摘要:

J O U R N A L OF THE CHEMICAL SOCIETY. TRANSACTIONS. aommittu of @ubIkatiotr : H. T. BROWN, LL.D., F.R.S. A. W. CROSSLEY, D.Sc., Ph.D. WYNDHAM R. DUNSTAN, M.A., LL. D., P. F. FRANKLAND, LL.D., F.R.S. F. R. S. M. 0. FORSTER, D.Sc., Pl1.D. H. MCLEOD, F.R.S. E. J. MILLS, D.Sc., LL.D., F.R.S. Sir W. RAMHAY, K. C.B., LL. D., F. R.S. A. SCOTT, D.Sc., F.R.S. W. A. TILDEN, D.Sc., F.R.S. W. P. WYNNE, D.Sc., F.R.S. &;bitor : G. T. MORGAN, D.Sc. SuIY-&bitar : A. J. GREENAWAY. - 1904. Vol. LXXXV. LONDON: GURNEY & JACKSON, 10, PATERNOSTER ROW. 1904.RICHARD CLAY & SONS, LIMITED, BREAD STREET HILL, E.C., AND BUNQAY, SUFFOLK.J O U R N A L OF THE CHEM1CA.L SOCIETY. TRANSACTIONS. H. T. BROWN, LL.D., F.R.S. A. W. CKOSSLEY, D.Sc., Ph.D. WYNDHAM R. DUNSTAN, M.A., LL.D., M.0. FORSTER, D.Sc., Ph.D. P. F. FRANKLAND, LL.D., F.R.S. F.R.S. H. MCLEOD, F.R.S. E. J. MILLS, D.Sc., LL.D., F.R.S. Sir W. RANSAY, K. C. R., LL. D., F. R.S. A. SCOTT, D.Sc., F.R.S. MT. A. TILDEN, D.Sc., F.R.S. W. P. WYNNE, D.Sc., F.R.S. @hitar : G. T. MORGAN, D.Sc. Sulr-@f;bifor : A. J. GREENAWAY. 1904. Vol. LXXXV. Part I. LONDON: GURNEY & JACKSON, 10, PATERNOSTER ROW. 1904.RICHARD CLAY & SONS, LIMITED, BREAD STREET HILL, E.C., AND BUNGA\;, BUFFOLK.J O U R N A L OF THE CHEM1CA.L SOCIETY. TRANSACTIONS. H. T. BROWN, LL.D., F.R.S. A. W. CKOSSLEY, D.Sc., Ph.D. WYNDHAM R. DUNSTAN, M.A., LL.D., M. 0. FORSTER, D.Sc., Ph.D. P. F. FRANKLAND, LL.D., F.R.S. F.R.S. H. MCLEOD, F.R.S. E. J. MILLS, D.Sc., LL.D., F.R.S. Sir W. RANSAY, K. C. R., LL.D., F. R.S. A. SCOTT, D.Sc., F.R.S. MT. A. TILDEN, D.Sc., F.R.S. W. P. WYNNE, D.Sc., F.R.S. @hitar : G. T. MORGAN, D.Sc. Sulr-@f;bifor : A. J. GREENAWAY. 1904. Vol. LXXXV. Part I1 LONDON: GURNEY & JACKSON, 10, PATERNOSTER ROW. 1904.RICHARD CLAY & SONS, LIMITED, BREAD STREET HILL, E.C., AND BUNQAY, SUFFOLK.C O N T E N T S . PAPERS COXXUNICATED TO THE CHEMICAL SOCIETY. PACE 1.-The Estimation of Metliyl Alcohol in presence of Ethyl By THOMAS EDWARD THORPE, C.B., F.R.S., and 11.-Halogen Derivatives of Diphenyl and Dihydroxydiphenyl. 111.-Separation and Estimation of Silver Cyanide and Silver Chloride. By ROBERT HEXRY ADERS PLIMMER, D Sc. 1V.-Action of Malt Dkstase on Potato Starch Paste. By V.-The Action of Halogens on Compounds containing the V1.-Derivatives of Menthyl Cyanoacetate.By DOUGLAS AN- VII. -Optically Active Esters of P-Ketonic and P- Aldehydic Part IV. Condensation of Aldehydes with Menthyl By ARCHIE CECIL OSUORN HANN and ARTHUR V1II.-Notes on some Natural Colouring Matters. By ARTHUR 1X.-The Four Optically Isomeric &Men thylamines and their X.-Peroxylaminesu1phon:ttes and Hydroxylaminetrisulph- By TAMEMASA Alcohol. JOHN HOLXES . . 1 By JOHN CANNELL CAIN . . 7 (Grocers’ Company’s Ilesearch Student) . . 12 BERNARD F. DAVIS, B.Sc., and ARTHUR R. LINU . . 16 Carbonyl Group. By ARTHUR LAPWORTH . . 30 DERSON BOWACK and ARTHUR LAPWORTH . . 42 Acids. Acetoacetate. LAPWORTR . . 46 GEORGE PERKIN, F.R.S., and SAMUEL PHIPPS . . 56 Salts. By FRANK TUTIN and FREDERIC STANLEY KIPPING . 65 onates (Sulphazilates and Metasulphazilates). HAGA, D.Sc.. . 78 XI.-Peroxylaminesulpho~lic Acid. By EDWARD DIVERS . . 108 XI1.-Constitution of Nitric Peroxide. By EDWARD DIVERS . 110 XII1.-The Solubility Curves of the Hydrates of Nickel Sulphate. By BERTRAM DILLON STEELE, D.Sc., and F. M. G. JOHNBON . . 113 X IV.--The Relative Strengths of the Alkaline Hydroxides and of Ammonia as Measured by their Action on Cotarnine. By JAMES JOHNSTOX DOBBIE, M.A., D.Sc., ALEXANDER LAUDER, B.Sc., and CHARLES KENNETH TINKLER, Research Student of the University of Edinburgh . . 121i v CONTENTS. XV.-uaa-Dimethylbutane-u/38-tricarboxylic Acid, y-Keto-PP-di- methylpentamethylene-a-carboxylic Acid, and the Synthesis of Inactive a-Campholactone, of Inactive a-Campholytic Acid, and of P-Campholytic Acid (isoLauronolic Acid).By WILLIAM HENRY PERKIN, jun., and JOCELYN FIELD TBORPE . XVI. - o-Nitrobenzoylacetic Acid. By EDWARD RUSHTONEED- HAM and WILLIAM HENRY PERKIN, jun. XVI1.-The cis- and tram-Modifications of aay-Trimethyl- glutaconic Acid. By WILLIAM HENRY PERKIN, jun., and ALICE EMILY SMITH, B.Sc., 1851 Exhibition Scholar of University College, Bangor . XVIII. -Derivatives of P-Resorcylic Acid and of Protocatechuic Acid. By WILLIAM HENRY PERKIN, jun., and EMANUEL SCHIESS . X1X.-The Formation of Phloroglucinol by the Interaction of Ethyl Malonate with its Sodium Derivative. By CHARLES WATSON MOORE . XX.-The Resolution of dLMethylhydrindamine. Isomeric Salts of d- and LMethylhydrindamines with d-Chloro- camphorsulphonic Acid. By GEORGE TATTERSALL, B.Sc., XX1.-The Influence of Substitution in the Nucleus on the Rate of Oxidation of the Side-chain. I. Oxidation of the Mono- and Di-chlorotoluenes. By JULIUS BEREND COREN and JAMES MILLER . XXI1.-Derivatives of Highly Substituted Anilines. By FREDERICK DANIEL CHATTAWAY and JOHN MELLO WADMORE . XXII1.-The Condensation of Furfuraldehyde with Sodium Succinate. By ARTHUR WALSH TITHERLEY and JAMES FREDERICK SPENCER, B.Sc. XXIV,-The Constitution of Epinephrine. By HOOPER ALBERT DICKINSON JOWETT . XXV.-The Resolution of up-Dihydroxy butyric Acid in to its Optically Active Constituents. By ROBERT SELBY MORRELL and EDWARD KENNETH HANSON . Part I. Reactions with the Halogens and other Inorganic Sub- stances. By JAMES DEWAR and HUMPHREY OWEN JONES . Part 11. Reaction with Aromatic Hydrocarbons in presence of Aluminium Chloride.Synthesis of Aldehydes and Anthracene Derivatives. By JAMES DEWAR and HUMPHREY OWEN JONES . XXVII1.-Optically Active Nitrogen Compounds. d- and I-Phenylbenzylmethylethylammonium Salts. By HUMPHREY OWEN J O ~ E S . , XXV1.-The Chemical Reactions of Nickel Carbonyl. XXVI1.-The Chemical Reactions of Nickel Carbonyl. PAUE 128 148 155 159 165 169 174 179 183 192 197 203 212 223CONTENTS. V PAGE XX1X.-Diortho-substituted Benzoic Acids. Part V. Forma- tion of Salts from Diortho-substituted Benzoic Acids and Organic Bases. By JOHN JOSEPH SUDBOROUGH and WILLIAM ROBERTS . . . . 234 XXX.-Studies on the Electrolytic Oxidation of Phenols. Part I. By ARTHUR GEORGE PERKIN and FREDERICK MOLLWO PERKIN . . 243 XXX1.-The Intel dependence of the Physical and Chemical Criteria in the Analysis of Butter-fat.By THOMAS EDWARD THORPE, C.B., F.R.S. . . 248 XXXI1.-A Simple Thermostat for Use in Connection with the Refractometric Examinxtion of Oils and Fats. By THOMAS EDWARD THORPE, C.B., F.R.S. . . 257 XXXII1.- The Action of Nitrogen Sulphide on Organic Substances. Part I. By FRANCIS ERNEST FRANCIS and OLIVER CHARLES MINTY DAVIS . , 259 XXX1V.-Aromatic Compounds obtained from the Hydro- aromatic Series. Part I. The action of Bromine on 3:5-Dichloro-l : 1 -dimethyl-A2'4-dihydrobenzene. By ARTHUR WILLIAM CROSSLEY . * * . . 264 XXXV.-A Microscopical Method of Determining Molecular Weights. By GEORGE BARGER, Scbolar of King's College, Cambridge. . . 286 Part XIII. Action of Nitrogen Peroxide on 1-Nitrocamphene.By MARTIN ONSLOW FORSTER and FRANCES MARY GORE MICKLETHWAIT . 325 XXXVII. T h e So-called '' Hydrocellulose." By ARTHUR LANDAUER STERN, D.Sc. . . 336 XXXVII1.-Intramolecular Rearrangement in Derivatives of the Aromatic Aminoketones. By FREDERICK DANIEL CHATTAWAY . . 340 XXX1X.-The Separation of p-Crotonic Acid from a-Crotonic Acid. By ROBERT SELBY MORRELL and ALBERT ERNEST XL.-Certain Organic Phosphorus Compounds. By AUGUSTUS XL1.-The Action of Sodium Hypochlorite on the Aromatic By HENRY STANLEY RAPER, JOHN THOMAS XLI1.-The Esterification of r-Mandelic Acid by Menthol and XLII1.-Isomeric Change of Diacylanilides into Acylamino- XL1V.-The Constitution of Phenolphthalein. By ARTHUR XXXV1.-Studies in the Camphane Series. BELLARS . . 345 EDWARD DIXON, M.D.. 350 Sulphonamides. THOMPSON, and JULIUS BEREND COHEN . . 371 Borneol. By ALEXANDER MCKENZIE . . 378 ketones. By FREDERICK DANIEL CHATTAWAY . . 386 GEORGE GREEN ftnd ARTHUR GEORGE PERKIN . . 398vi CON TENTS. XLV.-Freezing Point Curves of Dynamic Isomerides : Ammonium Thiocyanate and Thiocarbamide. By ALEXANDER FINDLAY . XLVI. -A Note on Phenyldimethylallylammonium Compounds. By ALFRED WILLIAM HARVEY . XLVI1.-A Note on the Composition of Distilled Oil of Limes and a New Sesquiterpene. By HERBERT EDWARD BURGESS and THEODORE HENRY PAGE . XLVII I .- 8-K etohexah ydrobenzoic Acid. By WILLIAM HENRY PERRIN, jun. . XLIX.-The Arrangement in Space of the Groups Combined with the Tervalent Nitrogen Atom. By FREDERIC STANLEY KIPPINQ and ARTHUR HENRY SALWAY .L.-Contributions to the Knowledge of the P-Diketones. By SIEGFRIED RUHEMANN and EDWIN ROY WATSON. L1.-The Formation of Periodides in Organic Solvents. By HARRY MEDFORTH DAWSON . Annual General Meeting . Presidential Address to the Chemical Society THE FARADAY LECTURE. Elements and Compounds. By WILHELM OSTWALD . LI1.-Mercuric Nitrate and its Decomposition by Heat. By PRAPULLA CBANDRA RAY, D.Sc. (Edin.) LTI1.-The Reduction of 2:6-Dinitrotoluene with Hydrogen Sulphide. By JULIUS BEREND COHEN and JOSEPH MARSHALL L1V.-Studies in the Acridine Series. Part I. By JOHN JACOB Fox and JOHN THEODORE HEVITT LV.-The Acid Esters of Methyl Substituted Succinic Acids. By WILLIAM ARTHUR BONE, JOHN JOSEPH SUDBOROUGH, and CHARLES HESRY GRAHAM SPRANRLING . LV1.-Chemical Dynamics of the Alkyl Iodides.By KATHARINE ALICE BURKE and FREDERICK GEORGE DONNAN LV1I.-Isomeric Change of Diacylanilides into Acylamino- ketones. Transformation of the Dibenzoyltoluidines into the Isomeric Benzoylaminomethylbenzophenones. By FREDERICK DANIEL CHATTAWAY and WILLIAM HENRY LEWIS LVII1.-Estimation of Hydrogen Peroxide in the presence of Potassium Persulphate by means of Potassium Perman- ganate. By JOHN ALBERT NEWTON FRIESD, M.Sc. . LIX.-The Heat of Formation of Glucinum Chloride. By JAMES HOLMS POLLOK, B.Sc. . LX.-The Action of Ethyl P-Iodopropionate on Ethyl Disodio- ethanetetracarboxylate. By OSWALD SILBERRAD, Yh.D. . . . . . PAGE 403 412 414 416 438 45 6 467 477 493 506 523 527 529 534 555 589 597 603 61 1CONTENTS. vii PAGE LX1.-A Comparison of the Prodiicts of the Hydrolysis of Potato Starch with those obtained from Cereal Starches.By JAMES OSULLIVAN . . 616 LXI1.-A Lzevorotatory Modification of Quercitol. By FREDERICK BELDING POWER and FRANK TUTIN . . 624 LXII1.-The Constituents of the Essential Oil of Californian Laurel. By FREDERICK BELDINO POWER and FREDERIC HERBERT LEES . . 629 LX1V.-Some Derivatives of Umbellulone. By FREDERIC HERBERT LEES . . . 639 LXV. -Picry1 Derivatives of Urethanes and Thiourethanes. By JAMES CODRINGTON CROCKER, B.A., and FRANK HAROLD LOWE, B.Sc. . . 646 Part I. Synthesis of Terpin, Inactive Terpineol, and Dipentene. By WILLIAM HENRY PERKIN, jun. . . . 654 LXVI1.-Ammoniacal Double Chromntes and Molybdates. By SAMUEL HENRY CLIFFORD BRIGGS . . 672 LXVI.11.-The Hexahydrated Double Chromates. Magnesium and Nickel Compounds.By SAMUEL HENRY CLIFFORD BRIGGS . . 677 LX1X.-Reduced Silicates. By CHARLES SIMMONDS, B.Sc. . 681 LXX.-Studies on Optically Active Carbimides. Part I. By ALLEN NEVILLE, B.So. (Lond.), and ROBERT HOWSON PICKARD . . 685 LXX1.-Hydrocellulose. By CHARLES FREDERICK CROSS and EDWARD JOHN BEVAN . . 691 LXXI1.-The Slow Combustion of Ethane. By WILLIAM ARTHUR BONE and WILLIAM ERNEST STOCKINGS . . 693 LXXII1.-Studies in the Tetrahydronaphthalene Series. Part 11. Halogen Derivatives of ur-Tetrahydro-/3-nnph- thylamine. By CLARENCE SMITH, D.Sc. . . 728 LXX1V.-Studies in the Tetrahydronaphthalene Series. Part 111. Reaction between ar-Tetrahydro-/3-naphthyl- amine and Formaldehyde. By CLARENCE SMITH, D.Sc. . 732 LXXV.-A Study of the Substitution Products of ui*-Tetra- hydro-a-naphthylamine.4-Bromo-ar-tetrahydro-a-naphthyl- amine and ar-Tetrahydro-a-naphthylamine-4-sul phonic Acid. By GILBEKTHOMAS MORGAN, FRANCES XARY GORE MICKLE- THWAIT, and HERBERT BEN WINFIELD . . 736 LXXV1.-The Action of Nitrosyl Chloride on Pinene. By WILLIAM AUGUSTUS TILDEN , . . . 759 LXV1.-Experiments on the Synthesis of the Terpenes.... V l l l CONTENTS. LXXVI1.-The Comparison of the Rotation-values of Methyl, Ethyl, and n-Propyl Tartrates at Different Temperatures. By THOMAS STEWART PATTERSON . LXXVIIL-A Revision of the Atomic Weight of Rubidium. By EBENEZER HENRY ARCHIBALD. . LXX1X.-The Action of Sodium Methoxide and its Homologues on Benzophenone Chloride and Benzylidene Chloride. Part 11. By JOHN EDWIN MACKENZIE and ALFRED FRANCIS JOSEPH .LXXX.-The Formation of Periodides in Nitrobenzene Solution. Part 11. Periodides of the Alkali and Alkaline Earth Metals. By HARRY MEDFORTH DAWSON and ETHEL ELIZABETH GOODSON, B.Sc. LXXX1.-Caproylthiocarbimide. By AUGUSTUS E. DIXON, M.D. LXXXI1.-The Action of Ihdium Rays on the Halides of the By WILLIAM LXXXII1.-The Viscosity of Liquid Mixtures. Part I. By ALBERT ERNEST DUNSTAN, B.SC. LXXXIV. -The Action of Heat on a-Hydroxycarboxylic Acids. Part I. a-Hydroxystearic Acid. By HENRY ROKDEL LE SUEUR . LXXXV.-The Constituents of Chaulmoogra Seeds. By FREDERICK BELDING POWER and FRANK HOWORTH GORNALL . LXXXV1.-The Constitution of Chaulmoogric Acid. Part 'I. By FREDERICK BELDING POWER and FRANK HOWORTH GORNALL . By OSWALD SILBERRAD, Ph.D., and THOMAS HILL EASTERFIELD, M.A., Ph. D. LXXXVII1.-The Nitration Products of the Isomeric Dichloro- benzenes. By PERCIVAL HARTLEY and JULIUS BEREND COHEN . LXXX1X.-The Fermentation of the Indigo-plant. By CYRIL BERGTHEIL . XC.-Studies in the Uarnphane Series. Part XIV. isoNitroso- camphor. By MARTIN ONSLOW FORSTER . XC1.-The Vapour Density of Hyclrazine Hydrate. By ALEXANDER SCOTT . XCIL-The Basic Properties of Oxygen. Additive Compounds of the Halogen Acids and Organic Substances and the Higher Valencies of Oxygen. Asymmetric Oxygen. By EBENEZER HENRY ARCHIBALD and DOUGLAS MCINTOSH . XCII1.-Limonene Nitrosocyanides. By WILLIAM AUGUSTUS TILI)EN and FREDERICK PEACOCK LEACH Alkali Metals and Analogous Heat Effects. ACKROYD . LXXXVIL-Studies on Ethyl Carboxyglutarate.. PAGE 765 776 790 796 807 81 2 81 7 S27 838 85 1 862 865 870 892 913 919 931CONTENTS. ix PAGE XC1V.-Estimation of Hydroxyl Groups in Carbon Compounds. XCV.-Influence of Moist Alcohol and Ethyl Chloride on the Boiling Point of Chloroform. By JOHN WADE, D.Sc., and HORACE FINNEMORE, A.I.C. . 938 XCV1.-The Mechanical Andtlysis of Soils and the Composition of the Fractions Resulting Therefrom. By ALFRED DANIEL HALL, M.A. . . 950 XCVI1.-The Effect of the Long-continued Use of Sodium Nitrate on the Constitution of the Soil. By ALFRED DANIEL HALL, M.A. . . 964 XCVIIL-The Action of Acotyl Chloride on the Sodium Salt of Diacetylacetone, and the Constitution of Pyrone Com- pounds. By JOHN NORMAN COLLIE, F.R.S. . 971 XC1X.-Note on the Hydroljsis of Starch by Diastase.By JOHN SIMPSON FORD . . 980 C.-Imino-ethers and Allied Compounds Corresponding with the Substituted Oxamic Esters. By GEORGE DRUCE LANDER 984 C1.-The Additive Products of Benzylideneaniline with Ethyl Acetoacetate and Ethyl Methylacetoacetate. By FRAA’GIS ERNEST FRANCIS and MILLICENT TAYLOR . . 998 CI1.-Notes on Analytical Chemistry. By GILBERT THOMAS MORGAN . . 1001 CII1.-The Constitution of Hydrastinine. By JAMES JOHN- STON DOBBIE, D.Sc., F.R.S., and CHARLES KENNETH TINKLER, Research Student of the University of Edinburgh, 1005 CIV. -The Absorption Spect’rum of p-Nitrosodimethylaniline. , 1010 CV.-The Electrolytic Estimation of Minute Quantities of Arsenic. By HENRY JULIUS SALOMON SAND, Ph.D., M.Sc., and JOHN EDWARD HACKFGRD . . 1018 CV1.-The Ultra-violet Absorption Spectra of Certain Enol-keto- tautomerides.Part I. Acetylacetone and Ethyl Aceto- acetate. By EDWARD CEARLES CYRIL BALY and CECIL CVI1.-The Action of Chromyl Chloride on Stilbene, Styrene, and Phenanthrene. By GEORGE GERALD HENDERSON and THOMAS GRAY . . 1041 CVII1.-Stereoisomeric Glucoses and the Hydrolysis of Gluco- sidic Acetates. By EDWARD FRANKLAND ARMSTRONG (Salters’ Company’s Research Fellow) and PAUL SEIDELIN ARUP C1X.-The Stereoisomeric Tetramethyl Methylglucosides and Tetramethyl Glucose. By THOMAS PURDIE, F.R.S., and JAMES COLQUHOUN IRVINE, Ph.D., D.Sc., Carnegie Fellow By HAROLD HIBBERT and JOHN JOSEPH SUDBOROUGH . . 933 By WALTER NOEL HARTLEY, D.Sc., F.R.S. HENRY DESCH, D.Sc. . 1029 . 1043 . 1049X CONTENTS. PAGE CX.-The Alkylntion of Galactose.By JAMES COLQUHOUN IRVINE, Ph.D., D.Sc., Carnegie Fellow, and ADAM CAMERON, M.A., B.Sc. . . 1071 CX1.-Ionisation and Chemical Combination. By JAMES WALLACE WALKER . . 1082 CXI I.-Ionisation and Chemical Combination in the Liquefied Halogen Hydrides and Hydrogen Sulphide. By JAMES WALLACE WALKER, DOUQLAS MCINTOSH, and EBENEZER ARCHIBALD . . 1098 CXII1.-Some Compounds of Aluminium Chloride with Organic Substances containing Oxygen. By JAMES WALLACE WALKER and ARTHUR SPENCER . . 1106 CX1V.-A Method for the Rapid Ultimate Analysis of Certain CXV.-The Influence of Solvents on the Rotation of Optically Active Compounds. Part V. The Optical Activity of Certain Tartrates in Aqueous Solution. By THOMAS STEWART PATTERSON . . 1116 CXV1.-The Influence of Solvents on the Rotation of Optically Active Compounds.Part VI. The Relationship between Solution-volume and Rotation of the Alkyl and Potnssium Alkyl Tartrates in Aqueous Solution. By THOMAS STEWART PATTERSON . . 1153 CXVI1.-The Comparative Nitrifying Power of Soils. By SYDNEY FRANCIS ASHBY, B.Sc., Carnegie Research Scholar . 1158 CXVII1.-The Action of Organic Rases on Olefinic Ketonic Compounds. By SIEGFRIED RUHEMANN and EDWIN ROY WATSON . . 1170 CX1X.-Sulphonphenylchloroamides and Sulphontolylchloro- amides. By FREDEKICK DANIEL CHATTAWAY . . 1181 CXX.-Studies in the Camphaoe Series. Part XV. Bornyl- carbimide. By MARTIN ONSLOW FORSTER and HERBERT MOORE ATTWELL . . 1188 CXX1.-Halides of the Acridines and Naphthacridines. By ALFRED SEXIER and PERCY CORLETT AUSTIK ., 1196 CXXI1.-Reactions Involving the Addition of Hydrogen Cyanide t o Carbon Compounds. Part 11. Cyanohydrins regarded as Complex Acids. By ARTHUR LAPWORTH . . 1206 CXXII1.-Reactions Involving the Addition of Hydrogen Cyanide to Carbon Compounds. Part 111. Action of Potass- ium Cyanide on Mesityl Oxide. By ARTHUR LAPWORTH . 1214 CXX1V.-The Bromination of Phenols. By JOHN THEODORE HEWITT, JAMES KENNER, and HARRY SILK . . 1225 Organic Compounds. By JOHN NORMAN COLLIE . . 1111CONTENTS. xi PAGE CXXV.-6-Aminocoumarin. By GILBERT THOMAS MORGAN and FRANCES MARY GORE MICKLETHWAIT . . 1230 CXXV1.-The Resin Acids of the Conifer%. Part I. The Con- stitution of Abietic Acid. By THOMAS HILL EASTERFIELD and GEORGE BAGLEY . . 1238 CXXVI1.-Studies in Asymmetric Synthesis. I.Reduction of Menthyl Benzoylformate. 11. Action of Magnesium Alkyl Haloids on Menthyl Benzoylformate. By ALEXANDER MCKENZIE . . 1249 CXXVII1.-The Relation of Position Isomerism to Optical Activity. 11. The Rotation of the Menthyl Esters of the Isomeric Chlorobromobenzoic Acids. By JULIUS BEREND COHEN and HENRY STANLEY RAPER . . 1263 CXX1X.-The Relation of Position Isomerism to Optical Activity. 111. The Rotation of the Menthyl Esters of the Isomeric Iodobenzoic Acids. By JULIUS BEREND COHEN and HENRY STANLEY RAPER . . 1271 CXXX.-The Chlorination of the Trichlorotoluenes in Presence of the Aluminium-mercury Couple. The Constitution of the Tetmchlorotoluenes. Part V. By JULIUS BEREND COHEN and HENRY DRYSDALE DAKIN . . 1274 CXXX1.-The Chemical Dynamics of the Reactions bet ween Sodium Thiosul phate and Organic Halogen Compounds.Part I. Alkyl Haloids. By ARTHUR SLATOR, Ph.D. . 1286 CXXXI1.-The Nature of a Solution of Iodine in Aqueous Potassium Iodide. By CHARLES HUTCHENS BURGESS and DAVID LEONARD CHAPMAN . 1305 CXXXII1.-Note on Methyl Fluoride. By JOHN NORMAN COLLIE, 1317 CXXX1V.-Acetylenic Ketones. By EDWIN ROY WATSON . 1319 CXXXV.-A Note on Bergamot Oil and other Oils of the Citrus Series. By HERBERT EDWARD BURGESS and THEODORE HENRY PAGE . . 1327 CXXXV1.-The Resolution of Externally Compensated Dihydro- a-methylindole. By WILLIAM JACKSON POPE and GEORGE CLARKE, jun. . . 1330 CXXXVIL-The Vapour Pressure of Sulphuric Acid Solutions and the Molecular Condition of Sulphuric Acid in Concen- CXXXVII1.-Reactions Involving the Addition of Hydrogen Cyanide t o Carbon Compounds.Part IV. Addition of Hydrogen Cyanide to Benzylideneacetopheuone, By ARCHIE CECIL OSBORN HANN and ARTHUR LAPWORTH . . 135.5 CXXX1X.-The Bromination of Silver Cyanate. By GEORGE DEAN, M.A. . . 1370 trated Solution. By BRYCE CEIUDLEIGH BURT . . 1339xii CONTENTS. PAGE CXL.-The Decomposition of Chloral Hydrate by Sodium Hydroxide and by Certain Salts. By EMIL ALPHONSE WERNER . . 1376 CXL1.-Contributions to the History of Glyoxylic Acid. By REINRICH DEBUS, Ph.D., F.R.S. . . 1382 CXLII.--A1:3-Dihydrobenzene. By ARTHUR WILLIAM CROSSLEY , 1403 CXLII1.-The Colouring Matters of the Stilbene Group. I. By ARTHUR GEORQE GREEN . . 1424 CXL1V.-The Colouring Matters of the Stilbene Group. 11. By ARTHUR GEORGE GREEN, FRED MARSDEN, and FRED SCHOLEFIELD .. 1432 CXLV -Researches on Chromorganic Acids : the Behaviour of Chromic Hydroxide towards Oxalic Acid and certain other Organic Acids. By EMIL ALPHONSE WERNER . . 1438 CXLV1.-Olefinic Ketonic Compounds. By SIEGFRIED RUHEMANN 1451 CXLVI1.-The Colouring Principle of the Flowers of the Butea Yrondosa. By ARTHUR GEORGE PERKIN, F.R.S., and, in part, the late JOHN JAMES HUMIEL . . 1459 CXLVII1.-Reduction Products of u/3-Dimethylanhydracetone- bend, and Condensation Products of Benzaldehyde with Ketones, By FRANCIS ROBERT JAPP, F.R.S., and WILLIAN MAITLAND, B.Sc., Carnegie Fellow in the University of Aberdeen . . 1473 CXL1X.-Interaction of Sodium Phenylglycidate with Phenyl- hydrazine. By FRANCIS ROBERT JAPP, F.R.S., and WILLIAM MAITLAND, B.Sc., Carnegie Fellow in the University of AberJeen .. 1490 CL.-a-Benzoyl-P-trimethacetylstyrene. By FRANCIS ROBERT JAPP, F.R.S., and WILLIAM MAITLAND, B.Sc., Carriegie Fellow in the University of Aberdeen . . 1496 CL1.-The Fractional Hydrolysis of Amygdalinic Acid. iso- Amygdalin. By HENRY DRYSDALE DAKIN. . . 1512 CLI1.-Studies on the Dynamic Isomerism of a- and p-Crotonic Acids. Part I. By ROBERT SELBY MORRELL and EDWARD KENNETH HANSON . . 1520 CLII1.-The Effect of Colloidal Platinum on Mixtures of Caro’s Persulphuric Acid and Hydrogen Peroxide. By THOMAS SLATER PRICE and JOHN ALBERT NEWTON FRIEND . . 1526 CL1V.-Note on the Influence of Potassium Persulphate on the Estimation of Hydrogen Peroxide. By JOHN ALBERT NEWTON CLV.-The Action of Nitrogen Sulphide on Organic Substances.By FRAXCIS ERNEST FRANCIS and OLIVER CHARLES FRIEND . , 1533 Part 11. MINTY DAVIS . . 1535CONTES'I'S. xiii PAGE CLV1.-Stuclirs of Dynamic Isonicrihm. 11. Solubility a s a means of determiuing the Proportions of Dynamic Isomerides in Solution. Equilibrium between the Normal and Pseudo- Nitro-derivatives of C:tmphoy. By THOMAS MARTIN LOWRY, D.Sc., and W 7 ~ ~ , ~ ~ ~ ~ ~ ROBERTSON, A .R. C.S., Leathei sellers' Compnny's Research Fellow . . 1541 CLVI1.--8tntlies of Dynamic Isomerism. 111. Solubility as a means of Deterrnining the Proportions of Dynamic Isomerides in Soluticn. Equilibrium in Solutions of Glucose arid of CLVIII.-Position-Isoniei i-in and Optical Activity. The Methyl a d Ethyl Esters of Di-0-, -m-, and -p-nitrobenzoyltartaric Acids.By PERCY FAEADAY FrraNKrAAsu and JOHN HARGER, Ph.D. . 1571 CI,IX.--Thc Decomposition of Methylcsrbamide. By CHARLES EDWARD FAWSITT, D.Sc., Ph.D., Cnimegie Research Fellow . 1581 CLX.-The Isomerism of the Amidines of the Napht,halene Serieq (Fifth Communication on Anhydro-bases). By RAPIrAEr, (ILXT.-The Spec trim geiiwally atti-ibu tecl to '( Chlorophyll " :tntl its Relation to the Spectrum of Living Green Tissues. CLXI1.-Studies on C'oinparati\-e Cryoscopy. P a r t I T . The 13y Prrirn WILFRED CLXI 11.-The Infliience of Substitution in the Nucleus on tlie Rate of 0xitl;ition of the Sidc-chain. 11. Oxidation of the Halogon Derivatives of Toluene. EJ- JULIU-; EERFX-~ COHEN and JAMES MILLER . . 1622 CLXIV.-'rhe Composition of Be1 TI. By J.iar~s HOLXS POLLOK, B.sc. . 1630 CLXV.-The Combustion of Ethylene. By WILLIAM ARTHLR BONE and RIC'IIARD VERNON WHEELER . 1637 CLXV1.-Isomeric Change of Dincylanilides into Acylamino- ketones. Transfor~nation of Dibenzoylaminobenzoplienone into l-Benzoylarnir~o-2:4-clibenzoyibenzene. By FI~EDERICR DANIEL CEATTAWAY and \ I 7 1 ~ 1 , 1 ~ a r HESRP LEWIS . . 1663 CLXVI1.-The Grignard Reaction ;I ppliecl to the Esters of Hydroxy-acids. By PERCY FARADAY FI~ANKI AND and DOUGLAS FRAXK TWISS. M.Sc. . . 1666 CLXVII1.-The Coustitntion of P y azolidone Deri\ atires : ~-Phen~lazoisovaleric Acid and s-P-PheuylhSdl.azinobi~t,~~ic Acid. By &IITRA~I PREXTICE . . 1667 Galactose. By r l ' ~ ~ ~ ~ ~ ~ ~ MARTIN LO~VRY, D.Sc. . . 1551 MELDOLA, F.R.S.? aiid JOSEPH TIEXILY LAXE . . 1592 By WALTER NOEL IIARrLEY , . 1607 ROBERTSON, B.A. . . 1617 Aromatic Acids_in Ptlenol Solution.Sl\' C'ON'I'ENTS. I'\c,E CJ,XIX.-The Rcylnt ion of A niitlcc:. Ey ARTHUR WATNT TITHERLEY . . lG73 C!T,X;Y.-A Ku'cw S) 111 licsis cbf i d 'a1111 olactoiie and (lei t:iin 1)erivatives. 1:y l ) , \ ~ r r > TREVOI~ JONES n11d GIEORGE . 1691 CLXXI.-~~iniclechloi.oio(litlii.;. By ~ 4 1 : 0 1 ~ 1 < Ditr CE IJAiyi)m and HARRY EDWIN LAWS . . 1695 CJXXlI.--The l>ecompositiL~n of Hlliylene Iodide under tlie Influence of the Ioditle 1011. By AIWIIUII SLATOR, P1i.D. . 1697 CLSXIIJ.-4a Oleic Acid. By IImnY E o m m Lr: SUEUR . 1708 CT,XXW.--'l'he L4finity Constants of Aniline ancl its Deriva- tives. By ROI~ICKI~ CI~OSBIE FARVEII, D.Sc., Pli.D., and FIIEDERICK J O H S WAR rrr, M.Sc. CLXXV.-The Formittion :mil React ions of lmiiio-compounds. Part, I. Condensation of Xthyl Cyanoacetnte with i t s Hodiiim Derivative. By HAJIOLD BARON, FREDERICK GEORGE Pi<itciT REMFRY, and JOCELYN Fmrm TNORPE . . 1726 r y L.4T'rlsIlS \T,TA . lt13

ISSN:0368-1645    

DOI:10.1039/CT90485FP001

出版商:RSC    

年代:1904

数据来源: RSC

摘要:

HALOGEN DERIVATIVES OF DIPHENYL AND DIHYDROXYDIPHENYL. 7 IL-Hdogeia Derivatives of Diphcnyl and Dihydroxy- diphen y6. By JOHN CANNELL CAIN. IN an investigation on the action of water on the diazonium salt prepared from 3 : 3’-dichlorobenzidine (Trans., 1903, 83, SSS), only a very small quantity of 3 : 3’-dichloro-4 : 4’-dihydroxydiphenyl was obtained, the chief product being of a quinonoid nature, It appeared, therefore, of interest t o study the behaviour of this diazonium salt when subjected to the processes employed in replacing the diazo-groups by hydrogen, chlorine, bromine, iodine, cyanogen, and carboxyl radicles. A very convenient method of preparing 3 : 3’-dichloro-4 : 4’-dihydroxy- diphenyl has been devised, wnich consists in chlorinating 4 : 4’-dihydr- oxydiphenyl in glacial acetic acid solution with the calculated quantity of chlorine. I n connection with this part of the work, both the monochloro- and the trichloro- derivatives were prepared, the limit of the chlorination being the tetrachloro-compound, which has already been described by Magatti (Bey., 1880, 13, 224).EXPERIMENTAL. 3 : :3’-Dichlorodi~henyZ. 3 : 3’-Dichlorobenzidine (25 grams) was dissolved in ethyl alcohol, a mixture of strong sulphuric acid and alcohol added, and then, after cooling, a slight excess of dry mdium nitrite. The alcoholic solution of the diazonium sulphate thus obtained was boiled for half a n hour, the alcohol evaporated off, and the residue distilled in a current of steam. The easily fusible yellowish-white solid collecting in the distillate was recrystallised from dilute alcohol.The 3 : 3’-dichloro- diphenyl thus obtained crystallises from dilute alcohol in white needles and is easily soluble in ether, alcohol, and benzene; i t melts at 29’ and boils at 298’. 0.1789 gave 0.2308 AgCI. C1=31*9. C,,H,CI, requires C1= 3 1 *8 per cent. 3 : 4 : 3’ : 4’-Tetrac~Zorodiplien~Z. 3 : 3’-Dichlorobenzidine (1 2.7 grams) was dissolved in 90 C.C. of hydro- chloric acid of sp. gr. 1.16, diluted with 45 C.C. of water, the solution being cooled and diazotised with 6.9 grams of sodium nitrite dissolved8 CAIN : HALOGEN DERIVATIVES OF in a very small quantity of water. The resulting brownish-yellow solution was filtered and added t o copper powder (the " copper bronze " of commerce) which had been moistened with hydrochloric acid.Nitrogen was immediately evolved, and on the following day the mixture was filtered and extracted with ether. After evaporating off the solvent from the extract, the dry residue was distilled under diminished pressure, and by this means t h e tetrachlorodiphenyl was freed from a red by-product. The solid distillate was crystallised twice from glacial acetic acid, from which it separates in fine white needles, melting at 172" and boiling at 230" under 50 mm. pressure. The tetrachlorodiphenyl thus obtained dissolves easily in ether, alcohol, or benzene. 0,1392 gave 0.2741 AgCl. C1= 48.70. C,,H,C'l, requires C1= 48-58 per cent'. 3 : 3'- Dichlo~o-4 : 4'-clibro~iodii~hen~~. 3 : 3'-l)ichlorobenzidine (1 2-7 grams) was diazotised as in the [me- ceding case, except t h a t sulphuric acid was used instead of the hydro- chloric acid ; the filtered solution was poured into a solution of 20 grams of potassium bromide, to which copper powder had been added.The mixture was left for a time, then filtered, a r d extracted with ether. The red residue obtained after removing the solvent was divtilled under diminished pressure. The dichlorodibromodiphenyl, which is soluble in the ordinary organic solvents, on crystallisation from glacial acetic acid separated in white needles melting a t 176-177'. 0.1784 gave 0.2969 AgCl + AgBr. Halogen = 60.89 C1,,H,CI,Br2 requires (21 + Br = 60.60 per cent. 3 : 3'- DiclJoro-4 ; 4'-cli-ioclodi~l~en?Z. A solution of the diazonium sulphate was added to 20 grams of potassium iodide dissolved in water.Nitrogen was at once evolved, and after about 12 hours the mass was filtered, boiled with water to expel traces of free iodine, dried, and distilled under diminished pressure. The product was recrystallised from glacial acetic acid and obtained i n pale yellow, fern-like aggregates of needles, melting at 162" and boiling at 275" under 10 mm. pressure; it is easily soluble in the ordinary organic solvents. 0,1552 gave 0.2448 AgCl + AgI. C,,H,CI,I, requires C1+ I = 68.39 per cent. The effect of metallic sodium on the two foregoing substances was studied in the hope of obtaining a new condensation product, for Halogen = 67.69.DIPH ENYL AND DI HYDROXYDIPH ENYL. 9 although Fittig has shown (AnnuZen, 1864, 132, 205) t h a t this metal has no action on 4:4'-dibromodiphenyl, yet a 4: 4'-dibromo- or 4 : 4'-di-iodo-diphenyl which contained a chlorine atom immediately adjacent t o each atom of bromine or iodine might conceivably be more easily decomposed.Experiments were made in both ethereal and benzene solutions, but no action could be detected either with the dichlorodibromodiphenyl or the di-iodo-compound. These sub- stances can even be heated with copper powder considerably above their melting points without any condensation taking place, Y%e iYih-iZe OJ 3 ; 3'-UichZo.1.ocli~henyZ- 4 ; 4'-dicarboxyZic Acid (3 : 3'-13ichlcvo-4 : 4'-dicycLnodip~~s.nyl). A solution of the diazonium salt was added t o a boiling solution of cuprous cyanide. After some time, the nitrile was collected, a small portion extracted with ether, the ethereal solution evaporated, and the red residue distilled, The red by-product was not volatile, and the nitrile was thus obtained as a white substance which crystallised from alcohol in white, flocculent needles melting at 152-153'.The bulk of the crude nitrile was saponified by boiling with dilute caustic soda for a few hours. On filtering and acidifying, the acid separated out and W R S filtered, dried, and crystallised, first from glacial acetic acid and then from alcohol. From the latter solvent, it separates in small needles melting a t 287-2889 The substance thus obtained is very sparingly soluble in water, but dissolves more easily in alcohol or ether. 0*1280 gave 0.11753 AgC1. C1= 22-71. CI,€€,0,C12 requires C1= 22.80 per cent.Chlorination qf 4 : P'-Dihydroxydi~henyZ. As already indicated, Magatti (Zoc. c i t . ) obtained a tetrachlorodi- phenol by the complete chlorination of 4 : 4'-dihydroxydiphenyl (7-diphenol) in acetic acid solution, Schmidt and Schultz (Annnlen, 1881, 207, 334), by treating y-diphenol with phosphorus pentachloride, obtained three substances, namely, (1) a chlorinated diphenol (m. p. 126'); (2) p-dichlorodi- phenyl {,m. p. 14s'); (3) pentmhlorodiphenyl (m. p. 179'). I have already shown t h a t the first product mas most probably not1 0 CALIN : HALOGEN DERIVATIVES OF a trichlorodiphenol as suggested by Schmidt and Schultz, but was identical with 3 : 3'-dichloro-4 : 4'-dihydroxydiphenyl (Zoc. cit.) These chemists, assuming that the first product is a trichloro-derivative, explain the formation of the third compound from it by the replace- ment of hydroxyl by chlorine.By chlorinating y-diphenol with bleaching powder solution in presence of acids, a deep violet coloration is produced, which was noticed by Schmidt and Schultz. If this operation is carried out quantitatively, the interesting fact is demonstrated that three mole- cular proportions of chlorine are absorbed by one of y-diphenol. The diphenol (1 gram) was dissolved in caustic soda, dilute sul- phuric acid added t o the solution, and a solution of bleaching powder introduced from a burette until a reaction was obtained with starch- iodide paper, The amount of chlorine used was 1.14 grams, this quantity being identical with that corresponding with three molecules of chlorine.The reaction does not appear t o go quite smoothly, as a pure sub- stance could not be isolated from the product of chlorination, but analyses indicated that a trichlorodiphenyl had been formed. The object of these experiments being to find a method of obtaining the dichlorophenol, the direct chlorination in acetic acid solution was studied, and it was found that the mono-, di-, and tri-chloro-derivatives could be prepared by taking calculated quantities of chlorine obtained by oxidising hydrochloric acid with a weighed amount of potassium dichrornate. 3-Chlor o- 4 : 4'- d ih y d rox y diphen y I . The diphenol (1.86 grams) was dissolved in glacial acetic acid, and a current of dry chlorine, obtained by warming 0.98 gram of potassium bichromate with hydrochloric acid, was passed into the solution a t the ordinary temperature.The gas was a t once absorbed, and at the conclusion of the experiment the solution was concentrated to a small bulk and poured into water. The monochloro-compound, which was obtained as a white precipitate, was recrystallised from dilute acetic acid ; it forms white needles, soluble in ether, alcohol, or benzene, and melting at 215'. 0.1628 gave 0.10463 AgC1. C1= 15-89. C,,H,O,CI requires C1= 16.08 per cent. 3 ; 3'-Dich2oro-4 ; 4'-dihydroxydi~henyZ. The chlorination of the diphenol was carried out exactly as in the preceding cam, except that twice the quantity of potassium dichromate was used.DIPHENYL AND DIHYDROXYDIPHENYL. 11 The crude dichloro-compound was recrystallised from hot water and obtained in fine, white aeedles melting at 124'.Its properties were identical with those of the 3 : 3'-dichloro-4 : 4'-dihydroxydiphenyl (rn. p. 124O), obtained by another method (Zoc. cit.), and a mixture of the two preparations melted exactly at 124'. This identity is, of course, a proof of the constitution of this and the preceding substance. C12H,02C1, requires C1= 27-81 per cent. 0.1827 gave 0.20763 AgC1. C1= 28-09. 3 : 3' : 5(!)-Trich?oro-4 : 4'-dihydrox~d.i~~enyl. This trichloro-derivative, produced by using the appropriate amount of potassium dichromate, was obtained from dilute acetic acid in white needles ; it is soluble i n ether, alcohol, or benzene, and melts at 179'. 0.0899 gave 0.13083 AgC1. Cl2H7O2C1, requires C1= 36.75 per cent. Although the orientation of the third atom of chlorine has not been absolutely demonstrated, yet there can be little doubt t h a t tbe halogen occupies the position indicated by the notation used in naming the compound, The tetrachloro-compound, which was also prepared, and found t o correspond exactly with the substance described by Magatti, has, in all probability, the following constitution : C1 C1 C1= 35.96. My thanks are due to Messrs. Levinstein, Limited, Manchester, for a supply of the pure 3 : 3'-dichlorohenzidine, and t o Messrs. K. Whitaker and J. Brothers, who assisted in carrying out certain portions of the practical work. MUNICIPAL TECHNICAL SCHOOL, BURY, LANCASHII~E.

ISSN:0368-1645    

DOI:10.1039/CT9048500007

出版商:RSC    

年代:1904

数据来源: RSC

摘要:

12 PLIMMEH. : SEPARATION AND ESTIMATION OF IIL-Sepamtion c m d Estimation 01 Silver Cyajjide and Silver Chloi*ide. By ROBERT HENRY ADERS P L m m R , D.Sc. (Grocers’ Company’s liesearch Student). ON boiling a mixture of silver chloride and cyanide with dilute nit,& acid, I noticed that the latter salt was easily dissolved with the evolution of hydrogen cyanide, and on collecting this gas in a solution of silver nitrate i t was found that the amount of silver cyanide produced was constant. Further experiments showed t h a t silver cyanide was quantitatively decomposed by the action of dilute boiling nitric acid, so that by this means it can be easily separated from silver chloride and estimated. The earliest and most complete investigations on silver cyanide were made in 1844 by Glassford and Napier (Phil.Mag., 25, 66), who state that nitric acid has no effect on silver cyanide except when con- centrated and boiling, and that: sulphuric acid diluted with its ow11 volume of water decomposes silver cyanide, liberating hydrogen cyanide and forming silver sulphate; by this means, the cyanide may be separated from silver chloride, which remains unchanged. These observers did not, however, collect the hydrogen cyanide and deter- mine its amount. This observation, although cited in Gmelin’s Hand- book, has apparently been overlooked, for ot’her treatises on analytical chemistry give only two mebhods of separation depending on the decomposition of silver cyanide by acids. These processes are (1) t h a t of Kraut (Zeit. anal. Chenz., 1863, 2, 243), which consists in oxidising silver cyanide with nitric acid (sp.gr. 1.2) in sealed tubes for several hours at 100’ or for one hour a t 150’, and (2) that described in Son- nenschein’s liundbuch der Anulytischeu Chemie (1871, p. 252), which depends on the action of hydrochloric acid, whereby the silver cyanide is converted into silver chloride, the difference in weight indicating the quantity of cyanogen. EXPERIMENTAL. The first experiments were carried out with silver cyanide prepared from potassium cyanide in the usual way and dried at 100’. A known weight was gently boiled in a small flask with 200 C.C. of dilute nitric acid, the Ptrength of which was about twice normal, the flask being con- nected with a condenser placed in a vertical position, to the end of which was attached a Volhard’s receiver containing excess of silverSILVER CYANIDE AND SILVER CHLORIDE.13 nitrate solution acidified with dilute nitric acid. The hydrogen cyanide passing over with the steam produced a white precipitate in the silver nitrate solution, but although after one hour the silver cyanide was almost entirely decomposed, yet a small quantity remained which was dissolved completely only after boiling for about two hours. This decrease in the rate of decomposition is in all probability due to the resistance offered by the hard lumps which are formed in drying the silver cyanide. The silver cyanide obtained in the receiver was weighed and indicated a loss of 8-10 milligrams; this deficiency was attributed t o a small residue of silver chloride, the presence of which was due t o the potassium chloride originally contained in the potassium cyanide under examination.Experiments were then performed with silver cyanide prepared from hydrogen cyanide obtained by the action of dilute eulphuric acid on potassium ferrocyanide. Here, again, a slight loss amounting to about 1 per cent, occurred, as will be seen from the following results : AgCN taken." ,QgCN obtained. Loss. 0.3524 0.3484 0-0040 0.5042 0.4994 0.0048 0-3778 0.3744 0.0034 0.2484 0,2446 0.0038 0.3328 0-3288 0*0040 I n every case, the silver cyanide at the commencement was rapidly attacked, but the last portions required prolonged boiling for 1-2 hours in order t o complete the decomposition. During this time, the nitric acid, which at first was of normal strength, or, in some cases, even weaker, became more concentrated, buh although this might have caused a slight oxidation of the silver cyanide, yet it seemed as if this loss were in a great measure due to experimental error, since a deficiency of almost the same amount occurred when the silver cyanide was dis- solved in warm ammonia and reprecipitated with dilute nitric acid.Heat was applied in this case because the salt dissolved very slowly in the cold. Two experime'nts were made. AgCN taken. AgCN obtained. Loss. 0.2590 0.25'72 0.0018 0.3996 0.3954 0.0042 The amount of silver in the silver cyanide produced from the hydrogen cyanide obtained in the foregoing distillation was estimated with the following results : * The tabulated weightr thronghout are expressed in grams.14 PLIMMER : SEPARATION AND ESTIMATION OF 0.2952 AgCN gave 0.2376 Ag.Ag = 80.49 per cent. 0.3948 AgCN ,, 0.3174 Ag. Ag=S0.39 ,, AgCN requires Ag = 80.56 per cent. The amount of silver in the silver cyanide reprecipitated from the ammonia solution was also estimated. 0.2484 AgCN gave 0.1996 Ag. Ag = 80.35 per cent. 0.38’74 AgCN )) 0.3120 Ag. Ag=80.54 ,, Although dry silver cyanide can in this way only be directly estimated with a n accuracy of about 1 per cent., it can be completely separated from silver chloride and indirectly estimated by difference. The following two resiilts were obtained with a mixture of these com- pounds : AgCN taken. AgCN obtained. Loss. AgCl taken. AgCl obtained. 0.3594 0.3552 0.0042 0,6970 0,6974 0.2624 0.2584 0.0040 0.2288 0.2290 From these experiments, i t will be seen t h a t i t is not necessary t o heat the mixture of silver cyanide and siiver chloride in a sealed tube with concentrated nitric acid when their estimation i s required.Silver cyanide, however, when freshly precipitated and not dried, is quantitatively decomposed into prussic acid by the action of dilute nitric acid. I n these experiments, R 2 per cent. solution of potassium cyanide was used; in each case, 10 C.C. were allowed to flow from a burette into a known quantity of water containing 5 C.C. of a 10 per cent. solution of silver nitrate. This solution was then acidified with nitric acid until its strength in some experiments was normal, in others semi- normal, and distilled.The distillate, as in the previous experiments, after passing through a condenser was collected in a Volhard’s receiver containing 5 C.C. of the solution of silver nitrate acidified with dilute nitric acid. The time taken to completely decompose the silver cyanide was from 4-2 hour, but t h e distillation mas continued for a n hour so as t o ensure that all the hydrogen cyanide had passed over. The silver cyanide obtained was collected on a tared filter paper, washed with cold water, dried at looo, and weighed. Two determinations of the amount of silver cyanide (+ silver chloride) given by 10 C.C. of the 2 per cent. solution of potassium cyanide directly were previously made with the following results : 10 C.C. KCN solution gave 0’3892 AgCN 10 C.C. 7 ) ), 0.3882 ,)SILVEli CYANIDE AND SILVER CHLORIDE.15 The small residue of silver chloride which remained behind and which, as already mentioned, was due to traces of potassium chloride in the potassium cyanide, wits neglected i n the first two experiments, but in the remaining six estimations its weight was also determined. Ten C.C. of the foregoing potassium cyanide solution were employed in each experiment, and the results were as follows : AgCN ob- tained. 0.3830 0.3844 0.3874 0.3864 0.3832 0.3826 0,3846 0.3844 Residue of AgCl. Total. Error - - - 0.0038 0.3912 + 0.0025 0.0044 0.3908 + 0.0021 0.0044 0-3876 0.0052 0.3878 0.00 1 0 0.3856 - 0.0031 0-0022 0-3866 - 0.0021 The variations in the amount of silver cyanide obtained are in all probability due to the experimental errors incurred in measuring out the 10 C.C.from a burette, or in drying the tared filter papers at 100'. A series of six experiments was also carried out with a mixture of freshly precipitated silver cyanide and silver chloride obtained by mix- ing 10 C.C. of a 2 per cent. potassium chloride solution with the same amount of the 2 per cent. potassium cyanide solution and 10 C.C. of aqueous silver nitrate, then acidifying with nitric acid, and distilling in the manner already described. The amount of silver chloride given by the potassium chloride solu- tion was estimated separately; two experiments with 10 C.C. yielded 0.3918 and 0,3912 gram of precipitate, giving a mean of 0.3915 gram. Hence the total amount of insoluble silver salts obtainable from 10 C.C. of potassium cyanide solution and 10 C.C. of potassium chloride solution is 0.7802 gram. The following table contains the results obtained with the mixture (KCN = 10 C.C. ; KCl= 10 c.c.) : AgCN obtained. AgCl obtained. Total, Error. 0.3840 0.3910 0.7750 - 0.0052. 0.3842 0.3954 0-7796 - 0.0006 0.3854 0.3922 0.7776 - 0.0026 0.3854 0.3940 0-7794 - 0 ~ 0 0 0 ~ 0.3866 0 3946 0.7812 + 0~0010 0*3832 0-3974 0.7806 + 0*0004 mean = - 0.0013 The foregoing experiments show that by thz action of hot dilute16 DAVIS AND LIR’G: ACTION OF MALT DIASTASE ON nitric acid on a, mixture of silver chloride and cyanide the latter com- pound may be entirely removed from the former and its amount directly estimated. CHEMICAL LABORATORY, LISTER INSTITUTE OF l’REVENTIVE MEDICINE, LONDON, S.W.

ISSN:0368-1645    

DOI:10.1039/CT9048500012

出版商:RSC    

年代:1904

数据来源: RSC

摘要:

16 DAVIS AND LIR'G: ACTION OF MALT DIASTASE ON By BERNARD F. DAVIS, B.Sc., and ARTHUR R. LING, Introductory. IT is well known that when starch paste is hydrolysed by a n aquems solution of malt diastase, the speed of the reaction as indicated by the diminution of the specific rotatory power, and the increase of the cupric reducing power of the products in a given time becomes less the more the temperature of hydrolysis exceeds a certain point, which is termed the optimum temperature of diastatic action. Brown and Heron (Trans., 1879, 35, 596) give numerous determina- tions of the specific rotatory power of the products of the hydrolysis of potato starch in the form of paste by malt extract at different temperatures after the lapse of definite intervals of time, and from their results i t may be deduced t h a t the optimum temperature of diastatic action lies between 50" and 60'.Kjeldahl, who, in the same year (Cornpt. rend. hbor. de Carlsberg, Copenhugen, 2, log), confirmed this conclusion by determinations of the cupric reducing powers of the products in question, found the optimum temperature to be 55". The velocity of the reaction between diastase and starch paste, if measured by the constants just referred to, becomes less, pcwi pussu, at temperatures above 55" up to the point at which the activity of the enzyme is permanently destroyed. Moreover, if solutions of diastase are heated above 55" before mixing with starch paste, the same apparent slackening of the reaction or weakening of the enzyme is observed. The effect of heat on diastase is usually spoken of a s restriction, a term we have adopted, it being understood t h a t in all the experiments recorded in this paper the diastase was invariably previously heated in aqueous solution.In a paper read before the Midland Counties Institute of Rrew- ing ( J . Fed. Inst. Brewing, 1902, 8, 475), we gave an account of a large number of experiments on the action of diastase (previouslyPOTATO STARCH PASTE. 17 heated in aqueous solution and in the dry state, at various tempera- tures for definite intervals of time) on potato starch paste. In the case of previously heated diastase solutions, we found t h a t when the temperature emplojed was not above the optimum point, the reaction with starch paste new the same temperature (not above it), provided a sufficient mass of the enzyme were employed, proceeded rapidly for the first 7 5 minutes, and then advanced steadily until, at the end of about 40 hours, the specific rotatory and cupric reducing powers of the product were ,zpproxima.tely those of maltose.When, however, the diastase solution was previously heated above the optimum temperature, the reaction was not only slower, as has been obrerved by others, but the products were apparently different. Thus we found t h a t by the action on starch paste of diastase solutions, restricted in this way at 70' (the hydrolysis being allowed t o proceed at 55'), d-glucose could invariably be detected afher the reaction had continued for several hours. On the other hand, the products of the transformation of starch made with diastase solutions which had been previously heated f o r 30-60 minutes at temperatures not exceeding 55" were found by US not to contain d-glucose, even when the reaction was taken t o its final stage.Nor could we detect d-glucose in the starch derivatives made with diastase, which had been previously heated in the dry state a t temperatures as high as 1 2 5 O . The only change in the enzyme observed in such cases was a weakening of its action. It therefore appewed t h a t the production of d-glucose was connected with the initial heating OF the diastase solutions a t temperatures above 55", and since the publication of. the earlier paper (Zoc. cit.) the work has been continued principally with the object of obtaining further information on this point, The diastase used in the experiments was prepared by C .J. Lintner's method (J. pr. Chem., 1886, ii, 34, 378), and, except where otherwise stated, from Odessa malt dried a t a temperature not exceed- ing 33". W e are indebted t o llr. R. E. Free, of Messrs. Free, Rodwell and Co., Mistley, for placing at our dispxal several samples of this low- dried malt. The starch used was the purest potato farina. The temperature of hydrolysis never exceeded 55', but in a, few cases it was a degree or two lower than this. The methods of analysis adopted are explained i n our earlier paper (Zoc. cit.), with the exception of t h a t used t o estimate d-glucose, which consisted in weighing t h e phenylglucosazone produced under standard conditions, and calctdating from the weight the percentage of the hexose on the total solid matter in the solution, The values obtained are denoted by the symbol G,,,.The symbol RaSg3 represents the VOL. LXXXV. C18 DAVIS AND LING: ACTION OF MALT DIASTASE ON cupric reducing power, expressed as percentage of maltose on the total solid matter, calculated by the solution factor 3.93 from the specific gravity of the solution. EXPERIMENTAL . I n order to give some idea of the power of the diastase preparations employed, we may quote the following experiment from our earlier paper, in which unrestricted diastase from t h e same Odessa malt (0.08 gram) was allowed t o act, a t a temperature of 55”, on starch (10 grams) made into paste of about 3 per cent. concentration. Time. [Qln 3’93’ *R,.93’ 114 hours 150.0” 78.8 184 9 ) 143-6 90.6 42 7 7 138.5 99.7 66 9 9 138.0 96.9 138 Y , 137.6 99.5 An experiment since carried out with diastase from the same source (0.5 gram) and starch (10 grams) made into a paste of about 2 per cent. concentration gave the following results, the hydrolysis being conducted at 47” :- Time. [.ID 3.93- R,. 93. 89 9 9 134.6 97.5 67 hours 135.5” 99.6 This solution, which gave well-defined ma1 tosazone but no glucos- azone on treatment with phenylhydrazine acetate, also yielded malt- ose in the crystalline form, These experiments shorn t h a t the reducing power attains a maxi- mum and then undergoes diminution, a phenomenon which we have previously referred t o as “reversion,” but for which we have not at present found a satisfactory explanation.It is invariably exhibited in the case of conversions with both unrestricted and restricted dia- stase, and it may occur at any point of the reaction if the latter has stopped, because an insufficient amount of diastase is present t o carry the hydrolysis to its final stage. I n addition to the cases already mentioned (Zoc. cit.), we have now obtained further evidence showing that not only does the reducing power diminish when the temperature of hydrolysis is maintained beyond a certain period, but that the rotatory poNer increases. The following experiments were all made with diastase restricted by heating in aqueous solution at various temperatures.POTATO STARCH PASTE. 19 Se~ies I. A . Three separate amounts of diastase, (a) 1 gram, ( b ) 0.5 gram, (c) 0.2 gram, were restricted a t 7i*5-7S0 for an hour.They were then added to three 10 gram quantities of starch, each made into paste with 375 C.C. of water, and placed in a thermostat at 52-55'. IDS 93- R3-93. A- - 43 h0~1-s l g i * i o 190.9~ 187.20 6.7 2.6 1.7 91 I , 184.5 191.4 189.7 15-3 4.4 5.8 187 19 181.7 191.1 189.4 18.7 4.5 5.4 Time. (a). ((5). ( c ) . (a). @). (c). - - 20.8 - 259 ,, 183.2 -- (a), on fractionation, gave a dextrin insoluble in 46 per cent. alcohcl having the constants [a]D3.93 = 184-0°, R,.,, = 2.36. A fraction soluble in 80 per cent. alcohoi having a reducing power of R,.,, = 57.3 was separated ; but as this was contaminated with foreign matter from the diastase, and its amount was too small to attempt purification, i t was not further examined ; (6) and ( c ) were fractionated and found t o contain no constituent capable of giving a crystalline phenylosaxone. B.An attempt was now made to carry this reaction further by employing a lower temperature of rest'rictioo. To this end, 0.5 gram of diastase was restricted for an hour a t 75', the solution being then added to 10 grams of starch made into paste with 375 C.C. of m t e r . The temperiiture of hydrolJsis was 52-55', Time. [.I 3-91. J33.93. 65 hours 171.8' 49.5 113 9 ) 172.9 44.7 161 9 9 173.9 47.0 260 ? ? 158.6 62.5 The reaction mould have undoubtedly proceeded further if more diastase had been employed. The final solution, which gave no insoluble osaxone, yielded a soluble os;tzone having the form of " iso- maltosazone" and melting below 150'.This result showed that d-glucose, if formed a t all, had again disappeared (see pp. 25-27). C. Diastase (2.25 grams) was restricted for 15 minutes a t 74", and subsequently for an hour at 75-75-5'. The solution was then added to a paste prepared from 30 grams of starch, and placed in n thermo- s t a t at 5 5 O , the total volume of the liquid being 700 C.C. Time. [.ID 3'93' R9.93' 16 hours 191.0" 10.2 88 7 , 190.0 1 l . T 187 ,) 186.i 16.4 c 220 DAVIS AND LING: ACTION OF MALT DIASTASE ON At tbe end of 187 hours, the solution still gave a blue coloration with iodine, and after adding 0 02 gram of unrestricted diastase it was again placed in the thermostat at 55". Time. [a], 3'93' R,. !)3. 65 hours 1 3 8 . 9 O 95.6 89 9 , 139.7 93.8 After 89 hours, the solution yielded a small amourit of insoluble osazone, but the main portion of the product obtained by heating with phenylhydrazine was soluble in hot water, and had the form of '' iso- ma1 tosazone." Subsequent experiments showed that the period of heating a t 75" was too long, and that the unrestricted diastase subsequently added was not in sufficient quantity t o complete the reaction.Any d-glucose which might have been formed would probably have dis- appeared again. Series 11. The diastase (1.432 grams) was restricted a t 75" for an hour, the solution filtered and added to 10 grams of starch made into a paste with water, the total volume being 400 C.C. After remaining in the thermostat a t 55' for 115 hours, more of the same restrlcted diastase (1.305 grams) was added, and a further addition of 1.572 grams was made a t the end of 238 hours.The quantity of diastase used, which in the final solution corresponds with about 500 grams OF malt, renders the constants (especially the specific rotatory powers) untrustworthy, although blank experiments and corrections were made for each addition of diastase. No insoluble osazone was obtained from the final solution and only a small yield of soluble osazone. When the portion of this solution soluble in 90 per cent. alcohol was evaporated, even in alcoholic solu- tion, it rapidly became brown. This phenomenon, which has been frequently observed by other workers in the case of the products of the hydrolysis of starch by restricted diastase, will be further dis-POTATO STARCH PASTE.21 cussed in a subsequent paper. The alcoholic solution of the final products of the conversion just described gave no evidence of the presence of maltose, and did not yield crystals even after a consider- able lapse of time. Series 111. Attempts were now made t o follow the reaction with lower tern- peratures of restrict ion. A . Diastase (0-2 gram) was restricted for a n hour a t 6 3 O , and the solution added to the paste prepared from 10 grams of starch. The solution, which contained rather more than 2 grams in 100 c.c., was placed in the thermostat a t 52". Time. 3' 9:P 43 hours. 160.3O 91 9 , 148-5 187 ) 3 145.5 The final solution yielded a small amount of glucosazone when heated with phenylhydrazine acetate. As 0.2 gram of this diastase, if unrestricted, is more than sufficient t o convert 10 grams of starch into maltose i n 50 hours, it will be seen that apart from the produc- tion of glucose the heating at 63" has produced a great alteration.Subsequent experiments showed that by employing a larger amount of the restricted diastase it is possible to carry the reaction still further than the point attained in t,his experiment at the end of 187 hours. B. Diastase (0.2 gram) was restricted for la hours a t 60°, and added to 10 grams of starch made into paste. The solution, which contained rather more than 2 grams of starch in 100 c.c., was placed in the thermostat at 55'. Time. [a], 3-93. R3.93' 65 hours 144.5O 88.7 113 ?, 145.5 87.9 The final solution was fractionated wihh alcohol, the portion soluble in 90 per cent.alcohol yielding, on treatment with phenylhydrazine acetate, a n osazone (m. p. 150°), entirely soluble in boiling water and cousisting of a mixture of the flat plates characteristic of maltosazone with the aggregates of '< isornaltosazone." If the evidence thus far adduced be taken in conjunction with the results published in our earlier paper (Zoc. cit.), i t will be seen that when a solution of diastase is heated from 60' to 7 8 O , the enzyme, besides being weakened, is modified, and, in virtue of this modification,22 DAVIS AND LING: ACTlON OF MALT DlASTASE ON different products result from its action on starch paste. The nature of these products remains to be determined, but we have established the fact t h a t d-glucose is formed when the heating of the diastase solution is carried out between 6 3 O and 70".Later experiments show t h a t d-glucose is produced when the heating takes place at higher temperatures (for example, 78O, p. 29) if this is only maintained for a short time. Having thus established the fact that this modification in the action of the enzyme is a resnlt of its restriction in aqueous solution, it became interesting t o ascertain whether this was due to a permanent altera- tion of the diastase molecule. The question also arose as to whether the d-glucose obt,ained when restricted diastase acts on starch owes i t s origin t o the action of the modified enzyme on maltose, assuming this to be previously formed. As a result of several experiments, we stated ( d i d .) t h a t d-glucose is not prcduced by the action of restricted diastase on maltose, but the point is so important that it was again investigated. Xei-ies IV. Diastase (6 grams) was heLrted at 68" for 18 hours with 100 C.C. of water, the solution filtered and made up to 250 C.C. (u) Forty C.C. of the solubion were added t o 15 grams of starch made into paste with 300 C.C. of wat,er. ( B ) One hundred and fifty C.C. of the solution were precipitated with alcohol, the diastase collected, and 0.3 gram of the recovered sub- stance dissolved in water at 5 2 O , the solution being added to 15 grams of starch made into paste with 300 C.C. of water. A blank experi- ment with some of this reprecipitated diastase was carried oKt at the same time. (c> Twenty C.C.of the original restricted diastase solution were added to 170 C.C. of a 4 per cent. solution ( c ~ . ~ ~ = 4) of maltose. The remainder of the original restricted diastase solution was used for a blank experiment. (4. . Time. [.Ill 3.93' R3.93. 19 hours 153.7' 71.4 43 , Y 151.8 79.1 67 ? 9 150.0 79.4 139 1Y 147.6 82.0 (b). Time. C a l D 3'93' R3*93' 17 hours 164.2" 59.3 154.1 72.2 113 Y ) 153-0 72.3 41 9 ) d-Glucose was produced in considerable amount i n both these experi- ments. It is therefore proved t h a t the alteration of the diastase by heating with water (in this case at 68') is a permanent one, as i tPOTATO STARCH PASTE. 23 retains the property of producing a certain amount of d-glucose from starch after being precipitated by alcohol and redissolved in water.It is conceivable that d-glucose may also result from the action of unrestricted diastase on starch paste, but that i t is condensed t o a polysaccharide by a secondary action of the enzyme, Experiments to test this point are now in progress.* Expeyirnent c.-Action of restricted diastase on maltose (see p. 22). R,. 93' Time. [ I D 3.93' / -, 19 hours 154 2" 99-96 100.12 139 9 9 134.0 99-12 99.18 There is no indication from these constants that d-glucose is formed by the action of restricted diastase on maltose, and this conclusion is confirmed by the fact that no insoluble osazone mas obtainable from the solution. The constants (which, as in all other cases, were fully corrected for the effect of the diastase remaining in the boiled solu- tion) differ from those of pure maltose to an extent beyond the limit of experimental error.To what this is due me cannot a t present say. The following experimeut illustrates the action of unrestricted diastase on maltose, giving the constants [alD 3.y3 = 137.8", R3.93 = 100. About 3 grams were dissolved in water, a solution of diastase (0.1 gram) added, and the whole made up to 100 C.C. This solution was placed in a thermostat f o r 48 hours at 55", and, on examination, gave the following values : [ a ] D 3 93 = 131-5', R,.,, = 99.5. The solution yielded no ghzcosazone, but the soluble osazone obtained crystallised in stellate groups of needles and melted a t 169-170O. The maltose, after the above-described treatment, was completely fermentable by yeast. It now became of interest to determine the amount of d-glucose formed by the action on starch paste of diastase, restricted for differ- ent lengths of time a t various temperatures.For this purpose, the sugars in a known volume of the solution mere converted into their phenylosazones under standard conditions, and the insoluble glucosazone collected and weighed. After about 50 determinations, the total mixed products were examined and identified as d-glucosazone. This result, taken iu conjunction with the rotatory and reducing powers possessed by certain fractionated products which gave the insoluble osazone in large amount, proves conclusively that the osazone was derived from d-glucose, and that this sugar is one of the products of the action of restricted diastase on starch paste.* Cornpare Ling (British Assoeiatioib h'eport, 1903, and J. bid. I?&. Brewing; 1903, 9, 450).24 DAVIS AND LING: ACTION OF MALT DIAS'L'ASE ON The osazone, as weighed, melted as a rule at 198' ; sometimes, how- ever, the melting point was higher. After being twice recrystallised from alcohol, it melted constantly at 204'. When i t was dissolved in glacial acetic acid, the solution had a Iaworotation (compare E. Pischer, Bey., 1890, 23, 2119). Maquenne (Compt. rend., 1891, 112, 799) and C. J. Lintner (Zeit. ges. Brauw., 1895, 18, 153) have both devised methods for estimating various sugars a s osazones. After numerous trials, we found that, for our purpose, exceedingly concordant results could be obtained in t h e estimation of d-glucose as osazone by working under the following conditions.Twenty C.C. of the solution, containing 2-3 grams of starch pro- ducts per 100 c.c., are mixed with 1 C.C. of yhenylhydrazine and 1.5 C.C. of 50 per cent. acetic acid in a boiling tube, and heated for a n hour in a bath of boiling water. At the end of this time, the liquid, which has evaporated t o a small bulk, is carefully poured on t o a tared Gooch crucible, and, after the mother liquor is removed, the crys- talline glucosazone is transferred t o the crucible and washed with a small quantity of boiling water (about 20-30 c.c.), so t h a t the total filtrate does not exceed 50 C.C. It mas found t h a t the maximum amount of pure glucosazone could be obtained by one hour's heating. If the heating i s continued for a longer time, decom- position of some of the soluble osazones ensues, and the products of this decomposition contaminate the glucosazone.Under these condi- tions, 0.1 gram of glucose mixed with various proportions of maltose gives 0.0505 gram of glucosazone. I n filtering, care must be taken to allom the mother liquor t o pass through the Gooch crucible before adding the "washing water, otherwise the soluble osazone is precipitated and, clogs the filter. Series V. These experiments were made in order t o ascertain what effect the time of previous heating of t h e diastase solution has on the amount of d-glucose formed. The diastase used was prepared from malt germinated by ourselves in the laboratory (see Ling and Davis, Zoc. cit., p. 484). Three portions of the diastase, amounting each to 0.3 gram, were restricted at 64' for 1 hour, 2 hours, aud 4 hours respectively.They were then each added t o three 15 gram portions of starch made into paste with 300 C.C. of water, the resulting solutions being placed in a thermostat at 53'. The following analytical results were obtained :POTATO STARCH PASTE. 2 3 Time of Time of cy.ga restriction. hydrolysis. (corr. 1. , ['ID 3'93' 1 hour 117 hours 4'291 150.i" 2 hours 117 ,, 4 -430 154.2 4 7 7 115 ) ) 4.1 59 151.4 78'9 ~ 6.5 7'4 74 -1 7'3 73.1 These results indicate that, when the time of restricting a t 66' is more than an hour, there is no substantial increase in the amount of d-glucose formed. Swies VI. A freshly prepared active sample of diastase from Odessa malt was employed ; 0.3 gram was used in each experiment and 15 grams of starch.The temperature of restriction was 65-66'. Tiiiie of restriction i n liours. u Time of hydrolysis ~ in hours. 1 17 I 41 I 113 209 17 41 113 209 4.072 4.147 4.345 4'384 4.081 I 4-175 4.053 i 4.278 I - 152'ii" ~ 154'0" 144'8 145.5 14.5 *;; 146'2 145':; I 147'8 :: 1 113 209 I I 17 41 113 209 74 '4 72.6 57% 85'1 87.1 j 83.5 85.4 1 83.4 4'2 ' 4.0 8 '1 8.0 9.9 9.2 4'3 7.6 2. I 4 . 3.873 3.988 4 034 4.079 3'8SO ~ 3'965 3.869 3.378 I 154.7" 147'8 147 '3 148'8 158.4" 153.2 153.3 153.1 66.3 73.4 73.4 74.5 nil 2.2 8.0 7.5 * In this experiment, a distinct amount of mitter insoluble in boiling water was obtained, but it was amorphous, and therefore not glucosazone. It is seen by these experiments that for a restriction temperature of 66" the maximum amount of d-glucose is formed when the period of26 DAVIS AND LING: ACTION OF MALT DIASTASE ON heating was hal€ an hour, It is interesting to note the marked diminution in tbe percentage of d-glucose, after the hydrolysis has pro- ceeded for 209 hours, as compared with the values in the preceding columns (1 13 hours).This is possibly due t o the condensing action of the enzyme. Series VII. The same diastase was used as in the last series, but the tempera- ture of restriction was 69'. The temperature of hydrolysis was 5'. Time of restriction i n hours. Time of hydrolysis 0.25. in hours, I I I 1 7 ;; I 137 l i 41 65 137 17 41 65 137 r I 17 1 41 65 137 3.924 3'811 3'724 3.643 154 -6' 141.4 139.1 139'4 __. - - 91'1 0.5. 4'044 3.876 3'923 3.810 1.4'093 3.950 3.894 - 2. 3.980 3'919 3'852 3-882 157.1" 144-3 143.1 143'0 161'5" 150'8 148'5 I 165'2" 157'7 150'7 151 *2 96'6 89 3 - 96 '6 90% ~ 81'4 7.8 11'6 11'8 10'8 8 -7 11-2 10.6 10.6 5 '4 8'2 7.2 * 7.9 - 69'4 73'3 75'2 1.1 7.5 6.5 1 *5 * The exact concentration of this solution was not deteriniued, and the figure G,.,,=7*2 is calculated on the concentration found for the solution after 41 hours. Seyies VIII. I n these experiments, the temperature of restriction was raised t o 70-5', but the time of heating was reduced. Temperature of hydrolysis = 5'.POTATO STARCH PASTE. 27 I i Time of hydrolysis in hours. I Time of restriction in minutes. _c____ __ _ _ _ ~ 5 . I 17. 1 30. 1 120. 4.079 4.121 1 3985 4 016 1 4'063 ' 4.005 3'995 4.061 I 3.926 19 43 67 4.027 4.009 3.969 166%" 162.3 162'2 19 8.9 ' 8.1 5'8 4'7 10-0 7.3 1 3-9 6'8 1 7-9 3'7 Series IX.A . 0.3 gram of diastase restricted at 61.5" for 45 minutes and added at 55" to 20 grams of starch made into paste with 400 C.C. of water. 1 4 335 4'255 4'271 ' I 148.2" ' 13S.7" ' 137% 1 51'2 1 96'3 1 ~__- I 66 - I, B. The amounts of diastase shown in t h e following table were88 - DAVIS AND LING ACTION OF MALT DIASTASE ON hydrolysis iu hours. - 18 4 2 66 Time of restriction in minutes. 5. 4.271 4.219 4.120 18 42 66 145'6" 136.1 135'3 1 5. I-_____ 4.107 L.082 4,077 15. _ _ 4.041 4.009 4.000 141.8" i 133'4 I 133'1 I 1453" 135'6 135.5 18 84.6 42 I 98.7 66 99.8 90.1 102.4 101.6 87.4 101.9 100.2 18 7.7 - 9 *7 66 10.7 8.9 9.4 9.6 11.4 1 11'0 C. One gram of diastasemas dissolved in water,nnd the solution, which was raised t o a temperature of 7 3 O in 5 minutes and maintained a t 73-73-5' for an additional 5 minutes, was then added to 20 grams of starch made into paste with 400 C.C.of water. Series X. I n this series, solutions containing the weights of diastase given in the table were restricted at the temperatures mentioned, rapidly cooled, and added to paste prepared from 20 grams of starch and 400 C.C. of water at 55" in each case. The hydrolysis was allowed to proceed for 66 hours.POTATO STARCH PASTE. 29 Amount of Temperature of diastase. restriction. 0.3 61'. 5 9 .5---60' 0.3 9 , 63" 0.3 :, 6 2' 1.0 97 76*5---77'5' I n the last experiment, waker, a t with the dry diastase, the mixture 76.5".The solution was raised to Time of restriction. G,. 43' 1 hour, 0.5 0-25 ,, 0.4 0-75 ,, 0.5 5 min. 3.9 a temperature of 78", was mixed having initially a tempereture of 77.5' in 5 minutes, after which i t was rapidly cooled and added to the starch paste. Gomlusions. The effect of heating a solution of diastase is t o cause a weakening of the action of the enzyme, and also t o produce an alteration in the diastase molecule. The latter effect, which is the more important in the foregoing experiments, is a permanent one, for diastase solution which has been heated above 55' retains its altered properties when reprecipitated from a solution by alcohol and allowed to act on starch paste a t a temperature of 55" or below, Tho alteration of the diastase appears t o commence when a solution is heated below 60°, although a complete change is not effected, inas- much as the amount, of d-glucose formed by the action on starch paste of diastase, previously heated for an hour at this temperature, is small. As the temperature of restriction is increased, the amount of d-glucose formed by the action of the enzyme on starch is augmented, and the maximum amount of d-glucose is produced by diastase which has been previously heated i n solution at 68-70". Above this temperature, the weakening of the enzyme is so rapid that a much larger quantity of it has to be employed in order t o attain the stage of the reaction a t which d-glucose appears, especially if the heating is prolonged ; never- theless, this hexose is formed by diastase restricted a t temperatures up to 78', and probably above this. I t has invariably been observed that, when the solution is kept a t the temperature of hydrolysis, usually 55*, after the maximum amount of d-glucose has been formed, this sugar diminishes i n amount, and the occurrence of this apparently condensing action of the enzyme may probably explain the occasional failure t o detect d-glucose among the products of hydrolysis (see Series I and 11). I n any case, the maxi- mum amount of d-glucose formed does not exceed 1 2 per cent. of the total hydrolytic products. 74, GREAT TOWER STREET, LONDON, E. C. - ----

ISSN:0368-1645    

DOI:10.1039/CT9048500016

出版商:RSC    

年代:1904

数据来源: RSC

摘要:

30 LAPWORTH: THE ACTION OF HALOGENS ON V.-The Action of Halogens on Compounds containing the Ca.i.bon yl GYO up. By ARTHUR LAPWORTH. THE question of the nature of the mechanism of substitution in carbon compounds has attracted much attention during recent years, more especially in certain cases where the compounds are benzenoid in character and in which the process of substitution in the aromatic nucleus appears t o involve the initial formation of a n additive product of the compounds with the agent used or of an intermediate substitution product in which the substituting atom or group i s not found in i t s final position of attachment. Considerably less is known of the mode in which substitution occurs in fatty compounds; and in what is possibly the simplest case of all, namely, t h a t of direct substitution such as occurs among the paraffins, it may be said that there is no evidence which affords any real assist ance in arriving at conclusions as t o the mechanism of the process, and generally these cases have been avoided as being the most difficult to solve.The case of substitution in the group of compounds containing the complex :CH*CO, such as ketones, aldehydes, carboxylic acids and their derivatives, is one of considerable interest, and in certain aspects has aroused much discussion, for there is here a possibility t h a t t h e characteristic replaceability of the a-hydrogen atom may be not a direct process, but one due to the initial formation of the enolic form :C:C(OH)-, and this view has appeared more probable since it has been shown that the nitro-paraffins, which in many respects resemble car- bony1 compounds, are apparently not capable of being brominated directly, but are easily converted into monobromo-derivatives if they are first transformed into the isonitro-form which corresponds with the enolic forms of carbonyl compounds.It is a general rule, too, that those carbonyl compounds are the most easily attacked which are known t o be capable of conversion into their enolir! forms or one of the corresponding metallic derivatives. The difliculty with which the paraffins m e attacked by halogens renders this question of the mechanism of their substitution most difficult t o investigate in a satisfactory way, and i t seems desirable, thereeore, that search should be made for some other class of more easily substituted compounds in which the process is direct, at least in the same sense as i t probably is in the paraffin series, and the work described in the present paper was commenced in the hope that, after all, the bromination of simple ketones might prove to be mainly theCOMPOUNDS CONTAINING THE CARRONYL GROUP.31 result of " direct " substitution. The results obtained, however, can only be interpreted on the opposite assumption; briefly stated, they were as follows. The action of bromine on acetone in dilute aqueous solution is ex- ceedingly slow, but becomes more rapid in presence of acids, the resulting accelerations being of the same order in the case of the more powerful mineral acids (sulphuric, hydrochloric, and nitric acids), and less obvious in the case of the weaker ones, such as acetic acid.The influence of hydrochloric acid on the velocity was not appreciably affected by the presence of a n eqiiivalent amount of potassium chloride or bromide. Neutral salts of strong bases and aeids in general did not produce any marked influence on the speed of reaction. I t was noticed, too, that the velocity observed in diflused daylight was not appreciably different from that in darkness. The effect of tthe three mineral acids was nearly proportional to the amounts used, but in the case of sulphuric acid, between the concen- trations 0.04- and O..l-O-normal, the effect was proportionately slightly greater a s the dilution increased. The velocity was nearly proportional to the concentration of acetone, but was practically independent of the concentration of the bromine.Discussing these points in the reverse order, i t may be observed that the independence of the velocity of reaclion on the concentration of bromine shows clearly, first, that the reaction proceeds in at least two stages, in one or more of which the bromine is not involved, and, gecondly, t h a t in the stage or stages in which the bromine takes part, the velocity of reaction is SO great that the time occupied is not measurable. The approximate proportionality of the velocity to the concentration of the acetone indicates t h a t in the reaction representing that stage, the velocity of which is measured, only one molecule of acetone takes part, whilst the observations as t o the influence of acids of different Concentration are best explained on the supposition that in this reaction one hydrogen ion is involved.The increasing degree of dissociation of sulphuric acid due to dilution becomes apparent in the slight increase of the velocity constants representing the speed of absorption of bromine per equi- valent of acid per litre. The effects produced by sulphuric, nitric, and hydrochloric acids a t the concentrations 0*40-nbrrnal were represented approximately by the numbers 1.19, 1.20, 1.36. These numbers, although of the same order of magnitude, are not proportional to the respective concentrations of the hydrogen ions. This discrepancy, however, is not without parallel, and does not militate seriously against the foregoing general conclusion.It seems probable, then, t h a t the bromination of acetone under the32 LAPWORTH: THE ACTION OF HALOGENS ON conditions maintained is best regarded 8s the result of a slow, reversible change effected in the acetone by the hydrogen ions, followed by an almost instantaneous bromination of the product, a change which is not appreciably reversible. This intermediate product is perhaps the enolic form of the ketone, as it has been already shown that in many cases the rapid attainment of equilibrium between the tautomeric forms of carbonyl compounds is brought about by acids (Trans., 1902, 81, 1503, and 1903, 83, 1121), whilst there is ample reason for believing that the enolic forms are the more rapidly attacked by substituting agents. It is clear, also, that the independence of the speed of reaction on the concentration of bromine shows that the velocity with which the second form of the acetone is brominated must be incomparably greater than that of the reverse change of the labile to the normal form, so that the observed velocity is a fairly precise measure of the speed with which acetone is converted from the normal into the less stable form.In the case of the interaction of chlorine and acetone, the speed of reaction is more obviously dependent on the concentration of the halogen, but as that concentration diminishes, the velocity decreases until i t approximates very nearly t o that observed when bromine is used under Pimilar conditions. This difference might be explained in a t least two ways : (1) that chlorine acts directly on acetone, or (2) that the halogen is capable of existing in the initial change in the ketone which precedes the actual substitution.Of these, however, the first possibility is apparently disposed of by experiments on the action of chlorine on neutral solutions of acetone, as in this case the initial velocity of reaction is far too small to account for the difference in the speeds with which chlorine and bromine are absorbed by acetone in presence of acid : in both cases, the speed increases with lapse of time, owing, doubtless, to the increasing amount of acid present. The last part of the paper contains an account of some experiments which were made for the purpose of ascertaining whether the action of chlorine and bromine on other carbonyl compounds is accelerated by acids, and the results show beyond question that the effect is a fairly general one and is well marked in the case of acetone and other ketones in solvents other than water, and also in those of carboxylic acids and their anhydrides and esters.The ease with which dry acetic acid may be brominated in presence of halogen hydrides leads to a simple explanation of the part played by small quantities of phosphorus in promoting the action of halogens on carboxylic acids. The phosphorus chlorides and bromides which are produced in the first instance, will react so as to remove the water present, supplying a t the same time the requisite hydrogen chloride or bromine ; in the absence of water, the halogen hydridesCOMPOUNDS CONTAIKING THE CARBONYL GROUP.33 will be produced by the interaction of the phosphorus halogen compounds with some of the carboxylic acid itself, The usual explanation, namely, that the halogen only attacks the acid chloride or bromide is no longer necessary since it has been shown that the accelerating effect of powerful acids is not confined to substitutive changes in the series of carboxylic acids. EXPERIMENTAL. Brorninitctzon of A c e t o n e . The action of bromine on acetone, either undiluted or dissolved in organic solvents, is difficult to control, and dilute aqueous solutions of the ketone were therefore employed, the experiments being made with the object of ascertaining, first, the effect of varying concentrations of acetone and bromine, and, secondly, the effects produced by foreign substances which might reasonably be expected to alter the velocity of reaction, either by their influence on the state of dissociation of the reacting substances or by retarding or accelerating the changes of structure which the ketone might undergo.In the preliminary experiments, a dilute aqueous solution of acetone was rendered yellow by the addition of bromine water and then divided between a number of stoppered bottles, to each of which was then added varying quantities of a number of electrolytes. The results showed clearly that the effect of neutral salts, such as sodium sulphate, potassium bromide, &c., was very slight, but that acids caused a very marked increase in the speed with which the colour of the bromine disappeared, so that, instead of occupying some days or even weeks, the action was at an end in :L few hours or minutes, according to the affinity and the amount of acid present.Thus with equivalent amounts of sulphuric acid, hydrochloric acid, and acetic acid, the first two acted very rapidly, and the last caused a marked acceleration; with acetic acid in presence of a n excess of sodium acetate,* the change was almost as slow as in the absence of acids. I n order to ascertain whether the product of the action of bromine on acetone in presence of dilute mineral acid was a simple substitution product, 30 grams of acetone were dissolved in a mixture of 200 C.C. of water and 60 C.C. of ordinary hydrochloric acid, the whole being allowed to remain for several weeks in a stoppered vessel with one molecular proportion of bromine.After the colour of the solution had entirely disappeared, the solution was filtered from a very small * I n this instance it was found necessary to submit the sodium acetdte to a prez liminary treatment with a small quantity of bromine, the excess of which was after- wards removed by a stream of air, :is the salt invariably absorbed a small quantity of halogen even after repeated crystallisation. VOL. LXXXV. D34 LAPWORI'H : THE ACTION OF HALOGENS ON quantity of crystalline matter, cooled in ice, and saturated with calcium chloride, the oil which separated being removed, dried, and fractionally distilled, The crystalline material was insoluble in water and crys tallised from ethyl acetate in fine needles melting at '75".0.3112 gave 0.6483 AgBr. R r = 88.6, CDH0Br5 requires Br = 88.5 per cent, The compound appeared to agree in all its propertieg with the penta- bromoacetone melting at 76O, The liquid portion of the product had the characteristic pungent odour of bromoacetone, and, when rnpidly distilled under atmospheric pressure, passed over for the moat part between 130" and 142O, a certain amount of a dark brown residue remaining in the flask. The fraction boiling at 130-142O was washed with dilute sodium car- bonate solution to remove the hydrogen bromide liberated during the distillation, dried over anhydrous sodium sulphate, and analysed. 0.1686 gave 0.2338 AgBr. Br = 59.0. CaH,OBr requires Br = 58.4 per cent. There is therefore no reason to suppose that the reaction between acetone and bromine in presence of dilute acids is in any way abnormal, It may be mentioned that in the quantitative experi- ments described below the products invariably had the pungent odour of bromoacetone, A series of quantitative experiments was made with a dilute aqueous solution of acetone at a constant temperature, the concentration of the bromine being determined from time to time by withdrawing aliquot portions of the solution by means of a pipette, and running these directly into a solution of potassium iodide; the amount of iodine liberated was ascertained by titration with a 0*05-normal solution of sodium thiosulphate, the exact value of which was checked from time t o time.The concentration of the acetone was kept somewhat low in order that its condition of hydration might be as nearly as possible the sitme i n different experiments, which will only be the case in dilute solution, Moreover, the relative amount of bromine employed at first was always considerably less than one molecular proportion, so that the concentratior of the unsubstituted portion of the acetone should not vary too widely ; it was found, as a matter of fact, that within the limits adopted the relative initial concentrations of the bromine and acetone did not appreciably affect the nature of the results.In every case in which a flask had to be opened several times during an operation, so that a measurable quantity of volatile materials mightCOMPOUNDS CONTkJNlNG TKE CARBONYL GROUP. 35 have escaped, a second flask was prepared simultaneously, in precisely the same way, and opened for titration only a t the beginning and at the end of the experiment ; in the few cases in which the titres did not correspond, the results were rejected.Further, in order that the results should have a t least a comparative value, the correct working of the thermostat and the concentration of the solutions were tested by another determination of the velocity of reaction in a solution of standard concentration, so thdt any material variation in the con- ditions could be readily detected and the necessary allowance made. These measurements were, however, made with the object of ascertaining the general character of the influence of the materials employed, and are t o be regarded as approximations only, but it is probably safe to suppose them comparable.The speed of removal of bromine by a dilute aqueous solution of acetone in the absence of free acid or alkali is very small; thus, in a solution containing 40 grams of acetone per litre, the free bromine a t the commencement of the experiment corresponded with 9.25 C.C. of N/20 thiosulphate per 25 C.C. of the solution, whilst a t the end of three days, during which time it remained at the temperature of the laboratory, the titre had only diminished to 9.05, and a t the end of a week it was 8.70. In the presence of acid, the speed of disappearance of the bromine was nearly constant. The numbers obtained in the following experi- ments, in which the concentration of acetone and sulphuric acid, as well as the temperature, are those which were adopted throughout as the standard for comparison, prove clearly that the speed at the end of the operation is practically identical with that at the commencement, The temperature throughout the series of experiments was 20.3O, except where a statement to the contrary occurs.The titres are those for 25 C.C. cif solution, and are given in terms of N/20 thiosulphate ; the initial and final numbers are expressed in the same terms,but were always determined by the titration of 50 C.C. of the solution, so that the numbers in these cnses are one-half of those actually obtained, and were used throughout for the determination of the approximate value of the constant k, this term being found by the aid of the formula : i%= 104 v/c1c2, where Y is the velocity of disappearance of free bromine in gram- molecules per litre, and c1 and c2 are the concentrations of the ketone in gram-molecules, and of the acid in gram-equivalents per litre respectively. The numbers in the third column of the following table are those calculated on the assumption that the reaction may be represented by a straight line between the initial and final points.0 236 LAPWORTH; THE ACTION OF HALOGENS ON Expepinaent A. Quantities employed : acetone = 40 grams ; hormal €€,SO, = 400 cx. per litre. Timc. Titre. Calculated. 0 19*25 - 10 minutes 17-05 16 -95 20 9 9 14.80 14.60 60 ,? 5.00 5.30 67 9 , 3.50 3.65 70 9 , 3.00 3.05 80 ,, 0.65 0.75 0.05 - k = 8.38 75 ,Y 1.60 1.90 83 ,> Two other experiments with the same concentrations of acid and ketone gave k=8.52 and 8.57.As these experiments indicated that the velocity of bromination was nearly independent of the amount of bromine present, two other experiments were made with small quantities of the halogens and these confirmed this conclusion, the same rectilinear character being evident and the constants found being (B) 8.40 and (0) 8-55. I n Fig. I (p. 37), the results of the last two experiments are compared with those given in the foregoing table. I n order to determine whether the initial change produced in the ketone by the acid was a reversible one, a solution containing 40 grams of acetone and 400 C.C. of normal sulphuric acid was prepared and allowed to remain for four days, when a measured bulk of bromine water was added and the whole at onc0 diluted to one litre with water a t 20.3", an exactly similar solution being mads simultaneously in which the ketone and acid were brought into contact only at the last moment.It was found that the titres of 25 C.C. of these solutions, five minutes after making up, were 17.2 and 17.4 respectively, whilst the corresponding velocity constants were k=8-31 and 8.43 respectively; it seems clear, therefore, that the initial change occurs only to a very minute extent and is of a reversible character. Eflect of the Concentration, of Retone ccnd Acid.--The line D in Fig. I represents a portion of a line joining the points correspond- ing with the initial and final titres obtained in an experiment in which the concentration of 'the acetone is only one-tenth of that present in A , B, and C; the reaction velocity was somewhat less than a tenth of that observed in the other three cases.COMPOUNDS CONTAINING THE CAHBONYL GROUP.37 The mean results obtained in a number of experiments a t 20.3' Itre given i n the following table, and represent the variation of k= lo4 x F/clc2 with the concentration of ketone and acid. Acetone (grams per litrc) Sulphuric acid. 4 10 20 40 0.40 gram-niols. per litre 8.07 8.24 8-38 8.40 > 9 s-53 8-59 8.71 0.20 - 9 9 S.81 8.93 0.10 - -- ?! 9.68 0.04 -- e v FIG. 1. 0 10 20 30 40 50 60 70 80 90 Afiniiles. With hydrochloric and nitric acids at a concentration of 0.40 gram-molecules per litre and 40 grams of acetone per litre, the reaction was also rectilinear, the constants found being 11-56 and 10.21 respectively.I n presence of potassium chloride and bromide with hydrochloric acid of the above concentration, the constants (k) were 11.69 and 11.54 respectively, in both cases, an amount of38 LAPWORTH: THE ACTION OF HALOGENS ON the salt equivalent to the acid present being employed. The results obtained with 0*40-normal acetic acid were very inconsistent, a rapid fall in the bromine concentration being observed a t first and due perhaps to some impurity in the acetic acid, which was not readily removed, even by distillation over sodium acetate. With acetic acid in the presence of two equivalents of sodium acetate which had been purified by a preliminary treatment with bromine, a rapid initial fall in the titre from 16-80 to 14.25 occurred in the course of a quarter of an hour, whilst subsequently the action became so slow that after an additional period of five days the titre had fallen only to 13.110, Chlorine and Acetone.On the whole, it was found that when chlorine was allowed to act on acetone in dilute aqueous solution in presence of mineral acids, this halogen invariably disappeared somewhat more rapidly than bromine. The following details of two simultaneous series of measurements made with two solutions of identical concentratioii as to acetone and acid will serve to show what was the general nature of the difference observed in the two cases. Quantities employed : acetone = 20 grams per litre ; normal H,SO, = 400 C.C. per litre. A. Bromine. Tim 0. Ti tr;! . 0 9-20 c.c. 12.5 minutes 7-75 ,7 34.0 ), 5-45 ), 65.5 ), 1.80 ,7 71-5 ,) 1-15 .7 57.5 ), 0.40 ), B.Chlorine. I-- Time. Titre. 11.0 minutes 11.00 C.C. 26.0 .) 7-70 ,, 38.5 1, 5.65 ? ) 47.0 ,, 4.50 ,) 55.5 ;, 3.40 ,, 6 4 0 9 7 2.25 ,, 81.0 ,, 0.35 ,, 0 (1) 19.0 ,, 8-90 ,, 74.0 ,, 1.10 ), It will be noticed that the chlorine a t first disappears with con- siderably the greater speed, but., as the concentration of the halogen diminishes, the velocity of chlorination approaches very nearly t o that of bromination, so t h a t it appears that the velocity of substitu- tion is not so nearly independent of the concentration of the halogen in the former as in the latter case. To test the question as t o whether chlorine exerts an independent or direct influence on the speed of substitution, the effects of t h e two halogens on dilute, initially neutral, aqueous solutions of acetone wereCOMPOUNDS CONTAINING THE CARBONYL GROUP.39 directly compared and the following results obtained, the concentra- tion of the acetone being 40 grams per litre. A . Bromine. Time. Titre. 0 10.70 C.C. 4 hrs. 5’ 10-45 ,, 23 ,, 53’ 10.70 ,, 87 ), 3’ 10.30 ,, 168 ., 0’ 9.10 ,) R. Chlorine. Time. Titre. 0 9.95 C.C. 3 hrs. 6’ 9.85 ,) 87 ,) 0’ 7.60 ,, 168 ,, 0’ 2-40 )) 23 ,, 6’ 4.55 $, Thus the action of chlorine alone on acetone is very slow indeed and does not account for the very considerable difference between the initial velocities of chlorination and bromination in the presence of acid. FIG. 2. 12 10 2 0 I0 20 30 40 50 60 70 80 90 MintLtes, Bromination of Acetone in Solvents other than Watev. Specimens of purified light petroleum, benzene, and chloroform were allowed to remain in contact with bromine for some hours and were then washed repeatedly with dilute alkali and water and finally dried.This treatment was found to be necessary, as almost all specimens of these liquids were found to decolorise a small quantity oE bromine, and the subsequent action of bromine on acetone dissolved in them was much too rapid for comparative experiments, owing, probably, to the production of free hydrogen bromide. Highly dilute solutions of aoetone, hydrogen chloride, and bromine40 LAPWORTH: THE ACTION OF HALOGENS ON in the purified solvents were then prepared, and i t was found on mixing the solutions of acetone and bromine that the disappearance of the colour of the latter was conveniently slow a t first and that addition of the hydrogen chloride solution produced a very marked acceleration.It was also observed that, when no hydrogen chloride was added, the disappearance of successive small quantities of bromine occurred with increasing rapidity, owing, no doubt, to the hydrogen bromide formed. Efect of Acids on the Speed of Brovninution and Chlorincdion of other Cnrbonyl Compounds. Many ketones are not, at first, easily attacked by bromine, but This effect when once the reaction has begun it proceeds rapidly. FIG. 3. 0 1 2 3 4 5 6 7 8 Days. may be noticed when, for example, methyl isopropyl ketone is treated with bromine in the cold or when a-bromocamphor is prepared by adding bromine to camphor which is being heated on the water-bath. Acetic anhydride, when mixed with bromine at the ordinary tempera- ture, is only very slowly affected, but, if previously saturated with hydrogen chloride or if mixed with a few drops of sulphuric acid and subsequently cooled, is so readily attacked t h a t on the addition of bromine the temperature rises appreciably and i n the course of a few minutes the colour of the halogen may disappear,COMPOUNDS CONTAINING THE CARBONYL GROUP.41 Diethyl malonate was examined as a type of ester which is corn- paratively easily brominated. When this substance is mixed with purified bromine a t the ordinary temperature, no marked effect is noticeable, often during the course of some hours; in presence of a small quantity of hydrogen chloride, however, the action proceeds very rapidly, even if the temperature is kept low.A striking experiment may be made by mixing a few grams of the ester with an approximately equal bulk of bromine in the cold; R few drops of the mixture are warmed in a test-tube over a Bunsen burner, and when the resulting action is complete the fuming product is cooled and added to the bulk of the mixture; a violent reaction soon occurs, hydrogen bromide is evolved in large quantities, and the colour of the liquid changes from a deep brown to a very pale yellow, the change being usually complete in less than a minute. AS is well known, bromine scarcely acts on acetic acid even a t its boiling point, and it was found that, even when saturated with hydrogen chloride or bromide, this acid, when containing 1 or 2 per cent. of water, is only sIowIy attacked by the halogen at the temperature of the water- bath.lf, however, i t is repeatedly purified by freezing, it becomes easy to prepare bromoacetic acid, first by saturating the dry product with hydrogen chloride, and then by warming it at SO-90' with a slight excess of bromine: thus, from 33 grams of 99 per cent. acetic acid saturated with hydrogen chloride, a yield of 54 grams of bromo- acetic acid or 71 per cent. of the calculated amount was obtained after 9 hours' heating with bromine on the water-bath. In another experiment, 100 grams of the acid containing 95 per cent,. of pure acetic acid were mixed wit,h 22 grams of acetyl chloride for the purpose of removing water and affording simultaneously the requisite hydrogen chloride. After 43 grams of this mixture had been heated for 5 hours on the water-bath, the product was treated with successive quantities of bromine and distilled at the end of 6 hours; a yield of 83 grams of crystalline bromoacetic acid was thus obtained corresponding with about 85 per cent, of the calculated amount. The effect of chlorine on dry acetic acid is similar; in diffused day- light, acetic acid' saturated with hydrogen chloride was only slowly chlorinated at looo, but this is also the caBe when phosphorus is em- ployed, and t,he speed in the two cases appears to be very similar. It is probable, therefore, that in direct sunlight t'he yield by this process might be good and the action as rapid as in the ordinary method, but no opportunity was obtained of trying the reaction under these conditions. Acetic acid was chosen t o illustrate the case of acids.42 BOWACK AND LAPWORTH : The author is indebted to the Research Fund Committee of t,he Chemical Society for a Grant which defrayed some of the cost of the investigation. CHEMICAL DEPARTMENT, THE GOLDSMITHS’ INSTITUTE, NEW CROSS, S.E.

ISSN:0368-1645    

DOI:10.1039/CT9048500030

出版商:RSC    

年代:1904

数据来源: RSC

摘要:

42 BoWACK AND LAPWORTH : VI.-Derivatives of Menthyl Cyanoucetate. By DOUGLAS ANDERSON BOWACE and ARTHUR LAPWORTH. THE esters of acetoacetic, cyanoacetic, and malonic acids contain hydrogen atoms, which, although directly attached to carbon atoms, a1 8 easily replaced by sodium, and the resulting metallic derivatives, a t least in the case of the first two classes, appear to be derived from the enolic modifications of the esters. The stability of the enolic forms o f the free esters appears to vary considerably, and only in the case of the derivatives of the acetoacetates is there any direct evidence that a measurable amount of free enol is present when an equilibrium is attained. I n the hope of obtaining further evidence on this point, some optically active derivatives of cyanoacetic acid were prepared, with the view of determining whether they exhibited any measurable mutarotation, as this phenomenon is apparently always associated with change in molecular structure, and, moreover, was well marked in the cape of certain derivatives of menthyl acetoacetate (Trans., 1902,81, 1502, and 1903,83, 1117).The following investigation had been practically completed when a paper by Tschugaeff appeared (J. RW8. Phys. Chem. ~ o c . , 1902, 34, 6069),in wbich fhe rotatory power of menthyl cyanoacetate was given, SO that the first compound described in the present paper is not new. We have not been able to consult the original paper, but the rotatory power of the ester as given in an abstract (Abstr., 1903, ii, 1) agrees satisfactorily with the number we had previously obtained.Menthyl cyanoacetate does not appear to exhibit a trace of muta- rotation, even in presence of traces of bases or acids, agents which have been found t o accelerate this change whenever it occurs. The rotatory power of the monobromo-derivative in benzene, however, altered somewhat rapidly from [a], - 23.42' to [a], - 32.919 It was expected that if mutarotation occurred in any of the deriv- atives of this ester, it would probably be most readily detected in the azo-compounds, particularly as the a zo-derivatives of ment hy 1 aceto-DERIVATIVES OF MENTHY L CYANOACETATE. 43 acetate exhibited this property in an extraordinary degree (compare Trans., 1903, 83, 1117). Moreover, Weissbach (J. pr. Chern., 1903, [ii], 6’7, 395) has shown that ethyl phenylazocyanoacetate may be obtained in three different forms, two of which he regards a s stereo- isomeric azocyanoacetates, and the third as ethyl a-phenylhydrazone- cyanoacetate.No appreciable change in the rotatory powers of the menthyl esters, however, could be detected. It is worthy of note that the rotatory powers of- the azo-compounds described in the present paper, unlike those of menthyl acetoacetate (compare Trans., 1903, 83, 1117), are within the usual limits found for menthyl esters of ordinary carboxglic acids. Menthyl bromo- cyanoacetate, however, has initially an abnormally small rotatory power, which, a s in similar cases, may perhaps be due to the presence of the asymmetric carbon atom present in the acyl residue. EXPER I MENTAL.Menthy2 Cyamoacetata, CN.CH2*C0,*C,,H,,. Menthol (43 grams) and ethyl cyanoacetate (30 grams), mixed in a distilling flask connected with a condenser, are gently heated over a n Argand burner a t such a temperature that about one drop of alcohol per minute is collected, and the heating is continued until the theoretical amount of liquid has thus been obtained. The product is then submitted to fractional distillation under a pressure of about 30 mm., so as to remove the considerable amount of menthene which is always formed; when the temperature of the vapour has risen t o about 150°, the distillation is interrupted, and the residue, which partly solidifies on cooling, is triturated with alcohol and spread on porous earthenware, the solid being 6nally recrystallised from alcohol. 0.2018 gave 0,5167 CO, and 0.1726 I1,O.C = 69.8 ; H= 9.5. C,,II,,O,N requires C = 70.0 ; H = 9.4 per cent. The ester is somewhat readily soluble in most of the ordinary organic media, and crystallises from alcohol in well-defined, small prisms or Ant needles melting a t 83 -84O. In plane polarised light, the crystals show straight extinction, and the directions of greatest elasticity and length are coincident, the double refraction being strong. When melted between glass slips, the compound solidifies readily in very long, flat needles, crystallographically identical with those obtained from alcohol ; in these, the optic axial plane cuts the crystals longitudinally, and in some cases a bisectrix, probably the obtuse, of a figure of wide angle, emerges noimally to the field, so that the acute44 BOWACK AND LAPWORTH : bisectrix is probably emergent at the apices of the crystah.For the determination of the rotatory power, a solution of 0.5000 gram of the ester in benzene (25 c.c.) was examined in a 2 dm. t u b e ; the rotation observed was ay = - 3*25O, giving [.ID = - 81.15'; no altera- tion of this value was noticed after the lapse of some days, and no change was effected by the introduction of traces of piperidine or t richloroacetic acid. The rotatory power of menthyl cyanoacetate was given by Tschugaeff as [air, = -SO.7l0 (Zoc. cit.). Menth) bronzocyanoacetnte, CN*OHBr*C02.C,oHlo, was made by add- ing the requisite quantity of bromine t o a solution of menthyl cyano- acetate in chloroform, the product being allowed to remain until the reaction was complete, when it was shaken repeatedly with water, dried over calcium chloride and evaporated, the solid residue being then crystallised from alcohol.0-1908 gave 0.1176 AgBr. Br = 26.4. C,9H2002NBr requires Br = 26.5 per cent. The substance is somewhat readily soluble in chloroform, benzene, and glacial acetic acid, but more sparingly so in alcohol and light petroieum. It separates from alcohol in well-defined, small prisms, which in plane polarised light have straight extinction and strong double refraction, the directions of greatest length and elasticity being coincident ; when melted between glass slips, i t solidifies in masses of very small, ill-defined, flat needles. For the determination of the optical activity, a solution of 0.4056 gram of the compound dissolved in benzene (25 ex.) had a n initial rotation in a 2 dm.tube of a, = 0*76O, whence [.ID = - 23.42'. The value rose within half an hour t o [a]* = - 3 2 * 9 O , afterwards remaining constant at this point, Menthyl p- ToZyZaxocya rzoacetate, C H,*C,H,*N,* CH(C N)* GO,* C,,H,,. It was not found possible to obtain menthyl phenylazoaceto- acetate in a crystalline form, but the preparation of the corresponding p-tolylazo-compound presented little difficulty. Menthyl cyanoacetate was dissolved in a large quantity of warm alcohol containing a n excess of sodium acetate, and t o the well-cooled liquid was slowly added one molecular proportion of p-tolyldiazonium sulphate dissolved in the smallest possible quantity of water.After some hours, during which the mixture remained a t the temperature of the laboratory, the whole was poured into water and the deposited oil collected, washed repeatedly with water, and dissolved in an equal bulk of alcohol. After some weeks, the azo-compound was deposited i n large crystals, which were freed from adherent oil and recrystallised from alcohol.DERIVATIVES OF MENTHYL CYANOACETATE. 45 0.2120 gave 0.5467 CO, and 0.1509 H,O. C,,H,70,N, requires C = 70.4 ; H = 7.9 per cent. The compound dissolves readily in ether, ethyl acetate, acetic acid, chloroform, and benzene, but is much more sparingly soluble in alcohol and light petroleum. It separates very slowly from warm super- saturated solutions in alcohol i n the form of beautiful, large, trans- parent, yellow plates which melt a t 93-95'.When crushed fragments of the crystals are examined in cedar-wood oil in convergent polarised light, a biaxial interferencefigure of wide angle is occasionally noticeable. If, as is probable, the figures observed were those surrounding the acute bisectrix, the double refraction is positive in sign and strong. After melting between glass slips, the substance could not be made to resolidify. For the determination of the optical activity, a solution of 0.7543 gram of the compouud in benzene (50 c.c.) was examined in a 2 dm. tube. The rotation observed as a mean of several concordant readings was uD = - 1-62', whence [.ID = -53.7'. The rotatory power did not change after the solution had remained for several days ; the addition of piperidine, however, caused a n immediate alteration of the observed rotation by 0.04', but this new value was also constant, so that the change was probably not due t o mutarotation ; no effect was produced by the addition of trichloro- acetic acid.The azo-compound does not appear to Cissolve in cold 30 per cent. aqueous sodium hydroxide, even if very finely powdered, and i t com- municates no colour whatever t o the liquid; even if the alkali is added to the alcoholic solution of the substance, when the liquid is poured into water, the latter is found to be colourless after the pre- cipitate has settled. The corresponding ethyl ester dissolves somewhat readily in dilute alkali, and the difference in properties between the two esters is doubtless to be attributed to the very great relative difference between their solubilities in water rather than to any chemical dissimilarity (compare Trans., 1903, 83, 11 17).C=70.3; H=7.9. iVe?xth?/l p-.Bromo~~enylazoc?/unoacetate, Br*C,5H,*N,*CH( CN) CO,* 910H19. This compound was prepared by a method exactly similar to that used in making the foregoing compound. It crystallised readily when its alcoholic solution was sown with a trace of the cryntals of the corresponding p-tolyl compound. 0.2005 gave 0.4155 CO, and 0.1092 H,O. C=56*5 ; H=6.0. C:,,H,,O,N,Br requires C: -- 56.15 ; H = 5.9 per cent.46 HA" AND LAPWORTH: OPTICALLY ACTIVE ESTERS OF The substance closely resembles that just described in regard to it8 solubility in various media, but appears to be somewhat less readily soluble.It separates from warm alcohol in the form of magnificent, transparent, yellow prisms or thick plates which melt at 97-98'. Crystallographically, the description given of the p-tolyl compound applies equally well to the [present substance. Occasionally it was found that another form of the compound separated during the crystallisation from alcohol. This modification presented the appear- ance of very fine needles and melted somewhat indefinitely between 95' and 105'. The difference between the two forms, however, appears to be of a crystallographicd and not a chemical character, as the rotatory powers in both cases are constant and identical, and by seeding the supersaturated solution of the acicular modification with a trace of the other the whole may be converted into the transparent tables characteristic of the form melting at 97-98". For the determination of the rotatory power, ft solution containing 0.3450 gram dissolved in benzene (25 c.c.) was examined in a 2 dm. tube. The rotation observed was a,, = - 1-18', whence [a],, -- -42.75". The authors desire to express their thanks to the Research Fund Committee of the Chemical Society for a grant which defrayed part of the cost of the investigation. CHEMICAL DEPARTMENT, THE GOLDSMITHS' INSTITUTE, NEW CROSS, S.E.

ISSN:0368-1645    

DOI:10.1039/CT9048500042

出版商:RSC    

年代:1904

数据来源: RSC

摘要:

46 HA" AND LAPWORTH: OPTICALLY ACTIVE ESTERS OF V1I.--Opticatly Active Esters of p- Ketonic and b-Aldehydic Acids. P a r t J V. Condensaftion o f A Idehydes with Menth y 1 Ace toacetate. By ARCHIE CECIL OSBOHN HANN and ARTHUR LAPWORTH. THE only a-substituted derivatives of menthyl acetoacetate which have yet been described are the azo-compounds (Trans., 1903, 83, 1114), which have been isolated in a solid condition and found to exhibit mutarotation in a very marked degree. All attempts to prepare the ordicary a-alkyl substituted derivatives, on the other hand, h a w failed, probably because, as obtained by the ordinary methods, they are mixtures of fusible isomerides, that is to say, of the I-menthyl esters of the d- and 2-alkylacetoacetates. Many of the alkylidenediacetoacetates, however, may be isolated@-KETONIC AND &ALDEHYDIC ACIDS. PART IV.A7 without difficulty in crystalline and apparently homogeneous forms. The method used in preparing them was usually that employed by Knoevenagel (Annalen, 1894, 281, 25; 3 ~ . , 1894, 27, 2345, k c . ) , namely, by treating a mixture of the alkyl acetoacetate and an alde- hyde with an organic base as a condensing agent. This synthesis has been shown by its discoverer to proceed in two stages, in the first of which condensation takes place between one molecule of the aldehyde and one of the ester, yielding the unsaturated alkylidenemonaceto- acetate, CR:C(C02-Alk)*CO*CH,, whilst in the second stage the above product unites with another molecule of the original alkyl acetoacelate affording the alkylidenebisacetoacetate, having the constitution CHR<CH(Co~A1k)*Co'C~13 The mechanism of the process is gene- 2H(CO,Alk) * UO* CH,' rally supposed to consist in the initial formation of a compound of the aldehyde and the base which, i t is usually stated, may be a primary or secondary but not a tertiary base; this initial compound then reacts with the ketonic ester, as, for example: and Knoevenagel has isolated these supposed intermediate compounds and shown that they react with the acetoacetic esters 'in the manner represented in the foregoing equation (Bw., 1898,31, 2596).The assumption that the condensation depends on the formation of auch intermediate compounds is, however, entirely unnecessary, and the authors have found that, contrary to general belief, tertiary bases, if sufficiently powerful, are effective in bringing about the condensa- tion, and there can be little or no doubt that the efficiency of a base depends mainly on its strength; thus, whilst pyridine scarcely acts at all, trimethylamine and tripropylamine in small quantities give good results, although they are not by any means so rapid in their action as the secondary bases, which are more powerful.In this and similar cases, the real effect of the bases is doubtless precisely similar to that which they exercise in bringing about the rapid attainment of equilibrium between the normcll aud iso-forms of tautomeric compounds, and in acceleratiug the union of hydrogen cyanide with carbonJvl compounds, namely, by lo wering the concentra- tion of the hydrogen ions and thus increasing that of the negative ions of the acidic acetoacetic esters.The bases may be assumed to form small quantities of the ammonium derivatives exactly analogous to the metallic derivatives of the /3-diketones or @-ketonic esters. The subsequent change may then be represented in the ordinary way as48 HA" AND LAPWORTH: OPTICALLY ACTIVE ESTERS OF the result of the addition of this ammonium compound to the carbonyl group of the aldehyde or more satisfactorily, we think, as t h e union of one of the ions* of the acetoacetic ester with the carbonyl group of the aldehyde, to form a complex ion of the same type as that of the cyanohpdrins (Trans., 1903, 83, IOOO), followed by the union of these negative ions to form the bydroxyl compound (analogous to the cyanohydrins), which is generally recognised t o be the first step in condensations of the type ; thus with acetaldehyde and ethyl acetate, ++ CH,*66* CH<CO,Et CHMe.0 ft the latter compound then losing water to yield the unsaturated ester CH3*CO*C<C02Et.The condensation of the last-mentioned substance with another molecule of ethyl acetoacetate under the influence of bases, and by what is doubtless a very similar process, furnishes the bisacetoacetate, >CHMe . CHMe CH,-CO* CH*CO,Et CH,*CO*CK*CO,Et I n the condensations of ment hyl acetoacetate with aldehydes, the reactions appear to proceed more slowly than when the ethyl ester is used, and in many cases they are completed only after prolonged heating or by the addition of a small quantity of sodium hydroxide, which is very much more eflicient than the comparatively weak organic bases.* We have previously suggested (Trans., 1902, 81, 1612) as a modification of an ionic view of tautonieric chauge which wo supposed to have been advanced for the first tinie by Briihl (BET., 1899, 32, 2329), that the change of internal structure occurs only in the ions, as, for example, in the abovo case : Q-CH=CH O=C----CII I CH, (!!O,Et I f - f CH, C!02Et Briihl's paper, unfortunately, contained no reference to previous suggestious of a similar nature put forward by Knorr (Annalen, 1896, 293, 38) and by Wislicenus ( TuutonaeTie, Ahrens-Snminlung, 897, et scq.). The latter had assumed, also, that iouisation might precede isomeric change, pointiiig out that when this was the case the change of internal structure would take place " more readily " than when a n intramolecular atomic or group migration was also involved.Wislicenus thus anticipated a most important point; in the views which we have put forward; he does not, however, appear to suggest that the change in the ion is a reversible one and tending towards an equilibiium (compare, in this respect, Lander, Trans., 1903, 83, 420), or that the ketonic form itself may undergo ionisation. The statement of t h e above vizw iii terms of an hypothesis which does not po.ztulate ionisation becomes virtually identical with Lander's suggestion (Zoc. cit., p. 421) that the metallic derivatives exist in desmotropic forms.P-KETONIC AND P-ALDEHYDlC ACIDS.PART IV. 49 The intermediate unsaturated esters, unlike those from the ethyl ester, may be occasionally produced in large amount by working at the ordinary temperature, and there is no difficulty in thus obtaining excellent yields of menthyl benzylideneacetoacetate, CHPh:CAc*CO,*C,,H,, whilst i n the preparation of the corresponding ethyl ester the tempera- tiire must be maintained below - 5' for more than 20 hours. The same remark applies t o the condensation with propaldehyde, which at the ordinary temperature yields first the crystalline menthyl propyl- ideneace toace t ate, CHEt CAc*CO2*CloHg, a1 though none of the corre- sponding derivatives of ethyl acetoacetate with fatty aldehydes appear to be obtainable in a similar may. The want, of success experi- enced in attempting to prepare other examples of these intermediate compounds is probably attributable to the failure of the substances to crystallise in t h e absence of suitable nuclei before they undergo further condensation.It is noticeable with nearly all the compounds dealt with that they crystallise with extreme sluggishness, this being a characteristic of the derivatives of menthyl acetoacetate which has already been mentioned on more than one occasion (Trans., 1902, 81, 1500, and 1903, 83, 11 17). To this property also is doubtless due the failure which has attended all efforts to prepare crystalline condensa- tion products from menthyl acetoacetate and formaldehyde. It is not our intention to discuss the moot question of the propriety of re- presenting some of the al kylidenebisacetoacetates as derivatives of cyclohexanone, a contention which appears to involve the improbable assumption that the esters are more stable under the influence of hydr- azine hydrate than under that of the trace of weak base which is usually employed in preparing them (compare Rabe and Eke, Annalen, 1902, 323, 83, and Knoevenagel, Rer., 1903, 36, 2118).Moreover, the point hasno very direct bearing on the interpretation of any of our observations. The menthyl esters of the alkylideneacetoacetic acids were not found to exhibit any very noteworthy mutarotation either in solvents or in the presence of traces of bases or acids. It is difficult to explain the reason for this apparent stability, more particularly as the specific rotatory powers of these esters are abnormally low, being in many cases not more than one-fourth of the value calculated from the observations of other workers on menthyl esters (Tschugaeff, J.Iluss. Phys. Chem. Soc., 1902, 34, 6069, and Cohen and Briggs, Trans., 1903, 83, 1213). I n the absence of all other data, the ab- normally low rotatory powers might have been reasonably attributed to the presence of an asymmetric carbon atom which originates in the acidic part of the molecule during the synthesis (compare Trans., 1903,83, l l l S ) , but the absence of any large amount of mutarotation, VOL. LXXXV. E50 HANN AND LAPWORTH: OPTICALLY ACTIVE ESTERS OF such as was observed in the case of the azo-derivatives of menthyl acetoacetate, is difficult t o recloncile with such a view, Still more diacult to understand are the rotatory powers of the intermediate unsaturated alkylideneacetoacetates, which, if correctly represented by the formula CHR: CAc*CO,*C,,H,,, contain no centre of asymmetry except that i n the menthyl residue, nor, apart from the latter, is the molecule built up in an enantiomorphous way.Never- theless, the rotatory powers of menthyl propylideneacotoacetnte, C HE t : CAc CO2*CloKl9, and benz ylideneacetoacetat e, CHPh:CAc*CO,*C,,H,,, have the molecular rotations [MI, - 97.70" and - 32*80°, numbers which are respectively about two-thirds and one-fifth of the lowest usual values for the menthyl esters of monobasic acids, or, t o look at the matter in another way, the latter of the two substances mentioned is apparently only the acetyl derivative of menthyl crotonate, CHPh: CH*CO,* CIOHlD, which has a rotatory power of about the normal value, namely, [M],-203.1° (Annalen, 1903, 327, 157).I n view of these observa- tions, Erlenmeyer may after all be corre.ct in attributing an enantio- morphous character to one of the cinnamic acids (Ber., 1903, 36, 2340. Compare also Sudborough and Thompson, Trans., 1903, 83, 1167). The possibility still remain?, however, that they may be re- ?---SMe , as, me believe, has already CHPh*C*CO,Et presented by the formula been suggested by Claisen. E X PER I M E N T AL. ll.ieth?jlene D e r i v a t i v e s . When molecular proportions of menthyl acetoacetate and form- aldehyde, together with a few drops of piperidine, are allowed to remain for about twenty-four hours, condensation occurs with rise of temperature, water separates, and a colourless oil is obtained, which solidifies in the course of a few days.All attempts to obtain this substance in the crystalline form have been unsuccessful. EthyEidene D e y i u a t i v e s . Numerous attempts were made to prepare menthyl ethylideneaceto- acetate by condensing menthyl acetoacetate with aldehyde in alcoholic solution, but without success. The conditions were varied by using excess of the aldehyde and by keeping the mixture at 0' or - loo; in each case, however, the dimenthyl ester alone was formed.@-KETONIC AND ,@-ALDEHYDIC ACIDS. PART IV. 51 CH3*CO*~H*C02*Cl,,H,, CH;CO*CH*CO2~ Cl,H,, Dimenthyl Ethylidenebisucetoacetate, CK,*F K This compound is best prepared by mixing two molecular propor.tions of the ester with one of acetaldehyde in alcoholic solution, a few drops of piperidine, die thylamine, or tripropylamine being added a t intervals. The oily liquid is then warmed on the water-bath for two or three days, by which time it has assumed a jelly-like consis- tence, and contains the condensation product in the form of excessively slender needles. The mother liquors from these crystals on treatment with a drop of strong aqueous sodium hydroxido furnish an additional supply of material. Some difficulty was experienced i n obtaining tbe substance in a satisfactory condition ; it was eventually found preferable to dry the compound thoroughly on a porous plate, then to dissolve i t in cold dry benzene and precipitate with light petroleum. 0.1969 gave 0.5120 CO, and 0.1745 H20.C,,H,,O, requires C = 71.1 ; H = 9.8 per cent. The compound is very readily soluble in all the usual media with the exception of water and light petroleum; it is obtained from a mixture of benzene and light petroleum in very slender, but well- formed, needles melting at 194-196'. The crystals have a weak double refraction ; the extinction direction in polarised light is straight, and the directions of greatest elasticity and length are coincident.. A solution of 0.4001 gram of the substance in 25 C.C. of benzene gave [all) = - 24*9", changing to - 26.5' on the third day. Experiments were also made in order to determine whether the rotatory power was altered by the addition of a trace of a base as an accelerator.For this purpose, an approximately one per cent. benzene solution was divided between two 2-dcm. tubes, and a trace of piperidine added to one ; the rotation in both cases, however, gave the same value, no mutarotation being observed during twenty-four hours. C = 70.9 ; H = 9.8. P r o p y l i d e n e D e r i v a t i v e s . Menthpl Propylideneacetoacetate, CH3*CH,CH:C(CO*CH3)*C02*CloH,, For the preparation of this compound, menthyl acetoacetate and propaldehyde in equivalent proportions were condensed with three or four drops of piperidine at the ordinary temperature. On the follow- ing day, the mixture-formed a viscid, oily liquid containing drops of water, and was induced t o solidify by the addition of a single drop of E 252 HANN AND LAPWORTH: OPTICALLY ACTWE ESTERS OF concentrated aqueous sodium hydroxide, the flask containing the liquid being shaken vigorously from time to time.Condensation was also effected by allowing the reaction mixture t o remain for some hours at 0'. I n one experiment, two molecular proportions of menthyl aceto- acetate were condensed with one of propaldehyde, the mono-menthyl ester being again formed. Another batch, prepared under the same conditions, yielded a compound melting a t about 200°, which was subse- quently shown t o be the men thy1 propylidenebisacetoacetate. Further condensations, however, whether effected with one or two molecular proportions of the menthyl ester only gave the unsaturated compound, the temperature a t which the reaction proceeded being, apparently, immaterial, 0.2033 gav? 0.5430 CO, and 0,1843 H,O.ClpH,,O, requires C = 72.8 ; H = 10.0 per cent. The substance is easily soluble in benzene, chloroform, ether, or acetone, and when recrystallised from hot alcohol is obtained in the form of plates meltiiig a t 84-SSO. Conclusive evidence as to the nature of the compound under exam- ination was afforded by its behaviour with warm sodium hydroxide solution, as a powerful odour of propaldehyde was evolved, and this decomposition is characteristic of the unsaturated ,alkylidene aceto- acetates. The crystals are rectangular, apparently orthorhombic plates which have straight extinction, the direction of greatest elasticity and length being coincident. The double refraction is strong. After melting between glass slips, this substance solidifies rapidly to fan-shaped masses which show aggregate extinction.Under the high power in convergent polarised light, the bisectrix of an interference figure of wide angle may be distinguished occasionally. The double refraction is positive, and the axial plane cuts the crystals in the directions of their greatest length. The action of the substance on polarised light was investigated, 0.3980 gram being dissolved in benzene and made up to 25 c.c.; with this solution,a rotation corresponding with [ = - 34.9' was obtained, and no alteration of this value was observed. C = 72.8 ; H = 10.0. CH,*CO* FH*CO,-C,,H,g CH,.CO* UH*CO,*CloH,g Dimenthyl Propylidenebiscccetocccetate, CH,.CH,* QH This ester is obtained by condensing the monomenthyl derivative with about an equal weight of menthyl acetoacetate and a few drops of piperidine and alcohol.The reaction i s considerably hastened by&KETONIC AND @-ALDEHYDIC ACIDS. PART IV. 53 warming on the water-bath, a viscid, oily liquid being obtained, which, on cooling, usually became almost solid in fifteen minutes. 0.1976 gave 0.5183 CO, and 0.1797 H,O. C = 71.5 ; H = 10.0. C,,H,,O, requires C = 71.5 ; H = 10.0 per cent. The substance is easily soluble in benzene, chloroform, or hot ethyl acetate; very sparingly so in ether or light petroleum, and is almost insoluble in alcohol. On recry stallisation from acetone, it melts at 20 1-207'. The crystallographic characters of the compound are precisely similar to those of dimenthyl ethylidenebisacetoacetate. A solution of 0.1301 gram in 25 C.C.of benzene had a constant rotation of [.ID = - 26.9'. Solutions in benzene in presence of a trace of piperidine were also observed in the polarimeter, but even here no mutarotation could be detected. N o r m a 2 B u t y l i d e l n e B e y i v a t i s e s . All attempts to prepare menthyl n-butylidenecccetoacetate were un- successful, the more complex ester being formed in each case, CH,*C0*~H*CO2*CloH,, Dinaenthy I n-But y Eidenebisacetoacet ate , CH,* CH 2* C €3,. VH This substance is prepared by mixing n-butaldehyde with a molecular proportion of the menthyl ester in presence of a few drops of piperidine. The mixture soon forms an oily liquid at the ordinary temperature, and the product is obtained in the solid condition by the addition of alcohol and a small quantity of aqueous sodium hydroxide.0,2023 gave 0.5339 CO, and 0.1853 H,O. C,,H,,06 requires C = 71.9 ; H = 10.1 per cent. The compound separates from ethyl acetate in fine needles melting a t 184'; it is easily soluble in ether, benzene, and chloroform, less so in alcohol, acetone, and light petroleum. Crystallographically, i t appears to be similar to the corresponding ethylideno derivative. A solution of O.lS57 gram in 25 C.C. of benzene gives [ When this substance is treated in chloroform solution with hydrogen chloride, a viscid mass is obtained on evaporating the solvent ; on triturating the substance with light petroleum and allowing the mixture to remain for some days, crystals are obtained melting a t 136*5-137*5*, but this material was formed in such small quantity that it could not be subjected to detailed examination.C = 71-9 ; H = 10.1. = - 16-8954 HANN AND LAPWORTH: OPTICALLY ACTIVE ESTERS OF isoB u t y I id e ne D e l * i u a t i v e s . CH,*CO*QH* CO,*C,,H,, C H,* GO* CH* CO,* C,,H,, Dimenthyl isoButylidenehisacetocicetate, CH( CH,),* Q H This compound is obtained under conditions similar to those employed i n the foregoing case, the addition of a drop of con- centrated sodium hydroxide solution being used to hasten the con- densa tion. 0.1647 gave 0.4331 CO, and 0-1500 H,O. C3,HS406 requires C = 71 09 ; H = 10.1 per cent. The substance crystallises from ethyl acetate in needles, which soften a t 193' and melt completely at 202'. The ester is fairly soluble in the usual organic media ; its crystals are slender needles, like those of the other alkylidenebisacetoacetates, but are always con- siderably larger and apparently somewhat better defined.A benzene solution of 0-2933 gram of the substance made up t o 25 C.C. gave [aID = - 42.6' ; here a slight mutarotation was observed, the rotatory power assuming a constant value of [a]* = - 46.0' a t the end of a week. C=71*71 ; H= 10.1. Belnxy l i d ene De!rivat i v e s . Menthy1 Benxylideneacetoacetate, C,H,* CH: C( CO* CH,) C02*C1,H,9. A mixture of menthyl acetoacetate and benzaldehyde in molecular proportion, together with a few drops of piperidine, was allowed to remain at the ordinary temperature for about 24 hours ; a cloudiness, due to the separation of water, was noticed at the end of an how, and a semi-solid mass was finally obtained.The crystalline substance which separated was freed from the remaining oil by filtration under pressure, and was then dried on a porous plate and recrystallised from hot spirit. 0.1960 gave 0.5491 CO, and 0.1487 H,O. C,,H,,O, requires C = 76.8 ; H = 8.5 per cent. The compound is easily soluble in the usual organic media, although but sparingly so in light petroleum; i t separates from alcohol in flattened, colourless needles, and melts sharply at 133- 134'. The crystals are well-formed, flat needles, or six-sided, elongated plates, which have straight extinction and are probably orthorhombic. The directions of greatest elasticity and length are coincident ; the double refraction is moderate.When melted on a glass slip beneath C = 76.4 ; H=8.4.B-KETONIC AND BB- ALDEHYDIC ACIDS. PART IV. 55 a cover-glass and then cooled, the compound solidifies fairly quickly in radiate masses of slender, flat needles, which are only distinguish- able under a high power. A. solution of 0.3995 gram of the substance in 25 C.C. of benzene gave [.ID = - 10*Oo, no alteration in this value being noticed during three days. CB,*CO*~H* CO,* C,,B,9 CH,* CO CH* GO,* CloH13 Dimenthy1 Renxytidenebisncetoacetale, C,H,*PH This ester was obtained by condensing the benzylidene compound with one molecular proportion of menthyl acetoacetate in presence of a small quantity of alcohol and a few drops of piperidine; the mixture, when warmed on the water-bath, became considerably more viscous, and at the end of 12 hours was semi-solid and translucent.The product showed a great tendency t o separate as a jelly from benzene, acetone, or ethyl acetate, but was obtained in the crystalline form by adding an equal bulk of light petroleum to i t s solution in cold chloro- form ; fine needles separated when the liquid evaporated at the ordinary tern perature. 0.2077 gave 0.5612 CO, and 0.1720 H,O. CS5H5206 requires C = 73.9 ; H = 9.2 per cent. The compound is very sparingly soluble in alcohol, ether, and light petroleum, but dissolves fairly readily in benzene, acetone, or ethyl acetate. Crystallo- graphically, the substance resembles the corresponding ethylidene derivative. A solution of 0,1437 gram in benzene made up to 25 C.C. and observed in a 2-dcm.tube gave a valiie €or [a],, = - 30.4". C = '73.7 ; H = 9.2. I t softens a t 203' and melts completely at 206'. Addsndzbm.-Tt has been mentioned in the preceding pages t h a t not only alkaline hydroxides and powerful primary and secondary organic bases, but also tertiary bases bring about the condensation of aldehydes with menthyl acetoacetate. This is found to be equally true with ethyl acetoacetate, as the following observations show. When ethyl acetoacetate and 40 per cent. formaldehyde are mixed with pyridine even in fairly large quantity, no noticeable rise of temper- ature occurs, and condensation does not appear to take place even after some weeks at the ordinary temperature. If, however, two or three drops of concentrated trimethylamine solution or pure tripropylamine are added to 5 C.C. of the mixture, the temperature rises very rapidly, and in a few minutes water separates; in fact, these bases act much in the same way as does diethylamine, brit considerably less rapidly weight for weight. As the products were liquid in the foregoing case,56 PERKIN AND PHIPPS: NOTES ON SOME a similar experiment was performed with a mixture of acetaldehyde (1 mol.) and ethyl acetoacetate (2 mols.) ; with 10 C.C. of such a mixture, 5 C.C. of pyridine produced no appreciable effect, but 20 drops of tripropylamine caused the separation of water within a few minutes a t the ordinary temperature, and after three days the mixture solidi- fied t o a mass of crystals identical with those obtained by using piperidine or dietbylamine in small quantities. On adding 8 grams of tripropylnmine t o R iriixture of 5 . 3 grams of bbnzaldehyde arid 14 grains of ethyl acetoacetate, both freshly distilled, a marked iise in temperature occurred at once, and after five days at the ordinary temperature the whole had solidified to a crystalline mass of cliethyl benzylidenebisacetoacetate. We are indebted t o the Research Fund Committee of the Chemical Society for a grant which defi-nj-ed a large part of the cost of this itivestigation. C' 11 1 7 3 1 I ~ & L DE PAIL'L'AL EKT, Go m s ~ i 1 ~ ~ s ' I KST rrurr IC, NKW CIL:)Ys, S.E.

ISSN:0368-1645    

DOI:10.1039/CT9048500046

出版商:RSC    

年代:1904

数据来源: RSC

摘要:

56 PERKIN AND PHIPPS: NOTES ON SOME By ARTHUR GEORGE PERKIN, F.R.S., and SAMUEL Prrr~rs. TIIIS investigation contains an account of the yellow colouring matters which are present in the flowers of I’mnus spinosa and the Japanese dyestuff ‘; Fukugi,” 1,ogether with some results which have been obtained during the further study of morin, myricetin, hesperitin, and curcumin. T h f e C o Z o u ~ i ~ t g A f u t t e ? - of t h e FZoweys of 2jrunu.s S 21 i 12. 0 S C(. Some years ago, while examining t h e dyeing properties of certain natural products, it was noted t h a t some quantity of yellow colouring matter exists as a gluooside in the flowers of Yrzcnus spinoscc or common blackthorn, A cursory examination carried out at the time resulted in the isolation 05 a product which was apparently a mixture, because its acetyl derivative did not melt sharply, the meltingpoint beingNATURAL COLOURING MATTERS.57 very low for this class of substance. The attempts then made to effect a separation were not successful, but more recently, i n t h e hope t h a t a new colouriag matter might be present, the subject has been again investigated, and the difficulty overcome in an exceedingly simplo manner. I n order t o facilitate the work, an extract of these flowers prepared by Merck of Darmstadt was chiefly employed. Two hundred grams of the extract dissolved in 2 litres of water were treated with 50 C.C. of hydrochloric acid, boiled for three hours, and, after cooling, extracted with etber to remove the colouring matter, which was thus obtahed as a brownish-yellow, crystalline mass (3.5 grams).This was purified by two or three crystallisations from dilute alcohol, and a portion then converted into the acetyl compound in order t o determine whether its melting point coincided with that of the corresponding derivative of some known substance of this class. It mas found t o melt somewhat indefinitely a t 133--134", and gave on analysis C = 60.09 ; H = 4.28, these figures indicating that i t was most probably a mixture. The main bulk of the colouring matter was now dissolved in a small quantity of boiling acetic acid, arid the crystals which separated on cooling were collected and recrystallised from the same solvent until no alteration in the melting point could be observed ; the yield was 0.S gram.Found C = 62.93 ; IT = 3.89. C,,H,,O, require:; C = 62.94 ; K = 3.49 per cent. The substance, which coiisisted of pale yellow, glistening leaflets melting a t 276', dissolved in dilute aqueous alkalis with a pale yellow c 010 rat i o ti. The ucetp? compound crj stallised from methyl alcohol in colourless needles which melted at about 116", resolidified at a higher tempera- ture, and melted again at lS1-182'. Found C = 60.77 ; 3 = 3.97. C',,HG06(C1,H,0), reqiiires C: = 60.79 ; H = 3.96 per cent. On fusing the colouriug matter with caustic alkali, phloroglucinol (m. p. 210') and p-hydroxybenzoic acid (m. p. 208--210°) were obtained. These facts, together with an examination of i t s dyeing properties, indicated without doubt that this colouring matter was kampherol.As this dyestuff has recently been found in at least four other plants, it is likely t o occur in many other vegetable species. The acetic acid mother liquors from which the kampherol had separated mere allowed to absorb moisture by exposure to the58 PERKIN AND PHtPPS: NOTES ON SOME atmosphere, which caused the deposition of a small quantity of a mixture of a kampherol and a second substance. This precipitate was removed, the filtrate treated with a small quantity of hot water, and the yellow precipitate, which slowly separated, was collected and purified by conversion into its cccetyl derivative. Found C = 58.67 ; H = 4.26. C1,H,O7(C,H,O), requires C = 58-59 ; H = 3.90 per cent. This substance, which melted a t 191°, was decomposed with acid in the usual manner, and the regenerated colouring matter crystallised from dilute alcohol.Found C = 59-56 ; H = 3.61. U,,U1,O7 requires C = 59.60 ; H = 3.31 per cent,. It formed glistening yellow needles soluble in alkali solutions with a yellow coloration ; on fusion with caustic pchash, it gave phloroglucinol (m. p. 210”) and protocatechuic acid (m. p. 193-195’). It was evidently quercetin, and to this colouring matter and kampherol the dyeing property of these flowers is evidently due. A cursory examination of the flowers of the violet (VioZcc odoratn) and the white clover (Trzj’olium repens) by a method similar to that employed above indicated in each case the presence of puercetin in the form of a glucoside. This colouring matter was recognised by the melting point of its acetyl derivative, and its decomposition products with caustic alkali, and in consequence of these observations a fuller investigation appeared unnecessary.The Japanese D y e s t u f f “Pukugi.” We are indebted to the kindness of Professor E. Yoshitake, of Tokio, for this material, wbich consists of the wood of a tree, and was obtained in the form of an almost colourless, coarse powder; it appears, a t least until recently, to have been employed to a considerable extent as a yellow mordant dyestuff, principally in the form of extract. A preparation of this kind was also procured and consisted of brittle, rectangular cakes (4” x 2y x ly) of a yellowish-brown colour, which weighe 1 approximately 410 grams. The coarsely powdered extract, dissolved in ten times its weight of water, was boiled with 100 C.C.of hydrochloric acid for two hours i n order to decompose the glucoside. A somewhat viscous precipitate of the impure colouring matter thus separated, which, when cold, was washed by decantation, drained on a tile, and allowed- to dry a t the ordinaryNATURAI, COLOURING MATTERS. 59 temperature. The product was extracted with boiling alcohol, the extract evaporated and poured into a large bulk of ether, which caused the separation of a resinous impurity, and on evaporating the ethereal liquid the colouring matter now obtained was of a much lighter colour. For further purification, it was dissolved in boiling alcohol containing a trace of acetic acid, lead acetate solution added, the resulting yellow precipitate removed, the filtrate evaporated to a small bulk and poured into ether.The pale yellow, etherealliquid was well washed with water, evaporated to dryness, and the viscid residue left for some days. Minute crystals slowly separated, which were col- lected, washed with a small amount of ether, and crystallised first from dilute ethyl alcohol and then from methyl alcohol until the melt- ing point was constant. The product frequently contained a trace of the lead compound, which adhered somewhat tenaciously, and was best removed by means of ether, i n which it dissolved with difficulty. Found, (i) C = 66.03 ; H = 6.04. (ii) C = 65.17 ; H = 3.97. Cl7H,,O, requires C = 65.3’7 ; H = 3.84 per cent. It consisted of a mass of minute, prismatic, canary-yellow needles, which melted at 288 - 2 9 0 O .When crystallised from dilute alcohol, the air-dried product contains one and a half molecules of %water of crys talli sation. Found, H20 = 7.56. This new colouring matter, for which the name fuhgetin is proposed, is readily soluble in hot alcohol arid dissolves in aqueous alkalis or in cold sulphuric acid with a pale yellow coloration. The solution in t h e latter solvfent, on heating, becomes dull violet-red, and finally assumes an orange-brown tint, and,on dilution with water, now deposits a brown, amorphous precipitate soluble in aqueous alkalis to a dull red solution. With lead acetate in alcoholic solution, an orange-yellow precipitate is formed, whilst alcoholic ferric chloride develops a brownish-black coloration; on the other hand, alcoholic potassium acetate gives no insoluble salt, and mineral acids do not react to form the usual com- pounds.When examined by Zeisel’s method, it was found to contain no methoxyl groups. Fukugetin readily dyes mordanted fabrics, and it was at once ob- served that the shades produced were almost identical, except as regards the iron mordanted portion, with those given by luteolin. C,,H2,0,2,3H20 requires H,O = 7-35 per cent. Cr. 81. sn. Fe. Fukugetin. Dull orange-yellow. Orange-yellow. Bright yellow. Olive-brown. Luteolin. Brown orange-yellow. 9 ) > ? 0 live-black.60 PERKIN AND PHIPPS: NOTES ON SOME Crystalline acetyl and benzoyl derivatives of this new colouring matter could unfortunately not be obtained either by the usual pro- ceses or by the pyridine method, Methylation also led to the formation of a viscous product, although i t is possible that these difficulties might have been surmounted if a larger quantity of substance had been available for experiment.Bromine Compozcnd.-One gram of fukugetin was added to a solu- tion of one gram of bromine in a little glacial acetic acid. After twenty-four hours, the product was drained on porous tile, ground u p with a small amount of acetic acid, filtered a t the pump, washed once or twice with acetic acid, and purified by crystnllisation From nitro- benzene, two or three drops of acetic acid being added t o the solution when cooling. Two distinct preparations were made. C,7Hlo0,Br, requires C = 43.22 ; H = 2.54. Found, (i) C = 43.47 ; H = 2.43. Bibromofickugeti?a forms minute, flat needles melting at 280°, readily soluble in hot alcohol, more sparingly so in acetic acid.On fusion with alkaii in the usual manner, fukugetin gave protocatechuic acid (m. p. 194-196") and phloroglucinol (m. p. The above results are, unfortunately, too meagre to allow of the prediction of the constitution of this substance with any certainty, but the similarity of most of the general properties of the compound with those of luteolin, and the fact that it contains similar nuclei, point to the probable close relationship between these colouring matters. Interesting in this respect is the stability of alkaline solu- tions of fukugetin when exposed t o the air, for these do not undergo oxidation even after many days. This property, as showh i n former investigations, is somewhat characteristic of flitvone compoundd such a s apigenin and luteolia, but is not possessed by flavanol derivatives, of which fisetin and quercetin may be yuoted as examples.It is possible that the distinction between luteolin and fukugetin consists chiefly in the manner by which the catechol nucleus is connected with the pyrone ring, and one or two formul~e suggest themselves as very probable representatives of this colouring matter, It is intended, should a further supply of raw material be forthcoming, to continue these experiments in the hope of elucidating with certainty the con- stitution of this interesting substance. An examination of the dyeing properties of " fukugi " showed, as was to be expected, that it behaved in this respect in a n analogous manner t o weld (Reseda Zuteola).The similarity in shade was so marked that, except in point of strength-for fukugi is a stronger dye than weld- (ii) C = 43.53 ; H = 1.95. 2 10").NATURAT, C!OIiOUHIN G MATTERS. 61 i t is impossible to distingukh between them, and there can be little doubt that prior to the introduction of the synthetical colouring matters this dyestuff would have been a valuable addition to those already in use. E t h y l a t i o n 0 f *MoI.in. Although quercetin and other members of the flavanol class readily give, on alkylation, well-defined crystalline substances, morin has only yielded a methyl ether in a stBate of purity (Trans., 1896, 29, i92), for on ethylation in the usual manner, viscous products result which have hitherto refused to crystallise.As it seemed possible that the impurities might be more readily removed after acetylation, the residue from former experiments carried out some years ago was treated in the following manner. The resinous mass was digested with boiling acetic anhydride for some hours, the solution evaporated to a small bulk, and diluted with about twice its volume of methylated spirit. After several days, a small quantity of crystalline matter separated, and the mixture was now set aside for some weeks; the product was then collected, crystallised two or three times from methyl alcohol, and thus obtained in colourless needles, readily soluble in hot alcohol and melting a t 121-1 23". Found, C = 65.70 ; H = 6.23. C,,H,O,(OEt),~C,H,O requires C = 65.78 ; H = 6.06 per cent.To prepare the free tetraethyl ether, the acetyl compound was digested with boiling alcoholic potassium acetate, the solution poured into a small quantity of dilute hydrochloric acid and the product crystallised from methyl alcohol. Found, C = 66.50 ; H = 6-63. C,,H,O,(OEt), requires C = 66.65 ; H = 6.28 per cent. Morin teti-aethyl ether forms pale yellow, prismatic needles, sparingly soluble in cold methyl alcohol, and melting a t 126-128'. I n general properties, it closely resembles the tetramethyl ether previously described (Zoc. cit.).62 PERKIN AND PHIPPS: NOTES ON SOME The B r o m i n a t i o a of M y r i c e t i n in t h e presemce of A 2 ~ 0 7 ~ 0 2 . A most interesting property of morin, C,,H,,,O7, the colouring matter of old fustic, is that when brominated in the presence of alcohol i t yields tetrabromomorin ethyl ether, C1, H,0GBr4*0 Et..This peculiar behaviour, which is apparently not possessed by other flavanol derivatives, is considered by Herzig (Monutsh., 1897, 18, 700) to render doubtful the constitution assigned to it by one of the authors (Trans., 1896, 29, 792). Being in possession of a small quantity of myricetin, which is apparently a flavanol derivative capable of yielding a tetrabromo- compound (Trans., 1896, 69, 1287), the authors have studied its behaviour in these circumstances. Myricetin (1.9 grams) in 20 C.C. of alcohol was treated with 3.4 grams of bromine and the mixture left for forty-eight hours, when on cnutiously diluting with water a small quantity of crystalline precipitate gradually separated and was recognised as tetrabrorno- myricetin (loc.c i t . ) ; this was removed after some hours, the filtrate treated with a large volume of water, and a second deposit collected and crystallised two o r three times from dilute alcohol. Found, C = 31.29 ; H = 1.68 ; Et = 4.36. Cl,H,0,Br4Et requires C = 50.81 ; H = 1.51 ; Et = 4.38 per cent. Tetrcdwomornyricetin ethyl ether formed colourless needles very soluble in alcohol; it becomes red a t l l O o , commences t o sinter at 132O, and melt!, with decomposition at 146". This melting point is given with reserve, owing to the possibilit,y that a trace of tetrabrorno- myricetin itself may be associated w i t h the product. The lack of raw material did not permit of further experiment, but the result indicates t h a t in these circumstances myricetin behaves in an analogous manner t o morin, though somewhat less readily.The M o l e c u l a r W e i y h t s of l l e s p e i a i t i a a n d Curcumin. In a previous communication (Trans., 1898, 31, 1031), it was shown that the properties of hesperitin were in accord with the constitution OH *C,H,( OC H3) CH: C H CO *O C,H,( OH),, previously indicated by Hoffmann (Ber., 1876, 9, 685) and Tiemann and Will (ibid., 1881, 14, 848). The fact, however, that this substance gave well-defined crystalline salts having the f ormulze (C16H1406)2C2H302K andNATURAL COLOURINQ MATTERS. 63 C,,H270,,K suggested that its molecular weight was C32H28012, or twice that assigned to it by these authors.More recently it was shown (Trans., 1903, 88, 127) that certain substances, the molecular weights of which were well known, also gave somewhat peculiar salts by similar methods. Thus from gallaceto- phenone, C,H,O,, the salt C,,H,,O,,K, and from daphnetin, C,H,O,, the salt C,,HllO,K resulted, 2nd other cases might be cited. It was accordingly evident that these salts do not in all cases furnish trust- worthy indications of the molecular weight, and cryoscopic experiments were therefcre carried out, advantage being taken of the ready solubility of acetylhesperitin in naphthalene. 0.3351 in 13.90 naphthalene gave At - 0,375'. 0.4310 ,, 13.S7 naphthalene gave At - 0.490". Found, 15 = 449. Found, M= 443. C,,H,,O,(C,H,O), requires M = 428. It is consequently evident that the molecular weight of hesperitin is represented by the formula C,,H,,O,, and that the above-mentioned potassium and sodium salts belong t o the class of '' semi-substituted " compounds (Zoc.cit.). It has been shown by Ciamician and Silber (Ber., 1897, 30, 192) that the molecular weight of curcumin is most probably represented as C2,H2,,06 rather than C,,H,,O,, the formula originally assigned to i t by Jackson and Menke (Amer. Chem. J, 1882, 4, 77). Analyses of i t s mono-potassium salt (Zoc. cit.), although agreeing approximately with the formula CzlH,,O6E, were not completely satisfactory, owing to the difficulty of purifying this somewhat soluble compound. It therefore appeared interesting t o confirm these results, if possible, by the cryoscopic method, for which purpose a benzoylcurcumin would probably be suitable.This derivative was readily prepared by treating 2 grams of cur- cumin dissolved in 30 grams of pyridine with 23 grams of benzoyl chloride. The product was washed with water, the viscous residue dissolved in alcohol, and the crystals, which gradually separated, were purified by cry stallisation from a mixtnre of this solvent and benzene. Pound, C = 73-87 ; €1 = 4.48. C,,H,i0,(C7H,0)3 requires C: = 76.11 ; H = 4.70 per cent. BenzoyZcurctmin consists of fine, lemon-yellow needles melting at 0.3256 in 13.23 naphthalene gave At - 0.25c. These results therefore indicate that the molecular weight assigned 176-1 78". Found, M = 688. C2,Hlp0,(C'7H,0), requires M = 680.64 NOTES ON SOME NATURAL COLOUHING MATTERS.t o curcumin by Ciamician and Silber is correct, and poiut to the fact that this colouring matter contains three hydroxyl groups, although only two have hitherto been suspected. Curcumin itself is somewhat soluble in naphthalene, but apparently not sufficiently so for molecular weight determination ; the cryoscopic experiments gave 31 = 429, whereas the formula C,lH,,O, requires M = 368. The isolation of curcumin from turmeric is a t best a tedious opera- tion, and as the yields obtained by the published methods were not satisfactory, the following process was adopted. An alcoholic ( xtract of turmeric was treated with lead acetate solu- tion (Daube, Ber., 1870, 3, 709), and the precipitated lead compound of the colouring matter collected, thoroughly washed with alcohol, and then with water. The product suspended in warm water was decomposed with dilute sulphuric acid, and the resulting mixture of curcumin and lead sulphate well washed, drained on porous tile, and extracted with boiling alcohol. After concentration, the extract was poured into ether, the solution decanted from tarry matter, evaporated to a small bulk, and diluted with carbon disulphide. The mixture, when left exposed t o the a i r at the ordinary temperature, gradually deposited crystals, which were collected from time t o time, and i n this way a yield of approximately 0.56 per cent. of curcumin mas isolated from the sample of root employed. Little or no loss should occur by this process, and the mother liquors contain only a, trace of the so-called turmeric resin. The authors express their thanks t o the Research Fund Committee of the Chemical Society for a grant, which has been partly employed to cover the expenses of this research. CLOTH w ORKERS’ RESE AIKX L ABO ILATO ii Y , DYEING DEPARTMENT, THE YOILKSHIRE COLLEGE, LEEDS.

ISSN:0368-1645    

DOI:10.1039/CT9048500056

出版商:RSC    

年代:1904

数据来源: RSC

摘要:

THE FOUR OPTICALLY ISOMERIC L-MENTHYLAMINES. 65 IX. - The Four Optically Isomeric I-Menthylamines and their Xults. By FRANK TUTIN and FREDERIC STANLEY KIPPINQ. IN the course of the investigation of the isomeric salts derived from hydrindamine (Kipping, Trans., 1903, 83, 873) and methylhydrind- amine (Tattersall and Kipping, Trans,, 1903,83, 918), it seemed par- ticularly important to try and obtain corresponding isomerides from some optically active base of a totally different type, and among such bases which are moderately accessible, menthylamine seemed to be the most suitable. Two compounds, distinguished as I- and d-menthylamines, have been known for some time: E-menthylamine was obtained by reducing nitromenthene with zinc and sulphuric acid (Xoriya, Trans., 1881, 39, 77), and also by reducing the osime of I-menthone with sodium and alcohol (Andres and Andreef, Ber., 1S98, 25, 609) ; d-menthylamine mas prepared from the oxime of d-menthone (Andres and Andresf, Zoc.cit.), and was also obtdined, together with the I-base, by heating I-men. thone with ammonium formate (Witllach and Kuthe, Annulen, 1893, 276, 306); in the latter case, the two bases mere separated by fractionally crystalliaing their formyl derivatives, which are the original products of the reaction. These I- and d-bases, which are liquids, have been characterised by preparing from them a number of simple derivatives, and the specific rotations of many of the latter have been determined by Binz (Zeit. physikal. Chem., 1893, 12, 727). Our investigations shorn that the base produced by the reduction of the oxime of '' I-menthone " is a mixture of four optically isomeric menthylamines, in which, however, three of the bases are present in relatively very small quantities.The base obtained by the action of ammonium formate on I-menthone is likewise a mixture of these four optical isomerides, but apparently in proportions different from those in which they occur in the reduction product of the Z-oxirne. The explanation of these facts is t o be found in the origin and in the methods of formation of the basic mixtures. Leaving out of con- sideration the reduction of nitromenthene, the other methods for the preparation of the base start from menthone, a ketone which contains two asymmetric groups and which, in its turn, is produced by the oxidation of menthol with sulphuric acid and dichromate, The menthone obtained by carrying out this oxidation with dilute sulphuric acid and dichromate at 30" has a specific rotation [a], - 26" to - 28' and is called Gmenthone ; when, however, oxidation is accom- VOL.LXXXV. F66 TUTIN AND KIPPING: THE FOUR OPTICALLY plished with the aid of concentrated acid at 30°, the product has a specific rotation [a], + 2 6 O t o +2S0 and is called d-menthone, the ‘‘ inversion ” being due to the action of the concentrated acid (Beck- mann, AnnaZen, 1889, 250, 322). The application of the terms ZGWO- and dextro- to these two products and the observation that they have approximately equal but opposite specific rotations seem to have caused some confusion as to the relationship between these two ketones (compare Richter, Organ.Chern., 1898, p. 340; Vorlander, Ber., 1903, 36, 268), That they are not enantiomorphously related is indicated by the differences in physical properties and more especially by the values of the specific rotations of their oximes, both of which compounds are hvorotatory, having specific roiations of [ ~ ~ ] ~ - 4 0 * 7 ~ to -42.5O and -4.85’ to - 6.67’ respectively. That the conversion of “I-menthone ” into ‘r d-menthone ” by the action oE acids or of alcoholic solutions of alkalis is not an optical “ inversion ” but a partial racemisation is also rendered highly pro- bable, even if not proved, by the fact that the product, ‘‘ d-menthone,” is optically active. A consideration of the constitution of menthone leads t o the same conclusion : assuming that the oxidation of menthol with dilute acid and dichromate gives one product only, then of the two asymmetric groups in this ketone which may be represented by - -, one only would probably undergo change under the influence of acids or alkalis, namely, that which is capable of keto-enolic tautomerism ; the result would be a mixture, probablyof unequal quantities,of the - - and - + isomerides, the formation of which may be indicated as follows :- Prp Prp Prg PrP I I C CH( 4- ) I I /Y-) / \ /\ CH( - ) / \ \./ FH2 FH*OH $!HZ 70 -+ $!H2 ?*OH -+ YH, 70 CH2 CH, CH, CH, f- CH, CH, +- CH, CK, \ / CHMe(-) I-Menthol. I-Meathone. Enolic form. (d-Menthone or) I-isoMeuthone. The values of the specific rotations of the partially racemised ketonic mixture would depend, therefore, on those of its two components and on the proportions in which they are present, and since it is quite possible that partial racemisation occurs to some extent even in the oxidation with dilute sulphuric acid and dichromate, ordinary I-menthone ” itself may be a mixture of the two optical isomeridea.Whether ‘’ I-menthone ” is one definite compound or not, the oxime repared from it in the usual way in alkaline solution is doubtless a \ / CHMe( - ) \ / CHMe( - ) CHMo( - )TSOMERIC L-MENTHP LAlfINES AN.D THBlR SALTS. 67 mixture of the oximes derived respectively from the - - and - + ketones, and consequently, on reduction, since a third asymmetric group is produced, four optically isomeric menthylamines will be formed, as experiment shows, however, in very unequal quantities : these four isomerides would be the forms - - - and - + - derived from the - - ketone, and - - + and - + + derived from the - + ketone.Similar arguments hold good in the case of the formation of the base by heating menthone with ammonium formate ; although there is here no freealkali, the high temperature would, no doubt, tend to give in the first place a mixture of two menthones, from each of which two menthylamines would then be produced ; these four compounds would be identical respectively with those obtained from the oxime, provided that in both cases the asymmetric group containing the methyl radicle undergoes no change ; were this group also to undergo inversion, then obviously four additional isomerides ( + - - , + + - , + - + , + + + ) would be formed, and an optically inactive mixture of four externally compensated bases would be the final result.As we show later that all the four bases obtained in these reactions are optically active, it is prove6 that throughout all the changes involved in the production of menthylamine from menthol one of the asymmetric groups escapes racemisat ion. Nomenclature.-If we assign to I-menthone the configuration - - , then d-menthone would have the + + configuration, and the ketone obtained from I-menthone by the action of acids or of alkalis would have the - + configuration, and might be named I-isomenthone. The two menthylamines derived from I-menthone may then be distinguished as I-menthylamine ( - - - ) and Eneomenthylamine ( - + -)! respec- tively (compare Forster, Trans., 1898, 63, 391 ; Tattersall and Hipping, ibid., 1903, 83, 919), those derived from the isoketone being named I-isomenthylamine and I-isoneomenthylamine respec- tively.The four isomerides derived from the true d-menthone (+ +) and from d-isomenthone (+ - ) could then be distinguished in a similar manner. We have adopted this system in dealing with the four bases described in this paper, and as the choice of the configuration origin- ally assigned t o any one isomeride is, of course, purely arbitrary, we retain the name I-menthylamine for the base produced in the largest quantity by the reduction of the oxime of ‘‘ I-menthone ” and assign t o it the configuration - - -. One of the other three compounds undergoes partial racemisation, giving a base which is not I-menthylamine, and as the latter and the other two isomerides are stable; we infer t h a t this partial racemisation takes place in the group >CH*NH,, which is known to change very F 268 TUTIN AND KIPPING: THE FOUR OPTICALLY readily in some cases ; if this is so, the base which undergoes change and that into which it is partially transformed would have the con- figurations - - + and - + +, since the - -+ - compound would give Z-menthylamine. The two isomerides in question are therefore named the Eiso-bases, the unstable one being distinguished as Z-isoneo- menthylamine ; the remaining compound is called Z-neomenthylamine, Isomeric l-Benthylaminne d-13romocampizol.szlphoncctes.--Havin,a ob- tained an optically pure kmenthylamine in sufficient quantity and having satisfied ourselves that the base did not undergo partial racemisa- tion under the conditions of our experiments, we were able to study the question of the existence of isomeric salts ; it was thus proved that Z-menthy lamine gives with the bromo-acid, isomeric salts cor- responding with those obtained from hydrindamine and methyl- hydrindamine, but, as in some earlier cases, i t seemed impossible to obtain the compound of lower molecular rotation in a pure condition, that is t o say, free from its iaomeride.The separation of the four isomeric menthylamines already men- tioned was accomplished by fractionally crystallising the hydro- chlorides, d-bromocarnphorsulphonates, deamphorsulphonates, formyl and benzoyl derivatives in the manner indicated in the experimental part of this paper.Z-Menthylamine is isolated from the reduction product of menthone- oxime without much difficulty by either of the first two processes, but in order to separate the remaining mixture of isomerides none of the first four methods is sufficient, and it is necessary to convert the bases into their benzoyl derivatives, which are then submitted t o a prolonged and troublesome process of fractional crystallisation. The bases are regenerated by hydrolysing their benzoyl derivatives with dilute sulphuric acid, but, unfortunately, in this process one of the isomerides (Z-isoneomenthylamine) undergoes partial racemieation, giving the Z-iso-base, so that we have been unable to obtain it, except in the form of its benzoyl derivative.The following table shows the principal cornpunds which have been prepared : I- isoneo- &Base. Z-neo-Base. Z-iso-Case. Base. 31. p. [a],. M.p. [aln. M.p. [ a ] , . 111.1). [a]D. d-Bromocamphorsulphonate 226" 4- 43 -2" 70--75"('!) - 166" + 65" - _ d-Camphorsulphonate ...... 158 - 5.3 188 f11'8" 177 +21'7" - Benzoyl derivative ... ...... ... 156 - 61.9 128 - 17.4 121 ~r22.7 104" - 3.8" The specific rotations of the salts were determined in aqueous solu- tions, those of the benzopl derivatives in chloroform.ISOMERIC L-MENTHYLAMINES AND THEIR SALTS. 69 EXPERIMENTAL. Isokctio2z of 1-Menthylamine Hgclrochlode. The base obtained by the reduction of the oxime of '( I-menthone " with sodium and alcohol was distilled in steam, neutralised with hydrochloric acid, and the salt systematically cry stallised from water ; the most sparingly soluble portion consisted of coarse needles of I-menthylamine hydrochloride, the more readily soluble fractions, which were apparently mixtures, separated in more slender needles.The specific rotation of the pure salt and those of the two most readily soluble fractions were determined with the following result : * I-Menthylamine hydrochloride. Mixture of hydrochlorides. [a],. r a],. Solvent, chloroform - 45.4" 7 9 9 , - 45.6 1 i::: } different samples. ,, water ...... - 36.6 - 28.0 L 31 ID. [ 11 ID. 9 9 ,, ...... - 70.1 - 53.5 The value obtained in aqueous solution for the pure salt is rather higher than that obtained by Binz (Zoc.cit.), whose sample possibly Contained an isomeride, the existence of which in the original reduction product is indicated by the lower specific rotations of the more readily soluble fractions, 1-Me~ethylamirie d - B r o r } i o c a t i L ~ ? L o ~ s ~ Z ~ ~ ~ o ~ ~ t e , C,,H,,*NH,,C,,H,,O Br*SO, H. The base from the most sparingly soluble hydrochloride (see above) gives, with d-bromocamphorsulphonic acid, a salt which crystallises readily in well-defined prisms melting at about 225'. When crystal- lised two or three times, this substance appears to be homogeneous and its meltiDg point hardly changes appreciably, but, as will be shown later, i t really consists of a mixture OF salts, both, however, derived from pure Z-menthylamine. Z-Menthg lamine d-bromocamphorsulphonate is very sparingly soluble i n ethyl acetate, sparingly so in water ; it dissolves readily in alcohol or chloroform, but is practically insoluble in light petroleum. The specific rotation of H sample which had been crystallised fifteen times from dilute alcohol was determined: in chloroform, [.ID + 4 8 5 O ; in water, [a], +43*25", [M!= being 201.5'.* I n these and in all futiire o p t i d determinations, unless otherwise stated, 20 C.C. of solution contained 0.5 gram of the substance.70 TUTIN AND KIPPING: THE FOUR OPPICALLY Taking the molecular rotation of the brornocamphorsulphonic acid as [MID + 270, that of the base would be [M,I, - 685, a result which agrees closely with that deduced from the specific rotation of the hydrochloride. This compound, when prepared from the base contained in the pure d-bromocamphorsulphonate, crystallised in large needles melting at 158"; it was moderately soluble in water, readily so in alcohol, and very soluble in chloroform ; when deposited from aqueous solution, it contained water of crystal lisat ion.The specific rotation was determined with a sample of the dried salt : in chloroform, [a], +9*5" ; in water, [.ID - 5*3", [MI,, in the latter case being - 20.5". Taking the molecular rotation of the acid as [MI, +51", that of the basic ion would be [MI, - 71-5", which is somewhat higher than the values previously obtained. Benxoyl-l-MenthyZcLmine, C,oH1,NH*CO*C,H,. The benzoy 1 derivative, prepared from the pure bromocamphor- sulphonate by the Schotten-Baumann method, crystallised from alcohol in large needles melting a t 156" ; in chloroform, [a],, = 61.9'.The Existence of Isomeric Merzth&mi~t,es iw the Reduction Product o j ( L 1-MentAoneoxime." Fractional crystallisation oE the hydrochloride of the crude base, obtained by reducing I-menthoneoxirne, gave, as already stated, products diff9ring in specific rotation ; the d-bromocamphorsulphonate, prepared from all the more readily soluble fractions of the hydrochloride, or from the original basic reduction product', proved t o be a mixture, from which, by repeated crystallisation from dilute alcohol, we isolated ( a ) a salt melting at 225', identical with pure Z-menthylamine d-bromo- camphorsulphonate ; (6) a salt melting very indefinitely a t 170-1'763, which was obviously a mixture, and the further treatment of which is described later.The salt melting at 225' formed by far the greater proportion of the whole product, even when the d-bromocamphorsulphonate was prepared from the more readily soluble portions of the fractionated hydro- chloride.ISOMERIC L-MENTHYLAMINES AND THEIR SALTS. 71 The For mat ion of Isomeric 1- Memt h ylarnine d -B?.onaoca~nZphors2Clpho1aCGte0. A considerable quantity of 1-menthylamine d-bromocamphorsulphon- ate was prepared partly by the fractional crystallisation from dilute alcohol of the salt obtained from the pure hydrochloride, and partly in a similar manner from the crude d-bromocamphorsulphonate ; when, judging by the melting point and crystallino form, it seemed that we had obtained a definite compound, the whole of the pnre material was separated into six fractions, and the first and last were examined polarimetrically in chloroform solution ; the first fraction gave [a]= + 48*5*, whilst the last fraction had [a]TJ +48.0°.As these two extreme fractions had practically the same specific rotation and melted simultaneously at 224--225+5O, it seemed that the salt was homogeneous ; nevertheless, we rejected the last fraction and its mother liquors. The remaining salt was then decomposed with barium hydroxide, regenerated from its component acid and base in the usual way (compare Trans., 1903, 83, 906), and the product systematically crystallised from dilute alcohol ; after thus obtaining nine fractions, each of which had been crystallised several times, and all OF which seemed identical, the melting points and optical properties of tho first and last fractions were determined. In water./-J-, In chloroform, M. p. r a I". [ M I D . [ a In, First. , . . . , 2 26' + 43.75O 203.8' 48-75' Last ...... 221 + 38% 180-8 42-8 These experiments afforded almost conclusive evidence of the exis- tencq of isomeric salts, but in order to establish this fact beyond all question the first fraction only was decomposed and regenerated from its components ; the salt thus obtained, when repeatedly crystallised from aqueous alcohol, gave extreme fractions having the same melting points as before (226' and 221'), and the specific rotation [.ID of the last fraction was found to be + 39.5O in water and + 43.1' in chloro- form, these results agreeing closely with those previously obtained.The last fractions (m. p. 221°) from the two preparations were added together and the mixture crystallised six times from dilute alcohol ; the first fraction then melted moderately sharply a t 222O, and its specific rotation in chloroform was [a], + 44.4'. In these results we have a complete analogy between the case of 2-menthylamine and that of d-hydrindamine (Zoc. cit.) or I-methyl - hydrindamine (Zoc. cit.) ; in spite of its apparent purity, the salt melting at about 221' is undoubtedly a mixture and contains a considerable quantity of the isomeride melting a t 226O, although it does not seem72 TUTIN AND KIPPING: THE FOUR OPTICALLY probable that a complete separation of the two components could be accomplished even by further crystallisation of very large quantities of material.Attempts to Isolate other Isomeric MenthgZamines. The salt melting indefinitely a t 170-176", which is obtained on crystallising from dilute alcohol the d-bromocamphorsulphonate of the base prepared by the reduction of '' I-menthoneoxime," forms tufts of short, slender needles and has a specific rotation of [.ID + 50" (ap- proximately) corresponding with a molecular rotation of [MID + 233' in aqueous solution. This substance had the characteristics of a mixture, and all attempts to isolate a pure compound by crystallisation from dilute alcohol were unavailing. As the salt of Z-menthylamine with Reychler's d-camphorsulphonic acid was found to crystallise very readily from water, a separation of the bases in this crude d-bromocamphorsulphonate was attempted with the aid of this .acid.We therefore liberated the basic mixture and prepared the d-camphorsulphonate, which crystnllised from water in needles ; after several crystallisations, the most sparingly soluble frac- tion, when dried in the air, melted a t 144-147", but when dried at looo for several hours it melted a t 164-165", this difference indicat- ing water of crystallisation. As this fraction of the salt appeared to be pure, its specific rotation in water was determined with the follow- ing result : [.ID + 5*8', [ MI, + 22-4". The molecular rotation of the base in this salt would therefore be [MID - 2 9 O , that of the acid being As we expected that the base would be "d-menthylamine," it appeared probable that this salt, in spite of its having been repeatedly crystallised, was redly a mixture containing a considerable proportion of the salt of the I-base ; it was therefore converted again into the d-bromocamphorsulphonate. On crystallising this salt from ethyl acetate containing a little chloroform, a further quantity of I-mecthyl- amine d-bromocamphorsulphonate, melting a t 225', was separated.The residue then crystallised from aqueous alcohol in very slender, bulky needles melting a t 164--167O, but after many further crystal- lisations it melted sharply and constantly at 170°, and appeared to be homogeneous. A sample thus prepared, when examined polarimetric- ally, gave [ a ] D + 63.5' in aqueous solution, whence [MI, + 295.9' ; this value indicating the presence of a dextrorotatory base having the molecular rotation [MID + 26O, whereas the value for '' d-mentbyl- amine," calculated from that of the hydrochloride examined by Binz, Not feeling satisfied that this salt was derived from pure " d-menthyl- arnine," and the qiiantity being too small for further crystallisation, we [MID +51*O0.is [MID 4-33'.ISOMERIC L-MERTHYLAMINES AND TEEIR SALTS. 7 3 prepared some base by heating Lmenthone with ammonium formate, and hydrolysed the crude mixture of formjl derivatives directly with hydrochloric acid. The base thus obt,ained was converted into the d-bromocamphor- sulphonate, and this salt, although showing a great tendency to separate as an oil from its solution in dilute alcohol, was finally obtained in tufts of fine needles, which, after recrystallisation, melted a t 168*, the melting point not being raised by further crystal- lisation.The specific rotation of this salt was determined with the following result : in chloroform, [.ID t-54.5'; in water, [a]= -t63.9', [MID being 297.7'. As the specific rotation of the salt melting a t 170' obtained from the products of the reduction of the oxime wits [ a ] D + 63.5' in aqueous solution, it seemed as if this substance was a pure salt of a d-base, but when a sample was converted into the hydyochloride, which crystal- lised from water in needles melting a t 230-232", and a fraction of this product was examined in aqueous 8olutior1, it was found to be optically inactive, whilst another fraction gave [ a]D + 6.8' in aqueous solution, and a third was laxorotatory.A solution of the base in dilute alcohol prepared from a portion of the inactive hydrochloride was also examined and found to be inactive. Isohtion of Pour Benxo?llmenthyEarrzines. The base in the d-bromocamphorsulphonate melting a t 170" is there- fore a mixture, even after the exhaustive purification which it has undergone; this was proved in the following manner: the benzoyl derivative was prepared by the Schotten-Baumann method from both the samples of d-bromocamphorsulphonates melting a t 1 68-170" and having specific rotations of 63.5" and 63.9' respectively. When crystallised from alcohol, both preparations were found to be mixtures, and as the result of a prolonged and very troublesome process of frac- tional crystallibation four benzoyl derivatives were ultimately isolated in a pure condition.(I) The most sparingly-soluble fraction, which cryetallised i u long needles, melted a t 156O, had- [a], - 61.9" in chloroform solution, and was identical with the benzoyl derivative of Lmenthylamine. (2) A compound which crystallised in long, glistening leaf-like plates, melted at 128', and had [&Ir, - 17.4' in chloroform solution. (3) A compound which crystallised in thick tufts of short, fine needles, mdted a t 104O, and had [ a ] D - 3.8' in chloroform solution. As this derivative was the most fusible isomeride and might there- fore have been a mixture, it was recrystallised three times from74 TUTIN AND KTPPING: THE FOUR OPTICALLY alcohol, and the specific rotation again determined in chloroform solution, was [a], - 3-9O, indicating that the substance is pure.(4) The most readily soluble fractions gave a benzoyl derivative which crystallised in very long, slender needles, melted at 121’, and had [ ulD + 22.7’ in chloroform solution. During the fractional crystallisation of the benzoyl derivatives, it was observed that when the original solutions were allowed to evaporate spontaneously, short, thick prisms mere obtained, together with needles ; when, however, these apparently homogeneous prisms were recrystal- lised, they gave needles and the glistening plates of the benzoyl derivative melting at 128’. The proportions of these four benzoyl derivatives actually isolated from the crude mixture were approxi- mately equal, but the compound melting a t 104’ was perhaps obtained in rather the largest quantity.The various mother liquors contained a very considerable fraction of the total material. At tempts to sepamte the Isorne r ic For rny Zm en ti& y lamin es. Having proved that the basic product of tbe reduction of “I-men- thoneoxime,” as well as that obtained by heating “I-menthone ” with ammonium formate, is a mixture of a t least four menthylamines, not easily separated through the agency of their benzoyl derivatives, and, moreover, having found that these benzoyl derivatives are hydrolysed only with great difficulty, i t seemed desirable to try and isolate the four arnines in the form of their formyl derivatives, especially as the latter were known to undergo hydrolysis with moderate ease, and could there- fore serve for the preparation of the bases themselves with less chance of partial racemisation. A considerable quantity of formylmenthylnmine was therefore prepared, and, instead of hydrolysing directly, the crude product was crystallised first from ether and then from ethyl acetate, from which it finally separated in well-defined, four-sided prisms melting at 112-113’.The melting point of this, the principal cryst,alline product, was constant, but the mother liquors deposited a small quantity of crystals melting at 117”; when these two prepara- tions were mixed together, the mixture melted at 115’. The two specimens were, therefore, not different substances, but the more sparingly soluble fractions (a. p. 112-113”) probably contained a small quantity of another formyl derivative not easily removed by cry st allisatio n.1 -isoLWenthyZamine. The solid formyl derivative (m. p. 112-113O) WHS then hydrolysed with strong hydrochloric acid ; the hydrochloride thus obtained, after crystallisation from water, melted at 186-187’. The base in this saltISOMERIC L-MENTHYLAMINES AND THEIR SALTS. 75 was then combined with d-bromocamphorsulphonic acid, and the com- pound thus obtained cry stallised from dilute alcohol in well-defined needles melting a t 1 6 6 O . The specific rotation of this salt was deter- mined in aqueous solution and found to be [a],+65", whence [MID + 303' ; this gives a molecular rotation of the base [MI, + 33", a value which is identical with that calculated from the molecular rotation of the '' d-menthylamine " hydrochloride described by Binz The base from this most sparingly soluble fraction of the d-bromo- camphorsulphonate gave a pure benzoyl derivative melting at 1 21°, but the most soluble portions of the d-bromocamphorsulphonate seemed impure, and when the base contained in them was cmverted into the benzoyl derivative, the latter on fractional cry stallisation gave, in addition t o the compound melting a t 12l0, a small quantity of the benzoyl derivative melting at 128'.The formyl derivative melting a t 112-113" is, therefore, impure in spite of repeated frac- tional crystallisation, and apparently the best way of obtaining a pure base is t o hydrolyse the formyl derivative and crystallise R salt pre- pared from the basic mixture.The salt of this base, I-isomenthyl- amine, with Reychler's d-camphorsulphonic acid, was prepared for the purpose of comparison with the d-camphorsulphonate of the base obtained on hydrolysing the benzoyl derivative melting at 1 2 8 O (p. 77). It was moderately soluble in water, cry stallising in needles which, when dried at loo", melted at 177". The specific rotation of this salt in aqueous solution was determined'and found to be [a], + 21*7', whence [MI, +83.9", so that the calculated value for the base is (ZOC. cit.). [MIL, + 33'. Furthe?' Examination of Formyl Derivatives. The ethereal mother liquors from the crystitllisation of the formyl derivative were evaporated, and the brown, syrupy residue distilled under 12 mm. pressure. After some unchanged menthone had passed over, about two-thirds of the remaining liquid distilled 2 t 208--215', giving an almost colourless, highly refractive, viscous liquid, to which a small quantity of ethyl acetate was added, when a larger quantity of the formyl derivative, melting at 112-113", was obtained than that which crystallised from the ethereal solution of the original substance. This product, when separated from a n uncrystallisable residue, was hydrolysed with strong hydrochloric acid and the base converted into the d-bromocamphorsulphonate. This salt, which appeared highly impure, and only crystallised partially when kept for some time in a vacuum, was therefore converted into the benzoyl derivative, the latter being fractionally crystallised from alcohol,76 TUTIN AND KIPPING: THE FOUR OPTICALLY Probably about 75 per cent.of this product consisted of the deriva- tive melting a t 12S0, this being identical with that obtained in small quantity from the formyl derivative melting a t 112-113°, but some of the benzoyl derivative melting a t 121O was also isolated, together with a small quantity of the isomeride melting a t 156". The distillation was stopped when the temperature reached 238' ; the residue in the flask was hydrolysed and converted into the benzoyl derivative, which, on fractional crystallisation from alcohol, was found to consist chiefly of the derivative melting a t 1 5 6 O , and a smaller amount of the derivative melting at 104O, although the proportion of the latter was not nearly so large as that obtained before in the fractional crystallisation of the benzoyl derivatives from the crude mixture of formyl derivatives ; this fact, and further evidence obtained later, seemed to show that the formyl derivative corresponding with this benzop 1 derivative had partially racemised on distillation.I n all the experiments in which the bases obtained from the formgl derivatives were separated by means of their benzoyl compounds, the proportion of the benzoyl derivative melting a t 156' was always less than that of the isomerides melting at 128' and 1 2 1 O . Hydrolysis of the Benxoyl Derivatives. The preceding experiments show that it is practically impossible, or at least very difficult, to separate the four formyl derivatives present in the original mixture ; the compound melting a t 112--113O, which is the only crystalline substance obtained in any quantity, serves for the preparation of one base only, namely, I-isomenthy lamine. We were therefore obliged to make use of the benzoyl derivatives for the preparation of the two remaining bases, and as i t was necessary t o prove that the bases did not racemise during hydroly,' ris, we recon- verted them either into the benzoyl derivative or into some salt which had bean previously shown to be homogeneous.The benzoylmenthylamines do not hydrolyse appreciably when boiled for many hours with strong hydrochloric acid, and when dilute sulphuric acid (1 : 1) is used, the only basic product obtained is a small quantity of ammonia. A sample of the benzoyl derivative of I-menthylamine was heated for 6-8 hours in a sealed tube at 149-160O with strong hydro- chloric acid and a small quantity of glacial acetic acid; at the end of this time, the benzoyl derivative was completely decomposed into benzoic acid and a quantity of tarry matter mixed with menthene and menthylamine.The base was combined with d-bromocamphor- sulphonic acid, and as the salt thus obtained melted a t 824' after recrystalliPation, the base seemed not to have racemised.ISOMEHIC L-MENTHYLAMINES AND THEIR SALTS. 77 Some of the pure benzoyl-derivative of Lisomenthylamine (m. p. 1'21') was hydrolysed in a similar manner, and the base again converted into the benzoyl derivative, which still melted a t 12l0, thus indicating that racemisation had not taken place to any appreciable extent.1- Neomenthylcbmine. As the benzoyl derivative melting at 128' appeared to be derived from a base which had not hitherto been isolated, it was analysed to prove that it really was a menthylamine derivative. Found, C = 78.80 ; H = 9.67. C17H,,0N requires C = 78.76 ; H = 9.65 per cent. This benzoyl derivative was then hydrolysed in the manner already described, but the base, which was isolated by distillation in steam, was obtained in very poor yield. The d-bromocamphor- sulphonate prepared from the distillate was dissolved in dilute alcohol and the solvent allowed to evaporate, but the salt separated as an oil, although, when slowly evaporated in a vacuum desiccator, the solution deposited nodular masses, which, when dried a t the ordinary temperature, melted a t 70-75'.Since this salt could not be ob- tained in well-defined crystals from the ordinary solvents, it was decomposed with caustic potash, and the base, when distilled in steam and combined with Reychler's d-camphorsulphonic acid, yielded a salt crystallising from the concentrated aqueous solution in Well-defined needles, which, after recrystallisation, melted constantly at 188' This salt had the appearance of a pure substance, and as it was less fusible than the d-camphorsulphonates of either of the other two bases we concluded that racemisation had not taken place to any appreciable extent. I-Neomenthylamine d-camphorsulphonate is moderately soluble in water, alcohol, or ethyl acetate, and dissolves very readily in chloro- form; it crystallises from water in a hydrated state. The specific rotation of this salt in aqueous solution was determined and found to be [a]. + 11*8', whence [MI, + 45.7'. This gives [MI, - 6" (approx- imately) for the molecular rot-ttion of the base, the constant for the acid being [MID + 5 1 -0". I-isoKeomenthylamine. The benzoyl derivative of I-isoneomenthylamine, melting a t 104", was hydrolysed in a similar manner, and the d-bromocamphor- sulphonate of the base dissolved in dilute alcohol ; the salt crystallised in fine needles, but had the characteristics of a mixture, arid after three recrystallisations melted a t about 169" ; from the mother liquors,78 HAGA : PEROXYLAMINESULPHONATES AND tufts of needles were obtained, which, after recry stallisation, appeared less impure than the more sparingly soluble fraction and melted at about 157'O. The base contained in this apparently impure d-bromocamphm- sulphonate was again benzoylated ; the product, after fractiona crystallisation from alcohol, consisted principally of the original benzoyl derivative melting at 1 0 4 O , but a certain amount of benzoyl Eisomenthylamine (m. p. 121') was contained in the more readily soluble fractions. It therefore appeared highly probable that Lisoneo- menthylamine had undergone change to a certain extent, and this evidence confirms that obtained previously in examining the distilla tion products of the formyl derivatives, but with the quantity of material at our disposal we were unable to obtain salts of the base free from its closely related isomeride. The authors desire to record their thanks to the Government Grant Committee of the Royal Society for financial assistance in carrying out this work. UNIVERSITY COLLEGE, NOTTINGE AM.

ISSN:0368-1645    

DOI:10.1039/CT9048500065

出版商:RSC    

年代:1904

数据来源: RSC

摘要:

78 HAGA : PEROXYLAMINESULPHONATES AND X.- Perox ylami.rzesul’homt es cum! Hydmx y7amirLetri- sdphonutes (Sulphazilntes and ~~etasul~fzaxl,loctcs). By TAMEMASA HAOA, D.Sc. PERHAPS the most interesting of the sulphazotised salts discovered by Fremy (Ann. China. Phys., 1845, [iii], 15, 408)are the two which result from the oxidation of one or other of the potassium hydroximino- sulphates (hydroxylaminedisulphonates) in aqueous solution by either silver oxide or lead peroxide or some other reagent. One of these products is the very unstable salt which he named sulphuxilate. This substance is remarkable for crystallising from its aqueous solution, which is of an intense bluish-violet colour, in brilliant golden-yellow needles, very slightly soluble in ice-cold water, but dissolving easily in hot water.It can seldom be preserved for any length of time, and gives a disagreeable odour to the skin, like that caused by manganates and ferrates. According to Fremy, it is easily fusible, but that is a mistake ; it is the products of its decomposition which melt. The other salt, his metasuZphaxiZate, is also sparingly soIuble in cold water, but is colourless and has considerable stability. It crystallises inHYDROXYLAMINETRISULPHONATES. 79 rhombic prisms which are so well defined that Fremy describes the compound as being the most beautiful of all the sulphazotised salts. These crystals appear to be isomorphous with those of potassium 5/6-normal hydroximinosulphate and the two salts can hardly be separ- ated by crystallisation. Its solution is quite neutral and gives a precipitate with basic lend acetate only.Premy expressed the com- position of the sulphazilate by the formula H07NS2K2 (here written with the atomic proportions now in use), which is ouly incorrect in iucluding hydrogen (Claus). He gave the composition of the meta- sulphazilate correctly as H,U,,N,S,K,. Claus (AnnaZen, 1871,158, 205), who gave details for the preparation of the coloured salt by lead peroxide, proved that in its production from potassium 5/6-normal hydroximinosulphate it is not necessarily accom- panied by sulphate ; he also demonstrated with tolerable certainty that it is the sole product of the oxidation; and found that it passed spon- taneously into the colourless salt, together with a fixed quantity of sulphate and a gas which is apparzntly nitrous oxide (compare page 89 of this paper).H e recognised the sulphonate constitution of both salts and gave to the coloured salt the name and formula ‘ oxysulph- azotate,’ (S03K),NL\N(S0,K), and to the white salt the name and formula, trisulphoxyazoate,’ O:N(SO,K),,H,O, that is, with the nitrogen quinquevalent in both formulae. It will be seen that, even empirically, these formulz differ a little from Premy’s. Claus also sought for, and, as he believed, obtained, the primordial sulphazotised salt which he formulated at first as SO,,NO,K (op. cit., 213), and afterwards as O:N(SO,K) (Ber., 1871, 4, 508). This would be the analogue of the trisulphoxyazoate,’ with the nitrogen only trivalent; but the existence of this salt has since been disproved (Trans., 1900, Raschig (Annulen, 1887, 241, 223) Laving found that the white salt, in a boiling and feebly acid solution, may yield sulphate to the extent of two-thirds of its sulphur, along with, apparently, hydroxyitminosulphuric (hydroxylaminemonosulphonic) acid, has recognised that i t behaves as a derivative of hydroxylamine.But because it does not decompose when in strongly alkaline solution, he will not allow that it is that base trisulphonated. He modifies Claus’.y two formulae, writing that 0 OH 77, 437). for the coloured salt as (SO&) N-----N(SO,K),, /O\ and that for the \o/ white salt as (S0,K),”O>N(S03K),,2H,0. 0 Hantzsch and Semple have found (Ber., 1895, 28,2744) that, when crystals of potassium 2/3-normal hydroximinosulphate form in a bluish-80 HAGA : PEROXYLAMINESULPHONATES AND violet solution of potassium sulphazilate, they may contain 1-4 per cent.of this salt, apparently in solid solution, and consequently show a bluish-violet colour. These chemists have therefore advanced the view that Fremy’s coloured salt, which they have renamed ‘ nitroxydisulphonate,’ is sulphonated nitric peroxide, the yellow cryst,als of which have double the molecuIar magnitude of the dissolved bluish-violet form, in analogy with the two forms of nitric peroxide itself. The formula for the bluish-violet modification is given in a foot-note as O*N:(SO,K),, in which, therefore, the nitrogen is repre- sented as being trivalent and the oxygen as univalent. A structural formula for the yellow modification is not given, but Raschig’s is rejected, as having two quinquevalent nitrogen atoms in union with aach other, a mode of combination which is without parallel.Raschig’s formula for the white salt is also rejected, but as the simpler one proposed by Claus is adopted in its place, the quinqne- valency of the nitrogen is maintained. On the authority of Schatz- man, and as a result of their own experiments in the case of hydriodic acid, these chemists state that, in acting as an oxidising agent, the coloured salt reverts to hydroximinosulphate. I n 1896, Sabatier (Comyt. yend., 122, 1417, 1479, and 1537; 123, 255) published the results of an investigation of the violet solutions produced by the action of reducing agents on a sulphuric acid solution of nitrososulphuric acid, and suggested that the colour is due to the formation of the acid of Fremy’s potassium sulphazilate.His suggestion is discussed on page 93 of this paper. I n the detailed examination of Fremy’s sulphazotised salts made by Dr. Divers and the author, the results of which have been described from time to time in the Transactions, the sulphazilate and metasul yhaziiate were purposely reserved for separate treatment, because they are distinguished from the other salts in being products of oxidation. In the present paper, the author endeavours to prove (1) that the sulphazilate is an oxime-peroxide (Scholl), or a peroxinze, (SO,K),NO* ON(SO,K),, the first and only inorganic peroxime yet known; (2) that the meta- sulphazilate is a triacykated hydroxylamine, (SO,K),NO(SO,B), being the only compound of this type having an established normal con- stitution (all others, such as tribenzhydroxylamine, being apparently of more complex constitution) ; and (3) that, consequently, the nitrogen in both these sulphazotised salts is only tri’valent, instead of being quinquevalent.From among the several constitutional names which suggest them’- selves for Fremy ’ s provisional ‘ sulphazilate ’ and ‘ metasulphazilate,’ that of perox?jZaminesuZphonccte for the former, and of hydroxylamine- trisulphonate for the latter, have been adopted as preferable. InHYDROXYLAMINETRlSULPHONATES. 81 consequence, i t has been found advantageous in this connection to call the parent salt hydrox~ylaminedisul~onate, instead of the alternative hydyoxirninosulphate, the name usually employed by Divers and the author.It has also been found convenient to treat of the hydroxyl- aminetrisulphonates before the peroxylaminesulphonates, from which they are apparently always derived, Hydyoxykuminelribu Zphonates (Metasui’phaxilates ; 5?’risuZ@hoxyxmntes). Potassium hydroxylaminetrisulphonate is most readily prepared by Fremy’s method, i n which there is no intermediate separation of its parent salt, the peroxylaminesulphonate. Somewhat a1 kaline potass- ium hydroxylaminedisulphonate is gently boiled and shaken with silver oxide or lead peroxide, until the solution, which a t first becomes intensely bluish-violet, just loses its colour. Then, by evaporation and cooling, the filtered solution can be made to yield nearly all its hydroxylaminetrisulphonate.Theoretically, all the hydroxylamine- disulphonate should be converted into hydroxylaminetrisulphonate and nitrite, 2Pb0, + 3HON(SO,K), + KOH = BPb(OH), + 20N(S03K), + KNO, ; but sulphate and nitrous oxide are always produced, usually accom- panied by very small quantities of nitrogen and aminemonosulphonate (aminosulphate). Nevertheless, 86 and 87.8 per cent. yields of the indicated quantity of the salt have been obtained, together with 78 and 85 per cent. of the full amount of nitrite as indicated by the urea method (p. 94). The production of such large quantities of the hydroxylaminetrisulphonate shows the inaccuracy of Claus’s descrip- tion of the changes concerned. According t o that account, which is endorsed by Raschig, no nitrite is formed, and the utmost yield of hydroxylaminetrisulphonate w-ould be equivalent to only 75 per cent.of tbe sulphur of the hydroxylaminedisulphonate. CorLslitution.-Strictly speaking, the product of the triacylation of hydroxylamine with sulphonate radicles can only be a disulphonate, the third sulphonate radicle becoming sulp6atic by its union with oxygen. But the name of hydroxylaminetrisulphonate is sufficiently appropriate for such a compound, since, although a sulphatic salt, it is not actually a sulphate, but a mixed anhydride of acid salts, one being the 2/3-normal hydroxylaminedisulphonate and the other the acid sulphate : (80,K)OH + HON(SO,K), = H,O + (SO,K)*O*N(SO,K),. Lossen (Bey., 1892, 25, 440) has already pointed out that dibenzhydroxamic acid may be regarded as the mixed anhydride of benzhydroxamic acid and benzoic acid, and similarly in the case of other diacylhydroxy1- VOL.LXXXV. G82 RAGA : PEROXYLAMINESULPHONATES AND amines." Nitrososulphuric acid (aitrosyl hydrogen snlphate), the mixed anhydride of nitrous and sulphuric acids, is an example of a mixed inorganic anhydride. But the present salt, as the anhydride of two different acid salts, finds its close analogue in potassium hyponitrososulphate, (SO,K)O(N,OK) (Pelouze's '' nitrosulphate," Trans., 1895, 87, 109s ; 1896, 69, 1610), which is the anhydride of an acid hyponitrite and a n acid sulphate. The two mixed anhydrides agree in being stable in alkaline solution and unstable in acid solution, and in not giving barium sulphate with barium hydroxide or chloride.The evidence that the metasulphazilates have the constitution of hydroxylaminetrisulphonates is simple and direct, and similar to that as t o the constitution of the hyponitrososulphates. In the first place, sodium amalgam decomposes them, apparently quantitatively (.p. 96), into sulphate and normal aminedisulphonate (iminosulphate) : KO*SO,*O*N(SO,K), + 2Na = KO*S02*ONa + NaN(SO,K),, no sulphite being formed. Instead of sodium amalgam, the zinc- copper couple may be used to reduce hydroxylaminetrisulphonates in boiling solutions (p. 97), but in this case the aminedisulphonnte is apt t o hydrolyse during the heating. The result of this reduction of the salts not only proves their sulphatic constitution but bhows also that neither the formula ON(SO,K), (Claus, Hitntzsch) nor this formula doubled (Raschig) can possibly be right, because its acceptance would require that the sodium should act as a "carrier " of oxygen t o the sulphonate radicle.Dunstan and Goulding (Trans., 1899, 75, 792) have found that trialkyloxamines, such as (CH,),N:O, are reduced to frialkylarnines by zinc and acid. Were metaeulphazilates also oxaminic in constitution, they too should be reduced to aminetrisulphonates (nitrilosulphates). Sulphi tee, and even sulphur dioxide, have no action on the hydroxylaminetrisulphonates (p. 98). I n the second place, the metasulphazilates behave as sulphonated hpdroxylamine. They reduce acidified permanganate ; they give up one-third of their nitrogen in the form of ammonia when they are heated with soda-lime (Claus) ; and they can be hydrolysed ultimately into hydroxylnmine and acid sulphate.Although very stable salts in other respects, they cannot, indeed, remain in solution very long or be * Twenty-six years ago, Koenigs (Ber., 1878, 11, 615 and 1588) found that benzenesulphinic and nitrous acids react to form hydroxylaminedibenzsulphinic (dibenzsulphydroxamic) acid, and that this with more nitrous acid becomes a tri- benzsulphinic compound. Preliminary experiments made for the euthor seem t o show that the latter will almost certainly prove to be hydroxylaminetribenz- sulphizlic acid. Its production may probably be expressed by the following equation : 6C,H,*SO,H + 4HO'NO = 2(G6H,'SO,),N'O*(SO,'C,H,) + N,O + 5H10.HYDHOXYLAMINETRISULPHONATES. 83 kept for many months in the solid state without beginning t o hydrolyse. But if small amount of potassium or sodium hydroxide or, much more conveniently, of ammonia is added to their solution, they are permanent even for years in closed vessels.The other less sulphonated hydroxylamines have no such stability, but always revert more or less to sulphite and either nitrit.e or nitrous oxide. The hydrolysis is expressed by the equation : (SO,K)ON(SO,K), + 3H20 = 3H2S0, + HOaNH,. Taking into corrsideration their water of cry stnllisation, the potass- ium and the ammonium hydroxylaminetrisulphonates can only be written with doubled formulae, thus in some degree supporting Raschig's action in doubling Claus's formula for the former salt. But a cryoscopic measurement (p. 100) of the molecular magnitude of the sodium salt has shown that the simple formula is correct.hydl'oxYIamil2etrisu~honute, 1 2 (SO,K)ON( S0,K) 2, 3H,O, hitberto the only known salt, occurs in flattened, monosymmetric prisms, measurements of which have been made by Fock (Raschig) Its solubility in water a t 1 8 O is one in 25.37 parts. It is neutral to phenolphthalein, litmus, met hyl-orange, and other indicators. When slowly heated t o 100-120' in the air, i t loses some of its water of crystallisation, and is then hydrolysed by the remainder, acting together with the moisture of the atmosphere, so that at first it loses in weight and then gains. The residual mass is strongly acid, owing to the presence of acid sulphate. It has not been found possible to avoid hydrolysis and to obtain the anhydrous salt, even when the compound is very gradually heated in a current of dried air, after having already been exposed in a desiccator at the ordinary tempera- ture.Its water, therefore, could only be determined by difference. As expressed by $he foregoing formula, which agrees with Fremy's empirical formula, i t is certainly 3/2H,O, although Cllaus made it out to be 1H,O only. In his paper, five concordant analyses of the anhydrous salt, besides four analyses of the hydrated salt, are given ; and so far from reference being made to any difficulty being experi- enced in rendering the salt anhydrow, i t is stated that the water of crystallisation easily escapes at 100'. But i t is important to note that his four determinations of the water give numbers which are all somewhat higher than those required by his calculation, although the salt occurs in large, clear, non-deliquescent crystals, and that the figures thus calcu- lated are but little if any higher than those obtained by the author in two direct determinations of the loss of water by heating, in which the residues were always acid and therefore contained water.The salt has also been analysed by Raschig, but his results are not decisive Potassium ( P o 99)- a 284 HAGA : PEROXYLAMINESUJ,PHONATES AND Sodium H y ~ ~ o x y l a m i n e t r i s u ~ ~ o n a l e , (S03Na)ON(S0,Na)2, 2H20.- This salt, now prepared for the first time, is obtained by boiling zt solution of 2/3 normal sodium hydroxylaminedisulphonate and i t s equivalent half-molecule of sodium hydroxide with lead peroxide.It is more difficult to purify from accompanying salts than t'he potassium salt, but by very cautious addition of sulphuric acid, these salts may be con- verted into sulphate, which can be easily separated from the hydroxyl- aminetrisulphonate by freezing. It crystalliscs in aggregates of small, tabular, monoclinic crybtals (p. 99). The solubility of the salt is considerable, one part requiring only 2.83-2.85 parts of water a t 21.5'. Like the potassium salt, i t is neutral to indicators, and, when heated, hydrolyses in its water of crystallisation. Ammonium HydroxyZain.inet&ulphonate, H3,O23N$, or 2( S03NH,)ON(S03MH,),,3H20. -The analysis of this salt confirms the view that the amount of water present in the potassium salt is greater than that found by Claus.The ammonium salt forms thick, rhombic plates and prisms, similar to those of the potassium salt and probably isomorphous with them. But goniometric examination was impracticable, for although some faces were 7-9 mm. long, others were too imperfectly developed for determination. The salt is neutral to litmus and methyl-orange, and generally like the potassium salt, but it is exceedingly soluble in water, one part dissolving in 0.61 part a t 16'. The salt examined was prepared by digesting the basic lead salt with ammonium carbonate and evaporating the solution on the water-bath until it had almost lost its alkalinity, and then concentrating it further under reduced pressure over solid potassium hydroxide.I t s nitrogen and sulphur were found to be in much closer agreement with the formula showing 3/2 molecules of water; but here again the difference between the numbers for the two formulze is not very great (p. 100). Hydroxy- lead Hydroxy Za~~irLetrisulpl~onate , ON(S0,PbO .PbOH),,3H2O. -This tetrabasic and very insoluble lead salt, which appears to be the only insoluble hydroxylaminetrisulphonate, was prepared by pouring a warm solution of the potassium salt into excess of carefully prepared basic lead acetate solution. It is a chalky powder readily decomposed by a solution of an alkali carbonate (p. 100). PeroxyZamines Lclphottates (SuZphuxiZates ; Oxysulphazotates ; Xitroxydi- Only silver oxide and lead peroxide have, as yet, been used in the preparation of a peroxylaminesulphonate, but many other oxidising agents produce the violet coloration, thus indicating the conversion of su Zphonates) .HY DROXY LAMIN ETRISULPHONATES.85 a hydroxylaminedisulphonate into a peroxy laminesulphonate, as was pointed out by Fremy ; even chlorine when used in limited quantityis able t o produce this change. Ozone is an excellent reagent, rapidly producing a strong solution of the peroxylaminesulphonate when it is passed into a faintly alkaline solution of the hydroxylaminedisulphonate. Nitrous fumes are absorbed by an ice-cold solution of this salt, which assumes a dark-brown colour, and this solution, when rendered alkaline, slowly acquires the violet colour of the peroxylaminesulphonate. Also, when an ice-cold solution of potassium hydroxylaminedisulphonate and nitrite is barely acidified (preferably with sulphur dioxide), similar effects are produced. The temporary production of a violet colour is frequently observed in experiments made with the compounds of potassium nitrite and potassium hydroxylaminedisulphonates (Trans., 1900,77, 432).Hydrogen peroxide, potassium ferricyanide, potassium permanganate, and alkaline cupric solutions do not interact with a hydroxylaminedisulphonate. Even freshly precipitated mercuric oxide has no action on it, although the oxide is more quickly affected by light when suspended in a solution of the salt. In preparing potassium peroxylaminesulphonate, Fremy showed a preference for the use of silver oxide, whilst Claus, who assumed that the action of silver oxide was apt to proceed too far, preferred lead peroxide.Silver oxide gives a somewhat better yield and none of the silver goes into solution, whereas a little of the reduced lead peroxide dissolves and renders the salt impure. But the dissolved lead is readily removed, and the lend peroxide presents the advantage of being a t hand when wanted, whilst the silver oxide has to be prepared each time and the metal afterwards recovered. Lead peroxide has therefore been used in the present research. Fremy used either the 2/3- o r the 5/6-normal potassium hydroxyl- aminedisulphonat e as the source of the peroxylaminesulphonate ; Claus used only the latter, and Raschig chose the former. The advantage lies with the 5/6-normal salt, for, when prepared from a less alkaline salt, the peroxylaminesulphonate proves to be less easily purified and consequently less stable.The 5/6-normal salt is always so far hydrolysed in dissolving that it is converted into the 2/3-normaI salt, the potassium hydroxide beiug left in solution, as noticed by Claus. The presence of free alkali, however, moderates the action of the oxidising agent, and to such a n extent that a sufficiently concen- trated solution of the very soluble normal sodium hydroxylamine- disulphonate is not attacked a t all by lead peroxide. Apparently, therefore, lead peroxide acts as an acid oxidiser, in the form ot plumbic anhydride, as huggested by Fremy. The salt, which must be prepared just when it is wanted, is produced by mixing about 6 grams of the 5/6-norma1 hydroxylaminedisulphon-86 HAQA : PEROXYLAMINESULPHONATES AND ate (or the same amount of the 2/3-normal salt together with a small quantity of potassium hydroxide) and a little more than the same weight of lead peroxide (or of the silver oxide precipitated from a little less than the same weight of silver nitrate) and making up with water to 25 C.C.The mixture is agitated for 15 minutes in water near to, but not above, 40'. Then the solution is decanted without delay, treated with carbon dioxide (when lead peroxide has been used), and filtered, before cry stallisation sets in. The solution should therefore be kept warm up to this point. When it has remained some hours in an ice-box, almoht the whole of the peroxylaminesulphonate will have separated as a crust of minute, yellow needles.These can be recrystal- lised, but not without material loss, from hot water made slightly alkaline with potassium hydroxide. When, as appears to have been the case with Fremy, much hydroxylarninedisulphonate has been left unoxidised, some of this will be found with the peroxylaminesulphon- ate, from which it can hardly be wholly separated by recrystallisation, its crystals remaining coloured by the peroxylaminesulphonate, as observed by Hantzsch and Semple. Any close determination of the yield cannot be made directly, since the salt can rarely even be roughly weighed before decomposition sets in. Its amount has therefore to be estimated by letting i t decom- pose, igniting the residue with ammonium carbonate, and weighing the potassium sulphate. In this way, the yield of separated salt was found t o be a very little over three-fourths of the calculated quantity when silver oxide was used; and a little less than two-thirds when lead peroxide was taken.But by indirect means the amount of the salt actually produced can be shown to be much higher than this. As already mentioned (p. Sl), the exhaustive oxidation by lead peroxide of a hot solution of hydroxylaminedisulphonate has given nearly 88 per cent. of the calculated quantity of hydroxylaminetrisul phonate, a fact which signifies that a t least as much peroxylaminesdphonate as is equivalent to this percentageof the total sulphur must have been formed, since its production is intermediate to that of the hydroxylaminetri- sulphonate.Potassium peroxylaminesulphonate is very unstable in water and very slightly soluble in the cold. I n N/iO-solution of potassium hydroxide, which fairly represents its usual mother liquor, it is more stable, but still not very soluble; 100 parts a t 3O dissolve only 0.62 part of the salt, and a t 29Oonly 6.6 parts (p. 101). It interacts in solution with normal potassium sulphite and then produces hydroxyl- aminetrisulphonate and hydroxylaminedisulphonate, evidently in mole- cular proportions (p. l O l ) , this change being a fact of great theoretical importance. Its chemical activity is manifested in oxidising certain easily oxidisable substances and being thereby reduced to its parentHYDHOXY LAMINETltISULPHONATES. 87 salt, hydroxylaminedisulphonate.Although i t liberates iodine from hydriodic acid, i t fails t o oxidise hydrochloric acid. When tho latter acid in concentrated solution is poured on the solid salt, it sets up the same decomposition as that which occurs spontaneously (p. 88). But here, as the rise of temperature is moderated, definite although minute quantities of aminomonosulphonate and of hydroxylamine (not i t s sulphonate) can be found. The salt has practically no action on alcohol ; nitrous and sulphurous acids rapidly reduce it, so also does sodium amalgam, first t o hydroxylaminedisulphonate (as already observed by Schatzman), and then this salt passes slowly but corn- pletely into aminedisulphonate (iminoaulphate). Clean granulated zinc slowly reduces the salt, but copper does not.The spontaneous decomposition of the salt may, however, easily be mistaken for its slow reduccion by a reducing agent, since in tbis case also, as will be pre- sently described (p. 89), hydroxylaminedisulphonate is produced. The difference is readily detected by testing for nitrite, which is produced only in the spontaneous decomposition of the salt. Manganese dioxide very slowly decomposes it, causing a minute effervescence ; lead peroxide is inact,ive. Potassium permanganate is reduced t o green manganate. Clean filter-paper, unlike the paper in use i n Fremy's time, does not affect it. Part of the instability of peroxylaminesulphonates must be attri- buted to the presence of oxidisable impurities. Thus, Fremy noticed the decomposing action of atmospheric dust ; whilst nitrite, another impurity liable t o be found in the salt, also greatly increases its instability.Acids hasten the decomposition of the salt ; alkalis retard it. When drained on the tile from an alkaline solution, the salt may, under cover, remain undecomposed for two hours or more; but if washed on the tile and thus deprived of the traces of its adherent alkaline mother liquor, it will decompose i n a very few minutes. Nevertheless, on one occasion some of the salt thus purified mas kept on a tile for 11 months in a desiccator, and only then decomposed through a n accident. This, however, must be regarded as a very un- common experience. The sensitiveness of potassium peroxylamine- sulphonate t o acids has been recorded by others, but has been some- what exaggerated.When the salt is free from every trace of nitrite, its cold acidified solution may remain coloured for 40 minutes. An alkaline solution may not lose all its colour when kept in a closed vessel for more than a month. If sufficiently pure, the solid salt ruaj be preserved for a day or so under water rendered slightly alkaline with potassium hydroxide. The nature of the decomposition of potassium peroxylaminesulphon- ate occurring in the absence of alkali has already been examined, although in all cases very imperfectly, by Fremy and by Claus, and inss HAGA : PEKOXYLAMINESULPHONATES AND the presence of alkali by Kaschig. According to Fremy, the solid salt decomposes explosively when heated; when exposed to the air, it becomes strongly acid ; and when heated in solution, it yields sulphate and a gas mistaken by him for oxygen, but which was really nitrous oxide.H e was also mistaken in stating t h a t it melts readily and that when left in a closed bottle it evolves nitric oxide. Claus found that, whether in the solid state or in solution, whether when cold or moderately heated, the decomposing salt yields hydroxylaminetrisul- phonate and nitrous oxide, together with acid sulphate equivalent to one-fourth of its sulphur, according to the equation 2K,N,S401, + H,O = 2KHS0, + 2K,NS,O,,, + N,O. Rwchig has confirmed Claus's statements and also states that the solid salt or its solution also decomposes in this way even when left in contact with alkali. H e also adds that its solution when acidified is decolorised in a few minutes, whilst in the presence of alkali it can in some cases be heated to boiling without change.All these statements by Claus and Raschig require t o be modified in order that they may accurately describe the behaviour of the salt, and even then they fail to indicate the primary change which the decomposing salt undergoes. Thus the acid sulphato produced is seldom equal to one-fourth of the total sulphur, although it may be so, as twice found by Claus, and indeed also in the present investigation, but only when the salt had been used with too small a quantity of water to dissolve i t all on warming. 0 wing to this fact, only a part of the nitrogen, which does not become hydroxylaminetrisulphonate, appears as nitrous oxide, along with a small amount of free nitrogen.Solid potassium peroxylaminesulphonate is too unstable when dry and free from alkali t o exist many minutes without rapidly and almost explosively decomposing. I n this decomposition, slight white fumes of ammonium salt (probably pyrosulphite and pyrosulphnte), nitrogen and nitrous oxide, and a small quantity of sulphur dioxide are given off, whilst the residue, when the mass of the salt has been at all considerable, gets very hot (above 300'2) and melts. This residue consists of potassium sulphate (principally pjrosulphate) with a very little ammonium salt. Sometimes a trace of amine- moiiosulphonate can be detected by the mercuric nitrate test ; also a trace of hydroxylamine (or other substance reducing alkaline cupric solution), but none of the other sulphonates, the temperature having been too high to leave these substances undecomposed.The true products of the spontaneous decomposition of a peroxgl- aminesulphonate are only found (in company with small quantities of apparently secondary products) when the salt is heated t o boiling with enough water to dissolve it, and i n presence of sufficient alkali t o prevent both the acidification of the solution during the decompositionHTDROXPLAMINETRISULPHONATES. 89 of the salt and also the secondary changes which would result from acidification. The alkali does not appear t o modify the nature of the primary change, although i t distinctly increases the stability of the salt, as already mentioned (p. 87). When carriedout in the foregoing manner, the decomposition of a peroxylaminesulphonate proceeds largely in such a way that not only do three-fourths of the sulphur of the salt, as suggested by Cllaus and by Raschig, together with one- half of its nitrogen, come out as hydroxylaminetrisulphonate, but the rest of the sulphur and one-fourth of the nitrogen become hydroxyl- aminedisulphonate again, whilst the remainiog one-fourth of the nitrogen appears as nitrite, although some nitroiis oxide and sulphate, besides minute and uncertain quantities of other substances, are always produced (p.92). This result explains the production of the large quantities of acid sulphate and nitrous oxide observed by Claw and Raschig, for the nitrous acid when not neutralised by alkali interacts with the hydroxylaminedisulphonate and yields acid sulphate and nitrous oxide (Trans., 1900, 77, 433).The regeneration of hydroxylaminedisulphonate in the spontaneous decomposition of a peroxylaminesulphonate accounts for the fact, met with in the present investigat,ion, that much more hydroxylamine- trisulphonate is obtainable Ly heating hydroxylarninedisulphonate in solution with excess of lead peroxide than can be derived from the decomposition (out of contact with lead peroxide) of the peroxylamine- sulphonate equivalent to that quantity of hydroxylaminedisulphonate (p. 81). For in the presence of lead peroxide, that hydroxylaminedi- sulphonate which is regenerated by the independent decomposition of the peroxylaminesulphonate is oxidised again to more of this salt, to be again decomposed in the same way, until the whole of the disulphonate has become trisulphonate and nitrite, except that part of it which is lost as sulphate and nitrous oxide.Remembering that 4(SO,K),NOH gives 2( S03K)4N202, the larger yield of hydroxylamine- trisulphonate which should result mill be seen, on comparing the equation on page 81 with that just given, to be theoretically in the ratio 4: 3. It will now, too, be evident, on reference to Claus’s memoir, that his incomplete knowledge of the nature of the decom- position of the peroxylaminesulphonate led him to object too much to Fremy’s account of the action of the oxidising agent in producing hy droxy lamine tri sulphonat e. Conatitution.-The constitution of a peroxylaminesulphonate as a sulphonate was recognised by Claw, and is deduciblz from the fact t h a t it is formed by the dehydrogenation of hydroxylaminedi-90 HAGA : PEROXYLAMINESULPHONATES A N D sulphonate.The problem of its constitution as a nitroxy-compound remains to be solved, and the description just given of the potassium salt amounts to a demonstration, first, that its constitution is that of a peroxide and therefore of a peroximide; and, secondly, that its nitrogen is trivalent. Among the facts bearing on its constitution as a peroxylamine, that ip, as a derivative of H,NO*ONH,, are, first, those of its mode of formation. The 2/3-normal hydroxylaminedisulphonate hses its two hydrogen atoms, at the ordinary temperature and when i t is in aqueous solution, by the action of ozone, lead peroxide, silver oxide, and a variety of other substances : but not, however, by oxygen itself; for Raschig's observation, that n solution of hydroxylaminedisulphonate when exposed to the air may assume a slight violet colour, applies in reality only to the case where the 2/3-normal salt is contaminated with nitrite, the pure salt never oxidising nor colouring in this way. The interaction with lead peroxide points clearly either to the peroxide constitution or, but with much less probability, to a rise in the combining power of the nitrogen to quadrivalency.The fact of the ready reversion, ah the cornwon temperature and in solution, of a peroxylaminesulphonate to a hydroxylaminedi- sulphonate by acting as an oxidising agent is equally strong evidence of the same constitution.This reversion is also quantitative to an extent that admits of its being used to estimate the amount of the salt present in a solution (Schatzmann, Hantzsch and Semple). Its combination with a molecule of normal sulphite (p. S6) affords convincing evidence to the same effect, since it is effeckecl through the oxygen atoms of the peroxylaminesulphonate : (SO,K),NO*ON(SO,K), + K*SO,K = (SO,K),NOT< -t- (SO,K)ON(SO,K),. This interaction will be again discussed on page 91. Inferen- tially in favour of the peroxide constitution are also the odour which the peroxplaminesulphonates impart to the skin, their colour, and their decomposition into nitrous acid and sul phonat'ed hy droxylamines. So soon as it is recognised that peroxylaminesulphonates are per- oxides, all doubt is removed as to the valency of their nitrogen, which then can be only that of a triad.Contrariwise, when such a con- stitution is not admitted, the nitrogen of a peroxylaminesulphonate, with equal certainty, cannot be trivalent. I n order, therefore, to strengthen the conviction that the peroxylaminesulphonates are indeed peroxides and peroximides, it becomes important to state theHYDROXY LAMINKTRISULPHONATES. 01 reasons against admitting the nitrogen of these salts to be quadri- valent or more than trivalent. To begin with, i t is extremely improbable that oxidation by lead peroxide, silver oxide, or ozone should raise the valency of the nitrogen to only quadrivalency and not to quinquevalency, and that it should raise it a t all without converting the sulphonate t o sulphate radicles.Neither Claus nor Raschig assumes that it does, for according to them the nitrogen of the hydroxy lamined isulphonate is itself quinquevalent, But there are also two strong reasons for rejecting the assumption that the valency of the nitrogen is raised by the oxidation of hydr- oxylaminedisulphonates to peroxylaminesulphonates. One of these is the nature of the products of the spontaneous decomposition of a peroxylaminesulphonate. These products, in so far as they contain nitrogen, are all trivalent nitrogen compounds, namely and in the main, hydroxylaminetrisulphonate, hydroxylaminedisulphonate, and nitrite; if nitrous oxide is also recognised, that fact will not affect the argument. No nitrate can be found among these products (p.102). It is, of course, the establishment of the trivalency of the nitrogen of the first-named product which has really settled the matter. B u t as it is only as yet on the chemical work of Divers and the author (Trans., 1894, 65, 523), that the adoption of the trivalency of the nitrogen in hydroxylaminedisulphonates can be based, the result of a determination by a cryoscopic method (p. 100) of the molecular magnitude of the normal sodium hydroxylaminedisulphonate may be adduced in support of it. This result shows that the molecule of the salt contains but one atom of nitrogen (necessarily, therefore, trivalent), and not two atoms as had been represented by Claus and by Haschig. Now, the spontaneous decomposition of a peroxylaminesulphonate can only be hydrolytic, and is therefore one not affecting the valenoy of the nitrogen ; or, should this be contested, i t can still be asserted that at least this decomposition cannot be interpreted as a change involving a diminution in the valency of the nitrogen.The other reason against the belief that the valency of the nitrogen changes when a hydroxylaminedisulphonate is oxidised t o a peroxpl- aminesulphonate is that of the production of the two compounds of trivalent nitrogen, the hydroxylaminedisulphonate and hydroxylamine- trisulphonate, by the union of a peroxylaminesulphonate with a normal sulphite (p. 86). These two reasons for rogarding the nitrogen of a peroxylaminesulphonate as trivalent seem to be conclusive, and there- fore support the view that these salts are constituted as peroxides or peroximides.Since the sodium salt is even more unstable than the potassium salt, the determination of thu molecular weight of a peroxylamine- sulphonate has not been possible. It would seem better to modify92 HAGA : PEROXYLAMINESULPHOKATES AND Hantzsch and Semple's suggestion concerning the molecular weights of the two forms of t h e potassium salt (p. SO), t o the extent of giving the simple formula, (S0,K),N,02, t o the violet form, and reserving the double formula, or even a higher multiple of this, for the yellow form. P~oducts of Decomposition.-Without further experiments than those described on pages 94 and 106, the number of the products and the great variations in their proportions are such that the nature of the spontaneous decomposition of a peroxylaminesulphonate cannot yet be fully determined.But its general character can be indicated, now that the constitutim of both peroxylanlinesulphonates and hydroxyl- aminetrisulphonates has been determined. It can hardly be doubted t h a t the molecule of peroxylaminesul- phonate becomes halved by hydrolysis and converted into the hydroxyl- aminedisulphonate, always found i n abundance, and the hydyoperoxyz- uminesui'phonute, as yet undiscovered because incapable of continued existence, 1 h u s : (S03K)2NO*ON(S0,K)2 + H,O = (SO,K),NO*OH + H*ON(S0,K).3. It is already known (Trans., 1889, 55, 765 ; 1894, 65, 539) tbat, in the presence of a1 kali, the nitroxy-radicles oE a hydroxylaminesul- phonate tend to separate from the sulphonate radicles.Such a tendency, exercised in the presence of undecomposed peroxylamine- mlphonate, will lead to the production of hydroxylarninetrisulphonate and nitrite in the case of hydroperoxylaminesul phonate, and of the former salt and hypouitrite in the case of hydroxylaminedisulphonate, thns : (SO,K),N,O, + (SO,K),NO*OH = Z(SO,K),NO(SO,K) + HO*NO ; (S03K),N202 + (SO,K),NOH = 2(SO,K),NO(SO,K) + h(HON),. When the three equations are combined, the intermediate products disappear and the following equation is left, 6(S0,K),N202+ H,O= G(SO,K),NO+ 2NO,H+N,O ............ (1) or, leaving the comparatively stable hydroxylaminedisulphonate unchaoged, 2(SO,K),N,O, + H,O = 2(SO,K),NO + (SO,K),NOH + NO,H .. (2) It is fairly certain that the sulphate which, in grei-ttlg varying although never very large quantity, is always produced, does not come from the hydrolysis of the salt itself or from t h a t of either the hydroxylaminetrisulphonate or hydroxglaminedisnlphonate derived from it.For the trisulphonate is remarkably stable in the presence of alkali, and the disulphonate, although unstable in its presence,HYDROXYLAMIN ETRISULPHONATES. 93 yields not sulphate but sulphite. As this is also true of hydroxyl- aminemonosulphonate, i t may be assumed to be so in the case of peroxylaminesulphonate. The sulphate should therefore have another origin, which may well be taken t o be the decomposition of the hydroperoxylaminesulphonate in circumstances i n which i t fails to interact with peroxylaminesulphonate, perhaps because the tempera- ture of the solution is too lorn.I n that case, i t will naturally hydro- lyse, one half becoming hydroxylaminedisulphonate by oxidising the other half into sulphate and nitrous acid, B(SO,K),NO*OH + H,O = (2S0,KH + N0,H) + (SO,K),NOH. Or, it may well hydrolyse wholly into sulphate and nitrous oxide, 2(SO,K),NO*OH + H,O = 4S0,KH + N,O. These equations combined with the primary equation give, 2(S0,K),N,02 + 3H,O = 2S04KH + 3(S0,K)2NOH + N0,H . .. (3) 2(SO, K),N2O2 + 3H,O = 4S0,KH + Z(SO,K),NOH + N,O . . . . . . (4) An equation t o account for the production of nitrogen, and another for that of aminemonosulphonate are easily framed : (SO,K),N,O, +2H,0=4S04KH +N, .............................. (5 ) (SO,K),N,O, -I- 3H20 = 3S0,KH + (SO,K)NH, + NO,H... . . . . . . (6) A justification of the lower of these equations and a n illustration of the nature of the change, expressed by i t are to be found in the pro- duction of aminemonosulphonate from hydroxylaminedisulphonate when decomposing in presence of copper sulphate (Trans., 1900, "7, 978). By combining these six equations in different ways, the various results obtained can be explained (p. 107), although the conditions for the occurrence of one mode of decomposition more than another are not yet ascertained. Sabutier's Bluish-violet Acid.-Sabatier has studied the nature of the bluish-violet colour produced in a solution of nitrososulphuric acid (nitrosyl hydrogen sulphate) in the monohydrate of sulphuric acid by sulphur dioxide, and in other ways (p. SO), and has found this colour t o be more closely like that of a solution of potassium sulphazilate than the colour of the latter is like that of a solution of potassium permanganate.Oa this ground and from a consideration of the circumstances which give rise to the colour, he has suggested that i t is due t o the presence in the solution of the acid of Fremy's salt, constituted according to the formula ON(SO,H),. Sabalier may be right, but there is much to be said against this opinion. Firstly, the tints of the two coloured solritions are not so similar asthe asserts.91 HAGA : PEROXYLAM"ESULPH0NBTES AND Secondly, certain striking contrasts may be observed in the chemical character of the two solutions. Potassium peroxylamineoulphonate is produced by the action of lead peroxide and is not attacked by it, whereas the coloured acid solution is a t once oxidised by lead peroxide.Conversely, whilst this acid solution is indifferent towards sulphur dioxide and produced by it, potassium peroxylaminesulphonate is a t once changed by this reagent. Then, again, it has not proved to be possible either t o convert potassium peroxylaminesulphonate into this violet acid solution or to effect the opposite change. Mr. S. Sekiguchi, a Post-graduate of this University, has kindly carried out some experiments in this direction. Making the mixtures very gradually and keeping them cold by ice and salt, he has poured the solution, prepared from nitrososulphuric acid and sulphur dioxide in sulphuric acid, into a solution of potassium hydroxide; and, on the other hand, an aqueous solution of potassium peroxylaminesulphonate into some concentrated sulphuric acid ; in both cases, an almost immediate disappearance of the violet colour results.In the former case, too, the alkaline solution mas evaporated and crystallised, without finding any of the hydroxylaminetrisulphonate which would result from the decomposition of peroxylaminesulphonic acid and might, to some extent, in accordance with its usual stability, escape decomposition. Details of Expeviments. The Exhaustive Action of Lead Peroxide 031 Hgdroxykaminedi- gdphonates.-Potassium 213-normal hydroxylaminedisulphonate was boiled with excess of lead peroxide in about 15 times its weight of water, containing from 1/5 to 2/5 of a molecule of potassium hydr- oxide, until the solution had again become colourless.To the cold filbrate, just enough barium acetate was added t o precipitate all sulphate present ; the filtrate was then evaporated, and the hydroxyl- aminetrisulphonate crystallised out, as far as possible, and weighed. Potassium nitrite, produced in large quantity, was estimated in the mother liquor and alcoholic washings of the crystals of the hydroxyl- aminetrisulphonate by the urea method. Sulphate was found partly in solution and partly in the lead residue, which was extracted alter- nately with dilute nitric acid and potassium hydroxide. The sulphate, both in solution and residue, was estimated, and, in two cases, the soluble lead also, as a measure of the lead peroxide consumed. In one experiment, 73.2 grams of salt gave 58.2 grams of trisulph- onate in crystals, that is, 58.5 mol.of trisulphonate from 100 mol. of dipulphonate, or 87.75 per cent. of the theoretical quantity. Nothing else was determined, and so high a yield of hydroxylaminetrisulph-HYDROXYLAMINETRIYULPHON A'I'ES, 95 onate was only reached by adding alcohol to separate the last portions of the salt from the very concentrated nitrite mother liquor. In another experiment, 125 grams of the disulphonate gave 97.33 grams of trisulphonate, equal t o 57.33 mol. of trisulphonate to 100 mol. of disulphonate, or 86 per cent. of the calculated quantity. The amount of potassium sulphate was 21.5 mol. per 100 mol. of salt takeo, which leaves sulphur for the trisulphonate equivalent to 59.5 mol., as against the 57.33 mol.of crystallised salt. Very much nitrite mas found (37.5 mol. per 100 mol. of disulphonate taken), indicating the production of very little nitrous oxide. The only way t o interpret this large production of nitrite is to assume that, whilst 89-25 per cent. of the salt was oxidised into trisulphonate and nitrite, and only 3 per cent. into sulphate and nitrous oxide, 7.75 per cent. was oxidised into sulphate and nitrite, an assumption which cannot be easily justified. I n an earlier experiment, in which the crystallisation of the tri- sulphonate was only imperfectly carried out, 136.33 grams of the disulphonate gave 84.33 grams of the crystalline product, that is, 100 mol. gave 45.56 mol., or 68.33 per cent. of the theoretical quantity. But since the quantity of sulphate, almost if not actually the only other sulphur compound produced, amounted to only 19 mol.per 100 of disulphonate, the actual yield of trisulphonate can have been little short of 60.33 mol. per 100. The nitrite, as determined by the urea method, was 28.4 mol. per 100 oE disulphonate taken, But the lead peroxide consumed was in this case determined, and made out to be 71.5 mol. per 100 mol. of disulphonate, and this indicates the produc- tion of 31.8 mol. of nitrite. Accepting the mean of these numbers for the nitrite, i t results that about 90 per cent. of the hydroxylamine- disulphonate was converted into trisnlphonate and nitrite, and the rest into sulphate and nitrous oxide, I n an experiment with 35 grams of potassium hydroxylaminedi- sulphonate, in which the crystds of hydroxylaminetrisulphonate were not weighed, 100 mol.yielded 13 mol. of sulphate and 26 mol. of nitrite. Calculating from these quantities, 78 per cent, of the salt was oxidised into trisulphonate and nitrite, 1 5 5 into trisulphonate and nitrous oxide, and 6.5 into sulphate and nitrous oxide. The tri- sulphonate produced will therefore have been about 93.5 per cent. of the calculated quantity, or 62.33 mol. per 100 mol. of disulphonate. Another experiment was made on the normal sodium hydroxyl- aminedisulphonate (Trans., 1894, 65, 546) in dilute solution, 1 P33 grams being taken without any addition of sodium hydroxide, because the alkalinity of the salt was sufficient to protect it. But in this experiment, only the quantities of lead peroxide consumed and of sulphate formed were estimated.Exactly as happened in the experi-96 HAGA : PEROXYLAMINESULPHONA'l'k3 AND ment with the potassium salt, 71.5 mol. of lead peroxide were consumed per 100 mol. of sodium salt. The sulphate amounted to 34 mol. per 100 mol. of salt used, more, that is, than in the experiments with the potassium salt. The calculated quantity of sodium hydroxylamine- trisulphonate was correspondingly lower, 55 mol. per 100 mol. or 82.75 per cent. of the theoretically possible quantity. Reduction, of Potassium ~ydroxylaminetrisul~honnte by Sodium Amalgam.-In the interaction between sodium amalgam and potassium hydroxylaminetrisulphonate in aqueous solution, the two liquids become warm, and the action is soon over if the two are well shaken together. No gas is evolved, and nothing is left in solution but the two salts, sulphate and aminedisulphonate (iminosulphate).The latter is easily recognisable by i t s separating as the very sparingly soluble 2/3-normal potassium salt when the solution is nearly neutralised with a n acid, and also by its nearly insoluble normal mercury-potassium salt (Trans. 1892, 61, 976; 1896, 69, 1629). But the salt was also analysed quantitatively (p. 97) in order to demonstrate i t s nature beyond question. By cautiously adding hydrochloric acid t o the cold solution until i t hns become almost neutral t o methyl-orange, and then pre- cipitating with barium chloride, the sulphate is partially separated from the aminedisulphonate; the latter may then be estimated as sulphate in the filtrate after hydrolysis at 150".I n an experiment carried out in this way on 2.447 grams of potassium hydroxylamine- trisulphonate, the barium sulphate precipitate was washed w i t h cold, and then with hot, water, ignited, and weighed. The sulphate from the hydrolysed aminedisulphonate was treated a s in an ordinary sulphate determination. I n this way determined, 34.79 per cent. of the sulphur came out a s sulphate and 64.88 per cent. as aminedisul- phonate, leaving 0.33 per cent. unaccounted for. I n accordance with t h e equation, the actual numbers should have been 33.33 and 66.67 per cent. respectively. By other experiments, it was, however, estab- lished that some of the aminedisulphonnte WRS precipitated with the sulphate.No doubt, also, some barium chloride was carried down. Potassium hgdroxylaminetrisulphonate, 1.441 grams, was reduced by sodium amalgam, and the solution neutralised and precipitated in the cold by barium chloride as above described. The washed pre- cipitate was then heated for 4 hours a t 150" with dilute hydrochloric acid in a sealed tube. The acid was nearly neutralised, and the barium sulphate collected, washed, and weighed as usual. The fil- trate from this yielded a fresh precipitate with barium chloride, for the barium aminedisulphonate, which was precipitated with the sulphate, had been hydrolysed into barium sulphate and ammonium hydrogen sulphate. Therefore, from the weight of t,he main pre- cipitate of sulphate was deducted that of the small quantity lastHYDIXOXYLAMINETRISULPHONATES.97 obtained, and the remainder taken as sulphate actually produced by the sodium reduction. It amounted to the equivalent of 34.20 per cent. of the total sulphur. The aminedisulphonate in the original filtrate from crude sulphate was determined by hydrolysing and weighing its sulphur as sulphate. To the weight of this was added twice that of the barium sulphate obtained, as just described, from the soluble sulphate extracted by hydrolysing the crude barium sulphate, because twice that quantity represented the total sulphur of the aminedisulphonate precipitated along with the actual sril- phate. This sum was equivalent to 65.75 per cent, of the total sulphur. That these data still deviate from the calculated numbers is no doubt due to the adhesion of a little barium chloride to the sulphate when precipitated in the cold.The barium of this chloride will have rendered insoluble some of the sulphate which should have dissolved out through the hydrolysis of the aminedisulphonate simul- taneously precipitated. There seems, therefore, to be no reason f o r doubting the quantitative accuracy of the equation given on p. 82. An experiment was then tried to see whether closer resdlts could not be got by removing as much as possible of the aminedisulphonate from the solution before precipitating the sulphate, first crystallising out most of it from the nearly neutralised solution, and then removing some of the remainder as the mercury-potassium salt, by digesting the solution with mercuric oxide.This method, however, did not give better results than the preceding. Reduction of Potassium HydroxplccminetrisuZphonccte by the Zinc- coppe?. Couple.-The reduction of the trisulphonate was successfully effected by boiling its solution (to which a few drops of sodium acetate solution had been added in order to protect the salt from hydrolysis) with some zinc-copper couple. But in consequence of the necessity of boiling the solution, hydrolysis of the aminedisulphonate is apt to set in. Some aminedisulphonate prepared by the sodium amalgam method, and another sample, prepared by the zinc-copper couple, were analy sed with the following results : By sodimn. By zinc-copper. Calc. Potassium.. . . . . . . . . . . 30.68 30.72 - 30.89 Sulphur,. , . .. , . , . . . . . 25.09 24.85 25-94 25.30 Nitrogen .. , , . . ... ... 5-32 8-16 6.64 Hydrolysis of cc z~ydroz?/~cci~~inetr~su~~~~o~~cct~.--The complete hydro- lysis of the hydroxylaminetrisulphonates is more difficult to effect than that of any other of Eremy’s salts. I n the quantitative analysis of the salts, it was found necessary to keep the acidified solution for 5 hours a t 180-200°. In the case of the potassium salt, the mean VOL. LXXXV. H98 HAGA : PEROXYLAMINESULPHONATES AND percentage of sulphur then came out as 23.18; at 150° only, for 4 hours, it was 22-55 ; and a t 90-100' for 5 hours, and then 3 hours at 130°, it gave only 22.64. In this case, the nitrogen of the hydroxyl- amine obtained (as measured by the iodine method) amounted only t o 2.5 per cent. I n another case, where the hydrolysis was allowed t o go on for 48 hours at 90-95', and then 2 hours a t 130-134', the nitrogen obtained as hydroxylamine was 2.71 per cent.(79.75 per cent. of total nitrogen). Imact%ty of 8ulphites towards ~ydroxy~c6m~netr~su~~honutes.-~o~ass- ium hydroxylaminetrisulphonate weighing 2 grams, in sufficient water to keep the salt in solution, was left for 3 days with 3 grams of potass- ium metasulphite, rendered slightly alkaline t o lacmoid paper (whilst strongly acid t o litmus). The sulphite was then precipitated by barium hydroxide and the filtrate evaporated. I n this way 1.98 grams of the hydroxylaminetrisulphonate crystallised out. The analysis of the salt thus recovered is given as that of I1 among the analyses of the salt below. Analysis of Potassiwnz ~ y c l i .o x y Z a n t i n e t r ~ s u ~ ~ ~ o ~ t a ~ ~ . - A l ~ h o u ~ ~ thia has been analysed by previous workers, it was necessary to make several careful and full analyses in order t o establish the fact that it contains more water of crystallisation than the proportion stated by Claus and by Raschig. Four separate preparations were analysed. I. 0.4954 substance gave 0.3117 potassium sulpbate ; 0,5088 gave 0.8581 barium sulphate ; 0.3387 gave 0*5680 barium sulphate ; 042881 substance, finely powdered and heated in a current of dried air, first a t 96' and then up to llOo, lost 0.0138 ; 0.2174 lost in this way 0*0101. 11. 0.2272 substance gave 0.1429 potassium sulphate ; 1.0676 treated with sodium amalgam for 34 hours and then hydrolysed at 150' for 3 hours, gave 1.7918 barium sulphate and ammonia = 25-59 C.C. N/10 acid.111. 0.2288 substance gave 0.1451 potassium sulphate ; 0.1003 gave 0.1710 barium sulphate. IV. 0.8505 substance gave 0.5347 potassium sulphate ; 0.34475 gave 0.5799 barium sulphate ; 2.4425, by sodium amalgam treatment and hydrolysis at 150" for 3 hours, gave ammonia = 51.38 C.C. NIlO acid; 0,7650, by the Dumas method, gave 22.3 C.C. moist nitrogen a t l6O and 758 mm.HYDROXYLAMINETRISULPHONATES. Potassium, . . . . . . . . . . . . . . . . . . . . . ) ) I1 .................................. -*d Found, I ) ) 111 ................................... ) ) IV ................................... Mean ........................................ Calculated for 1/1H,O ....................,, 3/2H,O ..................... Fremy .......................................... Claus, found (taking old atomic weights) 2 ) J j $ 7 2 1 Y ) 9 ) $ 9 9 , 9 7 Claus, mean ................................. calc. (taking old atomic weights) Raschig ....................................... ) ) ............................... * ' . - I ), 28'25 28 '24 28'47 28-23 25.30 25.96 28-32 28.02 28.63 28.55 28-67 28'79 25'66 28.88 28-47 28'64 Sulphur. ~ {;;:A: 23-07 23'42 23'12 23'18 23'71 23'19 23'40 Nitrogen. - - 3.37 - { 'g;' 3 -38 3'46 3 '39 3'48 - 1 3'24 23'69 - 23'76 3 *31 23.73 3-28 23.70 3.45 23'64 - 23.38 i - - - Water. (4'89) (4'65) - - - - (4.77) 4 '49 6-52 5-04 5.20 5'01 4-71 4.99 4 -44 - __ - - Claus has also given the results of five closely concordant analyses of the anhydrous salt, and should therefore have experienced no diffi- culty in rendering it anhydrous.I n the attempts to determine total water, recorded above, the residue was always acid in consequence of the unavoidable hydrolysis and fixation of some of the water of crys- tallisation. Amalysis of the Sodium Xalt.-Two distinct preparations of the sodium salt were analysed : I. 0.4910 substance gave 0.2801 sodium sulphate; 0,3845 gave 0,7174 barium sulph&e, after hydrolysis at 200' for 3 hours. Hydro- lysed at only 160' for 5 hours, 0.4548 gave 0.8378 barium sulphate, = sulphur 25.30 per cent. only. 11. 0-6097 substance gave 0.3455 sodium sulphate; 0.1750 gave 0.3268 barium sulphate, after hydrolysis at 210° for 3 hour?; 0.7533 gave 2400 C.C.moist nitrogen a t 760.8 mm. and 17O, = 0.027 nitrogen. A discussion of this matter is given on page 83. S odiu m . Sulphur. Nitrogen. - Found, I .................. 18.50 25.64 Na,S3N0,,,2H,O ......... 18.42 25.62 3.76 ,, I1 ................. 18.36 25.67 3-70 Crystallography of Sodium Hydroxykanzi~etrisul~~~o~ate.--Professor Jinbo has kindly given me the following description of the crystals of this salh, which were examined under his directions by Mr. M. Yatsuki, University Post-graduate. Thick, tabular, monoclinic crystals, about 3 mm. long and 2 mm. wide, elongated in the direction of the vertical axis. The observed faces are of seven kinds, of which b is the largest H 2100 HAGA : PlCROXYLAMINESULPHONATES AND and apparently the plane of symmetry.m, making with b an angle of about 115O, may be taken as a prism ; d, e, and f as pyramids ; c as the base, and g as a positive orthodome. Two other faces in the zone of the orthodiagonal are sometimes observed. A crystal laid flat on the clinopinacoid shows an extinction angle of 30' to the vertical axis, in the acute angle between this and the clinodiagonal. AnuZysis of the Ammonium SaZt.-The total nitrogen ol the am- monium salt was determined by tho Dumas method. Found. 2H,,01,N,Sy,3H,0. H,,O,,N,S,,H,O. Sulphur ......... 27.63 37.36 38.08 Nitrogen ......... 16.06 15.98 16.40 Anulysis of the Basic Lead Salt.-The salt wits dried for analysis in a current of dry air a t 100' in the case of preparation I, and at l l O o in that of 11. The salt was quite free from potassium but contained a trace of acetate.Found. Found. H,Q1,NS,Pb,. Lead ............... 74.41 74.14 74.7 1 ............ 5-79 Sulphur 5.99 - Determination of the Molecular Magnitude of Sodium Hydroxyl- aminetrisu2phonate.-This was carried out by Lowenherds method with melted sodium sulphate crystals (Zeit. physikul. Clam., 1896, 18, 70). Fused sodium Hydrated salt. Anhydrous salt. sulphnte. At. 11. w. 2.479 = 2.2411 59-41 1 - 0.369' 332.20 3.478 = 3.0210 57.520 - 0,510 335.56 OI0NS3Na3 requires 339.37 Molecular 3dagnitude of Normal Sodium HydyoxyZaminediuuL phonate.-HYDROXY L AMIN ETRISULPIIONATES. 101 Fused sodium Crystnllised salt. sulpiiate. At. M. W. 1.220 36.8180 - 0.39' 233 2.023 37.1980 - 0.74 239.6 O?NS,Na, requires 239.3 With this molecular weight the nitrogen is necessarily trivalent.Solubilily of Peroxylaminesulphonate in LVjlO Solution of Potassium Hydroxide.-'l'he purified salt, previously washed on the porous tile with some of the solvent, was shaken with i t for from 15 to 20 minutes, the temperature of the solution being 29'. After Some time, 5 C.C. of the clear solution were withdrawn with a pipette. The rest of the solu- tion, along with the undissolved salt, was left for some hours in ice, when again 5 C.C. mere taken out, the temperature being 3'. The two portions were each weighed and the amount of dissolved salt ascertained by a sulphur determination. It was thus found that 0.163 gram of salt was dissolved in 5.03 grams of its alkaline solution a t 29', and that 0.027 gram was dissolved in 4-980 grams of its solution a t 3'.Interaction of Potcrssiurn Pgrox~lc~nzinesul~~onate am! Nornatd Potassium Su2phite.-To a solution of 3.6 grams of potissium peroxyl- aminesulphonate, containing only a very small quantity of potassium hydroxide, a solution of normal potassium sulphite (neutral to phenolphthalein) was added from a burette, with constant stirring, until the violet colour of the solution was entirely discharged. The change took placs quickly but not instantly. The quantity of sulphite required was only a little more than that indicated by theory. After a short interval, baryta water was added to precipitate the excess of sulphite and the hydroxylaminedisulphonate. The excess of baryt a was removed from the filtered solution by carbon dioxide and the filtered solution evaporated so as to get out as much as possible of the sparingly soluble potassium hydroxylamine trisulphonate.Some more of this salt was precipitated by adding twice the volume of alcohol and leaving the mixture for some time. The total trisulphonate thus separated weighed 2.268 grams, or 81.5 per cent. of the calculated quantity. The barium precipitate was triturated in a mortar with very dilute acetic acid, added very slowly so as to avoid as far as possible having any local excess of acid. When the solution had become neutral to phenolphthalein, the undissolved barium sulphiie was filtered off. Potassium carbonate in slight excess was added and the whole left for a day. Then, the solution, filtered from the barium carbonate and neutralised with acetic acid, was concentrated in a vacuum over sul- phuric acid and mixed with twice its volume of alcohol.In 12 hours, the quantity of precipitated crystalline 2/3-normal bydroxylamine- disulphonate weighed 1 *55 grams, this being equal to 76 per cent. of the102 HAGA : PEROXYLAMINESULPHONATES AND calculated quantity. It mas pure, except for a trace of aminetri- sulphonate (nitrilosulphate), doubtless due to the action of the sul- phurous acid unavoidably liberated in the process of separating the barium sulphite from its own barium salt by acetic acid. It was identified by hydrolysis into sulphate and hydroxylaminemonosul- phonate, and above all by its producing the bluish-violet peroxylamine- sulphonate when warmed with lead peroxide and a small amount of alkali.No nitrite was found in the mother liquor of the hydroxylamine- trisulphonate, showing that the production of the latter salt had not been due to spontaneous decomposition of the peroxylaminesulphonate. Hydroxylaminetrisulphonate and djsulphonate are, in fact, the only substances which could be detected among the products of the inter- action of the peroxylaminesulphonate and sulphite. Since, therefore, the separated quantities of theee products were found to be in approximately molecular proportions, and as these salts are not in- soluble, even in their alcoholic mother liquors, it may be regarded as proved that the interaction which takes place is exclusively that represented by the equation on p. 90. Sporztuneous Decomposition of Potassium Peroxyk~~minesuZ~~~onate.- The principal products of the spontaneous decomposition of a peroxyl- aminesulphonate in hot alkaline solution are easy to recognise.Unless very dilute, the solution yields crystals on cooling and more on evaporation, A t first the sparingly soluble hydroxylaminetrisulphonate alone crystallises, and later on both this and the equally sparingly soluble hydroxylaminedisulphonate. In each case the crystals are characteristic and easily distinguished. The presence of the disul- phonate in the solution is quickly and distinctively indicated, as has just been mentioned, by warming with a small quantity of lead peroxide, which gives it again the bluish-violet colour of peroxylamine- sulphonate. By removing sulphate and hydroxylaminedisulphonate from the solution by barium hydroxide, nearly all the hydroxylamine- trisulphonate can be crystallised out ; the mother liquor containing the nitrite may then be tested in any of the usual ways for this salt$.It was important to know whether any nitrate is formed by the decomposition, and therefore necessary first to get rid of all the nitrite present by a process that does not convert any of it into nitrate. The nitrite was accordingly changed into aminetrisulphonate (riitrilo- sulphate) by adding enough potassium carbonate and then passing in sulphur dioxide’until the solution became acid, a t which point the aminetrisulphonate that had been produced a t once hydrolysed (Trans., 1892, 61, 954). Lastly, by blowing in air until all the re- maining sulphrrr dioxide had been expelled, the acid solution was left free from either nitrite or sulphite, and, therefore, ready for testing for nitrate.The application of the None of tbis salt mas found,HYDROXYI~AMINETRISULPHONATES. 103 process of sulphonating the nitrite to the determination of total nitrogen in solution, is described on p. 104. The testing for aminemonosulphonate (aminosulphate) among the products of decomposition of a peroxylaminesulphonate is not an easy matter. The method adopted was to oxidise all the hydroxylamine- disulphonate by boiling the solution with lead peroxide until i t was again colourless. The nitrite was then oxidised by pouring the solution into potassium permanganate solution to which sulphuric acid had been added. iUercuric nitrate solution then precipitated from it a little oxymercurjc aminemonosulphonate (Trans., 1896, 69, 1649), which, when treated with hydrogen sulphide, left the acid agGin in solution.By evaporation and addition of strong sulphuric acid, the acid was obtained in characteristic crystals (Zoc. cit., 1642), which were sometimes weighed. The quantitative examination of the solution is a troublesome and less satisfactory operation. The peroxylaminesulphonate can hardly be obtained for weighing in the dry and pure state, because of its instability. Therefore, after its composition had been found, from concordant analyses of four different preparations, to be that ascertained by previous workers, the preparation of t h e solution and its analysis after the salt had all decomposed were carried out in the following way. The peroxylaminesulphonate, recrys- tallised two or three times from hot water made alkaline with potassium hydroxide, was drained for a short time on a tile from its mother liquor, and at once dissolved in suitable quantity in water to which had been added a measured quantity of potassium hydroxide, The solution was maintained at the boiling temperature until colourless through the complete decomposition of the salt.The cold solution was then weighed off into four portions: one of 5 per cent. of the whole, for estimating the amount of peroxylaminesulphonate that had been dissolved; another of 15 per cent., for estimating the quantity of hydroxylaminetrisulphonate produced ; a third and a fourth portion, each of 40 per cent., for estimating i n one the quantity of sulphate, and in the other that of nitrite produced.The quantity of peroxyl- aminesulphonate taken was determined by weighing as barium sulphate the total sulphur in the solution. To ensure the hydrolysis of all the sulphonate, the solution was heated with hydrochloric acid in sealed tubes for 4-5 hours at 180-200". To determine the quantity of sulphate which had been produced, very dilute hydrochloric acid was added with constant stirring until t h e solution was only barely alkaline to phenolphthalein, then much ammonium chloride was added before precipitating with barium chloride, in order t o keep the hydroxylaminedisulphonate in solution as f a r as possible. The impure sulphate, washed with ammonium104 HAGA : PEROXYLAMINESULPHONATES AND chloride solution on the filter, was transferred t o a beaker, and digested in the cold with very dilute hydrochloric acid, washed again on the filter with boiling water, and then ignited in the usual way.The hydroxylaminetrisulphonate was estimated by leaving the solution with sodium amalgam for two days, occasionally shaking the two together so as to convert this salt into hydroxylaminedi- sulphonate, and then all the hydroxylaminedisulphonate in the solution into aminedisulphonate (iminosulphate). The mercury having been filtered off and washed, hydrochloric acid was added to the solution until it was only just alkaline t o methyl-orange, and then an excess of ammonium chloride was int'roduced. The sulphate was finally pre- cipitated and treated as before described.Deducting from this quantity of sulphate that which was present before the treatment with sodium amalgam, there remained the sulphate equivalent to one-third of the sulphur of the h-jdroxylaminetrisulphonate, from which the quantity of this salt was calculated. Assuming hydroxylaminedisulphonate t o be the only other sulphur compound produced in the decomposition of the peroxylaminesulphonate-an assumption which is newly exact- the amount of this salt was then calculated as being equivalent to the sulphur not found either as sulphate or hydroxylamine- trisulphonate. The slight error in this assumption is caused by t h e production of very small quantities of aminemonosulphonate (aminosulphate). As to the last-named salt, i t has not been possible t o do more than ascertain that its quantity is usually quite small, although 2 mol.of tho crystalline acid (p. 103) per 100 mol. of hydroxylaminedisulphonate oxidised by the lead peroxide were once actually obtained. I n ot'her words, the amount of sulphur found as aminemonosulphonate was in this instance 1.03 per cent. of that of the hydroxylaminedisulphonate used. To determine the total nitrogen in the solution, the nitrite was completely sulphonated to aminetrisulphonate (nitrilosulphate) by adding enough potassium carbonate for the purpose and then passing in sulphur dioxide until a piece of lacmoid-paper was just reddened (Trans., 1892, 61, 954). Next, the hydroxylaminetri- sulphonate in the solution was reduced by sodium amalgam, as above described, to sulphate and aminedisulphonate.Having thus brought all the nitrogen into aminesulphonates, the hydrolysis of these substances by hydrochloric acid was effected by heating, first, on the water-bath until all t,he sulphur dioxide had been expelled, and then for some hours in a pressure-tube a t 150O. The solution distilled with alkali gave up all its nitrogen as ammonia. The difference between this and that originally present as peroxylamine- sulphonate gives, indirectly, the quantity of nitrogen in the gases, whilst the difference, again, between the total nitrogen in the solutionHYDHOXYLAMINETRISULFHONATES, 105 and the sum of the quantities found as disulphonate and trisulphonate is the nitrogen which was present as nitrite. Although the experimental work in estimating sulphate and hydroxylaminetrisulphonate was performed with great care, no high degree of accuracy in the results could be expected. A test experi- ment was made t o see to what extent the method was imperfect. A solution was prepared by dissolving potassium sulphate, potassium hydroxylaminetrisulphonate, potassium hydroxylaminedisulphonate, and sodium nitrite in water to every 100 C.C.of which 5 C.C. of N/lO solution of potassium hydroxide had been added. The solution was twice analysed for sulphate and trisulphonate in the way described above. The quantities, taken and found, are here given in grams per 100 C.C. Taken. F o iuld. Trisulphonate.. .... 2.580 2.547 2.624 Sulphate ............ 0.347 0.380 0.373 Disulphonate ......0,622 0.629 0551 Nitrite ............ 0.208 0.212 0.217 From this experiment, i t seems that the sulphate may come out nearly 10 per cent. too high, no doubt for two reasons; one that being precipitated in the cold, the barium sulphate retained other salts with i t ; the other and principal reason being that, in the process of neutralising the solution, some of the disulphonate must be decom- posed, yielding sulphate. The numbers fop the trisulphonate are much more satisfactory, being less than 1.7 per cent,. too high, apparently because they represent the difference between two sulphate determinations, the error in t h e one counterbalancing the correspond- ing error in the other, When, however, we come to the numbers for the disulphonate, which are calculated from those for the other substances, it is Been how large the error may become, being in one case as much as 11.4 per cent.too low. Similarly, the :quantity of nitrite, calculated from those of the other substances, may come out as much as 4.5 per cent. too high, The expression of the errors as percentages only holds good, of course, where the salts in an actual experiment are nearly in the same proportions as here taken, as they were generally found to be. The quantities of nitrite and of gases yielded by the peroxylamine- sulphonate may also be each determined directly. The nitrite may be estimated by the urea method, as stated on p. 94, most of the sulphonate salts having first been crystallised out and washed with alcohol. The method for collecting and measuring the gases produced during the decomposition consists in letting this proceed in a closed vessel from which the air is withdrawn.A stout-walled, cylindrical bolt-head, of about 250 C.C. capacity, with a stopcock sealed on to it, mas exhausted106 RAGA : PEROXYLAMINESULPHONATE8 AND and then opened with its mouth in the solution of peroxylamine- sulphonate and potassium hydroxide. About 200 C.C. were allowed t o enter, holding between 6 and 7 grams of the salt in solution. The tube was again exhausted and the stopcock being then closed, the salt was decomposed by heating the solution. When cold, the apparatus was connscted with a Sprengel pump and the gases drawn off and measured. They proved t o be free from nitric oxide, but, on treat- ment with strong alcohol, a small proportion of nitrogen remained un- dissolved.The experiments on this method of determining the gases have been very few, and not such as have admitted of their utilisation in this paper, beyond giving proof that nitrogen in small quantity is generated along with the nitrous oxide, which is the main constituent of the gaseous mixture, and that the quantity of the gases may vary greatly in different experiments. Where the decomposition of the peroxylaminesulphonate proceeds in the presence of lead peroxide, as it is made to do in the prepara- tion of hydroxylaminetrisulphonate, no hydroxylaminedisulphonate can remain in the solution, and in place of i t is found principally an increase in the quantities of trisulphonate and nitrite. The absence of the disulphonate simplifies the analysis, as is seen on p.94. Eight analyses of the products of the spontaneous decomposition of the peroxylaminesulphonate were made. In Expt. 1, a solution holding 2.31 84 grams of potassium peroxylaminesulphonake and 60 C.C. of N/lO solution of potassinm hydroxide was made up to 150 C.C. and then found to weigh 150.79 grams. It was slowly heated to the boil- ing point., and kept boiling till decolorised. Expt. 2.-The sollition, weighing 234.3 grams and containing 2.547 grams of the salt and 72.3 C.C. of N/10 potassium hydroxide, was left in the cold for two days, and then boiled until colourless. During the boiling, a reflux condenser was used to retain the water in the solution. Expt. 3.-A solution, weighing 120.42 grams and measuring 120 C.C. of 1.22 grams of salt and 11-4 C.C. of N/lO potassium hydroxide, was decomposed by boiling. Expt. 4.-The solution weighed 134.9 grams, and contained 1.8576 grams of salt and 30 C.C. of N/10 potassinm hydroxide; i t was decomposed by boiling. Expt. 5.-A solution of 0.6601 gram of salt and 80 C.C. of X/10 potassium hydroxide, weighing 34.25 grams, was left in the cold for a week, when it had become colourless. Expt. 6.-Like the last, but the solution weighed 266.7 grams and the salt 5.27 grams, whilst the potassium hydroxide was taken in about the same proportion as before. Expt. 7.-The solation was a portion of the same as had been used for Expt. 2. When kept in a closely- stoppered flask, it had only lost all its coloiir after about five months. Expt. &--This experiment differed from the others in the use of baryta-water in place of potassium hydroxide, and to this must beHYDROXY LAMINETRISULPHONATES. 107 attributed the production of so much sulphate and hydroxylamine- disulphonate. I n the table, the ncmbers of molecules of the several products yielded by lOO(SO,K),N,O, are given according t o calculation from the analyses made in the way above described, and without any corrections €or the "probable, but variable, errors inherent in the method. The solution took a month t o lose all its colour. RIol. xeight. 1. 2. 3. 4. 5. 6. '7. 8. (SO,K),NO ......... S5 102.3 101.7 77.7 91.4 55.3 86 12.9 (SO,,I<),NOII: ...... 61 30 23-6 65.4 42-3 42 40.4 133.2 S0,KH ............ 23 33 47.8 36 41.2 60 61.2 94.7 HNO, ............... 49 36 b2'5 50'2 35 37 26'4 - Without fuvther experiments, i t does not seem possible to account for the wide variations in these numbers, except where baryta was used. From Expts. 2 and 7, started on portions of the same solu- tion, i t seems clear that, with the slow decomposition of the peroxyl- aminesulphonate which goes on in the cold, instead of the rapid change which occurs at a boiling heat, molecular quantities of hydroxyl- aminedisulphonate and sulphate take the place of some of the hydroxylaminetrisulphonate, and t h a t a little of the hydroxylamine- disulphonate is replaced by its equivalent of sulphate and nitrous oxide. This becomes more obvious when equations in these two cases are given with only 12 molecules instead of 100 molecules of decomposing peroxylaminenulphonate. This is possible without deviating from the numbers forind more than t'he imperfections of the analytical method allow. (2) 12(SO,K),N,O, + 6ET,O = 12(SO,K),NO + 4(SO,K),NOH + (7) 12(S03K),N,01 + 8H,O = lO(SO$),NO + 5(SO,K),NOH + 4SO,KB + 4KO,H + 2N,O. 8SO,HH + 3NO,H + 3N,O. The production of small quantities of nitrogen aad aminemono- sulphonate is of necessity ignored in the above calculabions. The author gratefully acknowledges his indebtedness to Dr. Divers, F.R. S., for a thorough revision of his manuscript. COI.T,R:GF, OF SCIENCE, IMITRIAL UNIVERSITY OF TOKYO.

ISSN:0368-1645    

DOI:10.1039/CT9048500078

出版商:RSC    

年代:1904

数据来源: RSC