摘要:

OF THE CHEMICAL SOCIETY, TRANSACTIONS. QammitfeE 01 H. E. ARMSTRONG, Ph.D., LL.D., E. 0. C. BALY. HORACE T. BROWN, LL.D., F.R.S. A. W. CROSSLEY, D. Sc., Ph.D., F. R.S. WYNDHAM R. DUNSTAN, D.Sc., Ph.D., F.R.S. F.R.S. @ublicrzfian : M. 0. FORSTER, D.Sc., Ph.D., F.R.S. R.. MELDOLA, F.R.S. CT. T. MORGAN, D.Sc. SirW.RAnlsAY,K.C.B.,LL.D.,F.R.S. A. SCOTT, M.A., D.Sc., F.R.S. W. A. TILDEN, D.Sc., F.R.S. JOHN WADE, D.Sc. ( m a r : J. C. GAIN, D.Sc., Ph.D. SnIY-&;bitaz : A. J. GREENAWAY. amistrrnt S6nb--@bitar : C. H. DESCH, D.Sc., P1i.D. 1907. Vol. XCI. LONDON: GURNEY & JACKSON, 10, PATERNOSTER ROW. 1907.RICHARD CLAY & SONS, LIMITED, BREAD STREET HILL, E.C., AND BUNQAY, SUFFOLK.J O U R N A L OF THE CHEMICAL SOCIETY. TRANSACTIONS. H. E. ARMSTRONQ, Ph.D., LL.D., E.C. C. BALY. HORACE T. BROWN, LL.D., F.R.S. A. W. CROSSLEY, D.Sc., Ph.D., F.R.S. WYNDHAM R. DUNSTAN, D.Sc. , Ph.D., F. R. S. F. R. S. M. 0. FORSTER, D.Sc., Ph.D., F.R.S. R. MELDOLA, F.R.S. G. T. MORGAN, D.Sc. Sir W. RAMYAY, K. C.B. , LLD., F.R.S. A. SCOTT, M.A., D.Sc., F.R.S. W. A. TILDEN, D.Sc., F.R.S. JOHN WADE, D.Sc. 6,bitar : J. C. CAIN, D.Sc., Ph.D. S&-@bitm : A. J. GREENAWAP. 3##isttmt Sub-@,bitxrx : C. H. DESCH, D.Sc., Ph.D. 1907. Vol. XCI. Part I. LONDON: GURNEY & JACKSON, 10, PATERNOSTER ROW. 1907.RICHARD CLAY & SONS, LIMITED BREAD STREET HILL, E.C., AND BUNOAY, SUFFOLK.J O U R N A L OF THE CHEMICAL SOCIETY. TRANSACTIONS. dommittee af @nbIkatian : H. E. ARMSTRONG, Ph.D., LL.D., E. C. C. BALY. HORACE T. BROWN, LL.D., F.R.S.A. W. CROSSLEY, D.Sc., Ph.D., F.R.S. WYNDHAY R. DUNSTAN, D.Sc., Ph.D., F. R. S. F. R, S. M. 0. FORSTER, D.Sc., Ph.D., F.R.S. R. MELDOLA, F.R.S. G. T. MORGAN, D.Sc. SirMr. RAMSAY, K.C. B., LL. D., F.R.S. A. SCOTT, M.A., D.Sc., F.R.S. W. A. TILDEN, D.Sc., F.R.S. JOHN WADE, D.Sc. &bitor : J. C. CAIN, D.Sc., Ph.D. 4inb-6biiar : A. J. GREENAWAY. 3srcirJftrIrf Snb-&War : C. H. DESCH, D.Sc., Ph.D. 1907. Vol. XCI. Part 11. LONDON: GURNEY & JACKSON, 10, PATERNOSTER ROW 1907.RICHARD CLAY & SONS, LIMITED, BREAD STREET HILL, E.C., AND BUNQAP SUFI'OLP.C O N T E N T S . PAPERS COMMUNICATED TO THE CHEMICAL SOCIETY. PAGE I.-Pinene Nitrolamine. By FREDERICK PEACOCK LEACH . 1 11. -A pseudo-Semicarbazide from Pinene. By FREDERICK PEACOCK LEACH . . 10 111.-The Liquid Volume of a Dissolved Substance.By JOHN SCOTT LUMSDEN . . 24 IT.-The Influence of Light on Diazo-reactions. I. By KENNEDY JOSEPH PREVIT~ ORTON, JOSEPH EDWARD COATES V.-On the More Exact Determination of the Densities of Crystals. By The EARL OF BERKELEY . . 56 V1.-Action of Reducing Agents on 5-Chloro-3-keto-l :l-di- methyl-A4-tetrahydrobenzene. By ARTHUR WILLIAM CROSSLEY and NORA REYOUF, Salters' Research Fellow . 63 VI1.-The Viscosity of Liquid Mixtures. By ALBERT ERNEST DUNSTAN and ROBERT WILLIAM WILSON . . 83 VIII. -Relation between Chemical Constitution and Physio- logical Action in the Tropeines. By HOOPER ALBERT DICKINSON JOWETT and FRANK LEE PYMAN . . 92 IX.-4-Hydroxyphthalic and 4-Methoxyphthalic Acids. By WILLIAM HENRY BENTLEY and CHARLES WEIZMANN .. 98 X.-3-Hydroxyphthalic and 3-Methoxyphthalic Acids and their Derivatives. By WILLIAM HENRY BENTLEY, RONA ROBINSON, and CHARLES WEIZMANN . . 104 XI.-A Relation between the Volumes of the Atoms of Certain Organic Compounds at the Melting Point and their Valencies. Interpretation by Means of the Bsrlow-Pope XI1.-The Optical Influence of Contiguity of Unsaturated Groups. By JULIUS WILHELM BRUHL . . 115 XII1.-The Action of Acid Chlorides on Thioureas. By AUGUSTUS EDWARDIXON and JOHN HAWTHORNE . . 122 X1V.-Transformations of Highly Substituted Nitroamino- benzenes. 11. s-Tribromo-1-nit roaminobenzene. By ALICE EMILY SMITH and KENNEDY JOSEPH PREVITE ORTON. . 146 (and, in part, FRANCES BURDETT) . . 35 Theory. By GERVAISE LE BAS, B.Sc. . . 112i v CONTENTS.XV.-The Affinity Constants of Aminocarboxylic and Amino- sulphonic Acids as determined by the aid of Methyl-orange. By VICTOR HERBERT VELEY . XVL-Tetraketopiperazine. By ALFRED THEOPHILUS DE MOUILPIED and ALEXANDER EULE . XVIL-Synthesis of Terebic, Terpenylic, and Homoterpenylic Acids. By JOHN LIONEL SIMONSEN (Schunck Research Fellow in the University of Manchester) . XVII1.-Preparation of Chromyl Dichloride. By HERBERT DRAKE LAW and FREDERICK MOLLWO PERKIN . X1X.-Benzoyl Derivatives of N-Methylsalicylamide. By JAMES MCCONNAN and MORRIS EDGAR MARPLES . XX.-Disalicylamide. By JAMES MCCOXNAN . XXL-The Relation between Absorption Spectra and Optical Kotatory Power. Part I. The Effect of Unsaturation and Stereoisomerism. By ALFRED WALTER STEWART (Carnegie Research Fellow) .XXI1.-Organic Derivatives of Silicon. Part I T . The Synthesis of Benzylethylpropylsilicol, its Sulphonation, and the Resolu- tion of the dl-Sulphonic Derivative into its Optically Active Components. By FREDERIU STANLEY KIPPINQ . XX1II.-Derivatives of Multivalent Iodine. Part I T . Action of Heat on p-Iodoacetophenone Dichloride, p-Iodoacetanilide Dichloride, and on the Dichlorides derived from 0-, m-, and p-Iodotoluene. By WILLIAM CALDWELL and EMIL ALPHONSE WERXER . XX1V.-The Condensation Products of Triacetic Lactone with Acetoacetic Ester and P-Aminocrotonic Ester. By FREDERICK NOEL ASHCROFT FLEISCHMANN, M.A., Oxon. . XXV.-Oxidation of Hydrocarbons of the Benzene Series. By HERBERT DRAKE LAW and FREDERICK MOLLWO PERKIN . XXV1.-The Condensation of Salicylauide with Aryl Alde- hydes.By C,HARLES ALEXANDER KEANE and WILLIAM WALTER SCOTT NICHOLLS . XXVI1.-The Condensation of Diethylmalonamide with Alde- hydes. By HARRY BURROWS and CHARLES ALEXANDER KEANE . XXVII1.-The Constitution of Umbellulone. Part 11. The Reduction of U'mbellulonic Acid. By FRANK TUTIN , XX1X.-The Reduction of Hydrouylaminodihydroumbellulone- oxime. By FRANK TUTIN . XXX.-Some Constituents of Natural Indigo. Part I. By ARTHUR GEORGE PERKIN and W. POPPLEWELL BLOXAM . c' PAGE 153 176 184 191 193 196 199 209 240 250 258 264 269 271 275 279CONTENTS. V PAGE XXX1.-The Alkylation of d-Fructose. XXXI1.-Studies on Optically Active Carbimides. By THOMAS PURDIE, F.R.S., and DAVID MCLAREN PAUL, B.Sc., Carnegie Scholar Part V. The Aryl Esters and the Amides of 1-Menthylcarbamic Acid.By ROBERT HOWSON PICKARD and WILLIAM OSWALD LITTLEBURY . . 300 XXXII1.-Note on the Arsenates of Lead and Calcium. By SPENCER U. PICKERINQ, M.A., F.R.S. . . 307 XXX1V.-The Absorption Spectra of Phthalic, isoPbthalic, and Terephthalic Acids, Phthalic Anhydride, and Phthalimide. By WALTER NOEL HARTLEY and EDGAR PERCY HEDLEY . 314 XXXV.-The Absorption Spectra of Benzoic Acid, the Benzoates, and Benzamide. By WALTER NOEL HARTLEY and EDGAR PERCY HEDLEY . . 319 XXXVL-A Reaction of certain Colouring Matters of the Oxazine Series. By JOCELYN FIELD THORPE . . 324 XXXVIL-The Alkaloids of Ergot. By GEORGE BARGER and FRANCIS HOWARD CARR . . 337 XXX VII I. --aa 7-Trimethyl- and aa y y-Te tramet h yl- tricarballylic Acids and ay-Dimethyl butane-ap8-tricarboxylic Acid.By HERBERT HENSTOCK and CHARLES HENRY GRAHAM SPRANK- LING . . 354 XXXIX.-Influence of Substitution on the Formation of Diazo- arnines and Aminoazo-compounds. Part VI. The Partially Methylated 4:6-Diamino-m-xylenes. By GILBERT T. MOR- QAN and FRARCES M. G. MICKLETHWA~T . . 360 XL.-Experiments on the Synthesis of the Terpenes. Part I. (con- tinued). Direct Synthesis of Terpin from Ethyl cycZoHexan- one-4-carboxylate. By FRANCIS WILLIAar KAY and WILLIAM HENRY PERKIN, jun. . . 372 XLL-The Rapid Electroanalytical Deposition and Separation of Metals. The Metals of the Silver and Copper XLI1.-Derivatives of Naphthacenequinone. By WILLIAM HENRY BENTLEY, ARTHUR FRIEDL, FREDERICK THOMAS, and CHARLES WEIZMANN [with an addendum by E. C. C. BALY XLII1.-Constituents of Natural Indigo, Part 11.By ARTHUR XL1V.-Association of Phenols in the Liquid Condition. By XLV.-The Constitution of Hydroxyazo-compounds. By 289 * Part I. Groups and Zinc. By HENRY JULIUS SALOMON SAND . . 373 and W. B. TUCK) . . 411 GEORGE PERKIN. . 435 JOHN THEODORE HEWITT and THOMAS FIHLD WINMILL . . 441 WILLIAM BRADSHAW TUCK . . 449vi CONTENTS. PAGE XLV1.-Resolution of Tetrahydro-p-toluquinaldine into its Optically Active Components. By WILLIAM JACKSON POPE and, THOMAS CONSTANTINE BECK . XLVI1.-Displacement of Halogens by Hydroxyl. I. The Hydrolytic Decomposition of Hydrogen and Sodium Mono- chloroacetates by Water and by Alkali, and the Influence of Neutral Salts on the Reaction Velocities. By GEORQE SENTER . XLVII1.-New Cerium Salts.By GILBERT T. MORGAN and EDWARD CAHEN . XL1X.-Experiments on the Synthesis of the Terpenes. Part X. Synthesis of Carvestrene and its Derivatives. By WILLIAM HENRY PERKIN, jun., and GEORGE TATTERSALL . L.-The Influence of Solvents on the Rotation of Optically Active Compounds. Part IX. A New General Method for Studying Intramolecular Change. By THOMAS STEWART PATTERSON and ANDREW MCMILLAN, M.A. L1.-Camphor-P-sulphinic Acid and Camphorylsulphonium Bases. By SAMUEL SMILES and THOMAS P. HILDITCH LIP.-Derivatives of Multivalent Iodine. Part 111. The Action of Heat on Iodobenzene Dichloride, and on the nz- and p- Nitro- and p-Uhloro-derivatives. By WILLIAM CALDWELL and EMIL ALPHONSE WERNER . LII1.-Depression of the Freezing Point of Aqueous Solutions of Hydrogen Peroxide by Potassium Persulphate and other Compounds.By THOMAS SLATER PRICE, D.Sc. . LIT.-The Reduction Products of 0- and p-Dimethoxybenzoin. By JAMES COLQUHOUN IRVINE, Ph.D., D.Sc., and AGNES MARION MOODIE, M.A., B.Sc., Carnegie Scholar . LV.-The Action of Ethylene Dibromide and of Propylene Dibromide on the Disodium Derivative of Diacetylacetone. By ALEXANDER WILLIAM BAIN . LV1.-Volume" Changes which Accompany Transformations in the Sptem Na,S,O, : 5H,O. By HARRY MEUFORTH DAWSON and COLIN GYRTH JACESON . LVI1.-The Constitution of Chaulmoogric and Hydnocarpic Acids. By MARMADUKE BARROWCLIFF and FREDERICK BELDING POWER. . LVII1.-The Formation and Reactions of Imino-compounds. Part 111. The Formation of 1 :3-Naphthylenediamine and its Derivatives from o-Toluonitrile. By ERNEST FRANCIS JOSEPH ATKINSON, HARRY INOHAM, and JOCELYN FIELD THORPE . By JAMES CODRINGTON CROCRER, M.A.. . . LIX. -The Velocity of Hydrolysis of Aliphatic Amides. 458 460 475 480 504 519 528 531 536 544 55 2 557 578 593CONTENTS. vii PAUE LX.-Interaction of Alkali Starch and Carbon Disulphide. Xanthogenic Esters of Starch. By CHARLES FREDERIC CROSS, EDWARD JOHN BEVAN, and JOHN FREDERIC BRIGGS . Annual General Meeting . . - . Presidential Address . Obituary Notices . LX1.-The Hydrolysis of Amygdalin by Acids. By ROBERT J. CALDWELL, B. Sc. (Lond. ), Leathersellers’ Company’s Re- search Fellow, and STEPHEN LEWIS COURTAULD, B.A. (Cantab.) . LXI1.-Mandelonitrile Glucosides. Prulaurasin. By ROBERT J. CALDWELL, B.Sc. (Lond.), Leathersellers’ Company’s Research Fellow, and STEPHEN LEWIS COUETAULD, B.A.(Cantab.) . LX1II.-The Interaction of Ammonium Salts and the Con- stituents of the Soil. By ALFRED DANIEL HALL, M.A., and CONRAD THEODORE GIMINGHAM , LX1V.-The Reduction of Carbon Dioxide t o Formaldehyde in Aqueous Solution. By HENRY JOHN HORSTMAN FENTON . LXV.-An Extension of the Benzoin Synthesis. By REGINALD W. L. CLARKE and ARTHUR LAPWORTH . LXV1.-Studies in Optical Superposition. Part 111. By THOMAS STEWART PATTERSON and JOHN KAYE LXVI1.-Influence of Non-electrolytes and Electrolytes on the Solubility of Sparingly Soluble Gases in Water. The Question of Hydrates in Solution. By JAMES CHARLES PHILIP . . . LXV 111.-Organic Derivatives of Silicon. Part 111. dl-Benzyl- methylethylpropylsilicane and Experiments on the Resolu- tion of its Sulphonic Derivative.By FREDERIC STANLEY KIPPINB . LX1X.-Electrolytic Reduction. Part 111. By HERBERT DRAKE LAW . LXX.-The Estimation of Small Quantities of Nitrogen Per- oxide. By ROBERT ROBERTSON, M.A., D.Sc., and SIDNEY SCRIVENER NAPPER . LXX1.-The Evolution of Nitrogen Peroxide in the Decomposi- tion of Guncotton. By ROBERT ROBERTSON, M.A., D.Sc., and SIDNEY SCRIVENER NAPPER . LXXI1.-An Isomeric Change of Dehydracetic Acid. By JOHN NORMAN COLLIE and THOMAS PERCY HILDITCH . LXXII1.-Measurements of the Velocities of Saponification of the I-Menthyl and I-Bornyl Esters of the Stereoisomeric Mandelic Acids. By ALES. MCKENZIE and HERBERT BRYAN THOMPSON, M.Sc. . 612 615 626 660 666 671 677 687 694 705 711 717 748 761 764 78 7 789...V l l l CONTENTS. LXX1V.-The Action of Ethyl Oxnlate on Thioacetanilide and LXXV.-The Magnetic Rotation of Hexatriene, CH,:CH*CH:CH*CH:CH,, and its Relationship to Benzene and other Aromatic Com- pounds: also its Refractive Power. By SIR WILLIAM BENRY PERKIN . LXXVI.+'he Action of Tribromopropane on the Sodium Deriv- d i v e of Ethyl Malonate. Part I. By WILLIAM HENRY PERKIN, jun., and JOHN LIONEL SIMONSEN (Schunck Research Fellow in the University of Manchester) LXXVIL-The Action of Tribromopropane on the Sodium Derivative of Ethyl Malonate. Part 11. Formation of Aa~-Heptadi-inene-6carboxylic Acid (q-m-Toluic Acid), (CHIC*CH,),C(CO,H),. By WILLIAM HENRY PERKIN, jun., and JOHN LIONEL SIMONSEN (Schunck Research Fellow in the University of Msnchester) . LXXVII1.-The Action of Tribromopropane on the Sodium Derivative of Ethyl Acetoacetate.By THOMAS EDWARD GARDNER and WILLIAM HENRY PERKIN, jun. LXX1X.-Aromatic Azoimides. Part I. Parahydroxyphenyl- azoimide. By MARTIN ONSLOW FORSTER and HANS EDUARD FIERZ . LXXX.-Studies in the Carnphane Series. Part XXIII. Oximes of Camphorylsemicarbazide and Camphorylazoimide. By MARTIN ONSLOW FORSTER and HANS EDUARD FIERZ . . LXXX1.-The Constituents of the Essential Oil of American Pennyroyal. Occurrence of a Dextro-Menthone. By MARMADUKE BARROWCLIFF . LXXXI1.-The Constitution of HomoeriodictyoL-A Crystal- line Substance from Eriodictyon Leaves. By FREDERICK BELDING POWER and FRANK TUTIN . LXXXII1.-Contributions to the Chemistry of Oxygen Com- pounds. 11. The Compounds of Cineol, Diphenylsulph- oxide, Nitroso-derivatives, and the Carbamides with Acids and Salts.By ROBERT HOWSON PICKARD and JOSEPH KENYON . LXXX1V.-Freezing Point Curves of the Menthyl Mandelates. By ALEXANDER FINDLAY and EVELYN MARION HICKMANS . LXXXV.-Acyl-+-derivatives of Iminothiocarbamic Acid and their Isomerides. By AUGUSTUS EDWARD DIXOET, and JOHN TAYLOR . LXXXV1.-The Chemical Action of the Radium Emanation. Part I. Action on Distilled Water. By SIB WILLIAM RAMSAY, K.C.B., F.R.S. . its Homologues. By SIEGFRIED RUHEMANN . . . PAGE 797 806 816 840 848 855 867 875 88 7 896 905 912 931CONTENTS. iX PA GI5 LXXXVI1.-The Chemical Changes induced in Gases submitted to the Action of Ultraviolet Light. By DAVID LEONARD CHAPMAN, SAMUEL CHADWICK, and JOHN EDWIN RAMS- BOTTOM . . 942 LXXXVII1.-The Velocity of Hydrolysis of the Aliphatic Amides by Alkali.By JAMES CODRINGTON CROCKER, M.A., LXXX1X.-Arsenic Di-iodide. By JOHN THEODORE HEWITT and THOMAS FIELD~WINMILL . . 962 XC.-Separation of Cadmium from Zinc as Sulphide in the presence of Trichloroacetic Acid. By JOHN JACOB FOX . 964 XC1.-Mixed Semi-ortho-oxalic Compounds. By G. DRUCE LANDER . . 967 XCIL-The Influence of Substitution in the Nucleus on the Rate of Oxidation of the Side-Chain. 111. The Oxidation of the Nitro- and Chloronitro-derivatives of Toluene. By JULIUS BEREND COHEN and HENRY JAMES HODSMAN . . 970 XCII1.--The Interaction of Cyanodihydrocarvone, Amy1 Nitrite, and Sodium Ethoxide. Part I. By ARTHUR LAPWORTE and ELKAN WECHSLER . . 977 XC1V.-Studies of the Perhalogen Salts. Part I.By CHARLES KENNETH TINKLER, B.Sc. . . 996 XCV.-The Formation and Reactions of Imino-compounds. Part IV. The Formation of 1 :4-Naphthylenediamine from Ethyl y-Imino-a-cyano-y-phenylbutyrate. By JOCELYN FIELD THORPE . . 1004 XCV1.-Some Compounds of Guanidine with Sugars. Part I. By ROBERT SELBY MORRELL and ALBERT ERNEST BELLARS . 1010 XCVI1.-Esterification Constants of Substituted Acrylic Acids. Part 11. By JOHN JOSEPH SUDBOROUGH and EBENEZER REES THOMAS . . 1033 XCVII1.-The Addition of Iodine t o Acetylenic Acids. By THOMAS CAMPBELL JAMES and JOHN JOSEPH SUDBOROUGH . 1037 XC1X.-Mercury Derivatives of Pseudo- Acids containing the Group *CO*NH*. By S. J. MANSON AULD, Ph.D. . . 1045 C.-The Constitution of the Diazo-compounds. By JOHN CANNELL CAJN . . . . . 1049 C1.-Experimental Investigation into the Process of Dyeing. By JULIUS HUBNER .. 1057 (311.-Brazilin and Hzmatoxylin. Part VII. Synthesis of Derivatives of Hydrindene closely allied to Brazilin and Haematoxylin. By WILLIAM HENRY PERKIN, jun., and ROBERT ROBINSON . . 1073 D.Sc., ancl FRANK HAROLD LOWE, M.Sc. . . 952 I,X CONTENTS. CII1.-The Action of Aluminium Chloride on Naphthalene. FACE By ANNIE HOMER, ILA., Bathurst Student at Newnharn College, Cambridge. . . 1103 CIV.-A!Ioleculsr Weight of P-Naphthol in Solution in Solid Naphthalene. 13y EDGAR PHILIP PERMAN and JoIrN TiUGHEs DAVIES , . 1114 CV.-Phenol 2’-Sulphoxicle. By SAMUEL SMILES and ALEXANDER WILLIAM BAIN . . 1118 CV1.-The Relation between Absorption Spectra and Chemical Constitution. Part VII. Pyridine and some of its Derivatives.By FRANK BAKER and EDWARD CHARLES CYRIL BALY . . 1122 CVII. -0xime Formation and Decomposition in Presence of C VII1.-nibromoaminoazobenzene. By JOHN THEODORE HEWLTT and NORMAN WALKER . . 1138 CIX.--The Interaction of Methylene Chloride and the Sodium Derivative of Ethyl Malonate. By FRANK TUTIN . . 1141 CX. --The Chemical Composition of Petroleum from Borneo. By HUMPHREY OWEN JONES and HUBERT ARTHUR WOOTTON . 1146 CX1.-The Relation between the Crystalline Form and the Chemical Constitution of Simple Inorganic Substances. By WILLIAM BARLOW and WILLIAM JACKSON POPE . . 1150 (3x11.-Studies in Asymmetric Synthesis. VI. The Asym- metric Synthesis of the Optically Active Tartaric Acids. By ALEX. MCKENZIE and HENRY WREN . . 1215 CXII1.-Calmatambin : a New Glucoside.By FRANK LEE PYWAN . . 1228 CX1V.-The Condensation of Aldehydes with Mixtures of a-Naphthol and a-Naphthylamine. Synthesis of 7-Aryl- a-N-a I -dinaphthacridines. By ALFRED SEXIER and PERCY Mineral Acids. By ARTHUR LAPWORTH . . 1133 B-CH-p CORLETT AUSTIN . . 1233 CXV.-The Synthesis of Phenonaphthacridines : Trirnethyl- phenonaphthscridines. By ALFRED SENIER and PERCY CORLETT AUSTIN . . 1240 CXV1.-The Affinity Constants of Aminosulphonic Acids as Determined by the Aid of Mtehyl-Orange. By VICTOR HERBERT VELEY . , 1246 CXVII. -Golour and Constitution of Rzo-compounds. Part 1. By JOHN THEODORE HEWITT and HERBERT VICTOR MITCHELL 1251 CXVII1.-Some Properties of Radium Emanation. By ALEX- ANDER THOMAS CAMERON, M.A., B . ~ c . , and S I R WILLIAM RAMSAY, K.C.B., F.R.S.. . 1266CONTENTS. xi ?AGE CX1X.-Some Derivatives of 2-Phenyl-l:3-naphthylenediamine. CXX.-New Derivatives of Diphenol (4’:4’-Dihydroxydiphenyl). CXX1.-A Series of Coloured Diazo-salts Derived from Benzoyl- 1 :4-naphthylenediamine. By GILBERT T. MORGAN and WILLIAM ORD WOOTTON . . 1311 CXXI1.-The Oxidation of Hydrazines by Free Oxygen. By FREDERICK DANIEL CHATTAWAY . . 1323 CXXII1.-Studies in the Barbituric Acid Series. I. 1:3-Di- phenylbsrbituric Acid and some Coloured Derivatives. By MARTHA ANNIE WHITELEE- . . 1330 CXX1V.-Aromatic Azoimides. Part 11. Ortho- and Meta- hydroxyphenylazoimides. By MARTIN Omtow FORSTER and HANS EDUARD FIERZ . . 1350 C‘XXV.-Methyl Dicarboxyaconitate. By SIEGFRIED RUHEMANN . 1359 CXXV1.-The Action of Heat on a-Hydroxycnrboxylic Acids.Part 111. aa’-Dihydroxysebacic Acid and i t s Diacetyl Derivative. By HENRY RONUEL LE SUEUR . . 1365 C‘XXVI1.-An Improved form of Apparatus for the Rapid Estimation of Sulphates and Salts of Barium. By WILLIAM ROBERT LANG and THOS. BOLES ALLEN . . . 1370 CXXVII1.--A Method for the Determination of the Equilibrium in Aqueous Solutions of Amines, Pseudo-acids and -bases, CXX1X.-The “ True ” Ionisation Constants and the Hydration Constants of Piperidine, Ammonia, arid Triethylamine. By TOM SIDNEY MOORE . . 1379 CXXX. -The Application of Baeyer’s Reduction t o Benzoin and its Derivatives. By JAMES COLQUHOUN IRVINE, D.Sc., Ph.T)., and JOHN WEIR, M.A., B.Sc., Berry Scholar in Science . . 1384 CXXX1.-The Influence of Mercuric Iodide on the Formation of Sulphonium Iodides.By THOMAS PERCY HILDITCH and SAMUEL SMILES . 1394 CXXXI1.-The Decomposition of Mercurous and Silver Hypo- nitrites by Heat. By I’RAFULLA CHANDRA RAY and ATUL CHANURA GA~GULI . . 1399 CXXXII1.-Mercurous Hyponitrite. Ry PRAFULLA CHANDRA R ~ Y . . . 1404 CXXX1V.-Cupric Kitrite. By PRAFULLA CirANmA RAY . 1405 CXXXV.-Researches on Morphine. Part 111. By FREDERIC HERBERT LEES . . 1408 Part I. By NORMAN LEES and JOCELYN FIELD THORPE . 1282 By JAMES MOIR, D.Sc., h1.A. . . 1305 and Lactones. By TOM SIDNEY MOORE . . 1373xii CONTENTS. CXXXV1.-Phenylbenzornetoxazone and Related Derivatives, CXXXVI1.-isoNitroso- and Nitro-dimethyldihydroresorcin. By CXXXVII1.-The Action of Hydrogen Peroxide on Potassium CXXX1X.-The Diazotisation of Dini tronnisidines and Related Compounds.By RAPHAEL MELDOLA, F.R.S., ant1 JAMES GORDON HAY . . 1474 By MA? THEW MONCRIEFF PATTJSON &1UIR . 1485 By FRANK BAKER . 1490 PAGE By ARTHUR WALSH TITHERLEY . . 1419 PAUL HAAS . . 1433 Cyanide. By ORME MASSON, D.Sc., F.K.S. . 1449 CXL.-Permanganic Acid. CXL1.-The Structure of Carbonium Salts. CXLT1.-A New Colouring Matter from Nyctnntlies Arbor- tristis. By ERNEST GEORGE HILL and ANNODA PRASAD SIRKAR . . 1501 UXLII1.-The Diazo-derivatives of Benzenesulphonylbenzidine. By GILBERT T. MORGAN and JAMES MORTON HIRD . . 1505 CXLIV. -The Interactions of Aromatic Amines and para- Diazoimides. By GILBERT T. MORGAN and;FRA~c~s M. G. MICKLETHWAIT . . 1512 CXLV.-Succinic Acid and its Potassium Salts. By HUGH MARSHALL and ALEXANDER THOMAS CAMERON .. 1519 CXLV1.-The Relation between Absorption Spectra and Optical Rotatory Power. Part T I . The Tartaric Acids. By ALFRED WALTER STEWART, D.8c. (Carnegie Research CXLVI1.-The Wandering of Bromine in the Chlorination of Bromoanilines. By WALTER WILLIAM REED and KENNEDY JOSEPH PREVIT~ ORTON . . 1543 CXLVII1.-Isomeric Change in Benzene Derivatives. Replace- ment of Halogen by Hydroxyl in Chlorobromodiazobenzenes. By KENNEDY JOSEPH PREVITE ORTON and WALTER WILLIAM REED . . 1554 CXL1X.-The Relation between Absorption Spectra and Chemical Constitution. Part VIII. The Phenylhydrazones and Osazones of a-Diketones. By EDWARD CHARLES CYRIL BALY, WILLIAM BRADSHAW TUCK, EFFIE GWENDOLINE CL.-The Fluoresceins and Eosins from 4-EIydroxyphthalic, 4-Methoxyphthalic, and Hemipinic Acids.By ARTFZUR CL1.-Derivatives of Naphthacenequinone. Part 11. By WILLIAM HENRY BENTLEY, ARTHUR FRIEDL, and CIIARLES WEIZMANN . 1588 ’ Fellow) . , 1537 I MARSDEN, and (in part) MAUD GAZDAR . . 15’12 FRIEDL, CHARLES WEIZMANN, and MAX WYLER” . . 1584... CONTENTS. X l l l PAGE CLT1.-The Chemical Action of Radium Emanation. Part 11. On Solutions Containing Copper, and Lead, and on Water. By ALEXANDER THOMAS CAMERON, M.A., B.Sc., and SIR CLII1.-Molecular Aggregntion in Solution as Exemplified in Aqueous Mixtures of Sulphuric Acid with Ingoranic Sul- phates. By JOHN HOLMES and PHILIP JOHN SAGEMAN. . 1606 (2 : 8-Dih y droxy-5-phenyl-3 : 7-dimethyl- acridine). By ALBERT ERNEST DUNSTAN and LOUISA CLEAVERLEY . . 1619 CLV.-Researches on Anthraquinones and Phthaleins.By WILLIAM HENRY BENTLEY, HENRY DENT GARDNER, jun., and CHARLES WEIZNANN . , 1626 CLV1.-The Velocity and Mechanism of the Reaction between Iodine and Hypophosphorous Acid. By BERTRAM DILLON STEELE . . 1641 CLVI1.-The Action of Bromine on 5-Phenylacridine and its Halogen Derivatives. By ALBERT ERNEST DUNSTAN and THOMAS PERCY HILDITCH . . 1659 CLVIII.--The Adsorption of Iodine by Carbon. By OLIVER CHARLES MINTY DAVIS . . 1666 CLIX.-Adsorption Formulx!. By JAMES W. MCBAIN . . 1683 CLX.-The Formation and Reactions of Imino-compounds. Part V. The Formation of Methyl Derivatives of 1 :3-Naphthylenediamine from the Three Tolylacetonitriles. By ERNEST FRANCIS JOSEPH ATKINSON and JOCELYN FIELD THORPE . . 1687 CLXI.-The Atomic Volumes of Phosphorus, By EDMUND BRYDQES RUDHALL PRIDEAUX, M.A., D.Sc.. . 1711 CLXI1.-Indican. Part I. By ARTHUR GEORUE PERK~N and WILLIAM POPPLEWELL BLOXAM , . 1715 CLXIIL-The Relation between Viscosity and Chemical Con- stitution. Part I. The Viscosity of Pgridine Solutions. By ALBERT ERNEST DUNSTAN, FERDINAND BERNARD THEODORE THOLE, and JOHN SAMUEL HUNT . Part XI. Synthesis of 4-isoPropylidenecyclohexanone and its Derivatives. 3y WILLIAM HENRY PERKIN, jun., and JOHN LIONEL STMONSEN . . 1736 THE FARADAY LECTuRE.-synthetical Chemistry in its Relation t o C'LXV.-The Occurrence of Quercitol (Quercite) in the Leaves of CLXV1.-Gocositol (Cocosite), a Constituent of the Leaves of WILLIAM RAMSAY, K.C.B., F. R.S. , . 1593 CLIV.-Benzoflavol . 1728 CLX1V.-Experiments on the Synthesis of the Terpenes.Biology. By Prof. EMIL FISCHER, F.R.S. . . 1749 Chamcerops iwnzilis. By HUGO MULLER . . 1766 Cocos n'lccifera and Cocos plumostc. By HUGO MULLER . 1767xiv CONTENTS. P.2CTr. CLXVI J.-Inositol (Inosite). By HUGO MGr,Lm . . 1780 CLXVIIL-Hydrates of Some Quaternary Bases. By DAVID CLX1X.-pm-Toluidine Monohydrate. By JAMES WALKER and HEATHER HENDERSON BEVERIDGE (Carnegie Research CLXX.-The Production of Orcinol Derivatives from the Sodium Salt of Ethyl Acetoacetnte by the Action of Heat. By JOHN NORMAN COLLIE and EDWIN RODNEY CHRYSTALT, . . 1802 CLXXL-Derivatives of the Multiple Keten Group. By JOHN NORMAN COLLIE . . 1806 CLXXI1.-Racemisation by Alkali as Applied to the Itesolution of ?*-Mandelic Acid into its Optically Active Isomerides. By ALEX. MCKENZIE and HERMANN AUGUST MULLER .. 1814 CLXXII1.-The Optical Activity of Cyclic Ammonium Com- pounds. By FRANK BUCKNEY, B.A., and HUMPHREY OWEN JONES . . 1831 CLXX1V.-Some Double Ferrocyanides of Calcium, Potassium, and Ammonium. By JAMES CAMPBELL BROWN, D.Sc. , . 1826 CLXXV.-The Condensation of Acetaldehyde and its Relation to the Biochemical Synthesis of Fatty Acids. By HENRY STANLEY RAPER . . 1831 CLXXVL-The Influence of Solvents on the Rotation of Optically Active Compounds. Part X. Effect of the Configuration and Degree of Saturation of the Solvent. By THOMAS STEWART PATTERSON, ANDREW HENDERSON, M.A., B.Sc., and FRANK WALTER FAIRLIE, B.Sc. . . 1838 CLXXVI1.-Two Volumetric Methods for the Determination of Chromium. By ARNOLD WILLIAM GREGORY, B.Sc. ( LoND.), and JAMES MCCALLUM .. 1846 CLXXVIl.1.-The Atomic Weight of Tellurium. By HERIHCILT BRERETON BAKER and ALEXANDER HUTCHEON BENNETT CLXX1X.-Gaseous Nitrogen Trioxide. By HERBERT BRERETON BAKER, &LA., D.Sc., F.R.S., and MURIEL BAKER . . 1862 CLXXX.-The Decomposition of Hyponi trous Acid in Presence of Mineral Acids. By PIZAFULLA CHANrjRA I~AY and ATUL CHANDRA GA~GULI . . 1866 CLXXX1.--Contributions to the Chemistry of the Terpenes. Part 11. The Oxidation of Limonene with Chromyl CLXXXI1.-Studies in the Camphane Series. Part XXIV. Camphoryldithiocarbamic Acid and Camphorylthiocarbimi(1e. By R~ARTIN ONSLOW FORSTER and TrIoMAs JACKSON . . 18‘7’7 COWAN CRICHTON (Carnegie Research Scholar) . . 1793 Scholar) . . 1797 . 1849 Chloride. By GEORGE GEHAT~D HENIIERBON . . . 1871COSTENTS. xv PAGE CLXXXI11.-Aromatic Amides and h i d e s of Camphoric Acid.CLXXX1V.-Ethyl a-Cyano-ay-phenylacetoacetate. By ARTHUR RICHARD SMITH and JOCELYN FIELD THORPS . . 1899 CLXXXV.-Chemical Exiinmttion of the Koot and Leaves of X o ~ - i m Z c ~ ZOI/:J~$O,YL By MARMAUUKE BARROWCLIFF and FRANK TUTIN . . 1907 CLXXXV1.-The Interaction of Cy;tr~odiliyd~ocarvone, Amy1 Nitrite, and Sodium Ethoxide. Part 11. The Constitution of the Products. By ARTHUR LAPWORTH and ELKAN CLXXXVI1.-The Syrithesih of Acridines and Phenonaphtli- acridines : Tetra- and IZexa-methylacridines : Dimethyl- pherionaphthacridines : Dixyly lmethylenediamines. By CLXXXVIII.--Fiotex By NORMAN THOMAS MORTIMER WILS- MORE . . 1938 CLXXX1X.-Aromatic Azoimides. Part 111. The Naphthyl- azoimides and their Ni tro-Derivatives.By MARTIN ONSLOW FORSTKR and HANS EDUARD PIERZ . . 1942 CXC.-The Action of Phosphorus Pentachlode on H ydroxytri- methylsuccinic Ester. 1 :%DimethylcycZopropane-1 : 2-dicarb- oxylic Acid (1 :2-D~methyltrimethylene-1:2-dicnrboxylic Acid). By HERBERT HENSTOCK aud ~ J E R T H A ELIZABETH WOOLLEY . . 1954 CXC1.-The Vapour Pressui-es of Triethylamine, of 2:4:6-'l!ri- methylpyridine, and of their Mixtures with Water. By ROBERT TABOR LATTEY . . 1959 CXCII. -Liquid Triethylamiiie. By ROBEET TABOR LATTEY . 1971 CXCIII. -The Alcohols of the Hydroaromatic and Terpene Series. Part I . Resolution of the Alcohols into their Optically Active Components and the Preparation of the Borneols. By ROBERT HOWSON PICKARD and WILLIAM OSWALD LITTLEBURY . . 1973 CXC1V.-The Interaction of Metallic Sulphates and Caustic CXCV.-The Chemistry of Bordeaux Mixture. By SPENCER CXCV1.-Emulsions. By SPENCER UMFREVILLE PICKERIXG, CXCVI1.-The Electrolytic Preparation of Disulphides. Part I. Dibenzyl Disulphide and Diethyl Disulphide. By THOMAS SLATER PRICE and DOUGLAS FRANK TWISB . . 2021 CXCVII1.-The Double Nitrites of Mercury and the Alkali Metals. By PRAFULLA CHANDRA RAY . . 2031 By F'VILLIAM ORD \~OOTTON . . 1890 WECHSLER . . 1919 I ALFRED SEXIER arid ARTHUR CohirToN . . 1927 Alkalis. By SPENCER UMFREVILLE PICKERING, M.A., F.R.S. 1981 UMFREVILLE PICKERING, M. A,, F.R.S. . . 1'388 M.A., F.R.S. . . 2001xvi CONTEXTS. CXC1X.-Silver-mercuroso-mercuric Oxynitrates and the Iso- PAGE morphous Replacement of Univalent Mercury by Silver. By PRAFULLA CHANDRA RAP . . 2033 CC.-The Constituents of the Essential Oil of Nutmeg. By FREDERICK BELDING POWER and ARTHUR HENRY SALWAY . 2037 CC1.-The Resolution of sec.-Octyl Alcohol [Methylhexylcarbinol. Octane-2-01]. By ROBERT HOWSON YICKARD and JOSEPH KENYON . . 2058 By WILLIAM JACKSON POPE and CHARLES STANLEY GIBSON . . 2061 By ARTHUR GEORGE PERKIN . . 2066 Part IV. The Action of Caustic Alkalis on para-Nitrotoluene and its Derivatives. By ARTHUR GEORGE GREEN, ARTHUR HUGH DAVIES, and RONALD SMITH HORSFALL , CCV.-The Replacement of Alkyl Radicles by Methyl in Substituted Ammonium Compounds. By HUMPHREY OWEN JONES and JOHN ROBERTSHAW HILL . . 2083 COIL-The Alkyl Compounds of Gold. CCI1I.-Methyl Ethers of some Hydroxyanthraquinones. CC1V.-The Colouring Matters of the Stilbene Group. . 2076

ISSN:0368-1645    

DOI:10.1039/CT90791FP001

出版商:RSC    

年代:1907

数据来源: RSC

摘要:

10 LEACH : A PSEUDO-SEMICARBAZIDE FROM PINENE. BY FREDERICK PEACOCK LEACII. THE reaction between pinene nitrosochloride and potassium cyana te does not, as one might expect, lead to the production of a carbimide by the replacement of the chlorine by the -N:C:O group, but instead gives rise to a somewhat complex ring compound having the empirical formula CI2Hl70,N,. Interaction bet ween the nitrosochloride and potassium cyanate takes place quite readily in alcoholic solution a t 45-50', two molecular proportions of the cyanate reacting with one of the aitrosocliloride. The constitution of the new compound is probably best expressed by the formula or one of the tautomeric forms, This conclusion has been reached by considering the following ex- perimental evidence : (I) The substance behaves like an imide, having a feebly acidic character, dissolving i n caustic alkalis, and giving alkali salts like succinirnide or phthalimide. (2) When reduced by dilute acetic acid and zinc dust it loses carbon dioxide and ammonia, owing to liberation of cyanic acid, and a very stable peudocarbamide is formed : c H <?=No-co>NH + 2H2 = l2 CMe*NH*CO C 7 H l 2 < ~ ~ - - ~ ~ > C O + NH, + CO,.(3) Warm concentrated sulphuric acid hydrolyses the imide and the ring undergoes disruption ; carbon dioxide and ammonia are liberated and pinene nitrolamine is formed :LEACH : A PSEUDO-SEMICARBAZIDE FROM PINENE. 11 The mechanism by which the seven-membered ring is produced from the nitrosochloride has not been fully explained, but there seems no doubt that the condensation is brought about in some way by free cyanic acid, which can be rscognised in the liquid by means of the cobalt acetate test.The most probable explanation depends on the resolution of the bimolecular nitrosochloride into the unimolecular (oximino) form, and replacement of the chlorine by the group -N:C:O ; interaction of the free cyanic acid with the oximino-group would give a carbamic derivative of the oxime, which then undergoes rearrangement, forming the complex imide : This new compound is exceedingly stable towards oxidising agents. Whilst pinene and its compounds are, generally speaking, readily oxidiaed or altogether destroyed by nitric acid, the new compound can be boiled with concentrated nitric acid (sp. gr. 1*42), and on dilution with water crystallises in needles.I n a similar manner, when dis- solved in cold alkali and treated with alkaline hypobromite, the unchanged substance is precipitated from the solution. Towards reducing agents the substance is very sensitive, and as already pointed out i t gives rise by the action of zinc and dilute acetic acid to a pseudocarbamide from which the corresponding nitroso-$- carbamicie and peudosemicarbazide have been obtained. These sub- stances have a close relationship to the corresponding derivatives of camphor, recently isolated and examined by Porster and Fierz (Trims., 1905,87, 110 and 722) : Piny1 - I/I - carbamid e . Caruphoryl-$-carbamide. The pseudocarbamide from pinene possesses a very stable ring structure, for it sublimes unchanged at 224' and is scarcely acted on by hot 30 per cent.caustic potash or dilute acids. The camphoryl compound possesses a labile hydrogen atom, owing to which the ring can be opened by dilute acids, giving the carbamide of aminocamphor, from which alkalis regenerate the peudocarbamide. The action of nitrous acid on the pseudocarbamide from pinene12 LEACH : A PSEUDO-SEMICARBAZIDE FROM PINENE. gives rise to a nitroso-derivative, crystallising in beautiful yellow plates with a delicat.,e pink lustre. The stable nature of the ring in the pseudocarbamide makes it difficult to determine the position taken up by the nitroso-group : for the present, therefore, it is not possible to decide between the f ormuls CH---NH>Co C H 'I l2 <$!H*N(No) CMe--NH and C 7 H 1 2 < ~ ~ e .~ ~ ~ ~ ) ' A similar uncertainty exists in the case of the pseudosemicarbazide. Although remaining unchanged in the dark the nitroso-$-carbamide when exposed to light undergoes a series of interesting changes : in sunlight the colour changes in the course of a few minutes from the characteristic yellow with pink reflex to a bright green, whilst after some hours the green begins to fade and is followed by a dull yellow colour, further exposure causing no alteration ; besides change of colour the crystals become opaque and '' pitted " on the surface owing to escape of gas. This change, which is accompanied by decrease of fusibility, has been proved to be due to the elimination of the nitroso- group, with the regeneration of the pseudocarbamide.The readiness with which the nitroso-group is detached appears from the fact, that if a few crystals of the nitroso-compound are placed in a test-tube with a little potassium iodide and starch solution, and one drop of dilute sulphuric acid is added, the blue colour due to the liberation of iodine makes its appearance in the course of a few minutes. Cazeneuve (Compt. rend., 1889, 109, 185) noticed somewhat similar changes of colour in the case of nitrosocamphor (compare Claisen and Manasse, Annalen, 1893, 2'74, 72) : The introduction of the nitroso-group into the pseudoaarbamide renders the product soluble in dilute caustic soda, from which the sodium salt is precipitated on further addition of cold concentrated caustic soda ; if, however, the solution is heated, decomposition takes place, gas being evolved and an oil having a camphoraceous odour being produced.The reduction of the nitroso-t)-carbamide gives rise to a crystalline pseudosemicarbazide : The products of the reaction are still under investigation. The tendency, however, for the nitroso-group to become eliminated as ammonia is very considerable, and unless the conditions given for the preparation of the pseudosemicarbazide are adhered to, a product is obtained which is very difficult to purify.LEACH : A PSEUDO-SEMICARBAZIDE FROM PINENE. 13 The new base res'kmbles semicarbazide itself in combining with great readiness with aldehydes and ketones to form the corresponding pseudo- semicarbazones ; with acetone, however, no condensation product has been obtained.The quinone-$-semicarbazone crystallises in bright yellow needles and contains one molecule of water of crystallisation, which it loses a t 100'; products obtained by condensation of the pseudosemicarbazide with aldehydes, however, are free from solvent. The hydrochloride of the base when heated with nitrous acid at 0' regenerates the pseudocarbamide, and if excess of hydrochloric acid is present, the nitroso-$-carbamide is obtained, owing to the action of the nitrous acid on the pseudocarbamide. The reaction is most probably expressed as follows : (I) C 7 H , , < ~ ~ ~ ~ ~ ~ > C 0 + HNO, = 7H1 2<gEz!E >CO + N20 + H,O. (11) C , H , , < ~ ~ ~ ~ ~ > C O + HNO, = This observation is in agreement with that of Emil Fischer (Annalen, 1877, 180, 158), who found that when sodium nitrite acted on phenylmethylhydrazine in dilute sulphuric acid the nitroso- compound of pheoylmethplamine was obtained, C,H5(CH,)N*NH, + 2HN02 = C,H,(CH,)N*NO + 2H,O + N20, this action doubtless also takes place in two stages.The behaviour of the camphoryl-$-semicarbazide (Forster and Fierz, Trans., 1905, 87, 826) resembles that of the pinene compound, if the reaction is carried out in acetic acid solution, when the pseudo- carbamide is obtained, but excess of sodium nitroso-$-carbamide ; it differs, however, in nitrate of the camphoryl-q-semicarbazide is the ring undergoes disruption, with the azoimide. The compounds of pinene described in inactive. nitrite does not yield the the fact that when the treated with nitrous acid formation of camphoryl this paper are optically EX P E R I MENTAL. The most satisfactory method of obtaining this compound is to treat the nitrosochloride of pinene in quantities of 20 grams at a time,14 LEACH : A PSEUDO-SEMICARBAZIDE FROM PINENE.larger quantities cause the formation of more resinous matter. Twenty grams of freshly prepared pinene nitrosochloride were ground to a fine powder with 18 grams of potassium cyanate and the mixture added to 150 C.C. of rectified spirit, the whole being shaken from time t o time. I n the cold, the reaction proceeds very slowly, but on allowing to stand at 45-50' the nitrosochloride gradually disappeared and potassium chloride was precipitated along with a quantity of small, hard crystals of the imide, which is only very sparingly soluble in cold alcohol ; the solution developed a pale yellow colour, owing to the formation of a certain amount of a yellow, resinous oil, and in about four days the whole of the nitrosochloride had disappeared; sufficient water was added to dissolve the potassium chloride and on filtering there was left an almost pure residue of the new compound, which after two recrystallisations from hot alcohol was quite pure.On pouring the alcoholic solution into a large volume of water a yellowish- white, bulky solid, mixed with small quantities of oily matter and re- generated pinene,wasprecipitated, from which after filtering, drying, and extracting, with light petroleum, the crude imide was obtained. The light petroleum, on evaporation, left a brown, resinous oil having an odour of turpentine, and after some time crystals were deposited, which when recrystallised twice from alcohol melted at 131" and gave no de- pression when mixed with nitrosopinene.From 100 grams of pinene nitrosochloride, 70 grams of the crude imide were obtained. The imide dissolves moderately in hot alcohol, crystallising in rosettes of hard prisms having the appearance of truncated octahedra, and after two recrystallisations the substance is quite colourless and melts at 238-240" with some previous discoloration. In cold solvents the new compound is only very sparingly soluble, but crystsllises from hot, dilute acetic acid in prismatic needles, from hot methyl alcohol in small prisms, and from hot water, in which it is only slightly soluble, in needles ; in basic solvents such as aniline or pyridine, the h i d e is readily soluble : 0,1139 gave 0.2388 CO, and 0.0704 H20.C=57*18; H=6*96. 0.1326 ,, 0.2788 CO, ,, 0,0843 H20. C=57.34; H=7*06. 0.1226 ,, C12H170,N, requires C = 57-37 ; H = 6.77 ; N = 16.73 per cent. 18.2 C.C. moist nitrogen at 19" and 766 mm. N = 17.19, C,,H,,O,N, ,, C = 57.14 ; H= 7.14 ; N = 16.66 ,, ,, When boiled with dilute hydrochloric or sulphuric acid the substance is not changed and the solution when made alkaline does not reduce Fehling's solution ; prolonged boiling, however, with con- centrated hydrochloric acid decomposes it, giving oily products, and the solution yields a red precipitate of cuprous oxide on addition of Fehling's solution and caustic alkali.LEACH : A PSEUDO-SEMICARBAZIDE FROM PINENE.15 Action of Nitric Acid.-The imide dissolves readily in cold concentrated nitric acid (sp. gr. 1-42), forming a colourless liquid with but slight development of heat ; the liquid on boiling becomes yellow and a reaction appears to take place with evolution of red fumes: addition of water., however, precipitates the unchanged imide in fine needles, This behaviour is remarkable in a pinene derivative and supports the view that the substance is a ureide or ring compound of a very stable nature. Potassium Salt.-2.5 grams of the imide were ground to a fine powder and mixed with 15 C.C. of cold alcohol, 0.6 -gram of caustic potash dissolved in the smallest quantity of water was then added ; the imide dissolved and almost immediately a solid, white mass of the potassium salt was precipitated, which, after filtering and washing with a little absolute alcohol, was dissolved in absolute alcohol and re- precipitated by addition of dry ether : 0.5855 gave 0.1737 K,SO,.K = 13.31. C,,H,,O,N,K requires K = 13-49 per cent. The potassium salt is extremely soluble in cold water, and when carbon dioxide is passed into the solution the imide is precipitated as a very bulky mass of fine needles; exposure t o air causes the salt to decompose slowly owing to the action of moisture and carbon dioxide. It dissolves readily in warm alcohol, from which it crystallises in large, rhombic prisms, but is insoluble in dry ether. Sodium Salt.-This is prepared in a similar manner to the potassium salt ; it differs, however, in being more soluble in cold alcohol.Addition of dry ether precipitates it in white and somewhat opaque needles. ActioPa of Alkali.-The imide dissolves very readily in dilute aqueous caustic alkalis, being reprecipitated by addition of dilute acids ; if, however, the substance is boiled with 30 per cent. aqueous caustic potash, the liquid acquires a red colour and evolves ammonia. During the course of the reaction a crystalline deposit appeared in the con- denser and proved to be nitrosopinene (m. p. 131') ; after the evolution of ammonia had ceased the liquid was diluted with water and acidified with hydrochloric acid, when evolution of carbon dioxide and the separation of crystalline matter took place ; the latter after recrystal- lisation yielded a considerable quantity of nitrosopinene : CNOH CNe*NH,' Conversion into Pinene Nitrolamine, C,H,,< I Five grams of the imicle were added gradually to 20 C.C.of concen- trated sulphuric acid, when considerable development of heat occurred,16 LEACH : A PSEUDO-SEMICARBAZIDE FROM PINENE. and a colourless solution was formed; on heating to 85O, effervescence took place with evolution of carbon dioxide and formation of ammonium sulphate, the liquid became pale yellow and finally red. After tbe evolution of gas had ceased, the liquid was cooled and poured on to crushed ice, yielding a. clear solut.ion. Addition of aqueous caustic soda gave a crystalline precipitate which immediately dissolved in excess of the alkali, and the colour of the solution changed from red to yellow; carbon dioxide changed the colour to red again and pro- cipitated a crystalline deposit of fine needles, which, when filtered and recrystallised from alcohol, softened a t 118' and melted a t 1 2 3 O with evolution of gas.Further recrystallisation did not alter the melting point, and the substance remelted at 129-131", behaving exactly like pinene nitrolamine : 0.1800 gave 24.0 C.C. moist nitrogen a t 20' and 772 mm. N = 15.50. C,,H,,ON, requires N = 15.38 per cent. When mixed with pinene nitrolamine, obtained by the action of ammonia on pinene nitrosochloride (see preceding paper, page 4), no depression of the melting point took place. It forms a hydro- chloride identical with that of pinene nitrolamine, and therefore its identity is established : I n order to ascertain whether free nitrogen was eliminated during the reaction between the sulphuric acid and imide, a weighed quantity of the latter was placed in a small flask attached to a carbon dioxide apparatus and a nitrometer in the usual manner, when it was found that the whole of the gas expelled on warming the flask to 100' was absorbed by the caustic potash in the nitrometer, and on adding caustic potash to the diluted sulphuric acid solution in the flask, ammonia was evolved.CH--NH l2 CMe*NH PinyZ-$-carbamide, C H < I >GO. Twenty grams of the imide were powdered and suspended in a mixture of 75 C.C. of glacial acetic acid and 40 C.C. of water, 35 grams of zinc dust were gradually added to the pasty liquid, and the mixture shaken from time to time, the temperature not being allowed to rise above 50".I n a short time the liquid became frothy, owing to the evolution of carbon dioxide, and had an odour recalling that of an isocyanate. The elimination of ammonia took place simultaneously, and was detected by addition of caustic alkali to aLEACH : A PSEUDO-SEMICARBAZIDE FROM PINENE. 17 small portion of the solution. When the liquid had become quite clear, it was heated on the water-bath for an hour, and on adding ammonia, a bulky, white precipitate of small needles, mixed with some oily matter, was obtained, which when filtered and dried gave a pale brown product with an odour of peppermint, due no doubt to the formation of small quantities of the ketone (Wallach's pinocamphone). From 100 grams of the imide, 60 grams of the crude, dry pinyl-+- carbamide were obtained, giving, after recrystallisation from hot dilute alcohol, aggregates of colourless but almost opaque prismatic needles melting at 224' without decomposition.The crystals when deposited from the solution were transparent, but after separating and drying in the desiccator became opaque, probablydue to loss of solvent of crystallisation : 0.1121 gave 0.2782 CO, and 0.0940 H,O. C = 67.67 ; H = 9-31. 0.1798 ,, C,,H,,ON, requires C = 68.04 ; H = 9.26 ; N = 14.43 per cent. The pseudocarbamide is readily soluble in hot water, methyl alcohol or acetic acid, sparingly so in chloroform or ether, whilst in light petroleum it is almost insoluble. Cold concentrated sulphuric acid dissolves the pseudocarbamide, which is reprecipitated by ammonia.When heated with 30 per cent. aqueous caustic potash no ammonia was evolved, the substance appearing quite unchanged. The very stable nature of the pseudocarbamide is further emphasised by the fact that, when heated in a dry test-tube, it sublimes and condenses in small leaflets on the sides of the tube. 22.6 C.C. moist nitrogen a t 27" and 758 mm. ..N = 14.61. Beduction, of the Imide by Glccciul Acetic Acid and Zinc. I n the first experiments on the reduction of the imide it was noticed that if glacial acetic acid and zinc dust were used, a white, crystalline, but very insoluble compound separated from the liquid, and although a certain amount of the pseudocarbamide was produced, it was largely contaminated with this insoluble substance, Thirty grams of the imide were suspended in 200 C.C.of glacial acetic acid and 40 grams of zinc dust gradually added with shaking ; after a short time an almost clear solution resulted, and the reaction was com- pleted by heating for several hours on the water-bath. Water was then added t o dissolve zinc acetate, and the liquid on being decanted from the zinc residues contained the insoluble matter in suspension ; after filtration and washing with water, a colourless, crystalline com- pound was left which was insoluble in boiling alcohol or other solvents, except hot acetic acid, from which it crystallised on cooling in small, hard prisms which did not melt below 300'. The filtered liquid when poured into water gave a further quantity VOL. XCI. C18 LEACH : A PSEUDO-SEMICARBAZIDE FROM PINENE.of the insoluble substance, and after filtration and addition of ammonia a crystalline deposit of the pseudocarbamide was obtained : 0.1282 gave 0.3000 CO, and 0.1026 H,O. 0.1418 ,, 15.7 C.C. moist nitrogen at 19' and 753 mm. N = 12.59. C,2H200,N, requires C = 64.28 ; H = 8.92 ; N = 12.50 per cent. When this substance was heated in the water-oven, acetic acid was given off, and after being dried at 100' it lost 10 per cent. of its weight; the whole of the acetic acid, however, was not evolved, because on warming a small portion of the dried substance in a test- tube the pungent and characteristic odour was noticed. This compound is insoluble in dilute acids and alkalis, but dissolves in concentrated sulphuric or nitric acid, and on dilution is precipitated unchanged.Reduction of the imide by alcoholic hydrochloric acid and zinc dust also yielded small quantities of the same insoluble com- pound, and it is hoped that further investigation will elucidate its constitution. C = 63.52 ; H = S%9; Twenty grams of the pseudocarbamide were made into a paste with water and mixed with 200 C.C. of water and 20 C.C. of concentrated hydrochloric acid, the liquid was cooled to Oo by the addition of crushed ice, and 10 grams of sodium nitrite added in small portions at rz time with stirring. The pseudocarbamide was rapidly attacked, and a pale yellow, bulky solid was precipitated; after standing for an hour the liquid was filtered, when 19 grams of a bright sulphur-yellow nitroso- compound were obtained which crystallised from alcohol in small, yellow, hexagonal plates with a distinct red lustre when viewed by reflected light : 0.1 127 gave 0.2436 CO, and 0.0798 H,O.C = 58.95 ; H = 7.86. 0.1072 ,, 17.4 C.C. moist nitrogen a t 1 7 O and 754 mm. N = lS.68. C1,H170,N3 requires C = 59.19 ; H = '7.62 ; N = 18.83 per cent. The nitroso-$-carbamide gives the Liebermann reaction in all its stages, but so far its action towards aniline has not been studied ; it is readily soluble in methyl or ethyl alcohol, from which i t crystallises in plates ; it dissolves in chloroform or acetic acid, being precipitated from the former by light petroleum in clusters of needles ; in warm benzene it is only moderately soluble, and very sparingly so in light petroleum.Action of Caustic AE?caZi.-The nitroso-$-carbamide dissolves in 10 per cent. alkali, giving a colourless solution, and on additiori of a concentrated solution of the alkali the sodium salt is precipitated in pearly leaves, which, after filtration, washing with a little alcohol, and drying on a porous plate, yield a colourless but impure substance. If,LEACH : A PSEUDO-SEMICARRAZIDE FROM PINENE. 19 however, the nitroso-compound is warmed with 25 per cent. aqueous caustic soda it partially dissolves, nncl on further warming a yellow oil appears with evolution of gas ; the liquid has a camphoraceous odour, and on cooling yields a semi-solid, crystalline mass ; addition of dilute sulphuric acid with a few drops of starch and potassium iodide solution gives an intense blue colour, showing that nitrous acid has been with- drawn from the nitroso-q-carbamide.The investigation of the pro- ducts 'of the reaction is not yet complete. Action of' Light on the Nitroso-+-curbamide. When freshly prepared the nitroso-compound is yellow with a delicate pink reflex; it was noticed, however, that if left exposed to light and air the crystals soon developed a bright green colour. Some experiments were therefore made in order to ascertain to what cause this change of colour is due. When the nitroso-+-carbamide is spread out in a thin layer on a flat-bottomed dish, covered with a clock glass, and exposed to sunlight, the colour of the crystals changes in the course of a few minutes to a bright, opalescent green and after some time to a deeper t i n t ; examined by the lens, the surface of the crystals appears quite bright and the colouring uniform, but after exposure for some hours the green tint begins to fade and the surface becomes white and opaque.The crystals lose their trans- parent character and finally, after about a week's exposure, they become dull yellow, further exposure causing no alteration. The melting point of the pure nitroso-$-carbamide is 16l0, but after exposure the crystals did not melt until 190' was reached, and then after considerable previous softening. On examination under the microscope, the crystals were no longer bright and transparent, but of a dull uniform yellow colour, the surface of the crystals appear- ing '' pitted '' as if gas had escaped and minute crystals had grown on the surface of the larger ones, whilst the angles had lost their sharp and well-defined character.The product obtained after exposure differed from the nitroso-+-carbamide in being insoluble in dilute caustic alkalis and in not giving the Liebernlann reaction ; after recrystallisation from dilute alcohol the melting point gradually rose to 2 2 2 O , and on mixing with the pinyl-+-carbamide no depression was observed. I n order to prove its identity with the latter substance, a small quantity of the recrystallised product was added to crushed ice mixed with a little dilute hydrochloric acid; addition of sodium nitrite precipitated the original nitroso-1C/-carbamide melting at 16 lo. The fact, therefore, that the nitroso-$-carbamide eliminates the nitroso-group when exposed to light is proved ; it appears probable, c 220 LEACH : A PSEUDO-SEMLCARBAZIDE FROM PINENE. however, that this change is brought about by the action of moisture, causing hydrolysis : This hypothesis was tested by placing a small quantity of the nitroso-compound in a test-tube with two or three C.C.of distilled water, and a few drops of potassium iodide and starch solution, but no colour appeared after several hours ; on repeating the experiment with the addition of one drop of dilute sulphuric acid, the blue colour appeared in a few minutes. CHON( NH,) CMe-NH Pinyl-+-semicadaxide, C7H12< I >CO. Twenty grams of the nitroso-+-carbamide were made into a paste with 20 C.C. of water, and mixed with 150 C.C. of water and sufficient crushed ice to reduce the temperature below 5 O . Twenty-five C.C.of glacial acetic acid were added, and 25 grams of zinc dust stirred in gradually, together with more ice if necessary. The yellow nitroso- compound dissolved slowly, forming a clear solution, and after half- an-hour had elapsed 10 C.C. of acetic acid were added, the re- duction being complete in about two hours. The liquid was then filtered from zinc and evaporated to 500 C.C. The acetic acid, after being partially neutralised by addition of concentrated ammonia, caused the precipitation of brown, viscid matter, and after filtration a nearly colourless liquid was obtained, from which by further addition of ammonia the pseudosemicarbazide was precipitated in a fairly pure condition. From 20 grams of the nitroso-#-carbamide, 9 grams of the pseudosemicarbazide were obtained, which crystallised from hot alcohol in colourless, small, rhombic prisms melting at 209".The specimen analysed was dried at 100' for half-an-hour : 0.1360 gave 0.3138 CO, and 0.1158 H,O. 0.1074 ,, 19.2 C.C. moist nitrogen at loo and 752 mm. N = 20.32. C,,H,,ON, requires C = 63.15 ; H = 9-09 ; N = 20.09 per cent. The pseudosemicarbazide dissolves readily in warm methyl or ethyl alcohol, chloroform, or acetic acid, and moderately in warm acetone or benzene, crystallising from the latter in transparent plates; it is sparingly soluble in ether, and insoluble in light petroleum, and crys- tallises from water in t u f t s of minute needles. Towards ammoniacal silver nitrate it acts as a powerful redncing agent, giving a black deposit of metallic silver in the cold ; with Fehling's solution, however, no action takes place, but on warming a copious precipitate of cuprous oxide is deposited, evolution of gas occurs, and an oil separates, having at first an odour of peppermint (probably pino- C = 62.92 ; H = 9.46.LEACH : A PSEUDO-SEMICARBAZIDE FROM PINENE.21 camphone) and, after the lapse of a few minutes, distinctly that of carvone. This reaction appears to be similar to that observed by Forster and Fierz (Trans., 1905, 87, 727), who found that oxidation of camphoryl-y?-semicarbazide with Pehling's solution gave rise to camphor. Ferric chloride added to a cold alcoholic solution of the JI-semi- carbazide caused a slight evolution of gas which became much more brisk on warming ; addition of water precipitated a white, crystalline substance.The pseudosemicarbazide did not give a platinichloride, for on warming the solution became dark, evolved gas, and yielded a tarry residue with an odour of turpentine; in this respect the pseudosemi- carbazide of pinene behaves like semicarbazide itself (Thiele and Stange, Annalen, 1894, 283, 21). The hydrochloride was obtained by passing dry hydrogen chloride into a solution of the pseudosemicarbazide in ether, a finely-divided, crystalline precipitate separated, and when filtered and recrystallised from absolute alcohol was deposited in thin, lustrous plates decomposing indefinitely at 250' : 0.3978 dissolved in water required 16.4 C.C. N/lO AgNO,. C1= 14.58. C,,H,,ON,Cl requires C1= 14.45 per cent.No indicator need be used in the titration because the slightest excess of silver is shown by the solution turning black, owing t o the strong reducing action of the pseudosemicarbazide. Towards hot concentrated hydrochloric acid the base is quite stable, the hydro- chloride being deposited on cooling. Copper Nitrate Double Salt.-The base, dissolved in the 1ea.st quantity of dilute nitric acid, was added to a concentrated solution of copper nitrate in absolute alcohol ; from the green solution bright blue needles were deposited, and after recrystallisation from hot water the czcpri- nitrate was obtained in tufts of blue needles decomposing about 175' : Cu = 8.79. (C1,H190N,,HN0,)2,Cu(N0,), requires Cu = 8.68 per cent. 0.1760 gave 0.0194 CuO.The PinyZ-$-semicarbazo~~es. Pinyl-$-semicarbazide combines with aldehydes and ketones with great readiness ; with acetone, however, no condensation product has been obtained. The base is dissolved in dilute acetic acid, diluted largely with water and the requisite quantity of the aldehyde or ketone, also dis- solved in dilute acetic acid, added. The liquid becomes turbid, and on gently warming the pseudosemicarbazone separates, of ten as a viscid oil, soon becoming crystalline, or directly in a crystalline condition.22 LEACH : A PSEUDO-SEMICARBAZIDE FROM PINENE. With the exception of the quinone-$-aemicarbazone, there appears to be little or no tendency to combine with the solvent such as was exhibited in the case of the corresponding camphoryl derivatives (Forster and Fierz, Trans., 1905, 87, 725); the quinone compound, however, retains one molecule of water, which is not lost in the desiccator, but on heating to 100" is completely eliminated.Benxylidene Pin~l-~-senzicarbuxolze, is precipitated by the addition of benzaldehyde to the solution of the base in dilute acetic acid. It crystallises from alcohol in rhornbic prisms which melt at 180", remelting at the same temperature. It dissolves readily i n cold chloroform, and is reprecipitated by light petroleum in colourlees, rhombic prisms ; it dissolves readily in cold acetic acid, but is much less soluble in ether and almost insoluble in light petroleum : 0.1491 gave 18.4 C.C. moist nitrogen at 18" and 770 mrn. N = 14.43. C,,H,,ON, requires N = 14-14 per cent.The benzylidene derivative is insoluble in dilute hydrochloric acid, but when heated hydrolysis takes place, giving a strong odour of benzaldeh y de. Salicylidene I'iiz~l-~-semicarbccxone, when crystallised from hot alcohol, in which it, is only moderately soluble, yields small, hard, rhombic prisms melting at 252'. It; is moderately soluble in chloroform, methyl alcohol, or acetic acid, sparinglyso in warm benzene and insoluble in light petroleum : 0.1522 gave 17.6 C.C. moist nitrogen a t 18' and 770 mm. N = 13.54. C18H2302N3 requires N = 13.41 per cent. The salicylidene derivative dissolves in dilute aqueous caustic potash, and is reprecipitated on addition of dilute hydrochloric acid. The alcoholic solution with ferric chloride gives an intense green coloration, which is not altered by dilute hydrochloric acid.m-Niti*obenxplidene Pinyl-i,!r-semicai.baxone, separated from the solution as a yellow, viscid solid, which soon hardened and crystallised. It aissolves sparingly in nearly all solvents, forming yellowish-green solutions ; from hot alcohol i t crystallises in pale yellow, small, hard prisms melting at 216". On cooling, itLEACH : A PSEUDO-SEMICARBAZIDE FROM PINENE. 23 solidifies to a clear, glassy mass, then crystallises, and on reheating melts a t a lower temperature : 0.1056 gave 15 C.C. moist nitrogen at 17.5' and 765 mm. N = 16.54. p - Methoxy benx y 1 idene Pin yl-$-semicar baxone, C18H2,03N, requires N = 16.37 per cent. separates from hot alcohol in transparent and well-defined rhombic prisms melting a t 224-225", and remelts at the same temperature.It dissolves readily in warm alcohol, chloroform, or acetic acid, and is sparingly soluble in warm ether or ligbt petroleum, crystallising from the latter in small clusters of prisms; from dilute acetic acid clear flat prisms were deposited, but the odour of the aldehyde was distinctly noticeable in the liquid, owing no doubt to a partial hydrolysis : 0.1622 gave 18.7 C.C. moist nitrogen at 23' and 771 mm. N = 13.16. Ciitnarnylidene Pinyl-$-semicarbaxone, C,,H2702N, requires N = 12.79 per cent. crystallises from hot alcohol in small, colourless prisms melting at 236' with slight discoloration, It dissolves sparingly in cold methyl or ethyl alcohols, but readily in the warm solvents, and crystallises from the former in transparent, four-sided prisms; it is soluble in chloroform or warm benzene, but sparingly so in ether or light petroleum : 0.1504 gave 17.2 C.C.moist nitrogen a t 21' and 766 mm. N = 13.12. C20H2,0N3 requires N = 1 3.00 per cent. Addition of the quinone to the base caused the immediate separation of a bulky, brown crystalline precipitate from the deep red solution. When crystallised from alcohol, dark yellow needles are formed, which decompose a t 194' with evolution of gas. The substance dissolves readily in chloroform, methyl or ethyl alcohol, or acetone, giving deep orange-coloured solutions; it is sparingly soluble in ether or light petroleum, giving bright yellow solutions; i t dissolves also in warm dilute caustic potash to an orange-coloured solution, and on addition of dilute hydrochloric acid a deep green precipitate is obtained. When heated to looo, the colour changes from yellow to orange, and the compound loses weight corresponding to one molecule of water ; two separately prepared specimens were analysed :24 LUMSDEN: THE LIQUID VOLUME OF 0.1644 gave 19.2 C.C. moist nitrogen at 22' and 770 mm. N = 13.40. 0.2126 lost 0.0118 at 100' ; H20 = 5.55. 0.1480 ,, 17.3 C.C. 9 , 19' ,* 766 ,, N=13*54. ClvH210zN3 requires N = 14.04 per cent. C,7H,,0,N,,H,0 ,, Acetone Pin$-+sernicarbaxone.-Addition of acetone to the dilute acetic acid solution of the base gave no precipitate on warming; in dilute ammoniacal solution an oil separated, from which, on standing, the pseudosemicarbazide crystallised. N = 13.24 ; H,O = 5.67 per cent. Action of Nitrous Acid on the Hydrochloride of the pseudo-Xernicarbaxid. The hydrochloride was dissolved in water and cooled to 0' by the addition of ice, and exactly one molecular proportion of sodium nitrite was added. The liquid became turbid, and a white, crystalline pre- cipitate of the pseudocarbamide separated : vH*N(NH2) C7H12<(lMe_--" >CO + HN02 = CH-NH C 7 H , 2 < b ~ e .NH >CO + N20 + H20. The presence of the nitrous oxide was not proved. When the pseudosemicarbazide was dissolved in dilute nitric or hydrochloric acid and sodium nitrite added, a white precipitate separated at first, and soon afterwards a yellow oil which crystallised, and on examination proved to be the nitroso-$-carbamide melting at 161'. ROYAL COLLEGE OF SCIENCE, LONDON, SOVTH KENSINGTON, S. W.

ISSN:0368-1645    

DOI:10.1039/CT9079100010

出版商:RSC    

年代:1907

数据来源: RSC

摘要:

24 LUMSDEN: THE LIQUID VOLUME OF 111.-The Liquid Volume of a Dissolved Substance. By JOHN SCOTT LUMSDEN. THE following investigation was undertaken in order to obtain some information regarding the volume assumed by a solid, liquid, or gas when dissolved in a liquid on which it exerts no chemical action. It is well known that the values determined for atomic volumes and atomic refractions from experiments made on pure liquids hold with fair accuracy when applied to solids and liquids in solution; and the inference is, that a liquid retairis its own volume when dissolved and that a solid assumes in solution the volume which theA DISSOLVED SUBSTANCE. 25 same weight would have if it existed as a liquid at the same temperature. If that inference is correct, or if it can be proved to vary from exactness in a rational manner, a law of the li.quid volume of a dis- solved substance is revealed and the experimental results here recorded show that there is such a law, which holds, not only for the volume assumed by a solid or liquid, but also for the volume taken by a dissolved gas.A t the beginning of the investigation it was found necessary to exclude from consideration solutions in which water was the solvent, since solution in water is of the nature of combination and is always accompanied by a marked shrinking i n volume ; a further contraction also occurs if the dissolved substance becomes ionised. The first experiments were designed to prove that a dissolved substance behaves as a liquid and does not undergo any sudden change in volume as the temperature is raised above its normal melting point or boiling point.A number of substances of widely different composition were chosen ; these were dissolved in various solvents and the volume of the molecular weight in grams of each substance was measured at several temperatures. A quantity of substance was weighed in a short-necked, stoppered flask, the solvent was added and the flask was reweighed. A pyknometer was filled with the solution obtained in this way by inserting the point of the instru- ment into the flask and withdrawing the liquid, and a similar pykno- meter was filled with the solvent. The pyknometers were then placed together in a thermostat and after remaining a sufficient time a t the desired ,temperature they were removed, dried, and weighed.The capacity of each pyknometer was carefully determined at several temperatures and by interpolation the capacity a t any desired temperature was obtained. All the weighings were corrected to the weight in a vacuum and the densities are referred to water at 4O, thus making the number which expresses the molecular volume represent also the volume in cubic centimetres of the molecular weight in grams of the substance at the temperature given. The molecular volume in solution was calculated by the usual i- - ’ where M is the molecular weight formula : Vm = - D of the substance, D the density of the solution, d the density of the solvent, and s the weight of the solvent used to dissolve the molecular weight in grams of the substance. 2’26 LUMSDEN: THE LIQIJID VOI.CME O F Mol ecu 2 ~ 1 ' Yo Zzt me of Ntcphth ale ne i n To1 uene .2.7935 grams of naphthalene mere dissolved in 19.7216 grams of toluene : sp. fir. Temp. toluclle. 15" 0.8706 25 0.8612 40 0.8476 60 0.8296 so 0.8113 100 0.7931 Sp. v. 0.8885 0.8'791 0.8653 0.8473 0 8287 0-8104 solnt?on. Vol. of 128 g. nnphthalene. T I n solution. As liqiiid. 123.28 - 124.25 - 128.42 130'92 * 131'05 (98'4") 133'64 133'04 t 126.05 (79 .9") * Schiff, A.imcdeii, 1884, 223, 261. f Nasini, Gnxetta, 1885, 15, 84. Molecular Volunie of I'hen ylacetic Acid in Toluene. 3.1889 grams of acid were dissolved in 19.6646 grams of toluene : Temp. 15" 25 40 60 80 100 sp. 91.. toluene. 0.8706 0.8612 0-8476 0.8296 0,8113 0.7931 Vol. of 136.08 g. acid. A sp. 8''. / \ solntion.In solution. As liqnid. 0.8998 119.91 (7 6 '6") 0 '8 9 0 6 120.60 125.50 0*8770 122.04 O*S590 123.84 (86 *2"1 * 0.8405 125.88 i26.41' (89-5") 126.73 0'8223 127-90 -x Schiff, A~~nalen, 1884, 223, 260. iliolecular Yolume of llhynzol iq~. Benzene. 2-0108 grams of thymol were dissolved in 14.1864 grams of benzene : Temp. 15" 25 35 45 55 65 Vol. of 150 g. thymol. Sp. gr. Sp. gr. F A \ 0.8846 0'8943 154.74 0.8742 0'8842 156*01 0-8639 0'8740 157 -50 157'91 benzene. solution. I n solution. As liquid. * ( 49'3") 158.99 (58'3") 159.08 (64") 0.8638 0.8536 0'8432 0'8535 160 -58 0.8328 0.8432 162.26 159.78 * Schiff, Amalen, 1884, 223, 259.A DISSOLVED SUBSTANCE. 27 Jfolecular Volume of Dichlorobenxene in, Carbon Tetrachloride. 2.0677 grams were dissolved in 30.3615 grams of carbon tetra- chloride : Vol. of 146 -9 g.dichlorobenzene. s;). $"'. Sp. gr. A- Temp. CC1,. solation. I n solntion. As liquid. 15" 1 '6039 1.5794 113.93 - 25 1.5845 15608 114'77 - 35 1.5652 1'5435 45 1 *5462 15244 116.33 55 1.5275 1'5065 117.18 65 1.5075 1.4876 117.95 115.48 (5$ 117'63 (63") 118'36 ' Schitf, A?~?inlen, 1884, 223, 263. i I l o l e c d ~ r Voltone of o-iVhrophenol in Chlorofoma. 1.1628 grains of nitrophenol were dissolved in 12.9120 grams of chloroform : Vol. of 139 Q. nitrophenol. 'l'enip. CIECI,. solution. In solution. As liquid. sp. 6'. 81'. gr. r 2. \ 15" 1.4898 1 *4774 102.80 * (35") 106'48 25 1 *4721 1 '4605 103.56 35 1-4531 1 -4423 104'31 (45.2") 45 1.4344 1,4247 105-06 107.38 108'29 55 1.4163 1.4071 105'91 (55") + Schiff, Annalcn, 1884, 223, 263.Moleculur Qolunte of Chloroform in Toluene ; Vol. of 119.4 g. chloroform. Tciiil). toluene. solution. I n solution. As liquid. 4 0" 0'8472 0'9647 82-98 (20") 80.21 * 60 0.8290 0.9427 85.39 (40 ) 83-33 80 0'8105 0'9203 88.02 (60 ) 84.62 * Thorpe, Trans., 1880, 37, 196. Sp. gr. Sp. gr. c A > Moleculccr Volume of Bromine in Carbon Tetrachloride. 3.4716 grams of bromine were dissolved in 28.3596 grams of CCI, : Vol. of 79.96 g. bromine. Temp. CCl,. solution. I n solution. As liquid. 40" 1.5555 1.6379 27'70 26-22 * 50 1.5362 1-6178 27 '98 26'52 60 1.5173 1.5981 28-27 26.83 70 1'4969 1'5769 28-57 - 75 1.4892 1 -5687 28.74 * Thorpe, Trans., 1880, 37, 174. Sp. gr. Sp. gr. c A -I28 Temp. 15" 40 80 120 160 200 220 LUMSDEN: THE LIQUID VOLUME OF Molecukar Volume of Nap?&alene in, Quinoline : Vol. of 128 g.naphthalene. Sp. gr. /- h \ solution. I n solution. As liquid. SP. gr. quinoline. 1,0978 1.0887 123.73 130'34 1-0785 1-0691 126'40 1'0478 1.0378 130.85 (130.7") 1-0150 1.0057 134'61 136.78 (173'8") 141-99 0'9826 0,9735 139'20 0.9489 0.9394 144.93 (193 '6") 143'37 0.9319 0.9234 146'56 (217") 14757 (7G) * Lossen and Zander, Annnlen, 1884, 225, 111. These molecular volumes are represented by curves on the accampanying diagram and the continuity of the curves makes it apparent that with rise of temperature the increase of volume is regular and that no breaks occur at the normal melting points or boiling points of the dissolved substances. Liquids, such as bromine and chloroform, when in solution were raised to temperatures above their boiling points, but their volumes did not nndergo any sudden change ; similarly, solids such as naphthalene and thymol when in solution were raised to temperatures above their melting points, but their curves of volume are continuous ; and in the example given of a solution of naphthalene in quinoline, the change of temperature includes the regions a t which the naphthalene normally exists as solid, liquid, and gas, yet there are no breaks in the curve of volume.I n solution there is, therefore, only one phase, namely, the liquid phase, and a substance in solution a t any temperature behaves as a simple liquid. The next point on which information was sought was the relation between the volume of a pure liquid and its volume when dissolved.The substances employed in the foregoing experiments had in every case been examined by previous workers and their volumes determined in the liquid state a t several temperatures. From these measurements, the molecular volumes were calculated,and the values obtained aregiven in the last columns of the preceding tables and are indicated on the volume diagram by dotted lines. It is seen that naphthalene and phenylacetic acid dissolved in toluene have volumes in solution almost identical with their volumes as pure liquids ; bromine in carbon tetrachloride, thymol in benzene, and chloroform in toluene show greater volumes in solution, whilst nitrophenol in chloroform and dichlorobenzene in carbon tetrachloride have smaller volumes when dissolved. Two liquids may therefore be mixed without any change of volumeA DISSOLVED SUBSTANCE. 29 taking place, but usually mixing is attended either by a small con- traction or a small expansion.Some very accurate experiments on the mixing of carefully purified FIG. 1. Molecular volumes of various substances in solution. 10" 20" 30" 40" 50" 60" 70" 80" 90" 100" liquids are recorded by Young and Fortey (Trans., 1902, 81, 742 and 772; 1903, 83, 45), and by Thorpe and Rodger (Trans., 1897, 71, 367), and in order to indicate the extent of the change of volume30 LUMSDEN: THE IJQUID VOLUME OF accompanying mixing, I: giro the memnrements made by these investigators : Mixtures of Voln1mFs. Tolueiie and etliylbenzenc .................... Eqiiiiiiolt~q1:~r Hexniie and octane ............................. 7 , Carbon tetrachloride and benzene ............I , 7 ) ,, methyl alcoliol 1 , Ethyl acetate and ethyl propionate ......... 7 9 Benzene and tolnene ............................. > 7 Chlorobenzene aiid bromobenzene ........... ¶ I 9 , ... Beiizene and ethyl alcohol ..................... 31 per cent. alcohol Ether and chloroform ........................... 84 per cent. chlorofoi 111 Carbon disulphide and methyl iodide ..... 78.4 per cent. methyl iodide Il1stc~:Wl of Ob- 100 C . C . servers. 99.966 Y. & F. 99.966 ), 99.849 ,, 99'820 ,, 100*015 ), 100'161 ,, 100~000 ), 100~000 99.185 T. k R. 100*Pl7 ,, F I G . 2. M o l e c d a y voluwic of nnplzlhalelie iiz quinolinc. 150 i$ % 140 $ T5 u 5 130 2 120 0" 5 0" 100" 150" 200" I n no case do these measurements by Young and Portey indicate a change of volume on mixing as great as one-fifth of 1 per cent., and according to Thorpe and Kodger, a mixture of the two dissimilar liquids, ether and chloroform, is accompanied by a change which does not exceed 1 per cent.Referring again to the volume diagram it will be observed that the curve indicating the volume of the pure liquid at different temperatures runs parallel with the curve showing the volume of the substance in solution. One learns from this that whatever change takes place on mixing two liquicls a t one temperature, the same amount of change will take place on mixing them at another temperature. It also leads to a second important generalisation: if the volume of a pure sub- stance over the range of temperature when i t is liquid can be repre- sented by a curve which coincides with or runs parallel to the volume curve of the substance in solution, then, as the trend of the solution curve is regular, it may safely be concluded that if the pure substance remained liquid, its volume, at any temperature below or above the temperature of the normal liquid state, mould be represented by a point on an extension of the liquid volume curve continued parallel to the curve of the volume in solution.A DISSOLVED SUBSTAKCE.31 It follows directly from this that, if the two curves coincide, the conditions of the law of liquid volume are fulfilled, and the law may be stated thus : When cc substance in tibe liquid state dissolves without change of volume, tlhe same substance when in the stcde of solid OY US wild, when dissolved in the same solvent, chccnge to the volume which the same weight of it would have if it were a pure liquid at the temperature of solution.Should, however, the two curves run parallel, the deviation from the law may be expressed as follows : When a substtcnce in the liquid state, on being dissolved, changes in volume by cc certaiiz amount, the same substunce, when in the state of solid or gas, will, when dissolved, assume a volume which difers fyom tlhe volume which it would have if liquid at the sccme temperatum, by the same amount. These two definitions may be combined in a general statement: the volume occupied by a substance in solution is the same as that of the pure substance at the same temperature if it were liquid; or if it is not identical, it deviates by the same amount at all tempera- tures.When two pure liquids were mixed it was seen that the change in volume was very small, and the deviation from conformity with the law of liquid volume can in no instance be considerable, yet it seemed of interest to inquire further concerning the cause of the change of volume when two liquids are brought together. The cause must be looked for in the distribution of the particles of the solute throughout the solvent producing an adjustment of spacing, since it might be expected that molecules differing in size, shape, and weight, when mixed, will arrange themselves so that the new volume is not exactly the sum of the volumes added. The change, moreover, cannot entirely be ascribed to the dissolved substance; the solvent must also be affected, and if that is the case it is evident that the true volume which a substance occupies when in solution cannot be measured, since the amount of change of each constituent is unknown. From these considerations it was reasonable to predict that alteration of the amount of solvent and the employment of different solvents would give different values for the volume of a dissolved substance, and the following experiments were made to obtain information on these points.Solutions were prepared containing approximately 5, 10, and 20 molecules of naphthalene in 100 molecules of benzene, toluene, xylene, and carbon tetrachloride. Four pykno- meters were employed; one to contain the pure solvent, the others the three solutions made with this solvent.The pyknometers were heated in a thermostat to 1 5 O , removed a t the same time to ensure that they were all a t exactly the same temperature, dried, and weighed :32 Solvent. Benzene Toluene.. .... Xylene ...... Carbon tctra- chloride LUMSDEN: THE LIQUID VOLUME OF Mols. naph- thalene. i 5 10 20 5 10 20 5 10 20 5 10 20 Naph- thalene in grams. 2.4151 2.3258 2.0620 2.0382 2.1583 2.2576 1-9115 2.0811 3,8963 2,1084 2.7271 5.4420 Sol vc n t in grams. 32.0184 149250 7.0862 29'7285 15.8576 7'6144 30.8078 16'7844 17.7555 54'9772 32.8754 36 '236 3 sp. gr. solvent. 0.8848 Y > 7 ) 0.8712 7 ) 7 7 0.8678 9 ) > 9 1.6043 7 ) 9 ) Sp. gr. solution. 0.8938 0.9025 0.9150 0'8802 0.8883 0'9046 0.8761 0-8836 0.8940 15741 1.5425 1'5006 Vol.of 128 g. naph- thalene. 123 '90 123'63 123'48 123'43 123.30 123'17 123-88 123'69 123.55 121.23 121-46 121.98 These molecular volumes of naphthalene, calculated as before on the assumption that each solvent retains the volume it has in the pure state, show that there is in solutions in benzene, toluene, and xylene a distinct diminution in volume with increase of concentration, whilst in carbon tetrachloride the volume becomes greater as the amount of solvent decreases. Several experiments with carbon tetrachloride gave the same result : a diminution in the volume of the dissolved substance on dilution. The cause of these changes will be discussed later on. An experiment was then made in order to find the change in volume of the dissolved substance when different solvents were used. Solutions containing approximately 10 molecules of naphthalene to 100 molecules of benzene, toluene, xylene, and carbon tetrachloride were prepared, these were heated a t 154 removed from the bath at the same moment, and weighed : Naph- Vol.of thalene. Solvent Sp. gr. Sp. gr. 128 g. naph- in grams, in grams. solvent. solution. thalene. Benzene ..................... 2-8556 19'7194 0.8847 0'9014 123.52 Toluene ..................... 2.6164 25.8188 0.8708 0.8837 123.55 Xylene ..................... 2.3361 19'3979 0.8679 0-8832 123.67 Carbon tetrachloride ... 2.2266 27'4185 1.6043 1.5421 122.57 The volume of naphthalene is seen to be nearly the same in benzene, toluene, and xylene, but there is a great diminution when carbon tetrachloride is the solvent, These experiments prove that the volume occupied by a substance in solution a t any given temperature alters with the solvent employed and also wifh the concentration of tho solution. The foregoing results enable one to form a conception of what takes place when two liquids are mixed, If a pure liquid is a collection of like molecules which are i nA DISSOLVED SUBSTANCE.33 constant motion jostling each other and changing their direction and motion a t every moment, and that to permit of this jostling there are spaces between the molecules, then the question arises : is the inter- space per molecule at the same temperature the same for each liquid3 Kopp did not recognise the existence of interspaces, and in the atomic volumes deduced by him are included atom and space, and the sum of the atomic values make up the whole volume of the liquid ; but accord- ing to Horstmann and Traube there must be added to the sum of the values which they assign t o the atoms a co-volume of 25.9 C.C.a t 15' in order to obtain the molecular volume, and this co-volume has a. higher value as the temperature rises. Now it is very improbable that the molecular interspaces in different liquids should have the same dimensions. The molecules differ in size, shape, and weight, and any value for the co-volume must be an average number from which the real value may in any given case differ considerably. If, however, the co-volume be different in different liquids, then, when two liquids are brought together, an adjustment of the dimensions of the interspaces will sufficiently account for the change in volume.With regard to this adjustment, little can be inferred from the size and shape of the molecules, but considering only their mass, the direction of the change of volume may in many cases be explained. It was seen that when naphthalene was dissolved in carbon tetra- chloride the volume was smaller than when the solvent was benzene, and that, whilst in carbon tetrachloride the volume diminished on dilution, in benzene the volume was greater as the amount of solvent was increased. When the molecules of naphthalene were introduced amongst the heavier molecules of carbon tetrachloride they would be subjected to greater pressure than if they existed as liquid naphthalene, since the mass attraction between the molecules of carbon tetrachloride is greater than between naphthalene molecules.This cause would lead to a diminution of volume. At the same time the carbon tetrachloride molecules would be separated from each other by the intrusion of the naphthalene molecules ; their mutual attraction would be diminished and expansion would result. The latter action must be the smaller since the experiment showed a contraction on mixture. When more solvent was employed, the separated naphthalene molecules would be subjected to still greater attraction by the heavy carbon tetrachloride molecules and thus prcjduce the diminution which was noticed on dilution, I n the case of naphthalene in benzene, the dissolved molecules are the heavier, they would be under less pressure than if in liquid naphthalene, and this would permit expansion; at the same time the 'VOT,.XCI. D34 THE LIQUID VOLUME OF A DISSOLVED SUBSTANCE. naphthalene molecules would be separated from each other, their mutual attraction would be diminished, and further increase of volume would take place. On adding more solvent the naphthalene molecules would become still more widely separated, their attraction for each other mould again be lessened, and the expansion which was noticed on dilution mould be brought about. Observed changes in volume may thereFore in many cases be accounted for by the mass attraction between the molecules of solvent and solute, but the shape and size of the molecules which are brought together must also affect the adjustment.Speaking generally, when the molecules of two substances resemble each other in size, shape, and weight, there will be little change on mixing, but when there is marked difference in the structure and weight of the molecules a con- siderable change may be expected. The following is an illustration: methyl iodide was dissolved in carbon tetrachloride and in benzene and the molecular volumes deter- mined : Vol. of wt, of 141.97 g. methyl Wt. or Sp. gr. Sp. gr. methyl Solvent, iodide. solvent. solvent. solution. iodide. Benzene ..................... 10.0459 26.5893 0.8847 1.0607 63'37 Carbon tetrachloride .., 6.8050 39.5385 1'6043 1.6778 62.09 ............ - 2'2924 - 61-93 Methyl iodide - The volume of the pure methyl iodide is seen to differ very little from its volume in carbon tetrachloride, but the increase in volume is very marked when solution is in the much lighter liquid benzene.One point in the preceding investigation demands notice: it was assumed as true that the curve of the volume of the subjtance in solution coincided with or ran strictly parallel to the curve of volume of the pure substance. The experimental results indicate that this is the case, and the examination of some measurements made by Thorpe and Rodger (Trans., 1897, 71, 367) on the densities of mixtures of carbm tetrachloride and benzene and carbon disulphide and methyl iodide leads also to the conclusion that when definite weights of two liquids are mixed the amount of change of volume which occurs a t one temperature is the same as the change a t another temperature. But it is improbable that any such regularity shonld hold ; for when two liquids have different rates of expansion the amount of change of vdume on mixing must vary somewhat with the temperature. As this variation has not been experimentally noticed, one must conclude that it is very small, more especially when the dissolved substance bears no great proportion to the total volume, and it cannot be of sufficient- magnitude t o invalidate the law of liquid volume which is based on the parallelism of the volume qurves.THE INFLTJENCE OF LIGHT ON DIAZO-REACTIONS. I. 85 In the foregoing discussion, proof has been adduced that the true volume of a dissolved substance cannot be known, and that the volume varies with the solvent and with the concentration of the solution ; but it has also been shown that the change i n volume when two liquids are mixed is very small, and that the volume assumed in solu- tion by a solid, liquid, or gas is never far removed from the volume that the same weight would occupy if liquid a t the same temperature. The law of the liquid volume of a dissolved substance is therefore seldom strictly accurate, but it deviates so little from the truth that it deserves a definite position as a guide when dealing with problems relating to solutions in liquids where dissociation cannot take place. UNIVERSITY COLLEGE, DUNDEE.

ISSN:0368-1645    

DOI:10.1039/CT9079100024

出版商:RSC    

年代:1907

数据来源: RSC

摘要:

THE INFLTJENCE OF LIGHT ON DIAZO-REACTIONS. I. 85 1V.--The I n j u e n c e of Light orb Diazo-reactions. I. By KENNEDY JOSEPH PREVITE ORTON, JOSEPH EDWABD COATES (and, in part, FRANCES BURDETT). THE voluminous literature of the diazo-group does not indicate that the remarkable effect of light on certain reactions of this class of compounds has been closely investigated, notwithstanding the fact that more than one '' diazo-type " photographic process has been pat en ted. * * Feer (D.R -P. 53455) patented a process in which a film, coated with a mixture of a diazosulphite and a phenol or an amine, was exposed to light. A decomposition of the former occurred, which was followed by coupling with the phenol or amine, and hence the production of a coloured negative. The unchanged sensitive material was washed away after exposure.Green, Cross, mid Bevitn (I>.R.-P. 56606 ; Ber., 1890, 23, 3131 ; and J. SOC. C'/mn. Ind., 1890, 9, 1001) brought forward a method for the use of the diazo- tlcrivative of priiiiuline for a similar purpose. A " negative '' was obtained by ex- posing films coated with the diazo-compound, the decomposition of which was pro- portional to the intensity of the light. A '. positive " was developed by treatment with iin amine or a phenol. I n regions of faint illumination, where the diazo-com- pouiid had not been deeoinposed, a colour developed ; where the illumination had been intense, all the diazo-compound had been decomposed and the positive was colourless. They further established that the red end of the spectrum was the more active, and that nitrogen was evolved from the diazo-compound.They, however, express themselves as " undecided whether the product is a phenol, . . . . or whether the primuline residue enters, the molecule of cellulose." They conclude, moreover, " that molecular union with the medium is a necessary condition, . . . . for the free dinzopriniuline, when exposed t o light in a thin film is either not decomposed at all, or only after very prolonged exposure.') t Ruff and Stein (Be?., 1901, 34, 1668), using a similar photographic method, have 0 236 ORTON, COATES, AND BURDETT: THE INFLUENCE OF I n the course of an investigation of some reactions of s-trisubsti- tuted diazobenzenes, notably s-tribromodiazobenzene (Orton, Trans., 1903, 83, 796; 1905, 87, 99), it was observed that the diazonium salts, the hydrogen sulphate, and the nitrate, both as solid and in solution, were exceedingly sensitive to light.The instability was the more remarkable, inasmuch as this type of diazonium salt is singularly permanent at the ordinary temperature. The effect of exposure to light could accordingly be most easily demonstrated and studied in the case of such s-trisubstituted diazonium salts. The nature of the decomposition of the diazonium salt depends on the solvent. I n water, a phenol is formed; in methyl alcohol, a methyl ether, ArnObCH, j in ethyl alcohol, an ethyl ether, Ar*O*C,H,, and in acetic acid, the phenyl acetate, Ar*O*CO*CH,; thus, for example : Ar*N(HSO,)tN + CH,'CO,H = Ar*O*CO*CH, + H,SO, + N,, If the salt is a chloride or a bromide, the diazo-group is also replaced to some extent in aqueous solution by chlorine or bromine.The influence of light is well illustrated by the behaviour of dilute solutions of 5-bromo-m-xylene-, or 6-bromo-~-cumene-diazonium hydrogen sulphates. Solutions of these salts can apparently be pre- served indefinitely at the ordinary temperature if light is rigidly excluded; thus in ten weeks no measurabIe volume of nitrogen was evolved from a 1 per cent. solution of either of these salts, If such solutions are boiled, transformation to the corresponding phenols is rapid and quantitative. Exposure to diffused daylight is followed by evolution of nitrogen; in direct sunlight, the speed of the reaction is considerable and the yield of phenol quantitative, The case of s-tribromodinzobenzene is of particular interest, inasmuch as it has been shown, by all who have investigated this substance, to behave abnormally when its solutions in water, in methyl or ethyl alcohol, or in acetic acid are heated. Silberstein (J.pr. Chem., 1883, 27, 113) could isolate no s-tribromophenol in the decomposition of aqueous solution of the diazonium nitrate. Hantzsch (Bey., 1900, 33, 2517) confirmed this observation, and, in addition, ascertained that no s-tribromophenyl methyl- or ethyl-ether was formed on heating the solutions in the corresponding alcohols, s-tribromobenzene being the sole product. Similarly, he detected no s-tribromophenyl acetate in the reaction with acetic acid, s-tribromobenzene again being alone isolated.The changes which occur when aqueous solutions of these tribromo- investigated the effect of the constitution of the diazo-compound on its " sensitive- ness." O n the basis of some experiments of Andresen (Photogrcqhische Corre- spo7~dei~z, 1595), they conclude that the diazo-compound midergoes the phenolic decomposition.LIGHT ON DIAZO-REACTIONS. I. 37 benzenediazonium salts * are heated were first described by one of us (Trans., 1903, 83, 802); i t was found that the diazonium salt mainly decomposed into dibromoquinonediazide, bromine appearing in the ionic condition, thus : C,H,Br,*N(HSO,)iN + H,O = O,:C,H,Br,:N, + HBr + H,SO,. I n the course of this research, this reaction has been again investi- gated, the diazonium salts being now also heated in solution in 63 per cent.sulphuric acid, a method first employed by Heinichen in the preparation of 2 : 6-dibromophenol (Annulen, 1889, 253, 281). Although such s-trisubstituted benzenediazonium salts, as those obtained from 3 : 5-dibromo-o-toluidine and 3 : 5-dibromo-p-toluidine, which do not undergo the phenolic decomposition when their aqueotis solutions are heated, are nearly quantitatively converted into the corresponding cresols, if 63 per cent. sulphuric acid is used as a medium, yet s-tribromodiazobenzene is still refractory. The diazonium hydrogen sulphate was rapidly decomposed, but no s-tribromophenol was formed. Subsequent to the publication of the preliminary notice (Proc., 1905, 21, 168), Gain and Norman (Proc., 1905, 21, 206) showed, however, that some 2 per cent.of s-tribromophenol could be obtained if the method described in the German patent (D.R.-P. 95339), namely, heating the diazonium salt with dilute sulphuric acid and sodium sulphate, were used. This result has been confirmed by the authors, who have isolated small quantities of s-tribromophenol from among the products of decomposition of s-tribromobenzene- diazonium hydrogen sulphate, when it is treated according to the directions in the patent. The main product of the reaction is a material resulting from a transformation of the quinonediazide, which is itself not permanent under the conditions. The decomposition, in fact, under these conditions mainly follows the course of that of the aqueous solution. I n the face of such observations it was scarcely to be expected that a means of converting s- tribromodiazobenzene quantitatively into s-tribromophenol could be found. Nevertheless, such a complete con- version of the diazonium salts in aqueous solution is induced by light.Further, both the s-tribromophenyl methyl- and ethyl-ethers and s-tribromophenyl acetate are produced if solutions in methyl or ethyl (90 per cent.) alcohols or acetic acid are exposed to light. The yield of the phenyl acetate is quantitative, but under the most favourable conditions some 30 per cent, of s-tribromobenzene is formed together with the ethers. Solutions of the diazonium salt in methyl o r ethyl * The hydrogen snlphate mas mainly used, since there is sonie difficulty in prc- serving the nitrate ; further, the chloride cannot be easily isolated, an acid chloride being precipitated from the acetic acid solution by ether.38 ORTON, COATES, AND BURDETT: THE INFLUENCE OF alcohol differ in some respects.Whilst the solution in methyl alcohol remains unchanged in the dark, that in ethyl alcohol slowly decom- poses, but, in marked contrast to the decomposition induced by light, now only s-tribromobenzene is formed. Solutions (or suspensions) in several other media have been examined. When dissolved in 95 per cent. sulphuric acid, the phenolic decomposition takes place slowly, no other substance being produced. Solutions in fuming nitric acid appear to behave similarly, but here a secondary reaction, namely, displacement of the bromine by the nitro-group, complicates the phenomenon.Formic acid solutions yield only s-tribromobenzene, thus : C,H2Br3*N(HS0,)IN -t H*CO,H = C,H3Br3 + H,SO, + N, + CO,. I n propionic acid, the diazonium salt is insoluble ; nitrogen is evolved from the suspension, but the reaction is exceedingly slow. The diazonium salts of 2 : 4 : 5 : 6-tetrabromodiazobenzene, 2 : 6-di- bromodiazobenzene, 2 : 4 : 6-tribromo-3-nitrodiazobenzene, 3 : M i - bromo-p-diazotoluene? and 3 : 5-dibromo-o-diazotoluene, in so far as they have been studied, behave in a completely analogous manner. Aqueous solutions of benzen ediazonium salts ra.pi d 1 y clian ge when exposed t o sunlight a t 0" ; nitrogen is evolved and phenol formed, but the decomposition soon comes to ;L standstill, owing to a dark turbidity arising frcm some secondary reaction which prevents access of light.This diaculty is not met with in the case of $-cumenediazonium salts, which are, moreover, even less stable in aqueous solutions than benzenediazonium salts a t the ordinary temperature. When exposed t o light a t O", nitrogen is rapidly evolved, +-cumenol being formed, whilst if shielded from light this decomposition is very slow a t that Iow temperature. In marked contrast t o the sensitiveness of the diazonium salts is the stability of solutions of diazotates. Aqueous solutions of sodium p-nitrobenzenediamtate, 3 : 5-dibromo-p-toluenetZiazotate, and benzene- isodiazotate are unchanged after two or three days' exposure to light. A solution of potassium s-tribromobenzenediazotate in methyl alcohol is equally stable. Investigation of the effect of -variation in the concentration and nature of the acid on the decompositions of diazonium salts, which are accelerated by light, has shown that the former (concentration of the acid) has remarkably little influence on the rate of the transformation.Even up t o concentrations of 25 per cent., sulphuric acid does not diminish the speed; a t a concentration of 30 per cent., a slight decrease is perceptible, but, as mentioned in the foregoing, even solutions in 95 per cent, sulphuric acid yield phenol on exposure to light. The nature of the acid is only of consequence when the acidLIGHT ON DIAZO-REACTIONS. I. 39 radicle can itself replace the diazo-group ; in the presence of hydrogen chloride or bromide, light hastens not only the conversion into phenol, but also the replacement of the diazo-group by chlorine or bromine. The most marked effect of the presence of acids is seEn in the case of those halogendia zobenzenes which tend to undergo another decom- position, namely, the formation of a quinonediazide with the elimination of halogen.This reaction is markedly accelerated by light, and con- sequently takes place in solutions of diazonium salts exposed to light concurrently with the phenolic decomposition ; the latter, however, is always the dominant reaction. Thus i t was found that from a 1 per cent. solution of s-tribromobenzenediazonium acetate, the amount of bromine eliminated in a given time on exposure to light was three times that set free in a similar solution kept in the dark. No phenol was formed in the latter solution, whereas, in the former, 100 molecules of diazo-compound yielded phenol for every 77 which lost an atom of bromine.This acceleration of the quinonediazide reaction is still perceptible in solutions of the diazonium hydrogen sulphate. I n a 1 per cent. solution of the diazonium hydrogen sulphate, the pro- portion of molecules yielding phenol to those giving quinonediazide is 100 : 25, in a 15 per cent. solution of sulphuric acid i t has fallen to 100 : 12, whilst i n a 30 per cent. solution the elimination of bromine is no longer perceptible. The rate a t which the decomposition proceeds on exposure to light is greatly influenced by the extent to which the quinonediazide reaction is occurring, for the reason that, when exposed to light, all quinonediazides rapidly change into deeply-coloured, amorphous solids, which, remaining suspended in the solution, effectually prevent the access of light.According to the view previously explained (Orton, Trans., 1903, 83,796), the quinonediazide is the result of an interaction of diazonium {Ar*NiN)” and hydroxyl (OH)‘ ions. As the concentration of acid increases, the concentration of the hydroxyl ions becomes vanishingly small, and the formation of quinonediazide ceases. This change accompanying the replacement of the diazo-group by hydroxyl was observed to a greater or less degree in the case of all the halogendiazobenzenes. It is s-carcely detectable, if not entirely absent, in the decomposition of 5-bromodiazo-nz-xylene and 6-brcmodi- azo-$-cumene, is noticeable in that of the two 3 : 5-dibromodiazo- toluenes, and assumes still larger proportions as the number of negative bromo- and nitro-groups in the benzene nucleus is increased, until in the case of an aqueous solution of 2 : 4 : 6-tribromo-3-nitro- benzenediazonium hydrogen sulpha.te 46- 47 per cent.of one atomic proportion of bromine is eliminated.40 ORTON, COATES, AND BURDETT: THE INFLUENCE OF A suggestion as to the mechanism of the transformation of diazonium salts into phenols, which has attained considerable acceptance, was first given by Hantzsch (compare ‘‘ Diazo-Verbindungen,” Ahrens’ Sammlung), who represents the phenols as being primarily formed from the syn-diazohydroxides, thus : Ar-8 Ar HO--N -+ 4~ -k Nv by an ‘‘ intramolecular decomposition ” which is comparable to the decomposition of t,he syn-aldoximes into water and nitriles.Since solutions of the diazonium salts are particularly liable to this reaction, he accounts for the syn-diazohydroxide, which must on this view be present in such solutions, by the existence of a certain amount of hydrolysis of the diazonium salt. The free diazonium hydroxide formed in this manner has been shown (Hantzsch and Davidson, Ber., 1898, 31, 1612) to change partially into the isomeric sp,-diazohydr- oxide, so that an equilibrium exists which can be represented thus : The hydrated compound is suggested as an intermediate step. It should follow, therefore, that all conditions which favour hydro- lysis, for example, diazonium salts of weak acids or the salts of a weak diazonium base, should increase the speed of the phenolic decom- position; further, the presence of an excess of a strong acid should prevent or a t least decrease the rate of this transformation.It was shown, however, by Euler (Anncden, 1902, 325, 292) that the rate of the conversion of diazonium salts into phenols was inde- pendent of the presence of excess of acid, a t least in dilute aqueous solution. Euler maintains, therefore, that the conversion into phenol can be a purely diazonium reaction, and is not confined to sp-diazo- hydroxides. Recently (Bey., 1904, 37, 1087), Hantzsch has accepted this correction, and states that he is now of Euler’s opinion. The experiments described in this paper afford independent evidence for the view that diazonium salts in aqueous solution are directly transformed into phenols.As has been shown, the presence of a considerable excess of acid is no hindrance to the change ; under the influence of light the reaction takes place at the ordinary temperature in 30 per cent. sulphuric acid, with no decrease of speed. Moreover, it will even proceed, though but slowly, in a 95 per cent. solution of sulphuric acid; in such a medium, it is difficult to imagine even a vanishing trace of hydrolysis. Further, in the light of the experiments here recorded, there would appear to be little reason to think that the other decompositions, namely, the reaction with methyl or ethylLIGHT ON DIAZO-REACTIONS. I. 41 alcohols or with acetic acid, which lead respectively to ethers and acetic esters, are reactions of syz-diazo-compounds and not of diazonium compounds.These transformations appear to be regarded by Hantzsch (Zoc. cit., p. 6s e t seq.) as decompositions of a syn-diazo-compound. The presence of excess of acid is, in these reactions, however, not without effect, in that the product of the reaction induced by light is modified ; whereas, under all conditions yet investigated, s-tribromobenzene always accompanies the s-tribromophenyl methyl- and ethyl-ethers, the proportion of the former is increased in strongly acid solution. I n any case, the fact that excess of acid favours the replacement of the diazo-group by hydrogen affords strong evidence that this transforma- tion, a t least, is a reaction of the diazonium compound.Possibly t h g experiments which are now in progress on the accelerating influence of light on the replacement of the diazo-group by chlorine or bromine may illuininate further the mechanism of these diazo-reactions. With regard to the mechanism of the action of light, it may be suggested that the solvent becomes associated with the diazonium salt (or in dilute solutions, with the diazonium ion). Considering how freely formulz for hypothetical intermediate products in diazo-reactions have been brought forward in recent years, it is, perhaps, hazardous to attempt to represent graphically this additive product, But in any case it would seem that the quinquevalent " basic " nitrogen at,om, which is linked t o the acid radicle, cannot be directly involved, or undergo a change of valency, if the reactive compound is a diazonium , 1s derivative. Ar*Y*(HSO,) .OH*N*H From this point of view the expression, Ar*N( HSO,) not admissible, whereas the formula, , in which the fi ( H20) residual valency of the tervalent nitrogen is brought into play, is open to less objection. Such a complex may be supposed to be unstable, breaking up either under the influence of light or heat, yielding a phenol and nitrogen,% Further, it may be supposed that in the case of certain diazonium salts, such as those with several negative. substituents, s-tribromodiazobenzene and the like, this unstable com- plex may be resolved on mere heating into its constituents, water and diazonium salt, a fact which would account for the difficulty of con- verting the diazo-compound, just named, into the corresponding phenol.From the foregoing it is obvious that if such a complex exists, its formation is not materially affected by the presence of acid, The reactions of s-tribromobenzenediazonium hydrogen sulphate AP'N *( HS04) * Perhaps in solution in snlphuric acid, a complex is the sensitive #( H,S04) - - material.42 ORTOK, COATES, AND BURDETT: THE INFLUENCE OF l N Z N + 1 and &fN + I .LIGHT ON DIAZO-REACTIONS. I. 43 Solutions in methyl or ethyl (90 per cent.) alcohols or in acetic acid are equally sensitive, although, owing t o the solubility of the products of decomposition, the rapid change is only made obvious by the evolution of nitrogen when the flask containing the solution is con- nected with a nitrometer. In the case of this and similarly constituted diazonium salts, the decomposition of the aqueous solution pursues two courses, the main reaction results in the formation of s-tribromophenol, nitrogen being evolved ; a t the same time, however, bromine is eliminated in the ionic condition, and a quiiionediazide produced. The last-mentioned com- Found is itself changed by light, being transformed into a dark brown, amorphous powder.For the reasons given in the introduction, the presence of excess of acid should reduce the proportion of the subsidiary reaction whatever effect such an increase in acidity had upon the phenolic decomposition. The latter change can therefore be best followed in acid solution. On exposing a 1 per cent. solution of s-tribromobenzenediazouium hydrogen sulphate in 15 per cent.sulphuric acid to direct sunlight, a white solid which consisted of minute crystals was deposited, whereas in the absence of the acid a dark brown material separ- ated. The solid was collected, washed, and extracted with sodium carbonate, which left, in the case of the aqueous solution, a considerable quantity of brown solid undissolved. The phenol was precipitated from its solution in alkali and dissolved in dilute alcohol, from which it crystallised in long, slender needles melting a t 92' ; its melting point was unchanged by admixture with a specimen of s-tribromophenol : 0.1925 gave 0.3262 AgBr. CGH,ORr, requires Br = 72.50 per cent. Efect of the Concentration of the Xulphuric Acid o n tihe Decomposition of the Diaxoniuna Salt unde?* the Injluence of Light.-The salt appears to decompose most rapidly, as estimated by the evolution of nitrogen, in the presence of a 15-30 per cent, sulphuric acid, A t lower con- centrations, the evolution of nitrogen is slower, but the retarding influence may be due to the dark precipitate, which acts simply by preventing the light from gaining access to the liquid.At higher concentrations, the decomposition is again retarded, but the phenol is formed even in solutions in concentrated (95 per cent.) sulphuric acid. The following results will show the quantitative relation existing between the two reactions, the elimination of bromine and the phenolic decomposition, in different concentrations of sulphuric Br = 72.12. . - acid. (i) On exposing 50 C.C.of a 1 per cent. solution of the diazonium44 ORTON, COATES, AND BURDETT: THE INFLUENCE OF hydrogen sulphate for forty-eight hours (in October), 55 per cent. of the salt was decomposed, 11.8 C.C. of nitrogen were evolved, and the liquid yielded 0.0249 gram of silver bromide. Ratio of the number of molecules yielding phenol and nitrogen to the number giving quinone- diazide and bromine = 100 : 25. (ii) Two exactly similar experiments were made, using a 15 per cent. solution of sulphuric acid instead of water as solvent. ( a ) Eighty-six per cent. of the salt was decomposed, 21 C.C. of nitrogen were evolved, and the liquid yielded 0.0212 gram of silver bromide. ( b ) Sixty-six per cent. of the salt was decomposed, 16.5 C.C. of nitrogen mere evolved, and the liquid yielded 0.0176 gram of silver bromide.The ratio of the two decompositions was in each case 100 : 12. I n these experiments, the volume of the gas could only be approxi- mately measured, and, further, i t is assumed that nitrogen is formed only from the phenolic decomposition, an assumption which was shown to be justified by direct estimation (weighing) of the phenol. The un- changed diazo-compound was weighed as P-naphthol derivative, and hence the percentage of decomposed salt was obtained. Efect of Temperature on the Velocity of Becomposition.-There are great difficulties in the way of determining the velocity of a reaction which depends on the varying illumination of the sun. The difficulties are increased in the case of the phenolic decomposition of the diazonium salts by the precipitation of tribromophenol, which acts as a screen to the solute yet undecomposed. Equal amounts of two 1 per cent.solutions of the diazonium salt in 15 per cent. sulphuric acid were exposed in similar flasks attached to nitro- meters. One flask was immersed in ice and water, and the other in water at a given temperature, great care being taken that each flask was equally exposed to light. In these circumstances all irregu- larities in the illumination affected each solution equally. The progress of the decomposition was estimated by measuring the nitrogen evolved. Several experiments were made ; the following will illustrate the difference of temperature. Experiment 1.-Flask A, temperature 17", 50 per cent. of the diazonium salt was decomposed in two hours fifty minutes; flask B, temperature 2 O , 50 per cent, decomposed in four hours.Experiment 11.-Flask A , temperature 20°, 50 per cent. of the diazonium salt was decomposed in one hour forty-two minutes; flask B, temperature 2O, 50 per cent. of the diazonium salt was decom- posed in two hours twenty minutes. I n this experiment the illumination was more intense than in Experiment I. Action of Light on s-T&%omobenxenediuzotccte.-A solution of the diazotate was prepared by adding 0-25 gram of diazonium salt Attempts were made to ascertain the effect of temperature,LIGHT ON DIAZO-REACTIONS. 1. 45 dissolved in 25 C.C. of water t o 13 C.C. of a 10 per cent. solution of sodium hydroxide. The solution was exposed to sunlight on two successive days.Nitrogen was not evolved nor was bromine eliminated ; the solution, moreover, remained colourleas. Attempts to obtain s- Tribromophenol by Boiling Aqueous Solutions OJ the Diccxonium Sa Its. It has frequently been observed that substituted benzenediazonium salts do not yield phenols, or at least only in small quantities, when the aqueous solutions of their salts are boiled. I n the case of s-tribromobenzenediazonium hydrogen sulphate it has previously been shown that bromine is eliminated, and a dibromoquinonediazide formed, at least in the first instance (Orton, Trans., 1903, 83, 802) ; no s-tribromophenol was discovered. The decomposition of aqueous solutions of this salt has now been more exactly followed. Solutions varying in concentration from 1 to 10 per cent.were heated a t looo’ in an apparatus from which the air had been expelled by carbon! dioxide, so that the nitrogen evolved could be measured. Decomposi- tion was complete in two hours; from 75 to 80 per cent. of the total nitrogen was evolved, the lower number being obtained from the more concentrated solutions. No diazonium salt remained un- decomposed, but the yellow liquid contained quinonediazide, which could be extracted with chlorqform and coupled in the usual way with P-naphthol (compare Orton, Trans., 1905, 87, 104). From 58--60 per cent. of one atomic proportion of bromine was found in the solu- tion. The solid product of the reaction was a brown, amorphous powder, which contained small amounts of dibromoquinonediazide, and s-tribromobenzene.Both these could be extracted with alcohol, but the main part of the solid was insoluble in that solvent. The addition of reduced copper accelerated the evolution of nitrogen, but did not otherwise appear to affect the course of the de- composition. Since it has been noted by Heiniclien (Annalen, 1889, 253, 281) and others that the phenolic decomposition takes place more readily in fairly concentrated solutions of sulphuric acid, for example, in a solution of sulphuric acid boiling at 150°, attempts mere made to obtain s-tribromoyhenol by using 50-63 per cent. sulphuric acid as solvent. No s-tribromophenol could be obtained from the product of decomposition ; but a very little s-tribromobenzene was isolated. In the case of the 50 per cent. acid, only about 3 per cent.of one atomic proportion of bromine was eliminated, but from the 63 per cent. acid, which boils at 150°, as much as 35 per cent. was found, a difference which was probably to be attributed to the higher temperature. Tn46 ORTON, COATES, AND BURDETT: THE INFLUENCE OF all cases, the acid mother liquor was bright yellow, and contained quinonediazide. * Becomposition of the Dry Diazonium ,!?&.-The diazonium hydrogen sulphate (1 gram) was placed in a desiccator containing phosphorus pentoxide, and kept evacuated in the dark for twelve hours. On ex- posure to sunlight, the salt became discolonred, and, after a few hours, of a chocolate-coloured hue. On examination, it was found that the surface only had been affected, the dark solid was insoluble in water, and thus could be freed from the unchanged diazonium salt, It was found to contain halogen but no nitrogen; it was insoluble in alkali hydroxide, and in the usual organic solvents with the exception of glacial acetic acid, in which it could, at least partly, be dissolved.The quantity was to3 small to admit of further investigation, Acceleration of the Elimination of Bromine by Light.--The ex- periments were made with s-tri bromobenzenediazonium acetate, which undergoes the quinonediazide decomposition at a convenient rate (Orton, Zoc. cit.). A 1 per cent. solution of the diazonium hydrogen sulphate (0.25 gram) containing three equivalents of sodium acetate was exposed for five hours to the light i n a flask attached to a nitrometer. A bulky, brown solid separated, and a small amount (4.6 c.c.) of nitrogen was evolved.27.6 per cent. of one atomic proportion of bromine (AgBr= 0.0296 gram) was eliminated. The ratio of the number of molecules undergoing the phenolic decomposition to those undergoing the quinonediazide decomposition is therefore 100 : 77. An exactly similar solution kept in the dark for the same period evolved no nitrogen; the solution became yellow in colour, and a slight yellow precipitate formed. Ten per cent. of one atomic proportion of bromine ( AgBr = 0.0108 gram) was eliminated. Repetitions of the experiment gave a similar result. As was to be expected, variations in the intensity of light affected the phenolic decomposition to a greater extent thaii the quinonediazide decomposition.Decomposition of s-~ribromobenxe.lzedin,yonium II'ydrogen Sulphate in Itf ethyl Alcoholic Xolutim-The diazonium salt is readily soluble in methyl alcohol, and the solution when kept in the dark is stable ; * Dr. J. C. Gain drew the author's attention to the fact that the method of inducing the phenolic decomposition by heating the diazonium salt in a saturated solution of sodiiim sulphate was effective in converting a small proportion of s-tribromobenzenediazonium hydrogen sulphate into s-tribromophenol. An experi- ment was tried, usiug 10 grams of the diazonium salt in a solution made up of 14 C.C. of sulphuric acid and 32 C.C. of water, 18 grams of hydrated sodium sulphate being added. The mixture was distilled in a slow current of steam, the flask being heated in an oil-bath.A small quantity of s-tribromophenol (m. p. 88") mixed with another substance melting a t 75-76', which does not dissolve i n aqueous sodium carbonate, was oltained.LIGHT ON DIAZO-REACTIONS. I. 47 thus no nitrogen was given off from a 1 per cent. solution which was kept in the dark f o r twenty-eight hours (temperature 10.5'); but on exposure to sunlight for one hour 72 per cent. of the salt was decomposed. On again placing this solution in the dark, de- composition ceased. Although solutions in methyl alcohol at the ordinary temperature are stable if screened from light, decomposition rapidly occurs if the solution is boiled, s-tribromobenzene being alone produced. The main decomposition under the influence of light is accompanied by a small amount of-a secmdary reaction, namely, the elimination of bromine, and the formation of a quinonediazide. The decomposition of the latter in light causes the solution to bezome deeply coloured.The solid product of the reaction which remains in solution in the methyl alcohol was obtained by evaporating the solvent after decomposition had been completed, sodium carbonate having been added to neutralise the free sulphuric acid. The solid residue, which was highly coloured, was distilled in steam ; from the colourless solid distillate a small quantity of s-tribromophenol was extracted by sodium hydroxide. It melted a t the correct melting point, 95'. The main portion of the solid, which was insoluble in sodium hydroxide, melted a t 60-65'. It was thought that this solid was a mixture of s-tribromobenzene (m.p. 120') and s-tribromoanisole (m. p. 88'), but crystallisation from alcohol did not change the melting point.* It was therefore treated with hydriodic acid in order t o convert the ether into s-tribromophenol. Fmm the product both a-tribromobenzene and s-tribromophenol were easily isolated, no indications of the presence of a third substance being noticed. The relative proportions of these two substances were determined by estimating the methoxy-group and determining the percentage of bromine in the mixture. The two methods agreed closely, within one per cent., the mixture containing 63-61, per cent. of the ether. The methoxy-group was estimated by Zeisel's method, using a mixture of acetic anhydride and hydriodic acid to decompose the ether; two hours' heating at 160' was found necessary for complete decomposition.Efeect of the Presewe of Water or Acids.-Addition of acid or dilution of the methyl alcohol with water does not greatly change the rate of the decomposition in sunlight ; in both cases there is a slight decrease. In the presence of acid (15 per cent. H,SO,), bromine is * The solubilities of s-tribromobenzene and s-tribromoanisole are very siniilar in both methyl and ethyl alcohols. Both are moderately soluble in boiling 90 per cent, ethyl alcohol. At 15"' 100 C.C. of this alcohol dissolves 1'03 grams of the tribromo- anisole, and 0'4 gram of the tribromobenzene ; these are almost the proportions in which these two substances are found in the product of decomposition of the di- azonium salt in methyl alcoholic solution.48 ORTON, COATES, AND BURDETT: THE INFLUENCE OF not eliminited, and in consequence no colour, owing to the decom- position of quinonediazide, developed.The proportion of s-tribromobenzene and s-tribromoanisole is con- siderably modified in favour of the former, which now forms the main product of the reaction ; s-tribromobenzene separates in the pure state during the decomposition. Owing to this effect of acid, high concentrations of the diazonium hydrogen sulphate, 4 per cent. and upwards, yield mainly s-tribromobenzene on exposure to light. I n such a solution, the concentration of the sulphuric acid is initially decinormal, and as the decomposition proceeds becomes fifth - normal, Behaviour of A Zka Zidiaxo t ale in Met hp? A Icoho Z ic XoZut iolz.-T ho behaviour of methyl alcoholic solutions of sodium or potassium s-tri- bromobenzenediazotates offers st marked contrast to that of the diazonium salts.A 1 per cent, solution of potassium diazotate remained quite colourless and unchanged during four hours' exposure to light. Decomposition of s-~ribromobenxenediaxoniu~~ liydrogen SulplLate in Et?~yll AZcoltoZic 8oZution.-s-Tribromobenzenediazonium hydrogen sulphate is very sparingly soluble in ethyl alcohol at the ordinary temperature, 100 C.C. dissolving somewhat less than 0.2 gram. I n 90 per cent. alcohol, on the other hand, the salt dissolves freely. A suspension of the salt in absolute alcohol changes very slowly at the ordinary temperature when protected from the light, the amount of nitrogen evolved in twenty-four hours being only just detectable.On the other hand, the solution of the salt in 90 per cent. alcohol is unstable even in the dark; a 1 per cent. solution continuously evolves nitrogen (temperature, 11-12'>, 50 per cent. of the salt being decomposed in twenty-four hours. s-Tribromobenzene is the main product of the change, but a t the same time bromine is eliminated, representing about 10 per cent. of one atomic proportion. On exposure to sunlight, both the suspension of the salt in absolute alcohol and the solution (1 per cent.) in 90 per cent. alcohol decompose very rapidly. Whilst the 90 per cent. alcohol becomes very deeply coloured, the absolute alcohol assumes only a pale yellow tint. The solid products in the two cases do not materially differ, and consisted of s-tribromophenetole and s-tribromobenzene.Dilution of the alcohol with water retards the decomposition ; thus two similar solutions in 50 per cent. and 25 per cent. alcohol had decomposed respectively to the extent of 82 and 62 per cent. after exposure to diffused daylight for five and a half hours. I n both cases, s-tribromobenzene was the main product, a small amount of bromine being eliminated. The effect of the presence of excess of acid was tested byLIGHT ON DIAZO-REACTIONS. I. 49 exposing a 1 per cent. solution of the diazonium szlt in a 15 per cent. solution of sulphuric acid in 90 per cent. alcohol. The decomposition took place rapidly, the solution acquiring only a pale yellow tint.No bromine was eliminated, and therefore no quinonediazide formed, a result in accord with a11 previous observations as to the effect of acid on the decomposition of this diazonium salt. Co-related with the non- formation of the quinonediazide is the absence of colour. It is note- worthy that in this case also s-tribromobenzene is the only product of the reaction. The foregoing observations indicate that the most favourable conditions for the formation of the phenetole are to be found in the use of pure alcohol and the absence of acid. The preparation in quantity was accordingly carried out by exposing a suspension of the diazonium salt (4 grams) in 100 C.C. of alcohol, When all the solid had dissolved and the evolution of nitrogen had ceased, the solution mas evaporated to half its volume, whereupon pure s-tribromobenzene (m.p. 1 19-120°, 1.2 grams) separated. Since s-tribromobenzene is but slightly soluble in cold alcohol, almost the whole of this substance is thus found. The mother liquor was then evaporated to dryness and the product recrgstallised from alcohol, but such treatment failed to raise the melting point above 60-65 ', whereas s-tribromophenetole melts a t 74". Control experiments, moreover, showed that it mas difficult t o isolate from mixtures of s-tribrornobenzene and the phenetole, and then only with great loss, any pure phenetolc. The composition of the mixture was accordingly ascertained from estimations of bromine and the ethoxy group ; * both analyses agreed in showing that the mixture contained 70-72 per cent.of the ether. After treating the mixture with hydriodic acid, the resulting s-tribromophenol and s-tribromo- benzene could easily be separated by alkali. From these results it follows that the original mixture of s-tribromobenzene and s-tribromo- phenetole contained about 5.7 per cent. of the former. Decomposition of s-l'ribromobenzenediazonium Ifiidrogen Sulphate in Acetic Acid Solution.-s-Tribromobenzenediazonium hydrogen sulphate dissolves freely in glacial acelic acid (99 per cent.) ; the solution is quite stable in the dark at the ordinary temperature, but becomes coloured on boiling, s-tribromobenzene being formed. On exposing a solution (1 per cent.) t o sunlight, decomposition is rapid and complete; the addition of an equal volume of water causes.the ;y I n order to obtain an accurate estimation of the ethoxy-group in s-tribromo- yheiietole by Zeisel's method, very prolonged heating of the substance with hydr- iodic acid (1 vol.) and acetic aiiliydride (0-5 vol.) is necessary. Thus, in one deterniiiiation (s-tribromophenetole = 0.3426 grain), ethyl iodide only ceased to be given off after six hours' heating, the percentage of ethoxy-group being found = 11 '54, whilst C,H,Br,*OEt requires 12 -19 per cent. VOL. XCI. E50 ORTON, COATES, AND BURDETT: THE INFLUENCE OF separation of colourless needles which melt a t 8 2 O , the melting point of s-trihromophenyl acetate, C,H2Br;OAc. An analysis showed that this substance was quite pure : 0.2103 gave 0.3156 AgBr. Er = 64.4G. The effect of diluting the acetic acid or of adding sulphuric acid is t o decrease the rapidity of the decomposition, water having the greater influence.The solid product obtained from the dilute acetic acid consisted of a mixture of s-tribromoplienol and its acetyl derivative in about equal proportions, A small amount of phenol was also present in the product obtained from the mixture of acetic nnd sul- phuric acids. C,H,O,Br, requires Br = 64.33 per cent. Decomposition of s-Fribrornobe?~xenedic~xonium Hyclyogen XuZp?mte in Various Media. POY~ZZ'C Acid-The diazonium salt is readily soluble in formic acid (90 per cent.); in the dark, the solution was shble, no gas being evolved. On exposure to sunlight, a very rapid decomposition set in ; the solid product consisted mainly of s-tribromobenzene mixed with a small amount of s-tribromophenol ; no phenyl Eormate was discovered.Since the formic acid had acted as a reducing agent, carbon dioxide should be present in the evolved gas. Examination of the gas showed this supposition t o be correct. Propionic Acid.-The diazonium hydrogen sulphate does not per- ceptibly dissolve in propionic acid. When the suspension is exposed to sunlight nitrogen is slowly evolved, and the solution becomes coloured a deep yellow. Neither s-tribromobenzene nor s-tribromo- phenol are formed, but owing to the slowness of the decomposition sufficient material could not be accumulated to determine its identity with tribromophenyl propionate. SuZphuric Acid.-The diazonium salt is readily soluble in concen- trated sulphuric acid (95 per cent.).The colourless solution slowly evolves nitrogen in sunlight, On cautiously diluting the solution, pure s-tribromophenol crystrallises 0 1 7 t free from any trace of by- product. rli'itric Acid.-Fuming nitric acid (sp. gr. 1.5) dissolves the diazonium salt freely. The decomposition in sunlight is complicated by the concomitant decomposition of the nitric acid, and by the interaction of the acid with the primary product ,which is probably s-tribromophonol. Bromine is partly displaced by the nitro-group, and can be estimated in the solution. It was not possible to isolate a single substance from the mixture of nitrobromophenols, but picric acid appeared not to be present.LIGHT ON DIAZO-REACTIONS. I. 51 Organic Lipuids.-The diazonium salt does not dissolve to any extent in glycerol, lactic acid, butyric acid, or ethyl acetoacetate.The suspension in the two solvents first named decomposes fairly rapidly, s-tribromobenzene being formed in each case. I n the other two media, the decomposition is very slow. Decomposition of Other Substituted Biazobenxenes. 2 : 6-Dibromodiaxobenxene.-The behaviour of this diazonium hydro- gen sulphate towards light is similar to that of the s-tribroino-deriv- ative, and affords an extremely easy method of preparing 2 : 6-dibromo- phenol. In aqueous solution the decomposition is very rapid, a very small quantity of bromine (2.54 per cent. of one atomic proportion) being eliminated. The phenol was freed from a small quantity of brown solid, the decomposition product of the bromoquinonediazide, by dissolving in sodium hydroxide. The phenol melted a t 56’ and gave the following numbers on analysis : 0.147 gave 0,2186 RgBr.Br = 63.3. C,H40Br2 requires Br = 63.5 per cent. This phenol can also be prepared easily from the diazonium salt by Heinichen’s method (Zoc. cit.), using a 63 per cent, solution of sul- phuric acid. Decomposition is complete in three-quarters of an hour ; the yield is good and no appreciable amount of quinonediazide or other substance seems to be formed. 2 : 3 : 4 : 6-Tetrabromodic~xobenxe7ze.-In the decomposition of aqueous solutions of this diazonium hydrogen sulphate by sunlight, the quinonediazide decomposition takes a more prominent place, some 15 per cent. of one atomic proportion of bromine being eliminated.The tetrabromophenol which is mainly formed can be obtained in a purer state when the decomposition is effected in 15 per cent. sulphuric acid, the quinonediazide decomposition being then inconsiderable. The phenol melted a t 115’ : 0.1448 gave 0,2645 AgBr. Br = ‘77.7. When this salt was heated in 63 per cent. sulphuric acid solution, a rapid and complex decomposition took place. As much as 53.6 per cent. of one atomic proportion of bromine appears in the solution, Very small amounts of two crystalline products were noticed, but no tetrabromo2henol was isolated. 2 : 4 : 6-l’ribrorno-3-nitrodicmobelzxene.-The decomposition of this diazonium salt, which is very rapid when a a per cent. solution is exposed t o sunlight, appears t o be very complex ; 46-47 per cent.of one atomic proportion of bromine is eliminated, and the solid product C,H20Br4 requires Br = 78.01 per cent. E 252 ORTON, COATES, AND BURDETT: THE INFLUENCE OF is a mixture of the decomposition product of the quinonediazide and the phenol arising directly .from the diazonium salt. The addition of sulphuric acid reduced the proportion of the quinonediazide decom- position ; nevertheless some 17.8 per cent. of bromine was eliminated. p-n~itrodi~zobenxene.-"he existence of the remarkably stable y-nitrobenzenediazotates and the corresponding nitrosoamine has rendered possible the testing of the action of light on these classes of substances. A dilute aqueous solution of the pure sodium p-nitro- benzenediazotate was exposed to light for several days. The liquid darkened slightly, and about 2 C.C.of gas were evolved. Examination of the solution after exposure showed that the diazotate was mainly unchanged. p-NitropT~enyZnitrosou~nine (pnitrobenzenediazohydroxide), which was prepared by Schraube and Schmidt's method from sodium p-nitro- benzenediazotate, is insoluble in cold water and slowly decomposes at the ordinary temperature. In the dark a t 0' it is, however, quite stable. A suspension in water was exposed to sunlight in a flask which was immersed in ice and water, the light having access to one side of the flask. The substance rapidly darkened and nitrogen was slowly evolved, 4 C.C. being collected during two hours' exposure. Decomposition of Diaxobenaene in Light. Inasmuch as acid solutions of diazobenzene readily undergo the phenolic decomposition a t the ordinary temperature, testing of the accelerating effect of sunlight on this change was somewhat difficult, Moreover, sunlight produces other changes i n solutions of this diazonium salt, which result in causing the liquid to become dark and turbid, effects which prevent light from gaining access i o the liquid and thus stop the reaction. Two exactly similar solutions of the diazonium hydrogen sulphate were made up in 20 per cent.sulphuric acid, and placed in flasks connected with nitrometers. One was exposed to sunlight and the other placed in a dark room, each being immersed in mixtures of ice and water. The solution, which was exposed to sunlight, became dark and turbid, and nitrogen was slowly evolved.The solution in the dark did not change in appearance, but a small volume of nitrogen was evolved, at about a quarter of the rate of the solution exposed to light. The solutions, still thoroughly cold, were extracted with chloroform in order to isolate any phenol. The residues left after evaporating the chloroform were distilled in steam, and the aqueous solutions treated with bromine water. The distillate from the solution which was exposed to light gave a precipitate of s-tribromophenol (m. p. 95"), whilst that from the screened solution gave only a slight turbidity.LIGHT ON DIAZO-REACTIONS. I. 53 Similar experiments were made with a '' normal I' diazo-solution, which was made up by adding 25 C.C. of a solution of benzenediazonium chloride (from 1 gram of aniline) to 30 C.C. of a 10 per cent.solution of sodium hydroxide. This solution decomposes when kept in the dark a t the ordinary temperature, 25 C.C. of nitrogen being evolved in twentyfour hours. A similar solution, in which, however, 30 C.C. of a 30 per cent. solution of sodium hydroxide were used, instead of the 10 per cent. solution, was more stable, and decomposed very slowly in the dark; light did not appear appreciably to hasten the rate of decomposition. Decomposition of illeth~ldiaxobenxenes. 5-B~*o.rlzo-4-diaxo-m-xyZene.-TTnlike other s-trisubstituted anilines in which negative groups such as the nitro-group or bromine are present, 5-brorno-m-xylidine can be diazotised in dilute acid solution. The solid diazonium salts can be prepared very readily in the usual way.Aqueous solutions of the diazonium salts are quite stable a t the ordinary temperature, provided that they are screened from light. Thus a 1 per cent. solution of the diazonium hydrogen sulphate in 15 per cent. sulphuric acid was kept in a flask connected with a nitro- meter for seventy-three days, the temperature ranging from 10-15O during that period. No gas was evolved, but when this solution was exposed to sunlight, a rapid decomposition set in, gas being given off, and an oil separating. No bromine is eliminated and the diazonium salt can be converted quantitatively into the xylenol. This change can be brought about with equal readiness by boiling the aqueous solutions of the diazonium salts. Very different is the behaviour of solutions of the diazotates.I n the dark they are quite stable, and when exposed to sunlight only show signs of decomposition if the excess of alkali is slight and consequent,ly the hydrolysis considerable. , - 5-Byorno-m-4-x yleno I, BI-, )o M * OH This xylenol appears to have been prepared by Noelting, Braun, and Thesmar (Bey., 1901, 34, 2242) from the corresponding xylidine. These authors state that the xylenol is a solid melting a t 72'. We have, however, found that the xylenol obtained from 5-bromo- m-4-xylidine by diazotising and then decomposing the diazonium salt either by boiling or by exposing i t s aqueous solution to light, is an oil a t the ordinary temperature. Moreover, bromination of m-4-xylenol54 ORTON, COATES, AND BURDETT: THE INFLUEKCE OF also yields a monobromo-derivative which is identical with the substance obtained from the bromoxylidine.Bromifiation, of rn-Li-Xylenol.-A solution of bromine (6.55 grams) in acetic acid was added to a solution of m-4-xylenol(5 grams) in the same solvent in which fused sodium acetate (3.6 grams) was suspended. Bromination was instantaneous, heat being developed. The xylenol was separated by addition of water, and distilled in steam, and after separation from the aqueous distillate by chloroform and drying in the latter solvent, the oil was fractionated under reduced pressure. It was colourless, boiled a t 110.5" under 18 mm. pressure, and had a sp. gr. 1.4569 at 11'/4" : 0.1235 gave 0.1141 AgBr. Br = 39.89. The bromoxylenol prepared from the bromoxylidine by way of the diazo-compound, boiled at 112" under 20 mm.pressure, and had a sp. gr. 1.4607 a t 11"/4". An analysis of a specimen obtained by boiling a solution of the diazonium salt gave the following numbers : 0.1215 gave 0.1145 AgBr. A specimen obtained by exposing a solution of the diazonium salt to light gave the numbers : C,H90Br requires Br = 39.80 per cent. Br = 40.10 per cent. 0.1098 gave 0.1 018 AgBr. Br = 39.45. C8H90Br requires Br = 39.80 per cent. B-Bromo-$-cumidine (6-Bromo-5-ccmino-1 : 2 : 4-trimetl~yZbenxene).- This base has apparently hitherto not been described. It is readily prepared by brominatiog $-cumidine in acetic acid solution in the presence of sodium acetate, care being taken to add the solution of the base t o the solution of the bromine. The bromo-+-cumidine is precipitated by addition of water and purified by distilling in steam.It crystallises from dilute alcohol in long, colourless needles melting at 68-69' : 0.1906 gave 0.1675 AgBr. Br= 37.4. The salts of this base are not markedly hydrolysed by water, thus resembling those of bromoxylidine. It is very readily acetylated by heating for a short time with acetic anhydride a t 100'; the acetyl derivative crystallises in clusters of four-sided prisms melting at 206'. C,H,,NBr requires Br = 37.4 per cent.LIGHT ON DIAZO-REACTIONS. 1. 55 It can easily be diazotiscd in dilute acid solution, and the solid diazonium hydrogen sulphate can be prepared in the usual way. Acid solutions of bromo-+-diazocumene behave in exactly the same way as do those of bromodiazoxylene.Kept in the dark at the ordinary temperature they are quite stable, but on exposure to light, gas is immediately evolved, and a turbidity soon appears in the solution. Pure 6-bromocumenol (m. p. 32 -33') slowly separates in needles. Boiling of the aqueous solutions of the salts brings about a rapid and quantitative conversion into the bromocumenol. 5-Dinxo-+-cun~ene.-An attempt was made to contrast the de- composition of an acid solution of diazo-$-cumene exposed to light with one kept in the dark. A t the ordinary temperature, this diazo- compound decomposes fairly quickly, whether screened from light or not. A t 0-2', a marked difference is observed ; whilst the solution which is kept in the dark very slowly evolves nitrogen, the other decomposes rapidly. +-Cuinenol crystallised out as the decomposition proceeded, and melted a t 71". 3 : 5-Dibronao-o-dic~xotoluene, and 3 :~5-Di6rorno-p-diuxotoZuelze.-Th~ dibromodiazotoluenes resemble very closely s-tribromodiazobenzene. Solutions of the hydrogen sulphates are quite stable in the dark, but on exposure to light rapidly decompose. I n aqueous solution, a small amount of bromine is eliminated, and the 3 : 5-dibromocresol, which separates during the change, is discoloured by the products of de- composition of the quinonediazide. Quantitative experiments have shown, however, that only 10 per cent. of the diazonium salt under- goes the quinonediazicle decomposition, the remaining 90 per cent. being converted into cresol. If the decomposition is carried out in 15 per cent. sulphuric acid solution, no bromine is eliminated, and the cresol separates in almost pui e, colourless needles. The cresols can easily be isolated from the product of the action of light by distilling in steam. 3 : 5-Dibromo-o-cresol crystallised in long needles melting a t 55' : 0.13'72 gave 0.1932 AgBr. 3 : 5-Dibromo-p-cresol was obtained in needles melting a t 43-4 1" : 0.1506 gave 0 2123 AgBr. When dilute (1 pcr cent.) aqueous solutions of the sulphates are heated a t loo', rapid decomposition ensues; about 70 per cent. of the total nitrogen in the diazo-compound is given off a s gas. A dark brown, amorphous solid separated from which no cresol could be isolated; the filtrate was quite colourless and free from both un- changed diazonium compound or quinonediazide, but a trace of bromine mas present. Br = 59.93. C7H,0Br2 requires Br = 60.1 2 per cent. Br = 59.98 per cent.56 BERKELEY: ON THE MORE EXACT DETERMINATION OF The dibromodiazotoluenes differ from tribromodiazobenzene in that they readily yield the corresponding cresols when they are heated i n solution in 63 per cent. sulphuric acid. Decomposition is very rapid, and a crystalline substance distils over, which is mainly the cresol. Solutions of the sodium dibromotoluenediazotates can be easily prepared, and accordingly offer an excellent means of demonstrating the stability of these substances t o light, After three days’ exposure of the sodium derivative of dibromo-o-diazotoluene in 1 per cent. aqueous solution, the liquid was still quite colourless ; no measurable amount of gas had been evolved. The authors are indebted to the Chemical Society and to the British Association for the Grants which have largely defrayed tho cost of these researches. They wish to take this opportunity of expressing their thanks to these Societies. BANGOR. UNIVERSITY COLLEGE OF NORTH WALES,

ISSN:0368-1645    

DOI:10.1039/CT9079100035

出版商:RSC    

年代:1907

数据来源: RSC

摘要:

56 BERKELEY: ON THE MORE EXACT DETERMINATION OF V.-Oq$ the More Exact Determinfzation of the Densities of Crystals. By THE EARL OF BERKELEY. THIS communication mas read at the meeting of the British Associa- tion at Bristol in 1898. It has not hitherto been published as it was part of a somewhat lengthy research on the molecular volumes of crystals. The appearance of Messrs. Barlow and Pope's recent paper (Trans., 1906, 89, 1675) has so illuminated the subject, that it is not considered necessary to pursue the matter any further. A comparison of the several values obtained by different observers, for the density of one and the same salt, shows variations which in some cases amount to 10 per'cent. As the density is supposed to be independent of the may in which the crystals have been produced, these discordant results must be ascribed to errors of observation, - Of these errors the following seem to be the most important. (1) Errors in the operation of determining the density.(2) Errors caused by air adhering to the crystals. (3) Errors due to the hygroscopic nature of the salts. (4) Errors induced by the mother liquor occluded in the cryst'als. I n this paper I propose to describe the means whereby the amount of error due t o the first three causes have, I believe, been reduced.THE DENSITIES OF CRYSTALS. 57 ( 1) Opemtwn of Determining the Density.-Two similar conical pyknometers (Fig. l), 'of about 7 C.C. capacity, were made by Mr. Miiller from Jena thermometer glass. These are fitted with carefully ground thermometer stoppers and the thermometers are graduated in tenths of a degree such that the hundredth of a degree can be estimated.The thermometers were standardised a t Kew. The side capillaries are graduated in millimetres and were calibrated by running weighed mercury threads along the bores and reading their lengths. The capacity (7 c.c.) was chosen as being sufficiently great to keep down errors of weighing and of manipulation. capacity of the pyknometer the thicker the walls ; consequently it will take more than proportion- ately longer for the larger quantity of liquid to attain a constant temperature when in the balance case. Also a greater quantity of salt will be re- quired to keep the proportion of salt t o liquid the same, and hence the more difficult it will be t o dry and to free from adhering air.One of the pyknorneters was used throughout the weigh- ings as a counterpoise, and to obtain the most accurate results I found it essential that the surface of each pyknometer should be similarly treated ; if, for instance, the pyknometer itself had been filled with carbon tetrachloride and its surface wetted with that liquid, the surface of the counterpoise should also be wetted with the same liquid and both similarly dried before weighing. The pyknometers, after steaming for twenty minutes, were heated to 130' and cooled; this heating and cooling was repeat,ed about fifty The greater the FIG. 1. times so as to obtain, as far as possible, a constant state of molecular aggregation in the glass. It was filled with distilled water and placed in a small desiccator connected to a Sprengel pump.Vigorous boiling, which was continued for three- quarters of an hour, mas promoted by tapping the bottom of the desiccator. The pyknometer was then placed on the pan of an ordinary spring balance and the stopper inserted and pressed home, the reading of the balance index being noted so that in future the stopper could be pressed home with the same pressure ; the presumption is that with the same pressure and the same orientation of stopper to neck, the former will go home to the same extent. It is well, however, (a) The capacity of the pyknometer was then determined.58 BERKELEY: ON THE MORE EXACT DETERMINATION OF t o check this assumption by redetermining the capacity; for after much use the stopper is ground further into the neck, especially if powdered minerals have been used.After the pyknometer and its counterpoise have been wiped dry, they are placed on the pans of the balance, and when the level of the liquid in the capillary has, in consequence of evaporation round the neck, fallen below the highest graduation, the weight is determined, and at the same time the level in the capillary and the temperature of the liquid are noted; care, however, should be taken that the temperature is fairly constant. From these data the capacity of the pyknometer is calculated in the usual way, all weights being corrected for displaced air. The following are the values obtained for this capacity, reduced t o the zero mark OF the capillary : Temp. Cal'acity. 14-90" 7'15303 C.C.1 4 9 5 7-15322 ,, 14.95 7.15305 ,, 14-97 7'15293 ,, To1np. C:tlacit y. 15'27" 7.15315 C.C. 15.60 7.15208 ,, 15.52 7.15316 ,, .' 15'96 7'15311 ,, * The greatest difference between any two observations is 0.00029 C.C. and this corresponds to an error of 0.004 per cent. The mean of these numbers was taken as the capacity a t the mean temperature, and the capacity a t any other temperature was calculated from the known cubical expansion of the Jena glass. ( b ) The liquid used for determining the volume occupied by the crystals was carbon tetrachloride. It was purchased from Messrs. Kahlbaum and redistilled a t constant temperature after digesting with fused calcium chloride for several weeks. Both during the distillation and when drawing off the liquid for use, the access of moist air was prevented by means of calcium chloride tubes.The density of the carbon tetrachloride was found to be the same a t the end of a year as it was shortly after distillation. The pyknometer is 6lled with air-free carbon tetrachloride in a manner similar to that already described, and then wiped dry as in the case of water. Owing t o the high coefficient of expansion of the liquid, i t is im- portant that the pyknometer thermometer bhould register the true tem- perature of the liquid and glass. A double-walled glass case surrounding the balance case was found insufficient to secure a steady temperature, and eventually a zinc tank filled with water and placed over and round three sides of the balance, whilst the heat of the observer mas cut off on the fourth side by a glass trough filled with water, was substituted and found effectual.By this means, in about one and a half hours, These observations mere obtained after an interval of 5onie weeks.THE DENSITIES OF CRYSTALS. 59 after placing the pyknometer on the balance, the thermometer does not change by more than O.0lo in fifteen minutes. The following table gives the densities of the carbon tetrachloride used, and for comparison, those calculated from Prof, Thorpe's results (Trans., 1880, 37, 199) : Density. Temp. Self. Thorpe. 16-44' 1.60133 1.59980 16.33 1.60157 1'60003 16-17 1.60189 1.60033 15'55 1-60310 1'60155 Diff. 0.00153 0'00154 0.00156 0.00155 Density. Teinp. Self. Thorpe. 14.88" 1.60438 1.60286 14.68 1.60475 1.60324 13'94 1.60620 1.60467 Diff.0.00152 0 '001 51 0.00154 Thinking that the somewhat large differences between our values might be caused by dissolved air, I determined the density of my unboiled carbon tetrachloride with the following results : Temp. Self. Thorpe. Di K. 15.47" 1.60291 1.60171 0*00121 15.35 1 -60320 1.60195 0.00125 To show the effect of the rate of change of temperature when the pyknometers are on the balance pans, I append the following : Density. Temp. Rate of change. Self. Thorpe. Diff. 15-67' 0'04" in 20 minutes (fallii~g) 1.60274 1.60132 0'00142 14.34 0'02 ,, 10 ,, 7 , 1.60534 1~30390 0.00144 17.67 0.03 ,, 20 ,, ,> 159904 159741 0.00163 14.04 0.02 ,, 15 ,, (rising) 1.60584 1'60448 0.00136 16.92 0'02 ,, 20 ,, Y 9 1'60052 1-59887 0.00167 16-42 0.04 ,, 20 ,, $ 7 1.60144 1'59984 0'00160 (c) To determine the density of the crystals, the pyknometer, con- taining a known weight of salt, is placed in the " bulb desiccator " (shown in Fig.2), the bulb of which has previously been half-filled with carbon tetrachloride. by exhausting through A, and warming and tapping the bottom of the bulb. Tap A is then closed, and the exhaustion continued through B for a t least three-quarters of an hour, the bottom of the desiccator being vigorously tapped a t intervals so that the vapour of the liquid may penetrate among the powdered crystals and thus sweep out the air. The apparatus is then disconnected from the pump and while still vacuous is tilted so that the liquid in the bulb flows down the fine capillary, C, into the pyknometer.The pyknometer is then weighed as already detailed. The liquid is then caused to boil60 BERKELEY: ON THE MORE EXACT DETERMINATION OF The following results were obtained for the density of powdered and ignited quartz : Observed in water. - Temp. Density. 21.95" 2.6484 21 '75 2,6487 21.52 2.6487 21'48 2,6487 21 '24 2'6486 Density of Quartz. Observed in carbon tetracliloriile. r A I Density. Temp. 21-14" 2.6486 2.6486 21.07 2.6480 2.6480 20.18 2'6483 2%482 19.99 2'6485 2.6484 18-85 2.6483 2.6480 18'24 2,6489 2.6486 I n the last column, the density observed in carbon tetrachloride is corrected ti5 21' by the use of Fizeau's coefficient of ex- A pansion of quartz. The greatest diff eren'ce between any two of these is 0.0007, which corresponds to a maxi- mum error of 0.02 per cent.It was considered possible that there might be some difference in the densities of large and small fragments of the same substance. A clear specimen of barytes was selected, coarsely pow- dered, a n d t h e n s i f t e d through sieves of different mesh. The density of the fragments retained by the finest mesh, the openings of which average 0.36 by 0.33 mm., was compared with that of the fragments re- tained by the medium mesh The barytes fragments were heated to 200' and The results are as FIG. 2. )1 (0.59 by 0.54 mm.). cooled over sulphuric acid before each observation. follows : Density of Bmytes. Small fragments. Large fragments. Temp. Density. Tcmp. Density . / \ T h > * 15.76" 4'4700 * 16.46" 4'4702 * 15-96 4.4698 * 15.05 4.4707 16.67 4.4696 17.35 4'4701 16.75 4.4702 17-06 4.4697 16.07 4'4703THE DENSITIES OF CRYSTALS.61 The observations marked (*) were obtained with fragments immersed in water, the remainder in carbon tetrachloride. The greatest difference between any two observations is 0.0011, which corresponds to a maximum error of 0.025 per cent. It will be noticed that there seems to be no difference between the two sets of densities. (2) Ail- Ileld by the C?ystals.--In section (c) I have already FIG. 3. described the method whereby it was hoped that the air difficulty had been overcome. It is evident that the shape of the pyknometer lends itself to this method, for the salt, while conserving the same relative proportion of salt to liquid, can lie in a thinner stratum than in either a cylindrical or globular form of pyknometer.The ordinary method of covering the salt with the liquid and boiling in a vacuum leads to loss of salt through spirting, and also to the adhesion of small particles to the inside of the neck which prevents62 MORE EXACT DETERMINATION OF THE DENSITIES OF CRYSTALS. Tenip. Density. 16.20" 2.3320 16'14 2.3322 Tenil). Density. 16'13" 2.3314 17.00 2'3312 The maximum error is 0.04 per cent. (4) Bother Liquor in the CrPstaZs.--No general method of over- coming this source of error was found. Some substances give the same density when obtained under conditions which differ fairly widely, but others, such as potassium chloride, even when crystallised from a solution which was kept at a constant temperature and con- tinuously s tirred, give successive crops which differ markedly in their density. The greater part of this investigation was carried out a t the Christ Church Laboratory, Oxford; I am glad to have this opportunity of thanking Mr. A. Vernon Harcourt for his kind permission to use the resources of this laboratory. * A useful precaution to take is to note the rate at which the carbon tetrachloride evaporates normally (loss of weight) when on the balance ; the presence of particles in the neck will be indicated by an increase i n the rate.

ISSN:0368-1645    

DOI:10.1039/CT9079100056

出版商:RSC    

年代:1907

数据来源: RSC

摘要:

5-CHLORO-3-KETO-I : 1-DIMETHYL-A4-TETRAHY DROUENZENE. 63 VI.-Action of RedtLciiig Ayeiits o"r, 5-CIiloi.o-3-keto- I ; I -rl i?, LCJ t h y l - ~ " - t c t 7 TI Ii y d 1.0 be I 1 y e 1 z e. By ARTHUR WILLIAM CrtossLm and NORA RENOUF, Salters' Research Fellow. SOME little time since (Trans., 1905, 8'7, 14S7), the authors described the action of sodium in moist ethereal solution on 5-chloro-3-keto-1 : 1- dimethyl-A4-tetrahydrobenzene (I) and showed that the main product , I. 11. of the reaction was 3-hydroxy-1 : 1-dimethylhexahydrobenzene (11), which may be described as the limit reduction product of the chloro- ketone, The main object of the present investigation was to find reducing agents, less powerful than sodium in moist ethereal solution, which would be discriminating in their action; so that it might be possible to prepare from cliloroketodimethyltetrahydrobenzene, first, a ketodimethylletrahydrobenzene, differing from the former only in that chlorine would be replaced by hydrogen, and secondly, the corre- sponding ketodimo t hylhexahydrobenzene.Chloroketodimethyltetrahydrobenzene is readily prepared from dimethyldihydroresorcin (see page 69) by the action of phosphorus trichloride, the yield being $5 per cent. of the theoretical amount ; and as other substituted dihydroresorcins give equally good yields of the corresponding chloroketones, i t is evident that if the above- mentioned reactions could be realised, they would furnish very ready methods for preparing substituted ketotetrahydro- and ketohexahydro- benzenes, which substances, especially the former, are not easy t o obtain by the present known methods. Complete success has attended the experiments, and further work is in progress with the object of proving that the reactions are general ones.Purticular attention is being paid to the ketones (111 and IV) derivable from trimethyldihydroresorcio, on account of the great similarity in the Y 111. groupings which they contain when compared with those of camphor. The action of sodium in moist ethereal solution on chloroketo- dirnethyltetrahydrobenzene has been further investigated, and it has been proved that the addition of a small quantity of alcohol to the ether has a beneficial effect, considerably increasing the yield of hydroxydimethylhexahydrobenzene and rendering it much easier64 CROSSLEY AND RENOUF: ACTION OF REDUCING AGENTS ON to remgve the chlorine completely from the chloroketone.Further, several interesting substances have been isolated from the resinous by-product (Trans., 1905, 87, 1494) which are dicyclic in composition. Similar resins have been encountered in all the reducing actions which have been*tried, and as the constitutions of the substances derived from them have close relationship with one mother, it will be most convenient to describe first the single nucleus compounds produced in these reactions and afterwmds the dicyclic derivatives. Single Nucleus Conzpou?cds. Having found that alcohol had such a decided influence in the reaction between chloroketodimethgltetrahydrobenzene and sodium in moist ethereal solution, it was thought advisable to try the action of sodium in absolute alcoholic solution. The reaction proceeded, however, in an unexpected direction, and though giving an interesting body from quite anot'her point of view, did not further t'he object of the present inquiry.It demonstrated the fact that the chlorine atom in chloroketodimethyltetrahydrobenzene is very reactive, a fact which greatly enhances the possibilities of t h e use of this and similar chloroketones for synthetical purposes. The reaction gives rise to small quantities of hydroxydimethyl- hexahydrobenzene (11), but principally 3-l~ydroxy-5-ethoxpl : 1 - climethyl~~exctZiyclrobenxene (VI). Evidently the sodium ethoxide formed A , iNaiOEt v.------- VI. in the first stages of the reduction reacts with the chlorine atom of the chloroketone t o give the substmce rapresented by formula V, which is then further reduced to the corresponding saturated compound.The constitution of the latter is proved by analysis and by the facts that a Zeisel determination shows it to contain an ethoxy-group, and that, when treated with acetyl- or benzoyl-chlorides, it yields acetyl- or benzoyl-derivatives respectively. The next reducing agent employed was zinc dust in aqueous alcoholic solution, which, as previously shown (rrans., 1905, 87, 1497; 1906, 89, 43), readily replaces halogen by hydrogen in siturated hydroaromatic substances, but in the present instance its action is too powerful, as it gives a mixtureA of the ketones represented by formulze V I I and VIII, containing approximately 30 par cent.of the latter. However, 3-keto-1 : 1 -dirneth~2-~~-letrahydro- beizxene (VII) may be obtained quite pure by replacing zinc dust by $11, VfII.5-CHLORO-3-KETO-P : 1-DIMETHYL-A4-TETRAHYDROBENZENE. 65 zinc filings, either in the cold or on heating, or by using the zinc copper couple. It is a colourless liquid boiling a t 88.5' at 32 mm., and its ketonic nature is proved by. the fact that it gives a semi- carbnzone and an oxime. When oxidised with potassium per- inanganate in the cold, it yields as-diniethylsuccinic acid and the lactone of a-hydroxy-PP-dimethylglutaric acid : These products mere also obtained by the oxidation of chloroketo- dimethyltetrahydrobenzene (Trans., 1903, 83, 11 9) together with /3P-dimethylglutaric acid.The production of the lactone of a-hydroxy- PP-dimethylglutaric acid proves quite definitely the constitution of the ketone, although its formation cannot be expIained on the lines suggested in the case of the chloroketone. From the present instance, i t would appear that the production of this lactone must be regarded as almost certain in any oxidation where the degradation of a ring is concerned and which might reasonably be expected to yield P/3- d imet h y lgl u t a r ic acid. 3-Keto-1 : 1-dirnethyZ~~exa7Lydrobeizxene (VIII) may be produced from chloroketodimethyltetrahydrobenzene by heating it with zinc dust in glacial or dilute acetic acid solution. It is a colourless liquid boiling about 10' lower (75.5' a t 25 mm.) than the corresponding unsaturated ketone.It forms an oxime and a semicarbazone, and when oxidised with potassium permanganate gives only PP-dimethyladipic acid (IX), a fact which proves its constitution beyond doubt. One slight difference is observable in the specimens of the ketone, according as to whether glacial or dilute acetic acid is employed in their preparation. In the latter case, the ketone gives a faint colour reaction with concentrated sulphuric acid, indicating the presence of traces of ketodimethyltetrahydrobenzsne, which is not, however, produced in sufficient amount to influence the analysis of the substance, and which can be completely and easily removed by treatment with a small quantity of dilute potassium permanganate solution in the cold. The choice between dilute and glacial acetic acid would be influenced according a d to whether the solid by-product (m.p. 148', see page 82) was required for investigation, as a larger proportion of the latter substance is obtained when dilute acetic acid is employed, although the yield of ketodimethylhexahydrobenzene is not so good as when glacial acetic acid is used. VOL. XCI. F66 CROSSLEY AND RENOUF: ACTION OF REDUCING AGENTS ON Other reducing agents investigated were zinc dust in strongly alkaline solution, also zinc dust and hydrogen chloride i n alcoholic solution. I n the former case, the hydrolytic action of the potassium hydroxide overshadows the reducing action of the zinc, with the result that the only product isolated was dimethyldiliydrorosorcin (X). I n the latter case, a mixture of ketodimethyltetrnhydrobenzene and keto- dilnethylhexahydrobenzene was obtained, together with dimethyldi- hydroresorcin a.nd it,s ethyl ether (XI) (Trans., 1899, 75, 775).c H2--CO>CH cMe2<CH 2' C("H) X. XI. Here again hydrolysis must first take place, giving rise to dimethyldihydroresorcin, which is then esterified by the alcoholic hydrogen chloride. Dicyclic Compounds. The compounds of this nature met with are all derivatives of a substance formed theoretically by the removal of one hydrogen atom from each of two hexahydrobenzene rings, with consequent production of dic!clic derivatives. It has been decided to refer to this substance as dicyclohexane, and to indicate the positions of the various substitut- ing groups by adopting the following scheme of numbering : ,UH,*CH,, /CH2* ; H2, CH2Q t i)CH*CHFg: 3t 4?)CH2. \C: H2 CH 2/ CH2*CH2/ When zinc dust acts on chloroketodimethyltetrahydrobenzene in aqueous solution, there is obtaiued a mixture of ketodimethyltetra- hydrobenzene and ketodimethylhexahydrobenzene (VII and VIII), in which the former largely predominates.If this mixture of ketones is again treated several times with zinc dust, it is possible tto isolate pure ketodimethylhexahydrobenzene and a semi-solid mass from which a crystalline product has been separated, melting at 14S0, and having the composition C,,H,,02, and which is believed to be 1 : 1'-dihydroxy- 5 : 5 : 5' : 5'-tetramethyZ-A2:2'-dicyclohexene (XII). Another possibility XIT. for a substance of this composition would be that represented by formula XIII, which could be produced from chloroketodimethyltetra- hydrobenzene * by the zinc coupling two molecules together and then partially reducing the unsaturated diketone so formed.* To make the formnlce of these dicyclic compounds strictly comparable with those of the siiigle nucleus derivatives, chloroketodimethyltetrahydrobenzeiie should be writ ten CH,/ CRIe,'CH,. 'CCI, instead of as in forinula I. \CO--.CHY5-CHLORO-3-KETO-1: 1-DIMETHYL-A*-TETRAHYDROBENZENE. 67 XII1. Such a presumption is, however, a t once rendered impossible when it is remembered that the substance is not formed directly from the chloroketone but from the halogen-free mixture of ketones, obtained by the initial action of zinc dust on chloroketodimethyltetrahydro- benzene. There can be therefore no doubt in this case that the substance C16H2602 owes its origin to pinacone formation, an exactly analogous case having been observed i n the reduction of ketohexa- hydrobenzene (Trans., 1904, 85, 141 5), where considerable amounts of 1 : 1-dihydroxydicpclohexane (XIV), (ketohexamethylene pinacone) were formed.XIV. Moreover, the behaviour of dihydroxytetramethyldicyclohexene is quite in accord with that of a substance having formula XII, for i t does not give a colour reaction with concentrated sulphuric acid, nor can it be acetylated or benzoylated under the conditions employed. Further, its unsaturated nature is proved by the fact that it readily absorbs bromine with elimination of hydrogen bromide and formation of what is believed to be a tribromoanhydride, but the exact con- stitution of this compound is a t present doubtful.Also, when treated with sodium in moist ethereal solution, it absorbs four atoms of hydrogen to give 1 : l'-dihyclroxy-5 : 5 : 5' : 5'-~etrc~methyZclicyclofiexane (XV). Here again this saturated pinacone does not give a colour reaction with concentrated sulphuric acid, but it is surprising to find that it is acetylated or benzoglated very readily. No explanation of this fact can be offered on the present occasion, but i t is hoped that, as the work proceeds, other similarly constituted pinacones will be encountered, when the matter will receive further attention. It may a t first sight appear strange that zinc dust in aqueous alcohol is a reagent sufficiently strong to reduce the double bond in ket odimethyltetrahydrobenzene, giving ketodimethylhexahydrobenzene, and also strong enough to form dihydroxytetramethyldicyclohexene from ketodimethyltetrahydrobenzene, yet is not strong enough t o F 268 CROXSLEY AND RENOUF: ACTION OF REDUCING AGENTS ON reduce the dicyclohexene compound to the corresponding saturated derivative.But such is undoubtedly the case, for on boiling an aqueous alcoholic solution of dihydroxytetramethyldicgclohexene with zinc dust for twelve hours, no trace of any rednctioa having taken place could be detected and only the unsaturated dicpclohexene compo und was recovered. Moreover, the reduction of ketodimethyltetrslzydrobenzene t.0 keto- dimethylhexahydrobenzene by zinc dust in aqueous alcohol proceeds extremely slowly, and from the experiments described on page 75 it can only be concluded that, under the influence of this particular reducing agent, t.he unsaturated pinacone is more easily formed than ketodimethylhesahydro benzene.I n the preparation of hydroxydimethylhexahydrobenzene consider- able difficulty was experienced a t one t,ime (see page 70) in obtaining the product free from halogen, and on examining the resinous by- product formed under these conditions, two solid substances were separated from it melting respectively a t 178' and 173-174". The former of these has the composition C,,H,202 argd is apparently 3 : 3'-cZiketo-5 : 5 : 5' : 5'-tetmmethgl- A-I 'l'-dicyclohexene (XVI), formed XVI. by the direct coupling of 2 molecules of chloroketodimethyltetra- hydrobenzene by the sodium.It is highly coloured (yellow), gives a brick-red disemicarbazone, thus proving its diketonic nature, and is unsaturated as shown by its ready absorption of bromine. It could not be detected in the resin formed when alcohol was added t o the ether used in the reduction of chloroketodimethyltetrahydro- benzene, but much larger quantities of the second substance melting at 173-174" and also another compound melting sharply a t 2 1 2 O were isolated. The latter proved to be identical with 1 : 1'-dihydroxy- 5 : 5 : 5' : 5'-tetramethyldicycZohexane (see page 67). For a long time the substance melting a t 173-1 74" was thought to be homogeneous, as it gave on analysis numbers a.greeing with the formula C16H3002, nor mas its melting point altered by many recrystallisations, and moreover i t sublimed in needles which melted a t 171-172".Nevertheless i t was found t o be a mixture, for on acetylation it gave two diacetyl derivatives melting at 130" and 68", and on benzoylation, two dibenzoyl derivatives melting at 199" and 134". The former of the diacetyl and dibenzoyl compounds (m. p. 130' and 199") proved to be diacetyl- and dibenzoyl-1 : l'-dihydroxy-5 : 5 : 5' : 5'-tetramethyldi- cydohexane, which substance they yielded on hydrolysis,5- CHLORO-3-KETO- 1 : 1 -DIMETHY L-A4-TETRAHY DROBENZENE. 69 The above-mentioned derivatives melting a t 68’ and 134’ were separately hydrolysed with alcoholic potassium hydroxide, when they each gave a substance, C,,H,,O,, melting a t 183O, which is believed to be 3 ; 3’-dihydrozy-5 : 5 : 5’ ; 5’-tet~anwthyldkyclo?~xane (XVII).It XVII. is readily ncetylated and benzoylated, and, unlike the unsaturated 01’ saturated pinacones, gives a decided colour roaction with sulphuric acid. Its formation would be due to the further reduction of diketo- tetrsmethyldicyclohexene (XVI), although, unfortunately, sixflicient of the latter material could not be isolated to try the action of reducing agents upon it. The substance melting at 173-174e is therefore a mixture of 1 : 1’-dihydroxy-5 : 5 : 5’ : 5’-tetramethyldicyclohexane (XV) and 3 : 3’-di- hydroxy-5 : 5 : 5’ : 5’-tetramethyldicyclohexane (XVII), in the approxi- mate proportion of one part of the former to three parts of the latter, and it has been ascertained that a mixture of these substances in these proportions melts at 173-1’74’ and sublimes in needles meltinm 9 at 171-172’.It would appear, therefore, that in the reduction of chloroketo- dimethyltetrahydrobenzene with sodium in moist ethereal solution, dicyclic compounds are formed both by the process of pinncone forma- tion and by the coupling reaction of the sodium. Further, when the reduction is inefficient, there are formed 3 : 3’-diketo-5 : 5 : 5’ : 5’-tetra- rnethyl-Al’l’-dicycZohexene (XVI) and small amounts of 1 : 1’-di- hydroxy- and 3 : 3’-dihydroxy-5 : 5 : 5’ : 5’-tetrnmethyldicycZohexane ; but when the reduction is facilitated by addition of alcohol to the ether, the first of these three substances cannot be isolated, as it is further reduced to 3 : 3’-dihydroxy-5 : 5 : 5’ : 5’-tetramethyldicycZo- hexane.EX PERIMENTAL. Chloroketodimethyltetrahydrobenzene was prepared as already described (Trans., 1903, 83, 117), except that the heating with phosphorus trichloride was continued for three hours instead of two and a half hours. Moreover, after working up the product, the alkaline washings should be acidified with sulphuric acid, when a considerable amount of solid matter separates, consisting largely of unaltered dimethyldihydroresorcin, and if this is again treated with phosphorus trichloride, the yield of chloroketodirnethyltetrahydro- benzene may be increased t o 75 per cent. (instead of 66 per cent.) of the theoretical amountl. The boiling point of the ketone, after repebted distillation, is some-70 CROSSLEY AND RENOUF: ACTION OF REDUCING AGENTS ON what lower than previously stated (Zoc.cit.), namely 9 9 O at 20 mm,, and its great stability is a point worth calling attention to. On exposure to air and light, i t darkens in colour and deposits crystals of dimethyldihydroresorcin hydrochloride, but if protected from air and light i t may be kept for an almost indefinite period. A specimen which had been bottled in this way for three years was found t o be faintly yellow, and contained 1 gram of crystalline dirnethyldihydro- resorcin hydrochloride. After filtration, there remained 37 grams of a liquid, which were dissolved in ether, the ethereal solution washed with potassium hydroxide solution, then with water, dried over calcium chloride, and the ether evaporated. On distilling the residue in a vacuum, 36 grams passed over quite constantly with the above- mentioned boiling point of chloroketodimeth yltetrahydrobenzene. Reduction of CId oroketodimet~i~ltetrc6?~~dro be?izene, I.iti'th Sodium in moist Ethereal Solution. The main product obtained by this reaction is 3-hydroxy-1 : 1- dimethylhexahydrobenzene, which has already been described in det3ail (Trans., 1905, 87, 1494). Considerable difficulty mas ex- perienced at one time in obtaining this substance free from chlorine, until it mas redised that in the original preparation the ether employed had not been washed with water to remove alcohol. Further experiments have shown that, if the amounts of materials as already stated be used, with the addition of 20 C.C. of absolute alcohol to the ether, the product of the reaction is always free from halogen. Aforeover, the yield of hydroxydimethylhexahydrobenzene is thereby increased to 60 per cent.of the theoretical amount. During the preparation resinous matter is always formed, varying in amount from 25 to 30 grams from 100 grams of chloroketodimethyl- tetrahydrobenzene. The material obtained when difficulty was ex- perienced in producing hydroxydimethylhexahydrobenzene free from halogen was a thick, red jelly, which was dissolved in the smallest possible amount of light petroleum (b. p. SO-l0O0) and allowed to stand. A viscid, yellow solid gradually separated (2.3 grams from 75 grams of the jelly), which was repeatedly crystallised from methyl alcohol : 0.1078 gave 0.3076 CO, and 0.0871 H,O.3 : 3'-Diketo-5 : 5 : 5' : 5'-tetranaethyl-A1 '"-dicyclohexene, C = 77-82 ; H = 8.97. C,,H,,O, requires C = 78.04 ; H = 8.94 per cent. is readily soluble in the cold in chloroform or benzene, and crystallises5-CHLORO-3-KETO-1 : ~-DIMETHYL-A*-TETRAHYDROBENZENE. 71 from light petroleum (b. p. S0-1OO0), ethyl acetate, or methyl alcohol in deep yellow needles melting at 178'. When a solution of bromine in chloroform was added to a solution of the ketone in the same solvent and the whole slightly warmed, the bromine disappeared and hydrogen bromide was evolved. On evaporating the solvent, a white solid remained, which crystallised from absolute alcohol and melted a t 165" with evolution of gas, but the amount of material was too small t o permit of the reaction being thoroughly investigated.The disernicarbaxoTze was prepared in the usual manner and separated from the alcoholic solution as a micro-crystalline, brick-red powder melting about 273' with decomposition. On account of its insolubility in the ordinary organic solvents, it was not found possible to purify it by crystallisation, and it mas therefore analysed after being well washed with absolute alcohol : Found, N = 23.38. C,,H,,O,N, requires N = 23.33 per cent. The light petroleum solution of the original red jelly gave a second small crop of solid matter, which was white, and consisted of 1 : l'-dihydroxy-5 : 5 : 5' : 5'-tetramethyZdicyclohexane, melting a t 212", (see page 77) and of 3 : 3'-dihydroxy-5 : 5 : 5' : 5'-tetramethyldicycZo- hexane melting at 183" (see page 72).When the reduction of chloroketodimethyltetrahydrobenzene by sodium in moist ethereal solution is carried out as described on page 70, the by-product sets to a hard, transparent, reddish-yellow resin. This was dissolved in benzene, light petroleum (b. p. 40-60') added, and the whole allowed to stand, when solid matter separated, which was filtered and well washed with light petroleum. By treatment in this manner, 80 grams of resin yielded 15 grams of a white solid, from which two substances of constant melting point ( A and B) were separated by means of ;t somewhat tedious process of fractional ex- traction with ethyl acetate and repeated crystallisation from the same solvent. The smaller fraction A , weighing 2.2 grams, crystallised from ethyl acetate in oblique, square plates melting a t 212', and was proved by analysis and the preparation from it of acetyl and benzoyl derivatives, to be identical with 1 : l'-dihydroxy-5 : 5 : 5' : 5'-tetrarnethyZdicyclohexccne, described on page 77.The larger fraction, B (5-1 grams), was analysed with the following results : 0,1275 gave 0.3529 CO, and 0.1353 H,O. This substance crystallised from ethyl acetate in radiating clusters C=75.48; H= 11.79. C,,H,,O, requires C = 75.59 ; H = 11.81 per cent.72 CROSSLEY AND RENOUF: ACTION OF REDUCING AGENTS ON of transparent, leaf-like aggregates melting a t 173-174O,* nor was this melting point altered by repeated crystallisation. On account of this fact, and also because i t sublimed unchanged (m. p. 171-172') in long, silky needles, it was for a long time thought that the body was homogeneous and consisted of 3 : 3'-dihydroxy-5 : 5 : 5' : 5'-tetramethyl- dicyclohexane; but the following experiments prove that this is not the case.Action of Benxoyl Chloride on the Substance, m. p. 173--174'.-One gram of the substance was heated on the water-bath for two hours with excess of benzoyl chloride, the whole shaken with sodium hydroxide solution, extracted with ether, the ethereal solution washed with water until free from alkali, dried over calcium chloride, and the ether evaporated. The solid residue, weighing 1.6 grams, was dissolved in a large amount of absolute alcohol, when, on cooling, 0.4 gram of solid separated (filtrate = A ) melting a t 186-192", and, after a further crystallisation, a t 199'.This substance was proved by the mixed melting point method and by analysis to be identical with the dibenzoyl derivative of 1 : 1'-dihydroxy-5 : 5 : 5' : 5'-tetramethyldicycZohexane de- scribed on page 77, which latter substance (m. p. 212') it gave on hydrolysis with alcoholic potassium hydroxide. The filtrate A was evaporated, when several fractions of crystals (in all 1.0 gram) were obtained having the same melting point. These were purified by recrystallisation from ethyl alcohol : 0.1174 gave 0.3335 CO, and 0.0892 H,O. C,,H,,O, requires C = 77.92 ; H = 8.22 per cent. The dibenxoyl derivative of 3 : 3'-dihydroxy-5 : 5 : 5' : 5'-tetramethyl- dicyclohexane is readily soluble in the cold in benzene or chloro- form, moderately soluble in acetone or ethyl acetate, and crystal- lises from absolute alcohol in radiating clusters of flattened needles melting at 133-134'.When hydrolysed by boiling with alcoholic potassium hydroxide and the solution poured into water, a white solid separated which was purified by recrystallisat ion from benzene : C = 77.48 ; H = 8.44. 0.1071 gave 0-2968 CO, and 0.1121 H,O. 3 : 3'-Dihydroxy-5 : 5 : 5' : 5'-tetramethyZdicyclo?~exane, C=75.57; H=11*63. Cl,H,o02 requires C = 77.59 j H = 11 *8 1 per cent. is readily soluble in the cold in absolute alcohol or acetone, less so in * I t has since been ascertained that on standing the crystals become opaque and the melting point less sharp. A specimen melting at 173-174", when first isolated, melted after six weeks a t the same temperature, but did not become clear until 180", and two months later partially melted at 173-174", but did not clarify until 195".5-CHLORO-3-KETO-1: I-DIMETHYL-A4-TETRAHYDROBENZENE.73 ethyl acetate, crystallises From chloroform or benzene in clusters of scaly needles melting a t 183', and sublimes unchanged in fern-like aggregates of flattened needles. It does not decolorise a chloroform solution of bromine, gives with concentrated sulphuric acid a salmon- pink colour turning to deep orange, and is converted by benzoyl chloride into the above-mentioned dibenzoyl derivative melting at 133-134", and no other substance. On mixing three parts of this product with one part of 1 : 1'-dihydroxy- 5 : 5 : 5' : 5'-tetramethyldicyclohexane, that is, in the proportion which formed the constant melting mixt8ure ( 173-1 74") of these two sub- stances, the melting point was 172--173O, but complete clarification did not take place until 179'.Moreover, this mixture sublimed in silky needles melting a t 171-172" and becoming quite clear a t 176'. Action of Acetyl Chloride oy6 the Substance m. p. 173--174'.-One gram of the substance was heated with an excess of acetyl chloride for two hours, and the solvent evaporated, when the viscous residue so obtained rapidly solidified on rubbing with a few drops of alcohol. It was spread on a porous plate and crystallised from absolute alcohol, when 0.2 gram of needle-shaped crystals separated which melted a t 130°, and proved to be identical with the diacetyl derivative of 1 : l'-dihydroxy-5 : 5 : 5' : 5'-tetram6thyldicycZoh~xnne described on page 77.On addition of water to the alcoholic mother liquor, further amounts of needle-shaped crystals separated, which were purified by crystallisahion from dilute alcohol : 0.1124 gave 0,2916 GO, and 0.1060 H,O. C,oH3,0, requires C = 71.01 ; H = 10.06 per cent. The dicccetyl derivative of 3 : 3'-dihydroxy-5 : 5 : 5' : 5'-tetramethyl- dicyclohexane is extremely soluble in the ordinary organic media, and crystallises, as above stated, in clusters of slender needles melting at 68". It is readily hydrolysed by alcoholic potassium hydroxide, yielding 3 : 3'-dibydroxy-5 : 5 : 5' : 5'-tetramethyldicycZohexane melting at 183". C = 70.75 ; H= 10.47. 11. TVith Sodium in Absolute Alcoholic Solution. Twenty grams of cbloroketodimethyltetrahydrobenzene were dis- solved in 400 c .~ . of absolute alcohol in a flask attached to a reverse condenser, and 32 grams of sodium, cut in thin slices, gradually added. At the end of the reaction the whole was poured into a large volume of water, extracted three times with ether, the ethereal solution washed with water, dried over calcium chloride, the ether evaporated, and the residue distilled under diminished pressure, when the following fractions were obtained at 35 mm. : 95-135' = 4.5 grams, 135-150' = 10.7 grams, resinous residue = 1.5 grams.74 CROSSLEY AND RENOUF: ACTION OF REDUCING AGENTS ON The fraction 95-1 35' gave with sulphuric acid the marked colour reaction characteristic of 3-hydroxy-1 : 1 -dimethylhexahydrobenzene (Trans., 1905, 87,,1495), and no doubt consisted of a mixture of this substance with 3-J~ydroxy-5-ethoxy-1 : 1-dimetJ~yZJ~exahgdrobenxene (see below).The latter compound will, however, form the starting point of another investigation, and a detailed description of its properties and reactions will be reserved for a future communication. Thefi.action 135-150" was redistilled, when S grams of a colourless liquid passed over quite constantly at 135' a t 25 mm. : 0.1499 gave 0.3835 CO, and 0.1559 H,O. 3-Hy d roxy- 5 - e t J~oxy - I : 1 -dime t JL y 1 Jhexah y clr o be nxen e, C= 69.77; H = 11.55. C,,H,,O, requires C = 69-76 ; H = 11 -62 per cent. is a colourless, oily liquid boiling a t 135" at 25 mm., and possessing a faint celery-like odour. It does not solidify when cooled in a mixture of ice and hydrochloric acid, does not decolorise a soliition of bromine in chloroform, and with concentrated sulphuric acid gives only a very faint orange-pink colour.That it contains an ethoxy- group was proved by a Zeisel determination, carried out according to the directions given by Sir W. H. Perkin (Trans., 1903, 83, 1367) : 0.3445 gave 0,4397 AgI. C,H,,O*OC,H, requires -OC,H, = 26.16 per cent. The result is somewhat low, but, as pointed out by Perkin, ethoxy- determinations, as a rule, give results from 1 to 2 per cent. below the calculated. The acetyl derivative, prepared by the action of acetyl chloride, is a colourless, refractive, oily liquid boiling a t 129" a t 22 mm., and possessing a sweet, slightly camphoraceous odour : -OC,H, = 24.44. Found, C = 67.33 ; H = 10.41.C,,H,,O, requires C = 67.29 ; H = 10.28 per cent. The benxoyl derivative, obtained in the usual manner, is a faintly coloured, highly refractive liquid boiling a t 236' a t 50 mm., and having an odour somewhat resembling that of ethyl benzoate : Found, C = 73.75 ; H = S.85. CI7H,,O, requires C = 73-91 ; H = 8.69 per cent. III. FitJi Zinc Dust in Aqueous Alcoholic Solution. Two quantities of 29 grams each of chloroketodimethyltetrahydro- benzene were separately dissolved in 108 C.C. of 90 per cent. alcohol, 40 grams of zinc dust mixed with an equal volume of sand added, and the5-CHLORO-3-KETO-1 : 1 -DIMETHYL-A4-TETRAHYDROBENZENE. 7 5 whole heated on the water-bath for four to five hours. The major portion of the alcohol was then distilled off, the residue poured into water, extracted six times with ether, the ethereal solution washed with water, dried over calcium chloride, and the ether evaporated.The residue did not boil constantly (95-102" at 78 mm.), but the major portion passed over between 100-102° a t 7s mm., and was analysed with the following result : 0.1403 gave 0.3952 CO, and 0.1303 H,O. C = 76.82 ; H= 10.31. C,H,,O requires C = 77.42 ; H = 9&67 per cent. C,H,,O ,, C - 76.19 ; H = 11.11 ,, This colourless liquid, which was free from halogen, possessed a pungent, camphoraceous odour, and gave the marked colour reaction with concentrated sulphuric acid characteristic of 3-keto-1 : 1- dimethyl- A4-tetrahydrobenzene (see page 78), but the above analysis proved it to be a mixture of this substance with 3-keto-1 : l-dimethylhexahydro- benzene * (see page 81), and this is further proved by the fact that on oxidation as-dimethylsuccinic acid, the lactone of a-hydroxy-pfl- dimethylglutaric acid, and Pfl-dimethyladipic acid were obtained, and by the following experiments.Nineteen grams of the mixed ketones were dissolved in 52 C.C. of 90 per cent. alcohol, 19 grams of zinc dust and an equal volume of sand added, and the whole heated on the water-bath for ten hours. The major portion of the alcohol was distilled off, the residue poured into water and distilled in steam (residue of distillation=A). The distillate was extracted six times with ether, and the residue obtained on evaporation of the ether again heated with zinc dust in aqueous alcoholic solut,ion ; this process was repeated three times, when it mas found that the residue of the steam distillation did not furnish any further solid matter.The liquid volatile with steam (6 grams) still gave the colour reaction of the unsaturated ketone, and in order to remove these last traces it was treated with dilute potassium permanganate solution in the cold. Only a very small amount of the oxidising agent was used up and the recovered liquid, which boiled quite constantly a t 80" a t 36 mm., no longer gave a colour with sulphuric acid, and consisted of pure 3-keto-1 : I-dimethylhexahydrobenzeae (see page 81) : Found, C = 75.87 ; C,H,,O requires C = 76.19 ; H = 11.11 per cent. The semicarbazone crystallised from alcohol in radiating clusters of scaly needles melting a t 195O with decomposition and evolution of gas.* The action of zinc dust on chloroketodimetbyltetrahydrobeiizeiie iii the cold gives precisely these same results, €€ = 11 -14.76 CROSSLEY AND RENOUF: ACTION OF REDUCING AGENTS ON The residue of the steam distillation ( A ) was extracted with ether, the ethereal solution dried over calcium chloride, and the ether evaporated, when 5.7 grams of a viscid, semi-solid mass remained. This and similar material (in all 9.3 grams) from the residues of the other steam distillations were triturated with light petroIeum (b. p. 40-6O0) and, after filtering, yielded 3.9 grams of a clean, white solid, which after crystallisation from ethyl acetate gave 2.5 grams melting sharply at 148' : * 0,1092 gave 0.3077 CO, and 0.1048 H20.C,,H2,0, requires C = 76.SO ; H = 10.40 per cent. 1 : l'-Dihydrox~-5 : 5 : 5' : 5'-tetramethyl-A2 21-di~y~lohe~en~, C = 76.84 ; H = 10.66. is fairly readily soluble in the cold in chloroform, benzene, or acetone, less readily in alcohol or ethyl acetate, and crystallises from the latter solvent in stout, transparent, rhombohedral plates melting at 148O. It sublimes unchanged in microscopic, rhombohedral plates, and does not give a colour reaction with sulphuric acid, nor was it found possible to prepare acetyl or benzoyl derivatives under ordinary con- ditions. Action of Bromine.-One gram of the substance was dissolved in 15 C.C. of chloroform and a solution of bromine in the same solvent gradually added, when, without the solution becoming sppreciably warm, the bromine was rapidly absorbed and torrents of hydrogen bromide evolved.The chloroform was evaporated and the residue (2 grams) purified by crystallisation from benzene : 0.1360 gave 0.2026 CO, and 0.0560 H20. 0.1102 ,, 0.1316 AgRr. Br=50*81. The tribromoanhgdride (1) of dihg drox y tet ramethyldicyclohexene is very slightly soluble, even on boiling in alcohol, acetone, or ethyl acetate, but is sufficiently soluble to be crystallised from either benzene or chloroform, when it separates in small, glistening, flattened needles, which on heating in a capillary tube begin to darken a t 245' and melt with complete decomposition a t 250'. It only dissolves slowly when heated with fuming nitric acid, and, on cooling, faintly yellow, scaly needles separate, melting at 2 12' with decomposition, but no more definite information can be given a t the present time owing to lack of material.* There is a second product of lower inelting point present in this and also in the solid isolated from the action of zinc dust and acetic acid on chloroketodiinethyl- tetrahydrobenzene (see p. 83), but up t o the present time it has not been found possible to draw any very definite conclusions as t o the constitution of this sub- stance, though it certainly possesses the forniula C16H2602. C = 40.63 ; H = 4.57. C,,H,,OBr, requires C = 40.93 ; H = 4.47 ; Br = 5 1 *1'7 per cent.5-CHLORO-3-KETO-1 : I-DIMETHYL-A4-TETRAHYDROBENZENE. 77 Action of Sodium in moist Ethereal Xo1ution.-Two grams of dihydroxytetramethyldicyclohexene were dissolved in a mixture of 20 C.C.of alcohol and 40 C.C. of ether, the solution floated on 30 C.C. of water, and 12 grams of sodium, cut in very thin slices, gradually added. As the reaction proceeded, a white solid separated which dissolved on the addition of further small amounts of alcohol and ether. The major portion of the solvents was then evaporated, the residue poured into water, the solid which separated, filtered, washed with water, spread on plate (2.3 grams), and crystallised from ethyl acetate : 0.1077 gave 0.2985 CO, and 0.1154 H20. 1 : l’-Dihydroxy-5 : 5 ; 5‘ ; 5’-tetramet7~?/ldicyclo?~exane, C=75*58; H= 11.90. C,,H,,O, requires C = 75.59 ; H = 11.81 per cent. is but slightly soluble in chloroform or benzene, not readily so in acetone, alcohol, or ethyl acetate, and crystallises from the latter solvent in transparent, oblique, square plates melting at 212’.It sublimes unchanged in fern-like aggregates, and does not give a colour reaction with concentrated sulphuric acid. Although so readily formed by the action of sodium in moist ethereal solution on dihydroxytetra- methyldicyclohexme, no trace of it could be found on heating the iatter substance for twelve hours with zinc dust in aqueous alcoholic solution. The diacetyl derivative, prepared by the direct action OF acetyl chloride, is readily soluble in the cold in benzene, chloroform, acetone or ethyl acetate, and crystallises from alcohol in sheaves of needles or on slow crystallisation in well-formed rectangular prisms melting a t 130° : Found, C = 70.99 ; H = 10.31.C20H8404 requires C = 71.00 ; H = 10.06 per cent. The dibenxoyl derivative, prepared as described on page 72, is readily soluble in the cold in benzene or chloroform, moderately soluble on heating in aIcohol or acetone, and crystallises from ethyl acetate in transparent, four-sided plates melting a t 199’ ; Found, C = 77.82 ; H = 8-26. C,oH,,O, requires C = 77.92 ; H = 8.22 per cent. Both the diacetyl and dibenzoyl derivatives regenerate dihydroxy- tetramethyldicyclohexane (m. p. 2 12’) when hydrolysed with alcoholic potassium hydroxide.78 CROSSLEY AND RENOUF: ACTION OF REDUCING AGENTS ON IT. TrTith Zinc Filings in Aqueous AZcoT~oZic Solution. Twenty grams of chloroketodimethyltetrahydrobenzene were dis- solved in 108 c .~ . of 90 per cent. alcohol, 30 grams of zinc filings added, and the whole heated on the water-bath, during which time zinc chloride separated. The heating was continued for five hours, when the major portion of the alcohol was distilled off, the residue poured into water, the solution extracted six times with ether, the ethereal solution washed once with water, dried over calcium chloride, and the ether evaporated. The residue was again treated with zinc filings and 90 per cent. alcohol, and the whole process repeated six times, when the resulting liquid was found t o be practically free from halogen. On distilling under diminished pressure, the major portion (free from halogen) passed over quite Constantly a t 89.5' a t 30 mm., leaving a small residue which contained chlorine. This fraction was again distilled and analysed : 0.1227 gave 0.3471 CO, and 0.107s H,O.C8H,,0 requires C = 77.42 ; H = 9.67 per cent. As the yield of the ketone prepared in this manner is not very satisfactory, the reaction mas tried in the cold, when the amount formed is considerably increased, as is also the case when using the zinc-copper coup]& For this purpose 10 grams of chloroketodimethyl- tetrahydrobenzene were dissolved in 15 C.C. of 90per cent. alcohol, 10 grams of zinc-copper couple added, and the whole allowed to stand a t the ordinary temperature, when zinc chloride rapidly separated. After forty-eight hours i t was filtered (filtrate = A ) , the residue mashed with alcohol, the alcoholic solution evaporated, added to A , which was again treated with the zinc-copper couple and this process repeated four times, when the addition of fresh zinc-copper couple did not pro- duce any further separation of zinc chloride.The whole mas then poured into water and worked up as described above. On distilling the residue under diminished pressure, it passed over for the most part quite constantly, leaving but a small residue which contained chlorine, and after a second distillation it boiled a t 83.5' a t 25 mm. : C = 77-21 ; H = 10.01. C = 77.15 ; H = 9.76. 0.1183 gave 0.3349 CO, and 0.1066 H,O. C,H,,O requires C = 77.42 ; H = 9.67 per cent. As large quantities of this ketone are being prepared for another investigation, a description of the best method of obtaining it is re- served for a future communication.C H *CO 3-Keto-1 : 1-dimetl~yLA4-tetrahydrobenxene, CMe,<CH,2.CH>CH, is a colourless, highly refractive liquid, boiling a t 88.5' at 32 mm., and possessing an odour of almonds, which soon becomes disguised by a5-CHLORO-3-KETO-1 : 1-DIMETIIY L-A4-TETRAHYDROBENZENE. 79 pungent smell of camphor. When treated with a n equal bulk of con- centrated sulphuric acid it gives a blood-red colour, turning to plum- red, then gradually to violet and finally disappears, A solution of bromine in chloroform is immediately decolorised on addition of a chloroform solution of the ketone, and an attempt was made to determine the bromine absorption value, but without success, for although there is an apparent end reaction when 1 molecule of bromine has been added, yet a t t h i s point hydrogen bromide is evolved, and the amount increases rapidly with further addition of bromine.The semicurbaxone prepared by adding the ketone to a concentrated alcoholic solution of seniicarbazide acetate, crystallises from methyl alcohol in nacreous scales melting a t 195’ to a clear yellow liquid which slowly evolves gas. The preparation requires to be carried through as rapidly as possible on account of the ease with which tho semicarbazone decomposes, especially when in solution : Found, N = 23.39. Action of Nydroxylamine. -Two grams of hydroxylamine hydro- chloride were dissolved in the smallest amount of water, alcohol and 2 grams of the ketone added, the solution neutralised with sodium hydroxide and allowed to stand twelve hours.It was then poured into a saturated solution of brine, the whole extracted with ether, the ethereal solution washed with water, carefully dried over calcium chloride, and the ether distilled off. As the slightly coloured residue showed no sign of solidification on standing or on cooling, and as, unlike the oxime of the corresponding saturated ketone (see page Sl), it could not be distilled even under a low pressure without complete decomFosition, the nitrogen was determined in a specimen of the liquid prepared as above described : C9H,,0N, requires N = 23.20 per cent. Found, N = 11.15. Although the nitrogen found is not very closely in accord with the calculated amount, it is sufficiently near to show that the substance is a simple oxime and not a hydroxy lamino-oxime, which would require 16.27 per cent.of nitrogen. Moreover, .when the crude oxime was treated with benzoyl chloride, although decomposition took place resulting mainly in the formation of a dark coloured liquid, a small quantity of a solid benzoyl deriv- ative was isolated, crystallising from absolute alcohol in nacreous, scaly needles melting a t 171-172” and containing 6.10 per cent. of nitrogen, whereas the calculated amount for the benzoyl derivative of the simple oxime is 5.76 per cent. Oxidation of the Ketone.-Five grams of the ketone were suspended in 125 C.C. of water, and a cold saturated solution of potassium C,H,,ON requires N= 10.07 per cent.80 CROSSEEY AND RENOUF: ACTION OF l2EDUCING AGENTS ON permanganate added until no longer decolorised.As oxidation took place very rapidly, the solution was cooled by the addition of small quantities of ice and then worked up in the usual way, when 5.2 grams of a white solid were obtained. This was dissolved in water and the solution saturated with hydrogen chloride, when, on standing, 1 *8 grams of needle-shaped crystals separated melting a t 139-1 40°, nor was this melting point lowered on mixing with pure ns-dimethyl- succinic acid. The identity of this substance was further proved by converting a portion into the anilic acid, which crystallised from methyl alcohol in nacreous, scaly needles melting at 187' with evolution of gas. The mother liquor from the as-dimethylsuccinic acid was evaporated to dryness, i n d the solid residue (2.5 grams) heated with excess of acetyl chloride for two hours.On evaporation of the solvent, the residue solidified ra.pidly when stirred, and after frequent crystallisa- tion from benzene was obtained in stellar aggregates of transparent needles melting at 110-1 1 lo : 0.1100 gave 0,2142 CO, and 0,0654 H,O. 0.2019 required 12.85 C.C. N/lO NaOH. On heating the solution used for this titration, a further 11.5 C.C. of 8/10 NaOH were required for neutralisation. This substance is evidently, therefore, the lactone of a-hydroxy-PP-dimethylglutaric acid (compare Perkin and Thorpe, Trans., 1899, 75, 56). C = 53.10 ; I€ = 6-60. C7H,,0, requires C = 53.16 ; H = 6.33 per cent. Calculated, 12.78 C.C. C7H,,04 molecular weight calculated 158. Found, 157. V. Vith Zinc Dust in Acetic Acid Solution.Two quantities of 20 grams of chloroketodimethyltetrahydrobenzene were separately dissolved in 80 grams of glacial acetic acid contained in a flask attached to a reverse condenser and heated on a sand-bath. Thirty-three grams of zinc dust were gradually added, a t first in very small amounts as the reaction is a vigorous one. The operation takes about twenty hours, at the end of which time the whole was neutral- ised with sodium hydroxide and distilled in steam (residue = A), the distillate extracted six times with ether, the ethereal solution washed with potassium hydroxide, then with water, dried over calcium chloride, and the halogen free residue obtained on evaporation of the ether distilled under low pressure and analysed : 0.1080 gave 0.3017 CO, and 0.1090 H,O.The same substance may be obtained by using diIute instead of For this purpose, 20 grams of chloroketodimethyl- C= 76.18 ; H= 11-21. C,H,,O requires C = 76.19 ; H= 11.11 per cent. glacial acet'ic acid.5-CHLORO-3-KETO-1 : I-DIMETHYL-A*-TETRAHYDROBENZENE. 81 tetrahydrobenzene were dissolved in 48 grams of glacial acetic acid and 40 C.C. of water and treated with 33 grams of zinc dust. Towards the end of the reaction it was necessary to add small quantities of glacial acetic acid. The product was worked up as described above, when the steam distillate (residue of distillation = B ) yielded a liquid boiling a t 77.5" at 27 mm : 0.1316 gave 0.3660 CO, and 0.1319 H,O. C,HI,O requires C = 76.1 9 ; H = 11 -1 1 per cent. The only difference between this specimen of the ketone and that prepared by the action of glacial acetic acid was that the former gave a faint colour reaction indicative of the presence of the corresponding unsaturated ketone (see page 75).The amount present must have been extremely small, as it did not affect the above quoted analysis, and after treating this specimen of the ketone in the cold with dilute potassium permanganate it no longer gave the colour reaction. C- 75.86 ; H = 11.13. clear, colourless, refractive liquid boiling a t 75.50 at 25 mm. and possessing a strong camphoraceous odour. The yield when using glacial acetic acid is 50-55 per cent. of the theoretical amount, and with dilute acetic acid somewhat less. The ketone does not give a colour reaction with sulphuric acid. When dissolved in chloroform and a solution of bromine in the same solvent added, no bromine is absorbed for some little time, then the colour suddenly disappears, hydrogen bromide is evolved, and on adding more bromine it is rapidly absorbed and torrents of hydrogen bromide are given off.This seems, perhaps, an unusual behaoiour for a saturated compound, but it has been ascertained that ketohexahydrobenzene behaves in exact'ly the same way towards bromine, and the phenomenon is probably connected with the conversion of the bodies into derivatives of the aromatic series, a point which is receiving a t tention. The semicurbaxone, prepared in the usual manner, crystallises from absolute alcohol in radiating clusters of glistening, flattened needles melting at 195" with evolution of gas and much greater decomposition than the semicarbazone of the corresponding unsaturated ketone (see page 79) : Found, N = 22.72.C,HI7ON, requires N = 22.95 per cent. The oxime was prepared from 5 grams of the ketone exactly as described on page 79. It distilled quite constantly a t 132' a t 37 mm. as a clear, colourless, syrupy liquid with a sickly odour somewhat reminiscent of both camphor and celery : Found, N = 9*S3. C8H,,0N requires N = 9.93 per cent. As it did not solidify on cooling or on standing for some consider- VOL. XCI. G82 5-CHLORO-3-KETO-1 1-DIMEI'HPL-A4-TET€idHY DROBENZENE. able time, it was converted into the benaoyl derivative, which is readily soluble in the cold in the usual organic solvents, but crystallises from dilute alcohol in nacreous scales melting a t 69' : Found, N = 6-05, C,,H,,O,N requires Tu' = 5.7 1 per cent.This substance was then hydrolysed by warming with potassium hydroxide (1 : a), when suddenly the solution became quite clew, and on passing carbon dioxide through i t the oxime was prc- cipitated. I t was extracted with ether, Bc., when, on standing some time in a vacuum, it solidified completely. The solid melted a t 43-44', was extremely soluble in the cold in the usual organic media, and was proved by analysis to consist of the pure oxime. Oxidation of the Keto9zs.-Ten grams of the ketone were suspended in 250 C.C. of water and a saturated solution of potassium perman- ganate gradually added. The oxidising agent was only used up extremely slowly in the cold, and therefore the whole was heated on the water-bath, when the reaction required about forty hours for com- pletion. The product was treated in the usual way, yielding 5 grams of solid, which were dissolved in water and the solution saturated with hydrogen chloride, but even on long standing no crystals were deposited (compare Trans., 1906, 89, 1552). The solution mas evaporated, care being taken to get rid of' all the hydrogen chloride, and the residue crystallised from a mixture of chloroform and light petroleum, when 2.8 grams of radiating clusters of rhombic plates separated, melting a t 85-86", nor was this melting point lowered on mixing with pure PP-dimethyladipic acid : 0.1193 gave 0.2411 CO, and 0.08'79 H20. C,H1,O, requires C = 55.17 ; H = S.04 per cent. On evaporating the mother liquor from the dimethyladipic acid, there remained a solid residue, which was dissolved in water and the solution saturated with hydrogen chloride, but on standing only a few minute crystals separated. These were filtered and hydrogen chloride allowed to escape from the solution, when compact crystals formed, consisting of pure PP-dimethyladipic acid, thus proving that only minute traces of the isomeric aa-dimethyladipic acid could have been produced during the oxidation. The residue from the steam distillation A (see page 80) was acidified with acetic acid, extracted with ether, the ethereal solution washed with potassium hydroxide solution, then with water, dried over calcium chloride, and the ether evaporated, when a residue of 9.2 grams remained which partially solidified. This was triturated with light petroleum (40-60°), yielding 3 grams of solid, from which on crystallisation from ethyl acetate there were obtained 2 grams of pure 1 : 1'-dihydroxy-5 : 5 : 5' : 5'-tetramethyl-A2:2'-dicycZohexene (see C=55*12; H=S*18.THE VISCOSITY OF LIQUln MIXTURES. 83 page 76). The residue from the steam distillation B (see page 80) was treated in a similar manner, except that the trituration with light petroleum was unnecessary, when it yielded 1.4 grams of 1 : 1'-di- hydroxy-5 : 5 : 5' : 5'-tetramethyl- A2'2-dicyclohexene. Both the above solid residues from A and B contained rz large pro- portion of the low melting solid referred to in the footnote on page 76. The authors take this opportunity of expressing their thanks to the Research Fund Committee of the Chemical Society for a grant which has, in part, defrayed the expenses of this investigation. RESEARCH LABORATORY, PHARMACEUTICAL SOCIETY, 17, BLOOMSBURY SQUARE, W.C.

ISSN:0368-1645    

DOI:10.1039/CT9079100063

出版商:RSC    

年代:1907

数据来源: RSC

摘要:

THE VISCOSITY OF LIQUID MIXTURES. 83 VII.-- The Viscosity o,f Liquid Mixtures. By ALBERT ERNEST D UNSTAN and ROBERT WrLLrAnr WILSON. IN the two previous parts of this series, the viscosity conceutration curves of various liquid mixtures have been investigated, and it has been shown that these curves could be divided into three classes : (i) Those approximately obeying the law of mixtures, being concave to the axis of percentage composition, and having the greatest di- vergence from normal a t some point of simple molecular concentration. (ii) Those exhibiting definite maxima a t points corresponding with mixtures of simple molecular composition. Nearly all experimental work in this class has been done with aqueous solutions, and a great volume of evidence points to the conclusion that in such mixtures the formation of hydrates is always existent, producing groups of complexes in dynamic equilibrium even when definite compounds cannot actually be isolated.(iii) Those exhibiting minima which also are to be found at points of simple molecular composition. I n general, these liquid pairs which are made up of unimolecular non-associating components give viscosity concentration curves which, although frequently near the normal, yet sonietimes diverge consider- ably from it. I n the present communication, a brief account is given of certain empirical relationships which hold good for these viscosity concentra- tion curves (Zeit. physikal. Chem., 1906, 56, 370), and further u 254 DUNSTAN ANT, WILSON : experimental results in the shape of a curve for mixtures of water and sulphuric acid are adduced.It has been laid down in previous papers that increase in the viscosity coefficients implied increase in the masses of the colliding dipping particles whether they be simple molecules or loosely held complexes. Whereas, on the one hand, carbon disulphide, ether, the paraffins and other simple unimolecular liquids are mobile, the alcohols and acids are more viscous, glycol and glycerol notably so, whilst the comparatively enormous molecular massea of the jellies and colloids attain an almost infinite viscosity. A decrease in viscosity similarly may imply a decrease in complexity or the disintegration of the molecular groupings in solution, and this phenomenon is sometimes observed even when a more viscous com- pound is added to one of less viscosity.The experimental data in this work have been obtained in the same manner as in previous papers. The sulphuric acid was kindly supplied in considerable quantity by Dr. Messel, to whom we are glad of this opportunity of expressing our gratitude. The two specimens of this acid which we obtained were of special purity. The strength was determined by titration of the diluted acid, by conversion into barium sulphate, and from the density, using Pickering’s tables (Trans., 1890, 57, 64). Analysis of the first specimen : ‘1 By density .. . ,. . . . . By titration. .. . . . . . , ,, Gravimetrically . . . H2S0, = 09.57 ,, H,SO, = 99.5 per cent. H,SO, = 99.2 The second specimen gave as average of density determinations : H,SO, = 99.924 per cent.The water used was redistilled from alkaline permanganate and kept in well-stoppered Jena flasks. A large stock of 50 per cent. acid was made, and this served fo;. the middle determinations by addition either of water or acid. The strengths of the solutions were deter- mined mainly by Pickering’s tables of density ; frequent checks were made by titration and also by gravimetric analysis. The following table gives the percentage composition of the solutions, the density and the viscosity coefficients. These data are plotted on the accompanying curve (Fig. 1) :H2SO4 per cent. 99924 97 -513 95.723 93'410 92.300 91 -363 90-437 80.575 88.733 88.001 86.865 86.979 85.070 84.970 84-280 83.980 83'401 82.580 82.210 81 -544 110 100 90 80 70 j, u *$ 60 .'2.s 2 50 u u 40 4 30 20 10 THE VISCOSITY OF LIQUID MIXTURES. Density. 1'82714 1.83171 1'82986 1-823-18 1.81930 1'81476 1 '80982 1 -80525 1.799% 1 *79522 1.78650 1*78737 1.77160 1.77074 1 ,76447 1 T6069 1.75588 1.74750 1'74384 1'7371 9 Viscosity. 1 *06160 0 -8 57 61 0,83255 0.84211 0-85088 0.87158 Orn88508 0.951 32 0-91558 0 *9256S 0.93366 0.93527 0'94794 0.92966 0,92529 0 *9 1010 0 *go866 0'89842 0 *86 57 1 0.83108 FIG. 1. h2504 per cent. 81.086 80'243 79.838 79'528 78.242 76.271 74'746 70.519 69'205 67,209 64'643 58.356 51.640 49,858 43284 36'427 26.492 15.699 0 Density. 1.73197 1 '71844 1 *714 84 1 * i O O Y O 1.67756 1'65976 1'61049 1 *59488 1.57236 1 *54331 1'47457 1 '4 0596 1.38857 1 *32691 1,36759 1.18630 1.10413 0.99717 1.72287 85 Viscosity.0.78099 0.60272 0'74084 0.67228 057396 0.53603 0.40095 0'36450 032322 0.28042 0.20568 0'15370 0 '14706 0.11293 0.09239 0*07119 0.05851 0-00891 0w52 Percentuge H,SO,.86 DUNSTAN AND WILSON : In a useful summary of work done on the question of the molecular constitution of solutions of sulphuric acid, Burt (Trans., 1904, 85, 1351) points out that the conclusion that combination takes place in such solutions with the formation of complexes had been arrived a t mainly by cryoscopic methods. Pickering (Trans., 1890, 57, 64, 331), in his classical investigation on this subject, brings forward indisputable evidence as to the exist- ence of such complexes, an existence which in the case of some he proves by their actual isolation. With respect to density determina- tions, Pickering quotes Bfendel6eff’s experimental curves (Zeit.physikal. Chem., 1887, 1, 275 ; see also Crompton, Trans., 1888, 53, 116) in which after differentiation the following hydrates were deduced : H,SO,,H,O, H2S0,,2H20, H2S04,6H20, H2S0,,1 5OH,O. Pickering’s own curve after a similar process afforded seventeen straight lines equivalent to a complex first curve of seventeen parabolic components, which the author considered as the density curve of seventeen hydrates in solution. From the contractions on mixing, similar discontinuous sections identical with the above were found. H e investigated Kohlrausch’s conductivity curves, which gave five hydrates, and obtained the same results. Jones (J. Amer. Chem. Soc., 1894, 16, l), by investigating the lower- ing of the freezing point of acetic acid by sulphuric acid, claimed to have proved the existence of H,SO,,H,O and H2S0,,2H20 in solution.That the former hydrate is capable of existence and isolation is no longer doubted. Pictet (Compt. rend., 1894, 119, 642) obtained, by the crposcopic method, maximum and minimum points corresponding with H2S0,,H20, H2S0,,2H,0, and others. Ramsay and Shields (Trans., 1894,65, 179) found that the constant boiling liquid 1 2H2S0,,H20 had an abnormally high molecular weight and concluded that complexes had been formed. Graham’s work (PM. Ikans., 1846, A , 513 ; 1861, 373) on solutions of sulphuric acid and water brought out quite clearly the maximum at 85.1 per cent. of the acid corresponding with H2S04,H20; the remainder of the curve on both sides of this point is quite normal.Burt’s own conclusions (Zoc. cit.) drawn from his results on the vapour pressures of sulphuric acid solutions are of great interest ; he points out that : (1) The molecular weights calculated from the vapour pressures never rise above 32.7. (2) The molecular weights usually lie below 32.7, increase with temperature, and decrease with greater concentration. (3) Inversion points are of frequent occurrence in the curves ofTHE VISCOSITY OF LIQUID MIXTURES. 87 molecular weight x temperature. H e concludes t h a t complexes are formed, but finds no evidence for the existence of definite hydrates. Knietsch (Be?.., 1901, 34, 4069) made a n elaborate investigation of these mixtures, using not only determinations of viscosity, but also of the melting points, conductivities, and surface tensions.From the melting-point curve, he deduced the existence of H,SO,,H,O, and H,SO,,SO, at maxima, and OF BR,S0,,H20, 4H,SO,,SO,, and H2S0,,2S0, at minima. From the conductivity numbers, he found discontinuities at points corresponding with H2SO4,H20, and 2H,S0,,H20, and at 15 per cent. free SO,. The viscosity data show that the effect of adding sulphuric acid to water in gradually increasing amount is to cause a n equally gradual increase in the viscosity. The first maximum point is attained at 85 per cent., that is, the “monohydrate,” but i t is to be noticed that the increase in the viscosity is by no means commensurate with the simple addition of H,O to H,SO, or of H2S0, to H,O. So far as can be seen from the previous work on aqueous solutions, these maxima would more probably correspond t o aggregates such a s (H,SO,,H,O),,, where ‘‘ n ” may be of considerable magnitude.As will be noticed in the sequel, a very rough approximation for the addition of CH, in an homologous series is 0.001 unit of viscosity. Thus toluene to xylene, methyl to ethyl iodide, hexane t o heptane, ethyl bromide to propyl bromide give such increments. Larger increments are found in the alcohol and acid series, but in the case we are considering, the minimum point viscosity is O.OS3255, an3 the maximum point 10 per cent. from it is 0.094794, whilst water is 0.00891. From this maximum, further addition of water reduces the viscosity to rz minimum which is located at about 95 per cent.; after this point the viscosity again steadily increases through H,SO, until the second maximum at 50 per cent.free SO, (Knietsch, Zoc. cit.), both maxima corresponding with the two maxima of density. It will be noticed that in the appended curve there is a minimum point at 95 per cent. corresponding with 3H2S0,,H20. A similar minimum point was obtained with mixtures of benzaldehyde and alcohol and with benzene and alcohol. Such a point can be inter- preted as being the final result of the fission of sulphuric acid complexes by the water, the fission being complete when the water reaches the above concentration. The addition of more water causes more complex formation until this culminates in the building up of the monohydrate, which, at any rate in solution, may be the first anhydride of ortho- sulphuric acid.The position of this well-known compound is clearly indicated at 85 per cent. No further well-marked discontinuity occurs, at any rate, of the same order as the maximum already qucjtecl.88 DUNSTAN AND WILSON : Possibly more delicate apparatus would indicate such complexes of the ‘‘ second order.” The position of sulphuric acid and its “ monohydrate ” on the viscosity-molecular weight curves (v.s.) indicates the high degree of association it possesses. It will be readily seen from what has gone before that little obedience to the mixture law can be expected from two components like sulphuric acid and water, alcohol and benzene, or, in brief, wherever we deal with associated substances, and it is because of this reciprocal action of one on the other that all attempts to investigate these effects have failed.The formula given by Lees (Phil. Mag., 1901, [vi], 1, 12S), q n = ~ ~ q ~ ) t + w.,q2n, where “n” is a constant for the liquid pair, 7, qL, and y2 the viscosity coefficients for the mixture, and the two components respectively, and v102 the relative volume of the two components, fits in most closely with observed facts; at the same time it should be noticed thnt this can scarcely be described as a mixture law which has to be qualified in each case. Several regularities have been met with in the course of this investigation, especially in connexion with unimolecular liquids. A. Connexion between Moleculur WeigJLt and Angle between Tcmgent to Cuwe and Axis of Viscosity. I n any of the previously given curves (Trans., 1904, 85, 81 7 ; 1905, 87, 11) let tangents be drawn at the point where the curve meets the viscosity axis. Let a be the angle between the tangent and the viscosity axis.Then a is connected with the molecular weight of the liquid in question, as follows : TABLE I. Solution in benzene. Mol. wt. a. Product. Carbon tctraciiloride.154 52 7.9 Toluene .............. 92 93 8.55 Ethyl acetate ........ 88 94 8.27 Carbon disulphide ... 76 105 7.98 Ethyl ether ............ i4 102 7-55 Solution in alcohol. Mol. wt. a. Product. Carbon disulphide. 76 128 9-73 Mercaptan ......... 62 148 9.17 Acetone ............... 58 100 5 . 8 Eenzene ........... 78 48 3,72 Benzaldehyde ...... 106 62 6.57 It is to bo noticed that the last three alcoholic solutions give abnormal experimental results, in t h a t minima or exceptionally sbgged curves are shown.If such behaviour indicates dissociation, then the associated benzalde- hyde and benzene having a greater molecular mass than normal would, as shown in the sequel, give a steeper curve and a smaller angle a. I n all cases examined, the viscosity concentration curves are parabolic, and can be fairly represented by x = ay2 + by + c,THE VISCOSITY OF LIQUID MIXTURES. 89 dx therefore __- = Ky + iW, d?r hence a relation exists between the tangent of a and y, that is, the viscosity coefficient, or, as is shown here, between a and molecular weight. B. Connexion between iwolecular Weight and Viscosity, The following table (Dunstan, Zeit.phylsikal. Chent., 1905, 51, 738) further shows the close connexion between molecular weight and viscosity, and also illnstrates the great abnormality of the hydroxyl- ated liquids (see Thorpe and Rodger, I‘M. Trccns., 1897, 185, A , 397) : Liquid. v1M.V. x lo6. Benzene .................... 65 Ethyl acetate ............ 60 Ethyl iodide ............. 69 Ethyl bromide ............ 51 Chloroform ............... 67 Acetone .................... 43 Liquid. 7/M.V. x lo6. Watcr .................... 493 Methyl alcohol ......... 138 Ethyl ,, ......... 189 Propyl ,, ......... 262 Ally1 ,, ......... 180 1 Glycol .................... 2750 Benzaldehgde ............ 14 3 Acetic acid .............. 195 ~ Lactic ,, .............. 5410 A further relationship may be deduccd from the viscosity concentra- tion curves given in previous communications (Zoc.cit.). Taking again tangents to these curves a t the vertical axes and calling the angles between the curve and tangent “ b ” and “ c ” respectively, then the following statement holds good. The product of the molecular weight of each liquid with the angle ‘ ‘ c ” or “ 6 ” is constant, for the effect of liquid A on liquid B is measured by the angle “ b ” and vice uersb, the effect of B on A is measured by the angle ‘‘ c ’’ : Liquid A . Ethyl mercaptan . , . , , . Toluene ................ Carboii disnlphiJe.. .... Ethyl ether ............ Carbon disulpltide.. ... Ethyl acetate.. .......... - 62 92 76 i 4 76 88 - TABLE 11. -__ Ethyl alcohol ......... 46 13 Beiizene ............... 78 2 Methyl iodide .........142 4 Benzene ............... 78 15 Benzene ............... 78 3 Benzc-ne .............. 78 1290 DUNSTAN AND WILSON : C . Relation between MoZecuZu~ Teight aizd t'iscosity of Series of Compounds. A n important connexion between these quantities is evidenced when they are plotted as in Fig. 2, log. viscosity against nioleculsr weight. It mill be seen that the various menibe1.s of a chemical series lie on the same curve. The viscosity-molecular weight curves are parabolic. The FIG. 2. 60 so 100 120 140 160 simple esters lie closely together, and there is a similar proximity between the symmetrical and asymmetrical ketones. Chloroform is placed near the paraffins. The paraEns investigated by Thorpe and Rodger lie almost on a straight line; other available determinations show a considerable want of agreement with these and with themselves, It is to be noticed that the first members of each series diverge more or less from the logarithmic line and behave as though they had aTHE VISCOSITY OF LIQUID MIXTURES.91 larger molecular weight than normal (see also, for this association of the early members of homologous series, Ramsay and Shields, Trans., 1893,53, 1101). Benzene also occupies an anomalous position, giving evidence of considerable association (nearly 110 mol. wt.). Fig. 3 shows the logarithmic curves for the acids and alcohols. The two curves are very similar and indicate the same inconsistent be- haviour of the earliest members; from the points given by water and formic acid the curves follow almost parallel to each other. A con- FIG. 3. so0 600 400 200 sideration of these curves will show that water behaves as a liquid of molecular weight nearly 50, that is, (H20)3, and formic acid nearly 100, that is, (H*CO,H),, assuming that the other members are normal. Hence we may deduce the general law : where y is the molecular weight, A and B are constants depending on the particular series to which the liquid belongs, and y is the viscosity coefficient . It will be noticed that B, which measures the slope of the curves, is almost the same in the various series, and has therefore a general nature, A being the specific constant for each family. The authors desire to thank Prof. Trouton for his interest in this y = A + B log. r], investigation. EAST HAM TECIINICAL COLLEGE. UNIVERSITY COLLEGE.

ISSN:0368-1645    

DOI:10.1039/CT9079100083

出版商:RSC    

年代:1907

数据来源: RSC

摘要:

92 JOWETT AND PPMAN : RELATION BETWEEN CHEMICAL VII1.-Relation between Chemical Coristitution arm? Physiological Action in the Tnyeines. By HOOPER ALBERT DICKINSON JOWETT and FRANK LEE PY~IAN. IN a previous communication (Trans., 1906, 89, 357) it was shown by one of us, in conjunction with Mr. Hann, as the result of the physiological examination of a number of new tropeines : (1) That the peculiar difference in physiological action between a lactone and its corresponding hydroxy-acid, as exemplified by pilo- carpine and pilocarpic acid, also occurs in the case of a tropeine having a haptophore group similar to that in pilocarpine, namely, terebyl- tropeine, and also in the case of phthalidecarboxyltropeine. (2) That Ladenburg's generalisation, so far as it refers to the necessity for a mydriatic tropeine to contain a benzene nucleus, does not strictly hold since terebyltropeine possesses a distinct mydriatic action.I n order further to elucidate these two points the following tropeine was prepared and physiologically examined : ? /\.GO-- \/'CH(OH)*CH*CO*C,H,,ON I I ' Lactone of o - Cnrboxyphen ylglgceryltropeine. If Ladenburg's generalisation is valid, namely, that a tropeine to possess mydriatic properties must contain an acyl group attached to a benzene nucleus, and an aliphatic hydroxyl in the side-chain containing the carboxyl group, and if the observation that a lactone is much more active physiologically than the corresponding hydroxy-acid applies also in this instance, then the above tropeine should be a very powerful mydriatic, for it fulfils the requirements of Ladenburg's generalisation and is also a lactone.Its corresponding hydroxy-acid would contain two hydroxyl groups in the side-chain bearing the carboxyl, and the lactone of such a compound might naturally be expected to prove very active physiologically. It was found that this tropeine, on heating, readily lost the elements of water, forming isocozcma~.incurbox?/ltr~peilze, /\.co--- ? - /).CO-? \/*CH I t (OH)-CH-CO-C,H,,ON -+ (/CH: C*CO*C,H,,ON ' in a manner similar to the conversion of the lactone of o-carboxy- phenylglyceric acid into isocoumarincarboxylic acid (Bamberger and Kitschelt, Ber., 1892, 25, 896).CONSTITUTION AND PHYSIOLOGICAL ACTION IN THE TROPEINES. 93 This lactone was examined physiologically, and it was also thought to be of interest t o prepare and examine physiologically certain alkyl bromides of these tropeines, as well as those of homatropine.The necessary physiological experiments were conducted in the Wellcome Physiological Research Laboratories by Mr. C. T. Symons, to whom we wish to tender our best t*hanks, and he reports as follows : No effect was observed on instillation of aqueous solutions into the conjunctival sac, but a certain degree of mydriasis mas produced by intramuscular injection ; in this respect, therefore, they mere very much weaker than homatropine or atropine. Experiments were also made t o determine their action on the vagus nerve-endings in the heart, and in this respect also they proved t o be much less active than atropine.With regard to their action as lactones it mas found that, similarly to pilocarpine (compare Marshall, J. Yhysiol., 1904, 31, 153), they lost their action on the vagus nerve-endings in the heart after a molecular proportion of alkali had been added to the base, this change of activity being undoubtedly due to the conversion of the lactone into i t s corresponding hydroxy-acid. With regard to the alkyl derivatives of these tropeines, it was found that distinct differences in activity exist between the hydrobromides on the one hand and their corresponding methobromides on the ot,her. As has teen observed before with other alkaloids, so here, the introduc- tion of a methyl group, forming a quaternary nitrogen base, very much diminishes the action of the substance on nerve centres, and induces a more curare-like action on the motor nerve-endings in voluntary muscle. This is particularly noticeable in a comparison between the hydrobromide and the methobromide of the lactone of o-carboxyphenylglyceryltropeine, and also appears in a less pronounced degree in the case of isocoumarincarboxyltropeine. The alkyl salts of hornatropine were compared with homatropine hydrobromide as regards the mydriatic action produced on instillation OF 0.5 per cent.solutions into the conjunctival sac, and it was found that the pupils of cats’ eyes were dilated more completely and more quickly by the methobromide and methonitrate than by the hydro- bromide, but only very slightly by the ethobromide. The results of this investigation confirm and amplify the conclusions previously arrived a t (Zoc.cit.), and prove that Ladenburg’s generalisa- tion cannot be maintained, since it does not hold good in the case of terebyltropeine, which is mydriatic although not conforming to the generalisation, nor in the case of the lactone of o-carboxyphenyl- glyceryltropeine, which should according to the theory be very active, but does not prove t o be so. The tropeines were slightly mydriatic.94 JOWETT AND P’S’IVIAN : RELATION RETWEEN CHEhIICAL On the other hand, the difference in activity between the lactone and its corresponding hydroxy-acid, first noticed in the case of pilocarpine and pilocarpic acid by Marshall (Zoc. cit.), is shown in all the tropeines examined, and i t seems hardly open to question but that this difference possesses important physiological significance, and further inquiry into the reason of this difference should throw considerable light on the mode of action of these substances. E x P E R I M E N T A L.Lactone of o-Car6oxyphenyZglyceryZtropeine, /\*CO--? ‘0 CH(OH)*~H*CO*C,H,,ON This base was prepared by passing hydrogen chloride through a solution of tropeine neutralised with the lactone of o-carbosyphenyl- glyceric acid, and maintained a t a temperature of 120-125’ for two to three hours (Tauber, D.R.-P. 95853). The resulting dark brown gum was decomposed by ammonia, and the base, which separated in grey crystals, was purified by recrystallisation from absolute alcohol and obtained in rosettes of stout, acicular, colourless crystals which melted a t 172-173’.The base is insoluble in water and moderately soluble in alcohol : 0.2522 gave 0.6029 CO, and 0-1463 H20. C,,H,,O,N requires C = 65.2 ; H = 6.4 per cent. The hydrochloride separated from its aqueous solution, on evapora- tion i n a vacuum over sulphuric acid, as a viscid oil which gradually solidified, forming dense rosettes OF fine, acicular crystals. After recrystallisation from absolute alcohol, it was obtained in imperfect crystals, which melted a t 228-229’ and decoinposed a t 235’. This salt is anhydrous and is very easily soluble in water, but moderately so in absolute alcohol : C = 65.2 ; H = 6.4. 0.12 gave 0.0487 AgCI. C,sH,,O,N,HC1 requires C1= 9.6 per cent. The hydrobyomide separated from absolute alcohol in rosettes of fine, acicular crystals which melted a t 212-213’ ; it is very easily soluble in water and moderately so in absolute alcohol.,The air- dried salt contained 1 molecule of water of crystallisation, which was not entirely lost after five hours’ heating at 150’, and at a higher temperature the substance decomposed : C1= 10.0. 0.2078 air-dried salt gave 0.0906 AgBr. Br = lS.6. 0.1196 ,, ,, ,, ,, 0.0518 AgBr. Br=18.4. ClsH,lO,N,HBr,HzO requires Br = 18.6 per cent.CONSTLTUTION AND PHYSIOLOGICAL ACTION IN THE TROPEINES. 95 The hydriodide crystallised from absolute alcohol in microscopic prisms which melted at 204-205'; it is anhydrous and is very easily soluble in water, but sparingly so in absolute alcohol : 0.1812 gave 0.0916 AgI. 1=27*3. 'l'he nilrate crystallised from absolute alcohol in long, fine needles This salt is anhydrous and is very ClsH2105N,HI requires I = 27.6 per cent.which melted a t 174-175'. easily soluble in water and moderately so in alcohol : 0.0732 gave 0.1470 CO, and 0.0384 H,O. C,,H,,O,N,HNO, requires c! = 54.8 ; H = 5.6 per cent. When this salt is heated for some time a t 130' it decomposes, turning brown and losing water, and the decomposition product yields on recry stallisation from alcohol the nitrate of isocoumarin- cuboxyltropeine melting a t 238'. . 'l'he auricldoride separated from boiling water in stellate clusters of yellow needles which melted at 215-216"; it is anhydrous and is niodemtely soluble in boiling water, sparingly so in alcohol : C = 5 4 4 ; H=5.8. 0.3366 gave 0 0991 Au. C,,H,,O,N,HAuCl, requires Au = 29.1 per cent.Tht) platinicldoride separated from boiling dilute hydrochloric acid in groups of stout, yellow needles which melted and decomposed a t 193-1944 The air-dried salt contains 2 molecules of water of crystallisation which are only expelled a t a temperature of 150'; the anhydrous salt is redder than the hydrated salt : Au = 29.4. 0.2026 air-dried' salt lost 0.0063 H,O. 0.1448 ,, ,, ,, gave 0,0254 Pt. Pt = 17.5. 0.2902 ,, ,, ,, +, 0.0509 Pt. Pt = 17.5. H,O=3*1. (C,,H,,0,N),,MBPtC1,,2H,0 requires H,O = 3.3 ; Pt = 17.6 per cent. The picrate crystallised from hot water in short, yellow needles which melted at 218-220'. The methobroinide was prepared by adding excess of methyl bromide to a solution of the base in absolute alcohol at 0', and allowing to stand for one hour, when it Reparated in small needles.After crystallisation from absolute alcohol it melted a t 257-258' ; this salt is readily soluble i n water and very sparingly so in absolute alcohol : C,,H,,0,N,CH3Br requires Br = 18.8 per cent. 0.17 gave 0.0756 AgEr. Br= 18.9. isoCoumarincarboxyltropeine, 1 .v CIJ : C COO C,H,,ON This base mas prepared by heating the lactone of o-carboxyphenyl- glyceryltropeine to 120-1 25' until no further diminution in weight96 JOWE'lT -4ND PYMAN : RELATION BETWEEN CHEMICAL took place. The product was somewhat discoloured, and mas purified by repeated crystallisation from absolute alcohol ; the pure base formed colourless, glistening leaflets melting at 179-180°, which are only sparingly soluble in water, ether, and cold alcohol : 0*1804 gave 0.4561 CO, and 0.1025 H20.C=69*0; H=6*3. 0.2100 ,, 0.5315 CO, ,, 0.1185 H,O. C -69.0 ; Hs6.3. Cl,HI,O,N requires C = 69.0 ; H = 6.1 per cent. The Itydrocldoricle sepzrnted from its solution in absolute alcohol in tufts of slender needles ; it melted and decomposed a t 287--38S0, and is easily soluble in water, but sparingly so in boiling absolute alcohol. 0.2204 gave 0.0910 AgC1. C1= 10.2. C18H,90,N,HCI requires C1= 10.1 per cent. The hydrobromide, which separated from its solution in absolute alcohol in long, fine, matted needles, melted and decomposed at 252-2533; this salt is 'easily soluble in water and moderately so in absolute alcohol, and contains one-half a molecular proportion of water of crystallisation : The salt is anhydrous : 0.2811, dried a t looo, lost 0.0071 H,O at 120'.0.1016 ,, ,, 120°, gave 0.0494 AgBr. Br = 20.7. H,O=2*5. (Cl,H,,0,N,HBr)2,H,0 requires H,O = 2.2 per cent. C,,H,,O,N,HBr requires Br = 20.3 per cent. The hydq-iodide formed glistening scales which melted at 280-2W ; it is sparingly soluble in water and absolute alcohol, and contains one molecule of water of crystallisation : 0,3616 air-dried salt lost 0.0139 H,O a t 150". 0.2264 dried a t 150" gave 0*1208 AgI. H20=3%. I = 28.8. Cl,H,,04N,HI,H,0 requires H,O = 3.9 per cent. c!l, H15)04N,H1 9 , I = 28.8. The nityate was precipitated as a flocculent mass of glistening needles on adding dilute nitric acid to the solution of the base in absolute alcohol; the salt melted and decomposed at 228--229O, and is readily soluble in water and sparingly so in absolute alcohol, but insoluble in ether.It contains one half a molecular proportion of water of crystallisation, and after drying at looo : 0.4677 lost 0.0111 H,O a t 120". 0.1759 gave 0.3626 CO, and 0.0908 H20. (C,,H,,07N,),,H,0 requires H20 = 2.3 ; C = 56-1 ; H = 5.5 per cent. The aurichloyide was obtained as a yellow, crystalline precipitate ; on recrystallisation from absolute alcohol it separated in imperfect crystals which melted and decomposed at; 254-256O; the salt is H,O=2*4. C = 56-2 ; H = 5.7. 0.2015 ,, 0.4125 CO, ,, 0.1012 H,O. C=55*8; H=5*6.CONSTITUTION AND PHYSIOJ OG ICAL ACTION IN THE TROPEINES. 97 almost insoluble in water and very sparingly soluble in boiling absolute alcohol ; it is anhydrous : 0.1096 gave 0.0334 Au.C,,H,,O,N,H AuCI, requires AU = 30.2 per cent. The pkatinichloride separated as a flocculent, amorphous precipitate. It was recrystallised from dilute hrdrochloric acid and melted and decomposed at 264-265". The salt is almost insoluble in water and alcohol, and contains 1 molecule of water of crystallisation, which is lost at 120° : AU = 30.5. 0.1802 lost 0.0031 H20. H,O = 1.7. 0.1771, dried a t 120°, gave 0.0329 Pt. Pt = 18.6. (C,,H,,04N)2,H2PtC16,H,0 requires H,O = 1 *7 per cent. (C,,13,,0,N),,H2PtC1, requires Pt = 18.8 per cent, Tho picrate crystallised from strong alcohol in matted, yellow needles, which turned brown at 240°, and melted and decomposed at 2 6 5 O . The methobromide was prepared in the same way as the lactone of o-carboxyphenylglyceryltropeine methobromide. It separated from absolute alcohol, in which it is sparingly soluble, in matted needles ; it is readily soluble in water : 0.1168 gave 0.0542 ApBr. Br = 19.7.Ci8H1904N,CH3Br requires Br = 19.6 per cent. Honzatropine &thobromide, C,,H,,O,N,C,H,Br. This salt was prepared by heating homatropine with excess of ethyl bromide in a sealed glass tube at 100' for one hour, and mas purified by crystallisation from absolute alcohol ; it melted at 209-210°, and is readily soluble in water and moderately so in absolute alcohol, but insoluble in ether ; it is anhydrous : 0.2138 gave 0.1028 AgBr. Br = 20-5. C,,H2,03N,C,H,Br requires Br = 20.8 per cent. Homatropine methobromide, C,,H210,N,CH3Br, has already been prepared by Merck (D.R.-Y.145996), who gives the melting point 180-1819 On repeated recrystallisation from absolute alcohol, we have been able t o obtain the salt in a state of greater purity. The pure salt melts at 192-196", is very readily soluble in water, and moderately so in absolute alcohol; it is anhydrous : 0.2614 gave 0.1296 AgBr. Br=21.1. Cl,H2,O,N,CH3Br requires Br = 21.6 per cent. Honta t rop ine Method'phate, (Cl6H 2 1 OSN ) 23 ( CH3)2S04. This salt was prepared by heatiag an alcoholic solution of homatro- pine with dimethyl sulphate in a sealed glass tube st 100' for two VOL. XCL. H98 BENTLEY AND WEIZMANN : hours. On concentrating the alcoholic solution in a vacuous desic- cator over sulphuric acid, a syrup was obtained from which a small quantity of crystals separated.After recrystallisation from absolute alcohol, the salt melted at 172-1'74"; it is readily soluble in water and moderately so in absolute alcohol : S= 4.9. !C,gH2,0,N),,(CH~),S0, requires S = 4.7 per cent. Hornatropine Methowitrate, C,,H,,0,N,CH3*N0,. This salt mas prepared by the action of silver nitrate on an aqueous solution of homatropine methobromide. The silver bromide was removed by filtration, and the filtrate evaporated in a vacuum, first on the water-bath, then in a desiccator over sulphuric acid. It separated as a viscid oil, which gradually solidified, and after crystallisation from absolute alcohol melted a t 134-135' : 0.1582 gave 0.0563 BaSO,. 0,1875 gave 0.3963 CO, and 0.1 183 H,O. C = 57.6 ; I3 = 7.0. C,,H2,0,N,CH;NO, requires C = 57.9 ; H = 6.9 per cent. Tropine Methonitrate. This was obtained in an attempt to prepare hornatropine metho- nitrate by heating together homatropine and methyl nitrate in methyl alcoholic solution for two hours in a sealed tube a t 100'. The clear solution was evaporated in a vacuum over sulphuric acid, and gave a viscid oil from which a small quantity of crystals separated. These crystallised from absolute alcohol i n large, transparent cubes which began to turn brown at 280°, but did not melt at 300" : 0,2198 gave 0.3982 CO, and 0.1632 H,O. C = 49.4 ; H = 8.3. C8H,,0N,CH,*K03 requires C = 49.5 ; K = S.3 per cent, THE WELLCOYE ~IIEhfICAL WOKKS, DARTFORD, KEST.

ISSN:0368-1645    

DOI:10.1039/CT9079100092

出版商:RSC    

年代:1907

数据来源: RSC

摘要:

98 BENTLEY AND WEIZMANN : IX, -4- Hy d?-oxypht ha1 ic and 4 -Metkoxypk. tlmlic Acids. By \vILLIAlI HENRY BENTLEY and C'HAHLES WEIZMA". -IN connexion with some experiments which we have conducted on derivatives of naphthacenequinone and rhodamines, we had occasion to prepare considerable quantities of 4-hydroxyphthalic acid which was first investigated by Baeyer (Bey., 1877, lo, 1079), who prepared it from 4-aminophthalic acid. According to Baeyer, the acid is obtained quite pure by dissolving the sublimed anhydride in water and allow- ing to crystallise; he gives 180" (about) as the rnelt(ing point of the pure acid and 165-166' for the anhydride.4-HI'DROXYPHTHALIC AND 4-ME'J'HOXYPHTHALIC ACIDS. 99 Graebe (Ber., 1885, 18, 11 30)' who prepared 4-hydroxyphthalic acid by fusing 4-sulphophthalic acid with caustic soda, found 180-183" for the melting point of the acid, and his analysis shows more carbon and hydrogen than corresponds to hydroxyphthalic acid, indicating at once that the material was not pure, whereas Baeyer's analytical data for the acid on the contrary give no such indication.I n order to prepare 4-hy droxyphthalic acid, we fused snlphophthalic acid with caustic soda (Graebe, loc. cit. ; Rke, Annulen, 1886, 233, 232), and greatly to our surprise obtained an acid having all the properties ascribed to 4-hydroxyphthalic acid and giving good figures on analysis, but melting a t 204-205' and yielding an anhydride melting a t 171-173°. In several subsequent experiments we obtained an acid melting a t about 1 SOo, which,, after repeated crystallisations from water, melted a t 186-187" ; the mother liquors, however, on concentration yielded the acid melting a t 204-205".The acid melting a t 186-187" had also the properties ascribed to 4-hydroxyphthalic acid, but analysis, as well as the fact that its anhydride melted indefinitely between 150' and 170' even after being twice crystallised, proced i t to be impure. As we considered the subject of considerable importance we endeavoured to discover $he nature of the impurity in the acid malting at 186-187', and with this object prepared the imide, and, and dimethyl ester from each acid. These derivatives from the acid of higher melting point (204-205") mere easily obtained pure, but from the other acid (m. p. 186-1 87") repeated crystallisation was always necessary, and, finally, the derivatives obtained from each acid mere found to be identical.Moreover, the dimethyl ester from the acid of lower melting point yielded, on hydrolysis with alcoholic potash, the acid melting at the higher temperature. For some time we were unable t o discover the nature of the impurity in the acid melting a t 186-187", but when we endeavoured to prepare pure 4-methoxy- phthalic acid from each acid the results were so strikingly different that the impurity in the former was soon ascertained. 4-Nethoxy- phthalic acid, prepared from hydroxy-acid of higher melting point, was found to melt at about 170° with the formation of the anhydride melting a t 98-99O (Schall, .Bey., 1879, 12, 829, gives 138-144" and 93' respectively).When similar experiments were made with the acid of lower melting point, the product first melted at about 140' (see Schall, Zoc. cit.), and on crystallising from water yielded an acid melting at 108-109°, which on analysis gave numbers agreeing with methoxy- benzoic acid, and which yielded m-hydroxybenzoic acid (M. p. 209') on fusion with caustic potash. The impurity therefore in the acid in question and probably in samples of crude 4-hydroxyphthalic acid obtained by previous investigators is nz-hydroxybenzoic acid. Sub- H 2100 BENTLEY AND WEIZMANN : sequent experiments showed that when the fusion of 4-eulphophthalic acid with alkalis is prolonged or the temperature is too high, m-hydroxy- benzoic acid is always produced, and the crude 4-hpdroxyphthalic acid then always melts at about 180".When, however, the fusion is care- fully conducted, the formation of nz-hydroxybenzoic acid is avoided, and the 4-hydroxyphthalic acid obtained always melts directly at about ZOO". Graebe and Rke (Zoc. cit.) pointed out that m-hydroxybenzoic acid is sometimes found mixed with tho hydroxyphthalic acid produced by their fusion of sulphophthalic acid, but the material which they considered to be pure 4-hydroxyphthalic acid must have still contained m-hydroxybenzoic acid. EXPERIMENTAL. Xu Zpho nation of Ph tha Zic A nh y dy ide. I n a sealed tube or in the autoclave, phthalic anhydride is almost quantitatively sulphonated by heating with fuming sulphuric acid to 200O. I n our experiments me employed a copper autoclave in which a porcelain pot, containing a mixture of phthalic anhydride (300 grams) and fuming (73 per cent.SO,) sulphuric acid (500 grams), was placed. The autoclave was closed and heated to 200" for two to three hours; after cooling, the product, which consisted of a viscid syrup, was poured into water and neutralised with milk of lime. The soluble calcium salt mas extracted with hot water and converted into the sodium salt, the solution of which was then evaporated until crystullisation commenced. 4-Hydroxypht?~aZic Acid.-As soon as the sodium salt of sulpho- phthalic acid commenced to crystallise i t was transferred to a large nickel vessel or to the autoclave, carefully mixed with powdered caustic soda (1200 grams) and heated to 175-180O for three hours. The fused mass was then poured into a large dish, diluted with water, and acidified with hydrochloric acid.When the product contained m-hydroxybenzoic acid, this separated at once as a white precipitate while the liquid was hot, and the filtrate, on cooling, deposited a portion of the 4-hydroxyphthalic acid. After separating the latter, the liquid was extracted with ether, when a further portion of 4-hydroxyphthalicacid was obtained. The whole of the acid was then purified by crystallising from water, when, if the fusion had been conducted properly, it was obtained in warty masses melting at 204-205". If tha treatment with caustic soda had been too severe, the acid which separated after crystallibing from water was found to melt at about 180°, but by evaporating the mother liquors further quantities of 4-hydroxyphthalic acid were obtained almost pure and melting a t about 200".4-HYDROXYPHTHALTC AND 4-METHOXYPHTHALIC ACIDS.101 4-Hydroxyphthalic acid is sparingly soluble in cold water, easily so in the hot solvent; it dissolves readily in acetone, alcohol, or ether, but is almost insoluble in benzene or light petroleum. It melts at 204-205" with elimination of water and formation of the anhydride : 0.1410 gave 0.2714 CO, and 0.0427 H,O. 4Hyd~oxyphtiulic Anhydride.-The foregoing acid was fused and the beating continued until d l effervescence had ceased. On crystalli- sation from glacial acetic acid, the anhydride separated in ill-defined needles melting a t 171-173" : C = 52.49 ; H = 3-36. C8H,0, requires C = 52.7 ; H = 3.3 per cent.0.1237 gave 0.2644 and 0.0281 H,O. C8H1,0, requires C = 58.5 ; H = 2.4 per cent. It is almost insoluble in cold w$er but readily soluble in the hot solvent, and the solution on cooling deposits the free acid. It dissolves readily in alcohol or acetone ; in boiling toluene it is only sparingly soluble. 4-Hydroxyphthuli~~ide.--'l'his was prepared by heating the anhydride in a stream of dry ammonia and crystallising the product from alcohol. It separates in prismatic needles melting a t 290" [RBe gives C = 58.3 ; H= 2.5. 288-289' (~oc. ,it.)] : 0.3213 gave 24.5 C.C. nitrogen a t 20' and 756 mm. C,H50,N requires N = 8.6 per cent. 4-Hydroxyphthalimide is soluble in boiling acetone, but only very sparingly so in boiling toluene. 4-Hyd~oxypht~cc~unilic Acid, C0,H*C,H,(OH)*cO*NH*c6H~-This acid was prepared by dissolving 4-hydroxy phthalic anhydride (5.5 grams) in acetone and adding aniline (3.1 grams).The mixture became warm and, after evaporating the acetone, the residue was ground to a powder and extracted with cold aqueous sodium carbonate. From the filtered solution the aniiic mid was precipitated by the addition of acetic acid, and purified by crystallising from alcohol; it separates in pale yellow leaves : N = S.7. 0.1840 gave 9.1 C.C. nitrogen at 17' and 756 mm. Cl4Hl1O,N requires N = 5.4 per cent. The substance dissolves in cold aqueous sodium carbonate with a pale yellow colour which disappears when the solution is boiled. This is due to hydrolysis of the anilic acid, since the latter is not precipitated from the solution on acidifying with acetic acid.The anilic acid appears to melt at about 2G0°, but it is converted into the anil a t a much lower temperature, and the melting point observed is really that of the latter. 4-Hydroxyp~thaZc6niZ, C,H,(OH)(CO),:N*C6H5.-This substance was prepared by heating the anilic acid until it melted and then crystallising N = 5.7.102 BENTLEY AND WEIZMANN : the residue from alcohol, from which the a d was obtained in yellow leaves melting a t 263-264O : 0.2432 gave 12.2 C.C. nit,rogen a t 15" and 764 mm. C,,H,O,N requires N = 5.8 per cent. It is almost insoluble in cold sodium carhonate solution, but dissolves with hydrolysis on boiling. It dissolves in cold dilute caustic soda, giving a yellow solution which yields the anilic acid.This can be precipitated with acetic acid and is apparently identical with the anilic acid just described. When dissolved in an excess of cold aqueous caustic soda the anil is completely hydrolysed, the yellow colour of the solution disappearing a t the same time. Methyl 4- Hgd7*oxyphthalate, C6H3( OH) (CO,Me),. - 4 -Hy drox y ph t halic acid is esterified very readily when treated with methyl alcohol and sulphuric acid. The acid (30 grams) was dissolved in methyl alcohol (150 c.c.), mixed with concentrated sulphuric acid (100 c.c.), and warmed on the water-bath for a few hours. The cold product was poured into ice-cold water, the oil which separated extracted with ether, and the ethereal extract washed with a little sodium carbonate solution, dried, and evaporated.An oil remained which soon solidified, and after leaving in contact with porous porcelain until dry and crystallising from toluene, the methyl ester was obtained pure in minute plates melting at 107-108" [Rde, (Zoc. cit.), gives 102O]. The same substance was obtained from crude 4-hydroxyphthalic acid (m. p. 186-187'), but required s&ersl crystallisations before it was pure. On hydrolysis with alcoholic potash i t then yielded 4-hydroxyphtbalic acid melting a t once at 204-205' (see p. 100) : N=5.9. 0.1 934 gave 0,4022 CO, and 0.0844 H,O. C1,H1,O, requires C: = 57.1 ; H = 4.7 per cent. Methyl 4-hydroxyphthalate is readily soluble in alcohol or ether, sparingly so in cold water, but more easily in the hot solvent o r toluene ; it dissolves readily in cold aqueous sodium carbonate, from which solution it can be extracted by ether.Owing to this property, a further quantity of the dimethyl ester was obtained when the extract, obtained by shaking the ethereal solution with sodium carbonate (see above), was acidified. Methyl 4-Metl~oxyphtha2te, C6H3( OMe)( CO,Me),.-Pure 4-hydroxy - phthnlic lacid (50 grams) was dissolved in aqueous caustic soda, and dimethyl sulphate (200 grams) added in small portions a t a time, the mixture being constantly shaken and kept alkaline. At the end of the operation the product was heated for a short time on the water-bath, cooled, acidified, and extracted with ether. The ethereal solution was dried, evaporated, and the residue dissolved in methyl alcohol (250 c.c.), mixed with concentrated sulphuric acid C = 56 7 ; H = 4.8.4-HYDROXYPHTEIALIC AND 4-METHOXYPHTHALIC ACIDS. 103 (160 c.c.), and heated a few hours on the water-bath.The cold product was then poured into ice-cold water, the oil which separated extracted with ether, the ethereal solution washed with dilute caustic soda, dried, and evaporated, when an oil remained which was pur;L%ed by distillation under reduced pressure. Methyl 4-methoxgpl~thaZate is an oil which distils a t 195-197"/20 mm. and does not solidify a t - 10" : 0.1466 gave 0,3144 CO, and nJ37i2 H,O. C=58*5 ; H=5.4. c~,H,*,o, requi-ies C = 58.9 ; H = 5.3 per cent. 4-Jfet?~oxgphtitaZic Acid, C,H,(OMe)(CO,H),.-This acid was prepared horn the foregoing ester by hydrolysis with alcoholic potash on the water-bath ; after diluting with water and evaporating until the alcohol had been removed, the solution was acidified with hydro- chloric acid, when the aJid was precipitated.It was collected and purified by recrystallisirlg from water, from which i t was obtained in glistening needles : 0.1110 gave 0.2253 CO, and 0.0411 H,O. 4-nfethox~pl~thaZic acid is readily soluble in alcohol, acetone, or ether. When rapidly heated i t melts a t about 178" with effervescence. Slowly heated, it melts a t about 170". As stated in the introduction, when we attempted to prepare 4-methoxyphthalic acid from the crude 4-hydroxjphthalic acid (m. p. lS6-187") we obtained first zn acid melting a t about 140° with effervescence, which on recrystallising from water melted a t 108--10V', and proved on examination to be m-methoxybenzoic mid : 0.1 137 gave 0.2620 CO, and 0.0533 H,O.C8H803 requires C = 63.1 ; H = 5.3 per cent. 4-~Methoxyp?~t?~aZic Anhydride, C,H,( ONe)( CO),O.-This substance was prepared by heating the corresponding acid until it melted, and crystallising tho product from glacial acetic acid, from which it separ- ated in glistening leaflets melting a t 98-99' [Schall (Bey., 1879, 12, 829) gives 93'1 : C=54*9; H=4*1. C,H,C, requires C = 55.1 ; H = 4.1 per cent. C = 62.8 ; H = 5.2. 0.1 182 gave 0,2625 CO, and 0,0363 H20. C,H,O, requires C = 60.7 ; H = 3.4 per cent. It is readily soluble in alcohol, acetane or warm benzene ; in cold water it is almost insoluble, bat melts in boiling water and gradually passes into solution, from which the freJ acid separates on cooling.4-iClethoxgpl~t?~cdinzide, C,H,(OMe)(CO),NH.-This imide was ob- tained by heating the anhydride in a stream of dry ammonia gas and crystallising the product from alcohol, when i t separates in prismatic plates melting at 224-225" : C = 60.6 ; H = 3.4.104 BENTLEY, ROBINSON, AND WEJZMANN : ~-HYDROXYYHTHALIC 0.1711 gave 11-8 C.C. nitrogen a t 16" and 764 mm. C,H70,N requires N = 7.9 per cent Tf, is soluble in acetone, sparingly soluble in Cold toluene, but more 4 - Methoab,l .' q,lUniJic Acid, C,H,(OMe)(CO,H)CO*NH*CGH,.-In 08. reaulAe derivative, the anhydride (10 grams) W a s dis- order t o prepare c_ -1 mixed with aniline (4.7 grams). The solved in warm benzene temperature of the mixture rose ray.,, s- and the unilic acid suddenly separated as a white, amorphous powder, which, frf+dA buxbb;;,,g by the aid of the pump and washing with benzene, was quite pure and melted at 148-149" with effervescence : the boiling solvent. 0.2727 gave 13.2 C.C. nitrogen at 17" and 764 mm. It is readily soluble in alcohol or acetone and separates from dilute alcohol in leaflets, 4-Methox~~l,,tl~alaniZ, C,H,(O~le)(CO),:N~C,H,.-This was prepared by heating the anilic acid a t its melting point u r t i l effervescence had ceased. On crystallising the residue from alcohol, the anil separated in colourless needles melting at 1 7 9 O : N=5*2. C,,H,,O,N requires N == 5.2. 0.2928 gave 13.S C.C. nitrogen at 17" and 764 mm. C,,H,,O,N requires N = 5.5 per cent. 4-MetJ~ox?/;u?~tl~aZaniZ dissolves in hot dilute aqueous caustic soda, from which solution acetic acid precipitates an anilic acid, This, when purified by dissolving iii sodium carbonate and reprecipitating with acetic acid, melts at 148-149", and is probably identical with the anilic acid described above. N=5.5. THE UNIVERSITY, MANCHEWER.

ISSN:0368-1645    

DOI:10.1039/CT9079100098

出版商:RSC    

年代:1907

数据来源: RSC

摘要:

104 BENTLEY, ROBINSON, AND WEJZMANN : 3-HYDROXYYHTHALIC X. By WILLIAM HENRY BENTLEY, RONA ROBINSON, and CHARLES WEIZMANN. DURING the course of some experiments connected with the synthesis of m-hemipinic acid, it became necessary to prepare 3-methoxyphthalic acid. This acid hnd previously been prepared by Jacobsen (Ber., 1S8, 18, 1965) hy the cxidation of 6-methoxy-2-toluic acid with alkaline permangsnate, but as 1 : 5-dihydroxynaphthalene is now comparatively easy to obtain in large quantities, it was consideredAND 3-METHOXYPHTHA LIC ACIDS AND THEIR DERIVATIVES. 105 that a simpler method of preparation of this acid would be the oxidation of the mono- or di-methyl ether of this substance : Me0 Me0 ONe /\A /\A /\CO,H . I l l o r I I I - + {)C02H \/'\/ OMe \/\/ O H Considerable quantities of 3-methoxyphthnlic acid and its anhydride were prepared in this manner, but the melting points of these substances were found to differ so widely from those given by Jacobsen (Zoc.cit.) that i t was thought desirable to reinvestigate the whole subject and prepare some derivatives for the purpose of future identification. The results of this investigation, coupled with the fact that Jacobsen published no analytical data in his paper (Zoc. cit.), lead to the presumption that Jacobsen must have been dealing with impure materials, unless, indeed, the errors respecting the melting points are simply clerical. I n order to prepare 1 : 5-dihydroxynaphthaIene, naphthalene was sulphonated in the cold with fuming sulphuric acid, and the sodium salt of the disulphonic acid was fused with caustic soda at 300'.The 1 : 5dihydroxynaphthalene obtained in this way melted at 2 6 5 O , which is a little higher than the melting point given in the literature. 1 : 5-Dihydroxynaphthalone is readily rnethylated by means of dimethyl sulphate and caustic soda, and yields the mono- and di-methyl ethers, which are easily separated owing to the solubility of the mono- methyl ether in aqueous c:iustic soda. The dimethyl ether melts a t 183--184", and, on nitration in acetic acid solution, yields a mono- nitro-derivative melting a t 165-1 66' and a dinitro-derivative melting at 270". The monomethyl ether melts a t 140' and yields, on oxidation with permanganate in cold alkaline solution, three substances, namely (1) an acid of the empirical formula Cl1H,O, melting with decomposition above ZOO', (2) methoxyphthnlonic acid melting at 190-19 lo, (3) 3-rnethoxyphthslic acid melting a t 173-174" (Jacobsen gives 160") with formation of the anhydride.3-Methoxyphthalic anhydride (but not the free acid) is also obtained by the oxidation of methoxy- phthalonic acid in dilute sulphuric acid solution with cold per- manganate, the anhydride separating as a white precipitate during the operation. This anhydride melts a t 160-161' (Jacobsen gives 87"), and gives a fluorescein when heated with resorcinol. When the anhydride is treated in hot toluene solution with aniline, the corre- sponding unilic acid is precipitated, which melts at 164' with elimina- tion of water and formation of the unil (m.p. 188.5-190"). Heated in a stream of dry-ammonia gas, 3-methoxyphthalic anhydr-106 BENTLEY, IIOBINSON, AND WEIZMANN : 3-IIYDltOliYPIITWALIC ide yields the imide., which sublimes in pale yellow needles and melts a t 221-222O. When methoxyphthalonic acid is heated with phenyl hydrxzine, x condensation product is obtained, probably corresponding to that prepared by Henriques ( B e y . , 1SS8, 21, 1608) from phthalonic acid, namely, an anhydro-hydrazone, C , H , ( O S ~ e ) < ~ ~ ' Z H ) ~ ~ ~ P h . It forms yellow needles melting a t 186-lS8". From 3-methoxyphthalic acid, Jacobsen obtained S-hydraxyphthslic acid by fusion with caustic potash. This acid had also been prepared from the corresponding sulphophthalic acid (Stokes, Aamer. Chem. J. 1884, 6, 282) and from aminophthalic acid (Bernthsen, Semper, Ber., 1885, 18, 167 ; 1887, 20, 937).Prepared by Jacobsen's method, 3-hydroxyphthalic acid was found to melt at about 150" Kith formation of the anhydride ; the latter even after being twice recrystallised did not melt sharply, softening a t 150°, and gradually melting as the thermometer rose to 190'. Jacobsen gives 145-148O as the melting point of the anhydride, but remarks on the difficulty attending its purification. 3-Hydroxyphthalic anhydride, when t,reated in hot toluene solution with a molecular proportion of aniline, gives the unilic cccid melting at 145" with evolution of gas and formatmion of 3-?i?ldroxy~hthalccniz, which crystallises from dilute alcohol in short prisms and melts a t 174 -1 75'. EXPERIMENTAL.I : 5-Dihydroxync~~?~t?~a~~ne. This was prepared in considerable quantities by adding the dry powdered sodium salt of naphthalene-1 : 5-disulphonic acid to two and a half times its weight of fused caustic soda (or potash) and gradually raising the temperature to 300" with constant stirring. The fused mass was dissolved in water, acidified with hydrochloric acid, and the 1 : 5-dihydroxynaphthalene crystallised from alcohol. It melts a t 3 6 5 O . Methylatiorn of 1 : 5-~i?~~~roxync6~ht?~u~ene.--~ : 5-Dihydroxynaphtha- lene (160 grams) was dissolved in caustic soda solution, mixed with a little methyl alcohol, and treated alternately with small quantities of dimethyl sulphate and caustic soda solution, the whole being well shaken and cooled during the operation.When all the dimethyl sulphate (250 grams) had been added and sufficient caustic soda to render the liquor strongly alkaline, the product was heated on the water-bath for a short time, and afterwards diluted with water and filtered. The solid on the filter was well wasbed with water, driedAND 3-METHOXY PHTHALIC ACIDS AND THEIR DERIVATIVES. 107 and recrystalliscd several times from alcohol, from which it separated in white needles melting at 183-184'. A quicker method of purification consists in distilling the crude brown substance from a retort at the ordinary pressure and then crystallising from alcohol. 0-1300 gave 0.3654 CO, and 0.0794 H,O. 1 : 5-Di~~etliox~~za~l~tl~uZ~i?ae is readily soluble in hot alcohol or glacial acetic acid, but only sparingly so in the cold solvents.1 : 5-Methoxync~pht?~oZ.-TThe alkaline filtrate from the above solid contains the monomethyl ether, and in order to isolate this the liquor was acidified with hydrochloric acid, the brown precipitate collected, dried, and then distilled from LZ retort. The distillate was crystallised from glacial acetic acid, when the 1 : 5-rnethoxynaphthol separated in leaflets melting at 140'. C = 76.66 ; H= 6.78. C,,H1,O, requires C = 76.59 ; H = 6.38 per cent. 0.1135 gave 0.3171 CO:! and 0.0575 H,O. Nononitro-1 : 5-di??zethozynccpht~uZe~e.-This was prepared by dis- solving 1 : 5-dimethoxynaphthalene (32 grams) in glacial acetic acid and gradually adding a mixture of nitric acid (18.2 grams, sp. gr. 1.42) and acetic acid, the liquid being kept well stirred and cooled during the addition.The product was then heated on the water-bath until all the crystals which separated out in the first instance had redissolved. On cooling, the nitro-compound separated, and was collected and crystallised from glacial acetic acid, from which it was obtained in yellow, rhombic plates melting at 165-166'. C = 76-21 ; H=5*63. C,,HlOO, requires c1= 75.86 ; H = 5.75 per cent. 0.1340 gave 7.5 C.C. nitrogen at 20' and 752 mm. C,,HllO,N requires N = 6.0 Z per cent. iVr~trodinzetl~ox~nuplhtluZe?ie is only sparingly soluble in acetic acid or toluene in the cold, but more readily so on warming. Reduced with zinc dust and acetic acid or with tin and hydrochloric acid, it yields a very dark-coloured substance which has the properties of an amino- compound, but was so difficult to purify that it was not further investigated.Binitro- 1 : 5-dirnetl~oxynaplthaZene.--This substance was prepared in the same manner as the preceding one, with the exception that twice the quantity of nitric acid was employed. Purified by repeated crystallisation from acetone, it was obtained in pale orange-coloured prisms melting a t 275". N = 6.33. 0.1350 gave 12.2 C.C. nitrogen at 20" and 752 mm. Diiaitro-1 : 5-dimethoxy?a~~~ht~aZene i s very sparingly soluble in the N = 10.22. C,,Hl,0,N2 requires N = 10.07 per cent.108 BEXTLEY, ROBINSON, AND WEIZMANN : 3-HYDROXYPHTHALIC usual organic solvents in the cold, and dissolves sparingly even in hot acetic acid or toluene, but i t is more readily soluble in boiling acetone.Like the mononitro-derivative, when reduced with zinc dust and acetic acid it yields an amino-compound, which, however, is not easily purified, as i t rapidly turns very dark in the air. Oxidution of the itfethy? Ethers of 1 : 5-Dihyclroxy92ccplzthcctene.--1: 5-Di- methoxynaphthalene is scarcely attacked by cold alkaline perman- ganate even after several days. When, however, the mixture is boiled for several hours, the permanganate is reduced, and small quantities of 3-methoxyphthalic acid can ultimately be extracted with ether from the acidified liquor. !Phe yield is only small, and experiments showed that it is more advantageous to oxidise the mono-methyl ether, which is readily attacked by alkaline permanganate in the cold. 1 :5-Methoxynaphthol (32 grams) was dissolved in a very dilute solution of caustic soda (7.5 grams), the solution was cooled by the addition of ice, and treated with a solution of potassium permanganate until the colonr of the latter remained permanent for several minutes. During the addition, the liquid was strongly agitated and a current of carbon dioxide passed through it.A t the end of the operation, the liquid was boiled and filtered from the manganese precipitate; the latter was extracted several times with boiling water and filtered. The united filtrates mere nearly neutralised with hydrochloric acid, evaporated t o a small bulk and acidified, when a small quantity of a light brown substance separated which was collected and dried. This substance is a n acid which is very insoluble in most organic solvents ; it dissolves in hot acetic acid, but does not appear to crystallise from it.It was purified by dissolving in sodium carbonate and precipitating again with acid; the precipitate was then collected, and dried first on porous plate and afterwards in a vacuum over sulphuric acid. When obtained in this way it is a light brown powder which melts above 200' apparently with decomposition, and yields on analysis numbers corresponding to the empirical formula CIlH,O,. 0,0988 gave 0.2324 CO, and 0.0358 H,O. C = 64.15 ; H = 4.02. 0.1180 ,, 0.2770 CO, ,, 0.0420 H,O. C = 64.01 ; Hs3.95. This new acid forms soluble salts with the alkalis and the alkaline earths. The barium salt was prepared by boiling the acid with Ftater and barium carbonate for several hours, filtering and evaporating the filtrate to a small bulk, when the barium salt separated in brown plates.Cl,H,04 requires 0 = 64-70 ; H = 3.92 per cent. The salt was dried at 100'. 0.2165 gave 0.0861 BaSO,. Ba= 23.38. C,,H,,O,Ba requires Ba = 25.23 per cent. C,,H,,O,Ba + 2H,O ,, Ba = 23-66 ,,AND 3-METHOXYPHTHALIC ACIDS AND THEIR DERIVATLVES. 109 The silver salt was prepared by adding silver nitrate to a neutral solution of the ammonium salt. A brown flocculent precipitate was obtained which was collected, washed well with hot water, dried on porous plate, and finally :tt looo. 0.3135 gave 0.1014 Ag. Ag= 32.34. C,,H704Ag requires Ag = 34.72 per cent. Cl1H7O4Ag +H20 ,, Ag = 32.85 ,, The analytical data of the free acid and its barium and silver salts seem to point to the conclusion that the latter are salts of ar) acid of the empirical formula C,,Hl0O5, and that the free acid Cl,H80, is a lactone derivative.Henriques (Zoc. cit.), by the oxidation of a-naphthol with alkaline permanganate, obtained a similar insoluble acid corresponding to t h e . empirical formula CloH704, and which formed an easily soluble barium Salt, (C,,H60,),Ba. 5-Methox1~phthaZonic Acid.-After the separation of the acid just described, the aqueous liquors were extracted with ether, and the ethereal extract after evaporating deposited an oily acid from which, when placed in a desiccator over sulphuric acid, a solid very gradually separated. This was collected and purified by recrystallisation from a small quantity of water; it proved on analysis to be methoxy- phthalonic acid.0.1 198 gave 0.2366 CO, and 0.0394 H20. C,,H,06 requires C = 53.57 ; H = 3-57' per cent. 3-iMelhox~p~~thaZo?~ic acid is readily soluble i n alcohol, ether, or water, and crystallises froin the latter solvent extremely slowly in plates melting a t 190-191". Oxidised with potassium permanganate in acid solution it yields 3-methoxyphthalic anhydride. C = 53%6 ; H = 3.65. Anhyd~.ophen?lZl~ydraao1Le of Methoxpphtldonic Acid, -This substance was prepared by boiling methoxyphthalonic acid in aqueous solution with phenyl hydrazine hydrochloride, filtering from some dark-coloured, oily substance, and evaporating the filtrate. A yellow solid Separated, which was purified by dissolving in alcohol and precipibating with ether, when i t was obtained in yellow needles melting a t 186--1SS".0.0802 gave 6.8 C.C. nitrogen at 19" and 762 mm. C16H120,N, requires N = 0.46 per cent. 3-Methoxyphthalic anhydvide.-The oily mother liquors from which the methoxyphthalonic acid had separated were distilled under reduced pressure and yielded a solid distillate which was purified by recrystallis- N = 9.77.110 BENTLEY, ROBINSON, AND WEIZMANK : 3-HYDROXYPHTHALIC ing from toluene, when 3-methoxyphthalic anhydride was obtained in prisms. C = 60.22 ; H = 3-56. 4 4 (1) 0.1326 gave 0.2928 CO, and 0.0424 H,O. (2) O.1010 ,, 0.2240 CO, ,, 0.0324 H20. C=60*48 ; H = 3.56. CgH,O, requires C = 60.67 ; H = 3.37 per cent. 3-Methoxyphtl~alic an?uj&ide melts a t 160- 161°, and when heated with resorcinol yields a fluorescein.It is almost insoluble in cold water, but dissolves somewhat slowly in hot water, from which after long standing the free acid separates. 3-Methoxypht~udic acid.-This acid mas prepared from the anhydride by dissolving the latter in hot water and allowing the solution to evaporate in a desiccator over sulphuric acid. It separates in minute prisms melting a t 173-1'74' with evolution of gas and formation of the anhydride. It is readily soluble in water, alcohol or ether. 0.1170 gave 0.2368 CO, and 0.0438 H,O. CgH,05 requires C = 55.10 ; H = 4.08 per cent. The same acid was also prepared from metlioxyphthalonic acid, which, as already stated, yields, on oxidation in cold acid solution with per- manganate, 3-methoxyphthalic anhydride. 3-Methoxyphthalonic acid (1 gram) was dissolved in a small quantity of water, mixed with dilute sulphuric acid and cooled with ice to 0".An ice-cold sulution of potassium permanganate (0.39 gram) was run i n , and after a few minutes the permanganate became decolorised, carbon dioxide was evolved and a white precipitate separated. This was washed with a little water and dried; it then melted a t 160°, and was evidently 3-methoxyphthalic anhydride. It dissolved slowly in hot water, from which solution on long standing in a desiccator over sul- phuric acid crystals separated which melted a t 174" and gave on analysis figures proving it to be 3-methoxyphthalic acid. C = 55.17 ; H = 3.99. C=55*19; H=4*15. 0.1 122 gave 0.2270 CO, and 0.0403 H,O. CgHH,05 requires C = 55.10 ; H = 4.08 per cent.3-M&oxypl~thaZimide.-This substance mas prepared by heating the anhydride in a stream of dry ammonia gas, when it sublimed in pale yellow needles. Crystallised from methyl alcohol, it was obtained in almost colourless needles melting at 22 1-222". 0,1234 gave 8.5 C.C. nitrogen at 18" and 756 mm. CgH70,N requires N = 7.91 per cent. 3-Met~~ox~phthaZuniZic acid, C,H,(OMe j(CO,H)CO*NHPh.-In order to prepare this derivative, 3-methoxyphthalic anhydride (1 gram) was dissolved in a small quantity of hot toluene and mixed with a solution of aniline (0.52 gram) in toluene. A white solid soon separated which N = 7.91.AND ~ - M E ~ . ~ ~ ~ X Y P H ~ ~ I A L I C ACIDS AND THEIR DERIVATIVES. 11 1 was collected and recrystallised from dilute alcohol, when i t separated in colourless plates melting a,t'164' with the formation of the anil.N = 5.47. 0.1317 gave 6.2 C.C. nitrogen a t ISo and 755 mm. C,,H,,O,N requires N = 5.16 per cent. 3-il.lelhoryphthcclan~1, C,;H3( OMe)<CO>NPh.-The co foregoing anilic acid melts a t 164O with the evolution of gas, then solidifies and only melts again when the temperature of the bath reaches 180'. The product was purified by recrystallising from alcohol, from which it mas obtained in colourless plates melting at 188.5-190'. 0.1618 gave 7.8 C.C. nitrogen a t 20' and 764 mm. N = 5.54. C,,H,,O,N requires N = 5.53 per cent. 3- Z€ydroxypidLalic acid .-This acid was prepared by fusing 3-methoxyphtbalic acid wit,h caustic potash. The methoxy-acid (1 part) was added to strong caustic potash (10 parts) at 120°, when the temperature of the fusion immediately rose to 200'.After a few minutes, the product was dissolved in water, acidified strongly with hydrochloric acid and extracted repeatedly with ether. After evaporating the ether, an oily acid was obtained which probably comisted of a mixture of hydroxy- and methoxy-phthalic acids. I n order to separate the hydroxyphthalic acid, the crude oily acid was esterified by warming on the water-bath with methyl alcohol and ~ulphuric! acid for several hours. The cooled product was then poured into water, extracted with ether, the ethereal solution washed first with a solution of sodium carbonmate and then with dilute caustic: soda. The latter extract was acidified and again extracted with ether, when, after evaporating, a viscous oil was obtained which did not crystallise after standing two days.This oil was mponified with alcoholic potash and the resulting acid extracted with ether. The ethereal extract, after the removal of the ether, yielded again an oily acid, which, however, solidified when placed in a desiccator over sulphuric acid. The solid was pressed on porous porcelain and recrystallised from water, from which it separated, after long standing in a dessicator, in short prisms melting indefinitely at 150°, gas being evolved a t 160'. As stated by Jacobsen, it yields a fluorescein with resorcinol and gives a cherry-red coloration with ferric chloride. S-B~droxypI~thalic Anhydride.-3-Hydroxyphthalic acid readily loses water even at 100' with the formation of the anhydride. I n order to prepare this substance, the acid was heated in a sulphuric acid bath until it melted and the evolution of gas had ceased. The residue was recrystallised twice from toluene, when the anhydride separated112 LE BAS: RELATION BETWEEN VOLUMES OF ATOMS OF partly amorphous and partly in minute needles which melted in- definitely between 150' and 190'. 0.1055 gave 0.3258 CO, and 0.0260 H,O. C8H40, requires C = 58.53 ; H = 2.44 per cent. 3-ETydi.oxy~hth~Za?zilic Acid.--This derivative was prepared in exactly the same manner as 3-methoxyphthalanilic acid (p. 110). It crystallises from dilute alcohol in long, slender needles melting a t 145' with evolution of gas. I t s alcoholic solution gives a reddish-brown color- ation with ferric chloride. 3-Hyd~oxyphthaZaniZ.--The anilic acid just described was heated in a sulphuric acid bath t o 150°, and after crystallising the residue from dilute alcohol, the ccnil separated in short prisms melting a t C = 58.30 ; H = 2.73. 174-1 75". 0.0962 gave 4.8 C.C. nitrogen a t 19" and '762 mm. Like the auilic acid, the anil gives a reddish-brown coloration with N = 5.75. C1,H,O,N requires N = 5.85 per cent. ferric chloride. CHEMICAL LABORATORIES, UNIVERSITY OF MAKCHESTER.

ISSN:0368-1645    

DOI:10.1039/CT9079100104

出版商:RSC    

年代:1907

数据来源: RSC