摘要:

J O U R N A L OF THE CHEMICAL SOCIETY. TRANSACTIONS. A. UHASTON CHAPMAN. A.W. CROSSLEY,C.M.G.,D.SC.,F.R.S. M. 0. FOWI'ER D.Sc. Ph.I). F.K.S. A. HARDEN DSc. Ph.D. P.R.S. T. A. HENRY D.Sc. '1'. M. LOWRY O.R.E D.Sc. F.R.S. J. C. PHILIP D.Sc. Ph.D. W. J. PoPE,C.B.E.,M.A.,D.SC.,F.R.S. F. L. PYMAN D.Sc. Ph.D. A . SCOTT M.A. D.Sc. F.R.P. G. SENTER D.Yc. Ph.D. S. SMILES D.Sc. J. F. THORPE C.B.E. D.Sc. Ph.D., F.R.S. $bifor : J. C. CAIN D.Sc. Ph.D. Su&-&fibitax : A. J. GREENAWAY. 2,bsisfLtirt Sub.-@&itar : CLABEX'CE SMITH D. Sc. 1917 Vol. CXI. Part I. pp. 1-588. LONDON: GURNEY & JACKSON 33 PATERNOSTER ROW E.C. 191 7 PRINTED IN GREAT BRITAIN BY RICHARD CLAY & SONS LIB~ITED, BRUNSWICK ST. STAMFORD ST. 9.E. 1, AND BUNGAY SUFFOLK CONTENTS.PAPERS COMMUNICATED TO THE CHEMICAL SOCIETY. PAGE 1.-Studies in Ring Formation. Part 11. The Action of Aromatic Amines on Acetylacetone and Renzoylacetone. I I .-T he 8 y n t’hesis of Hydrox y quercetin. By MAXIM I LIAN KIERESSTEIN . 111.-The Friedel-Crafts’ Reaction. Part I. Phthalyl Chloride and the Mechanisni of its Reaction with Benzene. By MAURICE COPISAROW . 1V.-The Resolution of Asymmetric Quinquevalent Nitrogen Compounds. Part I. The Salts of d- and I-Phenylbenzyl-methylallylammonium Hydroxide with cl- and I-a-Brotno-camphor-rr-sulphonic Acid. By JOSEPH REILLY . . V.-Lead Subiodide and an Improved Method for Preparing Lead Suboxide. The Solubility of Lead Iodide. By HENRY GEORGE DENHAM , V1.-The Displacement of Sulphonic Acid Groups in Amino-sulphonic Acids by Halogen A4toms.By JOHN JOSEPH SUDBOROUGH and JAMIAT VISHINDAS LAKHUMALANI VI1.-Xelationship between the Physical Properties of Isomeric Cobaltammines and the Electro-valencies of their Co-ordination Complexes. By RAJENDRA LAL De . VII1.-Spinacene A New Hydrocarbon from certain Fish Liver oils. By A. CHASTON CHAPMAN . 1X.-The Nitration of 2-Acetylamino-3 4-dimethoxybenzoic Acid and 3-Acetylaminoveratrole. By CHARLES STANLEY GIBSON JOHN LIONEL SIMONSEN and MADYAR GOPALA RAU . X.-The Detergent Action of Soap. By SPENCER UMFREVILLE PICKERING . XI.-Mercury Mercapticle Nitrites and their Reaction with the Alkyl Iodides. P a r t 111. Chain Compounds of Sulphur. By PRAFULLA CHANDRA RAY . By EUSTACE EBENEZER ‘FCJRNER .. 1 4 10 20 29 41 51 56 69 86 101 XIL-Azoxycatechol Ethers and Related Substances. By GERTRUDE MAUD ROBINSON . . 109 XII1.-Evidence of the Existence i n Malt of an Enzyme Hydrolysing the Furfuroids of Barley. By JULIAN LEVETT BAKER and HENRY FRANCIS EVERARD HULTON . 121 X1V.-“ Stepped ” Ignition. By RICEIARD VERNON WHEELER . 130 XV.-Studies of the Carbonates. Part 11. Hydrolysis of Sodium Carbonate and Bicarbonate and the Ionisation Constants of Carbonic Acid. By CLARENCE ARTHUR SEYLER and PERCY VIVIAN LLOYD . . 13 iv CONTENTS. PAGE XV1.-Cadmium and Zinc Nitrites. By PRAFULLA CHANDRA RAY . . 159 XVI1.-Notes on the Effect of Heat and Oxidation on Linseed Oil. By JOHN ALBERT NEWTON FRIEND . . 162 XV1II.-Relation between Chemical Constitution and Physio-logical Action in Certain Substituted Aminoalkyl Esters.Part 11. By FRANK LEE PYMAN . . 167 X1X.-Boric Anhydride and its Hydrates. By JAMES ECKERSLEY MYERS . . 172 XX.-A Simple Apparahus for the Washing of Gases. By HAROLD HEATII GRAY. . 179 XX1.-Solvent Effect and Beer’s Law. By ALFRED WALTER STEWART and ROBERT WRIGHT . 183 XXI1.-Acyl Derivatives of Paradiazoiminobenzene. By GILBERT T. MORGAN and ADOLPH WILLIAM HENRY UPTON . 187 XXII1.-Chromium Phosphate. By ALFRED FRANCIS JOSEPH and WILLIAM NORMAN EAE . . . . 196 SOME MAIN LINES OF ADVANCE IN THE DOMAIN OF MODERN ANALYTICAL CHEMISTRY. A Lecture delivered before the Chemical Society on March 19th 1917. By A. CHASTON CHAPMAN . . 203 XX1V.-The Nitration of Isomeric Acetylaminoi~~ethoxybenzoic Acids.By JOHN LIONEL SIMONSEN and MADYAR GOPALA I<AU . . 220 XXV.-The Detection of Traces of Mercury Salts for Toxico-logical Purposes. By KERTDALL COLIN BROWNIKG . . 236 XXV1.-The Action of Bromine Water on Ethylene. By JOHN READ and MARGARET MARY WILLIAMS . . 240 XXVT1.-Trimethyl Glucose from Cellulose. By WILLIAM SMITH DENHAM and HILDA WOODHOUSE . . 244 XXVII1.-The Le Chntelier-Brmu Principle. By LORD RAYLEIGH O.M. . 250 XXIX.-The Structure of Inorganic Compounds. By SAMUEL HENRY CLIFFORD BRIGGS . . 253 XXX.-The Propagation of Flame in Mixtures of Acetone and Air. By RICRARD VERNON WHEELER and ARNOLD WHITAKER . . 267 ANNUAL GENERAL MEETIXG . . 273 PRESIDENTIAL ADDRESS . . 288 OBITUARY N~TICES . . 312 XXX1.-The Action of Sulphur Dioxide on Metal Oxides.Part I. By DALZIELLEWELLYN HANMICK . 37 CONTENTS. V PAUR XXXI1.-Studies in Catalysis. Part VI. The Mutual Influence of two Reactions Proceeding in the Same Medium. By ROBERT OWEN GRIFFITH ALFRED LAMBLE and WILLIAM CUDMORE MCCULLAGH LEWIS . 389 XXXII1.-The Properties and Constitution of some New Basic Salts of Zirconium. By ERNEST HARRY RODD . . 396 XXX1V.-Methyl Nonyl Ketone from Palm Kernel Oil. By ARTHUR HENRY SALWAY . . 407 XXXV.-The Infliience of Pressure on the Ignition of a Mixture of Methane and Air by the Impulsive Electrical Discharge. By RICHARD VERNON WHEELER . . . 411 XXXVL-Velocity of Decomposition and the Dissociation Con-stant of Nitrous Acid. By PRAFULLLA CHANDRA RAY, MANIK LAL DEP and JNANENDRA CHANDRA GHOSH .. 413 XXXVIL-A Simple Method of Preparing Potassium Stanni-chloride. By JOHN GERALD FREDERICK DRUCE . . 418 XXXVXI1.-The Alkaloids of Ipecncuanha. Part 11. By FRANK LEEPYMAN . . 419 XXX1X.-Studies on the Walden Inversion. Part P. The Kinetics and Dissociation Constant of P-Phenyl-a-bromo-propionic Acid. By GEORGE SENTER and GERALD HARGRAVE MARTIN . . . . 447 XL.-Studies in Catalysis. Part VII. Heat of Reaction, Equilibrium Constant and Allied Quantities from the Point of View of the Radiation Hypothesis. By WILLIAM CUDMORE MCCULLAGB LEWIS . . 457 XLI-The Hydration of Ions and Metal Overvoltage. By EDGAR NEWBERY . . 470 XLI1.-The Crystal Form and Isomerisin of Some Ferro-XLII1.-Compounds of Calcium Chloride and Acetone. By LANCELOT SALISBURY RAGSTER .. 494 XL1V.-The Constitution of Internal Diazo-oxides (Diazo-phenols). Part 11. Hy GILBERT T. MORGAN and HENRY PHILIP TOMLINS . . . 497 XLV.-Alkaloidal Derivatives of Mercuric Nitrite By PRAFULLA CHANDRA R l i ~ . . 507 XLV1.-Synthesis of ap-Thiocrotonic Acid. By PRAFULLA CHANURA RAY and MANIK LAL DEY . . 510 XLVII. -Studies in the Phenylsuccinic Acid Series. Part IV. The I-Menthyl Esters of the Diphenylsuccinic Acids. By HENRY WREN and CHARLES JAMES STILT . . 513 XLVII I. -At temp t s t o Prepare Asy tnme tric Quinquevalent Nitrogen Compounds. Part I. 5-Aminosalicylic Acid and Related Compounds. By (the late) RAPHAEL MELDOLA, cyanides. By GEORGE MACDONALD BENNETT . . 490 HENRY STENNETT FOSTER and RAINALD BRIGETMAN . . 53 vi CONTENTS.XL1X.-Attempts to Prepare Asymmetric Quinquevalent Nitrogen Compounds. Part 11. Nitrated Hydroxydi-phenylmines. By (the late) RAPHAEL MELCOLA HENRY L.-Attempts t o prepare A symmetric Quinquevalent Nitrogen Compounds. Part 111. Hydroxyphenylglycine. By (the late) RAPEAEL MELDOLA HENRY STENNETT FOSTER and RAINALD BRIGHTMAN . STENNETT FOSTER and RAINALD BRIGHTMAN . . L1.-The Constitution of Cyanamide. By EMILE COLSON . LI1.-Separation of Secondary Arylamines from Primary OBITUARY NOTICE . LII1.-Contributions to the Chemistry of Caramel. Part I. Caramelan. By MARY CUNNINGHAM and CRARLES DORI~E . L1V.-Action of Acetaldehydeammonia on Quinones. By PRAPHULLA CHANDRA G H ~ S H . LV.-'l'he Conversion of o-Nitroamines into isoOxadiazole Oxides and of o-Nitrosoamines into isoOxadiazoles.By ARTHUR G. GREEN and FREDERICK MAURICE ROWE . . LV1.-The Phosphates of Calcium. Part IV. The Basic Phcsphates. By HENRY BASSETT jun. LVII.-(' Spark-Lengths " in Various Gases and Vapoure. By ROBERT WRIGHT . LVII1.-Constitution of the Salts of XAlkylthiocarbamides. By JOHNTAYLOR . . . . . . L1X.-Phosphorescent Zinc Sulphide. By ELIZABETH MAC-DOUGALL ALFRED WALTER STEWART and ROBERT WRIGHT . LX.-Salts of Thiocarbamide. By AUGUSTUS EDWARD DIXOS . LX1.-Catalysis. P a r t 111. Some Induced Reactions. By LXI1.-Catalysis. Part IV. Temperature Coefficients of LXII1.-A Synthesis of Tropinone. Ey ROBERT ROBINSON . LX1V.-The Pungent Principles of Ginger. Part I. A New Ketone Zingerone (4-Hydroxy-3-methoxyphenylethyl Methyl Ketone) occurring in Ginger.By HIROSHI NOMURA LXV.-The Pungent Principle of Ginger. Part I. The Chemical Characters and Decomposition Products of Thresh's '( Gingerol." By ARTHUR LAPWORTH (MRs.) LEONORE KLEI z PEARSON and FRANK ALBERT ROYLE . LXV1.-The Pungent Principles of Ginger. Part 11. Synthetic Preparations of Zingerone Methylzingerone and some Related Acids By ARTHUR LAPWORTH and FREDERICK HENRY WYKES . Amines. By JOHN THOMAS . NILRATAN DHAB. . Catalysed Reactions. By NILRATAN DHAR . YAGE 546 55 1 554 562 572 589 608 612 620 643 650 663 684 690 707 762 769 777 79 CONTENTS vii PAGE LX VIL-The Determination of Ozone and Oxides of Nitrogen in the Atmosphere. By FRANCIS LAWRY USHER and BASRUR SANJIVARAO . LXVII1.-Compounds of Ferric Chloride with Ether and with Dibenzyl Sulphide.By AQUILA FORSTER CHRISTOPHER COOPER and GEORGE YARROW , LX1X.-The Effect of Additional Auxochromes on the Colour of Dyes. Part T I . Triphenylmethane and Azo-dyes. By PRAPHULLA CHANDRA GHOSH and EDWJN ROY WATSON . LXX.-The Absorption Spectra of Substances containing Con-jugated and Unconjugated Systems of Triple Bonds. By ALEXANDER KILLEN MACBETH and ALFRED WALTER STEWART . LXX1.-The Uniform Movement of Flame in Mixtures of Acetylene and Air. By WILLIAM ARTHUR HAWARD and SOSALE GARALAPURY SASTRY . Part I. The Mechanism of the Interaction of Formaldehyde and Ammonium Chloride ; the Preparation of Methylamine and of Dimethylamine. By EHIL ALPHONSE WERNER . LXXIIL-The Liberation of Hydrogen Sulphide from Gob Fires in Coal Mines.By THOMAS JAMES DRAKELEY . LXX1V.-The Constitution of Carbamides. Part IV. The Mechanism of the Interaction of Urea and Nitrous Acid, LXXV.-A Theory of the Mechanism of the Phytochemical Synthesis of certain Alkaloids. By ROBERT ROBIXSON . LXXV1.-Reduction of Aliphatic Nitrites to Amines. By PANCHANAN NEOGI and TARINI CHARAN CHOWDHURI . LXXVI1.-Experiments on the Orientation of Substituted Catechol Ethers. By THOMAS GILBERT HENRY JONES and ROBERT ROBINSON . LXXVII1.-The Scission of Certain Substituted Cyclic Catechol Ethers. By GERTUDE MAUD ROBINSON and ROBERT ROBINSON . . . By ELLEN MARGARET HINDMARSH ISABEL KNIGHT and ROBERT ROBINSON . By ANNIE MARY BLEAKLY ORR ROBERT ROBINSON and MARGARET MARY WILLIAMS .LXXXI. -Veratricsulphinide. By JANET FORREST MCGILLIVRAY BROWN and ROBERT ROBINSON . LXXXI1.-Researches on Pseudo-bases. Part 11. Note on some Berberine Derivatives and Remarks on the Mechanism of the Condensation Reactions of Pseudo-bases. By GERTRUDE MAUD ROBINSON and ROBERT RORINSQN LSXI1.-Methylation by Means of Formaldehyde. By EMIL ALPHONSE WERNER . . . LXXIX.-5-Bromoguaiacol and some Derivatives. LXXX.-The Action of Halogens on Piperonal. . 799 80'3 815 829 841 8 44 s53 863 876 899 903 929 940 946 952 95 ... V l l l CONTENTS PAQE LXXXII1.-The Absorption Spectra of some Polyhydroxy-anthraquinone Dyes in Concentrated Sulphuric Acid Solu-tion and in the State of Vapour. By DAVID B. MEEK . 969 LXXX1V.-Action of Phenylhydrazine on Opianic Nitro-opianic and Phthalonic Acids Some Derivatives of Hydrazo- and Azo-phthalide.By PRAFULLA CHANDRA MITTER and JNAKENDRA NATH SEN . . 985 LXXXV.-Studies of the Carbonates. Part 111. Lithium, Calcium and Magnesium Carbonates. By CLARENCE ARTHUR SEYLER and PERCY VIVIAN LLOYD . . 994 INTERNATIONAL ATOMIC WEIGHTS . . 1001 LXXXV1.-The Temperature of Ignition of Gaseous Mixtures. By JAMES WALLACE MCDAVID . . 1003 LXXXVI1.-Disodium Nitrite an Additive Compound of Sodium Nitrite and Sodium. By EDWARD BRADFORD MAXTED . . 1016 LXXXVIX1.-Studies in the Phenylsuccinic Acid Series. Part V. The Inter-conversion of the Esters of r- and meso-Diphenylsuccinic Acids. By HENRY WREN and CHARLES JAMES STILL . 1019 LXXX1X.-Derivatives of n-Butylauiline. By JOSEPH REILLY and WILFRID JOHN HICKINBOTTOM . . 1026 XC.-The Limitations of the Balance. By EERTRAM BLOUNT 1035 XCL-3 4-Di-p-nitrotetraphenylfuran. By ARTHUR GORDON FRANCIS . . 1039 XCI1.-The (‘ Uniform Movement ” during the Propagation of Flame. By WALTER MASON and RICHARD VERNON WHEELER 1044 XC1II.-The Hydrolysis of Sodiuin Cyanide. By FREDERICK PALLISER WORLEY and VERE ROCHELLE BROWNE . 1057 XC1V.-The Polysulphides of the Alkali Metals. Part 111. The Solidifying Points of the Systems Sodium Mono-sulphide-Sulphur and Potassium Monosulphide-Sulphur. By JOHN SMEATH THOMAS and ALEXANDER RULE . XCV.-Studies in Catalysis. Part VJ 11. Thermochemical Data and the Quantum Theory. High Temperature Xeactions. Ey WILLIAM CUDMORE MCCULLAGH LEWIS. . . 1086 THE RELATION BETWEEN CHEMICAL COXSTITUTION AND PHYSIO-LOGICAL ACTION. A Lecture delivered before the Chemical Society on December 6th 1917. . . 1063 By FRANK LEE PYMAN. ‘110

ISSN:0368-1645    

DOI:10.1039/CT91711FP001

出版商:RSC    

年代:1917

数据来源: RSC

摘要:

4 NIERENSTEIN THE SYNTHESIS OF HYDROXYQUERCETIN. 1 I. - The Synthesis of Hydwxyquercetin. By MAXIMILIAN NIERENSTEIN. BY the oxidation of quercetin (I) with chromic acid Nierenstein and Wheldale (Ber. 1911 44 3487) obt,ained quercetone (11), which yields hydroxyquercetin (111) on simult'aneous acetylation and reduction and subsequent saponification NIERENSTEfN THE SYNTHESIS O F HYDROXYQUERCETIN. 5 Hydroxyquercetin is isomeric with gossypetin quercetagetin, and myricetin b u t not identical with either of them (compare Nierenstein T. 1915 187 869). The synthesis of hydroxy-qucrcetin which was undertaken with the view of establishing the correctness of the above formula was carried out on the same lines as that of quercetin (Kostanecki Lampe and Tambor Ber., 1904 37 1402) and is based on the following scheme of reactions, which are fully described in the experimental p a r t : Me0 Me0 0 OMe (VI.) (VII.) The demethylation of this pentamethoxy-compound yielded liydroxyquercetin with the properties previously described (Zoc.cit.). E X P E R I M E N T A L . The 1 2 3 5-tetrahydroxybenzens (phentetrol) required for this investigation was prepared according to Oettinger's method (Monatsh. 1895 16 248) who seems to have met with difficulties in preparing it from picric acid on a large scale. These difficulties can apparently be overcome by using the following slight modifi-cation of his method. It' consists in adding hydrochloric acid during the transformation of trihydroxyaniline into tetrahydroxy-benzene and subsequently maintaining the solution strongly acid.This modification rendered possible also the preparation of the following substances : 2 3 4 6-Tetrahydroxybenzoic acid C,H(OH),*CO,H is prepared by the actisn of potassium hydrogen carbonate on tetrahydroxy-benzene a stcream of carbon dioxide being constantly passed through the liquid (compare Clibbens and Nierenstein T. 1915 107 1493). The acid crystallises from water when slightly acidified with dilute sulphuric acid in needles which melt and evolve carbon dioxide a t 308-310°. A t 130-135O the acid loses 1 molecule of water. (Found H,O = 9.42. C7H,0,,H,0 requires H,O = 9.11 per cent.) The acid gives all the colour reactions described by Oettinger for tetrahydroxybenzene and also the violet coloration with concen 6 NIERENSTEIN THE SYNTHESIS OF HYDROXYQUERCETIN.trated nitric acid described by Kostanecki (BeT. 1885 18 3206; compare also Dean and Nierenstein Ber. 1913 46 3871) for pyrogallolcarboxylic acid : 0.1753 gave 0.2907 CO and 0.0572 H20. The tetra-acetyl derivative C7H202(OA~)4 crystallises from 0.1512 gave 0.2782 CO and 0.0652 H,O. C,,H1401 requires C=50*55 ; H =4*49 per cent. The tetrabenzoyl derivative C,H202(OB~)4 which is prepared in the usual way using pyridine as a solvent crystallises from alcohol in long prismatic needles melting a t 248-249O: Cz45.23; H=3*66. C,H606 requires C = 45-17 ; H = 3-28 per cent. alcohol in needles melting a t 274-276O: C=50*17; H=4.83. 0.1508 gave 0.3926 CO and 0.0458 H20. Methyl 2 3 4 6-tetramethoxybenzoate C,H(OMe),*CO,Me is It C=70*99; H=3-40.C35H22010 requires C = 69.77 ; H = 3-66 per cent. obtained by the action of diazomethane in ethereal solution. crystallises from benzene in silky needles melting a t 134-136O : C=56*44; H=6'20. 0.1214 gave 0.2512 CO and 0.0672 H20. 2 3 4 6-Tetramethoxybenzoic acid C,H,O,(OMe), is obtained by hydrolysing the above-mentioned methyl ester. It crystallises from a mixture of alcohol and benzene in needles melting a t Cl2HI6O6 requires C =56*25 ; H = 6.25 per cent. 184-186' : 0.1462 gave 0.2918 CO and 0.0722 H20. CI1Hl4O6 requires C = 54.55 ; H = 5.79 per cent. 2 3 4 6-Tetramethoxybenzoyl chloride C6H(OMe)4*COC1 is prepared by warming 2 grams of the acid with a slight molecular excess of phosphorus pentachloride and removing the phosphoryl chloride formed at 35-400/10-12 mm.The residue is dissolved in light petroleum and filtered when the product separates in hair-like needles which melt a t 104O: C =54.44 ; H= 5.53. 0-2004 gave 0-1114 AgCl. C1= 13.76. C,,H,,O,Cl requires C1= 13.63 per cent. 2 3 4 6 Tetrahydroxyacetophenone C6H(OH),*COMe. Ten grams of 1 2 3 5 tetrahydroxybenzene are dissolved in freshly distilled glacial acetic acid and heated for fifteen t o twenty minutes with granulated zinc chloride which is prepared by pour-ing molten zinc chloride into s-tetrachloroethane. After cooling, the solution is diluted with water and the precipitate crystallised from alcohol. Faintly yellow needles melting a t 204-205O ar NIERENSTEIN THE SYNTHESI3 OF HYDROXYQUERCETIN.7 obtained from alcohol and also from dilute acetic acid. is 84-85 per cent. of the t,heoretical: The yield 0*1568* gave 0.2989 CO and 0.0637 H,O. C8H80 requires C = 52.17 ; H = 4.35 per cent. The phenylhydrazone C,H(OH),*CMe:N2Ph crystallises from s-tet,rachloroethane in deep red prismatic needles melting and decomposing a t 248-251O : C=51.98; H=4*54. 0.1039 gave 9.5 C.C. N (moist) a t 22O and 760 mm. CI4Hl4O4N2 requires N = 10.26 per cent. N=10*35. 2 6-Bih ydroxy-3 4-dimethoxyacetopheno?~e, C,H(OMe),(OH),*COMe. To a boiling alcoholic solution of 10 grams of tetrahydroxyaceto-phenone saturated for some time with hydrogen 15 grams of methyl sulphate and 8.6 grams of sodium hydroxide dissolved in alcohol are slowly added and the mixture is kept boiling for three to four hours hydrogen being passed through all the time.After evaporation of the alcohol steam and hydrogen are passed through, when a small quantity of tetramethoxywetophenone, CGH (0 Me),. co Me, passes 0ver.t (This crystallises from dilute alcohol in colourless, silky needles melting a t 92-93O. It is best obtained by the action of diazomethane on tetrahydroxyacetophenone in ethereal suspension. Found C= 59-63 ; H = 6.94. C12Hl,0 requires C=59.96; H=6*67 per cent.) On acidification with dilute sulphuric acid a precipitate is formed which crystallises from dilute alcohol in colourless silky needles melting a t 166-168O. The yield is 94 per cent. of the theoretical: 0.1798 gave 0.3746 CO and 0.0919 H,O. C=56*73; H=5.72.Cl0H,2O5 requires C = 56.56 ; H = 5-65 per cent. 2-Hydroxy-3 4 ; 6-trimethoxyacetophenone, CGH (OMe)3(0H)*COMe. The reaction is carried out on the same lines as t h a t used by Waliaschko (Ber. 1909 42 727) for the methylation of quercetin. Ten grams of the dry disodium salt of 2 6-dihydroxy-3 4-dimeth-oxyacetophenone are triturated in a mortar with 13.7 grams of methyl sulphate. After some time evolution of heat occurs and * Dried at 150". t Mr. H. F. Dean when working in this laboratory found that a modification on similar lines of Perkin and Weizmmn's method (T. 1906 89, 1649) for the preparation of trimethoxygdlic acid gives better yields than bhose obtained by them the increase amounting to about 16 per cent 8 NIERENSTEIN THE SYNTHESIS OF HYDROXYQUERCETIN.the product is then allowed to remain in a desiccator for two to three days. On acidification 2-hydroxy-3 4 6-trimethoxyaceto-phenone and 6-hydroxy-2 3 4-trimethoxyacet~phenone are obtained which can be separated by fractional crystallisation the former being less readily soluble in alcohol than the latter. 2-Hydroxy-3 4 6-trimethoxyacetophenone crystallises from alcohol in large cubes which melt a t 125-126O. The yield is 95 per cent. of the theoretical : C=58*01; H = 6.95. 0.1826 gave 0.3884 CO and 0.1054 H,O. CtllH140 requires C = 58.41 ; H = 6.19 per cent. The constitution of this compound can be regarded as proved, since it forms on oxidation with chromic acid in acetic acid solu-tion 3 4 6-trimethoxy-2 5-quinoacetophenone, This crystallises from glacial acetic acid in red cubes which melt and decompose a t about 235-238O: 0.1794 gave 0.3627 CO and 0.0654 H20.I n order to convert the quinone into the corresponding C=55*10; H=4-06. C1,H120 requires C = 55.00 ; H = 4.88 per cent. 2 5-dihydroxy-3 4 6-trimethoxyucetophenoneJ C,(OMe),(OH),-COMe, it is heated with zinc dust and acetic anhydride the resulting white precipitate being hydrolysed with dilute sulphuric acid. The product crystallises from alcohol and water in microscopic, faintly yellow plates which melt a t 174-176O : 0.2100 gave 0.4218 CO and 0.1088 H20. 6-Hydroxy-2 3 4-trimet?~oxyacetopheno.lze, C=54*75; H=5-75. C11H1406 requires C= 54.54 ; H = 5-78 per cent. C,H(OMe),(OH)*COMe, crystallises from alcohol in needles melting a t 164-65O.It does not yield a quinone on oxidation with chromic acid: 0.1788 gave 0.3824 CO and 0.1046 H20. C =58*33 ; H = 6-55. CI1Hl4O5 requires C =58*41; H = 6.19 per cent,. 2-Hydroxy-3 4 6-trimethoxypheilzyl 3 4-Dim.ethoxystyry1 Ketone (IV). To 10 grams of 2-hydroxy-3 4 6-trimethoxyacetophenone and 7 grams of veratraldehyde dissolved in 50 C.C. of alcohol are added 20 grams of a 50 per cent. solution of sodium hydroxide in water. Themixture is left for about three to four days during which tim NIERENSTEIN THE SYNTHESIS OF HYDROXYQUERCETIN. 9 i t solidifies. After acidification with dilute hydrochloric acid and drying on a porous plate it crystallises from alcohol in yellow needles which melt a t 143O. The yield corresponds with 84 per cent.of the theoretical : 0.1206 gave 0.2839 CO and 0.0646 H,O. The acetyl derivative crystallises from alcohol in colourless 0.1696 gave 0.3943 CO and 0.1026 H20. C=64*21; H=5*99. C2,HE07 requires C = 64.17 ; H =5*89 per cent. needles melting a t 168-169O : C =63*41; H = 6.77. C,,H,,O requires C = 63.48 ; H = 5-82 per cent. 5 7 8 31 4~-Pentamethoxyflavanone (V). Five grams of the above ketone are dissolved in 750 C.C. of alcohol containing 25 C.C. of concentrated hydrochloric acid and 75 C.C. of water. The solution is heated under reflux for thirty hours and is then left to remain in an open dish for about a week when at first yellow crystals of the unchanged ketone (0.84-1-26 grams) separate. 'The filtrate gives after longer keeping (about three to four days) the flavanone which is nearly colourless.It is purified by dissolving it in a little s-tetrachloroethane from which it separates as a colourless powder. It crystallises from alcohol in long colourless needles which melt a t 186-187O. The yield of the crystallised flavanone is about 64 per cent. of the theoretical : 0.1334 gave 0.3129 CO and 0.0712 H,O. C=63*97; H=5*97. C,,H2207 requires C = 64-17 ; H =5*89 per cent. 3-isoiVitroso-5 7 8 3' 4r-pe?ztamethoxyflavanone (VI). Five grams of the flavanone dissolved in alcohol are boiled with 15 grams of amyl nitrite and 150 C.C. of concentrated hydrochloric acid. The isonitroso-derivative is purified after the evaporation of the alcohol by dissolving in a 10 per cent. solution of sodium hydroxide in water and precipitation with acetic acid.It crystal-lises from alcohol in faintly yellow needles which melt and decorn-pose a t about 218-220°: 0.1829 gave 5.8 C.C. N (moist) a t 22O and 758 mm. N=3*66 CvlHelOsN requires N = 3.47 per cent. 5 7 8 ; 31 4~-Perctamethoxyflavonol (VII). Five grams of the isonit,roso-derivative are dissolved in glacial acetic acid and heated with dilute sulphuric acid under reflux for about five hours when the flavonol separates 011 keeping. It crystallises from alcohol in small needles which melt a t 147-149O, B 10 COPISAROW THE FRIEDEL-CRAFTS’ REACTlON. PART I. as found by Nierenstein and Wheldale (Zoc. cit.) for this product, with t,he exception that it does not sinter a t 136-138O as previously observed. (Found C = 61.92 ; H = 5-14. C,,H,,O, requires C= 61-85 ; H = 5-10 per cent.) Hydroxy quer ce tin (111). The free hydroxyquercetin is obtained on heating the penta-methoxy-derivative for several hours with concentrated hydriodic acid (Zeisel). It crystallises from dilute alcohol in small yellow needles melting a t 354-355O (Nierenstein and Wheldale give 352-355O). The melting point is not depressed when mixed with hydroxyquercetin from quercetone (Nierenstein and Wheldale Zoc. c i t . ) or isoquercetone (Nierenstein T. 1915 107 869). (Found * : C=56.42; H=3*38. C,,H,,08 requires C=56*63; H=3.17 per cent.) It yields on treatment with diazomethane in ethereal suspension the hexamethoxy-derivative previously described by Nierenstein (Zoc. cit. p. 872) which crystallises from alcohol in colourless needles melting a t 142-143O as previously observed. The product was not analysed. BIOCHEMICAL LAB ORATORY, CHEMICAL DEPARTMENT, UNIVERSITY OF BRISTOL. [Received October 18th 1916.

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J O U R N A L O F THE CHEMICAL SOCIETY. TRANSACTIONS. A. CHASTON CHAPMAN. A. W. CROSSLEY C.M.G. D.Sc.,F.R. S. M. 0. FOIZSTER D.Sc. Ph.D. F.R.S. A. HARDEN Ii.Sc. Ph.D. F.R.S. T. A. HENRY D.Sc. T. M. LOWKY O.B.E.,D.Sc. F.R.S. J. C. PHILIP D.Sc. Ph.D. Qantmitfee o f @ubIitrrtiait : W.J.POPE C.B.E. M.A.,D.Sc. F.R.S. F. L. PYMAN D.Sc. Ph.D. A. SCOTT M.A. D.Sc. F.R.S. G. SENTER D.Sc. Ph.D. S. SMILES D.Sc. J. F. THORPE C.B.E. D.Sc. Ph.D., F. R. S. &bitor : J. C. CAIN D.Sc. Ph.D. S u b - m t a r : A. J. GREENAWAY. 8seistzt.d Sub-$bitor : CLAREX’CE SMITH D.Sc. 1917. Vol. CXI. Part 11 pp. 589-end LONDON: GURNEY & JACKSON 33 PATERNOSTER ROW E.C. 1917 PRINTED IN GREAT BRITAIN BY RICHARD CLAY & SONS LIB~ITED, BRUNSWICK ST. STAMFORD ST. 9.E. 1, AND BUNGAY SUFFOLK

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10 COPISAROW THE FRTEDEL-CRAFTS' REACTlON. PART I. IIL-The Friedel-Crafts' Reaction. Part I. Phthalyl Chloride and the Mechanism oj'its Reaction with Benzene. By MAURICE COPISAROW. FRIEDEL and Crafts (Compt. rend. 1877 84 1452; Ann. Chim. Phtys. 1884 [vi] 1 523) and Baeyer (Annalen 1880 202 51) by condensing phthalyl chloride with benzene in the presence of aluminium chloride obtained diphenylphthalide (phthalophenone) as the main product and some anthraquinone and o-benzoylbenzoic acid as by-products. Haller and Guyot (Bull. Soe. chim. 1897, [iii] 17 873) on repeating the condensation succeeded in isolating a small quantity of diphenylanthrone. Scheiber (Annalen 1912 389 121) however found the main product of the reaction when carried out a t a low temperature t o be o-benzoylbenzoic acid.Zoc. cit. p. 3490). * Dried at 160" when it loses 1H,O (compare Nierenstein and Wheldale COPXSAROW THE FRIEDEL-CRAFTS' REACTION. PART r. 11 The present author in studying this reaction isolated in addi-tion to the abovementioned substances phenyloxanthranol and a new acid tetraphenylmethane-o-carboxylic acid. This acid and diphenylanthrone were also obtained by condensing diphenylphthalide with benzene. These results taken in conjunction with the work of Ott (Annulen 1912 392 274) and Scheiber (Bey. 1913 46 2368) on the isomerism of phthalyl chloride; of Meyer (Monatsh. 1904 25, 475 1177; 1907 28 1211) on the isomeric chlorides and esters of o-bsnzoylbenzoic acid * ; and of Copisarow and Weizmann (T, 1915, 107 878) on the formation of phthalides of the benzene naphth-alene and carbazole series throw much light on the mechanism of the reaction but indicate i t to be of a complex character.The complexity of the relaction is due to : (1) The tendency of phthalyl chloride and its condensation pro-ducts t o pass under the influence of aluminium chloride from the open-chain to the cyclic form by ( a ) isomeric change and ( b ) elimin-ation of one o r more molecules of water or hydrogen chloride and (2) The capacity of the cyclic compounds so formed t o condense further with one or more molecules of benzene. Theref ore by changing the e'xperimental conditions such as tem-perature duration of the reaction ratio of substances taken and manner and order of introduction of the reagents (the necessity of the latter is as yet not quite realised) a whole series of products may be obtained.The yield of the products of the advanced stages of the reaction is influenced not only by the experimental condi-tions referred to above but also by the configuration of the sub-stances in question steric hindrance being brought into prominence, thus greatly inhibiting the progress of the reaction. The formation of diphenylanthrone was attributed by Haller and Guyot (Zoc. cit.) to the condensation of benzene not with phthalyl chloride but with phthalylene tetrachloride assumed t o be present in phthalyl chloride the proof being the formation of diphenyl-anthrone on condensing phthalylene tetrachloride with benzene. The evidence brought forward in this paper all goes to show that diphenylanthrone phenyloxanthranol and tetraphenylmethane-o-carboxylic acid are all products of the condensation of phthalyl chloride with benzene.The evidence is as follows: (1) The formation of diphenylanthrone and tetraphenylmethanec o-carboxylic acid by the condensation of diphenylphthalide with benzene. * Meyer's results are contradicted by Martin ( J . Amner. Chem. SOC. 1916, 38 1142) and McMullen (ibid. 1228). B" 12 COPISAROW THE FRIEDEL-CRAFTS’ REACTION. PART I. (2) The uniform character of the reaction with samples of phthalyl chloride derived from different sources and obtained with certain modifications in the method of preparation. (3) The yield of these products whilst being very small (the combined total is about 2 per cent.) owing to skric hindrance so generally manifest in the tetraphenylmethane series still fluctuates so considerably as t o suggest that their formation is due to a whole series of consecutive reactions rather than a one-stage reaction, subject to the usual effect of experimental conditions.(4) Estimations of chlorine in various specimens of phthalyl chloride do not indicate the presence of phthalylenel tetrachloride. (5) Such reactions are not without precedent as cases are known where carboxylic acids were’ obtained by the condensation of y-lactones with benzene and its homologues. Thus Eijkman (Chem. Weekblnd 1904 1 421) by condensing y-methylbutyro-lactone and phenyl-y-methylbutyrolactone with benzene and toluene respectively obtained y-substituted butyric acids according t o the scheme 7 €3,.C RR’ $lH,*CRR’R’‘ CH,--CO CH,*CO,H ’ >O + HR’ = I n the present instance the acid originally formed losing one molecule of water under the influence of the condensing agent, passes t o a large eatent into a closed-chain compound (diphenyl-anthrone) a process not uncommon in the aromatic series. The formation of phenyloxanthranol in the course of the reaction between phthalyl chloride and benzene cannot be attributed t o the condensation of benzene with phthalylene tetrachloride (Haller and Guyot Zoc. cit.) as there is no indication of the presence of the latter in phthalyl chloride or t o the isomerisation of diphenyl-phthalide according to the scheme : OH I which might suggest itself,* as the experimental evidence does not corroborate this view.Considering the fact that the chlorine is far more stable in the asymmetric than the symmetrical form of acid chlorides (Ott Zoc. c i t . ) it is quite possible that whilst the main portion of the isomerised chloride of o-benzoylbenzoic acid reacts according to * Such isomerisation simultaneous with chlorination does take place on treating diphenylphthalide with phosphorus pentachloride (Haller and Guyot, loc. cit.) COPISAROW THE PRIEDEL-CRSFTS’ REACTION. P-4RT I. 13 equation V a small proportion condenses according to equation X, phenyloxanthranol being formed from its chloride which is derived from the isomerised o-benzoylbenzoyl chloride. This conception finds support in a number of known cases of Friedel-Crafts’ reac-tions where the oxygen and not the halogen atom of the molecule takes part in the condensation (Combes Bull.SOC. chim. 1886, [ii] 45 226; Biltz Ber. 1893 26 1952; Dienesmann Compt. rend. 1905 141 201; Boeseken Bec. trav. chirn. 1911 30 381; Frankforter and Kritchevski J . Amer. Chem. SOC. 1914 36 1511; 1915 37 385). Considering the mechanism of the reaction between phthalyl chloride and benzene in the light of the new facts it is necessary to deal with the method and conditions of formation of each of the numerous products of reaction. (1) o-Benzoylbenzoic A 4.-The formation of the acid is repre-sented by the equations: (11.) and the most favourable conditions are paratively short duration of reaction and benzene and aluminium chloride before chloride thus preventing the latter from densation.low temperature com-the introduction of the that of the phthalyl isomerising before con-(2) A nthraquinone.-The formation is represented by equations I and (111.) the best conditions being molecular quantities of benzene and phthalyl chloride the order of introduction remaining the same as in the previous case. The low yield of anthraquinone is due to the fact that the reac-tion ceases with the formation of o-benzoylbenzoyl chloride when carried out in the cold. On warming isomeric changes of the phthalyl and o-benzoylbenzoyl chlorides take place which in the presence of benzene lead to diphenylphthalide. It is difficult to represent any appreciable part of the anthraquinone as being derived from the phthalic anhydride contaminating the phthalyl chloride first because the anhydride is present in very small amount and secondly the o-benzoylbenzoic acid is not readily con-verted into anthraquinone (Pechmann Ber.1881 14 1865) 14 COPISAROW THE FRIEDEL-CRAFTS’ REACTJON. PART I. (3) Diphenylphtha1ide.-The formation is represented either by equations I and (V. 1 or by equations (VII. ) (Copisarow and Weizmann loc. cit.). When the aluminium chloride is introduced as the last reagent and the reaction started a t a comparatively low temperature (below loo) which is gradually raised the condensation is represented by stages I IV and V. When the reaction is started a t a higher temperature and the benzene introduced after the pht’halyl chloride and aluminium chloride the condensation is represented mainly by stages VI and VII as in this case the isomerisation of the phthalyl chloride from the symmetric to the asymmetrical form precedes the condensation with benzene.(4) Tetmphe;lzylmethane-o-carboxylic A cid C Z ~ L ~ Biphenyl-anthrone.-The formation of these compounds is represented by the equations : 1 (VIII.) (IX.) the favourable conditions being excess of benzene and aluminium chloride and a comparatively high temperature. (5) Phenyloxanthrano1.-The formation of this is for reasons stated above probably represented by equations I IV and (XII. COPISAROW THE FRIEDEL-CR-4FTS' REACTION. PART I. 15 Estimations of chlorine in several specimens of phthalyl chloride from different sources indicate a lower percentage of chlorine than that' theoretically required.The explanation may be found in the fact that small quantities of phthalic anhydride are tenaciously retained in solution by the phthalyl chloride (Bruhl Amnalen 1886 235 13; Ott Zoc. cit.). This affords also an explanation of the observation that whatever the experimental conditions may be the product of condensation of phthalyl chloride with benzene invariably contains some o-benzoyl b enzoic acid. A t temperatures high enough to exclude the formation of this acid from phthalyl chloride the amount of acid accompanying the product of condensation does not exceed 0.25 per cent. I n these cases the percentage of o-benzoylbenzoic acid formed serves as an approximate estimate of the amount of phthalic anhydride dissolved in the phthalyl chloride as the o-benzoyl-benzoic acid does not readily undergo further condensations (Pech-mann koc.cit.). EXPERIMENTAL. Analysis of s-PhthLnlyt Chloride. As a preliminary investigation four specimens of phthalyl chloride were analysed namely (1) Kahlbaum's ; (2) Schuchardt's; (3) prepared by Graebe's method (Amualen 1887 238 329); and (4) prepared by using a large excess of phthalic anhydride as com-pared with the phosphorus pentachloride so as to ensure the absence of phthalylene tetrachloride. The products of preparations (3) and (4) were freed from t'he accompanying phthalic anhydride by repeated cooling filtration, and distillation under diminished pressure (1 2-15 mm.). The analytical data as compared with those theoretically required for phthalyl chloride and certain mixtures of pht,halyl chloride with phthalylene tetrachloride and phthalic anhydride are given below.Substance. Phthalyl chloride (Specimen No. 1) ................................. ................................. Y t (Specimen No. 2) 9 9 (Specimen No. 3) 1 (Specimen No. 4) ............................... 9 theoretical .......................................... + 1 per cent. phthalylene tetrachloride 9 +2 per cent. 9 9 9 -.. 9 9 + 3 per cent. 9 9 99 ". + 1 per cent. phthalic anhydride +2 per cent. , ............ f 3 per cent. , , ............ ............................... ... 9 , ............ 9 7 $ 9 9 1 Chlorine, per cent. 34.87 34.9 34-86 34.88 34-95 35-15 35-35 35.55 34.6 34.2 33.16 COPISAROW THE FRIEDEL-CRAFTS7 REACTION. PART I. The possible suggestion that phthalyl chloride contains both phthalylene tetrachloride and phthalic anhydride thus rendering the chlorine estimation of no value as a guide is scarcely accept-able on the following grounds : (1) Phthalic anhydride being more easily chlorinated than phthalyl chloride it is not! probable that the chlorination of the latter will take place while the former is present. (2) The o-benzoylbenzoic acid which as mentioned above affords an approximate estimate of the proportion of phthalic anhydride in phthalyl chloride indicates only very small quantities of the former in properly purified phthalyl chloride. The benzene employed in the condensations to be described was freed from thiophen first by means of concentrated sulphuric acid and then with aluminium chloride according t o Halier and Michel's method (Bull.SOC. chim. 1897 [iii] 15 1065). The phthalyl chloride used was partly Schuchardt's and partly prepared by the author according to Graebe's method (Zoc. cit.). Condensation of Phthnlyl Chloride with Benzene. Experiment 1.-Forty grams of s-phthalyl chloride were dissolved in 350 C.C. of benzene and 50 grams of finely powdered aluminium chloride added in four or five portions. The reaction which slackened after three t o four hours was completed by heating the mixture on the steam-bath for two 'hours. The mixture was treated with ice and hydrochloric acid and a current of steam passed through to remove the excess of benzene and ensure the complete decomposition of the aluminium organic compounds.The mixture was cooled and filtered the residue washed with cold water and then extracted twice with a hot solution of sodium carbonate and filtered.* On acidifying the cooled filtrate a white powder was precipitated. This was collected washed with cold water and extracted several times with boiling water. On cooling the filtrate white slender needles separated which gave a pure yellow coloration with con-centrated sulphuric acid and were identified as o-benzoylbenzoic acid (crystallised from toluene m. p. 127O). The portion insoluble in boiling water gave a deep green colora-tion wit'h concentrated sulphuric acid unchanged on heating but discharged by water and hydrochloric acid.Owing to the small quantity of material the following method had to be employed in dealing with this product: to below. * The effect of using sodium hydroxide instead of the carbonate is referre COPISAROW THE FRIEDEL-CRAFTS’ REACTION. PART I. 17 The fractions derived from all condensations isolated in a manner identical with that just described and all giving the same coloration with concentrated sulphuric acid were mixed together. The amount so obtained was very small and the investigation of this product was necessarily somewhat limited. Tetraphenylmethane-o-carboxylic A cid.-The acid is fairly readily soluble in all ordinary organic solvents and separates from benzene in small white crystals melting a t above 184O (one crystal-lisation).The magnesium salt was obtained by adding a concentrated solu-tion of magnesium chloride to a solution of the ammonium salt and filtering; on cooling the magnesium salt separated in white, lustrous plates. The silver salt a white crystalline powder which gradually darkens on exposure to light was prepared by treating a boiled ammoniacal solution of the acid with dilute silver nitrate : 0.1306 gave 0.3145 GO and 0.0463 H,O. C=65*68; H=3*94. 0’2860 , 0.0651 Ag. Ag=22*72. C,,H,,O,Ag requires C = 66-24 ; H = 4.07 ; Ag= 22.90 per cent. The main portion insoluble in sodium carbonate was thoroughly extracted with hot arcohol and the smdl residue a white powder, was identified as anthraquinone (crystallised from glacial acetic acid m. p. 285O).The alcoholic extract was found to contain the main product of the reaction namely diphenyphthalide and small quantities of diphenylanthrone and phenyloxanthranol. The separation and identification of these products was effected in the following manner. On cooling the alcoholic solution yellow crystals were obtained, which were collected ; the filtrate somewhat concentrated by evaporation was cooled and a second crop of crystals collected. On adding water t o the filtrate now amounting t o about 15-20 c.c. a white viscid substance separated giving a purple-red colour with concentrated sulphuric acid. It crystallised from glacial acetic acid in white rhombic crystals melting at 208O and was identified as phen yloxant hranol. The purplered coloration with sulphuric acid was found to be a useful guide in detecting traces of phenyloxanthranol.The two crops of crystals obtained above were mixed tdgether, dissolved in alcohol and a dilute solution of potassium hydroxide, equal to about three times the volume of alcohol taken was gradu-ally added with stirring t o the gently boiling alcoholic solution. On cooling white crystals separated which were collected and recrystallised from glacial acetic acid. White needle-shaped crystals melt4ing a t 1 9 2 O were obtained which were identified a 18 COPISAROW THE FRIEDEL-CRAFTS' REACTION. PART I. diphenylanthrone. The alkaline filtrate contained the main pro-duct of the reactLon namely diphenylphthalide as the potassium salt of triphenylcarbinol-o-carboxylic acid (Baeyer A nnalen 1880, 202 51).On acidifying the solution a white precipitate which when crystallised from alcohol melted a t was obtained 1 1 5 O gave a greenish-yellow coloration with concentrated sulphuric acid and was identified as diphenylphthalide (which can be regarded as the lactone of triphenylcarbinol-o-carboxylic acid). When sodium hydroxide was substituted for sodium carbonate in the first treatment of the crude product the extracted acids were found to be contaminated with diphenylphthalide indicating that a hot aqueous solution of sodium hydroxide has some hydrolysing effect on diphenylphthalide. Experiment 2.-When the reaction was carried out a t a some-what higher temperature (just above SO0) the only difference observed in the product was that it was more contaminated by tarry colouring matter.Treatment with alcoholic potassium hydr-oxide was found t o be an excellent means of obtaining pure white diphenylphthalide. Experiment 3.-When the reaction was carried out in a carbon disulphide solution (1 mol. of phthalyl chloride and 4 mols. of benzene) no tetraphenylmethane-o-carboxylic acid or diphenyl-anthrone could be detected in the product and but traces of phenyl-oxanthranol were found. The difference in the products is probably due to the compara-tively low temperature of reaction in a carbon disulphide solution. Experiment 4.-Forty grams of pht,halyl chloride were treated with 50 grams of powdered aluminium chloride in the cold when a dark brown liquid was immediately formed. The formation of this liquid was accompanied with but little evolution of hydrogen chloride.On adding benzene a vigorous reaction took place with the evolution of hydrogen chloride. Continuing the experiment as in No. 1 the product was found to contain merely traces of anthra-quinon'e and phenyloxanthranol the yield of the diphenylphthalide not being appreciably affected. Experiment 5.-The dark brown liquid obtained on treating s-phthalyl chloride with aluminium chloride on keeping or warm-ing begins to evolve hydrogen chloride slowly. The product is a brownish-yellow somewhat. viscid crystalline material which react COPISAROW THE FRIEDEL-CRAFTS’ REACTION. PART I. 19 with benzene but feebly in the cold and even on heating the reac-tion is far from being vigorous or complete.When the mixture containing an excess of benzene (after six hours’ heating on the steam-bath) was treated as in experiment 1, the product was found to consist of phthalic acid and impure diphenylphthalide the yield of the latter being not more than 50 per cent. of that theoretically possible as compared with a yield exceeding 90 per cent. in the first and second experiments. It seems from these results and the work of Ott (Zoc. cit.) and Scheiber (Zoc. cit.) that the aluminium chloride forms with s-phthalyl chloride a very reactive additive compound (dark brown liquid) which on keeping or warming loses hydrogen chloride and passes into a comparatively inert crystalline substitution com-pound in which the phthalyl chloride having undergone an isomeric change is present in its asymmetric form.The reaction of the substitution compound with benzene being very feeble the result is that a considerable proportion of the asymmetric phthalyl chloride remains unacted on and the product, on being extracted with sodium carbonate as in experiment 1, yields the sodium salt of phthalic acid. On prolonged heating, tarry highly coloured substances are formed which greatly con-taminate the main product. Formation of Anthraquinone.-To a mixture of 30 grams of finely powdered aluminium chloride and 8 grams (1 mol.) of benzene in 200 C.C. of carbon disulphide 20 grams (1 mol.) of phthalyl chloride were gradually added. The mixture was kept in ice for four hours so as not to allow the temperature of the mixture to rise above loo and then left over-night a t the ordinary temperature the reaction being completed by heating the mixture on a steam-bath for one hour.The product on being treated as in experiment 1 was found to contain 2 per cent. of the theoretically possible quantity of anthra-quinone the rest of the product being o-benzoylbenzoic acid and some diphenylphthalide. Experiment 7.-When the reaction mixture from experiment 6 was treated- with ice and hydrochloric acid without previously heating it on the steam-bath that is carrying out the reaction below ZOO anthraquinone was found only in traces the product consisting of benzoylbenzoic acid and some phthalic acid. Experiment 8. Condensation of Biphenylphthnlide with Benzene.-Twenty-eight grams of diphenylphthalide were dissolved in 250 C.C.of benzene and 50 grams of powdered aluminium chloride added in two o r three portions. The feeble reaction was stimu-Experiment 6 20 REILLY THE RESOLUTION OF ASYMMETRIC lated by heating the mixture on the steam-bath for six hours. The brown product on being treated in a manner identical with that adopted in experiment 1 was found t o consist of a little tetra-phenylmethane-o-carboxylic acid and diphenylanthrone the main portion consisting of unchanged diphenylphthalide. No phenyl-oxanthranol could be detected. About 15 per cent. of the crude product consisted of a reddish-brown substance insoluble in alcohol or glacial acetic acid and but sparingly soluble in benzene or toluene. As this product was not obtained by the direct condensation of phthalyl chloride with benzene its investigation does not come within the scope of this paper.* Experiment 9.-In order t o determine whether phenyl-oxanthranol is formed to any extent from diphenylphthalide 1,y isomeric transformation pure diphenylphthalide was treated with aluminium chloride in carbon disulphide solution. The product was found to contain no phenyloxanthranol. I n conclusion the author wishes to express his indebtedness to the authorities of the Chemical Department for the facilities and encouragement given in connexion with this work. CHEMICAL DEPARTMENT, THE UNIVERSITY MANCHESTER. [Received September ISth 1916.

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20 REILLY THE RESOLUTION OF ASYMMETRIC IV.-The Resolution of Asyniwielric Qriinqueucclent NitqBogen Compounds. Part I. The Salts of d- and 1- Pheriyl benz ylmeth ylallylammonizim 11 ydroxide with d- and l-a-Rrornocamphor-~-sulphonic Acid. By JOSEPH REILLY. THE study of the structure of compounds containing an asymmetric nitrogen (or other) atom has to a large extent developed from the analogy between these compounds and corresponding carbon derivatives. I n general a similarity is observed between the two classes of compounds but in some particulars striking differences are observed. For example the optically active scids show greater * It is quite possible that the substance is formed by the action of duminium chloride on diphenylphthalide a reaction somewhat analogous to that described by Scholl and Seer (Annulen 1912 3W 111; Monulsh.: 1012,33 1) QTJIWQUEVALENT NITROGEN COMPOUNDS.PART I. 21 variation with regard to the facility with which they can be employed as agents for the resolution of compounds containing asymmetric nitrogen atoms than for the resolution of similar carbon compounds. With asymmetric quinquevalent nitrogen com-pounds such as the quaternary ammonium compounds and par-ticularly with the cyclic derivatives this difference is very marked. I n this respect it is also noticed t h a t it is much more difficult to resolve the cyclic ammonium coinpounds than other quinquevalent compounds in which the nitrogen does not form part of the ring. Taking the case of compounds containing a quinquevalent nitrogen atom attached to five different univalent radicles the following brief summary will show the different behaviour of the optically active acids with regard to their power to facilitate resolution (Reilly Proc.Camb. Phil. SOC. 1915 18 177). By fractionally crystallising the compound obtained by displacing the iodine in dl-phenylbenzylmethylallylammonium iodide by the d-or l-P-camphorsulphonate radicle Pope and Peachey (T. 1899 75, 1127) succeeded in resolvirjg the ammonium compound yet Wede-kind (Ber. 1899 32 517) had previously failed to obtain the two modifications by repeated crystallisation of the d-tartrate or d-camphoric acid derivative. Jones later failed t o separate the d- and Z-phenylmethylethylallylammonium d-P-camphorsulphonates even after repeated crystallisation from various solvents whilst he found that the d- or l-a-bromocamphorsulphonate of the inactive base could be readily resolved by fractional crystallisation.It might therefore be considered t h a t the stronger the optically active acid employed to effect the resolution the more easily would such a result be achieved. This however is not dways the case, as the following account shows. The base mentioned above which Pope and Peachey resolved by the aid of camphorsulphonic acid, is much more difficult t o resolve if the agent employed is bromo-camphorsulphonic acid. Recently Komatsu (Mern. Coll. Sci. Kyoto Zmp. Uniu. 1915 1 123) subjected to repeated crystallisa-tion from acetone and ethyl acetate the bromocamphorsulphonates of this base b u t failed t o bring about a separation.Wedekind (Zeitsclb. physikal. Chem. 1903 45 235) aware of the previous work of Pope and his pupils attempted to resolve p-tolylbenzyl-methylallylammonium iodide into its two antipodes by the aid of d-6-camphorsulphonic acid but failed yet Jones (T. 1908 93, 1790; compare also Homer Proc Camb. Phil. Soc. 1907 14 196) succeeded by crystallisation of the hydrogen d-tartrate. Several other instances have been recorded in which resolution is brought about by the aid of the compara.tively weak acids d- or Z-tartaric or d- or Z-camphoric where the much stronger acids such as d- o 22 REILLY THE RESOLUTION OF ASYMMETRIC Z-j3-camphorsulphonic or h or Z-a-bromocamphor-n-sulphonic have been unsuccessful. Resolution may fail in some instances owing to the formation of a partly racemic compound by the crystallisation of which the isomerides cannot be separated.This explanation may also be suggested to account for the difficulty in separating into d- and Z-modifications certain cyclic ammonium compounds such as the a- and &substituted pyridinium compounds or the tetrahydro-quinolinium derivatives of the type CSH,,:NR/R/’X. These com-pounds should be capable of existing as optical antipodes since their molecules have no plane of symmetry (Jones T. 1903 83, 1400). Hydrolytic dissociation of the salts it is thought in other cases will account for the results obtained. Identical solubilities of the two derivatives formed from the d- and Z-base and the optic-ally active acid could be offered as another explanation but this suggestion is not sufficient.This selective action of optically active acids in their power to bring about the resolution of extern-ally compensated compounds noticeable much more frequently in the case of nitrogen than of carbon derivatives would suggest that the non-resolution in particular cases is due to some other causes than to those indicated The present work was undertaken in order to investigate more fully this selective action of the optically active acids. The original quaternary iodide resolved by Pope and Peachey is readily obtained in the d- and Z-forms by fractional crystallisation of the d- and Z-B-camphorsulphonates of the inactive ammonium base and formation anew of the iodides by the action of aqueous potassium iodide.Substituting a-bromocamphor-n-sulphonic acid for P-camphorsulphonic acid in the above experiments on fractional crystallisation of the a-bromocamphor-n-sulphonates a separation of the two isomerides is not so readily obtained. I n order t o ascer-tain if racemisation sufficiently accounts for the different behaviour of the P-camphorsulphonates and the halogenated compounds an attempt was made to obtain the pure d- and Z-compounds of the base with d- and Z-a-bromocamphor-n-sulphonic acid by an indirect method and to investigate the compounds formed. By the reaction of anhydrous silver a-bromocamphor-n-sulphonate with d-phenylbenzylmethylallylammonium iodide in dry acetone under certain conditions the compound d-phenylbenzylmethylallyl-ammonium d-a-bromocamphor-?r-sulphonate was obtained pure.By combination of the d- and Z-iodides with silver d- and Z-a-bromo-camphor-n-sulphonates under conditions stated later the following compounds were obtained dBdA dBZA ZBZA and IBdA. These compounds are of the same order of stability as the correspondin QUINQUEVALENT NITROGEN COMPOUNDS. PART I. 23 P-camphorsulphonates and show very little tendency t o racemise. I n alcohol and chloroform solution small racemisation effects have been observed. The further study of these racemisation effects is much facilitated both by the very high specific rotations of the bromocamphorsulphonates and by their solubility in both water and non-aqueous solvents. EXPERIMENTAL. R esolut i o n of dl-Ph e l ~ y l b emylm et hylallylammonium Iodide.The details of the method employed in the resolution of the iodide differ somewhat from those previously employed. The quaternary iodide in dry acetone was heated with a molecular pro-portion of silver d-P-camphorsulphonate for several hours. The solution was filtered and the insoluble portion extracted three or four times with boiling acetone. The acetone from the extract was distilled off and on cooling the syrupy residue quickly crystal-lised forming a hard mass which consisted of a mixture of the d-P-camphorsulphonates of the d- and Z-bases. The acetone filtrate from the sulphonates on evaporation on the water-bath gave a partly viscous residue which was extracted with dry ethyl acetate and most of tohe solvent evaporated off. It was t'hen placed in a vacuum desiccator when the main crop of crystals was obtained.The two fractions together gave a nearly theoretical yield. The separation of the isomerides and the preparation of the pure d-iodide were carried out according to Harvey's modification of the method devised by Pope and his co-workers (T. 1905 87 1482). The following determinations of the rotatory power were made with a chloroform solution of the iodide containing 0.3065 gram made up to 30 C.C. a t 1 7 O in a 4-dcm. tube: Hggree,,. Hgyellow. Na elluw-a ............ +2-83" $- 2.44" + 2.30" [MI ......... 253 218 205 [u) ......... 69.2 59.7 56.3 The rotation dispersion ratio for Hggree,l/NaJ-allo,v = 1.230 and for Hgyellow/ The value [a]= 56.7O obtained by Harvey (loc. cit.) is in agree-Nayellow= 1.061.ment with these results. Preparation of d-PhenylbenzyZmethylallylammonium d-a-Bromo-cam phor-?r-sulph onat e. Silver a-bromocamphor-n-sulphonate (70 grams dried at looo) was digested with dry acetone (300 c.c.) under reflux and a mole-cular proportion of the pure d-quaternary iodide added in smal 24 REILLY THE RESOLUTION OF ASYMMETRIC quantities a t a time. The mixture was boiled for about two hours and then filtered. To the filtrate were added washings with acetone of the insoluble silver iodide. The greater portion of the acetone was distilled off and the residue set aside overnight when it set to a crystalline mass which was extracted in a Soxhlet apparatus xrith dry ethyl acetate. On cooling the ethyl acetate solution deposited the sulphonate in colourless crystals which were collected.The filtrate on the addition of light petroleum (b. p. 40-60°) gave a further deposit of crystals. The substance was subsequently crystallised twice more from dry ethyl acetate. It melted and decomposed a t 155-159O. It was very readily soluble in alcohol or chloroform readily so in water or acetone sparinglyso in ethyl acetate and insoluble in light petroleum. It was dried a t looo in a vacuum until constant in weight before being analysed : 0.1174 gave 0.2550 CO and 0.0692 H,O. 0.1425 , 0.0487 AgBr and 0*0585 BaS04. Br=14.54; C=59*23; H=6.55. S = 5.63. C,,H,,O,NBrS requires C = 59-13 ; H= 6-21 ; Br = 14.59 ; S = 5-85 per cent. The compound was again crystallised from the same solvent, An aqueous solution containing 0.1655 gram in 30 C.C.a t 14O when the final determinations of the rotatory power were made. in a 4-dcm. tube gave: Hayreen. Hg e ~ l c w . Nayc~low. a ............ +2*23" + 1-91" + 1.80" [a] ......... 101.1 86.5 81.5 [MI ...... 554 474 44 7 The rotation dispersion ratio for Hgg,ee,,/Nayellow= 1.239 and for Hgyellow/ Na ellow = 1.06 1. The corresponding values for the ammonium salt of the acid are 1.243 and 1.059 (Pope' and Read T. 1910 97 2201). Taking the molecular rotation of the d-bromocamphorsulphonic acid ion as [MIL 279O (Pope and Read Zoc. cit.) this gives the molecular rotatory power of the d-phenylbenzylmethylallylammon-ium ion [Nln + 168O agreeing well with t'he value [MI +166*4O obtained by Pope and Harvey (T.1901 79 828) from the study of the d-P-camphorsulphonate derivatives. The quaternary iodide was recovered by the addition of an aqueous solution of pot'assium iodide and it gave in chloroform solution [a] + 56*1°. The bromocamphorsulphonate in aqueous solution showed only a very slight tendency towards racemisation and after two months in a thermostat a t 20° the substance gave [ a ] 79.9O QUINQUEVALENT NITROGEN COMPOUNDS. PART 1. 25 The compound separated from water in large well-defined, anhydrous colourless needle-shaped crystals in radiant bunches. The specific rotatory power however had fallen to [aID 79'1O. On warming an aqueous solution of the compound it became cloudy, and after some time oily globules consisting of the tertiary base, appeared.With prolonged boiling the solution gradually lost its activity owing not to optical inversion but probably t o decomposi-tion. The inactive ammonium iodide was also caused to react with silver d-a-bromocamphor-.rr-sulphonate in dry acetone solution under similar conditions to those employed. in the above experiments. Working with the inactive iodide there was greater difficulty in obtaining a crystalline derivative. On filtering from the silver iodide and concentrating the solution the product tended t o separate in a partly crystalline mass. I n this form it was macer-ated with dry acetone and the mixture boiled and filtered the filtrate afterwards being evaporated to small bulk. The solid matter which separated was spread on a porous tile and dried in a vacuum desiccator over sulphuric acid until quite hard and recrys-tallised several times from dry acetone.It was then obtained in a crystalline form melting indefinitely from 145O to 1 5 0 O . After re-peated crystallisation from acetone the specific rotation determined in aqueous solution altered only from [a]Eo 51.3O t o [a] 53*0° a t which figure it remained constant. The latter figure gives [MI 291° a value sufficiently near that of ammonium bromo-camphorsulphonate ([MI 279O) t o indicate that very little resolu-tion has been accomplished under these conditions. A series of fractional crystallisations from ethyl acetate showed indications of resolution but the pure active compound was not easily obtained. The acid used in the above experiments was prepared from d-a-bromocamphor.This compound was converted into the sulphonic acid derivative by fuming sulphuric acid and then purified by means of its ammonium salt. The latter salt was decomposed by baryta solution and the silver salt obtained by the action of silver hydroxide as described by Pope and Read (T., 1910 97 2200). d-Ph enyl b en z y lm e t h ylally lamm onizi m 1-a-Bro m oca m p h OFT-sulphonn t e. The d-iodide and silver 1-a-bromocamphor-.rr-sulphonate do not react readily in very dry organic solvents whilst if a little water is added the sulphonate obtained is partly racemised. The follow-ing procedure gave satisfactory results. One molecular proportion of anhydrous silver a-bromocamphor-.rr-sulphonate was added t 26 REILLY THE RESOLUTION OF ASYMMETRIC dry ethyl acetate boiling under reflux ; one molecular proportion of the d-base was added in small quantities a t a time and the mixtlure boiled for about two hours.After filtration the soluble portion together with two or three washings with ethyl acetate of the silver iodide was evaporated to dryness and the viscous residue left over sulphuric acid in a desiccator until the whole mass crystal-lised. When very hard this mass was pulverised and extracted in a Soxhlet apparatus with ethyl acetate. On evaporation t o a small bulk and adding a little light petroleum the required com-pound was precipitated and it became crystalline very quickly. It melted and decomposed a t 146-148O. The compound had [a] -23O (in aqueous solution) but on three crystallisations from ethyl acetate this number changed to [aID -20-56O.This value on subsequent crystallisation from non-aqueous solvents did n o t alter. The substance crystallised from water in large needles and clusters of radiant crystals. Although no exact measurements have yet been made of the solubility of this compound it appears however from general examination to be more readily soluble than d-phenylbenzylmethyl-allylammonium d-a-bromocamphor-?r-sulp'honate in ethyl acetate. It would be expected therefore that ethyl acetate might be a suit-able solvent to bring about the separation of the isomerides from an inactive mixture of the two by fractional crystallisation but, as already shown this is not the case. By the interaction of silver d-a-bromocamphor-71.-sulphonate with partly resolved &iodide the pure d-a-bromocamphor-r-sulphonate of the d-base was obtained after several crystallisations from dry ethyl acetate.The following determinations of the rotatory power were made with an aqueous solution containing 0.1240 ++ gram in 30 C.C. a t 20° in a 4-dcm. tube: Hggreeii. Hgyellow. Nayellow. a ............ - 0.45" - 0.37" - 0.34" [a] ......... 27-22 22.4 20.5 [MI ......... 149 123 113 The rotation dispersion ratio for Hggrecn/NZtye\low = 1.323 and for Hgyellow/ Nayellow= 1.088. The number for the molecular rotation compares well with the molecular rotatory power obtained by calculation from the mole-cular rotatory power of d-phenylbenzylmethylallylammonium d-a-bromocamphor-.Ir-sulphonate. The molecular rotation of the basic ion is 166.4O.Pope and Peachey have shown (T. 1899 75 1084) that the molecular rotatory powers of the basic and acidic ions may be * Dried at 100" QUINQUEVALENT NITROGEN COMPOUNDS. PART I. 27 calculated from the molecular rotatory power of the salts dBdA, dBlA as follows provided the determinations are made in dilute solution : [MI of dBdA + [MI of dBlA= twice [MI of dB ion. [MI of dBdA- [MI of dBZA= twice [MI of dA ion. Applying these formulae toi the values found above we obtain the following molecular rotations for sodium light : dB ion 167O. d A ion 279’6O. The Z-a-bromocamphor-7r-sulphonate was prepared in a similar manner to the d-compound starting from 1-camphor as described by Pope and Kipping (T. 1893 63 576).l-Phenylbenzylmethylallylammonium l-a-Bromocamphor-7;-sulphona.te. The solvent from the mother liquor obtained from the fractional crystallisation of the d-P-camphorsulphonates was distilled off and the pure Z-p’heenylbenzylmethylallylammonium Z-P-camphorsulphon-ate prepared in the manner described by Harvey (T. 1905 87, 1482) using acetone as solvent. The Z-iodide was obtained by adding a concentrated solution of potassium iodide to an aqueous solution of the camphorsulphonate and subsequent treatment as in the case of the d-compound. A determination of the rotatory constants with a chloroform solution containing 0.1215 gram in 30 C.C. of solution at 15O in a 4-dcm. tube gave: H g g r e m . Hgyellow. Nayellom-a. ........... - 1.12” - 0.97” -0.91” [u] .........69.1 59.9 56.2 [MI ......... 252 219 205 The rotation dispersion ratio for Hggraen/N&yellow = 1.230 and for Hgyellouv/ Nayellow= 1-066. The figure for the rotatory constant with sodium light is in close agreement with the value [a] -56-4O obtained by Harvey (Zoc. The method of preparation and purification of Z-phenylbenzyl-methylallylammonium Z-a-bromocamphor-.lr-sulphonate is similar t o that used in the case of its enantiomorphously related isorneride. After one crystallisation the substance had [a]= - 7 7 * 3 O and sub-sequent crystallisation altered this to the constant value [alD - 81.2O. The following determinations of the rotation con-stank of a purified sample were made: cit .) 2 8 ASYMMETRIC QUINQUEVALENT NITROGEN COMPOUNDS. 0.1154 gram in 30 C.C.of aqueous solution a t 20° in a 4-dcm. tube gave: Hggreen- Hgyellow- Nayellow. a ............ - 1.54" - 1.32" - 1-25' [u] ......... 100.1 85.8 81.2 [MI ......... 548 470 445 The rotation dispersion ratio for Hgg,ee,,/Na.,eil.w = 1.232 and for HgyellOw/ The molecular rotatory power of the l-phenylbenzylmethylallyl-ammonium ion is [MI -166O a value agreeing well within experi-mental error with that obtained for the d-base. NaJ7ello,,. = 1 * 0 5 6. l-Ph enyl b e n z ylm e t h ylallylmn monium d-a-BTomocaniph or-7r-sulphonat e. This compound was also prepared in a similar manner to its isomeride and had similar properties. It melted a t 147-149O. The rotatory constants were determined in aqueous solution ; 0.2360 gram made up to 30 C.C. a t 1 7 O in a 4-dcm. tube gave: Hggreet Hgyellow. N%allow. a. ........... + 0-85" + 0.70" + 0.64" [Q] ......... 27.0 22.2 20.3 [MI ...... 148 122 111 The rotation dispersion ratio for Hgg,een/Nayellow = 1.328 and for Hg,ellc,,r/ Nayellow = 1.094. The molecular rotatory power of this salt ([MID +11l0) gives a value which agrees within experimental errors with t h a t assigned to its enantiomorphously related isomeride and also with the value obtained by calculation from d-phenylbenzylmethylallylammonium d-a-bromocamphor-.rr-sulphonate. The recovered quaternary iodide had [aID -56*5O. There is no immediate prospect of continuing this work or the comparative study of the corresponding derivatives of the optically active acids with the cyclic ammonium compounds owing to the undertaking of other duties. For this reason the work is pub-lished in its present form. I desire to acknowledge my indebtedness t o Prof. Pope for his suggestion of this work and for his kind interest during the course of the experiments. THE CHEMICAL LABORATORY, THE UNIVERSITY, CAM RRIDGE. [ I?ccci~ecl A'occiriher 161h 1916

ISSN:0368-1645    

DOI:10.1039/CT9171100020

出版商:RSC    

年代:1917

数据来源: RSC

摘要:

DENHAM LEAD SUBIODIDE ETC. 29 V.-Lead Subiodide and an Iniproved Method for The Solubility of Lead Preparing Lead Suboxide. Iodide. By HENRY GEORGE DENHAM. THE existence in aqueous solutions of subvalent salts of lead has been demonstrated by the joint work of Denham and Allmand (T. 1908 93 424) wherein it is shown that in the presence of platinised platinum hydrogen is capable of reducing bivalent salts of lead to a lower state of valency. Further support of this was obtained from. the “ circulation ” experiments in which it was shown that by maintaining a constant flow of an aqueous solution of lead acetate over a heated column of lead appreciable quantities of the metal could be dissolved and again precipitated on cooling the solution. .These two results were summarised by the authors in the equations Pb++ + H K Pb+ +El+ Pb+ + + Pb c 2Pb+.A further possible explanation has since been suggested by Pick and Ahrens (Abegg’s “Handbuch,” 4 t e Gruppe Blei 637) the mechanism of the second reaction being represented according t o their view by the equation Pb+++Pb=Pb2++. Further evidence as to the existence in aqueous solutions of the ions Pb+ or Pb,++ has recently been furnished by the work of Bell (Trans. Faraday SOC. 1916 11 1 79) who investigated the problem by comparing the weight of lead actually dissolved in various electrolytes during the passage of an electric current with that calculated from the electrochemical equivalent for bivalent lead. The discrepancy observed was found to substantiate the earlier work of Denham and Allmand.The obvious method to obtain sub-salts of metals which give definite suboxides for example lead (Tanatar Zeitsch. anory. Chem. 1901 27 304; Brislee T. 1908 93 154)) is to act on this suboxide with the necessary acid; but this method failed utterly owing to the following decomposition : Pb,O -+ Pb+PbO. Other methods such as the action of finely divided lead on the various solutions of lead salts also gave negative results. It has been shown that the vapour of methyl iodide acting on heated cupric oxide gives cuprous iodide without the liberation of iodine (Denham Zeitsch. anorg. Chenz. 1911 71 303). This sug 30 DENHBM LEAD SUBIODIDE AND AN IMPROVED gested that the vapour of methyl iodide acting on lead suboxide might yield a lower iodide of lead and although many unforeseen difficulties have been met with this method has ultimately proved successful.A preliminary experiment was carried out by distilling methyl iodide over lead suboxide a t a temperature of 250-260°. After a distillation lasting about thirty minutes the apparatus was cooled and the reaction tube examined. The substance in the tube was found to have changed from its original dark grey colour to a dark yellow with globules of lead scattered throughout the mass, but in the immediate neighbourhood of the glass walls a homo-geneous bright yellow band was clearly to be seen. The inner mass was extracted with hot water and the filtrate gave on cool-ing a copious crop of lead iodide crystals whilst the yellow band under similar treatment not only gave no such deposit but the filtrate gave no trace of a precipitate with potassium chromate.This reaction several times repeated pointed to the desired reac-tion having proceeded with considerable evolution of heat-sufficient to raise all but the layer in contact with the relatively cool walls to a temperature a t which the subiodide decomposed into a mixture of lead iodide and lead the melting of the metal proving that the temperature had risen a t least 70°. This supposi-tion was a t once tested by mixing the suboxide with four times its weight of silica and it was found that the tendency to decom-position was by this means completely checked. Before describing in detail the apparatus and method used in preparing the subiodide the details of the method for obtaining pure samples of lead suboxide merit attention.Methods of Preparation of Lead Suboxide. Two methods have been described for the preparation of this suboxide namely that of Glaser (Zeitsch. anorg. Chem. 1903 36, 1) and that of Tanatar (Zoc. cit.) but the actual working details of their methods have been so sparingly given that it is wellnigh impossible to follow their work without repeating the whole of their experiments. Glaser for example records that so long as the temperature does not exceed 235O lead oxide is quantitatively reduced to the suboxide and not to lead. The duration of this reduction is how-ever not mentioned. On the other hand the author has found that samples of lead oxide prepared by the decomposition of lead oxalate in a stream of air are reduced t o lead at temperatures that do not exceed 2 2 0 O .In an experiment a t this temperatur METHOD FOR PREPARINQ LEAD SUBOXIDE. 31 lasting 100 hours not the slightest sign of a halt in the neigh-bourhood of a composition approximating t o that of lead suboxide was found. Glaser has pointed out in the case of copper oxide that the actual temperature of reduction depends on the previous history of the oxide and it is highly probable that the samples of oxide used in this research possessed a finer grain than the speci-mens used by Glaser hence the difference in the temperature of reduction. Obviously a method of preparation depending for its success on a knowledge of the particular temperature of reduc-tion of each sample used is of little value as a method of prepara-tion and attention was then turned to that of Tanatar.This author describes how he prepared the suboxide “by heat-ing the lead oxalate in a combustion tube a t the lowest possible temperature carbon dioxide being led through the apparatus during the decomp~sition.’~ It has required a considerable amount of work to rediscover the conditions that enabled Tanatar to obtain a product showing the properties of lead suboxide; under no con-ditions has the author been able t o obtain a pure product when using a stream of carbon dioxide for considerable traces of this gas were always tenaciously retained possibly as subcarbonate. If nitrogen is used according to Tanatar’s suggestion this objec-tion is removed but the inordinate length of time necessary for the decomposition-nearly a week a t 300°-is a great disadvantage.Consequently the author has been compelled t o introduce various modifications in Tanatar’s original method and to lay down pre-cisely those conditions that enable an independent worker to repeat his experiments. I n the first place the dilution effect obtained by the passage of an inert gas was obtained by removing the products of decom-position (carbon monoxide and carbon dioxide) by an automatic threefall Sprengel pump. Provided the total pressure does not exceed 5 cm. the carbon monoxide does not reduce the suboxide to lead. The main part of the decomposition was carried out a t 270-275° but when the pressure had fallen nearly to zero the temperature was steadily increased to a maximum of 335O.Under these conditions it is possible to convert the oxalate into’ suboxide in twenty-six hours. The product is a dark powder exhibiting all the properties ascribed to it by Tanatar. So far as the preparation of the suboxide itself is concerned the author has been unable to find any reason why the temperature of decomposition should not rise as high as 375O. Even a t this temperature no decomposition into lead and lead oxide occurs but the product becomes distinctly paler in colour and in this form is much less reactive especially towards methyl iodide 32 DENHAM LEAD SUBIOT)IDE AND AN IMPROVED Table I gives the composition of the last. nine samples of lead suboxide prepared according to the met,hod outlined above.TABLE I. Experiment ... 1 2 3 4 5 6 7 8 9 Lead per cent. 96.16 95-93 95.99 96.04 95-74 95.86 96.16 96.19 96.01 (theory 96.28) Method of Prepration of the Subiodide. Although it is relatively easy t o prepare samples of the sub-iodide approximating in composition to the theoretical i t has been found t,hat the pure substance may be obtained only by the closest attention t o the conditions stated below. A FIG. 1. C The apparatus found to be most satisfactory for the preparation of the subiodide is shown in Fig. 1. J was a distillation flask into which methyl iodide could be introduced from K a t the completion of the decomposition of the oxalate into suboxide; H was a tube cont,aining phosphoric oxide; G a spiral of thin glass; P E-bulbs containing the reaction mix-ture of lead oxalate and silica; D a bulb containing lead oxalate capable of being sealed off a t the conclusion of the decomposition of the oxalate into suboxide and separately analysed; C a water condenser; M a receiver into which the tube from the condenser projected to a considerable extent so that after the first few C.C.of methyl iodide had been condensed the evolution of any ga METHOD FOR PREPARING LEAD SUBOXIDE. 33 could be noted; A a manometer; B a by-pass to enable the pump to remove evolved gases rapidly from both bulbs thus ensuring that the manometer registered the pressure ruling throughout the whole apparatus-a very necessary precaution f o r it may be noted that when more than two bulbs are used owing to the difficulty of keeping down the pressure in the inner bulbs reduction of the suboxide by the carbon monoxide ensues and the inner bulbs give a variable product much richer in lead than the suboxide and this occurs even although the gauge does not register a pressure above 5 cm.The taps f e d were protected with mercury seals, as the vapour of methyl iodide rapidly attacks the tap grease during the distillation; g was a three-way tap; L an electrically heated oven. All temperatures were recorded on a platinum resistance thermo-meter which was repeatedly checked against a standard. I n an experiment about 0.5 gram of oxalate intimately mixed with four times its weight of silica was introduced into each of the bulbs E and F a little glass-wool being first placed at the bottom of each bulb; and into the sample bulb D was brought about 0.4 gram of oxalate.The apparatus after being sealed together as in the figure was exhausted until the pump (‘ hammered ” and its tightness was tested. The electric oven was then steadily heated until a temperature of 270-275O was reached. A t this stage a steady evolution of gas set in and with three fall-tubes in use a pressure of 4-5 cm. was generally reached in an hour after the evolution of gas first set in. The decomposition then proceeded as already described. When no further gas was evolved the oven was cooled to 250°, and a slow stream of dry nitrogen freed from traces of oxygen by slow bubbling through alkaline pyrogallol and over red-hot copper was introduced until the pressure had risen to 75 cm.The bulb D containing the sample of suboxide was then sealed off; methyl iodide was introduced into R oxygen thoroughly boiled out and the tap h closed a little mercury being also dropped into the cup. I n this way the iodide could be easily introduced into the flask J without a trace of oxygen entering. By cutting out the by-pass B the vapour of the iodide could be driven a t any desired rate through the bulbs by suitably adjusting the temperature of the flask J. The most satisfactory rate of distillation proved to be such that 5 C.C. condensed in the receiver M in about twenty minutes. The total duration of the distillation was generally between fortyfive and fifty-five minutes. I n many cases the reaction as shown by the evolution of gas in the receiver was com-plete in fifteen minutes but occasionally the suboxide appeared to VOL.cxr. 34 DENHAM LEAD SUBIODIDE AND A N IMPROVED react more slowly and a longer distillation was necessary. After tlie distillation liad begun the temperature of the oven was slowly raised to a maximum of 262O and it was so arranged t h a t this maxinium temperature was maintained for the last twenty minutes of the distillation. After the conipletioii of the distillation the t a p f was opened and tlie pump started whilst the receiver ill was cooled with a mixture of ether and carbon dioxide. When the pressure had fallen to 4 cm. the methyl iodide receiver was sealed off a t 0 and b likewise the apparatus to the right of the point c ; a t these points it may be noted constrictions had been made in setting up the apparatus.The object of reducing the pressure to 4 em. before sealing off is t h a t only when the pressure has fallen to this point is it possible to seal off any parts of the apparatus withoxt the liberation of iodine. The pump was allowed to con-tinue in action for twelve hours the oven being kept a t a tempera-ture of 245Ok5O. The bulbs were then sealed off and the contents were available for analysis. The necessity for introducing nitrogen prior to the distillation arises from the fact t h a t the methyl iodide reacts much more readily under atmospheric than under diminished pressure ; for example in two experiments a spiral condenser cooled by carbon dioxide and ether was used and no nitrogen introduced into the apparatus.After one hour’s distillation scarcely any reaction between the methyl iodide and the suboxide had occurred. So far as the limits of the temperature are concerned the reac-tion has been found t o proceed too slowly below 250° and a t 264O a slight decomposition of the methyl iodide occurs with the libera-tion of iodine. The result is t h a t a t all temperatures above 263O there is a slow evolution of gas throughout the whole of the dis-tillation and an examination of the product shows t h a t it always consists of a mixture of lead suboxide and considerable quantities of lead iodide the actual amount of each depending on the tempera-ture and the duration of the distillation. Thus a t 280° when the distillation lasted ninety-five minutes the mixture contained 44 per cent.of iodine whilst a t 270° with a duration of eighty-three minutes the iodine content was 43 per cent. (PbI contains 55.1, and P b I 38 per cent. of iodine). Moreover it is to be noted t h a t so long as the temperature does not exceed 262O it’ is possible to distil the vapour through the reaction bulbs for an hour after the evolution of gas has ceased and the percentage of iodine does not rise above t h a t of the suboxide (38) whilst even a few minutes’ distillation a t any temperature above 263O will give a product containing distinctly more than 38 per cent. of iodine. The velocity of the distillation must be such that the vapou METHOD FOR PREPARING LEAD SUBOXIDE. 35 approximately reaches the temperature of the oven before coming into contact with the suboxide.This is ensured by the presence of the spiral; but if this precaution is neglected the reaction will rarely proceed to completion and one obtains a mixture of the suboxide and subiodide. This can a t once be seen since such a mixture even though containing but 2 per cent. of the suboxide, has no longer the characteristic yellow colour of the pure subiodide, but has a distinct green tint. The object of the lengthy exhaustion of the apparatus a t the completion of the experiment is that a slightly volatile yellow product condenses in the reaction bulbs during the distillation, and this can be best removed by thorough exhaustion a t as high a temperature as is consistent with the stability of the salt. This difficultly volatile product slowly distils off during exhaustion and condenses in a clearly defined yellow band just outside the oven.It contains neither lead nor iodine and appears to be a condensa-tion product of an aldehyde formed during the reaction. The following experiment illustrates the effect of insxficient exhaus-tion The exhaustion was continued for two hours and a bright yellow product was obtained which contains I = 36-6 Pb = 59.7 per cent. The ratio P b I is exactly that for lead subiodide (62:38), but the sample was evidently vitiated by the presence of the above-mentioned condensation product. M e t hods of A nalysis. ( a ) I n the case of lead oxalate the lead was estimated by intro-ducing a weighed quantity into a platinum crucible adding dilute sulphuric acid and weighing as sulphate after evaporation and ignition.( b ) The lead in the suboxide was estimated by introducing a weighed quantity from a bulb into a platinum crucible dilute nitric acid was added and the whole evaporated to dryness the lead being finally weighed as sulphate according t o the method outlined in (a). ( c ) I n the analysis of the lead in the subiodide a weighed quantity of the mixture of subiodide and silica was introduced into a weighed platinum crucible; dilute nitric acid was added and the whole evaporated t o expel iodine and excess of nitric acid and the total weight of lead sulphate and silica obtained as in (a). The weight of silica was subsequently obtained by washing out the lead sulphate with hot concentrated ammonium acetate and hence the weight of lead sulphate derived from the original subiodide estimated.( d ) I n the estimation of the iodine the weighed quantity of c 36 DENHAM LEAD SUBIODIDE AND AN IMPROVED ~ubiodide and silica was brought into a beaker and moistened with moderately concentrated acetic acid ; after remaining about fifteen minutes on a water-bath 250 C.C. of water were added and the whole digested until complete solution of the subiodide had occurred. The silica was filtered off and estimated the iodine in the filtrate being weighed as silver iodide. (A slight deposit of carbonaceous matter never more than 0.1 per cent. was always left undissolved with the silica.) Analytical Results. (a) Lead 0xalate.-Samples of this salt were prepared by the action of oxalic acid on an acid solution of lead acetate.Found Pb per cent. Sample 1 ................................... 70.1 1 70.13 .. 2 ................................... 70.11 70.04 , 3 .................................. 70.14 , 4 ................................... 70.17 Theoretical ............ 70- 18 (b) Methyl iodide was prepared by the usual method and after washing repeatedly with sodium hydroxide and water was distilled from phosphoric oxide. The boiling point of the iodide did not vary by more than 0'25O. (c) Lead Subiodide. Found Pb Found Pb Found, per cent. per cent. I per cent. Expt. in suboxide. in subiodide. in subiodide. 1 - 62.1 37.45 2 95.87 62.7 37.4 3 96.16 62.3 38.2 4 95.74 62.4 (36.0) 5 96.04 61.8 37.5 6 95.70 61.0 38-3 7 96.16 62.3 37.65 8 - 62.0 37.8 Mean ......95-94 62.07 37.76 Theoretical 96.28 62-01 37.99 ~- - -_ - - -(In experiments 1 and 8 no samples of the suboxide were taken; in taking t,he mean of the iodine percentages experiment 4 has been omitted.) Properties of the Subiodide. The much vexed question as to whether the substance the formula of which is Pb,O is a true suboxide and not an equi-molecular mixture of lead and lead oxide has been convincingl METHOD FOR PREPARING LEAD SUBOXIDE. 37 answered by Tanatar (loc. c i t . ) and by Brislee (loc. cit.). That the subiodide is also a true chemical compound and in no sense a mixture is clearly demonstrated in the first place by its colour. The bright yellow of the subiodide is only obtained when the pro-duct has a composition very close to the theoretical value.The presence of even 1 per cent. of the dark suboxide in the sample of subiodide is sufficient t o change the colour from the clear yellow to a green or even a dark yellow. Thus in one experiment wherein the suboxide had been heated to 360° during its formation thereby forming the pale grey unreactive form the subiodide obtained had a distinct green appearance and analysis showed that the ratio of lead to iodine was 65 35 (theory is 62 38). If the subiodide is heated to 300° in a vacuum the colour slowly becomes much darker and with a lens it is possible to distinguish the heterogeneity of the mixture. By the action of heat the sub-stance decomposes in accordance with the equation 2PbI -+ Pb+PbI,.The presence of the lead iodide in this dark mixture can readily be demonstrated by boiling i t for a few minutes with water filter-ing and cooling; a copious crop of lead iodide crystals is a t once obtained whilst if the undecomposed yellow subiodide is boiled with oxygen-free water and rapidly filtered not only is there an entire absence of any such separation of lead iodide crystals but the filtrate gives no trace of a precipitate with potassium chromate or with hydrogen sulphide the latter reagent producing a faint darkening only. By the action of acids (hydrochloric sulphuric and acetic) a decomposition similar to that brought about by heat takes place. The subiodide appears to undergo slow oxidation on exposure to the air. Thus after removing the silica from the reaction mixture by sifting in the open air the following analysis was obtained : Lead =60*9 per cent.Iodine =37.2 ,, Oxygen= 1.9 ,, the oxygen being determined by reduction in a stream of hydrogen. As a final proof of the chemical individuality of the substance, its solubility as well as that of the normal iodide was determined by the conductivity method. A vessel of the type shown in Fig. 2 was constructed. Into the side-tube before the capillary tap was sealed on there was introduced a glass tube containing mercury, and also a small bulb containing the salt under investigation. After the tap had beea sealed on a stream of conductivity wate 38 DENHAM LEAD SUBIODJDE AND AN IMPROVED was drawn through the apparatus in order to remove all traces of impurity arising from acid products of combustion.When a constant resistance of 20,000 ohms had been registered? both side-tubes were connected to a water-pump and the water boiled for ten to fifteen minutes under diminished pressure in order to remove traces of oxygen from the apparatus. After closing both taps and cooling the contents t o 3 5 O the bulb was broken by means of the hammer and after thorough shaking the vessel was placed in a thermostat at 25O and conductivity readings were taken until constant. I n the case of lead iodide about 0.3 gram was brought into a small bulb and after thorough exhaustion by a Topler pump the bulb was sealed off in order to make the conditions quite com-parable with those under which the solubility of the subiodide was determined.I n ten minutes after the bulb was broken in the conductivity vessel a resistance of 138 ohms was recorded and thi METHOD FOR PREPARING LEAD SUEOXIDE. 39 remained constant until the apparatus was opened to the atmo-sphere. I n order to obtain tlie solubility of the s-abiodide a sniall bulb of this substance was prepared by the uiual method and a second and larger bulb retained for a control analysis. It is essential in this determination that oxygen be rigidly excluded both from the bulb and the conductivity vessel itself. I n ten minutes after break-ing the bulb a resistance of 1250 ohnis was recorded and during the next twenty-four hours this underwent no change. It appears therefore that if the ionic mobilities of the iodine and the lead ions from the subiodide (whether Pb+ or Pb,++) be assumed to be the same as in the case of the normal iodide the solubility of the subiodide is 0.35 milli-equivalent per litre that is about one-ninth that of the normal salt.This relative insolu-bility of the lower iodide is interesting inasmuch as i t falls into line with the corresponding cases of copper mercury etc. The S o l d i l i t y of Lead Iodide. Numerous deterininations of the solubility of l e d iodide have been recorded notably by Lichty (Auzer. Chew. J. 1903 25 469), v. Ende (ZeitscJb. anorg. C'Aem. 1903 26 162) and Bottger (ZeitscJt,. pJiysika1. CJt,ern. 1903 42 602). Lichty and v. Ende both used the direct method in their estimation of the solubility, the former obtaining 1-65 riiilliniols and the latter 1.58 millimols per litre at 25O.On the other hand Bottger arrived a t a dis-tinctly lower value. His measurements were made by the con-ductivity method and on the assumption that 97 per cent. of the salt is dissociated in the saturated solutions he finds that 1-31 millimols dissolve in a litre of water a t 20*lo. By using the apparatus just described the following readings were obtained a t 2 5 O : in 10 min. 140 ohms 9 40 9 141 9, 97 100 J 141 9 , wlieiice L the specific condnctivity is 461.7 (corrected for the con-ductivity of water). A second sample of lead iodide was prepared by precipitation, and after repeated washing i t was recrystallised three timcs from water. A saturated solution in conductivity water was then pre-pared a t 40° and brought into the conductivity vessel witliout exposure t o the air.I n ten minutes a constant reading was obtained whence L = 472.2 (corrected for the conductivity of the water) 40 DENHAM LESD SUBIODIDE ETC. Assuming complete dissociation and that' the ionic conductivities of lead and iodine are 71.8 and 76.4 respectively the solubility is 1.58 millimols per litre a t 25O in exact agreement with the value obtained by v. Ende but decidedly higher than that obt'ained by Bottger (1.31 a t 20*1°). On the other hand it has been noticed that if in the prepara-tion of the solution of lead iodide it is exposed appreciably t o the atmosphere the conductivity is abnormal. The resistance set up by a solutJon that had been thus exposed amounted t o 139 ohms in ten minutes and in sixteen hours it had risen to 148 ohms.This is attributed by the author to the following reactions: Pbf + CO + H,O -+ PbCO + 2H1, 4HI + 0 + 2H,O + 21,, for it was possible by admitting gaseous impurities to induce an exactly similar change in a solution prepared by breaking a bulb of lead iodide in the conductivity vessel. When a perfectly constant reading for the solution prepared as already described, in the absence of air had been obtained a little carbon dioxide and oxygen were introduced into the apparatus and the whole shaken. I n seventy hours the resistance rose steadily from 140 t o 152 ohms. It appears therefore that in using the conductivity method for t'he determination of the solubility of lead iodide and possibly also of lead bromide (see Bottger Zoc.cit. p. 575 on the variation noted in the conductivity of this salt) extreme care must be exercised in excluding gaseous impurities but with due precautions the method gives rapid and accurate results. Sum rnary. (1) Lead suboxide may be best prepared by heating in a vacuum lead oxalate a t a temperature as high as 376O provided the pressure of the evolved gases does not rise above 5 cm. (2) Above 335O the suboxide becomes paler in colour and a t the same time much less reactive. (3) Lead subiodide may be obtained by distilling the vapour of dry methyl iodide at a maximum temperature of 262O through the suboxide. (4) The subiodide thus prepared is of a pure yellow colour which darkens on heating above 300° owing to decomposition into lead and lead iodide. (5) The subiodide has a solubility about one-ninth that of t'he normal iodide is slowly oxidised by air and is completely decorn-posed by acids THE DISPLACEMENT OF SULPHONIC ACID GROUPS ETC. 41 Further work on the sub-salts of lead etc. is now in progress. The author desires t o record his appreciation of the facilities placed a t his disposal by the Walter and Eliza Hall Trust for the prosecu-tion of this research. CHEMICAL LABORATORY, UNIVERSITY OF QUEENSLAND, BRISBANE. [Received November 30th. 1916.

ISSN:0368-1645    

DOI:10.1039/CT9171100029

出版商:RSC    

年代:1917

数据来源: RSC

摘要:

THE DISPLACEMENT OF SULPHONIC ACID GROUPS ETC. 41 VL-The Displacement of Sulphonic Acid G~oups in Amino-sulphorhic Acids by Halogen Atoms. By JOHN JOSEPH SUDBOROUGH and JAMIAT VISHINDAS LAKHUMALANI. IN the preparation of 2 6dibromosulphanilic acid from sulphanilic acid tribromoaniline is always obtained as a by-product and the amount of this becomes very appreciable unless certain precautions are taken (Heinichen A m a l e n 1889 253 268). The formation of s-tribromoaniline is also observed during the formation of 2 6-dibromo-paminobenzoic acid. These observations indicate that a sulphonic or carboxylic group in the para-position with respect to an amino-group is readily displaced by bromine. This has been confirmed by exeriments on the action of bromine water on solutions of 2 6-dibromosulphanilic acid ; the results prove that' an almost quantitative yield of s-tribromoaniline can be obtained in the cold and that the other product is sulphuric acid.An examination of the literature shows that s-tribromoaniline is also formed during the bromination of o-aminobenzenesulphonic acid but not during the bromination of the isomeric meta-acid. The displacement of halogen atoms by nitro-groups is a well-known phenomenon and has been studied by Zincke ( J . pr. Chem., 1900 [ii] 61 561) Dahmer (Awnulen 1904 333 346) Robert-son (T. 1908 93 793) Gibbs and Robertson (ibid. 1914 105, 1885) and Robertson and Briscoe (ibid. 1912 101 1964) in the case of brominated phenols. The displacement of carboxylic groups by halogen atoms has also been observed by Gibbs and Robertson (Zoc.c i t . ) and the displacement of *CO,H *CHO *CO*C'H, groups by nitro-groups in the case of aromatic hydroxy-compounds has been investigated by Salway (ibid. 1909 95 1155) Harding and Weizmann (ibid. 1910 97 1126) Harding (ibid. 1911 99, 1585; 1914 105 2790) and Thomes and Siebeling (Ber. 1911 42 SUDBOROUGH AND LAKHUMALANI THE DISPLACEMENT OF 44 2115). The reactive positions are the 2- 4- and 6-positions with respect to the hydroyl group and compounds in which the displaceable groups are in the 3- and 5-positions are not decom-posed by nitric acid. A reaction of somewhat analogous type is the scission of certain aminobenzhydrols by the action of bromine (Clarke and Patch, J . Amer. Chem. Soc. 1912 34 912; Esselen and Clarke ibid., 1914 36 308).For example with p- or o-aminobenzhydrol C,H,*CH(OH)*C,H,*NH + Br -+ C,H,*CHO + C,H,Br*NH + HBr, the complex -C,H,*CH(OH) * becomes displaced by bromine. Here also decomposition does not occur with m-amino- or with unsubstituted benzhydrols but does with all benzhydrols contain-ing an amino- or alkylated amino-group in the ortho- or para-position with respect to the C,H,*CH(OH)* group. Blanksma (Rec. trav. chinz. 1905 24 320) has observed that during the reduction of certain aromatic nitro-compounds by tin and hydrochloric acid atoms or groups of atoms are elimjnated from the benzene nucleus and displaced by hydrogen. The groups thus displaced are bromine iodine carbosylic and sulphonic provided that they are in the ortho- or para-position with respect to the original nitro-group.For example: (N02)2C,H,*C0,H + C6H,(NH,),. 2 4 1 2 4 The halogen atoms in o or p-substituted anilines can also be For example removed by a process of reduction. CH,*C,H B ,*NH + CH,*C6H,*NH2 1 2 4 6 3 1 3 (compare also Jackson Atner. @hem. J. 1896 18 467; Jacobson, Ber. 1888 21 2826). Kelbe (ibid. 1882 15 39; 1883 16 67) and Heller (ibid. 1913 46 2703) have observed the removal of sulphonic acid groups from hydroxyanthraquinonesulphonic acids by means of halogens and Schmidt ( B e y . 1904 37 68) has shown that the nitro-group in a-nitroanthraquinone can be displaced by the sulphonic acid group by merely warming the nitro-compound with an aqueous solution of neutral alkali sulphite.He has also proved t h a t a sulphonic acid group in the a-position in the anthra-quinone molecule is readilg displaced by ethoxy- or methoxy-groups. Blanksma (Rec. t m u . chinz. 1910 29 377) has made use of the readiness with which sulphonic acid or carboxylic acid groups in the ortho- or para-position with respect t o an amino-group can be displaced by bromine f o r elucidating the constitution of certai SULPHONIC ACID GROUPS I N AMINO-SULPHONIC ACIDS ETC. 43 aminosulphobenzoic acids containing all three groups-NH,, CO,H SO,H. All these researches indicate the reactivity of certain sub-stituents when in the positions 2 4 or 6 with respect to ali amino-or hydroxy-group in an aromatic compound. The experiments described in this paper were undertaken with the object of studying the action of halogens on various amino-sulphonic and amino-carboxylic acids including some of the naphthalene series.The results indicate t h a t when bromine is employed an almost quantitative yield of the compound formed by displacing the sulphonic acid group by bromine is obtained. For example: NH2 NH2 33 1" \ B 1' + U,/>B, \/ I 1 \/ Rr S08H 2 6-Dibromosulphanilic acid. s-Tribromoaniline. The displacement can be brought about by means of bromine water fresh potassium hypobromite solution or an acidified solu-tion of potassium bromide and bromate. The yield in all cases is more than 90 per cent. and the other product is sulphuric acid. Similar results are obtained when 4 6-dibr~moaniline-2-sulphonic acid is used.Chlorine reacts with the two isomeric dibromoanilinesulphonic acids but the products are not pure 4-chloro-2 6-dibromo- and 2-chloro-4 6-dibromo-anilines but mixtures containing tribromo-aniline. The' formation of such mixtures can most easily be ex-plained by assuming t h a t bromine is displaced from one molecule of the dibromo-acid and reacts with a second molecule yielding tribromoaniline. The displacement of bromine by chlorine in bromoanilines has already been observed by several investigators. Wegscheider (Monatsh. 1897 18 329) was able to show that a t 240° hydrochloric acid transforms s-tribromoaniline into the corresponding tricEloro-compound. Chattaway and Orton (T., 1901 79 822) have shown that the chlorine atom in acetylchloro-amino-2 4-dichlorobenzene is able to displace bromine in such compounds as s-tribromoaniline and 2-chloro-4 6-dibromoaniline, and in the latter case they were able t o isolate a certain amount of a dichlorobromoaniline.Orton and Reed (ibid. 1907 91, 1543) have shown t h a t in the chlorination of 2 4-dibromoaniline and other bromo-derivatives of aniline mixtures of dichlorobromo-anilines and s-tribromoaniline are formed. From the products from 2 4-dibromoaniline they obtained by fractional crystallisa 44 SUDBOROUGH AND LAKHUMALANI THE DISPLACEMENT OF tion a well-defined crystalline substance melting at l l O o and the results of analysis proved that this consisted of 59.3 per cent. of tribromoaniline and 40.7 per cent. of dichlorobromoaniline, assuming that these are the only two compounds present.I n some of our experiments on the action of chlorine on 4:6-dibromo-aniline-2-sulphonic acid a crystalline product was obtained from which well-defined crystals softening a t 107-109O and melting a t l l O o were isolated after four crystallisations from alcohol. A 'p 122 118 114 110 106 102 98 Melting point curve o j mixtures of 2-chloro-4 6-dibronionniline and s-lribrosnonni line. product with the same melting point was also obtained by the action of chlorine on 2 4-dibrornoaniline. The analysis of these crystals agreed closely with the results given by Orton and Reed (Zoc. cit.). A melting-point curve of mixtures of s-tribromoaniline and 2-chloro-4 6-dibromoaniline has been examined (see figure) and it is shown that this curve is almost a straight line and that a mixture melting a t 1 2 0 O has almost the composition given by Orton and Reed.Solutions of iodine have no action on the dibromoaniline-sulphonic acids even a t looo but the displacement of the sulphoni SULPHONIC ACID GROUPS IN AMINO-SULPHONIC ACIDS ETC. 45 acid group by iodine can be effected by means of iodine mono-chloride dissolved in glacial acetic acid. The products formed are respectively 2 6-dibromo-4-iodoaniline and 2 4-dibromo-6-iodo-aniline neither of which has been previously prepared. NH2 NH2 NH NH2 \/ SO@ Br/\S03H + B r O I Br()Br -f Brf\sr I 1 Br \/ Br \/ I Experiments were also made with the corresponding dibromo-aminocarboxylic acids. The carboxylic group is more difficult t o displace.With bromine good yields of s-tribromoanilines were obtained but with chlorine and iodine monochloride displacement was not observed in the case of the para- and only to a very slight extent in the case of the ortho-compound. Comparative experiments were made with the object of deter-mining whether the ortho- o r para-sulphonic acid group is the more readily displaced by bromine. Although the experiments do not show close agreement among themselves they indicate that the sulphonic acid group which is in the ortho-position to an amino-group is more reactive than the same group when in the para-position; in most of the experiments made the yield of tri-bromoaniline was greater when aniline-o-sulphonic acid was used. I n order to show that a sulphonic acid group in the meta-position with respect to the amino-group is inactive and not readily displaced by halogen the action of chlorine bromine and iodine monochloride on 2 4 6-tribromoaniline-3-sulphonic acid and the corresponding carboxylic acid was studied but in no case was the formation of a tetra-halogena.ted aniline observed.\/ E x P E R I M E N T A L . I. Experimeiats with 2 4-l)ibroniosulpl~anilic The acid was prepared by passing air saturated with bromine vapour through an aqueous solution of sulphanilic acid. After the requisite amount of bromine had been used the precipitate of s-tribromoaniline was removed and the clear filtrate concentrated, when nearly colourless crystals of the dibromosulphanilic acid were obtained. cid. A. Displacement of the Sulphonic -4ciCF Group b y &ornine.The theoretical amount of bromine water was added t o a well stirred aqueous solution of 0.4008 gram of potassium 2 4-dibromo. sulphanilate NH,*C6H,Br,*S03K at the ordinary temperatur 46 SUD’BOROUGH AND LAKHUMALANI THE DISPLACEMENT OE’ (23-26O). The precipitate of tribromoaniline was removed, washed with water and dried in the air until constant. The pre-cipitate weighed 0.353 gram and the melting point was 110O. This corresponds with a 98.6 per cent. yield of tribromoaniline the melting point of which is 119-4O. I n some of these experiments the filtrate from the tribromo-aniline was tested for sulphuric acid and the amounts found varied from 90 to 106 per cent. of the theoretical value. The theoretical amount of freshly prepared potassium hypo-bromite solution (1 mol.) was gradually added to an aqueous solu-tion of 0.512 gram of the dibromo-acid and the precipitate treat’ed as before.The weight of the precipitate was 0.426 gram and its melting point 118-119°. This corresponds with a 90 per cent. yield. A solution of 0.5462 gram of the dibromo-acid containing a slight excess of potassium bromate and potassium bromide! was gradually acidified with sulphuric acid and the precipitated tri-bromoaniline removed. The weight was 0.49 gram and the melt-ing point 116-118O corresponding with a 97 per cent. yield. B. Displacement of the Sulphonic Acid Group by Chlorine. -+ Br’ ‘Br. GI I 1 \/ The action of chlorine water on aqueous solutions of the free 2 6-dibromosulphanilic acid and of its potassium salt was studied, but definite products could not be isolated only small amounts of dark brown precipitates.A crystalline product was obtained by adding the theoretical amount (2 niols.) of a standard solution of chlorine in glacial acetic acid to a solution of the dibromo-acid in a mixture of water and glacial acetic acid (1 8). This crystalline product melted a t 97-99O whereas 4-chloro-2 6-dibromoaniline melts a t 95’5O and the yield was 83 per cent. of the theoretical. After recrystallisa-tion from alcohol the melting point had risen to 103-104° (com-pare p. 47). C. Displacement of the Sulphonic Acid Group b y Iodine. An 83 per cent. yield of 2:6-dibromo-4-iodoaniline melting a t 147-148O was obtained as follows : One and a-half times the theoretical amount of a glacial acetic acid solution of iodine monochloride was added to 0.454 gram o SULPHONIC ACID GROUPS I N AMINO-SULPHONIC ACIDS ETC.47 the dibromo-acid dissolved in 6 C.C. of glacial acetic acid and a few drops of water. The mixture was warmed and allowed to crystallise. A further quantity of crystals was obtained by con-centrating the mother liquor. I n similar experiments the yields varied between 60 and 89 per cent. 3 6-Dibrot?io-l-iodoa?iiZi~~ e crystallises from glacial acetic acid, light petroleum (h. p 60-80°) or alcohol in glistening white needles nielting a t 147-148O : 0.2782 gave 0.4506 AgI + AgBr and after treatment with I = 33.42 ; Br = 43-61. 2 6-Dib?.omo-4-iocloncetct12i2ide.-A 90 per cent.yield of the nionoacetyl derivative can be obtained by using Smith and Orton's inethod of acetylation (T. 1908 93 1242). It crystallises from alcohol in colourless needles melting a t 246-247O : chlorine 0.3176 AgCI. CG1&NBr2I requires I = 33.68 ; Br. = 42.42 per cent. 0.2240 gave 0.3264 AgI + AgBr. C,II,ONBr,I requires AgI + AgBr = 0.3264. 2 6-Dibror~io-4-iodoclictcetic~iilide C,,H,O,NBr,I prepared by Smith and Orton's method (Zoc. c i t . ) crystallises from alcohol in small needles melting a t 166-167O. 11. Experiments with 4 6-Dibromonniline-2-sul~~~o?~~c Acid. Bromoaniline-o-sulphonic acid was prepared by Kreis's method (Annalen 1895 286 380) and was further brominated in the same manner as sulphanilic acid (p. 45). The dibromo-acid crystallises anhydrous in small rhombic crystals or with 1H,O in prismatic crystals.A. Displacemetit of t h e SLCZV~OIZZ'~ Acid Group b y Bromine. The experiments made were similar to those in which the isomeric 2 6-dibromoaniline-4-sulphonic acid was used (p. 43). The yield of tribroinoaniline in these experimeii ts varied from 92 to 98 per cent. and the melticg point of the uncrystallised pro-duct from 1 1 5 O to 1 1 9 O . B. Displacement of t h e Sulphonic Acid Group b y Chlorine. The calculated amount of a glacial acetic acid solution of chlorine was added to a warm solution of 0.348 gram of the dibromo-orthosulphonic acid dissolved in a mixture of 2 C.C. of water and 4 C.C. of glacial acetic acid. On cooling colourless crystals melting a t 100-104° were deposited and on pouring into water a pink precipitate (m.p. 95-96O) was obtained. The tota 48 SUDBOROUGH AND LAKHUMALANI THE DISPLACEMENT O F weight was 0.190 gram. The melting point of pure 2-chloro-4:6-dibromoaniline is 99O. Furt'her experiments in which a slight excess of chlorine solu-tion was added were made. The yields were respectively 78 and 75 per cent. and the product after crystallisation from alcohol melted a t 105-106O. Attempts to prepare pure 2-chloro-4 6-dibromoaniline by the chlorination of 2 4-dibromoaniline were also fruitless crystalline products melting a t 105-106° or after three crystallisations from alcohol a t l l O - l l l o being obtained. C. Displacement of the Sulphonic Acid Group b y Iodine. One and a-half times the theoretical amount of a glacial acetic acid solution of iodine monochloride was added t o a warm solu-tion of 0.325 gram of the dibromo-acid in 2.5 C.C.of water and 5 C.C. of glacial acetic acid. On cooling a 41.6 per cent. yield of a crystalline product melting a t 123-124O was obtained. By using twice the theoretical amount of iodine monochloride, 1.5 C.C. of water and 5 C.C. of glacial acetic acid f o r dissolving the dibromo-acid and after removal of the crystals pouring the filtrate into water a total yield of 88.5 per cent. was obtained. 4 6-Dibromo-2-iodoaniZine crystallises from alcohol or glacial acetic acid in glistening needles melting a t 124-125O: 0.2090 gave 0.3402 AgI+AgBr and after treatment with I = 32.04 ; Br = 43.98. 4 6-Dibromo-2-iodoacetanilide crystallises from alcohol in 0.2180 gave 0.3180 AgI + AgBr.chlorine 0-2387 AgCl. C6H4NBr21 requires 33'68 ; Br = 42.42 per cent. slender feathery needles melting a t 237O : C,H,ONBr,I requires AgI + AgBr = 0.3178 per cent. 111. Experiments with 2 4 6-Tribromoanili?ze-3-~ulphonic Acid. The theoretical amoant of bromine water was added to an aqueous solution of the tribromo-acid but no precipitate of a brominated aniline was obtained and even after remaining for some time the amount of free bromine present in the solution corresponded with the amount originally added. Similar experiments were made by using acidified hypobromite and acidified potassium bromide-bromate mixture but with negative results. By the action of chlorine dissolved in glacial acetic acid or of iodine monochloride a substituted aniline could not be isolated SULPHONIC ACID GROUPS I N AMINO-SULYHONIC ACIDS ETC.49 IV. Comparative Ezperiments on the Displacement of the Sulphonic Acid Group by Bromine in Aniline-o- and p-Sulphonic Acids. The experiments were made by using dilute (namely 1 per cent.) aqueous solutions of the respective acids and running in the theoretical amount (2 mols.) of carefully standardised bromine water from a burette the point of which dipped under the surface of the sulphonic acid solution in order t o avoid loss of bromine vapour. I f the reaction proceeds normally then the only product should be the corresponding dibromoaminosulphonic acid but if the sulphonic acid group is removed a precipitate of tribromo-aniline is obtained.I n all cases the formation of a precipitate was observed but only towards the end of the addition of the bromine water. I n each experiment the precipitate was removed, washed dried and weighed. During the addit,ion of bromine water the solutions were kept well agitated by means of a mechanical stirrer. The result of a large number of experiments is to show that in the case of sulphanilic acid the following factors affect the yield of tribromoaniline to a very slight extent only: ( a ) Temperature the range examined was froin Oo to 44O ; ( h ) rate of addition of bromine solution; (c) rate of stirring; (d) exposure to light. The following results were obtained with a solution of bromine containing 0.01433 gram of bromine per c.c.and using 50 C.C. OF the 1 per cent. solutions of the sulphonic acids: Ortho-acid Para-acid Tri bromoaniline. Tri bromoaniline. Gram. Gram. 0.1688 0.0914 0.1824 0.0710 0.1916 0.0202 0-1918 0.0214 The following results were obtained by adding the theoretical quantity of standard hypobromite to solutions of the sulphonic acids acidified with hydrochloric acid : Ortho-acid. Gram. 0.1336 0-0774 0.0612 Para-acid. Gram. 0.0214 0-0298 0.0068 The results appear t o justify the conclusion that the ortho-sulphonic acid group is relat,ively more reactive than the para. V. Experiments with Dibromoaniline-o- and -p-Carboxylic Acids. As the carboxylic acids are extremely sparingly soluble in water, solutions of their ammonium salts were used.0'445 Gram of VOL. CXI. 50 THE DISPLACEMENT OF SULPHONIC ACID GROUPS ETC. 4 6d~bromoanilins2-carboxylic acid was dissolved in excess of ammonia solution and bromine water added gradually care being taken that the solution was always alkaline. Considerably more than the theoretical amount of bromine was required as part was used up in oxidising the ammonia t o nitrogen. An 84 per cent. yield of s-tribromoaniline somewhat discoloured and with the low melting point 11 1-1 13O was obtained. A further experiment was made by dissoliing 0.261 gram of the same acid in excess of ammonia and mixing the solution uith an excess of potassium bromide and bromate. Dilute sulphuric acid was added and then dilute ammonia and these additions were alternated until the addition of sulphuric acid produced no further precipitate.The repeated addition of ammonia was to dissolve the dibromoamino-acid precipitated together with tribromo-aniline on the addition of sulphuric acid. A 91 per cent. yield of almost pure tribromoaniline melting a t 118-119° was obtained. A ctiolz of ChZorine.-0*36 Gram of the dibromo-o-amino-acid was dissolved in 5 C.C. of glacial acetic acid and the theoretical amount of an acetic acid solution of chlorine added. No crystals separated after being kept f o r some time so the solution was poured into excess of water and the resulting precipitate treated with dilute ammonia in order to remove any undecomposed acid. The portion insoluble in ammonia melted a t 95-97O and after crystallisation from light petroleum gave a fraction melting a t 103-105° indicating the formation of mixtures similar to those obtained from the dibromoamino-o-sulphonic acid and chlorine Similar results were obtained when the corresponding 2 6-dibromoaniline-4-carboxylic acid was used. 0.362 Gram of the acid gave a 90 per cent. yield of almost pure tribromoaniline melting a t 11 7-1 1 go. Definite substances could not be isolated from the products of the action of chlorine on the above acid. I n most cases the original acid was recovered. Experiments on the displacement of the carboxylic acid group by iodine in the case of both the ortho- and the para-acids were unsuccessful. Attempts t o displace the carboxylic group in 2 4 6 -tribromo-aniline-3-carboxylic acid by bromine were also unsuccessful. (P. 47). DEPARTMENT OF GENERAL AND ORGANIC CHEMISTRY, INDIAN INSTITUTE OF SCIENCE, BANGALORE. [Received August 15th 191 6.

ISSN:0368-1645    

DOI:10.1039/CT9171100041

出版商:RSC    

年代:1917

数据来源: RSC

摘要:

RELATIONSHIP BETWEEN THE PIXY SICAL PROPERTIES ETC. 5 1 VII.-Relationship between the Physical Properties of Isomeric Cobaltammines and the Electm-valencies of their Co-ordination Complexes. By RAJENDRA LAL DE. ACCORDING to Richards ( J . Anier. Chem. Soc. 1914 36 2417), elements are compressible substances and he has shown from indirect evidence that chemical affinity is responsible f o r the con-traction in volume which occurs when two different elements form a compound. Thus according to him chemical affinity instead of merely holding the atoms together exerts pressure in their inter-action. The primary object in undertaking the work described below was to study the chemical affinity (valency) in connexion with this attractive force. The above-mentioned attractive force is directly connected with molecular volume (that is density) and attempts have been made to study the influence of these forces by determining the densities of a few isomerides of a complex cobalt compound.(i) Triamminecobalt nitrite [(H3N)3C~(N02)3]. The isomerides chosen were : (ii) Dinitrotetra-amminecobalti-tetranitrodiamminecobaltiate, (iii) Hexa-am mine cob a1 t i-hexani t r ocob a1 t ia t e , For the sake of comparison double the molecular formulae of the isomeride (i) will be taken. It will then be observed that the number of NH3-groups NO,-groups and cobalt atoms is the same in the case of all the isomerides. Moreover the number of auxiliary valencies in them is the same but on account of a difference in the number of NH3- and NO,-groups around the respective cobalt atoms there is a variation in the number of electro-valencies.I n the isomeride (i) there is an absence of electro-valency in (ii) there is only one electro-valency whilst in (iii) there are three. Now if chemical affinity (valency) exerts an attraction the densities of the isomerides according to the hypo-thesis of compressible atoms ought to increase gradually as we pass from (i) to- (iii) for the number of electro-valencies has increased in the isomerides in the same order. It will be seen later that such a gradual increase in density has been found t o occur. I n preparing these isomerides it was noticed that their solu-0 52 DE RELATIONSHIP BETWEEN THE PHYSICAL bilities differed appreciably from one another. It was therefore desirable to make quantitative measurements of this property in order to find a relation between electro-valency and solubility.The results of these measurements go t o show that the solubility of the isomeride decreases as the number of its electro-valencies increases. E X P E R I M E N T A L. Triammi?aecobalt Nitrite.-This was prepared according to Jorgensen's method (Zeitsch. anorg. Chem. 1896 13 172). The salt obtained was a crystalline brownish-yellow substance. Its constitution was determined by Werner who has shown from con-ductivity measurements that i t is non-ionisable (Zeitsch. physiknl. Chenz. 1893 12 35; 1896 21 227). To confirm Werner's state-ment an aqueous solution of the salt was added to a ferric hydr-oxide sol; no precipitate could be detected; the salt was therefore a non-electrolyte.The cobalt in the compound was estimated as sulphate and the total nitrogen was determined by Dumas's method. As regards nitritic nitrogen although Jorgensen (Zoc. cit.) has stated that he was able to estimate it by simple titration with potassium per-manganate it was found impossible to do so mainly owing to its sparing solubility. The salt was therefore heated with potassium hydroxide to expel ammonia the cobalt precipitated as oxide and the nitro-groups converted into nitrite. The solution was then filtered and the filtrate made up to a definite volume. The amount of nitrite was determined by titration with permanganate and also calculated from the volume of nitrogen evolved when the solution was treated with carbamide in a nitrometer.(Found: Co=23'67; N=33*22; NO,=18.12. Calc. Co=23'76; N=33*86; NO,= 18.55 per cent.) Dinitrotetra-amminecobalti-tetra,Litro~~amminecoba~tiate. - This compound exists in two stereoisomeric forms. One was prepared by double decomposition of potassium tetranitrodiamminecobaltiate, K[Co(NO,),(NH,),] with flavocobalt nitrite (1 2-dinitritotetra-amminecobalt nitrate [Co(NH,),(NO,),]NO, and the other with croceocobalt chloride (1 6-dinitritotetra-amminecobalt chloride, [Co(NH,),(NO,),]Cl according to the equation given below (Jorgensen Zoc. cit.) : %here X= acid radicle. (Found for 1 2-derivative co1=23'51, N .=33*19 NO = 18.82 j f o r 1 6-derivative Co =23-62 N = 33-52 PROPERTIES OF ISOMERIC COBALTAMMINES ETC. 53 NO,= 18-48.Calc. Co= 23-76 ; N = 33-86 ; NO,= 18.55 per cent.) Hexa-amminecobalti-hexanitrocoba1tiate.-This compound was prepared by double ilecomposition of luteocobalt chloride (hexa-amminecobaltic chloride [Co(NH,),]Cl with sodium cobalti-nitrite according to the equation given below (Jorgensen Zoc. c i t . ) : PWNH,),IC~~ + ~ ~ ~ c ~ ( N o ) I = [ co( N H3),]I1' - [ c 0 (N O2),]II1 -t 3 Na C1 . (Found Co = 23.54 ; N = 32.98 ; NO = 18-02. N=33*86; NO,=18.55 per cent.) Calc. Co= 23-76 ; D e t er nzinn t io 1% of D ensi t y . The densities of the isomerides were determined a t 32-33O, compared with water a t 4O and with xylene as a filling liquid in the same way as was done in the case of the hyponitrites (T. 1916, 109 128). In the following table are given the densities and molecular volumes of the isomerides : Name of isomeride.Tria.mminecobalt nitrite . . . . . . . . 1 2-Dinitrotetramminecobalti-tetranitrodiamminecobaltiate 1 6-Dinitrotetramminecobalti-tetranitrodiamminecobalt iate Hexamminecobaltihexanitroco -baltiate Mol. V O ~ . = Mean MoI. Wt. Density. density Density { 2.0006 248.0 { 2.0323 I 3.0324 344.3 {%I%!!/ 2.0291 241.6 I i:::;? 2.0626 310.5 2-0001 j 2.0348 2.0300 I 2-0652 [ For the sake of comparison twice the usual molecular formula has been employed in the case of triamminecobalt nitrite. The densities of 1 2-dinitrotetra-ammiiiecobalti-tetranitrodiammi~~e-cobaltiate and its stereoisomeride are practically equal but the table shows that the density increases as we pass froin triammine-cobalt nitrite t o hexa-amminecobalti-hexanitrocobaltiate.Further, from the data of molecular volumes i t will be noticed that the difference between the molecular volume of triamminecobalt nitrite and that of dinitrotetra-amminecobalti-tetranitrodiamminecobaltiate is about 4 which is also practically the difference f o r hexa-ammine-cobalti-hexanitrocobaltiate and dinitrotetra-amminecobalti-tetra-nitrodiamininecobaltiate. The difference in the number of electro-valencies of triamminp 54 DE RELATIONSHIP BETWEEN THE PHYSICAL cobalt nitrite and dinitrotetra-amminecobalti-tetranitrodiammine-cobaltiate is 1 whilst in the case of hexa-amminecobalti-hexanitro-cobaltiate and the latter compound it is 2. If the contraction of molecular volume had been proportional to the number of electro-valencies in the isomeride the difference between the molecular volume of hexa-amminecobalti-hexanitrocobaltiate and that of dinitrotetra-amminecobalti-tetranitrodiamminecobaltiate would have been doubled.The decrease in molecular volume however, along with the increase in the number of electro-valencies seems t o indicate that chemical affinity (valency) exerts an attaraction. From compressibility measurements Richards (Zoc. cit.) has calculated the amount of contraction which an alkali metal under-goes during the formation of its chloride. The contractions are recorded below in order to compare them with those of the above isomerides. Hypothetical contraction of metal Alkali metal. on combination.Lithium ........................... 5.1 Sodium ............................ 9.0 Potassium ......................... 20.6 Rubidium .......................... 24.3 Csesium ............................. 41.1 It will be noticed that the contraction for lithium is small and is comparable with the small contractions found in the isomerides. Solubility Determirta,tions. The isomerides were only sparingly soluble in water so that the determination of their solubilities from the amount of cobalt dis-solved in the solutions could not be trusted. The amount of the compound dissolved was therefore determined from the estimation of ammonia combined with cobalt atoms in the compound. The substance was shaken with a small quantity of water f o r some time until a saturated solution was obtained.The solution was then filtered and to a definite amount of the filtrate sodium hydr-oxide was added. Ammonia which was then distilled off was absorbed in sulphuric acid of known strength and was estimated by nesslerisation and also by titration of the acid in the receiver when possible. Water free from ammonia was always used in these experiments . The solubilities of the isomerides were determined a t the ordinary temperature. The data are given below PROPERTIES OF ISOMERIC COBALTAMMINES ETC. 55 Ammonium chloride found in 1 litre of the solution. Name of isomeride. Grams. Mean value. [ 1-8821 \ Triamminecobalt nitrate ... ... . . . 11.84861 1 2-Dinitrotetra-amminecobalti- f 2.3806 1- 2.3848 tetranitrodiamminecobaltiate..\ 2.38901 1 6-Dinitrotetra-amminecobalti- 0.2564) 0.2572 tetranitrodiamminecobaltiate.. { 0.25791 Hexa-amminecobaltihexanitroco-baltiate ...... ... ... .. ......... ...... {:} 0*0139 Weight of isomerides dissolved in 1 litre. Grams. 2-8820 3-6800 0.3977 0.0215 The ratio between the solubilities of triamminecobalt nitrite and 1 6-dinitrotetra-am1ninecobalti-tetranitrodiamminecobaltiate is 7.3:1 and that between the solubilities of the latter compound and hexa-amminecobalti-hexanitrocobaltiate is 18.5 1. The ratio between the solubilities of 1 2-dinitrotetra-amminocobalti-tetra-nitrodiamminecobaltiate and its stereoisomeride is 9.3 1. This great difference in the solubilities of the stereoisomerides is prob-ably due to the difference in their spacial configurations.1 N On N On Flavocobalt radicle. Croceocobalt radicle. (1 2-Dinitrotetra-ammine- (1 6-Dinitrotetra-cobalt radicle.) amminecobalt radicle.) It will be observed that in the flavocobalt radicle the two nitro-groups are in contiguous positions whilst in the croceocobalt radicle they are widely apart from each other. In organic sub-stances acid radicles in contiguous positions have been found to impart greater reactivity to the compound. The high solubility of the isomeride obtained f rom flavocobalt nitrate in comparison with that of its isomeride obtained from croceocobalt chloride may therefore be due t o the contiguous positions of the two nitro-groups in the flavocobalt radicle of the former compound. Exceptc ing the abnormal behaviour of the isomeride obtained from flavo-cobalt nitrate the solubilities of the isomerides will be observed t o decrease as the number of electro-valencies in them increases. For studying the change which is produced by valency alone, these isomerides are very suitable as the physical properties possessed by elements and groups of elements in them remain th 56 CHAPMAN SPTNACENE A NEW HYDROCARBON same. in this line employing isomerides of other complex compounds. The author therefore wishes to cont,inue his investigations I n conclusion my thanks are due t o Prof. P. C. R2y for the encouragement I received from him during the above investigation. CHEMICAL LABORATORY, PRESIDENUY COLLEGE, CALCUTTA. [Received December 21d 1916.

ISSN:0368-1645    

DOI:10.1039/CT9171100051

出版商:RSC    

年代:1917

数据来源: RSC

摘要:

56 CHAPMAN SPTNACENE A NEW HYDROCARBON By A. CHASTON CHAPMAN. IN September 1915 a sample stated to consist of cod-liver oil was submitted 'to me with the request that' I would report on its genuineness. I n the course of its examination the following results were obtained : Specific gravity (15'/15') .......................... 0.8666" Iodine value (Wijs) ................................ 358 Saponification value .................................. 22.5 Unsaponifiable matter.. ............................. Iodine value of unsaponifiable matter ......... 376.2 Free fatty acid (as oleic acid) ..................... 0.42 per cent. I reported that the sample consisted of a mixture of approsirn-ately 89 parts of some unsaturated hydrocarbon oil with approximately 11 parts of some fish oil.Whilst it was clear that I could not have arrived a t any other conclusion as to the general composition of the sample the analytical numbers perplexed me very greatly. I knew of no hydrocarbon or other unsaponifiable substance having the iodine value and the other properties which this appeared to possess and I began to wonder whether the sample might not be an abnormal and not an adulterated specimen of oil. I therefore decided for my own satisfaction to submit it t o a systematic investigation. As bearing on the origin and authenticity of this sample it is necessary to follow the history of the oil a little further before describing the results of its chemical investigation. Some weeks after the work had commenced I received a copy of a report which greatly stimulated my interest in the matter.The vendors of the oil in Lisbon repudiated the suggestion that it was not genuine and submitted a sample to Dr. Hugo Mastbaiun of 89.1 per cent. Bromine precipitate insoluble in ether ......... 76.5 , , FROM CERTAIN FISH LIVER OILS. 57 that city who obtained results similar to mine and expressed the same opinion. As the vendors were still not satisfied they sub-mitted portions of the fish livers to Dr. Mastbaum who again obtained similar results with the expressed oil. Finally Dr. Mast-baum witnessed the actual extraction of the livers of two different species of fish from which the oil in question had been derived. These fish which will be referred t o more fully below appear t o be known in Portugal as " Barroso " and (' Carocho " respectively.The fish according to1 Mastbaum were about 1 metre in length, were quite fresh and the livers were ('smooth and oily and when pricked with a knife considerable quantities of oil immediately separated the bulk of the liver substance being transformed in the course of a few hours into an oily liquid." I n a subsequent communication (Chem. Zeit. 1915 39 139 SSS), the following results are given by Mastbaum for these two samples of oil: '' Barroso." '' Carocho." Specific gravity (15"/15" ) ............ 0.8637" 0-87 11" Butyro-refractometer at 25". ........ 102 93 Polarisation in 200 mm. tube ...... -0.3 - 2.33 still liquid becomes turbid ................... at -7" a t -7" 36.7 -c Solidification point Saponification value ..................15.4 Free acids (calculated as oleic acid) 0.097 per cent. 0.165 per cent. Until quite recently I was unaware that Dr. Mastbaum had published this note and I therefore wrote to him pointing out that I had completed the first part of an investigation of the oil and asking him to give me any information he could in reference to its origin. He replied informing me that the oil in question was obtained from the two species of fish above referred to and added the information that according to a standard Portuguese dictionary the scientific descriptions of the above fish are Ceiztro-phorus granulosus and Scymmus lichia respectively. He also informed me that these fish are caught in deep water off the Moroccan coast and that they have only come into1 the Portuguese market since the employment of steam trawling in those fishing grounds.He suggests that it is owing to this fact that the exist-ence of fish-liver oils containing so large a proportion of unsaponi-fiable matter has hitherto1 escaped observation. Assuming that the fish in question were not in any way abnormal the existence of liver oils containing nearly 90 per cent. of an unsaturated hydrocarbon is a matter of very considerable interest both from the analytical and from the physiological points of view. The fact that samples of oil having approximately the same composition were derived from fish which had been caught during periods extending over several weeks and the fact that the D 58 CHAPMAN SPINACENE A NEW HYDROCARBON consignment represented by the sample submitted t o me amounted t o nearly 5000 litres must I think be regarded as tending t o negative any suggestion of abnormality.It may be recalled that cod-liver oil rarely contains more than 2 per cent. of unsaponifiable matters and that according to Lewkowitsch liver oils obtained from coal-fish tunny skate ling, haddock and hake rarely contain more than about the same amount. On the other hand shark-liver oil appears to contain in some cases as much as 20 per cent. which has been stated to consist largely of cholesterol. I n this .connexion it is of interest to note that the two fish above referred to belong to the Spinacid= or Squalid=) a family of the Selachoidei or sharks. E X P E R I M E N T A L . The sample of oil weighing 330 grams was heated on the water-bath with sufficient sodium hydroxide dissolved in alcohol to effect the complete saponification of the saponifiable portion.After evaporating the alcohol the residue was heated for some time with water and the unsaponified oil extracted by shaking with ether. The ether was distilled off and the remaining oil was heated in a current of steam until the aqueous distillate was free from odour. The oil which did not show any tendency t o distil with the steam, was again extracted with ether the solution dried over calcium chloride and the ether removed by distillation. The residual oil was then submitted to fractional distillation under a pressure of 10 mm. with the following results: ... ... ... 264-268' ...50 grams 268-269' ... ... ... ... 235 ,, 269-2'70' ... ... ... 5 ) ... The residue in the flask welghing about 10 grams was very viscous and dark coloured. From the first fraction there separated on keeping a small quantity of solid which proved t o be cholesterol. The main fraction gave on analysis numbers which indicated that it was a hydrocarbon with a small quantity of some oxygen-containing impurity the percentages of carbon and hydrogen amounting t o 99.6. A preliminary experiment having shown that metallic sodium was without action on the hydrocarbon this frac-tion was distilled over sodium under diminished pressure. There was a little action a t first but this soon ceased and the melted sodium remained quite bright throughout the distillation. The main fraction so obtained consisted of a colourless and fairly mobile oil having a faint and pleasant odour suggestive o FROM CERTAIN FISH LIVER OILS.59 1emOh oil terpenes. terpene-like odour. It burned with a smoky flame producing a C=87.63; H=12*51. It boiled a t 280° (corr.)/l7 mm.: 0.1381 gave 0.4438 CO and 0.1555 H,O. 0.135 , 0.4344 CO , 0.154 H,O. C=87-74; H=12*67. The following results represent the average of five analyses: C = 87.75 ; H:= 12.45. C,H, requires C = 87.80 ; H = 12.20 per cent. The average of four series of estimations by different observers of the molecular weight as determined by the depression of the freezing point in benzene solution was 375 whilst C30H50 requires 410. It will be seen therefore that the determined molecular weight agrees more closely with the formulae CZ7H, or C,,H,, with which the analytical results would also correspond.On the other hand the analyses of the crystalline hexahydrochloride and of the bromine derivative are in better agreement with the higher mole-cular formula. Assuming that the results obtained by the cryo-scopic method as applied to this hydrocarbon are normal there would appear to be a discrepancy which cannot a t present be explained. I would point out that the saturated hydrocarbon gives numbers agreeing better with one of the lower molecular formulae than with the higher. This hydrocarbon does not appear t o be identical with any known hydrocarbon and I propose for it the name spinacene since both Centrophorus granulosus and Scymnus lichia; belong to the natural family of the Spinacidz.It is optically inactive and does n o t solidify when cooled to - 2 O O . Its specific gravity a t 15°/150=0*8641 and a t 2O0/2Oo=0*8616. The following are the results of determinations of its index of refraction a t Z O O : nHa = 1'4932 nD =1.4967 ?LHP = 1.5054 mHy = 1.5130. A t 15O its index of refraction for the B-line is 1.4987. Its specific refraction calculated by the 7z2 - expression is 0.3394, and the molecular refraction 139.1. Taking Conrady's average numbers for the atomic specific refrac-tions (D-line) C30H5 with six ethenoid linkings requires 137.7. Employing the n2 formula the specific dispersive power of spinacene r y - ra is 0.0114 and its molecular dispersion ( r y - m ) M , 4.67.Taking Eisenlohr's numbers for the atomic dispersions for the a- and the y-hydrogen lines the calculated number is 4-33. It (72fT2)d D* 60 CHAPMAN SPINACENE A NEW HYDROCARBON will be seen therefore that the molecular dispersion like the molecular refraction is high. I n this connexion it is worthy of note that both the molecular refraction and the molecular dis-persion of the saturated hydrocarbon obtained from spinacene and described later agree well with the calculated numbers. Viscosity (Time of Efiucc).-Fifty C.C. of spinacene required 78 seconds to flow through the aperture of a Redwood viscometer a t 21° as compared with an average of 370 seconds for rape oil. Absorption of Ozygelz.-1*662 Grams of spinacene were exposed in a flat-bottomed glass dish to an atmosphere of oxygen a t the ordinary temperature.A t the end of two months the hydrocarbon had absorbed 0.397 gram of oxygen and had become so viscous that it would not flow Thin films of the hydrocarbon when exposed to the air formed a hard skin similar to that given by linseed oil. Action of Hydrogen Chloride. Spinacene Hexahydrochloride, C30H50 6 HCl. Dry hydrogen chloride was passed into a well-cooled solution of spinacene in dry ether until the liquid appeared to be saturated. After remaining for some hours a quantity of a well crystalline, colourless solid separated. This was collected washed with ether, and dried in an exhausted desiccator over sulphuric acid and solid sodium hydroxide. More of the solid separated from the filtrate after keeping for twenty-four hours and when this was removed a further quantity formed on remaining for several days.When heated with any of the liquids ordinarily employed for purposes of purification the substance appeared to undergo decomposition but it could be crystallised from a cold mixture of benzene and alcohol. From this solvent it separates in well-defined plates together with some needles the substance being polymorphous : 0.1058 gave 0.2242 CO and 0.0847 H,O. 0.20 , 0.2727 AgCl. C1=33.81. 0.25 , 0.3402 AgCl. C1=33*75. C=57*78; H=8*89. C,H6,,6HCl requires C = 57-23 ; H = 8-90 ; C1= 33.86 per cent. When heated the hexahydrochloride commences to shrink a t 108O and begins to melt a t l l O o . On raising the temperature to about 140° hydrogen chloride is freely evolved.I n a future communication I hope t o deal with the nature of the hydrocarbon left when the elements of hydrogen chloride are removed from the compound either by heating or by the action of reagents FROM CERTAIN FISH LIVER OILS. 61 I propoee also to investigate more closely the properties of spinacene from the point of view of its saturation with other elements or groups. I n particular t,he action of ozone is being studied as i t is expected that this will throw considerable light on the constitution of the hydrocarbon. Spiiuzcene Trihydrochloride CaH,,,3HC1. A current of dry hydrogen chloride was passed through a thoroughly cooled solution of spinacene in ether. As soon as the hydrogen chloride appeared to be in excess the solution was set aside for twenty-four hours and the resulting crystalline hexa-hydrochloride removed by filtration.The ethereal filtrate was shaken with sufficient aqueous solution of sodium carbonate t o remove the excess of hydrogen chloride and was then washed with water dried and evaporated under diminished pressure without the application of heat. A viscous oil remained together with a little of the crystalline hexahydrochloride. The residue was dis-solved in the smallest possible quantity of dry ether and filtered in order to separate the crystals. The ethereal solution after treatment with a little charcoal, was transferred t o a desiccator and the ether allowed to evaporate under diminished pressure. The residue consisted of a pale yellow, viscous oil having a specific gravity 18°/180=1*0137.It is of interest to note that when in one experiment the ethereal solu-tion was treated with sodium carbonate solution immediately after its saturation with hydrogen chloride the resulting oil contained but little chlorine. It is evident therefore that the formation of even the trihydrochloride requires some appreciable time f o r its completion : 0.2607 gave 0.2408 AgCl. C1= 22.90. C3,H,,,3HCl requires C1= 20.5 per cent. The excess of chlorine is due t o the impossibility of separating the hexahydrochloride completely as on keeping a little of the crystalline substance always separates from the oil. When the trihydrochloride is dissolved in ether and the liquid saturated with hydrogen chloride the crystalline hexahydrochloride is formed.Action of Bromine. The action of bromine on spinacene is somewhat complicated, since not only does the saturation of the double bonds appear t o take place in two stages but substitution derivatives are simultaneously formed. Even when a dilute solution of bromine in dry ether or in carbon tetrachloride is added slowly t o a dilut 62 CHAPMAN SPINACENE A NEW HYDROCARBON solution of spinacene in the same solvents a t a temperature of - loo hydrogen bromide is formed in considerable quantity from the very beginning. A solution containing 0.445 gram of bromine in 25 C.C. of carbon tetrachloride was added t o 20 C.C. of a solution containing 0.1996 gram of spinacene in the same solvent'. Both solutions were well cooled in a freezing mixture and immediately after the addition the excess of bromine was determined by titration with sodium thiosulphate after the addition of potassium iodide in the usual way.It was found that 0.39 gram of bromine had entered into the reaction corresponding with 10 atoms of bromine for one molecule of spinacene. The following experiments will illustrate this behaviour. This experiment was repeated with a similar result. I n the next experiment 50 C.C. of the bromine solution (0.89 gram of bromine) were added to the same volume (20 c.c.) of the spinacene solution and t h e excess of bromine determined after keeping f o r three hours a t the ordinary temperature. 0.1996 Gram of spinacene had reacted with 0.566 gram of bromine correspond-ing with rather more than 14 atoms for one molecule.I n these experiments hydrogen bromide was given off in apparently considerable quantities. The following experiments were then made with the object of differentiating between the bromine uniting directly with the hydrocarbon and the bromine existing as hydrogen bromide formed during the operation as the result of substitution. The well-cooled bromine solution was run as before into the well-cooled solution of spinacene in carbon tetrachloride in an apparatus so arranged as t o permit of the estimation of the hydrogen bromide formed. To 0.2007 gram of spinacene 0.557 gram of bromine was added. Immediately after the addition, it was found that 0.427 gram of bromine had reacted, of which 0.0673 gram existed as hydrogen bromide.From this it will be seen that the weight of spinacene taken has united directly with 0.427 - (0.0673 x 2) = 0.2924 gram of bromine which corre-sponds with rather more than 7 atoms for one molecule. I n a further experiment still more carefully arranged so as to prevent the loss of any hydrogen bromide i t was found that the amount of bromine with which one molecule of spinacene united directly corresponded with 6.7 atoms. The above results show that under the conditions obtaining in the last two experiments that is t o say when the temperature was kept low when the solutions of the hydrocarbon and of the bromine were dilute and when the titration of the uncombine FROM CERTAIN FISH LIVER OIL3. 63 bromine was made a t once only three of the six ethenoid linkings are saturated.This fact coupled with the existence of the tri-hydrochIoride and of the other tri-derivatives referred to below, appears t o indicate that three of these linkings are differently situated in the molecule from the remaining three. The fact that the above results are slightly in excess of the six atoms corre sponding with three ethenoid linkings may be due to the com-mencement of the saturation of the remaining linkings or to the union of the spinacene with some of the hydrogen bromide a t the moment of its formation. The most probable explanation of this behaviour with bromine is that three of the ethenoid linkings are in the open chain and the remaining three in some ring system. This view is supported by the way in which spinacene reacts with hydrogen chloride and by some other considerations which will be referred to later.Spinuc erne Dode ca b ro mide C30H50Br12. When a solution of bromine in dry ether is added to a solution of spinacene in the same solvent the colour of the bromine rapidly disappears and after a time a white finely crystalline substance commences to separate. This was filtered washed with ether and purified by the cautious addition of alcohol t o a solution in tetra-chloroethane when it separated in a crystalline condition. From the filtrate which contained an excess of bromine a further quantity of the same compound seEarated on keeping for some days and when this was removed some more crystallised on further keeping : 0.1252 gave 0.123 CO and 0.0416 H20. C=26.79; H=3*69.0.150 , 0.2453 AgBr. Br=69.7. C30H50Br12 requires C = 26-27 ; H = 3-64 ; Br = 70.07 per cent. When heated the substance commences to darken a t about 160° and melts and decomposes at. about 1 8 5 O . It is not appreciably soluble in alcohol or ether is sparingly soluble in acetic acid carbon tetrachloride o r chloroform and is moderately soluble in pyridine or trichloroethylene. It was found that a portion of the bromide which separates from the ether was insoluble in tetrachloroethane the remainder being freely soluble, This contained the same percentage of bromine as the soluble portion so that it would seem that the dodecabromide exists in two modifications. The compound soluble in tetrachloroethane exhibits the pheno-menon of polymorphism the same microscopical preparation often showing needles plates and nodules.I n some cases the trans-formation of one form into the other as for example the forma 64 CHAPMAN SPTNACENE A NEW HYDROCARRON tion of needles from spherical nodules can be observed. When solutions in carbon disulphide are allowed to remain for some time they become converted into a jelly. The filtrate from the above insoluble bromine derivatives was shaken with a slight excess of an aqueous solution of sodium hydroxide. The ethereal liquid was washed with water dried, and evaporated under diminished pressure without the applica-tion of heat. A viscous oil remained which on the addition of a mixture of light petroleum and alcohol and stirring with a glass rod gradually solidified.It was purified by crystallisation from a mixture of ethyl acetate and alcohol or from a mixture of benzene and alcohol. From the latter solvent it forms colourless, spherular masses of radiating needles. This contained 63.7 per cent. of bromine corresponding almost exactly with nine atoms of bromine but owing to the complex character of the reactions involved and to the impossibility of distinguishing by analysis between additive compounds and those in which there has been some substitution i t is inadvisable a t the moment to assign a definite formula to this derivative. The study of this and of other compounds formed during the action of bromine is being continued. Spinacene Trin itrosoch loride C3)H5"( N0C1)3. Two grams of spinacene were mixed with 5 C.C.of amyl nitrite, and to the liquid cooled to -15O a mixture of 6 C.C. of hydro-chloric acid (D 1-19> and 12 C.C. of glacial acetic acid was added. The mixtnre when vigorously shaken became green and in a very short time almost solid. It was allowed to remain in the freezing mixture for one hour and was then treated with water and filtered. An attempt was made to crystallise the air-dried substance from various solvent's but the heating necessary to bring about solu-tion invariably caused decomposition. It was finally obtained in a roughly crystalline form by dissolving it in cold tetrachloro-ethane and gradually adding light petroleum in which it is insoluble. It forms a pale buff-coloured substance which when dry is moderately stable. The above conditions must be closely followed if the solid nitrosochloride is to be obtained and as is the case with the majority of the compounds of spinacene the best results are got by working with small quantities of substance: 0-2533 gave 0.1889 AgC1.Cl=18.48. 0.252 , 16.4 C.C. N2 a t 20° and 752 mm. N=7-36. C3,H,,03N3C13 requires Cl= 17.50 ; N = 6.92 per cent FROM CERTAIN FISH LNER OILS. 65 So far as I am aware this is the first instance of the prepara-tion of a nitrosochloride containing three NOCl groups. The excess of chlorine is due to the impossibility of .obtaining this conipound free from a little of the hexanitrosochloride these com-pounds being unstable and consequently difficult to purify. S 2 r i n ~ r ~ n ~ Dinitrosochloride Mononit?.ol~'p~ridi~p, C3oH,,,(NOC1)2NOC,NH,o.When piperidine was added to the solid spinacene trinitroso-chloride the latter dissolved readily with development of heat. After heating the solution gently in order to avoid decomposition, cold water was added. The precipitated substance was collected, dissolved in dilute sulphuric acid and precipitated by the cautious addition of dilute sodium hydroxide solution. It was then purified by dissolving i t in cold alcohol and precipitating by the gradual addition of water. When dry i t formed a buff-coloured substance which was very readily soluble in dilute acids and in the ordinary organic solvents. When heated it commenced to shrink a t about l l O o and melted and decomposed at about' 146O : 0.2140 gave 17.0 C.C. N a t 15O and 758 mm.This substance forms a crystalline hydrochloride. In the above preparation although the amount of piperidine was in excess of that required to react with the three NOCl groups, it will be seen t h a t only one was attacked. N=9.10. C3,H,;,,0,N,C12 requires N = 8.60 per cent. Sp'nacen~ Trinifroli?ipell.i~~de C,,H,,(NOC,NH,,,),. In the preparation of this compound the nitrosochloride was added to a quantity of piperidine in excess of that required to react with the three NOCl groups. As before there was con-siderable development of heat but' in this case as soon as the reaction had slackened the liquid was heated nearly to the boil-ing point of piperidine. From the resulting dark brown liquid, water precipitated a gummy substance which was purified by dis-solving it in dilute sulphuric acid and precipitating with a dilute solution of sodium hydroxide this operation being repeated three times.The resulting substance which had a pale brown colour, was very readily soluble in alcohol and unlike the mononitrol-piperidide was not precipitated by the addition of water : 0.2041 gave 20.4 C.C. N a t 15O and 758 mm. When dry hydrogen chloride was passed into a solution of this N=11.52. C,,H,,O,N requires N = 11.20 per cent 66 CHAPMAN SPINACENIX A NEW HYDROCARRON compound in ether a crystalline substance separated which how-ever became gummy when attempts were made to dry it. Spinaceite Dinitrosochloride Mononitrolb en2 ylamide, C,,H,,( NOCl),NO*NH*CH,* C,H,. Spinacene nitrosochloride was added little by little to benzyl-amine the latter being in excess of the quantity required to react with the three NOCl groups.There was a vigorous reaction and when this had subsided the mixture was gently warmed and allowed to remain at the ordinary temperature for an hour. On treating the resulting pasty mass with cold water a plastic brown substance remained undissolved. This was purified by dissolving it in cold alcohol and precipitating it by the gradual addition of water the process being repeated several times. Finally the substance after drying was obtained as a buff-coloured powder : 0.2027 gave 15.4 C.C. N a t 20° and 752 mm. N=8*59. 0.1696 , 0.076- AgC1. C l = l l . l l . C,7H,80,N4Cl requires N = 8-27 ; C1= 10.50 per cent. Spinacene Triizitrol b enzylamide C30H,,(NO-NH*CH,*C,H5)3.Spinacene nitrosochloride was treated with an excess of benzyl-amine as in the preparation of the preceding compound but after the first reaction had subsided the mixture was heated to the boil-ing point of benzylamine for a few minutes. On the addition of water to the resulting dark red solution a viscous substance separated. This was purified by repeated solution in alcohol and precipitation with water and finally by dissolving it in glacial acetic acid diluting with water and precipitating with ammonia. The substance thus obtained had when dry a pale yellow colour, dissolved readily in dilute acids and appeared t o form a crystal-line hydrochloride : 0.1653 gave 15.8 C.C. N a t 21O and 740 mm. C,,H,,O,N requires N = 10.27 per cent. It will be seen that the action of benzylamine on the nitroso-chloride is similar to that of piperidine that is to say one mole-cule of NOCl is much more readily attacked than the remaining two.N=10*58. Spina c e n e H e xn n 1 t TOS o c h7oride C,,H (NO C1) 6. I n the preparation of the trinitrosochloride as described above a substance was obtained on one occasion which on analysis wa FROM CERTAIN FISH LIVER o m . 67 found to give the following results corresponding approximately, as will be seen with the composition of a hexanitrosochloride: 0.2381 gave 22.4 C.C. N a t 21° and 754 mm. N=10*62. 0.2305 , 0.255 AgCI. C1=27*42. C,0H5,0,N,C16 requires N = 10.46 ; C1= 26-52 per cent. The experimental conditions attending the preparation of the above compound did not differ intentionally from those which in other cases resulted in the formation of the trinitrosochloride.The percentage of chlorine is high but the compound is not very stable and is difficult to purify. Spins c e n e N i t rosa t e C3,H5 (N 0 *N 0,) 3. A mixture of spinacene with twice its volume of amyl nitrite was cooled in a freezing mixture to -15O and to this solution a well-cooled mixture of nitric acid and glacial acetic acid way added little by little with constant shaking. After remaining at the above low temperature for one hour the mixture which had become viscous was poured slowly into cold water. A yellow substance separated which could not be satisfactorily recrystal-lised from any of the ordinary organic solvents. The substance is practically insoluble in light petroleum sparingly soluble in ether or carbon disulphide somewhat more readily soluble in alcohol benzene chloroform o r carbon tetrachloride and very readily soluble in acetic acid tetrachloroethane or acetone.When heated it decomposes a t 85O with the formation of a considerable volume of gas. When prepared as above described it consisted of a yellow powder but when kept in a specimen phial for several weeks at the ordinary temperature i t underwent gradual decomposition, becoming converted into a dark brown spongy mass: C,HmO,,N requires N = 12.30 per cent. 0.2704 gave 31.0 C.C. N a t 1 9 O and 739 mm. Many attempts were made to prepare a nitroso- or an isonitroso-derivative of spinacene but without success. When to a solution of spinacene in light petroleum cooled to -15O a concentrated aqueous solution of sodium nitrite was added followed by the addition of acetic acid the mixture acquired a bright green colour, indicating the formation of a nitroso-compound but no crystal-line substance could be obtained.N=12.80. W y clr og e n a t i o n of S p i ~ a c e I L e . Fifteen grams of spinacene were introduced into a test-tube together with rather more than 1 gram of freshly prepared an 68 CHAPMAN SPINACENE A NEW HYDROCARBON ETC. very active platinum black. The tube was supported in an air-bath which was so heated that the contents of the tube could be maintained a t a temperature of 180° t o 190° throughout the experiment. A slow current of dry purified hydrogen was passed through the heated spinacene by means of a piece of glass tubing drawn out to a fine orifice and passing to the bottom of the tube, so as to keep the platinum black in a state of suspension.The iodine value which a t the commencement of the experi-ment was 350 (Wijs’s method) fell rapidly a t first and then more slowly until after the hydrogen had been passing for about thirty hours i t had fallen to 18 at which point i t remained almost stationary. The contents of the tube were separated from the platinum black and fractionally distilled over metallic sodium under 18 mm. pressure. Almost the whole of the liquid passed over a t 274-275O (corr.) as a perfectly colourless odourless oil, which burned with a smoky flame and a slightly resinous odour : C=85.23; H=14-67.0.138 gave 0.431 CO and 0.1822 H,O. It will be seen that the above formula is that of a paraffin. That this hydrocarbon is not a normal paraffin is shown by the fact that it remains liquid when cooled to -20° and for several reasons it seems improbable that it is one of the isoparaffins. The specific gravity of the hydrocarbon a t 20°/200= 0.8172O. The following are the results of determinations of its index of refraction a t 20°: C,H, requires C = 85-30 ; H = 14.70 per cent. ttHa= 1.4525 nD =1*454$ 9lHy = 1.4655. n1lp = 1.4607 Employing the n2 formula the specific refraction of this com-pound is 0.3318 and its molecular refraction 140.0. The theoretical number for a saturated hydrocarbon having the formula C,,H,, is 140.1. Its specific dispersion ry-ra is 0.0082 and its molecular dis-persion 3.46.Taking Eisenlohr’s numbers for the specific atomic dispersions of carbon and hydrogen for the a- and y-hydrogen lines, the calculated value is 3.47. The nature of this hydrocarbon like that of spinacene itself, must for the present remain a matter f o r conjecture. That spinacene is a chain compound containing a ring system is exceed-ingly probable but more than this can scarcely be said until the oxidation products have been thoroughly studied. As soon as the opportunity occurs I hope to deal as fully as possible with thi NITRATION OF 2-ACETYLAMINO-Q 4-DIMETHOXYBENZOIC ACID. 69 aspect of the subject. I would merely remark that some pre-liminary experiments in this direction tend to strengthen the view that this hydrocarbon may prove t o be in some way related to the t erpenes. Since this communication was submitted t o the Society I have seen a recent paper ( J . Z d . Eng. Chem. 1916 8 889) by M. Tsujimoto dealing with an unsaturated hydrocarbon obtained from the livers of certain Japanese sharks to which he has given the name “sgualene,” and which if not identical with spinacene, resembles i t closely. My best thanks are due to my assistant Mr. Frederick T. Harry, and to my late assistant Dr. B. Ghosh for valuable help in connexion with this investigation. 8 DUKE STREET ALDGATE E.C. [Received November 25th 1916.

ISSN:0368-1645    

DOI:10.1039/CT9171100056

出版商:RSC    

年代:1917

数据来源: RSC

摘要:

NITRATION OF 2-ACETYLAMINO-Q 4-DIMETHOXYBENZOIC ACID. 69 1 X . - The Nitration of 2 -A ce t y 1 a mino - 3 4 - d irne t hoxy -benxoic Acid and 3- Acetylaminoveratrole. By CHARLES STANLEY GIBSON JOHN LIONEL SIMONSEN and MADYAR GOPALA RAU.* IN a recent communication (T. 1915 107 SZS) Simonsen and Nayak described experiments on the nitration of 3-acetylamino-2-methoxytoluene which were undertaken with the object of synthesising 4-nitro-2 3-dimethoxybenzoic acid. Since the isomeric nitroamines obtained could not be converted into the correspond-ing nitrophenols the investigation did not lead to the desired result and i t therefore occurred t o us that if 6-nitro-3-amino-veratrole could be prepared it would readily yield the required acid on displacement of the amino-group by a carboxyl group.With this object in view we have examined the action of nitric acid on 2-acetylamino-3 4-dimethoxybenzoic acid (I) and 3-acetyl-aminoveratrole (IV) and although the reaction has not proceeded in the manner expected,+ it has yielded results of some interest. * An abstract of this paper was read a t the Third Indian Science Congress held in Lucknow on January 14th 1916. t Since the paper was prepared for publication (March 1916) we have received from Professor Majima a copy of a paper by Majima and Okazaki (Sci. Rep. Tdhoku Imp. Univ. 1916,5 215) in which the synthesis of 4-nitro-2 3-dimethoxybenzoic acid is described. The same authors have also shown the 5 6-dinitro-2 3-dimethoxytoluene prepared by Cain and Simonsen (ZOC. cit.) to be the 4 6-dinitro-isomeride 70 GIBSON SIMONSEN AND RAU THE NITRATION OF \ When 2-acetylamino-3 4-dimethoxybenzoic acid (I) was nitrated (see p.74) the sole product of the reaction was found to be 6-?~itro-2-ucetylarr~ino-3 4-dimethoxyl1 enzoic acid (11). The con-stitution of this acid was proved by the fact that on hydrolysis it lost carbon dioxide and yielded 5-nitro-3-aminoveratrole which on elimination of the amino-group gave 4-nitroveratrole. 5-Nitro-3-arninoveratrole has also been obtained in the form of its acetyl derivative by the nitration of 3-acetylaminoveratrole (IV) and this is probably the simplest method for the preparation of this substance. When 5-nitro-3-aminoveratrole was diazotised and treated with cuprous cyanide it yielded 5-nitro-2 3-dimethoxyb enzonitde (V), which on hydrolysis gave 5-nitro-2 3-dimethoxybenzoic acid (VI).This acid was found to be identical in every respect with the acid previously described by Cain and Simonsen (T. 1914 105 159),* and there can therefore be no doubt as t o its constitution. I n view of the discrepancy as to the melting point of 6-nitro-2 3-dimethoxybenzoic acid Perkin and Robinson (T. 1914 105, 2390) stating that it melted a t 178-5O whereas Wegscheider and Klemenc (Monatsh. 1910 31 709) gave 189O we have thought it advisable to prepare this acid by the methods given by these * The melting point of 5-nitro-2 3-dimethoxytoluene should be read 75-76O and not 176-176" ELE is given in this paper 2-ACETYLARIINO-3 4-DIMETHOXYBENZOIC ACID ETC. 7 1 investigators and also to compare it with the acid prepared by Cain and Simonsen (loc.cit.). We have found that the acid pre-pared by any of these three methods melts a t 185-186O (corr.), and it would therefore appear that the melting point found by Perkin and Robinson was somewhat low. When 2-acetylamino-3 4-dimethoxybenzoic acid was nitrated under conditions slightly different from those which were found to give a nearly quantitative yield of the nitro-acid a substance was obtained which decomposed a t 241° and is considered to be 4 5-dinitro-3-acetylarninoweratrole (VII). This substance was also formed together with an isomeride 5 6-dinitro-3-acetyiarnino-veratrole (VIII) when either 3-acetylaminoveratrole (IV) or 5-nitro-3-acetylaminoveratrole (111) was nitrated with fuming nitric acid.The constitution of the substance decomposing a t 241O was proved by the fact that on displacement of the amino-group by hydrogen 4 5-dinitroveratrole was obtained whilst the constitu-tion of the isomeride may be directly deduced from its prepara-tion by the nitration of 5-nitro-3-acetylaminoveratrole. 4 5-Dinitro-3-acetylaminoveratrole was found to be a substance of considerable interest. It was soluble in sodium hydroxide or barium hydroxide solution giving a yellow solution which slowly became red on keeping. It was reprecipitated unchanged on the addition of dilute acids or on passing carbon dioxide through a solution of its salts so that it behaved like a phenol. So far as we are aware this is the first secondary amine of this type namely, an acetylamine which has been found to possess this property of forming salts.Other secondary amines soluble in alkali are of course well known and we may mention as an example picryl-aniline and even picrylmethylaniline (compare T. 1906 89 583 ; Bey. 1910 43 1549) although the latter belongs t o a somewhat different type being a tertiary amine. That the acidic properties are connected with the secondary amino-group is shown by the fact that the amine 4 5-dinitro-3-aminoveratrole was quite insoluble in alkali. The salt may be represented by the two formulz (X) and (XI) : OMe /\OM 72 GIBSON SIMONSEN AND RAU THE NITRATION OF and we are inclined to the view that formula (X) is the more probable since the solution of the freshly prepared salt is yellow, whereas one would expect an ortho-quinonoid salt of formula (XI) to be deeply coloured.It is possible that the red colour which developed on keeping the yeIlow solution of the salt may be due to the slow formation of a salt having the quinonoid structure. It is interesting to note that 5 6-dinitro-3-acetylaminoveratrole was found to be quite insoluble in alkali and this difference in properties between the two isomerides afforded a simple method for their separation. I n a series of papers Meldola and his collaborators have shown that when nitromethoxyamines are diazotised under suitable con-ditions the nitro-group in the ortho- or para-position with respect to the amino-group is eliminated and may be replaced by a halogen. Thus for example Meldola and Eyre (T.1902 81, 989) have shown that dinitro-p-anisidine (XII) yields chloronitro-anisole (XIII). OMe OMe OMe (XiI). (XIII.) (XIV.) OMe OMe Cl (XV.1 (XVI.) So far as material has permitted we have investigated the products obtained by diazotising the two dinitroamines described in this paper. We have found that 4 5-dinitro-3-aminoveratroIe, when diazotised in acetic acid and sulphuric acid solution readily couples with &naphthol yielding the azo-dye which was found to be a strong phenol and we consider it to be best represented by formula (XIV) one of the methoxy-groups having undergone hydrolysis. When the amine was diazotised in a mixture of acetic and hydrochloric acids and the resulting diazonium salt heated with alcohol a halogenated phenol was obtained one of the nitro-groups having been eliminated.To this substance from a consideration of Meldola's results we ascribe formula (XV) although owing t o the small amount. of material available we can offer no direct evidence in support of this constitution. When 5 6-dinitro-3-aminoveratrole was diazotised with amy 2-ACETYLAMINO-Q 4-DIMETHOXYBENZOIC ACID ETC. 73 nitrite in absolute alcoholic solution the main product of the reaction was a substance which crystallised from alcohol in which i t was somewhat sparingly soluble and melted a t 1 8 1 O . I n spite of the somewhat high melting point we consider this substance to be 3 4-dinitroi~eratrole (XVI) and the molecular weight deter-mined by Barger’s method supported this view.At the same time, a small quantity of a phenol was isolated which on methylation gave a methyl ether melting a t 89-90O; for this substance we are unable t o suggest a formula. The results described in this paper seem to be of some interest from the point of view of orientation in the benzene ring. It will be observed that on nitrating both 2-acetylamino-3 4-dimethoxy-beiizoic acid and 3-acetylaminoveratrole it is the methoxy-group in the ortho-position with respect to the acetylamino-group that appears to exercise the sole directing influence the nitro-group entering the para-position with respect to this methoxy-group. The second nitro-group then assumes mainly the para-position with respect t o the other methoxy-group only a small quantity of the 5 6-dinitro-derivative being formed.If we ascribe the directing influence to the subsidiary valencies of the methoxy-group i t would then appear that such valencies are much intensified by the juxta-position of the positive acetylamino-group. This is the exact opposite to the results observed when the methoxy-group has a negative group in the ortho-position with respect to it since as has been shown by Perkin and Robinson (loc. cit.) o-veratraldehyde (XVII) on nitration gives as sole pro-duct a nitro-derivative (XVIII) in which the nitro-group has entered the para-position with respect to the methoxy-group furthest away from the negative group. (XVII.) (XVIII.) (XTX.) I n fact as Prof. Robinson has kindly informed us i t has been observed in a large number of cases examined by him that when a negative group is in the ortho- or para-position with respect to a positive group it neutralises such a group and the orientating effect is exercised by the second positive group.That this view cannot be of quite general application is however proved by the fact t$hat Cain and Simonsen (loc. cit.) found that o-veratric acid (XIX) gave on nitration 5-nitro-2 3dimethoxybenzoic acid (XX) 74 GIBSON SIMONSEN AND RAU THE NITRATION OF EXPERIMENT A L. Nitration of 2-Acetylnmino-3 4-dimethoxybenzoic Acid (I).* 6-Nitro-2-amino-3 4-dime t hoxy b enzoic A cid. The following method was found to give an almost quantitative yield of the above-mentioned nitro-acid. To a well-cooled mixture of nitric acid (D 1.4; 9 c.c.) and sulphuric acid (6 c.c.) 2-acetyl-amino-3 4-dimethoxybenzoic acid (3 grams) was gradually added with vigorous stirring.The acid slowly passed into solution and after ten minutes the mixture was poured on ice. A clear solu-tion was thus obtained which gradually became cloudy and the nitro-acid was deposited in fine pale yellow crystals. These were collected and purified by crystallisation from water containing a little alcohol. (Yield 3-5 grams.) For analysis the acid was dried at looo -f 0.1000 gave 0.1708 CO and 0.0398 H20. 0.1715 , 15.8 C.C. N a t 33O and 756 mm. N=9*7. C,,H,,07N2 requires C = 46.5 ; H = 4.2 ; N = 9.8 per cent. 6-Nitro-2-acetylamino-3 4-dimethoxybenzoic acid crystallises in very pale yellow prismatic needles which soften a t 215O and decompose a t 220O.It is very sparingly soluble in cold water, benzene ethyl acetate or chloroform but more readily so in acetone or hot water and very readily so in alcohol. On titration with a standard solution of barium hydroxide, 0.0812 gram neutralised 0.0247 gram of Ba(OH), whereas a mono-basic acid C11H1207N2 should require 0.0245 gram. The silver salt is very readily soluble in water but separates from an aqueous solution on the addition of alcohol in fine yellow needles : C=46.6; H=4.4. 0.1491 gave 0.0414 Ag. Ag=27.8. C,,H,,07N,Ag requires Ag= 27.6 per cent. * The acetylamino-acid was prepared by the method described by Pschorr and Sumuleanu (Bey. 1899 32 3411) when it was obt.ained in colourless plates which decomposed at 195-196". (FoundC=55.8; H=5.5; Ac= 18.0; Calc.C=55.2; H ~ 6 . 4 ; Ac-18-0 per cent.). It was stated by Pschorr and Sumuleanu to melt a t 191" and to crystallise in needles. On one occasion we obtained the acid in the form of needles which decomposed at 195-196" and the substance would therefore appear to be dimorphous (compare Chattaway and Lambert T. 1915,107 1766). t With the majority of substances described in this paper considerable difficulty was experienced in obtaining accurate analytical results. It was found necsssary to carry out the combustions very slowly and to interpose a U-tube filled with pumice moistened with sulphuric acid between the calcium chloride tube and the carbon dioxide absorption apparatus (compare Kletz and Lapworth T. 1915,107 1259) 2-ACETYLAMINO-3 4-DIMETHOXYBENZOIC ACID ETC.75 6-Nitro-2-amino-3 4-dimethoxybenzoic A cid. Much difficulty was a t first experienced in hydrolysing the acetyl group in the nitroacetylamino-acid since alkaline hydrolysis resulted in the formation of uncrystallisable oils whereas hydro-lysis with hydrochloric acid eliminated simultaneously the carboxyl group (see below). When however the acetylamino-acid was mixed with three times its weight of concentrated sulphuric acid and heated on the water-bath for half an hour hydrolysis readily took place a deep red solution being obtained. This was cautiously added to cold water and the excess of mineral acid removed by the addition of ammonia when a pale brown solid separated. This was collected and purified by repeated crystallisa-tion from ethyl acetate: 0.0728 gave 0.1186 CO and 0.0302 H,O.0.1283 , 14.4 C.C. N2 a t 30° and 760 mm. N=12*0. C,H,,0,N2 requires C=44-6; R=4*1; N=11-6 per cent. 6-Nitro-2-amino-2 4-&met hoxy b enzoic acid crystallises in pale yellow glistening needles which soften a t 185O and decompose a t 194-195O. It is readily soluble in alcohol or acetone somewhat readily so in ethyl acetate and very sparingly so in water benzene, or chloroform. It is a weak base being soluble in concentrated mineral acids separating however on dilution with water. C=44*4; R=4.6. 5-Ni t ro-3-aminovera t rol e (111). For the preparation of this substance 6-nitro-2-acetylamino-3 4-dimethoxybenzoic acid (3 grams) was mixed with hydrochloric acid (50 per cent.; 30 c.c.) and heated for two hours in a reflux apparatus.The excess of acid was removed on the water-bath, and the aqueous solution of the hydrochloride basified with ammonia when the nitroamine separated as a brown crystalline powder. This was collected and purified by crystallisation from dilute methyl alcohol when i t was obtained in pale brown pris-matic needles melting a t 105-106° : 0.1036 gave 0.1845 CO and 0.0498 H,O. C,H,,0,N2 requires C = 48.5 ; H = 5.3 per cent. 5-Nitro-3-aminoveratroZe is readily soluble in most organic solvents but only sparingly so in cold water more readily in hot water. The hydro-chloride and the sulphate are somewhat sparingly soluble in water. The platinichloride was obtained as a very sparingly soluble, microcrystalline yellow powder : C?=48.6; H=5.3.It does not appear to be volatile in steam 76 GIBSON SIMONSEN AND RAU THE NITRATION OF 0.0905 gave 0.0216 Pt. Pt=23*9. The acetyl derivative' separated from alcohol in faintly yellow, 0.1075 gave 0.198 CO and 0.0464 H,O. The b enzoyl derivative crystallised from acetic acid in colour-0.1645 gave 15.2 C.C. N a t 30° and 760 mm. (C,H,,04N2HC1),PtCl requires Pt = 24.1 per cent. glistening leaflets melting a t 172-173O : C-50.2; H2=4*8. C,,H,,O,N requires C = 50.0 ; H = 5.0 per cent. less glistening needles which melted a t 145-146O : C,,H,,0,N2 requires N'= 9.3 per cent. N=9.7. Dinzotisation of 5-Nitro-3-aminoveratrole. I. Formation of 4-Nitroveratrole. I n carrying out this experiment the nitroamine (0.5 gram) was dissolved in alcohol (5 c.c.) and sulphuric acid (0.5 gram) was added when the sparingly soluble sulphate separated in glisten-ing leaflets.To the well-cooled solution amyl nitrite (0.7 gram) was slowly added when the sulphate gradually passed into solu-tion. When the reaction was complete the clear solittion was carefully heated on the water-bath until all evolution of nitrogen had ceased. On pouring into water 4-nitroveratrole separated as an oil which rapidly solidified. It was crystallised from methyl alcohol when it was obtained in fine needles melting a t 95-96O, and this melting point was unaltered on admixture with a speci-men of 4-nitroveratrole from another source. 11. For m,rr I 1'0 ?a of 5 -Nit r 0-2 3-dim e tho my b e ti zo ti i t ril e (IV) . The amine (3 grams) was mixed with dilute sulphuric acid (H,S04 5 grams) when the sparingly soluble sulphate separated.This was diazotised in the usual manner with sodium nitrite and the clear liquid was gradually added t o a hot solution of cuprous cyanide (potassium cyanide 4.2 grains ; copper sulphate 3.7 grams). The mixture was heated on the water-bath until no more nitrogen was evolved (about thirty minutes) and the brown solid which had separated was dissolved in ether the ethereal solution filtered to remove a little insoluble resin washed with alkali to remove any phenol formed dried and evaporated when the nitrile was obtained as a brown powder (2.1 grams). It was purified by repeated crystallisation from dilute methyl alcohol with the aid of animal charcoal when i t was obtained in pale brown prismati 8-ACETYLAMINO-3 4-DIMETHOXYBENZOIC ACID ETC.77 needles which melted at about 127-128O but it is doubtful if it was quite pure. It was readily soluble in most organic solvents: 0.1304 gave 15.7 C.C. N at 30° and 752 mm. N=12.9. C9H,0,N requires N = 13.4 per cent. Hydrolysis of 5-Nitro-2 3-dimethoxybenzonitrde. The hydrolysis of the nitrile to the corresponding acid offered much difficulty and ultimately the following method was adopted although the yield was by no means satisfactory. The nitrile (1 gram) was mixed with barium hydroxide (3 grams) dissolved in water (10 c.c.) and heated in a reflux apparatus for three hours when all evolution of ammonia had ceased. The brown solution was filtered from a little resinous matter and acidified when a pale yellow solid separated and was collected.This was found to consist of a phenolic acid mixed with a little of the dimethoxy-acid the aqueous solution giving a deep red colour with ferric chloride. The crude acid was converted into the scarlet potassium salt and the dry salt heated with excess of methyl sulphate in a stoppered bottle on the water-bath the treat-ment being repeated three times when the greater part of the phendlic acid was methylated. The acid obtained in this manner was dissolved in dilute sodium carbonate solution and oxidised on the water-bath with potassium permanganate in order to remove any unmethylahd phenolic acid. After filtering off the man-ganese dioxide the solution was concentrated and acidified when 5-nitro-2 3-dimethoxybenzoic acid (VI) separated.This was collected and crystaIlised from hot water when it melted a t 174-175O and was found to be identical in every way with the acid obtained by Cain and Simonsen (Zoc. cit.). The ethyl ester melted a t 78-79O and this melting point was unaltered on admixture with an equal amount of the ethyl ester which had been prepared by Cain and Simonsen. The methyl ester crystallised from dilute methyl alcohol in fine needles melting at 76-77O. As this melting point was only slightly different from that of the methyl ester of the isomeric 6-nitro-acid a mixture of equal parts of these two esters was made, and was found to' melt indefinitely a t about 60°. (Found: N= 6.4. It is of interest to note that the methyl ester has apparently a lower melting point than the ethyl ester which is somewhat unusual (compare Meyer " Analyse und Konstitutionsermittelung organischer Verbindungen," p.107) Calc. N=5*8 per cent. 78 QIBSON SIMONSEN AND RAW THE NITRATION OF 6-Nitro-2 3-dirnethoxyber~aoic Acid. As has already been mentioned (see p. 70) in view of the different melting points obtained for this acid we have prepared it by the methods of Wegscheider and Klemenc and also by that of Perkin and Robinson. The acid prepared by either of these methods separated from water in leaflets melting a t 184-185° (corr.). The methyl ester was also prepared and melted a t 78-79O (Perkin and Robinson give 8l0) and this melting point was unaltered on admixture with a specimen of the methyl ester of this acid prepared by Cain and Simonsen.There can therefore be no doubt that the acid obtained by these three methods is identical. 4 5-Dinit ro-%ace t ylalrni~overatrole (VII). If the conditions adopted for the nitration of 2-acetylamino-3 4-dimethoxybenzoic acid are slightly varied then in addition to the formation of 6-nitro-2-acetylamino-3 4-dimethoxybenzoic acid a substance was obtained which f o r reasons already given (see p. 71) is considered to be 4 5-dinitro-3-acetylaminoveratrole. I n one experiment the acetylamino-acid (22 grams) was added to a well-cooled mixture of nitric acid (D 1.4; 44 grams) and sulphuric acid (88 grams); the solution became deep red and a vigorous evolution of gas was observed. After fifteen minutes, the mixture was poured on ice and the solid ( A ) which separated was immediately collected.The filtrate on keeping desposited a further quantity of solid (3 grams) which was found to be nearly pure 6-nitro-2-acetylamino-3 4-dimethoxybenzoic acid. On extraction with ether the filtrate yielded a small quantity of an acid (0.6 gram) which crystallised from hot water in colourless, prismatic needles decomposing a t 191O. Unfortunately a sufficient amount of this acid could not be obtained for a detailed examina-tion to be made. The main product of the nitration ( A ) was dissolved in dilute sodium hydroxide and the deep reddish-brown solution was saturated with carbon dioxide when a colourless solid separated (3.8 grams).* This was collected and purified by crystallisation from alcohol when 4 5-&nitro-3-acetylaminoveratrole separated in long glistening colourless needles which decomposed a t 241O : 0'123 gave 0.191 CO and 0.0413 H,O.C=42*3; H=3*7. 0.1865 , 26.2 C.C. N a t 33O and 759 mm. N=14.9. C,,H,,O7N3 requires C=42*1; H = 3.8 ; N = 14.7 per cent. * The sodium carbonate solution on acidification yielded a further quantity of 6-nitro-2-acetylamino-3 4-dimethoxybenzoic acid 2-ACETYLAMINO-Q 4-DIMETROXYBENZOIC ACID ETC. 79 The substance is readily soluble in sodium hydroxide or barium hydroxide yielding a yellow solution which becomes red on keep-ing. When 4 5-dinitro-3-acetylaminoveratrole was heated for one hour with acetic anhydride containing a little pyridine and the acetic anhydride removed in a vacuum 4 5-dinitro-3-diacetylamino-veratrole was obt'ained.This substance which was readily soluble in most organic solvents was purified by repeated crystallisatioii from benzene when i t was obtained in faintly yellow prisms melt-ing a t 130-131O: With ferric chloride it gives no coloration. 0.1042 gave 0.1700 GO and 0.0384 H,O. Cl2HI3O8N3 requires C = 44.0 ; H = 3.9 per cent. 4 5-Dinitro-3-diacetylaminoveratrole was found to be quite insoluble in alkali; it was somewhat readily hydrolysed to the monoacetylamine. C =44-4 ; H,=4.0. 4 5-Dinitro-3-aminoverat rol e. This substance was readily obtained by dissolving the acetyl-amino-derivative in concentrated sulphuric acid and heating for not more than ten minutes a t looo when on pouring into water, the amine separated as a flocculent powder.It was purified by crystallisation from methyJ alcohol : 0.1066 gave 0-1553 CO and 0.0384 H,O. 4 5-Dinitro-3-ami~ove~atrole crystallises in terra-cotta needles melting at 112-113O. It is insoluble in alkali but dissolves in hot concentrated hydrochloric acid being reprecipitated on dilu-tion. C=39.7; E=4.0. C8H,0,N3 requires C= 39.5 ; H = 3.7 per cent. 3-A minoveratrole (IV). The following method was found to give an excellent yield. 2-Amino-3 4-dimethoxybenzoic acid (10 grams) was suspended in glycerol (90 per cent.; 50 grams) and the mixture heated in an oil-bath a t 170-180° when the acid gradually passed into solu-tion and a vigorous reaction took place with the evolution of carbon dioxide. After keeping a t this temperature for thirty minutes the mixture was heated a t 215O for fifteen minutes cooled, and mixed with water when the amine separated as an oil.This was dissolved in ether the ether dried and evaporated and the residual oil fractionated under diminished pressure : 0.0924 gave 0.2134 CO and 0.0568 H,O. 3-Arninoveratrole is a colourless oil which boils at 137O/10 mm., C=62.9; H=6-9. C8Hl,0zN requires c= 62.7 ; H = 7.2 per cent 80 GIBSON SIMONSEN AND RAU THE NITRATION OF and possesses a faint odoar reminiscent of aniline. to the air it rapidly darkens in colour. steam and somewhat readily soluble in water. On exposure It is readily volatile in The picrate crystallises from alcohol in needles melting at 0.1015 gave 14.5 C.C. N a t 29O and 760 mm.The acetyl derivative separates from hot water in which it is 0.1443 gave 9.8 C.C. N a t 30° and 760 mm. The b ensoyl derivative crystallises from alcohol in glistening, 0-1094 gave 6.0 C.C. N a t 30° and 762 mm. 173-175': N=14.9. C8H,,0,N,C,H30,N3 requires N = 14.7 per cent. readily soluble in well-formed cubes melting a t 8 5 O : N=7-3. C,,H,303N requires N = 7.2 per cent. striated needles melting a t 1 0 7 O : N=5*9. C,,H,,03N requires N = 5.4 per cent. A'itration of 3-9 cetylami,zoveratrole. I . Forination of 5-Nitro-3-acet ylaminov erntrole (111). 3-Acetylaminoveratrole (1 gram) was added gradually with vigorous stirring to well-cooled nitric acid (D 1.4; 5 grams); the acetylamine gradually passed into solution and the nitro-deriv-ative crystallised out the whole mass becoming pasty.After fifteen minutes the mixture was poured on ice and the nitroacetyl-amine collected. (Yield 0.85 gram.) The 5-nitro-3-acetylamino-veratrole prepared in this manner crystallised in the glistening leaflets characteristic of this substance melted a t 172-1 73O and was found to be identical in every way with the acetylamine described above (see p. 76). On hydrolysis it yielded the nitro-amine melting a t 105-106°. 11. Formation of 4 ; 5-Dinitro-3-acetylaminoveratrole ( V I I ) and 5 6-Dir~itro-3-acetylaminoveratrole ( V I I I ) . 3-Acetylaminoveratrole (1 7 grams) was gradually added to nitric acid (D 1-52; 60 grams) which was well cooled in a freez-ing mixture the temperature not being allowed t o rise above 0".The acetylamine dissolved in the nitric acid with a hissing sound, and towards the end of the reaction the liquid became pasty owing to the crystallisation of the products of the nitration. After keep-ing for fifteen minutes the mixture was poured on ice and the solid was collected. The crude product obtained in this manner was repeatedly ground up with small quantities of dilute sodium hydroxide solu-tion until nothing further was dissolved. The insoluble portio 2-ACETYLL4MINO-3 4-DIMETHOXY BENZOIC ACID ETC. 81 was collected and the filtrate was reserved for further examina-tion (see below). The residue was purified by crystallisation froiii alcohol when it was obtained in faintly yellow needles melting a t 178-179O. (Yield 4.7 grams) : 0.1016 gave 0.1555 CO and 0.0365 H,O.5 6-Dinitro-3-acetylamino~1eratrole was found to differ from its isomeride in being quite insoluble in alkali. 5 6-Dinitro-3-aminoveratrole was readily obtained by hydrolysing the acetyl derivative with concentrated sulphuric acid. It crystal-lised from dilute alcohol in long yellow prismatic needles melting a t 141-142O. It appeared to be a somewhat stronger base than its isomeride its salts however being readily dissociated by water : 0.1039 gave 0.1504 CO and 0.0366 H,O. C,H,O,N requires C = 39-5 ; H = 3.7 per cent. The alkaline filtrate from which the 5 6-dinitro-3-acetylamino-veratrole had been separated was acidified and the solid which separated was collected. (Yield 11.4 grams.) It was purified by crystallisation from alcohol when it was obtained in colourless needles decomposing a t 241° and was found to be 4:5-dinitro-3-acetylarninoveratrole.(Found C = 42.4 ; H = 3.9. Calc. C = 4 2 1 ; 11-3.8 per cent.) C=41*9; H=3*9. Cl,H1,0,N3 requires C = 42.1 ; H = 3.8 per cent. C=39*5; H=3-9. Nitru tiom of 5-Nitro-3-ace t ylumii~ov era t role (111). 5-Nitro-3-acetylaminoveratrole was nitrated with nitric acid (D 1.52) under the conditions just described. The products were separated by means of alkali when from 0.3 gram of the nitro-acetylaniine 0.24 gram of the 4:5-dinitro- and 0.1 gram of the 5 6-dinitro-isomeride were isolated. Diuzotisution of 4 5-Dinitro-3-amii~overatrole. I. Formutiou of 4 5-Dinitroueratrole. The base (1.65 grams) was dissolved in alcohol (15 c.c.) and after the addition of sulphuric acid (1 gram) amyl nitrite (1.5 grams) was gradually added t o the well-cooled mixture when the sparingly soluble sulphate slowly dissolved.When the diazotisation was complete zinc dust (0.2 gram) was added and the mixture heated in a bbiling-water bath until the evolution of nitrogen was com-plete. The filtered solution was poured into water and the reddish-brown semi-solid oil which separated was dissolved in ether. The ethereal solution was washed with dilute alkali to remove the phenol dried and evaporated when a small quantity of a sub-stance was isolated which crystallised from methyl alcohol in VOL. CXI. 82 GIBSON SIMONSEN AND RAU THE NITRATION OF leaflets melt,ing a t about 140O. It was not obtained in sufficient quantity for analysis.The alkaline solution on acidification yielded a phenol which was not purified but was methylated in the usual manner with methyl sulphate when the methyl ether was obtained as a brown powder. This was crystallised from dilute acetic acid when it separated in yellow needles melting a t 127-128O and evidently consisted of 4 5-dinitroveratrole since the melting point was not depressed on admixture with a specimen of this substance from another source. (Found N= 12.6. Calc. N= 12.3 per cent.) 11. 4 5-Dinitro-2 -h ydrox y-1 -m e t hox y-3-az o-fl-naph t hot (XIV) . For the preparation of this substance the amine (1 gram) was dissolved in acetic acid (5 c.c.) and after the addition of sulphuric acid (0.8 gram) a solution of sodium nitrite (0.2 gram) was added to the well-cooled solution.The mixture was carefully added to an alkaline solution of &naphthol and the sparingly soluble indigo-blue sodium salt which separated was collected and decomposed with dilute acetic acid. The reddish-brown azo-compound was purified by repeated crystallisation from pyridine when i t was obtained in purple leaflets with a golden bronze metallic reflex decomposing a t 222O : 0.105 gave 0.2037 CO and 0.0342 H,O. The substance was found to be a strong phenol being readily soluble in dilute alkali yielding a reddish-purple solution so that there can be little doubt that one of the methoxy-groups had undergone hydrolysis. I n sulphuric acid it dissolved yielding a purple solution which became red on dilution.C=52.9; H=3*6. C,,H,,O,N requires C= 53-1 ; H = 3.1 per cent. 111. 4-Chloro-5-nitroguuiacol (XV). I n one experiment, the amine (1 gram) was dissolved in acetic acid (5 c.c.) and after the addition of hydrochloric acid (1 gram), a solution of sodium nitrite solution (0.25 gram) was added. When the diazotisation was complete an equal volume of alcohol was added and the mixture heated on the water-bath until all evolution of nitrogen had ceased. The mixture was poured into water the oil which separated was dissolved in ether the e'thereal solution washed with alkali t o remove the phenol dried and evaporated when a small quantity of an oil remained which was not further investigated. The alkaline solution on acidification deposited the phenol as a somewhat viscid red solid.This was collected and purified by crystallisation from hot water whe 2-ACETYLAMINO-3 4-DIMETHOXYBENZOIC ACID ETC. 83 4-cJ~loro-5-~~itroguaiacol was obtained in glistening pale brown leaflets or clusters of prismatic needles which melted a t 161-162O : C7H,0,NC1 requires C1= 17.4 per cent. 0.1236 gave 0.0834 AgCl. C1=17*1. Uiazotisation of 5 6-Dinitro-3-nnzi~zoveratrole 3 4Dinitro-? ; e m trol e (XVI). In the diazotisation of the 5 6-dinitroamineY the conditioris described above for the preparation of 4 5-dinitroveratrole were used. 3 4-Dinitroveratrole separated from alcohol in which it was somewhat sparingly soluble in glistening pa10 yellow prisms melt-ing a t 1 8 1 O : 0.1012 gave 0’1556 CO and 0-0333 H,O. C,H,O,N requires C = 42.1 ; H = 3.5 per cent.A molecular-weight determination carried out by Barger’s method using pyridine as the solvent and benzil as the standard, gave a molecular weight of about 235.8 whereas C,H,O,N requires M.W. = 228. From the diazotisation a small quantity of a phenol was isolated; this was converted into the methyl ether in the usual manner and the methyl ether recrystallised from methyl alcohol when it was obtained in pale yellow leaflets melting at about 88-89O. Unfortunately this substance was not obtained in sufficient! amount for complete purification. C=41.9; H=3*6. A dde tidum. From the difference in behaviour towards alkali of 4 5-dinitro-3-acetylaminoveratrole ( A ) and of ti 6-dinitro-3-acetylamino-veratrole ( B ) i t was considered that the examination of the absorption spectra of these compounds in alcoholic solution and in the presence of alkali might yield interesting results.The alkaline solutions contained five equivalents of potassium hydr-oxide. Mr. J. E. Purvis very kindly examined the absorption spectra and we are greatly indebted to him for the trouble he has taken and for his report which is as follows : “The sources of light were an iron spark and a molybdenum-uranium spark duplicate photographs being ta,ken in each case and the absorption curves drawn. “It will be seen that substance A exhibits one strong band with-out and with the addition of the alkali. The effect of the alkali is to make the band a little narrower and t o cause a considerable shifting of the line of general absorption towards the red end.( ( The neutral solution of the substance 13 shows two fairly well-E 84 GIBSON SIMONSEN AND RAU THE NITRATION OF marked bands whereas the alkaline solution gives only rapid extensions of the line of general absorption. There can scarcely be any doubt that the change in colour brought about by the Oscillation fi-equencies. 2400 2800 3200 3600 4000 4400 4800 3.6 3.2 2.8 2.4 2.2 1.8 1.4 10 Lower curves. I Upper curves. 4 5-Dinitro-3-acetylanzinoverutrole 5 6-Dinitro-3-acetylarninovcrwtrolc (4 I (B)* Neutral solution continuous line. I Neutral solution continuous line. Alkaline solution broken line. Alkaline solution broken line. addition of the alkali has produced a considerable change and it is possible that this may be due to decomposition whereby the vibrations of the original molecule are almost obliterated.“The single band of substance A is not unlike except in posi 2-ACETYLAMINO-3 4-DIMETIXOXYBENZOIC ,4CID ETC. 85 tion the band in the cases of phenol and the clihydroxybenzenes (Hartley T. 1888 53 651; ITartley Dobbie and Lauder T., 1902 81 929; Baly and Ewbaiik T. 1905 87 1347). On the other hand the two bands of the compound 13 are coinparable with the bands of aniline and certain derivatives of aniline for example the anisidines except' again in posit ion (Hartley and Huntington PJjil. TTUUS. 1879 170 I 257 ; Purvis T. 1915, 107 660). '' A consideration of the structure of the two substances indicates a probable sat isfactory explanation of these differences.In the case of substance A where one of the nitro-groups is in the ortho-position with respect to the acetylamino-group the former neutralises the influence of the latter aiid the methoxy-groups can then exert a more powerful influence. This close relationship is not present in the case of substance H where the nearest nitro-group is in the meta-position with respect to the acetylamino-groull. The latter has here more freedom of motion and hence the vibra-tions of the molecule become comparable with those of aniline. " I n the case of the alkaline solution of the substance A the curves indicate t h a t the vibrations are damped b u t t h a t no con-siderable change in the constitution of the substance has taken place. It has been suggested t h a t the solubility of the substance A in alkali may be due to the formation of an unstable salt but this would not largely alter the vibrations for the reason t h a t the influence of the acetyliniino-group would still be locked up by the atljacent :N<:" group. The fact that the absorption spectra of the neutral and the alkaline solutions of the substance A are so similar clearly proves t h a t the not improbable conversion of the nitro-group iii the ortho-position with respect to the acetylamino-/ 0 I\' group into the group N N ~ is not sufficient to effect any funrla-mental change in the inflneuce of the niethoxy-groups." THE CHEMICAL LABORATORY. THE PRESIDENCY COLLEGE, THE UNIVERSITY MADRAS, CAMBRIDGE. SOUTH INDIA. [Received Nozvlnber I7th 191 6.

ISSN:0368-1645    

DOI:10.1039/CT9171100069

出版商:RSC    

年代:1917

数据来源: RSC