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J O U R N A LOFTHE CHEMICAL SOCIETY.TltAN SACTIONS.H. BREILETON BAKER, M.A., D.Sc.,J. N. COLLIE, Ph.D., F.11.S.A. W. CROSSLEY, D.Sc., Ph.D., F.R. S.B. G. DONNAN, Rl.A., Ph.D., F.R.S.FERNARDYER, D.Sc.31. 0. FO~W~EIL, D.Sc., Pli.D., F.R.S.F. R. S.6ontntiiiet of @ublicatba :T. M. LOWRY, D.Sc.W. H. YERKIN, Sc.Ii., LL.D., F.R.S.J. C. PHILIP, D.Sc., P11.D.A. Scow, BI.A., D.Sc., F.R.S.G. SENTER, D Sc., Ph.IlF. 13. POWER, Ph.D., LI2.D.s. SMILES, D.8c.Qbitox :J. C. CAIN, D.Sc., P1i.D.sub. - 6bitrrr :A. J. GREEKAWAY.3asjistairt Snb-Ebifor :CLARESCE SMITH, D.S(:.1914 Vol. CV. Part I.LONDON:GURNEY Crlt JACKSON, 33, PATERNOSTER ROW, E.C.1314YRIXTEII IN GREAT BHITAlN BYRlCHAKD CLAY & SONS, LIMITED,BRUNSWICK ST., STAMFORD ST., S.L,AND RUN'GAY SUFFOLKCONTENTS.PAPERS COMMUNICATED TO THE CHEMICAL SOCIETY.I.-The Viscosity of Sugar Solutions. By CHARLES WILFRIDROBERTS YOWELL ,11.-The Absorption of Light by Uranous Chloride in DifferentSolvents. By THOMAS RALPH MERTON .111.-The Action of Amino-acid Esters on Ethyl Dicarboxy-glutaconate. By STANLEY ISAAC LEVY . .1V.-The Condensation of Chloral Hydrate and Carbamide. ByNOEL GUILBERT STEVENSON COPPIN and ARTHUR WALSHTITHERLEY . ,V.--The Action of Hydrogen Peroxide on the Sodium AlkylThiosulphates. By DOUGLAS FRANK Twiss . , .V1.-Organic Derivatives of Silicon. Part XX. Some Con-densation Products of Di benzylsilicanediol. By ROBERTROBISON and FREDERIC STANLEY KIPPINGV 11.-The Optical Rotatory Power of Derivatives of SuccinicAcid in Aqueous Solutions of Inorganic Salts.Part I. ByGEORQE WILLIAM CLouax ,By (the late)JAMES TUDOR CUNDALL (with appendix by MUNQO MCCALLUMFAIRGRIEVE) .1X.-The Configuration of the Doubly Linked Nitrogen Atom.Optically Active Salts of the Semicarbazone and Benzoyl-phenylhydrazone of cycZoHexanone-kcarboxylic Acid. ByWILLIAM HOBSON MILLS and ALICE MARY BAIN .X.--A Contribution to the Study of the Constitution of theMethyl Pentoses. Part I. Synthesis of an i-MethylTetroee and an &Methyl Tetritol. By ROBERT GILMOUR .XI.-The Rotatory Dispersive Power of Organic Compounds.Part IV. Magnetic Rotation and Dispersion in SomeSimple Organic Liquids. By THOMAS MARTIN LOWRY .XI1.-The Rotatory Dispersive Power of Organic Compounds.Part V.A Comparison of the Optical and MagneticRotatory . Dispersions in Some Optically Active Liquids.By THOMAS MARTIN LOWRT, ROBERT HOWSON PICKARD, andJO~EPH KENYON , .XIIT.-The Porosity of Iron. By WILLIAM HUGHES PERKINS .X1'V.-The Relative Activities of Certain Organic Iodo-com-pounds with Sodium Phenoxide in Alcoholic Solution.Part 111. The Temperature-coefficients. By DAVIDSEGALLER ,X V.-The Relative Activities of Certain Organic Iodo-com-pounds with Sodium Phenoxide. Part IT. The Influenceof the Solvent. By DAVID SEGALLER . ..VII1.-The Action of Sulphuric Acid on Copper.PAUE1232732364049606473819410210611iv CONTENTS.XV1.-Constitution of the ortho-Diazoimines. Part IV.PAUE' y 117Isomeric Benzenesulyhonyl-3 : 4-tolylenediazoimides.GILBERT T.MORGAN and GODFREY EDWARD SCHARFFXVI1.-Derivatives of p-Iodoaniline. By FREDERICK DANIELCHATTAWAY and ALFRED BERTIE COBSTABLE . . 124XVIIL-The Distillation of Coal in a Vacuum. By MAURICEJOHN BURGESS and RICHARD VERNON WHEELER . , 131X1X.-The Composition of Coal. By DAVID TREVOR JONES andRICHARD VERNON WHEELER . . 140XX.-Interaction of Glycerol and Oxalic Acid, By FREDERICKDANIEL CKATTAWAY . . 151XX1.-Nitro-acids Derived from 2 : 3-Dimethoxybenzoic Acidand 4-Methoxyphthalic Acid, By JOHN CANNELL CAIN andJOHN LIONEL SIMONSEN . . 156XXI1.-Aromatic Compounds Obtained f rorn the Hydro-aromatic Series. Part 111. Bromoxylenols from Dimethyl-dihydroresorcin. By ARTHUR WILLIAM CROSSLEY and NORARENOUF .. 165XXII1.-The Polysulphides of the Alkali Metals. Part I. ThePolysulphides of Sodium. By ALEXANDER RULE and JOHNSMEATH THOMAS . . 177XX 1V.-Researches on Residual Affinity and Co-ordination.Part I. Metallic Acetylacetones and their AbsorptionSpectra. By GILBERT T. MORGAN and HENRY WEBSTERMoss. . 189XXV.-Chemical Examination of Sarsaparilla Root. ByFREDERICK BELDING POWER and ARTHUR HENRY SALWAY . 201XXV1.-The Identity of the Supposed (3-2 : 5-Dimethyl-piperazine. By WILLIAM JACKSON POPE and JOHN READ . 219XXVI1.-The Relation of Uranous Salts to Thorium. ByALEXANDER FLECK . . 247XXVII1.--Fluorone Derivatives. Part 11. Resorcinol-benzein.By FRAKK GEORUE POPE . . 251XXIX.-The Surface Tension of Mixtures.Part I. Mixturesof Partly Miscible Liquids arid the Influence of Solubility.By RALPH PALIJSER WORLEY . . 260XXX.-The Surface Tenvion of Mixtures. Part 11. Mixturesof Perfectly Miscible Liquids and the Relation betweenTheir Surface Tensions and Vapour Pressures. By RALPHPALLISER WORLEY . . 273SXXI. -The Condensation of Ethyl Glutaconate. By RAYMONDCURTIS and JAMES KEXNER . . 282XXXI1.-The Influence of Colloids nnd Fine Suspensions on tlieSolubility of Gases in M'ater. Part IV. Solubility ofNitrous Oxide a t Pressures Lower than Atmospheric. ByALEXANDER FINDLAY and OWEN RIIYS HOWELL (University.Student in Chemistry) . . 29CONTENTS. VXXXIL1.-The Hydrolysis of Mixed Secondary Amides byAlkalis. By ARTHUR WALSH TITHERLEY and LEONARDSTUBBS .XXX1V.-The Miscibility of Azobenzene and Azoxybenzene inthe Solid State and the Supposed Existence of a Stereo-isomeride OF Azobenzene.By HAROLD HARTLEY and JOHNMCARTHUR STUART .XXXV.-The Equilibrium of Dilute Hydrochloric Acid andGelatin. By HENRY RICHARDSON PROCTER . .XXXV1.-A.bsorption of Gases by Celliiloid. By VICTORLEFEBURE .XXXV11.--6’-Aminoquercetin. By EDWIN ROY WATSON . .XXXVII1.-The Mutual Solubility of Formic Acid and Benzene,and the System : Benzene-Formic Acid-Water. ByARTHUR JAMES EwxxsXXX1X.-The Absorption Spectra of Nitrated Phenylhydr-azones. By JOHN THEODORE HEWITT, RHODA MARIANNEJOHNSON, and FRANK GEORGE POPEXL.-The System : Ethyl Ether-Water-Potassium Iodide-Mercuric Iodide. Part I. The Underlying Three Com-ponent Systems.By ALFRED CHARLES DUNNINGHAM .XL1.-Unstable Compounds of Cholesterol with Barium Meth-oxide. By EDGAR NEWBERY .XLI1.-The Reaction Between Iodine and Aliphatic Aldehydes.By HARRY MEDFORTH DAwsoN and JOSEPH ~IARSHALL .XLII1.-Dyes Derived from Quercetin. By EDWIN ROYWATSON and RIJUUD BEIIARI SENXL1V.-Condensation of Ketones with Phenols. Part I.Condensation with a-Naphthol. By HEMENDRA KUMARSEN-GUPTA . . .XLV.-Acylation as influenced by Xteric Hindrance : the Actionof Acid Anhydrides on 3 : 5-Dinitro-paminophenol. ByRAPHAEL MELDOLA and WILLIAM FRANCIS HOLLELYTheElectrical Conductivity of Potassium Salts of Fatty Acids.By HUGH MILLS BUNBURY and HERBERT ERNEST MARTIN .XLVI1.-Non aromatic Diazonium Salts.Part 111. 3 : 5-Di-methylpyrazole-4-diazonium Salts and their A zo-derivatives.By GILBERT T. MORGAN and JOSEPH EEILLYXLVII1.-The Water-Gas Equilibrium in Hydrocarbon Flames.By GEORGE WILLIAM ANDREW .XL1X.-The Action of Phosphorus Pentachloride on the Estersof Glyceric Acid. Optically Active ap-Dichloropropionates.By PERCY FARADAY FRANKLAND and ANDREW TURNBULL ....XLV1.-Studies of the Constitution of Soap Solutions..PAGE29930931332833835036436838038638939941041 74354 44456L.-The Colour Intensity of Iron and Copper Compounds. BySPENCER UMFREVILLE PICKERINC . . 46vi CONTENTS.L1.-Organic Derivatives of Silicon. Part XXI. The Condensa-tion Products of Dipheny lsilicanediol. By FREDERIC STAXLEYKIPPIKGI and ROBERT ROBISON .. 484By JULIUSBEREND COHEN and PAVITRA KUMAR DUTT . . 501By ERNALD GEORGEJUSTINIAN HARTLEY . . 521ByJOSEPH MARSHALL . . 527PAGELII.-The Progressive Bromination of Toluene.LII1.--a- and /3-Trimethyl Cobalticyanide.L1V.-The Action of Aldehydes on the Grignard Reagent.LV.-Phytin and Phytic Acid. By GEORGE CLARKE . . . 535LV1.-The Oxidation of Some Benzyl Compounds of Sulphur.Part 11. Benzyl Tetrasulphoxide. By JOHN ARMSTRONGSMYTHE . . 546LV1I.-The Constituents of Solanurn nngustifolium : Isolationof a New Gluco-alkaloid, Solangustine. By FRANK TWINand HUBERT WILLIAM BENTLEY CLEWER . . 559LVII1.-The Polymerisation of Cyanamide. By ~ E O R G E YEANCISMORRELL and PETER BURGEN . . 576L1X.-The Absorption Spectra of the Vapours and Solutions ofVarious Substances Containing Two Benzene Nuclei.ByJOHN EDWARD PURVIS . . 590LX.-Ionisation and the Law of Mass Action, Part 11. TheOsmotic Data in Relation to Combined Water. By-WILLIAM ROBERT BOUSFIELD . . . 600LX1.-The Decomposition of Carbamide. By GEORGE JOSEPHBURROWS and CHARLES EDWARD FAWSITT . . 609LXIL-The 3fechanism of Denitrification. By WILLIAM HULME 623LXII1.-The System m-Xylene-Ethy 1 Alcohol-Water. ByALFRED HOLT and NORMAN ~ ~ T J R R A Y BELL . . 633LX1V.-The Ageing of Alloys of Silver and Tin. By WILLIAMARTHUR KNIaHT . , 639LXV.-The Production of High Vacua by means of FinelyDivided Copper. By THOMAS RALPH MERTON . , 645LXV1.-A Study of the Vapour Pressure of Nitrogen Peroxide.By ALFRED CHARLES GLYN EGERTON .. 647LXVI1.-The Absorption Spectra of Some Mercury Compounds.By CECIL REGINALD CRYMBLE (1851 Exhibition ResearchScholar) . . 658LXVII1.-The Relation Between the Absorption Spectra ofAcids and their Salts, Part 11. By ROBERT WRIGHT (1851Exhibition Scholar) . . 669LX1X.-Organic Derivatives of Silicon, Part XXII. TheSo-called Siliconic Acids. By JOHN ARTHUR MEADS andFREDERIC STANLEY KIPPING . 679LXX.-The Rate of Transformation of Ammonium Cyanate inAbsolute Alcohol. By JOHN DAVID MCBEATH Ross (VansDunlop Scholar in Chemistry, University of Edinburgh) . 69CONTENTS. viiPAGELXXL-The Conversion of d-Gllucosamine into d-Mannose. ByJAMES COLQUROUN IRVINE and ALEXANDEB HYND (CarnegieFellow) .LXXIL-The Electro-deposition of Zinc at High CurrentDensities.By JOHN NORMAN PRING and URLYN CLIFTONTAINTON . . . .LXXII.1.-The System : Ethyl Ether-Water-Potassium IodideMercuric Iodide, Part 11. Solutions saturated withRespect to Solid Phases in the Four-component System.By ALFRM) CHARLES DUNNINGHAM . .LXX1V.-A New Formula for the Latent Heat of Va.pours.By MALCOLN PERCIVAL APPLEBEY and DAVID LEONARDCHAPMAN .LXXV.-2-Hydrindamine. By JAMEEI KENNER and ANNIEMOORE MATHEWS .LXXV1.-The Viscosities of Some Binary Liquid Mixtures Con-taining Formnmide. By ERNEST WYNDHAM MERRY andWILLIAM STEPHEN TURNER .LXXVI1.-A Relation between Chemical Constitution andDepth of Colour of Dyes. By EDWIN ROY WATSON .LXXVII1.-The Constituents of the Leaves and Stems ofDaviesia kctifolin.By FREDERICK BELDINCI POWER andARTHUR HENRY QALWAY .LXX1X.-The Solubility of the Nitrates of Potassium, Barium,and Strontium, and the Stability of the Double Nitrate ofPotassium and Barium, By ALEXANDER FINDLAY, IDWALMORGAN, and IVOR PRYS MORRIS.LXXX.-The Relation between Viscosity and Chemical Consti-tution. Part VIII. Some HomoIogous Series. By ALBERTERNEST DUNSTAN, FERDINAND BERKARD THOLE, and PERCYBENSON .LXXX1.-The Composition of Some Mediaeval Wax Seals. ByJAMES JOHNSTON DOBBIE and JOHN JACOB FoxLXXXI1.-The Variable Rotatory Powers of the d-a-Bromo-camphor-P-sulphonates. By WILLIAM JACKSON POPE andJOHN READ .LXXXTIL-The Optical Activity of Compoiinds of SimpleMolecular Constitution. Ammonium d- and Z-Chloroiodo-methanesulphonates. By WILLIAM JACKSON POPE andJOHG READ .LXXX1V.-The Isomerism of the Oximes.Part 111. TheHydroxy benzaldoximes. By OSOAR LISLE BRADY andFREDERICK PERCY DUNN .LXXXV.-Investigations on the Dependence of Rotatory Poweron Chemical Constitution. Part V. The Simpler Estersof the Carbinols CH;CH(OH)*R. By ROBERT HOWSONPICKARD and JOSEPH KENYON ...6987107 2473474574876976777978279580081 182 183...V l l l CONTENTS.PAGELXXXV1.-The Influence of Configuration on the CondensationReactions of Polyhydroxy-compounds. Part I. The Con-stitution of Mannitoltriscetone. By JAMES COLQUHOUNIRVINE and BINA MARY PATERSON (Carnegie Fellow). . 898LXXXVI1.-The Formation of Ethers from Mannitol.A nExample of Steric Hindrance. By JAMES COLQUHOUS IRVINEand BINA NARY PATERSON (Carnegie Fellow) . . 915LXXXVII1.-The Constitution of Carbamides. Part I. ThePreparation of isociirbamides by the Action of MethylSulphate on Carbamides. By EMIL ALPHONSE WEANER . 923LXXX1X.-Condensations of Cyanohydrins. Part 11. TheCondensation of Choralcyanohydrin with Choral Hydrateand with Bromal Hydrate. By HORACE LESLIE CROWTEIER(Priestley Research Scholar of the University of Birming-ham), HAMILTON RICCOMBIE, and THOMAS HAROLD READE . 933XC.-The Connexion between the Dielectric Constant and theSolvent Power of a Liquid. By WILLCAM ERNEST STEPHENTURNER and CRELLYN COLGRAVE BISSETT . . 947XC1.-The Action of Sulphur on Amines. Part 11. Aniline.By HERBERT HENRY HODGSON and ALFRED GILBERT DIX .952XCI1.-Studies of the Constitution of Soap Solutions : TheAlkalinity and Degree of Hydrolysis of Soap Solutions. ByJAMES WILLIAM MCBAIN and HERBERT ERNEST MARTIN . 957XCII1.-Syntheses with Phenol Derivatives Containing a MobileNitro-group. Part VI. Substituted ,41kyl- and Aryl-phenylamines : Colour in Relation to Tautomerism. ByRAPHAEL MELDOLA and WILLIAM FRANCIS HOLLELY . . 977XC1V.-Menthyl Esters of Chloroacetic, Menthoxyacetic, andMethylanilinoacetic Acids. By PERCY FARADAY FRANKLANDand FRED BARROW . . 990XCV.-The Relative Strengths of Ammonium and the Substi-tuted Ammonium Hydroxides, as Measured by their Actionon a Pseudo-base. Part I. By CHARLES KENNETH TINRLER 995XCV1.-The Lower Limits of Inflammation of Methane withMixtures of Oxygen and Nitrogen.By ALBERT PARKER . 1002XCVI1.-An Adiabatic Calorimeter. By FI~ANCIS WILLIANGRAY . 1010XCVII1.-Experiments on the Rate of Nitrification. ByRICHARD MOORE BEESLEY . . 1014XC1X.-Deliquescence. Part I. The Deliquescence of Salts ofAmmonium Bases. By CYRIL JAMES PEDDLE . . 1025(3.-Hydrazoximes of Methyl- and Pheayl-gloxals. By BIMANRIHARI DEY . . 1039(31.-Derivatives of 3 : 4-l>imethoxyacetophenone and 4 : 5-Bimethoxy-o-tolyl Methyl Ketone, and the Synthesis ofPhenylglyoxalines Containing Substituents in the BenzeneRing. By HENRY STEPHEN and CHARLES WEIZMANN . . 104CONTENTS. ixPAGECI1.-The Action of Chromic Chloride on the Grignard Reagent.By GEORGE MACDONALD BENNETT and EUSTACE EBENEXERTURNER .. 1057CIIL-Dibenzoylglncoxylose : A Natural Benzoyl .Derivative ofa new Disaccharide. By FREDERICK BELDING POWER andARTHUR HENRY SALWAY . . 1062CIV.-The Ignition of Some Gaseous Mixtures by the ElectricDischarge. By HUBERT FRANK COWARD, CHARLES COOPER,and JULIUS JACOBS . . 1069CV.-The Catalytic Activity of Acids in Ethyl-alcoholicSolution. By HARRY MEDFORTH DAWSON and FRANKPowrs . . 1093CV1.-The Action of Thionyl Chloride on Lactic Acid and onEthyl Lactate. By PERCY FARADAY FHANKLAND andWILLIAM EDWARD GARNER . . 1101CVI1.-Investigations on the Dependence of Rotatory Poweron Chemical Constitution. Part VI. The Optical RotatoryPower of Methyl-tert.-butyl-, Methylbenzyl-, Methylphenyl-ethyl- and Methyl-a-naphthyl-carbinols.By ROBERT HOWSONPICKARD and JOSEPH KENYON . . 1115C VI TI.-The Oxidation of Carbohydrates and Related Substancesby means of Potassium Persulphate. By JOHN KERFOOTWOOD and NELLIE WALKER (Carnegie Scholar) . . 1131CIX. -The Reaction between Sodiiim Benzylthiosiilphnte andIodine. By THOMAS SLATER PRICE and ARTHUR JAQUEB . 1140CX.-Synthesis of dl-Tyrosine and dG3 : 4-Dihydroxyphenyl-alanine. By HENRY STEPHEN and CHARLES WEIZMANN . 1152CX1.-The Action of Sulphuric Acid on Para€ormaldehyde. ByJOHN GUNNING MOORE DUNLOP . . 1155CXI1.-An Extremely Delicate Colorimetric Method for Detect-ing and Estimating Nitrates and Nitrites. By EDAWNDALBERT LETTS and FLORENCE WILLIAMSON REA . . 1157ANKUAL GENERAL MEETING . . 1162PREBIDENTXAL ADDRESS .. 1176OBITUARY NOTICES . 1189CXII1.-The System : Silver-Silver Sulphide. By CRELLYNCOLGRAVE BISSETT (1851 Exhibition Scholar) . . 1223CX1V.-Optically Active Derivatives of d-Dimethoxy- andd-Diethoxy-succinic Acids. By CHARLES ROBERT YOUNG . 1228CXV.-The Constitution of the Glycerylphosphafes. TheSynthesis of a- and /3-Glycerylphosphates. By HAROLDKING and FRANK LEE PYMAN . . 1238CXVI.-The Inversion of Sucrose by Acids in Water-AlcoholSolutions. By GEORGE JOSEPH BURROWS . . 1260CXVI1.-Direct Combination of Nitrous Acid with Primary,Secondary, and Tertiary Amines. By PANCKANON NEOQI . 127x CONTENTS.CXVII1.-The Dynamics of the Action of Halogens on AliphaticAldehydes. Keto-enol Isomerism of the Aldehydes. ByHARRY MEDFORTH DAWSON, DOKALD BURTON, and HARRYARE .. . 1275CX1X.-Some Derivatives of as-Dipropyl- and -diamyl-oxamicAcids, By HARFORD MONTGOMERY ATKINSON . . 1290CXX.-Rate of Evolution of Gases from SupersaturatedSolutions. Part 11. Carbon Dioxide in Solutions ofGelatin and of Starch. By ALEXANDER FINDLAY andGEORGE KING (Priestley Research Scholar, University ofBirmingham) . . 1297CXXL-The Velocity of Saponification of the Acyl Derivativesof the Substituted Phenols, Part I. Phenyl Benzoate.By HAMILTON MCCOMBIE and HAROLD ARCHIBALDSCARBOROUGH (Research Scholar of the University ofBirmingham) . . 1304CXXIL-The Atomic Weight of Vanadium. By HENRYVINCENT A ~ R D BRISCOE and HARRY FRANK VICTOR LITTLE . 131 0CXXII1.-Researches on Santalin. Part 11.By JOHN CANNELLCXX1V.-The Constitution of Camphene. Part 11. Experi-ments on the Synthesis of Several Degradation Products ofCamphene. By WALTER NORMAN HAWORTH and ALBERTTHEODORE KING . . . . 1342, '7 1351CXXV.-Studies of Ammonium Solutions.ROLAND EDQAR SLADE .CXXV1.-The Action of ay-Dibromobutane on the SodiumDerivatives of Ethyl Acetoacetate and Benzoylacetato. ByROBERT GEORGE FARGHER and WILLIAM HENRY PERKIN,CXXVI1.-Contributions to the Chemistry of the Terpenes.Part XVII. The Action of Hypochloroue Acid onCamphene. By GEORGE GERALD HENDERBON, I8IDOR MORRISREILRRON, and MATTHEW HOWIE . . 1367CXXVII1.-The Absorption Spectra of Various SubstancesContaining Two, Three, and Four Benzene Nuclei. ByJOHN EDWARD PURVIS . * . . 1372CXXTX.-The Alloys of Aluminium and Silicon.By CHARLESEDWARD ROBERTS . . 1383CXXX.-Partially Methylated Glucoses. Part 111, Mono-methyl Glucose. By JAMEEI COLQUHOUN IRVINE and THOMAE~PERCIVAL HOGG (Carnegie Scholar) . . 1386CXXX1.-The Interaction of Naphthasulphonium-quinone andSubstances Containing the Thiol Group. By BROJENDRANATHGHOSH and SAMUEL MILES . . a . . 1396UXXX1I.-The Atomic Weight of Lead from Ceylon Thorite.By FREDERICK SODDY and HENRY HPMAN (Mackay SmithScholar, University of Glasgow) . , 1402PAGECAIN, JOHN LIONEL SIMORSEN, and CLARENCE SMITH . . 1335A Correction.jun. . . . , 135CONTENTS. XiPAQECXXXII1.-Thujin, By ARTHUR GEORGE PERKIN . . . 1408FARADAY LECTURE. The Theory of Electrolytic Dissociation.By SVANTE ARRHENIUS .. . . 1414CXXX1V.-The Addition of Negative Radicles to Schiff’sBases. By THOMAS CAMPBELL JAMES and CLIFFORD WILLIAXCXXXV,-Studies in the Diphenyl Series. Part VI. TheConfiguration of Diphenyl and its Derivatives. By JOXINCANRELL GAIN and FRANCES MARY GORE MICKLETHWAITCXXXV1.-Studies in the Diphenyl Series. Part VII. Iso-meric 0- and m-Dinitro-o-tolidines. By JOHN CANNELLGAIN and FRAKCES MARY GORE MICKLETHWAIT. . 1442CXXXVI1.-Compounds of Phenanthraquinone with MetallicSalts. By JOSEPH KNOX and HELEN REID INNES (CrtrnegieResearch Scholar, University of Aberdeen) . . , 1451CXXXVIIL-Researches on Pseudo-bases. Part I, SomeCondensation Reactions of Cotarnine, Hydrastinine, and&~o-&uinoline Methyl Hydroxide. By GERTRUDE MAUDROBINSON and ROBERT ROBINSON .. 1456CXXX1X.-Quinone-ammonium Derivatives. Part 111. Di-haloid, Monoazo-, Bisazo-, Nitrotriazo-, and Bistriazo-com-pounds : Attempts to Prepare Derivatives Containing anAsymmetric Quinquevalent Nitrogen Atom. By RAPHAELMELDOLA and WILLIAM FRANCIS HOLLELY . . 1469CXL.-The Interaction Between Nitric Acid and Brucine inthe Presence of Metallic Nitrates. By EDWARD HENRYRENNIE and ALFRED ERNEST DAWKINS . . 1487CXL1.-The Reactivity of Antimony Haloids with CertainAromatic Compounds. Part I. By I~RNEST VANSTONE . 1491CXLI1.-Reactions by Trituration. By LESLIE HENRY PARKER, 1504CXL1II.-A Criticism of the Hypothesis that Neutral SaltsIncrease the Dissociation of Weak Acids and Bases. ByJAMES WILLIAM lkfcB.41~ and FREDERICK CHARLES COLEMAN 1517Part I.By JULIAN LEVETT BAKER and HENRY FRANCIS EVEHARDHULTON .. . . 1529CXLV.-The Resolution of 5-Nitrohydrindene-2-carboxylic Acid.By WILLIAM HOBSON MILLS, HORACE VICTOR PARKER, andROBERT WILLIAM PROWSE . . 1537CXLV1.-Equilibrium in the System : Ethyl Alcohol, AceticAcid, Ethyl Acetate and Water, and its Apparent Dis.placement by Mineral Chlorides. By JAMES FLETCHER andWILLIAM JACOB JONES . , 1542CXLVIL-The Mechanism of Cyanidion Catalyses. By WItLIaMJACOB JOKES . . . 1647CXLVIIL-The Interaction between Hydrogen Cyanido andAldehydes and Ketones in Dilute Solution. By WILLIAMJACOB JONES . . 1560JUDD . . , 1427. 1437CXL1V.-The Action of Diastase on Starch Granulesxii CONTENTS.CXL1X.-Experiments on the Synthesis of the Benzoterpenes.Part I.Derivatives of Benzonor-p-menthane. By FRANOISWILLIAM KAY and ALLAN MORTON . . 1565CL.-Action of Grignard Reagents on Acid Amides. By ALEX.MCKENZIE, GEOFFREY MARTIN, and HAROLD GORDON RULE . 1583CL1.-The Alkaloids of Ipecacuanha. By FRANCIS HOWARD CARRand FRANK LEE PYMAN . . 1591CLI1.-The Relation Between the Absorption Spectrit, andthe Constitution of Certain isoQuinoline Alkaloids and ofthe A1 kaloids of Ipecacuanha. By JAMES JOHNSTON DOBBIEand JOHN JACOB FOX . . 1639CLII1.-The Reactions of a-Amino$- hydroxy-compounds ascyclic Structures. By JaMas COLQUHOUN IRVINE andALEXANDER WALKER FYFE (Carnegie Scholar) . . . 1642CL1V.-The Viscosities of Mixtures of Forinamide with theAlcohols.By SOLOMON ENaLTsH and WILLIAM ERNESTSTEPHEN TURNER . . 1656ByWALTER NORMAN HAWORTH and ALEXANDER WALKERFYFE (Carnegie Scholar) . . 1659CLV1.-The Action of Nitro-substituted Aryl Haloids onAlkali Thiosulyhates and Selenosnlphates. By DOUGLASFRANK TWISS . . 1672CLVIL-The Alkaloids of Dcqhzcmh-a rrticva7ttha. By BRAN KLEE PYMAN . . 1679CLVIII. -The Interaction of Benzoin and the Chlorides ofDibasic Acids. By HAMILTON MCCOMBIE and JOHNWILFRID PARKES . . 1687CL1X.-The Thermal Decomposition of Methyl Alcohol. ByWILLIAM ARTHUR BONE and HAMILTON DAVIES . . 1691CLX.-The Fractional Distillation of Petroleum. By JAMESMCCOKNELL SANDERS. . . . . 1697CLX1.-Existence of Racemic Compounds in the Liquid State.Part 11. By CLARENCE SMITH .. 1’703CLXIL-Contributions to the Chemistry of the Terpenes.Part XVIII. Camphenanic Acid and its Isomerides. ByGEORGE GERALD HENDERSON and MAGQIE MILLEN JEWBSUTHERLAND . , 1710CLXII1.-Studies in the Camphane Series. Part XXXV.Isomeric Hydrazoximes of Camphorquinone, and SomeDerivatives of Aminocamphor. By MARTIN ONSLOWFORSTER and ERNEST KUNZ . . 1718CLX1V.-Studies in the Succinic Acid Series. Part I. TheChlorides of Succinic and Mothylsuccinic Acids, and theirCLXV.-Dinaphthathioxonium Salts. By BROJENDRANATN CHOSHand SAMUEL SMILES . . 1739PAGECLV.-Synthetic Hydrocarbons Allied to the Terpenes.Constitution. By GEORQE FRANCIS MORRELL . . 173CONTENTS.CLXV1.-The Interaction of Nitric Acid and the Sutphides of/%Naphthol. By CHARLES GRAHAM HUTCHISON and SAMUELSMILES .CLXVZI. -T he Influence of Solvents on Molecular Weights.Part I.Salts. By WILLIAM ERNEST STEPHEN TURNER andCORNELIUS THEODORE POLLARDCLXVIII. -The Molecular Weights of Some Salts of the AlkaliMetals and an Account of the Compounds of these Saltswith the Alcohols. By WILLIAM ERNEST STEPHEN TURNERand CRELLYN COLGRAVE BISSETT .CLX1X.-The Nature of Molecular Association. Its Relationto Chemical Combinat ion. By WILLIAN ERNEST STEPHENTURNER and SOLOMON ENGLISH .CLXX.--a-Bromonaphthalene : its Physical Properties and itsApplication to the Determination of Water in MoistAlcohol.Part 111.Utilisation of the Osmotic Data and a New Dilution Law.By WILLIAM ROBERT BOUBFIELD, K.C.CLXXI1.-The Constituents of the Flowers of Aiathmais izobilis.By FREDERICK BELDING POWER and HENRY BROWNING, jun.CLXXII1.-The Constituents of Cbmatis vitaZ6a. By FRANKTUTIN and HUBERT WILLIAM BENTLEY CLEWER .CLXX1V.-The Dilu tion-limit s of Inflammability of GaseousMixtures.Part I, The Determinat.ion of Dilution-limits.Part 11. The Lower Limits for Hydrogen, Methane, andCarbon Monoxide in Air. By HUBERT FRANK COWARD andFBANK BRINSLEY .CLXXV. --Experiments on the Migration of para-HalogenAtoms in Phenols. By IVAN RICHARD GIBBS and PHILIPWILFRED ROBERTSON .CLXXVL-Position-Isomerism and Optical Activity. ByJULIUS BEREKD COHEN .CLXXVI1.-The Nitrogenous Constituents of Hops. ByALFRED CHASTON CHAPMAN .CLXXVII1.-The Chlorination and Bromination of SubstitutedToluenes.By JULIUS BEREND COHEN and COLIN JAMESSMITHELLS . . .Part IV.o-Nitrobenzylidenearylamines and their PhotoisomericChange. By ALFRED SENIER and ROSALIND CLARKE .CLXXX.-Calcium Nitrate. Part 111. The Three-componentSystem : Calcium Nitrate-Limewater. By HENRY BAS-~ E T , jun., and HUGH STOTT TAYLOR . 0CLXXXL-Ionic Equilibria Across Semi-permeable Membranes.By FREDERICK GEORGE DONNAN and ARTHUR JOHN ALLMANDCLXXXI1.-Some Derivatives of Safrole. B y ROBINSON PERCYvBy MARIAN JONES and ARTHUR LAPWORTH .CLXX1.-Ionisation and the Law of M~tss Action..CLXX1X.-Studies in Phototropy and Thermotropy.. a . X l l lPAQE1744175117771786180418091829.184518591885189218951907191719261941FOULDEI and ROBERT ROBINSON .. 196xiv CONTENTS.CLXXXII1.-Studies in Substituted Quaternary Azonium Com-pounds Containing an Asymmetric Nitrogen Atom. Part11. Resolution of Phenplbenzylmethylazonium Iodide intoOptically Active Components. By BAWA KARTAR SINGH . 1972CLXXX1V.-The Influence of Acids and Alkalis on theOptical Activity of Some Amino-acids, By JOHN KERPOOTWOOD . . 1988CLXXXV.-The Estimation of Carbon Monoxide. By JOSEPHIVON GRAHAM and THOMAS FIELD WINMILL . . 1996CLXXXV1.-The Effect of Ring-Formation on Viscosity. ByFERDINAND BERNARD THOLE . . 2004CLXXXVI1.-Oxidation of Papaveraldine Methosulphate. ByFREDERICK ALFRED MASON and WILLIAM HENRY PEBKIK,jun. . . . . 2013CLXXXVIII.--d- and dl-Epicamphor. By REUINALD FUR NEB^CLXXXIX. --The Firing of Gases by Adiabatic Compression.Part I.Photographic Analysis of the Flame. By HAROLDBAILY DIXON, LAWRENCE BBADSHAW, and COLIN CAMPBELL. 2027CXC.-The Firing of Gases by Adiabatic Compression. Part 11.The Ignition-points of Mixtures Containing ElectrolyticGas, By HAROLD BAILY DIXON and JAMES MURRAY CROFTS 2036CXC1.-The Action of Cold Concentrated Hydrochloric Acid onStarch and Maltose. By ARTEIUR JOHN DAISH . . 2053CXCI1.-The Velocity of Hydrolysis of Starch and Maltose byCold Concentrated and Fuming Hydrochloric Acid. ByARTHUR JOHN DAISH . . 2065CXCII1.-Quinone-ammonium Derivatives. Part IV. Productsof the Extreme Alkylation of Alkylated isoPicramic Acid.By RAPHAEL MELDOLA and WILLIAM FRANCIS HOLLELYCXCIV.-Synthetical Experiments in the Group of theisoQuinoline Alkaloids.Part IV. The Synthesis ofP-Gnoscopine. By EDWARD HOPE and ROBERT ROBINSON . 2085CXCV.-The Isomerism of the Oximes. Part IV. The Con-stitution of the N-Methyl Ethers of the Aldoximea and theAbsorption Spectra of Oximes, their Sodium Salts, andMethyl Ethers. By OSCAR LISLE BRADY . . 2104CXCVL-The Velocities of Combination of Sodium Derivativesof Phenols with Olefine Oxides. By DAVID RUNCIMAN BOYDand ERNEST ROBERT MARLE . . 2117CXCVI1.-The Osmotic Properties and Physical Constitution ofCaoutchouc Solutions. By WILLIAM AuausTus CASPARI . 2 139CXCVII1.-Tho Velocities of Flame in Mixtures of Methaneand Air. . 2150CXC1X.-Action of Monochloroacetic Acid on Thiocarbamideand Monoalkylated Thiocarbamides.By PRAFULLA CHANDRARAY and FRANCIS VITO FERNANDES , . 2159PAGEand WILLIAM HENRY PERKIN, jun, . . . 2024. 2073By ALBERT PARKER and ALAN VICTOR RHEACONTENTS. xvPAGECC.-M ium Boride and Amorphous Boron. By RAMEBCC1.--T uu action of Magnesium Phenyl Bromide on DerivativesBy IDA SMEDLEY MACLEAN andCCI1,-The Constitution of the Arylidenedimethylpyronev andBy ALFRED ARCHIBALD BOON, FORSYTH JAMESCCII1.-p'roluoylacetic Acid, o-Nitro-p-toluoylacetic Acid, and6 : 6'-Dimethylindigotin. By JAMES COOPER DUFF . . 2182CCIV.-The Chemical Constitution of Dioximines. By LEOALEXANDROVITSCH TSCHU GAEF . . . 2187CCV.-Colour and Constitution of Azo-compounds. Part VI.By JOHN THEODORE HEWITT, GLADYS RUBY MANN, andFRANK GEORGE POPE . . 2193CCV1.-The Volumetric Estimation of Carbon in AliphaticSubstances in the w e t way.By EGERToN CHARLES GREY(Beit Memorial Research Fellow) . . 2204CCV1I.-Orgnno-derivatives of Bismuth. Part I. The Prepara-tion and Properties of some Tertiary Aromatic Bismuthinesand their Halogen Derivatives.CCVII1.-The Condensation of Furan-2 : 5-dialdehyde withMalonic Ester and Malonic Acid. By WILLIAM FRANCISCOOPER and WALTER HAROLD NUTTALL . . . 2218CC1X.-Investigations on the Dependence of Rotatory Poweron Chemical Constitution. Part VII. Some Esters of theCarbinols of the Formula C,H;CH(OH)*R. By JOSEPHKENYON . . . * . . . 2226CCX.-Investigations on tbe Dependence of Rotatory Power onChemical Constitution. Part W I T . The Optical RotatoryPowers of the Normal Esters of Methylbenzylcarbinol. ByJOSEPH KENYON and ROBERT HOWSON PICKARD ., 2262CCXL-The Constituents of the Flowers of Matvicariacharnomilla. By FREDERICK BELDING POWER and HENRYBROWNING, jun. . . 2280CCX 11.-Experiments on the Conversion of Certain Dibromidesof the Type of Ethylene Dibromide into the CorrespondingGIycols. By ERNEST GRAHAM BAINBRIDGE . . 2291CCXIIL-Electromotive Forces in Alcohol. Part IV. Com-binations of t h e Hydrogen and Calomel Electrodes. ByREGINALD FURNESS, ROBERT TAYLOR HARDMAN, and EDGARNEWBERY . . 2302CCX1V.-Tho Dissociation of Gaseous Nitrogen Trioxide. ByBERNARD MOUAT JONEB . . 2310CCXV.-The Influence of Solvents on the Rotation of OpticallyActive Compounds. Part XX. Isomeric Solvents. ByTHOMAS STEWART PATTERSON and ERNEST FERGUBON POLLOCE 2322CHI KAY .. 2162of Phenyl Styryl Ketone,SIBYL TAITE WIDDOWS . . 2169their Salts.WILSON, and ISIDOR MORRIS HEILBRON . . 2176By FREDERICK CRALLENGER 221xvi CONTENTS.CCXV1.-Studies in Catalysis. Part I. Hydrolysis of MethylAcetate, with a Theory of Homogeneous Catalysis. ByALFRED LABIBLE and ~TILLIAM CUDMORE ~ ~ C ~ U L L A G H LEWIS . 2330CCXVI1,-The Metallography of German Silver. By FHANKCHARLES THOMPSON . . 2342CCXVIII. -The Colouring Matters of Rhanmus catharticus. ByJOSEF OESCH and ARTKUR GEORGE PEREIN . . 2350CCX1X.-The Methylation of Cellulose. Part I T . Hydrolysisof Methylated Cellulose. By WILLIAM SMITH DENHAM andHILDA WOODHOUSE (Carnegie Fellow) . . . 2357CCXX.-A Class of Salts which Contain two Solvents ofC’rystallisation.Ey JAMES ERNEST MARSH . . 2368CCXX1.-Interaction of Alkali Alkyl Sulphates and AlkaliNitrites : Theories of the Formation of Aliphatic Nitro-compounds. By PAKCHANON NEOGI . . 2371CCXXI1.-Some Derivatives of o?*tho-Vanillin. By WILLIAMHENRY PERKIN, jun., and ROBERT ROBINSON . . 2376CCXXII1.-Some Derivatives of isocoumarin and isocarbostyril.By DAVID BAIN, WILLIAM HENRY PERK~N, jun., and ROBERTROBINSON . . 2392CCXX1V.-1 : 2-Diketo-5 : 6-dimethoxyhydrindene. By WILLIAMHENRY PERKIN, jun., WALTER MORRELL ROBERTS, and ROBERTROBINSON . . 2405CCXXV.-The Isomerism of the Oximes. Part V. nz-Methoxy-benzaldoxime, Vanillinoxime, and Veratraldoxime. ByOSCAR LISLE BRADY and FREDERICK PERCY DUNN .. 2409CCXXV1.-Overvoltage. By EDGAR NEWBERY . . . 2419CCXXVIL-The Reaction of p-Benzoquinone with SulphurousAcid and with Alkali. Part I. By Jorm WALLIS DODGSON 2435CCXXVIIL-The Rate of Combination of Gaseous Nitric Oxideand Chlorine. Part I. By JOSEPH EDWARD COATES and ADAFLNNEY . . . . . . 2444CCXX1X.-A General Method for the Preparation of Glyoxalsand their Acetals. By HENRY DRYSDALE DAKIS and HAROLDWARD DUDLEY . . 2453Part V.Polymorphic 4-Hydroxybenzylideneamines produced byTrituration and by the Influence of Sunlight. By ALFREDSENIER and ROBERT BENJAMIN FORSTER . . 2462-3 : 4 : 3‘ : 4’-tetracarb-oxylic Acids. By JAMES KENNER and ANNIE MOOREMATHEWS . . 2471CCXXXIL-The Absorption Spectra of the Vnpours andHolutions of Various Derivatives of Benzaldehyde.ByJOHN EDWARD PURVIS . . 2482CCXXXII1.-Hydrogen Potentials of Mixtures of Acetic Acidand Sodium Acetate. By GEORQE STANLEY WALPOLE . . 2501PAGECCXXX.-Studies in Phototropy and Thermotropy.CCXXXI.--Diplienyl-2 : 3 : 2’ : 3‘- anCONTENTS. xviiPAGECCXXX1V.-The Etiect of Dilution on the Hydrogen Potentialsof Acetic Acid and c‘ Standard Acetate” Solutions. ByGEORGE STANLEY WALPOLE . . 2521CCXXXV.-The Atomic Weight of Mercury. By HERBERTBRERETON BAKER and WALTER HENRY WATSON . . 2530CCXXXVI. -Adiabatic and Isothermal Compresibilities ofLiq i d s between One and Two Atmospheres’ Pressure.By DANXEL TYRER . . 2534CCXXXVK-Electromotive Forces in Alcohol. Part V. TheDropping Electrode in Alcoholic Solutions.By EDGARNEWBERY . . 2553CCXXXVI1I.-The Composition of Coal. Part 11. By DAVIDTREVOR JONES and RICRAED VERNON WHEELER . . 2562CCXXX1X.-Photokinetics of Sodium Hypochlorite Solutions.Part 11. By LEO SPENCER . 2565ANNUAL REPORT OF THE INTERNATIONAL CONYITTEE ON ATOMICCCXL.-Catalysis. Part XVIII. The Reactions of both theIons and the Molecules of Acids, Eases and Sa1t.s: TheReactions of Alkyl Haluids with Phenoxides and Ethoxides.By JOHN HANSTON SHRODER and SOLOMON FARLEY ACREECCSL1.-The Limits of Inflammability of Illixtures of Methaneand Air. By MAURICE JOHN BURGESS and RICHARD VERNONWHEELER . . 2591COXLI1.-The Propagation of Flame in ‘‘ Liniit ” Mixtures ofMethane, Oxygen and Nitrogen. By MAURICE JOHNBURGESS and RICHARD VERNON WHEELER.. 2596CCXLII1.-The Propagation of Flame in Mixtures of Methaneand Air. The ‘‘ Uniform Movement.” By RICHARD VERKONWHEELER . . 2606CCXLIV.-Volatile Oil from the Leaves of Barosma vewsta.By ERNEST GOULDIXQ and OSWALDIGBY KOBERTS . . 2613CCSLV.-Sodium Amalgams : Specific Volumes and ElectricalConductivities. By ERNEST VANSTONE . . 2617CCXLV1.-The System : Ethyl Ether-Water-Potassium Iodide-Mercuric Iodide. Part 111. Solutions Unsaturated withRespect to Solid Phases in the Four-component Systerri.By ALFRED CHARLES DUNNINGHAM . . 2623C CXLVII. - Resol LI t ion of trans-cycZoPen tane- 1 : 2-d icarbox y licAcid. By LEONARD JAMES GOLDSWORTHY and WILLIAMHENRY PERRIN, jun. .CCXLVIII. -Investigations on the Dependence of RotatoryPowor on Chemical Constitution.Part IX. The RotatoryPowers of 1-Naphthyl-n-hexylcarbinol and its esters, ByJOSEPH KENYON and ROBERT HOWSON PICKARD. . . 2644CCXL1X.-Carboxylic Scids Derived from cycZoButane, cyclo-Pentane, cycZoHexane, and cycZoHeptane. By LEONARDJAMES GOLDSWORTHY and WI~LIAM HENRY PERKIX, jun.WEIGHTS, 1915 . . 2577. 2582. 2639. 266xviii CONTENTS.CCL-Investigations on the .Dependence of Rotatory Power onChemical Constitution. Part X. The Optical DispersivePower of Tetrahydro-2-naphthol a.nd its esters. By JOSEPHKENYON and ROBERT HOWSON PICKARD . . 2677CCL1.-The Keduction Products of Ethyl Hydrindene-2 : 2-di-carboxylate. By JAMES KEKNER . . 2685CCLT1.-Studies in the Succinic Acid Series. Part 11. Anilidesand Anilic Acids, and the Effect of Steric Hindrance on theCCLII1.-A Magnetic Study of Compounds of Water and ofAqueous Solutions.By FRANCIS WILLIAM GRAY andWILLIAMILNE UIRSE . . 2707CCLIV.-The Influence of Nitro-groups on the Reactivity ofSubstituents in tho Benzene Nucleus. By JAMES KENNER . 2717CCLV.--'l'he Alkaloids of Quebracho Bark. Part I. The Con-stitution of Aspidospermine. By ARTHUR JAMES EWINS . 2738CCLV1.-Some Homolopes of Alizarin. By HARRY BRADBURYand CHARLES WEIZMANN . . 2748CCLVII. --The Dissociation Pressures of the Alkali Bicarbonates.Part 11. Potassium, Xubidium, and Cssium HydrogenCarbonates. By ROBERT MARTIN CAVEN and HENRY JULIUSSALOMON SAND . . 2752CCLVII1.-The Isomeric Transformation of Ammonium MethylSulphate, and of Substituted Ammonium Methyl Sulphntea ;the Interaction of Aniines and Methyl Sulphate. By EMILALPHONSE WERNER .. 2762CCLIX.-Studies in the Camphano Series. Part XXXVI.N-Chloronminocamphor. By MARTIN ONSLOW FOR~TER andMAX SCHLAEPFER . . . . 2770CCLX.-The Corrosion of Iron and its Application to Determinethe Relative Strengths of Acids. By JOHN ALBERT NEWTONFRIEND and CHARLES WILLIAM MARSHALL . . 2776CCLXI. -Rotatory Power and Refractivity. Part I. TheRotatory Powers, Refractivities and Molecular Solution-volumes of Cinchonicine and Borneo1 in Certain Solvents.By DAVID HENRY PEACOCK . . 2782CCLXII. -Substitution in Aromatic Hydroxy-compounds. Part11. Acetyl-nitro-substitution. By VICTOR JOHN HARDING 2790CCLXII1.-The Mechanism of the Action of Fused Alkalis.Part I. The Action of Fused Potassium Hydroxide onDihydroxystearic Acid and Dihydroxybehenic Acid. ByHENRY RONDEL LE SUEUR and JOHN CHARLES WITHERSPart 11.The Polysulphides of Potassium. By ALEXANDER RULE andJOHN SMEATH THOMAS . . 2819By CRELLYNCOLORAVE BISSETT . . 2829PAGE. Formation of the Amides. By GEORGE FRANCIS MORRELL . 2698. 2800CCLX1V.-The Polysulphides of the Alkali Metals.CCLXV.-The Removal of Sulphur from SilverCONTENTS. xixPAGECCLXV1.-Researches on Silicon Compounds. Part VI.Preparation of Silicon Tetrachloride, Disilicon Hexachloride,and the Higher Chlorides of Silicon by the Action ofChlorine on 50 per cent. Ferrosilicon, Together with aDiscussion on their Mode of Formation. By GEOFFREYMARTIN . . 2836CCLXVI1.-Researches on Silicon Compounds. l'it13t VII.The Action of Etliyl Alcohol on Disilicon Hexnchloride.CCLXV1II.-The Isomerism of the Oximes. Part VI. p-Di-methylaminobenzaldoxime. Ey OSCAR LISLE BRADY andFREDERICK PERCY DUNN . . 2872CCLX1X.-The Reaction Eetween Eenzylamine and the Di-bromosuccinic Acids. Iiy EDWARD PERCY FRANKLAKD . 3879CCLXX.-Some Properties of Solutions of the Boric Acids inAlcohol. A Modified Boiling -point Apparatus. By JAMESBRIERLEY FIRTH and JAMES ECKERSLEY MYERS . . 2887CCLXX1.-Contributions to Our Knowledge of Semicarb-azones. Part IV. Action of Hydrogen Chloride?. ByFORSYTH JAMES WILSON, ISIDOR &ionnIs HEILBRON, aridMAGGIE MILLEN JEFFS SUTHERLAND . . 2898CCLXXI1.-The Absorption Spectra of Snlphurons Acid andSulphites. By ROBERT WI~IGRT . . . 2907By GEOFFREY MARTIN . . 2Sd

ISSN:0368-1645    

DOI:10.1039/CT91405FP001

出版商:RSC    

年代:1914

数据来源: RSC

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ZJ. N. COLLIE, Ph.D., F.R.S.A. W. CROSSLEY, D.Sc., PI1.D.. F.R.S.Y. G. DONNAK, bI A., l’h.D., P.R.S.BERNAKD DYEW, D.Sc.M. 0. FOKSTER, D.Sc., Ph.D., F.R.S.OFJ. C. PHILIP, D.Sc., Ph.D..F. B. POWEII, PbD., LL.D.A. SCOTT, M.A., D.Sc., F.R.S.G. SENTER, D.Sc., Ph.D.S. SMILES, D.So.THE CHEnilICAL SOCIETY.TRANSACTIONS.H. BRERETON BAKER, M.A., D.Sc., T. M. LOWRY, D.Sc.F.R.S. I w. H. PERKIN. Sc.D.. LLD., F.R.S.0Ii;biiar :J. C. CAIN, D.Sc., Pi1.D.Snb- dbitar :A. J. GRERNAWAY.3ssiatanf Siub-6F;bihx :CLARENE SMITH, D. Sc.1914 Vol. CV. Part 11.LONDON:GURNEY ck JACKSON, 33, PATERNOSTER ROW, E.C.1914PRIhTEU IN GREAT BRITAIN B YRICHARD CLAY & SONS, LIMITED,BRUNSWICK ST., STAMFORD ST., S.E.,AND BDNGAY SUFFOLIC

ISSN:0368-1645    

DOI:10.1039/CT91405FP021

出版商:RSC    

年代:1914

数据来源: RSC

摘要:

BIERTON: THE ABSORPTION OF LIGHT, ETC. 2311.-The Absorption of Light by UranousChloride in Diferent Solvents.By THOMAS RALPH MERTON.IN aIl nttempts to bring the study of the absorption spectra ofsolutions from the descriptive to the rational stage, the profoundand apparently anomalous influence of the solvent has offered thegreatest difficulty, and although various theories have been putforward, it cannot be said that they have met with much success.Observations of the absorption spectra in mixed solvents seemto have thrown some light on the subject. The first measurementsof any importance in this direction are those of Deussen (Ann.Phys. Chem., 1898, [iii], 66, ll28), who investigated the absorp-tion spectra of uranyl salts in mixtures of water and alcohol andwater and glycerol.Deussen found that if ethyl alcohol was addedto an aqueous solution of uranyl nitrate, the bands were shiftedtowards the red. After a certain concentration of alcohol hadbeen reached, the bands began to move again towards the violet,until in pure alcohol they lay further towards the violet than inpure water. The importance of this inveetigation was to show tha24 MERTON: THE ABSORPTION OF LIGHT BYin mixed solvents the positions of the bands are not necessarilyintermediate between their respective positions in the puresolvents.Jones and his collaborators, in a series of papers (Amer. Chem.J., 1911 and 1912), have photographed a large number of absorp-tion spectra in pure and mixed solvents, and have shown that inma.ny cases the bands peculiar to one solvent are replaced by bandspeculiar to another, as the one solvent is replaced by the other,without a gradual shift.This, however, is no proof that aggregatesof mixed composition are not formed, but that if they are presentthey do not absorb the wave-lengths intermediate between thebands in the two pure solvents.I n a previous investigation (Proc. Roy. SOC., 1912, A , 87, 138)the absorption spectrum of uranous chloride was examined in anumber of solvents, and in certain cases the extinction curveswere given. It was found that in a number of caws strikingchanges in the character of the absorption were brought about bythe presence of free hydrogen chloride in the solution, this changehaving been first observed in the case of the acetone solution byJones and Strong (Amer.Chem. J., 1911, 45, 122). In thepresence of the free mid the relatively broad and nebulous bandsbecome much sharper and narrower, and, in certain cases, arebroken up into a number of very narrow, sharply-defined bands.I n the present work a further investigation of these bands hasbeen made, with a view to obtain some further evidence as to theirorigin and the circumstances in which they appear.The uranous chloride, and other materials, used in this investi-gation were obtained from Kahlbaum. The spectra were examinedvisually, and photographed. For visual examination a large modelconstant deviation spectroscope by Hilger was used, the wave-lengths being read on a helical drum with an average accuracy of1 i .U . For ths photographs of the spectra a concave gratingspectrograph by Hilger was used, having a l a inch grating of4 feet radius of curvature, and 20,000 lines to the inch. It wasmounted according to the method described by Eagle (Astrophys.J., 1910, 31, 120). Wratten and Wainwright’s “ M ” plates onspecially thin glass were used. They were bent in the plate-holderto a circle of radius equal to the radius of curvative of the grating.Eagle (Zoc. cit.) has shown that in these circumstances the spectrumobtained is as normal as is obtained by Rowland’s mounting. Forthe whole of the plate to be in perfect focus, it should be bent to acircle of half this radius, but it was found that over the rangeused the spectra were not appreciably out of focus.The solutions examined were contained in parallekided glasURANOUS CHLORIDE IN DIFFERENT SOLVENTS.25cells in front of the slit of the spectrograph. As a source of light,the positive crater of a small carbon arc was used. The carbonswere brushed over with a dilute solution of lithium nitrate, andthe red and orange lithium lines and the sodium B lines served asstandards. The scale of the photographs was almost exactly10 1. U. per millimetre.I n pure solvents the absorption spectra ar0 not very sharplydefined, and the narrow bands, when present, could only be identi-fied with difficulty, being to a great extent masked by broad,diffuse absorption bands. When, however, the solution was satur-ated with dry hydrogen chloride or a few drops of concentratedhydrogen chloride in aqueous solution were added, the broad,diffuse bands disappeared, and were replaced by a sharply-definedand very characteristic spectrum.It was found that in some casesthe absorption spectrum obtained by saturating with the dry gaswas very different from that obtained by adding a few drops ofconcentrated hydrochloric acid in aqueous solution, whilst in othersthe two spectra were identical, or showed very small differences.I n the plate, which has a wave-length scale in juxtaposition toeach spectrum, No. 1 shows the absorption spectrum in pure acetone,which had been dried over barium oxide. Bands in the neighbour-hood of 670 and 654 could be seen, but were so masked by thegeneral absorption that they do not appear in the reproduction.This occurs also in the other pure solvents. No.2 is the spectrumof the same solution after saturation with dry hydrogen chloride.It will be seen that in place of the general absorption extremelycharacteristic bands have appeared. No. 3 is the same solutionafter adding a drop of concentrated hydrochloric acid in aqueoussolution.It will be seen that these two spectra are very different. Anotherexample of this change is shown in strips 4 and 5, which are of asolution in ethyl acetoacetate treated with dry and aqueoushydrogen chloride respectively. (In strip 4 a much thinner layerof solution was used in order to show the less refrangible bands,which in a thicker layer were somewhat masked by the generalabsorption.)I n acetonitrile, however, the spectrum is the same, whether thesolution is treated with dry or aqueous hydrogen chloride.Strips6 and 7 are the spectra in pure acetonitrile and in acetonitrilewith hydrogen chloride respectively. Strip 8 is a solution in ethylalcohol, with aqueous hydrogen chloride. When observed with thesingle prism spectroscope, there appeared to be a difference betweenthe solutions in ethyl dcohol with aqueous and dry hydrogenchloride. The higher dispersion of the grating, however, shows tha26 MERTON: THE ABSORPTION OF LIGHT, ETC.this only consists of a sharpening of the bands in the former case.Strip 9 is the spectrum in acetophenone with hydrogen chloride.The changes may be tabulated as follows:(1) A general absorption which disappears on treatment withhydrogen chloride, whether a small quantity of water is presentor not.(2) The group of bands between 5900 and 6050 which appear inacetone, acetonitrile, ethyl acetoacetate, ethyl alcohol, and aceto-phenone, on t,reatment with hydrogen chloride, whether water ispresent or not.(3) Bands a t about 654 and 670 visible in acetone and ethylacetoacetate, on treatment with hydrogen chloride.These bandsdisappear on adding a, trace of water. The bands are just visiblein pure acetone, but are almost completely masked by the generalabsorption. (The band a t 626 in the acetone solution with dryhydrogen chloride appears to be peculiar to this solution.)(4) BandB a t about 635 (faint), 657, 659, 666, 671, 676, etc.,visible in acetone and ethyl acetoacetate with hydrogen chlorideand a trace of water, and in ethyl alcohol and amtonitrile withhydrogen chloride with or without water.(The ethyl alcohol andacetonitrile were dried over barium oxide.) The relative intensitiesof these bands vary somewhat in the different solvents, althoughthere can be no doubt that the bands in question correspond.The spectrum in acetophenone appears to be peculiar to thatsubstance.It does not appear possible to explain the phenomena withoutassuming that different kinds of aggregate co-exist in the solutions,and that the vibrators responsible for the less refrangible bands aresituated in different aggregates to those responsible for the morerefrangible bands.It follows that the true molecular extinction-coefficient for aparticular radiation cannot be derived from a measurement of theextinction-coefficient of the solution and a knowledge of its con-centration; thus a weak absorption band in a concentrated .solutionmay be due either to a small extinction-coefficient, or to the factthat only a small number of molecules are in the condition toabsorb that particular radiation.In the case of the rare earths,Koenigsberger (see Houstoun, Proc. Roy. SOC. Edin., 1913, 33,161) has assumed that the absorption is due to exceptionalmolecules. The molecular extinction-coefficient of a solution wouldtherefore appear to be the coefficient of the average aggregate,rather than that aggregate which is actually absorbing.I n most physico-chemical meaauremenb, such as density, viscosity,surface tension, etc., what really is measured is the property of th[To face p . 26LEVY: THE ACTION OF AMINO-ACID ESTERS, ETC. 27average aggregate. An aggregate identical with the averageaggregate for one property of a solution might be quite differentfrom the aggregate which was the average aggregate in determininganother property.I n conclusion, I should like to thank Mr. H. B. Hartley, ofBalliol College, Oxford, for his kind advice.25, GILBERT STREET,LONDON, W

ISSN:0368-1645    

DOI:10.1039/CT9140500023

出版商:RSC    

年代:1914

数据来源: RSC

摘要:

LEVY: THE ACTION OF AMINO-ACID ESTERS, ETC. 27111.-The Action o,f Amino-acid Esters on EthylDicarboxyglutaconate.By STANLEY ISAAC LEVY.WHEN ethyl dicarboxyglutaconate, CH(CO,Et),*CH:C(CO,Et),, ofwhich the sodium derivative is obtained by the action of chloroformon ethyl sodiomalonate (Conrad and Guthzeit, Annalen, 1883, 222,256), is allowed to remain for some days with concentrated aqueousammonia, i t decomposes, with elimination of ethyl malonate, form-ing ethyl aminomethylenemalonate, NH2*CH:C(C0,Et), (Ruhemannand Morrell, T., 1891, 59, 744). The mechanism of this change,and the actions of various ammonia derivatives on ethyldicarboxyglutaconate, have been studied by Ruhemann and hispupils, and it has been found that the reaction is one of verygeneral application ; thus analogous derivatives have been obtainedby the action of aniline and aromatic diamines, primary andsecondary aliphatic amines and diamines, hydroxylamine, hydr-azine, phenylhydrazine, piperidine, etc. (compare Ruhemann andMorrell, T., 1892, 61, 791; Ber., 1894, 27, 2743; Ruhemann andMiss Sedgwick, Ber., 1895, 28, 822; Ruhemann, Ber., 1897, 30,821, 1083; Ruhemann and Hemmy, Ber., 1897, 30, 2022).Thereaction has now been extended to amino-acid esters, and it isfound to apply generally to a-amiuo-compounds of this class.The change takes place very readily when a solution of ethylsodiodicarboxyglutaconate in boiling alcohol is treated with thecalculated quantity of the ester hydrochloride in the same solvent;the yellow colour of the sodium compound is rapidly discharged,with separation of sodium chloride.In the case of ethyl glycinehydrochloride, for example, the reaction is expressed by theequation :CO,Et.CH,*NH,,HCl + CNa(CO,Ef),*CH:C(CO,Et), =CO,Et*CH2*NH*CH:C((3'O,Et), + Cs(COaEt), + NaC128 LEVY: THE ACTION O F AMINO-ACIDethyl glycylmethylenemalonate, together with ethyl malonate, beingobtained. Analogous derivatives have been prepared, by the samemethod, from the ester hydrochlorides of alanine, aminobutyric,and aminoisobutyric acids, and leucine ; but whereas the glycinecompound is a colourless, odourless, crystalline solid, melting at98-99O, the homologues hitherto obtained are yellow, viscous oils,which show no tendency to solidify, and possess de'finite odoursrecalling that of mustard oil.The reaction has been shown to takeplace also with the ester hydrochlorides of tyrosine, aspartic acid,and o-aminobenzoic acid; the products in these cases also areyellow oils, but since they decompose when distilled in a vacuumit has been impossible to obtain them in the pure state.I n chemical behaviour the new derivatives very closely resembleethyl aminomethylenemalonate, of which a further examinationhas been made in an effort to prepare from i t some saturatedderivatives. Several attempts have been made to reduce this sub-stance, with the view of establishing a more convenient synthesisof B-alanine, according to the scheme :NH,*C'H:C(CO,Et), + NH,*CH,*CH(CO,Et), +NH,*CH,*CH(CO,H), -+ NH2*CH,*CH,*C02H,but none has been successful.On account of the ease with whichthe compound decomposes in acid or alkaline solutions, neutralreducing agents have been employed; but zinc aiid magnesium, inthe presence of neutral salts, the zinc-copper couple, aiid finallyhydrogen in the presence of colloidal palladium, are all withouteffect. Bromine in glacial acetic acid in the cold causes hydrolysis,according to the equation:NH,-CH:C(CO,Et), + Br, + 2H,O =NH,Br -1- H*CO,H + CHBr(CO,Et), ;it similar decomposition occurs when dry hydrogen chloride ispassed into the benzene solution. The ester is equally sensitive tothe action of alkaline reagents ; when treated with sodium ethoxidein absolute alcohol solutioii it decomposes, with evolution ofammoniz, and separation of ethyl sodiomalonate.Ethyl glycylmetliylenemalonate and its homologues show a closeparallel with this behaviour.They dissolve readily in cold concen-trated sulphuric and hydrochloric acids, giving solutions fromwhich the various products of hydrolysis are obtained on dilution ;they are not attacked by neutral reducing agents, and are decom-posed by alkalis and by bromine in the cold. When heated withaniline they decompose according to the equation (for the glycinecompound) :COaEt*CH,*NH*CH:C(C0,Et)2 i- 2C6H5*NH2 =CO,E t*CB,*NH2 + C6H,-NH*CH: Cf C0,E t) *GO -NH*CbH, + E t OHESTERS ON ETHYL DICARBOXYGCUTACONATE. 29yielding the amino-acid ester and the monoanilide of ethyl anilino-methylenemalonate in precisely the same way as ethyl amino-methylenemalonate, when heated with aniline, gives ammonia andthe monoanilide (Ruhemann and Rtorrell, Ber., 1894, 27, 2743).EXPERIMENTAL.Ethyl GlycylnieIJL?/Zen?.alonate, CO,Et*CH,*NH*CH:C(CO,Et),.A solution of ethyl sodiodicarboxyglutaconate (7.1 grams) inboiling alcohol is treated with ethyl glycine hydrochloride (3 grams,1 mol.), dissolved in the same medium.Sodium chloride begins toseparate a t once, and the yellow colour of the solution is rapidlydischarged. The mixture is heated on the water-bath until thealcohol Bas been almost completely removed; on addition of waterthe sodium chloride dissolves, leaving an oil, which sets almost a tonc0 to a mass of crystals. The solid is collected by the aid of thepump, ethyl ma-lonate passing through with the filtrate; the solidis then dissolved in hot dilute alcohol, from which it separates oncooling in colourless prisms melting a t 97-98O:0.2027 gave 0.3900 CO, and 0.1272 H,O.C,,H,,O,N requires c? = 52-76 ; H = 6-96 per cent.The ester is very readily soluble in ether or alcohol; on dilutingthe alcoholic solution with water, it separates as an emulsion, whichsolidifies on keeping.The amide, NH,*CO*C€12*NH*CH:C(@0,Et),, is obtained ondissolving the ester in concentrated aqueous ammonia; after keep-ing for a short time, the solution sets t o a semi-solid.The amideis collected and crystallised from boiling water, in which it isreadily soluble; on cooling it separates in colourless needles, whichsoften a t 178O and melt and decompose a t 180-181°:C=52*47; H=6*97.0.2053 gave 0.3705 CO, and 0.1205 H,O.C'= 49.21 ; H = 6-52.0.1970 ,, 19.8 C.C. N, at 2 3 O and 771 mm. N=11*50.C,oH,60,N, requires C=49.18; H=6*55 ; N = 11.47 per cent.The amide dissolves a t once in cold concentrated sulphuric acid,forming a greenish-yellow, fluorescent solution ; on pouring on iceafter two days, it is deposited unchanged, but if the solution iswarmed, it darkens rapidly, and decompoeition occurs.E: t h y 1 A lan ylme tlhyl ertemal onat e, CO,Et* CHMe*NH*CH : C(C0,E t)z.When ethyl sodiodicarboxyglutaconate (7.0 grams), dissolved inboiling alcohol, is treated with ethyl a-alanine hydrochloride(3.2 grams, 1 mi.) thg colour is discharged, and sodium chlorideis precipitated; after the removal of alcohol on the water-bath30 LEVY: THE ACTION OF AXINO-ACIbaddition of water causes the separation of an oil, which does notsolidify, even when cooled in a freezing mixture.The oil isextracted with ether, the ethereal solution dried, and the brownoil left after removal of the solvent fractionated under diminishedpressure. Ethyl maloiiate distils at 90-95O/ 12 mm. ; the tempera-ture then rises sharply, and a t 206-212O/12 mm. a yellow oildistils, a slight tarry residue remaining in the distilling flask. Onredistillation the oil passes over completely a t 206-207O/ 10 mm.,and is then obtained as a pale yellow, viscous liquid; the yield isalmost theoretical :0.2370 gave 0.4720 COB and 0.1550 H20.C=54*32; H=7.27.C1,H,,O,N requires C = 54.35 ; H = 7-32 per cent.The oil dissolves readily in cold concentrated sulphuric acid.When after keeping for a day the cold solution is poured on asmall quantity of ice, a white solid separates; from the ease withwhich this dissolves in water, and the reddish colour observed whenferric chloride is added to the aqueous solution, this was identifiedas the salt of the amino-acid; on diluting the filtrate, a yellow oilis precipitated. A clear solution is also obtained when ethyl alanyl-methylenemalonate is treated with cold concentrated hydrochloricacid; on diluting after one day, an oil separates, which has thed o u r of ethyl malonate. Decomposition also occurs when the esteris treated with three equivalents of cold alcoholic potassiumhydroxide, or with bromine in glacial acetic acid.Attempts were made to reduce the ester with the zinc-coppercouple. A solution in 95 per cent.alcohol was heated with thisreagent for two hours on the water-bath. After filtering, thealcohol wm removed by evaporation; the residue on addition ofwater formed an oil, which was extracted with ether, and found bydistillation to be the unchanged ester.Ethyl alanylmethylenemalonate does not react when treated withaniline in glacial acetic acid solution at the ordinary temperature;if the mixture is heated on the water-bath, decomposition occurs.No reaction occurs if a mixture of the ester with aniline alone isheated on the water-bath for two hours; but if this mixture is keptat 150° for the same time, a dark, oily product is obtained, whichsolidifies on cooling.The solid dissolves readily in warm alcohol;after boiling with animal charcoal, the filtered and concentratedsolution deposits on cooling a pale yellow solid, which is obtainedon crystallisation from dilute alcohol in elongated needles, meltinga t 118-119O:0.1910 gave 15.0 C.C. N, at 21° and 772 mm. N=9*08.This analysis and the melting point show the substance to be@lsH,80sNz requires N=9.03 per centESTERS ON ETHYL DICARBOXYGLUTACOWATE. 31the monoanilide of ethyl anilinomethylenemaZamte. The motherliquor on concentration yields a small quantity of malondianilide,arising, as in the action of aniline on ethyl aminomethylenemalon-ate (Ruhemann and Morrell, Eoc.cit.), from the further action ofaniline on the first substance.The monoanilide has also been recognised in the products of theaction of aniline on ethyl glycylmethylenemalonate and on ethyldimethylglycylmethylenemalonate (see below), and there can be nodoubt that the reaction is a general one for this series of compounds.Eth yE Dimet hylglyc ylmethylememalonat e,C0,Et. CMe,*NH*CH :C( C0,E t)2'This compound is obtained by the action of ethyl a-aminkso-butyrate hydrochloride on ethyl sodiodicarboxyglutaconate, themethod being the mme as that employed in the preparation of thealanyl derivative. The reaction in this case proceeds more slowly,however, and the yield is not quite so good. The oil distils a t220-222*/ 18 mm., with slight decomposition :0.1930 gave 0.3940 CO, and 0.1270 H,O. C =55*67; H= 7-31.C14HB06N requires C = 55-81 ; H= 7.64 per cent.E thtyl Ethylgl ycylmethylenemdonate,CO& t CEI E t -NH*CB: C( C0,E t)2.This compound, isomeric with the above, is prepared, in the sax138way, from ethyl a-aminobutyrate hydrochloride. It is a pale yellowoil, boiling at 214--215O/12 mm.:0.1820 gave 0.3720 CO, and 0.1240 H,O. C=55*74; H=7'57.C14H,,0,N requires C = 55.81 ; H'= 7.64 per cent.Bth yl Leuc ylmet h yl enemalonate,CHM%* CH( C 0,E t ) NH- CH C ( C02E t)*This substance, obtained from ethyl leucine hydrochloride bythe same method as the above, is a yellow oil distilling with slightdecomposition a t 233-234O/ 12 mm. :0.1680 gave 0.3590 COB and 0.1220 H,O. C=58*28; H=8*21.C,,H,,O,N requires C = 58-36 ; H= 8.21 per cent.In conclusim, I wish t o express my sincerest thanks t o Dr. 8.Ruhemann, who suggeeted to me this investigation, and has helpedme throughout by his kind advice.CAMBRIDGE.UNIVERSITY CHEMIUAL LABORATORY

ISSN:0368-1645    

DOI:10.1039/CT9140500027

出版商:RSC    

年代:1914

数据来源: RSC

摘要:

32 COPPIN AND TITHERLEY: THE CONDENSATION OFIV.- The Condensation of C'lzloyal Hydyate andCad am ic-le.By NOEL GUILBERT SWEVENSON COPPIN andARTHUR WALSH TITHERLEY.THE study of the condensation between chloral and carbamide,described in the present paper, was made in order to facilitate theinvestigation now being undertaken of the mechanism of condensa-tion of glyoxylic acid and carbamide, which it is hoped willeventually lead to the synthesis and proof of constitution of certaindegradation products of allantoin and uric acid, such as allanturicacid and oxonic acid, the chemical nature of which is still obscure.Jacobsen (Annalen, 1871, 157, 246), by adding chloral hydrateor alcoholate to a nearly saturated solution of carbamide, obtaineda crystalline solid (m.p. 150°), which he regarded as the doublecompound, C'Cl,*CH:O,CO(NH,),, and also obtained a secondcompound (m. p 190.) in smaller amount, which on analysiscorresponded with the formula 2CCl3*CH:O,CO(NH&..The nature and conditions of formation of these two derivativeshave been examined by the authors, who find that they are normalcondensation derivatives, analogous in constitution to the methylolderivatives obtained by Einhorn (Annalen, 1905, 343, 207 ; 1908,361, 131) in the condensation of formaldehyde and amides. Thatis, the solid of lower melting point is fl-trichloro-a-hydroxyethyl-carbamide, CCl,*CH(OH)*NH*CO*NH, (I), whilst the other isdi (P-trichloro-a-hydrox y ethyl) carbamide,CI(=l,CH( OH) *NH* CO NH* CH (OH) *CCI, (11).Although the reactions leading t o their formation are reversible,owing to the ease with which they crystallise out under suitableconditions, no difficulty is experienced in their isolation and puri-fication.Both these substances, which are sparingly soluble inwater, are interesting in showing phenolic properties, by readilydissolving in aqueous alkali, owing to the -negative influence of theCCl, group on the neighbouring hydroxyl. Whilst, however, theymay be recovered unchanged from the alkaline solution by acidifi-cation, they are unstable towards alkali on warming, and readilyyield chloroform and other products.It has been found that whilst in concentrated aqueous solutionsequivalent quantities of chloral hydrate and carbamide react slowlyat the ordinary temperature to give mainly the simple condensationderivative (I), small quantities of the compound (11), derived fromtwo molecules of chloral hydrate and one of carbamide, were alwaysformed, and that this secondary reaction is be& prevented by usinCHLORAL HYDRATE AND CARBAMIDE.33two molecular proportions of carbamide to one of chloral hydratein the condeiisation. When hydrochloric acid is present catalyst,the velocity of the condensa.tion is greatly accelerated, especiallythat leading to the formation of the compound (11) melting a t196O, which results even when two molecular proportions of carb-amide to one of chloral hydrate are used. The same compound isfound in considerable quantity without an acid catalyst whenchloral hydrate and an excess of carbamide are heated at 80°without solvent; and i t is also slowly formed from the compound (I)and chloral hydrate in aqueous solution in the absence or presenceof hydrochloric acid.The yield, however, by this method is muchless than in its direct formation in the wet way from carbamide.I n no case was any evidence obtained of the formation of trichloro-ethylidenedicarbamide, CCl,*CH(NH*CO*NH,),, in the wet con-densation of chloral hydrate and carbamide, with or without acidcatalyst. This substance has already been described by Pinner andLifschutz (Ber., 1887, 20, 2346), who obtained it by heating amixture of chloral cyanohydrin and carbamide at 90°. It wasfinally obtained by the present authors by the condensation of8-trichloro-a-hydroxyethylcarbamide and carbamide (in excess) inpresence of acetic anhydride at looo.The unsaturated compound,trichloroethylidenecarbamide, CCl,*CH:N*CO*NH,, was obtained ina pure form, as silky needles of high melting point, by a similarmethod to that employed by Diels and Seib (Ber., 1909, 42, 4065)in the dehydration of chloralurethane, namely, by the action ofacetic anhydride on 8-trichloro-a-hydroxyethylcarbamide (I) in thepresence of aqueous alkali.EXPERIMENTAL./3-Trichloro-a-h,ydToxye t h $car bamide, CCl,* CH (OH)*NH*CO*NH,.ThO best conditions for the preparation of this substance were asfollow: Twelve grams of carbamide (2 mols.) in 10 C.C. of waterand 16-5 grams of chloral hydrate (1 mol.) in 10 C.C.of water weremixed and left in a corked flask at the ordinary temperature.Transparent crystals began t o separate in a few hours, and a t theend of three days, wbeii no more was deposited, the crystals, con-sisting of nearly pure 8-trichloro-a-hydroxyethylcarbamide, weighed14.8 grams (66 per cent. of the theoretical) and melted at 146O.After slow recrystallisation from a mixture of methyl alcohol antibenzene it was obtained in large, transparent pyramids, melting at150O. (Found, Cl=51.16; N= 13.65. C,H,O,N,Cl, requiresC= 54-33 ; N = 13.49 per cent.).When, instead of using the above proportions, equimolecularv01,. C V . I 34 COPPIN AND TlTHERLEY : THE CONDER3ATIOX 014'quantities of chloral hydrate (16.5 grams) and carbamide (6 grams)are taken, after two days a mixture (12 grams) is obtained, consist-ing essentially of 8-trichloro-a-hydroxyethylcarbamide, but contain-ing 3 per cent.of di@-trichloro-a-hydroxyethy1)carbamide. It ispossible to separate the two by cautious, rapid, fractional crystal-lisation from warm water.P-Trichloro-a-hydroxyethylcarbamide is soluble in 25 parts ofwater a t 1 5 O ; i t is very readily soluble in methyl and ethylalcohols, or acetone, somewhat sparingly so in ether, and almostinsoluble in chloroform or benzene. It is easily soluble in hot water,and on rapidly cooling separates out again without appreciableloss, but owing to slow hydrolysis into chlmal and aarbamide theamount which separatm out on cooling decreases with the lengthof time of heating.Moreover, owing t o the gradual appearancein the solution of free chloral hydrate and carbamide in equi-molecular proportions, di(@-trichloro-a-hydroxyethy1)carbamide isslowly formed. By weighing the crystals of impure /3-trichloro-a-hydroxyethylcarbamide which separated, and allowing for solu-bility, it was found that whilst in 50 per cent. aqueous solution a t70" no appreciable hydrolysis occurs in thirty seconds, in fifteenminutes about 25 per cent. of the substance becomes hydrolysedinto chloral and carbamide. On continued heating a t 70° (in50 per cent. aqueous solution) di(P-trichloro-a-hydroxyethy1)carb-amide, which is sparingly soluble in hot water and apparently lesseasily hydrolysed than the mono-derivative, continually separatesand disturbs the equilibrium.After an hour the solid mixture,which was isolated after cooling, weighed 50 per cent. of theoriginal /3-trichloro-a-hydroxyethylcarbamide, and consisted of about70 per cent. of the mono- and 30 per cent. of the di-derivative.After three hours' heating at 70° the solid mixture obtained bycooling (51 per cent. of the original weight) waa richer in thedi-derivative (53 per cent.).P-Trichloro-a-hydroxyethylcarbamide readily dissolves in aqueoussodium hydroxide, and is precipitated again in not too dilutesolution by acids. On warming the alkaline solution rapid decom-position occurs, with the formation of chloroform.D i (8- t rich1 o r 0-a-?A y d r o x y e t hyl) car b a rnide,CCl,*CH(OH)*NH*CO*NH-CH(OH) qCC1,.Six grams of carbamide in 5 C.C.of water were mixed with33 grams of chloral hydrate in 10 C.C. of water, and 20 C.C. ofconcentrated hydrochloric acid were added. I n a short time a fine,white, insoluble, micro-crystalline powder separated, and increaseduntil finally the whole mass became largely solid. After threa dayCHLBRAL HYDRATE AND CARBAMIDE. 35the insoluble solid was collected, and found to be pure di(P-tri-chloro-a-hydroxyethy1)carbamide (25 grams, or 71 per cent. oftheory). Thel mother liquor deposited a further 0.5 gram 011keeping. The substance after recrystallisation from aqueous alcoholseparated in small, pearly flakes, melting a t 196O. (Found,Cl = 59.58; N = 7.99. CSH,0,N2C1, requires C1= 60.0 ; N = 7.9 percent.)1 he formation of this compound has been observed wheneveraqueous chloral hydrate and carbamide are present in equi-molecular proportions, or even in the ratio of 1 mol.: 2 mole. inthe presence of hydrochloric acid; thus 16.5 grams of chloralhydrate and 12 grams of carbamide dissolved in 120 C.C. of waterand 5 C.C. of concentrated hydrochloric acid gave, after twelvehours, 2.8 grams, and in a week 3.6 grams of pure di(B-trichlorcl.a-hydroxyethy1)carbamide. The aqueous filtrate contained8-trichloro-a-hydroxyethylcarbamide (1 2 grams). A much largeryield of the di-derivative (15.5 grams) was obtained from the abovequantities of chloral hydrate and carbamide when dissolved in only15 C.C. of water and 27 C.C. of concentrated hydrochloric acid, themixture being allowed to remain for several days.Di(8-trichloro-a-hydroxyethy1)carbamide is practically insolublein water, chloroform, or benzene, somewhat sparingly soluble inether, a r d moderately easily soluble in alcohol or acetone, Itdissolves at once in aqueous sodium hydroxide, and is precipitatedunchanged by acids, but if the alkaline solution is kept or heated,slow or rapid decomposition occurs, with the formation of chloro-form.Trichloroe t h y lidenecnrb amidc, CC1,* CH: N= CO *NH,.Ten grams of /3-trichloro-a-hydroxyethylcarbamide, dissolved in100 C.C.of ice-cold N-sodium hydroxide (2 mols. NaOH), weretreated gradually. and with continual agitation. with 5 grams ofacetic anhydride. The temperature was kept low by surroundingthe vessel with ice, and the addition of acetic anhydride, whichimmediately produced a white precipitate, occupied ten minutes.After a further ten minutes the mass .was made distinctly alkalineby stirring with a little aqueous sodium hydroxide, and the snow-white, solid powder was collected and washed.It consisted of puretrichloroethylidenecarbamide, and the yield (9.3 grams) was practi-cally theoretical. It was obtained in fine, silky needles by cautiousrecrystallisation from a mixture of alcohol and benzene, and melteda t 234O:0.1330, by Kjeldahl’s method, required 13.9 C.C. NI10-HC1.N = 14-63,0 36 TWISS: THE ACTION OF HYDROGEN PEROXIDE0.1534 gave 0.3482 AgC1. C1=56.1.C,H30N,C'1, requires N = 14.78 ; (31 = 5 6 3 per cent.The substance is readily soluble in alcohol or acetone, sparinglyso in ether, and practically insoluble in chloroform.benzene, orwater.Trichloroe t h ylidenedicarb amide, CC?13*CH(NH CO-NH,),.Twelve grams of carbamide (2 mols.) and 20.8 grams of P-tri-chloro-a-hydroxyethylcarbamide (1 mol.), both very finely powdered,were heated on the water-bath with 12 grams (1 mol.) of aceticanhydride for six hours. The clear liquid began to deposit a whitesolid after about half-an-hour, and ultimately the contents of theflask became largely solid. The mass wits extracted with alcohol,and after washing with the Iatter the insoluble white powder wasdigested with 10 per cent. sodium hydroxide and washed. Theresidual crude trichloroethylidenedicarbamide (7 grams) gave lowvalues (between 20 and 21 per cent.) for nitrogen on analysis; itwas purified by dissolving in warm concentrated sulphuric acid,and after cooling cautiously precipitating by water and digestingwith aqueous alkali. It was obtained in this way in fine needles(with considerable lorn), sparingly soluble in boiling acetic acid,and pra,ctically insoluble in all the usual solvents. (Found,C1= 42-70 ; N = 22.0. C,H,O,N,Cl, requires C1= 42.69 ; N = 22.45per cent.)ORGANIC LABORATORY,UNIVERSITY OF LIVFIWOOL

ISSN:0368-1645    

DOI:10.1039/CT9140500032

出版商:RSC    

年代:1914

数据来源: RSC

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36 TWISS: THE ACTION OF HYDROGEN PEROXIDEV.-I’he Action of fTydro,qen Peroxide on the SodiumA lk y 1 Thiosti lphates.By DOUGLAS FRANK TWISS.A SHORT time ago it was shown by Fichter and Sjostedt (Ber., 1910,43, 3422) that organic sulphur compounds, such as benzyl sulphideand disulphide, can be subjected to electrolytic oxidation in glacialacetic acid containing hydrogen chloride, with formation ofsulphoxides, sulphones, and sulphonium compounds. I n the hopeof obtaining similar results with organic diselenides, dibenzyldiselenide was submitted t o similar treatment, but the result wasdisappointing ; the diselenide molecule is apparently less stable thanthe disulphide, and the only isolated products were benzyl chlorideand seleniumON THE SODIUM ALKYL THIOSULPHATES.37As the preparation of oxidation products of the diselenides, forexample, the diselenoxides or diselenones, appeared to be of interest,endeavours were made to achieve this end by the application ofhydrogen peroxide, which has proved useful with the analogoussulphur compounds (compare Hinsberg, Ber., 1908,41, 2836 ; 1910,43, 289). Again, however, the results were not those expected, forin acetic acid solution the oxidation gave almost entirely benzylalcohol and selenious acid. Experiments in this direction have alsobeen recently made incidentally by Fromm and Martin (AnmaZen,1913, 401, 185), who merely remark that they did not succeedin converting dibenzyl diselenide into the diselenoxide by means ofhydrogen peroxide. ThO experiments recorded in the present paperwere completed before this publication was made,I n the failure of the two above methods, experiments were triedon the oxidation of sodium benzyl selenosulphate by hydrogenperoxide, and as the results appeared tu be favourable, it prelimin-ary investigation was made with the analogous thiosulphatecompounds.It is found that in acid solution the sodium alkyl thiosulphatesare smoothly oxidised by hydrogen peroxide, with the formationof the corresponding disulphides.The process is very convenientas a method of preparation of the latter class of substance, andappears to possess some slight advantage over the methodspreviously described for the conversion of sodium alkyl thiosulphatesinto disulphides (Price and Twise, T., 1907, 91, 2021; 1908, 93,1395; 1909, 95, 1489).It is interesting that whereas electrolyticreduction necessitates the application of neutral or alkaline solu-tions (T., 1907, 91, 2021), oxidation by hydrogen peroxide requiresan acid solution. I n the presence of excees of alkali, oxidationyields no insoluble substance, but appears to attack the character-istic disulphide grouping, with formation of sulphur oxy-acids andof organic carboxylic acids. The apparently general applicabilityof the method is evidenced by the preparation of disulphides ofthe radicles benzyl, o-nitrobenzyl, pnitrobenzyl, and even allyl.An extension of the method to potassium o-nitrobenzylseleno-sulphate gave the production of di-o-nitrobenzyl diselenide, thusencouraging the hope that it may be useful for the preparation ofdiselenides also.Oxidation of DibenzyZ Diselenide.A cooled suspension of 13 grams of dibenzyl diselenide in 75 C.C.of glacial acetic acid was stirred continuously whilst 20 C.C.ofhydrogen peroxide solution (30 per cent.) were added slowly indrops from a tap funnel. After the introduction of the hydrogel38 TWISS: THE ACTION OF HYDROGEN PEROXIDEperoxide, most of the solvent was removed by distillation underdiminished pressure. The yellow residual oil in the flask partlycrystallised on keeping, and the crystals were found to consist ofselenious acid, which on reduction by a mixture of hydrochloricand sulphurous acids yielded practically the whole of the seleniumoriginally present in the diselenide.The oil from which the selenious acid had crystallised, whendistilled, gave a large fraction (b.p. 203--210°), consisting ofbenzyl alcohol.The only other substance that could be isolated was one whichcrystallised in very small quantity from the acetic acid distillateobtained in the first process after the oxidation; this formed needlesmelting at 55O.Oxidation in acetone solution gave still lecjs satisfactory results,but a minute quantity of the substance melting at 5 5 O was againobtained, but i t was again insufficient for further examination.Oxidution of the AIkyl I'hioszdphute Compounds.The oxidation was effected in aqueous solution, and as the oxida-tion generates acid, all that is required is the addition of hydrogenperoxide solution :2C,H,*CH2*S20,Na + H20, = (C,H,*CH,)S, + ZNaHSO,.The addition of a little acid, however, greatly accelerates the action,so that in a few hours at the ordinary temperature more than90 per cent.of the theoretical yield of almost pure disulphide isobtained.Taking sodium benzyl thiosulphate as a typical example, 3 gramsof this substance were dissolved in 40 C.C. of water, 4 C.C. of dilutesulphuric acid were added, and then 4 C.C. of 30 per cent. hydrogenperoxide solution. The solid which deposited melted a t 71'5Owithout recrystallisation. The oxidation can be accelerated if neces-sary by warming without diminution of the yield. The additionof a little ferrous sulphate, although it catalyses the reaction,renders the product less pure.Similar results were obtained with sodium o-nitrobenzyl thio-sulphate and with sodium p-nitrobenzyl thiosulphate, the produceddisulphides again being almost pure without further treatment.I n experiments in which sodium o-nitrobenzyl thiosulphate wastreated with hydrogen peroxide in aqueous solution containing suffi-cient' sodium carbonate or sodium hydroxide t o maintain an alkalinereaction to litmus, no disulphide or any other solid separated,although the thiosulphate compound was completely changed.Acidification of the solution by hydrochloric acid gave a precipitatewhich was identified as o-nitrobenzoic acidON THE SODIUM ATJKYL THIOSULPHATES.39Sodium a-llyl thiosulphate was not isolated, but a solution preparedin the usual manner by heating together an alcoholic solution ofallyl bromide with an aqueous solution of the equivalent quantityof thiosulphate, was first deprived of its alcohol by partial distilla-tion under diminished pressure; the cold residual solution was thentreated with hydrogen peroxide, when diallyl disulphide slowlyseparated as an undistillable, yellow oil.(Found, S =42.3. C,H,,S,requires S -43.5 per cent.*)An attempt to prepare the disulphide by the action of iodine ona hot solution of sodium allyl thiosulphate (compare Price andTwiss, T., 1909, 95, 1489) did not yield a satisfactory result.Potassium o-nitrobenzyl selenosulphate (1.5 grams), dissolved inapproximately 100 C.C. of water and treated with a little acetic acidand 3 C.C.of 30 per cent. hydrogen peroxide solution, gave a thickdeposit of di-o-nitrobenzyl diselenide, the action being complete inone-half to one hour. When once crystallised from alcohol thesubstance was pure and of the correct melting point.With potassium pnitrobenzyl selenosulphate under similar condi-tions the reaction appeared to proceed in an analogous manner, butthe product was a substance melting at 11B0, the melting point ofthe corresponding diselenide prepared by the action of iodine being107'5O. The cause of this discrepancy is not yetl clear.The application of hydrogen peroxide in this direction for thepreparation of disulphides and diselenides is being further extended,especially as it appears to be particularly well suited for the produc-tion of such compounds where other methods are known to give riseto by-productJs of unpleasant d o u r .It is also hoped to submit the chemical action to a physico-chemical examination.The author wishes to express his appreciation of the friendlyinterest of Dr. T. Slater Price in the above investigation.CHEMISTRY DEPARTMENT,MUNICIPAL TECHNICAL SCHOOL,BIRMINGHAM.* The sulphur was estimated by the electrolytic process of Gasyarini (CTamtta,1907, 37, 426), but considerable care was necessary in the introduction of the nitricacid on account of the vigour of the reaction on mixing

ISSN:0368-1645    

DOI:10.1039/CT9140500036

出版商:RSC    

年代:1914

数据来源: RSC

摘要:

40 ROBISON AND KIPPING :VI.-Organic Derivatives of Silicon. Part X X ,Some Condensation Products of Dibenx y bilicanediol.IN the last four papers on organic derivatives of silicon (T., 1912,101, 2108, 2125, 2142, 2156) it was shown that certain disub-stituted silicanediols of the type SiR2,(0H),, in which a t least oneof the radicles is aromatic, are capable of existence a t the ordinarytemperature, and, therefore, are mole stable than the correspondingderivatives of methane.Such compounds, however, readily undergo change when theyare heated alone, or when they are treated in solution with variousreagents, such as alkali hydroxides, ammonia, or mineral acids.The result, as a rule, is the formation of a mixture of open- andclosed-chain condensation products ; from such mixtures representa-tives of the following types have already been isolated:By ROBERT ROBISON and FREDERIC STANLEY KIPPING.HO*SiR,*O*SiR,-OH8iR,,<0.8iR 0- Si K 2>oHitherto very little attention has been paid to the conditionsunder which each of these different types of condensation productis formed; the mixtures of these compounds were obtained more orless by chance during the preparation or purification of the diols.Now the importance of gaining further information respectingthese condensation products need hardly be emphasised ; the studyof the reactions by which they are formed cannot fail t o throw somelight on the processes, doubtless of an analogous character, whichlead to the production of the complex mineral silicates.For this reason we have continued our investigations alongvarious lines, and Pave more particularly directed our attention toan examination of (a) the conditions under which the diols undergocondensation, ( b ) the conditions under which the open-chain areconverted into closed-chain compounds, and ( c ) the comparativereadiness with which the closed-chain compounds containing two,three, or four atoms of silicon respectively are formed.The resultsobtained from the study of dibenzylsilicanediol and its condensationproducts are described in this paper.Dibenzylsilicanedio: is very readily acted on by various reagents(p. 41), giving, as a rule, a mixture of anhydrobisdibenzylsilicane-diol and trianhydrotrisdibenzylsilicanediol.The former compounddoes not seem t o yield any further condensation product by thedirect elimination of the elements of water ; so far, we have not beeORGANIC' DERIVATIVES OF SILICON. PART XX. 41able to prepare from it either dianhydrobisdibenzylsilicanediol,0 Si(CH,Ph)<o> Si( CH,Ph),, or the analogue of tetra-anhydrotetra-kisdiphenylsilicanediol. In alcoholic solution, however, in presenceof hydrogen chloride, anhydrobisdibenzylsilicanediol is transformedinto trianhydrotrisdibenzylsilicanediol ; this change is doubtlessdependent on the hydrolysis of some of the anhydrobisdibenzyl-silicanediol to dibenzylsilicanediol, but whether the trianhydro-coinpound is formed by the subsequent condensation of the dibenzyl-silicanediol Q ith the unchanged anhydrobisdibenzylsilicanediol, ' orby the direct condensation of three molecules of the simple diol, isnot known.Dianhydrotrisdibenzylsilicanediol,HO*Si(CH2Ph),*O*Si(CH,Ph)2*O*Si(CH2Ph)2*OX3,the analogue of dianhydrotrisdiphenylsilicanediol, may be obtainedby carefully hydrolysing trianhydrotrisdibenzylsilicanediol withpotassium hydroxide or hydrogen chloride in acetone solution ; itis readily converted into trianhydrotrisdibenzylsilicanediol by tracesof hydrogen chloride in alcoholic solution.These facts show thatthe hydrolysis and formation of these closed oxy-silicon chains areeasily reversible reactions under the given conditions; it may alsobe concluded that the closed chain composed of three silicon andthree oxygen atoms alternately linked together, is more easilyformed than those containing either two or four atoms of both ofthese elements.EXPERIMENTAL.Dib ei.mylsilicamedio1.Dibenzylsilicanediol is converted into anhydrobisdibenzylsilicane-diol when it is heated at about l l O o (Zoc.cit., p. 2148), treated withhydrogen chloride in alcoholic solution (Zoc. cit., p. 2150), ortreated with acetyl chloride; in the last two cases trianhydrotris-dibenzylsilicanediol is also formed and may even be the principalproduct, but no other crystalline substance has been isolated fromthe oily matter, which is usually produced from the diol in theseand other experiments.Dibenzylsilicsnediol is also condensed by alkalis ; when a solutidnof the diol in a 6 per cent.solution of sodium hydroxide is kepta t the ordinary temperature exposed to the air, in the course of aday o r two it deposits an oil, soinetimes a solid, which is insolublein a dilute aqueous solution of sodium hydroxide, but completelysoluble in cold ethyl alcohol; this product is t.herefore probably amixture of anhydrobisdibenzylsilicanediol and dianhydrctrisdi-benzylsilicanediol (p. 43). I f , however, the alkaline solution i42 ROBISON AND KIPPING :heated a t about looo during some hours, the precipitate is onlypartly soluble in cold alcohol, and contains a considerable propor-tion of trianhydrotrisdibenzylsilicanediol.The separation of these condensation products from a cold alkalinesolution of the diol certainly takes place more quickly in thepresence than in the absence of air; it is improbable, however,that the atmospheric carbon dioxide has any direct action exceptthat of diminishing the concentration of the sodium hydroxide.Apparently the solution contains the sodium derivative, orderivatives, of the diol in equilibrium with a very small quantityof one or more of the condensation products of the diol:Si(CH,Ph),(ONn), + H29 ++ Mi(CIT2Ph),(ONa)*OH + NaOHH,O + 2Si(CH2Ph),(ONa)*OH ++EO*Si(CH,Yh),*O*Si(CH2Ph)2*0 H + 2Na0 €1,and the conversion of the alkali into carbonate merely disturbs theequilibrium.The behaviour of all the other diols towards dilute solutions ofalkali hydroxides appears to be similar to that of the dibenzylcompound, but except in the case of diphenylsilicanediol, the con-densation products have not been isolated; it would also seem thatdibenzylstannanediol undergoes condensation under similar con-ditions (Smith and Kipping, T., 1913, 103, 2034).Dibenzylsilicanediol also undergoes condensation when its alcoholicsolution is treated with a drop or two of piperidine; trianhydro-trisdibenzylsilicanediol is formed, together with an oil, the com-ponents of which have not keen' isolated.Anhtydrobisdib enaylsilkcanediol.Several further attempts have been made t o convert this com-pound into dianhydrobisdibenzylsilicanediol, o<s' s, (C (cH H2Ph 2Ph), '2>0,or tetra-anhydrotetrakisdibenzylsilicanediol, but without success.Acetyl chloride, as already stated (Zoc. cit., p.2154), seems to havelittle or no action on the compound; in a recent experiment asolution of anhydrobisdibenzylsilicanediol in excess of the acidchloride was kept during some months and then evaporated, but theoily residue was readily and completely soluble in ethyl alcohol, andappeared to be free from higher condensation products.Thealcoholic solution subsequently deposited crystals of trianhydro-trisdibenzylsilicanediol, but this compound liad probably beenformed by the action of traces of hydrogen chloride on anhydrobis-dibenzylsilicanediol (see below).The behaviour of anhydrobisdibenzylsilicanediol towards alkaliORGANIC DERIVATIVES OF SILICON. PART XX. 43was also examined in alcoholic solution, but crystalline compoundscould not be isolated from the oily product which was formed inthe course of some days. The action of piperidine in alcoholicsolution was similar to that of potassium hydroxide, and led tothe formation of an oily condensation product.Anhydrobisdibenzylsilicanediol was also heated with phosphoricoxide ; the oily product was completely soluble in ethyl alcohol,and apparently did not contain trianhydrotrisdibenzylsilicanediol inappreciable quantity.When, however, an alcoholic solution ofanhydrobisdibenzylsilicanediol, to which a few drops of concentratedhydrochloric acid had been added, was kept at the ordinarytemperature, cryst.als of trianhydrotrisdibenzylsilicanediol weredeposited in the course of twenty-four hours. It must therefore beconcluded that the anhydro-derivative is hydrolysed by the hydro-chloric acid, giving dibenzylsilicanediol, which then undergoes con-densation under the influence of the same reagent.Dianhydro t risdi b enzy lsilicanedio 2,HO*Si(CH,Ph),*O*Si( CR,Ph),-O*Si(CH,Ph),*OH.Although this compound is very probably present in the oilswhich are formed by the action of dilute alkali hydroxides ondibenzylsilicanediol and on anhydrobisdibenzylsilicanediol, it hasnot yet been isolated from these products.Attempts were thereforemade to prepare it by the hydrolysis of trianhydrotrisdibenzyl-silicanediol in accordance with the equation :The trianhydro-derivative, although practically insoluble inalcohol, slowly dissolves in an alcoholic solution of potassiumhydroxide a t the ordinary temperature, owing t o the occurrence ofhydrolysis ; from freshIy prepared solutions water precipitates asolid, and the filtered solution gives with acetic acid a precipitate ofdibenzylsilicaiiedioL An examination of the solid obtained in thisway from the alkaline solution showed that it consisted of anhydro-bisdibenzylsilicanediol, or of a compound melting a t 8 2 O , or of amixture of these two substances, and that its nature varied withthe conditions of the experiment, owing to the occurrence of pro-gressive hydrolysis. I n order t o find a suitable method for thepreparation of the compound melting a t 82O, which was the desireddianhydro-derivative, various experiments were made under differentconditions; the results showed that with the aid of acetone, i44 ROBISON AND KIPPING :which trianhydrotrisdibenzylsilicanediol is readily soluble, theprimary product of hydrolysis is readily obtainable as follows :A solution of trianhydrotrisdibenzylsilicanediol in cold acetoneis treated with a 3 per cent.solution of potassium hydroxide(2 mols.), and thirty seconds afterwards a slight excess of diluteacetic acid is added. The solution is then further diluted withwater, and the Qily precipitate is separated by filtration or extractedwith ether. The ethereal solation of the oil is mixed with lightpetroleum and left t o evaporate; the crystals which separate arethen recrystallised several times from a mixture of the two solventsjust mentioned.Dianhydrotrisdib enzylsilicanediol is thus obtained in large,transparent crystals, melting at 8 2 O ; the samples for analysis weredried over sulphuric acid:0.1899 gave 0,5019 CO, and 0.1088 H,O.C = 72.2 ; H =: 6.4.0.1733 ,, 0.4600 CO, ,, 0.0993 HZO. C=72*4; H=6*4.C42H4404Si3 requires C = 72'3 ; H = 6.3 per cent.Molecular-weight determinations were made by the cryoscopic0.253, in 13.55 grams of benzene, gave At - 0'12O.0.446, ,, 13'55 ,, >, ,, At -0.21'. M.W. =771.These results agree only moderately with the calculated molecularweight (C,,H,,O,Si, requires M.W. 696), and indicate a consider-able degree of association in benzene solution ; in this respect theycorrespond closely with the values obtained under similar conditionsin the case of other condensation products of this character, suchas anhydrobisdiphenylsilicanediol and dianhydrotrisdiphenyl-silicanediol (Kipping, Zoc.cit., p. 2132, 2134); they may thereforebe regarded as satisfactory.Dianhydrotrisdibenzylsilicanediol is readily soluble in ether oralcohol, and in all the other common organic solvents with theexception of cold light petroleum, in which it is only sparinglysoluble; it is practically insoluble in water, and also in a colddilute solution of potassium hydroxide.It is obvious from the above-descriked method of preparation ofdianhydrotrisdibenzylsilicanediol that the rupture of the closedchain contained in the trianhydro-derivative takes place veryrapidly under the influence of the potassium hydroxide, whereas thefurther hydrolysis, which results in the formation of anhydrobis-dibenzylsilicanediol and dibenzylsilicanediol takes place more slowly.Although the above-mentioned quantity of the alkali was generallyused, the proportion of this substance seemed to be of much lessimportance than the time during which hydrolysis was allowedmethod in benzene solution :M.W.= 761ORGANIC DERIVATIVES OF SILICON. PART XX. 45to proceed. If, for example, more than a few minutes elapsebetween the addition of the alkali and that of the acetic acid, theproduct always contains a considerable quantity of dibenzylsilicane-diol, even when only two molecular proportions of potassiumhydroxide are present.Hydrolysis of Trianhydrotrisdibenz.?llsilicanediol with HydrogecnC it Eorid e.It has already been shown that dibenzylsilicanediol is slowlyconverted into trianhydrotrisdibenzylsilicanediol when it is treatedwith concentrated hydrochloric acid in alcoholic solution (loc. cit.,p.2150), and that under similar conditions anhydrobisdibenzyl-silicanediol is aiso transformed into the same condensation product.I n the latter case it is clear t,hat hydrolysis of the anhydro-derivative must precede condensatibn ; the reaction brought aboutby the hydrochloric acid is therefore a reversible one, and the pro-duction of trianhydrotrisdibenzylsilicanediol in almost theoreticalquantities is determked merely by the insolubility of the latter inalcohol. Experiments were therefore made to ascertain whetherunder suitable conditions trianhydrotrisdibenzylsilicanediol couldbe hydrolysed with hydrochloric acid; it was thus found that thetrianhydro-derivative could be converted into dianhydrotrisdibenzyl-silicanediol in the following manner.Trianhydrotrisdibenzylsilicanediol is dissolved in acetone andone drop of concentrated hydrochloric acid is added; after abouthalf an hour's time the solution is diluted with water and stirredvigorously.The precipitated solid is separated by filtration, andextracted with cold alcohol, which leaves a residue of unchangedtrianhydrotrisdibenzylsilicanediol ; the alcoholic solution is thendiluted with water and the oily precipitate extracted with ether.The ethereal solution contains dianhydrotrisdibenzylsilicanediol,which is purified by recrystallisation from a mixture of ether andlight petroleum. I n this way only about 15 per cent.of thetrianhydro-derivative is transforzed into the dianhydro-compound,but by submitting the unchanged substance to the same treatmentagain, further quantities of the dianhydro-compound may beobtained.It might be concluded therefore that in acetone solution thehydrolysis of trianhydrotrisdibonzylsilicanediol by hydrogen chlorideis a reversible reaction 46 ROBISON AXD KIPPING :and that under the conditions described above, equilibrium isattained when the proportion of dianhydrotris- to trianhydrotris-dibenzylsilicanediol is about 1 : 5 or 1 : 6. Probably the aboveequation expresses only one of several reversihle reactions whichoccur, others being the following :2Si(C M,Yh),(O H )2 t+ HO*Si(C H2Ph),*0.Si(r;’H,Ph)2*OH + H,O.Conversion of Di- into Tri-anhydrotrisdib enzylsilicanediol.If the formation of dianhydrotrisdibenzylsilicanediol from thetrianhydro-derivntive in the manner just described is really areversible reaction, then in alcoholic solution the change expressedby the above equation should proceed almost completely from rightto left, owing to the insolubility of the trianhydro-compound inalcohol.When an alcoholic solution of dianhydrotrisdibenzylsilicanediol,to which a drop of concentrated hydrochloric acid has been added,is kept a t the ordinary temperature, it soon deposits a crystallineprecipitate, melting a t 98O, which consists of pure trianhydrotris-dibenzylsilicanediol.A quantitative experiment, made in the following manner, showedthat the change is practically complete.A known quantity ofdianhydrotrisdibenzylsilicanediol, contained in a weighing bottle,was dissolved in alcohol, t o which one drop of concentrated hydro-chloric acid had been added; after the solution had been kept forabout twelve hours, during which time it deposited crystals oftrianhydrotrisdibenzylsilicanediol, it was evaporated in a desiccatorover sulphuric acid and potassium hydroxide, and the residue wasdried a t about 90° until constant in weight. The loss amountedto 2.48 per cent., against a theoretical loss of 2.58 per cent.Dianhydrotrisdibenzylsilicanediol also undergoes condensation inalcoholic solution in presence of a trace of sodium hydroxide, evenmore readily than in presence of hydrogen chloride; within anhour, crystals of trianhydrotrisdibenzylsilicanediol are depositedfrom the solution.Acetic anhydride seems to nave little action on dianhydrotris-dibenzylsilicanediol ; a small quantity of the compound was heatedwith this reagent for a short.time, but was afterwards recoveredunchanged.I n one experi-ment the residue obtained by evaporating an acetyl chloride solutionof the dia nhydro-compound a t the ordinary temperature was treatedThis conclusion was fully confirmed by experiment.The action of acetyl chlorida was also studiedORGANIC DERIVATIVES OF SILICON. PART XX. 47with alcohol ; i t yielded crystals of trianhydrotrisdiberizylsilicane-diol. I n another experiment, a weighed quantity of the substancewas gently warmed with a small amount of acetyl chloride untilthe latter had evaporated, apd was then heated t o 1 1 0 O ; no loss inweight, however, could be detected. The same sample was againtreated with acetyl chloride, and after the latter had beenevaporated, the residue was heated to about 125O in the courseof forty-five minutes.The total loss in weight was 2.9 per cent.,the theoretical loss for one molecule of water being 2.6 per cent.When the residue was warmed with alcohol, it gave a sparinglysoluble powder, which separated from a mixture of ether and lightpetroleum in crystals melting a t 98O. These results prove thatdianhydro- may be converted into trianhydro-trisdibenzylsilicanediolby the treatment described, but they do not show whether it isthe- acetyl chloride itself which brings about condensation, orthe traces of hydrogen chloride which are doubtless formed in thecourse of the experiment.Effect of Hent o n Dirtnh,ydrotrisdibenzylsilica~ed~ol.Although dianhydrotrisdibenzylsilicanediol is so readily convertedinto the closed-chain compound by acids or alkalis, this changecannot be satisfactorily accomplished by merely heating thedianhydro-compound (in the air).Quantitative experiments showedthat a t 130° only a very slow loss in weight took place; a t highertemperatures, the loss was more rapid, but the residue had a strongodour of benzaldehyde, probably owing to atmospheric oxidation.In one case, during one hour a t 175O, 0.3125 gram of substancelost 5.4 per cent., but there was no indication of a constant weighthaving been attained; as the theoretical loss for one molecule ofwater is only 2.58 per cent., more than one-half of the observedloss was doubtless due to the volatilisation of the benzaldehydeformed by atmospheric oxidation.The residue yielded less than0.1 gram of trianhydrotrisdibcnzylsilicacediol, together with an oilfrom which crystah of dianhydrotrisdi benzylsilicanediol (m. p. 82O)were isolated.Trianh ydro trisLil: b enzy lsilican ediol.Crystals of this compound deposited from a mixture of chloroformand light petroleum have been examined for us by Mr. VernonStott under the direction of Mr. A. Hutchinson, M.A., of themineralogical laboratory, Cambridge ; we are indebted to thesegentlemen for the following report 48 ORGANIC DERIVATIVES O F SILICON.PART XS.System : oblique. Sub-class : holohedral.Forms developed: a{100}, c{OOl), m{110}, s{101}, T{TOl).Table of angles :a : b : ~ = 2 ' 7 9 7 : 1 : 1.643 ; 6 =94'38'.Angle.100 : 101101 : 001100 : $01001 : lo1To1 : loo100 : 110101 : 110110 : i i o101 : 110- 031 : 110Number ofmeasurements. Limits.9 59"dO'-6O01 1'9 25 14 -26 139 85 2 -85 4011 27 2 -28 49 66 31 -67 423 70 0 -70 3633 80 0 -80 3316 39 11 -39 4342 88 13 -88 5447 96 59 -97 58Mean.59"43'25 3885 2227 3866 5170 1 480 1539 2888 3097 33Calculated.59'29'25 5327 4770 1680 388 2i97 38---The crystals are prismatic in habit, being elongated in a directionThe ?ii faces are in general muchAt our request, Dr. I. M. I-Teilbroa has very kindly photographedperpendicular t o t.he diad axis.larger than the a faces.Oscillatioit frequcncies.32 31 36 38 400042 44 46Pull curve : Dibenzylsiticanediol i?z alcohol, with or wilhoztt alknli.Dot curve : Anhydrobisdibenzylsilieancdiol in alcohol.Dash curve : Dianhydrotrisdibemylsilieanediol in nlcoitol.Dash-dot curve : l'riunhydrotrisdibenzylsilica~~ediol in chloroforin.the absorption spectra of dibenzyl.silicanedio1 and of the variouscondensation products of this diol, which, so far, have been preTHE OPTICAL ROTATORY POWER, ETC. 4 9pared. From the curves, which are given in the accompanyingdiagram, i t will be seen that the spectra of all the four compoundsare very similar, and show one fairly broad band, which covers theregion of the first four or five bands shown by benzene (Baly andCollie, T., 1905, 87, 1332). In the case of those compounds whichcontain four or six benzyl groups, this band is found at lowermolecular concentrations than in the case of dibenzylsilicanediolitself. It will also be seen that the addition of alkali t o thealcoholic solution of the last-named compound brings about noalteration in the absorption spectrum.The authors are indebted to the Government Grant Committee ofthe Royal Society for a grant in aid of this investigation.UNIVERSITY COLLEGE,NOTTINQH AM

ISSN:0368-1645    

DOI:10.1039/CT9140500040

出版商:RSC    

年代:1914

数据来源: RSC

摘要:

THE OPTICAL ROTATORY POWER, ETC. 4 9MI.-The Optical Rotatory Power of Dwivatives ofSuccinic Acid in A queous Solutions of InorganicSalts. Part I.By GEORGE WILLIAM CLOUGH.WORKERS on thO Walden inversion have been confronted by thefundamental difficulty that there are a t present no means ofascertaining whether, when a group attached to an asymmetriccarbon atom of an optically active compound has been displacedby another group, a change of configuration has or has notoccurred. For example, in the transformation I-malic acid 2d-chlorosuccinic acid -+ &malic acid it is impossible to statewhich of the two reactions is accompanied by a change of con-figuration. The various hypotheses that have been advanced inexplanation of the phenomenon are concerned with the mechanismof the reaction, but, its Frankland stated in his PresidentialAddress, (‘ unfortunately all the attempts which have hitherto beenmade to apply these explanations to specific cases have been singu-larly unfruitful ” (T., 1913, 103, 726).In his investigation of therelative effects of the various reagents that have been employed,Frankland makeis the tentative hypothesis that the change of signwhich almost invariably accompanies the action of phosphoruspentachloride o r phosphorus pentabromide is, in the absence ofevidence to the contrary, to be regarded as betraying a change ofAg20VOL. cv. 50 CLOUGH: OPTICAL ROTATORY POWER OF DERIVATIVES OFconfiguration. The same author, however, emphasises the possibilitythat, notwithstanding the usual change in sign, the action ofphosphorus pentachloride may be a ‘‘ normal ” action.It is evident,therefore, that, until confirmatory evidence is forthcoming, thissuggestion can only be accepted with the greate& reserve.The present investigation has been undertaken in the hope thata study of the influence of solvent, concentration, and temperaturerespectively on the rotation of certain similarly constituted com-pounds of the same configuration will reveal regularities which maybe subsequently utilised for the dgtermination of configurativerelations in doubtful cases. The large amount of experimentalmaterial already accumulated in this field exhibits few regularitieswhich may be justifiably employed for this purpose.Frankland,however, has used the method in order to prove that the esters ofaj3-dichloropropionic acid obtained by the action of phmphoruspentachloride on the lzevorotatory esters of glyceric acid haveidentical configurations. Ahhough the higher esters obtained areoptically opposite t o the methyl ester, they are configurativelysimilar to the latter, inasmuch as rise of temperature diminishestheir lzvorotation, but increases the dextrorotation of the methylester (Zoc. cit., p. 718).The present author proposes t o make a comparative study of therotation of optically active derivatives of succinic acid in the purecondition, in aqueous solution and in aqueous solutions of certaininorganic salts. The rotatory power of many derivatives of succinicacid is particularly msceptible to the influence of solvent, concen-tration and temperature, and it appears to be more than a coinci-dence that compounds which exhibit the phenomenon of anomalousrotatory dispersion usually possess rotations which vary widelywith the conditions under which they are measured.The influenceof a large number of electrolytes on the rotation o€ aqueous 2-malicacid a t a constant temperature has been investigated by Stubbs(T., 1911, 99, 2265), whilst Patterson and Anderson have studiedthe effect of inorganic salts on the rotatory power of ethyld-tartrate (T., 1912, 101, 1833).I n the present paper the effects produced by sodium and bariumhaloids on the rotation of aqumus solutions of d-tartaric acid,methyl d-tartrate, ethyl d-tartrate, and d-tartramide respectively a tvarious temperatures are described.The results bear a strikingresemblance to those obtained by Stubbs and by Patterson andAnderson. The salts employed cause a relatively large depressioiiof the dextrorotation of theBe compounds in aqueous solution, andin some instances they cause a reversal of the sign of rotation.The curves in Fig. 1 represent the rotation of tartaric acid iSUCCINIC ACID IN AQUEOUS SOLUTIONS OF INORGANIC SALTS. 51FIU. 1.Tartaric Acid.--4T.11.1x1.IV.V.0 10 20 30 40 50 60l'emnperattere.I. Watcr (p=16'67).11. Water (~'50).111. Aqz~eous sodium chloride (~~13.95).1V. AqzLeous sodiwm chtoride (p = 44.76).V. Tmrtaric acid.The aqueous sodium chloride contains 11.7 grams of sodium chloride in50 grams of water52 CLOUGH: OPTICAL ROTATORY POWER OF DERIVATIVES OFaqueous solution and in aqueous sodium chloride.The dextro-rotation of an aqueous solution of tartaric acid increases consider-ably both with dilution and with rise of temperature. Althoughthe specific rotation of sodium hydrogen tartrate in aqueous solutionis higher than that of tartaric acid, the rotation of tartaric acid inaqueous sodium chloride is much less than in aqueous solution.It is again obvious from the curves that the more dilute solutionof tartaric acid in aqueous sodium chloride has a greater rotationthan the more concentrated solution, and that the temperature-coefficients for all the solutions are positive. For the sake ofcomparison, the values calculated by Winther by extrapolationfor the rotation of tartaric acid in the pure state are representedby the dotted curve (Zeitsch.physikal. Clhem., 1902, 41, 161). Thedepression of rotation caused by sodium bromide is greater thanthat caused by sodium chloride, but less than that caused bysodium iodide. These salts thus exert the same relative effects onaqueous tartaric acid as on aqueous ethyl tartrate (Patterson andAnderson, Zoc. cit.). Stubbs similarly observed that potassiumiodide influenced the rotation of malic acid to a greater extentthan potassium bromide, which in turn had a greater effect thanpotassium chloride. Moreover, these regularities extend to theinfluence of barium haloids, which cause a greater alteration inthe rotation than equivalent quantities of the correspondingsodium salts.The rotation curves for methyl tartrate in the pure condition,in aqueous solution, and in aqueous sodium chloride, are drawn inFig.2. The curves for the pure ester and for the aqueous solutionsare drawn from the valuable data given by Patterson. The dissolu-tion of methyl tartrate in water considerably raises the rotation ofthe ester, and whilst the temperature-coefficient for the pure esteris positive, that for the aqueous solution is negative. The presenceof sodium chloride in the aqueous solution has a remarkable effect,for not only is the rotation greatly reduced, but rise of temperatureis now accompanied by an increase of rotation. The influence ofbarium bromide on the rotation of aqueous methyl tartrate is againmuch greater than that of sodium chloride.The curvea for ethyltartrate are very similar to those for the methyl ester. Patterson’scurves for the pure ester and for the aqueous solution, which arereproduced in Fig. 3, show that the rotation of the ester is muchgreater in aqueous solution than in the pure condition. The specificrotation in aqueous sodium chloride, however, is lower than thatof the pure ester, but the temperature-coefficients are now similar.The relative effects of barium bromide and sodium chloride on therotation of ethyl tartrate are of the same order as those of thesSUCCINIC ACID IN AQUEOUS SOLUTIONS OF lNORGANIC SALTS. 532220i a1614.$ 12uu 2 s u” 1c0ae440FIG.2.Methyl tartrate.710 20 30 40 50 00 70Temperature.I. Water (p=5-17).11. Water (p=49-8).111. Aqueozu sodiicm chloride ( ~ ~ 4 . 0 4 4 ) .IV. Methyl tartrate.V. Aqueous sodium chloride ( p = 43‘02).The aqueous sodium chloride contains 5 *85 grams of sodium chloridein 20 grams of water,I I.1x1.I v.1754 CLOUGH: OPTICAL ROTATORY POWER O F DERIVATIVES OFsalts on tartaric acid and methyl tartrate. The comparatively large1zvorota.tion of methyl and ethyl tartrates in aqueous bariumbromide at low temperature is particularly noticeable.The other derivative of tartaric acid which has been examinedFIG. 3.Ethyl tartrate.10 20 30 40 50 60Temperature.I. Water (p = 50).11. Ethyl tartrate.111.Aqueozcs sodium chloride (p=43%2),IV. Aqueous barium bromide (p=36.45).The aqueous sodium chloride contains 5.85 grams of sodium chloride in 20 gramsof water and the aqueous barium bromide contains 14.86 grams of barium bromidein 20 grams of water.is tartramide. This compound is only sparingly soluble in water,but the aqueous solution is strongly dextrorotatory. The dextro-rotation is diminished by sodium chloride, and still more eo bybarium bromide. Increase of temperature slightly reduces thSUCCINIC ACID IN AQUEOUS SOLUTIONS OF INORGANIC SALTS. 55specific rotation, both in aqueous solution and in aqueous sodiumchloride.In order to account for the results obtained in the case of malicacid Stubbs advanced the view that the influence of the salts ismainly due to a direct and distinctive power possessed by theinactive molecules in solution to affect the asymmetry of the activeones within their sphere of influence without actual chemicalcombination.Patterson and Anderson maintain that the influence of inorganicsalts is of the same order ag that of organic solvents.Some yearsago Patterson suggested that there was a relation between therotatory power of a substance in a given solvent and the internalpressure of that solvent. This pressure, it was pointed out, wouldchange the volume and also the shape of an asymmetric molecule,but as the shape of the molecule conditions the value of therotation, alteration of volume would be accompanied by changeof rotation (T., 1901, 79, 189).It would thus appear that thereis little difference between the explanation put forward by Stubbsand that previously advanced by Patterson for the more generalcase. In a recent paper Patterson expresses the belief “that thepotentialities of the asymmetric carbon atom and of the most simplephysical conceptions of those inter-molecular forces to which lique-faction is due are ample to account for all the observed behaviour ”(T., 1913, 103, 173).This conception implies that a gradual alteration of temperatureor concentration, o r the gradual addition of an inactive substanceproduces a corresponding gradual alteration in the shape or asym-metry of the molecules, and consequently a change of rotation.Although this hypothesis may explain the changes of rotation inmany cases, i t appears to be inadequate to account for the greatvariations in the rotation of such compounds as tartaric acid andits esters, or for the phenomenon of anomalous rotatory dispersion.More than sixty years ago Biot showed that a substance whichexhibits anomalous rotatory dispersion behaves in this respect inprecisely the same way as a mixture of two substances havingopposite rotations and different dispersive powers (Ann.Chim.Phys., 1852, [iii], 36, 405). This interesting suggestion has beenrecently elaborated by Armstrong and Walker (Proc. Roy. SOL,1913, A , 88, 388), who advance the hypothesis that substancespossessing anom alouz rotatory dispersive power consist of iso-dynamic forms having different rotatory powers ; for example, anaqueous solution of d-tartaric acid contains an equilibrium mixtureof a dextrorotatory form and a lzevorotatory form, the formerpreponderating at high temperatures and in dilute solution56 CLOUGH: OPTICAL ROTATORY POWER OF DERIVATIVES OFInasmuch as the equilibrium is conditioned by solvent, concentra-tion, and temperature, change of rotation is also dependent ont h a e factors.The present author believes that this is the mostsatisfactory explanation that can be advanced a t present to accountfor the large variations of rotation described in this paper. It isevident that the presence of certain inorganic salts in aqueoussolution profoundly alters the equilibrium of the two isodynamicforms. The reason for the great difference between water andaqueous salt solutiom is not a t present clear.The influence ofthe salts is certainly opposite to that of dilution, but the rotationof ethyl tartrate in aqueous sodium chloride may be less than thatof the ester in the pure condition. The rotation curves of theesters of tartaric acid indicate that the influence of temperature isnot always the same, for in some solvents the temperature-coefficientis positive, whilst in others the coefficient is negative.An interesting point which appears to have received little atten-tion is the phenomenon exhibited by some opticdly activecompounds of possessing, under certain conditions, no rotation. Ifthe asymmetry of the molecule is the cause of optical activity itis difficult to conceive how a solution of similar asymmetricmolecules could be optically inactive. The hypothesis of Armstrongand Walker, however, presents a ready solution of the difficulty.Under such conditions the rotations of the isodynamic formsexactly counterbalance one another.Armstrong and Walker suggest four possible formuls for theisodynamic forms of tartaric acid:C*OH C(OH),CH*OH/\\/YHooH 0 CH*OH Ho>C CH*CO,H p**" \/ co 0 C0,H C-OH(1.) (11.) (111.) UV.1but consider that the forms preponderating in aqueous solution arerepresented by the carboxylic formula (I) and the lactonic formula(111).There can be little doubt but that the dextrorotatory formof d-tartaric acid is represented by the carboxylic formula, butthere is little evidence in support of the lactonic formula for thelaevorotatory isodynamic form of d-tartaric acid.It seeme probablethat further work on the rotatory powers and rotatory dispersionsof similar compounds will throw some light on the constitutionof the latter form. The hypothesis should prove a useful guidein the investigation of the rotatory power of other derivatives ofsnccinic acid on which the author is at present engagedSUCCINIC ACID IN AQUEOUS SOLUTIONS OF INORGANIC SALTS. 57EXPERIMENTAL.In order that the results might be comparable with those ofother workers, the solutions have been prepared in such a mannerthat, whilst the weights of active substance and water are keptconstant, the weights of the salts added are equivalent; thus therotation of tartaric acid in water (p=16*667) should be comparedwith that in aqueous sodium chloride (p=13'95).Tartaric Acid i m Water.Tartaric acid (10 grams) in water (50 grams).t ..........14". 20.5". 29". 39". 50". 59". 69'. 80".(1?=4) ... +8'34 8.91 9.57 10'21 10.77 11'12 11'48 11.78[a]: ......... + 11-58 12.41 13.38 14.34 15.20 15.75 16-32 16.83Densities determined : t . . . ... 13". 23". 40". 55" 72"d...... 1.080 1.076 1.068 1-061 1'054p = 16.667 :dt ............ 1'080 1.077 . 1.073 1.068 1.063 1.059 1,055 1-050Tartaric acid (50 grams) in water (50 grams).t.... ........... 16.5". 30". 36". 48".d ............ 1'272 1.261 1.256 1.247a; (1=2) ... +8.76 10.95 11.90 13.50[alt ......... +6'89 8.68 9'47 10'83Densities determined : t ......23". 35". 55".d ... 1.266 1.257 1.243.p= 50.00 :Tartaric Acid in Aqueous Sodium Chloride.Tartaric acid (10 grams) and sodium chloride (11.7 grams,1 /5 gram-mol. weight) in water (50 grams),p= 13-95 :t ..................... 7". 15". 30". 46". 56". 64".cl ..................... 1.207 1-202 1.193 1.184 1.178 1.173a', (1=2) ........ - 0.08 +0'51 1.36 2.06 2-37 2-64[a]: .................. -0.24 +1*52 4.09 6'24 7'21 8.07Densities determined : 1 ...... i6". 31" 47". 64".d ...... 1.201 1.193 1.183 1'173Tartaric acid (50 grams) and sodium chloride (11.7 grams)in water (50 grams).p = 44.76 :t ..................... 16". 18". 27.5". 38". 54".d ..................... 1.333 1-332 1.327 1.320 1.309a', (Z=2) ...........- 0.20 i-0.22 2-26 4-22 6'52[a][, ................. - 0.17 f 0 . 1 8 1-90 3.58 5.56...... Densities determined : t 24". 40". 53".d ...... 1.329 1'318. 1.3058 CLOUGH: OPTICAL ROTATORY POWER OF DERIVATIVES OFTartaric Acid in Aqueous Sodium and Barium HaIoids.Tartaric acid (10 grams) and ths respective weights of anhydrousSalk in water (50 grams).Weiglr t Gram-mol.Salt. of salt. weight. p . d'f. a?(Z=2). [a]:?.Sodiumchloride ... 5%5 15'19 1.136 +2%3 + 7 ~ ...... 13.95 1.196 - 3.30'$ 9 13'43 1217 0 *67 1'90 .... 14.22 1.200 2 40 7-03,) 11 -70) ) 14-62)) bromide.. 10 *3 27J ,) 20% 12.41 1.309 0 70 2.159 ) 11.66 1.363 0 *07 0.22 ...... 1.71 5-11 ) ) iodide 15.0 cv 13'33 1.2579 7 )) ..... 37 5 10'26 1'482 -0.87 -2.88Barium chloride ......10.41 2n 14-20 1.223 -0'55 - 1.58,) bromide ..... 14-84 23 13.36 1.286 -0.80 -2'342 ) ,, ...... 37'2 n 10'29 1'564 -3'34 -10.88* Interpobted.) ? ...... !...... $ 9- ...... ,) 25-76 I2 9 ), ...... 29 72 2s 11.15 1.468 -2'89 - 8 831.................. + 12.98* None.. - I 16.67 1-075 -MethyI Tartrate in Aqueous Sodium Chloride.The methyl tartrate used gave a: ( I = 2 ) + 5.70°. Methyl tartrate(1.09 grams) in water (20 grams), p=5*17; weight of sodiumchloride added, 5.85 grams.p = 4'044 :t ....................... 18". 27". 35.5". 43".d ........................ 1'178 1.173 1'168 1.165a: (1 = 4) .............. + 1-16 1.31 1 '44 1.51[a] .................... +6'08 6'89 7'62 8 -33Densities deteimined : t ...... 17". 27". 41".d ...1.179 1'173 1.166Patterson's values for methyl tartrate in water (p=5-17) are:[ C Z ] ~ ' ~ + 21.10°, [a]E' 20*81°, 20.2a"(T., 1904, 85, 1150).Methyl tartratep=43*62 :(20 grams) and sodium chloride (5.85 grams)in water (20 grams).t ..................... 16". 18.5". 23". 35". 49".d .................... 1.254 1.252 1.249 1-240 1-229ak(Z=2) ............ +0'80 0'86 1-32 2'24 3'11Densities determined : t ...... 17". 29". 40".[u]: .................. +0.73 0.80 1-21 2-07 2.90d ... 1.253 1.245 1'23SUCCINIC ACID IN AQUEOUS SOLUTIONS OF INORGANIC SALTS. 59Methgl Tartrate in Aqueous Barium Bromide.Methyl tartrate (20 grams) and barium bromide (14.86 grams)in water (20 grams).p = 36-45 :t ......................... I f " . 29". 36".d ..........................1.473 1,464 1.468~4,(Z=2) .................. -12.69 -- 10*79 - 9.66[uJ; ........................ - 12-02 - 10.11 - 8-93Densities determined : t ...... 13". 24". 35".d .. 1476 1'468 1.459Patterson's values for pure methyl tartrate are:[a]E* + 1*83', [a]: 2 07", [a]:" 2 * 6 4 O , [a]$"s 3-60',and for aqueous methyl tartrate (p=49*77) :(T., 1904, 85, 766, 1150).+ 14.710, ~ ~ 1 ~ 3 14.590, [ . 1 ~ ' 7 14.130Ethyl Tartrate in Aqueous Sodiam Chloride.Ethyl tartrate (20 grams) and sodium chloride (5.85 grams)in water (20 grams).t ........................ 17". 28". 36". 50".d ........................ 1.202 1.193 1.187 1.176p=43*62:a4, (Z=2) .............. + 2.30 3'22 3-86 5-04[a]: ..................... +2*19 3-09 3.73 4-92Densities determined : t ......18". SO". 44".d ... 1.202 1-192 1.181Ethyl Tartrate in Aqueous Bariam Bromide.Ethyl tartrate (20 grams) and barium bromide (14.86 grams)in water (20 grams).t ..................... 15". 38". 45". 29".a? ................... 1-430 1.409 1-403 1-418p=36*45 :~E,(2=4) ............ -16'54 10.84 8-74 12-84[a]; .................. -7'93 5-03 4-27 6.21Densities determined : t ...... 15". 26.5". 41'.d ... 1'430 1.420 1'407ThO following are Patterson's values for the pure ester (T., 1913,103, 173):[a]", + 7-64', [ c c ] ~ ' . " 9*39', [a]:" 11 * 4 5 O ,whereas the ethyl tartrate used in the above experiments gaveu: + 18.92O (1=2). For aqueous ethyl tartrate (p=50) Pattersongives :[a]:' + 17-44', [a]?'' 17-34', [a]?'* 17.1'7', 16-91', [a]: 16-76'(T., 1901, 79, 201)60 CUNDALL :Tartramide in Water.Tartramide (0.5 gram) in water (50 grams).t ......................... 17". 27". 37".d ........................... 1.001 0 '999 0.998p = 0.99 :a; (I= 4 ) ............... + 4 *42 4 '40 4.38[a]: ........................ + 111.5 111.1 110 8Densities determined : t... ... 17". 31". 50".d ... 1,001 0.999 0.996.Tartramide in A p e o u s Sodium Chloride.Tartramide (0.5 gram) and sodium chloride (14.62 grams)in water (50 grams).t ........................... 16". 27". 40".d ........................... 1.176 1'170 1 -1 63as ( I = 4) .................. f 3 '20 3-12 3.02Densities determiiied : t ...... 17". 36". 46".d ... 1.175 1.165 1-159p = 0.768 :[aJt ....................... + 88'6 86.8 84.5 .The relative effects of sodium chloride and barium bromide areindicate 3 by the following values for solutions containing the saltsand tartramide (0.5 gram) in water (50 grams):Weight Gram-mol.Salt. of salt. weight. ~i42~. ~ 2 , ~ ( 2 = 4 ) . [a]:.Sodium chloride 11.7 B 1 '139 + 3.36 + 90'2Barium bromide. ..... 29.7 25 1'453 +1'97 +54'41 ......The author wishes to thank the Research Fund Committee of theChemical Society for a grant towards the expenses of this investi-gation.BIRKBECK OOLLEGE,LONDON, E.C

ISSN:0368-1645    

DOI:10.1039/CT9140500049

出版商:RSC    

年代:1914

数据来源: RSC

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60 CUNDALL :VITL-The Action of Xuiphuric Acid on Copper.By (the late) JAMES TUDOR CUNDALL (with appendix byMUNGO MCCALLUM FAIRGRIEVE).SOME time ago, in order to demonstrate the formation of coppersulphide in the preparation of sulphur dioxide by the action ofconcentrated sulphuric acid on copper turnings, I poured the darkliquid obtained into a large quantity of water, when I was surpriseTHE ACTION OF SULPHURIC ACID ON COPPER. 61to find that a bright red precipitate was produced instead of ablack one.A number of experiments were then made, in which differentsamples of copper were heated under varying conditions withsulphuric acid in order to investigate the nature of this precipitate.It was found a t first that the formation of the red precipitate wasapparently capricious, variations in the sample of copper, and ofsulphuric acid, in the time of action, and in the temperature havingno constant effect; but in general it was noticed that the brightestred precipitates were usually obtained when the copper andaulphuric acid were heated until a brisk action occurred, the flamethen removed, and the liquid allowed to remain a little beforebeing poured off.The necessary delay was shorter the more finelydivided the copper. I n order to avoid contaminating the precipitatewith copper sulphide or particles of copper carried over mechani-cally in the liquid, the latter was filtered through asbestos in aGooch crucible into the water.It was then found that not only was the red precipitate formedwhen a sample of copper was acted on by successive quantities ofacid, but also if portions of the liquid were drawn off a t all stagesof the action until the copper was nearly all dissolved.The red precipitate was formed most strikingly when the filtrate,although clear, was of a reddish-brown colour, and only appearedas the l i p i d diffused into the water.It was extremely finelydivided, only settling after some hours. When collected and wmhedon a Gooch filter it assumed a metallic appearance, forming brightfilms of a coppery lustre t.hat floated in the crucible. The weightsof the precipitate were small, and could not be materially increasedby increasing the amount of the acting substances or the time ofaction. They varied from 0.03 to 0.22 gram in weight, and werequite similar whether commercial copper turnings, “ pure precipi-tated copper,” finely divided copper obtained by reducing purecopper oxide in hydrogen, or very pure electrolytic foil free fromarsenic were used.The precipitates were then analysed, 0.135 gram yielding 0.135gram of copper, and 0.223 gram yielding 0-220 gram of copper.They were therefore practically pure copper.Other samples wereexamined for sulphur by conversion into barium sulphate, yieldingonly 0.24, 0.16, and 0.03 per cent.The red precipitate being therefore metallic copper, is formed inall probability by the decomposition of cuprous sulphate by wafer,as shown by Recoura (Compt. rend., 1909, 148, 1105):and 8 sample of cuprous sulphate prepared by Recoura’s methodc ~ 8 o , = c u s o , + c u .. . . . . (1gave with water a red precipitate identical in appearance with thatobtained by the process described above.Suspicion having been aroused that the concentration of thesulphuric acid was the condition deciding the formation of the redprecipitate, a series of experiments was made, in which sulphuricacid of various strengths was made to act on pure copper foil. If" pure distilled sulphuric acid " (D15 1.8399) containing approxi-mately 95.4 per cent. of H,SO, was used, the red precipitate couldnot be obtained, and i t was only on diluting it until the percentageof HzSO, was reduced to about 94 that it definitely appeared,becoming well marked a t 91 per cent., and perhaps at its best atabout 87 per cent.A t lower percentages red precipitates wereproduced, but the action of the acid on the copper only continuedof itself if the mixture was heated repeatedly.On examining the course of the action in the various cases itwas seen that the reddish-brown liquid mentioned above as givingthe red precipitate best when poured on to water was always t obe noticed as pouring off the copper, but whereas in the weakeracids it persisted, in the more concentrated it rapidly became darkgreenish as it passed away from the neighbourhood of the copper.If the reddish-brown liquid is allowed to remain or is gentlyheated it darkens and deposits a greyish-black precipitate. Thisprecipitate when collected and washed resembles cuprous sulphide,and a portion weighing 0.0210 gram gave 0.0158 gram or 75 percent.of copper (Cu,S=:79.9 per cent. Cu and crUS=66*5 per cent.Cu).When more strongly heated the reddish-brown liquid becomesgreenish-black, and deposits a greenish-black precipitate, of which0.318 gram gave 0.2114 gram (=66*5 per cent.) of copper, and wastherefore pure cupric sulphide, although if the heating is continuedthe precipitab dissolves with evolution of sulphur dioxide :It thus approximates t o cuprous sulphide.CUS + 4H2S04= CuSO, + 450, + 4H,O . . . (2)The final result of the reaction, if carried as far as possible,results in the maximum production of sulphur dioxide, as indicatedby the equation:showing a ratio of copper dissolved to sulphur dioxide set free of1 to 1 (which may be observed by w i n g that no solid residue isobtained).I f the cupric sulphide is left unacted on, the ratio of copper tosulphur dioxide rises to 3 : 1, and the ratio of copper as coppersulphate t o copper as sulphide becomes 5.7 : 1, a relation whichmay be expressed by the formula:C?u+2R2S04=CuS04+SOz+2H,0 .. . . (3)6Cu + 8H2S04 = 5CuS0, + CUS + 250, + 8H90 . . (4THE ACTIQN OF SULPHUHIC ACID ON COPPER.. 63If plenty of copper is lsft unacted on, cuprous sulphide isobtained, and the ratio of copper used to sulphur dioxide producedrises to 6 : I, the equation for this being:GCU + 6H2S0, = CUSO, + CU,S + SO, + 6H2O . . (5)Note on Abozie.The late Mr. Cundall left the draft of his research thus inc0.m-plete, but from an earlier manuscript and from conversation withhim I gather that he might hawe completed it and summarisedhis results somewhat as follows:The primary reactions of copper and sulphuric acid may berepresented by the following equations :(0) 8Cu + 4H2S04 = 3c’u2s04 + C 9 S + 480,( h ) 2Cu + 2H,SO, = C!u,S04 + 2H20 + SO,,(c) 5Cu2S0, + 4H2S0, = Cu,S + 8C%SO, + 4H20,( d ) crU,8 t 2H2S0,= CuS + CuSO, + 2H20 + SO,,(e) CuS + 4H280, = Cuso, + 450, + 4H20.Ckprous sulphate is the primary product, both when the sulphuricacid is concentrated, and when it is diluted with water [“Thereddish-brown liquid was always to be noticed as pouring off thecopper,” see above], although a maximum value is given when thediluted acid approximates to one containing molecular proportionsof sulphuric acid and water. In hot concentrated acid, however,the cuprous sulphate is even more unstable than in the slightlydiluted acid, and reacts almost at once, as indicated by equation ( c ) .Equation (a) is apparently specially a lcw-temperature reaction,and it is interesting t o note that if combined with (c) in theproportion of 5 (a) + 3 ( c ) we get:5cU + 4H&30, = cu2s + 3cuso4 + 4H20,one of Pickering’s fundamental reactions (T., 1878, 33, 112).whilst the secondary reactions of the products formed are :andEquation (5) is made up of a+ 2b + c,To get the ordinary equation for the completed action (3) it is,of course, possible t o use either I ‘ a ” or ‘‘ b ” in combination withMr.Cundall’s results, therefore, on the whole confirm the finalresults of Pickering, although the mechanism of the changesinvolved is different, inasmuch as cuprous sulphate is regarded asthe primary substance formed.SCIEXCE DEPARTMENT,THE EDINBUXGH ACADEMY.and (4) ), ,, U.+2b+c+2d.( I c,’) KC d,” and (( e.>

ISSN:0368-1645    

DOI:10.1039/CT9140500060

出版商:RSC    

年代:1914

数据来源: RSC

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64 MILLS AND BAIN: THE CONFtQURATION OF THE1X.-The Conjguration of the Doubly LinkedNitrogen Atom. Optically Active Salts of tlaeSernicarbuzone ayid Benzoylphen~lhydrazone o jcycloHexanone-4-carboxylic Acid.By WILLIAM HOBSON MILLS and ALICE MARY BAIN.IN spite of the facts that a certain number of phenylhydrazonesand semicarbazones have been found to occur in isomeric modifica-tions, and that these are exclusively of the asymmetrical typeR,R,C:N*NHX, for several reasons-of which the most importantare the greater irregularity in the occurrence of the isomerism andthe absence of significant chemical differences between theisomerides, like the differences in ease of dehydration of thealdoximes, or in the course of the Beckmann transformation in theketoximes-it is probably generally held that the evidence for theexistence in these compounds of a geometrical isomerism, condi-tioned by the presence of nitrogen doubly linked to carbon inaccordance with the hypothesis of Hantzsch and Werner, is by nomeans so strong as it is in the case of the oximes. It thereforeseemed desirable to extend to the semicarbazones and phenylhydr-azones the method which we had previously employed (T., 1910,97, 1866) f o r the examination of the configuration of doubly linkednitrogen in the case of the oximes, namely, that of investigatingthe possibility of the existence in an optically active form ofphenylhydrazones and semicarbazones of such constitution that theyare molecularly symmetric or asymmetric according as the threevalencies of the doubly linked nitrogen which they contain are,or are not, in one plane.Our experiments on the oximino-groupwere carried out on the oxime of cycZohexanone4-carboxylic acid(Perkin, T., 1904, 85, 416). I n the present communication anaccount is given of the investigation from a similar point of viewof derivatives of the hydrazone of this acid. I f in the hydrazoneof cycZohexanone-4-carboxylic acid (or its N-substitution deriv-atives) the valencies of the doubly linked nitrogen lie in one planethe molecule possesses a plane of symmetry (Fig. l), and thecompound must therefore be incapable of optical activity. If, onthe other hand, the three valencies of this nitrogen atom are notin one plane (Figs. Za, Zb), then the molecule possesses neither aplane nor a centre of symmetry, and must therefore exist in twoenantiomorphous forms exerting equal and opposite effects on planepolarised light DOUBLYFIG.l.*H C@,H'*.. %\ /C/\ 7% p 2\/CH, CH,LINKED NITROGEN ATOM."./c *-./c65' Therefore if an N-substitution derivative of the hydrazone ofcy clohexanone-4-carboxylic acid can be obtained in an opticallyactive form, the conclusion must be drawn that in that compoundthe three valencies of the nitrogen atom do not lie in one plane.Unfortunately, the plienylhydrazone of cycZohexanone-4-carb-oxylic acid could not be investigated on account of experimentaldifficulties. The action of phenylhydrazine on this acid wasexamined by Perkin (loc. cit., p.428), and the resulting phenyl-hydrazone was found to be an un6table oil, readily decomposing,under the influence of acids, into ammonia and tetrahydrocarbazole-3-carboxylic acid.The X-substitution derivatives of the phenylhydrazone are, how-ever, naturally much more stable. W e prepared the N-methyl andY-benzoyl compouuds, and found them t o be well defined, crystal-line substances. The former did not give salts of a satisfactorycharacter with the common alkaloids, but the benzoylphenylhydr-azone was readily obtained in a dextrorotatory form by means ofits quinine salt. The sodium salt, obtained from the quinine saltby decomposing it with excess of sodium hydroxide, was found,after the removal oE the quinine, to have in the aqueous alkalinesolution a molecular rotation of [MID 238.6O.The optically activesolutions of sodium or ammonium salt obtained in this mannershowed marked autoracemisation, which, in the ammonium salt,proceeded in accordance with the unimolecular formula. As hadbeen found to be the case with the corresponding oxime, the auto-racemisation was retarded by the presence of alkaline hydroxides.The strong alkali hydroxides, however, even in dilute solution,brought about a t the same time some chemical alteration (probablyheavy lines, those behind the plane of the paper by dotted lines.* In these diagrams bonds projecting in froiit of the paper are represented byVOL. cv. E66 MILLS AND BAIN: THE CONFIGURATION O F THEin the first place elimination of the benzoyl group), and in thepresence of these the observed rate of diminution of optical activitydid not follow the unimolecular law.On acidification of the activesolutions complete racemisation waa brought about, apparentlyinstantaneously.Since the quinine salt contains the dextrorotatory form of theacid combined with the more highly laevorotatory quinine, itssolutions must show initially a small lzevorotation, increaaing as theautoracemisation of the acid component of the salt proceeds, untilit reaches the value corresponding with that of the quinine saltof the inactive acid. I n the case of both the quinine and themorphine salts of the corresponding oxime it was possible to observesuch mutarotation (Zoc. cit., p. ISSO), but in the benzoylphenyl-hydrazone the change proceeds so rapidly that unfortunately itwas invariably found to have entirely completed itself within thebrief time necessary to prepare a solution and observe its rotation.On account.of the rapidity of this change it was evidently hope-less t o attempt to obtain more highly active preparations of thebenzoylphenylhydrazone by recrystallisatisn of its quinine salt.The molecular rotation of the optically pure compound, therefore,could not be determined.These facts explain why the I-acid cannot be obtained from themother liquor from which the morphine salt of the d-acid hascrystallised. On concentration this yields nothing but the 6-acidsalt. The isolation of the dextrorotatory modification depends,therefore, on a process of activation, rather than of resolution, bymorphine.A similw phenomenon was observed by Pope andPeachey in the case of the methylethylpropyl tin salts (P., 1900,16, 42, 116).The semicarbazone of cyclohexanone-4-carboxylic acid (Perkin,Zoc. cit., p. 427) was similarly examined, and with the aid ofmorphine we succeeded in obtaining the ammonium salt of thiscompound also in an optically active condition. After crystallisingthe morphine salt from dilute alcohol, decomposing it withammonia, and removing the morphine, strongly dextrorotatorysolutions were obtained. The values observed for the molecularrotation of the ammonium salt which they contained lay in mostcases between [MI, 30° and [MI, 40°. Even at temperatures in theneighbourhood of Oo the solutions showed rapid autoracemisation,proceeding strictly in accordance with the unimolecular formula.The autoracemisation was retarded by free alkali, but even in thepresence of Lv / 5-soclium hydroxide (together with a little ammonia)the period of half change at 1.lo was as short ;t8 3.6 hours.Onacidifying the solutions the optical activity immediately disapDOUBLY LINKED NITROGEN ATOM. 67peared. There is thue a very close correspondence between theoptically active forms of the oXime, the semicarbazone, and thebenzoylphenylhydrazone of cycZohexanone4-carboxylic acid withregard t a the conditions which affect their autoracemisation.The effect of temperature on the rate of racemisation of thesemicarbazone in alkaline solution was also examined.The velocity-constant was increased 3.49 times by a rise of temperature of 7O.Assuming that the constant is increased in a fixed ratio by equalincrements of temperature, this corresponds with a quotient forloo of 5.96, a. number greatly in excess of the usual value 2 to 3.Dimroth (Aizmlen, 1904, 335, 8) found similarly high values inthe case of the transformation, in various solvents, of methyl5-hydroxy-l-phenyl-l : 2 : 3-triazole-4-carboxylate into the correspond-ing neutral (diazo) compound, and, regarding the two compoundsa t that time as a pair of keto-enol desmotropes, he suggested thata high temperature-coefficient might be characteristic of desmo-tropic change. The fact that the effect of temperature is unusuallyIarge in the present case also indicates the possibility of a hightemperature-coefficient being of frequent occurrence in intra-molecular transformations.The above observations prove beyond doubt that, in the formof their salts, the benzoylphenylhydrazone and the semicarbazoneof cycEohexanone-4-carboxplic acid can exhibit very considerableoptical activity. There would appear to be no reason to supposethat the salts differ in constitution from the acids from which theyare derived, or that the acids themselves are constituted otherwisethan in accordance with the general view as to the structure of thesemicarbazones and phenylhydrazones of cyclic ketones, Sincecompounds of the type C0,LI.CH<c,2--C: ' H2°GH2> C*NH*NR,R2 wouldalmost certainly be less acidic than the corresponding hydrazones,i t is most highly improbable that the active salts should be derivedfrom tautomeric modifications of the hydrazones of this character,containing an asymmetric carbon atom of the ordinary type.The conclusion would therefore appear justified that the molecularasymmetry which arises when the carbonyl oxygen of the symmetri-cal cyclohexanonecarboxylic acid is replaced by the hydrazoneresidue is only to be explained satisfactorily by supposing that theconfiguration assumed by this residue in the resulting hydrazoneacid is such that its distal portion, the substituted amino-group, isdrawn into a position considerably to one side o r the other of theplane which was previously the plane of symmetry of the keto-acid.These experiments accordingly very strongly support the.hypothesisthat in the hydrazones, as in the oximes, the three valencies of theF 68 MILLS AND BAIN: THE CONFIGURATION OF THEdoubly-linked nitrogen atom do not lie in one plane, but aredirected along the three edges of a trihedral angle.EXPERIMENTAL.cycloHexanone-4-carboxylic Acid Bensoylphenylhydrasone.When as-benzoylphenylhydrazine, cyclohexanone - 4 - carboxylicacid, and acetic acid are dissolved in equimolecular proportionsin a small amount of alcohol and the mixture is allowed t o remainat the ordinary temperature, colourless crystals of the abovehydrazone are slowly deposited. By recrystallisation from a largevolume of benzene the compound is obtained in a state of purity,melting a t 169-171O.The yield of recrystallised hydrazoneamounts t o 60-70 per cent. of the theoretical:0-2137 gave 0.5620 CO, and 0.1170 H,O. C=71-74 ; H= 6.08.0.1922 ,, 14.4 C.C. N, (moist) at 18O and 7.38 mm. N=8-4.C,,H,,O,N, requires C = 71-43 ; H = 5-95 ; N = 8.3 per cent.0-3543 required for neutralisation 10.60 C.C. N / 10-NaOH.Equivalent = 334. C20Hl,0,N2H requires 336.Optically Active Salts of cycloHexamne-4-carboxylic AcidBemzo ylphen ylh ydrason e.The dextrorotatory metallic salts of cyclohexanone-4-carboxylicacid benzoylphenylhydrazone were obtained by the aid of quinine.The benzoylphenylhydrazone (3.86 grams) and anhydrous quinine(3.72 grams) were dissolved in 34 C.C. of methyl alcohol; waterwas then added in quantity just short of that required to producea permanent turbidity (about two volumes were necessary), andthe solution inoculated with a few crystals of the quinine salt froma previous preparation.The I-quinine-d-acid salt was slowly deposited in the form ofsmall clusters of silky needles.It was recrystallised from dilutemethyl alcohol. The air-dried salt melts a t 139-141°, and containsone molecule of water of crystallisation :0.3615 lost 0'0095 KO. H20=2.63.The, salt after .drying for three hours at 90-looo gave the follow-0.2511 gave 0.6688 CO, and 0,1547 H,O. C= 72-64 ; H = 6-84.0-3078 ,, 22-26 C.C. N, (moist) at 14.9O and 771 mm. N=8-57.C,H,,03N2,C,,H,02N2,H20 requires H20 = 2 * 65 per cent.ing results on analysis:C20H,03N,,C20H~0,N2 requires C= 72-72 ; H = 6-73 ;N = 8-5 7 per cent.I n order to obtain the dextrorotatory sodium salt a weigheDOUBLY LINKED NITROGEN ATOM.69quantity of the quinine salt was triturated with such a quantityof sodium hydroxide in aqueous solution that the final solutionwould be fifth-normal with respect to the excw of sodium hydr-oxide. The separated quinine was washed with a little water, thefiltrate and washings were extracted three times with chloroform,made up to the required volume and polarimetrically examined, alloperations being conducted at the temperature of melting ice; forexample, 1.2 grams of quinine salt having been treated in thismanner with 0.197 gram of sodium hydroxide, the following polari-metric observation was made, the volume of the solution being15.5 c.c.:1 = 2, C *=7.74, a, =5*44O, [MID = 238.6'.Thle Autoracemisation Phenomena.(a) Arn?ionium Sdt inPresence of N/ 10-A mmonium Hydroxide.The solution of dextrorotatory ammonium salt was prepared ina manner similar to that described above for the potassium salt,1.0 gram of quinine-d-acid salt being employed, together with a suffi-cient excess of ammonia t o leave the solution approximately deci-normal with respect to ammonium hydroxide after decompositionof the quinine salt. The volume of the solution wil.8 12.1 c.c., thetemperature maintained at 19*9O, and the polarimetric observationsmade in a 2-dcm. tube:t (mins.).0 .o5.0810.4722 4330'1740'4249-03Rotation. 1 Itlog.a/a - 2.2.71" -2'22 0.01i01.79 0.01711.15 0'01660'85 O * O l c i i0.55 0*01710.40 0.0169(b) Potassium Salt in Presence of N f 20-Potassium Hydroxide.One gram of quinine-d-acid salt was trea-ted with 10.58 C.C. of aA7/5-solution of potassium hydroxide. The volume of the solutionmas made up after removal of the quinine to 12 c.c., the tempera-ture was maintained a t 19.7O, and the observations were made ina 2-dcm. tube:1, (mins.). Rotation. l/tlog.a/a - x.0 .o 5.93" -4 *54 5.49 0.0073710.01 5-16 0*0060421 24 4'63 0.0089630.03 4 '27 0.0047549.03 3'49 0.00469* This refers t o the ammonium salt70 MILTAS AND BAIN: THE CONFIGURATION OF THEThese tables show first, that in the presence of N/lO-ammoniumhydroxide solution racemisation proceeds rapidly, and in accurd-ance with the unimolecular formula, and secondly, that the substi-tution of potaasium hydroxide for ammonium hydroxide greatlyretards the racemisation (the initial rate is about twenty-six timesless in the latter case).That in the presence of potassium hydr-oxide the rate of diminution of optical activity as the racemisationproceeds shows marked deviation from that. to be expected in asimple unimolecular reaction is not surprising, for towards the endof the forty-eight hours during which the solutions were underobservation they became turbid and discoloured, indicating thatsecondary changes were taking place. As i t was also found bytitration that the quantity of free potassium hydroxide had greatlydiminished, it is probable that elimination of the benzoyl groupwas taking place, followed by decomposition of the resulting unstablephen yl hydrazone.cycloNezanone-4-carboxylic A cia! Phenylmet h ylh ydrazone.A solution of as-phenylmethylhydrazine (2.3 grams) in 50 percent. acetic acid (20 c.c.) was added to a solution of cyclohexanone-4-carboxylic acid (2.6 grams) in water (60 c.c.).As the hydrazoneotherwise tends to separate as an oil, a few crystalline nuclei froma previous preparation were added. After half an hour the crystal-line deposit was collected, dried, and recrystallised from ethylacetate. The phenylmethylhydrazone is a colourless compound,melting and decomposing at 138-139O. Its solutions become redon keeping:0.2026 gave 0.5103 CO, and 0.1327 H,O.C=68*7; H=7.3.0.2551 ,, 25.6 C.C. N, at 21° and 759 mm. N=11*4.CI4Hl8O2N2 requires C'= 68.2 ; H = 7.3 ; N = 11.4 per cent.Optically Active Salts of the Semicarbasone of cycloHexanone-4-car b oxylic A cid.The semicarbazone of cyclohexanone-4-carboxylic acid, preparedas described by Perkin (loc. cit., p. 427), was obtained in the formof its alkaline salts in a dextrorotatory modification with the aidof morphine.The semicarbazone (2.7 grams), dissolved in a hot mixture ofmethyl alcohol (60 c.c.) and water (16 c.c.), was added to a hotsolution of morphine (4.13 grams) in methyl alcohol (30 c.c.). Themorphine salt separated on cooling, usually in well-formed prisms,which contained no water of crystallisation. I n order to obtainthe dextrorotatory ammonium salt, the very finely-powderedmorphine salt was triturated a t Oo with so much ice-cold aqueouDOUBTJY LINKED NITROGEN ATOM.71ammonia that the excess of ammonia, after dilution of the solutionto the required volume, would be of decinormal strength. Theprecipitated morphine was removed by filtration, washed with alittle ice-water, and the filtrate and washinge, polarimetricallyexamined in a tube round which ice-cooled water was circulated.The amount of morphine left in the solution was found to be sominute and was so readily allowed for by observing the slight,laevorotation which appeared when the autoracemisation was com-plete, that it seemed inadvisable to attempt to remove it. Theammonium salt obtained in tkis manner from 1 gram of morphinesalt was examined polarimetrically with the following result :I = 2, C = 3.258, U, = 1*17O, [MI, = 38.8'.The solutions of ammonium salt obtained from different prepara-tions of morphine salt showed the following molecular rotation :[nil,, 37 80 37.1" 32.5" 27-9" 32.5"The Autoracemisation of the Optically Active Salts of th.eSemicarbasone.(I) Ammonium Salt in Presence of N 10-Ammonium Hydr-ozide.-Morphine salt (1 gram) was triturated with an aqueoussolution of ammonia (0.0584 gram), and, after removal of theprecipitated morphine, the filtrate and washings were made up to13.7 C.C.The observations were made in a 2-dcm. tube maintaineda t 2.3O:t (mins.). 1: o tation. l/tlog.a/(a - x).0.0 1'15" -4'45 1 '07 0.007113-4 0.89 0.008328 -4 0-69 0.007835 '8 0 60 0.007946 -3 0'48 0 -008255 '1 0.41 0.008265.7 0 -35 0.007980-2 0.25 0'0082(2) A mmonium Salt and Amntonium Hydroxide (N/lO) withthe Addition of Sodium Hydroxide (N/ lo).-The solution (11 c.c.)was prepared from 2-43 grams of morphine salt.The observationswere made in a 2-dcm. tube maintained at 1.9O:t (mins. ) Kotation. l/tlog.a/(a -a).0 '0 2-43" -9.5 2-16 0.005413 '1 1-95 0-005327'2 1.75 0 005240 '1 1 *52 0.005163 -0 1-15 0'0052105.7 0.70 0-0051152.1 0'41 0-0051(3) Ammonium Salt and A mmonium Bydroxidc (N/ 10) withthe ddition of Sodiim Eydroxide (N/5) at 1*l0.-The solutio72 CONFIGURATION OF THE DOTJBLY L I S I ~ D NITROGEN ATOM.(12 c.c.) was prepared from 2.5 grams of morphine salt.observations were made in a 2-dcm.tube:Thet (m ins.)0.015.82,s-254.6115'8234'0337.3453.6582-7Rotation.2-80'2-672.582 3 51'941'320 '940.650.445l/llog.Q(n - 2). -0.002310 001410.001390-001380.001390 *001410'00:390~00137(4) Amrn,mium Salt and Amrnonizcm Hydro-xide (N/10) with theaddition of Sodium Hydroxide (N/5) nt 8*l0.--The sulution wasprepared as in experiment (3), but the observation tube was main-tained a t a higher temperature:f (inins.)0'09 -624 *O48.1F4-7118 4155.611 o tation. 1 /tl og. n(n - x).2.42" -2 16 0 00511 *85 0-00481'44 0.00470.92 0'00490.66 0.00480'43 0'0048The first three tables show clearly the effect of an increase inthe hgdroxyl-ion concentration (or diminution in the hydrogen-ionconcentration) on the stability of the optical activity, the diminish-ing values of the constant in the three cases, 0*0081, 0*0052, and0.00139, corresponding with increasing periods of half racemisationof 37 mins., 58 mins., and 217 mins.Comparison of the third and fourth tables shows the effect oftemperatures on the rate of autoracemisation. A rise of tempera-ture from 1-lo to 8-1° was associated with an increase in thevelocity constant from 0-00139 to 0.00485, that is t o say, theconstant was increased 3.49 times by a rise of 7 O .Acidification produces an instantaneous disappearance of theoptical activity. I n illustration of this the following experimentmay be quoted. An alkaline ice-cold dextrorotatory solution wasacidified by addition of 1 C.C. of A'-hydrochloric acid; 1 C.C. ofN-sodium hydroxide solution was then added as rapidly as possible.On polarimetric examination the resulting alkaline solution wasfound to be quite inactive.The authors desire to express their .thanks to the ChemicalSociety for a grant in aid of this work.UNIVERSITY c 11 E M ICAL L A B 0 KAToRY, NOR'T'HF,I~N 1'0LY TPCHN I C 1 XSTI'I'LJTIC,Ca M B K I n Q E. HOLLOWAY, LONDON, N

ISSN:0368-1645    

DOI:10.1039/CT9140500064

出版商:RSC    

年代:1914

数据来源: RSC