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J O U R N A L OF THE CHEMICAL SOCIETY. TRANSACTIONS. Committat of @nblicatiotr : E. C. C. BALY C.B.E. F.R.S. 0. L. BRADY D.Sc. A. W. CROSSLEY C.M.G. C.B.E., D.Sc. F.R.S. C. H.DESCB D.Sc. Ph.D. F.R.S. C. 5. GIBSON O.B.E. bLA. B.Sc., M.SC. I. M. HEILBRON D.S.O. D.Sc. Ph.D. J. C. IRVINE C.B.E. D.Sc. F.R.S. T. M. LOWRY C.B.E.,D.Sc. F.R.S. J. W. MCBAIN M. A. Ph.D. F. R.S. J. I. 0. MAssoN M.B.E. D.Sc. W. H. MILLS M.A. Sc.D. F.R.S. J. C. PHILIP O.B.E. D.Sc. Ph.D., R. H. PICKARD D.Sc. Ph.D. F.R.S. 'l'. S. PRICE 0. B.E. D.Sc. Ph.D. N. V. SIDGWICK M.A. Sc.D. F.R.S. J. F. TNORPE C.B.E. D.Sc. F.R.S. IV. F. WYNNE D.Sc. F.R.S. F.R.S. Cbitaxs : A. J. GREENAWAY. CLAREKCE SMITH D.Sc. &Mistant ,&rirextr : A. A. ELDRIDGE B.Sc. MARGARET LE PLA BSc.1923 VOL CXXIII. Part I pp. 1-1647. I 0 N D 0 N : GURNEY & JACKSON 33 PATERNOSTER ROW E.C. 4. 1923 PRINTED IN GREAT BRITAIN BY RICHARD CLAY & SONS LIMITED, BUNGAY SUFVOLK C 0 N T E N T S PAPERS COMMUNICATED TO THE CHEMICAL SOCIETY. PAQE 1.-Investigations on the Dependence of Rotatory Power on Chemical Constitution. Part XIII. The Spatial Configuration of the Unbranched Aliphatic Chain. By ROBERT HOWSON PICKARD JOSEPH KENYON and HAROLD HUNTER . . 1 11.-Investigations on the Dependence of Rotatory Power on Chemical Constitution. Part XIV. The Normal Aliphatic Ethers of d-p-Octanol. By JOSEPH KENYON and REGINALD ARTHUR MCNICOL . . 14 111.-Investigations on the Dependence of Rotatory Power on Chemical Constitution. Part XV. Some n-Alkyl Ethers of d-Benzylmethylcarbinol.By HENRY PHILLIPS 22 1V.-Investigations on the Dependence of Rotatory Pox er on Chemical Constitution. Part XVI. The Di-d- P-octyl Esters of the Saturated Dicarboxylic Acids. By LESLIE HALL . . 32 V.-Investigations on the Dependence of Rotatory Power on Chemical Constitution. Part XVII. A New Type V1.-Nitration of 3-Chloroacenaphthene. By GLADYS FAR-NELL . . . . 6 0 VI1.-The Chemistry of the Glutaconic Acids. Part XIII. The Isomerism due to Retarded Mobility. By JOCELYN FIELD THORPE and ARTHUR SAMUEL WOOD . . 62 VII1.-The Higher Oxide of Cobalt. By OWEN RHYS HOWELL . . . 65 1X.-The Relation between the Crystal Structure and the Constitution of Carbon Compounds. Part I. Com-pounds of the Type CX,. By ISABEL ELLIE KNAGGS .71 X.-Elimination of the Amino-group of Tertiary Amino-alcohols. Part I. By ALEX. MCKENZIE and ANGUS CAMP BE^ RICHARDSOX ’ . . 79 XI.-The Transition from the Colloidal to the Crystalloidal State. Solutions of Potassium Oleate. By LOUIS LEIGHTON BIRCUMSHAW . . 91 of Walden Inversion. By HENRY PHILLIPS . . 4 iv CONTENTS. XI1.-Studies in the n-Butyl Series. Part 11. The Four Stereoisomeric py-Di-p-tolylamino-n-butanes. By GILBERT T. MORGAN and WILFRED JOHN HICKINBOTTOM . XII1.-Investigations on the Dependence of Rotatory Power on Chemical Constitution. Part XVIII. The Di-I-menthyl Esters of the Saturated Dicarboxylic Acids. By LESLIE HALL . X1V.-Ring-chain Tautomerism. Part IV. The Effect of the Methyl Ethyl Grouping on the Carbon Tetrahedral Angle.By BALBIR SINGH and JOCELYN FIELD THORPE XV.-The Forniat ion and Stability of spi ro-Compounds. Part X. spiro-Compounds Derived from cyc2o-Heptane. By JOHN WILLIAM BAKER and CHRISTOPHER KELK INGOLD . . XV1.-Varying Valency of Platinum with Respect to Mercaptanic Radicles. By SIR PRAFULLA CHANDRA RAY XVI1.-Phenyltrimethylammonium Perhaloids. By HAMIL-TON MCCOMBIE and THOMAS HAROLD READE XVII1.-Benzbisthiazoles. Part 11. By STEPHEN RATH-BONE HOLDEN EDGE . . . X1X.-Synthesis of Substituted Thianthrens. Part I. Thianthren and Nitrothianthren. By SRI KRISHNA . XX.-The Determination of the Dissociation Pressures of Hydrated Salts by a Dynamical Method. Part 11. By JAMES RIDDICK PARTINGTON and DONALD BENNETT HUNTINOFORD . . XX1.-Production and Reactions of 2-Dithiobenzoyl.By MARY MCKIBBEN and ERNEST WILSON MCCLELLAND . XX1I.-The Investigation of meso-Thioanthracene Deriv-atives. Part I. Observations on the Production of Dit hioant hraquinone Dithiodiant hrone and other Closely Related Derivatives. By ISIDOR MORRIS HEIL-BRON and JOHN STANLEY HEATON . . XXII1.-Photocatalysis. Part 111. The Photosynthesis of Naturally Occurring Nitrogen Compounds from Carbon Dioxide and Ammonia. By EDWARD CHARLES CYRIL BALY ISIDOR MORRIS HEILBRON and HAROLD JACOB STERN . Part IV. The Influence of the Base on the Velocity of Sapon-ification of Esters. By ALBERT ERIC CASEMORE HAMIL-TON MCCOMBIE and HAROLD ARCHIBALD SCARBOROUGH. XXV.-Castelamarin-A Bitter Principle from Castela Nicholsoni. By LOUIS PIERRE BOSMAN , XX1V.-The Velocity of Reaction in Mixed Solvents.PAQE 97 105 113 122 133 141 153 156 160 170 173 185 197 20' CONTENTS. V PAGE XXV1.-The Speed of the Uniform Movement of FIame in By WALTER ~NASON XXVI1.-The System Tin-Arsenic. By QASIM ALI MANSURI XXVIII.-peri-Naphthindigotin. By SIKHIBHUSHAN DUTT . XX1X.-Dyes derived from Diphenic Anhydride. By SIKHIB-HUSHAN DUTT . XXX.-The Upper Limit of Diazotisability in the Benzene Series. Diazo-derivatives of Mesitylene. By GILBERT T. MORGAN and GLYN REES DAVIES . XXX1.-The Reactivity of Doubly-conjugated Unsaturated Ketones. Part IV. The Effect of Substitution on the Reactivity of 4’-Dimethylamino-2-hydroxydistyryl Ketone. By ISIDOR MORRIS HEILBRON and ABRAHAM BRUCE WHITWORTH .XXXI1.-Some Derivatives of Methylenediquinaldinc and their Relationship to the Carbocyanines. By FRANCES MARY HAMER . XXXII1.-An Examination of the Alleged Antimonious Hydr-oxides. By CHARLES LEA and JOHN KERFOOT WOOD . XXX1V.-2 5-Iminodihydro-1 2 3-triazole. Part I. Con-stitution of Dimroth’s 5-Anilinotriazole. By PAVITRA KUMAR DUTT . XXXV.-The Absorption of Moisture by Coal (and other Fuels). Part I. A Relation between Degree of Humidity in the Air and Moisture Content of Coal. By BURROWS MOORE and FRANK STURDY SINNATT . The Metallurgical Applications of Physical Chemistry. A Lecture Delivered before the Chemical Society on December 14th 1922. By CECIL HENRY DESCH . XXXV1.-The Constitution of the Disaccharides. Part VII. Sucrose. By WALTER NORMAN HAWORTH and WILFRED HERBERT LINNELL XXXVI1.-The Constitution of the Disaccharides.Part VIII. Sucrose. By WALTER NORMAN HAWORTH and JAMES GIBB MITCHELL . XXXVII1.-Isolation of the Oxide of a New Element. By ALEXANDER SCOTT . XXX1X.-The Configuration of the Doubly-linked Tervalent Nitrogen Atom. The Resolution of the Pyridylhydrazone of cycZoHexylene Dithiocarbonate. By WILLIAM HOBSON MILLS and HANS SCHINDLER . XL.-The Sorption of Iodine by Carbons Prepared from Carbohydrates. By JAMES BRIERLEY FIRTH . Mixtures of the Paraffins with Air. 2 10 214 224 225 228 238 246 259 265 275 280 294 301 31 1 312 32 v i CONTENTS. PAQBD XLI.The Chemistry of the Glutaconic Acids. Part XIV. Three-carbon Tautomerism in the cycloPropane Series.By FRANK ROBERT GOSS CHRISTOPHER KELK INOOLD, and JOCELYN FIELD THORPE . . 327 XLI1.-The Tautomerism of Amidines. Part I. 2 4- and 2 5-Diphenylglyoxalincs. By RICHARD BURTLES and FRANK LEE PYMAN . . 361 XLII1.-The Tautomerism of Amidines. Part 11. The Alkylation of Open-chain Amidines. By FRANK LEE PYMAN . . . 367 XL1V.-The Quantitative Absorption of Light by Simple Inorganic Substances. Part 11. The Chlorides of Arsenic Antimony and Bismuth. By ALEXANDER KILLEN MACBETH and NORAH IRENE MAXWELL . . 370 XLV.-The Influence of Papaverine on the Optical Activity of Narcotine in Acid Solution. By HAROLD EDWARD ANNETT . . 376 XLVI.4tudies in the Anthracene Series. Part IV. By EDWARD DE BARRY BARNETT and MARCUS AURELIUS MATTHEWS . . 380 XLVI1.-Derivatives of Semioxamazide.Part I. Ketonic Semioxamazones. By FORSYTH JAMES WILSON and ERIC CHARLES PICKERINQ . . 394 XLVII1.-The Densities of Dilute Solutions of Potassium Salts and the Volume Changes Occurring on Solution. By HAROLD HARTLEY and WII;T,TAM HENRY BARRETT . 398 XL1X.-The Estimation of Acetone in Met,hyl Alcohol and the Purification of Methyl Alcohol by Sodium Hypoiodite. By HENRY HUTCHINSON BATES JOHN MYLNE MULLALY, and HAROLD HARTLEY . . 401 L.-Di- and Tri-hydroxydeoxybenzoina. By ERNEST CUP-BEAN and HENRY STEPHEN . 404 L1.-Determination of the Isoelectric Point of Gelatin. A Criticism of Patten and Kellems’s Method. By THOMAS SLATER PRICE . . . . 410 LI1.-The Propagation of Flame in Complex Gaseous Mix-tures. Part V. The Interpretation of the Law of Speeds.By WILLIAM PAYMAN . . 412 LII1.-The Rate of Detonation in Complex Gaseous Mixtures. By WILLIAM PAYMAN and NOEL STANLEY WALLS . 420 LIV.-The Effect of Pressure on the Limits of Inflammability of Mixtures of the Paraffin Hydrocarbons with Air. By W m PAYMAN and RICHARD VERNON WHEELER . 42 CONTENTS. vii PAGE LV.-Investigations on the Dependence of Rotatory Power on Chemical Constitution. Part XIX. The Rotatory and Refractive Dispersions and the Absorption Spectrum of d-,-Nonyl Nitrite. By ROBERT HOWSON PICKARD and HAROLD HUNTER . LV1.-Researches on Residual Affinity and Co-ordination. Part XV. Interactions of Acetylpropionylmethane and the Tetrachlorides of Selenium and Tellurium. By GILBERT T. MORGAN HARRY GORDON REEVES .LVI1.-The Adsorption of Stannous Chloride by Stannic Acid. By GEORGE ERNEST COLLINS and JOHN KERFOOT The Electrolytic Form-ation of Stibine in Sulphuric Acid and in Sodium Hydr-oxide Solution. By HENRY JULIUS SALOMON SAND, EDWARD JOSEPH WEEKS and STANLEY WILSON WORREU L1X.-The System Chromium Trioxide-Nitric Acid-Water. By STANLEY AUGUSTUS MUMFORD and LIOKEL FELIX GILBERT . LX.-The Action of Alcohol on the Sulphates of Ammonium. By HORACE BARRATT DUNNICLIFF . LX1.-The Nitration of Benzaldehyde and the Monotropy of o-Nitrgbenzaldehyde. By OSCAR LISLE BRADY and SAMUEL HARRIS LXI1.-Bromo-derivatives of 4-Methylglyoxaline. By FRANK LEE PYMAN and GEOFFREY M~LLWARD TIMIMIS . LXII1.-The Formation of Quaternary Ammonium Salts. Part I. By EDWARD DE BARRY BARNETT JAMES WE-FRED COOK and ERNEST PERCY DRISCOLL LX1V.-The Constitution of Polysaccharides.Part VI. The Molecular Structure of Cotton Cellulose. By JAMES COLQUHOUN IRVINE and EDMUND LANGLEY HIRST . LXV.-Researches on Pseudo-Bases. Part IV. A New Synthesis of Tertiary Amines of the Form R.CH2.NR1R2. By GERTRUDE MAUD ROBINSON and ROBERT ROBINSON LXV1.-Preparation and Reactions of Bromopicrin. By LOUIS HUNTER LXVI1.-The Constituents of Indian Turpentine from Pinus hgifolia Roxb. Part 11. By JOHN LIONEL SIMONSEN and MADYAR GOPAL RATJ . LXVII1.-Complex Metallic Ammines. Part VITI. The Introduction of Di- and Tri-basic Organic Acid Radicles into the Pentamminecobaltic Complex. By JAMES COOPER DUFF . WOOD . LVII1.-Studies on Metal Hydrides. . 434 444 452 456 47 1 476 484 494 503 618 532 543 549 56 viii CONTENTS.LX1X.-Chloroiodogcetic Acid. By HOLLAND CROMPTON LXX.-Interfacial Tension. By JAMES ROBERT POUND . LXX1.-Rotatory Dispersion of the Esters of Lactic Acid. Part I. Normal Esters. By CHARLES EDMUND WOOD, JOHN EDWARD SUCH and FRANK SCARF LXXI1.-Inorganic Complex Salts. Part 11. Erdmann’s Salt and its Derivatives. By WILLIAM THOMAS . LXXII1.-The Preparation of Xylose from Maize Cobs. By ARTHUR ROBERT LING and DINSHAW RATTONJI NANJI LXX1V.-Bromination of Glyoxnline-4-carboxyanilide. By HAROLD Kmct and WI~LIAM OWEN MURCH LXXV.-Studies in Hypophosphorous Acid. Part V. Its Reaction with Silver Nitrate. By ALEC DUNCAN ~ T C H E L L . LXXV1.-Silver Salvarsan. By WILLIAM HERBERT GRAY .LXXVIL-Tesla-luminescence Spectra. Part I. The Form of Apparatus and the Spectrum of Benzene. By WILLIAM HAMILTON MCVICKER JOSEPH KENNETH MARSH and ALFRED WALTER STEWART LXXVII1.-Perhalides of Quaternary Ammonium Salts. By FREDERICK DANIEL CHATTAWAY and GEORGE HOTLE . LXX1X.-The Formation of Derivatives of Oxalacetic Acid from Tartaric Acid. By FREDERICK DANIEL CHATTAWAY and GEORGE DAVID PARKES . LXXX.-The Higher Oxide of Nickel. By OWEN RHYS HOWELL . LXXX1.-Derivatives of Tetrahydrocarbazole. Part 11. By WILLIAM HENRY PERKIN jun. and SYDNEY GLENN PRESTON PLANT LXXXI1.-The Conditions of Reaction of Hydrogen with Sulphur. Part I. Direct Union. By RONALD GEORGE WREYFORD NORRISH and ERIC KEIGHTLEY RIDEAL . LXXXII1.-Heterogeneous Equilibria between the Chlorides of Calcium Magnesium Potassium and their Aqueous Solutions.Part I. By WILLIAM BELL LEE and ALFRED CHARLES EGERTON . LXXX1V.-Studies of the Glucosides. Part 11. Arbutin. By ALEXANDER KILLEN MACBETH and JOHN MACKAY. LXXXV.-Co-ordination Compounds and the Bohr. Atom. By NEVIL VINCENT SIDGWICK . LXXXVI.TThe Hydrogen Sulphates of the Alkali Metals and Ammonium. By HORACE BARRATT DUNBICLIFF . and KATE MYFANWY CARTER . . . PACE 576 578 600 617 620 62 1 629 635 642 654 663 669 676 696 706 71 7 725 73 CONTENTS. ix PdClE LXXXVI1.-A Direct Synthesis of Certain Xanthylium Derivatives. By DAVID Do10 PRATT and ROBERT ROBINSON . . . LXXXVII1.-A Synthesis of Pyrylium Salts of Antho-cyanidin Type.Part 11. By DAVID D o ~ a PRATT and ROBERT ROBINSON . . LXXXIX .-Physostigmine. Part I. Alkylation Products of Eseroline. By GEORGE BARGER and EDGAR STEDMAN XC.-Spinacene its Oxidation and Decomposition. By A. CHASTON CHAPMAN . XC1.-The Molecular Configuration of Polynuclear Aromatic Compounds. Part 11. 4 6 4’-Trinitrodiphenic Acid and its Resolution into Optically Active Components. By GEORGE HALLATT CHRISTIE and JAMES KENNER . XCI1.-Heteromorphism of Calcium Carbonate. Marble, Synthetic and Metamorphic. By MAURICE COPISAROW . XCII1.-Heteromorphism of Calcium Sulphate. Alabaster and its Synthesis. XC1V.-Reactions of Thiosemicarbazones. Part 11. Action of Esters of a-Halogtmated Acids. By FORSYTH JAMES WILSON and ROBERT BURNS . XCV.-The Application of the Hofmann Reaction to Sub-stituted Carbamides.By GEORGE ROBERT ELLIOTT . XCV1.-Phosphorous Acid Esters. The Influence of the Character of the Groups R’ R” R”’ on the Stability of the Molecular Complexes R’R‘’R”’C*O*PCl and R’R’’R’’’C*O*P( OH)2. Part I. By DAVID RUNCIMAN BOYD and GUY CHIONELL . XCVI1.-Tesla-luminescence Spectra. Part 111. The Effect of Varying Temperature and Pressure on the Benzene Spectrum. By WILLIAM HAMILTON MCVICKER and JOSEPH KENNETH MARSH . XC VII1.-The Fluorescence Spectrum of Benzene Vapour. By WILLIAM HAMILTON MCVICKER and JOSEPH KENNETH MARSH . XC1X.-Studies of Electrovalency . Part I. The Polarity of Double Bonds. By THOMAS MARTIN LOWRY . C.-The Action of Methyl Sulphate on Diphenylamine and on Methyldiphenylamine.By CHARLES STANLEY GIBSON and DUDLEY CLOETE VINING . C1.-The Properties of Ammonium Nitrate. Part V. The Reciprocal Salt-pair Ammonium Nitrate and Potassium Chloride. By EDGAR PHILIP PERMAN and HORACE LEONARD SAUNDERS . By MAURICE COPISAROW . * 739 745 758 769 779 785 796 7 99 804 813 81 7 820 822 831 84 X CONTENTS. CI1.-Preparation of Potassium and Sodium Arylsulphoniodo-amides. By ELWYN ROBERTS . CII1.-The Chemistry of Polycyclic Strbctures in Relation to their Homocyclic Unsaturated Isomerides. Part IV. The Simulation of Benzenoid Properties by the Five-carbon Intra-annular Nucleus. By CHRISTOPHER KELK INQOLD ERNEST ARTHUR SEELEY and JOCELYN FIELD THORPE . . C1V.-Studies in Organic Compounds containing Sulphur.Part I. The Effect on General Absorption due to the Valency and Mode of Linkage of the Sulphur Atom. By DAVID TEMPLETON GIBSON HUGH GRAHAM and JAMES REID . CV.-Isolation of the Oxide of a New Element. A Correction. By ALEXANDER SCOTT . CV1.-The Form of the Vapour Pressure Curve a t High Temperatures. Part 11. The Curve for Sodium Cyanide. By CHRISTOPHER KELK INGOLD . CVI1.-Anodic Formation of a Perchloride of Manganese. By ALAN NEWTON CAMPBELL . CVII1.-Mercury Cleansing Apparatus. By AUGUSTUS EDWARD DIXON and JAMES LYTTLE MCKEE . Some Constitutional Problems of Carbohydrate Chemistry. A Lecture Delivered before the Chemical Society on February 22nd 1923. By JAMES COLQUHOUN IRVINE, C.B.E. F.R.S. . ANNUAL GENERAL MEETING . Symbols and Formulae.Presidential Address. Delivered a t the Annual General Meeting March 22nd 1923. By SIR JAMES WALKER D.Sc. LL.D. F.R.S. . OBITUARY NOTICES . CIX.-An Electrolytic Method for' the Preparation of Mercury Dimethyl. By J. LEWIS MAYNARD and HENRY C. HOWARD jun. CX.-Action of Sulphur Monochloride on Mercaptans. By GOPAL CHANDRA CHAKRAVARTI . . CX1.-The Oxidising Properties of Sulphur Dioxide. Part IV. Molybdenum Sulphates. By WILLIAM WARDLAW and NORMAN DARBY SYLVESTER (2x11.-The Morphine Group. Part I. A Discussion of the Congtitutional Problem. By JOHN MASSON GUL-LAND and ROBERT ROBINSON . CXII1.-The Morphine Group. Part 11. Thebainone, Thebainol and Dihydrothebainonc. By JOHN MASSON GULLAND and ROBERT ROBINSON . . PACE 849 853 874 881 885 892 895 898 922 93 9 946 960 964 969 980 99 CONTENTS.xi PAGE CX1V.-Benzbisthiazoles. Part 111. By STEPHEN RATH-BONE HOLDEN EDGE . . CXV.-The Energy of Activation in Heterogeneous Gas Reactions with Relation to the Thermal Decomposition of Formic Acid Vapour. By CYRIL NORMAN HINSHEL-WOOD and BRYAN TOPLEY . . CXV1.-On the Propagation of the Explosion-Ware. Part I. Hydrogen and Carbon Monoxide Mixtures. By HAROLD BAILY DIXON and NOEL STANLEY WAUS CXVI1.-Yohimbine (QJebrachine). Part 11. apo-Yohimbine and Deoxy-yohimbine. By GEORGE BAR-GER and ELLEN FIELD . CXVII1.-The Molecular Configurations of Polynuclear Aro-matic Compounds.. Part 111. Diphenyl-3 5 3’ 5’-tetracarboxylic Acid. By HAROLD BURTON and JAMES KENNER . b . CX1X.-The Interaction of Hydrogen Sulphide Thio-cyanogen and Thiocycznic Acid with Unsaturated Corn-poun’ds.By FREDERICK CHALLENGER ALAN LAW-RENCE SMITH and FREDERIC JAMES PATON CXX.-Studies on the Dolomite System. Part I. The Nature of Dolomite. By ALLAN ERNEST MITCHELL . CXX1.-The Oxime of Mesoxamide (isoNitrosomalonamide) and some Allied Compounds. Part 111. Ring Form-ation in the Tetra-substituted Series. By EDITH HILDA USHERWOOD and MARTHA ANNIE WHITELEY . CXXI1.-The Conversion of Malonic Acid into d-Malic Acid. By ALEX. MCKENZIE and HAROLD JAMES PLENDER-CXXII1.-Researches on Residual Affinity and Co-ordin-ation. Part XVI. Normal and Acid Salicylatotetr-amminocobaltic Salts. By GILBERT T. MORGAN and J. D. MAIN SMITH . . CXX1V.-Studies on Thallium Compounds.Part 11. The Reduction of Thallic Compounds with Ferrous Sulphate and with Sodium Arsenite. By ARTHUR JOHN BERRY CXXV.-Preparation of Hydrazine by Raschig’s Method. By REGINALD ARTHUR JOYNER . CXXV1.-The Labile Nature of the Halogen Atom in Organic Compounds. Part VIII. The Action of Hydrazine on the Halogen Derivatives of Acetoacetic and Benzoyl-acetic Esters and of Benzoylacetone. By ALEXANDER KILLEN MACBETH . . LEITH . 101 1 1014 1025 1038 1043 1046 1055 1069 1090 1096 1109 1114 112 xii CONTENTS. CXXVI1.-The Labile Nature of the Halogen Atom in Organic Compounds. Part IX. The Electrical Con-ductivities and the Reduction of Derivatives of Nitro-form. By THOMAS HENDERSON EDMUND LANULEY HIRST and ALEXANDER KILLEN MACBETH .. CXXVII1.-Synthesis of 4-Hydroxy-1 2-dirncthylanthra-quinone. By ARTHUR FAIRBOURNE and JOHN MILDRED GAUNTLETT . CXX1X.-Investigation of the Mannan Present in Vegetable Ivory. By JOCELYN PATTERSON . CXXX-Imino-aryl Ethers. Part 11. The Thermal De-composition of N-Arylaryliminoaryl Ether Hydrochlor-ides. By ARTHUR WILLIAM CHAPMAN . CXXX1.-The Action of Hypochlorous Acid on Bornylene. By GEORUE GERALD HENDERSON and JOHN ALEXANDER MAIR . CXXXI1.-Organo-derivatives of Thallium. Part VI. Com-pounds of the Type R,TlX. By ARCHIBALD EDWIN GODDARD CXXXII1.-The aa'-Dichlorodialkyl Sulphides. By FREDERICK GEORGE MANN and WILLIAM JACKSON CXXX1V.-The Isomeric Trithioacetaldehydes. By FREDERICK GEORGE MANN and WILLIAM JacKSoN CXXXV.-The Sulphides of Ammonium.By JOHN SMEATH THOMAS and RICHARD WILLIAM RIDINU CXXXV1.-The Isomerism of the Oximes. Part XI. Carbethoxy-derivatives. By OSCAR LISLE BRADY and GERALD PATRICK MCHUQH . CXXXVI1.-The Photochemistry of Unstable Substances. By EDMUND JOHN BOWEN . CXXXVII1.-Ring-chain Tautomerism . Part V. The Effect of the gem-Dipropyl Grouping on the Carbon Tetrahedral Angle. By LESLIE BAINS and JOCELYN FIELD THORPE CXXX1X.-Dyes of the Aurin Type. Part I. By HARRY BAINES and JOHN EDMUNDRIVER. CXL.-Some Factors Governing the Complete Sorption of Iodine by Carbon from Chloroform Solution. By JAMES BRIERLEY FIRTH and FRED SHEASBY WATSON . CXL1.-Change of Properties of Substances on Drying. Part 11. By HERBERT BRERETON BAKER . POPE . POPE . . PAQE 1130 1137 1139 1150 1155 1161 1172 1178 1181 1190 1199 1206 1214 1219 122 CONTENTS.... XUI PAQE CXLI1.-The Molecular Refractions of Chloro- Dichloro-, By PAULE LAURE VANDER-CXLII1.-The Velocity of Reaction in Mixed Solvents. Part V. a. The Velocity of Formation of Quaternary Ammonium Salts. b. The Study of an Intramolecular Change. By JOHN DEXTER HAMILTON MCCOMBIE and HAROLD ARCHIBALD SCARBOROUGH . CXL1V.-Oxidation of Nickel Sulphide. By JOHN STANLEY DUNN and ERIC KElCfHTLEY RIDEAL CXLV.-The Combustion of Complex Gaseous Mixtures. Part 11. Mixtures of Carbon Monoxide and Hydrogen with Air. By WILLIAM PAYMAN and RICHARD VERNON WHEELER CXLV1.-The Influence of Nitro-groups on the Reac tivity of Substituents in the Benzene Nucleus.Part VII. Reactions of 2 5- and 4 5-Dinitro-m-xylenes. By KATHLEEN IBBOTSON and JAMES KENNER CXLVI1.-Nitro-derivatives of m-Cresol. By GEORGE PHILIP GIBSON CXLVII1.-The Structure of Sucrose. By MAX BERGMANN CXL1X.-The Action of Thiosulphates on Cupric Salts. By HENRY BASSETT itnd REGINALD GRAHAM DURRANT CL.-The Sodium Salts of Phenolphthalein. By HENRY BASSETT and PHILE HALTON . CL1.-The So-called Pre-pressure Interval in Gaseous Ex-plosions. CLI1.-Substitution in the Pyrazole Series. Halogen De-rivatives of 3 5-Dimethylpyrazole. By GILBERT T. MORGAN and ISIDORE ACKERMAN . b CLII1.-The Adsorption of the -B and -C Members of the Radium and Thorium Series by Ferric Hydroxide. By JOHN ARNOLD CRANSTON and ROBERT HUTTON . CL1V.-y-Oxalyl Derivatives of Pp- and aP-Dimethylacrylic Acids.By LUCY HIGGINBOTHAM and ARTHUR LAP-CLV.’The Influence of Temperature on Two Alternative Modes of Decomposition of Formic Acid. By CYRIL NORMAN HINSHELWOOD and HAROLD HARTLEY. CLVI .-The Ternary System Ammonium Chloride-Ferric Chloride-Water. By FREDERICK WILLIAM JEFFREY CLENDINNEN . . CLVI1.-A Critical Solution Temperature for Solids in the Binary System Ammonium Chloride-Manganous Chloride Dihydrate. By FREDERICK WILLIAM JEFFREY CLENDINNEN and ALBERT CHERBURY DAVID RNETT . and Chlorobromo-acetates. STICHELE . By JOHN DAVID MORGAN . WORTH . 1225 1229 1242 1251 1260 1269 1277 1279 129 1 1304 1308 1318 1325 1333 1338 134 xiv CONTENTS. CLVII1.-The Structure of the Normal Monosaccharides.Part I. Xylose. By EDMUND LANGLEY HWT and CLIFFORD BURROUGH PURVES . Part I. The Influence of the cycZoHexane Ring on the aP+y Change. By STANLEY FRANCIS BIRCH GEORGE ARMAND ROBERT KON and WOODFORD STANLEY GOWAN PLUCK-NETT NORRIS [with an Introductory Note by Prof. J. F. CLX.-Binary Critical Solution Temperatures as Criteria of the Purity of Acetic Acid. By DAVID CHARLES JONES . CLX1.-Ternary Critical Solution Temperatures as Uriteria of Liquid Purity. By DAVID CHARLES JONES . CLXI1.-Benzopyrylium Salts of Distyryl Ketones. Part 11. Salts and Metallic Complexes of 4’-Dimethylamino-2-styrylbenzopyrylium. By JOHANNES SYBRANDT BUCK and ISIDOR MORRIS HEILBRON CLXIIL-Optical Rotations of the Sugars. Part 11. The Methyl Pentoses and the Glucosides.By JOHN GWILLXAM MALTBY . . CLX1V.-Estimation of Tin in Wolfram. A Modification of Powell’s Method. By OCTAVIUS FRANCIS LUBATTI . CLXV.-The Swelling of Agar-agar. By FRED FAIRBROTHER and HAROLD MASTIN . . CLXVI.-The Action of Sulphuryl Chloride on Organic Substances. Part 11. By THOBUS HAROLD DURRANS CLXVI1.-Investigations of the Chromates of Thorium and the Rare Earths. Part I. The System Thorium Oxide-Chromic Anhydride-Water at 25’. By HUBERTHOUS STANLEY BRITTON . CLXVII1.-The Propagation of Flame from a Spark in a Closed .Tube through a Homogeneous Inflammable Mixture. By OLIVER COLIGNY DE CHAMPFLEURELLIS CLX1X.-Promotion of Catalytic Reactions. Part I. By SAMUEL MEDSFORTH CLXX.-The Mobility of Symmet,rical Triad Systems. Part 11. The Conditions Relating to Systems Terminated by the o-Phenylene Group.Derivatives of Indene. By CHRISTOPHER KELK INGOLD and HENRY ALFRED PIGGOTT . By OSCAR WALTER SNOW and JOHN FREDERICK SMERDON STONE . CLXXIL-The Action of Sodium Hyposulphite on Cupric Chloride in Aqueous Solution. By JAMES BRIERLEY FIRTH and JOHN HIGSON . CL1X.-The Chemistry of the Three-carbon System THORPE] . . CLXX1.-A Note on the Photosynthesis of Amines. PAQP 1352 1361 1374 1384 1395 1404 1409 1412 1424 1429 1435 1452 1469 1509 151 CONTENTS. xv PAGE Baeyer Memorial Lecture. Delivered on May loth 1923. By WIL,LIAM HENRY PERKIN LL.D. F.R.S. . . CLXXII1.-The Preparation and Properties of 4’ 4’’ -Tetra-methyldiaminoanthrafuchsone. By FREDERICK ALFRED MASON .. . CLXX1V.-Dyes Derived from Phenanthraquinone. Part 111. Phenanthriminazoles. By ANUKUL CHANDRA SIRCAR and GOPAL CHANDRA SIRCAR. CLXXV.-The Protective Action of Potassium Oleate on Gold Sols in Water-Alcohol Mixtures. By ERIC KEIGHTLEY RIDEAL and LOUIS LEIUHTON BIRCUM-CLXXV1.-The Isomerism of Reduced Derivatives of Quinoxaline. Part I. The Four Stereoisomeric 2 3-Diphenyl- 1 2 3 4 - Tetrahydroquinoxalines. By GEORGE MACDONALD BENNETT and CHARLES STANLEY GIBSON . CLXXVII.-Substitution in Vicinal Trisubstituted Benzene Derivatives. Part I. By WILLIAM DAVIES . CLXXVII1.-The Ultra-violet Absorption Spectra of Eugenol and isoEugeno1. By GARTHA THO~SON . CLXX1X.-The Properties of some Silver Organosols. By JOHN KENNETH GILES and CYRXL SEBASTIAN SALMON .CLXXX.-The Freezing-point Curve for Mixtures of Potassium Nitrate and Sodium Nitrate. By HENRY VINCENT AIRD BRISCOE and WALTER M~TTHEW MADUIN. CLXXX1.-Reduction of Ethyl Ethylidenemalonate as Affected by Choice of Reducing Agent. By LUCY HIGUINBOTHAM and ARTHUR LAPWORTH . . CLXXXI1.-The Theory of Acid-Alkali Solution Equilibrium as Applied to Salts of Moderately Strong but Sparingly Soluble Acids. By EDMUND BRYDUES RUDHALL PRIDEAUX . CLXXXIIL-Mixed Crystals and Double Salts A Com-parison of Systems containing Water Ammonium Chloride and a Chloride of Manganese Iron Cobalt, Nickel or Copper. By ALBERT CHERBURY DAVID RIVETT and FREDERICK WILLIAM JEFFREY CLENDINNEN. CLXXX1V.-Hydroxynaphthoic Acids. Part I. By FRANK ALBERT ROYLE and JACK ARNOLD SCHEDLER CLXXXV.-Hydroxynaphthoic Acids.Part 11. By CARL-TON BUTLER and FRANK ALBERT ROYLE . CLXXXV1.-Researches on Phellandrenes. Part I. By HENRY GEORGE SMITH ERIC HURST and JOHN READ , SHAW . . . . . . 1520 1546 1559 1565 1570 1575 1594 1597 1608 1618 1624 1634 1641 1649 165 xvi CONTENTS. CLXXXVI1.-Investigations on the Dependence of Rotatory Power on Chemical Constitution. Part XX. The Rational Study of Optical Properties including Refrac-tion. By HAROLD HUNTER . CLXXXVII1.-Ring-chain Tautomerism. Part VI. The Mechanism of the Iceto-cyclol Change in the Propane Series. By ERIC WILLIAM LANFEAR and JOCELYN FIELD THORPE CLXXX1X.-The Conditions of Reaction of Hydrogen with Sulphur. Part 11. The Catalytic Effect of Oxygen.Part 111. The Mechanism of the Reaction of Hydrogen with Sulphur and its Catalysis by Oxygen. By RONALD GEORGE WREYFORD NORRISH and ERIC KEIGHTLEY RIDEAL . . . . CXC.-The Mechanism of the Pinacol-Pinacolin and Wagner-Meexwein Transformations. By CHRISTOPHER KELK INGOLD . . CXC1.-The Conversion of Sabinol into Thujene. By GEORGE GERALD HENDERSON and ALEXANDER ROBERT-CXCI1.-The Correlation of Additive Reactions with Tauto-meric Change. Part I. The Aldol Reaction. By EDITH HILDA USHERWOOD . . Part IV. The Polysulphides of Ammonium. By JOHN SMEATH THOMAS and RICHARD WILLIAM RIDING . . CXC1V.-Hydrolysis of the Sulphoxide and the Sulphone of pp’-Dichlorodiethyl Sulphide. By ALBERT ERIC CASHMORE . CXCV.-Intermittent Current Electrolysis.Part I. The Influence of Intermittent Current on Overvoltage. By SAB~UEL GLASSTONE . CXCV1.-The Behaviour of Activated Sugar Carbon in Contact with Hydrogen Peroxide Solution. By JAMES BRIERLEY FIRTH and FRED SHEASBY WATSON CXCVI1.-The Formation of Derivatives of Tetrahydro-naphthalene from y-Phenyl Fatty Acids. Part 111. The Influence of Substituents on Ring Closure. By ARTHUR JOHN ATTWOOD ARNOLD STEVENSON and JOCELYN FIELD THORPE . CXCVIIL-The Action of Halogens on Phenylhydrazones. Part I. The Action of Bromine. By JAMES ERNEST HUMPHRIES EDWARD BLOOM and ROY EVANS CXC1X.-The Constitution of the Higher Oxide of Nickel. By OWEN Rms HOWELL . SON CXCII1.-The Polysulphides of the Alkali Metals. . PAGE 1671 1683 1689 1706 1713 1717 1726 1738 1745 1750 1755 1766 177 CONTENTS.xvii PAQE CC.-The Isomerism of the Oximes. Part XII. Hydro-chlorides. By OSCAR LISLE BRADY and FREDERICK PERCY DUNN . CC1.-Influence of Hydrogen Cliloride on the Enolising Action of Grignard’s Reagent. By VINAYAK KESHAV BHAGWAT CCII.-Constitutional Studies in the Monocarboxylic Acids derived from Sugars. Part I. Tetramethyl Galactono-lactone and the Structure of Galactose. By JOHN PRYDE CCII1.-Metallic Hydroxy-acid Complexes. Part I. Cupri-lactates. By IAN WILLIAM WARK . CC1V.-Metallic Hydroxy-acid Complexes. Part 11. Cupri-malates. Their Formation Properties and Composition. By IAN WILLIAM WARK . CCV.-The Absorption Spectra of the Vapours of Various CCV1.-The Oxidation of Sltbinene with Hydrogen Peroxide.By GEORGE GERALD HENDERSON and ALEXANDER ROBERTSON . CCVI1.-Temperature Coefficients of Reactions in Tropical Sunlight. By NILRATAN DHAR . CCVII1.-Electron Valency Theories and Stereochemistry. By SAMUEL SUGDEN . CC1X.-Note on the Theory of Free Rotation. By THOMAS MARTIN LOWRY . CCX.-New Halogen Derivatives of Camphor. Part 111. a‘p- and a’x-Dibromocamphor. By HENRY BURGESS and THOMAS MARTIN LOWRY . CCX1.-Resolution of the as-Dihydroxy-a-methyl-8-isopro-pyladipic Acids. By THOMAS ANDERSON HENRY and HUMPHREY PAGET . CCXII.4tudies on the Dolomite System. Part 11. By ALLAN ERNEST MTCHELL Les Gaz Rares des Gaz Naturels. A Lecture Delivered before the Chemical Society on June 14th 1923. By PRO-FESSOR CHARLES MOUREU President of the Soci6t6 Chimique de France .CCXII1.-The Molecular Configurations of Polynuclear Aromatic Compounds. Part IV. 6 6’-Dichloro-di-phenic Acid; its Synthesis and Resolution into Optic-ally Active Components. By GEORGE HAUATT CHRISTIE CUTHBERT WILLIAM JAMES and JAMES KENNER Quinones. By JOHN IZDWARD PURVIS . 1783 1803 1808 1815 1826 1841 1849 1856 1861 1866 1867 1878 1887 1905 194 xviii OONTENTS. CCX1V.-The Viscosity of some Cellulose Acetate Solutions. By ERNEST WALTER JOHN MARDLES CCXV.-Mercaptans of the Purine Group. Part I. By SIR PRAFULLA CHANDRA RAY GOPAL CHANDRA CHAK-RAVARTI and PRAFULLA KUM& BOSE . . CCXV1.-The Isomeric I-Menthyl Phenylchloroacetates. By ALEX. MOKENWE and ISOBEL AGNES SMITH . CCXVI1.-The Determination of the Degree of Hydration of Salts by a Radioactive.Method.By HENRY TERREY and VICTOR GEORGE JOUY . CCXVII1.-The Action of Bromine on p-Hydroxy- and p-Methoxy-sulphonic Acids. By ANDREW NORMAN MELDRUM and MADHAVLAL S u m SHAH CCX1X.-"he Constitution of' Sulphosalicylic Acid and of Related Substances. By ANDREW NORMAN MELDRUM and MADHAVLAL SUKHLAL SHAH . CCXX.4tudies in the Anthracene Series. Part V. By EDWARD DE BARRY BARNETT JAMES WILFRED COOK, and MARCUS AURELIUS MATTHEWS . CCXX1.-The Relative Influences of Water Vapour and Hydrogen upon the Explosion of Carbon Monoxide-Air Mixtures at High Pressures. By WILLIAM A. BONE, DUDLEY M. NEWITT and DONALD T. A. TOWNEND . CCXXI1.-The Action of Silica on Electrolytes. By ALFRED FRANCIS JOSEPH and JOHN STANLEY HANCOCK CCXXII1.-Dissociation of Complex Cyanides.By GEORGE JOSEPH BURROWS . CCXX1V.-Reduction Products of the Hydroxyanthra-quinones. Part 11. By JOHN HALL and ARTHUR GEORGE PERKIN . CCXXV.-Cryoscopic Measurements with Nitrobenzene. By HUGH MEDWYN ROBERTS and CHARLES R. BURY . CCXXV1.-The X-Ray Investigation of Fatty Acids. By ALEX. M ~ E R . CCXXVI1.-The Isomerism of the Dinitrobenzidines. By OSCAR LISLE BRADY and GERALD PATRICK MCHUGH . CCXXVIII.-Chromoisomerism in the Stilbene Series. By NICHOLAS MICHAEL CULLINANE . CCXXIX.-Surface Phenomena in Sucrose Solutions. By RAYMOND RENARD BUTLER . CCXXX.-The Structure of the Benzene Nucleus. Part 111. Synthesis of a Naphthalene Derivative involving a Bridged Phase of the Nucleus. The Constitution of Naphthalene and Anthracene.By WILLIAM ARTHUR PERCIVAL CHALLENOR and CHRISTOPHER KELK INGOLD . . PAGE 1951 1937 1962 1979 1982 1986 1994 2008 2022 2026 2029 2037 2043 2047 2053 2060 206 CONTENTS. x 18 PAGE CCXXX1.-The Structure of the Benzene Nucleus. Part IV. The Reactivity of Bridged Linkings. By CKRISTO-PHER KELK INGOLD CCXXXII.-Sintering Its Nature and Cause. By ROBERT CHRISTIE SMITH . CCXXXII1.-Derivatives of Phthalonic Acid 4 5-Di-methoxyphthalonic Acid and 4 5-Dimethoxy-o-tolyl-glyoxylic Acid. By (Miss) CHIKA KURODA and WILLIAM HENRY PERKIN jun. . CCXXXIV.4tudies of Electrovalency . Part 11. Co-ordinated Hydrogen. By THOMAS M~RTIN LOWRY and HENRY BURGESS . . . . CCXXXV.-The Diffusion of Oxygen through Silver.By LEO SPENCER . CCXXXV1.-The Properties of Ammonium Nitrate. Part VI. The Reciprocal Salt Pair Ammonium Nitrate and Potassium Sulphate. By EDGAR PHILIP PERMAN and WILLIAM JOHN HOWELLS . . CCXXXVII.4omplex Pormation in Lead Nitrate Solu-t,ions. Part I. The Ternary Systems Lead Nitrate-Sodium Nitrate-Water and Lead Nitrate-Potassium Nitrate-Water. By SAMUEL GLASSTONE and HAROLD NICHOLASAUNDERS . CCXXXVII1.-The Preparation of N-Derivatives in the Carbazole Series. By THOUS STEVENSTEVENS and STANLEY HORWOOD TUCKER . CCXXX1X.-Tesla-luminescence Spectra. Part 111. Some Mono-substitution Products of Benzene. By WILLIAM HAMILTON MCVICKER JOSEPH KENNETH ~WARSH and ALFRED WALTER STEWART . CCXL.-The Isomerism of the Oximes. Part XIII. Phenyl-ethyl- Dieth yl - and a- Naph th yl-Carbamyl Derivatives.By OSCAR LISLE BRAUY and DUDLEY RIDGE Part 111. The Sulphones Sulphinic and Sulphonic Acids of the Series. Extension of StuBer’s Law. By SIR PRAFULLA CHANDRA RAY CCXLII.4ondensation of Amidines with Ethoxymethylene Derivatives of (%Ketonic Esters and of 8-Diketones. By PRAFULLA CHANDRA MITTER and JOGENDRA CELANDRA BARDHAN CCXLII1.-The Calorific Value of Carbon Compounds. By DIMITRI KONOVALOV . CCXL1V.-The Quinhydrone Electrode as a Comparison Electrode. By STIG VEIBEL . . . CCXL1.-Triethylene Tri- and Tetra-sulphides. 2081 2088 2094 2111 2124 2128 2134 2140 2147 21 63 2174 2179 2184 220 xx CONTENTS. CCXLV.-Bromination of Compounds containing the Car-bony1 Group.(a) Pyruvic Acid. ( b ) Acetophenone. By CHARLES FREDERICK WARD . CCXLV1.-The Isomorphism of the Amides and Substituted Amides of Dichloro- and Chlorobromo-acetic Acids. By PHYLLIS V. MCKIE . CCXLVI1.-The Hydrates of Potassium and Lithium Platinocyanides and the System Potassium Platino-cyanide-Lithium Platinocyanide-Water. By HENRY TERREY and VICTOR GEORGE JOLLY CCXLVII1.-The System Ferric Oxide-Phosphoric Acid-Water. A New Phosphate. By SYDNEY RAYMOND CARTER and NORMAN HOLT HARTSHORNE . CCXL1X.-Bromination of Aliphatic Acids. By BRIAN DUNCAN SHAW CCL.-The Reaction between Phosphorous Acid and Iodine. By ALEC DUNCAN MITCHELL . CCL1.-The Colloidal Electrolyte extracted from Carrageen (Chondmcs Crispus). By FRANK COURTNEY H~RWOOD . CCLI1.-Triazole Compounds.Part I. Some Substituted Hydroxybenzotriazoles and their Methylation Products. By OSCAR LISLE BRADY and JAMES NELSON EDMUND DAY . CCLII1.-Piperitone. Part V. The Characterisation and Racemisation of Z-Piperitone. By JOHN READ and HENRY GEORGE SMITH . CCL1V.-Studies in Phototropy. The Reversed Phototropy of Cinnamaldehydescmicarbazone and its Methoxy-derivatives. By ISIDOR MORRIS HEILBRON HERBERT EDWARD HUDSON and DORIS MABEL HUISH CCLV.-Studies in Mutual Solubility. Part I. Intro-ductory. The Mutual Solubility of Glycerol and Aliphatic and Aromatic Ketones. By BASIL CHARLES MCEWEN CCLVI.-E%udies in Mutual Solubility. Part 11. The Mutual Solubility of Glycerol and Alcohols Aldehydes, Phenols and their Derivatives. By BASIL CHARLES MCEWEN CCLVI1.-Dyestuffs Derived from Heterocyclic Bases con-taining Reactive Methyl Groups.By JAMES LEONARD BRIERLEY SMITH . CCLVII1.-The Relationship of the Tautomeric Hydro-gen Theory to the Theory of Induced Alternate Polarities. By FRED ALLSOP and JAMES KJEXNER . . PAGE 2207 2213 2217 2223 2233 2241 2254 2258 2267 2273 2279 2284 2288 229 CONTENTS. xx 1 PAQE CCLIX .-Researches on Antimony. Part I. Tri-m-xylyl-stibine and its Derivatives. By ARCHIBALD EDWIN GODDARD CCLX .-Some Properties of Electrolytic Manganese. By ALAN NEWTON CAMPBELL CCLX1.-The Photochemical Decomposition of Chlorine Monoxide. By EDMUND JOHN BOWEN . CCLXI1.-Benzbisthiazoles. Part IV. By STEPHEN RATH-BONE HOLDEN EDGE . CCLXII1.-6 6’-Diacetylamino- 1 1 ‘-diethylcarbocyanine Iodide.By FRANCES MARY HAMER CCLX1V.-The Estimation of Alkalis in Rocks by the Indirect Method. By FREDERICK WALKER . CCLXV.-Equilibrium of the Ternary System Bismuth-Tin-Zinc. By SHEIKH D. MUZAFFAR CCLXVI.-Studies in the Benzothiazole Series. Part I. The Pseudo-bases of the Benzothiazole Quaternary Salts. By WILLIAM HOBSON MILLS LESLIE MARSHALL CLARK and JOHN ALFRED AESCIILIMANN . CCLXVII.4tudies in the Benzothiazole Series. Part 11. Thio-2-meth lbenzothiazolone and its Oxidation Pro-ducts. By XILLIAM HOBSON MILLS LESLIE MARSHALL CLARK and JOHN ALFRED AESCHLIMANN . CCLXVII1.-The Kinetics of the Reaction between Ferrous Phosphate and Sulphur Dioxide in Phosphoric Acid Solution. By SYDNEY RAYMOND CARTER and JOHN ALFRED VALENTINE BUTLER .CCLXIX .-The Reaction between Ferrous Phosphate and Sulphur Dioxide in Phosphoric Acid Solution ; the Nature of the Decomposition Products. By SYDNEY RAYMOND CARTER and JOHN ALFRED VALENTINE BUTLER . CCLXX .-Chlorosulphonyl Derivatives of Aromatic Amines. By ROWLAND NICHOLAS JOHNSON and SAMUEL SMILES. CCLXX1.-Derivatives of ortho-Thiolphenols. By DAVID TEMPLETON GIBSON and SAMUEL SMILES . CCLXXIL-Derivatives of Tetrahydrocarbazole. Part 111. Amino-compounds. By GEORGE ALFRED EDWARDS and SYDNEY GLENN PRESTON PLANT . CCLXXII1.-Derivatives of Tetrahydrocarbazole. Part IV. By WILLIAM HENRY I’ERKIN jun. and GEORGE CLIF-FORD RILEY . . CCLXX1V.-Calcium Carbonate Hexahydrate. By JOHN EDWIN WCKENZIE . 2315 2323 2328 2330 2333 2336 2341 2363 2362 2370 2382 2384 2388 2393 2399 240 xxii CONTENTS.CCLXXV.-The Constitution of Soap Solutions Migration Data .for Potassium Oleate and Potassium Laurate. By JAMES WILLIAM MCBAIN and RICHARD CHARLES BOWDEN CCLXXVL-The Distribution of Normal Fatty Acids be-tween Water and Benzene. By FREDERICK STANLEY BROWN and CHARLES R. BURY CCLXXVI1.-The Isomerism of the Oximes. Part XIV. 3-Nitro- and 3-Bromo-p-dimethylaminobenzaldoximes. By OSCAR LISLE BRADY and RICHARD TRUSZKOWSKI . CCLXXVIIL-The Chemistry of the Three-carbon System. Part 11. Tautomeric Nitriles and Cyano-esters. By STANLEY FRANCIS BIRCH and GEORGE ARMAND ROBERT KON . CCLXXIX.-The Low Temperature Activation of Hydrogen. By ALLAN ERNEST ETCHELL and ABRAHAM LINCOLN MARSHALL .CCLXXX.-The Hydroferrocyanides and Hydroferricymides of the Organic Bases. Part 11. By WILLIAM MURDOCH CCLXXX1.-Reduction of Nitronaphthalenes. Part I. Reduction of a-Nitronaphthalene. By WILLIAM MUR-DOCH CUMMING and JAMES KING STEEL CCLXXXI1.-Chlorination of Benzoyl Chloride. Part 11. By EDWARD HOPE and GEORGE CLIFFORD RILEY . CCLXXXIIL-The Relative Stability of Open-chain Di-basic Acids containing Odd and Even Numbers of Carbon Atoms. By WILLIAM ARTHUR PERCIVAL CHAL-LENOR and JOCELYN FIELD THORPE . CCLXXXIV. Hydrolysis of f@’-Dichlorodiethyl Sulphide and Action of Hydrogen Halides on Divinyl Sulphide. By SIDNEY HARTLEY BALES and STANLEY ARTHUR NICKELSON . . . CCLXXXV.-A s-Methyldihydroarsindole. By EUSTACE EBENEZER TURNER and FRANK WARD BURY CCLXXXVI.-Selective Solvent Action by the Constituents of Aqueous Alcohol.Part 11. The Effect of some Alcohol-soluble Semi-solutes. By ROBERT WRIGHT . CCLXXXVI1.-Nitrosation of Phenols. Part I. 3-Chloro-4-nitrosophenol and its Conversion into Two Isomeric Chloroquinonemonoximes. By HERBERT HENRY HODG-SON and FRANCIS HARRY MOORE By PERCIVAL WALTER CLUTTERBUCK and JULIUS BEREND CUMMINU 0 . . . CCLXXXVIIL-The Aryl and Alkyl Sulphonamides. PAQE 2417 2430 2434 2440 2448 2457 2464 2470 2480 2486 2480 2493 2499 COHEN . . 250 CONTENTS. xxiii PAQE CCLXXX1X.-The Absorption Spectra of the Vapours and Solutions of Various Ketones and Aldehydes. By JOHN EDWARD PURVIS . . CCXC.-Styrylbenzopyrylium Salts. Part 111.The 7-Styryl Derivatives of 7-Hydroxy-2-phenyl-4-methyI-benzopyrylium Chloride. By JOHANNES SYBRANDT BUCK and ISIDOR MORRIS HEILBRON CCXC1.-Muconic and Hydromuconic Acids. Part 11. The Isomerism of the Muconic Acids. By ERNEST HAROLD FARMER . CCXCII.-Studies in the Anthracene Series. Part VI. By EDWARD DE BARRY BARNETT and MARCUS AURELIUS MATTHEWS . CCXCII1.-The Resolution of Hydratropic Acid. By HENRY STANLEY RAPER . 0 0 . CCXC1V.-Chemical Reactivity and Con jugation the Re-activity of the 2-Methyl Group in 2 3-Dimethylchrom-one. By ISIDOR MORRIS HEILBRON HARRY BARNES, and RICHARD ALAN MORTON . CCXCV.-Absorption Spectra and Molecular Phases. Part I. By RICHARD ALAN MORTON and HARRY BARNES . CCXCV1.-Colorimetric Estimation of Small Amounts of Oxygen.By PERCY GEORGE TERRY HAND . CCXCVI1.-The Constitution of Carbamides. Part XV. A Delicate and Trustworthy Test for the Recognition of Cyanic Acid. By EMIT. ALPHONSE WERNER . CCXCVII1.-The Increased Solubility of Phenolic Sub-stances in Water on Addition of a Third Substance. By CHARLES REYNOLDS BAILEY . . Part XXVII. A Probable Example of Tervalent Silicon. By F’RED-ERIC STANLEY KIPpmcx . CCC.-Organic Derivatives of Silicon. Part XXVIII. Octa-phenyldiethylsilico tetrane. By FREDERIC STANLEY KIPPINGl . 0 . 0 . . . 0 CCC1.-Reduction Products of Hydroxyanthraquinones. Part 111. By ARNOLD BREARE and ARTHUR GEORGE PERKIN . . CCCI1.-Application of the Grignard Reaction to some Acetylenic Compounds. Part I. Preparation of Di-acetylenic Glycols.By FORSYTH JAMES WILSON and WILLIAM MCNINCH HYSLOP . . CCCII1.-The Short-lived Radioactive Products of Uranium. By WILLIAM GEORGE GUY and ALEXANDER SMITH RUSSELL . . CCXC1X.-Organic Derivatives of Silicon. 2515 2521 2531 2549 2557 2559 2570 2573 2577 2579 2590 2598 2603 2612 261 xxiv CONTENTS. CCC1V.-Studies in the Anthracene Series. Part VII. By EDWARD DE BARRY BARNETT and JAMES WILFRED COOK CCCV.-The Constituents of Indian Turpentine from Pinus Zonqifolia Roxb. Part 111. By JOHN LIONEL SIMONSEN CCCV1.-Studies on Starch. Part I. The Nature of Poly-merised Amylose and of Amylopectin. By ARTBUR ROBERT LING and DINSHAW RATTONJI NANJI . CCCVI1.-The Velocity of Reaction in Mixed Solvents. Part VI. The Velocity of Saponification of certain Methyl Esters by Potassium Hydroxide in Methyl Alcohol-Water Mixtures.By WALTER IDRIS JONES, HAMILTON MCCOMBIE and HAROLD ARCHIBALD SCAR-CCCVII1.-The Preparation of the Isomeric hlethoxybenzyl Bromides. By JOHN BALDWIN SHOESMITH . CCCIX-Condensation of Diphenylformamidine with Phenols. Part I. A New Synthesis of 0-Resorcyl-aldehyde. By JOHN BALDWIN SHOESMITH and JOHN HALDANE . CCCX.-Use of the Salts of the Arylsulphonhalogenoamides in the Estimation and Iodination of Phenols. By ELWYN ROBERTS . NoTEs.-constitution of Benzene. By RONALD FRASER . Solubility of Sodium Chlorate. By HUGH CHESTER BELL Esterification of Oxalic Acid. By PAVITRA KUMAR DUTT Electrolytic Generator for Pure Hydrogen. By VISCOUNT ELVEDEN and ERIC SINKINSON A New Method for the Resolution of Asymmetric Com-pounds-A Reply.By JULIUS BEREND COHEN . CCCX1.-The Adiabatic Cooling of Water and the Tem-perature of its Maximum Density as a Function of Pressure. By NICOLAI AIWONOVITCH PUSHIN and ELIJAH VASIWEVICH GREBENSHCHIKOV . CCCXIL-Two Heterogeneous Gas Reactions. By CYRIL NORMAN HINSHELWOOD and CHARLES Ross PRICHARD CCCXII1.-A Homogeneous Gas Reaction. The Thermal Decomposition of Chlorine Monoxide. Part I. By CYRIL NORMAN HINSHELWOOD and CHARLES Ross PRICHARD . CCCX1V.-The Dissociation of Certain Oxalato-salts. By GEORGE JOSEPH BURROWS and GEORGE WALKER . CCCXV.-The Formation of Stable p-hctones. By LESLIE BAINS and JOCELYN FIELD THORPE . BOROUGR PAQE 2631 2642 2666 2688 2698 2704 2707 2712 2713 2714 2715 2716 2717 2725 2730 2738 274 CONTENTS.xxv PAGE CCCXV1.-The Additive Formation of Four-membered Rings. Part I T . The Conditions which confer Stability on the Dimethinediazidines. By CHRISTOPHER KELK INGOLD and HENRY ALFRED PIGGOTT . CCCXVI1.-The Photochemical Reactivity of Ozone in presence of Other Gases. Part I. By ROBERT OWEN GRIFFITH and WILLIAM JAMES SHUTT CCCXVII1.-The Photochemical &activity of Ozone in presence of Other Gases. Part 11. By ROBERT OWEN GRIFFITII and JANE MAC~ILLIE . CCCX1X.-Condensation of Aryldiazonium Salts with Mono-alkylated Malonic Acids. By THOMAS KENNEDY WALKER. CCCXX.-Preparation and Chlorination of Rp-Alkylacyl-carbamides. By ELWYN ROBERTS . CCCXX1.-Synthesis of Derivatives of Phenothioxin.By SRI KRISHNA . CCCXXI1.-Synthesis of Substituted Thianthrens. Part 11. By SRI KRISHNA . C C C X X I I I - Substituted Phenyldichloroamiqes. By KENNEDY JOSEPH PREVIT~ ORTON and (the late) JOHN EDWIN BAYLISS . CCCXX1V.-The Colour of Monocyclic Substances Calculated by Assigning an Absorption Band to Each Possible Tautomeric Form. CCCXXV.-The Cyanine Dyes. Part VII. A New Method of Formation of the Carbocyanines. The Constitution of the Thioisocyanines and of Kryptocyanine. By WILLIAM HOBSON MILLS and WALTER THEODORE KARL BRAUNHOLTZ . CCCXXV1.-The Solubility of the Phenylenediamines and of their Monoacetyl Derivatives. By NEVIL VINCENT SIDGWICK and JAMES ACHESONEILL CCCXXVI1.-The Solubility of the Hydroxybenzaldehydes and the Hydroxytolualdehydes.By NEVIL VINCENT SIDGWICK and ERIC NEWMARCH ALLOTT . CCCXXVII1.-A New Absorption Pipette for Gas Analysis. By SIDNEY WALTER SAUNDERS . CCCXX1X.-Reduction of m-Methoxybenzyl Bromide by Hydrogen Iodide. By JOHN BALDWIN SHOESMITH . CCCXXX.-Organic Derivatives of Silicon. Part XXIX. Preparation Properties and Condensation Products of Di-p-tolylsilicanediol. By HERBERT SHEPPARD PINK and FREDERIC STANLEY KIPPINQ . . By JAMES MOIR . . 2745 2752 2767 2775 2779 2782 2786 2790 2792 2804 2813 2819 2826 2828 283 xxvi CONTENTS. CCCXXX1.-Separation of Octoic and Decoic Acids from Cocoanut Oil. By ERIC EVERARD WALKER . CCCXXXIL-Substitution in Vicinal Trisubstituted Benzene Derivatives. Part 11. By WILLIAM DAVIES and LEON RUBENSTEIN .CCCXXXII1.-Ring-chain Tautomerism. Part VII. The c$B-Trisubatituted Glutaric Acid Type. By KANTILAL CHHAGANLAL PANDYA and JOCELYN FIELD THORPE . CCCXXX1V.-Ring-chain Tautomerism. Part VIII. The Effect of the cycZoHexane Nucleus on the Carbon Tetrahedral Angle. By ERIC WILLIAM LANFEAR and JOCELYN FIELD THORPE . CCCXXXV.-The Preparation and Properties of Selenium Trioxide and Chloroselenic Acid. By RICHARD ROBERT LE GEYT WORSLEY and HERBERT BRERETON BAKER . CCCXXXV1.-Optical Activation of Racemic Acid by d-Malic Acid. By ALEX. MCKENZIE HAROLD JAMES PLENDERLELTH and NELLIE WALKER . CCCXXXVI1.-The Conversion of Paraf ormaldehyde into Glycollic Acid. By DALZIELLEWELLYN HAMMICK and ALFRED REGINALD BOEREE . CCCXXXVII1.-w-Trichloro- and o-Tribromo-quinaldine and the Preparation of Quinaldinic Acid.By DALZIEL LLEWELLYN HAMMICK . CCCXXX1X.-The Interaction of PB'-Dichlorodiethyl Sulphide Sulphoxide and Sulphone with Glycine Ester and with Potassium Phthalimide. By ALBERT ERIC CASHMORE and HAMILTON MCCOMBIE CCCXL.-The Interaction of Potassium Tetroxide with Ice and with Dilute Sulphuric Acid. By HERBERT HAWLEY and HENRY JULIUS SALOMON SAND . CCCXL1.-Note on Glasstone's Discussion of Over-voltage Measurement. By HENRY JULIUS SALOMON SAND and EDWARD JOSEPH WEEKS . CCCXLI1.-Preparation and Stability of Cuprous Nitrate and Other Cuprous Salts in presence of Nitriles. By HOWARD HOULSTON MORGAN . CCCXLIl1.-Derivatives of Thionaphthacoumarin. By SAMUEL SMILES amd LESLIE RALPH HART . CCCXLIV.-The Melting-point (Solidus) Curve for Mixtures of Potassium Nitrate and Sodium Nitrate.By WALTER MATTHEW MADGIN and HENRY VINCENT AIRD BRISCOE . CCCXLV.-Piperitone. Part VI. The Reduction of Piperitone. By REGINALD SLATER HUGHESDON, HENRY GEORGE SMITH and JOHN READ . PAQE 2837 2839 2852 2865 2870 2875 2881 2882 2884 2891 2896 2901 2907 2914 291 CONTENTS. xxvii PAQE CCCXLVI.-Intermittent Current Electrolysis. Part 11. By SAMUEL CCCXLVII.4uccinylfluorescein and its Derivatives. By SIDNEY BIGGS and FRANK GEO. POPE CCCXLVII1.-A New Type of Reduction-Oxidation System. Part I. Cysteine and Glutathione. By MALCOLM DIXON and JUDA HIRSCH QUASTEL . CCCXL1X.-The Accurate Determination of Elevation of Boiling Point. By KAZIMIERZ JABECZYASKI and STANISLAW KON .CCCL.-Experiments on the Synthesis of the Polyacetic Acids of Methane. Part VIII. An Improved Synthesis of Methanetriacetic Acid. By MARCEL HENRY DREIFUSS and CHRISTOPHER KELK INGOLD . CCCLI.-Chloro-o-xylenols. Part I. 5-Chloro-o-3-xylenol, 6- Chloro - 0-3- x ylenol and 5- Chloro -0-4- x ylenol. By LEONARD ERIC HINKEL WILLIAM THOMAS COLLINS, and ERNEST EDWARD AYLINQ . CCCLI1.-Inorganic Complex Salts. Part 111. Racemis-ation and the Stability of Complex Ions. By WILLIAM THOMAS and RONALD FRASER . CCCLIIL-Sodium 6-Chloro-5-nitro-m-toluenesulphonate-a New Reagent for Potassium. By HERBERT DAVIES and WILLIAM DAVIES . CCCL1V.-Derivatives of the Four Isomeric Sulphonic Acids of m-Tolyl Methyl Ether. By ROBERT DOWNS HAWORTH and ARTHUR LAPWORTH .CCCLV.-The Corrosion of Iron in Water and in Neutral Salt Solutions. By JOHN ALBERT NEWTON FRIEND . CCCLV1.-Alkyl Hypochlorites. By FREDERICK DANIEL CHATTAWAY and OTTO GUIDO BACKEB~RG CCCLVI1.-Yohimbine (Quebrachine). Part 111. Esteri-fication of Yohimbic Acid. By ELLEN FIELD . CCCLVIII.-StuCiies of Electrovalency. Part 111. The Catalytic Activation of Molecules and the Reaction of Ethylene and Bromine. By RONALD GEORGE WREY-FORD NORRISH CCCL1X.-Cadmium Sulphide and the Estimation of Cad-mium. By ALFRED CHARLES EGERTON and FRANK VICTOR RALEIGH . CCCLX.-The Vapour Pressure of Cadmium and its Alloys with Zinc. By ALFRED CHARLES EGERTON and FRANK VICTOR RALEIGH . Overvoltage Study of the Lead Electrode. GI.ASSTONE . . 2926 2934 2943 2953 2964 2968 2973 2976 2982 2996 2999 3003 3006 3019 302 xxviii CONTENTS.CCCLX1.-Products of the Destructive Distillation of Sodium Anthraquinone- 1 - and -2-sulphonates. By ARTHUR GEORGE PERICIN and WILLIAM GAWAN SEWELL . CCCLXI1.-The Relationship between Colour and Con-stitution in the Nitrobenzaldehydehydrazones. By FREDERICK DANIEL CHATTAWAY and GEORGE ROGER CLEMO . CCCLXII1.-A Quantitative Investigation of the Photo-chemical Interaction of Chlorine and Hydrogen. By MURIEL CATIXERINE CANNING CHAPMAN . CCCLX1V.-The Interaction of Bromine with Acetic Anhydride. By KENNEDY JOSEPH PREVIT~ ORTON, HERBERT BEN WATSON and (the late) JOHN EDWIN BAYLISS . CCCLXV.-The Bromine Compounds of Phenanthrenc. Part 11.By HERBERT HENSTOCK . CCCLXV1.-Quantitative Measurements of the Reactivity of the Halogens in Aromat.ic Compounds. By ARTHUR HENRY RHEINLANDER . CCCLXVII.4tudies in Nitration. Part I. The Velocity of Nitration of Phenol. By FRANCIS ARNALL . CCCLXVII1.-Some Derivatives of the Vinyldiaceton-alkamines. By FREDERIC STANLEY KIPPING . CCCLX1X.-The Constitution of the Disaccharides Part IX. Gentiobiose Its Identity with Amygdalin Biose. By WALTER NORMAN HAWORTH and BIRKETT WYLAM. CCCLXX.-The Constitution of Raffinose. By WALTER NORMAN HAWORTH EDMUND LANGLEY HIRST and DAVID ARTHUR RUELL . CCCLXXI.-Condensation of Aldehydes with Cyano-acetamide. By RONALD HAMILTON CURTIS JAMES NELSON EDMUND DAY and LIONEL GEORGE KIMMINS CCCLXXIL-The Formation and Stability of spiro-Compounds.Part XI. Bridged spiro-Compounds from cycloPentane. By CHRISTOPHER KELK INGOLD ERIC WILLIAM LANFEAR and JOCELYN FIELD THORPE . CCCLXXII1.-An X-Ray Investigation of Certain Organic Estem and other Long-chain Compounds. By GEORGE SHEARER. CCCLXXIV.-Further X-Ray Measurements of Long-chain Compounds and a Note on their Interpretation. By ALEX MULLER and GEORGE SHEARER CCCLXXV.-The Influence of Dilution on the Hydrolytic Dissociation of some Oxime Hydrochlorides. By LEONARD BEAUMONT TANSLEY . . PAGE 3032 3041 3062 3081 3097 3099 3111 31 15 3120 3125 3131 3140 3152 3156 316 CORTENTS. xxix PAQE CCCLXXV1.-A Synthesis of m-Opianic Acid. By WILLIAM HENRY PERKIN jun. and FRANCIS WLLBERT STOYLE CCCLXXVI1.-The Condensation of Aromatic Amino-sulphonic Acids with isoCyanic Acid Phenylcarbirnide, and Cyanamide By JOHN RICHARD SCOTT and JULIUS BEREND COHEN .CCCLXXVII1.-Sulphonation of para-Substituted Phenyl-carbamides. By JOHN RICHARD SCOTT . CCCLXX1X.-The Conditions of Reaction of Hydrogen with Sulphur. Part IV. The Direct Union of Oxygen and Sulphur. By RONALD GEORGE WREYFORD NORRISH and ERIC KEIGHTLEY RIDEAL . CCCLXXX.-The Hafnium Content of Zirconium Ores. By GEORGE HEVESY and VALDEMAR THAL JANTZEN . CCCLXXX1.-The Chemistry of Posidonia Fibre. Part I. By JOHN CAMPBELL EARL . CCCLXXXI1.-The Action of Highly Concentrated Hydro-chloric Acid on Cellulose and on some Derivatives of Glucose and of Xylose. By EDMUND LANGLEY HIRST and DONALD ROBERTSON MORRISON .CCCLXXXII1.-Preparation of 2 3- 2 6- and 3 4-Dinjtrotoluenes. By HAROLD JAMES PAGE and BENJAMIN RICHARD HEASMAN . CCCLXXXIV .-Dihydropent indole and its Derivatives. Part I. By WILLIAM HENRY PERKIN jun. and SYDNEY GLENN PRESTON PLANT . CCCLXXXV . - Nitration of p - Dichlorobenzene. By HAROLD JAMES PAGE and BENJAMIN RICHARD HEASMAN CCCLXXXV1.-The Partial Pressures of Sulphuric Acid over Concentrated Aqueous Solutions of the Acid a t High Temperatures. By JOHN SMEATH THOMAS and ALEXANDER GEORGE RAMSAY . . CCCLXXXVII.4tudies in the Organic Polysulphides. Part I. The Action of Anhydrous Potassium Penta-sulphide on some Alkyl Halides. By RICHARD WILLIAM RIDING and JOHN SMEATH THOMAS . CCCLXXXVII1.-The Chemical Constitution of Bacterial Pigments. Part I. The Isolation of Pyocyanhe and the Preparation of its Salts. By HAMILTON MCCOMBIE and HAROLD ARCHIBALD SCARBOROUGH . CCCLXXX1X.-The Action of Hydrogen Sulphide on Lithium Ethoxide. Lithium Hydrosulphide. By JOHN HENRY JONES and JOHN SNEATH THOMAS , 3171 3177 3191 3202 3218 3223 3226 3235 3242 3247 3256 3271 3279 328 XXX CONTENTS. CCCXC.-Use of the Quinhydrone Electrode for the Estima-tion of Amino-acids and of Acid and Basic Functions. By LESLIE J. HARRIS . . CCCXC1.-The Chemistry of Polycyclic Structures in Relation to their Homocyclic Unsaturated Isomerides. Part V. Orientation in the gem-Dimethyldicyclopntene Series. By ROBERT CHARLES GRIMWOOD CHRISTOPHER KELK LNGOLD and JOCELYN FIELD THORPE CCCXCI1.-The Interaction of Primary Amines and 2-Dithio-benzoyl. By ERNEST WILSON MCCLELLAND and JOHN LONGWELL . CCCXCIII.-Studies in Fluorescence Spectra. Part I. Some Benzoid Hydrocarbon Vapoum. By JOSEPH KENNETH ~NARSH . . Part III. Valency Interchange in the Hydromuconic System. By ERNEST HAROLD FARMER CCCXCV.-Experiments on the Synthesis of Substances Possessing the Ladenburg Formula. Part I. Associated Three-carbon Ring Systems. By ERNEST HAROLD FARMER . Part XV. Three-carbon Tautomerism in the cycZoPropane Series. Part 11. By FRANK ROBERT GOSS, CHRISTOPHER KELK INGOLD and JOCELYN FIELD THORPE . CCCXCM1.-The Tautomerism of Amidines. Part 111. The Alkylation of Open-chain Amidines (continued). By FRANK LEE PYMAN . CCCXCVIII . -Bromon it ro cou marins and their React ion with Alkalis. By BIMAN BIHARI DEY and KARNAD KRISHNA Row CCCXC1X.-Diazo- transf ormations of Aminocoumarins and Aminonaphthapyrones. By BIMAN BIHARI DEY and HARIDAS DALAL . CCCC.-The Freezing-point Curves of Binary Mixtures of some Substituted Acetanilides. By GLYN OWEN . Van Der Waals Memorial Lecture. Delivered on November 8th 1923. By DR. JAMES HOPWOOD JEANS Sec. R.S. NOTES.-~ Improved Filter-pump. By KENNETH CLAUDE DEVEREUX HICKMAN . A Laboratory Water Motor. By KENNETH CLAUDE DEVEREUX HICKMAN . . . . CCCXC1V.-Muconic and Hydromuconic Acids. CCCXCVI.-The Chemistry of the Glutaconic Acids. PAGE 3294 3303 3310 3315 3324 3332 3342 3359 3375 3384 3392 3398 3414 ,341 CONTENTS. XXXl PAGE A Thermostat Refrigerator. By KENNETH CLAUDE DEVEREUX HICKMAN . . 3416 Sulphur Dioxide as an Oxidking Agent. By WILLIAM WARDLAW and NORMAN DARBY SYLVESTER . . 3417 The Reaction between p-Dibromobenzene and Magnesium. By HERBERT SHEPPARD PINK . . 3418 Action of Hydrazine Hydrate on Phenanthraquinone. SIKHIBHUSHAN DUTT and NIRMAL KUMAR SEN . " 3420 OBITUARY NOTICES . 342

ISSN:0368-1645    

DOI:10.1039/CT92323FP001

出版商:RSC    

年代:1923

数据来源: RSC

摘要:

14 EENYON AND MCNICOL INVESTIGATIONS ON THE 11.-Investigatioons on the Dependence of Rotatory Power on Chefiaical Constitution. Part X I V. The Normal -4 liphatic Ethers of d-P-Octanol. By JOSEPH KENYON and REGINALD ARTHUR McNrcoL. IN the preceding parts of this scries of investigations the optical rotatory and rotatory dispersive powers of a considerable number of secondary alcohols and of esters derived from them have been examined. From the results obtained three main conclusions may be drawn. (1) In a homologous series of optically active alcohols of the general formula R*CH( OH)*Rf where R represents the growing aliphatic chain departures from what may be termed the normal alteration of rotatory power with increase of molecular weight are observed when R consists of a chain of five or ten (eleven) carbon atoms.(2) A similar phenomenon is observed in homologous series of esters of the formula R1R2*CH*O*CO*R when the growing chain R contains five or ten (eleven) carbon atoms. It will be noticed that this case differs from (1) above in that R is not directly attached to the asymmetric carbon a.tom. (3) Alcohols of simple chemical constitution possess simple rotatory dispersive powers under widely varying conditions of tem-perature whereas the aliphatic esters derived from them show simple rotatory dispersive powers only a t low temperatures ; at higher temperatures and in solution the dispersive powers become complex. The results obtained by observing the rotatory powers of these two classes of compound both in the homogeneous state over a wide range of temperature and in solution at the temperature of the laboratory make it highly probable that the differences i DEPENDENCE OF ROTATORY POWER ETC.PART XIV. 15 dispersive power are due to some change in the molecular con-stitution of the esters occurring with change of conditions and it has been suggested that this phenomenon may be due to some specific property of the carboxylic portion of the molecule. I n view of the possible effect of adjacent oxygen atoms in the carboxylic portion of the molecule it was thought advisable t o examine the rotatory powers of substances in which this possible disturbing factor is not present. To this end a series of ethers was prepared containing in each case as the asymmetric portion of the molecule the sec.-octyl radicle and as the second radicle, one of the normal alkyl groups methyl ethyl up to n-nonyl.Such a series of compounds semis to fulfil the conditions laid down above. sec.-Octyl alcohol was chosen as the parent alcohol because it is the most readily obtainable of the optically active alcohols of simple chemical constitution. The investigation of the optical properties of these ethers has led to the following interesting results-at all temperatures between 15" and 130" they exhibit simple rotatory dispersion for a t no point within these limits does the dispersion ratio a4358 /x5461 fall below the value 1.677 and in addition when the reciprocal of the rotation is plotted against the square of the wave-length of the light used linear curves are obtained for every ether examined, showing that the one-term Drude equation expresses the relation between rotatory power and wave-length of the light used.Determinations of the rotatory powers of the ethers in the homogeneous state over a range of temperatures 15-130" for light of different wave-lengths show the presence of marked depressions in the optical rotatory power in the case of the members containing the n-propyl n-amyl and hexyl and n-octyl radicle. It is considered that these investigations show that the magnitude of the rotatory power may be influenced by the approximate closing of the spiral arrangement of three types of chain present in all these compounds. These are (a) any complete chain through the molecule ( b ) the chain of atoms up to and including the asymmetric carbon atom and ( c ) the chain of atoms attached to the asymmetric carbon atom.I n the mse of the secondary alcohols dealt with in the earlier parts of these investigations, oonclusive evidence has been obtained that the rotatory power is affected at intervals not only by the chain of the whole molecule, but also by the chain attached to the asymmetric carbon atom, whilst in the case of the esters of these alcohols as shown in Part XI11 (this vol. p. 1) the influence of chains of t'he types ( b ) and (c) is demonstrated. I n the case of the ethers herein described the evidence is not conclusive but points to the possi 1 G KENYON AND MCNICOL INVESTIGATIONS ON THE bility that the magnitudes of the rotatory powers of different members of the series are affected by the completion of a spiral in chains of all three types.The irregularities due to this cause may be most clearly demon-strated by plotting rotatory powers as ordinates a.gainst the number of carbon atoms in the growing chain as abscissE. In the figure, FIG. 1. I I -I 4 I 1 - 1 . -1 2 3 4 5 6 7 8 9 Numbw OJ carbon atoms in growing alkyl chain. The ethers of d-p-Octanol. A. [a]M61 in 5% solution in carbon disulpkide. B. [alpw in the homogeneous state. D. [a],,, in 5% solution in ethyl alcohol. c. lal;&l 9 9 Y 9 9 9 99 . the values actually plotted are for but strictly similar curves are obtained’by plotting the specific rotatory powers for any of the wave-lengths employed. A very unusual effect was observed when the rotations of these ethers were determined in 5 per cent.solutions in carbon disulphide and in ethyl alcohol; in all previous cases in this series of investi-gations it has been found that the former solvent effects a consider DEPENDENCE OF ROTATORY POWER ETC. PART xw. 17 able depressing action and the latter solvent an exalting action, although to a less degree. In the series of ethers now being con-sidered however the reverse is the case for carbon disulphide causes enhanced rotations and ethyl alcohol depressed ones. As may be seen from the diagram the deviations from what may be regarded as the normal values are the same in solution as for the substances in the homogeneous state. The ethers may be prepared either according to the method of Ferns and Lapworth (T.1912 101 273) in which potassium p-octyloxide is added to a n-alkyl p-toluenesulphonate or by allowing potassium p-octyloxide to react with a normal alkyl haloid. Samples of an ether prepared by either method are identical in rotatory power and this fact allows of a strong presumption that no racemisation occurs during either process. E x P E R I M E N T A L . Action of Potassium on d- p-0ctanol.-To clean potassiuni (4 grams) covered with dry benzene (or dry ether) there was added slowly d-p-octanol (23 grams) a t such a rate that the reaction did not become too vigorous; when most of the potassium had dis-solved the reaction was completed by gentle warming. The reaction mixture was then poured into ice-water in an atmosphere of carbon dioxide and the whole distilled in a current of steam.The distillate was extracted with ether the ethereal extract dried and after removal of ether and benzene distilled under reduced pressure. The octyl alcohol thus obtained showed + 19-36' in a 2-dcm. tube whereas the original alcohol showed + 19.40". Thus it is evident that no racemisation occurs under these conditions. General Method of Preparation of the Optically Active Ethers. To the solution (or suspension) of potassium p-octyloxide in ether (or benzene) was added the theoretical amount (calculated on the potassium used) of the alkyl bromide (or iodide) and the reaction mixture gently heated under reflux for about twenty hours care being taken to prevent the access of moisture during this period.In the cases of methyl and ethyl iodides and ethyl bromide reacting with an ethereal solution of potassium P-octyloxide heating is not necessary standing a t the ordinary temperature for several hours being quite sufficient. The potassium bromide (or iodide) was washed out with water and the dried ethereal (or benzene) solution mixed with sufficient phthalic anhydride to convert unchanged see-octyl alcohol into its hydrogen phthalic ester. After removing the ether (or benzene) the residue was heated at 110-115" fo 18 KENYON AND MCNICOL INVESTIGATIONS ON THE TABLE r. Determinations of Density (D$) and of Rotatory Power ( u50mm.) for the Ethers in the Homogeneous State. D 0.8076 at 19"; 0.7870 at 43.4"; 0.7700 at 62"; 0.7536 at 81.4"; 0.7391 a6438 2.67" at 14" 2.07' at 53"; 1-85' at 61"; 1.56" at 81.5"; 1.36" at 101".a5461 3-57' at 14"; 2-70' at 51.4"; 2.67" at G1"; 2-33" at 82"; 1.86" at 104". a5066 4.29" at 14" ; 3.24" at 53.5"; 3.16" at 61" ; 2.05" at 81-5" - 2.43" at 98". a4goo 4.81' at 14" ; 3-66" at 54" ; 3-84" at 61" ; 3.09" at 81" ; 2183" at 98". aqS7 5.06" at 14" ; 3.75" at 55" ; 3.70" at 61" ; 3.22" at 81.5" ; 3.00" at 98". a4358 5.87" at 14"; 4.60" at 51"; 4-18' at 01"; 8-76" at 82"; 3.22" at 98". Methyl d-sec.-octyl ether. at 99.4". Ethyl d-sec.-octyl ether. DiZ 0.7895 at 17.2"; 0-7719 at 39.7"; 0.7545 at 58.5"; 0.7387 at 79.0"; a6438 5-86' at 17.8"; 4.94" at 56"; 4-63' at 81"; 4.15" at 06"; 3.89" at 113". a5461 8-08" at 17.8" ; 6-97' at 54" ; G.24" at 79" ; 5-68' at 97"; 5-47" at 110".a5088 9.61" at 17.8"; 8-04" at 56"; 7-30" at 81"; 6.69" at 07"; 6-31" at 112". adWO 10.47" at 17.8"; 9.10" at 55.5"; 8.29" at 80"; 7-56" at 96"; 7-12' at 112". a4678 11-31' at 17.S"; 0.65" at 55"; 8.69" at 79"; 7-99' at 95"; 7-50" at 110". a,,, 13.09" at 17-8" ; 11-19' at 54" ; 10.04' at 79" ; 9-19" at 95" ; 8.81" at 105". 0.5202 at 100.6". n-Propyl d -sec. - oc tyl ether. DS 0.7971 at 12" 0.7598 at 61'; 0.7435 at SO"; 0.7303 at 90". a,', 8.30" at 16.5"; 7.27" at 50.6"; 0s.76" at 67"; 6.10" at 97"; 5.61" at 121". aPa6, 13-42" at 16-5"; 11-70" at 50.5"; 10.97" at 67"; 9-77" at 9G"; 9-12" at 120'. n-Butyl d-sec.-octyl ether. DZ 0.7971 at 18.5"; 0.7766 at 45"; 0.7568 at 70"; 0-7226 at 103"; 0.7063 at 135". aB438 6.62" at 20" ; 5-64' at 56" ; 5.24" at 74" ; 4-75" at 102" ; 4.47" at 119".u54Bl 8-94' at 20"; 7.75" at 57" ; 7.18" at 76" ; 6.70" at 98" ; 6.05" at 118". a6,,86 10.41" at 20"; 8.88" at 59"; 8.41" at 75"; 7.66" at 101"; 7-10' at 119". 11.82" at 20" ; 9-98" at 59" - 9.20" at 75" * 8.59" at 101" ; 7-89" at 119". u~~~~ 12-34' at 20" ; 10.60" at 58' ; 9.80" at 76' ; 9-21' at 99" ; 8-38" at 119". aPgj8 14.38"at 20"; 12-16' at 67"; 11-37' at 76"; 10.62" at 98"; 9.69 at 118". n-Amy1 d-sec.-octyl ether. DS 0.7989 at 20"; 0.7820 at 42.6"; 0.7696 at 60"; 0.7484 at 84.4"; 0.7233 5-25" at 17"; k.91" at 35"; 4.61" at 53"; 4-18' at 56"; 4-00' at 101"; 05461 7-38' at 17"; 6-94" at 35"; 6.34" at 54"; 5.90" at 72"; 5.41" at 105'; ~5~~~ 8.47" at 17"; 8-19" at 32"; 7-57' at 53"; 6.92" at 77.5"; 6.44" at 100"; adm 9.03" at 17"; 9.17" at 31"; 8.57" at 54"; 7.84" at 77.5"; 7.33" at 1 0 0 " ~ a4678 10.23" at 17".9.62" at 30°; 8-92" at 56"; 8.19" at 76"; 7.64" at 100"; at 114.8" * 0,7023 at 139.6". 3.50' at 135". 4.47" at 135". 5.73' at 129". 6-58' at 130". 6.93" at? 131'. a4s58 11.79" at 17"- 11-08" at 36"; 10.33" at 54"; 9.50" at 74"; 8-75" at 102"; 71S5" 133" DEPENDENCE OF ROTATORY POWER ETC. PART XIV. 19 TABLE I .- (continued). n-Hexyl d-sec.-octyl ether. D: 0.8047 a t 17.0" ; 0-7881 a t 40.4" ; 0.7723 a t 62.0" ; 0.75GS at 82.5" ; 0.7149 a t 137". a6438 4.69" at 21.2" ; 4-29' a t 42" ; 3-77" a t 80" ; 3-39' a t 108" ; 2.98" at 137". agq61 6-52' a t 21.2" ; 6-02" at 41" ; 5-41" a t 78" ; 4-77' at 109" ; 4.17" at 138". am8& 7-48' at 21.2" ; 6.96" at 42" ; 6-17" a t 80" ; 5.59" a t 106"; 4.88" a t 137".a4soo 8-45' a t 21.2" ; 7-87' a t 42" ; 6.92" at 80" ; 6.26" a t 107" ; 6-60" at 136". a4678 8-89' at 21.2" ; 8.33" at 42" ; 7.26" at 79" ; 6.46" a t 108" ; 5.87" at 136". a4368 10.35" a t 21.2" ; 9.67" a t 42" ; 8.34" at 78" ; 7.51" at 108" ; 6.56" at 138". n-Heptyl d-sec. -oc tyl ether. Di 0.8034 at 22"; 0.7776 a t 59"; 0.i672 at 73"; 0,7440 at 101"; 0.7290 at a6438 5.38" a t 16"; 4-51" a t 42"; 4.42" a t 64"; 4-20' at 85"; 3.88" at 117". a5461 7-50" a t 16" ; 6.81" at 43" ; 6.47" a t 61" ; 5-99' at 86"; 6-49" at 121". aS086 8'81" a t 16" ; 8-02' at 42"; 7-29" at 66" ; 6.80" at 85" ; 6.18" at 118". a4808 0.81" a t 16"; 9.09" at 43"; 8.38" at G3"; 7.90" at 83"; 7.09" a t 118". a4678 10.49" a t 16"; 9-48" at 44"; 5-89" at 64"; 8.49" at 80"; 7.23" at 119".a4358 12.08" at 16"; 10.fj7" at 46"; 10.18" at 64"; 9-50' at 82"; 8.41" at 120". 125". n- Octyl d-sec. -octyl ether. I)$ 0.5099 at 15'; O.iO29 a t 43"; 0.7780 at 66"; 0.7459 at 109"; 0.7264 4-36' at 20"; 4.01" at 42"; 3-75" a t GO"; 3.07' a t 108". 2.S7" at 130". aaqB 6-20' at 20"; 5-59' at 43"; 5.16" at 61"; 4.35" a t 108"; i.22" at 130". a;086 7-10' at 20" ; 6-51" a t 42" ; 6-01" a t 61" ; 5.00" at 108" ; 4.79" a t 130". 8-05' at 20" ; 7.35" at 42' ; 6.68" at 62" ; 5-54' at 108' ; 5-37' at 130". a4678 8-39' a t 20"; 7.58" at 43"; 6-97" a t 62'; 5.81"st 109"; 5-57' at 130". a4358 9.98" a t 20" ; 8.92" at 44" ; 8-36' at 62" ; 6.80" at 105' ; 6-59' at 126". at 143". n-Nonyl d-sec.-octyl ether. DS 0.8110 at 17"; 0.7911 at 47"; 0.7741 at 66'; 0-7573 at 89"; 0.7409 at a6438 4.49" a t 20"; 4-17' a t 45"; 3-72' a t 75"; 3-48' at 97'; 3-30' at 116".a5461 6.13" a t 20"; 5-77' at 44"; 6.19" at 75"; 4-86' at 95'; 4.54" a t 118". Q~~~ 7-27" a t 20" ; 6-62" at 4G" ; 6-10' a t 75" ; 5.66" a t 96" ; 5.39" at 117". u48w 8.18" at 20" ; 7.50" a t 46" ; 6.74" at 75" ; 6-29' a t 95"; 8-93" at 117". aOIp8 8.63" a t 20" ; 8-96" a t 45" ; 7.05" a t 76' ; 6.71" at 93'; 6-21' a t 115". aPaj8 9.97" at 20"; 9.19" a t 44"; 8.27" a t 76"; 7.86" at 92.6"; 7.37' at 115". ten hours. The cold reaction product was dissolved in ether, extracted with dilute sodium carbonate solution dried the ether evaporated and the resulting P-octyl alkyl ether purified by dis-tillation under reduced pressure. In no cam was any evidence obtained of the presence of unsaturated compounds.The sodium carbonate washings after acidification gave d- P-octyl hydrogen phthalate of the usual rotatory power. Preparation of Ethyl d-sec.-OctyZ Ether by the Use of Ethyl p-Toluene-sulphona te . The procedure described by Ferns and Lapworth (Zoc. cit.) was closely followed. Potassium d- p-octyloxide in benzene solution was allowed to react with the calculated amount of ethyl p-toluene-110" TABLE 11. Physical Properties of Ethers of d-@-Octunol. Ether. B. p. "C. mm. Methyl ............... 76-77'/44 E thy1 .................. 63-65 / 14 n-Propyl ............ 76 / 18 n-Butyl ............... 85-86/14 n- Amy1 ............... 99 I 1 5, n-Hexyl ............... 115 /1 a n-Heptyl ...... 1.. ...129/18 n-Octyl ............... 146/13 n-Nonyl ............... 163/18 Ether. Methyl .................. Ethyl ..................... n-Amy1 .................. n-Hexyl .................. ti . Hept yl ............... n-Propyl ............... n-Butyl .................. n-Octyl .................. n-Nonyl .................. 7 h 6438. 6-42 14.68 16.63 13.03 11.68 13.18 10.80 10-98 -ago. 0.8094 0.7861 0.7887 0.7923 0.7958 0.7983 0.8017 0.8038 0.8042 n%a 1.4212 1.4136 1.4148 1.4168 1.4218 1.4252 1.4267 1.4301 1.4326 D * Molecular refractive power. / /. \ Diff. from Found. calc. value. 46.27 - 0.13 50.11 + 0.07 54.59 - 0-05 59.32 + 0.07 (33.84 - 0.03 68.65 + 0-13 72.98 - 0.13 77.87 + 0.11 82.61 - 0.16 TABLE 111.Cornprison of Specijk Rotatory Powers at 20" A 5461. 8.63 20.33 20.51 22.46 18.19 16.29 18-41 15.33 15.45 A h 5086. 4500. 10.20 11.66 24-13 26.95 26.13 29-64 22.09 23.83 18.68 21-05 21.58 24-11 17-59 19-96 18-41 20.26 - -h 4678. 12.23 28-46 31-01 26-42 22.45 25-72 20.S4 21.35 -[.]',""a 7 A 4358. 13.59 32.86 32.92 36.13 29.06 25-95 29.75 24.7 7 24.60 I h 6438. 3.02 10.79 12.34 10-34 €4.65 10.42 7.95 8-98 TABLE IV. Compmison of Specijc Rotatmy Yozem in 5 per (1) In carbon clisulphide solution a t romi temperature in n 20-cin. tube. Observed rotation. Grams in . Ether. 100 C . C . 6438. 5461. 5086. 4800. 4678. 435% Methyl ......4-97 1.52 2.03 2.42 2.79 2.89 3-37 Ethyl . ........ 4.73 2.34 3.15 3.91 4.42 4.62 5-62 n-Butyl ...... 4.56 2.19 3.08 3.61 4.18 4-41 5.37 n-Amy1 ...... 3.53 1.34 1.78 2.16 2.41 2.59 3.09 n-Hexyl ...... 3.17 1-14 1.52 1-87 2.11 2.22 2.59 n-Heptyl ... 4.96 1.63 2.23 2.80 3.21 3.37 3.85 n-Octyl ...... 3.41 1-10 1.43 1.77 1.99 2.05 2-42 n-Nonyl ...... 3.30 - 1.42 - - - 2-47 6.16 - n-Propyl ... 5.47 - 3.44 - -7-6135. 12.31 24.27 24.58 19.00 1i.97 19-15 16.14 --( 2 ) In absolute et,hyl alcohol solution at room temperature in a 20-cm. Grams in Ether. 20cc. 6438. 5461. Methyl ...... 3-92 0.50 0.59 Ethyl ......... 4-96 1-38 1.75 n-Propyl ... 5.10 - 1.76 n-Butyl ...... 4-83 1.42 1-80 n-Amy1 ...... 4-81 1.19 1-49 n-Hexyl ......3.52 0.91 1.07 n-Heptyl ... 4.84 1.25 1-71 n-Octyl ...... 2.93 0.60 0.81 n-Nonyl ...... 4-21 - 1.26 Observed rotation. 5086. 4800. 0-70 0.73 2-20 2.51 2.18 2.44 1.81 2.03 1.31 1-41 2-03 2-24 0.92 1.04 - I - -- 4678. 4358. 0.79 0.96 2.63 2.97 - 2.96 2.54 3.03 2-10 2-43 1-54 1.70 2-42 2-76 1.08 1-30 - 1-99 6438. 6.37 13-04 -15.67 12-37 12.91 13-22 10.96 22 PIXILLIPS INVESTIGATIONS ON THE DBPENDENCE OF sulphonate dissolved in benzene. The gelatinous precipitate which had formed during six hours' heating on the water-bath was removed by filtration and the filtrate warmed with aqueous alkali, washcd with water dried and fractionally distilled under diminished pressure. In this way there were obtained by the use of 8 grams of potassium 5.4 grams of ethyl d-sec.-octyl ether with a b. p. 65"/16 mm. and C X ~ ~ ~ ~ + 8.03" for 100 mrn. These figures are in very close agreement with those given by the ether prepared by the general method described above using either ethyl bromide or ethyl iodide. All the ethers which were obtained in yields of 50-60 per cent. of the theoretical are colourless mobile liquids. The lower members possess somewhat penetrating but not unpleasant odours ; some of their physical constants are collected in Table 11. Measurements of the rotations of these substances in ethyl alcohol and carbon disulphide solution were made at room temperature and a t approximately 5 per cent. concentration. The authors desire to thank Rlr. 13. Hunter for valuable assistance, and the Government Grant Committee of the Royal Society for a grant with which most of the material used has been purchased. BATTERSEA POLYTECHNIC S.W. 11. [Received Novembg lst 1922.

ISSN:0368-1645    

DOI:10.1039/CT9232300014

出版商:RSC    

年代:1923

数据来源: RSC

摘要:

22 PIXILLIPS INVESTIGATIONS ON THE DBPENDENCE OF 111.-Investigations on the Dependence of Rotatory Power on Chemical Constitution. Part X V. Some n-Alkgl Ethers of d-Benxylmet~ylcarbinol. By HENRY PHILLIPS, OF the optically active compounds which exhibit complex rotatory dispersion the great majority contain the carboxyl group (or its equivalents the carboalkyloxyl or the xanthogenic ester group) and therefore it has been suggested that complex rotatory disper-sion may be a general property of the carboxyl group and may even be specifically due to the variable valency of the oxygen atoms contained in it. It is accordingly of interest to examine other optically active compounds containing an oxygen atom in the molecule in order to test this point. In the earlier parts of these investigations it has been shown that most secondary alcohols under very varied con-ditions of temperature exhibit simple rotatory dispersion whilst in Part XIV (this vol.p. 14) there is described a homobgous series of nine optically activc ethcrs all of which show simple rotatory dispersion. An extension of the latter investigation appearc ROTBTORY POWER ON CHEMICAL CONSTITUTION. PART XV. 23 desirable and accordingly a series of normal alkyl ethers of d- benzyl-inethylcarbinol was prepared and examined with results which are discussed and detailed in this paper. d-Benzylmethylcarbiol wa8 chosen for this purpose because its rotatory power is high and only slightly influenced by temperature. It can also be obtained fairly readily in a state of optical purity (Part VI T.1914 106, 11 13). 1 O( F I G . 1. I -$-I -,~"-'-Q- 1 2 3 4 6 6 7 8 9 Number of carbon atoms in growing alkyl chain. The Et li eru of d - Beiaz ylmeth ylcarb inol. I. [a]us in 5(v0 solution in carbon dbulphide. 11. [ a ] u ~ , , , , ethyl alcohol. 111. [a]:?; in the homogeneouo atate. Nine members of the series C,H,*CH,*CH(CH,)*OR where R represents a normal alkyl group have been prepared by the method described in Part XIV (Zoc. cit.) and shown to exhibit simple rotatory dispersion over the temperature range 20-140". Further support is thus afforded to the view that complex rotatory dispersion must be regarded as a property of the carboxyl group as a whole and not of any one atom in it. That is to say it is to the prapinquity of the oxygen atom8 in this group that the equi 24 PHILLIPS IWESTIGATIONS ON THE DEPENDENCE OF librium -C<gH e -C< / O I I with consequent complexity of OH' rotatory dispersion is probably due.In alcohoIs R-OH and ethers R*O*R1 it may be concluded that oxygen atoms in different molecules are not able to approach sufficiently near to each other to employ their subsidiary valencies with the result that there is only one kind of molecule present in the substance which there-fore shows simple rotatory dispersion. This is well borne out by the fact that ethers and alcohols are known to associate only slightly if a t all. The magnitudes of the rotatory powers of the members of this series of ethers as will be seen from Fig. 1 show remarkable irregu-larities.Assuming that the normal alteration of specific rotatory power with the growth of the alkyl chain is correctly indicated in the figure it will be seen that depressions in the rotatory power occur at the propyl amyl heptyl and octyl members. By analogy with previous results the depressions a t the propyl and octyl members are ascribed to the influence of the chain of five or ten atoms up to and including the asymmetric carbon atom that a t the heptyl member to the influence of the chain CH,*CH (CH,Ph)*O*C ,H 15, whilst the depression a t the amyl member, CH,*CH(CH,Ph)*Oi*C5Hll, is analogous to similar alteration in rotatory power exhibited by the valerates in some series of esters as for example, CH,*CH( C,H,,)*Oj*CO*C,H,. E X P E R I M E N T A L .Preparation of d-Benxylrnethylcarbino1.-The optically active alcohol required for this research was prepared by the method given in Part VI. One thousand six hundred and seventy grams of benzyl methyl ketone were obtained by the passage of 2660 grams of phenylacetic acid dissolved in 11,450 grams of glacial acetic acid through a silica tube heated a t 400" and half filled with thoria. The ketone was reduced in boiling ethyl alcoholic solution by means of sodium to the corresponding alcohol which was converted into the hydrogen phthalic ester. One thousand nine hundred grams of this ester were obtained fractional crystal-lisation of the brucine salt of which from acetone yielded the pure ZBdA salt. From this pure salt 230 grams of pure d-benzylmethyl-carbinol were obtained.@" = 0.9877; n2& = 1-5194; a z l + 32-76"; + 33.22"; + 33.28". The yield of ZBdA salt was diminished in the resolution by the crystallisation from the concentrated mother-liquors of the corre Methyl .... . . .. . Ethyl . ..... . ..... Propyl . . . . . . . . Butpl . . . . . . . . . . . Amy1 ............ Hexyl . . . . . . . . . . . . Heptyl . . . . . . . . . Nonyl . . . ... . . . . . . Octyl ... . . . . . . . D3". 0.9314 0.9162 0.9093 0.8991 0.8900 0.8878 0.8828 0-8815 0-8820 Boiling 'C/mm. 85'/12 93/19 103113 115112 127114 137/14 156119 170112 126/1 point. TABLE I. n-Alkyl Ethers of d-Benxyl~,et~~yl~rblLylcnrbnol. F A 6438. 1.4875 1.4842 1.4i87 1.4761 -I 1.4722 1.4i20 -A 5896.1.4909 1.4875 1-4818 1.4791 1-4761 1.4756 1.4750 1.4748 1.4747 A 5461. 1.4942 1.4906 1.4849 1.4819 1.4787 1.4783 1.4778 1.4775 1.47'73 ny, d A 6086. 1.4978 1.4942 1.4874 1.4854 - -1.4807 1.4804 I A 4800. 1-5015 1.4976 1.4916 1-4884 I -1.4837 1.4832 26 PHILLIPS INVESTIGATIONS ON THE DEPENDENCE OF sponding 1BZA salt. Complicated mixtures of the two salts were obtained on recrystallisation which however finally resulted in the isolation of a sinall quantity of almost pure ZBlA salt. Froin this were isolated 6 grams of E- benzylmethylcarbinol E& - 30.90". Action of Potassium on BenxyZmeth~ZcurbinoZ.-Fiftcen grams of a partly active alcohol with E til- 6-13" in a 50 mm. tube dissolved in 100 C.C.of dried benzene were treated with 2 grams of powdered potassium. On complete dissolution of the metal the Z-alcohol was recovered. It had General Method of Preparation of the Aclive Ethers.-Except for the use of 3 grams of potassium with 11 grains of the d-alcohol, dissolved in benzene the method emplQyed was the same as that given in Part XIV (Zoc. cit.). The yield was 30-40 per cent. of the theoretical. The lower members of the series are pleasant-smelling liquids ; the methyl and ethyl ethers have odours reminiscent of nerol. In Table I are given some physical properties of the ethers, whilst in Table I11 are recorded the specific rotatory powers cal-culated from the observed rotatory powers given in Table 11. The determinations of rotatory power in ethyl alcohol and in carbon disulphide are tabulated in Tables IV and V respectively.The densities were determined in a pyknometer holding about 3 C.C. The rotations were measured in 50 mm. tubes round which heated mineral oil was circulated by means of a pump but are here given as for 100 mm. - 6-09" in a 50 mm. tube. TABLE 11. Observations of Density (DS) and Rotatory Power ( u ~ ~ ~ . ) in the Homogeneous State of the n-Alh~l Ethers of d-Re?iz?lZm.ethylcn7.binoZ. Methyl. Density 0-92i3 at 2 7 O ; 0.9135 at 47.5"; 0-8909 a t 74.5"; 0.8718 at 96.3"; a,,498 4.34" a t 18'; 4-20" a t 29.8" *; 3.68" a t 47.5"; 3-24" at 67"; 2.64" at a5461 6.00' at 18" ; 6.10" at 36.4" *; 4-76" at 45" ; 4.18" at 62" ; 3-60' at 83' ; a5086 7.32" at 18"; &G8" at 28"; 588" at 47.5"; 4-92" at 65'; 3.88" a t 88"; a4800 8.34" at 18"; 7-92" at 27"; 6.83" at 47.5"; 5SO" at G3"; 4.G2" at 88"; 44678 8-80" at 18'- 8.28" at 36" *; 7.20" at 47.6"; 6.3s" at 62.5"; 4.94" at a4358 10.22" at 18"; 9-04" at 34" *; &9G0 at 61"; 6.26" at i 0 " ; 5-52" at 0.8550 at 112"; 0.8392 at 131.5".88"; 2.04" at 109". 2.80" at 106". 3-16' at 108". 3-66" at 107". 87"; k00" a t 106". 83.5" ; 4-38' at 102" ; 4-60" at 100'. * WhiIo cooling ROTATORY POWER ON CHEMICAL CONSTITUTION. P9RT XV. 27 TABLE 11.-(continued). Ethyl. Deiisity O.OLi1 at 24" 0.00G8 rrt 36.5"; 0.5781 at 71.8"; 0.S510 at 101.5"; a6438 16-18' at 22"; 15-46" at 43"; 14.22" at Gi'; 13-30" at 87.2'; 12-10' at aj401 23-80' at 19"; 20.48" at 67"; 18-98" at 87"; 17.72" at 112"; 16-84' at a5088 27-60" at 22"; 26.20" at 43"; 24-44' at 67"; 22.64" at 85"; 21.10" at a4800 32.02" at 22"; 30.46" at 43"; 28.40' at 67"; 26.52" at 57"; 24.30" at a4678 34.38" at 22"; 32.25" at 43"; 30.42" at 67"; 28.22' at 87"; 26-16' at 41.00" at 19"; 38.14" at $4"; 35.92" at 05"; 32.92" at 8'7"; 30.58" at 0-8344 at 123" ; 0.81 15 at 144.5".111" *; 11.42" at 133". 121"; 15.90" at 140". 111" *; 19-88' at 133". 113" *; 22.80" at 133". 113" *; 24-703 at 13.3". 112"; 28.24" at 131 . n- Prop yl. Density 04038 at 28"; 0.8571 nt 6.3"; 0.SGG2 at 78"; 0.8486 at 99"; 0.8342 01643@c 16*10" at 23" ; 15-34' at 43"; 14.G2" at 60" ; 14.42" at 70" * ; 13.96" at a5461 23-52" at i2" ; 22-16' at 4i0 ; 20.86" at 62" ; 20.22" at $2" *; 19-72" at a6086 27-74" at 23" ; 26-32' at ; 24.98" at 60.5" ; 24-26' at 70.4" *; 23.38" a4800 31.78" at 23" ; 30.06" at 43" ; 28.42" at 61"; 27.72" at 71" * ; 26-86" at a4678 33.80" at 23"; 32.00" at 45"; 29.98" at 62"; 28-34' at 80"; 27-04' at a,,,,~40-60" at 23"; 37-76" at 45"; 3G.08" at 61.5"; 34.50" at 72" *; 33.88" at 114"; 0.8312 at 120".81" - 13.26" at 95.5" * 12.66" at 111". 81"; 18.86" at 94". 17.98" at 111". at 81"; 22.36" at 95"; 21.62" at 110.5". 81"; 25-66' at 95"; 24.65" at 11.1". 94.5" ; 26.16" at 110". at 81"; 32.51" at 94"; 30.98" at 110.5". n- Bu tyl . Density 0.8973 at 2i"; 0.8837 at 43"; 0.5686 at 65"; 0-8528 at 84"; 0-8308 a0438 17-46" at 21"; 16-78" at 48"; 1G.02' at 60.5"; 15.52" at 77"; 14.64" at a5401 24.94" at 21.5"; 23-96" at 43"; 22-40" at 63"; 21.68" at 75.5"; 20.20' a50B6 34-18' at 21"; 32-40' at 45"- 30.54" at 61.5"; 29.54" at $5'; 25.04' at 04800 29-76" at 21".28.24" at 4 5 O ; 26.74" at 61" 25-72' at 77"; 24.46" at a1078 35.86" at 21"; 34-10" at 44"; 32.32" at 62"; 31.14" at 75"; 29.44" at a4358 43.36" at 22" * 38-54' at 62"; 37.08" at 76" ; 35.9s" at 84" * ; 34.04" at at 112". 94"; 14-32" at 104.6" *; 13-66" at 121". at 98"; 19.88" at 108.5"; 19.26" at 118". 96"; 27-28" at 105"; $6-30" at 120". 94.6"; i3.82" at 104.5" *; 22-96' at 120". 96.5" 25.62" at 108" *; 27.76" at 119". 97.5" ; $4.00" at 10G" ; 33.00" at 120". n- Amyl. Density 0.8871 at 29"; 0.8777 at 42"; 0.8454 at 80"; 0-8301 at 102"; 0.8153 20.26" at 22". 19.12" at 41". 18.62' at 58"; 17.98" at '74"; 16-84' at a5161 24.00" at 20.5"; 22-72" at 41".21.98" at 55"; 21.32" at 73"; 19-88' a4358 41.50" at 21"; 39-30" at 41"; 37-90' at 57"; 36.48' at $2"; 33.90" at at 122"; 0.5994 at 141". 90"; 1g74" at 110"; 1A.16" at 120". at 93"; 19.36" at 106"; i8-06" at 120". 93"; 32-42" at 106"; 31.14" at 119". * l"'hiIc cooling 28 PHILLIPS INVESTIGATIONS ON THE DEPENDENCE OF TABLE II.-(continued). n-Hexyl. Density 0.8845 at 28.5"; 0.8742 at 43"; 0-8562 at 67"; 0.5420 at SG"; a5893 20-28" at 20.5". 19.40" at 40"; 19-38" at 45.5"; 18.58" at GO"; 17.20" a5461 24-08" at 265"; 22-50" at 40"; 21.64" at 59"; 20.68" at 54"; 19-70' a4358 41.22" at 21" - 39.22" at 40" ; 38.50" at 46" ; 33.90" at 73.5"; 34.44" at 0.8230 at 108"; 0.7990 at 140". at 93". f6-26" at 123". at 98"; 19.26" at 111"; 18-68" at 122.5".94"; 3$-18" at 112"; 32.30" at 122.5". n-Heptyl. Density 0.8816 at 27"; 0.8728 at 39"; 0.8430 at 82"; 0.8287 at 100"; 0.8167 16.00" at 19"; 15.20" at 43"; 14.44" at GO"; 13.36" at 88.5"; 13.04" a 5 4 6 1 22-90' at 19"; 21-70' at 44"; 20.00" at 71"; 19.22" at 89"; 18-14' at a5086 26-98' at 19"; 25-48" at 44"; 24.00" at 62"; 22-78" at 88.5"; 21-52" a4800 30.92" at 19" 29.22" at 44"; 25-44' at 64"; 26.16" at 88"; 24-74' at a4s78 32.68" at 19" 30.98" at 44.6"; 29.02" at 67" ; 27-78' at 88" ; 26.34" at a4358 39-32" at 19'; 36.84" at 43"; 34.04" at $1"; 32-60" at 89"; 31.06" at at 116"; 0.8052 at 131.5". at 111.5"; 12-18" at 134". 111"; 17.32" at 134". at 111.5"; 20-32" at 134". 111"; 23-16' at 134". 111"; i4.58" at 134". 110.5"; 29.58" at 134".n- Octyl. Density 0.8809 at 26"; 0.8iOO at 41.6"; 0.8565 at GO"; 0.8397 at 84"; agaS8 15-26' at 20.5"; 14.64" at 32"; 14.28" at 54"; 13.46" at 71.5"; 12.9s" 0.8195 at 114"; 0.5981 at 143". at 89"; 12.46" at 111.5"; 11.90" at 129". 93"; 17.88" at 109"; 17.18" at 126". 89" ; 20.i6" at 110" ; 20k2" at 128.5". at 90"; i4.04" at 109"; 23.10" at 128.2". at 90.5" ; 25.62" at 107" ; 24.42" at 1 2 P . 93"; 30.42" at 109.5"; 28.84" at 126". "5461 22.08" at 20.8" * 21-50' at 32" ; 20.68" at 61"; 19.t0" at 51"; 1S.GG" a t a5086 25-84" at 20.5" * 25-26" at 33" - 24.32" at 53" ; 22-86' at 71" ; 22.12" at aq8,,, 29.70" at 20.5" - 29.08" at 33.5" ; 27.94" at 58.4" ; 26.54" at 50"; 25-36' 04678 31.54" at 20.5"; 30-82" at 36"; 29-56" at 61.6"; 28.10" at 69"; 26.78" a4360 31.44" at 21"; 36.83" at 32"; 35.26" at 51"; 33.08" at $7"; 31.52" at n-Nonyl .Density 0.8822 at 25"; 0.8688 at 44"; 0.8561 at 63"; 0.8377 at 87.5"; aKnBs 18-32' at 21"; 17.68' at 37.5"- 16.40" at 66"; 15-96' at S5.5"; 15.46" 4 6 4 6 1 21-88" at 21"- 21-10" at 38"; 20.34" at 49"; 19-72" at 6S.8"; 18.76" at aaS5@ 37.14" at 22"; 36.62" at 37.5"; 34.66" at 50"; 33.34" at 67.5"; 32.16" 0.8128 at 122" * 0.7989 at 143". at 98.5"; 15.10" at 111" ;; 14.94" at 122". 85"; l & l O " at 100"; 17-34" at 120". at 85" *; 30.86" at 100"; 29-42" at 119". * Whilo cooling to. 20" 40 60 80 100 120 D$ 0.9354 0.9187 0.9013 0.8842 0.8670 0.8490 A 6438. 4-58' 4.20 3-73 3-26 2.68 2.19 Methyl ether, [a]:. /-h h A 5461. 5086. 4500.6.35" 7.63' 8.75' 5.53 6.71 7.75 4.73 5.75 6.68 4.07 4.77 5-61 3-40 3-99 4.57 2.il 3.23 3-60 n-Propyl ether. [ajy. TABLE-111. Etaera of d-Benz?llnzeth~lcnrbinol. A 4678. 9-28' 8.23 7.12 6.06 4.94 3.98 7 A 435s. 10.80" 9.2 7 6.4 7 5.38 4.35 r I- I ' i i ) t3. Lou" 40 60 80 100 120 140 Di'. 0.9203 0.9035 O.S8G5 O.StiY7 0.8527 0.8358 0.8189 to. 20" 40 60 80 100 120 D:". 0-9132 0.8968 0.8804 0.8639 0.8474 0.8308 A 6438. 17.78" 17.3 1 16-79 16-15 15.38 14-83 A 5461. 25.93' 25.09 23.90 22.78 21.83 21-15 A 6086. 30.66' 29.75 28.39 27.08 26.10 25.32 A 4800. 34.99O 33-08 32.62 30.97 29.59 29.10 A 4678. 37.26' 35.97 34.42 32-80 31.49 30-86 A 4358.44.63' 43-00 41-02 39.21 37-58 36-59 to. 20" 40 60 80 100 120 140 D$. 0.9032 0-88i2 0.8713 0.8556 0,8398 0,8239 0.808 t o . 29" 40 60 89 100 123 140 to. 20° 40 60 80 100 120 140 n-D$ 0.8935 0.8789 0.8G31 0.847G 0.8322 0.816G 0-so1 1 DZ. 0,8862 0.8719 0.8572 0.8430 0.8287 0.8142 0.8005 ,Amy1 ether. 14;. 7-A h 5893. 5461. 22.75' 26.85' 22.08 25-99 21-43 25.23 20.66 24-46 19.71 23-45 18.66 22-31 17.73 21.17 7 A 4358. 46.48' 45.03 43.5 1 41.88 39.94 38.04 36.20 7 A 6438. 18.10' 17.55 16-85 16.43 15.93 15.52 15.16 n-Heptyl ether. TABLE 111.-(continued). Ethers of d-Benxylmethylcarbi?~ to 20' 40 60 80 100 120 140 n-Hexyl ether.[4. .- h \ h A h D$. 5893. 5461. 4358. 0.8917 23-83' 27.03' 46.40' 0,8765 22-18 26.01 44-77 0.8611 21.53 25.11 43.21 0.8460 20.83 24-18 41-79 0-8307 20.27 23.52 40.68 0.8155 19.91 23.00 39.S2 0.8005 19.79 22.81 39.22 A 546 1. 25.84' 24.99 24.03 23.20 22.49 21-86 21.28 h A 6086. 4800. 30.43' 94-92' 29.43 33.75 28.34 32.59 27.45 31.61 26.67 30.60 23-84 29-87 24-98 28.61 h 4678. 36.90' 35.82 34.60 33.50 3 1-49 30.35 32-48 7 A 4355. 44-26' 42-67 41.08 39.53 38.32 37-35 36.38 to. 20" 40 GO so 100 120 140 D$. 0.8850 0.8707 0.8665 0.8422 0-8279 0.8135 0.799 ROTATORY POWER ON CHEMICAL CONSTITUTION PART xv.31 TABLE IV. Determinations of Rotatory Power in (approx.) 6 per cent. Eth$ Alco/d Solution. Length of observation tube 20 cm. T = 17". Grams of sub-stmce in 100 C.C. of Ether. solntion. Methyl ......... 5.00 Ethyl ............ 4.95 Propyl ......... 5.01 ButyI ............ 5.00 Amyl ............ 4.01 Heptyl ......... 5.07 Nonyl ............ 5.04 irexyi ............ 5.04 Octyl ............ 4.95 0 bservecl rotation. [a];. -\-.. ,- F h A A h A h 6803. 5461. 4358. 6893. 5461. 4358. 0.28' 0.49' 0.73' 2.8' 4-9' '7.3' 1.95 2.42 4.07 19.7 24.4 41.1 2-11 2-41 4-14 21.1 24.0 41.3 3.53 3.06 4-94 25.3 30.6 49.4 2.52 3.06 5-02 25.6 31.1 61.1 2.57 3.00 5-06 25.5 30.7 60.3 2-51 3.02 6.00 24.8 29.8 49.3 3-40 2-95 4.85 34.2 29.8 49.0 2.46 2.99 4.00 24.4 29.7 48.6 TABLE V. Determinations of Rotatory Power in (approx.) 5 per cent. Carbon Disulphide Xolution. Length of observation tube 20 cm. T = 17'. Grams of sub- Observed rotation. stance in ,--\ 100 C.C. of A A h Ether. solution. 5893. 5461. 4358. Methyl ......... 8-00 3.62" 3-05" 8.13' Ethyl ............ 5.01 4.45 5.15 9.45 Propyl ......... 5-00 4-28 5-21 9.32 Amyl ............ 5.0 1 4.16 4.83 8-92 Hexyl ............ 4.99 4-11 4-98 9.01 Heptyl ......... 4.87 3-71 4.60 8.00 Octyl ............ 5.05 3-82 4.60 8.26 Nonyl ............ 4.SG 3-72 4.43 8.00 Butyl ............ 4.98 4.26 5-28 9-49 [a]:. / h A 5893. 5461. 36.2' 39.5' 44.4 51.4 42.8 52-1 42-7 53.0 41.5 48.1 41-2 49.9 38.1 4'5.2 37.9 45.6 37.5 44.6 7 A 4358. 81.3' 94.3 03.2 95.2 89.1 90.3 82. I 81.9 80.6 Part of the expense of this investigation was defrayed by a grant from the Government Grant Committee of the Royal Society, and in addition the author wishes to express his thanks to the Department of Scientific and Industrial Research for a personal grant and to Dr. J. Kenyon and Mr. H. Hunter for their interest and help. BABTTERSE.4 POLYTECHNIC S.W. 11. [Received November let 1922.

ISSN:0368-1645    

DOI:10.1039/CT9232300022

出版商:RSC    

年代:1923

数据来源: RSC

摘要:

32 HALL INVESTIGATIONS ON TIIE DEPENDENCE OF IV.-Investigations on the Dependence of Rotatory Power on Chemical Constitution. Part X V I . The Di-d-P-octyl Esters of the Saturated Dicarbozglic Acids. By LESLIE HALL. ~ o N G the results which emerge from this series of investigations arc thc interesting differences which havc been observed in the optical rotatory and rotatory dispersive powers of aliphatic secondary alcohols and aliphatic cthers derived from them on the one hand and of aliphatic cstcrs dcrivcd from thc same alcohols, on the other. Considering the rotatory powers first it has becn shown that those of the esters are in general much more susccpt'ible to the influences of temperature dissolution and concentration than are those of the alcohols from which they are derived and of the ethers which may be derived from the same alcohols.Compare for example the differences in thc temperature-rotation curves of d-sec.-octyl alcohol and of d-sec.-octyl acetate (Part I T. 1911, 99 50; Part V T. 1914 105 837) and in the alterations in rotatory powcr which they respectively exhibit in certain solvents, notably carbon disulphidc. A legitimate deduction which may be drawn from a consideration of these and other facts is that the differences in behaviour shown by the esters may be due to some inherent property of the carb-oxyl group and in order to obtain further evidence bearing on this point a series of optically active esters derived from d-sec.-octyl alcohol and some saturated aliphatic normal dicarboxylic acids has been prepared and their optical behaviour investigated.A series of optically active esters of aliphatic dibasic acids has been previously described in the literature by Walden ( J . Russ. Phys. Chem. Xoc. 1898 30 767) who used the fermentation smyl alcohol ; this however was not optically pure (compare Marckwald and McKenzie Ber. 1901 34 485) so that any deductions' derived from it consideration of his results are unreliable. Moreover in this and other earlier work the optical rotatory powers were determined for light of one wave-length only and the measurements made only at the temperature of the laboratory. The results of the polarimetric determinations tabulated on pp. 41 and 42 show that the esters herein described exhibit com-plex rotatory dispersion under all conditions employed namely, in the homogeneous condition at temperatures from 20" to 130" ROTATORY POWER ON CHEMICAL CONSTITUTION.PART XVI. 33 and in solution in carbon disulphide and in ethyl alcohol a t the ordinary temperature. Not more than one ester however d-8-octyl succinate was observed to exhibit anomalous rotatory dispersion in the region w 3 Y 1 2 3 4 5 G 7 8 9 10 11 Number of tnethylene groups in acid (n). The d-8-octyl esters of the dibusic aci& (CH,),(CO-OH),. A. in the homogeneous state. B . [a]wa in 57; soltition in ethyl alcohol. c. [a15m3 99 99 , , carbon disulphide. of the spectrum studied and then only in 5 per cent. solution in ethyl alcohol a t 18". An examination of the curves (Fig. 1) obtained by plotting the specific rotatory powers of the various esters against the number of methylene groups in the respective acids shows : (1) The oxalic ester possesses a particularly large optical rota-tion a similar result was observed by Hilditch in tho case of VOL.CXXTIT. 34 HALL INVESTIGATIONS ON THE DEPENDENCE OF E-nieiithyl oxalate (T. 1909 95 1581) and the explanation of this given by Hilditch namely that the contiguity of the two carboxyl groups in the oxalic acid residue is the cause of the exaltation in its outera appears to be satisfactory. Now it has been observed in these series of inv6stigations that chains of five, ten fifteen etc. atoms arc often associated with peculiarities in optical behaviour. If the formula of this ester be written as follows, (2) The succinic ester has a very small rotation.CH,*CII( C,H,,) *O*CO*yH, H,C*CO* 0 * CH (C,H,,)*CH, it is apparent that there is the possibility of two chains con-taining fivc atoms or of two containing ten atoms each influencing abnormally the magnitude of the optical rotatory power. (3) The rotation values are alternately high and low as the series is ascended. This may bo due to the alternate members of the oxalic acid series possessing a cis- or trans-configuration respectively. An analogous alternation is also known in a number of other physical properties of this series for example the melting points solubility in water solubility of the cdciuiii salts melting points of the methyl esters. This view of the alternate cis- and trans-structure of this series has received support from thc recent work of Irvine and Steele (T.1915,107 1221) and Pricc and Brazier (ibid. 107 1719). The latter authors as a result of their work on the formation of additive compouiids of complex metallic ammines with these dicarboxylic acids make the tentative suggestion that oxalic, succinic and aclipic acids possess a tram-configuration whilst malonic and glutaric acids possess a cis-configuration. Such con-siderations on stereochemical grounds render untenable any assump-tion of the configuration of the succinic ester as containing chains of fifteen or twenty atoms but it is suggested that the assumption of a configuration made up of two spirals agrees with the hypo-thesis advanced t o account for the low rotation of the ester.I3 X P E R I M E N T A L. The active p-octanol required for the preparation of the esters was made by the method described by Kenyon (T. 1922 121, 2540). Of the dibasic acids employed suberic and sebacic acids were obtained from Kahlbaum whilst the others were prepared by the following methods : Glutaric acid from frimethylene cyanide (Auger Ann. Chim. Phys. 1901 [vi] 22 357) ROTATORY POWER ON CHENICAL CONSTITUTION. PART XVI. 35 Adipic acid by the oxidation of cyclohcxanol with nitric acid (Bouveault and Locquin Bull. SOC. chim. 1908 [iv] 3 438). Pimelic acid froin trimethylene bromide and malonic ester (Blaise and Koehler ibid. 1909 [iv] 5 687). Azelaic acid froin castor oil (Maquenne ibid. 1899 [iii] 21, 1061). n-Nonane- n- decane- and n- undecane-dicarbou ylic acids from undecenoic acid.Thc undecenoic acid was converted into o-bromo-undecoic acid by the method of Walker and Luinsden (T. 1001,79, 1191). After a nuinbcr of trials it was ascertained that good yields of o-bromoundecoic acid caii only be obtained by this method if the undecenoic acid is carefully purified beforehand by rapid distillation under dirninishcd pressure. The acid chlorides were prepared by mixing the pure dry acids with thionyl chloride (H. Meyer Monatsh. 1901 22 421); the acid chlorides of the highcr members of the series were not dis-tilled owing to their instability a t the high temperatures necessary. d-P-OctgZ oxalate was prepared by three methods (i) by heating anhydrous osalic acid with four times its wcight of d-P-octyl alcohol a t 150" for two hours followed by fractional distillation under diminished pressure; (ii) by heating cthyl oxalate with d-p-octyl alcohol (2 inols.) (a) at 175-180" for about ten hours in an uncorked flask or (6) a t 195-205" for about ten hours in a small aluminium autoclave followed in each casc by fractional distil-lation; (iii) by using methyl oxdatc and working up the product as under (ii).The following products were isolated as colourless liquids : d-p-octyl oxalate b. p. 198-199"/11 inni. very faint odour; d-p-octyl ethyl oxalate b. p. 138-140"/20 min. fruity odour ; and d-a-octyl methyl oxalate b. p. 130-132"/20 inm. fruity odour. d-p-Octyl malonate was prepared by method (ii) as described under the oxalate using ethyl inalonate and also by iiiethod (i) with the modification that the mixture of malonic acid (7 grams) and d-p-octyl alcohol was treated with dry hydrogen chloride until 1 gram had been absorbed before it was heated a t 100" for three hours.The reaction product was washed with sodium carbonate solution before distillation. The following substances were isolatcd as colourlcss liquids : d-13-octyl malonate b. p. 158-160°/19 mm. fruity odour; and d-p-octyl ethyl malonate b. p. 198-200"/19 mm. fruity odour. d-p-Octyl ethyl malonate was prepared also by the interaction of d-p-octyl alcohol and the acid chloride of ethyl hydrogen malonate. c TABLE I. Refractive Indices (nA) of h h A Ester. Temp 6438. 6896. 5461. d-8-Oc tgl ouala%e 26" 1.4309 1.4229 1.4347 mallonate 26.2 succinate 25.8 glutarate 25.8 rzdipate 25 pimelate 25-8 suberate 25-7 azelate 25 sebacate 25.8 n -nonane-cu-di-carboxylate 25 n-decane-aedi-carboxylate 25.8 n-undecane-ah-dicarboxylate 25 methyl oxalate 25 ethvl oxalate 26 ethil malonate 26 methyl succinate 25 ethyl succinate 25.6 d-B-Octyl I-5-Octyl d-S-Octyl 1.4320 1.4349 1.4365 1.4392 1.4400 1.4412 1,4421 1,4453 1.4234 1.4249 1.4289 1.4349 1-4367 1.4384 1.4402 1,4409 1.44 19 1-4432 1.4441 1-4448 1.4463 1.4456 1.4261 1-4253 1.4269 1.4305 1.4308 1-4365 1.4386 1.4401 1.4421 1.4429 1.4439 1.4450 1*44&0 1.4466 1.4485 1.4475 1.4280 1.4277 1.4286 1-4323 1.4326 the Esters.A A A A 5086. 4800.4678. 4358. 1.4366 1.4384 1.4407 1 *4423 1.4450 1.4459 1.4470 1.44'79 1.4385 1.4404 1.4427 1.4441 1.4470 1-4476 1.4490 1-4499 1-4395 1.4412 1.4435 1.4452 1.4479 1.4486 1.4501 1.451 1 1.4426 1.4443 1.4463 1-4480 1.4497 1.4509 1.4516 1.4532 1.4538 1.4845 1.4601 1.4521 1.4530 1.4560 1.4553 1.4357 1.4304 1.4311 1.4320 1.4348 1.4303 1.4323 1.4333 1.4361 1-4399 1-4346 1.4364 1.4374 1.440 ROTATORY POWER ON CHEMICAL CONSTITUTION. PART XVI. TABLE 111. Observed Densities am? Rotatory Powers of the Esters. ltotations are here given as for it 1-dcm. tube. d-p-octyl oxalate. D$ 0.9147 at 26'; 0-9040 at 40.5"; 0.8863 at 63'; 0.8720 at 80.5'; 0-8563 45893 20.94" at 18.8"- 20.45" at 27.3"; 19.98" at 41"; 17.20' at 82"; 16.62" a 5 4 6 1 24.52" nt 18.8"- 23.78" at 27.5"; 21-64' at 49"; 19.84" at 80"; 18.86" a4358 37.62" at 19.4"; 36.76" at 27.5"; 33.26" at 40"; 31.46" at 80'; 29.80' at 100".at 970; 115.940 at 1210. at 95"; i7.98" at 130". at 98"; 28.20" at 130". d- P-Octyl malonate. Di 0.9189 at 21.2"; 0.9005 at 45.5"; 0.8837 at 66'; 0-8i06 at 80"; 0.8574 a0438 8-48' at 19.2"; 7.32" at 40"; 5.74" at 77"; 5.04" at 102'; 4.72" at 122"; a j p b l 11-76' at 19.2'- 10.24" at 41'; 8-16" at 76'; 7.04' at 100'; 6-34' at 45086 13.60" at i9.2"; 11-60" at 40"; 9-08' at 77"; 7.70" at 102"; 7.08" at aJso0 15.18" at (9.2"; 12.86" at 40"; 10.02" at 77'; 8-56' at 102"; 7-86" at aJo,8 15.64" at 19.2"; 13-52" at 40"; 10.70" at 77"; 9.14" at 102"; 8.28' at a0358 17-82" at 19.2"; 15-02' at 41"; lI.SG" at 76"; 10.12O at 100"; 9.00" at at 99" ; 0.8396 at 132.5".4-12' at 158". 122" * 5<2" at 158". 122"- 6-28" at 157". 122"; 6-72" at 157". 122"; 7-26" at 157". 122"; 7-72" at 15s". d-p-Octyl succinate. D$ 0,9175 at 19.7"; 0.8982 at 44.6"; 0.8853 at 60.3"- 0.8700 at 81.2"; 0.8511 at 107"; 0.8406 at 120.6"; 0.8222 dt 142"; 0.8072 at a6438 3-76' at 19-2*; 3-36" at 57"; 3-14' at 81"; 3-10' at 129'; 3.14' at 144". 45481 5-04" at 19.2"; 4-64' at 56"; 4-14' at 82"; 4.26' at 126O; 4-06" at 144". a5086 6-48" at 19.2"; 4.86" at 57"; 4.60" at 81"; 4-64" at 128"; 4-56" at 144". ao800 6.12" at 19.2"; 5-28" at 59O; 4.96" at 81"; 4.94" at 128"; 4-88' at 144". ad6,* 6.46" at 19.2"; 5.60" at 59"; 5.44" at 81"; 5.30" at 128"; 6-12" at 144".aJ36a 7.02" at 19.2"; 6-02" at 56"; 5.72" at 81"; 5.56" &t 126"; 5-52" at 144". 162.5". d-p-Octyl glutarate. DF 0.9204 at 15"; 0.9040 at 35.5"; 0.8921 at 60.5"; 0.8688 at 82.5"; 0.8643 a6438 6-70' at 17"; 5-92" at 3 7 - G O ; 4-70' at 69'; 4-lk" at 98"; 3.80' at 125"; 9-78" at 17" ; 8-32" at 37.2" ; 6-84' at 68" ; 5-78' at 99'; 5-24' at 122" ; at 100"; 0.8358 at 124"; 0.8213 at 1.43'- 0.8035 at 164'. 3-52" at 147'. 4.74' at 148". aSo8@ 10.88" at 17"; 9-52' at 37.6'; 7.48" at 6D"; 6.52" at 98'; 5-62" at 126"; uaao0 12.12" at 17"; 10-50° at 37.6"; 8.22" at 69"; 7.18" at 98"; 6-56' at 125"; "4678 12.60" at 17" 11.02" at 37.6'; 8*iOo at GO"; 7-56' at 98"; 6-98' at 125"; a4358 14.88" at 17". 12.38' at 37.2"; 10.04" at 68"; 8.68" at 99"; 8.00" at 6-42' at 147".6-08" at 147'. 6.38" a; 147". 122"; i:12" at 148" 38 HALL INVESTIGATIONS ON TIIE DEPENDENCE OF d-S-Octyl adipate. at 124". DiZ 0-9072 a t 28"; 0.8933 at 46-25'; 0.8774 a t 6s"; 0-8602 a t 90.5"; 0.8371 a5899 10.20" a t 19.8"; 9-90' at 28.5"; 5-50" at 60"; 7-36' at 85"; 6.74" a t 11.58" at 19.8". 11.14" at 28.6"; 9.34" a t 59"; 8-42" at 84"; 7-24" at u~~~~ 15.30" a t 19.8"; 17.32" at 28.6"; 15.10" at 59"; 13-28' atl 84"; 11-46' 108"; 6.02" a t 121". 10s"; 6.<6" rtt 122". nt 108"; 10.86" a t 122". d-p-Octyl pimelate. DS 0-9111 a t 21"; 0.8945 at 41.6"; 0.8792 at 63.5"- 0.8666 at SO-5"; 0.5519 a0138 8.68" a t 19.5"; 7.76" at 37.2"; 6.32" a t 73.5"; 5.78" at 97"; 5-10" at a5401 12.02" at 19.5"; 10.38" at 39"; 8.32" at '13.6"; 7-58' at 99.2"; 6-78' a 5 0 8 0 14.00" a t 19.5".12.40" at 38"; 9-70" at 76"; 8-70' a t 97"; 8-08" a t aq800 15.85" a t 19.5"- 13.78" at 38"; 10.62" a t 74"; 9-92' at 97"; 9.02" a t 16.60" at 19.5"; 14-22" at 39"; 11.06" at '13"; 10.58" at 97'; 9-56" a t a435.8 1S.SO" a t 10.5"; 16.02" at 40"; 12-86" a t 73"; 11.54" a t 99.2"; 10.60" at 99.5"; 0.8347 at 123"; 0-8181 a t 143'; 0.8058 at 161". 127"; 4.68" at 145". a t 126"; 6.20" at 145". 127"; 7.4i" at 145". 121"; 8-62' a t 145". 127"; 9.00" at 145". at 186"; 10.04" at 145". d-p-Octyl subcrate. Ds 0.9084 a t 20"; 0.8925 at 41"; 0.8785 a t 60.7"; 0.8640 a t 80.5"; 0.8492 at 100"; 0.5285 a t 128". ajsg3 9.80" a t 22.G" ; 8-92" a t 149" ; T.56" at 76" ; 6.56" at 93" ; 6.06" a t 102" ; 5-56' at 137". a51G1 11.56" at 22.6"; 10.04" at 48"; 8.42" at 75"; 7.76" at 92"; 7-56' a t a 4 3 5 8 17-58" at 23.6"; 15.50" st 48"; 14.2G" at 76"; 12.92" at 92"; 12.08" a t 102"; 7-14' at 127".103"; 10.72" at 127". d-p-Octyl azelate. DS 0.0053 at 20"; 0.8908 at 40.8"; 0-8768 a t 60.7"; 0.8640 at 80"; 0.8486 a t 100"; 0.8324 a t 121"; 0.8191 at 142"; 043037 at 163"; 0.7874 at 185" * 0.7695 at 210". us438 8.18" at 19.4'. 644" at 51.7"; 6.48" at 67"; 6.98" at 95"; 5.30" at 107"; 4.b8" a t 129". a54G1 11.66" at 19.4"; 9.94" a t 45'; 8-98" at 67"; 8-26" at 80"; 7.80" at 95O; 7-62' at 107" ; 7-04' at 129". a5080 13.28" a t 19.4"; 11-52' at 51.7"; 10.36" a t 67"; 9-98' at 80"; 8-94" at 95"; 8-58' a t 107"; 7-52' at 129". 14-76' at 19.4"- 12.62" at 51.2"; 11.50" at 67"; 10.90" at 80"; 9-94' at 95"; 6-38" a t 107"; 8-40" at 129".15.40" at 19.4"; 12.92" at 51.7". 11-98' a t 67"; 11-24' at 80"; 10.24" at 95" ; 9.82" a t 107" ; 8-66" at 129". a4358 17.96" at 19.4"- 15-12" at 47"; 13-56" at 67O; 13.08" at 80'; 11.90" a t 95"; 11-&3" at 107"; 10.52" at 129" ROTATORY POWEE OW CHEMICAL CONSTITUTIOh'. PART XVI. 39 d- p - Octyl sebacat.e. D$ 0-0935 at 20.6"; 0.8898 at 39.8"; 0.8730 at 59"; 0.8474 at 90.8'; 0-8306 ao038 7.98" at 19.8" ; 6.38" at 48.8" ; 5.46" at 78" ; 4.88" at 99" ; 4.64" a t 128' ; a5161 10-86" at 18.8"; 9.34" at 51"; 7.56" at 77.5"; 6-50' at 106"; 5.94" a t ajo80 12-84" at 18.8"; 10.58" at 18.8"; 8.8s" at 78"; 7-84' at 100"; 7.04" at 14.36" at 18.8"; 11.64" at 48.S"; 9-62' at 79"; 8.80" at 101"; 7.56" at a d o 7 8 15-28' at 18.8"; 12-30" at 48.8"; 9.88" at 80"; 8.88" at 102"; 8-42" at a4358 17.16" at 18.8"; 13.72" at 51"; 12.00" at 77.5"; 0.94" at 106"; 9.10" at 123"; 0.8137 at 246"; 0.8019 at 163".4-12' at 182". 130"; 5-26" at 155" 128"; 6-42' at 152" 128". 128". at 130.5"; 5-70" at 155". d- f3 -0ctyl n-nonane-a6 - dicarboxylate. Di 0-8991 at 25"; 0.S830 at 46"; 0.8744 at 61.5"; 0.8612 at i9"; 0.8463 at 98". a3803 9.3G" at 20" ; 8.42" at 37' ; 5.04" at 48.2" ; 7.40" at 65" ; 6.98" a t 81" ; 5-96' at 103"; 5.20" at 120"; 4.64" a t 132". u51(11 10.64" at 20"; 9-50' at 37"; 8-54" at 47"; 8-26" at 65"; 7.62" at 81"; 6.70" at 97" * 6.02" at 118" - 5-34" at 132". 44358 16.58" at 20"; 14148" at 370; 1i.58" at 47"; 12.68" at 650; 11.58" a t 81" ; 10.58" at 97" ; 8.90" at 120" ; 8.22" at 133".d-a-Octyl n-decane-m-dicnrboxylate. at 124"; 0.8110 at 142". 5.92" at 99" ; 5.60" at 120". 6.70" at 99" * 6.16" at 120" ; 8.90" at 133". at 85" ; 10-72" at 99" ; 9.50" at 150". D$ 0.8960 at 30"; 0.8810 at 50.5"; 0.8678 at G9"; 0.8543 at 59"; 0.S26G ajsgg 9.38" at 20.2"; 8.24" at 35"; 7.60" at 54"; 6-94' at 71"; 6.26" at 85"; a5p61 10.22" at 20.2" ; 9-68" at 33" ; 8.40" at 54" ; 7-06" at 71" ; 7.24" at 85" ; a4358 15.38" at 20.2"; i4.20" a t 33"; 12.50" at 54"; 12.00" at 71"; 11-32" d-p-Octyl n-undecane-EX-dicarboxylate. DiI 0.8894 at 31"; 0.8746 at 61'; 0.8606 at SO"; 0.5468 at 90"; Oaf3231 a t 120"; 0.8021 at 142". 45893 8-28" at 21"; 7.94" at 32"; 7-52" at 49'; 7-32" at 71"; G-86" at 95'; 6-66' at 110" ; 6.26" at 126". a5461 9.96' at 21". 9-44" at 32"; 8-90' at 50"; 8.16" at 71"; 5.58" at 95'; 7-00' a't 110" - 6.68" at 126".4p358 15.66" at 21"; 14.46" at 32"; 13.50" at 60"; 12.18" at 51"; l l . O & " ati 95"; 10.14" at 110"; 9-66' at 126". d- p -0ctyl methyl oxalate . DS 0.9745 at 30"; 0.8563 at 60"; 0.9380 at 70.5"; 0.9183 at 90"; 0.8894 at ajsoa 14.04" at 19"; 13-08" at 34"; 11.90" at 64"; 11-14" at 90"; 10.24" at a54el 16.54" at 19'; 15-04" at 35"; 14.00" at GO"; 12-38" at 90'; 11-44" at aaSs8 25-72" at 19"; 24-00" at 34"; 22.10" at 69"; 19.62" at 90"; 18.68" at 119" ; 0-8636 at 140". 112'; 9-56" a t 126". 112" ; 10.74" at 126". 112"; 17.42" at 126" 40 I-IALL INVESTIGATIONS ON THE DEPENDENCE OF d-p-octyl ethyl oxalate. l$ 0.9574 at 26.5" ; 0.9428 at 43" ; 0.9251 at 62.5'; 0.9067 at 82".a5893 13.20" at 24"; 11.85" a t 53'; 11-58" at 73"; 11.08" at 96"; 10.84' at ab401 1540"at 24'; 13.60" a t 53"; 12.62" at 73'; 12.14" at 96"; 11.60" a t 116'. 44358 23.68" at 24"; 21.24" a t 53"; 19-46" at 73"; 1848" a t 96"; 16JXi" at 116". 116". d p-Octyl ethyl malonate. DF 0.9519 at 28"; 0.9328 a t 49"; 0.9176 at 68"; 0.8867 a t 100.5". a&8a3 8-82' a t 21.5"; 7-86' at 35"; 7.02" at 54"; 6-24" at 75"; 5-90' at 92"; ab&1 10.38" a t 21.5" ; 9.16" at 35" ; 7.92" a t 55"; 7-18' a t 75"; 6-64' at 03" ; a4358 16.52" at 21.5"; 14.94" at 38"; 13-02" a t 65'; 11.84" at 75'; 10.64" a t 5.18" at 108". 6-78" at 111". 93"; 8.86" at 110". Z-p-Octyl methyl succinate. DF 0.9627 a t 25"; 0.9508 at 39.5'; 0.9330 a t GO"; 0.9164 at 80'; 0.8989 a t agaB3 - 3.42" at 19.5"; - 3-32' a t 36"; - 3-12" at 58"; - 2.88' at 84'; ab411 - 3.84" at 10.5"; - 3.76' at 34"; - 3 ~ 4 6 ~ at 58"; - 3.14" a t 86'; a4358 - 8-64" at 19.5"; - 5-46' at 35"; - 5.04" at 58"; - 4.64" at 86"; 100" ; 0.8782 a t 123".- 2-58" a t 106"; - 2.38" a t 126". - 2.84" a t 106"; - 2-56' at 125". - 4.34" a t 106"; - 4.08" at 125". d-p-Octyl ethyl succinate. DiZ 0.9614 at 17.4"; 0.9434 at 39.5'; 0.9223 at 63.3"; 0.9090 a t 79'; 0.8904 a8438 2.40" at 18-2"; 2.24" a t 30.2"; 2.16" a t 52"; 2.06" a t 79"; 1.94 at 107'; a548 3.58" at 18.2"; 3.36" at 30.5"; 3.22" a t 51"; 3.06" at 80"; 2.80" at 107"; aL086 3-84" at 18.2"; 3.68" at 30.2"; 3-46" a t 52"; 3.20" at 7s"; 2.92" at Q~~~~ 4-21" at 18.2" ; 4-08" at 30.2" ; 3-72' a t 52" ; 3.50" a t 78" ; 3.40' a t 107" ; u ~ ~ ~ 4.42" at 18.2" ; 4-28' at 30.2"; 3-92' a t 62" ; 3.74" a t 78" ; 3.68' a t 107".Q~~~~ 5.22" at 18.2"; 4.90" at 30.5"; 4-58" at 51"; 4.28" at 80"; 4.08" at 107". d-p-OctyZ succinate was prepared by method (ii) using ethyl succinate by method (iii) using methyl succinate and also by the interaction of succinyl chloride and d- p-octyl alcohol. The products obtained were d-p-octyl succinate b. p. 208-211"/16 mm. very faint odour ; d-p-octyl ethyl succinate, b. p. 160-162"/16 mm. fruity odour; and Z-P-octyl methyl suc-cinate b. p. 163-164"/15 mm. fruity adour. The remaining esters were obtained by the interaction of d-p-octyl alcohol and the required acid chloride as colourless somewhat viscous almost odourless liquids and possessed the following boiling points glutarate b.p. 175-177"/3 mm. ; adipate b. p. 175"/2 mm. ; pimelate b. p. 188-190"/3 mni. ; suberate b. p. 202-204"/3 mm. ; azelate b. p. 208-210"/2 mm.; sebacate b. p. 240-242"/7 mm.; m-nonanedicarboxylate b. p. 305-207"/1 mm. ; n-decanedicarb-at 102"; 0.8746 at 123". 1-64" at 124". 2.76" at 120". 107"; 2-93" a t 121". 3-22" at 121" to. 20' 40 60 80 100 120 to. 20' 40 GO 80 100 120 to. 20" 40 60 80 100 120 to. 20" 40 60 80 100 120 d-19-Octyl olEa1at.a TABLE IV. Densities and Rotcttory Powers of the 0.9043 21.56 24.93 38.77 0.8884 20.60 23.72 37-15 0-8i25 19.86 22-83 35.96 0.8561 19.32 22.26 34.92 0.8397 18-98 21.77 34-00 d-B-Octyl succinate. Dz- [aI6438. [a15461* [a150860 [OT14800' 0-9171 4-08' 5.54' 6-00' 6.65' 0-8861 3.77 5.21 5.60 6-21 0.8710 3.63 5.10 6.49 6-04 0.8555 3.55 5.05 5-45 5.96 0.8393 3.53 5-03 5.43 5.91 0.9017 3.93 5.32 5-77 6.39 d-P-Octyl adipate.DY. [aI5893* [a15461. 0.9135 11-23" 12-66" 0.8984 10.42 11-64 0.8832 9.55 10.69 0.8682 8.69 9-81 0.8530 7.90 9.01 0.8380 7.19 S-23 d-p-Octyl suberate. DS. La] 5 893- [a15461* 0.9084 11.01" 12.95' 0-8937 9-89 11-59 0-8780 8.85 10.47 0-8642 8-03 9-54 0-8493 7.35 8-96 0.8346 6-85 8.46 DS. 0.9198 0.9038 0.8883 0.8529 0.8574 0.8424 [a14678. [ a l 4 3 5 s * 7.02' 7-63' 6.50 7.00 6.36 6-82 6.22 6.69 6.12 6.41 6.70 7-23 6438' 9.19' 8-08 7.09 6.42 5.95 5-51 D:. 0.9161 0*9005 0.8851 0-8iOO 0-8543 0.8388 [a143 ii 8-19.93' 18.34 16.93 15-52 14.23 13.17 [a14358-19-59' 17-97 16.77 15.79 14.84 13.88 D:.0.9105 0.8954 0.8810 0.8666 0.8518 0.8363 Dia. 0.9050 0.8912 0.8770 0.8627 0-8485 0-8340 ['164S8' 9.53" 8-49 7-72 7.13 6-76 6-53 La] 6488' 9-02' 8-3 7 7.75 7.16 6-64 6-23 12.83" 11.33 10.18 9.17 7.76 d-[a15461. 8.40 C'i6438. 7-12" 6-33 5.70 5-22 4.87 4-60 13.18" 11.52 10.31 [ 12.76' 11-10 TABLE IV (continued). Densities and Rotatory Powers of the d-&Octyl sebacate. d-B-Octyl n-nonane-ar-to* cs* [c]6438. [a]5461* [a]5086. [a14600* [a14676. [a14358. Dt'a [a15893. [a15461. 30" 0.9038 8-45" 12.04' 14-16' 15.80" 16.75' 18-87' 0.9027 10.3i" 11.77" 40 0.8897 7.64 10.84 12-76 14.03 14.86 16.86 0.8882 9.39 10.54 GO 0.8752 6.95 9.iG 11-43 12-48 13-35 15.04 0.8737 8-63 9.66 80 0.8611 6-39 8.83 10-36 11-29 12.08 13.51 0.8594 7-84 8.87 100 0.8470 5.95 8.03 8.40 10.34 11-10 12.26 0.8448 7.08 8-120 0.8326 5-62 7.45 8.72 9-61 10.31 11.29 0.8303 6.29 7.18 d-B-Octyl n-undecane-ah-dicarbosylate.d-B-Octyl methyl oxalate. D% [a]5893. [a15161' [ Q I ~ 3 5 8 * D;'* la] 5 8 93' La] 54 6 1' [.I4 20' 0-8975 9-25' 11.12" 17.4;' 0.9840 14.22" 16-64' 25-40 0.8827 8.77 10.35 16.02 0.9656 13.32 15-24 24.25 GO 0.8680 8.48 9-75 14.79 0.9471 12.72 14-42 22.96 80 0-8533 8-27 9.33 13.78 0.9285 12.22 13.77 21-100 0-8386 8-02 8-96 12.83 0.9100 11-59 13.21 21.01 120 0.8237 7.89 8.74 11-99 0.8915 11.39 12.68 20.19 d-8-Octyl ethyl malonate.I-8-Octyl methyl suceinate. to. D% [415893- [a15461* [a14358. D$- [ ~ I ~ s w [ a l 5 4 6 1 * [a14358* D$* 20' 0.9596 9-27' 10.83" 1740' 0.9672 -3.54" -3.97' -5.85" 0-9600 60 0.9234 7.36 8.41 13-74 0.9331 3-30 3.71 5.42 0.9252 40 0.9415 8-10 9.28 15.19 0.9501 3.39 3.83 5.62 0.9425 SO 0-9054 6.67 7.73 12.59 0.9160 3.12 3.56 5.20 0.9080 100 0.8872 6.13 7-17 11.61 0.8991 2.94 3.38 5.00 0.8912 120 0.8691 5-66 6.72 10.81 0.8822 2.77 3.17 4.78 0.874 TABLE V. Determinations of Rotatory Power in approximately 5 In ethyl alcohol. I A 1 /-Grams of Grams of eater in ester in 100 C.C. of 100 C.C. of Ester- solution. Temp. a58g3. 45101. 64358. [t~]5~83. [a14358. solution. Temp. d-8-Octyl oxalate 4-99 18' 2.37' 2.75' 4-36" 23-73" 27-54" 43.66" 4.97 16' malonate 5.04 ,) 0.97 1-06 1.62 9.63 10.52 16-07 4.99 17 succinate 5.10 9 ) 0.18 0.17 -0.03 1-77 1-67 -0.29 5-03 ,, glutarate 5.07 9 ) 0.85 0.96 1.47 8-39 9.48 14.51 5.05 ), adipate 5.03 3) 0.95 1.04 1.68 9.45 10.35 16.72 5-11 ,, pimelate 5.04 , 0.95 1.11 1.81 9.43 11.03 17-98 5.09 IS subera to 5.03 19 0.90 1.08 1-78 8.95 10.74 17.70 5-01 ), azelate 5.15 0.95 1.12 1.66 9.22 10.86 16.11 5.03 ,) sebacate 5.00 ii 0.57 1.04 1-68 5-71 10.41 16-81 4-06 ), sz-nonane-at-dicarboxylate 6.04 ,) 0.90 1.02 1-65 8-93 10.12 16.36 4.97 ,, a-decane-au-dicarboxylate 5.01 19 0.93 1.00 1-66 9-29 9.98 16-88 4.97 )) n-undecane-ah -dicarboxylate 4-62 ,) 0.87 0.93 1-40 9.41 10.06 15-15 4.71 ,) d-8-0ctyl "Z-~-Octyl d-8-Octyl methyl oxalate 4.85 20 1.30 1.61 2.41 13.14 16-28 24.36 4.57 20 ethyloxalate 4.99 18 1.36 1.80 2-56 13.61 18.03 25-64 5.01 18 13 methylsuccinate 5.05 20 -0.13 -0-22 -0-30 -1.29 -2-18 -2.97 5.06 20 ethyl succinate 5.07 15 0.19 0.27 0.45 1-87 2*GG 4-73 4-09 17 0 ethyl malonate 5-04 21 0.74 0.82 1.38 7-34 8.14 13.70 5-06 19.44 PBILLIPS INVESTIGATIONS ON THE DEPENDENCE OF oxylate b. p. 205-210"~l mm. ; and n-uiidccanedicarboxylate, b. p. 215-217"/2 mm. The last ester in the list solidified on keeping to a mass of colour-less plates which melt a t 21". The esters were not analysed in the usual way as agrcement between the experimentally dctcrmined and the calculated values of the molecular refraction was considered to be a more satis-factory criterion of purity. Density determinations mere carried out between 20" and 130", a carefully calibrated pyknometcr of about 3 C.C. capacity being used. Refractive indices were determined a t a constant temperature for light of several wave-lengths by means of a refractometer of the Pulfrich type, The polarimetric measurements were made in a 5.0 mm. jacketed tube round which mineral oil was circulated by ineans of a pump. Observations were made from 20" to about 140" a t temperaturo intervals of about 20° but in Table I11 rotations are given as for a 1-dcm. tube. That no racemisation had occurred during the preparation of the esters or during their subsequent heating or treatment with solvents was proved by the fact that all the esters on subsequent hydrolysis yielded sec.-octyl alcohol of maximum rotation. For observations of rotatory power in solution about 1 gram of the active ester was dissolved in the solvent and the solution made up to 20 C.C. at the temperature of the laboratory. Determinations of rotatory power were made in a 2-dcm. tube. The author wishes to express his thanks to the Department of Scientific and Industrial Research for a maintenance grant which has enabled him to carry out this work and also to Dr. J. Kenyon and Mr. H. Hunter for their interest and guidance. BATTERSEA POLYTECHNIC S.W. 11. [Received November Id 1922.

ISSN:0368-1645    

DOI:10.1039/CT9232300032

出版商:RSC    

年代:1923

数据来源: RSC

摘要:

J O U R N A L OF THE CHEMICAL SOCIETY, TRANSACTIONS. E. C. C. BALY C.B.E. F.R.S. 0. L. BRADY D.Sc. A. W. CRoasLEY C.M.G. C.B.E., D.Sc. F.R.S. C. H. DESCH D.Sc. Ph.D. F. R.S. C. S. GIBSON O.B.E. M.A. B.Sc., bf. Sc. I. M. HEILBRON D.S.O. D.Sc. Ph.D. J . C. IRVINE C.B.E. D.Se. F.R.S. T. M. LOWRY C.B.E. D.Sc. F.R.S J. W. MCBAIN M.A. Ph.D. F.R.S. J. I. 0. MASSON M.B.E. D.Sc. W. H. MILLS M.A. Sc.D. F.R.S. J. C. PHILIP O.B.E. D.Sc. Ph.D., R. H. PICKARD n.Sc. Ph.D. F.R.S. T. S. PRICE O.B.E. D.Sc. Ph.D. N. V. SIDGWICK M.A. Sc.Q.,F.R.S. J . F. THORPE C.B.E. D.Sc. F.R.S. W. P. W-YNNE D.Sc. F.R.S. F.R.S. Qbitarw : A. J. GREENAWAY. CLARENCE SMITH D.Sc. &sisttrlrt Jnbexrr : A. A. ELDRIDOE B.Sc. MARGARET LF. PLA B.Sc. 1923. Vol. CXXIII. Part II. pp. 1649-end. LONDON: GURNEY & JACKSON 33 PATERNOSTER ROW E.C. 4. 1923 PRINTED IN GREAT BRITAIN BY ~ I C H A R D CLAY & YONS LIbIITED, BUNGAY SUFFOLK

ISSN:0368-1645    

DOI:10.1039/CT92323FP033

出版商:RSC    

年代:1923

数据来源: RSC

摘要:

44 PHIUIPQ INVESTIGATIONS ON THE DEPENDENCE OF V.-Investigations on the Dependence of Rotatory Power on Chemical Constitution. Part X V I I . A New Type of Walden Inversion. By HENRY PEILLIPS. IN the examples of the Walden inversion so far recorded an entire group attached to the asymmetric carbon atom of an optically active compound suffers two or more displacements. By thi ROTATORY POWER ON CHEMICAL CONSTITUTION. PART XVII. 45 means either the same compound of opposite configuration is obtained or by conducting one displacement under two different sets of conditions products are obtained which are opposite in sign >+ d-Malic acid I-Malic acid PCI, \ I-Malic acid --+ d-Chlorosuccinic acid The above scheme due to Walden (Ber. 1896 29 113) illus-trates both types.They are therefore processes occurring in two stages. At one of these stages an " abnormal " reaction occum resulting in a change of configuration but at which one i t is im-possible to decide. In both reactions a group attached to the asymmetric carbon atom is replaced. Does the entering group in the f i s t displacement take up the same position relative to tho three remaining groups as that vacated by the group displaced? The sign of rotation of the product cannot be relied upon to give a correct answer to this question. Many instances are known in which substitution occurs remote from the asymmetric carbon atom yet produces a reversal of sign. I n such cases no change of configuration can be assumed and therefore it is evident that change of sign does not necessarily coincide with change of con-figuration.Attempts have been made to overcome this difficulty and to provide a method of determining whether a given reaction is abnormal from a consideration of the mechanism of the reactions in question by inter nZios Armstrong (T.p 1896 69,1399) Gadamer (Chem. Ztg. 1910 34 lOM) and Biilmann (Annulen 1911 388, 338). Further Clough (T. 191S 113 526) has suggested certain principles by which the relative configurations of similarly con-stituted compounds can be determined. I n the examples of the Walden inversion to be described how-ever we can on general grounds single out the particular reactions which occur with configurational change. When d-benzylmethyl-carbinol is allowed to react with p-toluenesulphonyl chloride in the presence of pyridine beiizylmethylcarbinyl p-toluenesulphonate is obtained.I n this reaction complete substitution of a group attached to the asymmetric carbon atom does not occur the hydrogen atom of the hydroxyl group alone suffers displacement. It is justifiabl 46 PHILLIPS INVESTIGATIONS ON THE DEPENDENCE OF therefore to refer to the sulphonic ester prepared in this way from the dextrorotatory alcohol as the d-sulphonate and it is interesting to note that when this is dissolved in benzene chloroform ethyl alcohol carbon disulphide or pyridine the solutions obtained are all dextrorotatory. When this d-sulphonate is treated with sodium ethoxide in benzene or better heated under reflux in absolute alcoholic solution in the presence of solid potassium carbonate the ethyl ether of benzylmethylcarbinol is.formed and has in this case a lavo-rotation. If however d-benzylmethylcarbinol be converted into its potassium derivative and the latter allowed to react with ethyl p-toluenesulphonate the ethyl ether of benzylmethylcarbinol produced has a dextrorotation. C,H,*CH,\ OH (i.) CR,/~<H a% + 33.02" (for [a],, + 3 1.1 1" (in benzene ; 100mm.). \ c = 5 ) . 100 mm.). - 19.90° (for Dextro-rotation and -configuration. \ x Dextro-rotation and -configuration. Laevo-rotation and -configuration. . + 23.50° (for 100 mm.). Dextro-rotation and -configuration. a2.2"d M61 + 19~84~ (for 100 mni.). Dextro-rotation and -configuration. What is the sign of rotation of the ethyl ether which corresponds in configuration to the d-alcohol? This can be decided by the fact that the potassium derivative of the d-alcohol gives a dextro-rotatory ethyl ether when treated with ethyl bromide a reaction in which configurative change is unlikely to occur.I n the first series of reactions however the laevorotatory ethyl ether of benzylmethylcarbinol is obtained from the dextrorotatory sulphonate which can be said to have the Bame configuration as d-benzylmethylcarbinol. The conclusion can therefore be drawn that when the dextrorotatory sulphonate reacts with ethyl alcohol in the presence of potassium carbonate the Z-ethyl ether of benzyl-methylcarbinol is produced the configuration of which is the opposite to that of the dextrorotatory sulphonate used.This is a definite change in configuration in one stage and there-fore it is a definitely " abnormal " reaction. How does this conclusion agree with the usually adopted view ROTATORY POWEE ON CHEMICAL CONSTITUTION. PART XVII. 47 of the mode of reaction of sulphonic esters? Ferns and Lapworth (T, 1912 101 273) have shown that the reactions of these esters resemble very closely those of the alkyl lialoids. 'GH .Fi°CH2> C <H CH iO*S02*C,H7 C,H,*CHZ>C<H (1.) *EtOiH (TI.) CH OiK i+ K,CO Et i0 *SO,*C 7H7 Adopting thcse views i t is apparent that in reaction I involving the complete replacement of a group from the asymmetric carbon atom change of configuration is possible but in reaction 11 in which bonds of the asymmetric carbon atom remain undisturbed, it is unlikely.On examination of the magnitudes of the rotations of the ethyl ethers of benzylmethylcarbinol obtained by the threc separate methods another important conclusion can be drawn. The ' ' abnormal " reaction occiirs with almost complete configurative change. The rotatory power of the ether prepared from the potassium derivative of thc alcohol and ethyl bromide is higher than that of the ether prepared by the other two methods in which a loss in rotatory pow-cr might be suspected. It was decided to extend the investigation and endeavour to prepare a compound from d-benzylmethylcarbinyl p-toluene-sulphonate with complete change of configuration. For such a purpose the compound should be one from which the alcohol could be recovered by methods not likely to cause racemisation or con-figurative change so that the rotation of the recovered alcohol could be compared with that of the original.It was found that such compounds for example benzylmethylcarbinyl esters of carboxylic acids could be readily prepared by the interaction of the potassium salts of these acids and the p-toluenesulphonate in alcoholic solution. Lzvorotatory benzylmethylcarbinyl acetate was prepared from pure d- benzylmethylcarbinol by the following cycle of reactions : This is in agreement with the results obtained. (111.) (IV. O~Z. $- 33.02" (for 100 mm.). + 31.11" (in benzeno solution). CH:>c<~*CO*CH CH 'OH CGH,*CH -. CGH5*CH,>C,H (V. 1 (VI.) 42;. - 7-06' (for 100 mm.). - 32.18" (for 100 mm.). * Or sodium othoxide 4s PHILLIPS INVESTIGATIONS ON THE DEPENDENCE OF The esters derived from d-bmzylmethylcarbinol and the normal aliphatic acids have been prepared and their optical properties fully described in Part VIII of these investigations (T.1914 105, 2261). The acetate prepared from the d-alcohol by the action of acetic anhydride is dextrorotatory ( a z l $- 7-13" *) and on hydro-lysis with alcoholic sodium hydroxide yields the d-alcohol of unchanged rotatory power. That both these reactions should be accompanied by complete configurative change is unlikely and hence it may be assumed that dextrorotatory benzylmethylcarbinyl acetate has the same configuration as the destrorotatory alcohol. I n the above cycle of reactions however this ester is obtained with a laevorotation from a dextrorotatory sulphonate the configuration of which can be said to be dextro.The passage from I V to V therefore occurs by a definitely abnormal reaction and the almost complete inversion of con-figuration is clearly demonstrated by these reactions. The I-ethyl ether of benzylmethylcarbinol was also formed during the preparation of the acetate being produccd by the interaction of the d-sulphonate and ethyl alcohol used as the reaction medium in the presence of potassium acetate. It had a& - 21*92" being higher in rotation than that prepared pre-viously. Its presence necessitated very careful fractional distil-lation of the product since the boiling points of the acetate and of the ethyl ether are fairly close. To ensure that the ester obtained was uncontaminated with this ether a further series of reactions was undertaken in which the n-valerate was substituted for the corresponding acetate.I n these reactions a specimen of I- benzylmethylcarbinol with - 24.94" was converted through the corresponding sulphonate into the n-valerate which had .Elo + 9-76' and gave when hydro-lysed a d-alcohol with a$l + 23-98". Again the loss in rotatory power was small and complete confirmation of the other reaction was thus obtained. Ferns and Lapworth (Zoc. cit.) also raise another point which is of interest. Discussing the reaction which occurs between phenyl p-toluenesulphonate and sodium ethoxide they point out that in this case it must be regarded as occurring in two stages : C,H,*O,SO,*C,H + Na OEt C,H,*ONa + EtO*SO,*C,H, C,H,*O Na + Et,O*SO,*C,H --+ EtO=C,H + NaO*SO,*C,H,.The reasons they advance are first that the reaction proceeds readily a fact which does not seem to indicate the breakage of * All observed rotations recorded in this paper are for 100 mm ROTATORY POWER ON CHEMICAL CONSTITUTION. PART XVII. 49 an 0-C linking the carbon of whioh forms part of a benzene nucleus ; and secondly that in none of its simpler reactions does phenyl p-toluenesulphonrtte reveal the 0 - C linking as the weakest part of its structure. For example it does not yield aniline on treat-ment with ammonia. During this investigation it was also observed that pheny 1 p-toluenesulphonate would not react with potassium acetate in ethyl alcoholic solution although under the same conditions ethyl p - t oluenesulp honat e rapidly produced e t h y 1 acetate .As an explanation of the reaction Ferns and Lapworth put forward the suggestion outlined above that an exchange of radicles occurs an 0-S linking breaking in the process and the sodium phenoxide and ethyl p-toluenesulphonate produced reacting in the usual manner. Assuming this explanation to be correct and applying it to the reaction between the potassium derivative of I-benzylmethyl-carbinol and phenyl p-toluenesulphonate we should expect the following sequence of reactions to take place : 1." Since we have adopted the suggestion that an exchange of radicles occurs as indicated by the dotted lines in A the potassium deriv-ative of the I-alcohol and phenyl p-toluenesulphonate will give rise to I-benzylmethylcarbinyl p-toluenesulphonate and potassium phenoxide.These products will react (B) and the phenyl ether of benzylmethylcarbinol will be produced with inversion of con-figuration it being assumed that sodium ethoxide and potassium phenoxide react in an identical manner with the I-sulphonate. Two experiments could therefore be performed. The potassium derivative of the 1-alcohol could be allowed to react with phenyl p-toluenesulphonate (A) or potassium phenoxide with Z-benzyl-methylcarbinyl p-toluenesulphonate (B). They mould virtually * 1. and d. configuratione fio PHILLIPS INVESTIGATIONS ON THE DEPENDENCE OF be identical reactions thc phenyl ether of the alcohol being pro-duced during each experiment ~ i t h inversion of configuration, and therefore the sign of rotation of the ethers obtained should be the same.Should however the explanation be incorrect that is should phenyl p-toluenesulphonate react in the same manner as ethyl p-toluenesulphonate it would when treated with the potassium derivative of the Z-alcohol produce a phcnyl ether without con-figurative change; and there would result in the two experiments outlined above phenyl ethers of opposite sign. Experimentally it was found that whethcr the reaction was commenced as indicated in A or its course being anticipated as in B,* the phenyl ethers produced had the same sign of rotation, both being dex trorot a tory. If therefore the rtssumption is made that potassium phenoside and sodium ethoxide react in thc same manner with the Z-sulphonate, these two experiments give considerable support to the view of the mode of reaction of phenyl p-toluenesulphonate put forward by Ferns and Lapworth.Discussioit of Results. McKenzie and Clough (T. 1913 103 687) by effecting the interconversion of the optically active phenylmethylcarbinols, showed for the first time that the phenomenon of the Walden inversion was not confined to compounds containing a carboxyl or carboallryloxy-group. Research on the Walden inversion has, however been mainly confined to carbosylic acids containing also an amino- or a hydroxy-group or a halogen atom. During the reactions of these compounds involving the complete removal of a group attached to the asymmetric carbon atom a certain amount of ‘‘ displacement ” racemisation (Senter Drew and Martin T., 1918 113 156) occurs.The compounds are also liable in some cases t o undergo “ catalytic ” racemisation which renders their isolation and purification without loss of rotatory power difficult. When therefore the optical enantiomorph of such compounds is obtained after two displacement reactions a determination of its rotatory power does not truly indicate to what extent the ‘‘ abnormal ” reaction predominates. If however the series of reactions described in the interconver-sion of the enantiomorphously related benzylmethylcarbinols be examined it will be seen that throughout the compounds involved are stable both as regards their chemical and their optical pro-* Using however sodium phenoxide instead of potassium phenoxide ROTATORY POWER ON CHEMICAL CONSTITUTION.PART XVII. 51 perties. They are compounds which can withstand without catalytic racemisation the experimental conditions to which they are subjected and also a t one stage only (the interaction between the d-sulphonate and potassium acetate) is any displacement racemisation likely to occur. To this fact is partly duc the observed completeness of inversion, and moreover it points to the stage a t which the “abnormal” reaction occurs as the source of the very slight decrease in rotatory power which is approximately 2 per cent. This decrease is so small that it must be carefully borne in mind during any attempt to explain the mechanism of this particular reaction. The tendency for the reaction to occur in a definite manner accompanied by inversion of configuration is obviously overwhelming.I n other words it can be said that the group entering the asymmetric molecule is compelled to occupy only one position relative to thc ather three and this is a position which entails configurative change. This position it seems possible to assume corresponds t,o a portion of the surface of the asymmetric carbon atom which is potentially unsaturated. An examination of the constitutional formula (VII) together with a knowledge of the fact that the sulphonic ester exhibits a strong tendency to lose the elements of the corresponding sulphoiiic acid enables this possibility to be visualised. (VII.) CH,/ ‘9 SO,*C,H , It is postulatcd that under certain conditions such as increase of temperature the sulphonic ester molecule assumes an active condition arising through the weakening of the attachment of the a-hydrogen atom t o the asymmetric carbon atom ; this weakening being due to the ester oxygen atom of the O*SO,*C,H group exerting its residual valencies.The ester molecule then in its active condition contains a hydrogen atom held partly by the residual valencies of the ester oxygen atom and partly by the valency of the asymmetric carbon atom. Thus the portion of the latter atom to which the hydrogen is now but loosely linked is in possession of residual valency. It is postulated that in an alcoholic solution of potassium acetate, an indirect “ abnormal” reaction takes place by the addition o 52 PHILLIPS INVESTIGATIONS ON THE DEPENDENCE OF a molecule of potassium acetate to this unsaturat'ed portion through the agency of the carbonyl oxygen atom which i t contains (VIII).The a-hydrcgen atom is displaced by the potassium and the acetyl group usurps the whole affinity of the portion of the asym-metric carbon atom to which it was previously only loosely attached. The potassium p-toluenesulphonate formed during this displace-ment leaves the molecule the hydrogen liberated during its form-ation occupying the position thus vacated (IX). ~o,*c,H, It is suggested also that a direct reaction can occur to an extent sufficient to account for the observed loss of rotatory power. Commencing as before with the molecule of the sulphonic ester in an active condition it is assumed that i t is approached by a molecule of potassium acetate possibly in an ionised condition (X).No addition occurs at the unsaturated portion of the surface of the asymmetric carbon atom but instead the potassium atom displaces the or-hydrogen atom which assumes its normal state and position in the molecule (XI). Potassium p-toluenesulphonate is then eliminated from the molecule leaving the acetyl group to enter the position vacated by the group 0*S0,*C,H7 (XII). This would leave an acetic ester of the same configurafion as the original sulphonic ester. I n each of these hypothetical molecular interactions the form-ation of potassium p-toluenesulphonate in the complex and its subsequent departure do not necessarily imply that only three valencies of the asymmetric carbon atom are utilised a t any par-ticular instant.This salt when formed can still remain moment-arily attached by the residual valencies of the ester oxygen and moreover the portion of the asymmetric carbon atom by which i t is thus loosely held would be in a partly unsaturated condition ROTATORY POWER ON CHEMICL4L CONSTITUTION. PART XVII. 53 It would therefore be likely that the atom or group set free through the formation of potassium p-toluenesulphonate would be attracted to this position. The arrangement within the bi-molecular complexes before final disruption occurs can therefore be represented as follows : C,IS,*CH2 ,H YH3 rc.~~o-c:o It is conceivable that a certain proportion of such molecular interactions may miscarry at one or other of the stages through which it is suggested they pass and in such cases an unsaturated hydrocarbon will result.Experimental evidence of the formation of varying amounts of an unsaturated hydrocarbon has been obtained ; in attempting to prepare the ethyl ether of benzylmethylcarbinol from the corre-sponding sulphonate if sodium ethoxide be used instead of potassium carbonate the product consists almost entirely of such a compound, this being due presumably to the too rapid withdrawal of the elements of the sulphonic acid from the molecule. It will be noticed also that the explanation of these reactions depends on the presence in the ester molecule of a detachable hydrogen atom linked to the same carbon atom as the O*S02*C7137 group. &om thcse assumptions it would follow that ethyl p-toluene-sulphonate CH3*CH2*0*SO2*C,H7 should react readily with potass-ium acetate in alcoholic solution whilst phenyl p-toluenesulphonate, C&,*O*S02*C7H7 should only react with difficulty if at all.This conclusion is completely borne out; by experiment. An explanation is still required to account for the slight loss of rotatory power observed during the reactions involved in the preparation of the ethyl ethers. I n this connexion it is noteworthy that the loss of rotatory power is the same whether these compounds are prepared through the agency of the sulphonic ester of the optically active alcohol or of ethyl p-toluenesulphonate. This case therefore permits of a different explanation from that advanced in the case of the esters.Bearing in mind the supposed anomalous behaviour of phenyl p-toluenesulphonate (p. 40) it is postulated that in the reaction between ethyl p - toluenesulphonate and the potassium derivative o 64 PHILLIPS INVESTIGATIONS ON THE DEPENDENCE OE' benzylmethylcarbinol there is a tendency for an exchange of radicles to occur : J/ &Ether. d. 9 I-E ther. The sulphonic ester exercises its ability to decompose with breakage of an 0-S linking and the exchange occurs as indicated by the dotted lines. That the amount of interchange would be small is accounted for by the ease with which ethyl p-toluene-sulphonate reacts with the potassium derivative of the alcohol and hence the rapidity with which the d-ether is produced. The yield of I-ethyl ether from the right-hand side of the equation will necessarily be small but since the " abnormal " reaction results in a product of almost full activity the amount produced need not be large to cause the small loss of rotatory power observed.This explanation is presumed to be equally applicable to the interaction of d-benzylmethylcarbinyl p-toluenesulphonate and ethyl alcohol in the presencc of potassium carbonate. d. E-E ther. d. In the above forinuke the dotted lines indicate the method of exchange and the arrows the double decomposition. Again it is evident that the extent to which rcaction takes place between substances on the right-hand side of the scheme will not be large under the conditions of the experiment. It is significant, however that if the reaction is carried out in thc presence of potass-ium acetate which would react with any ethyl p-toluenesulphonatc formed the product has a higher rotation that is less d-ether is produced.It will be seen that these cxplanations are in accordance wit ROTATORY POWER ON CHEMICAL CONSTITUTION. PART XVII. 55 the view which has been frequently advanced that a reaction which results in configurational change proceeds indirectly being preceded by addition whilst a normal reaction involves direct substitution. That the decrease in rotatory power or racemisation which accompanies reactions in which the phenomenon of Walden inversion is observed is due rather to the simultaneous formation of the product possessing both d- and 1-configurations has also been previously postulated.Holmberg (drkiv Kern. Min. Geol., 1916 No. 8 6) has shown that when chlorosuccinic acid is con-verted into xanthosuccinic acid the reaction follows two courses simultaneously : Z-Bromosuccinic acid ti-santhosuccinic acid / 'A d-malolactone + I-xanthosuccinic acid Similarly Senter and his collaborators (T. 1915 107 638 et seq.) showed that the action of ammonia on halogen-substituted acids yields both d- and 1-amino-acids. The explanation given of the small loss in rotatory power which accompanies the inversions described is perhaps so far based on meagre evidence. It is evident however that the predominance of the reaction which results in inversion of configuration prevents acceptance of the view that it occurs with racemisation.The occurrence of racemisation (luring a reaction suggests a haphazard interaction between two lrinds of molecule. It is inconceivable that such an interaction could result in products of the degree of optical purity obtained. E X P E R I M E N T A L. d-BenxylmethylcarbinyJ p-ToZuenesu1phonate.-This was prepared as required by the interaction in the cold of equivalent quantities of the alcohol and p-tolucnesulphonyl chloride in the prescnce of pyridine. The reaction was complete after twelve hours. On pouring the reaction mixture into water the ester crystallised, and after filtration was purified by recrystallisation from glacial acetic acid or ethyl alcohol. It had m. p. 94". 0.7392 Gram of ester required 0.1007 gram of sodium hydroxide for complete hydrolysis the theoretical amount being 0.1019 gram.The following determinations of its optical rotatory power were made. The solutions were prepared by dissolving about one gram of the ester in the solvent and diluting to 20 C.C. The observations were taken in a 2-dcm. tube 56 PHILLIPS INVESTIGATIONS ON TIIE DEPENDENCE OF Grams of Solvent. solut,e. Ethyl alcohol ... 0-5364 Benzene ......... 1.0126 Chloroform ...... 1.0136 Carbon disulphide 1.0046 Pyridine ..... . . .. 0.0010 Observed rotation. I \ A h h 5893 5461 4358 + 1.66' + 1.84' 3-3.30' 2-82 3.15 5-83 2.53 3.05 5 4 7 3-09 3.75 6.87 2-54 3.46 5.88 [.I*. , - \ A A A 5893 5461 4388 +30.90° +34-30' +61.3'i0 27.85 31-11 57-58 24-97 30-09 53.98 30.76 37-33 68-28 28.59 34-91 59.33 Reaction bet ween the Potassium Derivative of d-Benzylmethyl-carbinol and Ethyl p- Toluenesulphonate .-Four grams of clean potassium were shaken in hot toluene the latter when cold was replaced by 200 C.C.of dry benzene and 16 grams of the d-alcohol were added. When dissolution of the potassium which was hastened by gentle warming was completed the mixture was cooled and 40 grams of molten ethyl p-tolucnesulphonate were slowly added a voluminous precipitate forming. When the reaction began to slow down the mixture was shaken vigorously for twenty-two hours. It was then treated with a solution of sodium hydroxide and distilled with steam. To the benzene extract of the distillate dried with potassium carbonate 20 grams of phthalio anhydride were added and the solution was boiled, the benzene being allowed to distil off slowly up a fractionating column.The residue having been heated for ten hours a t 110", was poured int,o dilute sodium carbonate solution and after re-maining over-night this solution was extracted with ether. The benzylmethylcarbinyl ethyl ether obtained from the dried ethereal extract was distilled under reduced pressure and after three frac-tionations 9 grams were obtained; b. p. 92-93"/19 mm. d:!' 0.9168 nE% 1.4845 and + 19-84". Beaction between Xodium Ethoxide and Benzy1,methylcarbinyl p- ToEuenesulphonate.-The most successful experiment of this series was conducted as follows Twenty grams of the sulphonic ester (prepared from a sample of partly active alcohol with a& - 7.82" and having [cx]5461 - 6.92" in benzene) were dissolved in 100 C.C.of anhydrous ethyl alcohol and while the solution was being warmed on a water-bath a solution of 2 grams of sodium in 50 C.C. of alcohol was added during three and a half hours. The alcohol was then distilled off through a column the residue poured into water and the oily layer whieh formed extracted with ether. The product obtained from the dried ethereal extract was repeatedly distilled and gave two main fractions. It was optically inactive after four redistillations. It rapidly decolorised bromine water had n:& 1.5331 0.9046 and was an unsaturated hydrocarbon. Fraction A b. p. 62-65"/14 mm. amounted to 3 grams ROTATORY POWER ON CHEMICAL CONSTITUTION. PART XVII. 57 Fraction B b. p.85-88"/14 mm. closely resembled the ethyl ether of benzylmethylcarbinol. About 1.5 grams were obtained having 4- 4.12". Reaction between d-Benzylmethylcarbinyl p-Toluenesulphonate and Ethyl Alcohol in the presence of Potassium Carbonate.-A mixture of 20 grams of the d-sulphonic ester prepared from the pure d-alcohol 150 C.C. of absolute alcohol and 20 grams of dry finely powdered potassium carbonate was heated under reflux for thirty-seven hours. The alcohol was then distilled off and the residue poured into water. The oil which separated was extracted with ether. Since benzylmethylcarbinol might have been formed during the reaction by hydrolysis of the sulphonic ester the product was heated with phthalic anhydride for ten hours a t 100-110" and poured into sodium carbonate solution from which the required product was isolated in the usual way by extraction with ether.On distillation a very small quantity of a hydrocarbon was isolated. The main fraction 6.9 grams boiled at 85-100"/20 mm. After two distillations the mixed ether (5 grams) had b. p. 92-94"/20 mm., G'" 0.9177 ng6 1.4878 and a$il - 19-90' which was unchanged by subsequent distillation. Reaction between d- Benxylmethglcarbinyl p- Toluenesulphonate and Pdassium Acetate.-Thirty grams of the pure d-ester were dissolved in 150 C.C. of absolute alcohol and 21 grams of freshly fused potass-ium acetate were added. The clear solution obtained on warming soon became clouded by a gelatinous precipitate which rapidly changed to white crystalline plates. After six hours' heating under reflux the alcohol was distilled off and the residue poured into water.The oil which separated was isolated with ether in the usual manner. On distillation a small fraction b. p. below 100"/16 mm. was obtained the main fraction 14.8 grams boiling a t 100-113"/16 mm. After three €ractionations 7.8 grams of Z-benzylmethyl-carbinyl acetate b. p. 112-114"/18 mm. were isolated having <f5' 0.9978 np& 1.4881 and a z l - 7.06". On hydrolysis with sodium hydroxide 1.0660 grams required 0.3391 gram of NaOH (theory 0.2395 gram). The remainder of the 1-acetate was hydrolysed in alcoholic solution. The regenerated 1-benzylmethylcarbinol had b. p. 108"/21 mm. and - 32-18" whereas the d-alcohol used for the preparation of the sulphonate had olzil + 33-02'.The lower-boiling portions of the distillate were heated with alcoholic sodium hydroxide and from the product any active alcohol present was removed in the usual way with phthalic anhydride. The product obtained was separated by distillation into two fractions A. b. p. 78-79"/20 mm. €5. b. p. 90-95"/20 mm 58 PIIIIILIPS INVESTIGATIONS ON THE DEPENDENCE OF A weighed about 1.6 grams and consisted mainly of an un-saturated hydrocarbon. B when redistilled had b. p. 93'/19 mm., ?%ZP fimG 1.4909 di 0.9230 and a'~& - 10.96" in a 50-mm. tube. Its refractive index and density are thus both somewhat higher than those obtained for the ethyl ether of benzylmethylcarbinol by the other methods. This experiment was repeated using a partly active alcohol - 7.82') which gave a p-toluenesulphonate having [a]5Jsl - 6-92" in benzene solution.Twenty grams of this ester dissolved in 120 C.C. of alcohol were heated under reflux with 14 grams of potassium acetate ; 3.8 grams of benzylmethylcarbinyl acetate were isolated b. p. 107"/14 mm. di? 0.9965 nzi6 1.4897 and + 2.0". On hydrolysis it yielded a benzylmethylcarbinol having aZl + 7.44'. Other products of the reaction were a hydrocarbon and the ethyl ether of benzylmethylcarbinol which were not compl&ely isolated owing to the small bulk oE the mixture. Reaction between Benxylmethylcarbinyl p-Toluenesulphonnte and Potassium Acetate when dissolved in Glacial Acetic Acid .-Nineteen grams of the sulphonate - 6-92" in benzene solution), prepared from an alcohol having -7*82' were dissolved in 100 C.C.of glacial acetic acid. The mixture was warmed for twenty-four hours on a water-bath and remained quite clear. It was poured into water the acid neutralised with sodium carbonate, and the solution extracted with ether. The product obtained from the ethereal extract was carefully fractionated. After three distillations 5.7 grams of benzylmethylcarbinyl acetate were obtained which had dy 0.9961 nZ$' 1.4896 and aEzl + 1.06". This on hydrolysis gave an alcohol having + 3-74" nG& 105214 and GF 0.9579. Reaction bet ween Benxylmethglcarbinyl p- Toluenesulphona fe and Potassium n- Valerate.-Potassium n-valerate was prepared by neutralising 9%-valeric acid with the theoretical quantity of potassium carbonate dissolved in the minimum of water and evaporating the mixture to dryness.Forty grams of the residue were dissolved in 182 grams of absolute alcohol and 90 grams of benzene and the solution dried by distillation until the temperature was 78.3". Thirty grams of the sulphonate prepared from benzylmethylcarbinol (a:$ - 24.94") were added to the alcoholic solution and the mixture was heated under reflux for six hours. On isolation of the product as described in previous experiments 9-S grams of benzylmethyl-cnrbinyl n-valerate were obtained b. p. 147-14So/19 mm. $!' 0.9605 n:& 1.4817 and On hydrolysis it gave an alcohol having a:'$l + 23.98". + 9-76" ROTATORY POWER ON CHEMICAL CONSTITUTION. PART XVII. 59 During this reaction also thc lower fractions obtained were small in bulk and consisted largely of benzylmethylcarbinyl ethyl ether.Reaction between Sodium Phenoxide and BenzyEmeth$carbinyl p-ToZuenesuZphonate.-To a solution of sodium phenoxide in absolute alcohol prepared from 5% grams of phenol and 1-35 grams of sodium 17 grams of benzylmethylcarbinyl p-toluenesulphonate, prepared from a partly active alcohol (%El - 6-44') were added, and the mixture was heated under reflux for four hours. The alcohol was distilled off the residue poured into a dilute solution of sodium hydroxide and after extraction with ether fractional distillation of the product gave two main fractions (1) an un-saturated substance about 2 grams b. p. 68-70"/14 mm. ; (2) benzyl-methylcarbinyl phenyl ether 4 grams b. p. 156-157'/14 mm. + 14*12" d? 1.0288 n'Jr 1-5573 and [R&& 66-40 (calc.65.91). Reaction between Phenyl p-Toluenesztlphoncte and the Potassium Derivative of BenxyEmethylca~bino1.-Twelve grams of partly active alcohol (a:z1 - 6.44") were added to 120 C.C. of dried benzene in which were suspendcd 3 grams of finely divided potassium. When all the metal had dissolved 5t benzene solution of 20 grams of phenyl p-toluenesulphonate was added. The solution remained clear for some time then a voluminous precipitate suddenly formed. The mixture having been heated under reflux for five hours and sodium hydroxide added was distilled with steam. The distillate was extracted with benzene and the residue from the dried benzene extract distilled. Three fractions were obtained A b. p. 70-80'/17 mm. (less than 1 gram). B b. p. 103'/17 mm. (7 grams). C b. p. 157-160"/17 mm. (1.5 grams). A appeared to be identical with the hydrocarbon previously obtained. B was benzylmethylcarbinol having - 4-36", whilst C was similar to the phenyl ether obtained in the previous experiment and had + 10.20". Although the sign of rotation of this ether is definite the magni-tude of the rotation is not above suspicion since the small amount obtained made efficient purification difficult. The author desires to express his thanks to Dr. R. H. Pickard, F.R.S. and Dr. J. Kenyon for their guidance during the course of this research and to acknowledge the receipt of a personal grant from the Department of Scientific and Industrial Research. The materials used were purchased in part with a grsnt made by the Government Grant Committee of the Royal Society. BATTERSEA POLYTECHNIC S.W. 11. [Received November l s f 1992.

ISSN:0368-1645    

DOI:10.1039/CT9232300044

出版商:RSC    

年代:1923

数据来源: RSC

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60 FARNELL NITRATION OF 3-CHLOROACENAPHTHENE. VI.-Nitration of 3-Chloroaccnap~fhene. By GLADYS FARNELL. IN the nitration of 3-chloroacenaphthene described below a uniform product was not obtained and it can be shown that the nitro-group has taken up alternative positions. 3-ChZoro-4-nitro-acenuphthene m. p. 136-138" was isolated and its constitution proved. A second product not entirely uniform and melting a t 160-166" was obtained and this also appears to be a mononitro-derivative of chloroacenaphthene. Nitrution.-Twenty grams of 3-chloroacenaphtheneY m. p. 69", prepared by Crompton and Walker's method (T. 1912 101 958) and purified by distillation and crystallisation from alcohol were dissolved in the minimum quantity of glacial acetic acid and 4.4 C.C. of nitric acid (d 1.5) so added with vigorous shaking that no appreciable temperature change occurred.The liquid which changed from yellow to red deposited crystals long pale yellow needles after three hours and later spherical clusters. By repeated crystallisation from alcohol it was possible to isolate from the crude product the two compounds already mentioned melting at 160-166" and 136-138" respectively which are formed in about equal quantity. The final yield of the latter was only 10 per cent. of the theoretical; attempts to improve the yield by varying the conditions of the nitration were not successful [Fodnd N = 6.07, 6.06; C1 by the lime method = 15-23 15.05 by Rosenmund's method (Ber. 1918 51 575) = 16.30. C,,I3,O2hTC1 requires N = 6.02; C1 = 15.20 per cent.].The results indicate that the compound is a mononitrochloro-acenaphthene. A study of its reduction products served to establish its constitution. Reduction.-The chloronitroacenaphthene was first reduced with sodium hyposulphite by Sachs and Mosebach's method (Ber., 191 1 44 2855). The product after purification by crystallisation from hot water was calourless and melted at 145" (Found C1 by Rosenmund's method = 16.89. C,,H,NCl requires C1 = 17.46 per cent.). Chloroaminoace~~hthene crystallises in fine colourless needles from water alcohol or alcohol-water mixtures. It darkens on heating or on exposure to light. Its solutions are coloured blue by ferric chloride and in the presence of acid give a green pre-cipitate with sodium nitrite. In these points it closely resembles the ordinary aminoacenaphthene in which as shown by Graebe (Annulen 1903 327 Sl) the amino-group is in the position FARNELL NITRATION OF ~-CHLOROACEXAPHTHENE.61 (or 4). This analogous behsviour suggested that the amino-groups in the two compounds are in similar positions which could only be the case if the nitro-group had originally entered S-chloro-acenaphthene in the position 4. Wcre this so the replacement of the chlorine of the above chloroaminoacenaphthene by hydrogen should yield the familiar 3-aminoacenaphthene. Such a replacement occurs in the reduction with hydrogen described above but a simpler method of arriving a t the same result was discovered in the direct reduction of the original chloro-nitroacenaphthene. This compound was reduced with hydrogen in the presence of palladium.It was found Ghat in addition t o the removal of the chlorinc the nitro-group mas reduced to an amino-group. When purified thc amino-compound thus obtained resembled 3-aminoacenaphthene perfectly in its appearance and behaviour. It melted a t 107" alone or mixed with this substance, and gave the colour reactions with ferric chloride and sodium nitrite already described. I t is therefore the aminoacena'phtheno of known constitution with the amino-group in the position 3 (or 4). The production of this compound by the direct reduction of the chloronitroacenaphthene melting at 136-138" in which chlorine is in the position 3 proves that the nitro-group is in the position 4. On oxidation with chromic acid i t gives the corresponding chloro-nitronuphthalic acid.This was obtained as a yellow powder and, on crystallisation from glacial acetic acid it gave pale yellow, shining leaflets of the anhydride (Found N = 4-69. C,,H,O,NCl requires N = 5.04 per cent.). Sodium calcium and bariutm salts were prepared and the calcium s d t was analysed (Found Ca = 11.76 11.69. The compound melting at 160-166" formed along with the above chloronitroacenaphthene in tihe nitration of S-chloroacenaph-thene was not obtained in sufficient quantity in a pure state for its complete examination. It was found to contain 6.04 per cent. of nitrogen and therefore is probably also a mononitrochloro-acenaphthene or a mixture of such compounds. C,,H,O,NClCs requires Ca = 11.99 per cent.). This work was suggested to me by Mr. H. Crompton and I am BEDFORD COLLEGE, ndebted to him for guidance in carrying it out. REGBNT'S PARK N.W. 1. [Received November 6th, 1992.

ISSN:0368-1645    

DOI:10.1039/CT9232300060

出版商:RSC    

年代:1923

数据来源: RSC

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62 TEORPE AND WOOD : VI1.-The Chemisiry of the Glutaconic Acids. The Isomerism due to Retarded Mobility. By JOCELYN FIELD THORPE and ARTHUR SAMUEL WOOD. EAJXLY this year Feist (Annulen 1922 428 25) published a theoretical discussion of the evidence which has accumulated during the past seventeen years regarding the structure of the glutaconic acids and reached the general conclusion that the isomerism of these acids is of the “ordinary” geometrical type and that the adoption of a symmetrical formula for glutaconic acid is unnecessary. He supports his conclusion by some further experimental work embodied in three papers (with Breuer ibid., 59 6s; and with Breuer and Lubricht ibid. 40) in two of which he dcals with the products formed by the decomposition of the ozonides of certain acids of the series and in the third with the question of the existence of the three isomerides of p-phenyl-a-methylglutaconic acid isolated by us (T.1913 103 1574). Feist gives an excellent summary of the experimental facts which have led to the conclusion that the formulae of glutaconic acid and those of its derivatives which contain a mobile hydrogen atom must differ from those of the ordinary unsaturated dicarb-oxylic acids in some fundamental manner but unfortunately he does not criticise these facts or their theoretical bearing in detail, and therefore it is difficult to follow his general reasoning. Never-theless i t would seem that our views and his are not in reality, vcry different because when he says that “ the absence of a second form of glutaconic acid is readily explicable on the assumption that the double bond changes position,” he can only mean that the absence of isomerism is due to symmetry because it is obvious that any movement of the double bond in glutaconic acid will produce-as does the movement of the double bonds in either of the Kekul6 benzene individuals-a substance having an identical space formula.It is true that he guards himself by the alternative “ oder ausschliesslich die stabilere trans-modification bilden wird,” but of course this cannot be the case because the only known form of glutaconic acid is a cis-form that is it readily passes into the anhydride a behaviour which is quite different from that of the known trans-forms of the series such as trans- aa-dimethyl-glutaconic acid or trans-a@-trimethylglutaconic acid which do not form anhydrides or for the matter of that of the tram-modification of p-phenyl- a-methylglutaconic acid which he himself mentions in his paper.In his ozone experiments Feist prepares the ozonides of the two Part XIII TIIE CHEMISTkY OF THE GLUTACONIC ACIDS. PAltT XIII. 63 forms of aP-dimethylglutaconic acid and of his two forms of p-phenyl-a-methylglutaconic acid and studies the products obtained from them on degradation. If however such evidence were accepted as proof of structure the formula of benzene would have been settled when Harries carried out his classical researches on the formation and degradation of its ozonide. Still the experiments described by Feist are instructive because they show that the ozonides from both the " cis " and " trans " forms of ethyl p-phenyl-a-methylglutaconate yield the same four products and that two pairs of these are those which would normally have been derived from two esters having tho formulz C0,Et-CH,*CPh:CMe*CO,Et and CO,Et*CH:CPh*CHMe*CO,Et respectivcly.In other words, the behaviour towards ozone is exactly that which one would expect if the esters had reacted in the '* normal " form. Finally, Feist has succeeded in isolating only two forms of P-phenyl-a-methylglutaconic acid. One of these is the trans-labile modification (m. p. 155") described by us (Zoc. cit.). The other melts at 161" and is evidently a cis-acid because it is readily converted into an anhydride (m. p. 94").' The two other acids of this formula pre-pared by us were the "normal" acid (m.p. 120") and the cis-labile acid (m. p. 108"). Feist considers that these two acids are impure specimens of his acid (m. p. 151") and attempts t o prove his point by determining the melting points of varying mixtures of the trans-labile acid (m. p. 155") and his cis-acid (m. p. 151"). As our acids were made by the hydration of the pure anhydride, i t is not possible for them to have contained any of the trans-modification. Moreover our acids were pure compounds and the repeated recrystallisation of specimens which remained in our possession has failed to alter the melting points given above. The explanation of the discrepancy in our results and those of Feist without doubt rests on the fact that the anhydride (hydroxy-anhydride) prepared by Feist from his acid melting a t 151" is a different substance from that prepared by us from the acids melting at 120" and 108" respectively.The two anhydrides melt a t much the same temperature but they react very differenfJy on hydration, and although we have not succeeded in isolating the pure anhydride prepared by Feist we have been able to show that our anhydride is at any rate partly converted into Feist's anhydride when it is distilled under diminished pressure. This follows because a specimen of our anhydride which before distillation gave on hydration the acids melting a t 120" and 108" as sole products, yielded after distillation a mixture of acids from which we were able to isolate a small quantity of Feist's cis-acid melting a t 151".It is evident therefore that in a glutaconic system such as tha 64 THE CHEMISTRY OF THE GLUTACONIC ACIDS. PART XIII. which is contained in the molecule of p-phenyl- a-methylglutaconic acid the mobility of the hydrogen atom is so far decreased as to render possible the isolation of two forms of the hydroxy-anhydride which can be represented by the formulae I and 11. SMe-CQ FMe=C(OH) $!HMe*CO,H EPH >o GPh CH-CO CH*CO,H Y"h_ =o CH-C(0H) (1.) * (11.) (111.) The hydroxy-anhydride (11) gives on hydration Feist's acid (111), and the hydroxy-anhydride (I) a mixture of the " normal " acid (IV) and the cis-labile acid (V) ; the trans-acid being represented by (VI). hl. p. 94" (T. and W.). M. p. 93-94" (F.) ci8-acid m. p. 151' (F.).-F]Me*CO,H 5Me.C 0,H CO,H*EMe YHPh YPh YPh *CH*CO,H CH,*CO,H CH,-CO,H (IV.) * (V-) * (VI.) * Two other compounds of this formula should also be capable of isolation namely the tram-acid (VII) corresponding with Feist's cis-acid (111) and the " normal " anhydride (VIII), M. p. 120' (T. and W.). M. p. 10s" (T. and W.). %. p. 155" (T. and W. F.). yHMe*CO,H *$Ne-CO (VII.) RPh HFPh >O (VIIz.) C 02H *CH *CK-CO but we have not a+~ yet been able to isolate these substances. From these experiments i t would appear therefore that a glutaconic acid in which the presence of groups in the three-carbon system SO far retards the movement of the tautomeric hydrogen atom its to enable i t to remain within either the three-carbon system or one or other of the systems C.C.0 can be isolated in five forms-two trans- two cis- and 0ne " normal." THE IMPERIAL COLLEGE OF SCIENCE AND TECHNOLOGY, S. KENSINGTON. [Received December I s t 1922.1 4 The structures of the compounds marked * are we consider fixed by the fact that the three acids IV V and VI give isobutenylbenzene, CHMe:CPh-CH, when they are boiled with dilute mineral acid (compare Thorpe and Wood Zoc cit. p. 1572)

ISSN:0368-1645    

DOI:10.1039/CT9232300062

出版商:RSC    

年代:1923

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HOWELL THE HIGHER OXIDE OF COBALT. 65 VII1.-The Higher Oxide of Cobalt. By OWEN RHYS HOWELL. THE precipitation of a higher oxide of cobalt from solution by means of alkali and an oxidising agent has received considerable attention (Baylcy Chem. News 1879 39 81; Carnot Compt. rend. 1889 108 610; Schroder Chem. Zentr. 1890 i 931 ; Vort-mann Ber. 1891 24 2744; McLeod Rep. Brit. ASSOC. 1892 669; Mawrow 2. anorg. Chem. 1900 24 263; Hiittner ibid. 1901, 27 81; Metzl ibid. 1914 86 358) but the nature of the oxide does not appear to have been satisfactorily established. An attempt was therefore made to throw light on the subject by a quantitative examination of the precipit,ates formed by the action of alkaline hypochlorites on cobalt sulphate. In one series of experiments, the cobalt salt was precipitated with sodium hydroxide and sodium hypochlorite; in a second series lime and bleaching powder were used.E x P E R I M E N T A L. Materials.-The cobalt sulphate was free from nickel and con-tained only a trace of iron. The sodium hypochlorite was made by passing washed chlorine into aqueous sodium hydroxide below 15" until chlorination was almost complete a little free alkali being left to retard decomposition of the hypochlorite. The calcium hypochlorite was prepared by extracting bleaching powder with water. Method of Investigation .-A solution containing 15 grams of cobalt sulphate in 100 C.C. of water was precipitated with the requisite amount of alkali and hypochlorite dissolved in 500 C.C. of water, after determining accurat'ely the concentration of the hypochlorite (by liberation of iodine) and of the alkali (by adding hydrogen peroxide to remove the hypochlorite and then titrating due allow-ance being made for the acidity of the hydrogen peroxide).The mixture was stirred for two hours during which any excess of hypochlorite was decomposed by the catalytic action of the oxide. The precipitate was allowed to settle over-night filtered on a Buchner funnel washed collected in a porcelain dish and weighed. For analysis samples of about 8 grams were weighed in small tubes, and dropped into a solution of potassium iodide acidified with hydrochloric acid; the liberated iodine was titrated and the available oxygen calculated. In later experiments the suspended precipitate was titrated immediately after thc completion of the decomposition of the VOL.CXXTIJ. 66 HOWELL THE HIGHER OXIDE OF COBALT. hypochlorite without waiting for it to settle. I n this way it was establishcd that the oxide once formed is quite stable since the same value was found for the available oxygen immediately after precipitation and after the precipitate had been kept for some weeks. Action of Hypochlorite Alone.-The following results were obtained with sodium hypochlorite free from alkali : Equivalents of NaOCI. 0.776 1.400 1.960 2.494 3.576 4.988 TABLE I. Equivalents of available oxygen in the precipitate. Per equivalent of Per equivalent of Co taken. Co precipitated. 0.471 1.050 0.700 1.045 0-786 1.050 0.834 1.056 0-885 1.048 0.934 1.053 The amount of available oxygen was estimated as described above and the amount of cobalt in the precipitate was also estimated in cach case by taking an aliquot part of the suspension of the oxide filtering washing and reducing to metal in a stream of hydrogen.The composition of the precipitate is seen to be inde-pendent of the amount of hypochlorite used the proportion of available oxygen being constant at 1.05 equivalents The direct act>ion of the hypochlorite is therefore to yield the sesquioxide, which would contain 1 equivalent of available oxygen. The results are shown graphically in Fig. 1 where the amount of available oxygen found in the precipitate is plotted against the total amount taken. The slope of the curve indicates that the reaction proceeds initially according to the equation 2CoS0 + 3NaOC1+ H,O = Co,O + 0 + 2NaHS0 + NaCl + Cl,, the course of which is represented by the tangent (NaOC1 Co,O = 3 1) in Fig.1 (A); but as the amount of hypochlorite is increased there is probably an increased tendency to produce neutral sodium sulphate as shown in the equation 3CoS0 + 4NaOCl= C O ~ + 0 + 2Na2S0 + 2C1,. Since the composition of the precipitate is constant its content of available oxygen is a measure of the amount of cobalt pre-cipitated ; the ordinates denoting this quantity fall away rapidly from thc tangent showing that a very large excess of hypochlorite would be iiecessary to secure complete precipitation of the cobalt. This is attributed to the fact that the particles of sesquioxide appear to be coated with a higher oxide which catalytically decompose HOWELL THE HIGHER OXIDE OF COBALT.67 the hypochlorite an action that is specially rapid in these alltali-frce solutions. Action of Hypochlorite in .Prc.wnce of Alkali.-A constant excess of alkali was used with varying amount's of hypochlorite. The results obtained with the sodium compounds arc given in Table I1 and those with the calcium compounds in Table 111. The values are plotted in Fig. 1 (B). FIa. 1. NaOH. 1.469 1.400 1.400 1-421 1-421 1.410 1.341 1.421 1.390 1.406 9 3 4 Equicalents of Tqpochlorite. Na,CO,. 0.044 0.022 0.022 0.01 1 0.022 0.01 1 0.069 0.022 0.045 0.022 Total alkali. 1-513 1.422 1.422 1.432 1.443 1.421 1.410 1.443 1.435 1428 TABLE $11.Available NaOCl. Nil 0.320 0.405 0.562 0.601 0.703 1.051 1.640 2-629 5.192 Available oxygen in the precipitate. 0.060 0.712 0.886 1.119 1.155 1-162 1.149 1.121 1-106 1.095 Available oxygen in the oxygen in the Ca(OH),. Ca(OCl),. precipitate. Ca(OH),. Ca(OC1)2. precipitate. 1.192 Nil 0.084 1.181 0.745 1.151 1.192 0-248 0.550 1.192 1-007 1.142 1.192 0.396 0.829 1.192 2.002 1.140 1-187 0.507 1.000 1.215 3.026 1.130 1.204 0.596 1.142 2) 68 HOWELL THE HIGHER OXIDE OF COBALT. In every case the quantities are given in equivalents per equivalent of cobalt the equivalent of a hypochlorite being taken as the quantity which contains 8 grams of available oxygen. Since in presence of an excess of alkali precipitation is always complete the available oxygen calculated on the cobalt taken is the same as on the cobalt precipitated.It is seen that owing to atmospheric oxidation of the hydroxide, the precipitate contains more oxygen than that supplied by the hypochlorite so long as the quantity of the latter is less than the quantity (half an equivalent) that is required to oxidise all the hydroxide to sesquioxide. If more than this quantity is added, oxidation again proceeds beyond the stage of sesquioxide and the peroxide so formed catalytically decomposes the hypochlorite. FIG. 2. Equivalents of alkali. Since however the peroxide appears t,o be stabilised by the excess of alkali (see p. 69) the action of the hypochlorite proceeds further than when hypochlorite is used alone the extent depending on the excess of alkali.When still more hypochlorite is used the available oxygen in the precipitate falls off towards the slightly lower value given by hypochlorite alone. Action of AZkaZi.-A oonstant amount of hypochlorite was used with variable amounts of alkali. The results with the sodium compounds are given in Table IV and those with the calcium compounds in Table V. The values are plotted in Fig. 2. The two curves are not directly comparable because the precipitating solutions were not of the same composition in the two cases. Both curves exhibit a break at one equivalent of alkali. Up to this point the precipitation of the cobalt is incomplete since in the absence of alkali a very large excess of hypochlorite is require HOWELL THE HIGHER OXIDE OF COBALT.69 NaOH. Nil 0.190 0.462 0.740 0.908 1.104 1.502 1.910 2.342 2.910 Na,CO :, Nil 0.032 0.020 0.018 0.018 0.01 1 0.018 0.01 1 0.042 0,023 rrotai alkali. Nil 0.222 0.482 0.758 0.926 1.118 1.520 1.921 2.384 2.933 TABJ,E Iv. Available oxygen in the pre-cipit,ate calculated on NaOCI. 1.400 1.393 1.393 1.400 1.416 1.393 1.383 1.400 1.400 1.500 (ii) cobalt (i) cobalt taken. precipitated. 0.700 1.050 0.786 1.099 0.895 1.072 1.002 1.075 1.072 1.089 1-106 1.150 1.184 1.226 1,280 TABLE V. Available oxygen calculated on Ca(OH),. 0.01 1 0,512 0.821 1.200 1.721 2-278 3.206 Ca( OCI) ,.1-143 1.153 1.147 1.153 1.153 1.153 1.143 (i)-cobalt taken. (ii) cobalt precipitated. 0.619 1.052 0.881 1.097 1.055 1.125 1.140 1.150 1.182 1.156 to throw down all the cobalt whereas the precipitation of the cobalt by alkali is quantitative. The figures in the last oolumn show that the precipitate is in every case a slightly peroxidised sesquioxide ; the proportion of available oxygen which it contains is however not constant but increases with the amount of alkali that is used. I n the case of sodium hydroxide the increase con-tinues when the alkali is in excess of one equivalent and is even more rapid than when smaller quantities of alkali are being used to precipitate the cobalt. In the case of lime this secondary increase in presence of an excess of alkali does not take place, since the active mass of the calcium hydroxide is limited by its sparing solubility.The lowest figures in the last column of Tables IV and V are those given by hypochlorite alone even when present in large excess Some additional factor must therefore be introduced t o account for the higher degree of oxidation which results from the use of alkali. For this reason it is suggested (i) that cobalt hydr-oxide is more readily peroxidised than cobalt sulphate and (ii) that the peroxide thus formed is perhaps hydroxylated for example, OH*Co*O*OH and in this form is more stable than cobalt peroxide precipitated directly from solution by sodium hypochlorite 70 HOWELL THE HIGHER OXIDE OF COBALT. Action of Sodium Carbonate.*-A number of experiments have been made in which the cobalt solution was precipitated with a mixture of sodium carbonate and sodium hypochlorite.Under these conditions an almost black gelatinous precipitate is obtained, and a green solution which deposits the black substance slowly, but more rapidly on dialysis. The green solution appears to be colloidal and gives the Tyndall cone. The precipitate contains the carbonate radicle in addition to " available " oxygen and appears to be a peroxidised carbonate. This action will be made t,he subject of furthm investigation. InJluence of Temperature.-In this series of experiments the composition of the reacting solutions was the same in each case. Both solutions were warmed to the requisite temperature before mixing and kept a t this temperature while stirred for half an hour.NaOCl1.35 equivs. (a) Precipitating solution NaOH 1.35 equivs. Temp. of precipitation ... 15" 30" 60" 80" 80" t Available oxygen ......... 1.166 1-176 1.150 1.179 1.181 (b) Precipitating solution Ca( OH) 1.24 equivs. Ca( OCI) 1-40 equivs . Temp. of precipitation ............ 16" 30" 42" GO" 80" '70" t Available oxygen .................. 1.150 1.157 1.161 1.166 1.167 1.157 t After boiling for four hours. It is evident that the temperature of precipitation has practically no influence on the composition of the precipitate formed. More-over the substance is a very stable one for even after boiling for four hours there was no decrease in the content of oxygen. Injluence of Concentration.-In this series of experiments all conditions were constant except the concentrations of the reacting solutions.I n B the concentration was the same as in all previous experiments ; in A it was half and in C double this value. NaOCl1-35 equivs. (a) Precipitating solution NaOH 1-35 equivs. A. B. C. Concentration ............ half unity double Available oxygen ......... 1 . 150 1.150 1.156 (b) Precipitating solution Ca( OH) 1 *68 equivs. Ca( OCI) 1.46 equivs. A. B. C. Concentration ............ half unity double Available oxygen ......... 1.147 1.150 1.155 * Compare Durrant (P. 1396 12 244) and McConnell and Hanes (T., 1597 71 589) who have examined tho precipitation of cobalt solutions by bicarbonates and hypochlorites THE RELATION BETWEEN THE CRYSTAL STRUCTURE ETC.PART I. $1 It is evident from these figures that the concentration of the reactants has practically no influence on the composition of the precipitate. Summary . 1. Hypochlorites free from alkali immediately precipitate from aqueous solutions of cobalt sulphate a slightly peroxidised cobalt sesquioxide of constant composition containing about 1.05 equiv-alents of available oxygen ; but since the peroxide catalytically decomposes the hypochlorite the precipitation is far from quantitative. 2. When less than half an equivalent of hypochlorite is used with an excess of alkali more available oxygen is found in the pre-cipitate than was used in the hypochlorite; this is attributed to atmospheric oxidation of the precipitated hydroxide. 3. A higher degree of oxidation is reached with hypochlorite and alkali than with hypochlorite alone. This is attributed to the formation of a hydroxylated peroxide by direct oxidation of cobalt ous hydrosi de . 4. The temperature has no important influence on the corn-position of the precipitate. The oxide is very stable since it can be kept indefinitely and prolonged boiling causes no loss of available oxygen. 6. The concentration of the reacting solutions likewise has practically no influence on the composition of the precipitate. The author would express his thanks to Principal B. Mouat Jones and Prof. T. C. James for giving him every facility for carry-ing out this work and to Prof. T. M. Lowry for his kindly interest. UNIVERSITY CHEMICAL LABOR4TORY, THE EDWARD DAVIES CHEMICAL LABORATORIES, CAMBRIDGE. ABERYSTWYTH. [Received December Bth 1922.

ISSN:0368-1645    

DOI:10.1039/CT9232300065

出版商:RSC    

年代:1923

数据来源: RSC

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THE RELATION BETWEEN THE CRYSTAL STRUCTURE ETC. PART I. $1 IX.-The Relation between the Crystal Structure and the Constitution of Carbon Compounds. Part I. Compounds of the Type CX4. By ISABEL ELLIE KNAGGS. CONSIDERING the large number of organic compounds which have been examined crystallographically it is remarkable that no kind of comprehensive generalisation connecting their crystalline form with their molecular structure appears to have been reached. Ye 72 KNAGGS THE RELATION BETWEEN THE CRYSTAL STRUCTURE i t is abundantly clear that a coniiesion between the two must exist and no doubt the difficulty which workers have had in interpret'ing their results is to be traced to thc complexity of t,hc relations hip. The extensive investigations which have been carried out in the X-ray analysis of crystals since von Laue's discovery in 1912 of the diffraction of X-rays by crystals have already gone far to solve the problem as regards inorganic compounds.But in organic com-pounds the structures are essentially more complex and present difficulties in the way of X-ray analysis which it will not be easy to surmount. I n the case of aromatic carbon compounds recent work of Sir William Bragg (Proc. Phgsical Xoc. 1921 34 1) on the X-ray analysis of naphthalene and anthracene has afforded striking evidence of the persistence of the benzene ring in one of its forms and therefore perhaps also of the chemical molecule in the crystalline state. If this should be generally applicable to aromatic compounds, the problem in their case would be considerably simplified.In the case of the aliphatic compounds however no such evidence is yet to hand and a t the present stage of the problem it would appear that it is only as the result of the examination of the crystal-line form of the simplest molecular types and the observation of regiilarities which they present that any progress can be expected. Therefore a t the outset of the investigation of which the present communication constitutes a preliminary part it is proposed to examine those aliphatic compounds which are simplest in molecular structure. Before these experiments were commenced or the literature searched the author held as a working hypothesis that the most symmetrical molecular structures should give rise t'o the most symmetrical crystallographic forms although the converse would not necessarily be true.Thus the most symmetrical of all types, namely the type CXa in which X is an element or symmetrical group such as CH3 and which itself possesses cubic symmetry (although not the highest symmetry possible in that system) should give rise to crystals of the cubic system; whilst compounds of this type in which X is a less symmetrical group should give rise to tetragonal crystals. Considered as an expression of what is un-doubtedly a strong general tendency this hypothesis * is fully borne * This rule has already been of service in providing evidence of constitu-tion. The synthesis of methanetetra-acetic acid has recently been described by Ingold and Nickolls (T. 1922,121 1645) and its crystallographic properties are given on p.78. When this acid was first prepared there was doubt as to its constitution which might have been that corresponding with any one of the formula3 C( CH,:CO,H), (CO,H.CH,),CH.CH( CO,TI)~CH,~CO,H and CO,H~CH2~CH2~C(CO,H)(CH2~CO,H),. The crystallographic evidence pointe AND THE CONSTITUTION OF CARBON COMPOUNDS. PART I. 73 out by the evidence brought forward in this papcr and is in agree-ment with the conclusions drawn by Wahl (Proc. Roy. XOC. 1914, [ A ] 90 1) as a result of the optical investigations of a number of simple carbon compounds. The modifications necessary in its detailed application will be discussed hereunder. The first case which has to be considered is that in which X is a single univalent element. There are four examples on record: Wahl has examined the crystalline form of methane (ihid.1912, [ A ] 87 377) and of carbon tetrachloride (ibid. 1913 [A] 89 330), Wahl (Zoc. cit.) and Zirngiebl (Groth " Chem. Kryst." I 330) carbon tetrabromide and Gustavson (op. cit. p. 229; Annulen, 1874,172,173) carbon tetraiodide. Methane itself crystallises below -185.8" in the cubic system. Carbon tetrachloride at -22" crystallises in grains which are isotropic and therefore belong to the cubic system but at -47" a transition into a doubly refracting mass takes place. Carbon tetrabromide crystallises in the cubic system above 46", there being a transition a t that temperature into a monoclinic variety which however has a marked cubic habit the crystals very closely approaching regular octahedra.Carbon tetraiodide crystal-lises in octahedra which are isotropic and therefore cubic in symmetry; no accurate measurements have been made owing to the unstable character of the compound. There does not appear to be an example of a substance CX in which X is a group of two atoms but an instance of one in which X is a group of three atoms is provided by tetranitromethane which has been examined by Wahl (Proc. Roy. SOC. 1913 [A] 89 333). This substance crystallises in the cubic system although a t low temperatures there is a transition into a modification which shows very weak double refraction and probably belongs to a uniaxial system. Of compounds in which X is a group of four atoms one of which must necessarily be carbon or some other quadrivalent element an example is afforded by tetramethylmethane which Wahl (ibid.1913 [ A ] 88 359) found to be cubic with a low-temperature doubly refracting modification which is probably te fragonal. I n all these cases in agreement with the original hypothesis the crystalline form stable at the higher temperature is cubic. The lower-temperature modification with a lower degree of symmetry shown by four of these compounds may reasonably be supposed to plainly to a formula of the typo CX,. The &st formula was therefore accepted by the investigators concerned as a satisfactory basis for further work and was fully confirmod several months later by purely chemical methods (Zoc. C i t . ) . D 74 KNAGGS THE RELATION BETWEEN THE CRYSTAL STRUCTURE be due to a closer packing of the molecular units at lower temper-atures .* The symmetry of a molecule of the type CX, in which X is a single atom is that of a regular tetrahedron that is of Evans’s CBu (hexakis tetrahedral) class of the cubic system possessing there-fore six diagonal planes of symmetry fhe four trigonal symmetry axes of the cubic system and three digonal axes of ordinary symmetry which are also tetragonal “ contra-directional ’ ’ (Evans, Jfin.Nag. 1910 398) axes or Hilton’s (ibid. 1906 261) axes of the second sort. T t might be expected therefore that compounds of this type would crystallise with cubic symmetry as has actually been found. Since each of the bonds from the central carbon atom represents one of tshe four axes of trigonal symmetry essential to all classes of the cubic system compounds of the type CX, in which X is a group of such a nature as not to destroy the trigonal symmetry about these bonds should yield cubic crystals.The compound tetramethylmethane, C(CH,), is one of these three hydrogen atoms being arranged symmetrically about a carbon atom at each corner of the tetrahedron (Fig. 1). It is consistent therefore C to find this compound crystallising in the cubic system. In the compound tetranitromethane C(NO,), the configuration of the nitro-group is uncertain beyond that the nitrogen atom is directly attached to the carbon atom. Of the possible configurations, the linear arrangement *N:O:O is the only one which would allow of the persistence of the four trigonal axes and so lead to the expecta-tion of cubic crystals as actually found.Turning now to more complex cases pentaerythritol C(CF&*OH),, has been examined by Martin (Neues Jahrb. Min. 1891 Beil. Bd. 7, 18) and found to be tetragonal and to crystallise in the ditetragonal-pyramidal class that is the IV Bu class of Evans (Min. Mag. 1907, 360) and therefore to possess a uniterminal axis. The author examined this compound a t Cambridge in 1918 and after repeated FIG. 1. c c * An analogy with this behaviour is to be found in that of the minerals andalusite and kyanitc both of which have the chemical composition Al,SiO,. Andalusite possesses orthorhombic symmetry and kyanite only triclinic symmetry. The density of kyanite (3.62) is higher than that of andalusite (3-18) which would indicate closer packing in the less symmetrical variety AND THE CONSTITUTION OF CARBON COMPOUNDS.PART I. 75 experiments was unable to find the existence of a unitcrminal axis or t o assign other than the symmetry of Evans's IV Bc (holohedral) class to the crystals. Pentaerythritol tetrabromide was found by Jaeger (2. Kryst. Min. 1908,45,543) to belong to Evans's I1 Uc class (holohedral) of the monoclinic system. He regards the symmetry as pseudo-cubic, since by a suitable transformation of face symbols an axial ratio of nearly 1 1 1 and an axial angle of nearly 90" may be obtained. Pentaerythritol tetranitrate pentaerythritol tetra-acetate and methanetetra-acetic acid all crystallise with tetragonal symmetry and with the exception of pentaeryt'hritol tetra-acetate in which the class is uncertain in Evans's IV Bc (holohedral) class.They are described in t'he experimental part of this paper. Tetraethyl orthocarbonate, FIG. 2. C(O*CH,*CH,),, according to Wahl crystallises in the tetragonal system and is pseudo-cubic. Tetraphenylmethane has been ex-amined by Wahl (Proc. Roy. Xoc. 1913, [A] 89 338) who describes the crystals as needles which optically appear to be orthorhombic. Of thesc seven compounds in which S is a complex group five crystallise in the tetragonal system. Of the remaining two tetraphenylmethane, crystallising in the orthorhombic system is perhaps a special case, in which the four phenyl groups have the predominant influence. Pentaerythritol tetrabromide however does appear to be an exception to the general rule though it might be contended that it has a tendency towards a more symmetrical structure as shown by its pseudo-cubic nature.I n molecules of the type CX, in which the X groups are of the type CY,Z i t can easily be seen that the trigonal axes can no longer remain for there can be no three-fold grouping about the corners of the tetrahedron. The symmetry is reduced t o that of Evans's IV Bk (scalenohedral) class of the tetragonal system,* as shown in Fig. 2 which represents the appearance of such a molecule projected on the basal plane. '2, \, \ * E. von Fcdoroff (2. Kryst. Min. 1913 52 22) explained the lack of cubic symmetry in crystals of compounds such as pentaerythritol as due to the carbon atom having a form which is only an approximation t o a regular tetrahedron.In the same paper he put forward the view that the " crystal molecule " is composed of several chemical molecules. D* 76 KNACCGS THE RELATION BETWEEN THE CBYBTAL STRUCTURE By the combination of four such molecular cells in the manner shown in Fig. 3 the symmetry is raised to that of Evans’s IV Bu (ditetragonal-pyramidal) class of the tetragonal system which possesses a uniterminal tetragonal axis and in which therefore, crystals are unlike at the two ends of that axis. By a further combination of two such complex cells one inverted with respect to the other holohedral tetragonal symmetry that is, the symmetry of Evans’s IV Bc class may be reached. Such combinations of cells may be regarded as analogous to the ultra-microscopic twinning considered to be the cause of the assumption of higher symmetry in certain minerals.From these considerations it might reasonably be expected that compounds of the type C(CY,Z) * would crystallise in any of Dhe FIG. 3. classes I V Bk IV Bu IV Bc of the tetragonal system. As already stated above with the exception of pentaerythri-to1 tetrabromide the remain-ing five compounds of this type known all crystallise in t’he tetragonal system and in the case of three of them in the IV Bc (holohedral) class. In the case of two of them, namely penta,erythritol tetra-acetate and tetraethyl ortho-carbonate the class has not certainly been determined. That tetrmethyl orthocarbon-ate should be included with the compounds of the type C(CY,Z) necds perhaps a little explanation From its structural formula co-linear oxygen linkings being assumed it is evident that the groups at the oorners of the tetrahedron are of the type CY,Z.The linking of each of these groups to the central carbon atom by way of an oxygen atom does not affect the symmetry of the molecule. Pentaerythritol constitutes a particularly interesting example, since apparently it may assume either the synimetry of the I V Bu (ditetragonal-pyramidal) class as observed by Martin (Zoc. cit.) or that of the IV Bc (holohedral) class as observed by the author. * It will be seen that in the compounds here discussed Y is hydrogen and with one exception (in which it is bromine) Z is a complex group but one which can be 80 syrnmotrically arranged as to be equivalent to a single atom as far as the symmetry of a molecule of this type is concerned.The latter will always be the cam provided that Z has (t plane of symmetry AND THE CONSTITUTION OF CARBON CO51POUNDS. PART 1. 77 As far as the compounds discussed in this paper are concerned, there is strong evidence that their crystallographic symmetry is an expression of their molecular structure since from the consideration of their molecular configurations (where these are known) the observed crystallographic symmetry may be deduced. Should this be found by further research to be the case for a large number of organic compounds i t would become legitimate to employ crystallographic evidence in determining stereochemical con-figurations in cases where these have not yet been determined by chemical methods.Other compounds of the type CX are in course of preparation for this investigation and it is proposed also to examine compounds of the type @XU and CX,Y,. E x P E n I IVI E N T A L. Pentaerythritol Tetranitrate C(CH,*O*NO,),. This compound was submitted to me for examination by Sir William Pope and ineasuretl by myself a t Cambridge in 1918 when working under Dr. Rutchinson's direction. Crystal system tetragonal. Class liolohedral. Axial ratio : a c = 1 0.506. Forms observed A = (100); p = (111). Angle measured : No. of Meen measurements. Limits. obs. CaIc. Ap = (100) (111) 16 65' 37'-65" 46' 65" 42' 65" 42' p p = (111) (111) 11 48 32-48 40 48 36 * Cleavage (1001 imperfect.Habit square second-order prism terminated by pyramids The crystals are colourless and transparent and of a Optical characters refractive indices as determined by immersion Density determined by suspension in liquid @ = 1.773 (Fig. 4). fair size and quality. in oils o = 1.554 E = 1.553. (corr.). Pentnerythritol Tetra-acetate C(CH,*O*CO*CH,),. Crystal system tetragonal. Class unoertain. Axial ratio : Cleavage perfect basal. Habit long narrow second-order prisms terminated by blunt or sharp pyramids (Fig. 5). The cryshals are colourless and transparent but extremely small and badly developed. The I?-yramid faces when distinguishable are very minute and the only angular measurement obtainable has been from a face of the blunt a c = 1 0.324.Forms observed A = (loo) p = ( I l l ] 78 THE RELATION BETWEEN THE CRYSTAL STRUCTURE ETC. PART I. pyramid p = jlll) on to the prism A = {loo) this angle being 72" 53'. OpticuE characters .- refractive indices as determined by immersion in oils E = 1.483 w = 1.433. Density .- determined by suspension in liquid d;? = 1.213 (corr . ) . FIG. 4. ma. 5. i~et7~n.laetetra-acetir Acid C(CH,*CO,H),. Cryqtal system tetragonal. Class holohedral. Axial ratio : Angle measured : a c = 1 0.560. Forms observed m = {110) p = [llll. No. of Mean measurements. Limits. obs. Calc. p p = (iii) (iii) 9 102 59 103 344 103 11 103 13 p p = (111) ( i i i ) 19 51 61 52 18 52 6 * p p = (111) (iii) 13 127 45.j 128 5 127 54t 127 54 Cleavage none observed.Habit pyramidal with short first-order prisms (Fig. 6). p p = (111) (iii) 9 76" 23j'-76" 59;' 76" 45' 76" 47' pm = (111) (110) 12 51 2O-& 61 49 51 33; 51 364 The crystals are extremely small but moderately well developed and'are clear and colourless. Optical chnracters refractive indices as determined by immersion Density determined by suspension in liquid (carbon tetra-in oils E = 1.518 o = 1.487. chloride and light petroleum) d? = 1.460 (corr.) I desire to express my thanks to Dr. J. W. Evans for his kind help I am also greatlyindebted tlo the Organic and interest in this work, Chemistry Department of the Imperial College, and especially to Dr. C. K. Ingold for much helpful interest and for the facilities which they are offering’ in the preparation of com-pounds for this in-vestigation. My thanks are moreover due to Colonel Lyons and the authorities of the Science Museum for their kindness in lend-FIG. 6. 111 . ing valuable apparatus without which this work could not have been undertaken, IM-PERIAL COLLEGE OF SCIENCE AND TECHNOLOGY, SOUTH KENSINGTON. [Received November Ist 1922.

ISSN:0368-1645    

DOI:10.1039/CT9232300071

出版商:RSC    

年代:1923

数据来源: RSC