摘要:

J 0 u R N A L J. DEWAR, LL.D., F.R.S. E. DIVERS, M.D., F.R.S. WYNDHAM K. DUXSTAX, M.A., F.R.S. H. J. H. FENTON, M.A., P.R.S. C. E. GXOVES, F.R.S. OF J. EMERSON REYNOLDS, n.Sc., F.M.S. A. Scor~, D.Sc., F. R. S. T. E. THORPE, LL.D., F.R.S. W. A. TILDEN, D.Sc., F.R.S. THE CHEMICAL SOCIETY, TRANSACTIONS. &;bitor : W. I?. WYNNE, D.Sc., F.R.S. %b-@;bitDK : A. J. GEEENAWAY 1801. VOl. LXXIX. LONDON: GURNEY L! JACKSON, 1, PATERNOSTER ROW. 1901.RlC€IARD CLAY & SONS, LIMITED, LONDON & BUNGAY.J O U R N A L OF THE CHEMICAL SOCIETY, TRANSACTIONS. H. E. ARMsmoNG, Ph.D., F.R.S. J. DEWAR, LL.D., F.R.S. E. DIVERS, M.D., F.R.S. WYNDHAM R. DUNSTAN, M. A., F. R.S. H. J. H. FENTON, M.A., F.R.S. C. E. GROVES, F.R.S. R. MELDOLA, F.R.S. J. EMERSON REYKOLDS, D.Sc., F.R.S. A.SCOTT, D.Sc., F.R.S. T. E. TEIORPE, LL.D., F.R.S. W. A. TILDE-V, D.Sc., F.R.S. @bitor : W. P. WYNNE, D.Sc., F.R.S. %julo-@bitor : A. J. GREENAWAY. 1901. Vol. LXXIX. Part I. LONDON: GURNEY & JACKSON, 1, PATERNOSTER ROW. 1901.RlC€IARD CLAY & SONS, LIMITED, LONDON & BUNGAY.J 0 U R N A 1, OF THE CHEMICAL SOCIETY TRANSACTIONS. H. E. ARMSTRONG, Ph.D., F.R.S. J. DEWAR, LL.D., F.R.S. E. DIVERS, M..D., F.R.S. WYNDHAM K. DUXSTAN, M A , F.R.S. H. J. H. FENTON, M.A., F.R.S. C. E. GROVES, F.R.S. R. MELDOLA, F.R.S. J. EMEESON HEYNOLDS, n.Sc., F.X.S. A. SCOW, D.Sc., F.R.S. T. E. THORPE, LL.D., F.R.S. W. A. TILDEN, D.Sc., F.R.S. cebitor : W. Y. WYNNE, D.Sc., F.R.S. %sub-6;bitor : A. J. GREENAWAY. 1901. Vol. LXXIX Part 11. LONDON: GURNEY St JACKSON, 1, PATERNOSTER ROW.1901.RICHARD CLAY & SONS, LIMITED, LONDON & BUNOAY.RICHARD CLAY & SONS, LIMITED, LONDON & BUNOAY.C O N T E N T S . PAPERS COMMUNICATED TO THE CHEMICAL SOCIETY. PA(*I.: R,nmmelsberg Memorial Lectnre. By H. A. MIERS, M.A., D.Sc., F.R.S., Waynflete Professor of Mineralogy in the University of Oxford . . 1 1.--2 : 3 : 5-Trichlorobenzoic Acid. By FRANCIS EDWARD MATTHEWS . . 43 TI.-The Nitration of Benzeneazosnlicylic Acid. By JOHN THEODORE HEWITT and J. J. Fox. . . 49 111.-Oxidation of Benzalthiosemicarbazone. By GEORGE YOUNG, Yh.D., and WILLIAM EYRE, B.Sc. . 54 1V.-A Simplified Nethod for the Spectrographic Analysis of Minerals. By WALTER NOEL HARTLEY, F.R.S., and HUGH RAMAGE, F.I.C., A.R.C.Sc.1. . . 61 V.-The Alkaloid of Hposcyanzus muticus and of Datum Stwmo- nium grown in EgFpt.By WYNDHAM R. DUNSTAN, F.R.S., and HAROLD BROWN, Assistant Chemist in the Scientific Y1.-The Inversion of the Optically Active ccc-Tetrahydro-/3- naphthylamines prepared by the aid of cl- and LBromo- camphorsnlphonic Acids. By WrLLIAnr JACKSON POPE and ALFRED WILLIAM HARVEY . . 74 V1I.-The Alkaloids of Corydalis cava. Conversion of Cory- bulbine into Corydaline. By JAMES J. DOBBIE, D.Sc., M.A., VIT1.-Relationships of Oxalacetic Acid. By HENRY J. HORST- MAN FENTON, F.R.S., and HUMPHREY OWEN JONES, B.B., B.Sc. 1X.-Interaction of Urethanes and Primary Benzenoid Amines. X.-Infracampholenic Acid, an Isomeride of Campholytic and XI.-Tutu. Part I. Tutin and Coriamyrtin. By THOMAS HILL EASTERFIELD, Professor of Chemistry, Victoria College, Wellington, N.Z., and BERNARD CRACROFT ASTON, Chemist Department of the Imperial Institute .. . 71 ALEXANDER LAUDER, B.Sc., and PHOTIOS G. PALIATSEAS . 87 9 1 By AUGUSTUS EDWARD DIXON, M.D. . . 102 isoLauronolic Acids. By MARTIN ONSLOW FORSTER . . 108 to the New Zealand Department of Agriculture . . . 120iv CONTENTS. XI1.-Some a-Alkyl Substitution Products of Glutaric, Adipic, XII1.-Santalenic Acid. By ALFRED C. CHAPMAN, F. C. . X1V.-The Interaction of Ethyl Sodiomethylmalonate and Mesityl Oxide. XV. -Ammonium Bromide and the Atomic Weight of Nitrogen. By ALEXANDER SCOTT . . XVI. -The Nitration of the Three Tolueneazophenols. By JOHN THEODORE HEWITT and JAMES HENRY LINDFIELD . XVI1.-The Bromination of o-Oxyazo-compounds and its bearing on their Constitution. By JOHN THEODORE HEWITT and HENRY ABLETT PHILLIPS .XVII1.-The Influence of Solvents on the Rotation of Optically Active Compounds. I. Influence of Water, Methyl Alcohol, Ethyl Alcohol, 92-Propyl Alcohol, and Glycerol ou the Rotation of Ethyl Tartrate. . X1X.-On the Union of Hydrogen and Chlorine. Parts I to 111. By J. W. MELLOR . XX.-On the Nature of Polyiodides and their Dissociation in Aqueous Solution. By HARRY MEDFORTH DAWSON, Ph.D., B.Sc., late 1851 Exhibitioner . XX1.-The Decomposition of Chlorates. Part 111. Calcium Chlorate and Silver Chlorate. By WILLIAM H. SODEAU, B.Sc. XXI1.-The Action of Ethylene Dibromide on Xylidine and $-Cumidine. By ALFRED SENIER and WILLIAM GOODWIN . XXII1.-The Action of Phenylcarbimide on Diphenyl-, Dialphyl-, and Dinaphthyl-diamines. By ALFRED SENIER and WILLIAM GOODP~IN .XXIV.-Note on the use of Pyridine for Molecular Weight Determinations by the Ebullioscopic Method. By WILLIAM Ross INNES, M.Sc., Ph.D. . XXV.-The Amide, Anilide, and 0- and p-Toluidides of Glyceric Acid. By PERCY FARADAY FRANKLAND, FREDERICK MALCOLM WHARTON, and HENRY ASTON XXVI. -The Preparation of Acetylchloraminobenzene and some related Compounds. By F. D. CHATTAWAY and X. J. P. ORTON . XXVI1.-The Preparation of Esters from other Esters of the same Acid. By T. 8. PATTERaoN and CYRIL DICKINSON . XXVII1.-Note on Tecomin, a Colouring Matter derived from the Heart-Wood of Bignonia Teconza. By THEOPHILUS H. LEE . XX1X.-Iron Nitride. By GILBERT JOHN FOWLER, M.Sc. (Vict.) and Pimelic Acids.By J. W. MELLOR . By ARTHUR WILLIAM CROSSLEY . By T. 8. PATTERSON . PAGE 126 134 138 147 155 160 167 216 238 247 254 258 26 1 266 274 280 284 285CONTENTS. V YAGE XXX.-The Heat of Formation and Constitution of Iron Nitride. By GILBERT JOHN FOWLER, M.Sc. (Vict.), and PHILIP JOSEPH HARTOG, B.Sc. (Lond. and Vict.) . XXX1.-The Preparation of lodic Acid. By ALEXANDER SCOTT and WILLIAM ARBUCKLE . XXXI1.-The Reaction between Ethyl Alcohol and Hydro- chloric Acid. By THOMAS SLATER PRICE, D.Sc. (late 1851 Exhibition Scholar) . XXXII1.-The Collection and Examination of the Gases pro- duced by Bacteria from certain Media. By WALTER CHARLES CROSS PARES and WALTER HENRY JOLLYMAN . XXX1V.-Tetramethylenecarbinol. By W. H. PERKIN, jun. . XXXV.-The Action of Aluminium Chloride on Camphoric Anhydride.XXXV1.-The Action of Hydrogen Bromide on Carbohydrates. By HENRY J. HORSTMAN FENTON, F.R.S., and MISS MILDRED GOSTLING, B.Sc. . XXXVI1.-The Ketonic Constitution of Cellulose. By CHARLES FREDERICK CROSS and EDWARD JOHN BEVAN. . XXXVII1.-Isomeric Hydrindamine Camphor-r-sulphonates. Racemisation of a-Bromocamphor. By FREDERIC STANLEY KIPPING, Ph.D., D.Sc., F.R.S. . XXX1X.-aa-Hydroxycamphorcarboxylic Acid. By ARTHUR LAPWORTH and EDGAR M. CHAPMAN XL.-The Bacterial Decomposition of Formic Acid into Carbon Dioxide and Hydrogen. By WALTER CHARLES CROSS PAKES and WALTER HENRY JOLLYMAN . . By F. H. LEES and W. H. PERKIN, jun. . XL1.-Preparation of Substituted Amides from the Correspond- ing Sodamides. By ARTHUR WALSH TITHERLEY, M.Sc., Ph.D.XLI1.-A New Method of Preparing Diacetamide. By ARTHUR WALSH TITHERLEY, M.Sc., P h .D. XLII1.-Note on Two Molecular compounds of Acetamide. By ARTHUR WALSH TITHERLEP, M.Sc., Ph.D. . XL1V.-A New Method fop the Measurement of Ionic Velocities in Aqueous Solution. By B, D. STEELE, B.Sc., 1851 Exhibition Scholar (Melbourne) . XLV.-Isomeric Salts containing Quinquevalent Nitrogen. Part VII. Benzylhydrindamine Bromocamphorsulphonates. By FREDERIC STANLEY KIPPING, Ph.D., I).Sc., F.R.S., and HAROLD HALL, A.I.C. XLV1.-Isomeric Hydrindamine Mandelates and Phenylchlor- acethydrindnmides. By FREDERIC STANLEY KIPPING, Ph.D., D.Sc., F.R.S., and HAROLD HALL, A.I.C. . 299 302 303 322 329 332 36 1 366 3 70 377 386 39 1 41 1 41 3 414 430 442vi CONTENTS. PAGE XLVII. -Organic Derivatives of Silicon.Triphenylsilicol and By F. STANLEY KIPPING, Ph.D., XLVII1.-The Bacterial Oxidation of Formates by Nitrates. By WALTER CHARLES CROSS PAKTW ant1 WALTER HENRY JOLLYMAN . 459 XL1X.-The Action of Acetylchloro- and Acetylbronio-amino- benzenes on Ainines and Phenylhydrazine. By F. D. CHATTAWAY and K. J. P. ORTON . . 461 L.-The Preparation of o-Cbloroaniline. By F. D. CHATTAWAY and K. J. P. ORTON . . 469 L1.-Condensation of Phenols with Esters of the Acetylene Series. Part IV. Benzo-y-pyrone ant1 its Homologues. By SIEGFRIED RUHEMANN and HAROLD W. BAUSOR, B.A. . 470 LI1.-Optical Activity of Certain Ethers and Estei-s. By Professor PHILIPPE A. GUYE . . 475 LII1.-The Influence of Solvents on the Rotation of Optically Active Compounds. Part 11.Influence of isoButyl Alcohol and of sec.Octy1 Alcohol (Methylhexylcnrbinol) on Ethyl Part 11, The Absorptive Powers of Dilute Solutions of Salts of the Alkali Metals. By H. M. DAWSON and J. MCCRAE . 493 LV.-Influence of a Heterocyclic Group on Rotatory Power ; the Ethyl and Methyl Esters of Dipyromucyltartaric Acid, By PERCY F. FRANKLAND and FRANCIS W. ASTON, late Forster Research Scholar . . 511 LV1.-Formation of Amides from Aldehydes. By ROBERT Howso~ PICKARD, D.Sc., PbD., and WILr,IaM CARTER . 520 LVI1.-Additive Compounds of a- and P-Naphthylamine with Trinitro-derivatives of Benzene. By JOHN J. SUDBOROUGH . 523 LVII1.-Acetylation of Arylamines. By JOHN J. SUDBOROUGH 533 L1X.-A Form of Tautomerisrn occurring amongst the Thio- cyanates of Electronegative Radicles. By AUGUSTUS EDWARD DIXON, M.D.. . 541 LX.-Halogen-substituted Thiosinamines. By AuausTus LX1.-Researches on Morphine. Part 11. By S. B. SCHRYVER and FREDERIC H. LEES . . 563 LXI1.-The Constitution of Pilocarpine. Part 11. By HOOPER ALBERT DICRINBON JOWETT, D.Sc. . . 580 LX1II.-Pheno-a-ketoheptamethylene and its Derivatives. By FE~EDERIC STANLEY KIPPING, Ph.D., D.Sc., F.R.S., and ALBERT E. HUNTER . . 602 Alkyloxysilicon Chlorides. D.Sc., F.R.S., and LORENZO L. LLOYD . 449 Tartrate. By T. S. PATTERSON . . 477 L1V.-MetakAmmonia Compounds in Aqueous Solution. EDWARD DIXON, M.D. . 553CONTENTS. vii PAOE LXIV. -The Chemical Action of Bacillzcs coli comnaunis and Similar Organisms on Carbohydrates and Allied Compounds. By ARTHUR HARDEN . . 610 LXV.-The Action of Alkyl Haloids on Aldoximes and Ketoximes.Part 11. Alkylated Oximes and isoOximes, and the, Constitution of Aliphatic Oximes. By WYNDHAM R. DUNSTAN and ERNEST GOULDING . . 628 LXV1.-The Supposed Existence of Two Isomeric Triethyl- oxamines. By WYNDHAM R. DUNSTAN and ERNEST GOULDING . . 641 LXVI1.-Studies in the Camphane Series. Part 11. Nitro- camphene, Aminocamphene, and Hydroxycamphene. By MARTIN ONSLOW FORSTER . . 644 LXVII1.-Studies in the Camphane Series. Part 111. Action of Hydroxylamine on the Anhydrides of Bromonitro- camphane. By MARTIN ONSLOW FORSTER . . 653 LX1X.-Contribution to the Chemistry of the Triazoles. 1-Methyl-5-hydroxytriazoles. By GEORGE YOUNG, Ph.D., and WILLIAM HENRY OATES, late 1851 Exhibition Scholar . 659 LXX.-Preparation of o-Dimethoxybenzoin and a new method of preparing Salicylaldehyde Methyl Ether, By JAMES C.IRVINE, B.Sc. (1851 Exhibition Research Scholar). (St. Andrews University) . . , 668 LXX1.-Researches on Moorland Waters. Part 11. On the Origin of the Combined Chlorine. By WILLIAM ACKROYD, F. I. C. . 673 LXXI1.--On the Estimation of Cocaine and on Cocaine Hydr- iodide Periodide. By W. GARSED, Salters’ Company’s Research Fellow in the Research Laboratory of the Pharma- ceutical Society of Great Britain, and J. N. COLLIE, F.R.8. 675 LXXII1.-Note on Acetonylacetone. By TEOMAB GRAY . . 681 LXX1V.-Condensation of Acetonylacetone with Hydrazine Hydrate. By THOMAS GRAY . , 682 LXXV.-Preparation and Properties of 2 : 6-Dibromo-4-nitroso- phenol. By MARTIN ONSLOW FORSTER and WILLIAM ROBERTSON, A.R.C.S.. 686 LXXV1.-Alkylation of Acylarylamines. By G. DRUCE LANDER , . 690 LXXVI1.-Preparation of A liphatic Imino-ethers from Amides. LXXVII1.-Preparation of Synthetical Glucosides. 11. By HUGH RYAN, M.A., D.Sc., and W. SLOAN MILLS, M.A. By G. DRUOE LANDER . . 701 704vi ii CONTENTS. LXX1X.-The Influence of Cane-sugar on the Conductivities of Solutions of Potassium Chloride, Hydrogen Chloride, and Potassium Hydroxide, with Evidence of Salt-formation in the last Case. By C. J. MARTIN, M.B., D.Sc., and ORME MASSON, M.A., D.Sc. LXXX.-A Modification of Gutzeit’s Test for Arsenic. By EDWIN DOWZARD . LXXXL-Tapour Pressure of Aqueous Ammonia Solution. Part I. By EDGAR PHILIP PERMAN, D.Sc. 1. . LXXXII. -Influence of Sodium Sulphate on the Vapour Pressure of Aqueous Ammonia Solution. By EDGAR PHILIP PERMAN, D.Sc.LXXXII1.-The Synthetical Formation of Bridged Rings. Part I. Some Derivatives of Dicyclopentane. By W. H. PERKIN, jun., and J. F. TI-IORPE [and in part, c. WALKER] . &XXXIV.-Lead Silicates in Relation to Pottery Manufacture. By T. E. THORPE, C.B., F.R.S., and CHARLES SIMMONDS, B.Sc. LXXXV.-Derivatives of Methylfurfural. By HENRY J. HORSTMAN FENTON, F.R.S., and MISS MILDRED GOSTLING, B.Sc. LXXXV1.-The symmetrical Chlorodibromo- and Dichlorobromo- anilines and Chloro- and Bromo-amino-derivatives of Chloro- bromo-acetanilides. By E. D. CHATTAWAY and K. J. P. ORTON . LXXXVI1.-The Replacement of Bromine by Chlorine in Anilines. LXXXVII1.-Optically Active Nitrogen Compounds and their Bearing on the Valency of Nitrogen.d- and Z-a-Benzyl- phenylallylmethylammonium Salts. By WILLIAM JACKSON POPE and ALFRED WILGIAM HARVEY . LXXX 1X.-Hydroxyoxamides. By ROBERT HOWSON PICKARD, D.Sc., Ph.D., and WILLIAM CARTER . XC.-Note on Pyromucylhydroxamic Acid. By ROBERT HOWSON PICKARD, D.Sc., Ph.D., and ALLEN NEVILLE, B.Sc. . XC1.-The Absorption Spectra of Cyanogen Compounds. By WALTER NOEL HARTLEY, F.R.S. ; JAMES J. DOBBIE, D.Sc., M.A. ; and ALEXANDER LAUDER, B.Sc. XCI1.-A New Method for the Determination of Hydrolytic Dissociation. By ROBERT CROSBIE FARMER, B.Sc. (Vict.), Ph.D. (Wurzburg), Priestley Scholar in the University of Birmingham . Annual General Meeting . Obituary Notices . By F. D. CHATTAWAY and K. J. P. ORTON . . PAGE 707 715 718 725 729 791 807 816 82 2 828 841 847 848 863 87 1 888CONTENTS.ix PAGE XCII1.-The Chlorine Derivatives of Pyridine. Part VII. Some Condensation Products. By W. J. SELL, M.A., F.R.S., and F. W. DOOTSON, M.A., D.Sc. . . 899 XC1V.-The Action of Lead Thiocyanate on the Chlorocar- bonates. Part TI. Carboxymethyl- and Carboxyamyl-thio- carbimides and their Derivatives. By ROBERT ELLIOTT DORAN . . 906 XCV.-A Laboratory Method for the Preparation of Ethylene. By G. S. NEWTH . . 915 XCV1.-Condensation of Phenols with Esters of the Acetylene Series. Part V. Homologues of Benzo-y-pyrone. By SIEGFRIED RUHEMANN . . 918 XCVI1.-The colloid form of Piperine, with especial reference to its Refractive and Dispersive Powers. By HENRY G. MADAN, M.A. . . 922 XCVII1.-The Condensation of Phenyl Ethyl Ketone and Benzaldehyde.By ROBERT DUNCOMBE ABELL, B.Sc. (Wales), 1851 Exhibition Scholar of the University College of North Wales, Bangor . 928 XCIX.-The Decomposition of Chlorates. Part IV. The Supposed Mechanical Facilitation of the Decomposition of C.-The Nutrition of Yeast. Part 111. By ARTHUR L. STERN, D.Sc. . 943 GI.-Oroxylin. By WILLIAM ARTHUR HARRISON NAYLOR and CHARLFS STANLEY DYER . , . 954 CI1.-Optically Active Dimethoxysuccinic Acid and its Deriva- tives. By THOMAS PURDIE, F.R.S., and JAMES C. IRVINE, B.Sc. . 957 CTI1.-The Influenc'e of Solvents on the Rotatory Powers of Ethereal Dimethoxysuccinates and Tartrates. By THOMAS PURDIE, F.R.S., and WILLIAM BARBOUR, B.Sc., Berry Scholar in Science . . 971 C1V.-The Occurrence of Paraffins in the Leaf of Tobacco. By T. E.THORPE, C.B., F.R.S., and JOHN HOLMES . . 982 CV.-Studies in the Camphane Series. Part IV. The Isomerism of a-Benzoylcamphor. By MARTIN ONSLOW FORSTER . . 987 CVI.-Studies in the Camphane Series. Part V. Halogen Derivatives of pCymene from substituted Nitrocamphanes. By MARTIN OHSLOW FORSTER and WILLIAM ROBERTSON, A.R.C.S.. . . 1003 CVI1.-Reduction of ay-Dibenzoylpropane and Dibenzoyl- diphenylbutadiene. By FRANCIS R. JAPP, F.R.S., and ARTHUR C. MICHIE, B.Sc. . . 1010 Potassium Chlorate. By WILLIAM H. SODEAU, B.Sc. . . 939X CONTENTS. PAGE CVII1.-Homologues of Anhydracetonebenzil. By FRANCIS R. JAPP, F.R.S., and ANDREW N. MELDRUM, B.Sc. . . 1024 C1X.-The Direct Union of Carbon and Hydrogen. Part 11. By WILLIAM A. BONE and DAVID 5. JERDAN . . 1042 CX.-On the Decomposition of Carbon Dioxide when submitted to Electric Discharge at Low Pressures, By J.NORMAN COLLIE, Ph.D., F.R.S. . ‘1063 Part 111. By H. M. DAW- SON and J. MCCRAE . . 1069 Part IV. The Influence of Temperature on the Dissociation of Copper-Ammonia gulphate. By H. M. DAWSON and 5. MCCRAE . . 1072 CXI1I.-Additional Notes on Dinitro-o-anisidine. Chemical Reaction in which one of the Products continues the same Reaction. By RAPHAEL MELDOLA, F.R.B., and JOHN VABGAS EYRE . . 1076 CX1V.-Some relations between Physical Constants and Con- stitution in Benzenoid Amines. Part 11. By PAUL GORDAN and LEONHARD LIMPACH . * . . . 1080 CXV.-The combined action of Diastase and Yeast on Starch- granules. By GEORGE HARRIS MORRIS, Ph.D,, B.Sc. . . 1085 CXV1.-Action of Bromine on the Three Tolueneazophenols.. 1090 CXVI1.-Nitrilosulphates. By EDWARDIVERS and TAMEMASA HAGA . . 1093 CXVIIL-Ammonium and other Imidosulphites. By EDWARD DIVERS and MASATAKA OGAWA . . 1099 CX1X.-Ethyl sec.Octy1 Tartrate and its Dibenzoyl and Diacetyl Derivatives. By JOHN MCCRAE. . . 1103 CXX.-The Aluminium-Mercury Couple. Part 111. Chlorina- tion of Aromatic Hydrocarbons in presence of the Couple. The Constitution of the Dichlorotoluenes. By JULIUS B. . 1111 CXX1.-The Esterification of 3-Nitrophthalic Acid. By ALEX. MCKENZIE, Grocers’ Company Research Scholar . . . 1135 CXXI1.-Derivatives of 3-Nitrotolyl-4-hydrazine. By FRANK GEO. POPE and JAB. MORTON HIRD . , 1141 CXXII1.-The Constituents of the Sandarac Resins. By THOMAS ANDERSON HENRY, D. Sc. (Lond.), Salters’ Com- pany’s Research Fellow in the Laboratories of the Imperial Institute .. 1144 By CORNELIUS O’SULLIVAN, F.R.S. 1164 CXI. -Metal-Ammonia Compounds in Aqueous Solution. Salts of the Alkaline Earth Metals. CXI1.-Metal-Ammonia Compounds in Aqueous Solution. By J. T. HEWITT and JOHN N. TERVET . COHEN and HENRY D. DAKIN, the Yorkshire College . CXX1V.-Gum Tragacanth.CONTENTS. xi PAUE CXXV.-Condensation of Phenols with Esters of the Acetylene Series. Part TI. By SIEGFRIED RUHEMANN and ERNEST WRABG, B.A. . . 1185 CXXV1.-The Hydrobromides of Undecylenic Acid. By JAMES WALKER and JOHN S. LUMSDEN . . 1191 CXXVI1.-n-Decanedicarboxylic Acid. By JAMES WALKER and JOHN S. LUMSDEN . . 1197 CXXVII1.-The Action of Sodium Methoxide and its Horno- logues on Bonzophenone Chloride and Benzal Chloride.By JOHN EDWIN MACKENZIE, D.Sc., Ph.D. CXX1X.-Action of the Chlorides of Phosphorus on Aromatic Ethers of Glycerol. Diaryloxyisopropylphosphorous Acids. . 1221 CXXX.-Autofermentation and Liquefaction of Pressed Yeast. By ARTHUR HARDEN and SYDNEY ROWLAND . . 1227 CXXX1.-Non-existence of the so-called Suboxide of Phosphorus. Part 11. By CHARLES HUTCHENS BURGESS and DAVID LEONARD CHAPMAN . . 1235 CXXXIL-The Action of A.mmonia on Metals at High Temperatures. By GEORGE THOMAS BEILBY and GEORGE GERALD. HENDERSON . , 1245 CXXXIII. -Condensation of Benzil with Dibenzyl Ketone. By GEORGE GERALI?) HENDERSON and ROBERT HENRY CORSTORPHINE, B.Sc. . . 1256 CXXX1V.-The Form of Change in Organic Compounds, and the Function of the a-meta-Orientating Groups. By ARTHUR LAPWORTH .. 1265 CXXXV.-The Constitution of Camphanic Acid and of Bromo- camphoric Anhydride. By ARTHUR LAPWORTH and WALTER HENRY LENTON . . 1284 CXXXV1.-The Chlorodibromo- and Dichlorobromo-benzenes. By WILLIAM HOLDSWORTH HURTLEY, D.Sc. (Lond.) . . 1293 CXXXVIL-Experiment s on the Production of Optically Active Compounds from Inactive Substances. By J. B. COHEN and C. E. WHITELEY. . . 1305 CXXXVIIL-The Products of the Action of Fused Potassium Hydroxide on Diliydroxystearic Acid. By HENRY RONDEL LESUEUR . . 1313 CXXX1X.-Note on the Supposed Formation of an Oxide of Hydrogen higher than the Dioxide. By WILLIAM RAMSAY, F.R.S. . . 1324 CXL.-The Electrolytic Reduction of Nitrourea. By G. W. F. HOLROYD . . 1326 CXL1.-The Constitution of Pilocarpine. Part 111. By HOOPER ALBERT DICKINSON JOWETT . , 1331 . 1204 By D. R. BOYD .xii CONTENTS. PAGE CXLII.--A New Synthesis of a-Ethyltricarballylic Acid. By HOOPER ALBERT DICKINSON JOWETT . . 1346 CXLII1.-Benzoylation of Fatty Acids in the Presence of Ammonia. Formation of Amides. By K. J. P. ORTON . 1351 CXL1V.-Liquid Nitrogen Peroxide as a Solvent. By PERCY FARADAY PRANKLAND, Ph.D., F.R.S., and ROBERT CROSBIE FARMER, M.Sc. (Vict.), Ph.D. . . 1356 CXLV. -The Action of Aluminium Chloride on Camphoric Anhydride. Part 11. By W. H. PERKIN, jun., and J. YATES. . . 1373 CXLVL-Brazilin and Hzematoxylin. Part I. By A. W. GILBODY, W. H. PERKIN, jun., and J. YATES . 1396 .xii CONTENTS. PAGE CXLII.--A New Synthesis of a-Ethyltricarballylic Acid. By HOOPER ALBERT DICKINSON JOWETT . . 1346 CXLII1.-Benzoylation of Fatty Acids in the Presence of Ammonia. Formation of Amides. By K. J. P. ORTON . 1351 CXL1V.-Liquid Nitrogen Peroxide as a Solvent. By PERCY FARADAY PRANKLAND, Ph.D., F.R.S., and ROBERT CROSBIE FARMER, M.Sc. (Vict.), Ph.D. . . 1356 CXLV. -The Action of Aluminium Chloride on Camphoric Anhydride. Part 11. By W. H. PERKIN, jun., and J. YATES. . . 1373 CXLVL-Brazilin and Hzematoxylin. Part I. By A. W. GILBODY, W. H. PERKIN, jun., and J. YATES . 1396 .

ISSN:0368-1645    

DOI:10.1039/CT90179FP001

出版商:RSC    

年代:1901

数据来源: RSC

摘要:

MATTHEWS : 2 : 3 : 5-TRlCHLOROBENZOIC ACID. 43 By FRANCIH EDWARD MATTHEWS. IN a paper on the hexachlorides of benzonitrile, benzamide, and benzoic acid, it was stated that alcoholic soda acted on the nitrile in two stages, the first being the removal of three molecular proportions of hydrogen chloride, with the production of trichlorobenzonitrile, and the second the hydrolysis of the cyano-group, with the formation of a mixture of sodium trichlorobenzoates. On repeating this work on a larger scale, it was found that, by the continued fractional crystallisa-44 MATTHEWS : 2 : 3 : 5-TRICHLOROBENZOIC ACID. tiori of the barium salts of the mixed acids, a new trichlorobenzoic acid could be isolated in a state of purity. The process had to be carried out on a considerable scale to obtain a satisfactory result, and the yield of the pure acid left much to be desired.Shortly afterwards, it was found that by the action of quino- line on the nitrile, the nitrile of the same trichlorobenzoic acid could be obtained almost quantitatively, and this proving to be readily volatile with steam, was easily purified. Of the six theoretically possible trichlorobenzoic acids, four have already been obtained, the missing ones being : CO,H TI. E:l)”’ \ As the acid obtained from the nitrile did not agree in its properties with any of those previously described, the new acid must have one of the formuh given above, It was therefore thought worth while to subject it to a complete investigation, with a view of determining its constitution, and also of preparing derivatives by which it could after- wards be readily identified.Early in the research, the position of the chlorine atoms relatively to one another was readily shown to be 1 : 2 : 4, but as both formulae conform in this respect, the position of the carboxyl group was still uncertain, and many attempts were made to determine its position by preparing nitro- and other derivatives of the acid, but no definite evidence was thereby obtained. The position of the carboxyl group was finally fixed by a process of elimination, I n formula 11, both ortho-positions relatively to the carboxyl group are replaced by chlorine, and as Victor Meyer and his pupils have shown in similar cases, the acid thus constituted should not be capable of esterification by the action of hydrogen chloride and alcohol.As the new acid is found to yield an ester readily under :these conditions, i t follows that formula I1 is inadmissible, and that the substance is 2 : 3 : 5-brichloro- benzoic acid. EXPERIMENTAL. Eenxonitvile Hexachloride and Alcoholic Xoda. Benzonitrile hexachloride was warmed with excess of alcoholis sodium hydroxide. The alkali first removes three molecular propor- tions of hydrogen chloride, the hydrolysis of the cyano-group taking place subsequently when the solution is boiled. On completion of the reaction, and when no further evolution of ammonia was observed, the mixture was treated with excess of hydrochloric acid, and the precipi-MATTHEWS : 2 : 3 : 5-TRICHLOBOBENZOIC ACID. 45 tated acids, after thorough washing, were converted into the barium salts by boiling with water and excess of barium carbonate.On fractional crystallisation, the barium compound was found t o be a mixture, and, with some difficulty, a nearly pure barium salt was obtained, which gave the following figures on analysis : 0-3140 gave 0.0269 H,O and 0.1144 BaSO,. H,O = 8-56; Ba = 21.42. C,,H,O,CI,Ba,3H,O requires H,O = 8.44 ; Ba = 21.42 per cent. The acid obtained from this salt melted at 156'. It was afterwards found that neither it nor the barium salt was quite pure, and as a much better process for the preparation of the acid was found, the decomposition of the nitrile by means of sodium hydroxide was abandoned. Benxonitde Hexccchloride and Quinoline. Preparation of 2 ; 3 : 5-Y'ri- The removal of three molecular proportions of hydrogen chloride from benzonitrile hexachloride can be more conveniently effected by interaction with quinoline than with sodium hydroxide, and as the trichlorobenzonitrile is volatile with steam, it is easily obtained in a pure condition.The method by which the preparation was carried out is as follows. Ten grams of benzonitrile hexachloride are placed in a 30-40 OZ. fractionating flask, and treated with quinoline in slight excess. No reaction takes place in the cold, but on warming, the nitrile dissolves, and decomposition occurs, indicated by the change in colour of the solution. The reaction, once started, proceeds without any further application of heat, although towards the close it may be advisable to heat slightly in order to complete it.The solid mixture, when cool, is treated with slight excess of dilute sulphuric acid and subjected to distillation with steam, the almost colourless solid trichlorobenzonitrile distilling over readily. After recrystallisation from alcohol, the tri- chlorobenzonitrile was analysed, with the following result : chlorobenzonitrile. 0.1026 gave 0.21 41 AgCl. C1= 51.62 C7H,NCI, requires C1= 51 57 per cent, 2 : 3 : 5-ITrichZorobenzonitrile crystallises from aqueous alcohol (50-*60 per cent,) in beautiful, long, white, lustrous needles which melt sharply at 87'. It has a most nauseating odour, is readily volatile with the vapour of water or alcohol, dissolves easily in all the ordinary organic solvents, and'is readily hydrolysed by alcoholic alkali hydroxides, forming a salt of the corresponding benzoic acid,46 MATTHEWS : 2 : 3 : 5-TlU.CHLOROBENZOIC ACID.2 : 3 ; 5-Trichlorobsn~oic acid. The acid can be obtained by precipitation of a solution of the potass- ium or sodium salt with a mineral acid, and may be purified either by recrystallisation from water or by conversion into the barium salt. It crystallises from hot water in small, colourless needles. In cold water, it is practically insoluble. It melts a t 163O without decomposition. It is very soluble in most ordinary organic solvents, but large crystals have not been obtained from any solution. It does not volatilise with steam. On analysis, the following figures were obtained : 0.3464 gave 0.6606 AgC1. C1= 47.18. C7H,02CI, requires C1= 47.23 per cent.In order to determine the position of the chlorine atoms, an attempt was made to remove carbon dioxide from the acid by means of caustic baryta. On heating together 2 grams of the pure acid with excess of baryta, a very violent reaction resulted in the loss of all the material employed. A more successful result was attained in the following manner. Two grams of acid were heated in a sealed tube with sul- phuric acid (75 per cent.) for 29 hours at 300O. On opening the tube there was a considerable pressure of gas and a good deal of charring had taken place, but on the surface of the almost black sulphuric acid a nearly colourless layer of oil was floating, This was extracted with ether and the ether distilled off, an oil being left which had the odour of trichlorobenzene and remained liquid on standing.To prove its constitution, it was nitrated and the solid nitro-compound obtained, after purification, melted a t 58-59'. The oil, therefore, was 1 : 2 : 4- trichlorobenzene, and the position of the chlorine atoms, relatively to one another in the original acid, was thus fixed. The barium salt, (C,H,Cl3=CO2),Ba,3I2O, is readily prepared in the pure state by boiling together in water a mixture of the acid and excess of barium carbonate until no further action takes place. On filtering off the excess of barium carbonate and concentrating the solution, the barium salt crystallises out in very characteristic lustrous thin plates. The appearance of the crystals is much altered by the presence of even very small quantities of other substances.The salt is readily soluble in hot water but only sparingly so in cold, being much less soluble than the corresponding strontium and calcium salts ; it is therefore the best salt to select for purifying the acid. 0.4245 gave 0.0353 H,O and 0,1547 BaSO,. H,O = 8.32 ; Ba= 21.58. The strontium salt, (C,H,C'l,*C02),Sr,3H,0, is prepared similarly 0.2436 ?) 0.4642 AgC1. C1= 47.14. On analysis : C,,H,0,CIGBa,3H,0 requires H,O = 8.44 ; Ba = 2 1.42 per cent.MATTHEWS : Z : 3 5-TRICHLOROBENZOIC ACID. 47 to the barium salt, analysis : It crystallises in fine colourless prisms. On 0,4351 gave 0,0401 H,O and 0.1339 SrSO,. H20= 9.22 ; Sr = 14.68. The calcium salt, (C,H2Cl3*CO2),C'a,4H20, prepared similarly to the On C,,H4O4Cl6Sr,3Hz0 requires H,O = 9.15 ; Sr = 14.82 per cent.barium salt, crystallises from water in beautiful, lustrous needles. analysis : 0.1831 gave 0.0234 H20 and 0.0439 CaSO,. H20 = 12.78 ; Ca= 7.05. The silver salt, C6H,C1,*C02Ag, is prepared by the double decom- position of a hot solution of any of the above salts with silver nitrate, and crystallises in rosettes of needles. It is anhydrous and almost insoluble in cold water, but dissolves slightly on heating. On analysis : C,,H,0,CI,Ca,4H20 requires H20 = 12.65 ; Ca = 7.13 per cent. 0.2199 gave 0.0940 AgCl. Ag = 32-17. The low result is due to the difficulty of completely decomposing the salt with hot strong hydrochloric acid, The salt is not sufficiently soluble in hot water to obtain a solution from which the silver can be precipitated. The chloride, C,H,CI,*COCl, was obtained by the action of excess of phosphorus pentachloride on the acid.After the action ceased, the mixture was thrown into cold water, when an oil separated which very soon solidified; this was dried and then dissolved in hot benzene. On evaporation, an oil was again left which crystallised when cold, and melted at 36". This was again crystallised by spontaneous evaporation from a solution in ethyl acetate and the crystals thus obtained also melted a t 36O. On analysis : C,H202CI,Ag requires Ag = 3250 per cent. 0.1440 gave 0.3380 AgC1. C1= 58.06. C7H,0C1, requires C1= 58.19 per cefit. The anzide, C6H,CI,*CO*NH2, prepared by the action of ammonium carbonate on the acid chloride, crystallised from hot dilute acetic acid in small needles melting a t 204-205".The same substance has also been obtained by the action of quinoline upon the hexachloride of benzamide. This reaction does not yield a single product, as the amide obtained has to be recrystallised several times before the melting point above mentioned is reached. The puri- fied amide from this source was hydrolysed, and the acid thus obtained was compared, by means of its salts, with t h e acid prepared from tri-48 MATTHEWS : 2 : 3 : 6-TRICHLOROBENZOIC ACID. chlorobenzonitrile, when the identity of the two was established. analysis : On 0,1037 gave 0,1973 AgCI. C1= 47.07. C7H,0NC13 requires C1= 47.43 per cent. Yrichloronitrobenxoic Acid, N0,*C,HC13*C02H. Trichlorobenzoic acid is readily nitrated, The acid dissolves at once in fuming nitric acid on warming.On allowing the mixture t o stand a t a temperature of about 60° for some hours and then diluting with water, a yellowish oil separates which soon crystallises. This acid, on recrystallisation from alcohol, melts sharply at 158'. The fact that it is a mononitro-acid was ascertained by the preparation and analysis of its barium salt. Some of the acid was boiled with hot water, under which it fused, and excess of barium carbonate was added ; the acid dissolved gradually and, after filtration and evaporation, a harium salt was obtained which crystallised in yellowish, flat needles having a silky lustre. On analysis : 0.3322 gave 0°0423 H,O and 0.0980 BaS04. H,O = 12-73; Ba = 17.35- 0.5522 ,, 0.0657 H,O. H20= 11.89. C,,H,08N,Cl,Ba,5H20 requires H,O = 11 *75 ; Ba = 17.8 per cent.The want of sharpness in these figures is probably caused by the presence of a small amount of the barium salt of a dinitro-acid. On losing its water of crystallisntion, the substance becomes bright yellow in colour. Many unsuccessful attempts mere made to remove carbon dioxide from the acid and from the barium salt in order to obtain the corre- sponding trichloronitrobenzene, and thus throw light upon the consti' tution of both the trichlorobenzoic acid and its nitro-derivative, Heat- ing with lime or baryta gave too vigorous a reaction, and decomposition in a sealed tube at 250-300' with '75 per cent. sulphuric acid gave chiefly tarry substances, although in one experiment a very small amount of a crystalline substance was isolated.It could not be identified, however, as the present literature of the trichloronitro- benzenes is far from complete. A dinitro-acid is also produced by the action of a mixture of strong sulphuric and nitric acids on the mononitro-acid. It gave a barium salt which crystallised from water in canary-yellow, nodular masses. As no definite evidence as to constitution was obtained by its means, it was not further investigated. Attempts were also made to reduce the mononitro-acid to the corre- sponding amino-derivative. With sodium amalgam, an acid mas ob-THE NITRATION OF BENZENEAZOSALICYLIC ACID. 49 tained which crystallised from alcohol in colourless needles, melted sharply at 228O, and gave a bright grass-green copper salt on precipi- tating its solution with cupric acetate. As, however, in the meantime, definite evidence of the constitu- tion of the trichlorobenzoic acid was obtained by another method, the investi*tion of these compounds was not carried further. Efhy2 Tichloroberazoctte.-Since the trichlorobenzoic acid must have one of the formulae .previously mentioned, an attempt was made to esterify it by means of hydrogen chloride and aleohol. Two grams of the pure acid were dissolved in absolute alcohol and the mixture was saturated with hydrogen chloride and allowed t o stand over- night. On the addition of water, an oil was precipitated which smelt like ethyl benzoate, but less powerfully; this was washed with sodium carbonate solution and water and thoroughly dried but after standing for one month did not crystallise. 14 volatilised with steam fairly readily, but after purification in this way still remained liquid. On analysis : 0.2132 gave 0.3611 AgCL C1= 41.90. C,H70,C1, requires C1= 42.01 per cent, This result agrees well with that required for ethyl trichloro- benzoate, and on this evidence the constitution of the trichloro- b,enzoic acid (C0,H : GI,= 1 : 2 : 3 : 5 ) is considered to be proved. THE ROYAL INDIAN ENGINEERINU COLLEGE, COOPERS HILL.

ISSN:0368-1645    

DOI:10.1039/CT9017900043

出版商:RSC    

年代:1901

数据来源: RSC

摘要:

THE NITRATION OF BENZENEAZOSALICYLIC ACID. 49 11.-The Nitration of Benzeneaxosalicy lic Acid. By J. T. HEWITT and J. J. Fox. ALTHOUGH nitro-derivatives of benzeneazosalicylic acid have already been described, the compounds have been produced by coupling a diazotised nitraniline with salicylic acid, and hence contained the nitro-group in the benzene nucleus. By this process, Meldola (Trans., 1885, 47, 666) obtained p-nitrobenzenertzosalicylic acid, and Gebek the corresponding mets-derivative (Annalen, 1888,251,188). Isomeric com- pounds containing a nitro-group in the salicylic acid residue have not hitherto been described, although from the results obtained on submit- ting benzeneazopheaol to the action of warm dilute nitric acid (Trans., 1900, 77, 99) it appeared very probable that a benzeneazo-o-nitro- salicylic acid should be formed by a similar nitration of benzeneazosali- cylic acid.As a matter of fact, benzeneazosalicylic acid furnishes VOL. LXXIX. E50 HEWITT AND FOX: THE NITRATION OP a nitro-derivative different from any of the nitrobenzeneazosalicylic acids, and the compound produced was found to be identical with a synthetical benzeneazonitrosalicylic acid, in which the nitro-group stood in the ortho-position relatively t o the hydroxyl group, On the other hand, benzeneazosalicylic acid nitrated in concentrated sulphuric acid solution furnished p-nitrobenzeneazosalicylic acid, the reaction therefore being quite analogous to that observed by Noelting (Ber., 1887, 20, 2997) in the case of benzeneazophenol. This observation furnishes an indirect proof that even the azosalicylic acids are con- verted into quinonehydrazones by strong acids, although no sa.lts with such acids have been isolated.CO,H Be~xeneaxo-o-nitrosaZ~c~Z~c Acid, C,H, =N: N-' 'OH - \-/ * NO2 Ten grams of benzeneazosalicylic acid were made into a paste with 45 C.C. of water and 20 C.C. of nitric acid (sp. gr. 1*36), and warmed gently to 65-70'. The thermometer suddenly rose to about 8 5 O , nitrous fumes were evolved, and a reddish, pasty mass resulted. This was quickly poured into water, cooled, and the flocculent precipitate collected and washed free from nitric acid with cold water. The sub- stance, after drying, was usually found t o weigh 58 to 6 grams, and to melt between 160' and 170'. After two recrystallisations from dilute alcohol, a substance melting constantly at 19'7' * was obtained. The substance separates in clusters of small, yellowish-red needles ; it is easily soluble in alcohol, acetone, or glacial acetic acid, whilst it is also fairly easily soluble in boiling water.The solubility in hydrocarbon solvents is, however, slight. On analysis, results were obtained show- ing that the substance, crystallised from dilute alcohol and air dried, contains one molecular proportion of water of crystallisation. 0.8456 lost 0.0498 on drying a t 1104 0.1100 gave 13.2 C.C. moist nitrogen at 19' and 756 mm. N= 13.72. H,O = 5.88. C,,H,O,N,,H,O requires H,O = 5-90 ; N = 13.80 per cent. The dried sub.stance was also analysed : 0.0807 gave 0,1619 CO, and 0.0225 H,O.0.1112 C = 54.72 ; H= 3-18. ,, 15.5 C.C. moist nitrogen at 23' and 746 mm. N = 15.31. In order to determine the constitution of the substance, various un- successful attempts were made to remove the carboxyl group. It was thought that prolonged heating with acetic anhydride might effect the * This melting point as well as the others given in this paper ar0 not corrected for the apparent coefficient of expansion of mercury. C,,H,O,N, requires C = 54.32 j H = 3.1 6 ; N = 14.66 per cent.BENZENEAZOSALICYLIC ACID. 51 elimination of carbon dioxide, whilst the hydroxyl group would be acetylated a t the same time. Instead of this, the carboxyl group was found to be very firmly attached, and this and the nitro-group being both in ortho-positions relatively t o the hydroxyl, protected the latter from acetylation.Heating in a reflux apparatus with benzoyl chloride led t o the production of tarry substances, from which no crystalline matter could be isolated. The process of heating the barium salt with an excess of caustic baryta was also a failure, explosion regularly occurring as soon as a temperature of 155' was reached. The substance had of necessity to be compared with a synthetical product obtained by coupling phenyldiazonium chloride with an alkaline solution of nitrosalicylic acid, [CO,H : OH : NO,= 1 : 2 : 31. The latter compound was obtained by nitration of salicylic acid in an acetic acid solution, and separated from the 1 : 2 : 5-isomeride by Hubner's method (Annulen, 1879, 195, 6), which depends on the sparing solubility of the barium salt of the 1 : 2 : 3-compound.The purity of the nitrosalicylic acid was checked by the melting point. I n coupling the nitrosalicylic acid with diazonium compounds, the same difficulty is experienced as in the case of o-nitrophenol, reaction taking place slowly and incompletely. Since the diazonium salt yields decomposition products difficult of removal, it is as well to use the nitrosalicylic acid in slight excess. The process consists in adding a well-cooled solution of phenyldiazonium chloride to an alkaline solution of nitrosalicylic acid, and allowing the interaction to proceed for three days in a cool place ; the solution is then filtered from de- posited matter and acidified. The precipitate contains the desired azo-compound mixed with a considerable excess of nitrosalicylic acid, To effect a separation, the mixed acids are dissolved in hot dilute ammonia solution and ammonium and barium chlorides added.Barium o-nitrosalicylate, although easily soluble in boiling water, is very spar- ingly-soluble in the cold, whilst the barium salt of the azo-acid dissolves very slightly even in boiling water, The precipitate obtained con- sists essentially, therefore, of barium benzeneazo-o-nitrosalicylate, and if the acid is liberated from the salt and the process of purification by means of the barium salts repeated, it is obt'ained in such a condition that when mixed with the product of direct nitration no depression of melting point is observed. I n addition to this direct proof of the constitution of the azo-acid, it may be mentioned that by reduction of an alkaline solution with hydrogen sulphide, aniline as one of the fission products may be detected with the greatest certainty by the ordinary reactions (volatility with steam, isonitrile reaction, bleaching powder test, and production of tlibromoaniline).We have been unable to isolate the E 252 HEWITT AND FOX: THE NITRATION OF diaminosalicylic acid, which must form the other fission product, on account of its ready oxidisability. Benzeneazo-o-nitrosalicylic acid dissolves in concentrated sulphuric acid with a far yellower shade than benzeneazosalicylic acid ; possibly the nitro- and carboxyl groups in the ortho-position relatively to the hydroxyl exert a sufficient attraction on the hydrogen of the hydroxyl to prevent isomerisation of the compound to the quinone- hydrazone form.This subject will, it is hoped, be further examined ; if it were found that nitration in concentrated sulphuric acid solu- tion led to the production of p-nit;robenzeneazo-o-nitrosalicylic acid, it would at least be rendered probable that isomerisation had taken place. A solution of the acid in ammonia or fixed alkalis is red in colour. The ammonium salt was found to furnish the following precipi- tates : Xilver Nitrate.-Concentrated solutions give an orange precipitate somewhat soluble in water and easily soluble in ammonia. Lead Acetate.-Yellowish-red precipitate insoluble in hot water. Mercuric Chloride.-A yellow precipitate, somewhat soluble in a large quantity of water. Stannous Chloride.-A yellow precipitate even in dilute solutions. This dissolves on warming, and does not appear to come down again on cooling, Excess of sodium hydroxide gives a deep red solution turned to a light red shade by excess of dilute hydrochloric acid.Ferrous Su&hate.-A chocolate-coloured precipitate,:turning greenish- brown on warming, The liquid becomes at the same time deep red. Ferric Cldoride.-A dark red solution and precipitate. Cobalt Nitrate.-A yellow precipitate soluble in hot water. Nickel SuZplmte.-A dirty yellow precipitate soluble in hot water. Magnesium Cl&wide.-An orange precipitate slightly soluble in hot water. Barium and Calcium ChZorides.-Orange precipitates, soluble in a large quantity of boiling water. Dyeing experiments were also made, Wool mordanted with iron gives a rich brown, with alumina a bright yellow, and with potassium dichromate, a dull yellow shade.The methyl ester was prepared from 2 grams of the acid, 10-12 grams of methyl alcohol, and 1 C.C. of sulphuric acid. The mixture was warmed in a reflux apparatus for 5 hours, poured into water aFter the greater portion of the alcohol had been distilled off, and the pre- cipitate collected, washed, and recrystallised from spirit. The substance forms small, brown needles melting at 132-134".BENZENEAZOSALICYLIC ACID. 53 0.0827 gave 0-1675 CO, and 0.0294 H,O. 0.1080 ,, 12.6 C.C. moist nitrogen a t 18' and 760 mm. N = 1.348. 0.1094 ,, 13.2 C.C. ,, 18' ,, 759 mm. N=13.92. The ethyl ester was prepared in a similar manner from the acid, sul- It forms very small, N = 12-91.C = 55-23 ; H = 3.95. $ 9 C,,H,,O,N, requires C = 55.77 ; H = 3.68 ; N = 13.96 per cent. phuric acid, and 95 per cent. ethyl alcohol. yellow needles melting at 128-129'. 0.1290 gave 14.7 C.C. moist nitrogen a t 22' and 760 mm. p-Nitrobenaeneazosalicylic cccid has already been described by Meldola (Trans., 1885, 47, 666). It may be obtained by gradually adding 2.1 grams of powdered pobassium nitrate, in small portions a t a time, to a solution of 5 grams of benzeneazosalicylic acid in 100 C.C. of concentrated sulphuric acid. Care should be taken that the tem- perature does not rise above 20' during the operation ; the mixture is then allowed to stand in the cold for 48 hours, after which it is poured into a large volume of water, collected, washed free from acid, and dried.The substance is already practically pure and the yield nearly theoretical. On recrystallisation, it was obtained as brilliant red needles. Meldola states that the melting point of the substance cannot be observed on account of blackening taking place above 225'. Our specimen, as well as one obtained from diazotised p-nitraniline and salicylic acid, did not blacken until a considerably higher tem- perature was reached, and by immersing the melting point tubes in sulphuric acid previously heated to 245--250', both specimens were observed to melt a t 253-254' (uncorr.), decomposition and blackening then taking place. The two preparations when mixed showed no de- pression of melting point. 0.1124 gave 14.7 C.C. moist nitrogen at 16' and 750 mm. N = 15.04. C,,H,O,N, requires N = 14.66 per cent. The ethyl ester of this acid was prepared from both specimens in the usual manner. Each preparation melted at 220-225', a certain amount of decomposition taking place. 0.1165 gave 14.3 C.C. moist nitrogen a t 23' and 759 mm. N = 13.82. C,,H,,O,N, requires N = 13-33 per cent. Both the m- and p-nitrobenzeneazosalicylic acids resist the action of dilute nitric acid to a greater degree than the unsubstituted acid. At- tempts at nitration, even at loo', led t o the recovery of nearly the whole of the original acids in an unchanged condition. C,,HI30,N, requires N = 13.33 per cent. On analysis : EAST LONDON TECHNICAL COLLEGE.

ISSN:0368-1645    

DOI:10.1039/CT9017900049

出版商:RSC    

年代:1901

数据来源: RSC

摘要:

5 4 YOUNG AND EYRE: OXIDATION OF 111.-Oxidation of Benxalthiosemicarbaxone. By GEORGE YOUNG, Ph.D., and WILLIAM EYRE, B.Sc. IT has been shown by Marckwald (Bey., 1892, 25, 3098; 1899, 32, 1081) that certain thiosemicarbazides, for example, C,H,*NH*N:C(SH) *NIT,, exist in two forms, of which the labile modification when treated with phosgene yields a mercaptotriazole, whilst the stable form with the same reagent yields an aminothiodiazolone. This difference, Marck- wald ascribes to stereoisomerism, thus : Young and Witham having found that benzalsemicarbazone could be oxidised by ferric chloride to phenylhydroxytriazole (Trans., 1900, 77, 224), C,H,*CH:N*NH*CO*NH, - C,H5*C< N>C*OH, we thought it might be of interest to apply the same reaction to benzalthiosemicarbazone in order t o determine, if possible, whether this compound would act as a mixture, or as one or the other of the two possible stereoisomeric forms : N*NH The substance represented by formula I would yield a n amino- phenylthiodiazole, 111, whilst that represented by I1 would yield a phenylmercaptotriazole, IT.The oxidation of benzalthiosemicarbazone . by ferric chloride takes place much more easily than that of benzalsemicarbazone ; the latter requires to be heated with an alcoholic solution of ferric chloride in sealed tubes a t 130-140°, whereas the thio-compound is oxidised by aqueous ferric chloride between 70" and 80°. The product consists almost entirely of the hydrochloride of a base which has the properties to be expected of an aminothiodiazole. I n one or two ex- periments, there was also obtained a trace of R substance of high melting point and soluble in alkali, which may have been the mer-BENZALTHIOSEMICARBAZONE. 55 captotriazole, but the quantity obtained was too small to admit of purification.Benzalthiosemicarbazone reacts, therefore, with ferric chloride almost, if not entirely, as if i t had the constitution represented by formula I. Changes in the conditions under which the oxidation took place produced no effect on the nature of the product. We endeavoured, but without success, to obtain a second form of benzalthiosemicarbazone. Our results being negative do not preclude the possibility of a second form, but, on the other hand, the substance may be tautomeric, and might, with another oxidising agent, yield the mercaptotriazole in the same manner as, according to Marckwald and Bott (Bey., 1896, 29, 2 9 14), benzoyl-4-phenylthiosemicarbazide yields phenylamino- phenylthiodiazole when treated with acetyl chloride, but diphenylmer- captotriazole when acted on by excess of benzoyl chloride, or when heated above its melting point, C,H, c<,>c N*N NH*C6H5.C,H,* C0.NH.N: C( SH)*NH* C,H, < C,H,*U<zFH$>C*SH. Benzal-4-phenylthiosemicarbazone and benzal-4-methylthiosemicarb- azone undergo oxidation by ferric chloride to the corresponding phenyl- amino- and methylamino-phenylthiodiazole : Traumann (Annulen, 1889, 249, 53) showed that the aminothiazoles can be equally well represented as iminothiazolines : HE-N HR*NH HC-S HC-S >C:NH. >C*NH, or Gabriel (Ber., 1889, 22, 1144; 1898, 31, 2832) found the amino- H,C*N thiazolines, H$+s>C*NH2, to react sometimes as such, sometimes as the tautomeric form, H2Y*NH H,C--S >C:NH.The aminothiodiazoles discussed in this paper are very similar in structure to the above compounds, and although we make use, as far as possible, of the " amino " nomenclature and constitutional formulze, the reactions and properties of our substances might be represented just as well by the '' imino " constitution. The structure of the methyl and acetyl derivatives of aminophenyl- thiodiazole is of some interest in connection with the work of Pulver- macher and of Freund on the aminothiodiazoles. Pulvermacher (Ber., 1894, 27, 61 3) found that phenylaminothiodi-56 YOUNG AND EYRE: OXIDATION OF azole on methylation aDd subsequent decomposition yielded aniline and methylamine, and he therefore gave to the base, the methyl deri- vative, and the acetyl derivative the respective formulae : Freund and Meinecke (Ber., 1896, 29, 251 1) methylated aminothio- diazole and aminomethylthiodiazole, and by comparison with the cor- responding synthetical bases prepared by Pulvermacher, determined the constitution of the methyl derivatives to be CHq8 N N(CH .3>C:NH ) and CH3*C<N"(CHs1>C:NH, S- and, following Pulvermacher's example, assumed that the acetyl derivatives were similarly constituted : Ami-nophenylthiodiazole yields with methyl iodide a methyl deriva- tive which is isomeric, and not identical with the methylaminophenyl- thiodiazole which we have prepared by the oxidation of benzal-ri-methyl- thiosemicarbazone : C,H,*CH:N*N:C(SH)*NH*CH, - C,H,*C<,->C*NH*CR,. N=EJ To the methyl base prepared by methylation and to its acetyl deri- vative, we must ascribe the constitutional formulze : Aminophenylthiodiazole yields with acetic anhFdride an acetyl derivative which has distinctly acid properties.It is easily soluble in dilute alkalis, and forms stable sodium and silver derivatives. The action of methyl iodide on the silver acetyl compound yields a methyl acetyl derivative which is identical with the above acetyl derivative of the methylated aminophenylthiodiazole. The acetyl derivative of aminophenylthiodiazole must therefore have the constitution We consider that there is no ground for the assumption that the methyl and acetyl groups take up the same position when an amino- thiodiazole is methylated or acetylated, and as our acetylaminophenyl- thiodiazole closely resembles the acetyl derivatives described by FreundBENZALTHIOSEMICARBAZONE.57 and Meinecke, we are of opinion that the constitution which they ascribe to theseacetyl compounds is open to doubt, and that their substances would be better represented by the formulae : HC<i>C*NH-CO*CH,, N N and CH,*C<~~>C*NH-CO*CH,. The acetyl derivative of methylaminophenylthiodiazole has probably the constitution : EX P ERI M ENT AL. Benxalt~~ioseinicurbaxons, C,H,* CH : N* N C( SH) *NH,.-T h iosemi- carbazide, prepared according to the method described by Freund and Imgart (Ber., 1895, 28, 948), was dissolved in warm alcohol and benzaldehyde added.On cooling, part of the benzalthiosemicarbazone crystallised ont in hair-like needles, and the remainder was precipitated by the addition of water. Benzalthiosemicarbazone is easily soluble in warm alcohol, and slightly so in boiling water, from which it crystallised, on cooling, in long, thin, shining plates which melted at 156'. After recrystal- lisstion from alcohol, the substance melted at 159-160'. Benzalthiosemicarbazone has slightly acid properties, as it is fairly soluble in caustic soda, and is reprecipitated by dilute hydrochloric acid. 0.2140 gave 0.2716 BaSO,. S = 17.41. C,H,N,S requires S = 17.87 per cent. Benzalthiosemicarbazone is easily oxidised by aqueous ferric chloride. The oxidation commences at about 70'.The best results were obtained by suspending the benzalthiosemicarbazone in water, adding rather more than one molecular proportion of ferric chloride, and warming for half an hour in a water-bath at 80-90°. After filtering from a small amount of solid matter A, the filtrate was slightly ccncentrated, if necessary, and and allowed to cool. The hydrochloride of the oxidation product crystallised out in white needles which, after recrystallisation, melted at 213 -214". Further quantities of less pure hydrochloride were obtained by concentrating the mother liquors. The hydrochloride contains one molecular proportion of water of crystallisation, which is given off at 90'. 0.2904 gave 0*1810 AgC1. HC1 e 15-86. 0.51'72, at 90°, lost 0.0420 H,O.0.3312, dried at 90°, gave 0.2182 AgC1. H,O = 8-12. HC1= 16-76. C,H?N,S,HCl requires HC1= 17.10 per cent. C,H,N,S,HCl,H,O requires HC1= 18-76 ; H,O = 7.77 per cent.58 YOUNG AND EYBE: OXIDATION OF The solid matter, .A, consisted principally of unchanged benzalthio- semicarbazone, but in some experiments contained also a very small amount of a , substance of higher melting point which was soluble in alkalis. This substance, which was not further investigated, may have been the mercaptotriazole isomeric with the base which formed the chief product. Aminophenylthiodiccxole, C,H,* C<!3C NH, .-T he hydrochloride obtained by the oxidation of benzalthiosemicarbazone was dissolved in water and excess of ammonia added. The precipitated base on re- crystallisation from 50 per cent.alcohol, formed colourless, micro- scopic hexagonal plates which melted a t 222-2233. 0.2148 gave 0.4294 CO, and 0*0800 H,O. 0.2570 ,, 55 C.C. moist nitrogen at 23' and 755.2 mm. N = 23.96. 0.2456 ,, 0,3194 BaSO,. S=17.83. C,H,N,S requires C = 54.24 ; H = 3.95 ; N = 23.72 ; S = 18.08 per cent. The base is easily soluble in dilute acids. On addition of concen- trated hydrochloric acid to the solution in dilute acid, the hydrochloride described above is obtained. C = 54-52 ; H= 4.14. Acetykaminophenylthiodiazole, C6H5* C<s>C*NH* N*N CO* CH,.-The base was added to an equal weight of acetic anhydride. The mixture rapidly became hot and soon solidified. The product on recrystal- lisation from boiling alcohol formed small needles which melted at 276'.0.3052 gave 0.3214 BaSO,. The acetyl compound is very slightly soluble in water, moderately so in boiling alcohol, and easily so in aqueous alkalis. A sodium derivative is precipitated by the addition of concentrated aqueous caustic soda to the solution in the dilute alkali. The silver derivative was prepared by dissolving the acetyl com- pound in dilute ammonia and running the solution into aqueous silver nitrate. S = 14.44. C,,H,ON,S requires S = 14.6 1 ;per cent. The white precipitate was washed with water and alcohol. 0.1742 gave 0.0576 Ag. Ag = 33.07. CloH80N,SAg requires Ag = 33.13 per cent. -The silver acetyl derivative was treated with methyl iodide and methyl alcohol, and after standing overnight was heated for half anBENZALTHIOSEMICARB AZONE. 59 hour a t 100' in a sealed tube.ing alcohol, formed prismatic needles melting a t 144'. The product, recrystallised from boil- 0.2378 gave 37.7 C.C. moist nitrogen at 14" and 751.2 mm. N = 18.43. 0,2578 ,, 0.2534 BaSO,. S= 13.48. Iminometl~yl~~en?lZthiodicczoline, C,H,* C<E*N(cH3)>C:NH.- Aminophenylthiodiazole was heated with methyl iodide and methyl alcohol in a sealed tube f o r 1 hour a t 100'. On cooling, the hydr- iodide of the new base crystallised out in large, Ant prisms which melted a t 245-246'. On addition of aqueous caustic potash to the hydriodide, the base separated as an oil. The hydrochloride melts at 218-219', and the platinichloride at 217-218'. On analysis of the latter : C11Hl,0N3S requires N = 18.03 ; S = 13.73 per cent. 0.3134 gave 0.0776 Pt.Pt=24.76 On adding the base to acetic anhydride heat was developed and on cooling the acetyl derivative crystallised out. This compound has the same melting point (144O) and crystalline appearance as the acetylimino- met hylphenylthiodiazoline described above. It was analysed with the following result : 0.1410 gave 22.4 C.C. moist nitrogen at 16.5'and 744.2 mm. N = 18.08. (CgH,N3S)2,H2PtCI, requires Pt = 24.62 per cent. C,,H,,ON,S requires N = 18.03 per cent. Benzal-4-methylthiosemicarbazone, C,H,*CH:N*N: C( S H) *NH* CH,, was prepared according to Pulvermacher's directions (Be?.. , 1894, 27, 623) and its properties agreed with his description. 0.1368 gave 26.2 C.C. moist nitrogen a t 16'and 740.0 mm. N = 21.72, This compound was oxidised with ferric chloride in exactly the same way as benzalthiosemicarbazone.The hydrochloride which separated was treated with aqueous caustic potash and the base thus obtained was crystallised from alcohol. C,HgN3S requires N = 21 *76 per cent. moderately soluble in hot alcohol, from which it separates in shining plates melting at 183-184'; it is fairly soluble in benzene, from which it crystallises in flat needles, and very slightly soluble in hot water from which i t is deposited in microscopic, rough needles. 0-0950 gave 18.3 C.C. moist nitrogen at 15' and 744.2 mm. N= 22.07. C9H,N3S requires N = 21.99 per cent,60 OXIDATION OF BENZALTHIOSEMICARBAZONE. From the hydrochloride a platinichloride was prepared which melted a t 208-209*. 0.5526 gave 0.1352 Pt. Pt = 24.46.(C,H,N3S),,H,PtC16 requires Pt = 24.62 per cent. Meth ylccce t y Zaminophen y Zthiodiazole, C,E,* C@iy>C *N<' CO*CH,'- H3 Methylaminothiodiazole was added to an excess of acetic anhydride. The acetyl compound crystallised from alcohol in long needles which melted at 1959 0.1314 gave 20.6 C.C. moist nitrogen at 15' and 744.2 mm. N = 17.99. CllHIION,S requires N = 18.03 per cent. Benzal-4-phen ylt hiosemicarbazone, C,H,*CH : N-N : C( SH)*NH* C,H,, mas made by the action of benzaldehyde on 4-phenylthiosemicarbazide. It melted a t 190' and agreed in its properties with those described by Pulvermacher (Zoc. cit.). It was boiled for half an hour with an alcoholic solution of ferric chloride. The product, which separated on dilution and evaporation of the alcohol, was treated with caustic soda. The resulting base, which melted a t 199-200°, was easily soluble in boiling alcohol, It formed a hydrochloride insoluble in water but soluble in alcoholic hydrochloric acid. With acetic anhydride, it formed an acetyl derivative melting a t 140'. The properties of the base agree fully with Marckwald and Bott's (Zoc. cit.) description of phenylaminophen ylthiodiazole, C,H,*C<!L!>C NH- C,H,. 0.3464 gave 3.3266 BaSO,. When an alcoholic solution of the base is poured into alcoholic S= 12.35. Cl,HIlN3S requires S = 12.65 per cent. silver nitrate, a white precipitate is formed. On analysis : 0.6860 gave 0.2070 Ag. Ag= 30.17. Cl,HloN,SAg requires Ag = 30.00 per cent. This silver derivative when air-dried is stable at the ordinary tem- perature ; when suddenly heated, i t decomposes with explosive vio- lence and with the evolution of phenylisonitrile. UNIVERSITY COLLEGE, SHEFFIELD.

ISSN:0368-1645    

DOI:10.1039/CT9017900054

出版商:RSC    

年代:1901

数据来源: RSC

摘要:

SPECTROGRAPHIC ANALYSIS OF MINERALS, 61 JV.-A Simplified Method foy the Spectroyruphic Analysis of Minerals. By WALTER NOEL HARTLEY, F.R.S. and HUGH RAMAGE, F.I.C., A.R. C. Sc.1. PRIOR to the close of the eighteenth century the composition of minerals was never stated quantitatively, and even now in all cases where the analysis of a mineral is of importance, it is necessary first to know the nature of its constituents before determining their pro- portions. Testing by the blow-pipe mas first systematically employed by J. Gahn, and very extensively applied to mineral analysis by him and by Bergman (Thomson’s “Annals of Philosophy,” 1818, 40, 40-47. See Thornson’s “History of Chemistry,” 2, 199, edition of 1831) ; it was afterwards in many respects perfected by Wollaston and Plattner.Its application is limited when unaided by other methods, thus in minerals of a complex composition it is difficult t o detect small quantities of beryllia and some of the other rare earths when associated with alumina and magnesia. The method of dissolving minerals by the action of special solvents and separating their constituents by the addition of suitable precipit- ants was first systematised by Klaproth, and largely practised by Vauquelin, who not only improved analytical processes, but reduced the a r t of analysis to a greater degree of simplicity and precision. The work was advanced to a greater measure of perfection by Berzelius, Heinrich Rose, and many others down to the present day. This is the method pay excellence both for qualitative and quantitative purposes, but it is tedious when carried out in minute detail, and requires to be applied with considerable judgment, tact, and skill.It is frequently necessary to supplement it by other methods, as for instance in the detection of small quantities of beryllium, yttrium, cEsium, or rubidium. Spectrum analysis of minerals found a pioneer in Swan (Trans. Roy. SOC. Edin., 1853, 20, 335), the inventor of the collimator, and Bunsen, who with Kirchhoff devised the first serviceable spectroscope for the chemist’s use, and applied it practically to mineral analysis, It is hardly necessary to refer to the discoveries of gallium, indium, thallium, rubidium, and ciesium. Spectrum analysis is the only absolute method of diagnosing the chemical composition of a mineral, or of a substance separated by precipitation in the course of a chemical analysis. As no two substances can give the same spectrum, it follows that the spectrum of a substance is peculiar to itself, and, provided that light sufficient in amount and in purity can enter the instrument, i t is immaterial how far from a self-luminous object the62 HARTLEY AND RAMAGE: A SINPLIFIED METHOD FOR observer is distant.Moreover, it is possible to determine the com- position of materials too minute in quantity to be handled, and which cannot therefore be submitted to chemical analysis. llTe are also able to determine the composition of a substance the constituents of which are not amenable to any known process of chemical separation. Notwithstanding these advantages, this method in some directions does not completely satisfy the requirements of the chemist. It is desirable that a marked distinction should be drawn between chemical analysis, spectrum analysis, and merely chemical testing.The first implies the actual separation of the constituents of a sub- stance by taking advantage of their differences in volatility, solubility, or other chemical properties ; spectrum analysis is the separation in the order of wave-length of the rays proceeding from any material either self-luminous or not, and the identification of these rays with the presence of a substance whether element or compound to which these rays belong. This physical method when suitably modified in detail can very advantageously be employed as an aid to, and with certain limitations even instead of, chemical analysis.The Method of Spectrographic Anulysis. Oxyhydrogen flame spectra both of elements and compounds have been closely investigated and described by one of us and shown to be capable of very useful applications (Hartley, Phil. T~ans., 1894, 185, A, 161, 1029). Photographs of spectra are produced with extreme ease either from metals, oxides, or other compounds in the solid or liquid state. The alkali metals were proved to be volatilised from refractory silicates by reason of the high temperature em- ployed. A general application of this fact led to a method of examination being devised whereby the spectra of the alkalis can be separated from those of the alkaline earths even in a Bunsen flame (Hartley, Trans., 1893, 63, 138).We have also shown by a study of manganese slags and siliceous minerals containing this element that it can be volatilised in the oxyhydrogen flame by simply heating the silicate. Owing to the high :temperature to which the substances are sub- jected, it has already been shown that platinum wire supports are of no use, and fragments of a highly crystalline silicate of alumina in the form of the mineral kyanite have been substituted (Hartby, “Flame Spectra a t High Temperatures,” Phil. Trans., 1894, 185, A, 16s). Later it was found that little rods of pure alumina, also chips off the bowls of clay tobacco pipes, could serve the purpose of supports, and that solutions as well as solid salts, minerals, or metals could conveniently be examined therewith.THE SPECTROGRAPHfC ANALYSIS OF MINERALS.63 We propose now to give an account of a simplification of the method of obtaining these spectra, together with some examples of its appli- cation to the chemical analysis of very minute quantities of mineral substances, If the substance to be examined is a metal it should be in the form of filings, turnings, powder, or metallic sponge. If a mineral, it should be finely powdered. I n either case, the powder in quantity up to half a gram is rolled up in one-half of an (‘ ashless ” filter paper about 5 inches in diameter, the powder is spread equally over the paper with exception of a strip a t the edge, and is kept as near to the centre of the roll as possible, that it may be in the midst of the reducing gases given off by the paper when charred and in contact with the carbon.I n this manner a t so high n temperature, some oxides which are non-volatile or are volatilised with great difficulty, as they do not undergo dissociation in the flame, are actually reduced and a spectrum of the metal is thus obtained. F o r example, we find that certain lines in the spectrum of zinc and even that of aluminium may be photographed when the oxides are burnt in this way. AS regards the thermochemistry of the substance, this fact is of con- siderable interest because it informs us of the possibility of reducing aluminium oxide in presence of carbon a t the temperature of the oxyhydrogen flame. I n the electric arc the product is aluminium carbide. The lines referred to have approximately the wave-lengths 3962 and 3944, and correspond with two of the strongest lines of aluminium common to the arc and spark spectrum, namely, those with wave-lengths 3961.68 and 3944.26 (Kayser and Runge). I n front of the spectrograph is a quartz lens 3 inches in dia- meter, which projects on to the slit of the instrument the eimage of the flame from an oxyhydrogen blow-pipe.It is advisable to make the focal length of the lens 4 or 5 inches. That used by us has a focus of 3 inches, and molten particles which adhere to the quartz are liable to be projected on t o it, necessitating the repolishing of the lens. The flame may take a vertical or horizontal direction, or a direction inclined towards the optic axis of the instrument. The operator having placed the dark slide containing the sensitive plate in position and exposed it, protects his eyes by wearing very dark neutral tint or black glasses and, seated near the flame, introduces the point of the paper pencil containing the ore or mineral into the lowest part of the flame.As i t burns rapidly it is pushed farther in until it becomes necessary to hold the last two or three inches with platinum pointed forceps. Some minerals burn with sparks, others form fused globules which drop off, and care should be taken with these that they do not fall into and choke the oxygen jet of the blow- pipe. One pencil suffices, as a rule, to yield a strong spectrum. The64 HARTLEY AND RAMAGE: A SlMPLlFlED METHOD FOR time occupied in burning is about two minutes, and five spectra can very conveniently be photographed on one plate.A short spark spectrum is generally photographed on the middle of the flame spec- trum, by turning the slit of the spectrograph towards the spark emitted by an alloy giving well-known and clearly defined lines, from the measurements of which wave-lengths along the whole spectrum may be deduced by means of a curve. Of course it is advisable first of all to ascertain definitely the substances to be found in the filter papers used ; Sclileicher and Schull’s ashless filters generally gave weak lines of sodium, and weaker lines of potassium, calcium, and iron. These elements are present in the ash of the filter paper and the dust of the air. Precipitates may be collected on ashless filters and the paper burnt. If the precipitate be small, as, for instzznce, a few milligrams in weight, the paper is cut into strips and so burnt.The photographs are taken on Edwards’ ‘‘ Snap Shot ” isochrornatic plates or Cadett’s spectrum plates, and are developed with quinol, the development occupying from two t o three minutes, When burnt in the manner described, the lines in the spectra are not obscured by the emission of white light, but the presence of a large quantity of sodium salts is decidedly disadvantageous, inasmuch as it overpowers or suppresses weak lines of other elements. The spectra observed for the most part have already been described (Phil. Trans., 1894, 185, A, 168, 1029). In one or two cases we have considered it advisable to revise these spectra. The -water-vapour lines from the flame, the lines of iron, calcium, and sodium, may be very commonly observed.Precipitates show the spectrum of potassium in a manner which leads to no other conclusion than that this element remains in combination with insoluble hydr- oxides much more frequently than is generally supposed. The lines in the spectra are measured directly by applying an ivory scale to the photograph and clamping it to the glass as described else- where in the examination of absorption spectra (Hartley, Phil. Trans., 1885, 176, 471). We have used divided scales 4 inches long with 200 divisions to an inch. A very little practice with a sufficiently powerful magnifier or low-power microscope enables each division to be subdivided by judgment into fifths. With a curve constructed from the principal lines of iron and either Kayser and Runge’s wave-lengths or Rowland’s solar lines, we may determine the wave-lengths of any line so accurately that as a rule for the identification of lines of known wave-lengths nothing more is necessary.But occasionally it becomes desirable that wave-lengths be determined with still greater accuracy, and micrometer measure- ments are resorted to. As an example of what may be accomplishedTHE BPECTROORAPHIC ANALYSIS OF MINERALS. 65 in this manner, we give in a tabulated statement the lines observed in "blast furnace metal" from Middlesbrough, side by side with the lines with which they have been identified in the solar spectrum or in the arc spectrum of iron. It will be seen that the agreement between the wave-length numbers is very close.We proved the identity of the lines due to foreign metals by carefully executed chemical analyses aided by measurements from the photographs of the spectra of the various precipitated substances which were separated in the process, and not solely from the spectrum of the crude metallic iron. Lines may be identified in many spectra by simultaneous coinci- dences with groups of lines on photographed spectra of the elements, without precisely measuring their wave-lengths. In this case, the one plate is placed film to film against the other. Spectrogyaphic unulysis of the crude metal with which the converters are The iron wus heuted in the oxyhydrogen churged at Miclcllesbrough. same on suppwts of cyunite. Wave-leiigt hs of lines.(Row land's scale.) 5735'2 5622'2 5582'4 5371'7 5328'6 5270-2 4481 -7 61'5 27 *3 15'7 05.1 75 -8 25'5 07.9 4253.9 i 4 . 6 71-5 54'4 26'8 16.9 02 '4 4171'6 43'6 31 -4 4071% 63 '4 4383.1 Lines in solar spectiuiii for comparison. ( Rowland.) 5371 '686 5328 '696 5 328 *7 47 52iO-533 4482.336 61.81 8 27'482 15'293 04.927 4383*i20 76.1 07 25 939 L s s * I l y l 4269 853 i4.958 i l . 9 3 4 54 505 ~d 904 15.i2 01 98 417 2 '21 1 44.038 31'235 4071 '908 63'755 Remarks and references showing by figures the intensity of' the lines, (1) being the lowest. Narrow band Edge of band more refrangible. Edge of band more refrangible. Fe, C!r (7) Fe (2) Fe (2) Fe (4) Fe Fe (4) Fe (5) Fe ( 6 ) Ft! (10) Fe (15) Fe (6) Fe (8) Fe (6) Cr (5) Cr (7 d) Fe ( 6 ) Cr (8) ('a (20 d 1) lit), Rowland, also 4216'351 Fe (3 d P) KI), Itowland, also 4202'198 Fe (8) 3a (1) Fe (15) Pe (10) Fe (15) Fe ( Y O ) VOL.LXXlX. F66 HARTLEY AND RAMAGE: A SIMPLIFIED METHOD FOR Spectrographic cwlalysh, &c. (continued). Wave-lengths of lines. (Rowland's scale.) 4047.4 45 '8 44-0 34.5 33.2 31 '0 05 -3 3969.1 305 28 '0 22.8 20.0 06.4 3899-9 95.9 86.2 78.9 72.9 65.6 60.1 56.6 49.6 40 '2 34 '2 27.3 25-9 24 *5 20.6 15.6 1.2'6 3799'4 98'5 94'9 87'9 67'2 63.8 58'4 49 -3 48'2 45.8 37-4 35 '1 33 *3 27.9 22 '5 19'9 09.3 07'9 05.7 3687.1 83'6 79.9 47 '8 Lines in solar spectium for comparison. (Rowland.) 4047.338 45.975 44.294 34.641 33,224 30'914 05.408 3969 -413 30.450 28 *075 23.054 20.410 06.628 3 89 9 -8 50 95-803 86.421 78'720 72.639 65'674 60.055 56-524 50,118 40'580 34'364 27'973 26.027 24.591 20.566 15.987 13-100 3799.693 98-662 95-147 88'046 67'341 63'945 58.379 49'631 48-408 45'717 37'231 35'014 33.469 27.778 22'692 20.086 09.397 08'068 05-711 3687 -607 83.202 80-064 47'995 Remarks and references showing by figures the intensity of the lines, (1) being the lowest.TRE SPECTROGRAPHIC ANALYSIS OF MINERALS.Spectrographic analysis, &c. (continued). 67 Wave-lengths of lines. ( Rowland's scale.) 3631 '2 18 '7 09 '0 05-3 3593'7 87.6 85 *5 81'5 78.8 70.1 65.5 58'6 25'9 25 *O 21 -2 13.7 3497'6 90.7 76 '6 75'4 71.9 66'0 43.8 40'7 3301.9 01 '4 3273'6 47 -0 Lines in solar spectrum for comparison. (Row land. ) 3031.619 18'924 09.015 05.483 3593 -636 87'130 85,479 81 '344 78.832 70.225 65'528 58-670 45.986 24.677 21 '404 13.947 3497 '991 90.721 76.831 75.594 71.499 ? 65'991 44-032 40'759 3303.1 07 02.501 3274 -092 47.680 Remarks and references showing by figures the intensity of the lines, (1) being the lowest.Fe (20) Fe (20) Fe (15) Cr (4) Cr (9) Pe (8) Fe (7) Fe (40) Cr (10) Fe (20) Fe (12) Fe ( 8 ) Fe (7) Fe (6) Fe (7) Fe (10) Fe (8) Fe (10) Fe (3). Identity with 3471.499 doubt- ful. I t is more probably 3472'06 Fe, a reversed line in the arc spectrim (Kayser and Rnnge). E "0) Fe (6) Na (5) Na (6) c u (6) cu (9) ;: {Z) The Spectrographic Analysis of Silicates. Silicates are sometimes of a very refractory nature and do not yield spectra of the bases present other than the alkalis unless these are in some way liberated and converted either into oxides or salts. A means universally applicable for removing the silica had to be devised.Several methods were tried, but only one which has been in use for thirteen years past in the laboratory of this college appeared in all cases to be satisfactory; that is, to decompose the silicate with a mixture of pure ammonium fluoride and strong sulphuric acid warmed in a platinum crucible which is covered by a lid. It is necessary that the ammonium fluoride and the acid should be pure. To purify the ammonium fluoride from silicon fluoride and from all fixed bases, it is necessary to distil it in a platinum retort, an operation which is not F 2(1) Corundum ... (2) Corundum ... (3) Spinel ......... (6) Rutile ......... (6) Basalt ......... (7) Serpentine Co. Donegal (8) Hornblende granulite ...(9) Felsite ......... (Orthoclase). (12) Plumose mica (14) Beryl, (1) Ruby ......... (10) Felspar (11) Muscovite ... (1 3) Lepidolite ... Glencullen, Co. Dublin (16) Schiat con- taining large garnets ...... Garnets and mica slate, Airolo, Can- ton Ticino. (16) Garnets ...... (17) Mica slate ... Minerals from a coar8e granite from Co. Dublin. (18) Felspar ...... (19) Mica ......... (20) Quartz ......... (21) Clay, Shank. hill Quarry, Co. Dublin.. (22) Residue, in. soluble i n HCI, from Cleveland clay iron. stone ......... (23) Shale from ironstone beds ......... (24) Bauxite from Wales ...... - .r( $ e 's - Li Li Li Li Li Li Li - $ $ m - Na Na Na Na Nfl Na Na Na Na Na Na Na Na Na Na Na Na Na Na Na Na Na Na A'a - - ii & .r( W a3 4J - K K K K K K K K K K K K K K K K K K K K K K K R - Examples of the spectrographic analysis oj refi.actory minerals.- .rl El 2 P - Rb Rb Rb Rb Rb Rb Rb Rb Rb Rb Rb Rb Rb F; I% e u - c u c u c u c u c u c u c u c u cu c u c u c u c u Cn c u c u c u c u c u cu c u c u cu - - E * S W .2 3 d o - Ca CaO CaO CaO CaO CaO CaO CaO CaO CaO CaO CaO CaO CaO CaO CaO CaO CaO CaO CaO CaO Ca - 3 :z ; a Sr Sr Br Sr Sr Sr sr Sr Sr Sr - .r( !i c( R s - Ga Ga Ga Ga Ga Ga Ga Ga Gtl Ga Ga Ga Ga Ga Gs Ga Ga Ga Ga Ga Ga - d 2 Fe Fe Fe Fe Fe Fe Fe Fe Fe Fe Fe Fe Fe * - Fe Fe Fc Ft? Fe Fe Fe Fe Fe Fe Fe - M 4 iz - Ni Ni Ni Ni Ni Ni Wi Ni Ni Ni - - 2 % Fi i - Mn Mn Mn Mn MU Mn Mn Mn Mn Mn Mn Mn Mn Mn Mn hl n Mn MH Mn Mn - $ 'ii 2 d 0 - Cr Cr Cr Cr Cr Cr Cr Cr - W $ 4 - Pb Pb Pb Pb Pb Pb Pb Pb Pb Pb Pb Pb Pb Pb Pb Pb Pb Pt- Pi Remarks.iVhere the symbol of the element is printed in italics, it means that there werr traces only. Jpinel contains more Cr and Ga than ruby. Ruby contains Mn and Cu, and more Fe than spinel. rhe symbol Ca indicate8 the calcium line 4228. When the quantity of substance is small this very strong line alone is photographed. rhe formula CaO shows that the calcium oxide bands in addition are conspicuous. MgO indicates bands of magnesium oxide. Gallium doubtful herr. The mica slate contains also TiOa as rutile. Practically all the Mn, Cs, as, and Ag cr!s- tallic~e in the mica. The felrpar contains alarger proportion of Na, Ca, and Pb, but smaller pro- portions of Rb and Fe. It is a little doubtful whether chromium is present here.70 SPECTROCRAPTi[IC ANALYSIS OF MINfiRALS.difficult, since the salt distils freely and does not solidify in the neck of the retort. The purity of the sulphuric acid is of course easily ascertained by ignition in a platinum dish, when it should leave no fixed residue. The proportion of fluoride found convenient will of course differ with the nature and composition of the silicate to be examined. If we take the substance which is perhaps the most refractory, namely, cyanite, because it contains about 96 per cent. of aluminium silicate, we may reckon that for every gram of the mineral there will be required at least two and a half times its weight of ammonium fluoride and five times its weight of oil of vitriol. I n practice we find three times its weight of ammonium fluoride and seven times its weight of oil of vitriol are sufficient.These materials may be intimately mixed with the very finely powdered mineral and kept for some time a t a temperature of about 50°. When silicon fluoride ceases to be evolved, the temperature may be gradually raised until the sulphuric acid and ammonium sulphate are completely ex- pelled. The solid may be then converted into mixed bases by re- peatedly heating with ammonium carbonate and igniting gently. Lead is found sometimes in ordinary concentrated oil of vitriol by the appearance of one lead line in the spectrum, but when it is desirable to get rid of this impurity, the acid made from sulphur trioxide may be used. The only impurities observed in the spectra, including those yielded by the paper and the sulphuric acid, were traces of sodium, potassium, calcium, and the merest trace of iron.Otto Vogel has described the use of the oxy-coal gas flame for spec- trum analysis, using pieces of retort carbon from gas-works as a sup- port for the substance (Zeit. anorg. Chem., 1894,5, 42-62). The spectra were not photographed. Such observations were made by one of us using iridium wires as a support as far back as 1885, and the methodof examin- ing such minerals as heavy-spar, fluorspar, felspar, and mica in such a flame was taught in the laboratory of the Royal College of Science, Dublin, from that time until 1889 and 1890, when the oxyhydrogen flame and cyanite supports were used. Silicates such as felspar, mica, &c., we now examine in the following manner. The residue from the treatment of 1 gram with ammonium fluoride, &c., after ignition to expel the ammonium sulphate, is boiled with water and a slight excess of ammonia.The precipitate which contains the alumina, &c., is collected by filtration, dried, and ignited in a roll of filter paper. The residue from the filtrate, after ignition, is collected in a small quantity of water, and the mixture poured on to a filter paper, which is dried and burnt. Two spectra are thus obtained from each mineral, the one of bases precipitable, the other of those which are not precipitable by ammonia, Silicates such as basalt, and those present in siderolites, &c., may contain iron (ferrous or ferric oxide),HYOSCYAMUS MUTICUS AND DBTURA STRAMONIUM. 71 calcium oxide, and magnesium oxide, besides the alumina and alkalis. The residue is dissolved in hydrochloric acid, and before precipitating with ammonia theiron must beoxidised. The calcium in thefiltrate is pre- pitated by ammonium carbonate, and the magnesium in the filtrate from this by ammonium phosphate. The filtrate from the magnesium phos- phate is then examined as in the preceding case for the alkalis, The reaction for caesium and rubidium is more delicate if these bases are first separated from the bulk of the potassium and the sodium by precipitating with platinic chloride and boiling the precipitate with water. Potassium and sodium yield strong continuous spectra which mask weak lines of other elements, Lithium is only detected in the photographed spectra by its blue line and one in the ultra-violet when it is present in appreciable quantity, but traces may be easily detected by eye observation of the red line. On pp. 68 and 69 a tabulated statement is given of the substances detected by spectrographic analysis in a number of very refractory minerals which were analysed by the method here described.

ISSN:0368-1645    

DOI:10.1039/CT9017900061

出版商:RSC    

年代:1901

数据来源: RSC

摘要:

HYOSCYAMUS MUTICUS AND DBTURA STRAMONIUM. 71 V.-The Alkaloid of Hyoscyamus muticus and of Datura Xtramonium grown in Egypt. By WYRDHAM R. DUNSTAN, F.R.S., and HAROLD BROWN, Assistant Chemist in the Scientific Department of the Imperial Institute. 1. Hyoscyamus rnuticzcs. IN a previous paper (Proc., 1898, 14, 240; Trans., 1899, 75, 72), we have shown that the ETyoscyamus muticus of India, which has long been used in Indian medical practice, contains the alkaloid hyoscyamine, unaccompanied by other mydriatic alkaloids, so that its isolation in the pure state is a comparatively easy operation. The percentage of hyoscyamine found by us in the stems and leave of this sample of the Indian plant was 0.1 per cent, Since the publication of this paper, a short communication has appeared (Arch.Pharm., 1898, 236, 704) by Dr. Gadamer, in which he states that he has examined Epcyamus muticus grown in Egypt;, and has found in the seed capsules and seeds 1.34 per cent. of hyos- cyamine, and in the leaves as much as 1.393 per cent., whilst the stems contained 0.569 per cent. As these quantities are more than ten times as great as those found by US in the Indian plant, we have examined the alkaloid furnished by plants grown in Egypt, which72 DUNSTAN AND BROWN: THE ALKALOID OF have been collected for us through the kindness of Mr. E. A. Floyer, Member of the Egyptian Institute, The material received weighed about 1-6 kilograms, and consisted of the leaves, stems, and flowers. In many cases, the fruits were fully formed and the seeds ripe.The seed was removed for examination whilst the stems and leaves were operated upon together. Seeda.-About 60 grams were obtained and thoroughly dried in a current of warm air (about 40O). They were then ground to a fine powder, and the alkaloid extracted by the process previously described (Zoc. cit.). As in the case of the Indian plant, the hyoscyamine was ob- tained in a crystalline condition. The quantity corresponded with 0.57 per cent., calculated on the dry material. I n fractionally crystfillising this alkaloid, by adding light petroleum to its solution in dry chloro- form, it was nearly all obtained in white, silky needles melting at 105O, which furnished a crystalline aurichloride melting at 160' and con- taining 31.55 per cent. of gold. There is therefore no doubt that the crystalline alkaloid is pure hyoscyamine.As two very small fractions presented themselves in a gummy, semi-crystalline state, they were converted into aurichloride, and this was fractionally crystallised. Nothing, however, was obtained beyond an aurichloride melting at 160' and containing 31.3 per cent. of gold, so that no other alkaloid than hyoscyamine was present, Xiems and Leaves.-The mixture of stems and leaves was thoroughly dried, finely powdered, and the alkaloid extracted. It amounted to 0.59 per cent, on the dried material. This alkaloid crystallised readily from its solution in chloroform and possessed all the properties of hyoscyamine. A quantity was converted into the aurichloride and fractionally crystallised. All the fractions melted between 159O and 160' and contained between 31 and 31.5 per cent.of gold, so that it may be safely concluded that no other alkaloid than hyoscyamine was present. A non-alkaloidal substance was, however, isolated from the crystalline material first obtained. It was noticed in crystallising the original alkaloid from chloroform. On recrystallising this sub- stance from alcohol, it was obtained in flat, rectangular plates melting a t 196-198'. It was not readily dissolved by cold water, although easily soluble when heated ; the aqueous solution was quite neutral. It left no residue on ignition, and although it contained nitrogen, did not react with alkaloidal reagents, nor did it exhibit the properties of a base. It was also devoid of acid properties, being only sparingly soluble in cold aqueous alkalis, whilst the solution obtained by heating deposited, on coding, the unchanged substance.It did not reduce Fehling's solution before or after boiling with dilute sulphuric acid. I t s taste was distinctly bitter. The quantity of the Substance avail- The plant is very abundant in the desert.HYOSCYAMUS MUTICUS AND OF DATURA STRAMONIUM. '73 able did not allow of its further investigation, but we intend, when a fresh supply of material has been obtained, to investigate its pro- perties more fully. It thus appears that Hyoscyamus muticus grown in Egypt resembles that grown in India in containing practically pure hyoscyamine. The amount of this alkaloid furnished by the Egyptian plant is, how- ever, considerably greater than that yielded by the same plant grown in India.It must, however, be borne in mind that, so far, only one sample of the Indian plant has been examined, and it is well known that the quantity of alkaloid in atropaceous plants varies con- siderably with their age. The examination of other samples of the Indian plant will, therefore, be necessary before it can be definitely concluded that the larger proportion of alkaloid now found is due to the growth of the plant in Egypt. The rather larger percentages recorded by Dr. Gadamer may be partly accounted for by his having employed Keller's volumetric method of estimation, whereas we have isolated and weighed the crystalline alkaloid; and partly also by the age of the plant ex- amined, as to which we have no information.The percentages of hyoscyamine recorded for Hyoscyamus muticus grown in Egypt are very much higher than those hitherto recorded for any atropaceous plant, and this, taken with the fact that hyos- cyamine can be so readily obtained in a pure condition from this material, makes Hyoscyamus muticus a valuable commercial source of this alkaloid. Mr. Floyer informs us that any quantity can be readily grown in the Egyptian desert, and that a demand for a large supply could easily be met. 11. Datura Xtramoniurn. Through the kindness of Mr. Floyer, we have been enabled to examine a specimen of the Datura Stramonium grown in Upper Egypt. The European plant is well known, and somewhat extensively used in medicine. It was a t one time supposed to contain an alkaloid daturine, which subsequent research proved to be a mixture of atropine and hyoscyamine.As difference of climate and soil is known to produce considerable alteration in the constituents in plants, we were glad of the opportunity to examine the Egyptian Stramonium. From the plant as received, consisting of thick, succulent stems, holding large, ripe fruits but very little leaf, the seeds were removed, and the remainder, consisting of the stem, broken leaves, and fruit cases, separately examined. They were then examined in precisely the same manner as those of Eyos- Seeds.-About 42 grams were obtained and dried in the air.74 POPE AND HARVEY: THE INVERSION OF THE C y ~ ~ U 8 muticw. 0.35 per cent. of the crystalline alkaloid was obtained melting at 104O, and showing all the characters of hyoscyamine.Its aurichloride, after recrystallisation, melted a t 1 5 9 O , and contained 31.29 per cent. of gold. The whole of the alkaloid was converted into aurichloride, and this was fractionally recrystallised. I n no case was any aurichloride obtained other than that of hyoscyamine. Stems and Leaves.-The mixture of stems and leaves, amounting to about 80 grams, was air-dried and examined in the same manner as Hyoscyamus muticus. 0.3 per cent, of alkaloid was obtained, which, however, did not crystallise readily, but separated in a semi-gummy state. The whole of i t was therefore converted into aurichloride and fractionally crystallised. With the exception of a minute, granular fraction melting below 130°, which was probably the aurichloride of atropine, the whole of the gold salt was obtained in shiny, crystalline scales characteristic of hyoscyamine aurichloride. They melted at 159", and contained 31.37 per cent. of gold. The influence of minute quantities of other alkaloids in hindering the crystallisation of hyos- cyamine is well known. It therefore appears that the Datura Stramonizcm of Egypt differs from that grown in Europe in containing hyoscyamine unaccompanied by other atropaceous alkaloids, although, as has been pointed out in the previous paper, the nature of the alkaloid contained in plants belonging to this natural order is liable to vary considerably with age, and therefore this difference may not be in reality a fundamental one. It is obvious that both these plants merit the attention of those concerned with their utilisation in medicine and pharmacy, as an abundant supply of either could be obtained in Egypt. SCIENTIFIC DEPARTMENT, IMPERIAL INSTITUTE, 5. W.

ISSN:0368-1645    

DOI:10.1039/CT9017900071

出版商:RSC    

年代:1901

数据来源: RSC

摘要:

74 POPE AND HARVEY: THE INVERSION OF THE VL-The Inversion of the Optically Active ac-Tetra- hydro-p-naphthylames prepared by the aid o f d- and l-Bromocamphorsulphonic Acids. By WILLIAM JACKSON POPE and ALFRED WILLIAM HARVEY. IN order to further investigate the possibilities of the methods devised during recent years for the resolution of externally compensated basic substances (Pope and Peachey, Trans., 1898, 73, 893 ; 1899, 75, 1066, 1127 ; 1900, 77, 1072 ; Pope and Rioh, Trans., 1899,75, 1093), theOPTICALLY ACTIVE AC-TETRAHY DRO-6- NAPHTHY LAMINES. 7 5 study of Bamberger and Muller's ac-tetrahydro-/3-naphthylnmine (Ber., 1888, 21, 847) was undertaken; this substance, according to the constitution assigned to it by these authors, contains an asymmetric carbon atom. Reso Zution of Externally Compensated ac-Tetrahydyo- CH.CH:Q*CH;~H, CH~CH: C*CH,~CH~NH,' p-naph t h y Zamin e, I I Crude racemic ac-tetrahydro-/3-naphthylamine hydrochloride is puri- fied by precipitating the carbonate of the base from ether as described by Bamberger and Muller and subsequently evaporating to dryness with hydrochloric acid, or by the simpler but equally efficient method of crystallising it several times from moist boiling acetone ; it melts at 242-243' (Noyes and Ballard, Ber., 1894, 27, 1450).I n accord- ance with the method devised by Pope and Rich (Zoc. cit.), hot con- centrated aqueous solutions of one molecular proportion of ammon- ium d-bromocamphorsulphonate and of two molecular proportions of racemic tetrahydro-P-naphthylamine hydrochloriae are mixed.An immediate separation of the least soluble salt possible in the system takes place in accordance with the equation : d-B,ECl+ Z-B,HCl + NH,,d-A = NH4Cl + I-B,HCl + d-B,d-A, and, by the time that the solution has cooled to the ordinary temper- ature, a practically quantitative separation of the d-tetrahydro$- naphthylamine d-bromocamphorsulphonate as a mass of colourless needles has been effected. After filtering and washing with cold water, the salt is crystallised from boiling spirit and then from hot absolute alcohol, ethyl acetate being added to the latter solution before cooling. It may be remarked that this resolution partakes more of the nature of a separation by precipitation than of a separation by frac- tional crystallisation. d-ac- Tetrah ydro-P-naphth y Zarnine d- Bron Locamphoraulhonat e, C1,H,,~NH,,C,,H1,Br0 SO,H.The salt crystallises in long, colourless needles melting with decom- position at 185-188', and a solution of 0,4471 gram made up t o 25.1 C.C. with absolute alcohol gave aD + 3.08 at 12O in a 200 mm. tube ; whence the specific rotatory power [a], +86*5. It is very soluble in hot alcohol, but less so in ethyl acetate and very sparingly soluble in boiling water, The following analytical results were obtained :76 POPE AND HARVEY: THE INVERSION OF THE 0.1642 gave 0-3146 CO, and 0,0949 H,O. 0.4006 ,, 0.16'79 AgBr. Br- 17.86. C20H,,0,NBrS requiros C = 52.40 ; H = 6.11 ; Br = 17.47 per cent. Ammonium l-BromocamphorszcZ~honat~ .-The Z-camphor required for the preparation of the hitherto unknown I-bromocamphorsulphonic acid is conveniently obtained by treating Schimmel and Co.'s Z-borneol with successive quantities of nitric acid of sp.gr. 1-42 until no further evolution of red fumes takes place; the product is then poured into water and the precipitated camphor collected, well mashed with cold water, and dried. The Lcamphor thus obtained is bromin- ated by Armstrong and Matthews' method (Chem. News, 1878, 37, 4), and after crystallisation from boiling spirit, Z-a-bromocamphor is abtained in long, colourless needles melting at 76' (compare Haller, Compt. rend., 1887, 105, 66). The rotatory power was determined in benzene solution, and compared with that of the enantiomorphously related d-a-bromocamphor, with the following results : 0,4195 gram of d-bromocamphor, made up to 25.0 C.C.with benzene, gave u,, + 3-93' at 19' in a 200 mm. tube: whence [a]D + 117-1'. 0.4172 gram of Ebromocamphor, made up to 25.1 C.C. with benzene, gave uD - 3.93' at 19' in a 200 mm. tube : whence [a], - 118.2O. The I-bromocamphor, on sulphonation and subsequent treatment by Kipping and Pope's method (Trans., 1895, 6'7, 356), yields ammonium I-bromocamphorsulphonate having properties similar to those of its stereoisomeride, as is shown by the following determinations of rota- tory power : 0.4531 gram of ammonium d-bromocamphorsulphonate, made up to 25 C.C. with water, gave uD +3*06' in a 200 mm. tube at 1 8 ~ 5 ~ : whence [ .]D + 84.4' and [MID 4- 277'. 0.4559 gram of ammonium I-bromocamphorsulphonate, made up to 25-1 C.C.with water, gave aD - 3-06' in a 200 mm. tube at 18*6O: C=52*25 ; H-6-42. 0.1719 ,, 0.3285 CO, ,, 0.0989 H,O. C=52*12 ; H=6*39. whence [a]D - 84.2" and [MID - 276'. The description of derivatives of laevo- and of externally com- pensated bromocamphorsulphonic acids will form the subject of a future paper. I-ac-Tetrahydro-/3-naphthylavnime 1-Brornocamphoraulphonate, CloH11*NH2,Cl,Hl,BrO*S0,H. The mother liquors remaining after separation of the d-bromocamphor- snlphonate of the d-base are treated with a trifle more than the requisi$e amount of soda to liberate the base, which is then exhaus-OPTICALLY ACTIVE AC-TETRAHYDRO-P-NAPHTHYLAMJNES. 77 tively extracted with ether ; after washing the ethereal solution with water, the base is precipitated as carbonate, and the latter, dissolved in just the requisite amount of hydrochloric acid, is then treated with a hot aqueous solution of one equivalent of ammonium I-bromocam- phorsulphonate.A crystalline precipitate of I-tetrahydro-/3-naphthyl- amine I-bromocamphorsulphonate a t once falls, and is purified in the same way as its enantiomorphously related isomeride. The salt crystallises in colourless needles melting at 185-188' with decomposition, and, after drying at loo', was analysed with the fol- lowing results : 0.1527 gave 0.2922 CO, and 0.0891 H,O. 0.4219 ,, 0.1747 AgBr. Br= 17.65. C2,H,,0,NBrS requires C = 52.40 ; H = 6.11 ; Br = 17.47 per cent. A solution of 0.4206 gram, made up to 25.1 C.C. with absolute alcohol, gave aD -2.89' at 16' in a 200 mm. tube : whence [a], -86*2', a result numerically identical with that obtained for the antipodal isomeride.It may be remarked that, by the successive application to an ex- ternally compensated base of the enantiomorphously related d- and I-bromocamphorsulphonic acids, the practically quantitative resolution of the inactive base into its optically active components becomes possible. C -- 52.19 ; H= 6.48. 0.1668 ,, 0.3206 CO, ,, 0.0965 H,O. C=52.42 ; H=6*43. d-ac-17etra~ydro-P-na~lzthylcGntine Hydrochloride, C,,H,,*NH,,HCl. On suspending &-tetrahy dro-P-naphthylamine d-bromocamphorsulphon- ate, having the specific rotatory power [a], + 86.5', in a little water, adding rather more than sufficient soda to liberate the base, extract- ing with ether, washing the ethereal solution with water, and distilling off the ether after addition of hydrochloric acid, a crystalline residue of the hydrochloride is obtained. This salt, however, proves to be a mixture of the dextro- and racemic hydrochlorides ; on crystallisation from hot water, a deposit of salt was obtained which melted at 239-241', and had it specific rotatory power of [a], + 32.9' in a 2 per cent.aqueous solution, corresponding to a molecular rotatory power of [MI, +59', which, as shown later, is an impossibly low value for d-tetrahydro-/3-naphthylamine hydrochloride. Further, on dealing with a large quantity of carefully purified d-bromocamphor- sulphonate and systematically crystallising the mixture of hydro- chlorides from water and dilute acetone, a specimen of the pure racemic hydrochloride was isolated which melted a t 242-243', did not depress the melting point of an undoubted sample of the salt, and78 POPE AND HARVEY: THE INVERSION OF THE was optically inactive.The racemic salt was isolated as the most sparingly soluble component of the mixture, and from the mother liquors, pure d-tetrahydro-P-naphthylamine hydrochloride was separ- ated as the most soluble constituent by repeated crystallisation. d-Tetrahydro-P-naphthylamine hydrochloride crystallises from boiling moist acetone in colourless needles melting at 343-245" and separates in long, flatten'ed needles of glassy lustre during the spontaneous evap- oration of itscold aqueous solution. It is practically insoluble in dry organic solvents, but readily dissolves in water.The following analytical results were obtained with the salt dried at 100" : 0.1426 gave 0.3415 CO, and 0.1007 H,O. C= 65.31 ; H= 7.85. 0.1308 ,, 0.3136 CO, ), 0.0916 H,O. C=65*39; H=7*78. 0.2160 ,, 0.1699 AgC1. C1= 19.46. Cl,H,,NC1 requires C = 65-43 ; H = 7-63 ; C1= 19.30 per cent. A solutionof 0-3645 gram, made up to 25.2 C.C. with water, gave uD +2.08" a t 12" in a 200 mm. tube; whence [a], +71*9* and [MID + 131-9". In moist acetone solution, the salt has about twice as high a rota- tory power as in water; since, however, the values vary with the amount of moisture present in the acetone, they need not be quoted. Lac- Tet rcchy dro -P-naphtA y lamim B y drochloride, C,,Hll*NH,,HCI. I n just the same way, it was found that optical inversion takes place during the preparation of Ltetrahydro-P-naphthylamine hydrochloride from its I-bromocamphorsulphonate ; the racemic hydrochloride is first isolated as the least soluble constituent, whilst the mother liquors contain the hydrochloride of the Ebase which is ultimately purified by repeated crystallisation from moist acetone.The salt melts a t 243-245', and was analysed with the following result : 0.2238 gave 0,1765 AgCI. C1= 19.51. Calculated C1= 19.30 per cent. A solution of 0-1206 gram, made up to 25.1 C.C. with water, gave aD - 0.67 a t 16" in a 200mm. tube: whence [aID - 69.7"and [MI, - 128". d-ac- Tetrahydro-@ naph tlly lamine d - Camphorsulphonat e, CloH11*NH,,C,oH,,0*S0,H,3H~~H20. The preceding results indicate that both d- and Z-tetrshydro-b-naph- thylamine undergo a partial racemisation during the conversion of their bromocamphorsulphonates into the corresponding hydrochlorides ; it is, in consequence, very difficult to isolate the optically active hydro- chlorides in a state of sufficient purity to allow of their properOPTICALLY ACTIVE AC-TETRAHYDRO-6-NAPHTHYLAMINES. 79 characterisation.It seemed probable that the active bases would be most conveniently characterised by means of their more soluble salts with optically active acids, and to this end the salts with Reychler's d-camphorsulphonic acid were prepared. The base was separated from the d-bromocamphorsulphonate of [ U] + 86.5" as described above, and the ethereal solution evaporated to dryness with the corresponding weight of pure d-camphorsulphonic acid, the solid residue being subsequently crystallised from hot water.The greater part of the product consists of d-tetrahydro-P-naphthyl- amine d-camphorsulphonate, which was easily obtained i n a state of purity. It crystallises in long, colourless needles from hot water, and in stout prisms several centimetres in length by spontaneous evapo- ration of its cold aqueous solution ; the crystals contain &H,O and melt at 210-211O. 0.3338 air-dried salt lost 0*0078 H,O at 100. 0.1225 dried salt gave 0.2817C0, and 0,0858 H,O. C = 62.71; H = 7.78. 0-1168 ,, ,, 0.3689 CO, ,, 0.081 6 H,O. C = 62.79; H = 7.77. 0.2530 ,, ?, 0.1623 BaSO,. S=8*81. C,,H,,O,NSrequiresC = 63.32; H= 7-65; S = 8-44; $H,O = 2032percent. A solution of 0.3156 gram of the dried salt, made up to 25.1 C.C.with water, gave uD + 1*20° in a 200 mm. tube at 12.5'; whence [a], + 47.7" and [MI, + 180.9'. Since Pope and Peachey have shown (Trans., 1899, 75, 1085) that the d-camphorsulphonic ion has [MI, + 51-7", that of the d-tetrahydro-/3-naphthylammonium ion should be [MID + 129.2' ; this value agrees well with that obtained above for the molecular rotatory power of d-tetrahydro-P-naphthylamine hydro- chloride, namely, [MI, + 13 1.9'. After the major portion of this salt has separated, the solution begins to deposit I-tetrahydro-P-naphthylamine d-camphorsulphonate in the characteristic form of colourless scales; this salt owes its formation to the partial optical inversion of the d-tetrahydro-P- naph thy lamine. The following analytical results were obtained : H,O = 2.33.1-ac- Tetrahydro-PJnuphth ylanzim d-Camphoraui'phonate, C10HIl*NH2, C,,H,,0*S0,H,H20. This salt cannot be conveniently isolated from the mother liquors containing the inversion product of the d-base, but was prepared by extracting the base from I-tetrahydro-P-naphthylamine Ebromocam- phorsulphonate with soda and ether, and subsequently evaporating the ethereal solution with the requisite quantity of d-cnmphorsulphonic acid. It crystallises from water in small, colourless scales containing 1H,O, and on heating melts first in its water of crystallisation a t80 POPE AND HARVEY: THE INVERSION OF THE 83', and for the second time at 207-208'. results were obtained : The following analytical 1.2016 air-dried salt lost 0,0555 H,O at 100. 0.1195 dried salt gave 0.2768 CO, and 0.0814 H,O. C = 63.17; H = 7.57.0*2205 ,, ,, 0.1403 BaS04. 8 = 8.74. C20H,,0,NSrequiresCf = 63.32; H = 7.65; S = 8.44; lH20 = 453percent. A solution of 001429 gram of the dried salt, made up to 25.2 C.C. with water at 16', gave uD -0.11' in a 200 mm. tube, whence [a], - 9 ~ 7 ~ and [MI, - 36'8'. Bince it has aleady been shown that the molecular rotatory powers of the tetrahydro-P-naphthylammonium and camphor- sulphonic ions are 130' and 5 1 * 7" respectively, I-tetrahydro-P-naphthyl- amine d-camphorsulphonate should have the molecular rotatory power [MI, - 68' ; the salt was evidently still contaminated with a little of the racemisation product of the 1-base, its purification from which is very difficult. H,O=4*61. 0.1264 ,, 9 , 0.2920 GO, ,, 0,0890 H20.C = 63.00; H = 7.82. 1-Carnphorsulphonic Acid a n d i t 8 S a l t s with the Optically I-Camphorsulphonic acid was prepared from I-camphor by the method which Reychler used for the preparation of d-camphorsulphonic acid (Bull. 8oc. Chirn., 1898, [iii], 19,120), and was purified by crystallisation from acetic acid and ethyl acetate ; on converting a portion of the pro- duct into ammonium salt, the following determination of the rotatory power of the latter showed it to be enantiomorphously related to ammonium d-camphorsulphonate, which has [MI,, + 51.7" (Pope and Peachey, Trans., 1899, 75, 1086). A solution of 0.4965 gram, made up to 25.1 C.C. with water at 17', gave uD - 0.82' in a 200 mm. tube ; whence [a]D - 20.7" and [MI, - 51.6'. The following two salts were prepared from d- and Ltetrahydro- P-naphthylamine d- and I-bromocamphorsulphonates respectively, with the aid of I-camphorsulphonic acid, for purposes of comparison with their enantiomorphously related isomerides.A G t iue Tetra h y d TO-p-nap h t h y 1 am ines. Lac-Tetrahydro-P-naphthyzarnine 1-CamphorsuIphonate, C,oH,l*NH,,CloH,,O*SO,H,~H,O. This salt crystallises from water in long, transparent prisms contain- ing #H20, which is lost at 100'; it melts at 210-211') and was analysed with the following results : 0,8662 lost 0.0205 H,O at 100'. 0.1137 dried salt gave 0.2627 CO, and 0.0792 H,O. H20 = 2.36. C=63-01; H = 7.74.OPTICALLY ACTIVE AC-TETRAHYDRO-@-NAPHTHYL AMINES. 8 1 0-1109 dried salt gave 0.2569 CO, and 0.0791 H20. C2,H,,0,NS requires C = 63.32 ; H = 7.65 ; &H,O = 2.32 per cent. A solution of 0.3284 gram of the dried salt, made up to 25.1 C.C.with water, gave uD - 1.24O at 17' in a 200 mm. tube : whence [a]D - 47.4' and - 179*6', values in close numerical agreement with those given for the antipodal isomeride. C=63.18 ; H = 7.92. d-ac-Tetrahydro-P-naphthylamine 1-CwnphorsuZphonate, C,,H,1NH,,C1,H,,O0SO,H,I3[,0. This salt crystallises from water in glistening scales containing 0.3268 air-dried salt lost 0.0144 H20 a t 100'. 0,1185 dried salt gave 0.2753 CO, and 0.0833 H,O. C,,H,,O,NS requires C = 63.32 ; H = 7.65 j 1H,O = 4.53 per cent. A solution of 0.1320 gram of the dried salt, made up to 25.1 C.C. with water, gave an +0.14" a t 16" in a 200 mm. tube : whence [.ID + 13.3O and [MI, +50.4".1H,O, and, after drying, melts at 207-20S0. H20 = 4.41. C= 63.36 ; H = 7.81. d-ac-Tetrahydro-/3-nwphth ylamine platinichloride, 2 C1,Hll*NHP, H,PtCl,, 2H20. On adding the requisite amount of platinic chloride to an aqueous solution of d-tetrshydro-/3-naphthylamine d-carnphorsulphonate acidi- fied with hydrochloric acid, a crystalline precipitate of the platinichloride is obtained ; it crystallises from hot, di1ute:hydrochloric acid in golden- yellow scales which blacken at 235' and melt, with decomposition, at 240'. The salt is practically insoluble in water, and its rotatory power could not be determined. 0.7007 lost 0.0333 H,O at 100'. 0.2941 gave 0.0776 Pt. H20 = 4.75. Pt = 26-38. C,,H,,N,Cl,Pt requires Pt = 26-33 ; 2H,O = 4-84 per cent. The Racemisation of d- a n d l - l i r e t r a h y d r o - / 3 - ~ a p ~ t ~ y ~ a m ~ ~ ~ It has been proved above that, on preparing the hydrochloride or the camphorsulphonate from d-tetrahydro-/3-naphthylamine d-bromo- camphorsulphonate, a certain proportion of the optically active base is inverted; the only alternative t o this view is that the original bromo- camphorsulphonate is a kind of partially racemic compound containing several equivalents of the d-base to one of the I-base.That this cannot YOL. LXXIX. a82 POPE AND HARVEY: THE INVERSION OF THE be accepted we have proved by treating a pure sample of d-tetrahydro- Pnaphthylamine d-camphorsulphonate with soda, extracting with ether, and once more preparing the d-camphorsulphonate from the ethereal extract. The salt obtained proved to be a mixture of d* and Idtetrahydro- Pnaphthylamine d-camphorsulphonates.It follows that, in general, the optically active tetrahydro-P-naphthylamines undergo partial race- mieation when liberated from their salts by soda and converted into other salts, During which of these two distinct operations the race- misation takes place is not decided ; but i t is at least probable that it is connected with the liberation of the base, rather than with its recombination, because on preparing a solution of the hydrochloride of known rotatory power, evaporating it to dryness with somewhat less than an equivalent of sulphuric acid, dissolving in water and making up to the original volume, the rotatory power is found to be unchanged. Some kind of momentary tautomerism seems to exist during the liberation of the base from its salts; this tautomerism, however, does not persist after the new salt is formed because no alteration in rotatory power attends the heatbg of the optically active salts in solution.I n the hope that the facility with which racemisation occurs might be applied to the conversion of the externally compensated base into one enantiomorphous component as was done with the compounds containing an asymmetric tin atom (Pope and Peachey, Proc., 1900, 16, 42, 116), the following experiment was performed. The base was liberated from 20 grams of pure racemic tetrahydro-/3-naphthylamine hydrochloride by soda and extracted with ether ; the ethereal solution was then treated with sufficient d-bromocamphorsulphonic acid solution to combine with all the base, and the solution slowly evaporated to dryness.The base was then liberated from the whole by addition of soda and extracted with ether, the ethereal solution being then evaporated and the residual base distilled under about 15 mm. pressure. The pure product thus obtained had the rotatory power uD +0-05' in a 100 mm. tube. It was once more treated with d-bromocamphor- sulphonic acid in a sealed tube and the whole heated a t 100' for three days, after which the base was liberated, extracted with ether, and distilled under reduced pressure as before. The distillate now had the rotatory power uD +0.18* in a 100 mm. tube. These results in- dicated that the externally compensated base was slowly becoming optically active under this treatment, but this might well be because the I-base, which remained always dissolved, was more liable to undergo slight oxidation than its d-isomeride which was mainly present as solid salt.OPTICALLY ACTIVE AC-TETRAHYDRO-p-NAPHTHYLAMINES. 83 d-ac- Tet r c c h y d ~ o - P - n c c ~ h t ~ y l a ~ ~ ~ ~ . d-Tetrahydro-P-naphthylamine was prepared by treating d-tetra- hydro-P-naphthylamine d-bromocamphorsulphonate of [a], + 86.5' with a slight excess of soda solution, extracting with ether, drying the ethereal solution with potash, and distilling the base under about 15 mm.pressure. It is a colourless oil which is very viscous and does not fume in the air. One preparation had the rotatory power uD +30*5' in a 100 mm. tube at 16', whilst another had the value uD +37*24' in a 100 mm.tube a t 15'. The difference between the rotatory powers of these two preparatioris indicates that racemisation had taken place to a certain extent. 0,2632 gram of the base of uD +37*24' was made up to 25.1 C.C. with water containing the calculated quantity of hydrochloric acid ; the solution had Q, +0*71' a t 15.5' in a 200 mm. tube : whence [ a ] , + 33.8' and [MI,, -+ 49.8'. Since we have shown that the d-tetrahydro-P-naphthylammonium ion has the molecular rotatory power [MI, + 130°, it follows that, if no racemisation attends the formation of the hydrochloride from the free base, pure d-tetrahydro-/3-naphthylainine should have a rotatory power of about a,, +96' in a 100 mm. tube, and our best specimen of aD + 37-24" consisted of 70 per cent, of d- and 30 per cent.of 1-base, Benxylidene-d-ac-tetrcc?~yd./~o-P-~ap~t~ylccmine, C,,H,, -N: CH*C,H,. d-Tetrahydro-P-naph thylamine carbonate was precipitated from an ethereal solution of the base obtained by treating the d-bromo- camphorsulphonate of [a], + 86.5' with a little more than the equiva- lent proportion of soda, On heating this carbonate with 1 molecular proportion of benzaldehyde on the water-bath, reaction occurs readily with formation of the benzylidene derivative of the base. On crys- tallisation from spirit, the product is found to consist of two sub- stances; the less soluble constituent is present in the larger quantity and is the racemic benzylidenetetrahydro-P-naphthylamine prepared from the inactive base by Bamberger and Kitschelt (Ber., 1890, 23, 876). It crystallises readily in anorthic plates of rhomboidal habit and melts a t 51-52'; its identity was established by comparison with the benzylidene derivat.ive prepared from inactive tetrahydro-p- naphthylamine carbonate as described by Barnberger and Kitschelt.It is accompanied by 5 or 10 per cent. of a dextrorotatory isomeride which separates from the mother liquors in spherical aggregates of colourless needles and may be obtained in an apparently pure state by mechanical separation during fractional crystallisation from alcohol. G 284 POPE AND HARVEY: THE INVERSION OF THE The purest sample which we succeeded in obtaining melted at 58-60' ; it was analysed with the following results : 0.1046 gave 0.3322 CO, and 0*0700 H,O.C = 86.61 ; H = 7.44. 0,1119 ,, 0.3553 CO, ,, 0.0745 H20. C =86*59 ; H= 7.40. Cl7HI7N requires C = 86.81 ; H = 7-23 per cent. A solution of 0.3657 gram made up to 25.0 C.C. with absolute alcohol at 18*5', gave uD +0*81' in a 200 mm. tube : whence Benzoyl-d-ac- tetra hydro-/3-rtaphthy lamine, CloH,,*NH* CO-C,H,. On treating powdered d- t etra h y d ro-P-napht h y lamine d-bromocamphor- sulphonate of [.ID + S6.5' suspended in water, with benzoyl chloride and soda by the Schotten-Baumann method, benzoylation readily occurs with separation of an oil which immediately solidifies. The product, after preliminary puri6cation in the usual way, is found to be very slightly optically active in alcoholic solution, the specific rotatory power of different preparations varying from 1' to 3'; it consists almost entirely of the inactive benzoyltetrahydro-P-naphthylamine prepared by Bamberger and Miiller (Bey., 1888, 21, 850), and contains but a small proportion of the dextrorotatory benzoyl derivative.A product containing more of the latter compound is obtained by adding benzoyl chloride to an ethereal solution of the base cooled to 0'; after extract- ing the ethereal solution with water, the tetrahydro-P-naphthylamine hydrochloride recovered from the aqueous solution was found to be still highly dextrorotatory, so that the base unacted upon by the benzoyl chloride does not undergo extensive racemisation. After evap- orating the ethereal solution to dryness and fractionally crystallising the residue from dilute acetone, a considerable proportion of it is found to consist of the racemic benzoyl derivative melting a t 150-1!51', whilst some 5 per cent.or so consists of benzoyl-d-tetrahydro-/3-naph- thylamine. The latter is much more readily soluble than its racemic isomeride, and is ultimately obtained from the acetone solution in felted needles of a woolly appearance; the purest sample obtained melted at 155-157c, and was analysed with the following results : [ u ] D +27*6'. 0.1007 gave 0.2994 CO, and 0.0624 H20. C = 81-07 ; H = 6.89. 0.1053 ,, 0.3134 CO, ,, 0.0657 H,O. C=S1*16; H=6.93. C,,H,,ON requires C = 81.27 ; H = 6.77 per cent. A solution of 0.0238 gram, made up to 25.1 C.C. with acetoneat 19*, gave aD + O.1lo in a 200 mm. tube ; whence [.ID -i-58'.OPTICALLY ACTIVE AC-TETRAHYDRO-6-NAPHTHYLAMINES.85 A cetykd-ac-tetrahydvo-P-naphth ykcmine, CI,Hll*NH* CO-CH,. On adding one-half a molecular proportion of acetyl chloride dis- solved in benzene a t 0' to a benzene solution of d-tetrahydro-P-naphthyl- amine prepared from the d-bromocamphorsulphonate of [a], + 86*5O, a mixture of the racemic tetrahydro-P-acetonaphthalide melting a t 107-108°, which was prepared by Bamberger and Muller (Bey., 1888, 21, 850), with Some 5 per cent. of its dextrorotatory isorneride is obtained. The latter is much more soluble than the racemic com- pound, and may be separated by continued fractional crystallisation from benzene. It crystallises from the latter solvent in long, colourless needles melting a t 104-106°, and on rubbing the crystals with a glass rod they exhibit vivid triboluminescence resembling that of orthoben- zoicsulphinide (Pope, Trans., 1895,67, 98.5) ; this property is lost when the crystals are kept and the racemic compound does not show it a t all.The purest sample of the active compound obtained was analysed with the following results : 0.1062 gave 0.2960 CO, and 0.0777 H,O. C=76-02; H=8*13. 0.1085 ,, 0.3026 00, ,, 0.0790 H,O. C = 76-07 ; H=8.09. C1,Hl,ON requires C = 76.19 ; H = 7.94 per cent. A solution of 0.1122 gram, made up to 25.1 C.C. with benzene, gave + 0 * 3 3 O a t 16.5' in a 200 mm. tube : whence [a], + 36.9'. The Optical Invevsion of Amino-compounds. Although the present investigation was undertaken with a view t o further extending the methods available for resolving externally com- pensated bases, it has led to the observation of a previously unrecorded property which may be exhibited by certain optically active sub- stances, that, namely, of a partial optical inversion attending the liberation of a base from its salts by means of alkali; it has further been found that on preparing the benzylidene, benzoyl, and acetyl de- rivatives from an active base racemisation may occur, and t o a much greater extent than on simply liberating the base from its salts.Two cases of the latter kind are already known : Emil Fischer has shown (Bey., 1900,33, 2370) that partial racemisation occurs on benzoylnting leucine, CHMe,*CH,*CH(NH,)-CO,H, in presence of soda and also on hydrolysing optically active benzoylleucine ; Fischer has also shown, (Ber., 1899, 32, 2466) that considerable inversion takes place on benzoylating optically active glutaminic acid, CO,H CH , CH,* CH (NH,) C0,H.Tetrahydro-P-naphthylamine is more liable to undergo inversion than .86 OPTICALLY ACTIVE AC-TETRAHYDRO-p-NAPHTHY LAMINES. either leucine or glutaminic acid, because racemisation attends the liberation of the former base from its salts, whilst this is not observed with the other two substances. Fischer’s observations, together with our own, allow of some con- clusions respecting a branch of knowledge in which stereochemical methods will doubtless ultimately prove of the greatest importance, that, namely, which concerns the mechanism of chemical change. The R’ H three bases just mentioned all contain the group R,,>C<NK, ; fur- ther, salt decomposition and the formation and hydrolysis of acidic derivatives are operations involving the conversion of triad into pentad nitrogen and vice versd. The probable cause of the optical in- version is as follows : The salts of tetrahydro-P-naphthylamine con- tnin pentad nitrogen, and consequently also the group Rt>c<NH,x ; when treated with soda, they decompose, with separation of HX, in two ways, The two atomic groups, H and X, may both come from the nitrogen atom, so as to lead to the immediate formation of the stable base, 01- X may come from the nitrogen and H from the asymmetric carbon atom, leading to the momentary liberation of the transition product, Rt,>C:NH,, which immediately becomes converted into the stable base by isomeric change.That part of the material which passes through this intermediate stage is necessarily obtained as an externally compensated end-product. This explanation of the partial optical inversion of the base itself is directly applicable, mutatis mutandis, to the formation of the much more nearly compensated acidic and benzylidene tetrahydro-/3-naphthylamines. A view similar to this has been advanced by Armstrong (Trans., 1900, 77, 1049) to explain the conversion of phenylacetylchloramine into p-chloracet- anilide and the optical inversion of glutaminic acid. Further, the environment of the asymmetric carbon atom is certainly tetrahedral, whilst that of the pentad nitrogen atom is probably either that of a pyramid upon a square base or of a double pyramid upon a triangular base, the group X occupying the apex of a pyramid ; it would follow that, in the molecule, the distance between H and X attached to the nitrogen atom is of the same order of magnitude as one of the distances between X on the nitrogen atom and the three groups H, R’ and R , attached to the carbon atom. I n the case when H and X attached to carbon and nitrogen respec- tively are at a distance similar to that separating H and X attached to nitrogen alone, the acid HX would be expected to leave the molecule in both of the two ways indicated above. This case apparently fits that of tetrahydro-/3-naphthylamine, leucine, and glutaminic acid ; R’ H R’THE ALKALOIDS OF COKYDALIS CAVA. 87 R' other substances containing the group ,.>C<,", , such as alanine, 2 do not undergo optical inversion, probably because in their additive compounds, R or R", but not H, on the carbon atom, and X on the nitrogen atom, are a t a distance apart comparable with that separating H and X attached to the nitrogen atom alone. The incompatibility of the environments of the tetrad carbon atom and the pentad nitrogen atom may well be responsible for the peculiar course taken by many reactions involving the conversion OF triad into pentad nitrogen, and vice vei-sd, reactions such as those concerned, for instance, in the interconversions of isomeric oximes. GOLDSMITHS' INSTITUTE, NEW CROSS, S.E.

ISSN:0368-1645    

DOI:10.1039/CT9017900074

出版商:RSC    

年代:1901

数据来源: RSC

摘要:

87 THE ALKALOIDS OF COKYDALlS CAVA. VIL-The Alkaloids of Corydalis cava. Conversion of Corybulbine into Corydaline. By JAMES J. DOBBIE, D.Sc., M.A., ALEXANDER LAUDER, B.Sc., and PHOTIOS G. PALIATSEAS. IT has been shown in a previous paper (Trans., 1894, 65, 25) that the formula of corybulbine differs from that of corydaline by CH,, and that the former alkaloid contains only three methoxyl groups, whilst the latter contains four. Having regard to this relation between the formuls of the two substances, and to the fact that corybulbine is readily soluble in caustic alkalis, in which corydaline is insoluble, and, as shown in this paper, forms an acetyl derivative, the two alkaloids would appear to be related to one another in the same manner as morphine, C,,H,,ON(OH),, and codeine, C,,H,,ON(OH)*OCH,, cory- daline being the higher homologue of corybulbine. The present paper contains an account of the experiments by which this supposed relation was established and the one alkaloid converted into the other. When corydaline and corybulbine are treated with hydrogen iodide, the methoxyl groups which they contain are replaced by hydroxyl radicles.If corybulbine and corydaline are related to one another in the manner above suggested, the phenolic derivatives yielded by the two alkaloids should be identical. The relation of the two alkaloids to one another having been thus established, the conversion of corybulbine into corydaline by the methods formerly employed in similar cases was next successfully attempted. I n 1881, Grimaux converted morphine, C,,H,,ON(OH), into codeine, C1,H,,ON(OH)*OCH,, by treating it with methyl iodide This was found to be the case.88 DOBBIE, LAUDER AND PALIATSEAS : in presence of potassium hydroxide (Compt.rend., 1881, Sa, 1140, 1228 ; 93, 67,217) and ten years later, Grimaux and Arnaud converted cupreine, C,,H,,N,(OH),, into quinine, C,,H,,N,( OH)*OCH,, by the same method (Compt. rend., 1891, 112,766,1364 ; 1892,114,548, 672). By similar treatment, corybulbine is convorted without difficulty into corydaline. The yield, however, is much larger than that obtained by Grimaux in the case of quinine. The corydaline formed can be isolated without difficulty, since the solubility of corybulbine in sodium hydroxide affords a means of separating any unchanged corybulbine, and the methiodides of both alkaloids being unstable in hot solution, no complication in effecting the separation is caused by their presence.The corydaline thus prepared, and the salts which we have ex- amined, agree in all respects with the natural alkaloid and its corresponding salts. The position of the hydroxyl group in corybulbine has not yet been definitely ascertained, but the evidence, so far as it goes, points t o its presence in the isoquinoline nucleus. When corydaline is oxidised with nitric acid, it readily yields corydic acid, C,,H,N(OCH,),( CO,H),,$H,O (Trans., 1897, 71, 657), which contains an isoquinoline nucleus. This acid, on further oxidation, yields, amongst other products, metahemi- pinic acid, [(CO,H), : (OCH,), = 1 : 2 : 4 : 51, but no hemipinic acid [(CO,H), : (OCH,), = 1 : 2 : 3 : 41.Since corydaline on oxidation yields both hemipinic and metahemipinic acids, the benzene ring from which the former acid is derived must be the ring which is destroyed by the oxidation with nitric acid. If the hydroxyl group of corybulbine occurred in this ring, we should expect to obtain corydic acid on oxidising the alkaloid with nitric acid. All attempts, however, to obtain this acid from corybulbine have hitherto failed. EXPERIMENTAL. Action of Acetic Anhydride on Corybulbine. Corybulbine was dissolved in a considerable excess of acetic anhy- dride, and the solution boiled for 4-5 hours under a reflux condenser. The greater part of the acetic anhydride was then distilled off under reduced pressure, and the concentrated solution set to crystallise in a desiccator.The product, which separated as a thick crystalline crust, was crystallised from carefully dried alcohol, from which it separated in tufts of slender, colourless needles melting a t 160'. It was dried over sulphuric acid, and, on analysis, proved to be acetylcorybulbiru, C,,H,,N(OCH,),* O*C,H,O. 0.2676 gave 0.6820 CO, and 0,1736 H,O. C = 69.50 ; H = 7.20. C,,H,70,N requires C = 69.47 ; H = 6-87 per cent.THE ALKALOIDS OF CORYDALIS CAVA. 89 Action of Hydrogen Iodide on Corybuulbine. The corybulbine was boiled with a strong solution of hydrogen iodide under a reflux condenser until all the methyl iodide was ex- pelled, 2 grams of corybulbine and 20 C.C. of hydrogen iodide being used for each operation.The cry-stalline solid which separated on cooling was collected by the aid of the pump, well pressed between filter paper, and then recrystallised several times from water. The fine yellow crystals thus obtained were exactly similar in appearance to those of the corresponding substance prepared from corydaline. Both substances behaved in precisely the same way when heated side by side in capillary tubes, melting a t about 270' to a clear brown liquid ; both dissolve easily in water or alcohol, but only sparingly in ether, and not a t all in chloroform. The iodine in the hydriodide obtained from corybulbine was estimated by Carius' method in the substance dried at 100'. 0.2813 gave 0.1496 AgI. I= 28-73. C18H,,N(OH),,HI requires I = 28.79 per cent. Conversion of Corybulbine into Cwydaline.The corybulbine used for this purpose was purified from traces of corydaline by dissolving in potassium hydroxide, in which corydaline is insoluble, and subsequently precipitating with carbon dioxide. It was afterwards repeatedly recrystallised from alcohol. The purified corybulbine, in quantities of 2.5 grams a t each operation, was boiled under a reflux condenser for 15-20 hours with the equivalent quantity of methyl iodide and potassium hydroxide dissolved in methyl alcohol. After cooling, the contents of the flask were filtered. The residue was found to consist almost entirely of unaltered corybulbine, which is very sparingly soluble in cold alcohol. The filtrate, which contained corydaline mixed with a small quantity of corybulbine, was evaporated to dryness and dissolved in dilute hydrochloric acid.The corydaline was then precipitated from the acid solution with oxcess of potassium hydroxide and afterwards boiled repeatedly with the alkali, t o get rid of the last traces of corybulbine. The crude corgdaline was washed with water until free from alkali, and recrystallised repeatedly from alcohol. Under these conditions we found that from 25 to 30 per cent. of the corybulbine was converted into corydaline. The purified substance was dried a t 100° and analysed, with the following results : 0.2515 gave 0.6586 GO, and 0.1740 H20. 0.4088 ,, 0-1089 Pt. N = 3.84. C=7141; H='i*68. C,,H,70,N requires C = '71.54 ; H = 7-32 ; N = 3.79 per cent.90 THE ALKALOIDS OF CORYDALIS CAVA. The corydaline thus obtained was carefully compared with the natural alkaloid.Specimens of the two were heated side by side in capillary tubes, and were found to behave in exactly the same way, both of them melting at 135'. The solubilities of the two substances in alcohol, ether, chloroform, benzene, or carbon disuIphide were com- pared, but no difference could be detected between them. The specific rotatory power was determined, with the following result : d 2Oo/4O, 0.7961 ; c, 0.7251 ; I, 2 dcm. ; UT +4*6O; [u]?" + 317.1'. Two determinations of the specific rotatory power of the natural alkaloid gave [u]T = +31l0 and + 309-5' (Trans., 1895, 67, 17). Platinichloride of synthetica2 Coryda1ine.-The platinichloride of syn- thetical corydaline was prepared by dissolving the alkaloid in dilute hydrochloric acid and precipitating with platinic chloride.The pale yellow precipitate was collected and washed with cold water till free from acid. It was dried at 100' for analysis : 0.3058 gave 0,0517 Pt. (C,,H,704N)2,H2PtC16 requires Pt = 16 *97 per cent. The salt was exactly similar to corydaline platinichloride in appear- ance, and the behaviour of the two substances, when heated side by side in capillary tubes, was identical. Both softened at 194", began t o decompose a t 2 0 3 O , and were completely decomposed at 210'. The two salts were compared as regards their solubility in water, alcohol, and ether, and were found to agreo in all respects. Ethyl Sulphate of synthetical CorydaZine.-This salt is easily prepared by adding a solution of potassium ethyl sulphate to a solution of the sulphate of synthetical corydaline. It forms large, colourless, prismatic crystals, and is identical in appearance with the corresponding salt of the natural alkaloid. The two salts, when heated side by side in capillary tubes, melt between 150° and 160' to a clear yellow liquid. No difference could be detected between the solubility of the two salts ; both are easily solublo in hot water, alcohol, or chloroform, but only sparingly so in cold water, and insoluble in ether. The hydriodides of the natural and artificial alkaloids were also compared and found to be identical. Pt = 1690. UNIVERSITY COLLEGZP OF NORTH WALES, BANGOR.

ISSN:0368-1645    

DOI:10.1039/CT9017900087

出版商:RSC    

年代:1901

数据来源: RSC

摘要:

FENTON AND JONES: RELATIONSXIPS OF OXALACETIC ACID. 91 VII I.-Re1 a tionships of Oxalacetic Acid. By HENRY J. HORSTMAN FENTON, F.R.S., and HUMPHREY OWEN JONES, B.A., B.Sc. IT has been shown by the authors in a previous communication (Trans., 1900, 77, '77) that malic acid, when oxidised by hydrogen dioxide in presence of ferrous iron, gives free oxalacetic acid, and that the latter may readily be isolated by extraction with ether under certain con- ditions, Some of the properties of the acid were then described, and the present paper gives a n account of further studies in this direction. Special attention is given to such reactions as necessitate the use of the free acid rather than its esters, since the latter have been well in- vestigated. Action of PhenyZhydraxine.-It was previously shown that on mix- ing molecular proportions of phenylhydrazine acetate and oxalacetic acid in aqueous solution, in the cold, the hydrazone is precipitated and is obtained on recrystallisation from ether in the form of coloiirless, transparent prisms." This substance when heated turns yellow and decomposes without melting at about 95O, and on crystallising the resulting product from hot alcohol pale yellow needles are obtained which melt a t 192'. It was shown in the previous paper t h a t when the hydrazone of oxalacetic acid is heated with excess of dilute sulphuric acid, it is changed almost immediately into a crystalline mass consisting of l-phenyl-5-pyrazolone-3-carboxylic acid, identical with that previously obtained from the esters by Wislicenus and by Buchner.No visible evolution of gas occurs in this reaction. It has now been observed that if pure water be substituted for the dilute acid, a brisk evolution of carbon dioxide takes place ; the whole goes into solution, and almost immediately a crystalline precipitate separates. This, when recrystal- lised from alcohol, separates in pale yellow needles which melt at 19Z0, and is evidently identical with the product obtained by the action of heat alone. It coincides exactly in melting point and other properties with the hydrazone of pyruvic acid. On analysis the following results were obtained : * That this is the hydrazone, and not the hydrazide, is proved by its behaviour as a dibasic acid. 0'3940 required 33-9 C.C. of N/10 KOH for neutralisation, the calculated amount being 35.5 C.C.A solution of the substance in dilute alcohol was precipitated with excess of silver nitrate dissolved in the same solvent, the resulting salt being washed, and dried in a vacuum desiccator in the absence of light. Ag=49*77. C,,H,O,NBAg, requires Ag= 49'54 per cent. For example : 0.2883 gave 0.1428 Ag.92 FENTON AND JONES: XELATIONSHIPS OF OXALACETIC ACID. 0.1506 gave 0.3334 CO, and 0.0761 H20. The changes which take place are therefore represented as follows : (1) When excess of dilute sulphuric acid is used : (2) when water only is employed : C = 60.37 ; H = 5.61. C9Hlo0,N, requires C = 60.67 ; H = 5.61 per cent. CIOW1,o,N, = C10H,03N2 + H,07 CloHlo0,N2 = C9Nl0O2N, + CO,. When the concentration of the acid falls below a certain value, both reactions occur simultaneously, and the nature of the change can easily be followed by measurement of the evolved carbon dioxide.Using decinormal sulphuric acid, for example, about 26 per cent. of the hydrazone was found to undergo the second change, and the proportion of carbon dioxide became less and less as more concentrated solutions of the acid were employed, until with acid of about normal strength the amount of gas was not perceptible. Experi- ments were now made with other acids, using decinormal solutions and making the conditions exactly the same in each case, and it will be seen that the stability of the hydrazone, as regards retention of the 4-carbon molecule, is evidently a function of the concentration of the hydrogen ions.The experiments were made by placing about 0.1 gram of the hydrazone in a tube having a capacity of about 15 c.c., covering it with 7.5 C.C. of the decinormal acid, and heating t o boiling for about 2 or 3 minutes in a water-bath. The evolved carbon dioxide was collected in a Lunge's nitrometer, the residual gas swept out of the tube by a current of about 40 C.C. of purified air, and the estimation made by absorption with potash in the usual manner. The accompanying sketch will give an idea of the apparatus employed. A preliminary experiment was made with pure Iceland spar in order t o test the apparatus, and the result showed that the accuracy was well within the limit desired for the purpose, as 0.1065 gram gave 23.6 C.C. of carbon dioxide (cow.), the calculated volume being 23% C.C.The order obtained in the table on p. 93 very closely approximates to that of the relative strengths or ' affinities ' of the acids as measured by the well-known methods. In the case of trichloroacetic acid (with regard to which there was a t one time a discrepancy), it is probableFENTON AND JONES : RELATIONSHIPS OF OXALACETIC ACID. 93 Corrected volume of co,. that the high result is due to hydrolytic action a t the temperature employed. It would appear, therefore, that the process described affords a very simple method of comparing the affinities of acids a t looo, that is, of placing them in ' order of merit.' The exact interpretation of the numbers themselves can scarcely be arrived at from the few and relatively rough determinations here recorded, but the authors hope to make more extended observations in this direction.If it be admit- ted, as above conjectured, that the results depend upon the con- centration of the hydrogen ions, it is easy t o understand why the full proportion of carbon dioxide is not obtained even in the case of pure water, since the resulting product is also an acid, and therefore tends to increase the stability of the still undecomposed hydrazone. CO, for 1 gram substance. Weight of substance. Nature of acid. I- Nitric.. .......................... Hydrochloric .................. Suiphuric ....................... Sulphuric.. ..................... TrichIoroacetic .............. Tartaric ........................ Malic ............................ Succinic.. ......................Citric .......................... Acetic ........................... [Pure water .................... 0.0992 0.0993 0.0990 0*1050 0'0980 0.0990 0-0990 0-0998 0.0995 G.0984 0.1200 I 1.65 1'73 2.56 2.84 3-96 6 4 8 6 *76 7 -21 7 -30 7.72 10.90 16.6 17.4 25 '8 27-0 50.8 66'9 68.2 72 *I 73 '3 78-6 90'01 Action of Hydrazine.-When well cooled alcoholic solutions of oxalacetic acid and hydrazine hydrate are mixed in molecular propor- tion, the mixture being surrounded by ice and salt, an immediate turbidity is produced and a heavy oil separates which is quickly changed to a hard, white, apparently amorphous mass. This was separated from the liquid, the examination of which will be described below, thoroughly ground with several changes of absolute alcohol and dried in a vacuum desiccator.The yield was about half the weight of acid taken. It dissolves easily in cold water, the solution gives a red colour with ferric chloride, and quickly reduces Fehling's solution in the cold. It melts sharply and with violent decomposition a t 99'. On analysis, the following results were obtained : 0.1656 gave 0.1614 CO, and 0.0835 H,O. C = 26.58 ; H = 5.60. 0.1041 ,, 28.6 C.C. nitrogen a t 18.5' and 734 mm. N=31*17. C4Hlo0,N, requires C= 26.97 ; H = 5.61 ; N = 31.46 per cent. The substance is therefore the Aydrazine salt of the hydrazone, or of94 PENTON AND JONES : RELATIONSHIPS OF OXALACETIC ACID. the hydmzide of oxalacetic acid, C0,H*C(N,H2)~CH2*C02H,N2H, or C0,H G O CH,* CO*N,H,,N,H,.* When an aqueous solution of this product is heated for a short time in a water-bath it undergoes a marked change.The solution now gives with ferric chloride a very intense brownish-violet colour, and after concentration the solution sets to a soft mass which is seen under the microscope to consist of long, transparent prisms. These, after washing with alcohol and drying in a vacuum desiccator, melted at 196'. On analysis, the following result WAS obtained : 0*1696 gave 58.6 C.C. nitrogen at 20' and 737 mm. C,H,O,N, requires N = 39 -43 per cent. Rothenburg (Bey., 1892, 25, 344l), by the action of hydrazine hydrate on ethyl oxalacetate, obtained (1) a product easily soluble in alcohol, which is the ester of pyrazolone-3-carboxylic acid, and (2) one nearly insoluble in alcohol which melted at 2 3 8 O , and had the composition C,H,O,N,.The latter he considers to be the hydrazide of py razolone-3-carbox y lic acid (Pyrazolon-3-carbonyl h y drstzin), N= 39.16. It appears highly probable that this second product is identical with the one obtained in the present case, although there is considerable discrepancy as to the melting point. The alcoholic solution which remained after separating the hydrazine salt above described was allowed to evaporate in a vacuum desiccator, and the partly solid residue was treated with cold water, In this way a nearly white, granular residue was left which is very aparingly soluble in cold water, and separates from boiling water in minute crystalline aggregates. For analysis, it was purified by dissolving i n alcohol, precipitating with ether and light petroleum, and drying in a vacuum.It turned dark brown, or nearly black, without melting, at about 260-270'. On analysis : 0*1110 gave 0.1514 CO, and 0.0353 H20. C=37*20; H=3.53. 0.1102 ,, 20.9 C.C. nitrogen at 20' and 735 mm. N = 21.46. C,H,O,N, requires C = 37-50 ; H = 3.12 ; N = 21-87 per cent. This product therefore corresponds entirely in composition and pro- perties w it h the pyazolonecarboxy Zic acid which Rot henburg obtained from the ester above mentioned by hydrolysis with alkalis or con- centrated hydrochloric acid. Action. of Hydroxy~amirze.-when an alcoholic solution of hydroxyl- amine, prepared by Wohl's method (Ber., 1893, 26, 730) is mixed * This composition explains the comparatively small yield, since only one mol. of hydrazine was employed.l?ENTON AND JONES : RELATIONSHIPS OF OXAT,ACETIC ACID, 95 with oxalacetic acid, also dissolved in alcohol, in molecular proportion, a turbidity is produced which almost immediately disappears, and the solution after standing for some hours and evaporation in a vacuum desiccator leaves a thick syrup which sets to a white, crystalline mass on stirring or on long standing. This when recrystallised from anhydrous ether melts and decomposes with violent frothing at 133' when gradually heated, or 142-143' if quickly heated. It is very soluble in water or alcohol, but less so in ether ; with ferric chloride, the solution gives a, brownish or yellow colour.On analysis : 0.1758 gave 0.2135 GO, and 0.0550 H20. C,H50,N requires C = 32.65 ; H = 3.40 per cent. When the substance is mixed with excess of acetic anhydride or acetyl chloride, i t dissolves, and if the resulting solution be allowed to stand for a day or two and then kept in a vacuum desiccator over solid potash and sulphuric acid, the product on treatment with water gives an intense indigo-blue colour with ferric chloride, Piutti (Chem.Centr., 1888, 68; Gaxx., 1888, 18, 457), by the action of the sodium derivative of ethyl oxalacetate upon hydroxylamine hydrochloride, obtained the compound (CO,Et),*CH,*G:NOH, and the compound CO,Et*CH,*G(NOH)*CO,H by partial hydrolysis. From the latter, Cramer (Be?., 1891, 24, 1206) obtained the free acid P-oximidosuccinic acid or the 6 oxime of oxalacetic acid.' This melted at 88' and gave a characteristic 6Zue colour with ferric chloride." Ebert (Annalen, 1885,229, 76), by the action of nitrous acid on ethyl succinosuccinate, had obtained an acid having the same composition, but this decomposed with frothing a t 126O, and gave, with ferric chloride, a brown o r yellow colour.Cramer (Zoc. cit.) showed that these two acids are stereoisomerides, and gives reasons for assigning to them the following constitutions (see also Hantzsch, Ber., 1891, 24, 1192) : C=33*12; Hz3.47. a-acid (Ebert's) c02"* 8 *CH2* (labile), HO*N @acid (Cramer's) Co2H*8 *CH2* (stable). N*OH By the action of concentrated sulphuric acid, acetyl chloride, or acetic anhydride the a-acid (or its compounds) can be transformed into the p-form, the product then giving the characteristic blue or violet colour with ferric chloride. It would naturally have been expected that the action of hydroxyl- * From the somewhat high percentage of carbon in the product obtained in the present case, it is possible that it is not absolutely pure j the numbers, however, are practically identical with those obtained by Cramer, who found C=33'16 and 33.22 ; H=3*10 and 3'16 per cent.96 FENTON AND JONES: RELATIONSHIPS OF OXALACETIC ACID.amine upon free oxalacetic acid would give rise to the P-acid, but this evidently is not the case. The properties of the product obtained in the present case closely resemble those of Ebert's a-acid, and the action of acetic anhydride transforms it into a derivative of the P-form. This difference between the behaviour of the free acid and the ethyl ester may possibly be due to the tautomeric difference previously suggested (Michael and Bucher, Ber., 1896, 29, 1792).Action of Ammonia.-By mixing together alcoholic solutions of oxal- acetic acid and ammonia in different proportions, white precipitates are immediately produced which, after washing with alcohol and drying in a vacuum desiccator, have a composition varying between that required for a normal and an acid salt. If, however, a fairly dilute solution of the acid in absolute alcohol be poured into an excess (slightly more than 3 mols.) of alcoholic ammonia with continuous and vigorous shak- ing, the precipitate obtained, after washing and drying as before, corresponds in composition to the normal salt. 0.1638 gave 24.9 C.C. nitrogen a t 22' and 750 mm.The salt melts and decomposes at 75-77', giving a yellow liquid which solidifies t o a crystalline mass on cooling. It has a neutral re- action, and gives a deep red colour with ferric chloride. When the ammonium salt is left exposed t o the air, it is transformed into a yellow, gummy mass which no longer gives the red colour with ferric chloride. I n order to ascertain whether a further action of ammonia could be induced, the ammonium salt was heated in a stoppered bottle for some hours at 100' with alcoholic ammonia in large excess. A white, crys- talline crust of ammonium carbonate was obtained, and a yellow, gummy mass separated at the bottom of the vessel (the alcoholic liquid left only a trace of residue on evaporation). This gummy mass was dissolved in water and acidified with dilute sulphuric acid.A white precipitate was thus obtained which, after washing and drying, melted and decom- posed at 273O, gave a reddish-yellow colour with ferrous sulphate and appeared to agree in all respects with the methylpyridinecarboxy~~c acid (m. p. 2'74') which Bottinger (Annalen, 1877, 188, 330) obtained by the action of alcoholic ammonia on pyruvic acid. Action of Urea.-On mixing alcoholic solutions of oxalacetic acid (1 mol.) and urea (rather over 2 mols.) and allowing the mixture to stand in a vessel surrounded by ice, a crystalline precipitate is formed on stirring. This, when washed with alcohol and dried in a va,cuum, melts and decomposes at 124' and has the composition of a normal urea salt. N= 17.27. C,H40,,2NH, requires N= 16.86 per cent.0.1866 gave 23.5 C.C. nitrogen a t 17' and 747 mm. N= 14.62. C,H,0,,2CON,H4 requires N = 14.58 per cent,FENTON AND JONES: RELATIONSHIPS OF OXALACETIC ACID. 97 The salt is fairly easily soluble in water and gives a deep red colour with ferric chloride. When heated alone or with phosphorus oxy- chloride, it yields crystalline products which have not yet been examined, Action of Aniline.-When ethereal solutions of the acid and aniline are mixed in molecular proportion, a white precipitate is formed which melts a t 65-66'. An aqueous solution of this salt remained clear for over a week and gave no precipitate on boiling. If the enolic formula be ascribed to oxalacetic acid, this observation would further confirm the hydroxyfumaric constitution as suggested by Nef and by Michael (compare Michael, Bey., 1886, 19, 1372; Michael and Bucher, Zoc.Action of Benzylphenylhydi.axine.-On mixing oxalacetic acid, dis- solved in a small quantity of water, with benzylphenylhydrazine dis- solved in acetic acid, in molecular proportion, and cooling the mixture with ice, a certain quantity of gummy substance separates at first, but after standing for several hours a nearly white precipitate is obtained. This was collected and washed, first with strong and then with dilute acetic acid, dried in a vacuum desiccator, and crystallised from ether. It melted at 105-106'. cit.). 0.1207 gave 10.4 C.C. nitrogen a t 18Oand 757 mm. N = 10.20 per cent. The substance is therefore probably not an oxalacetic acid derivative (the benzylphenylhydraxone of which would require N = 8.9 per cent.), but the corresponding hydrazone of pywvic acid, C16H2602N2, which requires N = 10.44 per cent.On using alcoholic solutions of the acid and the hydrazine, a yellow gum is obtained, which never quite solidifies, even on long standing in a desiccator. By treating this with light petroleum and dissolving the residue in ether, a certain amount of yellow, crystalline substance was obtained, but the quantity was too small for examination. Oxidation of the Acid.-When an aqueous solution of the acid is acted upon by bromine in molecular proportion, a product is obtained, as was previously shown, which gives an intense bluish-violet colour with ferric chloride in presence of caustic alkalis, whilst this on acidification with dilute sulphuric acid is changed to a transient emerald green.The colour-changes, in fact, exactly resemble those given by hydroxymaleic acid with the same reagents (Trans., 1894, 65, 904). If other solvents, such as acetic acid or ethyl acetate, be employed instead of water, a similar result is obtained, but the violet colour appears more slowly. It is probable that a bromo-acid (bromoxalacetic or bromohydroxyfumaric acid) is first produced and then hydrolysed. On evaporating the acetic acid or ethyl acetate solution in a vacuum, or by extracting the aqueous product with VOL. LXXIX. H98 FENTON AND JONES: RELATIONSHIPS OF OXALACETIC ACID. ether, a thick syrup is obtained which does not crystallise but still gives the ferric chloride reaction." A product giving similar colour reaction is o6tained when oxalacetic acid is oxidised with the calculated quantity of hydrogen dioxide in presence of ferrous iron, or when malic acid is so oxidised, using nearly two atoms of oxygen to one molecule of the latter acid.All attempts to isolate this colour-giving acid have so far been unsuc- cessful. It is evidently very unstable and does not separate under the same conditions as those employed in the isolation of dihydroxymaleic acid nor can i t be extracted with ether. The authors are, therefore, inclined to the opinion that it is isomeric and not identical with the latter acid, being probably the ketonic modification, CO,H*CO*CH(OH)*CO,H. Further light is thrown upon this question by the action of phenyl- hydrazine. It was shown that the solution obtained by oxidising malic acid in presence of iron gives with phenylhydrazine in the cold a voluminous orange precipitate, which by recrystallisation from hot chloroform is obtained in brilliant orange needles melting at 217-219'.This product gave very constant results on analysis, the mean of four concordant analyses made with distinct specimens, prepared on different occasions, giving, C = 63.20 ; I3 = 5.17 ; N = 20.16 per cent.? These numbers do not correspond to those required for a derivative of oxalacetic acid, but t o a more oxidised product, and since no such compound can be obtained by the direct action of phenylhydrazine on oxalacetic acid, it is probable that it is the result of further oxidation by the hydrogen dioxide, which attacks a portion of the oxalacetic acid as fast as i t is formed.It can, in fact, be prepared by oxidising oxalacetic acid in presence of ferrous iron, or by adding a further quantity of the dioxide in the oxidation of malic acid, and subsequent addition of phenylhydrazine acetate. Prepared in the latter manner, the recrystallised product melted at 223-224'. On analysis, the following result was obtained : 0.1259 gave 0,2909 CO, and 0.0561 H,O. * When excess of bromine was employed and the mixture heated, crystalline plates were obtained which no longer gave the above reaction. They melted at about 92" and gave, on analysis, Br=64.61 per cent. This product is evidently dibromopyruvic acid, which requires Br = 65.04 per cent. .t. The properties of this substance are, in some respects, very similar to those of the osaaone of hydroxypyruvic acid discovered by Nastvogel, and in composition the two nubstances do not differ widely.C,,H,,N40, requires C = 63'82, H = 4-96, N=19*85 per cent. The two conipounds are, however, at once distinguished by the melting points and by other properties which will be described below. C=63*01; H=4*94.FENTON AND JONES : RELATIONSHIPS OF OXALACETIC ACID. 99 These numbers correspond to those required for a derivative ob- tained by the addition of three molecules of phenylhydrazine to one molecule of either dihydroxymaleic or dioxosuccinic acid,* with elim- ination of three molecules of water, C,H,O, + 3N,H,Ph - 3H,O requires C = 63.15 ; H = 5-26 ; N = 20.09 C,H,O, + 3N2H,Ph - 3H20 requires C = 6346 ; H = 4.80 ; N = 20.19 I n order to throw light upon the constitution of the compound, the following experiments were made, The well dried substance was mixed with excess (about ten times its weight) of acetic anhydride and heated on a water-bath, when a considerable evolution of gas took place and a clear, dark coloured solution resulted.The latter, on standing, deposited a mass of orange crystals, which when recrystallised from hot alcohol appeared in the form of beautiful, bright, orange-red needles melting a t 149-1 50'. On analysis : per cent. per cent. 0.1502 gave 0.3729 CO, and 0.0616 H,O. C1,H,,ON, requires C = 68.18 ; H.= 4-54 per cent. The composition, melting point, and other properties of this product show that it is identical with that which Knorr obtained by the action of acetic anhydride upon the osazone of hydroxypyruvic acid (Bey., 1888, 21, 1201), and which Will prepared from the same source by tho action of hydrogen chloride in alcoholic solution (Bey., 1891, 24, 3831).It was also obtained by Knorr (Zoc. c k ) by heating the corre- sponding pyrazolonecarboxylic acid at its melting point, and was shown by him to be phenylhydrazineketophenylpyrazolone, C = 67-72 ; H = 4.55. r P h * C O N= CH >C:N*NHPh. This being a derivative from a 3-carbon acid, it was important to ascertain the nature of the other products of the reaction; and the experiment was therefore repeated in such a manner that the gaseous product could be displaced by a current of inert gas, the substance being heated with acetic anhydride as before, a current of purified nitrogen passed through the flask, and the product collected in an excess of lime-water.In this way, abundant evidence of the presence of carbow dioxide was obtained. After the resulting mixture had been allowed to stand for a day or two, the mother liquor from the crystals was mixed with excess of sodium hydroxide solution and * That is ' anhydrous ' clihpdroxytartnric acid, C02H*CO*CO*C0,H. Compare Anschiita and Parlato (Ber., 1892, 25, 1977). l I 2100 FENTON AND JONES : RELATIONSHIPS OF OXALACETIC ACID. distilled in steam, when a notable quantity of aniline was found in the distillate. These experiments fairly well establish the fact that the substance in question is a 4-carbon derivative, and it must therefore be regarded either as FO*CO,H CH(OH)* CO,H’ (1) The dihydrazide-hydrazone of the ketonic acid, tautomeric with dihydroxymaleic acid, or as (2) The monohydrazide-dihydrazone of dioxosuccinic acid.* F( N,HPh)*CO*N,H,Ph S(N,HPh)*CO,H (l) CH(OH)*CO*N2H2Ph Or (2) C(N,HPh)*CO*N,H,Ph I n the first case, the formation of aniline can easily be explained by the oxidation of the CH*OH group by phenylhydrazine, and the change might be expressed by the equation The second formula, however, perhaps better explains the acidic character of the substance (for example, the formation of a crystalline sodium salt when heated with sodium carbonate solution), and in this case the production of aniline must be accounted for in the decompo- sition of the phenylhydrazine residue by heat (compare Reissert and Kayser, Ber., 1890, 23, 3703).I n either case, the initial product would be the ketonic acid, CO,H*CO*CH(OH)*CO,H. It has already been suggested (Fenton, Trans., 1896, 69, 547) that dihydroxymaleic acid may undergo tautomeric change into this form, and further evidence in this direc- tion mill be afforded in a subsequent communication. Experiments were therefore made in order to ascertain whether the product at present under discussion could be produced from dihydroxy- maleic acid. It has previously been shown (ibid., 548) that by the action of phenylhydrazine on this acid in acetic acid or alcoholic solution, the normal phenylhydrazine salt is produced, C,H40,,2N,H3Ph. This salt was now heated on a water-bath with excess (about 2 mols.) of phenylhydrazine acetate and water for about 2 hours.The result was an orange-coloured product, which, when recrystallised from hot chloroform, melted at 222O and had all the properties of the malic acid derivative under discussion. 0.1210 gave 20.8 C.C. nitrogen a t 20° and 756 mm. N = 19.98 per cent. .It It might, of course, be the phenylhydrazine salt of the corresponding pyrazolone- carboxylic acid ; but this is improbable from the fact that the sodium salt, when decomposed by hydrogen chloride, gives back a product which melts practically at the same temperature, and appears to be identical with the parent substance.FENTON AND JONES : RELATIONSHIPS OF OXALACETIC ACID. 101 Reviewing the whole of this evidence, the authors are inclined to prefer the second formula suggested for the substance, that is, to re- gard it as the monohydrazide-dihydrazone of dioxosuccinic acid, since it seems improbable that the CH*OH group represented in the first formula would resist the action of phenylhydrazine in the experiment last recorded; this formula also agrees somewhat bebter with the results of analysis.Surnmayy. The principal results obtained in the present investigation may briefly be summed up as follows. Oxalacetic acid by interaction with phenylhydrazine yields the phenyZ- hydrazone, CO,H-CH,*C( N,HPh)*CO,H, which readily loses carbon dioxide when heated with pure water giving the hydrazone of pyruvic acid. This decomposition is prevented by acids if the latter are of suffi- cient concentration, the result in this case being phenylpyrazolone-3-carb- oxylic acid. By comparing the influence of different acids in this respect, i t is easy to compare their relative ‘ strengths ’ or affinities.’ Hydrazine hydrate gives the hydrazine salt of the hydrazone CO,H*CH,*C(N,H,)- CO,H,N,H, together with Rot henburg’s pyyazo- Zonecarboxylic acid. The first named salt when heated with water gives a white, crystalline compound which is probably the jiydrcczide of the latter acid. Hydroxylaminegivesrise to the compound CO,H*CH,*C(NOH)*CO,H which contrary t o expectation appears to be identical with Ebert’s a-oximidosuccinic acid and not the /3-compound. It yields, however, a derivative of the latter by action of acetic anhydride or acetyl chloride. Ammonia and urea give the respective normal salts and the former salt, when heated with excess of alcoholic ammonia, gives a substance corresponding with Bottinger’s methylpyridinecarboxylic acid. When oxalacetic acid is oxidised with hydrogen dioxide in presence of iron, a product is obtained closely resembling dihgdroxymaleic acid in properties but which has not yet been isolated. The authors give reasons for considering that this acid has tbe tautomeric formula CO,H-CO*CH(OH)*CO,H. When treated with phenylhydrazine, this product gives a bright orange compound melting at 222-224O. The latter has been the subject of an exhaustive examination and the evi- dence leaves little room for doubt that it is the hydrazide-dihydrazone of dioxosuccinic acid.

ISSN:0368-1645    

DOI:10.1039/CT9017900091

出版商:RSC    

年代:1901

数据来源: RSC

摘要:

102 DIXON : INTERACTION OF URETHANES AND IX.-Intcrastion u f Urethanes and Primary Benxenoid Amines. By AUGUSTUS EDWARD DIXON, M.D. IN a paper published some years ago (Trans., 1895, 67, 562), the author gave, incidentally, a brief account of cd-phenyl-p-tolylcarb- amide; this substance was prepared from phenyl isocyanate and ptoluidine, the melting point of a specimen only once recrystallised being 212-213O (corr.). The writer regarded the compound as new, havingoverlooked descriptions of i t given by Huhn (Bey., 1886,19,2408), who records €he melting point as 211', and by Coldschmidt and Meissler (Ber., 1890, 23, 273); the latter chemists obtained it by heating p-tolyl isocyanate with thiocarbanilide, and give the melting point as 211' also ; whether corrected or otherwise is not mentioned in either case.These descriptions appear to have escaped the notice of Manuelli and Comanducci, who state in a recent paper (Gaxx., 1899, 29, ii, 142) that it is produced by heating phenylurethane withp-toluidine ; a complete analysis is appended, and the melting point given as With a view to ascertain the cause of this discrepancy, some experi- ments were undertaken, of which an account is given helow. Amongst the acidic derivatives of urea, isomeric forms are now known to exist (compare Trans., 1899,75,375), and i t struck the writer as just possible that the substance melting a t 260' might be a 'labile' form of the symmetrical carbamide, for instance, PhN: C( OH) *NH*C,H7. The probability, however, of this being the explanation was slight., considering that phenylurethane and aniline yield ordinary carbanilide, CO(NHPh),, and not an isomeride (Wilm and Wischin, Anncclen, 1868, 147, 160); moreover, the nwriter observed some years ago that the (sec.)-dibutylcarbamide produced from butylurethane and butylamine (Trans., 1895, 67, 561) is identical with that obtained by desulphur- ising ab-(set.)-dibutylthiocarbamide with silver nitrate.Before examining the interaction between phenylurethane and p-toluidine, it was decided to once more verify the melting point of ab-phenyl-p-tolylcarbamide, notwithstanding that Paal and Van- volxem have also recorded it as 212' (Be?., 1894, 27, 2426); their preparation was made from phenyl isocyanate and p-toluidine, but it is not stated whether the melting point was corrected.* * It is hardly necessary to remark that, a t these somewhat high temperatures, the correction is occasionally considerable, amounting to several degrees ; the melting points recorded by the writer in the present paper are all corrected for the exposed thread of mercury.25 9-2 60'.PRIMARY BENZENOID AMINES. 103 The urea was this time prepared by desulphurising the correspond- ing thiocarbamide (from phenylthiocarbimide and p-toluidine, m. p. 141-1 42') with silver nitrate. After recrystallisation from boiling alcohol, the substance was pure white, and melted a t the temperature previously recorded, namely, 212-213O ; it occurred in long, flexible, flattened needles, having a brilliant, silvery lustre, becoming electrical on friction, and afforded, by wet combustion, 74.32 per cent.of carbon, against 74.29, calculated for C,,H,,ON,. It should be added that the melting point of this specimen, when several times recrystallised from alcohol, rose somewhat, becoming eventually constant at 21 5'. I n the experiments with bases and urethanes, the method first adopted was to heat exactly equivalent proportions of the constituents in a sealed tube; but on learning subsequently that Manuelli and Comanducci had boiled them together in an open vessel under a reflux condenser, their preparations were carefully repeated under the pre- scribed conditions. PT~nyZuwthccne artd p-Toluidins.-A very slight excess of the ure- thane was taken, the mixture being heated in a paraffin bath at about 185' for 3 hours, using a tube as condenser.The product, when cold, formed a greenish-brown, friable, crystalline mass, penetrated by a dark oil. After washing with water acidified with hydrochloric acid, and then with spirit and ether, it became white; the yield of dry product amounted to something over 40 per cent. of the weight of materials employed. It mas dissolved in the least possible quantity of boiling alcohol, in which it is rather sparingly soluble; on cooling, a felted mass of pearly crystals was obtained, resembling thiocarb- anilide in appearance, and becoming highly electrical on friction ; the mother liquor gave a second crop of the same substance melting at 260-261'. Presently a third crop of crystals separated, in flattened white needles, becoming moist at 212O, and melting, rather indistinctly, between 213' and 216'.This was no doubt phenyl-p-tolylcarbamide, containing a little of the substance of higher melting point ; a fourth crop melted a t 213-2144 and was, consequently, the real phenyltolyl compound, practically pure, but the amount was not enough for analysis. The nitrogen in the substance melting at 260-261' was estimated : 0-2 gave 20.4 C.C. nitrogen at 17' and 760 mm. N = 11.83 per cent. Another determination gave 11-75 per cent.; these figures are too low for phenyltolylcarbamide, or its possible isomeride, which would require N = 12.43 per cent. An examination of the oil, removed from the original crude product, showed it to contain a large amount of aniline. Once in possession of this fact, the course of the interaction becomes easy to understand ;104 DIXON : INTERACTION OF URETHANES AND the p-toluidine, even though present in less than equivalent propor- tion, attacks to a greater or less extent the phenyltolylcarbamide first produced, the interactions running as follows : (I). PhNH*CO*OEt + C7H7*NH2 = PhNH*CO*NH*U7H7 + EtOH.(11). PhNH*CO'NH*C+H7 + C7H7*NH2 = PhNH, + CO(NH.C7H:)2. The substance melting a t 260-26 1' is thus di-p-tolylcarbamide (melting point 260°, Manuelli and Ricca-Rosellini, Gaxz., 1899, 29, ii, 124) ; this requires N = 11.70 per cent. ; the nitrogen found, as just stated, amounted to 11-83 and 11.75 per cent. A similar experiment was also performed in a sealed tube; in the first case, 14 grams were heated for 3 hours at 200'; in the second, 17 grams for 4 hours at 2104 the latter giving a much better yield.Aniline was formed, together with a solid, which began to soften at 250°, and was melted at 256'; by recrystallisation, this yielded di-p- tolylcarbamide, softening a little at 259', and melting at 260-260.5O ; the mother liquor gave a crop of needles, melting, after a couple of recrystallisations, a t 21 1-21 Z', and consisting of phenyl-p-tolylcarb- amide. pToZyZzcretAane and Aniline.-In this converse experiment, the above constituents were heated, under pressure, for 3 hours at 220-230°, the urethane being in very slight excess. Washing with spirit removed the adherent oil, and left a white solid, melting, somewhat indistinctly, at about 205-206' ; this was eventually resolved into a main quantity of phenyl-p-tolylcarbamide melting at 213-214' (found N = 12.3 per cent.), and a minimal quantity of a substance melting at about 256-257', probably dip-tolylcarbamide, but the amount was in- sufficient for complete purification and analysis, only about 0.2 gram being obtained from 10 grams of material.In this case, no doubt, the aniline at first expels some p-toluidine from the phenyl-p-tolyl- carbamide, the change reversing itself to some extent with the free p-toluidine when the large excess of aniline has been diminished by interaction with the urethane. This experiment was also repeated by boiling the conetituents in an open vessel, but no difference worth recording was observed in the phenomena, save that the only product isolated was the phenyl-p- tolyl compound (m.p. found, 211.5-212.5O). From the above results it would appear that p-toluidine is much more active in expelling aniline than vice uers&. Phylwethccne and o-Tohidine.-Two experiments were made under pressure, the mixture in one case being heated for about half an hour at 270°, in the other, for three hours at 220'; no material difference was observed in the results. A dark-coloured solid was obtained, mixed with an oil, which gave the reactions of aniline; the formerPRIMARY BENZENOID AMINES. 105 became white on washing with alcohol and ether ; it began to shrink at 224', and melted, indistinctly, between 226' and 229'. It was boiled with a quantity of alcohol insufficient to dissolve i t com- pletely, and the residue (which now shrank a little a t 239' and melted about 242-243'), was recrystallised from the same solvent.It is rather sparingly soluble, and was deposited on cooling in slender, vitreous prisms melting at 249-250'. Obviously this substance could not be phenyl-o-tolylcarbamide, whose melting point, according to Huhn (Bey., 1886, 19, 2410), lies at 212q or carbanilide (m. p. 238'); presumably, therefore, i t was di-o-tolylcarbamide. The melting points given by various observers for this compound are too divergent to be of much use for identifi- cation, but a nitrogen determination gave figures agreeing with those required for the ditolyl derivative, CO(NH*C,H7), : Found N = 11.97. Out of the alcoholic extract, exceedingly fine needles separated in woolly-looking clumps ; after a couple of recry stallisations they became soft at 202' and melted at 203-204'; they proved to consist of nearly pure phenyl-o-tolylcarbamide : Cl,H160N2 requires N = 11-70 per cent.Found N = 12.6. An experiment made by heating the constituents together a t 185' in a reflux apparatus for 4 hours gave similar results, save that a rather larger proportion of the phenyl-o-tolyl derivative was obtained. The melting point just recorded for the latter compound lies a good deal below that given by Huhn, who obtained the substance (Zoc. cit.) from carbophenyl-o-tolylimide and weak alcohol ; this lowness, i t seemed, might be due to the presence of traces of di-o-tolylcarbamide, since the latter is less soluble in alcohol than phenyl-o-tolylcarbamide ; however, to make certain, the compound was again prepared, first by desulphurising ab-phenyl-o-tolylthiocsrbamide (m.p. 142') with silver nitrate, and next by combining phenyl isocyanate with o-toluidine. When several times recrystallised from strong alcohol, both products were deposited in very minute needles melting at 207-208'. C1,Hl,0N2 requires N = 12.43 per cent. Cl4K,,ONP requires N = 12-43 per cent. Found N = 12.5. Phe.nyZ-a-~p~~tlTLyZcarbccmide.-Amongst other compounds described in Manuelli and Comanducci's paper is a symmetrical phenyl-a-naphthyl- carbamide, obtained from a-naphthyla mine and phenylurethane ; it is said to blacken at about 274", and melt at 27'7-278'. In order to verify this statement, the carbamide was prepared, first, by desul- phurising the corresponding thiocarbamide (m.p. 163') with silver nitrate, and next, by combining phenyl isocyanate and a-naphthyl-106 DIXON : INTERACTION OF URETHANIIS ANb amine in dry benzene. The latter method gave a pure white solid : after three recrystallisations from a mixture of benzene and alcohol, it occurred in snowy-white, silky, microscopic needles, which softened at 223O, as if about to melt; they did not fuse, however, but at 224' hardened again. On raising the temperature, the substance gradually darkened from about 230°, and became moist, until at about 244' i t melted, evolving gas. If put into the melting point apparatus at or above 223O, it melts to a water-clear liquid, resolidifying almost immediately ; if put in only two or three degrees below this temperature, it melts, becoming clear, on reaching it; in a moment, however, it resolidifies, and now melts, somewhat indistinctly, at the higher temperature, to a black liquid.The specimen prepared by the former method retained, even after several recrystallisations, a very faint buff tinge ; its behaviour on heating was, however, similar to that of the isocyanate product, save that its melting point was a degree lower, namely, 222O. Found N = 10.88 ; CI7H,,ON, requires N = 10.64 per cent. The properties just described do not agree very satisfactorily with those attributed by Manuelli and Comanducci to phenylnaphthylcarb- amide; it was, of course, possible that the not very marked softening at 223Omight have escaped their notice, but even if so, there still remained a large discrepancy.In order to clear the matter up, their experiment was repeated. Phenylwrethne and a-~ap~t~~Zccmi~.-Equal weights, as prescribed (corresponding to over 15 per cent. of base in excess of the calculated quantity), were heated in a paraffin-bath at 220-230'. In about halF an hour, solid matter began to appear, and before an hour had elapsed the contents of the flask were apparently solid ; the heating was con- tinued, however, in accordance with the directions, for nearly three hours. When cool, the product was broken up, and washed with dilute hydrochloric acid; from the washings, by treatment with excess of alkali, a colourless liquid was precipitated ; this was extracted with ether, and remained on evaporation of the latter, as a yellowish oil, which gave all the reactions of aniline, and was further identified by the production, with phenylthiocarbimide, of thiocarbanilide, The residue was ground up in a mortar with cold spirit, filtered, washed with more spirit until practically colourless, and then boiled with a large volume of alcohol ; as it proved to be nearly insoluble in this solvent, the mixture was filtered whilst still hot, and the residue, which was now snow-white, examined.It formed a micro- crystalline powder, becoming highly electrical on friction ; when heated in a capillary tube, it showed no sign of change up to about 270°, when it began to darken a little ; neither, when put into the apparatusPRIMARY BENZENOID AMINES. 107 CH, .............................. 151" C2H, ............................1 100 ................... i 155 C,H5*CH(CH,) ............... 156 I at 230' or 240', did i t melt or soften. At 2 8 3 O , it darkened greatly, and melted at 286-287', with effervescence, to a black liquid. The anticipation that this compound would prove t o be dinaphthyl- carbaniide, CO(NH* CloH7)2, was confirmed by the results obtained on making a complete analysis : Found C=80*78; H=5*16 ; N=9*24. C,,H,,ON, requires C = 80.75 ; H = 5.14 ; N = 9.00 per cent. Appended are the figures required for phenylnaphthylcarbamide, together with those obtained by Manuelli and Comanducci ; the writer is unable to explain the discrepancy, but recognises that their data entirely justify the conclusions at which they arrived : Calculated for Cl7HI40N2, C = 77-86 ; H = 5.34 ; N = 10.64 per cent.Found ........................ C = '77.52 ; H = 5-68 ; N = 10.51 ,, ,, The alcoholic washings from the above compound, when diluted with water, gave a small quantity of a purplish solid; after a couple of recrystallisations from alcohol, using animal charcoal, the substance was obtained in masses of woolly needles, still retaining a very faint pinkish tinge ; they melted about 221°, resolidifying quickly, and commencing then to darken at about 230O; the amount was barely suflicient for analysis, but the compound was obviously phenyl- a-naphthylcarbamide, nearly, but not quite, pure, (C2H,),CH*CH, ............ C,H,*C(CH,),*CH, .......... CgHlg ........................ C,,H,,. ....................... I n connection with the various results detailed above, it may be noted that Manuelli and Comanducci have also described a symme- trical phenylamylcarbamide, obtained from phenylurethane and amy I - amine, and separating, after numerous recrystallisations, from dilute alcohol, in slender white prisms melting at 238'.Now all the known symmetrical disubstituted ureas containing one phenyl, together with one purely fatty, radicle, melt a t temperatures NHPh far below this; in the appended list of such compounds, , the variable radicle, R, alone is given. Radicle. 1 M. p. 1 Radicle. I I M. p. 70" 103-106 63 99 ~~ - Moreover, normal amylamine is stated t o have been employed in preparing the phenylamylcarbamide in question : in this case, the melting point might be expected to lie below 155' (that of phenyl-108 FORSTER : INFRACAMPHOLENIC ACID, AN ISOMERIDE OF isoamylcarbamide), instead of 83' above it.It seems not impossible that this interaction runs a course resembling that between aniline and p-tolylurethane (p. 104) ; and that the sripposed phenylamyl- carbamide is really carbanilide, which, according to Young and Clark (Trans., 1898, 73, 367), melts at 238-239O. This, however, is a mere conjecture, the writer having no opportunity of carrying out the experiment with normal amylamine, and is advanced with reserve, in view of the analytical evidence which Manuelli and Cornan- ducci have brought forward in support of their statements. Summary. Phenylurethane, when heated with an equivalent proportion of 0- or p-toluidine, or with a-naphthylamine, yields in each case a symmetrical (mixed) disubstituted carbamide containing one phenyl group, together with a group derived from the base used; this product is always accompanied by the corresponding (simple) disubsti- tuted carbamide containing the radicle of the base alone: with a-naphthylamine, little but dinaphthplcarbamide is obtained ; with ptoluidine, the simple carbamide also largely preponderates ; with o-toluidine, the proportion of ditolylcarbamide obtained in the mixture is considerably lower. The simple carbamide is less soluble than the mixed, in the cases mentioned ; consequently the process is not a satis- factory one for the preparation of such mixed derivatives i n a state of purity. pTolylurethane and aniline yield mainly ab-phenyl-p-tolylcarbamide : a secondary product, obtained in very limited quantity, appeared to be di-p-toly lcarbamide. Experimental reasons are assigned for concluding that the phenyl-p- tolplcarbamide and phenyl-a-naphthylcarbamide of Manuelli and Comanducci (Gaxz., 1899, 29, ii, 136) are di-p-tolyl- and di-a-naphthyl- carbamide respectively. CHEMICAL DEPARTMENT, QUEEN'S COLLEGE, CORK.

ISSN:0368-1645    

DOI:10.1039/CT9017900102

出版商:RSC    

年代:1901

数据来源: RSC