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J O U R N A LOFTHE CHEMICAL SOCIETY.TRANSACTIONS.H. BRERETOK BAKER, M.A., D.Sc.,J. N. OOLLIE, Ph.D., F.R.S.A, W. CROSSLEY, D.Sc., Ph.D., F.R S.F. G. DONNAN, M.A., Ph.D., F.R.S.BERNARDYER, D.Sc.M. 0. FORSTER, D.Sc., Ph.D., F.R.S.F.R.S.T. M. LOWKY, D.Sc.A . MCKENZIE, M.A., D.Sc., PILL).W. H. PERKIN, Sc.D., LL.D., F.R.S.J. C. PHILIP, D.Sc., Ph.D.F. R. POWER, Ph.D., LLD.A. SCOTT, MA., D.Sc., F.R.S.S. SMILES, D.Sc.Qbitar :J. C. GAIN, D.Sc., Ph.D.S,ub-&biiar :A. J. GREENAWAY.1913. Vol. CIII. Part I._ _ _ _ _ _ _ _ ~ .LONDON:GURNEY & JACKSON, 33, PATERNOSTER ROW, E.C.1013RIOHAHD CLAY 4z SONS. LIMITEDBRUNSWICK STREET, STAMFORD STREET, S.E.,AND BUNOAY, GUFFOLILCONTENTS.PAPERS COMMUNICATED TO THE CHEMICAL SOCIETY.PAGEI -Nitrites of the Alicylic Ammonium Series.Nitrosopiper-azinium Nitrite. By PRAFULLA CHANDRA RAY and JITENDRANATH RAKSHIT . . 111.-Chlorides of the Mercurialkyl- and Mercurialkylaryl-ammonium Series and their Constitution as based on Conduc-tivity Measurements. By PRAFULLA CHANDRA Rbu andNILRATAN DHAR . 3111.-Equivalent Conductivity and Ionisation of Nitrites. ByPRAFULLA CHANDRA RAY and NILRATAN DHAR . . 101V.-Viscosity and Association. Part 111. The Existence ofRacemic Compounds in the Liquid State. By FERDINANDBERNARD THOLE . . 19V.-The Formation of Tetrahydro-oxazoles from a-Hydroxy-p-anilino-up-diphenylethane and its Homologues. By HORACELESLIE CROWTHER and HAMILTON MCCOMBIEV1.-The Action of Halogens on Silver Salts. By H U ~ H STOTTTAYLOR (1851 Exhibition Scholar, University of Liverpool) .VI1.-Diphenylene. Part 11.By JAMES JOHNSTON DOBBCE,JOHN JACOB Fox, and ARTHUR JOSIAH HOFFMEISTER GAUGE .VII1.-Synthetical Aminoglucosides Derived from 'd-Glucos-amine. By JAMES COLQUEIOUN IRVINE and ALEXANDERHYND, M.A., B.Sc. (Carnegie Fellow) .1X.-The Condensation of a-Keto-/3-anilino-a-phenylethane andits Homologues with Carbonyl Chloride, Phenylcarbimide,and Phenylthiocarbimide. By HAMILTON MCCOMBIE andHAROLD ARCHIBALD SCARBOROUGH .X. -Studies in the Camphane Series. Part XXXIII. Orienta-tion of Tiemann's isoAminocamphor. By MARTIN ONSLOWFORSTER and HUBERT ARTHUR HARBY HOWARDXI.-The Constitution of the ortho-Diazoimines. Part 11. Thep-Tolyl-P-nsphthatriazoles.By GILBERT T. MORGAN andFRANCES M. G. MICKLETHWAIT .XI1.-Co-ordination Compounds of Vanadium. Part I. TheAcylacetonates. By GILBERT T. MORGAN and HENRYWEBSTER Moss, A.I.C., A.R. C.Sc.1. . . .XII1.-Chemical Reactivity and Absorption. Part 11. TheVariation of Absorption with Concentration. By EDWARDCHARLES CYRIL BALY and FRANCIS OWEN RICE . . .X1V.-The Constitution of Cytisine, the Alkaloid of CytbusEabuwmm. Part I. The Synthesis of a-Cytisolidine andof /3-Cytisolidine. By ARTHUR JAMES EWIN~ .X V.-The Synthesis of Some New Dimethyltetrahydroquinolines.By ARTHUR JAMES EWINS and HAROLD KING ...2731364156637178919710iv CONTENTS.XVI.4ptically Active Glycols Derived from the Phenyl-lacticPAGEAcids. Part I. By ALEX.MCKENZIB and GEOFFREY MARTIN 11 2XVI1.-Dibenzyl- and Diphenyl-silicols and -silicones. ByXV1II.-The Photography of Absorption Spectra. By THOMASRALPH MERTON, B.Sc. (Oxon.) .X1X.-The Relation between Viscosity and Chemical Constitu-tion. Part VI. Viscosity an Additive Function. ByALBERT EFLNEST DUNSTAN and FERDINAND BERNARD THOLE .XX.-The Relation between Viscosity and Chemical Constitu-tion. Part VII. The Effect of the Relative Position ofTwo Unsaturated Groups on Viscosity. By ALBERT ERNESTDUNSTAN, THOMAS PERCY KILDITCH, and FERDINAND BERNARDTHOLE .XX1.-An Attempt to Harmonise, Qualitatively, the Relationbetween Temperature and Rotation for Light of all Re-frangibilities of Certain Active Substances, both in theHomogeneous State and in Solution, By THOMAS STEWARTPATTERBON .SXI1.-Quinone-ammonium Derivatives.Part 11. Nitro-haloid, Dihaloid and Azo-compounds. By RAPHAEL MELDOLAand WILLIAM FRANCIS HOLLELY .XXII1.-The Constituents of the Rhizome and Roots ofCadophyllum thalictroides. By FREDERICK BELDINCJ POWERand ABTHUR HENRY SALWAY .GEOFFREY MARTiN .XX1V.-Quercetagetin. By ARTHUR GEORGE PERKIN .XXV.-The Chlorination of Iodophenols. Part 11. TheChlorination of o-Haloid Derivatives of 1)-Iodophenol. ByGEORQE KINQ, M.Sc. (Priestley Research Scholar of theUniversity of Birmingham), and HAMILTON McCoar BIZ .XXVL-2 : 2’-Ditolyl-5 : 5’-dicarboxylic Acid. By JAME~ KENNERand ERNEST WITHAM .XXVIL-The Action of Ammonia and Alkylamines on Reduc-ing Sugars. By JAMES COLQUHOUN IRVINE, ROBERT FRASERTHOMSON, M.A., B.Sc., and CHARLES SCOTT GAFLRETT, B.%.XXVII1.-The Form of Extinction Curves : Cobalt NitrateSolutions.By TBOMAS RALPH MERTON, B.Sc. (Oxon.) .XX1X.-The Influence of Water on the Partial Pressures ofHydrogen Chloride above its Alcoholic Solutions. ByWILLIAM JACOB JONES, ARTHUR LAPWORTH, and HERBERTMUSCHAMP LINGFORD .XXX.-The Presence of Helium in the Gas from the Interiorof an X-Ray Bulb. By Sir WILLIAM RAYSAY, K.C.B. .XXX1.-Vaubel’s Supposed Phenyldi-imine. By MARTIN ONSLOWFORSTER and JQHN CHARLES WITHERHXXXIL-&Derivatives of Adipic and p-Methyladipic Acids,and the Preparation of Muconic and /3-MethylmuconicAcids. By HENRT STEPHEN and CHARLES WEIZMANN . ..11912412713414517719120922023223824925226426626CONTENTS.XXXII1.-The Chemistry o# the Glutaconio Acids.Part VII.The Normal and Labile Forms of ay-DimethylgluhonicAcid and their Reduction to cis-uy-Dimethylglutaric Acid.By JOCELYN FIELD THORPE and ARTHUR SAMUEL WOOD .X XX1V.-The Measurement of Tryptic Protein Hydrolysis byDetermination of the Tyrosine Liberated. By SAMUELJAMES NANSON AULD and THOMAS DUNCAN MOSSCROP, B.Sc.XXXV.-The Solubility of Sulphanilic Acid and its Hydrates.By JAMES CHARLES PHILIP .XXXV1.-The Alkaloids of Xa?tthoxglzcm brachymunthum. ByHOOPER ALBERT DICKINSON JOWETT and FRANK LEE PYMANXXXVI1.-The Precipitation of Lead Thiosulphate and itsBehaviour on Boiling with Water. By WILLIAM HUGEIESPERKINS and ALBERT THEODORE KING.XXXVIK-Ionisation and the Law of Mass Action.ByWILLIAM ROBERT BOUSFIELD, M.A., K.C. .XXXIX.-Viscosity and Association. Part IV. The Viscosityof the Aromatic Amines. By FERDINAND BERNARD THOLE .XL.-The Reaction between Ferric Salts and Thiosulphates.By JOHN THEODORE HEWITT and GLADYS RUBY MANN .XL1.-Hexahydropyrimidine and its Benzoyl Derivatives, ByARTHUR WALSH TITHERLEY and GERALD EYRE KIRKWOODBRANCH .XLT1.-The Interaction of Bromine and the Sulphidev ofp-Naphthol. Part 11. By THOMAS JOSEPH NOLAN andSAMUEL SMILES .XLII1.-Researches on the Constitution of Physostigmine.Part 11.. The Synthesis of 3-Dimethy1aminoacetyl-Z-methylindole and 2-a-dimethy lamino-y-hydroxypropylindole.By ARTHUR HENRY SALWAY .XL1V.-Synthetical Experiments in the Group of the iso-Quinoline Alkaloids. Part 111.The Constitution ofAnhydrocotarnineacetophenone, etc., together with anAccount of Some New Condensation Product8 of Cotarnine.By EDWARD HOPE and ROBERT KOBINSONXLV.-Contributioris to Our Knowledge of Semicarbazones.Part 11. Semicarbazones of Nesityl Oxide. By FORSYTHJAMES WILSON and ISIDOR MORRIS HEILBRON .XLV1.-The Chemical Nature of Some Radioactive Disintegra-tion Products. By ALEXANDER FLECK, B.%. .XLVI1.-The Identification of Ipuranol and Some Allied Com-pounds as Phytosterol Glucosides. By FREDERICK BELDINaPOWER and ARTHUR H.ENRY SALWAYXLVII1.-The Absorption Spectra of Substances ContainingLabile Hydrogen Atoms. By PETER JOSEPH BRANNIGAN,ALEXANDER K ILLEN MACBETH, and ALFRED WALTER....VPAGE27628 128429030030731732433034035136 137 738 1399STEWART .. 40vi CONTENTS.XL1X.-The Presence of Neon in Hydrogen after the Passageof the Electric Discharge through the latter at LowPressures. By JOHN NORMAN COLLIE and HUBERT SUTTONPATTERSON .L.-The Double Platinic and Cupric Iodides of SubstitutedAmmonium Bases. By RASIK LAL DATTA . .LT.-The Absorption Spectra of Simple Aliphatic Substances inSolutions and as Vapours. Part 11. Unsaturated Alde-hydes and Ketones. By JOHN EDWARD PURVIS and NIALPATRICK MCCLELAND .LT 1.-A Novel Method for Resolving Externally CompensatedAmines : Derivatives of d- and I-Oxymet hylenecamphor.By WILLIAM JACKSON POPE and JOHN READLII1.-The Mode of Combustion of Carbon.By THOMAS FREDERIC RHEAD and RICHARD VERNON WHEELERLIV.-Existence of Racemic Compounds' in the Liquid State.By ALEU DUNCAN MITCEELL and CLARENCE SMITH . .LV.-The Interaction of Chlorine and Hydrogen. The Influenceof Mass. By DAVID LEONARD GRAPHAN and LEO KINGSLEYUNDERHILL ,LV1.-Quinonoid Salts of Nitroanilines. By ARTHUR QEORQEGREEN and FREDERICK MAURICE ROWELVI1.-The Estimation of Mercury as Metal by the DryMethod. By ALEXANDER CHARLES CUMMINQ and JOHNMACLEOD .LVII1.-The Latent Heats of Chloroform and Benzene and oftheir Mixtures Between 0" and 80". By JAMES FLETCHERand DANIEL TYREB .L1X.-The Relation Between the Absorption Spectra of Acidsand their Salts, Part I. Sodium Salts. By ROBERTWRIQHT (1851 Exhibition Scholar) .LX.-Metaphosphoric Acid and its Alkali Salts. By ALFREDHOLT and JAMES ECKERSLEY MYERS .LX1.-The Action of Chlorine on Thymol and on m-Cresol.ByHORACE LESLIE CROWTHER and HAMILTON MCCOMBIE .LXI1.-The Constituents of the Oil of Cydnzls i n d b 8 . ByEDWIN ROY WATSON ,LXIIL-Studies on Cyclic Ketones. Part 111. By SIEGFRIEDRUHEMANN and STANLEY ISAAC LEVY .LX1V.-Partially Methylated Glucoses. Part I. 5-MonomethylGlucose and yd-Trimethyl Glucose. By JAMES COLQUHOUNIRVINE and JAMES PATTERSON SOOTT, M.A., D.Sc. (CarnegieFellow) .LXV.-Partially Methylated Glucoses. Part 11. py-Dimethyla-Glucose and py-Dimethyl p-Glucose. By JAMESCOLQUHOUS IRVINE and JAMES PATTER~ON SCOTT, M.A.,D.Sc. (Carnegie Fellow) ....PAUP:41942643344446 148949650851 351752853253664855 15645 7CONTENTS.viiPACELXVI.4tudies in the Diphenyl Series. Part IV. TheAbsorption Spectra of the Two Isomeric o-Dinitrobenzidines.By JOHN CANNELL CAIN, ALEXANDER KILLEN MACBETH,and ALFRED WALTER STICTVART . . .LXVI1.-The Influence of the Constitution of Tertiary Baseson the Rate of Formation of Quaternary Ammonium Salts.Part I. By EBENEZER REES THOMAS . .LXVII1.-Studies in Substituted Quaternary Azonium Com-pounds containing an Asymmetric Nitrogen Atom. Part I.Resolution of Phenylmethylethylazonium Iodide intoOptically Active Components. By BAWA KAI~TAR SINGH .LXIX.-The Formation of Cyclic Compounds from Deriv-atives of 2 : 2'-Ditolyl. By JAMESRENNER .LXX.-The Vapour Pressures of the Lower Alcohols and theirAzeotropic Mixtures with Water.Part I. Ethyl Alcohol.By RICHARD WILLIAM MERRIMAN, M.A.LXX1.-The Influence of Colloids and Fine Suspensions on theSolubility of Gases in, Water. Part 111. Solubility ofCarbon Dioxide at Pressures lower than Atmospheric. ByALEXANDER FINDLAP and THOMAS WILLIAMS, B.Sc. (1861Exhi bition Science Bursar, University College of Wales,LXXIL-A New Iron Bacterium. By ERNES~! MOORELXXII1.-Gossypetin. 3 y ARTHUR GEORUE PERKIN .LXXIV.4tudies in the Camphane Series. Part XXXIV.Configuration of the Eight Oximino-derivatives of Cam-phorquinone. By MARTIN ONSLOW FORSTER .LXXV.-Externally Compensated Hydroxyhydrazinohydrin-dene, its Derivatives, and Resolution into Optically ActiveLXXV1.-The Action of Ozone on Cellulose.Part 111.Action on Beech Wood (Lignocellulose). By CHARLESDORSE and MARY CUNNINUHAM .Part IX.The Jnterconversion of the Optically Active Phenyl-methylcarbinols. By ALEX. MCEENZIE and GEORGEWILLIAM CLOUGH .ANNUAL GENERAL MEETING .PRESIDENTIAL ADDRESS .OBITUARY NOTICES . .LXXVII1.-The Action of Tartaric Acid on Tin in the Presenceof Oxygen. By ALFRED CHASTON CHAPMAN .LXX1X.- Some Double Salts with Acetone of Crystallisationand the Crystallisation of Silver Iodide, Silver Bromide,and Cuprous Iodide. By JAMES ERNEST MARSH and WILLIAMCLAUDE RHYMES ..Aberystwyth) . . .MUMFORDComponents. By DAVID HENRY PEACOCK . . .LXXVI1.-Experiments on the Walden Inversion.58659460461362863664565066266967768770071374277578viii CONTENTS.LXXX.--Notes on the Determination of the Electrical Con-ductivity of hlutions. By HAROLD HAEPTLEY and WILLIAMHPINRT BARRETT .LXXX1.-The Preparation of Conductivity Water. By ROBERTBOURDILLON .LXXXI1.-The Reaction between Ferric Salts and Thiocyanates.By JAMES CHARLES PHILIP and ARTHUR BRAMLEYLXXXII1.-'"Jon-aromatic Diazonium Salts. Part I. Anti-pyrilkediazonium Salts and their Azo-derivatives. ByGILBERT T. MORGAN and JOSEPH REILLY, B.A., B.Sc.,A.R.CY.Sc.1,LXXX1V.-The Constitution of the Anhydro-bases derivedfrom Tetrahydroberberine Alkyl Hydroxides. By FRANKLEE PYMAN . . .LXXXV.-Optical Activity and Enantiomorphism of Molecularand Crystal Structure.By THOMAS VIPOND BARKER andLXXXV1.-The Preparation of Pure Bromine. By ALEXANDERSCOTTLXXXVIL-The Application of Hofmann's Reaction to Di-alkylacetamides. By FRANK LEE PYMAN .LXXXVII1.-Constitution of Aliphatic Diazo-compounds. ByMARTIN ONSLOW FOWTER and DAVID CARDWELL .LXXX1X.-The Conversion of Sodium Hydrosulphide intoSodium Monosulphide. By JOHN SMEATH THOMAS andALEXANDER RULE .XC.-The Absorption Spectra of Some Derivatives of theNitroaminophenols in Relation to their Constitution. ByRAPHAEL MELDOLA and JOHN THEODORE HEWITT .XC1.-The Carbinol-Ammonium Base Isomerism in Connexionwith Azomethine Bases. Part 1. Derivatives of Cinn-amylidene-p-toluidine. By CHARLES KENNETH TINKLER .XCI1.-The Constitution of Oxadiazole Oxides (Furazan Oxidesor Dioxirne Peroxides). By ARTHUR GEORGE GREEN andFREDERICK MAURICE ROWE .XCII1.-Naphthathioxin and boNaphthathioxin.By THOMASJOSEPH NOLAN and SAMUEL SMILESXC1V.-Studies of Dynamic Isomerism. Part XIV. Suc-cessive Isomeric Changes in Camphorcarboxylamide andCamphorcarboxypiperidide. By THOMAS MARTIN LOWRYand WALTER HAMIS GLovEit .XCV.-Quinonoid Addition as the Mechanism of DyestuffFormation. By AETEUB GEORUE GREEN .XCV1.-Influence of Increase of Initial Temperature on theExplosiveness of Gaseous Mixtures. By ALBERT PARKER, B.Sc.XCVZ1.-Allylamine Derivatives. By WILHELM GLUUD, Ph.D.XCVII1.-Experiments on the Synthesis of apoMorphine. By.JAMES ERNEBT MARSH ..FRANCIS WKLLIAhi KAY and AM& Prciimi .PAGE78679 179580881 783784785286 187 187 688589790191392593494094CONTENTS.ixPAGEXCIX. -A Criticism of Some Recent Viscosity Investigations.C.-Reactions of Halogen-substituted Acids. Effect of Alkalisin Methyl-alcoholic Solution on Bromoacetic, a-Bromo-propionic, and Monobromosuccinic Acids. By EBIK H~STMADSEN . . 965CI.-Cyanogen Bromide and Cyanogen. By AUGUSTUS EDWARDDIXON and JOHN TAYLOR . . 974CI1.-Derivatives of o-Xylene. Part 111. The Presence of aMobile Nitro-group in Each of the Two Trinitro-o-xylenes.By ARTHUR WILLIAM CROSSLEY and WALTER RYLEY PRATTSynthesis of 4 : 5-Dibromo-3-o-xylenol, By ARTHUR WILLIAM CROSSLEY andSYDNEY SMITH . . . . 989C1V.-The Behaviour of Calcium and Magnesium Salts withSoap Solutions and the Determination of Hardness ofWater. By HELEN MASTERS and HENRY LLEWELLYN SMITE 992CV.-Carbamido- and Other Derivatives of up-Dipropylnmino-and Up-Diallylamino-propionic Acids. By EDWARD PERCYFRANKLAKD and -HENRY EDGAR SMITH . . 998CVL-The Estimation of Zinc as Zinc Ammonium Phosphateand Zinc Pyrophosphate. By THOMAS MATTHEW FINLAYand ALEXANDER CHARLES GUMMING , . 1004C VI1.-Mechanism of the Transformation of AmmoniumCyanate into Carbamide, and of the Decomposition ofCarbamide by Heat. The Polymerisation of Cyanic Acid.CVII1.-The Synthetical Preparation of the d-Glucosides ofSitosterol, Cholesterol, and Some Fatty Alcohols. ByARTHUR HENRY SALWAY . . 1022C1X.-Oxidation of Sphingosine and the Isolation and Purifica-CX.-Synthesis of Unsymmetrical Derivatives of Deoxybonzoin.By JOHN CANNELL CAIN, JOEN LIONEL SIMONSEN, andCLARENCE SMITH .. 1035CXL-The Estimation of Small Quantities of Lead. By ALFREDVINCENT ELSDEN and JOHN FIRTH STANSFIELD . . 1039CXI1.-The Hpontaneous Cry stallisation of Solutions of Potas-sium Chloride, Bromide, and Iodide. By BERNARD MOUATJONES and POPATLAL GOVINDLAL SHAH . . 1043CXII1.-The Chemical Nature of Some Radioactive Disintegra-tion Prodncts. Part 11. By ALEXANDER FLEUK . . 1052CX1V.-The Rotatory Dispersive Power of Organic Compounds.Part I. The Measurement of Rotatory Dispersion. ByTHOMAS MARTIN LOWRY . . 1062CXV. -The Rotatory Dispersive Power of Organic Compounds.Part 11. The Form of the Rotatory Dispersion Curves.ByTHOMAS MARTIN LOWRY and THOMAS WILLIAM DICKSON . 1067By EUQENE &OK BINQHAM . . . 959382CIII. --Derivatives of o-Xylene. Part IV.By EMIL ALPHONSE WERNER . . 1010tion of Cerebrone. By ARTHUR LAPWORTH . . 102X CONTENTS.CXVL-Perezone. By FREDERICK GEORUE PERCY REMFRY . 1076CXVI1.-The Absorption Spectra of Various Derivatives ofBenzene. By JOHN EDWARD PURVIS and NIAL PATRICKMCCLELAND . . . . . 1088CXVII1.-Viscosity Maxima and Their Interpretation. ByFERDINAND BERNARD THOLE, ALBERT GEORGE MUSSELL, andALBEET ERNEST DUNSTAN . . 1108CX1X.-Preparation of Secondary Amines from CarboxylicAcids. Part 111. Disecondary Amines from DicarboxylicBy JAMES WALKER, D.Sc.,PACEAcids. By HENRY KONDEL LE SUEUR . . 1119VAN’T HOFF MEMORIAL LECTURE.Ph.D., LL.D., F.R.S.. 1127CXX.-Derivatives of o-Xylene. By JOHN LIONEL SIMONSEN . 1144CXX1.-The Relative Activities of Certain Organic Iodo-com-pounds with Sodium Phenoxide in Alcoholic Solution. Part I.Some Normal Primary Alkyl Iodides.CXXI1.-Rate of Evolution of Gases from SupersaturatedSolutions. Part I. Influence of Colloids and of Suspensionsof Charcoal on the Evolution of Carbon Dioxide. ByALEXANDER FINDLAY and QEORUE K INO (Priestley ResearchScholar, University of Birmingham) . . 1170CXXIIL-The Relation between the Absorption Spectra andConstitution of Piperine, Nicotine, Cocaine, Atropine,Hyoscyamine, and Hyoscine. By JAMES JOHNSTON DOBBIEand JOHN JACOB Fox . . 1193CXX1V.-A Case of Isomerism in the Methylated Ferrocyanides.By ERNALD GEORGE JUSTINIAN HARTLEY .. 1196CXXV.-Solubilities of Salts of Ammonium Bases in Waterand in Chloroform. Part I. Solubility as a ConstitutiveProperty. By CYRIL JAMES PEDDLE and WILLIAM ERNESTSTEPHEN TURNER . . 1202CXXV1.-The Mode of Combustion of Carbon: the Effect ofDrying the Oxygen. By THOMAS FRED ERIC RHEAD andRICHARD VERNON WHEELER . . 1210CXXVI1.-Studies of Dynamic Isomerism. Part XV. TheInfluence of Light on Isomeric Change. By TEOMAS MARTINLOWRY and HAROLD REUBEN COURTMAN . . 1214CXXVII1.-The Estimation of Nitrites by means of Thiocarb-amide, and the Interaction of Nitrous Acid and Thio-carbamide in the Presence of Acids of Different Strength.By MAY EMILY COADE and EMIL ALPHONSE WERNER.The Constitution of d-Sylvestrene andits Derivatives.By WALTER NORMAN HAWORTH, WILLIAMHENRY PERKIN, jun., and OTTO WALLACH . . 1228CXXX.-Cantharene and Other .Hydrocarbons Allied to theTerpenes. By WALTER NORMAN HAWORTH . . 1242CXXX1.-The Synthesis of o-Aldehydophenylglycine. By W IL-HELM GLUUD . . 1251By DAVID SEGALLER 1154. 1221CXX1X.-SylvestreneCONTENTS. xiPAGECXXXI1.-The Purification of Acetone by means of SodiumCXXXII1.-Colour and Constitution of Azomethine Compounds.By FRANK GEORGE POPE and WINIFRED ISABELCXXX1V.-The Absorption Spectra of Some Thio-derivativesCXXXV.-The Constituents of Hops. By FREDERICK BELDINGCXXXV1.-The Preparation and Analysis of Methane. ByCXXXVI1.-Derivatives of o-Xylene. Part V. 5-Bromo-By ARTHUR WILLIAMCXXXVIIL-The Refractivities of Acenaphthene and its Mono-By HOLLAND CROMPTON and WILHEL-Iodide.By KATHLEEN SHIPSEY and EMIL ALPHONSE WERNEB 1255Part 111.WILLETT . . 1258of Benzene. By JOHN JACOB Fox and FRANK GEORGE POPE 1263POWER, FRANK TUTIN, and HAROLD ROGERSON . . 1267COLIN CAMPBELL and ALBERT PARKER . . 1292o-4-xylenol and 6-Bromo-o-4-xylenol.CROSSLEY and DOROTHY JESSIE BARTLETT . . 1297halogen Derivatives.MINA REBECCA SMYTH . . 1302CXXX1X.-Dibenzoyldiaminoacetic Acid. By PAUL HAAS . 1304CXL.-Keto-enolic Tautomerism and the Absorption Spectra ofthe Aliphatic Ketones. By HARRY MEDFORTH DAWSON , 1308CXL1.-The Nickel Salts of the Benzildioximes. By FREDERICKWILLIAM ATACK . . 1317CXLII. -The Rotatory Dispersive Power of Organic Compounds.Part 111.The Measurement of Magnetic Rotatory Disper-sion. By THOMAS MARTIN LOWRY . . 1322CXLIIL-Some Derivatives of Desylamine. By ALEX. Mc-KENZIE and FRED BARROW . . 1331CXL1V.-The Constitution of Allantoin. By ARTHUR WALSHTITHERLEY . . 1336CXLV.-Geranyl Chloride. By MARTIN ONSLOW FORSTER andDAVID CARDWELL . . 1338CXLV1.-The Action of Ozone on Cellulose. Part IV. CellulosePeroxide. By CHARLES DOREE . . 1347CXLVI1.-Note on Cupric Malate and Citrate. By SPENCERUMFREVILLE PICRERING . . 1354CXLVIIL-Organic Ferric Salts. By SPENCER UMFREVILLEPICKERING . . 1358CXLIX. -The Iodocinnamic Acids. By THOMAS CAMPBELLJAMES . . 1368CL.-Guanidine Thiocyanate : Its Formation from AmmoniumThiocyanate. By HANS KRALL . . . 1378CL1.-The Constitution of the ortho-Diazoimines. Part 111.The a- and p-Acyl-3 : 4-toIylenediazoimides as StructuralIsomerides. By GILBERT T.MORGAN and FRANCES &I. G.MICELETHWAIT . . 1391CLI1.-Hydroxyazo-compounds. The Action of SemicarbazideHydrochloride on the p-Quinoaes. By ISIDOK MORRIS HEIL-BRON and JAMES ALEXANDER RUSSELL HENDERSON . . 140xii CONTENTS.PAGEC!LIII.-The Relative Activities of Certain Organic Iodo-com-pounds with Sodium Phenoxide in Alcoholic SoIution. Part11. ko-, w.-, and te?*t.-Alkyl Iodides. By DAVID SEGALLER 1421CL1V.-The Change of Colour of Metallic Haloid Solutions. ByCHARLES SCOTT GBRRETT . , 1433CLV.-'rhe Action of Sulphur Dioxide on Copper at HighTemperatures. By CLIFFORD MORGAN STUBBS . . 1445CLV1.-The Molecular Condition of Mixed Liquids.Part I.Mixtures of the Lower Aliphatic Alcohols with Water.By WILLIAM RINGROSE GELSTON ATKINS and THOMASARTHUR WALLACE . . 1461CLVIL-Isomerism of p-Azophenol. By PHILIP WILFREDROBERTSON. . 1472CLVII1.-The Azo-derivatives of 2 : 2'-Diphenol. By PEILIPWILFRED ROBERTSON and OSCAR LISLE BRADY . . 1479CLIX .-The Constitution of the Tr initro-paminophenols andTrinitropanisidines. By RAPHAEL MELDOLA and FRBD~RICREVERDIN . . 1484CLX.-Non-aromatic Diazonium Salts. Part 11. Azo-deriv-atives from Antipyrinediazonium Salts and their AbsorptionSpectra. By GILBERT T. MORGAN and JOSEPH KEILLY . 1494CLXL-Contributions to Our Knowledge of Semicarbazones.Part 111. Action of Heat on the Semicarbazones of PhenylStyryl Ketone and the Preparation of the CorrespondingPhenylsemicarbazones. By ISIDOR MORRIS HEILBRON andFORSYTH JAMES WILSON .. 1504CLXI1.-The Ten Stereoisomeric Tetrahydroquinaldinomethyl-enecampbors. By WILLIAM JACKSON POPE and JOHN READ. 1515CLXII1.-A New Method of Preparing m-Uhlorobenzoic Acidand the Investigation of its Hydroxylamine Salt. ByWILHELM GLUUD and RICHARD I~EMPF . . . . 1530CLX1V.-The Influence of Temperature and Pressure on theVolatility of Zinc and Cadmium. By TREKETH KUMARANNAIR and THOMAS TURNER . . 1534PartXVI. The Oxidation of Bornylene with Hydrogen Peroxide.CLXV1.-The Reduction of Mercuric Chloride by SodiumFormate. By ALEXANDER FINDLAY and MORTON JAMESPRYCE DAVIES . . 1550CLXVI1.-Polybromides in Nitrobenzene Solution.By ALFREDFRANCIS JOSEPEI . . 1554CLXVIII. -Preparation of Secondary and Tertiary Acid Amidesfrom their Metallic Derivatives. By JITENDRA NATHRAKSHIT . . 1557CLX1X.-Equivalen; Conductivities' of Sodium Hyponitrite,Calcium Hyponitrite, and Hyponitrous Acid. By PRAFULLACHANDRA RAY, RAJENDRALAL DE and NILRATAN DHAR . . 1562CLXX.-The Vapour Density of Ammonium Nitrate, Benzoate,and Acetate. By PRAFULLA CHANDRA RAY and SARATCHANDRA J A N A . . 1565CLXV.-Contributionrto the Chemistry of the Terpenes.By GEORGE GERALD HENDERSON and WILLIAM CAW . . 154... CONTENTS. X l l lPAGECLXX1.-The Chemistry of the Glutsconic Acids. Part VIII.P-Phenylglutnconic Acid and the /I-Yhenyl-a-methyl-glutaconic Acids. By JOCELYN FIELD THORPE and ARTHURSAMUEL WOOD .. 1569Part IX.A Method for Distinguishing Between the Esters of theNormal and Labile Acids. By JOCELYN FIELD THORPE andARTHUR SAMUEL WOOD . . 1579CLXX 111.-T he Formtttion and React ions of Iminocompounds.Part XVIII. The Condensation of cycloHexanones withCyanoacetamide Involving the Displacement of an AlkylGroup. By JOCELYN FIET~D THORPE and ARTHUI SAMUELWOOD . . 1586CLXX1V.-The Replacement of Alkyl Groups in TertiaryAromatic Bases. By JOCELYN FIELD THORPE and ARTHURSAMUEL WOOD . . 1601CLXXV.-The Isomerism' of ;he Oximes. Part I: Tie Di-phenylcarbamyloximes. By OSCAR LISLE BRADY andFREDERICK PERCY DUNN . . 1613CLXXV1.-The Isomerism of the Oximes. Part 11. TheNitrobenzaldoximes. By OSCAR LISLE BRADY andFREDERICK PERCY DUNN .. 1619ByJOHN THEODORE HEWITT, RHODA MARIANNE JOHNSON, andFRANK GEORGE POPE. . 1626CLXXVII1.-The Methylation of Quercetin. - By ARTHURGEORGE PERKIN . . 1632CLXX1X.-The Absorption Spectra of Various Derivatives ofAniline, Phenol, and Benzaldehyde. By JOHN EDWARDh R V 1 S . . . 1638CLXXX.-The Viscosity of Cellulose Nitrate Solutions. ByFRANK BAKER . . 1653CLXXX1.-Adiabatic and Isothermal Compressibilities of SomeLiquids between One and Two Atmospheres Pressure. ByDANIEL TYRER . . 1676CLXXXI1.-The Relation Between Residual Affinity andChemical Constitution, Part IV. Some Open-chain Com-pounds. By HANS THACHER CLARKE (1851 ExhibitionScholar) . . 1689CLXXXTI1.-The Volatile Constituents of Coal. Part 111. ByARTHUR HERBEBT CLARK and RICHARD VERNON WHEELER[with CLAUDE BERNARD PLATTI .. 1704CLXXX1V.-The Volatile Constituents of Coal. Part IV. TheRelative Inflammabilities of Coal Dusts. By EICHARDVERNON WHEELER . . . . 1715ULXXXV.-A New Method for the Determination o€ theConcentration of Hydroxyl Ions. By FRANCIS FRANCIS andFRANK HENRY GEAKE . . 1722CLXXXV1.-The Methylation of Cellulose, By WILLIAM SMITHCLXXI1.-The Chemistry of the Glutaconic! Acids,CLXXVI1.-The Structure of the Salts of Nitrophenols.DEWHAM and HILDA WOODHOUSE (Carnegie Scholar) . . 173xiv CONTENTS.PAGEANNUAL REPORT OF THE INTERNATIONAL COMMITTEE ON ATOMICWEIGHTS, 1914 . . 1742CLXXX V1I.-The Neutrh and Acid Oialates of 'Potakium.By HAROLD HARTLEY, JULIEN DRUGMAN, CHARLES ARCHI-BALD VLIELAND, and ROBERT BOURDILLON .. 1747PartX. The Alkylation of the Ethereal Salts. By JOCELYNFIELD THORPE and ARTHUR SAMUEL WOOD . . 1752CLXXXIX-Note on the Structure of Certain LactonesFormed by the Fission of the gem-DimethylcyclopropaneRing. By WILLIAM HENRY PERKIN, jun., and JOCELYNFIELD THORPE . . 1760CXC.-The Resolution of 2 : 3-Diphenyl-2 : 3-dihydro-1 : 3 : 4-naphthaisotriazine into Optically Active Components.WILLIAM JACKSON POPE and CLARA MILLICENT TAYLOR 1763CXCL-2-Phenyl-5-styryloxazole. By ROBINSON PERCY POULDSand ROBERT ROBINSON . * . 1768CXCI1.-The Action of Magnesium Aryl Haloids on Glyoxal.By HENI~Y WREN and CHARLEEI JAMES STILL . . 1770CXCIIL-The Mutual Solubilities of Ethyl Acetate and Waterand the Densities of Mixtures of Ethyl Acetate and Ethyl,CXCIV.-The Azeotropic Mixtures of Ethyl Acetate, EthylAlcohol, and Water at Pressures Above and Below theAtmospheric Pressure. Part I.By RICHARD WILLIAMMERRIMAN . . 1790CXCV.-The Azeotropic Mixtures of Ethyl Acetate, EthylAlcohol, and Water at Pressures Above and Below theAtmospheric Pressure. Part 11. By RICHARD WILLr AMMERRIMAN . . . . 1801CXCV1.-The Dynamics of Bleaching. By SYDKEY HERBERTHIGQINS . . 1816CXCVI1.-The Constitution of Aconitine. By OSCAR LIBLEBRADY . 1821CXCVII1.-T& Mis'cibility of Solid;. Pirt 11'. The influenceof Chemical Constitution on the Thermal Properties ofBinary Mixtures. By ERNEST VANSTONE . . 1826CXC1X.-Coumaranone Derivatives, Part 11. The Constitu-tion of Ethyl Coumaranonecarboxylate. By RICHARDWILLIAM MERRIMAN .. 1838CC. -Coumaranone Derivatives. Part 111. Acylazo-derivativesof Coumaramonecarboxylic Acid. By RICHARD WILLIAMMERRIMAN . . 1845CC1.-Uondensation of Acid Chlorides with the Ethyl Esters of(a) Cyanoacetic Acid, (b) Malonic Acid, and (c) AcetoaceticAcid. Part I. By CHARLES WEIZMANN, HENRY STEPHEN,and GANESH SAKHABAM AGASHE. . . 1855CCI1.-The Action of Sulphur Chloride and of Thionyl Chlorideon Metallic Salts of Organic Acids : Preparation ofAnhydrides. By WILLIAM SMITH DENHAM and HILDAWOODHOUSE (Carnegie Scholar) . . . 1861CLXXXVII1.-The Chemistry of the Glutaconic Acids.Alcohol. By RICHARD WILLIAM MEBRIMAN . . 177CONTENTS. xvLADENBURG MEMORIAL LECTURE . . 1871CCII1.-The Mechanism of the Condensation of Glucose withAcetone.By JAMES LESLIE AULD MACDONALD (CarnegieScholar) . . 1896CC1V.-The Solubilities of Alkali Haloids in Methyl, Ethyl,Propyl, and isohmy1 Alcohols. By WILLIAM ERNEST STEPHENTURNER and CRELLYN COLGRAVE BISSETT . . 1904CCV. --Nitration of 1 -Chloro-2 : 4-dinitronaphthalene. By MAXRINDL . . . . 1911CCV1.-Constitution of Furoxans (Dioxime “ Peroxides ”), ByMARTIN ONSLOW PORSTER and ATTH THEW FELIX BARKER . 1918CCVI1.-Investigations on the Dependence of Rotatory Poweron Chemical Constitution. Part IV. The Rotations of theNormal Secondary Alcohols of the Formula C,H;CH(OH)-R.By ROBERT HOWSON PICKARD and JOSEPH KENYON . . 1923CCVII1.-The Rate of Hydration of Acid Anhydrides : Acetic,Propionic, Butyric, and Benzoic.By BERNARD HOWELLWILSDON and NEVIL VINCENT SIDGWICE . . 1959CC1X.-Harmine and Harmaline. Part 11. The Synthesis ofisoHarman. By WILLIAM HENRY PERKIN, jun., and ROBERTROBINSON , . 1973By’FEEDERICK DANIEL CHATTAWAY and ROBERT REGINALDBAXTER . . 1986CCX1.-Researches on the Constitution of Physostigmine.Part 111. The Formation of Substituted Indoles fromm-4-Sylidine, and the Reduction of 3-Nitro-p-tolylacrylicAcid. By ARTHUR HENRY SALWAY . . 1988CCXI1.-The Action of Chlorine on m-Iodoaniline and onm-Bromoaniline. By HAMILTON MCCOMBIE and PERCY JAMESWARD . . 1995By FRANK TUTIN 2006PAGECCX.-The Action of Nitrogen Iodide on Methyl Ketones.CCXIIL-The Constituents of Senna Leaves.CCX1V.-The Conversion of Orthonitroamines into iso0xa-diazole Oxides (Furoxnns).By ARTHUR GEOEQE GREEN andPREDERICK MAURICE ROWE . . . 2033CCXV. -Substituted Dihydroresorcins. 1-Methyldi hydroresorcinand 2-Methyldihydroresorcin. By CHARLES GILLING . . 2029CCXV1.-A Study of Some Organic Derivatives of Tin asRegards their Relation to the Corresponding Silicon Com-pounds. Part 11. Condeusation Products of Dihydroxy-dibenzylstannane. By THOMAS ALFRED SMITH and FREDERICSTANLEY KIPPING . . 2034CCXVI1.-Some Derivatives of Oleanol. By FRANK TUTIN andWILLIAM JOHNSON SMITH NAUNTON . . 2050CCXVII1.-The Interaction of Sodium Amalgam and Water.By HERBERT BRERETON BAKER and LESLIE HENRY PARKER . 2060CCX1X.-The Action of Variously Treated Water on SodiumAmalgam. By LESLIE HENRY PARKER .. 207xvi CONTENTS.CCXX.-Studies in the Diphenyl Series. Part V. Derivativesand Substitution Products of the Two Isomeric o-Dinitro-benzidines and Synthesis of Derivatives of Benzerythrene.By JOHN CANNELL CAIN, ALBERT COULTRARD, and FRANCESMARY GORE MICKLETHWAIT . . 2074Part111. Trinitrobenzene, Trinitroanisole, and Picric Acid.By EDWARD CHARLES CYRIL BALY and FRANCIS OWENRICE . . 2085CCXX1I.-The 'Fractionation ok Alioys and kner'als ih theElectric Micro-furnace. By ARNOLD LOCKHART FLETCHER . 2097CCXXIII. -Resolution of a-Anilinostearic Acid. By HENRYRONDEL LE SUEUR . . 2108CCXX1V.-Bismuthinitrites. By WALTER CRAVEN BALL andHAROLD KELLING ABRAM . , 2110C!CXXV.-The Nitrites of Thallium, Lithium, Caesium, andRubidium. Ry WALTER CRAVEN BALL and HAROLD HELLINGABRAM . . 2130Evaluation of theActivities of the Hydrogen Ion and the Undissociated Acid.By HARRY MEDFORTH DAWSON and FRANK POWIS . . 2135CCXXVI1.-Contributions to the Theory of Solutions. TheCCXXVII1.-The Determination of Viscosity. By MALCOLMPERCIVAL APPLEBEY . . 2167CCXX1X.-A Series of Mixtures of Nitro-compounds andAmines, which are Coloured in the Liquid State only. ByCHARLES EENNETE TINKLER . . 2171CCXSX.-Derivatives of o-Xylene. Part VI. 5-Bromo-o-3-xylenol. By ARTHUR WILLIAM CROSSLEY. , , . , 2179CC XXX1.-Z-Epicamphor (I-/3-Camphor). By JULIUS BREDT andWrLLIAM HENRY PERKIN, jun. . . 2182CCXXXI1.-Synthesis of d- and LSylvestrene. By WALTERNORNAN HAWORTH and WILLIAM HENRY PERKIN, jun. . . 2225CCXXXII1.-Some Derivatives of Phorone. Part 1. ByFRANCIS FRANCIEI and FRANCIS GEORQE WILLSON . , 2238CCXXX1V.-Amalgams Containing Silver and Tin. ByWILLIAM ARTHUR KNIGHT and REGINALD ARTHUR JOYNER . 2247CCXXXV.-The Influence of Solvents on the Rotation ofOptically Active Compounds. Part XIX. The Rotation ofCertain Derivatives of Lactic Acid. By THOMAB STXWARTPATTERSON and WILLIAM COLLINS FORSYTH (Carnegie Re-search Scholar) . . 2263CCXXXV1.-The Tautomerism of Thioanilides. By PERCY MAY 2272CCXXXVI1.-Mechanism of the Decomposition of Carbamideand Biuret by Heat, and of the Formation of Ammelide.By EMIL ALPHONSE WERNER . . 2278CCXXXVII1.-The Absorption Spectra of Various Derivativesof Pyridine, Piperidine, and Piperazine in Solution and asVapours. By JOHN EDWARD PURVlS . . 2283PAGECCXX1.-Absorption Spectra and Chemical Reactivity.CCXXV1.-The Catalytic Activity of Acids.Intermiscibility of Liquids. By JOHN HOLIES . . 214

ISSN:0368-1645    

DOI:10.1039/CT91303FP001

出版商:RSC    

年代:1913

数据来源: RSC

摘要:

RAY AND DHAR: CHLORIDES ETC. 311.- Chlorides of the Mercuyialkyl- and Mercuri-alkyEa?-yl-ammonium Series and their Constitutionas based on Conductivity Measurements.By PRAFULLA CHANDRA R-i? and NILRATAW DHAR.IN our previous investigation on the nitrites of the mercurialkyl-and mercurialkylaryl-ammonium series (T., 1912, 101, 687) wehave noticed a striking analogy between these and the correspond-ing chlorides as described by Pesci ( Z e i t s c h . anorg. C?bem., 1897,B 4 RAY AND DHAR: CHLORIDES OF THE MERCURIALKYL-15, 225). It occurred to us that fresh light might be thrown onthe vexed question of the constitution of the latter class of saltsby a study of their conductivities, for which purpose they havebeen found to be sufficiently soluble in water.It will be shownbelow that our surmise has proved to be correct, and that thesimplest formula is acceptable in every case, and that each andall of these compounds belong t o the ammonium type of salts.Pesci, for instance, describes mercuribenzylammonium chlorideas a (‘ triple salt” with the complicated formula:C7H8NHgCl i- C,H,-NH,,HCl+ HgCI,.Prom the conductivity measuremenh it would appear that thesimpler formula, C7H7*NH,,HgCl,, is more appropriate, and that i tyields the ions (CjH7-NH,,HgC1)’ and C1’ in aqueous solution.Franklin, on the other hand, has been led to propose’ a differentsystem of nomenclature ( J . Amer. Ckern. SOC., 1907, 29, 35; 1912,47, 361). According to him, these compounds should be termedmercuric chloride with “ amine, pyridine, and quinoline, etc., ofcrystallisation,” or “ ammonobasic mercuric chlorides.”EXPERIMENTAL.Method of Preparation.-The composition of this class of saltsvaries considerably according to the method of preparationadopted. Pesci (loc.cit.) and Andre (Cornpt. rend., 1891, 112,995) and others have often used cold or boiling aqueous or alco-holic solutions of mercuric chloride or of the amines. We rigidlyadhered to a uniform method, consisting in adding an aqueoussolution of the amine to a concentrated solution of mercuric chloridewith continuous stirring until the ammoniacal d o u r becamepersistent.As the presence of the minutest trace of amine hydrochlorideformed during the reaction would seriously interfere with theconductivity measurements, the precipitate was in each case verycarefully and repeatedly washed by the aid of the pump, andfinally dried, as a rule, in the steam-oven. It remains only to addthat whereas mercuric nitrite invariably forms with amines, com-pounds of the ‘( additive ” type, mercuric chloride, on the otherhand, yields, under similar conditions, compounds both of the“ additive ” and “ subatitutive ” types ; the latter tendency is verymarked, probably owing to the fact that an atom of chlorine ofmercuric chloride often combines with an atom of hydrogen of theamine to form hydrogen chloride.On account of wide divergencein their solubilities, no exact comparison is available, but a generalidea may be easily obtainedAND MERCURIALRY LARYL-AMMONIUM SERIES, ETC.5Since these compounds are sparingly soluble, and a minutequantity of impurity would seriously affect the accuracy of theresults, very pure water is necessary; much precaution was there-fore taken in purifying the water used for these conductivitymeasurements: its conductivity was 1.1 x 10-6 a t 30°.Mercuriammonium Chloride or Znfusible 'Ct'hite Preci$ate,NH,HgCl.The precaution necessary for the preparation of this substance ina state of purity has already been given in detail (Zeitsch. anory.Chem., 1902, 33, 197). This compound has been included in theseries, as it may be regarded as the parent substance from whichthe rest have been derived.Hercurimethylammonium Chloride, NMe(HgCl),.This remarkable compound has not been described, as far as weare aware, by previous workers in this field.The equation of itsformation, namely, NH%Ie,+ 2HgC12= NMe(HgCl), + 2HC1, shouldincline one to regard it as methylamine in which two atom: ofhydrogen have been replaced by the two'HgCl radicles. l t sconstitution will be discussed in the proper place.Found : Hg = 81.73 ; C1=*13*95 ; C= 2.00.CH3NCl,H& requires Hg- 80.00 ; C1= 14.20 ; C = 2-40 per cent.It is worthy of note that under the ordinary conditions we havenot succeeded in preparing ethyl and propyl substituted compoundsof the present series.Pesci, it is true, has described the ethyl derivative, NHEtHgCl;but our attempts to prepare it ended in failure. The compoundwhich was obtained by treating mercuric chloride with ethylamiriegave Hg = 84.19, whilst NHEtHgCl requires Hg = 71-52 per cent.Propylamine yielded a dirty reddish-brown compound, which gaveHg = 84-88 per cent.It is evident that in both these cases highly basic (oxy) saltswere obtained, which enormously raised the percentage of mercury.Me rcu riiso b u t y lamm onium chloride, N H (C4H9) Hg C?l .Found : Hg = 66.61.C,H,,NClHg requires Hg = 65.15 per cent.Mercuripiperaainium chloride, C4H9N,*HgCl.Found : Hg= 62.38. C,HgN2ClHg requires Hg= 62.30 per cent.Merczcrib enay Zammonium chloride, C6H,-CH,*NH2,HgC1,.Found : Hg =54-64. C7HgNC1,Hg requires Hg=53*05 per cent.df ercurib enzylmeth?/lnmmoniz~m chloride,C6H,*CH2*NHMe,HgC1,6 RAY AND DHAR: CHLORIDES OF THE MERCURIALKYL-Found : Hg = 51-75 ; C1= 18.41.C18Hl,NClzHg requires Hg =Mercuribenzyletl~ylarnmonizcm clJoride, C6H,*CHz*NHEt,HgC1,.Found : Hg = 49.76. C9H13NClzHg requires Hg = 49.26 per cent.Mercuriethylenediammonium chloride, C2H,(NH),,2HgC12.Found : Hg= 67.25 ; C1= 23.56.Merczcripyridinium chloride, C,H,N,l+HgCI,.Found : Hg= 61.06. Theory requires Hg = 61.89 per cent.LMer c u r ip*c o Zinium cldo ride, C",H,MeN, H g C 1,.Found : Hg = 54.61. C6H,NC12Hg requires Hg = 54-94 per cent.Mercurinicotinium chloride, CloH,,N,,1~HgCl2.Found : Hg = 50.88 ; CP= 19.95. Theory requires Hg = 52.77 ;Mercuripipem'dinium eldoride, C,Hl1N,2HgCl2.Found : Hg = 65.30 ; C1= 21-93,Mercurihexamethylenetetrammonium chloride,Found : H&= 57.94. C6H,,N4C1,Hg2 requires Hg= 58-65 per cent.The piperidine compound is of a deep yellow colour, and isobtained by adding an aqueous solution of piperidine to mercuricchloride solution, and then diluting with water.The other membersof this group are either colourless or pale yellow.51.02; C1=18*11 per cent.C&r6N,C1,Hgz requires Hg =66.44; C1=23*58 per cent.C1= 18-73 per cent.C,H,,NCl,Hg, requires Hg =63-79; C1=22-4 per cent.(CH2)6N4,2HgC12*,Wercuriammoniunz Chloride (Infusible White Precipitate),NH,HgCl.Dilution. conductivity. Dilution. conductivity.950.2 '420'48 425-1 210'241900 '4 460'64 950.2 230.323800-8 480.68 1900 '4 240.347601.6 498'34 3800.8 249'17Molecular EquivalentMe r c ZL rri e tlhylu m tt LO IL izc iti Chloride, C'H,N (Hg el),.3380 323.58 845 80.896760 367'93 1690 91-9713520 395 *32 3380 98-8327040 416.58 6760 104.13M el.cui,ipiperidiitium C?~ZoricZe, C,H1,N,2HgC1,.2090 262'92 522.5 6:) '724180 275.35 10454 68'838360 285-32 2090.0 71.3336720 313.50 4180'0 78-3AND MERCUR1AI.KPLARYL-AMMONIUM SERIES, ETC.7,~~ercurietAylenediarntt~(~?~iu~L Cldoride, C,H4(NH,),,2HgCl,.hf olecular EquivalentDilution. conductivity. Dilntion. conductivity,1000 207.35 250 51.842000 222.32 500 55.584G00 235.35 1000 58'848000 240'58 2000 60'1416000 251.52 4000 62.8357 8 109.32 144.51156 132.73 289.02312 145'42 578.04624 150.35 1156.09248 155'38 2312.027.3333-1836'4737'5938.84Mtrcuribeii.zylet?~2.yla.m71.lonium Chloride, C,H7*NHEt,HgC12.3700 284.48 1850 142-2474 00 286.32 3700 143'1614800 290'35 7400 145.1729600 320.36 14800 155'18Memurib enzylrnet~,,?/lumnionium Chloride, C,H7*NH&le,HgC12.2735 260.47 1367.5 130.235470 273.68 2735.0 136-7910940 275.18 5470'0 137.5921880 280.42 10940-0 140.21Merczcrl;beizsylammonz'zcm Chloride, C7H7*NH,,HgC12.1080 * 190-2021 60 216.004320 230'328640 235-6417280 248'56540108021604320864095.10108'00115.16117.82124 -28Mercuriisobatylamntonium Chloride, C4H,*NH*HgCI.3075.0 95'32 1537'54612.5 98.58 2306'29225'0 109.53 4612518450.0 120-35 9225-047.6649'2954.7660.17Mercuripiperazihiurn Chloride, C,H,N,HgCI.113122624524904811896125'66 565-5130.32 1131.0133'56 2262-0137.38 4524 *O139'98 9048-062'8365-1666-7868 '6969'99* The value of the molecular conductivity depends on the velocity of the ionsso that it is to be expected that its value would be different in different compounds.There is thus partial deviation from Werner's numbers8 RAY AND DHAR: CHLORIDES OF THE MERCURIALKYL-Mercuripicolinium Chloride, C5H4NMe,HgCl,.Molecular EquivalentDilntion.conductivity. Dilution, conductivity.7280 1137.50 3640 568.7514560 11 50 -35 7280 575.1729120 1205.85 14560 602.92Mercuripyridinium Chloride, 2C5H5N,3HgCl2.18206 1887.53 3034.4 3145936412 1892.33 6ofia.8 315.3972824 1900.38 12137.6 318'39Merctcrinicotinium Chloride, 2C,,,H14N,,3HgC1,.2520504020160iooao420-00 420 70.00460.32 840 75.87520.36 1680 86.72560.56 3360 93'42This compound evidently gives three chloridions (Cl') and acomplex tervalent ion containing mercury.Discussion of Results.From the foregoing table it is evident that the molecular conduc-tivities of some of the salts are about 100 a t a dilution of 1000,whilst others have a value of about 250 a t the same dilution,except infusible white precipitate, which is probably decomposedinto simpler parts, namely, NHgzCl ahd NH,Cl (compare Zeitsch.anorg. Chem., 1902, 33, 205).Adding to Werner's rule (Werner and Miolati, Zeitsch. physikal.Chem., 1893, 12, 35; 1894, 14, 506), it is probable that the formerclass of compounds yields two univalent ions in solution, whilst thelatter, with an average of 250 as their molecular conductivity,yield three ions; the nicotine compound yields four ions, the valueof its molecular conductivity being 450 a t the same dilution.Mercurimethylammonium chloride appears to be of special interest.Th3 two radicles, HgCl, are symmetrically disposed. It would,therefore, be reaisonable to expect that the two chloridions (Cl')would behave similarly.The conductivity measurements actuallybear this out. I n solution the salt gives two chloridions (Cl') andon0 complex bivalent positive ion containing mercury. The resultobtained in this case confirms Werner's rule. Although thiscompound was provisionally regarded as methylamine in whichtwo atoms of hydrogen have been replaced by the radicle HgCl, inreality i t is an ammonium derivative.The pyridine and nicotine compounds are so very sparinglAND MERCURIALKYLARYL-AMMONIUM SERIES, ETC.0soluble that no definite trustworthy conclusions can be drawn fromtheir conductivity measurements.I n all these compounds mercury forms a part of a complex ion,so the ordinary tests for dimercurion (Hg”) fail (for example,precipitation with hydroxidion (OH/) or carbanion (C’O,//).Previous workers have designated these as additive compounds,but most probably they are not of this nature, as is evident fromthe considerations which have been already applied in the case ofthe corresponding nitrites (Zoc. cit.), namely :(1) Ordinary tests for dimercurion (Hg”) fail, so mercuricchloride cannot exist as such.(2) The sum of molecular conductivities of the separate constitu-ents is generally very much less than the actual conductivity of thesalt (especially in the cases of piperazine, ethylenediamine, andbenzylamine compounds).(3) Tests for hydroxidion (OH’) would be obtained if the aminesare in the free state, as they yield hydroxidion in water; but thesolutions give no such test.Moreover, the constituents (mercuricchlorides and amines) are easily soluble in water, whilst the saltsformed from them are practically insoluble.From the above arguments it is almost certain that thesecompounds are not of an additive nature, but are typical complexsalts. I n the case of the most soluble ones (for example, hexa-methylenetetramine and pyridine compounds), silver chloride isprecipitated when argention (Ag’) is introduced into the solution ;thus, chloridion (Cl’) exists in the free state.So, in those com-poiznds which yield only two ions the negative one is chloridion(Cll), whilst the positive ion is a complex radicle containingmercury ; for example, in hexamethylenetetrammonium mercuri-chloride the two ions are (CE2)6N4Hg2C13* and C1’ respectively.By the introduction of argention (Ag’) silver chloride is depositedand equilibrium is disturbed, and the whole of the chlorine isprecipitated.Adopting Werner’s idea in these compounds it is evident thatsome of the chlorine atoms are directly combined with mercury,and form a part of the complex ion (compare Jorgensen (Zeitsch.arnorg. Che,m., 1897, 14, 410). As in the other class of salts alreadystudied (Rgy, Dhar, and Dey), the direct linking is not quite asstable as those described by Werner (compare “New Ideas onInorganic Chemistry,’’ English Trans., pp.3 9 - 4 3 ) .The mercurisulphine compounds studied by Hilditch and Smiles(T., 1907, 91, 39) are also complex compounds.Silver compounds with the halogens as part of the complexpositive ion have also been studied by Hellwig (Zeitsch. unorg10 RAY AND DHAK : EQUIVALENT CONDUCTIVITYC'hnz., 1900, 25, 187). Mercuric chloride and mercuric nitrite arefeebly ionised, even a t high dilutions. It is always seen that thoseelectrolytes which are feebly ionised can easily form complexes(for example, mercuric iodide, mercuric cyanide, etc.). Abegg, inhis '( Theory of Electrolytic Dissociation " (English Trans., p. 117),has given a list of complex mercury compounds.There is thus a distinct tendency in the case of mercury to formcomplex compounds.From these arguments i t is evident that the ammoniacal mercuricchlorides are typical complex salts wit%h a tervalent, bivalent, orunivalent complex radicle, containing mercury and the other partis always chloridion (Cl').Thus, these bivalent salts behave like a simple chloride, such asbarium chloride or zinc chloride, whilst the univalent salts arequite similar to chlorides, such as ammonium chloride or sodiumchloride.It will be seen that the present investigation and the previousone on the corresponding nitrites mutually strengthen and confirmeach other.CHEMICAL LABORAI'ORY,PRESIDENCY COLLEUR, CALCUTTA

ISSN:0368-1645    

DOI:10.1039/CT9130300003

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年代:1913

数据来源: RSC

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10 RAY AND DHAK : EQUIVALENT CONDUCTIVITYIII.-Btpivalent Conductivity and Ionisation cfNitrites.By PRAFULLA CHANDRA RAY and NILRATAN DHAR.THE study of nitrites from the point of view of equivalent conduc-tivity and ionisation was undertaken by Pick (Diss., Breslau, 1906),but he worked only with a very limited number of salts. Ley andKissel (Bey., 1899, 32, 1363) measured the equivalent conductivityof mercuric nitrite alone. RBy and Mukherjee (P., 1910, 26, 173)studied the ionisation of a series of alkali nitrites from theircryoscopic behaviour. I n our study of the nature of the complexesof potassium mercurinitrite we have incidentally measured theequivalent conductivities of mercuric nitrite, potassium nitrite, andpotassium mercurinitrite (T., 1912, 101, 965).With the view ofthrowing light on the constitution of this important group of salts,an exhaustive study of their equivalent conductivities and ionicbehaviour has been undertaken. As ;I rule, crystals of thesAND IONISATION OF NITRITES. 11nitrites were prepared, and freed from adhering mother liquor.Generally, these salts were obtained by double decompositionbetween silver nitrite and the corresponding chloride and evapora-tion in a vxuum of the filtrate. Evaporation on the water-bathhad t o be avoided, as these nitrites undergo marked hydrolysis a thigh temperatures. The nitrites of the alkylammonium bases whichhave been included in this paper are those recently described byR2y and Rakshit (T., 1911, 99, 1470; 1912, 101, 141, 216). Some-times, also, salts in solution only were obtained by double decom-position between barium nitrite and equivalent proportion of thecorresponding sulphate in a tall cylinder (compare R2y and Dhar,loc.cit.). This procedure was necessary for those nitrites thesolutions of which decompose when their concentrations areincreased (for example, copper and nickel nitrites). The tempera-ture was 20° +Om lo.The water used in these measurements was purified by continuousdistillation with a tin condenser, first by means of acid perman-ganate, and then of alkaline permanganate; all the joints also wereof tin. This arrangement was that of Jones and Mackay (Zeitsch.physikcrl. CA,em., 1894, 14, 317) with a few alterations. The con-ductivity of the water used was 1 x 10-6 a t 20°.I n the following tables the value of the maximum equivalentconductivity is obtained by adding the separate ionic mobilities ofthe cation and anion, since the maximum equivalent conductivitycannot be exactly obtained by ordinary measurements, the valuesbeing sometimes highly affected by hydrolysis.The values of ionic mobility for the univalent ions at 18O areprimarily based on Kohlrausch’s figures.The small changes aredue to the use of 0.496, instead of 0.497, for the cation transferencenumber of potassium chloride and to the change of atomic weightadopted in 1911. The corrections for temperature were made byKohlrausch’s equation :where K , and Kl are the conductivities at the temperatures t2, t , ;A K,.is the temperature-coeacient which gives the change of con-ductivity expressed as a function of conductivity, K18, at 1 8 O for achange in the temperature of lo.Also the following equation of Kohlrausch can be very advan-tageously used in obtaining the migration velocity of an ion a ttemperatures not far removed from 18O:U[=U18- x ( l + ~ t ( t ~ - 1 8 ~ ) +F(t0-lS0)2}.The values for a and fl are taken from Kohlrausch’s tablcs(Sitzuiiysber. K. dliad. It’iss. Berlin, 1901, 1031)12 RAY AND DHAR : EQUIVALENT CONDUCTIVITYEquivalentDilution. conductivity.20 -7 96'7262.1 104 '54The ionic mobility of nitrosion (NO,') at 25"=61'7 (Vogel,Zeitsch. anorg. Chem., 1903, 35, 403), whilst Pick (loc. cit.) givesit as 63 a t 2 5 O and 57 a t 18O.The latter values are probably alittle too high, since he has taken the equivalent conductivity ofsilver nitrite a t a molar concentration of 0-0265 = 69.4, the valuewhich is actually found. This value is, however, higher than theactual value owing to hydrolysis.EquivalentDilution. conductivity.186.3 107.69558.9 110'92E uivaleritDilution. conkctivity.6 70.3218 75.0054 91.52EquivalentDilution. conductivity.162 100'00486 102.05The calculated value of A, for lithium nitrite a t 20° is 93.7.SodiumCrystals were used.Dilution. couductivity.9 78'9827 94.4081 103.05Eqnivalen tNitrite.EquivalentDilution. conductivity.243 109.55729 119.50The calculated value of A, for sodium nitrite a t 20° is 104.3.Calcium Nitrite.Crystals of this salt were used.EquivalentDilution.conductivity.5-8 79'9917.4 96'6652.2 103.57The calculated value of A, forEquivalentDilution. conductivity.156.6 108.75469'8 130'26calcium nitrite a t 20° is 112.9AND IONISATION OF NITRITES,EquivalentDilution. conductivity.12 85.5536 92-30108 111'1113EquivalentDilution. conductivity.321 120.00972 124.91Barium Nitrite.Crystals were used.EquivalentDilution. conductivity.6-31 78'8818-93 97.5656'79 111-61EquivalentDilution. conductivity.170 *37 122'38511.11 124-12The calculated value of A, for barium nitrite at 20° is 116.75.Disturbances due to hydrolysis are very marked in this case.Magnesium Nitrite.The conductivity experiment was made with solution.EquivalentDilution. conductivity.15'5 91.1546 -5 108-65Equivaleu tDilution.conductivity.139.5 120'55418'5 127.15The calculated value of A, for magnesium nitrite at 20° is 106.9.Zinc Nitrite (in Solution).EquivalentDilution. conductivity.12'4 59-2737 -2 80-87111-6 104-30EquivalentDilution. conductivity.334.8 116.251004'4 117.66The calculated value of A, for gnc nitrite a t 20° is 108*1.This solution is very feebly acid. This is due to the hydrolysisof the salt.Silver Nitrite.Crystals (purified by recrystallisation) were used.EquivalentDilution. conductivity.70-6 70'32211'8 85.73EquivalentDilution. conductivity.635'4 110.32The calculated value of A, for silver nitrite at 20° is 115.214 KAY AND DHAR : EQUIVALENT CONDUCTIVITYT e t ra 71) e t hjy7amm o rt i u m Ni f Tit e ,EquivalentDilution.conductivity.20.4 83-5240-8 95.5181-6 101.12Equi valeutDilution. conductivity.163-2 103'833264 106'53652.8 109.65The calculated value of A, for tetramethylammonium nitrite atZOO is 99.2.Crystals were used,EquivalentDilution. conductivity.25.6 79.1176-8 82-82230'4 87 '68EquivalentDilution. conductivity.691'2 93-242073'6 93.806220.8 94.20The calculated value of A, for phenyldimethylammoniurn nitritea t 20° is 85.4. This salt is feebly alkaline to litmus.isoButylammonium Nitrite.Crystals were used.EquivalentDilution. conductivity.28 75-5584 80-35EquivalentDilution. conductivity.252 81.12756 81 *92The calculated value of A, for isobutylammonium nitrite at20° is 91.3.The solution is almost neutral t o litmus.Bu.tylammonium Nitrite.Equivaleritnil ntion.eonduc tivity.16 65 '9132 66'9964 67'85EquivalentDilutioa. conductivity.128 75-23256 84-10512 89 -50The calculated value of A, for butylammonium nitrite a t ZOOis 91.3.The solution is feebly alkaline to litmusAND IONISATION OF NITRITES. 15A llylammonium Nitrifc.Viscous liquid was used.EquivalentDilution. conductivity.17'8 79.4653'4 87.12EquivalentDilution. conductivity.160.2 96'50480'6 102.25The calculated value of A, for allylammonium nitrite' a t 20°is 94.The solution reacts feebly acid.Crystals were used.EquivalentDilution. conductivity.24 69 -5572 79.15EquivalentDilution.conductivity.2: 6 81'13648 85-12The calculated value of A, €or dipropylammonium nitrite a t 203is 82.9.Ths solution reacts very feebly alkaline.Propylunt monium Nitrite.EquivalentDilution. coiiciuctivity.7'4 75.5122-2 867166'6 93-83EquivalentDilution. conductivity.199'8 105.15599'4 111'00The calculated value of A, for propylammonium nitrite a t 20°is 95.4.The solution reacts very feebly acid.Tripopglammo nium flitri t e .Equivalerr tDilution. coucluct ivity.20 '4 60-0063'1 73'65EquivalentDilution. conductivity.189.3 79.85567.9 91'80The calculated value of A, for tripropylammonium nitrite a t20° is 78.2.The solution is almost neutral to litmus16 RAY AND DHAR : EQUIVALENT CONDUCTIVITYCrystals were used.EquivalentDilution. conductivity.23.3 81.5569'9 90.25EquivalentDilution.Conductivity.209 -7 95 -53629 -1 100'32The calculated value of A, for diethylammoiiium nitrite a t 20°The solution reacts very feebly alkaline.is 88.7.Triethylammonium Nitrite.EquivalentDilution. conductivity.60 85-52180 89'21EquivalentDilution. conductivity.540 91-25The calculated value of A, for triethylammonium nitrite atThe solution is almost neutral to litmus.20° is 105.2.NickeZ Nitrite (in Solution).EquivalentDilution. conductivity.18'17 57-3254-51 78.52EquivalentDilution. conductivity.163.53 95.35490'59 114-12The calculated value of A, for nickel nitrite a t 20° is 94.0.The solution is feebly acid to litmus.Copper Nitrite (in Solution).EquivalentDilution. conductivity.18-12 58-5554'36 79'92EquivalentDilution. conductivity.162.58 99'46487'74 111.18The calculated value of A, for copper nitrite a t 20° is 106.8.The solution is feebly acid.Sodium dlercurim*trite.(RBy, T., 1907, 91, 2031,)Equi r den tDilution.conductivity.100 229-35300 250.00EquivalentDilution. conductivity.900 266'7AND IONISATION OF NITRITES. 1 7Tike its potassium analogue (Zoc. c i t . ) , in concentrated solutionsonly this salt behaves as n complex salt with the ions Na' andmercurinitrosion, Hg(NO,),,"; but as it is diluted it begins todecompose into its constituents, as is seen in the table; thus a t adilution of about 1000, the equivalent conductivity is nearly 265,showing that this salt behaves like a salt decomposing into threeions (compare Werner and Miolati, Zeitsch.physikal. Chem., 1893,12, 35; 1894, 14, 506). At. higher dilutions the value of theequivalent conductivity increases very fast owing to decomposition.The solution has a slightly acid reaction due to hydrolysis ofmercuric nitrite, which more than counterbalances the alkalinitydue to the hydrolysis of sodium nitrite.Tetramethylammonim Mercum'nitrite.Crystals were used.EquivalentDilutiou. conductivity a t 30".76 101 -60228 115;72EquivalentDilution. conductivity a t 30".684 129.31Similarly, this salt behaves in a concentrated solution like acomplex salt. On dilution i t begins to decompose, and the equiva-lent conductivity attains the value of about 150 instead of nearly100 a t a dilution of 1000 (compare Werner and Miolati, Zoc.cit.).It shows slight acidity, due to the same reason as in the previoussalt.Hercurosomercuric Nitrite, 2Hg(NO,),,HgNO, (in, solution).Dilution.187561Equivalentconductivity.62'3380.10The preparation of this salt* has been described by one of us(RGy, T., 1902, 81, 645). It behaves like a univalent salt, givingonly two ions in solution; thus the equivalent conductivity at a dilu-tion of about 1000 litres is nearly 100. A t very high dilutions thesalt, like other complex salts, begins to dissociate into simplerparts.I n this salt the ions are mercurosion (Hg') and the univalentcomplex ion dimercurinitrosion, Hg,(NO,),'.At very high dilutionsthe complex begins to decompose, and causes acidity due t o thehydrolysis of mercuric nitrite which is formed.* This salt exists only in solution ; on evaporation it is converted into thenitrate.VOL. CIII. 18 EQUIVALENT CONDUCTIVITY AN11 IONISATION OF NITRITES.Biscussion, of R c s i t ? Is.The equivalent conductivities of the nitrites, as is evident fromthe foregoing tables, do not reach a maximum value since theyundergo hydrolysis. I n the alkali and alkaline earth nitrites, aweakly basic reaction is obtained, since the corresponding hydr-oxides are strong bases; whilst in the case of copper, zinc, nickel,mercury nitrites, etc., there is a feebly acid reaction since thehydroxides are very feeble bases, and this indirectly proves alsothat nitrous acid is not a very weak acid, thus corroborating theevidence of Schuinann (Ber., 1900, 33, 1527) and Blancharrl( Z e i t s c h .physikal. Chem., 1902, 41, 681).I n the case of the alkylammonium nitrites the behaviour wouldalso depend on the strength of the amines (compare Bredig, Zeitsch.physikal. Chem., 1894, 13, 191).I n the compounds studied by us, effects due to hydrolysis mustbe reckoned with, for on account of the high velocities of hydrionand hydroxidion, the value of A, is-seriously affected, even if thedegree of hydrolysis is very small. The hydrolysis in the case ofcalcium nitrite is rendered evident from the milkiness of thesolution when evaporated on a water-bath. I n the case of strontiumnitrite i t is much more marked; in fact, a pellicle of strontiumcarbonate is formed on the surface, and the solution is found to bemore and more alkaline. Pick also noticed the turbidity of calciumnitrite solution, but has overlooked the real cause of it (Zoc. cit.,p. 16). Hence the value of the equivalent conductivity of thenitrates as measured by Kohlrausch, Noyes, and Jacobsen is a littlelower than the corresponding nitrites at a similar dilution, althoughthe ionic mobility of nitranion is almost equal to that of nitrosion.It is evident from this work that the amine nitrites behave liketypical ionogens, and are similar to alkali and alkaline earthnitrites.It will also be seen that the results arrived a t by the conductivitymeasurements corroborate in the main those deduced from thecryoscopic method by R2y and Mukherjee.We are now engaged in measuring the viscosity and the degree ofhydrolysis of the nitrites, so that the true degree of dissociation ofthese salts may be ascertained.CHEMICAL LABORATORY,PRESIDENCY COLLEGE, CALCUTTA

ISSN:0368-1645    

DOI:10.1039/CT9130300010

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年代:1913

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J 0 U R N A LOFTHE CHEMICAL SOCIETY.T RAN SAC TION S .H. BHERETON BAKER, M.A., D.Sc.,J. N. COLLIE, Ph.D., F.R.S.A. W. CROSSLEY, D. Sc., Ph.D., F.R.S.l!’. G. DONNAN, M .A., Ph. D., F.R.S.BERNARD DYER, D.Sc.M. 0. F O H S ~ E R , D.Sc., Ph.D., 1.R.S.F. R.S.aomnrittat of @ublitiltion :T. M. LOWRY, D.Sc.A. MCKENZIE, K A . , D.Sc., Ph.D.W. H. PERKIN, S C . ~ . , LLD., F.R.S.J. C. PHILIP, D,Sc., Ph. D.F. B. POWER, Ph.D., LL.D.A. SCOTT, M.A., D.Sc., F.R.S.S. SMILES, D.Sc.6bitor :J. C. CAIN, D.Sc,, P1i.D.Sub-Qbitor :A. J. GREENAWAY.1913, Vol. CIXX. Part 11.LONDON:GURNEY ct; JACKSON, 33, PATERNOSTER ROW, E.C.1913RICHAND CLAY & SONS, LIMITED,BRUNSWICK STREET, STAMFORD STREET, S.E.,AND BUNQAY. BUFFOLK

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DOI:10.1039/CT91303FP017

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年代:1913

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THOLE : VISCOSITY AND ASSOCIATION. PART 111. 19I V.- Viscosit!y cmcl Association. Pcwt 111. l'heExistence of Rucemic Compounds in the LiyuiclState.By FERDINAND BERNARD THOLE.THE question of the existence of liquid racemates is one that hasreceived considerable attention during the1 past twenty years, andin few such problems have the experimental data and resultingdeductions been more contradictory.Such a result is somewhat to be expected, for the conclusions, inpractically every case, have been based on the study of physicalprope'rties and constants, and few of these are sufficiently consti-tutive or accurate to give figures the interpretation of which is notopen to doubt, especially as liquid racemates, if they do exist, areprobably dissociated to a great extent into their components.I n two previous papers (T., 1908, 93, 1815; 1910, 97, 1249)the author attempted to solve the problem by determining theviscosities of active and inactive isomerides, since viscosity is un-doubtedly one of.the most valuable constitutive properties, and,moreover, is one which gives very accurate results with a limitedquantity of material. The results showed that racemic compoundscan exist in solution, although in most cases the racemate onsolution dissociates either completely or to a very considerableextent into the mixture of dextro- and laevo-forms.The following is a summary of the chief researches that havebeen published on this question:CoZow.-Byk has shown (Zeitsch. physikal. Chem., 1904, 49,682) that solutions of copper tartrate and copper racemate differin colour, the former being blue and the latter greenish-blue.Molecular Volume.-Marchlewski found that tartaric acid inaqueous solution has a smaller specific volume than racemic acid,but Ranken and Taylor have pointed out (Proc.Roy. SOC. Edin.,1907, 27, 172) that these results, which agree with those of Perkin(T., 1887, 51, 362), require confirmation.Molecular Weight.-Anschutz and Raoult, who first determinedthe molecular weights of active and racemic dimethyl diacetyl-tartrat.es by the cryoscopic method, obtained no evidence of racemiccomplexes in solutions. Bruni and his co-workers ( A t t i R. Accad.Lincei, 1902, [v], 11, 212; 1904, [v], 13, 349) have more recentlyshown that whilst this result is true for dilute solutions, dissocia-tion is only partial in more concentrated solutions in the cases ofdimethyl racemate, dimethyl diacetylracemate, ammonium hydrogenracemate, and ethyl dl-dibromophenylpropionate.c 20 THOLE : VISCOSITY AND ASSOCIATION.PART 111.Afinity Constnn t.-According to Ostwald (ZeitsclL. physikal.Clum., 1889, 3, 372)) active and inactive tartaric acids have thesame conductivity.Temperature Effects.-Pasteur and Ladenburg have shown thatwhen certain dextro- and laevo-isomerides (d- and I-tartaric acidsand d- and I-coniine) are mixed in the liquid condition heat isevolved, but Adriani (Zeitsch. physikal. Chern., 1900, 33, 453) doesnot accept this as evidence of racemate formation.Freezing-poiwt Curues.-A great deal of work has been done inthis connexion on the lines laid down by Roozeboom (Zeitsch.physikal.Chem., 1899, 28, 494), the chief workers in this fieldbeing Adriani, who obtained curves consisting of two eubcticsand one maximum a t 50 per cent. in the cases of dimethyl tartrate,dimethyl diacetyltartrate, mandelic acid, and benzoyltetrahydro-quinaldine, and Findlay and Hickmans (T., 1907, 91, 905),who obtained similar curves with the E-menthyl mandelates. Thelatter authors have confirmed their conclusions by a series of solu-bility measurements (T., 1909, 96, 1386). Kipping considersthat racemic compounds may have a free existence in the liquidstate, since d-hydrindamine db-mandelate is resolvable by crystal-lisation from water, whilst dl-hydrindamine d-mandelate could notbe so resolved (T., 1909, 95, 405, 1386).Absorption Spectra.-Stewart (T., 1907, 91, 1537) determinedthe absorption spectra of aqueous solutions of dextro-, meso-,and racemic tartaric acids, and found that the absorption curve ofthe last-named acid began to diverge from that of the other formsa t concentrations above 14 per cent.Viscosity.-Ranken and Taylor have pointed out that in moder-ately concentrated solutions racemic acid has a lower viscosity thantartaric acid.Beck (Zei2sch.physikal. Chem., 1904, 48, 670) has determinedthe viscosities of a number of active and inactive compounds in thefused state. I n the cases of camphoroxime and carvoxime allmethods agree that the inactive substance is a 3-racemic mixtureand not a true racemate.I n the cases of dimethyl racemate anddimethyl diacetylracemate, freezingpoint curves and cryoscopicmeasurements show the free existence of the racemic compound.Beck states, however, that his viscosity results show no indicationof a liquid racemate in any of the above-mentioned substances.I n two previous papers (T., 1908, 93, 1815; 1910, 97, 1249)the author investigated the viscosities of a number of active andinactive compounds in solution. I n some cases the results mustbe taken with some reserve, owing to the difficulty of careful puri-fication without inducing racemisationTHOLE : VISCOSITY AND ASSOCIATION. PART 111. 21Definite evidence was, however, obtained that racemic acid canexist to a limited extent in aqueous solution, the dissociation being,however, nearly complete a t low concentration. The dextre andinactive octyl hydrogen phthalates in benzene solution possessidentical viscosities, as do the mandelic acids in water and pyridinesolutions. I n the case of the mandelic acids in amyl acetate solutionthere appears to be a slight divergence of the viscosity-conceatra-tion curves for solutions of the active and inactive acids.The differences are, however, very small, and, as was emphasisedin the paper, the evidence afforded was merely suggestive, and notconclusive, of the existence of racemic mandelic acid in thesolution.From the above results the following conclusions may be fairlydrawn :(1) Although racemic compounds undoubtedly exist in many casesin the solid state, the evidence for their existence in solution or inthe fused state is conflicting.(2) The majority of the evidence seems to point to the limitedexistence of liquid racemate complexes, although dissociation takesplace t o a very considerable extent when a racemate passes into theliquid condition.(3) In dilute solutions all the results show complete dissociation,and only in the case of more concentrated solutions is any evidencefound of racemate existence ; moreover, the degree of dissociationa t a given concentration and the rate of dissociation with dilutiondepend on the nature of the solute and the solvent.I n fact, theposition appears precisely analogous to that of the electrolytic dis-sociation of salts in dilute solution, and is on a par with that of theexistecce of double salts in solution.Through the kindness of Dr.Pickard and Mr. Kenyon a numberof active and inactive alcohols have been placed a t the author’sdisposal, and an opportunity has been thus afforded for extendingconsiderably the previous viscosity determinations in connexionwith this subject. A t the same time, owing to very considerableimprovements in the apparatus used, i t has been possible to extendthe measurements to a considerably wider range of substances.EXPERIMENTAL.The manipulative difficulties involved in the determination ofviscosities of the substances detailed below were considerablyincreased by the limited quantity of material and by the necessityfor investigating in the fused state certain compounds which aresolid a t the ordinary temperature.It was necessary, therefore, todesign a viscometer which should be capable of giving fairly accurat22 THOLE : VISCOSITY AND ASSOCIATION. PART 111.results with not more than 1 C.C. of liquid, and a t the same timeobviate the difficulty and waste of filtering fused solids into theapparatus (a precaution quite necessary with the older forms ofviscometer).The type of instrument used is figured below, and while basedessentially on the Ostwald principle is provided with a horizontalcapillary and with two small wells or sumps into which particles offoreign matter may settle.The smaller instrument (Fig. 1) was used in the investigation ofthe active alcohols, and had a capacity of 0.7 C.C. The receivinglimb was made of glass tubing of 3 cm.bore, and had a bulb ofF I G . 1.adFIG. 2. . dabout 0.3 C.C. capacity near its lower end. The horizontal capillarywas 5 cm. long and 0.03 cm. bore, and the measuring limb 20 cm.long and 0'2 cm. bore. The viscometer was suspended verticallyin the thermostak, and filled with liquid until the meniscus regis-tered with the etched lines cd, any excess being removed with acapillary pipette. Twenty minutes were allowed for completedrainage from the sides of the receiving limb, and the levels werethen finally adjusted. The liquid was then drawn above the etchedline a, and the time of flow of the upper meniscus from a to Z,noted, a lens being used to give increased accuracy in timing.Theexperimental results show that even on such a small scale consistentvalues can be obtainedTHOLE : VISCOSITY AND ASSOCIATION. PART 111. 23The average error is indicated by the following typical resultswith viscometers of the smaller type (0.7 C.C. capacity).Viscometer A .-Z-Heptan-j3-01.Time of flow in seconds.213'4214.2 211.4 Mean =214'0.214.0Viscogity. Density.Viscometer A 1-heptan-8-01 ..................... 0.05055 0.8155,, C d-heptan-B-ol ..................... 0'05042 0.8155,, A d-n-bntylisopropylcrbinol ... 0.07088 0.821 0 ,, C d- + Z-butylisopropylcarbinol.. 0.07070 0 8212I n all the other cases sufEcient material was available to permitthe use of the larger apparatus (Fig.2), which had a capacity of2.4 c.c., and has now been adopted as the standard type of instru-ment in the present series of researches. For use with volatile orhygroscopic substances guard tubes of the type described in aprevious paper (T., 1910, 97, 2598) may be ground to the openends of the limbs.The viscometers were calibrated with ethylene dibromide, and incertain cases with aniline, liquids which are particularly suitable,as they can be readily obtained in a high state of purity.The specific gravities a t 25O were determined in Sprengel pykno-meters, and at the higher temperatures in a small bulb of 3 C.C.capacity .I n the experiments at 25O the temperature of the bath was main-tained withir. O*0lo by means of a Lowry spiral thefmoregulator.For the higher temperatures a large beaker of water was used,the heating being controlled by hand, and the temperature main-tained within O - l O .Control of the temperature was greatly facili-tated by covering the water with a film of mineral oil, whichprevented rapid evaporation.The octyl hydrogen phthalates were prepared from sec.-octylalcohol by tho, method described by Pickard and Kenyon (T.,1907, 91, 2058).The menthyl mandelates .were prepared from the acids andmenthol by the Fischer-Speier methods described by McKenzie andFindlay and Hickmans respectively (T., 1904, 85, 1254; 1907,The esters of tartaric and mandelic acids were purified byrepeated fractional distillation under diminished pressure, carebeing taken to prevent the' absorption of moisture by these sub-stances (compare Beck, Z e i t s c h .physikal. Chem., 1904, 48, 670).The d- and Z-carvoximes were purified by crystallisation, and the91, 905)24 THOLE : VISCOSITY AND ASSOCIATION. P w r I I I .inactive oxime was prepared by melting together equal weights ofthe isomerides.The alcohols were lent by Dr. Pickard and Mr. Kenyon, and usedwithout further purification.TABLE I.The Octyl Hydrogen Phthalates.Deztro.Time of flowTemperature. (in seconds).65" 151.671 113.676 90.280 77.485 63.51waclizt.e.Time of flowTemperature. (in seconds).65" 153.970 120.175 94 -080 77-585 63'4Owing to lack of material, accurate density-determinations couldnot be made, and therefore times of flow were measured over atemperature range.The results when plotted are found to lie on asingle curve, showing that no racemic compound is present.This conclusion was previously arrived at from the viscosities ofbenzene solutions of these esters.TABLE 11.The ac-TPe trahydronaph t hots.Dexlro.Time of flowTemperature. (in seconds).34" 231.340 141'748 81 -755 54.0Inactive.Time of flowTemperature. (in seconds).31.1" 296.438.0 165.044'0 106.050-0 71.655.0 53 '462.4 36'7I n this case also the results lie on a single curve, showing theabsence of any racemate in the inactive mixture.TABLE 111.The AIcohols at 25O.Viscosity.Alcoh 01. v d l (found). dE ( c ~ l ~ u l ~ t e zPhenylethylcarbiiiol ... 0.1393 0.1306 0.1349 0'1344Heptan-8-01 ............0.05042 0.05055 0.05055 0 '05048Octan-B-ol ............... 0-06328 OuO6550 0.06490 0'06460I n the case of octan-/3-ol the value in the third column is that ofa m-ixture containing GO per cent. of the dextro-form, and thTHOLE : VISCOSITY AND ASSOCIATION. PART 111. 25viscosity value in column 4 is calculated for a mixture of thiscomposition.The results in the last two columns indicate clearly that theinactive mixture is only a conglomerate.TABLE Tv.The Carvoximes.Fwed at 95".Viscosity.Dextro ......... 0.0476Inactive ......... 0.0474In amyl acetate solulioit at 25"(1 gram goxima in 7 c.c. of8olvcttt).Viscosity.Dcxtro ......... 0.01109Inactive ......... 0 '01 11 1ISince the active forms of this oxime melt a t 73O and the mixturea t 9Z0, this might be expected a t first sight to be a genuine caseof the existence of a racemate.Adriani has, however, shown thatthe freezing-point curve exhibits a maximum a t 50 per cent., butno eutectics. In other words, the substance melting a t 9 2 O consistsof t)-racemic mixed crystals, and is not a genuine racemic compound.This conclusion is amply confirmed by the viscosity results, both inthe fused state and in solution. Beck has also determined theviscosities of various mixtures of d- and Lcarvoximes, and his resultsare in full agreement with those detailed above.TABLE V.The Tartaric Esters.Ester. Temperature. Viscosity.Methyl d-tartrate .................. 85" 0.133,, racemate .................85 0.130Y 9 ,, +methyl tar-trate (50 per cent.) ............ 85 0-131Ethyl d-tartrate .................. 25 3 -457, , racemate .................... 25 1.360The esters of tartaric acid (particularly the ethyl esters) arenotably difficult to purify, especially in view of their hygroscopicnature.In the cases investigated, therefore, repeated vacuum distillationww employed until approximately constant viscosity-values wereobtained.In the case of dimethyl racemate several methods, notablyf reezing-point curves and cryoscopic measurements, seem to indicatethat this substance is capable of actual existence. The ester wasinvestigated by Beck, who determined the viscosities of a range ofmixtures of the dextre and inactive esters.He concluded that hisresults were in sufficient agreement to predyde the possibility o26 THOLE : VISCOSITY AND ASSOCIATION. PART 111.the existence of a racemate. When plotted, however, they lie onby no means a smooth curve, and must be accepted with somereserve. The viscosities detailed above seem to indicate the probableexistence to an appreciable extent of both dimethyl and diethylracemates in t.he liquid state, the racemate, as in the case of thefree acid, possessing it lower viscosity than the active form.Beck further investigated the viscosities of fused dimethyldiacetyltartrate and dimethyl diacetylracemate, and concluded thatthe two esters had the same viscosity, showing the absence of anyracemic compound. His results are appended, and it will be noticedthat they are capable of another interpretation, since with oneexception the viscosity falls with increasing concentration of themactive ester.TABLE VI.Dimethyl Diacetylturtrate and Diacetylracemute at 1 0 4 O (Beck).Viscosity(77 of water at 25"= 1).Pure racemate ........................6,7646'6666'912Pure active ester ..................... 6'933Mixture.90 per cent. racerirate,, racemate...............110 ,, active ester ........................ { :: ,, active ester ............Bruni has proved by cryoscopic measurements that dimethyldiacetylracemate can exist in non-dissociating solvents, such asethylene dibromide, and Adriani's freezing-point curve shows twoeutectics and a maximum a t 50 per cent.of each active form.TABLE VII.The 1-Menthyl Nandelates.In amyl acetalc solistion at 25"(1 '1 gram of ester in 7 C.C. of solvcitl). Fused at 85".Viscosity. Viscosity.,, 1-mandelate ... 9.0632 0.01085L - n - L i i t hyl dl-mandelate ... 0.0653 0~01110These esters have been fully investigated by Findlay and Hick-mans, who conclude from freezing-point curves and solubility deter-minations that the partly racemic ester is capable of free existence.This conclusion is fully borne out by the above viscosity results.TABLE VIII.The E't7tyl Mnndelates at 25O.Ester. Viscosity.Ethyl dl-mandelate ..................... 0.1971 ,, l-mandelate ........................ 0.197THE FORMATION OF TETRAHYDRO-OXAZOLES, ETC. 27These r e s u h demoiistrate clearly that ethyl cll-mandelate iscompletely dissociated under the conditions of the determinations.Summary of Results.(1) I n most cases dl-liquids and solutions are merely conglomer-ates. This has been shown in the cases of octyl hydrogen phthalate,uc-tetrahydronaphthol, phenylethylcarbinol, heptan-j3-01, octan-8-01,carvoxime, and ethyl mandelate.I n certain instances proof has been afforded by viscosity, and insome cases confirmed by other physical methods, of the existencein solution and in the fused state of racemic complexes.The cases investigated in the present research were methyl andethyl racemates and I-menthyl r-mandelate. It is perhaps worthyof mention that nearly all the definitely established liquid racematesare derivatives of the hydroxy-carboxylic acids.(2) I n the cases where racemate existence in solution has beensubstantiated, dissociation is very considerable, even a t fairly highconcentrations in a comparatively non-dissociating solvent.The author desires to express his thanks to Dr. Pickard andMr. Kenyon for the loan of material, and to the Research FundCommittee of the Chemical Society for a grant which has partlycovered the expenses entailed.EAST LONDON COLLEGE

ISSN:0368-1645    

DOI:10.1039/CT9130300019

出版商:RSC    

年代:1913

数据来源: RSC

摘要:

THE FORMATION OF TETRAHYDRO-OXAZOLES, ETC. 27V. - The Formation o f Tetrahydro-oxazoles fi-oma- Hydroxy- p-anilino- a6 - diphenylethane and itsIlomol ogues.By HORACE LESLIE CROWTHER and HAMILTON MCCOMBIE.IT has been shown by McCombie and Parkes (T., 1912, 101, 1991)that u-keto-8-anilino-afi-diphenylethane (I), when condensed withcarbonyl chloride in toluene solution, yields 3 : 4 : 5-triphenyl-2 : 3-dihydro-2-oxazolone (11). It was found impossible, however, to con-vert this dihydro-oxazolone into a tetrahydro-oxazolone by the actionof reducing agents, as the compound was either recovered un-changed or converted into dibenzyl, with complete destruction ofthe oxazole ring. I n this respect the oxazole ring behaves ver28 CROWTHER AND McCOMBlE :similarly to the glyoxaline ring, which it is found impossible tohydrogenise by the direct action of reducing agents :>CO C~~Ph(OH).CHPh.NIfI’ti COPh*CHPh*NHPh CPh-EPh-N Ph(1.1 (11.1 (111Attempts have been made by the authors to obtain tetrahydro-oxaxolones from a-keto-/3-anilino-a@-diphenylethane by first reducingthat compound to a-hydroxy-b-anilino-u8-diphenylethane (111),employing the method described by Voigt ( J .pr. Chem., 1886, [ii],34, 9), forming the ethylcarbonato-derivative (IV), and eliminatingalcohol according to the method described by McCombie and Parkes(Zoc. cit.). This method, however, resulted merely in the regenera-tion of the original hydroxy-compound. A successful synthesis oftetrahydro-oxazolones was attained by the direct condensation ofa-hydroxy-fl-anilino-aj3-diphenylethane (111) with carbonyl chloridein toluene solution, when theretetra.hydr0-2-oxazolone~ (V), :CO,Et-O*CHPh*C HPh*NHPhUV.1By similar condensations theresulted 3 : 4 : 5-triphenyl-2 : 3 : 4 : 5-HPh*NPh>Co YH,*Y Ph>CoXHPb--* CH,--0 L(V.) (VI.1corresponding m- and ptolyl and8-naphthyl derivatives were obtained, in which these substituentsare attached to the nitrogen atom. It was found impossible toprepare the 0-tolyl analogue because the conditions necessary forthe reduction of a-keto-fI-o-toluidino-a/3-diphenylethane to thecorresponding hydroxy-compound could not be discovered.The tetrahydro-oxazolones described in this communication areclosely related to 3-phenyl-2 : 3 : 4 : 5-tetrahydro-2-oxazolone (VI),which is described by Nemirowski ( J .pr. Chem., 1885, [ii], 31, 175)and by Otto (ibid., 1891, [ii], 44, 17).These tetrahydro-oxazolones were found to be very stable sub-stances. They were not reduced by sodium amalgam, or even bysodium in amyl-alcoholic solution. Phosphorus trichloride waswithout action on them, and their basicity was so slight that nohydrochloride or picrate could be isolated.It was thought possible that compounds similar to the sulphin-azoles described by McCombie and Parkes (Zoc. c i t . ) might beprepared from these hydroxy-compounds by substituting thionylchloride for carbonyl chloride in the reaction described above. Inthe case of the aniline comppund a very small quantity of a con-densation product was obtained.In the case of the other com-pounds, no trace of a condensation product could be isolated, sothat evidently there is little or no tendency for thionyl chloride toyield cyclic compounds with these hydroxy-derivatives. SimilaTHE FORMATION OF TETRAHYDRO-OXAZOLES, ETC. 29negative results were obtained when sulphuryl chloride was substi-tuted for carbonyl chloride.EXPERIMENTAL.a- E t IL y 1 car b o nu to -@-an il in o-a S-di ph en y l e t ha me, C',HsO,N.This compound wits obtained by dissolving the base in dimethyl-aniline and adding excess of ethyl chlorocarbonate. The mixturewas allowed to remain in the cold for twelve hours, and was thenpoured into dilute hydrochloric acid. The carbethoxy-compoundseparated as a viscid mass, which, when recrystallised from dilutealcohol or light petroleum, melted a t 114O :0-2000 gave 7.2 C.C.N, a t 14O and 739 mm. N=4.07.This carbethoxy-compound, on treatment with alcoholic potassiumC,,H,,O,N requires N = 3.88 per cent.hydroxide, gave a-hydroxy-8-anilino-all-diphenylethane.3 : 4 : 5-Triphenyl-2 : 3 : 4 : 5-tetrahydro-2-oxazolone, C,,H,,02N.This substance was obtained by dissolving 2 grams of a-hydroxy-@-anilino-a@-diphenylethane in 25 C.C. of dry toluene, and adding8 grams of carbonyl chloride in toluene (20 per cent. solution). Themixture was allowed to remain overnight, when a white productseparated. The excess of carbonyl chloride was removed on thewater-bath, and the solution was poured into light petroleum inorder to precipitate the oxazole completely.The yield was nearlytheoretical. The product, when crystallised from alcohol, separatedin fine, white needles, which melted a t 216O:0.1781 gave 0.5200 C02 and 0.0914 H,O. C=79*75 ; H=5*7.0.1700 ,, 6-55 C.C. N, a t 16O and 75-35 mm. N=4.44.C2,H,,0a requires C= 80.00 ; H = 5.4 ; N = 4-45 per cent.The tetrahydreoxazolone is readily soluble in glacial acetic acid oracetone, fairly so in amyl alcohol or toluene, especially on heating,but quite insoluble in light petroleum.The compound is very stable; attempts to reduce it with sodiumamalgam, or even with sodium in amyl alcohol, yielded theunchanged substance, and phosphorus trichloride was found tobe without action on it. No salts with hydrochloric acid or picricacid could be prepareda-Elydroxy-#&m-t oluidino-a/3-diphenyl e t hane, C21H210N.This compound was prepared from a-keto-~-m-toluidino-aS-di-phenylethane (McCombie and Park-, Zoc.cit., p. 1996) by reduc-tion with sodium amalgam in exactly the same manner aa tha30 THE FORMATION OF TETRABYDRO-OXAZOLES, ETC.described later for the preparation of the j3-naphthylamino-corn-pouii(1. It crystallised more easily than that, cornpound fromrnethylated spirit, separating in colourless needles which melt, at133O :0.1825 gave 0.5544 CO, and 0.1180 S O . Cl=82.84; H=7*18.C2,H,,0N require,s C = 83.17 ; H = 6.93 per cent.4 : ~ - ~ ; l ) ~ i ~ t t ~ ~ ? - 3 - m - t ~ ) ~ ~ ? - 2 : 3 : 4 : 5-tuf?.iil,~dl.o-2-o.mxolonP.This compound after recrystallisation from methylated spirit (inwhich is is only sparingly soluble), or from amyl alcohol, melteda t 1 8 9 O :0.1808 gave 0.5329 @O, and 0*0906 H,O.C = 80.38 ; H = 5.57.C2,H,,02N requires C = 80.24 ; H = 5.78 per cent.4 : 5-Dip?~nyl-3-p-tolyl-2 : 3 : 4 : 5-tetruhydro-2-oxuzolone.When recrystallised from amyl alcohol or methylated spirit0.1846 gave 0.5440 CO, and 0.0985 HaO. C=80*37; H=5*93.this substance melted a t 209O:C2,H,,02N requires CX- 80.24 ; H = 5.78 per cent.a-Hydrox y-8-2-naph t h ylamino-a/%diphenyl e t hane,OH*CHPh*CHPh*NH*C,,H,.This substance was prepared from the corresponding keto-compound by reduction with sodium amalgam.To 10 grams of a-keto-P-2-naphthylamino-a/3-diphenylethane dis-solved in 100 c .~ . of inethylated spirit were added 50 grams offreshly prepared sodium amalgam (4 per cent.), and the mixturewas kept almost a t the boiling point for two t o three hours. Itwas not found necessary to dissolve the compound completely inalcohol, for as the reduction proceeded, the compound was dis-solved. The solution became dark in colour, and when reductionwas complete, t,he solution was poured into boiling water, andallowed to remain for several hours before filtering. The separatedsolid was washed with dilute hydrochloric acid to remove anynaphthylamine, and was then boiled with a ;mall quantity of lightpetroleum until a white product was obtained. The mixture wascooled, the liquid was decanted from the white solid, and the latterwas recrystallised from a larger bulk of light petroleum. Unlessthe impurities were removed by a preliminary extraction with lightpetroleum, recrystallisation was found to be impossible.When pure, this substance is a white, crystalline solid, extremelTAYLOR: THE ACTION OF HALOQENS ON SILVER SALTS.31soluble in all ordinary solvents, except light petroleum, from alarge quantity of wliicli it crystallises well and melts a t 124-125O :C,,H,,ON requires C = S4.95 ; H = 6.20 per cent.0-1831 gave 0.5694 CO, and 0.1011 H,O. cO=84.81; H=G.14.4 : 5-Diphen?/l-3-8-napT~tT~~yl-2 : 3 : 4 : 5-tetraT~ydro-2-oxazolone.The recrystallised hydroxy-compound was dissolved in hottoluene, and, from time t o time, small quantities of a 20 per cent.solution of carbonyl chloride in toluene were added, whilst thesolution was kept hot on a sand-bath. After a time a white solidwas precipitated, and when excess of carbonyl chloride had beenadded, the mixture was allowed to remain for some time. Theexcess of carbonyl chloride was removed by evaporation, and thesolution, when cold, was poured into a large excess of light petrol-eum, which precipitated the oxazolone completely.The substance when recrystallised from methylated spirit oramyl alcohol separated in large, white, silky needles, which melteda t 231O. I f the hydroxy-compound was pure, the yield of theoxazolone was nearly theoretical. The solubilities of the naphthylderivative were very similar to those of the corresponding anilinecompound :0.1772 gave 0.5335 CO, and 0.0864 H,O. C=S2*13; H=5*42.C21H190$I requires C = 82.19 ; H = 5-21 per cent.CHEMICAL DEPARTMENT,THE UNIVERSITY, EDGBASTON,BI RMINOHAM

ISSN:0368-1645    

DOI:10.1039/CT9130300027

出版商:RSC    

年代:1913

数据来源: RSC

摘要:

TAYLOR: THE ACTION OF HALOQENS ON SILVER SALTS. 31VI. The Action of’ Halogens on Silver Salts.By HUGH STOTT TAYLOR (1851 Exhibition Scholar,University of Liverpool),IN. a recent communication it has been shown by Normand andCumming (T., 1912, 101, 1852) that the halogens react with silversalts to yield an insoluble silver haloid, an acid, and one or moreoxidation products either of the acid or the haloid. In the simplercases considered, namely, those in which no secondary oxidationsoccurred, interesting conclusions were drawn as to the variation inthe products of reaction with the halogen used; thus (Zoc. cit.,p. 1855), it is pointed out that reactions with iodine usually resultin the formation of an iodate. With chlorine and bromine thereactions yield, however, hypochlorous and hypobromous acids32 TAYLOR: THE ACTION OF HALOGENS ON SILVER SALTS.That iodine is quite analogous to the halogens chlorine andbromine in its action on alkali hydroxides has long been known.Schonbein ( J .pr. Chem., 1861, 84, 385) established this in 1861,and his observations have since been extended and amplified(Berthelot, Ann. Chim. Phys., 1878, [v], 13, 20 ; Schwicker, Zeitsch.physikal. Chem., 1895, 16, 302; Foerster and Gyr, Zeitsch. E l e k t m -chem., 1903,9, 1; Skrabal, Monatsh., 1907, 28, 319; 1911, 32, 167,815). It would therefore be expected that in reactions with silversalts a similar analogy would be found to hold.Thus, the interaction of iodine and an alkali yields hypoiodouqacid according to the equation:With excess of alkali an equilibrium is set up:& + OH’= HOI + If.HI0 + OH’= 10’ + H,O.Further, dissolved hypoiodites are unstable, and are converted incourse of time into iodate according to the equation:2HOI + 10‘ = 10,’ + 2HI.With silver salts, therefore, owing to the insolubility of the silveriodide, the following equilibria would be expected :’With excess of tlie silver salt the reaction should then proceed tothe iodate stage in accordance with the equation:The mechanism of reaction suggested by3irnbaum (Annalen, 1869,152, 111) and by Normand and Cumming (Zoc.c i t . , pp. 1853, 1854)represents, according to such views, the sum of the two reactions(1) and (2).As is evident from a study of the action of iodine on alkalihydroxides, the alkali hypoiodites are much less stable than thecorresponding salts of chlorine and bromine, conversion to iodateoccurring with a much greater velocity than is the case in theformation of chlorate or bromate.The velocity of conversion, also,is accelerated by rise of temperature and increase of concentration.It is probable, therefore, that with silver salts also the initialformation of hypoiodite will be the more easily demonstrable thelower the temperature of experiment and the smaller the concen-tration of the solutions employed. The validity of these assumptionswas tested with iodine and silver nitrate in the following experi-ments, which were carried out some months previous t o the appear-ance of the paper by Normand and Cumming.The analogousexperiments with silver acetate have been performed subsequent tothe publication of the work in question.AgX+I,+&O=AgI+HX+HIO . . . (1)3HIO + 3AgX = AgIO, + 2AgI + 3HX . . . (2TAYLOR: THS ACTION OF HALOGENS ON S~LVER SALTS. 33R. L. Taylor (Mem. Munchester Phil. Soc., 1897, [viii], 41, 1) ina paper on hypoiodous acid and hypoiodites first demonstrated thatsilver nitrate reacts with aqueous iodine solutions, the resultingsolution giving all the reactions for hypoiodite. By titrating thesolutions obtained with a standard solution of indigo-carmine, theauthor showed that the bleaching action immediately after theaddition of silver nitrate corresponded with the formation of 95 percent. of the hypoiodite demanded by theory.Further, it was shownthat the solution so obtained was extremely unstable, and thatafter five minutes it had lost 90 per cent. of its bleaching power.EXPERIMENTAL.dletkod of Estimation of Hypoiodite.It was noticed by R. L. Taylor that considerable uncertaintyattaches to titration with indigo-carmine. With iodine-water anexcess of indigo- may be added and apparently bleached, but onkeeping the blue colour returns. Similar difficulties were observedin the initial stages of the present investigation. Consequently, themethod was rejected in favour of Schwicker’s method (Zeitsch.physilal. Chem., 1895, 16, 303). By the addition to a hypoioditesolution of excess of a solution of sodium hydrogen carbonatesaturated with carbon dioxide and also a solution of an iodide, itwas shown by Schwicker that iodine is liberated equal in amountto twice the amount of iodine present as hypoiodite.The iodineliberated can then be titrated with sodium arsenite solution.Silver Nitrate and lodine.-An aqueous solution of iodine whentreated with a solution of silver nitrate yields a pale yellow liquidcontaining silver iodide in a finely divided condition. If thevolumes of the solutions are so chosen that equimolecular quantitiesof the two substances react, $he Bolution obtained, when testedimmediately for hypoiodite by the method of Schwicker, gives atitre corresponding on an average with the formation of 96 percent. of the amount of hypoiodite required according to theequation :hgNOs + I, + H,O = AgI + HI0 + HNO,.If the amounts taken are in the ratio of one atom of iodine toone molecule of silver nitrate, immediate titration for hypoioditedemonstrates the presence of about 90 per cent.of the total hypo-iodite required by theory.The low values obtained are due to the rapid decomposition ofthe hypoiodite into iodide and iodate according to the equation :2HIO + 10’ = 10, + 2HI.The hydriodic acid formed is removed as insoluble silver iodide.VOL. C11I. 34 TAYLOR: THE ACTIOK OF HALOGENS ON SILVER SALTS.The decomposition is the more rapid the greater the concentrationof silver salt present, as is evident from the following time reactionseffected with solutions containing approximately 1, 2, and 3 mole-cules of silver nitrate respectively for each molkcule of iodine. Themethod of procedure adopted in these experiments was to take agiven vollfime of solution containing the materials in the requiredproportions, and then to titrate aliquot portions thereof a t definiteintervals of time.The first column indicates the time in minutesintervening between mixing and titration, the remaining columnsthe percentage of hypoiodite present.Percentage hypoiodite with 1 molecule iodine andI A \ Time. 1 mol. AgNO,. 2 mols. AgNO,. 3 mols. AgNO,.1 ............ 92.5 72.8 35 *53 ........... 81.8 53-66 ............ 76.2 38.0 10.511 ..... : ...... 71.0 24'0 6-94.5 16 ............ 68.7 -21 ........... 67.3 14*2 3.328 ............ - 10.5 -80 - - .......... i. 64 ' 5-I n the first example in which the materials are present in approxi-mately equimolecular quantities, the hypoiodous acid is slowlyconverted into hydriodic acid and iodic acid.I n its initial stagesthe conversim is assisted by the slight excess of silver salt necessaryfor the attainment of the first reaction, but after a period of time,during which the silver is removed as insoluble silver iodide, therate of decomposition sensibly diminishes. Further, i t is knownthat a mixture of hydriodic and iodic acids decomposes to yieldiodine :5HI + HIO, = 31, + 3H20.Regeneration of iodine would therefore be expected in the progressof the above reaction. That this occurs can be demonstrated bytreating a mixture of molecular quantities of iodine and silvernitrate solutions with starch paste.No coloration is observed onaddition, but the characteristic blue colour slowly develops.In more concentrated solutions than it is possible to obtain byusing aqueous solutions of iodine, the reaction between silvernitrate and the halogen still proceeds through the hypoidite stageto the iodate. This can be demonstrated by the following experi-ment. A N/ZO-iodine solution in LV/ 10-potassium iodide wastreated with an amount of standard silver nitrate sufficient toremove the potassium iodide as silver iodide and to allow twomolecules of the silver salt to react with each molecule of iodinepresent. Even in such concentrated solutions, in which obviouslythe decomposition of hypoiodite is greatly accelerated, it waTAYLOR: THE ACTION OF HALOGENS ON SILVER SALTS.35possible to show the presence, immediately after reaction, of 5 to10 per cent. of the total hypoiodite required by theory. Thevariation in the amount titrated varied with the rapidity withwhich the reaction was effected.Silver A c e t a t e and Zodirte.-With silver acetate, iodine reactsin the same manner as with silver nitrate. One molecule of iodinein aqueous solution reacts with a molecule of silver acetate, ther e d ting solution, tested immediately, containing 97 per cent. ofthe theoretical amount of hypoiodite. With the materials presentin the ratio of one molecule of iodine to two molecules of silversalt, immediate titration showed the presence s f 90 per cent. of thetheoretical amount.Time reactions with silver acetate present in the ratios of 1.1and 2 molecules respectively for each molecule of iodine gave thefollowing results :Percentage b ypoiodite with1 molecule iodine andr - -1.1 mols.Time.silver acetate.1 .................. 94.73 ..................6 .................. 69.311 ................. 60'116 .................. 62'422 ..................36 .................. 60'850 ..................76 .................. 49'3---72 mols.silver acetate.69.560 *751538.230-927'215'6--The possibility of following, from the point of view of reactionkinetics, this decomposition of hypoiodite into iodide and iodateis at present the subject of investigation by the author.Summary.Iodine reacts with silver salts in a manner analogous to thatobserved in reactions with chlorine and bromine t o yield insolublesilver iodide, hypoiodous acid, and another acid. The reactionoccurring may be represented by the equation:AgX + 1, + H,O = AgI + HI0 + HX.Owing to the instability of hypoiodous acid a second reactionoccurs, accelerated by rise of temperature, increase in concentra-tion, or presence of soluble silver salts, in which reaction the hypo-iodous acid is converted into iodide and iodate. This secondaryreaction may be generally represented by the equation:3HI0 + 3AgX = 2AgI + AgIO, + 3HX.0 96 DOBBIE, FOX, AND dAUGE! DIPHENYLBNE. PART IT.The simple equation of Birnbaum and of Normand andGumming,represents the Slim of the two preceding equations.In conclusion, I wish to express my indebtedness to Prof. HenryBassett, of University College, Reading, for his valuable assistanceand advice during the course of this research.31, + 3H20 + 6AgX = 5AgI + AgIO, + 6HX,W M . GOSSAQE LABORATOBIEB, NOtrEL INSTITUTE O F PHY6ICAL CHLMIBTRY,UNIVERSITY OF LIVERPOOL. EXPERIMENTALPALTET,SWEDEN

ISSN:0368-1645    

DOI:10.1039/CT9130300031

出版商:RSC    

年代:1913

数据来源: RSC

摘要:

36 DOBBIE, FOX, AND GAUGE! DIPHENYLBNE. PART IT.VI i .--Diphenylcn e. 11.By JAMES JOHNSTON DOBBIE, JOHN JACOB Fox, andARTHUR JOSIAH HOFFMEISTER GAUGE.IN previous papers dealing with the preparation and proper-ties of 2:2/-dibromodiphenyl it was shown that the action ofsodium on this substance results in the formation of the hydro-carbon diphenylene, C,,H, (T., 1911, 99, 683, 1617). I n theexperiments by which this substance was first obtained the sodiumwas employed in the form of thin slices. The reaction proceededslowly, but gave only a small quantity of by-products. The amountof these was reduced by substituting light petroleum for ether,whereas it was increased by the use of benzene, probably becauseof the ready solubility of the by-products in this medium.Byusing finely-divided sodium the rate of the reaction was increased,but the yield of diphenylene was greatly reduced owing to theformation of compounds of high molecula8r weight. One of thesewas found by analysis and determination of the molecular weightto have the formula Cs4H,,Br,.We have made numerous experiments in the hope of finding amore convenient method for the preparation of diphenylene, butso far without success. I n one of these attempts o-di-iodobenzenewas heated with copper powder, both in air and in closed exhaustedtubes to 250O. Only resinous products were obtained, from whichno diphenylene could be isolated, although there was reason tobelieve that a small quantity had been formed. Silver diphenatesuggested itself as another possible starting point for the prepam-tion of diphenylene.On subjecting this salt to dry distillation it,was observed that a t a particular temperature' sudden decomposi-tion set in, accompanied by much charring and a violent evolutionof carkon dioxide. The distillate condensed to a mass of yellowcrystals, which dissolved almost completely in light petroleumDOBBIE, FOX, AND GAUGE: DIPHENYLENE. PART 11. 37This solution deposited pale yellow crystals, which on recrystallisa-tion melted a t 92O. The crystals agreed in character with thelactone described by Graebe and Schestakov ( A nnalen, 1895, 284,316) under the name of “ biphenylmethylolid,” C,Ht-C,H4=CO*0,and by Griess (Ber., 1888, 21, 981) and Richter. Bromination ofthe crystals resulted in the formation of the bromo-derivativemelting a t 194O prepared by Richter ( J .pr. Chem., 1883, [ii], 28,294). Their identity with the lactone derived from o-hydroxy-diphenylcarboxylic acid is therefore established. The motherliquors from this substance were evaporated to dryness and distilledin a current of steam, when crystals of pure diphenyl were obtained.No trace of diphenylene was found in these operations.To obtain a supply of material for the further examination ofthe reactions of diphenylene we were compelled to revert to theoriginal method of preparation described in our first paper onthe subject. We have been obliged in consequence to limit ourinvestigation for the present to a few of the simpler derivatives.A dinitrodiphenylene was obtained by heating diphenylene withdiluted nitric acid under pressure. By the action of the fumingacid a tetranitro-derivative was formed. Considerable loss ofmaterial occurred in both cases, resinous and waxy substancesbeing formed, which were not sufficiently well defined for investi-gation. Bromine reacted with diphenylene with the formation oftwo products, namely, 2 : 2/-dibromodiphenyl and a dibromo-diphenylene.By the oxidation of the latter, p-bromobenzoic acidwas obtained, together with an acid which yielded a stronglyfluorescent solution when condensed with resorcinol. The f orma-tion of pbroniobenzoic acid indicates that under the conditionsdescribed substitution takes place in the meta-position with respectto the middle ring.The behaviour of diphenylene when heated with diluted nitricacid is of special interest.From the products of the reaction threedefinite substances were isolated, namely, (1) a dinitrodiphenylene,(2) diphenylene oxide, and (3) a nitrophthalic acid. I n addition, aquantity of waxy matter of indefinite character was formed.It is quite clear from the production of diphenylene oxide by theoxidation with dilute nitric acid, on the one hand,1 10and from the regeneration of 2 : 2’-dibromodiphenyl on the other,C,H4:CGH4 -+ C,H4Br-C6H4Br, that the diphenylene molecule israther unstable. It is probably owing to this instability tha38 DOBBIE, FOX, AND GAUGE: DIPHENYLENE PART IT.diphenylene forms waxy substances so readily under the influenceof various reagents, and that the formation of substitution deriv-atives is accompanied by so much loss of material.EXPERIMENTAL,Finely divided sodium was immersed in dry ether, and dried2 : 2/-dibromodiphenyl was added.An immediate reaction resulted,the’ solution became deep brown, and a quantity of red, insolublematter separated. The reaction was complete in a very short time.The ether and suspended solid matter were separated fromunchanged sodium, and the ethereal liquid was filtered. When theinsoluble matter was boiled with a little water to remove sodiumbromide a yellow powder was left behind. This dissolved readilyin cold benzene and chloroform, from the solution in which it couldbe precipitated by light petroleum or alcohol.The substance wasreadily purified by repeated treatment with a mixture of benzeneand light petroleum, from which it separated as an amorphous,yellow powder, melting and decomposing at 306O:0-1246 gave 0.3756 CO, and 0.0532 H,O.0.1036 ,, 0.0312 AgBr. Br=12*8.0.2876 in 18.74 benzene gave E = 0.037.C = 82.2 ; H=4.7.M.W. = 1180.C,,H,Br, requires Q=82*3; H=4*6; Br=13’1 per cent.M.W. = 1224.The formula of this substance may be written (C,,H,),Br2 whenit is seen to be derived from the action of sodium on two moleculesof 2 : 2/-dibromodiphenyl, the product of which then reacts witha third molecule, and so on until the compound having eighty-fourcarbon atoms is reached, which is insoluble in ether. The compoundCs4H5,Br2 is similar in character to the compound C,8H52Br2described by Goldschmiedt (Monufsh., 1886, 7 , 40) and Hosaeus(ibid., 1893, 14, 323), which results from the action of sodium onthe various dibromobenzenes. The ethereal filtrate from thecompound C,,H5,Br, contains the diphenylene formed in the reac-tion, together with other substances similar in character toC,,H,Br,, but soluble in ether.These may be readily separatedfrom diphenylene by taking advantage of their insolubility in lightpetroleum or in cold alcohol.*Bromimtion of Diphe?byiene.--The diphenylene to be operatedon was covered with water, four times its weight of bromine wasadded a little a t a time, and the whole mass ground up in a mortar.No perceptible rise) of temperature resulted, and only a smallamount of hydrogen bromide was evolved.The whole mass was* The behaviour and properties of these substances are not described here, as theyhave no bearing on the derivatives of diphenyleneDOBBIE, FOX, AND GAUGE: DIPHENYLENE. PART 11. 39treated with dilute aqueous sodium hydroxide solution until allthe unchanged bromine was removed, the residual solid collected,washed with water and a little alcohol, and dissolved in benzene.Colourless needles separated, which did not melt sharply, but aftera second crystallisation melted at 80°. This substance was identicalwith 2 : 2/-dibromodiphenyl formerly described by us (T., 1911, 99,1618). The mother liquors on concentration deposited furthercrops of crystals, of which the first fractions, judging from the lowmelting point, contained more 2 : Z’-dibromodiphenyl.The lastfractions consisted chiefly of a substance which melted after severalcrystallisations a t 171°, and had the composition of dibromodi-pTixnyZene :0.1330 gave 0.1624 AgBr. Br=52*0.C,,H,Br2 requires Br = 5 1 * 6 per cent.The yield of pure substance was not more than 30 per cent., alarge proportion of the diphenylene operated on having been con-verted into 2 : 2/-dibramodiphenyl and waxy substances of indefinitecharacter containing halogen. Dibromodiphenylene dissolves fairlyreadily in benzene and alcohol, from which it separates in long,stout, colourless needles. When oxidised by chromic acid it yieldsa mixture of acids. One of these was recognised as a phthalic acidby the strongly fluorescent solution obtained by condensing it withresorcinol.The other was proved by its equivalent weight andmelting point (248O) to be p-bromobenzoic acid.Nitration of DiphenyZene.-One part of diphenylene was dissolvedin ten parts of concentrated sulphuric acid, and the mixture cooledwith ice; four parts of nitric acid (D 1.5) were then added a littleat a time, keeping the whole immersed in a. freezing mixture. Whenthe action, which a t first was very violent, had moderated, the flaskcontaining the mixture was heated on a water-bath for one hour.The contents of the flask after being allowed to cool were pouredinto ten times their volume of ice-water; the solid which separatedwas collected, washed with water and a little alcohol, and dried.The yield of crude solid was about 30 per cent.of the weight ofthe diphenylene taken. The dried precipitate was boiled with alarge quantity of alcohol, from which it crystallised on cooling infine, yellow needles, melting at 223O :0.2372 gave0.3768 CO, and 0.0304 H,O.0.1038 ,, 15.1 C.C. N, at 19’5O and 768 mm. N=17.1.The substance is therefore a tetranitrodiphenylene.C=43*3; H=1*4.C,H,O,N, requires C =43-4 ; H = 1.2 ; N = 16.9.It dissolvessparingly in alcohol and glacial acetic acid, but is almost insolublein other organic solvents40 DOBBIE, FOX, AND GAUGE: DIPHENYLENE. PART 11.-4ction of Diluted Nitric Acid on Biphemylene.Diphenylene was heated in a sealed tube for sixteen hours a t150° with twenty times its weight of diluted acid (D 1.2).Con-siderable decomposition resulted, and a yellow, ’semi-crystalline massremained. This was washed with water, digested with ether, andfinally with alcohol and benzene. The residue obtained after thistreatment consisted of pale yellow needles, which dissolved sparinglyin alcohol. It separated from its alcoholic solution in small needlesmelting at 204O. Analysis showed that the substance was a dillzitro-Oscillation frequencies.810,00050002500100502510Diphcnylenc oxide i n alcohol.diphenylene. The yield was small. Dinitrodiphenylene is almostinsoluble in ether, benzene, or carbon disulphide, but dissolvessparingly in alcohol, acetone, or glacial acetic acid:0.1236 gave 0.2678 CO, and 0.0334 H,O.C = 59.1 ; H = 3-0.0-1314 ,, 13.4 C.C. N, at 17O and 761 mm. N=11*8.C,,H,O,N, requires C= 59.5 ; H= 2.5 ; N= 11.6 per cent.The ethereal solution was treated with aqueous sodium hydroxide,whereby a small amount of an acid was removed. On evaporatingoff the ether a waxy mass was left behind, which was redissolveIRVINE AND HYND : SYNTHETICAL AMINOCXLUCOSIDEG. 41in alcohol. From the alcoholic solution small plates deposited. Onredissolving these plates and treating with picric acid, a picrateseparated out from the concentrated alcoholic solution, which onrecrystallisation melted a t 95O. By acting on the picrate withaqueous sodium hydroxide and extracting the resulting liquid withether a crystalline solid was obtained melting at 78-79O, and pos-sessing the properties of diphenylene oxide. Its identity with thissubstance was clearly established by its melting point, the meltingpoint of its picrate, and by its absorption spectrum. The absorptionspectrum of diphenylene oxide (see diagram) is strikingly character-istic. It possesses two bands; the heaa of the larger and morepersistent band is a t l / h 3530, and of the small narrow banda t l / h 4000. The spectrum of the substance from diphenyleneis identical with this.The aqueous liquid remaining after the reaction contained anacid which was purified by means of its sodium salt. It correspondedin molecular weight and in the melting point pf its methyl esterwith 3-nitrophthalic acid (Ag salt: Found, Ag=49*9. Calc., Ag=50.5 per cent.).We hope in a future paper to give a more particular accountthan has yet been possible' of the physical properties of diphenylene.GOVERNMENT LABORATORY,LONDON

ISSN:0368-1645    

DOI:10.1039/CT9130300036

出版商:RSC    

年代:1913

数据来源: RSC

摘要:

IRVINE AND HYND : SYNTHETICAL AMINOGLUCOSIDES. 41V1II.-Synthetical Arninoglmosicles Derived fromd- Glucosamirw .Bv JAMES COLQUHOUN IRVINE and ALEXANDER HYND, M.A., B.Sc.(Carnegie Fellow).THE action of acyl bromides on glucosamine, which was first studiedin this laboratory four years ago, has opened up the way for thepreparation of glucosamine derivatives of a new type. We havealready in previous papers (T.? 1911, 99, 250; 1912, 101, 1128)described the use of bromotriacetylglucosamine hydrobromide inthe preparation of a-arninomethylglucoside (methylglucosamine),and in the present paper it is shown that the bromo-compoundfunctions as a general synthetic reagent, by means of which theglucosamine residue may be coupled with any hydroxy-compoundpossessing the requisite solubilities.In this way synthetic amino-glucosides may be prepared, which can be regarded either asderivatives of glucosamine or of glucose42 IRVJNE AND HYND : SYNTHETlCAL AMINOGLUCOSIDESExpressed in the simplest general terms, the reaction involvedconsists in the condensat,ion of bromotriacetylglucosamine hydro-bromide with a hydroxy-compound in presence of a base whichcombines with the liberated hydrogen bromide. The product ofthis first reaction is the salt of a triacetylated aminoglucoside,from which the acyl groups are removed by heating with a dilutesolutior, of hydrogen chloride in methyl alcohol. The most obviousinterpretation of the changes is shown in the following scheme: ,--- 0 ~OAc*CH,*CH(OAc)*CH*CH(OAc)* $J HdHBr + ROH -+NH,,HBrr-------O-OAo*CH,*CH(OAo)*CH*CH(OAc)*$lH*~H*OR -+NH2,11Br ,--- o---OH*CH,*CH(OH)-UH*CH(OH)*$JH*dH*OR .. . , (4NH,,HC1but in the partkular case of a-aminomethylglucoside we indicatedthat the einiple general formula of the type ( A ) cannot be reason-ably applied to the compound, and we suggested the followingvariation, which includes a modified betaine ring in the molecule:It appeared to us of interest to prepare a number of amino-glucosides on mcount of their possible importance as a first stepin developing the synthetical chemistry of the glucoproteins, andto ascertain if both types ( A ) and ( B ) can exist.The csnclusion arrived a t is that, when the group condensedwith the glucosamiae residue consists of a short open chain, theproduct.possesses properties similar to those of a-aminomethyl-glucoside, and thus belongs to the type (B). On the other hand,the derivatives of glucosamine which contain a benzene nucleus inthe glucosidic position do not differ essentially from true glucosides,except i n so far as the properties of the compounds are modifiedby the presence of the basic amino-group. As examples of thisclass, to which the general formula ( A ) applies, we have a-amino-benzylglucoside, a-aminosalicin, a-aminohelicin, and a-amino-morphineglucoside.So far, then, as generalisations may be made from the data nowavailable, the aminoglucosides related to glucosamine may bDERIVED FROM D-GIJJCOSAMINE. 43divided into the above two classes, which differ sharply in theirproperties.Those in which nitrogen is linked to oxygen areremarkably stable towards the hydrolytic action of hydrogenchloride; they are also unaffected by emulsin, and form additivecompounds with silver iodide. I n sharp contrast to this behaviour,the normal glucosides are easily hydrolysed by acids, and in thecase of aminohelicin and aminosalicin are apparently alsohydrolysed by emulsin. The general question of the action ofenzymes on compounds of both types now described is evidentlyimportant, and Prof. H. E. Armstrong has kindly undertaken t oextend our experiments in this direction.Unfortunately, no definite description can be given of theworking methods employed t o prepare aminoglucosides from bromo-triacetylglucosamine hydrobromide, as the process has t o bemodified to suit each individual case.Reference to the experi-mental part will show that when the hydroxy-compound to becoupled with the glucosamine residue is a volatile liquid, it shouldbe used in large excess. With liquids of high boiling points, onthe other hand, it is necessary to restrict the amount used to onemolecular proportion so as to avoid, as far as pmsible, the inevit-abla decomposition of the product which results during the removalof the excess of the reagent. With solid hydroxy-compounds, ether,chloroform, or other indifferent solvent may be employed, but insuch cases the base used must also be soluble.The use of bromotriacetylglucosamine hydrobromide is, in fact,beset with difficulties.Owing to the instability of the compound,its limited range of solubility, and the fact that it cannot beemployed in solution a t temperatures exceeding 60°, its use insynthetical work is much more restricted than that of tetra-acetylbromoglucose. Even in successful reactions the yieldsobtained were in most case3 small owing to the difficulty .experi-enced in removing deliquescent by-products. I n the followingtables lists are given of the aminoglucosides and their constants,the nomenclature employed expressing the relationship of thecowpounds to d-glucose :TABLE I.9 cetylated Aminoglucosides.Decomposition [a]? in methyltemperature. alcohol. Type.Triacetyl-a-aminomethylglucoside (HBr) * . 230-233" +20-26" (B)Triacetyl-a-aminoethylglucoside (HBr).. . . . . 250-251 12'46 ( B )Triacetyl-a-aminoamylglucoside (HBr) ...... 227" 10.38 (B)Triacetyl-a-aminobenzylglucoside (HBr) .. 235-236 52'1 ( A )Triacetyl-a-aniinohelicin (HBr) .. . ......... .. . 215 -216 200"++ 43'6 ( A )* T., 1911, 99, 25044 IRVINE AND HYND : SYNTHETICAL AMINOGLUCOSIDESTABLE 11.A min oglu cosides.Decompositiontemperature.190" a- Aniinometh ylglucoside hydrochloride * . . .a- Aminoethylglucoside 9 J ... 213-214a- Aminoben zylgliicoside I , ... 176a-Aminobelicin 2 9 ... 180a- Aminosalicin J , ... 178-179a-Aminomorphineglucoside .................. 246-248* T., 1911, 99, 250.[a]? inwater. Type.27-75 (B)51-15 ( A )8.97 ( A )18-99 ( A )113.45 ( A )-24'2" ( B )I n addition t>o, the above, a number of cases were examined inwhich condensation occurred, but the product could not be isolatedin the pure stnte.Probably the most important compounds now described are thesalts of a-amino-o-aldehydophenylglucoside and a-aminosaligenin-glucoside, and the constitution of each was accordingly determinedso as to establish their relationship with the natural glucosideshelicin and salicin. We find that in a-amino-o-aldehydophenyl-glucoside both the amino- and aldehydic groups remain intact;the compound, moreover, has no phenolic or reducing properties.This at once limits the constitution to the formula: ,---+- IOH*CH,*CH(OH)*CH*CH(OH)* F H*C~H*(J*C,H,*CKO.NH,,HClThe compound is thus to be regarded as the hydrochloride ofa-aminohelicin.At the same time attention should be drawn tothe fact that the observations made on the rotatory power oftrimetyl-a-aminohelicin seem at first sight in disagreement withthis view. The account of this optical behaviour is here given indetail, as an indication of the caution with which changes inrotation must be accepted as a proof of reversible isomeric change.Pseudo-mu taro ta t ion of Triace t yl-a-aminohelicin Hydro bromide.I n contrast with the othea aminoglucosides examined, the com-pound now under consideration showed curious optical changes insolutiori resembling closely those displayed by reducing sugars.When dissolved in methyl alcohol the specific rotation was initiallydextro, but rapidly diminished on keeping.An idea of the magni-tude and speed of the change can be gained from the followingobservations DERIVED FROM D-QLUCOSAMfNE.c = 1.4943, 1 = 2, f. = 20'.Time from the first reading.Minutes ......... 0 ,, ......... 25,, ......... 90), ......... 265Hours ............ 28), ............ 65,) ............ 1500a.+ 6-98"5'885-043'932'441-751 -30a5[ U j y .+ 200.09"196'7168.6131.58 1-6358.544 3 -49 (constant)The curve illustrating the complete optical change was differentfrom the records usually obtained in the case of true mutarotation,in that the initial fall was slow compared with the normal steepnessof the curve. Two reactions, one resulting in a slight rise and theother in a pronounced fall in rotatory power, thus appear to proceedsimultaneously.The solvent was removed, under the ordinarypressure, from a solution which had attained the permanentrotatory power, and, on the addition of petroleum of low boilingpoint, the original compound was precipitated in the crystallinestate unaltered in melting point and composition. On redissolvingthis specirr,en in methyl alcohol the above optical changes wererepeated, the solution once more showing downward mutarotation.This behaviour might reasonably be interpreted as indicating thatthe reducing group of the glucosamine residue had remained unsub-stituted, and was thus undergoing the usual a /3 transformationin solution; the precipitation by petroleum in such a case wouldcause the separation of the less soluble labile form.We are of the opinion, however, that the rotatory changesreferred to are due to temporary combination with the solvent toform a methyl alcoholate of the type:0--, /\OA~*CH,=CH(OA~).~H*CH(OA~)-~ H - C H ~ I \//\ ......:NH,,HRr cH /;OMe/OH j ...............which readily loses methyl alcohol in the manner indicated by thedotted line. This is supported by the fact that evaporation at10°/12 mm. of a solution which had attained the permanentrotatory power ([a],, + 43O) gave no crystalline product, but a colour-less syrup. A portion of this syrup was preserved in a vacuumdesiccator for several weeks, when it gradually solidified to a massof crystals conaisting of the original compound. The remainder ofthe syrup was dried a t 40°/15 mm.until constant in weight. AZeisel estimation then gave OMe = 5.00, the theoretical value fo46 lHVINE AND HYND : SYNTHETICAL AMINOOLUCOSIDESthe methyl alcoholate formulated above being OMe = 5.9 per cent.Evidently a small amount of the combined methyl alcohol had beenexpelled during the drying process, and this view was confirmedby the fact that the analysis specimen showed slight mutarotationin the downward sense on being re-dissolved in methyl alcohol.These changes are summarised below, the values being calculated onthe1 concentration of the glucoside salt used : -Second+200*1" --3 +43*5" -+ +73.6" -3 f43.8"Initial [uID. Permanent [a],. [ulD After drying. permanent [.ID.(OMe = Nil). (OMe = 5.0 per cent.).Considerable support was given to this explanation by the factthat aqueous solutions of triacetyl-a-aminohelicin hydrobromideshowed a constant rotation when preserved for a week.Possible ReZatifolzship of' Aminoglucosides to Glucoproteins.So far, no simple' aminoglucosides of the nature of the com-pounds described in this paper have been isolated from naturalsources, but nevertheless i t is highly probable that substances ofthis type do actually exist in nature.A t the present time con-siderable attention is being directed to the study of the simplernitrogenous constituents of plants, and the recent work of Schultzeand his pupils (Zeitsch. physiol. Chem. 1912, 79, 235, and previouspapers) has shown that betaine and complexes containing ringstructures similar to betaine are far from being unique, and arewidely distributed. Moreover, the proofs given by van Romburghand Barger of the constitution of hypaphorine, and by Barger andEwins of the structure of ergothioneine (T., 1911, 99, 2068, 2336),a.ff ord additional examples that betaine complexes of differenttypes must now be regarded as forming a distinct class of naturalproducts.Presumably natural aminoglucosides which possess a betaine-like structure are most likely to occur in organisms in which chitinis deposited as a protective layer, and we have accordinglycommenced a systematic search for such compounds in the fungi.It is also evident that aminoglucosides, derived from glucosamine,possess a special interest, as they may be closely related to gluco-proteins.It is true, as Abderhalden has stated, that in theparticular case of betaine the compound seems to play no specificpart in the protein molecule, and is not likely to be encounteredin protein cleavage products. Schultze, who agrees with this view,holds that betaine derivatives resemble alkaloids which, when onceformed, take no further part in plant reactions. These statements,however, do not seem applicable to the betaine-like or glucosidiDERIVED FROM D-QLUCOSAMINE. 47derivatives of glucosamine where the existence of the potentialamino-group and three hydroxyl groups naturally confers consider-able reactivity on the molecule.A review of the somewhat scanty and diffuse informationregarding glucoproteins shows that there is a t least a strong prob-ability that they are closely related to aminoglucosides, andsuggests th9 possibility of synthesising complexes which wouldbear the same relationship to glucoproteins that synthetic poly-peptides do to proteins; thus the fact that mucins, when boiledwith 2.5 per cent.hydrogen chloride, undergo only partialhydrolysis to give non-reducing intermediate products which areonly convert'ed into glucosamine when the hydrolysis is carried outby more concentrated acid, has given rise to considerable discussion.The reaction, however, seems capable of a simple explanation.Hitherto it has been held that this behaviour is a proof that theamino-sugar is not present as ouch in the protein molecule, but isformed as a decomposition product. Our results on the hydrolysisof acetylated aminoglucosides of the type (B) offer a remarkableparallel to this behaviour, as treatment with 2.5 per cent. hydro-chloric acid removes only the substituting acyl groups, and leavesthe " glucosidic " residue unaffected.The 'action of alkalis on thetwo classes of compound also shows marked similarity. AcetylateEiaminoglucmides are thus deprived of the acyl groups only, and inthe case of glucoproteins the hydrolysis is likewise only partial, andgives non-reducing products. It would thus appear that in theglucoproteins amino-acyl residues occupy the amino-position, andpossibly alsq all the hydroxyl positions with the exception of theglucosidic group. Inspection of the available data on the reactionsof glucoproteins seems to us to indicate that, a t all events someof these compounds may he regarded as analogues of triacetyl-a-aminomethylglucoside, in which the substituting groups areamino-acyl residues, and according t o this view the structure wouldfall into line with Fischer's constitution for tannin (Bey., 1912,45, 915).A general formula of this !type would be represented by theexpression : ,---_ o--CH,(OR,)*CH(OR,).CH.CH(OR,).QH.+HN-0where G represents the glucosidic group, and R,, R,, etc., stand foramino-acyl residues, which are probably short polypeptide chains.A complex of the above type would give, on hydrolysis with dilut48 IRVINE AND HYND : SYNTHETICAL AMINOQLUCOSIDEShydrogen chloride, the amino-acids corresponding with R,, R,, etc.The latter wouId also be removed by the action of alkalis, but theresidue G would be much more stable to both acids and alkalis.Consideration of (1) the average carbon, hydrogen, and nitrogencontents of the mucins, (2) the number and amount of the amino-acids formed from them on hydrolysis, and (3) the relative yield ofglucosamine salt produced in each case', shows that the abovestructure is in satisfactory agreement with experimental data.An alternative structure for the mucins may, however, be con-sidered, namely, that a complex polypeptide chain is simplyattached t o the glucosamine residue through the amino-group.Thisstructure seems highly unlikely, as not only would the compoundsshow reducing powers, but hydrolysis in definite stages by meansof acids would be less likely to occur, and could in no case give aglucoside. Moreover, it is difficult to imagine, in the case of a longside-chain of this description, that condensation with the freehydroxyl groups would not occur.The above considerations as to thO structure of gluco-proteins are,of course, largely speculative, but are given here in view of therecent appearance of a preliminary note by Hopwood and Weiz-marin (P., 1912, 28, 261), who describe the action of certain bromo-acyl haloids on glucosamine, the obvious extension of their workbeing the formation of aminoacyl derivatives of the amino-sugar.We think it only right to state here that, during the past two years,workers in this laboratory have also been engaged in introducingbromoacyl residues into glucosamine.Our investigations are, how-ever, directed to the preparation of complexes in which the gluco-sidic and hydroxyl groups, as well as the amino-group, are substi-tuted, and we take this opportunity of stating that syntheses of thenature indicated in the above theoretical discussion are being vigor-ously prosecuted.EXPERIMENTAL.*A c e t y 1 a t ed 9 ,rn in o 9 Z u c o s i d e s.Condensation of Bromo triace t y Zglucosamine Hydro b romide withE fhyZ AZcohol.Triacetyl-a-aminoethylglucoside was, in the first instance, preparedby dissolving bromotriacetylglucosamine hydrobromide (1 mol.) inethyl alcohol (3 mols.) and pyridine (1 mol.). Although the yieldof crude condensation compound thus obtained was quite satisf ac-tory, the removal of the deliquescent by-products proved to be so* All the reagents employed were pure and were specially dried before use.Except where otherwise stated, evaporations and concentrations were conductedunder diminished pressureDERIVED FROM D-GLUCOSAMINE.49troublesome that the method was abandoned in favour of thefollowing process.11.7 Grams of the crude bromo-compound, which, as explainedin a previous paper (loc. c i t . ) , should contain 10 grams of the puresubstance, were extracted with excess of cold ethyl alcohol, and thesolution filtered from glucosamine salts. Meanwhile, a solutionof 6.3 grams of dry morphine in ethyl alcohol had been prepared,and the two solutions were then mixed without delay.The separa-tion of the morphine hydrobromide began in a few minutes, andwas complete in twelve hours. Only slightly less than the theoreti-cal amount of the morphine salt was thus obtained. The filteredliquid on concentration yielded two crops of crystalline product,and even the final mother liquor on evaporation to dryness gave acrystalline residue.After recrystallisation from a concentrated solution in ethylalcohol, the product was washed with cold alcohol and then withether. The material used in the following determinations was driedin a vacuum until constant in weight.The total yield was almost quantitative.Found : C= 40.42 ; H= 5.86 ; Br = 19.30 ; OEt = 10.68.C,,Hl8O7N-OEt,HBr requires C = 40.56 ; H = 5-84 ; Br = 19.30 ;OEt=10*87 per cent.Triace t yl-a-ami?Lo e thylglucoside hydro bromide forms colourlessneedles, which begin to turn brown at 220°, and melt, with com-plete decomposition, a t 250O.The compound gives a very sharpglucosidic reaction with Fehling’s solution, and is only hydrolysedinto its constituenh when boiled with concentrated aqueoushydrogen chloride. Like the other compounds of this type, it isdextrorotatory :Solvent : Methyl Alcohol. c = 1.806, 1 = 2, a + 0*45O, [a]: + 12’5O.Any variatian of the method of preparation just described isliable to give complex, uncrystallisable syrups ; thus, for example,the use of dry acetone in sufficient amount to dissolve the brom+compound gave rise to considerable decomposition, the substitutionof silver carbonate for morphine gave a ‘similar result, and allattempts t o carry out the condensation in absence of a base merelyregenerated glucosamine hydrobromide.Condemation of Bromotriacetp?glucosamine Hydrobromide .withiAmy1 A Zcohol.I n this particular instance, the condensation is unsuccessful whenmorphine is used to remove hydrogen bromide. Ten grams of thebromo-compound (1 mol.) were mixed with 5-28 grams of amylVOL. CIII.50 IRVINE AND HYND : SYNTHETICAL AM INOOLUCOSIDESalcohol (3 mols.) containing 1.50 grams of pyridine (1 mol.). Onvigorous shaking, the bulk of the material passed into solution, and,after forty-five minutes, the liquid set to a stiff paste. The reactionwas complete in two hours.The solid product, after removal ofthe excws of amyl alcohol by draining on porous porcelain, wasextracted with ethyl alcohol, and the solution, after filtration fromglucosamine salts, concentrated in a vacuum desiccator. Theproduct then mparated in the crystalline state, and was purifiedby recrystallisation from ether containing 40 per cent. of ethylalcohol.The yields obtained by this process were never more than 20 percent. of the theoretical amount, and were not improved by anymodifications of the method.Found : C?= 44.52 ; H = 6-72 ; Br = 17-53.C,H,,O,N*O*~~H,,,HBr requires C = 44-71 ; q= 6-63 ;Br=l7*52 per cent.TriacetyLa-aminoamylgl2lcosi~e hydrobromide crystallises readilyin delicate needles from solutions in ethyl acetate, amyl alcohol, ora mixture of ether and alcohol.The compound, however, shows amarked tendency to separate in a gelatinous form, which onlybecomes crystalline when stirred with dry ether. The crystals turnbrown a t 217O, and decompose a t 227O. The compound behaves asa glucoside towards Fehling's solution, but is remarkably stable tohydro'lysis. Contrary to expectation, all attempts to remove theacetyl groups resulted in profound decomposition, and thus theunsubstituteci glucoside was not isolated.The specific rotation in methyl alcohol for c= 1.687 wits + 10-4O.It should here be stated that the amyl alcohol used in the prepariltion of this glucoside showed a -0'76O for Z = 1 . The excess ofamyl alcohol which remained uncombined was recovered from thetiles and purified. It then showed no appreciable alteration inrotatory power from the original value.Condensation.of Bromo triace t ylgtucosamine Eydrob romide withBertpyl Alcohol.The preparation of triacetyl-a-aminobenzylglucoside presentedconsiderable difficulty, and the following process, although far fromsatisfactory, was the only one to give a crystalline product:Eighteen grams of the .pure recrystallised bromo-compound(1 mol.) were gradually mixed with 4-32 grams of benzyl alcohol(1 mol.), containing 3.18 grams of pyridine (1 mol.). The mobile,syrupy liquid thus obtained gradually gelatinised. The mass wasthen thoroughly mixed with dry ether, the solvent poured awayDERIVED FROM D-GlLUCOSAMINE, 51and the residue dissolved in chloroform.On the cautious additionof carbon tetrachloride an oil was precipitated, which was extractedwith a mixture of alcohol and benzene. The product crystallisedslowly from this solution. Several recrystallisations from a mixtureof ether (3 parts) and alcohol (1 part) were necessary to obtainthe glucoside salt in a state of purity. The yield was less than1 gram.Found: C=47*65; H=5-69; Br=16-63.Cl,Hl8O7N*OdC7H,,HBr requires C = 47-88 ; H = 5-50 ;Br=16*79 per cent.Triacetyl-aaminob en zylglucoside hydrobromide melts and decom-poses a t 235-236O. It does not reduce Fehling's solution, but isreadily hydrolysed, and is thus a normal glucoside. The compoundis completely decomposed when heated with barium hydroxidesolution.Solvent : Methyl Alcohol.c = 1.372, 1 = 2, t = 20°, a +- 1*43O,[ayi + 52*11*.Condensation of Bromo t riace t ylglucosamin e Hydro b romide withh'alicylaldeh yde.The success of this reaction is entirely dependent on the purityof the materials employed. The purest salicylaldehyde obtainablefrom Kahlbaum was used, and the bromo-compound was recrystal-lised until quite colourless. Thirteen grams of triacetylbromo-glucosamine salt (1 mol.) were suspended in dry ether containing2.3 grams of anhydrous pyridine (1 mol.). A solution of 10.8 gramsof salicylaldehyde (3 mols.) in dry ether was then quickly added,and the mixture- vigorously shaken for an hour, during which timethe sides of the bottle became coated with a yellow oil. The clearliquid wm poured off, and diluted with petroleum of low boilingpoint until no further precipitate was formed.I n this way theglucmide salt was obtained in excellent yield in golden-yellowneedles, which were purified by solution in ether and precipitationwith petroleum.Found: C=46*60; €€=4*92; Br=16.40; N=2.91.C,H,,O,N*O*CI,H,*CHO,HBr requires cC=46*51; E=4.94 ;Br=16.32; N=2*86 per cent.Triacetyl-a-amino-o-aldehydophenylghcoside 6ydrobromide, whenpure, is quite white, but the crystals are usually faintly yellow.The compound begins to turn brown a t 170°, and completely decom-poses at 216O. The solubility shows great variation with the degreeof purity, as minute traces of salicylaldehyde render the compoundfreely soluble in practically all organic solvents, including ether.J352 INVINE AND HYND : SYNTHETICAL AMlNOGLUCOSIDESThe pure substance is, however, dissolved readily only by the loweralcohols, and sparingly by water.Fehling's solution is reduced onlyafter hydrolysis, the removal of the salicylaldehyde residue takingplace with extreme ease.The constitution assigned to the compound in the introduction isdeduced from the following properties. When suspended in nitrousacid solution, nitrogen is evolved, thus indicating the presence ofthe aminegroup. That the compound is a glucoside is shown by itsbehaviour towards Fehling's solution before and after hydrolysis,and, as a positive result was obtained with Schiff's reagent, thearomatic aldehydic group remains unsubstituted, and is not linkedt o the sugar residue.No definite hydrazone or oxime could, how-ever, be' isolated as the compound was decomposed by phenyl-hydrazine or hydroxylamine. The addition of ferric chloride to a 'methyl-alcoholic solution of the glucoside gave only a pale greencoloration, which became violet when the solution was diluted withwater, but this result was, in all probability, due t o slight hydro-lysis. The absence of a phenolic group was confirmed by the factthat acidification of the glucoside salt dissolved in sodium hydroxidegave no precipitate. The compound is thus regarded as the salt oftriacetyl-a-aminohelicin. The pseudo-mutarotation &own by thecompound in methyl-alcoholic solution is described and discussed inthe introduction.Unsuccess fd A t t empts t o Prepare Ace tyla ted A minoglucosidesfrom Bromo triac e t y lglucosamin e Hydro b romide.The experiments summarised below refer t o reactions in which,'as a rule, condensation did occur, but the products could not beisolated in a pure condition in sufficient quantity for detailedexamination.I n each case the experimental methods employedwere varied by the use of different solvents and bases, or by thesubstitution of sodium derivatives for the free hydroxy-compounds.Reagent used.Ethylene glycol.. ..........I-Menthol ..................Saligenin .................Va&p} ................Ethyl mercaptan .........Phenyl mercaptan ......Result.Condensation occurrcd : product amorphous and deli-Condensation occurred, but only a trace of crystallineReaction took place, but the acetyl groups wereReaction occurred in each case.The products were, { however, uncrystallisable syrups.No reaction.No reaction.quescent.product was isolated.partly removed during the changeDERIVED FROM D-OLUCOSAMINE. 53Unsubstituted Amircoglucosides.a-A mino e t hylglucoside Hydrochloride.The preparation of this compound from triacetyl-a-aminoethyl-glucoside was carried out exactly as described (loc. cit.) in the caseof the corresponding methyl compound. Unless carefully recrystal-lised material is used in the preparation, the product is liable to becontaminated with the salt of aminomorphineglucoside, which issubsequently described. The hydrochloride of a-aminoethylglucosideis, however, easily obtained pure by crystallisation from ethylalcohol.Found : C = 39-31 ; H = 7.44 ; C1= 14-70.C,H,,O,N~OEt,HCl requires C"= 39-41 ; H = 7.44 ;Cl= 14.55 per cent.Solvecnt : Water.c = 2.6850, I = 2, t = 20°, a - 1*49O, [a]: - 2775O.The compound resembles a-aminomethylglucoside hydrochloridevery closely. It crystallises in well-formed, prismatic needles, andis insoluble in organic solvents with the exception of the loweralcohols. It possesses no definite melting point, but turns browna t 195O and decomposes a t 213-214O (corr.). Towards Fehling'ssolution the behaviour is characteristic of a glucoside, but hydro-lysis only takes place on prolonged boiling wit,h concentrated hydro-chloric acid. It may be mentioned that a 1 per cent.solution ofthe compound in 5 per cent. aqueous hydrogen chloride wasunaffected in rotatory power by heating for ten hours a t looo.a-Aminobenzylglucoside Hydrochloride.Owing to the difficulties experienced in obtaining pure triacetyl-a-aminobenzylglucoside hydrobromide it was necessary to modifythe usual method of preparing the unsubstituted -glucoside. Bromoctriacet.ylglucosamine hydrobromide and dry morphine were mixedin molecular proportions and suspended in dry ether; a large excess(6 mols.) of benzyl alcohol was then added, and the mixture shakenfor three days. The dissolved material was then precipitated bythe addition of ether, and, after filtration, the solid matter wasextracted with cold alcohol.The extract, on evaporation to dryness,gave a semi-crystalline residue, which was shaken with ether andfiltered. The product thus obtained was not uniform, and consistedof a mixture of the salts of partly acetylated aminobenzylglucoaides,but this did not interfere with the preparation of the uasubstitutedglucoside. The complete removal of the acetyl groups wit8 carriedout by heating at 70° for three hours with methyl alcohol containin54 IRVINE AND HYND : SYNTHETICAL AMINOGLUCOSIDES2 per cent. of hydrogen chloride, and the further treatment didn& differ in any essential respect from the other hydrolysesdescribed. The crude product was purified by solution in methylalcohol and fractional precipitation with ether.Found: C=50*90; H=6*78; C1=11.56.C6H,,04N*O*CH,*C6H,,HC1 requires C = 51.03 ; H = 6.59 ;C1= 11.60 per cent.I n crystalline form, solubilities, and behaviour towards Fehling'ssolution the compound resembles the other aminoglucosidesdescribed ; i t is, however, easily hydrolysed. Ths salt decomposes,after preliminary browning, a t 176O (corr.), and shows in aqueoussolution (c = 1) the specific rotation - 51.2O.a-A minohelicin Hydrochloride.The removal of the acetyl groups from triacetyl-a-aminohelicinwas complete on boiling in methyl alcohol containing 2 per cent.of hydrogen chloride for ninety minutes.During this process thespecific rotation diminished from +192O t o +13*7O. The productwas isolated in the form of the hydrochloride in the usual manner,and was crystallised from ethyl alcohol containing a little ether.Found: C=48*56; H=5*77; C1=11.94.C6H,20,NoO*C16~40C1E3[0,HC1 requires C= 48.81 ; H = 5.68 ;Gl= 11.10 per cent.a--4 minohelicin hydrochloride crystallises in prismatic needles,which decompose a t 180° (corr.). The solubilities resemble thoseof the other aminoglucoside salts, but the compound is unique withrespect t o the ease with which it is hydrolysed. The specific rotationin water was - 8'97O (without mutarotation), but this value is liableto correction, as the specimen appeared t o contain a trace of glucos-amine hydrochloride.a- A minosalicin Hydxo chloride.A solution. of dry saligenin (3 mols.) in anhydrous ether wasadded to finely-powdered bromotriacetylglucosamine hydrobromide(1 mol.), the mixture shaken for several hours, and put aside forone day.The ethereal layer, which was strongly acid, w a ~ thendecanted, the solid residue washed with ether, and the treatmentwith saligenin repeated. The mixture was in this case boiled forfive hours. After filtration, the solid residue was washed with&her and extracted with cold methyl alcohol. The solution thusobtained on evaporation to dryness gave a syrupy residue consistingof a mixture of the salts of the partly acebylated derivatives ofa-aminosalicin. This was hydrolysed in the usual manner in methylDERIVED FROM D-OLUCOSAMINE. 55alcoholic solution. During this change the solution became verydark, but the colour disappeared on neutralisation and subsequenttreatment with animal charcoal.The crude salt was crystallisedfrom methyl alcohol, and amounted to 20 per cent. of the weight ofthe bromo-compound originally used.Found: C=48*20; H=6.36; C l = l l . l l .C,H,,04N*O*C,H4*C'H,*OH,HC1 requires C=48.51; H= 6.27 ;C1==11.02 per cent.~ - ~ 4 minosalicin hydrochloride crystallises in colourless prisms,which decompose a t 179O (corr.). The compound shows the usualglucosidic reaction with Fehling's solution, and is hydrolysed slowlyon heating with 5 per cent. aqueous hydrogen chloride. The specificrotation in water (c=3'606) was -18*99O, and no mharotationwas detected. No colour reaction was given by ferric chloridesolution, and thus the coupling of the glucosamine and saligeninresidues must take place through the phenolic group.a-A minomorphin eglucoside.In all the condensation reactions involving bromotriacetylgIucos-amine in which morphine was employed to remove hydrogenbromide, a small proportion of the base reacted with the bromo-compound.This was notably the case in the preparation of themethyl- and ethyl-aminoglucosides, where the morphine was usedin solution. The essential product of this side-reaction is anacetylated aminoglucoside of morphine, which is found in themother liquors after recrystallisation of the crude triacetyl-a-amino-alkylglucoside salts.The material thus collected in the course of experiments involv-ing the decomposition of 30 grams of the bromo-compound washydrolysed in the usual manner by boiling for three hours in methylalcohol containing 2 per cent. of hydrogen chloride. The liquid wasthen neutralised Fith eilver carbonate, decolorised with charcoal,and concentrated to a syrup. The residue crystallised on keeping,and, after draining on porous porcelain, the crystals were purifiedby solution in methyl alcohol and fractional precipitation withether.Found : C = 61-77 ; H= 6.92.C6Hl~0,N*O*C,7H180,N requires C = 61-84 ; H = 6.78 per cent.a-B minomorphineglucoside crystallises in needles, which becomebrown at 160° and decompose a t 248O. The compoun'd has noaction on Fehling's solution, but is very easily hydrolysed to givemorphine and glucosamine salts. The specific rotation in methyl-alcoholic solution (c = 1) was - 113'5O. The properties of the corn56 McCOMBIE AND SCARBOROUGH : THE CONDENSATION OFpound showed that in its formation the reducing group of thesugar residue is coupled to the alkaloid through condensation witha hydroxyl group. This was confirmed by the fact that the basegave a glucosidic dihydrochloride, This crystallised in diamond-shaped plates, which decompmed a t 204O (corr.).Found : C1= 13.53.C''H,,O,N*O*C,,H,,OzN,2HC1 requires C1= 13.65 per cent.The authors gratefully acknowledge a research grant receivedfrom the Carnegis Trust in aid of the above investigation.CHEMICAL RESEARCH LABORATORY,UNIVERSITY OF ST. ANDREWS.UNITED COLLEGE OF ST. SALVATOR AND ST. LEONARD

ISSN:0368-1645    

DOI:10.1039/CT9130300041

出版商:RSC    

年代:1913

数据来源: RSC

摘要:

56 McCOMBIE AND SCARBOROUGH : THE CONDENSATION OFIX.-The Condermation of a- Keto-$-anilino-a-phenyl-ethane and its Homologues with Carbonyl Chloride,Phenylcurbinjide, and Phenylthiocarbir,~~~e.By HAMILTON MCCOMBIE and HAROLD ARCRIBALD SCARBOROUGH.IT has been shown by McCombie and Parkes (T., 1912, 101, 1991)that dihydro-oxazolones can be obtained from a-keto-/3-anilino-a/3-diphenylethace by two methods, namely, (i) the ketone was con-verted into ita carbethoxy-derivative (I), which on treatment withpotassium hydroxide in alcoholic solution lost the elements ofalcohol with the formation of 3 : 4 : 5-triphenyl-2 : 3-dihydro-2-oxazo-lone (11); (ii) by the direct action of carbonyl chloride in toluenesolution on the Beto-compound, in the presence of pyridine, thesame dihydro-oxazolone was produced :gPh*NPh>COC0Ph.CHPh.N Ph*CO,Et CPh--0(1.1 (11.)Attempts have now been made to extend this reaction to thepreparation of dihydro-oxazolones containing one phenyl group lessthan the compounds described by McCombie and Parkes.Thestarting Eoint for this work was a-keto-8-anilino-a-phenylethane(111), which is easily prepared from a-bromoacetophenone by con-densation with aniline. Attempts to prepare dihydro-oxazolonesfrom this compound through the carbethoxy-derivative failed, asall attempts to prepare the latter yielded only the unchangedketone. Success, however, attended the efforta when the secona- K ETO-@- AN1 LINO-a- PHENY LETHAN E, ETC. 57method of synthesis was employed. u-Keto-/3-anilincm-phenylethane,in the presence of pyridine, when condensed with carbonyl chloridein toluene solution, yielded 3 : 5-diphenyl-2 : 3-dihydro-2-oxazolone(IV) in almost quantitative yields :EH*NPh>COCOPh*CH,=NHPh CPh-0(111.) (IV.1By similar condensations the corresponding o-, m-, and (ptolyland B-naphthyl derivatives were obtained, these substituents beingin each case attached to the nitrogen atom. The u-naphthyl deriv-ative could not be prepared, but some of the substance was formed,and floated in the toluene layer, but could not be isolated andrecry stallised.These dihydro-oxazolones are very stable, the presence of thedouble bond did not lead to the addition of bromine, and thehydrogen atom in position 4 could not be substituted by bromine.The basicity of these compounds is so slight that no hydrochlorideor picrate could be isolated.Compounds similar to the sulphinazoles described by McCombieand Parkes (Zoc.cit.) might have been expected to arise from theseketones by condensation with thionyl chloride instead of carbonylchloride. With u-keto-8-anilino-a-phenylethane and thionylchloride, however, no change took place, the compound beingrecovered unchanged. With the analogous p-toluidine and8-naphthyl compounds a black, tarry mass was obtained, fromwhich no crystalline product could be isolated; thus, thionylchloride appears incapable of forming ring compounds with thisseries of ketones.Brazier and McCombie (T., 1912, 101, 2352) have shown thatu-keto-B-anilino-aP-diphenylethane and its homologues can be con-verted into ring compounds of the type 1 : 3 : 4 : 5-tetraphenyl-2 : 3-dihydro-2-glyoxalone (V) by condensation with phenylcarbimide.This synthesis has now been extended to include a series of dihydro-glyoxalones having one phenyl group less.Thus when phenylcarbimide was condensed with u-keto-p-anilino-a-phenylethane (111) there resulted 1 : 3 : 4-triphenyl-2 : 3-dihydro-2-glyoxalone (VI) :>co EPh-NPhCPh-NPh >co $Ph*NPbC H--N Ph(IT.1 (VI. 1By similar condensations the homologous tolyl and B-naphthylderivatives were obtained. The a-naphthyl derivative could notbe isolated; an olivegreen mass was formed, which could not berecryst allised58 McCOMBIE AND SCARBOROUQH : THE CONDENSATION OFThese glyoxalones are stable compounds, and their basicity is ofsuch an order as.to give rise t o picrates but no hydrochlorides.o-Tolylglyoxalone did not form a picrate which could be isolated,but the evidence seems to show that on0 is formed in hot glacialacetic acid solution.Brazier and McCombie (Zoc. cit.) found that two series ofpicrates were formed by the glyoxalones which they described, theseries depending on the group attached t o the nitrogen atom inposition 3, and that the colour varied with the composition. Onlyon0 series of picrates was formed with these new glyoxalones, inwhich one molecule of the acid was combined with one moleculeof the base, and the colours of the picrates varied between deeporange and red.It has been shown by Brazier and McCombie (loc.cit.) thatphenylthiocarbimide condenses with a-keto-Bdanilino-aB-diphenyl-ethane to give 1 : 3 : 4 : 5-tetraphenyl-2 : 3-dihydro-2-glyoxalthione(VII). This condensation has been extended so as to give a seriesof dihydroglyoxalthiones containing one phenyl group less ; thus,when phenylthiocarbimide reacted with a-keto-P-anilino-a-phenyI-ethane we obtained 1 : 3 : 4-triphenyl-2 : 3-dihydro-2-glyoxalthione(VIII) :>cs gPh*NPhCPh*NPh >as #Ph*NPhCH-NPh(VII.) (VIII.)By a similar series of condensations, the analogous 0-, m-, andp-tolyl compounds were obtained. The a- and 8-naphthyl com-pounds could not be isolated, as all attempts a t crystallisation ofthe a-naphthyl derivative resulted in a viscid, syrupy liquid, andthe 8-naphthyl derivative gave a white, crystalline substancemelting a t 166--167O, and having a nitrogen content of 7-30 percent.EXPERIMENTAL.3 : 5-Diphenyl-2 : 3-dihydro-2-oxazolone (IV).This compound was prepared by dissolving 2.1 grams of a-keto-/il-anilino-a-phenylethane in 10 grams of pyridine, and adding10 grams of a toluene solution of carbonyl chloride (20 per cent.).The mixture was cooled in ice, and, after eighteen hours, waspoured into dilute hydrochloric acid t o remove the pyridine.Theoxazolone was precipitated in the toluene layer a.s a brown, floccu-lent mass, which was separated by filtration, decolorised by boilingwith animal charcoal, and recrystallised three times from toluene,when it melted at 167-168O.The yield was nearly theoreticalu-KETO-~-ANILINO-U-PHENYLE'J"HANE, ETC. 590*1500 gave 0'4180 CO, and 0-0627 -0. C= 76-00 ; H =4-65.0.1500 ,, 7.9 C.C. N2 a t 15'5O and 725.3 mm. N=5.83.Ci,H,,O,N requires C = 75.97 ; I3 = 4-64 ; N = 5.91 per cent.3 : 5-DiphenyZ-2 : 3-dihydro-2-oxazolone crystallises in white, glis-tening needles, which are soluble in glacial acetic acid or alcoholin the cold, and moderately so in most organic solvents on warming.No salt with picric acid could be prepared in glacial acetic acidsolution, or by fusing with the acid alone. Bromination of thecompound in chloroform solution could not be effected. No hydro-chloride could be isolated in an alcoholic or a glacial acetic acidsolution.5-PhenyG3-o-tolyl-2 : 3-dihydro-2-oxazotone, Cl6Hl,O,N.This compound was prepared in the same manner, except thatit was allowed to remain for three days before the condensationwas complete.The yield was 60 per cent. of that required bytheory, and the substance melted at 124-125O:0.2000 gave 0.5602 CO, and 0.0937 H,O. C = 76.4 ; H= 5.20.0*2000 ,, 9.95 C.C. N, a t 21° and 752 mm. N=5*57.C,6H,,02N requires C= 76.4; H=5.18; N= 5.58 per cent.a-Keto-#3-m-tolwidino-a-phenylethane, C,,H,,ON.This substance was prepared by dissolving 10 grams of u-bromeacetophenone in 40 grams of alcohol, and then adding 11 gramsof m-toluidine. After remaining at room temperature for thirtyminutes, the liquid changed to a yellow, almost solid mass. Thissolid was separated and recrystallised three times from alcohol,when it melted a t 113-114O.The compound crystallises in small,lemon-yellow needles, which are soluble in all common organicsolvents. The yield was theoretical :0*2000 gave 0.5866 CO, and 0.1216 H,O. C=79*99; H=6*70.C16H,0N requires C = 80.0 ; H= 6-66 per cent.The analogous aniline and o-toluidine compounds have beenprepared by Bischler (Ber., 1892, 26, 2860), the a- and 8-naphthyl-amine derivatives by Kunckell (Ber., 1897, 30, 575), and theptoluidine compound by Lellmann and Donner (Ber., 1890, 23,167). They were prepared more easily by the authors in themanner described for a-keto-S-m-toluidino-a-phenylethane.5- Pit en.9 I -3-m- t oly 1-2 : 3 4 i h ydro-2-oxaaoEone, Cl,H,,O,N.This oxazolone is soluble to a greater extent in toluene, and anincreased.yield is obtained by evaporating, in a brisk draught60 MCCOMBIE AND SCARBOROUGH : THE CONDENSATION OFthe toluene layer which is formed on pouring the condensationmixture into dilute acid. The crystals are needle-shaped, and uniteto form clotted masses, which melt at 84-85O:The yield was 60 per cent. of the theoretical:0*2000 gave 0.5594 CO, and 0.0950 H,O. C=76*29; H=5*27.Cl6H1,O,N requires @= 76.40 ; H= 5.18 per cent.5-Phenyl-3-p-tolyl-2 : 3-d~~ydro-2-oxazolone, C,,H,,O,N.This compound crystallises from toluene in long needles, which0*2000 gave 0,5608 CO, and 0.0950 H,O. @= 76.43; H=5*27.0*2000 ,, 10.05 C.C. N2 at 21'5O and 748 mm. N=5.59.unite to form clotted masses, and melts a t 173-174O:C,,$I,,02N requires C=76-40; H=5.18; N=5.58 per cent.5-Ph enyl-3-fl-naph th yL2 : 3-dihydro-2-oxazolone, C19H1,0&I.This compound crystallises from toluene in shining needles melt-0.2000 gave 0.5870 CO, and 0.0822.C= 80.04 ; H = 4.57.0-2000 ,, 8.85 C.C. N, a t 16O and 739.5 mm. N=4.92.ing a t 193-194O:Cl,Hl,O,N requires C = 80.00 ; H = 4.53 ; N- 4-88 per cent.1 : 3 : 4-Triphenyl-2 : 3-dihydro-2-glyoxalone (VI).This compound is prepared by heating on a water-bath for threehours a mixture of a-keto-B-anilino-a-phenylethane (2.1 grams) andphenylcarbimide (1.5 grams). A clear solution is first formed,which gradually solidifies. On further heating water is eliminatedand a white mass obtained. This mass is dissolved in alcohol, and1 C.C.of concentrated hydrochloric acid is added, and the solutionheated under reflux for three hours. On cooling, the glyoxaloneseparates in clotted, white masses, which after five recrystallisationsmelted at 164-165O The substance can be equally well recrystal-lised from toluene, and is soluble on warming in all common organicsolvents. The yield was 2.5 grams:0*2010 gave 0.5958 CO, and 0.0936 H,O. C = 80.84 ; H = 5-1 7.0.1518 ,, 12.5 C.C. N2 a t 21° and 735 mm. N=9-01.C2,H1,ON2 requires C=80*76; H=5*12; N=8*97 per cent.The picrate was prepared in a boiling acetic acid solution, fromwhich it crystallisee in deep crimson needles melting at 130-131O.This salt is readily decomposed by boiling with water, alcohol, oralkali, with regeneration of the glyoxalone :0.2094 gave 0.4594 CD, and 0.0676 H,O.C=59.84; H=3.58.C21H160NZ,C6HS0,N3 requires c = 59-88 ; H = 3-51 per cent~z-KETO-~-ANILINO-~Z-PHENYLETHANE, ETC. 613 : 4-Diphem$-l-o-toly&2 : 3-dihyd~o-2-glyoxalone, C,,Hl8ON2.This compound crystallises from alcohol in small, glistening0.2099 gave 0.6251 GOz and 0.1066 H,O. C = 81.15 ; H=5*64.C,,H18~N, requires C = 80.98 ; €Z = 5.52 per cent.No picrate of this glyoxalone could be isolated, either by fusingwith picric acid or by boiling with picric acid in acetic acid solution,although the mixture assumed a deep red colour, similar to thatexhibited by the other glyoxalones.needles, which melt a t 159-160°:3 : 4-Diph.e~~yL1-m-tolyl-2 : 3dihy&o-2-glyoxalone, C,H,,ON,.This substance crptallises from alcohol in fine, white needles,0.2152 gave 0.6384 CO, and 0*1101 q0.C=80.90; H=5.68.The p-crate crystallises from glacial acetic acid in deep scarlet,glistening needles, which melt a t 126-127O :0.2061 gave 0.4563 CO, and 0.0747 H20. C=60.39; H=4.02.~,H180N2,~6H30,~3 requires C= 60.53 ; H = 4’02 per cent.which unite to form clotted masses, and melt a t 135-136O:C,,H180N2 requires C= 80.98 ; H =5*52 per cent.3 : 4-Diph enyLl-p-to&2-2 : 3dihydro-2-~yoxalone, C,H120N2.This substance crystallises from alcohol in fine, small needles,0*2000 gave O.5924 CO, and 0.1018 H20.0.3000 ,, 23.4 C.C. N, at 2 2 O and 748.5 mm. N=8.65.The picrate separates from glacial acetic acid in deep red, glisten-0.2086 gave 0.4638 CO, and 0.0729 H20.C= 60.61 ; H=3*88.C,H180N,,C,H,0,N, requires C= 60.53 ; H=3*78 per cent.which melt at 165-166O:@=80*78; H=5*65.c,&tl8ON, requires c= 80.98 ; H = 5’52 ; N = 8.59 per cent.ing needles, which melt a t 136-137O:PheTcyl-B-naph thylb enzo ylme t hytcm bamide,CH2Bz.N (C1&) CO NHP h.I f a mixture of a-keto-/3-2-naphthylamino-a-phenylethane (2.6grams) and phenylcarbimide (1.5 grams) is heated very gently ona water-bath, a white product is obtained. This is kept for a shorttime in contact with alcohol, aad ig then recrystallised fromtoluene, when it melts at 167-168O:0.1390 gave 0.4026 CO, and 0,0652 H,O. C=78*97; H=5*21.C,,H,O,N, requires C = 78.93 ; H = 5-26 per cent62 MCCOMBIE AND SCARBOROUQH : THE CONDENSATION, ETC.This compound, on boiling with alcohol, loses water, and isconverted into the glyoxalone.3 ; 4-Dipher&-l-&naphthyl-2 : 3-di7~ydro-2-glyoxalone, C25H,80Nz.This substance crystallises from alcohol or toluene in glistening0.20QO gave 0'6074 CO, and 0.0903 H20.C=82*83; H=5.02.The picrate crystallises from glacial acetic acid in orange-brown0.2002 gave 0.4620 CO, and 0.0664 H20. C= 62.96; H= 3.70.needles, which melt a t 175-176O:C&H180N% requires C = 82 87 ; H = 4.97 per cent.needles, which melt at 167-168O:~,H,,ON,,C,H,O,N, requires C = 62.93 ; H = 3-53 per cent.1 : 3 : 4-Triphenyl-2 : 3-dihydro-2-glyoxalthione (VIII).This substance was prepared by heating 2.1 grams of a-keto-B-anilin~u-phenylethane and 1.7 grams of phenylthiocarbimide in anoil-bath a t 130-140° for three t o four hours.The product witsthen crystallised from toluene, when it separated in smdl, glisten-ing needles, melting a t 170-171O. The needles are not quite white0~011 after seven recrystallisations, but have a slight yellow tinge.The compound can be recrystallised from alcohol, and is solublein most organic solvents, The yield is about 30-40 p0r cent. ofthe theoretical :0.2066 gave 0.5810 CO, and 0.0893 H,O. Cz76.70; H=4.80.0-1525 ,, 11.6 C.C. N2 a t 15O and 744.3 mm. N=8.68.0.2817 ,, 0.2019 BaSO,. S=9.84.C,,H,,N,S requires C=76.82; €€=4*87; N=8*57; S=9*75 per cent.3 : 4-Diphenyl-1-o-tolyl-2 : 3dihydro-2-gEyozalthiorce, CnHI8N2S.This compound crystallises from toluene in small, glistening0.1650 gave 0.4680 CO, and 0.0786 -0. C=77*33; H=5.29.needles, melting a t 165-166O :C,H,,N,S requires C = 77.20 ; H=5.29 per cent.3 : 4-Diphenyl-1-m-tolyl-2 : 3-dihydro-2-glyoxalthione, C,2H,,N,S.This substance crystallises from toluene in small, white needles,0*17,38 gave 0.4920 CO, and 0.0836 H,O. C=77.29; H=5-3.melting a t 168--169O:C,HI8N2S requires C = 77.20; H= 5-26 per centSTUDIES IN THE CAMPHANE SERIES. PART XXXIII. 633 : 4-Diph e n y I- 1- p- t o l y 2-2 : 3-dih y a ? ~ ~ - 2 -9 l y o xal t hi0 n e, C,H,, N,S.When recrystallised from toluene, this substance separates inlong, white needles, which unite to form clotted masses melting at192-193O :0.1533 gave 0.4355 CO, and 0*0710 H20. C=77.46; H=5*15.C&H,,N2S requires @= 77-20 ; H= 5-26 per cent.CHEMICAL DEPARTMENT,BIRMINGHAM.THE UNIVERSITY, EDGBASTON

ISSN:0368-1645    

DOI:10.1039/CT9130300056

出版商:RSC    

年代:1913

数据来源: RSC