摘要:

J O U R N A L THE CHEMICAL SOCIETY. H. E. ARXSTRONQ Ph.D. F.R.S. W. CROOKES F.R.S. F. R. JAPP M.A.,Ph.D.,F.R.S. A. X. MILLER Ph.D. HUGO MULLER Ph.D. F.R.3. W. H. PEEKIN,P~.D. B.R.S. s. u. PIOKEEIXa M.A. R. T. PLIXPTOX Ph.D. W. J. RUSSELL Ph.D. F.R.S. J. MILLAR THOMSOX F.R.S.E. T. E. THORPE Ph.D. F.R.S. Cbitor : C. E. GROVES F.R.S. $trb-Qbitor: A. J. GBEENAWAY. Vol. LI. 1887. TRAKSACTIONS. L O N D O N : GURNEY & JACKSON 1 PATERNOSTER ROW. 1887 LOSDON : HARRISON AND SONS PRIKTERS IN ORDINARY TO HER MAJESTY ST. MARTIN’S LAS C O N T E N T S . PAPERS READ BEFORE THE CHEXICAL SOCIETY. PAGE I.-On the Synthetical Formation of Closed Carbon-chains. Part TI. On some Dcrivatii-cs of Tctramethylene. By 11.-Preparation and Hydrolysis of Hydrocyanides of the Di-ketones.By FRANCIS R. JAPP F.R.S. and N. H. J. MILLER, Ph.D . 29 111.-Note on some Double Thiosulphates. By J. B. COHEN, Ph.D. Assistaut Lecturer Owens College Mancliester . f38 lV.-O11 the Action of Silicon Tetrachloride on the Aromatic hmido-compounds. By ARTIIT:R HARDEN 13.Sc. Dalton V.-Reduction of Nitrites to Hydroxglamine by IIydrogen Sul-VI.-On Morindin and Morindon. By T. E. TIIOKPE F.R.S., VI1.-Spectroscopic Notes on the Carbohydrates and Albu-By W. K. UARTLEP F.R.S. Professor VII1.-The Action of Salicylic Aldehyde on Sodium Succinate i n presence of Acetic Anhydride. By GIBSON DYRON Ph.D., Demonstrator of Chemistry Normal School of Science, 1X.-Decomposition of Sodium Carbonate b y Fusion. By SPENCER UIIFREVILLI. PICKERISG M.A.Professor of Che-X.-The Eeat of Hydration of Salts. Cadmium Chloride. By W. H. PFRKIN Jun. Ph.11. . . . 1 Chemical Scholar in the Owens College . . 40 phide. By EDVVARD DIVERS and TAXEMASA HAGA . . . 48 and T. H GREESALL . . 52 mino’ids from Grain. of Chemistry Royal College of Science Dublin . . 58 South Kensington . . 61 mistry a t Bcdford College . . 72 mistry at Bedford College . 75 SPENCER UYFREVILLE PICKERISU M.A. Professor Of Che-XI.-Contributions from the Laboratory of Gonville and Caius College Cambridge. No. VIII. On Bismuthatcs. By M. &I, PATTISOX MUIR M.A. Follow and DOUGLAS J. CARSEGIE, XI1.-Derivatives of Tolylbenzene. By THOXAS CARNCLLEY, D.Sc. (liond.) and ANDREW T~~OYSON M.A. B.Sc. (Edin.), University College Dundee . . 8i B.A.Scholar of Gonville and Caius College . . 7 iv CONTENTS. XII1.-The Amount of Chlorine in Rain-water collected at Cirencester. By EDWARD KIBCH Royal Agricultural College, Cirencester . X1V.--Some Analogous Phosphates Arsenates and Vanadates. By JOHN A. HALL Studeiit in the Laboratory of Owens College . XV.-On some Azines. By l?RAXCIS R. JAPP F.R.S. and CosJro INNES BURTON B.Sc. . XV1.-Researches on the Constitution of Azo- and Diazo-derivatives. I. Diaeoamido-compounds. By RAPHAFL MELDOLA F.R.S. Professor of Chemistry and F. W. STREATFEILD Demonstrator of Chemistry in the Finsbury Technical College City and Guilds of London Institute . XVI1.-On the Distribution of the Nitrifying Organism in the Soil. By R. WARINGTON . XVII1.-The Influence of Silicon on the Properties of Iron and Steel.Part I. By THonras TURNER Assoc. R S.N., Lecturer on Metallurgy Mason College Birmingham . . I. The Action of Bromine on the Dibromonitrophenols. By ARTHUR. LING . XX.-Researches on the Relation between the Molecular Structure of Carbon Compounds and their Absorption Spectra. Part VIII. A Study of Coloured Substances and Dyes. By W. N. HARTLEY F.R.S. Professor of Chemistry Royal College of Science Dublin XX1.-Some Silicon Compounds and their Derivatives. I. The Action of Silicon Tetrabromide on Thiocarbaniide. By J. EXERSON REYNOLDS M.D. F.R.S. Professor of Che-mistry University of Dublin . XXI1.-Notes on the recent papers by A. von Baeyer and Julius Thomsen ‘‘ On the Constitution of Benzene.” By ALEX. K.MILLER Ph.D. . XXII1.-Agricultural Experiments with Iron Sulphate as tt Manure during 1886. By A. B. GRIFFITHS Ph.D. F.R.S.E., Principal and Lecturer on Chemistry School of Science, Lincoln late Lecturer on Chemistry Technical School, Manchester &c. . XX1V.-The Action of Triphenylniethyl Bromide on Ethplic Sodiomalonate. By G. G. HENDERSOX M.A. B.Sc., Assistant to the Professor of Chemistry University of Glasgow . XXV.-The Synthetical Formation of Closed Carbon-chains. Part 11 continued. Some Derivatives of Tetramethylene. By H. 0. COLXAS B.Sc. and W. H. PERKIX Jun. Ph.D. . XIX.-Isomeric Change in the Phenol Series. , 92 94 98 102 118 129 147 152 202 ‘208 215 224 22 CONTENTS 1-PAGE XXV1.-The Synthetical Formation of Closed Carbon-chains.Part 111. Some Derivatives of Yentamethylene. By W. H. PERKIN Jun. Ph.D. . XXVI1.-Absorption of Gases by Carbon. By CHARLES J. BAKER B.A. Demonstrator of Chemistry University Xuseum Oxford. . XXVII1.-An Explanation of the Lams which govern Substi-tution in the case of Benzenoid Compounds. By HENRY E. ARSiSTROSG F.R.S. XX1X.-The Action of Chlorine on Organic Thiocj anates. Part I. Xethyl Thiocyanate. By J. WILLIAS JAMLS, Ph.D. University College of South Wales Cardiff XXX.-The Decomposition of Potassium Chlorate and Per-chlorate by Heat. By PERCY F. FRANKLBXD Ph.D. B.Sc., By FUNK L. TEED L).Sc. . I3y J. WILLIAN JAUES Ph.D. F.C.S. University College of South Wales Cardiff . XXXIIL-The Influence of Temperature on the Heat of Dissolutioii of Salts By SPENCER UXFKEVILLE PICK~RIXG, M.A.Professor of Chemistry at Redford College XXX1V.-Contributions from the Laboratory of Gonville and Cnius College Cambridge. Xo. IX. Periodates. By C. K. KIIIXIXS D.Sc. B.A. late Scholar of Downing College, Cambridge . . XXXV.-On Tartaric and Racemic Acids and the Nagnetic Rotation of their Ethereal Salts. By W. H. PERKIS Ph.D., F.R.S. By EDTTARD H. RESXIE M.A. D.Sc. Professor of Chemistry in the University of Adelaide South Australia XXXVI1.-Further Notes on the Di-Haloid Derivatives of Thiocarbamide. By GEORGE XCGOWAN Ph.D. Demon-strator of Chemistry University College of North Wales, By EVIL A. VERNER Assistant in the Cheniical Laboratory Uni-versity of Dublin . SXX1X.-Supersaturation of Salt Solutions.By W. W. J. NICOL M A. D.Sc. F.R.S.E. Lecturer on Chemistry, Mason College Birmingham , By ARTHUR . A.R.S.M. and JOHN DIXGWALL . . XXX1.-Potassium Chlorate and Perchlorate. XXXI1.-On the Formation of Ethglic Cyanacetoacetate. . XXXT'I.-Tlie Colouring Xatter of Drosera Whzttakeri. , Bangor . . . . XXXVI1I.-Researches on Chrom-organic Acids. XL.-Action of Heat on Peroxide of Nitrogen. 240 249 258 268 2 74 283 287 290 356 362 371 378 383 38 Vi COSTENTS. PABE RICHARDSON Ph.D. Assistant Lecturer University College, Bristol . . 397 XL1.-Formation of Pyridine-derivEbtives from Citric Acid and on the Constitution of Pyridine. By Dr. S. RCHEJIANX, Jacksonian Demonstrator in the University of Cambridge . XLI1.-On Silver containing Bismuth.By WILLIAM GOWLAKD, Associate of the Royal School of Mines Chemist and Assayer of the Imperial Mint Osaka Japan and YOSHI~IASA KOGA Assistant Assayer . . 410 XLII1.-Snboxide of Silver Ag,O. By G. H. BAILEY D.Sc., Ph.D. and G. J. FOTLER B.Sc. the Owens College . 416 XL1V.-Anhydracetonebenzil. By FRANCIS R. JAPP F.R.S., and COSMO INNES BURTON B.Sc. . . 490 XLV.-Condensation Compounds of Benzil with Ketones. By FRANCIS R. JBPP F.R.S. and COSXO IWES BURTOX B.Sc. . 431 XLV1.-Researches on the Constitution of Azo- and Dinzo-derivatives. 11. Diazo amido-compounds (coiztinved). RAPHAEL MELDOLA F.R.S. Professor of Chemistry and E. fv. STREATFEILD Demonstrator of Chemistry in the Finsbury Techuical College City and Guilds of London Institute .. . . . . 434 Annual General Meeting . t . 452 XLVI1.-Dehydracetic Acid. By W. H. PERKIS J u n . Ph.D. . 484 XLVII1.-A Contribution to the Study of Well Waters. By ROBERF WARINGTON F.R.S. . 500 XLIX.-Constitution of Glycosine. By FRANCIS R. JAPP, L.-Diphenylglyoxaline and Methyldiphenylglyoxaline. By L1.-On the Atomic Weight of Gold. LI1.-On the Atomic Weight of Silicon. By T. E. THORPE, LII1.-Note on Substitution in the Benzene Nucleus. By F. H. L1V.-An Explanation of the Laws which govern Substitution in the case of Benzenoid Compounds. (Second Notice.) By HENRY E. ARMSTRONG F.R.S. . . . . 583 LV.-Researches on Silicon Compounds and their Derivatives. 11. A New Chlorobromide of Silicon. By J. EDIERSON REYKOLDS N D . F.R.S. Professor of Chemistry University of Dublin .. 590 403 F.R.S.,and E. CLEMIKSHBW &LA. . . 552 FRAXGIS R. JAPP F.R.S. . . . . 557 and A. P. LAURIE B.Sc. F.R.S.E. . . 565 F.R.S. and J. W. YOUSG B.A. . . 576 ~IORLEY MA. . . 579 By T. E. THORPE Y.R.S. CONTESTS. vii PAGE LV1.-On the Thermal Phenomena of Neutralisation and their bearing on the Nature of Solution and the Theory of Residual Affinity. By SPEXCER UNbREVILLE PICh.ERIXG, K A . Professor of Chemistry at Bedford College . By J. E. STEAD and C. H. RIDSDALE and Crystals from the Basic Slag. By H. A. MIERS M.A. F.G.S. . LVII1.-Ozone from Pure Oxygen its Production and its Action on Mercury with a Note on the Silent Discharge of Electricity. By W. A. SHESSTOSE Lecturer on Che-mistry in Clifton College and J.TUDOR CCXDALL L1X.-The Volumetric Relations of Ozone and Oxygen. A Lecture Experiment. By W. A. SHENSTONE and J. TUDOR CUNDALL . LX.-The Action of Metallic Alkylates on Mixtures of Ethereal Salts with Alcohols. By T. PURDIE Ph.D. RSc. Pro-fessor of Chemistry in the University of St. Andrews . LX1.-On Phlorizin. By EDWARD H. RENNIE &LA. D.Sc., Professor of Chemistry in the University of Adelaide South Australia . LXI1.-Further Notes on the Chemical Action of Bacterium aceti. By ADRIAN J. BROWN . LXII1.-The Composition of Prussian Blue and Turnbull’s Blue. By EDGAR J. REYNOLDS . LX1V.-On the Formation of Hyponitrites. By WYNDHAQI R. DUNSTAN Professor of Chemistry t o the Pharmaceutical Society and T. S. DYMOXD . LXV.-The Relation between Sulphites and Nitrites of Metals other than Potassium.By EDWARD DIVERS M.D. F.R.S., and TAMEYASA HAGA F.C.S. Imperial University TdkyG, LXV1.-Anacardic Acid. By Dr. s. RUHEMAXX and S. SKINNER LXVI1.-Sulphinic Compounds of Carbamide and Thiocarb-amide. By GEORGE MCGOWAN University College of North Wales Bangor . LXVII1.-Note on a New Class of Voltaic Combinations in which Oxidisable Metals are replaced by Alterable Solu-tions. By C. R. ALDER WRIGHT D.Sc. F.R.S. Lecturer on Chemistry and C. THOXPSO?; Demonstrator of Chem-istry in St. Mary’s Hospital Medical Scliool LX1X.-The Determination of Atomic Weights by means of the Normal Sulphate. By G. H. BAILEY DSc. . LXX.-The Action of Acetyl Chloride on Acetoximes. By VICTOR NEYER and ARTHUR W. WARKINGTON B.Sc.. LVI1.-Crjstals in Basic Converter Slag. . Japan . . . . 59s 601 610 6-25 627 634 63s 644 646 659 663 666 672 676 68 viii CONTENTS. LXX1.-Note on an Improved Form of Apparatus for the Separation of Iodine Bromine and Chlorine. By M. DECHAN F.C.S. . LXXI1.-Notes on Anhydro-bases. I. Ethenyltriamidonaph-thalene. By RAPHAEL JIELDOLA F.R.S. and F. W. STREAT-LXXT.11.-Dibenzyl Ether. By C. W. LOWE Student in t h e Oweiis College . LXX1V.-The Synthetical Formation of Closed Carbon-chains. Part I1 ( c o n t h u e c l ) . On the Action of Trimethylene Bromide on the Sodium Compounds of Ethylic Aceto-acetate Benzoylacetate Paranitrobenzoylacetate and Acetonedicarboxylate. By W. H. PERKIK Jun. Ph.D. . LXXV.-On Aluminium in the Ashes of Flowering Plants.By HIKOROKURO YOSHIDI F.C.S. Assistant Professor of Chemistry College of Science Imperial University Tokyo, Japan . . TdXXV1.-Some Ethereal Salts of the Vanadium Acids. By JOHX A. HALL Omens College LXXVI1.-Evaporation and Dissociation. Part VII. A Study of the Thermal Properties of a Nixture of Ethyl Alcohol and Ethyl Oxide. By WILLIAJI RAMSAY Ph.D. and SYDKET LSXVIIL-The Compounds of Ethyl Alcohol with Water. By D. ~IESDEL~EFF . LXX1X.-Isomeric Change in the Phenol Series. (Second Kotice.) By ARTHUR R. LINQ . LXXX.-The Effects of Dilution and the Presence of Sodium Salts and Carbonic Acid upon the Titration of Hydroxyl-amine by Iodine. By TAMEIIASA HAGA . LXXX1.-The Action of Light on the Hydrides of the Halogens in Presence of Oxygen.By ARTHUR RICHARDSOX Ph.U., Lecturer on Chemistry Unirersity College Bristol LXXXIL-Note on the Influence of Liquid Water in promoting the Interaction of Hydrogen Chloride and Oxygen 011 Exposure to Light. By HENEY E. ARMSTRONG F.R.S. . LXXXIIL-On the Magnetic Rotation and Densities of Chloral, Chloral Hydrate and Hydrated Aldehydes. By W. H. PERKIK Ph.D. F.R.S. LXXX1V.-The Synthetical Formation of Closed Carbon-Chains. Part I ( c o n t i w e d ) . The Action of Ethylene FEILD B’.I.c. . . YOUKG T ) . s C . . . FABB 690 69 1 700 702 748 s5 1 e- I 103 778 782 794 801 SOG 808 Bromide on the Sodium-deriGatives of Ethylic Acetoacltate, Benxoylacetate and Acetonedicarboxylate. By P. C. FREER, Ph.D. and TV. H. PERGIN Jun. Ph.D. . 82 GONTEKTS. ix PAGE LXXXV.-The Synthetical Formation of Closed Carbon-chains. Part I (continued). Trimethylenedicarboxylic Acid By W. H. PERKIN Jun. Ph.D. . . 849 LXXXVL-Experiments for the purpose of comparing the Equivalent of Zinc with that of Hydrogen. By Lieut.-Colonel H. C. REYNOLDS late R.E. and Prof. TIT. Raaisiy, Ph.D. . 834 LXXXVK-Note on the Atomic Weight of Gold. By T. E. THORPE and A. P. LAURIE Esq. B.A. . . 866 LXXXVIIL-Certain Products from Teak. Preliminary Notices. By R. ROMANIS D.Sc. Y.C.S. Rangoon College . 86

ISSN:0368-1645    

DOI:10.1039/CT88751FP001

出版商:RSC    

年代:1887

数据来源: RSC

摘要:

29 11.-Preparation and Hydrolysis of Hydrocyanides of the Diketones. By FRANCIS R. JAPP F.R.S. and N. H. J. MILLER Ph.D. THE first hydrocyanide of a diketone-benzil dihydrocyanide-was discovered by Zinin who prepared it by dissolving benzil in boiliria alcohol and adding about an equal weight of nearly anhydrous hydro-cyanic acid. A compound of 2 mols. of hydrocyanic acid with 1 mol. of benzil C14H,,0,( HCN), was obtained. According to Zinin this compound is not altered by boiling with water or with hydrochloric acid. As the compound may be regarded as a nitrile of diphenyltartaric acid thus-C,H,.C(OH).CN CsH,* c ( 0 H) *CN ’ we determined to study its behaviour towards hydrolytic agents in order if possible to obtain this acid. With a similar view we pre-pared the hitherto unknown hydrocyanide of phenanthraquinone in order to arrive a t the corresponding diphenylenetartaric acid.We had been engaged on this work €or some time when a pre-liminary note on the same subject mas published by B. S. Burton (Ber. 16 2232). Guided by the same idea this author had studied the action of hydrolytic agents upon Zinin’s compound. By sub-jecting i t to the action of a solution of hydrobromic acid in glacial acetic acid he succeeded in obtaining not diphenyltartaric acid but its amide-C,H,*C(OH)*CONH, I I C6H5*C(OH)*CONH As this work differed from our own both in the experimental con-ditions adhered t o and i n the results obtained we at once published a preliminary note (Ber. 16 2416) giving a brief account of the research upon which we were engaged.The object of the present paper is to supplement and in some respects to correct the state-ments made in that preliminary publication. Bend Dihychocyanide. I n the reaction about to be described we did not isolate the benzil dihydrocyanide ; indeed we afterwards found that with the pure cornpound no action occurs. The following method was employed : 30 JAPP AND MILLER PREPARATION AND HYDROLYSIS Benzil was dissolved in a quantity of alcohol sufficient to retain in solution the dihydrocyanide which is formed and a considerable excess of anhydrous hydrocyanic acid was added. The liquid was then saturated with gaseous hydrochloric acid cooling with ice-water during the operation after which it was allowed to stand for some weeks On poiiring the solution into water a yellow viscid substance separated the quantity of which was increased by exposinq the whole for some days to the air in a shallow vessel in order that the excess of alcohol might evaporate.The viscid substance was boiled with a solution of sodium carbonate which extracted an acid. The residue was dissolved in boiling alcohol and on cooling sepa-rated in lustrous pale-yellow laminae or flat needles melting con-stantly at 196-197"; some also separated from the hot sodium carbonate solution on cooling. It is sparingly soluble in boiling water and benzene readily soluble in boiling alcohol. Warm strong hydrochloric acid dissolves it on cooling and deposits colourless laminae ; these if washed wit)h water or dilute hydrochloric acid or on drying become yellow again.The yellow compound therefore, apparently possesses weak basic properties forming unstable colour-less salts. Analysis of the yellow compound gave figures which led to the for-mula C16H,,K,0 :-Substance. co,. HQO. I 0.1502 0.4263 0.0728 I1 0-1198 0.s390 0.0558 111. 0.1032 gram burnt with copper oxide in a Vacuum gave 9.8 C.C. of moist nitrogen at 21" and under 758.5 mm. pressure. Calculated for Found. Cl6Hl2N2O. r-- 7 rL-7 I. 11. 111. c16 192 77.42 77.41 77-17 -H,, 12 4.84 5.39 5.17 * -N2 28 11.29 - - 10.78 0 . 16 6.45 248 100.00 - - -- -Different preparations were analysed. The compound contains in its molecule an atom of oxygen less than benzil dihydrocyanide :-CiciH12Nz02 = C1J312N20 + 0.Benzil dihydrocyanide. New compound. It may be heated with fuming hydrochloric acid a t 170" withou O F HYDROCYANIDES OF THE DIKETONES. 31 undergoing any change beyond being converted into the unstable salt above referred to. Aqueous potash is without action upon it. The yield of the substance was very small and we were therefore unable to undertake the studr of its decompositions. In the above reaction the benzil dihydrocyanide is for the most part converted into acids. If the alcoholic solution of benzil hydro-cyanic acid and hydrochloric acid is allowed to stand too long the aqueous solution which is obtained after the separation of the viscid yellow substance contains a mixture of acids which we found it im-possible t o separate. On one occasion however we succeeded in isolating a nitrogenous acid which dissolved in boiling water and OIL cooling was deposited in colourless prisms melting at 196".The analytical figures pointed to the formula ClsHl3NO :-Substance. cop H,O. I 0.1160 0.2876 0.0506 11. 0.1144 burnt with copper oxide in a vacuum gave 5.0 C.C. of moist nitrogen at 20.7" and under 768 mm. pressure. Calculated for Pound. ClGH13N04* r --/-" - 7 r-- 7 1. 11. C1G.m 192 67.84 67-62 -H, . 13 4-59 4-85 -5.03 N 14 4.95 O* 64 22.62 283 100.00 -- -- -This is the formula of an acid which would be derived from benzil dihydrocyanide by the conversion of one cymogen-group into car-boxy1:-CGH5.C (OH) *COOH C,H,.C(OH).CN I The quantity of substance at our disposal was unfortunately in-sufficient for further examination, Benzil dihydrocyanide may be readily prepared by passing a large excess of gaseous hydrocyanic acid into alcohol in which benzil is suspended cooling during the process.On standing for some days, the benzil gradually dissolves whilst white crystals of the dihydro-cyanide are deposited.* After washing with alcohol in the cold the crystals are practically pure. * We also noticed the formation of ethylic benzoate a decomposition alread 32 JAPP AND MILLER PREPARATION AND HYDROLYSIS Benzil dihydrocyanide dissolves i n strong alcoholic hydrochloric Tbe compounds mid but appears t o undergo little or no change. above described are not formed under these conditions. Phenanthraquinone Dihydrocyanide. The method em-ployed in the preparation of the benzil-compound was first tried but failed to yield the new compound in a condition suitable for analysis, as alcohol even when considerably diluted with water retained it in solution.The following plan was adopted with success :-Very finely powdered phenanthraquinone was treated in the cold with a large excess of aqueous 30 per cent. hydrocyanic acid (a more dilute acid is almost without action) shaking the flask from time to time. The quinone assumed a vermilion colour; a t the same time, part of it dissolved. The liquid soon began t o deposit tufts of very slender white needles. The moment this separation commenced the liquid was quickly filtered in order to remove unaltered phenanthra-quinone. The filtrate deposited a considerable quantity of the above-mentioned needles.When exposed in a moist state to the air the new compound decomposed very readily. Even in drying over sulphuric acid it turned reddish-brown on the surface owing to a regeneration of phensnthraquinone. It was therefore after drying washed with chloroform to remove the phenanthraquinone and again dried over sulphuric acid. After this treatment the compound which was now almost colourless was analysed. It gave figures agreeing with the expected formula C,,H8O2(HCN) :-This compound had not hitherto been prepared. Substance. 00,. HcO. I 0.1586 0.4243 0.0622 I1 0.1085 0.2908 0.0430 111. 0.1036 gram burnt with copper oxide in a vacuum gave 9.65 C.C. of moist nitrogen a t 19" and under 751.5 mm. pressure. Calculated for Found.-7 CI,H,P,O,. r-h-r-&- 7 I. 11. 111. C, 192 73.28 72-96 73-09 Hlo 10 3-82 4.35 4-40 -Nz - 28 10.69 o2 32 12-21 262 100.00 -- 10.58 - - -- -described by Michael (Amer. Chem. J. 7 No. 3). the amount of this decomposition and is therefore to be avoided. An excess of alcohol increase OF HYDROCFANIDES OF THE PIKETONES. 33 The melting point could not be determined as the compound evolves hydrocyanic acid on heating and is converted into phenanthra-quinone. In a desiccator it may be preserved for an indefinite time ; but exposure to moist air speedily turns it reddish-brown. Boiling with water totally decomposes it ; but it dissolves in hot dilute hydro-chloric acid and provided too long boiling is avoided may be recrys-tallised from this solvent with only slight decomposition.The ready solubility of this compound even in very dilute alcohol, as compared with the sparing solubility of benzil dihydrocyanide is anomalous as diphenylene-compounds are usually much less so3 uble than the corresponding diphenyl-compounds. The above was the method employed in obtaining the compound for analysis. In studying its hydrolysis we at first proceeded as in the case of the benzil-compound acting with hydrochloric acid upon the compound in alcoholic solution in presence of an excess of hydro-cyanic acid. Afterwards nearly pure phenanthraquinone dihydro-cyanide was treated with fuming aqueous hydrochloric acid. In order to prepare the dihydrocyanide for this purpose the same pro-cess was employed as in the preparation of the substance for analysis, except that instead of filtering the mixture of fiiiely powdered phenanthraquinone and 30 per cent.hydrocyanic acid was allowed to stand in a strong flask for two or three days shaking from time t o time ic order to break up the cake of dihydrocyanide and unchanged quinone which was formed. At the end of this time there were only traces of quinone left and these were visible only on treating a sample of the product with alcohol. The substance was then filtered through a cone removing the liquid so far as possible by means of the filter-pump. The substance thus prepared was introduced without previous drying into a stout flask and a large excess of the strongsst hydro-chloric acid was added. In the first experiment made in this way, the flask was corked up and left overnight; but in the morning i t was found that the cork had been blown out and the contents of the flask scattered about.In repeating the experiment a delivery tube was therefore attached to the flask when i t was found that carbonic anhydride was given off. When this evolution of gas which con-tinued for some days had ceased water was added t o the contents of the flask and the undissolved substance was separated by filtration and dried. Two compounds having respectively the formulae C,,H,NO and C15H,,N0,,* could be isolated from it. Their separation was a matter of some difficulty. * In the preliminary note already referred to the formule C,,H,,NO and Cl6Hl,NO2 were erroneously assigned to these compounds.The difference in per-centage composition between the c, and (216 formuh is very slight (vide imzva), VOL. LI. 34 JAPP AND MILLER PREPARATION AND HYDROLYSIS The relative quantities of these two compounds formed appea,r to vary considerably in different experiments. In our first experiment, (in which a somewhat different method of hydrolysis was employed from that described above) we obtained the compound C15H9N0 by direct crystallisation of the product from benzene. Working as above it is the compound CI,Hl1NO2 which is thus obtained. This last method is the most convenient and the compound Cl,H9N0 can be obtained from the same crude product by modifying the treat-ment. When therefore the crude product prepared as above wag dis-solved in boiling benzene the solution on cooling deposited tufts of' slender needles which after recrystallising several times from the same solvent were obtained colourless with a constant melting point of 183".The results of analysis agreed with the formula C15HllN02 :-Substance. cop H,O . I 0.1336 0.3726 0*0600 Ir 0.1314 0,3650 0.0604 111. 0-0820 gram gave 4.15 C.C. of moist nitrogen at 21" and nnder 759 mm. pressure. Calculated for Found. C15HllN02.* r-A- -7 r--7 I. 11. 111. C 180 75.95 76-06 75.76 -HI,. . 11 4.64 4-99 5-11 -N . . . . . 14 5.91 -O2 32 73-50 237 100*00 - 5.75 - - - - -This compound is formed from phenanthraquinone dihydrocya.nide according to the equation-CwjHioN2Oz + 2H20 = ClsHuNO2 + NH + CO,. affecting chiefly the hydrogen which was found too high in the earlier analyses.At the time of writing the note which appeared rather hurriedly on account of the publication of Burton's paper we had not been able t o examine any salts of these eompounds and we thus lacked the most important clue to their molecular weight. Moreover in the method which we a t that time employed in preparing the com-pounds the evolution of carbonic anhydride escaped our notice ; hence we the more readily accepted without question analyticd results which appeared to prove that the compounds contained the same number of carbon-atoms as the dihydrocyanide from which they were derived. * The formula C16HlsNOa which was assigned t o this compound in the pre-liminary note requires C 76.49 H 5.18 and N 5-58 per cent OF HYDROCYANIDES OF THE DIEKTONES.35 We experienced some difficulty in obtaining the substance free from the compound C15HgN0 formed at the same time as this has nImost the same solubility in benzene and is deposited from this solvent in very similar forms; the latter compound however is formed in smaller quantity and remains in the benzene mother-liquors. The ouly satisfactory proof of the absence of the compound C15H,N0 which we have been able to find is to dissolve a sample of the substance in a solution of sodium carbonate and digest on the water-bath as long as a separattion of amorphous reddish- brown matter continues-a process which requires three or four days for completion. On acidifying the filtered liquid with hydrochloric acid there will he no precipitate if the compound C15H9N0 is absant.Both com-pounds dissolve in a solution of sodium carbonate and are preci-pitated on the addition of hydrochloric acid; but the compound C15H11NO2 is decomposed by heating with the alkaline carbonate, ammonia being evolved and the above reddish-brown substance depo-sited ; whereas the other compound is stable under these conditions. The compound CI5HllNO2 is therefore an acid inasmnch as it dig-solves in solutions of alkaline carbonates expelling carbonic acid and is precipitated by stronger acids. Owing however to its instability in presence of bases we were unable to obtain the salts in a condition fit for analysis. The sodium and barium salts became dark-coloured when heated t o 100"; the latter salt after drying at this tempe-rature in order t o expel water of crystallisation contained Ba 23.67 per cent instead of 22.49 as calculated for the formula (C15H10N02)2B~.The silver salt obtained as a white precipitate by the addition of silver nitrate t o a solution of the acid in ammonia became black in a few eeconds. It seemed possible that by the abstraction of the elements of water, this acid might be converted into the compound C15HgN0. We there-fore boiled it for an hour with acetic anhydride; but on allowing the mixture to cool the acid crystallised out unchanged. When heated in a test-tube to above 200" i t gave off a gas smelling strongly of ammonia whilst at the same time a sublimate of very high melting point was formed. This was insoluble in glacial acetic acid hut dissolved in concentrated sulphuric acid with a deep-blue colour and was therefore in all probability diphenanthrylene-azotide.When dissolved in acetic acid and oxidised with chromic anhy-dride it yields phenanthraquinone. On the first occasion on which we prepared this acid we had ex-tracted it from the product of the hydrolysis by heating the latter with a solution of sodium carbonate ; and in our prelimiriary note we stated our impression that this acid had been formed from the above-0 36 JAPP AND MILLER PREPARATION AND HYDROLYSIS mentioned anhydride (which we had alread~ obtained and analysed) by the action of the alkali. This supposition is incorrect the anhy-dride (vide infra) cannot be changed into this acid by any means which we have been able to discover and so far from a digestion with sodium carbonate being necessary to the formation of the acid, the acid itself is as above stated merely decomposed by this treat-ment.The compound Cl,HgNO which is formed by hydrolysis along with the above acid is best obtained pure by destroying the acid with which it is mixed. For this purpose either the crude product of hydrolysis or better the substance which collects in the benzene mother-liquors in purifying the acid is dissolved in sodium car-bonate and digested over the water-bath for several days. The liquid is filtered from the reddish-brown substance which separates and again digested at 100" as long as any further separation occurs. From the clear solution the compound C15H9N0 is precipitated on the addition of hydrochloric acid.By cry stallising from benzene and decolorising if necessary with animal charcoal it is readily obtained pure. It is deposited from hot benzene solutions on cooling in tufts of colourless silky needles melting constantly at 241". At a higher temperature it sublimes without decomposition. The results of analysis agreed w i t h the formula C,HI,NO :-Substance. 60,. H,O. I 0.1224 0.3678 0.0491 I1 0.1312 0.3944 0.0520 111. 0.0938 gram gave 5.1 e.c. of moist nitrogen at 19" and under 756.3 ram. pressure :-Calculated fcr Found. 7 Ci,r,HgNO.* r-h-7-- 7 I. 11. Irr. - ejI5 180 82.19 81.94 81.98 Hg 9 4.11 4-45 4.40 N . . . . . 14 6.39 -O . . . . . 16 7.31 - - --- 6-22 - -219 100.00 The formation of this compound from phenanthraquinone dihydro-cyanide may be expressed by the equation-C16HioN20 + HZO = CIbHgNO + CO + NH3.* The formula C,,HllNO would require C 82-40 H 4.7'2 and N 6-01 per cent OF HYDROCYANIDES OF THE DIKETONES. 37 The compound CI5HgNO when heated with a solution of sodium carbonate dissolves expelling carbonic acid and on cooling the solu-tion deposits lustrous thin six-sided plates of the formula C15H-10N02Na,4H20. 0.1949 gram of the air-dried salt lost at 100” 0-0432 gram of water. There was no further loss at 120”. The resulting 0.1517 gram anhy-tlrous salt yielded by ignition with sulphuric acid 0.0414 gram of sodium sulphate. Calculated €or 21-75 Calculated for C15H10N0,Na. Found. C151110N0,Na,4H20. Found. 22.1 7 H20 in 100 parts .. . . . . Na in 100 parts . . . . . . . . 8-88 8-84 The barium salt was obtained by boiling the compound C,,H,NO It was deposited from the hot with barium carbonate and water. solution on cooling in forked crystals having the formula ( CBH~ONOZ)~B~ 7H2O. On adding hydrocliloric acid to the solutions of these salts the compound CI5HgN 0 is at once precipitated. The compound C,,H,NO is thus the “internal amide” (lactim or lactam) of an acid of the formula Cl5H1,NO2 (isomeric with that already described) inca,pable of existing in the free state. Unlike the acid C15H,,N02 the compound C,H,NO does not yield phenanthraquinone on oxidation. Owing to want of material we have not been able t o examine these derivatives of phenant hraquinorie dihydrocyanide more thoroughly, phenanthraqixinone-the starting-point in the preparation of these substances-having become of late years very difficalt to obtain. Normal School of Xcieme, Xazcth Kensing ton

ISSN:0368-1645    

DOI:10.1039/CT8875100029

出版商:RSC    

年代:1887

数据来源: RSC

摘要:

38 IX-Note on some Double Thiosulphates. By J. B. COHEN . Ph.D. Assistant Lecturer Owens College, Manchester. Hydrated Potassium Czcprous Thiosulphate. RAMMELSBERG found that when cupric sulphate or acetate is added to a solution of potassium thiosulphate and the resulting green liquid is allowed to stand sulphur-yellow crystals are deposited consisting of a double thiosulphate of copper and potassium of the formula R2S~OJ,Cu2S20,,2H,O. These crystals are needles grouped in clusters, and are readily decomposed on warming with water copper sulphide being deposited. If however the addition of potassium thiosulphate be continued until the green colour disappears and gives place to a pale yellow tint (1 part of hydrated cupric sulphate requires about 2 parts of potassium thiosulphate) the resulting solution may be boiled for a long time and only a very slight deposition of a brown precipitate occurs.On standing this solution deposits a small quan-tity of brilliant orange-coloured crystals which consist of groups of six-sided prisms terminated by basal planes and belong to the hexagonal system. The crystals were washed with cold water dried in the air and analysed with the following results :-Found. Calculated for r----h-- 1 H,O 8-03 7.53 -K 23.21 - 23.27 23.34 - -Cu 18.74 - 19.62 - 19.51 19.67 S - - 27.57 - - 28.57 CU.LS,O~,~K,S,O,,~H,~. 1.X 11. 111. IV. V. - - -The substance cannot be recrystallised from water as it is scarcely soluble in the cold and dissolves with slight decomposition in hot water. Hydrochloric acid decomposes it with evolution of sulphur dioxide and the formation of copper sulphide.Caustic soda preci-pitstea cuprous oxide and if exposed to the air in contact with ammonia it dissolves forming a blue solution. It may be distin-guished from Rammelsberg's salt by its crystalline form its greater stability in hot aqueous solution and by the fact that the slight decomposition which then occurs is not accompanied by the formation of sulphate. It may be kept unaltered iu the air for several days, but slowly blackens after several weeks even in a well-closed vessel. It immedia.tely turns black when heated to 100-110". * Each number denotes a fresh preparation of the salt COHEN ON SOME DOUBLE THIOSULPHATES. 39 Anhydrous Potassium Cuprous Thiosulp hate.If 1 part hydrated copper sulphate be added to rather less than 4 parts potassium thiosulphate in hot concentrated aqueous solution, the liquid remains colourless and on cooling a mass of colourless silky needles is deposited. The purification of this salt is attended with some difficulty as although almost insoluble in excess of potas-sium thiosulphate it is very soluble in the cold in pure water. Nor can the substance be reprecipated with alcohol as in this case almost the whole is converted into the yellow modification described above, which separates out in minute hexagonal plates. The needles were therefore freed from mother-liquor by washing them with small quantities of cold water on the filter-pump ; there was considerable loss however. The air-dried substance gave the following results on analjsis corresponding with the formula Cu2S20J,2KLS20J :-Found.Calculated for r-hd-Cu&0,,2K,S,03. I. 11: Cu 20.38 20.65 20.02 Its behaviour with reagents is similar to that of the yellow salt. It does not change colour nor lose weight at 100-110" ; but begins to blacken at 120" with evolution of sulphur dioxide. Barium Cuprozcs Thiosulphate. The colourless and yellow salts both give with barium chloride the same white curdy precipitate of a barium cuprous thiosulphate which dissolves readily in boiling water but is scarcely soluble in cold water. The analyses of the barium salt dried at 100-110" gave results which apparently do not correspond with any simple formula. Found. f-A-, I. 11. x i . Ba 34.08 34-36 33.78 Cu 16.85 S 17.84 - - - -Nos.1 and 2 are analyses of the barium compound obtainedfrom different preparations of the yellow potassium salt ; No. 3 is obtained from the anhydrous white salt. Potassium Silver Thiosutphate. A double tbiosuIphate of silver and potassium has been prepared by Herschel by adding t o a solution of silver chloride in sodium thio 40 HARDEN ON THE ACTION OF SILICON TETRACHLORIDE sulphate a strong solution of potash or a potassium salt. If 2 parts of potassium thiosulphate in solution is added t o 1 part of silver nitrate in solution and boiled a black precipitate of silver sulphide is formed and snlphur dioxide evolved. On the other hand if the FO~U-tion whilst boiling be kept slightly alkaline with pot'assium carbo-nate the amount of black precipitate is very much diminished and the filtrate on standing deposits long colourless transparent prisms of the double salt some of them an inch long. Analyses of the com-pound gave the following results corresponding approximately wilh the formula Ag2S203,2K2S203. Found. --z Calculated for ~ g 2 S O 3 ~ ~ ~ 0 . I. K 22-03 - 22-19 S 27.11 26.62 86-58 Ag 30.50 33-14 33.12 The salt does not lose weight at 100-110" but a few brown specks It is decomposed by acids and alkalis but make their appearance. does not change in the air nor on keeping f0r.a 1eng:th of time

ISSN:0368-1645    

DOI:10.1039/CT8875100038

出版商:RSC    

年代:1887

数据来源: RSC

摘要:

40 HARDEN ON THE ACTION OF SILICON TETRACHLORIDE IV.-On the Action of Silicon Tetrachloride on the Aromatic Amido-compounds. By ARTRUR HARDEN B.Sc. Dalton Chemical Scholar in the Owens College. WHEN anhydrous ammonia is passed into silicon tetrachloride a violent reaction takes place ammonium chloride and a nitride of silicon being formed (Deville and Wohler Annulen 104 256). I n order to obtain compounds in which only a portion of the hydrogen is displaced I undertook at the suggestion of Dr. J. B. Cohen the investigation of the action of silicoii tetrachloride on the substituted ammonias the aromat,ic amido-compounds being chosen on account of their greater stability. Dichlorosilicon Diphenyldiamide SiCl,(NH*C,H,),. When silicon tetrachloride is added to aniline a violent reaction takes place accompanied by considerable development of heat the whole solidifying to a white amorphous xriftss.The aniline was there-fore diluted with about twice its weight of benzene which had bee ON THE AROJEATIC AMIDO-COMPOUNDS. 41 carefully dried over sodium and the silicon tetrachloride also diluted with dry benzene was added gradually with continual agitation until the reaction was completed; the presence of a slight excess of the chloride being easily recognised by its characteristic acid vapour. It was then found that 1 mol. of silicon tetrachloride was required for 4 mols. of aniline. Calculated (11.) 7.9 grams aniline required 3.6 grams SiC14. Calculated The liquid was then filtered in a current of dry air in order to prevent absorption of moisture and consequent decomposition.This was effected by aid of the apparatus sketched below. A wide tube A to which one of a smaller bore has been fused at B serves as a funnel. The opening at the wider end is closed by a cork, (I.) 9 grams of aniline required 4.5 grams of SiC1,. 4.1 grams. 3.8 grams. through which passes a calcium chloride tube D to dry the air entering the apparatus and a tap-funnel E by means of which the precipitate can be washed without the admission of moist air. A plug of asbestos is placed at B and the stem inserted in the cork of a flask H which is connected by it conducting tube and calcium chloride tube F to an aspirator. In practice a current of dry air is first aspirated through th 42 HARDEN ON THE ACTION OF SILTCON TETRACHLORIDE appai-atus; the cork C is then removed the liquid to be filtered poured in the cork replaced and the processes of filtration and washing proceeded with.The white residue mas washed with benzene and dried in a vacuum over sulphuric acid. It was readily soluble in water and alcohol, leaving only a slight residue of silica (less than 1 per cent.). On heating it sublimed in white needles gave the carbnmine reaction when heated with chloroform and alcoholic potash and possessed all the other properties of aniline hydrochloride. On analysis-0.554 gram of substance gave 0.0054 gram of silica and 0,6079 gram of AgCI. Calculated for Found. C6H5.NHo,HC1. Chlorine . 27.14 2 7.41 The platinochloride separated from solution on the addition of On analysis-0.3925 gram of substance gave 0.1255 gram of platinum.alcohol in small pellow needles. Calculated for Found. (C,H,N) ,,H,PtC16. Platinum. 32-23 32.86 The compound was therefore aniline hydrochloride. In order to ascertain how much of this was formed the precipitate in one expe-riment after careful washing was dried and weighed. It was thus found that half of the aniline that is 2 out of the 4 mols. required for 1 mol. of silicon tetrachloride had been converted into the hydro-chloride :-Cal- 10.2 grams of aniline yielded 6.7 grams of hydrochloride. The filtrate from the aniline hydrochloride was eraPoratted in a vacuum over sulphuric acid and left a thick viscous liquid which, 09 being exposed in a desiccator on a porous plate for some days, solidified to a nearly white amorphous mass.In the dry state it is almost insoluble in benzene and all attempts to crystallise it from other solvents were unsuccessful. The data already given as to the relative amounts of the substances used and of the hydrochloride of the base formed indicate the course of the reaction very clearly and it was therefore only neces-sary to determine the percentages of two of the constituents viz., the silicon and chlorine in order to establish the composition of the compound formed. culated 7 grams ON THE AROXATIC AMIDO-COMPOUNDS. 43 The method of analysis adopted depends on the fact that the com-pound is readily decomposed by water silica and aniline hydro-chloride being formed. The silicon and chlorine can therefore both be determined in one portion of the substance in the following way :-About 0.5 gram of the substance is weighed out into a beaker and treated with water ; the greater portion of the silica is thus preci-pitated but the remainder goes into solution as soluble silicic acid.The solution is filtered and the precipitate aftel. having been well washed with hot water is ignited and weighed as silica. I n hhe filtrate the hydrochloric acid is precipitated with silver nitrate and the silver chloride collected washed and weighed as usual. The filtrate from the silver chloride is then treated with snf-ficient hydrochloric acid to remove the excess of silver filtered and the filtrate evaporated to dryness with strong hydrochloric acid on the water-bath. The residue is moistened with hydrochloric acid, and the insoluble silica collected washed ignited and weighed in the usual way the weight being added to that of the first precipitate.The silicon may be more readily determined by decomposing a weighed portion of the compound with water in a platinum crucible, evaporating to dryness with an excess of acid on the water-bath, igniting and weighing as silica. The results obtained in this way agree extremely well with those given by the other method. The aniline compound gave the following analytical results :-I. 0.6386 gram of substance gave 0.1262 gram SiO2 and 0.6281 gram AgCl. 11. 0.5210 gram of substance gave 0.1062 gram SiOz. Found. r-&- -7 I. 11. SiCl,(NI€C6H,)2. Calculated for Silicon 9.01 9.51 9.90 Chlorine 24.28 - 25.03 The formula of the compound is therefore SiCl2(NH*CsH5), and the reaction by which it is formed is expressed by the following equation :-SiC1 + 4C6H5*NH = SiClz(NH*C6H5) + 2C,H5*NH2,HCl.The difficulty of obtaining this compound (and its homologues) in EL state of purity is much increased by the circumstance that the viscous liquid left on the ex-aporation of the benzene solution soli-difies gradually in crusts which have t o be removed from time to time. Exposure to the air for a short period is necessary for this purpose and consequently absorption of moisture takes place. The decomposition effected by water is expressed by the following equa-tion :-SiCl,(NH*C6H5) + 2H,O = SiOs + 2C6H5-NHz,HCl 44 HARDEN ON THE ACTION OF SILICON TETRSCHLORIDE Cold water decomposes the compound quietly but hot water pro-duces a violent reaction.The dry cornpound does not melt when heated but decompose#, leaving a blackened residue containing a large amount of silicon (about 14 per cent.). Several aiialogoizs substances which closely resemble the aniline compound in their properties have been prepared by the action of silicon tetrachloride on various primary aromatic amido-compounds ; they have all been obtained and analysed by the methods just described. Dichlorosilicon- orthodito ly ldiamide S i C1 (NH-C H7) ,. This compound was obtained by adding an excess of silicon tetra-chloride to orthotoluidine the method described for the preparation of the aniline compound being followed in every particular.7.3 grams of orthotoluidine required 3.4 grams of silicon tetra-The precipitate was a white granular powder and after washing 0.6953 gram gave a trace of silica and 0.6833 gram AgCl. chloride. Calculated 2.9 grams. and drying weighed 5.1 grams. Calculated 4.9 grams. On analysis-Calculated for Found. C7HgN.HCl. Chlorine . 24.26 24.69 The compound was therefore toluidine hydrochloride. The solution on evaporation in a vacuum yielded the silicon com-It pound which resembles the aniline-derivative in every respect. gave the following analytical results :-I. 0.6348 gram of substance gave 0.1208 gram SiO,. 11. 0.4130 gram of substance gave 0.0752 gram SiO and 0.3954 Found. gram AgC1. r- -7 Calculated for I. 11. SiClz (NHC7H,),. Silicon 8.88 8.50 9.01 Chlorine - 23-65 22.78 The compound therefore has the formula SiCl,(NH*C7H7),.DDichlorosilicon-diyly ld~amide SiCl,(NH*C,Hg),. An excess of silicon tetrachloride was added as before t o 8.6 grams of isoxylidine. The liquid became hot showing that the reaction had taken place but no precipitate was produced at first xylidin ON THE AROMATIC AMIDO-COMPOUNDS. 45 hydrochloride ever a crystal to be xylidine being slightly soluble in benzene. On cooling how-line precipitate was formed which on analysis proved hydrochloride. 0-435 gram of substance gave 0.3983 gram of AgCI. Calculated for Found. CsHllN HC1. Chlorine. . 22-60 22-49 The liquid was filtered and the benzene removed from the filtrate by distillation on the water-bath. The addition of anhydrous et,her to the liquid residue produced a precipitate the principal portion of the hydrochloride being thrown down together with a small quantity of the silicon compound.The liquid was again filtered and was then evaporated in a vacuum. The residue obtained in this way however, was not perfectly pure but still contlained some hydrochloride as will be seen from the analysis:-0.35'20 gram of substance gave 0.0532 gram of SiOz and 0.3129 gram of AgC1. Calculated for Pound. SiC12( NH.C,H,) 2, Silicon 7.05 8.27 Chlorine 21.97 20.89 The compound resembled the aniline-derivative in all its pro-perties. DichZorosiZicon-~-di~zapl~t~~Zdicxmide SiCl,(NH.CloH,)2. About 8 grams of P-naphthylamine dissolved in a large quan-tity of benzene were treated with an excess of silicon tetrachloride.An exceedingly bulky precipitate of the hydrochloride was formed, the whole mass becoming semi-solid and proving extremely difficult to filter. The filtrate was evaporated in the usual manner and yielded the silicon compound as a white or slightly pink powder no viscous liquid being formed; the compound therefore was obtained in a purer state than any of the preceding. It gave the following analytical results :-0.1990 gram of substance gave 0.0263 gram of SiO and 0.1478 A determination of nitrogen by Dumas's absolute method gave the 0.3865 gram of substance gave 22.1 C.C. of nitrogen measuyed at gram of AgCl. following numbers :-759.1 mm. and 17" 46 HARDEN ON THE ACTION OF SILICON TETRACHLORIDE Calculated for Found.SiC12(NH.C,oH~)2. Silicon 7-32 7.31 Chlorine 18.33 18.49 Nitrogen 7.47 7.31 On heating it decomposed without .melting in the same manner as the aniline compound. Several experiments were also made to ascertain the action of silicon tetrachloride on the secondary amines. For this pnrpose an excess of silicon tetrachloride was added t'o a solution of diphenyl-smine in benzene. No heating effect was noticeable but after standing for some time a small quantity of a white crystalline deposit was formed. On analysis this proved to be diphenylamine hydro-chloride :-0.3262 gram of substance gave 0.001 gram of SiO and 0.227 gram of AgCl. Calrulated for Found. ( C6H5),NH,HCl. Chlorine 17.18 17.24 The silicon cornpound however couId not be obtained in the pure state.Another preparation was made ether being used instead of benzene but with the same lack of success. The action of silicon tetrachloride on the tertiary bases such as quinoline and pyridine is of quite a different nature to the foregoing. When the chloride is added to quinoline immediate conibination takes place accompanied as in the previous cases by a considerable development of heat and the whole solidifies to a white amorphous mass. After washing with chloroform the substance smells strongly of the tetrachloride and loses a considerable portion of this on expo-sure to the air or on drying in a vacuum. The same result is obtained by heating the mixture in a sealed tube a t 100". On adding the silicon tetrachloride gradually to pyridine diluted with benzene it was found that 1 mol.of the chloride was required for 2 mols. of pyridine. 11.7 grams of pyridine required 12 grams of Sic&. Calculated 12.5. The filtrate from the dense white precipitate formed contained no silicon. These compounds lose silicon tetrachloride when gently heated, whilst when more strongly heated further decomposition takes place, and a charred residue containing silicon is left. All these properties point to the fact that these substances are simply double compounds A similar reaction occurs in the case of pyridine ON THE AROMATIC AMIDO-COMPOUNDS. 47 containing 1 mol. of silicon tetrachloride to 2 mols. of the base. The analyses show that from one-fifth to one-third of the silicon tetra-chloride has been lost in drying.Both the compounds absorb moisture very readily silica and the hydrochloride of the base being formed. P y r i d i n e Siliconchloride 2C5H5N,SiCI4. This compound which is prepared as described above is a white amorphous powder which rapidly loses silicon tetrachloride in the air. On analysis-(I.) 0.7802 gram substance gave 0.1175 gram of SiO,. 0.916 , , 1.2902 , AgCl. (11.) 0.5355 gram substance gave 0.069'; gram SiO and 0.7018 gram AgG1. Found. f----7 Calculated for I. 11. 2C&ISN,SiC1,. Silicon 7.03 6.07 8.53 Chlorine 34-75 32.35 43-29 The fact that these compounds are derived from the double com-pound by loss of silicon tetrachloride is shown by the practical identity of the ratio of the chlorine to the silicon in the three cases :-Ratio of C1 to Si 4-94 5.33 5.07 1.11. Calculated. Qzcinoline Siliconchloride 2 C9H7 Sic&. This compound is formed in a similar manner to the preceding but is much less stable. I t losp silicon tetrachloride so readily and absorbs moisture so eagerly that satisfactory analyses could not be made. On decomposition with water it forms quinoline hydro-chloride and silica. This was proved by treating a portion with water filtering from the precipitated silica converting into the platinochloride and analysing the latter :-(I.) 0.1953 gram of Pt salt gave 0.0-543 gram of Pt. (TI.) 0.4970 , , 0.0255 gram H,O and 0.1380 gram of Pt. Found. (-.-A- 7 Calculated for I. 11. (C&€iN),,H&C'l + 2Hz0. Water - 5.13 5-11 Platinum. . 27.80 27.76 27-82 I propose to continue these investigations employing the fatty amines for those of the aromatic series and to endeavour to obtain analogous compounds from the elements allied to silicon

ISSN:0368-1645    

DOI:10.1039/CT8875100040

出版商:RSC    

年代:1887

数据来源: RSC

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48 V.-Reduction of Nitrites t o Hydroaylainine by Hydrogen Sulphicle. By EDWARD DIVERS and TAMEMASA HAGA. THE solution of an alkali nitrate saturatled with hydrogen sulphide, and then acidified with hydrochloric or sulphuric acid yields sulphur, nitric oxide and ammonia but no hydroxylamine,* the presence of this being incompatible with that of what is known as free nitrous acid. When the escaping gases are collected out of contact with air, they slowly deposit sulphur and do so more quickly on bubbling through water into tlie air in consequence of reactions between hydrogen sulphide nitric oxide and oxygen but still no hydroxyl-amine appears. When however siZz;er nitrite suspended in water is treated with hydrogen sulphide besides the sulphur nitric oxide and ammonia, still abundantly formed and the silver sulphide a considerable quantity of hydroxylamine is also produced.On filtering off the silver sulphide adding hydrochloric acid to convert the hydrosul-phides into hydrochlorides and evaporating to dryness a mixture of f NOTE BY EDWARD DIVERS on the dropping the ‘ ( 1 ” out of the word hydroxyl-ornine.-It seemed to me unnecessary to urge anything in justification of my action when I ventured to use the spelling hydroxyamine in a paper which appeared in the Society’s Journal Trans. 1885 597 j but the Editor’s note attached to that paper h a r i q shown me my mistake I now make good the omission. If as is cer-tainly the case the composite names in use in chemistry should conrey their eigni-ficance equally to the ear as to the eye then it seems much bettor to call oxyammonia hydrox’yamine or hydrox’amine than to call it hydroxy l’amiae and thus avoid accenting an insignificant syllable.It is true that meth’ylamine phm~ylnmine and the like are also commonly pronounced methyl’amine phenyl’amine but there i s no diniculty in giving these worcls their correct and useful sounds whereas although the pronunciation hydrox‘ylamine is not an impossible one the “ 1 ” in it proves unpleasantly de trop. As we say hydroxyacetic acid for oxyacetic acid and simi-larly throughout the series of Iiydroxyl CornpoundR so should we say hydroxyamine for oxyamrnoaia. Already we do say hydroxyammonium and h<ydroxamic acids. Then again we say nitroscminea and not nitrosylamines. Thcre is another ad-vantage in dropping the (‘ 1,” for by doing so the chance is avoided of confounding tlie last syllable of oxyl with the first one of xylene as in nitroxylene.(Cf. A. H. Allen Chem. News 54 83.) LIhe term “ hydroxylarnine” is one which orcurs in every text-book and manual is universally employed by chemists and is applied to a compound very generally used by those engaged in organic research. There appears to be no reason why we should discard this name and adopt a new word to designate this well-known substance. I may point out that the argument adduced by Dr. Divers, in this note in favour of dropping the “ 1 ’’ from “ hydroxylamine ” applies with equal force to rnet>hylamine cthylamine benzylamine &c. mhich would become methyamine ethyamine and benzyami)$e respectivelj.-TEE EDITOH.REDUCTION O F NITRITES TO HYDROXYLAMINE. 49 ammonium and hydroxyammonium chlorides is obtained. Heating the filtrate without first adding an acid causes destruction of the hydroxylamine by the hydrogen sulphide. Two estimations were made of the quantity of hydroxylamine in the solution after this had been heated with hydrochloric acid. Silver nitrite 0-6926 gram was found by titration with iodine to have yielded about one-sixth of its nitrogen as hydroxylamine whilst in another case 0.0644 gram yielded as much as three-elevenths of its nitrogen in this form, In the Societyqs Abstracts of Proceedings p. 95 there is a prelimi-nary note by us on the reaction between mercurous nitrate and nitric oxide and between mercurous nitrate and alkali nitrites in which the formation of hydroxylamine is described together with separation of metallic mercury and some yellow prismatic crystals of unde-termined nature.Soon afterwards one of us succeeded in getting the supposed non- existent mercurous nitrite and this we then identified with our yellow prisms found in the reactions just referred to. Un-avoidable delay in completing the examination of mercury nitrites has caiised us to put off publishing this paper until now ; it is expected that t h a t on mercury nitrites will soon be ready. Mercurous nitrite yields just the same products as silver nitrite when it is treated with hydrogen sulphide ; but as this salt occurs in hard crystals and is exceedingly insoluble in water it is difficult t o decom-pose it completely by soluble chlorides including even hydrochloric acid Accordingly it resists decomposition by hydrogen sulphide for a long time and when what appears to be mercury sulphide (and sulphur) is boiled with water a nitrous odour is observed and mercury goes into soliition due no doubt to the decomposition of some residual nitrite.It was t o the above reaction between mercurous nitrite and hydrogen sulphide that the formation of hydroxylamine was due, when we treated mercurous nitrate first with nitric oxide or alkali nitrite and then with hydrogen sulphide-mercury nitrite being formed in the reaction we were investigating and hydroxyl-amine only by the hydrogen sulphide reducing this nitrite. We cannot indeed affirm positively that hydroxylamine is absent from the mercurial solution before hydrogen sulphide is added because it is not easy to find a reagent capable of precipitating the mercury-mercuric as well as mercurous-without decomposing any hydroxyl-amine that might be present.AS we know however that nitrite is present in aluundatice dissolved in the acid mercury solution," and as * Evidence of this will be submitted in our forthcoming paper on mercury nitrites together with an account of the formation of the nitrite and the precipita-tion of the metallic mercury. VOL. LI. 50 DIVERS AND H X ~ A REDUCTION OF NITRITES this would certainly give hydroxylamine with hydrogen sulphide, whilst the production of this base from mercurous nitrate and nitric oxide alone is most improbable there is now no ground whatever for believing that it is thus formed.On leaving metallic copper in contact with silver nitrite in water, a bluish-green solution is obtained from which a little hydroxylamine can be formed by treating it with hydrogen sulphide. A much larger yield can be got from the green mixture of solutions of copper sulphate and potassium nitrite. From the account we have @van of the behaviour of hydrogen sulphide towards nitrites it may be seen that those nitrites of which the metals-mercury silver copper-have especially well marked affinities for nitrogen and which therefore have R certain stability in presence of acids are capable of being reduced to hydroxylamine. In great part indeed even these nitrites are decomposed by the hydrogen sulphide in such a way as to yield merely the products of the decomposition of this acid by water and additional hydrogen sulphide ; but the rest appears to react as follows :-AgNO + 2H,S = AgNHsOH + H,O + 2s; 2AgNH*OH + HZS = 2NH,*OH + AgZS.As a means of preparing hydroxylamine the action of hydrogen sulphide on a nitrite has no apparent value. The interest of it lies in the light it may help to throw on the constitiition of the oxygen compounds of nitrogen. Experiments made in our laboratory and already published in the Society’s Journal serve to show that the metals of the zinc-tin class convert nitric acid into ammonia and not hydroxylamine when no other acid is present; and into hydroxyl-amine without ammonia when acting in conjunction with hydrochloric or sulphuric acid (Trans.1885 615) and further that in the conver-sion of nitric acid to hydroxylamine no nitrous acid nitric peroxide, or nitric oxide shows itself as an intermediate product (Trans. 1883, 461 462). An alkali nitrite brought suddenly in contact with hydro-chloric acid and zinc sometimes yields a little hydroxylamine (Trans., 2883,454) but as pointed out the probable conversion of the nitrous acid into nitric acid and nitric oxide before it comes in contact with the zinc leaves the point doubtfnl whether the little hydroxylamine obtained does not come from nitric instead of from nitroas acid. Thus it has been left uncertain whether an inorganic nitrite could be converted into hydroxylamine. By the reaction of the nitrites of the silver class of metals with hydrogen sulphide this uncertainty is at length removed.In connection with the subject of this paper it is of interest t o consider the well-known behaviour of the nitmhydrocarbons. Th TO HYDROXYLAMINE BY HYDROGEN SULPHIDE. 51 application of reducing agents if appropriate converts them t o amines but never to hydroxylamines. And yet the paraffin members of the series yield simple or substituted hydroxylamines by appropriate treatment. Plainly it must be impossible by simple reduction to convert the nitro-compound int,o the corresponding oximido-compound, because of the difference in valency between the nitroxy- and ox-imido-radicles ; the reaction therefore proceeds probably as follows :-EtNdO + 2H = EtN(OH),, EtN(OH) + 4H = EtNH + 20Hz. Rut when under special conditions the hydrocarbon radicle is made to undergo change it becomes possible to form an oximido-compound (Kissler) or at least hydroxylamine itself (V.Meyer). In these cases the hydrocarbon acts as the reducing agent on the nitroxyl. Thus nitroethane at 140" and in presence of water and hydrochloric acid yields hydroxylamine passing probably through the following stage :-in which acethydroxaruic acid results from the interaction of 2 mols. of the nitroethane and then as usual under the circumstances, suffers hydrolysis into hydroxylamine and acetic acid. Again by the interaction of sodium nitroethane and benzoic or acetic chloride, diacethydroxamic acid is actually obtained as the end-product :-'LMeCNaHNO + 2BzC1 = (MeCO),NOH + Bz,NOH + 2NaCl. In this case each oximido-radicle finds ready for it two univalent radicles in place of the one united to the nitroxyl in consequence of the elimination of the sodium and chlorine its sodium chloride. It is thus seen that under suitable conditions both nitrites of the metals and organic nitrites (nitronites) reduce t o hydroxylamines. It is further seen that the conversion of inorganic nitrites to hydroxylamine lends no support to the view that they have an oxylic constitution, because organic nitrites beyond doubt non-oxylic also reduce to oximido-compounds

ISSN:0368-1645    

DOI:10.1039/CT8875100048

出版商:RSC    

年代:1887

数据来源: RSC

摘要:

52 VI.-On Morindin and Morindon. By T. E. THORPE F.R.S. and T. H. GREL 4 UALL. THE roots of various species of Morinda particularly M. citrifdia and 34‘. tinctoria are extensively employed in various parts of India innder the general trade name of Xurmji as a dye-stuff more especially f o r dyeing reds purples and chocolates. These plants are to be met with in nearly all the provinces of India either wild as in the jungles of Bengal or cultivated in small patches in betel-nut plantations or near the homesteads of the dyers. In Bengal the plazlt is usually propagated by slips or cuttings but in other parts it is raised from seed as well as from cuttings. When the plants have attained a height of some 5 or 6 feet that is as a. rule, at about the end of the third year the straight spindle-shaped roots, xhich extend into the ground to a depth of 3 or 4 feet are dug out, and the upper portions of the plant are cut into slips to serve for the propagation of the next crop.The colouring matter is found principally in the root-bark and is developed in greatest quantities at about the end of three o r four years depending upon the character of the soil. After this time the dyeing-matter gradually disappears and the matured trees which eventually attain the height of a mango tree contain hardly a trace of it. The thin roots are the most valuable roots thicker than half an inch being thrown away as worthless. A’l or Aich as the root is called in Bengal is mainly used for dye-ing the thread or yarn from which the coloured borders of the cottou garments worn by the lower classes are woven But it is also occa-sionally employed for dyeing the coarse cotton fabric called “ KhArua,” or for dyeing the silk thread which forms the border of the silk fabric known as “ Endi” cloth.The colours given by A’l range from a reddish-yellow through pink and various shades of red to a dark brown-red. The tint seems primarily to depend upon the age of the root and upon the proportion of root-bark to root-stem which is employed. The root-bark gives the best reds ; the dye in the woody part of the root is yellow and hence when the wood preponderates over the bark the resulting dye is reddish-yellow. The methods of A’l-dyeing differ considerably in various parts OI India. The usual plan in Bengal is t o steep the cloth or yarn in a mixture of powdered castor-oil seeds and the ashes of plantain leaves or other alkaline ashes and water for some days with alternate washing and drying THORPE AND GREENALL ON MORINDIN AND MORINDOS.53 after which it is boiled with the dyeing solution prepared by treating the pounded roots or sometimes the root-bark only with water. Myrabclans turmeric the bark or leaves of Xy mpkocos racenm~a,, alum certain gums and various other substances are occasionally used as mordants or auxiliaries eitber immediately after the cleansing process or along with the dye-stuff ; frequently however the cloth is transferred directly from the cleansing liquor to the decoction of the root and no mordant is employed. Purple and chocolates are obtained by adding sulphate of iron to the dyeing liquor.* It will be observed that this process bears considerable resemblance in its main features t o that of Turkey-red dyeing by means of madder, and i t is not surprising therefore that some attempts should have been made to introduce Xuranji into this country as a substitute for the roots of Rubia tinctorurn.Morinda citrifolia indeed belongs t o the same natural order as the madder plant. The trials made nearly half-a-century ago by Turkey-red dyers in the neighbourhooii of Glasgow to make use of Xuranji as a dye-stuff were however with-out success. The first inquiry into the nature of the colouring matters of A’l was made by the late DY. Anderson (Trans. Roy. Xoc. Edin. 16 i v ; Anr/,aZen 71 216). Anderson found that on boiling the powdered root-bark wit’h alcohol it deep brownish-red solution was obtained, which on cooling deposited the greater part of the colouring mattcr in brown flocks mixed with a small quantity of a red substance which was not further examined.By repeated crystallisation from dilute alcohol (50 per cent.) the admixed red substance was removed and the main product which Anderson named morindin was obtained in fine needle-shaped lustrous crystals of a yellow or orange-yellow colour. On analysis they gave nnmbers from which Anderson deduced the formula C2,H,,O,,. On heating morindin in closed tubes it fused to a deep brown liquid ; this a t a higher temperature decomposed with the formation of an orange.coloured vapour which condensed to long red needle-shaped crystals leaving a residue of light porous charcoal.This crystalline product was termed worindorz by Anderson. The crystals were insoluble in both hot and cold water but readily soluble in alcohol and ether. Caustic alkalis and also strong sulphuric acid dissolved them with the production of an intense violet colour. With alum an ammoniacal solution gave a beautiful red lake and with baryt,a-water a cobalt-blue precipitate. Anderson’s analytical iiurnbers obtained from confessedly imperfectly purified material led him to express the composition of morindin by the formula C,,H,,O,,. * For further details see Liotard “ On Indian Dyes;” also IIcCann “Dyes and Tana of Bengal. 54 THORPE AND GREENALL ON MORINDIN AXD MORINDON. Hence it might be assumed to be derived from rnorindin by the elimination of 5 mols.of water a view of its origin which Anderson held to be substantiated by the mode of action of oil of vitriol upon morindin. After treatment with the acid the solution of morindin gave on dilution with water a yellow flocculent precipitate insoluble in water but soluble in alkalis with the violet colour characteristic of morindon. According to Rochleder ( Wiert. Akad. Ber. 7 SOS) Anderson’s morindin is probably identical with rubererythric acid C2,H2,014 the formula of which agrees practically as well with Anderson’s ana-lytical numbers as that which he himself deduced from them. Hence, therefore morindon would probably be identical with alizarin to which indeed from Anderson’s description of its physical properties, i t bears considerable resemblance.This view of the nature and relation of morindin and morindon was supported by Stenhouse (Chem. SOC. J. [1864] 17 333) mainly from a comparison of the absorp-tion spectra of morindon and alizarin. It would appear therefore, that the colonring matters of A’1 and of madder were probably identical. Several facts however seem to be inconsistent with this supposi-tion. We have first the circumstance of the inability of the Glasgow dyers to procure madder colours from 8uranji. Anderson also was unable to obtain more than a brownish-red colour in a trial of the Turkey-red process with pure morindin. Morindon on the other hand, he found to combine readily with mordants giving with alumina a deep rose-red and a violet or black colour with oxide of iron.Stein also (J.pr. Chem. 97 234) has adduced evidence t o show that Anderson’s morindin is not identical with rubererythric acid and that morindon is not identical with alizarin. According to Stein morindin is distin-guished from rubererythric acid by its insolubility in ether by the violet colour of its barium-compound and by its behaviour with caustic potash. It is like rubererythric acid a glncoside and by heating alone or by the action of alkalis is converted into products which reduce an alkaline solution of copper oxide. It melts at 245”, hut even below this temperature it gives it crystalline sublimate of morindon. Stein found that the readiest way of preparing morindon was to hy drolyse a dilute alcoholic solution of moriiidin with hydrochloric acid when the greater part of the morindon is deposited on cooling, as a bright reddish-yellow flocculent precipitate.In this manner morindin yields about half its weight of morindon whereas ruber-erythric acid if decomposed in accordance with the equation C,,H,,O, + 2H20 = C14H,04 + 2C6HI2O6 gives only 42.5 per cent. of alizarin. Morindin dissolves in oil of vitriol forming a solution which is a THORPE AND GREENALL ON MORINDIN AND MORINDON. 55 first indigo-blue but this gradually changes to a reddish-purple and eventually becomes yello wish-red. Alizarin gives a reddish-purple coloured solution at once. With ferric chloride an alcoholic solution of morindon gives a dull green colour whereas with alizarin the colour is reddish -brown.When oxidised with nitric acid morindon gives no phthalic acid but only oxalic acid. According to Anderson (Zoc. cit.) however the nitric acid solution of morindon after long continued boiling and subsequent neutralisation with ammonia gives no precipitate with salts of lime. Stein found that the optical behaviour of solutions of morindon agreed perfectly with the descrip-tion given by Stokes and on which Stenhouse based his assumption of the identity of morindon and alizarin. This conflict of testimony respecting the real nature of the colouring matter of A'1 seemed to warrant fresh investigation. Thanks to the kindness of the Director of the Royal Gardens Kew who mas good enough to make application to the India Office on our behalf we obtained about 10 lbs.of the roots of M. citrifdia. The method of extraction we employed was substantially that described by An-derson the powdered root-bark being repeatedly treated with hot dilute alcohol so long as anything seemed to be dissolved. The roots as received from the India Office were in two parcels the one parcel consisting of thick and evidently old roots the other of thin roots as a rule not more than $ inch thick these alone appeared to contain any sensible quantity of the colouring matter. The alcoholic extracts were concentrated by evaporation and the precipitates which formed on standing were collected and treated first with benzene and then with absolute alcohol so long as any red colouring matter passed into solution. The residue was then dissolved in hot 50 per cent.alcohol and purified by repeated crystallisation. In this manner about a gram of pure morindin was obtained. After being dried a t loo" it yielded the following numbers on analysis :-I. 0.2024 gram gave 0.4098 gram CO and 0.0930 gram H,O. 11. 0.2088 , 0.4236 , , 0.0951 ,, Calculated for C26H28014. (rubererythric Calculated for Anderson's acid). C2sH300 15' analysis. I. 11. c . . . . 55.33 55.44 55.43 55.27 55.37 H . 4.96 4-95 5-11 3-11 5.06 0 . . . . 39.71 39-60 100~00 100.00 - - -It will be observed that our analytical results are in close agree-ment with those of Anderson and that both sets of numbers ar 56 THORPE AND OREENALL ON MORINDIN AND MORINDON. almost as well expressed by the formula C28H30015 as by that of ruberery thric acid.Through the kindness of Dr. Schunck who forwarded us a speci-men of rubererythric acid we have been enabled to make a corn-parison of thc properties and modes of decomposition of that substance with those of morindin. In appearance the two substances were almost exactly similar. When heated in capillary tubes placed side by side they both decomposed with charring at about the same tempera-ture and yielded reddish or violet vapours condensing to crystalline sublimates. Contrary to the statements of Rochleder and Stein, rubererythric acid was found t o be practically insoluble in ether. Rubererythric acid and morindin are however at once distinguished by their reaction with potash both give bright red solutions but on boiling that of rubererythric acid at once changes to a dark purple, whilst that of morindin does not alter even after long-continued boiling this reaction is Fery striking and characteristic.A further proof that rubererythric acid and morindin are not identical is afforded by their behaviour on hydrolysis. 0.4354 gram rubererythric acid and 0.4884 gram morindin were separately dis-solved in 80 c . ~ . boiling 50 per cent.' alcohol together with 8 c . ~ . strong hydrochloric acid solution. The solutions were heated by steam under a reflux condenser for about four hours when the hydro-lysis was found to be complete. The precipitates were then collected, washed with water dried at 120° and weighed. The weights were-From rubererythric acid 0.1832 gram = 42.1 per cent. , morindin , 02369 , = 48.5 ,, The proportion of the hydrolysed product to the morindin em-ployed agrees closely with the result obtained by Stein the amount of the hydrolysed product in the case of the rubererythric acid is nearly 66 per cent.lower and is almost ideiitical with that required by the equation C2sH28014 + 2H,O = C14H804 + 2C6HEc,,0, which gives 42.5 per cent. of alizarin. Moreover the two products behaved very differently towards re-agents. That from rubererythric acid gave a blue-purple colour with potash unchanged on standing ; in t,he case of that from morindin t'he colour was reddish-purple and gradually faded. With ferric chloride, the rubererythric acid product gave a dull brownish-yellow coIora-tion ; with the morindin product the colour was sage-green.With concentrated sulphuric acid the product fi-om ruberery thric acid gave a bright yellowish-red ; whereas in khe case of the morindin product the coloration was first dark-blue and then purple. Seen under the microscope the forms of the two products as crystallised from benzene were quite distinct. The two products were then submitted t TIIORPE AND GREENALL ON MORINDIN AND MORINDON. 57 analysis after being heated side by side at 130° with the following results :-Product from rubererythric acid :-0.1437 gram gave 0.3726 gram CO and 0.0458 gram H,O. Calculated for alizarin, Found. C,,H,O,. C 69.74 70.00 H 3.49 3-33 0 26.77 26.6 7 100~00 100.00 -Product from morindin-0.1604 gram gave 0.3906 gram CO and 0.0554 gram H,O. Calculated for Calculated.for trihydroxymethylanthra- isopurpurm, Found. quinone Cl5HlOO5. c 1 4 6 3 0 5 . C 66.41 66.66 65.62 H 3.83 3-70 3.12 O . . . . . . 29-76 29.64 31.26 100~00 100~00 100*00 -There would seem therefore to be no doubt that morindin and rubererythric acid are not identical as was supposed by Rochleder and Stenhouse. The true nature of morindon has still to be de-termined; the amount of material at our disposal was unfor-tunately insufficient for its further investigation. In many of its react'ions morindon closely resembles isopurpurin although t'he numbers afforded by its analysis agree more nearly with those required by trihydroxymethylanthraquinone. In either case its formation by hydrolysis is not very readily explained. We made attempts to.determine the quantity of sugar yielded by the decom-position of a known weight of the morindon but the amount obtained ( 3 5 per cent.) threw no light upon the mode in which the morindin is derived or upon its probable formula. It is however quite certain that morindin is not identical with the only trihydroxy-methylanthraquinone at present known viz. the Bwwdin discovered by Warren De la Rue and Hugo Muller in rhubarb root (Chenz. SOC. J. 10 304). Our thanks are due to Dr. Hugo Muller for his kindness in affording us the opportunity of comparing the properties of the two products. Since the experimental work in connection with this communication was concluded Mr. Thomas Wardle of Leek has kindly placed a quantity of the roots of M. citrifolia and M. tifzdoria at our disposal. As however we are unable to prosecute the wor 58 HARTLEY SPECTROSCOPIC NOTES OX THE in common any further we have ventured to bring the results obtained up t o now before the Society. One of us hopes to be shortly in a position to present the results of a fuller investigation. A portion of the work was done in the laboratory of the Yorkshire College our thanks are due to Mr. C. W. Gamble a former student, of that institution for his assistance in the extraction of the crude colouring matter from the roots

ISSN:0368-1645    

DOI:10.1039/CT8875100052

出版商:RSC    

年代:1887

数据来源: RSC

摘要:

58 HARTLEY SPECTROSCOPIC NOTES OX THE VII.-8pectroscopic Notes on the Carbohydrates cnzd Albuminaids from Grain. By IV. N. HARTLEY F.R.S. Professor of Chemistry Royal College of Science Dublin. ACCORDING to C. v. Nageli (“ Theorie du GGhrung”) fermentation is a pyocess which may be described as the transference to fermentable matter of the molecular or rather intramolecular vibrations of the differant constituent substances entering into the composition of living protoplasm (which remains itself unchanged in composition) and herice the equilibrium of the molecules of the fermentable matt’er becomes so disturbed as to cause their resolution into simpler mole-cules. In this case the intramolecular vibrations of the substances are transferred through the cell-wall of the saccharomyces to the molecules of sugar outside.It appears by no means improbable that the diastatic ferments may have some such action; therefore any facts bearing on this matter are of interest. The vibrations of the active substances must be either of greater amplitude than those of the carbohydrates or else of much greater frequency ; for if of the same frequency but of lesser amplitude they could not cause any such effect as that described. Now it seemed to me to be possible to learn something of the mode and rate of vibration both of the molecules of the carbohydrates and of the diastatic ferments. Accordingly I have photographed the absorption spectra transmitted by solutions of saccharose glucose and starch as also those of several albumino’id compounds and egg-albumin.For specimens of diastase from malt and invertase from yeast I am indebted to Mr. Cornelius O’Sullivan who kindly placed specimens at my disposal some two years and a half since with the offer of a further supply if necessary. While the work was in progresB M. I;. Soret published his fift CARBOHYDRATES AND ALBUMINOIDS FROM GRAIN. 59 memoir on the absorption of ultra-violet rays by different substances, which included an examination of the various forms of albumin (Archives des Sciences Physiques e t NaturelEes 10 139 ; Cornpt. rend,, 97 642) the carbohydrates glucose saccharose and gelatin. My results proved to be in strict agreement with his as regards these snbstances ; it is proposed therefore to give them in abstract only. Considerable difficulty was encountered in photographing some of the liquids on account of their opalescence which prevented more than thin layers of liquid from being examined.In one or two cases as with gelatin and with starch the liquid was allowed to dry on plates of quartz and the rays were passed through the dried films. This proved decidedly advantageous but on the whole the turbidity of the solutions has been a source of much trouble. GeZatin.-(1.) A yellow specimen sold for photographic purposes, said to be of Nelson’s preparation b u t without any distinchive label. A solution containing 5 per cent. of the solid and 1 mm. in thickness was allowed to dry on a plate of qnartz. It transmitted a continuous spectrum to wave-length 2265 but beyond 2313 the rays were weak.(2.) A very fine colourless sample made in sheets which in the original form transmitted all rays to 2265. A solution containing 5 per cent. and 1 mm. in thickness dried on a plate of quartz transmitted all rays to wave-length 2265 in full intensity. Maize Xiarch.-Brown and Polson’s corn flour. A solution of 1 part to 12 of water and 1 mm. thick dried on a plate of quartz trans-mitted a spectrum of normal strength as far as wave-length 2145. Cane-sugar.-A solution Containing 10 per cent. transmits all rays through as much as 25 mm. as far as wave-length 2145. Very highly diactinic. A solution containing 10 per cent. transmitts all rays through a thickness of 10 nim. as far as 2145. According to &I. Soret’s measurements, the following wave-lengths have been reckoned :-2 mm.diluted with water twice from about Glucose.-A very pure specimen. Albunzin.-White of egg. Absorption-band. 2880 to 2650 34 3 , five times from I ¶ I , 4 9 3 , nine times , 9 9 9 The same absorption-band occurs when albumin is acidified. Pure Albumin.-When a solution of pure a1 bumin containing 37 grams per litre is examined 2 mm. of the liquid exhibit an absorption-band from about 2948 to 2572 wave-lengths. Cmezn.-A solution containing 6.5 grams per litre. 8 mm. and 9 rnm. 8erin.-Solution containing 10.5 grams per litre. 4 mm. t o 5 mni. A similar band. Absorption-band from about 2948 to 2572 60 HARTLEY SPECTROSCOPIC NOTES. Solutioiis of invertase and diastase were prepared from Mr. O’Sullivan’s specimens.Invertase was also prepared from compressed porter yeast by simple treatment with water and filtration the yeast being from the brewery of Messrs. A. Guinness and Sons. The solu-tions were difficult to examine especially the diastase; the con-siderable quantity of matter dissolved rendered filtration difficult, and they showed a certain degree of turbidity not easily removable. The possibility of manipulating the liquids so as to clarify them was interfered with by reason of the facility with which they putrefy and the necessity of avoiding the addition of any preservative to them. The following is a description of the spectra :-Invertase.-A solution containing about 1 per cent. or 0.1 grani dissolved in as little water as possible between 8 C.C. and 10 c.c. and filtered.Wave- Oscillation lengths. frequencies. 20 mm. continuous spectrum to 2418 4136 15 ?7 7 7 7 2313 4326 10 9 9 9 2263 4420 5 4 and 3 mm. continuous spectram to 2193 4555 2 and 1 mm. continuous spectrum to. 2148 4658 Yeast Water.-The same result was obtained as with invertase. Diastase.-A solution containing about 1 per cent. or 0.1 gram in 10 C.C. of water. The turbidity of this solution weakened the spectrum throughout when a thickness of 10 Em. was examined. Wave- Oscillation lengths. frequencies. 10 mm. 9 mm. and 8 mm. con-tinuous to 2988 3359 A strong line faintly visible at 2568 3890 7 mm. and 6 mm. continuous to 2568 3890 The albuminoYds invertase and diastase are eridently of very dif-ferent constitution from albumin casein and serin all of which as Soret has shown have something in common which is disclosed by the absorption-band common t o their spectra.Gelatin tliff ers from these forms of albumin. While albumin casein and serin exhibit absorption-bands in dilute solutions and in small thicknesses of such solutions gelatin invertase diastase starch glucose and smccharose, under like circumstances are seen to be highly diactinic and show no absorption-bands. It does not therefore appear likely that a sub-stance of the character of albumin could affect the carbohydrates, while on the other hand it is possible that the intramolecular vibra DTSON THE ACTION O F SALICYLIC ALDEHYDE. 61 tions of invert'ase and diastase might be communicated to sacchaross and starch. Froin this of course it folIows that there may be in yeast-water or within the yeast-cell some similarly constituted albu-mino'id capable of acting on glucose in a manner similar to the action of invertase on saccharose but yielding different products.Setting aside theoretical considera,tions touching fermentation it is of great interest to find that substances of such complex coinposition as the sugars so extraordinarily diactinic for this is quite in character with what we know of their constitution. It is no less interesting to learn that the albumino'id compounds associated with the carbo-hydrates are evidently different in constitution from those forms of albumin found in the animal organism. The probability presents itself of these albuminoi'ds being derived from the carbohydrates.The examination of specimens of gelatin shows that the difficulty in obtaining photographic plates sensitive to the most refrangible rays, lies entirely with the character of the gelatin. Ordinarily the spectrum extends Do wave-length about 2146 Cd. Some plates prepared many years ago by Wratten and Wainwright called ordinary dry plates, were used for photographing a series of metallic spectra which extend to wave-length 2024 Zn and there is little doubt that they were capable of receiving impressions of lines still more refrangible. Since then plates of every kind by every maker have been tried but most of these transmit nothing beyond 2146 Cd. A sample from Mawson and Swan was recently found to photograph as far as 2024 but half a dozen other batches from the same makers were deficient in this respect notwithstanding that they were supposed to be of exactly the same character. As the plates were prepared in precirely the same way there can be no doubt that the difference was in the gelatin which must have contained some very slight trace of impurity which could not otherwise be detected

ISSN:0368-1645    

DOI:10.1039/CT8875100058

出版商:RSC    

年代:1887

数据来源: RSC

摘要:

DTSON THE ACTION O F SALICYLIC ALDEHYDE. 61 VII1,-The Action of Salicylic Aldehyde o n Hodiurn Succirzate in presence of Acetic A&ydritle. By GIBSON DYSON Ph.D. Demonstrator of Chemistry Normal School of Science South Kensington. IN order to see if Perkin’s reaction is equally applicable to the hydroxyaldehydes I undertook at the request of Professor Fittig to study the action of salicylic aldehyde on sodium succinate. J a p e (Annalerz. 216 97) has shown that by acting on sodiu 62 DYSON THE ACTION OF SALICYLIC ALDEHYDE ON succinate with benzaldehyde at a temperature of 100-120" phenpl-paraconic acid is principally formed. It was therefore t o be expected that by substituting salicylic aldehyde for benzaldehyde hydroxy-phenylparaconic acid woiild be obtained.This was not found to be the case however the product being a neutral substance having the composition CleHlo04 which subsequent investigation proved t o be dicoumarin. I n 1872 Zwenger (Annalen Sup. 8 32) showed that when coumarin in aqueous solution is treated with sodium amalgam, i t gives melilotic acid C,HloO, by acting with sodium amalgam on a saturated alcoholic solution of coumarin however the reaction pro-ceeded quite differently ; in this case he obtained the sodium salt of a new acid which he called hydrocoumaric acid CleHl,O6. The characteristic properties of this acid are that its sodium salt is practically insoluble in alcohol and that on being heated it gives off 2 mols. H,O forming an anhydride melting at 222.6". Cohen (Inaugural Uissertation Munchen 1884) by the reduction of p-methylumbelliferon-paramethyl ether in alcoholic solution with sodium amalgam obtained a compound CZ2Hz2O6 which he regarded as belonging to the same class of compounds as Zwenger's acid.As the substances above mentioned are the only dicoumarins known it seemed desirable that the dicoumarin obtained by the action of salicylic aldehyde on sodium succinate should be submitted t,o a thorough investigatiou. Preparation of Dicoumarilz. A mixture of salicylic aldehyde sodium succinate (dried at 140" C.) and acetic anhydride in the proportions of their respective molecular weights was heated for 24 hours on the water-bath in a flask connected with a reflux condenser. It is essential t o the success of $he experiment that every trace of moisture should be excluded from the apparatus and that all the material used should be perfectly dry.The contents of the flask which had darkened in colour were treated with hot water to remove sodium succinate and the acetic anhydride which still remained unacted on ; and the excess of salicylic aldehyde was removed by a current of steam. The dicoumarin after being washed with ether to remove a tarry substance which is always formed in small quantity remained as a pale-yellow crystalline powder insoluble in all the ordinary solvents. It was recrystallised from hot glacial acetic acid in which it is only sparingly soluble ; on cooling it separated out in needle-shaped crystals. The analysis of this compound indicated the composition C,H,,O ; it is formed by the condensation of 2 mols.of salicylic aldehyde with 1 mol. of succinic acid SODIUM SUCCINATE I N PRESENCE OF ACETIC ANHYDRIDE. 63 As by the above method the greater part of the aldehyde remained unacted on the following modification was tried and the results being more satisfactory it was adopted for the preparation of all the material used in this research. A mixture of 10 grams of sodium succinate 15 grams of salicylic aldehyde and 13 grams of acetic anhydride was heated in a sealed tube for 40 hours at 140". The contents of the tube were then extracted with hot water and thc residne which consists of dicou-marin and nnalkered salicylic aldehyde was treated in exactly the same manner as previously described. From 10 grams of salicylic aldehyde about 5 grams of dicoumarin were obtained.It was found that an excess of acetic anhydride did not increase the yield of dicou-marin but gave rise to the formation of various complicated condcn-sation products which have not been further investigated. The dicou-marin was purified by recrystallisation from hot glacial acetic acid ; the product thus obtained was slightly yellow and it was found impossible by this method of purification to render i t colourless. It can however be completely decolorised by dissolving it in a hot solution of soda and then reprecipitating it by the addition of hydro-chloric acid. On fusing it with caustic soda salicylic acid is formed. The melting point of dicoumarin lies above 330". The following are the analytical results obtained :-I.0.2012 gram of substance gave 0.55'22 gram of CO and 0.0650 gram of H,O. Calculated for C18H1004* Found. C . 74.48 per cent. 74.84 per cent. H . 3-45 , 3.54 ,, 11. Analysis (after being recrystallised). 0.285 gram of substance gave 0.7775 gram of GO2 and 0.0908 of H20. Calculated for c18H1004- Found. C . 74.48 per cent. 74.40 per cent. H . 3-45 , 3.53 ,, Dicoumarin is an extremely stable compound insoluble in ether, alcohol and benzene but slightly soluble in chloroform and glacial acetic acid ; it is not acted on at the ordinary temperature by sodium carbonate ammonia or caustic soda. On boiling it for some time with a solution of sodium or barium hydrate it slowly dissolves, forming a yellow solution from which it is reprecipitated unchanged on addition of an acid 64 DYSON THE ACTION OF SALICYLIC ALDEHYDE ON The following is an analysis of the product thus obtained :-0,220 gram of substance gave 0.6003 gram of CO and 0.0726 gram of HZO.Calculated €or C,,H,OO,. Found. C . . . . . . . . . H . . . ,. . . 3.45 , 3-66 ,, 74.48 per cent. 74-45 per cent. If however hydrochloric acid is gradually added to the alkaline solution and this is kept cool by means of a freezing mixture a pre-cipitate is obtained which redissolves on addition of sodium carbonate. On attempting to separate this precipitate by filtration it is imme-diately decomposed dicoumarin being regenerated. It is probable that the compound formed is an unstable oxyacid similar in fact to that obtained by dissolving dicoumarin in caustic soda.The formation of dicoumarin from salicylic aldehyde and succinic acid may be represented by the following equation :-Actiorz of Sodium Anznlgam o n Dicournari.12. An alkaline solution of dicoumarin prepared by dissolving dicou-marin in hot concentrated caustic soda and diluting with water was treated on the water-bath with sodium amalgam (containing 5 per cent. of sodium) until the precipitate produced by the addition of hydro-chloric acid redissolved completely on adding sodium carbonate. I n order that the reduction may not proceed too slowly it is neces-sary to keep the solution as nearly neutral as possible. This is done by the occasional addition of hydrochloric acid. The alkaline liquid was decanted from the mercury acidified with hydrochloric acid and the precipitate formed collected on a filter.It is not soluble in chloroform or benzene and only slightly so in water and ether but dissolves freely in alcohol ; i t is also soluble in a solution of sodium carbonate with evolution of carbon dioxide. T t was purified by recrystallisation from dilute alcohol. The product thus obtained was found to have an indefinite composition and it was therefore, assumed to be a mixture. Proceeding on this assumption various methods of separation were tried and it was finally found that by converting it into the barium salt and fractionally recrystallising the latter the pure acid could be obt,ained. The mixture was accordingly dissolved in a solution of barium hydrate and the excess of barium precipitated from the hot solution by a current of carbon dioxide.On filtering and allowing the filtrate to cool a barium salt separated out having the composition (C1,H1305)2Ba + xH20 being in fact SODIUM SUCCINATE IN PRESENCE OF ACETIC ANHYDRIDE. 65 barium hydrodicoumarate. In the mother-liquor there still remained flr small quantity of the last-named salt together with a salt much more easily soluble in water. The latter is undoubtedly the barium salt of the acid obtained by further reduction of hydrodicournaric acid. I t was found that when the reduction of the dicoumarin was only continued until i t was all decomposed very little of this more highly-reduced acid was formed. Bychodicoumaric Acid C,H,,Oa. This acid was obtained as a white precipitate by adding hydro-chloric acid to a solution of the barium salt.It is insoluble in chloro-form and benzene and dissolves only slightly in hot water or ether, but freely in alcohol. By recrystallisation from dilute alcohol it was obtained in needle-shaped crystals. When heated at 130" it loses the elements of water forrming an anhydride C&&& Dried over sulphuric acid (when dried at 100" it lost weight pro-bably due to the formation of a small quantity of the anhydride) it yielded on analysis the following figures -0.0215 gram of substance gave 0.5485 gram of CO and 0.0906 gram of HZO Calculated for CISH1405. Found. C . 69.67 per cent. 69.58 per cent. H 4-51 , 4.67 ,) Barium Salt (C18H1305)2Ba + xH2o. It is only slightly soluble in cold water but more readily in hot from which it separates on cooling in well-defined crystals.These on exposure to the air effloresce and become opaque rendering it impossible either to determine the water of crystallisation or the crystalline form The following are the analytical figures obtained :-I. 0.3861 gram of salt gave on heating at 130" 0,04725 gram of water and on treatment with sulphuric acid 0.1047 gram of barium sulphate. Tlie preparation of this salt has already been described. Calculated for the dried salt. Found. Ba 18.18 per cent. 18.14 per cent. The formula (C18H1306)2Ba + 6H2O requires 12.51 per cent. of water. Found 12.2 per cent. vor,. Lr. 6t; DYSON THE ACTION OF SALICYLIC ALDEHYDE OX 11. 0.31275 gram of the salt gave 0.05675 gram of water and on treatment with sulphuric acid 0.0767 gram of barium sulphnte.Calculated for the dried salt. Found. Calculated for (Cl8HI3O6)Ba + 9H20 = 17-66 per cent. of water. B a . . 18.18 per cent. 18-34! per cent. Found 18.14. /%he?- X d t C,8H130,Ag. On adding silver nitrate to a solution of the barium salt the silver salt was obtained as a white curdy precipitate which on standing became crystalline. It is almost insoluble in water. The analysis of the salt dried over sulphuric acid gave the following figures :-0.2325 gram of the salt yielded 0.4427 gram of CO, 0.0687 gram of H,O and 0.0595 gram of Ag. Calculated for Ci8H1305Ag* Found. C 52.13 per cent. 51.93 per cent. H 3-12 , 3.28 ,, A g . . 2-5.82 ? 25-59 ,, The calcium salt obtained by treating the ammonium salt with calcium chloride is almost insoluble in water.€Fyd~odicournarin C,,H,,O,. Hydrodicoumaric acid as has already been mentioned splits up on being treated at 133" into the anhydride hydrodicoumarin and water. I n order to prepare hydrodicoumarin hydrodicoumaric acid which for the purpose need not be quite pure is melted between watch-glasses. The melt on cooling is first washed wit8h alcohol in order to remove any unaltered acid asd then dissolved in hot cliloroform ; on allowing the chloroform to stand hydrodicoumarin is deposited in small but well-defined crystals. It can also be precipitated directly by the addition of alcohol. Hydrodicoumarin is insoluble in water, alcohol and ether ; i t melts at 2.56" and wheii heated above this tem-perature it sublimes with partial decomposition in needle-shaped crFstals ; the vapour has an odour resembling that of coumarin.On analysis the following numbers were obtained :-0.2217 gram of the anhydride yielded 0.6028 gram of CO and 0.0833 of H,O. Calculated for C14H1204. Found. C 73.97 per cent. 74.09 per cent. H 4.11 , 4.17 , SODIUi\l SUCCINATE IN PRESENCE OF ACETIC ANHYDRIDE. 67 In order to see if it could easily be reconverted into the acid i t was boiled with water for three days ; at the end of which time it was found to be unaltered. It is not attacked when boiled with sodium carbonate or dilute caustic soda but if heated for some time with a concentrated solution of caustic soda it is recoiiverted into the acid. The crystals of hydrodicoumariii obtained from its solution in chloroform were not satisfactory and it was thought that a better product might be obtained by recrystallising it from dilute acetic acid.Hydrodicoumarin was therefore dissolved in hot glacial acetic acid and water added until the precipitate formed just redissolved on boiling. After two crystallisations a well-crystallised substance was ob-tained which on analysis gave the following results :-0.2173 gram of substance gave 0.5581 gram of CO and 0.091 gram of H,O. Calculated for hydrodicoumaric acid, Cl8H405- Found. C . . . . . . . . 69.97 per cent. 70.00 per cent. H 4-51 , 4.65 ,, Prom the above result i t would follow that by boiling hydro-dicoumarin with acetic acid hpdrodicoumaric acid is reformed.I hope to be able to give more details regarding this reaction in my next paper. Action of Bromine o n Hydrodicoumaric Acid. Hydrodicoumaric acid suspended in chloroform was treated with the calculated quantity of bromine (2 mols. of Br to 1 mol. of the acid). It is necessary in order t o prevent the formation of substitu-tion products to keep the mixture cool by surrounding it with ice ; if this precaution is taken no hydrogen bromide is given off. A clear solution was obtained which after a time deposited a white pre-cipitate ; it was impossible however to analyse this compound as on attempting to dry it i t immediateIy decomposed giving off hydrogen bromide and leaving a white insoluble substance. This was purified by dissolving it in hot glacial acetic acid from which on cooling it separates out in crystals On analysis the following numbers were obtained -0.291 gram of the substance gave 0.1499 gram AgBr.Calculated for ' C16HllBr04. Found. BY . . . . . . . 21.56 per cent. 21-92 per cent. F 68 DYSON THE ACTIOS OF SALICYLIC ALDEHYDE ON The compound is consequently inonobromohydrodicoumarin. It is insoluble in alcohol and ether and dissolves only slightly in chloro-form. In the original solution there still remained a compound, easily soluble in chloroform which has not yet been analysed. As dicoumarin is formed by the condensation of 2 mols. of salicylic aldehyde witlh 1 mol. of succinic acid it follows that the simplest constitutisn that can be assigned t o i t is It has further been been shown that by limited reduction dicou-marin yields a monobasic acid to which the constitution has been given.Prom this it would appear as if it were necessary in order for the oxgacid to be stable that the COOH group be combined with a saturated carbon-atom. It was therefore to be expected that by further reduction of hydrodicoumaric acid a bibasic acid would be formed which should be identical with Zwenger's acid. Action of Xodium Amalgam on. Hydrodicoumaric Acid, Hydrodicoumaric acid was dissolved in a solution of sodium carbo-nate and treated repeatedly on the water-bath with sodium amalgam (containing 5 per cent. of sodium). The reduction must be continued for several days and the solution kept as nearly neutral as possible. On decanting the alkaline solution from the mercury and acidifying with hydrochloric acid the new acid was obtained as a white pre-cipitate.It can be purified by recrystallisation from water o r dilute acetic acid. The best method however to obtain i t perfectly pure is to convert it into the calcium salt which can be purified by recrystal-lisation from hot water. As the calcium salt of hydrodicoumaric acid is nearly insoluble in the last-named solvent an easy separation of the two acids can be effected. The new acid crystallised from dilute acetic acid forms colourless crystals soluble in alcohol but insoluble in chloroform. When heated above loo" it is slowly decomposed without changing its outward appearance forming an anhydride. The analysis shows it to have the same composition as 2; wenger's hydrocoumaric acid C,,H,,O,, with which however it is not identical.This acid may be named dihydrocowmaric acid. If forms an insoluble silver' salt and a sodium Halt soluble in alcohol SODTUM SUCCINATE IN PRESENGE OF ACETIC ANHYDRIDE. Cj!) 0-2216 gram of the acid yielded 0.5333 gram of CO and 0.1101 gram of H20. Calculated for CHHt306. Found. C 65-45 per cent. 65.63 per cent. H 5.45 , 5.52 ,, Calcium Dihydrocoumarate C1sH1606Ca -t 6H20. This salt was prepared by boiling the acid with water containing calcium carbonate in suspension. On filtering from excess of calcium carbonate and concentrating the filtrate it separated on cooling in radiating groups of acicular crystals containing 6 mols. H20 which it loses at 140". I. 0.3084 gram of the salt gave 0:0710 gram of water and on I1 on addition of sulphuric acid OG393 gram of calcium sulphate.Calculated for ClsH&&h f 6&0. Found. Ca 8.40 per cent. 8.52 per cent. H,O 22.69 , 23.00 ,, 0.1616 gram of salt gave 0.036 gram of water and 0.0466 grain of calcium sulphate. Calcdated for C18H1606Ca -k 6H20. Found. Ca 8.4 per cent. 8.48 per cent, H,O 22.69 , 22.27 ,, Silver salt ClsH,606Ag2. adding silver nitrate to a solution of tlie calcium salt (if the ammonium salt be used the producf is impure) the silver salt was obtained as a white voluminous precipitate which on standing became crystalline. The analysis of this salt dried at loo" gave the following results -0.1945 gram of salt yielded 0-2831 gram of GO2 0.0578 grain of H20 and 0.0768 gram of Ag.Calculated for clSH1608 Found. Ag 39.70 per cent. 39-48 per cent. c 99-70 , 39-76 ,, E 2.96 , 3.26 ,, Second determination of the silver: 0.2377 gram of salt gave 0.0939 gram of Ag 70 DYSON THE ACTION OF SALICYLIC ALDEHYDE ON Calculated . Found. Ag . . . . . . 39.7 per cent. Dih ydrocouni arin C18H1404. 39.5 per cent. The anhydride was obtained by melting the acid between watch glasses. The melt was then washed with alcohol in order to remove any undecomposed acid and dissolved in chloroform ; from this solution it separated out on the addition of alcohol or on standing, in needle-shaped crystals. It melts at 222-2234" and sublimes with partial decomposition when heated above this temperature ; the vapours have an odour similar to that of coumarin ; on boiling with water or carbonate of soda it is not altered but when heated with caustic soda it is slowly dissolved being reconverted into the acid ; when it is fused with solid caustic soda salicylic acid is formed.The following are the analytical results obtained :-0.169 gram of the substance gave 0,4554 gram of CO and 0.0754 gram of HaO. Calculated for C18IJ1404. Found. 4 C 73.47 per cent. 73.49 per cent. H . . . . . . . . 4.76 , 4-81 ,, The anhydride seems to be identical with that obtained by heating Zwenger's acid possessing as it does the same chemical composition and melting point. As the properties of the acid from which the anhydride was pre-pared do not correspond with those given by Zwenger to his acid, it was thought desirable to prepare it specimen of the acid according t o his directions.Preparation of H!ydrocozcrnaric Acid. 20 grams of coumarin were dissolved in about 50 C.C. of absolute alcohol and treated repeatedly on the water-bath with sodium amalgam ( 5 per cent. of sodium). In it short time the insoluble sodium salt separated and the quantity was further increased by the addition of more absolute alcohol. The salt after washing with alcohol in order to remove coumarin sodium coumamte and sodium melilotate was dissolved in water and the solution acidified with hydrochloric acid; on standing for about two days the acid was deposited in acicular crystals. That this acid is not identical with that obtained by the. reduction of hydrodicoumaric acid is shown by the different solubilities of the sodium salts in alcohol ; hydrocoumaric acid is also much more readily soluble i n water and the difference between their calcium salts is most marked SODIUM SUCCINATE IN PRESENCE OF ACETIC ANHYDRIDE.71 Calcium Hydrocoumarate CleH1606Ca + 2H20. Calcium hydrocoumarate was prepared by boiling a solution of the acid in water with calcium carbonate until no more carbon dioxide was evolved. On filtering of€ the excess of calcium carbonate and coilcentrating the filtrate the salt separated in crystals containing 2 moh. H,O which were driven off on heating at 133-140". I t dissolves only slightly in either hot or cold water ; if anything, it is rather more soluble i u cold than hot water. On analysis the following results were obtained :-0.3167 gram of the salt on heating at 140° gave 0.0101 gram of water and on addition of sulphuric acid 0.0422 gram of calcium sulphat e.Calculated for c,,H~,jo,Ca + 2H2O. Found. H,O 8-00 per cent. 7.97 per cent. Ca 10*00 , 9-79 ,, Hydrocounzarin C1,Hl4Oa. Hydrocoumaric acid was melted between watch-glasses and the product after solidifying washed with alcohol till colonrless. It was then dissolved in boiling chloroform and from hhis solution it separated on the addition of alcohol in fine acicular crystals. It melted at 222O and on analysis gave the following iiumbers :-0.2066 gram of the substance gave 0.5596 of GO and 0.09 gram of HJ3. Calculated for clE H14°4- Found. C 73.47 per cent. 75.87 per cent. H 4*?6 , 4.84 ,, The existence of two isomeric acids having the composition ClaHl6OG has thus been proved.Both these acids when heated, yield an anhydride CleHHOa melting at 222-224". Whether they are identical o r not is at present an open question the identity of the melting points being possibly a mere coincidence. By reconverting tlie anhydrides into acids and studying the products thus obtained, there is no doubt but that this question could be satisfactorily settled. If the anhydrides are found to be identical we have here another case of isomerism similar to that observed by Perkin (Chem. Xoc. J., 39 4U9) as existing between a- and p-coumaric acids ; on the other hand should they prove t o be different hydrocoumaric acid must have a constitution different from that generally assigned to it 72 PICKERING DECOMPOSlTION OF The investigation of these compounds is being continued. I take the present opportunity of thanking Professor Fittig for the valuable advice he has given me whilst engaged upon the above work

ISSN:0368-1645    

DOI:10.1039/CT8875100061

出版商:RSC    

年代:1887

数据来源: RSC

摘要:

72 PICKERING DECOMPOSlTION OF 1X.-Decomposition of Sod izcm Carbonate by Fusion. By SPENCER UMFREV~LLE PICKE RING M.A. Professor of Chemistiy xf Bedford College. BERTHELOT ascertained (Ann,. Chim. Phys. 29 311) that anhydrous sodium sulphate after fusion dissolves in water with a considerably greater evolution of heat than it does before fusion; this the author has shown (Trans. 1889,686) to be due to the existence of the salt in two modifications the one becoming transformed into the other about 200". A similar difference of nearly the same extent in the behaviour of fused and unfused sodium carbonate was also observed by Berthelot,* and suggested the idea that this salt like the sulphate existed in more than one modification. I n order to investigate the matter a considerable quantity of the hydrated salt was allowed to cfftoresce in air and different portions of it were fully dehydrated at various temperatures ; the heat of dissolu-tion of eachpreparation was then measured.The results are given in the accompanying table (p. 73).t The first eight specimens deby-drated at temperatures between 60" and the fusing point of the salt, yield identical results and the fused specimen itself (No. 9) gives a number which is exactly the same as the mean of the others 5521 cal. No. 1 which was prepared at the lowest temperature gives a somewhat lower number 5492 cnl. due probabl7 to the retention of traces of water and is therefore omitted from the mean. As these numbers afforded no explanation of Berthelot's observa-tion another fused specimen No.10 was prepared and examined at three different periods after its preparation. It gave results notably higher (ZOO cal.) than the other samples and this excess did not appear to be much diminished on keeping; the result after 48 days (No. 13) is it is true somewhat lower than the previous ones but no great value can be attached to this decrease as t,he fused salt dissolveb so slowly that the resulta obtained with it can be regarded as approxi-* Tilden also obtained somewhat discrepant results with different samples (Prop. Roy. Soc. 38 407). t. For details see Trans. 1886 266 Heat of Di.csoltdio?t of Alih ydroiis Xodium Carbonate. Preparation. 1. Dehydrated a t 60" C. . 2. . . . . 100 . 3. . . . . 130 . 4. , ) 155 , . 5. , 200 ,) .6. . . . . 260 9. Fused 24 days previously 10. Fused four hours previously 7 . Dehydrated below a red heat 8. at a red heat 11. The same after seven days [12. Nos. 2-8 mixed 13. The same after 41 days more [14. Nos. 2-43) mixed 15. Reated to redness four hours pre-viously 16. Fused atnd then kept in GOz for 20 days [l7. Nos. 2-8 mixed 18. Fused 11 d a y preyiously 19. The same after being kept in C 0 2 for [20. Nos. 2-8 mixed 21. Nos. 2-8 mixed after being kept in GO2 for 11 dajs . 11 days Weight of salt taken. 8.811 grs. 8.800 ,, 8.834 ,, 8.821 ,, 8.798 ,, 8 -814 ), 8.792 ,, 8.719 ,, 8.823 ,, 8.817 ,, 8 -817 ,, 8.765 ,, --8.784 ,, 8.781 ), 8.813 ), 8.789 ), 8.741 ,) -Water equivalent of the solution, BiC.609.83 grams 9 ) 9 , 1 , ), 9 9 9 7 ), ,, 609 *is' grams 609-75 ,, --609.88 ,, 609.71 ,, 609.66 ,) -,! -609-66 ,, Initial temp. t. 1.8 '815" C. 18.815 ,, 18'815 ,, 18.825 ,, 18.815 ,, 18.815 ,, 18.820 ,, 18 -815 ,, 18 %20 ), 18.975 ,, 21 975 )) 15.&0 ,, 9 ) 21 -775 ,, 12.855 ,, ,, 9'95 ,, 9-95 ,, 9.95 ,, , 74 DECOMPOSITION OF SODIUN CARBOXATE BY FUSION, mations only. As the dissolutions were not effected at the same tempe-rature the results obtained with the specimen under examination were compared at each temperature with those given by the normal salt-a mixture oE specimens 2 to 8-with which two determinations were made in each case the mean being given in brackets in the table; this affords the means of reducing all the results to the one tempera-ture of 18.815" C.as has been done in the last column of the table. Having found a difference in the case of the fused salt another specimen heated just short of fusion was prepared No. 15 but it gave the same results as in the previous similar experiment with No. 8. No temperature short of that of fusion will therefore induce any change. It seemed to me possible that fusion had effected a partial decom-position of the carbonate and in order to test this a sample which ha,d been fused was kept in a bottle of carbon dioxide for 20 days and then examined (No. 16). Considerable absorption of the gas had taker1 place and the salt now gave results more than 400 cal. beZow, instead of above the normal salt.This experiment was repeated more fully with Nos. 18 and 1 9 ; here the sample which after keeping 11 days in air evolved 80 cal. above the normal when kept for the same time in carbon dioxide, evolved 400 cal. below the normal. In experiment 21 some of the unfused salt which had been kept i n carbon dioxide was found to have remained unaltered. The excess in the heat of dissolution of the fused salt is therefore, evidently due to a certain amount of the carbonate having been de-composed; and the deficit in the case of the fused salt after exposure to carbon dioxide is not difficult to explain the carbonate would decompose into oxide but during the necessary pounding and sifting of the salt this would no doubt be converted by atmospheric moisture into the hydroxide which on exposure to carbon dioxide would give the acid carbonate a salt which absorbs a considerable amount of heat on dissolution.The greatest excess noticed (200 cal.) would indicate the conversion of 1.4 per cent. of the carbonate into hydroxide whilst the greatest deficit noticed would show the presence of about 4 per cent. of the acid carbonate. The hydroxide formed would probably be under-estimated owing to its absorbing sufficient water from the air to effect partial hydration and this excess of moisture would entail t\re subsequent formation of more of the acid carbonate than would correspond to the hydroxide. The amount of decomposition occurring on simple fusion is probably about 3 per cent

ISSN:0368-1645    

DOI:10.1039/CT8875100072

出版商:RSC    

年代:1887

数据来源: RSC

摘要:

75 X.-The Heat of Irydration of Sa>lfs. Cadmium Chloyide. By SPNNCER UDIFREVILLE PICKERING M.A. Professor of Chemistry at Bedford College. UL'RIKG the recent discussion on the nature of solution at the Birmingham meeting of the British Association Dr. Nicol drew attention to arid laid considerable weight on the supposed fact that the heat of hydrationX of cadmium chloride was a negative quantity (Chem. News 54 191). His line of argument would appear to be :is follows The heat developed on the hydration of a salt does not give any measure of the affinity of the salt for solid water for other (unknown) physical changes must occur at the same time as is proved by the heat of hydration bearing no relation to the degree of hydration and by the existence of an instance cadmium chloride in which the heat of hydration is actually a negative quantity all spontaneous chemical changes being exothermic.Qud argument this appears to me to be very insufficient. What is observed in the 113-dration of a salt is repeated in every instance of chemical combi-nation. Thus in the chlorination of various metals the heat tleveloped per atom of chlorine bears no relation to the number of atoms which are assimilated; and if we are permitted to assume various unknown physical changes as being t o a great extent the cause of the heat evolved in the combination of two substances in the same state we must at once reject all therniocheuiical evidences. The statement that all spontaneous chemical changes are exothermic is itself robbed of whatever truth it may contain for we may iii every case as here doubt the change being a purely chemical one.My attention had previously been attracted to the case of cadmium chloride not so much on account of its heat of hjdration being negative but that it was absolutely the only known instance of an inorganic salt where such a fact occurred. As the heat of dissolution of the salts had been determined only once (by Thomsen Therrno-chem. 3 'LOl) it seemed not altogether improbable that some mistake liad arisen and I therefore determined to repeat the work. Two samples of the anhydrous salt were prepared one at 200° the other being fused. The results which are given in the accompanying table? (see p. 76) can only be regarded as approximations for on the * By '' heat of hydration," I mean throughout the number obtained after due dlowance has been made for the heat of fusion of the water present in the hgdruted salt.t For the calculation of results and other details see Trans. 1836 266 76 FICKERING THE HEAT OF HYDRATION OF SALTS. Weight taken. one hand it was f o n d impossible to dehydrate the salt completely without fusion while on the other fusion was impossible without a certain amount of d'ecomposition (the specimen No. 2 contained 0.5 per cent. of oxide). The numbers however are sufficiently concordant to show that the fused and unfused salta give practically the same results (3382 and 3211 cal. respectively) and that these are identical with that obtained by Thomsen (3011 cal. at about 18'). Heat equiva-lent of solution, &c.Heat of' Dissolution of the Chlorides of Cadmium in 400 H,O. Rise of temp. Substance. Observed heat of dissolu-tion. CdC1,. 1. Prep. at 200°C. 2. Fuwd . . . . . . 15 -168 grms. 25'125 )) 16'717 ), 18*200 ,, CdCLJ,H,O. 3. . *. 610 -04 grms. 610.04 ,, 611.54 )) 613.22 , 4. I . * * * . 0 '4609" C. 0,4364 ,) 0'0853 ,) Fdl of t,emp. 0.3104 )) 3382 c d . 3211 ,, 625 ,, -2284 ,, I Init i a1 temp. 18*14O C. 18'135" ,, 18.135 ,, 18.00 ,, The hydrated salt (No. 3) on dissolution at the same temperature, gave 625 cal. a number evidently identical with that obtained by Thomsen-760-but on analysis it was found to consist of 2 monohydrate instead of a dihy drate as Thomsen states containing 9.617 per cent.water ; theory 9.120 per cent. This monohydrate was uniformly obtained whenever a solution of the salt was evaporated at a high temperature; when however a cold solution was evaporated crystals not easily distinguishable from the monohydrate wem obtained but consisting of the dihy drate, containing 17.035 per cent- water the theoretical number being 16.450 per cent. It is evideut therefore that some error must have occurred in Thomsen's statement; he certainly used the monohydrate in the calorimetric determination and unless his entry that it was found on analysis to contain 2.01 H,O be a mere Zapsws caZami it is probable that the analysis was performed on a different specimen prepared as he imagined under identical conditions but in reality at a lower temperature.According to the numbers here given the heat of hydrat'ion of cadmium chloride is by no means a negative quantity [CdCI2 + H20 This dihydrate on dissolution absorbed 2284 cal MUIR AND CARNEGIE ON BISJIUTHATES. 77 (solid)* being 1092 cal. and [CdCl + 2H,O (solid)] 2421 cal. or 1210 x 2 numbers which are considerably larger than in the case of sodium carbonate (588 cal. per H20) strontium nibrate (421 cal.), and sodium sulphate (320 cal.). Atnongst organic substances there is one salt i n which the heat of hydration would appear to be negative sodium benzenesulphonate, - 250 cal. per H20 besides the case of racemic acid in which it is exactly nil. This latter instance kas been well established and in my opinion tends t o show that the so-called hydrated acid does not contain water of crystallisation at all but possesses a constitution different from that of the anhydrous acid ; a similar explanation may hold good with the sodium benzenesulphonate but BR this instance rests at present on one determination only (Berthelot’s) it should in the first place be more fully investigated

ISSN:0368-1645    

DOI:10.1039/CT8875100075

出版商:RSC    

年代:1887

数据来源: RSC