor- tions are mixed, Since colloidal silicic acid has but little effect on the freezing point, the degree of hydrolytic decomposition of the silicates can be calculated from the lowering of the freezing point of their solutions. Silicates of the general formulae M,SiO, and MHSiO, are practically completely hydrolytically dissociated when one gram-molecule is contained in 48 litres. Silicates of the general formula M,Si,O,, are practically completely decomposed by water when one gram-molecule is present in 128 litres.A comparison of the electrical conductivity of silicate solutions with that of solutions of the alkali hydroxides shows that the values of the former approach the latter as the solutions become more dilute, the retarding influence that the silicic acid has on the mobility of the ions gradually becoming less. Fzom the results of the above investigations, it appears safe t o con- clude that, in natural waters, silicic acid always occurs in the colloidal state; only in very rare instances are the solutions of the silicates so concentrated that they are not practically completely hydrolytically decomposed. H. C. Sodium Oxides. By ROBERT DE FORCRAND (Compt. wnd., 1898, 127, 364--366).-When dry air, free from carbonic anhydride, is passed through sodium heated somewhat above its melting point, the first product is a bulky, grey, arborescent mass, consisting of the sub- oxide Na,O, mixed with a small proportion of sodium.If the heating is continued, this substance burns, and is converted into a yellow mixture of the monoxide and dioxide, or completely into the dioxide Na,O?, which, however, generally retains a small proportion of water. No trioxide is formed. The suboxide does not rapidly absorb water vapour, but is gradually oxidised when exposed to air ; if thrown into water, it reacts violently, with liberation of pure hydrogen. E. C. R. Solutions of Silicates of the Alkalis. C. H. B. 7-296 ABSTRACTS OF CHEMICAL PAPERS. Interaction of Sodium Arsenite and Sodium Thiosulphate.By LEROY W. MCCAY (Chem. News, 1898, 78, 209).-When sodium thiosulphate and sodium arsenite in the theoretical quantities are made into a thick paste with caustic soda and rubbed in a mortar, the following change takes place : Na,As03 + Na2S203 = Na,As03S + Na2S03. The sodium orthomonothioxyarsenate is separated by treat- ing the paste with water, filtering, and crystallising. It is generally obtained by similar treatment of a paste of sulphur, caustic soda, and arsenious oxide in stochiometrical amounts. D. A. L. By H. VAN ERP (Rec. Trau. Chim., 1898, 17, 296-299).-As a rule, the efflorescence formed on walls consists almost entirely of sodium sulphate and carbonate, with varying quantities of water of crystallisation ; nitrates, nitrites, phosphates, and ammonium salts can seldom be detected, but calcium carbonate and sand are usually present.In the case of a wall of a corridor in the Harlem Museum, which had been covered for some time with a ciirtain, it was found that, beneath the latter, a deposit of slender needles, several centimetres in length, of pure sodium sulphate (with 10H20) had formed. Ammoniacal Lithium Chlorides. By J. BONNEFOI (Compt , rend., 1898, 127, 367-369).-The compound LiCI,NH3 is formed by the action of dry ammonia on pure and dry lithium chloride at a tem- perature exceeding 85", or by heating the compounds containing a higher proportion of ammonia. Its heat of dissolution at 15" is + 5.385 Cal. and hence, LiCl sol. + NH, gas = LiCl,NH, sol. develops + 11.842 Cal. Saline Efflorescence of Walls.W. A. D. Its vapour pressures are as follows. t 8 8 O 9 6" 109.2" 119" p 256 mm. 367 mm. 646 mm. 975 mm. and the heat of formation calculated by Clapeyron's formula agrees closely with the number directly determined. The compound LiCI,BNH, is obtained by the action of ammonia on lithium chloride between 60" and 85", or by heating the higher com- pounds between these limits. Its heat of dissolution is +2.668 Cal. hence, LiCl sol, + 2NH3 gas = LiCl,BNH, sol. develops + 23.355 Cal Its vapour pressures are i? 68.5" 7 7" 83' 89.2" p 373mm. 658 mm. 739 mm. 980mm. The compound LiCl,SNH, is formed between 20" and 60". Its vapour pressures are t 43" 5 0" 60" 62.2" 65' p 320 mm. 473 mm. 790 mm. 882 mm. 1011 mm. The oompound LiC1,4NH3 is formed below 13"; its heat of dissolution is + 0.292 Cal., hence LiCl sol.+ 4NH, gas = LiC1,4NH3 sol. develops + 43.335 Cal., LiCl,SNH, sol. + NH, gas = LiC14NH3 sol. develops + 8.879 Cal. Its vapour pressures are t O0 9" 14.5" P 384 mm. 640 mm. 850 mm.INORGANIC CHEMISTRY. 97 The heat developed by the combination of the four successive molecules of ammonia with the lithium chloride is + 11.843, + 11.517, + 11 -097, and + 8.879 Gals. respectively. In all cases, Ulapeyron's formula gives results that agree with the direct determinations (compare Abstr., 1897, ii, 371). Dicalcium Phosphate. By A. BAR ILL^ (Chew. Cents*., 1898, i, 434-435 ; from Rgp. Pharm., 1897, 529).-When ammonia is added to a solution of monocalcium phosphate, half the phosphoric acid remains in solution as ammonium phosphate, and dicalcium phosphate is precipitated.By adding calcium chloride solution to the filtrate, the rest of the phosphoric acid is precipitated as monocalcium phos- phate. According to the author, the latter reaction takes place in three phases. Ammonium chloride, tricalcium phosphate, and tetra- hydrogen calcium phosphate are first formed, then by the action of water the last compound forms tricalcium phosphate and phosphoric acid, and finally the whole of the tricalcium phosphate acts on the phosphoric acid t o form monocalcium phosphate. To prepare dicalcium phosphate, 1000 grams of well burnt bone ash are stirred with hot water and then gradually mixed with 1454 grams of commercial hydrochloric acid of sp.gr. = 1.17. When the action is completed, 3 litres of hot water are added, the solution of monocalcium phosphate and calcium chloride is filtered, the filtrate diluted to 10 litres and a mixture of 442 grams of ammonia of sp. gr. = 0.925 with 20 times its weight of water is slowly added. The precipitated dicalcium phosphate, after collecting, washing with water until free from acid and drying at 60°, is a light, snow-white, lustrous powder, which consists of flat, hexagonal crystals. Dicalcium phosphate crystallises with 4H,O. I t s solution is not decomposed by boiling or evaporating, and its saturated solution in water containing carbonic anhydride contains 0.069 per cent. of the salt, and might be used medicinally instead of Crystallisation of Anhydrous Calcium and Strontium Sul- phides.By A. MOURLOT (Compt. rend., 1898, 127, 408-410).- Calcium or strontium sulphide can be obtained in a crystalline condi- tion by heating a moderately large quantity of a mixture of the cor- responding sulphate with carbon for a few minutes only in an electric furnace with a current of 1000 amperes and 60 volts. If the amorphous sulphides are heated in a carbon dish in an electric tube furnace until they are completely melted, they crystallise on cooling. Both sulphides crystallise in the cubic system; the sp. gr. of the calcium compound = 2.8 a t 15O, and of the strontium compound = 3.7 at 15O. I n chemical properties, they closely resemble anhydrous barium sulphide (Abstr., 1898, ii, 376). Composition of Phosphorescent Strontium Sulphides.By Josh R. MOURELO (Compt. rend., 1898, 127, 229-231).-Strontium sulphide, prepared from minerals, contains strontium sulphate, in quantity depending on the degree of exposure to air, and also small quantities of sodium chloride ; it may also contain calcium, barium, iron, and aluminium compounds. When prepared from pure strontium C . H. B. tricalcium phosphate. E. w. w. C. H. B.9s ABSTRACTS OF CHEMICAL PAPERS. sulphate, carbonate or oxide, it usually contains some sulphate, but if special precautions are taken and it is obtained quite pure, it is non- phosphorescent. 0. H..B. Phosphorement Strontium Sulphide. By Josk R. MOUIZELO (Compt. rend., 1898, 127, 372--374).-Strontium thiosulphate, pre- pared by the action of sodium t,hiosulphate on strontium chloride, retains with great tenacity small quantities of sodium chloride, and consequently this salt is present in any strontium sulphide prepared from it by the action of heat ; the phosphorescence is yellowish-green, and somewhat intense.An intensely phosphorescent sulphide is obtained by a method very similar to that adopted by Verneuil for the preparation of calcium sulphide. For 100 grams of strontium carbonate, 2 grams of bismuth subnitrate, 2 grams of sodium carbonate, and 0.12 gram of sodium chloride is taken ; after moistening the carbonate with the sodium salts, it is heated to redness, and then mixed with 21 grams of sulphur and the bismuth salt, and heated to bright redness for 4 hours. The pro- duct is relatively very stable. C. H. B. Double Compounds of Cerium Tetrachloride.By IVAN KOPPEL (Zeit. anorg. Chem., l898,18,305--31l),-A solution of cerium tetra- chloride is obtained by treating hydrated cerium dioxide, suspended in methylic or ethylic alcohol, with dry hydrogen chloride ; it forms a yellowish-brown solution, which deposits yellow, crystalline crusts when evaporated in a vacuum, and decomposes at once, with evolution of chlorine, when removed from the mother liquor or when brought into contact with water. This solution forms stable, double compounds with pyridine, quinoline, and the triethylamine chlorides, but not with mono- or di-ethylamine hydrochloride. I n the preparation of these compounds, the author employed commercial cerous oxalate, and he points out that by precipitating the cerium in the form of one of these double salts, a very easy method is obtained for the preparation of pure cerium compounds.Dipyrzne cerium hexachloride, ( U,NH,),,H2CeC16, obtained by adding pyridine hydrochloride to the above solution of cerium tetra- chloride and then precipitating with ether, crystallises in small, lustrous, quadratic leaflets, is easily soluble in methylic alcohol, less so in ethylic alcohol, and is at once decomposed by water, with evolu- tion of chlorine. Diquirzolim cer6m-z hexachlode, (C,NHy),,H2CeC1,, obtained in a similar manner to the preceding salt, is a yellow, crystalline precipi- tate, less soluble than the preceding salt, and at once decomposes when treated with water. Di-triethylarnirye cerium hexachloride, (NEt,),,H,CeCI,, crystallises well from alcohol in octahedra.Yellow, crystalline salts, which are probably the double compounds K,CeCl, and (NH,),CeCI,, are obtained by adding finely powdered potassium or ammonium carbonate to the solution of cerium tetra- chloride containing strong hydrocbloric acid, and then shaking with a large quantity of ether ; when separated from the solution, they a tINORGANIC CHEMISTRY. 99 once decompose, with evolution of chlorine. to obtain double salts with calcium, mercury, or ferric chloride. The author was unable E. C. R. Praseodymium. By CARL VON SCHEELE (Zeit. cmorg. Chem., 1898, 18, 352-364. Compare Abstr., 1898, ii, 519).-Praseodymium chloride, PrCl, + 7H20, crystallises in large, deliquescent crystals when the concentrated solution is allowed to remain over sulphuric acid ; sp.gr. at 16' = 2.251. The bromide, with 6H20, is obtained by dissolving the oxide in hydrobromic acid. The ptutinochloride, PrCl,,PtCI, + 1 2H20, crystallises in large, yellow crystals and slowly gives off water when allowed to remain over sulphuric acid. The platinobromide, with 10H20, separates in large, dark red crystals and effloresces when allowed to remain over sulphuric acid. The uuri- chloride, with 10H,O, crystallises in beautiful, deliquescent crystals and is very soluble in water. The auribi-omide crystallises in long needles which deliquesce extremely rapidly on exposure to the air. Praseodymium pZatinocyanide, 2Pr(CN),,3Pt(CN), + 1 8H20, obtained by adding the theoretical quantity of praseodymium sulphate to a solution of barium cyanide and platinum cyanide, crystallises in black, fluorescent prisms ; i t effloresces over sulphuric acid, becoming red, and giving off 4H20 ; sp.gr. at 1 6 O = 2,663. PrcGseodymium nitrate, Pr(N03)3,+ 6H20, cry stallises in long, deli- quescent needles. The double sodzum salt, Pr(N03),,2NaN0, + H30, crystallises in small, deliquescent needles. The ammmium salt, with 4H20, crystallises in large, deliquescent crystals ; sp.. gr. = 2.155. Praseodymium sulphute, Pr,3S04 + 158H20, is obtained by allowing a dilute solution to crystallise very slowly ; it crystallises with 8H20 at the ordinary temperature; sp. gr.=2-822; and with 5H20 when a saturated solution is concentrated on the water-bath. The an- hydrous salt has the sp. gr.=3*720; 23.64 parts are soluble in 100 parts H,O at O', and 17.7 parts are soluble in 100 parts H20 at 20'.The double potassium salt, Pr2(S0,),,3K2S0, + H20, is a heavy, crystalline precipitate, very sparingly soluble in water and easily soluble in hydrochloric and nitric acids ; sp. gr. = 3.275. The double ammonium salt, with 8H20, separates in large crystals, is not altered by exposure to the air or by remaining over sulphuric acid, is sparingly soluble in water, and becomes anhydrous when heated a t 1'70'; sp. gr. = 2.532. Praseodymium selenate, Pr,(SeO,), + 8H20, ig obtained by allowing a solution of the oxide in selenic acid to crystallise over sulphuric acid ; sp. gr. = 3.094. It crystallises, with 5H20, in prisms when the solution is concentrated on the water-bath; the anhydrous salt is' obtained by heating the preceding salt a t 200' ; sp.gr. = 4.305. The double potassium salt, Pr2(SeO4),,3K2SeO, + 4H20, is similar to the corresponding sulphate. A double salt with ammonium selenate could not be obtained. Pruseodyinium dithionnte, Pr2(Sa06)s.+ 12H,O, obtained from praseodymium sulphate and barium dithionate, crystallises from the syrupy solution mhsn it is exposed over sulphuric acid, rapidly deli-100 ABSTRACTS OF CHEMICAL PAPERS. quesces on exposure t o the air, and evolves sulphurous anhydride when warmed. The acid selenite, Pr,(SeO,),,H,SeO, + 3H20, obtained by pre- cipitating the sulphate with sodium selenite and then adding a solution of selenic acid, crystallises in slender needles. The carbonate, Pr2(C0,), + 8H,O, obtained by treating the hydroxide, suspended in water, with carbonic anhydride, or by precipitating the chloride with ammonium carbonate or potassium hydrogen carbonate, crystallises in small, lustrous scales.The oxalate, Pr2(C204), + lOH,O, is a crystalline precipitate, soluble in concentrated acids, and does not form double salts with alkaline oxalates. The acetate, with 2H,O, crystallises in slender needles at the ordinary temperature, and with 1+H20 in small, slender needles at the temperature of the water-bath. The propionate, when evapor- ated over sulphuric acid, crystallises, with 3H20, in large prisms, and on the water-bath, with lH,O, in large, thin, lustrous leaflets. Behaviour of Thallium in Acid Solution towards Hydrogen Bulphide in Presence of Arsenic, Antimony, and Tin.By JOSEF LOCZKA (Chem. Centr., 1898, i, 657 j from Magyar Chrnicci Folybirat, 3).-Thallium is not precipitated by hydrogen sulphide in acid solu- tions, but in presence of dissolved arsenic, antimony, or tin, red precipitates are formed which contain thallium. The larger the amount of acid present, the less the amount of thallium precipitated, and, with a large excess of acid, no thallium is thrown down. The arsenic precipitate, TlAsS,, occurs naturally in a crystalline form in the realgar from Alchar in Macedonia. By ROBERT MELDRUM (Chern. News, 1898,78, 209--210).-In these experiments, 7 feet of bright copper wire, &-inch in diameter, was exposed, in a test tube, to 100 C.C. of the water ; lake water, waters with and with- out free ammonia, and distilled water were all found to dissolve copper to a certain extent, some hundredths per 100,000 even in 24 hours.I n the lead experiments, pieces of the same lead piping, 2 inches long and $-inch bore, were closed at one end and each frequently filled and agitated with a different water during various periods. One water with a total hardness of 3 * 5 O and a permanent hardness of 3 9 O , dissolved considerably more lead than another with a total hardness of 18.6O and permanent hardness of 5 ’ ; a relationship that was not altered by charging both with carbonic anhydride. But the activity of the first was destroyed by thoroughly agitating with precipitated calcium carbonate and filtering. Cause of the Retention and Release of Gases Occluded by Metallic Oxides.By THEODORE W. RICHARDS (Amer. Chern. J., 1898, 20, 701--732).--Scott has recently stated (Trans., 1897, 559) that copper oxide prepared by exposing the nitrate to a “full red heat” in a muffle-furnace, contains only one-tenth the volume of occluded gas previously found by the author to be present in ignited copper oxide (Abstr., 1891, 805); the statement is, however, not a E. C. R. E. W. W. Action of Water on Metallic Copper and Lead. D. A. L.INORGANIC CHEMISTRY. 101 contradiction of the latter's results, since these were obtained at much lower temperatures, in most cases not exceeding 700". Experiments are now described which confirm the conclusions formerly arrived at : that copper oxide prepared by the ignition of the nitrate by Hampe's method, contains between 4-5 times its volume of occluded gas, and that the latter is partially expelled at a red heat.Nearly the whole of the gas is retained until the temperature rises above 850', when nine-tenths of it is rapidly evolved ; a t higher temperatures, the oxide is partially decomposed, with loss of oxygen. The amount of gas retained by the oxide below 850' does not depend on the time of ignition, although it is dependent on it above this temperature. When zinc oxide, prepared by heating the pure nitrate during a long period a t 280°, is ignited a t temperatures between 660' and 880', the amount of gas retained diminishes as the temperature rises, other con- ditions being the same ; continued heating a t one temperature causes a slow evolution of the gas. The total amount of gas occluded by zinc oxide varies greatly according to the method used for preparing the latter, and according to its physical condition. Whilst the actual amount of nitrogen occluded by the same specimen of zinc oxide is independent of the temperature a t which it is subsequently ignited, the quantity of oxygen retained decreases as the temperature is increased. Richards and Rogers' results (Abstr., 1894, ii, 45) are thus confirmed, whilst Morse and Arbuckle's statement to the contrary (Abstr., 1897, ii, 334) is shown to be incorrect.In the case of copper oxide, the more rapid evolution of occluded oxygen a t high tempera- tures is still more marked, but it is not so evident in the case of magnesium oxide. From his results, the author concludes that the occluded gas is due t o a residue of basicnitrate imprisoned in the oxides in question; that the oxygen escapes more rapidly than the nitrogen when this residue is decomposed, is explained by assuming that the loss takes place, not by diffusion, but by chemical transference.According to this hypothesis, the particles of copper oxide in immediate contact with the imprisoned gases dissociate into copper and oxygen, and then remove a portion of the occluded oxygen by combining with it ; the oxygen is subsequently transferred from molecule to molecule by changes similar to those assumed to take place by Clausius's theory of electro- lysis, until it finally escapes. This view is supported by the fact that the occluded oxygen is lost much more rapidly by copper oxide than by the oxides of zinc and magnesium, which are far less easily dissociated. That metallic copper is liberated when copper oxide is ignited a t a red heat is shown by a great increase in the latter's conductivity ; under the same conditions, the conductivity of zinc oxide was much less changed, whilst that of magnesium oxide re- mained unaffected.It also appears th& when copper oxide is heated in a vacuum a t 790", oxygen is evolved as long as i t is rapidly removed, cuprous oxide being formed. The apparent volatility of cadmium oxide a t high temperatures is probably due to its initially dissociating into oxygen and cadmium, which sublimes and i s then reoxidised. W. A. D.102 ABSTRACTS OF CHEMICAL PAPERS. Action of Hydrogen Phosphide on Cupric Sulphate. By E.RUB~NOVITCH (Compt. rend., 1898,127,270-273).-When hydrogen phosphide is allowed to act on cupric sulphate solution without any special precautions, the composition of the product is complex and variable, but if the pure gas, prepared from phosphonium chloride, is allowed to act on the copper salt in complete absence of oxygen, a black product is obtained which consists solely of the phosphide P2Cu5 + H,O. One-third of the phosphorus in the hydrogen phosphide is converted into phosphoric acid, and the acid of the cupric salt is found in the free state in the liquid 10CuS04+5Ph,+6H20= 2(P2Cu5 + H,O) + H3PO4 + 10H2S04. The changes in the colour of the solution indicate that part of the cuppic salt is first reduced to cuprous salt. The black phosphide begins to lose water at 80' and is completely dehydrated at 150°, the colour changing to red-brown. It oxidises much more readily when anhydrous than when hydrated ; in contact with the liquid in which it was formed, it is readily oxidised by air with liberation of metallic copper and formation of more phosphoric acid.Nitric acid and bromine attack the phosphide readily ; potassium per- manganate oxidises it, and concentrated sulphuric acid dissolves i t with liberation of hydrogen phosphide. C. H. B. Aluminium as a Reducing Agent. By LBON FRANCK ( C h m Zeit., 1898, 22, 236--245).-When aluminium in a finely divided state is heated to redness in an atmosphere of hydrogen and phosphorus vapour, a vigorous reaction takes place, and a dark-grey, infusible phosphide is produced having the composition AI3P7.An intimate mix- ture of aluminium and phosphorus, heated to white heat in a current of hydrogen, yields another phosphide, A15P3, which forms a yellowish- grey, infusible mass. Dark blue, shining needles are obtained in small quantity by heating aluminium and phosphorus in sealed tubes, but their exact composition has not been determined. Two other phos- phides, A1,P and A1,P2, which have a metallic appearance and a crys- talline fracture, are obtained by the use of the electric furnace. All the above phosphides give off phosphine when treated with water or acids. A mixture of aluminium and sodium metaphosphate, when heated t o redness in a current of hydrogen, yields half the phosphorus in tho free state, whilst half remains combined with the metal, forming AI,P3 ; if silica be added to the mixture, the whole of the phosphorus is liberated.Calcium phosphate behaves in a similar manner, but calcium metaphosphate containing calcium sulphate cannot be employed in this experiment, as the presence of the latter salt causes explosions when the mixture is heated. Aluminium, like magnesium, decomposes carbonic anhydride and carbonic oxide, forming the oxide of the metal and free carbon. A mixture of the metal and lampblack, when heated to a white heat, gives rise to a certain amount of aluminium carbide, which, however, cannot be separated from the excess of carbon. The carbonates OF lithium, sodium, potassium, calcium, strontium,INOI.1CIANIC CHEMISTRY. 103 and barium are reduced on heating with aluminium, the products being alumina, carbon, and the free elements ; the latter alloy with the excess of aluminium, and in all cases a small amount of aluminium carbide is formed, Aluminium reduces the metallic oxides when heated with them t o sufficiently high temperatures; in the case of the oxides of silver, copper, and lead, the reaction proceeds with explosive violence.The oxides of iron, manganese, cobalt, nickel, chromium, and molybdenum are all partially reduced ; boron and silicon are easily obtained from their oxides. A mixture of powdered aluminium and sodium peroxide, when moistened with water, ignites spontaneously. Formation of Alums by Electrolysis. By J. LEWIS HOWE and E. A. O'NEAL (J. Amer. Chem. Xoc., 1898,20, 759--765).-The preparation of manganese alums, the primary object of the research, was not effected ; various alums were, however, prepared by passing currents of 0.02-0.1 9 amperes through solutions of sulphates of the metals together with excess of sulphuric acid.The anode consisted of a platinum dish or crucible, and the cathode, which was immersed in a porous cup, of a platinum wire. Iron ammonium alum was prepared by passing the current through a solution of the sulphates of ammonium and iron acidified with sulphuric acid; the alum is formed a t the anode, I n a similar manner, iron potassium alum, iron rubidium and iron casium alums, cobalt rubidium and cobalt cssium alums were prepared. Chromium ammonium alum was formed when the cathode dipped into a solution of ammonium chromate acidified with sulphuric acid.With manganese aulphate and the sulphates of ammonium, rubidium, and cssium, no satisfactory results could be obtained, although Piccini has just stated that he obtained caesium manganese alum by electro- lytic oxidation (Abstr., 1898, ii, 521). From solutions containing ruthenium, no alum was obtained, but it was observed that ruthenium tetroxide was evolved at the positive pole. Actionof Water and Saline Solutions on Metallic Iron. By ROBERT MELDRUM (Chem. News, 1898, '78, 202-203).-Numerous ex- periments have led the author to the conclusion that the oxidation of iron in water takes place in the absence of ammonia, carbonic an- hydride, or of bacteria and other forms of life, but it is uncertain whether the action is due to the water itself or to dissolved oxygen.The experiments were made with piano wire, in glass bottles free from lead, in the light ; generally, a white cloud formed immediately round the metal, which extended and in 15 minutes the whole liquid became cloudy and then yellow ; a yellow precipitate forming in 3 or 4 hours. Sometimes the internal surface of the glass was coated with an iridescent film, Erom which glistening plates became detached, and were found in the precipitate of hydrated oxides; this occurred when the surface of the iron exposed was great in proportion to the volume of water, and when there mas free contact with the air. I n bottles half full of solutions of pure salts, activity was observed in the following cases, the solutions employed being of 1 per cent, G.T. M. G. W. F. H.104 ABSTRACTS OF CHEMICAL PAPERS, strength-ammonia, sodium carbonate, sodium hydrogen carbonate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium metaphosphate, sodium pyrophosphate, and potassium borate, whilst sodium biborate and potassium biborate gave white precipitates. The following do not show any action : calcium hydroxide (saturated solu- tion), sodium peroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, strontium hydroxide (5 per cent. solution). The experi- ments extended, in some cases, to 4 weeks, It seems that alkaline potassium salts are more active than the corresponding sodium salts. D. A. L. A Double Iron Tungsten Carbide. By P. WILLIAMS (Corn@. rend., 1898, In, 410--412).-0n heating a mixture of tungstic an- hydride, 150 grams ; iron, 250 grams, and petroleum coke, 80 grams, in a carbon crucible in an electric furnace with an arc from a current of 900 amperes and 45 volts, an iron tungsten carbide, most probably 2Fe3C,3W,C, is obtained.The product is treated two or three times with hot concentrabed hydrochloric acid, and the double carbide, which is highly magnetic, is separated by means of a magnet. It is then treated with aqua regia, which dissolves about half the crystals and leaves a residue of definite composition. The double carbide thus obtained forms very brilliant, microscopic prisms with the colour of pyrites ; it scratches glass easily, but not rock crystal ; sp. gr. = 13.4 at 18'. At a red heat, it is not affected by hydrogen or by hydrogen sulphide, but is attacked by chlorine, bromine, iodine, and oxygen ; it is not affected by water vapour a t the softening point of glass, but oxidises slowly in moist air.Gaseous hydracids have no action, but their solutions decompose the carbide in sealed tubes at about 250' : nitric and sulphuric acids dissolve it rapidly, and it is also decomposed by alkalis.ind by oxidising agents. C. H. B. Tungsten Silicide. By EMILE VIGOUROUX (Compt. rend., 1898, 12'7, 393-395).-Tungsten silicide, W,Si,, forms beautiful, steel-gray plates with a metallic lustre; sp. gr. = 10.9. It is attacked by chlor- ine, with incandescence between 200' and 300' ; by bromine, without incandescence, below a red heat, and by iodine, without incandescence, above a red heat.I n oxygen, it burns very brilliantly a t about 500°, and in air it oxidises below a red heat, but does not burn ; nitrogen is without action at any temperature. The ordinary acids, including hydrofluoric, have no action even on heating. Aqua regia is practi- cally without action, but a mixture of nitric and hydrofluoric acids attacks the silicide violently, even at the ordinary temperature. Alkalis in solution have little action, but fused alkali hydroxides and carbonates decompose the silicide very readily, whilst fused potassium nitrate acts with somewhat less energy. Tungsten silicide is prepared by heating in the electric furnace a mixture of 100 grams of silicon wibh 230 grams of tungsten oxide obtained by heating ammonium tungetate. The heavy, brittle, crys- talline product is suspended in dilute hydrochloric acid (1 in lo), and connected with the positive pole of a battery of two or three cells, a carbon plate placed in the liquid being connected with the negativeINORQANTC CHEMISTRY. 105 pole.The metal dissolves, and the silicide, which collects a t the bottom of the vessel, is treated successively with aqua regia, ammonia, and hydrofluoric acid, and any carbon silicide that may be present is separated by means of methylenic iodide. By GRBGOIRE N. WYROUBOFF and AUGIUSTE VERNEUIL (Compt. rend., 1898, 127, 412--414).-The mineral is dissolved in the usual way, and the solu- tion, which must contain sufficient acid to prevent precipitation of the phosphates, is Precipitated with half the quantity of oxalic acid necessary for complete precipitation, The oxalates are washed until free from phosphoric acid, converted into carbonates by means of a hot solution of sodium carbonate (1 : lo), and some sodium hydroxide added to insure complete precipitation of the thorium.The carbonates are washed until free from oxalic acid, dissolved in just the necessary quantity of hydrochloric acid, and mixed with successive small quan- tities of barium peroxide suspended in water until the liquid gives no precipitate with hydrogen peroxide. The precipitated peroxide con- tains all the thorium, together with 20 to 30 per cent. of impurities; it is washed and dissolved in cold concentrated hydrochloric acid, barium eliminated by means of sulphuric acid, enough water added to yield a solution containing 15 per cent.of acid, and the bases precipi- tated with oxalic acid. The oxalates are washed, and treated with a highly concentrated solution of ammonium carbonate mixed with sufficient ammonia to form the normal salt. By two or three succes- sive treatments, all the thorium is dissolved, and the solution is precipitated by means of sodium hydroxide, the precipitate well washed and dissolved in not more than the requisite quantity of nitric acid, and the liquid poured into sufficient water to yield a solution containing not more than 2 per cent. of thorium, Excess of hydrogen peroxide is then added, and the precipitate is well washed. The precipitate is dissolved in nitric acid and reprecipitated with hydrogen peroxide in order to eliminate all the cerium.It is next dissolved in hydrochloric acid, precipitated with oxalic acid, and the oxalate decomposed by pure sodium hydroxide. After careful washing, the precipitate is again dissolved in hydrochloric acid and precipitated with ammonia. This final precipitate is well washed, dissolved in nitric acid, and the nitrate crystallised. I n treating 5 tonnes of monazite, the authors never obtained, either in the hydrogen peroxide precipitate or in the ammonium carbonate solution of the oxalates, any element corresponding with the Russium of Chrustchoff. C. H. B. By EMIL WOHLWILL (Zeit. Elektro- chern., 1898,4,379,402, and 421).-Solutionsin potassium cyanidecannot be used, becauoe silver and copper are deposited along with the gold. When neutral solutions of auric chloride or of hydrogen aurichloride, HAuCl,, are used, chlorine is evolved and the gold anode is not attacked.With hydrochloric acid alone, even so dilute as 0.4 gram per litre, or with solutions of hydrogen aurichloride acidified with hydrochloric acid, no chlorine is evolved, and the gold is dissolved ; C. H. B. Extraction of Thorium on EL large Scale. From this point, all the reagents must be pure. Electrolytic Gold Refining.106 ABSTRACTS OF CHgMTCAL PAPERS. the chlorides of the alkalis or of ammonium have the same effect as hydrochloric acid. I n order that the gold anode shall dissolve, it is, therefore, necessary that the conditions permit of the formation of AuCI, ions. The behaviour of gold chloride solutions towards silver nitrate confirms Hittorf's conclusion as to the existence of these ions ; reddish-yellow precipitates are invariably formed on adding the silver nitrate ; they are, however, much less stable than the analogous silver platinochloride.The dissolution of the anode is also promoted by raising the temperature to 60' or TO', and in n hot solution containing about 3 per cent. of hydrochloric acid, an anodic current density of 3000 ampfires per square metre may be employed without separation of free chlorine ; this is more than sufficient for practical purposes. At the cathode, a fairly high current density may be employed without injury to the gold deposit, and without necessitating the use of too concentrated a gold solution ; the deposit is usually coarsely crystal- line, and sufficiently adherent to permit of thorough washing without loss.The greater the concentration of the gold solution, the better the deposit; 30 grams of gold per litre is, however, sufficient, even with 3000 ampires per square metre, No trouble is experienced from the formation of dendritic deposits, so that the electrodes may be placed close together, and a considerable output be obtained from a fimall plantl. Of the impurities in the gold, platinum and palladium pass into solution, but are not deposited a t the cathode ; after they have accumu- lated sufficiently, the solutions are worked up to recover them. Silver remains, mainly as a mud of silver chloride; the small p r t which dissolves in the hot acid solution does not pass into the deposited gold.The refined gold is very seldom less than 999.8 fine, not infrequently it is 1000. The E.M.F. required with a current density of 1000 amperes per square metre is less than 1 volt. On the assumption that only tervalent gold exists in the solution, 2-45 grams should be deposited per ampkre hour. The author's experi- ments, as well as the results obtained in large scale working, show that more nearly 3 grams per ampere hour are obtained. A considera- tion of the loss of gold a t the anode gives the explanation of this. Part of the loss is due to the separation of fine particles of gold which are found, for the most part, in the silver chloride mud. These par- ticles are equal to about one-tenth of the amount of gold deposited on the cathode, and are not merely mechanically detached from the anode, but are due to the formation of aurous chloride at its surface, which subsequently decomposes into metallic goId and auric chloride.In support of this view, the author shows that the particles are much purer than the anode itself; that aurous chloride may be detected in the solution, and that, under certain circumstances, small crystals of gold separate out throughout the mass of the solution. The presence of aurous gold with three times the dectro-chemical equivalent of the auric gold readily accounts for the large deposit observed. The part of the gold dissolved from the anode in the aurous state, which decom- poses into metallic gold and &uric chloride, never reaches the cathode, and, therefore, the loss at the anode is always greater than the deposit at the cathode. A series of experiments with varying anodic currentNINERALOGICAL CHEMISTRY. 107 densities shows that the formation of univalent gold ions diminishes as the curreil t density increases. With 15 00 amperes per square metre, 2-48 grams of gold per ampere hour were deposited (instead of 2-45), and the loss at the anode and gain at the cathode, in two experiments, were (1) 105.2 : 104.5 ; (2) 107.7 : 105. Here, therefore, tervalent gold was present almost exclusively, Such results are only obtained when the liquid is well stirred; otherwise, owing to the accumulation and decomposition of aurous chloride at the anode, the loss there is much in excess of the cathode gain. I n experiments with very small current densities, the non-electrolytic solution of gold in the hot, acid auric chloride solution must be allowed for. This appears to be reversible, a sheet of gold losing weight when the temperature is raised, and gaining it when it is lowered again. After allowing for this chemical attack, the author obtained with 1 ampere per square metre a deposit of 4.33 grams per ampere hour, and an anodic loss of 6.01 grams, that is, 72.5 per cent. of the gold had dissolved in the aurous state. T. E. Claims of Davyum to Recognition as an Element. By JOHN W. MALLET (Amsr. Chrn. J., 1898, 20, 776--783).--Kern (this Journal, 1877, ii, 278 and 712) has stated t h a t platinum ores contain a small quantity of a new metal, “davyum,” characterised by its chloride combining with that of sodium to form a sparingly soluble double salt. I n the hope of separating this metal, the author has examined the sparingly soluble residue remaining after clearing a solution of platinum ore in aqua regia from osmiridium by decanta- tion, removing the platinum by adding ammonium chloride, adding a n excess of common salt, evaporating to dryness, and extracting the residue with a minimum of water. It was found, however, to consist only of quartz, zircon, iridium, rhodium, and osmium. From a large quantity of rose-coloured crystals of sodium chloride recovered during the manufacture of platinum, a very small amount of a metallic substance was isolated, which, judging from an analysis of the double chloride, appeared to have an atomic weight of about 151.5, corresponding with the value 154 attributed by Kern to davyum. Its solution also in aqua regia gave a red coloration with potassium thiocyanate, a reaction characteristic of davyum. Since, however, it was found to consist merely of rhodium and iridium with a trace of iron, the existence of davyum is considered as very doubtful. W. A. D.

ISSN:0368-1769    

DOI:10.1039/CA8997605087

出版商:RSC    

年代:1899

数据来源: RSC

摘要:

97 Organic Chemistry. Action of Bromine on Propylic Bromide in presence of Aluminium Bromide. By A. MOUNEYRAT (Compt. rend., 1898,127, 273-276).-The author has applied t o propylic bromide the method already used in the case of ethylic bromide (this vol., i, 1). One hundred grams of the substance t o be brominated was heated with 20 grams of aluminium bromide and the calculated quantity of bromine. I n this way, he has readily prepared propylenic bromide, CH,* CHBr*CH,Br, from propylic bromide, and tribromopropane, CH,. CHBr* CHBr,, from the propylenic bromide. I n the formation of the tribromo- propane, which is accompanied by small quantities of its isomeride, CH,Br*CHBr*CH,Br, and a tetrabromopropane, it is probzbble that the propylene bromide loses hydrogen bromide, and is converted into bromopropylene, which at once combines with bromine, or possibly with hydrogen bromide.Z'et~abromoproparze, CH,Br* CHBroCHBr,, is obtained in a similar way from either of the derivatives CH,* CHBrGKBr,, or and, in its turn, yields pentabromopropane, CHBr2* CHBr*CHBr,. CH2Br CH Br-CH2Br, C. H. B. Action of Acetylene on Mercuric Nitrate. By KARL A HOFMANN (Bey., 1898, 31, 2783-2787. Compare Abstr., 1898, i? 635).-H. Erdmann and Kothner (this vol., i, 21) describe a substance obtained by the action of acetylene on a hot solution of mercuric nitrate as a double compound of mercurous carbide and nitrate, HgCiCHg,HgNO,+ H,O. I t is not an acetylide, however, for it gives no acetylene when heated with hydrochloric acid, but aldehyde instead. Neither is it a mercurous compound, for, when it is digested for hour with dilute hydrochloric acid, 83.8 per cent.of mercuric chloride is formed, but only 2.3 per cent. of mercurous chloride, and this, no doubt', on account of the reducing action of the aldehyde simultaneously formed ; further, potassium cyanide solution dissolves the compound without deposition of mercury, and ammonia produces no black coloration. The substance analysed by Erdmann and Kothner contained a little mercury ; af ter removal of this by digestion with dilute nitric acid, the analytical numbers agree with the formula NO,*Hg*C( :Hg,:O) *CHO, that of a substituted aldehyde, The compound is best prepared by dissolving yellow mercuric oxide (20 grams) in dilute nitric acid (70 C.C. of 30 per cent.acid and 500 C.C. of water), filtering, and passing a fairly rapid current of acetylene for 2 hours through the solution a t a temperature of 189 The precipitate is then collected, digested three times with 8 per cent. nitric acid (150 c.c.) at the ordinary temperature for 6 hours, filtered, washed with alcohol and ether, and dried under diminished pressure over sulphuric acid. C. F, B. VOL. LXXVI. i h98 ABSTRACTS OF CHEMICAL PAPERS. Acetylene Tetrabromide and Tribrornethylene. By KARL ELBS and J. NEWMANN (J. p'. Chern., l89S, [ii], 58, 245--254).-1n preparing acetylene tetrabromide from acetylene generated from calcium carbide, the gas is best purified from hydrogen phosphide by passing it through a solution of mercuric chloride acidified with hydro- chloric acid.The pure tetrabromide is an almost colourless liquid boiling a t 124-126' under a pressure of 15 mm. When reduced with zinc dust and acetic acid, or zinc dust and sodium ethoxide in alcoholic solution, the principal products are acetylene di bromide and tri- bromethy lene, and small amounts of ethylene dibromide. Aluminium amalgam reduces the tetrabromide so rapidly and completely to ace- tylene dibromide that it may be used as a means of preparing that substance. Attempts to replace bromine in acetylene tetrabromide by iodine or acetyl groups proved unsuccessful ; the action of aniline, dimethyl- aniline, or alcoholic ammonia causes the production of t r i bromethylene. When the tetrabromide is heated with bromine and aluminium in sealed tubes a t 90-95", hexabromethane is produced.Bromine acts readily on tribromet hylene, producing pentabrom- ethylene ; iodine reacts but slightly, whilst chlorine gives rise t o chlorotribromethylene, crystallising in coIourless needles melting a t 3 5 O (compare Denzel, Abstr., 1880, 228), and uniting with bromine to form chloropentabromethane melting at 170". Zinc dust acts on tribromethylene, producing acetylene ; concen- trated sulphuric acid gives rise to pentabromethane ; fuming sulphuric acid decomposes the substance completely ; and nitrous anhydride produces tribromonitroethybne as a heavy, pale yellow liquid, with penetrating odour, boiling a t 108-110" at 21 mm. (compare Scholl and Brenneisen, Abstr., 1898, i, 345) Chlorine acts on pentabromethane a t 200-205", with production of chlorotribromethylene, whilst antimony pentachloride gives rise to hexachlorethane.A. W. C. Hydrocarbon, C,H,, a Secondary Product of the Decompo- sition of Barium Pyromucate. By PAUL FREUNDLER (BUZZ. SOC. Chim., 1897, [iii], 17, 614-616).-The hydrocarbon, C,H,, obtained when barium pyromucate is distilled (see this vol., i, l20), has a some- what aliaceons odour, and precipitates an alcoholic solution of mercuric chloride, but not ammoniacal cuprous chloride or silver nitrate. When treated with bromine, i t yields a small quantity of a dibrmide boiling a t about 50" under reduced pressure, but the chief product is a tetrabromide, C,H,Br,, a liquid boiling a t 162" at 20 mm. pressure. This compound has not been obtained pure, as it is extremely hygroscopic, and as it is not identical with allylene tetrabromide, it is probable that the hydrocarbon has the constitution CH2<rH.CH J. J. S. Action of Ammonia on Zinc and Mercuric Cyanides, and on Haloid Double Salts of the Latter. By RAOUL VARET (Ann. Chin2. Phys., 1897, [vii], 10, 5-18. Compare Abstr., 1896, i, 3, 633, ii, S8, 149, 513; 1897, i, 685, ii, 38, 9'3).-l'he conzpou?adORGANIC CHEMISTRY. 99 Zn(CN),,2NH3,H,0, obtained in transparent, prismatic crystals is produced by the action of ammonia on aqueous solutions of zinc cyanide ; the compound Zn(CN),,.2NH3, is formed in alcoholic am- moniacal solutions, or by the action of dry ammonia on the heated cyanide. Both these substances are very soluble in aqueous and alcoholic ammoniacal solutions, and rapidly decompose on exposure t o the air. The compound 2Hg(CN),,4NK3,H,0 separates in white, prismatic needles when a saturated solution of mercuric cyanide in concen- trated ammonia is cooled in a freezing mixture; the compound 2Hg(CN),,2NH3,H,O is obtained when a saturated solution of mercuric cyanide in less concentrated ammonia is allowed t o crys- tallise at 0'; both substances are very unstable, and are completely resolved into their constituents when heated to 100".The compound Hg(CN),,2NH3 results from the employment of alcoholic solutions ; it separates in transparent, prismatic needles, which decompose rapidly on exposure to air. The cornpound Hg(CN),,NH,, produced in an aqueous ammoniacal solution of mercuric cyanide in the presence of excess of the salt, separates from the filtrate in hard, granular crystals; it is more stable than the preceding compounds, but is completely decom- posed on heating a t 100'.No definite compound results from the action of dry, gaseous ammonia on warm mercuric cyanide. The double salt, Hg(CN),,HgCl,, when treated with alcoholic ammonia, is resolved into its components; mercuric chloride gives rise t o an insoluble compound, 2HgC1,,3NH3, whilst mercuric cyanide yields the substance Hg(CN),,2NH3. A greyish-white su6stance, 2Hg2(CN),C1,,3NH,, is obtained by the action of dry ammonia on gently heated mercuric chlorocyanide. The chlorocyanide, when treated with aqueous am- monia, gives a precipitate of mercuric ammonium chloride, NH,HgCl ; if zinc cyanide be added to the mixture, the precipitate redissolves, and on concentrating the solution the double salt, 2Hg(CN),,ZnC12,4NH,, is obtained in nodular crystals ; this compound is also produced by the action of aqueous ammonia on the double salt, 2Hg(CN),,ZnC1,,7H20.The latter method is employed in preparing the following series of analogously constituted double salts. 2Hg(CN),,ZnBr,,4NH3 ; 2Hg(CN),,CuCl2,4NH3 ; 2Hg(CN)2,CuBr2,4NH, ; 2Hg(CN),,CdBr2,4NH,,2H20 ; 2Hg(CN),,CdBr,,4NH3 ; 2Hg(CN)2,Ud12,4NH3. These compounds are crystalline, and the copper and cadmium derivatives do not evolve ammonia when heated to 100'. Action of Chlorine on Secondary Alcohols. By ANDRB BROCHET (Am,. Chirn. Phyg., 1897, Lvii], 10, 134-144).-This paper gives a detailed account of the ultimate action of chlorine on iso- propylic alcohol and methylhexylcarbinol ; the results obtained have already been published (see Abstr., 1895, i, 259 ; 1897, i, 4). G.T. M. G. T. 3%. Action of Chlorine on Primary Alcohols. By ANDRJ~ BROCHET (Am&. Chz'm. Phys., 1897, [ vii], 10, 289--380).-This paper contains a very detailed account of work which has already been published. The theory of the chlorination of ethylic alcohol is fully discussed, and the work of previous investigators compared with the results h . 2100 ABSTRACTS OF CHEMICAL PAPERS. obtained by the author with other primary alcohols. The action of chlorine on methylic alcohol (Abstr., 1895, i, 637, and 1896, i, 276), on propylic alcohol (Abstr., 1896, i, 114), and on isobutylic alcohol (Abstr., 1892, 1292; 1894, i, 484; and 1897, i, 3, 4) has already been made known.When chlorine acts on any primary alcohol, except methylic alcohol, the first product of reaction is a dichloro-derivative, CnH2,C1*CHC1*OH ; this either passes into a monochloraldehyde, CnH2nCl*COH, by loss of hydrogen chloride, or condenses with another molecule of alcohol to form an unsymmetrical dichloroxide, C,H2,C1*CHCl*O*CH2*CnH2n+l. This statement has been verified in the case of ethylic, propylic, isobutylic, and isoamylic alcohols (Abstr., 1898, i, 549). I n the case of methylic alcohol, the initial product is chloromethylic alcohol, which, by elimination of water, is converted into symmetrical dichloromethylic oxide. G. T. M. By ANDRI~ BROCHET (Ann. Plys. Chim., 1897, [ vii], 10, 381-387).-Chlorine has no action on cold dimethylethylcarbinol in diffused daylight, but at the boiling point of the alcohol, it is rapidly absorbed without evolution of gas. The products of the reaction are fractionated ; the lowest fraction contains tertiary amylic chloride (2-methyl-2-chloro- butane), CMe2C1* CH,Me, and chloramylene (2-methyI-3-chlorobutene), CMe2:CMeC1.This mixture is treated with bromine and sub- sequently steam distilled, wheu amylic chloride is obtained in the distillate and chloramylene dibromide remains in the residue. The higher fractions contain some unattacked alcohol and higher chlorinated derivatives of isopentane (2-methyl butane), dichloriso- pentane, CNe,Cl* CHMeC1, and trichlorisopentane, have been isolated. The latter boils at 176", its sp.gr. = 1.215 a t 15'/4", and its index of refraction nD= 1.472 a t 21'. The chief product of the action of chlorine on the cold alcohol in the presence of sunlight is the above-mentioned dichlorisopentane. When the gas is passed into a boiling mixture of the alcohol and water, the chief product is trichlorisopentane ; chloro-derivatives of higher boiling point, acetone, acetic, formic, and carbonic acids are also formed, but no amylic chloride could be detected. The first action of chlorine results in the formation of CMe,Cl* CHMeCl, this substance loses hydrogen chloride and forms CMe2:CMeCl, addition of chlorine t o the chloramylene produces CMe2C1* CMeCl, ; the amylic chloride is produced by a secondary reaction between the hydrochloric acid liberated and the unattacked alcohol. By PHILIPPE BARBIER and GEORGES LESER (BUZZ.Soc. C h k , 1897, [iii], 17, 590--596).-When pure licareol (boiling a t 86-88" under 10 mm. pressure) is heated with its own weight of acetic anhydride during 8 hours at 150-160' and the product rectified under a pressure of 10 mm., three fractions are obtained. The first passes over between 50' and SO', and consists mainly of terpenes ; the second, passing over between 80" and 105", consists mainly of unaltered licareol, and the third, boiling at 105-130", when further fractionated with the aid of a dephlegmator, The author puts forward the following generalisation. Action of Chlorine on Tertiary Amylic Alcohol. G. T. M. Dextro-licarhodol.ORGANIC CHEMISTRY. 101 yields a colourless liquid boiling at 11 9-1 20' under 10 mm.pressure ; this has the composition C,,H,,* OAc. The higher fractions contain an ether, (C,oH,1)20, boiling at 145-150° under 10 mm. pressure. The acetate is hydrolysed when the theoretical quantity of alcoholic potash is run in at the ordinary temperature, and the mixture then heated to 100' for an hour. The alcohol, Cl0H,,O, licarhodol, thus obtained boils a t 1 1 2-1 14' under 9 mm. pressure, has an agreeable odour, sp. gr. at Oo= 0.904, and rotatory power [ a],, = + 4' 8'. The yield is about 800 grams from 5 kilos, of licareol. When oxidised with perman- ganate, licarhodol gives dimethyl ketone, terebic acid melting a t 174", and levulinic acid. When oxidised with chromic mixture, the products are methylheptenone, CMe,:CH*CH,*CH,Ac, a small quantity of geranial-citral, and an acid, C,H,,O,, probably methyl- heptenonecarboxylic acid.The following is the constitution suggested for licarhohol, CH,:CMe* CH(CH,OH)*CH,* CH:CMe,. Action of Neutral Salts on Glucose at a Higher Tempera- ture. By H. C. PRINSEN GEERLIGS (Chem. Centr., 1898, i, 712; from ds.ch. Javasuikerindustrie, 1898). - The author finds that, not only do the salts of weak organic acids bring about the inversion of sugar in presence of glucose, but that at looo they also act on the glucose, converting the dextrose into levulose, or when the latter is in excess, inversely converting it into dextrose; the same change is effected by the alkali salts of strong mineral acids (see following abstract), but t o a very much smaller extent.The amount of change is proportional to the time during which the action has proceeded and to the concentration of the solution of the salt. A portion of the glucose is converted into organic acids, and it is these acids which sometimes interfere with Romijn's test for dextrose with iodine solution containing borax (Arch. Xuikerindustrie, 1897, 1001) by absorbing iodine and forming iodoform. The feeble rotatory power of molasses containing much invert-sugar is due to the fact that the raw sugar molasses contain considerable quantities of salts of organic acids. E. w. w. Inversion of [Cane] Sugar by Neutral Salts in Presence of Glucose. By H. C. P~INSEN GEERLIGS (Chem. Centr., 1898, i, 71 1 ; from Arch. Suikerindustrie, 1898).-The quantity of sucrose inverted by neutral salts in presence of glucose (see Arch.Xuikerindusti+e, 1895) is approximately proportional to the time during which the action takes place and to the amount of glucose originally present; the quantity of salt (sodium chloride) has only a very slight influence on the action. The action of the glucose is due to the liberation of a very small quantity of acid by the formation of a glucosate of the base, but when calcium carbonate or a salt of a weak organic acid is added, the inversion is retarded or prevented. The more easily dissociated salts are the more active, thus magnesium chloride and the chlorides of the alkaline earths are more effective than the chlorides of the alkalis. Tho acids contained in the salts also have a great influence; the following salts of potassium are arranged in order of decreasing activity : chloride, bromide, nitrate, sulpha te, J.J. S.102 ABSTltACTS OF CHEMICAL PAPERS. chlorate, oxalate, and succinate. Since Ohe monosaccharides, dextrose, levulose, galactose, and lactose act like glucose, whilst the alcohols and the di- and tri-saccharides are inactive, the presence of an aldehyde group may be necessary t o bring about the reaction. E. W. W. Inversion ,of Saccharose by Water. By BOHUSLAV RA<MAN and OTTOKAR SULC (Chem. Centr., 1898, i, 608-609 ; from Zeit. 2ucL.- Tnd. Bohrn., 22, 233-248. Compare Abstr., 1898, i, 34S).- Saccharose is inverted by water at temperatures above l l O o , but when acid is added the change takes place a t a lower temperature. When extremely pure water is used, 10 per cent.and weaker solutions of saccharose are not affected by boiling for some hours, but when the water has a considerable conductivity, the action com- mences ; generally speaking, the more concentrated the solution is after boiling, the more quickly inversion begins. When platinum vessels are used, the action occurs more rapidly, no matter how small the conductivity of the water, and in vessels of other metals inversion takes place with varying rapidity. The action of the metals of the platinum group in powder was investigated ; of these, palladium induced the most rapid change, iridium alone retarded the action, and in many cases a faint acidity of the solution could be detected by Congo-red. When metallic vessels were used, this acidity was only apparent in the cases of copper and silver.The author ascribes the influence of metals partly to a hydrolytic action and partly t o the formation of acids from the sugar; like acids, the metals are supposed to increase the chemical activity or “ionisation” of the water. The acid compounds are formed by a process of migration of the oxygen atoms analogous to certain reactions of sugars with alkalis and water. The oxidation of hydroxy-aldehydes and hydroxy- ketones is explained by a process of successive dehydration and hydration, whereby the groups CH,*OH and CH*OH become CH, and CH, respectively, and the terminal carbon atoms either form carboxyl groups, formic acid, or carbonic anhydride. At the same temperature, increase of pressure diminishes the inversion effected.E. W. W. Hydrolysis of Polysaccharides by Yeast Enzymes. By AKUSCIIAWAN KALANTHAR (Zeit. physiol. Chem., 1898, 26, 88-101). -The author has studied the hydrolytic action of yeasts from various wines and beers, and from the Russian beverage ‘‘ kissly-schtschi ” and the Armenian beverage ‘6 mazun ’) on the polysaccharides. Pure cultures were prepared in each case, and both fresh and dried cells and aqueous extracts were employed. The polysaccharides experimented on were cane-sugar, maltose, lactose, melibiose, trehalose, melitriose (raffinose), melicitose, and a-methylglucoside ; 10 per cent. solutions were submitted to the action of the yeast, a little toluene being added to prevent alcoholic fermentation. The amount of monosaccharide produced was determined either by titra- tion with Fehling’s solution, or in the case of those polysaccharides which themselves reduce Fehling’s solution, by ascertaining the amount of osazone produced with phenylhydrazine ; the resultsobtained are tabulated, and they indicate that the dried yeast and the aqueous extract possess a greater hydrolytic action than the fresh cells.Cane-sugar and rafinose were readily hydrolysed by all the forms o€ yeast employed. Maltose and a-methylglucoside were usually decomposed to the same extent, but in one or two cases the latter compound appeared to be more readily attacked. Although melibiose and lactose are formed from t,he same components (d-glucose and d-galactose), they behave somewhat differently towards enzymes ; the amount of the former hydrolysed varied with the temperature, only oiie wine yeast being capable of hydrolysing it a t 25’, but in every case negative results were obtained with lactose.Trehalose was hydrolysed by all the yeasts in the dried condition (compare Abstr., 1895, i, 441), except in the case of an orange-red yeast from ‘‘ mazun ’’ ; fresh wine or distillery yeast also induced appreciable hydrolysis. Melicitose was hydrolysed by all the beer yeasts, with one exception. The author adds a description of the preparation of “mazun” from milk. This beverage contains, besides bacilli and micrococci, nine species of yeast cells; seven of these have been isolated by Lindner and the author, and a table showing their hydrolytic action on maltose, a-met hylglucoside, trehalose, lactose, and cane-sugar is included in the paper.Q. T. M. Formation of Furfuraldehyde from Starch and its Derivatives. By FAUSTO SESTINI (L’Orosi, 1898, 21, 109-113).- Furfuraldehyde, t o which the odour of new bread is partly due, is produced by the simple heating of all varieties of bread, the crumb requiring to be heaOed to 140-160°, whilst for the crust, which has been already more strongly heated in the cooking, a temperature of 110-115° is sufficient. The aldehyde does not exist ready formed in the bread, since none is obtained from i t by steam distillation, and its production must be attributed to the decomposition of pentoses derived from the bran, or t o that of the starch and allied carbohydrates. Dry starch of various kinds was found to yield furfuraldehyde when heated to lSOo and upwards, whilst if previously moistened with a minute quantity of sulphuric or hydro- chloric acid, even a temperature of 100’ was sufficient for its produc- tion.Nageli’s ‘‘ starch granulose,” deprived of every trace of free acid, .evolves furfuraldehyde at 100’ or a few degrees higher, and the different varieties of dextrin behave in a similar manner. Fur- furaldehyde may be obtained from pentoses without the aid of acids, as various kinds of gum were found to yield this substance when heated in the dry state to 180-200°, and also, if slightly moistened with water, at 120”. Two specimens of purified rice starch, when distilled with hydrochloric acid of sp. gr. = 1.06, yielded respectively 1.16 and 0.44 per cent. of furfuraldehyde, quantities far greater than could be derived from traces of pentoses possibly present in the starch and which, moreover, could not be detected therein.It follows from these results that the amount of furfuraldehyde obtain- able from starch and allied carbohydrates is by no means a neglige-108 ABSTRACTS OF CHEMICAL PAPERS able quantity, and this fact must be taken into account in estimating pentoses by the furfuraldehyde method. Derivatives of Bromethylamine and Bromopropylamine. By SIEGMUND GABRIEL and ERNST LEUPOLD (Bey., 1898, 31,2832-2839). -Orthohydroxybenxylidenebromethylamine, OH-C,H;CH :N*C,H, Br, formed by the condensation of bromethylamine hydrobromide with salicylaldehyde in presence of an alkali, crystallises in yellow needles, melting at 56-57'.Ethylenepseudothiocarbamide is converted by nitrous acid into N. L. ?H2* S CH;N >CPh; the picrate crystallises in lemon- p-phenylthiazoline, yellow needles, which s:ften a t 165' and melt at 173--174', whilst the dichromate, (C,H,NS),,H2Cr207, forms orange-yellow needles. The formation of this compound favours the supposition that ethylenepseudothiocarbamide contains a n amido-group, and has the YH2* S constitution CH2,N>C* NH,. The thiazoline derivative is accom- panied by a substance crystallising in flat, yellowish needles which melt and decompose at 203-204". This compound is probably nitroethylenepseudothiocarbamide, but has not been obtained in suffi- cient quantity for further examination. FHMe S p-Phen y l-P-me t hyl t hiazoline, CH,--N >CPh, is obtained from propylenepseudot hiocarbamide, and ?s identical with that previously obtained from thiobenzamide (Gabriel and von Hirsch, Abstr., 1897, i, 1 20).Nitropopylenepseudothiocarbamide, C4H7NS*N0,, cry stallises in flat, oblique needles, which melt and decompose a t 166". Mercaptothiazoline is decomposed by hydrochloric acid at 155" with formation of amidomercaptan. Mercaptomethylthiazoline, when treated in a similar manner, yields c~midopropyZ-/3-mercaptan hydrochloride, SH*CHMe-CH,*NH,,HCI, which crystallises in microscopic tablets and melts at 87-88"; the picrate crystallises in com- pact, rhornbic tablets melting at 143-144' ; on treatment with iodine, it yields diamidopropylic P-bisulphide, the hydrochloride of which, C6Hl,S2N212HC1, melts at 213-214', the picrate forms short, thick prisms melting at 162-163'.Chemical Activity of Organic Ammonium Salts. By WOLFGANG BRENDLER and JULIUS TAFEL (Ber., 1898, 31,2683-2686. Compare Tafel, Abstr., 1898, i, 47 l).-T~irnethylacetonylammonium bromide, COMe*CH,*NMe,Br, obtained on passing trimethylamine into an ethereal solution of bromacetone, crystallises in well-formed, colourless needles when the alcoholic solution is exposed t o an atmos- phere of ether; it melts at 190°, and a t 195' gives rise t o a yellow distillate and tetramethylammonium bromide. The phelzylhydraxone is a crystalline substance which dissolves more readily in water than in alcohol ; Fehling's solution precipitates a yellow oil which is volatile in steam. Bromacetonyltrimethybmmoniurn bromide, C,Hl,NOBr2, obtained by the action of bromine on trimethylacetonylnmmonium bromide, A.H.ORGANIC CHEMISTRY. 105 crystallises from alcohol. If bromine water is employed instead of the undiluted halogen, a reddish-yellow, crystalline precipitate is formed having the properties of an ammonium tribrornide ; when an attempt is made to dry this substance, hydrogen bromide is elimi- nated, and bromacetonyl trimethylammonium bromide is formed. The aqueous solution of the last-named substance yields trimethyl- amine when heated. M. 0. F. Propylnitramine and its Alkyl Derivatives, and the Probable Existence of a New Glass of Neutral Nitramines. By HERM. UMBGROVE and ANTOINE P. N. FRANCHIMONT (Rec. TTUV. Chirn., 1898, 17, 2 70-2 86).-DipropyZdinitroxa~ide, C,O,( NPr *NO,),, prepared by leaving dipropyloxamide in contact with six times Its weight of concentrated nitric acid for 48 hours, and pouring the product into ice cold water, crystallises from alcohol in large tables, and melts a t 44".When dissolved (65 grams) in concentrated aqueous ammonia (150 c.c.), oxamide separates, whilst the ammonium derivative of propylnitramine remains dissolved ; on adding dilute sulphuric acid to the clear solution, nearly the theoretical quantity of propylnitramine is obtained. Etl~~Z~opyZnitram~ne, prepared by boiling a mixture of the potas- sium derivative of ethylnitramine (26 grame), propylic iodide (32 grams), and methylic alcohol (100 c.c.) during 30 hours, is a colourless liquid with a characteristic odour ; it boils a t 108" under t~ pressure of 22 mm., and has a sp.gr. = 1.028 at 15". It dissolves in concen- trated sulphuric acid without evolution of gas, giving rise, apparently, t o nitrosulphuric acid and a substance possessing cupric-reducing power, which is probably a hydroxylamine or an imine. From the lower fractions obtained in purifying the crude ethylpropylnitramine by fractional distillation, a substance isomeric with the latter was isolated, differing from it in boiling point (65' under a pressure of 20 mm.) and i n its behaviour with concentrated sulphuric acid. On heating ethylpropylnitramine with 10 per cent. aqueous potash for 9 hours at 150-160°, it is decomposed into propylamine, nitrons acid, and acetaldehyde; tliis is in accordance with van Erp's views (Abstr., 1895, i, 590 ; and 1897, i, 6) regarding the action of alkalis on mixed aliphatic nitramines.It appears that, in this decomposition, the heavier radicle separates combined with the amido-group, and the lighter in the form of an aldehyde. The principal product formed on leaving the silver derivative of propylnitramine (82 grams) in contact with ethylic iodide (60 grams) dissolved in ether (500 grams) during 12 hours in the dark, and sub- sequently heating the mixture during 6 hours a t 50", is iso-ethylpropyl- mitrumine ; this distils unchanged at 58.5" under a pressure of 16 i-nm., has a sp. gr. = 0.9755 at 15', and does not give a colorat-ion with an acetic acid solution of a-naphthylamine, either alone or in presence of zinc. It differs in this respect from an isomeric substance formed simultaneously, which decomposes when distilled into nitrogen, water, acetaldehyde and propaldehyde ; together with this unstable iso- meride, a small quantity of ethylpropylnitramine is also formed.On heating iso-ethylpropylnitramine with 10 per cent. aqueous potash,106 ABSTRA(!TS OF CHEMICAII PAPERS. nitrogen is evolved, and propaldehyde appears to be formed, although this immediately polymerises, giving a resin. ~ s o ~ r o ~ ~ l e t h y l n i t r c ~ ~ ~ ~ i ~ e , prepared by acting on the silver derivative of ethylnitramine with an ethereal solution of propylic iodide, boils at 65' under a pressure of 20 mm., and has a sp. gr.=0*9783 a t 15'; at the same time, propylethylnitramine is formed, together with an isomeric substccnce, which decomposes when heated, giving nitrogen and propaldehyde.When isopropylethylnitramine is heated with 10 per cent. aqueous potash, it gives rise to nitrogen and acetaldehydo, in accordance with van Erp's rule (Zoc. cit.). Isopropylmethylnitramine, prepared by leaving the silver derivative of methylnitramine in contact with propylic iodide dissolved in ether during 5 days at the ordinary temperature, boils a t 51' under a pressure of 18 mm., and has a sp. gr. = 1.012 a t 15' ; altbough no gas is evolved when i t is heated at lOO', it gives a marked coloration with an ace t'ic acid solution of a-naphthylamine. When decomposed by aqueous potash, i t apparently gives rise to formaldehyde. W. A. D. Action of Sulphuric Acid on Aliphatic Nitramines and their Isornerides. By ANTOINE P.N. FRANCHIMONT and HERM. UMBGROVE (Rec. Trau. Chim., 1898, 1'7, 287-295).-Concentrated sulphuric acid acts in the same manner on the silver and mercury derivatives of methylnitramine as on methylnitramine itself ; in each case, nearlythe theoretical quantity of nitrous oxide is evolved, no other gas being formed. From ethylnitramine, however, and its potassium derivative, a small quantity of an inflammable gas, probably an olefine, was also obtained, and the same is true of propyl- and butyl-nitramine. The behaviour of ethylpropylnitramine with concentrated sulphuric acid has been dealt with in the preceding abstract ; the action is the same, but slower, when 40 per cent. sulphuric acid is employed, partial decomposition only taking place.The isodialkylnitramines are, however, rapidly decomposed by this mid a t the ordinary tempe- rature, giving nitrous oxide and two alcohols, that formed by the alkyl radicle directly attached to the nitrogen also giving rise, as a rule, to an olefine, except in the case when the radicle is methyl. This behaviour was verified in the case of iso-ethylmethyl-, isomethylethyl-, isodiethyl-, iso-ethylpropyl-, isopropylethyl-, and isopropylmethyl- nitramines. The ease with which the isodialkylnitramines undergo de- composition when treated with 40 per cent. sulphuric acid is explained by attributing to them the general formula NKNO*OR ; or, assuming that the acid nitramines have the general formula O<,->o THR (Briihl), by giving the neutral isonitramines the general structure W.A. D. K N . TR OR' Neurine and its Derivatives. By WL. GULEWITSCH (Zeit. physiol. Chem., 1898, 26, 175-188).-The author describes the ap- pearance, as seen with the un3rsisted eye and with th9 microscope, ofORGANIC CHEMISTRY. 107 precipitates obtained with dilute solntions of synthetically prepared neurine hydrochloride and the usual reagents for alkaloids. These precipitates obtained with dilute solutions of neurine are far less soluble than those from choline. Contrary to Brieger's observation, the author finds that phosphotungstic acid gives a precipitate with neurine hydrochloride which is distinctly visible even in solutions containing only ,$aBth of the base. Neurine picrate forms golden-yellow needles melting at 263-264O ; it is very insoluble in cold water and alcohol. Neurine platino- chloride melts a t 195.5-19S0, contains no combined water, and differs in its crystalline form from the corresponding choline salt. The aurichloride, C5H1,NAuC14, forms golden-yellow needles melting at 228--232O, and contains no water of crystallisation.On the addition of mercurous chloride to an alcoholic solution of neurine hydrochloride, two double sults are precipitated ; the less soluble, C5H12EU'C1,6HgCl,, forms colourless, tabular crystals and melts at 230*5--234O ; the more soluble, C,H12NCl,HgC1, crystallises in aggregates of narrow prisms and melts at 198*5-199-5°. Dilute solutions of neurine are not decomposed on boiling, but concentrated solutions give off trimethyl- amine. Neurine hydrochloride, when recrystallised from water, has no tendency t o take up one molecule of the solvent and become trans- formed into choline hydrochloride.G. T. M. Constitution of Ornithine and Arginine. By ERNST SCHULZE and ERNST WINTERSTEIN (Zeit. physiol. Chem., 1898, 26, 1-14. Compare Abstr., 1898, i, 2Sl).-Ornithine, C,H,,N,O,, was originally discovered by Jaffk (Abstr., 1878, SSS), who suggested that its consti- tution might be that of a diamidovaleric acid ; i t does, in fact, closely resemble the diamidopropionic acid prepared synthetica.lly by E. Klebs (Abstr., 1894, i, 439). A rginine, C,H,,N40,, prepared either from the seedlings of Lup'nus luteus 013 by heating albumin with hydrochloric acid, yields ornithine and carbamide when hydrolysed with baryta water.Ornithuric acid, the dibenzoyl derivative of the former base (JaffC., Zoc. cit.), is obtainedfrom the crude product of reaction by the Schotten-Baumann method ; this compound is hydrolysed by con- centrated hydrochloric acid, first into a monobenzoyl derivative, and then into ornithine, the yield of benzoic acid aiid ornithine dihydro- chloride being almost theoretical. Ornithine, on treatment with nitrous acid, loses the whole of its nitrogen, but the hydroxy-acid which should be formed has not been investigated. Phenanthraquinons gives no quinoxaline derivative with ornithine, and the authors there- fore suppose that the amidogen groups are not attached t o contiguous carbon atoms. If ornithine be assumed to be a diamidovaleric acid, then arginine might have the following constitution, which resembles those of glycocyamine and creatine.The yield of ornithine from arginine is only 40 per cent. of the theoretical quantity. This may be due, as in the case of creatine, t o the fission of the molecule taking place in two ways, but no other well- characterised product of hydrolysis has yet been isolated. NH:C(NH,)*NH*CH,-CH,*CH,*CH(NH,)*COOH, G. T. M.108 ABSTRACTS OF CHEMICAL PAPERS. The So-called Nitroazoparaffins. By EUGEN BAMBERGER (Be+*.., 1898, 31, 2626--2635).-1n accordance with modern views, the ‘‘ nitroazoparaffins ” of Victor Meyer must be regarded as hydrazones containing the grouping *C(NO,):N*NH*, and, therefore, as true nitro- compounds, whilst their salts must be looked on as derived from the tautomeric isonitro-azo-compounds, the above group having become *C(NOOH) *N :No.When L nitroazoparaflins ” are subjected to alkaline hydrolysis, they are decomposed v i t h production of acidylhydrazines and nitrous acid. Thus ‘‘ phenyl-nitroam propane," or nitropropionalde(pheny1)- hydrazone,” as the author prefers to term it, when heated on the water-bath, with a 1 per cent. solution of soda, is almost quantitatively converted into /3-propionylphenylhydrazine, probably iu accordance with the equation, NO,*CEt:N*NHPh + H,O = COEt-NH-NHPh + HNO,. NitroacetaZde(phenyZ)hydraxone, NO,*CMe:N*NHPh, is produced in nearly theoretical amount by the foregoing process. Nitroethane (10 grams) is quickly dissolved in an ice cold solution of soda (5.2 grams) in water (3 grams) and mixed at once with an ice cold solution of the diazonium acetate made by dissolving aniline (12 grams), concentrated hydrochloric acid (30 grams), sodium nitrite (9.4 grams), and crystallised sodium acetate (44.4 grams) in water (2 litres).The sub- stance separates quickly as a yellow oil, which soon solidifies ; it does not exhibit either Meyer’s or Konowaloff’s reaction, and cannot, there- fore, be the ‘‘ iso-” form, NOOH:CMe*N:NPh. It crystallises from alcohol in golden-yellow, and from benzene in orange-red, leaflets, and melts a t 141-142’. It decomposes slightly when kept in a closed vessel, and then has an odour of acetic acid; in one instance, it decomposed, giving nitrous and acetic acids and diazobenzene nitrate. When nitroacetalde(pheny1)hydrazone is warmed with a dilute solu- tion of soda in dilute methylic alcohol for 2 hours, it is decomposed, giving an appreciable quantity of an isodiazotate, ammonia, phenyl- hydrazine, and a neutral oil, but the principal product is P-acetyl- phenylhydrazine. Nitropropionalde(pheny1) hydrazone, NO,*CEt:N*N HPh, prepared by a method similar to that used in the case of the acetaldehyde compound, forms hard, orange-yellow crystals, and melts a t 98-5-99.5’ (com- pare Meyer, this Journal, 1876, ii, 93).It does not, as stated by Meyer, give an immediate violet-red coloration when treated with strong suIphuric acid, but a fiery-red, the violet tone being a later development ; a similar statement holds true in the case of the acetalde- hyde compound. Nitropropionalde( pheny1)hydrazoa e, is, as hasalready been mentioned, almost completely converted into nitrous acid and P-propionylphenylhydrazine when warmed with dilute soda.Nitrovaleralde(phenyl)hydraxone, C,H,: C(N0,) :N*NHPh, is obtained when nitropentane is treated with the diazonium acetate ; it exists in two forms. The P-modijkation obtained by crystallising the substance from alcohol, separates in golden-yellow leaflets having a bronze-like lustre, and melts at 92-5-93’, dissolves readily in acetone, and decom- poses when kept for a long time in a closed vessel ; its solution in sulphuric acid is a t first fiery red, but gradually becomes violet-red * The author omits the “phenyl ” in his paper.-[EDITORS.]ORGANIC CHEMISTRY. 109 spontaneously, and at once on the addition of dichrornate.The u-rnod.2- cation obtained from the former by boiling it with heavy petroleum, separates from the solution on cooling in long, silky needles, which are orange-red by reflected and golden- yellow by transmitted light, and have a metallic-blue reflex; it has the same composition as the u-form, but melts at 51*5-52", and is very readily dissolved by light petroleum ; it may be converted into the P-modification by dissolving i t in boiling alcohol, and if the melted substance is allowed to solidify, it melts once more a t 86-87', indicating a more or less complete conver- sion into the /3-form; a similar change is found to have occurred when its solution in alkalis is precipitated by means of an acid. By trent- ment with alkali, p-nit rovaleralde(pheny1)hydrazone is .converted into P-valerophenylhydrazide ; the latter melts at 112-112.5° and not at 101' as stated by Autenrieth (Abstr., 1888, 251).A. L. Formhydroxamic Acid.-By JOHN U. NEF (Ber., 1898, 31, 2720-2721).-1n view of the paper recently published by Schroeter (Abstr., 1898, i, 623), the author points out that investigations on form- hydroxamic acid and its derivatives are in progress in his laboratory. The ethers of this acid can be obtained by heating formic acid with a-alkylhydroxylamines. Benzylhydroxamic acid, for example, can readily be prepared in this way, and is a thick oil with strongly acid properties. A. H. Action of Semicarbazide on Formaldehyde. By JOHANNES THIELE and JAMES BAILEY (Annalen, 1898, 303, 91--93).-When a 4 per cent. solution of formaldehyde is added to aqueous semicarbazide hydrochloride, a gelatinous precipitate is formed, and this compound, after being washed with water and dried at 95", has the composition C,H,,N,O, + $.H20 ; it is, therefore, a hydrated condensation product of semicarbazide (2 mols.) with formaldehyde (3 mols.).H. Thoms (Ber. deutsch. Pharm. Ges., 7, 5 ) has recently obtained a normal pro- duct of condensation. The substance dissolves in 60 per cent. hydro- cyanic acid, yielding a compound which crystallises from dilute acetic acid, and melts a t 12'7.5"; no definite formula has been assigned to it. M. 0. F. Aldehyde-ammonia. By ROBERT DE FORCRAND (Compt. rend., 1898, 126, 248-250).-The author's calorimetric experiments con- firm those by which Delepine (Abstr., 1898, i, 462) demonstrates that aldehyde-ammonia in the solid state consists of the more or less polymerised hydrate of ethylidenimine, and that, when dissolved in water, a gradual change into the simple form takes place.Two series of calorimetric determinations were made on the heat developed by the action of dilute sulphuric acid on solutions of alde- hyde-ammonia which had been kept for different periods of time. In one case, the aldehyde-ammonia solution was prepared by adding weak ammonia to a dilute solution of aldehyde, and in this series of determinations the heat effect at first decreased until a minimum was reached after 8 days, and then increased until the end of 50 days. When the solution was prepared by dissolving solid aldehyde- ammonia in water, the heat developed by the action of the acid was110 ABSTRACTS OF CHEMICAL PAPERS.least after 7 minutes, aiid gradually increased until the end of 50 days. I n the first series, there is a rapid change of aldehyde-ammonia into polymerised ethylideniminc, and, at the same time, this polymeride slowly passes into the simple form; in the second series, the poly- meride gradually dissociates into the simple imine. G. T. M. Amidoaldehydes. By EMIL MA ASS and RICHARD WOLFFENSTEIN (Ber., 1898, 31, 2687-2692. Compare Abstr., 1898, i, 44).-For reasons which are discussed in the original paper, the authors regard those amidoaldehydes which are convertible into piperidine deriva- tives as capable of acting in accordance with the tautomeric formula, :C,H,*NH:O; from this point of view, they belong to the group of oxides obtained by the action of hydrogen peroxide on 1-alkylpiperidine bases (Wernick and Wolffenstein, Abstr., 1898, i, 536).The facts which have led to this conclusion are as follows. The benzoyl derivative of orthamidomethylphenylacetaldehyde (Abstr., 1898, i, 44) yields benzoic acid on oxidation with potassium permanganate. Benzoic acid is also produced by the oxidation of the benxoyl derivative of 8-amidovaleraldehyde (Abstr., 1892,1484), which melts a t 66O; the other product is a hygroscopic syrup which is also formed when piperidine is oxidised with potassium permanganate. Carbon bisulphide converts 6-amidovaleraldehyde into the dithio- carbamate of piperidine (m, p. 169-171°), and by its action on amido- valeropropaldehyde, gives rise to the dithiocwbamate of coniine, which melts at 58-61".I n the behaviour of amidovaleraldehyde towards nitrous acid, however, i t resembles ordinary amidoaldehydes. M. 0. F. Action of Water on Acraldehyde Dibromide. By CORNELIS A. LOBRY DE BRUYN (Rec. Y'yav. Chim., l898,17,259--262).-Although acraldehyde dibromide is converted into bromacraldehyde when boiled with a 50 per cent, aqueous solution of sodium acetate (Piloty and Stock, Abstr., 1898, i, 402), it apparently gives rise to glyceraldehyde when left in contact with water, either a t the ordinary temperature, or, better, at that of the water-bath. On removing the hydrobromic acid from the solution by successive treatment with lead carbonate, hydrogen sulphide, and moist silver oxide, and subsequently concen- trating in a vacuum, a syrup is obtained which reduces Fehling's solution, and gives rise to glycerosazone when mixed with a solution of phenylhydrazine acetate.[NOTE BY AssTRAcToR.-since the original paper was published, Wohl (Ber., 1898, 31, 2394) has prepared glyceraldehyde from the acetal of acraldehyde, in the form of a white, crystalline powder.] W. A. D. Acetylrnethylheptenone (2 Methyl-2-nonene-6 : 8-dione). By PHILIPPE BARBIER and GEORGES LESER (Bull. Xoc. Chim., 1897, [iii], 17, 748--751).-Nstural methylheptenone (Z-methyl-2-heptene-6-one) readily reacts with ethylic acetate in the presence of sodium, with the formation of ci,cRt~li,znthyZl~e~~e~~o~ze, CMe,:CH*CH,*CH,*CO*CH,* COMe. The latter is purified by conversion into its copper derivative, a paleORGANIC CHEMISTRY.211 blue, crystalline powder melting a t 132-133', from which it is regenerated by the action of dilute sulphuric acid. Acetylmethyl- heptenone is a colourless liquid of powerful aromatic odour and having a sp. gr. = 0.954 a t 0'. It boils at 114-115' under a pressure of 15 mm., and at 233-234', with slight decomposition, a t the ordinary pressure. Treatment with the theoretical quantities of hydroxylamine hydrochloride and sodium carbonate converts it into the oxaxole, CMe,:CH*CH,*CH,*C< CH:(?Me, which boils at 118-119' under a pressure of 14 mm., whilst the dioxirne, a crystalline substance melting at 109-llOo, is also formed. N-0 Ace tylme th y lhep tenone Forms a sodium derivative, CMe,: CH-CH,*CH,*CO CHNa COMe, which, when warmed for some hours with ethylic monochloracetate, is converted into a mixture of the ethylic salts of 2-methyl-2-hexenoic acid, levulinic acid, and 2-methyl-2-nonene-6-onoic acid.The first two of these compounds are formed by the action of alcohol, and the third by the action of water, on the normal product of the reaction, which would have the composition CMe,: CH*CH,*CH,*CO* CH( COMe) CH, COOEt. Ethylic 2-methyZ-2-hexenoate, CMe2:CH.CH;CH2*COOEtj, is a colour less liquid of agreeable odour which boils a t 182-184' and has a sp. gr. = 0.928 at 0'. On hydrolysis, it yields 2-methgl-2-hexenoic acid, which is a colourless liquid boiling at 216-218". Ethylic 2-methyZ-2-nonene-6-onoate boils a t 152-1 54' under a pressure of 14 mm. and has a sp.gr. =Om988 a t 0'. The corres- ponding acid cry stallises from light petroleum in colourless needles melting at 57". The ethylic salt forms a phenylhgdraxone, which melts at 93' and boils at 235-240" under a pressure of 15 mm. The sodium derivative of acetylmethylheptenone reacts with ethylic iodide to form acetylmet?Lylethylheptenone, which boils a t 133-135' N. L. Conversion of Ketones into Diketones. 111. By MICHELE FILETI and GIACOMO PONZIO (J. pr. Chena., 1898, [ ii], 58, 362-367).- Further investigations have confirmed the conclusions already arrived a t (Abstr., 1897, i, 317). Ethyl butyl ketone yields a mixture of two diketones, acetylualergl and propionyZbwtg?*yl, and two dinitrohydrocarbons ; of the former, the mixture of dioximes was so far separated by fractional crystallisation from dilute-alcohol t h a t fractions melting at 168-170'and 141-144' were obtained ; as regards the dinitrohydrocarbons, potassiodinitro- ethane is more soluble than the corresponding butane derivative.Ethyl amyl ketone behaves in a similar manner ; acetylhexoyl and propionyl- valeryl are the diketones ; the dioxime and osazone of the latter melt at 139-141" and 96-97' respectively ; as regards the dinitrohydro- carbons, potassiodinitroethane is more soluble than the corresponding pentane derivative. Ethyl isoamyl ketone yields acetylisohexoyl and dinitroethane only ; the dioxime of the former was also prepared from ethylic isoamylacetoacetate. Ethyl isohexyl ketone yields under a pressure of 15 mm. acetylisoalnylacetyl and dinitroethane only. c.F. 6,112 ABSTRACTS OF CHEMICAL PAPERS. Acetylation with the help of Sulphuric Acid. By ZDENKO H. SKRAUP (Monatsh., 1898, 19, 458-460).-The author points out that Franchimont (Abstr., 1880, 159) was the first to draw attention to the value of sulphuric acid as an addition to acetic anhydride in acetyl- ating (compare Thiele, Abstr., 1898, 469), and the method has long been employed in the author's laboratory. The reaction is liable to become uncontrollable unless precautionary measures are taken. By the action of acetic anhydride containing Less than 1/100 per cent. of its weight of sulphuric acid on mucic acid, tetracetylmucic acid is easily produced in amount equal to 79 per cent. of that theo- retically possible. By the usual method of heating the acid with acetic anhydride and anhydrous sodium acetate, only amorphous products are obtained. With smaller quantities of sulphuric acid ( l / l O O O O per cent.), the reaction still goes on, but is probably in- complete.The method of estimating acetyl used by Wenzel (Abstr., 1898, i, 234) was published 6rst by Franchimont (Ber., 1879, 12, 1940), and modified later by the author (Abstr., 1894, i, 15). By DIOSCORIDE VITALI (L' Orosi, 1898, 21, 114--117).--0ne hundred parts of dry sodium valerate and 117 parts of crystallised zinc sulphate are separately dissolved in the smallest possible quantity of hot water, the solutions mixed, the liquid evaporated t o dryness at a temperature not exceeding 70°, and the finely powdered residue extracted with 95 per cent.alcohol. On concentrating the alcoholic extract by evaporation a t 70°, zinc valerate is obtained in a very pure crystalline condition. This process is simpler and more economical than those commonly employed. A . L. Preparation of Zinc Valerate. N. L. Wax of the Humble Bee. By ERNST E. SUNDVIK (Zeit. physiol. Chern., 1898, 26, 56-59).-Samples of wax taken from the nests of Bombus musca!runz and B. lapidarius have the same chemical proper- ties. The mixture of wax and pollen, freed from eggs and larvse, and extracted with ether or chloroform, yields a crude wax of brownish- yellow colour, melting at 35-40', and having an agreeable odour resembling honey. This substance still contains fat and colouring matter. The principal constituent of the wax is an alcoholic sub- stance, which is freed from glycerides by treating the partly purified product with weak potash on the water-bath.After repeated crys- tallisations from alcohol, the unaltered residue melts at 74-75', and its composition agrees with the formula C,,$,,O ; it forms flexible, woolly needles which can be easily kneaded into a pale yellow cake. A berhzoyl derivative, C3,H,,0Bz, obtained by heating the substance with benzoic anhydride a t 150-1 60', crystallises from alcohol, benz- ene, and petroleum, and melts a t 55'. Ethylic P-Isopropylacetobutyrate and Stereoisomeric Di-isopropylbutenedicarboxylic Acids. By PHILIPPE BARBIER and V. GRIGNARD (Compt. rend., 1898, 126, 251-253).-Ethylic isobutylideneacetoacetate and ethylic malonate suffer condensation in the presence of potassium ethoxide, yielding a liquid which, when G.T. M.ORGANIC CHEMISTRY. 113 distilled, first under ordinary and subsequently under reduced pressure, gives rise to two substances; the chief product, a colourless liquid boiling a t 170' under atmospheric pressure, consists of ethylic p-isol3?.opylacetobutyrate, CH2Ac*CHPrN2H,* COOEt ; the product obtained in less quantity is an unstable intermediate com- pound, COOEt*CHAc*CHPr~*CH(COOEt),, boiling at 189-191' under a pressure of 10 mm., which passes into the preceding substance by the loss of two COOEt groups. When ethylic P-isopropylacetobutyrate is treated with sodium ethoxide, two molecules of the former coalesce, and condensation takes place, accompanied by the elimination of two molecules of acetone.The ethereal salt, C,,H,,O,, which is obtained, boils at 156' under a pressure of 10 mm., and on hydrolysis furnishes a mixture of two isomeric di-isopro~yl6utenedicurboxylic acids, having the formula COOH- CH,* CPrp:CPrP*CH,*COOH ; one crystallises in needles melt- ing at 156-15S0, and the other in colourless plates melting a t 11 7-1 19'. The stereoisomeric relationship of these isomerides has not yet been determined. G. T. M. Syntheses with Ethylic Cyanacetate. By TIMOTH~E KLOBB (Ann. Chim. Phys., 1897, [vii], 10, 145-214).--EthyZic isovaleryl- cyanacetate, CHMe,. CH,. CO*CH(CN)*COOEt, produced by adding an ethereal solution of isovaleric chloride to an alcoholic solution of ethylic cyanacetate in the presence of sodium ethoxide, separates in white needles when the oily product is cooled to - 36'; it melts at +21°, boils at 138-140' under a pressure of 21 mm., at 144-148' under 31 mm., and decomposes when distilled at the ordinary pressure ; its specific gravity = 1.030 a t 24'.The substance is a strong acid, not only decomposing carbonates, but its alcoholic solution dissolves the metals, magnesium, zinc, iron, aluminium, copper, cobalt, and nickel, with the evolution of hydrogen ; silver, bismuth, and antimony are not attacked. The mag?zesiurn, ferrous, and coppel. derivatives obtained in this manner by the displacement of the hy- drogen in the CH group are described. Methylic isovalerylcyanacetate, prepared like the ethylic salt, crys- tallises in rhombic plates melting a t 41-42', and boils without decom- position a t 171-172' under a pressure of 100 mm.; its sodium, cal- cium, 6arium, and silver derivatives are crystalline. Both ethereal salts are insoluble in water, but dissolve easily in the usual organic solvents. When boiled with aqueous potash, they undergo hydrolysis, am- monia, the potassium salts of carbonic, acetic, and isoyaleric acids and the corresponding alcohol being produced ; long continued boiling with water results in the formation of tarry products and a small quantity of a compound having the formula C,,H,,N,O, and crystallising in white needles melting a t 133-134'. The preparation of the alkylic derivatives of diphenacylcyanacetic acid (PP-dibenzoylcyanisobutyric acid) is given in detail ; the propylic salt, obtained by the action of bromacetophenone on ruethylic cyanacetate, dissolved in propylic alcohol, in the presence of sodium propyloxide, crystallises from alcohol in nacreous leaflets and melts at 114'.The isobutylic salt could not be obtained by this method ; the VOL. LXXVI. i. i114 ABSTRACTS OF CHEMICAL PAPERS. methylic and ethylic salts have been previously described (see A.bstr,, 1894, i, 592; 1897, i, 531). Phenylhydrazine gives rise to no definite hydrazones with these ethereal salts. On hydrolysis with boiling alkalis, they yield diphenacylacetic acid (PP-dibenzoylisobutyric acid). The preparation of the alkylic phenacylcyanacetates (a-cyano-/3-benz- oylpropionates) is described at some length; an account of these com- pounds and of the free acid has already been published (see Abstr., 1896, i, 126).P-Benzoylpropionic acid is the final product of the action of potash on these ethereal salts. The syntheses based on the displacement of the hydrogen of the group CH in the above ethereal salts have already been studied (Abstr., 1896, Zoc. cit., and 1897, i, 419 ; 1898, i, 586) ; the prepara- tion of the methylic, ethylic, and benzylic substitution products are fully described in the paper. Ethylic and methylic a-cyano- P-acetylpropionates have already been described (Abstr., 1896, Zoc. cit.). G. T . M. Constitution of Tetric Acid and of the Lactone of 7-Hydroxydimethylacetoacetic Acid. By MAX CONRAD and RICHARD GAST (Ber., 1898, 13, 2726--2731).-Methylic monobromo- dimethylacetoacetate, which has been previously described (Abstr., 1897, i, 321), boils a t 225-230" under atmospheric pressure, under- going slight decomposition.When the acetate prepared from this compound by means of potassium acetate is kept for some months at the ordinary temperature, it yields methylic acetate and the lactone of y-hydroxydirnethylacetoacetic acid (2 : 2-dimet hyl-3-butanone-4-oloic acid, CMe,<CO,O , which is a coIourless oil of sp. gr. = 1.147 at 18'/15O, and boils at 208-212' without decomposing. The dilute alcoholic solution gives no reaction with ferric chloride. Bromine converts the lactone into a monobromo-derivative, which is decomposed by water with formation of the lactone of dihydroxydimethylaceto- acetic acid. Aniline converts the original lactone into a derivative, C,,H,30,N, which crystallises in compact, lozenge-shaped crystals melting a t 88' and boiling at 300-310"; this compound, which is decomposed by aqueous baryta and by platinic chloride, probably has the constitution CMe,<~&~~>CH,.The lactone readily reacts with hydroxylamine hydrochloride to form an oximidolactone, OH N:C<CMe2. CO' which melts at 134", and gives no coloration with ferric chloride ; the corresponding phenylhydraxone melts at 131", and is sparingly soluble in light petroleum. Methylic tetrate, CO*QH, CH,--F) CB2-0 OMe*CGCMe. bo, prepared by the action of methylic iodide on silver tetrate, is a colourless liquid boiling at 215-220"; it is isomeric with the lactone just described, but does not yield derivatives with hydroxylamine or phenylhydrazine, whilst acids reconvert it into tetric acid.The fact that the lactone of y-hydroxydimethglacetoacetic acid is soORGANIC CHEMISTRY. 115 dissimilar from tetric acid both in chemical behavionr and boiling point renders it improbable that the latter is the lactone of y-hydroxy- methylacetoacetic acid, having the formula CO-0 CHMe<(J*.&,' A. H. Reduction of Aconic Acid to Paraconic Acid. By HANS REITTER (Ber., 1898, 31, 2722--2725).--Aconic acid is readily con- verted into paraconic acid when it is treated with glacial acetic acid and zinc dust, although Fittig (AnnaZen, 1883, 216, 97) was unable t o effect this reduction by means of sodium amalgam. The ready formation of paraconic acid affords further evidence in favour of the formula COOH*C< CH-? for aconic acid proposed by Fittig.CH, CO A. H. Syn thesis of Terebic Acid. By EDMOND E. BLAISE (Compt. vend. , 1898, 126, 349--351).-Ethglic bromosuccinate and acetone are mixed together in the presence of a copper-zinc couple and the mixture is occasionally shaken during 24 hours. The double zinc compound pro- duced is decomposed by dilute sulphuric acid, and the ethylic terebate is extracted by means of ether and hydrolysed by aqueous potash. The acid is liberated by hydrochloric acid and purified, first by conver- sion into its soluble barium salt, and subsequently by recrystallisation from water and alcohol ; it melts a t 174", and is furthur identified by conversion into methyl-2-pentanolide. The yield of terebic acid from ethylic bromosuccinate is 10-12 per cent., that from pinene is less than 2.G. T. M. Tautomeric Forms of Ethylic Isaconitate and of Ethylic Dicarboxyglutaconate. By MAX GUTHZEIT (Ber., 1898, 31, 2753--2758).-Ethylic isaconitate is a thin, colourless liquid which boils at 178-180' under a pressure of 20 mm. and has the sp. gr. = 1.1291 at 20°/200. This constitutes the enolic form of the compound, and gives a deep blue coloration with ferric chloride, whilst it also forms a copper salt, and is a t once coloured deep yellow by sodium carbonate. This form is always obtained by the ordinary methods of preparation, but changes very slowly, if kept, into the ketonic or true form, which is also produced in a few hours when a small amount of piperidine is added t o the enolic form. The ketonic form is a very viscid, deep yellow oil which cannot be distilled without undergoing decomposition, and has a sp, gr.= 1.1432 at 20°/200. It gives no colorittion with ferric chloride, does not yield a copper salt, and is only slowly coloured yellow by sodium carbonate. When it is dissolved in alcoholic sodium ethoxide and the solution acidified, the enolic form is regained. Both forms ham the same molecular weight as determined by the boiling point method. The two forms of this compound probably have the following constitutions, COOEt*CH:CH*CH(COOEt), ; COOEt*CH:C H*C(COOEt):C(OH)*OEt Ethylic dicarboxyglutaconate appears also to exist in two forms, the enolic form being that which has previously been described, whilst the i 2116 ABSTRACTS OF CHEMICAL PAPERS. ketonic or true form, which is produced by the action of piperidine and is also formed when the enolic form is kept for along time, crys1,allises in monosymmetric crystals melting at 101-102'.The latter have only been obtained in very small amount, and are being further in- vestigated. A. H. Condensation of Ethylic Malonate with Aldehydes under the Influence of Ammonia and Organic Amines. By EMIL KNOEVENAGEL (Be?., 1898,31, 2585-2595. Compare Abstr., 1894, i, 570, &c.)-Methylenebispiperidine and methylenebisaniline react readily with ethylic malonate when heated with i t on the water-bath, yielding ethylic methylenebismalonnte. When aniline is added to ethylic malonate mixed with formaldehyde, no action takes place a t the ordinary temperature, and methyleneaniline does not react with ethylic malonate t o form ethylic methylenebisrnalonate. The best method for the production of the latter substance is to add a small quantity of an amine, usually piperidine or diethylamine, to a mixture of formaldehyde and ethylic malonate mixed in the requisite pro- portions. Ethylic ethylidenebismalonate, prepared in a manner similar t o the above, boilsat 208-209' under a pressure of 17 mm.; it is accom- panied by ethylic ethylidenemalonate. The derived P-methylglutaric acid melts at 87", and its anhydride a t 47".Ethylic isobutylidenebis- mazonate boils at 198' under a pressure of 12 mm., and /3-isopropyl- glutarir: acid prepared from it melts at 96-5-97' (Schryver, Trans., 1893, 1345, gives 99-looo), and affords a silver salt, C',H1204Ag2, which is sparingly soluble in water.Ethylic P-isopro~ylglutarcLte is a thick oil having a pleasant odour, and boils a t 250' under atmospheric pressure. Ethylic &soamyZidenebismcllonate, C19H3208, boils at 204' under a pressure of 15 mm. P-&obutylghtaric acid crystallises in long, white needles, and melts at 48'; it is very soluble in ether, alcohol, glacial acetic acid, and water, and somewhat readily in carbon bisulphide and light petroleum; its copper, zinc, and lead salts are insoluble in water, and the silver salt, C,Hl,04Ag2, is a white, curdy precipitate. Ethylic cenanthylidenebismalonate, C21H3608, boils at 195' under a pressure of 16 mm. ; the corresponding P-liexylgluturic acid was obtained in very small amount, and melted at 215-236O. Aromatic aldehydes and ethylic malonate condense in molecular proportion under the influence of amines.Ethylic benzylidene malonate is easily obtained by treating a mixture of benzaldehyde (1 mol.) and dry ethylic malonate (1 mol.), with a little piperidine or alcoholic ammonia. [With F. GIESE.]--Ethy&c cumylidenemalonate, C17H2204, i s a light yellow oil, and boils at 205-208' under 15 mm. pressure. [With H. HoFFMANN.]-E~~,Y~~c pcbranitrobenxylidenemaZorzate, CI4H,,O9N, forms colourless needles and melts at 94'; it dissolves readily in hot alcohol, light petroleum, and benzene, but only sparingly in ether. F(CO0Et):CH CO O>'GH49 is made by Ethylic coumarincarboxylate, the condensation of salicylic aldehyde with ethy lic malonate by meansORGANIC CHEMISTRY. 117 of piperidine or ammonia; it forms crystals, and melts at 94"; coumarincarboxylic acid melts at 185-1 87".[With A. G~oos.]--Ethylic ccnisylidinemalonate, Cl5HI8O5, boils at 200-211° under 14 mm. pressure, and melts at 38-40' ; It dissolves readily in ether, benzene, and alcohol. Ethylic rnethylsalicylidene- rnalonate, C,,H,,O,, boils at 193-195O under a pressure of 14 mm., and could not be soldified. [With F. GIESE.] -Ethylic piperonylidenemalonate boils a t 2 16-219' under a pressure of 11 mm., crystallises from alcohol in beautiful, colourless prisms, and melts at 63' ; it is readily soluble in cold benzene and aceticacid, and in warm ether and alcohol, and is sparingly soluble in light petroleum. Et hylic f urfurylidenemalonate, which may be produced in several different ways by the condensation of furfuraldehyde and ethylic malonate, is obtained in small amount by merely warming the com- ponents together on the water-bath, but the yield is greatly augmented by the addition of a little piperidine. Uric Acid and the Murexide Reaction.By DIOSCORIDE VITALI (L'Oposi, 1898,21, 73--80).--The fact that the presence of small quantities of iodides in urine cannot be directly demonstrated by the usual methods has been attributed to the oxidation of organic compounds, especially uric acid, by the iodine at the moment of its liberation, with simultaneous formation of hydriodic acid. The pro- duction of the latter is shown by the immediate liberation of iodine on adding iodic acid, and by means of this reagent traces of iodine in the form of iodides may readily be detected in urine.I f , moreover, a solution of iodine be gradually added to a solution of potassium urate mixed with a little starch paste, no blue coloration appears until a considerable amount of iodine has beon absorbed; the liquid a t the same time becomes acid from the production of hydriodic acid, and deposits a crystalline precipitate of ixric acid. A por- tion of the latter is simultaneously oxidised to carbamide and alloxan, as was proved by the isolation of urea oxalate and by the fact that the liquid gave the murexide reaction when evaporated to dryness and gently heated. This formation of murexide (ammonium purpurate) is probably due t o the action of the ammonia, produced by the decomposition of the carbamide, on the alloxantin formed by the reduction of the alloxan by hydriodic acid.Instead of iodine, chlorine, bromine, iodic acid, and nitric acid may be used. In the last case, the necessary reduction in the latter phase of the reaction is, perhaps, brought about by nitric oxide or nitrous acid, but the action of chlorine is not easily explained. The use of bromine or iodine instead of nitric acid in the murexide test for uric acid is recom- mended as giving more certain results, with less liability to failure from excessive heating. Hypoxanthine, xanthine, theobromine, and caffeine, when subjected to successive oxidation and reduction under the same conditions as uric acid, also yield murexide, and the absorp- tion of iodine by urine is partly due to the presence of the two first- named compounds. It is found, in fact, that the elimination of the uric acid and urates from urine does not wholly obviate the difficulties in the detection of traces of iodides therein, N.L. A. L.11s AI3STRACTS OF CKEMICAI, PAPERS. Nitrobiuret and Amidobiuret. By JOHANNES THIELE and EMIL UHLFELDER (AnnaZen, 1898, 303, 93--107).--Nitro6izlret, NO,* NH* CO *NH* CO *NET,, prepared by adding biuret in small portions to a mixture of concen- trated nitric and sulphuric acids, separates from water as a white, crystalline powder, which melts and decomposes a t 165'; it does not develop colour with alkali and copper sulphate, but gives the nitramine reaction with ferrous sulphate and sulphuric acid, and is resolved by boiling water into carbonic anhydride, nitrous oxide, and carbamide. Tbe potassium and silver derivatives are anhydrous.Dinitrobiuret, NH( CO *NH*NO,),, produced when the finely divided nitro-derivative is added t o fuming nitric acid cooled with a freezing mixture, crystallises from methylic alcohol in white needles, and explodes a t 124'; it gives the nitramine reaction, and is resolved into nitrous oxide, carbonic anhydride, and ammonia under the influence of boiling water. The potccssium derivative crystallises from water in colourless, rhombic plates, Benxylidenearnidobiuret, CHPh :N*NH* CO *NH* CO *NH,, obtained on reducing nitrobiuret, and treating the product with benzaldehyde, crystallises from alcohol in small, white needles, and melts a t 202". Amidobiuret hydrochloride is formed when the benzylidene derivative, moistened with alcohol, is heated with concentrated hydrochloric acid on the water-bath ; i t crystallises from alcohol in plates, and melts a t 185'.It dissolves readily in water, and is gradually resolved into ammonium chloride and hydrazodicar bonimide (urazole) when the aqueous solution is boiled ; i t reduces cold, ammoniacal silver nitrate and. hot Fehling's solution. The nitrate crystallises from boiling alcohol in beautiful needle^, and melts a t 165' ; i t is best prepared by the action of concentrated nitric acid on the acetone (P-propylidene) compound, CMe,:N*NH* CO-NH* CO-NH,, which crystallises in white needles and me1t.s a t 1 8 9 O . The picrate melts at 175'. CN*CMe,*NH.NH*CO*NH*CO*NH,, prepared by the action of hydrogen cyanide on the acetone compound of amidobiuret, crystallises in prismatic plates and melts a t 146'; oxidation with potassium permanganate converts i t into allophanyl- axoisobutyronitrile, (2" CMe,*N:N* CO *NH* CO *NH,, which crystal- lises from benzene in yellow, rhombic plates, and melts and decomposes at 127".A ZZopharLyZhydraxoio~utyronitriZe,~ N N AZZophanaxide, NH,* CO *NH* CO *N<r I , obtained by the action of nitrous acid on amidobiuret, melts and decomposes at 195'; i t is insoluble in water, but dissolves in aqueous ammonia and in alcohol, undergoing decomposition. Silver nitrate precipitates, from the alco- holic solution, a white, highly explosive substance, which dissolves in ammonia and nitric acid. When the azide is heated with boiling alcohol, diazoimide is eliminated, and ethylic allophanate produced.Z'etwret, NH(C0 *NH*CO *NH2)2,. prepared by the action of am- monia on allophanazide, crystallises in colourless, rhombic prisms, and AlZophC~il~ll is the name given by the authors t o the: radicle NH,*CO*NH*CO.ORGANIC CHEMISTRY. 119 melts at 186" ; copper sulphate and alkali develop a deep violet colora- tion, more intense, but less red than the biuret reaction. M. 0. I?. Nitrodicyanodiamidine and Amidodicyanodiamidine. By JOHANNES THIELE and EMIL UHLFELDER (Annalen, 1898, 303, 107-1 14).-Nitrodicyanodia~~aidine, N02*NH* CO *NH* C(NH,):NH, prepared by adding :dicyanodiamide to a mixture of concentrated nitric and sulphuric acids, forms a microcrystalline powder soluble with difficulty in water and in alcohol; i t is neutral in reaction, and when heated with water, becomes alkaline, with elimination of nitrous oxide and carbonic anhydride, guanidine carbonate crystallising from the liquid.The silver derivative decrepitates when heated. Amidodicyanodiamidine dihydrochloride forms white needles and melts at 181"; the picrate becomes brown at 1 9 8 O , and melts at 336". The benzylidene compound forms a hgdrochloride, which crystallises from alcohol in white prisms and melts a t 226". Acetoneamidodicyanodiamidine hydrochloride, CMe,:N*NH* CO *NH* C(NH,):NH,HCl, crystallises from alcohol in small, white leaflets and needles, and melts at 206". Guanidinecarboxylazide hydrochloride, N,. CO *NH* C(NH,):NH, HCI, prepared by adding cold, aqueous amidodicyanodiamidine hyd Po- chloride to chloroform saturated with dried nitrous anhydride, melts at 157", and explodes when heated on platinum foil.Boiling alcohol eliminates diazoimide, and yields the compound C,H,,N ,05, which crystallises in elongated, thin prisms and melts at 187". &I. 0. F. Chemistry of Acetylene. By GEORG SCHROETER (Annalen, 1898, 303, 114-132. Compare Abstr., 1898, i, 614).-Acetaldehydedi- sulphonic acid, COHO CH(S0,H)2, produced by the action of concen- trated sulphuric acid on acetylene, has not been obtained crystalline, but forms a syrup which dissolves in alcohol. The bayium salt con- tains 2H,O, and the basic barium salt, which is less readily soluble, crystallises from water in needles containing 4H,O ; the potassium sait contains 1H,O, and when treated with potassium hydrogen sulphite, yields the potassium hydrogen sulphite compound of potassium acetaldehydedisulphonate, already obtained by Rathke from chloral and potassium sulphite.The sodium salt dissolves in water more freely than the barium and potassium salts, and contains 1H,O ; the silver, copper, and lead salts are also readily soluble, and the basic lead salt contains 1H,O. Acetaldoximedisulphonic acid, NOH:CH* CH(SO,H),, forms a potassium salt which crystallises from water in lustrous needles con- taining 1 H,O. Acetaldehydephenylhydrazonedisulphonic acid, NHPh*N:CH- CH(SO,H),, forms a barium salt which crystallises from water in leaflets contain- ing 2H20. Acetalazinetetrasulphonic acid, N,[ :CH* CH(SO,H),],, forms a barium salt which contains 6H20 ; the hyclraxine salt contains 2H20, and decomposes a t 200O.The SuZplzates of acetaldehydedisulphonic acid, S,O,H* CH(OH)CH(SB,H),, and SO,[* O*CH(OH)*CH(a03€T).L]2,120 ABSTRACTS OF CHEMICAL PAPERS. are also produced when fuming sulphuric acid is saturated with acetylene. M. 0. F. 1 : 2-Acetylfurfuran ; and its Occurrence in Wood Tar. By LOUIS BOUVEAULT (Compt. Tend., 1897, 125, 1184--1186).-This com- pound is produced synthetically by heating together on the water- bath ethylic pyromucate and ethylic acetate in the presence of sodium. The product, after treatment with dilute hydrochloric acid, yields 1 : Z-ethylic pyrornucylacetate, C,OH,* CO*CH,* COOEt, which boils at 142-143' under a pressure of 10 mm. and has a n odour resembling that of ethylic acetoacetate.7H:CH CH:CAc 2-A cet ylfitifuran, >O, produced by the hydrolysis of the preceding compound with 25 per cent. sulphuric acid, boils a t 67" under a pressure of 10 mm., solidifies to a mass of crystals melting at 29*5", and has an odour recalling that of acetophenone. The oil boiling between 150-200°, obtained by the distillation of beech- and oak-wood after removal of the phenolic and basic sub- stances, is rectified under reduced pressure. The fraction boiling between 60" and 70" under a pressure of 10 mm. is treated with excess of hydroxylamine ; the product distilled under the same pressure yields a mixture of oxirnes boiling at 105-115". The distillate yields a crop of crystals melting a t 127-128', and consisting of the oxime of methylcyclopentenone, C,H,O, a compound already obtained from wood tar.By warming the oxime with acetic anhydride, a n acetyt derivative, C,H,N* OAc, is produced, which boils a t 123" under a pressure of 10 mm., and crystallises in needles melting a t 73'. The greater portion of the rectified oximes remains liquid, and on treatment with acetic anhydride yields the acetyl derivative of 1 :2-acetylfurfuranoxirne which boils a t 135' under a pressure of 10 mm., and crystallises from ether in needles melting a t 96'. 1 : 2-Acet~lfwfurunoxirne is obtained by bydrolysing the acetyl corn- pound with alcoholic potash ; i t boils at 110-1 11' under a pressure of 10 mm., and crystallises from ether in well-defined prisms melting a t 104". When the oxime is hydrolysed with 25 per cent.sulphuric acid, 1 : 2-acetylfurfuran is regenerated. G. T. M. Decomposition of Pyrornucates of the Alkaline Earths. By PAUL FREUNDLER (Bull. #OC. Chirn., 1897, [iii], 17, 609-612).-The author has prepared furfuran by Limpricht's method (Annulen, 1873, 165, 281), namely, by heating barium pyromucate with soda-lime. It is not advisable to use more than 100 grams of the barium salt at once, and the yield is extremely poor, only some 4-6 grams of furfuran being obtained from 100 of the barium salt. A considerable amount of gas is evolved during the reaction, and this consists of equal volumes of an unsaturated hydrocarbon, C,H, (this vol., i, 98), and of carbonic oxide, or hydrogen when an excess of soda-lime is employed. No better yield could be obtained by employing the calcium in place of the barium salt.Experiments have also been made by heating the barium salt with barium oxide under reduced pressure, and also byORGANIC! CHEMISTRY. 121 heating the barium salt alone, both under atmospheric and reduced pressures; the products obtained in all cases mere furfuran (10-12 per cent., hydrocarbon, C,H, (5-6 per cent.), carbonic oxide (3-4 per cent.), hydrogen and the ketone, (C,H,O),CO (1-2 per cent.). J. J. S. A New Series of Cyclic Ketones. By AUGUSTE BEHAL (Compt. rend., 1897, 125, 1036--1038).--The heavy oil obtained by the distillation of wood t a r consists of a mixture of acidic, basic, and neutral substances; the new ketones are separated from the neutral portions by extraction with concentrated hydrochloric acid, in which they are soluble. The acidic extract, diluted, and subjected t o distillation with steam, yields a distillate containing the ketones in the form of a supernatant, yellow oil having an odour of menthol, and boiling between 180' and 205'.The ketones differ in their solubility in hydrochloric acid, and a partial separation may be effected by the use of various strengths of acid. The greater portion of the mixture is dissolved by a solution of dilute acid (1 : 2), and this portion, when rectified, distils a t 190-192'. The ketones in the distillate are converted into oximes, and these into their benzoyl derivatives. The latter can be separated into two distinct substances, the one less soluble in benzene, alcohol, and ether, and melting at 167O, the other far more soluble in these solvents and melting at 128-129'.The oximes are regenerated by the alkaline hydrolysis of the two benzoyl derivatives, that derived from the less soluble benzoyl derivative (m. p. 1G7°):melting a t 121*5', and that from the more soluble compound (m. p. 129') a t 102.5'. The parent ketones are obtained by distilling the oximes with 20 per cent. hydrochloric acid. The oxime of higher melting point yields a ketone which boils at 192' under a pressure of 760 mm., and is soluble in water and the ordinary organic solvents. This ketone can be obtained in crystals and melts a t 12'; its sp. gr. =Om9866 at Oo. Another ketone, which also boils a t 192O, is furnished by the oxime of lower melting point ; i t does not solidify when cooled to - 27'; it is soluble in water and the ordinary organic solvents, and its sp.gr. =0*9539 a t 0'. The quantity of these ketones in the heavy oilof wood tar amounts to 16 per cent., and they belong chiefly to the tetrahydrobenzene series. G. T. M. Action of Potassium Hydrosulphide on Orthocyanobenzylic Chloride. By SIEGMUND GABRIEL and ERNST LEUPOLD (Bey., 1898, 31, 2646-2654. Compare Abstr., 1890, 1249)-When orthocyano- benzylic chloride is treated with potassium hydrosulphide, a compound, C,H,NS, is produced, which may be regarded either as orthocyano- benzylic mercaptan, CN- CGH,* CH,. SH, or as thiophthalimidine, N-rI --UH, C6H4<C(NHPS. The continued action of potassium hydrosulphide . I CH produces dithiophthcclide, C6H4(CS$S, which crystallises in reddish, flat plates melting a t 68'; this substance again is converted by excess of the snlphide into a sparingly soluble compound, C,,H1,S,, which122 ABSTRACTS OF CHEMICAL PAPERS, crystallises in needles with a green reflex, and probably s ti t u t ion CH,<CF>C: C<-">CS.acid, this compound is converted into dithiodiphthalyl, On oxidat ion 6 4 C6H4 has the con- with nitric which crystallises in loni, greenish-ydlow needles, and melts at 332-333O (uncorr.). Fuming nitric acid converts dithiodiphthalyl into diphthalylic acid, C,,H,,O,,. and i t s constitution is thus established. When this is boiled with alkalis, i t yields a salt of the corresponding hydroxy-acid, which is decomposed by acids, with formation of the dilactone. When a solution of dithiodiphthalyl in alcoholic sodium methoxide is treated with methylic iodide, the tetramethylic derivative SMe* CO*C,H,* C(OMe):C(OMe)*C,H,* CO*SMe, of this acid is pro- duced, which crystallises in yellow, six-sided tablets melting at 160-161° ; on reduction, this methylic derivative is converted into two isomeric compounds, Cl6H1,O4, one of which is an acid, and the ot'her an indifferent substance.The former crystallises in oblique prisms and melts a t 228-229', whilst the latter forms snow-white needles melting at 255-257'; the constitution of these two com- pounds is shown by the fact that they are both formed when deoxy- benzoinorthodicarboxylic acid, COOH. C6H4* CH,. CO-C,H,* COOB, is heated, and are reconverted into this acid when they are heated with alkalis.The indifferent substance is, therefore, an inner anhy- dride of deoxybenzoindicarboxylic acid, whilst the acid is a lactonic acid, the exact constitution being still uncertain in both cases. A. H. Electrolytic Reduction of the Nitro-group. BY WALTHER LOB (Zeit. Elektvochem., 1898, 4, 428. Compare Abstr., 1897, i, 331 ; and 1898, i, 14).-The author's object was to isolate intermediate reduction products by adding a substance which will combine with them, and so withdraw them from further reduction. When a mixture of 10 grams of nitrobenzene, 35 grams of fuming hydrochloric acid, 25 C.C. of water, arid 70 C.C. of alcohol is placed in a porous cell containing a lead cathode, and this is immersed in dilute sulphuric acid (1 : 10) contain- ing a platinum anode, aniline is practically the only product obtained with E.M.F.'s from 2.5 to 6 volts, and temperature from 20'to 80'.When the 25 C.C. of water is replaced by 25 C.C. of 40 per cent. form- aldehyde solution, and the electrolysis conducted with 5 volts and 2 amperes, a t 45-60", a polymeride of pa,ranhydrohydroxylamino- benzylic alcohol, (OH* CH,* C6H,-NH* OH - H,O),, is obtained. This compound is also formed by the interaction of phenylhydroxylamine and formaldehyde i n presence of hydrochloric acid. It is a red, amorphous powder, which yields paraleucaniline with aniline and aniline hydrochloride, whilst with nitrous acid a diazo-derivative is formed which yields parahydroxybenzaldehyde on boiling. Its hydro- chloride dissolves in warm, concentrated hydrochloric acid, and the free base is obtained by pouring this solution into dilute ammonia.The base decomposes a t high temperatures without melting, may be boiled with caustic soda without decomposition, is iasolnble in mastORGAN 1C CHEMISTRY. 123 solvents, slightly soluble in chloroform, and more so in aniline and concentrated sulphuric acid. When the electrolysis is carried out with 2.8-3 volts at 30°, methylenediparanhydroamidobenzylic alcohol, HN* C,H,* CH, CH2<HN* C,H,* CH,>09 is the only product. This substance has not previously been described, and may be obtained by the direct interaction of aniline and formalde- hyde. The hydrochloride and platinochloride were analysed. The base is a pale yellow, amorphous powder, soluble in dilute acids, chloroform, and aniline, less soluble in alcohol and glacial acetic acid, insoluble in water, ether, alkalis, and light petroleum.Its solutions in acids are yellow or red. When nitrobenzene (10 grams), 40 per cent. formaldehyde (10 grams), alcohol (10 grams), and fuming hydrochloric acid (35 grams) are gradually treated with zinc dust (20 grams) a t 50°, paranhydro- hydroxylaminobenzylic alcohol is formed almost quantitatively. I n order to prevent the reaction of the formaldehyde with the hydrogen atom in the para-position to the nitro-group, experiments were tried with paranitrotoluene. Paranitrotoluene [(lo grams), alcohol (100 c.c.), water (4 c.c.), and sodium hydroxide (5 grams) were electrolysed as above described with 1.3 amperes and 5-6 volts, A quantitative yield of paraxotoluene was obtained.Paranitrotoluene (10 grams), suspended in fuming hydrochloric acid (100 c.c.), and electrolysed with 5 volts and 1-7 ampi?res, gave a, quantitative yield of paratoluidine. Paranitrotoluene (10 grams), alcohol (80 c.c.), water (35 c.c.), and fuming hydrochloric acid (35 gra,ms) electrolysed with 1.5 amperes and 4 volts, also gave an almost quantitative yield of paratoluidine. I n the last case, when the water was replaced by 40 per cent. form- aldehyde, two substances were obtained in nearly equal quantities, namely, paradime t hyl t oluidine and paradimet hylenedi t oluidine, C,H,Me*N<CH2>N* C,H,Me. The latter is formed almost quantitatively by the action of formalde- hyde on paratoluidine in acid solution? and crystallises from dilute alcohol in slender needles melting a t from 119-125'; it cannot be reduced, either chemically or electrolytically, to paradi- methyltoluidine, except in presence of formaldehyde, when the reduc- tion proceeds perfectly smoothly, yielding paradimethyltoluidine and paratoluidine.T. E. CH2 Reduction of 2-Nitro-3 : 5-dimethylphenylnitrornethane [ ~-2-Dinitromesitylene]. By EUGEN BAMBERGER and MAX WEILER (J. pr. Chena., 1898, [ii), 58, 333-361).-When ~-2-dinitromesitylene, NO2* C6H2Me2* CH2-N02 (Konowaloff, Abstr., 1896, i, 674), is dissolved in 95 per cent. alcohol, and reduced with 4 per cent. sodium amalgam at - loo, 2-amido-3 :5-dirnet?~ylbenxaZloxinze, NH,* C,H2Me,* CH:NOH, is formed ; this melts a t 170-171°, dissolves in dilute mineral acids and caustic alkalis, forms a clibenxoyl derivative melting a t I42--142*5O9124 ABSTRAC'TS O F CHEMICAL PAPERS.and a yellow compound melting a t 179-180°, when mixed with meta- nitrobenzaldehyde in dilute hydrochloric acid solution. When boiled with dilute sulphuric acid, i t yields 1-amido-3 : 5-dimethylbenxuldehyde, NH,* C,H,Me,* CHO, identical with a product obtained from mesitylene in the manner described below ; this is yellow, and melts at 48-49'; with phenylhydrazine, it yields a substance melting at 142-143", and possibly not a normal hydrazone, as it is not soluble in acids. When the oxime is boiled for a short time with acetic anhydride, i t forms 2-C~cetcLmidomesitylenolnitrile, NHAc* C,.H,Me,* CN, together with a sub- stance that melts at about 150"; the nitrile melts at 196*5-191.5", and is insoluble in dilute acids and alkalis, but when warmed with these it is converted into a substance that melts at 271.5-272.5"; the latter has the properties of a quinazolone (Weddig&, Abstr., 1885, 661 ; 1887, 1044), and must, therefore, be trimethylpuinazolone, C,H,MO,<~& Me ; its orange-yellow platinochloride is still un- melted at 345O.When the oxime is dissolved in a mixture of acetic acid and anhydride, and the mixture is saturated with gaseous hydrogen chloride at 0" and allowed t o remain (Beckmann's mixture), the product, which melts at 166*5--168O, has the properties of an acetylisindazole (Auwers, Abstr., 1892, 186 ; 1896, i, 504), and con- CO *NH CH sequently must be acetyldimethylisindccxole, CGH2Me2<NAc>N ; it is soluble in cold, dilute hydrochloric acid, but not in cold, aqueous caustic potash; when boiled with the latter, it dissolves gradually, and f r m the solution acetic acid precipitates a substance melting at 19 1 *5-192*5", which possibly may be 2-acetamido-3 : 5-dimethyl- benzaldoxime.When the amidodimethylbenzaldoxime is diazotised in hydrochloric acid solution with sodium nitrite, the product is . dimethylindiaxone oxinae, C~H,Me,<C(NoHN)>N --- ; this is yellow, melts and decomposes at 181*5-182.5", and dissolves in cold, dilute mineral acids and alkalis, but is decomposed by these on boiling, the products being, when acid is used, hydroxylamine ; amidodimethylbenzaldehyde (see above) ; dimethybulicylccl~ehyd~, which solidifies at about 1 5 O , and forms an oxime, OH* C,H,Me,*C'H:NOH, melting at 138-5-139.5O ; and a substance which forms an oxime melting at 99--100*5O and is devoid of acid character.If w-2-dinitromesitylene is dissolved in commercial absolute alcohol and reduced with 4 per cent. sodium amalgam at - 5' to O", the pro- ducts then obtained are a resin ; mesitylenic acid ; amidodimethylbenz- aldoxime ; a base, ( C,HI,NO\,, possibly C,H,( OH),(CGH2Me,*NH,),, which melts at 260" ; another buse, or mixture of bases, which melts at 133-147*5", and has the composition C, 70.2-72.0; H, 8.26-8.51 ; N, 9.15 (these last two bases are insoluble in alkalis); and a small quantity of a n acid containing nitrogen. 2-Amido-3 : 5-dimethylbenzaldehyde was prepared from rnesitylene by oxidising it t o bimethylbenzaldehyde with chromyl chloride in carbon bisulphide solution ; or, better, by converting it into mesitylic bromide and oxidising this with chromate or lead nitrate, nitrating the aldehyde with a solution of potassium nitrate in strong sulphuricORGANIC CHEMISTRY.125 Bromopropionate . . . Bromophenyl- acetate ............ Bromobutyrate . . . . . . Bromisobutyrate . . Bromisovalerate . . . acid cooled by a freezing mixture, and reducing the 2-nitro-3 : 5-di- methylbenxddehyde, NO,. C,H,M:e,* CHO, which melts a t 102-1 03", with ferrous sulphate and ammonia. Hydrolysis of Ethanedicatechol 1 Dicatechol Acetylenic Ether]. By CHARLES MOUREU (Compt. Tend., 1898,127, 276 -278).- The compound C,H,O,, obtained by boiling dicatechol acetylenic ether with dilute sulphuric acid, is orthohydroxy~J~enoxyacetic m i d , OH* C,H,* O-CH,.COOH. It is acid to litmus, phenoIphthalein, methyl-orange, and the blue-C4B, gives an intense blue coloratiori with ferric chloride, and reduces ammoniacal silver nitrate in the cold, but gives no coloration with rosaniline hydrogen sulphite. Its phenyl- hydrazone crystallises in white, rectangular scales which melt and decompose at 193'. When heated, it forms a lactone which crystal- lises in large, elongated prisms melting a t 54-56', and when boiled with water is reconverted into the acid melting a t 130-131". The same acid is obtained by heating sodium monochloracetate with monosodium catechol and treating the product with hydrochloric acid. It is probable that when the dicatechol acetylenic ether is boiled with the dilute acid, the first product is a compound, C,H,: 0,: CH* CHO, which, by hydration, is converted into OH* C,H,* O*CH(O€I)* CHO, and the latter, being unstable, changes by intramolecular migration of an oxygen atom into the acid OH*C,H,*O*CH,*COOH.C. H. B. By PIERRE H. BAYRAC (Ann. Chim. Phys., 1897, [vii], 10, 18--79).-This paper gives full details of work which has already been published (see Abstr., 1895, i, 412, 416; 1896, i, 605, 606). Formation of Chains. XXVII. Benzylaniline. XXVIII. Diphenylamine. By CARL A. BHCHOFF (Be?., 1898,31,2672-2677, 2678-2683. Compare Abstr., 1898, i, 182).-Chain formation occurs less readily in the case of benzylaniline and of diplienylamine than with the secondary bases discussed in the preceding papers; this is indicated by the numbers in the following table, which give the approxi- mate extent in percentages of the theoretical maximum to which action takes place between the amines and ethylic salts there tabulated. C.F. B. Preparation of Paraquinones from Indophenols. G. T. &X. At A t At At 100". 110". 120". 100". Nil 29.2 50.9 1 1 40.3 ' 27.0 14.0 1 Xi1 Nil ~ Ethylic salt. Benzylaniline. Diphenylamine. At A t At 110". 120". 170-175". Nil 36.1 33'5 42'0 4'4 8.3 9'1 3'0 At 195-200". 55.8 The following new substances were prepared in the course of the Phenylbe.nxylgZycine, CH,Ph-NPh*C H,* COOH, prepared from investigation.126 ABSTRACTS OF CHEMICAL PAPERS. benzylaniline, chloracetic acid, and sodium acetate, crystallises from alcohol in needles, and melts a t 121-123" ; it decomposes on exposure to light and air, when an intense odour of benzaldehyde becomes perceptible.a-Bromopropionobenzylc~nilide, CH,Ph*NPh*CO*CHMeBr, formed by the action of a-bromopropionic bromide on benzylaniline, separates from alcohol in crystals belonging to the rhombic system and melts at 7 8'. a-Bromo but yro benx ytanilide, CH,Ph *NPh CO CH E t Br, is d e- posited by dilute alcohol in colourless crystals and melts at 50-54" ; a-b~-omisobutyrobenxylaniZide, CH,Ph*NPh*CO*CMe,Br, is an oil. a-BromisovaZerobenxyZaniZide, CH,Ph*NPh*CO*CHBr*CHMe,, crystal- lises from 96 per cent. alcohol in aggregates of colourless prisms and melts at 95-96'. a-BromopopionodiphenyZamide, NPh,*CO*CHMeRr, separates from hot alcohol in colourless, transparent crystals belonging to the monoclinic system and melts a t 109".a-BromobutyrodipT~enykcmide, NYh,* CIO*CHEtBr, is deposited by alcohol in large, lustrous crystals and melts a t 85" a-B!romiso6utyrodip~enyZa~~ide, NPh,*CO*CMe,Br, crystallises from alcohol in plates, and melts a t 82". a-B!romisovalerodiphenylcwnide, NPh,*CO*CHBr*CHMe,, crystallises in colourless, four-sided plates, and melts at 110.5". By AUGUSTIN BISTRZYCHI and FRITZ ULFFERS (Ber., 1898, 31, 2788-2790. Compare Abstr., 1894, i, 181, and Kay, ibid., 77).-Phenacetine, OEt*C,H,*NHAc, is boiled for several hours with a large excess of acetic anhydride in a reflux apparatus, moisture being excluded by means of a calcium chloride tube; the acetic acid formed and some of the anhydride is distilled over ; the residue is boiled again with more acetic anhydride, the product distilled under 15 mm.pressure in an oil bath at 180°, and the residue poured out. I n this way, diacetopJhenetidide, OEt*C,H,*NAc,, is obtained ; it melts a t 53-5-54", and boils a t 182' under a pressure of 12 mm. ; when kept in stoppered bottIes, it is decomposed very slowly by the moisture of the air, acetic acid being formed ; its physiological action is similar to that of phenacetine, and the same effect is sometimes obtained, although i t is commonly less lasting, with a smaller dose, than in the case of phenacetine. M. 0. F. Peracetylation of Phenacetine. C. F. B. Potassiodiphenylamine. By CARL HAUSSERMANN (J. p-. C'hem., 1898, [ii], 58, 367-368).-Diphenylamine (30 parts) is melted in a strong, round-bottomed flask in a boiling water-bath, potassium (1 part) is added little by little, and as soon as the violent action has ceased, the flask is exhausted of air and the heating is continued for 3-4 hours until the potassium has disappeared, after which un- changed diphenylamine is removed by digestion with absolute ether, The product, presumably NPh,K, is a yellow, sandy powder, which absorbs oxygen from the air, turning black, and unites with dry car- bonic anhydride to form potassium dipJienyZthiocurbamate, NPh, *COOK, a white powder which is decomposed by water into diphenylamine and potassium hydrogen carbonate. C.F. B.ORGANIC CHEMISTRY. 127 Nitroso-derivatives of Aromatic Amines. By CAMILLE MATIGNON and DELIGNY (Cornpt.Tend., 1897, 125, 11 03-1 lO5).-The authors have made a comparative study of the heats of combustion of the following nitroso-compounds of aromatic amines : diphenylnitros- amine, nitrosophenylaniline, and paranitrosodimethylaniline. They find t h a t the introduction of a nitroso-group into the aromatic nucleus lowers the heat of combustion by 15 calories, whereas its attachment t o the nitrogen of the side-chain lowers this by 9.8 calories. This difference explains the readiness with which the nitroso-group migrates from the nitrogen atom into the nucleus. Provided that the molecules originally contain a sufficient number of atoms, the introduction of a new radicle produces the same change in the heats of cornbustion if the entering group becomes similarly attached in each case.G. T. M. Behaviour of Substituted Amidonitriles towards Aromatic Aldehydes inpresence of Alkali. By WJLHELM YON MILLER and JOSEF PLOCHL (Bey., 1898, 31, 2699-2717).-Substituted amido- nitriles yield alkylideneamides with aromatic aldehydes, just as they give rise to amides under the influence of water. [With BR. BRUHN.]-The compound C,,H,,N,O, obtained by the action of benzaldehyde on benzylideneaniline under the influence of alcoholic potassium cyanide, is also produced gradually in absence of benzaldehyde ; it crystallises from atiiylic alcohol or nitrobenzene in microscopic needles and melts a t 249". The isonaeride, formed a t the same time, crystallises from alcohol in pale yellow prisms melting a t 208" ; i t is accompanied by a small quantity of a substance which crystallises i n pink leaflets and melts at 151".The compound C,,H,,N,O, is also produced ; i t melts and decomposes a t 194' and is distinctly acidic in character. The three compounds are formed when alcoholic potassium cyanide acts on the nitrile of phenylanilidoacetic acid and benzaldehyde, and they are all resolved into benzaldehyde, ammonia, and phenylanilidoacetic acid under the influence of boiling dilute hydrochloric acid. The less readily fusible isomeride is converted into that melting a t 208' by the action of boiling alcoholic potash, and of boiling glacial acetic acid ; the action in each case is reversible. [With LUDWIG GE~N~~oss.]-~rorn phenylanilidoacetonitrile and cuminaldehyde dissolved in alcoholic potash, two indifferent, isomeric compounds, CzaH2,N20, are obtained melting at 226" and 198" respectively ; they are also produced by the action of cuminaldehyde on benzylideneaniline, along with an acidic compound, C,,H,,N,O,, and the nitrile, C25H,,N,0, which melt at 208" and 256' respectively.The indifferent compounds are interconvertible, and, like the acid, yield cuminaldehyde, ammonia, and phenylanilidoacetic acid with boiling hydrochloric acid ; phenylhydrazine gives rise to cuminphenyl- hydrazone. Cumelnykanilicloacetonitrile, CI7Hl8N2, from cumylideneaniline and hydrogen cyanide, cry stallises from alcohol in lustrous, monoclinic prisms and melts a t 86". Cumenylanilidoc~cetamide, C,7H,oN,0, obtained by the action of concentrated sulphuric acid on the nitrile, forms colourless prisms melting at 1 5 9 O , and yields a nitroso-deriva-128 ABSTRACTS OF CHEMICAL PAPERS.tive which melts a t 132'. Curnenylanilidoacetic acid, Cl7Hl0NO2, crystallises in small aggregates of needles ; it melts and decomposes at 158'. [With P. SCH~r~z.]-~enxylideneparanisidine, C,,H,,NO, crystallises in leaflets and melts a t 72"; hydrogsn cyanide converts i t into the nitrile of phenylparanisidoacetic acid, which melts at 85', whilst the amide melts at 120'. Phenylparanisidoacetic acid, C,,H,,NO,, melts and decomposes at 184'. The two indifferent compounds, C,,H2,N,0,, obtained from the nitrile with benzaldehyde and alcoholic potash, melt at 222' and 193' respectively ; the acidic compound, C,,H,,N,O,, melts at 1 9S', with effervescence, and the corresponding nitrile, C,,H,lN,02, melts at 233'.[With R. LUPPE.]-Anhydroformaldehydeaniline with benzaldehyde and potassium cyanide, or anilidoacetonitrile with benzaldehyde and alcoholic potash, yields two indifferent compounds, C,,H,,N,O, melt- ing at 219' and 169' respectively, along with an acidic compound, C,,H,,N,O,, which melts and effervesces a t 239' ; when the com- pound melting a t 169' is recrystallised from alcohol, it is in part con- verted into the isomeride, the change being complete on exposing the substance to a temperature of 170" during some hours. Boiling 20 per cent. hydrochloric acid resolves tLe substance into benzaldehyde, ammonia, and anilidoacetic acid. [With WILHELM SIEBER.]-T~~ indifferent compounds, Ci,Hl,N20, obtained from anhydroformaldehydeparatoluidine with benzaldehyde and potassium cyanide, melt a t 245' and 168' respectively; the acidic compound, CI7Hl8N2O3, melts a t 228'. Paratoluidoacetic acid, C,H,Me*NH*CH,*COOH, obtained by hydrolysing with 20 per cent.hydrochloric acid the compound which melts at 245', crystallises from light petroleum in large, lustrous, monoclinic plates, and melts at 132" (compare Bischoff and Hausdorfer, Abstr., 1892, 1335) ; the nitrile melts and decomposes a t 61", and the amide, which melts a t 16S3, yields a nitroso-derivative melting at 158'. [With J. H~b~~u~~E~].-Ethylideneaniline, with benzaldehyde and potassium cyanide, yields a n indifferent compound, C,,H,,N,O, which melts a t 203', and an acidic compound, Ci7HlSN20,, melting at 220'. [With W.Ko~~~ao~s~~.]-Benzylidenemethylamine, with benz- aldehyde and potassium cyanide, yields a n indifferent compound, C,,H,,N,O, which melts at 152', and an acidic compound, Ci7Hl,N,0,, melting at 179'. Hydrolysis resolves these substances into benz- aldehyde, ammonia, and phenylsarcosine. M. 0. F. Stereochemistry of Quinoneoximes. By FRIEDRICH KEHRMAWN (Annalen, 1898, 303, 1-33. Compare Abstr., 1894, i, 460).-The two modifications in which both the benzoyl and methyl derivatives of metachloroquinoneoxime are produced have been regarded by the author (loc. cit.) as stereoisomerides ; further evidence in support of this view has been derived from a determination of the molecular weight of the two isomeric acetyl derivatives, and from an examina- tion of the behaviour of parachlorotoluquinone towards hydroxylamine hydrochloride.It being exceptional for the meta-halogen derivatives of toluquinone to yield isomeric oximes, the author concludes that itORGANIC CHEMISTRY. 129 is only in the case of a slight difference in the stability of the two forms that the phenomenon is noticeable; when the difference is great, one form only is produced. [With HUGO GRAB.]-T~~ stable modification of the acet$ deriva- tive of metachloroquinoneoxime crystallises from benzene in amber- coloured, four-sided prisms, and melts a t 166-167'; the labile compound dissolves more readily in benzene, from which it crystallises in yellow leaflets, and melts a t 136-137'. Both forms give normal figures for the molecular weight in glacial acetic acid, and yield 4 : 6 : 2-chlorodinitrophenol and 6 : 4-chloramidophenol on oxidation with nitric acid, and on reduction with stannous chloride and hydro- chloric acid respectively. The isomerism consequently meets with explanation on the hypothesis of Hantzech and Werner.When metachloroquinoneoxime is heated with alcoholic hydroxyl- amine hydrocliloride in a reflux apparatus, it yields metachloro- quinonedioxime ; the diacetyZ derivative of this substance occurs only in one modification, which crystallises from benzene in colourless prisms and melts a t 171--172". Oxidation and reduction of the dioxime lead to 1 : 3 : 6-chlorodinitrobenzene and 2 : 1 : 4-chlorodiamido- benzene respectively. ParadiciLZorozuinoneoxime, C,H,C1N02, separates from benzene in two crystalline forms, and melts indefinitely a t 155-160'; it is uncertain whether the dieerence in crystalline structure represents stereoisomerism.The acetyl derivative crystallises from benzene in amber-coloured prisms, and melts at 149". [With MICH. TICHYINSKY.]-T~~ oxirne of 4-chlorotoluquinone occurs in two modifications, which are separated by a method described in the original paper. The more sparingly soluble isomeride crystallises from alcohol in lustrous, brownish-yellow prisms, and decomposes a t 170" ; the ucetyl derivative melts at 158-159'. The more readily soluble modification crystallises from alcohol and from toluene i n aggregates of slender, pale yellow needles, and decomposes a t about 165" ; the acetyl derivative crystallises in long needles from the benzene mother liquor of the isomeride, and melts a t 141-142'.Chloramidocresol [Me : NH, : C1: OH = 1 : 2 : 4 : 51, obtained by re- ducing either modification of the oxime with stannous chloride and hydrochloric acid, forms colourless leaflets and melts at 204-205' ; the diacetyl derivative crystallises f r o p benzene in colourless needles and melts a t 162'. Chlorodinitrocresol [Me : (NO,), : C1 : OH = 1 : 2 : 6 : 4 : 51, produced by the action of dilute nitric acid on either modification of the oxime, crystallisus from alcohol in yellow leaflets and melts a t 108". [With CARL RUST.]-~-B'/'O~ZO~O~U~U.~~O~~ [Me : 0, : Br = 1 : 2 : 5 : 41, prepared by treating toluquinone with fuming hydrogen bromide and oxidation of the product with chromic acid, crystallises from alcohol in large, yellow plates and melts at 105".The oxime occurs in two modifications, the more sparingly soluble forming brownish-yellow needles which decompose at 186', whilst the more readily soluble crystallises from toluene in slender, pale yellow needles and decom- poses a t 178--180"; the acetyl derivatives melt a t 166-167" and 131-1 32" respectively. The corresponding benxylic ethers melt at VOL. LXXVI. i. 7,.130 ABSTRACTS OF CHEMICAL PAPERS, 95-96' and 80--81° respectively ; the latter crystallises in the asymmetric system, and has the axial ratio a : b : c =; 1.7562 : 1 : 1.1580. B~omnlzz,icZo~~~etccc~csoZ [Ne : NH, : Br : OH = 1 : 2 : 4 : 51, prepared by reducing either oxirrie, forins silvery leaflets, and decornposes at 205 -208' ; the dicccetp? derivative crystallises from toluene in colourless prisms and melts at 17 1-1 72'.Bro.nzoclinitrometcccresoZ [Me : (NO,), : Br : OH = 1 : 2 : 6 : 4 : 51, ob- tained from both modifications of the oxime by the action of moderately concentrated nitric acid on the water-bath, crystallises from petroleum in sulphur-yellow octahedra and melts at 115-116' ; trinitrocresol, which melts a t 106-107', is produced along with it. M. 0. F. Ethers of Toluquinoneoxime and their Bearing on the Space- isomerism of Nitrogen. By JOHN L. BRIDGE and WILLIAM C. MORGAN (Amer. Chem. J., 1898, 20, 761-776).-Toluquinoneorth- oxime, which is readily prepared by the action of nitrous acid on metacresol, melts at 155", not at 145-150°, as stated by Beilstein; toluquinonemetoxime, prepared similarly from orthocresol, melts at 134'.The silver derivative, C7H,N0,Ag, of the metoxime, when freshly prepared, is a light reddish-brown powder, which slowly decomposes on exposure to the air, and when thoroughly dry ignites spontaneously on being heated above 60'; when shaken with methylic iodide dissolved in light petroleum, it is partially converted into the corresponding methyl derivative, C,H,NO, ; this can be better obtained, however, by adding the calculated quantity of methoxylamine hydrochloride to toluquinone dissolved in a large quantity of water. The product in either case, after being recrystallised several times from light petroleum, melts indefinitely between 55' and 70°, and appears t o consist of a mixture of two stereoisomerides; one more sparingly soluble in light petroleum, can be isolated by fractional crystallisation and melts at 73-74', but the second modification cannot be separated.The Corresponding ucetyl derivat,ive, C,H,NO,,. formed in small quantity on adding acetic chloride to the silver derivative suspended in ether or light petroleum, is resolved by fractional crystallisation from the latter into two stereoisomerides; one of these melts a t 112-113', and crystallises in thick prisms, whilst the other forms spherical aggregates of minute crystals and melts at 85-87'. The benxoyl derivative, C1,HliNO,, prepared by acting on the sodium salt of toluquinonemetoxime prepared from orthocresol, is identical with that obtained from the oxime prepared from toluquinone and hydroxylamine hydrochloride ; both products are mixtures of two stereoisomerides, one crystallising in bright yellow needles and melting at 193", the other separating in thick prisms, and melting probably at 142-144", although fractions were obtained melting at 129'.No trace of the orthoxima could be detected in the product obtained from toluquinone. On adding bromine t6 a chloroform solution of the benzoate of the metoxime, the dibromide, C14HllBr,N0,, is obtained ; it crystallises from glacial acetic acid in white prisms, melts and decomposes a t 165", and is converted by boiling alcohol into a mixture of two stereoisomeric be72xoccte,~, C,,H,,BrNO3, of bromotoluquinonemetoxime ; the crudeORGANIC CHEMISTRY. 132 product melts and decomposes at 155-1 70", hut after fractional crystallisation from alcohol melts and deconiposes a t 174".The silve?. derivative, C,H,NO,Ag, of toluquinoneorthouiiue closely resembles the corresponding meta-derivative, but is much more stable than the latter. The ntethyl derivative, C,H,N02, obtained from it crystallises from light petroleum in long needles, melts at 6 9 O , and appears to exist only in one form; when the calculated quantity of bromine is added to its solution in chloroform, the clibyomide, C,H,Br2N0,, is obtained which crystnllises from light petroleum in white prisms and melts at 112'. The same acetyl derivative as was prepared by Wurster and Riedel (Abstr., 1880, 109) from acetic anhydride and toluquinoneorthoxime is formed in small quantity by acting on the silver derivative of the latter with acetic chloride.The corresponding benxoyl derivative, C14H11N0,, crystallises from alcohol in flat, brownish-yellow prisms, and melts and partially decomposes at 177" ; the dibromide, C,,Hl1Br2NO3, crystallises from glacial acetic acid in stunted orthorhombic prisms, and melts and decomposes a t 159'. I n discussing his results, the author emphasises the fact that, whereas the preparation of derivatives of toluquinonemetoxime gives rise to two stereoisomerides, the corresponding derivatives of the orthoxime exist only in one form; it is suggested, as tt possible explanation, either that, in the latter case, the proximity of the side- chains prevents the formation of a space-isorneride, or that isomeric substances exist which cannot be distinguished by the ordinary methods.Since no trace of the orthoxime is formed on treating toluquinone with hydroxylamine hydrochloride, Kehrmann's rule (Abstr., 1889, 243) concerning the influence of side-chains in quinones on the position taken by the entering isonitroso-group is confirmed ; the latter's views of the space-isomerism of the quinoneoximes also explain the existence of stereoisomeric modifications in the cases dealt with above. W. A. D. Beckmann's Transformation. By KARL AUWERS and H. CZERNY (Bey., 1898, 31, 2692-2698).-The production of indazole derivatives by the action of glacial acetic acid with acetic anhydride and hydro- gen chloride on the oximes of aromatic orthamidoketones (compare Auwers, Abstr., 1896, i, 503), suggested the possibility of obtaining analogous indoxazenes, C6H4e:>N, from the oximes of aromatic orthohydroxyketones.Contrary t o expectation, however, the oxime of unsymmetrical orthohydroxymetamethylbenzophenone, OH* C,H,Me*CPh:NOH, undergoes the Beckmann transformation, yielding benzenyl-3-amido- paracresol, C,H,Me<z>CPh, and the anilide of 4-hydroxymeta- toluic acid. I n addition to Beckmann's mixture, zinc chloride, phos- phorus pentachloride, phosphoric anhydride, and anhydrous copper sulphate induce this change, which also occurs when the substance is distilled under ordinary and reduced pressures ; the action of copper sulphate gains in interest from the fact that i t has, hitherto, been k 2132 AESTRACTS OF CHEMICAL PAPERS employed when transformation of an oxime is to be avoided.The result of heating the oxime of orthohydroxymetamethylbenzophenone gives support to Beckmann's opinion that the transformation of oximes into amides is an instance of catalytic action (Abstr., 1894, i, 240). The oxime of unsymmetrical orthohydroxymetamethylbenzophenone, OH* C,H,Me*CPh:NOH, crystallises from glacial acetic acid in small, white needles, and melts at 126-128.5". action of Beckmann's mixture, melts a t 104" ; concentrated hydro- chloric acid at 150-160° converts it into benzoic acid and 3-amido- paracresol. The dibenxoyl derivative of S-amidoparacresol, NHBz*C6H,Me*OBz, crystallises from alcohol in white leaflets and melts a t 190-191O; hydrochloric acid precipitates from the solution in caustic soda the benxoyl derivative, NHBz- C,H,Me*OH, which crystallises in nacreous leaflets and melts at 191".When either of these compounds is boiled during a few minutes, i t yields benzenyl-3-amidoparacresol. The anilide of 4-hydroxymetatoluic acid, obtained by the action of zinc chloride on the oxirne of orthohydroxymetamethylbenzophenone, melts at 158-159", and not at 5S0, as stated by Bargioni ; the hychogen phosphate melts a t 18'7-189'. M. 0. F. Action of Alkylic Salts of ,&Ketonic Acids on Paraphene- tidine. By ERNESTO FOGLINO (Chem. Centr., 1898, i, 501 ; from Ann. Chim. $'arm., 26, 535-541).-By the action of paraphenetidine on ethylic benzoylacetate a t 120-130°, alcohol and benzoylacetophene- tidine, OEt*C9H,*NH* CO*CH2Bz, are formed ; the latter crystallises from alcohol in white needles, melts a t 139-140°, and is insoluble in cold water.With the ethylic salts of acetoacetic, methylacetoacetic, diethylacetoacetic, benzoylacetoacetic, and acetylsuccinic acids, para- phenetidine at 140---150" yields alcohol, a ketone, and Wenghofer's paradiphenetoilcarbamide, CO(NH* UGH,* OEt),. The last compound is also formed by the action of benzoylacetoacetamide on paraphene- tidine. E. W. W. Action of Piperidine on Carbonates Derived from Phenols : Formation of Aromatic Urethanes. By PAUL CAZENEUVE and MOREAU (Compt. rend., 1897, 125, 1107-1109). -When piperidine acts on carbonates derived from phenols, urethanes alone are produced, there is no formation of carbamide derivatives. Piperidine and phenylic carbonate, when simply mixed together, form a urethane, C,H,,N*COOPh, which melts at 80°, and dissolves in the ordinary organic solvents ; it is hydrolysed by caustic potash into phenol and piperidine.The urethane, C,H,N* COO*C,H,* OMe, from guaiacol carbonate and piperidine, crystallises from alcohol in white prisms, melts at 44O, and boils at about 330'. The corresponding P-napl&ylic uq*ethane, produced by mixing together /3-naphthylic carbonate and piperidine, crystallises in needles and meltsORGANIC CHEMISTRY. 133 at 107". The a-naphthylic compound has not yet been obtained crys- t alli n e. When treated with concentrated sulphuric acid, these urethanes yield piperidine sulphate and a sulphonic acid of the corresponding phenolic compound. G. T. M. By PAUL CAZENEUVE and MOREAU (Conzpt. ?*end., 1898, 126, 481-483.Compare preceding abstract).-Conicine and phenylic carbonate, when heated together for 1 hour, form the urethane, C,H,,N*COOPh, a viscous liquid boiling a t 325" ; its rotation in alcoholic solution is [ a3j + 3-66'. The urethane, C,H,,N* COO*C,H,* OMe, is obtained in similar manner from guaiacol carbonate; i t forms a viscous liquid boiling a t 277". The a- and P-naphtlLyl urethanes, C,H,,N* COO*C,,H7, are very viscous liquids boiling above 300". All these substances are hydrolysed by caustic potash at 150°, and are decomposed by concentrated sulphuric acid with evolution of car- bonk anhydride. G. T. M. Aromatic Urethanes of Conicine. Pseudophthalimidine and Orthocyanobenzylamine. By SIEG- MUND GABRIEL and WILLY LANDSBERGER (Bey., 1898, 31, 2732-2740).-Kiel (Inuug. Diss. Bonn., 1896) has shown that pseudophthalimidine probably has the constitution, NH:C<-'A>CH,, which was formerly assigned by Graebe to phthalimidine. The authors have examined the molecular weights of these compounds in order to ascertain whether they both correspond with this formula. Pseudo- phthalimidine itself is not adapted for this purpose, since it cannot be purified by distillation, and the corresponding nitro-derivative was, therefore, substituted for it. Orthocyanobenzylic chloride is converted by nitration into 5-nitro-2-cyanobenxylic chloride, CH,Cl* C,H,(NO,)*CN, which forms yellowish crystals and melts at 94". When heated with hydro- chloric and acetic acids a t 140-150", i t is cwverted into 5-nitro- phthalide, a reaction which indicates the constitution of the corn- pound.The nitro-compound can readily be converted by hydrolysis with sulphuric acid into o-chZoro-5-nitro-ort?~otoZuamide, CH,Cl* C,H,(NO,)* CO*NH,, which crystallises in matted, snow-white needles melting at 228O when rapidly heated. When heated for some time a t l l O o , it is con- C H verted into 5-nitropsezcdopl~thcLlimidine. NO,* C,H,<-CH2->0, which C(NH) crystallises in needles melting a t 158". The hydrocldoride decomposes in aqueous solution, forming ammonium chloride and nitrophthalide. The picrate melts at 158", whilst the platinochloride crystallises in narrow, orange-yellow prisms and decomposes at about 120°, and the auyichloride crystallises well, This compound and phthalimidine itself have the normal molecular weight, determined by the boiling point method.Hence it appears that phthalimidine has the constitution C,H,<-"->NH, whikt CH2134 ABSTRACTS OF CHEMIICAI, PAPERS. pseudophthalimidine receives the formula assigned to it by Kiel. When orthocyanobenzylphthalimide is heated with hydrochloric acid at 190--200°, a small amount of phthalimidine is formed. I n former experiments, this was isolated as nitrosophthalimidine, the formation of which was, however, ascribed to the action of the nitrous acid on the orthocyanobenzylamine which is also present in the product. Renewed experiments have, however, shown that orthocyanobenzyl- amine is not attacked by nitrous acid, but that it is converted into phthalimidine by the continued action of acids, This formation of phthalimidine affords further evidence in favour of the formula ascribed to it above.Orthocyanobenzylarnine is best obtained by heating orthocyanobenzylphthalimide with alcoholic potash. The hydrocldoride decomposes at about 2 0 7 O , whilst the picrate melts and decomposes a t about 219". Alcoholic potash cannot be employed for the preparation of other amines from their phthalimide compounds ; benzylphthalimide, for example, when treated in this way, does not yield the amine, but is converted into benx~lphthalccminic acid, C,H,*NH* CO*C,H,* COOH, which crystallises in needles and melts and decomposes a t 154", benzylphthalimide being again produced. A. H. Diazomethane and Nitroso-acidamides. By HANS VON PECFI- MANN (Ber., 1898, 31, 2640-2646).-When nitrosomethylurethane is decomposed by alcoholic potash, only half the theoretical yield OF diazomethane is obtained, and this is due t o the fact that the re- mainder of the urethane is decomposed by the potash in the following mays.I, Formation of nitrous acid and urethane, NO *NMe*COOEt + H,O = HNO, + NHMe* COOEt ; 2, formation of carbonic acid, nitrous acid, and methylamine, NO *NMe* COOEt + 2H,O = OH* COOEt + HNO, + NH,Me. Nitrosoethylurethane, nitrosobenzylurethane, and nitrosobenzoylbenzylamine are decomposed in a similar manner., whilst it has been found that benzylamine acts as an alkali in the same way as the potash. Nitrosoethylurethane, prepared in the same way as the methyl derivative, is an oilfwhich boils at 90' under a pressure of 42 mm. and has a sp.gr.=1*0735 a t 15'/15'. When treated with alcoholic potash, 20 per cent, of the theoretical amount of diazoethne is produced; this is very similar to diazomethane, but its solution in ether is of a darker colour. When nitrosoethylure- thane is treated with benzylamine, nitrogen is evolved and benzyl- urethane produced, the diazoethane, which is, no doubt, the first product, being immediately decomposed. Benxylwethccne crystallises in colourless plates melting a t 44O, and is converted by nitrous acid into nitrosobenxylurethane, which is a reddish-yellow oil, and cannot be distilled; when this is treated with alcoholic potash, it yields stilbene and benzylic methylic ether. Nitrosobenxobenxylamide crys- tallises in pinkish prisms, melts a t 46-47O, and gradually decom- poses when kept, yielding nitrogen and benzylic benzoate.When heated with alcohol, i t decomposes in all the ways already described in t,he case of nitrosomethyluretliane : (1) into benzoic acid and phenyl- cliazomethane, which appears in the product partly as benzylic ethylic othcr, and partly as benzylic benzoate; (2) into nitrous acid andORGANIC CHEMISI'HY. 135 benzoylbenzylamine ; and (3) into benzoic acid, nitrous acid, and benzylamine. Attempts to bring about the direct elimination of nitrogen from diazomethane by heating it, and by the use of powdered copper, platinum black, &c., proved unsuccessful. A. H. New Representatives of Primary Disazo-dyes of the Benzene Series. By CARL BULOW and HANS WOLFS (Ber., 1898,31,2775-2783, Compare Abstr., 1898, i, 308).-The following additional colouring matters have been prepared; they have the general formula NMe,.C,H,(OH)(N,R) *N2R "Me, : OH : N,R : N2R' = 1 : 3 : 4 : 61, and the groups tabulated under 4 and 6 are the groups 11 and 12' respec- tively; the method of preparation is t h a t already indicated. 4. Ph l-CI0H7 1-C1,0H7 PI1 2-CloH7 2-C10H7 1-C10H7 2-CloHV 1-C10H'7 2-C,0H7 1-C10H7 2-C10H7 2-C,H4Me 2-C,H4Me 4 - C,H4Me 4-C6H,Me 2 : 4-C6H,Me, 2 : 4-C6H3Me, 6. CoIour. ' Melting point. 1 Dark red Violet-red Dark brown Claret -red Brown Brown Black Dark green Dark brown Dark green Green Dark brown Red Dark green Dark red Dark red Red Dark green 178" 176 180-181 176 196 154 185-1 86 132 182 187 182 153 180 141 175 154-155 , 147-148 171-172 C. F.B. Ketochlorides and Orthodiketones of Phenylazimido- benzene and Phenyl-$-aeimidobenzene. By THEODOR ZINCKE and E. PETERMANN (J. pr. Chein., 1898, [ii], 58, 234-244. Compare Abstr., 1898, i, 537).-The paper contains a preliminary account (without experimental details) of experiments with phenylazimido- benzene and phenyl-$-azimidobenzene, carried out on similar lines t o those already described with azimido benzene (Zoc. cit.). Like the latter substance, they can be converted into ketochlorides and ortho- diketones, possessing a strong analogy t o those derived from azimido- benzene. The analogy is not complete, however, for the presence of the phenyl group, and the difference in constitaution of the nitrogen ring, exert an influence on the results. For example, the phenyl group of the azimido-derivative does not react mit'h chlorine, whereas substitu- tion tnkcs placc in the phenyl group of the $-derivative.A. w. c'.136 ABSTRACTS OF CHEMICAL PAPERS. Hydrazides of Meta- and Para-bromobenzoic Acid. By THEODOR CURTIUS and EDUARD PORTNER (J. pr. CJLem., 1898, [ii], 58, 190-205. Compare preceding a bstract).-Metabromobenxhydraxide, C,H,Br-CO *NH*NH,, prepared from hydrazine hydrate and ethylic metabromobenzoate according to directions already given (J. pr. Chem., [ii], 50, 295), forms long, glistening, silken needles, melts at 151", is soluble in alcohol, but almost insoluble in ether, chloroform, and benzene, and reduces Fehling's solution and ammoniacal silver nitrate in the cold. The hydrochloride forms small leaflets melting and giving off gas a t 248' ; the sodium salt, small plates ; and the cccetyl deriva- tive colourless, silken prisms melting a t 169".Benxylidenernetabromobenzhydraxine, CHPh :N*NH* CO *C6H4Br, pre- pared by the action of benzaldehyde on the hydrazide, crystallises from alcohol in beautiful, long, colourless needles melting at 105" ; boiling dilute mineral acids decompose it into its components. The cor- responding ortJhohydroxybenxylidene compound forms tufts of colour- less needles melting at 192", and the acetone [P-propylidene] deriva- tive, small needles melting at 88.5". Dimetabromobenxhydrazidu, (NH*CO*C,H,Br),, obtained by the action of iodine on the bromo- benzhydrazide, crystallises from glacial acetic acid in small, glistening needles melting at 265'.When boiled with dilute mineral acids, it is converted into bromobenzoic acid and a hydrazine salt. Metabrornobenxaxide, CGH4Br*C0 *N3, obtained by the action of nitrous acid on bromobenzhydrazide, is a colourless oil with a n un- bearable odour producing tears, and explodes violently when heated in a test tube. Metadibrornodiphentjlcarbarnide, CO(NH* C6H,Br),, prepared from the azide by boiling with water, forms long, colourless, silken prisms melting at 262". It is volatile without decomposition, sublimes in small needles, and, when boiled with acids, is decomposed into meta- bromaniline and carbonic anhydride. E'thylic rnetabromophenylcarbamate, CGH,Br *NH* COOEt, obtained by the action of absolute alcohol on metabromobenzazide, is a thick, colourless oil boiling a t 193-194" under a pressure of 17 mm., and is decomposed into its components by concentrated acids.The cor- responding methylic salt is a colourless oil boiling at 165-16'7' under a pressure of 75 mm. The following corresponding para-compounds are also described. Bromobenxhydraxide, long, colourless prisms melting at 164" ; i t s hydrochloride, small, glistening needles melting at 262" ; acetone- [P-propylidene]bromobe~x~h~dr~~~ide, long needles melting at 194.5" ; benxylidenebi.omobenxJhydraxide, colourless, silken prisms melting at 235" ; brornobenzazide, colourless plates melting a t 46" ; ethylic bromo- phenylcarbamate, long, white needles melting at 81" ; the corresponding metJLylic salt melts at 81" ; dibrornodipJienyZcarbamide, clusters of nacreous needles melting at 2'74' ; and bromophenylbi*omobenxoylsemi- carbaxide, C,H,Br *NH* CO *N,H,- CGH4Br, microscopic plates melting at 248". When parabromobenzazide is dissolved in carbon tetrachloride, and bromine added, a colourless, crystalline substance, probably dibromo- carbanil, is obtained. A.W. C.ORGANIC CHEMISTRY. 137 P henylsernicarbaxide. By THEODOR CURTIUS and ADOLF BURKHARDT (J. pr. Chem., 1898, [ii], 58, 205-233. Compare Abstr., 1896, i , 647).--In continuance of the researches of Curtius and Hof- mnnn (Zoc. cit.), i t is now shown that phenylcarbamazide does not undergo rearrangement, as do ordinary acid azides of the type RCON,. When heated with water in sealed tubes, i t is completely converted into carbonic anhydride, diphenylcarbamide and hydrazoic acid ; alcohol decomposes it into hydrazoic acid and phenylurethane ; aniline produces the cnrbanilide, and bromine gives pccrabrorno~lzeIayZcnrbam- axide, C6H,Br*NH.CO*N3, separating from alcohol in rhombic crystals melting at l26', which are acted on by water, with produc- tion of paradibromocarbanilide. The solid, microcrystalline product formed on adding sodium nitrite to a n aqueous solution of oxalhydrazide hydrochloride is not a product of the rearrangement of the oxazide, but the dihydrazide of oxalic acid, produced by the oxidation of the hydrazide.Phenylsemicarbazide may be obtained by the action of hydrazine hydrate on ( a ) the phenylurethanes, NHPh*COOR + N2H,0H = NHPh*CO*NH*NH, + ROH + H,O ; (6) on mono- or di-phenylcarb- amide,CO(NHPh), + N,H,*OH = NHPh*CO*NH*NH, + NH,Ph + H20; ( c ) on phenylcarbirnide.The best yields are obtained from diphenylcarbnmide, all the other reactions being more or less compli- cated, and the isolation of the base difficult. Phen ylsemicarbazide hydrochloride forms colourless, transparent prisms melting a t 215'; the sodium compound crystallises in yellowish needles, and the acetyl derivative in colourless needles melting a t 169'. EthyZic phenylsenzicarbaxideacetoacetute, NHPh- COON H*N:CMe* CH,* COOEt, formed by the interaction of ethylic acetoacetate and the semicarb- azide, crystallises from alcohol in small, colourless needles melting at 151". HydrcLxidicarbonanilide, N HP h* GO NH NHGO *NHPh, obtained by the action of iodine or of heat alone on phenylsernicarbazide, crystallises from glacial acetic acid in long, colourless prisms melting at 245O, without decomposition, is with difficulty soluble in the ordinary organic solvents, and possesses basic properties.When heated with hydrochloric acid in sealed tubes, a t 180-200°, it is completely converted into carbonic anhydride, aniline, and hydrazine hydr ochlor- ide. Bromine acts on it in glacial acetic acid solution, forming a tetrabromo-compound, C,,H,,N,Br,, crystallising in needles and melting at 215-218O. Axo-dicarbonanilide, N2( C'O*NHPh),, produced by the action of nitric acid on hydrazidicarbonanilide, crystallises from acetone in bunches of dark red needles melting a t 182-183'. On rubbing, the substance becomes strongly electric, and is reconverted into hydrazidicarbon- anilide by boiling with acids, alkalis, or tin and hydrochloric acid.Phen?lZca,i.bamirtccxide, NHPh*CO*N,, prepared by the action of138 ABSTRACTS Ok' CHEMICAL PAPERS. sodium nitrite on an aqueous solution of phenylsemicarbazide hydro- chloride, crystallises in colourless leaflets melting at 103-104°. A. W. C. Catecholglyoxal. By CHARLES MOUREU (Compt. rend., 1898, 127, '324-326).-The compound, C,H,O,, obtained by J. Hesse by boiling with dilute sulphuric acid the product, C,H,:O,:CH*CH(OEt),, prepared by the action of dichloracetal on disodiumcatechol, is identical with the hydroxyphenoxyacetic acid obtained by the author under similar conditions from dicatecholacetylenic ether. It is clear that, although the aldehyde catecholglyoxal has not been isolated, it must be the first product of the hydration of the compound C,H,:O,:CH*CH(OEt),, and hence may be assumed to be an intermediate product in the hydration of catechol acetylenic ether, since the final product is the same in both cases (compare this vol., i, 125).Beneoyl Derivatives of Acetonitrile and Paratoluoylaceto- nitrile. By 0. SEIDEL (J. pr. Clzem., 1898, [ii], 58, 129-159).- Benzoylacetonitrile (cyanacetophenone) is best obtained by the action of concentrated hydrochloric acid on benzacetodinitrile. Obregia (Abstr., 1892, ii, 324) obtained from it, by the action of phenylhydrazine, a yellow, crystalline substance melting at 134-135°,whereas Burns (Abstr., 1893, i, 314),by the action of phenyl- hydrazine on benzacetodinitrile, obtained yellow needles melting at 121", although the reaction should give the same substance as that obtained by Obregia.The author now shows that the twosubstances are identical, and must be regarded as the phenylhydraxorze of cyan- acetophenone melting a t 146-147", the difference in the observed melting points being accounted for by the fact that, on warming, or on exposure to air, or by repeated crystallisation from dilute alcohol or chloroform, it is partially converted into an isomeride, 1 : 3-dipheng1- 5-inaidopgraxoZine, C,,H,,N,, crystallising in white, rhombic plates and melting a t 129.5"; this cannot be reconverted into the phenylhydr- azone, than which it is much more stable, and possesses basic properties. The hgdrochloride is not stable in air, and the platinochloride crystal- lises in large, prismatic needles melting and decomposing a t 191".Both isomerides, when treated with acetic anhydride, give the same nzonacetyl derivative, crystallising from benzene in beautiful, white needles melting at 149". When the phenylhydrazone is treated with nitrous acid in ether, benzene, alcohol, or chloroform solution, nothing but tarry products are produced, but when dissolved in acetic acid, whereby it is converted into its isomeride, two substances are formed which can be separated by the difference initheir solubilities in acetic acid or benzene; the one is the true nits.oso-clerivative of diphenylimidopyrazoline, C1,H1,N,O, crystal- lising from benzene in dark red, glistening prisms melting at 207", which, when heated with concentrated hydrochloric acid, is converted into 4-isonitroso-1 : 3-cliphenylpyrazolone (compare Knorr a i d K lot z, C.H. B.ORGANIC CHEMIS'MiY. 139 (Abstr., 1887, 1121), and the other, of the composition C30HZRNp crystallises from glacial acetic acid in canary-yellow needles, melting a t 317'. It is not acted on by concentrated sulphuric acid or hydro- chloric acid when heated with it in sealed tubes a t 160', and is pro- bably formed by the condensation of 1 molecule of the red substance with 1 molecule of the iinidopyrazoline. Phenylhydrazine reacts with paratoluacetodinitrile, forming :% phenylhydraxone crystallising in yellow needles and melting a t 153". When heated, or dissolved in acetic acid, it is converted into the isomeric l-phenyl-3-paratolyl-5-imidopyrazoline, from which, by the action of nitrous acid a ?wed substance, C,,H,,N,O, melting a t 2 3 2 O , and a yellow substance, C,,H,?N,, melting a t 212', are produced.Burns (Zoc. cit.) and Obregia (loc. cit.) have stated that cyanaceto- phenoneoxime is only stable in the form of its isomeride phenylisox- nzoloneimide, whereas Pro bst believes the oxime of paratolylacetodini- trile t o be a true oxime. The author cannot substantiate Probst's conclusions, and regards the substance as 7-paratolylimidoisoxazoline. C z1 H, ?N R, obtained by the action of diphenylhydrazine on an alcoholic solution of cyanaceto- phenone, crystallises from dilute alcohol in yellow prisms melting a t 148'; it cannot be converted into an isomeride either by the action of heat or by dissolving i t in glacial acetic acid.3-Phenyl-5-imidopy~axoZine, C,H,N,, produced by the action of hydrazine sulphate on cyanacetophenone, forms white crystals melting at 125'. The hydrochZoq*ide crystalliscs in small needles, and the platinochloride forms large, yellow prisms melting and decomposing a t 225'. 1 : 3 : 5-Tripl~enyl-4-cyanopyrccxoZe, C,,H,,N,, obtained by the inter- action of dibenzoylacetonitrile and phenylhydrazine hydrochloride, crystallises from alcohol in white needles melting at 189", is insoluble in potassium hydroxide, is not attacked by hydrochloric acid when heated with it in sealed tubes at 160°, o r by sulphuric acid, in which it is soluble, and does not form a platinochloride; when hydrolysed, it is converted into 1 : 3 : 5-triphen~l-4-~y~u~oleca~~~oxyZic acid, which crystallises in white needles melting a t 23S0, and when heated alone, is changed into 1 : 3 : 5-pyrazole, with loss of carbonic anhydride.When the silver salt of dibenzoylacetonitriie is treated with methylic iodide, the methylic salt is obtained in small, yellow needles melting at 117-118"; it is neutral, and is readily decomposed by water into dibenzoylacetonitrile and methylic alcohol. Tq.i6enxoyZcccetonitriZe, CN*CBz,, or CN*CBz:CPh*OBz, obtained from the above silver salt by the action of benzoic chloride, forms compact, white crystals melting a t 13S0. Alkalis decompose it at once into dibenzoylacetonitrile and benzoic acid ; aniline gives the corresponding ccnilide crystallising from alcohol in silken needles melting at 165", and phenylhydraziiie proclwes 1 : 3 : 5-triplienyl-4- cyanopyrazole.During the original reaction (benzoic cliloride and acetonitrile), a substance, C17H,,N,0, is also produced, crystallising in golden needles melting a t 204'; it could not be obtained in quantity sufficient for Cyanccce tophenone diphenyllb y draxone, complete investigation. a. w. c,140 ABSTRACTS OF CHEMICAL PAPERS. Condensations with Phenylacetone [Benzyl Methyl Ketone]. 11. By GUIDO GOLDSCHMIEDT and GUSTAV KNOPFER (Monatsh., 1898, 19, 406-436. Compare Abstr., 1898, i, 31).-The ketone, C1,H1,ClO, obtained by t h e action of hydrochloric acid on a mixture of benzyl methyl ketone and benzaldehyde, may be made t o yield stilbene by distillation with lime, It dissolves gradually in cold, strong sulphuric acid, giving a colourless solution, which becomes yellow and finally brown when warmed.When heated with a n alcoholic solution of hydroxylamine hydro- chloride, chlorobenzylphenylacetone, a s the author terms the above ketone, yields a n oxime, CI,H,,NO, which crystallises in beautiful, colourless, silky needles, melts at 153", and is insoluble i n alkalis or acids; when boiled with acetic anhydride, i t affords a substance, possibly an acetyl derivative, which crystallises from alcohol in beautiful, white needles, and melts a t 92". When chlorobenzylphenylacetone is warmed, in alcoholic solution, with an equal weight of potassium cyanide, a compound, C17Hl,NO, is produced which crystallises from alcohol in needles and melts at 193' ; i t sublimes without decomposing, and dissolves in strong sulphuric acid, giving a yellow solution which, when warmed, exhibits a feeble violet fluorescence.It was not possible t o obtain the correspond- ing acid by hydrolysis. The ketone, C1,H,,O (m, p. = 53", Zoc. cit.), yields a thick oil on dis- tillation with lime, but stilbene could not be detected in it. The ketone dissolves in sulphuric acid, giving an emerald green solution, which assumes a bluish-violet fluorescence when warmed. It is at once destroyed by permanganate solution, but is not appreciably affected by potassium hydroxide, or dilute alcoholic hydrochloric acid. It does not yield a crystallisable additive product with bromine. The ketone, C,,H,,O (m. p. = 71'), comports itself towards perman- ganate and on distillation exactly like its isomeride.Its solution in sulphuric acid is lemon-yellow, and, when warmed, becomes red, exhibiting a strorig green fluorescence. It evolves the odour of benz- aldehyde when warmed with alcoholic hydrochloric acid, and the solu- tion on cooling, especially after dilution, deposits oily drops and crystals of the unaltered substance. The dibromide, C,,H,,OBr,, made by adding bromine to a solution of the ketone in chloroform, crystallises in beautiful, silky needles, melts at 93', and dissolves very readily in ether and benzene, but only sparingly in alcohol and light petroleum. Triphenyltetrahydro-y-pyrone, when warmed with alcoholic hydro- chloric acid, is decomposed into benzaldehyde and the ketone melt- ing at 71"; the inverse change is effected by shaking a mixture of benzaldehyde and the unsaturated ketone with aqueous potash during 48 hours ; the saturated ketone does not afford the pyrone derivative under these conditions ; under certain circumstances, the substance melting at 175" is also formed by this process of condensation (Zoc, cit.). The analysis and molecular weight of the latter compound points to the formula C41H3803,.hence its formation from benzyl methyl ketone and benzaldehyde is probably effected in similar manner t o that of dibenzylidenetriacetophenone, by the condensation of aceto- phenone and benzaldehyde ; its constitution is probably, therefore,ORGANIC CHEMISTRY. 141 Para ........ .... dOMe*CPh(CHPh*CHPh*COMe),. Benzylidenetriphenylacetone dia- solves in strong sulphuric acid, and forms a lemon-yellow solution, which darkens spontaneously and becomes ruby-red when warmed.When hydrogen chloride is passed into a n imperfectly cooled mix- ture of benzyl methyl ketone and benzaldehyde, a substance, C25H220, is sometimes obtained ; this forms yellowish crystals, melts a t 140°, and may be distilled without decomposing. It is probably pro- duced by the condensation of an intermediate 1 : 5-diketone in the usual manner, being, therefore, 1 -metlql-2 : 3 : 4-triphenylcycZo-A'- hexenone-5, CMe<:EPh' cHl$>CHPh. It gives an oxime, C,,H,,NO, which forms aggregates of crystals, melts a t 204", and dissolves sparingly in alcohol, but readily in other media. Dibenzyl ketone and benzaldehyde condense in presence of dry hydrogen chloride, forming a substance which has the composition C,,H,,C10, and is, therefore, the hydrogen chloride additive product of benzylidene dibenzyl ketone ; it melts a t 143', and, on distillation, yields phenylacetic chloride and stilbene.Of the above isomeric ketones, C1,H,,O, t h a t melting a t 53" is saturated and produced by a ready elimination of hydrogen chloride from the substance C,,H,,ClO, and is, therefore, in all probability a cyclic compound, 1-phenyltetrahydro-P-naphthenone, CHPh* $JHz C6H4<CH2--co 9 whilst the isomeric unsaturated ketone (m. p. = 71") probably has the constitution CHPh:CPh*COMe. The hydrocarbon melting a t 120°, which was obtained from benz- aldehyde and benzyl methyl ketone by the use of sulphuric acid (Zoc.cit.), turns out t o be stilbeno (compare Miller and Rohde, Abstr., 1S90, 978). A. L. By ARNOLD F. HOLLE- MAN (Rec. 2"yav. chirn., 1898, 1'7, 247--258).-The following table gives the solubilities of ortho-, meta- and para-nitrobenzoic acids in water, chloroform, and absolute alcohol a t temperatures of 1 5 O , 25", and 35'; the numbers represent grams of acid dissolved in 100 grams of the solvent, except in the case of alcohol, when they represent gram-molecules per litre. Solubilities of the Nitrobenzoic Acids. 0*0213 1 0.0235 0'0419 0.088 1 Nitrobenzoic acid. A bs 01 tit e Water at 11 Cliloroform at 1 I The solubility in water of a mixture of the para-acid with either the ortho- or meta-acid is approximately equal to that calculated142 ARSTRACTS OF CKEMTCAT, PAPERS.frorri Nerust's t)ieory of the diniinntion in solubility of one substance i n presence of another haviug ;iu ion in conimon with it. An increase of solubility of the three acids occws, however, when they are all present simultnneously in solution ; and the same is true of a mixture of the ortho- and meta-acids. To explain this anomaly, combination is assumed t o take place between the substances present together (compare Le Blanc and Noyes, Abstr., 1891, 388); this would eluci- date the difficulty experienced in separating ortho- and meta-nitro- benzoic acids by crystallisation from water. W. A. D. Piperonal Derivatives. By S. BAUDE and ALBERT REYCHLER (Bull. SOC. Chim., 1897, [ iii]) 17, 616-618).-EthyZic methylenedioxy- cinnumute, CH2<O>C,H,* CH:CH* COOEt, obtained by the action of metallic sodium on a mixture of piperonal and ethylic acetate, crys- tallises in needles melting at 65-68", is soluble in alcohol and ether, and distils, with slight decomposition, at about 317'.Its dibromide forms colourless plates melting at 84O, and is readily soluble in ether or alcohol, but insoluble in light petroleum. CiC*COOH, ob- 0 Methylenedioxyphenylpopiolic acid, CH,<O>C,H,* 0 tained when the dibromide is repeatedly boiled with alcoholic potash, crpstallises from dilute alcohol i n pale yellow needles, turns brown at 145", and melts and decomposes at 166". Met?~yle~dioxy~?~en~Zc~~etyZene, obtained by heating the above acid with tlhree to four times i t s weight of dry aniline at 150-160°, is a yellow oil.J. J. S. Condensation of P h t h a l a l d e h y d i c Acid with Acetone and Acetophenone. Ey ARTHUR HAMBURGER (Monatsh., 1898, 19, 427-455. Compare Goldschmiedt, Abstr., 1S92, 179, and Hemmel- mayr, Abstr., 1893, i, 181, and 1894, i, 151).-Phthaldehydic acid and acetone condense readily a t 40-60" i n presence of dilute soda ; the liquid, after remaining for 24-48 hours, is acidified with hydrochloric acid, when the mixture acquires a milky appearance, and a gelatinous precipitate slowly forms. This is separated by filtration, washed, and dissolved in alcohol, from which, on cooling, di~~?~t?~aZidedimet?ayl ketone, (CO<??:>CH* CH,),CO, crystallises in the form of white, felted needles which melt at 156-157". On evaporating the filtrate from the above precipitate, or extracting*it with ether, it yields R much larger quantity of a second substance, p?At?Lalidedimethyl hetone, CO<"G"~CH* CH,.CONe, which crystallises from water i n quad- ratic plates of considerable size and melts at 67-68", dissolves readily in water, alcohol, ethylic acetate, and benzene, and more sparingly i n chloroform and light petroleum. Both compounds dissolve slowly in cold, but readily in hot, potash, giving intensely yellow colorations ; with bromine, they give substitution, not additive, compounds. l)'i1117Lt?~alitledinaf!thyZ keto:cinza, CISH1605N, is nearly insoluble in water, -0ORGANIC! CHEMISTRY. 143 :icetic acid, cthylic acetate, and benzene, atid o d y very s1)aringIy iu alcohol, nielhylic alcohol, ether, acetone, and chloroforni, but dissolves readily in cold potash, iind is reprecipitated by acids ; i t is iudistiiictly crystalline, sinters a t lSl", and melts at 197-203". When hydroxylamine acts on phtlialidedimethyl ketone, two isomeyic oxinaes, C,,H,,NO,, are formed; one of these, obtained by acidi- fying the product with hydrochloric acid, crystallises from dilute alcohol in yellowish forms arid melts a t 127-12fi0 ; i t dissolves very readily in methylic or ethylic alcohol or ether, less readily in water, sparingly in benzene and chloroform, and is more easily soluble in alkali than in water.The second oxirne is formed by dissolving the first in boiling water, from which it separates i n white, felted leaflets, or by heating it for some at 100" ; it melts a t 59-61', and dissolves readily in the usual media and in alkalis.Both oximes, when treated with the "Beckmann mixture," give an oil and an acetyl compound: Cl,Hl,N04 ; this forms slender needles, and on warming with fuming hydrochloric acid gives phthalidedimethyl ketone. Phthalidedimethyl ketone reacts with phenylhydrazine and with bromine, hydrogen bromide being evolved in the latter instanc.e ; in neither case, however, is a crystalline compound produced. Phthalaldehydic acid and acetophenone interact in presence of soda at 40" ; the product, phenylphthalidernethyl ketone, ?GH4>CH*CH2*COPh, crystallises from alcohol in long, white, felted needles, and melts at 141-142'. It dissolves instantly in warm alkalis, with a yellow coloration, and is sparingly soluble in water and ether, but dissolves somewhat readily in alcohol.Phenyl pihthalidernethyl ketoxirne, Cl6HlSNOS, forms white needles, sinters a t 1'77O, and melts a t 181-182'; a second substance is obtained simultmeously which is insoluble in soda, and decomposes, evolving gas, a t 180' and melts at 215'. The former is some- what readily soluble in alcohol, ether, and hot benzene, and is very unstable in presence of light, becoming yellow ; potash quickly dissolves it, but it is deposited unaltered on adding an acid. When subjected t o treatment with (' Beckmann's mixture," it yields coo 3-carboxyp?~enyL5-p~~en yZisoxaxoZine, C P h q N O>CH * C,H; COOH. CH, Bromine acts on phenyl phthalidemethyl ketone, hydrogen bromide being evolved, but the product is not crystalline; it is not affected when shaken with benzylic chloride and aqueous soda.When a mixture of phenylhydrazine and phenyl phthalidemethyl ketone is warmed on the water-bath, a substance of the composition -C6H4- C',,H,,N,O,, probably CO<N2Hph>CH' CH,* COPh, is formed. This crystallises from alcohol in yellowish, glistening needles and melts at 118---123O ; i t is very readily soluble in chloroform and alcohol, some- what less readily in benzene and acetic acid, sparingly in ether, and is nearly insoluble in water. When heated with strong sulphuric acid, it becomes dark-red, but quickly dissolves, forming a yellow solution which soon becomes green, especially on the addition of a drop of144 ABSTRACTS OF CHEMICAL PAPERS. solution of ferric chloride. is not affected by hot alkalis or bv concentrated hvdrochloric acid.It does not reduce Fehlingjs solution, and An isomeric Eonymnd, C22H,iN20, possibly " COOH. C,H,.CH<~~~* Gph, NPhON is produced when phenyl phthalidemethyl ketone and phenylhydrazine are heated together in sealed tubes at 170-1900 for 5 hours. It crys- tallises from alcohol in rosettes of needles and melts between 170' and 200', is sparingly soluble in benzene, but dissolves readily in alcohol, ether, glacial acetic acid, and nitrobenzene. I t s solution in concen- trated sulphuric acid is red, becoming dark blue on the addition of a, drop of ferric chloride, owing t o the formation of a sparingly soluble blue compound, and on adding potassium dichromate, a violet coloration is produced which changes successively to dark blue, red, and yellow- ish-brown ; in the latter instance, subsequent dilution of the liquid causes the separation of a red precipitate; dilute nitric acid instantly turns the substance blue; it does not reduce Fehling's solution.It. dissolves i n sodium carbonate solution, producing a liquid which readily forms a lather, and when excess of soda is used, a sodium salt is formed, which crystallises in beautiful, transparent needles. The first isomeride, when heated in a closed tube at 170°, suffers almost complete conversion into the second. When phenyl phthalidemethyl ketone is heated at 170-190° in sealed tubes with phenylhydrazine (2 mols.), a third substnnce, C2,H,,N,0, possibly CO<G$3G>CH* CH,* CYh:N*NHPh, is ob- tained, which is nearly insoluble in water, alcohol, ether, and light petroleum, but dissolves readily i n hot amylic alcohol, ethylic acetate, and glacial acetic acid, sinters at 157', and melts at 163-175'.Sulphuric acid dissolves it, forming a dark green solution in which a trace of ferric chloride, potassium dichromate, or sodium nitrite pro- duces a red coloration. It is insoluble i n boiling alkalis, and does not reduce Fehling's solution. A. L. Behaviour of Phthalide on Distillation with Lime. By HANS KRCZMAR (Monatsh., 1898, 19, 456--460).-A mixture of phthalide and lime was cantiously heated a t about 290' in a long glass tube, through which a slow stream of hydrogen was passed; the distillate contained a clear liquid and a crystalline solid. The liquid portion consisted for the most part of benzene and probably, in part, of toluene, as on oxidation with chromic acid the odour of benzoic acid made itself perceptible.The solid substance was anthracene, probably contaminated with diphenyl. A. L. Condensation of Malonic Acid with Aromatic Aldehydes by means of Ammonia and Amines. By EMIL KNOEVENAGEL [and in part FR. BAEBENROTH and 0. ~OLLWEBER] (Be?-., 1898,31,2596-2619). -When malonic acid is warmed with substituted benzylidenebisalkyl- amines or benzylidenebisdialkylamines, interaction as a rule takes place readily, and acids of the acrylic or malonic series are produced. In the case of benzylidenebispiperidine and malonic acid, the action is represented by the equation CHPh(C,NH,,), + CH,(COOH), = CHPh:CH* COOH + CO, + 2C5H,,N.ORGANIC CHEMISTRY.145 Many benzylidenealkylamines act i n a similar manner, but by using benzylidine-a(or /3)-naphthylamine and benzylidenemetanitr- aniline, no cinnamic acid was obtained. Hydrobenzamide reacts with malonic acid in a fashion which is analogous to the behaviour of other substituted benzylideneamines ; the equation is N,(CHPh), + 3CH2(COOH), = 3c02 + 3NH, + 3CHPh:CH. COOH. Salicylideneaniline and malonic acid yield coumarincarboxy lie acid, aniline, and water. It is not necessary to isolate the salicylidene- aniline, mere addition of aniline to a solution of malonic acid and salicylic acid, or of the aldehyde t o aniline malonate, being all that is required. Similar results with analogous trios of substances have shown that, in general, the order of interaction exerts only a quanti- tative influence on the product obtained.The intermediate product in these reactions, namely, the alkylidine- malonic acid, may be isolated if t h e temperature of the reaction be kept sufficiently low, the optimum point depending on the nature both of the base and of the aldehyde employed. With ammonia, the temperature at which carbonic anhydride is eliminated is lower than where aniline is the condensing agent, and, in consequence, a smaller yield of alkylidenemslonic acid is obtained. It is to be noted that the requisite proportion of base varies with the nature both of the base itself and of the aldehyde used ; it is found, moreover, that, with some bases, little or none of the desired products are obtainable. The necessary duration of the action is also found to vary; in some cases, a short time only is advisable, and in others the reverse holds true.The paper concludes with a detailed description of the experiments on which the foregoing statements are based, and the following substances are described for the first time. Anisyliclenemalonic acid is obtained when anisaldehyde (1 *3 grams) and normal ammonium malooate (1.4 grams) are covered with alcohol and the whole rapidly evaporated on the water-bath nearly to dryness, and is precipitated by means of sulphuric acid from its alkaline solution as a yellow, flocculent substance which melts and effervesces briskly at 185-189' ; i t yields paramethoxycinnamic acid when boiled with alcohol, Pi3-eron~lidenemc~lonic acid is made by warming piperonal with malonic acid and alcoholic ammouia (2 mols.) or with normal am- monium malonate.It is thrown down from i t s solution in soda, on acidification, a s a white, flocculent precipitate, which melts and eff er- vesces at 190-195°. When a mixture of furfuraldehyde and malonic acid is cooled and treated with aniline, the whole soon solidifies and, on subsequently adding hydrochloric acid, crystals of a nitrogenous substance are deposited; this is sparingly soluble in water and dissolves in alcohol, forming a red solution which deposits violet crystals having a metallic lustre. It is completely destroyed by warm soda, and when warmed with sodium carbonate solution t h e colour is destroyed, hut is restored on adding an acid. A. L. VOL. LXXVI. i.I146 ABSTHACTS OF CHEMICAL PAPERS. Condensations of Acid Derivatives of Ethylic Malonate with Ethylic Benzylideneacet oacetat e. E y EMIL KNOEVE NAGEL and W. FABER (Ber., 1898, 31, 2768--2'772).-When ethylic benzyl- ideneacetoacetate (Abstr., 1896, i, 232) and either ethylic isobutyryl- malonate (see below) or ethylic benzoylmalonate (Claisen, Annaclen, 1896,291,72), are heated with a little alcohol until a homogeneous mix- ture has been formed, alcoholic potassium ethoxide then added, and the whole allowed t o remain for several days, the product in both cases is diethylic 5-phenyl-1 : 3-diketocyclohexane-4 : 6-dicarboxylate (Abstr., 1894, i, 576), the isobutyryl o r benzoyl group being removed. "o<:%oEt ): CHPh + COOEt*CHBz*COOEt co<CH,-- CH(COOEt)*CHPh co>CH* COOEt.E:thyZic isobutyylmalonate, CHMe,* CO~CK(COOEt),, prepared from isobutyric chloride and ethylic sodiomalonate, boils at 133-1 34' under 14 mm., and at 126-127' under 10 mm. pressure. C. F. B. Condensing Action of Diethylamine. By EM IL KNOEVENAGEL and W. FABER (Bey., 1898, 31, 2773-2775).-When ethylic benzyl- ideneacetoacetate, CHPh:CAc* COOEt (Abstr., 1896, i, 232), dissolved in a little alcohol, ethylic cuminylideneacetoacetate (Abstr., 1898, i, 404), or benzylideneacetylacetone (Abstr., 1895, i, SO), is mixed with a little diethylamine and allowed t o remain, the product is ethylic benzylidenediacetoacetate, CHPh(CHAc* COOEt), (Abstr., 1896, i, 210 ; Hantzsch, Abstr., 1886, 77), ethylic cuminylidenediacetoacetate or benzylidenediacetylacetone respectively. I n the first case, a similar condensation took place, even when ethylic isobutyrylmalonate was present ; no condensation with the latter substance occurred.C. P. B. Orthaldehydophenoxy-acids. By H E R & i m N CAJAR (Ber, 1898, 31, 2803-281 l).-SodiosaZicylaldehyde, CHO*C,R,* ONa, was pre- pared by treating salicylaldehycle with sodium ethoxide in the presence of a large quantity of alcohol; it is lemon-yellow. When it is suspended i n benzene and treated with ethylic chloroformate, and the product distilled under 90 mm. pressure, a n oil comes over at 197", which is presumably ethylic orthaldehydophenylic cc~bonate, CHO*C,H,* O*COOEt. A41coholic soda appears t o hydrolyse this t o the sodium salt, but the latter is a t once decomposed by water, with formation of salicylalde- hycle ; the ethylic salt forms, however, a yellowish phenylhytlmxone melting at 101 --102', and with aqueous semicarbazide hydrochloride, a yellow product melting at 11l0, which apparently has the composition COOEt*O*C,H,* CH:N*NH* CO *N:CH* C,H,- O*COOEt ; with aqueous hydrnzine hydrate, i t yields salicylaZdehyde iiydmxone, NH,*N:CH*C,H,*OH, melting at 96' (this can also be obtained by adding a solution of hyclrnzine hydrate in dilute alcohol t o an alcoholic solution of snlicylnldehyde ; when treated with acids, i t yields Curtius and Jay's hydroxybenzalazine [Abstr., 1889, 3931) ; with salicylalde-ORGANIC: CHEMISTRY.147 liyde hydrazone, the ethylic salt yields a compound, OH* C',H,*CH:N*N:CH* C,H,* O*COOEt, which melts a t 11 4-1 15', and forms hydroxybenzalazine when treated with acids (salicylaldehyde hydrazone also forms a compound, melting at 11 3-1 14', with ethylic acetoacetate) ; with hydrazine sulphate in aqueous solution, it forms the compound N,(:CH* C,H,* 0-COOEt),, which is bright yellow and melts at 109-110'.With hydroxylsmine, the ethylic salt does not react; by warming salicylaldoxime with ethylic chloroformate in concentrated alcoholic solution, a compound melting at 69.5' is obtained, but this, probably, has the constitution COOEt- 0 *N:CH* C,H4* OH, for salicylaldehyde itself does not react in an analogous fashion. With ethylic malonate, after 3 hours heating on the water-bath, the ethylic salt forms coumarincarboxylic acid, 0--yo Stuart, Trans., 1886, 40, 366).'GH4<CH: C*COOH ( Orthaldehydophenoxyacetic acid (Rijssing, Abstr., 1885, 388) was prepared by heating salicylaldehyde (1 mol.) with monochloracetic acid (1 mol.) and aqueous caustic soda (2 mols.) of sp. gr. = 1.2 ; when boiled with 3 per cent. methyl alcoholic hydrochloric acid, it yields the rnethylic salt, CHO*C,H,*O*CH,* COOMe, which melts at 55-56', and forms a yellow hydrazone, N,(:CH* C,H,* O*CH,* COOMe),, melting a t 159-160' (the allied opianic acid yields a pseudo-salt ; compare Wegscheider, Abstr., 1 892, 1208). With hydrazine hydrate, the acid gives a yellow hydrazone, N,(:CH* C,H,* O*CH,* COOK),, which me1 t s and decomposes a t 222' (and not a phthalazone; compare Abstr., 1893,371). When heated with hydroxylamine hydrochloride in 80 per cent.alcoholic solution, it yields the ethylic salt of orthaldoxime- phenoxyacetic acid (Elkan, Abstr., 1887, 259), NOH:CH* C,H,*O*CH,*COOEt ; this melts at 80'. By P. GENVRESSE (Bull. Soc. Chim., 1897, [iii], 1'7, 599-609. Compare Abstr., 1897, i, 240).-Phenylene bisulphide, (C,H,S),, and an isomeric compound are obtained by the action of sulphur on benzene in the presence of aluminium chloride. The diphenylene bisulphide may be removed by treating with boiling glacial acetic acid until the residue gives a n emerald green colour with concentrated sulphuric acid ; the impure isomeride is then freed from excess of sulphur by washing with carbon bisulphide, and is dissolved in hot benzene, in which it is sparingly soluble and from which it separates on cooling in an amorphous condition.It melts a t 295', but begins to sublime even at lower temperatures, is sparingly soluble i n hot benzene or chloroform, and is insolnble in most other solvents. Chromic acid oxidises i t to isodiphenylene disulphone, C,H4<So2>C,H4, which has not been obtained in a crystalline form, but is colourless, melts above 360°, is non-volatile, and only sparingly soluble in benzene, and when heated with Concentrated sulphuric acid a t 200" is converted into n sitbstnnco soluble in water. C. F. B. An Isomeride of Diphenylene Bisulphide. so2 1 2148 ABSTRACTS O F CHEMICAL PAPERS. Fuming citric acid oxidises tho isobisulphide, yielding a mixture of products which have not been separated. Fuming sulphuric acid yields a colouring matter isotvioxyphenylene hisuZphide, C,S2H40?, when heated in sealed tubes at 120-125° with the isobisulphide ; this compound is readily soluble in water or alcohol, giving red solutions, but is insoluble in benzene, chloroform, &c.I n the solid state, it is brown, and with sulphuric acid gives a green solution; it may be obtained in a crystalline form from dilute sulphuric acid, but not from its aqueous or alcoholic solubions. I t s aqueous solution, when mixed r i t h a solution of sodium chloride, yields a brownish red precipitate, containing 70 per cent. of sodium chloride, and insoluble in alcohol. Sodium hydroxide turns the red, aqueous solution black, and a precipitate is slowly formed ; a precipitate is also obtained with sodium carbonate, but no evolution of gas occurs.Barium hydroxide gives a dark brown precipitate, which, on adding an excess of hydroxide, becomes white; it is sparingly soluble in hot water, and its composition is represented by the formula C,S,H,O,Ba. The dark coloured precipitate can also be obtained in a crystalline form, and has the composition (U,S2H30,),Ba. A tyiacetyl derivative, C,S,O,HAc,, is obtained when the compound is boiled with acetic anhydride, but when the acetyl derivative is boiled with barium hydroxide, only one acetyl group is removed. The acetyl derivative forms a hard, black mass, soluble in water. The brown coiouring matter gives azo-colours with aromatic amines. J. J. S. Hydrazides and Azides of Sulphonic Acids. By THEODOR CURTIUS and FERDINAND LORENZEN (J. pr. Chein., 1898, [ ii 1, 58, 160-189.Compare this vol., i, 136).-The ethereal salts of aromatic sulphonic acids, R.SO,H, are completely hydrolysed on standing in the cold with hydrazine hydrate, the hydrazine first formed taking up water, with the production of the diammonium salt of the sulphonic acid, whereas the ethereal salts of sulphinic acids are not only hydrolysed, but decomposed by the reducing action of the diamide according t o the following equation, 4PhS0,Et + 3N2H,*OH = 2Ph2S, + 4EtOH -I- 7H,O + 3N,. The hydrazides of the sulphonic acids can also be obtained by the action of hydrazine hydrate on the acid chloride; they reduce an ammoniacal solution of silver nitrate and Fehling's solution, and precipitate mercury from mercuric oxide. Iodine converts them into bisulphides and disulphoxides, but the latter could not be isolated, a similar reaction taking place when the sulphonehydrazides are heated.Like the hydrazides of the carboxylic acids, they are of a basic character, and condense with one molecule of an aldehyde or ketone, Acetic anhydride replaces one hydrogen of the hydrazine residue by an acetyl group, and nitrous acid converts them into the sulphon- azides, which, unlike the azides of carboxylic acids, are not changed by heating with water or alcohol ; neither are they acted on by bromine, and only with great difficulty by alkalis. Be.lzxeizesuZ~~~~oize~~~~~.ccsine, PhSO,*NH*NII,, crystallises from alcohol in large plates or prisms melting and giving off gas at 104-106".ORGANlC CHEMISTRY. 149 The ?qlu'rocldoriiZe separates from alcohol in fine needles melting, with evolution of gas, a t 150--152O, and the sodium salt, PhSO,*NNa*NH,, forms glistening plates.Benxyl idene benxenesulphonehydra~i~z~, SO,Ph* NH*N : CHPh, formed by the action of benzaldehyde on the hydrazide, crystallises from dilute alcohol in colourless needles melting at 110-1 12" ; the corresponding acetoiLe [P-propylidene] derivative forms glistening leaflets melting a t 143-145", and the acetyl derivative crystallises in groups of glisten- ing needles melting a t 1S3-1S4'. DibenxenesuZphoneh3draxide, SO,Ph*NH*NH*SO,Ph, produced by the interaction of benzenesulphonic chloride and benzenesulphone- hydrazide, crystallises from alcohol or water in glistening needles melting and giving off gas at 228'.It reduces Fehling's solution and ammoniacal silver nitrate slowly in the cold, and is decomposed by iodine with evolution of nitrogen, Boiling dilute sulphuric acid decomposes it very slowly, but boiling alkalis decompose it readily with production of benzenesulphinic acid. BenxenesuZphonaxide, SO,YhN,, is a yellowish oil which does not solidify when cooled, has a sweet odour, and when reduced with zinc dust and acetic acid is converted into benzenesulphonamide ; it may be obtained by the action of nitric acid on benzenesulphonehydrazide. Biamnzonium benxenesulpl~onc~te, SO,Ph*N,H,, obtained by the action of hydrazine hydrate on methylic benzenesulphonate, is a crystalline substance melting and decGmposing a t 175". When further acted on by benzenesulphonic acid, it yields the diamrnonnium salt, N,H,(PhSO,III),, crystallising from alcohol in glistening leaflets, which begin to de- compose when heated t o 250" and are not completely melted at 275".The corresponding diammonium salt of benzenesulphinic acid, N,H,(Ph,SO,H),, crystallises from alcohol in glistening leaflets melt- ing and decomposing at 139-141". P-Nap~Lt?~ylsuZp?~one7Lydrc~xicZe crystallises from alcohol in colourless needles melting and evolving gas a t 137-139', and when boiled with dilute sulphuric acid, is converted into P-naphthylsulphinic acid and hydrazine sulphate. The hydrochloride f orms tufts of needles melting at 148-150", and the sodium salt crystallises from alcohol with lEtHO in glistening leaflets, which do not melt when heated t o 275'.BenxyZidene-P-napTLt?~~Z~ulpT~onehydraxine, C,,H7* SO,* NH* XCHPh, obtained by the action of benzaldehyde on the sulphonehydrazide, crystallises in colourless needles melting and giving off gas at 150-1 52", and the corresponding acetone [P-propylidene] derivative forms glistening plates melting and decomposing at 156-158'. Aceto-P-naphthyZszc~hone~~y~rax~d~, C,,H7*S0,*NH*NHAcl prepared by the action of acetic anhydride on the sulphonehydrazide, forms colourless, glistening needles melting a t 208-209". Di-/?-naphth ylsuljd~onehydraside, ( C,,H7* SO,*NH),, formed by the in- teraction of the aulphonehydrazide with P-naphthylsulphonic chloride, crystallises from alcohol in slender needles melting and decomposing a t 2 15". Dilute sulphuric acid converts it into P-naphthylsulphonic acid and hydrazine sulphate.The sodium salt is a yellow powder, not melting when heated to 275'.150 ABSTRACTS OF CHEMIC'AI, PAPERS. p-N~~~l~tl~~lsull-'honccxicZe, Cl,H7S02*N,, crystallises in white leaflets melting at 44-46", but not exploding when heated to a higher tem- perature; when reduced with zinc dust and acetic acid, it is con- verted into P-naphthylsulphonamide. Hydrazine hydrate acts on ethylic benzenesulphinate and methylic P-naphthylsulphinate, giving respectively phenylic bisulphide and /3-naphthylic bisulphide, and not the sulphinehydrazides. A. W. C. 4 : 4-Diamidodiphenyl-3 : 3'-dicarboxylic Acid. By CARL BULOW and ULRICH VON REDEN (Ber., 1898, 31, 2574--2582).-This acid, C,,H,(NH,),(COOH),, is prepared by reducing orthonitrobenzoic acid in alkaline solution, and boiling the hydrazo-compound thus produced with concentrated hydrochloric acid. When it is dissolved in caustic soda, and the solution is shaken with benzoic chloride and kept cold meanwhile, 4 : 4'-dibenxamidodiphenyl-3 : 3'-diccc~boxyZic acid, melting at 302-304O, is formed (the ummonium salt crystallises with 2H20) ; with acetic anhydride instead of benzoic chloride, the diacet- ccmido-compound is formed ; this melts a t about 300°, and is converted into benzidine when it is boiled in glycerol solution.When the acid is dissolved in dilute hydrochloric acid and treated with sodium nitrite, and the hydrochloride formed is repeatedly dissolved in water and precipitated with a mixture of alcohol and ether, yellow 4 : 4'-tetraxodip7~enyZ-3 : 3'-dicarboxyZic acid, C12H,(N:N* OH),(COOH), + 2H20, is obtained, and this, if boiled with 1 per cent.sulphuric acid, yields 4 ; 4'-dihydroxydiphengZ-3 : 3'-dica~boxylic acid, which melts at 302--305O, and yields 4 : 4'-dihydroxydiphenyl when heated with lime. When heated with bromine in hydrobromic acid solution, the tetrazo-acid yields a perbromide from which, by means of ammonia, greyish-green 4 : 4'-disdiaxoinzidodiphenyZ-3 : 3'-dicarboxylic acid, Ci2H,(N,)2(COOH),, decomposing at 165', is obtained. Reduced by prolonged boiling with absolute alcohol, it yields diphenyl-3 : 3'-dicarb- oxylic acid, from which diphenyl can be obtained by heating with lime ; the latter acid forms a meth,yZic and an ethylic salt, melting at 100-102" and 68' respectively, when it is dissolved in the correspondingalcohol and the solution is saturated with hydrogen chloride.When reduced with sodium sulphite solution, the tetrazo-acid yieldsdiphnyZ-4: 4'-dihydraxine- 3 : 3'-dicarboxyZic acid, C12H6( NH*NH,!,(COOH),, which is greyish t o reddish-white, carbonises without melting when heated, and condenses with acetone at 40-50" to form the dark green disacetonediphenyZ- 4 : 4'-dihydraxone-3 : 3'-dicurboxyZic acid, C12H,(NH*N:CMe2)2(COOH)2, melting at 265-267". With phenol in strong caustic soda solution, the tetrazo-acid condenses to form the red 4 : 4'-disphenoZaxodiphnyZ- 3 : 3'-dicarboxyZic acid, Ci2H6(N:N* C6H,* OH),(COOH), ; with ethylic acetoacetate in aqueous sodium acetate solution, it gives 4 : 4'-disetlbyZic acetoacetate-uxodiphenyl-3 : 3'-dicarboxylic acid, C,,H,(N:N* CHAc* COOEt),(COOH), + H20, melting a t 275-278" ; with ethylic malonate in the presence of dilute alcohol and sodium acetate, it yields, after crystallisation of the C,,H,(NHBz),(COOH),, ci ,H,(OH) 2 (COOK) 2 9ORGANIC CHEMISTRY. 151 product from alcohol, brownish-yellow ethylic 4 : 4'-ilisethyZic nzesoxaltcte- clih?/drccxonedi~~~iei~yZ-3 ; S'-diccwbozylcte, C,,H,[N.N:C(COO~ti,1,(C'OOEt), + 2lI,c), which melts at 257".Parahydroxyphenylphthalide, and its Conversion into Deri- vatives of Anthracene. By AUGUSTIN BISTRZYCKI and D. W. YSSEL DE SCHEPPER (Ber., 1898, 31, 2790-2802).-The hydroxy- phenylphthalide, GO<, >CH* C,H4* OH, previously described (Abstr., 1894, i, 600), yields paramethoxyphenylphthnlide (Nourrisson, Abstr., 1886, 1029) when methylated, and so must itself be a para- hydroxy-compound ; similar conclusions may be drawn as to the con- stitution of the other substances described at the same time.When parahydroxyphenylphthalide is reduced in alkaline solution by boiling with zinc dust, it yields 4-?iyd~oxydiphen?/lmet?~ane-2'-ca~b- oxylic acid, COOH. C,H,*CH,- C,H,*OH, which melts :at 145-146' ; i t s anhydrous silves. salt was analysed. When i t is dissolved in strong sulphuric acid at a temperature not exceeding 30°, and the solution is poured into water, the product is 2-J~ydrox~acntl~mi~oZ, C. F. €3. -0- 6 4 C,H4<8EH)>c6H,* OH ; this melts at 221', and forms a diucetyl derivative melting at 141-142'; the latter, when oxidised with chromic acid in acetic acid solution, yields a product identical with P-acetoxyanthraquinone. 4-l1yd?oxy- 2-metl~yldiphenylrnetl~ane-2'-carboxylic acid, COOH- C,H4* CH,* C,H3Me* OH, melts at 168-169'; i t s anhydrous bakum salt WRS analysed.2-l~ydroxy-4-meti~yZc6nt?ri.a~aol, C,H4<bH -->C,H,Me* OH, melts at 224O, its diacetgl derivative at 172-173". 2-Acetoxy-4-methylaril.tl~ra- quinone, C6H,<co>C,K,Me* OAc, melts a t 134-1 35', is yellow, and, when hydrolysed with alcoholic potash, yields the 2-lLyds.oxy-com- pound, which is yellow and melts at 299-300°, beginning to sublime at about 200". Metacresylphthalide yields a similar series of products. C(OH) co 4 : 5' : 6'-Trinzethoxybenxoyl-2'-benxoic acid, COOH- C,H,(OMe),* CO*C,H,* OMe, formed when hemipinic anhydride is heated i n benzene solution with anisoil and aluminium chloride and the product treated with hydro- chloric acid, melts at 215-216'; its anhydrous silver salt was analysed.When reduced with zinc dust in alkaline solution, i t yields O--- paramethoxypherLyl~seudomeconine, GO<, (OISle), >CH* C6H4* OMe, which melts a.t 111-lZ3°. With zinc dust and hydrochloric acid in acetic acid solution, 4 ; 5' ; 6'-trimethoxydiphenyl.met?~mae-2'-ca~boxyl~c acid, GOOH* C6H,(OMe),* CH,* C,H,* OMe, melting at 122-124', is obtained ; strong sulphuric acid converts this into 2 : 3' : 4'-tvirnethoxy- 6 2 dihydronnthyone, C,H,(OMe),<Co->C,H,*OMe, which melts at CH2152 ABSTRACTS OF CHEMICAL PAPERS. 169-170', and is oxidised by chromic acid in acetic acid solution to 2 : 3' : 4'-trinzetI~oxyanth~aquinone, C,H,(OMe),<~~>C,H,* OMe, which is yellow, melts a t 235', and yields flavopurpurin when heated with aluminium chloride at 210'.Dinit~.oiuara~?/ds.ox~p~~eny~~~t~aZide? CO<-o->CH*C6H,(N0,),*OH [(NO,), : OH = 3 : 5 : 4, probably], obtained by treating parahydroxy phenylphthalide with the theoretical quantity of nitric acid (sp. gr. = 1.50) in concentrated acetic acid solution, is yellow, and melts at 1 87". Amido~al.cchydroxyphenl/~~~tJbaZide, CGH4 CO<igT>CH- C,H,(NH,')*OH [NH, : OH = 3 : 4, probably], is obtained" b i reducing tho corresponding nitro-corupound (Abstr., 1894, i, 600) with tin and hydrochloric acid; it is yellowish, and melts a t 229-230'. When a mixture of phthalaldehydic acid and 1-naphthol is stirred into 73 per cent.sulphuric acid at O", the product is 4-hydroxy- nc6pJ~thyl23~thcclide, CO<,&->CH* C,,H,*OH ; it melts at 322-223". An isomeric substance [OH = 2 (I)], obtained in a similar way from Electrolytic Reduction of Aldehydes and Ketones. By HUGO KAUFFMANN (Zeit. EZektvocJbem., 1898, 4, 462. Compare Abstr., 1896, i, 649).-Benzaldehyde, dissolved in alcoholic caustic soda, gives a good yield of the two hydrobenzoins when quickly reduced by means of a fairly large current. Other aldehydes and ketones behave similarly, acetophenone giving acetophenonepinacone, and the ketone, the corresponding benzhydrol. I n acid solution, the reaction takes place less smoothly, benzaldehyde giving large quantities of resinous products.Benzil (10 grams), dis- solved in boiling alcohol (150 c.c.) and 10 per cent. solution of sodium hydroxide (30 c.c.), and electrolysed for 6 hours at 70-80" with 2-3 amperes, gives, besides benzoic and benzilic acids, symmetrical tetra- phenylerythritol or benxoinpinacone, OH* CHPh*CPh(OH)*CPh(OH)*CHPh*OH, the yield of the latter being about 10 per cent. of the b e n d used. This substance melts at about 235", crystallises from alcohol in slender needles, and is most readily soluble in alcohol containing some alkali, but very sparingly in other solvents. When evaporated, the mother liquor of the benzoinpinacone deposits thick crystals which, after recrystallisation from chloroform, melt a t 175' and have the composi- tion C?8H,,03. Benzoinpinacone was also obtained by the electrolytic reduction of benzoin ; when heated at 235-240' in a vacuum, it loses 1H@, forming benzoin, With acetic chloride, it loses water and 6 4 2-naphthol, melts at 234-235'. c.P. B. CO[C6H*'N(cH3),]p - CHPh*CPh*OAc forms a diacetyl compound, probably O<CHph,&h.OAc ; this Crys- tallises from alcohol in white plates melting at 198', The substance C,,H,,@, does not undergo the pinacone decomposi-ORGANIC CHEMISTRY. 153 tion ; it forms a monacetyl compound, losing 1H,O a t the same time. The author considers that i t s constitution is probably OH CHPh*CPh(OH)*CHPh BCHPh, OH. Condensation of Mandelonitrile with Phenols. By AUGUSTI~~ BISTRZYCICI and HUGO SIMONIS (Ber., 1898, 31, 2812-2813).- a-Hydroxydiphenylacetolactone can be prepared directly from com- mercial mandelonitrile by acting on the latter with sulphuric acid and phenol, and this greatly lessens the cost of production.Neither the lactone nor the sodium salt of the acid appears to pro- duce any definite physiological effect on dogs. 7-Lactones of Phenolic Acids. By GUSTAV CRAMER (Ber., lS9S, I . Derivatives of Ort?Lo?~ydroxydipheny lace to Zactone. -Eth y lic o d m - hydroxydiphenylucetate, OH- C,H,* CHPh*COOEt, obtained by the action of alcoholic hydrogen chloride on the lactone, crystallises in stellate groups of prisms melting at 104-106O. y-Lactones of alcoholic acids, on the other hand, are usually converted into chloro- acids by this treatment. ~ r t ~ ~ o ~ ~ y d r o x y d ~ p ~ ~ e n y ~ a c e t a m ~ ~ e is obtained by the action of ammonia on the lactone, and crystallises in slender needles melting at 161-162'.When i t is heated at 180°, i t is con- verted into the lactone. OH* C6H4* CHPh*CO *NHMe, prepared by the action of methylamine on the lactone, crystallises in small needles melting a t 180-182'; the anilide, obtained in a similar manner, crystallises in lustrous, white plates melting a t 1 4 3 - 1 4 6'. OH* C,H,* CPh( NHJ-CO-NH,, is formed by the action of aqueous ammonia on orthohydroxydiphenyl- bromacetolactone, and melts and decomposes a t 150-15 1'. When it is boiled with hydrochloric acid, it is converted into the orthohydroxy- diphenylglycocine ?hydyochZoride, which melts a t 275-27s'. The cor- responding cccid crystallises in very hygroscopic needles melting a t 210-2 15',and probably has the constitution OH* C,H,* CPh<:%>O. It follows from this that the additive product obtained by the action of ammonia on the bromolactone is a true hydroxyamide and does not contain the lactone ring.Ortho~~ycl~ox~diphenyZacetcclnidoacetoluctone, NHAc*CPh<!EEj>O, obtained by the action of acetic anhydride and sodium acetate on the hydrochloride of orthohydroxydiphenylglycocine, crystallises in slender, lustrous needles melting at 225 -228'. II. Derivatives of Phenplparacresy Zucetoluctone. - PlbenyZpamcresyl- ucetamide, OH* C,H,Me*CHPh*cO *NH,, crystallises in stellate groups of lustrous prisms and melts a t 139-1 40'. PILenyZ~ccrucresyZ~rom- acetolactone, CPhBr<2Cb->0, forms well developed, tabular mono- symmetric crystals [u : b : c = 1.8482 : 1 : 2.1060 ; ,G = 85' 13'1.Phenyl- paracresylanzidoacetanaide, OH* C,H,Me*OPh(NH,)*CO *NH,, forms lustrous crystals me1 ting a t 1 4 6 - 1 4 So. I'henylpcci.acresylglycocine, OH* C,H3Me*CPh(NHz)*C00H, which is almost insoluble in any of T. E. A. H. 31, 2813-2821). The corresponding metl~ykurnide, OYt?Loh ydroxydiphen y Zanzidoacetunaide, c' H Me154 ABSTRACTS OF' CHEMTCAT, PAPERS. the ordinary SoIvents, melts st 190-102° ; the IiydrochZuride readily loses hydrogen chloride if left in n desiccator. P?Len?l~~ctracresylucet- ~lirLidoucetoluctore, NHAc*CPh<"C&->O, C H Me crystallises in lustrous needles melting at 2 14-2 16". ~hen~~ccrcccres~~ethoxyuceto~ac~one, OEt* CPh<?:_">O, crystallises in lustrous prisms melting at 1 22".Y~~en~2parucres~Zet~ox~acetic acid, OH* C,H,Me*CPh(OEt)*COOH, crystallises in slender needles melting at 131-134", and its ccmide in small needles melting a t 103-105°. 111. Beriz.atiues of Phe~~~lmetacresykcccetoluctone.-PJ~erzylmetacresy~- ucetccrnide crystallises in lustrous prisms melting at 163-1 66". PhenylnzetucresylbrornucetoZactone forms pale yellow, lustrous plates melting a t 96 -97". Pl~enyZmetcccresyZet?~oxyacetolccctone crystallises in lustrous prisms melting at 91-93". Condensation of Mandelic Acid with ,&Naphthol, Resorcinol, and Orcinol. By HUGO SIMONIS (Ber., 1898, 31, 2821-2830).- Phenyl-P-hydroxynaphthylacetolnctone is best prepared by the action of mandelonitrile on P-naphthol. The basic bccrium salt, C,,H,,O,Ba, crystallises with 3H,O in small, soluble prisms, whilst the norr.mal salt, (C,,H,,O,),Ba + 2H,O, is sparingly soluble, and crystallises in long, thread-like needles.~heny~-~-?cydroxynup?~t~~~bro~c6cetokcc~CPhBr<ygz>O, produced by the action of bromine on t h e lactone, forms well-developed, greenish-yellow, monosymmetric crystals [a : 13 : c = 1,2894 : 1 : 0.480 ; P= 91" 30'1, and melts a t 121'. Phenyl-P-hydvoxy- IztcplitlL?/Zmet~ox~ucetoZccctone, OMe* C P h < ~ ! j f Q O , obtained by the action OF methylic alcohol on the foregoing compound, crystallises in yellow prisms melting at 136". Phenyl-P-hydroxynccphthylethoxy- cccetolactone forms colourless crystals melting at 145") and is accom- panied by two deep yellow substances melting at 187" and 233" respectively. The corresponding acid forms a basic buriurn salt, C',,H,,O?Bs, as well as a norind salt, both of which are sparingly soluble in water.I'henyZ-~-I~ydrox~lmuplitl~~Zbenzylox~acetolctctone, CH,Ph* O*CPh<-~O~>O, C H obtained by the action of benzylic alcohol on the bromo-compound, forms colourless crystals and melts at 181", whilst the corresponding phenoxy-derivative melts a t 160". Mandelic acid reacts with resorcinol in presence of sulghuric acid t o form two isomeric lactones. Phe~z?~lresorcylacetolactone melts at A. H. >GO. YH:CH* E-CHPh 133", and probably has the constitution OH*C:CH -C---0 It forms tabular asymmetric crystals [a : 6 : c = 0.6007 : 1 : 0.7010 ; ~ = 7 5 " 4 2 ' ; P=11Go 19'; y=108" 16'1. The isomeric compound, isop?~enyl~esorcylacetoZuctone, melts at 125") and probably has the constitution (?HiC(oH)* f?CHPh>CO.The crystals belong t o the rhombic system [a : b : c = 0.895 : 1 : 0.7841. CH .CH---C---0ORGANIC CHEMISTRY. 155 Both lactones yield homo-derivatives, that of the normal lactone welting a t 145", and that of the isolactoiie at 142". 1)ibi,o,)Lol,~~en?/l- resol.c?lZ~6celoZactor~e, C,,H,O,Br,, is obtained from the lactone melting a t 183", and probably has the constitution CO<-, ->G6H2Br*OH. Plwzylorcyl- acetoluctone crystallises in slender needles melting at 155". The SO- lactone melts at 172". iMonobyonzophenylorcyZacetolctctone forms brown- ish crystals melting a t 185', whilst the dib?.omo-Zuctone melts a t 205". By R~OSES GOMBERG (J. Amer. Chem. Xoc., 1898,20,79O).---On mixing solutions,in benzene o r carbon bisulphide, of triphenylbromomethane and excess of icdine, a periodide, CPh,BrI,, crystallises out ; after recrystallisation from benzene or carbon bisulphide, it melts at 121-122'.The periodide may be obtained in bluish-green, iridescent, hexagonal prisms or in small needles. On .two occasions, the unusual phenomenon of the formation of hollow crystals was observed, the canal apparently coinciding with the longitudinal axis of the crystal. The author points out that all periodides hitherto described ale those of metallic salts or of bases, whereas triphenylbromomethane is not a base. CPhl3r Orcinol, like resorcinol, yields two isomeric lactones. A. H. A Periodide of Triphenylbromomethane. G. W. F. H. Tetraphenylmethane. By MOSES GOMBERG (J.Anaey. Chein. Soc., 1898, 20, 773-780),-This paper is a revision of the author's work on tetraphenylrnethane (hbstr., 1897, i, 623). Triphenylmethane is brominated, and the triphenylbromomethane produced treated with phenylhydrazine, when it yields triphenylmethanehydrazobenzene ; this, when oxidised with nitrous anhydride, gave triphenylmethane- azobenzene melting a t 110-112', which, on heating at 1 10-120°, evolves nitrogen, forming tetraphenylmethane, the yield being, how- ever, very poor. Tetraphenylmet ham crystallises from benzene in white, glistening needles. That tetraphenylmethane is really formed, is indicated, not only by the analysis, but by a cryoscopic determination of the molecular weight ; moreover, the substance is readily and completely converted into a tetranitro-derivative melting a t 275'; this does not yield ,z sodium derivative by the action of sodium ethoxide, whereas the nitro- phenylmethane derivatives, CH,[C,H,(NO,),],, N 0,.C,H,- CH,. CN, CH(C6H,*N0,),, which still contain hydrogeniattached t o the methane carbon atom, readily yield sodium derivatives. Tetranitrotetra- phenylmethane appears to be reduced by zinc dust and acetic acid to leucopararosaniline. G. W. F. H. Constitution of Phthalyl-Green. By ALBIN HALLER and ALFRED GUYOT (Compt. rend., 1897, 125, 1153-1 156. Compare Abstr., 1881, 587, and 1898, i, 483). The colouring matter produced by the condensation of phthalyl tetrachloride and dimethylaniline is identical with 0. Fischer's phthalyl-green. There are many points of resemblance between this compound and malachite-green, and the authors put forward the formula, NMe,* C,H,* COO C,fT;CCl(C!,H;NMe,) ,,156 ABSTRACTS OF CHEMICAL PAPERS.as being most in accordance with the reactions of the former sub- stance ; in other words, phthalyl-green is malachite-green containing the radicle, NAIe,* C,H; Go, introduced into an ortho-position in tbe non-substituted phenyl group. The leuco-base obtained from such a colouring matter should have the formula, ~~~e,*C,H,*CO*C~H;~H(C,H~*NMe,),, which is in agreement with 0. Fischer's analytical results. Rosenstiehl has shown that the basic colouring matters of the triphenylmethaue series containing n atoms of amidic nitrogen are capable of combining with (n + 1) molecules of hydrochloric acid t o form polyhydrochlorides, of which pararosaniline tetrahydrochloride, CCI( C,H,*NH2,HC1),, may be taken as the type.Phthalyl-green behaves like pararosaniline, and forms a tetrahydro- chloride. This compound, although containing four chlorine atoms ought not t o combine with 2 molecules of platinic chloride, since the formation of a platinochloride is due only to the presence of quinque- valent nitrogen atoms. It might be expected, however, that 2 molecules of the tetrahydrochloride mould combine with 3 molecules of platinic chloride. The platinochloride obtained by the addition of platinic chloride t o a solution of the colouring matter in concentrated hydro- chloric acid has the formula (C,H3,N30C1),,3H2PtC1,. By EUGEN BAMBERGER Bey., 1898, 31, 2624--2626).-The author has obtained with ,&naphthol results similar to those described by Dimroth (this vol., i, 54) in the case of phenol.p-H?ldrox?lnaphthyl-l-naercztric acetate, OH*C,,H,*Hg*OAc, is made by adding P-naphthol (13.2 grams) to a clear solution of mercuric oxide (20 grams) in hot acetic acid (520 c.c.) ; it separates a t once as a heavy, crystalline precipitate, and can be purified by recrystallisation from hot acetic acid. It crystallisesin white, shining needles, and, when quickly heated, melts and decomposes at 185' ; it is sparingly soluble in most of the usual media, but dissolves readily in soda, and is reprecipitated on addition of acetic acid; on addition of ammonium sulphide to its aqueous solution, a voluminous, yellow precipitate is produced which blackens when the liquid is heated, mercuric sulphide being formed.The mercury is very loosely attached to the naphthol nucleus, and the union is destroyed by the addition of soda or of diazotates, P-naphthol being formed in the first case, and phenolazonaphthols being produced in the second. G. T. M. Mercurial Compounds of ,%Naphthol. A. L. Synthetical Isoborneols ; their Identity with the Fenchylic Alcohols. By GUSTAVE BOUCHARDAT and J. LAFONT (Cow@. rend., 1898, 126, 755--757.)-Synthetically prepared dextrorotatory iso- borneol, obtained by the authors by the action of certain acids on lsvorotatory turpentine, consists of a mixture of the dextrorotatory and inactive fenchylic alcohols; these, on oxidation, give rise t o ltevo- rotatory and inactive fenchone respectively.The former is the optical antipode of the dextrorotatory fenchone obtained from oil of fennel ; both compounds have the same crystalline form and melting point, and their specific rotations are equal in magnitude but opposite in sign. The corresponding fenchone oximes bear similar relations toORGANIC CHEMISTRY. 157 each other, and when equal weights of them are mixed together, in ethereal solution, a racemoid form, melting at 154-1556', is obtained on evaporation. When lsvorotatory fenchone is reconverted into dextrorotatory fenchylic alcohol by reduction with alcoholic potash or sodium and alcohol, the optical activity of the substance is less than it was originally. G. T. 31. Beetroot-resin Acid. By KARL ANDRL~K and EMIIL VOTOCEK (Chem.Centr., 1898, i, 621-622 ; from New Zeit. RGb.-Zzcck.-lnd., 40, 39-44).-According to the authors, the substance obtained from the scum formed in the first treatment of the sugar liquors with lime and carbonic anhydride is not isocholesterol, as Kollrepp sup- posed, but a kind of resin to which they give the name beetroot-resin acid. It is prepared by treating the scum with dilute hydrochloric acid and extracting the dry, insoluble material with alcohol. The scum on the waste water of the factory, the deposits in the heating apparatus for the diffusion process, and the diffused juice also contain this substance. It crystallises from alcohol in colourless, silky needles, melts at 299-300", has a specific rotatory power [ a ] n = + 74.4" at 20°, is insoluble in water, easily soluble in boiling alcohol, amylic alcohol, and isobutylic alcohol, and less soluble in methylic than i n ethylic alcohol.It dissolves easily in glacial acetic acid, but the solution, on evaporation, does not yield the original compound. When heated above the melting point, it sublimes and partially decomposes, forming a liquid and a crystalline sublimate; the latter melts and chars a t 241'. The resin-acid bas the composition C,H,O, and crystallises with 1 H20. The colour reactions with sulphuric acid and acetic anhydride are like those of ahietic acid, vitine, ursone, gentiol, cholesterol, and many resin-acids. The sodium and potassium salts were prepared. E. W. W. Aloins. By EUG~NE LEGER (Compt. rend., 1898, 12'7, 234-236. Compare Abstr., 1898, i, 445).-TrichZoroburbaZoin, C,,H,,CI,07 + H20, obtained by the action of potassium chlorate on a solution of barbaloin in concentrated hydrochloric acid, crystallises from alcohol of 90 per cent.in monoclinic, rhomboidal tablets [a : b : c = 1.5448 : 1 : 1.38801. Unlike barbaloin, it dissolves in sodium carbonate solution, but i t does not displace carbonic acid. When heated in sealed tubes with acid chlorides, it yields tricLcet?lltricl~ZorobarbuZoin, which crystallises in very thin, microscopic, rhomboidal lamellae, and tribenxoyZtl.icl~Zorobarb- aZoin,anamorphous compoundvery solubleinacetone,but almost insoluble in alcohol. Under different conditions, barbaloin itself yields only a diacetyl or dibenzoyl derivative, but there can be no doubt t h a t barbaloin contains three hydroxyl groups, which have EL phenolic function, for i t gives a n olive-green coloration with ferric chloride, dissolves in alkali hydroxides, but not in the carbonates, and when heated with sodium hgpobromite in excess, yields carbonic and oxalic acids and carbon tetrachloride.IsobarbnZoi?A, C,,H,,07, is found in the last fractions of the crystal- lisntion of a mixture of aloins. I t crystallises from methylic alcohol in opaque nodules, composed of elongated and truncated, micro-158 ABSTRACTS OF CHEMICAL PAPERS. scopic lamelh which contain 3H20 and are efflorescent ; when crys- tallised from water, i t forms pale yellow, prismatic needles which contain 2H,O. With benzoic chloride in presence of pyridine, it yields dibenxoylisobnrbnloin, very similar to the corresponding barb- aloin derivative., Tric~lorisobarbaloi, obtained by the action of potassium chlorate and hydrochloric acid, forms brilliant yellow, prismatic needles ; when heated in sealed tubes with acetic chloride, it yields a crystallisable triacetyltrichlorisobarbaloin. Tribromiso- bcwbaloin is identical with the compound hitherto described as tribromobarbaloin. The relative proportions of barbaloin and isobarbaloin vary greatly in aloes from different localities. C. H. B. Kosin. By GIROLAMO DACCOMO and GIOVANNI MALAGNINI (L’ Ovosi, 1897, 20, 361-371).-Commercial kosin, obtained from the flowers of Hugenia a6yssiniccc, melts a t 147-149.5O, and appears to be a mixture of at least two substances, since, on fractional dissolution in, and crystallisation from, alcohol, i t yields products having melting points ranging from 105’ to 161’. The portion of highest melting point is the principal constituent of the commercial substance, and resembles in its properties the kosin described by Fluckiger and Buri; it crystallises in long, yellow needles, which are insoluble in water but more or less soluble in organic solvents, and dissolves in alkalis, yielding solutions from which it is reprecipitated unchanged on the addition of acids.Its solutions give a violet coloration with ferric chloride, reduce an ammoniacal solution of silver nitrate, and react with phenylhydrazine to forrn resinous products, and probably a hydrazone ; no reaction takes place, however, with Fehling’s solution or with hydroxylamine.This substance, to which the term ‘‘ kosin ” is properly restricted, is shown by analysis and by cryoscopic mole- cular weight determinations (found, 411 ; theory, 402) to be more accurately represented by the formula C,,H,,07, than by the formula C,,H,,O,,, proposed by Fluckiger and Buri. Triacetylkosin, C22H,, Ac,07, obtained by the action of acetic anhydride on kosin, crystallises from alcohol in small, colourless needles. The corresponding benxoyl derivative, obtained by the action of benzoic chloride on a solution of kosin in caustic potash, forms small, almost colourless crystals. The analyses of these compounds and cryoscopic molecular weight determinations are in accordance with the formula proposed for kosin by the authors. Kosin readily undergoes oxidation in alkaline solution, with the formation of isobutyric acid arid complex resinous substances.With potassium permanganate, oxalic acid is also obtained, whilst when bromine or iodine is employed, bromoform and iodoform are respec- tively produced. Kosin resembles filicic acid in many respects, but differs from i t in not reacting with Fehling’s solution or with hydroxylamine. Thc existence of three hydroxyl groups in the molecule of kosin is shown by the formation of the acctyl and benzoyl dcrivatives, whilst its behaviour with plienylhydrazine and with oxidising agents indicates the presence of a ketonic nucleus t o which an isopropyl group is probably attached. N. L.ORGANIC CHXMISTRY. 159 Strophanthin. By LEOPOLD KOIIN and VICTOR KULISCH (Monntsh., 1898, 19, 385-402.Compare Abstr., 1898, i, 326 and 327).-The strophanthin which the authors have described (Abstr., 1898, i, 329) is not identical with Feist's preparation (ibid.), The seeds from which they obtained the principle were those of Strophanthus Konzb6 or 8. hispidus, probably the former, as they appear to be identical with those employed by Feist, and the isolation of the substance was achieved by Arnaud's process (Abstr., 1888, 1310). The seeds, carefully freed from the adherent hairs, were powdered as finely as possible, washed in a Soxhlet's apparatus with light petroleum, and extracted with 70 per cent. alcohol. To the alcoholic extract, basic lead acetate and lead hydroxide were added, the lend being subsequently eliminated from the filtered liquid by means of hydrogen sulphide ; the filtrate was then evaporated in a vacuum, and the crude strophanthin so obtained purified by repeated crystallisation from water ; i t appears t o be identical with Merck's '' crystallised strophanthin," which is obtained from Strophanthus hispidus. The substance is inactive ; it is very hygroscopic and, when damp, melts a t 100'; the melting point of the anhydrous substance is very uncertain, but lies near 179'.The authors' analyses gave numbers in close agreement with those obtained by Arnaud, but it is as yet uncertain which of the formulz, C,,H,,O,, or C,,H,,O,,, represent the true composition of the substance. d trophanthin appears to contain a methoxy-group ; a determination by Zeisel's method gave a methoxyl content = 3.77-3.4 per cent., a number which points t o the second of the above formulz as being the correct one.AcetyZst?*ophanthin, C,,H,,O,(OAc),, or C,,H,,O,,(OAc),, is made by heating strophanthin with acetic anhydride and anhydrous sodium acetate, and can be purified by recrystallisation from hot alcohol ; i t forms very long, slender, colourless microscopic needles, melts at 236--238', and is insoluble in water. Strophanthidin crystnllises from hot alcohol in beautiful, slender, white needles which aggregate to form silky leaflets. It melts at 195', does not dissolve in water, but is very hygroscopic; it cannot be dried at loo", as it suffers slight decomposition a t that temperature. It has the formula C,,H,,O,, or C,,H,,O,, but, like strophanthin, its methoxyl content is too low, and is lower even than that required by the latter formula.A. L. Action of Cinnamaldehyde on Phenyltoluidoacetonitrile. By WILHELM VON MILLER and JOSEF PLOCHL (Bey., 1898,31, 2718-2720). -In distinction from the behaviour of aromatic aldehydes, which yield two indifferent isomeric compounds with anilido-derivatives or with amido-nitriles, aliphatic aldehydes yield but one indifferent pro- duct (compare this voI., i, 127). Tn order to examine the behaviour of unsaturated aldehydes under similar conditions, the action of cin- namaldehyde on phenyltoluidoacetoiiitrile has been studied. Diphenyltol yl2i9wo line, 7 C'Ph>N* C,H,Me, obtained by heating CH. CPh160 AUSTRACTS OF CHEMICAL PAPERS. phenyl toluidoacetonitrile wit h cinnamaldehyde and potash inalcobo1,crys- tallises from alcohol in lustrous prisms, and melts a t 181'; it arises from the union of the aldehyde and nitrile in molecular proportion, involving elimination of water and hydrogen cyanide, also in molecular proportion.The additive compound, CHPh:CH. CH(OH)* CPh(CN)-NH*C,H,Me, melts and decomposes at 175' ; it doubtless represents an intermediate stage in the production of diphenyltolylpyrroline, which is generated along with hydrogen cyanide when the substance is heated. 31. 0. F. Distillation of Mix:ures of Pyridine and Aliphatic Acids. By GUSTAVE ANDR~ (Conzpt. wad., 1897,125, 1187-1 189).-Chemical combination evidently occurs when formic, acetic, and propionic acids are mixed with pyridine, for a n appreciable amount of heat is developed, but when the mixture is titrated with standard baryta, using turmeric or phenolphthalein a s indicators, the acidity is found to be equal to the whole amount of acid added.After six fractionations of a mixture of propionic acid and pyridine, in molecular proportion, a distillate is obtained boiling at 150-151" under a pressure of 760 mm. This liquid has approximately the composition 2C,H,02,C,H,N, and i t boils 11" higher than propionic acid and 37' higher than pyridine. When boiled under reduced pressure, the mixtkire has no definite boiling point, and the first distillates contain more pyridine than is required by the above formula. A mixture of acetic acid and pyridine behaves in a similar manner; the least volatile portion boils at 139-140" under 760 mm., and i t s composition cori-espontls with 3C21i402, 2C,H,N.When fractionated, this portion is gradually dissociated ; ebullition always commences at looo, and the temperature rises slowly to 139--140'; when distilled under a pressure of 60 mm., it passes over unchanged a t 74", but under 20 mm. i t i s dissociated. A mixture of pyridine and formic acid, in molecular proportion, after seven fractionations, yields a distillate boiling at 148-151' (760 mm.), of the composition 5CH2O2,2C,H,N ; this mixture, when distilled under a pressure of 36 mm., boils a t 74" without dissociation. G. T. M. Ammonio- and Pyridine Salts and Hydrates of Bivalent Metals. By FRITZ RXITZENYTEIN (Zed. cmory. Chew?,., 1898, 18, 253-304. Compare Abstr., 1895, i, 121 ; 1897, i, 38O).-The author discusses the relations between the ammonium salts, hydrates, and pyridine compounds of metals.The repeated occurrence of the same type in the three series is most easily explained hy Werner's theory. The character of the acid residue which is combined with the metal becomes of more importance as the number of pyridine molecules increases ; and the influence of the metallic atom varies in the inver,*e manner. The greatest number of pyridine molecules which can be combined is six, and this occurs in the compounds with CuBr2, CdBr,, and Cdl,. The greatest number of qiiinoline moIecules is four, occurring in the compounds with CaCl, and CoCI,. Isomerides of theORGANIC CHEMISTRY. 161 formula zMeX22Py, which, according to Jorgensen's and Werner's theories, are possible, have not been obtained.The author gives a table of all the known ammonium, pyridine, and quinoline salts and hydrates, and describes the following new com- pounds. Monopyridine nickel chloride pentahydrate, NiCI,,C5H,N,5H,0, is obtained by exposing monopyridine nickel chloride to the air for 4-5 days. Nickel chloride monopyridine hydrochloride, NiC12,C5H,N,HCI, is ob- tained by treating finely divided nickel chloride with pyridine, dis- solving the product in concentrated hydrochloric acid, and evaporating the solution on the water-bath. It crystallises in flesh-coloured needles, deliquesces in the air, gives a green solution in water, and characteristic precipitates with potassiam ferrocyanide and ferricyanide. When the mother liquors obtained in the preparation of this salt are evaporated, a compound is obtained which separates in blue crystals, and is probably a tetrahydrochloride compound.Nickel chloride dipyridine hydrochloride, NiCl,,( C,H,N?HCl),, was obtained on one occasion by dissolving nickel oxide in pyridine hydro- chloride, and concentrating the solution on the water-bath, but the author was unable to obtain it again. The solution, on evaporation, first yields the salt 2NiC1,,3C,HGN, crystallising in greenish- yellow needles ; on further concentration, it yields NiCl,,C,H,N, then NiCl,,C,H,N,HCI, and finally NiC1,,4C5H,N, which crystallises from pyridine in bright blue needles. Nickel swlphate tripyridine dihydrate, NiSO,, 3C,H5N,2H,O, obtained by adding excess of pyridine to an aqueous solution of nickel sulphate, then adding alcohol and boiling, is a bluish-green, crystalline mass soluble in water, and gives a green precipitate with potassium ferro- cyanide.Cobalt chloride tetrapyridine, CoCl2,4C5H,N, is obtained by heating a mixture of cobalt chloride and excess of pyridine hydrochloride in alcoholic solution ; when dissolved in alcohol, i t yields a blue compound, probably CoC1,,2C5H,N,2EtOH, which quickly decomposes into the dipyridine compound. Cobalt chloride monopyridine pentahydrate, CoC1,,C5H,N,5H,0, is obtained as a reddish, crystalline mass by allowing cobalt chloride monopyridine to remain exposed to the air for a few days. Dicobalt chloride pentapyo*idim hydroshloride, 2CoCl,,( C5H6F,HC1),, obtained by heating the tetrapyridine compound dissolved in water with excess of hydrochloric acid, and also by the action of concen- trated hydrochloric acid on a mixture of cobalt chloride and pyridine, is a dark blue, crystalline powder, and gives a red solution in water ; when treated with silver nitrate, all the chlorine is precipitated.Cobalt chloride dipyyidine monohydrochloride, CoC1,,2C,H5N,HCI, obtained by treating the preceding compound in alcoholic solution with the theoretical quantity of silver oxide, crystallises in dark blue crystals, melts a t 1 5 5 O , is soluble in cold water with a red coloration, and, when heated in the air-bath at 150" is converted into the basic chloride, CoCl?,CoO. When treated with excess of silver oxide in alcoholic solution, it is converted into cobalt chloride dipyridine.VOL. LXXVI. i m162 ABSTRACTS OF CHEMICAL PAPERS. When cobalt chloride dipyridine is treated with ammonia and hydro- chloric acid, a salt of the composition CoC1,,(C,H,NC1,NH4C1),,3H,0, is obtained, which crystallises from absolute alcohol in bright blue needles, darkens at 120", melts a t 128-130", and when exposed to the air quickly turns red. The tetrapyridine and dipyridine com- pounds of cobalt chloride, when exposed to the air, take up water and give off pyridine in varying proportions according to the time of exposure, and compounds of the following composition were obtained, UiCl,, 2CiH,N,2H20 ; CoCl,, 1+C5H5N,3iH,0, and CoC1,.3C,H,N,3H,O. Cobalt euZphccte tripyridid' d&&te, *CoSO4,3C5H5N,2H20, ob- tained by treating an aqueous solution of cobalt sulphate with pyri- dine, separates in blood-red crystals, cannot be recrystallised from absolute alcohol or pyridine, is decomposed by warm water with pre- cipitation of cobalt hydroxide, and, when treated with barium chloride, gives a quantitative precipitate of barium sulphate.When allowed t o remain exposed t o . the air for a month, it is converted into the compound CoS04,C5H5N,2H,0. Cobalt nitrate, when heated with pyridine, yields a red compound, which can be recrystallised from absolute alcohol, smells strongly of pyridine, and is probably Co(N0,),,4C5H,:N. The author was unable to obtain a compound of ferrous chloride with pyridine in aqueous solution. When solid ferrous chloride is shaken with pyridine, the compound FeC12,3C5H,N,2H,0 is obtained ; this is a yellow, crystalline powder, has a strong odour of pyridine, is very easily decomposed, and is slightly soluble in water.Ferrous sulphate tripyridirze dihydrate, FeS04,3C,H5N,2H,0, ob- tained in brownish-yellow crystals by adding pyridine to an aqueous solution of ferrous sulphate, has a strong odour of pyridine, is easily decomposed with the formation of basic saltas, and, with barium chloride,. gives the theoretical quantity of barium sulphate. Cudmzum sulphate tripyridine dihydrate, CdS04,3C,H5N,2H,0, ob- tained in a similar manner to the preceding compound, is a white, crystalline precipitate, soluble in water. When heated a t 120" for 1 hour, or allowed to remain 35 days exposed to the air, the pyridine is eliminated and CdS04,2H,0 remains.When anhydrous copper sulphate is treated with pyridine,a dark blue, crystalline powder is obtained, which is probably 2CuS04,C,H5N,H20. It is very unstable, and cannot be obtained in a pure state. It is partially soluble in water with the formation of a basic salt, insoluble i n pyridine, and when boiled with absolute alcohol is converted into a green powder, When allowed to remain exposed to the air, it be- comes bluish-green, and thus has the composition 2CuS04,C5H5N,4H20. The compound, 2CuS04,3C5H,N, obtained by digesting anhydrous copper sulphate with absolute alcohol and excess of pyridine for some time, is a bright blue powder, which, when boiled with absolute alcohol, is converted into the compound CuS04,C5H5N, identical with the pyridine copper sulphate obtained by Jorgensen by heating copper dipyridine sulphnte, and by Lang by heating the compound CnS04,C,H5N,3H,0 at 110".OKGANIC CHEMISTRY.163 Lead chloride pyridine, PbCl,,C,H,N, obtained by boiling lead per- oxide with a solution of pyridine hydrochloride in hydrochloric acid, crystallises quickly from the filtered solution in beautiful, white crystals. Manganese tetrachloride dipyridine, MnC1,?2C5H,N, is obtained by warming freshly precipitated manganese dioxide with pyridine hydro- chloride dissolved in hydrochloric acid. On concentrating the filtrate on the water-bath, it separates in large, bright green crystals, which give a colourless solution with water; when allowed to remain ex- posed to the air, it loses chlorine and is converted into the compound MnC1,,2C,H5N.34angccnous chloride dipyridine, MnC1,,2C,H5N, obtained by adding excess of pyridine to a concentrated solution of manganous chloride, separates in brown crystals which darken on exposure, is easily soluble in warm water, and when heated at 160-165O is converted into the compound MnC1,,1 &C,H,N. Mccnganous chloride dipuinoline, MnC1,,2C,H7N, obtained by adding excess of quinoline to an alcoholic solution of manganous chloride, sepa- rates in brown crystals, is insoluble in cold water, dissolves in hot water with decomposition, and is soluble in cold alcohol. Cadmium bromide dipuinoline, CdBr,,2C,H7N, obtained by boiling cadmium bromide with excess of quinoline, separates from absolute alcohol in white prisms, and is sparingly soluble in cold water.E. C. R. Pyridine Compounds of Quadrivalent Palladium.-By ARTHUR ROSENHEIM and THEODOR A. MAASS (Zeit. anorg. Chem., 1898, 18, 331--338).-Amine bases of quadrivalent palladium have not yet been obtained. The dipalladamine chloride, Pd,CI,(NH,Cl),, described by Devilleand Debray (Compt. rend., 86, 926) is amixture consisting for the most part of ammonium palladium chloride (NH,),PdCI,, and this is the only compound which the authors were able to isolate by the action of chlorine water on palladosamine chloride in the cold. By the action of chlorine water a t higher temperatures, ammonium palladious chloride, (NH,),PdCl,, is formed, with evolution of nitrogen. The action of bromine on palladosamine chloride takes place in a similar manner.The pyridine bases of quadrivalent palladium are, however, easily obtained. Palladodipyridine chloride, Pd(C,H,N),CI2, is obtained by adding pyridine to a solution of palladious chloride; a red precipitate is obtained which dissolves when boiled with excess of pyridine, and on adding strong hydrochloric acid,, palladodipyridine chloride is precipi- tated as a bright yellow, crystalline powder. PalZadidipyridine chloride, Pd(C,H,N),Cl, obtained by the action of chlorine on the preceding compound suspended in chloroform, crystallises in small, dull, orange prisms, gives off chlorine when exposed to damp air, and is fairly stable in dry air ; when heated with potassium hydroxide, a brown precipitate of palladium hydroxide is obtained, and when the cold product is carefully neutralised with hydrochloric acid, potassium palladichloride, K,PdCl,, crystnllises out in characteristic cherry-red octahedra.When shaken with an 111 2164 ABSTRACTS OF CHEMICAL PAPERS. aqueous solution' of potassium iodide, two atoms of chlorine are eliminated, and palladodipyridine chloride is formed. Palladidipyridine dibromochloride, Pd( C5H5NBr,),Br,C12, obtained by shaking palladodipyridine chloride suspended in chloroform with bromine, is a deep orange-red, crystalline powder, and is much less stable than the preceding compound. When boiled with potassium hydroxide and then neutralised, potassium palladichloride is obtained. The authors were unable t o obtain a similar compound by the action of bromine on palladodipyridine bromide. Palladidipgridine di-iodochloridt3, Pd(C,H,N),I,CI,, obtained in a similar manner to the preceding compounds, crystallises in brown needles, and is remarkably stable on exposure to the air.When boiled with water or with potassium hydroxide, it is completely decomposed, with the formation of black palladious iodide. When, however, it is shaken with pure carbon bisulphide, it gives off two atoms of iodine, and is quantitatively converted into palladodipyridine chloride. E. C. R. Derivatives of Nicotinic Acid. By A~nb PICTET and G . SUSSDOKFF (Chem. Centr., 1898, i, 677-678 ; from Arch. Sci. phys. nat. Gedve, [iv], 5, 113--128).-An 52 per cent. yield of nicotinic acid is obtained by pouring a solution of 10 grams of nicotine in 100 C.C. of water and 20 grams of concentrated nitric acid into 250 grams of concentrated nitric acid, and heating the mixture on the water- bath until no more red fumes are evolved ; the nitrate of the acid, which is obtained -on evaporation, melts at 185'.Nicotinic acid, prepared from the nitrate by means of the copper compound or by heating with acetic anhydride or by distilling alone, crystallises in white needles and melts at 229". Ethylic nicotinate, obtained by treating the acid with alcohol and hydrochloric acid, boils a t 220-221' under a pressure of 724 mm.; the nitrate melts a t 185", and the hydrochloride at 126-127". By the action of fatty amines on ethylic nicotinate, the following amides were prepared. MethyZnicotinatmide,C5NH,.CO*NHMe, crystallises from chloroform in long needles and melts a t 104-105O ; the methiodide, C7H,N02,MeI, crys tallises in needles, melts a t 1'74O, and with silver nitrate forms the corresponding nitrate which crystallises from-a mixture of alcohol and ether in prisms, and melts at 155-156'.By treating methylnicotinamide methiodide with silver oxide, an aqueous solution of the hydroxide is obtained, which, on evaporation, decomposes into methylamine and trigonellin. Amyl- nicotinamide boils at 19 1-1 93' under a pressure of 8 mm., and is easily soluble in ether. Allylnicotinamide boils at 186--189" under a pressure o€ 8 mm., at 315-316" under the ordinary pressure, and cannot be purified by distillation. By preparing the chloride by acting on nicotinic acid with phosphorus pentachloride, removing the phosphorus oxychloride, and then treating the residue with aromatic amines, hydrochlorides of substituted aromatic amides are obtained, and these, with sodium carbonate, yield the free amides.Nicotinanilide, C5NH,.CO*NHPh, crystallises from water in needles containing 2H,O and melts at 85' ; the anhydrous compound crystallises from a mixture of light petroleum and benzene or light petroleum and chloro-ORGANIC CHEMISTRY. 165 form in needles and melts at 132'. Nicotinopu~atoluidide crystallises from water in needles and melts at 150". Attempts to introduce a methyl group into allylnicotinamide failed, but potassium-methyl- nicotinamide and allylic iodide yield meti~ykullylnicotinami~e as a viscous liquid. Attempts to remove water from the latter compound, and to obtain nicotyrine from met hylnicotinamide and allylic alcohol a t 160-170' also failed.- Piperidine nicotinute, C,NH,*COOH,C,NH,,, crystallises in long, colourless needles and melts at 122'. E. W. W. Transformation of Fatty Ketazines and Aldazines in to Bv THEODOR CURTIUS and ED. ZINKEISEN Pyrazoline Derivatives. J."p9*. Chem., 1898, [ii], 58, 31b-332. Compare Abstr., 1894, i, 348). N=QR [R:R:Me=3:5:5],are -Mahates of pyrazolines, NH<cRMe. CH, obtained by treating ketazines, CRMe:N*&::CRMe (Abstr., 1891, 1355), with maleic acid, sometimes in alcoholic solution, and purifying the product by dissolving i t in alcohol and precipitating it with ether ; the free base is obtained by treating this product with potash. Only ketazines which contain at least one methyl group, >C:N*N:CMe-, are capable of reacting in this way ; diethylketazine, CEt,:N*N:CEt,, for example, will not do so.The pyrazoline derivatives obtained distil without decomposition under diminished pressure ; the boiling point and index of refraction increase with the molecular weight, whereas the specific gravity decreases. They are stable in the presence of acids, yielding no hydrazine salt, even on boiling, but potassium per- manganate oxidises them readily, the molecule being completely broken up. They are not coloured by oxidising agents in dilute solution (Knorr's pyrazoline reaction ; probably only given by deriva- tives in which the NH-group has become NPh). Of the compounds described, only 5-methylpyrazoline resembles pyrazoline itself (Abstr., 1895, i, 24s) in other respects; the rest do not form azo-dyes, they are not coloured yellow by nitrous acid, they do not colour a pine splint yellow, and they are not oxidised to pyrazoles by bromine.3 : 5 : 5-Trimethylpyrazoline boils a t 57-59' under 14 mm. pressure; sp. gr. = 0.903 at 18', 0.907 at 10'; index of refraction nD= 1.46149 a t 10' ; when oxidised with dilute permanganate nitrogen, carbonic anhydride and pyruvic acid are formed ; when treated with bromine in chloroform solution, its own hydrobromide, which melts at 171", is the product. 5-Methyl-3 : 5-diethylpyrccxoline boils at 90-93' under 20 mm., at 78-80' under 14 mm. pressure ; sp. gr. = 0.898 a t 18'; the hydrochloride, platinochloride, picrate, methiodide, and benzoyl derivatives are oils which would not crystallise ; with bromine, an oily product was obtained that was not the hydrobromide; in the air, this pyrazoline evolves nitrogen, and yields a substance, C,H,,O, boiling at 157-1558', which forms an oily compound with phenylhydrazine, and decolorises an ethereal solution of bromine, and so is probably CEtO*CH:CMeEt, a homologue of mesitylic oxide, although it does not, like the latter, condense with hydrazine; this substance is also obtained as a bye-product in the preparation of the pyrazoline.5-Methyl-3 : 5-dipopyZpyraxoZine boils at 101-103' under 14 mm., a,t166 ABSTRACTS OF CHEMICAT, PAPERS. 113-1 15' under 20 mm. pressure ; sp. gr. = 0.884 a t 18", 0.888 at 10'; yhD = 1.46318 ; in other respects, it resembles the previous compound. 5-ilfethyl-3 : 5-dil~exylpy~axoline is not formed very readily, and was obtained only in small amount. Ethylideneccxine, CHMe:N*N:CHMe, can be prepared by shaking an ethereal solution of acetaldehyde with an aqueous solution of hydrazine hydrate, and cooling with water ; it boils a t 95-96' under 760 nim.pressure, and has sp. gr. = 0.832 at 17' ; a t 180°, it is almost unchanged, but at a higher temperature it gives off nearly all its nitrogen as gas, no butylene being formed, however ; it is fairly stable towards alkalis, but acids decompose it into acetaldehyde and hydr- azine. With maleic acid, it yields the maleate of 5-methyl'yruxoline, and this, when decomposed with caustic potash, and the product frac- tionated, yields a small quantity of the pyrazoline, together with much of a bye-product (see below).The base boils at 73' under 55 mm., at 68' under 46 mm. pressure; the benxoyl derivative melts and decomposes at 156' ; a red tolueneaxo-derivative, with green reflex, was obtained; and with bromine in chloroform solution, 5-methylpyrazole appears t o be formed. The bye-product mentioned above, C ~ ~ H ~ G N G , possibly has the constitution FH* C,N,H,Me C3N2H4Me' OMe<CH. C,N,H,Me ; its hydrochloride and picrate melt and decompose a t 148' and 142' respectively; it takes up 6Br, gives a yellow coloration with nitrous acid, colours wood yellow, and reduces ammoniacal silver solution. C. F. B. Stereoisomerism in Piperazine and Ethylenediamine Deri- vatives. By WILLEM VAN RIJN (Chem. Centr., 1898, i, 727; from Ned. Tijdsck. Plzawn., 10, 43-52.See this vol., i, 77).-DiethyZ- pipermine, prepared by warming an aqueous solution of piperazine with a n excess of potassiiim ethylic sulphate, is purified by crys- tallising the platinochloride from hot dilute hydrochloric acid. By the action of methylic iodide (4 mols.) on piperazine, the compound NHMeI<:2: ;2>NMe,I is formed ; it crystallises from water in small prisms, decomposes at 260' without melting, and, with cadmium iodide (1 mol.), forms a double salt which crystallises in small, white prisms. The compound NEt<CH,. '*2* CH2>NEt,I, cH, prepared by the action of ethylic iodide on piperaGne, &ystallises from alcohol in white needles, melts at 240°, and is insoluble i n cold water, ether, chloroform, light petroleum, benzene, and carbon bisulphide ; the cadmium iodide compound crystallises in white needles.The action of propylic iodide on piperazine is analogous t o that of ethylic iodide. Attempts to prepare an isomeride of the hydrochloride of dibenzyl- piperazine methiodide by the action of freshly precipitated silver chloride on the dibenzylpiperazine methiodide obtained from the hydrochloride by means of sodium hydroxide, resulted only in the production of the original compound. By the action of propylic iodide on methylethylethylenediamine, the mono- and di-propiodidesORCIANIC CHEMISTRY. 167 are formed, and may be separated by means of the platinochlorides. The platinochloride of the former crystallises in reddish needles, and that of the latter in reddish-yellow leaflets.No other salts could be obtained in a crystalline form. By PAUL CAZENEUVE and MOREAU (Con@. rend., 1897, 125, 1182-1 184)-Molecular pro- portions of piperazine and phenylic carbonate, when heated in alcoholic solution for 20 hours, give an almost theoretical yield of the d,iurethccne, CO0Ph.N :C,H,:N* COOPb, which forms prismatic crystals and melts a t 177--178O ; its constitution is established by hydrolysis with potash, and by decomposition with concentrated sulphuric acid. The a- and P-nuphtlbylic diurethanes, prepared in a similar manner, form white, mammelated crystals somewhat insoluble in ordinary solvents; the a-compound melts a t 190-191", the p- a t 220'. The guaiacol derivative, C,N,H,( COO*C,H,* OMe),, crystallises from alcohol in plates and melts a t 181'.Derivatives of Triasole. By JOHANNES THIELE and WILHELM MANCHOT (Annalen, 1898, 303, 33-56. Compare Thiele and Heidenreich, Abstr., 1894, i, 57).-Formamidoguanidine nitrate, COH*NH*NH* C( :NH) *NH,,HNO,, prepared by heating amido- guanidine nitrate with 90 per cent. formic acid and one drop of nitric acid on the water-bath, crystallises from water and melts a t 143'; the picrate crystallises in needles and melts at 193". Oxalylamido- guanidine, COOH. CO *NH*NH* C(NH) *NH,, obtained on adding amidoguanidine hydrogen carbonat,e to a concentrated aqueous solu- tion of oxalic acid, and boiling the liquid in a reflux apparatus, crys- stallises from water, and melts and evolves gas a t 231-232'. Ammonia is readily eliminated from amidomethyltriazole under the influence of dilute sulphuric acid at 180-190°, the other products being carbonic anhydride, hydrazine, and acetic acid; a 30 per cent, solution of caustic potash or soda, however, leaves the amido-compound for the greater part unchanged.The benxoyl derivative of amido- methyltriazole melts and decomposes at 285-290' ; the cccetyl deriva- tive crystallises from water, and remains unfused at 270". E. W. W. Aromatic Diurethanes of Piperasine. G . T. M. NH*N Met h y Ztriazoleaxodirneth y landhe, NMe,* C,H, * N,. cGN-- 8 Me, pre- pared by adding dimethylaniline hydrochloride t o a solution of diazo- tised amidomet hyltriazole, crystallises f rom alcohol, and melts and decomposes a t 238" ; reduction with stannous chloride and hydro- chloric acid destroys the colour, which is redeveloped under the influence of ferric chloride. is a red powder, with green, metallic reflex, and melts and decom- poses a t 270".The colour is destroyed by reducing agents, and is not redeveloped by ferric chloride. C'hloromethyltriaxole, CCIGN- - 8 Me, obtained by diazotising amido- methyltriazole in concentrated hydrochloric acid, and evaporating the HN*N168 ABSTRACTS OF CHEMICAL PAPERS. liquid a t tho ordinary temperature, melts at 1 4 7 O ; it is volatile in steam, and sublimes when heated on the water-bath. The silvey derivative is sparingly soluble in water, but readily in ammonia and nitric acid. NH*N Benxylidenemethyltriaxyl?tydraxine, CHPh:N*NH*CqN _- 8 Me, pre- pared by reducing diazotised amidomet hyltriazole, under special pre- cautions, and combining the product with benzaldehyde, crystallises from alcohol and melts at 263'; the ltydrochloride separates from alcohol in needles, and melts a t 256'.Amidotskcxole, NH2* C< NH'y obtained on heating aqueous N-CH' formamidoguanidine nitrate with sodium carbonate, crystallises from ethylic acetate and melts at 159' ; it closely resembles amidomethyl- triazole, but differs from the latter, which is feebly alkaline and has no reducing action, whereas amidotriazole is neutral, and slightly reduces a boiling, ammoniacal solution of silver nitrate. The nitrate melts and decomposes a t 174', and the picrate, which crystallises in yellow needles, melts and decomposes at 227-228". Axotriaxole, N2(C2H,N3),, prepared by oxidising amidotriazole with potassium permanganate in alkaline solution, dissolves in alkalis, and is pre- cipitated by acids.Hydrazotriazole Itydyochloride, which is formed when azotriazole is reduced with stannous chloride and hydrochloric acid, crystallises in white needles and melts a t 227-230", beginning to decompose before this temperature is reached. It reduces ferric chloride and ammoniacal silver nitrate, and aqueous solutions readily undergo oxidation when exposed to the air. ~riaxoleaxo~i~aethylccniline, produced on adding dimethylaniline hydrochloride t o a solution of diazotised amidotriazole, crystallises from alcohol, and melts and decomposes at 250'. NH.8 ChZoroti*iaxole, CClGN_ H, prepared by diazotising amidotri- azole in concentrated hydrochloric acid, crystallises from benzene in slender needles, and melts at 167'; it sublimes when heated, and is volatile in vapour of benzene.It yields salts with acids, and also forms metallic derivatives. obtained by NH.8 Amidotriaxolecarboxylic acid, NH2* C< N- C-COOH ' heating oxalylamidoguanidine (2 mols.) with sodium carbonate on the water-bath, melts a t 182' with elimination of carbonic anhydride and production of amidotriazole ; it dissolves readily in alkalis, and is pre- cipitated by acids. The picrate melts at 176', and the hydrochloride melts and decomposes at 171-172' ; the sodium salt is anhydrous, and the ethylic salt crystallises from alcohol and melts at 247'. Diccxotriaxolecarboxylic acid, C,HN,O, + H,O, prepared by diazotis- ing amidotriazolecarboxylic acid, decomposes at 96' ; it does not explode when touched with a hot wire, and detonates with difliculty when struck.Chlorotriazole is produced on heating the substance with hydrochloric acid, and triazole results from boiling an alcoholic solution in a reflux apparatus ; triazole obtained in this manner meltsORGANIC CHEMISTRY. 169 a t 120--120.5', and is identical with the compound described by Bladin and by Andreocci. M. 0. F. Hydrazine Derivatives of Propionic Acid. By JOHANNES THIELE and JAMES BAILEY (Anr~den, 1898, 303, 75-91. Compare Thiele and Heuser, Abstr., 1896, i, 340).-The semicarbaxone of acetaldehyde crystallises from alcohol in white needles, and melts at 1 6 2 '. Cur bonccnhid o h y draxopopionitrile , N H, C 0 CH NH CM e C N , prepared by the action of 60 per cent.hydrocyanic acid on the semicarbazone of acetaldehyde, crystallises from alcohol and melts a t 131' ; i t has a powerful reducing action, and yields hydrogen cyanide when heated. Carbonarnidohyclmxopropionccmide is obtained by the action of cold concentrated hydrochloric acid on the nitrile for 24 hours; it separates from water in lustrous crystals containing 1H,O, and melts at 99-106'. or a t 142' in the anhydrous condition. Y . Dihydroxynaethyldil~ydrotriaxine, OH* C<";rCj-%s>CMe, prepared by treating the foregoing nitrile with fuming hydrochloric acid during 48 hours, diluting the liquid with twice its volume of water, and boiling the product for 3 hours in a reflux apparatus, crystallises from alcohol in lustrous scales and melts at 214". Dihydvoxymethyl- triccxine, OH* C<E' c(oq>CMe, is obtained by oxidising the di- hydro-derivative with bromine water ; it softens at 206' and melts at 209'.The imido-ether of carbonamidohydrazopropionic acid is obtained in the form of the hydrochloride, NH,. CO- NH*NH* CHMe*C(OEt) :NH,2HCl, when an alcoholic solution of the nitrile is saturated with dried hydro- gen chloride ; it is very hygroscopic, deliquescing rapidly on exposure to the air, and melts at 124-128', when it decomposes vigorously. On dissolving the hydrochloride in water, neutralising one-half of the hydrochloric acid with sodium carbonate, evaporating to dryness, and extracting with ethylic acetate, ethylic carbonamidohydvaxopropionate, NH,*CO*NH*NH*CHMe*COOEt, is produced ; it melts at 1 0 8 O .The free acid, obtained by hydrolysis with baryta, melts and decom- posesat 166-1 68'. Hydrazidopropionicacid, NH,*NH* CHMe*COOH, prepared by the action of boiling 80 per cent. sulphuric acid on e thylic car bonamidohydrazopropionate, is identical with the com- pound described by W. Traube and Longinescu (Abstr., 1896, i, 340). The semicarbnzone of pyruvonitrile, NH,* GO *NH*N:GMe.CN, ob- tained by oxidising carbonamidohydrazopropionitrile with potassium permanganate, is a sparingly soluble crystalline powder, which melts and decomposes at 215'; the semicarbazone of pyruvamide and the semicarbazone of ethylic pyruvate melt and decompose at 230' and 206' respectively. Ethylic hydrccxopropionate, N,H,(CHMe*COOEt)2, prepared, under specified conditions, from hydrazine, aldehyde-ammonia, and hydrogen cyanide, by hydrolysing an alcoholic solution of the product with hydrogen chloride, crystallises from benzene, petroleum, or water in thin, elongated prisms; it melts at 78", and boils at 2 4 5 O170 ABSTRACTS OF CHENICAI, PAPERS.under a pressure of 750 mm. The salt can also be obtained from hydrazidopropionic acid, aldehyde-ammonia, and hydrogen cyanide. The methylie salt melts a t 93', m d boils a t 220' under a pressure of 720 mm. The free acid, which crystallises from concentrated aqueous solutions in microscopic needles, begins to darken at 180°, and melts and evolves gas at 198'. If. 0. P. Characteristic Oxidation Reaction of some Cyclic Amines. By EUGEN BAMBERGER and ANTON VON GOLDBERGIER (Ber., 1898, 31, 2636--2640).-The authors have found that the hitherto unknown izimidindazole, C6H4<h (NH2)>NH, may be oxidised in various ways, but in most cases the product is Weddige and Fluger's hydroxy-P- phenotriazine, the so-called benzazimide, C,H,<N $?(OH) 'fi; N A similar change of structure occurs also when the monomethyl, and dimethyl-izimidindazoles are oxidised ; these yield the corresponding monomethyl- and dimethyl-hydroxy-P-phenotriazines. Hydroxy-/3-phenotriazine partakes of the nature of a diazoamido- compound, as its formula indicates.It gives a brilliant red colour with /3-naphthy lamine, and with melted resorcinol it yields a colouring matter, benzamidocceoresorcinol, which crystallises in rosettes of dark- red needles. Its structure is probably NH,*OO*C,H**N,*C,H,(OH)~.When izimidindazole is oxidised in alkaline solution by means of a ferricyanide or even by air, a basic substance is formed, which has colouring properties and forms crystals having an intense green metallic sheen; it gives a sparingly soluble nitrate, and may be diazotised. A. L. Azo- and Hydrazo-compounds of Tetrazole. By JOHAXNES THIELE (Annalen, 1898, 203, 57-75. Compare Abstr., 1894, i, 61), When amidotetrazole is oxidised by potassium permanganate in feebly alkaline solution, it is completely decomposed, but in presence of much alkali, derivatives of azotetrazole are produced. The sodium, potassium, and barium derivatives contain bH,O, and the calcium derivative 8H,O, the ammonium derivative is anhydrous, and crystallises from water in yellow needles, which decrepitate at 2 10' without exploding. The hydroxylamine derivative contains ZH,O, and explodes violently at high temperatures ; the hydraxine derivative also contains 2H,O, and the ccmidoguanidine derivative crystallises in long, yellow needles containing 1H20.The diaxoguanidine derivative, C,H,N,,, is anhydrous. When an aqueous solution of azotetrazole is treated with excess of a mineral acid, tetrazylhydrazine is produced, with elimination of nitrogen and formic acid; oxalic acid gives rise t o diazoimide. On adding dilute acid to a n aqueous solution of sodium azotetrazole covered with ether, the latter takes up a considerable amount of azotetrazole ; the yellow solution rapidly becomes turbid, however, from separation of a brick-red substance of unknown composition, but which probably contains one tetrazole ring.ORGANIC CHEMISTRY.171 Hydrazotetrazole, prepared by boiling an aqueous solution of sodium azotetrazole with magnesium powder, is a white, amorphous compound, insoluble in organic media, and dissolving with great difficulty in boiling water ; the substance is precipitated by ammonia and alkalis from the solution in concentrated hydrochloric acid, and the aqueous solution yields precipitates with many metallic salts. DibromoformaZtetraxylhydraxone, CBr2:N*NH*CN,H, obtained by the action of bromine water on a solution of hydrazotetrazole in con- centrated hydrobromic acid, crystallises from ether in white needles containing $H,O ; it becomes brown when heated, and melts at 177".Concentrated sulphuric acid eliminates hydrogen bromide and carbonic anhydride, forming tetrazylhydrazine. Further treatment of hydrazo- tetrazole with bromineconvertsitinto isocyanogen tetrabromide(Zoc. cit.). MetAyZic uxinocarbonccte, N,[:C(OMe),],, prepared by the action of potash dissolved in methylic alcohol on isocyanogen tetrabromide, separates from etbylic acetate in beautiful crystals, and melts at 111' ; dilute acids resolve the substance into methyliccarbonate and hydrazine. The sodium derivative of the amide of tetrazoleazocarboxylic acid, obtained by oxidising an alkaline solution of tetrazylsemicarbazide (Abstr., 1896, i, 107) with potassium permanganate, crystallises from water in lustrous, orange plates containing 2H,O ; caustic potash eliminates ammonia, and gives rise t o the potassium salt of tetrazole- carboxylic acid, which is decomposed by dilute acids, yielding carbonic anhydride, formic acid, nitrogen, and hydrazine, not tetr- azole.Tetrazoleazodimethylaniline is decomposed by dilute acids in the same way. Derivatives of Amido-orcinol. By FERDINAND HENRICH (Honatsh., 1898, 19, 483-517. Compare Abstr., 1897, i, 446),- Tribennzoykamido-orci~oZ, NH13z*C,H,Me(OBz)2, formed when amido- orcinol-is shaken with an excess of benzoic chloride and soda, crystallises from absolute alcohol in white, prismatic needles, melts a t 165-1 66" (uncorr. ), dissolves readily in benzene, chloroform, and hot alcohol, fairly readily in cold alcohol, and sparingly in ether ; it yields 3-hydr- oxy-2'-phenyl-l-methylbenzoxazole when distilled and hydrolysed.3-Hydroxy-2'-pheny1-1-methylbenzoxazole has a normal molecular weight in boiling acetone, is not altered by boiling with strong hydro- chloric acid, but is hydrolysed when heated with it, under pressure, at 183' for 5 hours. vielding. benzoic acid and amido-orcinol. M. 0. F. , # " >CPh, is made by 3-Ht~droxy-2'-phenylbenxoxaxo Ze, QH:"Hf" OH*C:CH*C*O treating amidoresorcinol with benzoic chloride, heating the product for 15 minutes at its boiling point, and finally hydrolysing with alco- holic potash the benzoyl derivative thus obtained ; it crystallises from benzene in colourless, compact crystals, melts at 2 16-2 1 7", dissolves readily in acetone, acetic acid, hot alcohol, and ether, but sparingly in light petroleum, cold chloroform, and benzene.Its alkaline solution is reddish-yellow and has a lilac fluorescence. When 3-hydroxy-2'-phenyl-l-methylbenzoxazole is treated with strong nitric acid,.the 2 ; 4-dinit.ro-compound, C~,H,O,N(NO,),, is formed. This separates from alcohol and chloroform in yellow, rhombohedra1172 ABSTRACTS OF CHEMICAL PAPERS, crystals and melts a t 188--189O, is sparingly soluble in cold alcohol, ether, acetic acid, and petroleum, but dissolves somewhat more readily in hot benzene and chloroform ; it has very feeble tinctorial properties, decomposes carbonates, liberating carbonic anhydride, and gives n crys- talline sodium salt. 3-Hydroxy-2'-phenyl-l-methylbenzoxazole is not affected by nitrous acid, but reacts in alkaline solution with diazobenzene, yielding benxeneaxo-3-h ydrox y- 2 '-3Jlen yl- 1 -methy Zbenxoxaxole , C,,H,,N,O,, which crystallises from glacial acetic acid in brownish-yellow needles and melts a t 169-170', dissolves readily in benzene and chloroform, but sparingly in cold alcohol and ether ; sulphuric acid dissolves it, form- ing a yellowish-red solution which becomes redder on dilution.The hydrochloride, C,oH,5N,02,HCI (?), separates on passing hydrogen chloride into an ethereal solution of the base ; it decomposes very quickly in presence of moisture. Acetoxybenxeneaxo-3-hydroxy-2'-phen y 2-1-methylbenxoxaxole, (&oH14N30&, made by heating the foregoing base with acetic chloride and anhydrous sodium acetate, crystallises from alcohol in long, orange-coloured, apiculate prisms and melts a t 182-183O; it is only slowly hydrolysed by boiling aqueous or alcoholic alkalis.The corresponding hydraxo- compound, made by heating it with zinc dust and acetic acid, crystal- lises from acetic acid in long leaflets and melts at 184-185'; it dissolves in strong sulphuric acid, giving a faintly coloured solution having a steel-blue fluorescence; on oxidation with nitrous acid, it yields the original hydroxyphenylmethyl benzoxazole. The corres- ponding benxoyl derivative, C,oHl,N,O,Bz, crystallises from absolute alcohol in light, brownish-yellow, prismatic, pointed crystals, sinters a t 160', and melts at 171"; it resembles the corresponding acetyl com- pound in its behaviour towards concentrated sulphuric acid and alkalis. On reduction, it yields a compound which dissolves in alkalis and in sulphuric acid, and the solution in the latter instance has a steel-blue fluorescence ; it gives hydroxyphenylmethylbenzoxazole on treatment with nitrous acid.Paramethoxybenxeneaxo-3-phenyl-I -methyZbenxoxaxole, C,oH,,N,O*OMe, produced when the azo-compound is treated with sodium methoxide and methylic iodide, crystallises from absolute alcohol in small, yellow needles, sinters at about 135O, and melts at 149-150'; it dissolves readily in cold benzene, chloroform, ethylic acetate, ether, and hot alcohol, but only sparingly in light petroleum and cold alcohol. E">CMe, formed when triacetylamido-orcinol is hydrolysed with diluted sulphuric acid or concentrated hydrochloric acid, crystallises from alcohol or benzene in long, colourless needles, melts a t 2 1 O', and dissolves readily in acetic acid, warm ether, and alcohol, but only sparingly in benzene and light petroleum.I t s acetyl derivative, C,,H1,O,N, formed by heating triacetylamido-orcinol at its boiling point for some time, crystal- lises from petroleum in white needles, melts a t 65', and is readily soluble in the ordinary media; it yields the preceding compound on hydro- lysis with alcoholic potash. The benxoyl derivative, C,H,02N* COPh, 3 -Hydroxy- 1 : 2'-dimeth y Zbenxoxaxo Ze, YH ' C( 0H):CH.C 0ORGANIC CHEMISTRY, 173 crystallises from petroleum, melts a t 108-1 lo', and dissolves readily in the usual solvents, with the exception of light petroleum. Benzeneaxo-3-hydroxy-1 : 2'-dimethyZbenxoxaxole, made by the action of diazobenzene' in alkaline solution on hydroxydimethyl benzoxazole, melts a t 116-118", and dissolves readily in the usual media ; it be- haves towards strong sulphuric acid like the corresponding derivative of phenylmethylbenzoxazole, but is much more readily soluble in soda. Formamido-ominol, C7H,(OH),-NH* CHO, obtained when sodium formate and anhydrous formic acid are heated with amido-orcinol hydrochloride at the temperature of a glycerol bath, sinters at 180°, melts and becomes red a t 195-198', and dissolves readily in alcohol and hot water, somewhat sparingly in ether, benzene, and chloroform, and is insoluble in light petroleum.It is quickly dissolved by aqueous soda, and reduces Fehling's solution and ammoniacal silver nitrate. - 3-EFydroxg-1 -methyZbenxoxaxoZe, OH* C7H5<E>CH, produced when the formyl compound is heated at 208', forms long, colourless leaflets and melts a t 162-163" after sintering slightly ; it is readily soluble in acetic acid, alcohol, and ether, somewhat readily in benzene, and sparingly in chloroform and light petroleum, especially in the cold ; it dissolves in strong soda ley, forming a colourless solution, but is not dissolved by a dilute solution of soda; it yields amido-orcinol when hydroly sed by strong hydrochloric acid.3-Benxoxy-l-met?~yZbenxoxccxole, C,H,NO,Bz, is readily soluble in alcohol, ether, benzene, acetic acid, carbon bisulphide, and chloroform, but only sparingly in cold petroleum. It is insoluble in alkalis, melting to an oil when warmed with them. Benxeneazo-3-hydroxy- I-methyZbenxoxaxoZe, C,,H,IN,O,, forms elongated leaflets having a n intense purple colour, and melts a t 186"; it dissolves readily in benz- ene and chloroform, but only sparingly in petroleum and in cold alcohol or acetone; i t ,forms a yellowish solution in strong sulphuric acid, which becomes a deeper red on dilution, and dissolves more readily i n aqueous soda than do the corresponding 2'-phenyl- and- 2'-methyl- derivatives, A. L.New Synthesis of Paraxanthina-Bv EMIL FISCHER and HANS C L E ~ M (Ber., 1898, 31, 2622-262$).-ChZoroparaxanthine, rMe*CO*g*NMe N>CC1, is formed when 1 : 7-dimethyluric acid is CO NH* C-- heated with phosphorus oxychloride at 135-140' for 3 hours, and can be purified by boiling with alcohol and subsequent recrystallisa- tion from a large bulk of hot water; it melts at 284' (295O corr.), dissolves in 170 parts of hot water, and crystallises from it on cooling in colourless, interlacing prisms ; it is more readily soluble in hot alcohol. When heated, it melts and sublimes readily, slight decomposition occurring.The sodium salt is sparingly soluble in cold water, and separates from hot water in slender, shining needles ; the potassium salt is more readily soluble, and crystallises in spherical aggregates of slender, colourless needles. Chloroparaxanthine dis- solves readily in cold dilute ammonia, and the solution gives, with silver nitrate, a white, amorphous precipitate which blackens when174 ABSTRACTS OF CHEMICAL PAPEHY. warmed, and dissolves in warm dilute nitric acid, the solution depositing slender needles on cooling.Chloroparnxanthine is readily reduced to paraxanthine when warmed with hydriodic acid and phosphonium iodide. Xanthine Bases &om Uric Acid. By ERNST E. SUNDVIK (Zeit. physiol. Chem., 1898, 26, 131--132).-1n a previous paper (Abstr., 1897, i, 598), it is stated that, by reduction of uric acid, xanthine and hypoxanthine are probably formed. This view is now shown to be correct, the bases having been isolated and analysed. Some Properties of Caffeine. By E. TASSILLY (BUZZ. SOC. C h h . , 1897, [ iii], 17, 596--599).--Hydrated caffeine, C,H1,N,O, + H,O, does not lose all its water of crystallisation even a t 150°, at whlch bemperature it is partially volatile. At 1 lo", the anhydrous compound does not lose in weight, whereas the hydrate undergoes a loss of 6.93 per cent.Caffeine is not volatile with steam, Calcium hydroxide solution decomposes the alkaloid at looo, ammonia being evolved, whilst with magnesia under similar circumstances no trace of am- monia is given off. The partition of caffeine between different solvents ceases t o be normal when other extractive substances are present. J. J. S. By Emr, FISCHER (Bey., 1898, 31, 2547-2549).-Pinely-powdered trichloropurine, C,HN,Cl,, is added t o 10 times its weight of hydriodic acid (sp. gr. 1-96), excess of powdered phosphonium iodide added, and the mixture kept, first for an hour a t Oo with frequent shaking, and then shaken a t the ordinary temperature for 24 hours by means of a motor ; the product is then warmed to 40°, filtered, evaporated a t 40--50° under diminished pressure, mixed with a little water, and again evaporated ; the crys- talline residue is washed with a little cold water and recrystallised from dilute hydriodic acid, warming gently only. In this way, the hgdriodide of hydurinephosphoric acid, C4H,N,P0,,HI + H20, is obtained ; by treatment with water and freshly preclpitated silver iodide, i t can be converted into the hydrochloride, C,H,N,PO,,HCI.These salts are soluble in water, but the solution soon turns red ; this coloration is hindered by the preseiice of a little halogen acid, but promoted by alkalis, the colour when ammonia is present becoming eventually that of a potassium permanganate solution. When heated with dilute hydrochloric acid on the water-bath, the hydrochloride yields ammonium chloride and phosphoric acid, but no phosphorous acid.The base corresponding with these salts is hydurinephosphoric acid, which is probably C,H7N,*PO(OH),, derived from a hypothetical base hydurine, C4H8N4, in the same way as is the amidophosphoric acid, NH,*PO(OH),, from ammonia, NH,. A. L. W. D. H. Hydurinephosphoric Acid. C. F. B. Purine and its Methyl Derivatives. By EMIL FISCHER (Bey., 1898, 31, 2550-2574).-2-lodo-7-metl~yZpu~*ine, bI C--N>CH, N:CH*g*NMe is obtained by reducing 2 : 6-dichloro-7-methylpurine (Abstr., 1898, i, 97) with hydriodic acid in large excess and phosphonium iodide a t 0" ;ORGANIC CHEMISTRY. 176 it melts at 225' (c0r.r.). verted into 2-oxy-7-methyZpzc~ine, When boiled with normal potash, it is con- >CH + H,O, which T:CH---g *NMe CO*NH* C--N decomposes a t about 323") and with normal potassium hydrosulphide solution in large excess, into an analogous, yellow thio-compound which decomposes at about 295".With half-saturated alcoholic am- monia a t 145-150", i t yields 2-a.mi~o-7-meth~Zpur~~e, melting at 283' (corr,), \which can also be obtained from 2-chloro- 7-methylpurine (see below), a conipound that is more easily prepared than 2-iodo-7-methylpurine. When boiled with zinc dust and water, I & : CH* E*NMe it yields 7-methyZpuvine, CH:N, --N >CH; this melts at 184" (corr.), its ?nercurichZos.ide at 25Z0(corr.), and its methiodide a t 231-232" (corr.). : CH*fi*NMe 2-Cl~Zoro-7-met~~~~ul.ine, CCI:N,C __ >CH, obtained by boiling 2 : 6-dichloro-7-methylpurine or trichloro-7-methylpurine with zinc dust and water, melts a t 200-201" (corr.), the mercurichloride at 206-20'7".When it is boiled wlth normal potash solution, a com- pound, C,H,N,Cl, which melts and decomposes a t about 251", is deposited, whilst 2-oxy-7-methylpurine remains-dissolved in the alkali. 2 : 6-Di-iodopus.ine, CT.N* c-N>CH, obtained by heating tri- chloropurine (Abstr., 1898, i, 47) with hydriodic acid and phosphonium iodide, melts and decomposes at about 224'; when heated with hydrochloric acid (sp. gr. = 1.19) a t 100" in a sealed tube, it yields xanthine, and when boiled with zinc dust and water, the insoluble zinc salt of purine itself is formed, and remains mixed with the excess of r : CI* g*NH iy: CH.@NH zinc dust.Purine, CH:N,C-,N >CH, is a readily soluble, well crystallised substance, which forms salts both with acids and with bases, and as regards its character in general falls naturally in the series uric acid, xanthine, hypoxanthine, purine. It melts at 216 -217" (corr.) ; the nitrate, with IHNO,, melts and decomposes at about 205" ; the yellow picrate, with 1C,H,N,07, melts at about 208' ; the base is very stable towards oxidising agents, and in consequencc does not give the murexide reaction. 2(?)-ChZoro-9-lnzethyZpu~ine, prepared by boiling trichloro-9-methyl- purine (see below) with zinc dust and water, Gelts at 135-136' (corr.). When heated with half-saturated alcoholic ammonia a t 150°, it is converted into 2(l)-amino-9-methylpurine, which melts a t 247" (corr.); with hydriodic acid (sp.gr. =1*96) at the ordinary tem- perature, it yields 2(?)-iodo-9-methylpurine melting at 171-1 72" (corr.). This, when boiled with zinc dust and water, yields 9-methylpurine, >CH, which melts at 162-163° (corr.). CH:N*C*NMe 7: CH* g--N P~eparation of Tricl~loYo-9-)net?L~l~)u~w~~~e.--T his is best prepared with-176 ABSTRACTS OF CHEMICAL PAPERS. out the use of phosphoric chloride ; 2 : 6-dichloro-8-oxy-9-methylpurine (I part) is heated with phosphorus oxychloride (25 parts) for 10 hours at 160-1 65', the product is evaporated under diminished pressure, and the residue washed with cold water and then with cold dilute caustic soda, and recrystallised from alcohol. Identification of Xanthine.-This is best effected by heating the supposed xanthine (1 part) with bromine (5 parts) a t ZOO' in a sealed tube, opening the tube and heating it to 140-145" to expel bromine, washing the residue with sulphurous acid, dissolving i t in warm am- monia and precipitating with hot, dilute sulphuric acid.The bromo- xanthine formed (1 part) is dissolved in normal caustic potash (1 3 parts by vol.), and heated with methylic iodide (24. parts) in a sealed tube a t 80' with constant shaking for 2 hours ; the bromocaffeine which separates is washed with very dilute caustic soda and recrystallised from water; it melts at 206'. This (1 part) is boiled for 5 minutes with 10 per cent, alcoholic potash (7 parts), the mixture is diluted with 3 times its volume of water, and the ethoxycaffeine, which soon separates, is recrystallised from water ; it melts at 140'.By boiling it (1 part) with 10 per cent. hydrochloric acid (10 parts by vol.) it can be converted into hydroxycaffeine, which melts at 345O. All these processes can be carried out with 0.5 gram of xanthine, and in the space of 24 hours. Behaviour of 2-hido-6 : 8-dioxypurine towards Chlorides C. F. B. of Phosphorus, By EMIL FISCHER (Be;., 1898, 31, 2619-2621).- 6-ChZoro-2-amido-8-oxypurine, NH,. ---N-C.NH >COY made by boil- I)' :CCl f*NH - ing 2-amido-6 : 8-dioxypurine wit6 phosphorus pentachloride dissolved in phosphorus oxychloride, can be purified by dissolving it in warm dilute ammonia and treating with animal charcoal ; the filtered liquid, heated t o drive off ammonia, deposits the substance in bundles of slender, microscopic needles.It decomposes at a high temperature without melting, dissolves sparingly in hot water and still more sparingly in alcohol, is readily soluble in warm dilute mineral acids, and fairly readily in dilute ammonia. When heated a t 130' with hydrochloric acid, it yields the hydrochloride of 2-amido- dioxypurine. When 6-iodo-2-amido-8-oxypurine, C,H,N,OI, obtained when chlor- amido-oxypurine is heated,with f uming hydriodic acid and phosphonium iodide at lOO', it is converted into a colourless? granular, indistinctly crystalline powder, which resembles in properties the original chloro- compound, but is more sparingly soluble. Bases Isomeric with Cinchonine. By VICTOR CORDIER VON LOWENHATJPT (Monatsh., 1 S98, 19, 461--482).-When cinchonine hydrobromide is heated with alcoholic potash, a mixture of bases is obtained which may be separated, by means of ether, into two portions.The least soluble portion may be further resolved by crystal- lisation from alcohol, and on treatment with sulphuric acid gives a salt, (C,,H,,N,O),,H,SO, + 2H,O, which has the same crystalline form as Hesse's homocincbonine sulphate (Abstr., 1881, 61 5) and melts a t 199*5', and also the sulphate of a new base, tnutocinchonine, This A. L.ORGANIC CHEMISTRY. 177 base resembles homocinchonine in some respects ; it dissolves in 144 parts of absolute alcohol at 20°, melts at 262*5', and has [a]D= + 209.42' ; its dihydriodide, ClgH,,N,0,2HI, forms beautiful, yellow prisms and melts at 238'. If that portion of the product of hydrolysis of cinchonine hydro- bromide which is readily soluble in ether is treated with hydro- chloric acid and potassium iodide, it yields a-isocinchonime dih ydviodids, which forms beautiful, yellow, prismatic crystals, and melts a t 205-2206', whilst the mother liquor from which it has been deposited contains a mixture of bases, and by successive treatment with hydro- chloric acid and zinc chloride may be made to yield 8-cinchonine hydrochloride and the zincochloride of a new base, E-cinchonine.When cinchonine hydrobromide is hydrolysed with alcoholic silver nitrate, a mixture of bases is obtained which appear to be identical with those produced when alcoholic potash is employed, and only differ in their relative proportions. c-Cinchomine, C,,H,,N,O, melts at 152', dissolves very readily in alcohol, but more sparingly in ether ; it crystallises from the latter in long, slender needles, and its specific rotation in 1 per cent.alcoholic solution a t 20' [.ID = 66.99. Its hydrochloride, C19H22N20,HCI, is anhydrous and crystallises in thick prisms. When water is used to hydrolyse cinchonine hydrobromide, a product is obtained from which ether dissolves s-cinchonine and a-isocinchonine, leaving pseudocinchonine and what is probably apoisocinchonine (allocinchonine 'I). When hydrobromic acid acts on cinchonine, not only is cinchonine hydrobromide formed, but the hydrobromides of a-isocinchonine, pseudocinchonine, and Gcinchonine are also produced. By FERDINAND ROQUES (Ann. Chim. Phys., 1897, [ vii I, 10, 234-288).-The production of crystallised cinchonicine has already been described (Abstr., 1895, i, 688). Full details of the method employed are set forth in the paper ; the specific rotation of the base obtained either from cinchonine or cinchonidine is ROW given as [a]D= 57.60' ; it was formerly stated to be 48.25'.The base from either of the two alkaloids melts at 49-40', differing in this respect from von Miller and Rhode's cinchotoxine,.which melts a t 58-59' ; the two bases are otherwise very similar, and they may be identical (compare Abstr., 1895, i, 434). The basic nitrate crystallises readily in prisms, which melt and decompose at 160'; [a], = 29*5S', the nol.ma2 nitrate in yellow, silky needles, extremely soluble in water ; its alcoholic solution is yellow, the colour disappearing when half the acid is neutralised by potash. The nwmal succinate, C,,H,,N,O,C,H,O, + H,O, crystal- lises in prisms. The double zinc and cadmium chlorides, and the alkylic haloid salts have already been described (Abstr., 1895, i, 688). Chemistry of the Atropine Alkaloids. By ADOLF PINNER (Chem. Centr., 1898, i, 679; from Centr. prakt. Augeralteilk., 20, 1-9). -According to the author, the plants of the order of SoZanacece, and the A. L. Cinchonicine. G. T. M. VOL, LXXVI. i. 92178 ABSTRACTS OF CHEMICAL PAPERS. species Atropa, Byoscyamus, Datwa, Mandragora, 8okanZcm, and Ani- sodua contain at least the two alkaloids, hyoscyamine, C17H23N03, and hyoscine (scopolamine). The former, by the action of alkalis, yields atropine, which may, perhaps, occur in small quantities in the plants, whilst hyoscine, with alkalis, forms inactive scopolamine (atroscine). By the loss of water, hyoscyamine and atropine form apoatropine, which, by an intramolecular change, yields belladonnine. Atropine is always present in commercial hyoscyamine and inactive hyoscine (atroscine), hyoscyamine and atropine are contained in conimercial scopolamine, whilst duboisine contains hyoscyamine, hyoscine, and other alkaloids. All the alkaloids, when hgdrolysed, yield tropic acid ; C9H1003,and tropine, C8H,,N0, is formed from atropine, and oscine (sco- poline), C8H,,N02, from hyoscine-scopolamine ; the alkaloids can be partially regained from these products. Ketones of the Tropine Group, XII. Constitution of Ecgonine. By RICHARD WILLSTATTER and WILHELM MULLER (Ber., 1898, 31, 2655-2669. Compare Abstr., 1898, i, 603).-Hydroecgon- idineamide, C,H,,N* CO *NH2, prepared by the action of ammonia on the ethylic salt of hydroecgonidine, crystallises in long, six-sided tablets melting at 126-127'. When this substance is heated with E. W. W. CH2* $3H-$!H*NH2 I potassium hypobromite, it yelds isotropykamine, J yMeyH2 9 CH2* CH-CH, which is isomeric with the tropylamines formed by the reduction of tropinonoxime; it is a colourless oil, which boils at 206-207' (corr.), and solidifies at 8.5'. The mercurichboride is soluble in hot water, and crystallises in characteristic tablets ; the hydrochlmide crystallises in compact, six-sided tablets, and sublimes when carefully heated ; the picrate melts and decomposes a t 236-237', and the platinochloride decomposes a t 261°, whilst the aurichloride could not be obtained of definite composition. The thiocarbamide, NHPh* CS*NH* C8Rl,N, crystallises in colourless, swallow-tail forms, and melts at 138-139O. Nitrous acid does not convert the base info iqotropine, but into trop- idine. Tsotropylarnine can also be prepared from hydroecgonineamide by Curtius' method. The hydrazide forms a picrate melting at 172O, and, when treated with nitrous acid, yields di-isotropylcarbamide, from which isotropylamine can be prepared by the action of hydrochloric acid. When ecgonine is oxidised by means of chromic acid, it yields tropinone, and this reaction shows that the hydroxyl group of ecgonine is in the same position as that of tropine and $&-opine. Moreover, since the properties of ecgonine are those of a p- and not of a y-hydroxy-acid, it follows that ecgonine has the constitution I. I. 1 rMeyH*OH 11. I YMegH CH2* VH-YH' COOH CH2* 7H-Y"' COOH CH,. C H-CH2 CH2* CH-CH Anhydroecgonine, therefore, has the constitution 11, which is in harmony with the formation from i t of 6-cycloheptatrienecarboxylic acid melting at 32'; this, as shown by its behaviour to alcoholicORGANIC CHEMISTRY. 179 potash (Einhorn and Willstatter, Abstr., 1895, i, 92), does not contain an ethylene linking in the Al-position. Alkaloidal Constituents of Camarilla, Bark. By WILLIAM A. H. NAYLOR (Phurm. J., 1898,5Q, 279).-Two bases are obtained by extracting the powdered bark with chloroform water containing 3 per cent. of oxalic acid. The one allied to choline forms a platinochloride crystallising in yellow, hexagonal plates, and a crystalline hydro- chloride which gives off trimethylamine on heating; analysis of the former salt indicates that the base is in reality, not choline, but betaine. The second base, cascurilline, isolated for the first time, forms a buff-coloured plutinochloride, which is soluble in alcohol and crystallises from water in prismatic plates. By Fa. KUTSCHER (Zeit. physiol. Chem., 1898, 26, 110-122. Compare Abstr., 1898, i, 611).-Antipeptone is not a peptone, neither is it a chemical unit (cnrnic acid) as alleged by Siegfried. It is a mixture of heterogeneous substances which, by means of phosphotungstic acid, can be divided into two parts, basic and acid. Among the bases, histidine, arginine, and another base of unknown nature were found; among the acids, aspartic acid was separated. W. D. H. Guanylic Acid f'rom Pancreas and its Decomposition Pro- ducts. By IVAR BANG (Zeit. phpiol. Chern., 1898, 26,133-159).- The potassium salt of guanylic acid, obtained by heating pancreas or nucleoproteid on the water-bath with 2 per cent. caustic potash, sepa- rates from the filtered extract as a voluminous sediment, which re- dissolves in hot water without decomposition, and is again precipitated as the solution cools. After repeating this treatment several times, the Ealt gives neither the Millon nor the biuret reaction. The free gwnylic acid liberated by the addition of 5 per cent. acetic acid to the warm solution of the potassium salt, is obtained, after washing with alcohol and ether, in the form of a white powder. The other nucleic acids are not liberated from their salts by acetic acid, but in this case the free acid is obtained, and the use of acetic acid is preferable, since guanylic acid is slowly decomposed by hydrochloric acid at ordinary temperatures. Guanylic acid may be prepared directly from nucleo- proteid by extraction with hot water, but the yield is smaller than by the above process. The free acid has a feebly acid reaction; it dissolves readily in alkalis and ammonia, and also in dilute mineral acids ; its aqueous solution gives precipitates with solutions of the heavy metals, but not with albumin dissolved in dilute acetic acid, an acidic solution forms precipitates with phosphotungstic, tannic, and picric acids. Neither iron nor sulphur are present in guanylic acid ; it contains less phosphorus and more nitrogen than the other nucleic acids, the ratio of these elements being P : 3N, whereas in the latter compounds it is P : 5N ; hence the latter ratio can no longer be re- garded as characteristic of these compounds. The analytical results agree most closely with the formula C22H,,Nl,P,0,7, and although it is unlike other nucleic acids in composition and in many of its pro- perties, the products of its decomposition show it to be closely related A. H. G. T. M. Antipeptone.180 ABS'EBACTS OF CHEMICAL PAPERS. to this class of substances. On boiling guanylic acid with dilute mineral acids, it decomposes, yielding a substance belonging t o the pentose group, guanine, phosphoric acid, and ammonia. The exact nature of the pentose derivative has not been determined; i t reduces Fehling's solution, forms an osazone melting a t 151-154', is un- fermentable, and cannot be obtained crystalline ; the quantity pro- duced, calculated in terms of glucose, amounts to about 30 per cent. of the original substance. Nine-tenths of the nitrogen originally present in guanylic acid is obtained, after hydrolysis, in the form of guanine; this is the first example of a nucleic acid giving rise to only one xanthine base, and it is on this account that the name guanylic acid is given to the compound. The only other nitrogenous product of decomposition is ammonia ; no trace of thymine could be obtained, either from guanylic acid or from nucleoproteid. G. T. M. Ovimucoid and a New Glucoproteid from Blood-serum. By CARLO U. ZANETTI (Chem. Centr., 1898, i, 624-625 ; from Ann. Chim. E%rm., 26, 529-534. Compare Henriques, Abstr., 1897, 570).-The author attributes the reducing action of blood to the presence of a substance which is closely related to, or identical with, ovimucoid. Ovimucoid is prepared from egg-albumin by dissolving it in 10 times its volume of a 5 per cent. solution of sodium chloride, adding acetic acid, removing the albumin and globulin by coagulating, filtering, con- centrating, and finally precipitating with alcohol. It can be purified by dissolving in water and precipitating with alcohol, the sodium chloride being removed by dialysing. The white, pulverulent mass cont,ains C = 48*75-48*94, H= 609-6.94, N = 12.46, S = 2.22 per cent., and with hydrochloric acid gives glucosamine, and one third of its sulphur in the form of sulphuric acid. The serum of the blood of oxen yields a similar substance, possibly identical with ovimucoid. E. w. w. Existence of the Proteid Radicle suggested by Bertrand in the Oxydases. By JOSEPH DE REY-PAILHADE (Bull. Xoc. Chim., 1897, [iii], 17, 756-757).-1t has been suggested by Bertrand (Abstr., 1897, ii, 493) that the oxydases contain a radicle of proteid character capable of entering into loose combination with manganese or hydro- gen, and the author points out that philothion, a substance discovered by him in 1889 and subsequently described on many occasions, possesses the 'properties required of such a compound. The existence of philothion and analogous substances in animal tissues in the presence of manganese suggests a series of combinations and decom- positions which offer a clear explanation of the mechanism of respira- tion in the tissues. N. L.

ISSN:0368-1769    

DOI:10.1039/CA8997600097

出版商:RSC    

年代:1899

数据来源: RSC