年代:1912 |
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Volume 101 issue 1
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Journal of the Chemical Society, Transactions,
Volume 101,
Issue 1,
1912,
Page 001-018
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J O U R N A LOFTHE CHEMICAL SOCIETY.TRANSACTIONS.H. BRERETOS BAKER, M.A., D.Sc.,HORACE T. BROWN, LL.D., F.R.S.J. N. COLLIE, Ph.D., F.R.S.A. W. CROSSLEY, D.Sc., Ph.D., F.R.S.F. G. DONNNANN, M.A., Ph.D., F.R.S.BERNAKD DYER, D.Sc.M. 0. FOESTER, D.Se., Ph.D., F.R.S.F. R. S.P. F. FRANKLAZTD, Ph.D., LL.D.,C. E. GROVES, F.R.S.A. MCKENZIE, M.A., D.Sc., PILD.J. C. PHILIP, D.Sc., Ph.D.A. SCOTT, MA., D.Sc., F.R.S.S. SMILES, D.Yc.F.R.S.Qbiior :J. C. GAIN, D.Sc., Ph.D.Snb - CbiiDax :A. 3. GBEENAWAY.1912. VoL CI. Part I.LONDON:GURNEY & JACKSON, 33, PATERNOSTER ROW, E.C.1912RICHABD CLAY & SONS, LIMITED,BRUNS WICK STREIGT, STAMFORD STREET, 4. E.,AND BUNOAY, SUFFOLKCONTENTS.PAPERS COMMUNICATED TO THE CHEMICAL SOCIETY.PAGEI.-Chemical Examination of the Root of Ipomoea orixabenais.By FREDERICK BELDINQ POWER and HAROLD ROQERSON .111.-The Influence of Neutral Solvents on Velocity of Reaction.Part I. Transformation of Anisspaldoxime in VariousSolvents. By THOMAS STEWART PATTERSON and HARVEYHUGH MONTaOMERIE, M. A., B.Sc. (Carnegie ResearchScholar) . . 26111.-The Velocity of Interaction of Iodic and Sulphurous Acidsin Various Media. By THOMAS STEWART PATTERSON andWILLIAM COLLINS FORSYTH . . 401V.-Diphenylcyclopentenone. By SIEGFRIED RUHEMANN andWILLIAM JOHNSON SMITH NAUNTON . . 42V.-The Porosity of Iron and its Relation to Passivity andCorrosion. By JOHN ALBERT NEWTON FRIEND, D.&. . . 50V1.-The Action of Aliphatic A mines on s-UibromosuccinicAcid.Part I. By EDWARD PERCY FRANKLAND and HENRYEDGAR SMITH . . 57VI1.-Complex Thio-oxalates. By CHARLES STANLEY .RoBrNsoNand HUMPHREY OWEN JONES . . 62V1II.-The Absorption Spectra of Quinine, Cupreine, 6-Methoxy-quinoline, and 6-Hydroxyquinoline. By JAMES JOHNSTONDOBBIE and JOHN JACOB Fox . . 77Part 11.By DAN TYRER . . . . 81By JOHN NORMAN PRIXG andDORIAN MACEFIELD FAIRLIE . . 91Part11. Solubility of Oxalic Acid in Other Acids. By JAMESIRVINE ORHE MASSON (1851 Scholar of the University ofMelbourne) . . 103XI1.-The Alcohols of the Hydroaromatic and Terpene Series.Part 11. The Menthols Corresponding with Optically In-active Menthone. By ROBERT HOWSON PICKARD andWILLIAM 0 s WALD LITTLEBURY . . 109XII1.-The Conductivity and Dissociation of DiacetyltartaricAcid. By STELLA DEAKIN and ALBERT CHEBBURP DAVIDRIVETT ., 1271X.-Latent Heats of Vaporisation of Mixed Liquids.X.-The Methane Equilibrium.XI.-The Solubility of Electrolytes in Aqueous Solutions.iv CON TENTS.X1V.-The Decomposition of Nitric Acid by Light. ByWILLIAM COLEBROOK REYNOLDS and WILLIAM HENRYTAYLOR ,XV.-Nitrites of the Alkylammonium Series. Part 11.Propylammonium Nitrite and Butylammonium Nitrite andtheir Decomposition by Heat. . By PRAFULLA CHANDRAR ~ Y and JITENDRA NATH RAHSHIT .XV I.-Amino-derivatives of Arylsulphonanilides and Aryl-sulphon-P-naphthalides. By GILBERT T. MORGAN andFRANCES M. G. MICKLETHWAIT .XVI1.-Electrolytic Reduction. Part V. Benzylidene Bases.By HERBERT DRAKE LAW .XViI1.-The Formation of Dichlorocarbamide and its BehaviourTowards Amines.By RasIg LAL DATTA .X1X.-The Transformation of Ammonium Cyanate into Carb-XX.-Copper Salts and their Behaviour with Alkalis. BySPENCER UMFREVILLE PICKERING, M.A., F.R.S. .XX1.-Molecular Rotatory Power in Normal HomologousSeries. Part I. Optically Active Derivatives of theHigher Aliphatic Alcohols and Acids. By THOMAS PERCYHILDITCH .XXII. Molecular Rotatory Power in Normal HomologousSeries. Part 11. The Menthyl Esters of the a-Bromo-aliphatic Acids. By HAROLD CHRISTOPHER and THOMASPERCY HILDITCH .XXI1I.-The Preparation of Conductivity Water. ByFERDINAND BERNARD THOLE .XXIV. -The Thio-analogues of Coumarin and its Derivatives.By ARTHUR CLAYTON and WILLIAM GODDENXXV.-Nitrites of the Alkylammonium Series.Part 111.Triethylammonium Nitrite arid its Decomposition and Sub-limation by Heat. By PRAFULLA CHANDRA RAY andJITENDRA NATH RAKSHIT .XXV1.-The Action of Ammonia on 6-Chloro-2-phenyl-l:3-benz-oxazine-4-0110. By ERNEST CHISLETT HUGHES and ARTHURWALSH TITHERLEY .XXVI1.-An Experimental Investigation of the BleachingProcess. By SYDNEY HERBERT HIQGINS .XXVIII.-1:2-Diketohydrindene. By WILLIAM HENRY PERKIN,jun., WALTER MORRELL ROBERTS, and ROBERT ROBINSON .XXIX .-The Esterification Constants of Some Substituted Aceticand Benzoic Acids. By JOHN JOSEPH SUDBOROUGH andMARGARET KATHLEEN '~'URNER .1amide. By FREDERICK DANIEL CHdTTAWAY ..PAGE1311411431541661701741922022072102162192222522 3CONTENTS.VPAGEXXX.-The Influence of Solvents on the Rotation of OpticallyActive Compounds. Part XVII. The Relationship betweenthe Chemical Constitution and the Influence of a Solvent.By THOMAS STEWART PATTERSON and ELIZABETH FINDLAYSTEVENSON, M.A., B.Sc., late Robert Donaldson Scholar ofGlasgow University .XXX1.-The Formation and Reactions of Imino-compounds.Part XVII. The Alkylation of Imino-compounds. ByJOCELYN FIELD THORPE .XXXI1.-isoNarcotine. By ERNEST GRIFFITHS JONES, WILLIAMHENRY PERKIN, jun., and ROBERT ROBINSON.XXXII1.-isooxyberberine. By NORMAN BLAND, WILLIAMHENRY PERKIN, jun., and ROBERT ROBINSONXXX1V.-The Relation between the Absorption Spectra ofMetallic Ions and their Valency. By CECIL REGINALDCRPMBLE (1 85 1 Exhibition Research Scholar)XXXV.-The Preparation and Properties of Sulphonic Esters.XXXVL-Menthyl Nitrilotriacetate.By PERCY FARADAYFRANKLAND and HUGH HENRY O'SULLIVAN .XXXVI1.-The Constituents of Commercial Chrysarobin. ByPRANK TUTIN and HUBERT WILLIAM BENTLEY CLEWER .XXXVIIL-The Aryl Ethers of Glycide, Glycerol, and Glycerol-a-monochlorohydrin. By ERNEST ROBERT MARLE .XXX1X.-The Direct Esterification of Saturated and Unsat-urated Acids. By EBENEZER REES THOMAS a.nd JOHN JOAEPHSUDBOROUGE .XL.-The Quantitative Estimation of Hydroxy-, Amino-, andImino-derivatives of Organic Compounds by means of theGrjgnard Reagent, and the Nature of the Changes takingplace in SoluZion. By HAROLD HIBBERT .XL1.-A Method for Determining the Relative Reactivity ofOrganic Compounds. By HAROLD HIBBERT..XLI1.-A New Method for the Separation of Tertiary fromSecondary and Primary Amines. By HAROLD HIBBERT andARCHIBALD WISE .XLII1.-The Viscosity of Aqueoiis Solutions of Sodium Palmitateand the Influence of Electrolytes on the Same. By FREDERICKDENNY FARROW .XL1V.-The Determination of Sulphur in Petroleum. ByJAMES MCCONNELL SANDERS. ,XLV.-The Absorption of the Halogens by Dry Slaked Lime.By WILLIAM ARTHUREGINALD WILKSXLV1.-The Methyl, Ethyl, and isoButyl Esters of Di-trichloro-acetyltartaric Acid, and the Existence of Minima in theirTemperature-rotation Curves. By THOMAS STEWARTPATTERSON and ALFRED DAVIDSON, B.Sc....By JOHN FERNS and ARTHUR TJAPWORTH ...24124926726226627328729030531 732834134434735836637 vi CONTENTS.XLVI1.-Perhalides of Diphenyliodinium Iodide.XLVIII.-Experiments on the Walden Inversion.By MARTINONSLOW FORSTER and JOHANNES HEINRICH SCHAEPPI .Part VIII.a-Amino-a-phenylpropionic Acids. By ALEX. MCKENZIEand GEORGE WILLIAM CLOUCIH .XLIX.-Chemical Examination of Scammony Root and ofScammony. By FREDERIC BELDING POWER and HAROLDROGERSON .L.-The Hydyolysis and Saponification of Esters of Saturatedand Unsaturated Acids. By THOMAS WILLIAMS and JOHNJOSEPH SUDBOROUGR .L1.-The Viscometric Determination of Transition Points. ByALBERT ERNEST DUNSTAN and HAROLD LANQTON .LI1.-Hydroxymethylphosphinic Acid and Some Homologues.By HAROLD JAMES PAGE .L1II.-An Exact Investigation of the Three Component System :Sodium Oxide-Acetic Anhydride- Water.By ALFREDCHARLES DUNNINUHAM .L1V.-Researches on Bleaching Powder. Part 11. The Actionof Dilute Acids on Bleaching Powder. By ROBERTLLEWELLYN TAYLOR and CLIFFORD BOSTOCK .LV.-The Influence of Three- and Four-membered CarbonRings on the Refractive and Dispersive Power of OrganicCompounds. By GUSTAF JIM OSTLING .MOISSAN MEMORIAL LECTURE. By Sir WILLIAM RAMSAY, K.C.B.,F.R.S. .LV1.-The Triazo-group. Part XX. Azoimides of the PropaneSeries. By MARTIN ONSLOW FORSTER and JOHN CHARLESWITHERS .LVI1.-The Action of Ozone on Cellulose. By MART CUNNING-HAM and CHARLES DOR~E .LVII1.-The Catalytic Action of Copper at 300" on SomeAlchohols of the Terpene Group.By GEORGE BALLINGALLNEAVE . .L1X.-Isomeric Change of Halogen-substituted Diacylanilidesinto Acylaminoketones. By ANDREA ANGEL .LX.-Asymmetric Quinquevalent Nitrogen Compounds of SimpleMolecular Constitution. By WILLIAM JACKSON POPE andJOHNREAD . .LX1.-The Synthesis of Glyoxaline Derivatives Allied to Pilo-LXI1.-The Constitution and Synthesis of Damascenine, theAlkaloid of NigeEZa damascena. By ARTHUR JAMES EWINS .LXII1.-Viscosity and Association. Part 11. 'She Viscosityof Geometrical Isomerides. By FERDINAND BERNARDTHOLE . .carpine. By FRANK LEE PYMAN . . .PAGE38239039841 241842343144445747 748949751351551953054456CONTENTS. viiPAGELXIV.4ubstituted koThiohydantoins. By AUGUSTUS EDWARDDIXON and JOHN TAYLOR ..LXV.-Syntheses of 3-0xy-( 1)-thionaphthen. By ARCHIBALDMORITZ HUTCHISON and SAMUEL SMILESLXV1.-Calcium Nitrate. Part I. The Two-componentSystem : Calcium Nitrate-Water. Part 11. The Three-component System : Cakium Nitrate-Nitric Acid-Water at25'. By HENRY BASSETT, jun., and HUGH STOTTAYLOR .LXV1I.-The Behaviour of Alloys when Heated in a Vacuum.By CLARENCE RICHARD GROVES and THOMAS TURNER .LXVII1.-Electro-reduction of A lkylnitrosoamides. By HILMARJOHANNES BACKER .LX1X.-The Reciprocal Influence of Unsaturated Centres andits Effect on the General Absorptive Power of Compounds.By ALEXANDER K ILLEN MACBETH, ALFRED WALTERSTEWART, and ROBERT WRIGHT .LXX.-Derivatives of pHydroxystilbene. By JOHN THEODOREHEWITT, WILLIAM LEWCOCK, and FRANK GEORGE POPE .LXX1.-Nitrites of the Alkylammonium Series.Part IV.isoButy1-, Diethyl-, Dipropyl-, and Tripropgl-ammoniumNitrites. By PRAFULLA CHANDRA RAY and JITENDRA NATHRAKSHIT .LXXII. --Nitrites of the Mercurialkyl- and Mercurialkylaryl-ammonium Series. By PRAFULLA CHANDRA RAY, JITENDRANATH RAKSHIT, and RASIK LAL DATTALXXII1.-Investigations on the Dependence of Rotatory Poweron Chemical Constitution. Part 11. The Rotations ofSome Secondary Alcohols containing the isoPropyl Group,By ROBERT HOW~ON PICEARD and JOSEPH KENYON...ANNUAL GENERAL MEETINQ .PRESIDENTIAL ADDRESS .OBITUARY NOTICES .LXX1V.-The Alkylation of the Ferro- and Ferri-cyanides. ByERNALD GEORGE JUSTINIAN HARTLEY .LXXV.-Some Reactions of P-Naphthasulphoniumquinone. ByHAROLD CHRISTOPHER and SAMUEL SMILES .LXX VI .-Asymmetric Quaternary Arsonium Compounds andtheir Attempted Resolution.By THOMAS FIELD WINMILL .LXXVI1.-The Four Stereoisomeric Optically Active 2:4-Di-m ethyltetrahy droquinolines.LXXVII1.-Some Mixed Phosphonium Derivatives. By WILLIAMJACKSON POPE and CHARLES STANLEY GIBSONLXX1X.- The Alkaloidal Salts of PhenylmethylphosphinicAcid. By WILLIAM JACKSON POPE and CHARLES STANLEYGIBSON . . .By JOHN THOMAEI ..5585705 7658559259960461261662063965468870571071872573574...v111 CONTENTS.LXXX.-The Optical Activity of Salts and Derivatives ofd-Camphor-P-sulphonic Acid. By JOSEPH IVON GRAHAM( 185 1 Exhi bition Research Scholar)LXXXI.-The Externally Compensated and Optically ActiveHydroxyhydrindamines, their Salts and Derivatives. ByWILLIAM JACKSON POPE and JOHN READLXXXI1.-Triketomethylenedioxyhydrindene. By SIEGFRIEDRUHEMANN .LXXXII1.-The Action of Chloral on Ethyl Tartrate and onEthyl Malate. By THOMAS STEWART PATTERSON and ANDREWMCMILLAN, M.A., D.Sc. .LXXX1V.-Purpurogallin. Part 11. By ARTHUR GEORGEPERKIN .LXXXV.-The Use of Phenolphthalein as an Indicator. TheSlow Rate of Neutralisation of Carbonic Acid. By JAMESWILLIAM MCBAIN .LXXXVL-The Absorption Spectra of Some Metallic Solutions.By SIR WALTER NOEL HARTLEY .LXXXVI1.-The Absorption Spectra of Permangauates. BySIR WALTER NOEL HARTLEY .LXXXVIIL-The Rate of Reduction of Carbon Dioxide byCarbon.By THOMAS FRED ERIC RHEAD and RICHARDVERNON WHEELER .1XXXIX.-The Combustion of Carbon. By THOMAS FREDERIC RHEAD and RICHARD VERNON WHEELER .XC.-The Chemistry of the Glutaconic Acids. Part 111.Glutaconic Acid and its P-AIkyl Derivatives. By NORMANBLAND and JOCELYN FIELD THORPEXC1.-The Chemistry of the Glutaconic Acids. Part IV. TheEsters of the Glixtacouic Acids. By NORMAN BLAND andJOCELYN FIELD THORPE .XCI1.-The Condensation of Ethyl Sodiomalonate with EthylCitraconate and the Synthesis of P-MethyltricarballylicAcid. By EDWARD HOPE .XCII1.-Quinone-Ammonium Derivatives. Part I. The Methyl-ation Products of Picramic and isoPicramic Acids. ByRAPHAEL MELDOLA and WILLIAM FRANCIS HOLLELY .XC1V.-Nickelo- and Pallndio-dithio-oxal ic Acids.By HUMPHREYOWEN JONES and CHARLES STANLEY ROBINSONXCV.-Dithiomalonates. By HUMPHREY OWEN JONES andCHARLES STANLEY ROBINSON .XCV1.-The Resolution of Benzoylalanine into its OpticallyActive Components. By WJLLIAM JACKSON POPE andCHARLES STANLEY GIBSON .XCVII. -Nor-hyoscyamine and Nor-atropine ; Alkaloids Occur-ring in Various Solanaceous Plants. By FRANCIS HOWARDCARR and % 7 ~ ~ ~ ~ ~ ~ COLEBROOK REYNOLDS .....PAGE74675878078880381 482082683184685687189291293293593994CONTENTS. isPAGEXCVIII. -The Monohalogen Derivatives of Acenaphthene. ByHOLLAND CROMPTON and MAGWE WALKER . . 958XCIX. -The Molecular Conductivities of Potassium Nitrite,Mercuric Nitrite, and Potassium Mercurinitrite. ByYRAFULLA CHANDRA HAY and NILRATAN DRAR .. 965C. -The Clilorination of Iodophenols. Part I. The Chlorina-tion of p-Iodophenol. By SIDNEY ALBERT BRAZIER, M.Sc.(Priestley Research Scholar of t h e University of Birming-ham), and HAMILTON MCCOMBIE . . 968C1.-Researches on the Constitution of Physostigmine. Part I.By ARTHUR HENRY SALWAY . . 978CII.-l:3-Keto-enolic Ethers and Derivatives of Dibenzoyl-methane. By ROBERT DUNCOMBE ABELL . . 989C1II.-Derivatives of Phenyl Styryl Ketone. Part I. TheTautomeric Forms of Dibenzoylmethane. By ROBERTDCNCOMBE ABELL . . 998C1V.-The Constitution of Aminotyrosine and the Action ofOxydases on Some Tyrosine Derivatives. By CASIMIRFUNK . 1004CV.-The Viscosity of Compounds Containing Tervalent Nitro-gen.Part I. The Amines. By ALBERT GEORGE MUSSELL,FERDJNASD BERNARD THOLE, and ALBERT ERNEST DUNBTAN . 1008CV1.-Electrolytic Reduction. Part VI. Unsaturated Alde-hydes and Ketones. By HERBERT DRAKE LAW . . 1016CVI1.-Aromatic Antimony Compounds. Part 111. SomePrimary Aryl Derivatives. By PERCY MAY . . 1033CVII1.-Aromatic Antimony Compounds. Part IV. Com-pounds of Antimony Trichloride with Diazonium Chlorides.By PERCY MAY . . 1037C1X.-Chemical Examination of the Bark of Evonym~satropurpureus. By HAROLD ROGEHSON . . 1040CX.-The Constituents of West Indian Satinwood. By SAMUELJAMES MANSON AULD and SAMUEL SHROWDER PICKLES . . 1052CX1.-Researches on Santalin. Part I. Santalin and itsDerivatives. By JOHN CANNELL CAIN and JOHN LIONELSIMONSEN .. 1061CX11.- Furan-2:5-dialdehyde. By WILLIAM FRANCIS COOPER,B.A. (Cantab.), and WALTER HAROLD NUTTALL, F.I.C. . 1074CXIIL-Studies on Platinocyanides. By LEONARD ANGELOLEVY, M.A. . . 1081CX1V.-The “Crude Fat” of Beta vulgaris. By ALLANNEVILLE . . 1101CXV.-Latent Heats of Vaporisation of Mixed Liquids. Part111. Mixtures of Associated with Non-associated Liquids.New Criteria for the Detection of Solvates in Mixtures ofLiquids. By DANIEL TYRER . . 110X CON TENTS.CXV1.-Azo-dyestuff s of the Triphenylmethane Group. ByARTHUR GEORGE GREEN and RAJENDRA NATH SEN . . 1113CXVI1.-Aniline-black aud Allied Compounds. Part 11. ByARTHUR GEORGE GREEN and ARTHUR EDMUND WOODHEAD . 11 17CXVII1.-The Rotatory Powers of the cl- and Z-Methylethyl-phenacylthetine Salts.By CLARA MILLICENTAYLOR . 11 24CX1X.-The Conversion of d-Glucosamine into cl-Glucose. ByJAMES COLQUHOUN IRVINE and ALEXANDER HYND, M.A.,B.Sc. (Caruegie Fellow) . . 1128CXX.-The Two Sulphides of &Naphthol. By CECIL REGINALDCRYMBLE, KENNETH Ross, and SAMUEL SMILES . . 1146CXXT. -The Oxidation of Atmospheric Nitrogen in Presence ofCXXI1.-The Mechanism of the Racemisation of Some Hydroxy-acids by Heat. By DAN IVOR JAMES and HUMPHREY OWENJONES . . 1158CXXIII. -The Dynamic Isomerism of Ammonium Thiocyanateand Thiocarhmide. By WILLIAM RINGROSE GELSTONATKINS and EMIL ALPHONSE WERNER . . . . 1167CXX1V.-Properties of Mixtures of Ally1 Alcohol and Water.Part I. By THOMAS ARTHUR WALLACE and WILLIAMRINGROSE GELSTON ATKINS .. 1179CXXV.-The Vapour Density of Ammonium Nitrih. ByPRAFULLA CHANDRA RAY, NILRATAN DHAR, and TINCOWRYDE . . 1185CXXV1.-A Modification of the Beckmann Apparatus. ByEDMUND KNECHT and JOHN PERCY BATEY . . 1189CXXVI1.-The Action of. Sodium Methoxide on 2:3:4:5-Tetrachloropyridine. Part I. By WILLIAM JAMES SELL . 1193CXXVIIL-Configuration of the Stereoisomeric DibromosuccinicCXX1X.--N-Chloro-derivatives of Benzylidene-diamides. ByFREDERICK DANIEL UHATTAWAY and ALAN EDULF SWINTON 1206CXXX.-The Absorption Spectra of Certain Aromatic Nitro-arnines and Nitroamides. By GILBERT T. MORGAN, EDGARJOBLING, B.Sc., and RAYMOND T. F. BARNETT, B.Sc.CXXX1.-The Exhaustive Alkylation of Tetrahydroberberine.By JAMES WALLACE MCDAVID, WILLIAM HENRY PERKIN,CXXXI1.-The Formation and Hydrolysis of Esters of KetonicCXXXIIL-Some Hydroxy-ketonic Dyes.By JATINDRA MOHANCXXXIV. -The Spectroscopic Investigation of the Carbinol-Benziminazole and isoQuino-PAGEOzone. By THOMAS MARTIN LOWRY . . 1152Acids. By ALEX. MCKENZIE . . 1196. . 1209jun., and ROBERT ROBINSON . . 1218Acids. By JOHN JOSEPH SUDBOROUQH . . 1227DUTTA and EDWIN ROY WATSON . . 1238Ammoniuru Base Isomerism.line Derivatives. By CHARLES KENNETH TINKLER . . 124CONTENTS. x iHippuric Acid. By PAUL HAAS . . 1354PAGE:CXXXV.--a-Hydroxyhippuric Acid and a New Test forCXXXVL-Tbe Refractivity of Sulphur in Various AliphaticCompounds. By THOMAS SLATER PRICE and DOUGLASFBANK TWISS . . 1259CXXXVI1.-Morphotropic Relationships between Racemic Com-pounds aud their Optically Active Components.By GEORGEJERUSALEM . 1268CXXXVIIL-The Velocity of the Hydrogen Ion, and aGeneral Dissociation Formula for Acids. By JAMESEENDALL, M. A., B. Sc. (Vans Dunlop Scholar in Chemistry,University of Edinburgh) . . 1275CXXX1X.-Some Derivatives of Oxazole. By JOSEPH LISTERand ROBERT ROBIKYON . . 1297CXL.-The Absorption Spectra of Various Derivatives ofNaphthalene in Solution and as Vapours. By JOHNEDWARD PURVIS . . 1315CXL1.-Studies in the Camphane Series. Part XXXI. Con-densation of Camphorquinone with Nitromethane, EbhylCyanoacetate, and Phenylacetonitrile. By MARTIN ONSLOWFORSTER and JOHN CHARLES WITHERH . . 1327OXLI1.-Studies in the Camphane Series. Part XXXII. Stereo-isomeric Modifications of isoNitrosoepicamphor, the Thirdand Fourth Monoximes of Camphorquinone. By MARTINONSLOW FORSTER and HANS SPINNER .. 1340CXLII1.-The Triazo-group. Part XSI. Benzenoid AzoimidesContaining Multivalent Iodine. By MARTIN ONSLOWFORSTER and JOHANNES HEINRICH SCHAEPPI . L 1359CXL1V.-Tho Formation of Neon as a Product of RadioactiveChange. By Sir WILLIAM RAMSAY, K.C.B., F.R.S. . . 1367CXLV.-An Analysis of the Waters of the Thermal Springs ofBath. By IRVINE MASSON, M. Sc , and SIR WILLIAM RAMSAY,K.C.B., F.K.S. . 0 . . 1370CXLV1.-The Constitution of the Aldol Bases. By MURIELGWENDOLEN EDWARDS, RALPH EDDOWES GARROD, andHUMPHREY OWEN JONES . . 1376CXLVII. -Some Quinoline and Tetrahydroquinoline Derivativesobtained from Aldol Bases, By RALPH EDDOWES GARROD,HUMPHREY OWEN JONES, and PERCY EDWIN EVANS .. 1389Part I.Starch, Saponarin, and Cholalic Acid. Ey GEORGE BAWERand ELLEN FIELD . . 1394CXL1X.-The Viscosity of Ether-Alcohol Mixtures. By FRANKBAKER . . 1409CL.-Contributions to the Chemistry of the Terpenes. PartXIII. The Preparation of Pure Boruylene. By GEORGEGERALD HENDERSON and WILLIAM CAW . . 1416CXLVII1.- Blue Adsorption Compounds of Iodinexii CONTENTS.CL1.-The Interaction of Bromine with the Two Sulphides ofP-Naphthol. By THOMAS JOSEPH NOLAW and SAMUELSMILES . . 1420CLI1.-Investigations on the Dependence of Rotatory Power onChemical Constitution. Part 111. The Rotations of ac-Tetrahydro-2-naphthol and Some of its Esters. By ROBERTHOWSON PICKARD and JOSEPH KENYON .. 1427CLII1.-The Essential Oil of the ‘‘ Nepal Sassafras ” or ‘‘ NepalCL1V.-The Continuous Fractional Distillation of Water. By . 1443CLV.-Pyrogenic Decompositions. Part I. Benzene. ByCLARENCE SMITH and WILLIAM LEWCOCK . . 1453CLV1.-The Influence of Colloids and Fine Suspensions on theSolubility of Gases in Water. Part 11. Solubility ofCarbon Dioxide and of Hydrogen. By ALEXANDER FINDLAYCLVII.-A Theory of Fluorescence. By EDWARD CHARLES CYRILBALY and RUDOLF KRULLA. . 1469CLVIIL-Chemical Reactivity and Absorption Spectra. Part I.By EDWARD CHARLES CYRIL BALY and FHANCIS OWEN RICE. 1475CL1X.-Contributions to our Knowledge of Semicarbazones.Part I. Semicarbazones of Phenyl Styryl Ketone. ByISIDOR MORRIS HEILBRON and FORSYTII JAMES WILSON.. 1482CLX.-The Chemistry of the Aconitic Acids. Part I. TheLabile Modification of Aconitic Acid and the Hydroxy-anhydro-acid. By NORMAN BLAND and JOCELYN FIELDTHORPE . . 1490CLX1.-Substituted Thiolazo-derivatives of Benzene. By JOHNJACOB Fox and FRANK GEORGE POPE . . 1498CLXI1.-The Conditions of lsodynamic Change in the AliphaticKetones. Part I. The Autocatalytic Reaction betweenAcetone and Iodine. By HARRY MEDFORTH DAWSON andFRANK POWIS, MSc. . . 1503CLXIIL-The Absorption Spectra of Some Substances Con-taining Two Benzene Nuclei. BY JOHN EDWARD PURVISand NIAL PATRICK MCCLELAND . . 1514Part 1.The Action of Hydroxylamine and of Phenylhydrazine onC-Acetyldimethpl- and C-Acetyltrimethyl-dihydroresgrcins.By ARTHUR WILLIAM CROSSLEY and NORA RENOUF (Salters’Fellow) .. 1624CLXV.-The Colouring Matters of the Flowers of the Ced~eZatoona. By ARTHUR GEORGE PERKIN . . 1538CLXV1.-Electrolytic Reduction. Part VII. The CatalyticPAGECamphor ” Tree. By SAMUEL SHROWDER PICKLES . . 1433WILLIAM ROBERT BOUSFIELD, M. A., K.C. .and BUCCHOK SHEN, M.Sc., A.I.C. . . 1459CLX1V.-Acyl Derivatives of the Dihydroresorcins.Action of Copper. By HERBERT DRAKE LAW . . 154... CONTENTS. X l l lPAGECLXVI1.-Nitrites of the Mercurirtlkyl- and Mercurial kyl-aryl-ammonium Series. Part 11. By PRAFULLA CHANDRARPY, NILRATAN DHAR, and TINCOWRY DE . . 1552Part V.The Preparation of Esters of the Labile Acids. ByNORMAK BLAND and JOCELYN FIELD TEORPE . . 1557CLX1X.-Studies on Certain Aliphatic Hydroxy-acids.ByHENRY JOHN HORSTMAN FENTON and WILLIAM ARTHURREGINALD WILKS . . 1570CLXX.-4-Alkyl-1:4-thiazans. BY HAKS THACHER CLARKE (1851Exhibition Scholar) . . 1583CLXX1.-p-Hydroxy-up-dimethyladipic Acid and P-Hydroxy-a$?-trimethyladipic Acid. By VICTOR JOHN HARDING . 1590CLXXI1.-isoQuinoline Derivatives. Part VII The Prepa ra-tion of Hydrastinine from Cotarnine. By FRANK LEEPYMAN and FREDERIC GEORGE PERCY REMFRY . , 1595CLXXIII. --Nitrites of Primary, Secondary, and Tertiary Bases.BY PANCHXNAN NEOGI, M.A. . - 1608CLXX1V.-The Essential Oil of the Leaves of Atherospemaamoschatum (" Australian Sassafras "). By MARGARET E.SCOTT . . 1612CLXXV.-Alkaline Cupri-compounds. By SPENCER UMFREVILLEPICKERINQ, M. A., F.R.S. . .1614CLXXV1.-The Colour Intensity of Copper Salts. By SPENCERUMFREVILLE PICKERISG, M.A., F. R.S. . 1625CLXXVI1.-The State of Amines in Aqueous Solution. ByTOM SIDNEY MOORE and THOMAS FIELD WINMILL . . 1635CANNIZZARO MEMORIAL LECTURE. By SIR WILLIAM A. TILDEN,D.Sc. , LL.D., F.R.S., Past-President of the ChemicalSociety . . . . 1677CLXXVII1.-The Action of Sulphur on Amines. Part I.o-Toluidine. By HERBERT HENRY HODGSON, M.A., B.Sc.,3Ph.D. . . 1693CLXX1X.-The Resolution of sec.-Bu t,ylamine into OpticallyActive Components. By WILLIAM JACKSON POPE andCHARLES STANLEY GIBSON . . 1702CLXXX.-Hydrolysis of Acetic Anhydride. By KENNEDYJOSEPH YREVIT~ ORTON and MARIAN JONES, B.Sc. (ResearchStudent of the University of Wales) . . 1708CLXXXL-Acetic Anhydride : The Pure Material, its PhysicalProperties, and its Reaction with Bromine.By I~ENNEDYJOSEPH PREVIT~ ORTON and MARIAN JONES . . 1720CLXXXI I.-The Action of Aliphatic Amines on s-Dibromo-succinic Acid. Part T I . Allylamine. By EDWARD PERCYFRANKLAND and HENRY EDGAR SMITH . . 1724CLXXXII1.-Studies on Cyclic Ketones. Part I. By SIEGFRIEDEUHEMANN . . 1739CLXVII1.-The Chemistry of the Glutaconic Acidsxiv CONTENTS.PAGECLXXX1V.--The Chemistry of the Glutaconic Acids. PartVI. Conditions which Confer Stability on the trans-Formsof the Labile Acids. By NORMAN BLAND and JOCELYNFIELD THORPE . . 1739CLXXXV.-The Configuration of Substituted Ammonium Com-pounds. By HUMPHRES OWEN JONES and JOHN GUNNINGMOORE DUNLOP . . 1748CLXXXV1.-The Action of Sodium Hypobromite on CarbamideDerivatives. Part I.By FRANK WILLIAM LINCH . . 1755CLXXXVII.-3-Aminocoumarin. By F’BANK WILLIAM LINCH . 1758CLXXXVII1.--Derivatives of o-Hydroxyazobenzene. By JOHNTHEODORE HEWITT and WILLIAM HENRY RATCLIFPE . . 1765CLXXX1X.-The Absorption Spectra of Nitro-compounds. ByJOHN THEOBORE HEWITT, FRANK GEORGE POPE, and WINIPREDISABEL WILLETT . . 1770CXC.-Harmine and Harmaline. Part I. By WILLIAM HENRYCXC1.-The Relation between Residual AfX nity and ChemicalConstitution. Part 111. Some Heterocyclic Compohds.By HANS THACHER CLARKE (1851 Exhibition Scholar) .CXCII. -The Absorption Spectra of Simple Aliphatic Sub-stances in Solutions, Vapours, and thin Films. Part I.Saturated Aldehydes and Ketones, By JOHN EDWARDPURVIS and NIAL PATRIOK MCCLELAND .. 18102 : 4- and 2 : 6-Dibromo-phenol. By FRANK GEORGE POPE and ARTHUR SAMUELW O O D . 1823ANNUAL REPORT OF THE INTERNATIONAL COMMITTEE ON ATOMICWEIQHTS, 19-13 . . 1829CXC1V.-The Influence of Solvents on the Rotation of OpticallyActive Compounds. Part SVILT. The Effect of In-organic Salts on the Rotation of Ethyl Tartrate in AqueousSolution and in the Homogeneous Condition. By THOMASSTEWART PATTERSON and DUNCAN GEDDES ~NDERSON, B.Sc. . 1833CXCV.-Studies in the Azine Series. Part 11. By EATHLEEKBALLS, JOHN THEODORE HEWITT, and SIDNEY HERBERTNEWMAN . . 1840CXCVL-The Action of Halogens on Silver Salts and onPotassium Cyanate in Presence of Water, with a Noteon the Decomposition of Cyanic Acid in Aqueous Solution.By CHARLE~ WILLIAM BLYTH NORMAND and ALEXANDERCHARLES CUMMING .. 1852CXCVIL-The Refraction and Dispersion of Trirtzo-compounds.Part 11. By JAMES CEARLES PHILIP . . 1866CXCVI1I.-The Action of Acyl Chlorides on Primary Amides.By ARTHUR WALSH TITHEBLEY and THOMAS HALSTEADHOLDEN . . 1871PERKIN, jun., and ROBERT ROBINSON . . 1775. 1788CXCII1.-The Bromination of PhenolCONTENTS. xvPAGECXCIX.-The Action of Benzotrichloride on Primary Amides.By ARTHUR WALSH TITHERLEY and THOMAS HALSTEADHOLDEN . . 1881CC.-Carbon Disulphide as Solvent for the Determination of the‘‘ Refraction Constant.” By PR~D~RIC SCHWER~ . . . 1889CC1.-Studies of Dynamic Isomerism. Part XIII. Camphor-carboxylamide and Camphorcarboxypiperidide. An Illus-tration of Barlow and Pope’s Hypothesis.By WALTERHAYIS GLOVER and TEOMAS MARTIN LOWRY . . 1902CCI1.-Some New Diazoamino- and o-Aminoazo-compounds. ByGEORGE MARSHALL NORMAN . . 1913CCII1.-The Molecular Condition of Some Organic AmmoniumSalts in Bromoform. By WILLIAM ERNEST STEPHEN TURNER 1923CCIV. -The Preparation of Glycogen and Yeast-gum fromYeast. By ARTHUR HARDEN and WILLIAM JOHN YOUNG . 1928CCV.-The Rate of Reaction of Alkyl Haloids with CertainTertiary Bases. By RICHARD WILLIAM DADES PRESTON andHUMPHREY OWEN JONES . . 1930C‘CV1.-The Action of Sodium Rlethoxide on 2 : 3 : 4 : 5-Tetra-CCVIL-Studies in Phototropy and Thermotropy. Part 111.Arylideneamines. By ALFRED SENIER, FREDERICK GEORGESHEPHEARD, and ROSALIND CLARKE .. 1950CCVII1.-Properties of Mixtures of Ally1 Alcohol, Water, andBenzene. Part 11. By THOMAS ARTHUR WALLACE andWILLIAM RTNGRO~E GELSTON ATEINS. . 1958CC1X.-The Migration of the para-Halogen Atom in Phenols.By PHILIP WILFRED ROBERTSON and HENRY VINCENT AIRDBRISCOE . . 1964CCX.-The Constitution of Camphene. Part I. The Structureof Camphenic Acid. By WALTER NORMAN HAWORTH andALBERT THEODORE KINU . . 1976CCX1.-The Influence of Certain Salts on t h e Dynamic Isomerismof Ammonium Thiocyanate and Thiocarbarnide. By WILLIAMRINGROSE GELSTON ATHINS and EMIL ALPHONSE WERNER , 1982CCXI1.-The Condensation of a-Keto-p-anilino-up-diphenyl-ethane and its Hornologues with Ethyl Chlorocarbonateand Thionyl Chloride. By HAMILTON MCCOMBIE and JOHNWILFRID PARKES . .1991CCXII1.-A Study of Some Dicyclic Quaternary AmmoniumCCX1V.-The Alkaline Condensations of Nitrohydrazo-com-pounds. Part 11. By ARTHUR GEORQE GREEN andFREDERICK MAURICE ROWE . . 2003BBCQUEREL MEMORIAL LECTURE . . . 2005chloropyridine. Part 11. By WILLIAM JAMES SELL . . 1945Compounds. By JOHN GUNNING MOORE DUNLOP . . 199xvi CONTENTS.CCXV.-Studies of the Constitution of Soap in Solution :Sodium Myristate and Sodium Laurate. By JAMES WILLIAMMCBAIN, ELFREIDA CONSTANCE VICTORIA CORNISH, andRICHARD CHARLES BOWDEN . . 2042CCXV1.-The Wet Oxidation of Metals. Part 11. The Rustingof Iron (continued). By BERTRAM LAXBERT . . 2056CCXVI1.-The Oxidation of Some Benzyl Compounds ofSulphur. Part I. By JOHN ARMSTRONQ SMYTHE . .2076CCXVII1.-Studies of Chinese Wood Oil. P-Elsostearic Acid.By ROBERT SELBY MORRELL . . 2082CCX1X.-The Condensation of Pentaerythritol with Aldehydes.By JOHN READ . . 2090CCXX.-The Electrochemistry of Solutions in Acetone. Part11. The Silver Nitrate Concentration Cell. By ALEXANDERKOSHOESTWENBKY and WILLIAM CUDMORE MCCULLAGH LEWIS 2094CCXX1.-The Influence of Neutral Solvents on Velocity ofReaction. Part 11. Transformation of Auisspaldoximein Various Solvents. By THOMAS STEWART PATTERSON andHARVEY HUQH MONTGOMERIE, M.A., B.Sc. .CCXXI1.-Organic Derivatives of Silicon. Part XV. TheNomenclature of Organic Silicon Compounds. By FREDERICSTANLEY KIPPING . . 2106CCXXIIL-Organic Derivatives of Silicon. Part XVI. ThePreparation and Properties of Diphenylsilicanediol.ByFREDERIC STANLEY KIPPINQ . . 2108CCXX1V.-Organic Derivatives of Silicon. Part XVII.Some Condensation Products of Diphenylsilicanediol. ByFREDERIC STANLEY KIPPINQ . . 2125CCXXV.-Organic Derivatives of Silicon. Part XVIII. Di-benzylsilicanediol and its Anhydro-derivative. By ROBERTROBISOX, B.Sc., Ph.D., and FREDERIC STANLEY KIPPINGCCXXV1.-Organic Derivatives of Silicon. Part XIX. ThePreparation and Properties of Some Silicauediols of theType SiR,(OH),. By ROBERT ROBISON, B.Sc., Ph.D., andFREDERIC STANLEY KIPPING . . 8156TheProperties of Formamidine Disulphide and its Salts. ByEMIL ALPHONSE WERNER. . . 2166CCXXVIIL-The Action of Nitrous Acid on Thiocarbamideand on Formamidine Disulphide A New StructuralFormula for Thiocarbamide.CCXX1X.-The Preparation of Durylic and Pyromellitic Acids.CCXXX.-The Synthetical Production of Derivatives of Di-nayhthanthracene.By WILLIAM HOBSON MILLS andMILDRED MILLS. . . 2194CCXXX1.-The Essential Oil of Cocoa. By JAMES SCOTTBAINBRIDQE and SAMUEL HENRY DAVIES . . 2209PAGE. 2100. 2142CUXXVI1.-The Interaction of Iodine and Thiocarbamide.By EMIL ALPHONSE WERNER 2180By WILLIAM HOBEION MILLS . . . . 219CONTENTS. xviiPAU F:CCXXXII. -The Constituents of Cluytia sirnilis. By FRANKTUTIN and HUBERT WILLIAM BENTLEY CLEWER . . 2221CCXXXTI1.-Hydrazoximes of Benzyl and Diacetyl. By MARTINONSLOW FORSTER and BIMAN BIHARI DEY . . 2234CCXXX1V.-The Oxidation of Aconitine. By FRANCISHOWARD CARR . . 2241CCXXXV.-Electromotive Forces in Alcohol.Part 111.Further Experiments with the Hydrogen Electrode in Dryand Moist Alcoholic Hydrogen Chloride. By ROBERTTAYLOR HARDMAN and ARTHUR LAPWORTH . . 2249CCXXXV1.-Absorption Spectra of the Cobalto-derivativesof Primary Aliphatic Nitroamines. By ANTOINE PAULNICOLAS FRANCHIMONT and HILMAR JOHANNES BACKER . 2256CCXXXVI1.-Pilosine : A New Alkaloid from PiZocurpsmicrophyllus. By FRANK LEE PYMAN . . 2260CCXXXVIIL-The Effect of Heat on a Mixture of Benzalde-hydecyanohydrin with m-Chloroaniline and with m-Tolu-idine. By CLEMENT WILLIAM BAILEY (Priestley ResearchScholar of the University of Birmingham) and HAMILTONMCCOMBIE . . 2272CCXXX1X.- The Ignition of Electrolytic Gas by the ElectricDischarge. By HUBERT FRANK COWARD, CHARLES COOPER,and CHRISTOPHER HENRY WARBURTON .. 2278CCXL.-Contributions to the Chemistry of the Terpenes.Part XIV. The Oxidation of Pinene with Hydrogen Per-oxide. By GEORGE GERALD HENDERSON and MAQGIEMILLEN JEFFS SUTHERLAND, B.Sc. . . 2258CCXL1.-The Intramolecular Rearrangement of Diphenylamineortho-Sulpboxides. Part dv. By THOMAS PERCY HILDITCHand SAMUEL SMILES . . 2294CCXLI1.-Studies in the Diphenyl Series. Part 11. The Di-nitrobenzidines: a New Form of Isomerism. By JOHNCANNELL CAIN, ALBERT COULTHARD, and FRANCES MARYGORE MICKLETHWAIT . . 2298CCXLI 11. -Stul 1 ies in the Diphenyl Series. Part 111. Di-phenyldiphthalamic Acids and Pyronine Colouring Matterscontaining the Diphenyl Group. By JOHN CANNELL CAINand OSCAR LISLE BRADY .. 2304CCXL1V.-The Relation between Constitution and RotatoryPower amongst Derivatives of Tetrahydroquinaldine ByWILLIAM JACKSON POPE and THOMAS FIELD WINMILL. . 2309CCXLV.-The Absence of Optical Activity in the a- andp- 2:5-Dimethylpiperazines. By WrLLIAnr JACKSON POPEand JOHN READ. . . 2325CCXLVI -The Change in the Boiling Points of the Trioxideand Tetroxide of Nitrogen on Drying. By HERBERTBRERETON BAKER and MURIEL BAKER . . 233xviii CONTENTS.CCXLVlI.-Z - PbenyI - 1 :4:5:6 - tetrahydropyrimidinePAGIiandBenzoyl-ay-diaminopropane. By GERALD EYRE KIRKWOODBRANCH and ARTHUR WALSH TITHERLEY . . 2342CCXLVII1.-The Condensation of a-Keto-p-anilinoa-P-diphenyl-ethane and its Homologues with Phenylcarbimide aud withPhenylthiocarbimide. By SIDNEY ALBERT BRAZIEB, M.Sc.(Priestley Research Scholar of the University of Birming-ham), and HAMILTON MCCOMBIE. . 2352CCXL1X.-The Catalytic Decomposition of Nitrosotriaceton-amine by Alkalis. By DOUQLAS ARTHUR CLIBBENS andFRANCIS FRANCIS . . 2358CCL.-Photo-kinetics of Sodium Hypochlorite Solutions. ByWILLIAM CUDMORE MCCULLAGH LEWIS . . 2371CCL1.-Inositol and Some of its Isomerides. By HUGO MULLER 2383CCLI1.-The Constituents of Taraxacum Root. By FREDERICKBELDING POWER and HENRY BROWNING, jun. . . 2411CCLII1.-The Purification, Density, and Expansion of EthylAcetate. By JOHN WADE, D.Sc., and RICHARD WILLIAMMERRIMAN, M. A. . 2429CCL1V.-The Vapour Pressure of Ethyl Acetate from 0" to100'. By JOHN WADE, D.Sc., and RICHARD WILLIAMCCLV. -The Alkaline Condensations of Nitrohydrazo-compounds.Part 111. Influence of ortho-Groups on their Formationand Condensation. By ARTHUR GEORGE GREEN andFREDERICK MAURICE ROWE . . 2443CCLV1.-The Existence of Quinonoid Salts of o-Nitroaminesand their Conversion iuto Oxsdiazole Oxides. By ARTHURGEORGE GREEN and FREDER~CK MAURICE ROWECCLVI1.-The Velocity of Reaction between Potassium Chloro-acetate and Some Aliphatic Amines. By TOM SIDNEYMOORE, DONALD BRADLEY SOMERVELL, and JOHN NEWTONDERRY . . 2459CCLVII1.-Properties of Mixtures of Ethyl Alcohol, CarbonTetrachloride, and Water. By THOMAS HENRY HILL . 246'7CCL1X.-Position-Isomerism and Optical Activity : HalogenDerivatives of Methyl Dibenzoyltartrate. By PERCYFARADAY FRANKLAND, BIDNEY RAYMOND CARTER, and ERNESTBRYAN ADAMS . . 2470CCLX.-Studies in Chemical Crystallography. Part I. Co-ordination, Isomorphism, and Valency. By THOMAS VIPONDCCLX1.-The Constitution and Reactions of Thiocarbamides.CCLXIL-The Influence of Sodium Salts of Organic Acids onBy GEORGE SENTER andMERRIMAN, M.A. . . 2438. 2452BARKER . . 2484By AUGUSTUS EDWARD DIXON and JOHN TAYLOR . . 2502the Rate of Hydrolysis by Alkali.FRITZ BULLE . . 252
ISSN:0368-1645
DOI:10.1039/CT91201FP001
出版商:RSC
年代:1912
数据来源: RSC
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Front matter |
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Journal of the Chemical Society, Transactions,
Volume 101,
Issue 1,
1912,
Page 019-020
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摘要:
J O U R N A LTHE CHEMICAL SOCIETY.TRANSACTIONS.__Gammittet of B$nblicatimt :H. BXERETON BAKER, M.A., D.Sc.,HORACE T. BROWN, LL.D., F.R.S.J. N. COLLIE, Ph.D., F.R.S.A. W. CROSSLEY, D.Sc,, Ph.D., F. R.S.F. 0. DONNAN, M.A., Ph.D., F.R.S.BERNARDYER, D.Sc.M. 0. FORSTER, D.Sc., Ph.D., F.R.S.F.R.S.P. F. FRANKLAND, Ph.D., LLD.C. E. GROVES, F.R.S.A. MCKENZIE, M.A., D.Sc., Ph.D.J. C. PHILIP, D.Sc., Ph.D.A. SOOTT, M.A., D.Sc., F.R.S.5. SMILES, D.Sc.F. R. S.@bitox :J. C. GAIN, D.Sc., Ph.D.Sub-Qbitor :A. J. GREENAWAY.1912. Vol. CI. Part 11.LONDON:GURNEY & JACKSON, 33, PATERNOSTER ROW, E.C.1912RICHABD CLAY & SONS, LIMITED,BRUNS WICK STREIGT, STAMFORD STREET, 4. E.,AND BUNOAY, SUFFOLK
ISSN:0368-1645
DOI:10.1039/CT91201FP019
出版商:RSC
年代:1912
数据来源: RSC
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II.—The influence of neutral solvents on velocity of reaction. Part I. Transformation of anissynaldoxime in various solvents |
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Journal of the Chemical Society, Transactions,
Volume 101,
Issue 1,
1912,
Page 26-39
Thomas Stewart Patterson,
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26 PATTERSON AND MONTGOMERIE: THE INFLUENCE OFIT.--The Influence of Neutral Solvents on Velocityoj’ Reaction. Part I. Transformation of Anis-synaldoxime in Various Solvents.By THOMAS STEWART PATTERSON and HARVEY HUGH MONTGOMERIE,M.A., B.Sc. (Carnegie Research Scholar).A FEW years ago, Patterson and McMillan (Trans., 1907, 91, 504;1908, 93, 1041; Ber., 40, 2564; Proc. Roy. Phil. SOC. Glasgow,1910-11, 42, 26) devised a method for following quantitatively, bymeans of the polarimeter, certain desmotropic changes. The methodconsisted in dissolving a labile substance in an optically activesolvent, and observing the gradual change in rotation of the solutionaa the alteration in constitution of the inactive solute proceeded. Inthis way the velocity of bransformation of sy+ into anti-oximeNEUTRAL SOLVENTS ON VELOCITY OF REACTION. PART I.27(Trans., 1907, 91, 504 ; Ber., 1907, 40, 2564) ; of o-isonitrotolueneinto a-nitrotoluene (Trans., 1908, 93, 1048); of the a- or enol- intothe 6- or aldeform of phenylfurmylacetic ester (Trans., 1907, 91,519), and of other changes, has been measured.In the first of these papers it w a also shown that the methodwas one by means of which the effect of indifferent solvents on thevelocity of these apparently unimolecular reactions could beexamined. To similar solutions of anissynaldoxime in ethyltartrate there were added respectively, equal volumes of isobutylalcohol, of chloroform, and of benzene, when it was found that notonly was the total change of rotahion which occurred in each casequite different, but that the velocity of reaction was different also.I n view of the interest which attaches t o the influence of solventsin modifying the velocity of chemical remtions, we thought itdesirable to extend this part of the investigation.I n the presentpaper we give a description of our method and results, and concludewith a, short comparison of the latter with the results of otherinvestigators in this field.The ethyl tartrate was prepared by the hydrogen chloridesaturation method. The anissymldoxime was prepared in the usualway on the afternoon previous tol its use. On the morning of theexperiment it was recrystallised from benzene, and quickly driedon porous plate in an evacuated desiccator over sulphuric acid.The experiments were done in duplicate, always with separatelyrecrystdlised, and often with freshly prepared, synoxime.Themelting point of the sample used lay, almost invariably, between135O and 137O.I n order t o determine the most favourable conditions for con-venient work, we made a few preliminary experiments, anddetermined, in the first place, the rate of transformation of thepure anissynaldoxime in the ethyl tartrate alone, with the resultsquoted in table I on p. 28.A solution was then made up of 5 C.C. of ethyl tartrate and 5 C.C.of methyl alcohol with 5 per cent. by weight of anissynaldoxime,but the total change of rotation in a day, at 20°, was only 0*3O,and after several days it was only 0.4O. This is too small a changeto work upmi, so a similar solution, but containing 10 per cent.ofoxime, was tried. This, however, only gave a total change of 0*67O,still undesirably small. We therefore reduced the proportion ofindifferent solvent in the mixture, and made up a solution of 75 percent. by volume of ethyl tartrate and only 25 per cent. by volumeof methyl alcohol, to which was added 5 per cent. of anissynald-cixime. The change observed in the first day in this case waa 0*7O,whilst the total change was over lo; but the time which elapse28 PATTERSON AND MONTGOMERIE: TEE INFLUENCE OFTABLE I.AnissynaZdoxime in Ethyl Tartrate."I : p = 96.13 ; a = 2-61'.T (mio.).067133164219234271309CX)a:. 1000:k. + 13 -32" -13.212 0.6413'126 0'5813.056 0.6512.99 0'6212.975 0.6112-925 0.6112237 0'6110*71.-Mean ...... 0.62-T (min.).0314961758810718521223126129031336000a:.+ 13-32"13'26813-23613'22213.20213'17413.13613 '03613.01012'97712.94012-9012-8712-8110.71Mean ......1000 k.0.6710 -660'630.610.650.690'620 *590.610.600 -610.800.60-- -0.63* In this and the following tables, p indicates grams of ethyl tartrate per100 grams of solution ; a is the total change of rotation from time 0 to time 00.The initial rotation is got by extrapolation from the other data.before the transformation could be considered at an end was sogreat that we decided to work at a, higher temperature, moreespecially as the room temperature was apt, occasionally, to rise alittle above 20°.Therefore, starting afresh, the velocity constantwas d.etermined in undiluted ethyl tartrateresults :TABLE 11.Anissynaldozirne in EthylNo. ofsolution. P. d.111. 96.17 2-32"I v. 96.17 2-30at 26O, with the followingTartrate.1000 k.[,\.lean of1000 k. two series.]1-71 -1.78 1.745Tha total change of rotation at 2 6 O (2.31') is thus less than a t20' (2-61°), but the transformation is about three times ;LS rapid.The ethyl tartrate used had C$ +10.074°. The temperature waskept constant within 0'05O. The solvent9 were all carefully distilledover sodium,* and the solutions were made up as follows: 15 C.C.ethyl tartrate were delivered from a pipette into a small flask andweighed.To this were added 5 C.C. of the solvent, and the flask* Except ally1 alcohol and benzyl alcohol, which were digested with fusedpotassium carbonate and distilledNEUTRAL SOLVENTS ON VELOCITY OF REACTION. PART I. 29a:. 1000 k.10.645 2 -0710.51 2-1910.478 2.0510.43 2.1210.37 5'1210-32 2.0510.27 2.1110.25 2 *08+ 10.82" -9'646 -Mean ...... 2.10and contents again weighed. This mixture of ethyl tartrate andsolvent waa divided into two approximately equal parts, each beingweighed; these were used on successive days. To each part, asnearly as possible 4-76 per cent., by weight, of synaldoxime wasadded.* Immediately the oxime had dissolved the solution wastransferred to a 100 mm. polarimeter tube, which had been lyingfor some time previously in the thermostat of the polarimeter toacquire the desired temperature, ';he first reading being usuallymade after the lapse of about an hour.The results obtained withmethyl alcohol, ethyl alcohol, n-propyl alcohol, isobutyl alcohol,ally1 alcohol, benzyl alcohol, and water are recorded in the followingtables, the data for the first-named being given in full, whilst theremainder are summa.rised :T (min.) a",".0 f 10 -72"29 10.65465 10.580129 10'460162 10-418184 10,370250 10*250297 10'220315 10 -200ca 9'624Mean ...TABLE 111.Transformation of Anissynaldoxime 6.w Presence of &'thy2 Tartrateand Hethyl Alcohol.V: E.T.:8.:0.= VI : E.T. : S. : 0. =77.86 : 17.38 : 4.76; a = 1*1?4O.77.86 : 17.37 : 4-77 ; a = 1.096O.T (min.)078140168192230271300320og1000 k.2'142-112'101 '992.092 '062'052 '04--,.. 2.07~ ~ ~~~* That is, 4.76 grams of oxime per 100 grams of the mixture of ethyl tartrate,solvent, and oxinie. It might, perhaps, have been better to add a constantweight of oxime for a given volume of solution, but this would make practicallyno difference in the constants obtained30 PATTERSON AND MONTGOMERIE: THE INFLUENCE OFTABLE IV.Transformation of Anissynuldoxime in Presence of Ethyl TartrateSolvent.Ethyl alcoholn-Yropyl ,,isoButyl ,)A8yl 1:Benzyl ,,WZL)ter+ "Y Y , YY 9 Y SY 7 Y7Y >No.VII.VIII.IX.X.XI.XII.XIII.XI v. xv.XVI.XVII.XVIII.r E.T.: S. : 0. a.77.99 17.25 4.76 1.31"77.99 17.25 4-76 1'3077.66 17.58 4'76 1'4677-67 17-57 4-76 1.4977'f9 17'44 4.77 1'4377-79 17'45 4.76 1'4376-90 18'34 4.76 1-3316-90 18-34 4'76 1-4073.72 21.51 4.77 2-1274.87 21-29 3'84 0-3874-86 21-29 3.85 0.36i3.76 21-51 4'73 2-09a& various Solvents.Compositionof solution.1000 k.1 -921 *861.7751.6761 -000.9751-6261,6203-148'428.608 791000 k.[Meanof twoseries.]1 -891.7250-9871 *6233-288-69------In this case, on account of the solubility relationships, it was necessary to useless oxime.This series of experiments had practically exhausted our stockof ethyl tartrate, and as it was possible that the active ester hadbeen slowly changing with lapse of time, we thought it advisableagain to determine the velocity of transformation of the pure oximein the ester alone, for comparison with the original values.Theresults are given below.TABLE V.Anissynaldoxime in Ethyl Tartrate.1000 k.No. of [Mean ofsolution. P* a. 1000 k. two aeries.].XIX. 96 -1 5 2'29" 1.85 -x x. 96-16 2'28 1 '85 1'85It will be observed that the velocity constant has the same valuein both of these experiments, but that it is distinctly greater thanthat obtained at the commencement of our work, having increasedfrom 1.745 to 1-85. This has the effect, of course, of making themore recently determined constants relatively greater than theearlier ones, and we thought it worth while to apply a correction,which will be discussed later on.For the next series of solveiits a fresh sample of ethyl tartratewas prepared, which with pure anissymldoxime gave the followingresults NEUTRAL SOLVENTS ON VELOCITY OF REACTION. PART I.31TABLE VI.Anissynaldoa-ime in Ethyl Tartrate. (Fresh sample.)1000 k.No. of [Mean ofXXI. 96-14" 2'40" 0-559 -XXII. 96'15 2'40 0.567 0 -563a. 1000 k. two series. solution. P.This sample of tartrate had been subjected to a distillation morethan that first used, and the effect of this clearly appears in thelower value of the velocity consbant. The ester was, in fact,unnecessarily pure, so that our experiments book tool long to runto completion. In the following tables it is practically only readingsmade on the first day of the experiment that have been used incalculating the values of the constant, and generally the tube hadto be set aside in a thermostat at 2 6 O for about a week before therotation ceased to show any change.As an early experiment hadshown that benzene considerably hastens the reaction, we did notanticipate that the slowness of the tartrate would be 240 troubleeomeas was actually the case. Using this sample of ester, we examinedthe influence of benzene, o-xylem, m-xylene, pxylene, mesitylene,toluene, and nitrobenzene, in the order mentioned, on the velocityof transformation of anissynaldoxime.TABLE VIITransformation, of Anissynarldoxime in Presence of Ethyl Tartrateand various Soiuents.Compositionof solution.Solvent.No.Benzene XXIII.9 9 XXIV.o- X ylene xxv.9 9 XXVI.m-Xylene XXVII.I $ XXVIII.p-Xylene XXIX.Y 9 xxx.Mesi tylene X X X I.9 9 XXXII.Toluene XXXIII.9 9 XXXIV.Nitrobenzene X XXV.9 ) XXXVI.i T .76-5476.5476.4576 '4476.7976.876.7976.7976 *876.7576-776.7571.3871-373: s. : 0.18.70 4.7618.70 4-7618-79 4-7618'79 4-7718'44 4.7718'44 4-7618'45 4-7618-44 4-7718'49 4'7118-48 4'7718.48 4-8218-49 4'7623.86 4.7723-86 4.76a.2-57'2.302 *322.4552-682-712-662-692'542-652.672 '632.872 '901000 k.1 -001-030.730.7540-8130.8030.8720 *850.7720.7650.8610'8581-151 -061000 k.[Mean ofof twoseries.]1'0150.7420 -8080 '8610.7680'8591 '1 05-------Finally, we made a control experiment with anissynaldoxime andethyl tartrate alone, in order to ascertain what dteration, if any,had taken place in the tastrate while this second series of experi32 PATTERSON AND MONTGOMERIE: THE INFLUENCE OFments was being caxried out, and found, as in the previous case,that the ester was distinctly quicker than before, the constant being0.67 instead of 0.563.TABLE VIII.Anassynaldosime in Ethcyl Tartrate.XXXVI I.96'17 2.356" 0.67I nthe second column is shown the total change of rotation for eachsolution. We have here not taken a mean value, but have giventhe greater of the two changes. When the total change in oneexperiment is less than in its fellow, it indicates that a little moretransformation has occurred before the observations commenced,but this does not influence the value of the velocity constant.Itmay be noticed that the total change of rotation in the tartratealone is not strictly comparable with the changes in the presenceof the neutral solvents, since in the former case the oxime isinfluencing 100 per cent. of active ester, and in the latter only75 per cent.TABLE IX.Rate of Transformadion of A.Itissynaldoxime in Various Sotventsat 26O.No. P. a. 1000 k.In table IX we have collected together the data observed.Total changeinSolvent. rotation.1. No diluent ......... 2.32"2. Water ............... 0'383. Methyl alcohol ... 1.1744. Ethyl alcohol ... 1.315. n-Propyl alcohol 1 '496.boButyl alcohol 1'437. Ally1 alcohol.. .... 1 '408. Benzylalcohol ... 2-129. No diluent ...... 2'291. No diluent ......... 2-402. Benzene ............ 2.573. Toluene ............ 2-674. o-Xylene ......... 2.4555. m-Xylene ......... 2.716. p-Xylene ......... 2-697. Mesitylene ...... 2.658. Nitrobenzene ... 2.909. No diluent ...... 2.3561000 k.1'7458-692'0851-891 -7250-9871.6233 -281.850.5631.0150-8590.7420'8080-8610.7681.1050.67The total change in the case of water1000 k. 1000 k.Corrected Corrected forfor alteration inalteration ethyl tartiatein ethyl and referredtartrate. to one standard.1-745 1'7458 '26 8 '262 *07 2.071 *862 1-881.687 1-690.958 0.961 -565 1 -563-14 3.140'563 1 -7451.009 3-130.752 2'330.708 2-190.754 2'340-786 2-440.686 2-130'947 2.94- -- -is very small, only 0*3B0,and, perhaps in consequence of this, the values of k, after abouNEUTRAL SOLVENTS ON VELOCITY OF REACTION.PART 1. 33one hundred minutes, were not so constant as for the other solvents.The total change is greater in methyl alcohol than in water, andit rises, through ethyl alcohol, t o reach a maximum of 1.49O inn-propyl alcohol. In isobutyl alcohol and in ally1 alcohol it is alittle less than in n-propyl alcohol. It is to be noticed that in thearomatic compounds the total change is markedly greater than inthe aliphatic alcohols, the value rising a little from benzene t otoluene and t o m-xylene, and being greatest in nitrobenzene.The influence of the benzene nucleus is clearly evidenced by thehigher value for benzyl alcohol as compared with the aliphaticalcohols.In the third column are given the values for k as found, whilstin column four we give these values corrected for the alterationwhich takes place in the active ester on keeping.This correctionwas made by subtrading the initial from the final constant in ethyltartrate alone (I -85 - 1.745 = 0.105), and aauming that one-eighthof this increment took place between each of the experiments ofthe series; thus in the case of !+propyl alcohol, which was the thirdto be used, the tartrate would have become more rapid by3 x 0*013=0-039, so that its constant would be 1.784, instead ofthe original 1.745, and calculating back t o the latter value we have1.725 x 1*745/1*784=1.687 as the true value of the constant forn-propyl alcohol referred to ethyl tartrate, the constant of which un-diluted is 1.745.In the fifth column the numbers for the aromatichydrocarbons are calculated in a similar manner with reference to anethyl tartrate of constant 1.745 instead of 0.563, so that all thenumbers in this column are directly comparable.I n table X are shown, in comparison with our own, the resultsof other workers so far as is possible. Columns 2, 3, and 4 representrespectively the data given by Menschutkin for the reactionbetween acetic anhydride and sec.-propyl alcohol at looo, for thereaction between acetic anhydride and isobutyl alcohol, and for thecombination of triethylmine with ethyl iodide. Columns 5 and 6contain the d a b given by Dimroth for the conversion of the enol,methyl 5 - hydroxy-1-phenyl-1 : 2 : 3-triazole-4-carboxylate (Annden,1904, 335, 7), into methyl anilidodiazomalonate ( A n d e n , 1910,373, 344) a t two different temperaturea Column 7 shows thevelocity constanb obtained by Tubandt for the inversion ofmenthone.Column 8 gives v. Halban’s numbers for the rate ofdecomposition of triethylsulphine bromide, whilst the last containsour own results. The numbers given are, in all c a a except ourown, relative, not actual, constants, whereas with regard to ourdata, since the value for isobutyl alcohol is almost unity, and thisis the smallest, the numbers given are practicdlg identical withVOL 01.34 PATTERSON AND MONTGOMERIE: THE INFLUENCE OFSolvent.TABLE X.Menschutkin.> Aceticanhydride eLand G O - "2 Tub-Dimroth. andt.Isomerisni Inver-ofa siontriazole ofderivative. Mentli-v. Hal-ban.Decom-positionof tri-ethyl-sulphinebro-mide.7v.7Pat-tersonandMont-gomerie.Anis-syn-intoanis-anti-oxime.26".Water .................. 0'0043 - - - 8.26Methyl alcohol ...... - - 286.6 1'00 1.00 1-00 1-0 2.07Ethyl alcohol ......... - - 203.3 1'92 1-94 2'60 1.0 [?I 1-86n-Propyl alcohol ... - - 3-38 1.8 1.69n-Butyl alcohol ......isoButyl alcohol.. .... - - 143-3 - - 4'64 - 0.96Amy1 alcohol ................. 240.5 - - 0'63 - 1.56 Ally1 alcohol - -Benzyl alcohol ......- - 742'2 - 2.08 0.37 - 3'14Benzene ............... 1'00 1'00 38.2 - - - - 3-13- 2 '33 Toluene ...............- 2-19 o-Xylene ...............m-Xylene ........... 1'25 ** 1'37 ** 15.9 - - - - 2 '34- 2'44 p-Xglene ...............I 2-13 Mesity lene ............Nitrobenzene ......... - - - - 86-80 - 180.0 2'94Hexane - - ............... 2.07 2.18 1'0 - - -Acetone .............. - - 337.7 9.94 9.94 - 290'0 -24.50 - - Ether .............................. 50.90 39.80 - 230.0 - ChloroformisoButyl alcohol ,,- - -- - -- 4-10 - - - - - -- - - - - - - -- - - - - -- - - - - -- - - - - -- - - - I -- -_ - - -- - -- 1'00 -1'14 -2'44 -n-Butyl alcohol [25"] - - - - -set.-Butyl alcohol ,, - - - - -tert.-Butylalcohol ,, - - - - - 5'48 - -- - - - - --* Zeitsch.physikal. Chem., 1887, 1, 629.t Zeitsch. physikal. Chem., 1890, 6,. 41.$ Annulen, 1904, 335, 7; see also Dimroth (Annulen, 1910, 373, 368) forconstants a t 50°, i n methyl and ethyl alcohol, acetone, and chloroform, for thechanges of methyl hydroxybeuzyltriazolecarboxylate into the benzylamide of methyldiazomalonate.!I Annalen, 1907, 354, 259. $j Annalen, 1910, 377, 131.l T Zeitsch. physikal. Chem., 1909, 67, 129.** Menschutkin does not state which xylene was used.those which would be found by referring the data t o the constantfor isobutyl alcohol as unity.On the whole, the data thus obtained by very different processesfor reactions varying greatly in type, show some remarkable regu-larities.Menschutkin in his first experiments found that thereaction between acetic anhydride and n-propyl alcohol and aceticanhydride and isobutyl alcohol were both influenced in much thes3me way by the solvents benzene, xylene, and hexane, beingslowest in the first- and fastest in the last-named. In his nexNEUTRAL SOLVENTS ON VELOClTY OF REACTION. PART I. 35investigation he examined the reaction between triethylamine andethyl iodide, finding it to be influenced by the solvents mentionedin just the opposite order, being slowmt in hexane and quickestin benzene, the effect of the solvent being also very much moremarked. His investigation extended to other wlvenh, some ofwhich are iuciuded in the table, when it was found that the velocitywas still greater in the monatomic saturated alcohols, very rapidin acetone, and most rapid in benzyl alcohol, being over sevenhundred times as fast as in hexane and nearly twenty times asfast as in benzene.The velocity becomes less as the homologousseries of alcohols is ascended, and it will be noticed that in ourexperiments the same is the case. The closeness of the similaritybetween Menschutkin’s results and ours will, however, be betterseen from table XI, in which the former are referred to theconstant for isobutyl alcohol as unity.TABLE XI.Patterson andSolvent. Menschutkin. Montgomerie.,ko-Butyl alcohol ............... 1.0 0.96Ethyl , , ............... 1 ‘42 1 *86Ally1 , , .............. 1 *68 1-56Methyl ,, ............... 2.0 2’07Benzyl , , ............... 5’18 3 -14It will be observed that the sequence in these alicohols is thesame, except in regard to the positions of ethyl and allyl alcohol,Menschutkin’s reaction proceeding more rapidly in allyl alcohol,whilst we found the reverse to be the case.Apart from this, thenumbers found are strikingly alike, not merely in sequence, buteven in magnitude.Comparing Menschutkin’s results and ours for aromatic solvents,there is at once a resemblance and a difference. Menschutkin foundthat in benzene and xylene triethylamine combines much lessrapidly with ethyl iodide than in the alcohols mentioned, whilst wefind that, on the whole, the oxime transformation takes placedistinctly more rapidly in the benzene series of solvents than in theopen-chain alcohols. The sequence, however, is again the same,both reactions proceeding more slowly in xylene than in benzene,the difference being much greater in his case than in ours.It isdifficult to account for the position occupied by benzyl alcohol inMenschutkin’s table. It might be expected that if benzene itselfhas so considerable it retarding influence, the introduction of theC6HS-gToup into carbinol would bring about a diminution insteadof an increase. Our result for benzyl alcohol seems t o be in betteragreement with the behaviour of benzene and methyl alcohol. Itu 98 P A ~ E R S O N ANb MoNTBOMLRIE: TEE INFLUENCE OFwill be noticed that our constmt for toluene is a little lower thanthat for m-xylene; this, we think, is due to slight over-correction,the experiments with this solvent having been done out of theirproper order. The constant for benzene is greater than that fortoluene, that for toluene is almost certainly greater than that form-xylene, whilst that for m-xylene is in turn greater than thatfor m esitylene.Our results f o r the xylenes are, so far as we are aware, the firstfrom which it is possible to compare the relative effects of 0-, m-,and p-substitution.The effect is quite marked; the reactionproceeds most rapidly in p-xylene, and most slowly in o-xylene. Itis perhaps worthy of remark that m-nitrobenzsymaldoxime trans-forms into the anti-form more rapidly than does o-nitrobenzsyn-aldoxime (Patterson and McMillan, Proc. Roy. Phil. SOC.Glasgow,1910-11, 42, 29).Turning now t o the other columns of table X, several pointsmay be noticed. I n the first place, it will be observed that thesequence is the same for Dimroth’s transformation, for the inversionof menthone, and for the decomposition of triethylsulphine bromide,but this sequence is just the opposite of that found by Menschutkinand ourseives; the velocity of reaction increases as the homologousseries of alcohols is ascended, and in somewhat the same manner ineach case; thus the inversion of menthone takes place 2.6 times asrapidly, whilst Dimroth’s transformation proceeds about twice asrapidly, in ethyl as in methyl alcohol. The results of v. Halbanare of a similar kind.Again, it may be noticed that whilst Dimroth’s reaction takesplace very much more slowly, ours takes place much more rapidlyin water than in methyl alcohol, so that there is here a distinctagreement at lea& of a qualitative character.Any definite effect due t o the presence of a double bond is scmcelyto be discerned. We find for ally1 alcohol a constant, 1-56, veryclose to that for n-propyl alcohol, 1-69; Menschutkin’s consfant fallsbetween those for methyl and ethyl alcohol, whilst Tubandt’s isdistinctly lower than that for methyl alcohol.Our data are insufficient to allow of any definite statementregarding the effect of isomerism in the aliphatic series, but fromanalogy to the constants for methyi alcohol, 2.07, ethyl alcohol,1-86, and n-propyl alcohol, 1.69, it seems probable that the constantfor n-butyl alcohol would be about 1.5, distinctly greater than thatfound for isobutyl alcohol, 0.96.Branching in the carbon chainwill therefore probably be found t o lower the rate of the reaction.Tubandt examined this point more thoroughly, and observed thatthe constant for his reaction incremes from n-butyl, through isoNEUTRAL SOLVENTS ON VELOCITY OF REACTION. PART T. 37and sec.-, to tert.-butyl alcohol, and since his reaction is influenced,in ot’her solvents, in just the opposite way from ours, this is inagreement with the conclusion we arrive a t from our experiments.We may also refer to the fact that the range through which ourvelocity constant varies is smaller than. for the other investigationsquoted. It must be remembered, however, that in Menschutkin’sexperiments, for example, one volume of reaction mixture wasdiluted with fifteen volumes of the solvent, whilst in OUTS, onevolume of reaction mixture was diluted with only one-third of avolume of the solvent, and if it be permissible t o assume that theeffect of the solvent will bear a fairly direct relationship to itsquantity, then the range of our constants would probably be con-siderably increased in the presence of a larger proportion of solvent.That the effect of so small a proportion of solvent can be detectedthus clearly is a sign of its great importance.Some other investigations which cannot be summarised intable X, may be briefly referred to.Walker and Kay (Trans., 1897,71, 504) fouxid that the velocity of transformation of ammoniumcyanate into carbamide is vory greatly accelerated by the additionof ethyl alcohol, the value of the constant for 90 per cent.alcoholbeing nearly one hundred times as great as the value for pure water,and this in spite of a co-existent retardation which the alcoholeffects by diminishing the number of active molecules present inthe solution. Other neutral substances were found to exert asimiIar accelerating influence in the following order of increasingrapidity : glycerol, ethyl alcohol, sucrose, glycol, methyl alcohol,acetone. Lowry (Trans., 1899, 75, 211) followed the mutarotationof nitrocamphor in various solvents ; Lowry and Robertson (Trans.,1904, 85, 1548) found that 8-bromcqb-nitrocamphor apparentlypasses much more rapidly in benzene solution than in chloroformsolution into its stable form; Lowry and Magson (Trans., 1908,93, 110) give for the change of nitrocamphor into +-nitrocamphorthe following velocity constants : in ethyl alcohol, 0.0048 ; aceticacid, 0.0025 ; ether, 0.00149 ; and in benzene, 0*00013.Dawson andMiss Leslie, studying the reaction between acetone and iodine,assume, with Lapworth (Trans., 1904, 85, 30), that the acetonebefore being acted on by the iodine, undergo- a tautomeric changeinto the enolic form, and they have measured the velocity of thischange in various solvants. They find that it is greatest in methylalcohol, diminishing successively in nitrobenzene, benzene, carbontetrachloride, whilst in water the velocity is, relatively, nil ;although these data are perhaps rather scanty, it may neverthelessbe noticed that the sequence-methyl alcohol, nitrobenzene, benzene-is the same as that found by us, except that in the former cm38 PATTERSON AND MONTOOMERIE: THE INFLUENCE OFthe above order is one of diminishing velocity, whereas in the latterit is that of increasing velocity.The position of water, however,as Dawson and R!hs Leslie remark, does not seem t o be in harmonywith their other results. Again, it may be mentioned that Klein(J. Physical Chem., 1911, 15, 1) finds the reaction between hydrogensulphide and sulphur dioxide to take place readily in alcoholicsolution, whilst it does not appear to occur a t all in benzene.I n general, therefore, reviewing the experimenk which have beenquoted and sane others to which no reference has been made, i tappears that solvents influence quite different reactions in a uniformmanner, although the manifestation of this effect may be of anoppmite character; a given set of solvents may hasten a particularreaction in a certain sequence, whilst in the same or very nearlythe same sequence they retard another reaction.The property orproperties of the solvents which bring this about are probably thesame throughout, just as, in a similar manner, a given force mayaccelerate the velocity ol a body moving in one direction, whilst itwill retard the motion of a body moving in the opposite direction.The apparently opposite effects are manifestations of the samecause. Although other investigators have discussed some of thephenomena we have referred to, with a view t o exhibiting a relation-ship between the magnitude of the velocity constants and thedielectric constant of the solvents, without any marked success, wenevertheless think that the character of the results generally issuch as indicates a physical cause for the influence of the solvent.The most recent correlation of this character has been made byDimroth, who adopts a suggestion of van’t Hoff connecting thevelocity of transformation of a labile substance in various mediawith its solubility in these media. That the application of thisinterwting idea is likely to be attended with difficulty must beclear from the fact, amongst others, that one chemical individualmay have several different solubilities in the same liquid, the solu-bility being a function of the state of aggregation of the solute.I f , however, the maximum solubility-that, prgsumably, of theliquid solute-were chosen, the difficulty referred to might, to someextent, disappear.* It is, a t least, certain that the solubilitiesfound by Dimroth, which probably, from the method of determina-tion, are really those of the liquid solute, show a remarkable rela-tionship to the values found for the velocity constant (AnnaZen,1910, 377, 131).The rate of transformation of the mi-formbecomes greater as its solubility diminishes. This suggestion hasalso been considered in the case of the tautomerism of acetoaceticester by K.H. Meyer ( A m l e n , 1911, 380, 229).* Mutually miscible liquids present an obvious difficultyNEUTRAL SOLVENTS ON VELOCITY OF REACTION. PART I. 39The idea of complex formation has been less readily accepted inthis than in some other fields, and it might, we consider, be expectedthat, if these effects were due to complex formation, the influenceof each solvent on each reaction would probably be specific, in whichcase the general results ought to be quite erratic. The suggestionof hydrogen ion catalysis has also been made, but has met withno success.Whether all reactions are catalysed or not, the one we haveexamined certainly is, although we have not yet found an oppor-tunity t o investigate the nature of the catalyst. Since, however,it has been shown by Tubandi; (dnnalen, 1911, 377, 284) that theinfluence of solvents on the velocity of inversion of menthone maydiffer to some extent according to the catalyst used, this mightprove to be the case with our reaction also, and we were afraid, incommencing our work, that solvents purified without any veryspecial precautions might perhaps contain small quantities offoreign subst.ances which would catadyse the oxime transformationerratically. This, however, does not appear to be the case, moreespecially since Dunstan and Mussdl (this vol., p. 571) were unableto bring about the transformation of the mimes a t all, even a trelatively high temperatures, in water, ethyl alcohol, benzene, andamyl acetate.Unfortunately, our collaboration was brought to an end soonerthan we had expected and before the programme we had arrangedwas completed, but we hope to have a future opportunity of carryingour work a, stage further.I n conclusion, we wish to express our thanks to the CarnegieTrustees for the Universities of Scotland, who kindly placed at thedisposal of one of us the large polarimeter with which this researchwas carried out.ORGANIC CHEMISTRY DEPARTMENT,UNIVE.RSITY OF GLASGOW
ISSN:0368-1645
DOI:10.1039/CT9120100026
出版商:RSC
年代:1912
数据来源: RSC
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III.—The velocity of interaction of iodic and sulphurous acids in various media |
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Journal of the Chemical Society, Transactions,
Volume 101,
Issue 1,
1912,
Page 40-41
Thomas Stewart Patterson,
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40 PATTERSON AND FORSYTH : VELOCITY OF INTERACTION OF111.-The Velocity of Interaction of Iodic andSulphurous Acids in Variozcs Media.By THOMASTEWART PATTERSON and WILLIAM COLLINS FORSYTH.IN connexion with the experiments detailed in the preceding paper,we thought it would be of interest to examine some other type ofreaction, and chose, as one perhaps allowing of very simple observa-tion, the well kiiown experiment of Landolt on the reduction of iodica i d by sulphurous acid (Ber., 1886, 19, 1340; 1887, 20, 745).Dilute solutions of these reagents are mixed, a small quantity ofstarch solution being present, and after the lapse of a definite time,depending on the concentration of the solutions and the tempersture, a blue colour suddenly appears, due to the action of theliberated iodine on the starch.Landolt himself made some experi-ments regarding the influence of added inactive substances, andfound that acids-sulphuric, hydrochloric, oxttlic, acetic-hasten thereaction the more the greater is the afhity constant of the acid.Sodium chloride and ammonium chloride were also found to acceler-ate the reaction, but to a less extent. Similarly, alcohol in theproportion of 7 to 3 of water in the solution reduced the timenecessary for the appearance of the blue colour from 102.2 sea. to90.4 secs. He says that the influence of alcohol is thus not great,and that he was unable to find a liquid which definitely retardedthe velocity of the reaction.For the following experiments oar reagents were made asfollows: Of a saturated solution of sulphur dioxide, 50 C.C.werediluted to a litre, whilst 10 grams of iodic a i d were dissolved in1 litre of water. For an experiment, 10 C.C. of sulphur dioxidesolution were first mixed with 2 C.C. starch solution, and to thiswere added 106 C.C. of diluent, water, for example. To thismixture 10 C.C. of iodic acid solution were quickly added, thetemperature being about ZOO in all cases. In the above instancethe blue cdour flashed out in nineteen seconds. In other experi-ments, instead of the 100 C.C. of water, 100 C.C. of pure methyl,ethyl, n-propyl alcohol, or acetone, or mixtures of these with waterxn known proportiom were added. The colour which appeared inthe solution was blue or yellow, according to the proportion ofneutral solvent added.In the case of methyl alcohol the following r e d & were obtained:Percentage of methyl alcoholin 100 C.C.of added diluent. Time.0 19 seconds50 9 7 7100 .z 9IODIC AND SULPHUROUS ACIDS IN VARIOUS MEDIA. 41It thus appears that the addition of methyl alcohol hastens thisreaction very considerably, and practically in direct proportion tothe quantity of alcohol added. It was then found that ethyl andn-propyl alcohol behaved in a manner quite similar to methylalcohol, the accuracy of the method of investigation being insuffi-cient to detect any distinct variation.On the additioa of acetone the results were somewhat different,as the following table shows :Percentage of acetonein 100 C.C.of added diluent. Time.25 23 ¶ *50 24 Y Y75 15 ))100 3 9 )0 19 seconds60 2o Y JThe velocity of tho reaction increases at first as the proportion ofacetone increases up to about 50 per cent., todiminish again rapidlythereafter.It is not possible much to extend the examination of this reaction,since the scriveiits used must (1) be neutral or acid, and (2) bemiscible with water, two conditions which considerably limit thenumber of available liquids. In addition, although the reaction isone which can be timed fairly accurately, the variation in colour ofthe starch iodide and also the complexity of the whole reactionrender the results at least difficult of interpretation.We need only remark that an increase in the velocity of areaction, on the addition of a neutral solvent, to reach a maximumhas been observed in numerous cases; thus, Dawsm (Trans., 1911,99, 1) found the reaction between iodine and acetone with a littlesulphuric acid in presence of ethyl alcohol t o be very greatly reducedby the addition of small quantities of water, whilst Tubandt(Annalen, 1907, 354, 259) has recorded a somewhat similarobservation in regard to the inversion of menthone. For otherreferences Dawson’s paper should be consulted.ORGANIC CHEMISTRY DEPARTMENT,UNIVERSITY OF GLASGOW
ISSN:0368-1645
DOI:10.1039/CT9120100040
出版商:RSC
年代:1912
数据来源: RSC
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5. |
IV.—Diphenylcyclopentenone |
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Journal of the Chemical Society, Transactions,
Volume 101,
Issue 1,
1912,
Page 42-50
Siegfried Ruhemann,
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摘要:
42 RUHEMANN AND NAUNTON : DIPHENYLCYCLOPENTENONE.IV. --Diphen y Zcyclopen tenone.By SIEGFRIED RUHEMANN and WILLIAM JOHNSON SMITH NAUNTON.THE study of ths cyclic ketonic compounds, in which one of ushas been engaged for some time, led to the knowledge of triketo-hydrindene, the first member of the cyclic triketones containingthree adjacent ketonic groups in an isocyclic system. This oom-pound appears to be of especial interest on account of its closeresemblance t o alloxan and of its characteristic colour reactionswith proteins and their hydrolytic products.With the view of preparing similar substances and examiningtheir behaviour, we have subjected 3 : 4-diphenylcycZopentenone,which Japp and Burton (Trans., 1887, 51, 420)obtained by the action of hydriodic acid on anhydroacetonebenzil,to the same treatment as the mono- and di-ketones of hydrindene.On applying Sachs and Barschall's method of transformingmethylene groups into ketonic groups (Ber., 1901, 34, 3047), it wasfound that pnitromdimethylaniline reacts with the cy clopentenonemainly to f orrn 2 : 5-2,is-dzmet~~Za.mir~oaniZo-3 : 4-diphenglcyclwpen-ternone (I), but a t the same time a compound is produced, theGPh*$X N- C,H,*NMe, EPh*$XN*C,H,*NMe,CPh CO CPh CN*C,H,*NMe,CH2'f?PhCO<CH,*cPh'\/C :N*C,H,*NMe,\/C:N*C,€I,*NMe2(1.1 (11.)analytical results of which point to a, compound of the formula (11).It8 formation is to be explained by the assumption of the partialreduction of the former compound, and its subsequent condensationwith another molecule of pnitrdimethylaniline.This constitu-tion is supported by its behaviour towards mineral acids, since bothslubstances yield 5-c€.t'met&Zaiminoando-3 : 4-diphe?yZcyclopentene-1 : 2-dione :CPh : CPh NMe,*C,H,*N: C<GO-60 *The fact that, 'under the influence of acids, the groups:N*C,H4*NMe2 are removed with the exception of one of them, ismost remarkable in view of the observations of Sachs and hiscollaborators, and of the fact tha.t bis-dimethylaminoanilo-a-hydrin-done on treatment with acids readily yields triketohydrindenehydrate (Trans., 1910, 97, 1438). The stability of 5-dimethylamineanile3 : 4-diphenylcyclopentene-l : 2-dione is, in fact, so great thaRUHEMANN AND NAUNTON : DIPHENYLCYCLOPENTENONE.43the removal of the group :N*C,H,*NM% could not be accomplishedwithout effecting at the same time a deep-seated change to diphenyl-maleic anhydride :This transformation takes place very slowly and incompletely onboiling the compound with potassium hydroxide or hydrochloricacid under the ordinary pressFre, but more readily on heatingwith concentrated hydrochloric acid a t 130-140° for several hours.The change of 5-dimethylaminoanilo-3 : 4-diphenylcyclopentene-l : 2-CO-gPhCo<C**CPh’dione into 4 : 5-diphenylcyclopentene-l : 2 : 3-trione,cannot be effected by means of either nitric acid or bromine. Thesereagents mainly yield substitution products.With fuming nitric acid it forms a deep red dinitro-derivative,C2,H180,N,(N0,)2, whereas bromine reacts with the compound toform a yellow monobromo-derivative, C2,H1902N2Br, when thereagents are used in molecular proportions.From the fact thatthis bromo-substitution product, on heating with concentratedhydrochloric acid, yields diphenylmaleic anhydride, it follows thatsubstitution has taken place in the benzene nucleus of the dimethyl-aminoanilo-group, and that therefore its constitution is t o berenresented thus : I CPh:$JPh NMe,*C, H,Br*N :C< co-co ’in which only the orientation of the bromine atom is doubtful. Onusing, however, two molecules of the halogen to one molecule of thesubstance, a yellow, crystalline compound is obtained, which loseshalogen even om drying in the air. This substance is undoubtedlythe perbromide of a bromo-substitution product of the azomethine.On boiling with alcoh,ol, this perbromide decomposes, and yieldsbesides the former yellow mmobromesubstitution product, a deepred dibromo-derivative of the azomethine.The red solution of the compound, C25HW02N2, in glacial aceticacid is readily decolorised by zinc dust t o yield colourless base,C,,H,O,N,, which is to be regarded as 5-dimethyl~minoanilo-3 : 4-diphenylcyclqentane-1 : 2-dime :This constitution follows from the fact that the substance onheating with concentrated hydrochloric acid decomposes to formx-diphenylmccinic acid.The azomethine, C,,H,,O,N,, is orange or red, and has baai44 RUHEMANN AND NAUNTON : DIPHENYLCYCLOPENTENONE.propertim, forming salts with acids, which, with the exception ofthe platinic salt, are readily dissociated by water.The compoundis practically insoluble in cold alcohol, but on boiling it dissolvessparingly, and on cooling small, deep red plates separate from theconcentrated solutions, whereas it crystallises from more dilutesolutions in absolute alcohol in orange needles. If a little wateris added t o the hot alcoholic solution of the compound, no crystalsseparate on cooling, but the whole sets to a transparent jelly, whichaccording to the concentration is yellow or yellowish-red. This gel,when kept at the ordinary temperature, gradually liquefies, andin the course of one to two days completely disappears, with separ%tion from the resuiting solution of the azomethine in orange needles.The transformation of the substance into the colloidal state occurswith solvents which are miscible with water, and therefore takesplace with acetone, but it is not observed in solvents like chloroformor benzene, which are immiscible with water.It is probable thatthis phenomenon is accompanied by the formation of a hydrate,which spontaneously loses water and yields the original compound.This exceptional property of the azomethine, which is not t o befound with ih bromcl. or nitro-substitution products, will besubjected to a, closer study.EXPERIMENTAL.A ction of p-Nitrosodimet~tylanili?te o n 3 : 4-D~phelzyZcyclopenternone.The cyclopentenone was prepared from anhydroacetonebenzilaccording to the directions of Japp and Lander (Trans., 1897, 71,131), with the difference that the product which is obtained on thereduction of anhydroacetonebenzil was twice recrystallised fromalcohol wit.h the use of animal charcoal, instead of distilling underdiminished pressure, as stated by these authors.The compound wasobtained in colourless needles melting at llOo. On treatment withp-nitrosodimethylaniline it was found that two condensationproducts are produced, which contain two and three dimethylamino-ado-groups respectively, even when the reagents are used in theproportion of one molecule of the pentenone to two molecules ofthe nitrowderivative. On account of this fact an excess of thenitroso-compound was used, and the reaction was carried out asfollows : The pentenone (5 grams) and p-nitrosodimethylaniline(10--12 grams), dissolved in hot alcohol, are mixed, and a littleconcentrated dcoholic potassium hydroxide is gradually added tothe cold solution of the mixture.The green colour of the solutionchanges t o brown, and a dark solid separates, which increases inquantity in the course of three to four days. To remove impuritiRUHEMANN AND NAUNTON : DIPHENYLCPCLOPENTENONE. 45it is boiled with alcohd, in which it is only sparingly soluble, anddried in t@he steam-oven; the product dissolves in hot chloroformto yield a dark red solution, and on cooling partly crystallises inbrown needles, whereas the other part d m not separate until thesoluti~n is considerably concentrated or mixed with alcohol. Thesubstance which is lms soluble in chloroform melts at 255O, buton repeated crystallisation from the same solvent it is obtainedin cho@ate-coloured needles, which melt at 265O after softening afew degrees before :0.2031 gave 0.5856 CO, and 0.1190 H,O.@= 78.62; H = 6.51.0.2012 ,, 0.5807 CO, ,, 0.1175 H20. C=78.71; H=6*49.0.2021 ,, 24.5 C.C. N, at 2 1 O and 755 mm. N=13.67.C41H40N6 requires C= 79-87 ; H = 6-49 ; N = 13'63 per cent.The substance appears to be 1 : 2 : 3-tris-dimethylaminoanilo-4 : 5-dipheenylcyclopentene (11, p. 42).The deficit in the percentage of carbon is probably due to asmall quantity of impurity, although after more frequent recrystal-lisation results were obtained on analysis which do not materiallydiffer from those given above.The purification of the main product of the action of p-nitroso-dimehhylanihe on diphenylcgclopentenone, which product iscontained in the mother liquor of the former condensation product,can be readily accomplished.It separates on distilling the largerportion of the chloroform and adding alcohol to the hot concen-trated solution until crptallisation commences. If the substanceis twice recrystallised from a, mixture of chloroform and alcohol, it isobtained in bronze needles, which melt at 211-212O:0.1760 gave! 0.5125 (20, and 0.0965 H,O.0.1633 ,, 15-8 C.C. Nz at 19O and 775 mm. N=11.34.This compound is 2 : 5-bis-dimethylaminoanilo-3 : 4diphenylcyclo-U=79-42; H=6'09.C,H,ON, requiresl C= 79-51 ; H = 6-02 ; N = 11.24 per cent.pentenone (I, p. 42).5-D.lmetli ylaminoanilo-3 : 4-diphcnylcyclopentene-l : a-dione,NMe,*C, H ,-N : C< CPh:$?Phco--coBoth substances which are formed by the condensation ofp-nitrosodimethylaniline with the cyclopentenone show the samebehaviour; they have bmic properties, and dissolve in cold hydrechloric or sulphuric acids to yield deep red solutions, whichgradually at the ordinary temperature, but rapidly on warmingon the water-bath, become turbid; a yellow, tenacious, and elasticproduct separates, which in the course of a day sets to a hard46 RUHEMANN AND NAUNTON : DIPHENYLCYCLOPENTENONE.brittle mass, turning red on washing with water.This substancedissolves in boiling absolute alcohol, and on cooling crystallises inorange needles, melting a t 191-192O :0.1681 gaveO.4865 CO, and 0,0790 H20.0.1733 ?, 11.4 C.C.N, at 23O and 764 mm. N=7*45.C,,H,02N, requires C = '78.95 ; H = 5-26 ; N = 7.37 per cent.&Dime t hyZttminoanilo-3 : $-diphew Zcyclopelzt ene-1 : 2-dione is spas-ingly soluble in ether, almost insoluble in cold +lcohol; it dissolvessparingly in boiling alcohol, 1 gram of the substance requiring110 C.C. of boiling alcohol; from this solution the compoundseparates in smdl, deep red plates as compared with the orangeneedles, in which it crystallises from less concentrated solutions inabsolute alcohol. It has been mentioned above @. 44) that thebehaviour of the substance is quite different if water is added evento the dilute solution in absolute alcohol; on cooling in thiscase no crystals separate, but the whole sets to a transparent jelly,which gradually liquefies, and at the same time deposits orangeneedles of the original compound.The same phenomenon occursif acetone is used as a solvent instead of alcohol. The compound,C,,H,,O,N,, is very soluble in benzene or chloroform, but the redsolutions which are formed do not gelatinise on the addition ofwater.The azomethine has basic properties, forming salts with acids,which, however, are dissociated by water. On the addition ofhydrochloric acid it turns yellow, and yields a gelatinous hydrechloride identical with the salt which is formed in the preparationof the azomethine from the cc4ndensatisn-products of diphenylcyclo-pentenone with pnitrosodimethylaniline. The hydrochloridegradually solidifies to a brittle mass, which on washing with waterloses hydrogen chloride and turns orange.The hydrochloridereadily dissolves in alcohol t o yield a yellow solution, which ontreatment with platinum chloride forms a platinichloride, separatingin bunches of yellow needles; they soften a t 232O, and melt anddecompose at 236O:C= 78.93 ; H =5*22.0.3055 gave 0.0509 Pt. Pt=16*66.The orange substance, C,&O,N,, also forms a yellow sulphitt;e,(C,,H,,0,N,),,H2PtCl, requires Pt = 16-68 per cent.which is readily decomposed by water into base and acid.Formation of Diphenylmaleic Anhydride from 5-Dimethyl-aminoamilo-3 : 4-diphenylcyclopentene-l : 2-dione.The compound, @25H200&2, on boiling with concentrated aqueouspotwium hydroxide or with hydrochloric acid under the ordinarRUREMANN AND NAUNTON : DIPHENYLCYCLOPENTENONE. 47pressure is only slightly attacked, but when heated with concen-trated acid in a sea.led tube to 130-140° for four hours it is trans-formed into a pale yellow solid.This is collected, washed with water,and digested with dilute potassium hydroxide, when it almost com-pletely dissolvm. On adding hydrochloric acid to the alkalinefiltrate a, floccG1ent substance is precipitated, which readily dissolvesin hot alcohol, and crystallises from dilute alcohol in faintly yellowneedles, melting at 156-157O. The melting point and the proper-ties characterise this compound as diphenylmaleic anhydride,co<*--c* GPh:(?ph . Its composition has been verified by analysis.(Found, C= 76.85 ; H = 4.01.Calc., C= 76.80 ; H = 4-00 per cent.)The action of hydrochloric acid on the azomethine, therefore, notonly effects the replacement of the group :N-C,H,*NMe2 by oxygen,but at the s m e time the removal of the adjacent ketonic goup.All attempts to produce 4 : 5-diphenylcyclopentene-l : 2 : 3-trione(p. 43) or its hydrate from the compound @25H2002N2 have beenunsuccessful.Action of Bromine and *Vitric Acid on the Compound C25H200,N2.By the action of these reagents the removal of the group:N*C,H,*NMe2 does not take place, but substitution productsare formed instead. I f bromine (1 gram) is gradually added tothe solution of the ammethine (2.3 grams) in chloroform, thehalogen rapidly disappears, the colour of the solution becomesyellow, and no precipitate is formed if the reagents are used inexact equimolecular proportions.On mixing the chloroformsolution with light petroleum a yellow solid is precipitated, whichdissolves in much boiling alcohol, and on cooling slowly crystallisesin long, yellow prisms, which soften at about 152O, and melt a t1 5 4 O to a red liquid:0.2017 gave 0.4828 CO, and 0.0770 H,O. C=65*28; H=4*24.0.2545 ,, 0.1038 AgBr. Br=17*35.C25H,90aN2Br requires C= 65.36 ; H = 4.14 ; Br = 17.43 per cent.The bromoderivative is sparingly soluble in ether or cold alcohol.With mineral acids it forms salts, which are readily dissociatedby water. The hydrochloride dissolves in warm alcohol, and thecold yellow solution on the addition of platinic chloride yields aplatinichloride, which gradually separates in yellow needles, soften-ing at 189O and melting at 195O:0'2730 gave 0.0395 Pt.Pt=14*47.The bromwderivative, which does not show the phenomenon of(C,,H,,O,N,Br),,H,PtCI, requires Pt = 14.67 per cent48 RUHEMANN AND NAUNTON : DIPHENYLCYCLOPENTENONE.being transformed into bhe colloidal state, on heating with concen-trated hydrochloric acid in a closed tube a t 135-140° for about fivehours, suff em a similar decomposition to the azomethine, C25H2002N2.An almost colourless solid is formed, which dissolves in hot dilutepotassium hydroxide, and is precipitated from the alkalinesolution on the addition of hydrochloric acid. The substance crystal-lises from dilute alcohol in pale yellow prisms, which are free fromhalogen and melt at 156-157O.These properties characterise itas diphenylmaleic anhydride. Its formation leads to the conclu-sion that the bromine has entered into the benzene nucleus of thedimethylaminoado-group of the azomethine, and that, therefore,the bromederivative has the formula :NM~~-c,H,B~~N:c< CPhfp?hco-coQuite different, however, is the action of bromine on theazomethine, C2,HWO2N2, if two molecules of halogen are slowlyadded to a solution of one molecule of the compound in chloro-form; in this case a precipitate consisting of bunches of yellowneedles is produced. This product, which is very sparingly solublein chloroform, is very unstable, since it constantly loses brominein a vacuum desiccator or even on drying in the air. Thisbehaviour, which points to the view that the substance is a per-bromide, prevented us from fixing its composition by analysis,but the decomposition which it suffers on boiling with alcohol, inwhich it yields a, mixture of the mono- and dibromo-derivatives ofthe azomethine, indicates that it is the perbromide of the yellowmonobromMompound, Cz5H,,02N,Br, and that, theref ore, it isprobably rapresented by the formula:NMe,*C,H,Br*NBr,: C<The perbromide dissolves in much boiling alcohol to yield ayellow solution, from which, on cooling, red needles separate; these,however, do not represent a pure substance, but a mixture of theyellow bromoccompound, C2,H,,02N2Br, and a red dibromederivative of the azomethine.Owing to the fact that the dibromo-compound is less soluble than the monobromclderivative, theisolation of the former can be effected by recrystallisation fromboiling alcohol. After repeating the process of purification threetimm, the dibrom,o-derivative is obtained in long, scarlet needles,which soften at 212O, and melt a t 214O:0.2076 gave 0.4262 CO, and 0'0625 H20.0.2090 ,, 0.1450 AgBr. Br-29-53.C= 55-99 ; H = 3-34.C,H,@zN,Brz requires C = 55.76 ; H = 3.34 ; Br = 29.73 per centRUHEMANN AND NAUNTON : DIPHENYLCYCLOPENTENONE. 49The alcoholic liquor from this compound, on concentration,yielded yellow prisms, which were identified as the monobromo-compound, C2,HI90,N,Br, by the melting point.Fuming nitric acid readily reacts with the azomethine,C,,H,,O,N,.On adding an excess of the acid to the cold solutionof the compound in glacial acetic acid, a dinitro-derivative,CBH&~T\I’,(NO,),, gradually separates. It is sparingly soluble inboiling alcohol, readily so in hot glacial acetic acid, and crystallisesin well-defined scarlet prisms, which soften a t 220° and melt anddecompose a t 2244:0.2027 gave 0.4766 CX), and 0’0733 H,O. C = 64-12 ; H = 4.01.0.2254 ,, 24 C.C. N, a t 20° and 759 mm. N=12*16.C2,H,,0,N, requires C= 63-83 ; EL‘= 3-83 ; N = 11.91 per cent.The positions of the nitro-groups in this compound have notbeen ascertained, but judging from the action of bromine on theazomethine, C,,H,,O,N,, there can hardly be any doubt that atleast one of them is contained in the benzene nucleus of thedimethylaminoanilo-group. Simultaneously with the formation ofthe dinitrederivative, there is produced a smdl amount of diphenyl-maleic anhydride, which is contained in the mother liquor of theproduct of the reaction, and is precipitated on the addition ofwater.It was purified by dissolving it in warm alkali, and repre-cipitating it with acid. After recrystallisation from dilute alcohol,it melted at 156-157O.5-Dime thylaminoanilo-3 : 4-daphen.yZcyclopentane-1 : 2-dione,As yet only the action of zinc dust on the solution of the azemethine in glacial acetic acid has been examined, with the resultthat a colourless compound, with the composition C2,H,0,N,, isproduced. The red solution of the azomethine (5 grams) in aceticacid is readily decolorised by zinc dust, and on adding water to thefiltrate a colourless solid (3.5 grams) is precipitated, which dissolvesin much boiling alcohol, and, on cooling, crystallises in colourlessneedles, melting a t 210-21lo :0.2168 gave 0.6255 CO, and 0.1155 H,O.0-1997The substance has basic properties, forming a hydrochloride0.2470 gave 0.0393 Pt.VOL.CI. EC?=78*68; R=5.92.C2,HB0,N, requirw C= 78.53 ; H= 5-75 ; N = 7.33 per cent.,, 13.3 C.C. N, at 18O and 742 mm. N=7*50.which, with platinic chloride, yields a pZatinichZoride :Pt = 15.91.(C~E,O,N,),,H,PtCl, requires Pt = 15.72 per cent50 FRIEND: THE POROSITY OF IRON AND ITSThe base, C,,H,02N2, on heating with concentrated hydrochloricacid a t 130-140° for three hours, decomposes in a manner similarto 5-dimethylaminoanib3 : 4-diphenylcyclopentene-l : 2dione to yields-diphenylmccinic acid. The colourless solid which is produced inthis reaction is collected, washed with water, and dissolved in hotdilute alcohol or acetic acid.; from these mlutions the acid separatesin colourless needles or prisms, which melt a t 252O. (Found,C=71m18; H-5.30.The sltatements as to itsmelting point differ widely.Reimer (Ber., 1881, 14, 1803), as wellas Chalaney and Knoevenagel (Ber., 1892, 25, 296), give 229O;Anschutz and Bendix ( A n d e m , 1890, 269, 61), 245O; whereasRoser (AnnuZen, 1885,247, 152) found 252O, which latter statementagrees with our observation. An explanation for these great differ-ences cannot as yet be given. The acid mother liquor fromP-sdiphenylsuccinic acid, which is formed by the decomposition ofdimethylaminoanilodiphenylcyclopentanedione, also contains, inaddition to dimethyl-pphenylenediamine, a-s-diphenylsuccinic acid.This wits extracted with ether, and after evaporation of the etherwm recrystallised from water, in which it is rather soluble. It fusesa t 183O, then solidifies, and finally melts at 220-221O; this observa-tion agrees with Reimer’s statement (Zoc. cit.).Calc., C=71.11; H=5*19 per cent.)This acid is P-diphenylsuccinic acid.The behaviour of diphenylcyclopentenone recorded in this paperis of sufficient interest to merit a closer study. This work is inprogress as well as the investigation of other cyclic ketonic com-pounds on the same lines as those employed in the case of theketones of the hydrindene eeriea.UNIVER~ITY CHEMICAL LABORATORY,CAMBRIDGE
ISSN:0368-1645
DOI:10.1039/CT9120100042
出版商:RSC
年代:1912
数据来源: RSC
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6. |
V.—The porosity of iron and its relation to passivity and corrosion |
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Journal of the Chemical Society, Transactions,
Volume 101,
Issue 1,
1912,
Page 50-56
John Albert Newton Friend,
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50 FRIEND: THE POROSITY OF IRON AND ITSV.-The Porosity of Iron and its Relation toPassivity and Corrosion.By JOHN ALBERT NEWTON FRIEND, D.Sc.APPARENTLY the earliest attempt to explain pmsivity was madeby Schonbein,” in 1836, who suggested that the inactivity of theiron was caused by the presence of a thin layer of iron oxide* A full account of the passivity of iron with exhaustive references is given in“The Corrosion of Iron and Steel” (Longmans, 1911), Chap. XII, by the presentauthorRELATION TO PASSIVITY AND CORROSION. 51covering the surface of the metal. This yiew was apparentlyconfirmed by the fact that all powerful oxidisers are capable ofrendering iron passive, whilst reducing agents readily render thepassive metal active. In view of the more recent work of Heathcote( J .ij’oc. CAem. Id., 1907,26, 899), Krassa (Zeitsch. Elektrochem.,1909, 15, 490 and 98l), Manchot (Ber., 1909, 42, 3492), andDunstan and Hill (Trans., 1911, 99, 18531, there can be no doubtthat in many cases this is the correct explanation. Dunstan and Hillhave drawn attention to the fact that iron is rendered passive byimmersion in alkaline solutions. They do not, however, offer anyexplanation of the fact, inasmuch as there would appear to be nopossibility of the formation of a protective layer of oxide on thesurface of the metal.It seemed of importance, therefore, to study more carefully thephenomena of passivity as induced by this method. In the presentresearch the test for passivity was that suggested by Dunstan andHill, namely, the immersion of the sample of iron in water alongsideof, but not actually in contact with, a similar piece of metalknown to be active, and observing the times required for pronouncedrusting to occur.The mtive metal always showed clear signs ofrust in .the course of eight or ten minutes, whereas the passivemetal retained its bright .surface for much longer periods. Theseobservations coincide entirely with those of Dunstan and Hill.Series 1.-Pieces of Kahlbaum’s pure iron foil measuring4 x 4 cm. in area were cleaned with emery paper and immersed inconcentrated solutions of sodium hydroxide (approx. 6 N ) for aperiod of three weeks. On removal they were thoroughly washedin a stream of distilled water, laid in shallow porcelain dishes, andjust covered with a small quantii?y of distilled water, being shieldedfrom dust and evaporation by glass covers.On applying the usualflame test for sodium with clean platinum wire, no trace of thatmetal could be detected in the water in the dishes, showing thatthe iron had been properly washed. After about ten hours a traceof sodium could be detected in solution; and twenty-four hours laterthe reaction wits well marked, the Bunsen flame assuming a brightand persistent yellow colour. Examination with the spectroscopeconfirmed the presence of sodium. Blank tests simultaneouslycarried out proved that the sodium could not have dissolved outof the basin itself, nor yet have entered the dish with particles ofdust.An exactly similar series of experiments was carried out, in whichthe sodium hydroxide was replaced by an equally strong solutionof potassium hydroxide.In this case the potassium could not bedistinctly recognised by the flame test within forty-eight hours.It must therefore have dissolved out of the iron.E 52 FRIEND: THE POROSITY OF IRON AND ITSAfter about sixty hours the reaction was as decided a53 that forsodium.Froin this it would appear that the iron is slightly porous, andthe passivity induced by immersion in alkaline solutions is due tothe absorption of minute quantities of the alkali. This hypothesisreceives confirmation from the following series of experiments.Series ZZ.-Pieces of pure iron foil which had been immersed forthree weeks in concentrated solutions of pckassium hydroxide werethoroughly washed with wabr, dried, and vigorously polished withemery paper.After a second thorough washing they were placedin shallow porcelain dishes with other similar pieces of active foil,and covered with water. Whilst the active metal corroded in eightor ten minutes as usual, the samples that had previously been inthe alkali remained bright for several hours, and then slowly begant-, oxidise. In twenty-four hours no difference between the twoset@s of kpecimens was apparent, showing that the passivity haddisappeared.Now all experimenters agree that ordinary passivity is rapidlylost, even on gently handlipg the metal. Clearly, therefore, apassivity capable of withstanding the vigorous action of emerypaper must be of a very different type, and one which is .not con-cerned merely with the surface of the metal.In this cme theoxide theory is untenable, the only feasible explanation being thatthe metal is protected by traces of alkali absorbed into its pores.This further explains why the metal was found to rust in a normalmanner after a few hours, for the absorbed alkali would graduallydiffuse out of the metal into the water, become neutralised withcarbon dioxide, and thus cease to protect the metal.Series ZZZ.-Pla;tes of wrought iron, No. 22 B.W.G., andmeasuring 14x 10.5 cm. in area, were treated in the followingmznner :Nos. 1 and 2 were cleaned thoroughly with emery paper.Nos. 3 and 4 were “pickled” for ten hours in dilute sulphuricacid, thoroughly washed with water, dried first with filter paper,and then by warming for ten minutes in a steam*ven.Ncs.5 and 6 were “pickled” in dilute sulphuric acid for thesame perid of time as Nm. 3 and 4. They were then thoroughlywashed with water, and immersed in 2N-sodium hydroxide for onehour. After again washing, they were dried for ten minutes in astem-oven.The above six plates were now weighed, and placed in a thermostat, being arranged round the internal circumference of the vesselin a vertical position, a indicated in the figure. Each plate restedon a.n earthenware beehive, which latter stood on a, plate oRELATION TO PASSIVITY AND CORROSION. 53para.ffin wax covering the bottom of the thermostat. The upperpark of the platm leaned against a glass rod bent in the form ofa hoop to fit inside the thermostat.These precautions were essentialin order to prevent galvanic action from taking place between theseveral plates. Water was continuously passed into the thermostatthrough C, and on reaching the level A was rapidly syphoned offthrough B until its level fell to D. I n this way the plates werealternately exposed to wet and dry, each refilling of the vesseltaking some two hours.cleaned, dried in the steam-oven, and weighed.given in the following table:After six days the plates were removed,The results areInitial weight, Loss in weight, Mean loss, Reln ti vePlate No. grams. grams. grams. corroLioii. 0"::; } 0-31 100 1 75.532 71.893 72.824 72.465 72-986 6C.90~:~~ } 0-48 155145 0.440.46 } 0'45A second similar set of experiments entirely confirmed theseresults .It is evident that the plates which had been placed in acidcorroded more rapidly than the others, showing that the acid isnot immediately washed out of the iron by water.That plates 5and 6 corroded more rapidly than 1 and 2 shows that either thealkali had not had time to soak in as far as the acid had done, or,what is moreprobable, that it had neutralised the acid in the poresof the metal and had remained there as sodium sulphate, not beingcompletely washed out in the 'final rinsings, and thus stimulatingthe corrosion, although not to so great an extent as the free acidwould have done. Ail these experiments therefore agree in illus-trating t.he porou: nature of iron, and an explanation is thusafforded for the fact, well known to painters, that the acid i54 FRIEND: THE POROSITY OF IRON AND ITSexcessively difficult to remove, by the mere process of washing, fromthe surface iron that has been treated with acid t o remove theadherent mill scale.This, in fact, is one of the great difficultiesin the trade.Conclusions.The above experimenb lead us to the following importantconclusions :(1) The surface of iron is slightly porous, so that when the metalis immersed in certain solutions the latter are absorbed to a minuteextent.This observation is of particular interest in view of the numerouscatalytic reactions in which finely divided iron plays an importantpart.(2) The passivity induced by immersion of iron in alkalinesolutions, such as those of potassium and sodium hydroxides, is dueto absorption of minute quantities of these substances within thepores of the metal.This affords a ready explanation for tlie facts that such passivity:( a ) Is gradually lost by the iron when immersed in water, for the( b ) May be rapidly removed by the addition of small quantities( c ) May be retained for long periods, if kept dry, since the alkali(d) Varies in intensity according to the concentration of the(3) There are more kinds of passivity than one.Since the above explanation of the passivity induced by dkalinesolutions cannot possibly apply to that caused by powerful oxidiserssuch as nitric acid, we have here for the first time a definite proofthat there: are more kinds of passivity than one.This removes oneof the great difficulties in the way of accepting any theory ofpassivity, for it is generally assumed that one theory shouldexplain every case. De Benneville ( J . Iron Steel Inst., 1897, ii, 40)showed that the passivity induced by concentrated silver nitratesolution is identical in kind with that resulting from immersionin strong nitric acid; and this is what we might expect when twosuch similar solutions are employed. Fredenhagen (Zeitsch.pliysikal. Chem., 1908, 63, l), on the other hand, has observeddifferences in the behaviour of iron rendered passive by anodicpolarieation in sulphuric acid from that passivified by immersionin strong nitric mid.He therefore suggests that the two kinds ofpassivity may be different, but no definite proof has been forth-coming. Similarly Senderens (.7. Iron Steel Inst., 1897, ii, 78)alkali slowly diffuses out again.of any acid.is unable to escape.alkali amd the time during which the metal is (‘ soaked.RELATION TO PASSIVITY AND CORROSION. 55draws attention to the fact that unannealed iron is more active thanannealed iron when both are immersed in nitric acid, whereas thereverse is true in silver nitrate solution. Whilst these peculiaritiesmay simply be due to differences in intensity of the passivity, inview of the above proof that different kinds of passivity can exist,it is clear that each case must be judged on its own merits, and noone theory required to explain every cam.Furthermore, in studying the phenomena of passivity, particularcare must be taken t o ensure the absence of traces of solutionswithin the pores of the metal.Herein probably is to be found anexplanation for many of the conflicting statements as to theproperties of passive iron, with which the literature of passivityabounds.The Relation of Passivity to Corrosion.These results have a very important bearing on the varioustheories advanced to account for corrosion. In a recent paper(Proc., 1910, 26, 179) an apparatus is described showing that watermay be distilled on to iron in an acid-free atmosphere withoutproducing any trace of rust, and this experiment may be regardedas a definite proof of the acid theory of corrosion.Dunstan andHill (Zoc. cit., p. 1848), however, argue that the absence of corro-sion is4 attributable to passivity induced by previous immersion ofthe metal in potassium hydroxide, and that, until this passivity hasbeen removed by traces of acid, the iron cannot rust.I n order to show that continued washing with water wouldremove the alkali from the pores of the metal and render it active,strips of iron which had been rendered passive as above by prolongedimmersion in concentrated potassium hydroxide solution wereplunged into boiling water and the latter allowed to boil vigorouslyfor varying lengths of time. The strips were then removed, andtested for passivity in the usual way. It was found that boilingfor three minutes produced but little effect, the metal remainingdecidedly passive; after ten minutes’ boiling the metal was onlyslightly passive, and soon corroded; but after boiling for half anhour the passivity had entirely disappeared.In my experiments,therefore, in which the, iron, in the apparatus referred t o above,was washed by condensing steam on it for many hours, therecacnot be the slightest doubt that all the alkali was completelywashed out of the pores. Hence the fact that an acid must beintroduced into the apparatus, which Dunstan himself acknowledges,in order to induce corrosion, is simply a restatement of the acidtheory of corrosion. The main function of the alkali is to dissolveout the traces of acid from the pores of the metal, and thus torender its surface clean and free from acid56 FRIEND: THE POROSITY OF IRON.The Action of Va*.ious Electrolytic Solutions on Iron.Dunstan and Hill (loc.cit., p. 1850) give a table purporting toillustrate the action of various electrolytic solutions on iron, zinc,aluminium, copper, and magnesium. Heyn and Bauer, however, intheir monumental researches (Mitt. Ronigl. NateTial-piifungsamf)1908, 26, 2) into the action of various solutions on iron clearlydemonstrated in a quantitative manner for all the commonsalts the important effect produced by varying the concen-tration of bhe electrolyte; thus, not only does dilute sodiumcarbonate fail to inhibit the corrosion of iron, but it actuallystimulates it, whereas in the presence of more concentrated solutionsiron may be kept bright for an indefinite time.The same is truefor the ferro- and ferri-cyanides of potassium. Furthermore, J. H.Brown and the author (Trans., 1911, 99, 1302) have shown that thetemperature a t which the experiments are carried out is likewisean important item ; thus, whilst dilute sodium chloride solutionsabove 1 3 O tend to retard corrosion, below this temperature theystimulate it.In the table drawn up by Dunstan and Hill both the tempera-ture and concentration axe omitted, so that the results are notmerely useless but pOaitively misleading. It is interesting to notea t the bottom of the table that potassium ferrocyanide is said bothto inhibit and to allow the corrosion of iron. This is true forconcentrations of 2.0 grams and 0.2 gram per litre respectively. I fthe second potassium ferrocyanide is a misprint for the ferricyanide,the statement is less true. One per cent. solutions of either salt willcompletely inhibit corrosion.This shows how important it is that full quantitative particularsshould be given, for qualitative mixtures chosen at randominevit'ably lead to confusion.In conclusion, I have pleasure in acknowIedging my indebtednessto the Research Fund Committee for a grant which is enabling meto continua these studies of corrosion.THE TECHNICAL COLLEGE,DARLINOTON
ISSN:0368-1645
DOI:10.1039/CT9120100050
出版商:RSC
年代:1912
数据来源: RSC
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7. |
VI.—The action of aliphatic amines ons-dibromosuccinic acid. Part I |
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Journal of the Chemical Society, Transactions,
Volume 101,
Issue 1,
1912,
Page 57-61
Edward Percy Frankland,
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ACTION OF ALIPHATIC AMINES ON S-DIBROMOSUCClNIC ACID. 57VI.-The Action of Aliphatic Anzines ons-Dibrowtosuccinic Acid. Part I.By EDWARD PERCY FRANKLAND and HENRY EDGAR SMITHTHE authors have investigated the action of n-propylamine and72-butylamine on s-dibromosuccinic acid in alooholic solution withthe view of obtaining the dialkylaminosuccinic =ids of the typeR*NH*$!H*CO,HR*NH*CH*CO,HThese compounds were prepared by the method described byE. P. Frankland (Trans., 1911, 99, 1775) for dibenzylminosuccinicacid, and the reaction appeared to proceed in a similar manner,yielding in the case of propylamine the amine salts of dibromosuc-cinic acid and .bromomaleic acid, but no bromopropylaminosuccinicacid. The final product was in each case a mixture of the dialkyl-aminosuccinic acid and its amine salt, the pure aminclacid beingobtained by recrystallisation from hydrochloric acid or ammonia.The dipropylamine and dibutylamino-succinic acids are crystal-line solids, sparingly soluble in water, and forming salts with copperand with hydrochloric acid, and dinitrosederivatives of the typeR-N( NO)*QH-CO,HR.N(NO)-CH-CO,H'EXPERIMENTAL.Action of Prolrylamilte on s-Dibromosuccinic Acid inEthyl-alcoholic Solution.(a) DipropyZamine Salt of Dibromosuccimk Acid and Monopro&-amine Salt of Mombromomleic Acid.-A solution of 10.0 grams ofdibrommuccinic acid in 100 C.C.of absolute ethyl alcohol wastreated with 8'55 grams of propylamine (4 molecules). The solutionbecame warm, and a white precipitate was deposited.This wascollected, washed with alcohol and ether, and dried; it weighed14.3 grams. Theory requires 14-28 grams of the dipropylaminesalt of dibromosuccinic acid. The substance crystallised in small,hexagonal plates, and melted a t 139O,* decomposing at 1 6 5 O :0.1714 gave 97.03 C.C. CO, and 9-57 C.C. N,.+ C=30.48; N=7.01.C,,H,,O,N,Br, requires CT= 30.46 ; N = 7.11 per cent.A small portion of the substmce was dissolved in water, and an* All temperatures here given are uncorrected.t Dry CO, and N2 at N.T.P. ; carbon and nitrogen combustion in a vacuum58 FRANKLAND AND SMITH: THE ACTION OF ALIPHATICaqueous solution of silver nitrate added. A white, crystallineprecipitate Df the disil rer salt of dibromomccinic acid was deposited,which darkened on exposure to light.On warming this substancein aqueous solution, silver bromide separated :0.1586 gave 0.1205 AgBr. Ag=43-65.C,sO,Br,Ag, requires Ag = 44.08 per cent,A portion of the dipropylamine salt was dissolved in alcoholcontaining a little water, and the solution evaporated to dryness onthe water-bath. The residue was then dissolved in absolute alcohol.Propylamine hydrobromide (Found, Br = 56.71. Calc., Br = 57-14per cent.) and the monopropylamine salt of monobromomdeic acidwere isolated from the solution by fractional crystallisation fromalcohol. The monopopylamine salt of monobromdomaleic acidseparated from alcoholic solution in long, needle-shaped crystals,which melted at 93O.The cold aqueous solution decolorised permanganate :0.1586 gave 97.96 C.C.GO, and 6.81 C.C. N,, C = 33.25 ; N =5*39.( 6 ) Dipropglaminosuccinic Acid.-A solution of 10.0 grams ofdibromwuccinic acid in 100 C.C. absolute alcohol was treated with8-55 gra.ms of propylamine, and heated to boiling on the water-bath.The dipropylamine salt dissolved, and after heating for aboutforty-five minutes another substance began to deposit, completeprecipitation being obtained after about seven hours’ heating.The substance was washed with alcohol and ether, and whendried weighed 5.9 grams. A little moreof this substance was obtained by evaporating the mother liquor.This substance, dipropylaminosuccinic acid, was purified bydissolving it in the least possible quantity of concentrated hydrochloric acid, and diluting with water, when a white powder wasilr.mediately deposited.The mother liquor yielded some propyl-amine hydrochloride, and when beuzoylated, mpropylbenzamidewas obtained, melting a t 85c. (Found, C=73*11; H =8.18;N = 8.78. Calc., C= 73.62 ; H = 8-00 ; N=8.59 per cent.)DipropjlaminosuccirLic acid crystallised from queous solution inplates. It was insoluble in alcohol or ether, sparingly soluble inhot water, and readily so in concentrated acids and ammonia. Aspecimen of dipropylaminosuccinic acid recrystallised fromammonia decompased at 278O. The aqueous solution was neutralto litmus:C =51.62; N=12.07.C,H,,O,NBr requires C = 33.07 ; N = 5-51 per cent.It decompmed a t 283O.Om04 gave 96-25 C.C. CO, and 9-65 C.C.N,.0.0858 ,, 0.1618 CO, and 0.0676 H,O. C=51*43; H=8*75.Clo13,004N2 requires C=51*72; H=8*62; N=12.07 per centAMINES Oh' S-DIBROMOSUCCINIC ACID. PART I. 59Monohydrochloride of Dipropylaminosuccinic ,4 cid.On warming a solution of dipropylaminosuccinic acid in 25 percent. hydrochloric acid on the water-bath, the unchanged acid couldiiot be reprecipitated by dilution of the solution with water. Afterevaporating the solution to a small bulk a.nd stirring with alcohol,a white, crystalline solid was deposited.On recrystallising from a solution in alcohol containing a fewdrops of hydrochloric acid, a hydrochloride separated in long,needleshaped crystals, which melted and decomposed a t 187O. Itwas readily soluble in water, and insoluble in absolute alcohol orether.The aqueous solution wits acid to litmus:C=44*24; N=10*34.C,,H2,0,N,,HCl requires C = 44-69 ; N = 10.43 ; Cli= 13.22 per cent.0.1187 gave 97-53 C.C. C'O, and 9.77 C.C. N,.0.8139 ,, 0.4262 AgC1. C1=12.96.Dihydrochloride of Uipropylaminosuccinic Acid.When dipropylaminosuccinic acid was dissolved in a smallvolume of concentrated hydrochloric acid and the solution evapor-ated over sodaArne and sulphuric acid in a vacuum, a white solidwas deposited. This was stirred with concentrated hydrochloricacid, collected, and washed with dry acetone and ether. It decom-posed somewhat on further treatment with acetone and ether, givinga pink solid, which had a chlorine content lying between those ofthe mono- and di-hydrochlorides of dipropylaminosuccinic acid.Thefirst product gave the following result on analysis:0.7560 gave 0.7874 AgCl. C1=25*77.On concentrating a solution of the substance in aqueous ammoniaItC,,&,0,N2,2HC1 requires C1= 23.28 per cent.on the water-bath, dipropylaminosuccinic acid was deposited.decomposed a t 278O.Dinitrosodilrroyylnminoszlccinic A cid.One gram of dipropylaminosuccinic acid was dissolved in a smallvolume of concentrated hydrochloric acid, and the solution dilutedslightly with water. On adding a solution of the molecular quantityof sodium nitrite (2 molecules) to the well-cooled acid solution withfrequent stirring, a white solid was gradually deposited in groupsof minute needles. This was collected, washed with water, anddried.The substance was insoluble in cold water, extremelysoluble in alcohol or ether. It melted and decomposed at 157O, andgave the Liebermann test for a, nitrosecompound60 FRANKLAND AND SMITH: THE ACTION OF ALIPHATIC0*1051 gave 80-24 C.C. CO, and 16.2 C.C. N,. C=41*10; N=19*36.CIoHl8O,N, requires C =41*38 ; N = 19.31 per cent.Copper Salt of Dipropylarninosuccinic Acid.An excess of copper carbonate was gradually added t o 1 gram ofdipropylaminosuccinic acid in boiling water. The solution wasmade up to 200 C.C. with water, boiled ftor some time, and filteredwhile hot.The residue was then boiled with dilute acetic acid to removethe excess of copper carbonate, thoroughly extracted with boilingwater, filtered, washed with alcohol and ether, and dried.Thecopper salt was a light blue powder, insoluble in water and organicsolvents.Under the influence of heat it gradually changed colour t o alight red a t about 230O; it then gradually assumed the colour ofreduced copper at 240--245O, shot up the melting-point tube a t250°, and finally decomposed at 262-263O :0.4756 gave 0.1309 Cu$. Cu=21.97.C,,H,,O,N,Cu requires C'u = 21.66 per cent.A c t ion of n- 2I.u t y la mine on sDib romosucci& A cid.A solution of 5.0 grams of dibromosuccinic acid in 70 C.C. absolutealcohol was treated with 5.4 grams (4 molecules) of n-butylamine.The solution became warm, and deposited the di-n-butylamine saltof dibromosuccinic acid as a white, crystalline precipitate. Onheating on the water-bath, this precipitate quickly dissolved, andafter forty-five minutes' heating another precipitate began todeposit.This was collected from time to time, washed with alcoholand ether, and dried. It weighed 3-05 grams, and decomposed at288O. After purification by dissolving in the least possible quantityof concentrated hydrochloric acid and precipitating with water, thesubstance decomposed a t 289-290O. It was sparingly soluble inhot water, insoluble in alcohoI and in ether, and easily soluble inconcentr&t#ed acids and aqueous ammonia. The aqueous solution wa.sneutral to litmus:0.1422 gave 0.2872 CO, and 0.1206 H,O.0.0932 ,, 95.61 C.C. CO, and 8-11 C.C. N,. C=55.23; N=10*93.C=55*08; H=9.40.CIBH2A0,N2 requires C = 55.38; H = 9.23 ; N = 10.77 per centAMINES ON S-DIBROMOSUCCINIC ACID.PART I. 61MonoltydroclhZoride of Bibutylarninosuccinic A cid.A solution of dibutylaminosuccinic acid in concentrated hydrclchloric a.cid was evaporated to small bulk on the water-bath, andthe residue dissolved in waxm alcohol, from which a white, crystal-line solid separated out. This was recrystallised from alcohol con-taining a few drops of ooncentrated hydrochloric acid, and wasdeposited in shining plates, which decomposed a t 195-196O. It wasreadily soluble in water, sparingly so in alcohol, and insoluble inether. The aqueous solution wm strongly acid to litmus:0.0996 gave 0.0468 AgC1. C1= 11.62.C,2H,404N2,HC1 requires C1= 11-97 per cent.0.9 Gram of dibutylaminosuccinic acid was dissolved in a smallvolume of concentrated hydrochloric acid, and the solution dilutedsomewhat with water. On adding a solution of the molecularquantity (2 molecules) of sodium nitrite, a precipitate was depositedin minute needles. The mixt,ure was allowed to remain for a time,and the precipitate collected. After washing with water anddrying, the substance melted and decomposed at 147O. It wasinsoluble in cold water, m d extremely soluble in alcohol or ether:0.1034 gave 86-41 C.C. CO, and 14-31 C.C. N,. C=44*99;N = 17.39.C12E&0,N, requirea CI = 45-28 ; N = 17.61 per cent.Copper SaZt of Bi-n-bu,tyZaminosuccinic Acid.This compound was prepared a,s described for the copper salt ofdipropylaminosuccinic acid. It was a light blue powder, insolublein water and organic solvenh. It exhibited characteristic behaviourwhen heated. It changed to light red a t 230-235O, shot up thetube a t 245--250°, and findly decomposed at 265-267O :0.3816 gave 0.0943 CuO. Cu=19.73.C,,H,,O,N,Cu requires Cu = 19.75 per cent.CHEMICAL DEPARTMENT,THE UNIVERSITY, EDGBASTON,BIRMINGHAM
ISSN:0368-1645
DOI:10.1039/CT9120100057
出版商:RSC
年代:1912
数据来源: RSC
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8. |
VII.—Complex thio-oxalates |
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Journal of the Chemical Society, Transactions,
Volume 101,
Issue 1,
1912,
Page 62-76
Charles Stanley Robinson,
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62 ROBINSON AND JONES : COMPLEX THIO-OXALATES.VI I.- Complex Thio- oxal a tes.By CHARLES STANLEY ROBINSON and HUMPHREY OWEN JONES.IN a former paper (Jones and Tasker, Trans., 1909, 95, 1904) i twits shown that highly colourd complex compounds are formedwhen solutions of nickel or cobalt salts are added to a solutionof potassium dithio-oxalate. These colours persist through a longrange of dilution, being appreciable a t a dilution of one part ofnickel or cobalt in 40,000,000 of water. A complex salt containingnickel wits isolated and shown to have tb composition of a potassiumsalt of nickelodithieoxalic acid, H,(COS),Ni. The intense colourof solutions of this salt is so remarkable that it was considered ofinterest to prepare other salts, and also to isolate the compoundformed by the interaction of solutions of a cobalt salt and ofpotassium dithio-oxalate.\We have prepared several metallic and some organic salts ofnickelodithio-oxalic acid ; a similar series of salts of palladiodithiooxalic acid has been obtained, and it has also been shown that saltsof the complex ferrodithio-oxalic acid are formed, but these areextremely unstable.The complex salts derived from cobaltidithio-oxalic and rhodii-dithio-oxalic a d s have been isolated.The molecular weights and electrical conductivities in aqueoussolution of some of these salh have been determined. The resultsof these experiments indicate that nickeldithio-oxalic acid andcobaltidithio-oxalic acids are dibasic and tribasic respectively.Thethermal decomposition of certain salts of these acids was studiedwith a view to obtain some insight into their constitutions. Theexperimental evidence at present available is in agreement withthe formula M’(COS),*Ni*(CDS),M’ for salts of nickelodithio-oxalic acid, which is shown to be an acid of about the same strengthas sulphuric acid. The salts of palladioc and ferrGdithio-oxalicacids are derived from dibasic acids of similar constitution.The cobalti- and rhodii-dithio-oxalates are, however, derived fromtribaslic acids, and the formula of the cobalt compound can best berepresented as :/(COS>,M’CO-- (COS),M’ .\(COS),M’When potassium cyanide is added to solutions of potassiuROBINSON AND JONES : COMPLEX THIO-OXALATES. 63nickelodithio-oxalate, p o h i u m pdladiodithio-oxalate, or potassiumferrodithio-oxalate, the colour of these solutions is discharged.It was found that approximately four molecules of potassiumcyanide were needed to decolorise one molecule of potassium nickelo-dithieoxdate.Potassium cyanide, however, decomposes cobalti- or rhodiidithio-oxalates only when concentrated.Experiments are in progress with the object of preparing the freeacids and the esters of the above-mentioned complex acids, andalso for preparing similar complex salts derived from thiomalonates,thiosuccinates, and thiocarbonates, with the view of tracing arelationship between the constitution, colour, and stability of thesecomplex compounds.As large quantities of potassium dithio-oxalate were needed forthis investigation, experiments were made with the object of deter-mining the best conditions for the preparation of this salt.As ethyland phenyl mercaptans are objectionable on account of their odours,amyl dithio-oxalate was prepared by the action of amyl mercaptanon oxalyl chloride. It is a pale yellow oil, boiling at 205O/20 mm.From this ester the potassium salt is produced by saponificationwith alcoholic potassium hydrosulphide, the best yield beingobtained when the calculated quantities of a normal solution ofpotassium hydrosulphide and amyl ester are gently warmed togetherfor a short time.Sodium dithio-oxalate, (COSNa),, which had not been previouslyobtained, was prepaed by the action of alcoholic sodium hydro-sulphide on amyl dithio-oxalate.When m y 1 dithio-oxalate is warmed with a slight excess ofN-alcoholic sodium hydrosulphide solution, saponification takesplace, and the sodium salt separates on keeping.It was recrys-tallised from hot alcohol, and separated as colourless plates. Asolution of this salt gives the same characteristic colour as thepotassium salt when mixed with a solution of a nickel salt:0.1570 gave 0.1340 N+SO,. Na=26'60.(COSNa), requires Na=26.72 per cent.With the view of obtaining barium dithio-oxalate, cold con-centrated solutions of barium chloride and potassium dithio-oxalatewere mixed. A white precipitate separated, but, contrary toexpectation, this precipitate wits found to be a mixture of bariumsulphide and barium oxdate.A niline di t hio-oxala t e, (GO S- NH,.C6H&, separates in orange-coloured plates when cold aqueous solutions of aniline hydwchloride and potassium dithio-oxdate are mixed. I& solutions i64 ROBINSON AND JONES : COMPLEX THIO-OXALATES.warm water, cold alcohol, or acetone undergo rapid decompositionwith evolution of hydrogen sulphide and separation of oxanilide.Owing to the extreme ease with which this salt decomposes, itcould not be prepared pure. Freshly prepared aqueous solutionsof salt give the characteristic nickelodithisoxalate colour on admix-ture with it solution of a nickel salt, but no colour is developedif the solution of the aniline salt is allowed to remain for some timebefore adding the nickel salt.Potassium nickelodithio-oxalte, K2(COS),Ni, separates as ablack, crystalline precipitate when equal weights of nickel chlorideand potassium dithieoxalate in concentrated aqueous solutions axemixed. This salt crystallises from hot water in dark red octahedra.As the composition of this salt is of fundamental importance, itwas analped several times.The results obtained for carbon, hydrogen, and sulphur agreeso clmly with those given in the former paper (Zoc.cit., p. 1908)that the determination of the percentage of nickel only need begiven here to supplement the results already published:0,4200 gave 0.0870 NiO. Ni=16.2.E,(COS),Ni requires Ni = 16.8 per cent.Sometimes it wits found that potassium nickelodithio-oxalateseparated it5 needles, whilst at other times it separated as octahedrafrom aqueous solutions.Both forms had the same composition,and on investigation this was found to be a case of dimorphism.On cooling a solution of potasium nickelodithisoxalate to 22*,octahedra only separate, but if the solution is cooled rapidly toloc, needles separate. Above 20°, needles in contact with waterchange slowly into octahedra, whilst if theoctahedra are kept under water in an icechamber for several hours, they change slowlyinto needles.The transition temperature is approxi-mately 20'.Mr. A. Hutchinson has kindly provided thefollowing report on the octahedral form basedon meamrements made by Mr. A. F. Halli-mond.'' Crystal system : Oblique. a : b : c =/3 = 70'56'. 1.7637 : 1 : 2.8664.and s{ T11) large, A { 1001 small.Forms observed : pjlll Thesmall black crystals are about 3 mm. in length, and belong to theholohedra'l subclass oE the oblique system. The habit is pyramidal,p and J' being equally developed. This is shown in the figure,which is a plan on the plane of symmetryROBINSON AND JONES : COMPLEX THIO-OXALATES. 65The following angles were observed :Angle No. ofmeasured. measurements. LimitsPS =(ill) : (iq 16 58Q26i-5a052fps' = ( i l l ) : (111) 14 34 30 -34 50SRf =(111) : (ill) 7 61 16 -61 23pp' = ( i l l ) : (111) 8 76 30 -77 42Ap=(lOO) : (111) 4 55 36-56 5=(loo) : (iii) 4 65 38-65 40Mean58O35'34 4461 194 *77 112 77O2.1'55 52 55 464observed. Calculated.fY65 364 65 384Cleavage : A {loo} perfect, B(O1O) imperfect.The specific gravity is 2.132 a t 18'4O (compared with water at4O).I n very thin flakes the crystals are transparent and transmitbrownish-red light. The extinction of a cleavage flake paraillel toA was found to be parallel. to B, and a flake parallel to B appearedto extinguish parallel to the edge AB. The crystals are verystrongly pleochroic, vibrations parallel to the edge AB being totallyabsorbed. I f the light is vibrating perpendicular to A {loo}, onlydeep red is transmitted; pale brown is transmitted if the vibrationsare perpendicular to B. An approximate value of 1.54 was obtainedby the immersion method for the index of refraction of lightvibrat-ing perpendicular to A ."The potassium salt is too sparingly soluble in cold water to allowof trustworthy determinations of its molecular weight in solutionto be made.The electrical conductivity, however, shows that itionises into three ions.EZectm'cal Conductiuit y of Potassium Nickelodithio-oxdat e inA peous Solution.Concentration . . . .. , .. . . . . . . . . . .Molecular conductivity ...... 217.3 227.4 265.1 276'0M/32 MI64 MI1024 MI2048If E , and E,, be the equivalent conductivities at dilutionsH/32 and M/1024 per litre, thenThe salt is therefore derived from a dibasic acid, for whichWith increasing dilution a constant value for the conductivitycannot be obtained.Barium nickelodithio-oxahzte, Ba(CtOS)INi,4H,0, is sparinglysoluble in cold water, and is precipitated on mixing solutions ofVOL.CI. 66 ROBINSON AND JONf6 : COMPLEX THIO-OXALATES.barium chloride and potassium nickelodithio-oxalate. It sepaxateson cooling hot aqueous solutions in black, iridescent needles:0.7780 gave 0.3485 BaSO,.0.4225 gave 0.0640 NiO.0.5060, dried in a desiccator for two days, gave 0.1680 C02 amd(This result indicates that the salt still retained some water.)Ba(COS),Ni,4H20 requires Ba=26*9; S=25.2; Ni=11*6;C = 9.44 ; H,O = 14.10 per cent.Lead Ns'ckelodit~Lzo-oxuEate, Pb(COS),Ni,2HZO. - This saltseparates in lustrous needles when solutions of lead acetate andpotassium nickelodithi+oxala.te are mixed. It is almost insolublein cold water, and decomposes on boiling with sepalation of leadsulphide :Ba = 26.33.Total BaSO, = 1.395. S = 24%.Ni = 11.9.0'0760 -0.C = 9.05 ; H,O = 15.0.0.6092 gave 0.1935 GO, and 0'0435 H,O.0,5220 ,, 0.2860 PbSO, and 0.6780 BaSO,. Pb=37.4;c'= 8.63 ; H,O = 7.1.S = 23.3.Pb(C0S),Ni,2H2O requires C! = 8.8 ; H,O = 6.6 ; P b = 38.2 ;S=23*6 per cent.Ammonium nickelodithio-oxalate, (NH4)2(COS),Ni,4H,0, wasprepared by mixing hot concentrated solutions containingequivalent quantities of ammonium sulphate and barium nickel+dithio-oxalate. After filtering off the barium sulphate, the remainingsolution on evaporation yields the ammonium nickelodithboxalatein beautiful, lustrous, almost black needles.On boiling with potassium hydroxide solution, 1.15 gave offammonia which neutralised 5.57 C.C. of N-sulphuric acid.NH, = 8.71.0.5955 gave 0.2505 CO, and 0-202 H,O.The residue from the combustion was reduced, ignited, and gave0*1090 NiO.Ni = 14.4.C=1lo5; H=3*77.(NH4),(C~OS),Ni,4HzO requires NH, = 8.84 ; C = 11.79 ; H = 3.9 ;Ni = 14.5 per cent.k i o l e d a r Weight of Ammonium Nickelodithio-oxalate.0.192, in 25 C.C. of water, gave A t - O ' l O . M.W.=138*2, butHence it appears that the salt has dissociated into three ions.(NH4)2(COS)4Ni,4.H.,0 require5 407ROBINSON AND JONES : COMPLEX THIO-OXALATES. 67Conductivity of Ammonium Nickelodithio-oxalate in AqueousSOl'llti07L.Concentration ............... 41/32 ill11024Molecular conductivity.. . . . . 227 276E1oar-E32 ~ - -- = 2 7 w - 2 2 7 1 2 = 2.4.10 l oThe salt is therefore derived from a dibasic acid.At greater dilutions the conductivity incremes still more, andwithin the limits of practical determination a constant value cannotbe reached.Sodium Izickelodithio-oxdate, Na,(COS)4Ni,24H,0, was preparedby mixing concentrated solutions of sodium dithio-oxalate andnickel chloride.The sparingly soluble sodium nickelodithio-oxalateseparates in black prisms, which do not exhibit such a high lustreas the other salts:0.2750 gave 0.1255 GO, and 0*0310 H,O. C = 12.44; H,O = 11.3.N~(COS),NiY24H,O requires C= 12.3 ; HBO= 11.5 per cent.When merctiric chloride in excm is added to a solution ofpotassium nickelodithio-oxalate, the mercury salt is not obtained,but the solution is decolorised, and a yellow precipitate is formed,which was found to be a mixture of mercury sulphide with mercuryoxalate.When excess of mercuric chloride is avoided, a coloured pre-cipitate, probably of mercury nickelodithio-oxalate, is f orrned, andgradually decomposes, giving the yellow solid and carbon monoxide.The nickel, cobalt, and silver salts of nickelodithio-oxalic aciddecompose on keeping, with formation of a sulphide of the heavymetal.I n fact, with the exception of lead, few salts of a metalwhich yields am insoluble sulphide are sufficiently stable to beprepared in the ordinary way.Aniline n~ckeloclit~io-oxnlate, (C,H,*NH3),(COS),Ni, separates asa reddish-brown, microcrystalline powder when a solution of anilinehydrochloride is adzed to one of potassium nickelodithio-oxalate :C = 39.0 ; 0.3200 gave 0.4576 CO,, 0.0930 H,O, and 0.0505 NiO.0.2950 gave 0.5590 BaSO,.22500 ,, 11.4 C.C.N, at Oo and 760 mm. N=5-72.H= 3.24 ; Ni = 12.4.S= 26.0.(C,H,*NH,),(COS),Ni requires C = 39.4 ; E= 3.3 ; Ni = 12.1 ;S=26*28; N=5.75 per cent.This salt is so insoluble in water containing an excess of anilinehydrochloride that the supernatant liquid is colourless; it wasthought therefore that its formation might be utilised in theP 68 RORIKSON AND JONES : COMPLEX TBIO-OXALATES.estimation of aniline. Fairly accurate results were obtained withconcentrated solutions, but at greater dilutions the method wasnot a, success, probably owing to hydrolysis of the salt.Thermal Decomposition of Aniline Nickelodithio-oxalate.When aniline nickelodithio+oxala;te is heated, decompositionbegins a t 180°, and is completed slowly a t 210°.Among theproducts of this decomposition, oxanilide, aniline, hydrogensulphide, and carbon monoxide were identified, whilst the residuecontained only nickel and sulphur.An attempt was made to estimate these decomposition productswith the abject of ascertaining the mode of decomposition, and,if possible, of obtaining some insight into the constitution of thesalt. A weighed quantity of the salt wadj heated to 210° in a hardglass tube fitted to an air condenser.The carbon monoxide and hydrogen sulphide escaped, and thecontents of the tube and condenser were extracted with hotbenzene, which dissolved both the aniline and the oxanilide. Thisbenzene solution was shaken with a solution of hydrochloric acid.The aqueous layer containing aniline hydrochloride was separatedfrom the benzene layer containing the oxanilide. Both solutionswere evaporated to dryness, and the residues weighed.It was only possible to get approximate values for the amountsof aniline and oxanilide, partly on account of the loss of anilinedue t o hydrolysis, and partly on account of the slight solubility ofoxanilide in benzene.Experiment 1 .4 ' 8 1 3 gave 0.241 aniline hydrochloride and 0.134oxanilide. Hence aniline per gram-molecule = 103 grams ;oxanilide = 80 grams.Experiment ZZ.-0*860 gave 0.250 aniline hydrochloride and0.1 60 oxanilide. Hence aniline per gram-molecule = 99 grams ;oxanilide = 89 grams.Experiment IZZ.-1*34 gave 0.334 aniline hydrochloride and0.278 oxanilide.Hence aniline per gram-molecule = 93 grams;oxanilide = 109 grams.The gases evolved when a weighed quantity of the salt was heatedin a vacuum were collected by means of a Topler pump, and thevolume of gas was measured before and after treatment with con-centrated aqueous potassium hydroxide solution.The residual gas was carbon monoxide, whilst the gas absorbedby the alkali was hydrogen sulphide, with pomibly carbonylsulphideROBINSON AND JONES : COMPLEX 'I'HIO-OXALBTES. 69Experimemt Z.-0*198 gave 44.5 C.C. at 18O and 756 mm., ofwhich 18.7 C.C. were carbon monoxide.Total gasCarbon monoxide= 44.3 ,, 9 , Y 9Residue = 0.043 =I 110.5 grams, 39 > 9= 108.5 litres per gram-molecule of salt.Experiment I1.-Total gasCarbon monoxide== 43.0 ,, Y, 9 9Residue =106*0 grams 9 1 99= 106.2 litres per gram-moleculo of salt,Experiment 211.-Total gasCarbon monoxide= 43.5 ,, ,, 9 7Residue = 106.0 grams 9 9 9 ,= 110.0 litres per gram-molecule of salt,From these results, which a;re fairly consistent with each other,it appears that each molecule of aniline nickelodithio-oxalate givestwo molecules of carbon monoxide and five molecules of hydrogensulphide or of a mixture of this gas with carbonyl sulphide.Itwits found impossible to decide whether both these gases werepresent by liquefaction and fractional distillation, but the behaviourof the gas towards an aqueous solution of lead acetate indicatedthat some carbonyl sulphide wits present.In order to ascertain if carbonyl sulphide was present, and todetermine its amount, ~?~enyltrimethyl~m~onium nickelodithio-o x d a t e , [~6~,*N(CH,),],(COS),Ni, was prepared by mixing solutionsof the iodide of the organic base with the potassium salt of theacid, when it separated in diamond-shaped, red plates, showing aremarkably high lustre, which melted and decomposed at215-216':0.2030 gave 0.3430 CO, and 0.0884 H,O.[C,H,*N(CH,),],(~OS),Ni requirm c = 46.2 ;A weighed quantity of this salt was heated to about 250° in astream of dry nitrogen, the evolved gases were passed through aU-tube cooled by ice, in order to condense dimethyl sulphide, andthen into a receiver cooled in liquid air.I n this way the carbonyl sulphide was solidified, whilst thenitrogen and most of the carbon monoxide escaped; a small amountof carbon monoxide, however, appears t o be retained by the solidoxysulphide.The cooled receiver was then connected to a gasburette, and by allowing the temperature to rise slowly the Solidifiedgas vaporised, and was swept into the burette by a stream ofnitrogen.C = 46.1 ;* H = 4.84.= 4.91 per cent70 ROBINSON AND JONES : COMPLEX THIO-OXALATES.The volume of gas was measured before and after treatment withaqueous potassium hydroxide ; the contraction represents the volumeof carbonyl sulphide Fvolved from the phenyltrimethylammoniumsalt. Fro'm this the number of litres of carbonyl sulphide evolvedfrom a gram-molecule of phenyltrimethylammonium nickelodithio-oxalabe is calculated.It seems reasonable t o assume that the gram-molecule of theaniline salt gives the same, amount of carbonyl sulphide.Experiment Z.-0*412 gave 16.3 C.C. COS, corrected to Oo and760 mm.Hence one gram-molecule of the salt gives 22.6 litresc o s .Experiment ZZ.-0-405 gave 15.6 C.C. COS, corrected to Oo and760 mm. Hence one gram-molecule of the salt giverr, 22.0 litres COS.Therefore one gram-molecule of the salt yields one gram-moleculeof carbonyl sulphide.The results obtained in the above experiments indicate that thedecomposition of aniline nickeldithi6oxalate is best representedby the equation:2Ni( COS),( C?6H5*NH3)2 =Ni,S, + 4C10 + 200S+ 3H2S + 2C6H5*NH2 + (CO*NH*C,H,),.Products of Decomposition per Gram-molecule of Salt.Found. Calculated .Carbon monoxide ...........43 -8 litres 44.4 litresCarbonyl sulphide ............ 22 -3 , , 22'2 ,,Hydrogen sulphide.. .......... 42 '0 , , 33.3 ,,Oxanilide ........................ 109 '0 , , 120.0 ,,Aniline ........................... 97 -0 grams 93'0 grainsNickel sulphide ............... 110.6 , , 103.0 ,,The only discrepancy is observed in the amount of hydrogensulphide foufd, and at8 this value is obtained by differences, thismay be due t o the decomposition of some of the carbonyl sulphideinto hydrogen sulphide and carbon dioxide by moisture.A very large number of organic bases, such it5 aromatic amines,quinoline derivatives, and alkaloids, give crystalline nickelodithio-oxalates which are very sparingly soluble in water.Of these, theguanidine salt is the most striking, as it is very sparingly solublein cold water, and separates from hot water in long, black, lustrousneedles.Nick: e I o di t hio- o zalic A c i d .It seemed reasonable to suppose that by mixing sulphuric acidand barium nickelodithio-oxalate in equivalent. quantities, freenickelodithio oxalic acid would be obtained in solution.However, on evaporation of the resulting solution, after removaROBINSON AND JONES : COMPLEX THIO-OXALATES. 71of the barium sulphate, decomposition with evolution of hydrogensulphids and separation of nickel malate took place.The behaviour of this acid in solution can, however, be followedby measuring the electrical conductivity.A solution of barium nickelodithio-oxalic was made, and itselectrical conductivity measured; 10 C.C.of this solution were mixedwith 10 C.C. of an equivalent sulphuric acid solution. The resultingsolution, neglecting the barium sulphate which is precipitated,should be a solution of nickelodithicmxalic acid.Its con8uctivity was measured, and was found to be nearly fourtimes that of an equivalent solution of the barium salt. Moreover,the conductivity of this acid increased with dilution, but decreasedsteadily on keeping, which would be expected if the acid decorn-posed into insoluble substances, such as nickel oxalate, sulphur, andcarbon monoxide, or into such a feeble electrolyte aa hydrogensulphide.Strength of solution of barium salt ... M/361 MI722Molecular oonductivity ..................181 196oxalic acid.. ............................... MI722 ikq1444Molecular conductivity .................. 736 767A comparison of the conductivity of this acid with that ofequivalent solutions of hydrochloric and sulphuric acids shows thatit is a comparatively strong acid, with a conductivity approximatelyequal to that of sulphuric acid. (The molecular conductivity ofsulphuric acid a t a dilution of 722 litres is 742.)Strength of solution of nickclodithio-PaEladiodWiio-oxdat es.Po t assium p n l l a ~ ~ o d i t h i o - o x ~ ~ t e, K2(C0 S),Pd .-W hen a solutionof palladium chloride is added to a concentrated solution ofpotassium dithio-oxalate, a yellow, crystalline precipitate separates.This salt is deposited from a hot aqueous solution as yellow,fluorescent prisms :0.3240 gave 0.1280 cy),.0-3100 ,, 0.6970 BaSO,.S=30-8.0,4885 ,, 0.1250 P d and 0.5870 K,Pta,. K= 19.2 ; Pd= 25.6.K2(COS),Pd requires C = 11.3 ; K = 18.5 ; S = 30.5 ;Pd = 25.0 per cent.Barium pdlndiodithw-oxalate, Ba(COS),Pd,3H20, was preparedby adding barium chloride solution to a, solution of the potassiumsalt.C= 10.8.It separates in orange-coloured needles :0'2915 gave 0.0960 CO, and 0.0295 H,O. C=8.3; H,O=10*1.Ba(COS)*Pd,3H20 requires C = 8.95 ; H,O = 10.0 per cent73 ROBINSON AND JONES : COMPLEX THIO-OXALATES.A nilime paZZadiod&%io-oxaZat e, (C,H,*NH&( CO S),Pd, separatesfrom a solution of potassium palladiodithio-oxalate on addition ofa solution of aniline hydrochloride its a yellow, microcrystallineprecipitate :0-3435 gave 0.4540 CO, and 0.0935 H,O.0.4710 ,, 0.0880 Pd.Pd=18*7.0.2400 ,, 0.4280 BaSO,. S=24.5.(C,H,*NH,),(COS),Pd requires C= 36.7 ; H = 3.06 ; S = 24.4 ;Pd=18-2 per cent.Solutions of palladiodithio-oxalates have an intense yellow colour,which persists at high dilutions, and is probably due to the forma-tion of a complex anion containing palladium. I n agreement withthis we find that the ordinary tests for palladium when appliedt o t.hese solutions fail; thus potassium iodide does not precipitateinsoluble palladium iodide, whilst hydrogen sulphide does not causeseparation of palladium sulphide.This complex acid radicle is fairly stable, as the colour isnot destroyed by dilute mineral acid, but potassium cyanidedecolmises solutions of palladiodithiocoxalates.The followingreactions were examined :Silver Izitrute gives a yellow precipitate, which immediatelydecomposes with evolution of carbon monoxide and formation ofsilver sulphide.Mercuric chloride gives a yellow precipitate which blackens onkeeping.Lead acetGte gives an orangered precipitate which darkens afterkeeping.Nickel chloride causes formation of a moderately soluble brick-rednickel salt.Cobalt chloride causes formation of a fairly soluble cobalt salt.When a solutioii af palladium chloride in excess is added to oneof potassium palladiodithio-oxalate rapid decomposition takes placewith separation of palladium sulphide, so that when preparingpotassium pdadiodithieoxalate it is important to use an excessof thio-oxalate.@= 36.1 ; H = 3.0.Ferrodithio-oxaktes.When a solution of ferrous ammonium sulphate is added to oneof potsssium dithio-oxahate, a brownish-purple colour is developed.This colour is due t o formation of a complex ferrodithieoxalate,but owing to the instability of this substance, ferrous sulphideseparates when solutions of ferrous ammonium sulphate andpotassium dithio-oxdate are mixed, and the isolation of a puresalt proved to be difficult. I f , however, dilute solutions were usedROBINSON AND JONES : COMPLEX THIO-OXALATES. 53it was possible to isolate the sparingly soluble aniline salt by theaddition of aniline hydrochloride to the filtered solution.Aniline f errodithio-oxalate separated in black needles, whichwere collected .rapidly and dried in a vacuum over sulphuric acid.Even when dry, this saJt decomposed slowly, with evolution ofhydrogen sulphide and formation of oxanilide, so that no consistentanalytical results were obtained, but the following serve to establishthe composition of the salt:0.1525 gave 0.2085 CO, and 0-0485 H,O.0.2600 ,, 13 C.C.N, a t 23O and 763 mm. N=5*67.0.1880 ,, 0.3780 BaSO,. S=27.6.C= 37-35 ; H = 3.53.(C,H,*NH3)2(COS),Fe,H,0 requires C = 38-2 ; H = 3.58; S = 25.5 ;N = 5-77 per cent.Cobaltidithio-oxalat es.When solutions of cobalt salts and potassium dithio-oxalate aremixed, an intense reddish-brown colour results, and this colouris recognisable a t dilutions as great as one part of cobalt in40,000,000 parts of water.This colour, unlike the corresponding colour for nickel, is notdischarged by potassium cyanide or by boiling with moderatelystrong hydrochloric acid.The colour is therefore due to theformation of a stable complex cabaltidithio-oxalate.When concentrated solutions of equal weights of cobalt chlorideand potassium dithio-oxalate are mixed, an intense reddish-browncolour is developed, and much cobalt sulphide separates. Thesolution was filtered, and to the filtrate barium chloride solutionwas added. A reddish-brown, microcrystalline precipitate separated.This was dissolved in hot water, and on cooling very minute,reddish-brown needles separated.Analysis showed this salt to be potassium barium cobaltidithio-oxalat e, BaK(CY)S)6Co,4H,0.The potassium was estimated by decomposing the salt by nitricacid; the barium was then removed as barium sulphate, thesolution was made alkaline by ammonia, and the cobalt removedas cobalt sulphide.The liquid was then evaporated to dryness,ignited, and the potassium in the residue estimated as platini-chloride, but the results obtained were always low:2.1860 gave 0.7735 BaSO, and 0.1890 Co. Ba=20'8; Co=8.64.0.3545 ,, 0.7385 BaSO,. 8=28-6.0.6515 ,, 0.2655 C'O, and 0.0715 H,O. C = l l * l ; H20=11'0.0.7485 barium salt gave 0.231 K,PtCl,. K=4.95.BaK(CTOS)6Co,4H20 requires C = 10.8 ; H,O = 10.8 ; S = 28.78 ;Ba=20.53; C0=8*7; K=5*83 per cent74 ROBINSON AND JONES : COMPLEX TH10-OXALATES.Potassium cobait%dithio-oxaZnte, K,(~OS)6Co,2H,0, was preparedby mixing solutions of equivdent quantities of potassium sulphateand barium potassium cobaltidithieoxalate, removing the bariumsulphate, and evaporating the filtrate until the tripotassium saltsepara-ted in very dark brown, stumpy prisms.This ‘was recrystal-lised from hot water:0.5015 gave 0’2270 CO, and 0.0330 H,O. C = 12.35 ; H,O = 6.58.0.6890 ,, 0.93’70 K,PtCl, and 0-0712 Co. K=21*4; Co=10.34.0*5000 ,, 1.2120 BaSO,. S=33*3.K3(CO~),Co,2~,0 requires K = 20.45 ; C = 12.58 ; S= 33-54 ;Co= i0.31; H,O= 6-29 per cent.The behaviour of cobaltidithio-oxalates in solution was studiedby meam of the freezing point and conductivity of solutions inthe case of the corresponding nickel compounds:0-4140 potassium salt in 20 C.C.water gave At - 0‘22O. M.W. = 167.1*C300 in 40 C.C. water gave At -0’37O. M.W. = 172.Average iW.TA7. = 169.5.Ks(C08)&0,2H,O requires M.W. =572.Hence the salt appears to ionise, giving four ions-3K’ andco( co 8)6”’.Conductivity Experiments.Molecular conductivity.. ....... 306 330’6 360 400Dilution ........................... MI32 MI64 MI128 M/1024Hence :Cobaltidithiocrxalic acid is theref ore tribaic.-4 n&me cob altidit hb-oxaht e, (c,H,*NH,),( COS)6,2H,0, separatesas a dark reddish-brown, crystalline precipitate on mixing concen-trated solutions of aniline hydrochloride and potassium cobalti-dithimxalate. The sparingly soluble salt separates from hot waterin small, dark brown octahedra:C=39*3;H=3*51; Co=7-59.0.3765 gave 0.5425 CiO,, 0.1190 H,O, and 0*0300 Co.0-3235 gave 15-4 C.C.N, a t 15O and 779 mm. N=5.75.0.3030 ,, 0.5800 BaSO,. S-26.28.(~6H,*NH3)3(COS),Co,2H20 requires C = 39.08 ; H = 3.80 ;Co= 8-00 ; N = 5.70 ; S = 26.0 per cent.I f to a solution of potassium cobaltidithieoxalate a solution ofquinine sulphate is added, quinine cobaltidithieoxalate separates asa brownish-yellow, microcrystalline precipitate. This salt is app*rently quite insoluble in water, so that ita formation might be usedto est,imate quinineROBINSON AND JONES : COMPLEX THIO-OXACATES. 7.5Lead, silver, nickel, and cobalt salts of cobaltidithio-oxalic acidwere not isolated, as they decompose immediately after formationwith deposition of sulphides and evolution of carbon monoxide, and,as in the case of nickelodithio-oxalic acid, only those metals whichdo not form insoluble sulphides give stable salts.The thermal decompmition of aniline cobaltidithicmxalate wasexamined in the manner already described in the case of anilinenickelodithio-oxalat e.This salt decomposes a t about 200°, giving oxanilide, aniline,hydrogen sulphide, carbon monoxide, presumably carbonylsulphide, and a sulphide of cobalt.I.0.1620 gave 38.6 C.C. gas at 1 7 O and 754 mm.After KOH absorption, 13.3 C.C. gas at 17O and 754 mm.Hence :164 litres gas per gram-molecule of salt.55.6 litres carbon monoxide per gram-molecule of salt.11. 0-5330 gave 0.079 residue = 109 grams per gram-molecule111. 162 litres total gas per gram-molecule.IV.161.8 litres total gas per gram-molecule.V. 0.6380 gave 0-1430 oxanilide and 0.1320 milina hydro-of salt.55.7 litres carbon monoxide per gram-molecule.54.4 litres carbon monoxide per gram-molecule.chloride.Hence :150 grams aniline per gram-molecule.165 ,, oxanilide per gram-molecule.It was not found possible to estimate carbonyl sulphide in thiscase as the phenyltrimethylammonium salt is very soluble, andwas not obtained pure.The equation which represents the decomposition of the anilinesalt most nearly is:~ C O ( COS)6( C6H,*NH,),,2H20 =2H,O + (CO.NH*C,H,Sd+4C6H,*NI-I, I- 4118 + 5COS + 5CO + C%S,.Products of Decompositio?z per Gram-molecule of Salt.Found. Calculated.Carbon monoxide ........................ 55.6 litres 55.5 litresHydrogen sulphide and rerbonj 1sulphide ............................... 107'4 ,. 99.9 ),Aniline .................................... 150.0 grams 186.0 gramsOxanilide ................................ 165 -0 , ) 120.0 ),Cobalt sulphide.. ........................ 109.0 , , 107~0 ,76 ROBINSON AND JONES : COMPLEX THIO-OXALATES.Rhodiidithio-oxalates.On adding a solution of sodium rhodiichloride to a concentratedsolution of potassium dithio-oxalate no apparent change takesplace; the addition of barium chloride to the mixed solutions doesnot cause separatioE of barium rhodiidithio-oxalate. On warmingthe solution becomes orange-coloured, and barium chloride nowcauses separation of a brilliant yellow microcrystalline precipitate.This is soluble in hot water, and separates on cooling as orange-yellow needles of potassium Z, arium rhodiidit h io-oxala t e,KBa(COS),Rh,4E20 :0.2710 gave 0*0870 BaSO,.0.6460 ,, 0.2470 (20, and 0.0680 H,O. C=10.43; H20=10.5.Ba= 18.9.BaK*(COS),Rh,4H20 requires Ba=19*2; C=10m13;H,O=10*12 per cent.A.rLiZine R~odiidit~io-oxalate, (C,H5-NH3),(COS),Rh,H20, separates in orangered needles when a solution of barium rhodiidithiooxalat'e is added t o a solution of aniline hydrochloride:0.2625 gave 0.3610 CO, and 0.0840 H,O.0.2290 ,, 0.4270 BaSO,. S=25*6.C= 37.5 ; H = 3.5.(CE,H,*??H,),(COS),Rh,H,O requires C = 37.7 ; H = 3-40 ;S=25.2 per cent.Solutions of rhodiidithio-oxalates have an intense yellow colour,which persists a t great dilutions.The expenses of this investigation have been partly defrayed bygrants from the Government Grant Committee of the RoyalSociety, for which we are glad to ma.ke this grateful acknowledg-ment. We also desire to record our thanks t o Professor Pope forkindly supplying us with the salts of palladium and rhodium usedi n this work.UNIVERSITY CHEMICAL LABORATORY,CAMBRIDGE
ISSN:0368-1645
DOI:10.1039/CT9120100062
出版商:RSC
年代:1912
数据来源: RSC
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9. |
VIII.—The absorption spectra of quinine, cupreine, 6-methoxyquinoline, and 6-hydroxyquinoline |
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Journal of the Chemical Society, Transactions,
Volume 101,
Issue 1,
1912,
Page 77-81
James Johnston Dobbie,
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摘要:
THE ABSORPTIOX SPECTRA OF QUININE, CUPREINE, ETC. 77VIII.-The Absorption Spectra of Quinine, Cupreine,6-Methoxyquinoline, and 6- Hyciroxyyuinoli?ie.By JAMES JOHNSTON DOBBIE and JOHN JACOB Fox.IN a recent paper (Trans., 1911, 99, 1254) it wm shown that theabsorption spectra of solutions of cinchonine and quinoline arepractically identical, notwithstanding the fact that the molecule ofthe former has a mass more than twice aa great as that of the lather.The object of the investigation described in the present paperwas to ascertain whether a similar relation exists between thespectra of quinine and cupreine, on the one hand, and those of6-methoxy- and 6-hydroxy-quinoline, on the other. It was shownin the paper referred to that the quinine spectra are much morecomplicated than those of cinchonine, and it was assumed that thisgreater complexity is associated with the presence of a methoxy-group in the quinoline half of the molecule, since no other structuraldifference is known t o exist between the two alkaloids.I f thisassumption was justified, it was to be expected that the spectra of6-methoxy- and 6-hydroxy-quinoline would bear as close a relationto those of quinine and cupreine ae, the spectra of quinoline to thespectra of cinchonine. Our anticipations on this point were fullyjustified by the results of our investigation.The structural relations of the four compounds under con-sideration are exhibited by the following formulz:/\N/Cupreine.CH CH6-Methoxyquinoline. 6-Hydroxyquinoline78 nOBBIE AND FOX : THE ABSORPTION SPECTRA OF QUININE,The absorption spectra of sohtions in alcohol of these foursubstances exhibit three bands, the head of the principal bandFIG.1.2321191715ci -5 13;3uh3 5 112% 7$ 50 00 - 935 ' 23 s -4 u 2 216 190s4 17 -3Y B 151311975Upper curves : - Quinine i n alcohol.Lower curves : - 6-Methoxgquinoline in alcohol.being at 1 jh 3050, and of the others at l / h 3500 and l/h 3750respectively. The spectra me almost identical, those of the alkaloids- - - - - - ,, hydrochloride.$ 9 hydrochloride. ---._CUPREINE, 6-METHOXYQUINOLIME, AND 6-HYDROXYQUINOLINE. 7Cdiffering from the others only in showing very slightly greateigeneral absorption .*These spectra are the same as hhe spectra of the alkaloids i nFIG.2.Oscillation frequencies.10050Q, *20 23 10 g8 g ;u -6 24 55 .*5100 2& w-i* uryf;50 42010864Upper curve : Cupreine in abohol.Lower ,, 6-Hyd~oxyquinoli~ne in atcohol.combination with one equivalent of acid. When, however, theamount of acid present is sufficient to combine with both nitrogen* The curves of quinine now published were drawn from photographs of a largernumber of thicknesses of solution than the curves on p. 1260 (loc. c k ) , and there-fore show the shape of the bands more completely. The position and extent of thebands, however, is in no way affected80 THE ABSORPTION SPECTRA OF QUININE, CUPREINE, ETC.atoms of the quinine, the spectrum is similar to that of 6-methoxy-quinoline hydrochloride, although the difference in general absorp-tion is slightly more marked than in the alcoholic solutions.It k clear from an inspection of the curves (Figs.1 and 2) thatthe absorption spectra, of quinine and cupreine, as well as those ofcinchonine, are due to the quinoline portion of the molecule, andare but little affected by the presence of the reduced rings.The 6-hydroxyquinoline used in this work was crystallised severaltimes from alcohol, and melted a t 1 9 4 O . It was converted into6-methoxyquinoline by the action of potassium hydroxide andmethyl iodide under the condit.ions described by Skraup (Monatsh .,1882, 3, 544; 1885, 6, 762). The viscous oil obtained in this waywhen distilled under diminished pressure came over as a faintlyyellow liquid, which turned dark, not only in contact with the air,but also when kept in closed vessels.No difference, however, wasobserved between the spectrum of the N / 1000-solution of the freshlydistilled oil and that of a solution of the same strength after theoil had undergone this change of colour.The range of distillation of 6-methoxyquinoline under varyingpressure is given by the following table:740 mm. ......................... 304-305" (Skraup)310 ,, ........................... 254"220 , , ........................... 236-237"50 ,, ........................... 193" (Skraup)35 , , ........................... 186" ,,The cupreine was obtained from recrystallised cupreine sulphateby treatment with aqueous ammonia and warm ether and sub-sequent crystallisation of the base from absolute aloohol.An interesting point in connexion with these substances is thatthe sulphate of 6-methoxyquinoline is, as Skraup pointed out,strongly fluorwent like quinine sulphate.The accompanying tableshows the limits of absorption obtained from N/ 100-solutions ofthe two sulphates in excess of sulphuric acid:Thickness of Quinine sulpha t e. Me thoxyq uinol ineN/lOO-solution Continuous suIphate. Continuousin mm. absorption to l / h . absorption to l/h.60 2419 248650 2419 248640 2419 251930 2486 251925 2486 251920 2486 251915 248% 251912 2519 25198 2519 25596 2519 2614It is noteworthy that the physiological properties of quinine areThe conclusion appears to he not shared by 6-methoxyquinolineLATENT HEATS OF VAPORISATION OF MIXED LIQUIDS. 81justified that the action of quinine as a febrifuge is not due aloneto the presence of the methoxy-group, the only point in which itdiffers structurally from cinchonine, but to the presence in thesame molecule of this group and the reduced part which is commonto quinine and cinchonine.GOVERNMEST LABORATOKY,LONDON
ISSN:0368-1645
DOI:10.1039/CT9120100077
出版商:RSC
年代:1912
数据来源: RSC
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10. |
IX.—Latent heats of vaporisation of mixed liquids. Part II |
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Journal of the Chemical Society, Transactions,
Volume 101,
Issue 1,
1912,
Page 81-90
Dan Tyrer,
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摘要:
LATENT HEATS OF VAPORISATION OF MIXED LIQUIDS. 81IX.-Latent Heats of Vaporisation of MixedL i p i d s . Part II.By DAN TYRER.IN the previous paper (Trans., 1911, 99, 1633) a method wasdescribed for determining the latent heats of vaporisation of binarymixtures of liquids. It was pointed out that a mixture of twoliquids has two latent heats of vaporisation, which have been termed“ latent heat at constant pressure” and “ latent heat a t constantcomposition,” and denoted by the symbols L, and L, respectively.These two magnitude are simply related in a manner shown asfollows : u’Take a large quantity of the mixhre, the composition of which interms of one of the constituents is x. Let its boiling point under thenormal atmospheric pressure be T. Allow 1 gram of the liquid toevaporate a t the constant temperature 5”.The heat absorbed is(Lp)s. Let the composition of the vapour be y. Separate the vapourfrom the liquid, and compress it completely t o liquid a t the consfanttemperature T. The heat evolved in this process is (L&. Now allowthe 1 gram of liquid thus produced to mix with the original liquid.Let the heat of mixture be H. Clearly we have from the first lawof thermodynamics the relation :( L p ) z = ( L ) V + H .It must be noted that all the terms of this equation refer to theconstant temperature T.Knowing, then, L, and H , we can calculate L, for a liquid thecoinposition of which is the same as the composition of the vapourwhich boils off from a mixture the latent heat of which at constantpressure is L,.I n the present work the compositions of mixed vapours whichare in equilibrium with mixed liquids of known compositions a ttheir boiling points have been determined for the cases previouslyinvestigated, and complete results for two new cases have also beenrecorded.VOL.CI. 82 TYRER : LATENT HEATS OF VAPORISATIONEXPERIMENTAL.Betermination of Composition of Vapaur in Equilibrhm withBoiling Liquid of Know Composition.The metbod employed to determine the composition of the vapourwhich boils off from a mixture of two liquids of known compositionconsists in principle in determining the density of the vapour, andFIG. 1.from this cdculating the composition by asuming the validity ofthe additive law for mixed vapours.The mixture of liquids to be investigated is placed in the vesml A(Fig.l), where it is boiled. The vapour which comes off passes intothe upper portion of A , into the condenser C , and then returns asliquid into A again. A is connected by the tube X and ground-glassjoint to the veFYsel B. B is provided with two taps, T and TI, whichcan be opened or closed from the outside by the aid of springs. ThOF MIXED LIQUIDS. PART 11. 83vessel B is heated in the vapour jacket D to a temperature somewhathigher than the boiling point of the mixture. The v a p u in thejacket I) comes from the liquid boiling in the flask E, a n d afterpassing through D it is condensed in C’, and returns to the boilingflask. In carrying out an experiment, the vessel B containing airis placed in position with the taps T and TI closed.The liquids inA and E are boiled, and after the temperature has become constantthe tap TI is first opened and then T, and B is filled with vapourfrom A by attaching the end of the tube F to an aspirator. After allthe air in B has been diqlaced, the tap T is closed, and after a fewminutes tap T’ is also closed. A sample of the boiling liquid in 4is then taken off in the pipette P for analysis. The temperature inD is read to a tenth of a degree, and the barometric pressure noted.The vessel B is then taken out and cleaned and weighed. Air is thendrawn through it, and it is then again weighed and filled with airat a known temperature and pressure. From the data thus obtainedand from the known volume of B, the density of the mixed vapourfor the particular temperature and pressure recorded can be calcu-lated.The densities of the vapours of the pure constituents aredetermined in a similar manner, and then assuming the additivelaw of mixtures to hold for mixed vapours, the composition of themixture of vapours is easily calculated. The sample of liquid drawnoff in the pipette is transferred to a pyknometer, and its specificvolume determined. From its specific volume its composition canbe calculated in a manner explained in the previous paper. ’ Allthe data required are now obtained. It remains only to plot theexperimental results on squared paper, and to read off from thesmoothed curve values a t even points.AS the amount of liquid in d is fairly large (about 250 c.c.), andthe vapour space above it relatively small, the composition of theliquid will be fairly constant throughout the experiment, and thesample abstracted in the pipette will have the proper composition;also, in the passage of the vapour from the vessel A to B thearrangement of the apparatus obviates any possibility of it condens-ing, which would of course entirely vitiate the results.The vapouris drawn off from as near the surface of the boiling liquid as possible,so as to be sure we are dealing with vapour arising directly fromthe boiling liquid, and not from re-condensed liquid adhering tothe walls of the vessel. I n regard to the assumed validity of theadditive law for mixed vapours, the error of this assumption willbe negligible.With the liquids themselves the additive law is onlyslightly violated, and with the mixed vapours the deviation from thelaw will be still smaller.G 84 TYRER : LATENT HEATS OF VAPORISATIONThe compositions of the vapours in equilibrium with the liquid(1) Carbon tetrachloride and ether.(2) Chloroform and benzene.(3) Carbon tetrachloride and ethyl acetate.(4) Ethyl bromide and benzene.The lhtent heats a t constant pressure in the first two cases wererecorded in the previous paper. From the now measured composi-tions of their mixed vapours, their latent heats at constant composi-tion have been determined. For particulars of the method ofdetermining latent heats at constant pressure the previous paper(loc.cit.) must be consulted.mixtures have been determined in the following cases:El e sul t 8.Latent Heats at Constant Pressure of Mixtures of CarbomTetrachloride and Ethyl AcetateThe carbon tetrachloride used in these experimentsl was obtainedfrom Kahlbaum's pure material by washing repeatedly with water,drying over calcium chloride and phosphoric oxide, and then distil-ling, the first and last portions being rejected; 500 C.C. distilled overwithout the boiling point changing more than 0m070. It had aspecific volume at 23'13O of 0.63002, boiled at 75'92O/745 mm., andhad.a latent heat (at 75'92O) of 47.29 calories. This result for thelatent heat wits calculated from the value 46-85 at 77'75O found inD L previous experiments by the aid of the formula LiK= RTlog -0,'where L is the latent heat, M the molecular weight, D , and D,.thedensities of liquid and vapour respectively at 2' degrees, and R is aconstant.The ethyl acetate was obtained by the further purification ofKahlbaum's pure material. At 23'15O it had a specific volume of1.11495, and b d e d at 76-50°/745 mm.Latent €fea.t of Pure E'thyl Acetate.-Three consecutive deter-minations were made, and the following results obtained :Pressure. Temperature. Latem t heat.755 mm. '76.95" 87'67 calories.747 Y , 76-51 88-21 ,,743 ,¶ 7647 88'02 ) )These results calculated to the temperature 76*50° give as amean value 87-97 calories. Results by other observers are : Ramsayand Maxshall (Phil. Mag., 1896, [v], 41, 38), 88.1; Kahlenberg(J.Physicd Chem., 1901, 5, 215, 284), 90-9; Brown (Trans., 1903,81, 987), 88.37OF MIXED LIQUIDS. PART 11. 85Latent Heats at Constant Pressure of Mixtures.-The resultsgiven in the following table were read off from a smoothed curveof experimental values.Composition of liquid.(Per cent. of CC1,. )0102030405060708090100Temperature ofboiling (745 mm.).76'50"76.0675.5675-1074.74'74.3574.0774'1074-3474'8975'92Latent heat st constantpressure.87-97 calories.83.70 ) )79.60 ,,75.45 ) )71'35 ),67'35 ,)6325 ,,59-20 ,,55'22 ),47.29 ), 51 20 2 ) ,Latent He&s at Constant Pressure of Mixtuyes of Ethyl Bromideand Benzene.The ethyl bromide used in these experiments was prepared byadding bromine to a mixture of alcohol and red phosphorus.Tofree it from ether, which appeared t o be the chief impurity, it wasboiled, and the vapour passed through a slightly acid solution ofpotassium permanganate at looo. It was then washed, dried overcalcium chloride and phosphoric oxide, and fractionated. About700 C.C. distilled over without the boiling point changing more than0.15O. It hapd a'specific volume of 0.69163 a t 25O, and boiled at38*38O/760 mm.The pure benzene was the same as that used in the previousexperiments described in the first paper.Latent Heat of Pure Ethyl Bromide.-Three experiments gavethe results:'Pressure. Temperature. Latent heat.749 mm. 37.98" 59.70 calories.749 ¶ > 38 *02 59-89 ,)761 9 9 38-42 60.05 ?,Mean result at 38*38"/760 mm.is 59 88 calories.Wirtz ( A m . Phys. Chem., 1890, 40, [iii], 438) obtained theresult 60.37.Latent Keats of Mixtures at Cohmtant Pressure.-The resultsgiven in the following table were read off from a smoothed curve ofexperimental results 86 TYRZR : L9TENT HEATS OF VAPORISATIONComposition of liquid.(Percentage of ethyl bromide).Temperature of boilingat 760 mm.0 80.25"10 74'8620 70.0030 65.3940 60'8450 56.5260 52'5970 48'7880 45.1090 41 4 9100 35'38Latent hcat atconstant pressure.94-3586-6079.8074'169 *966.764.663 .O61-8560.8559.88Composition of the Vapour Roiling off from a Mixture ofKnotwn Composition.The following results have been read from smoothed curves ofexperimental values :Composition of vilponr.ICarbon tetrachlorideand ether.(Percentage ofComposition carbon tetra-of liquid.chloride. )0 010 1-7220 4 *2830 8.040 12-750 18.560 25.470 34.680 47.290 67.8100 100E t h zChloroform Carbon tetrachloride bromideand and ethyl acetate. and benzene.benzene. (Percentage of (Percentage(Percentage of carbon tetra- of ethylchloroform.) chloride. ) bromide.)0 0 015.6 10.7 26.627'2 21 -1 46.840'6 31.2 61 '453 *o 41 2 72 *O65.0 51 '1 80 '475.0 60-4 8 6 483-0 70.4 91.090.0 80'4 94'696'1 90.2 97 -6100 100 100Latent Heats at Cor&stmt Composition.From the foregoing results we can calculate by aid of the equation(LP)% = (Lc)y + H the latent heats at constant composition.We must,however, know H , the heat of mixture. Now with normal liquidsthe heat developed on mixing is very small, and possibly negligible,but as this was not certain, a few rough experiments were madeto test it.In the case of carbon tetrachloride and ethyl itcetate the composi-tion of the vapour is so near to that of the liquid that the heat ofmixture H is almost immeasurably small. H , it must be remem-bered, is the heat developed when 1 gram of liquid, the compositionof which is the same as the composition of the vapour boiling offfrom a large quantity of a mixture of known composition, is addedto this latter large mass of liquid. The value of A in the case oOF MIXED LIQIJIDS. PART 11.87carbon tetrachloride and ethyl acetate is less than 0.01 calorie.To about 150 C.C. of a mixture of chloroform and benzene containing49 per cent. of the former were added 20 C.C. of a mixture containing64 per cent. of chloroform, which is approximately in the samepropbrtion as the compositions of liquid and vapour. The total risein temperature was only 0*032O, and calculating from the knownspecific heat of the mixture, the approximate value of H was foundto be 0.08 calorie. In another experiment €€ was found to be about0.12 caiorie. In this case, therefore, we caa consider H to benegligible. In a similar manner it has been proved that €8 can bedisregarded as negligibly small in the other two cams. We cantherefore write the above equation :( M Z .= (Lc)il.By plotting the values of (Lp)z against the compositions y, andreading off from the curve, values for L, a t even points, the followingtables of results have been obtained:Carbon Tetrachiloride and Ether. YComposition.(Percentage of carbontetrachloride.)0102030405060708090100Ternpera-ture.34.75"41-3544.8448'9853'0957-1665'5469-7373.7077-7661 '44Latent heat atconstant composition.Calories.86'4483 -179-475 -771 -968.364.660-656-551 -946-86Chloroform and Benzene.Composition.(Percentage ofchloroform. )0102030405060708090100Tempera-ture.80-65"79.8679.0378'1377.1575.9574'6072.8470'4867-0061-45Latent heat a tconstant composition.Calories.94-3591-187-984-651 '478.275-071 *668'364.459 *288 TYHER : LATENT HEATS OF VAPOKlSAl'lONCarbon Il'etrachloride and Ethyl Acetate.Composition.Latent heat at(Percentage of Tempera- constant composition.carbon tetrachloride. ) ture. Calories.0 76.50" 87'9710 76-05. 84'1020 75.58 80.0530 75.12 75.9540 74.72 71-9550 74'35 67 '9060 74-10 63-7570 74-10 59.6080 74-29 55-5090 74'83 51'40100 75.92 47 *29Ethyl Bromide andComposition.(Percertage ofethyl bromide. ).0102030405060708090100Tempera-ture.80.25"78.3376.3074'1371.7669-1065-8661 '7656-7249-9038.38Ben2 en e.Latent heat atconstant composition.Calories.94'3591-688 '685.381.978.374.670.967 '163.559.88Discussion of Results.Tha latent heat of a mixture at constant pressure does not appearto bear any simple relation t o the composition. It is not by anymeans an additive property, an, might have been expected. Thisconclusion has already been established in the cases previouslyinvestigated, and the results for the two fresh cases investigated inthe present work support this conclusion.In regar'd to the latent heat a t constant composition, this appearsto approximate clmely to a linear function of the composition.Thisis shown graphically by the curves in the figure. It will be observedthat with the exception of the line for carbon tetrachloride'andether, which is slightly curved, the lines are practically straight.Theethyl bromide + benzene and the benzene.+ chloroform lines are justa little curved at one extremity.We may therefore regard the latent heat of a liquid mixturea t constant composition as approximately a linear function of thecomposition.The well known relation of Trouton:L'- -- constant, OF MIXED LIQUIDS. PART 11. 89where L is the latent heat, M the molecular weight, and T theabsolute boiling point, is not applicable, as was shown in theprevious paper, to latent heats of mixtures a t constant pressure,but holds for latent heats at constant composition. For iK theremust be taken the mean molecular weight of the molecules in themixture (see Trans., 1911, 99, 1644).FIG. 2.u 6 u s9590858075706560555045@ 10 20 30 40 50 60 70 80 90 100 %B Composition.AIn the following tables are given values of L a ! / ' calculated fromthis equation :Carbon tetrachloride and ether. Chloroform and benzene.C. M.0 74-0910 78*:?020 82.6530 8 7 . i 340 ' 93.4650 100.4560 107.5370 116.2880 126.5890 138.89100 163.84.LJI1' '20.8120'7020.6520.6220 6120'7820.7720.8120.8720'7920.55_-,C.0102030405060708090100Af.78.0580.9583-8687.2390.6094.5698.52103.24107.96113.67119 -39LCM T'20 .a420.8320.9421.0221 -0621'1921 -2621-3821-4721 -5321.090 LATENT HEATS OF VAPORISATION OF MIXED LIQUIDS.Carbon tetrachloride and ethyl acetate.LCMC.M. T'--0 88'06 22-16 .10 92'59 22-3120 96-92 22-2630 101.67 22.1840 106.91 22.1250 113.67 22.2260 119.21 21.8970 126'49 21.7280 134.70 21.5390 144'40 21.34100 153'84 20.85Ethyl bromide and benzene., .LcMC. kf. 7.78-05 20.8510 80.33 20'9420 82 '94 21'0430 85-32 20.9640 88.05 20-9250 90.97 20.82GO 9448 20-7170 97-41 20 '6380 100 99 20.5590 104-84 20.62100 109.00 20.96As will be observed, the relation holds fairly closely. The valueof L,M/T must, however, vary slightly in those cases for which thepure constituents do not give quite the same constant, as, forexample, in the case of carbon tetrachloride and ethyl acetate.However, we can take as the true value of the constant the meanof the constants for the pure constituents, and the equation:could be used for calculating latent heats of mixtures a t constantcomposition with a fair degree of accuracy. This equation gives theratio L,/T as a linear function of the compmition: - _ - - a + bC,Twhere a and b are constants.The validity of Trouton's equation for mixtures proves thenormality of those mixtures, that is to say, the different moleculesof the liquids retain their individual existence when mixed together,and do not dissociate or associate. With mixtures of associatedliquids, like water and the alcohols, to which it is hoped to extendthese investigations, the above relations will probably not hold, thevalues of Le/ T perhaps showing maxima; or minima.I n conclusion, the author desires to state that a portion of theexpense of this work has been defrayed by a Research Grant fromthe Chemical Swiety, and for which the author expresses his thanks.THE CHEMISTRY LABORATOBIES,THE UNIVERSITY, MANCHESTER
ISSN:0368-1645
DOI:10.1039/CT9120100081
出版商:RSC
年代:1912
数据来源: RSC
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