摘要:

J O U R N A L OF THE CHEMICAL SOCIETY. TRANSACTIONS. H. T. BROWN, LL.D., F.R.S. A. W. CROSSLEY, D.Sc., Ph.D. BERNARD DYER, D.Sc. M. 0. FORSTER, D.Sc., Ph.D., F.R.S. WYNDHAM R. DUNSTAN, M. A. , LL. D., F. R. S. H. MCLEOD, F.R.S. R. MELDOLA, P.R.S. E. J. MILLS, D.Sc., LL.D., F.R.S. Sir W. RAMSAY, K. C.B., LT,. D., F. R.S. A. ScorT, D.Sc., F.R.S. W. A. TILDEN, D.Sc., F.R.S. 6bitm : G. T. MORGAN, D.Sc. %lib - &titar : A. J. GREENAWAY. 1905. Vol. LXXXVII. LONDON: GURNEY & JACKSON, 10, PATERNOSTER ROW. 1905.RICHARD CLAY & SONS, LIMITED, BREAD STREET HILL, E.C., AND BUNGAY, SUFFOLK.J O U R N A L H. T. BROWN, LL.D., F.R.S. A. W. CRossLmr, D.Sc., Ph.D. WYNDHAM R. DUNSTAN, M.A., LL.D., BERNARDYER, D.Sc. M. 0. FORSTER, D.Sc., Ph.D., F.R.S. F. R.S. OF H. MCLEOD, F.R.S.R. MELDOLA, F.R.S. E. J. MILLS, I3 Sc., LL.D., F.R.S. Sir TIT. RAMSAY, K.C. R., LL. D., F.R.S. A. SCOTT, D.Sc., F.R.S. W. A. TILDEN, D.Sc., F.R.S. THE CHEMICAL SOCIETY, TRANSACTIONS. Cbitm : G. T. MORGAN, D.Sc. Sub- QbitlTr : A. J. GREENAWAY. 2Jssistaat S,zzb.-dFbifxrr : C. H. DESCH, D.Sc., Ph.D. 1905, Vol. LXXXVII. Part I. LONDON: GURNEY & JACKSON, 10, PATERNOSTER ROW. 1905.RICHARD CLAY & SONS, LIMITED, BREAD STREET HILL, E.C., AND BUNOAY, SUFFOLK.J O U R N A L OF THE CHEMICAL SOCIETY. TRANSACTIONS. H. T. BROWN, LL.D., F.R.S. A. W. CROSSLEY, D.Sc., Ph.D. WYNDHAM R. DUNSTAN, M.A., LL.D , BERNARD DYER, D.Sc. M. 0. FORSTER, D.Sc., Ph.D., F.R.S. F. R. S. H. MCLEOD, F.R.S. It. MELDOLA, F.R.S. E. J. MILLS, D.Sc., LL.D., F.R.S. Sir W. RAMSAY, K.C.B., LL.D., F.R.S.A. SCOTT, D.Sc., F.R.S. W. A. TILDEN, D.Sc., F.R.R. &;birfal: : G. T. MORGAN, D.Sc. %nb - Q bif JYl : A. J. GREENAWAY. &a&efarrt Sab-Qbifxrr : C. H. DESCH, D.Sc., P1i.D. 1905. Vol. LXXXVII. Part If. LONDON: GURNEY 2s JACKSON, 10, PATERNOSTER ROW, 1905.RICHARD CLAY & SONS, LIMITED, BREAD STREET BILL, E.C., AND BUNGAY, BUFFOLH.C O N T E N T S . PAPERS COMMUNICATED TO THE CHEMICAL SOCIETY. PAGE 1.-A Nethod for the Direct Production of Certain Aminoazo- compounds. By RAPHAEL MELDOLA, F.R.S., and LEWIS EYNON, B.Sc., F.1.C. . 11.-The Diazo-reaction in the Diphenyl Series. Part IT. Ethoxybenzidine. By JOHN CANNELL CAIN . . 111,-The Sulphate and the Phosphate of the Dimercurammonium Series. 1V.-The Viscosity of Liquid Mixtures. Part 11.By ALBERT ERNEST DUNSTAN, B.Sc. . V.-The Combination of Mercaptans with Olefinic Ketonic Compounds. By SIEGFRIED RUHEMANN . TI.-Hydrolysis of Ammonium Salts. By VICTOR HERBERT VI1.-Studies in Optical Superposition. Part I. By THOMAS YII1.-The Available Plant Food in Soils. By HERBERT INGLE 1X.-The Constitution of Nitrogen Iodide. By OSWALD SILBERRAD, Ph.D. . X.-The Metallic Derivatives of Nitrogen Iodide and their Bearing on its Constitution. By OSWALD SILBERRAD, Ph.D. XI.-The Diazo-derivatives of the Benzenesulphonylphenylene- diamines. By GILBERTHOMAS MORGAN and FRANCES MARY GORE MICKLETHWAIT . . ’ . XIL-The Reduction Products of Anisic Acid. By JOHN SCOTT LUMSDEN . XIIT,-The Physical Properties of Heptoic, Hexahydrobenzoic, and Benzoic Acids and their Derivatives. By JOHN BCOTT LUMSDEN .XIV.-Transformations of Derivatives of s-Tribromodiazo- benzene. By KENNEDY JOSEPH PREVITE ORTON. . By PRAFULLA CHANDRA RAY . TIELEY . STEWART PATTERSON and FRANCIS TAYLOR, B.Sc. . 1 5 9 11 17 26 33 43 55 66 73 87 90 99 XV.-The Determination of Acetyl Groups. By ARTHUR GEORGE PERKIN, F.R.S. . . 107iv CONTENTS. XV1.-Studies in the Camphane Series. Part XVI. Camphoryl- carbimide and Isomeric Camphorylcarbamides. By MARTIN ONSLOW FORSTER and HANS EDUARD FIERZ . XVI1.-The Influence of Solvents on the Rotation of Optically Active Compounds. Part VII. Solution-volume and Rotation of Menthol and Menthyl Tartrates. By THOMAS STEWART PATTERSON and FRANCXS TAYLOR, B.Sc. XVIII. -A Farther Analogy between the Asymmetric Nitrogen and Carbon Atoms. By HUMPHREY OWEN JONES .X1X.-Nitrogen Halogen Derivatives of the Sulphonamides. By FREDERICK DANIEL CHATTAWAY . XX.-Theory of the Production of Mercurous Nitrite and of its Conversion into Various Mercury Nitrates. By PRAFULLA CHANDRA RAY . XX1.-The Nitrites of the Alkali Metals and Metals of the Alkaline Earths and their Decomposition by Heat. By XX.11.-The Addition of Sodium Hydrogen Sulphite to Ketonic Compounds. By ALFRED WALTER STEWART, B.Sc., 1851 Exhibition Scholar of the University of Glasgow XXII1.-The Molecular Condition in Solution of Ferrous Oxalate. By ~AMUEL EDWARD SHEPPARD and CHARLES EDWARD KENNETH MEES XX1V.-The Determination of Molecular Weight by Lowering of Vapour Pressure. XXV.-Electrolytic Oxidation of Aliphatic Aldehydes.By HERBERT DRAKE LAW. I XXV1.-The Analysis of Samples o€ Milk referred t o the Government Laboratory in connection with the Sale of Food and Drugs Acts. By THOMAS EDWARD THORPE, C.B., F.R.S. . XXVI1.-The Nitration of Substituted Azophenols. By JOHN THEODORE HEWITT and HERBERT VICTOR MITCHELL XXVII1.-Studies in the Camphane Series. Part XVII. Con- figuration of, isoNitrosocamphor and its Unstable Modifica- tion. By l M ~ ~ ~ ~ N ONSLOW FORSTER . XX1X.-The Estimation of Saccharin. By CHARLES PROCTOR, F.I.C. XXX.-The Relation between Nntural and Synthetical Glyceryl- phosphoric Acids. By FREDERICK BELDING POWER and FRANK TUTIN . XXX1.-The Formation of Magnesia from Magnesium Car- bonate by Heat, and the Effect of Temperature on the Properties of the Product.By WILLIAM CARRICK ANDERSON PRAFULLA CHANDRA R A Y . By EDGAR PHILIP PERMAN . . PAGE 110 122 135 145 171 177 185 189 194 198 206 225 232 242 249 257CONTENTS. XXXI1.-The Latent Heat of Evaporation of Benzene and some other Compounds. By JAMES CAMPBELL BROWN, D.Sc. XXXII1.-The Constitution of Phenylmethylncridol. By JAMES JOHNSTON DOBBIE, D.Sc., F.R.S., and CHARLES KENNETH TINKLER . XXX1V.-The Ultra-violet Absorption Spectra of certain Diazo- compounds in Relation to their Constitution. By JAMES JOHNSTON DOBBIE, D.Sc., F.R.S., and CHARLES KENNETH TINKLER . XXXV.-Action of Hydrogen Peroxide on Carbohydrates in the Presence of Ferrous Sulphate. Part V. By ROBERT SELBY MOREELL and ALBERT ERNEST BELLARS XXXV1.-The Reduction of isoPhthalic Acid. By WrLLralwr HENRY PERKIN, jun., and SAMUEL SHROWDER PICKLES. .XXXVII. -The Influence of Solvents on the Rotation of Opti- cally Active Compounds. Part VIII. Ethyl Tartrate in Chloroform. By THOMAS STEWART PATTERSON . XXXVIIL-Studies in Chlorination. The Chlorination of the Isomeric Chloronitrobenzenes. By JULIUS BEREND COHEN and HUGH GARNER BENNETT . XXX1X.-Linin. By JAMES STUART HILLS, Salters' Research Fellow, and WILLIAM PALMER WYNNE . XL.-The Influence of Temperature on the Interaction between Acetyl Thiocyanate and Certain Bases. Thiocarbamides, including Carboxy-aromatic Groups. By the late ROBERT ELLIOTT DORAN ; compiled by AUGUSTUS EDWARD DIXON . XL1.-Pinene isoNitrosocpnide and its Derivatives. By WILLIAM AUGUSTUS TILDEN and HARRY BURROWS XLI1.-Gynocardin, a New Cyanogenetic Glucoside.By FREDERICK BELDING POWER and FREDERIC HERBERT LEES . XLII1.-The Action of Ethyl Dibromopropanetetrxcarboxylate on the Disodium Derivative of Ethyl Propanetetracarboxyl- ate. A Correction. By WILLIAM HENRY PERKIN, jun. . XL1V.-Glutaconic Acid and the Conversion of G lutaric Acid into Trimethylenedicarboxylic Acid. By WILLIAM HENRY YERKIN, jun., and GEORGE TATTERSALL, B.Sc. . XLV.-Studies in the Camphane Series. Part XVIII. A Xew Formation of Acetylcamphor. By MARTIN ONSLOW FORSTER and HILDA MARY JUDD, B.Sc. XLV1.-Photographic Radiation of Some Mercury Compounds. By ROBERT DE JERSEY FLEMING STRUTHERS and JAMES ERNEST MARSH . XLVI1.-Nitrogen Halogen Derivatives of the Aliphatic Di- amines. By FREDERIUK DANIEL CHATTAWAY . . . V PAGE 265 269 273 280 293 313 320 327 331 344 349 358 361 368 377 381vi CONTENTS.XLVII1.-Tran sf ormations of Highly Substituted N itroamino- benzenes. By KENNEDY JOSEPH PREVIT~ ORTON an'd ALICE EMILY SMITH . XL1X.-The Constituents of Gambier and Acacia Catechus. 11. By ARTHUR GEORGE PERKIN, F.R.S. . L.-Preparation and Properties of 1 :4:5-Trimethylglyoxaline. By HOOPER ALBERT DICKINSON JOWETT L1.-The Velocity of Oxime Formation in Certixin Eetones. By ALFRED WALTER STEWART, B.Sc., 1851 Exhibition Scholar of the University of Glnsgow LI1.-Limonene Nitrosocyanides and their Deyivatives. By FREDERICK PEACOCK LEACH LII1.-The Action of Acetylene on Aqueous and Hydrochloric Acid Solutions of Mercuric Chloride. By JOHN SAMUEL STRAFFORD BRAME . L1V.-The Action of Carbon Monoxide on Ammonia.By HERBERT JACKSON and DUDLEY NORTHALL-LAURIE LV.-The Condensation of Phenylglycinoacetic Esters in Pre- sence of Sodium Alkyloxides. By ALFRED THEOPHILUS DE MOUILPIBD . LV1.-An Asymmetric Synthesis of Quadrivalent Sulphur. By SAMUEL SMILES, D.Sc. LVI1.-The Combination of Mercaptans with Unsaturated Ketonic Compounds. LVII1.-The Tautornerism of Acetyl Thiocyanate. By AUGUSTUS EDWARD DIYON and JOHN HAWTHORNE L1X.-The Chemical Dynamics of the Reactions between Sodium Thiosulphate and Organic Halogen Compounds. Part 11. Halogen-substituted Acetates. By ARTHUR SLATOR, Ph.D. LX.-The Kinetics of Chemical Changes which are Reversible. The Decomposition of as-Dimet hylcarbamide. By CHARLES EDWARD FAWSITT . Widicenus Memorial Lecture. By W. H. PERKIN, jun. .Annual General Meeting . Presidential Address Obituary Notices . LX1.-The Resolution of Inactive Glyceric Acid by Fermenta- By PERCY FARADAY FRANKLAND and . . . By SIEGFRIED RUHEMANN . . tion and by Brucine. EDWARD DONE, M.Sc. LXI1.-C-Phenyl-s-triazole. By GEORGE YOUNG . LXII1.-Isomeric Salts of the Type NR,R,R,. A Correction. Isomeric Forms of d-Bromo- and d-Chloro-camphorsulphonic Acids. By FREDERIC STANLEY EIPPINQ . PAGE 389 398 405 410 41 3 427 433 435 450 461 468 481 49 4 501 535 546 565 618 625 628CONTENTS. vii PAGE LXIV.-Experiments on the Synthesis of the Terpenes Part 11. Synthesis of A3-p-Ment henol( 8), A3.s(9)-p-Menthadiene, p-Menthanol( 8), Aqg)-p-Menthene, and p-Menthane. By WILLIAM HENRY PERKIN, jun., and SAMUEL SHROWDER PICKLES . LXV.-Experiments on the Synthesis of the Terpenss.Part 111. Synthesis of Aliphatic Compounds similar in con- stitution to Terpineol and Dipentene. By WILLIAM HENRY PERKIN, jun., and SAMUEL SHROWDER PICKLES LXV1.-Experiments on the Synthesis of the Terpenes. Part IV. Synthesis of A3-Normenthenol( 8), h”.”g)-Nor- menthadiene, Normenthanol(8), As(%Normenthene, &c. By K~ICHI MATSUBARA and WILLIAM HENRY PERKIN, jun. . LXVI1.-Some Derivatives of Anhydracetonebenzil. By FRANCIS ROBERT JAPP, F.R.S., and JOSEPR KNOX, B.Sc., Carnegie Scholar in the University of Aberdeen LXVII1.-The Dihydrocyanides of Benzil and Phenanthra- quinone. Second Notice. By FRANCIS ROBERT JAPP, F.R.S., and JOSEPH KNOX, B.Sc.., Carnegie Scholar in the Uni- versity of Rberdeen . LX1X.-A Condensation Product of Mandelonitrile. By FRANCIS ROBERT JAPP, F.R.S., and JOSEPH KNOX, B.Sc., Carnegie Scholar in the University of Aberdeen By FRANCIS ROBERT JAPP, F.R.S., and JAMES WOOD, M.A., B.Sc., Carnegie Scholar in the University of Aberdeen LXX1.-Condensations of Phenanthraquinone with Ketonic Compounds.By RANC CIS ROBERT JAPP, F.R.S., and JAMES WOOD, M.A., B.Sc., Carnegie Scholar in the University of Aberdeen . LXXIL-Cyanomaclurin. By ARTHUE GEORGE PERKIN, F.R. 8. LXXII1.-Studies in the Camphane Series. Part XIX. Camphoryl-$-semicarbazide. By MARTIN ONSLOW YORSTER and HANS EDUARD FIERZ . LXX1V.-Estimation of Potassium Permanganate in the presence of Potassium Persulphate. By JOHN ALBERT NEWTON FRIEND, M.Sc, . LXXV.-The Purification of Water by Continuous Fractional Distillation.By WILLIAM ROBERT BOUSPIELD, M.A., X.C., M.P. LXXV1.-The Influence of the Hydroxyl and Alkoxyl Groups on the Velocity of Saponification. Part I. By ALEXANDER FINDLAP and WILLIAX ERNEST STEPHEN TURNER, WSc. . By WALTER CRAVEN BALL, B.A. . , . LXX. -Action of Hydrazine on Unsaturated y-Diketones. . LXXVI1.-Complex Nitrites of Bismuth. 639 655 661 673 68 1 701 707 712 715 723 738 740 747 761... V11L CONTENTS. LXXVII1.-The Ultra-violet Absorption Spectra of Certain Enol-keto-tautomerides. Part 11. By EDWARD CHARLES CYRIL BALY and CECIL HENRY DESCH . LXX1X.-The Basic Properties of Oxygen at LOW Tempera- tures. Additive Compounds of the Halogens with Organic Substances containing Oxygen. By DOUGLAS MCINTOSH . LXXX.-The Constitution of Pilocarpine. Part V.Con- version of isoPilocarpine into Pilocarpine. By HOOPER ALBERT DICKINSON JOWETT LXXX1.-The Chlorination of Methyl Derivatives of Pyridine. Part I. 2-Methylpyridine. By WILLIAM JAMES SELL, M.A., F.R.S. . LXXXI1.-Further Studies on Dihydroxymaleic Acid. By HENRY JOHN HORSTMAN FENTON, M.A., F.R.S. LXXXIII. -Behaviour of Solutions of Propyl Alcohol towards Semi-permeable Membranes. By ALEXANDER FINDLAY and FREDERICK CHARLES SHORT LXXX1V.-Oxymercuric Perchlorates and the Action of Alcohol on Mercury Perchlorates. By MASUMI CHIKASHIG~ LXXXV.-Studies in the Camphane Series. Part XY. Cam- p horylazoimicle: By MARTIN ONSLOW FORSTER and HANS EDUARD EIERZ . LXXXV1.-The Action of Magnesium Methyl Iodide on Pinene Nitrosochloride. By WILLIAU AUGUSTUS TILDIEN and JOSEPH ARTHUR STOKES, 36.8~.. LXXXVI1.-The Reduction of isoPhthalic Acid. Part 11. By WILLIAM GOODWIN and WILLIAM HENRY PERKIN, jun. . LXXXVII1.-The Replacement of Hydroxyl by Bromine. By WILLIAM HENRY PERKIN, jun., and JOHN LIONEL SIMONSEN LXXX1X.-The Ethereal Salts and Amide of Dimethoxyprop- ionic Acid derived from d-Glyceric Acid. By PERCY FARADAY FRANKLANU and NORMAN LESLIE GEBHARD, M.Sc. XC.-The Constitution of Barbaloin. Part I. By HOOPER AT~BERT DICKINSON JOWETT and CHARLES ETTY POTTER . XC1.-The Constituents of the Seeds of Eydnocaqms Wightiafia and of Hydnocarpus aw,thelmi?zthiczcs. Isolation of a Homo logue of Chaulmoogric Acid. By FREDERICK BELRING POWER and MARMADUKE BARROWCLIFF XCI1.-The Constituents of the Seeds of Gynocardia odorata. By FREDERICK BELDING POWER and NARMADUKE BARROW- XCII1.-A Contribution to the Study of Alkylated Glucosides.By JAMES COLQUHOUN IRVINE, Ph.D., D.Sc., Carnegie Fellow, and ADAM CAMERON, M.A., B.Sc., Carnegie Scholar . CLIFF . PAGE 766 784 794 799 804 81 9 822 82 6 836 84 1 855 864 878 884 896 900CONTENTS. iX PAGE XC1V.-The Thermal Decomposition of Formaldehyde and By WILLIAM ARTHUR BONE and ]BENRY XCV.-The Synthesis of Formaldehyde. By DAVID LEONARD XCV1.-The Diazo-derivatives of the Monoacetylated Aromatic By GILBERT THOMAS MORGAN and FRANCES XCVX1.-Influence of Substitut,ion on the Formation of Diazo- amines and Aminoazo-compounds. Part 111. Azo-deriv- atives of Symmetrically Disubstituted Primary Meta- diamines. By GILBERT THOWAS MORGAN and WILLIAM ORD WOOTTON . . 935 XCVIIL-Influence of Substitution on the Formation of Diazo- amines and Aminoazo-compouncls.Part IV. 5-Bromo- as(4)-dimethyl-2:4-diaminotoluene. By GILBERT THOMAS MORGAN and ARTHUR CLAYTON . . 944 XC1X.-The Action of Hypobromous Acid on Piperazine. By FREDERICK DANIEL CHATTAWAY and WILLIAM HENRY LEWIS 951 C.-Tetramethylammonium Hydroxide. By JAMES WALKER GI.-Tetrethylsuccinic Acid. By JAMES WALKER and ANNIE CI1.-The Synthesis of Substances Allied to Epinephrine. By CI.11.-Our Present Knowledge of the Chemistry of Indigo. By C1V.-Influence of Various Sodium Salts on the Solubility of CV.-The Dielectric Constants of Phenols and their Ethers Dissolved in Benzene and m-Xylene. By JAMES CHARLES PHILIP and DOROTHY HAYNES . . 998 CV1.-Racemisation Phenomena during the Hydrolysis of Optically Active Menthyl and Bornyl Esters by Alkali.By ALEXANDER MCKENZIE and HERBERT BRYAN THOMPSON, Bl.Sc., Priestley Research Scholar in the University of Birmingham . . 1004 CVI1.-Synthesis from Glucose of an Octamethylated Disacchar- ide. Methylation of Sucrose and Maltose. By THOMAS PURD~E, F.R.S., and JAMES COLQUHOUN IRTTINE, Ph.D., D.Sc., By Acetaldehyde. LLEWELLYN SMITH . . 910 CHAPMAN and ALFRED HOLT, Sun. . . 916 Para-diamines. MARY GORE MICKLETHWAIT . . 921 and JOHN JOHNSTON, Carnegie Research Scholar . . . 955 PURCELL WALKER . . 961 GEORGE BARGER and HOOPER ALBERT DICKINSON JOWETT . 967 WILT~IAM POPPLEWELL BLOXAM . . 974 Sparingly Soluble Acids. By JAMES CHARLES PHILIP . 987 Carnegie Fellow , . 1022 THOMAS MARTIN LOWRY . . 1030 CVII1.-The Design of Gas-regulators for Thermostats.x CONTENTS.PAGE CIX.-Studies in Chlorination. 11. The Action of Chlorine on Boiling Toluene. Preliminary Notice. By JULIUS BEREND COHEN, HARRY MEDPORTH DAWSON, and PERCY FIELD CROSLAND . . 1034 CX.-The Determination of Melting Points at Low Tempera- tures. By LEO FRANK GUTTMANN, Ph.D., A.I.C. . . 1037 CX1.-Association in Mixed Solvents. By GEORGE BARGER . 1042 (3x11.-A precise Method of Estimating the Organic Nitrogen in Potable Waters. By JAMES CAMPBELL BROWN, D.Sc. 1051 (2x111.-Studies in the Acridine Series. Part IT. Action of Methyl Iodide on Benzoflavine (2:8-Diamino-5-pheuyl-3:7- dimethylacridine). By JOBN THEODORE HEWITT and JOHN JACOB Fox . 1058 CX1V.-Note on Certain Derivatives of cycZoPropene. By DAVID TREVOR JONES .. 1062 CXV.-Experiments on the Synthesis of the Terpenes. Part V. Derivatives of ortho-Cymene. By FRANCIS WILLIAM KAY and WILLIAM HENRY PERKIN, juu. . . 1066 Part TI. Derivatives of meta-Cymene. By WILLIAM HENRY PERKIN, jun., and GEORGE TATTERSALL, 1851 Exhibition Scholar of University College, Nottingham CXVI1.-Bromine in Solutions of Potassium Bromide. By CXVII1.-The Relation of Ammonium to the Alkali Metals. A Study of Ammonium Magnesium and Ammonium Zinc Sulphates and Selenates. By ALFRED EDWIN HOWARD TUTTON, M.A., D.Sc. (Oxon.), F.R.S. . . 1123 CX1X.-Topic Axes, and the Topic Parameters of the Alkali Sulphates and Selenates. By ALFRED EDWIK HOWARD TUTTON, M.A., D.Sc., F.R.S. . . 1183 CXX.-The Relation of Position Isomerism to Optical Activity. IV.The Rotation of the Menthyl Esters of the Isomeric Nitrobezrzoic Acids. By JULIUS BEHREND COHEN and HENRY PERCY ARMES . . 1190 CXX1.-Dinitroanisidines and their Products of Diazotisation. By RAPHAEL MELDOLA, F.R.S., and FRANK GEORGE C. STEPHENS . . 1199 CXXI1.-Labile Isomerism among Benzoyl Derivatives of Salicylamide. By ARTHUR WALSH TITHERLEY and WILLIAM LONGTON HICKS . * I. . 1207 CXXII1.-Preparation of Benzeneazocoumarin ; its bearing on the Constitution of p-Hydroxyazo-compounds. By HERBERT VICTOR MITCHELL . . 1229 CXV1.-Experiments on the Synthesis of the Terpenes. . 1083 FREDERICK P. WORLEY, M.A. . . 1107CONTENTS. xi PAGE CXX1V.-The Combustion of Acetylene. By WILLIAM ARTHUR BONE and GEORGE WILLIAM ANDREW . . 1233 CXXV.-Studies on the Origin of Colour. Derivatives of Fluorene.By IDA SMEDLEY . . 1249 CXXVL-Note on the Zeisel Reaction in the Case of Di-ortho- substituted Phenolic Ethers. By DAVID RUNCIMAN BOYD and JOHN EDMUND PITMAN . . 1355 CXXVI1.-The Mechanism of the Hydrogen Sulphide Reduc- tion of Nitro-compounds. By JULIUS BEREND COHEN and DOUGLAS MCCANDLISH . . 1257 CXXVII1.-The Significance of Optical Properties as connoting Structure : Camphorquinone-Hydrazones-Oximes-Di- azo-derivatives ; a Contribution to the Theory of the Origin of Colour and to the Chemistry of Nitrogen. By HENRY E. ARMSTRONG and WILLIAM ROBERTSON, A.R.C.S., Leather- CXX1X.-Solubility as a Measure of the Change undergone by Isodynamic Hydrazones : (1) Camphorquinonephenylhydr- azone, (2) Acetaldehydephenylhydrazone. By WILLIAM ROBERTSON, A.R.C.S., Leathersellers’ Company’s Research Fellow .. 1298 CXXX.-The Arylsulphonyl-p-diazoimides. By GILBERTHOMAS MORGAN and FRANCES MARS GORE MICKLETHWAIT . . 1302 CXXX1.-The Reversibility of Photographic Development and the Retarding Action of Soluble Bromides. By SANUEL EDWARD SHEPPARD . . 1311 CXXXI1.-The Ultra-Violet Absorption Spectra of Aromatic Compounds. Part I. Benzene and Certain Mono-sub- stituted Derivatives. By EDWARD CHARLES CYRIL BALY and JOHN NORMAN COLLIE . . 1332 CXXXII1.-The Ultra-Violet Absorption Spectra of Aromatic Compounds. Part 11. The Phenols. By EDWARD CHARLES CYRIL BALY and ELINOR KATHARINE EWBANK . . 1347 CXXX1V.-The Ultra-Violet Absorption Spectra of Aromatic Compounds. Part 111. Disubstituted Derivatives of Benz- ene. By EDWARD CHARLES CYRIL EALY and ELINOR KATHARINE EWBANK .. 1355 CXXXV.-Studies in Chlorination. 111. The Progressive Chlorination of Benzene in Presence of the Aluminium- Mercury Couple. By JULIUS BEREND COHEN and PERCIVAL HARTLEY . . 1360 CXXXV1.-Estimation of Hydrogen Peroxide in the Presence of Potassium Persulphate. By JOHN AT~RERT NEWTON FRIEND, M.8c. . . . . 1367 sellers’ Company’s Research Fellow . . 1272xii CONTENTS. PAGE CXXXVIL-The Interaction of Sul phuretted Hydrogen and Arsenic Pentoxide in Presence of Hydrochloric Acid. By FRAKCIS LAWRY USHER and MORRIS WILLIAM TRAVERS, D.Sc., F.R.S. . . 1370 CXXXVII1.-Studies in Asymmetric Synthesis. 111. The Asymmetric Synthesis of I-Lactic Acid. The Optical Activity of Fermentation Lactic Acid. By ALEXANDER MCKENZIE .1373 CXXX1X.-The Action of Phenylpropiolyl Chloride on Ketonic Compounds. By SIEGFRIED RUHEMAXX and RICHARD WILLIAM MERRIMAN . . 1383 CXL.-The Influences regulating the Reproductive Functions of Saccharomyces Cerevisia. By ADRIAN JOHN BROWN . 1395 CXL1.-Some Oxidation Products of the Hydroxybenzoic Acids and the Constitution of Ellagic Acid. Part I. By ARTHUR GEORGE PERKIN, F.R.S., and, in part, MAXIMILIAN NIERENSTEIK, 9h.D. . . 1412 CXLI1.-Molecular Refractions of some Liquid Mixtures of Constant Eoiling Point. By IDA FRANCES HOMFRAY, 36.S~. . 1430 CXLIIL-Molecular Refractions of Dimethylpyrone and its Allies and the Quadrivalency of Oxygen. By IDA FRANCES HOMFRAY, B.Sc. . . 1461 By JAMES CorAQuHouN IRVINE, Ph.D., D.Sc., Carnegie Fellow, *and AGNES MARION MOODIE, M.A., B.Sc., Eerry Scholar in Science .) .1462 CXLV.-The Interaction of Acridines with Magnesium Alkyl Halides. By ALFRED SENIER, PERCY CORLETT AUSTIN, and ROSALIND CLARKE . . 1469 CXLV1.-New Method of Determining Molecular Weights. By PHILIP BLACKMAN . . 1474 CXLVIL-a-Benzylphenylallylmethylammonium Compounds : a Complete Series of Four Optically Active Salts. By ALFRED WILLIAM HARVEY . . 1481 CXLVII1.-Synthesis of 1 :1-Diniethylhexahydrobenzene and of 1 :l-Dimethyl-h3-tetrahydrobenzene. By ARTHUR WILLIAM CROSSLEY and NORA RENOUF, Salters’ Research Fellow . 1487 CXL1X.-Solid Solutions. By REINITOLD FREDERICK KORTE . 1503 CL.-The Bromo-derivatives of Camphopyric Acid By JOHN ADDYMAN GARDNER, M.A. . . 1516 CL1.-The Reduction of Metallic Oxides by Aluminium Carbide.By JOHN NORMAN PRING, B.Sc. . . 1530 CLI1.-Syntheses by means of the Silent Electric Discharge. By JOHN NORMAN COLLIE, F.R.S. . . 1540 CLII1.-The Rusting of Iron. By WYNDHAM ROWLAND DUNSTAN, F.R.S., HOOPER ALBERT DICKINSON JOWETT, D.Sc., and CXL1V.-The Alkylation of Mannose. ERNEST GOULDIKG), D.Sc. . . 1548... CONTENTS. XI11 PAGE CL1V.-Studies in Comparative Cryoscopy. Part 111. The Esters in Phenol Solution. By PHILIP WILFRED EOBERT- SON, Rhodes Scholar . . . . 1574 CLV.-The Iodides of Copper. By JAMES WALLACE WALKER and MARY VIOLETTE DOVER . . 1584 CLV1.-The Interaction of Alcohols and Phosphorous Halides. By JAMES WALLACE WALKER and FREDERICK MURRAY GODSCHALL JOHNSON . . 1592 CLVI1.-The Electrical Conductivities of some Salt Solutions in Acetamide.By JAMES WALLACE WALKER and FREDERICK MURRAY GODSCHALL JOHNSON . . 1597 CLVII1.-The Atomic Weight of Nitrogen. By ROBERT WHYTLAW GRAY. . . 1601 CLIX.-Contributions to our Knowledge of the Aconite Alka- loids. Part XVI. Indaconitine, the Alkaloid of Aconitum chasmanthum. By WYNDHAM ROWLANDUNSTAN, F.R.S., and ALBERT EDWARD ANDREWS, Salters’ Company’s Re- search Fellow . . 1620 CLX.-Contributions to our Knowledge of the Aconite Alka- loids. Part XVII. Bikhaconitine, the Alkaloid of Aconitum spicatum. By WYNDHAM ROWLAKD DUNSTAN, P.R.S., and ALBERT EDWARD ANDREWS, Salters’ Company’s Research Fellow . . 1636 CLX1.-Contributions to our Knowledge of the Aconite hlka- Ioids. Part XVIII. The Aconitine Group of Alkaloids. By WYNDHAM ROWLANDUNSTAN, F.R. S., and THOMAS ANDERSON HENRY, D.Sc.. . 1650 CLXI1.-The Influence of Water and Alcohols on the Boiling Point of Esters. I. A Modification of Mnrkownikoff’s Method of Preparation. By JOHN WADE, D.Sc. . 1656 CLXII1.-The Constitution of Glutaconic Acid. By JOCELYN FIELD THORPE . . 1669 CLX1V.-Some Alkyl Derivatives of Glutaconic Acid and of 2:6-Dihydroxypyridine. By HAROLD ROGERSON and JOCELYN FIELD THORPE . . 1685 CLXV.-Note on the Formation of P-Methylglutaconic Acid and of c$-Dimethylglutaconic Acid. By FRAXCIS VERNON DARBISHIRE and JOCELYN FIELD THORPE . . 1714 CLXV1.-The Stereoisomerism of Substituted Ammonium Compounds. By HUMPHREY OWEN JONES . . 1721 CLXVI1.-Researches on the Freezing Points of Binary Mix- tures of Organic Substances : the Behnviour of the Dihydric Phenols towards p-Toluidine, a-Naphthylamine, and Picric Acid. By JAMES CHARLES PHILIP and SYDNEY HERBERT SBI~TH .. 1735xiv CONTENTS. PAGE CLXVII1.-Simple Methcd for the Estimation of Acetyl Groups. By JOHN JOSEPH SUDBOROUGH and WALTER THOMAS . . 1752 CLX1X.-Application of the Microscopic Method of Molecular Weight Determination to Solvents of High Boiling Point. By GEORGE BARGER and ARTHUR JAMES EWINS . . 1756 Part I. Dextro-A2 (or 3)-dihydro-1-naphthoic Acid. By ROBERT How- SON PICKARD and ALLEN NEVILLE, B.Sc. (Lond.) . . 1763 CLXX1.-Tetrazoline, Part 111. By SIEGFRIED RUHEMANN and RIUHARD WILLIAM MBRRIXAN . . 1768 CLXX1T.-Green Compounds of Cobalt produced by Oxidising Agents. By REGINALD GRAHAM DURRANT, M.A. . . 1781 CLXXII1.-The Preparation of Murexide from Alloxantin and CLXX1V.-The Absorption Spectra, of Uric Acid, Murexide, and the Ureides in relation to Colour and to their Chemical Structure. By WALTER NOEL HARTLEY, D.Sc., F.R.S. . 1796 CLXXV.-Observations on Chemical Structure and those Physical Properties on which the Theory of Colour is based. By WALTER NOEL HARTLEY, D.Sc., F.R.S. . . 1822 CLXXV1.-The Action of Nitrogen Sulphide on Organic Sub- stances, Part 111. By OLIVER CHARLES MINTY DAVIS . 1831 CLXXVI1.--The Action of Nitrogen Sulphide on Organic Sub- stances.-Part IT. By FRANCIS ERNEST FRANCIS . . 1836 CLXXVII1.-Esterification Constants of Substituted Acrylic Acids. Part I. By JOHN JOSEPH SUDBQROUGH and DAVID JAMES ROBERTS . . 1840 CLXX1X.-Hydrizino-halides derived from Oxalic Acid. By DOUGLAS ANDERSON BOWACK and ARTHUR LAPWORTR . . 1854 CLXXX.-Silicon Researches. Part IX. Bromination of Silicophenyl-imide and -nmide, and Formation of a Corn- pound including the Group (SiN). By J. EMERSON REYNOLDS, M.D., Sc.D., F.R.S. . . 1S70 CLXXXI. - Condensation of Ketones with Mercury Cyanide. By JAMES ERNEST MARSH and ROBERT DE JERSEY FLEMING CLXXXI1.-A Contribution to the Chemistry of o-Benzoic Sulphinide. By FREDERICK DANIEL CHATTAWAY . . 1882 CLXXXII1.-The Action of Heat on a-Hydroxycarboxylic Acids. Part. 11. a-Hydroxymargaric Acid, a-Hydroxy- palmitic Acid, a-Hyclroxypentadecylic Acid, and a-Hydroxy- myristic Acid. By HENRY RONDEL LE SUEUR . . 1888 . " y 1906 ERNEST LINDER and HAROLD PLCTON . CLXX.-Optically Active Reduced Naphthoic Acids. Alloxan. By WALTER NOEL HARTLEY, D.Sc., F.R.S. . . 1791 STRUTHERS . 187s CLXXX1V.-Solution and Pseudo-solution. Part IV.

ISSN:0368-1645    

DOI:10.1039/CT90587FP001

出版商:RSC    

年代:1905

数据来源: RSC

摘要:

CAIN: 1’HE DIAZO-REACTION IN THE MPHENYL SERIES. 5 11.- T?ae Diazo-reaction in tlze Dipkcnyl Seiqies. Part I I . Et hoxybenxidine. By JOHN CANNELL CAIN. IN an investigation on the action of heat on an acid solution of the diazoninm salts derivecl from dianisidine and 3 : 3’-dichlorobenzidine (Trans., 1903, 83, 688), it was shown that these substances behave very differently from the corresponding salts derived from benzidine and tolidiiie. Whereas, as is well known, the diazonium salts prepared from the two latter bases give the normal diazo-reaction and yield the corresponding hyclroxy-compounds (diphenols) on boiling with dilute acid, thus : Q6H4*N2Dc1 -+ C]fjH4*OH and C 1 6 H 3 Me*N,*Cl -~ C , 6 H Me*OH C,H,*N,*Cl C6H4*0H C6H,Me*N,*C1 C,H,Me*OH ’ the yield being nearly quantitative.A very different reaction apparently occurred in the case of the former pair of bases, thus, dinnisidine gave no trace of a phenol and dichlorobenzidirie yielded only a very slight amount of the dichlorodi- phenol, the chief products being probably of A quinonoid nature. The introduction of a methoxy-group or a chlorine atom in the ortho-position to the amino-group apparently has a great influence in modifying the conrse of the reaction, and it was obviously of much interest to investigate the mechanism of the reaction in the case of a similarly mono-substituted derivative. A difficulty a t once, however, presented itself in that no chlorobenzidine is known, and methoxy- benzidine is not readily procurable. The corresponding ethoxy- benzidine is, however, prepared on the commercial scale, and in view6 CAIN: THE DIAZO-REACTION IN THE of the difficulty of preparing the methoxy-derivative it was thought that an investigation carried out with the ethoxy-compound would be of equal value ; and, indeed, the interesting results obtained have confirmed this anticipation. When the aqueous solution of the cliazonium salt is boiled with dilute sulphuric acid, or when a current of steam is passed through its mid solution for some time, nitrogen is evolved, and, on cooling, long, brown, needle-shaped crystals separate out.After drying, these mere found to contain sulphur in the form of sulphuric acid, which was easily removed by treatment with sodium carbonate, the substance being therefore a salt of this acid with some base. The substance when very carefully tested for nitrogen by the sodium method gave a negative result, but on making a nitrogen determination as much as 8 per cent.was fonnd. The substance, when dissolved in water, com- bined instantly with b-naphthol, forming an azo-colouring matter, and its identification as a diazonium salt 'was thus complete. Analyses showed that one of the diazoniuin groups of the original tetrazo-salt had remained unattacked by boiling with dilute acicl, whilst the other had been entirely replaced by the hydroxyl group. This one diazoniuin group is exceedingly stable, whereas the other is completely decom- posed by boiling with dilute acid, exactly as in the case of the diazonium salt from benzidine. The question a t once arises as t o which diazonium group has been substituted : that in the ethoxyphenyl ring or that in the unsubstituted nucleus.Since the presence of the methoxy-group in the ortho-position with respect t o the diazonium group very greatly increases the stability of the latter (compare Trans., 1902, 81, 1438), one is justified in concluding that in the case of the tetrazo-salt from ethoxybenzidine it is the diazonium complex next to the ethoxy-group which remains unattacked by boiling dilute acid under the conditions of the experiment. It should, however, be men- tioned that prolonged boiling for many hours also effects the decom- position of this group, but the product has not been further examined. The formation of the new substance may therefore be expressed as follows : OEt OEt This is, so far as I know, the first example of a substance containing two diazonium groups which undergoes such a change.The diazonium sulphate is exceedingly stable, for when dried on a porous plate it may be preserved either in a desiccator or in the open air for months without undergoing any decomposition, except that on exposure to the light it becomes slightly dmker in colour.DIPHENYL SERIES. PART 11. ETHOXYRENZIDINE. 7 The free Lase olhined by neutralisation with sodium carbonate has been combined with different acids, the salts of which are described in the sequel, the details regarding the azo-derivatives snd substitution products being reserved for a future communication. EX P E R I 31 EN T! A L. 4'-Hyd?-ox y- 3-etlioxyd iphe 2ql- 4-diaxonium ,Su Zpl&+--T he ethoxy- beiizidine used in these experiments was obtained from Messrs.I;. Cassella and Go., Frankfort, and the author wishes to express his acknowledgment of the kindness of this firm in providing him with a quantity of this material. The technical product is purified by extraction with benzene, the pure ethoxybenzidine being obtained from the filtered solution on evaporatiou. This base is then diazotised in the usual way; 15 grams are dissolved in hot water, acidified with 40 C.C. of concentrated hydro- chloric acid, the solution cooled with ice to 5', and an aqueous solution of 8.7 grams of sodium nitrite added. The ethoxybenzidine is thus completely diazotisecl, both amino-groups being changed into diazonium groups. The diazo-solution is now poured into a mixture of 60 C.C.of sulphuric acid and 120 C.C. of water, and heated t o boiling, either over the free flame or by the introduction of a current of steam, until the evolution of nitrogen has ceased. This operation may take half an hour. The hot solution is allowed to cool, when long, needle-shaped crystals separate out, which are colleztecl and dried on a porous plate, the yield being about 14 grams. The crystals in this form are dark brown, bnt when powdered the produc t exhibits an orange-brown tint. The hot solution may also be separated with common salt when the cliazonium sulphate is precipitated as a yellow powder. The diazonium salt thus prepared may be recrystallised from boiling dilute sulphuric acid. I t is easily soluble in water, forming a pale yellow solution, which combines a t once with '' R salt," forming a violet azo-compound.When dried in the air on a porous plate, the sulphate contains two molecules of water, which are eliminated by drying in a desiccator over sulphuric acid; the anhydrous saIt is thus obtained without any change of colour being observed. If, however, the hydrated salt is dried at 1 OOO, it turns green and undergoes decomposition. 0.2092 gave 0,3446 GO, and 0.0927 K,O. 0.2051 ,, 0.12283 BaS0,. S = 8.22. 2.6 lost, over sulphuric acid, 0.2692 H,O. C = 44-93 ; H = 4.92. 0.2192 ,, 0.3620 CO, ,, 0.0859 H,O. C= 45.03 ; H = 4.35. H,O = 10.77. C1,H1,0,N,S,2H,0 requires C = 44.92 ; H = 4.81 ; S = 855 ; N,O = 9.6 per cent.8 CAIW: THE DIAZO-REACTION I N THE DIPHENYL SERIES.The mhydrous salt gave the following numbers : 0.2889 gave 0.5252 CO, and 0,1118 H2U. 0,1963 ,, 0.13193 BaS@,. S= 9.23. 0.2596 ,, 18.4 C.C. nitrogen :it 15' and 750 mm. N 8.35. C = 49.58 ; H = 4.30. C,,H,,O,N,S requires C = 49.70 ; I1 = 4.14 ; S = 9.46 ; K = 8-28 per cent. Both the hydrated a i d anhydrous salts dissolved easily in cold water, giving a light yellow solution which, on the addition of aqueous sodium carbonate, yielded a lilac-coloured precipitate, this being soluble in excess of alkali to form it blood-red solution. On acidifying with hydrochloric acid, the lilac-coloured compound did not reappear, but a green precipitate resulted which was insoluble in excess of acid and mas not further examined. The lilac-coloured precipitate thus obtained is the free diazonium hydroxide, HO*C,H4*C,H3( OEt)-N(OH)iN, or possibly its anhydride, Y6H4O--- >NiN.C6HdOEt) This substance was dried over sulphuric acid, but a subsequent analysis showed that decomposition had taken place. For the pre- paration of the different salts, the base was isolated as a paste and then dissolved in the hot dilnte acid, the corresponding saltr crystallis- ing out on cooling. The diasoiziusiz clJorit7e crystallises from the hot solution in fine golden-brown needles. 0.1329 gave 0.2852 CO, and 0.0563 H,O. 0.2030 ,, 0.10393 AgC1. C1= 12.66. 0.1655 ,, 0.0S653 hgC1. C1= 12.93. C=58.53; H=4-70. C,,H,,O,N,Cl requires C = 60.78 ; H = 4-70 ; C1= 12.80 per cent. The dinxoaizcnz bromide crystallises from the hot solution of the base in dilute hydr obromic acid in fine golden-yellow needles.After drying over sulphuric acid, the salt had turned brown on the surface, so that the rather high percentage of bromine found on analysis is probably due t o a slight decomposition. 0.1946 gave 0.12123 AgBr. Br = 26.52. Cl4Hl3O2N2Br requires Br = 24.92 per cent. The dircxoniunt iodide is a dull yellow powder, which is still more unstable than the bromide and must be prepared without the aid of heat by triturating the base with cold hydriodic acid. After drying in a desiccator, the salt had become green on the surface, this slight amount of decomposition accounting for the high value obxained in the iodine estimation.SULPHATE AND PHOSPHATE OF nIJIERCT'€~.~MMOPU'T'~I SERIES. 9 0.1568 g t t ~ 0.10403 AgI. I: = 55-84. C,,H1,O,N,I requires I = 34-44 per cent, The diaxo.iziunz. n i t m t e crystallises from the hot solution in clusters of reddish-yellow needles. 1 Like the snlphate ancl chloride, it is fairly stable and remains michangecl in the desiccator, 0.2162 gavc 26.5 C.C. nitrogen at 20' ancl 754 min. N = 14-28. C,,H,,O,N,, requires N = 13.86 per cent. The platinichloride is obtained as a cnnary-yellow precipitate on adding platinic chloride to n solution of tlie dinzoninm chloride. 0.1 109 p v e 0.0230 Pt. Pt = 20.74. (C,,H,,O,N,),,H,PtCl, requires Pt = 21.90 per cent.

ISSN:0368-1645    

DOI:10.1039/CT9058700005

出版商:RSC    

年代:1905

数据来源: RSC

摘要:

SULPHATE AND PHOSPHATE OF nIJIERCT'R.~MMOPU'T'~I SERIES. 9 IIII.-Tlze Sulphate and the Phosphate of the By PRAFULLA CHANDRA RAY. THE preparation of dimercurainnioniuin nitrite, NHg,NO,, having already been described (Trans., 1902, 81, 644), it occurred to me that by treating this compound with an acid, the NO, group would be destroyed and the corresponding salt of the reacting acid would be formed. It was, however, found that a halogen acid completely breaks up the molecular structure, giving rise to double salts of the type 2NHg2X,NH,X, where X represents a halogen atom; but on sub- stituting nitric acid for the halogen acid, the nitrate of the series was readily obtained (Zeit. c6nor.g. Chem., 2902, 33, 209). It therefore seemed probable that an oxy-acid would behave differently from a Iialogen acid.Acting on this hint, I have lately treated dimercurammonium nitrite with sulphuric and phosphoric acids respectively, and have succeeded in preparing the corresponding salts. T!Le S2cll3~ccte.-Dimercurammonium nitrite is gently heated to boiling for some time with dilute snlphuric acid, whennitrous fumes are liberated. As both the parent substance and its derivatives are insoluble, pro- longed digestion is necessary before the NO, group is completely removed. A white, bulky, crystalline powder is obtained, which is washed free from the adhering mother liquor and dried in the steam- oven. The sulphate thus prepared is soluble in hydrochloric acid and conforms to the formula (NHg,)2S0,,H,0.10 SULPITATE AND PHOSPHATE OF DIMERCUR AMMONIUM SERIES.Fu 11 lid. 7- Caluulat ecl. I. 11. 84.00 .- 2.97 . 3.26 - Hg ........................... 84.92 N ........................... so* ........................... 10.19 10.96 10.21 H20 1.92 - ........................ The foregoing analyses were made with different preparations. The salt gives off moisture when heated in a bulb tube. The Phosphate.--This salt is prepared in much the same way as the siilphate ; it is only necessary to lay stress on the fact that as phosphoric acid attacks the NO, group much inore slowly than sulphuric acid, continued digestion a t 50-60’ for 2 to 3 days has been found to be necessary. The salt is obtained as a white, crystalline powder, which is washed and dried just as in the case of the sulpliate; it has the formula NHg,,H,PO,. The malyses given below wen3 made with three distinct prepamtions.Fouiid. h r- 7 C’i~lcl~lnte(1. 1. 11. 111. Hg ........................ 78.30 78.54 77.4 78.07 N. ......................... 2-74 2.00 - Po..... ..................... 6-07 6.44 6.33 - - It has a11 along been pointed out that when mercury is directly attached to the nitrogen atom, R more stable compound is formed than when it is linked to nitrogeii tlirough the intermediary of an oxygen atom, and this is strikingly shown in the behaviour of sodium sulphate totrards mercuric nityite and nitrate respectively (Trans., 1897, 71, 1103). It is also well known that a haloid of mercury is attacked by sulphuric acid with considerable difficulty. The ‘‘ nitronic ” or haloid constitution of the salts in both cases goes to account for this resistance of the SO, ion. I n the dimercurammoniun1noniun~ complex, NHg,, also, owing to the nitrogen atom being directly related to the mercury atoms, the molecular structure remains unaffected when the salt is subjected to the action of an oxy-acid, biit at once succumbs to the attack of a lialogen acid. It is also of interest to note that whilst both the hydrogen atoins of snlphnric acid are replaced by t h e group NHg,, only one atom of the tribasic phosphoric acid is similarly affectecl. This is what might have been expected, considering that in ordinary circumstances even a strong base like caustic soda can only yield the disodium phosphate. ‘]’HE DAVY-FARADAY RESEARCH LABORATORY, THE ROYAL INSTITUTION.

ISSN:0368-1645    

DOI:10.1039/CT9058700009

出版商:RSC    

年代:1905

数据来源: RSC

摘要:

DUNSTAN : THE VISCOSITY OF LlQITlD BfIXTtTRES. PART 11. 11 IV.--T/Zc Viscosity of Liquid M i s t w e s . Pwt 11. By ALBERT ERNEST DUNSTAN, B.Sc. IN Part I of this investigation (Trans., 1904, 85, 817, and Zeit. physioZ. Ch,en2., 1904,49, 590), I gave an account of the variation of absolute vis- cosity with concentration in the cases of the following pairs of liquids : 1, benzene-ethyl acetate ; 2, ethyl alcohol-carbon clisulphide ; 3, mer- captan-ethyl alcohol ; 4, acetone-etli yl alcohol ; 5, benzene-ethyl alc3hol; 6, benzaldehyde-ethyl alcohol ; 7, ethyl a lcohol-water ; 8, methyl alcohol-water ; and 9, acetic acid-water. The curves thus obtained could be divided into three classes : 1, sagged curves, approxi- mating to the normal (Nos. I , 2, 3, and 4) ; 2, curves showing minimal values of viscosity (Nos.5 and 6), and 3, curves giving one or more maximal values of riscosity (Kos. 7, 8, and 9). Based on the fact that hydroxylated, associated liquids such as water and the alcohols have a relatively high value of viscosity, the conclusion was deduced that a maximum point in a viscosity-concen- tration curve meant further association proceeding in the components, whilst the existence of a, minimum point pointed to the opposite view, namely, that some dissociation had resulted. Further experiments bear out the conclusion arrived a t in the former paper. The apparatus has been modified iii various ways with the result that a higher degree of accuracy has been attained. A large copper rect- angular tank provided with windows is used as the bath.The viscometers are much larger and are employed in duplicate, one for mixtures of high, and the other for those of l o w viscosity. Larger specific gravity tubes have been employed, having a capacity of 10 C.C. The liquids used, which were obtained from Kahlbauiii, have been carefully rectified and fractionatsd, and the components of the various mixtures have been weighed out to the milligram. E x P F, R I RI E N T A J,, 1. AZZyZ Alcoliol (sp. gr. 0.8500 a t 25’/0°) c m t l TT’nter. The curve afforded by this pair of liquids is of precisely the same form as was given by ethyl alcohol-water a i d methyl alcohol--water. There is it very well-marked maximum at 51-52 per cent. of allyl alcohol corresponding with 1 allyl alcohol, 3 water; a t this point, the viscosity of the mixture is 0,01895, or about twice that of water.It is somewhat remarkable that, in the two cases just quoted, there are also maxima a t 1 alcohol, 3 water. There is also a distinct inclicatioii of a discont8inuity a t 40 per cent.12 DUNSTAN: THE VISCOSITP OF LIQUID MIXTURES. PBRT TI. of allyl alcohol ; a t this concentration, the iiiolecular proportions are 1 allyl dcohol, 5 water. Allyl t~.lcoIiol, 0'0 100.0 14 -06 25.98 33-70 35.53 36-53 45.21 46'88 %. ?I* 0.00891 0.01232 0*01349 0'01682 0-01TSO 0'01Y34 0.0184ci 0'01888 0-01 895 Allyl nlroliol. %. 47.31 47,82 48.56 56 *6:3 65.00 69'56 83 2 0 9. 0.01887 0.01891 0.01892 0.01591 0 417 96 0 *01750 0.01537 2. n-Propgl Alcohol (sp. gr. 0.8009 at 2.cioi4") ccnd TT'clter. Again, as in previous cases of alcoholic solution in water, a very A great rise in viscosity takes place on mixing the components.Pei-cciLZogr coinposition. clearly marked maximum occurs at 61-62 per cent. of n-propyl alcohol, corresponding with 1 propyl alcohol, 2 water. At this point, the viscosity of the mixture is 0,02725, which is notDUNSTAX: THE VISCOSITY OF LIQUID MIXTURES. PART 11. 13 so far removed from that of the alcohol as appears from the curves for methyl aid ethyl alcohols. The viscosities of methyl, ethyl, and propyl alcohols are 0.005564, 0.01 113, and 0.01962 respectively, whereas the maximum values for the corresponding mixtnres in water are 0*01600, 0.02368, and 0.02725. 12-Propyl alcohol. %* 0.0 8.55 9'29 22.61 24-91 25-59 28-31 35-15 36.42 rl. 0.00891 0.01289 0-01312 0'01986 0-02047 0*02110 0.02188 0'02456 0'02438 .n-Prop.yl alcohol.43 '40 52-90 53-58 64.94 69.40 69'87 79'43 83.89 86-60 %. 100.0 7. 0 '026 16 0.02688 0.02707 0.02703 0-02620 0.02605 0.02450 0.02364 0-02311 0 '01962 3. Glycol (sp. gr. 1.1110 a t 25°/00) alzd Water. Contrary t o expectation, this mixture did not provide a curve which agreed with those afforded by other hydroxylated compounds in aqueous solutions. A few prcliminary experiments with glycerol also gave negative results and were abandoned. Graham in his classical paper on viscosity found a siinilar occurrence with glycerol (compare Trans., Zoc. cit.). So far from further association taking place, the reverse is indicated. It is quite possible that this substance, being already greatly associated in consequence of its two hydroxyl groups (as is shown by it,s very high coefficient of viscosity), is broken down by the water into simpler complexes.It would, therefore, be interesting t o ascertain the magnitude of its <' molecular weight " at varying concentration, using the depression of freezing point of the aqueous solutions. Glycol. Glycol. %. 71. %. rl. 0'0 0.00891 60 '84 0'04488 14'11 0 *O 125 8 69-52! 0.06227 33'11 0.01621 75'64 0'09202 45 1 3 0 -02860 1 0 0 ~ 0 0'1733 49.55 0.03199 The greatest divergence from the normal occurs at about 64 per cent. of glycol, this point corresponding with 1 glycol, 2 water.14 DUXSTAW : TEE VISCOSITY OF 1,IQTJID MIXTURES. PART IT. 4. Lccctic Acid (sp. gr. 1.2060 at 25'/4') am? Wutev. This hydroxyacid has a, different hehaviour from that of acetic acid.No maximum point is observed, whereas that of acetic acid is markedly FIG. 2. 0 10 20 30 40 50 60 70 80 90 100 Ptwentaye composition. prominent, On the contrary, a very sagged curve is obtained, giving a maximal divergence with about 70 per cent. of lactic acid, corre- sponding with 1 lactic acid, 2 water. Again, it seems probable that this very viscous, dihydroxylated substance breaks down in the presence of water to a simpler com- plex, as was noticed in the case of glycol and glycerol.DUNSTAN: THE VISCOSITY OF LIQUID MIXTURES. PART 11. 15 Lactic acid. Lactic acid. %. v. %. 17. 0-0 0'00891 43'98 0.02733 12.76 0 '01 186 53-30 0.03591 21.71 0.01455 60'24 0-03621 30.85 0.01849 75.75 0-07995 33'69 0.01782 100'0 0.4033 34.76 0*02026 5.Bemetbe and Acetic Acid (sp. gr. 0,8738 and 1.047 at 25',/4' respectively). Considering tlie fact that acetic acid in benzene solution gives abnormal results for the depression of freezing point, leading to the supposition that it contains double molecules, i t seemed of interest to study the behaviour of mixtures of these substances from the stand- point of viscosity, particularly as mixtures of benzene and ethyl alcohol afford a minimum point (Trans., Zoc. cit.), A specimen of pure acetic acid had been previously obtained by freezing out some of Kahlbaum's acid. This boiled a t 117*8"/752 mm., and by the freezing point method was found t o contain 99.9 per cent. of acetic acid. It was thought that this very small trace of impurity would not affect the results to any appreciable extent.The benzene used was supplied by Merck; it was distilled over sodium and boiled entirely between 80' and 81'. Alternate readings from two stop-watches were taken in all the following experiments, and they have been found t o agree to a very satisfactory extent. The time of flow for benzene is only 3'25", so that an accuracy greater than 1 in the third place of decimals is scarcely attainable. A distinct minimum was obtained a t 89 per cent. of benzene corre- sponding with 5 benzene, 1 acetic acid. This minimal value is 2 per cent, below that for acetic acid and seems to indicate a certain amount of dissociation. By the freezing point method, a distinct tendency is shown for the formation of complex molecules (compare Wal ker, Intru- dzcction to Physical Chemistry, p.204). Grams of acetic acid in 100 grams of benzene ...... 0'465 1.195 2'321 4.470 8.159 Molecular weight .,. .. , ... ... 110 115 117 122 129 It is not known, howevev, what is the molecular complexity of pure acetic acid in the liquid condition and at the ordinary temperature, It is quite possible, however, that its complexiky is greater than 2C&H,O,, for instance, so that altliongh in dilute solution iii benzene i t is approximately bimolecular, yet this condition may result from the breaking down of a more coniplex molecule.16 DUNSTSN: THE VISCOSITY OF LIQUID MIXTURES. PART 11. Beiizeae, %. 71. 0.0 0'0117.1 16.74 0 '008932 3493 0 .007341 48-29 0.006658 77.2ti 0 '005960 Benzene. %. 7.81 '42 0 '00596'2 89'73 0.005907 97'25 0.005941 100 *o 0.005973 6. Benzene ccwi n-Pro& Alcohol (sp. gr. 0.8'728 and 0.8009 at 25'14' respectively). The foregoing result with benzene and acetic acid ancl the previous case of benzene and ethyl alcohol made it of interest to investigate other benzene solutions. Although with benzene and wpropyl alcohol the minimum is not so well marked, it clearly exists, being about 1 per cent. below the value for benzene. It occurs a t 95 per cent. of benzene, corresponding with 12 benzene, 1 pi-opyl alcohol. n-Propyl alcohol. n- Pro] yl alcohol. %. '17. %. '17. 0.0 0.01962 8999 0.00598'3 83'10 0 '01 1 6 7 95.07 0.005917 70.22 0-00702s 100.0 0.005978 Preliminary experiments with mixtures of benzene and methyl alcohol gave similar results.SUV~TMLT~. Hydroxylated compounds give abnormal results, but, in the case of polyhydroxglated liquids this abnormality does not exist, probably because of the large degree of association originally existing in such substances. Discontinuj ties in the curves locate themselves at or near points of definite molecular composition, and this occurs so frequently that; one is compelled t o recognise the existence in solution of mole- cular aggregatos such as 1 ethyl alcohol, 3 water. On the other hand, abnormalities occur when hydroxylated substances are dissolved in benzene, but here they are opposite in nature, minimum points being obtained, a fact which indicates that the mole- cular complexes axe disturbed in this solvent, although, in the case of organic acid, the solute is not broken down to the monornoleciilar condition.At present there is no well-defined molecular constant of viscosity, owing perhaps to the large variation of viscosity with temperature and the difficulties of finding corresponding temperatnres, and consequently it is not possible to find the molecular condition of a liquid by deter- mining its coefficient of viscosity, but from a qualitative point of view it is obvious that associated substances are more viscous than mono-MERCAPTANS AND OLEFINIC KETONIC COMPOUNDS. 11 molecular substances. That there is a distinct difference between the two classes of substances may be seen from the following table, which gives the quotient of molecular volume by viscosity for the different compounds : Eeiizaldehyde . . . 6840 liquids. Methyl alcohol.. . 7240 Ethyl ,, ... 4930 Water . . . . . . . . . . . . 2020 Associated Acetone.. . . . . . . . . 23400 Acetic acid ... .,. 4970 I Benzene . . . . . . . . . . . . . . . 15300 Ethyl acetate.. ... ... 29700 Mono- Carbon disulphicie . . 16600 Ethyl mercaptaii ... 35400 Taking into account the foregoing consideration, it is quite clear that (with the exception of acetone) the associated liquids stand in a class by themselves (compare Thorpe and Rodger, J. P l d . Trans., 1694, II., A. 185). The nuthor intends to extend this research to other hydroxylated compounds. OWEN’S SCHOOL, ISLINGTON, N.

ISSN:0368-1645    

DOI:10.1039/CT9058700011

出版商:RSC    

年代:1905

数据来源: RSC

摘要:

MERCAPTANS AND OLEFINIC KETONIC COMPOUNDS. 17 V.-The Combination of He?*cuptam with Ole$nic Ketonic Compozi nds. By SIEGFRIED RUHEMANN. SINCE Gaurnann carried out his important researches on the mer- captoles, it has been Yosner especially who has studied the interaction of mercaptans with ketones and has applied it to olefinic ketones (Ber., 1901,34, 1395 ; 1902, 35, 799 ; 1904, 37, 502). His experiments led to the result that mercaptans, besides condensing with the ketonic group of the mono-olefinic ketones, also became attached to the ethylene linking, and thus yielded trithio-compounds, for instance : C,H,.CH:CH*CO*CH, + 3C,Hl,*SH = C,H,*CH(S.C51~11)*CH~.C(S* C,H,,),*CH,. He arrived, however, at the conclusion that, although the mercaptans united by addition with all the mono-olefinic ketones, the tendency of the memaptole reaction to take place was diminished if the ketonic group was adjacent to the ethylenic linking. This inhibiting influence of the etbylenic linking he found to increase with the accumulation of olkyl groups, especially of phenyl radicles in the olefinic ketone.Thus, benzylidenedeoxybenzoin, CGH5.CH:C(C,H,)*C0.CGH5, he showed, did not form a mercaptole, the mercaptans simply combining additive1 y a t VOL. LXXXVII. c18 RUHEMANN : THE COXBINATION OF the ethylenic linking. Posner further stated that diolefinic ketones of i I I 1 the type v:C*CO*C:y yielded additive products with 2 molecules of the mercaptans ; sometimes, however, along with the additive change, the mercaptole reaction took place, but the tetrathio-compounds thus formed on oxidation were transformed into ketodisulphones. His I l l 1 experiments on diolefinic ketones containing the grouping C:C*C:C-CO- led him to the view that they do not form mercaptoles, but additive products with 2 molecules of mercaptans.To bring about the action of mercaptans on the olefinic ketones, Posner either used hydrogen chloride alone or employed this agent together with zinc chloride in order t o facilitate the condensation of the mercaptaiis with the ketonic group. With the view of preventing the mereaptans from reacting with the ketonic group and to effect only the combination of the mercaptans with the olefinic ketone, I have chosen bases as catalytic agents instead of hydrogen chloride. I n my first experiments, sodium ethoxide was employed, but I have found since that piperidine acts more promptly; the reaction takes place with development of heat, yielding additive products only.These substances do not give a coloration with ferric chloride, they dissolve in cold concentrated sulphuric acid, forming yellow or orange solutions, On applying this reaction to a diolefinic ketone of the type I : C:C*CO*C:(;1, namely, dibenzylideneacetone, I find that either 1 or 2 molecules of a mercaptan may become attached. With regard to the action of mercaptans on diolefinic ketones of the type I1 : Q.C*C*C*CO-, I arrive, however, a t a result which differs from that which Posner has obtained. As mentioned before, he found that cinnamylideneacetone as well as ciiiiiaaiylideneacetophenone under the influence of hydrogen chloride takes up 2 molecules of a mercaptan, whilst I find that, on 'using piperidine as catalytic agent, cinnamyl- ideneacetophenone, an example of the type of ketones hitherto examined by me, united with 1 molecule only of either phenyl or isoamyl mercaptan.It would therefore seem that the additive action of mercaptans on cinnamylideneacetophenone and olefinic ketones of similar constitution varies according as hydrogen chloride or piperidine is used as catalytic agent. I may, ho\vever, point out that if Posner's results are correct, the action of mercaptaiis would differ most markedly from the behaviour of other compounds towards olefinic ketones. Knoevenagel (Bey., 1904, 37, 4038), for instance, has lately shown that although diolefinic ketones with the grouping I, on treat- ment with potassium hydrogen sulphite, yield hishydrosulphonic acids, those of type I1 unite with 1 molecule of the hydrogen sulphite I I I I I I 1 .1 1 IMEBCAPTANS WITH OLEFINIC KETONIC COMPOUNDS. 19 only. But the following fact induces me to doubt the correctness of Posner’s results. With one exception, he records only the analyses and properties of disulphones which he obtained by the oxidation of the products of the union of mercaptans with cinnamylideneacetone and cinnamylideneacetophenone respectively. The additive compound described by him (Ber., 1904, 37, 510) is the substance which he pre- pared from cinnamylideneacetophenone and phenyl mercaptan, and from the estimation of sulphur he concludes that it has the formula C6H;CH(S-C,H5)*CH2* CH( S*C6H,)*CH2* CO*C,H,.The melting point (102’) of this substance, however, closely agrees with 103-104°, which I find to be the melting point; of the product of the reaction of piperi- dine on the mixture of the ketone and the mercaptan. I have proved that the formula for this product is C,H,*CH:CH*CH( S*C?,H,)*CH,*CO*CnH,, and, moreover, having repeated Posner’s experimeut, I have ascertained that the compounds obtained by the two methods are identical. The constitution of the substance which is formed from cinnamyl- ideneacetophenone and phenyl mercaptan may be expressed either by the formula : I. C,H,*CH: CH* CH( S* C,H,) CH,*CO*C,H,, or, in the light of Thiele’s hypothesis, it may be formulated as follows : 11.C,H’,*CH( S*C,H,) CH: CH* CH,*CO* C,H,. I am, however, inclined to attribute to it the former formula, and the analogous constitution to the substance which I have obtained from oinnamylideneacetophenone and isonmy1 mercaptan, because both additive compounds dissolve in cold concentrated sulphuric acid, yield- ing a deep red solution, as do the diolefinic ketone itself and cinn- amylidenemalonic acid and cinnamylideneacetylacetone. Finally, it may be mentioned that the olefinic ketones seem t o react not only with mercaptans, but also with hydrogen sulphide. As yet, I have examined only the behaviour of this gas towards benzyl- ideneacetylacetone i n the presence of sodium ethoxide, and have found that thiobenzaldehyde is produced. Its formation is most likely the result of the decomposition of the first formed additive product, and takes place thus : C,H,*CH(SH)-CH(CO*CH,), = CiH,*CHS + UH,(CO-CH,),.This reaction, therefore, resembles the transforma- tion of the additive products of olefinic ketones with primary organic bases (Ruhernann and Watson, Trans,, 1904, 85, 1170).20 RUHEMANN : THE COMBINATION OF EXPER I M E N T A L . A c t i o n of M e r c a p t a m s 0 7 2 i W o ~ o - o Z e f i y ~ i c K e t o n i c c 0 l?b $3 0 fu 9% d s. Phe~zylthiolberzx~Zuceto~ze, CGH,* CH( 8. C,H,) .C H,*CO* CH,. Benzylideneacetone (2.6 grams) dissolves in slightly warm phenyl mercaptan (2 grams). On adding 2-3 drops of piperidine to the solution, it becomes hot, and in a short time sets to a hard solid. This is sparingly soluble in light petroleum (b.p. 50-60") and crys- tallises from its solution in dilute alcohol in colourless needles which melt at 58-59'. 0.2018 gave 0.5545 CO, and 0.1 155 H,O. This substance dissolves in cold concentrated sulphuric acid, yielding a green solution with a red fluorescence, but the colour slowly changes t o red. C = 74.93 ; H = 6.35. C,,H,,OS requires C = '75.00 ; H = 6.25 per cent. Ethyl PherLyZthiolbe~x?/Zacetoucetate, C6H,.CB(s.C6H,).CH(CO*CH~).cO,.~~H~. The union of phenyl mercaptnn with et.hyl benzylidenencetoacetnte has been brought about by means of a small quantity of an alcoholic solution of sodium ethoxide. When this is added to the mixture of the mercaptan (2 grams) and the freshly distilled ketonic ester (4 grams), the reaction takes place with development of heat, and, when cold, the whole solidifies. The substance readily dissolves in alcohol, chloroform, ether, or carbon disulphide, with difficulty, how- ever, in light petroleum, and crystallises from this solution in colcur- less needles which melt a t 72-73".0.2025 gave 0.5165 CO, and 0.1 146 H,O. The solution of this compound in cold concentrated sulphuric acid C = 69-56 ; H = 6 9 8 . C,,H,,O,S requires C == 69-51 ; H = 6.1 0 per cent. is orange. Eth;yZt?iiolhenxyZacetyZaceto?ze, C,H,*CH(S*C,H,)-CH( CO-CH,),. Benzylideneacetylacetone (3 grams) interacts with ethyl mercapt8an (1 gram) on adding a few drops of an alcoholic solution of sodium ethoxide. The solid which is formed, is washed with water and dis- solved in hot dilute alcohol; the solution, on cooling, deposits colour- less, silky needles, which melt at 75-76' and dissolve in cold concen- trated sulphuric acid, yielding a light yellow solution.MERCAPTANS WITH OLEFlNIC KETONIC COMPOUNDS.2 1 0.2003 gave 0.4943 CO, and 0.1335 H,O. c'= 67.30 ; H = 7.40. Ci4Hl8O2S requires C = 67.20 ; H = 7.20 per cent. isoA~tayZthioZbe?ix?~ZcccetyZaceto.,ie, C,H,*CH(S*C,Hl,)*CH(CO*CH,)2. The union of benzylideneacetylacetone (1 *8 grams) and isoamyl rnercaptan (1 gram) has been effected by sodium ethoxide dissolved in alcohol. The solid, which is produced after r?, few hours, dissolves in boiling light petroleum, and, on cooling, crystallises in colourless needles which melt a t 57-58". 0.2018 gave 0.5169 CO, and 0.1495 H,O. C = 69.85 ; H = 8.24. The solution of this substance in cold conceiztrated sulphuric acid is C,7H,,0,S requires C = 69.86 ; €€ = 8.22 per cent.yellow. Be./ax?lZtl~ioZbenxyZ~cet~Zacetone, C,H,*CH( S*CH,.C,H,)*CH(CO* CH,),. This compound is foriiied on adding a few drops of sodium ethoxide dissolved in alcohol to the mixture of benzylideneacetylacetone ( 3 grains) and benzyl mereaptan ( 2 grams). The white solid, which separates on stirring, readily dissolves in hot alcohol, and, on cooling, crystallises in colourless prisms which melt a t 77-78" and dissolve in cold Concentrated sulphuric acid, yielding a deep yellow solution. 0.2024 gave 0.5429 CO, and 0.1175 H,O. C = 73.16 ; H = 6.45. C,,H,,O,S requires C = 73.08 ; H = 6.41 per cent. P~~e~~y~th&oZberzxyZ~6ce~yZ~~ceto.12e, CY,H,bCH(S*C6H,)*CI(cO*c~~)2. On adding a small quantity of sodium ethoxide dissolved in alcohol to the mixture of phenyl mercaptan (3 grams) and benzylideneacetyl- acetone (5 grams), heat is developed, and the, whole becomes solid.This product, after mashing with a little cold alcohol, is dissolved in boiling alcohol ; the solution, on cooling, deposits colo urless needles, which are readily soluble in ether, chloroform, or carbon disulphide, but less so in alcohol ; the substance melts at 119-120", and its solu- tion in cold concentrated sulphuric acid is orange. 0.2012 gave 0.5347 CO, and 0.1112 H,O. 0.3183 ,, 0.2540 BaSO,. S= 10.96. C=72*47 ; H=6*14. C,,HX1,O,S requires C = '72.48 ; H = 6-04 ; S = 10.74 per cent. P~enylt~~ioEbenx?qlbeIl,zoylQcet~~~~, C,H,*CH( S*C,H,).CH( CO-OH,) *CO- C,H,.The union of benzylidenebenzoylacetone with phenyl mercaptan has been effected by mixing the diketone (4.5 grams) dissolved in benzene22 RUITEMANN : THE COMBINATlON OF with the mercnptan (2 grams) and adding 2-3 drops of piperidine, when, in a short time, the whole sets to a solid mass. This is washed with light petroleum and crystallised from alcoho1,jn which it dissolves with difficulty; colourless needles are thus obtained, which melt a t 140-141' and dissolve in cold concentrated sulphuric acid, yielding an orange solution. 0.2008 gave 0,5640 CO, and 0.1016 H,O. C = 76%3 ; H = 5.62. C,,H,,O,S requires C = 76-76 ; H = 5.55 per cent. isoAmylthiolbenxylbenxoylaceto?te, C6H5=CH( 8- C,H,,) CH( CO CH,) Coo C,H,. The action of piperidine on a mixture of benzylidenebenzoylacetone (2.4 grams) and isoamyl mercaptan (1 gram) dissolved in light petrol- eum is accompanied by development of neat.The solid which is pro- duced, is readily soluble in benzene or ether, less so in cold alcohol, but readily when hot, and crystallises from dilute alcohol in colourless needles which melt at 104-105". 0.2005 gave 0.5466 CO, and 0.1326 H20. The solution of this substance in concentrated sulphizric acid is C = 74.35 ; H = 7.34. C,,H,,O,S requires C =z 74.57 ; H = 7-38 per cent. yellow. Action. of Mevcccpta.lzs on Diolefinic Ketones. T7~e Union of I).ibe.laxylicleneacetone with Mevcaptcms. As already mentioned in the introduction, the union of mercaptans with dibenzylideneacetone yields either mono- or di-thio-compounds.The additive products, with 2 molecules of mercaptans, which Posner (loc. cit.) has already prepared, can readily be obtained in a pure state by the use of piperidine as catalytic agent instead of hydrogen chloride. But some difficulty may be experienced in getting the monothio-com- pounds pure, since their formation is accompanied by that of the additive products with 2 molecules of mercaptans. This is especially the case in the preparation of thiophenylbenzylbenzylideneacetone, which 1 have not yet obtained free from dithiophenyldibenzylacetone, isoAm~lthiol6enxylbenx ylideneacetme, C,H,*CH(X* C,H,,)*CH,*CO-CH:CH*C6H5. This substance is formed by mixing isoamyl mercaptan (0.5 gram) wit'h dibenzylideneacetone (1 -2 grams) dissolved in benzene, and add- ing 3 drops of piperidine.After several hours, the benzene isMERCAPTANS WITH OLEFINIC KETONIC COMPOUNDS. 23 evaporated ~ Y A vccczco, and, on stirring the residual oil, it solidifiee. The solid is readily soluble in benzene, chloroform, ether, or alcohol, and crystallises from dilute alcohol in colourless needles which melt at 60-61O. 0.2024 gave 0.5788 CO, and 0,1405 H,O. The solution of this compound in concentrated sulphuric acid is C = 77.99 ; H = 7.71. C2,H,,0S requires C = 78.10 ; H = 7.69 per cent. yellow. YlLe~?/ltlLiolberzxylbenx?/Zicleneacet one, C,H,* CH (M-C,H,) *CH,*CO*CH:CH*C,H,. On adding 2-3 drops of piperidine t o the mixture of phenyl mercaptan (I gram) and a benzene solution of dibenzylideneacetone (2.2 grams) and leaving the solution for half an hour, and then pouring into it light petroleum, a white solid is precipitated.This product dissolves somewhat readily in boiling alcohol, and, on cooling, crystal- lises in colourless needles which melt a t lf11-122°. On analysis, numbers were obtained which indicated that this product is a mixture of the additive compounds of the diolefinic ketone with one and two molecules of the mercaptan. The melting point is raised to 127-128" by a second crystallisation from the same solvent, but, as is indicated by the following analysis, the substance is still impure. 0.2010 gave 0*5S64 CO, and 0.1061 H,O. C = 79.56 ; H = 5.86. C,,H,,OS requires C = 80.23 ; H = 5.81 per cent. This componnd, which has been prepared before by Posner (Zoc. c i t . ) , is readily formed on adding piperidine to the benzene solution of equal weights (2 grams) of dibenzylideneacetone and phenyl mercaptan.After a short time, the mixtnre sets to a semi-solid which dissolves in boiling alcohol with difficulty and, on cooling, cry stallises in colourless, iridescent prisms. These, after n second crystallisation from the same solvent, melt at 134-135', as compared with 139-140' found by Poaner, and gradually dissolve in cold concentrated snlphuric acid forming an orange solution which slowly turns red. 0.2003 gave 0.5617 CO, and 0,1033 H,O. C= 76-48 ; H= 5-72. C29H260S2 requires C = 76-65 ; H = 5.72 per cent. !Phe Union of Jfercaptans with C i ~ P L c ~ n z ? / Z i d e 9 2 e a c e t o ~ ? ~ e ~ o ~ I have studied this reaction with special care in order to examine whether cinnamplideneacetophenone takes up 2 moleoules of mercap-24 RUHEMANN : THE COMBINATION OF tans, as stated by Posner ; but I find that it unites with 1 molecule only of isoarnyl or phenyl mercaptan and yields compounds which are isomeric with the additive products of dibenzylideneacetone with 1 molecule of these mercaptans.PJLenyl p-isoAmylthiol-y-benxylidenepropyl Ketone, C,,H,*CH: CH- CH ( S.C,H,,)*CH,* CO-C,,H,;. I have carried out two experiments; in the first, a mixture in molecular proportions of cinnamylideneacetophenone (2.2 grams), dis- solved in benzene, and isoamyl mercaptan (I gram) was treated with 3 drops of piperidine, and, after several hours, the benzene was evaporated. The residual oil, which solidified on stirring, crystnllises from dilute alcohol in colourless needles; these melt at 64" and dis- solve in cold concentrated sulphuric acid yielding a deep red solution.The second experiment has been performed in a similar manner except that equal weights (2 grams) of the ketone and the mercaptan have been used, and the solution has been kept overnight before evaporating off the solvent. The snbstance which is formed, after crystallisation froin alcohol, melts a t 64". The identity of the two preparations has been further verified by analysis : I. 0.2025 gave 0.5792 CO, and 0.1404 H,O. C = 78.00 ; H = 7.70. 11. 0.2012 ,, 0.5745 CO, ,, 0.1405 H,O. C=77.87; H=7.75. C2,H,,0S requires C = 78.10 ; H = 7.69 per cent., whilst the additive compound with 2 mols. of the mercaptan, C211H,,0S,, requires C = 73.30 ; H = 8.60 per cent.Phen y I /3- Phen y lt h io I- y- benx y lidempr op y Z Ketone, C,H,* CH: CH* UH (S* C,H,)*CH,*CO* C,H,. On mixing phenyl mercaptan and cinnamylideneacetophenone either in molecular quantities or in the proportion of 1 mol. of the ketone to 2 mols. of the mercaptan, and adding a few drops of piperidine t o the solutions of these mixtures in benzene, there is formed in both casea the same compound, which is precipitated by light petroleum. The substance is readily soluble in ether or chloroform, not so readily in cold alcohol, and crgstallises in colourless needles from its solution in hot dilute alcohol, Both specimens melt at 103-104", and their solutions in concentrated sulphuric acid are deep red. 0.2014 gave 0,5928 CO, and 0.1063 H,O.C = 80.27 ; H = 5.86, C23H2,0S requires C = 80.23 ; H = 5.81 per cent.MERCAP'I'ANS WITH OLEFINIC KETONIC COMPOUNDS. 25 C,,H,,OS,, the additive compound of the diolefinic ketone with 2 mols. of phenyl mercaptan, which, according to Posner (Zoc. cit.), is formed on using hydrogen chloride as a catalytic agent instead of piperidine, requires C = 76.65 ; H = 5.72 per cent. Although the close agreement of the melting points indicates that Posner's compound is identical with the one thus obtained, yet I have thought it advisable for direct comparison to prepare a specimen accord- ing to Posner's diredons. For this purpose, dry hydrogen chloride has been passed into a cold solution in glacial acetic acid of the mixture of cinnamylideneacetophenoiie (2 grams) and pheiiyl mercaptan (2.5 grams), when, after a short time, the whole sets to a semi-solid; the substance crystallises from alcohol in colourless needles which melt a t 103" and have other properties, such as the shape of the crystals and the solubility, resembling those of the compound formed under the influence of pipeyidine. I have, moreover, verified the composition of this specimen by analysis : 0*2008 gave 0.5902 CO, and 0*1508 H,O. C = 80.16 ; H = 5.85. C,,H,,OS requires C = 80.23 ; H = 5.81 per cent. Action of XIpdrogen Xu Zphicle on Henc yiideneace t y Zucet one. On passing hydrogen sulphide into a slightly warm alcoholic solution of benzylideneacetylacetone to which a little sodium ethoxide dissolved in alcohol has been added, a white solid is formed. This is insoluble in alcohol or glacial acetic acid, but readily dissolves in chloroform, and is precipitated from this solution by alcohol. The substance softens a t 75-86" and is identical with thiobenzaldehyde. 0.2017 gave 0 5065 CO, and 0.0920 H,O. I am engaged i n the further investigation of the action of mercap- tans on olefinic ketonic compounds in the presence of organic bases, and in the study of the additive products which are thus formed. C =68*49 ; H=5*06. C7H,S requires C = 68.85 ; H = 4.91 per cent. GONVILLE AND CAIUS COLLEGE, CAMBRIDGE.

ISSN:0368-1645    

DOI:10.1039/CT9058700017

出版商:RSC    

年代:1905

数据来源: RSC

摘要:

26 VELEY : HYDROLYSIS OF AMMONIUM SALTS. TI.-Hydrolysis of Ammonium Salts. By VICTOR HERBERT VELEY. Introductory. IN the ordinary text-books of chemistry it is stated in general terms that aqueous solutions of ammonium salts when boiled become acid with the evolution of a vapour of alkaline reaction. More definite statements are to the effect that, under such conditions, triammonium phosphate loses two-thirds of its ammonia, and is converted into am- monium dihydrogen phosphate; also that an aqueous solution of ammonium oxalate loses ammonia even at -lo. Such statements appear t o imply that these decompositions are to be classed among heat dissociation phenomena, namely, that ammonium chloride, for example, is decomposed when heated either in the dry state or in aqueous solu- tion, according to the same course of events.The object of the present communication is to show that although the net result is the same in both cases, yet the latter is consequent on hydrolysis, NH,Cl+ H20 t NH,OH + HC1 and NH,OH = NH, + H20, and not on heat dissociation. Investigations (Walker, Zeit. plysikat. Chern., 1889, 4, 319 ; Ar- rhenius, ibicl., 1894, 13, 407; Shields, Phil. Mug., 1893, [v], 35, 365; van't Hoff, Chemisehe Dynarnik, 1898, 121-126) on the hydrolysis of salts, such as the cyanides, acetates, and amides, have shown that three cases are possible : (1) salts formed from a weak base and strong acid, (2) salts from a strong base and weak acid, and (3) salts from a weak base and weak acid. Ammonium salts containing the relatively weak base ammonia would probably be included only in categories I and 111.I n the former, it has been shown both by inversion and concluc- tivity experiments that the amount of hydrolysis is dependent on the mass of water, namely, the dilution, and the condition of equilibrium is represented by the equation : In the latter, the amount of hydrolysis is independent of the dilution, and it,s equation of equilibrium is It will be shown in the sequel that the hydrolysis of ammonium salts, which results from boiling their aqueous solutions, presents these two cases, namely, that (1) its amount is dependent on the dilution, and (2) is independent of the dilution when beyond a certain limiting value,VELEP : HYDROLYSIS OF AMMONIUM SALTS. 27 There is, further, a third case in which hydrolysis is nil or inappreci- able a t any degree of dilution.EX P E R I MENTAL. The method of experiment consisted in boiling 100 C.C. of the several aqueous solutions in round-bottomed, Jena glass flasks of about 500 c.c, capacity fitted with inverted condensers," according to the ordinary process for determining the proportion of ethereal salts by saponifica- tion. The duration of each experiment was one hour, at the expiry of which, the flask was disconnected, its contents rapidly cooled, and the amount of free acid estimated and taken as a measure of the ammonia lost. I n most cases the proportion of this free acid was estimated by an ammonia solution of approximately decinormal strength, litmus being used as an indicator ; in the case of organic acids, which do not give a sharp definition with litmus, caustic soda solution of the same concentration was substituted for ammonia and phenolphthalein for litmus.Although a t the ordinary temperature there did not appear to be any riEk of the displacement of ammonia by the caustic soda added, yet it is not pretended that the results obtained are of the same order of accuracy. Such a method seemed, however, to be the only escape from an experimental difficulty. In the case of the tri- and di-ammonium phosphates, which are alkaline in react.ion, the process was reversed, a decinorrnal solution of hydrochloric acid being substituted for ammonia. A possible source of error would arise when the acid simultaneously liberated with the ammonia was volatile and might also escape, but, so far as observation went, such escaping acid would recombine with the ammonia, and the salt regenerated mould be washed back into the solution by the condensed water. A further source of error might arise from differences in roughness of the glass of different flasks, whereby the evolution of ammonia would be facilitated, but a com- parative experiment showed no appreciable difference in ammonia lost when two solutions of ammonium nitrate were heated under the same conditions for the same time, but to one of which half a gram of finely divided silica had been purposely added.The solutions taken for most series of experiments were of 1, 0.5, 0.2, 0.1, and 0.05 normal con- centrations respectively; but it will be evident that the method of experiment adopted is restricted on the one hand by the solubility of the salts for concentrated solutions, and on the other by the small If.The conderisers used were all of glass with straight internal tubes ; a slight error would, doubtless, be caused by the few drops which fell back into the main bulk of the solution after the operation of boiling had been stopped.28 VET,EP : HYDROLYSIS OF AMMONIUM SALTS. absolute amount of amnioiiia lost from very dilute solutions, whereby the experimental error is very largely increased. ,Wethod of Calculation and Bxpression cf h‘esults. I f Y represent the loss of ammonia from the solution and ill the amount of ammonia originally combined, then P102/M will be the per- centage molecular loss ; for the purpose of avoiding long decimals, the values have been multiplied by 10, and the numbers this obtained designated as X= YlO3/,’1.I.For example, two deciiiormal solutions of ammonium nitrate (0.8 gram in 100 c.c.) containing 0.17 gram of combined ammonia were placed in two sets of apparatus placed in parallel, and heated for the same period of time, as a comparative experiment. The values for IT found were 32.3 and 33.S or a differ- ence of 3 per cent. approximately, which is within the limit, about 5 per cent., of saponification experiments. The salts examined were the bromide, chloride, nitrate, sulphate, the three orthophosphates, formate, acetate, oxalate, succinate, citrate, ethyl sulphate, benzoate, salicylate, benzene- and naphthalene-a-sul- phonates ; such a list might be greatly extended, but the foregoing series appeared to be representative and served for the purpose of various comparisons.The salts of the organic acids, with the exception of the oxalate, were obtained from Kahlbaum ; the bromide, chloride, nitrate, sulphate, diphosphate, and oxalate were either fine crystalline specimens a t hand, or were recrystallised specially. The chlorate was prepared from the barium salt by precipitation with ammonium sulphate and recry stallising ; it contained a trace of chloride. The monophosphate was obtained by the addition of glacial phosphoric acid to concentrated ammonia solution until the solution was distinctly acid, a further quantity of acid was added until no precipitate was produced on the addition of barium chloride to a test portion ; the solution was partially evaporated and allowed to crystallise.The triphosphate was obtained by the cautious addition of concentrated ammonia to an aqueous solu- tion of the diphosphste ; the salt crystallised out in fine needles, which were dried partially by suction, and finally over sulphuric acid. No variation was made in the method of procedure except in the case of the oxalate, in which case the experiments were conducted in a dark room on account of the ready decomposition of solutions when exposed to sunlight (Downes and Blunt, Yroc. Roy. Soc., 1879, 28, 209 ; Richardson, Trans., 1894, 65, 450). Jn order to determineVEIiEY: HYDROLYSIS OF AMMONIUM SALTS. 29 whether the decoiiiposition of aqueous solutions of the salt, as stated above to occur even at - lo, is due to the hydrolysis of the salt at that temperature, or to its decomposition as induced by sunlight, two seminormal solutions of the salt were taken, one kept in the dark for 14 hours at the ordinary temperature, the other heated for the same time a t 40° in a dark chamber, namely, a bacteriological incubator.There was no appreciable loss of ammonia in either case, thus proving that exposure to sunlight was the determining cause in the above- mentioned observation. Experimental Results. In the tables given in the sequel, the molecular concentrations in terms of normality "are given in the first, and the found values for K in the succeeding columns. CATEGORY I. E y d ~ o l y s i s Nil 09- Inappreciable. 117. K. K. K. 1.0 - 1.3 0.7 0.5 0.01 7 1.2 2.7 0.2 nil 1-08 3.5 0.1 mi 1 1.4 4.0 0.05 nil 5-8 3-5 Groinide.Chloride. Benzenesulphoiiate. As regards these three salts, it is worthy of note that the three acids combined with the ammonia are those which give the highest value, according to Ostwald (J. pr. Chem., 1884, 29, 401-402), ( 1 ) for the hydrolysis of methyl acetate amd (2) for the inversion of cane sugar; thus, the persistence with which the ammonia is retained, serves as a measure of the activity of the acid. This point will be further alludecl to in the sequel. CATEGORY 11. AT. 2.0 1.0 0.5 0.2 0.1 0.05 Hydrolysis Dependent on Dilution. Nitrate. Xu1 phate. K. K * 5 . 3 19.0 7% 20.9 9.5 30.8 11-2 389 14.3 80.5 16.5 -30 VELEY: HYDROLYSIS OF AMMONIUM SALTS. I n the foregoing salts, the amount of hydrolysis increases pro- gressivelywith the dilution, and more markedly in the case of the nitrate than in that of the sulphate, the limit of which appears to be reached nearly a t the point at which the experimental method becomes im- possible.As regards the nitrate, the results of which show irregularity, it is probable that the main reaction of hydrolysis is complicated by the decomposition at the temperature used of the liberated nitric acid ; nitrous acid is formed, which interacts with the ammonia (liberated, but not completely boiled off) to give ammonium nitrite, which is a t once decomposed into nitrogen and water. ATEG GORP 111. Hydrolysis Independent of Dilution ut a Limiting Valzce. All the other salts examined come under this, the most common For the sake of convenience only, these ealh have been category.divided into inorganic and organic respectively. Salts of Ifiorgcmic Acids. Chlorate. Monophosphate. Diphosphate. N. K. K. K. 0.5 15.5 1 4 5 37.3 0.2 18.7 18.6 42.9 0.1 20.3 22.3 40.0 0.05 18.5 21.5 41.6 The value found for I . for the triammonium phosphate was 600 approximately, but the salt is relatively unstable, and probably both hydrolysis and dissociation proceed simultaneously. ,Salts of Oq-ganic Acids. These salts are further divided for the purpose of convenience into those of (1) paraffinoid and (2) benzenoid acids. Forniate, Acetate. N, K. K. 1'0 37'2 53.4 0-5 35.6 95.8 0'2 22.0 90'3 0 '1 20 -1 94.0 0-05 19'1 90.3 0 *025 I 100 *o Oxalate. Snceinate. Citrate. K. K. K. - 235'6 215.5 - 230.0 198.6 17.4 244'6 280.0 22.3 243.8 275.0 23 '2 240.0 282.0 23.8 - - Ethyl sixlphate. K.4.0 8'34 10'4 11.1 12% -VELEY : HYDROLYSIS OF AMMONIUM SALTS. 31 Xalts of Benzenoid Acids. N, K. K. K. 1 *o 3.1 0 *a 2 -6 0.5 9 -0 11.0 9 -0 0 '2 10.3 14.0 10.0 0 '1 10.6 16'0 15.0 0.05 11.1 14'4 14.9 Naphthnlene- Benzoate. Salicylate. a-sulyhonate. The only point of special notice in the foregoing table is the behaviour of the formate, which differs from all the other ammonium salts examined in that the value for K decreases with decrease of con- centration. Two series of experiments were conducted, but the values obtained were c3oncordant within the limits of experimental error. Hydrocyanic acid, which might be formed according to the equation HCO,NH, = HCN + 2H,O (and is thus produced when the dry salt is heated), was tested for, but with a negative result. At present, it is not proposed to offer any explanation of this discrepancy. Discussion of Results.I n a preceding section, it was observed that the nminonium salts of those acids which give the highest values for the hydrolysis of methyl acetate and of the inversion of cane sugar were those which gave the lowest values in the present investigation. It appeared worthy of interest to pursue this comparison further, and for this purpose the values for l/lOth molecular concentration have been selected, this being t'he concentration a t which such values have attained constancy. The nitrate and formate are omitted from the present discussion as hydrolysis in both these cases is doubtless modified by secondary reactions.I n the following table, the values of K for the remaining salts are arranged in order of increasing magnitude in column I, and their reciprocals l/Ii consequently in order of decreasing magnitude. Salts. K. Bromide ............................. nil Chloride .............................. 1'4 Benzenesulphonate ............... 4 .O Benzoate .............................. 10'6 Ethyl sulphnte ..................... 11.0 Bulphate .............................. 14'0 Salicylate ........................... 16'0 Chlorate .............................. 20 -3 Oxalate .............................. 22 '3 Diphosphate ....................... 40'0 Acetate .............................. 90.0 Succinate ...........................243.8 Citrate. .............................. 275 -0 Naphthalene-a-sulphonato ...... 15'0 1/K. 0'713 0-250 0'094 0.091 0'073 0.066 0.062 0-049 0.045 0.025 0.011 0'004 0 *003 cn Chloride = 100. 100.0 35.2 13.2 11'2 10.2 9.2 8 *7 6.9 6 '9 3.5 1.5 0 -57 0.51 -32 VELEY: HYDROLYSIS OF AMMONIUM SALTS. As a further comparison, the reciprocals 1 / K have been calculated in terms of the chloride t’aken as 100 (column 111). In the following table, the acids are arranged in the order of avidity for ammonia in column I, and in column I1 in their order (mean value) obtained in the investigptions of Ostwdcl (vide suprcc) so far a s the comparison may be instituted. I. H ydrohromic. Benzenesulphonic. * Ethyl sulphuric. Sulphuric. H yarochioric. 11. I. 11. Hytl rol )romic.Phosphoric. Phosphoric. Hen zt?ncsulphonic. Ace tic. Citric. Hydrochloric. Succinic. Succinic. Ethyl sulphuric. Citiic. Acetic. Cliloric. Sul pliuric. Osnlic. The siinilarity as regards the relative order of magnitude is very striking; the order of absolute magnitude differs generally as t o the high values of the two haloid acids, whereby all the values of most of the remaining acids are consequently reduced, and particularly as to the case of chloric acid, which should rank with the haloid acids, but as a matter of fact conies much below them ; but a consequent decom- position of the chloric acid formed in the reaction studied may possibly be a disturbing factor. This line of investigation might be further extended, not only to the ammonium salts of other acids, but also to t h e substituted ammonium salts of the same acids. The present comniunication may serve as a preliminary to further acconnts of investigations, although i t is not, of course, pretended that the method adopted is of such an order of accuracy as others on the magnitude of chemical change under definite conditions. I am indebted to Mi-. John, of Jesns College, Oxford, for assistance in the earlier portion of this work. When aqueous solutions of ammonium salts are heated at their boiling point, the evolution of ammoni;L and concomitant acidity of solutions result not froin a direct dissociation, but froin hydrolysis. Three cases are presented : (1) such hydrolysis is nil or inappreciable, (2) it is dependent on the dilution, and (3) i t is independent of dilution when beyond a certain limiting due. The persistence or avidity with which the several acids retain the -’ C’altlwell, Yroc. Roy. Soc., 1904, 74, 185.STUDIES IN OPTICAL SUPERPOSITION. PART I. 33 ammonia in combination is analogous to their activity or avidity in the cases of hydrolysis of methyl acetate, and inversion of cane sugar ; the relative, but not the absolute, order of magnitude is the same in all these three chemical changes.

ISSN:0368-1645    

DOI:10.1039/CT9058700026

出版商:RSC    

年代:1905

数据来源: RSC

摘要:

STUDIES IN OPTICAL SUPERPOSITION. PART I. 33 VII.-Studies in Optical Superposition. Part I. By THOMAS STEWART PATTERSON and FRANCIS TAYLOR, B.Sc. OPTICAL superposition is the somewhat unsuitable term which has been applied to the combination of two or more optically active radicles in one molecule. Such compounds have hitherto received but little systematic investigation, although i t seems possible that t'heir examination might lead to interesting results in regard to various phenomena such as those connected with solution or with the com- bination of radicles generally. When in a simple active molecule such as that of lactk acid the replaceable hydrogen atoms are substituted by radicles like methyl and ethyl or acetyl and benzoyl, the change in rotation which occurs with each substitution is probably due, not merely t o the addition of a new group, but also to a modifig,ation, a slight molecular rearrangement, of the active radicle itself.That is, the lactyl radicle, supposing it could be detached from a molecule of methyl lactate without suffering any other change, mould show, when examined polarimetrically, a rotation differing from that of a lactyl radicle separated, in the same manner, from a molecule of some other lactate. The inactive group would, of course, be expected to show a similar behaviour; for instance, it is probable that the ethyl radicle in ethyl lactate has not the same volume as in ethyl acetate. Polarimetric examination of compounds composed of an active and an inactive radicle can scarcely be expected to yield any information as to the changes taking place in both parts of the molecule, but more interesting results may be anticipated from the investigation of compounds formed of two active radicles.It must be noticed, however, that although in the latter case both parts of the molecule contribute to its rotation, it is not possible to estimate accurately the effect of each. The observed rotation is only a resultant, and for the present a resolution can, a t the best, be only very approximately effected by comparison of this resultant rotation with the rotations of substances containing these active radicles united to other inactive groups. VOL. LXXXVII. I)34 PATTERSON AND TAYLOR: STUDIES IN It is proposed in this and some succeeding papers to colleot rotation data for such compounds in order to determine as far as possible the mutual influence of the groups of which they are composed, the present communication dealing with menthol and certain of it8 derivatives.A sample of menthol which gave for its rotation in absolute alcoholic solution of c = 4.5 11 2 the value [a]: - 49.88' was care- fully distilled under diminished pressure and the rotation of the homogeneous substance determined at several different temperatures, with the following resnlts : Rotahion of Menthol. C. afd (66'04 mm.). Density. JOO'O" - 27.399" 0.8380 78.0 28.132 0.8551 70.2 28'380 0-8612 63'2 28-585 0'8666 58.3 28.720 0.8704 53.6 28.833 0'8742 48'2 28-937 0.8783 43 '0 29.085 0'8821 39 '6 29'118 0.8852 $6.2 29.177 0.8884 [a]:. - 49.51' - 49-82 49'90 49.95 49-96 49'94 49-89 49-88 49.82 49 973 [MI;.77.24" 77.72 77-85 77'92 77'94 77.91 77'83 77-82 77-72 77-58 Densities Determined : Temperature . . . . . . . . , 40 -9' 59" 80" Density .... .... ;......... 0,8839 0'8699 0.8534 Molecular rotation of menthol. Temperature. From these data, tJhe ciirve showing the variation of molecular The rotation rotation with change of temperature has been drawn.OPTlCBL SUPERPOSITION. PART I. 3 5 of fused menthol has previously been determined by W. H. Perkin (Trans., 1902, 81, 309), who found [a]: - 49-88', whence [MI% - 77%2", whilst from the foregoing curve the value [M]r-77.85° is obtained; these numbers agree with one another very closely. It will be noticed at once from this curve that f o r menthol there exists a temperature of maximurn negative rotation.As the temperature falls, the rotation, which a t 100' is - 77*24", gradually increases to reach its maximum value of - 77.94' a t 58-59'. A t this temperature, the menthol molecule has its greatest optical effect. A diminution of rotation occurs with further redaction of temperature, but this could only be investigated for a few degrees below the melting point (42O), as the substance did not long remain supercooled. It would appear, however, by extrapolation, that menthol a t 20' would have a niolecular rotation of about - 77-22', almost the same as a t 100'. Several somewhat similar instances have recently been discovered. Thus it has been shown that, in solutions of optically active com- pounds, maximum or minimum values of the rotation may be reached a t definite concentrations, the temperature being constant, as is the case with nicotine in dilute aqueous solution or camphor in valeric o r caproic acid (see Landolt, " Dns Optische Drehungsvermagen, Eng.ed., p. 199), and also with ethyl tartrate in various solvents (Patterson, Trans., 1901, 79, 178, 483 ; 1902, 81, 1099). Similarly, maxima, or minima may OCCUP at definite temperatures in solutions of certain concentrations, as has been found for solutions of ammonium and sodium molybdenylbimnlntes (Grossman and Pijtter, Rer., 1904, 37, 84) and for various tartrates (Patterson, Trans., 1904, 85, 1136). So far as we are aware, however, only one case strictly analogous with that of menthol has been observed. P. F. Frankland and Wharton (Trans., 1896, 69, 1587) found that ethyl dibenzoyltartrate exhibits a maximum negative rotation at a temperature close t o its melting point, the phenomenon being more pronounced than in the Lase of menthol, whilst ethyl di-o-toluyltartrate, another substance prepared by these authors, very probably has the same peculiarity.I n these two cases the phenomenon must be due-since the inolecule is symmetrical-to a configuration of inaxiiiiuni asymmetry having been reached. The same explanatioii may, of course, hold in the case of menthol, but here there is also the possibility that the variation of rotation with change of temperature is merely an indication of the successive preponderance of one or other of the asyinrnetric carbon atoms. It does not follow that a t the temperature of maximum rotation all three atre acting in the same sense or with their maximum power.l-MeuthpZ cl-tartrate was prepared by Patterson and Dickinson's method (Trans., 1901, 78, 280). Dry hydrogen chloride was passed 0 236 PATTERSON AND ThY LOR : STUD1 ES IN into a flask containing a mixture of 25 grams of ethyl tartrate (1 mol.) and 120 grams of menthol (4 mols. approximately). This soon caused liquefaction of the menthol, and the resulting solution generally ac- quired a red colour. The flask was then placed in an oil-bath and the temperature gradually raised to, and kept at, 120-130°, the passage of the hydrogen chloride being continued for about 24 hours. The excess of menthol was then distilled off under reduced pressure and the residue, a heavy yellow or red oil, which forms a resin on cooling, dissolved in a large volume-one to two litres-of wwin spirit, to which water was added until a slight turbidity occurred, which wits then just removed by alcohol.The substance has a considerable tendency to separate as an oil, but can be obtained without much trouble in the form of silky needles radiating from nuclei. It is generally advisable to dissolve the crystals in alcohol and boil with animal charcoal for an hour or two and hhen recrystallise several times. The cryst,als are sticky to the touch and melt a t 74-75". I n absolute alcohol (c = 2, 1 = 200 mm., t = 19.5') the observed rotation was - 2.843", whence [ a ] ~ ' " - 71*08", and [ M]1D9'50 - 302.4". 0.2939 gave 0.7244 (20, a i d 0.2644 R,O.C: = 67.21 ; H = 10.0. 0.2384 ,, 0.590s CO, ,, 0,2120 H,O. C = 67.59 ; H= 9.8s. C,,H,,O, requires C = 67.61 ; H = 9-86 per cent. Molecular weight determinations carried out in benzene and ethylene bromide gave the following resdts : Benxeue. Constant -- 50. Subs taiice. Svlvelr t. A. 11. w. 0.1596 I 1 '045 0'161 448.7 0.2695 10'964 0.276 445.8 0'3850 10'833 0.391 452.5 Ethylene Bromide. Constant = 11s. 0'1663 28.669 0'149 459.4 0'3766 28'669 0'349 444.1 C,,H,,O, requires M. W. = 426.0 These numbers show evidence of only slight association, and together with the analyses leave no doubt as to the identity of the substance. Further proof is, however, furnished by the fact that a specimen of the compound obtained from methyl tartrate instead of from the ethyl ester was found to be identicd in melting point and rotation with the foregoing preparation, thus conclusively proving the presence in the molecule of two menthyl groups.In order to ascertain whether the process of preparatiou had in allyOPTICAL SUPERPOSITION. PART I. 37 way affected the rotation of the menthol used, a small quantity of the ester was decomposed by boiling with dilute caustic soda solution, and the menthol obtained, after shaking with water and caustic soda solu- tion, dried, and distilled under diminished pressure. When dissolved in absolute alcohol and examined in the polarimeter, i t gave for c-4.5112, -49.21'. The original value for the same concen- tration was [u]F -49.88'; the slight difference between these numbers was doubtless due to imperfect purification of the small quantity of menthol recovered. !Phe rotation of this menthyl tartrate was then determined, and on account of the fact that it remains supercooled for a long time the observations could be extended far below the melting point.Rotation of l-Ai5eizthyl cl- Taytrccte. t, a: (40 mm.). 75 25.60 67 -5 26-05 61 *7 26.27 57'2 26-49 50.1 26 $4 39 *3 27 *25 20 -7 28 -09 8.5 28.58 5.5 28.75 100" - 24'61" Density. 0'9920 - 1.0117 1.0176 1 -0220 1 -0255 1 *0312 1-0397 1 '0540 1 -0636 1 *0660 r.1:. .62.02" 63.26 64.00 64.26 64-58 65.08 65.52 66-63 67.18 67.42 Densities Determined : Temperature ........ 80" 100" 134%' Density.. ... ..... ... 1.0110 0.9920 0'9654 [q. - 264.2" 269.5 272.6 273.7 275'1 277.2 279 '1 28i3.9 286.2 287 '2 163" 0'9436 As has already been mentioned, an idea of the effect of each of the two active radicles in a compound such as the above can only be obtained from analogy with the behaviour of other, simpler substances.The figures in the table must therefore be compared with the rotation data of compounds of tartaric acid with inactive radicles on the one hand and of menthol with inactive radicle3 on the other. The behaviour of a few tartaric esters as regards variation of rota- tion with change of temperature is known fairly completely (compare Trans,, 1904, 85,766), but although a considerable number of menthyl esters have been prepared, notably by Tschugaeff (Bey., 1898, 31, 364), the influence of temperature change 011 t,heir rotations does not appear to have been investigated, I n order, therefore, to obtain some informa- tion on this point, a specimen of menthyl acetate was prepared from menthol and acetyl chloride and distilled several times in vacuo, the last distillation being performed with a Hempel tube.The boiling point of the specimen used was very steady a t 116'38 PATTERSON AND TAYLOR : STtTDIES IN (bath, 182-185O ; 22 1~111. pressure). The substniice was examined in the polarimeter with the following results : 1Zotcction of 1-ikie.lzthp? Acetate. t. a: (40 nim.). Density. [a]:. [MI;. 13.0" - 29'637" 0'930; - 79.61" - 157'6" 16% 29'488 09278 79'46 157.3 36 -9 28'845 0'9115 79.12 156'7 53.0 28.408 0'8981 79.08 156'6 67 -1 27 -963 0.8865 78.86 156'1 98.1 27'071 0,8612 78'59 155.6 Deizsities Detemnined : TempePature ......... 16" '26.2" 46.8" 80.45" Density ...............0 *9292 0,9201 0.9034 0.8756 From these numbers, the value - 157.35" is found for the molecular rotation at 20°, whilst Tschugaeff (Zoc. c i t . ) gives - 15'7.25'. Although these values agree very well, it may be noted that onr number for observed rotation, - 73.5' (t = Z O O , I = loo), is somewhat higher than his ( - 72-95'), and this is also the case with the density. We find d20°/4'= 0.9251, whilst Tschugaeff gives d20°/4' = 0.9185. We have determined the density of two quite cliff went preparations with the same result in each case. The rotation of Z-nienthyl acetate is but little influenced by change of temperature, and it is affected in the same manner as is the rotation of the tartaric esters.By extrapolation from the data given in the table, the value -157.9" is obtained for the molecular rotation a t 0' and - 155.6' at 100'. If now the iiuinbera for menthyl acetate and meiithyl tartrate are coinparad with those for ineiithol itself, it wili be noticed in the first place that the maximum negative rotation observed in the case of the last named is not apparent in either of the esters. Menthol suffers very little alteration of rotation with variation of temperature. Between 60" and loo', the molecular rotation only changes by 0.7". The change of rotation of the acetate is also but slight, namely, - 2.3' between 0' and 100'. I n the case of the tartrate, however, the change is much greater, namely, 23.5' (from - 288' a t 0' to - 264.5' a t lOO"), and, arguing from analogy, the part of this variation due t o the two meiithyl groups should be about twice as great as in the acetate, 4-G0, PO that the remaining 18.9' would be due to the tartaryl radicle, a value which agrees as closely as could be expected with those for the same changes in methyl, ethyl, and va-propyl tartrates, namely, 114 169', and 15.85O (Trans., 1904, 85, 768).OPTICAL SUPERPOSITION. PART I.39 As regards the absolute value of the rotations, i t may be noticed that the substitution of an acetyl group for the hydrogen atom of the hydroxyl group in menthol lowers the rotation very considerably- from -77.22' t o -157.35' a t 20'. Now it has been found by Tschugaeff (Bey., 1898, 31, 364) that the substitutian of other homologous groups in place of acetyl in menthyl acetate is prac- tically without effect on the molecular rotation of the resulting compounds.But, as has just been shown, the molecular rotation of menthyl tartrate at 20" is - 284', and is due partly to the two menthyl residues and partly to the tartaryl radicle joining them. These two components will be opposed to each other, since tartaric esters containing inactive alkyl groups have at 20°, so far as is known, positive rotations. The rotatory effect due to the two rnenthyl groups in menthyl tartrate must therefore be greater than - 2 8 4 O , and must thus have a value approximating to twice the rotation of menthyl acetate. This would seem to indicate that, in spite of the considerable difference of composition, the group -CO*CH(OH)-, consisting of half the tartaryl radicle, has, when substituted for the hydroxylic hydrogen of menthol, an optical value much the same as that which is common to acetyl, n-propyl, and n-butyl. I-Menthyl Diucetyl-d-tartrate.This substance was prepared by heating menthyl tartrate with excess of acetyl chloride for 2 to 3 hours. The undecomposed acetyl chloride was then distilled off and the viscid residue shaken with dilute sodium carbonate solution and then with water. After being recrystallised several times from dilute alcohol, the ester melted at 84.5'. We had occasion a t a later period to make another preparation of this compound, and the crystallisation was started by sowing in a few particles of the original specimen, The melting point of the product was found, however, to be 108'.The melting point of the first sample -which had been left in a stoppered bottle for some months-was t'hen redetermined and found to be also 1 0 8 O . The rotation had nevertheless remained unaltered. I n order to verify these observations, a third specimen of the acetyl derivative mas made, using freshly-prepared menthyl tartrate, After the acetyl chloride had been distilled off, the crude product was treated as in the first case. The solid obtained melted a t 84'. A little of this substance was then melted on a spatula and allowed to cool, and a few small crystals of the preparation melting a t 108' mixed with it. The glassy substance obtained was powdered on porous plate. On heating, it appeared to soften at about 50°, and then, as the tempera- ture rose, it became opaque again and finally melted at' 106-108'.40 PATTERSON AND TAYLOR: STUDIES IN Z-Menthyl diacetyl-d-tartrate therefore exists in two crystalline forms, as is also the case with methyl tartrate (Trans., 1904, 85, 765).The original preparation in absolute alcoholic solution of c = 2 gave a rotation of -2.04" in a 200 mm. tube a t 1 5 O , whence [ a3r - 51.0" and [ M]F - 260.1'. 0.2608 gave 0.6259 00, and 0.2079 H,O. C =65*45 ; H=8-86. 0.2467 ,, 0.5927 CO, ,, 0,1981 H,O. C=65*52; H=8*93. C,,H,,08 requires C = 65-18 ; H = 9.02 per cent,. The composition of this substance was further verified by prepara- tion and analysis of the chloroacetyl derivative of menthyl tartrate (see p. 42) and by the following molecular weight determinations : Solvent : Belzxene.Constant = 50. M. W. = 510. Substance. Solvent. Concentration. A. M. W. 0'0414 7.537 0.549 0.054 508-5 0'3488 7.537 4.63 0.487 475'2 0.6213 6-805 9 *oo 1.014 455.0 0.9137 7'798 11.72 1'347 435 -0 1.0127 6.805 14.88 1.755 424-0 1 -3666 7.798 17.52 2.117 414.0 According to these numbers, the molecular weight diminishes with increasing concentration, which may perhaps be due to combination of solvent and solute. Somewhat similar cases have been observed by Kahlenberg and Lincoln (Jour. Physical Chem., 1899, 3, 19 ; Chern. Ccntr., 1899, i, 810) and Walker (Trans., 1904, 85, 11 10). Polarimetric examination of the ester gave the following numbers : Rotation of l-Menth yl Diacetyl-d-tarlrate, t. 99 *2O 73 *2 68 -9 62 '1 69.9 46.3 89.3 26 '6 14.4 20.0 a: (40 mm.).- 17.720" 18.700 18.873 19'102 19'337 19.870 20,198 20.755 21 -363 - Density, 0.9915 1'0100 lm013O 1-0180 1'0195 1.0292 1-0342 1 -0434 1-0522 I [.I;. 44.68" - 46'29 46-67 46.91 47 '42 48.27 48.83 49.73 50.76 50 *28 * [m15 I 227 '8" 236.1 237'5 239.2 24 1 23 246.2 249.0 253.6 258.9 256.4 * Densities determined : Temperature.. . . .. . . . . . . . , . 115" 0,9804 * Interpolated, 158.5" 0.9494 Density . . . . . . , , . . . . . . . . , . . .OPTICAL SUPERPOSITIOPU'. PART I. 41 With regard to these numbers, little can be said, itinsmuch 8s other data with which they might be compared are scarce. Ethyl diacetgltartrate appears to be the only diacetyl ester the rotation of which has been investigated as regards temperature change, and it, in its optical behaviour, seems in most points to be related to ethyl tar- trate in just the opposite way to that in which menthyl diacetyl- tartrate is related to menthyl tartrate, Thus the molecular rotation of ethyl tartrate is greater at tempera- tures between 0" and 100' than that of the diacetyl derivative. It might therefore be expected that the diacetyl-menthyl compound would have a greater negative rotation than menthyl tartrate, which is not the case.Again, the temperature-coefficient of ethyl diacetyltartrate is less than that of ethyl tartrate, whilst for the menthyl esters the opposite holds. Some explanation of this may be obtained, however, from the following table, in which such data as are available regarding the influence of the substitution of acetyl groups are collected : Ximple Tartaric Esters.Diacetyl Derivatives. Methyl ...... [M]2,0' i- 3*6B0.* [M]y - 37.2s" (in alcohol c = 3.566). Ethyl ... ... [M]y + 15-95'." [M.]:' + 9.9O.l n-Propyl . . . [M]r + 42.93O.S n-Butyl ... [M]y [ A ! ! ] ? + 61*59O.(1 [ M]y + 29.67O." It will be observed that, although in the methyl esters the rotation of the acetyl derivative is much lower than that of the simple ester, the difference in the case of the ethyl esters is considerably less, whilst in the propyl compounds the acetyl derivative has the greater rotation. Unfortunately, although Freundler has examined the rotation of n-butyl diacetyltartrate, he has not recorded the rotation of the simple ester, and therefore this point can only be .imperfectly discussed.It appears, however, that as the alkyl radicle increases in weight the diaerence between the rotations of corresponding -substances dimin- ishes, and finally the rotation of the acetyl compound becomes greater than that of the parent ester, and since the menthyl radicle is of considerable size it would naturally be expected to resemble the propyl group rather than the methyl group. As there is not much difference between the analytical numbers for the mono- and di-acetyl derivatives of menthyl tartrate, l-rnenthyl di- * Patterson, Trans., 1904, 85, 766. 5 Patteison and McCrae, Trans., 1900, 77, 1098. 6 Compt. rend., 1893, 117, 556, Pictet, Jahresber,, 1882, 856. /I Freundler, c'ompt. rend., 1892, 115, 609,42 STUDIES I X OPTICAT, SITPERPOSITION. PART I.monoch2oroacetyZ-d-tartrccte was prepared with the ohject of verifying the composition of the acetyl derivative. It has been shown (Frankland and Patterson, Trans., 1898, 73, 185) that whereas two acyl groups can be introduced into the methyl and ethyl tartrate molecules by the action of mono- and di-chloroacetyl chlorides, only one acyl group is introduced by trichloroacetylchloride. It is probable, therefore, that chloroacetyl chloride acts less readily than acetyl chloride, so that if the former yields a diacyl derivative (which can, of course, be very definitely determined by a chlorine estimation) the latter must yield a diacyl compound also. The substance obtained by the action of chloroacetyl chloride on I-menthyl d-tartrate was crystallised several times from methyl alcohol. It melted, rather indefinitely, at 99-102O. 0.2310 gave 0.1142 AgC1. C1= 12'23. C,,H,,08C1, requires C1= 12.25 per cent, Polarimetric examination of the compound in absolute alcoholic solution gave the following results : c = 1 ; t= 200 mm. ; t = 1 9 O , observed rotation = - 0*85", whence [ u ] Y - 42.5' and [ M]',9" - 246*1°. This investigation is at present being extended in other directions. The results so far obtained may be suinmarised as follows : (1) Menthyl acetate, menthyl tartrate, and menthyl diacetyltar- trate have been prepared, and their rotations examined between Oo and 100" and compared with each other and with that of menthol between the same temperatures. (2) Menthyl diacetyltartrate is dimorphous, one modification melt- ing at 84.5' and the other at 108'. (3) It has been found that for menthol there is a temperature (58-59O) of mininiurn rotation (maximum negative rotation), but no such temperature has been observed for its derivatives. (4) It seems possible, reasoning by analogy, to trace the separate effects of the different active groups composing menthyl tartrate and its diacetyl derivative. In conclusion, the authors desire to acknowledge their indebted- ness for grants from the Government Fund of the Royal Society and from the Chemical Society Research Fund, which defrayed the expenses of this investigption. THE UNIVEBBITY, QLASGO W, THE UNIVERSITY, LEEDS.

ISSN:0368-1645    

DOI:10.1039/CT9058700033

出版商:RSC    

年代:1905

数据来源: RSC

摘要:

INGLE: TBE AVAILAHLE PTAANT FOOD I N SOILS. 43 VIIL-l’he Availccble Plant Food in soils. By HERBERT INGLE. CONSIDERABLE attention has recently been devoted by agricultural chemists to the methods by which some knowledge of the amounts of the mineral constituents of plant food present in soil in a condition available to plants might be acquired. It has long been recognised that estimations of the total quantities of phosphoric acid, potash, and lime present in n soil are of little value as indications of its fertility or of its manurial requirements. I n a recent paper by Hall and Plymen (Trans., 1902, 81, 117), a review of the various methods proposed for the estimation of the avail- able phosphoric acid and potash is given, as is also a comparison of the results obtained by these methods, with the known manurial needs of several soils as indicated by field trials.These authors find that amounts of phosphoric acid and potash extracted by treatment of soils with dilute acids are much more closely proportional to the quantities present in an available condition than those obtained by the use of strong hydrochloric acid. They at the same time assert that no sharp line of distinction can be drawn between the available and non-available phosphates and potash, and that every method tried gave empirical results. They finally conclude that of all the methods used :-(1) extrac- tion with a 1 per cent, solution of citric acid, (2) with equivalent quantities of hydrochloric acid and acetic acid, (3) with a saturated solution of car- bonic acid, and (4) with an ammoniacal solution of ammonium citrate, the first named gave results most in agreement with the actual relative fertility of the soils, This particular strength of citric acid solution was apparently first suggested by Stutzer (Chenx.Cesztr., 1884, 5, 329; Abstr., 1885, 48, 439) as a solvent for extracting the “available” phos- phates froin manures, instead of the usual ammonium citrate eolu- tion. The method, the value of which as applied to manures was confirmed by Thomson (Abstr., 1886, 50, 392), mas recommended by Dyer (Trans., 1894, 65, 115) for estimating the available mineral plant food in soils. Dyer was led to use a 1 per cent. solution of citric acid from the results of the determinations of the average sap acidity of the roc,ts of a large number of plants, He showed by an applica- tion of the method to the barley soils of the Hoos Field, Rotharnsted, that its indications were endorsed by the results of actual field trials.Subsequent experience has confirmed the value of the process, which is now largely used in soil analysis under the name of (‘ Dyer’s method.’’ It occurred t o the writer that the growth of plants in soil from44 INGLE: THE AVAILABLE PLANT FOOD TN SOILS. which the available phosphoric acid and potash had been extracted by Dyer’s method might afford useful information. So far as he can ascertain, no experiments on these lines have been made.* Preparation of the Soil. About three hundredweights of soil from an arable field at the Garforth Experimental Farm were taken in February, 1901, to a depth of six inches and sent to the laboratory by rail.The soil was air-dried on a clean concrete floor for about a week with occasional stirring. It was then sifted through a sieve with quarter-inch square meshes and the fine portion preserved in a cask. This air-dried soil lost 11.6 per cent. of moisture when heated in the steam oven. A portion of the soil was extracted with a 1 per cent. solution of citric acid, exactly as in Dyer’s method. The extraction was performed in a large tin cylinder provided with a finely perforated double false bottom; between the two metal plates, a piece of fine linen cloth was placed and, by means of a filter pump attached to a tubulure in the cylinder below the false bottom, the extract could be filtered off.Filter paper was first tried, but the cloth was found to be much more serviceable. The cylinder was fitted with a rotatory wooden stirrer driven by a water motor. By means of this apparatus, ten kilograms of soil could be treated with a hundred litres of citric acid solution a t a time. Allowance was made for the water contained in the air-dried soil. At each extraction, the stirrer was kept running night and day for seven days, and periodically a quantity of the liquid from below was drawn off and added at the top so as to maintain the uniformity of the concentration of the liquid. After each extraction, the clear liquid was removed from below by means of the filter pump, an operation which took about two days, and the soil washed five or six times with distilled water.The soil was then drained as thoroughly as possible by suction, removed from the apparatus, and dried. By repeating this operation four times, about thirty-three kilograms of dried, extracted soil were obtained. This was well mixed together in order to secure uniformity, and used in the pot cultures. The soil mas taken from the field and * Since this account was written, a paper by Xoderbaum has appeared (Kungl. Landtbruks-Akademiens handhgar och tidskrift, 1903, 103-106 ; Bied. Centr., 1903, 32, 795-798), describing the results obtained by growing barley in soils which had previously been extracted for forty-eight hours with a 2 per cent. solu- tion of hydrochloric acid at the ordinary temperature. The results show that such soil is incapable of supporting plant life, but that the addition of calcium carbonate in a great measure restores its fertility.Neither analyses of the soil or crops nos determinations of the amounts of phosphoric acid and potash semoved by the acid treatment are given in this paper,INGLE: THE AVAiLABLE PLANT FOOD IN SOlLS. 45 the extraction made in the ear!y spring of 1901 and the plants were grown in the same year, but the pot cultures were repeated with more care i n 1902. The original soil was analysed with the following result : Per cent. Stones removed by 3 mni. sieve 2.27 Moisture .............................. 3 -77 Loss on ignition .................. 6.62 (containing nitrogen, 0.259 per cent.). Silica. and insoluble matter ...... 80.30 The fine soil contained : Per cent.Ferric oxide and alumina ..... 6.64 Lime ................................. 0.81 Magnesia ........................... 0‘31 Phosphorus pentoxide ............ 0 -1 6 Potash ................................. 0.14 Not deterniincd ..................... 1-24 I 00 -00 -- On treating the soil foy seven days witli ;t 1 per cent. solution of citric acid, the following constituents were extracted : 1)cr cent. Potash ........................... 0 -01 10 Phosphoric oxide .................. 0.062 Per cent. Lime ............................... 0.553 Nitrogen ............................ 0 -011 The soil which had been extracted with citric acid was lighter in colour and somewhat more coherent than the original soil. I n order to lessen any influence on the plants due to change in the physical properties of the soil by extraction, both the extracted and the original soils were mixed with ten per cent.of their weight of coarse silver sand, which was freed from any contained plant food by previous treatment with strong hydrochloric acid and thorough washing with water. The new flower-pots employed, which were six inches in diameter, were extracted before use for a t least an hour with hydro- chloric acid (one of strong acid to four of water) and thoroughly washed. The broken earthenware used for ‘‘ drainage ” a t the bottoms of the pots was subjected to the same treatment and one hundred grams were used in each pot,. The Ezperiments of 1901. These investigations were vitiated by the very hot weather, the attacks of insect pests, and, in the case of barley, by the depredations of sparrows.They are briefly described because, although the examination of the crops was not completed, the qualitative results may be of some interest. The three plants selected for experiment were : (1) Barley (Garton’s ( ( Standwell ”) ; (2) Turnip (“ Tweedale Green Globe ”) ; (3) Horse Bean (variety not ascertained).46 INGLE: THE AVA1LABT.E PLANT FOOD IS SOILS. Eight pots were assigned t o each crop, numbers 1 to 8 to barley, l a The soil allotted to each pot is shown in the following table : to 8a; to turnips, and l b to 8b to beans. Pot. Soil. 1, l a , and l b ... Original soil. 2, 2n, ,, 2b ... Water-washed soil. 3, 3c6, ,, 3h .. Extracted soil + lime, phosphate, and potash. 4, 4a, ,, 4b , , . Extracted soil + lime and potash.5, 5a, ,, 56 . . . Extracted soil + lime and phosphate. 6, 6a, ,, 6b .., Extracted soil only. 7, 7rc, ,, 76 . , , Extracted soil +lime. 8, Scc, ,, 86 .. , Extracted soil +potash arid phosphate. The lime, potash, or phosphoric acid restored to the extracted soil in certain of the pots was equal to that removed from the original soil by the citric acid treatment. The lime was added in the form of precipitated calcium carbonate, the potash as potassium nitrate, and the phosphoric acid as sodium phosphate. The two latter were added in aqueous solution, whilst the calcium carbonate was well mixed with the soil. The soils were moistened from below with distilled water, and on June 4th were seeded. Seedlings were visible in all the barley and turnip pots by the 10th of this month, but the beans were not all up before the 18th.The barley and turnip seedlings in the extracted soil (pots 6 and 6cc) were very feeble from the first, and the turnips in 6 a were dead on the 22nd. Additional seeds were sown in this pot on the 19th, and as it was thought that the death of those first sown might be due to lack of nitrates, about 0.15 gram of sodium nitrate was applied in solution to the surface soil in this pot. In the case of the turnips, and to a less extent with the barley, the signs of starvation soon showed themselves in the extracted soil (pots 6 and 6cc), as did also the advantages of a liberal supply of plant food (greatest and most readily available being in pots 3 and 3a). With beans, these differences were not so apparent in the early stages of growth, although they became so later. Unfortunately, the turnips, and to a less extent the beans, suffered so much from the attacks of aphides, and the barley was so damaged by sparrows, that it was deemed inadvisable t o expend the time and labour necessary for their analysis. With beans, the following are the weights of the &-dried plants (without roots) at the end of their growth :INGLE: THE AVAILABLE PLANT FOOD 1N SOILS.47 Pot. Weight in grams. Pot. Weight in grams. l b ......... 5.305 5b ......... 20.441 26 ......... 12.385 66 ......... 1,047 3b ......... 26.386 7 b ......... 1.454 46 ......... not recorded S6 ......... 17.975 With barley, less differences were shown, except with pot 6, the dry weight of the whole plants in this pot being about one-seventh of that of the others.8ucnaniary of i%e 1901 Experi.rrmts. The following general conclusions may be drawn : (1) I n soil treated for seven days with ten times its weight of a 1 per cent. solution of citric acid, the growth of plants is greatly hindered, especially at first, and the total produce is very small. (2) The restoration of an amount of potash and phosphoric acid, in soluble form, equal to that removed by the citric acid treatment enables the extracted soil to yield a larger crop than could be obtained from the original soil. I n other words, the restored plant food is more “ available ” than that originally present. (3) Extraction with a 1 per cent. solution of citric acid for seven days does remove from a soil at least the greater portion of the ‘6 available ” potash and phosphoric acid.In this connection, it must be borne in mind that the available mineral plant food in a soil is being continually renewed by processes of weathering, and that even if its quantity were absolutely nil at the commencement of the experiment, it would not remain so, but would increase by the action of moisture and air on the mineral matter. Another weakness of the method is also realised, namely, that the bacteriological condition of the soil may be affected by the treatment, and this may have an effect on the growth of the plants. How far the results aro affected by this influence, the writer is unable t o say. The Experiments of 1902. I n 1901, the plants had to be grown at Garforth, at some distance from the laboratory, and considerable difficulty was experienced in properly attending to them.In 1902, advantage was taken of the offer of one of the writer’s students, Mr. W. H. Dobson, t o undertake the personal supervision of the growth of the plants a t Stapleton Park Gardens, near Pontefract. Mr. Dobson, who is an experienced horticulturist, took the greahest care of the plants, and when he returned them at the end of their growth they were in perfect condition, Qot a leaf being deranged on any of them.48 INQLE: THE AVAILABLE PLANT FOOD IN SOILS. In this investigation, parallel growths of barley and beans were made in the original soil and in the citric acid extracted soil. I n each case, the soil was mixed with 10 per cent.of its weight of white sand which had been thoroughly extracted with hydrochloric acid, as in the previous year‘s experiments. The pots used and the earthenware employed for “drainage” were also treated with acid and well mashed. Pots 1,2, 5, and 6 contained the original soil to which 10 per cent. of washed sand had been added; pots 3, 4, 7, and 8 held a mixture of the citric acid extracted soil with 10 per cent. of sand. AS it was thought that the extraction and washing of the soil might affect the early growth of the plants by the removal of nitrates, the contents of all the pots were moistened with distilled water containing 10 grains of ammonium nitrate t o the gallon (0.143 gi*am per Iitre). On May 2nd, when the soil was thought to be in a suitable condition as to moisture, barley was planted in pots 1, 2, 3, and 4.The next day, beans were planted in pots 5, 6, 7, and 8. The plants were sub- sequently watered as required with distilled water. From notes taken by Mr. Dobson, the following are the chief points observed with respect to the growth of the plants :-1. With the comparatively small seeds of barley, the appearance of the seed- lings above the ground was considerably retarded in the extracted soil, the dates at which the young plants were first visible in the various pots being : Eight pots mere used, four for barley and four for beans. Each pot held 1475 grams of the mixture of soil and sand. In the case of the beans, Kith their larger seeds, no such effect was noted, seedlings appearing on Nay 22nd in Pots 5 and 8 and on May 23rd in Pots 6 and 7.This is doubtless due t o the growth of the barley being more dependent on an early supply of nutri- ment from the soil than that of the beans, the larger seeds of which supply nourishment to the young plant for a longer period. 2. With both barley and beans, the inferiority of the plants in the extracted soil was greatest during the early periods of growth and became less marked in the later stages, probably because the changes in the extracted soil mould gradually render available some of theINGLE: THE AVAILABLE PLANT FOOD I N SOILS. 49 mineral matter originally present in an unavailable condition. The following table gives the average height of the barley plants in each pot at the various dates : Average height in iiiches.Date. Pot 1. Pot 2 . Pot 3. Pot 4: June 20th ............ 5.8 4 9 2.8 3.3 July 4th ............... l2.S 10% 4 *5 8 '1 July 18th ........... 1 R 2 18.3 9 ' 6 10'0 August 3 st. ........... 20'0 21 '0 13.2 14.9 rlugust 15th ......... 20'0 21 '0 1'7'0 15.5 k Pot 1 2 -,-" Original soil. 3 4 -/ Citric acid extracted soil. With the beans, the relative progress may be gathered from the following table, giving the height in inches of each plant at the various dates : Pot 6. l'trt 7. Pot 8. -, 7-c- <-J-- w, *--' Date. 0. b. Mean. a. b. Mean. cc. b. Mean. a. 6. Mean. Pot 5 . Julie 6th ......... 1.5 2.3 19 1.5 2.0 1.8 1'0 1.3 1.2 2.5 I .5 2.0 June 20th ..... 9.0 - 9.0 7.0 6 . 5 6.8 4.5 3.0 3'8 6.0 5.0 5.5 J d y 4th ......... 19.3 5.0 12.1 18.3 17.0 16.6 17.8 4.8 6'3 11.0 9.5 10-3 August 15th ...37.0 16.0 26'5 30-0 30.0 30'0 17.0 17'0 17.0 21.0 16.0 18'5 VOL. LXXXVIl. E50 INGLE: THE AVAILABLE PLANT FOOD IN SOILS. It is to be noted that in Pot 3 (barley in extracted soil) two of the four plants became very sickly about the end of July, and were doad on August lst, and that one bean of the two in P o t r o t 5 6 c / Original soil. 7 8 Extracted soil. . PLATE II.-Ben?zs, 1902 experinze?at. 5 became ‘‘ blind” in June, but put out lateral shoots and afterwards grew vigorously. The plants were photographed on October 8th, by which date they had completed their growth and ripened their seed. They were kept in the laboratory until November 17th, when they were cut off a t t h s surface of the soil and preserved for analysis.INGLE: THE AVAILABLE PLANT FOOD 1N SOILS, 52 Analysis of t7ze Plants.The following determinations were made in the yield from each pot ; Weight of the whole air-dried plants. Weight of silica in straw. ,, seed. ,, phosphoric acid in straw. ,, straw. ,, potash iii straw. ,, dry iiiatter in straw, ,, phosphoric acid in seed, ,, ash in straw. ), potash iu seed. The determinations of silica are not very accurate, inasmuch as some of the lower leaves and straw, especially in the case of beans, were contaminated with particles of soil which it was difficult to remove entirely. The chief interest, however, attaches to the amounts of potash and phosphoric acid contained in the plants. I n the following tables are given the data for each pot, the mean amounts €or the two pots containing original soil and for the two containing the extracted soil, and also the ratio of thew means.BC6?'t?t?y, 1902. Original soil. Extracted soil. A F P Ratio Pot 1. Pot 2. Mean. Pot 3. Pot 4. Alean. ofmeans. Weight of whole crop. 4'9060 5.3383 5'1221 1'9000 2.1250 2'0125 2.55 : 1 ,, straw ...... 2'6276 2.9030 2'7653 1.2228 1.2104 1.2166 2.27 : 1 Number of grains ...... 54 72 63 23 30 27 2.32 : 1 Average weight of one grain .................. 0'0420 0.0324 0'0372 0'0291 0.0305 0'0298 1.25 : 1 .. grain ...... 2'2784 2'4353 2.3568 0'6772 0'9146 0'7959 2'95 : I In the whole plant : Phosphoric acid ...... 0.0206 0.0167 0.0187 0'0040 0.0051 0.0045 4.15 : 1 Potash .................. 0'0702 0'0662 0.0682 0.0188 S I 3.60 : 1 In the strnw : Phosphoric acid ......0.0040 0*0020 0.0030 0'0012 0*0018 0.0015 2'00 : 1 Potash .................. 0.0548 0.0472 0*0610 0.0172 0.0267 0'0219 2'35 : 1 Silica ..................... 0.1072 0'1163 0.1158 0.1200 0.1046 0'1123 1'00 : 1 Total dry matter ...... 2.3263 2,5636 2.4449 1.1073 1'1808 1'1440 2'15 : 1 Ash ........................ 0.2472 0.2345 0*2408 0*1780 0'1678 0'1729 1'40 : 1 I n the gvain: Phosphoric acid ...... 0.0166 0'0147 0.0157 0-0028 0'0033 0'0031 4.75 : 1 .................. 11.0 : 1 Potash 0.0154 0.0197 0'0172 0'0016 '1 - The weight of the barley grains used as seed in each pot was on the average 0.0828, the total weight therefore of 4 seeds would be 0,2112 gram. The phosphoric acid contained in the 4 grains would amount $0 0.00065, the potash to 0*00009 gram.E 252 INGLE: THE AVAILABLE PLANT FOOD IN SOILS. Becms, 1902, Original soil. Pot 5. Pot 6. Mean. Weight of whole crop. 14.2802 11'3890 12.8346 ,, straw ...... 8.3312 7.3875 7.8594 ,, seed ......... 5,9490 4.0015 4.9752 Number of seeds ...... 9 7 8 Average weight of one seed ................. 0.6610 0'5736 0.6163 Extracted soil. <-A-, Ratio Pot 7. Pot 8. Mean. of nieans. 2.4454 2.7122 2'5783 5.0 : 1 1.7924 2.2522 2'0223 3.9 : 1 0.6520 0,4600 05560 8.9 : 1 2 2 2 4'0 : 1 0'3260 0.2300 0'2780 2 . 8 : 1 IN the whole plant ; Phosphoric acid ...... 0.0341 0,0171 0.0256 0*0100 O*OOS9 0*0094 2.7 : 1 Potash ................. 0.1297 0'0848 0.1073 0.0465 0.0568 0.0516 2'1 : 1 I n t h e straw: Phosphoric acid ...... 0-0130 0'0082 0'0106 0.0042 0.0053 0.0047 2 2 : 1 Potash .................. 0.0928 0.0495 0.0711 0'0424 0.0545 0 0484 1.5 : 1 Silica ..................... 0.0537 0'0750 0.063-:3 0'0474 0.0146 0'0310 2.1 : 1 Total dry matter ......7'1700 6'2662 6.7181 1'5628 1.9432 1.7527 3.9 : 1 Ash ....................... 0.8538 0.7184 0.7861 0-1820 0.1770 0.1795 4'4 : 1 In the seed: Phosphoric acid ...... 0.0211 0.0089 0'0150 0.0058 0.0036 0.0047 3.2 : 1 Potash .................. 0'0369 0.0353 0'0361 0*0041 0.0023 0'0032 11.3 : 1 The following are the most important points indicated in the foregoing tables : 1. Weight of the mole Air-dried Crop. This was, in every case, muoh greater in the pots containing the original soil. With barley, the total produce of Pots 1 and 2 amounted to 10.2442 grams, that of the two pots containing the extracted soil to 4.0250 grams, these numbers being in the ratio of 2-55 to 1.In the case of beans, the difference was greater; the two pots of original soil yielded a total crop of 25,6692 grams, whilst the two pots of extracted soil only gave 5.1566 grams, these numbers being in the ratio of nearly 5 t o 1. 2. Weiyht of the Seed. The barley, 126 seeds, from the two pots of original soil weighed 4.7136 grams, that from the two pots of extracted soil, 53 seeds, 1.5918 grams, these numbers being in the ratio of 2.95 to 1. With beans, the difference in yield was greater, the aggregate weights being 9.9505 from the original and 1.1120 from the extracted soil, a ratio of s-9 to 1. The seeds produced in the original soil were not only numerically1NGLE: THE AVAILABLE PLANT FOOD IN SOILS.53 greater-barley, 126 against 53, beans, 16 against 4-but the average weight of the individual seeds was much greater, especially in the case of the beans. 3. The Amounts of Potash and Phosphoric Acid in the Plants. This was, perhaps, the most important part of the investigation, The tables show that the barley plants were able to abstract more than four times as much phosphoric acid and nearly four times as much potash from the original soil as they could from the extracted soil. From the manner in which the barley grew in the extracted soil, it appeared highly probable that the phosphates and potash were assimilated mainly in the later periods of growth, and that a t first the plants were amble to obtain very little of these substances from the soil.With beans, similar results were obtained, except that the plants were able to take much larger quantities from the soil, especially from the extracted soil. The figures in the table show that the beans grown in the original soil contained more than twice as much potash and more than twice as much phosphoric acid as those grown in the extracted soil. It would thus appear that beans are more capable than barley of readily assimilating both potash and phosphates. I n this connection, it is well to remember that the larger store of plant food contained in the seed of the bean would be able more effectually to tide the young plant over the early period, during which the soil was unable to supply potssh and phosphates, than would be the case with the smaller seeds of barley.It is also noteworthy that Dyer, in his deter- minations of the acidity of the root juices of various plants, found higher values for Legurninom than for cereals (Trans., 1894, 65, 133-134). His numbers are as follows : Sap acidity. In terms of hydrogen. In terms of citric acid, Beans (field grown) ............ 0.0159 1.11 per cent. Barley ........................... 0.0054 0.38 ,, After the conclusion of the experiment, the soil from Pots 3, 4, and 7 (extracted soil) were examined by Dyer's method for available pot- ash and phosphoric acid, due allowance being made for the presence of the added sand. As was expected, these soils, which had been deprived of their available plant food at the commencement of the experiment, were found a t its conclusion to contain considerable quantities of both potash and phosphates soluble in 1 per cent.solution of citric acid.54 INGLE: THE AVAILABLE PLANT FOOD TN SOILS, The numbers were as follows : Available phosphoric acid. Available potash. Pot 3 ............... 0.021 per cent. 0,0147 per cent, Pot 4 ............... 0.015 ,, 0.0147 ,, Pot 7 ............... 0.010 ,, 0.0072 ,, These figures show that by the chemical change which went OM in the soil during the growth of the plants large quantities of mineral plant food, particularly of potash, became soluble in citric acid solution, I n fact, the amount of this regained ‘‘ available potash ” in the case of the barley pots exceeds that removed by treatment with citric acid at the commencement of the experiment (0.0110 per cent.).These results indicate that soils, under favourable conditions as t o moisture, are possessed of remarkable recuperative powers, and that the renewal of the available plant food may take place with considerable rapidity. Xuwamnry . The general conclusion to be drawn from the results of this investiga- tion is that, whilst Dyer’s method affords a satisfactory means of measuring the relative amounts of available plant food in two soils at a given time, it may not accurately gauge their relative fertility, inasmuch as it leaves undetermimd the relative rapidity with which the available plant food is renewed by the processes of weathering and decay. However, under similar climatic conditions, the rate will probably be approximately the same for most soils. The method, therefore, should be of great value in comparing soils, the conditions of which as to climate, &c., are similar. But its indica- tions might lead t o erroneous views as to the relative fertility of soils from tropical countries when compared with those in temperate climates, since in the former a smaller amount of avai?able plant food in the soil, if renewed more rapidly, as it probably is, might furnish t o the plants an actually greater quantity of nutriment than would be yielded by a soil containing a considerably larger amount of available food, but i n which the processes by which the unavailable become available went on more slowly. Of the probable truth of these conclusions, the writer, from a com- parison of his analyses of the soils of the Transvaal with those of English soils, is fully persuaded, although he fully realises the favour- ing influences of abundant sunshine and high temperature which affect the growth of plants in South Africa, and whioh help to explain the fact that luxuriant crops are yielded by soils which, on analysis,appear to be extremely deficient in plant food,SILBERRAD : THE CONSTITUTION OF NITROGEN IODIDE. 55 The experiment.al work ill connectiou with this investigation was chiefly carried out in the Agricultural C'lieuiical Laboratories of the Yorkshire College, Leeds, and the author would liere gratefully acknowledge the help afforded him by his former colleague, Dr. H. M. Dawson, and by his brother, Dr. Harry Ingle. He is also indebted to Mr, W. H. Dobson for the care exercised in attending to the plants during their growth. THE CHEMICAL LABORATORIES, TRANSVAAL DEPARTMENT OF AGRICULTUI~E, PRETORIA.

ISSN:0368-1645    

DOI:10.1039/CT9058700043

出版商:RSC    

年代:1905

数据来源: RSC

摘要:

IX . - Th e Iodide. Ey OSWALD SILBERRAD, Ph.D. SINCE its discovery in 1812 by Courtois, the explosive compound pro- duced by the action of ammonia on iodine has been repeatedly investigated, with a view to establishing its chemical constitution, but many of the results given in the older chemical literature have been subsequently shown to be erroneous. The difficulties experi- enced by all workers in investigating the constitution of nitrogen iodide are mainly due to the extreme sensitiveness of the compound in the dry state, Originally, the compound was believed to be simply an iodide of nitrogen containing no other element. Marchand showed, however (J. p. Clte737., 1840, 19, l), that when nitrogen iodide was detonated, ammonium iodide was one of the products, thus proving the presence of hydrogen.By combustion over heated lead chromate, he showed that the percentage of hydrogen must be very small. Bunsen showed (A~mcclen, 1852, 84, 1) that nitrogen iodide could be prepared from ammonia and iodine in the complete absence of water, thus proving that oxygen was not present. H e also showed that the only by-product formed was hydrogen iodide, from which it follows that the reaction is one of direct substitution, and that nitrogen iodide is still a compound of the ammonia type, The observation of Gladstone (C'hem. Gazette, 1861, 9, 269) that animonin is set free in the preparation of nitrogen iodide from am- monium iodide and bleaching powder does not give any definite indication as to the formula of the compound, although Gladstone considered it an argument in favour of t'he formula NHI,.Sziihay found (Bey., 1893, 26, 1933) that when aminouia interacted56 SI1,BERRAD : THE CONSTITTTTION OF NITROGEN IODIDE. with iodine, half the iodine was convertecl into nitrogen iodide, the other half being found as ammonium iodide. This gives no informa- tion as to the composition of the nitrogen iodide, however, but only shows that nitrogen iodide is a direct substitution product of ammonia, that is, one molecule of hydrogen iodide (and hence of ammonium iodide) is formed for each atom of iodine which enters into combination with the nitrogen. Thus, taking, for instance, the formula N2H313, the formation of nitrogen iodide would be represented by the equation 5NH, + 31, = N2H,I, + 3NIJ,I, Ohattarnay’s experiments, in which nitrogen iodide was slowly decomposed by a stream of water and the residue analysed, can hardly be regarded as evidence for one formula more than another.I n this connection it shoidcl be pointed out, firstly, that the ratio of 1 : 2.54 found by him is very little nearer t o 1 : 3, which would favour the formation of Stahlschmidt’s coinpound, NI, (Poyye?zdo?$”s Am$,, 1862, 115, 653), than it is to^ the ratio 1 : 2, which agrees with Szuhay’s formula, NHI, (Zoc. c i t . ) , and, secondly, that the quantity of free iodine increased so mnch during the progress of the decomposition (amounting to 44.8 per cent. in the example quoted by Chattaway) that it could probably only be very imperfectly allowed for by the differential method of analysis employecl.The analyses of the products obtained by different workers have led to a number of different forinulq the following having been put forward by certain of the earlier workers : NI, (Gay-Lnsmc, Stahlschrnidt, Mallet). N2H313 and N,H,I,, (Bunsen). NHI, (Bineau, Gladstone, Ras- chig, Szuhay, Seliwanoff), NH,I (Millon, Marchand). N5H5110 and N,H,I,, (Guyard). The conflicting results arrived a t by different workers led to the belief that several iodides of nitrogen existed. Indeed, certain in- vestigators found that under diff ereiit conditions the composition of the products varied. Thus, Stahlschmiclt (Zoc. c i t . ) believed that he produced from aqueous ammonia and an alcoholic solution of iodine a compound having the formula NI,, whereas from alcoholic ammonia and iodine he obtained a product which he formulated as NH12.Mallet (Cl~ern. News, 1879, 39, 257) stated that the concentration of the aqueous ammonia employed influenced the composition of the final product. Later work has shown that the varying results obtained by different workers were chiefly due to impurities present in the nitrogen iodideSILREltRhD : THE CONSTTTUTIOK OF NTTIIOGEP; IODIDE. 57 owing to the unsuitable experimental conditions and to the deconipos- ing action of light. Besides this, however, the analytical methods employed were in most instances faulty, and this added to the uncer- tainty of the results obtained. The main difficulty in the determination of the composition of nitrogen iodide is due to the fact that the dry substance can only be handled with ext'renie caution.For this reason, direct analyses with weighed quantities of the dry compound have only recently been carried out. In all the earlier investigations, unknown quantities were treated in various ways, and conclusions were drawn from the ratios between the quantities of the different products. The reagents mainly eni- ployed for the decomposition were hydrogen sulphide and sulphurous acid. Thus Bineau (Cowpi. rend., 1844, 19, 764) and, later, Gladstone (loc. cit.) used hydrogen sulphide and determined the relative quanti- ties of hydriodic acid and ammonia formed. Bunsen (Amden, 1852, 84, I) decomposed the compound with hydrochloric acid and estimated the relative amounts of ammonia and hydriodic acid produced. Mallet (Zoc.cit.) used a solution of sodiuin sulphite and estimated the nitrogen as arnnionia and the iodine as silver iodide. Szuhay (Bey., 1803, 26, 1933) used free sulphurous acid of known strength and determined the iodine and ammonia. The above methods are, however, all open to objection, since the reduction t o ammonia never takes place quantita- tively, a certain amount of free nitrogen being always liberated, as was shown by Chattaway (Amer. Clhent. J., 1900, 24, 138). The most satisfactory method is that adopted by this investigator (Zoc. cit.), in which the nitrogen iodide is treated in the dark with standard sodium sulphite; the excess of sulphite is then titrated with standard iodine solution, and the ammonia is subsequently distilled, after the addition of alkali, I n some experiments, Chattaway used weighed quantities of the dry nitrogen iodide, thus gaining an additional check on the results obtained.By means of a series of analyses carried out on products prepared by different methods, Chnttaway showed that the same com- pound was obtained in every instance (Amer. Chem. S., 1900, 23, 363, 369; 1901, 24, 138, 159, 318, 331, 342). H e found the composition to agree in all cases with the formula originally assigned by Bunsen, namely, X2H313, and ascertained further that the iodide is a definite chemical compound, neither iodine nor hydriodic acid being present in loose molecular combination, as in periodides or acid iodides. Each atom of iodine was shown to be univalent and directly linked to nitrogen. Hixgot has shown (Compt.rend., 1900, 130, 505) that a t low tem- peratures compounds exist having the forinulz N,H613 and N,H 913.58 SILBERRAD : THE COKSTITTTTION OF NITROGEN lOnlDF,. These are, however, oiily capable of existence in presence of excess of ammonia a t very low temperatures, and dissociate very readily, re- generating ammonia and the corripouiid N2H313. This compound is thus the only one which need be considered a t the ordinary temperature. Although the empirical formula has been thus established, no investigations have hitherto given aiiy insight into the constitution of nitrogen iodide. Evidence as to the structure of the nitrogen iodide molecule can evidently only be obtained by a study of its derivatives. The conclusions drawn from the metallic derivatives have hitherto been rather misleading t’han otherwise. The conipound formulated by Guyard (Conipt.rend., 1884, 97, 526) as CuI,,2NH21 cannot be regarded as evidence in favour of the formula NH,I for nitrogen iodide, for the number of hydrogen atoms in the molecule is difficult to determine by analysis. Thus, whereas the above compound would theoretically contain 0.66 per cent. of hydrogen, a compound having the formula Cu,12,2NH3N13 would contain 0.50 per cent., so that no reliable deductions could be inade froin Guyard’s analyses as to the constitution of the compound (compare the following paper). Szuhay (Ber., 1893, 26, 1933) obtained ;t silver derivative of nitrogen iodide, to which he ascribed the formula AgNI,. This appears to render the formula NIII, probable for nit.rogen iodide.I n the following paper, however, the pure compound is shown to be a direct silver derivative of N,H31,. The reactions of nitrogen iodide with organic compounds have as yet been very little studied. The experiments of Stahlschmidt (Poggendorfs Ann., 1863, 119, 421) should be noticed, although the conclusions drawn by him from the results were erroneous. By the action of methyl iodide on nitrogen iodide, he obtained the following products : nitrogen, hydriodic acid, ammonium iodide, tetra- methylammonium pentaiodide, iodoform, iodine, and, further, a small quantity of an insoluble compound which was not further investi- gated. Froin the mother liquor, on addition of caustic potash, lie obtained ammoiiia and di-iodomethylaniine. I n view of the conflicting evidence as to the constitution of nitrogen iodide obtained by different authors, the preparation of direct sub- stitution products, which should leave no doubt as to the constitution of this compound, was desirable.The problem has now been definitely solved by a study of the interaction of zinc ethyl and nitrogen iodide. I n this way, the formula NH,:NE, has been established. Before carrying out this work, the question of the applicability of inagnesium alkyl iodides wss also considered, as their use mould probably be experimentally easier j but since the complete exclusion of rtlkyl iodides is of great importance, their application was regarded asSILBERRAI) : THE CONSTITUTION OF NITROGEN IODIDE. 59 unsatisfactory. For the ivagiiesiuni alkyl iodides inay contain traces of alkyl iodide, or may possibly themselves act in a n analogous manner to alkyl iodides, which would greatly complicate the reaction.By using zinc ethyl, which could be obtained completely free from iodine compounds, on the other hand, this objection was satisfactorily overcome. It was established by Cliattaway's work that the empirical forniula of the compound was N2H31,. Prom this it is seen that only two different constitutional formulz are probable, namely, NH,I:NHI, and NH,:NI,. These two compounds may be assumed to react with zinc ethyl in the inatlliier represented by the equations : I. ZNH21:NH12 + GZn(C,H5), = 6Zn(C2H,)I + 2C2H,*NH, + SNH(C,H,),. JI. ZNH:,NI,+ GZn(C,H,), = 6Zn(C2H,)I + ZNH, + 2N(C2H5)3. The latter of these equations was proved to be correct by the identification of ammonia and triethylamine as the prodncts of the react ion.EX P E R I ME N T A L. P?*e;uurution of Nitrogen Iodide.-The nitxogen iodide required for this investigation was prepared by allowing iodine chloride to act on aqueous ammonia (compare Bloxam's Chemistry, 4th edition, 1880, p. 180, and also Chattaway and Orton, J. Amer. Cl~enz. Xoc., 1900, 23, 363). Action of Zinc Ethyl on Nitrogen Iodide.-In the first place, it was necessary to find a solvent for zinc ethyl which would not. interact in any way with nitrogen iodide, and preliminary experiments showed that ether was the best suited to tlie purpose, whilst from the following iwnlts i t will be seen t8hitt the pure solvent is entirely without action on nityogen iodide.I n each experiment,, 100 C.C. of ether were used and allowed to remain a t 0" for various periods, after which tlie nitrogen iodide was filtered off and the uncombined iodine in solution shaken out wittli excess of ~ V / 1 0 sodium thio- sulpliate and estimated. The combined iodine was then estimated by boiling tlie ether for 24 hours with iinely granulated sodium, dissolving the latter in water, and determining the iodine with silver nitrate.Time during which nitrogen iodide and iodide removed Tinchaiigetl ni trogvn ether were (titrated in Free Combined 1 eft together. filtered residnc). iodine. iodine. (a) With methylatecl ether (sp. gr. 0.720) whicli had lwtn left for three m e k s 1 hour 1 .358 grains 0.118 0'0013 over ground caustic soda xiid suhsequcntly distilled.4 hours 1.570 ) ) 0.135 0-0015 48 > 7 1.326 ,, 0'446 0.0055 ( b ) With the above ether further purified by boiling for twenty-four hours with finely grannlated sodium (tliis ether was nseil in Experiments 1-4 dcscribed below). 24 holm Kot c*stinintrtl. I,PW than o*ooo.: (c) With ether pnrifietl as dtxrilwti l i r l o ~ nntl nw(i in F,xpei*inieiit 5. Nit d o r a t i o n with stni c h solidion. 48 hours 5 grains -- On repeating this first series of experiments and allowing the ether to evaporate spontaneously, iodoform was readily detected by its odour ; from this it would appear probable t'hat the reaction observed with less carefully purified ether is due to traces of alcohol. Indeed, the reaction appears to lend itself to the detection of very minute traces of alcohol in ethsr.A suitable diluent having been thus obtained, it became necessary to ascertain the nature of the reaction. To this end, a series of preliminary experiments was carried out with very small quantities of nitrogen iodide, which established the following points : (n) That it is impracticable to work with dry nitrogen iodide in any quantity, as explosions cannot be avoided; it mas therefore used under ether. ( b ) That ammonia is among the products. (c) That the reaction proceeds quietly and slowly, ancl that even a slight evolution of heat was noticeable only during the addition of the first portion of zinc ethyl. The following experiments were then carried out, the work being always conducted in red light : Expt.1.-Eleven g r a m of nitrogen iodide (prepared from 100 C.C. of a 14 per cent. solution of iodine chloride) were thoroughly washed by decantation, first with dilute ammonia, then ten times with absolute alcohol, until the latter gave no coloration with anhydrous copper sulphate, ancl after that as many times with absolute ether which had been prepared by leaving methylated ether (sp. gr. 0.720) over ground caustic soda for three weeks and then boiling for 24 hours with h e l y granulated sodium. A fresh quantity of absolute ether (50 c.c.) was run in, and then 14 grams of zinc ethyl dissolved inSILBERRAD : THE CONSTITUTION OF NITROGEN 10DIDE. 61 25 C.C. of ether were introduced. The whole was then left for 48 hours in the dark, after which the mixture was worked up in the manner described below.On distilling into water the product obtained by the action of the bases on ethyl oxalate, the latter became strongly alkaline. Since ammonia, mono- and di-ethylamines all react with et'hyl oxalate, it appeared probable that this base was triethylamine. The quantity, however, was too small to establish its identity. Expt. 2.-A duplicate experiment was therefore made with 120 grams of nitrogen iodide, and on this occasion the reaction was accompanied by a distinct effervescence, the product showing signs of clogging together, so that it was found necessary to leave the mixture for four days before it could be worked up with safety. On doing so, however, a distinct quantity of the alkaline distillate, which failed t o react with ethyl oxalate, was obtained. This was concentrated with excess of hydrochloric acid and treated with a drop of very concen- trated platinic chloride solution, when a readily soluble platinichloride was obtained.0,01677 gave 0.00561 Pt. Pt = 33.45. [NH(C,H,),],PtCI, requires Pt -- 31 ~84. [NH,(C,H,)2J,PtCl, requires Pt = 35.06 per cent, The quantity was, however, so small that the analytical results were not of sufficient accuracy to be regarded as establishing the nature of the compound. Expt. 3.-The foregoing experiment was repeated, but in this case the flask was fitted with stirring gear. Unfortunately, the stirrer slipped before many C.C. of the zinc ethyl solution had been added, and, falling on some unchanged nitrogen iodide, caused a violent explosion and considerable conflagration.Expt. 4.-The experiment was accordingly repeated, and this time successfully; but on working up the product of the action of ethyl oxalate on the bases no better results were obtained. Expt. 5.-Finally it was decided to work with 1 kilogram of nitrogen iodide, as this, judging from Experiment 2, should yield 0.14 gram of the platinichloride, which ought to be sufficient to obtain a reliable analysis. It had been noticed throughout that a slight evolution of heat occurred during the addition of the first portions of the zinc ethyl, but as the reaction between zinc ethyl and nitrogen iodide is so slow, the evolution of heat could hardly be traced to this cause; indeed, it appeared far more likely that; it was due to the presence of some impurities either in the ether or in the nitrogen iodide.It was therefore decided to exercise the utmost care in order to ensure the62 SlLBERElAD : THE CONSTITUTION OF NITROGEN IODIDE, highest degree of purity in both these compounds, and to this end the reaction was carried out in red light and in a refrigerator kept approximately at O0, the following precautions being observed. Pzcrzjicatior~ of ihe Etlt,ey.-Two hundred grams of caustic potash, dissolved in 100 C.C. of water, were added to each of 6 ‘‘ Winchester qiarts,” each containing 1500 C.C. of metbylated ether (sp. gr. 0,720). These bottles were then agitated in a shaking machine for two days, after which the ether was poured on to 1 kilograni of finely ground caustic soda contained in n 10 litre flask immersed in a large water- bath, and the mixture boiled with a reflux condenser for 24 hours.The ether was next decanted into another 10 litre flask, treated with 50 grams of finely granulated sodium, and again boiled for 24 hours, after which it was distilled off. These last two operations were repeated until the ether ceased to tarnish the sodium on boiling for 24 hours. During distillation, the ether was collected in bottles filled with dry carbon dioxide in order to prevent absorption of moisture or auto-oxidation on evaporation. Pzcrijccltion of the Nitvogen Iodide.--One kilogram of well washed nitrogen iodide was transferred to a 10 litre flask by means of absolute alcohol ; it was then further washed 9 times with this solvent, until the liquid gave no coloration with anhydrous copper sulphate, and then ten times with purified ether, 1 litre being used f o r each washing.The ether used for the last three washings contained no combined iodine, and gave no yeaction with nitrogen iodide on stand- ing for 48 hours. The flask containing 1 kilogram of nitrogeri iodide and about 1 litre of ether was then fitted up as shown in the diagram arid all the air displaced by means of dry carbon dioxide. The stirrer, d, was then set in motion with just sufficient rapidity to cause the nitrogen iodide lying on the bottom of the flask t o change its position continuously. A slow stream of pure ether was allowed to flow- in from the vessel, e, through the tube, f, and out through the tube, g , the pressures on the surface of the liquid in the flask and in the ether reservoir being rendered identical by means of the carbon dioxide generator, which was connected to the ether reservoir through the tube, h, and t o the flask through b.The tap, b’, was so adjusted that a few bubbles of carbon dioxide passed, from time to time, slowly up the tube, 9, together with the spent ether. The level of the liquid in the flask was thus kept constant. The washing with ether was continued for 4 hours, during which time aboub 4 litres of pure ether were passed through the flask. The spent ether, after filtration from a few grams of nitrogen iodide which had been carried over, was found to contain very minute traces of free iodine, but no combined iodine whatever.SILBERRAD : THE CONSTITUTION OF NITROGEN IODIDE.63 Action of Zinc Ethyl o n the Yurijed Nitmyen 1otlide.-The tube through which the ether made its exit was then closed by means of the cock, G’, 24 litres of pure ether were run into the flask, the dis- placed carbon dioxide being allowed to escape tlirough the mercury trap, k, by means of the tube, c, the cock, c’, having been previously opened for this purpose. The flask was then surrounded with ;L freezing mixture, and as soon as the temperature of its contents had fallen t o -5” the addition of zinc ethyl was commenced. In this manner, 1300 grains of zinc ethyl dissolved in 24 litres of pure ether were added from the coil- tainer, 2.” From time t o time during the addition of the zinc ethyl, and also at subsequent stages of the experiment, samples were run off by * The advantages of the piece of apparatus Z will be obvious from the diagram ; it mas so constructed that ether could be forced in froni the reservoir e by means of the carboil dioxide pressure on its siwface, arid that the whole apparatus could rcatlily be connected with the carbon dioxide system through wz m’, so that the dry gas displaced the zinc ethyl sohition as it floIved tlirongli thr cock 2”.The cock I”’ was attached in order to render it possible tn refill the apparatus wit11 zinc ethyl solution, as it was not large eiiougli to liolci the complete charge ; in doing so, the charge enters through the tap I”’ and Z”, whilst the displaced carbon dioxide 1)aSses out thrnngh 7’.64 SILBEREAD : THE CONSTITUTION OF NITROGEN IODIDE.means of the three-may cork, c'. I n every instance, even after the first addition of a few C.C. of the zinc ethyl, it was found that unaltered zinc ethyl was present in the solution. The stirring was continued for 48 hours ; during the first 24 hours, the refrigerator was kept a t Oo, but subsequently was allowed to warm up to the ordinary temperature. The black nitrogen iodide slowly changed into a white, amorphous powder. The reaction pro- ceeded quite quietly, and no evolution of heat was noticeable, indeed, the 'thermometers in the flask and in the cooling-bath indicated the same temperature during the whole of thisperiod. Half a litre of ether, which had previously been shaken with water, was then added, and as this produced no effervescence it was concluded that the reaction was completed, and excess of water was accordingly added and the mixture again stirred for 24 hours.Excess of hydrochloric acid was then run in and the ether removed by distilla- tion. At the commencement of the distillation, a large quantity of inflammable gas passed over. -4 sample of this was collected over mercury, freed froin ether vapour, and analysed. It was not absorbed by fuming sulphuric acid or concentrated nitric acid, and proved t o be a mixture of paraffins, evidently butane and ethane. Dry gas before explosion a t 99.2' and 75'7 mm. = 3.2 C.C. Moist gas after explosion a t 17.5' and 757 mm. = 36.8 C.C. ,, ,, together with oxygen added a t 99.2" and 769 mm. = 53.2 C.C. ,, ,, ,, absorbing carbon dioxide with caustic potash a t 17.5' The volumetric composition of the gas corresponds with 46 per cent.of butane and 54 per cent. of ethane. It was foreseen that zinc ethyl would first form double zinc amides with the amines formed (except tertiary amines) with evolution of ethane (Frankland, Juhresber., 1867, 428). These zinc amides hydrolyse readily, however, with hydrochloric acid t o zinc chloride and the original aniines. Thus the solution contained the hydrochlorides of the amines formed. From these, the bases were liberated with alkali and distilled into hydrochloric acid. The mixture of chlorides obtained on evaporation was then extracted several times with alcohol, in which a11 the ethylamine hydrochlorides are much more readily soluble than ammonium chloride.The least soluble fraction was recrystallised from water, after which a small portion was converted into its plntinichloride and analysetl. and 757 mm. = 29.0 C.C. 0.1182 gave 0.0517 Pt. Pt =43.74. (NR,),PtCl, requires Pt = 43.9 1 per cent,SILBERRAD : THE CONSTITUTION OF NITROGEN IODIDE. 65 The yield of ammonium chloride was 125 grams, or 95 per cent, of the theoretical. For the identification of the organic amines present, Hoff mann and Wallczch's method of separation was adopted (Jnhresber., 1861, 495 ; AmleaZen, 1876, 184, 33). The alcoholic extract of the hydrochlorides was evaporated, distilled with very concentrated caustic soda, and the distillate collected in absolute alcohol at Oo. A slight excess of ethyl oxalate was added and the mixture allowed t o remain a t a low temperature for 15 hours.On distillation from a water-bath, a strongly alkaline distillate passed over, whioh proved to be t rie t h ylamine. A crystalline deposit, which formed in the distilling flask, was recrystallised from alcohol, and in this way separated into two compounds, The major portion consisted of ethyl oxamate, melting at 1 14'. 0.0983 gave 10.4 C.C. moist nitrogen a t 16' and 753 mm. N = 12.28. CONH,*CO,*C,H, requires N = 12.0 per cent. The second product, which was sparingly soluble in alcohol, occurred only in a very small quantity ; it melted a t 210-211' and probably consisted of oxamic acid, The formation of ethyl oxamate confirmed the presence of ammonia in the original product. The oxamic acid was evidently produced as a by-product of the same reaction. Derivatives of primary or secondary amines were entirely absent. Since only the tertiary amines are unacted on by ethyl oxalate, it was to be expected that the distillate from the product obtained by the action of the amines on this ester would consist of triethyl- amine. The yield was far greater than was expected, and in order to determine it the distillate was made up to 250 C.C. and an aliquot portion titrated with N/iO acid with the following result : 3 C.C. required 9.3 C.C. N/10 hydrouhloric acid ; the yield was therefore 7.8 grams or 3.5 per cent. I n order to establish the identity of the base, the remainder of the distillate was acidified with excess of hydrochloric acid, concentrated t o a small bulk, and the hydrochloride converted into the readily soluble platinichloride. 0.3704 gave 0*11843 Pt. It thus becomes evident that the reaction is greatly dependent on the experimental conditions. The fact that the success of the reaction demands the entire absence of impurities is a definite proof that the formation of triethylamine is due to the interaction of zinc ethyl on nitrogen iodide, indeed in no other manner can the entire Pt = 31-98. [NH(C,H,),],PtCl, requires Pt = 31.84 per cent. VOL. LXXXVII. F66 SILBERRAD : THE METALLIC DERIVATIVES OF NITROGEN absence of mono- or di-ethylamine in the presence of so large an excess of ammonia be explained. My thanks are due to Mr. Smart for his assistance and t o the Explosives Committee for permission t o publish these results. RESEARCH LABORATORIES, ROYAL ARSENAL.

ISSN:0368-1645    

DOI:10.1039/CT9058700055

出版商:RSC    

年代:1905

数据来源: RSC

摘要:

66 SILBERRAD : THE METALLIC DERIVATIVES OF NITROGEN IIi.--Th,e Met a1 1 ic Dericat ives of Nitil-ogen Iodide and theb Beariizg on its Constitution. By OSWALD XILBERRAD, Ph.D. IN the preceding paper, the author has given a definite proof of the constitution of nitrogen iodide, and has a t the same time shown the uncertainty of much of the earlier work. For this reason, it appeared of interest to undertake a revision of the more important work on the derivatives of this compound, because, although a number of derivatives have been obtained by the action of metallic salts on nitrogen iodide or by the action of iodine on ammoniacal salt soln- tions, great uncertainty exists as to the composition of these sub- stances. A review of this work has shown that both the methods of preparation and of analysis were very unsatisfactory.The Copper Derivative.-Guyard (Conapt. rend. , 1884, 97, 526) ascribed the formula Cu212,2NH,I to the compound which he obtained by the action of a potassium iodide solution of iodine on copper ammo- nium sulphats. H e did not, however, support this formula by any analytical data, nor did he give any description of his methods of analysis. Further investigations of the subject have rendered it probable that he deduced the above formula from estimations of the iodine only. H e based its relationship to nitrogen iodide on the fact that on treatment with excess of ammonia the copper passed into solution with a simultaneous precipitation of nitrogen iodide. It must, however, be remarked that the copper compound itself possesses no explosive properties whatever, a circumstance which at once renders Guyard’s formula doubtful.The following investigation shows that the compound is a cuprosamine periodide. The compound is prepared by dropping a 20 per cent. solution of potassium iodide (100 c.c.) containing 5 grams of iodine into an aqueous solution con- taining a slight excess of cuprammonium sulphate in 1200 C.C. of water at the ordinary temperature. The compound separates in small,IODIDE AND THEIR BEARING ON ITS CONSTITUTION. 6’7 crystalline plates. Owing to its insolubility, it cannot be recrystal- lised from any solvent, and considerable care is therefore necessary €or the production of the compound in a pure state. It was found necessary t o devise special methods of analysis, and the following procedure was eventually selected as being most satisfactory. The com- pound was first warmed with dilute alkali and metallic aluminium for half an hour on the water-bath.This brought about complete precipita- tion of the copper. The precipitate was well washed with hot water, redissolved in a little hot nitric acid, and reprecipitated as cupric oxide and weighed, After the removal of the copper, the fiItrate was acidified in the cold with dilute sulphuric acid and treated with hydrogen peroxide and chloroform t o extract the iodine. The chloroform solution was then titrated with standard thiosulphate solution. For the estimation of the nitrogen in this compxmd, Dumas’ method was found to be the most satisfactory. For comparison, the percentages required by a compound having the formula suggested by Guyard are given in the final column of the following table : Found.%I29 (NH,),IB, H2O C%I2, ?NH,I <--- requires re quires Iodine ...... 76.19 $6.43 76.75 76-1 1 Nitrogen .. 7.53 7-32 7.08 4.21 Copper.. ... 12.87 12-96 12.s2 19.0s The compound manifests the characteristics of a periodide in many ways. On heating, it evolves iodine vapoiir; by treatment with potassium iodide solution, the loosely combined iodine is removed quantitatively, and, on titrating this solution with sodium thiosul- gbate, the following results were obtained : Loosely combined iodine found . . . . . , . . CU,I~(NH~)~I,,H,O requires . . . . , . . . , . . 51 -20 5 1 *12 per cent. 51.16 ,, The behnviour of the cuprosamine periodide towards ammonia, which was taken by Guyard to be indicative of its relationship to nitrogen iodide, must, however, be regarded as distinct evidence of its periodide character. According to the above formulation, the loosely combined iodine interacts with ammonia in a manner precisely similar to that in which potassium periodide acts on ammonia.It thus becomes evident that Guyard’s formula for this compound is incorrect, and con- sequently that its existence is no support of the formula NH,I for nitrogen iodide. Cuprosamine Iodide, CLI~I,,NH,,~H,O.-W~~~, in order to remove the loosely combined iodine, the above periodide is treated with potass- F 268 SILBERRAD : THE METALLIC DERIVATIVES OF NITROGEN ium iodide-preferably by warming with a 25 per cent.solution-a green, crystalline residue is left, which, when thoroughly washed and dried, is obtained as an olive-green powder insoluble in water, but soluble in ammonia, forming a blue solution. Founkl. C U 2 , N H s , 4H20 - requires Copper ............ 97-10 27.21 27.08 Iodine ............ 53.94 54.16 54-03 Nitrogen ......... 3.10 3.02 2-98 By the foregoing treatment, the cuprosamine periodide has therefore lost both iodine and ammonia. The Silver Derivative.-It was shown by Szuhay (Ber., 1893, 26, 1933) that a silver compound could be obtained from nitrogen iodide which was in all probability a direct derivative of the latter. H e prepared this silver compound by the addition of an ammoniacal solu- tion of silver nitrate to nitrogen iodide suspended in water, and ascribed the formula AgNT, to the product on the basis of determina- tions of the ratio of the elements to one another.It is obvious, however, from Szuhay’s paper that insufficient pre- cautions were taken for the production of a pure homogeneous com- pound ; for, since the substance cannot be recrystallised, it is necessary t o take extreme care to ensure absolute purity in the first instance. It is hardly to be expected that the conversion of one solid compound into another in this way will give rise to SL pure derivative. The heterogeneous character of Szuhay’s product is shown by the following analysis of three different preparations carried out exactly as prescribed by him with the exception that the experiments were performed in the dark and a t 0’ in order to minimise the decomposition of the com- pounds.Ailslytical results (weight in grams). Atomic proportions. /- \ -7 Nitrogen ...... 0.05623 0.04956 0.05696 4.58 6.98 4.75 Silver ....... 0.09469 0.05479 0.09243 1.00 1.00 1’00 Iodine . . . . . . . 0 5 3 6 4 0’4197 0’5327 4-82 6’51 4‘90 A (1) (2) (3) (1) ( 2 ) ( 3 ) These numbers show that it is practically impossible to obtain a homogeneous product by Szuhay’s method. The agreement of his analytical results with the formula AgNI, must therefore have been accidental. The weak point in Szuhay’s procedure appeared to be that the purity of the compound depended on tEe complete conversion of one insoluble solid into another. This difficulty was overcome in the following manner.lODIDE AND THEIR BEARING ON ITS CONSTITUTION.69 Twenty eight C.C. of a 5 per cent. solution of silver nitrate were added to 30 C.C. of 10 per cent. ammonia; the mixture was then cooled to Oo and treated with 6 C.C. of a 14 per cent. solution of iodine chloride (corresponding with 0.8 gram of iodine) also cooled to Oo. The black precipitate was washed by decantation in the dark. On attempting to dry this silver derivative, it underwent decomposi- tion with formation of silver iodide, I n order to establish its com- position, it therefore became necessary to determine the ratio of the elements present by working with the substance suspended in water. The analytical methods used by Szuhay were examined and found to be open to criticism. He treated the precipitated compound with aluminium turnings in order t o reduce the silver to the metallic con- dition and the nitrogen to ammonia.The ammonia was thereupon distilled off and estimated, the other elements being determined in the residue. He assumed that no loss of nitrogen would take place in this way. Trials of his method have shown, however, that the evolution of traces of nitrogen is practically unavoidable. After trying various methods,the following mode of procedure was found t o give the most satisfactory results. The compound suspended in water is first treated with sodium thio- sulphate. The nitrogen is thus converted quantitatively into ammonia, which, after the addition of caustic soda, is distilled off and estimated. The residue is then treated with finely divided aluminium; the silver is thereby reduced to the metallic state and can be filtered off, dis- solved in nitric acid, and estimated in the usual way.The iodine remains in solution as sodium iodide and can be readily estimated, The following analytical results were obtained in this way with four different preparations : Analytical results (weight in grams). Atomic proportions. c r- A \ (1) ( 2 ) ( 3 ) (4) (1) (2) (3) (4) Silver ...... 0.1895 0.2141 0.1890 02105 1.00 1-00 1.00 1-00 Iodine.. .,. 0'6753 0'7252 - 0-7437 3.03 2.88 - 3 '01 Nitrogen .. - 0'0560 0.0525 0'0549 - 2.02 2'14 2'01 The foregoing samples were prepared as follows : Expts. 1 and 3.--22*8 C.C. of a 5 per cent. solution of silver nitrate were treated with just sufficient 10 per cent. ammonia to redissolve the precipitate, cooled to O", and 6 C.C.of a 14 per cent. solution of iodine chloride added. Ex@. 2.-28-8 C.C. of a 5 per cent, solution of silver nitrate wexe treated with 30 C.C. of 10 per cent. ammonia cooled to 0", and 6 c,c. of a 14 per cent. solution of iodine chloride added. Expt. 4.-'Phis specimen was prepared from cyanogen iodide as described below.'ro SlLBERRAD : THE METALLIC DERIVATIVES OF NITROGEN The ratio Ag : I : N is thus undoubtedly 1 : 3 : 2. The compound is therefore derived from nitrogen iodide by the replacement of one atom of hydrogen by silver, and possesses the formula NH,AgNI,. The substance decomposes readily when left at the ordinary tem- perature, especially when exposed to light. I n the dry state, it explodes on the slightest friction. I'he Potassium Derivative.--Bzuhay observed that the foregoing silver derivative dissolved readily in t~ solution of potassium cyanide, and that on subsequent addition of ammoniacal silver nitrate the original compound was rogenerated.He did not, however, succeed in isolating any soluble derivative. Regarded in the light of the above investigation, the potassium derivative would receive the formula N13NH,K, and although a silver compound of this formula might well be formed it is very improbable that a direct derivative of potassamide would exist in aqueous solution. I n order to gain some insight into the nature of the reaction, the effect of potassium cyanide solution on nitrogen iodide itself was first studied. Action of Potassium Cyanide on iVitrogen Iodide.-It was observed by Millon, in 1839, that nitrogen iodide dissolves in potassium cyanide, but the products of the reaction have hitherto remained uninvestigated.For the elucidation of the mechanism of the reaction, experiments were first made to ascertain the relative quantities of nitrogen iodide and potassium cyanide taking part therein. Tlie nitrogen iodide was prepared by the addition of a standard solution of iodine chloride to dilute ammonia. From blank experiments carried out in a precisely similar manner with the same solutions, the yield of nitrogen iodide was found to be 97 per cent. of that calculated from the strength of the iodine chloride solulion used. The amount of a standard solution of potassium cyanide necessary to dissolve a known amount of nitrogen iodide prepared as indicated above was then estimated.I n this way, 10 C.C. of standard iodine chloride solution, corresponding with 0.385 gram of iodine, were converted into nitrogen iodide and titrated with a standard potassium cyanide (containing 0.01784 gram per c.c.). The volume required to cause complete solution of the nitrogen iodide was (1) 11.27, (2) 11.21, mean = 11.24 C.C. ; that is, after correcting for the yield of nitrogen iodide, 1 atom of iodine corresponds with 1 a034 molecule of potassium cyanide. Hence one molecule of nitrogen iodide (NH,:NI,) requires 3 molecules of potassium cyanide for its solution. Experiments in which varying quantities of ammonia were used showed that, provided the quantity present is sufficient to suppress the hydrolysis of the cyanide, excess of ammonia is without influence on the amount of potassium cyanide necessary for complete solution of the nitrogen iodide.IODIDE AND THEIR BEARING ON ITS CONSTITUTION.71 For the investigation of the products of the reaction, a quactity of well washed nitrogen iodide was covered with a little ice-cold water, and then treated with a concentrated solution of potassium cyanide, also at Oo, until the black precipitate had disappeared. A white, in- soluble residue remained, but this passed into solution on allowing the liquid to attain the ordinary temperature. A quantity of the white residue was collected a t O* and recrystallised from ether; it melted a t 146' and its properties agreed with those of cyanogen iodide (m. p. 146.5").The identity was confirmed by analysis : 0.1715 gave 13.6 C.C. moist nitrogen a t 18.5Oand 765 mm. N = 9.21. CNI requires N = 9.18 per cent. A further quantity of this product was obtained by extracting the solution with ether. A portion of the solution which had not been thus extracted with ether was allowed t o evaporate in a vacuum desiccator over concentrated sulphuric acid. Ammonia and cyanogen were evolved, the former in large quantities. As the solution became concentrated, crystals slowly separated ; these were collected in four fractions and found to consist of the following salts : 1st Fraction. 3rd ,, KI=93*5 ,, KI = 75.0 per cent. K,CO, = 23.8 per cent. 2nd 9 ? KI=91*9 ,, K,CO,= 7.99 ,, 4th ,, KI=78.5 ,, The fourth fraction contained, in addition, a quantity of potassium cyanate, which was identified by conversion into urea.With this object in view, the remainder was treated with ammonium sulphate and carefully evaporated to dryness. The residue was dissolved in a little water and a small quantity of 50 per cent. nitric acid added to the cold solution. The crystalline precipitate of urea nitrate which rapidly separated was collected, washed with water and alcohol to remove a small quantity of free iodine present, and further identified by means of the biuret test. The products thus isolated were am- monia, cyanogen, potassium iodide, potassium cyanate, and potassium carbonate, It was shown above that each molecule of nitrogen iodide re- quired 3 molecules of potassium cyanide for complete solution, thus : 3KCN + NH3N13 + 3H,O = 3CNI + 3KOH + 2NH, The cyanogen iodide was partially isolated as such, but if left in solution it gradually interacted with the free potassium hydroxide.The other compounds isolated must be considered as products of this secondary decomposition. Cyanogen chloride is known to yield potassium cyanate when treated with caustic potagh. Hence it is not surprising72 THE METALLIC DERIVATIVES OF NITROGEN IODIDE. to find that cyanogen iodide behaves in a similar manner, yielding potassium cyanate and iodide. The potassium carbonate and ammonia found were evidently products of the hydrolysis of potassium cyanate. As previously shown, the cyanogen iodide is present as an unstable, intermediate product, and is only isolated as a solid compound if the temperature is kept low and the solution sufficiently concentrated to prevent the iodide from dissolving and undergoing further decom- position.Action OJ Potassium Cyanide on the Xilver Compound.-The forego- ing experiments show that the solubility of the silver compound in potassium cyanide is more likely to be due to the formation of cyanogen iodide than to any soluble potassium derivative of nitrogen iodide. I n order t o elucidate this point, a freshly prepared and carefully washed sample of the silver derivative was suspended in a little water and treated with four molecular proportions of potassium cyanide at 0". A thick precipitate yesulted, which, after filtration, proved to be very sparingly soluble in ether. The soluble portion consisted of cyanogen iodide (m.p. 146') and the insoluble portion of silver iodide mixed with a small quantity of the cyanide. The aqueous solution yielded, on ovapora- tion, the same compounds as those obtained when nitrogen iodide itself is treated with potassium cyanide, together with a small quantity of silver iodide which separated from solution during evaporation. The reaction is thus to be represented as follows : NI,NH,Ag + 4KCN + 4H20 = 3CNI + AgCN + 4KOH + 2NH,. As already indicated the production of potassium carbonate was evidently due to secondary reactions. When the ice-cold solution of the silver derivative in potassium cyanide is allowed to attain the ordinary temperature, cyanogen is evolved, and the precipitate consists only of silver iodide. A second portion of the silver cornpound was therefore treated with a large excess of potassium cyanide.This increased the formation of cyan- ogen iodide considerably, upwards of 30 per cent. of the iodine being recovered as such. On acidifying the potassium cyanide solution, after extraction, 61.5 per cent. of the total iodine was recovered as silver iodide. It appears therefore that cyanogen iodide is not stable in presence of silver cyanide unless potassium cyanide is present in sufficient excess to prevent the precipitation of silver iodide. It still remained, however, to explain the regeneration of the silver compound on the addition of ammoniacal silver nitrate. In order t o elucidate this point, the action of cyanogen on ammonia and amrnoniacal silver solutions was studied. Experiment shows that cyanogen iodide does not precipitate nitrogen iodide from ammonia in the absence of silver. If, however, an ammo-THE BENZENESULPHONYLPHENYLENEDIAMINES. 73 niacal solution of silver oxide, nitrate, or cyanide is added t o cyanogen isdide, the silver compound is immediately precipitated. Thus 22.8 c. c. of a 5 per cent. solution of silver nitrate were treated with 30 C.C. of 10 per cent. ammonia, cooled to Oo, and treated with 50 C.C. of a 2 per cent. solution of cyanogen iodide to which 2 C.C. of 30 per cent. ammonia had been previously added. The washed precipi- tate gave the following analytical results : Ag. I. N. Atomic proportionr , . . 1 *OO 3.00 8.09 Weight in grams . . . 0.2105 0.7437 0.0549 The mechanism of the regeneration of the silver compound is thus explained. Evidently cyanogen iodide reacts with ammonia, forming traces of nitrogen iodide, but the concentration does not reach the point a t which the compound is precipitated. On the addition of silver solution, the more sparingly soluble silver compound at once separates out, and thus, by removing the nitrogen iodide from the sphere of action, admits of its further formation. I n conclusion, I wish to express my thanks t o Mr. Smart for his assistance and to the Explosives Committee for permission t o publish these results. RESEARCH LABORATORIES, ROYAL ARSENAL.

ISSN:0368-1645    

DOI:10.1039/CT9058700066

出版商:RSC    

年代:1905

数据来源: RSC