摘要:

J 0 U R N A 1,OFTHE CHEMICAL SOCIETY.TRANSACTIONS.E. C. C. BALY.HORACE T. BROWN, LL.D., F.R.S.A. W. CROSSLEY, D.Sc.) Ph.D. , F.R.S.WYNDHAM R. DUNSTAN, M. A., F.R.S.M. 0. FORSTER, D.Sc., I’h.D., F.R.S.J. T. HEWITT, M.A., D.Sc., Ph.D.R. MELDOLA, F.R.S.G. T. MORGAN, D.Sc.SirW. RAMSAY, K.C.B., LL.D., F.R.S.A. SCOTT, M.A., D.Sc., F.R.S.T. E. THORPE, C.B., LL.D., F.R.S.JOHN WADE, D.Sc.@;bitor :J. C. CAIN, D.Sc., Ph.D.%ub-&;bifor :A. J. GREENAWAY.gssistant Sub-&;bitor :C. I€. DESCH, D.Sc., Ph.D.1908. Vol. XCIII.LONDON:GURNEY & JACKSON, 10, PATERNOSTER ROW,1908RICHARD CLAY & SONS, LIMITED,BREAD STREET HILL, E.C., ANDBUNOAY, SUFFOLKJ O U R N A LOFTHE CHEMICAL SOCIETY.TRANSACTIONS.E. C. C. BALY.HORACE T.BROWN, LL.D., F.R.S.A. W. CROSSLEY, D.Sc.) Ph.D., F.R.S.WYNDHAM R. DUNSTAN, M.A.) F.R.S.M. 0. FORSTER, D.Sc., Ph.D., F.R.S.J. T. HEWITT, M.A., D.Sc., P&D.R. MELDOLA, F.R.S.G. T. MORGAN, D.Sc.Sir W. RAMXAY, K. C.B., LLD., F. R.S.A. SCOTT, M.A., D.Sc., F.R.S.T. E. THORPE, C.B., LL.D., F. R.S., JOHN WADE, D.Sc.&Max :J. C. CAIN, D.Sc., Ph.D.%7b-&?Jiiar :A. J. GREENAWAY.aeeietrrtrt Snb-dMfar :C. H. DESCH, D.Sc., Ph.D.1908. Vol. XCIII. Part I.LONDON:GURNEY & JACKSON, 10, PATERNOSTER ROW.1908RICHARD CLAY dt SONS, LIMITED,BREAD STREET HILL, E.C., ANDBUNGAY, SUFFOLKJ O U R N A LOFTHE CHEMICAL SOCIETY,TRANSACTIONS.E. C. C. BALY.HORACE T. BROWN, LL.D., F.R.S.A. W. CROSSLEY, D.Sc., Ph.D., F.R.S.WYNDHAM R.DUNSTAN, M.A., F.R.S.M. 0. FOKSTER, D.Sc., Ph.D., F.R.S.J. T. HEWITT, M.A., D.Sc., Ph.D.R. MELDOLA, F.R.S.G. T. MORGAN, D.Sc.SirW. RAMSAY, K.C. B., LL. D., F.R.S.A. SCOTT, M.A., D.Sc., F.R.S.T. E. THORPE, C. B., LL. D., F.R.S.JOHN WADE, D.Sc.ebitor :J. C. CAIN, D.Sc,, Ph.D.S,ub-&bifar :A. J. GREENAWAY.2JssistatTt Snb-@bitar :C. H. DESOH, D.Sc,, P1i.D.1908. Vol. XCIII. Part 11.LONDON:GURNEY & JACKSON, 10, PATERNOSTER ROW,1908RICHARD CLAY & SONS, LIMITED,BREAD STREET HILL, E.C., ANDBUNOAY, SUFFOLXC O N T E N T S .PAPERS COMMUNICATED TO THE CHEMICAL SOCIETY.PA GEI. -The Relation between Unsaturation and Optical Activity.Part I. The Menthyl and Bornyl Esters of P-Phenyl-propionic, Cinnamic, and Phenylpropiolic Acids.ByTHOMAS PERCY HILDITCH .11.-Note on the Iodates and Periodates of the Alkali Metalsand the Ammonium Radicle. By THOMAS VIPOND BARKER,B.A., B.Sc. (Oxon.) . . .111.-Acylogens and Thiocarbamides.DIXON and JOHN TAYLOR .1V.-Condensation of Ketones containing the Group*CH;CO-CH :with Esters in Presence of Sodium Ethoxide. By REGINALDW. L. CLARKE, ARTHUR LAPWORTH, and ELKAN WECHSLER .V.-The Elect'rometric Determination of the Hydrolysis of Salts.By HENRY GEORGE DENHAM, M.A., M.Sc., 1851 ExhibitionScholar, University of New ZealandBy AUGUSTUS EDWARD.P--N--PP-CWV1.-Attempted Synthesis of I -Dinaphthacridines ; Con-densation of Methylene Dichloride and l-substituted-2-naphthylamines. By ALFRED SENIER and PERCY CORLETTAUSTIN .VI1.-The Direct Interaction of Aryl Halides and Magnesium.By JAMES FREDERICK SPENCER and ELEANOR MARGUERITESTOKES .* . .V1II.-The Triazo-Group. Part I. Triazoacetic Acid andTriazoacetone (Acetonylazoimide). By MARTIN ONSLOWFORSTER and HANS EDUARD FIERZ1X.-The Influence of Acids and Alkalis on the Velocity ofFormation of Acetoxime. By ERNEST BARRETT and ARTHURLAPWORTHX.-A Colorimetric Method for the Determination of SmallPercentages of Iron in Copper Alloys. By ARNOLD WILLIAMGREGORY, B.Sc. (Lond.) .XI-Derivatives of Tetramethyl Glucose. By JAMES.1151830416368728593COLQUHOUN IRVINE, D.Sc., Ph.D., and AGNE~ MARIONMOODIE, M.A., B.Sc. (Carnegie Scholar) . . 9i v CONTENTS.XI1.-Studies of Dynamic Isomerism.Part VI. The Influenceof Impurities on the Mutarotation of Nitrocamphor. ByT. MARTIN LOWRY and EGBERT H. MAGSONXII1.-Studies of Dynamic Isomerism. Part VII. Note onthe Action of Carbonyl Chloride as an Agent for ArrestingIsomeric Change. By T. MARTIN LOWRY and EGBERT H.MAGSON .X1V.-The Effect on Heat on the Alkyl Iodides, By ZELDAKAHAN, B.Sc. .XV.-Derivatives of 8-Phenylphenazothioniurn. Part I. BySAMUEL SMILES and THOMAS PERCY HILDITCHXV1.-The Velocity of Reduction of the Oxides of Lead,Cadium, and Bismuth by Carbon Monoxide, and theExistence of the Suboxides of these Metals. By FRANCISJOSEPH BRISLEE, D.Sc.XVI1.-The Formation and Reactions of Imino-Compounds.Part VI. The Formation of Derivatives of Hydrindenefrom o-Phenylenediacetonitrile.By CHARLES WATSONMOORE and JOCELYN FIELD THORPEXVII1.-The Colonr of Cupric Salts in Aqueous Solution. ByNEVIL VINCENT SIDGWICK and HENRY THOMAS TIZARDX1X.-Organic Derivatives of Silicon. Part IV. The Sul-phonation of Benzylethylpropylsilicyl Oxide and of Benzyl-ethyldipropylsilicane. By HERBERT MARSDEN, B.Sc. (Vict.),and FREDERIC STANLEY KIPPING .XX.-The Esterification Constants of the Normal Fatty Acids.By JOHN JOSEPH SUDBOROUGH and JAMES MYLAM GITTINS .XX1.-Studies in Fermentation. Part 11. The Mechanism ofAlcoholic Fermentation. By ARTHUR SLATOR, Ph.D., D.Sc.XXI1.-Studies i n the Camphane Series. P a r t . XXV. Actionof Diazomethane on the Two Modifications of isoNitroso-camphor. By MARTIN ONSLOW FORSTER and HENRY HOLMESXXII1.-The Constitution of IJmbellulone.Part 111. ByFRANK TIITIN .XX1V.-Valency. By JOHN ALBERT NEWTON FRIEND, Ph.D. .XXV.-The Oxidation of Aromatic Hydrazines by MetallicOxides, Permanganates, and Chromates. By FREDERICKDANIEL CHATTAWAY .XXV1.-The Reaction between Calcium Carbonate and ChlorineWater. By ARTHUR RICHARDSON, Yh.D. .XXVI1.-Contributions to the Chemistry of the Terpenes.Part 111. Some Oxidation Products of Pinene. By GEORGEGERALD HENDERSON and ISIDORE MORRIS HEILBRONXXVII1.-The Effect of Constitution on the Rotatory Powerof Optically Active Ammonium Compounds. Part 11. ByHUMPHREY OWEN JONES and JOHN ROBERTSHAW HILL ....PAGE10711913214515416518719s21021724225226027028028829CONTENTS. VPAGEXX1X.-The Preparation of E-Benzoin.By ALEX. MCKENZIEXXX.-The Bromination of p-Hydroxydiphenylamine. ByXXX1.-The Reducibility of Magnesium Oxide by Carbon. ByROLAND EDGAR SLADE, M.Sc. . . 327XXXI1.-Constitution and Colour of Azo-compounds. Part 11.The Salts of Para-hydroxyazo-compounds with Acids. ByJOHN JACOB Fox and JOHN THEODORE HEWITT . . 333XXXII1.-The Influence of Foreign Substances on TransitionTemperatures and the Determination of Molecular Weights.By HARRY MEDFORTH DAWSON and COLIN GYRTH JACKSON . 344XXX1V.-Malacone, a Silicate of Zirconium. By ALEXANDERCHARLES CUNMING, D.Sc. . . 350XXXV.-The Influence of Solvents on the Rotation of OpticallyActive Compounds. Part XI. Ethyl Tartrate in AliphaticIIalogen Derivatives.By THOMAS STEWART PATTERSON andDAVID THOMSON, M.A., B.Sc. (late Carnegie Researchand HENRY WREN . . 309ALICE EMILY SMITH and KENNEDY JOSEPH PREVITE ORTON . 314Scholar) . . 355XXXV1.-The Refractive Power of Diphenylhexatriene andAllied Hydrocarbons, By IDS SMEDLEY . . 372XXXVI1.-The Temperatures of Spontaneous Cry stallisation ofMixed Solutions and their Determination by Means of theIndex of Refraction. Mixtures of Solutions of SodiumNitrate and Lead Nitrate. By FLORENCE ISAAC, ResearchXXXVII1.-Amphoteric Metallic Hydroxides. Part I. ByJOHN KERFOOT WOOD . 411XXX1X.-Anomalous Behaviour of the Hydrogen-Electrode inSolutions of Lead Salts, and the Existence of UnivalentLead Ions in Aqueous Solutions. By HENRY GEORGEDENHAM, MA., M.Sc., and ARTHUR JOHN ALLMAND, M.Sc.. 424XL.-The Preparation of Conductivity M’ater. By HAROLDHARTLEY, NORMAN PHILLIPS CAMPBELL, and REGINALDHOLLIUAY POOLE . . 428XL1.-The Formation of 4-Pyrone Compounds from AcetylenicAcids. Part I. By SIEGFRIED RuHElfANN . . 431XL1I.-Researches on the Anthraquinones. By WILLIAM HENRYBENTLEY and CHARLES WEIZMANN . . 435XLT1I.-Organic Derivatives of Silicon. Part V. Benzyl-ethylsilicone, Dibenzylsilicon, and other Benzyl and Benzyl-ethyl Derivatives of Silicane. By ROBERT ROBISON, B.Sc.,and FREDERIC STANLEY KIPPING . . 439XL1V.-Organic Derivatives of Silicon. Part VI. The Optic-ally Active Sulphobenzylethylpropylsilicy 1 Oxides. ByFREDERIC STANLEY KIPPING . . 457Fellow of Somerville College .. 38vi CONTENTS.XLV.-The Metallic Picrates. By OSWALD SILBERRAD, Ph.D.,and HENRY ABLETT PHILLIPS .XLV1.-Brazilin and HEmatoxylin. Part VIII. Synthesisof Brazilinic Acid, the Lactones of Dihydrobrazilinic . andDihydrohaematoxylinic Acids, Anhydrobrazilic Acid, &c.The Constitution of Brazilin, Haematoxylin, and theirDerivatives. By WILLIAM HENRY PERKIN, jun., andROBERT ROBINSON .XLV1I.-The Crystal Form of Halogen Derivatives of Open-chain Hydrocarbons with Reference to the Barlow-PopeTheory of Structure, By FRANS MAURITS JAEGER, Ph.D. .XLVII1.-The Residual Affinity of the Coumarins and Thio-coumarins as shown by their Additive Compounds. ByARTHUR CLAYTON, B.Sc. .XL1X.-Colour and Constitution of Azomethine Compounds.Part I.By FRANK GEORGE POPE .L.-Some Physico-Chemical Properties of Mixtures of Pyridineand Water. By HAROLD HARTLEY, NOEL GARROD THOMAS,and MALCOLM PERCIVAL APPLEBEY .L1.-The Viscosity of Aqueous Pyridine Solutions By ALBERTERNEST DUNSTAN and FERDINAND BERNARD THOLE .LI1.-The Action of Thionyl Chloride and of Phosphorus Penta-chloride on the Methylene Ethers of Catechol Derivatives.By GEORGE BARGER .PartXII. Synthesis of Terpins, Terpineols, and Trepenes de-rived from Methylisopropylcyclopentanes, Me*C,H;CHMe,.By WALTER NORMAN HAWORTH and WILLIAM HENRYL1V.-A P-Lactonic Acid from Acetone and Malonic Acid. ByANDREW NORMAN MELDRUM (Carnegie Research Fellow) .LV. -Deri vat ives of para-Diazoiminobenzene. By GILBERT T.MORGAN and FRANCES M.G. MICKLETHWAITLV1.-A Study of the Diazo-reaction in the Diphenyl Series.By GILBERT T. MORGAN and FRANCES M. G. MICKLETHWAITLVI1.-The Action of Mustard Oils on the Ethyl Esters ofMalonic and Cyanoacetic Acids. By SIEGFRIED RUHEMANNLVIIL-Substituted Dihydrobenzenes. Part 11. 1 :I-Di-methyl-A2’4-dihydrobenzene and 1 : 1 Dimeth~l-A~:~-dihydro-benzene. By ARTEIUR WILLIAM CROSSLEY and NORARENOUF, Salters’ Research Fellow .L1X.-The Affinity Constants of Bases as Determined by theAid of Methyl-orange. By VICTOR HERBERT VELEY .LX.-Traces of a New Tin-group Element in Thorianite. ByCLARE DE BRERETON EVANS .L1II.-Experiments on the Synthesis of the Terpenes.PERKIN, jun. . . . ..PAGE47448951752453253856156357359860261462 162965266CONTENTS. viiPAGELXT.-The Triazo-Group.Part 11. Azoimides of PropionicEster and of Methyl Ethyl Ketone. By MARTIN ONSLOWFORSTER and HANS EDUARD FIERZLXI1.-A New Form of Pyknometer. By WILLIAM ROBERTBOUSFIELD, M.A., K.C. .LXIIL-Para- and Meta-nitrosoacetanilide. By JOHN CANNELLCAIN .LX1V.-The Constitution of ‘‘ Thiocyanates ” containing anElectronegative Group. By AUGUSTUS E. DIXON andJOHN TAYLOR .LXV.-The Relation between Unsaturation and Optical Activity.Part TI. Alkaloid Salts of Corresponding Saturated andUnsaturated Acids. By THOMAS PERCY HILDITCH .LXVI .-The Action of Heat on a-Hydroxycarboxylic Acids.Part IV. Racemic aa’-Dihydroxyadipic Acid and meso-aa’-Dihydroxyadipic Acid, By HENRY RONDEL LE SUEUR .LXVI1.-The Wandering of Bromine in the Transformation ofNitroaminobromobenzenes.By KENNEDY JOSEPH PREVIT~~ORTON and CONSTANCE PEARSON .LXVII1.-The Action of Thionyl Chloride on the MethyleneEthers of Catechol Derivatives. Part 11. Piperonyloin,Piperil, and Hydropiperoin. By GEORGE BARGER andARTHUR JAMES EW~NS .LXIX.-The Solubility of Iodine in Water. By HAROLDHARTLEY and NORMAN PHILLIPS CAMPBELL .LXX.-The Sulphination of Phenolic Ethers and the Influenceof Substituents. By SAMUEL SMILES and ROBERT LEROSSIGNOL . * . . ..ANNUAL GENERAL MEETING .PRESIDENTIAL ADDRESS .LXX1.-Orthobromophenols and Some Bromonitrophenols. ByPHILIP WILFRED ROBERTSON .LXXI1.-The Optical Activity of Compounds having SimpleMolecular Structure. By WILLIAM JACKSON POPE andJOHN READ .LXXII1.-The Action of Potassium Sulphide on PotassiumTetrathionate in Aqueous Solution.By ARTHUR COLEFAX,M.A., Barrister-at-Law .LXX1V.-The Displacement of Halogen in 1-Phenylchloroacet’icAcid by Hydroxy- and Methoxy-groups. A Contributionto the Chemistry of the Walden Inversion. By ALEX.MCKENZIE and GEORGE WILLIAM CLOUGH .LXXV.-The Spontaneous Crystallisation of Sodium SulphateSolutions. By HAROLD HARTLEY, BERNARD MOUAT JONES,and GEORGE ADRIAN HUTCHINSON .66967968168470071672573574174576 377478879479881 182viii CONTENTS.LXXV1.-The Existence in Aqueous Solutions of a UnivalentCadmium Ion, a Subvalent Thallium Ion, and a BivalentBismuth Ion. By HENRY GEORGE DENHAM, M.A., M.Sc.,1851 Exhibition Scholar, University of New Zealand .833LXXVI1.-The Condensation of Epichlorohydrin with Phenols.By DAVID RUNCIMAN BOYD and ERNEST ROBERT MARLE . 838LXXVIIL-Constitution OF Hydroxyazo-compounds. Actionof Diazomethane and of Mercuric Acetate. By CLARENCESMITH [and, in part, ALEC DUNCAN MITCHELL] . . 842LXX1X.-The Quantitative Conversion of Aromatic Hydr-azines into Diazonium Salts. By FREDERICK DANIELCHATTAWAY . . 852ByJAMES FREDERICK SPENCER and MARGARET LE PLA . . 858Tsolationof a New Terpene (Origanene). By SAMUEL SHROWDERPICKLES, M.Sc. . . . . S62LXXXI1.-The Molecular Complexity of Amides in VariousSolvents. By ANDREW NORMAN MELDRUM and WILLIAMERNEST STEPHEN TURNER . . 876LXXXII1.-The Constituents of Olive Leaves.By FREDERICKBELDING POWER and FRANK TUTIN . . 891LXXX1V.-The Constituents of Olive Bark. By FREDERICKBELDING POWER and FRANK TUTIN . . 904LXXXV.-The Refraction and Dispersion of Triazo-compounds.By JAMES CHARLES PHILIP . . . . 918LXXXV1.-The Dissociation Constants of Triazoacetic anda-Triazopropionic Acids. By JAMES CHARLES PHILIP . . 925LXXXVI1.-The Spontaneous Crystallisation of Substanceswhich form a Continuous Series of Mixed Crystals. Mix-ture of Naphthalene and P-Naphthol. By HENRY A.MIERS, F.R.S., and FLORENCE ISAAC . . 927LXXXVII1.-The Influence of Solvents on the Rotation ofOptically Active Compounds. Part XII. Ethyl Tartratein Aromatic Halogen Derivatives. By THOMASTEWARTPATTERSON and DAVID PATERSON MCDONALD, M.A., B.Sc.. 936LXXX1X.-Acetylketen : a Polymeride of Keten. By FRANCESCHICK and NORMAN THOMAS MORTIMER WILSMORE . . 946XC.-The Coxidensation of Benzoin with Methyl Alcohol. ByJAMES COLQUEOUN IRVINE, D.Sc., Ph.D., and DAVIDMCNICOLL, M.A., B.Sc. . . 950XC1.-A New General Method of Preparing DiazoniumXC1I.-The Absorption Spectrum of Camphor. By WALTERPAGELXXX.-Quantitative Separation of Thallium from Silver,LXXX1.-The Constituents of Cyprus Organum Oil.Bromides. By FREDERICK DANIEL CHATTAWAY . . 958NOEL HARTLEY, D.Sc., F.R.S. . . 96CONTENTS. 1xPAGEXCII1.-The Chemical Action of Radium Emanation. Part 111.On Water and Certain Gases. By ALEXANDER THOMASCAMERON and SIR WILLIAM RAMSAY, K.C.B. . . 966Part IV.On Water. By ALEXANDER THOXAS CAMERON and SIRWILLIAM RAMSAY, K.C.B.. . 992XCV.-Molecular Volumes of the Nitrites of Silver, Mercury,and the Alkali Metals. By PRAFULLA CHANDRA RAY . 997XCV1.-The Mutual Solubility of 2-Methylpiperidine andXCVI1.-The Viscosity of Solutions. By CHARLES EDWARDFAWSITT . . 1004XCVII1.-A Criticism of Werner's Theory and the Constitutionof Complex Salts. By JOHN ALBERT NEWTON FRIEND, Ph.D. 1006XCIX.-The Reaction of Diazonium Salts with Mono- andDi-hydric Phenols and with Naphthols. By KENNEDYJOSEPH PREVITE ORTON and REGINALD WILLIAM EVERATT . 1010C.-Ethyl 6-Methyl-2-pyrone-3:5-dicarboxylate and its Deriv-C1.-The Melting Points of the Anilides, p-Toluidides, anda-Naphthalides of the Normal Fatty Acids. By PHILIPWILFRED ROBERTSON. .1033OIL-The Volumetric Estimation of Silver. By WILLIAMROBERT LANG and JOHN OBINS WOODHOUSE . . 1037CII1.-The Polarimetric Study of Intramolecular Rearrange-ment in Inactive Substances. By THOMAS STEWARTPATTERSON and ANDREW MCMILLAN, M.A., B.Sc. (CarnegieResearch Fellow) . . 1041Part11. Anilinobenzoxazole and the Supposed Anilodihydro-benzoxazole. By GEORGE YOUNG and ALBERT EDWARDDUNSTAN . . 1052CV.-The Relation between Dielectric Constant and ChemicalConstitution. Part I. Stereoisomeric Compounds. ByALFRED WALTER STEWART (Carnegie Research Fellow)CV1.-An Apparatus for Determining the Specific InductiveCapacity of Organic Liquids. By ALFRED WALTER STEWART(Carnegie Research Fellow) . . 1062CVI1.-Titani-dihydroxymaleic Acid, and the Detection ofTitanium.By HENRY JOHN HORSTMAN FENTON . . 1064CVII1.-The Triazo-group. Part 111. Bistriazo-derivatives ofEthane and of Acetic Ester. By MARTIN ONSLOW FORSTER,HANS EDUARD FIERZ, and WALTER PHILIP JOSHUA . . 1070XC1V.-The Chemical Action of Radium Emanation.Water, By OTTO FLASCHNER and BASIL MACEWEN . . 1000atives. By JOHN LIONEL SIMONSEN . . 1022OW.-Contributions to the Chemistry of the Amidines.. 105X CONTENTS.C1X.-Experiments on the Synthesis of 1-Methylcyclohexyl-idene-4-ace tic Acid, CH1Cle<CH2 CH -CH .CH2>C: CH*CO,H.Part I. By WILLIAM HENRY PERKIN, jun., and WILLIAMJACKSON POPE . . 1075CX.-The Synthesis and Constitution of Certain Pyranol SaltsRelated to Brazilein and Haematein. By WILLIAM HENRYPERKIN, jun., ROBERT ROBINSON, and (in part) MAURICERUSSELL TURNER .. 1085CX1.-Brazilin, Haematoxylin, and their Derivatives. Part IX.On Brazilein, Hzematein, and their Derivatives. By PAULENGELS, WILLIAM HENRY PERKIN, jun., and ROBERTROBINSON . . 1115(3x11.-The Interaction of Copper and Nitric Acid in Presenceof Metallic Nitrates Considered with Reference to theExistence of Hydrates in Solution. By EDWARD HENRYRENNIE, M.A., D.Sc., ALFRED J. HIGGIN, F.I.C., and WILLIAM:TERNENT COOKE, D.Sc. . 1162CXII1.-Condensation Products from AminopinenedicarboxylicAcid. By WILLIAM: GODDEN, B.Sc. . . 1171CX1V.-The Triazo-group. Part IV. Allylazoimide. ByMARTIN ONSLOW FORSTER and HANS EDUARD FIERZ . . 1174CXV.-Aromatic Arsonic and Arsinic Acids. By FRANK LEEPYMAN and WILLIAM COLEBROOK REYNOLDS .. 1180UXV1.-The Electrolytic Oxidation of Some HydroxybenzoicAcids. By ARTHUR GEORGE PERKIN and FREDERICK MOLLWOPEREIN . . 1186CXVI1.-The Thermal Decomposition of Hydrocarbons. Part I.[Methane, Ethane, Ethylene, and Acetylene.] By WILLIAMARTHUR BONE and HUBERT FRANK COWARD. . 1197CXVII1.-The Effect of Constitution on the Optical Activity ofNitrogen Compounds. By REGINALD WILLIAM EVERATT, B.Sc. 1225CX1X.-Acids as Accelerators in the Acetylation of the Amino-groups. By ALICE EMILY SMITH and KENNEDY JOSEPHPREVIT~ ORTON . . 1242CXX.-The Hydrolysis of Amygdalin by Emulsin. Part I. ByS. J. MANSON AULD, Ph.D. . 1251CXX1.-The Hydrolysis of Amygdalin by Emulsin. Part 11. ByS. J. MANSON AULD, Ph.D. . 1276CXXIL-The Formation of 4-Pyrone Compounds from Acetyl-enic Acids.Part 11. By SIEGFRIED RUHEMANN . . 1281CXXIIL---Methylcamphor and Fenchone. By WALTER HAMISGLOVER . . . . 1285CXX1V.-Viscosity Determinations at High Temperatures. ByCHARLES EDWARD FAWSITT . . 1299PAGE2 CONTENTS. xiPAGECXXV.-The Formation of Polyiodides in Nitrobenzene Solu-tion. Part 111. The Chemical Dissociation of the Poly-iodides of the Alkali Metals and Ammonium Radicles. ByHARRY MEDFORTH DAWSON . . . 1308CXXV1.-The Study of the Absorption Spectra of the Hydro-carbons Isolated from the Products of the Action ofAluminium Chloride on Naphthalene. By ANNIE HOMER,Fellow of Newnham College, and JOHN EDWARD PURVIS, M.A. 1319CXXVI1.-Cholestenone. By CHARLES DOREE and JOHNADDYMAN GARDNER .. 1328OXXVII1.-Apparatus for Experiments at High Temperaturesand Pressures, and its Application to the Study of Carbon.By RICHARD THRELFALL, F.R.S. . . 1333CXX1X.-The Rusting of Iron. By WILLIAM AUGUSTUS TILDEN 1356CXXX.-Some Esters of Arsenious Acid. By WILLIAM ROBERTLANG, JOHN FRANCIS MACKEY, and Ross AITKEN GORTNER 1364CXXX1.-Benzeneazo-2-pyridone. By Wr LLIAaf HOBSON MILLSand SIBYL T. WIDDOWS . . 1372CXXXI1.-Aromatic Selenonium Bases. By THOMAS PERCYHILDITCH and SAMUEL SMILES . . 1384CXXXIIL-The Relation between Unsaturation and OpticalActivity. Part 111. Optically Active Salts of Acids Con-taining Adjacent Unsaturated Groups. By THOMAS PERCYHILDIWH . . 1388CXXX1V.-The Preparation of Disulphides.Part 11. TheAction of Alkalis on Sodium Alkyl Thiosulphates. ByTHOMAS SLATER PRICE and DOUGLAS FRANK TWISS . . 1395CXXXV.-The Preparation of Disulphides Part 111. TheNitrobenzyl Disulphides. By THOMAS SLAYER PRICE andDOUGLAS FRANK TWISS . . 1401CXXXV1.-Solubility of Silver Chloride in Mercuric NitrateSolution. By BERTRAM HAWARD BUTTLE and JOHN THEODOREHEWITT . . 1405CXXXVI1.-The cis- and tmm-Modifications of 1-Methylcylo-hexan-2-ol-4-carboxylic Acid and their Conversion into1-Methyl-A1-cycZohexene-4-carboxylic Acid. By ANDREWNORMAN MELDRUM (Carnegie Research Fellow) and WILLIAMHENRY PERKIN, jun. . . 1416Part I.Glucose-anilide, -oxirne, and -hydrazone. By JAMESCOLQUHOUN IRVINE, Ph.D., D.Sc., and ROBERT GILMOURCXXX1X.-The Use of the Micro-balance for the Determina-tions of Electrochemical Equivalents and for the Measure-ment of Densities of Solids.By OTTO BRILL and CLARE DEBRERETOX EVANS. . . 1443CXXXVII1.-The Constitution of Glucose Derivatives.. 142xii CONTENTS.CXL.-The Fluorescence of Platinocyanides. By LEONARDANGELO LEVY . . 1446CXL1.-The Reduction of Aromatic Nitro-compounds to Azoxy-derivatives in Acid Solution. By BERNHARD FLURSCHEIMand THEODOR SIMON . . 1463CXLI1.-The Reduction of Refractory Oxides by Carbon. ByHAROLD CECIL GREENWOOD, M.Sc. . . 1483CXLII1.-The Production of Ferro-alloys. By HAROLD CECILGREENWOOD, MSc. . . 1496CXL1V.-The Proteins of Egg-yolk. By R. H. ADERS PLIMMER,D . Sc. . 1500CXLV.-The Action of Bromine on P-Hydrindone. By NORNANALLEN CREETH and JOCELYN FIELD THORPE .. 1507CXLV1.-The Constituents of Canadian Hemp. Part I.Apocynin. By HORACE FINNEMORE, B.Sc. . . 1513CXLVI1.-A New Synthesis of Apocynin. By HORACEFINNEMORE, B.Sc. . . 1520CXLVIIL-Aromatic a-Disulphones. By THOMAS PERCYHILDITCH . . 1524CXL1X.-On Polymorphism, with Especial Reference to SodiumNitrate and Calcium Carbonate. By WILLIAM BARLOW andWILLIAM JACKSON POPE . . , 1528CL.-The Action of Nitrous Gases on Dicyclopentadiene, ByALEXANDER RULE . . 1560CL1.-The Constitution of Co-ordinated Compounds. By SAMUELHENRY CLIFFORD BRIGGS . 1564CLI1.-The Rapid Electroanalytical Deposition and Separationof Metals. Part 11. Antimony and Tin. The Employmentof a Diaphragm. By HENRY JULIUS SALOMON SAND .. 1572CLII1.-The Electrolytic Chlorination of the Salts of OrganicAcids. By JOHN KENNETH HAROLD INGLIS and FREDWOOTTON . . 1592CL1V.-The Conductivities of the a-Oximino-fatty Acids. ByJOHN KENNETH HAROLD INGLIS and LOTTIE ENILY KNIGHT . 1595CLV.-The Formation of Ethers from Compounds of the BenzoinType. By JAMES COLQUHOUN IRVINE, Ph.D., D.Sc., andDAVID MCNICOLL, M.A., B.Sc. (Carnegie Scholar) . . 1601CLVL-Studies of the Perhalogen Salts. Part 11. By CHARLESKENNETH TINKLER . . 1611CLVI1.-The Relation between Unsaturation and OpticalActivity. Part IV. The Relative Influence of Bi-, Quadri-,and Sexa-valent Sulphur on Rotatory Power. By THOMASPERCY HILDITCH . . 1618CLV1II.-Coprosterol. Part I. By CHARLES DOHJ~E and JOHNADDYMAN GARDNER .. 1625PAG...CONTENTS. X l l lPAGECL1X.-Oxidation of Hydrocarbons of the Benzene Series.Part 11. Substances containing a Negative Radicle. ByHERBERT DRAKE LAW and FREDERICK MOLLWO YERKIN . 1633CLX.-The Measurement of a Homogeneous Chemical Changein a Gas. (The Thermal Decomposition of Ozone.) ByHERBERT EDMUND CLARKE and DAVID LEONARD CHAPMAN . 1638Dithiodiglycollic and Dithiodilactylic Acids. By THOMASSLATER PRICE and DOUGLAS FRANK Twrss . 1645CLXI1.-The Constituents of the Expressed Oil of Nutmeg. ByFREDERICK BELDING POWER and ARTHUR HENRY SALWAY . 1653CLXII1.-Syntheses with Phenol Derivatives containing aMobile Nitro-group. Part I. The Interaction of 2:3:5-Tri-nitro-4-acetylaminophenol and Amines. By RAPHAELMELDOLA, F.R.S., and JAMES GORDON HAY .. 1659CLX1V.-Contributions to the Chemistry of the CholesterolGroup. Part I. The Action of Hydrogen Peroxide and ofFused Potassium Hydroxide on Cholesterol. By ROBERTHOWSON PICKARD and JOSEPH YATES . . 1678CLXV.-Derivatives of S-Phenylphenazothionium. Part 11. BySAMUEL SMILES and THOMAS PERCY HILDITCH . . 1687CLXV1.-A Reaction Distinguishing Phosphoprotein fromNucleoprotein and the Distribution of Phosphoproteins i nTissues. By R. H. ADERS PLIMMER and F. H. SCOTT . . 1699CLXVI1.-The Colouring Matters of the Stilbene Group. Part V.The Action of Caustic Alkalis on Derivatives of para-Nitro-toluene.CLXVIIL-The Trithionates and Tetrathionates of the AlkaliMetals. Part I. By JOHN EDWIN MACKENZIE (ResearchFellow of the University of Edinburgh) and HUGH MARSHALL 1726CLX1X.-The Sporitaneous Crystallisation of Solutions of someCLXX.-The Relation between Absorption Spectra and ChemicalConstitution.Part IX. The Nitroso- and Nitro-groups.By EDWARD CHARLES CYRIL BALY and CECIL HENRY DESCH . 1747CLXX1.-The Synthesis of Complex Acridines. By PERCYCORLETT AUSTIN. . 1760CLXXI1.-The Solubilit’y of Lime in Water. By GERALDTATTERSALL MOODY and LEWIS THOMAS LEYSON. . . 1767CLXXII1.-The Chlorination of para-Nitroaniline. By BERN-HARD FL~~RSCHEIM . . 1772CLXX1V.-The Direct Action of Radium on Copper and Gold. . 1775CLXXV.-Syntheses with the Aid of Monochloromethyl Ether.Part I. The Action of Monochloromethyl Ether on theSodium Derivatives of Ethyl Malonste and Ethyl isoPropy1-CLX1.-The Preparation of Disul phides.Part IV. Esters ofBy ARTHUR GEORGE GREEN and JAMES BADDILEY . 1721Alkali Nitrates. By BERNARD MOUAT JONES . . 1139By EDGAR PHILIP PERMAN .malonate. By JOHN LIONEL SIMONSEN . . 177xiv CONTENTS.CLXXVL-The Effect of Constitution on the Rotatory Power ofOptically Active Nitrogen Compounds. Part 111. ByREGINALD WILLIAM EVERATT and HUMPHREY OWEN JONEEI , 1789CLXXVI1.-Relation between Chemical Constitution and Physio-logical Action in Certain Substituted Aminoalkyl Esters.CLXXVII1.-The Relation between Absorption Spectra andChemical Constitution. Part X. Unsaturated Acids ofthe Benzene Series. By EDWARD CHARLES CYRIL BALY andKONRAD SCHAEFER . . 1808CLXX1X.-The Relation between Viscosity and Chemical Con-stitution.Part 11. The Existence of Racemic Compoundsin the Liquid State. By ALBERT ERNEST DUNSTAN andFERDINAND BERNARD THOLE . . 1815CLXXX.-The Direct Interaction of Magnesium and AlkylHalides. By JAMES FREDERICK SPENCER and MARY S.CREWDSON . . 1821CLXXX1.-The Interaction of Metals of the Aluminium Groupand Organic Halogen Derivatives. By JAMES FREDERICKSPENCER and MARION L. WALLACE . . 1827CLXXXI1.-The Interaction of Hydrogen Dioxide and Sulphides.By MAUD GAZDAR and SAMUEL SMILES . 1833CLXXXII1.-The Influence of Solvents on the Rotation ofOptically Active Compounds. Part XIII. Ethyl Tartratein Aromatic Nitro-derivatives. Influence of Temperature-change on Rotation in Solution. By THOMAS STEWARTPATTERSON. . 1836CLXXX1V.-A New Form of Gas Burette.By ARTHUR EDWINHILL . . 1857CLXXXV.-The Triazo-group. Part V. Resolution of a-l'riazo-propionic Acid. By MARTIN ONSLOW FORSTER a.nd HANSEDUARD FIERZ . . 1859CLXXXV1.-The Triazo-group. Part VI. Triazoethyl Alcoholand Triazoacetaldehyde. By MARTIN ONSLOW FORSTER andHANS EDUARD FIERZ. . 1865CLXXXVI1.-Experiments on the Synthesis of the Terpenes.Part I (continued). Resolution of dl-1-Methyl-Al cyclo-hexene-4-carboxylic Acid and Synthesis of the OpticallyActive Modifications of Terpineol. By KENNETH FISHERand WILLIAM HENRY PERKIN, jun. . . lS71CLXXXVII1.-Experiments on the Synthesis of the Terpenes.Part XIII. Synthesis of isocarvestrene (A6:S(g)-m-Mentha-diene) and its Derivatives. By KENNETH FISHER andWILLIAM HENRY PERKIN, jun.. . 1876CLXXX1X.-Aromatic Arsonic Acids. By MARMADUKE BARROW -CLIFF, FRANK LEE PYMAN, and FREDERIC GEORGE PERCYREMFRY . . 1893PAGEBy FRANK LEE PYMAN . . 179CONTENTS. xvPAGECXC.-The Relation between Absorption Spectra and ChemicalConstitution. Part XI. Some Aromatic Hydrocarbons. ByEDWARD CHARLES CYRIL BALY and WILLIAM BRADSHAW TUCK 1902CXC1.-Colour and Constitution of Azomethine Compounds.Part 11. By FRANK GEO. POPE and ROBERT FLEMING . . 1914CXCI1.-The Relation between Viscosity and Chemical Con-stitution. Part 111. The Enol-ketonic Tautomerism. ByALBERT ERNEST DUNSTAN and JAMES ARTHUR STUBBS . . 1919CXCII1.-Contributions to the Chemistry of the CholesterolGroup. Part 11. Some Oxidation Products of Sitosterol.By ROBERT HOWSON PICKARD and JOSEPH YATES .. . 1928CXC1V.-The Condensation of Salicylaldehyde and Benzamide.By ARTHUR WALSH TITHERLEY and MORRIS EDGAR MARPLES. 1933CXCV.-Experiments on the Synthesis of 1-Methylc?jcZohexyl-iclene-4-acetic Acid. Part 11. By VICTOR JOHN HARDING,WALTER NORMAN HAWORTH, and WILLIAM HENRY PERKIN,Synthesisof Methane. By WILLIAM ARTHUR BONE and HUBERT FRANKCOWARD . . 1975CXCVI1.-The Chlorination of Methyl Derivatives of Pyridine.2-Methylpyridine. Part 11. By WILLIAM JAMES SELL . 1993CXCVII1.-The Chlorine Derivatives of Pyridine. Part IX.Preparation and Orientation of 3:5-Dichloropyridine. ByWILLIAM JAMES SELL . . 1997CXC1X.-The Chlorine Derivatives of Pyridine. Part X.Orientation of 2: 3 :5-Trichloropyridine.By WILLIAM JAMESSELL . . 2001CC.-Organic Derivatives of Silicon. Part VII. The Synthesisof dl-LCjulphobenzylethylisobutylsilicyl Oxide. By BERNARDDUNSTAN W~LKINSON LUFF, A.I.C. (1851 Exhibition Scholar),and FREDERIC STAXLEY KIPPING . . 2004CC1.-The Coumarin Condensation. By ARTHUR CLAYTON . 2016CCI1.-Studies on the Viscosity and Conductivity of SomeAqueous Solutions. Part I. Solutions of Sucrose, Hydro-gen Chloride, and Lithium Chloride. By W. HEBERGREEN, D.Sc. . . 2023CCIT1.-Studies on the Viscosity and Conductivity of SomeAqueous Solutions. Part 11. Mixtures of Solutions ofSucrose and Lithium Chloride. A Contribution towardsthe Elucidation of the Connexion between Ionic Mobility andthe Fluidity of the Solution.CCIV.-The Formation of Polyiodides in Nitrobenzene Solution.Part IV.The Electrolytic Dissociation of the Polyiodidesof the Alkali Metals and Ammonium Radicles. By HARRYMEDFORTH DAWSON and COLIN GYRTH JACKSON . . 2063CCV -Meteloidine : A New Solanaceous Alkaloid. By FRANKLEE PYMAN and WILLIAM COLEBROOK REYNOLDS . . 2077jun. . . 1943CXC V1.-The Direct Union of Carbon and Hydrogen.By W. HEBER GREEN, D.Sc. 204XVi CONTENTS.CCV1.-The Action of Phosphorus Pentachloride on the Methyl-ene Ethers of Catechol Derivatives. Part 111. The CyclicCarbonates of Dichloro-ethyl- and -propyl-catechol. ByGEORGE BARGER . . 2081CCVIL-The Synthesis of Thionaphthen Derivatives fromStyrenes and Thionyl Chloride. By GEORGE BARGER andARTHUR JAMES EWINS . . 2086CCVII1.-Organic Derivatives of Silicon. Part VIII. TheResolution of dl-Sulphobenzylethylisobutylsilicyl Oxide andthe Properties of the Optically Active Acids. By BERNARDDUNSTAN WILKINSON LUFF (1851 Exhibition Scholar) andFREDERIC STANLEY KTPPING . . 2090CCIX. -Some Molecular Compounds of Styphnic and PicricAcids. By CHARLESTANLEY GIBSON . . . 2098CCX.-The Formation of Some Carbides. By JOHN NORMANPRING , . 2101CCX1.-The Relation between Absorption Spectra and ChemicalConstitution. P a r t XII. Some Amino-aldehydes and-ketones of the Aromatic Series. By EDWARD CHARLESCYRIL BALY and EFFIE GWENDOLINE MARSDEN . . 2108CCXI1.-The Affinity of Certain Alkaloids for HydrochloricAcid. By VICTOR HERBERT VELEY . . 2114CCXII1.-The Affinity Constants of Bases as Determined bythe Aid of Methyl-Orange. By VICTOR HERBERT VELEY . 2122CCX1V.-Organic Derivatives of Arsenic. Part I. Dicam-phorylarsinic Acid. By GILBERT T. MORGAN and FRAKCESM. G. MICKLETHWAIT .CCXV.-Study of the Constitution and Properties of theRhodsnides of Inorganic Radicles. Part I. By AUGUSTUSEDWARD DIXON and JOHN TAYLOR . * 2148CCXV1.-Ester Catalysis and a Modification of the Theory ofAcids. By EDWARD F~TZGERALU and ARTHUR LAPWORTH . 2163CCXVI1.-Tellurium Dicyanide. By HERBERT EDWINCOCKSEDGE. . 2175CCXVII1.-Boron Thiocyanate. By HERBERT EDWINCOCKSEDGE. . 2177CCX1X.-The Viscosity of Fuming Sulphuric Acid.ALBERT ERNEST DUNSTAN and ROBERT WILLIAM WILSON ”? 21 79CCXX.-The Densities of Krypton and Xenon. By RICHARDB. MOORE, B.Sc. . 2181CCXX1.-An Examination of the Conception of Hydrogen Ionsin Catalysis, Salt Formation, and Electrolytic Conduction.By ARTHUR LAPWORTH . . 2187CCXXI1.-The Oxidation of Phosphorous Acid by Iodine. ByBERTRAM DILLON STEELE . . 2203OBITUARY . 2214PAGE. 214

ISSN:0368-1645    

DOI:10.1039/CT90893FP001

出版商:RSC    

年代:1908

数据来源: RSC

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IODATES AND PERIODATES OF THE ALKALI METALS 1511.-Note on the Iodates and Periodates of the AlkaliMetals and the Ammonium Radicle.By THOMAS VIPOND BARKER, B.A., B.Sc.(Oxon.).THE present communication deals with the chemicaI part of aninvestigation of certain iodates and periodates which were chiefly pre-pared for a crystallographic examination ; the results of the latterwill appear shortly in the Zeitschrift fur Krystaztographie.Of the analyses, the halogen estimations were effected by the Cariusmethod, which the author had previously found to answer well for theperchlorates; the heating was carried out in two operations, eachlasting four hours, the first to 150' and the second to 250'. Themetal was estimated by the usual sulphate method.The specific gravity determinations were made in capped specificgravity bottles with carbon tetrachloride as displacing liquid ;the solubility determinations mere carried out with 20 C.C.of thesaturated solutions.Kubidium lodute, RbIO,.-This salt, as well as the correspondingcasium compound, was first prepared by Wheeler (Amer. J. Xci., 1902,[iii], 44,123) by adding iodic anhydride to solutions of the carbonates.A good yield is obtained by passing chlorine into a hot concentrate1 6 BARKER : NOTE ON THE IODATES AND PERIODATES OF THEsolution of a mixture of rubidium iodide and hydroxide, wherebythe sparingly soluble iodate is precipitated :Specific gravity at 14"/4" = 4.559.Solubility : 100 parts of water dissolve 2.1 parts at 23" (WheelerCaesium lodale, CsIO,.-This salt was prepared in the same way asSpecific gravity a t 16'/4O= 4,831.Solubility : 100 parts of water dissolve 2.6 parts at 24' (Wheeler).The iodates of potassium, rubidium, and cesium form anisomorphous group, crystallising in what appear to be cubes, butwhich are really made up of four monoclinic sub-individuals, inter-penetratingly twinned.Potassium periodate, KIO,, is readily prepared by oxidising theiodate; a suitable method is to pass chlorine into a hot, stronglyalkaline solution of the iodate (Rammelsberg, Ann.Y l ~ y s . Chern.,1868, [ii], 134, 368) ; the very sparingly soluble periodate separatesin tetragonal bipyramids * :Mol. vol. = 57.14.the rubidium compound :Mol. vol. = 63.68.0.3080 gave 0.3106 AgT.Specific gravity a t 15"/4"= 3.618.Solubility : 100 parts of water dissolve 0.66 part at 13O, and thespecific gravity of the saturated solution at 13'/4" is 1.0051.Rubidium periodate, RbIO,, has not previously been obtained.Itwas prepared by the method mentioned above for the potassiuuicompound. The precipitated crystals mere washed and recry stnllisedtwice :I= 5 4 5 .KIO, requires I = 55.1 per cent.Mol. vol. = 63.60.0.3090 gave 0.2664 AgI.0.4045 ,, 0,1930 Rb,SO,. Rb = 30.54.RblO, requires I = 45.9 ; Rb = 30.91 per cent.The high value for iodine and the low value for rubidium point tothe presence of a small amount of potassium. The salt formsbeautiful, colonrless, tetragonal crystals, strictly isomorphous with thepotassium compound :I = 46.6.Specific gravity at 16'/4'= 3.918.Solubility: 100 parts of water dissolve 0.65 part at 1 3 O , and theMol.vol= '70.56.specific gravity of the saturated solution at 16'14' is 1.0052.* Potassium periodate was stated by Ranimelsberg to bc orthorhonibic and iso-niorl)hous with the perchlorate, but, iii spite of all efforts, the author did notsucceed i n obtaining an olthorhombic modification, so he communicated with Prof.Groth, of Munich, who fortunately had i n his possession the preparation originallymeasured by Ranimelsberg. Prof. Groth kindly had the crystals andysed, and theywere found to contain 110 trace of iodine, being, in fact, practically pure potassiuiiiperchlorateALKALI METALS AND THE AMMONIUM RADICLE. 17Cccesium periodate, CsIO,, was first prepared by Wells (Amer.Chem,.J., 1901, 26, 278) by neutralising periodic acid with cwsiumcarbonate. The salt may also be prepared by the chlorine method,but the yield is by no means good, much iodate precipitating with thecrystals of the periodate; the bulk of the author's salt was thereforeobtained by Wells's method :0.4601 gave 0.3321 AgT. 1=39*02.CsIO, requires I=39*20 per cent.Cesium periodate is fairly soluble in water, and crystallises in well-defined plates belonging to the orthorhombic system, and is thereforenot isomorphous with the potassium and rubidium compounds :Specific gravity at 15"/4'= 4,259.Solubility : 100 parts of water dissolve 2-15 parts a t 15", and thespecific gravity of the saturated solution a t 15'/4' is 1,0166.Ammoniunt periodate, NH,IO,, was obtained by neutralising asolution of periodic acid prepared by Wells's method (Eoc.cit.) withaqueous ammonia; the salt is isomorphous with the potassium andrubidium compounds :Mol. vol. = 76.04.Specific gravity a t 18'/4O= 3,056.Solubility: 100 parts of water dissolve 2-70 parts at 16', and thespecific gravity of the saturated Bolution at 16'/4O is 1.0178.Sodium periodate, NaIO,, crystallises in two forms : one anhydrous,isomorphous with the ammonium salt; the other with 3 molecules ofwater, in the rhombohedra1 system :Mol. vol. = 68.39.Specific gravities : NaIO, at 16'/4O- 3,865.The periodates of potassium, rubidium, ammonium, sodium, as wellas of silver and lithium (accoiding to Rammelsberg) form therefore anisomorphous group, crystallising in the tetragonal system. The groupis interesting, not only because the majority of the elements in thefirst group of the periodic classification are represented, but alsobecause the crystalline form is extraordinarily similar to that of theminerals of the scheelite group. The cause of this is, no doubt, to befound in the similarity of the type of composition, KIO,,CaWO,, justas it is in certain othor pairs of compounds, for example, calciumcarbonate and sodium nitrate, and potassium perchlorate and bariums ulpha t e.Mol. vol. = 55.37.97 NaI0,,3aq. at 18'/4'= 3.219. Mol. vol. = 83.28.The author's thanks are due to Prof. H. A. Rliere, in whoselaboratory the above work was carried out.hIINERBLOGICAL DEPARTMEN'r,OXFORD.UNIVERSITY MUSEUM,VOL XCIII.

ISSN:0368-1645    

DOI:10.1039/CT9089300015

出版商:RSC    

年代:1908

数据来源: RSC

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18 DIXON AND TAYLOR : ACTLOGENS AND THIOCARBAMIDES.I1 I.-Acylo,qens and Thiocarbarnides.By AUGUSTUS EDWARD DIXON and JOHN TAYLOR.IT has been shown in previous communications (Dixon and Taylor,Trans., 1907, 91, 912; see also Dixon and Hawthorne, ibid., 122)that the reaction between certain well-defined acylogens and thio-carbamide, or its aryl monosubstitution derivatives,” leads to theproduction of halogen salts derived from iminothiocarbamic acid,thus :(i) NH,*CS*NH, + R-COCI = HC1 -I- NH,*C(NH)+I*COR ;(ii) ArNH*CS*NH, + R*COCl= HC1+ ArNH*C(NH)*&COR.As a rule, salts of class (i) are easily hydrolysed with regecerationof thiocarbamide, but undergo molecular change when heated, the acylgroup becoming associated with one of the nitrogen atoms t o form anacyl-substituted thiocarbamide :NH,*C(NR)*S*COR,HCl-+ .ECl + RCO*NH*CS#NH,.Those of class (ii) are distinctly more stable, yielding, by cautiouswithdrawal of the combined halogen acid in the cold, a substance havingthe empirical formula of the corresponding base, namely,ArNH.C( NH).S*COR.This substance, however, is not the base, but an isomeride,RCO*NAr*CS*NH, ;the acyl group, as soon as the halogen acid is neutralised, parting fromthe sulphur to become associated with that nitrogen atom whichalready holds in combination a hydrocarbon radicle.Under the influence of heat, or of a dilute alkali (compare Hugers-* Although in many reactions thiocnrbamide behaves, not as CS(NH,),, but asiminothiocarbamic acid, NH:C(SH)*NH,, and the like is true as regards a largenumber of its substitution derivatives, yet in the prevent paper (save where Rdefinitely established structure forbids) they are all represented on the thiocarb-amide type, and named accordingly.This nsage is adopted, however, not toexpress any view as to their respective constitutions, but solely to avoid the clumsi-ness of attaching two or more names and formulz to a single compound. Forinstance, the so-called phenylthiocarbamide, PiiNH’CS’NH,, may react asPhN:C(SH)*NH,, or as PhNH*C(SH):NH ; possibly, also, as a true thiocarbamide ;or it may be a thiocarbamide in the static condition. The ab-disubstituted thio-carbamides, it would seem, are capable of reacting in three different forms, accordingt o circumstances ; if “ the constitution of a compound’’ is t o be inferred from itschemical behaviour, it is not easy to judge, in a case like this, how any save aconventional nomenclature is to be applied.The present being principally a descriptive paper, the authors desire to confinethemselves to the experimental results, and to the abovc statement of tho conven-tion respecting names aud formulEDIXON AND TAYLOR : ACYLOGENS AND TRIOCARBAMIDES.19hoff, Ber., 1899, 32, 3649), the first intramolecular movement of theacyl group is followed by a second; this time to the remainingnitrogen atom, where, in the configuration :the acyl radicle appears t o have reached a position of maximumstability.These statements outline in a merely approximate waythe mainresults hitherto observed. Deviations of various sorts occur j forexample, in certain cases, the benzoyl group, when liberated from thesulphur, moves so readily to the non-substituted nitrogen atom (toform an ab-disubstituted thiocarbamide) that, although the existenceof an an-form was recognisable (Eoc.cit.) through the characteristicreaction whereby thiocganic acid is produced,ArNAc*CS*NH, -+ KOH = KSCN + ArNHAc + H20,the movement could not be arrested at the substituted nitrogen atomlong enough to permit of the isolation of the aca-compound.On the other hand, in the case of the acyl groups, *C02Me and*C02Et, the electronegative character of which is somewhat feeble,the first transfer from sulphur t o nitrogen,PhNH* C( NH) *S* C0,Me -+ FhN( C0,Me) *CS*NH,,PhNH CS *NH( CO,Me),could not be accomplished; a failure the more remarkable, con-sidering that by other means the synthesis of the ab-compound presentsno difficulty,It may be noted, too, regarding the behaviour of compounds suchasPhNH*C(NH)*S*CO,R,HCl, that it is not a matter of indifferencewhether the radicle, R, be fatty-or benzenoid ; for, in the latter case,on the withdrawal by alkali of the combined hydrogen chloride, noua-thiocarbamide, PhN(CO,Ar)*CS*NH,, is formed, but, instead,decomposition occurs with production of carbon dioxide, the phenol,ArOH, and phenylthiocarbimide.Beyond the facts here roughly indicated, our knowledge of thebehaviour of acylogens with thiocarbamides does not extend very far ;interesting work has lately been carried out on the alkyl-+-thio-carbamides, derivatives of the type NH,*C(NH)*SAlk, but, for thepresent purpose, i t is unnecessary to particularise the conclusions.In this communication, the writers give the results of an inquirydirected mainly in order to learn (i) the effect of using an acglogenthe acid radicle of which contains a second halogen element, and (ii)the behaviour of certain acylogens towards thiocarbamides containingnon-aromatic substituting radicles.ArNH*CS*NH*COR,is brought about very readily, whilst the second, to producec 20 DIXON AND TAYLOR : ACYLOGENS AND THIOCARBAMIDES.Ex PEHI M E N TA L.a-Bvomopropionyl Bromide and Yhen~lt~~iocarbamide.If the reaction between these substances is analogous to thatwhere ordinary alkylogens are concerned, it must proceed primarily nsfollows :PhNH*CS*NH, + CH,*CHBr*COBr =On the other hand, when halogenised radicles are presented forcombination with the nitrogen of a thiocarbamide, ring-closingfrequently occurs with elimination of halogen acid ; thus, for example,Hirsch has shown (Ber., 1890, 23, 971) that methylthiocarbimideyields with /3-bromopropylamine, not the expected methylbromo-propylthiocarbamide, CH,*NH*CS*NH*CH,*CHBr*CH,, but, instead,the hydrobromide of an isomeric ring-compound,PhNH*C(NH)*S*CO*CHBr*GH,,HBr.CH,*NH.C<~J~, S CHMe .This action may obviously be represented by supposing thethiocarbamide first to be produced, and then to be changed i n t oN--C]H,SH CHMeBr' whence, by the labile or tautomeric form, CH,*NH*C<loss of t'he elements of hydrogen bromide, the above ring-compoundwould result.I n like manner, if phenylthiocarbamide were first t o yield witha-bromopropionyl bromide the product already formulated, this mighteasily transform itself into a ring-form, thus :Experiment gave the results described below.Vigorous action took place on mixing the constituents, dissolved inmolecular proportions, in warm acetone, and, on cooling, small, white,glistening plates were deposited, giving with water a clear acidsolution.When heated in a narrow tube, the solid darkened slightlyat 2 1 5 O , shrank at 230°, and melted with effervescence and charringa t 238-239' (uncorr.).From the solution in water or alcohol, no picrate could be obtained,from which it seemed improbable that a-bromopropionyl-q-phenyl-thiourea hydrobromide, PhNH*C(NH)*S*CO*CHBr*CH,,HBr, hadbeen formed ; neither did the solution in concentrated alkali yield anytrace of red coloration when acidified and treated with ferric chloride ;hence there mas no reason to suppose that migration of the acgDIXON AND TAYLOR : ACYLOGENS AND THIOChI1BAMIDES.21group had occurred with production of aa-bromopropionylphenyl-thiocarbamide, CH,* CHBr CO*NPh* CSONH,.A bromine determination, however, gave figures concordant withthe latter formula :0.368 required 19.75 C.C. Z/10 silver nitrate.C,,H,,ON,BrS requires Br = 27.87 per cent.But on further examination the compound proved to be a hydro-bromide, and, since it was not desulphurised by boiling with an alkalinesolution of lead, the sulphur must evidently be held in a closed-ring,which could have only the constitution figured above, namely,Br = 27-75.N*C N.70s*c ' &,, or, the alternative form, *C< That the latter ofthese is correct was shown by the fact that the substance, whenboiled with baryta water, gave with hydrochloric acid, ferric chloride,and ammonia the purple reaction characteristic of the thioglycollicacids, and hence contains the typical linking : *S-CH,*CO*.No indication was observed of the presence of any other productthan that described, which was obviously the hydrobromide of oneof the various forms of so-called phenylmethylthiohydantoin, probablyPhN:C<&-Xz'Te, otherwise, N-phenyl-a-methylthiourantoin (seeDixon, Trans., 1897, 71, 629, 639).Therefore, in the circumstances given, when two halogens (onebeing connected with the CO group of an acyl radicle, and the othera substituent in its hydrocarbon nucleus) are presented simultaneouslyto the SH group of PhN:C(NH,)*SH, the hydrogen of this combinespreponderantly, if not exclusively, with the substituent halogen ;hence the ring-formation which occurs also must depend mainly,if not altogether, on the union of the halogen of the *COBr withthe hydrogen of an amino- or imino-group.To ascertain whether temperature may influence either the directionof the primary combination (that is, which halogen unites with theSH-hydrogen) or the fact of ring-closing, the experiment was repeatedin a freezing mixture a t about - 8'.No substantial difference of anysort was noticed, the sulphur of the product appearing, just as beforeto be linked solely as *S*CHMe-.Chloroacetyl Chloride und Phenylthiocarbamide.Although, in view of the results described above, there couldbe little doubt as to how these substances would interact, the experi-ment was tried, the constituents being mixed in cooled acetone.The white product, a hydrochloride, decomposed at 230' withblackening and intumescence ; from its aqueous solution, whe22 DIXON AND TAYLOR : ACYLOGENS AND THIOCARBAMIDES.neutralised, a white solid crystallised out, having the melting point(1 77-178') of '' phenylthiohydantoin," and giving the reactions ofthis compound.JicetpE Chloride and Allyh?hiocarbcimide,These substances combined vigorously in presence of acetone, theproduct, a white, apparently crystalline powder, melting at 103-104°with decomposition and effervescence.Analysis showed it to be amolecular additive compound :0.389, dissolved in hot ammonia, gave 0.499 Ag,S, and the filtratecontained 0.2822 AgC1.C,HI,0N2S,HC1 requires S = 16-45 ; C1= 18025 per cent.S = 16t55 ; C1= 17.95.The interaction may be represented as follows :(i) C,H,*NH*CS*NH, + CH,*COCl = C 3 H 5H,N>C<g1 *NH*CO*CH,'and thenor(ii) C,H,*NH*C(NH)*SH + CH,*COCl=C,H,*NH*C(NH)*S*CO*CH3,HCl.Water dissolved the substance very freely, but with considerabledecomposition, so that the corresponding picrate, an orange-yellow,crystalline solid, could be obtained only in poor yield.Action of Caustic Alkali.-Twelve grams of the hydrochloride weredissolved in water, and to the solution, without delay, there was runin something less than one equivalent of N/3 alkali; the white pre-cipitate wag then collected by the aid of the pump.The filtrate,which was strongly acid, required for neutralisation about half anequivalent more of alkali, and now contained both chloride andacetate ; consequently, about one-half of the hydrochloride had under-gone hydrolysis with regeneration of allylthiocarbamide ; no thio-cyanate was present.The crystalline precipitate, free from chlorine, melted at 95-96",and, when recrystallised from dilute alcohol, formed brilliant needles,showing the same melting point as before.It was now practicallyinsoluble in hydrochloric acid, and its solution in dilute alcoholyielded no picrate; hence the product did not consist of the base :C3H, NH*C( NH) S* CO*CH,.It was soluble, however, in dilute alkali, the solution being de-sulphurised by heating with a lead salt; on the other hand, whenheated with strong (30 per cent.) potassium hydroxide, it gave a t firsta clear solution, which presently became turbid owing to the sepaxatioDIXON AND TAYLOR : ACYLOGENS AND THIOCBRBAMIDES. 23of an oil; the mixture, whilst reacting intensely for thiocyanic acid,was but slightly darkened by boiling with a lead salt, and hencepractically all the contained sulphur had been eliminated as thio-cyanate, the oil being doubtless allylacetamide.From the aboveresult, it appears that this form of decomposition, so characteristic ofthe aa-acylarylthiocarbamides (see Hugershoff, Ber,, 1899, 32, 3649 ;compare also Dixon and Hawthorne, Trans., 1907, 91, 133; Dixonand Taylor, ibid., 916), holds equally in the aa-acylalkyl class :C3H5*N(CO*Cl€,)*CS*NH2 + KOH 3KSCN + H20 + C,H,*NH*CO*CH,.The above formula was checked by analysis :0.316 required 40.2 C.C. N/10 barium chloride.C,Hl,0N2S requirea S = 20.25 per cent.It had now to be learned whether this second form of acetylallgl-thiocarbamide could be transformed, through migration of the acylgroup, into the third, or symmetrical, variety; that such is the case isproved by the result of the following experiment.Action of Heat.-A quantity of the aa-compound was maintainedfor some time a t a temperature between 100' and 105'.After half anhour, the liquid, when treated with caustic alkali, still reacted verystrongly for thiocyanic acid, but after some two hours' further heatingresponded but feebly to the test, On cooling, the brown meltsolidified, and the solid, when twioe recrystallised from boiling, dilutealcohol, formed long, silky needles melting at 73-74'. With hotwater, the product yielded an almost neutral solution, giving no pre-cipitate with excess of picric acid; it was soluble also in cold strongalkali, the solution being desulphurised by boiling with a lead salt,but giving with hydrochloric acid and ferric chloride no trace of redcoloration.On analysis :S= 20.4.0.158 gave 0.230 BaSO,.C,Hl,ON,S requires S = 20*25 per cent.This product, accordingly, was isomeric with the last described, andconsisted of ah-acetylallylthiocarbamide. The series of changes,starting from the compound of allylt hiocarbamide and acetyl chloride,may be summed up as follows :S = 20.0.C,H,*NH*C(NH)*S*CO*CH,,HCl -+ C,H,*N(CO*CH3)*CS*NH2 -+C,H,*NH*CS*NH*CO*CH,.When ab-acetylallylthiocarbamide mas cautiously heated somewhatabove its melting point, the pungent odour of acetylthiocarbimidebecame perceptible, and the fusion, when treated with water andferric chloride, gave an intense blood-red coloration. This behaviou24 DIXON AND TAYLOR : ACYLOOENS AND THIOCARBAMIDES.of acglated thiocarbamides has already been pointed out and discussed(Dixon, Trans., 1906, 89, 905).From the foregoing experiments, it may be concluded that when afatty acylogen reacts with a monosubstituted thiocarbamide thegeneral behaviour of the product, as regards intramolecular move-ment of the contained acid radicle, is independent of whether thesubstituting group of the thiocarbamide is cyclic or otherwise.Itremained for experiment to show how acetyl chloride would behavewith a disubstituted thiocarbamide containing the allyl' group.Acetyl Chloride and ab-Phenykcllylthiocarbamide.When acetyl chloride was added in slight excess to phenylallyl-thiocarbsmide dissolved in warm benzene, a clear, yellow oil wasprecipitated, showing even after long keeping no tendency to becomesolid.The product, a hydrochloride (containing a trace of phenyl-thiocarbimide), was rather sparingly soluble in water, but easilyso in alcohol, the latter solution yielding with alcoholic picricacid a picrate, crystallising in long, transparent needles, resemblingmonoclinic sulphur in colour and appearance, and melting at154-155' (corr.).With dilute caustic alkali, the aqueous solution of the hydrochloridegave an oil, soon changing t o a crystalline solid ; the latter, after tworecrystallisations from boiling dilute alcohol, sepa.rated in needlesmelting at 117-1 1 8 O (corr.). The product was slightly alkaline ;when treated with hydrochloric acid, it yielded again the oilyhydrochloride, and then in turn the picrate : hence it was plain thatthe acetyl group, if united originally to sulphur, had not undergonethe usual movement to a nitrogen atom, since in that case the basiccharacter would have been lost.Moreover, that the acetyl group hadnot remained attached to sulphur was evident from the facts, that onboiling the base with caustic alkali and a lead salt the mixture wasnot darkened, and that the alcoholic solution gave with silvernitrate a white precipitate, sparingly soluble in ammonia and showingno sign of desulphurisation when boiled with it.Boiling with concentrated nitric acid failed to produce any detectableamount of sulphuric acid ; nevertheless the compound containedsulphur, for on ignition with zinc filings, metallic sulphide wasobtained, and by fusion with caustic alkali and nitre, alkali sulphate.The sulphur therefore must form part of a ring; from which it wasinferred that the acetyl group had probably gone to saturate theallyl group, in which case, ring formation could easily occur in eitherof the following ways DIXON AND TAYLOR : ACYLOGENS AND THIOCARBAMlDES. 25(i) PhNH*CS*NH*CH,*CH:CH, + AcCl =if now, as usual, the chlorine and the SH-hydrogen interact,PhNH*CS*NH*CH,*CHAc.CH,CI,(ii) PhNH-CS*NH*CH,*CH:CH, + AcCl =whence, as before,PhNH*CS*NH*CH,*CHCl*CH,Ac ;Analysis, however, failed to substantiate this view, for :0.20 gave 24.6 C.C.moist nitrogen at 15" and 748 mm. N = 14.7,whilst the compounds just formulated would require N = 11-97 percent.The percentage of nitrogen found agrees closely with that calculatedfor phenylallylthiocarbamide itself, namely, 14.58, and a comparisonof the properties of the product with those of the isomeride of phenyl-allylthiocarbamide, N-phenylpropylene-$-thiourea,"obtained by Prager (Bey., 1889, 22, 2992) from the first-named andconcentrated hydrochloric acid at loo", shows them to be the onecompound, Prager gives for the melting points of base and picrate,11 7" and 154O respectively ; the authors' figures, as stated above, were117-118O and 154--155'.If the mechanism of this unexpected change operates as supposed,the chlorine of the acetyl chloride must have united primarily with themiddle carbon atom .of the ally1 group as represented in case (ii)above; here, by the simple exchange of hydrogen for acetyl, howeverthis be conditioned, the propylene configuration would result :Considering that allylthiocarbamide reacts with hydrochloric acidat 100Oin precisely the same way as does phenylallylthiocarbamide (thatN.7H2 ; see Gabriel,S--CH*CH,is, propylene-$-thiourea is formed, NH,*C<Bey., 1889, 22, 2985), it seems curious that the two should behave sodifferently with acetyl chloride.The question naturally arising whether an acylogen less electro-negative than acetyl chloride would behave similarly to the latter, thealkyl chlorocarbonates were selected for the purpose of experiment26 DIXON AND TAYLOR : ACYLOGENS AND THIOCARBAMIDES.Methgl Chlorocarbonate and Pherrylullyl~hiocatrbamide.Slight excess of methyl chlorocarbonate was added to a gentlywarmed solution of phenylallylthiocarbamide in acetone.No heatmas evolved, nor did the mixture become turbid, but on evaporation a tthe ordinary temperature, beautiful, large, vitreous prisms were ob-tained; after being well washed with ether and dried, they meltedwith copious effervescence a t about 87O.The product dissolved in sulphuric acid with frothing and evolutionof hydrogen chloride.0.3006 required 10.5 C.C. N/10 silver nitrate.About 88 per cent. of the theoretical yield was obtained.On analysis :C1= 12.4.C,,H,,O,N,S,HCl requires C1= 12-39 per cent.The gasexpelled by heating the hydrochloride proved to be carbon dioxide;by maintaining the heat cautiously until the effervescence ceased, anoily residue was obtained, the solution of which in water gave withcaustic alkali a white, oily precipitate having a strong odour ofmercaptan and yielding with a lead salt the yellow lead mercaptide.The chlorocarbonate residue therefore had become attached t o thesulphur atom (and not to the ally1 group), the change by heat pro-ceeding thus :C,H,*NH*C(N*C,H,) *S*CO,*CH,,HCl=CO, + C,H,*NH*C(N*CGH,)*S*CH,,HCI.ActioTe of Walein on the Hydrochloride.-When added to water, thehydrochloride yielded a very acid solution, which, if treated at oncewith picric acid, gave the bright yellow picrate; with caustic alkali,it furnished a white precipitate, soluble in excess, the solution havinga distinct odour of mercaptan, and undergoing desulphurisation whenheated with a lead salt.On the other hand, the aqueous solution,when kept for a short time, became turbid (the same change occurreda t once on warming), owing to the separation of an oil, soonchangingto a crystalline solid ; the liquor from this, when treated with picricacid, yielded no precipitate, neither did caustic alkali give any pre-cipitate or produce the odour of mercaptan; when the alkalinemixture was treated with a lead salt, no mercaptide was formed, butdesulphurisation occurred on warming :The material precipitated by the action of water on the dissolvedhydrochloride contained no chlorine and had lost all basic properties ;it was now insoluble in dilute hydrochloric acid,-and did not yield apicrate. When recrystallised from dilute alcohol, it formed long,colourless prisms, melting at 82-83O without effervescence.Thesolution in caustic alkali gave no mercaptan on heating, and whenmixed with a lead salt was slowly desulphurised by boilingDIXON AND TAYLOR : ACYLOGENS AND THIOCARBAMIDES. 27These phenomena are so nearly in aacordance with those observedfor the compounds of ethyl chlorocarbonate with phenylthiomrbamideand its congeners (Dixon and Taylor, Zoc. cit.) as to leave no doubtthat all belong to the same class,What occurs therefore in the attack by water may be explained asfollows. Dissociation of the hydroahloride takes place, the hydro-chloric aoid passing into solution] with liberation of the free base,either carboxymethyl-$-n-pheny 1 -v-allylt hiourea,C,H,*NH*C( NPh)*S*CO,Me,PhNH* C( N*C,H5)*S*C0,Me,which is unstable in presenoe of water, probably by reason of the feebleattraction between sulphur and the acidic group.I n a case such asthis, at least so far as we yet know, if neither of the nitrogen atomsof the thiourea be substituted, the acid group simply leaves themolecule by hydrolysis, whereupon the corresponding thiocarbamideis regenerated; but if one be substituted, the acyl group now movesto it, and there becomes attached, so as to produce an aa-disubstitutedthiocarbamide. In this particular instance, where both nitrogenatoms are substituted by different radicles, the acyl group mightbecome attached to either, or distributively to both ; it was observed,however, that in the attack by caustic alkali, phenylthiocarbimidewas always produced, a fact which gives some clue to the position ofthe phenyl group.For, when caustic alkali decomposes an aa-di-substituted acidic thiocarbamide, the interaction takes place almostquantitatively as follows :AcArN*CS*NH, = AcArNH -I- HSCN.or its tautomeride, carboxymethyl-v-pheayl-$-n-allylthiourea,That is, of the two hydrogen atoms available, one goes to form sub-stituted amide, the other yielding H*NCS, a compound which doesnot exist as such in contact with water, but passes rapidly into theform, H*SCN. If the behaviour of a trisubstituted derivative issimilar, then, when the one remaining hydrogen atom has passed overto the disubstituted nitrogen atom to form the corresponding amide,there remains only CSN*R, a thiocarbimide, the radicle, R, beingthat originally associated with the hydrogeniaed nitrogen.Since, then,in the above decomposition, phenylthiocarbimide is produced (nothiocyanie acid could be detected), there is at least some ground forsupposing the composition of the parent compound to be :C,H,*N( CO,Me)*CS-NH*C,H,,unless it be the isomeric (or tsutomeric) thiourea, from which atpresent there is no means of distinguishing it28 DIXON AND TAYLOR : ACYLOGENS AND THIOCARBAMIDES.To check the composition of the supposed trisubstituted derivative,0.250 gave 0.239 BaSO,.i t was analysed :S = 13.1.C,,HI,0,N2S requires 8 = 12.80 per cent.Ethy? Chlorocadonate and PhenyZa~Zylt~iocarbctmic2e.By operating as described in the last case, precisely similar resultswere obtained, the end product being a crystalline, white hydro-chloride, melting with effervescence (due to tho escape of carbondioxide) a t 96O :0*601 required 19.7 C.C.N/10 silver nitrate. C1= 11.6.C1,Hl,O,N,S,HC1 requires C1= 11 081 per cent.In all respects save one, the properties of t h i s hydrochlorideresembled those of the preceding, and hence need not be described indetail. The one point of difference was that the oily precipitate, whichseparated from the aqueous solution of the hydrochloride, did notsolidify, even after remaining for some time at - 8' and then for sixmonths in a vacuum desiccator. Otherwise it resembled the methylichomologue, being gradually desulphurised, for example, by hotalkaline lead tartrate, without yielding any odour of mercaptan.Trisubstituted thiocarbamides, containing hydrocarbon groups, arenot desulphurised readily, if at all, by this treatment ; it is probabletherefore that the change mentioned, which is markedly slowerthan in the case of the parent phenylsllylthiocarbamide, is due to thewithdrawal of the contained acyl group by means of the alkali.On analysis, the oil gave the following result :0.2664 yielded 0.232 BaSO,.S = 12.0.Cl,H,,02N,S requires S = 12.12 per cent.Hence it was a form of carboxyethylphenylallylthiocarbamide.I n addition to the above, a number of experiments were conductedwith the view of learning whether union could be effected of (1) benzylchloride with acetylthiocarbamide, and (2) acetyl chloride with benzyl-+-thiourea, thus :AcNH*CS*NH, + C7H~C1 = AcNH*C(NH)*S*C,HT,HCI ;NH,*C(NH)*8*C,H7 + A&= AcNH*C( NH)*S*C,H,,HCl,and if so, whether the products would be identical or would differfrom one another, owing to the occurrence of tautomeric forms.Both these combinations, it was found, could easily be effected,the latter occurring vigorously when the constituents, dissolved incold acetone, were mixed together; in each case, a white, crystallinehydrochloride was isolated, and shown by analysis to be an additivecompound.From each hydrochloride, too, a oorresponding base waDIXON AND TAYLOR : ACYLOGENS AND THIOCARBAMIDES. 29liberated, the sulphur contents of which agreed closely with the figurescalculated.Nevertheless, such considerable variations of melting point wereencountered amongst the hydrochlorides that no definite conclusioncould be drawn as to their identity or otherwise, and the same was trueregarding the bases.The melting points of the latter were generallywanting in sharpness, overlapping one another somewhere in the neigh-bourhood of 140’ ; by recrystallisation (during which benzyl mercaptanwas freely evolved), they could be made to coincide a t 210--211°, theproduct, acetylcarbamide, resulting, no doubt, from the acetylcyanamidoformed by loss of benzyl mercaptan :AcNH*C(NH)*S*C,H, = C,H7*SH + AcNH*CNThe compounds being so unstable that there seemed little prospectof isolating them in a really pure condition, the experiments in thisdirection were not pursued ; i t may perhaps be added that continuedwork with benzyl mercaptan is very disagreeable.With benzylthiocarbamide in acetone, acetyl chloride gave a whitehydrochloride, which became pasty even when kept in a desiccator,and had an odour of acetyl chloride.Ferric chloride gave with theaqueous solution no trace of red coloration ; but on treatment withstrong alkali, thiocyanic acid was produced in abundance, showingthat the acetyl group had migrated t o the benzylated nitrogen atom.The amount of material being small, no attempt was made to isolatethe aa-acetylbenzylthiocarbamide. The isomeric ab-compound,produced by Werner (Trans., 1891,59,562) from benzylthiocarbamideand acetic anhydride, gives no thiocyanic acid when treated withalkali.Sumrnary and Conclusion.Briefly put, the main results of the present inquiry are as follows :(1) When an ordinary acylogen, R*CO*X (X = halogen), uniteswith phenylthiocarbamide, the product is a derivative of phenyl-thiourea, PhNH*C(NH)*SH, having the form :PhNH*C(NH)*S*COR.If, howover, the acylogen contains a second halogen as substituent inthe aliphatic nucleus, R, the interaction takes place differently, thesulphur atom now becoming engaged, not with the carbon of the COgroup, but with the other carbon atom which originally was halogen-ised; concurrently, the halogen of the group *CO*X withdrawshydrogen from the non-phenylated nitrogen, and ring-closing occurswith production of a substituted “ thiohydantoin.”(2) Acetyl chloride behaves with allylthiocarbamide precisely aswith monosubstit uted arglthiocarbamides, yielding a hydrochloride30 CLARKE, LAPWORTH, AND WECHSLER : CONDENSATION OFC,H,*NH*C(NH)*SAc,KCl, the acetyl group of which may be causedto migrate within the molecule so as to yield, first,C,H,*NAc CS*NH,,and then C,H,*NH*CS*NHAc j the latter compounds melt at 96’ and7 4’ respectively.(3) With ccb-phenylallylthiocarbamide, acetyl chloride yields‘‘ A‘-phenylpropylene q-thiourea,” PhNH*C< I the acetylgroup being eliminated,(4) ab-Phenylallylthiocztrbamide unites with methyl chloro-carbonate to form a hydrochloride, probablyC,H, *NH *C(NPh) *S *CO,Me,HCi ;by mere dissolution in water, this substance loses hydrogen chloride,the carboxymethyl group thereupon migrating to yield a trisubstitutedt hiocarbamide, probably C,H,*N (C0,Me) CS4 NH Ph. With ethylchlorocarbonate, similar combinations are obtained.X* CH *CH3’CHEMICAL DEPARTMENT,QUEEN’S COLLEGE,COILK

ISSN:0368-1645    

DOI:10.1039/CT9089300018

出版商:RSC    

年代:1908

数据来源: RSC

摘要:

30 CLARKE, LAPWORTH, AND WECHSLER : CONDENSATION OFIV.--Condensa tion of lietones Containing the Group*CH2*C0 C I I : with Esters in Presence of SodiumEthoxide.By REGINALD W. L. CLARKE, ARTHUR LAPWORTH, and ELKANWECHSLER.THE acetoacetic ester condensation, in its most general form, is thatwhich occurs when a carboxylic, nitrous, or nitric ester (class E)is brought into contact with a ketone, carboxylic ester, or nitrile(class K) containing the group :CH*CO*, or :ClH.CN, in presence ofsodium ethoxide, sodamide, sodium, or similar agent. The questionof its mechanism has been the subject of much controversy and isassociated with numerous investigations. ** Geuther, Jahresber., 1863, 323 ; Zeitsch. f. Chent., 1868, 11, 662 ; Franklandand Duppa, Phil. Tram., 1866, 156, 37 ; Aanden, 1866, 138, 204, 328 ; Kolbe,Zeitsch.f. Chem., 1867, 10, 637 ; Wislicenus, Annalen, 1877, 186, 163 ; Baeyer,Ber., 1885, 18, 3640; Duisberg, Ber., 1883, 16, 133 ; Claisen and Lowman, Ber.,1887, 20, 651 ; 1888, 21, 1154 ; Bromnie and Claisen, ibid., 1888, 21, 1132 ;Claisen, ibid., 1894, 27, 114; 1905, 38, 708; also Annalen, 1893, 277, 184;1896, 291, 25 ; 1897, 297, 92 ; Michael, J. pr. Chem., 1888, [ii], 37, 507 ; Ber.,1900, 33, 3731; 1905, 31, 1922; Nef, Annalcn, 1897, 298, 319; Dieckmann,Ber., 1900, 33, 2670 ; Lapworth, Trans., 1901, 79, 1269 ; 1902, 81, 1512 ; Proc.,1903, 19, 190KETONES CONTAINING THE GROUP ‘CH;CO’CH: WITH ESTERS. 31I n spite of all evidence against it, Claisen’s theory of themechanism of the condensation (Ber., 1887, 20, 646; 1888, 21,1154) is still the one most frequently cited.The theory wasadvanced at a time when the general rule appeared to obtain that thesubstances of class K (abovo) must contain the group *CH2*CO*, orCH,*CN, and fell to the ground when Dieckmann explained theapparent absence of reactivity in compounds containing the group:CH*CO*, or :CH*CN (Ber., 1900, 33, 2670), and Perkin and Thorpediscovered a case which could not possibly be explained by Claisen’sproposition (Trans,, 1900, 79, 736 and 737).I n the work described in the latter part of the present paper, it isshown that certain simple ketones containing the group:CH*CO* CH,-,when submitted to the action of an alkyl nitrite under the conditionswhich with other esters lead, as usual, t o attack at the *CH,* group,are affected only at the :CH* group, and an explanation of this isafforded readily enough on general grounds and in the light ofDieckmann’s experiments.Claisen’s theory, however, is not appli-cable, and in this connexion his own words may be quoted : “Zuverwerfen sind natiirlich alle Vorstellungen, mit denen nur einzelne,nicht alle dieser Estercondensationen erklart werden ” (Ber., 1905,38, 715).Other views of the acetoacetic ester condensation have assumed apreliminary conversion of the compounds of class K into theirC-sodium derivatives, Na*6*CO*, or JYa*d.CN (Frankland and Duppa,Annalen, 1883, 219, 123; Baeyer, Ber., 1885, 18, 3640; comparealso Michael in numerous papers already cited), but recently thetendency has grown among chemists to suppose that the metallic deriv-atives of ketones, nitriles, kc., when they exist, are derived solely fromthe enolic forms, and such is doubtless the case with the solid com-pounds ; consequently, efforts have been made to explain the apparentlyanomalous reactions of these 0-sodium derivatives as involvingadditions at the double linking, for example :>C:d*ONa + CH,I -+ >CNe*g*ONa -+ >CMe*bO + NaII(Michael, J.pr. Chern., 1883, [ii], 27; 487; 1892, [ii], 46, 205 ; 1899,[ii], 60, 316), or, as the result of isomeric change in pre-formed0-substituted compounds :>C:’C*O*CH, --+ >CMe*&O(compare Claisen, Ber., 1905, 38, 714, where such a change isassumed as a part of the mechanism of the acetoacetic estersynthesis).32 CLARKE, LAPWORTH, AND WECHSLER : CONDENSATION OFSerious objections can be urged against such explanations, and weventure here to draw attention once more to what appears likely toprove the most satisfactory view, namely, that isomeric change isinvolved, but that it is to be looked for in the ionsof the metalderivative (WislicenuF, ‘‘ Tautomerie,” Ahrens’ Voi-trage, 897 et seq ;Knorr, Anncden, 1896, 293, 39; Lapworth and Hann, Trans., 1902,81, 1512; 1904, 85, 4 8 ; Lapworth, Proc., 1903, 19, 190) or inthe sodium derivative itself (Lander, Trans., 1903, 83, 420). Itmay here be noted that Bruhl has brought forward some evidence thatmetallic derivatives of camphor can actually be isolated in both theC- and 0-forms (Ber., 1904, 37, 2170).Apart altogether from the conception of electrolytic dissociation, theexceptional lability of metals, and especially those of the alkalis andalkaline earths as exemplified by the almost universal and instanta-rieous reactivity of the metallic salts and even organo-metallic com-pounds, is sufficient to render it likely that they must be more labilethan any other types of atoms or groups.Lander’s proposition mayusefully be employed as an alternative to the earlier ionic one, beingespecially attractive, since Kahlenberg’s experiments with the oleatesin which the metals exhibit their instantaneous lability in spite ofthe absence of noticeable dissociation.From this standpoint, there is, in solutions of the sodium deriv-atives of p-ketonic esters and allied compounds, a virtual or r e dequilibrium between the 0- and C-sodium derivative ::C:CONa +-+ :CNa.CO,and this may be a t once extended to the metallic derivaiives of othercompounds containing the groups :CH*CO*, :(3H.CN, :CH*NO,, &c.,and, where amines are employed as catalytic agents in promotingcondensations with such compounds, then the ammonium radicle,NR,H*, may be supposed to functionate as a metal.For convenience,however, in the following lines, the univalent metal or ammoniumradicle f unctionating as the positive, labile, polar ” portion (compareAbegg, Bey., 1905, 38, 4112 et S e q . ) will be represented by thesymbol M.The real or virtual existence of C-metallic derivatives OF thecompounds of class K (see p.30) having been postulated, a satis-factory explanation of the acetloacetic ester condensation, as wellas of a large number of other reactions which occur with thecompounds of class K in alkaline media, follows without difficulty.The C-metallic derivatives should exhibit the characters of organo-metallic compounds proper, and a little consideration of the factsshows this to be the case, for the reactions of the metallic derivativesof ketones, and class K generally, are either those of phenols (enolsKETONES CONTAINING THE GROUP 'CH;CO'CH: WITH ESTERS. 33or of organo-metallic compounds, although, in the latter instance,developed to a less marked degree owing to their lower potentialconsequent on the more "negative" character of the organo-radicle (Michael).I n the present instance, the question under consideration is that ofthe reactions of the isomeric M-derivatives with carbonyl and cyano-groups.Organo-metallic compounds proper are characterised by theextraordinary facility with which they form additive compounds withsubstances containing the carbonyl group :>C:O+M*Alk --+ >C<iE,and analogous compounds are formed by addition to *CN, *SO,*, *N:Ogroups.The C-metallic derivatives of ketones, esters, nitriles, and nitro-paraffins behave in the same way :OM>C:O +M*d*CO ++ >C<bsc0 .the change, when it ceases here, being known as the aldol condensa-tion, and being to some extent reversible. The carbonyl compound> C O virtually selects the C-metallic derivative rather than the0-derivative, but merely because the products of its condensation withthe latter :.. J0 .OM >c:o + &foci: . . f3 >c<o.c:d . .are of a type eminently unstable and revert a t once to their generators.The aldol condensation when brought about by bases may thus itselfbe regarded as an instance of the general reaction between organo-metallic compounds and substances of class K, and, moreover, isrecognised as a necessary stage in a very large number of reactionsto which special names have been attached, such as the croton-aldehyde condensation, the Perkin synthesis, and others.The acetoacetic ester condensation is also clearly only a particularcase of the interaction of esters and organo-metallic compounds.Thus one of the latter acting on ethyl formate yields an aldehyde :whilst with t h e C-metallic derivative of a carbonyl compound preciselythe same type of change occurs :X*CO*[b*C:O] + 11-OEt, ..a P-diketone or P-ketonic ester being formed.VOL. XCIII. 34 CLARKE, LAPWORTH, AND WECHSLER : CONDENSATION OFConfusion has probably arisen simply because the product inthe latter instance is, from its very nature, prone to further change,but the substances isolated are exactly those which the compoundX*CO*c'*C:O would yield under the experimental conditions. Withthe latter point, Dieckmann has already dealt (Zoc. cit.), and referencemay be made to his paper, but the following forms a very briefsummary of the possibilities.* *Representing the above Condensation product aswx*co*c*co*z,-irthen1.( a ) If X, W, Y, and Z are all alkyl groups, the compoundis unstable under the experimental conditions, and falls into itsgenerators :WX*CO*OEt + H*b*CO*Z,-iTby reversal, or (6) might break up into two new compounds :'CVX*CO*bH + OEt*CO*Z.ri-2. If either W or Y is a hydrogen atom, then the substance isconverted by the metallic alkyl oxide into a stable metallic derivativeof the enolic form, reversal thus being obviated.3. If Z (or X?) has the structure -CHR*CO*R' or *CHR.CN, tben,even if W and Y are both alkyl groups, a stable metal enolicderivative may be formed and reversal inhibited.Case 1 ( a ) has been dealt with by Dieckmann (Zoc.cit.), but case1 ( b ) has not yet been observed. Case 2 is the ordinary acetoaceticester type of synthesis so fully elaborated by Claisen. Case 3 is thatnoticed by Perkin and Thorpe (Trans., 1900, 79, 736 and 737).The condensations dealt with in the present paper were made withketones containing the groups *CH2*CO*6H and CH2*CO*C':C! respect-tively, the ester with which they were made to react being a nitrousand not a carboxylic ester. It has usually been supposed that, as withother esters, these condense only with ketones which contain thegroup *CH,*CO-, but such is, in reality, not the case. In theinstances we have examined, attack appears to be directed almostexclusively a t the :CH*CO* group.The behaviour of menthone with alkyl formates, on the one handKETONES CONTAINING THE GROUP 'CH;CO'CH: WITH ESTERS, 35and alkyl nitrites, on the other, is very instructive.instance, the initial products may be eitherIn the formerCH,-C( CHMe,)*CHO CH,4CH(CHMe,)dlH, 60 or 6H2 60eHMe*bH, kHMe*kH*CHOOf these, the former is perhaps formed more rapidly than the othera t first, but belongs to a highly unstable type and readily falls into itsgenerators, yielding, by absorption of alcohol, alkyl formate andmenthone, The latter, however, is rendered stable by conversion intothe sodium derivative of the enolic form, which the former cannotyield.With alkyl nitrite, the corresponding forms are :CH,-C( CHMe,)*NO CH,-CH(CHMe2)dlH, 60 and &€, 60~HM&H, dHRle*dH*NOand here the former type does not revert to its generators, owingno doubt to the greater stability of the linking *C*NO comparedwith *C*CO*.As a result, it is at the grouping *CaCO* that re-absorp-tion of the elements of alcohol occurs, and the next products in succes-sion are :. .bCH,--CH( CHMe,) *NOdlHMe*bH, dHMe*bH,CH,-C( CHMe,): No0 H6H2 C0,Et --+ dH, C0,EtThe compound obtained as the product of the reaction, on removingalcohol, neutralising, and extracting, has the properties of an ester, andthis, if boiled with alkalis, is converted into the same hydroximino-acidas is obtained by treatment of menthone with amyl nitrite and hydro-chloric acid, but the yield in the latter instance is comparatively verypoor.The first observation of this apparently anomalous behaviour ofnitrous esters when used in conjunction with sodium ethoxide wasmade by Hantzsch (Ber., 1887, 20, 579; compare also Dieckmann,Be?*., 1900, 33, 579), but referred to a-monosubstituted /3-ketonicesters, and he does not attribute any special significance to his results,probably because such compounds are resolved in so many differentways at the point between the a- and @carbon atoms.The compoundsdealt with in the present paper are simple ketones, and the investiga-tion was undertaken with the object of finding an explanation of theresults obtained when an attempt was made to prepare isonitroso-cyanodihydrocarvone (Lapworth and W echsler, Trans., 1907, 9 1,978and 1919). Here we mere forced to the conclusion that attack tookD 36 CLARKE, LAPWORTH, AND WECHSLER : CONDENSATION OFplace, not at the *CH,*CO.group, but exclusively at the :CH*CO*complex.From pulegone (I), by similar treatment, we obtained an esterhaving the structure (11) :NOH C02Etso that a migration of a hydrogen atom from the side-chain to thea-carbon atom must have occurred at an intermediate stage; in otherwords, a partial conversion of pulegone into isopulegone seems tohave taken place.The constitution of the product was determined by oxidising theacid with permanganate, when it was found to be converted intoformic, acetic, nitrous, and P-methyladipic acids :Other compounds examined in respect to their behaviour with nitrousCHBresters and sodium ethoxide were a-bromocamphor, C,H,,<bo ,which reacted readily, but yielded ordinary isonitrosocamphor, andfenchone which was unchanged, although a variety of conditions wasimposed, and thus further support is offered to the contention ofSemmler (Ber., 1906, 39, 2581) that fenchone contains the groupingc\ c- c G O * c-c./"C/ \cE x P E R I M E N T A L.Action of Amy? Nitvile on Jlenthone in Pszesence of SodiumE'thoxide.I n the first experiments on this reaction, it was found that an oilysubstance only was obtained if the product was isolated merely bydilution and extraction with solvents. This oily material, it masnociced, evolved a considerable quantity of amyl alcohol when treatedwith alkalis or acids, and this led to the surmise that esters werepresent, so that the following process was adoptedKETONES CONTAINING THE GROUP 'CH,'CO'CH: WITH ESTERS. 37Menthone was added to an ice-cold solution of slightly more thanone atomic proportion of sodium in absolute alcohol, and subsequentlya molecular proportion of amyl nitrite was introduced a t such a ratethat the temperature did not rise more than one or two degreesabove zero.After standing in the cold for some hours, the wholewas distilled with the aid of a current of steam until the distillatewas odourless, the resulting liquid being then agitated with a littleanimal charcoal and filtered. Hydrochloric acid was next added tothe cooled solution until no further precipitate formed, the oily sub-stance which separated being allowed to solidify, when i t was removedand crystallisod from methyl alcohol.I n this way, 75 grams wereobtained in a nearly pure state from 85 grams of menthone :0.3102 gave 0.6738 CO, and 0.2644 H,O.0,2153 ,, 15.45 C.C. moist nitrogen a t 14' and 746 mm. N = 7.1.C,,H,,O,N requires C = 59.7 ; H = 9.5 ; N = 7.0 per cent.0.961 required 4'7.1 C.C. N/10 NaOH for neutralisation, whence theequivalent = 204 (calculated = 201).As the properties of the acid agreed closely with those of theoxime of P[-dimethyloctan-E-onoic acid, obtained by the action ofamp1 nitrite on menthone in presence of acid as catalyst, some of thatoxime was prepared by the latter process. No difference between thetwo substances could be detected, and their melting points wereunaltered on admixture.The following new derivatives of the Rcidwere prepared.The p-nitrophenylhydraxone formed a bright yell0 w, crystallinepowder melting at 130" :0.1059 gave 11.9 C.C. moist nitrogen a t 16" and 758 mm. N = 13.1.The semicar6axone was obtained in small, white crystals :0*1208 gave 18.1 C.C. moist nitrogen a t 15' and 773 mm. N= 17.8.CllH2103N3 requires N = 1'7.3 per cent.These compounds were formed on warming the oxime with aqueoussolution, p-n i t rophen yl hydrazine acetate, and semicarbazide acetaterespectively, the hydroxylamine being eliminated with great ease.C = 59.3 ; H = 9.5.C16H2505N3 requires N = 13.1 per cent.Actiolz of Amyl Nitrite on Pulegone in Presence of Xodium Ethoxide.This reaction was carried out in a manner similar to that describedin the case of menthoce, but, as the esters formed appeared to be morestable, the product, some hours before the steam distillation, was mixedwith an excess of strong aqueous potassium hydroxide.The materialwhich separated on acidifying the aqueous residue at the end of thesteam distillation was very gummy, and it was found necessary t38 CLARKE, LAPWORTH, AND WECHSLER : CONDENSATION OFpurify it by dissolving it in ether and extracting the acidic matterfrom this by shaking it with sodium carbonate solution. Afterdissolved ether was removed from the .alkaline liquid, hydrochloric acidprecipitated a viscid mass, which slowly became semicrystalline aftertrituration with acetic acid. The solid portion was the oxime of a newacid, which we propose to term “isopulegonic acid,” in order to indi-cate its near relationship to isopulegone.I t was finally purified bycrystallisation from dilute methyl alcohol :0.2070 gave 0.4604 GO, and 0.1646 H,O. C= 60.7; H= 8.8.0.1538 ,, 9.9 C.C. moist nitrogen at 18’ and 738 mm. N= 7.2.CI,ET170,N requires C = 60.3 ; H = 8.5 ; N = 7.0 per cent,0,4115 required 20.5 C.C. N/10 NaOH for neutralisation, whence theequivalent = 201 (calculated = 199).The compound is readily soluble in methyl or ethyl alcohoI, ether,benzene, chloroform, ethyl acetate, or carbon disulphide, but dissolvesonly sparingly in light petroleum or hot water. It melts at 85’.When heated above its melting point, the compound decomposed,ammonia and an unpleasant smelling vapour being evolved.It reducesa hot ammoniacal solution of silver nitrate, but has no effect onFehling’s solution unless it has been previously heated with a mineralacid, when the product reduces this solution in the cold, a behaviourwhich indioates that the substance is the oxime of a ketonic acid.The compound gave no crystallisable compound on acetylation.Attempts to obtain a specimen of the pure ketonic acid in a statesuitable for analysis were unsuccessful. When it was warmed withhydrochloric acid, the product cooled, and extracted with ether, an oilwas removed in small quantity in which the presence of a ketonic acidwas proved by warming it with aqueous semicarbazide acetate. Thesemicarbaxone separated as a white solid, and, after repeated crystal-lisatian from alcohol, melted at 100’ :0.1060 gave 15.2 C.C.moist nitrogen at 9 O and 757 mm.C,oH160,N*NH*CO*NH, requires N = 17.4 per cent.Unlike the allied oxime of Pc-dimethyloctan-r-onoic acid, thehydroximino-acid from pulegone i s too stable to yield the semimb-azone or p-nitrophenylhydrazone when merely warmed with theacetates of the corresponding bases.N = 17.2.Oxidation of the Oxime of isoPulegonic Acid.As it was found impracticable to isolate pure pulegonic acid, theexperiment of oxidising the pure oxime itself was undertaken. Twelvegrams of that compound were dissolved in a solution of sodiumcarbonate, and to the ice-cold solution was added very gradually a2 per cent. solution of potassium permanganate. The colour of thKETONES CONTAINING THE GROUP 'CH,'CO'CH: WITH ESTERS. 39latter at first disappeared instantaneously, and the addition of theoxidising agent was continued until an appreciable interval elapsedbetween its introduction and the disappearance of the pink colour,which was the case when about 18 litres had been used.The liquidwas then freed from manganese dioxide in the usual manner, evaporatedto a bulk of about 100 c.c., mixed with carbamide, acidified withsulphuric acid, and distilled in a current of steam,(a). Volatile Acid Products.-The odour of fatty acids being percep-tible, three-fourths of the distillate was neutralised with normal sodiumhydroxide, mixed with tho remaining fourth, and the whole evaporated.The residue had the appearance of sodium acetate, and gave an esterhaving the odour of ethyl acetate on treatment with sulphuric acid andalcohol; i t was therefore redissolved in water, mixed with silvernitrate solution, and the silver salt which separated was washed, dried,and analysed :0.3066 gave 0.1981 Ag, whence the equivalent of the volatile acidThe solution from which the silver salt had been removed blackenedconsiderably on standing, a fact indicating the presence of a smallquantity of formic acid.(b).Non-uoZcctiZe P.rocZzccts.-The liquid from which the volatile acidshad been removed was acidified, extracted repeatedly with ether,which was afterwards washed with a little water, dried, andevaporated, the residue being freed from alcohol by frequent evapora-tions with water.A semi-solid mass was 6nttlly left which was foundto yield a considerable quantity of a sparingly soluble copper salt, andthe whole was therefore dissolved in water, neutralised with ammonia,and mixed with copper acetate, the precipitated copper salt beingremoved, washed with water, and decomposed with hydrogen sulphidein the usual way. In this manner, a semicrystalline material wasobtained which was freed from adherent oil and crystallised repeatedlyfrom ethyl chloride and light petroleum :was 60.1, the equivalent of acetic acid being 62.0.1511 gave 0.2920 CO, and 0.1047 H,O.0.1232 required 15.7 C.C. B/10 NaOH for neutralisation, whence theequivalent = 78.4, whilst a dibasic acid, C7H,,04, has theequivalent 80.0.The substance was readily soluble in most of the organic solventswith the exception of light petroleum, and separated in slender needlesmelting at 84-85'.It did not yield an anhydride when heated a t200', and had all the characters of P-methyladipic acid.To confirm the production of formic acid during the above oxidationa specimen of the pure oxime of isopulegonic acid was boiled with diluteC = 52.7 ; H = 7.7.C7H1204 requires C = 52.5 ; H = 7.5 per cent40 CONDENSATION OF KETONES WITH ESTERSsulphuric acid and potassium dichromate, and the distillate, which hada faint odour of formaldehyde, collected. The presence of form-aldehyde was confirmed by adding hydrochloric acid and phloroglucinolto a portion of the liquid, when a pink colour developed. Theremainder of the distillate was neutralised with sodium carbonate,evaporated, and tested for formate with ammoniacal silver nitrate andwith mercuric chloride, and in both cases a positive result was obtained.No appreciable quantities of products other than nitrous, formic,acetic and P-methyladipic acids could be detected as oxidationproducts.Action of Amy1 Nityite on a-Bromocanaphor in Presence of SodiumEthoxide.When a-bromocamphor was subjected to treatment in the mannerdescribed in the case of menthone, rapid action occurred, and potassiumbromide separated in considerable quantities. The product was dis-tilled in a current of steam, when much unchanged bromocamphorpassed over, and the residue, which was yellow, gave a solid pre-cipitate on neutralisation. This was collected and crystallised fromalcohol, when it was found to melt at 152-154'; it was insoluble insolutions of alkali carbonates, although freely soluble in sodiumhydroxide, and was therefore not a carboxylic acid. It containednitrogen, gave camphorquinona when boiled with formaldehyde andhydrochloric acid, and had all the other characteristics of ordinaryisoni trosocamp hor.Fenchone did not react with alkyl nitrites under the conditionsadopted in any of the experiments above described.Much of the cost of the investigation was defrayed by a grantawarded by the Research Fund Committee of the Chemical Society,for which we wish to express our indebtedness.CHEMICAL DEPARTMEKT,GOLDSMITHS' COLLEGE,NEW CROSS, S.E

ISSN:0368-1645    

DOI:10.1039/CT9089300030

出版商:RSC    

年代:1908

数据来源: RSC

摘要:

ELECTROMETRIC DETERMINATION OF THE HYDROLYSIS OF SALTS. 41V.-The Electrometric Determination of the Hydi*olysis0 f Salts.By HENRY GEORGE DENHAM, M.A., M.Sc., 1851 Exhibition Scholar,University of New Zealand.Introduction.NUMEROUS methods have been employed for measuring the amount ofhydrolysis in salt solutions. Amongst the most important of thesemay be mentioned those depending on the determination of theinversion of sucrose, the hydrolysis of methyl acetate, electricalconductivity, lowering of freezing point, and distribution betweentwo solvents. These methods have been employed in the researchesof Ley (Zeitsch. physikal. Chern., 1899, 30, 193); Bruner (Zeitsch.physikal. Chem., 1900, 32, 133); Walker and Aston (Trans., 1895,67, 576) ; Bredig (Zeitsch.physikd. Chew,., 1894, 13, 289) ; Kahlen-berg, Davis, and Fowler (J. Arne?*. Chem. Soc., 1899, 21, l), andCarrara and Vespignrtni (Gnzzetta, 1900, 30, ii, 35.None of these methods is really satisfactory for the measurementof very small concentrations of hydrogen ions, and, although Bredigand Fraenkel (Zeitsch. Elektrochem., 1905, 11, 525) have recentlydescribed a new method whereby concentrations of hydrogen ionsdown to N/lOCO can be accurately determined, nevertheless thepresence of neutral salts produces a disturbing effect, thus renderingthe practical applicability of the method rather difficult.In the present paper, the hydrogen electrode has been used for thepurpose of determining the concentration of the hydrogen ions inaqueous salt solutions.This method is particularly suitable whenwe are dealing with very small concentrations, and it thereforepromised to be very useful in many cases when the methods hithertoemployed become difficult of application. It suffers, however, fromthe disadvantage that it cannot be employed in the case of the saltsof metals less ‘ I noble ” than hydrogen, nor in the case of multivalentcations (such as Fe”’) which are reduced by hydrogen to cations ofsmaller electrovalency, nor is the method admissible in the case ofsalts with reducible anions as NO,’, CIO,’. During the course ofthis work, papers have been published by Bjerrum, in which the samemethod has been employed in the study of solutions of chromiumchloride. Reference will be made to these later42 DENHAM : THE ELECTROMETRICThe Equilibrium Equations of Progressive Suit HpdrolysiS.I n dealing with the salts of multivalent cations, the hydrolysis mayoccur progressively in several stages, to each of which corresponddefinite equilibria.If aluminium chIoride is taken as an example, theprogressive stages of the hydrolysis may be represented by the threofollowing purely stoichiometric equations :. . . . . . . AICI,+H20 =AICI,(OH) + HCl (1)AICl, + 2H,O - AICl(OH), + 2HC1 (2)AICI, + 3H,O = Al(OH), + 3HC1 (3). . . . . . .. . . . . . .The mechanism of equation (1) may be represented by the twoionic equilibria :. . . . . . . . (AlC12)* +OH' z2 AIC12(OH) , (14H ' + O H = H , O . (4)(AICl,). + H,O AlCl,(OH) + H' ( W.. . . . . . . . .which may be combined in the simple equilibrium equation :. . . . . . .Denoting molar concentrations by square brackets, we have from(la) and (4) :. . . . . . . . [AlCli]. [OH'] = k,,[AlCl,(OH)] ( 5 )[He]. [OH'] = K, (6) . . . . . . . . . . . . .and therefore[AlCI,'] = ~[AlCl,(OH)][H'J . . . . . . . . . (7). K wIf we now make the simplifying assumptions that aluminiumchloride and hydrochloric acid are completely ionisad according t othe equations :AICJ, AICl,D+Cl',HC1 H'+Cl',and if v denotes the molar dilution of the "total" aluminiumchloride (hydrolysed and non-hydrolysed), and x the fractionalamount hydrolysed, it follows from the above equations and assump-tions that[AlCI,'] = 3, [H'] = [AlCl,(OH)] = E,whence from (7) we haveIt must be observed that LX denotes the fractional amount oDETERMINATION OF THE HYDROLYSIS OF snrs.43hydrolysis according to the first stage (equation l), and that thevalidity of the equations, [H'] = [AlCl,(OH)] = depends on theusually made assumption that the value of [N'] is very considerablygreater than the value corresponding to the dissociation of pure water.This "first-stage" hydrolysis is due t o the formation of therelatively undissociated basic salt, AICI,(OH), which may be regardedas the hydroxide of the complex cation (AlCl,').Let us now imagine a state of affairs wherein the hydrolysis corre-sponds to the stoichiometric equation (2), that is to say, to the forma-tion of the relatively undissociated basic salt, AlCl(OH),.Regarding the latter as the hydroxide of the complex cation AlCl",we might suppose that the second-stage hydrolysis would correspondto more dilute solutions, wherein the dissociation of the aluminiumchloride would proceed chiefly or largely according to the equation :AlCl, AlC1" + 2Cl".Assuming that the dissociation of the aluminium chloride accordingto this equation is complex, and denoting by z the fractional amountof hydrolysis according to equation (2), we obtainU'X 2z [AlCl"] = A-y-?, [hlCl(OH),] = -, [H ] = -.The second-stage hydrolysis being controlled by the equilibrium :AlCl" + 2(OH) z AlCI(OH), . .. , . . , . . (9)together with (6), yields the equations :[AICl"][OH']2 = kb,[AlCI(OH),] and[AlCl"] = %2, [AlCl(OH),].[H'],,Kwwhich, on the above assumptions, givesKw2- K2 . . . . . . . . . . . . (10). (-=K2- X2The third-stage hydrolysis corresponding to the stoichiometricAssuming complete equation (3) may be dealt with in a similar way.dissociation of aluminium chloride according to the equationand a hydrolysis controlled by the dissociation equilibrium :AICI, Al"'+3C1',Al"' + 30H' Al(OH),,[Al"'] = %3[Al(OH)s] . [H*l3,we have [Al'.'] . [OH']3 = kb3[A1(OH)3]Ku44 DENHAM : THE ELECTROMETRICI - % X 3s and therefore, since [Al***] = -:, [Al(OH),] = --, and [H 3 = -2) V V ,For .z chloride of a bivalent cation, the first-stage hydrolysis corre-sponds t o equation (S), and the second stage t o equation (10).I n the case of a sulphate of a tervalent cation, such as aluminium,the stoichiometric equations representing the progressive hydrolysisare :A12(S04), + 2H20 = A12(S04)2(OH), + H2S0,,A12(S04)3 + 4H20 = Al,(SO,)(OH), + 2H,S04,AI2(SO4), + 6H20 = Al,(OH), + 3H2S04.Corresponding to the first of these equations, we have the dissociationequilibrium :which leads toAl,(SO,)** + 20H' t Al,(SO,),(OH),,[AI,(SO4)"] [OH']2 = kh[AI2(SO4),(OH)21-Assuming complete dissociation according to the equations :H2804 = 2H' + SO,"A12(S0,), = A12(S04)iD + SO4",and putting x=fractional degree of hydrolysis, we obtain as theequation for the first-stage hydrolysis :(12).. . . . . . . . . . . - ~ - - - XI - K " 2 - K l .(1 -x)v' 4kblIt might be possible t o write the dissociation equilibria, also, asfollows :A12(S04), 2AlSO,'+ SO,"Also,' +OH' z2 Al(SO,)(OH),leading thus to the equations :[AISO,'] .[OH'] = kb,[AlSO,OH][AlSO,'] =$ [AlSO,OH] . [H'].K*2x [H'] =;, and 2x In this case, [Also,.] = u, [AlSO,OH] = -,thus the equation corresponding to the first-stage hydrolysis would be(1 3). G" ~- - - = K l . . . . . . . . . . . .(1 -X)V 2kb,X 2On this view, the corresponding stoichiometric equation wou Id be :Al,(SO,), + 2H,O = 2AI(SO,)(OH) + H2S0,DETERMINATION OF THE HYDROLYSIS OF SALTS. 45Corresponding to the second-stage hydrolysis, we get by similarreasoning the equation :--- x5 - Kw4 = K z . a . . .(1 - X)V* 256 kb2where ka, is the dissociation constant of the basic salt,dissociating into the ions AI,SO,"" and 40H'.stoichiometric equation :I n the case of the third-stage hydrolysis, it is possible to write theAl,(SO,), + 6 H,O = 2Al( OH), + 3H,so,.The hydrolysis in this case may be supposed to be controlled by thedissociation equilibrium,[Al"' ][OH']3=k~,[Al(OH),].Assuming a complete dissociation of A1,(S0,)3 .according to theequation :we arrive at the equation :Al,(SO,), = i?Al'** + 3SO,",where cz is the fractional degree of hydrolysis according to the aboveequation.I n the case of a sulphate of a bivalent cation, there is only one stageof hydrolysis possible, and to this corresponds a cubic equation in x ofthe same form as equation (10) or (12). Similarly, for the sulphate ofa univalent cation, the equation of hydrolytic dissociation is the sameas (8).I n attempting to test any of the equations given in the precedingparagraphs, three points must be borne in mind.I n the first place,certain simplifying assumptions have been made with respect to thenature and degree of the ionisation of the salts and acids involved.I n the second place, the stages of the progressive hydrolysis consideredmay not be sharply marked off, with the result that a superposition ofthe different equilibria may occur. Finally, the solubilities of thebasic salts or hydroxides may be overstepped, so that heterogeneousequilibria are produced. Furthermore, if, as very often happens, thebasic salts or hydroxides separate in the form of colloidal pseudo-solutions or suspensions, it may be expected that no definite equilibriawill be obtained.The second and third of these difficulties reside in the nature of thephenomena themselves, and cannot be surmounted.The first difficult06 DENHAM : THE ELECTROMETRICmentioned may, however, be obviated to a certain extent by intro-ducing suitable corrections. Thus in the preceding theory the totalconcentration of the acid that must be produced according to thestoichiometric mass-relationship has been identified with the concentra-tion of the hydrogen ion. This will, however, not in general be true,even for the highly dissociated mineral acids. In the case of thechlorides of chromium and aluminium dealt with below, a correction hasbeen made for the undissociated hydrochloric acid on the assumption thatthe percentage amount of undissociated acid would be the same as ina pure hydrochloric acid solution of the same total concentration ofchlorine ions. I n the case of the sulphate of aluminium, it has notbeen possible to apply a similar correction, owing to the want ofsufficiently secure data concerning the dissociation of the ion HSO,'.Appuratus and Metlbod of Measurement,The hydrogen electrode employed was constructed after the typedescribed by Wilsmore (Zeitsch.physikal. Chem,, 1900, 35, 296). Theother half-element consisted of a normal mercurous chloride electrode.The hydrogen and mercurous chloride electrodes were connected by asaturated solution of ammonium nitrate, which Abegg and Gumming(Zeitsch. Elektrochem., 1907, 13, 17) have recently shown to annul theliquid potential difference.The rest of the apparatus consisted of aslide-wire bridge, accumulator, cadmium cell, and Lippmann electro-meter. The temperature at which the experiments were carried outwas 2 5 O , const,ancy of temperature being secured by a suitable water-thermostat. The hydrogen used for saturating the electrode wasprepared from electrolytic zinc and pure dilute sulphuric acid, andpassed through a waahbottle containing an alkaline solution of potassiumpermanganate.The solutions were always prepared from conductivity water(1.2 x 10-6 to 2.5 x by siphoning the required quantity on to aweighed amount of the salt. The solutions were kept in steamed-out Jena flasks, and whenever they were kept for more than a daythey were protected with a soda-lime tube to guard against the entryof carbon dioxide.The potential of the hydrogen electrode is given by the formula :where rL = the potential of a solution of concentration [H'];r,, = potential for a solution normal in respect to H'-ion, andR, T, P have their usual significations. 111 accordance with theagreement of the Commission on Electrode Potentials of the GermanBunsen Society, under electrode potential is here understood positivDETERMINATION OF THE HYDROLYSIS OF SALTS.47potential of the electrode-positive potential of solution. If we takethe absolute potential of the normal calomel electrode as + 0.56 volt,we may (Wilsmore, Zoc. cit.) put 7ro= + 0.277 volt. The method ofcalculation employed may, for the sake of clearness, be brieflyillustrated by two examples :( a ) Table I, p.48.Cell measured, H2 1 m/32C6H;NH,C1 { NH,NO, I Hg,Cl, electrode.Observed E.M.F. = 0.4655 volt (in direction indicated by tbearrow). Hence potential of the hydrogen electrode = 0.56-0*4655 =RT 0.0945 volt, and therefore Fl~ge[H'] = 0.0945-0.277 =3- ---RTF - 0.1825. As T = 273 + 35 = 298, we have - x 2.3026 = 0.059,0.1825 and therefore log[H'] = - - whence [H'] = 0.000807. Since0.059 'complete hydrolysis mould produce a value of [H'] 'equal to 1/32(assuming complete dissociation of the hydrochloric acid), the per-centage hydrolysis is given by the equation lOOx = 0.000807 x32 x 100, whence lOOx = 2-58 (x =fractional hydrolysis).(b) Table (XII), p.57.Cell measured, H, I m/4A1,(S04)3 I NH,NO, I Hg2C12 electrode.Observed E.M.F. = 0-4354 volt,Potential of H,-electrode = 0.56-0-4354 = 0.1246 volt.Hence 0.069 log[H'] = 0*1246--0.277 = - 0,1524, whence [H'] =0 ~00261.Since the solution is one-fourth molecular normal with respect toaluminium sulphate, complete hydrolysis according to the stoichio-metric equation :Al,(SO,), + 2H20 = Al,(SO,),(OH), + H2S04,mould yield a one-fourth molecular normal solution of sulphuric acid.I f one assumes complete dissociation of the sulphuric acid into theions H' and SOL', the molar concentration of the hydrogen ionwould be 0.5. Hence the percentage hydrolysis according to theabove reaction is given by the equation :__lfAniline Hydrochloride.The hydrolysis of this salt has been very carefully determined byBredig (Zeitsch.plqsikal, Chena., 1894, 13, 289) and by Walker an48 DENHAM : THE ELECTROMETRICAston (Trans., 1895, 67, 576). [Bredig used the conductivity method,and found 2-61 per cent. hydrolysed for v3, at 25'. Walker used theinversion method, and found 4.5 per cent. for v8,, at 60°. A re-determination of the hydrolysis of this salt appeared to be a usefultest of the method employed in this paper.The salt used was purified by recrystallisation from a saturatedsolution in acetone, the solvent being removed by repeated washingwith ether. It was finally dried over potassium hydroxide and con-centrated sulphuric acid in a vacuum desiccator.I n the table below, as well as in all following tables, v denotes themolecular dilution, E.M.F. the measured electromotive force of thecell in volts, rrl the absolute potential of the hydrogen electrodefor that solution, [H'] is the hydrogen-ion concentration in gram-mols. per litre, and 100~: is the percentage hydrolysis calculated fora first-stage hydrolysis, unless the contrary is stated.TABLE I.Aniline Hydrochloride.Cell, H, I C,H,*NH,Cl 1 NH4N03 I Hg,Cl, electrode.21. E. M. F. TI * H' x lo2. 1oox. Kl x lo4.16 0.4567 0.1033 0.1138 1'82 0.2124 0.4609 0'0991 0'0966 2.32 0.2332 0.4655 0'0945 0.0807 2.58 0.21Mean ... ... ... ... 0.216Under Kl are tabulated the values of the constant calculated fromequation (S), ___ = K l , as deduced for a first-stage hydrolysis of asalt of this type.The hydrolysis for v32 amounts to 2.58 per cent., avalue agreeing extremely well with that found by Bredig tit the sametemperature and dilution, 2-61 per cent.X3(1 -x)vThe Apparent Heat of Dissocicttion of Anilz'nium Hydroxide.''The hydrolytic constant of aniline hydrochloride is calculated fromx2equation (a), --- - ",. If the dissociation of a normal electrolyte(1 - x)v KOis measured over n range of temperature not too great, i t is generallyfound to be practically independent of the temperature. Therefore,knowing XI, at 25' and the variation of K, with the temperature, oneshould be able to calculate x for any other temperature. But as Kwat 60' is nine times as great as at 2 5 O , i t follows that the hydrolysisof aiiline hydrochloride for vs0 at 60' would be 7.5 per cent., whilsDETERMIBATION OF THE HYDROLYSIS OF SALTS.49Walker and Aston (Zoc. cit.) found only 4.5 per cent. The conclusionmust be drawn that the dissociation constant of “anilinium hydr-oxide ” is not independent of the tempernture. An application ofvan’t Hoff’s equation,d log& - RTddt Q__should therefore give information regarding q, the apparent heat ofdissociation. On integrating between the limits TI, T2, we getlog& - Q (T - .T’) ----- &’ R yl’yl ’where &“, Kb’ are the dissociation constants of ‘‘ anilinium hydroxide ”a t the temperatures T” and T.If 5 is calculated from the percentage hydrolysis obtained byWalker and Aston at 60°, the value !& = 0.707 x 10-4 results; a tas0, 5’ = 0.216 x and from these results q is calculated to be2860 calories ; q here refers to the heat absorbed in the dissociationof “ anilinium hydroxide ” plus the heat absorbed in the hydration ofthe anhydrous aniline.KbZ bKbAmmonium ChEoride.The hydrolysis of this salt mas recently measured by Veley (Trans.,1905, 87, 26).The method he used was to boil the solution for anhour, and then determine the loss of ammonia by titration. The con-clusion was drawn that the hydrolysis of ammonium chloride must bevary small indeed.As usual, the salt was freed from any traces OF acid by repeatedrecrystallisation from conductivity water. A normal solution wasfirst used, and the potential registered by the hydrogen electrodeamounted to - 0.0049 volt after thirty minutes, but in an hour it hadrisen to 0.0066 volt.This steady increase in potential, and thereforein hydrogen-ion concentration, pointed to the loss of ammonia, audthis was conclusively proved by passing the escaping gas into a solu-tion of red litmus. I n orderto overcome this loss of ammonia, three washbottles were insertedbefore the hydrogen electrode, all containing a solution of the samestrength as was being measured, One washbottle was outside thethermostat, and two within. Thus when the hydrogen reached thesolution containing the electrode, it was already in equilibrium withammonia a t that temperature and concentration.The observed potential wasIt very quickly turned a decided blue.One other difficulty still remained,VOL.XCIII. 50 DENHAM : THE ELECTROMETRICfound to fall to a minimum, and then rise a little to a fixed, but higher,value. The steady fall to a minimum is duo to the gradual saturationof the electrode with hydrogen, and the subsequent rise can only bedue either to the electrode having been supersaturated or to anincrease in the hydrogen-ion concentration. The first possibility maybe left out of consideration, for in no other salt used did this occur.The increase in the hydrogen-ion concentration can be readilyexplained as being due to the adsorption of ammonia by the electrodefrom the film of liquid in contact with it, The potential registeredwould be that of the surrouhding film, and mould consequently be toohigh. The hydrogen and ammonia gases are occluded by the platinum,the former probably with a much greater velocity, and hence thelowest potential registered would, on this assumption, correspondvery nearly to the true potential. Slight evidence in support of thisi s furnished by the fact that the hydrogen-ion concentrations calcu-lated from the higher potentials are practically the same, althoughthe concentration of the solution has changed from N/2 to N/32 ; butthe hydrogen-ion concentrations calculated from the lower potentialsshow differences much more in accord with the behaviour of allknown hydrolysed salts, that is, with increasing concentration of thesalt there is an increasing hydrogen-ion concentration, but a decreasingpercentage hydrolysis. As it was a matter of very great difficulty toobtain values for the minimuzh potential when it changes so quickly, anumber of independent experiments were carried out, and the meanminimum potential recorded,TABLE 11.Ammonium Chloride.2).281632Cell, H, 1 NH,C1 I NH,NO, ('Hg2C12 electrode.h'. M.F. Tl* [H-] x lo8. 1002. Kl x l o p .05732 - 0'0132 1'233 0'00246 0.3005911 - 0'0311 0.604 0'00479 0.290.5998 - 0.0398 0.427 0'0068 0.290.6056 - 0.0456 0'340 0-oioa 0.360 '3 1-Mean, . . . . . . . . . . .X2 The constant K , is calculated from equation (8), ~ - L c y = K l , for afirst-stage hydrolysis of a salt with univalent anion. The experimentalerror arising from the adsorption mentioned has prevented moredilute solutions being examined, but enough has been done to showhow small is the hydrolysis of this saltDETERMINATION OF THE HYDROLYSIS OF SALTS.51The ratio €or the hydrolytic constants of aniline hydrochloride andammonium chloride is seventy thousand, that is, aniline is seventythousand times as weak a base as ammonium. Bredig (Zeitsch. physikal.Chem., 1895, 13,289) has found the dissociation-constant of ammoniumhydroxide to be 0.0023, and Abegg (Die elekt. Dissociation-theorie,Ahreus’ ‘‘ Vortrage,” 8, 183) gives the dissociation-constant of anilineas 4.9 x10-10. The ratio of the constant of ammonia to that of‘‘ anilinium hydroxide ” is 60,000. Since the hydrolytic constant ofaniline hydrochloride agrees so well with that found by Bredig, weare justified in concluding that the hydrolytic constant of ammoniumchloride is tolerably correct.Moreover, Noyes, in his report, ‘‘ The Electrical Conductivity ofAqueous Solutions ” (p.346), has calculated the per cent. hydrolysis ofammonium chloride (v = 100) to be 0.02 a t 1 8 O , whilst extrapolationfrom the above values (Table 11) gives 0.018 for this dilution a t 25’.Chromium Chloride.A great deal of work has been done on the green and bluemodifications of chromium chloride, Amongst others, the work ofGodefroy (Compt. rend., 1885, 100, 105) ; Peligot (Compt. rend., 1885,100, 105) ; Recoura (Ann. Chim. Phys., 1887, [vi], 10,39) ; Wernerand Gubser (Ber., 1901, 34, 1579), and Gubser (Inccug. Diss., Zurich,1900) may be mentioned.The work of these goes to show that theformula of both varieties is CrCI,,GH,O, but in the green chloride twoatoms of chlorine cannot be precipitated by silver nitrate, as they formpart of a complex cation. Recently, Bjerrum (Zeitsch. physikal. Chem.,1907, 59, 336) has shown that the blue chloride, when dissolved inwater, is hydrolysed, thus :CrCl, + H,O = CrCI,(OH) + HC1.The hydrolytic constant of the green salt is only about one four-hundredth that of the blue. The method used by him to measurethe hydrolysis was the determination of the potential of the hydrogenelectrode and conductivity measurements.Hydrolysis of the Greeya Chloride.-This chloride was preparedaccording to the method described by Recoura (Eoc. cit,) and Wernerand Gubser (Zoc.cit.),Bjerrum has very carefully examined the solution of the greenchloride, using an apparatus whereby he was enabled to obtain a poten-tial within two minutes, and a conductivity measurement in even lesstime. He has found that tho hydrolysis as indicated by the potentialobserved is at first much less than for the blue chloride, but thatthere is a rapid increase of hydrolysis in the first few hours.Unfortunately, the apparatus used in the present work was unsuitableE 52 DENHAM : THE ELECTROMETKlCfor obtaining readings in such a short time, for it required a t leastten minutes to obtain a constant potential. A more or less qualita-tive series of experiments with the green solution has therefore beencarried out in order to check Bjerrum's results.A solution of the green chloride was prepared and divided into twoparts, and to one was added a few drops of concentrated hydrochloricacid.These two samples were allowed to stand at the ordinary tem-perature. In sixteen hours, that which had not been acidified wasbluish-green, whilst the other remained green. I n three days, thelatter was still unchanged, but the unacidified sample was blue. Theaddition of the acid had evidently retarded the formation of the bluesalt from the green, consequently the change of the green into theblue must be attended by the increase of acid concentration throughan increase of hydrolysis.A solution of concentration vO4 was then prepared, and readingswere taken for two hours; t denotes the time in minutes since thesolution was made.TABLE 111.Cell, H2 I CrCI, (green) 1 NHI,NO, [ Hg,CI, electrode.v = 64.t.E. ill. F. =1 [H'] x lo2.20 0 '4545 0.1055 0-12440 0.4526 0.1074 0-133120 0.4458 0.1142 0.174TABLE IV.1.20354575105v = 16.E. af. F. "1.0'4355 0.12450.4268 0.13320.4220 0.13800'4180 0'14200'4180 0.1420[ I I ~ x 102.0.2600.3173.44105140-514TABLE V.V = 32.t. I$. ill. l? = I ' [EI'] x 10'.15 0.4559 0.1041 0.11732 0.4471 0'1129 0'16655 0,4368 0'1232 0'247These experiments all show that there is a rapid rise in the hydrogen-ion concentration, and, as the hydrolytic constant found by Bjerrumand by me for the blue chloride is very much larger than thDETERMINATIOK OF THE HYDROLYSIS OF SALTS.53approximate constant found by him for the green chloride, he is quitejustified in his conclusion that the rapid increase in hydrolysis is dueto a progressive conversion of the green chloride into the blue.Chromium Chloride (blue).The salt was prepared as described by Higley (J. Amer. Chem. Soc.,1904, 26, 613).TABLE VI._I_, --Cell, H, I CrCl, I NH4N0, I Hg,Cl, electrode.V. E. M. F. R1' [H'] x loy. [H'] x lo2. 1002.4 0'4234 0,1366 0.417 0510 2.028 0 '4332 0.1278 0'296 0.351 2'8116 0'4382 0'1218 0'234 0'269 4 3 032 0.4455 0.1145 0.176 0.19T 6'30'64 0'4523 0.1077 0.135 0.148 9'47TotalI n Table VI, ' I total [H']" refers to the concentration of thehydrogen ion after a correction has been made for the undissociatedhydrochloric acid, as already explained.Figure 1 shows x plottedas a function of v.9.48163264TABLE VII.1oox. K~ x 103. K, x 107.2'02 0.10 0'652'81 0'10 0.434 '30 0'12 0-406'30 0.13 0.319.47 0.15 0.270 '12-Mean.. . . . . . . . . . ,Here Kl refers to the constant calculated for a first-stageX2 hydrolysis from equation (8), ~ - -q; (1 - x)vand K2 has been calcu-x3 lated for a second-stage reaction according to equation (10) - --- ' (1 - x)v2'x here being, also, calculated for a second-stage reaction, 'that is,half the values tabulated above. Although Kl varies somewhat, itsvariation is much less than that of K,. Undoubtedly, therefore, themain reaction must be represented by the ionic equation :CrCI,' + H,O CrCI,(OH) + H',but probably the basic salt, CrCl(OH),, is also produced in the dilutesolutions as in the equation :CrCl" + 2H,O CrCl(OH), + 2H'54 DENHAM : THE ELECTROMETRICAt any rate, Bjerrum (Zoc.c;t.) has also noticed the rise in the constantin the dilute solutions. The percentages of hydrolysis given inTable VI are slightly larger than Bjerrum found, for his constantamounts to 0.98 x but consideringthe great influence a slight erroy in the E.M.F. exerts, the agreementmust be considered quite satisfactory.as compared with 1.2 xFIG. 1.105116 64 256Aluminium Chloride.This salt was prepared from a specimen obtained from Merck byprecipitating it from a saturated solution with hydrogen chloride.The salt was left for a month in a vacuum desiccator over potassiumhydroxide to remove any traces of adhering acid.Preliminary experiments with zinc sulphate, which will be describedlater, had already shown that a solution of this salt does not give thDETERMINATION OF THE HYDROLYSIS OF SALTS.55April 26 ............ 0.4485,, 27 ........... 0.4607,, 26 ............ 0.4537same hydrogen-ion potential from day to day, but that an extra-ordinary change in the hydrogen-ion concentration of the solutionoccurs. Thus it was important to determine whether the solutionof each salt examined gave a constant potential over a considerablenumber of days, proving that the solution was in a state of equili-brium. This was done in a I' time" experiment, wherein a quantityof a solution was siphoned from the main stock into the apparatusevery day, and its potential ascertained for a sufficient number ofdays to show that equilibrium had set in.It was not necessary to dothis in the case of the chromium salts, because it is known from thework of Richard and Bonnet (Zoc. ait.) and Bjerrum that the solutionsslowly change their hydrogen-ion concentrations until equilibrium isreached ; nor were '' time " experiments carried out with aniline hydro-chloride or ammonium chloride, for here there is no possibility of solidbasic salts or hydrates complicating the ionic reactions.The '' time " experiment for aluminium chloride showed that withintwenty-four hours a state of equilibrium is reached, as is shown in thefollowing table.TABLE VIII.April 27 ............ 0.4607,, 29 ............0.4606,, 29 ............ 0'4605Cell, H, 1 AlCl, I NH,NO, ,- 1 Hg2C12 electrode.All solutions in the following experimenk were therefore allowedto stand in the thermostat for twenty-four hours before measure-ments were made.TABLE IX.Aluminium Chloride.Cell, H, I AlCl, I NH,NO, I Hg2C1, electrode. + --TotalV. E. M. F. =I - [H'] x lo2. [H'] x lo2. 1OOz.16 0'4492 0'1108 0'1520 0-1750 2.832 0.4567 0'1023 0-1140 0.1270 4-0664 0.4655 0.0945 0.0807 0,0885 5'66100 0.4720 0.0880 0.0626 0.0679 6.79128 0.4741 0.0859 0.0577 0.0620 7'93Figure 1 shows x plotted as a function of v56U.163264100138DENHAM : THE ELECTROMETRICTABLE X.1002. K~ x 104.2-80 0.504-06 0.535.66 0.536.79 0'407-93 0.530 5 1-Mean.. , .. . . . . . . .XI is calculated from equation (8) for a first-stage hydrolysis,2 2 - Kl ; the value obtained clearly shows that the hydrolysis ( l - z q v -proceeds according to the ionic equation :AlCI,' + H,O t AlCI,(OH) + He.A comparison of the percentage hydrolysis of chromium andaluminium chlorides at similar dilutions shows that the chromiumchloride is, on the average, hydrolysed 1.6 times as much as thealuminium chloride. From these experiments, it would appear thatchromium is about 1.6 times as weak a base as aluminium,Compa&on of Results for AZuminium ChZo.r.ide.Kahlenberg, Davis and Fowler (Zoc. cit.) have found 2.2 per cent.hydrolysed in a sixth-molecular normal solution at 55.5'. Ley (Zoc.cit.), working at 9 9 * 7 O , where the hydrolysis is much greater, obtainedthe following results.TABLE XI.9.326412825 65121002.8-0413'2019'7028.2041-40K~ x 104.2'23 -13 -84'35.7Here x and Kl refer to a first-stage hydrolysis, the latter beingX2calculated from equation (8), -- (I - x ) v - =I*His results at 99.7" are roughly about twice those observed by theLey has made one determination of the hydrolysis of aluminiumHe found 13.5 per cent.Bruner (Zoc.cit.) worked at 40' and found at w4 3.3 per cent., at v8He is the onlyauthor at a lower temperature.chloride by conductivity methods at 25'.hydrolysed at v,,,~~.2.9 per cent., and at vS2 2.9 per cent, hydrolysedDETERMINATION OF THE HYDROLYSIS OF SALTS.57worker who has not found increasing hydrolysis of this salt ondilution.Recently, Bjerrum (Zoc. cit., p. 349) carried out a series of experi-ments on the hydrolysis of aluminium chloride a t 25O, using con-ductivity measurements. He says '( Ley hat fruher die Hgdrolyse desAluminiumchlorids in 3/1024-molarer Losung zu 4.5 pro cent.(alle Salzsaure frei = 100 pro cent.) berechnet. Dieses entspricht13.5 pro cent. Hydrolyse nach der Gleichung AlCI, + H,O =AlC1,OH + HCl. Ich finde 16.6 pro cent." Two misstatementsoccur here. Ley worked throughout (Zoc. cit.) with molecular solu-tions, and it was in a solution 1/1024-~noZecuZar normal that heobtained 13.5 per cent. hydrolysis; secondly, the solution in whichBjerrum records 16.6 per cent.hydrolysis is, according to his owntable, one containing 0.000326 of a gram-molecule, that is, v = 3069.These misstatements both appear to be due to confusion betweenmolecular normality and equivalent normality. Further comparisonof Bjerrum's results must be left over until the errors mentionedhave been corrected.A lw niiniunh SuZpha t e .The salt was obtained from Merck, and was freed from any tracesof acid by precipitating it from a saturated solution by the additionof alcohol.Just as in the case of aluminium chloride, there was a slightchange of hydrolysis in the '' time " experiment during the first day,but after that time the potential registered remained quite constantfor the next three days. I n the following experiments, the solutionswere kept twenty-four hours in the thermostat before measurementswere made.TABLE XII.Aluminium Sulphate.Cell, IT, I AI,(SO,), I NH,NO, I Hg,Cl, electrode.v.E. M. F. n,. [H*] x lo2. 1 0 0 ~ . Kl x 108. K X 10".4 0'4354 0'1246 0-261 0.522 0 -88 0.688 0'4439 0-1161 0.187 0.748 0'66 0.7116 0-4505 0'1095 0.145 1 *160 0 '62 0.8532 0'4541 0.1059 0'126 2-016 0*82 1.3064 o m r i 0'1016 0.106 3.492 0.98 1-86256 0.4672 0 *0928 0.075 9.600 1'48 4.00Figure (1) shows the variation of x with v. In the above table, Klx3 is calculated from equation (12), _____- - Kl , for a first-stage hydro-(1 - 4 v 2lysis of a salt of this type, The rise in the value of Kl from w2558 DENHAM : THE ELECTROMETRICpoints to the probability that with increasing dilution the second-stage hydrolysis is becoming increasingly important.The reactionfrom v4 to wC4 is represented by the stoichiometric equation :and by the ionic equation :but in more dilute solutions we have also :A12(S04), + 2H20 = A12(S04)2(0H)2 + H2S04,A12(S04)2" + 2H20 t A12(S04)2(OH)2 + 2H',A12(S04), + 4H20 = A1,(S0,)(OH)4 + 2H2S0,Al,(SO,)"" + 4H20 Al,(SO,)(OK), + 4H'.The constant g i n the above table has been calculated from equationP3), (ix-qj. This equation has been deduced on the assumptionthat the reaction is represented by the stoichiometric equation :A12(S04), + 2H20 = 2A1(S04)(OH) + H2S04,and the ionic equation :AISO,' + OH' Z Al(SO,)(OH).The constant K shows considerably more variation than does Kl,although in the concentrated solutions K is as constant as can beexpected for such concentrations.X2Comparison of Res2jts for Aluminium SuEphate.Bruner (Zoc.cit.) at 40' found 1.3 per cent. hydrolysed a t v12, 1.4 perLey (Zoc. cit.) at 99*7O found 8.9 per cent. at v256, and 5.4 per cent,Kahlenberg, Davis and Fowler (Zoc. cit.) at 55.5' found a hydrolysisof 1.56 per cent. for v12.Finally, Carrara and Vespignani (Zoc. cit .) measured the hydrolysisof this salt at 25' by the inversion of methyl acetate. The basis ofthis method is to compare the constant of the reaction for a salt withthat obtained for a dilute solution of an acid where the dissociation iscomplete, that is, where the hydrogen-ion concentration can beidentified with the total-acid concentration.Now these workers havecompared their constant for aluminium sulphate with that of sulphuricacid, both fifth-molecular normal, and thus obtained a percentagehydrolysis of 2.6. It is obviously incorrect to identify the hydrogen-ion concentration of a fifth-molar solution of sulphuric acid with thatof the total acid, and any such assumption must cause a very largeerror in the calculation, If the percentage hydrolysis is calculatedfrom the constant of aluminium sulphate and that obtained bythem for hydrochloric acid (v&, according to the equation, percent-cent, at v2,,, and 1.7 per cent. at v , ~ .at '128DETERMINATION OF THE HYDROLYSIS OF SALTS. 59age s the result is 0.81. But a fifth-molar solution of hydrogenKavachloride is only dissociated t o the extent of 80 per cent,, and on cor-recting for this the percentage is found to be 0.65.This agreesextremely well with the value 0.52 given in Table XI1 for v4.ThaElous Sulphate.The salt was supplied by Kahlbaum, and was not further purified.The solutions were all acid towards litmus, and owing to the sparingsolubility of the sulphate only a few solutions were examined.Although the solution vI6 was observed for several days, no changein the amount of hydrolysis was detected. Apparently the hydrolyticequilibrium is established immediately on preparing the solution.TABLE XIII.-+ ---Cell, H, 1 Tl,SO, I NH,NO, I Hg,Cl, electrode.v. E. M. F. A1. [H'] x lo2. 1002. Kl x lo?.16 0.4137 0-1463 0.609 4.87 0*1532 0'4213 0.1387 0.448 7.15 0'170.4309 0'1201 0.311 9 *95 0 -17 640.16-Mean... ... ... ...X The constant XI is calculated from equation (S), A, for afirst-stage hydrolysis of a salt with univalent cation; the value ofKl is practically constant, and this shows that the hydrolysis mustproceed according t o the ionic equation :T1' + OH' =. Tl(0H).(1 - x ) vNickel Xulphate.The salt was prepared from a specimen of Kahlbaum's by carefulrecrystallisation. The *' time " experiment again showed a variationin the hydrogen-ion concentration, although much less than observedin the salts of zinc, magnesium, thorium, and cerium60 DENHAM : THE ELECTROMETRICTABLE XIV.Nickid SUlphC6te ; v = 32.Cell, H, I NiSO, I NH,NO, I Hg,CI, electrode.Days. E.Af. F. Tl' [H.] x lo30 0.5031 0.0569 0.1861 0.4966 0'0634 0'2303 0.4962 0.0638 0.2444 0-5023 0-0577 0.1925 0'5003 0.0597 0.2076 0'4098 0-0602 0.211---- >The first column denotes the age of the solution in days.In the following series of experiments, in order to make the resultscomparable, the potentials were measured ten minutes after the solu-tions were made; but as the "time" experiment shows a slightvariation in the hydrogen-ion concentration, one cannot expect toobtain a satisfactory constant.Cell, H, I NiSO,4 0.5302 0'02988 0'5362 0.023816 0.5400 0.020032 0-5518 0-008264 0.5637 -0.0037v. 3.AI.F. r1.TABLE XV.+ --NH4N03 I Hg,CI, electrode.[H-] 104. ~ O O X . K, x 1012. K x 108.0.647 0.013 0-14 0.420.512 0.020 0-1 3 0.520'440 0.035 0.17 0.770.278 0.044 0.09 0 '620.175 0.056 0'04 0'49 -Mean... , , . . . . . . . 0 '1 123 Kl has been calculated from equation (12), -I-- - = Kr, for a first-stage hydrolysis of a salt of this type; ZC is the constant calculatedfrom equation (13), - = K.(1 - x)v222(1 -x)wThe first constant Kl is sufficiently satisfactory to show that thehydrolysis proceeds according to the ionic equation :Ni" + 20H' t Ni(OH),.The constant K is again satisfactory, although the equation fromwhich it is calculated lacks the possible theoretical foundation that ithas in the case of aluminium and chromium sulphates.Eahlenburg, Davis and Fowler (Zoc. cit.) have measured thehydrolysis of nickel sulphate (v4) at 55*5", and found 0.045 per cent.hydrolysed. This compares well with that quoted in the above tablefor the same dilution, namely, 0.013 per cent.a t 25DETERMINATION OF THE HYDROLYSIS OF SALTS. 61Cobalt Xulphate.This salt was prepared from a specimen of cobalt carbonate (freefrom nickel) by the action of sulphuric acid. The sulphate so formedwas three times precipitated from a strong solution by the addition ofalcohol. Finally, the sulphate was recrystallised from water. The" time " experiment was followed for five days, but the hydrogen-ionconcentration showed very little change from the value first obtained.TABLE XVI.-+ --Cell, H, I CoSO, I NH,NO, I Hg,Cl, electrode.7'. E. M. F. =1. [H'] x 104. 100s. li; x K x lo9.2 0.5487 0.0113 0.313 0.0031 0 * i 6 0.484 05590 0*0010 0.210 0.0042 0 *46 0 '448 0'5675 -0.0075 0,163 0.0065 0.43 0-5316 0'5762 - 0.0162 0.107 0'0085 0'24 0'4532 0'5798 - 0.0198 0.093 0.0149 0.32 0.69-Mean... . . . . . . . . , 0 '4439 I n table XVI, Kl is calculated from equation (12), ____- = Kl,for a first-stage hydrolysis of such a salt. The value of Kl is muchtoo high in the strongest solution, but for the others it is sufficientlysatisfactory to show that the ionic reaction is :(1-x)v2CO" + 20H' Co(OH),.X 2 Here, also, K, calculated from the equation (13), -~ = K, (1 -x)vgives a much better constant, and yet this equation again appears tolack a theoretical basis.Nickel Chloride.The salt was purified by careful recrystallisation. A solution ofmedium strength was measured for four days, and a decided increaseof the hydrogen-ion concentration took place within the first twenty-four hours, rising from 0.00014 to 0*00018.No change beyond thelimits of error occurred on the three succeeding days. I n the follow-ing experiments, all solutions mere therefore allowed to stand inthe thermostat for twenty-four hours before being measured.In order to obtain the hydrolytic constant, a concentrated solutionwas prepared and its strength determined by analysis ; other solutionswere prepared from this by dilution62 ELECTROMETRICCell, H29. 3. M. F.4 ' 4 0'49278.8 0'503.217.6 0.510935.2 0.5229DETERMINATION OF THE HYDROLYSIS OF SALTS,TABLE XVII.I NiCI, I NH,NO, ['Hg,CI, electrode."1. [H'] x lo3.1oox. K~ x 105.0.0683 0'290 0.127 0.360.0568 0.184 0.16 0.290'0481 0.132 0'23 0 '270.0371 0.086 0.30 0'300 *30-Mean.. . , . . . . . . . ,XZ The values under Kl are calculated from equation (8), ____-for a first-stage hydrolysis of a salt with a univalent anion. Thesatisfactory nature of the constant shows that the reaction is correctlyrepresented by the ionic equation :NiCl' + OH' Z NiCl(0H).(1 - x)v,Zinc Sulphccte.The salt mas purified by recrystallising it three times from con-ductivity water ; an analysis gave SO4 = 33.43 and 33.41, whilsttheory requires SO, = 33.40 per cent.The "time" experiment for this salt was, as usual, carried outwith every precaution against chance impurities ; but, although varioussolutions were measured daily for four weeks, yet no sign appeared ofan equilibrium having been reached, the h ydrogen-ion concentrationvarying irregularly from day t o day.A solution of zinc chloride showed an exactly similar phenomenon.Owing to the similarity between zinc and magnesium sulphates, i twas expected that a similar variation in the hydrogen-ion concentra-tion, that is, in the hydrolysis, would be met with.The variationwas again observed, but not to so marked an extent as in zincsulphate. The percentage calculated for magnesium sulphate of con-centration v32 from the mean hydrogen-ion concentration is 0.0023,agreeing well with that found by Carrara and Vespignani. Theyused a fifth-molecular normal solution, and found 0.0047 per cent. atthe same temperature.The '' time "experiment again showed that the hydrolysis is by no means aconstant quantity. The variations were not large, but yet quitemeasurable.Solutions of cerium chloride showed undoubted variations in thehydrolysis from day to day. The mean percentage for vep is 0.14,whilst Ley found 0.5 for the same dilution a t 90.7".Thorium sulphate (v= 64) has also been examined.The mean percentage for v64 is 46ATTEMPTED SYNTHESIS OF DINAPHTHACRIDINES 63Finally, it may be mentioned that cobalt chloride shows considerablevariation in solution ; the mean percentage for g32 is 0.17, and forVI6 0.1 1.The most probable explanation of the peculiar behaviour of thesesalts lies in the theory that the hydrolysis leads to a heterogeneoussystem, and that basic salts and hydrates are present in colloidalsuspension.Xunzmary.1. The preceding experiments have proved that the hydrogenelectrode can be used to determine the hydrolysis of salt solutionseven when the hydrogen-ion concentration is as low as 0.3 x (seeammonium chloride).2. The hydrolytic constant of ammonium chloride proves ammoniato be about 70,000 times as strong a base as aniline.3. The salts of chromium are hydrolysed about 1.6 times as muchas the salts of aluminium, and chromium may therefore be consideredabout 1.6 times as weak a base as aluminium.4. Nickel salts are more strongly hydrolysed than those of cobalt,and in this connexion it is significant that the electropotential ofcobalt is higher than that of nickel (Wilsmore, Zoc. cit.).5. The salts of zinc, magnesium, cerium, thorium, cobalt, and, to aslight degree, nickel show peculiar behaviour in so far as theirsolutions present a variable degree of hydrolysis from day t o day.I n conclusion, I wish to acknowledge my deep debt of gratitude toProfessor F. G. Donnan for his ever-ready assistance and kindlyencouragement during the course of these experiments.THE MUSPRATT LABORATORY OFPHYSICAL AND E LECTRO- CH E JI ISTRY,UNIVERSITY OF LIVERPOOL

ISSN:0368-1645    

DOI:10.1039/CT9089300041

出版商:RSC    

年代:1908

数据来源: RSC

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ATTEMPTED SYNTHESIS OF DINAPHTHACRIDINES 63-Dinaphthacyidines :P-N-P V1.-Attempted Synthesis ofa-hHpCondensation of Meth ylene Dichloride and I-Sub-stituted- %napkt h ylarnines.By ALFRED SENIER and PERCY CORLETT AUSTIN.Two of the six theoretically possible dinaphthacridines (Senier andAustin, Trans., 1906, 89, 1387) are still unknown, and our attemptsto .synthesise derivatives of one of these by using P-naphthylamine64 SENIER AND AUSTIN: CONDENSATION OF METHYLENEin which the neighbouring a-position is substituted have led only tothe formation of dinaphthacridines of the ’-TmP type. But, al-a-CHathough we have not succeeded in obtaining the desired compounds,the results in themselves possess sufficient interest to be recorded.I n view of the experiments described in a former paper on halogenaddition compounds (Senier and Austin, Trans,, 1904, 85, 1196) andof recent work by A.E. Dunstan and Hilditch (Trans., 1907, 91,1659) on the substitution of halogens in acridines by working withhot solutions, the bromo-substitution derivative of ’-?-’ -dinaphth-a-CHaacridine described is worthy of note. It undoubtedly contains thehalogen in the meso-carbon position, for the linking of the naph-thylene groups by means of the meso-carbon must take place at thepcsition previously occupied by the bromine. Further, i t is importantto observe that this synthesis effectually removes any doubt thatremained as to the constitution of Reed’s dinaphthacridine, the proofof which until now was incomplete, since it depended in part on theassumption of Strohbach (Bey., 1901, 34, 4146) that the a-position inP-naphthylamine is more readily substituted than the other@position :N/ \ /, ,\/\Brl I I I j I I/*\/\I/\/\I I CBr I I\/\ -+I I I 1\/ CH,Cl, v \/ \/Taking into consideration the general fact that a linear arrange-ment of the rings in the synthesis of cyclic compounds is only ob-tained with difficulty (Senier and Austin, Zoc.c i t . ) , i t was expected ’-r-’ base, for this con- that it would not be easy to prepare theP-CHPtains a linear arrangement of rings on either side of the acridinenucleus, the only known dinaphthacridine containing a lineararrangement, and that only on one side, being Strohbach’s’-T-’ isomeride. Again, in view of the fact that when P-naphthyl- a-CHBamine condenses with methylene dihnlides or with formaldehyde theneighbouring a-position enters into the reaction, it was hoped that byfixing the a-position before the experiment by substitution the con-densation might then affect the other P-position and give the typeof acridine desired.Methylene dichloride was selected as a con-densing reagent, because, unlike formaldehyde, it reacts with both6- and a-naphthylamines and because the behaviour of formaldehydDICHLORIDE AND 1 -SUBSTITUTED-~-NAPHTHY LAMINES. 65with 1-substituted-2-naphtliylamines has already been the subject ofan investigation by Morgan (Trans., 1900, 77, 814), in which 110indication of the condensation we wished to bring about wasobserved.The results of our experiments shorn that when the a-position nextto that occupied by the amino-group in P-naphthylamine is taken byan easily replaceable element, such as chlorine or bromine, suchsubstituents are eliminated and condensation takes place a t thea-position with the formation either of Reed's base or, in the case ofbromine, of a bromo-derivative of that base; but that when thea-position is taken by such a substituent as the nitro-group, which isnot easily replaced, no condensation takes place.1.Interaction of Methylene DichZoride and l-ChZoro-2-n~p~t~~yl~~rnine.Five grams of 1-chloro-2-naphthylamine were heated in a closedtube with 24 C.C. (excess) of methylene dichloride for a short time toZOOo, when an orange sublimate was noticed at the end of the tube.After the first appearance of this sublimate, the heaticg was onlycontinued for about fifteen minutes.More prolonged heating orhigher temperatures led to unsatisfactory results. When the tubewas opened, the contents were first washed with a little cold acetone,then boiled with methylated spirit to which a little aqueousammonium hydroxide was added, and poured into cold water. Afterdecanting the liquid and recrystallising the dried residue frombenzene, large triboluminescent crystals containing no halogen andmelting at 2 1 6 O mere obtained, They mere identified with '-rep -dinaphthacridine (Reed).U-CHU2. Preparation OJ 1-Bromo-2-naphthylarnine.I n preparing 1-bromo-2-naphthylamine by the methodMorgan (Zoc.cit.), it was found to be of advantage togiven bywarm thesolution of aceto-p-naphthalide in glacial acetic acid to about 60' andtoaddmoreof the solvent whenever the mass became too thick tostir, otherwise an intimate mixture of the reagents was not obtained.Moreover, the brown precipitate thus formed was purified beforehydrolysis. This was done by boiling it with methylated spirit untilno more dissolved, and filtering, when it mas found that the alcoholicfiltrate contained bromoacetonaphthalide in a fairly pure condition.Thie solution was then hydrolysed by boiling with hydrochloric acid,and the hydrochloride thus obtained was treated with alkali to liberatethe base. One crystallisation from light petroleum was generallysufficient to yield crystals of pure 1 -bromo-2-naphthylamine.VOL. XCIII.66 SENIER AND AUSTIN: CONDENSATION OF METHYLENE3. Interaction of Methylene Dichloride azid I-Bromo-2-naphthylarnine.r l - B ~ o r n o - ~ - Y - ~ -dinaphthacridine, C,,H,cz i > C , , H,. U-CHUAfter several partially successful attempts to determine the properconditions, we found that a temperature of 230-240' was mostsuitable for bringing about the acridine condensation. I n our firstexperiment, we heated the closed tube to 200' and obtained as thechief product a black, non-crystdiisable substance, insoluble in benzene,but soluble in alcohol. Distillation of this black substance underreduced pressure gave rise to a yellow substance, which could not becrystallised and was not further examined.The latter compoundis possibly dinaphthacridone.Satisfactory results were, however, obtained by heating 5 grams of1-bromo-2-naphthylamine with 2 C.C. OC methylene dichloride in aclosed tube to 230-240' for three-quarters of an hour. It was notfound advisable to work with larger quantities. The contents of theopened tube were easily removed by boiling with methylated spiritcontaining some potassium hydroxide in solution.A heavy, black, oily substance was obtained, which, when washed bydecantation with cold water, solidified. This mas rubbed with a littlecold acetone, drained on a filter, and dried in a desiccator. It wasthen boiled with benzene, and the highly fluorescent, but dark, solutionfiltered from an insoluble residue, mixed with animal charcoal, boiledfor two hours under a reflux condenser, and again filtered and allowedto stand.The solution was thereby rendered much clearer, and slowlydeposited well-formed, pale brown crystals. One or two furtherrecrystallisations from benzene sufficed to purify them. When purethey are of a very pale yellow colour and melt at 215.5' (corr.) Theycontain bromine, but are not triboluminescent. On analysis :0.1564 gave 0*4011 CO, and 0.0500 H,O.0.1920 ,, 6.7 C.C. nitrogen a t 14' and 756 mm. N=4.08.0.0853 ,, 0.0452 AgBr. Br = 2254.C = 69.94 ; H = 3.54.C21H,,NBr requires C = 70.39; H = 3.35; N -- 3.91 ; Br = 22.34 per cent.The substance is evidently a rnonobromodinaphthacridine. It isessentially different from a dinaphthacridine bromide (compare Senierand Austin, Trans., 1904, 85, 1196), since it may be boiled withalcoholic potassium hydroxide and may even be distilled in a partialvacuum without decomposition.According t o the method of formation, it might be a derivativeeither of Reed's or of Strohbach's base, that is, either 7-bromo-p-N-p dinaphthacridine.'-r-' -dinaphthscridine or 1 -bromo-a- 6 Hp- Q- C HDICHLORIDE AND 1-SUBSTITUTED-2-NAPHTHYLAMINES. 67It is readily soluble in chloroform or carbon disulphide, less so inbenzene or toluene, and very sparingly so in alcohol. It dis-solves easily in hot glacial acetic acid, depositing yellow crystals oncooling. The latter melt at 273" and have not yet been investigated.The hydrochloride of the base is yellow, and is precipitated from analcoholic solution by means of hydrochloric acid.No method wasfound for purifying it. The preparation of double salts with metalswas difficult, owing to the fact that no very suitable solvent could befound.The aurichloride, [CzlH1,NBr],, [ HAuCI,],, was obtained as a yellow,flocculent precipitate when a few drops of auric chloride solutionwere added to a solution of the base in a mixture of alcohol and aceticacid. The yellow precipitate was washed with dry ether and dried a t105'. On analysis :0.0694 gave 0.0156 Au.The plcctinichZorride, [C,,H,,NBr],,H,PtC16, was obtained in a similarIt is a yellow powder, which wasThe specimen mas evi-Au= 29-47.C,3H,,N,C18Br,Au, requires AU = 22.46 per cent.way by using platinic chloride.washed with dry ether and dried at 105'.dently not quite pure :0.0603 gave 0.0108 Pt.Pt = 17-91.C,,€€,,N,C16Br,Pt requirea Pt = 17.31 per cent.4. Replacement of the Bromine in Monobromodinaphthacridine byHydrogen.I n order to prove the constitution of monobromodinaphthacridine, itwas necessary to replace the bromine by hydrogen. The reductiontook place readily by the action of an alcoholic solution of stannouschloride on the base partly dissolved and partly suspended in alcohol.Some tin and free hydrochloric acid were added, and the mixturewas boiled for several hours under a reflux condenser, when a greensubstance gradually formed. When cold, the liquid was removed byfiltration, and the green substance was separated mechanically fromthe residual tin. This green substance was boiled with methylatedspirit, in which it was moderately soluble, then treated with potassiumhydroxide, boiled, mixed with water, and the yellow, flocculent pre-cipitate obtained was dissolved in aqueous pyridine. The filteredsolution deposited orange crystals melting a t 243'. They wereidentified as bis-p-N-P -dinaphthacridine dihydride (Senier and Austin,Trans., 1906, 89, 1398), which is known to give a green hydro-chloride,A H aF 68 SPENCER AND STOKES: THE DIRECT INTERACTION OFThe bromodinaphthacridine is evidently therefore a derivative of '-r-' -dinaphthacridine (Reed).a- C Ha5. Interaction of MethyZe?ze Dichloride and 1 -Nitl.o-a-Ina~htl~yZami?ze.When 1-nitro-2-naphthylamine was heated to 210" in a closed tubewith methylene dichloride for one hour, it was found that no reactionhad taken place, for the original substance was recovered unchanged.Another attempt was made by heating the tube to 250-260' fortwo hours, when the contents of the tube were completely charred,although acridines are stable at this temperature.QUEEN'S COLLEGE,G A LW AY

ISSN:0368-1645    

DOI:10.1039/CT9089300063

出版商:RSC    

年代:1908

数据来源: RSC

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68 SPENCER AND STOKES: THE DIRECT INTERACTION OFVII.---The Direct Interaction of Aryl Halides andMagnesium.By JAMES FREDERICK SPENCER AND ELEANOR MARGUERITE STOKES.IN the course of a series of reactions involving the use of the Grignardreagent, we obtained evidence which led us to doubt the necessity ofthe presence of ether or any catalyst in the preparation of magnesiumnryl halogen compounds. Preliminary experiments showed that aryliodides and magnesium react, on heating, with the formation ofmagnesium aryl iodides, which in view of the subsequent action ofwater must be constituted according to the type R*Mg*I.The reaction took place with the evolution of a large amount ofheat, and was generally complete in two to tbree minutes; on theaddition of water, after cooling, the parent hydrocarbon was re-generated with the evolution of heat :RMgI + H,O = R*H + Mg(0H)I.The ease with which the combination occurred indicated that thiswas possibly a reaction suitable for removing halogens from cycliccompounds, and so capable of being used as a means of orientation i nthe case of substituted compounds.With the object of testing the suitability of the reaction for suchdeterminations, we have studied the action of magnesium with anumber of aromatic halogen substitution products, and have foundthat i t is possible to remove iodine and bromine from such compoundsalmost quantitatively, and to obtain a large yield of the parentsubstance 8s product of the reactionARYL HALIDES AND MAGNESIUM.69Thus m-broinoaniline gave a yield of 90 per cent.of the theoreticalquantity of aniline, and p - bromophenol gave 40-50 per cent. of thetheoretical yield of phenol,Halogen acids and nitro-compounds containing halogens did notyield the corresponding acids and nitro-hydrocarbons. I n the case ofthe acids, carbon dioxide was evolved, and with the nitro-compounds,nitrogen peroxide was evolved, which immediately reacted with themagnesium, giving rise to so much heat that the compound wascompletely charred, and, indeed, in one experiment the test-tubeme1 ted.Halogen derivatives of naphthalene react in the same way withmagnesium, a-bromonaphthalene yielding 70-80 per cent. of naph-thalene.Similarly, monobromoacenaphthene gave a yield of about 50 percent.of the theoretical quantity of acenaphthene when treated in thesame way.This reaction does not seem to be general for chloro-substitutionproducts ; out of six substances investigated, namely, benzylidenechloride, 0- and p-chlorophenol, a-chloronaphthalene, p-chlorotoluene,and o-chloroaniline, a reaction was found to take place only in thecase of o-chloroaniline; in this instance, a large yield of aniline wasobtained. Iodobenzene arid bromobenzene require special note, forwith these compounds it was found t h t the initial reaction proceededin two directions, as indicated by the equations :(1) C,H,I: + Mg = C,H,*Mg*I.(2 j 2C,H,T + Mg = C,H,*C,H, + MgI,.The products, benzene and diphenyl, were present in quantitieswhich indicated that the reaction represented by (1) had taken placewith about 45 per cent.of the iodobenzene, and the reaction repre-sented by equation (2) with about 55 per cent. of the iodobenzene.The formation of diphenyl was observed by Tissier and Grignard(Compt. rend., 1901, 132, 32) when carrying out the Grignardreaction under ordinary conditions.We have done little up to the present with aliphatic compounds, b u tpreliminary experiments have shown that methyl iodide, methyleneiodide, trimethylene iodide, and isopropyl iodide do not react at allwith magnesium when the two substances are heated together. Mono-bromosuccinic acid, however, does react, and the action commenceswithout initial heating after the substances have been mixed forabout two minutes.The product on treatment with water yieldssuccinic acid.On treating the magnesium aryl compounds with water, weobtained derivatives which may bo used for deciding the position o70 SPENCER AND STOKES: THE DIRECT INTERACTION OFsubstituting groups ; they can, however, also be used for purposes ofsynthesis. For example, magnesium phenyl iodide, prepared by themethod indicated, was ground ir^ a mortar with a little absoluteether and an excess of solid carbon dioxide for about five minutes,the product of this treatment yielded about half the theoreticalquantity of benzoic acid on the addition of dilute hydrochloric acid.I n the absence of ether, the yield of benzoic acid was much reduced.This reaction, effected without the use of a catalyst, indicates thatether is not absolutely necessary for the reaction, and the Grignaidcompounds are not necessarily formed through oxonium compounds ofthe type:but rather, the view put forward by Tschelinzeff (Bey., 1905, 38,3664) is the more correct one, namely, that the addition occurs firstbetween the iodide and the magnesium, and this then forms an additioncompound with ether :It1 + Mg = R*Mg'I.R * M g * I + 3 2 > 0 = C H C2H5>C)<I Mg*R .2 5 2 5EXPERIMENTAL.Interaction of Idobenzene and itfagnasizcm.--Dry iodobenzene(40 grams) was mixed with dry magnesium powder (9 grams) in asmall, hard, round-bottomed flask fitted with an air condenser.Themixture was carefully warmed over a free flame to the boiling point ofthe iodobenzene; after boiling for about a minute, the reactioncommenced, and proceeded without any additional heating.Theproduct was a light grey, homogeneous mass, which was slowlydecomposed by the moisture of tho air, forming benzene. When themass had cooled, cold water was slowly added to it ; this brought abouta decomposition which was accompanied by the evolution of heat. Assoon as the decomposition was complete, the products were distilledwith steam, when benzene, diphenyl, and unchanged iodobenzene werefound in the distillate. The yield of benzene was 44 per cent,, and ofdiphenyl 54 per cent., of that required by theory.The melting point of the diphenyI(7OO) was unchanged after mixturewith an equal weight of pure diphenyl.Interaction of Bromobenzeite and Mccgnesium.--In this case, thereaction did not occur a t all readily, it being necessary to boil themixture of bromobenzene and magnesium for about fifteen minutesbefore combination took place.The organic products and yields werethe same as in the case of iodobenzeneARYL HALlDEY AND MAGNESIUM. 71Interaction of p - Iodotoluene and Magne&m,- p - Iodotoluene(15 grams) and magnesium powder (2 grams) were mixed and gentlywarmed in a hard glass flask fitted with an air condenser. As soon asthe boiling point of the iodotoluene mas reached, the reaction alsocommenced, and proceeded without further heating ; it was, however,not as violent as with iodobenzene. The product was a light greymass, which was treated with water and distilled in steam.Thedistillate was extracted, dried, and fractionated, and shown to consistof toluene. The yield was 87 per cent,, and a small quantity ofunchanged p-iodotoluene was also recovered.Interaction OJ o-Byornotoluene und Magnesium-The interaction ofthese two substances took place in exactly the same way as in the caseof p-iodotoluene. The product was the same, and the yield was equallygood.Intemction of m- Bronzoanilins and Mccgnesium.-Dry m-bromo-aniline (15 grams) was mixed with magnesium powder (4 grams) andheated in the same way as the foregoing mixtures; after two minutes,a most violent reaction took place. A yellow, solid mass wasobtained, which reacted so violently with water that the liquid boiled.The whole mass was then distilled in steam, and the oil which passedover was extracled and fractionated.A yield of 90 per cent. ofaniline was obtained.Interaction of o-Cltlo?*oaniline and Hagnesiuna.-This reaction tookplace extremely readily when heat was employed, and a good yield ofaniline was produced.Interaction of p-Bromaphenol and Magnesium. -p-Bromophenol(8 grams) was mixed with magnesium powder (2 grams) and heated,the reaction commencing suddenly after about two to three minutes’heating. The product, a light grey, solid mass, was treated with waterand distilled in steam, when a yield of 40 to 50 per cent. of phenolwas obtained,When tribromophenol was substituted for phenol, the reaction tookplace with extreme violence and evolution of heat, causing the tube tosoften.The products contained less bromine than the originaltribromophenol, for on the addition of bromine water to the solutiona yellowish-white preoipitate oE tribromophenol was formed, butfurther identification was impossible, nor could the vigour of thereaction be lessened,Interaction of a-Brornonaphthalene and Magne&urn.-a-Bromo-naphthalene (20 grams), mixed with magnesium powder (4 grams), washeated to boiling point, when a vigorous reaction commenced, whichcompleted itself without any further heating, The product was awhite and apparently crystalline mass. When cold, the addition ofwater was attended by great evolution of heat, and the presence o72 FORSTER AND FIERZ: THE THIAZO-GROUP. PART I.naphthalene was at once evident from its odour. The mass was theudistilled in steam, when a 72 per cent. yield of naphthalene wagobtained. The yield mas improved by the use of excess of magnesium ;thus, whilst one atomic proportion of magnesium furnished a yield of44 per cent, of the theoretical, from three times the quantity a yieldof 72 per cent was obtained. The change in the yield is due to thesmaller amount of the bromo-compound escaping reaction.Interaction of Brornoncenaphthene and Mngnesiurn.-About 1 gramof bromoacenaphthene was mixed with excess of magnesium powderand heated over the free flame. The reaction did not commence forabout five minutes, and then proceeded quietly. Water WAS thenadded to the product, but action took place only on warming. Thiswas in all probability due to the fact that the magnesium acenaphthylbromide was protected from its action by being coated with unchangedbromoacenaphthene. The products after treatment with water wereextracted with alcohol, and the acenaphthene formed crystallised out ingood yield.The investigation of this reaction is being continued.CHEMICAL LABORATORY,BEDFORD COLLEGE,BAKEI: STKEET, W

ISSN:0368-1645    

DOI:10.1039/CT9089300068

出版商:RSC    

年代:1908

数据来源: RSC

摘要:

72 FORSTER AND FIERZ: THE THIAZO-GROUP. PART I.VIII.-The Ft*iazo-G.i*oup. Part I. Triuzoacetic Acidand Triazoacet one (Ace t ony lazoimid e) .By MARTIN ONSLOW FORSTER and HANS EDUARD FIERZ.DESPITE the variety of triazo derivatives which have been investigated,principally by Griess, Curtius, Noel ting, and their collaborators duringthe past forty pars, one class of these compounds would appear tohave escaped examination; we refer to those types in which the triazo-group has replaced hydrogen in carboxylic acids, ketones, aldehydes,and alcohols of the aliphatic series. So far as we have been able toascertain, the only triazo-ketone to be met with in the literature iscamphorylazoimide (Trans., 1905, 87, 836), and it is chiefly inconnexion with this compound that our attention has been drawn tothe subject.The " triazoacetic acid '' described by Cartius and Lang(J. p . C'hem., 1888, [ii], 38, 532), at first regarded as having theconstitution FOHSTER AND FIERZ: THE TRIAZO-GROUP. PART I. 73is now recognised as a bimolecular polymeride of diazoacetic acid;entitled bisdiazoacetic acid, it is variously represented asIn the present communication, we describe triazoacetic acid,N3*CH2*C0,H, its amide, and ethyl ester, along with the simplesttriazo-ketone, acetonylazoimide or triazoacetone, CH,*CO*CH,*N,.The last-named substance is the true analogue of camphorylazoimide,which it recalls in respect of its behaviour towards potash; theaction of alkali on the simpler molecule is very vigorous, alcoholicpotash liberating nitrogen from acetonylazoimide almost explosively,whilst the aqueous alkali, even when very dilute (2 per cent.), sets upa brisk effervescence. There is a distinction, however, betweencamphorylazoimide and triazoacetone in regard t o the quantitativeaspect of the change.We have shown that exactly two-thirds of thenitrogen is liberated from the camphor derivative, which passes intothe imine of camphorquinone :but the gasometric study of the alteration which acetonylazoimideundergoes with alkali shows that subsidiary to the change,CH,*CO*CH2*N, -+ CH,*CO*CH:NH --+ CH,*CO*CH:O,there occurs, t o the extent of, roughly, 15 per cent., elimination ofhydrazoic acid,CH,*CO*CH2*N, + H,O = CH,*CO*CH,*OH + HN,,which does not take place when camphorylazoimide is treated withboiling alkali.This difference in behaviour probably owes its originto the absence of the cycloid structure, which renders the camphorderivative more stable, and also to the more hydrcgenised condition ofthe carbon atom to which the triazo-group is attached in acetonyl-azoimide, as well as to the comparative freedom of the unsubstitutedmethyl group, because a preliminary experiment with 2-triazocyclo-hexanone has indicated that in this case, also, both changes proceedsimultaneously :Yields nitrogen and Yields nitrogen and Yields nitrogen only.hydrazoic acid. hydrazoic acid.The facility with which nitrogen is eliminated from these compound74 FORSTER AND FIERZ: THE TRIAZO-GROUP. PART 1.appears to depend on the immediate neighbourhood of t h e ketonic andtriazo-groups, and leads us to suggest, as a possible explanation, t h a tthe action of alkali is such as to bring about the formation of anunstable ring-system from which nitrogen is forthwith liberated :-CH*N<R -C:NH*R -C:NH-co -f ]/ --+ N2+ I-C--O -c:o IAccepting the common view of the triazo-group, a n d comparing itwith the diazo-complex as occurring in diazomethane and diazoaceticester,N--N<I I N CH,<#CO,Et*CH<N, Nit will be recognised that two-thirds of the nit,rogen in the first-namedradicle stands in that relation to the remainder which is borne by thenitrogen in alphatic diazo-compounds to the carbon with which i t iscombined.Now there exists a considerable body of evidence to showt h a t the nitrogen in diazomethane and diazoacetic ester is capable oftaking part in additive action, the products parting easily withthe element in question.For instance, Buchner (Annulan, 1893, 273,214; compare also Buchner and Papendieck, Zoc. cit., 232 and 246;Buchner and Witter, Zoc. cit., 239) found that when ethyl diazo-acetate acts on the esters of unsaturated acids, pyrazolinedicarboxylicesters are produced, which lose nitrogen when heated, yielding tri-methyleued i ca rboxy 1 i c esters :...................C*2Me*RH + W>CH*C02Me = CO,Me* 7”-i-N: ......... s;T iCH, N CH,--CH;C02Me ;von Pechmann, again (Bey., 1894, 27, lS90), obtained methylpyrazoline-4 : 5-dicarboxylate by the interaction of diazomethane andmekhyl fumarate,CO,Me*?H---C I H 2..+ QH”N= co2Me* CH:-N: N j’CO,Me*EHCO,Me*CH N= ......................the pyrazolinecarboxy lic esters being here represented in their pseudo-form t o indicate more clearly the loss of nitrogen.Another ring-system which readily parts with the element arises from diazomethaneand thiocarbimides, von Pechmann and Nold (Bey., 1896, 29, 2588)having shown that phenylaminothiodiazole,behaves in this manner when fused, whilst the recent conversionof aldehydes into methyl ketones by the action of diazomethanFORSTER AND FIERZ : THE THIAZO-GROUP. PART 1. 75(Schlotterbeck, Ber., 1907, 40, 479) has been explained with someplausibility by assuming the intermediate formation of furodiazoles,Hence the possibility of mutual satisfaction of affinity between thecarbonyl and triazo-groups appears by no means remote, and isindependent of the alternative representations,-N:NiN and -CH:NiN,which might be used for the azoimide complex and aliphatic diazo-radicle respectively.Another argument in favour of this explanation may be drawn fromthe behnviour of triazoformic, as compared with that of triazoacetic,ester. When ethyl triazoformate is treated with aqueous potash, thesubstance is promptly hydrolysed, nitrogen being eliminated exclusivelyin the form of hydrazoic acid :N,*CO,*C,H, + H20 = HN, + CO, + C,H,*OH ;here there is no hydrogen attached to the carbon atom with which thetriazo-group is combined, and consequently the tendency towards ring-formation as indicated above cannot find expression, whereas triazo-acetic acid so far resembles triazocamphor as to yield nitrogen whenboiled with excess of potash, unaccompanied by hydrazoic acid,N,*CH,*CO, K + N, + NH :CH*CO,H,although the negative hydroxyl group certainly exerts a powerfulretarding influence on the change.Whilst, however, this hypothesisof potential ring-formation appears to us a reasonable one, difficultyarises in connexion with triazoacetoxime and the oxime of camphoryl-azoimide. It has beon shown that the latter substance yields hydrazoicacid instead of nitrogen with alcoholic potash (Trans., 1907, 91, 874),but we now find that triazoacetoxime furnishes both hydrazoic acid andnitrogen with the utmost readiness, and a comparison of the formulae :does not suggest an explanation af this apparent discrepancy.Tri-azoacetoxime is a very labile substance, however, and cannot bedistilled, even under 2 mm. pressure, without undergoing decomposi-tion; moreover, we believe it has a tendency to undergo transforma-tion into the nitroso-modification, and consequently it may be supposedthat the liberation of nitrogen is due to intermediate association of thetriazo- and nitroso-groups76 FORSTER AND FIERZ: THE TRIAZO-GROUP. PART I.opportunity for which does not present itself in the case of thecamphoryl derivative.The properties of triazoacetic ester naturally invite comparisonwith those of the corresponding diazo-compound, prepared by Curtius,and the contrast between the two substances brings out once more thestability of the triazo-group as compared with the diazo-complex.Boiling water, iodine, mercuric oxide, and ammmiacal silver oxideleave the ester unchanged, and sodium does not dissolve in the coldsubstance; it is, moreover, colourless, and the odour is very faint.Furthermore, triazoacetic ester may be hydrolysed to the acid, whichis a well-defined substance, ,and does not decompose below iOOo,whereas attempts to liberate diazoacetic acid by passing carbon dioxidethrough the hydrolysed ester result in liberation of nitrogen, whilstconcentrated aqueous alkalis induce simultaneous hydrolysis and poly-merisation, leading to bisdiazoacetic acid,We are engaged in studying the triazo-derivatives of other typicalmembers of the aliphatic series, including alcohols, aldehydes, ketones,and esters ; such compounds have been prepared from methyl ethylketone, malonic ester, and acetoacetic ester, and we hope to describethese in a subsequent communication.E x P E R I hi E N T A L.T&xoacetic Acid, N,* CH,*CO,H.Fifty grams of triazoacetic ester were shaken with a, 20 per cent.solution of potassium hydroxide containing 21 grams, this being aslight deficit from one molecular proportion ; the temperature roseand the oil disappeared slowly, but there was no liberation of gas.After being twice extracted with ether, the neutral solution wastreated with the calculated amount of sulphuric acid and extractedfifteen times with ether, which, when dried with ignited sodiumsulphate, left a very pale yellow, oily liqlrid on evaporation.This washeated in boiling water during one hour under 2 mm. pressure, whenthe acid was found to be sufficiently anhydrous to solidify in meltingice, but there was no distillation at this temperature, and it was notconsidered safe to heat the substance more strongly.Triazoacetic acid crystallises in hygroscopic, glassy plates, andmelts a t about 1 6 O . I t has a very faint odour, suggesting that ofbutyric acid without the pungent effect; the substance is a strongacid, and feels greasy when rubbed between the fingers. On a hotplate, the acid detonates with a moderate explosion and takes fire,but when it is heated in a capillary tube a violent detonation occurs.It does not reduce ammoniacal silver oxide, even on boiling thesolutionFORSTER AND FIERZ: THE TRTAZO-GROUP.PART I. 77The analysis of trinzoacetic acid and ester has presented unusualobstacles, and more than twenty attempts have been made t o obtainsatisfactory results. The principal difficulty lies in the fact thatwhen combustion is conducted under ordinary conditions, methaneappears among the products, whilst adopting the device which hasbeen suggested to meet this drawback, namely, substitution of leadchromate for copper oxide and mixing the substance with cuprouschloride (Dunstan and Carr, Proc., 1896, 12, 48, and Haas, Trans.,1906, 89, 570), low results were obtained consequent on the pro-duction of methylamine. In the case of the acid, combustion for per-centage of carbon and hydrogen was finally carried out in a tubecontaining platinised asbestos, an attempt being made 60 maintainthroughout the operation a large excess of oxygen, which was usedinstead of air ; for the purpose of estimating nitrogen, advantage wastaken of the fact that when potassium triazoacetate is heated withexcess of potash the triazo-group undergoes disruption, and accordinglythe weighed substance was mixed with 20 per cent.aqueous potashbefore being placed in the combustion tube :0.3306 gave 0.2913 CO, and 0.0892 H,O.0.0947 ,, 34.25 C.C. of nitrogen at 18.5' and 747 mm. N = 41.64.C,H,O,N, requires C = 23.76 ; H = 2-97 ; N = 41.58 per cent.I n view of the violence with which aromatic azoimides lose nitrogenwhen treated with concentrated sulphuric acid, tho behaviour of theagent towards triazoacetic acid is remarkable; when mixed with con-centrated sulphuric acid on a watch-glass, no change takes placeimmediately, and only on vigorous stirring with a glass rod does gasappear, very slowly at first, but quickly increasing in briskness.Estimation of molecular weight was conducted in benzene and inphenol.I n the former solvent, 221 units represents the average ofthree experiments, whilst in phenol the mean of four amounted to 99units, the solution being brown ; the formula C,K,O,N, requires101 units.Salts of Triazoacetic Acid.-The silver salt, C,H,O,N,Ag, obtainedas a curdy precipitate on adding silver nitrate to a neutral solution ofpotassium triazoacetate, may be crystallised from boiling water inpresence of a few drops of dilute nitric acid, separating in colourless,lustrous needles. An attemptl t o estimate the silver by cautiousevaporation with nitric acid having led to a slight detonation, aweighed quantity of the substance was reduced with ammoniumsulphide, the silver sulphide thereby precipitated being convertedinto silver.For the purpose of estimating nitrogen, the saltwas mixed with 20 per cent. potash before being placed i n thetube :C = 24-03 ; H = 2.9978 FORSTER AND FlERZ: THE TKlAZO-GROUP. PART 1.0.2661 gave 0.1385 Ag. Ag= 52.05.0.1923 ,, 34.4 C.C. of nitrogen a t 19O and '745 mm. N = 20.50.C,H,O,N,Ag requires Ag = 51.92 ; N = 20.20 per cent.When heated on an iron plate, the substance detonates mildly andburns brightly.An attempt to prepare the copper salt led to a curious result.Having noticed that copper sulphate develops a deep green colorationwhen mixed with potassium triazoacetate, copper oxide was dissolvedin an aqueous solution of the free acid.It was noticed, however, thatthis solution steadily liberates gas when heated on the water-bath,and, although the liquid may be concentrated at 40°, an att.empt toobtain crystals of the copper salt by leaving the liquid in a desiccatorfailed, because at a high concentration gas was evolved, even at theordinary temperature. A dark green, hygroscopic powder finallyremained, and, on warming an aqueous solution of this product withdilute potash, it remain6d momentarily clear, but suddenly precipi-tated cuprous oxide and liberated ammonia,The potassium salt is freely soluble in water, and is precipitatedby concentrated potash.A neutral, moderately dilute solution issurprisingly stable, and may be boiled without evolving gas, but onadding to the hot liquid some 40 per cent. potash, torrents of gas areliberated, followed, after a momentary pause, by another rush of gas,consisting of nitrogen and ammonia, and the effervescence is continuedin this characteristic fashion by further addition of alkali. We havemade several attempts to isolate the products of this change, whichshould include glyoxylic acid, but hitherto we have been able to recog-nise onlyoxalic acid, which probably arises from glyoxylic acid by theaction of potash.When the potassium salt has been treated withexcess of alkali in the manner indicated above, the liquid depositscrystals on cooling, but the composition of this product appears tovary considerably according to the conditions of the experiment. Onone occasion, a small quantity of a substance was obtained which leftno residue on evaporation with concentrated sulphuric acid, andappeared to be an ammonium salt; it reduced ammoniacal silveroxide and Fehling's solutions immediately without warming, but thisproperty disappeared on boiling with potash, and the reaction is beingstudied therefore more fully.A neutral solution of patassium triazoacetate gives a lustrous,crystalline precipitate with lead nitrate, and a deep red colorationwith ferric chlorideFORSTER AND FIERZ: THE TRIAZO-GROUP.PART I. 79Ethyl Z'riccxoacetccte, N,*CH,*CO,*C,H,.Two hundred grams of ethyl chloroacetate and 100 grams of alcoholwere heated under reflux during three hours with 120 grams ofsodium azide, and sufficient water to maintain the salt in solution; acurrent of steam was then passed through the liquid, from which theester was quickly removed. On diluting the distillahe with water,adding a considerable quantity of crystallised sodium acetate, andallowing the heavy oil to separate, 190 grams of the substance wereobtained, and this mas shaken twice with water, dried with calciumchloride, and distilled under 2 mm. pressure, when it boiled to the lastfew drops a t 44-46'.The difficulties presented by the analysis of this ester have beenmentioned above, and aftor eight attempts, the indicated results ofwhich vary between 19.8 and 34.3 per cent.of nitrogen, we are stillunable t o record a satisfactory estimation of this element; by theuse of platinised asbestos, however, fairly concordant determinationsof carbon and hydrogen have been obtained, although these have beenusually too high, owing to the di6culty of avoiding the formation ofnitrous fumes, even in presence of silver gauze :0.1571 gave 0*2100 CO, and 0.0790 H,O.We are indebted to Dr. Joshua for an independent estimation of0.1202 gave 0 1621) CO,.It happens, unfortunately, that the gasometric estimation of nitrogeneliminated by concentrated sulphuric acid, hot potash, or stannouschloride cannot be used to supplement the above analytical dataregarding the ester, because the action in each case takes an abnormalcourse, and the percentage of gas evolved by these agents agrees moreclosely with half the azidic nitrogen (16.3 per cent.) than with two-thirds (21.7 per cent.). So regular is this discrepancy from theexpected result that we became suspicious, before the analyticaldifficulties mere surmounted, regarding the identity of the ester, as itseemed possible that the triazo-group had conferred on acetic ester thecapacity t o form an alcoholate, because i t happens by chance thattwo-thirds of the nitrogen required by the formula,N,*CH,*C(OEt),*OHamounts to 16.0 per cent., or, roughly, half the nitrogen content ofthe simple ester.Accordingly, a specimen of triazoacetic ester waaprepared by heating 50 grams of ethyl chloroacetate under reflux withsodium azide dissolved in water, but the product was found to corre-C = 36.30 ; H = 5.62.C,H70,N, requires C = 37.21 ; H = 5.43 per cent.carbon by oxidation with a mixture of sulphuric and chromic acids :C=36*76 per cent80 FORSTER AND FIERZ: THE TRIAZO-GROUP. PART I.spond in every respect with the ester prepared in presence of alcohol ;the action proceeds in the same way, but is much more sluggish thanwhen alcohol is used. Tbe abnormal behaviour indicated above stillawaits explanation, therefore, and we hope to furnish this later.Triazoacetic ester is a limpid, colourless oil, having a faint, sweetodour, more suggestive of chloroform than of ethyl acetate, theresemblance to the latter becoming more marked in steam, with whichthe substance is readily volatile; when inhaled for some seconds, thevapour produces a throbbing sensation in the head, and slight palpita-tion of the heart.On mixing with concentrated sulphuric acid, thereis no effervescence at first, but, on stirring vigorously, gas is liberatedslowly, the disengagement becoming ultimately quite brisk ; withstannous chloride dissolved in concentrated hydrochloric acid, nitrogenis evolved immediately. When the ester is shaken and warmed with10 per cent. caustic potash, i t is quickly hydrolysed, forming a clearsolution of potassium triazoacetate, but concentrated alkali (40 percent.) appears to leave the substance unchanged, unless alcohol is addedor the temperature raised. Freshly-cnt sodium does not dissolve in itunless the liquid is heated, when vigorous action takes place; thesubstance is indifferent towards mercuric oxide and a solution ofiodine in potassium iodide.The specific gravity of triazoacetic ester is 1.127 compared withwater at 20'.An estimation of molecular weight in benzene gave119, 125, and 127 units, the formula C4H70,N, requiring 129.Yriaxoacetccnzide, N,*CH,*CO*NH,.When shaken with aqueous ammonia, the ester dissolved, and, onevaporating on the water-bath, a pale red liquid remained whichsolidified on cooling ; this was drained on earthenware, and recrystal-lised twice from hot benzene :0-141 I gave 68.4 C.C.of nitrogen a t 20' and 758 mm.C2H40N, requires N = 56.00 per cent.Triazoacetamide forms tough, lustrous, colourless needles, frequentlyexceeding an inch in length, and melting at 58'; it is readily solublein water and in alcohol, but is most conveniently crystallised from hotbenzene, in which it is moderately soluble, whilst boiling petroleumalso dissolves it, but less freely. When thrown on a hot plate, i tdetonates feebly and takes fire.The substance is unusually resistant towards concentrated sulphuricacid, with which it must be warmed to about 50' before gas is liberated;cold 60 per cent. aqueous potash, however, attacks it immediately,torrents of nitrogen and ammonia being liberated, whilst more dilutesolutions of alkali disrupt the triazo-group very slowly.An aqueousN = 56.30FORSTER AND FIERZ: THE TRIAZO-GROUP. PART I. 81solution of the amide dissolves yellow mercuric oxide on boiling, butthe resulting compound, unlike mercury acetamide, does not lose themetal when treated with hydroxylamine hydrochloride, a precipitatebeing formed only on adding alkali, when effervescence takes place(compare Trans., 1898, 73, 785).Ethyl Triaxofoymccte, N,*CO,*C,H,.Methyl azoimidocarbonate was prepared by Curtius and Heidenreich( J . pr. Cheni., 1895, [ii], 52, 454) from ammonium azoimide andmethyl chlorocarbonate, and, in order to compare the condition of thetriazo-group in this type of compound with the behaviour of the samecomplex occurring in the acetic series, we have examined the corre-sponding ethyl ester, which was prepared by agitating 50 grams of ethylchlorocarbonate with an aqueous solution of sodium azide containing35 grams until the pungent odoiir of the original material was nolonger perceptible ; the heavy oil was then removed, dried with sodiumsulphate, and distilled under 2 mm.pressure, when i t boiled steadilyat 2 5 O .The colourless, limpid ester has sp. gr. 1.118 compared with water atIS0, and boils a t 114' under 769 mm. pressure, but is liable to explode ;the odour is more powerful than that of triazoacetic ester, and thedisagreeable effects of inhaling the vapour are much more marked.I t may be mixed with concentrated sulphuric acid or 40 per cent. potashwithout evolving gas, but the alkali hydrolyses it completely to hydrazoicacid, alcohol, and carbonic acid; it is therefore impossible to producetriazoformic acid, or even the salts, because a deficit of alkali merelyleaves the corresponding amount of ester unchanged.Alcoholicammonium sulphide reduces ethyl triazoformate to urethane, nitrogenbeing set free.Triaxoacetone (Acetonylazoimide), N,*CH,*CO*CH,.The monochloroacetone required for the production of triazoacetonewas prepared by Fritsch's method (Annalen, 1894, 279, 313), whichwe have found to yield excellent results.One hundred grams of chloroacetone (b. p. 119-12lo) mere shakenwith a concentrated aqueous solution of sodium azide containing 80grams, to which a few drops of glacial acetic acid had been added;after twenty-four hours, the pungent odour of chloroacetone being nolonger perceptible, the oil was extracted with ether, dried with sodiumsulphate, and distilled under 2 mm.pressure. The product, weighing90 grams, was shaken with freshly-ignited sodium sulphate, and againdistilled under 2 mm. pressure, the major portion boiling at 54*, andhaving sp. gr. 1.123 compared with water a t 18' :VOL. XCIII. 82 FORSTER AND FIERZ: THE TRIAZO-C4ROUP. PART I.0-2398 gave 0.3204 CO, and 0.1 132 H,O.0.1685C,H,ON, requires C=36.36 ; H=5*05 ; N=42*42 per cent.Freshly-distilled triazoacetone is a colourl6ss, highly refractiveliquid having a faint odour, but after a few days, even when preservedin a well-stoppered bottle and protected from light, the odour ofcarbylamine is noticeable in the specimen, which has become yellow.The substance exhibits no tendency to solidify, remaining quite limpidin a freezing mixture j it is sparingly soluble in water, and very readilyvolatile in steam.When dropped on a hot plate, triazoacetoneexplodes, and burns with a brilliant flame ; concentrated sulphuricacid decomposes the substance immediately, liberating nitrogen.Action of Alkali. -When triazoacetone is treated with concentratedaqueous potash (40 per cent.), nitrogen is liberated with almostexplosive violence, and the liquid becomes red; eyen with a 1 percent. solution of the alkali, gas evolution is quite brisk, and severalconcordant estimations of the nitrogen evolved during the changeindicated that this amounted to roughly 4 per cent.less than two-thirds :C = 36.44 ; H = 5.24.N=42*45. ,, 61.1 C.C. of nitrogen at 1 9 O and 761 mm.091550 gave 33.4 C.C. of nitrogen at 22' and 761 mm.C,H,ON, requires 2/3N = 28-3 per cent.By decomposing 5 grams of t,he triazo-ketone at one time, steamingthe product while alkaline, then adding dilute sulphuric acid and dis-tilling again, we were able to show that the deficit indicated above isdue to simultaneous production of hydrazoic acid, which mas easilyrecognised in the acid distillate. Excepting ammonia, however, theother products of the changes involved are not easily identified. Thefact that nitrogen, ammonia, and hydrazoic acid are eliminated, indi-cates that the following decomposition occurs :N = 24-3.I.N,*CH,*CO*CH, = N, + NH:CH*CO*CH,.11. NH:CH*CO°CH, + H20 = NH, + O:CH*CO*CH,.111. N,*CH,*CO*CH, + H20 = HN, + HO*CK,*CO*CH,.Accordingly, it should be possible to recogniso both pyroracemicaldehyde and acetol in the product, and, although we have failed toisolate these compounds, probably owing to the further action ofalkali, the presence sf reducing materials is indicated by vigorousaction on Fehling's solution and ammoniscal silver oxide.The 8emicarbazone.-On mixing 6 grams of triazoacetoue with6.5 grams of semicarbazide hydrochloride and 6 grams of sodiumacetate in water, the semicarbazone was precipitated immediately.After being recrystallised twice from absolute alcohol, it melted a t152' without evolving gas FORSTER AND FIERZ: THE TRIAZO-GROUP.PART I. 830.1258 gave 58.7 C.C. of nitrogen a t 22' and 761 mm.C,H,ON, requires N = 53.84 per cent.The semicarbazone crystallises from water or alcohol in long,brilliant needles ; it effervesces with aqueous potash and, moreslowly, with concentrated sulphuric acid.This derivative has been prepared from several specimens of triazo-acetone, as it forms a convenient substance by which to identify theketobe, and on one occasion the latter remained in association withexcess of semicarbazide during several hours. The product in thiscase was quite distinct from the semicarbazone described above, beingvery sparingly soluble in common media, and precipitated by alkalifrom solution in acids.A specimen recrystallised from glacial aceticacid was therefore analysed, but the combustion presented considerabledifficulty, as the substance has no definite melting point, and decom-poses a t a high temperature, leaving carbon :0.1476 gave 0.1733 CO, and 0.0763 H,O. C = 32.02 ; H = 5-78.0.1300 ,, 50.3 C.C. of nitrogen a t 17' and 758 mm. N = 45.43.C,H,,O,N, requires C= 32.25 ; H = 5.38 ; N = 45.16 per cent.We believe therefore that this compound is the his-semicarbazoneN = 54.06.of methylglyoxal,CH,*C( :N*NH*CO*NH,)*CH:N*NH*CO*NH,,because me have found that, under certain conditions, hydroxylamine iscapable of transforming acetonylazoimide into methylglyoxime,CH,*C(:NOH)*CH:NOH ;the latter change indicates a disposition to undergo oxidation on thepart of the terminal carbon atom, recalling the behaviour of fructosetowards phenylhydrazine, but, so far as we know, the alteration inquestion has not previously been effected by semicarbazide.Triaxoncetozime, Ns*CH,*C(:NOH)*CH,.Five grams of triazoacetone were warmed to 50' with a solution ofhydroxylamine containing 4 grams of the hydrochloride in 80 C.C.ofwater, neutralised with 3.2 grams of anhydrous sodium carbonate ; theoil dissolved, and the solution suddenly became turbid. After twohours' agitation, the product was extracted with redistilled, purifiedether, and dried with sodium sulphate, the solvent being removed byexpoeing the liquid to a pressure of 2 mm. during four hours :0.0786 gave 33% C.C.of nitrogen at 18' and 745 mm.This experiment was made subsequently to an attempt to distil50 grams of triazoacetoxlme under 2 mm. pressure. On this occasion,about 25 grams boiled a t 84O, whilst the residue in the flask graduallyN=49.01,C,H60N, requires N = 49.1 2 per cent.a 84 FORSTER AND FIERZ: THE TRIAZO-GROUP. PART I.became dark brown, finally exploding with coiisiderable violence ; thedistillate was colourless, and had a faint odour of prussic acid, whichalone indicates decomposition, since the undistilled oxime is odourless,and, moreover, when analysed, furnished an amount of nitrogen 2 percent. below that required by the empirical ormula C,H,ON,. It isnoteworthy that bromoacetoxime also undergoes explosive decom-position when distilled.Triazoacetoxime is colourless, and does not solidify in the freezingmixture ; its behaviour towards concentrated sulphuric acid resemblesthat of triazoacetic acid and ester, liberation of nitrogen occurringonly after some delay, and on vigorous agitation.When treated with40 per cent. potash, nitrogen is liberated in considerable quantities, buthydrazoic acid is also produccd; if, however, more dilute alkali(20 per cent.) is employed without heating, all the nitrogen is eliminatedin the form of hydrazoic acid, along with a substance having theproperties of the oxime of acetol :N,*CH,*C(NOH)*CH, + H,O = HN, + HO*CH,*C(:NOH)*CH,,Before the unstable character of triazoacctoxime was appreciated, anattempt was made to prepare this compound by the action ofhydroxylamine sulphate instead of the free base.Twenty grams oftriazoacetone were suspended in 300 C.C. of water, and agitated with32 grams of hydroxylamine sulphate in 150 C.C. of water; the oildisappeared gradually but, the odour of hydrazoic acid becomingperceptible, the product was allowed to remain ten days in order tocomplete the change. The liquid was then extracted three times withether, and on removing the solvent, after drying with sodium sulphate,9 grams of a lustrous, crystalline solid separated from the oily residue ;on recrystallising this product from hot benzene, of which 200 C.C.were required by 1 gram, it was found t o be methylglyoxirne, andwas obtained in minute needles, melting at 157" without evolvinggas :0.1189 gave 35.4 C.C.of nitrogen at 18' and 756 mm.C,H,O,N, requires N = 27.45 per cent.The production of methylglyoxime and the bis-semicctrbazone ofmethylglyoxal by the action of hydroxylamine and semi-carbazide respectively on triazoacetone, is an interesting case of thattype of oxidation which leads to the formation of osazones. A similarobservation has been made in connexion with chloroacetoxime byHantzsch and Wild (Annalen, 1896, 289, 285) and Scholl andMatthaiopouIos (Ber., 1896,29, 1550), methylglyoxime being obtainedwhen excess of hydroxylamine acts on the substituted ketoxime. It isprobable, also, that the same change occurs when hydroxylamine actson hydroxyacetone, because Kling (Ann. Chirn. Phys., 1905, [viii], 5,N = 27.74VELOClTY OF FORMATION OF ACETOXIME. 85482), who performed the experiment, recorda the production of acompound melting at 153O, and an analysis which furnished 26.6 percent. of nitrogen ; Kling suggests the constitutional formula,CH,*C( :NOH)*CH,*N€€*OH,but, as there is no evidence for this view, it seems to us more probablethat he had in hand an imperfectly purified specimen of methyl-glyoxime.Z’he p-Yohenesulphonic Berivutive.-The oxime being a n oil, it witsconsidered desirable to characterise the substance further by preparinga crystalline derivative. Triazoacetoxime dissolved in pyridine wasaccordingly treated with p-toluenesulphonic chloride ; the oil whichseparated on dilution with water quickly solidified, and was re-crystallised from boiling light petroleum, in which the substancedissolves sparingly, 1 gram requiring about 100 c.c., from whichit crystallises in large, lustrous, striated plates, melting a t 7 3 O :0.1090 gave 20.2 C.C. of nitrogen at 23’ and 757 mm. N = 21.29.C,,H,,O,N,S requires N = 20.90 per cent.The substance, although snow-white when freshly crystallised,rapidly deteriorates, becoming brownin a few days. Thrown on ahot plate, i t detonates, and burns with a, brilliant flame ; it ismoderately soluble in cold methyl or ethyl alcohol, disso1viDg freely inchloroform, benzene, or ethyl acetate.ROYAL COLLEQE OF SCIENCE, LONDON.SOUTH KENSINGTON, S. W

ISSN:0368-1645    

DOI:10.1039/CT9089300072

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年代:1908

数据来源: RSC

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VELOClTY OF FORMATION OF ACETOXIME. 85IX.-The InJEuence of Acids and Alkalis O ~ L theVelocity o f Formation o f Acetoxime.By ERNEST BARRETT and ARTHUR LAPWORTH.IN a paper which appeared in the July number of this Journal(Trans., 1907, 91, 1133), it was shown by one of us that acidsaccelerate oxime formation, and that certain oximes are formed withgreat ease even in presence of concentrated hydrochloric acid. At theconclusion of the paper, a subsequent communication on measure-ments of the velocity of reaction between hydroxylamine and acetoneand aldehyde in presence of both bases and acids was promised. Themeasurements referred to had been made some time before the firstpaper was submitted to the Society ; the work had been going on forsome eighteen months, and the further investigation vas in progress.I n the September number of the Amel-ican Chemical Joumal, 86 BARRETT AND LAPWORTH: THE INFLUENCE OF AClDS ANDpaper by Acree and Johnson appeared (Amer.Chenz,. J., 1907, 38,258), which dealt with many chapters of catalysis, and includedmeasurements on the equilibrium point of the reversible reactionbetween acetaldoxime, acetone, and hydroxylamine hydrochloride, thevelocity of hydrolysis of acetoxime with hydrochloric acid, and thevelocity of formation of acetoxime from acetone and free hydroxyl-amine (Zoc. cit., p. 308 et 8eq.).Towards the end of November, Prof. Acree wrote stating that hehad only recently seen Lapworth's paper for the first time, and drewour attention to his work with Johnson, expressing the hope that wemight see our way to abandon the investigation to him, In thecircumstances, we have decided to submit to the Society a brief accountof the more important observations we had made before last July,when the first communication of the proposed series appeared, and theobservations me select are those which appear to add something to thediscoveries of Acree and Johnson and other workers, but they do notsolve the question of the mechanism of the reaction.On the otherhand, we have agreed to abandon the further study of the velocity offormation and hydrolysis of oximes, at least for the present, in favourof the American authors.The work was begun some two years ago, after hearing fromStewart, the last worker on the velocity of oxime formation (Trans,,1905, 87, 410)) that he did not propose to extend his researches inthis direction.The measurements were made much in the mannerdescribed by Stewart, but were carried out at 0' with solutions inwhich the concentrations of acetone and hydroxylamine were 3/40 innearly all cases. Instead of sodium phosphate, sodium acetate wasused during the titrations, for it was desired to study the formationof aldoximes, in which case sodium phosphate was found to be useless.I n brief, our results supplement those of other workers in thefollowing points. The acceleration of oxime formation by alkalis,first noticed by Auwers (Ber., 1889, 22, 605), we find to be veryconsiderable and nearly proportional to the concentration of alkali.The acceleration of the reaction between hydroxylamine and acetoneby hydrochloric acid is rather less marked at first, but risea withincreasing proportions of acid very rapidly to a maximum, in whichthere is little or no suggestion of lag, to a point where there ispresent about 0.6 to 0.6 equivalent of acid, the velocity here beingmore than fifty times as great as with free hydroxylamine alone.It then falls almost as rapidly to the point where there is presentrather more than one equivalent of hydrochloric acid, after which thevariation of velocity with amount of acid present is small (seediagram, p.92).With acetaldehyde, more dificulty mas experienced in estimatinALKALIS ON THE VELOCITY OF FORMATION OF ACETOXIME. 87the greater velocity of reaction, and much higher dilutions werenecessary.The curve obtained on plotting our preliminary resultswas much like that for acetone, but the point of maximum velocitywas reached with a somewhat larger proportion of acid.The acceleration of oxime formation by addition of alkali, and theapproximate proportionality of the velocity to the concentration ofalkali present, suggests at once that the hydroxylamine behaves aa aweak acid and reacts with the carbonyl compound in much the samemanner as does hydrocyanic acid (compare Trans., 1903, 83, 99’7;1904, 85, 1214 and 1355, &c.),Thus, to take the simplest possible ionic view, the hydroxylaminemay be supposed to yield the ions H* and *NH*OH, the latter ofwhich, as a weak ion, forms a complex with the carbonyl compound :R2C = 0 + *NH*OH f+ R2C<NH.0H,+ -- 0-this complex ion formation being relatively very slow.The idea that ammonia in analogous cases reacts as an acid andin the parts H and NH, or NH,*OH has been suggested by Knorr(Bey., 1899, 32, 731), and revived in a slightly different form byLowry (British Assoc.Report, 1904,The question of the mechanism of the acceleration of oxirne formationby acids is certainly much less straightforward. From the fact thatan equilibrium is attained when acids act on acetoxime, Acree andJohnson conclude that the reaction involves the union of the hydroxyl-ammonium ion with the ketone as neutral constituent :+Dynamic Isomerism,” p. 11).+ +(CH,),CO + NH,*OH -+ (CH,),CO*NH,*OH.This is highly improbable; firstly, because of the already highelectro-affinity of the hydroxylammonium ion, and secondly, becauseall the evidence hitherto goes t o show that only negative groups becomeattached to the carbon atom of the carbonyl group.A more likely suggestion is that the hydroxylammonium ion is notdirectly concerned, but that the acetone forms complex ions withhydrogen ions which are present as the result of hydrolysis of thehydroxylamine salt : + 4 OH(CH3),C0 + 11.+-+ (CH,),C<+(the oxonium ion (CH,)2C:O<H being possibly formed at an inter-mediate step), and this positive ion then attacks the free hydroxyl-amine, forming a substituted hydroxylammouium ion 88 BARRETT AND LAPWORTH: THE INELUENCE OF ACIDS ANDAcree and john son'^ view would predict a regular rise in thevelocity from the state where free hydroxylamine is present to thatwhere there is one equivalent of acid, and after this a regular, butvery slight, fall.On the view now suggested, addition of acid to free hydroxylaminewould at first produce little effect, and afterwards a rapidly increasingacceleration for a time, leading to a curve at first distinctly conmvetowards the line A in the diagram, and near and beyond the pointwhere an equivalent of acid is present a maximum followed by a slightdecreasing velocity as with Acree and Johnson's proposition.It is not worth while at present to enlarge on these views.Neitherexplains the curious variation of the velocity between the points Aand B on the diagram.It seems hardly possible that this can beelucidated by any view as to the mechanism of oxime formation fromhydroxylamine and acetone. A supposition which would lead to acurve attaining a maximum value between these points would be oneassuming that the measured change involved the interaction of freehydroxylamine, hydroxylammonium ions, and acetone, but this would beroughly of the form y =.(a - x), and would show a rapid rise near A , aslow change near the maximum, and an increasingly rapid fall to B.The curve rather appears to suggest that its form may be due to apeculiarity either of acetone or of hydroxylamine itself. Is itpossible, for example, that hydroxylamine gives a salt, (NH,*OH),,HCl,yielding a basg, (NH,*OH),, by hydrolysis, and transformed byexcess of hydrochloric acid into NH,*OH,HCl 0 The tendency of theoxygenated derivatives of ammonia to form more complex aggregatesmay be recalled, and a salt of the formula quoted is known to beproduced readily enough in the solid form, but whether this exists toany large extent as such, or as its ions, in aqueous solution, does notappear to be known.A fact which seems to militate against suchan explanation is that the condition for maximum velocity withacetaldehyde does not appear to coincide with that with acetone, thepoint lying somewhat nearerethe line B.EXPERIMENTAL.In the following series of experiments with acetone, the initialconcentrations of hydroxylamine and acetone were, in all cases, N/40.The solutions in which the reaction was studied were prepared bymixing equal volumes of N/10 solution of acetone and hydroxylaminehydrochloride to the latter of which had previously bean added vary-ing quantities of sodium hydroxide or hydrochloric acid, it being soarranged that immediately after admixture there should be exactly1 gram-molecule each of ketone and total hydroxylamine per 40 litresOF solution, and all operations were ci-trried out a t 0'ALKALIS ON THE VEL~CITY OF FORMATION OF ACETOXIME. 89In the tables given, the amounts of hydrochloric acid or sodiumhydroxide present are also stated in gram-molecules per 40 litres, andit is to be understood that the stated amount of hydrochloric acid ineach case includes both the free acid and that combined with thehydroxylamine; similarly, in experiments I1 to IV, the amount ofsodium hydroxide given refers to the excess of the latter used overthat required to convert all the hydroxylamine present into free base.In the majority of the experiments, therefore, sodium chloride wasnecessarily present, but we have found that the effect of this salt washardly perceptible, and did not produce any effect on the velocity ofreaction sufficient to alter in any way the general conclusions towhich the investigation lends.After many preliminary trials, the method adopted for estimatingthe amount of oxime formed was to determine the quantity ofhydroxylamine which remained by oxidising it with excess of standardiodine solution as other workers have done, but having found that inalkaline media, such as sodium phosphate or bicarbonate, concordantresults could not be obtained in presence of aldehydes, we were finallyled to carry out the titrations in presence of sodium acetate.Thissalt, if highly purified, serves a similar purpose, and in its presencehydroxylamine may be determined with a very fair degree ofaccuracy, providing that much free acid is not present with thehy drox y lamine.In each case, the time which elapsed between the moment ofadmixture and that of withdrawing an aliquot portion of the solutionfor titration is given in minutes. The number indicating the amountof oxime formed represents the number of gram-molecules presentper 4000 litres, the maximum possible at the end point being, ofcourse, equal to 100, and was arrived at by subtracting the quantityof hydroxylamine unchanged in 40 litres from 100.The last numberin each case represents the quantity of oxime formed at the endpoint.I. No acid or alkali present (that is, the solution was preparedso as to contain 1 gram-molecule each of hydroxylamine, hydro-chlcride, and acetone per 40 litres, the free base being liberated byaddition of 1 gram-molecule of sodium hydroxide per 40 litres) :t= 2 5 10 20 30 -Oxime Somed= 5-8 17'0 29'2 43.7 52.9 99'5SERIES l.--In Presence of Alkali.11. 0.20 gram-molecule of free sodium hydroxide present. Inexperiments I1 to IV a quantity of acid sutlicient to neutralise th90alkali present was added to the sodium acetate before the titration ofhydroxylamine :BARRETT AND LAPWOKl'H: THE INFLUENCE OF ACIDS ANDt = 2 5 10 21 36Oxime formed= 33.9 52-2 69'6 83 '0 89.3111. 0.25 gram-molecule of sodium hydroxide present :t = 2 5 10 20 -Oxime formed= 49.5 68.3 81.6 90.9 98-8IV.1-00 gram-molecule of sodium hydroxide present :t= 1 2 5 10 20( a ) Oxime formed= - 64.3 82.7 92.3 97.1(6) ,, ,, = 51.4 66 -3 84.4 92'6 97.9SERIES 2.--In Presence of Acid.V, 0.066 gram-molecule of hydrogen chloride present :t= 3 5 10 20 30Oxime formed= 7.3 13.4 28.7 52'2 68.6VI. 0.25 gram-molecule of hydrogen chloride present :t= 2 5 10 20 30Oxime formed= 19.3 43.9 73.8 81.7 83-5VII. 0.30 gram-molecule of hydrogen chloride present :t= 1 2 5 10 15Oximeformed= 21.7 34.5 67'4 81'4 85 -0VIII.0.40 gram-molecule of hydrogen chloride present :t = 1 2 5 11 20Oxime formed= 19.1 38.0 64'7 72.6 77.6IX. 0.50 gram-molecule of hydrogen chloride present :t= 2 5 10 20 30Oxime formed= 49.8 54.5 65'2 68.9 70-4X. 0.60 gram-molecule of hydrogen chloride present :Oxime formed= 31'6 44.2 54.9 68.5 68'5 69'4XI. 0.75 gram-molecule of hydrogen chloride present :t.= 3 5 10 20 30Oxime formed= 31.3 46.5 50.4 58.7 61.1XII. 1 *00 gram-molecules of hydrogen chloride presentt= 1 2 5 18 25 36-99.5-10000-98.185.9-85 *8I77.6-71 *O-69.4-61 '9(that isto say, in this experiment, initially only acetone and hydroxylaminehydrochloride were present) :- t= 2 5 10 15 37Oxirne formed= 16.3 28.6 40'1 46.1 57 -1 60-ALKALIS ON THE VELOCITY OF FORMATlON OF ACETOXIME.91XILI. 1.50 gram-molecules of hydrogen chloride present ;t = 2 5 10 20 35 -Oxime formed= 3*6 7.7 21.5 32 -1 45'1 58.3XIV. 1 -5 12 gram-molecules of hydrogen chloride present :t = 1 2 5 10 25Oxime formed = 1 *6 4.7 12.6 23.5 32.7 58.3XV. 1064 gram-molecules of hydrogen chloride present :Oxime famed= 4 ' 1 13.4 18.5 28-0 35.3 55.0XVI. 2.024 gram-molecules of hydrogen chloride present :Oxime formed= 1.6 2.0 (2) 12.2 23.8 31-2 50.6-t = 2 5 10 20 30 -t = 1 2 5 11 25 -I n the last cited and in other experiments in which more than2 molecular proportions of acid were present, the disturbing influenceof the excess of acid on the titration of the hydroxylamine makesitself felt.I n all cases, the quantity of hydroxylamine found wasgreater than that really present, so that the amount of oxime calcu-lated on the same basis as in the preceding experiments appears lessthan is actually the case. Nevertheless, the results showed clearlyenough that., even when as much as 40 molecular proportions ofhydrogen chloride are present, oxime formation takes place withconsiderable velocity, and this does not appear to vary much withinvery wide limits. It had been our intention to examine thisregion, using sodium phosphate instead of acetate as the mediumduring titration.Fairly concordant numbers obtained on repeating a considerablenumber of the above experiments, indicate that the results may beregarded as correct within 2-3 units.We have also carried out experiments on similar lines, using acidsother than hydrochloric acid, but the results were without muchfurther significance.The most noteworthy points revealed by a glance a t the numbers inthe above tables are, first, that there is a minimum velocity at, or verynear, the point where only acetone and hydroxylamine are present(experiment I) ; secondly, that very large acceleration is caused bythe addition of alkalis or acids, the former having proportionately aconsiderably greater influence ; thirdly, that there is a maximumvelocity point between this point and that where the solution containsnothing but acetone and hydroxylamine hydrochloride.This is at aboutthe point attained in experiment JX,and, as will be seen, the amountof oxime formed here in two minutes is larger than in any other caseon the side where acid is present; fourthly, beyond this point rapi92 VELOCITY OF FORMATION OF ACETOXIME.fall in the velocity occurs, but even where an enormous excess of acidis present there is evidence that the velocity of oxime formationremains perhaps larger than when free hydroxylamine alone is present.Owing to the rapid change of the velocity with acidity (and thisvaries during each experiment), it is not possible to obtain velocityconstants, and the errors of time measurement in the first stages of theoxime formation render it difficult to obtain a value for the initialvelocity under any prescribed conditions. However, rememberingthat when much acid is present partial hydrolysis of the oximeoccurs, the reaction therefore being incomplete, a fair idea of therelative velocities with different canditions as to concentration of acidand alkali may be obtained by carefully plotting the results andascertaining the time required for the reaction to proceed half way t othe point a t which change ceases.It is clear, of course, that it wouldbe better to take points corresponding t o one-quarter, one-tenth, orless, but this leads to a magnification of other errors, and it maybe stated that the curves thus obtained are found to be very similar,showing precisely the some peculiarities.The following diagram exhibits the velocity of reaction estimated1.0 0-5Grammol. NaOH. Gmwi-mols.IFC1 per 40 Zitres.by taking the inverse of the time required for the reaction to proceedhalf-way towards completion. The vertical line at A correspondswith conditions when acetone and free hydroxylamine only are present ;to the left of this, alkali, and, to the right, acid is present. Thevertical line at B corresponds with the point where acetone andhydroxylamine hydrochloride only are presentCOLORIMETRIC METHOD FOR THE DETERMINATlON OF IRON. 93The velocities were found by ascertaining, graphically, the timerequired for the formation of one-half the amount of oxime preseut atequilibrium point, and the numbers given are one hundred times thereciprocals of these.The method of exhibiting the results, although rough, at leastaffords a general idea of some of the peculiarities in the formation ofacetoxime. It is difficult to state precisely the points or magnitudesof the maximum or minimum velocities, but greater or less deviationsthan those indicated have not been found in spite of repeated searchwith slightly varying conditions.It is noteworthy that the extension of the curve on the rightappears to be nearly horizontal beyond the limits shown; in otherwords, it seems that with excess of hydrochloric acid the velocityvaries only very slightly with the concentration.By varying either the amount of acetone or hydroxylamine whilekeeping the concentration of the other unaltered, me have ascertainedthat the velocity is nearly proportional to the concentration of each ofthese separately.The nature of the results we obtained in using acetaldehyde insteadof acetone have already been alluded to. We hesitate to give thedetails, because those experiments were of a preliminary character,and, owing to the much higher dilution necessary, eubject to errorswhich we hoped to be able to eliminate on repeating the measure-ments.Our thanks are due to the Research Fund Committee of theChemical Society for a grant, which helped to defray the cost of theinvestigation.GOLDSMITHS’ COLLEGE, NEW CROSS, S. E

ISSN:0368-1645    

DOI:10.1039/CT9089300085

出版商:RSC    

年代:1908

数据来源: RSC

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COLORIMETRIC METHOD FOR THE DETERMINATlON OF IRON. 93X.-A Coloiimetric Method foy the Determination ofSmall Percentages of I?;.on in Coppe,. Alloys.By ARNOLD WILLIAM GREGORY, B.Sc. (Lond.).IT is often n matter of considerable importance to be able to determineaccurately the amount of iron in copper alloys, on account of theeffect of this element on their physical properties. The gravimetricmethods are such that only by working with very large quantities ofmaterial can accurate results be obtained. Moreover, there is alwaysa danger OF iron being introduced into the solution of the alloy by theaddition of large quantities of reagents which may contain a trace o94 COLORIMETRIC METHOD FOR THE DETERMINATION OF IRON.that element, and from external sources during the lengthy method ofprocedure.The following method has been found to give extremely accurateresults ; it is simple in operation, and very rapid in execution.It isbased upon the colour reaction given by salicylic acid and ferricchloride. The violet coloration produced when salicylic acid is addedto ferric chloride, although affording a delicate test for iron underproperly chosen conditions, cannot be relied on for the quantitativedetermination of that element, since the colour is destroyed in thepresence of mineral acids and also by excess of alkalis.If, however, an excess of ti solution of sodium acetate be added to aferric salt, and then a solution of salicylic acid in acetic acid, a deepred colour is produced. Under these conditions, the depth of colouris proportional to the amount of iron present, and this method may beused for the estimation of small quantities of iron.I n the case of copper alloys, the blue or green colout.a€ the solutionentirely masks the red colour produced by the iron, This difllculty isovercome by the addition of a weak solution of potassium cyanide inquantity suficient for the formation of the colourless, complex cyanideof copper and potassium. The red colour is unchanged by this treat-ment. The exact method of procedure is as follows : 0.2 gram of thealloy is dissolved in a minimum quantity of strong nitric acid. If aprecipitate is produced, due to tin or antimony, the liquid is dilutedslightly and filtered,To this solution, 20 C.C. of a concentrated solution of sodium acetateare added, and 10 C.C.of a 2 per cent. solution of salicylic acid inglacial acetic acid. A 3 per cent. solution of potassium cyanide is nowadded gradually until the green colour of the solution has disappeared,and the precipitate of copper cyacide is re-dissolved. The solution,which is red if iron is present, is now made up t o a definite volume(depending on the intensity of the colour), and a measured amount istransferred to a Nessler comparison tube.Into a similar tube, 20 C.C. of sodium acetate solution and 10 C.C. ofthe salicylic acid solution are placed, and diluted to approximately thesame volume as the solution of the alloy. A standard solution offerric chloride is added drop by drop, with constant stirring, until thecolour produced is similar in intensity in the two tubes.From theamount of the standard solution used, the percentage of iron may becalculated.By this method, it is possible to detect as little as 0*00002 gram ofiron in the presence of 0.2 gram of copper.A strong solution of potassium cyanide must on no account be used,as this gives a coloured solution with pure copper salts, especially onwarming.Lead, if present, must be removed as sulphateDERIVATIVES OF TETRAMETHYL GLUCOSE. 95This test cannot be satisfactorily employed in the case of alloys con-taining considerable percentages of bismuth. Zinc and antimony,however, may be present without any appreciable error beingintroduced.Ex PE R I M ENT A L.A solution of pure copper sulphate was made, such that 1 C.C.wasequivalent to 0.02 gram of copper. Ten C.C. of this solution and3 C.C. of concentrated nitric acid were placed in each of seven beakers,and to all but the first of these varying amounts of a standardsolution of ferric chloride were added. The tests were then carriedout as described above, the solutions in each case being made up to100 C.C. Thesecond column shows the number of C.C. of ferric chloride solutionadded to the copper sulphate; the third gives the percentage of ironthat each quantity represents; the fourth gives the number of C.C.of ferric chloride required to produce the same colour as that obtainedin each of the test experiments, and the fifth shows the percentageof iron calculated from the volume of ferric chloride added :The results obtained are given in the following table.Number.1.2.3.4.5.6.7.C.C. ofFeC1, used.nil125101520Per cent, Fe.nil0.010 *020 -050.100.150.20C . C . ofFeCI, required.nil1'12.15.210.415.721 *oPer cent. Fenil0.0110.0210'0520.1040.1570'210APPLEBY IRON WORKS,FRODINGHAM

ISSN:0368-1645    

DOI:10.1039/CT9089300093

出版商:RSC    

年代:1908

数据来源: RSC