年代:1906 |
|
|
Volume 89 issue 1
|
|
1. |
Contents pages |
|
Journal of the Chemical Society, Transactions,
Volume 89,
Issue 1,
1906,
Page 001-020
Preview
|
PDF (844KB)
|
|
摘要:
J O U R N A L OF THE CHEMICAL SOCIETY. TRANSACTIONS. H. E. ARMSTRONG, Ph.D., LI,.D., F. R. S. E. C. C. BALY. A. W. CROSBLEY, D.Sc,, Ph.D. BERNARDYER, D.Sc. M. 0. FORSTER, D.Sc., Ph.D., F.R.S. R. MELDOLA, F.R.S. E. J. MILLS, D.Sc., LL.D., F.R.S. SirW. RAMSAY, K.C. R., LL.D., F.R.S. A. SCOTT, D.Sc., F.R.S. W. A. TILDEN, D.Sc., F.R.S. JOHN WADE, D.Sc. &hitorrs : (311. T. MORGAN, D.Sc. J. C. CAIN, D.Sc, Sub- - mitor : A. J. GREENAWAY. 3ssisfant %ub--@:bitJYr : C. H. DEBUH, D.Sc., P1i.D. 1906. Vol. LXXXIX. LONDON: GURNEY & JACKSON, 10, PATERNOSTER ROW. 1906.RICHARD CLAY & SONS, LIMITI~~, RREAD STREET HILL, B.C., AND BUNQAY, SUFFOCK.J O U R N A L H. E. ARMSTRONG, Ph.D., LL.D., E. C. C. BALY. A. W. CROSSLEY, D.Sc., Ph.D. BERNARD DYER, D.Sc. M. 0. FORSTER, D.Sc., Ph.D., F.R.S.P.R.S. OF R. MELDOLA, F.R.S. E. J. MILLS, D.Sc., LL.D., F.R.S. S~~W.RAMSAY,K.C.B.,LL.D.,F.R.S. A. SCOTT, D.Sc., F.R.S. W. A. TILDEN, D.Sc., F.R.S. JOHN WADE, D.Sc. THE CHEMICAL SOCIETY. TRANSACTIONS. @bitma : G. T. MORGAN, D.Sc. J. C. GAIN, D.Sc. Siub-@;bitar : A. J. GREENAWAY. %mistant %dr-&Fbifar : C. H. DESCII, D.Sc., Ph.D. 1906. Vol. LXXXIX. Part I. LONDON GURNEY ‘0: JACKSON, 10, PATERNOSTER ROW. 1906.RICHARD CLAP & SONS, LIMITED, BREAD STREET HILL, E.C., AND BUNOAY, SUFFOLKJ O U R N A L O F THE CHEMICAL SOCIETY. TRANSACTIONS. H. E. ARMSTRONQ, Ph.D., LL.D., E. C. C. BALY. A. W. CROSSLEP, D.Sc., Ph.D. UERNABD DYER, D.Sc. M. 0. FORSTER, D.Sc., Ph.D., F.R.S. F. R. s. R. MELDOLA, F.R.S. E. J. MILLS, D.Sc., LL.D., F.R.S.S~~W.RAMSAY,K.C.B.,LL.D.,F.R.S~ A. SCOTT, D.Sc., F.R.S. W. A. TILDEN, D.Sc., F.R.S. JOHN WADE, D.Sc. Qbifars : G. T. MORGAN, D.Sc. J. C. CAIN, D.Sc. Sub - 6bitor : A. J. GREENAWAY. asr~istarrt Sab-4€bitar : C. H. DESCH, D.Sc., Ph.D. 1906. Vol. LXXXIX. Part 11. LONDON: GURNEY & JACKSON, 10, PATERNOSTER ROW. 1906.RICHARD CLAY & SONS, LIYITED, BUNGAY, SUE’POLK. BREAD STREET HILL, E.C., ANDC O N T E N T S . PAPERS COMMUNICATED TO THE CHEMICAL SOCIETY. PAGE 1.-The Preparation and Reactions of Benzoyl Nitrate. By FRANCIS ERNEST FRANCIS . . 1 11.-The Diazo-derivatives of 1 5- and 1 :8-Benzenesulphonyl- naphthylenediamines. By GILBERT THOMAS MORGAN and FRANCES MARY GORE MICKLETHWAIT . . 4 111.---Azoderivatives of 4 : 6-Dimethylcoumarin. By JOHN THEODORE HEWITT and HERBERT VICTOR MITCHELL .. 13 1V.-Azo-derivatives of 4-Methyl-a-naphthacoumarin. By JOHN THEODORE HEWITT and HERBERT VICTOR MITCHELL . . 17 V.-The Action of Water on Diazo-salts. By JOHN CANNELL CAIN and GEORGE MARSHALL NORMAN . . 19 V1.-The supposed identity of Dihydrolaurolene and Dihydro- isolaurolene with 1 : 1-Dimet hylhexahydrobenzene. ARTHUR WILLIAM CROSSLEY and NORA RENOUF, Salters Research Fellow . . 26 VI1.-The Relation of Position Isomerism to Optical Activity. V. The Rotation of the Menthyl Esters of the Isomeric Dibromobenzoic Acids. By JULIUS BEREND COHEN and ISRAEL HYMAN ZORTMAN . . 47 VII1.-Caro’s Permonosulphuric Acid. By THOMAS SLATER PBICE, D.&. . . 53 1X.-Contributions to the Chemistry of the Amidines. 2-Aminothiazoles and 2-Imino-2 : 3-dihydrothiazoles. 2-Iminotetrahydrothiazoles and 2-Amino 4 : 5-dihydrothi- azoles.By GEORGE YOUNG and SAMUEL IRWIN CROOKES . 59 X.-The Influence of Certain Amphoteric Electrolytes on Amylolytic Action. By JOHN SIMPSON FORD and JOHN MONTEATH GUTHRIE . . 76 XI.-Studies on Optically Active Carbimides. Part 11. The Reactions between GMenthylcarbimide and Alcohols. By ROBERT HOWSON PICKARD, WILLIAM OSWALD LITTLEBURY, By JOHN JOSEPH SUDBOROUGH BS: A.I.C., and ALLEN NEVILLE, B.Sc. . . 93 XI1.-a-Chlorocinnamic Acids. and THOMAS CAMPBELL JAMES . . 105iv CONTENTS. PAGE XIIT.-Some Derivatives of Naphthoylbenzoic Acid and of Naphthacenequinone. By IAN QUILLER ORCHARDSON and CHARLES WEIZMANN . . 115 X1V.-Ethyl P-Naphthoylacetate. By CHARLES WEIZMANN and ERNEST BASIL FALKNER .. 122 XV.-Some New Platinocyanides. By LEONARD ANGELO LEVY and HENRY ARNOTT SISSON . 125 XV1.-Studies in Fermentation. I. The Chemical Dynamics of Alcoholic Fermentation by Yeitst. By ARTHUR SLATOR, Ph.D. . 128 XVI1.-The Slow Combustion of Carbon Disulphide. By NORMAN SMITH . . 142 XVIII. -The Liberation of Tyrosine during Tryptic Proteo- lysis. By ADRIAN JOHN BROWN and EDMUND THEODORE MILLAR . . 145 X1X.-Halogen Derivatives of Substituted Oxamides. By FREDERICK DANIEL CHATTAWAY and WILLIAM HENRY LEWIS. 155 XX.-The Osmotic Pressure of Solutions of Sugar in Mixtures of Ethyl Alcohol and Water. By PERCIVAL SMITH BARLOW. 162 XX1.-The Action of Ammonia and Amines on Diazobenzene Picrate. By OSWALD SILBERRAD, Ph.D., and GODFREY ROTTER, B.Sc. . .167 XXI1.-The Preparation of p-Bistriazobenzene. By OSWALD SILBERRAD, Ph.D., and BERTRAM JAMES SMART . . 170 XXII1.-Studies on Nitrogen Iodide. 111. The Action of Methyl and Benzyl Iodides. and BERTRAM JAMES SMART . . 172 XX1V.-Gradual Decomposition of Ethyl Diazoacetate. By OSWALD SILBERRAD, Ph.D., and CHARLES SMART ROY . . 179 XXV.-Action of Bromine on Benzeneazo-o-nitrophenol. By JOHN THEODORE HEWITT and NORMAN WALKER . . 182 XXV1.-The Condensation of Dimethyldihydroresorcin and of Chloroketodimethyltetrahydrobenzene with Primary Amines. Part I. Monamines.-Ammonia, Aniline, and p-Toluidine. XXVI1.-The Determination of Available Plant Food in Soil by the Use of Weak Acid Solvents. Part 11. By ALFRED DANIEL HALL, M.A., and ARTHUR AMOS, B.A. . . 205 XXVII1.-Studies in the Camphane Series.Part XXI. Benzenediazo-11/-semicarbazinocamphor and its Derivatives. By OSWALD SILBERRAD, Ph.D., By PAUL HAAS, B.Sc., Ph.D. . . 187 By MARTIN ONSLOW FORSTER . . 222CONTENTS. V PAGE XX1X.-Hydroxylamine-ap-disulphonates (Structural Isomerides of Hydroximinosulphates or Hydroxylamine-/3/3-disulphon- ates). By TAMEMASA HACIA . . 240 XXX.-Some Oxidation Products of the Hydroxybenzoic Acids. Part 11. By ARTHUR GEORGE PERKIN, F.R.S. . . 251 XXX1.-Contributions t o the Chemistry of Oxygen Compounds. I. The Compounds of Tertiary Phosphine Oxides with Acids and Salts. By ROBERT HOWSON PICKARD and JOSEPH KENYON . , 262 XXXI1.-A Synthesis of Aldehydes by Grignard’s Reaction. By GORDON WICKHAM MONIER-WILLIAMS . . 273 XXXII1.-The Effect of Constitution on the Rotary Power of Optically Active Nitrogen Compounds.Part I. By MARY BEATRICE THOMAS and HUMPHREY OWEN JONES . . 280 ML 0 XXX1V.-The Critical Temperature and Value of -- of some Carbon Compounds. By JAMES CAMPBELL BROWN, D.Sc. . 311 XXXV.-Some Reactions and New Compounds of Fluorine. By EDMUND BRYDGES RUDHALL PRIDEAUX, M.A., B.Sc. . 316 XXXV1.-Menthyl Benzeuesulphonate and Menthyl Naphthal- ene-P-sulphonate. By THOMAS STEWART PATTERSON and XXXVII. -The Attractive Force of Crystals for Like Molecules JOHN FREW, M.A. . . 333 in Saturated Solutions. By EDWARD SONSTADT . . 339 XXXVII1.-Cuprous Formate. By ANDREA ANGEL. . . 345 XXX1X.-o-Cyanobenzenesulphonic Acid and its Derivatives. By ANDREW JAMIESON WALKER and ELIZABETH SMITH, B.Sc. XL.-Preparation and Properties of Some New Tropeines.By HOOPER ALBERT DICKINSON JOWETT and ARCHIE CECIL OSBORN HANN . . 357 XLL-Studies in Asymmetric Synthesi.s. IV. The Application ’ of Grignard’s Reaction for Asymmetric Synthesis. By ALEXANDER MCKENZIE . . 365 XL1I.-The Resolution of 2:3-Dihydro-3-methylindene-2-carb- oxylic Acid into its Optically Active Isomerides. By ALLEN XLII1.-The Condensation of Dimethyldihydroresorcin and of Chloroke t odimethpl tetrahydroben zene with Primary Amines. Part 11. Diamines.-nz- and p-Phenylenediamine. By PAUL HAAS, D.Sc., Ph.D, . . 387 XL1V.-Silicon Researches. Part X. Silicon Thiocyanate, its Properties and Constitution. By J. EMERSON REYNOLDS . 397 350 NEVILLE, B.Sc. . . 383vi CONTENTS. PAGE XLV.-Studies in the Cnmphane Series. Part XXII.Nitrogen Halides from Camphoryl-$-carbamide. By MARTIN ONSLOW FORSTER and HANS GROSSXANN, Ph.D. . 402 XLV1.-Note on the Application of the Electrolytic Method t o the Estimation of Arsenic in Wall-papers, Fabrics, &c. By THOMAS EDWARD THORPE . . 408 XLVI1.-The Refractive Indices of Crystallising Solutions, with Especial Reference to the Passage from the Metastable to the Labile Condition. By HENRY ALEXANDER MIERS, D.Sc., F.R.S., and FLORENCE ISAAC . . 413 XLVII1.-The Relation of Position Isomerism to Optical Activity. VI. The Rotation of the Menthyl Esters of the Isomeric Chloronitrobenzoic Acids. By JULIUS BEREND COHEN and HENRY PERCY ARMES , . 454 XL1X.-The Action of Light on Benzaldehydephenylhydrazone. By FREDERICK DANIEL CHATTAWAY . . 462 L.-Studies on Optically Active Carbimides.111. The Resolu- tion of u-Phenyl-u’-4-hydroxyphenylethane by means of I-3Tenthylcarbimide. By ROBERT HOWSON PICKARD and WILLIAM OSWALD LITTLEBURY, A.I.C. . . 467 L1.-A Modification of the Volumetric Estimation of Free Acid in the Presence of Iron Salts. By C. CHESTER AHLUM . 4’70 LI1.-Slow Oxidations in the Presence of Moisture. By NORMAN SMITH . . 473 LII1.-Studies in the Acridine Series. Part 111. The Methyl- at ion of Chrysaniline (2-Amino-5-p-aminophenylacridine). By ALBERT ERNEST DUSSTAN and JOHN THEODORE HEWITT . 482 L1V.-The Relation between Absorption Spectra and Chemical Constitution. Part I . The Chemical Reactivity of the Carbonyl Group. By ALFRED WALTER STEWART (Carnegie LV.-The Relation between Absorption Spectra and Chemical Constitution.Part 11. The a-Diketones and Quinones. By EDWARD CHARLES CYRIL BALY and ALFRED WALTER STEWART (Carnegie Research Fellow) . . 502 LV1.-The Relation between Absorption Spectra and Chemical Constitution. Part 111. The Nitroanilines and the Nitro- phenols. By EDWARD CHARLES CYRIL BALY, WALTER HENRY EDWARDS, and ALFRED WALTER STEWART (Carnegie Research Fellow) . 514 LVI1.-The Theory of Alkaline Development, with Notes on the Affinities of Certain Reducing Agents. By SAMUEL EDWARD SHEPPARD , 530 Research Fellow) and EDWARD CHARLES CYRIL BALY . . 489CONTENTS. LVII1.-Fischer’s Salt and its Decomposition by Heat. By PRAFULLA CHANDRA RAY . L1X.-The Constitution and Properties of Acyl Thiocyanates. By JOHN HAWTHORNE LX.-Studies on Comparative Cryoscopy. Part IV.The Hydrocarbons and their Halogen Derivatives in Phenol Solution. By PHILIP WILFRED ROBERTSON . LX1.-The Occurrence of Methane among the Decomposition Products of Certain Nitrogenous Substances as a Source of Error in the Estimation of Nitrogen by the Absolute 3Slethod. By PAUL HAAS, D.Sc., Ph.D. LXI1.-Silver Dioxide and Silver Peroxynibrate. By ED WIN ROY WATSON . LXII1.-Influence of Substituents in the Trinitrobenzene Molecule on the Formation of Additive Compounds with Arylamines. By JOHN JOSEPH SUDBOROUGH and NORMAN PICTON . LX1V.-The Estimation of Carbon in Soils and Kindred Sub- stances. By ALFRED DANIEL HALL, NORMAN HARRY JOHN MILLER, and NUMA MARNU . LXV.-The Electrolysis of Salts of PP-Dimethylglutaric Acid. By JAMES WALKER and JOHN HERFOOT WOOD LXV1.-Bromo- and H ydrox y deriva tives of PPP’P’-Tetramethyl- suberic Acid. By JOHN KERFOOT WOOD .LXVI1.-An 1mpro;-ed Apparatus for Measuring Magnetic Rotations and Obtaining a Sodium Light. By Sir WILLIAM HENRY PERKIN . LXVIIL-The Relation between Absorption Spectra and Chemical Constitution. Part IV. The Reactivity of the Substituted Quinones. By ALFRED WALTER STEWART (Carnegie Research Fellow) and EDWARD CHARLES CYRIL BALY . LXIX.-A Mode of Formation of Aconitic Acid and Citrazinic Acid, and of their Alkyl Derivatives, with Remarks on the Constitution of Aconitic Acid. By HAROLD ROGERSON and JOCELYN FIELD THORPE . LXX.-The Interaction of Well-dried Mixtures of Hydro- carbons and Oxygen. By WILLIAM ARTHUR BONE and GEORGE WILLIAM ANDREW . LXX1.-The Explosive Combustion of Hydrocarbons.By WILLIAM ARTHUR BONE and JULIEN DRUGMAN LXXI1.-The Action of Phenylpropiolyl Chloride on Ketonic Compounds, Part 11. By SIEGFRIED RUHEMANN . . . . vii PAGE 551 556 567 570 578 583 595 598 604 608 618 631 652 660 682.. . V l l l CONTENTS. PAGE LXXII1.-Studies in Asymmetric Syntnesis. V. Asymmetric Syntheses from CBornyl Pyruvate. By ALEXANDER MCKENZIE and HENRY WREN, B.A., B.Sc., Ph.D. . . 688 LXX1V.-Aromatic Sulphonium Bases. By SAMUEL SMILES and ROBERT LE ROSSIGNOL . . 696 LXXV.-Acetyl and Benzoyl Derivatives of Phthnlimide and Phthalamic Acid. By ARTHUR WALSH TITHERLEY and WILLIAN LOKGTON HICKS . . 708 LXXV1.-Some Thio- and Dithio-carbamide Derivatives of Ethyleneaniline and the Ethylenetoluidines. By OLIVER CHARLES MINTY DAVIS .. 713 LXXVI1.-The Rusting of Iron. By GERALD TATTERSALL MOODY . . 720 LXXVII1.-The Dynamic Isomerism of Phloroglucinol. By EDGAR PERCY HEDLEY, A.R.C.Sc.1. . . 730 Annual General Meeting . 735 Presidential Address . . 745 LXX1X.-Condensation of Benzophenone Chloride with a- and P-Naphthols. By GEORGE WILLIAM CLOUGR, B.Sc. . . 771 LXXX.-Experiments on the Synthesis of Camphoric Acid, Part IV. The Action of Sodium and Methyl Iodide on Ethyl Dime t hylbutanetricar boxylate, C02Et.CH2-CH(C0,Et)CMe2.CN,.C02Et. By WILLIAM HENRY PERKIN, jun., and JOCELYN FIELD THORPE . 778 LXXX1.-Experiments on the Synthesis of Camphoric Acid. Part V. A Synthesis of Camphoric Acid. By WILLIAM LXXXI1.-A Product of the Action of isoAmyl Nitrite on By ARTEIUR GEORGE FERKIN, F.R.S., and ALEC LXXXII1.-Some New o-Xylene Derivatives.By GEORGE LXXX1V.-Note on the Constitution of Cellulose. By ARTHUR LXXXV.-The Constitution of Salicin. Synthesis of Penta- By JAMES COLQUHOUN IRVINE, Ph.D., D.Sc. LXXXV1.-Reciprocal Displacement of Acids in Heterogeneous HENRY PERKIN, jun., and JOCELYN FIELD THORPE . . 795 Pyrogallol BOWRING STEVEN, B.Sc. . . 802 STALLARD, M. A. . 808 GEORGE GREEN and ARTHUR GEORGE PERKIN . . a11 methyl Salicin. (Carnegie Fellow), and ROBERT EVSTAFIEFF ROSE, Ph.D. . 814 Systems. By ALFRED FRANCIS JOSEPH, A.R.C.S., B.Sc. , 823CONTENTS. ix PAGE LXXXVI1.-Experiments on the Synthesis of the Terpenes. A Synthesis of Tertiary Menthol (p-Menthanol- By WILLIAM LSXXVII1.-Experiments on the Synthesis of the Terpenes. Synthesis of the Optically Active Modifications By FRANCIS LXXX1X.-The Constitution of the Hydroxides and Cyanides obtained from Acridine, Methylacridine, and Phenanthridine Methiodides.By CHARLES KENNETH TINKLER, B.Sc. . . 856 XC.-The Residual Affinity of Coumarin as shown by the Form- ation of Oxonium Salts. By GILBERT THOMAS MOKGAN and FRANCES MARY GORE MICKLETHWAIT . . 863 XC1.-The Constitution of Ammonium Amalgam. By ELIZABETH MARY RICH and MORRIS WILLIAM TRAVERG, D.Sc., F.R.S. . 8'72 XCI1.-Aromatic Compounds obtained from the Hydroaromatic Series. Part I T . The Action of Phosphorus Pentachloride on Trimet.hyldihydroresorcin. By ARTHUR WILLIAM CROSSLEY and JAMES STUART HILLS . . 875 XCII1.-The Densities of Liquid Nitrogen and Liquid Oxygen and their Mixtures. By JOHN KENNETH HAROLD INGL~S and JOSEPH EDWARD COATES .. 886 XC1V.-The Chemistry of Organic Acid '( Thiocyanates " and their Derivatives. By AUGUSTUS E. DIXON, M.D. . . 892 XCV.-The Action of Light on Potassium Ferrocysnide. By GLPN WILLIAM ARNOLD FOSTER, B.Sc. (1851 Exhibition Scholar, Manchester University) . , . 912 XCV1.-The Action of Magnesium Methyl Iodide on dextvo- Cy WILLIAM AUGUSTCS TILDEN and FREDERICK GEORGE SHEPHEARL), B. Sc., Lond. . 920 XCVI1.-Dinitroanisidines and their Products of Diazotisation (Second Communication). By RAPHAEL MELDOLA, F.R.S., and FRANK GEORGE C. STEPHENS . . 923 XCVII1.-Electrolysis of Potassium Ethyl Dipropylmalonate. By DAVID COWAN CRICHTON, M.A., B.Sc. (Carnegie Research XC1X.-Resolution of Lactic Acid by Morphine. By JAMES C.-The Oxidation of Hydrocxrbons by Ozone a t Low Tempera- C1.--Reactions Involving the Addition of Hydrogen Cyanide to Carbon Compounds. Part V.Cyanodihydrocarvone. By ARTHVR LAPWORTH . . 945 Part VII. 4) and of Inactive Menthene (A3-p-Menthene). HERRY PERKIN, jun. . . 832 Part VIII. of A3-p-Menthenol(8) and A3W')pMenthadiene. WILLIAM HAY and WILLIARi HENRY PERKIN, jun. . . 839 Limonene Nitrosochlorides. Scholar) . . 929 COLQUHOUX IRVINE, Ph.D., D.Sc. (Carnegie Fellow) . . 935 tures. By JULIEN ORUGMAN . . 939X CONTENTS. PAGE CI1.-The Relation between Absorption Spectra and Chemical Constitution. Part V. The isoNitroso-compounds. By EDWARD CHARLES CYRIL BALY, EFFIE GWENDOLINE MARSDEN, and ALFRED WALTER STEWART (Carnegie Research Fellow) . CII1.-The Relation between Absorption Spectra and Chemical Constitution.Part VI. The Yhenylhydrazones of Simple Aldehydes and Ketones. By EDWARD CHARLES CYRIL BALY and WILLIAM BRADSHAW TUCK . . 982 CIV.-A New Method for the Measurement of Hydrolysis in Aqueous Solution based on a Consideration of the Motion of Ions. By ROBERT BECKETT DENISON, M.Sc., Ph.D., and CV.-The Solubility of Triphenylmethane in Organic Liquids with which i t forms Crystalline Compounds. By HAROLD HARTLEY, M.A., Fellow of Balliol College, and Nom GARROD THOMAS, Brackenbury Scholar, Balliol College . CV1.-Studies of Dynamic Isomerism. Part IV. Stereoisomeric Halogen Derivatives of Camphor. By THOMAS MARTIN LOWRY . . 1033 CVI1.-Studies of Dynamic Isomerism. Part V. Isomeric Sul- phonic Derivatives of Camphor.By THOMAS MARTIN LOWRY and EGBERT H. MAGSON, B.Sc. . . 1042 CVII1.-Influence of Substitution on the Formation of Diazo- amines and Aminoazo-compounds. Part Y. s-Dimethyl- 4 :6-diamino-m-xylene. By GILBERT THOMAS MORGAN and ARTHUR CLAYTON, B.Sc. . . 1054 C1X.-Ammonium Selenate and the Question of Isodimorphism in the Alkali Series. By ALFRED EDWIX HOWARD TUTTON, M.A., D.Sc. (Oxon.), F.R.S.- . . 1059 CX.-The Constituents of the Essential Oil frop the Fruit of Pittosporum undulatum. By FREDERICK BELDING POWER and FRANK TUTIN . . 1083 CX1.-A Study of the Reaction between Hydrogen Peroxide and Potassium Persulphate. By JOHN ALBERT NEWTON FRIEND, M.Sc. . 1092 P a r t 11. The Resolution of the Tetrahydronaphthoic Acids. By ROBERT HOWSON PICKARD and JOSEPH YATES . . 1111 CXII1.-The Constitution of Umbellulone.By FRANK TUTIN . 1104 CX1V.-Contributions to the Theory of Isomorphism based on Experiments on the Regular Growths of Crystals of One Substance on those of Another. By THOMAS VIPOND BARKER, B.A., B.Sc. (Oxon.), (Senior Demy of Magdalen College, 966 BERTRAM DILLON STEELE, D.Sc. . . 999 . 1013 CXI1.-Optically Active Reduced Naphthoic Acids. Oxford) . - ? a . . 1,120CONTENTS. xi PAGE CXV.-The Diazo-derivatives of the Mixed Aliphatic Aromatic w-Benzenesulphon ylaminobenzylamines. By GILBERT THOMAS MORGAN and FRANCES MARY GORE MICKLETHWAIT . . 1158 CXV1.-The Mobility of Substituents in Derivatives of P-Naphthol. By JOHN TEEODORE HEWITT and HERBERT VICTOR MITCHELL . . 1167 CXVI1.-A Possible Source of Error in Stas' Nitrogen Ratios.By ROBERT WHYTLAW GRAY . . 1173 CXVII1.-The Decomposition of Nitrocellulose. By OSWALD SILBERRAD, Ph.D., and ROBERT CROSBIE FARMER, Ph.D., D.Sc. . 1182 CX1X.-The Esters of Triacetic Lactone and Triacetic Acid. By FOSTER SPROXTON, B.Sc. . . 1186 CXX.-The Behaviour of the Vapours of Methyl Alcohol and Acetaldehyde with Electrical Discharges of High Frequency. By THOMAS PURDIE, By HERBERT JACKSON and DUDLEY NORTHALL-LAURIE . . 1190 F.R.S., and CHARLES ROBERT YOUNG, B.Sc. . 1194 F.R.S., and ROBERT EYSTAFIEFF ROSE, Ph.I?. . . 1204 CXX1.-The Alkylation of Rhamnose. CXXI1.-The Alkylation of I-Arabinose. By THOHAS PURDIE, CXXII1.-Saponarin, a New Glucoside Coloured Blue with CXX1V.-The Action of Xthyl Iodide and of Propyl Iodide on the Disodium Derivative of Diacetylacetone. By ALEXANDER WILLIAM BAIN, B.A., F.Sc.CXXV.-The Ethyl Esters of Acetonyloxalic and benzoyi- pyruvic Acids and the Action of Ethyl Oxalate on Acetanilide and its Homologues. By SIEGFRIED RUHEMANN . . 1236 CXXV1.-Aldehydrol and the Formation of Hydrates of Com- pounds containing a Uerbonyl Group. By WILLIAM MORRIS COLLES, jun. . . 1246 CXXVI1.-Studies on Optically Active Uarbimides. IV. The Resolution of ac-Tetrahydro-2-naphthol by means of FMenthylcarbimide. By ROBERT HOWSON PICKARD and WILLIAM OSWALD LITTLEBURY, A.I.C. . 1254 CXXVII1.-The Constitution of Acetone. By MILLICENT TAYLOR . 1258 CXX1X.-Tetrazoliue. Part IV. By SIEGFRIED RUHEMANN . 1268 CXXX.-The Hydrolysis of Animonium Salts by Water. ERNEST GEORGE HILrJ t . 1273 Iodine. By GEORGE EARGER .. 1210 . 1224 Byxii CONTENTS. PAGE CXXX1.-The Act-ion of Nitrous Acid on the Arylsulphonyl- metadiamines. By GILBERT THOMAS MORGAN and FRAKCES MARY GORE MICKLETHWAIT . . 1289 Cleve Memorial Lecture. By THOMAS EDWARD THORPE, C.B., F.R.S. . . 1301 CXXXI1.-Labile Isomerism among Acyl Derivatives of Sali- cylamide. By JAMES MCCONNAK and ARTHUR WALSH TITHERLEY . 1318 CXXXII1.-Some New Derivatives of Dicyclopentadiene. By CXXX1V.-Thiocarbamide as a Solvent for Gold. By JAMES CXXXV.-The Vapour Pressures of Binary Mixtures. Part I. The Possible Types of Vapour Pressure Curves. By ARTHUR MARSHALL . . 1350 CXXXV1.-A New Method for the Measurement of Hydrolysis in Aqueous Solutions, based on n Consideration oE the Motion of Ions. A Correction. By ROBERT BECKETT CXXXVIL-Dinaphthacridines. By ALFRED SENTER and PERCY CXXXVII1.-The Interaction of Chlorine and Hydrogen. By CXXX1X.-Notes on Derivatives of a-N-Alkylated Naphthyl- CXL.-Electrolytic Oxidation.By HERBERT DRAKE LAW, B.Sc. 143'7 CXL1.-The Properties of 2:3:4:5-Tetrachlorotoluene. ALEXANDER RULE, M.Sc., Ph.I). . . 1339 MOIR, M.A., D.Sc. . . 1345 DENISON and BERTRAM DILLON STEELE . . 1386 CORLETT AUSTIN . . 1387 CHARLES HUTCHENS BURGESS and DAVID LEONARD CHAPMAN 1399 amine. By RAPHAEL MELDOLA, F.R.S. . . 1434 A Correc- tion. By JULIUS BEREND COHEN and HENRY DRYSDALE DAKIN . . 1453 CXLI1.-A Method for the Formation of Succinjc Acid and of its Alkyl Derivatives. By ANNIE HIGSON and JOCELYN FIELD THORPE . . 1455 CXLII1.-Studies in the Acridine Series. Part IV. The Methylation of Chrysophenol.By ALBERT ERNEST DUKSTAN and JOHN THEODORE HEWITT . . 1472 CXL1V.-The Relation of Position Isomerism to Optical Activity. VII. The Rotation of the Menthyl Esters of Three Isomeric Dinitrobenzoic Acids. By JULIUS EEREND COHEK and HENRY PERCY ARMES . . 1479 Part 111. The Relative Catalytic Effect of Bases on the Compounds of A2-Dihydro-1-naphthoic Acid. By ROBERT HOWSON PICKARD and JOSEPH YATES . . 1484 CXLV.-Optically Active Reduced Naplithoic Acids.CONTENTS. xi11 PAGE @XLVI.-Estimation of Copper by Titanium Trichlaride. By CXLVI1.-The Gum of Cochlospemzum Gossypium. By HENRY CXLVII1.-Steric Hindrance in the Naphthalene Series. By CXL1X.-Electrolytic Reduction. I. Aromatic Aldehydes. By CL.-Electrolytic Reduction. 11. Use of Electrodes.By CL1.-Some Derivatives of 2- and 3-Phenanthrol. By HERBERT CLI1.-The Velocity of Chemical Change in the Polymethylene CLII1.-Separation of aa- and ,BP-Dimethyladipic Acids. By CL1V.-Action of Alcoholic Potassium Hydroxide on 3-Bromo- 1 : 1-dimethylhexahgdrobenzene. By ARTHUR WILLIAM CROSSLEY and NORA RENOUF . . 1556 CLV.-The Preparation and Properties of Dihydropinylamine (Pinocamphylamine). By WILLIAM AUGUSTUS TILDES and FREDERICK GEORGE SHEPHEARD, B.Sc. . . 1560 CLV1.-The Aminodicarboxylic Acid derived from Pinene. By WILLIAM AUGUSTUS TILDEN and DONALD FRANCIS BLYTHER . 1563 CLVI1.--The Description and Spectrographic Analysis of a Meteoric Stone. By WALTER NOEL HARTLEY, D.Sc., F.R.S. 1566 CLVlI1.-Malacone, a Silicate of Zirconium, containing Argon and Helium.By EDWARD STANHOPE KITCHIN and WILLIAM GEORGE WINTERSON, B.Sc. (Lond.) . . 1568 CL1X.-The Action of Nitrogen Sulphide on Certain Metallic Chlorides. By OLIVER CHARLES MINTY DAVIS . . 1575 CLX.-The Addition of Alkyl Halides to Alkylated Sugars and Glucosides. By JAMES COLQUHOUN IRVINE, Ph.D., D.Sc. (Carnegie Fellow), and AGNES MARION MOODIE, M.A., B.Sc. (Carnegie Scholar) . . 1578 @LXI.-The Direct Union of Carbon and Hydrogen a t High Temperatures. By JOHN NORMAN PRING and ROBERT SALMON HUTTON . . 1591 Part 111. By ARTHUR GEORGE GREEN and PERCY FIELD CROSLAKD . . 1602 EZRA LOBB RHEAD . . 1491 HALIBURTON ROBINSON, M.A. (Oxon.) . . . 1496 CLARENCE SMITH . . 1505 HERBERT DRAKE LAW . . 1512 HERBERT DRAKE LAW . . 1520 HENSTOCK . . 1527 Series. By NICHOLAS MENSCHUTKIN, sen.. . 1532 ARTHUR WILLIAM CROSSLEY and NORA RENOUF . . 1552 CLXI1.-The Colouring Matters of the Stilbene Group.xiv CONTENTS. PAGE CLXII1.-The Explosive Combustion of Hydrocarbons. 11. By WILLIAM ARTHUR BONE, JULIEN DRUGMAN, and GEORGE WILLIAM ANDREW . . 1614 CLX1V.-Derivatives of multivalent Iodine. The Action of Chlorine on Organic Iodo-derivatives, including the Sul- phonium and Tetra-substituted Ammonium Iodides. By EMIL ALPHONSE WERNER . . 1625 Part IX. The Preparation of cycZoPentanone-4-carboxylic Acid and of cycZoHexanone-4-carboxylic Acid (6Ketohexahydro- benzoic Acid). By FRANCIS WILLIAM KAY and WILLIAM HENRY PERKIN, jun. . . 1640 CLXV1.-Some Derivatives of Catechol, Pyrogallol, Benzo- phenone, and of Substances allied to the Natural Colouring Matters.By WILLIAM HENRY PERKIN, jun., and CHARLES WEIZMANN . . 1649 CLXVI1.-The Nature of Ammoniacal Copper Solutions. By HARRY MEDFORTH DAWSON . , 1666 CLXVII1.-A Development of the Atomic Theory which Corre- lates Chemical and Crystalline Structure and leads to a Demonstration of the Nature of Valency. By WILLIAM BARLOW and WILLIAM JACKSON POPE . . 1675 CLX1X.-Optically Active Dihydrophthalic Acid. By ALLEN CLXX.-The Relation between Natural and Synthetical Glyceryl- phosphoric Acids. Part 11. By FRANK TUTIN and ARCHIE CECIL OSBORN HANN . . 1749 CLXX1.-The Hydrolysis of ‘‘ Nitrocellulose ” arid “ Nitro- glycerine.” By OSWALD SILBERRAD, Ph.D., and ROBERT ULXXIL-Contributions to the Theory of Solutions. I. The Nature of the Molecular Arrangement in Aqueous Mixtures of the Lower Alcohols and Acids of the Paraffin Series.11. Molecular Complexity in the Liquid State. 111. Theory of the Intermiscibility of Liquids, By JOHN HOLMES 1774 CLXXII1.-The Relationship of Colour and Fluorescence to Con- stitution. Part I. The Condensation Products of Mellitic and Pyromellitic Acids with Resorcinol. By OSWALD SILBERRAD, Ph.D. , . 1787 CLXXIV.-Thiocarbonic Acid and some of its Salts. By IDA GUINEVERE O’DONOGHUE, B.Sc., and ZELDA KAHAN, B.Sc. . 1812 CLXXV.-Derivatives of Cyanodihydrocarvone and Cyanocarvo- CLXV.-Experiments on the Synthesis of the Terpenes. NEVILLE, B.Sc. . , 1744 CRosBrE FARMER, D.Sc., Ph.D. . . 1759 menthone. By ARTHUR LAPWORTH . . 1819CONTENTS. XV PAGE CLXXV1.-The Acidic Constants of Some Ureides and Uric CLXXVI1.-The Affinity Constants of Xanthine and its Nethyl CLXXVII1.-Xanthoxalanil and its Analogues.By SIEQFRIED RUHEMANN . 1847 CLXX1X.-The Influence of Various Substituents on the Optical Activity of Tartramide. Part 11. By PERCY FARADAY CLXXX.-The Influence of Various Substituents on the Optical Activity of Malamide. By PERCY FARADAY FRANKLAND and EDWARD DONE, M.Sc. . 1859 CLXXXI. -Reactions Involving the Addition of Hydrogen Cyanide to Carbon Compounds. Part VI. The Action of Potassium Cyanide on Pulegone. By REGINALD W. L. CLARKE and ARTHUR LAPWORTH . . 1869 CLXXXIL-Note on the Anhydride of Phenylsuccinic Acid. By FRANK BERNHARD DEHN and JOCELYN FIELD THORPE . . 1882 CLXXXIIL-Studies in Optical Superposition. Part 11. By THOMAS STEWART PATTERSON and JOHN KAYE .. 1884 CLXXX1V.-The Interaction of the Alkyl Sulphates with the Nitrites of the Alkali Metals and Metals of the Alkaline Earths. By PnAFuLLA CHANDRA R ~ Y and PANCHXNAN NEOGI, M.A. . 1900 CLXXXV.-The Formation and Reactions of Imino-compounds. Part 11. Condensation of Benzyl Cyanide Leading to the Formation of 1 :3-Naphthylenediamine and its Derivatives. By ERNEST FRANCIS JOSEPH ATKINSON and JOCELYN FIELY) THORPE . . 1906 CLXXXV1.-A New Trinitroacetaminophenol and its use as a Synthetical Agent. By RAPHAEL MELDOLA, F.R.S. . . 1935 Acid Derivatives. By JOHN KERFOOT WOOD . . 1831 Derivatives. By JOHN KERFOOT WOOD . . 1839 FRANKLANU and DOUGLAS FRANK TWISS, M.Sc. . . 1852CONTENTS. XV PAGE CLXXV1.-The Acidic Constants of Some Ureides and Uric CLXXVI1.-The Affinity Constants of Xanthine and its Nethyl CLXXVII1.-Xanthoxalanil and its Analogues. By SIEQFRIED RUHEMANN . 1847 CLXX1X.-The Influence of Various Substituents on the Optical Activity of Tartramide. Part 11. By PERCY FARADAY CLXXX.-The Influence of Various Substituents on the Optical Activity of Malamide. By PERCY FARADAY FRANKLAND and EDWARD DONE, M.Sc. . 1859 CLXXXI. -Reactions Involving the Addition of Hydrogen Cyanide to Carbon Compounds. Part VI. The Action of Potassium Cyanide on Pulegone. By REGINALD W. L. CLARKE and ARTHUR LAPWORTH . . 1869 CLXXXIL-Note on the Anhydride of Phenylsuccinic Acid. By FRANK BERNHARD DEHN and JOCELYN FIELD THORPE . . 1882 CLXXXIIL-Studies in Optical Superposition. Part 11. By THOMAS STEWART PATTERSON and JOHN KAYE . . 1884 CLXXX1V.-The Interaction of the Alkyl Sulphates with the Nitrites of the Alkali Metals and Metals of the Alkaline Earths. By PnAFuLLA CHANDRA R ~ Y and PANCHXNAN NEOGI, M.A. . 1900 CLXXXV.-The Formation and Reactions of Imino-compounds. Part 11. Condensation of Benzyl Cyanide Leading to the Formation of 1 :3-Naphthylenediamine and its Derivatives. By ERNEST FRANCIS JOSEPH ATKINSON and JOCELYN FIELY) THORPE . . 1906 CLXXXV1.-A New Trinitroacetaminophenol and its use as a Synthetical Agent. By RAPHAEL MELDOLA, F.R.S. . . 1935 Acid Derivatives. By JOHN KERFOOT WOOD . . 1831 Derivatives. By JOHN KERFOOT WOOD . . 1839 FRANKLANU and DOUGLAS FRANK TWISS, M.Sc. . . 1852
ISSN:0368-1645
DOI:10.1039/CT90689FP001
出版商:RSC
年代:1906
数据来源: RSC
|
2. |
II.—The diazo-derivatives of 1 : 5- and 1 : 8-benzenesulphonylnaphthylenediamines |
|
Journal of the Chemical Society, Transactions,
Volume 89,
Issue 1,
1906,
Page 4-13
Gilbert Thomas Morgan,
Preview
|
PDF (590KB)
|
|
摘要:
4 MORGAN AND MICKLETHWAIT : THE DIAZO-DERIVATIVES OF 11.-The Dicszo-derivatives oj' 1 : 5- and I : 8-Benzene- .suZphonylnapht h y Zenediamines. By GILBERT THOUAS MORGAN and FRANCES MARY GORE MTCKLETHWAIT. T m interactions of the diamines of the benzene series with nitrous acid afford a striking illustration of the influence of orientation on the properties of aromatic compounds. The ortho-diamines and their mono-acyl derivatives yield cyclic diazoimides which are generally colourless * and very stable towards hydrolytic agents, and although until recently condensation had not been detected among the para- diamines, yet about a year ago the authors obtained from the aryl- sulphonyl derivatives of these bases a new series of diazoimides which differ from their ortho-isomerides in having a distinctly yellow colour, and in readily undergoing fission on treatment with acids, phenols, or aromatic amines, the acids regenerating the diazonium salt, whilst the phenols and aromatic amines give rise to azo-derivatives (Trans., 1905, 87, 73, 921, 1302).The formation of these two series of diazoimides indicates very forcibly the profound mutual influence exercised by the substituents when they occupy the ortho- or para-positions of the aromatic nucleus, for in the meta-series this tendency for the diamines and their acyl derivatives to yield diazoimino-compounds by internal condensation seems to be absent. The marked differences in the physical arid chemical properties of the two series of diazoimino-derivatives point to fundamentally dis- similar configurations for the two groups of substances, and, as was stated in the firs5 communication on this subject (Eoc.cit., p. 73), the ortho-compounds which are at once formed, even in the presence of strong mineral acids, may be formulated either as diazoimides or as diazonium-imides, whereas the para-derivatives, which are produced only in faintly acid or neutral solutions, might be regarded as being * 2 : 3-Diazoimi1ioiiaplitlielenu is, however, described as being a yellow compound (Friedlmder aud Zakrzewki, Ber., 1S94, 27, 765).1 : 5- AND 1 : 8-BENZENESULPHONYLNAPHTHYLENEDTAMINES. 5 either diazoimides (I) or imitlo-~-quinonec\ittzides (II), the conditions of formation in this case excluding the dinzonium configuration. I. Hitherto no experimental evidence has been forthcoming to enable one to decide between these two formulz for the para-diazoimides, for although the former sufficed to explain the formation and modes of fission of these substances, yet their colour and great reactivity suggested a quinonoid structure.This question of the constitution of these coloured reactive para- diazoimides has now been put to the test of experiment by extending the investigation to the benzenesnlphonyl derivatives of two of the heteronucleal naphthylenedianiines. Benxenesulphonyl-I : 5-nc6phtl~yzenediamilze (111), a compound in which the substituents, although placed at the extremities of rz chain of four carbon atoms, are nevertheless situated a t the opposite ends of different benzene rings, shows no tendency to yield a diazoimide when treated with nitrous acid, this negative result indicating that the presence of one substituent in the 4- or %position with respect to the other does not in itself determine the formation of a diazo-anhydride by internal condensation, but that the orientation of the two groups in the aromatic nucleus is the more important factor.IIi. IV. v. BenxenesuZphonyI- 1 ; B-.iz~phtl~ylenediccmine (IV), which contains one substituent in the 3- or y-position with respect to the other, these two groups being situated in adjacent positions in the two rings, yields a diazoanhydride quite as readily and completely as its homo- nucleal para-isomeride (V) (Trans., 1905, 85, 929). The new peri- diazoimide (VI) is yellow and also comparable in all other respects with the isomeric para-diazoimide (VII) already described (Eoc.cit., p. 928), and as it contains its substituents in both rings of the naphthalene nucleus, it does not seem possible to construct its formula on the assumption that an intranucleal quinonoid rearrangement has6 MORGAN AND MICKLETHWAIT : THE DIAZO-DERIVATIVES OF occurred, and hence the cyclic structure (VI) adopted below is, in the present state of our knowledge, the simplest mode of representing the constitution of the compound, As, however, the properties of the para-diazoimides resemble so closely those of the peri-diazoimide, the adoption of a cyclic configuration (TI) for the latter compound leads by analogy to the acceptance of the cyclic structure (I) for the para- series in preference to the quinonoid formula (11). Accordingly the isomeric benzenesulphonyl-peyi- and -para-diazo- imides of the naphthalene series should be represented respectively by the following formulae : ---No soz c6 H, /\/\ I I I I N \/\/ -($ N = N - N-SO2*C,H, \ / /\/\ VI. \ / VII.The quinonoid formula being excluded, the colour of these diazo- imides milst now be referred to the presence in their molecules of the chromophore -N:N-, a group which is generally assumed to be present in the coloured diazoamines, diazosulphonates, diazocyanides, and azo-compounds. Thus, the acceptance of the cyclic formula for the yellow diazoimides brings these compounds into line with other coloured azo- and diazo-derivatives. On the other hand, the ortho- diazoimidee, many of which are colourless, are also formulated as containing this group, and from this point of view it seems desirable that the constitution of these substances should be reconsidered.Further evidence in support of the foregoing formula for the peri- dinzoimide has been obtained by applying the diazo-reaction to as-benxenesulphonyZ-N-metl~yZna~hthylenediccmine, a substance which readily gives rise in succession to a diazonium salt and an azo-/?-naphthol, but does not yield a diazoanhydride, thus proving that the production of the peri-diazoimide is due to the inter- action of the diazo-group with the complex NH*S02*C6H5, for when the labile hydrogen of the latter is replaced by methyl no condensation occurs. 1 : &Naphthylenediamine, when treated with nitrous acid, yields 1 : 8-diazoiminonaphthalene, C,,H,GH>N k (De Aguiar, Rer., 1874,1 : 5- AND 1 : 8-BENZENESULPHONYLNAPHTHYLENEDIAMINES. 7 7, 3 15), a red compound, which, unlike its foregoing benzenesulphonyl derivative, does not undergo fission when treated with cold concen- trated hydrochloric acid, and accordingly resembles the stable ortho- diazoimines.Hence, as regards its behnviour towards nitrous acid, pe&- or 1 : 8-naphthylenediamine occupies a position intermediate between the ortho- and para-diamines. Like the former, it yields itself a stable diazoimino-compound not decomposed by acids, the peri- derivative, however, differing from the ortho-diazoimines in being intensely coloured. The relationship of the peri-base to the para- diamines is plainly indicated by the analogous behaviour of their benzenesulphonyl derivatives, as set forth in the foregoing discussion, E: X P E RIME N TAL. Prepcwcbtion of 5 - and 8-Nit~o-a-nc~pht~?jZami~aes.The method of preparation employed, which was originally devised by Noelting, has already been dcscribed in this Journal (Meldola and Streatfeild, Trans,, 1893,83, 1054). It consists in nitrating a well- cooled solution of 100 grams of a-naphthylamine in 1000 grams of concentrated sulphuric acid with 64 grams of nitric acid (sp. gr. 1.42) mixed with 128 grams of concentrated sulphuric acid. The reaction being liable to get out of control, the solution of the base in the con- centrated sulphuric acid and the addition of the nitrating mixture must both be carried out very slowly a t low temperatures ; the pro- duct, when left overnight and poured into iced water, yields a dark brown precipitate which contains 5-nitro-a-naphthylamine sulphate.The filtrate, when neutralised with sodium carbonate, yielded crude 8-nitro-a-naphthylamine, which was purified by repeating several times the operation of dissolving the base in sulphuric acid, filtering the solution from sparingly soluble sulphate, and reprecipitating with sodium carbonate. The crude sulphate of the 5-nitro-base was dissolved in boiling water and the base set free from the filtered solution by sodium carbonate. Ultimately, the two isomerides were further purified by crystallisa- tion from petroleum, when the peri-base was obtained from the solvent boiling at 80-100' in red leaflets and scales melting at'95-97", whereas the 1 : 5-isomeride crystallised from the fraction (b.p. 100-120°) in dark red needles melting a t 114--116'. The yield of tnhe peri-base was about 5-6 per cent. of the weight of a-iiaphthylamine originally taken, and the nitration was repeated until about 30 grams of this material bad accumulated.8 MORGAN ANT, MICKLETHWAIT : THE DIAZO-DERIVATIVES OF Action of BemenesuZpl.onic CIA Zoride on the Two Nitro-a-naphth ylamincs. The nitro-base (1 gram) was dissolved in dry pyridine (10-20 c.c.), treated with 1 -5 grams of benzenesulphonic chloride, and the solution heated to boiling for some time. With the 1 : 5-base, the reaction was practically completed in three hours, but with the 1 : S-isomeride a large proportion of unaltered base was recovered, even after beating for 10-12 hours." The product was poured on to crushed ice, acidified with dilute liydrochloric acid, and the insoluble residue dissolved in aqueous sodium carbonate.The crude benzenesulphonyl derivative, when reprecipitated from the alkaline solution with dilute hydrochloric acid, was crystallised from dilute alcohol (1 : 1). Re.lzzenesuZphoia~Z-5-nit ro-a-naphtlhylamine, NO,* C,,H, *NH*SO,*C,H,, crystallised in needles and melted at 183'. 0.2008 gave 15.6 C.C. nitrogen at 19' and 753 mm. C,,H,,O,N,S requires N = 8-53 per cent. BenxenesuZp?~onyl-8-nnitro-a-naphthyZarniiae, when crystallised first from dilute and then from strong alcohol, separated in almost colour- less needles melting a t 194'. N = 8.85. 0.2128 gave 15-85 C.C.nitrogen at 19.5" and 744 mm. N=8*36. 0.1602 ,, 0.3434 CO, and 0-0539 H,O. C=58.46 ; H= 3.74. C,,H,,O,N,S requires N = 8-53 ; C = 58.53 ; H = 3.66 per cent. Reduction of the Benxenesulp?AonyZnitro-a-~p?At~~yZ~~m~nes. Five grams of the nitro-derivative were suspended in 250 C.C. of warm water and treated with 10 grams of iron and 1.5 C.C. of glacial acetic acid; the mixture was boiled for half an hour, when the reduc- tion, which took place with the same readiness for both isomerides, appeared to be complete. The mixture was rendered alkaline with sodium carbonate and filtered ; in both cases the benzenesulphonyldi- amine remained in solution and was at once precipitated with dilute acetic acid. Benzewsu@honyZ- 1 : 5-naphthyZenediacmi~ae, NH,-C,oH,-NH=SO,* UGH,, crystallised well either from alcohol or from toluene containing a small proportion of petroleum (b.p. SO-100'); from the former medium, i t separated in large aggregates of radiating, colourless, silky needles, some of the individual crystals being 1B inches long. Its melting point was 161O. * It was found that the colour of the recovered 1 : 8-base was much less intense than that of the original specimen, and that its melting point had risen to 98--100".0.1874 gave 15 C.C. nitrogcn nt, 19" and 779 mm. 0.37.00 ,, 0.2881 BaSO,. S = 10.69. N=9*44. C16H,40,N,S requires N = 9 *39 ; S = 10.73 per cent. Uenxenesulphonyl- 1 : 8-ni,tplrtTi ylenediamine crystallised less readily than its isomeride from dilute alcohol or from toluene and petroleum, and separated in pale grey needles melting at 166".0.2304 gave 19-0 C.C. nitrogen at 19' and 744 mm. N = 9.27 per cent. Action of Nitivzcs Acid on the BenxenesuZplmnnyl-1 : 5- and -I : 8- napht Jt y lenedianaines . One gram of the 1 : 5-isomeride, when suspended in 12 C.C. of glacial acetic acid and 8 C.C. of' concentrated hydrochloricacid and treated a t - 10' to -5' with 2-8 C.C. of aqueous sodium nitrite (20 per cent.), yielded a soluble diazonium chloride together with a brown, amorphous product. The latter was removed by filtration, the filtrate diluted with water, and again filtered from a small proportion of tarry matter ; the final filtrate, when treated with a large excess of aqueous sodinm acetate, remained clear and showed no indications of yielding an insoluble diazoimide.The diazotised product was shown to be still in the form of a diazonium salt by combining it with @naphthol. The red sodium derivative of the azo-naphthol, which XIS deposited almost completely from the alkaline solution, when collected and treated with acetic acid, yielded besaxe1aesu~T~on~l5-ami~aonc,tpT~tT~alene- 1-azo- P-naphthol, NH*SO,* C,H, /\/\ 9 I l l \/\/ HO* C,,H6-N, which separated from glacial acetic acid in red, felted needles and melted at 260'. Om16O0 gave 13.0 C.C. nitrogen at 19' and 755 mm. N = 9.52. C26H,i,0,N,S requires N = 9.27 per cent. The azo-compound developed an intense reddish-violet coloration witli cold concentrated sulph uric acid.10 MORGAN AND MICKLETHWAIT : THE DIAZO-DERIVATIVES OF BenxenesuZplLonyLl : 8-na~~thylenediaxoilnide, N,-N*SO,*C,H, 1 1 /\/\ I l l \/\/ Benzenesulphonyl-1 : 8-naphthylenediamine ( 1 *5 grams), suspended in 12 C.C.of glacial acetic acid and 12.0 C.C. of concentrated hydro- chloric acid, cooled to - lo", and slowly treated with 3.6 C.C. of aqueous sodium nitrite (20 per cent.),gave rise to a soluble diazonium chloride together with a small proportion of a greenish-brown, amor- phous precipitate. The filtered solution yielded a further deposit of viscid impurity on dilution, and, after filtration, was cautiously treated with dilute aqueous sodium acetate to remove last traces of resinous products. As soon as the acetate gave a slight permanent precipitate of cyclic diazoimide, the turbid solution was again filtered, and the clear, light yellow filtrate then treated with excess of concentrated acetate solution, when the diazoimide separated as a flocculent, orange- yellow precipitate, which on stirring became crystalline and lighter in colour.The deposit, which was collected and thoroughly washed successively with water, alcohol, and light petroleum, was dried in the desiccator until its weight was constant. The alcohol removed a red impurity, but otherwise the diazoimide was quite insoluble either in this solvent or in water ; when thoroughly dried, the compound, without further purification, gave the following numbers on analysis : 0.2353 gave 0.5368 CO, and 0.0754 H,O. C = 62.22 ; H= 3.56. 0.2416 ,, 0.5481 CO, ,, 0.0804 H20. C = 61.8s ; H= 3.69. 0.2486 ,, 0.5687 CO,. C = 62.39. 0.1524 ,, 17.2 C.C.nitrogen at 19' and 779 mm. N = 13-45. 0.2173 ,, 0.1673 BaSO,. S= 10.57. C,,H,,O,N,S requires C = 62.14 ; H = 3.56 ; N = 13.59 ; S = 10.35 per cent. When heated in the combustion tube, the substance decomposed energetically, evolving puffs of yellow smoke. It may be kept for an indefinite time in the dark, but is affected by light, rapidly becoming brown.* The sodium acetate filtrate from benzenesulphonyl-1 : S-naphthylene- diazoimide was added to alkaline P-naphthol, but no azo-colour was * The colour of the yellow dinzoimides assumes a paler hue, but is not entirely destroyed when the compounds are cooled to the temperature of liquid oxygen.1 : 5- AND 1 : 8-RENZENESULPHONYJ4NAPHTHYLENEDIAM1NES. 11 produced, thus showing that the conversion of the diazonium salt into the 1 : 8-diazoanhydride was complete. Pissi0.n of the peri-Diaxoimide.(1) Fission with Acids.-When suspended in 50 parts of cold glacial acetic acid, the diazoimide remained undissolved, and only passed into solution on warming on the water-bath. The deep red liquid, when poured into alkaline P-naphthol, yielded the alkali derivative of the am-compound, which was treated with glacial acetic acid in order to set free the azo-P-naphthol. The peri-diazoimide dissolved immediately in ice-cold concentrated hydrochloric acid to an almost colourless solution, which, when diluted with cold water and poured into alkaline P-naphthol, yielded the alkali azo-derivative, from which the free azo-naphthol was isolated by means of acetic acid. Another portion of the solution in hydrochloric acid after dilution with water was treated with excess of platinic chloride, when a pale yellow, crystalline diaxonium pialanzchloride was precipitated, which, when dried in the air, gave the following result on analysis : 0.2315 gave 0,0427 Pt.(C,H,*S0,*NH*C,,H,*N2),PtC16 requires Pt = 18.95 per cent. (2) Fission with Phenols.-Equal parts of the peri-diazoimide and @-naphthol were dissolved in dry pyridine and heated for two and a half hours on the water-bath. The deep red solution thus obtained was allowed to evaporate slowly, the solid residue was treated with excess of aqueous caustic soda and collected, the free azo-naphthol being then set free by glacial acetic acid. Pt = 18.44. BenxemesulphonyI-8-ccminonaphthalene- 1 -azo-p-naphthol, HO*C,,H,*N:N NH*SO,*C,H, /\/\ I l l \/\/ The azo-compound produced in the foregoing fission experiments was dissolved in benzene and precipitated from this solution by the addition of light petroleum.0.1802 gave 14.2 C.C. nitrogen a t 19.5' and 771 mm. C2,Hl9O3N:&3 requires N = 9.27 per cent. This compound, which was not obtained crystalline, melted some- what indefinitely at 1 70-180°, and developed an intense reddish-violet coloration with cold concentrated sulphuric acid. N = 9.18.12 AS-BENZENESULPHONYIJ-N-METHY Id- 1 : 8-NAPHTHY LENEDIAMINE BenzenesuZplt,on$-8 -nitro-N-rnetlTLyZ-a-na~ht~~~Zu~i?~e, N0,.G',,H,*N(C'H,)*S02*CGHF,. An alcoholic solution of 2 grams of recrystallised benzenesulphonyl- 8-nitro-a-naphthylamine and 0.3 grain of caustic soda was boiled for six hours with excess of methyl iodide (2 grams) added in small portions.The crystalline residue obtained after evaporating off the solvent was washed successively with aqueous caustic soda and water, and when crystallised repeatedly from alcohol separated in pale yellow needles melting a t 170". 0.2851 gave 2043 C.C. nitrogen at 19" and 766 mm. C,7Hl,0,N2S requires N = 8.18 per cent. The alkylation was practically quantitative ; the alkaline filtrates from the as- benzenesulphon yl- 8 4 tro-N-methy 1 -a-naph thy lami ne gave on acidifying no unmethylated nitro-compound, as-Benxenesulphony I-N-methy Z- 1 : S-napl~tlh$enedicmine was readily obtained from the foregoing nitroderivative by reducing 4 grams of this substance with 16 grams of iron, 2 C.C.of glacial acetic acid, and 200 C.C. of warm water, the heating being continued for an hour before the mixture was rendered alkaline with sodium carbonate. The alkaline filtrate from the iron oxide contained no organic base, the product being isolated from this insoluble residue by repeated extraction with alcohol. The new base did not crystallise well from this solvent, but was deposited in brownish-white, nodular crystals from its benzene solution on the addition of a small quantity of light petroleum. N = 8.45. 0.2898 gave 22.2 C.C. nitrogen at 19' and 772 mm. C,7HlG0,N,S requires N = 8-97 per cent. After repeated crystallisation, the substance melted at 161-1 62". N=8*95. as-BenxenesuZphonyZ-N-melhyl-8-uminonaphthalerne-l -ccxo-~-~aphthoI, /\/\ I l l HO* C,,H,*N:N N(CH,)* S02*C,H, \/\/ When diazotised with aqueous sodium nitrite in a mixture of con- centrated hydrochloric and acetic acids at - 10" to - 5 O , the preceding methyl base yielded a soluble diazonium salt, from the filtered solution of which aqueous sodium acetate precipitated no insoluble diazo- anhydride. The clear solution of the diazo-salt, when poured into an alkaline solution of @-naphthol, yielded an insoluble bright scarlet azo-AZO-DERIVATIVES OF 4 : 6-DIMETHYLCOOMARIN. 13 compound which crystallised readily from glacial acetic acid in trans- parent, ruby-red nodules. 0.2359 gave 18 C.C. nitrogen at 19" and 770 mm. This azo-derivative, which melted a t 215", developed an intense N=8.89. C,7H,,0,N,S requires N = 8-99 per cent. reddish-violet coloration with cold concentrated sulphuric acid. The authors' thanks are due to the Government Grant Committee of the Royal Society for a grant which has partly defrayed the expenses of this investigation. ROYAL COLLEGE OF SCIENCE, LONDON, SOUTH KENSINGTON, S. W.
ISSN:0368-1645
DOI:10.1039/CT9068900004
出版商:RSC
年代:1906
数据来源: RSC
|
3. |
III.—Azo-derivatives of 4 : 6-dimethylcoumarin |
|
Journal of the Chemical Society, Transactions,
Volume 89,
Issue 1,
1906,
Page 13-17
John Theodore Hewitt,
Preview
|
PDF (279KB)
|
|
摘要:
AZO-DERIVATIVES OF 4 : 6-DIMETHYLCOOMARIN. 13 I I I.-Azo-de rivatives oj’ 4 : 6 - Dimeth ylcouunccr ii 6. By JOHN THEODORE HEWITT and HERBERT VICTOR MITCHELL. IN a recent communication by one of the authors, it has been shown that the benzeneazocoumarin described by Borsche (Ber., 1904,37,346, 4116), when dissolved in aqueous alkali with formation of the coumarinate, is precipitated from solution either by excess of hydro- chloric acid or by carbon dioxide in the form of the azocoumarin, and not as an azocournarinic acid (Mitchell, Trans., 1905, 87, 1229). Such behaviour is more in accord with the hydroxyazo- than with the quinonehydrazone-structure of this and analogous compounds, and is not surprising, seeing that parahydroxy azo-compounds of the benzene series behave in practically all respects as if they possessed a hydroxy- azo-structure, and are almost universally regarded as having this configuration.I n the case of orthohydroxyazo-compounds, the facts are by no means as clear, for whilst alkylation both in the ortho- and para-series leads to oxygen ethers, some difference of view has been expressed as to the constitution of the substances formed by acylating orthohydroxyazo- compounds. The formation of acetanilide by the reduction of benzene- azo-p-tolyl acetate and of Meldola and East’s benzeneazo+-naphthyl acetate observed by Goldschmidt and Brubacher (Bey., 1891,24, 2300) certainly appears to favour a quinonehydrazone constitution for these substances, whilst the reduction of p-tolueneazo-p-naphthyl acetate studied by Meldola and Hawkins (Trans., 1893, 63, 926) led to a result which also points t o a hydrazone formula, aceto-p-toluidide being obtained as a chief product.14 HEWITT AND MITCHELL : Other objections to a hydroxyazo-formulation of these compounds may be seen in the insolubility of many o-hydroxyazo-compounds in aqueous alkalis: (compareMeldola,PhiZ.Mag., 1888, [v], 26,403 ; Meldola and Forster, Trans., 1891, 59, 710 ; and Meldola and Hawkins, Trans., 1893, 63, 923, concerning the possibility of the oxygen atom becoming a member of a closed chain) and in the fact that ortho-hydroxyazo- compounds do not appreciably associate in non-hydroxylic solvents (Auwers and Orton, Zed. physikd. Chem., 1896, 21, 337). Too much weight must not be placed on the above arguments ; that reduction of an acyl derivative of an azophenol should give rise to fission products in which the acyl group is attached to nitrogen is not altogether unexpected, as not merely might intramolecular change take place during the process of reduction, but also intermolecular change between the products of complete fission, the reaction being of very general occurrence.Auwers and Orton’s conclusions as to parahydroxyazo-compounds possessing a structure corresponding to their name, whilst the ortho- compounds are of quinonehydrazone type, are not justified by their own results. They find that ortho-substituted phenols generally show less association in non-hydroxylic solvents than the corresponding meta- or para-compounds, so that the complete inhibition of association by the somewhat negative and large nrylazo-group when in an ortho- position with respect to a phenolic hydroxyl is not unlikely.Moreover, it must be remembered that benzeneazo-p-cresol, when treated with bromine in acetic acid suspension, sodium acetate being present, gives benzeneazobromo-p-cresol in nearly quantitative yield, a fact strongly in favour of the hydroxyazo-formulation of the coiripound (Hewitt and Phillips, Trans., 1901, 79, 160). R*NH, + R’*CO,R” = R’OH + R*NH*CO*R’ EXPERIMENTAL. Some months ago an attlerript was made to nitrate benzeneazo-p- cresol with warm dilute nitric acid in the hope of confirming Hewitt and Phillips’ bromination results. So far the results have been dis- appointing, and we have now turned our attention to the behaviour of azocoumarins containing the azo-group in the ortho-position with respect to the oxygen atom of the lactonic ring.To obtain substances of this type, it was necessary t o use a coumarin in which the para- position to the oxygen atom mas already substituted. We hence chose the 4 : 6-dimethylcoumarin described by von Pechmann and Cohen (Ber., 1884, *17, ZlSS), as it is readily prepared by the con- densation of p-cresol with ethyl acetoacetate.AZO-DERIVATIVES OF 4 : 6-DIMETHYLCOUMARIN. 15 \/ co Dimethylcoumarin (1 -7 grams) was boiled with fairly concentrated potassium hydroxide until completely dissolved, when water and ice were added in considerable quantities. To this solution of potassium dimethylcoumarinate aphenyldiazonium chloride solution, prepared from 0.93 gram of aniline, 0.72 gram of sodium nitrite, 3 C.C.of fuming hydrochloric acid, and sufficient ice, was added. By acidification of the iutensely red Eolution of the alkaline salt of benzeneazodimethyl- coumarinic acid, a yellow precipitate is deposited consisting not of the acid, but of the corres1)oncling lactone. By twice crystallising from alcohol, the substance is obtained in lustrous, orange-red needles which melt at 199-200". 0.1169 gave 0.3162 CO, and 0.0583 H,O. CliH1402Nz requires C = 73.4 ; H = 5-0 per cent. Benzeneazodimethylcourllarin dissolves in alcohol, toluene, chloro- form, and pyridine; it is insoluble in light petroleum, Like the nitro-derivatives about to be described, it resembles the acyl deriv- atives rather than the azoplienols themselves.Although insoluble in cold alkaline solutions, prolonged boiling brings about solution with formation of an azocoumarinate and development of a n intense coloration. C=73*7; Hz5.5. This substance was prepitred in the usual manner. The colour of the solution of its alkaline azocoumarinate is reddish-violet. The free azocoumarin separates from chloroform as scarlet needles which melt a t 250" with decomposition. The substance is also soluble in pyridine, but dissolves sparingly in alcohol. 0.1082 gave 0.2507 GO, and 0.0404 H,O. C = 63.2 ; H = 4.1. 0.1465 ,, 16.4 C.C. nitrogen a t 13' and 748 mm. N = 13.0. Cl7H1,O,N, requires (I = 63.2 ; H = 4-0 ; N = 13.0 per oent,. m-Nitl.obep~cei~eaxo-4 : 6-d,ir,ietl~?/Zcou.11Lal-irt, prepared in the usual mmuer, separates from chloroform in large, transparent, reddish-16 AZO-DERIVATIVES OF 4 6-DIMETHYLCOUMARIN.brown tablets. of one molecule of chloroform of crystallisation. These soon become opaque owing to the volatilisation 3.3354 lost 0.8919 a t 120'. Loss = 26.75 per cent. C17H,,0,N,,CHC13 requires CHCl, = 27.05 per cent. The dried substance melted at 2 12' and gave the following figures on 0.1612 gave 18.2 C.C. nitrogen at 1Y and 760 mm. N = 13.4. 0.2482 ,, 28.1 C.C. ,, 12' ,, 733 mm. N=13*0. analysis : CI7H,,O,N, requires N = 13.0 per cent. nz-Nitrolsenzeneazo-4 : 6-dimethylcoumarin is also soluble in acetic acid, somewhat sparingly so in alcohol. The solutions of the alkaline coumarinates are red in colour. p-Nitrobenxenec~xo-4 : 6-dirnethylcoumarin was obtained by coupling potassium dimethylcoumarinate with p-nitrophenyldiazonium chloride ; its alkaline solution is intensely violet, the colour being far bluer in shade than is the case with the two isomerides. After the precipitated azocoumarin had been twice recrystallised from dilute acetic acid and once from chloroform, it was obtained as small, brown crystals melting at 229'.0.1018 gave 11.4 c.c. nitrogen at 15' and 755 mm. p-Nitrobenzeneazodimet hylcoumarin also dissolves in pyridine ; it is sparingly soluble in benzene and insoluble in light petroleum, The immediate production of lactones on acidification indicates the presence of ready-formed hydroxyl groups, and attention may again be drawn t o the fact that the passage of carbon dioxide into a solution of benzeneazocoumarin in alkali leads to the precipitation of benzene- azocoumarin (Rlitchell, Trans., 1905, 87, 1230).If we assume the equation N = 139. C,,H,,O,N, requires N = 13.0 per cent. C,H,*N:N*C76H,0Na + H,CO, = NaHCO, + C,H,*NH*N:C,H4:0 to be correct, we must express the first stage of the action of carbonic acid on the dipotassium salt of benzeneazocoumarinio acid by the eqiia tion C,H5*N:N*C,,H3(0K)*C2H2*CO2K + H2C03 = KHCO, + C,H,=NH*N: C,H,(: 0) *C2H,*C02K. The last foriuula indicates the sodium salt of a fairly strong carboxylic acid from which the weak carbonic acid would only liberate very small quantities of the corresponding free wid. The formation of benzeiieazocoumarin would then have to be represented by the following equations :AZO-DERIVATIVES OF ~!-METHYL-u-NAPHTHOCOUMARIN. 17 C,H,*NH*N:C,H,( :O).C2H2*C0,K + H2C03 f KHCO, + C6H,*NH*N:C,H3( :O)*C,H,*CO,H. C6H5*N:N*C,H,( OH)*C2HJ*C0,H. C,H5*NH*N:C,H,( :O)*C,H,*CO,H C,H,*N:N*C6 3(0H)*C2H2*C02H -+ H ~ O + c , H ~ ~ N : N ~ c , H ~ ~ ~ A > c o . Since the product on the right-hand side of equation (a;) can only be present in very small quantity, the equilibrium expressed in equation (6) must be established with enormous rapidity in order t o explain anything more than the very slow formation of a lactone. Such an extremely rapid establishment of equilibrium, even if not definitely disproved, is at least improbable. EAST LONDON COLLEGE.
ISSN:0368-1645
DOI:10.1039/CT9068900013
出版商:RSC
年代:1906
数据来源: RSC
|
4. |
IV.—Azo-derivatives of 4-methyl-α-naphthocoumarin |
|
Journal of the Chemical Society, Transactions,
Volume 89,
Issue 1,
1906,
Page 17-19
John Theodore Hewitt,
Preview
|
PDF (147KB)
|
|
摘要:
AZO-DERIVATIVES OF ~!-METHYL-u-NAPHTHOCOUMARIN. 17 IV. -A zo-derivutives of $-Methyl -a-naphthocoumarin. By JOHN THEODORE HEWITT and HERBERT VICTOR MITCHELL. IN continuation of earlier work on azocoumarins containing the azo- group in the para-position with respect to the lactonic oxygen (Mitchell, Trans., 1905, 87, 1229), it has been considered advisable t o examine representatives of the naphthalene series. Whilst benzene- azophenol cannot be directly prepared from quinone and phenyl- hydrazine, benzeneazo-a-naphthol was obtained by Zincke and Binde- wald (Ber., 1884, 17, 3026) by the interaction of phenylhydrazine and a-naphthoquinone. Further support for the formulation of benzene- azo-a-naphthol as a-naphthoquinonehydrazone is afforded by the re- action between this substance and te tramethy ldiaminoben zh yd rol discovered by Mohlau and Kegel (Bey., 1900, 33, 2858).As a convenient substance for our experiments, we have chosen the 4 -methyl-a-naph thocoumarin obtained by Bart sch, who condensed a-naphthol with ethyl acetoacetate (Berr., 1903, 36, 1966). Benaei-Leazo-4-meth y l-a-nap4 thocoumarin, /-\ \-/ c,~H,*N:N/ \ 0--co \-/--- \C(CH,) : bH’ was obtained by the action of phenyldiazonium chloride on a solution VOL. LXXXlX. CI8 AZO-DERIVATIVES OF 4-METHYL-a-NAPHTHOCOUMARIN. of potassium 4-methylnaphtlhocoumarinate. The colour of the alkaline solution produced is intensely red, and, on addition of dilute sulphuric acid, the azocoumarin is deposited as a scarlet precipitate. By recrys- tallisation from pyridine, orange-brown, long, flaky needles are ob- tained, which melt at 207O.The substance is also soluble in chloro- form and alcohol, but is insoluble in light petroleum. 0.0911 gave 0.2553 CO, and 0.0363 H,O. C,,H,,O,N, requires C = 76.4 ; H = 4.5 per cent. 0- Nitrobenxenemo - 4-meth y I-a-naphthocoumarin was obtained from d i - azotised o-nitroaniline in the usual manner ; the alkaline solution is reddish-violet. The azocoumarin crystallises from pyridine in small, brown flakes melting a t 268'. C = 76.4 ; H = 4-4. 0.1274 gave 13.6 C.C. nitrogen at 20' and 763 mm. The substance dissolves in chloroform, less readily in alcohol, and is insoluble in light petroleum. m-Nitrobenzeneccxo-4-methy l-a-nuphthocoumarin gives a1 kaline solutions possessing a colour similar to that of cobalt nitrate, although not blue in shade.On crystallisation from chloroform, light brown needles are obtained which melt a t 239'. Whilst soluble in pyridine, the sub- stance is nearly insoluble in alcohol. N=12.1. C,,H,30,N, requires N = 11 *8 per cent. 0.1224 gave 0.3004 CO, and 0.0426 H,O. C = 66.9 ; H = 3.S. C,,H,,04N3 requires C = 66.9 ; H = 3.6 per cent. p- i\i'itrobenxeneaxo-4-nzethyl-a-~~~p~~t~ocou~~~ur~~~ is remarkable, in that its alkaline solutions are indigo-blue in colour. On acidifying the alkaline solution, the azocoumarin is precipitated as a reddish-brown powder which, when recrystallised from toluene, melts a t 270-27 1'. 0.1 170 gave 0.2886 CO, and 0.0393 H20. The substance dissolves fairly readily in toluene, and only sparingly in alcohol ; it is gradually dissolved by solutions of hot alkalis with production of the indigo coloration. So extremely marked is the coloration that it seems advisable to inquire in.to the cause, especially in view of the fact that the p-nitrobenzene-4-azo-a-naphthol discovered by Bamberger (Bey., 1895, 28, 848; compare Hantzsch, ibid., 28, 1 124), although brownish-red in colour, gives violet alkaline solutions. Such difference in colour between an azophenol and its alkali salts only seems to occur when a nitro-group is present in the substituent arylazo-group in the para-position.We therefore prepared a specimen of p . nitrobenzenu-4-azo-a-naph- C = 67.3 ; H = 3-7. C,,HI,04N, requires C = 66.9 ; H = 3.6 per cent.THE ACTION OF WATER ON DIAZO-SALTS. 19 thol-2-carboxylic acid, which, itself brown in colour, dissolved in alkalis with a bluish-violet shade. If the colour were merely due to salt formation, one would expect the colouring matter to give a violet colour with an aluminium mordant. The colour obtained was, how- ever, brown, and since the lake obtained must contain the \CO,M grouping, one is inclined to assign another formula to the violet alkaline salts. The only apparent alternative is to assume the forma- tion of an honitro-group under the influence of alkali, which would, for instance, mean that the potassium salt of p-nitrobenzeneazo-a- naphthol must possess the constitution : /-\ \ / Ensr LONDON COLLEGE.
ISSN:0368-1645
DOI:10.1039/CT9068900017
出版商:RSC
年代:1906
数据来源: RSC
|
5. |
V.—The action of water on diazo-salts |
|
Journal of the Chemical Society, Transactions,
Volume 89,
Issue 1,
1906,
Page 19-26
John Cannell Cain,
Preview
|
PDF (503KB)
|
|
摘要:
THE ACTION OF WATER ON DIAZO-SALTS. 19 V.-The Action of Water on D,iazo-salts. By JOHN CANNELL CAIN and GEORGE MARSHALL NORBIAN. DURING an investigation carried out by one of us (J. C. C.) and Nicoll on the rate of decomposition of diazo-compounds, it was noticed (Trans., 1902, 81, 1440) that the products of decomposition of the tetrazo-salts prepared from oo-dichlorobenzidine and dianisidine were not the corresponding dihydroxy-compounds, as in the case of benzidine and tolidine, although the nitrogen mas evolved as usual. It was accordingly of much interest to investigate the nature of the sub- stances formed, and the result of this work was t o show that in each case the chief, if not the only product formed was of a quinonoid character (Trans., 1903, 83, 688). The very great difference in behaviour of these two tetrazo-salts as compared with those from benzidine and tolidine was apparently to be attributed to the presence of a chlorine and a methoxyl group respectively in the ortho-position to the diazonium group.With the object ol testing this view a search was made in the literature for any abnormal cases of decomposition of ortho-substituted c 220 CAIN AND NORMAN: diazo-salts belonging to the benzene series, and, curiously enough, all the instances found answered this description. It was therefore decided to make a thorough examination of these compounds with the object of discovering whether the alleged non-formation of phenols was to be explained by the presence of an ortho-substituent or otherwise. Methods of carrying ozct the Decomposition.What may be regarded as the normal method of decomposition of such diazo-salts is to diazotise in moderately strong mineral acid solu- tion (preferably hydrochloric or sulphuric acid) by adding a solution of sodium nitrite and then either heat to boiling the diazo-solution thus obtained or pass a current of steam through it. When, however, no phenol was found by this means, the method adopted by Heinichen (Artnalen, 1889, 253, 281) was tried. This consists in heating the strong diazo-solution with strong sulphuric acid, whereby the boiling point becomes raised to 150'. Heinichen, by this method, was success- ful in obtaining oo-dibromophenol from the corresponding diazo-salt, after the usual method had failed. Heinichen's method has been applied by various other workers in attacking similar problems, but often without success; thus Orton (23*oc., 1905, 21, 170) failed to obtain s-tribromophenol from the diazo-salt of tribromoaniline.This method of decomposition is, however, not a rational one owing to the fact that by using more concentrated sulphuric acid in order to reach a higher temperature a very considerable retarding influence is intro- duced. This retarding influence can be measured by determining the " coefficient of decomposition G " according to the method described by one of us and Nicoll (Zoc. cit., p. 1412). Thus, in the case of benzene- diazonium chloride the value of C is 0.0298 (Zoc. cit. p. 1420). A corresponding experiment with benzenediazonium sulphate (solution containing 1 per cent.H,SO,) gave nearly the same number, namely, 0.0302. When, however, the amount of sulphuric acid is increased until the solution contains about 35 per cent. of the acid, the value of C diminishes to 0.0197 (for details of this work, see Cain, Ber., 1905, 38, 2511). It follows, therefore, that an increase in the quantity of sulphuric acid produces an apparent increase in the stability of the diazo-compound, This is thought to be due (Zoc. cit.) to the withdrawal of water from the reaction by the sulphuric acid. A third method, which yields by far the best result with refractory substances, is that described in the English Patent No. 7233 of 1897 (Kalle and CO. i9.R.-P. No. 95339), which consists in dropping the diazo-solution into a mixture of dilute sulphuric acid and sodium sulphate heated to 136-145" and allowing any volatile products to distil over. This method, applied in the Patent Specification especially to theTHE ACTION OF WATER ON DIAZO-SALTS.21 production of guaiacol from the diazo-salt of o-anisidine, is successful where others have failed. Although by using this method we have been successful in obtain- ing phenols where previous observers have failed, many of the sub- stances examined have given good yields of the corresponding phenols under the ordinary conditions. This applies particularly to the cases of the diazo-salts from dibromoaniline, dibromo-p-toluidine, and bromo- and chloro-p-toluidines, which were described by Wroblewski in 1874 as yielding no trace whatever of phenols, but only the substituted hydrocarbon. More recently (in 1884), he attributes this abnormality to the presence of a minute quantity of alcohol in the diazo-derivative, left in during the preparation. This explanation is possibly correct, although it is evident that the quantity of alcohol contained in the diazo-salt must have been considerable.I n every case which has been examined, we have been able t o obtain the corresponding phenols, and therefore prove that there is, so far as we know, no case in the benzene series where an ortho-substituent hinders or diverts the course of the reaction, as is, apparently, the case in the diphenyl series. I n addition to this we have been able to throw some light on the course of the diazo-reaction as applied to the sub- stances here described.EXPERIMENT A L. o- Anisicline. Limpach (.Bey., 1891, 24, 4136) prepared the diazo-salt from this substance and passed steam through the solution, but (‘ es t r a t voll- stiindige Verharzung ein ” and no guaiacol could be detected. Gatter- mann (Ber., 1899, 32, 1136) attempted to prepare the hydroxy-com- pound, and remarks (( dass auch dieses (namely, o-anisidine) eine ungewohnlich bestandige Diazoverbindung bildet, die selbst nach dem Erhitzen in einer Bombe auf uber 100’ noch nicht zersetzt war.” As we have been able to isolate guaiacol in the products of decomposition as carried out in the usual may, and apparently by the same method as Limpach used, we give the full details of the experiment. o-Anisidine (24.6 grams) was dissolved in water and 60 C.C.of concentrated hydrochloric acid, and diazotised with addition of 200 C.C. of normal sodium nitrite at 20-25‘. Concentrated sulphuric acid (60 c.c.) was now added and steam passed into the diazo-solution in a large flask arranged for steam distillation. The decomposition proceeded very slowly and there was no violent evolution of nitrogen as in the case of more unstable diazonium salts. The colourless solution gradually turned pink, which was obviously due to the formation of an azo-colour- iug matter, this being found to dye wool direct from an acid bath.22 CAIN AND NORMAN: The colouring matter is therefore most probably produced by the com- bination of the diazonium salt with the guaiacol formed, and con- sequently possesses the formula CH3*O*C6H4*N:N*C6H3(OH)*O*CH,.A t a r gradually collected in the flask and an oil was seen to distil with the steam. The distillation was carried on for four to five hours, and the contents of the flask, when tested the following day, gave no colour with ‘‘ R salt,’’ showing that the diazonium salt had been com- pletely decomposed. Examination. of Residw-The solidified tar was filtered, dried, powdered, and in one experiment boiled out with water, which dissolved the foregoing azo-colouring matter. In other experiments this treatment with hot water was omitted. The dry powder was then extracted with ether, leaving a tarry residue. The ethereal solution was dried over calcium chloride, filtered, and the ether distilled off ; a viscid oil was left which distilled above 300O.The distillate was left for some days in a desiccator over sulphuric acid, when large, flat, square tables had crystallised; these were dried on porous porcelain and recrystallised from dilute acetic acid, when fern-like needles separated (m. p. 88-89’), The boiling point was a little above 310’. The substance was soluble in alkalis, being reprecipitated by acids. The high boiling point suggested the formation of a con- densation product, and analysis showed that probably the mono-methyl ether of o-dihydroxydiphenyl, OH(2)C,H,*C,H4( 2)0*CH,, had been formed. 1 2 5’ 9t 1’ The yield was very small. 0.1074 gave 0,3057 CO, and 0.0609 H,O. Cl3H1,O2 requires C = 77.96 ; H = 6.05 per cent. Examhaation of the Steam Distillate.-The aqueous distillate con- taining drops of oil was saturated with salt and extracted with ether, After evaporating off the ether from the dried solution, an oil was left which was distilled. The temperature rose gradually to nearly 300O.On rectifying, a large fraction,was collected at 195--205O, when the distillation was stopped. This oil was found to be gusiacol (b. p. 2 0 5 O , m. p. 33O) ; it solidified in a desiccator, gave a green colour with ferric chloride, and was identical with a sample of guaiacol prepared accord- ing to the above-mentioned English Patent. The residue in the distilling flask was extracted with ether and the oil left on evaporating off the ether solidified to large, square, tabular crystals. These were recrystallised from dilute acetic acid and melted at 88-89O. A further quantity of the methyl ether of o-dihydroxydiphenyl had thus distilled over with the guaiacol during the steam distillation.The diazo-salt from o-anisidine was also decomposed exactly as described in the fore- going English Patent and a satisfactory yield of gusiacol was obtained. C = 77-63 ; H = 6.30.THE ACTION OF WATER ON DIAZO-SALTS. 23 Dichloronniline (NH, : C1: C1= 1 : 2 : 5). Schlieper (Bw., 1893.26, 2465) was unable to prepare the diazo-salt of this substance, obtaining only the diazoamino-compound. This was also confirmed by Zettel (Rer., 1893, 26, 2471). As no mineral acid was used by these chemists, but the diazotisation attempted by the use of amyl nitrite, we were confident of being able to prepare the diazo- solution in the usual way, and a clear solution was easily obtained.I n one experiment the base was dissolved in hydrochloric acid, sulphuric acid added, and sodium nitrite solution dropped slowly into the boiling solution. A red solid formed in the flask was dried a.nd recrystallised from benzene, the solution yielding shining, bronze-coloured plates (m. p. 195O). 0.1330 gave 14.8 C.C. nitrogen at 18.5' and 755 mm. C,,H7N,Cl, requires N = 12.54 per cent. N = 13.0. By heating with glacial acetic acid and acetic anhydride, an acetyl compound was obtained, melting at 226'. The substance formed in the reaction was therefore t'he aminoazo-compound having the above formula; it dissolved with a red colour in concentrated sulphuric acid. During the progress of these experiments, a paper appeared by Noelting and Kopp (Ber., 1905, 38, 3506) describing a number of derivatives of this dichloroaniline and the preparation of the above aminoazo-compound by heating a mixture of the hydrochloride of the base, the diazoamino-compound, and the base itself. I n this way they obtained the aminoazo-compound corresponding exactly with the substance above described.They describe also the preparation of the dichlorophenol by decomposition of the diazo-salt, and therefore there was no necessity for us to carry on our work further in this direction. DibromoaniZine (NH2 : Br : Br = 1 : 2 : 4). Wroblewski (Bey., 1874, 7, 1061) obtained only dibromobenzene by the decomposition of the diazo-salt and detected no trace of the phenol. By using the method of the above-mentioned English Patent, the dibromophenol (m.p. 39') was isolated. Br = 63.0. C,H,OBr, requires Br = 63.5 per cent. 0.224 gave 0.3332 AgBr. s- T&hZoroaniline. Hantzsch (Ber., 1895, 28, 685) prepared a solution of the diazo- chloride of this substance, and was unable to detect the formation of the corresponding phenol by the action of heat. He says '' Trichlor-24 CAIN AND NORMAN: diazobenzolchlorid lasst sich mit Wasser, ja selbst mit salpetersalzsaure kochen, ohne Stickstoff zu entwickeln oder sich uberhaupt zu verandern.” Under the usual conditions we were also unable t o isolate any trichlorophenol, but by using the patented method a small quantity of this substance ci%lled over with the steam, and melted correctly, namely, at 68’. 0.2511 gave 0.5441 AgC1. Cl=53*4.C,H,OCl, reqliires C1= 53.8 per cent. s- T T ~ 5romoani line. Silberskein ( J. p. Chsm., 1883, 27, 98) was unable t o obtain any phenolic derivative by boiling s-tribromobenzenediazonium sulphate or nitrate with dilute acids. Ihntzsch also (Bey., 1900, 33, 2517) obtained ‘‘ gar kein Tribrompienol.” Orton (Proc., 1905, 21,170), by using Heinichen’s method, was unsuccessful in his attempt t o prepare this subRtance. We ca11 confirm the work of these chemists, as under ordinary conditions no phenol can be isolated. When, how- ever, the patented method is applied, a small quantity of s-tribromo- phenol (m. p. 92’) can be obt&md. 0.2113 gave 0.3590 AgBr. Br = 72.31. C,H,OBr, requires Br = 72-51 per cent. Chloro-p-toluidine (NH, : CH, : C1= 1 : 4 : 2). Wroblewski (Bey., 1874, 7, 1061 ; Ann., 1873, 168, 147) states that the diazonium salt of this substance on decomposition by boiling yields m-chlorotoluene and no phenol.By decomposing the diazo- solution according to the patented method and by extraction of the distillate with ether, an oil was obtained boiling at 191’. C1= 24.47. C,H,OCl requires C1= 24-86 per cent. 0.1621 gave 0.1 607 AgC1. The substance is therefore chlorocresol (OH : CH, : C1= 1 : 4 : 2). Brmo-p-toluidine (NH, : CH, : Br = 1 : 4 : 2). Wroblewski in this case also (Zoc. cit.) failed to obtain the bromo- cresol, but described the production of the m-bromotoluene ; due, no doubt, as indicated above, to the presence of alcohol. When steam is passed through the solution containing the diazonium salt, an oil (b.p. 214’) distils over, which is identical in every way with the bromocresol described by Schall and Dralle (Bw., 1884, 17, 2530). 0.2209 gave 0.22053 AgBr. Br = 42.48. CiH70Br requires Br = 42-78 per cent.THE ACTION OF WATER ON DIAZO-SALTS. 25 Dibromo-p-tohidime (NH, : CH, : Br : Br = 1 : 4 : 2 : 6). Here again Wroblewski obtained ‘ I nicht die geringste Spur von By the patented method we have Kresol,” but only dibromotolueno. had no difficulty in obtaining the expected dibromocresol (m. p. 48O). 0-211 gave 0.297 AgBr. Br = 59-90. C7H,0Br, requires Br = 60.15 per cent. It is to be concluded from the above experiments that the supposed cases of abnormal behaviour on boiling certain ortho-substituted diazonium salts with water have no foundation in fact.We do not claim to have examined every alleged exception to the general rule, but think that the number of examples shown in this paper is sufficient to indicate that any remaining instances which may possibly have been overlooked by us are to be regarded with suspicion. I n conclusion, we wish to express our grateful thanks to the Chemical Society for the grant from the Research Fund by means of which the cost of this work was partly defrayed. NOTE BY JOHN CANNELL CAIN.-with the completion of the fore- going work it may be of interest to summarise the general results of a series of researches on the diazo-reaction carried out by me during the past four years. The action of water on diazonium salts (mostly in presence of a mineral acid) has been investigated both quantita- tively and qualitatively, and the main conclusions are as follows : 1.Diazonium salts of the benzene and naphthalene series decom- pose according to the equation expressing a unimolecular reaction, namely : 1 A -log-- = C (a constant) t A - x (Trans., 1902, 81, 1412 ; 1903, 83, 206). Only one tetrazo-salt (from dichlorobenzidine) was found to conform to this rule. By the deter- mination of the value of “0” in the above equation, the relative stability of diazoniurn salts is obtained. 2. The rate of decomposition increases rapidly with the temperature, the values of “ C ” obtained being in accordance with Arrhenius’ formula for the temperature-coefficient, namely : (Trans., 1903, 83, 470). 3. The rate of decomposition (in the case of benzenediazonium salts) is independent of the quantity of mineral acid present (except sulphuric acid, which tends to withdraw water from the sphere of action), and Ct, = Ct,.e 4 Ti - TO) TI TO26 CROSSLEY AND RENOUF : DIHYDROLAUROLENE, DIHYDRO- is independent of the nature of the acid. Equivalent solutions of benzenediazonium chloride, sulphate, nitrate, and oxalate decompose at the same rate (Ber., 1905, 38, 2511). 4. The primary action in the decomposition (except possibly in the diphenyl series) is that phenols are formed. A number of apparent exceptions to this rule have been proved to be groundless (this paper). Unless special precautions are taken in the decomposition of very stable diazonium salts, the unchanged diazo-salt condenses with the phenol formed (probably yielding either a diazo-oxy-compound or an azo-colouring matter), and consequently the latter is not isolated (Zoc. I n the diphenyl series, the tetrazo-salts from dianisidine and dichlorobenzidine yield as chief products quinones and not phenols ; Thereas benzidine, tolidine, &c., behave normally (Trans., 1903, 83, 688). The tetrazo-salt from dichlorobenzidine behaves normally in the various other diazo-reactions (Trans., 1904, 85, '7). 5. The influence of a substituent in the ortho-position with respect to one diazonium group contained in a tetrazo-salt is very great, and it has been possible in such a case to decompose one diazonium group completely and leave the other intact, the hydroxydiazonium salt thus being obtained in the crystalline condition from boiling water (Trans., 1905, 87, 5). cit.). MUNICIPAL TECHNICAL SCHOOL, BURY, LANCASHIRE.
ISSN:0368-1645
DOI:10.1039/CT9068900019
出版商:RSC
年代:1906
数据来源: RSC
|
6. |
VI.—The supposed identity of dihydrolaurolene and dihydroisolaurolene with 1 : 1-dimethylhexahydrobenzene |
|
Journal of the Chemical Society, Transactions,
Volume 89,
Issue 1,
1906,
Page 26-46
Arthur William Crossley,
Preview
|
PDF (1340KB)
|
|
摘要:
26 CROSSLEY AND RENOUF : DIHYDROLAUROLENE, DIHYDRO- VI.-The supposed identity of Dihydrolaurolene and Dihydi8oisolaurolcne with 1 : 1 -Dinzethylhexahyclrobenxene. By ARTHUR WILLIAM CROSSLEY and NORA RENOUF, Salters’ Research Fellow. IT was stated in a previous communication (Trans., 1905, 87, 1487) that the main object the authors had in view when preparing 1 : 1-di- rnethylhexahydrobenzene was a comparison of its properties with those of dihydrolaurolene and dihydroisolaurolene, with which hydrocarbons it has been supposed by Zelinsky and Lepeschkin (AInnaZen, 190 1,319, 303) to be identical. As these authors based their conclusions on the physical properties of the hydrocarbons and gave no details of their chemical properties, such as oxidation products, it became necessary to prepare dihydrolauroiene and dihydroisolaurolene, and to investigate them from the chemical standpoint.ISOLAUXOLENE AND 1 : 1 -DIMETRYLHEXAHYDRORENZENE 27 The following is a list of the more important papers dealing with laurolene and isolaurolene, and all references in this communication are to these papers unless otherwise stated.Lacurole ne.-Wreden, Annalen, 1877, 187, 171 j Reyher, Inaug. Dissertation, Leipig, 1891, 51 ; Aschan, Annulen, 1896, 290, 185 ; Noyes, Amer. Chem. J., 1895, 17,432 ; Walker and Henderson, Trans., 1896, 69, 750 ; Zelinsky and Lepeschkin, Annalen, 1901, 319, 311. i s o L a u v o I ene.-Moitessier, Juhresber., 1866 ; Wreden, ibid. ; Damsky, Ber., 1887, 20, 2959; Koenigs and Meyer, Ber., 1894, 27, 3470; Blanc., Bull. sbc.chim., 1898, [iii], 19, 699 ; Zelinsky and Lepeschkin, ibid., p. 307. B i h y d r o I a zc r o lene. Laurolene was first prepared by the distillation of camphanic acid, and is a colourless, highly refractive liquid boiling at 119-122', by far the largest portion distilling at 119.5-120*5". It possesses the properties previously attributed to it except as regards optical rota- tion, which was never found to be as high as + 2 3 O (see p. 38), a point which is being further investigated. Laurolene is not identical with 1 : 1 -dimethyl-A3-tetrahydrobenzene (Trans., 1905, 87, 1600), with which it is isomeric. The conversion of laurolene into its hydriodide is an operation attended with great difficulty, which information would not be gathered from the description given by Zelinsky and Lepeschkin, who state that they obtained more than 70 per cent.of the theoretical quan- tity, boiling at 69O/15 mm., by heating the hydrocarbon with fuming hydriodic acid for five hours in a water-bath. The present authors, although varying the amount of hydriodic acid used and the length of time of, heating, could never obtain more than 25-30 per cent. of the theoretical quantity of hydriodide, boiling much higher than as above stated, namely, 101-106°/33 mm., and a certain amount of unchanged hydrocarbon was always recovered. Zelinsky and Lepeschkin do not quote an analysis of the hydriodide, nor was it found practicable on the present occasion to carry out an iodine estimation, as the substance cannot be distilled even in a vacuum without some decomposition and always contains free iodine.The agent employed by Zelinsky and Lepeschkin for the conversion of the hydriodide into dihydrolaurolene was zinc-palladium, but as experiment showed that reduction of the hydriodide by means of zinc dust and aqueous alcohol leads t o the same result the latter method was employed, as it is much less troublesome to carry out. The process is again a wasteful one, as only 30 per cent. of the theoretical quantity of the pure saturated hydrocarbon is obtained, which is28 CROSSLEY AND RENOUF : DIHYDROLAUROLENE, DIHYDRO- largely due to the fact that during reduction the elements of hydrogen iodide are to some extent removed from the hydriodide, giving rise to an unsaturated hydrocarbon, which is destroyed on treating the raw reduction product with potassium permanganate.That the dihydrolaurolene obtained by the above reactions differs from 1 : 1-dimethylhexahydrobenzene will be seen from the following comparison : 1 : 1-Dimethylhexa- 1 1200 0,7864 { resembling PP-dimethyl- hydrobenzene ... J geranium adipic acid Dihydrolaurolene 11 1 *5--114O 0.7633 camphoraceous oxalic acid oxidation b. p. sp. gr. odour. product. Regarding the probable constitution of dihydrolaurolene, there is not much to be said on the present occasion. Zelinsky and Lepesch- kin have shown that, when laurolene hydriodide is treated with di- methylaniline, the elements of hydrogen iodide are removed, and laurolene is recovered unchanged except that it is optically inactive. If, therefore, laurolene gave oxidation products containing the carbon complex present in the hydrocarbon, as is the case with isolaurolene, the determination of its constitution would not be a difficult matter, but it does not, and it has been found, in accordance with the observa- tions of previous experimenters, that the only definite oxidation pro- ducts obtainable from laurolene are oxalic and acetic acids.It seems probable that, as Zelinsky and Lepeschkin point out, laurolene (ibid., p. 312) is a mixture, for its boiling point is not par- ticularly constant, its behaviour towards hydrogen iodide is not that of a homogeneous substance, and, further, although prepared from pure camphanic acid under precisely similar conditions, its optical activity varies (see p. 38). Moreover, this view is supported by a considera- tion of its magnetic rotation (see p.36) and of the theory of its formation from camphanic acid (I), which takes place as here re- presented : C H , - G l CH,*$?H- CH,-C--CO = 2c02 + CH2*Y- 11. I 1 (pH,), 9 I 7(CH3)2 I c=, CH3 I. It is obvious that the bonds in a substance having formula I1 must at once undergo rearrangement to give a stable compound, and this may occur in a variety of ways, giving rise to pentamethylene or hexamethylene derivatives :ISOLAUROLENE AND 1 : 1-DIMETHYLHEXAEYDROBENZENE 29 111. IV. V. CH,--GH I V*CH, dH2*FH-6H, VI . CH, Experimental evidence is not yet sufficiently complete to allow a definite expression of opinion as to how the reaction takes place, but it may be pointed out that, although dihydrolaurolene is not identical with dihydroisolaurolene, there is, on theoretical grounds, no reason why the former should not contain a proportion of the latter, for, supposing that the intermediate product represented by formula I1 rearranges itself to form substances having either formula I11 or IV, then on treatment with hydriodic acid and reduction of the hydriodide formed there would be produced 1 : 1 : 2-trimethylcyclopentane identi- cal with dihydroisolaurolene.Under these conditions, however, some aa-dimethylglutaric acid should result from the oxidation of dihydro- laurolene, but up to the present stage of the inquiry it has not been found possible to isolate even traces of this acid. D ih ydroisolaurolene. isoLaurolene has usually been prepared by heating isolauronolic acid in sealed tubes for eight hours a t a temperature of 300-340° (Blanc, p.700; Zelinsky and Lepeschkin, p. 307), a process which, as pointed out, frequently means considerable loss on account of the bursting of tubes. A new method was therefore sought, and it was found that if isolauronolic acid is heated with one and a half times its weight of pure anthracene somewhat above the melting point of the mixture, a reaction sets in and isolaurolene slowly distils over, the end of the reaction being indicated by the fact that anthracene sublimes into the neck of the distillation flask. The reaction takes three to four hours for completion, but when once the temperature has been regulated no further attention is required, and the yield of isolaurolene is almost quantitative.When treated with fuming hydrioclic acid, isolaurolene is readily converted into the liquid hydriodide (yield 75 per cent. of the theoretical), which, on treatment with zinc dust in aqueous alcoholic solution, gives from 60 to 62 per cent. of the theoretical amount of dihydroisolaurolene, which hydrocarbon is not identical30 CROSSLEY AKD BENOUF : DIHYDROLAUROLENE, DIRYDRO- with 1 : 1 -dimethylhexahydro benzene, as seen from comparison : 1 : 1-Dimethglhexa- hydrobenzene . . . b. p. sp. gr. odonr. resembling geranium } 120' 0.7864 { sweet cam- Dihydroisolaurolene 11 3-1 13.5" 0.7762 the following oxidation product. @@dimethy 1- adipic acid aa-dimethyl- glutaric acid Constit&ion of Biluyo%oisoZauroZene. As the formula to be assigned to dihydroisolaurolene nahrally depends on the constitution of isolaurolene, the evidence in favour of the latter substance being 1 : 1 : 2-trimethyl-A2-cycZopentene must be very briefly reviewed.Damsky (p. 2959) was the first experimenter to investigate the properties of isolaurolene at all fully ; his oxidation experiments '( did not, however, give rise t o any solid product, but only to oily fatty acids." This oil must have been the ketonic acid, C,H,,O,, described on p. 46, which, on being extracted from the oxidation liquid, is accompanied by small amounts of acetic acid, and does not show any signs of solidificatiou until it has been distilled. In 1898, Blanc definitely established the constitution of isolaurolene in the following manner. Accepting his formula for isolauronolic acid (VII) as correct, he believed isolaurolene to be represented by formula VIII : CH,*F](CH,), =: co, + I p H 3 CH,* 7<""3>2 I p = 3 CH,* C CO,H C'H;CH VII.VIII. that is to say, that during the loss of carbon dioxide no change in the structure of the ring takes place. This was proved by the fact that isolauronolic chloride (IX), when treated with zinc methide, gave rise to the same ketone (X) as is produced by the action of acetyl chloride on isolaurolene in presence of aluminium chloride : "H,*$wH3)2 cII,*c*coc1 A CH,*y(CHd, I EaCH:3 + Zn(CH3)2 \ IX. I Ii-CH, cILI,-F(CH,), Z CH,.C*CO*CH3 CI3,nCH I g*CH3 + CH;COCl ,-" x. Blanc further showed that when isolaurolene is oxidised withISOLAUROLENE AND 1 : 1-DIMETHYLHEXAHYDROBENZENE 31 potassium permanganate there is obtained y-acetyldimethylbutyric acid (XI), previously obtained by him from the oxidation of isolau- ronolic acid (Bull. SOC.chim., 1898, [ iii], 19, 533) : and this ketonic acid, on further oxidation, gave m-dimethylglutaric acid (XII). As Blanc says, the formation of 7-acetyldimethylbutyric acid by the Oxidation of isolmrolene shows that it can only have the constitution represented by formula VIII and no other. ‘‘ Aucune ambiguite ici n’est possible.” Yet Zelinsky and Lepeschkin in 1901 did not accept this conclusion, but regarded isolaurolene as a six-ring compound. Accepting then the foregoing formula (VIII) for isolaurolene, the next point is to prove that when isolaurolene is treated with fuming hydr- iodic acid a t a temperature of 120-125O no change in the nature of the ring is produced.This might seem probable, because isolaurolene, when brought into contact with hydriodic acid at the ordinary tem- perature, gives a solid and very unstable hydriodide; whereas at- 120-1 25O, a comparatively stable and liquid hydriodide is produced. Nevertheless, it is easily demonstrated that this liquid hydriodide con- tains the same carbon complex as isolaurolene itself. For this purpose, the hydriodide was treated with diethylaniline, when it readily lost the elements of hydrogen iodide, giving an unsaturated hydrocarbon, C8HIQ, boiling at 108-1 08*5O, and possess- ing properties identical with those of isolaurolene. I n order that there should be no doubt on this point, the hydrocarbon was oxidised with potassium permanganate, when it yielded 7-acetyldimethylbutgric acid, and this, on further oxidation with sodium hypobromite, gave arc-dimethylglutaric acid. These are the same products as Blanc obtained by the oxidation of isolaurolene (see above), and conclusively prove that no isomeric change takes place during the production of the hydriodide, which must therefore have one of the following formulze : There is, moreover, no reason to suppose that heating this hydriodide with zinc dust in aqueous alcoholic solution would produce a change in the construction of the ring, and this is proved by the fact that when32 CROSSLEY AND RENOUF : DIHYDROLAUROLENE, DIHYDRO- the resulting hydrocarbon (dihydroisolaurolene) is oxidised with diluted nitric acid it gives rise to au-dimethylglutaric acid : that is, to the same oxidation product as isolauronolic acid yields when treated with diluted nitric acid (Blanc, Bull.Xoc. chim., 1898, [iii], 10, 284). These experiments prove conclusively that dihydroisolaurolene is a pentamethylene derivative and is 1 : 1 : 2-trimethyZcyclopenntalze, a deduction which receives striking confirmation from the magnetic rotation of dihydroisolaurolene, and to which Dr. Perkin makes allusion in his report (see p. 36). Zelinsky and Lepeschkin concluded, as a result of their experiments, that dihydrolaurolene and dihydroisolaurolene were identical, a con- clusion which does not seem to be warranted by the results obtained by the present authors. Further, from a consideration purely of the physical properties of dihydroisolaurolene, these authors supposed that it was a hexamethylene derivative, and, since laurolene hydriodide and isolaurolene hydriodide, both of which substances contain the same carbon ring as dihydroisolaurolene, when treated with diethylaniline regenerate lnurolene and isolaurolene respectively, that therefore the latter substances contain a six-membered carbon ring, which '' very probably is also present in isolauronolic and camphanic acids." '' Man konnte weiter gehen und schon voraussetzen, dass die Kamphersaure .. . einen Hexamethylenring besitzt." Komppa's synthesis of cam- phoric acid (Ber., 1903, 36, 4332) is a sufficient answer to the latter suggest ion, Zelinsky and Lepeschkin then argue that dihydroisolaurolene, C8HI6, must be a dimethylhexamethylene, and since it was not identical with 1 : 2-, 1 : 3-, or 1 : 4-dimethylhexahydrobenzene, all of which sub- stances have been described by Zelinsky, i t must be the only remain- ing possibility, namely, 1 : 1 -dimethylhexahydrobenzene, a conclusion which is certainly wrong.They attempt to explain the fact that the boiling point of their supposed 1 : 1 -dimethylhexahydrobenzene (1 14') is lower than the boiling points of the 1 : 2-, 1 : 3-, and 1 : 4-isomerides, because the two methyl groups are bound to one and the same carbon atom, and quote in support of this the fact that 1 : 3 : 3-trimethyl- hexahydrobenzene, which also contains two methyl groups attached to the same carbon atom, boils 4 O to 5 O lower than theisomeric 1 : 2 : 5-tri- methylhexahydrobenzene.We now know chat the boiling point of 1 : 1-dimethylhexahydrobenzene is almost identical with those of theISOLAUROLENE AND 1 : 1-DIMETHYLHEXAHYDROBENZENE. 33 isomeric hydrocarbons, as will be seen from the following table, and therefore the presence of the gem-dimethyl group does not in this case give a compound of lower boiling point than its isomerides : 0 bservers. b. p. sp. gr. 1 : 2-Dimethylhexahydrobenzene (Zelinsky and 1 : 3-Dimethylhexahydrobenzene (Zelinsky and 1 : 4-Dimethylhexahydrobenzene (Zelinsky and 1 : 1 -Dimethylhexahydrobenzene (Crossley and Lepeschkin, Annalen, 1901, 319, 319) ......... 116-118' 0.7733 Naumoff, Be?.., 1895, 28, 781) .................. 1195" 0.7688 Keformatsky, Ber., 1898, 31, 3207) ............119.5-12W Renouf, Trans., 1905, 87, 1498) ............... 120' 0,7864 0.7690 Zelinsky and Lepeschkin further state that, if dihydroisolaurolene were a pentamethylene derivative, it would be 1 : 1 : 2-trimethylcyclo- pentane,and its boiling point would not therefore be higher than ill', because the difference in boiling point for the homologues of this series is about 20°; but as it contains two methyl groups attached to the same carbon atom, so its boiling point would probably be below 11 1'. The boiling point of dihydroisolaurolene (1 : 1 : 2-trimethylcyclo- pentane) is now shown to be 113-113*5', or 22" higher than the boil- ing point of dimethylcyclopentane (91-91-4') as given by Zelinsky and Rudsky (Jour. Buss. Chem. Xoc., 1899, 31, 408), which is an almost identical difference as that found between the boiling points of cyclo- pentane, 50.3-50.7' ( Wislicenus, AnnaZen, 1893, 275, 329), and rnethylcyclopentane (Zelinsky, .I Buss.Chem. Soc., 31, 408) 72-72*2O, namely, 21.5'. The authors desire to express their warmest thanks to Dr. W. H. Perkin, sen., for the interest he has taken in this work, and for kindly determining the physical constants of the hydrocarbons, on which he reports as follows : Densities, Magnetic Rotations, a n d Refractive Powers of Lu u r o Ze n e, B i h y d r o Zacur o Zen e, is o Laur ol e me, a n d B ithydro- i s o l a u r o l ene. .Laurolene. Density : d4'/4'= 0.8097 ; d1O0/10' = 0.8048 ; d15'/15'= 0.8010 ; d2Oo/2O0 = 0.7974 ; d25'/25'= 0.7939. Magnetic rotation : t, sp. rot. Alol.rot. 19.1" 1.1737 5.987 VOL. LXXXIX. D34 CROSSLEY AND RENOUF : DIHYDROLAUROLENE, DIHYDRO- Refractive power : t= 19.5" ; d19*5'/4'= 0.79650. Index of Sp. refraction. 1101. refraction. P i ? p i f. Calculated. refraction, I*- H ...... 1.44253 0.5555 9 61,114 60.5 H ...... 1.45246 0.56806 62.486 H ...... 1,45845 057558 63.314 - - Dispersion Ha - H, = 2.20. Uihydrolaurohe. Density : d4'/4'= OW18 ; d1O0/1O0= 0,7670 ; d15'/15'= 0,7633 ; Magnetic rotation : d20°/200 = 0.7596 ; d25'/25'= 0.7567. t. Sp. rot. Mol. rot. 19.6' 1*0181 8.332 Refractive power : t = 19.8' ; dl9*8'/4O= 0.7588. Index of Sp. refraction. Mol. refraction. ; 5. Calculated. refraction. P-1. P* d If ...... 1.42424 054588 61.138 60.8 H ...... 1.42162 0.55561 62.228 H ...... 142591 0.56126 62.86 1 - - Dispersion Ha - H, = 1.723.isolaztrolene. I)eu.sitg : d-Lo/4* = 0,7953 ; dlOO/lO" = 0.7907 ; d15'/15'= 0,7867 ; dZO0/2Oo= 0.7830 ; d25"/25'= 0.7795. Magnetic rotation : t. Sp. rot. 1101. rot 14.3" 1,1270 8.749 Refractive power : t = ld*1° ; d16°10/40 = 0.785 10.ISOLAUTROLENE AND 1 : I-DIMETHYLHEXAHYDROBENZENE~ 35 Index of Sp. refraction. Mol. refraction. H ...... 1.43227 0.55059 60-565 60.5 H ...... 1.44136 0.563 16 61,847 - H ...... 1.44690 0.56923 62.615 Calculated. refraction. P-2, q p . P. d - Dispersion Ha - H, = 2.050. Dilt,ydroisoZauroZene. Density : d4'/4' = 0.7847 ; dlOo/lOo = 0*7800 ; dl5'/ 15'= 0.7762 ; d20'/20'= 0.7727 ; d25O/25" = 0.7694. Magnetic rotation : t. Sp. rot. Mol. rot. 1 4 ~ 3 ~ 1.0298 8.249 Refractive power : t = 16.2" ; d 1 6 .2 ' / ~ = 0.77463. Index of Sp. refraction. Mol. refraction. refraction. P - 1 P - 1 P- d T P . H ...... 1.43244 0.54534 61-078 H ...... 1.42998 0.55508 62.169 H ...... 1,43398 0 -5 6 02 4 62*815 Dispersion Ha - H, = 1 *7 37. Calculated. 60.8 - - t)n comparing the densities and magnetic rotations of dihydro- isolaurolene and isolaurolene, also of dihydrolaurolene and laurolene, respectively with those of 1 : 1-dimethylhexahydrobenzene and 1 : 1- dimethyl-AWdxahydrobenzene (Trans., 1905, 87, 149l), considerable differences are noticed : Magnetic Densities. Difference, rotations. Differeiice, ......... ;:;:; +0'099 1 : l-Dimethyl-A3-tetrahydrobenzene ... 0'8040 - o,0173 @3:: - o.154 1 : 1-Dimethyl-A3-tetrahydrobenzene ... 0.8040 - o,oo30 ;*iN); + o.084 1 : l-Dimethylhexahydrobenzene 0'7864 Dihydroisolanrolene........................... 0'7762 - o'0102 isoLaurolene ................................... 0 -7867 1 : l-Dimethylhexahydrobenzene ......... 0.7864 Dihydrolaurolene ............................. 0'7633 0'0231 :'ti: fo'182 Laurolene ....................................... 0'8010 I n the cases of dihydroisolaurolene and isolaurolene, me have large and irregular differences, which are dissimilar to those of dihydro- laurolene and laurolene. These iso-compounds are evidently different Crorn all the others of the same composition, and one especial 0 236 CROSSLEY .4ND 1tENoUF : DIHYDROLAUHOLENE, DIHYDKO- peculiarity is that the difference between the magnetic rotations of the saturated and unsaturated products is remarkably small, thus : Mol.rot. Dilference. ............... 0.500. isoLaurolene S.743 Dihydroisolaurolene ...... S-24'3 Now it has been shown that the average influence of uusaturation, mused by the loss of H, in the paraffin series, results in a rise of rotation of +05'20 (Trans., 1902, 81, 292), and that, when these unsaturated chain compounds are joined up by loss of H2 soas to form ring compounds, the result of unsaturation remains practically the same. This has been found to be the case with dihydrobenzene and with 1 : 1-dimethyl-A3-tetrahydrobenzene. This is, however, a much larger effect than that found in the case of dihydroisolaurolene and iso- laurolene ; but i t has been shown that in the lower menibera of the ali- phatic series the differences for unsaturation are exceptionally small, as seen in the halogen derivatives of ethylene and propylene (Trans., 1884, 45, 568).If the individual rotations of the unsaturated hydrocarbons be examined (Trans., 1895,67,261) it will be observed that in the case of amylene the difference amounts to only 0.578, and therefore we may assume that this would be about the influence of unsaturation in the corresponding ring compounds. It is very interesting to note that this is near to that found in the case of isolaurolene, indicating that this substance and its dihydro-derivative are trimethyl five carbon ring compounds. This is quite in agreement with the view of Blanc as regards isolaurolene and the results obtained by the authors of the present communication regarding dihydroisolaurolene.The differences observed in the cases of dihydrolaurolene and laurolene are difficult to interpret; for if these hydrocarbons are related to each other in the same way as dimethylhexahydrobenzene is related to dimethyltetrahydrobenzene, these differences should be similar for each of the properties, whereas they are much larger in the case of dihydrolaurolene. It is, however, worth while calling attention to the difference between the magnetic rotations of laurolene and dihydrolaurolene, which is as follows : Difference. ............. + 0.655. Laurolene.. 8.YS7 Dihydrolaurolene ... 8.332 This, it will be seen, lies between the effect of unsaturation of a five and a six carbon ring and might result if laurolene and dihydro- laurolene were mixtures of such compounds.Zelinsky and Lepeschkin (page 382) have proposed the two bridged ring f o r r n u l ~ f u r isolaurolene and laurolene :ISOLAUROLENE m n I : I-T)IMETHYT,HF,XAHTDRORENZENE. 37 Laurolene. but the magnetic rotations of such compounds mould be very much smaller than those found, because the effect of the bridged ring is quite different t o that of an ordinary double linking (Trans., 1902,81, 266). A comparison of the refractive values of these hydrocarbons, made on the same lines as that of densities or magnetic rotations, does not appear to afford much light in reference to their structure. EX P E R I M E N T A L. Preparation of Laurolene. Bromocamphoric anhydride was prepared according to the directions given by Zelinsky and Lepeschkin (p.310), except that the raw product was crystallised from glacial acetic acid instead of chloroform. The yield was about 75-80 grams from 100 grams of camphoric acid. This anhydride was then converted into camphanic acid by heating with a solution of sodium carbonate (Aschan, Ber., 1894, 2'7, 3506). The yield after crystallising from benzene is 55-60 grams from I00 grams of the anhydride. I n preparing lauroleno from camphanic acid, the very precise details given by Aschan (p. 187) were followed. The yield of laiirolene was 33 grams from 150 grams of camphnnic acid, and its purity was proved by analysis : 0.1 149 gave 0,3665 CO, and 0.1 326 H,O. C = 87.00 ; H = 12.82. C,H,, requires C = S7.27 ; H = 12-73 per cent. Pvoperties of the Hy~~occcrbon.-Laurolene is a clear, colourless, highly refractive liquid boiling at 119-122°/760 mm., by far the major portion distilling at 11 9.5-1 20-5O.It possesses an odour resembling both camphor and turpentine, but much less sweet than that of isolaurolene. With alcoholic snl phuric acid (carried out as previously described, Trans., 1905, 87, 1494), the hydrocarbon gives a green colour turning to bronze-green, and when treated with concentrated sulphuric acid in acetic anhydride solution there is produced a dark bronze-green coloration, changing to deep grass- green. Having observed that when laurolene was treated with hydriodic acid (see p. 40) some of the hydrocarbon remained mattacked and appeared to be iinaltered, except as regards optical activity, it was decided to examine the rotations of some of the preparations of38 CROSSLEY AND RENOTTF : DTHYDROLAUROLENE, DlHPDRO- laurolene.This seemed to be more desirable, as the observations of previous workers regarding this point do not, agree, RS mill be seen from the following table : Reference. Source . Rotation. Aschan (p. 189) . . . . .. . . . .. . .. . , .. ... Camphnnic acid . . . .. . [ uIi - 23.0" Walker and Henderson (p. 752) p o ~ ~ ~ ~ r a ~ ' l ~ ~ e ~ h . y l [ u], - 29.2' Tiemannn (Ber., 1900, 33, 2949) Aminolauronolic acid [u] + 19.9" Zelinsky and Lepeschkin (p. 31 1) [ ulD + 22.9" The last-named authors, after partial oxidation with potassium permanganate, obtained laurolene with a rotttion [aIn + 16*2', and express the opinion that on this account laurolene prepared from camphanic acid may possibly be a mixture of isomeric hydrocarbons. Four separately prepared specimens of laurolene have now been examined, and the following numbers obtained : 1.[a], + 11.4'. 2. Inactive. 3. [a], + 6.6". 4. [ a], + 4.1". This irregular rotation might be put down to a difference in the method of distilling camphanic acid, but Aschan gives such very definite instructions as to temperature and the number of drops of the distillate per minute, that it may certainly be said each pre- paration was carried out, as near as it is possible to do so, under identical conditions. The camphanic mid employed was always in the s m e state of purity, and, moreover, specimens 3 and 4 were prepared from the same bulk of camphanic acid. It, mas then thought that two hours' heating of lanrolene with metallic sodium might cause some change to take place, especially as the liquid becomes dark brown during the heating. Specimens 3 and 4 were therefore examined after drying over calcium chloride, and then at intervals during the heating with sodium, but no changa in the initial rotation was observed, and, so far, no satisfactory explanation of this behaviour has been found.Action of Bromine on Lauro2ene.- When a solution of bromine in chloroform is added to a solution of laurolene in the same solvent, cooled in ice-water, a green colour is at once produced, changing to brown, which is destroyed on further addition of bromine, returning as the bromine is used up, and ultimately the solution assumes a violet colour. If then an excess of bromine is added, the violet disappears as the bromine is absorbed, and the green, and finally violet, colorations return.During the whole operation, clouds of hydrogen bromide are evolved, and on evaporating the chloroform a green resin remains. Having found it iinpossible t o get any idea of the quantity of Camphanic acid . . . . . .ISOLAUROLEXE AXn 1 : 1-DIMETHYLHEXAIIYDROBEX’ZESE. 39 bromine used up in chloroform solution, carbon tetrachloride was tried in its place, as recommended by Aschan (p. 190). TJnder these conditions, bromine is gradually absorbed and hydrogen bromide evolved, but none of the colour changes noticed when using chloroform was observed. When 1,0641 grams of the hydrocarbon were taken, the 6rst indication of a permanent bromine colour was observed when 2.2156 grams of bromine had been added, the required amount for absorption of Br, being 1.5477 grams.Nor was the absorption then quite complete, as further :%mounts of bromine were slowly used up on standing. This does not agree with Aschan’s statement that under the above conditions laurolene absorbs exactly two atoms of bromine and no more. On evaporating the carbon tetrachloride solution, hydrogen bromide was evolved and a green resin remained. Oxidation of Laurolene. (1) Vith 21ritlpic Acid.-Six grams of Inurolene were heated in a flask, attached to a condenser, with 80 C.C. of one part fuming nitric acid and two parts water. The residue obtaiaed from this liquid by working it up in the usual way was proved to consist for the moat part of oxalic acid, together with a minute quantity of a dark oily liquid, smelling of burnt sugar, from which no definite chemical compound could be isolated.(2) With Potassium Permc6nganate.-Twenty grams of the hydro- carbon were suspended in 1 litre of water, and powdered potassium permanganate was gradually added until the coloration became per- manent, a result which required 50 grams and occupied seventy hours. The filtered liquid was evaporated to a small bulk, acidified with sulphuric acid, and distilled in steam. The distillate was neutralised with caustic soda, evaporated to complete dryness, and treated with concentrated sulphuric acid, when a volatile liquid passed over, which was proved to consist of acetic acid by its boiling point, and analysis of a silver salt prepared from it.0.21 10 gave 0.1363 Ag. Ag = 64.60. U,H,O,Ag requires Ag = 64 67 per cent. No product of a definite nature could be isolated from the residue of the above steam distillation, nor were any substances other than acetic and oxalic acids obtained by oxidising laurolene with potassium permanganate in acetone solution, or with a mixture of potassium dichromate and sulphuric acid (compare Aschan, p. 193). The action of a nitrating mixture on laurolene was found to give results coinciding with those recorded by Walker and Henderson (p. 752) and Aschan. The action of nitrosyl chloride on laurolene was tried in the hope of obtaining a solid derivative, but only dark green resinous sub-40 CROSSr,ET AICD RENOUF : DTHYDROTAUROJAENE, DIHYDRO- stances were obtained, similar in appearance to the products of the action of bromine on laurolene. taurolene Hydriodide.Laurolene, in quantities of 10 C.C. at a time, was heated, as directed by Zelinsky and Lepeschkin, with 50 C.C. of fuming hydriodic acid (sp. gr. 1.97) in an ordinary stoppered bottle in a water-bath for six hours. The resulting liquid was poured into water and the whole extracted with ether, the ethereal solution washed successively with water, aqueous sodium bicarbonate, a solution of sodium thiosulphate, and finally with water, dried over calcium chloride, and the residue obtained on evaporating the ether distilled under diminished pressure. After working up 33 grams of laurolene in this manner, the following fractions mere collected at 33 mm.Below 90°=10*5 grams; 101-106°= 18.7 grams; 106-150°=5*4 grams. The fraction below 90° was repeatedly distilled over metallic sodium, when it passed over as a clear, colourless, highly refractdive liquid boiling at 119*5-12lo. 0.1166 gave 0.3719 CO, and 0.1352 H,O. This liquid possessed properties identical with those of laurolene, except that it was optically inactive, It is, however, impossible to state, in view of the data given on p. 38, whether racemisation had taken place or not, as the optical activity of the laurolene used in this experiment was not tested before treatment with hydriodic acid. The fraction 101-106° was a greenish-brown liquid and consisted of laurolene hydriodide, which is very much more unstable than iso- laurolene hydriodide.Zelinsky and Lepeschkin (p. 313) give the boil- ing point of this substance as 69O/15 mm., and state that they obtained 15.5 grams from 10 grams of laurolene, but do not mention the quantity of hydriodic acid used or whether they recovered any unaltered hydrocarbon. Although the experiment was repeated under veryvaried conditions, no better yield of the hydriodidecould beobtained, and there was always recovered a certain quantity of unchanged hydro- carbon which, when again heated with fuming hydriodic acid for six hours, was only partially converted into the hydriodide. The fraction 106-1 50' was not further investigated. C = 87.00 ; H= 12.88. C,H,, requires C = 87.27 ; H = 12.73 per cent. Dihydro Zccuro Zene. Thirty-nine grams of laurolene hydriodide were dissolved in 210 C.C.of 90 per cent. alcohol, and 78 grams of zinc dust mixed with an equal volume of .and added, and the whole heated on the water-bath for tenhonrs and then worked up as previously described (Trans., 1905, 87, 1497). The hydrocarbon was suspended in water and treated with potassium permanganate until no further oxidation took place and the whole distilled in steam, when the hydrocarbon slowly passed over. It was separated from the water, dried with calcium chloride, fractionated over sodium, arid analysed : 0.1016 gave 0.3198 CO, and 0,1318 H,O. C,H,, requires C = 85.71 ; H = 14.29 per cent. Dihydrolaurolene is a clear, colourless, refractive liquid boiling at 11 1.5-1 14*/760 mm. and possessing a sweet camphoraceous odoixr ; it does not absorb bromine nor is i t acted on by potassium permangnnate, and gives no evidence of the formation of a nitro-derivative on treat- ment with a mixture of nitric and sulphuric acids.The yield is very much smaller than in the case of dihydroisolaurolene, amounting to about 35 per cent. of the theoretical quantity from the hydriodide employed. Oxidation with ,Vitric Acid.--Two grams of the hydrocarbon were treated in the usual way with 30 C.C. of fuming nitric acid. Large needle-shaped crystals separated from the residual liquid which were proved to consist of oxalic acid. On evaporating to complete dryness and heating with excess of acetyl chloride, only a minute syrupy residue resulted, which was too small to permit of further examina- tion. After finding that dihydroisolaurolene gave act-dimethylglutaric acid on oxidation with diluted nitric acid, dihydrolaurolene was again oxidised exactly as described on p.44. It was not found possible to establish the presence of even the minutest quantities of aa-dimethyl- glutaric acid in the oxidation products obtained. C = 85.83 ; H = 14.41. Preparation of isolauroZe.rze. isoLauronolic acid was prepared according to the directions given by Lees and Perkin (Trans., 1901, ’79, 341), and the yield obtained was as these authors state, namely, from 45-50 per cent. of the weight of camphoric anhydride used, but only when the purest form of aluminium chloride was employed. isoLauronolic acid, mixed with one and a half times its weight of pure anthracene, was placed in a double-necked (Claisen) distillation flask connected with a condenser and carefully heated, when a reaction began almost as soon as the mixture of substances became molten, and a colourless liquid slowly distilled.At the end of three hours, anthracene began to sublime into the neck of the distillation flask, which denoted that the reaction was almost complete, as on heating for62 CROSSLET AND RENOUF : DIHYDROLAUROLENE, DIHYDRO- two hours longer only one or two grams of hydrocarbon passed over. I n the first experiment, 10 grams of isolauronolic acid were used, but the reaction occiirs eqiially readily when 30 or 40 grams are heated a t one time. The hydrocarbon was dried over calcium chloride and dis- tilled from metallic sodium, when the whole passed over at 10S-109°. For the purpose of analysis, it was again distilled over metallic sodium in an atmosphere of carbon dioxide, when i t boiled quite constantly at 108-108*2O. 0.1332 gave 0.4260 CO, and 0.1532 H,O.C = 87.22 ; H= l24”i. C,H,, requires C = 87-27 ; H = 12.73 per cent. C H, * F( CHJ CH,*CH isolaurolene (1 : 1 : 2 -t,rirnetliyl-A2-cylopentene), I ;C;*CH3 , the yield of which is 85-90 per cent. of the theoretical, is a colourless, mobile, highly refractive liquid boiling at 108-108*2°/742 mm., and possessing a sweet odour resembling both camphor and turpentine. With sulphuric acid in alcoholic or acetic anhydride solution, it gives only a pale straw colour, and on adding a few drops of the hydrocarbon to a cold saturated solution of mercuric chloride and shaking, a cloudi- ness appears, and a sticky, amorphous mass separates, which, after standing for some days, becomes pinkish-brown (compare Zelinsky and Lepeschkin, p.308). When a chloroform solution of bromine is added to a solution of the hydrocarbon in the same solvent, coolod in ice-water, the bromine is absorbed without any evolution of hydrogen bromide, the reaction being a quantitative one for the absorption of two atoms of bromine. C,H,, requires Br, = 160. On careful evaporation of the chloroform solution, a practically colourless, crystalline solid was obtained which, when spread on porous plate, set to a waxF mass somewhat resembling camphor, and having a strong odour of camphor and turpentine. It was twice crystallised from methyl alcohol, in which solvent it is very readily soluble, dried as rapidly as possible, and the bromine estimated.1.1809 absorbed 1-7609 Br. Molecular absorption, Rr = 164. 0.1031 gave 0.1429 AgBr. Br = 58-98. C,H,,Br, requires Br = 59.25 per cent. bH,* CH Br readily soluble in the cold in the usual organic media, but can be crystallised from absolute methyl alcohol, when it, separates in fern-IWLAUKOLENE AND 1 : I-DIMETHYLHEXAHYDROBEKZENE. 43 like aggregates of needles melting a t 80-85'. On standing, it decomposes with evolution of hydrogen bromide and gradually resinifios. Damsky (p. 2961) has described the formation of this compound by the direct action of bromine on isolsurolene, but gave to it the formula C8H12Br2, and in support of this quotes a bromine estimation 60.30, whereas the calculated value for CsHI2Br2 is 59.70.Damsky did not in any way purify his compound, and it would probably contain some higher brominated products, which are formed, as Damsky points out, when bromine acts directly on the hydrocarbon. There can be no doubt that this substance is really the dibromo-additive compound of isolaurolene, for when prepared as above described, no hydrogen brom- ide is evolved. It seemed, however, useless to estimate the carbon and hydrogen, as the calculated numbers for C8H1,Br2 and C,H,,Br, are so close to one another as to prevent any accurate conclusions from being drawn. isoLaurolerze Hydriodide. Quantities of isolaurolene were worked up in the following manner. Ten C.C. of the hydrocarbon and 40 C.C. of fuming hydriodic acid" (sp. gr. = 1.96) were placed in an ordinary narrow-necked, stoppered bottle of 120 C.C.capacity, the stopper wired down, and the whole heated in a glycerol bath for six hours at 120-125'. The contents of the bottle were then poured into water, the heavy oil which separ- ated extracted with ether, the ethereal solution washed successively with water, dilute aqueous sodium carbonate to remove acid, dilute sodium thiosulphate solution to remove free iodine, and, finally, with water. It was then dried over calcium chloride, and, after evaporation of the ether, distilled under diminished pressure. At first, a very small amount of a volatile liquid passed over, which was proved to consist of some hydriodide and unchanged hydrocarbon ; then the thermometer rose rapidly, and the pure hydriodide distilled constantly at 101.5'/33 mm.(Zelinsky and Lepeschkin give the boiling point of this liquid as 75---80°/15-17 mm.) as a practically colourless, oily liquid with a pungent camphoraceous odour. The yield is about 75 per cent. of the theoretical amount. Dih ydyoisolaurolene. Thirty-six grams of the hydriodide were dissolved in 192 C.C. of 90 per cent. alcohol, and 72 grams of zinc dust, mixed with an equal * During the addition of hydriodic acid to the hydrocarbon, the formation of the solid hydriodide was observed (compare Damsky, p. 2961, and Zelinsky and Lepeschkin, p. 308).44 CROSSLEY AND RENOUF : DIHYDROLAUROT,ENE, DIHYDRO volume of sand, added, and the whole heated on the water bath for twelve hours and then worked iip as previously described (Trans., 1905, 87, 1497). A second quantity of 36 grams of the hydriodide was treated in exactly the same manner.The hydrocarbon obtained from both experiments was then suspended in 150 C.C. of water and 5 grams of powdered potassium permanganate gradually added, with constant shaking, when the colour of the oxidising agent remained permanent, even on heating t o the temperature of the water-bath for several hours. The whole was then distilled in steam, when the hydrocarbon passed over very readily, being notably more volatile with steam than dihydrolaurolene (see p. 41). It was then dried over calcium chloride, twice distilled from metallic sodium, and analysed. 0.1205 gave 0.3792 CO, and 0,1554 H,O. C = 85.82 ; H = 14.33. U,H,, requires C = 85.71 ; H = 14-29 per cent..Dihydroisolaurolene ( 1 : 1 : 2-trimethylcycZopentane), C H i p%), I p*CH,, CH,*CH, is a clear, colourless, refractive liquid boiling a t 113-113~5"/750 mm. and possessing a sweet camphoraceous odour. It does not decolorise a chloroform solution of bromine, nor is i t acted on by potassium permanganate. The yield of pure fractionated hydrocarbon is from 60-62 per cent. of the theoretical amount. Oxidation with Fuming Nitric Acid.--Two grams of the hydro- carbon were added t o 30 C.C. of fuming nitric acid, when, on warming slightly, a reaction started which gradually became more vigorous. Heating was therefore discontinued until the action had completed itself, and then the whole was heated for half an hour. After remov- ing the nitric acid in the usual manner and evaporating, the residue solidified.It was spread on porous plate, when a white solid was obtained, which was proved to consist entirely of oxalic acid. Oxidation with Diluted Nitric Acid. Five grams of dihydroiso- laizrolene and a mixture of 26 C.C. of fuming nitric acid and 14 C.C. of water were heated to boiling on a sand-bath in a reflux apparatus with a ground glass attachment, when oxidation took place slowly. After six hours, the unattacked hydrocarbon was removed and heated with a fresh quantity of nitric acid, and this process repeated until all the hydrocarbon had been oxidised. On evaporating the nitric acid liquors to dryness, an oily residue was obtained which slowly solidified. It was heated for two hours with excess of acetyl chloride, the solvent evaporated, and the residue (1.5 grams) distilled, when i t boiled for the most part at 260---265" (boiling point of aa-dimethylglutaricISOLAUROLENE AND 1 : 1-DIMETHYLHEXAHYDROBENZENE. 45 anhydride = 265" ; Blanc, Bull.SOC. cTt,im., 1898, [ iii], 19, 285). A portion was converted into the anilic acid, which crystallised from dilute alcohol in lustrous plates melting a t 141'; nor was this melting point altered on mixing the substance with pure aa-dimethylglutar- anilic acid. The remainder of the anhydride was dissolved in boiling water, the solution evaporated to dryness, and the solid residue crystal- lised from a mixture of benzene and light petroleum, when it separ- ated in bunches of minute needles melting at 83'. It was not con- sidered necessary to analyse this substance, as the melting point was unaltered on mixing with the analysed aa-dimethylglutaric acid obtained by the oxidation of y-acetyldimethylbutyric acid (see p.46). Action of Diethylaniliize on iso Laurolene Hydviodide. Thirty-three grams of the hydriodide and 50 grams of freshly dis- tilled diethylaniline were heated in a long-necked distillation flask attached t o a condenser, a thermometer being inserted in the liquid. The first signs of a reaction commenced at 150°, when the source of heat was removed. The temperature gradually rose to 154", when the whole suddenly became turbid and a rather vigorous reaction set in, which maintained the temperature of the mixture at 15'7". When com- plete, the thermometer was raised out of the liquid and the whole heated until everything boiling below 160' had passed over.The dis- tillate was then suspended in water, hydrochloric acid added, and dis- tilled in steam, and the separated hydrocarbon washed with water, dried over calcium chloride, and fractionated. It contained halogen, which could not be completely removed by a second treatment with diethyl- aniline, and it was therefore heated for two hours with 100 C.C. of a boiling saturated solution of alcoholic potassium hydroxide and dis- tilled in steam, the distillate poured into a large volume of water, and the separated hydrocarbon dried over calcium chloride and dis- tilled over sodium, when all but a few drops passed over between 108" and 109". This was again distilled over sodium in an atmosphere of carbon dioxide, when it boiled constantly at 108-108.5" and gave the following numbers on analysis : 0.1 11 1 gave 0.3558 CO, and 0.1278 H,O.C8H,, requires C = 87.27 ; II: = 12.73 per cent. This liquid, which was obtained in almost theoretical amount, had a sp. gr. 15"/15" = 0.7857, gave a solid dibromide melting at 80--85", and in other properties was identical with isolaurolene. 0zidcctioi-L with Potassiu~n I~erma?agccnate.--Fifteen grams of this hydrocarbon were suspended in 375 C.C. of water, and a 4 per cent. solution of potassium permanganate added during constant shaking. C = 87.34 ; H = 12.7s.46 DIHY DROISOLAUROLENE. The permanganate was used up fairly rapidly a t first, but for the completion of the reaction, which required 1030 C.C. of the oxidising agent, it was necessary to heat on the water-bath to a temperature of 60-65'. The solution was then filtered from manganese dioxide, which was washed with hot water, and the combined filtrate and washings evaporated to about 150 c.c., acidified with dilute sulphuric acid, and extracted ten times with ether. The ethereal solution was dried over calcium chloride, the ether evaporated, and the residue distilled under diminished pressure. At 47 mm., a few drops of a liquid smelling strongly of acetic acid first passed over, but the main portion (5 grams) distilled at 180-195' and solidified almost com- pletely after standing in a cool place for thirty-six hours. It was spread on porous plate and purified by crjstnllisation from water, in which it is very soluble, and from which it separated in transparent, four-sided prisms melting a t 48.5' ; nor was this melting point lowered on mixing the substance with dimethylhexanonic acid, kindly sent to us by M. G. Blanc. It gave the iodoform reaction, characteristic of ketonic acids containing the group CH,*CO-, and on analysis the following numbers were obtained : 0.1081 gave 0.3400 CO, and 0.0868 H,O. C8H,,0, requires C = 60.75 ; H = 8-86 per cent. These data prove conclusively that this substance is identical with the y-acetyldimethylbutyric acid (dimethylhexanonic acid) obtained by Blanc (p. 702) by the oxidation of isolaurolene. This acid was then further oxidised with sodium hypobromite (Blanc, ibid.). The oily oxidation product was heated with excess of acetyl chloride for two hours, the anhydride thus obtained distilled, and the portion boiling at 260-265O further examined, A portion was dissolved in boiling water, the solution evaporated to dryness, when it a t once solidified, and after recrystnllisation from a mixture of benzene and light petroleum melted a t 83'; nor was this melting point altered on mixing with pure aa-dimethylglutaric acid, kindly sent to us by M. G. Blanc. 0 = 60.55 ; H = 8.92. 0.1019 gave 0.1960 CO, and 0.0664 H,O. C7H1,0, requires C = 52.50 ; H = 7.50 per cent, Another portion of the distilled anhydride was converted into the anilic acid, which crystallised from dilute alcohol in lustrous plates melting a t 140-1 41°, the melting point of pure aa-dimethylglutar- anilic acid being 141". CY = 52-45 ; H = 7-24. RESEARC'IL LABORATORY, ~'HAKMACEU'I'ICA4L ~OCIISTY, 17, BLOOMSBURY SQUARE, W. C.
ISSN:0368-1645
DOI:10.1039/CT9068900026
出版商:RSC
年代:1906
数据来源: RSC
|
7. |
VII.—The relation of position isomerism to optical activity. V. The rotation of the menthyl esters of the isomeric dibromobenzoic acids |
|
Journal of the Chemical Society, Transactions,
Volume 89,
Issue 1,
1906,
Page 47-53
Julius Berend Cohen,
Preview
|
PDF (428KB)
|
|
摘要:
RELATION OF POSITION lSOMERlSM TO OPTICAL ACTIVITY. 47 VIL-Thc: Relation oj* Positiou Isomerism to O p t i d Activity. V. The Rotcttioib of the iVenthyl Estew of the Isome I& Diby-omobenao ic: Acids. By JUL~US BEREND COIIEN and ISRAEL HYMAN ZORTMAN. THE present paper is a continuation of previous investigations on this subject (Trans., 1903, 83, 1213; 1904, 85, 1262, 1271; 1905, 87, 1190) and contains an account of certain physical constants of the menthyl esters of the six isomeric dibromobenzoic acids and the products formed in their preparation. The esters were prepared by methods already described (Zoc. cit.), namely, by oxidising the six dibromotoluenes to the corresponding acids, which were then converted into the acid chlorides, and the latter into the esters by heating with menthol.The following tables contain the physical constants of the acids, acid chlorides, and esters. The details of their preparation are given in the experimental part. TABLE I. RI. p. of highest m. p. 11. 1). of i~ure acid, recorded by acid Substance. C. a i d Z.. previous obee~vers. chloride. 2 : 9- 2 ; 4- 168-169 149-150" (153 f 147" (Claus Hubner) and Lade)j60-62* 1 1 169 (Miller) I 166.5 (Claus and Weil) 47-49 151-152 { 153 (Claus a,ld wei1),-39--41 158 (Hdbner) 1 189 (Claus and Weil) 136-137" (Meyer and Sudborough) 229-230" (Hiibner) stadt) 232-233" (Halber- 209" (Claus and Weil) stein) 228-227" (Anger- 2 : 5- l'res- BI. 1). of IE. p. ul' sure 52-43" - - ester. ester. iu 111111. 242-2.15 16 - 48-14 238--240 16 - 151-152 - 41-42 241-244 15 - 245-250 20 Tho same relation subsists between the melting points of the acids and esters as was observed in the case of the dichloro- and chloro- bromo-benzoic acids and esters, namely, the lower the melting point of the acid the higher that of the ester.Table 11 contains the densities and specific rotations of the inenthyl esters, together with the molecular rotations of the three series of dihalogen esters.48 COHEN AND ZORTMAN: THE RELATION OF TABLE I1 Menthyl \ [ A l ] ~ o o . ester of Density at 20". [4F. Chlorobromo- dibromo- Dibrorno- ester, Dichloro- beuz- Before dis- After dis- Before dis- After dis- ester, C1 : BY, ester, oic acid. tillation. tillation. tillation. tillation. Br : Rr. Br : C1. C1 : el. 2 : 3- 1.4189 1'4170 - 41.41" - 39'79"" - 173.2" { - 172.9" 2 : 4- 1.4007 1.4060 -51.49 -51.62 - 215.8 { 1:;:; } -209.6 193 5 - - 2 : 6 - .f i n be1 3 : 4 - - 1 *4'L58 - -55.18" -230'7 { )- -227.5 8 : 5- 1'4114 1'4150 -54'57 -53'79 * -228'2 -235.9 -233.2 Menthyl - - - 90.92 { i%k;:;e) - 236'3 - - benzoate} * In the case of the 2 : 3- and 3 : 5-estersY a little acid separated on distillation, The rotation I n all other cases, and the product was probably less pure than the undistilled material. is therefore calculated from observations on the undistilled ester. the rotation is that of the distilled product, which is assumed to be purer. With the single exception of the 2 : 6-ester, the effect of the substi- tution of two bromine atoms is less than that of the substitution of two chlorine or one chlorine and one bromine atom. This result was anticipated from the relation which subsists between the monochloro- and monobromo-derivatives (Trans., 1903, 83, 121 6).The magnitude of the deviation beginning with the ester OF smallest rotation is as follows : 2:6-; 2 : 3 - ; 2 : 5 - ; 2:4; 3:5-; 3 : 4 - ; phenyl. The order is the same as that of the dichloro- and chlorobromo- esters with the exception of the 3 : 4- and 3 : 5-esters, the positions of which are reversed in the present case. The influence of the ortho- bromine atom in depressing the rotation is very clearly indicated in all cases, but most strikingly in that of the 2 : 6-ester. The steadily and rapidly decreasing rotation with the increasing atomic weight of the halogens in the di-ortho-positions induces one t o predict the almost complete annihilation of activity in compounds which contain iodine in place of the other halogens.The remarkably high melting point of the diortho-ester corresponds closely with the constants of the other 2 : 6-dihalogen compounds ; the dichloro-ester melts a t 134--135O, the chlorobromo-ester at 144-1 45", and the dibromo-ester at 151-152".POSITION ISOMERlSM TO OPTICAL ACTIVITY. V. 49 E x PER IMENTA L. Preparation of the Dibromohenxoic Acids, Acid Chlorides, and Menthy2 Esters. The method employed for obtaining the dibromobenzoic acids is pre- cisely that used in the former preparations of the dihalogen compounds (Zoc. cit.) and needs no general description. The acid chlorides were prepared and purified in the manner already described.As in former examples of diortho-acid chlorides, the 2 : 6-dibromobenzoyl chloride required a much higher temperature for esterification (I 75-180') than the isomeric acid chlorides, all of which react rapidly below 130' with menthol. The esters, with the exception of the 2 : 6-compound, were distilled under diminished pressure. The rotations before and after distillation varied slightly. I n the two cases already referred to, namely, those of the 2 : 3- and 3 : 5-esters, some decomposition occurred and a little free acid separated in the distillate. The effect was to lower the rotation slightly. It is evident that even a t this high temperature of distillation no racemisation occurs. Menthyl 2 : 3-Dibromoberzxoate.-The dibromobenzoic acid was pre- pared from 3-nitro-o-toluidine (obtained from aceto-o-toluidide by Reverdin and Crdpieux's method) (Bey., 1900, 33, 2498).The base was diazotised and converted into the bromonitro-compound, reduced to the bromoamine, and again diazotised as follows : This may serve to illustrate the series of reactions usually adopted in the preparation of the other dibromotoluenes. Sixty grams of nitro- toluidine gave nearly 20 grams of 2 : 3-dibromotoluene. The oxidation of the dibromotoluene was effected by heating in sealed tubes with dilute nitric acid (1 vol. of HNO,, sp. gr. 1.4, to 2 vols. of water) a t 130-135' for' five and a half hours. The acid which was separated from the product was very impure and, like the product of oxidation of the 3-chloro-2-bromotoluene (Trans., 1904, 85, 1266), contained a large quantity of a compound melting above 200' and also a substance melting below 135'.The crude material, amounting to 16 grams, was purified by repeated crystallisation from ligroin, in which the less fusible acid is nearly insoluble and the more fusible compound readily soluble, whilst the 2 : 3-acid dissolves in the boiling liquid, but is nearly insoluble in the cold. Eventually 4.2 grams of acid were obtained, which seemed to YOL. LXXXIX. E50 COHEN AND ZORTMAX: THE RELATION OF soften slightly a few degrees below 148' and then melted sharply. Recrystallisation did not seem to alter the melting point, but a small quantity of acid obtained a t a later stage on distilling the menthyl ester melted sharply a t 149-150', and may be taken as the true melting point.The acid was heated on the water-bath with an equal weight of phosphorus pentachloride and the product distilled under diminished pressure at 100" to remove most of the phosphorus oxy- chloride. The acid chloride, which solidified on cooling, was dissolved in benzene t o separate the insoluble phosphorus pentachloride and the benzene distilled off, the last traces being removed by heating to 100" in a vacuum. The residual solid cake was powdered and pressed on a porous plate and left in a vacuum desiccator to remove any remaining phosphorus oxychloride. The crude acid chloride melted at 55-60" and after one crystallisation from ligroin a t 60-62". The product, amounting t o 3.5 grams, was heated in an oil-bath with 2.5 grams of pure menthol (Kahlbaum), the specific rotation of which had been ascertained, and gave the correct number.The reaction began at 100-105'. The mixture was maintained at 130' for an hour, water and a little sodium carbonate solution were then added, and the ester submitted to distillation in steam until all trace of free menthol had been removed. The residue was extracted with ether, dehydrated with fused calcium chloride, and the ether removed by distillation. The product solidified on cooling and melted sharply a t 52-53', The fused substance had an amber colour, which, however, did not interfere with the polarimeter readings : I = 0.303 dcm., d/30° = 1.4189, aD - 17.74". The ester, after distilling under reduced pressure, was colourless. A little free acid which separated in the process was removed by dissolv- ing in light petroleum, in which the acid is insoluble, and filtering.The distilled product melted a t 49-52?', which is lower than the original material, and was therefore less pure. A redetermination of the rotation and density confirmed this: 1=0*303 dcm., dj20°== 1.4170, a,, - 17.03'. The analyses of this and the other esters are recorded in a table a t the end of the paper. Jlenthyl 2 : 4-Dibronzohenxoate.-The dibromotoluene which served for the preparation of the acid was obtained from 2 : 4-nitrotoluidine by the usual series of operations. Sixty grams of the base gave 35 grams of dibromotoluene boiling at 152-158' under 80 mm. pressure. Twenty grams gave, on oxidation at 120-125" for five hours, 16 grams of crude acid (m.p. 145-152'), which were subjected t o steam-distillation to remove a small quantity of less fusible substance which was volatile in steam. After recrystallisation from benzene, 6 grams of acid were obtained melting a t 164-166'. ThisPOSITION ISOMERISM TO OPTICAL ACTIVITY. V. 51 was successively converted in the usual way into the acid chloride (m. p. 43-45') and the ester, which gave the following polarimeter readings : I = 0.302 dcm., d,'20°= 1.4023, a, - 21.94". The dibromo- toluene gave in succession 15 grams of acid (m. p. 165-167'), 13 grams of acid chloride (m. p. 47-49'), and 13.5 grams of ester. The polarimeter readings (u) before and ( b ) after distillation were as follows : a. E = 0.302 dcm. ; d/20' = 1.4007 ; aD - 21.78". A second preparation was made in a similar may.b. I = 0.302 dcm. ; d/20"= 1.4060 ; a D - 21.92". Menthyl 2 : 5-Bibromober~xoate.-The 2 : 5-dibromotoluene was ob- tained from 2 : 5-nitrotoluidine. Sixty grams of base gave 35 grams of dibromotoluene (b. p. 155-170°/120 mm.). The crude acid was crystallised repeatedly from alcohol and benzene, and finally from water after boiling with animal charcoal to remove colouring matter. About 26 grams of dibromotoluene yielded 9 grams of pure acid (m. p. 150-151"). The latter gave 6 grams of acid chloride (m. p. 39-41'> arid finally 7.3 grams of ester (m. p. 42-44'). The following are the polarimeter readings : ( u ) before and ( b ) after distillation : a. I = 0.302 dcm. ; d/20° = 1.3809 ; U D - 21.7". b. 1=0.302 dcm. ; d/20°= 1.3821 ; a , - 21.27".itfenthyl 2 : 6-Dibromobenxoate.-The 2 : 6-dibromotoluene used for oxidation was obtained from 2 : 6-dinitroluene by a series of alternate re- ductions and diazotisations. The yield from 150 grams of dinitro-corn- pound amounted to 50 grams of dibromotoluene (b. p. 110-130"/30 mm.). The 29 grams of crude acid obtained on oxidation were first purified by esterifying with methyl alcohol and hydrochloric acid, The 2:6-acid is not attacked, whereas other acids which may be present as by-products are esterified, and can be removed by shaking out the alkaline solution with ether. The crude acid was then recrystallised from benzene, when 11 grams of pure 2 : 6-acid were obtained, which crystallised in hexagonal plates and melted at 146-141". It was converted into the acid chloride (m.p. 35-39"), which, on crystallising from light petroleum, formed colourless needles (m. p. 39-42O). Seven grams of acid chloride gave, after crys- tallisation from alcohol, 5 grams of pure menthyl ester in colourless needles (m. p. 151-152'). The rotation was determined in benzene solution as follows : 3.9104 grams in 25.07 C.C. of benzene ; I = 2 dcm. ; uD - 1-46". 10 C.C. of above solution and 10 C.C. of benzene; E=2 dcm.; a D - 0.64". E 252 RELATION OF POSITfON 1SOMERISM TO OPTICAL ACTIVITY. 2.3760 grams in 13 C.C. of benzene ; I = 2 dcm. ; 1 *2798 grams in 13 C.C. of benzene; I = 2 dcm. ; Menthyl 3 : 4-Dibromobenxoate.-The aceto-p-toluidide used in the pre- paration of 3 : 4-dibromotoluene was brominated and then hy drolysed, and the 3-bromo-p-toluidide thus obtained was then diazotised in the usual way.Thirty-four grams of bromotoluidine gave 23 grams of 3 : 4-dibromotoluene (b. p. 160-165'/65 mm.). On oxidation in sealed tubes, 10 grams of acid (m. p. 215-225') were obtained which were recrystallised from dilute alcohol with the addition of animal charcoal and then gave a colourless product (m. p. 227-229'). About 7 grams of pure acid gave a n equal weight of acid chloride (m. p. 64-66') The ester amounted to 7.8 grams of a brown, viscid liquid which showed a rotation of - 33*5', but as the colour interfered with the reading, the ester was distilled under reduced pressure, and the colourless distillate then gave the following result : I = 0.302 dcm., d/20° = 1.4-258, a, - 23-76'.The liquid solidified on standing for some weeks and then melted at 41.43'. Menthyl 3 : 5-dibromobenxoccte.--The 3 : 5-dibromotoluene was obtained from 3-bromo-p-toluidine (b. p. 166'/50 mm.), described above, which was brominated and the amino-group replaced by hydrogen i n the usual way. Thirty-seven grams of bromotoluidine gave 34 grams of 3 : 5-dibromotoluene (m. p. 38-39'). Thirty grams of dibromotoluene gave 26 grams of crude acid, which, after recrystallisation from benzene, gave 18 grams of pure substance (m. p. 213-214'). From the acid were obtained 15.5 grams of pure acid chloride (m. p. 41-42'), and finally 20 grams of menthyl ester. The following polarimeter readings were made : ( a ) before and ( b ) after distillation : uD - 1 ~ 9 8 ~ . aD - 0-SO". (a) 1=0.302 dcm. ; d/2Oo= 1.4114; UD - 23.26". (b) I = 0.302 dcm. ; UD - 23.00". d/20' = 1.4159 ; As a little acid separated in the process of distillation, the un- distilled product probably gives the more trustworthy value. It should be added that although the melting points of several of the esters lie much above 20", a t which the densities and polarimeter readings were taken, they are easily supercooled and remain in a fused state a t 20' without showing any signs of solidification. The tendency to supercooling is rather remarkable, and it has been frequently observed that when the fused liquid has been cooled to the ordinary temperature in the pyknometer and crystallisation has begun a t the capillary end, the main portion will remain liquid for a considerable time.PRICE : CARO'S PERMONOSULPHURIC ACID. TABLE 111. Analyses of the Dibromobenxoic Esters. 2 : 3- 0.1476 0.1338 38.58 2 : 4- 0'2154 0.1920 37'98 2 : 5- 0 '1 338 0'1185 37.70 2 : 6- 0.1236 0'1114 38.34 3 : 4- 0'1208 0.1087 38'30 3 : 5 - 0.1552 0.1392 38.16 C,7H,0,Rr., requires Br = 38.27 per cent. Menthyl ester. Substance taken. AgBr. Per cent. THE UNIVERSITY, LEEDS. 53
ISSN:0368-1645
DOI:10.1039/CT9068900047
出版商:RSC
年代:1906
数据来源: RSC
|
8. |
VIII.—Caro's permonosulphuric acid |
|
Journal of the Chemical Society, Transactions,
Volume 89,
Issue 1,
1906,
Page 53-58
Thomas Slater Price,
Preview
|
PDF (418KB)
|
|
摘要:
PRICE : CARO’S PERMONOSULPHURIC ACID. 53 VITII.-Caro’s Permonosulphtwic Acid. By THOMAS SLATER PRICE, D.Sc. THE results of the various investigations which have been made to determine the composition of permonosulphuric acid (Caro’s acid) have led t o the conclusion that the formula is either H,SO, or H2S2Og, the acid being monobasic in the former case and dibasic in the latter (compare Price, Trans., 1903,83, 543 ; also Mugdan, Zeit. EZektrocliem., 1903, 9, 719 ; Price and Friend, Trans., 1904, 85, 1536). The decision between these two formulae could readily be made if a pure salt, such as the potassium derivative, could be obtained. The simplest method would be to heat a weighed quantity of the salt and determine the weight of potassium sulphate l e f t ; tbe weight of residue obtained would vary according as to whether the formula was KHSO, or K2S20,.Although the author has not yet succeeded in overcoming the diffi- culties attending the preparation of the pure potassium salt, a mixture has been obtained, from the analysis of which it has been possible to show that the formula of the acid is H2S0,. The mixture consisted of the potassium salts of sulphuric, permonosulphuric, and perdisul- phuric acids and of pot,assiuni hydrogen sulphate. The proportion of each constituent was found a s follows : the permonnsulphate, calcu- lated as either KHSO, or K,S,O,, was determined by the liberation of iodine from a solution of potassium iodide and titration with thiosul- phate ; the perdisulphate by measuring the total oxidising power of the mixture by means of ferrous sulphate and potassium permangan- ate and allowing for that due to the permonosulphate.The amount of potassium hydrogen sulphste was estimated by a method which54 PRICE : CARO'S PERMONOSULPHURIC ACID. depends on the results obtained by Mugdan (Zeit. Elektrochem., 1903, 9, 719). Use was made of the fact that when permonosulphuric acid is decomposed by potassium iodide a diminution in acidity takes place, as shown by the equations H,S,09 + 4KI = 2K,SO, + H,O + 21, cw H,SO, + 2KI = K,SO, + H20 + I,. The liberated iodine was titrated with thiosulphate and then the acidity of the solution determined by means of standard caustic potash (free from carbonate). Knowing the amount of permono- sulphate present, the diminution in acidity which should take place could be calculated from the above equations ; the difference between the observed and calculated results gave the acidity due to the potassium hydrogen sulphate present.The amount of potassium sulphate was then determined by differ- ence, knowing the weight of the mixture and of the other constituents. All that was then necessary was to find the amount of potassium sul- phate obtained by heating a known weight of the mixture, then com- pare the experimental with the theoretical result. The following table gives a summary of the results obtained : --I-- -7-1 - Q) z cub 0 % d 22, 20 e E$ $ 11 grams 4.3780 4-6960 2.3800 4'3570 grams 4'4670 4'7743 2-4400 The results of the above experiments thus point to the formula KHSO, in preference t o K,S20, for potassium permonosulphate, and hence to the formula H,SO, for permonosulphuric acid. The difference of about 2 per cent.between the experimental and calculated values for the weight of the residue of potassium sulphate, assuming the formula €€,SO, for permonosulphuric acid, seems, a t first sight, to be rather large. As will be seen from the experimental details, however, the differences in weight i n the last column have been multiplied by 10,PRICE : CARO’S PERMONOSULPHURIC ACID. 55 the actual differences varying from 6 to 9 milligrams ; taking into consideration the number of different determinations which have t o be made in order to arrive a t the above results, it is very probable that the errors of experiment will account for these differences.All the apparatus used, including the weights, had been carefully calibrated. I t was thought a t one time that the error might be due to imperfect drying of the mixture; this was found not to be the case, however, since the errors in all four experiments are about the same, whereas the mixtures in the first two cases were dried for three days in an exhausted desiccator over sulphuric acid, whilst the last two mixtures were dried for five weeks in a vacuum over phosphoric oxide. It is possibIe that the error may be to some extent explained by the occlusion of some of the mother liquor in the crystals as they are slowly deposited during the concentration of the solution under diminished pressure (compare Richards, Zed. plqsikal. ClLem., 1903, 46, 189).This would account for the fact that in all cases the calculated weight of the residue is greater than the experimental weight. Since the results of previous researches have shown conclusively that the formula for permonosulphuric acid is either H,SO, or H2S209, the present investigation may be used to decide the question i n the same way as the determination of the specific heat of a metal is used to decide the atomic weight. Hence, the first formula must be regarded as the correct one. The constitution of the acid would 0 0.H 0 then be represented graphically by >S<o,o.H, the hydrogen in the hydroxyl group directly attached to the sulphur being presumably the one replaced by metals in the formation of salts. The remaining hydrogen atom would possess only very weak acid properties, i f any at all, as it is contained in the group -O*O*H, derived from hydrogen peroxide, which is only a very weak acid.Also, from analogy with other dibasic acids, the acidity would be very much diminished by the presence of the much more strongly acid hydrogen ion in the -OH group directly attached to the sulphur. Since perdisulphuric acid (H2S208) is d i basic, readily forming the salt K,S,O,, it would follow that the constitutional formula usually assigned to it, is the correct one, in which both the acid hydrogens are contained in -OH groups directly attached to the OH sulphur atoms, and not 05Sz<02H, as given by Kastle and Loewenhart (Arne?.. Chem. J., 1903, 29, 563; see also Price and56 PRICE : CARO'S PERMONOSULPHURIC ACID.Denning, Zeit. physikaZ. Clbem., 1903, 46, 101), since in the latter case the acid would probably be monobasic, judging by analogy with permonosulphuric acid. EXPERIMENTAL. A solution of permonosulphuric acid was made in the usual manner by the action of 25 C.C. of concentrated sulphuric acid on 25 grams of potassium perdisulphate (compare Price and Friend, Trans., 1904, 85, 1526) ; potassium perdisulphate was chosen because it is so easily puri- fied, The solution so obtained was diluted and neutralised a t the same time by being run very slowly into a solution of potassium carbonate (containing enough carbonate to neutralise the sulphuric acid taken), in which was ice freshly made from distilled water. The temperature of the aqueous potassium carbonate, which was - 7" before the solution of per- monosulphuric acid mas run in, gradually rose to about 0" during the process of dilution.The potassium sulphate which separated out was filtered off, the mother liquor being drained away as completely as possible. The filtrate generally contained an amount of persulphuric oxygen which was equivalent to about 18 grams of H,SO, per litre. If the mixture containing the acid was first diluted by being poured on to broken ice, and then neutralised with potassium carbonate, the filtrate was only about half the above strength. The filtrate was generally acid, and was neutralised by the further addition of anhydrous potassium carbonate, which was added carefully until no further effervescence took place. This method was accurate enough, since it was not essential that the solution should be exactly neutral (see p.57). The neutral solution was then further con- centrated by freezing ; the chief advantage of this process lay in the deposition of the potassium sulphate, and not in the increase in con- centration of the permonosulphate, since the residue of ice and potassium sulphate always contained an appreciable amount of adherent permonosulphate. Only one freezing was carried out ; a second was not found to be advisable, since the increase in con- centration of the permonosulphate thus obtained was very small. It is generally supposed that permonosulphuric acid and its salts are not very stable in solution, but it was found possible to evaporate the solution t o dryness by concentration in a vacuum desiccator over concentrated sulphnric acid.The process of evaporation lasted between a week and a fortnight, and the potassium sulphate, which separated out continuously, was filtered off from time to time until the solution became so concentrated that it could not be filtered without undergoing appreciable loss; it was then allowed to evapo- rate to dryness. During the evaporation of the solution, the con-PRICE : CARO’S PERMONOSULPHURIC ACID. 57 centration of the permonosulphate continually increases, but at the same time some of the salt decomposes with the formation OF potass- ium hydrogen sulphate. This is the reason why it is immaterial whether the neutralisation with potassium carbonate be exact or not. The mixture so obtained was powdered as finely as possible, and finally dried in a vacuum desiccator.It should be mentioned that the solutions containing the permono- sulphate generally had a strong odour resembling that of bleaching powder (Baeyer and Villiger, Bey., 1901, 34, 853); this generally disappeared during the concentration under diminished pressure, and the solid substance possessed no odour ; on exposure to the air, the solution acquired this characteristic odour after a short time, but its presence or absence did not :tffect the analytical results. No hydrogen peroxide could be detected by the titanium sulphate test, either in the solutions before concentration or in the solutions made from the solid residue obtained. Analysis of the h?ixtu,Ye.-- A weighed quantity of the dry mixture was dissolved in air free water and the solution diluted to 100 C.C.Aliquot portions of this solution were taken and the various in- gredients determined. For all the titrations, 2 C.C. of the solution were used and the measurements repeated several times. I n no case did the individual titrations vary more than 0.03 C.C. (on 10 to 25 c.c.). As has already been mentioned, the permonosulphate was estimated by the liberation of iodine from a solution of potassium iodide, the precautions observed being the same as those detailed in a previous paper (Price, Trans., 1903, 83,543). As is shown by the equations on page 54, a decrease in acidity takes place during this reaction. For this reason ft known amount of dilute hydrochloric acid was added to the aque- ous potassium iodide before the permonosulphate solution was introduced.After the iodine liberated had been exactly titrated with thiosulphate, the acidity of the resulting solution was determined by nieans of standard caustic potash. From the diminution in acidity which had taken place, the amount of potassium hydrogen sulphate present was calculated in the way already indicated. This method of determining the acidity of the mixture is indirect, but no direct method could be found which gave trustworthy results. The solution could not be directly titrated with caustic potash, using either methyl-orange or phenolphthalein as indicators. I n the former case, the indicator was rapidly oxidised, 2nd in the latter the colour change mas not sharp. This has been noticed by the author in previous investigations on Caro’s acid, but the difficulty could not then be over- come; the action with phenolphthalein is probably due to the slight acidity of the hydrogen ion in the -0OH group.Nor could satis-58 PRICE : CARO'S PERMONOSULPHURIC ACID. factory results be obtained by the method used by Armstrong and Lomry (PYOC. Roy. Soc., 1902, 70, 94). On heating an aliquot portion of the solution to decompose the persulphates and then titrating with caustic potash, the titrations varied greatly among themselves and were quite untrustworthy; this has also been noticed by Mugdan (Zeit. Elektrochem., 1 9 03, 9, 7 1 9). In the determination of the total oxidising power of the solution, concordant results could be obtained only in the following manner : a solution of sulphuric acid was boiled to expel all air and then cooled ; 5 C.C.of ferrous sulphate solution and 2 C.C. of the solution t o be analysed were then added in the order given, and the whole heated to boiling again in order to reduce the persulphate completely; the solution was then cooled and titrated with permanganate. The only other estimation necessary, which was the determination of the amount of potassium sulphate obtained from an aliquot portion of the solution, was performed by evaporating 10 C.C. of the solution t o dryness in a platinum crucible over the water-bath. The crucible was covered with a watch-glass until all the permonosulphate had decomposed, since there was a vigorous effervescence as soon as the solution became hot. The residue in the crucible was then carefully heated to decompose the potassium hydrogen sulphate and any per- sulphate remaining, and weighed as sulphate in the usual manner. Four different lots of 10 C.C. each were usually treated in this manner, Obviously the simplest method would have been t o heat a known weight of the solid mixture directly; there was the un- certainty, however, as to whether the ingredients were thoroughly mixed or not. It remains to be pointed out that the methods given above can only be used to discriminate between the formulae KHSO, and K,S,O,, which, indeed, is all that is necessary. A short calcula- tion will show that it is not possible t o distinguish between the formulae K,S,O, and KHS,O,, or between K,SO, and KHSO,, because of the method used to estimate the proportion of potassium hydrogen sulphate. CHEMICAL DEPARTMENT, BIKMINGHAM. MUNICIPAL TECHNICAL SCHOOL,
ISSN:0368-1645
DOI:10.1039/CT9068900053
出版商:RSC
年代:1906
数据来源: RSC
|
9. |
IX.—Contributions to the chemistry of the amidines. 2-Aminothiazoles and 2-imino-2 : 3-dihydrothiazoles. 2-Iminotetrahydrothiazoles and 2-amino-4 : 5-dihydrothiazoles |
|
Journal of the Chemical Society, Transactions,
Volume 89,
Issue 1,
1906,
Page 59-76
George Young,
Preview
|
PDF (1053KB)
|
|
摘要:
CONTRlHUTIONS TO THE CHEMISTRY OF THE AMIDIWES. 59 IX.-Contrib;z.ctions to the Chemistry of the Arniclines. 2- Aminothiaxoles and 2-lrnin 0-2 3 -d i7z yd?*othiuzoles. 2-~~~~inotetrahydrot~~iaxoles and 2-Amino-4 : 5- cliJhydrothiazoles. By GEORGE YOUNG and SAMUEL IRWIN CROOKES. THIS investigation was undertaken with the purpose of studying the constitutions of the derivatives of such amidines as have one of the nitrogen atoms and the carbon atom of the group -N:C*Nz forming part of a closed chain, whilst the second nitrogen atom lies outside of the cyclic nucleus; these are referred to in the following pages as '( partially cyclic " amidines. In the present paper, we describe the alkylation of some amidines belonging to the thiazole group, and the determination of the constitutions of the alkyl bases formed.Traumann (Annalen, 1888, 249, 31) found that the base formed by the action of chloroacetone on thiocarbamide, and to which he ascribed the constitution EHAS>C*NH2, yielded on methylation Cll/le*N >C:NH, and that similarly the base, the derivative @FhT:>C*NH2, obtained by heating thiocarbamide with phenacyl bromide, yielded the methyl derivative, CH--S 8Me-NMe EH-- '>CXH. CPh XMe We have methylated the bases obtained by heating methylthio carbamide, allylthiocarbamide, and phenylthiocarbamide with chloro acetone. Traumann (Zoc. cit.) has shown that the bases formed in this manner from monosubstituted thiocarbamides, have the constitution EH-S>C*NHR. The position of the hydrogen atom, which is CMe*N substituted on alkylation, is discussed later.The methyl derivative, obtained from the base with R-CH,, is identical with 2-methylimino-3 : 4-dimethyl-2 : 3-dihydrothiazole, CH--S >C:NMe, formed by the action of chloroacetone on s-cli- 8Me*NMe methylthiocarbamide. To determine the constitution of the alkyl derivatives of the bases with R = C3H5 and C,H,, we heated the methyl bases with concentrated hydrochloric acid at 250' in the expectation of obtairling a primary or secondary amine and the oxydihydrothiazole,60 YOUKG AND CROOKES: CONTRIBUTIONS TO THE CH- s NH2R + 8Me.N&Te >CO or GH--S >C:NR CMe-NMe >co. EH--S CMe*NH FH-'>C-NRMe -+ NHRMe + CMe*N' The high pressure in the tube after cooling, the evolution of hydrogen sulphide on evaporation of the mixture, and the separation of methylamine together with a less volatile primary amine (allyl- amine (1) and aniline respectively) from the products showed that the methyl bases had the constitutions >C:NPh, CH-- I I S>C:N*C,H, and CH--S CMe-NMe 8Me-NNe and that the hydrolysis had proceeded beyond the forination of the oxydihydrothiazole to, a t least, partial disruption of the thiazole nucleus. I n confirmation of this, it was found that 2-phenylaminothiazole, GH-S >C*NHPh, when hydrolysed with concentrated hydrochloric CMe*N acid at 350°, yielded aniline and small quantities of ammonia, hydrogen sulphide, and carbon dioxide. The methylation of the '( partially cyclic " amidines, VHR-S >C:NR', A' F H R ' S > ~ * ~ ~ ~ r CH,-N or CH,*NH has been studied by Gabriel, who methylated the bases with R=H arid CH,, and R=H, and obtained the derivatives (Ber., 1889, 22, 1142, 2984), whilst Prager, who methylated the bases of this type with R=CH, and R'=C,H, and o-C6H4Me (Ber., 1889, 22, 2998), obtained the derivatives YHMe-S $? HMe*S CH,- CH,-N N>C*NMePh and >C*NMe*C,H,Me.We have repeated Prager's preparations, have confirmed his results, and have extended the investigation to the metbylation and ethylstion of three bases in all, with R=CH, and R'=C,H,, o-C,H,Me, and p-C6H,3fe. On successive oxidation and hydrolysis of the alkylated bases, we obtained in each case p-methyltaurine and the secondary base : methyl- or ethyl-aniline, o-toluidine, and p-toluidine respectively, from which follows the constitution of the alkylated bases : CHMe*SO,H B.?Hn'e'S>C*NR'Alk --+ NHR'Alk + I CH,-N CH,*NH,CHEMISTRY OF THE AMIDINES. 61 Our results, together with those of Traumann, Gabriel, and Prager, show that “ partially cyclic ” amidines of the thiazole series, having a hydrogen atom which may be substituted directly by an alkyl group, yield on alkylation derivatives in which the alkyl is attached to the nitrogen atom of t h e nucleus, except when the ring is already partially reduced and R’ in the formula A is an aryl group, the alkyl group in this case going to the side-chain nitrogen atom, as in B. This rule is probably of general application to the alkylation of “ partially cyclic ’’ arnidines of any carbo-nitrogen heterocyclic series. The results of alkylating ‘‘ partially cyclic ” amidines are in accord with those obtained by von Pechmann on methylating “mixed” amidines, if the rule of alkylation be stated in the following form :- on alkylation of an amidine, the alkyl group goes t o the more negative nitrogen atom.Von Pechmann (Ber., 1895, 28, 3362 ; 1897, 30, 1780) found that NHR on metbylation of a “mixed” amidine, which might be -CGNK, NR or -CeNHX, with an R, an alkyl group, or a hydrogen atom, and R’, an aryl group, and in which the two nitrogen atoms must vary widely in basicity, there is obtained only one methyl derivative : in which the methyl is attached to the same nitrogen atom as in the aryl group, that is to say, to the less basic or more negative nitrogen atom, but on methylation of a ‘‘ mixed ” amidine with R and R’, two similar groups, as phenyl and o-tolyl (Ber., 1895, 88, 869) or phenyl and P-naphthyl (Ber., 1897, 30, 1783), in which the difference of the basicity of the two nitrogen atoms can be only small, a mixture of the two possible methyl derivatives is obtained.The negative nature of a nitrogen atom in an unsaturated hetero- cyclic nucleus, as exemplified by the ease with which the hydrogen atom of the group -NH- is substituted by metals, is well known, as is also the increase of the basicity of cyclic compounds on reduction. To quote one example of this : diphenyltriazole, CPh<sg>CPh (Pinner, Annalen, 1897, 299, 255), has hardly any basic properties, being soluble in dilute alkali hydroxides, but insoluble in dilute acids ; whereas diphenyldihydrotriazole, CPh<-NH-->CHPh N*NH (Pinner, Eoc. cit., p.266), is a strong base, forming with hydrochloric, nitric, and acetic acids stable salts which are not decomposed by water. Of the two possible “ partially cyclic ” amidines,62 YOUNG AND CROOKES: CONTRlBUTIONS TO THE '>C:NR, I. 8H-S>C*NR*Alk and J I . tRlemNAlk CH-- CMe*N the alkyl group is in the more negative position in 11, and there- fore, 2-phenylimino-3 : 4-dimethyl-2 : 3-dihydrothiazole is obtained on metbylation of the base >C:NK, CH-S or IV. 8Me-NH III. 8 H - S > ~ * ~ ~ ~ CMe *N which has R=C,H,. On the other hand, of the alkyl derivatives, '>C : NR , yHMe-- v. YHMe CH,--N ">C*NR*Alk or TI. CH, *NAlk derived from Gabriel and Prager's bases, FHMe-S >C:NR, CH,*NH >C*PU'HR or VIII.$!HMe*S VIT' CH,--N the alkyl is probably in the more negative position in V if R = a n aryl group, but in VI if R is a hydrogen atom or an alkyl group; hence Gabriel's methylated bases are of the latter, but Prager's of the former type. The constitution of the derivative obtained on alkylation of an amidine having been determined, it is assumed usually that the constitution of the amidine is to be represented by placing a hydrogen atom in the position taken up by the alkyl. Thus, according to von Pechmann (.Bey., 1897, 30, 1781), benzphenylamidine must be C6H5*C<NHph, because on methylation it yields the derivative NH N H C6H5'CeNMePh. I f , however, methylation of an amidine takes place not by direct substitution, but by addition of methyl iodide and subsequent elimination of hydrogen iodide, the intermediate additive product in the formation of the methyl derivative of benzphenyl- Beckmann and Fellrath, Annulen, 1893, 273, 24), which could be formed by addition of methyl iodide t o an amidine only of t b e constitution C6H,*CGNph. NH, This view of the mechanism of the alkylation of amidines is in agreement with the behaviour of ethylene-+-thiocarbamide and of propylene-+thiocarbamide. Gabriel, having determined the constitu- tion of their methyl derivatives (see p.60), represented these bases by the formulaeCHEMISTRY OF THE AMIDINES. 63 >C:NH. $: H Me* S CH,*NH '>C:NH and CH,- ~H,-NH Later, Gabriel and Leupold (Be?.., 1898, 31, 2832) treated these two bases with nitrous acid in benzene solution and obtained the derivatives >C*NO,, YHMe-S CH,--N ? HMe '> C C6H5 and CH2--X i.espectively, probably owing to the intermediate formation of diazo- compounds, pointing to the constitutions XE;i>C*N€€, and >C*NH, for the two bases.These constitutions are in agree- 7 HMe*S CH,--N ment with the imino-formulae for the methyl derivatives methylation takes place through the intermediate formation additive products if the of the YHMe-S >CI*NH, CH,*Nble ">CI *NII, and 7H2-- CH,-NMe or CH,-- '>C*NH, and yHMe--'>C*NH2. b H, N (MeI) CH,*N( MeI) Bamberger and Lorenzen (Annalen, 1893, 273, 274) have pointed out that the addition of methyl iodide takes place t o a tertiary, i n preference to a primary or secondary, nitrogen atom, Owing t o these considerations, we have ascribed formulae of the type 111 to the amidines which yield the alkyl derivatives 11, VII to those which form the alkyl derivatives VI, and VIII to the parent bases of the compounds V.The foregoing remarks apply only to the direct alkylation of amidines by the action of alkyl haloids a t the laboratory or higher temperature with or without a solvent, and not to indirect alkylation by the action of alkyl haloids on a metallic derivative of the amidine With the idea that methylation by the latter method might lead to the formation of the isomeric series of alkyl derivatives, we digeste the silver derivatives of the 2-arylimino-5-methyltetrahydrothiazoles VIII with one molecule of methyl iodide, but without obtaining more than traces of oily products which might be the alkylated amidines, the original base being recovered almost entirely in each case.Similarly, Bamberger and Lorenzen (Zoc. cit., p. 282) found that only very small amounts of 1 : 2 : 5-trimethylbenzimidazole were64 YOUNG AND CROOKES: CONTRIBUTIONS TO THE formed by the action of methyl iodide on the silver derivative of 2 : 5-dimethylbenzimidazole, whilst Meldola, Eyre, and Lane (Trans., 1903, 83, 1185) obtained the same alkyl derivatives from ethenyldi- aminonaphthalenes by the direct and the indirect methods of alkyla- tion, but in much the poorer yields by the latter process. We suggest that in reality no alkylation of these amidines takes place by the indirect method, the small amounts of alkyl derivatives formed being due to interaction of the alkyl iodide with the liberated amidine, especially as the best yields by the indirect method appear to be obtained when, as in the experiments of Meldola, Eyre, and Lane (Zoc.cit., p. li93), an excess of the alkyl haloid is employed. On the other hand, 2-acetylimino-3 : 4-dimethyl-2 : S-dihydrothi- azole, >C:NAc, is formed in good yield by the indirect method from the acetyl derivative of 2-amino-4-methylthiazole, as was 2-acety limino-5-phenyl-3-methyl-2 : 3-dihydrothiodiazole, fH-S CMe*NMe from 2-amino 5-phenylthiodiazole, studied by Young and Eyre (Trans., 1901, 79, 54), whereas attempts to methylate the last substance by the direct method met with no success. It may be that the greatly diminished basicity of the nitrogen atom of the side-chain consequent on the introduction of the acetyl group causes isomeric change to take place : the hydrogen atom being less labile when attached to the less negative atom, the subsequent direct substitution, on treatment of the silver derivative with methyl iodide, >C: NAc, CH--Is '>C:NAc --+ fCIMe*NMe CH- CMe NAg I I being due to the increased acidity of the molecule.E x P E R I BI E N T A L. 2-Aminothiaxoles a n d 2-lmino-2 : 3-dihyclrotT~iaxoZes. 2-Anilino-4 methylthiazole mas prepared by Hantzsch and Weber (Ber., 1887, 20, 3130) by the action of aniline on 2-hydroxy-4-methyl- thiazole, and was found by these authors to melt a t 117". Traumann (Eoc. cit.), who prepared the base by acting on phenylthiocarbamide with chloroacetone, found it to melt at 115".On repeating theCHEMISTRY OF THE AMIDINES. 65 preparation by Traumann's method, we obtained a substance which crystallised from dilute alcohol in long needles and melted at 11 7-1 18'. When boiled with acetic anhydride and sodium acetate, the base formed an acetyl derivative, which was readily soluble in alcohol or benzene, but only moderately so in light petroleum; from the last solvent it crystallised, on slow evaporation, in clusters of soft, white, silky, matted needles which melted a t 1 1 4 ~ 5 ~ . 0.1655 gave 17.0 C.C. moist nitrogen a t 1 6 O and 755 mm. C,,H,N,S*C,H,O requires N = 12.07 per cent. N = 11.95. 2- Phen ylimino- 3 : 4-dime th y Z - 2 : 3-dih ydr ot 7kixo Ze, El- '>C : NPh. CMe*NMe 2-Anilino-4-methylthiazole was heated with methyl iodide and methyl alcohol in a closed vessel for one hour in the water-bath, and the product, after being diluted with water and boiled to expel the methyl alcohol, made alkaline and extracted with benzene; the oily residue obtained on drying and distilling the benzene residue was allowed to solidify slowly in a desiccator over soda-lime. The base prepared in this manner was moderately soluble in warm light petroleum, frolri its solution in which it separated in small, white crystals melting at 65-66".0.1458 gave 17.4 C.C. moist nitrogen a t 14.5" and 755 mm. N = 13.93. The plutinicldoi-ide, formed by adding platinic chloride to the solution of the base in warm dilute hydrochloric acid, crystallised from the solution on cooling, and after being dried at 105" melted at 189-1 90°.CIIHl2N2S requires N = 13.72 per cent. 0.3446 gave 0.0584 Pt. Pt = 23-88. (C,,H,,N,S),,H,PtCI, requires Pt = 23.83 per cent. Hydrolysis of 3-Phenylimino- 3 : 4-dimethyl-2 : 3-diJqd~otJ~iaxole. The methylated base was heated with concentrated hydrochloric acid in a sealed tube at 245-250" for four and a half hours. After concentration on the water-bath, during which operation considerable quantities of hydrogen sulphide were evolved, an excess of potassium hydroxide was added and the product distilled in a current of steam, any alkaline vapours which passed through the receiver being retained by an acid trap. The distillate, after acidification and concentration, was again made alkaline and boiled in a reflux apparatus until no alkaline vapours could be detected on removal of the hydrochloric acid trap.The residual liquid in the boiling flask gave the isonitrile VOL. LXXXIX.66 YOUNG AND CROOKES: CONTRIBUTIONS TO THE reaction for primary amines and the bleaching powder reaction for aniline, whilst the solution from the hydrochloric acid trap gave only the first of these two reactions, but when made alkaline smolt strongly of methylamine. I n one experiment, a small amount of a white, solid substance separated from the distillate; it melted a t 78" and wits possibly 2-oxy-3 : 4-dimethyl-2 : 3-dihydrotliiazole. %Allylamino- 4-methylthiaxole, @Ec!>C? *NH * C,H,. The hydrochloride of this base was formed by gradually adding 1 mol. of chloroacetone to 1 mol. of allylthiocarbamide; as the re- action takes place with considerable development of heat, it was necessary t o cool the mixture with water.The cold product was treated with aqueous potassium hydroxide, and the solid thus obtained recrystallised from light petroleum, when it formed locg, white, silky needles. The base, which was observed to have a slight odour resembling that of thyme, melted at 40-41". N = 18.44, 0.2572 gave 40.9 C.C. moist nitrogen at 15O and 753 mm. 0*1780 ,, 0.2640 BaSO,. S = 20.66. C7H1,N,S requires N = 18-18 ; S = 20.78 per cent. The acetyl derivative, formed by boiling 2-allylamino-4-methyl- thiazole with acetic anhydride, was obtained as an oil which solidified slowly to a crystalline mass; it was readily soluble in benzene, but only moderately so in light petroleum, from which it orystallised in thin, square plates, It melted at 36-37" and had, especially before recrystallisation, an odour resembling that of impure aoe tamide, 0.2590 gave 0.3040 BaS04.S = 16.12. C7H,N,S*C2H,0 requires S = 16.33 per cent. '>C: N*C,H,. CH-- CMe*NMe 2-Allylimino-3 : 4-dimethyl-2 : 3-di?~ydi*othiaxole, I I The hydriodide formed by heating 2-allylamino-kmethylthiazole with methyl iodide and methyl alcohol in a closed vessel at 100" separated from the mixture after some days in almost colourless, large, prismatic plates. When dissolved in a small quantity of alcohol, in which it was readily soluble, and precipitated by addition of ether, the salt was obtained as a white, crystalline meal, which melted a t 1 1 6-1 17". 0.2035 gave 0.1616 AgT. 1=42.94.C,H,,N,S,HI requires I = 42.89 per cent.CHEMISTRY OF THE AMIDINES. 67 On treatment of the hydriodide with potassium hydroxide in con- centrated aqueous solution, extraction of the product with benzene, and evaporation of the extract, the free base was obtained as a slightly red, viscid oil possessing a characteristic odour ; it was readily soluble in dilute acids, and formed a crystalline platinichloride, which dissolved to only a slight extent in hot dilute hydrochloric acid. Hydyolysis of 2-Allylimino-3 : 4-dimethyl-2 : 3-dihydrothiazole, The methylated base was heated with concentrated hydrochloric acid in 5 sealed tube a t 230-240" for five hours. The product was concentrated, made alkaline, and distilled in a current of steam; the distillate was treated in the same manner as that obtained by the hydrolysis of 2-phenylimino-3 : 4-dimethyl-2 : 3-dihydrothiazole.Both the residual liquid from the reflux apparatus and the solution from the hydrochloric acid trap gave the isonitrile reaction, showing that the hydrolysis had resulted in the formation of two primary amines. 2-*4 cetylinzino- 4 -naetlq I- 2 : 3 -dihydrothiaxole, '>c: N AC. CH- EMe*NH 2-Amino-4-methylthiazole hydrochloride was prepared by the action of chloroacetone on thiocarbamide (Traumann, loc. cit.), and the base liberated by addition of concentrated aqueous potassium hydroxide and extracted with benzene. On evaporationof the extract, there was obtained a slightly pink oil, which, when cooled over calcium chloride in a desiccator, solidified t o a white, slightly hygroscopic solid melting a t 4 2 O .The acetyl derivative, formed by boiling the anhydrous base with 1 mol. of acetic anhydride in a reflux apparatus, is moderately soluble in warm water, from which it separates on cooling in shining, colourless crystals. The melting point was found to be 134O, as given by Traumann. On addition of 1 mol. of silver nitrate and 1 mol. of ammonia in aqueous solution to its solution in alcohol, the acetyl compound formed a silver derivative as a dense, white precipitate, which, after being well washed and dried a t loo", was fairly stable to light. 0.1962 gave 0.0809 Ag. Ag=41-23. C,H,N,SAg*C,H30 requires Ag = 41 *03 per cent. When heated with 1 mol. of methyl iodide in methyl-alcoholic solution in a closed vessel at looo, the silver derivative forms 2 -acet y Zimino - 3 ; 4dimeth y I - 2 : 3 -dihydrothiazole, '> c: N A ~ , CH--- k.!Me*NMe68 YOUNG AND CROOKES: CONTRIBUTIONS TO THE which, on evaporation of the methyl-alcoholic solution and re- crystallisation of the residue, was obtained in wbite, nodular, crystalline aggregates which melted at about SOo, or sharply at 1 1 3 O , after being dried over sulphuric acid in a vacuum (Hantzsch and Weber, Ber., 1887, 20, 3124).Methylation of 2-MethyZamino-4-methyZthiazole. The hydrochloride of 2-methylamino-4-methylthiazole was prepared by slowly mixing chloroacetone and methylthiocarbamide in molecular proportions; it was found necessary to keep the reacting mixture cooled by means of ice-water. The base was liberated by treatment of its hydrochloride with aqueous potassium hydroxide, and recrystal- lised from benzene, from which it separated as a slightly pink oil; this solidified slowly, forming long, white needles, which melted at 6 4 O and dissolved readily in methyl alcohol or light petroleum.Traumann (Zoc. cit.) gives the melting point of this base as 42'. The result obtained from the sulphur determination, together with the formation of 2-methylimino-3 : 4-dimethyl-2 : 3-dihydrothiazole, is sufficient proof of the constitution of our base. 0,1962 gave 0.3642 BaSO,. When heated with 1 mol. of methyl iodide in methyl-alcoholic solution in a closed vessel at 1 OOO, 2-methylamino-4-methylthiazole yielded 3-methylimino-3 : 4-dimethyl-2 : 3-dihydrothiazole hydriodide, CH-S >C:NMe,HI, which separated in stellate aggregates of 8Me-NMe crystals melting at 5 4 O , or at 164" after drying at 105O.Hantzsch and Weber, who prepared this salt by heating 2-amino- thiazole with 2 mols. of methyl iodide (Ber., 1887, 20, 3123), found it to melt at 54", or when anhydrous at 155O, whilst Traumann (Zoc. cit.), who obtained the base by treating s-dimethylthiocarbamide with chloroacetone, gives the melting point of the anhydrous hydriodide as 164". S = 25.52. C,H,N,S requires S = 25.06 per cent. 2-Im i 9% o t e t r u h y d r o t hi ax o 1 e s a n d %A mi n 0-4 : 5-d i h y d r o t h ia x o 2 e 8. 2 - Phsn~Zimino-5-methyZtetra~~ydi.ot~iazole, The hydrochloride, prepared by heating s-phenylallylthiocarbamide with concentrated hydrochloric acid in a closed vessel at looo, was treated with concentrated aqueous potassium hydroxide, and theCHEMISTRY OF THE AMIDINES.69 product recrystallised from hot dilute alcohol. The base obtained in this manner crystallised in needles and melted at 117' (Prager, zoc. cit.). 0.1673 gave 0-2044 BaSO,. 0.1577 ,, S = 16-79. 19.6 C.C. moist nitrogen at 11*5°and 755 mm. N = 14.71. The base formed a picrate, which crystallised from dilute alcohol in C,,H,,N,S requires S = 16.67 ; N = 14.58 per cent. rough, yellow needles and melted a t 154O. 0.1378 gave 20.7 C.C. moist nitrogen at 19' and 735 mm. N = 16.46. C,,H,,N,S,C6H30,N3 requires N = 16-63 per cent. When shaken with acetic anhydride, the base dissolved with slight development of heat, forming a clear solution; after some time, the mixture was dissolved in ether, and the ethereal solution was washed with aqueous potassium carbonate, dried, and distilled on the water- bath.The residual oil gradually solidified to a crystalline mass which melted at 47O. 0.1 808 gave 0,4069 CO, and 0.0993 H20. 0.1552 ,, 0.1557 BaSO,. S= 13.79. C,,H,,N2S~C2H,0 requires C = 61.54 ; H = 5-98 ; S = 13.68 per cent, The acetyl derivative was readily soluble in alcohol, ether, or benzene, less so in light petroleum, and separated from its solutions as an oil, which rapidly solidified on addition of a small quantity of the crystalline substance. When dissolved in alcohol and poured into an alcoholic solution of silver nitrate, the base formed the silver derivative, CloHI,N,SAg, which was obtained as a white precipitate.After being washed with dilute alcohol and dried at 904 the silver derivative detonated when heated on a piece of porcelain over the Bunsen flame, whilst when heated in a capillary tube it blackened and commenced to melt at 1 30°. C = 61.38 ; H = 6.10. 0,2473 gave 0.0890 Ag. CloH,,N2SAg requires Ag =I 36-08 per cent. With the object of obtaining possibly a methyl base isomeric with that prepared by Prager, the silver derivative was warmed with 1 mol. of methyl iodide in methyl-alcoholic solution and the product evaporated and shaken with benzene. The base obtained on evapora tion of the benzene solution was converted into its picrate, which crystallised in rough, yellow needles, melted at 154O, and gave analytical results agreeing with those required by the picrate of 2-phenylimino-5-methyltetrahydrothiazole. Ag = 35.99.70 YOUNG AND CROOKES: CONTKIBUTIONS TO THE 0.1279 gave 18.7 C.C.moist nitrogen at 17" and 756 mm. N = 16-86, CloH12N,S,C,K,07N, requires N = 16.63 per cent. C1,H,,N,SMe,CGH,O7N3 ,, N = 16.09 ,, ,, 2- P?LenyZ.nzet~hyZamino-5-met~LyZ-~ : 5 -dihydrothiaxoZe, YHMe.8 >C*NMePh. CH,-N As the action of methyl iodide on the silver derivative did not lead to the formation of a methyl base, 2-phenylimino-5-methyltetrahydro- thiazole was heated with 1 mol. of methyl iodide in methyl-alcoholic solution in a closed vessel at 100'. The base mas mixed also with an excess of methyl iodide, and the mixture was allowed to stand over- night in a flask cooled by ice-water (Prager, Zoc. cit., p.2997). By these two methods, the same methyl base was obtained as an oil, readily soluble in alcohol, ether, benzene, or dilute acids. The pZatinichZoride of the methyl base crystallised in salmon- coloured, nodular aggregates of plates and melted a t 184O. A,* 0.4758 gave 0*1132 Pt. Pt=23'79. B. 0.3254 ,, 0*0775 P t . Pt=23*81. (C,,Hl,N,S),,H,PtC16 requires Pt = 23.69 per cent, The yicrate of the methyl base melted under boiling water, in which it was slightly soluble, crystallising on cooling in soft, yellow needles ; it dissolved readily in alcohol, from which, on dilution, i t crgstallised in clusters of yellow needles. It melted at 114-1 15' ; Prager gives its melting point as 125". A. 0*1180 gave 17.1 C.C. moist nitrogen at 18" and 740 mm. N = 16.28, B. 0.1525 ,, 21.8 ,, ,, ,, 19' ,, 751 mm.N=16.23. C,,H,,N,S,C,H307N, requires N = 16.09 per cent. ? HMe's>C NEt Ph . CH,-N 2-Phenylirnino-5-methyltetrahydrothiazole was heated with 1 mol. of ethyl iodide in ethyl-alcoholic solution in a closed vessel at 100" and the product boiled with a small quantity of water, made alkaline, and extracted with benzene. On evaporation of the benzene, the ethyZ base was obtained as an oil, which was readily soluble in alcohol or ether, less so in light petroleum, and only sparinglyso in water, and had the peculiar odour characteristic of the group of compounds, On addition * The analyses A and B given for the platinichloride and piarate are for the salts sf the base prepared by the first and second methods of methylation respectively.CHEMISTRY OF THE AMIDINES.71 of platinic chloride to its solution in dilute hydrochloric acid, the base formed the platinichloride, which separated as a reddish-yellow, crystalline powder and melted and decomposed a t 156'. 0.6488, dried at 1 0 5 O , gave 0.1488 Pt. Pt = 82-93. (C,,H,,N,S),,H,PtCl, requires Pt = 22.94 per cent. Formation of P-Methyltauurine from 2-Phen~Zetl~~lc6mino-5-me~hyl-4 : 5 dih y h o t hiaxo Ze. The ethyl base was oxidised with potassium chlorate in slightly warm hydrocliloric acid, and the product evaporated to dryness and extracted with a mixture of alcohol and ether. The residue from this extract was heated with concentrated hydrochloric acid in a sealed tube at 150-200', and the solution filtered from tarry matters and evaporated to dryness.On extracting the dried product with absolute alcohol, a white residue was obtained, which, aftrer recrystallisation from 90 per cent. alcohol, separated from a small quantity of warm water in transparent, rhombic plates and agreed in its other properties with those of P-methyltaurine as described by Gabriel (Ber., 1889, 22, 2984). When powdered and heated in a capillary tube, P-methyltaurine melts a t 284-285'. 0.1732 gave 0.1638 (30, and 0.1015 H,O. 0.1845 ,, 0.3143 BaSO,. S= 23.39. 0,1936 C=25*79 ; El-6.51. ,, 1'7.5 C.C. moist nitrogen at 17' and 742 mm. N= 10.24, H = 6.48 ; N = 10.07 ; NH,=CH;CHMe*SO,H requires C = 25.90 ; S = 23.02 per cent, s-p- TolyZallylthiocarbmnide, C,H,Me:NH* C'S*NH*C,H,. This substance was prepared by boiling p-toluidine with a slight excess of allylthiocarbimide in alcoholic solution in a reflux apparatus. On removal of the alcohol and excess of the thiocarbimide by distillation in a current of steam, the product separated as a heavy oil, which solidified on cooling and, after purification by repeated crystallisation from dilute alcohol, was obtained in nodular aggregates of almost colourless needles which melted at 98'.09011 gave 0.2304 BaBO,. S= 16.75. CI1H1,N,S requires S = 15.53 per cent,72 YOUNG AND CROOKES: CONTRIBUTIONS TO THE YHMe* >c : N.C,H,. CH,*NH s-p-Tolylallylthioearbamide was converted into the corresponding tetrahydrothiazole by the action of concentrated hydrochloric acid at 100' under pressure. The clear solution thus obtained was evapor- ated to dryness, the residue treated with aqueous potassium hydroxide, and the liberated base purified by recrystallisation from alcohol.2 -p-Tolylimino-5-methylte trahydrot hiazole crys t allised from dilute alcohol in small, shining plates or broad needles, or from ether in diamond-shaped plates, and melted at 106". 0.1563 gave 0.3664 CO, and 0.0970 H,O. 0.1887 ,, 22.2 C.C. moist nitrogen at 16'and 750 mm. N = 13.49. 0.1759 ,, 0.2001 BaSO,. S= 15.64. C,,H,,N,S requires C = 64.08 ; H = 6.80 ; N = 13.59 ; S = 15.53 per The base dissolved readily in dilute hydrochloric acid, and on addition of platinic chloride formed the platiniddoride, which crystal- lised in small, rough, thick, yellow needles, and after being dried at 110" melted and decomposed a t 204'. C = 63.97 ; H = 6.90.cent, 0.5061 gave 0.1199 Yt. (C,,H,,N2S),,H,PtC1, requires Pt = 23.74 per cent. The acetyl derivative, C,,H,,N ,S*C,H,O, was formed by gently warming the base with acetic anhydride ; i t crystallised from light petroleum in white prisms and melted at 61'. Pt = 83.69. 0.1689 gave 0-1606 BaSO,. Cl3H1,ON2S requires S = 12-90 per cent. When boiled with dilute hydrochloric acid, the acetyl derivative gradually dissolved, and on addition of potassium hydroxide to the solution the parent base, melting at 106O, was precipitated. S = 13-08. 2-p- Tolylmethylarnino-5-methyl- 4 ; 5-dihydrothiaxole, ~HMe*s>C*NMe*C,H7. CH2--N On shaking 2-p-tolylimino-5-methyltetrahydrothiazolo with slightly more than one mol. of methyl iodide, the mixture became warm and changed to a clear liquid which gradually solidified.The product was boiled with a small quantity of water to free it from the excess OF methyl iodide, made alkaline, and extracted with ether. TheCHEMISTRY OF THE AMIDINES. 73 methyl base, which was obtained as an oil on evaporating the ethereal extract, dissolved readily in dilute hydrochloric acid, alcohol, ether, or benzene, and had the characteristic odour of the 2-amino-4 : B-dihydro- t hiazoles. The platinichloride melted and decomposed at 1104 0.2213 gave 0.0513 Pt. Pt=23.18. (C,,H,,N,S),,H,PtCI, requires Pt = 22.94 per cent. Oxidation of 2-p- Tolylmethykamino-5-metlr~yk-4 : 5-dihydrothiaxole. The p-tolylmethylamino-base was oxidised with potassium chlorate and hydrochloric acid, and the product treated as described under the oxidation of the phenylethylamino-base.The final residue, after extraction with absolute alcohol, crystallised from water in transparent plates, melted at 284--285O, and on analysis gave numbers agreeing with those required for P-methyltaurine. 0.1821 gave 0.3088 BaSO,. S = 23.32. C3H,03NS requires S = 23.02 per cent. The absolute alcoholic extract was evaporated with hydrochloric acid, treated with an excess of aqueous potassium hydroxide, and dis- tilled in a current of steam. On addition of hydrochloric acid and platinic chloride to the distillate, the platinichloride of methyl-p-tolui- dine separated as a red, crystalline powder, which was dried at 110'. 0.4109 gave 0,1222 Pt. Pt = 29-74. (C6H3[,MeoNHMe),,H~PtCls requires Pt = 29.91. 2-p-Tolylethylamino-5-methyl-4 : 5-dihydrothiclzole, CH,-N ~HMe*s>C*NEt*C,H7.2-p-Tolylimino-5-methyltetrahydrothiazole was heated with slightly more than one mol. of ethyl iodide in ethyl-alcoholic solution in a closed vessel for one hour a t looo, and the product boiled with water, made alkaline aud extracted with ether. The ethyl base was obtained, on evaporation of the ethereal solution, as an oil which was easily soluble in alcohol, benzene, or dilute acids. The plctinnichloride separated from its solution in warm dilute hydro- chloric acid in orange-coloured crystals, which melted and decomposed at 189-190'. 0.6832 gave 0.1505 Pt. Pt = 22.03. (C,,H,,N2S),,H2PtCI6 requires Pt = 22.21 per cent.74 YOUNG AND CROOKES: CONTRIBUTIONS TO THE Oxidation of 2-p-~olyZethyZ~mino-5-meth~Z-4 : 6-dihydrothiuxole. The p-tolylethylamino- base was oxidised with potassium chlorate and dilute hydrochloric acid, and the product hydrolysed with con- centrated hydrochloric acid a t 160-200'.The residue obtained on evaporation was extracted with absolute alcohol and recrystallised from waterl when it formed transparent plates and melted a t 284-285' (@-met h yltaurine). 0.1932 gave 0.3286 BaSO,. The alcoholic extract yielded the platinichloride of ethyl-p-toluidine, 0.8336 gave 0,0666 Pt. S = 23-38. C,H,O,NS requires S = 23.02 per cent. Pt = 28.51. (C,H,Me*NH Et),,H,PtC1, requires Pt = 28.68 per cent. YHMe S >C:N* C,H,. CH,*NH %o-~olyhino-5 -methyltetra~ydrothiaxob, This base mas prepared according to Prager's directions (Zoc. cit., p.2999) from s-o-tolylallylthiocarbamide ; i t crystallised in small plates and melted a t 126'. 0-1699 gave 0.1941 BaSO,. C,,H,,N,S requires S = 15-53 per cent. On addition of silver nitrate to its solution in alcohol, the base formed the silver derivative as a white precipitate, which was washed and dried a t 105'. S= 15.71. 0.9561 gave 0.3289 Ag. C,,H,,N,SAg requires Ag = 34.49 per cent. The acetyl derivative, C,,H1,N,S*C2H,0, was prepared by boiling the base with acetic anhydride and shaking the product with water ; it crystallised from light petroleum in stout prisms, melted a t 58", and was easily soluble in benzene, alcohol, ether, or acetone, but only sparingly so in light petroleum. Ag= 34-40. 0,1529 gave 0.3522 CO, and 0.0897 H,O. C = 62.82 ; H= 6.52.0.2137 ,, 0.2029 BaSO,. S= 13.05. C,,H,,ON,S requires C = 62-90 ; H = 6.45 ; S = 12.90 per cent. The acetyl derivative dissolved unchanged in cold dilute hydro- chloric acid from its solution, in which it was precipitated unchanged on addition of aqueous sodium hydroxide, but when boiled with the dilute acid it was hydrolysed, and the precipitate obtained on addition of the alkali hydroxide consisted of the parent base melting at 126".CHEMISTRY OF THE AMIDINES. 75 2 -0- To ZyZmet?ylamino- 5 -methyZ-4 : 5 -di?bydrot?&zoZe, \!HMe*S CH,-N >C*NMe* O,H,. This substance was obtained as an oil by shaking 2-o-tolylimino-5- methylte trahydrot hiazole with methyl iodide and liberating the methyl base with aqueous potassium hydroxide. The platinichloride melted and decomposed at about 200". Pt = 22.S8. 0.5318 gave 0.1217 Pt. (C,,H,,N,S),,H,PtCl, requires Pt = 22.94 per cent. On oxidising the base with potassium chlorate and hydrochloric acid and hydrolysing the product with concentrated hydrochloric acid at 150-200°, we obtained, as did Prizger, P-methyltaurine melting a t 2 84-285'. 0.3044 gave 0.5106 BaSO,. S = 23.31. C,H90,NS requires S = 23.02 per cent. 2-0- To Zyleth ylnrnino-5-meth y Z-4 ; 5 -dihydrot?hiaxole, YHMe* S>C*NEt*C7H,. CH,-N The hydriodide of this base was formed by heating 2-o-tolylimino-5- methyltetrahydrothiazole with ethyl iodide and ethyl alcohol in a closed vessel at 100". When liberated by means of potassium hydroxide, the base was obtained as an oil which had the characteristic odoiir and dissolved readily in alcohol, ether, benzene, or dilute acids. The plutinicldoride formed orange-red crystals which melted and decomposed at 203O. 0.7959 gave 0.1764 Pt. Pt=22*17. (Cl,H18N2S),,H2PtC1, requires P t = 22.21 per cent, The base was oxidised with potassium chlorate and hydrochloric acid, the oxidation product hydroly sed with concentrated hydrochloric acid, and the residue obtained by evaporation extracted with absolute alcohol. The part insoluble in absolute alcohol was P-methyltaurine, as after recrystallisation from 90 per cent. alcohol it melted at 284-2 85'. 001587 gave 0.1499 CO, and 0.0945 H20. 0.2173 ,, C-25-76; H=6.62. 19.2 C.C. moist nitrogen at 16' and 754 mm. N = 10.22. C,H,O,NS requires C = 25.90 ; H = 6-48 ; N = 10.07 per cent.76 FORD AND GUTHRIE: THE INFLUENCE OF CERTAIN The absolute alcoholic extract yielded the platinichloride of ethyl-o- toluidine. 0.2786 gave 0.0800 Pt. Pt = 28.70. (C,H,Me*NHEt),,H,PtCI, requires Pt = 28.68 per cent. We take this opportunity of thanking the Research Fund Com- mittee of the Chemical Society for a grant by which the expenses of this investigation were partly defrayed.
ISSN:0368-1645
DOI:10.1039/CT9068900059
出版商:RSC
年代:1906
数据来源: RSC
|
10. |
X.—The influence of certain amphoteric electrolytes on amylolytic action |
|
Journal of the Chemical Society, Transactions,
Volume 89,
Issue 1,
1906,
Page 76-92
John Simpson Ford,
Preview
|
PDF (1094KB)
|
|
摘要:
76 FORD AND GUTHRIE: THE INFLUENCE OF CERTAIN X.-The Jn$uence OJ' Certain APnphoteric Electrolytes o n Amylolytic Action. By JOHN SIMPSON FORD and JOHN MONTEATH GUTHRIE. Ilu a recent publication on Lintner'a soluble starch and the estimation of diastatic power (J. SOC. Chem. Ind., 1904, 23, 414), it was pointed out by one of us that under certain conditions the addition of aspara- gine to starch solutions undergoing hydrolysis by malt diastase gave rise to an increased production of maltose. From the experiniental results obtained by working with starch preparations of varying degrees of purification, i t was concluded that this augmentation of the hydrolysis was due, not to a specific action of the amide on the amylase, but to an indirect action in preventing or lessening the inhibitive influence of certain impurities in the starch solutions.It was established that the addition of asparagine to starches containing a1 kaline impurities increased the maltose production at temperatures above 40°, whereas addition to purer starches decreased the maltose production. It was also noted that asparagine was able to lessen the inhibitory influence of traces of copper, which were found to have a very destructive effect on amylolytic action. As these observations are of considerable interest and physiological import, we have further investigated this action of asparagine and also the influence of certain amino-acids on amylolytic hydrolysis. Preparation of the Sturch. It was pointed out by one of us (Zoc. cit.) that soluble starch, prepared by Lintner's method or otherwise, is extremely difficult to purify ; it obstinately retains traces of phosphorus compounds whichAMPHOTERIC ELECTROLYTES ON AMYLOLYTTC ACTION.77 prolonged washing with water does not remove, and which are not readily eliminated by solution and precipitation of the starch, Certain of the preparations of soluble starch used in this investiga- tion were prepared by Lintner's process as usual, then further purified by solution in water and repeated precipitation by means of alcohol, first in the presence of hydrochloric acid and then without addition of acid. The method is tedious and from twenty to thirty precipitations may be necessary before a neutral product is obtained. We have now found that prolonged digestion and extraction of ordinary preparations from maize with dilute acid (HCI) removes the phosphorus compounds completely.After this treatment and wash- ing with water, a few precipitations with alcohol yield an equally pure starcb. The criteria of purity we employ are neutrality to rosolic acid and phenolphthalein, and absence of indications of phos- phoric acid to molybdate solution in the ash of 5 grams ignited with sodium carbonate and nitrate. The latter is a severe test and it is not often that a preparation is obtained which does not shorn a faint coloration to this reagent. The specific conductivity of 2 per cent. solutions of such putified starches runs about 5 x reciprocal ohms per C.C. at 2 5 O , so that, although not pure, a close approximation to purity is evident.I n connection with the drying of alcohol-pre- cipitated preparations of starch, we have noticed on several occasions that starches which were neutral when tested immediately after filtration, showed faint acidity after drying. This acidity is probably due t o slight oxidation of the alcohol ; Duchemin and Dourlen (Compt. rend., 1905, 140, 1466) have recently shown that oxidation of alcohol takes place more readily than is generally supposed. Whatever the origin of the acidity may be, its formation renders the attainment of neutral preparations somewhat difficult if ordinary methods of drying in air be employed. We have found i t convenient to dispense with the final drying in many cases, and also to supplement the method of alcohol precipitation by that of freezing out, the separated starch being sucked free from mother liquor on a Buchner funnel, then dis- solved at once in boiling water.The strength of the solution is readily deduced from its specific gravity. Working in this manner we have obtained much purer preparations, the specific conductivity of 2 per cent. solutions being reduced to 1.5 x at 25'. The dried alcohol-precipitated specimens, when moistened with water, form a jelly-like mass which, on heating, gives a solution of specific rotation [ a]D4.00 = 200-202°. On hydrolysis with malt extract at 5 5 O , the transformation products are the same as those yielded by ordinary starch paste, having the constants [a], 150°, R. 80. Therefore, if ordinary starch is a mixture of amylocellulose and amylopectin (Maquenne and ROUX, Compt.rend., 1905, 140, 1303), our prepara-78 FORD AND CUTHRIE: THE INFLUENCE OF CERTAIN tions must evidently have retained the same proportion of acid modified amylopectin, notwithstanding the prolonged purification and separation into fractions by alcohol precipitation and freezing out, Preparation of the Amylase. Ordinary preparations of malt diastase by Lintner's method (J. pr. Chsm., 1886, [ ii]? 34, 3'78) are exceedingly impure, and are as 8 rule strongly alkaline in reaction. We have endeavoured to prepare purer Epecimens by modifying Lintner's alcohol method, the crude product being dissolved in water, containing potassium dihydrogen phosphate, and reprecipitated by addition of excess of ammonium sulphnte. The precipitate so obtained was dialysed for some days and again precipitated, this time with alcohol.The diastase so obtained had only feeble amylolytic properties, and was still far from pure as regards freedom from mineral substances. As our object was to obtain an enzyme of considerable activity and relative freedom from saline impurity, we did not further pursue this method of preparation. Osborne and Campbell (J. Anzer. Chem. Soc., 1895, 17, 503; 1896, 18, 536) have made elaborate investigations on the chemical nature of amylase, and have prepared specimens of great activity and purity by the methods of '' salting out " and dialysis. We therefore employed their methods, and from a, quantity of highly active malt extract, kindly presented to us by the Distillers' Co., Ltd., Edinburgh, obtained a small yield of a preparation (F,) suitable for our purpose.This had a diastatic power of fully 300" Lintner. The specific conductivity of a 2 per cent. solution was 7 . 0 ~ 10-4 at 25'. As only 1 C.C. of a solution of 5 to 15 milligrams per 100 C.C. was taken for the experi- ments to be described, the amount of impurity contributed hy the enzyme preparation was less than that of the distilled water used. I n addition to the experiments with the purified starch and diastase, we have to record several made with ordinary preparations of Lintner's soluble starch and malt extract, the results of which we will consider first, as this is rendered necessary by a recent publica- tion by J. Effront (Moniteur ScientijGpe, 1904, 61, 561), in which he traverses the conclusions deduced by one of us (Zoc.cit.), and reiter- ates his opinion that the accelerating influence of asparagine and certain amino-acids on amylolytic action is a specific one, is inde- pendent of the temperature and alkalinity of the medium, and is exercised with all natural starches of whatever origin. The results given in his memoir do not, however, justify this conclusion, as the four starches which he employed are by his own showing obviously very impure. The titration values he records indicate that all the starches were alkaline, whilst the fact that different amounts ofAMPHOTERIC ELECTROLYTES ON AMYLOLYTIC ACTION. 79 maltose were yielded by each starch on treatment with equal amounts of malt extract is conclusive proof that the starches contained varying amounts of impurity.It may be pointed out that his purest prepara- tion (D) is, as regards titration value to rosolic acid, ten times more impure than the most impure starch used as an example in the experiments recorded by one of us (Zoo. cit.), and, further, it is this starch which gives the smallest maltose production, which result is in our experience indicative of metallic contamination, Notwithstanding this, J. Effront, without making any effort to repeat his work on the lines suggested (Zoo. od.) with purer preparations, or to verify or disprove our contention as to the significance of these titration values, or the influence of metallic impurity, seeks t o extend his generalisa- tions. We do not for a moment doubt the accuracy of his observa- tions, but the mere repetition of experiments under the same conditions does not add additional value to the conclusions he has formed. In order to elucidate further the important and varying influence of the impurities in starches on amylolytic action, we have prepared several impure, as well as purified specimens, and, as will be seen from the results obtained with the more impure, it is possible to transcend the tenfold increase of maltose production mentioned by J.Effront and other workers. A normal preparation of Lintner's soluble starch was shaken with a natural water containing much calcium carbonate (0.4 gram per litre) and traces of iron salts. The starch (Pa) was then filtered, washed with distilled water, and dried. It contained 0.006 per cent.of iron. With colour indicators, tha values per 100 grams were as under : Rosolic acid .................. 7.2 C.C. N/lOH,SO,. Phenolphthalein ............ 8.0 C.C. N/l ONaOH. One C.C. of malt extract, 1.2 grams of malt (d. p. 3s' L.) to 100 c.c., was added to 70 C.C. of a 1.5 per cent. solution of this starch, one hour at 60.3'. Milligrams of maltose per 100 C.C. Starch and malt extract without addition ..................... 3'0 ,, plus 15 milligrams of asparagine.. . 73.0 9 ) 9 2 30 ,, ... 73-0 9 9 50 Y 9 ... 102'2 ,, 7 ) 3 9 70 , Y Y , ... 111.0 9' >, ' 9 100 Y Y 2 9 ... 114.0 ? > Y Y ;> 9 , ' Y Y , The original starch (P) under like conditions gave a decreased We give below several experiments made with a number of starches maltose formation in presence of asparagine.of varying degrees of purification.80 FORD AND GUTHRIE: THE INFLUENCE OF CERTAIN ImtJluence of Asparagine om u Early " Maltose Produclion. Series I.-One C.C. of malt extract, 0.6 gram of malt (d. p. 40°) per 100 c.c., to 70 C.C. of 1.5 per cent. solution of starch, one hour at 5 9 - 5 O . Milligrams of maltose formed. - PS. N. M. Mz. ............ 29.2 64.2 55.5 49.6 Starch solution andmalt extract without asparagine 9 , Y 3 ,, plus 10 milligrams of asparagine - 46'7 - 12.3 Y Y 9 , 9 , 7, 30 9 , >, 64.2 46'7 67'1 12.3 9 7 ., , I 9 9 50 9 , 9 9 67-1 32.1 55.5 12-3 The titration values of these starches per 100 grams were 9 7 39 ,> 7 7 > 7 100 >, 55.5 - 29.2 - as under: Rosolic acid. Phenolphthalein. PP. ............... 10.0 C.C.N/lOH,SO, 8*ON/1 ONaOH N. ............... 0.2 ,, N/lONaOB 18*ON/lONaOH M. ............... 0.3 ,, N/10H2S0, 14.6A7/10NaOH Mz. .............. 0.1 ,, N/lONaOH 0.2N/1 ONaOH 100 c.c., t.0 70 C.C. of 1.5 per cent. starch solution, one hour a t 5 9 O . Starch solution and malt extract without asparagine ............ 29.0 29'2 14'4 29'6 Series II.-One C.C. of malt extract, 0.4 gram of malt (d. p. 36O) per Mz,. P. M. N. J S 9 ) ,, plus 35 milligrams of asparagine 17.6 20.4 29.0 23'8 Y , 9 , Y , 9 9 50 3 , 9 9 14.6 14.6 29.0 18-0 The titration values of these starches were, per 100 grams : Rosolic acid. Phenolphthalein. Mz *................ neutral neutral P. ............... 2.0 C.C. NIlONaOH 19 .ON/ 1 ONaO H M. ............... 0.3 ,, N/lOH,SO, 14*6N/lONaOH N. ...............0.2 ,, N/I.ONaOH 18*0N/1 ONaOH The foregoing starches, with the exception of Pa, were free from We give below some metallic impurities such as iron or copper. results with starches containing metallic impurities. L Starch. Rosolic acid ......... 3.0 C.C. Phenolphthalein.. .lO*O C.C. iV/ 1 ONaOH ,, ,, ,, Copper .............. .0*04 per cent. NIlONaOH per 100 grams. One C.C. of malt extract, 4 grams of malt (d. p. 30') per 100 c.c., to 70 C.C. of 1.5 per cent. solution, one hour at 40".AMPHOTERIC ELECTROLYTES ON AMYLOLYTIC ACTION. 81 Nilligrams of maltose formed. Starch and malt extract without asparaaine ..................... 79 9 9 .. plus 15 mdligiams of asparagine ... 324 2 , $ 9 9 9 30 1 , 7 9 ... 333 7 , 3 , > 7 50 7 ) > 9 ... 330 > l 9 1 , 7 100 ? > 9 9 ... 324 Drosten's XtamiL.Rosolic acid ......... 3.0 C.C. N/lOH,SO, per 100 grams. Phenolphthalein.. . 12.0 C.C. N/lONaOH ,, ,, ,, Copper .............. .0.0075 per cent. One C.C. of malt extract, 4 grams per 100 c.c., to $0 C.C. of 1.5 per cent. solution, thirty-five minutes at 40'. Milligrams o f maltose formed. Starch and nislt extract without asparagine ..................... 84.6 > 7 9 9 plus 75 milligrams of asparagine ... 128'4 Numerous other experiments have yielded similar results, and in conjunction with those already published (Zoc. cit.) confirm con- clusively the opinion expressed there, that when augmentation of diastatic action of malt extract is obtained on the addition of asparagine, the augmentation is due to the influence of the asparagine in lessening the inhibitory effect of alkaline or other impurities present in the starch solutions, and not to a specific action in the amylase under such conditions.The conclusion we arrive at as to the influence of asparagine may be extended to the other substances which J. Eff ront (Eoc. cit. and Bull. Xoc. chim., 1904, [iii], 31, 1230) states stimulate amylolytic action. He concludes that the amino-group, and not the amide, accelerates the action, because he obtained augmentation with aspartic acid, sarcosine, glycine, alanine, leucine jasparagine), glut - aminic acid, and hippuric acid, whereas succinamide, acetamide and its homologues, benzamide, the amines, h ydroxylamine, and hydrazine exhibit a retarding influence. It is to be observed that the substances he enumerates in the favouring group are either weak acids or amphoteric compounds.In the paper already referred to, it was pointed out that asparagine, under the conditions of hydrolysis in question, was able to overcome or lessen the inhibitory effect of traces of copper on amylolytic action. We give in the following table some additional experiments as to its influence on metallic impurities. Inftuence of Aspurugine on Certuin Metallic Inapurities. One C.C. malt extract, 4 grams per 100 c.c., to 70 C.C. of 3 per cent, VOL. LXXXIX. G starch, P solution, one hour at 40°.82 FORD AND GUTHRIE: THE INFLUENCE OF CERTAIN Grams of maltose formed. Starch solution and malt extract without addition ..................... 0 32 0.06 9 , plzu 0 '1 milligram of copper as sulpliate .................. ,> ,, 0.1 7 9 ,, plus 0.1 grain of aspragine 0.29 9 , ,, 0.1 , , mercury as chloride .................0 -02 ,- 3 7 0.1 9 , ,, plus 0.1 gram of asparagine 0.01 ,, , , 0'1 ,, mercury 3s cyanide ................ 0.0s 9 , ,, 0.1 ,, , , plus 0.1 gram of asparaghe 0 *03 7 ) 7 , 10'0 ,, copper as aminosuccinainate ....... 0 '08 3 , J > 9 9 , , plus 0 '1 gram of asparaghe 0.27 J , ,! 100'0 ,, asparaghe ............................ 0 *31 These results indicate that the protective influence of asparagine in the case of copper is due to the formation of copper aminosuccinamate and its lessened dissociation in presence of excess of asparagine and its salts, the free copper ions being so reduced in quantity as not to inter- fere greatly with normal amylolytic action. We have here an explana- tion of the fact already recorded by us (J.Xoc. Chem. I n d . , 1905, 24, 605), that traces of copper, which greatly inhibit the amylolytic action of precipitated malt diastase (Lintner's), have much less effect on the activity of malt extract. It was pointed out (Zoc. cit.) that asparagine at temperatures above 40° reacted more strongly acid to colour indicators ; we now supply evidence to show that this acidity is really exhibited by ordinary recrystallised specimens of the amide. This is clearly shown by their action on sucrose solutions at temperatures of 40' and 60'. Acidic Function of Aspccragine ( p = 0*50). GI-ams of invert sugar per 100 c. c. 20 honrs a t 20 pcr cent. sucrose solution.50 C.C. of sucrose solntion, water to 100 C.C. ................................ Y , ,, plzcs 0.5 gram of' asparqine, plus water t o 100 C.C. ,, 1.0 7 , 9 , >, >, ~, 1.2 milligranis of hydrochloric acid, plus water t o 100 C.C. ,-> 40". 60". 0.013 0.019 0.019 0.255 0'020 0.343 - 0.971 0.146 -- The asparagine used in the preceding experiments was purified by recrystallisation from alcohol. The molecular conductivity at 25" for ZI = 16 was 0.50, a value in close agreement with that given by Walden (Zeit. physiktcl. Chem., 1891, 8, 4S3). As we now know that the active acidity of such recrystallised asparagine is mainly due to the presence of impurity, we will return t o this subject subsequently. We can infer that ordinary specimens of asparagine in virtue of their acid function overcome the inhibitive effect of hydroxyl ions present in our alkaline starches.We have not, however, so far offered any proof that starches with titration values indicating alkalinity, that is, requir-AMPHOTERIC ELECTROLYTES ON AMYLOLYTIC ACTION. 83 ing the addition of acid to bring about neutrality to rosolic acid, are really alkaline. The following experiment shows that such starches at least possess a potential, if not an actual, alkalinity. To 2 grams of each starch (in 70 C.C. water), 20 C.C. of 10 per cent. sucrose were added and 10 C.C. of dilute hydrochloric acid, equal to 1.2 milligrams of hydrogen chloride. Twenty C.C. of sucrose solution plus 10 C.C. of the acid were also made to a similar volume. The solutions (in Jena flasks) were kept for seventeen hours at 60".The invert sugar produced was as under : Starch. Grams of invert sugar. Mz2 ............................................................... 0,293 Pp ................................................................. 0.147 M .................................................................. 0.250 Aqueous sucrose plus 1.2 milligrams of hydrogen chloride 0.350 The starch Mz2 was neutral to rosolic acid and phenolphthalein ; the values of the other starches have already been given, As the viscosity effect would be the same in each case, the reduction of sugar inver- sion may be regarded as due to alkalinity or to a lessened dissociation of the acid caused by the salts present. The starches were free from chlorides, the salts being phosphates ; whether at such dilutions double decomposition may be looked for is doubtful.In any case this reduction of the number of free hydrogen ions is for our purpose tantamount to alkalinity. Experiments were made to see if these starches increased the rate of mutarotation of freshly dissolved glucose. The results were negative, the rats of change of rotation being the same with each starch. Possibly this indicates that no free hydroxyl ions are present in the so-cidled alkaline starches ; something, how- ever, is present which is capable of reducing the amount of free hydrogen ions of the added acid. We have already shown that ordinary preparations of asparagine exhibit distinctly acid properties a t 60°, whereas, allowing for reduced velocity of reaction, a t 40" it has practically no acidic function.As amylolytic action is admittedly greatly influenced by the degree of alkalinity or acidity of the medium, J. Effront's contention that the favouring influence of asparagine on amylolytic action is independent of the temperature and degree of alkalinity of the starch becomes un- tenable. Apart from the question of the active acidity of ordinary asparagine at higher temperatures, this amide, glycine and other amino-acids are amphoteric electrolytes, having potential acid and basic functions, capable of neutralising acid or alkali to an extent dependent on the relative proportions of acting substances and the temperature. This is shown by their influence on amylolytic action, t o be described later, and also by the following results obtained by f l 984 FORD AND GWTHRIE: THE INFLUENCE OF CER'I'AIN methods used by Walker (Zeit.physikal. Chem., 1889, 4, 389), Winkelblech (ibid., 1901, 36, 546), and others. The diminution in concentration of H' and O H ions in solutions of hydrochloric acid and caustic soda (due to salt formation) was observed by measurements of electrical conductivity. Aaparagine and Hydrochloric Acid at 25'. Molecular conduc- Concentration. tivity. N/10 hydrochloric acid ............ 381 '6 plus 0.012 niol. of asparaginc 345.1 ,, 0.025 7 , ,, 313.4 7 , 0.05 9 , ,, 248.4 7 9 0'10 2 , ,, 250.8 > 7 0.20 Y Y ,, 100.6 > 7 0 - 3 l ,, 2 , 86.3 Asparagine and Potccssium Chloride at 25". Molecular conduc- Concentration. tivity. hTJIO potassium chloride ............ 128.5 plus 0.05 mol.of asparagine 127.5 ?, 0.10 7, ,, 127'0 7 , 0.20 7 7 ), 125*4 ,? 0.40 7 7 ,, 120'1 Glycine and Caustic Soda at 25". Molecular conduc- Concentration. tivity. N/3 0 caustic soda ..................... 204 *6 plus 0.025 mol. of glycine . 168 *7 Y, 0-05 , 7 ,, 136.0 3 , 0.10 >, , 7 66.0 , 7 0.20 9 7 ,, 65.0 7 > 0.40 Y 7 3 ; 63 '5 7 ) 0'80 ,> >, 62.4 Aaparagine and Caustic Soda at 25". Molecular Concentrat ion. tivity. NJ10 caustic soda ..................... 204 06 plus 0 '025 mol. of asparagine 166 '6 9 , 0.05 Y , ,) 133'3 7 , 0-10 , 7 3 , 62.7 ,, 0'20 7 , > ) 56 *7 , 9 0'40 7 7 9 , 53'6 conduc- Glycine and Eydrochloiic Acid at 25". Molecular conduc- Concentration. tivity. N/10 hydrochloric acid ...........381.7 plus 0'025 mol. of glycine . 303'4 9 7 0.05 , I ,, 259'5 >, 6-10 9 , ,, 153.3 7 , 0.20 2 1 ,, 102.7 Y > 0.40 7 7 Y , 93.6 ? Y 0-80 9 9 ,) 87.6 Glycine and Potassium Chloride at 25". Molecular conduc- Concentration. tivity. NjlO potassium chloride ............ 128.5 plus 0'1 mol. ofglycine ... 127.2 a-Alanine and Hydrochloric Acid at 25". NJ10 hydrochloric acid ............ 381 *7 plus 0.025 mol. of a-alanine 303-4 7 9 0.05 7 : ,, 236.5 7 7 0.10 9 , 7 , 138.8 7 , 0.20 7 , ,, 96.7 7 ) 0.40 7 , ,, 86-1AMPHOTERIC ELECTROLYTES ON AMYLOLYTIC ACTION. 85 a-Alanine and Caustic Soda at 25". Molecular conduc- Concentration. tivity. N/10 caustic soda ..................... 204-4 plus 0.025 mol. of a-alanine 161'3 I , 0.05 I , ,, 124'4 ,, 0.10 9 , ,, 62'2 I , 0'20 ,, ,, 61'4 9 , 0.40 i f ,) 59.2 a- Alanine and Potassium ChEoride at 25".Molecular condnc- Concentration. tivity. N/lO potassium chloride . .. . . . , .. ... 1285 p l w 0-1 mol. of a-alanine ... 127.2 It is not necessary to enter into any general discussion of the above results, which we record simply to show in a qualitative manner the amphoieric nature of these substances. The theoretical and quantita- tive aspect of the subject is fully developed by Winkelblech (loc. c i t . ) and 'Walker (I'roc. Roy. Soc., 1904, 73, 155, and 74, 271). Purification of Asparagine. We stated previously that the active acidity exhibited by ordinary specimens of recrystallised asparagine is due to the presence of impurity. This impurity we find is present in all preparations we have examined which have been "purified" by the customary methods of recrystallisation.Walker bas recently shown (Zoc. cit.) from theoretical calculations that pure asparagine should have a molecular conductivity of 0.087 a t w = 16. By crystallisation from water twenty-four times he has prepared ;I specimen with p = 0.096, using water of k: = 0.7 x 10-6 a t 1 8 O . We have prepared asparagine of a similar degree of purity, and find by reducing the duration and temperature of dissolution that it is possible to obtain this purity after about twelve recrystallisations. We dissolve the finely-ground amide in a minimum amount of "conductivity" water at 60-65', cool rapidly, stirring vigorously so as t o obtain a crop of very small crystals. These are freed from the mother liquor and washed with a small quantity of ice-cold water, the treatment being repeated until a product of constant conductivity is obtained.The yield, from the nature of the process, is very small. Asparagine of this purity exhibits practically no active acidity; this is evident from its slight inversion of sucrose in the experiments recorded below, the small fall of angle being due to the production of aspartic acid. We find, under like con- ditions of heating, an obvious increase in the conductivity of aqueous solutions of asparagine ; heating on a water-bath for a short time is also sufficient to cause slight decomposition. This provides an ex- planation of the difficulty of obtaining pure asparagine by simple re- crystallisation ; when t h e substance is dissolved in hot or boiling86 FORD AND GUTHRIE: THE INFLUENCE OF CERTAIK Jater, aspartic acid is produced, and probably some of the ammonia also formed is driven off, as ammonium aspartate solutions lose ammonia on boiling.On cooling t o crystallise, or on addition of alcohol, it is probable that the aspartic acid forms a salt with the amide, the presence of which, or of the ammonium salt, in small quantity is competent to account for the apparent increase of acidity observed on heating solutions of such preparations of asparagine. Even in the presence of an excess of asparagine, the salt undergoes hydrolytic dissociation when the solutions are heated, giving rise to the presence of free hydrogen ions. Apart from this, if we regard asparagine as an internal ammonium salt, it is possible that its hydrolytic dissociation gives rise to the presence of the traces of free H' ions observed in the solutions of our pure asparagine.At the same time we consider that the marked acid function observed by our- selves and by Degener (Chern. Centr., 1897,2,936) is due mainly to the presence of saline impurity in our preparations. These observations, whilst they force us to modify somewhat our views as to the influence of pure asparagine on pure amylase and starch, do not invalidate our deductions from the foregoing experiments with more or less impure starches. It is perfectly certain that no one has hitherto worked with such pure asparagine, and opinions as to the influence of this amide on amylolytic action have been deduced from experiments made with ordinary preparations which contain an approximately constant amount of impurity.Further, the potential acid function of the pure substance is capable of neutralising impurities, so we need only modify our views to the extent that pureasparagine added to pure amylase and starch will have little influence, whereas ordinary specimens inhibit the action. The inhibition of action brought about by the addition of asparagine to the transformations with the purer starohes recorded in the preceding part of this paper is due t o the acid-forming impurity in the amide. Pure asparagine does not retard the hydrolysis, nor does it augment this reaction unless the starch contains certain impurities. Action of Asparagine, Glycilze, and a-Alanine on Sucrose.Rotation of solutions in a 2-dcm. tube a t 16'. After 20 hours a t - 40". 60". 50 C.C. of 10 per cent. sucrose solution, pZus 0.375 gram of 50 C . C . of 10 per cent. sucrose solution, plus 0.445 gram of 50 C.C. of 10 per cent. sucrose solution, plus 0.375 gram of glycine, diluted to 100 C.C. .................................... 6.62 6-61 a-alaniue, diluted t o 100 c.c.. .................................. 6-60 6 -58 asparagine," p = O - l O , diluted to 100 C.C. .................. 6'60 6 -50AMPHOTERIC ELECTROLYTES ON AMYLOLYTIC ACTION. 87 Action of Asparugins, Glycine, ccnd a-Alanine on Sicc~oss (continued). Rotation of solutions in a 2-dcm. tube at 16'. After 20 hours a t - 40". 60". 50 C.C. of 10 per cent. sucrose solution, plus 0.375 gram of asparaghe," p = 0 '20, diluted to 100 C.O................... 50 C.C. of 10 per cent. sucrose solution, plus 0,375 gram of asparaghe,* p==0*50, diluted t o 100 C.C. ................. 50 C.C. of 10 per cent. sucrose solution, plus 1.2 milligrams of hydrochloric acid, diluted to 100 C.C. ..................... 50 C.C. of 10 per cent. sucrose solution, plzcs 0.6 milligram of hydrochloric acid, diluted to 100 C.C. ..................... 50 C.C. of 10 per cent. sucrose solution, pZus water only, diluted to 100 C.C. ............................................... 6.57 6'47 6.50 6 -83 6-45 4.80 - 5.09 6 '62 6.60 Rotation of each solution before heating = 6 '63 5 0 '03". * At v=16. The potential basic function of the compounds is well illustrated by the manner in which they decrease the inversion of sucrose by acid.The salts formed undergo very considerable hydrolytic dissociation in dilute aqueous solution, hence a large excess of the base must be added to reduce this. As for our purpose we have only to consider the influence of the substances on minute traces of acid, the experiments recorded below were carried out with acid (HC1) in presence of a distinct excess of the base. Basic Function of Aspcwcbgine, Glycine, and a- Alnnim. Rotation of solutions in a 2-dcm. tube a t 16". After 20 hoiurs a t 50 C.C. of 10 per cent. sucrose solution, plzu 1.2 milligrams of hydro- chloric acid, diluted to 100 C.C. ......................................... 50 C.C. of 10 per cent. sucrose solution, plus 1.2 milligrams of hydro- chloric acid, plus 150 milligrams of asparagine, p = 0.10, diluted to 100 C.C................................................................... 50 C.C. of 10 per cent. sucrose solution, p l m 1.2 milligrams of hydro- chloric acid, $1726~ 150 milligrams of asparagine, ,u= 0.20, diluted to 100 C.C. ..................................................................... 50 C.C. of 10 per cent. sucrose solution, plus 7 -2 milligrams of hydro- chloric acid, plus 150 milligrams of asparagine, ,u = 0 *50, diluted to 100 C.C. ................................................................. 50 C.C. of 10 per cent. sucrose solution, plus 1.2 milligrams of hydro- chloric acid, plus 5 milligrams of asparagine, p = 0-10, diluted to 100 C.C. .................................................................... 50 C.C.of 10 per cent. sucrose solution, plus 1'2 milligrams of hydro- chloric acid, plus 75 milligrams of glycine, diluted to 100 C.C. ... 50 C.C. of 10 per cent. sucrose solution, plus 1.2 milligrams of hydro- chloric acid, plus 89 milligrams of a-alanine, diluted to 100 c. c.. . Rotation of each solution before heating = 6*66+_0*03". 40". 60". 6-50 4.60 6-68 5.85 6.55 5.82 6.53 5-60 - 4.95 6.62 6'06 6'62 6'0488 FORD AND GUTHKIE: THE INFLUENCE OF CERTAIK Influeme of Asparagine, Glycine, and a Ahnine 011 the Hydrolysis of Puri$ed Amylase and Starch. As these compounds are practically neutral substances, it might be presumed that they would have little influence ou amylolytic action when added to the purified starch and amylase described at the begin- ning of this communication.As a matter of fact, however, it mas found that they slightly augmented the action, more maltose being formed in their presence than in the aqueous solution without such addition. The first interpretation we made of this slight augmenta- tion was that the substances in virtue of their amphoteric properties neutralised such minute traces of acidity or alkalinity as were accidentally present in our solutions. Amylase in this relatively pure state is extremely sensitive to minute traces of impurity (compare Osborne and Campbell, Zoc. cit.), so much so that we have found it somewhat difficult to obtain concordant results in duplicate determinations. Normal amylolytic action does not take place under such conditions of laboratory experiment.I n the plant or natural product in which the enzyme works, the media contain mixed phosphates, other salts, amides, and amino-acids, which ensure the degree of neutrality most suitable for amylolytic action. This point has as yet received insufficient attention from biologists, mainly through the misleading values obtained by ordinary titration methods when applied to the examination of animal and vegetable fluids or extracts. Foa (Compt. rend. sbc. Biol., 1905, 58, SSS), by measurements of electromotive force with hydrogen electrodes, has lately given examples of this in the case of various animal fluids. In continuing our work and by using greater precautions to exclude accidental contamination, we came to the conclusion that such traces of acidity as might be incidental to our methods of working were insufficient to provide an explanation for certain apparently anomalous results obtained.It occurred to us that starch itself might possibly possess some feeble acid properties, and that if so it might be possible to obtain some evidence of salt formation by the observation of the conductivity of caustic soda solutions in presence of starch. A substance of such a feebly acid nature would form salts readily hydrolysable in aqueous solution. But, in accordance with the law of mass action, if sufficient starch were added the hydrolytic decomposition would be prevented. Such experiments cannot be carried out fully under the conditions available to us owing to the comparatively slight solubility of soluble starch.We have, however, made the determina- tions tabulated below, which are sufficient to prove that soluble starch of very great purity has feebly acid properties, which, feeble althoughAMPHOTERIC ELECTROLYTES ON AMYLOLYTIC ACTION. 89 they are, are adequate to explain many of the apparently peculiar results we obtained in our experiments with the purified soluble starch and amylase. Soluble Starch and Caustic Soda a t 25'. Molecular Concentration. conductivity. N/25 caustic soda., ............................................................. 209'5 ............ ,) ,, plus 0'42 gram of starch per 100 C.C. 191'6 9 1 ? ? 0.85 ,> ............ 179.6 ,, 9 , 1-70 9 , ............ 151.2 9 , 9 9 3'40 Y 7 7 > 9 > ) 9 9 9 9 9 9 , I 7 , 7 , ............114'5 Soluble Starc?& and Hydvochloric Acid a t 25'. Molecular Concentration. conductivity. Y/25 hydrochloric acid ...................................................... 390'3 > 7 9 ) 0.84 7 ) ,, ..... 385% 7 7 9 9 1.70 9 , , , ...... 381'3 7 , 7 , 3-40 ,I ,, ...... 372'0 7 ) ,, plus 0.42 gram of starch per 100 C.C. ...... 388.7 9 ) ¶ , 7 7 9 , 9 ) $ 3 Soluble Starch and Potassium Chloride at 25'. Molecular Concentration. conductivity. N125 potassium chloride ..................................................... 132.5 11 7 9 plics 0'42 gram of starch per 100 C.C. ... 132'2 , t 0.84 ), ... 131'7 7 9 1-70 >, ... 129'6 1 , 3-40 ) Y ... 126'0 7 9 1 9 9 , ,> 1 9 I 9 , I 7 , 9 , > 5 9 , I ) These experiments were made with a starch preparation which, in 2 per cent.solution, had a specific conductivity of 2-5 x 10-6 at 2 5 O , and so could not contain sufficient impurity to influence greatly the results tabulated. 0 bservations made with other preparations yielded similar values. It is obvious from the results with caustic soda that starch forms compounds with the alkali, the conductivity being reduced fully 45 per cent. by the addition of 3.4 grams of starch per 100 c.c., whereas with hydrochloric acid and potassium chloride the reductions are 4.7 and 5.0 per cent. respectively. The further bearing of these and other results on the nature and constitution of starch we reserve for a subsequent communication. Experiments with PurE$ied Amybse and Starch. Ir@uence of G lycine, a-A lanine, and Asparagine. Conditions of Experiment.-Starch: 70 C.C.of a 1.5 per cent. solution taken. Amylase: 5 milligrams of the preparation F, already described were dissolved in 100 C.C. of water; 1 C.C. of this added to each starch solution. The action was aliowed to proceed for one hour, when i t was stopped by the addition of caustic soda.FQRD AND GUTHRIE: THE INFLUENCE OF CEIiTAIX go I. 5 9.5O. Millipams of maltose formed. Starch solution and amylase withont addition .......................... 95 9 9 ,, ,, plus 75 milligrams of glycine ............ 100 9 , 9 , 1 , ,, 89 ,, a.alaniiie ......... 103 9 1 11 I , I f 150 ,, asparagine .,, .. 99 In this experiment, a dried alcohol-precipitated specimen of soluble starch mas used. A 2 per cent. solution had k*= 5 x a t 25”. 11. 45 minutes a t 54.5”.Milli- grams of maltose formed. Starch and amylase without addition ................................................. 50 ........................ 9 , ,, plus 0.01 milligram of caustic soda 42 3 , 7 , ,, 0.01 ,, hydrogen chloride.. 42 9 7 ,, ,, 50 milligrams of potassinm chloride.. ,. 64 9 ) ,, ,, glycine ............................ 7 , 75 45 3 ) ,, ,, 59 ,, a-alanine 64 7 , 150 ,, asparagine ‘‘ A ” .................... 55 f ) ,> 7 , 150 , , asparagine “ B ” 8 9 ) ,, ,, 1.0 milligram of caustic soda nil 9 , ,, 7 , 1.0 3 , ,, ,, plus 75 milligrams of glycine ......... 64 7 , ,, 3 , 1.0 >, ,, ,, plus 89 milligrams ,, ,, ,, 1.0 1 9 ,, ,, plzcs 150 milligrams .............. ... .......... .............................. 9 7 7 , .................... .......................... of a-alanine ......64 of asparagine “A” 60 The starch used was purified by “freezing out ” in the manner described. A 2 per cent. solution gave k = 2.0 x a t 25’. 111. 1 hour at 5 2 . 2 O . Milligrams of maltose formed. 224 Starch and amylase withont addition ................................ ......... ,> ,, plzcs 0.01 milligram of caustic soda 235 7 , ,, ,, 0.01 ,, hydrogen chloride. 207 , l ,> ,, 10.0 milligrams of potassium ahloride 250 ?, 7 7 ,, 37‘5 ,, glycine 257 ,, ,, ,, 44‘5 ,, a.alanine 269 ,, 75-0 ,, asparagine “ A ” ... 232 , Y 3 , ,, 75.0 ,, asparagine “ B ” 190 ............... ............ 7 , ,, ... A two per cent. solution of the starch gave k= 2.8 x at 25”. Amylase, F,, 15 milligrams to 250 c.c., 5 C.C. to each solution.The asparagine marked ‘‘ A ” i n series I1 and I11 was a highly purified specimen of p = 0-094. “ B ” was an ordinary laboratory ‘‘ pure ” * No correction has been made, in any of these values of k, for the conductivity of the solvent water for which k = 1 to 1 5 xAMPHOTERIC ELECTROLYTES ON AMYLOLYTIC ACTION. 91 specimen recrystallised five times from water, p = 0.50, v 3: 16. The glycine was a specially purified specimen, p = 0.05. The u-alanine was crystallised several times, but was not of the same degree of purity as the ‘‘ A ” asparagine or glycine, p = 0 *25, v = 16. The potassium chloride was a specially purified preparation used for conductivity values. The water used in the experiments detailed here had i%= 1 to 1.5 x We may mention incidentally that with the still and spray traps described by us (J.Fed. Inst. Brew., 1905, 11, 3, 218) water of this purity is easily obtained in quantity by a second distillation, a little calcium hydroxide being added to the contents of the still. Other experiments which we need not detail gave similar results. We, however, record a series of experiments where the amylase used was slightly acid. The acidity of 100 milligrams being equivalent to 0.86 C.C. of N/100NaOH with rosolic acid, 1.17 milligrams of this amylase was added in each case. The starch was the same as in No. I. at 2 5 O . The asparagine was the impure ‘‘ B ” specimen. IV. 1 hour a t 58.5’. Milligrams of maltose formed. 210 ............................ 236 Starch and amylase without addition ................................................ 5 , ,, plus 75 milligrams of glycine ................................... 215 7 ) 7 , ,, 89 ,, a-atlanine 7 7 150 ,, asparagine “By’ ..................... 45 3 , , f ,, 0.01 ,, caustic soda ...........................252 > 7 3 , >, 0-01 ,, ,, plus 75 milligrams of 9 ) > 7 ) ) 0.01 9, ,, plus 89 milligrams of ,> ? > glycine ............... 254 a-alanine ............ 276 asparagine “ B ... 50 ........................... nil glycine .............. 160 3 ) > ) ) > 0.01 Y , ,, plus 150 milligra2s of 9 ) > > 9 , 9 ) 5.0 > > 9 ) 7 , 9 , 6.0 5 , ,, p k s 500 ~nilligrams of The maltose formed was determined by gravimetric copper reduction, the only method in our opinion which yields sufficiently accurate results for such work.I n connection with the values for maltose formed it must be noted that glycine and a-alanine are not without slight influence on the copper reduction. We have applied experiment- ally determined corrections in obtaining the above maltose values. Further, owing to the extremely sensitive nature of amylase, even when taking the greatest precautions to exclude ritmospheric and other impurities, there is considerable risk of discrepant. results through adventitious contamination. Although it is possible that in all the highly purified starches with which we worked some unrecognised impurity may have been present, we feel nevertheless justified in92 AMPHOTERIC ELECTROLYTES AND AMYLOLYTIC ACTION. concluding that isolated amylase cannot bring about a normal hydrolysis in starch solutions which are free from saline substances. Even the addition of a neutral salt such as potassium chloride increases the velocity of the reaction (compare Osborne and Campbell, Zoc. cit.). The addition of certain other salts has a like effect ; for example, addition of a few milligrams of a mixture of lOKH,PO, + lNa,HPO, greatly increases the speed of hydrolysis. I n this case, we can con- ceive the increased action as being due, a t least partly, to the attain- ment of the degree of neutrality most suitable for amylolytic action. The increase with the mixed phosphates is greater than that with potassium chloride, hence we may assume that the influence of the neutral salt depends only on the change it produces in the osmotic pressure of the starch and enzyme solution. As we are unable to continue this line of investigation, me now record our results, which, although in themselves possibly not conclusive, are at least suggestive, and may be of some assistance to other workers who are in a position to prosecute such investigatioos under more favourable conditions than obtain in an industrial laboratory. We consider that our results are sufficient to establish that : (1) Asparagine and the amino-acids mentioned have no specific influence in augmenting the action of amylase: the apparent augmentation of action sometimes obtained by the addition of these amphoteric compounds (or of feeble acids) is due to their neutralising alkaline (or other) impurity in the starch or enzyme solution. I n the plant substance, this neutrality is brought about by equilibrium between the basic and acid compounds present. (3) Until the conditions influencing the action of enzymes are more fully established, i t is inadvisable to formulate mathematical laws as to the kinetics of enzymic hydrolyses. (4) Purified soluble starch has the properties of an extremely feeble acid ; it is capable of yielding negative ions under the influence of strongly positive ones. (2) Normal amylolytic action takes place in neutral solution.
ISSN:0368-1645
DOI:10.1039/CT9068900076
出版商:RSC
年代:1906
数据来源: RSC
|
|