摘要:

J 0 U li N A L OF THE CHEMICAL SOCIETY, TRANSACTIONS. A. J. ALLAIAND M.C. D.Sc. 0. 1,. BEADY D.Sc. A. W. CRossLm C.M.G. C.B.E., D. Sc. F. R.S. C. 11. DESCII D.Sc. P1i.D. M. 0. FO~LS'I'ER D.Sc. Ph.D. F.R.S. J. T. HEWITT M.A. D.Sc. Ph.D., J. C. IRVINE C.B.E. D.Sc. F.R.S. C. A. KTCANE D.Sc. Ph.D. P.R. S. T. br. LOWY u.B.E. D.s~. F.R.S. J. I. 0. MASSON M.B.E. D.Sc. G. T. MORGAN O.H.E. I).Sc. F.R.S. T. S. PATTERSON D.Sc.,Ph.D. J. C. PHILIP O.B.E. D.Sc. Ph.D., N. V. SIDGWICK M.A. Sc.D. J. F. TIIORPE C.B.E. D.Sc. F.R.S. Sir JAMES WALKER D.Sc. LL.D., F.R.S. F. K. S. @biters : J. C. CAIN D.Sc. A. J. GREENAWAY. %misf trirt @bitor : CLAREKCE SMITH D. Sc. a#air;titnt : A. A. ELDRIDGE BSc. 8 11 3r K er : MARGARET LE PLA B.Sc. 1921. Vol. CXIX.Part I. pp. 1-949. LONDON: GURNEY dz JACKSON 33 PATERNOSTER ROW E.C. 4. 1021 PRINTED IN GREAT BRITAIN BY RICHARD CLAY & SONS LIMITED, BUNGAY SUEFOL Some Properties of Explosives. A Lecture delivered before By SIR I -Preparation of Chloropicrin from Picric Acid and Trini-trotoluenes. By KENNEDY JOSEPH PREVIT~ ORTON and PHYLLIS VIOLET MCKIE . . 11.-The Decomposition of Tartaric Acid by Heat. By FREDERICK DANIEL CHATTAWAY and FRANCIS EARL RAY 111.-Trithiocarbonates and Perthiocarbonates. By ERNEST WICKHAM YEOMAN . 1V.-The Bromine Compounds of Phenanthrene. Part I. By HERBERT HENSTOCK . V.-Studies in Emulsions. Part 11. The Reversal of Phases by Electrolytes and the Effects of Free Fatty Acids and Alkalis on Emulsion Equilibrium. By SHANTI SWARUPA BHATNAGAR .. VL-p- Amino- p-phenylpropiophenone. By ALEX. MCKENZIE and FRED BARROW . VI1.-The Methylation of Cellulose. Part 111. Homo-geneity of Product and Limit of Methylation. By WILLIAM SMITH DENHAM . VII1.-The Reaction between Nitric Acid and Copper. By LANCELOT SALISBURY BAGSTER . . 1X.-The Formation of Derivatives of Tet,rahydronaphthalene from y-Phenyl Fatty Acids. By GEORGE ARMAND ROBERT KON and ARNOLD STEVENSON . . X.-The Action of the Chlorides of Sulphur on Substituted Ethylenes. The Action of Propylene on Sulphur Mono-chloride and the Synthesis of PP’-Dichlorodi-n-propyl Sulphide. By SAMUEL COFFEY . XI.-2 4 6-Trinitrotolylmethylnitroamine. By OSCAR LISLE BRADY and WILLIAM HOWIESON GIBSON XI1.-Organic Derivatives of Tellurium.Part 111. Crys-tallographic and Pharmacological Comparison of the a-and @-Dimethyltelluronium Dihaloids. By ISABEL ELLIE KNAGGS and RICHARD HENRY VERNON XII1.-The R6le of Protective Colloids in Catalysis. Part I. By THOMAS IREDALE . X1V.-Yeast Crops and the Factors which Determine them. By ARTHUR SLATOR . . the Chemical Society on December 16th 1920. ROBERT ROBERTSON K.B.E. F.R.S. . . . . * CONTENTS. PAPERS COBlISIUNICATED TO THE CHEMICAL SOCIETY. PAG P 1 29 34 38 55 61 69 77 82 87 94 98 105 109 11 iv CONTENTS. XV.-The Volumetric Estimation of Mixtures of Acids and of Bases and of Polybasic Acids or Bases. By HENRY THOMAS TIZARD and ALFRED REGINALD BOEREE XV1.-The Influence of the Solvent on the Temperature-coefficient of certain Reactions.A Test of the Radiation Hypothesis. By HENRY EDWARD Cox . XVI1.-Arylazoglyoxalinecarboxylic Acids. By ROBERT GEORGE FARGHER . XVII1.-The Constitution of Catechin. Part 111. Synthesis of Acacatechin. By MAXIMILIAN NIERENSTEIN . XIX-Influence of Colloids on the Rate of Reactions Involv-ing Gases. Part I. Decomposition of Hydroxylamine in the Presence of Colloidal Platinum. By ALEXANDER FINDLAY and WILLIAM THOMAS . XX.-Dihydroxynaphthaldehydes. By GILBERT T. MORGAN and DUDLEY CLOETE VINING . XX1.-ortho-Chlorodinitrotoluenes. Part 11. By GILBERT T. MORGAN and LESLIE AMIEL JONES XXI1.-The Constitution of the Disaccharides. Part V. Cellobiose (Cellose). By WALTER NORMAN HAWORTH and EDMUND LANGLEY HIRST . XXII1.-Derivatives of Gallic Acid.Part 11. Gallic Acid (and the Cresotic Acids) and Chloral. By RUPCHAND LILARAM ALIMCIIANDANI and ANDREW NORMAN MELDRUM XX1V.-Studies in Substituted Quaternary Azonium Com-pounds containing an Asymmetric Nitrogen Atom. Part IV. Additive Compounds of Thiocarbamide with Azon-ium Iodides. By BAWA KARTAR SINGH and MIRI LAL . XXV.-Condensation o€ p-fiitrobenzyl Chloride with Nitroso-compounds. A New Mode of Formation of A'-Oximino-ethers. By FRED BARROW and EVAN DALTON GRIFFITHS XXVI.-The Oxidation of Carbazole. By WILLIAM HENRY PERKM jun. and STANLEY HORWOOD TUCKER . XXVI1.-The Influence of Mercury Sulphur Arsenic and Zinc on the Catalytic Activity of Platinum. By EDWARD BRADFORD MAXTED . XXVII1.-On Reduction by Metals in Acid Solutions. Part I.The Reduction of Acid Ferric Sulphate Solutions by Zinc and Magnesium. By SAMUEL SUGDEN . XX1X.-Phenomena of the Ignition of Gaseous Mixtures by Induction Coil Sparks. By JOHN DAVID MORGAN and RICHARD VERNON WHEELER . XXX.-The Action of the Grignard Reagent on certain Nitric Esters. By HARRY HEPWORTH . XXXI.-The Melting Points of Mixtures of 0- and p-Toluene-sulphonyl Chlorides. By LEONARD HARDING . . . PAGE 132 142 158 164 170 177 187 193 20 1 210 212 216 225 233 239 251 26 CONTENTS. V PAUE XXXI1.-The Solubility of Ethyl Ether in Solutions of Sodium Chloride. By PERCY CYRIL LESLEY THORNE . XXXIIL-The Action of Ammonia on Acetone. By THOMAS STEWART PATTERSON and ANDREW MCMILLAN . XXX1V.-1 1 -DimethylcycZohexane from Methylheptenone.By ARTHUR WILLIAM CROSSLEY and NORA RENOUF . XXXV.-Gallotannin. Part XII. By MAXIMILIAN NIEREN-STEIN CHARLES WILLIAM SPIERS and ARTHUR GEAKE . XXXV1.-The Condensation of m-Dimethylaminophenol with Benzaldehyde. By SRI KRISHNA and FRAXK GEO. POPE XXXVI1.-Phenolcitraconein. By SRI KRISHNA and FRANK GZo. POPE . XXXVII1.-Additive Compounds of Antipyrylaminodiacetic Acid and its Salts with Neutral Salts. By ROBERT GEORGE FARGHER and HAROLD KING XXX1X.-An Investigation on the Influence of Negative Groups of Different Character on the Reactivity of Hydrogen Atoms Carried by the Same Carbon Atom. Part I. By BIRAJ MOHAN GUPTA . . XL.-The Conditions Underlying the Formation of Un-saturated and Cyclic Compounds from Halogenated Open-chain Derivatives.Part I. Products Derived from a-Halogenated Glutaric Acids. By CHRISTOPHER KELK INGOLD . . XL1.-The Mechanism Underlying the Reaction between Ethyl Cyanoacetate and Tautomeric Substances of the Keto-enol Type. By CHRISTOPHER KELK INGOLD . XLII .-Experiments on the Synthesis of the Polyacetic Acids of Methane. Part I. The Conditions Controlling Synthesis by the Cyanoacetic Ester Method and the Preparation of Methanetriacetic Acid. By CHRISTOPHER KELK INGOLD . . XLII1.-The Halogen Derivatives of Nitroform. By ALEX-ANDER KILLEN MACBETH and DAVID DOIG PRATT . XL1V.-Quantitative Reduction by Hydriodic Acid of Halogenated Malonyl Derivatives. Part I. The Amides and 8.-Di-alkyl- and -aryl-substituted Amides of Mono-and Di-bromomalonic Acid.By JOHNVALENTINE BACKES, RALPH WINTON WEST and MARTHA ANNIE WHITELEY XLV.-The Formation and Properties of Dithio-ketones (R,C:S:S) and Dithio-ethers (R,S:S). Part I. By KUVERJI GOSAI NAIK . XLV1.-Complex Metallic Ammines. Part V. cis-succinato-diethylenediaminecobaltic Salts and other Cobaltammine Salts containing a Seven-membered Ring in the Complex. By JAMES COOPER DUFF . . 262 269 271 276 286 259 292 298 305 329 341 354 359 379 38 vi CONTENTS. XLVI1.-Compounds of Hexamethylenetetramine with Com-plex Metallic Salts and Acids. By PRIYADARANJAN RAY and PULIN VIHARI SARKAR . XLVII1.-The Interaction of Sulphur Monochloride and Sub-stituted Ethylenes. By WILLIAM JACKSON POPE and JAMES LEONARD BRIERLEY SMITH . XL1X.-The Binary System Aniline-Acetic Acid.By EDMUND ARTHUR O’CONNOR . L.-Equilibria of Hydrofluosilicic Acid. By LAWSON JOHN HUDLESTON and HENRY BASSETT . L1.-The System Picric Acid-5-Phenylacridine. By HENRY BASSETT and THOMAS ARTHUR SINMONS LI1.-pp’-Dichlorodiethyl Disulphide. By GEORGE MAC-DONALD BENEETT . LII1.-Experiments on the Production of Compounds con-taining Arsenic as a Centre of Optical Activity. By GEORGE JOSEPH BURROWS and EUSTACE EBENEZER TURNER . L1V.-The Action of Alkyl Nitrates on Piperidine. By DAVID TEMPLETON GIBSON and ALEXANDER I~ILLEN MACBETH . . LV.-The Friedel-Crafts’ Reaction. Part 11. Migration of Halogen Atoms in the Benzene Nucleus. By MAURICE COPISAROW [with CYRIL NORMAN HUGH LONG] . LV1.-The Chlorovinylchloroarsines. By STANLEY JOSEPH GREEN and THOMASLATER PRICE LVI1.-The Determination of the Sorption of both Solvent and Solute.Part I. Preliminary. The System Benzene-Iodine-Charcoal. By ABU MOIZAMED BAHR and JOSEPH EDGAR KING . LVII1.-On Interfacial Tension. Part I. The Statical Measurement of Interfacial Tension in Absolute Units. By WILLIAM COLEBROOK REYNOLDS , L1X.-On Interfacial Tension. Part 11. The Relation between Interfacial and Surface Tension in Sundry Organic Solvents in Contact with Aqueous Solutions. By WILLIAM COLEBROOK REYNOLDS . . . LX.-Chlorine Overvoltages. By EDGAR NEWBERY . LX1.-The Stability of Tautomeric Formaldehydephenyl-hydrazones. By NEVIL VINCENT SIDGWICK and ELINOR KATHARINE EWBANK . Part XII. The Simultaneous Occurrence of 1 2- and of 1 3-Addition to “ Nascent ” Glutaconic Ester.By CHRISTOPHER KELK INQOLD and JOCELYN FIELD THORPE . . LXI1.-The Chemistry of the Glutaconic Acids. PAGE 390 396 400 403 416 418 426 438 442 448 454 460 466 477 486 49 CONTENTS. INTERNATIONAL PHYSICO-CHEMICAL SYMBOLS . ANNUAL GENERAL MEETING . OBITUARY NOTICES . LXII1.-The Influence of Salts on Chemical Equilibria in Solutions. By J. N. BRONSTED LX1V.-A Second Form of 6 6’-Dinitrodiphenic Acid and its Conversion into New Cyclic Systems. By JAMES KENNER and WILFRID VICTOR STUBBINGS . LXV.-Arylsulphonylnaphthylenediamines and their Sul-phonic Acids. By GILBERT T. MORGAN and WILLIAM ROBINSON GRXST . LXV1.-Researches on Residual Affinity and Co-ordination. Part 111.Reactions of Selenium and Tellurium Acetyl-acetones. By GILBERT T. MORGAN and HARRY DUGALD KEITH DREW . LXVI1.-The Soaps as Protective Colloids for Colloidal Gold. By THOMAS IREDALE . LXVII1.-The Interaction of Ethylene and Sulphur Mono-chloride. By FREDERICK GEORGE MA” WILLIAM JACKSON POPE and (the late) RICHARD HENRY VERNON . LX1X.-Organic Derivatives of Silicon. Part XXIV. dl-Derivatives of Silicoethane. By FREDERICK STANLEY KIPPING . LXX.-The Photochemical Reaction between Hydrogen and Chlorine and its Variation with the Intensity of the Light. By EDWARD CHARLES CYRIL BALY and WILLIAM FRANCIS BARKER . LXX1.-On some Carbamido-acids and their Hydantoins. By JOHN RICHARD SCOTT and JULIUS BEREND COHEN . LXXI1.-Organo-derivatives of Thallium. Part I.Some Reactions of Thalliumdialkyl Haloids. By ARCHIBALD EDWIN GODDARD . Mass-spectra and Atomic Weights. A Lecture Delivered before the Chemical Society on April 7th 1921. By FRANCIS WILLIAM ASTOX . LXXII1.-Organic Derivatives of Tellurium. Part IV. Action of Ammonia and the Alkalis upon ct-Dimethyl-telluronium Di-iodide. By (the late) RICHARD HENRY VERNON. . LXX1V.-Non-aromatic Diazonium Salts. Part VI. 3 5-Dime t h y lisooxaz ole -4 - diaz onium Salts and their Az o -derivatives. By GILBERT T. MORGAN and HENRY BURGESS . vii 502 513 529 PAGE 574 593 602 610 625 634 647 653 664 672 677 687 69 ... V l l l CONTENTS. LXXV.-Researches on Residual Affinity and Co-ordination. Part IV. The Constitution of Simple and Complex Cobaltic Quinoneoxime Lakes.By GILBERT T. MORGAN and J. D. MAIN SMITH . LXXV1.-Derivatives of m-Xylene. By SIDNEY ALBERT PEARMAN . . LXXVI1.-Some Physico-chemical Problems connected with the Stability of Explosives. By CYRIL NORMAN HINSHEL-LXXVIII.4-~-Methylaminoethylglyoxaline. By ROBERT GEORGE FARGHER and FRANK LEE PYNAN LXX1X.-Physical and Physiological Properties of some Hydrogenated Quinoline Compounds. By AKIRA SHIMO-MURA and JULIUS BEREND COHEN . . LXXX.-Interaction of Acetylene and Mercuric Chloride. Part 11. By WILLIAM JOB JENKINS . LXXX1.-The Catalytic Oxidation of Ferrous Salts in Acid Solutions. By RICHARD THOMAS and EDWARD THOMAS WILLIAMS . LXXXI1.-Ethylstannic Acid and Derivatives. By JOHN GERALD FREDERICK DRUCE . LXXXII1.-Note on Dithiocarbazinic Acid.By SINA M. LOSANITCH . LXXX1V.-Reduction of Emulsified Nitro-compounds. Part I. p-Phenylhydroxylamine from Nitrobenzene. By ARTHUR LAPWORTH and LEONORE KLETZ PEARSON . LXXXV.-Reduction of Emulsified Nitro-compounds. Part 11. Some Extensions of the Method. By ROBERT DOWNS HAWORTH and ARTHUR LAPWORTH . LXXXV1.-Determination of the Composition of Mixtures of Eugenol and isoEugeno1 Benzoates by means of Melting Points. By PHYLLIS VIOLET MCKIE . LXXXVI1.-Piperitone. Part I. The Occurrence Isolation, and Characterisation of Piperitone. By JOHN READ and HENRY GEORGE SMITH . LXXXVII1.-Studies in the Camphane Series. Part XXXIX. p- Aminophenylaminocamphor (Camphoryl-p-phenylene-diamine). By MARTIN ONSLOW FORSTER and WILLIAN BRISTOW SAVILLE .. LXXX1X.-Studies in the Resolution of Racemic Acids by Optically Active Alcohols. Part 11. The Resolution of Atrolactinic and a-Hydroxy- p-phenylpropionic Acids by E-Menthol. By HENRY WREN and EDWARD WRIGHT . XC.-The Hydrolysis of Cotton Cellulose. By GORDON WICKHAM MONIER- WILLIAMS . WOOD . . PAGE 704 717 72 1 734 740 747 740 758 763 765 768 777 779 789 79s SO CONTENTS. 1x PAGE XC1.-Amylases of the Cereal Grains-Rye. By JULIAN LEVETT BAKER and HENRY FRANCIS EVERARD HULTON XCI1.-The Formation and Stability of spiro-Compounds. Part IV. Ketones Derived from Open-chain and Cyclic Glutaric Acids. By GEORGE ARM~ND ROBERT KON . 810 XCII1.-Organic Derivatives of Silicon. Part XXV. Satu-rated and Unsaturated Silicohydrocarbons Si,Ph,.FREDERIC STANLEY KIPPING and JAMES EDWIN SAND? 830 XC1V.-Organic Derivatives of Silicon. T)- -L v37T7T Piper-idine as an Analytical Reagent By FREDERIC STANLEY KIPPING and JAMES EDWIN SANDS . . 848 XCV.-The Use of Aluminium Chloride and Ferric Chloride in the Preparation of Phenolphthalein. By CHARLES FREDERICK WARD . . 850 XCV1.-The Cumulative Effect of the Chlorine Atom and the Methyl and Sulphonyl Chloride Groups on Substitution in the Benzene Nucleus. Part I. By WILLIAM DAVIES . 853 XCVI1.-The Cumulative Effect of the Chlorine Atom and the Methyl and Sulphonyl Chloride Groups on Substitution in the Benzene Nucleus. Part 11. By WILLIAM DAVIES 876 XCVII1.-Mitragynine and Mitraversine Two New Alkaloids from Species of Mitragyne.By ELLEN FIELD . 887 XCIX-A New Degradation Product of Physostigmine. By EDGAR STEDMAN . . 891 C.-Dinitrotolylhydrazines. By OSCAR LISLE BRADY and JOHN HERBERT BOWMAN . . 894 C1.-Studies in the Anthracene Series. Part I By EDWARD DE BARRY BARNETT and JAMES WILFRED COOK . . 901 CI1.-Organo-derivatives of Bismuth Part IV. The Inter. action of the Halogen Derivatives of Tertiary Aromatic Bismuthines with Organo-derivatives of Magnesium and Mercury. By FREDERICK CHALLENGER and CHARLES FREDERICK ALLPRESS . 913 CII1.-Some Factors Governing the Sorptive Capacity of Charcoal. Sorption of Ammonia by Cocoa-nut Charcoal. By JAMES BRIERLEY FIRTH . . 926 C1V.-A Colloid Theory of the Corrosion and Passivity of Iron and of the Oxidation of Ferrous Salts. By JOHN ALBERT NEWTON FRIEND .. 932 CV.-The Conditions Underlying the Formation of Un-saturated and Cyclic Compounds from Halogenated Open-chain Derivatives. Part 11. Products Derived from a-Halogenated Adipic Acids. By CHRISTOPHER KELK INGOLD . 951 80 X CONTENTS. CVL-The Velocity of Reaction in Mixed Solvents. Part I. The Velocity of Saponification of Two Ethyl Esters in Ethyl Alcohol-Water Mixtures. By ALBERT ERIC CASHMORE HAMILTON MCCOMBIE and HAROLD ARCHI-BALD SCARBOROUGH. CVI1.-The Influence of Position on the Solubilities of the Substituted Benzoic Acids. By NEVIL VINCENT SIDG-WICK and ELINOR KATHARINE EWBANK CVII1.-Inff uence of Position on the Solubility and Vola-tility of the Mono- and Di-nitrophenols. By NEVIL VINCENT SIDGWICK and WILFRID MAJOR ALDOUS .C1X.-The Solubility and Volatilitly of the Chloro- and Nitro-anilines and of their Acetyl Derivatives. By NEVIL VINCENT SIDGWICK and HOWARD ERNEST RUBIE CX.-Photocatalysis. Part I. The Synthesis of Form-aldehyde and Carbohydrates from Carbon Dioxide and Water. By EDWARD CHARLES CYRIL BALY ISIDOR MORRIS HEILBRON and WILLIAM FRANCIS BARKER . CX1.-a-Monosodium Glyceroxide Its Structure and Application. By ARTHUR FAIRBOURNE and HAROLD TOMS . CXI1.-Electrochemical Conceptions of Valency. By JOHN ALBERT NEWTON FRIEND CXII1.-The Influence of Nitro-groups on the Reactivity of Substituents in the Benzene Nucleus. Part 111. The Partial Reduction of the Dinitrotoluenes by Stan-nous Chloride and Hydrochloric Acid. By HAROLD BURTON and JAMES KENNER .. CX1V.-The Influence of Nitro-groups on the Reactivity of Substituents in the Benzene Nucleus. Part IV. The Condensation of Ethyl 3- and 5-Nitro-2-chloro-benzoates with Hydrazines. By JAMES KENNER and ERNEST WITHAM . CXV.-Researches on Residual Affinity and Co-ordination Part V. Gallium wcetylacetone and its Analogues. By GILBERT T. MORGAN and HARRY DUGALD KEITH DREW . CXV1.-Researches on Residual Affinity and Co-ordination. Part VI. Selenodithionic Acid and its Metallic Salts. By GILBERT T. MORGAN and J. D. MAIN SMITH . CXVIL-Diazo-derivatives of 4’-Amino-l-phenyl-5-methyl-benzothiazole (Dehydrothio-p-toluidine). By GILBERT T. MORGAN and DOROTHY WEBSTER CXVIII.-p - Hydroxy - p - 3 4-methylenedioxyphenylethyl-amine and its Derivatives. By FREDERICK ALFRED MASON .. PAGE 9TO 979 1001 1013 1025 1035 1040 1047 1053 1058 1066 1070 107 CONTENTS. xi PAGE CXIX-Overvoltage. Part I. A Comparison of the Methods of Determination especially as Applied to the Mercury Cathode. By SYDNEY DUNNILL . . CXX.-Epicamphor. Part 11. By WILLIAM HENRY PERKIN jun. and ALAN FRANCIS TITLEY . CXX1.-Derivatives of Sulphur in Commercial Salvarsan. Part I. By HAROLD KJNG . CXXI1.-The Sorption of Hydrogen by Amorphous Palla-dium. CXXII1.-The Sorption of Alcohol and Water by Animal Charcoal. By JOHN DRIVER and JAMES BRIERLEY FIRTH . CXX1V.-Action of Magnesium Phenyl Haloids on Diphenyl-chloroacetyl Chloride. Constitution of Triphenylvinyl Alcohol. By ALEX. MCKENZIE and JOHN SCOTT WALKER BOYLE .CXXV.-Inorganic Complex Salts. Part I. Potassium Ferrioxalate and Potassium Cobaltimalonate. By WILLIAM THOMAS . CXXV1.-A New Method for Determining the Volatile Matter yielded by Coals up to Various Temperatures. By WILLIAM ARTHUR BONE and LEONARD SILVER . CXXVI1.-The Mechanism of the Oxidation of Drying Oils as Elucidated by a Study of the True Oxygen Absorp-tion. Part I. Linseed Oil and its Fatty Acids. By SAMUEL -COFFEY . CXXVIIL-Metallic Derivatives of Nitrophenolic Com-pounds. Part I. Interaction of Barium Strontium, and Calcium Hydroxides with the Mononitrophenols. By ARCHIBALD EDWIN GODDARD . CXX1X.-Interaction of Sulphur Monochloride and Organic Acid Amides. CXXX.-Some New Tricyclic Bases. By TOM SIDNEY MOORE and IDA DOUBLEDAY . CXXXI.The Structural Isomerism of the Oximes. Part I. Criticism of the Hantzsch-Werner Hypothesis and a New Theory of the Constitution of Isomeric Oximes. By FREDERICK WILLIAM ATACK . CXXXI1.-The Structural Isomerism of the Oximes. Part H. A Fourth Benzildioxime. By FREDERICK WILLIAM ATACK and LEONARD WHINYATES CXXXII1.-The Action of the Grignard Reagent on certain Organo-sulphur Compounds. By HARRY HEPWORTH and HENRY WILLIAM CLAPHAM. By JAMES BRIERLEY FIRTH . By KUVERJI GOSAI NAIE . . 1081 1089 1107 1120 1126 1131 1140 1145 1152 1161 1166 1170 1175 1184 118 xii CONTENTS. CXXX1V.-The Formation and Stability of spiro-Corn-pounds. Part V. Derivatives of CycZoHexanespiro-cyclohexane and of cycZoPentanespirocycZohexane. By WOODFORD STANLEY GOWAN PLUCKNETTE NORRIS and JOCELYN FIELD THORPE.CXXXV.-Dyes derived from Phenanthraquinone. By EDWIN ROY WATSON AND S~HIBHUSHAN DUTT. . CXXXV1.-Experiments on the Synthesis of the Polyacetic Acids of Methane. Part 11. Some Abnormal Con-densations of Malonic and Cyanoacetic Esters with Halogenated Methanes. By CHRISTOPHER KELU INGOLD and WALTER JAMES POWELL . CXXXVI1.-The Formation and Properties of Dithio-ketones (R,C:S:S) and Dithio-ethers (R,S:S). Part 11. By KUVERJI GOSAI NAIK . CXXXVII1.-An Improved Gas Combustion Furnace for Use in Organic Analysis. By THOMAS JOHNSON HEDLEY . CXXX1X.-The Action of the Grignard Reagent on certain Tervalent Organo-iodo-compounds. By HARRY HEPWORTH . CXL.-Accelerated Formation of Magnesium Alkyl and Aryl Haloids.By HARRY HEPWORTH . CXL1.-Aminoacylcholine Esters. Part I. Glycylcholine. By HAROLD WARD DUDLEY . CXLI1.-The Sulphonation of Toluene with Chlorosulphonic Acid. By LEONARD HARDING . CXLII1.-Studies on Hypophosphorous Acid. Part 111. Its Reaction with Mercuric Chloride. By ALEC DUNCAN MITCHELL. . CXL1V.-Negative Adsorption of Alkali Haloids by Wood Charcoal. By ALWYN PICKLES . CXLV.-On the Relation between ,the Occlusive Power of Palladium for Hydrogen and its Activity for Catalytic Hydrogenation. By EDWARD BRADFORD MAXTED . CXLV1.-The Action of Sodium on Phenyl Acetate. By WILLIAM HENRY PERKIN jun. . CXLVI1.-The Doebner-Miller Quinaldine Synthesis. By WILLIAM HOBSON MILLS JOHN EDMUND GUY HARRIS, and HERBERT LAMBOURNE . CXLVII1.-The Preparation of some Ally1 Compounds.By SANUEL COBFEY and CHARLES FREDERICK WARD . CXL1X.-Linolenic and Hexabromostearic Acids and some of their Derivatives. By SAMUEL COFFEY . PAGE 1199 1211 1222 1231 1242 1244 1249 1256 1261 1266 1278 1280 1284 1294 1301 130 CONTENTS. ... X l l l PAGE CL.-Organo-derivatives of Thallium. Part 11. Inter-action of Thalliumdialkyl Hydroxides with Nitrophenols and Nitrocresols. By ARCHIBALD EDWIN GODDARD . CL1.-The Formation and Stability of spiro-Compounds, Part VI. New Derivatives of cycZoPropane and cyclo-Hexanespirocyclopropane. By STANLEY FRANCIS BIRCH WILLIAM HENRY GOUGH and GEORGE ARMAND ROBERTKON . CLI1.-The Ternary System Ammonium Chloride-Manganous Chloride-Water. By FREDERICK WILLIAM JEFFREY CLENDINNEN and ALBERT CIIERBURY DAVID RIVETT .CLII1.-Synthesis of 1 6-Dihydroxy-2-methylanthra-quinone. By JOHN LIONEL SIMONSEN and MADYAR GOPAL RAU . CL1V.-Cupritartrates. By JOHN PACKER and IAN WILLIAM WARK . CLV.-The Labile Nature of the Halogen Atoms in Sub-stituted Nitrornethanes. By ALEXANDER KILLEN MACBETH and DAVID DOIG PRATT CLV1.-Colorations produced by Substituted Nitroforms. By HUGH GRAHAM and ALEXANDER KILLEN MACBETH . CLVI1.-The Hydration of the Fibres of Soap Curd. Part I. The Degree of Hydration determined in Experiments on Sorption and Salting Out. By JAMES WILLIAM MCBAIN Part 11. The Dew-point Method. By JAMES WILLIAM MCBAIN and CYRIL SEBASTIAN SALMON . CL1X.-Ethyl Hydrogen Sulphate. By HORACE BARRATT DUNNICLIFB and GERALD SNOWDEN BUTLER CLX.-Studies on the Configuration of ad-Dibromodibasic Acids.Part I. The Dibromoadipic Acids. Synthesis and Resolution of trans-cyclopentane- 1 2 3-tricarb-oxylic Acid. By WILLIAM HENRY PERKM jun. and ERIC ROBIXSON . CLX1.-Resolution of dZ-trans-cycZoPentane- 1 3-clicarboxylic Acid. By WILLIAM HENRY PERKIN jun. and HAROLD ARCHIBALD SCARBOROUGH CLXI1.-The Mechanism of the Oxidation of Drying Oils as Elucidated by a Study of the True Oxygen Absorption. Part 11. Linolenic and Linolic Acids. By SAMUEL COFBEY . CLXII1.-Derivatives of Sulphur in Commercial Salvarsan. Part 11. By HAROLD KING . . . and EiERBERT ERNEST MARTIN . CLVII1.-The Hydration of the Fibres of Soap Curd. . 1310 1315 1329 1339 1348 1356 1362 1369 1374 1384 1393 1400 1405 141 xiv CONTENTS.CLXIV .-Phenolcoumarein and Resorcinolcoumarein. By SRI KRISHNA . CLXV.-The Nitro- and Amino-derivatives of m-Hydroxy-benzoic Acid. By VICTOR FROELICHER and JULIUS BEREND COHEN . CLXV1.-A Comparison of some Isomeric isocyanines. By FRANCES MARY HAMER . CLXVI1.-A New Method for the Preparation of cc-Acyl-phenylhydrazines. By WALLACE FRANK SHORT . CLXVII1.-Some Additive Compounds derived from Arsines. By GEORGE JOSEPH BURROWS and EUSTACEBENEZER TURNER . Part 11. The Alkylation of Nitroprussic Acid. By GEORGE JOSEPH BURROWS and EUSTACE EBENEZER TURNER . CLXX.-The Influence of Steric Factors on Intramolecular Condensation. By JAMES KENNER and ERNEST WITHAM CLXX1.-9 10-Dihydrophenanthrene.By HERBERT HEN-CLXXI1.-The System Potassium Sulphate-Glucinum Sulphate-Water at 25”. By HUBERT THOMAS STANLEY BRITTON and ARTHUR JOHN ALLMAND CLXXI1I.-Researches on Pseudo-bases. Part 111. Di-alkylaminomethyl Alkyl Ethers and Sulphides. By CHARLES MAXWELL MCLEOD and GERTRUDE MAUD ROBINSON . CLXX1V.-Some Derivatives of Anthraquinonedi-imide. By LEON PIERRE GEORGE KEFFLER . CLXXV.-The Determination of Surface Tension from the Rise in Capillary Tubes. By SAMUEL STTGDEN . CLXXV1.-Contributions to the Chemistry of the Terpenes. Part XX. The Action of Hypochlorous Acid on Pincne. By GEORGE GERALD HENDERSON and JOSEPH KENNETH CLXXVI1.-The Reactivity of Doubly-conjugated Un-saturated Ketones. Part I. 4’-Dimethylamino-%hydr-oxydistyryl Ketone.By ISIDOR MORRIS HEILBRON and JOHANNES SYBRANDT BUCK CLXXVIII. - The Reactivity of Doubly-conjugated Unsaturated Ketones. Part 11. The Action of Hydroxylamine Semicarbazide and Phenylhydrazine on 4’-Dimethylamino-2-hydroxydistyryl Ketone and its Methyl Ether. By ISIDOR MORRIS HEILBRON and JOHANNES SYBRANDT BUCK . CLX1X.-The Constitution of the Nitroprussides. STOCK . . MARSIX . PAGE 14-20 1425 1432 1445 1448 1450 1452 1461 1463 1470 1476 1483 1492 1500 151 CONTENTS. xv PAGE CLXX1X.-Surface Tensions of Salts of the Fatty Acids and their Mixtures. By ERIC EVERARD WALKER . CLXXX.-ortho-Chlorodinitrotoluenes. Part 111. Bases de-rived from 2-Chloro-4 5-dinitrotoluene. By GILBERT T. MORGAN and WILLIAM ARTHUR PERCIVAL CIXALLENOR CLXXXL-Non-aromatic Diazonium Salts.Part VII. The Diazo-reaction in the isoOxazole Series. By GILBERT T. MORGAN and HENRY BURGESS CLXXXI1.-A New Type of Iodine Compound. By JOHN NORMAN COLLIE and AMY ADA BEATRICE REILLY . Photosynthetic Processes in the Air upon the Land and in the Sea in Relation to the Origin and Continuance of Life on the Earth. Hugo Miiller Lecture Delivered before the Chemical Society on June 16th 1921. By BENJAMIX MOORE D.Sc. F.R.S. CLXXSII1.-The ortho-Dimethylanthraquinones and their Derivatives. By ARTHUR FAIRBOURNE . CLXXX1V.-Experiments on the Synthesis of the Polyacetic Acids of Methane. Part 111. Conditions controlling Synthesis by the Cyanoacetic Ester Method-(continued). By CHRISTOPHER KELK INGOLD and EDWARD ARTKUR PERREN .. CLXXXV.-Harmine and Harmaline. Part V. The Syn-thesis of Norharman. By WILLIAM OGILVY KERMACK, WILLIAM HENRY PERKIN jun. and ROBERT ROBINSON. CLXXXVL-The Molecular Conductivity of some Sul-phonium Compounds in Acetone. By SIR PRAPHULLA CHANDRA R ~ Y and KALIKUMAR KUMAR CLXXXVI1.-The Essential Oil from Andropogolz Jwaran-czisa Jones and the Constitution of Piperitone. By JOHN LIONEL SIMONSEN . CLXXXVII1.-The Calculation of the Colour of " Cyclic " Coloured Substances. By JAMES MOIR . CLXXX1X.-The Hydration of the Fibres of Soap Curd. Part 111. Sorption of Sodium Palmitate. By MARY EVELYN LA IN^ CXC.-The Propagation of Flame in Mixtures of Ethylene and Air. By WILLIAM RONALD CHAPMAN . CXC1.-The Effect of Temperature on Platinum Black and other Finely-divided Metals.By ROBERT WRIGHT and ROBERT CHRISTIE SMITH . Part I. The Solubility of Lead Monoxide. By SAMUEL GLAS-. . CXCI1.-Physical Chemistry of the Oxides of Lead. STONE . . . . 0 b . 1521 1537 1546 1550 1555 1573 1582 1602 1643 1644 1654 1669 1677 1683 168 xvi CONTENTS. CXCII1.-The Mechanism of the Action of Fused Alkalis. Part 11. The Action of Fused Potassium Hydroxide on Phenylglyceric Acid. By (the late) HENRY RONDELE SUEUR and CYRIL CHRISTIAN WOOD CXC1V.-ortho- Chlorodinitrotoluenes. Part IV. 2-Chloro -3 4-dinitrotoluene. By GILBERT T. MORGAN AND THOMAS GLOVER . CXCV.-Dinaphtha-1 7 1’ 7’-diquinone. By GILBERT T. MORGAN and DUDLEY CLOETE VINING . CXCV1.-Chenopodium Oil. By THOMAS ANDERSON HENRY and HUMPHREY PAGET .CXCVI1.-m-Opianic Acid (4 5-Dimethoxy-o-aldehydo-benzoic Acid). By ROBERT GEORGE FARGHER and WILLIAM HENRY PERXIN jun. . Part 111. The Relationship of I-Glucosan to d-Glucose and to Cellulose. By JAMES COLQUHOUN IRVINE and JOHN WALTER HYDE OLDHAM CXC1X.-Studies in Emulsions. Part 111. Further In-vestigations on the Reversal of Type by Electrolytes. By SHANTI SWARUPA BHATNAGAR . CC.-Crystallographic Descriptions of some Pyridine and Picoline Derivatives. By MARY WINEARLS PORTER . CC1.-Studies of Ilalogenohydrins and Related Derivatives in the Cinnamic Acid Series. Part I. By JOHN READ and ALBERTA CATHERINE PRITCHARD ANDREWS CCI1.-The Application of Hofmann’s Reaction to Substi-tuted Phthalimides. By TOM SIDNEY MOORE MURIEL TREGARTHEN MARRACB and ANNIE KATHLEEN PROUD CCII1.-rn-Dithiobenzoic Acid.By SAMUEL SMILES and JESSIE STEWART . CC1V.-The Rate of Hydrolysis of Methyl Acetate by Hydrochloric Acid in Solutions containing Sucrose. By GEORGE JOSEPH BURROWS . CCV.-The Dimorphism of Potassium Ethyl Sulphate. By DALZIEL LLEWELLYN H-~MZMICK and JOHN MYLNE MULLALY CCV1.-The Friedel-Crafts’ Reaction. Part 111. Migration of Akyl Groups in the Benzene Nucleus. By MAURICE COPISAROW . CCVI1.-Derivatives of 3-0xy( 1)thionaphthen. By SAMUEL SMILES and ERNEST WILSON MCCLELLAND CCVIIL-A New Method for the Resolution of Asymmetric Compounds. By AKIRA SHIMOMURA and JULIUS BEREND COHBN . . . CXCVII1.-The Constitution of Polysaccharides. PAGE 1697 1700 1707 1714 1724 1744 1760 1769 1774 1786 1792 1798 1802 1806 1810 I81 COXTENTS.xvii PAGE CCIX .-Derivatives of Tetrahydrocarbazole. By WILLIAM HENRY PERKIN jun. and SYDNEY GLENN PRESTON PLANT . . . By THOMAS WALLACE and ALEXANDER FLECK . B i GEORGE MACDONALD BENNETT and EDITH MURIEL CCXI1.-Experiments on the Synthesis of the Polyacetic Acids of Methane. Part IV. Conditions of Formation by the Cyanoacetic Ester Method of Stable Methane-triacetic Esters. By CHRISTOPHER KELK INGOLD and EDWARD ARTHUR PERREN . CCXII1.-Experiments on the Synthesis of the Polyacetic Acids of Methane. Part V. The Preparation of Carb-oxymethanetriacetic Acid. By CHRISTOPHER KELK INGOLD and WALTER JAMES POWELL . CCX1V.-Dichloroacetates and Chlorobromoacetates from up-Dichlorovinyl Ethyl Ether.By HOLLAND CROMPTON and PHYLLIS MARY TRIFFITT . . CCXV.-Valency and Co-ordination. By SAMUEL HENRY CLIFFORD BRIGGS . CCXV1.-Studies in the n-Butyl Series. Part I. Aryl n-Propyl Ket0ne.s. By GILBERT T. MORGAN and WILFRED JOHN HICKINBOTTOM CCXVI1.-The Nitro- and Amino-derivatives of 4-Phenyl-glyoxaline. By REGINALD LINDSAY GRANT and FRANK LEE PYMAN . . CCXVII1.-The Explosion of Acetylene and Nitrogen. Part I. By WILLIAM EDWARD GARNER and KICHIMATSU MATSUNO CCX1X.-Physical Chemistry of the Oxides of Lead. Part 11. The Supposed Enantiotropy of Lead Monoxide. By SAMUEL GLASSTONE . CCXX.-Investigations into the Analytical Chemistry of Tantalum Columbium and their Mineral Associates. I. The Use of Tartaric Acid in the Analysis of Natural Tantalocolumbates.11. The Separation of Zirconium from Tantalum and from Columbium. By WALTER RAYMOND SCHOELLER and ALAN RICHARD POWELL . CCXX1.-Catalysis of the Mutarotation of Dextrose by Metals. By WILLIAM EDWARD GARNER and DOUGLAS NORMAN JACKMAN . CCXXI1.-The Decomposition of Ozone by Light of the Visible Spectrum. By ROBERT OWEN GRIFFITH and WILLIAM. JAMES SHUTT . CCX.-Some Properties of Fused Sodium Hydroxide. CCX1.-Some Derivatives of Monothioethylene Glycol. WHINCOP . . 1825 1839 1860 1865 1869 1874 1876 1879 I893 1903 1914 1927 1936 194 xviii CONTENTS. CCXXII1.-Syntheses in the Thianthren Series. Part I. By J~ANENDRA NATH RAY . CCXX1V.-The Solubility of Glucinum Sulphate in Water and Sulphuric Acid at 25".By HUBERT THOMAS STANLEY BRITTON . CCXXV.-Studies on the Dependence of Optical Rotatory Power on Chemical Constitution. Part IV. Aryl Derivatives of Bisiminocamphor . By BAWA KARTAR SINQH MAHAN SINGH and JIWAN LAL By CHRISTOPHER KELK INQOLD and WALTER JAMES POWELL . CCXXVI1.-Complex Metallic Ammines. Part VI. cis-Phthalato- cis-Homophthalato- and other Diethylene-diaminecobaltic Salts. By JAMES COOPER DUFF . CCXXVII1.-The Separation of Miscible Liquids by Dis-tillation. By ARTHUR FELIX DUFTON . CCXX1X.-The Colour of Iron Alum. By JANE BONNELL and EDGAR PHILIP PERMAN . CCXXX.-The Direct Iodometric Estimation of Lead Peroxide. By SAMUEL GLASSTONE . CCXXXL-The Conditions Underlying the Formation of Unsaturated and Cyclic Compounds from Halogenated Open-chain Derivatives.Part 111. Producks derived from Halogenated Glutaconic Acids. By ERNEST HAROLD FARMER and CHRISTOPHER KELK INGOLD . CCXXXIL-Studies in the Dihydronaphthalene Series. Part 11. The ar-Dihydro-a-naphthols and their Deriv-atives. By FREDERICK MAURICE ROWE and ESTHER LEVIN . Part I. Influence of Catalysts a Convenient Method of Chlorinating Benzene. CCXXX1V.-The Adsorption of Thorium-B and Thorium-C by Ferric Hydroxide. By JOHN ARNOLD CRANSTON and ROBERT ALEXANDER BURNETT . CCXXXV.-Metallic Derivatives of Nitrophenolic Com-pounds. Part 11. Some Nitrotolyloxides of Metals of Group 11. By DOROTHY GODDARD and ARCHIBALD EDWIN GODDARD . CCXXXV1.-The Reaction between Persulphates and Silver. By GEOFFREY ISHERWOOD HIGSON .CCXXXVIL-Structure and Colour of the Azine Scarlets. By JULIUS BEREND COHEN and HERBERT GRACE CRABTREE . . . CCXXV1.-The Reversibility of the Michael Reaction. CCXXXII1.-Researches on Sulphuryl Chloride. By OSWALD SILBERRAD . PAGE 1959 19G7 1971 1976 1982 1988 1994 1997 2001 202 1 2029 2036 2044 2048 205 xviii CONTENTS. CCXXII1.-Syntheses in the Thianthren Series. Part I. By J~ANENDRA NATH RAY . CCXX1V.-The Solubility of Glucinum Sulphate in Water and Sulphuric Acid at 25". By HUBERT THOMAS STANLEY BRITTON . CCXXV.-Studies on the Dependence of Optical Rotatory Power on Chemical Constitution. Part IV. Aryl Derivatives of Bisiminocamphor . By BAWA KARTAR SINQH MAHAN SINGH and JIWAN LAL By CHRISTOPHER KELK INQOLD and WALTER JAMES POWELL . CCXXVI1.-Complex Metallic Ammines. Part VI. cis-Phthalato- cis-Homophthalato- and other Diethylene-diaminecobaltic Salts. By JAMES COOPER DUFF . CCXXVII1.-The Separation of Miscible Liquids by Dis-tillation. By ARTHUR FELIX DUFTON . CCXX1X.-The Colour of Iron Alum. By JANE BONNELL and EDGAR PHILIP PERMAN . CCXXX.-The Direct Iodometric Estimation of Lead Peroxide. By SAMUEL GLASSTONE . CCXXXL-The Conditions Underlying the Formation of Unsaturated and Cyclic Compounds from Halogenated Open-chain Derivatives. Part 111. Producks derived from Halogenated Glutaconic Acids. By ERNEST HAROLD FARMER and CHRISTOPHER KELK INGOLD . CCXXXIL-Studies in the Dihydronaphthalene Series. Part 11. The ar-Dihydro-a-naphthols and their Deriv-atives. By FREDERICK MAURICE ROWE and ESTHER LEVIN . Part I. Influence of Catalysts a Convenient Method of Chlorinating Benzene. CCXXX1V.-The Adsorption of Thorium-B and Thorium-C by Ferric Hydroxide. By JOHN ARNOLD CRANSTON and ROBERT ALEXANDER BURNETT . CCXXXV.-Metallic Derivatives of Nitrophenolic Com-pounds. Part 11. Some Nitrotolyloxides of Metals of Group 11. By DOROTHY GODDARD and ARCHIBALD EDWIN GODDARD . CCXXXV1.-The Reaction between Persulphates and Silver. By GEOFFREY ISHERWOOD HIGSON . CCXXXVIL-Structure and Colour of the Azine Scarlets. By JULIUS BEREND COHEN and HERBERT GRACE CRABTREE . . . CCXXV1.-The Reversibility of the Michael Reaction. CCXXXII1.-Researches on Sulphuryl Chloride. By OSWALD SILBERRAD . PAGE 1959 19G7 1971 1976 1982 1988 1994 1997 2001 202 1 2029 2036 2044 2048 205

ISSN:0368-1645    

DOI:10.1039/CT92119FP001

出版商:RSC    

年代:1921

数据来源: RSC

摘要:

J O U R N A L OF THE CHEMICAL SOCIETY. TRANSACTIONS. domtnittee of @ublicntion : A. J. ALLMAKD M.C. D.Sc. 0. L. BRADY U S c . A. W. C'ROSSLEY C.M.G. C.B.E., D. Sc. F. R. S. 0. H. DESCIJ D.Sc. Ph.D. M. 0. FORSTER TI.%. Ph.n. F.R.S. J. T. HEW~TT M.A. D.Sc. PIi.D., J. C.IRVINE C.B.E. D.Sc. F.R.S. C. A. KEANE D.Sc. Ph.D. F.R.S. T. M. LGWRY C.B.E. D.Sc. F.R.S. J. I. 0. MASSON M.B.E. D.Sc. G. T. MoRGAN,O.B.E. D.Sc. F.R.S. T. S. PATTERSON D.Sc. Ph.L). J. C. PHILIP O.B.E. 1).Sc. Ph.D., N. V. SIDGWICK M.A. Sc.D. J . P. TIIORPE C.S.E. D.Sc. F.R.S. Sir JAMES WALKER D.Sc. LL.D., F.R.S. F.H.S. 6bitlIrtl: J. C. CAIN D.Sc. A. J. GREENAWAP. pseiatatrt &bitor : CLARENCE SMITH D.Sc. Bssistrrirt 2Jttbrt.er : A. A. ELDRIDGE B.Sc. MARGARET LE PLA KSc. 1921. Vol. CXIX. Part II. pp. 951-end. LONDON: GURNEY st JACKSON 33 PATERNOSTER ROW E.C. 4. 1921 PRINTED IN GREAT BRITAIN BY RICHARD CLAY &; SONS LIMITED, BUNGAY SUFFOLK

ISSN:0368-1645    

DOI:10.1039/CT92119FP021

出版商:RSC    

年代:1921

数据来源: RSC

摘要:

PREPARATION OF CHLOROPICRIN FROM PICRIC ACID ETC. 20 I.-Prepalration of Chloropickn from Picric Acid * and Trinitrotoluenes. By KENNEDY JOSEPH PREVITB ORTON and PHYLLIS VIOLET MCKIE. CHLOROPICRIN was first prepared by Shenstone (Annalen 1847 66, 241) from picric acid by the action of bleaching powder chlorine, potassium chlorate and hydrochloric acid or aqua regia. Hofmann (ibid. 1866 139 111) described in some detail the procedure when bleaching powder is used. He obtained a yield of 114 per cent., that is 53 per cent. of the maximum (215 per cent.) if all the nitro-grcups of the picric acid appear in the chloropicrin: C6H,(N0,),*OH + 3CC13*N0,. * Orton and Pope English Patent No. 1428.78 (1918) 30 ORION AND MCKIE PREPARATION OF CHLOROPICRIN Hcfmann’s yield is undoubtedly low; there is no difficulty in obtain-ing a yield of 150-160 per cent.a figure which is somewhat above the yield of 143.5 per cent. which corresponds with the appearance of two nitro-groups as chloropicrin : C,H,(NO,),*OH -+ 2CC13-N02.* A consistently better yield reaching 200 per cent. can be obtained by passing chlorine into a cooled suspension of picric acid (sodium picrake) in aqueous sodium carbonate. The products are chloropicrin and some nitric acid together with chloride and some hypochlorite and chlorate which has arisen from transf ormation of hypochlorite. No other compounds are present in appreciable quantity. From determinations of the hypochlorite chlorate and chloride in the aqueous product it is found that the proportion of the last accords well with the opinion that chloropicrin is formed in a reaction between hypochlorite (hypochlorous acid) and picric acid thus: that is, when the maximum yield would be 215 per cent.; or, C,H,(NO2),*OH + llHCl0 = 3CCl,*NO + 2HC1+ 3C0 + 6Hz0, C6H2(NO2),.OH + 11C1 + 5H,O = 3CC1,*N02 + 13HC1+ 3C02 (a) C,Hg(N0,)3*OH + 12C12 + SH,O = 2CCl,*NO + 18HC1+ 4C0 + HNO, (U) when the maximum yield would be 143.5 per cent.When the yield of chloropicrin is low however other substances appear among the products. The quantity of nitric acid in the product (delermined by boiling with excess of ferrous chloride and measuring the nitric oxide evolved) is a measure of the exieiit t o which the reaction has followed a course other than that represented by equation A .Nearly the whole amount of nitro-group of the picric acid-up to 96-97 per cent.-is accounted for by the chloropicrin and the nitric acid; probably most of the deficiency is due to want of preci-sion in measurement and to the loss of chloropicrin by evaporation during the preparation. Eflect of Degree of 3 llcatiizity O ~ L the Reaction.-According to equation A 23 equivalents of alkali are required by the left-hand side of the equation. The right-hand side however only needs 19 equivalents. Hence during the reaction the alkalinity would increase if 23 equivalents were used initially. Moreover, * Since the work described in this paper was completed Gardner and Fox (T. 1919,115 1188) have recorded that the yield by the Shenstone-Hofmmn method can be raised to 180-190per cent.when the proportion of the reagents and the quality of the bleaching powder are right FROM PICRIC ACID AND TRINITROTOLUENES. 31 6 of these 19 equivalents are required by carbon dioxide regenerat-ing carbonate which is again available for reaction with chlorine. Hence the minimum proportion of alkali for the reaction repre-sented by equation A is 13 equivalents. In equation B 25 equiva-lents of alkali are required on the left-hand side and 27 on the right-hand side; of these again 8 are in the form of carbonate and therefore available; hence the minimum number is 19. I n practice since under the best conditions nitric acid is always formed and therefore the reaction in part follows equation B it is best to use 15-17 equivalents of alkali.I n strongly alkaline media such as sodium hydroxide in place of sodium carbonate the yield is greatly diminished. When the sodium hydroxide is concentrated the react’ion is very slow for the solubility of the picrate is depressed and moreover only hypo-chlorite and not hypochlorous acid is present at least in the initial stages. At the same time a red solid appears as a product. I f the concentration of the sodium hydroxide is kept below 0.lX and the hydroxide (13 equivalents in all) added gradually during the reaction the yield of chloropicrin is as good as when sodium carbonate is used. When bleaching powder is used calcium hydroxide would be formed i f the reaction follows that course (equation A ) in which tlhe maximum yield is obtained thus : 2C,H,(N0,)3*OII -t- llCa(OCl),= GCCI,*NO + 6CaC03 + 2CaC1 + 3Ca(OH),.(Using bleaching powder containing 30 per cent. of “active chlorine,” 1 part of picric acid would require 3-4 parts of bleaching powder.) Owing to the low solubility of calcium hydroxide the aqueous medium in which probably the reaction only takes place, will not have an alkalinity above 0*04-Om02N which would not be an unfavourahle degree of alkalinity. TABLE I. , Yield of chloropicrin. Alkali. Per cent. NaOH 23 equivalents. Concentration N . . ........ 110 Na,C03 9 equivalents; NaOH 8 equivalents. ... 182 Na,CO 3 17 equivalents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 194 Soda ash (Na,CO, 90 per cent. ; NaOH 5 per cent.) 194 Na,CO, 12 equivalents ; NsHCO, 5 equivalents ...196 T”he temperature was in all experiments 2-5O. The Effect of Temperature.-A low temperature is favourable to the yield of chloropicrin that is t o the reaction represented b 32 ORTON AND McKlE PREPARAT'ION OF CHLOROPICRIN equation A . In table 11 17 equivalents of sodium carbonate were used throughout. TABLE 11, Temperature. Yield. 16-17O 168 per cent, 13-14*5" 173 1 oo 182 2-5O 192-1 94 O0 198-199 Only a small amount of heat is set free in the reaction when sodium carbonate is used. Effect of the Presence of Sodium C'h1oride.-The presence of sodium chloride is deleterious to the reaction in which chloropicrin is formed thus in 18 per cent. aqueous sodium chloride the yield was 149 per cent. and in 30 per cent. sodium chloride 92 per cent.The '' red solid " is formed in considerable proportion especially in the more concentrated salt solution. Owing to the depression of solubility in water of chlorine by sodium chloride the gas is absorbed poorly. Further the high concentration of chloridion keeps the concentration of free hypochlorous low (Jakowkin Zeitsch. physilcal. Chem. 1899 29 613) and the solubility of the sodium picrate is depressed by the sodium chloride; hence the reaction will be retarded. Again the concentration of chlorine will be greater, and any reaction with picric acid not leading t o chloropicrin there-fore favoured. Use of the filtrate (which contains about 8 per cent. of sodium chloride) from one operation is therefore inadvis-able; a second re-use causes a serious diminution of yield.It is not improbable that this effect of chloride accounts for the great in5uence of " quality " of the bleaching powder on the yield of chloropicrin when this agent is used. E X P E R I M E N T A L . Picric acid is dissolved in a hot solution of 4 parts of sodium carbonate (17 equivalents) in 50 parts of water. On rapidly cool-ing sodium picrate separates in small crystals. Large crystals should be avoided. 'The thin paste is cooled to below 5O and stirred slowly while a current of washed chlorine is introduced. The treat-ment with chlorine should either be intermittent or fairly slow. Too rapid a current of chlorine not only leads to loss of gas but also t o the production of chlorate. The speed of the reaction is mainly determined by the size of the crystals of the sodium picrate.The scdium picrat'e gradually dissolves and ultimately a colourless oil and a colourless solution are obtained. When industrial chlorin RROM PlUBlC ACID AND TRINlTROTOLUlGNES. 33 has been used the oil is yellow. The oil can easily be directly sepa-rated from the aqueous layer or distilled in a current of steam. It amounts to 1-17 parts by volume and is approximately pure chloropicrin. Solubility of G'kloropicrin in Water.-At loo the solubility is about 0.058 gram per 100 C.C. It rises somewhat with the tem-perature. By vigorous distillation 75 per cent. of the chloropicrin can be recovered from the solution. A smaller proportion can be salted out. 'The aqueous solution is stable for a long period and remains neutral after boiling for some time.Action of Hypochlorite Solution o n o- and p-Mononitro- and 2 4-Binitro-phenol.-2 4-Dinitrophenol behaves much as picric acid. There is a greater development of heat and ultimately a colourless oil and solution are obtained. The yield of chloropicrin is only 50 per cent. of the maximum. p-Nitrophenol gives a t first a heavy precipitate which ultimately dissolves yielding a colourless oil and solution. The yield oi chloropicrin is 33-34 per cent. of the maximum. o-Nitrophenol gives a deeply coloured precipitate and liquid. The solid resists t I eatment wilh hypochlorite. The yield of chloropicrin is only 10 per cent. of the maximum. Action of Nypochlorite O I Z Trinitrotoluene and on Trinitrotoluene Residues.-As these materials are insoluble in alkali contact is most easily effected by " sludging " with water and bleaching powder. As a result of many trials the proportion of 1 part of nitro-compound to 15 parts of bleaching powder (" active chlorine," 29 per cent.) and 25 parts of water were found best. The mixture is gradually heated and then a current of steam passed through. If the mixing has been thorough the colour of the paste is completely discharged save from trinitrotoluene residues. TABLE 111. Yidd ~ ~ 1 3 a. percentage of weight of Material used. material used. T.N.T. Grade I. ..................... 82 T.N.T. Grade 111. .................. 84 T.N.T. '' residues " .................. 70 Dinitrotoluene ........................ 4 s-Trinitrobenzene .................. 53 UXIVERSITY COLLEGE OF N. WALES, BANGOR. [Received NovembeT 22nd 1920.1 VOL. CXIY.

ISSN:0368-1645    

DOI:10.1039/CT9211900029

出版商:RSC    

年代:1921

数据来源: RSC

摘要:

34 CHATTAWAY AND RAY: 11.- The Decmyiosition of Tartaric Acid by Heut. By FREDERICK DANIEL CHATTAWAY and FRANCIS EARL RAY. ALTHOUGH the decomposition which tartaric acid undergoes when heated has been studied many times during the past hundred years there is no general agreement as t o the substances produced or as to their relative amounts nor has the course of the decomposition been made clear. Since many of the products described by previous observers are obviously the result of secondary reactions the decomposition has been carried out a t the lowest possible temperature and under diminished pressure. As under these conditions the primary products are removed immediately they are formed any side-reac-tions might be expected t o be avoided or reduced to a minimum.When heated in this way no substances of complicated structure are formed but the tartaric acid decomposes in two stages; in the first water alcne is liberated ; in the second carbon monoxide and carbon dioxide are produced together with formic acetic and pyruvic acids. The reactions which occur during the heating may be explained as follows: The tartaric acid a t first loses one molecule of water and there is produced a solid colourless substance of the nature of a lactide having half the acidity of the parent acid and reconvertible into it by hydrolysis. CO,H*CH (0 11 ) CH (OH) *C'O,H This stage may be formulated thus: -+ CO,H* CH( OH) *yH*yO CO,H*CH (OH) CH( OH) C0,H 2H20+ o i) I I CO-CH*CH (OH)*CO,H This loss of water must be followed a t a somewhat higher tem-perature by an intramolecular rearrangement of the nature of the Beckmann transformation hydrogen and hydroxyl changing places, thus : OH 13 H OH I 1 CO,H*CH-C-CO I I CO,H*CH*C-CO -+ I I 0 0 I I 0 0 I I I I COG-CH* C0,H CO* C-CH* CO,H 1 1 I t H OH OH THE DECOMPOSITlON OF TARTARIC ACID BY HEAT.35 The compound momentarily formed in this manner then breaks down in two ways producing in one decomposition carbon monoxide, carbon dioxide and acetic acid t h u s : Co2H'CH,*C(oH)*Co CO,H.(3H + CO + (lo I 0 b GO + CO + CH,*CO,H 1 I CO-C( OH) *CH,*CO,H and in the other decomposition carbon dioxide and pyruvic acid a ti ansf erence of hydroxyl again taking place thus : Cc),H*CH2*C( 0 E3)*CO I I 0 0 -+ I I UO--U(UH)*CH,*CO,H CH,* C(0H) *CO I.I 2c0 + 0 I I 0 c'o-- C(OH)*CH, The formic acid which is prodnced in sinall amount in the decom-position is probably formed by an intramolecular rearrangement of the undehpdrated acid followed by a rupture of the molecule similar to that which occurs when a tartrate is fused with sodium hydr-oxide the oxalic acid which is one of the primary products of the decomposition subsequently breaking down into carbon dioxi'de and formic acid. C02H C0,H CO,H I I I CH, CH*OH 1 CO,H E X P E R I M E N T A L . The heating was carried out in a bath of fusible metal the bulb of the flask being completely immersed. Reduction of pressure was effected by a water-pump or by a Sprengel pump when the gases were to be examined.Heating was not begun until the pressure had been reduced as far as possible. During the heating a pressure of 10-20 mm was maintained the pressure varying somewhat with the stage of the decomposition and the rapidity of the accompanying evolution of gas. The liquid products were condensed in one or more strongly cooled c 36 CHnTTAWAY AND RAY: receivers whilst the escaping gases after having been passed through cotton-wool were collected over mercury. Tartaric acid when heated in this way melts when the tempera-ture of the bath reaches about 150° and appears to boil vigorously, a clear colourless liquid condensing in the receivers. I f the pressure is kept at 19-15 inm. and the temperature of the bath not allowed to rise above 1 6 5 O the distillate is neutral but it becomes slightly acid if this temperature is exceeded.As the decomposition proceeds, the temperature of the bath being raised a few degrees above 165O, the contents of the flask gradually become more viscid a slight evolution of gas occurs and care is needed to prevent the mass distended by this gas and by water-vapour from frothing over. After some time tjhe frothing ceases liquid no longer condenses, and action a t this temperature appears t o come to an end. T'he contents of the flask if cooled a t this stage have a white spongy appearance somewhat resembling dried bread. When the temperature of the bath is further raised to about 180° action recommences the mass darkens slightly gas is very freely evolved and a clear yellow liquid of a pungent odour distils over.This decomposition continues until the whole mass has dis-appeared a very slight carbonaceous residue only being left behind in the flask. When a low pressure is maintained and the heating is slowly and carefully conducted this small amount of residue is unweighabl; and negligible. The liquid obtained in the first stage of the decomposition is water 1 gram-molecule approximately being given off by each gram-mclecule of tartaric acid. 'T'he colourless spongy solid then remaining is undoubtedly a compound of t.he nature of a lactide. It is brittle absorbs moisture from the air and therefore becomes sticky on exposure. It does not dissolve appreciably in benzene chloroform or ether. It dissolves very sparingly in cold water more freely in hot.When quickly dissolved in cold water it is neutralised by little more than half the amoant of alkali required to neutralise the parent acid. Such a neutralised solution becomes again acid on keeping or heating until finally the amount of alkali required for neutralisa-tion equals that which would have been required to neutralise the tartaric acid from which it was derived. On thus neutralising a large amount with potassium hydroxide and crystallising the salt in eight successive crops each proved to be ordinary neutral potass-ium tartrate,. On boiling it with ethyl alcohol and distilling under reduced pressure ethyl tartrate was obtained. The gas obtained in the second stage of the dewmposition con THE T)ECOMPOSITION OF’ TARTARIC ACID BY REAT. 37 sisted of carbon nionoxide and carbon dioxide roughly in the pro-portion of one volume of monoxide t o two volumes of dioxide.If the first stage of the heating is not carried out very slowly and the teniperature of the bath is allowed t o rise rapidly t o effect ccmplete decomposition more quickly the percentage of carbon dioxide in the evolved gas is considerably increased owing to the greater amount of tartaric acid decomposing without the initial formation of the lactide. The liquid distilling in the second stage of the decomposition is a mixture of formic acetic and pyruvic acids no other substances being produced. By fractionation under diminished pressure the distillate was resolved into its three constituents and each was separately purified and identified.The amount of each acid yielded by a known weight of tartaric acid was estimated the formic acid by Franzen and Greve’s method (J. pr. Chem. 1909 [ii] 80 383) the acetic acid by titration and the pyruvic acid by conversion into its p-bromophenylhydrazone. The average of several concordant esti-mations gave the following as the products obtainable by theadistil-lation of 1 gram-molecule of tartaric acid (150 grams) under diminished pressure and a t a temperature not much exceeding 180° water 18.8; formic acid 2.4; acetic acid 49; pyruvic acid, 14.1; carbon monoxide 21.3; carbon dioxide 43 grams a total less by 1.4 grams than the weight of acid used. The substances termed by Fremy (Annalen 1839 29 142) tar-tralic and tartrelic acids represent stages in the formation of the acid lactide which together with water is the sole product of the first stage of the decomposition. The formation of tarry matters and the subsequent charring which occur when tartaric acid is heated under the ordinary pressure are due to the decomposition of the pyruvic acid first formed and in no respect differ from the changes which take place when this acid is similarly heated. THE QUEEN’S COLLEGE OXFORD. [Received. November 26th 1920.

ISSN:0368-1645    

DOI:10.1039/CT9211900034

出版商:RSC    

年代:1921

数据来源: RSC

摘要:

38 YEOMAN TRITI-ITOOARBONATES AND PERTHIOCARBONATES. By ERNEST WICKHAM YEOMAN. THE fact that carbon disulphide reacts with soluble sulphides was first observed in 1821 by Zeise and the products were more fully investigated by Berzelius in 1826 ( A 7211. I ’ h p . Clbem. 1826 [ii] 6, 450) who showed that the salts produced are Lhe sulphur analogues of the carbonates and may be regarded as formed by direct coln-bination of carbon disulphide and sulphide. Berzelius prepared scluble and insoluble trithiocarbonates of most of the then known nietals but pointed out that owing t o their instability and ready loss of carbon disulphidc it was very difficult to obtain them in a pure condition. Since that date numerous publications refer t o the formation and preparation of trithiocarbonates + but except in the case of a number of donble salts of calcium trithiocarbonate and calcium hydroxide scarcely any of these appear to have been obtained in a pure condition.I n addition organic derivatives of orthothiocarbonic acid C(S€I)4 have been prepared such as ethyl orthothiocarbciiate (Claesson ,7. p r . Chem.. 1877 [ii] 15 212) but, as in the case of the corresponding orthocarbonic acid no inorganic salts have been obtained. It was generally supposed that the absorption of carbon d i d -phide from crude coal gas when this is purified by means of lime, was due t o its absorption by calcium sulphides with the formation of calcium trithiocarbonate. Colman (Thorpe’s ‘‘ Dictionary of Applied Cheniistry,” 2nd edition article “ Coal-gas ”) as the result of an investigation of the absorption of carbon disulphide by “sul-phided lime,” suggested that the active compound was calcium disulphide which readily combines with carbon disulphide a t the ordiiiary t cmperature forming not the trithiocarbonate but a new salt, t>he perthiocarbonate CaCS, thus CaS + CS = CaCS,.This a t once accounts for the known necessity for the presence of some oxygen for absorption to take place oxygen in limited quant)ity being required to bring about the fornistion of the disulphide from ihe hydrosulphide first produced 2Ca(SH) + O,= 2CaS2 -I- 2H@. Colman drew this conclusion since he found that the soluble monosulphides or hydrosulphides free from any polysulphide had * Abstract of Thesis approved for M.Sc. Degree (London).t These salts are commonly termed “ thiocarbonates,” but the same term is sometimes used for the derivatives of monothiocarbonic acid HS’CO’OH or HO’CS’OH. To avoid confusion the term ‘‘ trithiocarbonate” is used throughout this communication for the derivatives of the acid HS’CS’SH YEOMAN TRITHIOCARBONATES AND PERTITIOCARBONATES. 39 little if any action 011 carbon disulphide a t the ordinary tempera-ture but that if slifficientj sulphur were added to convert them into the disulphides tlhe reaction with carbon disulphide took place rapidly with considerable evoliztion of heat and the formation of a conipletely soluble product. If however more sulphur were added than was required to produce the disulphide of the metal the combination with carbon dis-dphide took place equally rapidly but the extra sulphur added over and above that required to form the disulphide was then precipitated as eleinentsry sulphur.It was also found that solutions of the normal trithiocarbonates readily dissolved sulphur and that the amount of sulphur taken up by any of these trithiocarbonate solutions was limited to one atom for each molecule of trithiocarbonate present. All these results pointed to the existence of a series of thiocarbonates containing one more atom of sulphur bhan the salts usually termed the trithiocarhonates ; these may be regarded as salts of the acid H,CS, which may be called perthiocarbonic acid. The detailed result,s of this investigation were not published as i t was found that almost similar observations had been published by G6lis (Compt.r p n d . 1875 81 282).* Since that date K. A. Hofmann (Zeitsch. tcnorg. Chem. 1897 14, 263; Ber. 1903 36 1146) has described numerous double thio-carbonates obtained by the action of carbon disulphide on ammonia-cal solutions of copper and other metallic salts and whilst most of these were derivatives of trithiocarbonic acid H,CS, he also obtained substances which were derivatives of perthiocarbonic acid, H,CS, one of these the copper salt having been obtained as bronze crystals CuCS, and analysed but no solnble perthiocarbonate appears yet to have been isolated in a pure condition; the various soluble trithiocarbonates also appear for the most part only to have bcen obtained in an impure state and probably have rarely been free from some admixea perthiocarbonate and thiosulphate.E X P E R I M E N T A L . As is well known the soluble sulphides all undergo hydrolysis in aqueous solution t o a considerable extent and both polysulphides and thiosulphates are formed in the presence of even small amounts of oxygen (Divers T. 1884 45 696; Bloxam T. 1900 77 750). Rule and !l%omns (T. 1911,99 558) have shown that pure hydro-sulphides of the alkali metals free from thiosulphate may be * Dammer (“ Handbuch der anorganischen Chemie,” 1894 Band 2 Theil 1, p. 412) and Beilstein (‘‘ Handbuch der organischen Chemie,” 1893 Band 1, p. 887) incorrectly refer to these compounds as derivatives of orthothio-carbonic wid C(SH), 40 YEOMAN TRTTTTTOCARRONATRS AND PERTTTTOCARRONATES. obtained by the action of hydrogen sulphide on an alcoholic solu-tion of the ethoxide and that on addition of sulphur t o the solu-tion pure polysulphides of the metals are obtained.The various sulphid es and polysizlphides of sodium and potassium required for the preparation of the alkali salts described below have all been obtained in this manner. Air and moisture have been excluded so far as practicable by oarrying out all the operations in a current of dry hydrogen. Methods of Analysis. Carbon and water were estimated by combustion of the salt mixed with lead chromate. Calcium was estimated as oxalate the other metals as sulphates. The total sulphur was estimated either by the Carius method or by combustion with lime. Oxidation of the sulphizr by bromine or other agents gives low results.To determine whether the compounds formed were pure other evidence is required besides that of the elementary analysis. For this purpose the quan-tity of sulphur ( a ) present as thiosulphate ( h ) evolved on acidifi-cation as hydrogen sulphide ( c ) present as " polysulphide " sulphur, was detlermined in addition to the total sulphur. A solution of cadmium clilcride was added t o a solution of the salt and the precipitate filtered etc. ; thiosulphate ( a ) was estimated in the solu-tion and the Eulphur evolved on acidification as hydrogen sulphide (6) in the precipitate by means of N / 10-iodine. " Polysulphide " sulphur was estimated by addition of cadniium chloride to another portion of the dissolved salt and determining the escess of sulphur 0~7er that present as cadmium sulphide by filtering washing and dissolving the precipitate in hydrochloric acid ; (,he " polysulphide " sulphur can then be filtered etc.and weighed. Alternatively the precipitate can be dried extracted with hot benzene {'he benzene evaporated and the residual sulphur weighed. Sodium Tri fi hio car b ona 8 e . Two grams of sodium were dissolved in 60 C.C. of absolute alcohol in a flask fitted with a reflux condenser; the air in the flask was displaced with dry hydrogen and the solution saturated with dry hydrogen sulphide. To the alcoholic solution of sodium hydro-sulphide thus obtained a slight excess of freshly distilled carbon disulphide was added ; hydrogen sulphide was immediately evolved, and the colour of the solutim became dark red.The solution was warmed to 60° dry ether added until a faint turbidity appeared, and the flask allowed to cool slowly in a current of hydrogen. The pinkish-yellow crystalline precipitate was filtmed in an atmospher YEOMAN TRITHIOCARBONATES AND PERTHIOCARBONATES. 41 of hydrogen washed with dry ether and dried in a brisk current of liydrogen a t 609* (Found (217.1; H,O=10.4; Na=26*8; total S = 56.2 ; S evolved as H,S = 17.7.f Na,CS,,H,O requires C= 6.97 ; H,O = 10.43 ; Na = 26-72 ; total S = 55.88 ; S evolved as &S = 18-63 per cent.). Sodium trithiocarbonate forms very deliquescent needles which have a pinkish-yellow colour and give a distinctly red aqueous solution. This colour especially in dilute solution seems t o be characteristic of all the soluble true trithiocarbonates and is markedly different from the distinctive yellow colour of the solu-tions of the perthiocarbonates.The salt is very soluble in water and dissolves in alcohol much more readily than the potass-ium salt although much less readily than sodium perthiocarbonate. It is insoluble in ether or benzene both of which liquids precipitate it from alcoholic solution. It is stable in dry air free from carbon dioxide but if moisture is present it quickly oxidises and decomposes losing carbon disul-phide. The crystals first deliquesce then lose their colour and become solid owing to the formation of sodium thiosulphate and hydroxide the latter being converted into carbonate in the presence of carbon dioxide. The course of the change is probably: Na,CS = Na2S + CS ; Na,S + H20 = NaSH + NaOH.2NaSH + 0 = Na,S + H,O ; Na,S + 3 0 = Na,S,O,. This receives confirmation from the fact that such a decomposed product contains thiosulphate and has an alkaline reaction and that in the case of the perthiocarbonates nearly pure thiosulphate results. Unless the carbon dioxide of the air has access no carbonate is formed. On strongly heating the salt decomposes into sodium sulphide and carbon disulphide. I f water is absent the salt is stable when heated in a stream of hydrogen to 60° but a t about 7 5 O carbon disulphide begins to escape the loss however not being very great even a t looo. A current of dry air free from carbon dioxide does not cause more decomposition of the dry salt than hydrogen.An aqueous solution remains stable if oxygen and carbon dioxide are rigidly excluded but i f oxygen is present loss of carbon disul-phide ensues with subsequent hydrolysis and oxidation of the sulphides producing thiosulphate and polysulphide ; the latter then loses sulphur t o any unaltered trithiocarbonate forming perthio-carbonate which in its turn loses carbon disulphide and by oxida-* A little xanthate is formed but remains in the solution (compere Holmberg, t " Polysulphide " sulphur and thiosulphate were present in traces only. J . p r . Chem. 1906 [ii] 73 239). 0 42 YEOMAN TRITHIOCARBONATES AND PEBTHIOCARBONATES. tion is transformed t,o thiosulphate; the colour of the solution a t first red becomes yellow and finally vanishes. Berzelius (Zoc.c i t . ) gave the following equation for the reaction between water and trithiocarbonates : Na,CS -I- 3H20 = Na,CO + 3H,S. It will be shown later that this equation represents the reaction only under certain conditions. Sodium trithiocarbonate when dis-tilled with air-free water excluding air and carbon dioxide gives off hydrogen sulphide and loses all its carbon disulphide which car! be recovered as such in the distillate aiid the residue contains sodium sulphide and its hydrolytic products but no carbonate and only traces of thiosulphatje the latter being due to the presence of a small quantity of air. Tarugi (Gazzetta 1909 39 i 405) also found this to be the case. I f a stream of air free from carbon dioxide is clrawii through a boiling solution of the trithiocarbonate, only a portion of the carbon disulphide can be recovered; part of it becomes converted to the carbonate and thiosulphate also remains in the solution.It was found on experiment that varying amounts of the carbon disulphicle up to 25 per cent,. were thus converted, ooly partial agreement being obtained with Tarugi (Zoc. cit.) who gives an equation demanding a 50 per cent. conversion: 2Na2CS3 + 2H,O + 4 0 = Na,S,O + CS + Na,C03 + 2H,S. If an air-free solution of the salt is heated in a sealed tube a t 100' carbonate is also formed and on opening the tube much hydrogen sulphide formed on hydralysis escapes. The reactions are as follows : Na,CS = Na,S + CS ; Na,S -t- 2E,O = 2NaOH -t 2H2S ; 6NaOH + 3CS = Na,C03 + 2Na,CS3 + 3H20. The trithiocarbonate formed again decomposes and the reaction, after prolonged heating reduces t o the one represented by the equation given by Berzelius.Experiment showed that the reaction is never quite complete the amount. of carbonate tending however, t9 approach the theoretical amount after a long time. I f air is present thiosulphate and polysulphide are formed as well. It should be noted t,hat Chancel aiid Parmentier (Compt. rend. 1884, 99 892) fonrid that on heating carbon disulphide with baryta water more barium Carbonate is formed than corresponds with the equation : 3CS + 3Ba(OH) = BaCO + tLBaCS -t- 3E€,O, and that the reaction should be represented by CS + 2Ba(OH) = BaCO + Ba(SH) + H,O ; this is in accord with the above explanation but the barium hydro YEOMAN TRITHIOCARBONATES AND PERTHIOCARBONATES.43 sulphide is not hydrolysed t o such an extent as in the case of the sodium salt. Carbon dioxide decomposes both the salt and its solution form-ing the carbonate and carbon disulphide; it is this reaction that is responsible for the carbonate found by many investigators. Sulphur dioxide converts the salt into the sulphite with loss of carbon disulphide. A solution of the salt dissolves a constant weight of sulphur, namely one atom of sulphur to one molecule of trithiocarbonate, thus confirming the observations of GBlis and Colman. I f the salt is impure then the amount of sulphur taken up varies according to the amount of polysulphide that has been formed. Tbis in con-junction with the results of thermochemical experiments to be described later confirms the view of GBlis and Colman that a new compound had been formed differing from the trithiocarbonates in containing an additional atom of sulphur.Sodi urn Pe I’ t hio car b ona t e. Sodium (2.3 grams) was dissolved in 40 C.C. of absolute alcohol in the same manner and with the same precautions that were taken i s the preparation of the trithiocarbonate. To tlhis solution a solu-tion of 2’3 grams of sodium in 40 C.C. of alcohol was added thus forming an alcoholic solutiori of sodium sulphide which was con-verted into the disulphide by the addition of 3.2 grams of sulphur. A slight excess of carbon disulphide was added the colour of the solution changing from yellow to red.‘ On addition of ether to this perthiocarbonate solution a reddish-yellow oil was precipitated, which slowly solidificd to a microcrystalline mass of brownish-yellow needles.On keeping the filtrate deposited a further amount in nodular aggregates of prismatic doubly refracting needles. The crystalline mass u7as collected washed with ether in an atmosphere of hydrogen and finally dried a t 60° in a stream of the same gas. Altern ativeiy the sodium diaulphide required may be prepared by the direct addition of sulphur to the sodium hydrosulphide without addition of a second molecule of sodium ethoxide the disulphide being then formed with the evolution of hydrogen sul-phide (Rule and Thomas Zoc. c i t . ) Working in this manner thio-sulphate is less likely to be present in the perthiocarbonate produced (Found C = 5.2 ; H,O = 22.2 ; Na = 19.6 ; total S = 53.8 ; polysul-phide,” S = 13.7 ; S evolved as H,S = 13*7.* Na,CS,,3H20 requires C = 4.99 ; H20 = 22.50 ; Na := 19.14 ; total S = 53.37 ; “ polysulphicle,” S=13.34; S evolved as H,S=13’34 per cent.Na2CS3,5H,0 * Thiosulphate present as a trace only. c* 44 YEOMAN TRITHIOCARBONATES AND PERTHIOCARBONATES. requires C = 4-92 ; H,O = 36.86 ; Na = 18.83 ; total S = 39.39 ; S evolved as K,S = 13-13 per cent.). The salt is very deliquescent dissolves readily in water forming a distinct yellow solution (compare trithiocarbonates) and is soluble in alcohol being precipitated therefrom by ether or benzene. I n dry air free from carbon dioxide the salt is stable but in mcist air it quickly decomposes losing carbon disulphide the residue being oxidised to almost pure thiosulphate (Found Na = 19.3 ; S =25*4.Na2S20,,5H,0 requires Na = 18.55 ; S =25*80 per cent.) the reactions on oxidation being : NasCS = Na,S + CS ; Na2S2 4- 3 0 + 5H,O = NazS,0,,5H,0. On heating the dry salt behaves in a similar manner to the tri-t,hiocarbonate except that the disulphide remains in place of the monosulphide. In the absence of oxygen the aqueous solution remains stable for a long time; if air is present the solution loses carbon disulphide, and becomes colourless thiosulphate remaining in the solution. On heating the air-free aqueous solution in a sealed tube thio-sulphate is always formed owing to the reaction between the poly-sulphide sulphur and the hydroxide produced by hydrolysis.On ccoling some sulphur separates and on opening the tube much hydrogen sulphide escapes. The reactions are the same as in the case of the trithiocarbonate except that the polysulphide sulphur always gives rise to thiosulphate. Finally after prolonged heating, nearly all the perthiocarbonate is converted into the carbonate. A solution of the salt distilled in the absence of air loses all carbon disulphide which can be recovered as such in the distillate: 0.3180 CS present as perthiocarbonate gave 0.3160 CS in the If however a current of air free from carbon dioxide is passed through the boiling solution some carbonate is formed but not to the extent demanded by the equattion given by Tarugi (Zoc. cit.), thus : 0.2820 CS present as the perthiocarbonate yielded 0.0120 CO = Many such experiments were carried out but the 50 per cent.conversion was never attained. I n every case the carbonate formed was Precipitated as barium carbonate collected washed and treated with dilute hydrochloric acid a little potassium dichromate being added to oxidise any sulphide remaining. The carbon dioxide set free after drying was collected in soda-lime tubes and weighed. Carbon dioxide quickly decomposes the salt with the formation of a carbonate and sulphur and the evolution of carbon disulphide distillate = 99.5 per cent. Carbonate in residue = nil. 0*0208 ; CS = 7.4 per cent. conversion YEOMAN TRITHIOCARRONATES AND PERTHIOCARBONATES. 45 and hydrogen sulphide. into thiosulphate and sulphur with loss of carbon disulphide : Sulphur dioxide completely converts it 2Na2CS4 + 3S0 = 2Na,S20 + 3s + 2CS2.According to the statements of GBlis the salt should not dissolve sulphur ; experiment confirmed this. (1) 0.8400 of the salt was dissolved in air-free water and allowed to remain with shaking for a long time with 0.2000 of sulphur; on filtering washing etc. sulphur recovered = 0.2000 = 100 per cent. (2) 0.6530 of the salt and 0.5000 of sulphur; sulphur recovered was 0.4930 = 98.6 per cent. m e additional sulphur atom in the perthiocarbonates is readily removable by reagents which have a direct action on sulphur such a3 hydrocyanic acid or sodiizni cyanide. When excess of the latter reagent is added to the pure yellow solution of the perthiocarbonatc the colour soon changes from yellow to the characteristic red of the t,rithiocarbonates the additional atom of sulphur being removed and converted by the cyanide into thiocyanate.HEAT EVOLVED BY COMRINATION OF CARBON I)ISULPHIDE WITH ( a ) SODIUM SULPIIIDE ( b ) SODIUM DISULPHIDE. It has already been stated that when carbon disulphide is dis-solved in a solution of sodium polysulphide the reaction is quicker and more heat is evolved than when the monosulphicle is employed. The heats disengaged were determined in an approximate manner by employing a simple calorimeter. The results obtained in this way whilst not possessing a high degree of accuracy give good com para tive figures. The react?ions to be considered take place too slowly in aqueous solution to permit of any calorimetric determinations so that absolute alcohol was employed as the solvent.It was found that : (I) Na,S + CS + alcohol = Na2CS3 + alcohol + 5700 cals. (2) Na,S2 + CS + alcohol = Na2CS4 + alcohol + 8550 cals. Na,S + S + alcohol = Na,S + X cals. Na2CS3 + S + alcohol = Na,CS4 + Y cals. take place too slowly and the apparatus a t the author's disposal did not permit of other determinations. It is however probable that the values of X and Y would not differ very much from those found using water as the solvent. Sabatier (Gompt. rend. 1880, 90 1557) found that: The reactions : Na + El + S + aq. = Na,S,aq. + 103,400 cals. Na + S + aq. = Na,Saq. + 102j000 cals. 46 YEOMAN TRITHIOCARRONATES AND PERTHIOCARBONATES. therefore : Na,S + S +- aq. = Na,S,aq. + 1400 cals.Assumiiig that the same evolution of heat occurs in alcoholic solution then Na2CS + S + alcohol = Na2CS + alcohol + 4290 cals. Hence in the formation of the perthiocarbonate by the addition of sulphur to the trithiocarbonate the heat evolved is three times that evolved in the formation of the disulphide from the mono-sulphide. T t therefore appears unlikely that mere solution or polysulphide formation has taken place. Pot as.siun& Tri t hiocar b ona t e . Two grams of potassium were dissolved in absolute alcohol and converted into the hydrosulphide with the same precautions as were taken in the preparation of the sodium salt the femperature of the solution being kept a t 45-50° and the proper amount of carbon disulphide added. On allowing the solution to cool slowly a yellow crystalline substance separated which was collected washed with dry ether and dried in a brisk current of dry hydrogen a t about 45O (Found c‘=6*1; H,O=l*O; K=41*6; total S=50.9; S evolved as H,S= 17*0.* K,CS requires C=6.44; K=41.95; total S=51.61; S evolved as H,S=17.20 per cent.).The salt can thus be considered as anhydrous; further efforts to remove the last traces of water resulted in its decomposition. The salt behaves in a manner entirely analogous to sodium trithio-carbonate i t is leas readily soluble in alcohol but exceptionally deliquescent in moist air ; aqueous solutions have the typical red colour and are capable oE dissolving one atom of sulphur for niolecule of the salt. Potassium Pert Iziocnrbonate. Two grams of potassiuin were converted into the polysu with the usual precautions; this was brought to a temperature of 40° and the requisite amoiznt of carbon disulphide added; on cool-ing slowly a yellow crystalline substance separated (not an oil as in the case of the sodium salt) which was collected washed with dry ether and dried in hydrogen at 45-50° (Found C 15.3 ; H,O =4*7 ; K = 34.6 ; total S = 56.2 ; ‘’ polysulphide ” S = 14.0 ; S evolved as H,S = 14-1.-f K,CS,,$H,O requires C = 5-28 ; H,O = 3.96 ; K = 34.39 ; total S = 56.37 ; ‘‘ polysulphide ” S = 14.09 ; S evolved as H,S = 14.09 per cent.). Attempt,s to dry the salt further resulted in it’s decomposition. * ‘‘ Polysulphide ” and thiosulphate present in traces only. every phid YEOMAN TRITHIOCARBONATES AND PERTHIOCARBONATES.47 The salt behaves in a similar way to the corresponding sodium com-pound; i t is more deliquescent less readily soluble in alcohol and, like all the perthiocarbonates will not combine with sulphur. C'alcium I'rithiocarbonates. All attempts to prepare the simple trithiocarbonate gave double compounds of calcium trit'hiocarbcnate and calcium hydroxide of the type previously described by Sestini (Gazzetta 1871 1 473), Walker (Chem. ATews 1874 30 28) Veley (T. 1885 47 478) and O'Donoghue and Kahan (T. 1906 89 1812). From aqueous solu-tions the author obtained reddish-yellow needles of the composition 3Ca(OH),,CaCS3,9H,O a i d from alcoholic solutions similar needles ccxresponding with the formula Ca(OH),,CaCS,,ZH,O. These basic compounds are more stable than the trithiocarbonates of sodium and potassium probably because they are less hygroscopic; in other respects they behave in a similar manner.It may be pointed out that in the case oE these basic salts it is scarcely possible to decide on the evidence of the elementary analysis alone whether they consist of basic trithiocarhonates or basic perthiocarbonates ; to decide this point the amount of sulphur evolved as hydrogen sul-phide or precipitated as sulphur on the addition of acid must be determined as well as the tlotal sulphur. The colour of the dilute sclution and its action on sulphur afford further evidence. The compounds described above evolve one-third of their sulphur as hydrogen sulphide on acidification give no polysulphide sulphur in dilute solution have the characteristic colour of the trithiocarbon-ahes and dis2 olve sulphur forming the yellow perthiocarbonate sc-lution.Calcium Per thiocar bonat es. Pure lime was converted into an aqueous solution of the poly-sulphide with the usual precautions the polysulphide then con-verted to the perthiocarbonate by the passage of a stream of hydro-gen saturated with carbon disulphide vapour and on evaporating t'he solution in a vacuum dark red needles were deposited (Found, c' = 2.2 ; H20 = 34.6 ; Ca =24.4 ; total S = 26.4 ; polysulphide S = 6-7 ; S evolved as H2S= 6*6.* CaCS4,2Ca(OH),,8H,0 requires C=2.54 ; H20 = 38.14 ; Ca = 25.43 ; total S = 27.12 ; polysulphide S = 6.78 ; S evolved as &-S = 6-78 per cent.). If alcoholic solutions were employed additlion of ether precipi-tated oils which took a long time to crystallise; the crystals dis-* Thiosulphate present as a trace only 48 YEOMAN TRTTHTOCARBONATES AND PERTKTOCARDONATRS.solved in water forming yellow solutions which gave the reactions for the perthiocarbonat,es but contaihed large and varying amounts of thiosulphate. On drying in a vacuum or in a current of hydro-gen they decomposed leaving a residue of hydrated calcium pol ysulphides. Barium Trithiocarb ona t e a Veley (T. 1886 49 369) states that although barium trithio-carbonate exists as a yellow substance yet owing to its instability he was unable to analyse it. Holmberg (Zoc. cit.) by the action of barium chloride and formaldehyde on a freshly prepared solution of potassium trithiocarbonate obtained a yellow amorphous substance, the analysis of which agreed with the formula BaCS,.In view of hhese facts Veley 's experiments were repeated. An aqueous solution of barium hydrosulphide was prepared from tlhe hydroxide with the usual precautions and this converted to the hrithiocarbonate by passage of hydrogen saturated with carbon disulphide. Addition of alcohol to this red solution precipitated a yellow substance which was collected and dried in a current of hydrogen or in a vacuum (Found C=4.9; Ba=55*8; total S= 39.4; S evolved as HzS=13m7; polysulphide S=O-3; S as thiosul-phate= 0.4. BaCS requires C = 4.90 ; Ba = 55-95 ; total S = 39.15 ; S evolved as H,8=13.05 per cent.). T'his compound can also be prepared in a slightly different way by suspending barium hydroxide free from carbonate in alcohol and removing the air with hydrogen; on passing a stream of hydrogen saturated with carbcn disulphide vapour the barium hydroxide finally disappears and a yellow precipitate remains which is collected and dried in a vacuum (Found C=5-2; Ba=56*0; S = 39.0 * per cent.).T'he yellow substance formed in either way is microcrystalline, insoluble in alcohol and sparingly soluble in water giving a red solution. Berzelius noted that the dilute solution was red but thought that the proper colour was yellow. Contrary to the state-ments of Veley the salt is comparatively stable for whereas all the other trithiocarbonates gradually decompose when kept in a stoppered bottle the barium salt remains unchanged for a very long time this being probably due to the fact that it is less hygroscopic than the other salts.A solution of the salt dissolves one atom of sulphur for each molecule of barium trithiocarbonate the colour changing from red t o yellow for example : (1) 0.6040 BaCS was dissolved in air-free water the vessel being * Thiosulphate and polysulphide were present i n traces 0711~ YEOMAN TRITHIOCARBONATES AND PERTHIOCARBONATEfi. 48 filled to the cork 0.5500 pure sulphur added and the vessel allowed to remain with continual agitation for a long time. After filtering, etc. the sulphur remaining was 0.4640. Sulphur dissolved = 0.0860 = 14-2 per cent. of the BaCS,. (2) BaCS taken 1.9360; S dissolved 0*2590=13*5. BaCS by theory can take up S=13*04 per cent.m e variation from the theoretical is due t o the fact that the salts used were not completely pure; the solution obtained from the latter experiment was mixed with sulphur and after eight weeks the extra sulphur dissolved was only 0.0020 gram. Barium trithiocarbonate behaves in a similar manner to the sodium salt on heating both when dry and in aqueous solution and in its behaviour towards acids etc. Barium Per thiocar bonat e . It was found as stat,ed above that a solution of barium trithio-carbonate will dissolve one atom of sulphur per' molecule and experiments showed that a solution of barium hydrosulphide with the necessary sulphur to correspond with the formula Bas (this compound has not been isolated) would dissolve carbon disulphide mcre readily and with greater evolution of heat than if the hydro-sulphide were employed.This is in conformity with the results obtained with the other sulphides and polysulphides; it seemed reasonable to conclude therefore that the perthiocarbonate existed, a t least in solutiion. All attempts to isolate the solid failed; alcohol precipitated a mixture of sulphur and more or less pure trithio-carbonate ; on evaporation of solutions which should contain per-thiocarbonate in a vacuum oxidation always took place with the formation of white crystals (Found Ba =51.4 ; S = 24.5. Ba,S20,,H,0 requires Ba = 51-39 ; S = 23.93 per cent.). Strontium Trithiocarhonate. Ten grams of strontium hydroxide were suspended in 60 C.C. of 95 per cent. alcohol and converted into the hydrosulphide by passing hydrogen sulphide the temperature being kept at about 70° and air being excluded as usual.Carbonate which was always present, was removed by filtration in an atmosphere of hydrogen; a slight excess of carbon disulphide was added t o the filtered solution which was allowed to remain with exclusion of air for thirty minutes a t 40°. Addition of ether tau this solution precipitated dark red needles which became yellow on drying in a vacuum (Found, C = 4.4; H,O = 27.0; Sr r- 33-G ; total S =36*1; S evolved as H2S 60 YEOMAN TRITHIOCARBONATES AND PERTHIOCARBONATES 12.8.* SrCS,,4H20 requires C=4*48; H20=2G*89; Sr=32*7l ; total S = 35.92 ; S evolved as H,S = 11.97 per cent.). Stront>ium trithiocarbonate is much more readily soluble in water than the barium or basic calcium salts.Strontizcm Per thiocar b ona t e . Ten grams of strontium hydroxide were suspended in alcohol ancl converted into the hydrosulphide a3 above. The calculated amount or" sulphur was added to form the disulphide which was then con-ver Led into the perthiocarbonate by addition of carbon disulphide. Addition of ether to the aicoholic solution precipitated a red oil, which crpstallised after some time forming yellow crystals which were collected washed with ether and dried in a vacuum (Found, C - 2.7 ; H,O = 39.0 ; Sr =. 23.7 ; total S = 34.5 ; polysulphide S = 8.4 ; S evolved as R,S = 8.4.1- SrCS3,8H,O requires C = 3-22 ; H,O = 38.73 ; Sr = 23-56 ; total S = 34.49 ; polysulphide S = 8.62 ; S evolved as H,S=S.62 per cent.).The yellow crystals dissolve readily in water forming a yellow solution which is incapable of dissolving sulphur; they are soluble in alcohol ancl precipilated by ether as a red oil which requires smie time t o crystallise (compare potassium and sodium perthio-carbonates). Jfagnesium Tri- n?id Per-tliiocarhonnte. Berzelins (Zoc. cit.) prepared magnesium trithiocarbonate by mix-ing solutions of barium trithiocarbonate and magnesium sulphate, the barium stzlphate being filtered off and the solution evaporated i n a vacuum; he obtained the salt in citron-yellow crystals which readily formed basic salts. On repeating these experiments adding the calculated amount of magnesium sulphate to solutions contain-ing ( a ) barium trithiocarbonate ( b ) barium trithiocarbonate with the requisite amount of sulphur corresponding with BaCS, and filtering solutions were obtained containing magnesium trithio- and perthio-carbonate respectively.The trithiocarbonate solution was red and capable of dissolving one atom of sulphur for each molecule of the trithiocarbonate. The perthiocarbonate was yellow and i n capable of dissolving sulphur. On evaporating these solutions in a vacuum yellow substances were obtained which were basic but very impure containing variable and large amounts of thiosulphate. If magnesium oxide is suspended in alcohol and hydrogen sul-phide saturated with carbon disulphide vapour passed in for a long * Polysulphide and thiosulphate present in traces only. TThiosulphate present as a trace only YEOMAN TRITHIOCARBONATES AND PERTHIOCARBONATES.61 time with exclusion of air hhen on filtering and precipitating with ether a crystalline substance is obtained which appears to be the trithiocarbonate. In a similar manner the perthiocarbonate is formed by employing a mixture of magnesia and sulphur. A mmonium l'rit hiocar b ona t e . Ammonia dried by passing over quicklime was dissolved in alcohol forming a 20 per cent. solution and this solution was satur-ated with dry hydrogen sulphide; after warming to 35-40° and simultaneously passing hydrogen to exclude air a slight excess of carbon disulphide was added and then dry ether until a permanent turbidity was produced. On allowing the solution to cool slowly a red crystalline substance separated which was collected in hydro-gen washed with dry ether and dried as completely as possible a t the ordinary temperature in a current of hydrogen (Found, C = 7.5 ; NH = 25.8 * ; total S = 65.7 ; S evolved as H,S = 23.1.j-(NH,)2CS requires C = 8.33 ; NH = 24.96 ; total S = 66-71 ; S evolved as H,S = 22.27 per cent.). The salt is soluble in waf,er giving the typical red solution of the trithiocarbonate ; the aqueous solution dissolves sulphur one atom for each molecule of the salt; i t is more readily soluble in alcohol than the perthiocarbonate and is precipitated from solution by ether. The salt gradually decomposes a t the ordinary tempera-ture first losing carbon disulphide (the analysis shows that the salt has lost some carbon disulphide) forming ammonium sulphide, which in its turn becomes dissociated into ammonia and hydrogen sulphide; on keeping for some time thiocyanate is also formed.On heating the freshly prepared dry salt in hydrogen a t looo ii; completely dissociates leaving no residue. Aqueous solutions of the salt are very unstable easily losing carbon disulphide hydrogen sulphide and ammonia in addition to which oxidation takes place as with the other trithiocarbonates. On boiling an aqueous solution in an open vessel this change takes place rapidly very little thiocyanate and no carbamide being formed. A mm,onium Per thiocar bonat e. A 20 per cent. alcoholic solution of dry ammonia was converted into the hydrosulphide and the exact amount of sulphur added to * The carbon was estimated by heating with alcoholic ammonia in a sealed tube a t 100" and determining the thiocyanate formed.In the NH deter-mination the salt was first heated for a short time with concentrated sulphuric acid since the ordinary procedure would cause formation of thiocyanate. t Thiosulphate polysulphide and thiocyanate were present in traces only 52 YEOMAN TRI'THIOCARBONATES AND PERTHIOCARBONATES. convert it into the disulphide (NH,),S, all the operations being made in the absence of air. On addition of carbon disulphide the perthiocarbonate was immediately precipitated as a yellow crystal-line solid. The crystals were collected washed with dry ether with the usual precautions and the ether was removed as completely as possible in a current of hydrogen a t the ordinary temperature (Found C = 6.3 ; NH = 18.2 ; total S = 66.0 ; polysulphide S = 17.0 ; S evolved as H,S= 16.3.(NH,)2CS4,H,0 requires C =6*18; H,O= 9-26; NH4=18.53; total S=66*03; polysulphide S=16-51; S evolved as H,S=16.51 per cent.). On allowing an alcoholic solution of ammonium perthiocarbonate ta evaporate slowly a t the ordinary temperature well-defined trans-parent crystals of the monosymmetric or asymmetric systems were obtained some of them being 10 mm. long 7 mm. wide and 2 mm. thick (Found C= 7.3 ; €I = 4.7 ; N = 15.3 ; total S = 73.0 ; polysul-phide S = 18.5 ; S evolved as H,S = 17.7. (NH,),CS requires C = 6.81 ; 13 = 4.57 ; N - 15.88 ; total S = 72.74 ; polysulphide S 18.18; S evolved as H,S=18*18 per cent.). The salt is very readily soluble in water forming a yellow solution which is incapable of dissolving sulphur but not very easily so in alcohol being precipitated therefrom by ether.It behaves in a very similar manner to the trithiocarbonate losing carbon disul-phide hydrogen sulphide and. ammonia a t the ordinary tempera-ture the residue becoming richer in sulphur. It completely deconi-pmes when heated a t 1 0 0 O in a stream of hydrogen leaving a residue of sulphur. A t the ordinary temperature aqueous solutions are only very s l o ~ l p converted into the thiocyanate excess of ammonia ha.stening the reaction. As with the trithiocarbonate the conver-sion to thiocyanate is complete' if the salt is heated in a sealed tube with alcoholic ammonia a t looo. The solutions of both ammonium trithiocarbonate and perthio-carbonate are very unstable partly because of the well-known change which ammonium trithiocarbonate undergoes whereby it loses hydrogen sulphide in two stages passing successively into ammonium dit hiocarbamate and ammonium thiocyanate and partly 02 account of the ready manner in which it undergoes complete dissociation iuto ammonia hydrogen sulphide and carbon disul-phide.This dissociation occurs so readily a t the ordinary tempera-ture that even inert gases such as hydrogen and nitrogen when passed through solutions of the ammonium thiocarbonates contain-ing less than 0.1 per cent. of carbon disulphide take up the latter to the extent of 1.1 milligrams per litre (50 grains per 100 cubic feet) YEOMAN TRITHIOCARBONATES AND PERTHIOUARBONATES. 53 l?rit?r iocarbonic and Pert hioca~boraic A cids.Many investigators have found that solutions of the thiocarbon-ates on treatment with acid yielded a reddish-yellow oil which soon decomposed giving off carbon disulphide and hydrogen sul-phide and was supposed to be trithiocarbonic acid H,CS3. O’Donoghue and Kahan (T. 1906 $9 1812) determined the sulphur in the dry oil and found that it agreed with the formula H,CS, but coiicluded that the oil was a solution of sulphur in trithiocarbonic acid basing their conclusions on the results of partial analyses of salts prepared from the acid oil. The author was unable to confirm their results but found that pure trithiocarbon-ates yielded no oil on addition of acid a t Oo provided oxygen was completely excluded; if oxygen had access or if sulphur or thiosul-phate was added to the solution then the insoluble oil was slowly fcrmed on addition of acid the amount varying and depending on the extent to which oxygen had access or to the quantity of thio-sulphate or sulphur present.Crude thiocarbonates and pure per-thiocarbonates on treatment with acid yield an oil immediately a t the ordinary temperature. The oils obtained in the several cases were conver1,ed into salts great precautlions being taken to exclude oxygen ; complete analyses of these partly dried salts showed them all to be perthiocarbonates. The formation of perthiocarbonates will equally take place whether the oil is H,CS or H,CS3 + S but in conjunction with the above it appears likely that the insoluble red oil is perthiocarbonic aczd H,CS, and that trithiocarbonic acid H,CS, exists and is soluble in water for otherwise addition of acid to a cold solution of a pure trithiocarbonate will cause the separation of the almost insoluble carbon disulpbide which separa-tion has not been observed.When oxygen has free access perthio-carbonate will be produced as shown earlier in this paper; and if thiosulphate or sulphur is present the trithiocarbonate will take up sulphur direct or from the thiosulphuric acid formed on the addition of acid in both cases forming the perthiocarbonate and thence the perthiocarbonic acid. Colour and Constitution ~f the Trithiocarbonates and Pert h io car bona t es. The alkyl deriva Lives of orthothiocarbonic acid and the numerous derivatives of carbonic acid in which one or two oxygen atoms are displaced by sulphur are colourless.A priori it would be expected that the trithiocarbonates would also be colourless whereas in fact, even when quite free froin perthiocarbonates they have a dee 54 YEOMAN TRITHIOCARRONATES AND PERTHIOCARH~NATES. yellow colour. Whether this colour would persist if the salts were ccmpletely anhydrous could not be determined owing t o the loss of carbon disulphide on prolonged drying but the anhydrous alkyl esters are all strongly coloured yellow liquids or deep yellow, crystalline solids. Chancel (Jnhrcsber. 1851 513) describes the alkyl potassium and alkyl sodium salts of trithiocarbonic acid as cclourless crystalline solids J Holmberg ( J . pr. ChmL. 1906 [ii] 73, 239) describes them as yellow substances.On repeating Chancel's experiment3 the author obt,ained yellow cryst'alline substances which were far from pure. The capacity for the direct; combination with sulphur appears t o be confined t o those derivatives of carbonic acid in which all three oxygen atoms are displaced by sulphur for example neither sodium xanthate nor ammoniutn dithiocarbamate is capable of combining with sulphur. Ethyl trithiocarhonate (C,H,),CS, does not combine with sulphur forming the perthiocarbonate but Idissolves sulphur in amounts varying with the temperature. In fact it was not found pcssihle to prepare ethyl perthiocarbonate although as shown by Berend ( f l y i n d e n 1865 128 333) the alkyl esters are capable of foi ming additive compounds with one molecule of bromine which are well-defined crystalline substances. I n many ways the relation of the trithiocarbonates t o the perthiocarbonates is analogous to that of the metallic sulphides t o the polysulphides. There are certain differences however the heat of formation of the combina-tion of trithiocarbonate with sulphur being three times that of the formation of disulphide from monosulphide and whereas the tri-thiocarbonates can only combine with one extra atom of sulphur, the sulphides can combine with as many as five or six. In conclusion the author wishes to record his indebtedness to Dr. H. G. Colnian both for valuable advice and for the opportunity of carrying out this work. CHEMWAL LABORATORY, 1 ARUNDEL STREET, STRAND W.C.2. [Received November 3rd 1920.

ISSN:0368-1645    

DOI:10.1039/CT9211900038

出版商:RSC    

年代:1921

数据来源: RSC

摘要:

THE BROMINE COMPOUNDS o$ PHICNANTHRBNE. PART I. 55 IV.-Ihe Bromine Compounds of Phenanthrene. By HERBERT HENSTOCK. WHEN it is coiisidered that phenanthrene is one of the principal aromatic hydrocarbons derived from coal-tar it seenis strange that up to now almost the only commercial use to which it has been put is the production of lamp black by its destruction. Several of the alkaloids notably morphine apomorphine and thebaine have the phenanthrene molecule as the chief basis of their structure and the hydrocarbon should also be a fruitful source of colouring matters. One of the chief reasons why its value has not been more appreciated is undoubtedly the very meagre knowledge which we have of its more common compounds. Its halogen derivatives offer a promising field for inquiry.The number of possible isoiiiexic bromophenan threnes is large, although few have been already described and still fewer thor-oughly investigated. Of the five possible monobromo-derivatives only 9-bromophen-anthrene (m. p. 63O) is known (Hayduck ,4?znaZen 1873 167 181). Of the twenty-five possible dibromo-derivatives only six are known, namely the 2 7 (m. p. 199-2OOO; Hayduck Zoc. cit. ; Schmidt and Mezger Ber. 1907 40 4562) the 9:lO (m. p. 181-182O; Hay-duck Zoc. cit. ; Schmidt and Ladner Ber. 1904 37 4404) the 3 9 (m. p. 146O; Zetter Ber. 1878 11 170; Schniidt and Ladner Ber., 1904 37 3571 ; Sandqvist Rer.. 1920,53 [B] 168) the 4 9 (or 10) (m. p. 113O Werner Aanalen 1902 321 331) the 10 (1 4 5 or 8) (ni. p. 123O Sandqvist B e r . 1915 48 1146) and a dibromo-deriv-ative melting a t 202O (Annnlen 1873 167 182).With the excep-tion of two o r three imperfectly described ones nothing is known of the sixty-one possible tribroino-derivatives. I n brominating phen-anthrene the 9 10-positions are those most readily attacked and this dibroniide is very unstable decomposing a t looo with the evolu-tion of hydrogen bromide and the formation of the 9-bromo-deriv-ative (Hapduck ZGC. cit.). I n the course of this work a 2( 2)- bronLoplzeiiarktitrene dibromide ( I ) was isolated which decomposed exactly as in the case of Hay-duck’s dibroniide (Zoc. c i t . ) leaving a 2( ?) 10-c7ib~omophenarthrene (11) 56 HENSTOCK THE BROMINB This will probably be found to be a general reaction for coin-pounds of this kind.m e preparation of the 9-bromo-derivative has been improved by Austin (T. 1908 94 1762) by using carbon tetrachloride as a diluting medium. A systematic examination of the reaction in this diluent has been made by the author by using varying amounts of bromine. With two atoms Austin’s results were confirmed. Three yielded 28 per cent. of the 9-bronio-derivative and 23 per cent. of 2( ?)-bromophenanthrene dibromide whilst four atoms gave 31 per cent. of the 9-bromo-derivative together with 30 per cent. of 2( 1)-bromophenanthrene dibromide which decomposed to 23 per cent. of the 2( 1 ) 10-dibromo-derivative melting a t 162O. The dibromo-derivative having the nearest melt,ing point ( 1 5 8 O ) to this is that of Zetter (Zoc. cit.) but his is readily soluble in alcohol and crystallises only in plates whereas the new one is soluble in alcohol only on boiling and crystalliscs most readily in needles but is dimorphous and can also be obtained in plates.The proof of the position of the bromine atom in position 10 is shown by the formation of a phenaiithrone on oxidation. Normally, phenanthrene or its compounds having the 9 10-positions unoccu-pied yield o-quinones but in this instance only one oxygen atom was found in positions was thus : the oxidised product indicating- that one- of these The reaction may be represented already occupied. (111.) The phenanthrone yielded a monoxinie but no dioxime as would have been the case had the 9 10-positions been occupied by oxygen. Additional evidence was f orthconiing on nitration where exactly analogous conditions hold ; a mononitrate but no dinitrate was obtained.It may therefore be concluded that position 10 is occupied by one of the bromine atoms. In an attempt to prove the position of the second bromine atom the evidence was of a negative character. If we consider the posi-tims I 2 3 and 4 which it might occupy number 3 is excluded, because Sandqvist (Zoc. c i t .) describes a dibroniophenanthrene melt-ing a t 1 4 3 O which he demonstrates to be the 10 3(or 6)-derivative. Of the remaining positions 2 was chosen for att)ack. 2-Ethoxyphen-anthrene was subjected t o exactly the same conditions of experi-ment in which the dibromo-derivative melting a t 162O was formed. The sole product was the lO-bronio-2-ethoxyphenanthrene so that, when position 2 is occupied the bromine enters the bridge only; from this it might be inferred that the second bromine ato COMPOUNDS OF PHENANTHRENE.PART I. 67 occupies position 2 but this evidence cannot be taken as conclusive, and the matter is still under investigation. E X P E R I N E N TAL. 2( 1 ) -2lromophenanthrene Dibromide ( I ) , A solution of 32 grams of dry phenanthrene in 50 C.C. of dry carbon tetrachloride was treahed with 57.4 grams (4 atoms) of previously dried bromine in 50 C.C. of the same solvent. After forty-eight hours 11 grams of pale yellow crystals had formed, which were fcund to be 9 10-dibromophenanthrene. ?"he filtrate was evaporated to dryness in a current of dry warm air no heat being applied when a yellow crystalline solid remained.On extrac-tion with three successive portions of cold light petroleum part dissolved leaving 10 grams of R pale yellow substance which crys-Lallised from glacial acetic acid in long flat lemon-yellow needles melting and decomposing at 100-102 (Found Br = 57.64. C,,HgBr requires Br = 57.55 per cent.). The bromine evolved as hydrogefi bromide was estimated by heating to l l O o and passing the gas into silver nitrate solution (Found Br = 18.79. C,,HgBr,(less HBr) requires Br = 19-10 per cent.). The compound can be boiled in glacial acetic acid solution with-out change but it gradually decomposes into the dibromo-derivative and hydrogen bromide if exposed t o a warm atmosphere. 2( ?) lO-Dibronto/ihe?tanthren~ (11). After heating 10 grams of the preceding compound a t looo until all hydrogen bromide ceased to be evolved it yielded 8 grams of a white solid which crystallised from a concentrated solution in boil-ing alcohol in long slender colourless needles forming throughout the liquid.On allowing the filtrate to remain no needles appeared, but very small colonrless plates formed on the sides of the dish. These were again crystallised from a concentrated boiling alco-holic solution when they separated in needles like the first crop. The needles (first crop) on the other hand separated from a dilute solution in boiling alcohol in plates. The needles melted a t 162O, the plates a t 1 6 1 O (Found [needles] C=50.00; H=2*68; Br= 47.68 ; [plates] C = 49-83 ; H = 2.43. C,,R8Br requires C = 50.00 ; H = 2-35 ; Br = 47.61 per cent.).T'he plates were found to be triclinic and the needles rectangular. The substance is therefore dimorphous. When kept for some months the needles gradually break down into plates 58 HENSTOCK THE BROMINE 2( 2) 10-7~l)ibron~o2lhenanthrene is fairly readily soluble in glacial acetic acid ether acetone chloroform or benzene less so in light petroleum or alcohol and insoluble in water. The solubility of the plates in ether acetone or glacial acetic acid is slightly less than that of the needles whilst the latter dissolve in alcohol rather less readily than the plates; in other solvents their solubilities are alike. Both plates and needles yield the same phenanhhrone and the same nitro-compound. 2( 1 ) 10-n;broniophena?Lthrone (111).Two grains of the above dibromo-derivative dissolved in 120 C.C. of glacial acetic acid were oxidised by heating for two hours with an equal weight of chromium trioxide. I f the solution becomes ccld yellow crystals appear but a better yield is obtained by cool-ing to about 30° and pouring into water. The precipitate (1.9 grams) crystallised from alcohol in slender lemon-yellow needles melting a t 2 G 3 O (Found C = 47-64 ; €I = 2-50. C,,H,OBr requires C =47*72 ; 13 = 2.27 per cent.). The compound is not so soluble in alcohol ether or glacial acetic acid as in most of the other organic solvents. Analyses of the substance prepared from both the plates and needles of the dibromo-derivative gave concordant results. It dissolves in warm concen-tiated sulphuric acid with a dark greenish-blue colour and is reprecipitated on dilution with water.The monoxinze is readily formed by boiling for three hours a 1 per cent. alcoholic solution of the substance milh two-fifths of its weight of liydroxylamine hydrochloride. After evaporating the alcohol the residize is boiled for some minutes with water and is then left as a greenish-yellow powder the yield being quantitative. It crystallises from benzene in bulky dull yellow hair-like crystals, which shrink considerably on drying and melt and decompose a t 239O (Found N = 4.05 ; Br = 43.44. C,,H,ONBr requires N = 3-81 ; Br = 43.59 per cent.). Although very readily soluble in ether acetone or alcohol it is insoluble in cold benzene. It does not form an anhydride when treated with alcoholic potassium hydroxide.A 1 per cent. solution of 2( 2) 10-dibromophenanthrene in glacial acetic acid is heated to 60-70° and then cold fuming nitric acid added until a slight permanent cloudiness remains the solution i COMPOUNDS OF PHENANTHRENE. PART I. 59 fipally boiled for five minutes and on cooling silky crystals (75 per cent. yield) are deposited which separate from alcohol in lemon-yellow feathery needles melting a t 1 8 8 O (Found N=3*39. C,,H70,NBr requires N= 3-61 per cent.). The nitro-compound is very readily soluble in chloroform or benzene but in acetone or alcohol only on boiling. On further addition of nitric acid or continued boiling of the mixture no dinitro-derivative was forined although several at tempts were made to obtain this; therefore the bromine atom in position 10 is not readily displaceable by the nitro-group.A similar type of compound namely 9-bromo-1 O-nitrophen-anthrene has been prepared by Schmidt and Ladner (Zoc. c i t . ) . $!(NH,)fBr C,H,-C,H,Br' 2 ( 1 ) lO-I).ibro~i.o-9-Q17i~iop~enanthre~e, The reduotion of the nitro-compound was effected by boiling for one hour with tin and hydrochloric acid. The amine was washed with hot waler dissolved in warm alcohol and the solution filtered. On pouring this into much water a brown flocculent precipitate was obtained which when dry was extracted with a little cold chloroform. The pale brown solid (35 per cent. yield) crystallised from dilute alcohol in colourless needles melting at 1 7 7 O (Found N =4.08.C,,H,NBr requires N = 3.98 per cent.). "he substance is very readily soluble in the usual solvents except light petroleum ether or chloroform although it does not crystal-lise readily from these. On prolonged exposure to light it gradually turns brown. It dissolves on boiling with dilute sulphuric acid, and on cooling flocculent crystals of the hydrogen sulphate appear. The acet91 derivative was prepared by heating the amine with twenty times its weight of acetic anhydride at 130-140° for six hours. The cold solution was poured into water and the resulting white granular solid after being washed with dilute sodium hydr-oxide solution and then with warm water crystallised from boiling alcohol in colourless flat tetragonal plates melting a t 2 0 2 O .The yield was SO per cent. of the theoretical (Found C =48*81; H = 3-01. C,,H,,ONBr requires C-=48-85; H=2.80 per cent.). It is very readily soluble in cold chloroform but dissolves in ether or alcohol only on boiling. Action of Alcoholic Potassium Hydroxide om 2( 12) 10-Dibromo-ph?enanthrene. When tha dibromo-compound (one-fifth of the weight of the potassium hydroxide) is gradually added to 10 per cent. alcoholi 60 THE BROMINE COMPOUNDS OF PRFNANTHRENE. PART I. potassium hydroxide and the solution boiled for four hours the liquid becomes reddish-purple and deposits a 90 per cent. yield of a blood-red precipitate which is insoluble in water and all the usual organic solvents with the exception of carbon disulphide and benzene in which it is sparingly soluble.It crystallises from the 1a.tter in small brilliant scarlet needles which do not melt below 350O. Its composition was not indicated by analysis (Found, C = 52.27; H = 3-03 per cent.). It leaves no residue on burning and is not acted on by strong acids or alkalis in the cold but is decomposed by the former on boiling. It is oxidised by chromium trioxide yielding a clear, yellow solution which on neutralisation with sodium hydroxide gives a yellow precipitat,e. The product is therefore not a quinone, neither is the red substance. Tbis is further shown by the fact that neither gives an oxime. The scarlet substance contains bromine. 9-Bromophenanthrene does not yield a red compound. Dibromo-hydrocarbon CI7HlGBr2. T%e three portions of light petrcleum extract from the bromina-tion of phenanthrene (p.57) were united and evaporated to dry-ness leaving a pale brown oil which solidified after twenty-four hours and crystallised from alcohol in pale yellow needles melting a t 216O (Found C = 53-64 ; H =4.04. C,,H,,Br requires C= 53-68 ; H=4*21 per cent.). The compound contains bromine and derivative of a hydrocarbon occurring phenanthrene. 2-Ethoxyphenanthrene (T. 1906 89, under exactly the same conditions as is evidently a dibromo-as an impurity in the yH=QEr cp C,H ox t 1527) was brominated when 2( P) 1Odibromo-phenanthrene was formed. The product when heated a t looo, evolved hydrogen bromide and left a yellowish-white mass which crystallised from glacial acetic acid in small colourless leaflets (81 per cent.yield) melting a t 148-149O (Found C=63*87; H=4"72; Br=26*34. Cl6HI30Br requires C=63*78; H=4.32; Br = 26-57 per cent.). It is very readily soluble in the usual solvents except methyl alcohol and glacial acetic acid. Since bromine attacks the 9 and 10 positions most readily it is reasonable to suppose that t,hese have been entered and the fact that hydrogen bromide is evolved on heating the crude produc BHATNAGAR STUDIES IN EMULSIONS. PART 11. 61 would substantiate this view a 9 10-dibromide being first formed and decomposing into the above substance and hydrogen bromide, just as in the case of Hayduck's dibromide (Zoc. cit.). Further evidence is afforded by the fact that 9 10dinitro-2-ethoxyphen-anthrene is not attacked by bromine under the same experimental conditions.Y(NO,):Y*NO, C,;H4-C6 H,*OEt' 9 lO-Dinitro-2-ethosyphenanthrene, ?"he dinitro-compound was prepared by treating a 3 per cent. glacial acetic acid solution of the ether with fuming nitric acid until a permanent cloudiness appeared and then adding a slight excess boiling for fifteen minutes and allowing to remain for twenty-f our hours. On pouring into water the dinitro-compound was precipitated and was dried a t 105O. After extracting with a little cold benzene the residue crystallised from the same boiling solvent in pale yellow shining rhombic prisms melting a t 247O (Found N t= 9'66. It is readily soluble in chloroform but not in carbon tetra-chloride. It. burns very easily with a small flash leaving no residue. C,,H,O,N requires N = 9.46 per cent.). The author wishes to express his thanks for grants from the Research Fund of the Chemical Society and from the Government Grant Committee of the Board of Trade towards the cost of the materials used in the work. CUEMIGAL RESEARCH LABORATORY, SCHOOL GARDENS, SHREWSBLJRY. [Received October 30th 1920.

ISSN:0368-1645    

DOI:10.1039/CT9211900055

出版商:RSC    

年代:1921

数据来源: RSC

摘要:

BHATNAGAR STUDIES IN EMULSIONS. PART 11. 61 V.-Studies Eniulsions. Part II. The Reversal of Phases by Electrolytes and the Eflects of F r e e Fatty Acids and Alkalis on Emulsion Equilibrium. By SHANTI SWARUPA BHATNAGAR. THE study of the effects of electrollytes on emulsion equilibrium is undoubtedly of greatl importance for the elucidation of the mechanism of emulsification but unfortunately very little quanti-tative data is available on the subject. The work of Clowes (6. Physical Chem. 1916 20 445) is restricted to! a particular typ 62 BHATNAGIAR STUDIES IN EMULSIONS. PART 11. of emulsion in which the volumes of the two phases are always equal. I n a previous paper (T. 1920 117,549) this work of Clowes has been discussed. Subsequent work on the problem has shown that the procedure of using alkaline solutions and free fatty acids in oils employe’d by Clowes is not quite satisfactory.When dilute sollutions of alkalis are used a comparatively large amount of free fatty acid in the) system is left unneutralised. The presence of free fatty acid or free alkali makes the system more complex. I n addition they seem t o have a definite effect on the emulsion equilibrium as will be shown later. Really corn-parable results can only be1 obtained and repeated by employing neutral oil and soap solutions. EXPERIMENTAL. Tn all experiments described in this paper various soaps were used instead of different alkalis. Sodium oleatel and potassium stearate were obtained from Kahlbaum. The lithium stearate was a sample prepared by Sir William Ramsay and preserved in this laboratory.Sodium lindeate and other soaps were prepared in 1 he manner advocated by MacBain ( Y ’ r u ~ s . b”imtZay SOC. 1913, 9 99). The electrolytes were1 pure chemical reagents (excepting nickel nitrate) and were recrystallised before making up the solutions. I n order to! ensure1 identical conditions for repeating the observ-ations the time for shaking the volume of the phases and the size and other conditions of vessel were always kept alike. It was found that under these conditions with carefully cleansed vessels, the observations could be repeated with a fair degree of accuracy. The emulsions were prepared in wide-mouthed bottes and the type noted by examining small portions of emulsions in a T-shaped glass container according to the method described in a previous paper (Zoc.c i t . ) and with frequent testings under the microscope. The two1 methods gave identical results for all fine-grained emulsions. Eqneriments with E’lectrolytes. Volume of oil phase = 10 C.C. Volume of aqueous phase=10 C.C. I2 = Inversion point BIIATNAGAR STUDlES CN EMULSIONS. PART 11. 63 TABLE I. Soul3 Used Sodium Oleate. The figures givea in the columns represent% the amount of the respective salts in niillimols at R1. Amount of soap in milli-mol. Ba(N03),. Sr(N03)2. Pb(NO,),. Ni(N03)2. A12(S04),. Cr,(S04),. 0.080 0.0398 0.0398 0.0396 0.036 0.014 0.016 0.101 0.0500 0.052 0.504 0.040 0.017 0.019 0.150 0.080 0.084 0.082 0.060 0.025 0.027 0.162 0.084 0.090 0.088 0.076 0.027 0.030 0.210 0-112 0.116 0.110 0.0798 0-036 0.039 TABLE 11.Soap Potassium Stearate. Soap in milli-mol. €3a(N0,)2. SI!(NO,)~. Ni(N0,)2. Pb(NO,),. Al,(SO,),. Cr2(S04),. 0.086 0.044 0.046 0.040 0.040 0.018 0.018 0.10 0.0508 0.0512 0.050 0.052 0.026 0.022 0.15 0.084 0.086 0-078 0.088 0.027 0.026 0.25 0.132 0.136 0.128 0.140 0.048 0.048 0.30 0.156 0.160 0.150 0.154 0.056 0.057 TABLE I 11. Soap Lithium Stenrate. Soap. Ba(NO,),. Sr(N03)3. Ni( NO3),. Pb(N0,)3. Al,(SO,),. Cr2(S04),. 0.09 0.040 0.040 0.036 0.042 0.015 0.016 0.12 0.058 0.058 0.050 0.056 0.021 0.023 0.16 0.090 0.094 0*080 0.094 0.028 0.029 0.20 0.102 0.104 0.096 0.106 0.03 0.032 TABLE. IV. Soap Sodium Linoleate. Soap. Ba(NO,),. Sr(NO,),. Ni(N03), Pb(NO,),. Al,(SO,),. Cr(SO,),. 0.083 0.068 0.068 0.058 0.072 0.028 0.028 0-112 0.100 0.106 0.090 0.116 0.038 0.037 0-125 0.128 0.134 0.120 0.136 0.042 0.043 0.18 0.198 0.20 0.178 0.200 0-061 0-063 The results shown in tables I 11 111 and IV indicate in a marked manner the difference in the amounts of various electro-lytes required to bring about the reversal of phases.The effect of the valency of the electrolyte is worth noting. The amounts of the tervalent electrolytes aluminium and chromium sulphates, required to bring about the reversal of phases are less t'han thos 64 BHATNBGAR STUDIES IN HIKULSIONY. PART 11. od bivalent elsctrolytw. The polwer oif reversing the phases in these electrolytes is in the order a1uminium)chr~mium) nickel>lead>barium>strontium. Calcium bivalent iron and magnesium are found to( have practically the same values as strontium and are therefofre not shown in the tables.The amount 09 electrolytes required to1 bring about the reversal of phases differs with different soapsl but the valency effect of the electrolyte still holds goold. Effect of Changz'n)g the Volume-ratio of t 7 ~ e Phases. I n all previous experiments the volumes of the oil and aqueous phases have been equal. Keeping all other conditions constant, some experiments were tried in order to find how tbhe action of ,electrollytes on the inversion point is affected by changing the volumerat,iol of the two phases. The results' are shown in table V TABLE V. Tot,al volume of emulsion always 20 C.C. Soap Lithium Stearate 0.12 ?tLillirtLoL. B. P.parafh in C.C. 2 5 8 10 11 13 15 Aqueous phase in C . C . 18 15 12 10 0 7 5 Ba(NO,) in millimol in the aqueous phase at R,. 0.078 0.070 0.060 0.058 0.054 0.044 0.040 Al,( SO& in millirnol at R,. 0.030 0.028 0.024 0.021 0.018 0.012 0.010 It is interesting to note that the amount of multivalent elwtro-lyte requireid to bring about the inversion of phases increases as the volume of the aqueous phase is increased and diminishes as it is reduced. A corresposnding increase in the oil phase has a reverse effect. Thus in table V the ratio1 between lithium stearate and barium chloride a t the inversion point was as 0.24 0.058 when the volumes of the two phases were as 10:lO. When the volume of the aqueous phase was increased so that the ratio between them was 15 :5 the amount of barium nitrate a t R increased to 0.070 millimol and was reduced to 0.04 when the ratio became 5:15, that is oln proportionately increasing the oil phase.Similar rwdts were olbtainable with other soaps and electrolytes used in this investigation BHATNAGAR STUDIES I N EMULSIONS. PART 11. 65 Effect of DiJution 0% the Reversal of Phases by Electrolytes. Emulsions can be diluted infinitely by the addition of the con-tinuous phase. Itl was considered desirable to find how dilution affects the actioln of electrolytes on the inversion point. A large quantity od fine-grained emulsions was prepared by vigorously shaking in a mechanical shaker some oil to which the aqueous phase was gradually added until the total volumes of the aqueous and oil phases became equal.This standard emulsion was divided into four equal portions of 20 C.C. each. One portion was kept un-diluted and the other three portions were differentally diluted with solutions of soap and different amounts of electrolytes added previous to a second shaking in the manner already described. Some of the results are given in tableu VI. TABLE VI. Soap Sodium Oleate. Amount of soldium odeate in each sample 0.101 millimol. BaCl in millimol at the inversion A12(S0,)S in milli-mol at the inver-20 C.C. of emulsion. point. sion point. 1. Standard emulsion ... ........ . ..... . ... 0.050 0.014 2 . SY , twice diluted ...... 0.0798 0.025 3. ? Y , thrice diluted. .. .. . 0-1 12 0.040 4.9 ) , four times diluted 0.156 0.057 The remlts in table VI indicate that the greater the dilutJon or the distance between the oil particles in an emulsion the larger is the amount of the' multivalentl electrolyte required tol bring about the reversal of phases. These results are in keeping with the previously observed effect of dilution on the rate of coagulation of colloidal sols by electrolytw (T. 1919 115 462). A few observations were also made to ascertain how the rate of coagulation of the typical natural emulsion milk is affected on dilution. The procedure consisted in preparing several different solutions of milk and water. Equal volumes of these solutions were placed in clean testitubes a definite volume of 0'4906N-sulphuric acid was added the tube well shaken and the times f o r the first perceptible change and complete ccagulation were noted.Table VII indicates some of the results o b t a i n d VOL. CXIX 66 BHATNAGAR STUDIES IN EMULSIONS. PART 11. TABLE VII. Time for first perceptible change on the addition of a known volume of sulphuria Volume of solution always 20 C.C. acid. Pure milk ............... Immediately after adding. Twice diluted ............ Thrice diluted ......... 12 minutes. Four times diluted ... 15 minutes 3 seconds. Five times diluted ...... 25 minutes 2 seconds. Eight times diluted ... 50 minutes. Ten times diluted ...... 70 minutes. 9 minutes 2 seconds. Another set of experiments was performed to find the strength of a known volume of acid which will produce a perceptible change immediately on addition to the solutions and it was found that the greater the dilution the stronger was the acid required to produce an immediate coagulation effect.It is t*hus evident that the reversal of phases by electrolytes in emulsio,ns the precipitation of colloidal sols in suspensions and the coagulation olf substances like milk in which the acids used act oln the casein membrane round the f a t globules are similarly affected on dilution. It is probable t(ha6 the cause or causes producing these identical effects are also identical and a thorough study of any one of these phenolmena may lead to the elucidation of the problem of coagulation. Effects of Free Fatty Acids and Alkalis on the Emulsion. Equili bm'um. The procedure adopted fosr investigating the irregularit'ies observed when free fatty acids and alkalis were used for emulsifi-cation consisted in preparing three sets of emulsions.All con-tained the same amount of sodium oleate and the same volume ratio the only difference being that in one set the oil contained free fatty acid in the second the aqueous phase contained free alkali and in the third set' neutral oil and soap solutions alone were used. The following table represents the results which show TABLE VIII. Soap Used Sodium Oleate. Emulsions Free containing otassium 0.162 millimol Eydroxide. of soap. Gram. 20 C.C. 0.01 SP 0.02 1 as 0 88 0 P? 0 Ba(NO)S in acid. required at 0 0.09 0 0.096 0.003 0.078 0*008 0.070 0 0.084 Free fatty millimol El* Gram BHATNAGAR STUDIES IN EMULSIONS.PART 11. 67 that the free fatty acids and1 free alkalis shift the inversion point in opposite directions. During the microscopic exaniination of these three sets of emulsions it was found that the average size of globules of oil was greater in emulsions containing free fatty acid and smaller in emulsions containing free alkali in the system than the average size for identical and equal shakings when neutral oil and soap solutions alone were used. Itl is interesting to note that the addi-tion of a little free alkali to a soap solution also decreases the size of the particles and results in turning a slightly turbid solution into a perfectly clear one whilst the addition of free fatty acid increases the size of the particles and1 makes the solution more turbid.This may possibly account for the difference in the sizes of particles in the above-mentioned emulsions. It is to be noted that as the degree of dispersion is an important factor in the stability of an ernulsion all attempts to arrange various emulsifying agents in order of their efficiency for emulsifi-cation without taking into account the size of the particles of these agents are defective. The size of the particles of an emulsifying agent has also been found by Pickering (T. 1907 91, 2001) to have a definite effect on the degree of dispersion. Discussiorz of Results. The results indicated in tablm I 11 111 and IV show that the tervalent electrolytes have a greater effect on the inversion of the emulsion than the bivalent ones.A similar conclusion has been drawn by Clowes (Zoc. c i t . ) . The effect of dilution and of increas-ing t’he distance between the oil particles in an emulsion is essenti-ally similar in nat’ure to the effect of dilution on colloidal sols. A complete discussion of the results obtained here will be reserved for a later contribution. The difference in the amount of electrolytes required to bring about the reversal of phases with different soaps points t o the probability of a difference in their protective actions. The results indicate tchat the soaps can be arranged in order of their protective action as potassium stearate>sodium stearate>sodium and potassium palmitates>potassium o1eate)sodium oleate for B .P. paraffin oil.The results have an important bearing on the cleansing power of soaps. The old hypothesis of Chevreul that the cleansing power of soap is due to the free alkali liberated is now discarded. The modern conception attributes the washing power of soap to its “emulsifying efficiency” and to its protective action which keeps the dirt and grease bolund in the form of an 0 68 BHATNAGAR STUDIES IN EMULSIONS. PART 11. emulsion. On this view the cleansing properties of maps will be considerably affected by the electrolytic impurities in water. Sodium linoleate and soaps with a little free alkali will be gmd for cleansing purposes as they give finer-grained emulsions than the sodium oleate solutions when pure water is employed for wash-ing. Large amounts of calcium or barium salts or salts of ter-valent metals in water will be injurious in these cases as well as when neutral or acid soap solutions are eniployed for the latter are also easily transformed into water-in-oil emulsions which are very sticky and difficult to remove by water.It is intended to study the varioius physical properties particu-larly viscosities of emulsions of two immiscible liquids sf equal densities in order to obtain more evidence as to the mechanism of the reversal of phases in emulsions and further work on the renewal of phases in emulsions prepared by insoluble emulsifiers is in progress. Summary. (1) It has been shown that tervalent electrolytes are more effective in bringing about the reversal of phases than bivalent ones. (2) Soaps and electrolytes have been arranged in the order of their emulsifying and precipitating powers respectively for B .P. paraffin oil emulsions. (3) It has been sholwn that the reversal of phases in emulsions, the precipitation of sols in suspensions,' and the coagulation of natural emulsions like milk are similarly affected by dilution. (4) The bearing of the results on the chemical interpretation of the washing power of soap is briefly discussed. (5) The effects of free alkalis and free fatty acids on soap emulsions have been investigated. The author takes 6his opportanity of t,hanking Prof. F. G. Donnan F.R.S. for the help afforded him during this investiga-tion. His thanks are also due to Dr. J. C. Ghwh and Mr. J. N. Mukherjee. CHEMICAL LABORATORY. UNIVERSITY COLLEGE, LONDON W.C.l. [Received October 12th 1920.

ISSN:0368-1645    

DOI:10.1039/CT9211900061

出版商:RSC    

年代:1921

数据来源: RSC

摘要:

@-AMINO-&PHENYLPROPIOPHENONE. 69 VI.-&Arnino-p-phenylpropiophenone. By ALEX. MCKENZIE and FRED BARROW. a-AMINO-KETONES. for example a-aminopropiophenone exhibit great instability in the free state on account of their tendency to condense in the presence of air to give substituted pyrazincs (Gabriel Ber., 1908 41 1127). On the other hand S-amino-ketones are much more stable; diacetoneamine is exceptional as it can even be dis-tilled but other ketones of this class are not nearly so stable; thus Gabriel (Ber. 1908 4 1 242) has shown that P-aminopropiophenone evolves ammonia when heated with aqueous potassium hydroxide, and it does not appear from his description that the compound is stable enough to be kept a t the ordinary temperature for any length of time.For the purpose of another research it was desired t o obtain a P-amino-ketone containing an asymmetric carbon atom and the preparation of B-amino-p-phenylpropiophenone was accordingly undertaken by the authors in the hope that this compound would be sufficiently stable to permit of its isolation. The preparation was carried out as follows. Cinnamic acid was converted into P-amino-& phenylpropionic acid from which the corresponding phthalimino-acid was obtained by heating with phthalic anhydride. The action of benzene and aluminium chloride on the chloride of the phthal-imino-acid led to ~-phthalimino-/3-phenylpropiophenone which was converted by means of aqueous alkali into the corresponding phthal-amic acid (compare Gabriel Ber. 1908 41 242 513 and other papers by the same author).T"he hydrolysis of the phthalamic acid was accomplished by a mixture of glacial acetic acid and concen-trated hydrochloric acid. The resulting hydrochloride on decom-position with ammonia gave P-amino-P-phenylpropiophenone as a solid melting a t 82-83O. The free amino-ketone is much more stable at €he ordinary temperature than is desylamine the related a-amino-ketone. An attempt was made t o obtain the ketone by a more direct method namely by the action of magnesium phenyl bromide on ~-amino-j3-phenylpropionanilide NH,*CHPh*CH,*CO*NHPh. The disruption of the additive compound by aqueous ammonium chloride led however to the regeneration of the anilide. The result would suggest that the additive compound may have been 7 HPh CH,*E*N Ph*MgBr NH*MgBr .0 J I . Ph MgB 70 MCKENZIE AND BARROW : in which case the rearrangement into a product giving the amino-ketone on hydrolysis did not occur. Now it has been found by McKenzie Martin and Rule (T. 1914 105 1583) that the action of Grignard reagents on allrylnted acid amides (for example, r-mandeloethylamide and I-P-hydroxy-/il-phenylpropionethylamide) does not always lead to the formation of the corresponding lretols, and it seems probable that the additive compounds formed in those cases may also have been of the oxonium type postulated above. v. Braun has in fact suggested the structure for the compounds obtained from dialkylated amides. The recent work of v. Braun Heider and Muller (Ber. 191'7 50 1637) and of v. Braun and Kirschbauin (Ber.1919 [B] 52 1725) on the action of Grignard reagents (prepared from bromoalkylsted anilines) on aldehydes and ketones respectively certainly lends support to the view that the first phase in the addition of a Grignard reagent to an aldehyde or a ketone consists in the formation of an oxonium compound where the reagent attaches itself to the oxygen atom of the carbonyl group of the aldehyde or ketone. Such an additive ccmpoiind would be labile enough to undergo as a general rule, iscmeric change with readiness prior t o its hydrolysis but appa-ren€ly it may sometimes happen that this rearrangement does not occur. T'he action of aluminium chloride on a solution of P-formylamino-,8-phenylpropionyl chloride in benzene took an unexpected course, the product being /3p-diphenylpropiophenone.Now it is shown in the present paper 1 hat P-phthalimino-/il-phenylpropionic acid decom-poses on heating into carbon dioxide phthalimide cinnsmic acid, and styrene the last-named substance being doubtless formed from the cinnamic acid (I). This result siiggested a similar course for R,N>,:o..,~~~f&~~lt: .R' c Ii *CIi.CH-CO('l 5 1 I .................................. . I i I b ; ; I I i NIC*CHO ................................. (11.1 the decomposition of P-f ormylamino-P-phenylpropionyl chloride into f ormamide and cinnamoyl chloride (11) aluminium chloride acting as a catalyst. The cinnamoyl chloride formed in this manner then reacts with benzene and aluminium chloride with the formation of Po-diphenylpropiophenone.The interaction of cinnamoyl chloride, benzene and aluminium chloride under the conditions described i 6-AMINO-6-PHENYLPROPIOPHENONE. 71 the experimental part gave a mixture of PP-diphenylpropiophenone and j3B-diphenylpropionic acid. B-Benzoylamino-P-phenylpropionyl chloride differed from the formyl compound inasmuch as it underwent the normal reaction with benzene and aluminium chloride the product being @-benzoyl-amino-& phenylpropiophenone . Some optically active derivatives of B-amino-j3-phenylpropionic acid are a t present under investigation by one of us (A. McK.). E X P E R I M E N TAL. @-A mino-8-phcnylpropionanilide. P-Amino-B-phenylpropionic acid was prepared by the action of hydroxylamine on cinnaniic acid according fo Posner's method (Ber., 1905 38 2316).Four grams of the well-dried and finely-powdered amino-acid were suspended in 20 C.C. of freshlydistilled acetyl chloride the mixt'ure was cooled in ice and treated gradually with 5.3 grams of finely-powdered phosphorus pentachloride. The mix-ture was shaken during the addition of the pentachloride (fifteen minutes) and the shaking was continued for half an hour longer at the ordinary temperature. The resulting solid 8-amino-P-phenyl-propionyl chloride hydrochloride was separated and washed with acetyl chloride and light petroleum. A solution of 2.5 grams of it were suspended in dry ether and treated a t the ordinary tempera-ture with a solution of 4.2 grams of aniline in ether. Water was then added the aqueous solution separated and made alkaline with sodium hydroxide.The anilide precipitated was crystallised from aqueous alcohol (Found C = 74.8 ; H = 6.9. Cl,Hl,0N2 requires C=75*0; H=6*7 per cent.). &Amino - fi - phenylpropio~aanilide NH,*CHPh*CH,*CO*NHPh, separates from ethyl alcohol in colourless plates melting a t 122O. It is readily soluble in ethyl alcohol or chloroform moderately so in benzene or ether and sparingly so in light petroleum. Attempts to prepare the amide and the piperidide of 8-amino-P-phenylpropionic acid by the action of dry ammonia and of piper-idine on a suspension of the chloride hydrochloride in dry ethereal solution gave amorphous products probably due to polypeptide formation. The anilide (1 mol.) was subjected to the action of magnesium phenyl bromide (6 mols.).On decomposing the additive compound with ammonium chloride the anilide was regenerated 72 McKENZIE AND BARROW : A ction of P-Formylamino-&phenylpropionyI Chloride on Benzene in the Presence of Aluminium Chloride. The formylation of the amino-acid was carried out as described by Fischer Scheibler and Groh (Ber. 1910 43 ZOZO) and the formyl acid then converted into its chloride by means of acetyl chloride and phosphorus pentachloride. The chloride prepared frcm 3.9 grams of the formyl acid was a viscid yellow oil; it was dissolved in 50 C.C. of benzene and acted on by 5 grams of alumin-ium chloride by heating on the water-bath for one hour. After decompdsition with hydrochloric acid and removal of the benzene, the product was crystallised twice from ethyl alcohol when lustrous needles (0.7 gram) separated.These melted a t 94-95O contained no nitrogen and consisted of PB-diphenylpropiophenone, CHPh,-CK,*COPh (Found C = 88.1 ; H = 6-5. Calc. C = 88.1 ; H=6.3 per cent.). Kohler (Amer. Chem. J. 1903 29 352) gives m. p. 96O. Action of Cinnamoyl Chloride on Benzene in the Presence of ,4 luminium Chloride. This action had already been investigated by Kohler Heritage, and Burnley (Amer. Chcm. J. 1910 44 60) under somewhat different conditions to those employed by us. They found that PP-diphenylpropiophenone was accompanied by 3-keto-1-phenyl-2 3-dihydroindene and P-chloro-6-phenylpropiophenone. The product obtained under the following conditions appeared t o consist entirely of PB-diphenylpropionic acid and p/3-diphenylpropiophenone.A mixture of 10 grams of cinnainic acid and 14.8 grams of phos-phorus pentachloride was heated on the water-bath for half an hour, the oxychloride removed under diminished pressure and the result-ing oil acted on by 50 C.C. of benzene and 10 grams of aluminium chloride. The action was completed by heating and the mixture allowed to remain overnight. Dilute hydrochloric acid was added, the product extracted with ether and the ethereal solution then shaken with sodium carbonate. On acidifying the alkaline extract with hydrochloric acid 5.1 grams of p/3-diphenylpropionic acid were precipitated which after crystallisation from ethyl alcohol separated in lusirous white needles melting a t 149-150°. Liebermann and Hartmann (Ber.1892 25 2124) who obtained the acid as one of the products of the action of sulphuric acid on cinnamic acid and benzene give m. p. 149O. (Equivalent =229.1. Calc. =226.) After being dried with sodium sulphate the ethereal solution on evaporation gave a red oil which solidified almost completely whe ,&AMINO-@-PHENYLPROPIOPHENONE. 73 kept in the ice-chest for two days. The solid was freed from a small quantity of oil and purified by crystallisation from alcohol. It amounted to 11.5 grams and consisted of PPdiphenylpropio-phenone. B- Benzoylamino-6-phenylpropiophenone. 8-Amino-P-phenylpropionic acid was converted into its benzoyl derivative which melted a t 194-195O whereas Posner (loc. cit.) gives 194-196O. Ten grams of the benzoylamino-acid were con-verted by means of acetyl chloride and phosphorus pentachloride into P-benzoylamino-P-phenylpropionyl chloride which crystallises in needles.The latter was dissolved in 50 C.C. of benzene and acted on by 10 grams of aluminium chloride. After the usual manipula-tion 4.1 grams of a solid were isolated. P-Benzoylamino- P-phenylpropiophenone, NHB z- CHP h CH2*COP h, separates from ethyl alcohol in lustrous slender colourless needles melting a t 152-154O (Pound C = 79.9 ; H = 6.1 ; N = 4.3. C2,H,,02N requires C = 80.2 ; H = 5.8 ; N = 4.3 per cent.). P-Ph thalimino-P-pheny Zpropionic A cid. A mixture of 11 grams of P-amino-p-phenylpropionic acid and 10.5 grams of phthalic anhydride were heated for two hours a t 155-165O a t the end of which time the phthalimino-acid com-menced to crystallise from the molten mass.On cooling the acid was dissolved in 20 C.C. of hot glacial acetic acid and 20 C.C. of benzene were added. On cooling 13 grams of the crude acid separated. Purification was effected by crystallisation from benzene. ~-P~thalimino-P-phenylpropionic acid, C,H,:(CO),:N*CHPh*CH,*C02H, melts a t 169*5-170*5O is very readily soluble in hot ethyl alcohol or hot glacial acetic acid moderately so in benzene and very spar-ingly soluble in hot water. It separated from alcohol in slender needles (Found C= 69.1 ; 13 = 4.7. C,,H,,O,N requires C = 69.1 ; H=4*4 per cent.). In a second preparation 35 grams of phthalic anhydride and 36 grams of the amino-acid gave 48 grams of the phthalimino-acid melting at 168-170° after one crystallisation from a mixture of 60 C.C.of glacial acet,ic acid and 60 C.C. of benzene. The acid chloride prepared by heating the acid with an excess of thionyl chloride for half an hour separates from benzene in needles melting a t 96-97O. For analysis it was dried over phos-D 74 McKENZIE AND BARROW : phoric oxide and paraffin wax (Found C1= 10.6. C,,H,O,NCl requires 11.3 per cent.). The anilide prepared by the interaction a t the ordinary tem-perature of aniline and the acid chloride in ethereal solution sepa-rates from glacial acetic acid in glistening prisms or rhomboidal plates melting at 238O. It is sparingly soluble in ethyl alcohol (Found N- 7.5. C,,H,,O,N requires N=7*6 per cent.). The methyl ester prepared by the esterification of the acid with methyl alcohol and hydrogen chloride separates from ethyl alcohol in plates melting a t 9 2 O (Found N=4-9.C18H,,04N requires N=4*5 per cent.). The action of heat on B-phthalimino-8-phenylpropionic acid was studied. Evolution of carbon dioxide began a t 240° and became vigorous at 300O. The temperature was maintained a t 320-350° for half an hour. 'The liquid which had a pronounced odour of styrene was then distilled under ordinary pressure. The residue was dissolved in ethyl alcohol and decolorised with charcoal ; phthal-imide was isolated from it. The distillate solidified to a white, crystalline mass which was crystallised twice from a mixture of ethyl alcohol and benzene; the product was identified as phthal-imide. The alcohol-benzene solutioii from which the phthalimide had been separated was extracted with aqueous sodium carbonate, and cinnamic acid was obtained from the alkaline solution by acidification and extraction with ether.B-P h t ha Zinzi?i.o -fl-phenylpropiophenone. The best conditions for the preparation of this compound were the following. Twenty-five grams of the phthalimino-acid were heated for half an hour on the water-bath with 20 grams of thionyl chloride until the evolution of hydrogen chloride ceased. The excess of thionyl chloride was removed by distillation under diminished pressure when the acid chloride remained as a very viscid yellow oil Benzene (100 c.c.) was added to the warm oil the greater part of which dissolved and on cooling separated in a mass of needles. Aluminium chloride (20 grams) was then added.Action soon started with evolution of hydrogen chloride. After remaining a t the ordinary temperature overnight the mixture was heated for twenty minutes when a further vigorous evolution of hydrogen cbloride took place. On cooling water and hydrochloric acid were added and the benzene removed by distillation in a current of steam. The ketone was left as a viscid pale yellow oil which solidified readily. It was separated and crystallised from ethyl alcohol. Yield 26 grams &AMINO -@-PHENYLPROPIOPHENONE . 75 B-Ph t halimino-&phenylpropiopheno ne, C,H,:C,O,:N*CHPh*CH~oC'BPh, separates from etlhyl alcohol in needles melting a t 116-117O. It is readily soluble in hot alcohol but only moderately so in the cold solvent.It crystallises sluggishly and tends to separate from hot concentrated solutions as an oil. B- Benzoy 1-a-ph enyle t hy l p h t halamic A cia?. B-Phthalimino-B-phenylpropiophenone (7.5 grams) was sus-pended in 20 C.C. of ethyl alcohol and heated on the water bath for ten minutes with 30 C.C. of N-sodium hydroxide. The solution was diluted with 200 C.C. of water and acidified with hydrochloric acid. The phthalamic acid was precipitated as an oil which on stirring coagulated to form a pasty mass and this on remaining overnight became quite solid and friable. It was purified by crystallisation from ethyl alcohol. B-Benzoyl-a-phenylethyl~~t~alamic acid, COPh*CH,-CHPh*NH*CO* C,H,-CO,H, separat'es from ethyl alcohol in needles melting a t 1 3 2 O (Found, N=3*T.C,,'H,,O,N requires 3.8 per cent.). It is readily soluble in acetone ethyl alcohol or glacial acetic acid moderately so in benzene and sparingly soluble in light petroleum. j3- A mino-6-pheny Zpropiophenone. A solntion of 10 grams of P-benzoyl-a-phenylethylphthalamic acid in 50 C.C. of hot glacial acetic acid was heated on the water-bath for one hour with 30 C.C. of concentrated hydrochloric acid; a small amount of a pale yellow oil separated on heating. On the addition of 150 C.C. of water a further quantity of oil was precipitated, which became pasty on shnkiug. The clear solution was separated and evaporated to about 50 C.C. under diminished pressure sepa-rated from a further small quantity of oil and finally evaporated to dryness under diminished pressure.The amino-ketone hydro-chloride was obtained in this way in slender colourless needles accompanied by a small amount of a viscid yellow oil. The aquecus soliition was extracted with ether and rendered alkaline with ammonia. The precipitated amino-ketone was extracted with ether the ethereal solution dried with sodium sulphate and the ether removed. The residual pale yellow oil solidified on cooling and was crystallised from a mixture of benzene and light petroleum. The yield was 0.75 gram. B-Amino-/3-phenylpropioyhenone NH,*CHPh*Cs*COPh crys-D* 76 P-AMINO-p-PHENYLPROPIOPHENONE. tallises in scft colourless leaflets melting a t 82-83O (Found, N=6.3. CI5Hl5ON requires N=6.2 per cent.). It is readily soluble in ethyl alcohol benzene ether or ethyl acetate and only sparingly so in cold light petroleum (b.p. 30-5OO). It is moderately stable differing in this respect markedly from desylamine; thus a specimen kept in a well-corked tube underwent n3 apparent change when kept for six days. It then became yellow the crystals adhered together and after a further four to five days it was transformed into a yellowish-brown semi-liquid mass. In another preparation where 15 grams of the phfhalamic acid were hydrolysed by heating for half an hour with 60 C.C. of hydro-chloric acid and 100 C.C. of glacial acetic acid the yield of amino-ketone (2.5 grams) was better than in the experiment just described. The picrate crystallises from ethyl alcohol in yellow leaflets (Found N = 12.4. C,,H,,ON,C6H30,N3 requires N= 12.3 per cent.) which commence to darken and sinter a t 175O and melt and decompose a t 193O. The platinichloride separates from dilute hydrochloric acid in brown needles (Found Pt = 22.5. (C,,H,,ON),H,PtCl requires Pt=22*7 per cent.). It shows no definite melting .point but com-mences to darken and shrink to a thin core a t 195O decomposition being complete a t 250O. The crude P-amino-j3-phenylpropiophenone hydrochloride result-ing from the hydrolysis of the phthalamic acid was shaken with benzoyl chloride and sodium hydroxide. The resulting solid was crystallised from ethyl alcohol from which it separated in needles melting a t 152-153O. This was identical with the benzoyl deriv-ative previously described (p. 73) obtained by the interaction of /3-benzoylamino-P-phenylpropionyl chloride and benzene in the presence of aluminium chloride. UNIVERSITY COLLEGE DUNDEE, UNIVERSITY OF ST. ANDREWS. BIRKBECK COLLEGE, LONDON E.C. [Received December 17th 1920.

ISSN:0368-1645    

DOI:10.1039/CT9211900069

出版商:RSC    

年代:1921

数据来源: RSC

摘要:

DENHAM THE METHYLATION OF CELLULOSE. PART m. 77 VIL-The Methylation of Cellulose. Part 111. Homogeneity of Product und Limit of Methylation. By WILLIAM SMITH DENHAM. IN previous'papers (Denham and Wooldhouse T. 1913 103 1735 ; 1914 105 2357; 1917 111 244) the methylation of cellulose and of starch was announced and some results were communicated of an investigation on the methyl ethers of cellulose and their hydrolytic proiducts. The latter include a well-defined crystalline trimethyl glucose to which a constitutional formula has been assigned. Immediate aims in the development of this research have been the preparation of a methyl ether of maximum methoxyl content in which the cellulose complex shall have undergone the minimum of degradation and the examination of the limiting and intermediate ethers and their degradation products.It is pro-posed to amplify and discuss in a subsequent communication the additional results now presented. For t8he preparation of a highly methylated cellulose the methood already described namely the treatment with methyl sulphate of cotton which has been soaked in a solution of sodium hydroxide, was found to be the most successful and repetitions of this process, variously modified have yielded a product containing 44.6 per cent. of methoxyl. This value approximates to the 45.6 per cent. od methoxyl required by theory for trimethyl cellulose. The slow rate of increase in the methoxyl content' during the final stages of the methylation itself an indication that the limit has been nearly approached has rendered advisable the additional observations now in progress before the limit can be definitely announced.That these ethers retain a high degree olf complexity is indicated by the almost complete absence of copper-reducing property in a product containing aboutl 40 per cent. of methoxyl in which as in more highly methylated preparations the fibrous structure ot cellulose persists. Further the displacement of hydrogen by methyl groups does not confer solubility in such solvents as alcohol, acetone or chloroform. The solubility of methylated cellulose in Schweitzer's reagent, on the other hand appears to decrease as the methoxyl content increases and products which contain about' 40 per cent. of methoxyl are insoluble. The question of the homogeneity of methylated cellulose is of great importance in relation to deduc-tions regarding the constitution of cellulose from the natur 78 DENHAM THE METHYLATION OF CELLULOSE.PART 111. of the hydrolytic products and some experiments which give information on this point may therefolre be referred to, although they were made primarily to ascertain whether by the restricted action of Schweitzer’s reagent especially on preparations of low average methoxyl content a highly methylated portion could be separated to servo as a convenient source of the crystalline trimethyl glucose. It was found that several preparations of methyl cellulose when treated with Schweitzer’s reagent so that only a part was dissolved yielded a residue with a methoxyl con-tent greater than that of the untreateid substance.The degree of heterogeneity thus revealed depends as might be expected on the manner of preparation of the methyl cellulose; f o r material of lolw average methoxyl content it was greatest where concen-trated alkali had been employed possibly owing to an unequal penetration of the cotton by the alkali. The most homogeneous product of those examined was one in the preparation of which an ethereal solution of methyl sulphate was employed and it may be nolted that the best yields apparent in an increased weight of material after methylation were obtained when etheir was present. A preparation containing about 40 per cent. of methoxyl gave indications of lack of uniformity explicable from its history; one containing 42 per cent.of methoxyl was quite insoluble in Schweitzer’s reagent and in alcohol acetone or chloroform and is therefore so far homogeneous. A comparison of the history of the sample of methylated cellu-lose which yielded the hydrolytic products already described and discussed (T. 1914 105 2357) with the histories of the prepar-ations made without ether which were examined by means of Schweitzer’s reagent indicates a superior uniformity in the earlier product as in the later ones there were fewer stages in the methyl-ation. It is thus probable that the trimethyl glucose was derived, not from a small proportion of highly niothylated substance but frolm a more general distribution of trimethyl glucose residues in the cellulose complex, As the limit is approached irrsgularitics in methylation will be smoothed out but the question of yield remains.The loss of material due to chemical action need not bei great. I n one series, 100 grams of cotton gave 104 grams of methyl cellulose containing 31.3 per cent. of methoxyl the yield being thus 91 per cent. of the theoretical ; the product had undergone four treatments that is it had been soaked in alkali treated with methyl sulphats and washed and dried folur times so that a t Isast a part of the loss was mechanical. Owing to losses due to mishaps the yields have not been followed continuously to the highest degree of methyl-ation attained; the loss is small however from stage to rrtage an DENHAM !CHE METHYLATION OF CELLULOSE. PART m. 79 is usually quite clearly mechanical loss sustained in manipulation.The conclusions seem to be justified1 that the limit of methyl-ation of cellulose lies in the neighbourhmd of that required for trimethyl cellulose and thatl a methyl cellulose of this limiting methoxyl content can be prepared which is representative of the whole of the original cellulose. The further investigation of these questions and of the fission products of methyl cellulose is in progress. EXPERIMENTAL. The following examples illustrate the yields obtained in several preparations of methyl cellulose and the behaviour of the products t olwar ds Sch w ei t z er ’s reagent . I. Methyl Cellulose condaining 20.4 per cent. of MethoxyJ.-The solution of sodium hydroxide employed contained 20 grams of the solid in 1OO.c.c. of solution.No solvent was employed for the methyl sulphate sIightly more of which was added than is represented by the ratio MI+~O,:N~OR. In each stage the temperature rose to1 70° during the reactioa and the mixture was afterwards warmed gently until acid throughoutl. 1st Stage.-l65 Grams of cotton wool 500 C.C. of sodium hydr-oxide solution 390 grams o€ methyl sulphate. Yield 135 grams. Methoxyl content not determined. 2nd Stage.-135 Grams of the product from the first stage, 400 C.C. of sodium hydroxide solution 236 grams of methyl sulphate. Yield 98 grains. OMe=20*4 per cent. Action of Schweitzer’s Reagent.-The prod-uct from the second stage after remaining for seven days with 4 litres of Schweitzer’s reagent leftl 42 grams of undissolved residue containing OMe=22*7 per cent.Three quantities of 3 grams each of the substance containing OMe= 22.7 per cent. were again treated each with 170 C.C. of Schweitzer’s reagent: (a) Residue after two days (1.5 grams) contained OMe= 23.1 per centl. ( 6 ) Residue after five days (1.3 grams) contained OMe=24.3 per centi. ( c ) Residue after seven days (1.3 grams) contained OMe=24.7 per cent. The mixed residues were completely soluble in Schweitzer’s reagent. ( d ) By the action of Schweitzer’s reagent on 28 grams of the substance containing OMe= 22.7 per cent. 4.4 grams of undis-solved residue were obtained which contained OM@= 23-4 per cent. The 4.4 grams were again treated with Schweitzer’s reagent so as to leave a small residue (weight not determined) which contained OMe=28 per cent 80 DENHAM THE METHYLATION OF CELLULOSE.PART 111. The Schwelitzer s reagent was prepared t y shaking freshly pre cipitated copper hydroxide with concentrated aqueous ammonia (D 0*88) and had D aboiut 0.93. It was not standardised as regards content of ammonia or copper but the reagent was tested to make sure that it dissolved cotton. The undissolved cellulosic residue was recovered by diluting the solution with aqueous ammonia filtration through nickel gauze and washing with aquelous ammonia and water. Small quantities were relcovered by allowing the filtered solution to settle. The methyl cellulose the hydrolytic prolducts froim which have beien described (T. 1914 105 2357) was prepared in six stages; in the first five the solution of sodium hydroxide cantaineld 17 grams of the solid in 100 c.c.and the product contained OMe=20.7 per cent. I n the final stage the sodium hydroxide solution contained 38.3 grams of the solid in 100 c.c. and the productl contained OMe = 23.6 per cent. 11. Methyl Cellulose con taming OMS = 39.5 peT cent .-This substance was prepared in nine stages. After three stages in each of which the material was impregnated with half its weight of sodium hydroxide added as a solution containing 21.4 grams of the sollid in 100 c.c. the OMe content was 24.8 per celnt. In all the stages somewhat less methyl sulphate was employed than is reipresented by the ratio Me2S0,:NaOH and the substance remainelcl alkaline after the reaction was over. From 160 grams of cotton wool were obtained 135 grams the yield being 7 9 per cent.of that obtainable of a product having OMe=24-8 per cent. In the later stages the1 sodium hydroxide solution contained 38.8 grams s f the solid in 100 C.C. Difficultiw were encountered in impregnating the1 material with the alkaline solution and the material was cut up into small pieces squeezed in a press pounded, etc. so’ that there was considerable loss. The percentage of metholxyl remained stationary from the eighth to the ninth stage (OMe = 39.7-39.5 per cent.). A c t i o n of Schweitzer’s Reagent.-2.8 Grams of the product con-taining OMe=39*5 per cent. after treatment with 50 C.C. of Schweitzer’s reagent for four days gave 2.6 grams of undissolved residue containing OMe =40 per cent. ; 2.4 grams of this residue, on further treatment with Schweitzer’s reagent were reduced to 2-2 grams which contained OMe=40*4 per ce!nt.Copper Reduction.-0*978 Gram of substance (OM@= 39.5 per cent.) was treated with Fehling’s solutioln as in the examination of cottoin. 0.15 C.C. olf iV/lO-sodium thiosulphate was required for the titratioin of the reduceld copper. 111. Preparation of M e t k p l Ce7liiloaP using Ether.-One Cu,O=Q~ll per cent DENHAM THE METHYLATION OF CELLULOSE. PART III. 81 hundred grams of cotton wool were soaked for one day in 1 litze od a solution of sodium hydroxide (20 grams in 100 grams of solution) and then drained and pressed so thatl 350 grams od‘ the solution (coataining 70 grams of sofdium hydroxide) were left. One hundred C.C. of methyl sulphate and 700 C.C.of ether were added the mixture was heated under reflux for a few hours and the ether was then removed by distillation. The weight of the washed and dried profduct was 105 grams. A repetition of this process gave 107 grams oif EL product containing OMe=24*5 per cent. In a third and fourth repetition of the process where the impregnation of the material by the solution ot alkali was assisted by exhausting the containing vessel less sodium hydroxide was retained. The product from the fourth treatment contained OMe=31-3 per cent. and weighed 104 grams the yield being thus 91 per cent. of the theoretical. The weights were determined under similar conditions after drying the material in a steam-oven. Action of Schweitzer’s Reagent.-From 2.88 grams of subst4ance (OMe=31.3 per cent.) after immersion in 100 C.C.of Schweitzer’s reagent for three hours 1.93 grams of undissolved substance (OMe=32.4 per cent.) were recovered. Eighty-eight grams of methyl cellulose containing OMe = 15.6 per cent. which had been made in one stage using ether were immersed in 600 C.C. of Schweitzer’s reagent for three days when 8.4 grams of undissolved material were recovered containing OMe=15.2 per cent. IV. Methyl Cellulose containing moTe than 40 per cent. of Metho&.-Highly methylated products were prepared by variants od the methods already described. For one of these the following analytical results were obtained (Found C =52-19 ; H = 7-63 ; OMe= 44.6 per cent. Trimdhyl cellulose C,H,,O,, requires C=52.9; H=7*84; OMq=45*6 per cent.). A ctim of Solvents.-The behaviour of a preparation containing OMe=42 per cent. was examined towards alcohol acetone and Schweitzer’s reagent. 1.8802 Grams after being extracted with alcohol for three hours in a modified Soxhlet apparatus weighed 1.8796 grams. The same sample was then extracted in the same way with acetone for three hours and afterwards weighed 1.8790 grams. 0.408 Gram of the same substance was immersed in Schweitzer’s reagent for twenty-four hours; the weight of the undissolved substance recovered was 0.407 gram. CHEMISTRY DEPARTMENT, ST. MARY’S HOSPITAL MEDICAL SCHOOL, PADDINGTON W. 2. [Received November 29th 1920.

ISSN:0368-1645    

DOI:10.1039/CT9211900077

出版商:RSC    

年代:1921

数据来源: RSC

摘要:

82 BAGSTER THE REACTION BETWEEN VIII.-The Reaction between Nitric Acid and Copper. By LANCELOT SALISBURY BAGSTER. ON attempting to measure the volume of nitric oxide produced by the action of 5N-nitric acid on copper under certain conditions, it was found that when the gaseous products were evolved and passed into sodium hydroxide solution in a vacuum complete absorption took place although a considerable volume of nitric oxide should have been obtained (Higley Amer. Chem. J. 1905, 3.7 IS). This reaction was investigated in the hope of throwing further light on the reaction between nitric acid and copper. Veley (P/~il. Trans. 1891 182 279) showed that the nitrous acid present was the cause of solution in dilute acid and proposed a series of reactions involving the reduction of the nitrous acid to nitric oxide followed by the oxidation of the nitric oxide to nitrous acid by the nitric acid.The work of Lewis and Edgar ( J . Amer. Chem. SOC. 1911 33 292) shows that there is an equilibrium between nitric acid nitric oxide and nitrous acid and that this equilibrium is butl slowly attained. It seems unlikely therefore, that in such case the nitric oxide would be completely and instantly oxidised as would1 be necessary to secure compleite absorption of the product in the experiment just described. The follolwing explanation of the procms in terms of well-known electrochemical theory is suggested (1) oxidation of the hydrogen film on the copper by the! nitrous acid which itself is reduced to hyponitroas acid the copper passing into solutioln to replace the hydrogen removed ; (2) oxidation of the hyponitrous acid to nitrous acid by nitric acid which itself is reduced to nitrous acid.I t may be assumed thatl the first reaction will pro+ duce hyponitrous acid in unimolecular form (H2+ HNO + M,O+ HNO') and as Divers (T. 1889 75 112) has sholwn that hyponitrous acid has the double molecule i t may be considered that a t the moment of formation it' will be in a reactive state corresponding with nascent hydrogen and completely oxidised by nitric acid. It will bei shown that the product of reaction with dilute acid is nitrous acid produced in quantity necessary to satisfy the above scheme. It might be expected that sufficiently dilute nitric acid would fail to oxidise completely the hyponitrous acid formed and in such case nitrous oxide the well-known decom-position product of hyponitrous acid should appear as a product NITRIC ACID AND COPPER.83 This has been found to be the case by Higley (Zoc. cit.) using 3N and more dilute acid. It would not be expected that much nitrous oxide should be obtained; i f the nitric acid were so weak that itl failed to oxidise most of the hyponitrous acid the reaction would cease when tho nitrous acid originally present was exhausted. This has been found to be the case with N/Z-nitric acid. Reaction started by addition of sodium nitrite ceased when the nitrous acid was destroyed but could be restarted by the addition of more nitrite. Divers (Zoc. cit.) has shown that nitrous acid oxidises hype nibrous acid with the formation of nitric oxide and water and in the course of the present work it was found that nitric oxide is the only gaseous product of reaction between copper and an excess of N / 3-nitrous acid prepared by adding sodium nitrite solution to excess of dilute hydrochloric acid.Here hyponitrous acid formed would in the absence osf nitric acid be oxidised by the excess of nitrous acid. As in the case of very dilute nitric acid, it would be expected that very dilute nitrous acid would also produce some nitrous oxide. This has been verified in the case of N/50-nitrous acid prepared as above reacting with an excess of copper. Nitric oxide was produced but at the end of the reac-tion the gas in solution was collected and found to consist largely of nitrous oxide.The nitrous oxide was probably formed when the nitrous acid had become nearly exhausted. It is unlikely that the hyponitrous acid will be oxidised by nitrous acid in the presence of much nitric acid as the nitrous acid in the neighbour-hood of the copper will react with it and conditions will con-sequently be favourable for oxidation of the product by the nitric acid if present# in quant<ity. Further Peters (Zeitsch. nnorg Chem. 1919 107 313) states that in the presence of carbon dioxide a 5 per cent. solution of sodium nitrite reacts with copper producing nitric and nitrous oxides nitrate being formed in solution. Known constants for nitrous and carbonia acids show that about' 0.25 per centl. of the nitrite will be present as free acid which a t this very small con-centration will react with the copper in the manner already dis-cussed the same products being obtained.The nitrate would be formeid by direct decomposition of the nitrous acid. Reference should finally be made to the work of Ackworth and Armstrong (T. 1877 32 54) where it is shown that copper salts in solution give rise to an increased yield of nitrous oxide. These authors used a small vcllume of nitric acid and itl is probable that as the acid became usedl up the nitrous acid accumulated in solu-tion would react with the hyponitrous acid formed. A deep blu 84 BABSTER THE REACTION BETWEEN collour characteristic of complex copper salts was noticed when copper was dissolved in nitrous acid during the present work. This complex in the case of Armstroag's wotrk would diminish the concentration of free nitrous acid thus leading to the form-ation of a greater quantity of nitrous oxide.It has been shown (Ihle Zedtsch. physdkal. C'hem. 1895 19 577) that nitric acid above 35 per cent. by volume will react in the absence of nitrous acid. This concentration corresponds with just under 8A7. Reference t c the table (p. 86) shows that such acid yields nitrogen peroxide as well as trioxide. As a secondary reaction is not apparent in the experiments described with dilute acid it is probable that the products obtained from stronger acid nearly represent primary ones. The nitrogen peroxide may be regarded as the product of the direct oxidation process by the nitric acid, the nitrous anhydride also obtained in quantity from 8N- and 1ON-acid being due to the simultaneous progress of both types of reaction.So far discussion has been confined to dilute acid. EXPERIMENTAL. When the experiment described a t the beginning oif this work wa8 carried out quantsitatlively itl was found thatl the absorbing solutions contained nitrite corresponding with from 310 to 320 C.C. of N/lO-permanganate for every gram of copper dissolved. This result wit& obtained with the proiduct of reaction from acid of shength from 5N to 15N. The theoretical quantity of perman-ganate corresponding with the reactions discussed is 318 c.c. being the same whether the product is nitrous anhydride nitrogen tri-oxide or nitrogen peroxide. Nitrous acid i f formed would be expected under the conditions described to distil as anhydride, owing to the equilibrium ZHNO H,O + N,O,.To distinguish between the possible prolducts it was necessary to determine the total nitrogen in the absolrption vessel apart from any that might distil there directly as nitric acid. For this pur-pose the apparatus shown in the figure was constructed. Nitric acid was admitted after exhaustion to the vessel A containing the copper by means of the funnel B. Nitric acid was condensed in C and returned to A . Gaseous products were absorbed in D and) 8 which contained sodium hydroxide solution. Connexion with the mercury pump was closed by a tap during reaction. Tesk with this apparatus in the absence of copper showed that n NITRIC ACID AND COPPER. 85 appreciable quantity of nitric acid distilled through the condenser when mled to loo.In tthe course of preliminary tests using 10N and weaker acid, it was found that when the condenser was cooled ta Oo nitric oxide was produced there the effect being still slightly apparent a t loo witb 6N-acid. The probable explanation is that gaseous trioxide being a mixture a t the lower temperature the nitrogen peroxide is partly coadensed thus allowing the nitric oxide to pass on and throlugh the alkali unabsorbed. This effect would a t once be apparent in the caw of trioxide; if excess of peroxide were also present' greater condensation would have to take place before the composition fell below that' corresponding with trioxide when complete absorption would cease and nitric oxide appwr.The production of nitric oxide will be accompanied by a diminished quant4ity of prolducts in the absorption train. I n carrying olutl an experiment the nitric acid was kept boiling, the temperatares shotwn in the table being the boiling points of the acid solutions in a vacuum. A slow stream of carbon dioxide was passed through the tube F to sweep the gaseous products from the condenser after removal of the acid vapour. For analysis the nitrite in a portion od the absorption soflution was determined with permanganate and the total nitrogen in the residue estimated as ammonia by distillation with Devarda's alloy. A series of results is shown in the following table. In each case 0.250 gra 86 THE REACTI.ON BETWEEN NITRIC ACID AND COPPER. of copper was used and a t least’ ten times the quantity of acid needed for solution.No. 1 2 3 4 6 6 7 8 9 10 Nitric acid. D. 1.40 1-40 1.30 3.30 1.30 1.25 1.20 1.20 1.20 1.17 Nor-mality of acid. 14.5 14.6 10 10 10 8 6 6 6 5 Nitrogen Total Temper- as N,Oa. nitrogen. ature. Gram. Gram. 60” 0.0553 0-0980 60 0.0546 0.1001 45-50 0.0557 0.0616 45-50 0.0560 0.0630 45-50 0.0542 0.0600 35-40 0.0542 0.0582 30 0.0550 0.0610 30 0.0490 0.0490 30 0.0420 0.0423 30 0.0546 0.0595 N,O& Per cent. 77 80 10.2 11.0 10-5 7.2 (10.8) -(9) Temper -Nitrogen ature of =NO. conden-Gram. ser. - 10” - 10 10 10 5 - 10 - 16 0.0045 10 0.0090 7 I 20 - - -The theoretical quantity of trioxide to satisfy the reactions suggested is 0.0555 gram the total nitrogen being the same when trioxide is the product and twice the amonnt if peroxide is the only product.The blank tests showed that in the case of experiments 1 to 6 there was no nitric acid distilled to make the total nitrogen value high. The small loss of nitrogen mentioned as occurring with the weak acid must still be considered as taking place however with the condenser a t 10”. Although as explained this loss will not be apparent in the trioxide value it will introduce an error of a few milligrams in the total nitrogen value. I n the case of experiments 7 and 10 the value for the total nitrogen is higher than it should be; the copper in the case of the 6N-acid relquirsd a considerable time for solution the acid occasionally “boiled with bumping,” and unless the temperature of the condenser was as low as loo nitric acid reached the absorbers by direct distillation.Values such as are shown were repeatedly obtained but it was not possible to secure a more definite result. As already indicated, the fact that the product from 5 N - and GN-acid more easily forms nitric oxide than that from 8N- and 10N-acid shows that it con-tains less peroxide. Considering the facts stated it may be con-cluded that the product from 5N- and 6N-acid is almost entirely nitrogen trioxide (nitrous anhydride). The low values for the products in experiments 8 and 9 will be raised tot the same value as the others if allowance is made for the nitrogen lost owing to the folrmation of nitric oxide this value being nearly that demanded by theory. Allowing for the correction suggested for the prGducts from more concentrated acid the product from 14.5H-acid will contain 85 to 90 per cent. of peroxide the residue being trioxide for 10N FORMATION OF DERIVATIVES OF TETRAHYDRONAPHTHALENE. 87 acid there will be about 15 t o 20 per cent. of peroxide and for the 8N-acid somewhat less. It was not practicable to carry out work with acid more dilute than 5A7 owing to the time taken for solution in a vacuum prob-ably on account of the continuous removal olf nitroius acid which in consequence could not ex& its usual ‘‘ autwatalytic ” effects. THE UNIVERSITY OF QUEENYLAND, BRISBANE. [Received Pebrumy 27th 19201

ISSN:0368-1645    

DOI:10.1039/CT9211900082

出版商:RSC    

年代:1921

数据来源: RSC