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J O U R N A LOFTHE CHEMICAL SOCIETY.TRANSACTIONS.6mmitftt rrf @ttIrlit&m :HORACE T. BROWN, LL.D., F.R.S.J. N. COLLIE, Ph.D., F.R.S.A. W. CROSSLEY, D.Sc., Ph.D., F.R.S.BERNARD DYER, D.Sc.M. 0. FORSTER, D.Sc., Ph.D., F.R.S.P. F. FRANKLAKD, PE.D., LL.D.,0. E. GBOVES, E.R.S.F. R. S.J. T. HEWITT, M.A., D.Sc., Ph.D.,A. MCKENZIE, M.A., D.Sc., Ph.D.G. T. MORGAN, D.Sc.J. C. PHILIP, D.Sc., Ph.D.Sir WILLIAM RAMSAY, K.C.B., LL. D.,A. SCOTT, M.A., D.Sc., F.R.S.F. R. S.3’. R. S.Qbiirn :J. C. CAIN, D.Sc., Ph.D.Sttb-Cbiiar :A. J. GREENAWAY.1911. VOL XCIX. Part I.LONDON:GURNEY & JACKSON, 10, PATERNOSTER ROW.1911RIC~ARD CLAP & SONS, L M ~ ,BRUNSWICK STREET, STAMFORD STREET^ as..AND BUNGUP, SUFFOLKCONTENTS.PAPERS COMMUNICATED TO THE CHEMICAL SOCIETY.PAGE1.-The Activity of Acids as Catalysts in Relation to the Natureof the Solvent Medium, By HARRY MEDFORTH DAWSON .111.-Cryoscopic, Ebullioscopic, and Association Constants ofTrimethylcarbinol. By WILLIAM RINaaosE GELSTON ATKINS. 10III.-6-Bromo-2-phenyldihydro-l:3-benzoxazine-4-one and Re-lated Derivatives. By ERNEST CHISLETT HUGHES and ARTHURWALSH TITHERLEY . . 231V.-Synthesis of Camphoric Acid. By GUSTAV KOMPPA . . 29V.-Hydroxycodeine : a New Alkaloid from Opium. By JAMESJOHNSTON DOBBIE and ALEXANDER LAUDER . . . 34V1.-Syntheses with Phenol Derivatives Containing a MobileNitro-group. Part 111. Complex Iminazoles, Azo-compounds, and Azides. By RAPHAEL MELDOU andHAROLD KUNTZEN . . 36VI1.-Investigations on the Dependence of Rotatory Power onChemical Constitution.Part I. The Rotations of theSimplest Secondary Alcohols of the Fatty Series. ByROBERT HOWSON PICJKARD and JOSEPH KENYON , . 45VII1.-The Chemistry of Mesothorium. By FREDERICK SODDY,M.A., F.R.S. . . 721X.-Attempts to Prepare Glycerides of Amino-acids. ByROMAN ALPERN and CHARLES WEIZMANN . . 84X.-Isomeric Chromous Chlorides. By WILLIAM ARTHUR KNIQHTand ELIZABETH MARY RICH. . . . 87XI.-Reactivity of the Halogens in Organic Compounds.Part V. Interaction of Esters of the Bromo-substitutedFatty Acids with Silver Nitrate in Alcoholic Solution. ByGEORQE SENTER . . . 95XI1.-Studies in the Carbazole Series. By CARL GUSTAVSCHWALBE and SALOMON WOLFF . . 103XII1.-The Absorption Spectra of Some Derivatives andIsomerides of 1 :2-Diketo-A3-cyclopentene.By JOHN EDWARDPTJRVIS . . 107XIV. -Preparation of Ammonium Nitrite by the Sublimationin a Vacuum of a Mixture of Ammonium Chloride andAlkali Nitrites. By PANCHANAN NEOOI, M.A. and BIRE-KDRABHUSAN ADHICARP, M.A. . . 116iv CONTENTS.XV.-On dE and d-A2-m-Menthenol( 8) and dl- and d-hea(@)-m-Menthadiene. By WALTER NORMAN HAWORTH (1 85 1Exhibition Scholar of Manchester University), WILLIAMHENRY PERKIN, jun., and OTTO WALLACE .XV1.-The Direct Action of Radium on Ammonia. ByEDGAR PHILIP PERMAN .XVI-I. -The Identity of Xanthaline and Papaveraldine. ByBESSIE DOBSON and WILLIAM HENRY PERKIN, jun.XVII1.-Organic Derivatives of Silicon. Part XIV. ThePreparation of Tertiary Silicols.By FREDERIC STANLEYI'hPPINO and JOHN EDWARD HACKFORD, A.I.C., B.Sc. .XIX.-Intramolecular Rearrangements of Diphenylmethaneo-Sulphoxide. By THOMAS PERCY HILDITCH and SAMUELSMILES .By JAMES COLQUHOUNIRVINE and ALEXANDER HYND, M.A., B.8c. (CarnegieScholar) .XXL-Cupritartrates and Analogous Compounds. By SPENCERUMFREVILLE PICICERING, M. A,, F.R.S .XXIL-The Reactions between Chemical Compounds and LivingMuscle-Proteins. By VICTOR HERBERT VELEY .XXII1.-Studies of the Constitution of Soap in Solution : TheElectrical Conductivity of Sodium Stearate Solutions. ByRICHARD CHARLES BOWDEN .XX1V.-Amalgams Containing Sijver and Tin. By REGINALDARTHUR JOYNER .XXV.-Additive Compounds of Phenols and Phenolic Etherswith Aromatic Polynitro-derivatives.By JOHN JOSEPHSUDBOROUGH and STANLEY HOSKINGS BEARDXXV1.-The Relative Effect of Ethylenic and AcetylenicLinkings on Optical Rotatory Power. By THOMAS PERCYHILDITCH (1 85 1 Exhibition Scholar) .XXVI1.-The Effect of Contiguous Unsaturated Groups onOptical Rotatory Power. Part VI. The Influence of theCarbonyl Group on Optical Rotatory Power. Part VIT.The Relative Influences of Aromatic and HydroaromaticNuclei on Optical Rotatory Power. Part VIII. TheInfluence on Optical Activity of Two Contiguous Un-saturated Groups in Comparison with that of OneUnsaturated Group at Varying Distances from the OpticallyActive Complex. By THOMAS PERCY HILDITCH (1851Exhibition Scholar) . ' .XXVII1.-The Triazo-group: Part XVI. Interaction of Nitro-sates and Sodium Azide.By MARTIN ONSI,OW FORSTER andFREDERIK MARINUS VAN GELDEREN .XX1X.-The Triazo-group. Part XVII. Nitrosoazides ofPinene and Terpineol. By MARTIN ONSLOW FORSTER andSIDNEY HERBERT NEWMAN ,.XX.-0-Carboxyanilides of the Sugars..PA4E11s13213513814516116918019119520921822423924CONTENTS. VPAQEXXX.-New Derivatives of d-Glucosamine. By JAMES COLQU-HOUN IRVINE, DAVID MCNICOLL, M.A., B.Sc. (CarnegieScholar), and ALEXANDER HYND, M. A., B.Sc. (CarnegieScholar) .XXX1.-The Interaction of Silver Nitrate and Potassium Per-sulphate and its Catalytic Effect in the Oxidation of OrganicSubstances. By PERCY CORLETT AUSTIN .XXXT1.-The Orientation of the Nitro-group in Nitromyristi-cinic Acid.By ARTHUR HENRY SALWAY .XXXTI1.-The Synthesis of 3-P-Aminoethylindole. By ARTHURJAMES EWINS .XXX1V.-The Colour and Constitution of Bromine Solutions.By ALFRED FRANCIS JOSEPH and JAMES NADORISJINENDRADASA .XXXV.-The Condensation of Aromatic Aldehydes withNitromethane. By FREDERICK GEORGE PERCY REMFRY .XXXV1.-The Interaction of Alloxan and Glycine. ByWILLIAM HOLDSWORTH HURTLEY and WILLIAH ORDWOOTTON .XXXVI1.-Diff erent Methods of Applying the CrignardReagents. By HAROLD DAVIES, A.I.C., and PREDERICSTANLEY KIPPING .ByJAMES CODRINGTON CROCKER, M.A., D.Sc., and FRANKMATTHEWB, B.Sc. .XXX1X.-Cholesterol and Fatty Acids. By JAMES RIDDICKPARTINGTON . . .XL. -a-Amino-a-phenylacetamide and Some of its Derivatives.By CHARLES HUGH CLARKE and FRANCIIS FRANCIS.XL1.-Iodobenzenemonosulphonic Acids.Part 111. 2:3-Di-iodo- and 2:3:4:5-Tetraiodo-benzenesulphonic Acids. ByMARY BOYLE .XLI1.-The Mechanism of Doebner and von Miller’s QuinaldineSynthesis. By HUMPHERY OWEN JONES and PERCY EDWINEVANS. .XLII1.-Experiments on the Formation of 4(or 5)-p-Amino-ethylglyoxaline from Histidine. By ARTHUR JAMES EWINSand FRANK LEE PYMAN .XL1V.-The Nitration of Acetylbenzoin and of StilbenediolDiacetates. By ARTHUR GORDON FRANCIS and CHARLESALEXANDER KEANE . . .PartXII. The Apparent Hydration Values of the Acid Systemsand of Salts deduced from a Study of the HydrolyticActivities of Acids. By FREDERICK PALLISER WORLEY,M. A., M.Sc., New Zealand, Leathersellers’ Company%Research Fellow, City and Guilds of London Institute,XXXVII1.-The Picraminobenzoic Acids and their Salts.,XLV.-Studies of the Processes Operative in Solutions.Central Technical College.. . . .2502622662702742822882963013133193 2533433934434ri CONTENTS.XLV1.-Studies of the Processes Operative in Solutions. PartXIV. The Determination of Apparent Hydration Valuesby means of Raffinose. By WALTER HAMIS GLOVER, Ph.D.,Salters’ Company’s Research Fellow, City and Guilds ofLondon Institute, Central Technical CollegeXLVIL-Studies of the Processes Operative in Solutions.Part XV. The Changes Effected by the ReciprocalInterference of Sugars (and Glucosides) and Salts inAqueous Solutions.XLVII1.-The Phosphoric Acids.By ALFRED HOLT and JAMESECKERSLBY MYERS .XL1X.-The Determination of Solubility Coefficients by Aspira-tion. By WILLIAM JACOB JONES (Fellow of the Universityof Wales) .L.-The Auto-reduction of Hydrazines. By FREDERICK DANIELCHATTAWAY and MONTAOUE ALDRIDGE.L1.-A Synthesis of Derivatives of Phenothioxin. By THOMASPERCY HILDITCH and SAMUEL SMILES .LI1.-a-p-Hydroxy-ni-methoxyphenylethylamine and the Resolu-tion of a-p-Hydroxyphenylethylamine. By CHARLES WATSONMOORE .LII1.-The Formation and Reactions of Imino-compounds.Part XV. The Production of Imino-derivatives of Piper-idine Leading to the Formation of the PP-DisubstitutedGlutaric Acids. By FERDINAND BERNARD THOLE andJOCELYN FIELD THORPE .LIV. +-Met hyl- AaA-dodecad ien e and P-Methyl- Aay-decadiene.By VICTOR JOHN HARDINO, GERTRUDE MAUD WALSH, andLV.-The Influence of Conjugated Linkings on GeneralAbsorptive Power.Part I. The Absorption Spectra ofSome Benzene Derivatives. By CECIL REGINALD CRYMBLE,ALFRED WALTER STEWART, ROBERT WRIGHT, and WILLIAMGERALD GLENDINNINO. .LVL-The Occlusion of Hydrogen by the Palladium-GoldAlloys. By ARTHUR JOHN BERRY .LVI1.-The Determination of the Dissociation Pressures ofHydrated Salts by a Dynamical Method. By JAMESRIDDICK PARTINUTON .LVII1.-Studies in the Camphane Series. Part XXIX. ANew Phenylhydrazone of Camphorquinone. By MARTINONSLOW FORSTER and ADOLPH ZIMMERLIL1X.-The Constituents of Witlzania somnifera. By FREDERICKBELDINO POWER and ARTHUR HENRY SALWAYLX.-The Constancy of Water of Crystallisation of HydratedSalts.Part I. By HERBERT RRPRETON BAKER andGEORGE HENRY JOSEPH ADLAM..By WALTER HAMIS GLOVER .CHARLES WEIZMANN ...PAGE37137938439240440841 642244845 146346647849050CONTENTS. viiPAGELX1.-Experiments on the Synthesis of the Terpenes. Part XVI.Resolution of dZ-l-lklethyl-A3-cyclohexene-3-carboxylic Acidand Synthesis of the d- and LModifications of A3-7.wMenthenol( 8) and A3's@)-m-Ment hadiene. By BERNARDDUNSTAN WILKINSON LUFF (1 85 1 Exhibition Scholar ofUniversity College, Nottingham) and WILLIAM HENRYPERKIN, jun. .LXI1.-Experiments on the Synthesis of the Terpenes.Part XVII. dA3-p-Menthenol(8) and d-A3:s(g)-pMenthadiene.By TSAN Quo CHOU and WILLIAM HENRY PERKIN, jun..LXII1.-The Optical Properties of Compounds Containing anAsymmetric '' Quaternary " Carbon Atom. Part I. TheSynthesis of P-Phenyl-P-methylvaleric Acid and of as-Methyl.ethylsuccinic Acid. By JOHN KENNETH HAROLD INGLIS .LXIV.-Fluorone Derivatives. By FRANK GEORGE POPE andHUBERT HOWARD .LXV.-Synthesis of dl-3 :4-Dihydroxyphenylalanine. By CASIMIRFUNKLXV1.-The Action of Hydrogon Sulphide on the Alkyl-oxides of the Metals. Part I. Sodium and PotassiumEthoxides. By ALEXANDER RULE .LXVI1.-The Application of Viscometryiito the Measurementof the Rate of Reaction. By ALBERT ERNEST DUNSTAN andALBERT GEORGE MUSSELL .LXVII1.-Synthesis of Dipeptides of a-Aminolauric Acid withGlycine, Alanine, Valine, Leucine, and Asparagine. ByARTHUR HOPWOOD and CHARLES WEIZMANN .ANNUAL GENERAL MEFTING .PRESIDENTIAL ADDRESS .OBITUARY NOTICES .LX1X.-Chemical Constitution and Hypnotic Action.AcidAmides and Products of the Condensation of Malonamidesand Malonic Esters. By FREDERIC GEORGE PERCY REMFRYLXX.-The Resolution of Asymmetrical Derivatives of Phos-phoric Acid. By FREDERIC STANLEY KIPPING and FREDEEICKCHALLENGER, B.Sc. (1 85 1 Exhibition Scholar)LXX1.-The Absorption Spectra of Permanganates in CertainSolvents. By THOMAS RALPH MERTON, B.Sc. (Oxon.) .LXXII. -The Interaction of Aromatic Disulphides and SulphuricAcid. By WILLIAM GEORGE PRESCOTT and SAMUEL SMILES .LXXII1.-The Volatile Constituents of Coal. Part 11. ByMauRIcE JOHN BURGESS and RICHARD VERNON WHEELER .LXX1V.-A New Synthesis of 4(or 5-)-P-Aminoethylgly-oxaline, one of the Active Principles of Ergot.By FRANKLEEPYMAN .LXXV.-Diphenylene. A New Aromatic Hydrocarbon. Part I.By JAMES JOHNSTON DOBBIE, JOHN JACOB Fox, and ARTHUR.JOSIAH I~OFFMEISTER GAUGE .51852653854555455856557157758859961062663764064966868...V l l l CONTENTS.LXXV1.-Molecular Association in Water. By CYRIL JAMESPEDDLE and WILLIAM ERNEST STEPHEN TURNER . . 685LXXVI1.-Physical Properties of Mixtures of Ether andSulphuric Acid. By JAMES EOBERT POUND, B.Sc. (VictorianGovernment Research Scholar) . . 698LXXVII1.-Isomeric Monothiophosphates. By WILLIAM GIDLEYEMMETT and HUMPHREY OWEN JONES . . 713LXXIX. -6-Nitro-3 :4 :3': 4'-te t rame thyldiphenyl. By ARTHURWILLIAM CROSSLEY and CHARLES HERBERT HAMPSHIRE .721LXXX.-Experiments on the Synthesis of the Terpenes.Part XVIII. Synthesis of A5-o-Menthenol(S), A%-Menthenol( S), and the Corresponding Menthadienes. ByWILLIAM HENRY PERKIN, jun. . . 727LXXX1.-Experiments on the Synthesis of the Terpenes.Part XIX. Synthesis of cis- and trans-A3-o-Menthenol(8),A4-o-Mentheno1(8), and the Corresponding Menthadienes.By W~LLIAM HENRY PERKIN, jun. . . 741LXXXI1.-The Condensation of Ethyl Crotonate and EthylMethylacrylate with Ethyl Cyanoacetate and Ethyl Bromo-acetate. Synthesis of y-Methylbutane-ap6-tricarboxylic Acidand Pentane-ups- tricarboxylic Acid. By EDWARD HOPEand WILLIAM HENRY PERKIN, jun. . . 762LXXXII1.-Synthesis and Resolution of Gnoscopine(d2-Narcotine).By WILLIAM HENRY PERKIN, jun., andROBERT ROBINSON . . 775LXXX1V.-Triketohydrindene Hydrate. Part 111. ItsRelation to Alloxan. By SEIGFRIED RUHEMANN . . 7921,XXXV.-Potassium Cupricarbonates. By SPENCER UMFREVILLEPICKERING, MA., F.R.S. . . 800LXXXV1.-The Absorption Spectra of Chlorobenzene andBromobenzene as Vapours, as Liquids, and in Solution.By JOHN EDWARD PURVIS . . . . 811LXXXVI1.-Preparation of Secondary Amines from CarboxylicAcids. Part 11. Preparation of the Heptadecyl andPentadecyl Derivatives of a- and P-Naphthylamine. ByHENRY RONDELE SUEUR . . 827LXXXVII1.-Chemical Action Induced by Cathode Rays andCanal Rays. By EDGAR PHILIP PERMAN . . 833LXXX1X.-The Element Cu I Cu,O Alkali I H, at 0". ByARTHUR JOHN ALLMAND ., 840XC.-A Standard Electrode with Alkaline Electrolyte :Hg I HgO Alkali. By FREDERICK GEORGE DONNAN andARTHUR JOHN ALLMAND . . 845XC1.-The Absorption Spectra of Chlorobenzene, the Dichloro-benzenes, and the Chlorotoluenes. By EDWARD CHARLESCYRIL BALY . . 856XCI1.-The Action of Carbon Dioxide in the Bleaching Process.By SYDNEY HERDERT HIGGINS . . 858PAGCONTENTS.XCII1.-The Condensation of Acetyl Chloride and Salicyl-amide. By ARTHUR WALSH TITHERLEY and WILLIAMLONGTON HICKSXC1V.-The Volume of a Solute in Solution, Part 11. TheInfluences of Molecular Association, Solvate Formation andIonisation. By DAN TYRER .XCV.-Molecular Association and its Relationship to Electro-lytic Dissociation. The Molecular Complexity. of Halogen-containing Compounds.By WILLIAM ERNEST STEPHENTURNER .XCV1.-Coumaranone Derivatives. Part I. By RICHARDWILLIAM MERRIMAN, M. A.XCVI1.-The Influence of Temperature on the Basic WaterValue of Ethyl Alcohol. By WILLIAM JACOB JONES andARTHUR LAPWORTH .XCVIII. The Constituents of Eryony Root. By FREDERICKBELDING POWER and CHARLES WATSON MOORE .XC1X.-The Constituents of Rhubarb. By FRANK TUTIN andHUBERT WILLIAM BENTLEY CLEWER .C.-The Occurrence of Alizarin in Rhubarb. By HUGOMULLER .C1.-The Action of Steam on Iron at High Temperatures. ByJOHN ALBERT NEWTON FRIEND, THOMAS ERNEST HULL, andJOSEPH HALLAM BROWN .CI1.-The Constitution of Dehydro-/3-naphthol Sulphide and theInteraction of Sulphuric Acid with Aromatic o-Hydroxy-sulphoxides.By THOMAS PERCY HILDITCH and SAMUELSMILES .CII1.-Apparatus for the Maintenance of Constant PressuresAbove and Below the Atmospheric Pressure. Applicationto Fractional Distillation. By JOHN WADE, D.Sc., andRICHARD WILLIAM MERRIMAN, M.A. .CIV.-Iduence of Water on the Boiling Point of Ethyl Alcoholat Pressures Above and Below the Atmospheric Pressure.By JOHN WADE, D.Sc., and RICHARD WILLIAN MERRIMAX,M.A.CV.-Influence of Minute Quantities of Ferric Salts and ofixPAGE86687 1880911917937946967969973954997Manganese Nitrate on the Rate of Solution of Mercury inCVL-Methylammonium nitrite. By PRAFULLA CHANDRA R ~ Yand JITENDRA NATH RAKSHIT . . 1016CVI1.-The Isomerism of Ferrocyanides. By SAMUEL HENRYCLIFFORD BRIUGS, D.Sc.. . 1019CVII1.-The Interaction of Copper and Nitric Acid in Presenceof Metallic Nitrates. Part 11. By EDWARD HENRY RENNIE,M.A., D.Sc., and WILLIAM TERNENT COOKE, D.Sc. . . 1035By CHARLES WATSONMOORE . . 1043Nitric Acid. By PRAFULLA CHAEJDRA R ~ Y . . . 1012C1X.-The Constitution of ScopoletinX CONTENTS.CX.-Reactivity of the Halogens in Organic Compounds.Part VI. The Mechanism of Negative Catalysis. ByGEORGE SENTER and ALFRED WILLIAM PORTER, F.R.S.CXL-The Relation of Position Isomerism to Optical Activity.Part IX. The Rotation of the Menthyl Esters of theIsomeric Fluoro- and Iodo-benzoic Acids and of the HalogenDerivatives of the Fatty Acids. By JIJL~US BEREND COHEN 1058CXI1.-The Dissociation of Cupric Bromide and Some Forms ofGlass Manometer.By COLIN GYRTH JACKSON . . 1066CXII1.-The Determination of the Density of Liquids. ByHAROLD HARTLEY and WILLIAM HENRY BARRETT . . 1072CX1V.-Mannitoboric Acid. By JOHN JACOB Fox and ARTHURJOSIAH HOFFMEISTER GAUGE . . 1075CXV.-The Course of Chemical Change in Quinol Under theInfluence of Radiant Energy. By WALTER NOEL HARTLEYand OTWAY HENRY LITTLE . . 1079CXV1.-The Intramolecular Condensation of Aromatic Sul-phinic Acids. Part 11. The Interaction of AromaticDisulphoxides and Sulphuric Acid. By THOMAS PERCYHILDITCH . . 1091CXVI1.-Hydroaromatic Ketones. Part 11. 1 :I :2-Tri-methylcyclohexan-3-one. By ARTHUR WILLIAM CROSSLEYand NORA RENOUF . . 1101CXVII1.-Electrolytic Reduction. Part IV. AromaticAldehydes. By HERBERT DRAKE LAW .. 1113CX1X.-The Conductivity and Viscosity of Aqueous Solutionsof Aniline Hydrochloride at 25". By NEVIL VINCENTSIDUWICK and BERNARD HOWELL WILSDON. . . 1.118CXX.-The Solubility of Aniline in Aqueous LHolutions of itsHydrochloride. By NETIL VINCENT SIDGWICK, PERCIVALCXX1.-The Solubility of Electrolytes in Aqueous Solutions.Part I. Solubility of Salts in the Corresponding Acids.By JAMES IRVINE ORME MASSON (1851 Exhibition Scholarof the University of Melbourne) . . 1132CXXI1.-The Effect of Temperature and of Pressure on theEquilibrium ~ C O S C O , + C. By THOMAS FRED ERICRHEAD and RICHARD VERNON WHEELER . . 1140CXXIIL-Synthetical Experiments in the Group of theisoQuinoline Alkaloids. Part I. Anhydrocotarninephthrtlide.By EDWARD HOPE and ROBERT ROBINSON .. 1153CXX1V.-Synthesis of Pinacones. Part I. By WILLIAMPARRY . . 1169CXXV.-The Decomposition of Diethylenesulphidemethyl-sulphine Hydroxide in Aqueous Solution. By LEILAGREEN and BRENDA SUTHERLAND,PAGE. 1049PICKFORD, and BERNARD HOWELL WILSDON . , 1122. 117CONTENTS. x1PAGECXXV1.-Purification of Acetic Acid. By KENNEDY JOSEPHPREVITI~ ORTON, MURIEL GWENDOLEN EDWARDS, andHAROLD KING . . 1178CXXVI1.-The Detection and Estimation of Small Quantitiesof Acetic Anhydride in Acetic Acid. By MURIEL'GWENDOLEN EDWARDS and KENNEDY JOSEPH PREVIT~ORTON . . 1181CXXVII1.-A Method of Chlorination. Chlorination ofAnilines and Phenols. By KENNEDY JOSEPH PREV~TBORTON and HAROLD KING. . 1185CXX1X.-Some Reactions of o-Bromomethylfurfuraldehyde.By WILLIAM FRANCIS COOPER, R.A.(Cantab) and WALTERHAROLD NUTTALL, F.I.C. . . 1193FARADAY LECTuRE.-T he Fundamental Properties of theCXXX.-Properties of Binary Mixtures of Some LiquefiedGases. By LANCELOT SALISBURY BAGSTER (VictorianGovernment Research Scholar) .CXXX1.-The Second and Third Dissociation Constants ofOrthophosphoric Acid. By EDMUND BRYDGES RUDHALLPRIDEAUX . . 1224CXXXI1.-Some Derivatives of Gelsemine. By CHARLESWATSON MOORE . . . . . 1231CXXXII1.-The Constituents of the Bulb of Buphanedisticha. By FRANK TUTIN . . 1240CXXX1V.-Orthophosphoric Acid as a Dehydrating CatalyticAgent. Part I. The Condensation of Acetone inPresence of Phosphoric Acid.CXXXV.-Trialkylammonium Nitrites and Nitrites of theBases of the Pyridine and Quinoline Series.Part I. ByPARCHANAN NEWI, M.A. . . 1252CXXXV1.-The Absorption Spectra of Cinchonine, Quinine,and their Isomerides. By JAMES JOHNSTON DOBBIE andALEXANDER LAUDER . . 1254CXXXVI1.-The Influence of Conjugated Linkings onGeneral Absorptive Power. Part 11. Some Open-chainand Cyclic Compounds. By CECIL REGINALD CRYMBLE,ALFRED WALTER STEWART, ROBERT WRIGHT, and FLORENCEWILLIAMSON REA . . 1262CXXXVII1.-New Derivatives of Aminolauronic Acid. ByJOHN WEIR, M.A., B.Sc., Ph.D. (Carnegie Fellow) . . 1270GXXXIX.-The Triazo-group. Part XVIII. P-Triazo-ethylamine. By MARTIN ONSLOW FORSTER and SIDNEYHERBERT NEWMAN . . 1277CXL.-Syntheses with Phenol Derivatives Containing a MobileNitro-group.Part IV. Quinone-irnides ; AsymmetricQuaternary Ammonium Compounds and AsymmetricCarbinols. By RAPHAEL MELDOLA and HAROLD K ~ T Z E N . 1283Elements. By THEODORE WILLIAM RICHAXDS . . 1201. 1218By PA~CHBNAN NEOGI, M.A. 124xii CONTENTS.CXL1.-The Action of Salt Solutions and of Sea-water on Ironat Various Temperatures. By JOHN ALBERT NEWTONFRIEND AND JOSEPH HALLAM BROWN . . 1302CXLI1.-Triketohydrindene Hydrate. Part IV. HydrindantinC X L 1 I I . T h e Alleged Complexity of Tellurium. By AUGUSTUSGEORGE VERNON HARCOURT and HERBERT BRERETON BAKER . 13 1 1CXL1V.-The Solubility of Carbon Dioxide in Beer. ByALEXANDER FINDLAY and BUCCHOK SREN, B.Sc., A.I.C. . 1313CXLV.-Synthesis of 4:6-Dimethoxy-2-/3-methylaminoethyl-benzaldehyde. By ARTHUR HENRY SALWAY .. 1320CXLV1.-Some New Inorganic Salts. By THOMAS VIPONDBARKER . . 1326CXLVI1.-The Action of Sodium Hypophosphite on CopperSulphate in Aqueous Solution. By JAMES BRIERLEY FIRTHand JAMES ECRERSLEY MYERS . . 1329CXLVII1.-Indicators of the Methyl-red Type. By HUBERTHOWARD and FRANK GEO. POPE. . . 1333CXL1X.-Di h ydrocinnamenylcarbamide. (p-Phenylethyl Go-Cyanate. By MARTIN ONSLOW FORSTER AND HERMANNSTOTTER . . 1337CL.-The Constitution of Berberine. By CHARLES KENNETHTINKLER . . 1340CL1.-Cupriglycollates, By SPENCER UMFREVILLE PICKERING,M.S., F.R.S. . . 1347CLI1.-The Synthesis of Derivatives of Thioxanthone fromAromatic Disulphides. By EFFIE GWENDOLINE MARSDENand SAMUEL SMILES . . 1353CLII1.-The Dissociation Pressures of Alkali Bicarbonates.Part I.Sodium Hydrogen Carbonate. By ROBERTMARTIN CAVEN and HENRY JULIUS SALOMON SAND . . 1359CL1V.-The Relation of the Velocity of Chlorination ofAromatic Compounds to Constitution. Part I. Chlorina-tion of Anilides. By KENNEDY JOSEPH PREVIT~ ORTON andHAROLD KING . . 1369Effect of the Constitutionof the Acyl Group on the Proportion of the Ortho- andPara-derivatives. By HAROLD KING and KENNEDY JOSEPHPREVIT~ ORTON . . 1377CLV1.-Aromatic Antimony Compounds. Part 11. The Actionof the Chlorides of Antimony on Aniline and its Derivatives.By PERCY MAY . . 1382CLVI1.-The Synthesis of Histidine. By FRANK LEE PYMAN . 1386CLVII1.-The Interaction of Metallic Oxides and PhosphorylChloride, Alone and in the Presence of Certain OrganicCompounds.By HENRY BASSETT, jun., and HUGH STOTTTAYLOR . , 1402By DAVID BORAR 1414PAGEand its Analogues. By $LEGFRIED RUHEMANN . . 1306CLV.--Chlorination of Acylanilides.CL1X.-Some Reducing Actions of Mercury... CONTENTS. X l l lPAGECLX.-Electromotive Forces in Alcohol. Part I. Concentra-tion Cells with Electrodes Reversible to Chlorine Ions. ByARTHUR LAPWORTK and JAMES RIDDICK PARTINGTON . . 1417CLX1.-Equilibrium in the System : Ethyl Alcohol, AceticAcid, Ethyl Acetate and Water, and its Apparent Dis-placement by Hydrogen Chloride. By WILLIAM JACOBJONES and ARTHUR LAPWORTH . . . . 1427ByWILLIAM ROBERT BOUSFIELD, M. A,, K.C., and THOMASMARTIN LOWRY, D.Sc. . . . 1432CLXII1.-Some Oxidation Products of the HydroxybenzoicAcids.Part 111. By ARTHUR GEORGE PEERIN . . 1442CLX1V.-The Interaction of Formic Acid and Cellulose. ByCHARLES FREDERICK CROSS and EDWARD JOHN BEVAN . 1450OBITUARY NOTICE . . 1457CLXV.-A Method for the Accurate Volumetric Determinationof the Oxygen in Air. By HERBERT EDMESTON WATSON(1851 Exhibition Scholar, University College, London)CLXVL-Tetramethylammonium Hyponitrite and its Decom-position by Heat. By PRAFULLA CHANDRA RAY andHEMANDRA KUMAR SEN . . 1466CLXVI1.-Nitrites of the Alkylammonium Bases : Ethyl-ammonium Nitrite, Dimethylammonium Nitrite, and Tri-methylammonium Nitrite. By PRAFULLA CHANDRA R ~ Yand JITENDRA NATH RAKSH~T . . 1470Benzyl-ammonium Nitrite and Dibenzylammonium Nitrite andtheir Sublimation and Decomposition by Heat.ByPRAFULLA CHANDRA R ~ Y and RASIK LAL DATTA . . 1475CLX1X.-The Density of Liquid Sucrose and of its Solutionsin Water. By FREDERIK SCHWERS . . 1478CLXX.-Triketohydrindene Hydrate. Part V. The Analoguesof Uramil and Purpuric Acid. By SIEGFRIED RUHEMANN . 1486CLXX1.-The Action of Ammonia and Amines on 2-Phenyl-1 :3-benzoxazine-4-one. By ARTHUR WALSH TITHERLEY andERNEST CHISLETT HUGHES . . 1493CLXXI1.-Optically Active Derivatives of 1-Methylcyclo-hexylidene-4-acetic Acid. By WILLIAM HENRY PERKIN, jun.,and WILLIAM JACKSON POPE . . 1510CLXXII1.-Some Reactions of Gum Kino. By JOHN LIONELSIMONSEN . . 1530CLXX1V.-Synthesis of Derivatives of Thioxanthone. Part111. 1 :4-Dihydroxythioxanthone. By HANS THACHERCLARKE and SAMUEL SMILES .. 1535CLXI1.-The Purification and Properties of Acetic Acid.. 1460CLXVII1.-Nitrites of the Benzylammonium Seriesxiv CONTENTS.CLXXV.-Contributions to the Chemistry of the Terpenes.Part IX. The Oxidation of Camphene with HydrogenPeroxide. By GEORGE GERALD HENDERSON and MAGGIEMILLEN JEFFS SUTHERLAND, B.Sc. (Carnegie ResearchCLXXV 1.-The Constitution of the Organic Ferrocyanides.By ERNALD GEORGE JUSTINIAN HARTLEY . . 1549CLXXVI1.-The Osmotic Pressure and Conductivity of AqueousSolutions of Congo-red, and Reversible Membrane Equi-libria. By FREDERICK GEORGE DONNAN and ALBERT BUCKLEYHARRIS . . 1554CLXXVIII. -Synthesis of Polypeptides of a- Amino-?a-nonoicAcid with Glycine, Alanine, Valine, Leucine, Asparagine,and Aspartic Acid.By ARTHUR HOPWOOD and CHARLESWEIZMANN . . 1577CLXX1X.-Substitution in Aromatic Hydroxy-compounds.Part I. The Action of Nitric Acid on Gallic Acid Tri-methyl Ethyl and Pyrogallolcarboxylic Acid TrimethylEther. By VICTOR JOHN HARDING . . 1585CLXXX.-Trialkylammonium Nitrites and Nitrites of theBases of the Pyridine and Quinoline Series. Part 11. ByCLXXX1.-Ionisation in Non-aqueous Solvents. Part I. ByHARRY MEDFORTH DAWSON and MAY SYBIL LESLIE, M.Sc. . 1601CLXXXI1.-Salts of 3:5-Dinitroquinol. By WILLIAM BAYLISSSHAW . . 1609CLXXXIII.-2:2’-Dibromodiphenyl and 2:2’-Dichlorodiphenyl.By JAMES JOHNSTON DOBBIE, JOHN JACOB Fox, and ARTHURJOSIAH HOFFMEISTER GAUGE . . 1615CLXXX1V.-The P-Chlorocinnamic Acids. By THOMASCAMPBELL JAMES . .1620CLSXXV.-The Condensation of Crotonaldehyde. By IDASMEDLEY (Beit Memorial Research Fellow). . . 1627CLXXXV1.-Latent Heats of Vaporisation of Mixed Liquids.Part 11. By DAN TYRER . . 1633OBITUARY NOTICES . . 1646CLXXXVI1.-The System : Palmitic Acid-Sodium Palmitate.By FREDERICK GEORQE DONNAPU’ and ALBERT SIMPSONWHITE . . 1668CLXXXVlI1.-The Chlorine Derivatives of Pyridine. PartXI. Some Interactions of 3:4:5-Trichloropicolinic Acidand of its Derivatives. By WILLIAM JAMES SELL . . 1679CLXXX1X.-The formation and Reactions of Imino-compounds.Part XVI. Reactions Leading to the Formation of Tri-carballylic Acid. By FERDINAND BERNARD THOLE andJOCELYN FIELD THORPE . . 1684PAGEScholar) . . 1539PARCHANAN NEOGI, M.A. . . 159CONTENTS. xvPAGECXC.-imQuinoline Derivatives.Part VI. neooxyberberine.By FRANK LEE PYMAN . . , 1690CXC1.-The Absorption Spectra of Various Chlorine andBromine Derivatives of Benzene and Toluene as Vapours,in Solution and in Thin Films.CXCI1.-Substances Related to Cochenillic and Carminic Acids.Part I. Synthesis of the Methyl Ether of /3- and ofy-Coccinic Acid. By ANDREW NORMAN MELDRUM (lateCarnegie Research Fellow) . . . 1712By JOHN EDWARD PURVIS . 1699CXCII1.-Myricetin. Part 111. By ARTHUR GEORGE PERKIN. 1721CXC1V.-The Photochemical and Thermal Interaction ofChlorine and Carbon Monoxide. By DAVID LEONARDCHAPMAN and FRANK HOUGHTON GEE . . 1726CXCV.-The Reactivity of Ketones towards Iodine and theRelative Rates of Tautomeric Change. Part 11.ByHARRY MEDFORTH DAWSON and HARRY ARK, M.Sc. . . 1740CXCV1.-The formation of Glyoxsllines from Acyl Derivativesof a-Keto-p-anilino-ap-diphenylethane. By ARTHUR ERNESTEVEREST (Priestley Research Scholar of the University ofCXCVI1.--The Effect of Heat on a Mixture of Benzaldehyde-cyanohydrin and Aniline. By ARTHUR ERNEST EVEREST(Priestley Research Scholar of the University of Birming-ham) and HAMILTON MCCOMBIE . . 1752CXCVII1.-Composition of the Essential Oil of Myrica Gale, L.By SAMUEL SHROWDER PICKLES . , . 1764CXC1X.-An Application of Kirchhoff's Equation to Solutions.(A Contribution to the Thermodynamic Theory of Solu-bility.) By ROBERT TAYLOR HARDMAN and JAMES RIDDICKPARTIKGTON . . 1769CC.-The Action of Benzylamine on s-Dibromosuccinic Acid.CC1.-A Method of Determining Casbon and Nitrogen inOrganic Compounds.By EDWARD PERCY FRANKLAND . . 1783CCI1.-The Absorption Spectra of the Isomeric Hydrazonesand Semicarbazones of Camphorquinone. By FREDERICKRUSSELL LANKSHEAR and ARTHUR LAPWORTH . . 1785CCII1.-The Solubility of Cuprous Oxide in Aqueous AmmoniaSolutions, and the Composition of the Cuprous-ammoniaComplex. By FREDERICK GEORGE DONNAN and JOHN SMEATHTHOMAS . . 1788CC1V.-The Synthesis of Hydrocarbons a t High Temperatures.By JOHN NORMAN PRmG and DOEIAN MACEFIELD FAIRLIE . 1796CCV.-Decomposition of Dry Ozone. By DAVID LEONARDC'CV1.-The Acid Character of Gallotannic Acid. By RAMNIBirmingham) and HAMILTON MCCOMBIE . . 1746By EDWARD PERCY FRANKLAND . . 1775CHAPMAN and HERBERT EDWIN JONES .. 1811PANIKER and EDMUND STIASNY . . . 181xvi CONTENTS.CCVI1.-Bimolecular Glycollaldehyde. By NIAL PATRICKMCCLELAND . . 1827CCVII1.-The Aerial Oxidation (Rusting) of Metals. ByWYNDHAM ROWLAND DKJNSTAN and JOHN ROBERTSHAW HILL. 1835CC1X.-The Passivity of Iron and Certain other Metals, ByWYNDHAM ROWLAND DUNSTAN and JOHN ROBERTSHAW HILL. 1853REPORT OF THE INTERNATIOSAL COMMITTEE ON ATOMIC WEIGHTS,1912 . . 1867CCX. -The Active Constituents of the Indian SolanaceousPlants Datura Stramonium, B. fastuosa, and D. Metel. ByALBERT EDWARD ANDREWS. . . 1871CCX1.-A New Stereoisomeride of Cyanodihydrocarvone. ByARTHUR LAPWORTH and VICTOR STEELE . . 1877CCXI1.-Some Properties of Phenyl isoPropyl Ketone, ByARTHUR LAPWORTH and VICTOR STEELE .. 1882CCXII1.-Contributions to the Chemistry of the Terpenes.Part X. The Action of Chromyl Chloride, Nitrous Acid,and Nitric Acid on Bornylene. By GEORQE GERALDHENDERSON and ISIDOR MORRIS HEILBRON. . . 1887CCX1V.-The Constitution of Camphene. By GEORGE GERALDHENDERSON and ISIDOR MORRIS HEILBRON. . . 1901CCXV.-The Action of Chlorine on Alkalis and of CarbonDioxide on Bleaching Powder. By ROBERT LLEWELLYNTAYLOR . . 1906Part VII.Action of Phosphorus Pentachloride and of ThionylChloride on Optically Active Hydroxy-acids and Esters.CCXVI1.-The Relation between Residual Affinity and ChemicalConstitution. Part 11. Certain Compounds of Nitrogen.By HANS THACHER CLARKE (1851 Exhibition Scholar)CCXVIIL-The Temperature-coefficient of the Electrical Con-ductivity of Hydrogen Chloride in Alcoholic Solution.ByJAMES RIDDICK PARTINGTON . . 1937CCX1X.- The Absorption Spectra of the Nitration Products ofDimethyl-p-toluidine. By GILBERT T. MORGAN and ARTHURCLAYTON , . 1941CCXX.-Decomposition of Hydrazides and Hydrazones byHeat. By FREDERICK DANIEL CHATTAWAY , CHARLES LINAEUSCUMMING, and BERNARD HOWELL WILSDON .CCXX1.-The Absorption Spectra of Triketohydrindene HydrateCCXXI1.-The Alkaline Condensations of Nitrohydrazo-com-pounds. Part I. By ARTHUR GEORGE GREEN and ERNESTARTHUR BEARDER . . 1960CCXXII1.-Trimercuridiethylammonium Nitrite. By PRAFULLACHANDRA RAY and JITENDRA NATH RAKSHIT . . 1972PAQECCXV1.-Experiments on the Walden Inversion.By ALEX. MCKENZIE and FRED BARROW .* 1910. 1937. 1950and Certain Derivatives. By JOHN EDWARD PURVIS . . 195CONTENTS. xviiPAGECCXX1V.-Studies of Ammonium Solutiona. Part I. AnCCXXV.-Studies in the Camphane Series. Part XXX. Con-stitution of Pernitrosocamphor (Camphenylnitroamine). ByMARTIN ONSLOW FORSTER, JOHN ROBERT TROTTER, andJACOB WEINTROUBE . . 1982CCXXV1.-The Constituents of the Seeds of Cusirniroa edulis.CCXXVI1.-Komppa's Synthesis of Camphoric Acid. ByCCXXVII1.-The Lower Limit of Inflammation of Mixtures ofthe Paraffin Hydrocarbons with Air. By MAURICE JOHNBURGESS and RICHARD VEBNON WHEELER . . 2013CC!XXIX.-~-2-Methoxynaphthylpropionic Acid and Methoxy-perinaphth-hydrindone. By GEORGE BARGER and WALTERWILLIAM STARLING . . 2030CCXXX.-Syntheses with Phenol Derivatives Containing aMobile Nitro-group.Part V. Quinoneimides, AsymmetricQuaternary Ammonium Compounds, and AsymmetricCarbinols (continued). By RAPHAEL MELDOLA and HAROLDKUNTZEN . . 2034CCXXX1.-The Synthesis of Derivatives of Thioxanthone.Part IT. Synthesis from Aromatic Sulphinic Acids. ByHAROLD CHRISTOPHER and SAMUEL SMILES. . . 2046CCXXXI1.-Some Derivatives of 4( or 5)-Methylglyoxaline. ByARTHUE JAMES EWINS . . 2052CCXXXIIL-The Triazo-group. Part XIX. Nitrosoazides ofDipentene, d-Limonene, and E-Limonene. By MARTINONSLOW FORSTER and FREDERIK MARINUS VAN GELDEBEN . 2059CCXXX1V.-Preparation of the Betaine of Tryptophan and itsIdentity with the Alkaloid Hypaphorine. By PIETER VANROMBURGH and GEORGE BARGER .. 2068CCXXXV.-Dihydroxydihycirindamine and its Resolution intoOptically Active Components. By WILLIAM JACKSON POPEand JOHN READ . 2071Part 11.Naphthylideneamines. By ALFRED SENIER and ROSALINDCLARKE . . 2081CCXXXVI1.-Isomeric Acetaldehydephenylhydrazones. ByERNYST GRAHAM LAWS and NEVIL VINCENT SIDGWICK . 2085CCXXXVII1.-Theory of Dyeing : the Coloui- and MolecularState of Picric Acid. By WILLIAM PORTER DREAPER, F.I.C. 2094CCXXX1X.-Formation of Six- and Seven-membered Ringsfrom Derivatives of 2:2'-Ditolyl. By JAMES KENNER andEMILY GERTRUDE TURNER . * . 2101Ammonium Electrode. By ROLAND EDGAR SLADE . . 1974By FREDERICK BELDING ~ O W E R and THOMAS CALLAN . . 1993GUSTAVE LOUIS RLANC and JOCELYN FIELD THORPE . . 2010CCXXXV1.-Studies in Phototropy and Thermotropyxviii CONTENTS.CCXL.-Synthetical Experiments in the Group of the &o-Quinoline Alkaloids.Part 11. The Constitution of theCondensation Products of Cotarnine and the Condensationof Cotarnine with Aliphatic and Aromatic Nitro-com-pounds. By EDWARD HOPE and ROBERT ROBINSON , . 2114CCXL1.-The Electrochemistry of Solutions in Acetone. PartI. By ALEXANDER ROSHDESTWENSKY and WILLIAM CUDMOREMCCULLAGH LEWIS . b . . 2138CCXLI1.-Chemical Examination of Calibar Beans. By ARTHURHENRY SALWAY . . 2148CCXLII1.-Contributions to the Chemistry of the Terpenes.Part XII. Synthesis of a Menthadiene from Thymol, andof a Diethylcyclohexadiene from Phenol. By GEORGEGERALD HENDERSON and ROBERT BOYD, B.Sc. (CarnegieResearch Scholar) .. 2159CCXL1V.-The Velocity of Addition of Alkyl Bromides toCyclic Tertiary Bases. By FRANK STEVENSON LONG . . 2164CCXLV.-Aminoalkylglyoxalines. By FRANK LEE PYMAN . 2 172CCXLV1.-The Probable Cause of the Elimination of aCarbethoxyl Group as Ethyl Carbonate by the Action ofSodium Ethoxide. By FERDINAND BERNARD THOLE andJOCELYN FIELD THORPE . . 2183Part I.Methods for the Preparation of the Alkylglutaconic Acidswhich Prove the Identity of the a- and y-Positions in theGlutaconic Acid Molecule. By FERDINAND BERNARD THOLEand JOCELYN FIELD TXIORPE . . 2187Part 11.The Reactions of the Alkylglutaconic Acids Having OneMobile Hydrogen Atom. By FERDINAND BERNARD THOLEand JOCELYN FIELD THORPE . . 2208CCXL1X.-Electromotive Forces in Alcohol. Part 11. TheHydrogen Electrode in Alcohol and the Influence of Wateron its Electromotive Force. By ROBERT TAYLOR HARDMANand ARTHUR LAPWORTH . . 2242CCL.-Polymorphic Phthalylhydrazides. By FREDERICK DANIELCHATTAWAY and DONALD FREDERICK SANDYS W~NSCH . . 2253CCL1.-The Influence of Inactive Electrolytes on the OpticalActivity of Z-Malic Acid in Aqueous Solution. ByCLIFFORD MORGAN STUBBS (1851 Exhibition Scholar of theUniversity of New Zealand) . . 2265CCLI1.-Organic Derivatives of Antimony. Part 11. TheOrienting Influence of Antimonic Substituents in theBenzene Nucleus. By GILBERT T. MORGAN and FRANCESM. G. MICKLETHWAIT . . 2286CCLII1.-The Preparation of the Ketones of the Higher FattyAcids. By THOMAS HILL EABTERFIELD and CLAM MILLICENTTAYLOR (New Zealand Government Research Scholar)PAOE;CCXLVI1.-The Chemistry of the Glutaconic Acids.CCXLVII1.-The Chemistry of the Glutaconic Acids.. 229CONTENTS. xix?AGECCL1V.-The Separation of Mixture8 of Organic Acide byPartial Esterification. By JOHN JOBEPH SODBOROUGH andEBENEEER REEB THOMAS . . 2073CCLV.-The Absorption Spectra of Various Iodine Derivativesof Benzene and Toluene as Vapours, in Solution, and inThin Films. By JOHN EDWARD PURVIS . . . 2318CCLV1.-Influence of Double Linking on Optical Activity ;Some fi-propyl and Ally1 Derivatives of Menthol. ByPERCY FARADAY FRANKLAND and HUGH HENRY O’SULLIVAN . 2325CCLVI1.-The Constitution of Ergothioneine : a BetaineRelated to Histidine. By GEORUE BARGER and ARTHURJAMESE~INB . . . . 2336CCLVII1.-Derivatives of o-Xylene. Part I. 3-Nitro-o-xyleneand 3:6-Dinitro-o-xylene. By ARTHUR WILLIAM CROSSLEYand GERTRUDE HOLLAND WREN . . 2341CCL1X.-Derivatives of o-Xylene. Part 11. Dinitro-o-xylidines.By ARTHUR WILLIAM CROSSLEY and GEORGE FRANCISMOHRELL , . 2345BERTHELOT MEMORIAL LECTURE . 235

ISSN:0368-1645    

DOI:10.1039/CT91199FP001

出版商:RSC    

年代:1911

数据来源: RSC

摘要:

10 ATKINS : CRY OSCOPIC, EBULLIOSCOPIC, AND ASSOCIATIONI I. - Cryoscopic, Rbul lioscopic, and AssociationConstants of Trimethylcarhinol.By WILLIAM RINGROSE GELSTON ATKINS.IT was suggested by Professor E. A. Werner that t.rimethylcarbino1might be a useful solvent for molecular-weight determinations bycryoscopy, its it was the only one of the lower alcohols that had aconvenient melting point, and was not likely to dissociate completelycertain organic compounds which were being studied by him.As the divergence between the values of E, the molecular loweringof freezing point, it8 found by experiment and as calculated fromthe heat of fusion, was very remarkable, the study of the e b u l bscopic and association constants was also undertaken.Trimethylcarbinol waa found by Paternb and Ampola (Gazzefta,1897, 27, i, 481) to give one minimum on the freezingpoint curvewith pbromotoluene, and one with thymol; they point out thatthe freezing points of these mixtures cannot be even approximatelycalculated by the formula E = RT2 -O With phenol they find a100s'complex curve, showing two maxima and three minima.CalculatioCONSTANTS OF TRIMETHYLCARBINOL. 11from their data shows that the compounds (CH3),C:*OH,2C6H,*OHand 3(dH&C*OH,C6H,*OH are present, making allowance for theflat nature of the curves.Patern6 ( A t t i R. Accad. Lincei, 1907, [v], 16, ii, 153) has shownthat the compound (CH,),C*OH,ZH,O exists from a study of thefreezing point diagram, but viscosity determinations show that itis completely dissociated a few degrees above the melting point ofthe pure alcohol. Subsequently, Paternb and Mieli ( A t t i R.Accad.Lincei, 1908, [v], 17, i, 396) drew the conclusion that therewas no correlation between the density curve and the temperature-composition curve for the phenol-trimethylcarbinol mixture.The melting point of the alcohol, 25’53O, is abnormally high forthe series. It seems that this is due to a combination of twofactors. It has been pointed out by Carnelley (Smiles, ChemicalConstitution and Some Physical Properties, p. 200) that amongisomerides the compound with the more symmetrical structurepossesses the higher melting point, whilst Markownikoff has shownthat the compound with the more highly branched chain of carbonatoms melts at the higher temperature.Now trimethylcarbinol isat once the most symmetrical alcohol, for the methyl group(CH,= 15) is very close to the hydroxyl group (OH =17) in weight,and the most highly branched form of carbon atom chain is alsopresent, hence the remarksbly high melting point.Cryoscopic Constant.Kahlbaum’s trimethylcarbinol wm purified by distillation withbenzene (S. Young, Fractional Distillation, p. 233), and placed inthe inner tube of a Beckmann apparatus, with stirrer and dryingtube attached. The following substances were employed as solutesto determine the constant : p-dibromobenzene, acetanilide, thio-carbamide, p-toluidine, and a-naphthylamine. The details are givenin the experimental part of the paper. The values of E rangedfrom 134.5 to 82.5 for p-dibromobenzene as t,he concentrationincreased, from 154.4 to 72.9 for acetanilide, from 152.5 to 137.4for a-naphthylamine, whilst thiocarbamide gave E = 83.7.Takingde Forcrand’s (Compt. rend., 1903, 136, 1034) value for the latent100s’where R =1.991 cal. and To is the melting point on the absolutescale, it is found that E (calc.) = 84.5.It appears a t first sight aa if the determinations had been madewith substances which dissociated in solution, and thus gave indilute solutions a, depression nearly twice as great it9 would beheat of fusion, s =20*978 cal., and evaluating the expression E = ~ R12 ATKINS : CRYOSCOPIC, EBULLIOSCOPIC, AND ASSOCIATIONexpected, whilst in concentrated solutions the theoretical value wasmore nearly approached.However, the chemical evidence isstrongly against the dissociation of the solutes employed to anythinglike the extent required, a t any rate. Moreover, it was found thatthe pure alcohol was practically a non-conductor, and when a littlep-toluidine was dissolved in it, no difference could be detected in itsconductivity, although a sensitive galvanometer was used.To test the possibility of the unexpectedly great lowering of thefreezing point being due to the hygroscopic nature of the liquid,the apparatus was allowed to remain for one day, when thedepression was found to be only Om02O lower than on the previousday. Taking into account the difficulty of obtaining two con-secutive readings with this solvent, which differ by less than O*0lo,it is clear that the slow absorption of water will not explain theresults. The decrease in E with increase in concentration is alsoagainst such an explanation.Separation of the solute with thesolvent would, of course, lower the value of E, and so need not beconsidered further.There still remains the possibility of error having arisen throughthe too great separation of the solvent on freezing, and through aradiation effect from the cooling bath. Accordingly, fresh deter-minations were made, using p-dibromobenzene as solute, the tem-perature of the bath being -0.8O and - 2 . 5 O below that of thesolution. The value thus obtained for A was corrected by Raoult'sequation (Compt. rend., 1897, 125, 751), A = A (obs.) (1 - KS), whereS is the supercooling in degrees, and K is a constant obtained fromthe expression :in which L is the heat of fusion of the solvent, T the water equivalentof t,he part of the apparatus wetted, R the water equivalent of thesolvent used, t the time from freezing to steady temperature, andT the time for the apparatus to cool or warm lo by radiation.Theresultant value was E= 128, which agrees well with the deter-minations of E in the main series.Thus for a dilute solution of pdibromobenzene the value of E is128, whereas theory requires i t to be 84.5. The discrepancy mustbe accepted as a fact, and an explanation attempted. On t,his basisthe nearly normal values obtained with more concentrated solutionsare to be accounted for as due to association of the solutes, whichis just what is to be expected, especially with substances containingamino-groups. pDibromobenzene was selected as a solute as beingin every way a " normal '' substance, giving a unimolecular liquidon fusion (Crompton, Trans., 1897, 71, 925).Accordingly, thCONSTANTS OF TRIMETHYLCARBINOL. 13vaIue for E found with it has been taken in preference to a meanvalue.It is of interest to calculate the values of E from data given byPaternb (Zoc. cit.) for the alcohol-water concent,ration-temperaturediagram. Here E=88*8 for an addition of 1.34 per cent. of water,but falls off considerably, due no doubt to association of the water.With 5-74 per cent. of water, E=64.6, and a t the minimum pointof the curve, E=45*1.As the depression of freezing point amountsto 6’6O for 1-34 per cent., it is probable that a higher value for Ewould be arrived at for smaller depressions. Considering the otherend of his curve, in which water is the solvent, with 5-79 per cent.of alcohol, we obtain E=19*1, and with 11.19 per cent., E=25.1.The molecular weight of the alcohol, of course, varies in the inversedirection. Taking E=18*7 for water, then M=72 and 55 a t therespective concentrations. Even allowing for the calculations beingmade on a percentage basis, not as grams per 100 grams, the resultswould appear to indicate dissociation of the alcohol, an appearancequite comparable with the behaviour of certain substances in thealcohol as solvent.If, however, with Crompton (Zoc.c i t . ) , we admit that theassociation of the solvent has to be taken into account as well asthat of the solute, we have to consider his third case, that of aunimolecular solute in an associated solvent, and must calculateRTi x 4 where “ a ” is the association factor Pu=RTx-, and E = -65 100s 0’of the vapour, ‘‘ x ” the association factor of the liquid, and s and Rdenote the heat of fusion and gas constant in calories. Then, asa = l and s=1.9 from 26-36O, it9 found by Ramsay and Shields’method (Carrara and Ferrari, Gazaetta, 1906, 36, i, 419):XThis value for E is sufficiently high to include *all the valuesfound by experiment, the lower values being, as before, attributedto association of the solute. As, however, the above relation ofCrompton has been rejected (Nernst, Theoretical Chemistry, Eng.Trans., 4th ed., p.268), this explanation can hardly be regardedaa satisfactory.Turning now to van’t Hoff’s equation, E = __ RT2 it is seen that 8 is1 Oh’the only value open to question. Taking the experimentally foundvalue, E=128, and using i t to calculate s, we obtain s=13*84 cal.,as against 20-98 cal. (de Forcrand, Zoc. cit.). De Forcrand haddoubts as to whether the definite state of the solid was reached atonce. If it is not, different values would, of course, be foun14 ATEINS : CRYOSCOPIC, EBULUOSCOPTC, AND ASSOCIATIONaccording to the length of time the alcohol remained solid. Hedetermined C, between -21‘5O and +14O, and concludes that itonly increases between his first determination and his last by 1 percent.at the most. In his firstexperiment, however, the alcohol was kept at - 2 1 ’ 5 O for four hours.Thus a quick change would escape detection by his method, the verylow temperature conducing to even greater rapidity. He proceedsfurther to test his values by the relation he had previously developed,Hence s cannot change either.’ 2 = 3 0 (28 to 32) (Compt. rend., 1903, 136, 945), where T is the Tabsolute boiling point, and L and S are the molecular heats, ofvaporisation at the boiling point and of fusion respectively. Then-- ’ + ’- 9428 -t 948 = 30.85, the agreement being satisfactory. If a1’ 355.8similar calculation be made, using s = 13.84 and consequently= 39.66, which is still within the S=1024, we obtainlimits of the constant.9426355.8The abnormally low value of Crompton’s relation (Zoc.cit,),-- Iosd- 1.00 (where d is the density at the melting point, which is1’represented by T on the absolute scale), which trimethylcarbinolaffords, namely, 0.54, may point to 20-98 being too low a value fors, but it seems far more likely that it is due t o the remarkablyhigh value of T, due to the influences referred to before.Now it is quite possible that in the case of trimethylcarbinolwe are dealing with a substance possessing two crystalline modifi-cations, the unstable rapidly passing into the stable. Indeed, anumber of facts seems to point to this conclusion. To begin with,wheq the alcohol is supercooled and suddenly solidifies, a feltedmass of needle crystals is produced.After keeping for a day at22O, none of this form can be found, but a number of plate-likeforms have appeared, which are often hexagonal in shape. In fact,in two or three hours but few of the needle form are to be aeen.Both forms illuminate and are extinguished when rotated on thestage of a microscope in plane-polarised light. The minute needlesand the longer ones formed more slowly give greys of the firstorder, as do the smaller plates, whilst the larger ones give allcolours. De Forcrand (Zoc. c i t . ) describes the crystals as derivedfrom a flattened orthorhombic prism with modifications h’. Hedoes not mention the needle form. Professor J. Joly verykindly examined both forms for me, and, while agreeing that thelarge crystals were orthorhombic, did not think it possible to assertto what system the needles belonged.In the crystallisation oCONSTANTS OF TRIMETHYLCARBINOL 15naturally occurring minerals, monoclinic substances very frequentlyassume an acicular form, and most organic compounds belong to thissystem, but, on the other hand, the birefringence of both platesand needles was very much the same. To sum up, examination ofthe crystals in polarised light gives no certain evidence for or againstthe existence of two modifications.An attempt wa made to study the change by taking a series ofphotographs under polarised light, a,s described by Pope (Trans.,1899, 65, 455) in his work on chloral hydrate. However, owing tothe difficulty of preventing the crystals from melting without adeposit of dew on the slide, I have not as yet been able to obtaingood photographs.It may be thought that in the passage from one crystalline con-dition to another the change in the heats of fusion would not be a tall so great as from 13.84 cal.to 20.98 cal., for in the case ofrhombic and monoclinic sulphur the difference is small. Withchloral hydrate, however, Berthelot (Compt. rend., 1880, 90, 842,1511) found s=17*52 cal. for the freshly melted crystals, ands=33'23 for those which had remained solid for some time. Popesubsequently proved that chloral hydrate was polymorphic, andquite a number of substances show these phenomena in a lesserdegree.That the discrepancy in the two heats of fusion of trimethyl-carbinol is due t o the existence of two crystalline modifications,one very unstable, seemed t o me to be all the more probable, asTammann (Ann.Yhys. Chem., 1899, [iii], 68, 553, 629) has found atriple point for the liquid and two solid phases at GOo and 1700kilograms pressure. From the triple point, two melting-point curvesbranch, and also a transition curve, giving the temperatures andpressures at which the modifications change in the solid state. Froma study of crystals which are absolutely stable only under highpressures, Skrabal ( Z e i t s c h . physikal. Chem., 1910, 73, 171) pointsout that there is a connexion between the velocity of a change andthe stability of the reaction products in such a way that the morerapid the reaction t.he greater is the possibility of obtaining the lessstable products.This, he states, is in accord with the results ofdirect experiment. Now, the separation of the needle crystals oftrimethylcarbinol is very rapid, and it seems probable that this isthe form which Tammann found to be stable only at high pressuresand temperatures. Its great instability at the ordinary temperatureunder atmospheric pressure accounta for its rapid disappearance,and also shows why the heat of fusion of the two forms is sodifferent16 ATKINS : CRYOSCOPIC, EBULLIOSCOPIC, AND ASSOCIATIONE bullioscopk Constant.Taking the mean of values obtained with p-dibromobenzene,carbamide, and naphthalene, the constant is found to have thevalue E=17*45.Lower values, E=13.77 and E=13*17, wereobtained with thiocarbamide and stearic acid respectively. Cal-culation from van't Hoff's equation gives E = 19-78.D. E. Tsakalotos (Compt. rend., 1907, 144, 1104) gives therelation :1where 11 is the absolute boiling point.agreement with van't Hoff's equation being good.This gives E=19*17, theAs, however, anE M T associated liquid is being considered, the expression - = ~ fCz M,Tlshould be used, where E is the value for another member of thehomologous series considered. Taking E = 11.5 for ethyl alcohol,the value of Ez is 18.97. This is in closer agreement with theexperimentally determined value.Baume and Tsakalotos (Comnpt. rend., 1907, 144, 373) give theRT2 dp equation L=- - where J is the mechanical equivalent of heat.JMp * d 2"and R is the gas constant, Combining this with &=0102Tz givesBNot being able to find a recorded value for * for trimethylcarbinol,dlL'that for propyl alcohol was taken, *=28*8.The above equationd 2'gives E = 19.53, in very close proximity to the previous values.taken, calculation givesTo sum up we have :Experimental. van't Hoff (calc.). Tsakalotos (calc,). Baume and Tsrtkalotos (calc..)E 17.45 19'78 19'17 and 18.97 19-53It thus appears that the experimental value is too low for someDe Forcrand's value for L was employed. I n his work,If, on the other band, the value of E from van't Huff's equation bed p - 28.4 for the tertiary alcohol.dl' -reason. Further doterminations are desirable,_ - _ _ _ - 9426 is given as 28-49, evidently a misprint for 26.5, which iaI' 355.8close t o the value given by the other alcoholsCONSTANTS OF TRIMETHYLCARBINOL 17A ssocia tion Factor.The calculation was made from Ramsay and Shields' formula fromvalues of yt recorded in the experimental portion of the paper.Thevalues of Carrara and Ferrari (Zoc. cit.), with which I subsequentlybecame acquainted, are given for comparison; x denotes theassociation factor, t represents the range of temperature.t. X.34'5-46.4" 1.40634'7-46.6 1.3iO46 '4-80.0 1.29646.6-79'5 1-31 3Meau 35 '0-47 '0 1 *388t. x: (Carrara).16-36" 1 *93436-40 1'51540-45 1 '268Mean 36-45 1.391The agreement between the two sets of values is satisfactory.Thehigh value of x at the lower temperatures is to be noted. It is ofinterest to compare these values with those arrived at by Walden'sequations(Zeitsch.physikaZ. Chem., 1908,65,129). Hegives 5 = const. = 417.9, where A, denotes the latent heat of evaporation at the boilingpoint, and a: is the specific cohesion at the same temperature. Herea2 = 9,gPCalculation shows some abnormality, for trimethylcarbinolgives const. = 24.8. Again, he gives &!= 1.16, and the divergence ofthis constant from its normal value may be taken as a measure of theassociation. The calculated constant is 1.06, which gives x = 1.094at the boiling point.Dutoit and Mojoiu (J. Chim. phys., 1909, 7, 169) have shown thatis approximately constant, varying from 0.01'73 to 0.0188, whereasRa2 Jf' varies from 0.0163 to 0.0205.They apparently take a2= 2,Y W PCalculating thus, the tertiary alcohol gives = 0.0253, a considerabledivergence.Longuinescu haw studied association by a different method (J. Chim.phys., 1908, 6,552). He finds for unassociated liquids that the followingrelation holds: (lo;;),)e=n, - where n is the number of atoms in themolecule. By a comparison of n (calc.) with m (theory), the degreeof association may be estimated. Taking Paternb's value for D,,,trimethylcarbinol gives m = 19-1 (calc.), n = 15 (theory) ; hence atOo, rc=1'27, which does not agree with the results of the othermethods. As it might not be permissible to use this value for Do,a:VOL. XClX. 18 ATKINS : CRYOSCOPIC, EBULLIOSCOPIC, AND ASSOCIATIONsince the melting point is 25*43O, the constant was calculated forpentane and hexane, as being in every way normal liquids, at 30°,taking the densities given by Young (Sci.Proc. Roy. Dublin Soc.,Y" - 100 (approx.) the 1910, 12, No. 31). Then for ----values 121.5 and 117.5 were obtained for pentane and hexane respec-tively a t 30°, also 116.2 and 113.0 at Oo. Substituting the meanconstant at 30°, and correcting for the constant at Oo being 114.6instead of 100, the value x = 1-12 at 30° is obtained. The agreementis no better than before. To sum up, the values arrived at byRamsay and Shields' method agree fairly with that found byWalden's equation for the boiling-point temperature. It will benoticed that the former measurements give the mean value over arange of temperature, whilst the latter give the value at a definitetemperature.The results obtained by Longuinescu's relation donot agree with those of the two previous methods, and judging bythe wide divergence of the constant even with normal liquids,such as pentane and hexane, but little more than qualitative resultscan be obtained from this method.2'D JGi-0' JG2EXPERIMENTAL,Cryoscop'c Constant.The apparatus used was the ordinary Beckmann, with a very wideair space between the freezing tube and the outer jacket, whichwas also an air space, as the freezing point of the alcohol was onlyslightly above room temperature. When the solvent was supercooled0'3O to 0*6O, the appearance of needle crystals was extremely rapid,and the temperature r a e .A steady state was soon reached, but asa considerable quantity of the solvent had crystallised out, the tubewas withdrawn, and the heat of the hand sufficed to melt mostof the crystals. The tube was then replaced and allowed to steadydown. It reached a point 0*04O to 0*05O above the former reading.This was taken as the true freezing point. It is worthy of notethat this is close to the correction calculated from Raoult's formulaand applied in the last experiment.The alcohol used all distilled over between 82.35O and 82'55Ounder 760 mm. pressure (corr.). I n the tables below, s denotes theweight of solute dissolved in 100 grams of solvent; A the depressionof freezing point; E the molecular lowering constant as calculatedfrom A ; and M tbe molecular weight of the solute as calcula.tedfrom A and the value of E obtained from van't Hoff's formula(namely, 84.5); t denotes the temperature of the outer air jacket,the inner air jacket being about 0'7O higher.From 10 to 12 gramsof alcohol were used in each experimentCONSTANTS OF TRIMETHYLCARBINOL.Solute : p-dibromobenzene, M = 236.S. A. E. &I* t.2'27 1.18 152.8 163 19.6"5 *42 2.31 100.5 198 21 '18 -99 3'14 82.5 242 -10.83 (3'61) - 19.9Fine crystals of the solute separaked before the solvent froze.0.31 0.17 128-0 155 19.7"1 '04 0 '47 106.6 187 -Solute : acetanilide, dl = 135.Solvent contained about 1 per cent. of p-dibromobenzene.S.0 '381-151 *936'31S .0 -33S .0 *270 '460'781.933.26S.0 -310.661-162'104'056-71Solute :A. E.Jf.0.43 154.4 750.97 112.3 1001'47 102.6 1113'41 72.9 156Solute : thiocarhamide, M = 76.A, E. M,0-4GIi 83.7 61Solute : p-toluidine, M = 107.A. E. n1.0.37 147'7 61 -70'65 152 5 59 '31 -07 147'2 61 '42 -50 138% 65.34'19 137'4 65-8Solute : a-naphthylamine, M = 143.A. E. M.0.247 112.1 108-60.54 116'9 103.40.89 109'8 110'01 '41 95.8 126.12-43 85 *7 141.03-73 79 '4 152'2water, M = 18. From Paternh's curve data,H,O per cent.1 *342'533'644-555 '748 '0012'03A. E.6'6 88 '812'2 86'815-3 75.518.0 67.320 6 64.625'4 57 -030'2 (max. A) 45'1M.17.117.520.021.323.526.733.6c 2120 ATEINS : CRYOSCOPIC, EBULLIOSCOPIC, AND ASSOCIATIONSolute : trimethylcarbinol, M = 74.Water its solvent.From Paternb's curve data.Alcohol per cent.5.797 -7411'19Solutes. A.0.295 0-1671-12 jobs. 1 '"' { 1-04 (corr.)The corre,ction wasA. E. Jf.1.5 19.2 722.4 23.0 613.8 25.1 55Revision Series.: p-dibromobenzene, M = 236.E. M. t.133-6 149.4 0.8" below m. p<128.1 :$: } 2.8" below m. p,-made from Raoult's equation,A = A (obs.) (1 - E-S),of alcoholof alcoholwhere(The notation has been previously explained.)The second term is negligible, as t = l min., T=20 min., andS = 0.08O. However, as T = 14.1, and R = 14.58 x 0.722, the cor-rection as a whole is considerable.Constants of trimethylcarbinol employed in calculations through-out the paper :Melting point 25*53O, and boiling point 82.55O (S.Young, Frac-t ional Distil Zat ion).Melting point 25'43*, and boiling point 82*S0, at 761 mm. pressure.(De Forcrand.)Sp. heat, liquid, Cl= O*i22 from 25.45O to 44 80°.Sp. heat, solid, C, = 0.550 from - 21.5O to + 14O.(Ue Forcrand.)(De Forcrand.)At 25.45O. (De Forcrand.) Heat of fusion, 8 = 20.978 cal.Molecular heat of fusion, S= 1552 cal. } At 82*8O. Heat of vaporisation, I = 127.38 cal.Molecular heat of vaporisation, L = 9426 cal.(De Forcrand, Zoc. cit.)p t =0.81388 - 0401256t (Paternh, Atti R. Accad. Lincei, 1907, [v],16, ii, 153). Paternb actually gives 0*0001256t, but I believe thisto be a misprint, as it does not agree with his own values for pf, orwith the values of Thorpe and Jones (Trans., 1893, 63, 278).Eb dtioscopic Constant.The apparatus used had a platinum wire fused in the bottom,This was filled with pure and wm surrounded by a vapour jacketCONSTANTS OF TRIMETHYLCARBINOL.21benzene, the boiling point of which differs only by 2.5O from thatof the alcohol. There was not enough of the pure alcohol to useas a jacket. A series of readings was taken in each case, andchips of a clay pipe stem were added from time to time to avoidsuperheating. The stem had been boiled with water after beingbroken up, and was heated to redness and allowed t o cool, justbefore use.8.2.015 *818.2711.67S.0.811 *18Solute : p-dibromobenzene, M = 236.A.0.1220-3710.5780.850Solute : t,hiocarbamide, M = 76.A.0'1400.213E.14-3115.0516 '5017.21E.13.1413.77Solute: carbamide, M=60, in presence of the thiocarbamide of theprevious series.S.0.6952 '07A.0.2050'596E.17-6917.24Solute : stearic acid, M = 284, in presence of carbamide and t h i ecarbamide, as before.9.1-133 *05A.0,0490.178E.12.5013-17Solute : naphthalene, M = 128, in presence of thiocarbamide,carbamide, and stearic acid, as before.9.1 -87A.0.150E.17.66Calculation from E = ___ "' gives the value 19.78 as against 17.45,1001a mean of the values obtained for carbamide, naphthalene, andthe highest value for p-dibromobenzene.It will be noticed thatthere is a rise in the value of E with rise in concentration, whichis the very reverse of the effect of association.This is most markedin the pdibromobenzene series, and is quite beyond the range ofexperimental error in determining the boiling point. The questio22 CONSTANTS OF TRJMETHYL CARBINOL.needs further investigation, but it seems possible that it may beexplained by the adsorption of the solute by the pipeclay chips,which were present in quantity.Assocktion Factor.The value of y was ascertained by measuring the height of theliquid in a capillary tube at various temperatures, using pure ethylether, carbon disulphide, and benzene to give constant temperaturevapour jackets. A thermometer capillary was used, after itsuniformity of bore had been tested. All measurements were madeon a falling column. Before taking a reading, the temperature wasmaintained constant to 0.05O for fifteen to twenty minutes. In thetables, h denotes the height in scale divisions, one division=0*0798cm. Radius of tube=0'009G cm., as found by calibration withmercury.Series A .The melting point of tho alcohol used was 23.95 ; p 2;c5=0*7829 ;from this, p: = 0.8143 was found by Paternb's formula, and the othervalues were calculated by it from the above value.ht. Pt. t . yt in dynes.68.1 0.7705 34 *5 19.4566.1 0.7556 46-4 18.2356'1 0.7133 80.0 17'84- 0.7103 82 *5 17.81 (calc.).Series B.The alcohol employed distilled over between 82'51O and 82.55Ounder 770 mm. pressure (corr.).A t . P t . t. 'yt *67'9 0-7703 34.7 19.3864-9 0.7553 46'6 18-1756.0 0.7140 79 -5 17-82- 0.7103 82.5 17.79 (calc.).From these values, the association factor x was calculated,employing the expression :MX =The values of y at the boiling point 82.5O were calculated bymeans of the coefficients 0.012 and 0.011 for the change in the vaIueof y expressed in dynes per degree in series A and B respectively.These were derived from the 46-80° range. The surface-tensionmeasurements were performed in the presence of dry air, not in 6-BROMO-2-PHENYLDIHYDRO-I ::3-BENZOXAZINE-4-ONE. 23vacuum.and Guye ( J . ChSm. plays., 1907, 5, 81).That this is quite permissible has been shown by RenardI take this opportunity of expressing my thanks to Professor S.Young for the use of apparatus and for the benefit of his advice.UNIVERSITY CHEMICAL LABORATORY,TRINITY COLLEGE, DUBLIN

ISSN:0368-1645    

DOI:10.1039/CT9119900010

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年代:1911

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J O U R N A LTHE CHEMICAL SOCIETY.TRANSACTIONS.HORACE T. BROWN, LL.D., F.R.S.J. N. COLLIE, Ph.D., F.R.S.A. W. CROSSLEY, D.Sc., Ph.D., F.R.S.BERNARD DYER, D.Sc.M. 0. FORSTER, D.Sc., Ph.D., F.R.S.P. F. FRANKLAND, Ph.D., LL.D.,C. E. GROVES, F.R.S.F. R. S.J. T. HEWITT, M.A., D.Sc., Ph.D.,F. R. S.A. MCKENZIE, M.A., D.Sc., Ph.D.G. T. MORGAN, D.Sc.J. C. PHILIP, D.Sc., Ph.D.Sir WILLIAM RAMSAY, K.C. B., LL.D.A. SCOTT, M.A., D.Sc., F.R.S.F. R. S.dM.m:J. C. CAIN, D.Sc., Ph.D.SnlT-Qbitm :4. J. GRBENAWAY.1911. Vol. XCIX. Part 11.LONDON:GURNEY Q JACKSON, 10, PATERNOSTER ROW1911RICHARD CLAP & SONS, LIYITED,BRUNBWICK STREET, STAMTORD GTRERT, S.E,AND BUNGAY, SUFFOLK

ISSN:0368-1645    

DOI:10.1039/CT91199FP021

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年代:1911

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6-BROMO-2-PHENYLDIHYDRO-I ::3-BENZOXAZINE-4-ONE. 231~1.-6-Bromo - 2 -phenyZdihydro-l : 3 - benxoxaxine-4-oneand Related Derivatives,By ERNEST CHISLETT HUGHES and ARTHUR WALSH TITHERLEY.IN a previous paper (Trans., 1910, 97, 1368) the authors describeda series of chlorederivatives in connexion with the study of theaction of chlorine on 2-phenyldihydro-l : 3-benzoxazine-4-one (I).The behaviour of the latter compound with bromine has now beenexamined, and it has been found that simple bromination occursin the benzene nucleus, yielding 6-bromo-Z-phenyldihydro-l : 3-benz-oxazine-4-one (11), whilst no substitution of the 2-hydrogen atomtakes place such as occurs in the corresponding experiments withchlorine ; that is, the expected unsaturated derivative, 6-bromo-2-phenyl-1 : 3-benzoxazine4-one (VI), is not produced.This com-pound, however, can be obtained by submitting 6-bromo-2-phenyl-dihydro-1 : 3-benzoxazine-4-one (11) to the action of chlorine insteadof to the further action of bromine, when in benzotrichloridesolution at l l O o substitution occurs a t position 2, yielding the inter-mediate 2-chloro-6-bromo-derivative (VIII), which immediatelyloses hydrogen chloride as in the case of the 2 : 6-dichloro-compound(Zoc. cit.). It is evident that the hydrogen atom at position 2 isreadily affected by chlorine, but not by bromine. Further, theunsaturated ring compound (VI) has been synthetically preparedfrom 0-benzoyl-5-bromoaalicylamide (V) (obtained by pyridinebenzoylation of 5-bromosalicylamide, IV) by the same dehydrationmethod aa that used in the preparation of the corresponding 6-chloro-compound.Further, the constitution of the dihydro-compound (11)has been confirmed by its independent synthesis from 5-bromo-salicylamide (IV) and benzaldehyde. The properties of the twobromo-oxazone compounds (I1 and VI) are in every respect similarto those of the corresponding chloro-derivatives, and whilst 6-bromo-2-phenyldihydro-1 : 3-benzoxazine-4-0110 (11) on treatment wit24 HUGHES AND TITHERLEY : 6-BROMO-2-PHENY LDIEIY DRO-pyridine and alkali yields a labile syn-benzylidene-5-bromosalicyl-amide (111), and with boiling dilute alkali, benzaldehyde and5-bromosalicylamide, 6-brome2-phenyl-1 : 3-benzoxazine-4-one (VI)is converted by treatment with alkali (or acid) into N-benzoyl-5-bromosalicylamide (VII), which on further hydrolysis gives5-bromosalicylamide and benzoic acid.The same reversible re-arrangement phenomena have been observed between 0- andN-benzoyl-5-bromosalicylamides (V and VII) as between the corre-sponding 5-chloro-derivatives a nd 0- and N-benzoylsalicylamides.The above relations are expressed in the scheme:(I. ) 2-Phenyldihydro- (11. ) 6-Bromo-2-phenyl- (111.) syn-Benzylidane-1 : S-benzoxazine- dihydro-1 : 3-benz- 5 - bromosalicyl-4-One. oxazine - 4 - one amide.(m. p. 223")./ /"Br/\/co*NH2Br/\/'OoNH2 + O:CHph Benzoylation I t ____, 1 1\/\.OH \/\O*COPh(IV. ) 5-Bromosalicylamide (V. ) 0- Benzo yl- 5 -bromosalicylamide(m. p. 238"). (m. p. 154").GO CO*NH*COPhHZ.0 Brf\f -+ Br/\ \N\/\OH1 "CPhc' \/v(VI.) 6-Bromo-2-pheiiyl- (VI I.) N-Benzoyl-5-bromo-1 : 3-benzoxazine-4-0ne (m.p. 208"). 249").salicylamide (m. p.t-HCIco coB r / \ A N HI I ICHPh0B~()/\NH C1 \A/ /CClPh +-0\/\(VIII.) Not isolated. (I1 : 3-BENZOXAZINE-4-ONE AND RELATED DERIVATIVES. 25EXPERIMENTAL.6-Brom-2-phenyldihydro-l : 3-b enzoxazine-4-one,C,H, Br< COgrH0-C HPB'(1) Bromination of 2-Phenyldihydro-l : 3-b enzoxazine-4-one.-Bromination proceeds easily in the cold, but owing to a secondaryreaction, in which some water appears to be produced, a considerablequantity of bromosalicylamide and benzaldehyde is formed as aby-product. A solution of 10 grams of 2-phenyldihydrel : 3-benz-oxazine-4-one in chloroform was gradually treated with 5.2 gramsof bromine; the red colour rapidly disappeared, and a pale yellowsolid separated (4-5 grams), which, after two hours, was collectedand recrystallised from alcohol.It melted at 235O, gave a strongviolet colour with ferric chloride, dissolved with slight fluorescencein sodium hydroxide, and was identified as 5-bromosalicylamide.(Found, N = 6.45 ; Br. = 36.68. Calc., N = 6.48 ; Br = 37.03 per cent.)From the chloroform filtrate, which contained impure benz-aldehyde, 6-bromo - 2 - phenyldihydro - 1 : 3 - benzoxazine-4-one (4.6grams) was isolated as a pale yellow solid by evaporation anddigestion with cold dilute sodium hydroxide. It was obtained pure,by recrystallisation from hot benzene, in fine, colourless needles,melting at 223O:0.3506, by Kjeldahl's method, required 11.2 C.C.NIlO-HCl. N =4*42.0.2186 gave 0.1340 AgBr. Br = 26.08.C,,H,,O,NBr requires N = 4.61 ; Br = 26-31 per cent.The compound is sparingly soluble in cold alcohol, benzene, oracetone, moderately so in cold chloroform, and readily soluble inhot alcohol or benzene, from both of which it crystallises well oncooling. It is readily decomposed on warming with dilute sodiumhydroxide, giving benzaldehyde.(2) Condensation of 5-Bromosalicylamide and 23enzaldehyde.-The requisite 5-bromosalicylamide (described by Kauschke, J . pr.Chem., 1895, [ii], 51, 211) was obtained by adding 60 grams ofbromine gradually to a boiling solution of 50 grams of salicylamidein 1500 C.C.of chloroform. A vigorous reaction took place, thecolour of the bromine disappearing immediately, and a copiousprecipitate of the bromclderivative being formed. The chloroformwas finally distilled off in order to remove the hydrogen bromide,which proved troublesome unless eliminated at this stage, and thesolid collected and washed with a iittle ether. After recrystallisationfrom alcohol, it melted at 238O (Kauschke gives 232O). The con-densation of 5-bromosalicylamide and benzaldehyde was easil26 HUGHES AND TITHERLEY 6-BROMO-Z-PHENYLDIHYDRO-effected. Five grams of bromosalicylamide were dissolved bywarming in 20 C.C. of benzaldehyde, and 0.5 C.C. of alcoholichydrogen chloride added. After heating a t looo for a few minutesand allowing to cool slowly, 6-bromo-2-phenyldihydro-l : 3-benz-oxazineQone separated, practically pure, as a thick mass of colour-less crystals (6 grams), which were collected and washed with alittle alcohol and ether.It melted a t 219O, and, after re-crystallisation from alcohol, at 223O. The substance was identicalin every respect with that obtained by the bromination method,and a mixture of the two melted at 223O :0.4666, by Kjeldahl’s method, required 15.5 C.C. N/lO-HCI. N=4.64.0-4104 gave 0.2540 AgBr. Br = 26.34.C,,H,,O,NBr requires N =4*61; Br = 26.31 per cent.syn-BenzyZidene-5-bromosalicylamide, C,H,Br<~~N:CHPh .Two grams of 6-brome2-phenyldihydro-l : 3-benzoxazine-kone in30 grams of pyridine were shaken with 20 C.C. of 10 per cent.sodium hydroxide for half an hour, after which time the brightyellow colour first produced had disappeared.The solution wasdiluted with water to 750 c.c., and acidified at Oo with dilute hydro-chloric acid. The resulting thick, white, amorphous precipitate,consisting of the syn-bromclderivative, was collected, repeatedlywashed with water, and dried on porous porcelain in a vacuum.The melting point (100--150°) was indefinite, and it was not foundpossible to crystallise the compound without rearrangement t o thecyclic isomeride, but it was practically pure, as shown by itsproperties and analysis.0.5166, by Kjeldahl’s method, required 17.2 C.C. N/10-HCI. N =4*66.0.1952 gave 0.1238 AgBr. Br=26.67.C,,H,,O~Br requires N = 4.61 ; Br = 26.31 per cent.The yield was quantitative :syn-Benzylidene-5-bromosalicylamide is very sparingly soluble insolvents in the cold, whilst in the hot in rearranges.On melting,it also rearranges in the course of about forty-five seconds to6-bromo-2-phenyldihydro-1 : 3-benzoxazine-4-one, which solidifies inthe tube, and then melts at 219-220°.co-E 6-Bromo-2-phenyl-l : 3-b enzoxazhe-4-one, C,HsBr< O-CPh.1. Preparation from 6-Brom-2-phenyldihydro-l : 3-6 enz-oxazine-4-one.The action of bromine on 6-bromcl2-phenyldihydro-l : 3-benz-oxazine-4-one was examined under a variety of conditions, but i1 : 3-BENZOXAZINE-4-OME AND RELATED DERIVATIVES. 27no case could the desired 6-bromo-2-phenyl-l : 3-benzoxazinekone beisolated. The action in all citses led t o fission of the ring, withproduction of 5-brom~alicylamide.Chlorine, however, gave thedesired result. Eight grams of 6-brome2-phenyldihydrel: 3-benz-oxazin&-one, dissolved in the minimum quantity of benzotri-chloride at l l O o , were treated with a rapid current of dry chlorinefor one hour. On cooling, a mass of fine needles separated, con-sisting of 6-bromo-2-phen yl-l : 3-b enzoxazine4-0ne, which, afterwashing with benzene, melted at 202O, and on recrystallisation frombenzene at 207O. The yield was 5 grams, and the product wasidentical in all respects with that obtained by method 2 (see below) :0’4078, by Kjeldahl’s method, required 13.7 C.C. N / 10-HCI. N = 4.67.0.4022 gave 0’2522 AgBr. Br = 26.68.C,,H,O,NBr requires N = 4.64 ; Br = 26-50 per cent.2.Preparation from 0-Benaoy 2-5-6 romosalic ylamide.The method employed was similar to that adopted by Titherley(Trans., 1910, 97, 208), using anisole w a solvent. A very slowstream of dry hydrogen chloride was passed into a solution of2 grams of 0-benzoyl-5-bromosdicylamide (p. 28) in 10 C.C. ofanisole at 150° contained in a, small distilling flak. The anisoleslowly distilled off, carrying with it the water formed in the reaction.The resulting yellow syrup, which solidified on cooling, was digestedwith 50 C.C. of dry boiling benzene. This left a quantity ofN-benzoyl-5-bromosalicylamide (0.2 gram), and the filtrate, oncooling, deposited 6-bromo-2-phenyl-l : 3-benzoxazine-4-one in apractically pure condition (1 gram), melting at 207O.On re-crystallisation from benzene, it wm obtained in small, white needles,melting at 208O:0.1770, by Kjeldahl’s method, required 6.0 C.C. N / 10-HCI. N = 4.75,0.1330 gave 0.0814 AgBr. Br=26-04.C,,H,O,NBr requires N = 4-64 ; Br = 26.50 per cent.The compound is sparingly soluble in cold alcohol, acetone, orbenzene, but readily so in the hot solvents, and it is moderatelysoluble in cold chloroform. It is not acted on by coId dilute sodiumhydroxide, but with strong aqueous or alcoholic ammonia, it givesbright orange needles like the corresponding chlorclderivative.Dilute acids in the cold do not affect the bromo-derivative, but inhot alcoholic solution the ring undergoes disruption with additionof water, yielding N-benzoyl-5-bromosalicylamide (m.p. 240°), whichseparates as a voluminous mass, the yield being quantitative. ThisN-benzoyl derivative waa identical with the product obtained by therearrangement of O-benzoyl-5-bromosaIic@mide (p. 28), and a28 6-BROMO-2:PHENYLDIHYDRO-1 : 3-BENZOXAZINE-4-ONE.mixture of the two melted at 240°, It gave the following figures onanalysis :0.3648, by Kjeldahl’s method, required 11.5 C.C. N / 10-HCl. N =4*41.0.1810 gave 0*1080 AgBr. Br = 25.53.C,,Hl0O3NBr requires N = 4.38 ; Br = 25.00 per cent.CO*NH, 0 - B enzo y Z-5- b romosalic ylamide, C,H3Br<o. COPhA solution of 10 grams of 5-bromosalicyIamide in 40 grams ofpyridine (dried over barium oxide) was treated with 10 grams ofbenzoyl chloride with continued shaking. The temperature was keptat -15O during the addition, which occupied one and a-half hours,and the resulting bright red mixture was kept at -15O for afurther hour.It was then treated with 50 C.C. of dry ether, theethereal pyridine solution decanted off, and the yellow, solid masstreated with dilute sulphuric acid at Oo. An insoluble buff powderremained, consisting of the crude 0-benzoyl derivative, which, afterwashing with water and ether, weighed 10 grams. On recrys-tallisation from boiling toluene, it separated in fine, colourlesB,glistening needles, melting a t 1 5 4 O :0.6488, by Kjeldahl’s method, required 20.3 C.C. iV/ 10-HCl. N = 4.38,0.4528 gave 0.2620 AgBr. Br = 24-73.C14E,,0,NBr requires N = 4-38 ; Br = 25.00 per cent.0-Benzoyl-5-bromosalicylamide is sparingly soluble in the usualsolvents.I n boiling alcohol it dissolves, but almost immediatelyrearranges to the N-benzoyl isomeride (m. p. 238O), which separateson cooling slightly.The same rearrangement occurs on melting, the liquid at 154Osetting in about forty-five seconds to the solid N-benzoyl derivative,which then melts at. 240O.N-BenzoyZ-5-bromosalicylamide, C,H,Br<OH CO*NH*COPh.Two grams of 0-benzoyl-5-bromosalicylamide were dissolved inthe least possible quantity of boiling alcohol, and the solutiondiluted to 200 C.C. with water at 80°. The temperature was thenkept a t the boiling point for a few minutes, when a thick, curdyprecipitate of the pure N-benzoyl derivative, melting a t 248*, wasobtained. On recrystallisation from pure acetic acid, the meltingpoint was raised to 249O:0.4526, by Kjeldahl’s method, required 14.2 C.C. N/lO-HCI. N = 4.39.0.3142 gave 0.1842 AgBr. Br = 24.95.C,,E,,O,NBr requires N = 4-38 ; Br = 25-00 per centKOMPPA : SYNTHESIS OF CAMPHORIC ACID. 29N-BcnzoyZ-5-bromsaZicyZamide is very sparingly soluble in all theusual solvents, hot or cold. It may, however, be recrystallised fromacetic acid if the operation be carried out fairly rapidly to avoidrearrangement. It gives intense yellow sodium and ammonium salts,which are sparingly soluble in water, from which, on acidification,the substance is precipitated in a colourless, gelatinous form.Rearrangement.-One gram of the N-benzoyl derivative wasboiled with 25 C.C. of glacial acetic acid for four hours. On cooling,0.2 gram of unchanged substance separ'ated out, and on dilutingthe filtrate with water, 0.5 gram of 0-benzoyl-5-bromosalicylamidewas obtained (m. p. 150°), which, on recrystallisation from toluene,melted at 1 5 4 O . It was completely identical in all its propertieswith the synthetic product.ORGANIC LABOR ATOlLP,UNIVERSITY OF LIVERPOOL

ISSN:0368-1645    

DOI:10.1039/CT9119900023

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年代:1911

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KOMPPA : SYNTHESIS OF CAMPHORIC ACID. 29IV. -Synthesis o j Cunaphoric Acid.By GUSTAV KOMPPA.A RECENT paper published simultaneously by G. L. Blanc andJ. F. Thorpe in France (BUZZ. SOC. chim., 1910, [iv], 7, 740) andEngland (Trans., 1910, 97, 836), throwing doubt on my synthesisof camphoric acid, suggests that I could never have obtained thatsubstance by the process described, and that my conclusions arebased on an error. Although in a position to reply immediately tothese critics, I thought it desirable first to make some complementaryexperiments, and at the same time possibly to show that Blancand Thorpe are themselves mistaken in drawing somewhat hastyconclusions from their incomplete treatment of the subject. Inthis I have now succeeded, and the present communication is myreply to their arguments.I n the first place, the above-mentioned investigators declare thatthe basis of my synthesis, methyl diketoapocamphorate, cannot beproduced in sufficient quantities (J.F. Thorpe, Proc., 1909, 25, 94;G. L. Blanc, Bull. SOC. chiin., 1909, [iv], 5, xvi). Blanc even goesso far as to say in his address, t‘ Le Camphre,” delivered before theSoci6tB Chimique, “ qu’il lui a 6tB personellement impossible dereproduire ” this substance, and that the reaction according to whichit waq obtained “ sur le papier ne prksente pas grande chance der6ussite.” When I published a complete account of my researches,including the method of preparing the substance, they were abl30 KOMPPA : SYNTHESIS OF CAMPHOBIC ACID.to make use of the latter for their own experiments; they foundit had the properties which I had previously described, although theyield which they obtained was not so good as it might have beenaccording to my prescription.It is unnecessary to dispute thispoint, however, because it is not easy for a worker unfamiliar withthis reaction to arrive at satisfactory results, towards the attain-ment of which I have been compelled t o persevere for years.Nevertheless, my assistants, on becoming accustomed to the task,have usually been successfdl. For example, Mr. A. LampBn’s yieldvaries from 45 to 70.5 per cent., Mr. B. Ingman’s from 49 to 67per cent., and Mr. W. Salve’n’s from 45 to 70 per cent., all beingcalculated as described in my paper.With the best intentions, it isnot always possible to give a sufficiently detailed description ofsuch a difficult and complicated method of preparation, and theyield may be affected by some condition as yet unknown; but Ihave had in my possession several hundred grams of methyl diketo-apocamphorate.The product obtained by Blanc and Thorpe on methylating thisdiketeester by my process was identical with mine, the meltingpoint being 85-88-0. In their last paper, these chemists argue thatthe methyl derivative is not, as I supposed, the C-methyl derivative(I), but the 0-methyl ether (11) :CO-CH*CO,Me I CMe, IThis they claim to have proved by treating the methyl derivativemelting at 85-8S0 with potassium hydroxide, obtaining an amountof potassium derivative corresponding with 50 per cent.ofmethyl diketatpocamphorate, and isolating from the mother liquor40 per cent. of PB-dimethylglutaric acid without detectingaBB-trimethylglutaric acid ; according t o this result, the methylgroup in the diketo-ester melting at 85-88O is eliminated by alkali.On the supposition that the methyl group is not attached to carbon,they argue that I could not have obtained camphoric acid from theester melting at 85--88O, and that my report is based on “an error.”They have made this statement wit,hout having even tried to reducethe substance according to my directions. They do not even seek toexplain what kind of error underlies my conclusions.I n considering whether a mistake has possibly been made, it isnecessary to point out that if the methyl group were attached tooxygen instead of to carbon, reduction would l e d to apocamphoriKOMPPA : SYNTHESIS OF CAMPHORIC ACID.31acid as the final product. This melts at about the same temperatureit9 T-camphoric acid, and although the appearance of the two sub-stances under a microscope is not exactly similar, yet confusion ispossible. But mixing together apocamphoric and r-camphoricacids causes a depression of 15-16O in the melting point, whereasthe saturated acid which I obtained from the ester melting at85-88O does not in the least depress the melting point of naturalr-camphoric acid. Moreover, there is a difference of 4 5 O in themelting points of the anhydrides of apocamphoric and camphoricacids.This fact, taken in coniunction with the dissimilarappearance, renders it impossible for any chemist to make such amistake. Furthermore, I have not only synthesised r-camphoricacid and its anhydride, but also r-isocamphoric acid and r-dehydro-camphoric acid, which synthetical acids I have compared directlywith the corresponding acids prepared from natural sources, demon-strating that these, when mixed together, do not effect a depressionin the melting point, and that they are also in other respectsidentical. I attach a special significance to the identity of syntheticdehydrocamphoric acid with r-dehydrocamphoric acid prepared fromr-camphoric acid. I n 1903 I described the properties of dehydro-camphoric acid (Ber., 1903, 36, 4334), obtained synthetically fromthe ester melting at 85-88O, whilst only two years ago I procuredthis acid from natural r-camphoric acid, and showed that they wereidentical (Annulen, 1909, 370, 212). That this synthetical dehydreacid cannot be the corresponding dehydrwpocamphoric acid is clearalso from the fact that the two acids, although having the samemelting point, cause a depression of 14O when mixed together.Even yet the facts are not all disclosed, but the foregoing issufficient evidence that an earnest chemist could not possibly commitan error such as Blanc and Thorpe would suggest, and that theexperimental results, as I have stated them to be, can beestablished.I n his quoted paper, Thorpe lays special stress on the passage:" It wits from the pure crystalline material that Komppa preparedcamphoric acid." As it appears from my laboratory notes that themethyl diketocamphorate used for my synthesis had been crystallisedonce only, I deemed it important t o show that the camphoric acidI obtained could not have arisen from any possible impurities inthe diketo-ester.Accordingly, with the assistance of Dr. 0. Routala,I have again prepared a thoroughly purified ester melting at85-88O, a d reduced it, first with sodium amalgam and then withhydrogen iodide, precisely as was stated in my complete report( A m Z e n , 1909, 370, 209), obtaining once more the same yield ofthe same dehydro-acid, melting at 223-224O (normal thermometer) 32 EOMPPA : SYNTHESIS OF CAMPHORIC ACID.the product, when mixed with r-dehydrocamphoric acid, again failedto cause depression of the melting point.This is the fifth occasionon which, with the aid of three different assistants, I have com-pletely synthesised the acid; as it is identical with r-dehydro-camphoric acid prepared from r-camphor, and as I have also threetimes, with two different assistants, changed this synthetical dehydro-acid into r-camphoric acid and also into isocamphoric acid, it seemsto me wholly impossible that other chemists should fail to preparecamphoric acid from the same substance.But how is it to be explained that Blanc and Thorpe have noteven tried to reduce the substance melting at 85--88O, in orderto ascertain whether they could obtain camphoric acid or dehydro-camphoric acid according to my method? It is evident from thediscussion following Thorpe’s paper that the reason for this neglectwas the supposition that, because the methyl group is removed byalkali from the ester melting at 85--88O, it is also removed byreducing, according to my prescription, with sodium amalgamfollowed by hydriodic acid.Here they have made the seriousmistake of not taking into account the fact that I do not reduce incaustic alkali solution, but in alkali carbonate, or rather in alkalibicarbonate, a rapid stream of carbon dioxide being led, duringthe whole operation, through the reducing solution. That sodiumcarbonate does not eliminate the methyl group from the substancemelting at 85--8B0 must be known to them, because in preparingthe latter accsrding to my method they separated it from the neutralproduct of methylation by extracting it several times with sodiumcarbonate solution, and isolating the ester by acidifying this liquid.It would surely have been worth while to reduce the ester in questionby my process, even if the methyl group is eliminated by causticalkali, a point which I have not yet had time to verify.I do not, however, admit that the ester melting at 85-88O is the0-methyl derivative (11), as claimed by Blanc and Thorpe onaccount of its behaviour towards alkali, because camphoric anddehydrocamphoric acids can be synthesised from it.That thisester is, as I have supposed from the outset, the C-methyl derivativeis demonstrated in the following manner.The ester in questionproduces, in common with all a-diketones, a yellowish-brown colour-ing matter (quinoxaline), which has a strong green fluorescencewhen dissolved in ether and in alcohol, developing with mineralacids a dark red coloration destroyed by water, properties whichcharacterise quinoxalines. I have not succeeded in crystallisingthis colouring matter, or the one from o-tolylenediamine, and havetherefore not been able to analyse it. When one takes into accountthe fact that the neutral ether, obtained by methylating d i k e KOMPPA : SYNTHESIS OF CAMPHORIC ACID. 33apocamphoric ester, and to which I have ascribed the followingcinstitition (111) :&If3(111.)does not give the abovementioned fluorescence, although it containsthe Sam; grouping of elements (IV) which Blanc and Thorpesuppose to exist in the ester melting at 85--88O, the colorationobserved is not to be ignored. The difference in constitutionbetween the ester melting at 85-88O and the neutral ester (111) isindicated more plainly when phenylenediamine hydrochloride isused instead of the free base.With this agent, the ester meltingat 85-88O develops a red coloration at the ordinary temperature,and slight heating produces the effect very easily, this intense redsolution not being given by the neutral ester (111). Attemptsto produce osazones from the.ester melting at 85-88O have led tooils, which have not been investigated further.The constitutional formulz which I have ascribed to these sub-stances are confirmed by the following determinations of themethoxy-group according to Zeisel's method :0.2500 (ester m. p. 85-88O) gave 0.4495 AgI.Formula I requires 24-?2; formula I1 requires 36.33 per cent.0.2106 (neutral ether) gave 0.5223 AgI.Formula I11 requires 34.44 per cent.As the methyl group in the ester melting at 85-88O is notremoved by boiling hydriodic acid, it is certainly not attached tooxygen, its suggested by Blanc and Thorpe, thus indicating theconstitution (formula I) which I have already advoca.ted, namely,that of diketocamphoric ester.From all these facts, it is evident that t,he criticisms of mycamphoric acid synthesis put forward by Blanc and Thorpe arecompletely baseless.MeO=23.74.0*2000 ,) Y, ,, 0.3620 AgI. Me0 =23%9.Me0 = 32-76.CHEMICALABORATORY,INSTlTUTE OF TECHNOLOGY,HELSINGFORS, FINLAND.VOL. XCIX.

ISSN:0368-1645    

DOI:10.1039/CT9119900029

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年代:1911

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34 DOBBlE AND LAUDEK : HYDROXYCODEINE :V.-Hydroxycodeine : a New Alkaloid from Opium.By JAMES JOHNSTON DOBBIE and ALEXANDER LAUDER.THE new opium alkaloid, which forms the subject of this communi-cation, was discovered by Messrs. T. and H. Smith, of Edinburgh,who were good enough to place a small quantity of the hydro-bromide in our hands for investigation. The alkaloid is found invery small quantity in the last mother liquors obtained in theworking up of the opium alkaloids, after all the other alkaloidshave been eliminated.The alkaloid is readily soluble in water, alcohol, ether, chloroform,benzene, or amyl alcohol, but, so far, has not been obtained in acrystalline condition. From all these solvents it separates in theform of a varnish. The alkaloid has no definite melting point; onheating, it begins to soften about 40°, and is completely meltedat 51O.Of the common salts, the hydrobromide and the hydrochtlodeboth crystallise well ; the hydrobromide is, however, much lesssoluble than the hydrochloride, and it was therefore selected foranalysis. It readily crystalIises from water in large, hard, prismaticcrystals, which contain no water of crystallisation.The crystalswere dried at looo, and gave the following results on analysis:0.3344 gave 0.6678 CO, and 0-1808 H,O.0.45020.2988 ,, 9 C.C. Nb (moist) ,, 14.4O and 754 mm. N=3*50.0.6056 7 7 0.284 AgBr. Br=19.95.0.5210 7 7 0.244 AgBr. Br=19-92.Mean, C = 54-41 ; H = 5.81 ; N =3.51; Br = 19-94.C = 54.46 ; H = 6-00.0.3318 ,, 0.6614 CO, ,, 0.1680 HZO.C=54.36; H=5*62.,, 14 C.C. N, (moist) a t 17O and 742 mm. N=3*52.C18H,10,N,HBr requires 54.54 ; H = 5-55 ; N = 3-53 ;Br =20.20 per cent.PtatimichZom'de.-The alkaloid was dissolved in dilute hydro-chloric acid, and precipitated with excess of platinum chloride; theprecipitate was well washed, and dried at looo for analysis:0-3258 gave 0.4942 CO, and 0.1296 H,O.0.2452 ,, 0.3725 C'O, ,, 0.0975 H,O. C=41*43; R=4*44.0.2744 ,, 7 C.C. N, (moist) at 14O and 755 mm. N =2*98.0.1768 ,, 0.0328 Pt. Pt=18.55.0.2764 ,) 0.2280 AgC1. C1=20*39.C = 41-36 ; H =4-42.(C,,H,iO,N),H,PtC1, requires C = 41-54 ; H =4*23 ; N = 2.69 ;Pt = 18.75 ; C1= 20.48 per cent.Betewnination of Methoxyl Grozcps.-The number of methoxy-groups was determined by Zeisel's methodA NEW ALKALOID FROM OPIUM.350.4052 gave 0.2408 AgI. OMe= 7.82.0*3426 ,, 0.2064 AgI. OMe=7.93.OMe-C1,HI8OSN,HBr requires OMe = 7.83 per cent.Methiodide.-The methiodide \was prepared by dissolving a smallquantity of the alkaloid in a mixture of methyl iodide and methylalcohol. The methiodide separated in colourless plates. It wasrecrystallised from methyl alcohol, and dried over sulphuric acid :0-2076 gave 0.1098 AgI. I=28.57.This result is sufficient to show that the alkaloid is a tertiarybase.Specific Rotatwn.-An aqueous solution of the hydrobromide isslightly dextrorotatory :I. 5-1884, in 100 of water, gave, in a 1-dcm. tube at ZOO,a + 0.9O; Dr 1.0158 ; whence [u]: + 17-07'.11. 5.0741, in 100 of water, gave, in a 1-dcm.tube at 20°,a + O 0 9 O ; DT 1.0154; whence [ax + 1 7 * 4 O .Colour Reactions.-With Frohde's reagent, the new alkaloid givesa yellowish-green colour, which gradually changes to blue; and withMandelin's reagent a yellowish-green, also changing to blue onkeeping. These reactions are practically identical with those givenby codeine with the same reagents.A bsorptioon Spectra.-The absorption spectra of an aqueous soh-tion of the hydrobromide were photographed. The spectra showa well-marked absorption band at l / h 3500. The position of thisband is identical with that of codeine (Hartley, Phil. Trans., 1885,Part 11, 471; Dobbie and Lauder, Trans., 1903, 83, 605), but thecodeine band is very slightly more persistent.The discoverers propose the name neopine for the new alkaloid.Although, owing to the small quantity of material at our disposal,the chemical evidence is still incomplete, the alkaloid is almostcertainly a hydroxycodeine, but it is not identical with the hydroxy-codeine prepared by Ach and Knorr (Bet-., 1903, 36, 3067) by theoxidation of codeine. Its formula differs from that of codeine onlyin the possession of an additional atom of oxygen, which, owing tothe solubility, is probably present in an hydroxyl group. Likecodeine, it contains only one methoxyl group. Further evidence ofthe close relation between the two alkaloids is afforded by thepractical identity of their absorption spectra.The physiological action of the new alkaloid has been investigatedby Professor Stockman, of Glasgow University.EDINBURGH AND EAST OF SCOTLAND COLLEGEC,,H,,O,NI requires I = 27.79 per cent.THE GOVERNMENTLABORATORIES, LONDOS. O F AGRICULTURE, EDIXIXTRGH.0

ISSN:0368-1645    

DOI:10.1039/CT9119900034

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年代:1911

数据来源: RSC

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36 ME1,DOLA AND KUNTZEN : SYNTHESES WITH PHENOLVI. --Syntheses with Phie~~ol Der ivutives Containing aMobile Nitro-group. Part 111. Complex 1mi.n-azoles, Azo-compourLds, and Azides.By RAPHAEL MELDOLA and HAROLD KUNTZEN.THE extreme mobility of the 3-nitro-group in 2 : 3 : 5-trinitro-4-acetylaminophenol when the latter compound is allowed t o interactwith primary arnines has been taken advantage of for the synthesisof iminazoles and other compounds and for the study of the influenceof the position of substituents in determining the yield of iminazole,etc. (Trans., 1906, 89, 1935; 1908,93, 1659; 1909, 95, 1033). Theobject of the present extension of the research was, in the first place,to ascertain whether complex iminazoles containing two iminazolerings attached to one benzene nucleus were capable of existence.Although the results in this direction have not hitherto beenpromising, we think it desirable to place upon record the principlewhich has been adopted, because we propose continuing the experi-ments in this direction.It will be seen from the general formulaof the iminazoles synthesised by this method:NO, N*Rthat t,here are t'wo groups in the benzene ring which might, undersuitable treatment, be made to furnish the iminazole ring, namely,the 6-hydroxy- and 7-nitro-group. I f , by the action of ammonia oramines on the iminazoles or their ethers (Trans., 1908, 93, 1672,etc.), an amino-group or substituted aminclgroup could be sub-stituted for the 6-hydroxyl group, dinitro-derivatives would beformed, which, on acylation and reduction, might be expected tofurnish compounds of the type of the hitherto unknown benzdi-iminazoles :NO,, NOR R*C=N N*R /\7\ (R)HAf \/\ I C*CH,.NH21 I C*CH, -+\/\/NH, N\/\/NO, NSIany experiments have been made with the methyl ether of theiminazole from aniline and the trinitro-compound, but the difficultyappears to be the initial step of substituting the amine residue forthe 6-hydroxy-group.It is well known, however, that the mobilitDERIVATIVES CONTAINING A MOBTLE NITRO-GROTJP. 37of the alkyloxy-group increases with the weight of the radicieattached to the oxygen atom, and the experiments will be continuedwith ethers cont'aining the higher homologues of methyl.The other direction in which the research has been pursued hadalso for its object the synthesis of compounds containing twoiminazole rings, but linked by a bivalent radicle.Compounds ofthis type would differ from the foregoing benzdi-iminazoles, andmight be termed bisiminazoles.N-R"----NThe type would be:As will be seen from the experimental section of this paper, acompound of this type has been prepared, but owing to its colloidalcharacter and the difficulty of obtaining any definite crystallinederivatives, it has not been found possible to characterise! the puresubstance.The formation of azo-derivatives by the interaction of the trinitro-compound and hydrazines was indicated in a former paper (Trans.,1906, 89, 1943). This new synthesis of azo-compounds by directsubstitution in the benzene nucleus has been further studied, andthe conditions which favour the maximum yield have been experi-mentally ascertained.I n this reaction, an intermediate hydrazo-compound is formed by catenation, and from the latter the azo-compound is formed by the oxidising action of the eliminatednitro-group :OH OH/\NO,NO,!, ,)N,-A~fiH*CO*CH,I n connexion with this synthesis, it has been discovered thatsecondary hydrazines of the types : Ar,N-NH2, ArRN-NH, donot form azo-compounds, whereas all primary hydrazines readilyundergo condensation with the trinitro-compound. Thus, phenyl-,tolyl-, and nitrophenyl-azo-compounds are readily obtained from thetrinitro-compound and the respective hydrazines, whilst phenyl-methylhydrazine and diphenylhydrazine give only resinous products,arising partly from the breaking down of the trinitro-compound, an38 MELDOLA AND KUNTZEN: SYNTHESES WITH PHENOLpartly from the decomposition of the hydrazine by the eliminatednitr +group.Another synthesis made possible through the mobility of the3-nitregroup is that of azides (triazecompounds), t>he trinitro-compound reacting readily with sodium azide to form the compound :OH2 : 5 - Dinitro- 4-acetylamin 0- 3- triazophcnol.The other product of t.he reaction is sodium nitrite.EXPERIMENTAL.The Zminazole from the Trinitro-compound and Acetyl-p-phenylene-diamin e .As bhe trinitro-compound does not give, the aminoiminazolerequired as an intermediate product by interaction with p-phenylene-diarnine (Trans., 1909, 95, 1033), the acetyl derivative of the latterwaa made use of.The trinitro-compound and three molecular pro-portions of acetyl-pphenylenediamine were boiled together inalcoholic solution for two hours, the product was extracted bydilute hydrochloric acid, and purified by alternate alkaline andacid treatment in the way described in connexion wit.h all the otheriminazoles synthesised by our method. Two grams of trinitro-compound gave 2-13 grams of iminazole. 4 : 7-ninitro-6-~~ydrox.y-1 - p - acetylaminophenyzyt - 2 - methylbenaiminazole crystallises fromalcohol, in which it is very sparingly soluble, in dense, ochreousscales, melting at 261*5O :N=18.85. 0-0722 gave 11.9 C.C. N, (moist) at 1 5 O and 742.4 mm.C,,H,iO,N, requires N = 18.87 per cent.Hydrolysis of the A ce t y Zaminoiminazo Ze.The removal of the acetyl group and the purification of theresulting aminoiminazole has proved a task of the greatest difficulty,and numerous unsuccessful experiments were carried out before therequired compound was obtained.The synthesis which had to berealised is shown by the formukeDERIVATIVES CONTAINING A MOBILE NITRO-GROUP. 39Alkaline bydrolysts are ineffective, and after many trials it wasfound that strong sulphuric acid was the best hydrolysing agent forthe purpose. The acetyl derivative is not basic, but dissolves in coldconcentrated sulphuric acid, and is precipitated on dilution withwater. In order to effect the hydrolysis, the acetyl derivative isdissolved in concentrated sulphuric acid, a little water added (notenough to precipitate the substance), and the solution heated untila drop remains clear on dilution with water, thereby showing thatthe basic aminoiminazole has been formed.I f the sulphuric acid istoo strong or the temperature raised above the point at whichhydrolysis is shown to have taken place by the test described,complete decomposition ensues, and the materials are lost. Afterhydrolysis, the solution is diluted with water, filtered, if necessary,and exactly neutralised with ammonia. The precipitate is collected,washed, and purified by solution in dilute hydrochloric acid, filter-ing, and reprecipitating with ammonia. This treatment is necessary,because some of the acetyl derivative escapes hydrolysis, and ondilution and neutralisation the precipitate appears to contain, notonly the required basic amin+compound, but also a salt of thelatter with the unchanged acid acetyl derivative.It is unsafe tocarry the hydrolysis to the extreme point on account of the tendencyto undergo decomposition.The purification of the aminoiminazole after separation from theunchanged acetyl derivative presented great difficulties on accountof the combined phenolic and basic character of the molecule. Thecompound forms salts with both acids and bases, so that somedifficulty was experienced in preparing a pure specimen for analysis.After many trials, it was found that the compound formed anammonium salt, which crystallised from water in stumpy, dullorange needles :0.0756 gave 15.6 C.C.N, (moist) at 1 6 O and 768 mm.C,,H,,O,N, requires N = 24.28 per cent.This ammonium salt, when dissolved in water and decomposed byexact neutralisation with dilute hydrochloric acid, gives the free4 : 7-dirtitro-6-hydroxy-l-p-aminoph enyl-2-m ethyl b enziminazole as anochreous, microcrystalline powder, very sparingly soluble in boilingalcohol, and separating from the latter solvent in ochreous nodules,having no definite melting point, but decomposing with charringfrom about 2 1 5 O :0.1800 gave 32.5 C.C. N2 (moist) at 18.5O and 756.5 mm. N=20*7.C,4H,,05N, requires N =21-21 per cent.On account of the difficulty of crystallising the substance, nofurther purification was attempted, but the product was acted onby trinitro-compound, as described below.N = 23.9940 MELDOLA AND KUNTZEN: SYNTHESES WITH PHENOLSynthesis of t h e Bisiminazole : 4 : 4/ : 7 : 7/-Tetranitro-6 : 6I-di-hydrox y-1 : ll-p-ph en yl en e-2 : 2I-dimet h ylb is b enzimimzole.NO, N C,H* N NO,/\/\OH\/\/CH3*C I 1 .H*/\/\I I C*CH3\/\/NO, N N NO,The aminoiminazole obtained as above was boiled in alcoholicsolution with trinitmxompound in the proportiqn of one moleculeof the latter to two of the former, and t'he ochreous granular sub-stance, which separated in the course of two or three hours, wassubmitted to the acid and alkaline treatment generally adopted.There is no doubt that the product is the bisiminazole required, butit was found impossible to crystallise it from any solvent, and nospecimen pure enough for analysis could be obtained.The com-pound is extremely insoluble in all the usual organic solvents, andthe minute quantity which does dissolve separates out in a colloidalstate on cooling. It is phenolic in character, dissolving in dilutealkalis with an orange colour, and being precipitated by acids &s abrown, gelatinous mass, which dries to a brittle, brown resin. Onadding silver nitrate to a solution of the ammonium salt, a brown,gelatinous, insoluble silver salt is precipit,ated, and this also dries toa brown resin. Analyses of this resin gave:Found, Ag= 27-74 and 29.43.C22H,20,,N8Ag2 requires Ag = 28.26 per cent.The general properties of this new type of substituted bis-iminazoles are not such as to encourage a further detailed studyof the compound.The existence of the type having, however, beenestablished, we propose extending the research with a view topreparing the isomeride containing the m-phenylene nucleus, in thehope that this compound may be more amenable to treatment byordinary chemical methods.Synthesis of Azo-compounds.3-Benzeneazo-2 : 5-dinitr0-4-acetylaminopheno1,OH/\NO,NO,,)N,*C,H, 'NH*CO*CH,has already been described (Trans., 1906,89, 1943) in a preliminaryway, and a further study of the compound now enables us to givemore complete and more correct details concerning its mode oDERIVATIVES CONTAINING A MOBILE NITRO-GROUP. 41formation and properties.I n the first place, we have found thatin order to ensure the production of a pure compound, the trinitro-acetylaminophenol and phenylhydrazine must be allowed t o interactonly in equimolecular proportions. I f excess of phenylhydrazine ispresent, some secondary reaction with the azo-compound takes place,and products arising from the reduction of the latter are formed.These impurities are extremely difficult to remove, and theirassociation with the azo-compound tends to disguise the charactersof the latter. Our first preparation of decomposing point 188O wasno doubt contaminated to a sufficient extent to depress the decom-posing point, as we now find that the pure compound decomposesat 248O.In order to prepare the azo-compound, equimolecular proportionsof the trinitro-compound and of phenylhydrazine are dissolved in asmall quantity of alcohol, and the solution is warmed until the redcrystalline salt, which at first separates out, passes into solution.When this stage has been reached it is better to remove the flaskfrom the water-bath and to allow the reaction to complete itself atthe ordinary temperature.I n the course of twelve hours, theformation of the azo-compound is complete, and the crystallinedeposit can be collected, washed with alcohol, and crystallised fromboiling glacial acetic acid. From this solvent it separates in large,ruby-red prisms, with a slight metallic lustre. It is but verysparingly soluble in boiling alcohol, but dissolves more readily inboiling pentachlorethane, forming a red solution, from which scarletneedles separate on cooling.The specimen used for analysis wascrystallised from glacial acetic acid :0.1318 gave 0.2350 CO, and 0-040 H,O.0.0783C,,H,,06N, requires C =48*68 ; H = 3-21 ; N = 20.29 per cent.The azo-compound dissolves in concentrated sulphuric acid withan orange colour, and is precipitated unchanged on dilution withwater. Attempt.s to eliminate the acetyl group by acid and alkalinehydrolysts led to negative results, the compound either not beinghydrolysed or else decomposing completely. The hydroxyl groupconfers phenolic characters on the compound, and it forms alkalinesalts, which are completely insoluble in presence of the slightestexcess of alkali. The sodium salt is of a deep violet colour, insolublein cold water, and dissolving in hot water with a dull red colour.On the addition of acid, the azo-compound is precipitated from thehot aqueous solution of the sodium salt in the colloidal state.The azo-compound can be acetylated by keeping it in aceticanhydride solution in the presence of a small quantity of con-centrated sulphuric acid for several days.Specimens withdrawnC = 48-62 ; H = 3.37.,, 13.8 C.C. N, (moist) at 17O and 761.5 mm. N=20.6442 MELDOLA AND KUNTZEN: SYNTHESES WITH PHENOLfrom time to time and andysed showed that the substitution ofacetyl for the hydroxylic hydrogen takes place but slowly. Theproduct, which is precipitated as a dark, ochreous, crystalline powderon diluting the solution with water, melts and decomposes at about203O :0.0671 gave 10.5 C.C.N, (moist) at 15'5O and 761.3 mm. N = 18.31.Cl6Hl,0,N, requires N = 18-09 per cent.This acetyl derivative decomposes on boiling with glacial aceticacid, with the evolution of nitrous fumes and the formation of someinsoluble resinous product, together with a definite compound whichcrystallises out from the solutlon, on cooling, in ochreous needles.The latter, by repeated crystallisation from glacial acetic acid, werefinally obtained with a definite decomposing point of 284-28507and containing nearly the same percentage of nitrogen (18.2 and18.01) as the original acetyl derivative, but less carbon. Thisproduct of decomposition appears t o be of interest, but we have notyet been able t'o determine its constitution, and its study will beresumed.3-p-flitl.06 enaeneazo-2 : 5-~~nitro-4-acetylamino~~eno~.I n order to prepare this compoynd, pnitrophenylhydrazine andtrinitroacetylaminophenol are dissolved in a small quantity ofalcohol, the hydrazine being in slight excess of the quantitycalculated for one molecular proportion of each compound.Thesolution is kept warm on the water-bath f o r an hour, care beingtaken to prevent actual boiling. #On removing from the source ofheat, and allowing to remain for some hours, the azo-compoundseparates out in crystalline nodules, which can be purified by washingwith alcohol containing hydrochloric acid and crystallisation fromglacial acetic acid. The compound dissolves in this last solventwith a deep orange colour, and separates, on cooling, in dark brown,glistening prisms, which appear ruby-red by transmitted light.Itmelts and decomposes a t 244-245O:0.1308 gave 23.8 C.C. N, (moist) at 13.5O and 765.5 mm. N=21.61.CI4H,,O8N6 requires N = 21.55 per cent.This azo-compound can also be acetylated by prolonged action ofacetic anhydride in presence of a little concentrated sulphuric acid.After five Zays a t the ordinary temperature, a dkcetyl derivativeis formed, which consists of an ochreous, crystalline powder, decom-posing at 160-168O:0.0744 gave 12-65 C.C. Nh (moist) a t 17O and 761.4 mm. N = 19.76.At the end of nine days under the same canditions, another acetylC,,H,,O,N, requires N = 19-45 per centDERlVATIVES CONTAINING A MOBILE NITRO-QROUP.43group is introduced, the resulting triacetyl derivative consisting ofan ochreous, micr6crystalline powder, decomposing at 162-1 64O :0.1926 gave 29.6 C.C. N2 (moist) at 19.5O and 767.7 mm. N= 17.57.C,sH,,O,,N, requires N= 17-73 per cent.These acetyl derivatives are decomposed on boiling with glacialacetic acid, with the evolution of nitrous fumes and the formationof resinous products. As all the compounds described under thissection are new, the formulze are subjoined :OH O*CO*CH,/\NO2 /\NO,/\NO,N02/\/N20C6H4*N02(p) N0d\/N2*c6H40N02(~)NH*CO*CH, NH*CO*CH,O=CO*CH, O*CO*CH,or NO,-/\): N*N*C,H,*NO,( p)'N*CO*CH,/\NO,NO,( IN *C H *NO,(p)N( CO* C'H,), I kO*CH, \ / z 6 42 : 5-Dini t ~o-4-ace tg Zamino-3-t ria zo ph eno 1.The trinitro-compound readily exchanges the 3-nitro-group for thetriazo-group by interaction with sodium azide.A slightly warmaqueous solution of the latter is prepared, and t o this the solidtrinitro-compound is added in small portions. After some hours atthe ordinary temperature, a crystalline deposit forms, and a furtherquantity of the triazo-compound is precipitated from the solutionon acidifying with hydrochloric acid. The product, after beingcollected and washed with water, crystallises from alcohol in flat,ochreous needles or golden scales, melting a t 167-168O :0.1288 gave 32.5 C.C. N, (moist) at 15-3O and 765.9 mm. N = 29.73.C,H606N, requires N =29*81 per cent.The compound is phenolic in character, dissolving in alkalis withan orange colour and being reprecipitated by acids.The triazo-compound could not be methylated either by methylsulphate and alkali, or by silver oxide and methyl iodide.Atkemptsto remove the acetyl group by acid and alkaline hydrolysts ledto negative results, the compound resisting hydrolysis or decom-posing completely. Acetylation was effected in the usual way bymeans of acetic anhydride and sulphuric acid. After three daysa product was obtained which, from the results of analysis, appearedto be a mixture of a diacetyl and a triacetyl derivative, and fro44 SYNTHESES WITH PHENOL DERIVATIVES, ETC.which, by repeated crystallisation from alcohol, the former wasisolated in nodular tufts of yellow needles, melting at 140-141O :N=25*66.0.0420 gave 9.3 C.C. N, (moist) a t 17O and 759.2 mm.On contact with dilute alkali the 0-acetyl group is at onceC,,,H,0,N6 requires N = 25.90 per cent.eliminated, and the original triazoccompound regenerated.The Zminaaole from the Trinitro-compound and Arninoaceto-phenone : 4 : 7-Dinitro-6-hydroxy-l-p-acetylphenyl-2-methylb ena-iminuzole.This codpound was prepared in the usual way by boiling analcoholic solution containing the trinitro-compound and twomolecular proportions of aminoacetophenone for about an hour,when the iminazole separates out in ochreous scales. Purificationcould not be effected in this case by the usual method of alkalinetreatment, as the compound is resinified by the action of alkalis.After crystdlisation from alcohol, in which it is but sparinglysoluble, the compound consists of ochreous scales, melting somewhatvaguely with decomposition at 246O :0,0624 gave 8.2 C.C. N2 (moist) at, 16.5O and 768 mm.C,,H,,O,N, requires N = 15.74 per cent.By the action of hydroxylamine acetate an o x h e was obtained,which crystallised from alcohol in small, ochreous scales, meltingat 223O:N = 15.55.0-0630 gave 10-3 C.C. N, (moist) at 13O at 754 mm.C,,H,,O,N, requires N = 18.88 per cent.The iminazole reacts also with phenylhydrazine, forming a phenyl-hydrazone, which crystallises from alcohol in ochreous noduleshaving a vague decomposing point of about 198O.N = 19.16.During much of this work we had the co-operation ofMr. J. Gordon Hay, to whom we desire t o express our thanks.FINSBURY TECHNICAL COLLEGE

ISSN:0368-1645    

DOI:10.1039/CT9119900036

出版商:RSC    

年代:1911

数据来源: RSC

摘要:

ROTATORY POWER AND CHEMIOAL CONSTITUTION. 45V I I . - r n ~ ~ e $ t ~ g ~ t ~ o ~ ~ , ~ on the Dependence o j RotatoryPower on Chemical Constitution. Part I. TheRotations of the Simplest Secondary Alcohols of theFatty Series.By ROBERT HOWSON PICKARD and JOSEPH KENYON.THE authors hope to communicate to the Society a series of papers inwhich will be discussed the qualitative and quantitative dependence ofrotatory power on chemical constitution, and Feel it desirable to stateat the outset their reasons for commencing yet a further investigationof this interesting problem.It is obvious that in the present state of knowledge much ofthe previous work * in this field is very difficult to correlate even in aqualitative manner. Now there are numerous investigations of thetype, as, for example, (a) the very extended and careful researchesof P.F. Frankland and his co-workers on the rotatory powers ofderivatives of the optically active glyceric and tartaric acids ; (b) theindependent work of Tschugaeff and of Rupe on the bornyl andmenthyl esters of various acids, and ( c ) the paper of one of us andLittlebury on the esters of I-menthylcarbamic acid, in which in eachcase the effect of various substituents on t h e rotatory power of someone optically active substance has been studied; that is to say, in theabove instances the effect of substituting the alcoholic or carboxylichydrogen atoms in glyceric and tartaric acids, in borneol, menthol, andmenthyicarbamic acid. I n the compounds described in such investiga-tions the substituent is not attached to an asymmetric carbon atom,and is in many cases far removed from it in the molecule, whilst inseveral of the parent substances of such investigations there are morethan one such carbon atom.It is thus often impossible to decidehow far the effect of the substituent is due to its relative massand how far to its structure, this particularly being the case incompounds containing the menthyl radicle (compare Pickard andLittlebury, Trans., 1907, 9 1, 301).I n addition to thie difficulty there is also the additional one that it isoften doubtful whether conclusions drawn from one group of com-paratively complex compounds can be applied safely to those drawnfrom another group of widely differing constitution. Thus, forexample, confusion may be introduced if the effect on the rotatory powerof substituting the alcoholic hydrogen atoms be compared in such widelydifferent compounds, as, for example, glyceric acid, menthol, or the* Up to the end of 1904 this is admirabIy surnmarised by Walden (Bcr., 1905,38, 345)46 PICKARD AND KENYON : INVESTIGATIONS ON THE DEPENDENCEoptically active amyl alcohol of fuse1 oil.Again, many of the com-pounds compared in such investigations are solids at the ordinarytemperature, and the rotations of these have been determined insolution, although the effect of solvents on rotatory power is asyet little understood. Further, the effect of temperature on therotatory powers of the pure liquids, considerable as it is in manycases, has been often disregarded, although in this respect theinvestigations of Frankland leave little to be desired.These and similar difficulties are well exemplified when a comparisonis made of the rotatory powers of the various compounds of P-phenyl-propionic, cinnamic, and phenylpropiolic acids which have beenprepared by several investigators to show the relative effect ofunsaturation on optical activity.I n table I will be found a list of the molecular rotatory powers ofseveral of the compounds previously described, and also those of theesters of the three acids with d- and I-methyl-n-hexylcarbinol (Trans.,1907, 91, 2058).These esters of a simple secondary alcohol giveresults differing from those obtained with more complicated secondaryalcohols, such as menthol and borneol.TABLE I.Molecukur Kotatory Powem of Esters and Salts of /3-Phcnylpropioni cCinnamic, and Pheizylpropiotic Acids.Acid.E h r or Alkaloid.I-Amyl alcohol * ..................(Methylethylcarbincarbinol)I-Menthol .f.........................) , $ ........................,, s{; ..........................................d-llorneo1 { a!.. ..................b .....................tE-Methvl-n-hexvlcarbinol 11.. ....Z-Rtethj.l-it-hcx?;lcarbinol ll'.. ....Coiiiine T ...........................Cinchouine 7.. ......................B-Phenyl-propionic.+ 5.0"- 161.9178.3171.5162% + 86.682.91- 32.1- 32.a- 5 *1 + 381 *9Cinnamic.$. 16.4"- 247.8235 51 7 1 %184'3$- 82.5SS.6f 104.4- 103.4- 20.6 + 475 '2Phenyl-propiolic.4- 12.1"-- 215'9- 166.7157'6 + 87-689 '4 + 131 '1- 130.9 - 19.7f 511.6* Walden (Zeitsch.physikal. Chcsn., 1896, 20, 569).Marckwald (Ber., 1902, 35, 1599), this alcohol is d-amyl alcohol..1. Tschugaeff (J. Rztss. Phys. Ch,e?n. SOC., 1902, 34, 606).ZRupe (Annalalz, 1909, 369, 311). Deternlinations in 10 per cent. benzene8 Hilditch (Trans., 1908, 93, 14). Deterniinations in 10 per cent. solution, (a) in11 The unsaturated esters have been quantitatively reduced to the saturated esterT Hilditch (Trans., 1908, 93, 713). Determinations iil 4 pey cent. chloroforinIn the nomenclature ofsolution.chloroform, ( b ) in acetone.(see page 67).solu tiouOF ROTATORY POWER ON CHEMICAL CONSTITUTION.PART I. 47These results (table I) show at once that no general conclusions canbe drawn as to the quantitative effect on the rotatory powers of thealcohols and alkaloids named when the alcoholic hydrogen atom isdisplaced by acid radicles (or salts are formed with acids) of closelyrelated constitution, but differing in the degree of unsaturation, for insome cases the ethylenic, and in the others the acetglenic, compoundhas the greater rotation.It is, however, convenient at this juncture to recall that thevast amount of painstaking and laborious work in this field has led tocertain well-founded, but very wide, generalisations. These need notnow be re-stated, but are well exemplitied by the investigations quotedin the table, which (with others) show that (we believe in everyknown case) the effect of unsaturation is exhibited in the exaltationof rotatory power.Considerations such as these make the following conditions desirablefor a re-investigation of this subject : (1) the active compounds comparedshould containonlyoneasymrrietric carbon atom; (2) the effect of variousradicles on the rotatory power should only be compared when theseare attached directly to the asymmetric carbon atom, and (3) thecompounds should be liquids and their rotatory powers should bemeasured in the pure state and at different temperatures.Thus, whilst previous investigators have as a rule studied thevariation in the rotatory power of some one compound caused byinactive substituents, the object of the present authors is to comparetbe rotatory powers of different series of comparatively simplecompounds. Optically active compounds, however, of the typerequired are very little known, and it becomes therefore necessaryto prepare them specially.No class of compounds seems so likely as the alcohols to fulfil ingeneral the third condition laid down, whilst the ease with which alltypes of alcohols can now be synthesised, thanks to the Grignardreaction and the catalytic reactions of the Toulouse school, makes thisclass of compounds particularly suitable for the purpose in view.Now one of us and Littlebury have described (Trans., 1907, 91, 1973)a method for what is believed to be the complete resolution of racemicalcohols, nameiy, by the fractional crystallisation of the salts formedby the combination of various optically active bases with the acidesters of the alcohol and a polybasic acid, whilst the present authorsin a similar way carried out the first successful resolution (Zoc.cit.) ofan aliphatic alcohol, namely, that of methyl-m-hexylcarbinol with[a]: 29.9". The method has since been found t o be a general one,and can be applied to several types of alcohols (see preliminary note,Proc., 1909, 25, 167); therefore, those types of alcohols whichcontain one asymmetric carbon atom, since they can be synthesise48 PICEARD AND KENYON : INVESTIGATIONS ON THE DEPENDENCEand resolved into their optically active components, and since theyhave as a rule low melting points, appear to be very suitab1e''for are-investigation of the problem of the dependence of rotatory power onchemical constitution.However, before describing the results obtained so far in thisdirection, attention should be called to the following evidence, whichwill furnish an answer to the very obvious question as to whethersuch results might not be vitiated by an incomplete resolution of theracemic alcohols.Now, firstly, that the method has effected completeresolutions in some cases seem certain. For example, one of us andLittlebury (Zoc. cit.) prepared by this method four borneols, which allseverally gave, when oxidised, camphors identical in rotatory powerwith tbe maximum exhibited by the natural products ; thus the d-borneoland the 2-isoborneol prepared each gave pure d-camphor, whilst theZ-borneol and the d-isoborneol gave pure I-camphor.Again, thed-methyl-n-heptylcarbinol described below has an equal but oppositerotatory power to that of the specimen of the same compound isolatedfrom oil of rue by Power and Lees* (Trans., 1902, 81, 1592).Secondly, in the case of the fourteen alcohols, the resolutions of whichare described below (with two exceptions),t there have been obtainedeither both the dextro- and laevo-rotatory forms of the alcohols withequal and opposite rotations, or both forms of the same acid esterwith equal and opposite rotation, or two preparations of the same acidester having identical rotations by fractional crystallisation of thesalts of two different alkaloids or two preparations of the alcohol withdentical positive rotation from two different acid esters.Thirdly,the recorded rotatory powers (see table 11, p. 49) of the alcoholsbelonging to the same series show a gradual alteration as the series isascended, and thus agree well one with the others. Fourthly, anexhaustive series of experiments failed to give any evidence againstthe optical purity of methyl-n-hexylcarbinol with [a]': +, 9.9'. I nthese, (a) the diethyl and dimethyl esters of d- and 2-tartaric acid wereallowed to remain in presence of hydrogen chloride with an excess ora deficiency of the d- or the I-alcohol, under which conditions the/I-octyl group more or less completely displaces the methyl or ethylgroup in the tartaric esters; ( b ) d- and I-tartaric acid were eachtreated in the same way with the two alcohols; ( c ) the P-octyl estersof the tartaric acids thus obtained were each hydrolysed partly withan insufficiency, or completely with an excess, of potassium hydroxide.In view of the experiments of Marckwald and McKenzie (Ber., 1901,d-Methyl-n-nonylcarbinol, as now obtained by synthesis, has a higher positiverotation than the lsvorotetory alcohol isolated by these investigators from thesame oil.t Methyl-n-decyl- and phenylmethyl-carbinolsOF ROTATORY POWER ON CHEMICAL CONSTITUTION.PART I. 4934, 469) on the varying velocity of esterification of an optically activeacid with the two optical isomerides of an alcohol and the varyingrate of hydrolysis of the corresponding esters, it was to be expectedthat such experiments carried out under many varied conditions(including those detailed by them) would yield a product of rotatorypower different from [a]:: k9.9' if this were not the constantrelating to optically pure methyl-n-hexylcarbinol.In no case,however, was a sample ol the alcohol obtained as a result of theseexperiments of either lower or higher rotatory power.Resolution of Fourteen Alcohots.The resolution of fourteen alcohols is described in this section ;twelve of these are of the general formula CH,*CH(OH)*R, where Rrepresents the normal groups ethyl to undecyl, isobutgl and phenyl,whilst the other two have the formula C,H,*CH(OH)*R, where R'represents n-hexyl and phenyl. The preparation of these activealcohols has been repeated, and in all cases but two-methyl-n-decyl-and phenylmethyl-carbinol- the pure optically active alcohols havebeen obtained in at least two ways.In Figs." 1 and 2 is illustratedthe variation of the specific rotations with the temperature, andtable I1 shows how in the series methyl-n-propyl- to methyl-n-undecyl-carbinol the molecular rotatory powers tend to approach a commonvalue. These resolutions have been carried out by the methoddescribed (Zoc. cit.) for methyl-n-hexylcarbinol, that is, by the frac-tional crystallisation from acetone or aqueous acetone of the alkaloidalsalts of either the hydrogen phthalic or succinic esters. Where aTABLE 11.Specijik and Nolecula~ Rotatory Powers of the Dextrorotatory Alcohols.Alcohol. [.1:0 [ M r [.I$ "3:Methylethylcarbinol ......+lS*87" +10*3" +12*48" +9'2" +11+84" +8.8'Methyl-n-propylcarbinol ... 3.370 12.1 12.89 11.3 12.56 11.2Methyl-n-butylcarhinol ... 11.57 11'5 11.02 11.2 10'90 11.1Methyl-n-amylcarbinol ... 10'32 12.0 9-89 11.5 9.60 11'1Methyl-n-hexylcarbinol ... 9'76 12.7 9'17 11.9 8.99 11.7Methyl-n-heptylcarbinol ... 8.99 12-9 8-55 12.3 8-30 12'0Methyl-n-octylcttrbinol ... 8-68 13.7 8'14 12.9 7.80 12'3Methyl-n-nonylcarbinol ... 8'13 14-0 7'66 13.2 7'28 12.5Methyl-n-decylcarbiriol ... 7-75 14.5 7-27 13.5 6-89 12.8Methyl-n-undecylcnrbinol . 7.22 14'4 6.67 13.3 6.39 12.7Methylisobutylcarbinol ... 20.54 20.9 19.25 19.6 18-32 18.7Ethyl-n-hexylcarbinol ...... 8-05 11'6 8.17 11.8 8.30 12.0Phenyimethylcarbinol ...... 42'86 52.3 42'68 52.1 41.60 50.8Phenylethylcarbinol .........27'73 37-7 32.52 44.2 35'54 48.3* It shonld be iioted that in Fig. 2 the scale of the ordinates is one-third that ofVOL. XCIX. Ethe scale of the ordinates i n Fig. 150 PICKAKD A N 0 KENYON : 1NVES'l'IGATIONS ON THE DEPENDENCEresolution was effected, in all cases brucine formed the least solublesalt (ZBdA) with the dextrorotatory hydrogen phthalic esters and thedextrorotatory hydrogen succinic esters of the two alcohols containingthe phenyl group, whilst with the purely aliphatic alcohols thisalkaloid formed the least soluble salt (ZBZA) with the lsvorotatoryFIG. 1.SPECIFIC ROTATORY POWERAT DIFFERENT TEMPERATURESD t;ester. Similar results were obtained with strychnine, whilst cinchoni-dine gave results of an opposite character, as with this alkaloid theleast soluble salts were ZBZA and ZBdA in the case of the hydrogenphthalates and succinates respectively.Thus, for example, thefollowing salts were found to be the least soluble component of themixture of salts formed by neutralising the hydrogen ester with thOF ROTATORY POWER ON CHEMlCAL CONSTITUTION. PART I. 51base : brucine and strychnine d-P-heptyi hydrogen phthalate, cinchoni-dine EP-heptyl hydrogen phthalate, brucine d-6-methyl-/l-amyl hydrogenphthalate, brucine Z-S-methyl-/l-amyl hydrogen succinate, and cinchoni-dine Z-phenylethylcarbinyl hydrogen succinate.Under the successful conditions employed in the other cases, noFIG.2.S P eC1 FIC ROTATORY POWERAT DIFFERENY TeMPERATURESDECREESresolution was effected with the brucine, strychnine, or cinchonidinesalts of the hydrogen phthalates of either yheny1r.net hyl- or phenvl-ethyl-carbinols, or with any salts of the hydrogen esters of tetra-chlorophthalic acid.In the optically pure state, none of the fourteen alcohols haspreviously been described, except methyl-n-heptylcarbinol, the laevo-E 52 PIUKARD AND KENYON : INVESTIGATIONS ON THE DEPENDENCErotatory isomeride of which was isolated from oil of rue by Power andLees (Zoc. cit.).By fermentation methods, Combes and Le Be1 (BUZZ. 800. chim.,1880, [ii], 33, 106, 147; 1893, [iii], 9, 676) obtained methylethyl-and methyl-n-butyl-carbinols with specific rotatory powers not exceeding[a]D - 0.5' and [a]D - 8' as against [a]: + 13.87' and [a]$' + 13-70'respectively for $he pure alcohols, whilst Meth (Bey., 1907, 40,695) obtained methylethylcarbinol with [a]D less than 1' by a methoddiscussed in a former paper by one of us and Littlebury (Zoc.cit.).Marckwald (Bey., 1905, 38, 809) has also obtained phenylmethyl-carbiaol with [a12 +2*7' (as against [a]: + 42.87') by the action ofnitrous acid on Z-phenylethylnmine with [a]: - 39.51'. Haller(Compt. rend., 1910, 151, 697) has quite recently isolated from cocoa-nut oil, feebly dextrorotatory forms of methyl-n-heptylcarbinol with[aID + 2*41°, and methyl-In-nonylcarbinol with [a], + 1*40°, laevo-rotatory specimens of these having been previously isolated from oilof rue by Power and Lees (Zoc.cit.).The number of optically active alcohols here described is obviouslytoo small to admit of any discussion of the results in so far as theyaffect the main object of the investigation. Attention, however, maybe drawn to the following points. The rotatory powers of the seriesof alcohols described do not differ much in general character from someof the series of normal esters described by other investigators, as, forexample, the series of the normal ester8 of diacetylglyceric acid(Frankland, Trans., 1897, 71, 270), where the rotatory powersgradually ascend to a maximum. Determinations of the molecularrotatory powers of the hydrogen phthalic esters in chloroform solutiongave results * which run practically parallel with those of the alcoholsin the pure state, although in the case of the esters the first memberoccupies apparently a normal place in the series and has not, as inthe case of the alcohols (as also in 80 many series described by otherinvestigators), an abnormal rotatory power.At the outset of the investigation it was thought possible thatamongst the alcohols of the type CH,*CH(OH)*R, some simple numericalrelation might be found to exist among the numbers expressing therotatory powers, It will be seen at once, however, that no comparisonis feasible, if the influence of temperature be taken into account.Whilst the curves in Fig.1 relating to the series (methyletbyl-carbinol excepted) become parallel as the temperature increases, yeta t no temperature up to 100' (the limit of the present experiments?)* See table, p.63.t The question as t o a possible relation or constant existing at or above theboiling points of the alcohols for the molecular rotatory powers is reserved forfurther discussion when more material is available, The values of the rotatorOF ROTATORY POWER ON CHEMICAL CONSTITUTION. PART I. 53can the rotatory powers of the members of the series be comparedwith those of the alcohols of other types (see Fig. 2), or indeed withthat of methylethylcarbinol.The question of the (as yet unsolved) problem of the effect ofassociation on the rotations of pure liquids (compare Walden, Zoc. cit.)naturally arises in this connexion. Does association account for the greatdifferences in the temperature-coefficients as illustrated in Figs.1 and 2 '1Now these alcohols as judged by Ramsay and Shields' capillarityascension method or by Longinescu's empirical formula * (Ann.Sci. Uniu. Jccssy, 1903, 2, 126) are only slightly associated. Thusempirically the association factor ford-Methyleth ylcarbinol is 1 *33d-Methyl-n-propylcarbinol , , 1 '24d-Methyl-n- butylcarbinol , , 1 -15d-Methyl-n-amylcarbinol ,, 1'14d-Methyl-n-hexylcarbinol , , 1.08d-Methyl-wheptylcarbinol , , 1 005d-Methyl-n-nonylcarbinol is 1 -01d-Ethyl-n .hexylcarbinol , , 1 -03d-Methyliwbutylcarbinol ,, 1-14d-Phenylmethylcarbinol , , 1'12d-Phenylethylcarbinol ,, 1-08whilst, for example, by the capillarity ascension method d-methyl-ethylcarbinol between 19.8' and 36.8O has a mean association factor1.8, and d-methyl-n-hexylcarbinol between 15' and 34' has 1.5.t Nowthe similarity of the temperature-coefficients for the alcohols in theseries, despite the decrease in association as the molecular weightincreases and the striking differences in the temperature-coefficients ofphenylmethyl- and phenylethyl-carbinols, of methyl- and ethyl+-hexyl-carbinols, and of methylethylcarbinol and the rest of the series, seems toshow that association has a very slight, if any, common influence onthe rotation of these pure liquids.Since, however, it is a matter ofsome difficulty to measure small differences in assaciation, the questionof its influence on the rotatory powers of the individual alcohols couldnot be followed further.The striking differences observed in the cases just mentioned in thevariation of rotatory power with the temperature may be due partlyto stereochemical causes, but possibly also to the more profoundchanges on the rotatory power of a complex, R*CH(OH)*CH,-, cawedby hydrogen than by a radicle (CH3),Methylisobutylcarbinol was resolved at an early stage of theinvestigation to ascertain whether the differences in the rotatorypowers of aliphatic alcohols corresponding with small differences inconstitution were likely to be large.The exaltation in rotatory powerpowers of methyl-n-butyl- and methyl-n-octyl-carbinols coiiimence t o rise a t about125", these being the only two alcohols investigated a t the higher temperatures.- &, where T = b.p. on the absolute scale, D=d,", and n = the mean.1. It has often been observed that the capillarity ascension method gives higher*loOD-number of atoms in the molecule.values for the association factor than those obtained by empirical calculation54 PICRARD AND HENPON : INVESTIGATIONS ON THE DEPENDENCEcaused by the isobutyl as compared with the n-butyl group is consider-able, and affords additional evidence of powerful influence of con-stitution on rotatory power.The halides corresponding with some of the alcohols have beenprepared, the molecular rotatory powers being recorded in table 111.In every case the conversion of the alcohol into a halide (CI, Br or I)was accompanied by a change of sign in the rotation.Attempts toreconvert these halides into the optically pure alcohols have not as yetproved successful, and the preparation of them with any degree ofcertainty that racemisation has been avoided is tedious and verycostly. This portion of the work has therefore not been extended forthe present in case further physical measurements of the alcoholsthemselves appear desirable as the investigation proceeds. It will benoticed from Fig. 2 that the specific rotation of d-P-bromo-octanesinks regularly as the temperature increases, the curve being a straightline, and in this respect analogous among the alcohols only withethyl-n-hexylcarbinol, for which, however, the specific rotation risesregularly with the temperature. The association factor for d-P-bromo-octane, calculated by Looginescu's formula, is 1.07.The authors are greatly indebted to Dr.T. M. Lowry for thedeterminations of the refractive indices of the dextrorototory alcoholsas recorded in table IV. Dr. Lowry has also undertaken thedetermination of the magnetic and optical rotatory dispersion. * I nrespect to the optical rotatory dispersion a somewhat strikingTABLE m.Rotatory Powers of the Halides.B-Iodobutane ............B-Iodopentane ............8- Iodohexan e ............B-Todo-octane ............7- Iodo n onan e ............B- Bromo-octane ........y-Bromononane .........B-Chloro-octane .........y-C hlorononane .........o-Chloroethylbenzene ...a-Chloropropylbenzene . .c q .- 31 -98"- 37.15 - 58-35- 40.56- 17'50- 27-47- 13-39- 2 0 4 4- 8'03- 5.80- 3.87[ M I 5- 58.8"- 57'0- 80'9- 90'4 - 44'4- 53.0- 27.7- 30.4- 13'0 - 8'2-6'0[.I:.-.-- + 39 -82" + 17'65 + 27 *53 + 12.90 + 20.40 + 7.71+ 3'79-connexion between this and the anomalous temperature-coefficientsalready mentioned has been observed. Thus, in a private communica-tion, he states that those active alcohols of which the specific rotatorypower varies normally with the temperature (see curves in Fig. 1 formethyl-m-propyl- to methyl-n-undecyl-carbinol) appear to give a,cnnstant value for the ratio u4a79/a54B1, which affords the most* The results of these determinations will be published separatelyOF ROTATORY POWER ON CHEMICAL CONSTITUTION.PART I. 55convenient measure of their rotatory dispersion ; on the other hand,those alcohols which have a different temperature-coefficient of opticalrotatory power (methylethyl-, ethyl-m-hexyl-, methylisobntyl-, phenyl-methyl-, and phenylethyl-carbinols) also differ in optical rotatorydispersion from the normal series, CH,*CH(OH)*R (where R = n-C3H7to n-C,,H,3), of active alcohols referred to above ; there is, however,no simple relationship between the sign of the temperature-coefficientand the relative magnitude of the dispersion ratio.TABLE IV.Refractive Indices of the Bextrorotatory Alcohols.n - 1 -.LIT.Alcohol. 92:. c l y . dhilethyle thylcarbin ol . . . . . . . . . . . . 1 -3954 0.8080 36 2Methyl-n-propylcarbinol . . . . . , 1 '4053 0.8103 44 '0Methyl-n- butylcarbinol ... .. , . . . 1'4 135 0-8150 51 '8Methyl-n-amylcarbinol . . . . , . . . 1 '4209 0-8185 59-6Methyl-n.-hexylcarbinol ......... 1.4256 0'8214 67 '4Methyl-it-heptylcarbinol.. . . . . . . 1'4299 0.8230 75'2Methyl-n-octylcarbinol . . . . . . . . . 1 -4344 0'8250 83'1Ethyl-n-hexylcarbinol.. . . , . . . . . . 1 '4308 0.8260 75.1Phenylmethylcarbinol.. , . . . . . . . . . 1.0135 63.7Phenylethylcarbinol . . . . . . . 1 *52OO 0-9940 71.1Mcthylisobutylcarbinol . . . . , . . . . 1 '4103 0.80ii 51'8Methyl-n-nonylcarbinol . . , . . . . . 1 '4369 0.8270 91'0Mcthyl-n-decylcnrbinol . . . . :. . . . 1 '4423 0-8315 99 .o1 *52 11Differencefor CH?.f *,S7.87.87.87'87.97'98.07 -4It is believed that the present paper shows that synthetical methodsmay be used to obtain accurate comparative values of the rotatorypowers of optically active alcohols. It is hoped that the furtherinvestigation of several other series of alcohols and also of acids ofsimilar constitution may give values which will be capable of easierinterpretation in a quantitative manner than the results of thoseinvestigators who have preceeded the present authors in this field.EXPERIMENTAL.The Racemic A Zcoho Is.Of the foiirteen racemic secondary alcohols which have beeninvestigated, thirteen * have been prepared either by the interactionof an aldehyde and a Grignard reagent, or by the reduction of thecorresponding ketone in aqueous alcoholic solution with sodium.The reactions bet ween acetaldehyde and magnesium ethyl bromide,magnesium propyl bromide (or chloride), and magnesium isobutylbromide respectively ; between n-heptaldehyde and magnesium ethylbromide ; between n-octaldehyde and magnesium methyl iodide, and* Methyl-n-hexylcarbinol is obtained comniercially by the distillation of a castornil soap with sodium hydroxide56 PICKARD AND KENYON : INVESTIQATIONS ON THE DEPENDENCEbetween benzaldehyde and magnesium methyl and ethyl iodides allproceed smoothly, and were carried out in the usual manner, thecheaper reagent being used in slight excess.In this way 60 to 70per cent. yields were obtained of crude methylethylcarbinol (b. p.92-99')," methyl-n-propylcarbinol (b. p. 1 18-1 22'), T methyliso-butylcarbinol (b. p.125-132"), T ethyl-n-hexylcarbinol (b. p.118-121'/65 mm.), methyl-n-heptylcarbinol (b. p. 91'/12 mm.),phenylrnethylcarbinol (b. p. 1 OO'/ 18 mm.),$ and phenylethylcarbinol(b. p. 105-108°/10 mm.).:'I'he reaction between magnesium m-butyl iodide and acetaldehydegave only about 10 per cent. of the calculated yield of methyl-n-butyl-carbinol (b. p. 136O), whilst methyl-n-heptylcarbinol and methyl-n-octylcarbinol form ti very small proportion of the products formedby the reactions between acetaldehyde and magnesium n-heptyl andn-octyl iodides.The n-octaldehyde used was prepared from n-octyl alcohol bySabatier's excellent method for the conversion of primary alcoholsinto the corresponding aldehydes. The alcohol was' heated in a flask,which was surrounded by a metal-bath kept at 200'.A rapid currentof pure hydrogen passing through this flask carried the alcohol t oa glass tube of which 50 cm. were packed with pumice stone coveredwith finely divided copper, and which was heated to 300-316O. Thealdehyde was washed out of the condensed products by a solution ofsodium hydrogen sulphite, and the process repeated four times withthe unconverted alcohol. The sodium hydrogen sulphite compoundof It-octaldehyde was crystallised from aqueous alcohol, and obtainedin nacreous leaflets, which did not melt below 270'. Decomposition ofthis compound with a strong solution of sodium carbonate, distillationof the product i n a current of steam, and subsequent rectification gavea 50 per cent.yield (calculated from the alcohol used) of n-octaldehyde(b. p. 77'/23 mm.). No by-products were observed in this preparation,the loss being due very largely to inefficient condensation of theproducts carried over by the hydrogen.The ketones required, CH,*CO*R, were prepared by passing thevarious acids, R*CO,H, mixed with five to seven times their weight ofglacial acetic acid, over thorium oxide heated to 400' (Senderens,Cornpt. rend., 1909, 149, 995 et sep.). The thoria was mixed withglass wool and loosely packed into a tube of Jena glass heated for50 cm. of its length. The normal acids used were hexoic, nonoic,* Methylethylcarbinol requires careful and repeated fractionation to separate itfrom ether.t Both of these crude alcohols contained paracetaldehyde.$ Each of these alcohols had a peculiar characteristic and pungent odour, whichwas not removed by repeated distillation, but was not present in the opticallyactive isomeridesOF ROTATORY POWER ON CHEMICAL COESTITUTION.PARTI. 57undecoic, and lauric acid. The solutions of these in acetic acid werepassed through the slightly inclined tube from a dropping funnel at anhourlyrate of about 50 C.C. I n emh case the products were practicallyneutral, and no charring took place in the heated tube. Fractionaldistillation of the products gave from 70 to 90 per cent. yields(calculated from the weight taken of the acids named) of the ketonesof the general formula CH,*CO*R, and from 30 to 10 per cent. yields ofthe ketones with the formula R*CO*R.The methyl m-amyl ketoneprepared in this manner was identical with a sample of the samecompound purchased from Schuchardt, which had been prepared bythe distillation of a mixture of barium hexoate and acetate. Someproperties of the ketones prepared are set out in table V.TABLE V.MeltingKetone. point.Methyl n-amyl ketone ......... -Methyl n-octyl ,, ......... -Diani y 1 ,, .........Dioctyl ,, ......... 53Methyl n-decyl ,, ......... 20"Methyl n-undecyl , , ......... 29tDidecyl ,, ......... 64-Diundecyl ,, ....... ..70-71Boiling Melting point ofpoint. semicarbazone. *150" 123'0"210 121'5144'111 mm. 122-123160"/16 mm. 126.0223" -- -* All obtained froni aqueous alcohol in the form of prismatic needles..1.The oxime of this ketone crystallises from aqueous needles in hair-like needles,which melt a t 27-53 and readily regenerates the ketone when boiled with dilutehydrochloric acid.It will be seen that the semicarbazones are of little value for thecharacterisation of the ketones, CH,*CO*R, for these all melt at about1 2 3 O , whilst the ketones, R*CO*R (where R contains more than fivecarbon atoms), do not form semicarbazones by the ordinary methodsfor the preparation of these compounds.The nonoic and undecoic acids used in the preparation of the above-mentioned ketones were obtained in almost quart titative yields * byDarzens' method (Compt. rend., 1907, 144, 329), in which the ethylesters of Al-nonylenic acid T and commercial undecenoic acid werereduced by hydrogen in the presence of finely divided nickel heatedto 180'.* Thus, for example, in one set of experiments 300 grams of undecenoic acid wereesterified and reduced.After hydrolysis of the resulting saturated ester and dis-tillation of the acid, 260 grams of undecoic acid (m. p, 28") were obtained. Fromthis was prepared 174 grams of methyl n-decyl ketone dong with a quantity ofdidecyl ketone, 43 grams of the acid being recovered ; 133 grams of methyl-n-decyl-carbinol were obtained by the reduction of this ketone..1. A1-Nonylenic acid was prepared by the excellent method of Harding andWeizmann (Trans,, 1910, 97, 299)58 PICKARD AND KENYON : INVESTIGATIONS ON THE DEPENDENCEThe ketones of the geneyal formula CH,*CO*R, as described above,and also methyl n-butyl ketone and methyl n-nonyl ketone (purchasedfrom Kahlbaum) were reduced in alcoholic solution by means ofsodium, the procedure of Thorns and Mannich (Ber., 1903, 36, 2544)adopted for their reduction of methyl rz-nonyl ketone being followed.The alcohols* thus obtained were (tho yields varying from 70-80per cent.) : methyl-n-butylcarbinol (b.p. 136O), methyl-n-amylcarbinol(b. p. 15s-160°), methyl-n-octylcarbinol (h. p. 210-21 lo), methyl-rz-nonylcarbinol (b. p. 11 9'11 2 mm.), methyl-n-decylcarbinol (m. p.about 5*, b. p. 140°/15 mm.), and methyl-n-undecylcarbinol (b. p.151'/11 mm.).The Rc~cemic Hydrogen Phthakic Esters.The hydrogen phthalic esters were prepared by heating the alcoholswith phthalic anhydride (equal mols.) for about ten hours at 115O inan oil-bath, except in the case of methylethyl- and methyl-n-propyl-carbinols, which were heated on a water-bath.The products,which generally contained some phthalic acid and unaltered an-hydride, were pawed when cold into a solution of sodium carbonate.After keeping for some hours to allow of the hydrolysis of anyanhydride, the alkaline solutions were extracted three times with ethert o remove unesterified alcohols and neutral phthalic esters, both ofwhich dissolve to a considerable extent in aqueous solutions of thesodium alkyl phthalates." The acid esters were then precipitated byhydrochloric acid, either as oils or solids of low melting point, andwere extracted with chloroform. Phthalic acid, being insoluble in drychloroform, is thus readily removed, whilst the dried extracts aftercomplete removal of the chloroform, at first on a water-bath, andfinally under diminished presmre, consisted of the hydrogen phthalatesin the form of opaque, crystalline masses.These acid esters are verysoluble in all the common organic media, but some of them crystallisereadily from light petroleum. The melting points of the racemichydrogen phthalates are recorded in table IX, p. 63, along withthose of the corresponding active compounds, whilst the compositionand purity of each were checked by titration in alcoholic solution withsodium hydroxide.The following compounds were also obtained :Phenylmeth ykcarbinyl hydrogen phthakate,C0,H*C6H,*C0,*CHMe* C,H,,which crystallises in opaque leaflets from either glacial acetic acid orbenzene, and melts at 108'.* All these alcohols were comparatively much purer than those obtained by theGrignard reactions.-t Such solutions cannot be warmed t o 70" or above without undergoing somedecompositionOF ROTATORY POWER ON CHEMICAL CONSTITUFIOS.PART J. 59An mid potassium salt of P-butyl hydrogen phthalate,C02K* C,R,*C02*C4H,,C0,H~C,H4~C0,*C4H9,which crystallises from acetone in very slender needles, melts a t166-168', and is decomposed by warm water.Found, K = 8-07. C2,H270,K requires K = 8.09 per cent.The Racemic Hyd2.ogen Succinates.Several acid esters of succinic acid were prepared by a methodsimilar to that employed for the corresponding phthalates. They are,however, best extracted by ether instead of chloroform, traces ofsuccinic acid being readily removed from the ethereal solutions bywashing with water.The following carbinols gave hydrogen succinatesin the form of viscous oils which did not solidify when kept at - 10' :methylethyl-, methyl-n-propyl-, methyl-n-butyl-, methyl-n-nonyl-,methylisobutyl-, and phenylethyl-carbinols, whilst that of phenyl-methylcarbinol crystallises from light petroleum in beautiful nacreousleaflets, and melts at 60-61".Brucins Salts of tfie Acid Esters.The method adopted in each case for the preparation of the purebrucine salt of the dextrorotatory acid ester was : A solution of pure*racemic acid ester in acetone is boiled with the calculated amount(equal mols.) of brucine,? which is added in small portions at atime until the alkaloid is completely dissolved.The solution, havingbeen filtered (if necesary) while warm, is then concentrated, and setaside in the ice-cheat for some hours. The crop of crystals is collectedand recrystallised several times under the same conditions. The firstmother liquor when acidified yields a laevorotatory acid ester, and isused for the preparation of the pure ltevorotatory alcohol, whilst thatfrom the first recrystallisation yields an acid ester, which is usuallyslightly dextrorotatory, and can be conveniently used for the pre-paration of the strychnine salt of the pure dextrorotatory acid ester.The melting points and rotation of the brucine salts become constantafter three t o ten crystallisations, whilst in most cases the solubility inwarm acetone decreases to a considerable extent as the salt becomespure.The actual solubility of the pure salts of the phthalates variesconsiderably and most irregularly even in the homologous seriesdescribed (see table VI) ; thus, for example, in the case of the memberof the series corresponding with octane, 100 grams of the purebrucine salt would require about 10 litres of hot acetone to dissolve it,* The snccess of the resolution largely depends on the purity of the acid ester. + All the alkaloids mentioned in this paper were the purest commercial specimenssupplied by Merck, and were recovered nnchanged in rotation60 PICKARD AND KENYON : INVESTIGATIONS ON THE DEPENDENCEwhilst the same quantity of the salt of tha.t corresponding with nonanewould require less than half a litre.The composition of the brucinesalts, as well as of the other alkaloidal salts described in this paper,mas determined by an estimation of the nitrogen content. In everycase, as was to be expected, the salt contained one molecule of eachcomponent. The brucine salts of the acid esters of succinic acid are, asa rule, much more soluble in acetone than the salts of the correspondingphthalates. The following salts were also prepared : Dibrucifie phthalate,C54H56012N4, which crystallises from warm alcohol in glisteninglamellae, which melt and decompose a t 113', and are very slightlysoluble in cold alcohol or chloroform. B?*ucine hydrogen phthalade,C31H3208N2, which crystallises from alcohol in clusters of prismaticneedles, melts at 216O, and when dissolved in chloroform bas [.ID + 13 -52'.Brucine hydrogen, succinate, C,7H3208N2, crystallisesfrom aqueous alcohol in needles, melts at 217-219', and in absoluteethyl alcohol has [a], - 17.70'.TABLE TI.Brucine Salts.Brucine salt of thehydrogen phthalate ofd-Methyleth ylcarbitiol . . . . . . . . . . .d-Methyl-n-propylcarbinol .. , , . .d-Methyl-n-butylcarbinol . . . . , ,d-Methyl-n-amylcarbinol . . . . . . . . .d-Methyl-n-hexylcarbinol . . . . . ,d-Methyl-n-heptylrarbinol . . . . . .d-Methyl-n-octylcarbinol . . . . . . . . .d-Methyl-n-nonylcarbinol .. . . . .d-Methyl-rL-decylcnrbinol . . . . . .d-Methyl-n-undecylcarhinol .. .cZ-Meth y lisobutylcarbinol . . . . . . . . .rZ-Ethyl-n- hexylcarbinol . . . . . . . . .Meltingpoint.154-1 65"154-155144-145137-138140-142136-138113-116123-124120-1 22167-168108-110151hydrogen szminate ofd Phenylmethylcarbinol . . . . . . . . .d-Phenylethy lcarbinol . . . . . . . . . . . .Z- Meth ylisobutylcarbiiol , . . . . . . .110'5103-1 0595Rotatory power * inethyl alcohol.Specific.- 2'93"- 3-914-084 '425-444'976 '015 '226.065.694'1911'41+ 15-3316'28- 22.41Molecular.- 18.1"- 24'626.029-136.634-142.137'244 -142.226 '978.5+94'4100-2 - 133.6* In all cases mentioned i n this paper where the rotatory power of a compoundhas been observed in solution, the solution was prepared by making up 1 gram ofthe compound to 20 C.C.with the Bolvent.Cinciionidine and Strychnine Salts of the Acid Esters.The cinchonidine salts of the acid esters were prepared, as a rule, inthe same way as the brucine salts, but hen dissolved in hot acetonethey often decompose and deposit the alkaloid. It was found prefer-able in some cases to adopt the following method, which was employedfor the preparation of the strychnine salts : Equimolecular proportionOF ROTATORY POWER ON CHEMICAL CONSTITUTION. PARTI. 61of the alkaloid and the acid ester are dissolved in chloroform ; thechloroform is then distilled off, and whilst the salt is still in the pastycondition, it is dissolved by the addition of the requisite amountof boiling acetone.For each recrystallisation the salt is dissolved inchloroform, and a like procedure followed.Most of the cinchonidine salts are very soluble in acetone, anddo not crystallise at all readily from aqueous acetone. The strychninesalts of the optically pure acid esters are only very slightly soluble incold acetone, and are always partly decomposed when boiled withacetone. The strychnine salts described in table VIII were allprepared from samples of acid esters possessing a slight positiverotation. Strychnine salts of the dl-hydrogen phthalates wereunaltered in rotation by recrystallisation in the manner described,whilst the rotation o€ the strychnine salt of a partially activehydrogen phthalate of phenylmethylcarbiaol was not affected bycry stallisation.TABLE VII.Cinchonidine Salts.Cinchonidine salt of the Meltinghydrogen phthalate of point.Z-Methyl-n-amylcarbinol ............108-109"Z-Methyl-n-hexylcarbinol ............ 112-116Z-Ethyl-n-hexylcarbinol ............... 11 5 -1 18hydrogen succinate ofd-Methyl-n-butylcarbinol ............ 89- 90d-Methylisobutylcarbinol ............ 100-102Z-Yhenylethylcarbinol ............... 161 -1 62TABLE VIII.Strychnine Salts.S trgchnine salt of thehydrogen phthalati? ofd-Methyl-n-propylcarbinol ............ d-Methylethylcarbinol.. ...............d-Methyl-n-amylcarbinol ............d-Methyl-m-hexylcarbinol ............d-Methyl-wheptylcarbinol ............d-Me t h yl-n-octylcarbinol .......: .......d-Methyl-n-nonylcarbinol ............d-Methy l-n-undecylcarbinol .........Meltingpoint.149-152"179--181203-204142-1 4 3136-137144-145142-143180Rotation in ethyl alcohol.cpecific. Molecular:- 70 '36" - 392.6"68.02 389'060.47 354'376.73 380'676 $4 379 '6118'46 628'2Rotation in chloroform.Specific.- 20*04"- 18-56- 18.89- 18-74- 19 '47-18'37- 17'11- 18'697 Molecular.- 2: *so30.731'732 *732 '234.838'236'6Optically Active Acid Esters of the Alcohols."The optically active acid esters were readily obtained from thebrucine and cinchonidine salts wheu alcoholic solutions of these were* Attempts were made to resolve the hydrogen tetrachlorophthalic esters ofmethylethyl-, methylisobutyl-, methyl-n-propyl-, and methyl-n-butyl-carbinols byfractional crystallisation of the brucine and cinchonidine salts, but in uo case wasany resolution effected under the conditions tried62 PICKARD AND KENYON : 1NVESTIGATIOn'S ON TEE DEPENDENCEpoured into dilute hydrochloric acid.Although the oily esters, whichwere at once precipitated, in many cases solidified to crystallinemasses, it was generally found necessary to dissolve them in ether, sothat by repeated washing with very dilute hydrochloric acid thehydrochloride of the alkaloid could be completely removed. Thestrychnine salts were decomposed in a somewhat different manner.Alcoholic solutions of these were poured into dilute ammonia, and,after the strychnine had been removed by filtration, the acid esterswere obtained on the addition of hydrochloric acid.The acid phthalic esters (see table IX) were all obtained ascrystalline masses after removal of the solvent, and in some cases arereadily recrystallised from light petroleum, but, like the acid succinicacids and all the corresponding racemic compounds, they are verysoluble in the common organic media.The optically active acidsuccinic esters were only isolated in three cases, being usuallyhydrolysed at once. They are all oils, which decompose whendistilled, so that the observed rotatory powers may be mis-leading, as the solvent (ether) may not have been completelyremoved. The hydrogen I succinate of d-methylisobutylcarbinol had[fit], + 14.52' in chloroform, and the corresponding Isvo-compound,[a], - 14.37'; d-P-hexyl hydrogen succinate had [a]= +6*19O inchloroform, whilst the hydrogen succinate of phenylethylcarbinol hada - 20.06' in a 25-mm.tube.The Optically Active Alcohols.The alcohols, except i n the case of methylethyl- and methyl-n-undecyl-carbinols, were obtained by the following method : The acidester is dissolved in a hot concentrated aqueous solution of potassiumhydroxides (24 mols.), and the alcohol formed by the hydrolysis isdistilled over in a current of steam. It is then extracted from thedistillate by ether, and the ethereal solution is dried by long keepingover freshly ignited potassium carbonate.The optically active alcohols obtained were comparatively stable inthe presence of alkali hydroxides. Although as a matter of pre-caution they mere removed from the prolonged action of potassiumhydroxide as rapidly as possible by a current of steam during thehydrolysis, yet in two or three cases (notably those of methyl-n-hexyl-and methyl-n-undecyl-carbinols) by actual experiment it was found thatthe rotation was unaltered by continued boiling under a refluxcondenser with aqueous alkalis.The alcohols were obtained as colour-less, strongly refracting liquids or low melting solids. They have faintcharacteristic odours, in all cases these being far less than those of theoptically inactive isomerides. There seems to be in some cases, foHydrogen phthalate ofMethylethylcarbinol .............................h1ethyl.n-propylcarbinol ...........................Me th y 1-n-bu tylcarbinol ..........................Methyl-n-amylcarbinol ...................Methyl-n-hexylcarbinolMethyl-n-heptylcarbinolhlethyl-12-octylcarbinolnlethyl-n-nonylcarbinolMethyl-n-decylcnrbinol ...........................Jlethyl-n -undecylcarbinol- 1 ........................ {i{{{..............................................................................................Ethyl-n-hexylcarbinol ...........................TABLE IX.The Hydrogen Phthalic Esters.Melting pointof 5 z z c - z Z56-57" "46-47" - -"60-61 "34- "2957-58 76.555 75"42-44 58-59"48-49 "38-39"49-50 "31-32- -- -- -- -- -- -50-51 "2858-59 "2647-49 54-55- -- -chloroform.+ 33-54' + + 33-51 t- + 36.94 + 43.39 + 108.5$43'89 +115*+43'94 +116'-43.81 - 115.7 + 42-94 + 119'- 43-27 - 120.3+41*17 $120'+41*04 +119-+39-01 +119* + 39.11 + 119.7+37*34 f119.5+37*19 f118.8+35*59 +121* + 3554 + 124.0 + 35.13 + 1223 + 13-78 +[a], EW,$87-- 13.62 -* Denotes a melting point determined of the crystalline mass drained on a poroust B denotes from briicine salt ; S from strychnine salt, and C from cinchoaidin64 PICKARD AND KENYON : INVESTIGATIONS ON THE DEPENDENCEexample, phenylethylcarbinol, a slight difference in the aroma of thedextrorotatory and laivorotatory forms.Specimens of some of the alcohols of each type described were foundt o be unaltered in rotatory power after exposure to light for manymonths whilst stored in common glass bottles. Several of them werereconverted into the hydrogen phthalic esters, these being readilyobtained without recrystallisation with the maximum rotation observed,showing that at least these alcohols will not undergo racemisationwhen removed from natural products by the " phthalic anhydride"method (compare Haller, Compt.rerand., 1910, 151, 697). At least30 C.C. of each of the active alcohols mentioned below have beenobtained and the preparations repeated. The densities have beendetermined in a pyknometer holding 3.5 c.c., and the rotations injacketed tubes of 50 and 100 mm. long.MethyZethyZcarbirzoZ.-Since this alcohol is very difficult to separatefrom ether, it was '( salted out" of the distillate obtained from thehydrolysis of the hydrogen phthalic ester by means of potassiumcarbonate.Specimens of the dextrorotatory alcDhol obtained from thebrucine and strychnine salts of this acid ester agreed in rotatorypower, this being unaltered by keeping over freshly-ignited bariumoxide.The dextrorotatory alcohol boiled at 99O/760 mm., had CZ~''~ 0.8206,i7 0.8025, 0 7717, and i7'5 0.7566 ; and [.ID + 14.83' at 4*b0, + 14.03'at 17*8', + 13.52Oat 27O, + 13.08' a t 36-5O, + 1257O at 48*7', + 12.15'at 58O, + 11-77" at 7 2 O , and + 11.83O at 91.7O.The alkaloidal salts of the I-P-butyl hydrogen phthalate and of thecorresponding succinates crystallise badly, and are decomposed whenwarmed with acetone.Several attempts have been made by oneof us and W. 0.Littleburyto resolve this alcohol by the ' 6 menthylcarbimide " method (see Trans.,1906, 89, 465, 1254). dl-P-Butyl I-melzthylcarbamate,C,,H,,-NH* CO,*C,H,,was readily obtained by warming equimolecular quantities of thecarbinol and I-menthylcarbamide. It crystallises in large prismatictablets, which melt a t 54O, and have M, - 162.4 in chloroform.When recrystallised several times from aqueous ethyl alcohol, themelting point rose to 71", and the molecular rotatory power fell t o- 152.49 The resolution, however, was not complete, as d-S-butyl1-menthylcarbamate, prepared from the dextrorotatory alcohol describedabove, melted at 72', and had [a], - 5 5 ~ 7 8 ~ and M, - 142.2'in chloro-form. Experiments in this direction were not completed, as it wasfound impossible to hydrolyse the carbamate except by means ofalcoholic potassium hydroxide, and then the separation of the carbinolfrom the ethyl (or methyl) alcohol used required too much materialOF ROTATORY POWER ON CHEMICAL CONSTITUTION.PARTI. 65l-p-rodobut~cne.--SeveraI comparative experiments were carried outto determine the conditions for displacing the bydroxyl group of thecarbinol by iodine without racemivation of the compounds. Theproduct of highest lzevorotatory power mas obtained when the dextro-rotatory alcohol was saturated at 0" with hydrogen iodide (free fromiodine) and warmed in a sealed tube for thirty minutes a t atemperature not exceeding 60". The lsvorotatory iodo-compound thusprepared boiled at 118", had di7 1.5970, and [u]: -3198".Attemptst o convert this iodide into optically active methylethylcarbin-cnrbinol (sec.-butylcarbinol) by successive treatment with magnesium(in ethereal solution) and formaldehyde (trioxymethylene) gavenegative results ; under the conditions tried, the products were alwaysoptically inactive, racemisation probably taking place during theformation of the Grignard reagent.d- Methyl-n-prop ylcarbinol. --This alcohol, prepared either from thebrucine or the strychnine salt of the dextrorotatory hydrogen phthalicester, boiled at 118*5-119*5". Determinations of the density gaved:2'3 0.8169, iG'8 0.8058, iG'8 0.7967, :7.3 0,7871, 64°'5 0.7751 ; and of thespecific rotatory power : [a]; + 14*38', + 13-56' a t 19", + 13.44" at27*5O, + 13-14' a t 38', + 12 91" a t 49', + 12-79' at 55*5', + 12-55' a t73", and + 12.56' at 90.5'.I-P-lodope.ntane.-This compound wits prepaied as follomv : Thedextrorotatory alcohol was saturated with pure hjdrogen iodide at0", and heated at 100'in a sealed tube for thirty minutes.Afterpurification in the usual manner, the iodide boiled a t 143", haddi7 1,5067, and [.]a - 37.15'.d-HetlhyZ-n-butylcarbinol, of identical rotatory power, was obtainedfrom the brucine salt of the dextrorotatory hydrogen phthalic esterand from the cinchonidine salt of the dextrorotatory hydrogen succinicester. It boiled at 137-13S0, had G?:'~ 0.8179, F'5 0*8021, F3 0.7903,Fo 0,7726, and :33 0,7134, and [u]L + 12*08', + 11.60' at 19", + 11-45"at 26*8', + 11.27' at 35*7', + 11.05' at 48', + 10.87' a t 59', + 10.77'at 72O, + 10-77" at 93', and + 11.28' at 133'.1-P-Ioclohesans was prepared in a similar manner to the corre-sponding pentane derivative.d-Methyl-n-am&arbinoZ.-This alcohol boiled a t 73-5'/20 mm., hadci;O 0*8190, i5 0.8050, :' 0.7920, 0.7815, and [a]: + 10-21', + 10.14'at 31", + 9.95' at 46O, and + 9-75' at 69.3O.I-~sthyl-n-~cmytcarbinol had very similar constants to the dextro-rotatory alcohol.It boiled at 74.5'/23 mm., had at;" 0.8184, and[ap - 10*52O, - 10.48O at 17', and - 9.58' at 91".d- and l-Metl~~Z-n-hexyZcarbinob.-These alcohols (Pickard andKenyon; Zoc. cit.) have been prepared in larger quantities thanany of the other alcohols here described The following additiondIt had di7 1.4354, and [a]; - 38.35'.VOL.XCIX. 66 PICHARD AND KENYON : INVESTIGATIONS ON THE DEPENDENCEconstants have been determined for the dextrorotatory compound :d y 0*8170, di5 0.8095, dj6 0.8019, and [a]D + lo*ooo at go, +9.51' at26.5', + 9.40' at 35.5", + 9.19' a t 48', and + 8-98' at 91.5'.dl-Methyl-n-hexyZcarbinoZ.-Several investigators have observed thatordinary commercial methylhexylcarbinol (sec.-octyl alcohol) possessesa slight rotatory power. Samples supplied by Kahlbsum hada'' -0.15' in a 2-dcm. tube. This alcohol was converted into thehydrogen ph thalic ester, and recrystallised twice from glacial aceticacid and once from light petroleum. The alcohol recovered from thispurified ester possessed approximately the same rotatory power.Itmas therefore assumed that the commercial alcohol contained a smallamount of the I-alcohol. To it was then added the calculated amountof the d-alcohol, so that an inactive product was obtained. This mastreated with phthalic anhydride, and the ester purified as before. Thealcohol prepared by the hydrolysis of this thrice-recrystallised esterwas found to be completely inactive. The experiments describedbelow, in which an inactive methylhexylcarbinol mas used, werecarried out with a product prepared in this way.Esters of MetlTLyl-n-l~exylcarbinol.d-P-Octylacetate, CHs*CO2*CHMe*C0H3.-This was obtained as apleasant-smelling, mobile liquid, boiling at 86-88'/22 mm. It haddi7 0.8569, and [a]: + 7*65', whilst when hydrolysed with potassiumhydroxide it gave the optically pure d-alcohol.d-P-OctyZ P-phnylpropionate, CH,Ph*CH,*CO,*CHMe*C,H,,.-Theacid was converted into the chloride by heating on the water-bathwith the calculated amount of thionyl chloride.The product wasthen warmed with the d-alcohol until hydrogen chloride ceased t obe evolved. The oily ester was then purified in the usual manner,and it was found that redistillation did not alter its rotatory power :0-1176 gave 063354 CO, and 041036 H,O.CI7H,,O, requires C = 77.86 ; H = 9.92 per cent.The ester is a transparent and odourless liquid of somewhatviscous character, which boils at 192-196'/27 mm., and hasd:7 0.9483. The rotation observed in a 1-dcm, tube gave uD + 114560,whence [a]: -t-12.19'. A second preparation, made by the methodof saturating a solution of the acid in the d-alcohol with hydrogenchloride, had [a]: -t- 12.26'.The corresponding Zaevo-compound was prepared in a similar mannerby the first of the methods indicated above.It boils at 200-202@/32 mm., and has dI7 0'9476. I n a 1-dcm. tube it gave aD - l l * 8 5 O ,whence [a]:- 12.51'. From each of these two esters there werqC = 77-78 ; H = 9.80OF ROTATORY POWER ON CBEMICAL CONSTITUTION. PART 1. 67recovered, by hydrolysip, alcohols with [u?: 9 ~ 9 ~ . The correFpondinginactive ester boils at 190--192O/27 mm., and has di7 09315.Esters of Cinnamic Acid. -Theso mere prepared by passing hydrogenchloride for forty-five minutes through a mixture of equivalentproportions of the alcohols and cinnamic acid, which was kept at 110".The esters were purified in the usual manner, and were obtained asclear, colourless liquids without odour.The d-p-octyl cinnamate thus prepared boiled at 21So/2S mm., had~l:~0*9694, and in a 50-mm.tube + 19*48", whence [a]: + 40.19".The alcohol recovered from this ester had [u]: +9*66". The ester,which wae quite free from chlorine, when repeatedly treated withaluminium smaIgam in moist ethereal solution was quantitativelyconverted into the corresponding ester of P-phenylpropionic acid,which had [u]; + 12.36O.The corresponding Zaevo-ester boiled a t 21 1°/23 mm., had di7 + 0.9692,alid [u]: - 39-78", whilst the dl-eater boiled at 2 13"/28 mm., and haddi7 0.9715 :0.1261 gave 0.3620 CO, and 0.1065 H,O.C17H2402 requires C = 78*46 j H = 9.23 per cent.E8ters of Phenylpropiolic Acid.-The esters of phenylpropiolicacid were prepared in the same manner as those of cinnamic acid.They were obtained free from chlorine, and when hydrolysed gavethe optically pure alcohols. They are colourless, highly refractiveliquids, which possess faint odours, The d-ester boiled at 206--308"/20 mm., had d:' 0.9823, and in a 50-mm. tube gave u17" + 24*95O, whence[a]: + 50.80". Repeated treatment with aluminium amalgam in moistethereal solution converted the unsaturated ester into the correspondingderivative OF P-phenylpropionic acid, which had [a]: + 13.06". TheE-ester boiled at 209'/37 mm,, had di7 0.9719, and gave - 13.33"in a 25-mm. tubo, whence [u]; -50.75".The dZ-ester boiled at228--331*/48 mm., and had di7 0,9767.Eslers of the Tartar& Acids.--The rotatory powers of the esters ofthe tartaric acids with the methyl-n-hexylcarbinols have been deter-mined in the hope that the results might be useful in supporting theconclusions of Patterson (Trans., 1907,9 1,705) as to the non-validityof van't Hoff's theory of optical superposition. The rotatory powersobserved were not in accordance with this theory, b u t owing to the failureof all attempts to prepare the corresponding esters of i-tartaric acidthese results do not give a strict proof of its von-validity, such as Patter-son has furnished in his work on the menthyl tartrates. McCrae hasdescribed ethyl /I-octyl d-tartrate (Trans., 1901,79, 1103) and di-p-octyl d-tartrate (Trans., 1902, 81, 1231) as viscous oils with a rancidodour, and the latter as having a yellow coluur, The esters mentionedC=78*51 j H=9*38.u 68 PICKARD AND KENYON : INVESTIaATIONS ON TEE DEPENDENCEin table X have all been obtained 8s highly-refracting, colourlessliquids, somewhat viscous and practically odourless.The preparationof the di-P-octyl tartrates is readily carried out; BS follows : 40 gramsof the required methyl-n-hexylcarbinol and 10 grams of the diethylester of the tartaric acid are mixed and saturated at a temperaturebelow 0' with hydrogen chloride. After some days, the hydrogenchloride and about 5 C.C. of the mixture are distilled off underdiminished pressure on a wster-bath. The main bulk of t h e mixtureis then again saturated with hydrogen chloride as before, and kept fora week.The excess of alcohol, along with the hydrogen chloride, isnow removed by distillation under a pressure of about 20 mm., and theester carefully fractiouated under a pressure of about 6 mm. Onedistillation is generally sufficient to give a product of constant rotation,the neutral esters boiling between 302' and 210°/6 mm.In view of the discrepancy between McCrae's results and those hererecorded, specimens of di-P-oc tyl d-tartrate were prepared from Ka61-baum's alcohol (with a slight I~evorotation) and both diethyl anddimethyl d-tartrate, each preparation being found to have [u]: + 10*99",whereas McCrae's value is [u]g + 7-06". Similar preparations from thepure clLalcohol and diethyl and dimethyl d-tartrates had [a]: + 11*1$'and -+ 11.02' respectively.I n the preparation of these esters from Kahl-baum's alcohol i t was found that the rotation of the unesterified alcoholvaried slightly from that of the original sample. As purchased, it had, ina 2-dcm. tube, a - 0.14'to - 0*17', whilst the unesterified alcohol hada - 0.05' to - 0.07'. I n the course of the lengthy series of experimentssummarised on p. 48, ethyl dl-P-octyl d-tartrate was isolated. Itboils a t 187-190°/7 mm., has d i' 1.0568, and [a]:: + 8-55', a valuehigher than that recorded by McCrae (Zoc. cit.), who gives [u]E + 7.63'.Attempts to prepare the pure P-octyl esters of i-tartaric acid werefailures, these compounds apparently decomposing before distillation.*TABLE X.The Di-P-Octyl Esters of the Tmtaric Acids.Specific Rotcctory Powers and Bensitie8.&Tartaricacid.d-Methyl-n-hexylcarbinol, [a]i7 ...+ 24.062-Methyl-n-hexylcarbinol, [a]:' ... - 1-93dl-Methyl-n-hexylcarbinol, [a]'' .. , + 11 02di7 ...... 1.0165di7 ...... 1.0171di7 ...... 1.0148&Tartaric r-Tartaricacid. acid.3- 2-06 + 14'121.0081 1'0047 - 24 *20 - 14-031 -0059 1 '0058 - 11.00 -1.0069 -* The anthors are greatly indebted to Dr. M. 0. Forster, F.R.S., wlio attemptedHe found t!int violent decomposition set in to distil a sample of one of these esters.at about 160' when the pressure was ouly 0.5 nmOF ROTATORY POWER ON CHEMICAL CONSTITUTION. PARTI. 69Halides Correspo?adisag with the Methyl -n-hexylcarb ino Is.d- and Z-Methyl-n-hexylcarbinols react fairly readily with hydrogeniodide, bromide or chloride, the formation oE the halide being accom-panied by a change in the sign of the rotation, The P-iodo-octanesare obtained when the alcohols are saturated at 0" with hydrogeniodide and kept for about five hours.I n the case of the bromides andchlorides, the mixtures similarly prepaped are heated at 100" in sealedtubes for one hour.These halides are partly racemised if the reactions are not carriedout under the above conditions, higher temperatures or prolongedheating always resulting in the products formed being of lowerrotatory power, All the preparations obtained were unaltered inrotatory power after prolonged shaking with cold concentratedsulphuric acid.These active halides do not appear to undergoautoracemisation, as a specimen of LP-bromo-octane was found to beunaltered in rotatory power two and a-half years after its preparation.Various constants for these halides are given in table XI; thefollowing additional ones were determined for I-P-bromo-octane :d?'* 1.0927, 7 1.0805, :7 1.0688, and i3 1.0532; [.ID - 31-07" a t 4",- 30.33' at 13.19 - 29.05" at 30", - 28.62" at 37.4", - 27-81" at 50",- 26-56' at 69O, and - 25.18" at 92".TABLE XI.a17 inBoiling point. 47. 50-mm. tube. ;7.d-B-Bromo-octane ... i4"/18 ,, 1.0895 + 14-95 + 27'53Z-p-Chloro-octam ... 70"/25 ,, 0.8628 - 8.82 - 20'44d-8-Iodo-octane ...... 101"/22 mm. 1-3314 + 26-51" + 39-83"2-B-Iodo-octane ... .. . 92'/12 , , 1-3299 - 26 *97 - 40'567-&Hromo-octnne ... 71'/14 ,, 1.0914 - 14.99 - 27'47d-B-Chloro-octane ... 75"/28 ,, 0.8658 f 8 - 8 3 -i- 20-40Several experiments were carried out in which the halides weretreated under varying conditions with potassium acetate. Althoughin every case the resulting P-octyl acetate had a rotation opposite insign to the halide used, yet it was never obtained optically pure, someracemisation invariably taking place during the formation of theacetate, whilst possibly the halides themselves were not opticallypure70 PXCKARD AND KENYON : INVESTIGATIONS ON THE DEPENDENCEd-Metlql-n-heptyl-, d-Melhyl-n-octyl-, and d-~0thyl-n-non~l-carbinob.These were each prepared in two ways, namely, from the brucine andErom the strychnine salts of the dextrorotatory hydrogen phtbaliuesters.d-Methyl-n-heptylcarbinol boiled at 105'/19 mm., had d!s*l 0.8281,0.8202, y.z 0.8129, FS5 0.8043, :6 0.7799, and [ u ] ~ +8*98O at 19O,+8*88' a t 26.5', +8*'7lo at 34', +8*55' at 49.5', +8.44' at 66O,and +8*39" at 72'.0.8293, Y'' 0,8220, i2'3 0.8096, 0.7935, and i4' 0.7222, and [a]D + 8*74O at 17",+8*55O at 26*4", +8*37' at 35.4', +8*02' at 58*9', +7*75O at 93',and +7.81" at 146O.d-Methyl-n-nonylcarbinol boiled at 128'/20 mm.and solidified whencooled to a mass of stellate needles, which melted at 1 2 O . It haddi4 0-8318, f" 0,8226, i7'' 0.8145, f4'9 0.8017, 0.7896, and [.]I + 8.40'at 6O, + 8*18" at IS', + 8-03' at %To, + 7.88" at 35O, + 7.67O at 48*7", + 7-55' at 59', + 7 ~ 3 4 ~ at 73", and + 7.27' a t 92O.d-Methyl-n-decylcarbinoz, obtained from the brucine salt of t.hedextrorotatory hydrogen phthalic ester, boiled at 146'/24 mm., and,when cooled, set to a mass of stout, prismatic rods in a crystallinematrix. This melted at l8*7", had di2' 0.8369 (in a supercooledcondition), i7'4 0.8265, 3q8'9 0.8182, r'2 0.8090, r'6 0+3016, and [ u ] ~ + 7.80'at 19', +7*66' at 27O, +7.5l0 a t 36.5', +73*2" at 46*5', +7.1fio at57*5', + 7.00° at "lo, and + 6-88' at 93'.d-Methyl-n-undecylcccrbinol, obtained either from the brucine orstrychnine salt of the dextrorotatory phthalic ester, boiled at 156-157'/17 mm., and set to a glistening, crystalline mass of prismatic needles,which melted at 30'.It had d:'" 0.8215, 447'3 0.8109, ?'6 0.8012, and[u],, + 7-10" at 25*5O (when supercooled), + 6.98' at 33.5q + 6.74' at48", + 6-55' at 56.5', + 6-42' at 71.9', and + 6-37' at 93'.d-Methyliaobutylcarbinol was obtained from the brucine salt of thedextrorotatory hydrogen phthalic ester and from the cinchonidine saltof dextrorotstory hydrogen succinic ester.It boiled a t 65*5'/45 mm.,had dig 0.8083, :* 0.8014, :o 0.7824, y'5 0.7596, and [a], + 21.35" at 6.3',+ 2 0 ~ 8 6 ~ at 14O, + 20.4O at 21.3', + 20.04O at 29*5", + 19.69" at 38*7',+19*48O a t 43O, +19.1lo at 57", +18*65' at 73', and +18.25' at94.3'.l-Meth~liso6utyZcarbino2, obtained from the brucine salt of thelaevorotatory hydrogen succinic ester, had [u]g - 20.80".d-Ethyl-n hexylcarbinol, obtained from the brucine salt of the dextro-rotatory hydrogen phthalic ester, boiled at 97"/17 mm., had di6" 0.8281,i6.3 0.8202, :''' 0.8129, F'4 0.8043, i8'5 0.7799, and [a]D f 8.09" at 6.1'The following constants were determined :d-Methyz-n-octylcclrbinol boiled at 110-1 1 lo/ I 1 mm., haOF ROTATORY POWER ON CHEMICAL CONSTITUTION. PART I. 71+8.05" at 20*6', +8.13' at 37*8O, -1-8.14' at 4S*2', and +8.27' at70.5'.l-Ethyl-n-hexyZcarbinoZ, obtained from the cinchonidine salt of thelaevorotatory hydrogen phthalic ester, boiled at 94'113 mm., haddt7 0,8277, and [a]: - 7-96'.Table XI1 shows some of the properties of the y-chloro-, bromo-, andiodo-nonanes, which were prepared by the methods used in the case ofthe corresponding p-octane derivatives. In each case the alcoholyielded a halogen derivative with a rotatory power of opposite sign.TABLE XII.y-Halogen Derivatives of n-Nonnne.d-y-Chlorononane ............... 87-89"/24 mm. 0.8588 + 7.71"2-7- Chlorononane ............... 101"/40 ¶, 0.8540 -8.03d- y-Bromononane ............... 112"/32 ,, 1.0900 + 12.90Boiling point. di7. [.I".2-y-Bromononane ............... 96-97"/22 ,, 1.0897 -13 392-y-Iodononane .................. 122'137 9 y 1'2873 - 17.50d- y-Iodononane .................. 120"/27 ,, 1'2940 4- 17.65d-PAenyZmethyZcarbinoZ, C6H,*CH(OH)*CH,, obtained from thebrucine salt of the dextrorotatory hydrogen succinic ester, boiledat 100°/lS mm., had di3'3 1.0191, 1.0079, :g'2 lv0O19, 0.9911,y'4 0.9846, :o'2 0,9646, and [a], + 42.90' at 6', + 42-85' a t 27', + 42.74'at 36.8', + 42-69' at 47', + 42.53' a t 58', + 42.27' a t 71', and + 41w339at 94".d-PhenyZethyZcarbinoZ, obtained from the brucine salt of the dextro-rotatory hydrogen succinic ester, boiled at 115-1 16'125 mm., haddi7 0.9962, and [a]" + 27.35'.l-Pheny~ethy~caTbino~, obtained from the cinchonidine salt of thecorresponding lsevorotstory ester, boiled a t 115-1 16'/25 mm., had d:3'80.9982, F'8 0.9872, r7 0.9755, zg'5 0.9538, and [a], - 24.76' at 5*3',- 26-83' a t 15.2', - 29.07" at 27*2", - 30.34' at 35', - 33.90' at 645",and - 35-58' at 94'.The corresponding chloro-compounds were obtained when thesethree alcohols were saturated at 0' with hydrogen chloride and keptfor some hours.l-a-ChZoroethyZbenzene, C,H,*CHCl*CH,, from the dextrorotatorycarbinol, boiled at 86O/22 mm., had di7 1.0642, and [a]g - 5-80'.The Isevorotatory pheuylethylcarbinol yielded d-a-chZoropropyZbenzene,which boiled at 86--87'/15 mm., had di7 1.0429, and [a]" + 3.79'. Thecorresponding dextrorotatory chloro-compound boiled at 95'/25 mm.,and had d:7 1,0430 and [a]E - 3.87'.The authors have much pleasure in acknowledging the assistancegiven to them by Miss Annie Higson, B.Sc. (Lond.), who prepared an72 SODDY : THE CHEMLSTRY OF MESOTHORIUM.carried out many experiments with metbyletbylcarbinol, and by Mr.G. T. Bjrne, B.Sc. (Mane), who has repeated several of the resolutionsdescribed.Further, the authors desire to express their thanks to the Govern-ment Grant Committee of the Royal Society for repeated grants, whichhave partly defrayed the heavy expenses of this investigation.MUNICIPAI, TECHNICAL SCHOOL,BLACKBURN

ISSN:0368-1645    

DOI:10.1039/CT9119900045

出版商:RSC    

年代:1911

数据来源: RSC

摘要:

72 SODDY : THE CHEMLSTRY OF MESOTHORIUM.VIII.-The Chemistry of Mesothonhm.*By FREDERICK SODDY, M.A., F.R.S.MESOTHORIUM, the first product of the thorium disintegration series,and the parent of radiothorium, was discovered three years ago by0. Hahn (Ber., 1907,40, 1462). Although for the past few monthspowerfully radioactive preparations of this substance, prepared byHahn during the course of the manufacture of thorium salts frommonazite sand in the works of Dr. Knofler & Co., Plotzensee, Berlin,have been put on the market, nothing has been allowed to transpireconcerning the chemical processes by which the separation iseffected. Rutherford, in a Royal Institution Lecture (January31st, 1908), drew attention to the value of mesothorium as a possiblesubstitute for radium in many experiments, owing to the largescale on which thorium compounds are commercially manufactured.Although mesothorium is not a permanent source of radioactivity,like radium practically is, yet the period of average life, abouteight years, is sufficiently long to make it a very useful substanceif it could be prepared on a large scale.A t the beginning of thepresent year, powerful sources of thorium radioactivity were neededf o r certain experiments, and as a t that time there seemed nopossibility of obtaining it in any other way, experiments were under-taken on the separation of mesothorium from thorium minerals,commencing with thorianite.The discovery of radiothorium by Sir William Ramsay and0. Hahn, which preceded that of mesothorium, was made in thecourse of the treatment of a large quantity of thorianite for radium.The material was fused with potassium hydrogen sulphate, theinsoluble residue being treated in the same way as the radium-* Since this paper was written there has appeared a communication on the szmesubject by W.Marckwald (Ber., 1910, 43, 3420) which anticipates the discovery ofthe chomical identity of mesothorium-1 and radiumSODDY: THE CHEMISTRY OF MESOTHORIIJM. 73containing residues from pitchblende, to extract the barium aschloride. Radiothorium was discovered in this product (Sir W.Ramsay, J . Chim. Phys., 1905, 3, 617; 0. Hahn, Jahrb. Radioactiv.Elektromik., 1905, 2, 234). Subsequently a study of the chemicalproperties of radiothorium by Elster and Geitel (Physikal.Zeitsch.,1906, 7, 445) and G. A. Blanc (Phil. Mag., 1905, [vi], 9, 148), andthe work of Boltwood (Amer. J . Sci., 1907, [iv], 25, 93), resultedin the view a t present held, that radiothorium resembles thoriumcompletely and cannot be separated from it by chemical processes,and that the radiothorium prepared by Hahn was due to theseparation of mesothorium and the spontaneous production ofradiothorium from it with the lapse of time. What little is knownof the chemistry of mesothorium we owe to Boltwood, who showedthat the original process employed in the separation of thorium-X(Rutherford and Soddy, Trans., 1902, 81, 343, 837) in the filtrateafter precipitation of thorium by ammonia, separated also themesothorium.He also precipitated barium sulphate in a dilutesolution of a thorium salt, thinking that the adsorption of radio-thoriulh by the barium sulphate might explain Hahn’s results withthorianite. He found, however, that mesothorium, but not radio-thorium, was separated with the barium sulphate, and concludes :“It appears quite likely therefore that the entraining action ofbarium sulphate on mesothorium was directly responsible for thepresence of radiothorium in the thorianite residues [of Hahn].”Since Sir W. Ramsay and Hahn were dealing with a mixture ofradiothorium and mesothorium in genetic relationship, nothing canbe learnt from the original papers on radiothorium (loc. cit.) ofthe chemistry of mesothorium,” as it is uncertain throughout towhich substance the reactions apply, whilst in Hahn’s later paperson mesothorium (Zoc.cit., and PhysikaZ. Zeitsch., 1907, 8, 277) noinformation on this subject is given.Thorianite is, from the radioactive point of view, the mostcomplex material it is possible to work with, as it contains everyone of the thirty or more radioactive elements known, in importantquantity, the penetrating radiation contributed by the uraniumand thorium series being, for the specimen of thorianite examined(which contained about three times its much thorium as uranium),of very similar intensity. The thorium disintegration series, as atpresent known, is shown below to facilitate reference, and nophenomena were encountered in the course of the work which could* Thus Sir W.Ramsay, for example, in his paper “Radio-thorium” (J. Chim.Phyr., 1905, 3, 623) says, “ Le nouveau corps se prhcipite partiellement avec leradium, en ajoutant aux sels de thorium d‘abord un sel de baryum et ensuite del’acide snlfurique ; et l’on peut effectuer sa separation du radium par un desprocedes dont nous avons donne la description.’74 SODDY : TEE CHEMISTRY OF MESOTHORIUM.not readily be explained by this succession of changes and by theknown changes in the radium series.Throughout, y-ray methods of measurement with lead electroscopes (Soddy and Russell, Phil. Mag., 1910, [vi], 19, 752) have beenemployed whenever possible, as by these means the difficulty ofcomparing toget,her specimens differing greatly in density andweight is avoided.The only objection to it is that considerableamounts of material must be employed to produce effects sufficientlylarge to measure with accuracy. In dealing with monazite, st specialvery large lead cylindrical elect,roscope (22 cm. high and 22 cm.diameter) was constructed so as to give greater sensitiveness. Thelead used, which was 3 to 4 mm. thick, was taken from the roof of avery old building, in which any radielead initially present wouldhave decayed (Ann. Reports, 1906,3, 365), so that the natural leakmight be as small as possible. A very It proved very successful.complete study of the y-radiation of the various radio-elements, inconjunction with Mr. Russell, has recently been concluded, and thesection dealing with the y-rays of thorium has appeared in thePhilosophic& Magazine (1911, [vi], 21, 130).It suffices to state herethat the two thorium types of y-rays, from mesothorium-2 andthorium-D, both in penetrating power and in the ratio of theirintensity to that of the accompanying &rays, are extremely similarto the radium type of y-rays which are given by radium-C.Radium-C, mesothorium-2, and thorium-D, alone of all the knownradioactive constituents, give y-radiation of sufficient intensity toaffect the measurements. When &ray methods are employed, thepossible effects due to uranium-X, radium-&’, and, perhaps,actinium-C must also be remembered, but the y-rays from thesesubstances are negligible. In all measurements of y-rays, thepreparations were contained in sealed tesbtubes, so as to retain theradium emanation completely.In spite of the complexity ofthorianite, no difficulty was ever experienced in deducing from thevariations of the y-activity with time the radioactive constituentspresent and their relative amount, although two of the periodSODDP : THE CHEMISTRY OF MESOTHORIUM. 75(those of the radium emanation and thorium-X) controlling they-ray variations are identical.For the specimen of thorianite worked with, moreover, they-activity contributed by thorium-D was very similar in intensityto that contributed by radium-C, so that, frequently, preparationsappeared to remain of constant activity for long periods, whenwhat was really taking place was a simultaneous complete decay ofthorium-X (and in consequence thorium-D) and a concomitantreproduction of radium emanation (and in consequence radium-C)from the radium.The analysis of the effects was no doubt enor-mously simplified, because, as will appear in the sequel, meso-thorium-1, radium, and thorium-X appear to form a trio ofchemically non-separable elements.Experiments were started with a solution of thorianite in nitricacid by the two known methods, capable of separating mesothorium,due to Boltwood. The repeated precipitation of the solution withammonia and evaporation and ignition of the filtrate, as in tbepreparation of thorium-X, effects a complete separation in sufficientlydilute solution, but in an attempt to apply it to considerablequantities with more concentrated solutions, the separation waspartial, and the fraction separated varied capriciously.The pre-cipitation in the thorianite solution of barium as sulphate, althoughat first not very successful, was found ultimately, under properconditions, to yield good results, even in concentrated solutions theReparation being nearly complete. In one experiment 26 grams ofbarium nitrate was dissolved in a solution of 600 grams of thorianitein nitric acid, from which most of the excess of acid had beenevaporated. The solution, of volume about 1.5 litres, was put in aWinchester quart bottle, excess of dilute sulphuric acid added, andthe bottle shaken for an hour on a shaking machine. Theseparation of the mesothorium was practically complete, a secondprecipitation yielding a precipitate possessing an activity not greaterthan could be accounted for by the regeneration of thorium-X inthe time ljetween the precipitations.About 5 kilograms of thorianite were treated by this method,and the y-activity of the products, sealed up in test-tubes, was keptunder observation for some time.The first precipitate from thesolution increased rapidly in y-activity by about 50 per cent. in thecourse of two days, and then remained nearly constant. Duringfiltering and drying, mesothorium-2 is usually produced in nearlyequilibrium amount before the first measurement. The increasefor the first two days is due to the formation of thorium-D fromthorium-X. After that time the decay of thorium-X just balancedthe production of radium-C from the radium as.already explained'I6 SODDY : THE CHEMISTRY OF MESOTEORIUM.so that the activity remains sensibly constant. For the subsequentprecipitates the y-activity was due mainly to thorium-X, regeneratedbetween the precipitations, and, after reaching the maximum,steadily decayed.In this way, from the 5 kilograms of thorianite a total weight ofabout 200 grams of barium sulphates of various activities wasseparated. Up to this time it was considered, as Boltwood hadsupposed, that the mesothorium was merely adsorbed by the bariumsulphate. Uranium-X was, in a recent research (F. Soddy andA. S. Russell, PhiZ. Mag., 1909, [vi], 18, 620), frequently separatedby adsorption with barium sulphate, and was found to be readilyseparable fkom the barium after solution of the barium sulphate,by precipitating with ammonia in presence of a trace of iron.In the hope of being able t o effect a preliminary concentration ofthe mesothorium from the barium, to a portion of one of thesulphate precipitates, after conversion into chloride, a smallquantity of dilute sulphuric acid was added to precipitate a smallfraction of the barium as sulphate.The precipitate so obtained,however, was no more and no less active than the same weight oforiginal material. Other' attempts to concentrate the mesothoriumfrom the barium, chemically, failed, and the conclusion was drawnthat the separation of mesothorium with barium is due, not toan adsorption by the barium sulphate, as had previously beenassumed, but t o a chemical resemblance between the two elements.The whole of the active barium sulphate was converted intochloride by ignition with sugar-carbon in separate small quantitiesin quartz crucibles, and the barium sulphide dissolved in hydrechloric acid.The crude chlorides in acid solution were freed fromlead by hydrogen sulphide, made alkaline with ammonia, and filteredfrom the small iron and thorium hydroxide precipitate. A frac-tional crystallisation of the barium chloride was then commencedt o concentrate the radium present from the barium. The variousprecipitates had been sorted inta three grades, according to theiractivity, and worked up into pure chlorides separately. The rawmaterial for the fractionations thus comprised three preparationsof weights' 52, 69, and 105 grams, and relative activities roughlyas 5 : 2 : 1.As it was then unknown whether the separation of thebarium from the mesothorium would be possible, the fractions werenot mixed, but dissolved separately. Fractionation was carried outfor separating radium from barium in the usual way, the motherliquor of the richer fraction being used to dissolve the crystals ofthe next richest. Preliminary tests showed that the process wasvery effective in concentrating the mesothorium as well as theradium from the barium. I n a few days three fractions werSODDY : THE CHEMISTRY OF MESOTHORIUM. 77again made up, of weights 57, 97.5, and 76.5 grams. Mesothorium-2was separated from each separately by adding 10 milligrams ofthorium nitrate, and precipitating with ammonia.The relativeactivities of these mesothorum-2 precipitates were as 25.3 : 4.3 : 1.The mesothorium in equal weights of barium chloride was thereforeas 34: 3.4: 1. This showed that the mesothorium had been effec-tively concentrated by the fractional crystallisation, the crystalsbeing enriched, and the mother liquor impoverished, as in the caseof radium. The three fractions were dissolved, left for a week,then evaporated to dryness and sealed up in testrtubes, and they-activity measured over a period of six weeks, 10 grams only of thefirst fraction being taken for the test. The ratio between the initialand subsequently generated activity gives the relative proportionsof mesothorium and radium.These ratios were in order of richnessof the preparation, 0.52, 0.46, and 0.56. Hence mesothoriunifollows the radium extremeIy closely in the fractionations. Thesmall differences in the ratio, since the raw material of the frac-tionations was not homogeneous, but derived from differentquantities of thorianite, are not greater that might be accountedfor by variations in the composition of the mineral, or by thepresence, possibly, of thorium-X from regenerated radiothorium.The measurements were only rough, whereas those which followwere done with the greatest possible accuracy.In order to settle whether any alteration at all in the proportionof the mesothorium and radium was produced by fractionalcrystallisation, the most active fraction, all but the 10 gram samplesealed up for the previous tests, was refractionated as before.T'herichest fractions, withdrawn from the process after the fifth andeighth successive fractionations, were combined and labelled A A .A part of the 10 gram sample of the original material was taken,and labelled A . The two specimens were dissolved in water at thesame time, freed from mesothorium-2 by precipitation of thoriumhydroxide in the solution as before, evaporated, and sealed up.A weighed 2.38 grams, and A A 2-09 grams. The y-rays werecompared after two days, when mesothorium-2 is again in equi-librium, and at intervals subsequently. The measurements givethe means of telling exactly whether any alteration in the ratio ofthe radium and mesothorium has been effected by the furtherfractionation.Fraction A A proved to be 8'75 times as active as fraction A ,showing that a concentration of the active material in the ratio10: 1 had been effected.Nevertheless, the proportions of radiumand mesothorium in the two preparations were identical. Theratio of the activities remained unchanged within the error o78 SoDbY : THE CHEMlSTRTt OF MI&OfHORIuM,measurement, which may be estimated at less than 2 per cent., overthe period from the first day after preparation onward, duringwhich the activity more than doubled, owing to the accumulationof the radium emanation. In order the more accurately to comparethe two preparations, measurements were taken not only of the twoin the same position beneath the electroscope, but also of thestronger preparation at a greater distance, so that the effectscompared should be of the same order.The following table showsthe actual readings of the electroscope in divisions per minute,corrected for the natural leak (about 4*8), and the ratio betweenthem for the two positions.Day. Fraction A . Fraction AA. Ratios. - - 1st ............... 10.5 91-5 12-05 8.7 1'142nd ............ 13.1 115.0 14'95 8-8 1'143ra ............ 15.0 133.0 17.35 8.85 1'157th ............ 19 -65 170.8 22-3 8.7 1-1334th ............ 26 *O 224.0 29.5 8.6 1-1413th ............ 23.9 203.0 26-6 8.5 1-12The fractionation process, from which the fraction A A wmderived, was continued until twenty-four sets of fractionations hadbeen performed.The products were then combined in two finalfractions, the one, labelled C, consisting of the weak, and the other,labelled B, of the rich fractions. Thus the most active fractionof the original material was obtained in three fractions, A A , B,and C, the weights of which were 2-09, 2.27, and 38 grams respec-tively, and the relative activities as 4.6 : 3-85 : 1. The concentrationsof the raaioactive matter in the three fractions were therefore aa84: 64: 1. Fractions B and C were kept dissolved in water forsome days, so that mesothorium-2 should be initially in equilibrium,then evaporated to dryness, sealed up in test-tubes, measured imme-diately, and again after twenty-one days. The relative activity ofthe two fractions was exactly the same in the two tests, showingthat the fractionation process which had altered the concentrationof the radioactive matter sixty-two times had not affected the ratioof the two radioactive constituents.For each fraction the prcr-portion of the activity contributed by the mesothorium wits almostexactly onehalf that contributed by the radium, which is practicallythe same as that found initially.This experiment proves conclusively therefore that in the frac-tional crystallisation of barium chloride, containing mesothoriumand radium, the mesothorium and radium behave as a singlesubstance, and there is no hope of separating them by this method.With the knowledge gained of the chemical nature of rn-6thorium, a good many further experiments were done on itSODDP : THE CHEMISTRY OF MESOI'BORIUM.79separation from thorianite, which need not be detailed. They allbore out the view that mesothorium and barium are chemicallyanalogous. It was found that a practically complete separation ofthe mesothorium and radium from thorium in the thorianitesolution could most favourably be effected by adding a smallquantity of barium nitrate and a considerable quantity of strongnitric acid, and precipitating the thorium with oxalic acid in thestrongly acid solution. The mesothorium is precipitated from thefiltrate by pouring it into excess of sodium carbonate solution(which keeps the uranium dissolved), and recovered from thesolution of the precipitate in nitric acid by precipitating the bariumwith sulphuric acid.I n the first experiment with monazite sand, 400 grams weredissolved, by heating it with twice its weight of sulphuric acid andstirring the product with cold water, exactly as in the technicalworking up of the material.The muddy liquor obtained wasdecanted from the unattacked sand, which constituted about 20 percent. of the whole, and left to deposit its sediment. This weighed4.8 grams, and consisted largely of calcium sulphate. It waslabelled A . One gram of barium nitrate was dissolved, and addedslowly to the clear monazite solution, with efficient stirring. Theprecipitate (labelled B ) weighed 1.8 grams. Tested by y-raymethods, the undissolved sand retained about 4.5 per cent.of thetotal activity of the material, The &activities of the sediment Aand precipitate B were as 1 to 3 initially, and as 1 to 2 after fortydays. Thus, under the ordinary conditions of the thorium manu-facture, an important part of the mesothorium is lost in the insolublesediments. The chemical behaviour of mesothorium, as is to beexpected, is indefinite in the absence of sufficient barium to bequantitatively separable. Monazite contains much less uraniumand therefore radium, relatively t o thorium, than thorianite, andthe y-rays of the preparation B in consequence fell to about halfits maximum value in the course of a month, owing to the effectof the decay of thorium-X exceeding the growth of radium-C.Further experiments with 400 and 800 grams of monazite sandwere made as before, except that about 0.1 per cent.of bariumcarbonate was mixed with the sand before heating. The sedimentobtained from the muddy solution now contained practically all themesothorium and radium in the monazite. One such Bediment,from 800 grams of monazite sand, weighed 14.5 grams and containedpractically the whole of the mesothorium in the material. Itsy-ray activity a t the maximum, three days after preparation, wasabout 70 per cent. of that of the original material. The unattackedsand retained 8 per cent, A further precipitate of 1.6 grams o80 SODDY : THE CHEMISTRY OF MESOTHORlUM.barium sulphate formed in the clear monazite solution possessed asmall initial activity, due to regenerated thorium-X only, whichalmost completely decayed in the course of a month.Certainlyless than 5 per cent. of the mesothorium in the sediment was present.As throughout the work thorium-X, mesothorium, and radium havealways been separated together, the presence of thorium-X andabsence of mesothorium in this precipitate may be regarded as clearevidence that practically the whole of the mesothorium can beseparated from monazite by the method described. They-radiation of the main sediment fell to about 57 per cent. of itsmaximum value after a month, as the effect of the decay ofthorium-X overpowers the increase due to the generation ofradium-C.I n the course of two or three years it is t o be expected thatthe preparation will rise in activity to somewhat more than itsinitial value, due to the regeneration of radiothorium, and in con-sequence thorium-X (and also of radium-C, which does not con-tribute to the initial activity). Then it will decay exponentially,with the period of mesothorium-1, to the constant small proportioncontributed by the radium.A part of this sediment was boiled with sodium carbonate, washedfree from sulphates, and dissolved in hydrochloric acid.It left aninactive residue, mainly silica, whilst from the solution practicallythe whole of the radioactive matter was precipitated with thebarium chloride by saturating it with hydrogen chloride. This isfurther evidence of the resemblance between mesothorium andradium. All the methods effective in the concentration of thelatter which were tried serve equally well for mesothorium.In going over all the measurements, which refer t o more thanthirty preparations, the activity of which was kept under observationfor a month or longer, there is clear evidence also that thorium-Xis always separated in any chemical operation in the same pro-portion as mesothorium and radium.It appears that the behaviourobserved by Boltwood for the one reaction, precipitation withammonia, is general. Certain apparent exceptions shown in thepreparations measured were found, on referring back to the detailsof the separation, to be due to a lapse of time after the thorium-Xhad been separated from the mineral before the first measurement.In these circumstances, owing ts the decay of the thorium-Xafter separation, its proportionate activity compared with that ofmesothorium and radium appears low.Although no separateexamination of the point has been made, there is good reason tobelieve that mesothorium, radium, and thorium-X are a chemicallyinseparable trio. It should be mentioned, however, thaSODDY : THE CHEMISTRY OF MESOTHORIUM. 81G. Hoffmann (Yhysikal. Zeitsch., 1907, 8, 553), from a comparisonof the coefficient of diffusion and ionic mobility of thorium-X insolution, deduced from Nernst’s theory that the thorium-X ion issingly charged, and is therefore univalent. The conditions underwhich the radioactive measurements were carried out, however,were very far from definite. I n the more recent work of Stromholmand Svedberg (Zeitsch.anorg. Chem., 1909,61, 338; 63,197), someimportant additions have been made to the chemistry of the radio-elements. The method employed was new and ingenious. Bycrystallising various salts in solutions containing radioactive con-stituents, they sought to determine to which of the known elementsthe radio-elements were isomorphous. They concluded that nodifferences existed, even from the quantitative point of view,between thorium-X, actinium-X, and radium. So far as thorium-Xis concerned, this agrees perfectly with the results given in thispaper. They point out that in the thorium, actinium, and uranium-radium series the three emanations are identical chemically, beingmembers of the family of inert gases. The preceding members,t.horium-X, actinium-X, and radium, are again identical, all beingmembers of the alkaline earth family.Next to these come radio-thorium, radioactinium, and ionium, which are all similar, but theyare inclined to put in the Periodic Table the respective groupsionium, uranium-X, radieuranium ; radioactinium, actinium ; andradiothorium, mesothorium, thorium, as analogous to the rare-earthgroup lanthanum to ytterbium, as follows :0. 1. 2. 3-4.5th Period ...... Xe 0 s Ba La-YbRaEm - Ra Ionium (UX, RaU)ThEm - ThX RaTh,MsTh,ThAcX RaAc,AcTheir work on mesothorium is indefinite and in disagreement, forthe most part, with the results in this paper, that mesothorium-lis identical chemically with radium and thorium-X. For examplethey state that ammonia precipitates all elements of the thoriumseries except thorium-X, and that mesothorium is not precipitated,like radium, along with barium sulphate, citing in support of thislast some experiments, which, in their second paper, they withdrawbecause they have not been able to repeat them.It is clear thatthe chemical identity of mesothorium with radium completelynegatives the above attempt to bring the radio-elements into thePeriodic Table. The elements radiothorium, mesothorium, thoriumsuggest anything rather than the rare-earth group lanthanum toytterbium.It appears that chemistry has to consider cases, in directVOL. XCIX. 82 SODDY : THE CHEMISTRY OF MESOTHORIUM.opposition to the principle of the Periodic Law, of complete chemicalidentity between elements presumably of different atomic weight,and no doubt some profound general law underlies these newrelationships.Apart from the case of the three emanations, forwhich chemical identity is necessarily a common property of thewhole group, we have, in addition t.0 the case of radiolead (210.4)and lead (207*1), which are chemically inseparable, two well-definedgroups of triplets : (1) Thorium (232*4), Ionium (230*5), Radio-thorium (228.4) ; (2) Mesothorium-1 (228*4), Radium (226*4),Thorium-X (224.4), in which the chemical similarity is apparentlyperfect. The atomic weights, estimated, for the unknown cases, bysubtracting from the atomic weight of the parent substance theknown number of helium atoms expelled in their formation, showa regular difference of two units between the successive members ofthese two groups.The first group consists of quadrivalent elementsof the fourth vertical column and the second of bivalent elementsof the second column of the Periodic System, and yet the atomicweight of the last member of the first, and first member of thesecond, group are, as f a r as is known, the same.The chemical identity of the members of the above two groupsis almost certainly much closer than anything previously known.I n the rare-earth group, elements with neighbouring atomic weightaare often so closely allied that they can only be separated after themost laborious fractionation, and distinguished by the differencein their equivalents. But as the latter are always very close, thetest is a very rough one in comparison with what is possible forradio-elements.Take, f o r example, the case of ionium and thorium.Boltwood, Keetman, and, lastly, Auer von Welsbach have all failedcompletely to concentrate ionium from thorium, the latter after amost exhaustive examination, in which his unrivalled knowledgeof the rare-earths was supplemented by the new, powerful methodsof radioactive analysis (Mit teilungen. der Radium Rommission, VI,Sitzzcngsber. K. Akad. Wiss. Wien, 1910, 119, ii, a, 1). Thequestion naturally arises whether some of the common elementsmay not, in reality, be mixtures of chemically non-separable elementsin constant proportions, differing step-wise by whole units in atomicweight.This would certainly account for the lack of regularrelationships between the numerical values of the atomic weights.The examples given include all the known radio-elements withperiods of average life longer than a year, except uranium," whilstfor this element the fact that it alone gives two a-particles peratom disintegrating, which probably are not derived from two* Actinium can hardly be considered in this connexion as its chemistry is stillrelatively imperfectly knownSODDY : THE CHEMISTRY OF MESOTHORLUM. 83rapidly succeeding changes on account of the lowness of their range,is good ground for considering that uranium may also be a mixtureof two chemically non-separable elements in constant proportiondue to their genetic relationship, differing in atomic weight by fourunits.On this view, uranium may be analogous to thorium andradiothorium, except that there is no intermediate product ofdifferent chemical nature to reveal their separate identities.It is natural that relationships such as these, even if they weregeneral, should a t first appear to be confined to the longer-livedradbelements. For the shorter-lived substances, not only onaccount of the evanescent character of the material is it difficult todetermine their true chemical nature. Adsorption plays a muchlarger part in the separation of the short-lived products than itdoes in the case of the longer-lived. The reason is not far to seek.Radioactivity is a function, not of mass, but of mass divided bythe period of average life. Thus a given amount of an adsorbentmay be able to adsorb similar amounts of two radioactive substancesbefore becoming saturated. I f , however, the one is much longerlived than the other, when quantities, not equal, but possessingsimilar radioactivity are acted on, the separation may be practicallycomplete for the shorter-lived substance, and for the other prac-tically inappreciable.* Polonium, although its period of average lifeis less than a year, has well-defined chemical properties, which havebeen elucidated by the exhaustive investigations of Mme. Curie andMarckwald. It will be interesting to see whether it does not proveto be identical with the still non-isolated " di-tellurium " ofMendelbeff, for the existence of which some recent evidence isforthcoming (W. R. Flint, Anzer. J . Sci., 1910, [iv], 30, 209). Itwould a t least be interesting to a.pply to the supposed mixtures oftellurium and di-tellurium the methods uscd by Marckwald inseparating polonium from tellurium.I desire to acknowledge the capable assistance of Mr. W. T. Munroin the preparation of the purified active barium chloride fromthorianite.PHYSICAL CHEMISTRY LABORATORY,UNIVERSITY OF GLASGOW.' This point of view also explains a t once the remarkable observation of Bitzel(Zeitsch. pAplsikaZ. Chem., 1909, 67, 725) that a trace of thorinm sulphate completelyprevents the adsorption of uraninm-X by charcoal. For, according t oand Keetman, uranii1m.X is coinpletely analogous cliemically to thoriumbe separated from it.Marckwaldand cannot2

ISSN:0368-1645    

DOI:10.1039/CT9119900072

出版商:RSC    

年代:1911

数据来源: RSC

摘要:

84 ALPERN AND WEIZMANN: ATTEMPTS TOIX .-At tempts to Pyepare Glyce Tidesacids.PREPAREof Amino-By ROMAN ALPERN and CHARLES WEIZMANN.THE intention of the authors in commencing this work was to prepareglycerides of the simple amino-acids, for example, triaminotriacetin,NH,-CH2*CO*O*CH(CH,=O~CO*CH2*NH,),, since in all probabilitysubstances of this nature would possess great physiologicalimportance.The direct combination of glycerol and glycine was found to beimpossible, and while experiments in this direction were proceeding,Abderhalden (Zeitsch. physiol. Chem., 1910, 65, 53) published theresults of experiments on the same lines, from which he drew thesame conclusion.The combination of a-halogen substituted acids with glycerol wasthen carried out, with the ides of subsequent< displacement of thehalogen by the amino-group.EXPERIMENTAL.Preparation of Trichlorotm'acetin.It was found that the preparation could be carried out con-veniently in two ways:(1) Direct condensation of chloroacetic acid and glycerol by meansof zinc chloride:Chloroacetic acid (3 mols.), freshly distilled, is dissolved inglycerol (1 mol.). To this mixture is added zinc chloride (3 mols.),and the whole is heated on the water-bath for five hours.Wateris then added, the trichlorotriacetin extracted with ether, theethereal solution washed with water, then with sodium carbonatesolution, dried, and distilled. The yield is 60 per cent. of thetheoretical.Trichlorotrkcetin is a colourless, viscid oil, with a bitter taste;it boils at 205-208°/10 mm.:0.1098 gave 0.1334 CO, and 0.0376 H,O. C = 33.1 ; H = 3.8.C,H,,OGCl, requires C = 33.5 ; H = 3-4 ; C1= 33-0 per cent.By condensing glycerol with bromoacetic acid in molecularquantities in an exactly similar manner, a-monobromaacetin,OH*CH,=CH(OH)*CH,*O*CO.CH,Br, is obtained. This is a yellowoil, possessing a bitter taste, and boiling at 217-219°/10 mm. :0.1526 ,, 0,2050 AgC1. Cl=33*0.0.1555 gave 0.1670 C.0, and 0.0560 H,O. C = 28.4 ; H =4-0.C,H,04Br requires C = 28.1 ; H = 4.2 per centGLYCERIDES OF AMINO-ACIDS. 85(2) By the action of dry hydrogen chloride on a mixture ofglycerol and either chloroacetyl chloride or chloroacetic anhydride :Dry hydrogen chloride is passed into a mixture of glycerol andeither chloroacetyl chloride or chloroacetic anhydride until, in thefirst case, a homogeneous, viscous mass is obtained, and, in thesecond, two layers separate. Water is then added, and the tri-chlorotriacetin isolated as before.This method is also applicable to the preparation of triacetin, avery good yield being obtained.aar-Dipro pionin.Propionic anhydride (2 mols.) and glycerol (1 mol.) are condensedas described above.A colourless, mobile liquid is obtained in 45per cent. yield, which possesses an aromatic odour, but also recallsthat of propionic acid. It’ boils at 170-173°/10 mm.:0.1174 gave 0.2264 CO, and 0.0826 H20.The displacement of the halogen in trichlorotriacetin by the amino-group was not found possible under the conditions employed.Dry gaseous ammonia, even at, Oo, hydrolyses the ester with theproduction of glycol and chloroacetamide.On boiling trichlorotriacetin in xylene solution with potassiumphthalimide, reaction evidently took place.There was an abundantseparation of potassium chloride, but from the viscous mass left bythe evaporation of the xylene, nothing definite except phthalimidecould be isolated.C=52*6; H=7.8.C9HI6O5 requires C=52*9; H = 7 . 8 per cent.aa’-Diacetoacetin, OH*CH(CH,* 0 COD CH2Ac)2.I n the hope of obtaining B-amino-derivatives of the glycerides,ad-diacetoacetin was prepared by condensing ethyl acetoacetatewith glycerol by means of concentrated sulphuric acid.To a mixture of glycerol (10 grams) and ethyl acetoacetate (30grams), 40 to 50 drops of concentrated sulphuric acid are addedvery slowly with constant shaking.After ten minutes, the twolayers should have disappeared, and warming gently to about 50°facilitates this. I f the layers do not now mix, a few more dropsof sulphuric acid are added. The mixture is then kept for twelvehours; after i t has been extracted with ether, the yellow etherealsolution is washed with a little water, dried, and distilled:0.0926 gave 0.1762 CO, and 0.0666 H20.aa’-Diacetoacetin is a viscid, yellow oil, boiling a t 157-160°/It isC = 51.7 ; H = 7.9.C,,R,,O, requires C = 52.9 ; H = 7.8 per cent.14 mm., with an odour resembling that of ethyl acetoacetate86 ATTEMPTS TO PREPARE OLY CERIDES OF AMINO-ACIDS.insoluble in sodium carbonate solution, and gives a reddish-browncoloration with ferric chloride.An attempt was then made to condense ad-diacetoacetin withethyl glycine (compare Fischer, Ber., 1901, 34, 433).A very small quantity of a substance was obtained, which wasneither the product of condensation of ad-diacetoacetin and ethylglycine nor diketopiperazine, but the amount was too small to permitof further investigation.I f , instead of concentrated sulphuric acid, a stream of dryhydrogen chloride is used as a condensing agent, aP-dichlorohydrincondenses with ethyl acetoacetate to form a8-dichloro-a'-acetoacetilz,which is a yellow oil, boiling at 103-105°/14 mm.:0.1230 gave 0.1778 CO, and 0.0554 H,Q. C=39*4; H=4*9,C7H1003C12 requires C = 39.4 ; H = 4.6 per cent.N-Allylglycine and its Ethyl Ester.Attempts were also made to combine various derivatives of glycerolwith ethyl glycine.Epichlorohydrin, dichlorohydrin, and acrolein did not condensewith ethyl glycine under all the conditions employed by the authors.Allylamine, however, readily condenses with ethyl bromoacetateto form ethyl N-allylgly cine, CH,:CH* CH,*NH*CH,*CO,E t.The condensation is carried out as follows. The calculatedquantity of allylamine is added to ethyl bromoacetate in etherealsolution in small quantities at a time, the whole being cooled to Oo.A t the end of an hour a 33 per cent.solution of sodium hydroxideis added, and then dry potassium carbonate until the aqueous layeracquires a syrupy consistency. This is extracted several times withether, the ethereal solution dried, and distilled.The ester boils at75--78O/15 mm. :0.0586 gave 0.1248 CO, and 0.0498 H,O.0.1383 ,, 11.5 C.C. N, at 19O and 756 mm. N=9*5.0.1184 ,, 10.1 C.C. N, ,, 18O ,, 756 mm. N=9.8.The best yield of the corresponding acid was obtained by ,C =58*1; H =9*4.C,H,,O,N requires C = 58.7 ; H = 9.1 ; N = 9.8 per cent.hydrolysing the ester with methyl-alcoholic barium hydroxide. Thebarium is precipitated as sulphate, and the filtrate evaporated todryness in a vacuum. The residue is extracted with water, and thesolution evaporated to dryness in a vacuum. The productKNIGIIT AND RICE : ISOMERIC CHROMOUS CELOBIDES. 87N-allylglycine, separates from methyl alcohol as a colourless,crystalline powder, melting at 158-159O :0.1189 gave 12.8 C.C. N2 a t 15O and 752 mm.I n order to obtain a characteristic derivative of the acid, both thea- and B-naphthalenesulphonyl derivatives were prepared.N-a-nlTaphth.ale~eszcZ~honylalZylglyci~e was prepared in the usualway. It is precipitated as an oil, which solidifies only after somedays. It does not crystsllise well from water.It isprecipitated as an oil, which solidifies in a short time. It crystallisesfrom water in colourless, glistening plates, melting at 131-132O :C =58.7; H =4*92.N= 12.47.C5H,O2N requires N = 12.17 per cent.N - ~ - N a ~ h t h a l e n e s z c ~ p ~ ~ o ~ ~ l ~ Z y l ~ l y ~ i ~ e was also prepared.0.1320 gave 0.2841 CO, and 0.0585 H,O.C,,H,,O,NS requires C = 59.0 ; H = 4.9 per cent.I n conclusion, the authors wish to express their indebtedness tothe Research Fund Committee of the Chemical Society for tho grantwhich has enabled them to carry out this research.THE UNIVERSITY,MANCHESTER

ISSN:0368-1645    

DOI:10.1039/CT9119900084

出版商:RSC    

年代:1911

数据来源: RSC