摘要:

J O U R N A L O F THE CHEMICAL SOCIETY. TRANSACTIONS. H. E. ARMSTRONG, Ph.D., F.R.S. E. DIVERS, M.D., F.R.S. WYNDHAM R. DuNs'rAN, M.A., F.R.S. H. J. H. FENTON, M.A., F.R.S. P. F. FRANKLAKD, LL.D., F.R.S. H. MCLEOD, F.R.S. 1 Sir WILLIAM RAMSAY, K.C.B., LL. D., F.R.S. J. EMERSON REYNOLDS, Sc.D., F.R.S. A. SCOTT, D.Sc., F.R.S. T. E. THORPE, C.R., LL.D., F.R.S. W. A. TILDEN, D.Sc., F.R.S. &bitax : W. P. WYNNE, D.Sc., F.R.S. S;ub-@:bifor : A. J. GREESAWAY. 1902. Vol. LXXXI. LONDON: GURNEY & JACKSON, 1, PATERNOSTER ROW 1902.RICHARD CLAY 8 SONS, LIMITED, LONDON & BUNQAYJ O U R N A L OF THE CHEnilICAL SOCIETY. TRIANSACTIONS. H. E. ARMSTRONG, Ph. D., F.R.S. E. DIBERS, M.D., F.R.S. WYNDHAM R. DUNSTAN, M. A., F. R.S. H. J. H. FENTON, M.A., F.R.S. P. F. FRANKLAND, LL.D., F.R.S.H. MCLEOD, F.R.S. Sir WILLIAM RAMSAY, K. C. B., LL.D., J. EMERSON REYNOLDS, Sc. D., F. R.S. A. SCOTT, D.Sc., F.R.S. T. E. TIIoRm, C.B., LL.D., F.R.S. W. A. TILDEN, D.Sc., F.R.S. F. R. S. mifar : W. P. WYNNE, D.Sc., F.R.S. Snb- @:,bitor : A. J. GREENAWAY. 1902, Vol. LXXXI. Part I. _______ LONDON: GURNEY & JACKSON, 1, PATERNOSTER ROW. 1902.ILlCfiARD CLAY & SONS, LIMITED, LONDON & Buh-GAY.J O U R N A L O F THE CHEMICAL SOCIETY, TRANSACTIONS. dthrnmittte o f H. E. ARMSTRONG, Ph.D., F.R.S. E. DIVERS, M.D., P.R.S. WYNDHAM R. DUNSTAN, M.A., F.R.S. H. J. H. BENTON, M.A., F.R.S. P. F. PRANKLAND, LL.D., F.R.S. H. MCLEOD, F.R.S. gnXr1icwtion : Sir WILLIAM RAMSAT, K.C. R., LL.D., J. EMERSON REYNOLDS, S C . ~ . , F.R.S. A. SCOTT, D.Sc., F.R.S.T. E. THORPE, C.B., LL.D., F.R.S. W. A. TILDEN, D.Sc., F.R.S. F.R.S. @;bitox : W. P. WYNNE, D.Sc., F.R.S. 1902. Vol. LXXXI. Part 11. -I LONDON : GURNEY & JACKSON, 1, PATERNOSTER ROW. 1902.RICHARD CLAY 8s SONS, LIMITED, LONDOX & BUNGAY.RICHARD CLAY 8s SONS, LIMITED, LONDOX & BUNGAY.C O N T E N T S . PAPERS COMMUNICATED TO THE CHEMICAL SOCIETY. 1.-The Oxidation of Sulphurous Acid to Dithionic Acid by Metallic Oxides. By H. C. H. CARPENTER . 11.-The Production of hitherto unknown Metallic Borides. By SAMUEL AUCHMUTY TUCKER, Ph.B., and HERBERT R. MOODY, B.S., M.A. 111.-The Constitution of the *4cids obtained from a-Dibromo- camphor. By ARTHUR LAPWORTH and WALTER H. LENTON. 1V.-Note on the Reduction of Trinitrobenzene and Trinitrotolu- ene with Hydrogen Sulphide.By JULIUS B. COHEN and HENRY D. DAKIN . V.-The Synthesis of A1 kyltricarbnllylic Acids. BJ’ WILLIAN A. B o ~ and CHARLES H. G. SPRANKLING TI.-The Byomination of Trimetliylsuccinic Acid and the Inter- action of Ethyl Bromotrimethylsuccinate and Ethyl Sodio- cyanoacetate. By WILLIAM A. BONE and CHAHLEY H. G. SPRANKLING . VI1.-The Constituents of the Essential Oil of Asamma canudense. By FREDERICK 56. POWER and FREDERIC H. LEES VII1.-Derivatives of Gallic Acid. By FREDERICK B. POWER and FRANK SHEDDEN . 1X.-Thiocarbnmide Hydrochloride. By HENR 1’ P. STEVENS, M.A.,Ph.D. . X.-A Method for Determining Small Quantities of Carbon- ates. By ALFRED DANIEL HALL and EDWARD Joim ~ J S S E L L XI.-Influence of Substitution on the Formation of Dimoarnines and Aminoazo-compounds.By GILBERTHOMAS MORGAN,D.SC. XI1.-Cyanohydroxypyridine Derivatives from Diacetonitrile. New Derivatives of $-Lutidostyril. By JAMES MOIR, M.A., B.Sc., 1851 Exhibition Scholar of Aberdeen University . XII1.-The Determination of Available Plant Food in Soils by the use of Weak Acid Solvents. By ALFRED DANIEL HALL and FRANCIS JOSEPH PLYMEN . X1V.-Corydalino. Part VII. The Constitution of Cory- daline. By JAMES J. DOBBIE, M.A., D.Sc., and ALEXANDER LAUDER, B.Sc. . Berberidic Acid. By JAMES J. DOBBIE, M.A., D.Sc., and ALEXANDER LAUDER, B.8c. . . . XV.-The Relationship of Corydaline to Berberine. PAGE 1 14 17 26 29 50 59 73 i 9 81 86 100 117 145 157iv CONTENTS. XV1.-Studies in the Camphane Series, Part VI. Stereo- isomeric Halogen Derivatives of a-Benzoylcamphor. By XVI1.-The Action of Phosphorus Thiocyanate on Alcohol.By AUGUSTUS EDWARD DISON, M.D. . XVII1.-The Relationship between the Orientation of Sub-' stituents in and the Constitution of Benzeneazo-a-naphthol. By JOHN THEODORE HEWITT and SAMUEL JAMES MANSON AULD XIX. -The Magnetic Rotation of some Polyhydric Alcohols, Hexoses, and Disaccbaroses. By W. H. PERKIN, sen., Ph.D., F.R.S. . XX.-The Constitution of Hydrocyanic, C:y%nic, and Cyanuric Acids, By F. D. CHATTAWAY and J. MELLO WADMORE . XX1.-Myricetin. Part 11. By ARTHUR GEORGE PERKIN, F.R.S.E. . . - . XXI1.-The Colouring Matters of Green Ebony. By ARTHUR GEORGE PERKIN, F.R.S.E., and SAMUEL HENRY CLIFFORD BRIGGS, B.Sc. . XXII1.-Qn Rrnzilic Acid and the Constitution of Brazilin.By W. H. PERKIN, jun. , XX1V.-Brazilin and Hamat oxylin. Part 111. The Consti- tution of Hzematoxylin. By W. H. PERKIN, jun., and J. YATES . XXV.-On uu-Dimethylglut,aconic Acid and the Synthesis of isoCamphoronic Acid. By W. H. PERKIN, jun. . XXV1.-Tetrazoline. Part 11. By SIEGFRIED RUHEMANN and H. E. STAPLETON XXVI1.-Studies in the Camphane Series, Part VII. Con- version of Hyd roxycamphene into ,&Halogen Derivatives of Camphor. By MARTIN ONSLOW FOMTER . X XVIII. -Resolution of Trimethylh y drindonium Hydroxide in to its Optically Active Components. By FREDERIC STANLEY KIPPING . XX1X.-The Action of Methylene Diiodide on Aryl- and Naphthyl-amines, Diarylmethylenediamines, Acridines, and Naphthacridines. By ALFRED SENIER and WILLIAM GOODWIN XXX.-The Polymerisation of Cyanic Acid : Cyanuric Acid, and Cyamelide.By ALFRED SENIER and THOMAS WALSH . XXX1.-Magnetic Rotation of Riiig Compounds. Camphor, Limonene, Carvene, Pinene, and some of their Derivatives. By W. H. PERKIN, sen., Ph.D., F.R.S. XXXI1.--A Modification of Zeisel's Method for the Estima- tion of Methoxyl Groups. By J. T. HEWITT and T. S. MOORE . . . . B'IARTIN ONSLOW FORSTEZ and FRANCES fix. G. MICKLETHWAIT . PAGE 160 168 171 177 191 203 210 321 335 246 26 1 264 2 75 2so 290 292 318CONTENTS. V PAGE XXXIII. -The Radioactivity oE Thorium Compounds. I. An Investigation of the Radioactive Emanation. By E. RUTHERFORD, M, A., D.Sc., Macdonald Professor of Physics, and FREDERICK SODDY, B, A. (Oxon.), Demonstrator in Chemistry, McGill University, Montreal .XXX1V.-Solubilities of the Calcium Salts of the Acids of the Acetic Series. By JOHN S. LUMSDEN, D.Sc., Ph.D. . XXXV.-The Equilibrium between a Solid and its Saturated Solution at Various Temperatures. By Jorrx S. LUMSDEN, D.Sc., Ph.D. . XXXVL-Enzyme Action. By ADRIAN J. BROWN . XXXVI1.-The Velocity of Hydrolysis of Starch by Diastase, with some Remarks on Enzyme Action. By HORACE T. BROWN, LL.D., F.R.S., and T. A. GLENDINNING, F.I.C. XXXVII1.-The Union of Hydrogen and Oxygen. By H. BRERETON BAKER, M.A. , XXX1X.-Studies in the Camphane Series. Part VIII. m-Nitro benzoylcamphor. By MARTIN ONEILOW FORSTER and FRANCES M. G. MICKLETHWAIT . XL.-On the Union of Hydrogen and Chlorine. Part IV. The Draper Effect. By J. W. MELLOR and W. R. ANDERSON XLL-Condensation of Phenols with Esters of Unsaturated Acids.Part VII. By SIEGFRIED RUHEMANN , XLI1.-Mesoxalic Semi- Aldehyde. By HENRY JOHN HORST- MAN FENTON, F.R.S., and JOHN HENRY RYFFEL, B.A., B.Sc. XLIII. - The Picriminothiocarbonic Esters. By JAMES CODRINGT~N CROCKER, B.A., Scholar of St. John’s College, Cambridge. . XL1V.-Isomeric Additive Compounds of Dibenzyl Ketone and Deoxybenzoin with Benzylidene-p-toluidine, m-Nitro- benzylideneaniline, and Benzylidene-m-nitraniline. Part 111. XLV.-The Bases contained in Scottish Shale Oil. Part I. By FREDERIC CHARLES GARRETT and JOHN ARMSTRONG SMYTHE . By B. D. STEELE, B.Sc., and R. B. DENISQN, B.Sc. (1851 Exhibition Scholars) . XLVII. -Rhamnazin and Rhamnetin. By ARTHUR GEORGE PERKIN, F.R.S.E., and JOHN RAYMOND ALLISON, B.Sc. . XLVII1.-Robinin, Violaquercetin, Myrticolorin, and Osyritrin.By ARTHUR GEORGE PERKIN, F.R.S.E. By FRANCIS E. FRANCIS, B.Sc., Ph.D. XLV1.-The Transport Number of very Dilute Solutions. -21 350 363 373 388 400 406 41 4 41 9 426 436 44 1 449 456 469 473vi CONTENTS. XL1X.--The Influence of Salts and other Substances on the By EDGAR L. -The Nitration of s-Trihalogen Anilines. By K. J. P. ORTON. L1.-Some s-Chlorobronionitroanilines and their Derivatives. By LI1.-The Nitration of s-Trihalogen Acetanilides. By K. J. P. ORTON . LIII.--Prepamtion of Sdphamide from Ammonium Amido- sulphite. L1V.-The Constitution of Limettin. By W. A. TILDEN and H. BURROWS . LV.-A Method of Determining the Ratio of Distribution of a Base between Two Acids. By H. M. DAWSON and F. E. GRANT .LV1.-The Molecular Complexity of Acetic Acid in Chloroform Solution. By H. M. DAWSON . LVI1.-The Existence of Polyiodides in Nitrobenzene Solution. I. By H. M. DAWSON and R. GAWLER . LVII1.-The Slow Oxidation of Methane at Low Temperatures. By WILLIAM A. BONE and RICHARD V:WHEELER LIX.-Derivatives of a-Aminocnmphoroxime. By ARTHUR LAPWORTH and ALFRED WILLIAM HARVEY LX.-The Absorption Spectra of Metallic Nitrates. By v-ALTER NOEL HARTLEY, D.Sc., F.R.S.. . LX1.-The Resolution of Pheno-a-amin ocyclohep tane in t o its Optical Isomerides. Tartrates of Pheno-a-aminocycloheptane and of Hydrindamine. By FREDERIC S. KIPPING and ALBERT EDWARD HUNTER . LXI1.--Colouring Matter from the Flowers of Del’himhz Consolida. By ARTHUR GEORGE PERKIN, F,R.X.E., and EDWARD JOHN WILKINSON .LXII1.-Synthesis of Imino-ethers. J-Aryl Benzimino-etheys. By G. D. LANDER . LX1V.-Polymerisation Products from Diazoacetic Acid. By OSWALD SILBERRAD, Ph.D. . Annual General Meeting . Obituary Notices . LXV.-Nitrogen Chlorides containing the Propionyl Group. By F. D. CHATTAWAY . LXV1.-Dimercurammonium Nitrite and its Haloid Derivatives. By PRAFULLA CHANDRA RAY, D.Sc. (Edin.) LXVI1.-Influence of Substitution on the Reactivity of the Aromatic m-Diamines. By GILBERT THOMAS MORGAN, D.Sc*. . Vapour Pressure of Aqueous Ammonia Solution. PHILIP PERMAN * . -K. J. P. ORTON . By EDWARD DIVERS and MASATAKA OGAWA . . . . PAGE 4so 490 49 5 500 504 508 512 521 584 535 549 556 574 585 591 598 609 625 637 644 650CONTENTS. vii PAGE LXVII1.-The Influence of Certain Acidic Oxides on the Specific Rotations of Lactic Acid and Potassium Lactate.By GEORGE GERALD HENDERSON and DAVID PRENTICE, Ph.D. LX1X.-Oxonium Salts of Fluoran and its Derivatives. By J. T. HEWITT and J. N. TERVET . LXX.-Action of Hydrogen Peroxide on Carbohydrates in the Presence of Ferrous Sulphate. 111. By ROBERT SELBY MORRELL and JAMES MURRAY CROFTS . LXX1.-Preparation and Properties of 4-isoPropyldihydro- resorcin. By ARTHUR WILLIAM ,CROSSLEY . LXXII. -The Influence of Temperature on Association in Benzene Solution, and the Value of the Molecular Rise of Boiling Point €or Benzene at Different Temperatures. By WILLIAM Ross INNES, M.Sc. (Vict.), Ph.D. (Heidelberg) . LXXII1.-The Preparation of Absolute Alcohol from Strong Spirit. By SYDNEY YOUNG, D.Sc., F.R.S. .LXX1V.-The Properties of Mixtures of the Lower Alcohols with Water. By SYDNEYOUNG, D.Sc., F.R.S., and EMILY C. FORTEY, B.Sc. LXXV.-The Properties of Mixtures of the Lower Alcohols with Benzene and with Benzene and Water. By SYDNEY YOUNG, D.Sc., F.R.S., and EMILY C. FORTEY, B.Sc. . LXXV1.-Fractional Distillation as a Method of Quantitative Analysis. By SYDNEYOUNG, D.Sc., F.R.S., and EMILY C. FORTEY, B.Sc. LXXVI1.-The Vapour Pressures and Boiling Points of Mixed Liquids. Part I. By SYDNEY YOUNG, D.Sc., F.R.S. . LXXVIII. -Correction of the Boiling Points of Liquids from Observed t o Normal Pressure. By SYDNEY YOUNG, D.Sc., F.R.S. . LXX1X.-Vapour Pressures and Specific Volumes of isoPropyl isoButyrate. By SYDNEY YOUNG, D.Sc., F.R.S., and EMILY C. FORTEY, B.Sc. LXXX.-Influence of the Methyl Group on Ring Formation.By A. W. GILBODY and C, H. G. SPRANKLING LXXX1.-The Preparation of Highly Substituted Nitroamino- LXXXI1.-Nitrogen Bromides containing the Propionyl Group. By F. D. CHATTAWAY . LXXXIII. -Substit uted Dihydrobenzenes. Part I. A2:4-Di- methyldihydrobenzene. By ARTHUR WILLIAM CROSSLEY and HENRY RONDEL LN SUEUR , . benzenes. By K. J. P. ORTON . . * 658 663 666 6 75 682 70 7 717 739 752 768 777 783 787 806 814 82 1... V l l l CO NTE N TS . LXXXIV. -The Radioactivity of Thorium Compounds. 11. The Cause and Nature of Radioactivity. By E. RUTHERFORD and FREDERICK SODDY . LXXXV.-The Radioactivity of Urrtniuin. By FREDERICK SODDY . LXXXV1.-Studies in the Camphane Series. Part 1X. Com- parison of Bromonitrocamphane with Bromonitrocnmphor.By MARTIN ONBLOW FORSTER . LXXXVII.--2 : 4-Dibromo-5-nitro- and 2 : 4-Dibromo-3 : 5-di- nitrotoluenes and their Behaviour on Reduction. By WILLIABI A. DAVIS . LXXXVTI1.-Taxine. By T. E. TIIOHPE, C.B., F.R.S., and GEORGE STUBBS . LXXX1X.-The Sampling of Soils. By JOHN WALTER LEATHER. XC.-Some Excessively Saline Indian Well Waters. By JOHN WALTER LEATHER . XCL-Bromonitro-derivatives of Fluorescein. By J. T. HEWITT and ALFRED WILLIAM GEORGE WOODFORDE . X.CI1.-Studies in the Tetrahydronaphthalene Series. I. The D iazoamino-compounds of w-Te trahy dro-/3-napht halene. By CLARENCE SMITH, B.Sc., A.R. C.S. XC1II.-The Variation with Temperature of the Surface Energies and Densities of Liquid Oxygen, Nitrogen, Argon, and Carbon Monoxide. By E. C. C. BALY and F.G. DONNAN . XC1V.-Phosphorus Tetroxide. By CHARLES A. WEST, B.Sc., A.R.C.S. . XCV.-The Absorption Spectra of Phloroglucinol and some of its Derivatives. By W. w. HARTLEY, L).sc., F.R.S., JAMES J. DOBBIE, D.Sc., M.A., and ALEXANDER LAUDER, B.Sc. XCV1.-The Colour Changes exhibited by the Chlorides of Cobalt and some other Metals, from the Standpoint of the Theory of Electroaffinity. By FREDERICK G. DOHNAN and HENRY BASSETT, jun., [and, in part, C. J. J. FOX] XCVI1.-Isomeric Additive Products of Methyl, ‘ Ethyl, and Propyl Benzyl Ketones with Benzylideneaniline. Part IV. By FRANCIS E. FRANCIS, B.Sc., Ph.D., and ERNEST BOWMAN LUDLAM, B.Sc. . XC!VIII.-The Stereochemical Formulae of Benzene. By JAMES E. MARSH . XC1X.-The Action of Chlbrine and Bromine on Nitroamino- benzenes.Part I. s-Trisubstituted C hloronitroamino- benzenes. By K. J. P. ORTON . Raoult Memorial Lecture. By J. H. VAN’T HOFF, Memberof the Prussian Academy of Science, and Professor in the Univer- sity of Berlin . . . . PAGE 83 7 860 865 8’70 874 883 887 893 900 907 923 929 939 956 961 965 969CONTENTS. ix PAGE C.- Substituted Nitrogen Chlorides containing the Azo-group. By F. D. CHATTAWAY . 982 C1.-Nitrogen Chlorides and Bromides derived from Ortho- substituted Anilides. By F. D. CHATTAWAY and J. MELLO WADMORE , . 984 Dinitro- p-Anisidine and Derivatives. By RAPHAEL MELDOIA, F.R.S., and JOHN VARGAS EYRE . . 988 (2111.-Tribromophenol Bromide (Dibromobenzene Ketodibrom- ide. By EDWARD W. LEWIS (Salters’ Research Fellow) . 1001: CIV. -Some Hydroxypyrone Derivatives.By T. TICKLE (former Salters’ Company’s Research Fellow in the Research Labor- atory of the Pharmaceutical Society of Great Britain) and J. NORMAN COLLIE, F.R.S. . . 1004 CV.-Brazilin and Hzmatoxylin. Part IV. On Dimethoxy- carboxybenzoylformic Acid, Brazilinic Acid, &c. By W. H. PERKIN, jun. . 1008 CV1.-Brazilin and Hsmatoxylin. Part V. The Oxidation of Trimethylbrazilin with Chromic Acid. By A. W. GILBODY and W. H. PERKIN, jun. . . 1040 CVI1.-Brazilin and Hzmatoxylin. Part TI. The Oxidation of Tetramethylhzmatoxylin with Chromic Acid. By W. H. PERKIN, jun. . . 1057 CVII1.-The Decomposition of Chlorates. Part V. Potassium Chlornte in presence of Oxides of Manganese, and the Theory of Perchlorate Formation. By WILLIAM H. SODEAU, B.Sc. . 1066 C1X.-An Accurate Method of Measuring the Compressibilities of Vapours.By B. D. STEELE, D.Sc. (1851 Exhibition Scholar) . . 1076 CX.-The Solvent Properties of Mixed Liquids in Relation to the Chemical Characters and Solvent Properties of their Components. By HARRY MEDFORTH DAWSON . . 1086 CX1.-The Influence of Solvents on the Rotation of Optically Active Compounds. Part 111. Influence of Benzene, Toluene, 0-X ylene, m-Xylene, p-X ylene, and Mesitylene on the Rotation of Ethyl Tartrate. CXI1.-The Influence of Solvents on the Rotation of Optically Active Compounds. Part IV. Influence of Naphthalene on the Rotation of Ethyl Tartrate. CXIIL-The Decomposition of Oxalacetic Acid Phenylhydrazone in Aqueous and Acid Solutions, and a New Method of Determining the Concentration of Hydrogen Ions.By HUMPHREY OWEN JONES, B.A., B.Sc., Jacksonian Demon- strator in the University of Cambridge, and OWEN WILLANS RICHARDSON, B.A., B.Sc., Coutts Trotter Student of Trinity College, Cambridge . . 1140 CI1.-Elimination of a Nitro-group on Diazotisation. By T. S. PATTERSON . 1097 By T. S. PATTERSON . 1134X CONTENTS. PAGE CX1V.-The Dissociation Constants of Oxalacetic Acid and its Phenylhydrazone. By HUMPHREY OWEN JONES, B.A., B.Sc., Jacksonian Demonstrator in the University of Cambridge, and OWEN WILLANS RICHARDSON, B.A., B.Sc., Coutts Trotter etudent, Trinity College, Cambridge . . 1158 CXV.-Constituents of Acacia and Garnbier C'atechus. Part 1'. By ARTHUR GEORGE PERKIN, F.R.S.E., and E. YOSHITASE . 1160 CXVI.--Notes on Luteolin and Apigenin.By ARTHUR GEORGE PERKIN, F.R.S.E. . . 1174 CXVI1.-The Action of Ungerminated Barley Diastase on Starch. Part I. By JULIAN LEVETT BAKER . . 1177 CXVII1.-The Preparation of Mixed Ketones by Heating the Mixed Calcium Salts of Organic Acids, By ERNEST BOWMAN LUDLAM, B.Sc. (Vict.) . . . . , 2185 CX1X.-A Simple form of Landsberger's Apparatus for Deter- mining the Boiling Points of Solutions. By ERNEST BOWMAN LUDLAM, M.Sc. . . 1193 CXX.--The Action of Substituting Agents on Benzoneazo-P- CXX1.-The Condensation of Dimethylaminobenzaldeliyde with By JOHN THEODORE HEWITT, ALFRED JOHN CXXIL-The Action of Ethyl Chlorofumarate on Monoalkyl- CXXII1.-The Solubility of Mannitol, Picric Acid, and CXX1V.-Di-sec.-Octyl Tart rate and Di-sec.-Octyl Di benzoyl- CXXV.-Glycogen from Yeast.By ARTHUR HARDEN and w. J. YOUNG . . 1224 CXXVL-Atomic and Molecular Heats of Fusion. By P. W. ROBERTSON . 1233 CXXVI1.-Revision of the Atomic Weight of Lanthanum. By BOHUSLAV BRAUNER, Ph.D., and FRANTI~EK PAVL~~EK, Bohemian University, Prague. (Communicated by Pro- fessor Bohuslav Brauner) . 1243 CXXVIIL-The Action of Acetylene on the Acetates of Mer- cury. By EMIL BURKARD, Ph.D., and MORRIS W. TRAVERS, D.Sc. . 1270 CXX1X.-The Preparation of Pure Chlorine and its Behaviour towards Hydrogen. By J. W. MELLOR and EDWARD JOHN KUSSELL . . 1272 CXXX.-The Union of Hydrogen and Chlorine. V. The Action of Light on Chlorine Gas. . 1280 naphthol, By J. T. HEWITT and 8. J. M. AULD . . . 1202 P-Naphthol. TURNER, B.Sc., and SIDNEY WALLACE BRADLEY . . 1207 malonic Esters.By SIEGFRIED RUHEMANN . . 1212 Anthracene. By ALEXANDER FINDLAY . . 1217 tartrate. By JOHN MCCRAE , . 1221 By J. W. MELLOR .CONTENTS. x1 PACE CXXX1.-The Union of Hydrogen and Chlorine. VI. The CXXXI1.-The Decomposition of Water Vapour by the Electric Spark. By D. L. CHAPMAN and F. AUSTIN LIDBURY . . 1301 CXXXII1.-Derivatives of Dibenzoylmesitylene. By WILLIAM HOBSON MILLS, Fellow of Jesus College, Cambridge, and THOMAS HILL EASTERFIELD . CXXX1V.-The Chlorination of the Dichlorotoluenes in Presence of the Aluminium-Mercury Couple, The Constitution of the Trichlorotoluenes. Ey JULIUS B. COREN and HENRY D. DAKIN . . 1324 CXXXV.-The Constitution of the Nitro- and Dinitro-derivatives of the Dichlorotoluenes. By JULIUS €3. COHEN and HENRY D. DAKIN, The Yorkshire College .. 1344 CXXXV1.-Iodonium Compounds of the Type IR’R’”’’‘ and the Configuration of the Iodine Atom. By HAROLD PETERS, A.I.C. 1350 CXXXVI I .-T he Molec rilar Configuration of P hosphoryl Chloride and its Derivatives. By ROBERT MARTIN CAVEN, D.Sc., F.I.C. . . 1362 CXXXVIIL-Influence of Substitution on the Formation of Diazoamines and Aminoazo-Compounds. Part 11. By GILBERT THOMAS B~ORGAN, D.Sc., [and, in part, with GEORGE M. NORMAN] . . 1376 CXXX1X.-Observations on the Phenomena and Products of Decomposition when Normal Cupric Acetate is Heated. By ANDREANGEL, B.A., Dixon Scholar, and A. VERNON HARCOURT, M.A., F.R.S., Lee’s Reader in Chemistry, of Christ Church, Oxford . . 1385 CXL. -The Resolution of P-Hydroxybntyric Acid into its Optically Active Components.By ALEX. MCKENZIE . 1402 CXLI. -The Rate of Decomposition of Diazo-compounds. Part I. Diazo-compounds of the Benzene Series. By JOHN UANNELL CAIN and FRANK NICOLL . . 1412 CXLI1.-Studies of the Terpenes and Allied Compounds. Sulphonic Derivatives of Camphor. I. Camphorsulphonic Acid (Reychler) : the Formation of Anhydramides. HENRY E. ARMSTRONG and T. MARTIN LOWRY The Sulphonation of Camphor. 11. P-Bromocamphor and its Derivatives. P-Bromocamphoric Acid. By HENRY E. ARMSTRONG and T. MARTIN LOWRY . . 1462 The Sulphonation of Camphor. 111. The Optical Inversion of Camphor and the Mechanism of Hetero- and Meso-sulphon- ation, of Homo- and Hetero-bromination, and of Dehydr- ation. Period of Induction. By J. W. MELLOR . . 1292 . 1311 . ’ y 1441 . CXLIIL-Studies of the Terpenes and Allied Compounds.CXL1V.-Studies of the Terpenes and Allied Compounds. By HENRY E. ARMSTRONG and T. MARTIN LOWRY . 1469xii CONTENTS. PAG1 CXLV.-The Action of Nitric Acid on’ Bromophenolic Com- CXLV1.-Derivati ves of Normal- and iso-Butyrylpyruvic Acids. By ARTHUR LAFWORTR and A. C. OSBORN HANN . CXLVIL--Optically Active Esters of /I-Ketonic and /I-Aldehydic Acids. Part I. Menthyl Formylphenylacetate. By ARTHUR LAPWORTH and A. C. OSBORN HANN . . 1491 CXLVII1.-Optically Active Esters of @Ketonic and /I-Alde- hydic Acids. Part 11. Menthyl Acetoacetate. By A. LAPWORTH and A. C. OSBORN HANN . * 1495 UXL1X.-The Mutarotation of Camphorquinonehydrazone and Mechanism of Simple Desmotropic Change. By ARTHUR LAPWORTH and A. C. OSBORN HANN . . 150E CL. --The Action of Sodamide and Acyl-substituted Sodamides on Organic Esters. By ARTHUR WALSH TITHERLEY, D.Sc., PkD. . 152C CL1.-3 : 5-Dichloro-o-xylene and 3 : 5-Dichloro-o-phthalic Acid. By ARTHUR WILLIAM CROSSLEY and HENRY RONDEL LE SUEUR . . 1533 CLI1.--Non-existence of the Gaseous Sulphide of Carbon described by Deninger. By EDWARD JOHN RUSSELL and NORMAS SMITH . . 1538 CLII1.-Note on the Localisation of Phosphates in the Sugar CL1V.--Isometric Anhydrous Sulphates of the Form M”S0,,R’2S0,. By FREDERIC R. MALLET . . 1546 CLV.-Asymmetric Optically Active Selenium Compounds and the Sexavalency of Selenium and Sulphur. d- and I-Phenyl- methylselenetine Salts. By WILLIAM JACKSON POPE, F.R.S., and ALLEN NEVILLE, B.Sc. CLV1.--Hydroxyoxamides. Part 11. By ROBERT HOWSON PICKABD, CHARLES ALLEN, WILLIAM AUDLEY BOWDLER and WILLIAM CARTER . . 1563 CLVI1.--The Constituents of Commercial Chrysarobin. By HOOFER ALBERT DICKINSON JOWETT and CHARLES ETTY POTTER . 1575 CLVII1.-The Constituents of an Essential Oil of Rue. By FREDERICK B. POWER and FREDERIC H. LEES . . 1586 CL1X.-Methyl /3-Methylhexyl Ketone. By FREDERIC HERBERT LEES . . 1594 CLX.--The Constitution of the Metallic Cyanides as Deduced from their Synthetic Interactions. The Constitution of Hydrogen Cyanide. By JOHN WADE, D.Sc. . 1596 pounds. By WILLIAM ROBERTSON, A.R.C.S. . 147! . 148: Cane. By CHAS. HENRY GRAHAM SP~~ANKLINU . . 1543 . 1552

ISSN:0368-1645    

DOI:10.1039/CT90281FP001

出版商:RSC    

年代:1902

数据来源: RSC

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14 TUCKER AND MOODY: THE PRODUCTION OF 11.-The Production of hitheyto unknown Metallic Borides. By SAMUEL AUCHMUTY TUCKER, Ph.B., and HERBERT R. MOODY, B.R., M.A. UNTIL the electric furnace made their formation comparatively easy, the borides were almost unknown and even now there have not as yet been reports concerning many of them. Moissan has described a few of these compounds, notably those of iron, cobalt, nickel, carbon, calcium, strontium, barium, and, lately, silicon.HITHERTO UNKNOWN METALLIC! BORfDES. 15 So far as they have been investigated, the borides present evidence of definite composition and crystallisation, they are stable and fuse at comparatively high temperatures. As a consequence of their high fusing point, hardness, and good crystallisation, it is quite possible that some of them may prove to have industrial uses.The available processes for the production of borides are two in number, In the first, the two elements are heated together in the electric furnace, and in the second, boron chloride is passed over the metallic element. The former of these was gelected as being the most practicable for the preparation of the borides described in this paper. The utmost care was taken t o prevent the addition of carbon, silicon, &c., t o the product in each case, and in our opinion the borides described were entirely free from these elements. The boron in each case was determined directly by Gooch’s method (Amer. Chem. J., 1887, 8, 23). Zirconium Boride.-The zirconium salt available for the preparation of this borido happened to be the nitrate.In order to reduce this to the elementary state, two processes were tried. I n the first, the nitrate was ignited until it was wholly converted to the oxide, This was then subjected to the regular Goldschmidt process, which did not prove to be satisfactory. I n the second, the nitrate was dissolved in cold water and the hydroxide precipitated from this solution by sodium hydroxide. Cold water was used in washing the precipitate, inasmuch [as hot water causes it to become insoluble. After being washed, the hydroxide was dissolved in hydrofluoric acid and to this solution neutral potassium fluoride solution was added, forming a precipitate of the double fluoride, 3KF,ZrF,. When dry, this salt was reduced by means of powdered aluminium and the cake thus formed was boiled for three days with concentrated hydrochloric acid.It was found impossible to filter the product rapidly, even with the aid of suction. After being washed with hot water, the metal was ready for we. The elementary boron was prepared by fusing boric acid and reducing the oxide thus formed with metallic magnesium, To remove magnesium salts, the cooled mass was boiled with dilute hydrochloric acid, filtered, washed, and then boiled for three days with hydrochloric acid of 8p. gr. 1.2. After filtering and washing, the residue mas boiled for several hours with hydrofluoric acid, and after a final washing it was dried. For preparing the zirconium boride, 15 grams of the zirconium were mixed with 2.2 grams of boron and the whole heated for 5 minutes in a carbon crucible with the aid of a current of 200 amperes and 65 volts, The product was a button, blackish on the outside, brittle, and of a steel grey colour on fracture.Under the microscope, it proved to16 PRODUCTION OF HITHERTO UNKNOWN METALLIC BORIDES. be an agglomeration of brilliant, tabular, translucent t o transparent crystals, many of these being colourless. It had B sp. gr. 3.7 and a hardness 8. It was slowly attacked by hot concentrated acids and aqua regia. Boiling liquid bromine attacked it feebly. Analyses of the compound were made and 86 per cent. of zirconium was found to be present. This corresponds very closely with the theoretical amount of zirconium in a boride in which zirconium is quadrivalent ; therefore the formula of this compound is undoubtedly Zr,B,.Chromium Boride.-This boride was made by heating a charge con- sisting of 10 grams of metallic chromium and 2.1 grams of boron for 6 minutes by the aid of n current of 175 amperes and 60 volts. The product was a well formed button, greenish on the outside and of a greyish metallic lustre on fracture. It had a sp. gr. 5, a hardness 8, was distinctly crystalline, and had a conchoidal fracture, It was weakly attacked by hot acids and was not altered by exposure to the sir. Analyses of the product gave 82 per cent. of chromium, a result which indicates CrB as the probable formula of the compound. Tzcngsten Boride.-As tungsten is closely related to chromium, it was selected as a promising element and a trial was made of its affinity for boron.The metal tungsten may be prepared from alkali tungstates by acidifying their solutions with hydrochloric acid. This causes the precipitation of the trioxide. After being dried, the trioxide can be reduced in the electric furnace, the charge used containing 10 parts of tungsten trioxide to one part of carbon. For the preparation of the boride, 4 grams of tungsten were mixed with 0.2 gram of boron and then heated for 5 minutes by the aid of a current of 175 amperes and 66 volts, This produced a good fusion and the product was silvery and metallic on fracture. It WRS very brittle and under the microscope was seen to be crystallised in perfect octahedra, It was slowly attacked by concentrated acids, and vigorously by aqua regia. Analyses of the product showed the presence of 89 per cent.of metallic tungsten, a result which indicated the formula to be WB,. Atolybdenurn Boride.-The final compound prepared was a boride of molybdenum. This was selected, as the element molybdenum is closely related to chromium and tungsten and the metal is rather easily prepared. The molybdenum was obtained by heating 300 grams of molybdenum trioxide and 30 grams of coke for 26 minutes with a current of 200 amperes and 65 volts. For making the boride, 6 grams of metallic molybdenum were mixed with 1 gram of boron and heated for 20 minutes by the aid of a current of 230 amperes and 70 volts. This gave a homogeneous button with a Its hardness was 8 and its sp. gr. 9.6.CONSTITUTION OF ACIDS OBTAINED FROM U-DIBROMOCAMPHOR. 17 hardness of 9. I t was quite brittle and on fracture showed a brilliant metallic lustre resembling that of pale brass. It was crystalline in structure, and its sp. gr. was 7.105. The substance was moderately attacked by hot concentrated acids and vigorously by hot aqua regia. The formula Mo,B, was given to this compound as the result of several analyses which showed the presence of 86 per cent. of molybdenum. An attempt to make the borides of copper or bismuth failed entirely ; in fact, there does not seem to be any affinity between boron and the membersof the copper group. COLUMBIA UNIVERSITY, NEW PORK.

ISSN:0368-1645    

DOI:10.1039/CT9028100014

出版商:RSC    

年代:1902

数据来源: RSC

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CONSTITUTION OF ACIDS OBTAINED FROM U-DIBROMOCAMPHOR. 17 III.-The Constitution of the Acids obtained from a-Uibrornocamphor. By ARTHUR LAPWORTK and WALTER H. LENTON. WREN a-dibromocamphor is warmed with moist silver salts, it is in part transformed into the unsaturated monocyclic acid, bromocam- phorenic acid (Trans., 1899, 75, 1134), in which, as has already been shown, the complex (2) :y-y: (1) (3) :$I ?Me,, CH,* CMe*CO,H must be assumed to be present, the ethylenic union existing between the atoms 1 and 2, or 2 and 3, t o one of which also the bromine atom mnst be attached. The facts on which these statements were based are, briefly, as follows :-(1) the substance readily affords homocam- phoronic acid on oxidation with mild oxidising agents (Trans., 1899, 75, 988), and (2) it is obtained from camphor, which contains the group *CMe,*CMe*CO*, by a process which involves no violent action.Tn the first paper, in which the constitution of bromocamphorenic acid was discussed, it was shown that when the acid is converted into a-monobromocampholid, the lactonic oxygen atom becomes attached to the ring at the brominated carbon atom, the group *CBr:CH* becoming converted into . This conclusion was confirmed later by the observation that camphonic acid, the acid which is formed on hydro- lysing the lactone, contains the carbonyl group *COO in the ring, indicating that the first stage in the hydrolysis is the formation of an acid in which the group *C(OH)Br* is present. *QBr*CH,* VOL. LXXXI. C18 LAPWORTH AND LENTON: THE CONSTITUTION OF THE Arguing from the behaviour of simpler lactones, it was presumed that a 7-lactone would be formed in preference to a Blactone, the bromine atom would then be attached to the carbon atom labelled 1 or 3, and it is here that the first dubious point in the argument appears, for it is by no means always legitimate to apply generalisa- tions based on the behaviour of open chain compounds t o substances containing closed rings.For this reason, we have again taken up the investigation, with the object of ascertaining t o which of the oarbon atoms, 1, 2, or 3, the bromine atom is attached, for, in so doing, the constitution of the interesting series of compounds obtained from a-dibromocamphor would be determined beyond question. It may be worth while to point out that the view t o which one of us had come respecting the position of the bromine atom in question led to conclusions which did not appear to be altogether satisfactory. Thus, assuming that the bromine atom was attached to the carbon atom in position (l), the behaviour of camphonic acid towards substi- tuting agents was not easily explained (compare Trans., 1900,77, 451), whilst the supposition that it was associated with carbon atom (3) led to the view that both camphonic and camphononic acids must be re- presented by formula containing the groupiug *CH,* CO*CH,* (Trans., 1899, 75, 1139), a conclusion which, although in excellent agreement with the properties of camphonic acid, is altogether unsatisfactory in regard to the other substance, which behaves exactly as would an acid containing the complex C--C*CO, c\ forming, for example, no additive C/ compound at all with hydrogen cyanide (compare Trans., 1901, The first part of the investigation was therefore devoted to proving that, in the formation of camphonic acid from bromocamphorenic acid, no change oE structure occurs, and that the ketonic oxygen atom occupies the position of the lactonic oxygen atom in the campholids.For this purpose, camphonic acid was reduced with sodium amalgam, and the product shown to be identical in all respects witb the hydroxy- acid obtained by Forster on hydrolysing campholid itself (Trans., 1896, 69, 57). The view already advanced of the mode of formation of camphonic acid seems, therefore, to be correct. For the second part of the investigation, the tribromolactone ob- tained from camphonic acid (Trans., 1900, 77, 458) was used as a starting point.This substance, being obtained by gentle treatment of camphonic acid with bromine, must be supposed to be derived from the tetrabromo-acid containing the group *CBr,* CO-CBr,.. It was hydro- lysed by careful treatment with alkali, and the product, which we did not attempt to isolate, was oxidised by means of cold sodium hypo- 79, 379).ACIDS OBTAINED FROM a-DIEROMOCAMPHOR. 19 bromite, which was found to be the most suitable agent for the purpose. The oxidation product was isolated in the usual way and found to be a mixture, which, on further investigation, proved to contain trimethyl- succinic acid, a small quantity of camphoronic acid, and a relatively large amount of an acid, C9HI2O6, which proved to be the substance hitherto known as 6-hydroxycamphoronic acid (Bredt, ArflnaZen, 1898,299,158).The formation of camphoronic acid from tribromocnmphonolactone shows that the latter contains the complex '7: :g ?Me2 CH,* CMeG J On inspecting the skeleton formula of camphorenic acid (p. 17) and remembering that the bromination of camphonic acid probably results in the first instance in the formation of a tetrabromo-acid containing the group *CBr2*CO*CBr2*, it will be seen that the only possible formula for this tetrabromo-acid is expressed by I, hence camphonic acid itself must have the constitution represented by I1 : ?0--QBr2 QO--QH, CH,-CMe* C02H CH2*CMe*C02H Tetrabromo-acid. Camphonic acid. I. YBr, ?Me, 11.QHz ?Me2 It follows of necessity, therefore, that in bromocamphorenic acid the bromine atom occupies the position of the ketonic oxygen in this formula, or in other words it is attached to the carbon atom 2 in the skeleton formula. This, in itself, does not enable us to decide whether the double bond is situated between the atoms 1 and 2, or 2 and 3 ; the first alternative, however, is in all probability the correct one, for in this event homo- camphoric acid and camphononic acid will have the formuh 111 and IV. 70,H 70,H CH2*y0 CH,-CMe* CO,H CH2 * CMe C02H Honiocamphoronic acid. Camphononic acid. This conclusion is in complete agreement with the feeble ketonic pro- perties of camphononic acid, whilet the readiness with which cam- phonic acid forms additive compounds is explained by the presence in it of the complex *CH,*CO*CH,*.The conclusion thus arrived at harmonises with the whole of the known properties of the substances obtained by Forster (Trans., 1896, 69, 36) and by Lapworth and Chapman (Trans., 1899, 75, 986; 1900, "7, 446) and explains the apparent anomalies which have 111. QH2 ?Me2 IV. I $!Me2 c 220 LAPWORTH AND LENTON: THE CONSTITUTION OF THE appeared from time to time, The formula of camphononic acid, moreover, is what it should be on the basis of Bredt’s Formula for camphor and the relationship which has been firmly established between this acid and the simpler camphor derivatives (Trans., 1900, 77, 1056; 1901,79, 1284). The formation of bromocamphorenic acid from a-dibromocamphor may be expressed by the scheme, CH,*CiK-CBr, CH,-CBr: $33.1 yhIe2 I + H,O = I ?Me, + HBr. CH,*CMe-CO CH,--CMe*C02H It is not impossible that at an intermediate stage a trimethylene ring is produced and that this afterwards breaks down, the carbon atom originally exterior to the ring having become merged in it. Thus intermediate compounds such as CH------ \\ ’ /CH C‘Br I \/ CHB1-AMez I Or I co I CH,---CMe*CO,H might afford bromocamphorenic acid by scission at the points indicated by the dotted lines. The ready formation of trimethylene rings in certain cases, notably in the production of carone and of the caronic acids (Perkin and Thorpe, Trans., 1899, 75, 522), makes i t appear likely that the phe- nomenon is not so infrequent as is generally supposed. The assumption that an unstable trimethylene ring is formed in many other changes would probably be of great value in explaining their progress.Thus the curious transformations of campholytic and isolauronolic acids one into the other (Walker, Trans., 1900, 77, 378), and into derivatives of tetrahydro-xylic acid (Perkin and Lees, Trans., 1901,79, 323), may be the result of reactions like the following : CH,*CMe 1 h l e b H , I t CH=yMe UH, CH,* QMe CH,* C CO,H / isoLauronolic acid. I ?Me’ +++ I ?Me k’ CIH,*CH*CO,H CH,*CH*CO,H ,. ,~ gH2*gEe Campholytic Intermediate $?€€Me acid. compound. CH,* C*CO,H Tetrahydro-xylic acid.ACIDS OBTAINED FROM a-DIBROMOCAMPHOR. 21 Similarly, the formation of camphene derivatives from borngl chlor- ide and the allied substances, may be the result of a similar parti- cipation of a methyl group in the formation of a trimethylene ring, and most of the apparently anomalous properties of these compounds point to such an explanation as being the correct one (compare Marsh, Proc., 1899, 15, 54).As already mentioned, '( P-hydroxycamphoronic acid " is produced to a far greater extent than camphoronic acid in the oxidation of the pro- duct of hydrolysis of tribromocamphonolactone. It may appear a t first sight to be somewhat remarkable that this should be the case, as it is impossible to suppose that the substance is obtained by the oxidation of camphoronic acid, If it be remembered, however, that the product of hydrolysis consists largely of ketonic substances, which are usually easily attacked by hypobromites, there is no great difficulty in explain- ing the formation OF the '' hgdroxy "-compound.Thus, for example, the product in the first instance may consist of a mixture of substances such as yo-yo v0,H qO,H CH,*CMe*CO,H CH,--CMe* C0,H and either of these might be attacked by the hypobromite, the latter, for example, affording successively the substances represented by the formuh CO,H CO,H CO,H /CO CO,H /CO f I I / I /' I GO CMe, --+ C0,O CMe, --+ ./O CMe, I I I / I 1 CHBr* CMe* C0,H CH-CMe*CO,H CH--CMe*CO,H The substance known as 6-hydroxycamphoronic acid is, in reality, a lactonic acid containing water of crystallisation and should more correctly be termed P-camphoranic acid, employing the word used by Bredt for the isomeric substance. The hydrated acid, C,H,,O,, 2H,O, is dibasic and may be boiled with excess of NflO alkali for half an hour without suffering any appreciable amount of hydrolysis into the hydroxy-acid.This fact rendered its identification a matter of con- siderable diEculty, for it is described as a tribasic acid both by Kach- ler and Spitzer and by Bredt. It was necessary, therefore, to prepare the acid directly from camphoronic acid, by the process which is described later, and it was then found that the conclusions which wehad arrived at with regard to the acid from tribromocamphonolactone held good with regard t o the other, the two substances being identical in every respect. vMe2 and 70 ?Me, 922 LAPWORTE AND LENTON: THE CONSTITUTION OF THE EXPERIMENTAL. Beduction o f Camphonic Acid. Camphonic acid, dissolved in 10 per cent.aqueous sodium hydroxide, was placed in an evaporating dish, carbon dioxide passed rapidly through the solution, and sodium amalgam added in small quantities during the course of several hours, until a small portion, after acidifi- cation with acetic acid, gave only a slight precipitate with p-bromo- phenylhydrazine acetate, indicating the absence of all but a trace of the ketonic acid, The liquid was separated from the mercury, acidified with dilute sulphuric acid and extracted repeatedly with ether ; the ethereal solution was then washed with a very little water, dried, and evaporated. The colourless, oily residue slowly solidified to a mass of needles, which was crystallised from ethyl acetate. The hydroxy- acid finally formed large prisms, which melted and evolved gas at 178-1 79".On analysis : 0.1236 gave 0.2902 CO, and 0.1073 H,O. C1,Hl,O, requires C = 64.5 ; H = 9.7 per cent. The acid dissolved slowly in strong sulphuric acid, and on pouring the colourless solution into water a flocculent, white mass separated. This was collected, dried, and crystallised from light petroleum, from which it was deposited in fern-like, camphoraceous crystals melting at 177-178"; i t had the properties of a lactone and was identical with the campholid obtained by the action of strong sulphuric acid on camphorenic acid (Forster, Trans., 1896, 69, 56). The hydroxy-acid was identical with that which Forster obtained on hydrolysing the lactone (Zoc. cit.). Degradalion of Camphowic Acid. Camphonic acid was first converted into tribromocamphonolactone by the method described in a former paper (Trans., 1900, 77, 458), and the lactone carefully purified by crystallisation from chloroform, The pure substance, which was in the form of large crystals, was finely powdered and covered with a 25 per cent.solution of potassium hydroxide containing some alcohol. No considerable rise of tempera- ture occurred. The whole was allowed to remain for a week, then warmed on the water-bath for 15 minutes and poured into twice its bulk of water, the alcohol being got rid of by repeated evaporation with water nearly to dryness. The aqueous solution of the residue was then acidified, and extracted repeatedly with ether in the usual way. The ether, on evaporation, deposited an oily mass which slowly solidified, This was not closely examined, but was found to contain C=64*0; H a 9 .6 .ACIDS OBTAINED FROM a-DIBROMOCAMPHOR. 23 only a trace of bromine ; it exhibited marked ketonic properties and its solution in alkalis had a distinct yellow colour. The oil was dissolved in dilute sodium hydroxide, cooled to O', and to this solution sodium hypobromite solution was added, in small quan- tities at a time; after each such addition, a notable rise in tempera- ture occurred, and the process was continued until, after the lapse of 15 minutes, hypobromite could be detected in the liquid. Sodium sulphite was then added, the solution neutralised with hydrochloric acid and evaporated to a small bulk, a large excess of hydrochloric acid added, and the deposit of sodium chloride and bromide removed by filtration and thoroughly washed with ether.The filtrate was ex- tracted twenty times with ether, and the ethereal solution dried and evaporated. The oily residue thus obtained was dissolved in a little water, the solution made alkaline with baryta water, and the very slight deposit of insoluble matter removed. The filtrate was then heated to boiling, when a second and much larger deposition of insoluble substance occurred ; this was removed, washed with water, decomposed by means of hydrochloric acid, and the product examined. The amount of acid obtained from the precipitate was too small for analysis as well as satisfactory examination. The substance was found to melt at 137O when very slowly heated, and at higher tem- peratures when the capillary tube was plunged into sulphuric acid already a t that temperature.It formed an anilic acid melting at 146O, and a faintly alkaline solution of the ammonium salt gave no precipi- tate with barium or calcium chloride in the cold, but a copious one on boiling. In fact, the chemical and crystallographical properties of the acid were identical in every respect with those of camphoronic acid. As it appeared, from the small quantity of camphoronic acid ob- tained, that this substance did not constitute the principal product of the oxidation, the acids in the filtrate from the barium camphoronate were liberated, extracted with ether, and, after the usual process of purification, were allowed to remain with a little water for several months.During this time, the mixture became semi-solid, and was a t last spread on porous earthenware to drain. The solid portion was crystallised repeatedly from boiling water, when it was finally obtained in beautiful, lustrous prisms, which, after drying in the air for 2 days, did not lose their brilliancy, but on exposure at 100' rapidly became opaque and diminished in weight, owing to loss of water. On analysis: C9H1206 requires C = 50.0 ; H = 5.6 per cent. 0.1648 gave 0.3212 H,O and 0.0852 H,O. C=49*8 ; H=5*7. The equivalent was determined by titration against N/10 sodium24 LAPWORTH AND LENTON: THE CONSTITUTION OF THE hydroxide in presence of phenolphthalein. The number found was 10’7, whereas a dibasic acid of the formula C,H,,O, requires 108. The substance dissolved fairly readily in hot water, and in ethyl acetate, alcohol, or acetone, but only very sparingly in benzene, and was insoluble in light petroleum.The crystals from water were well-formed, rectangular plates or stout prisms, belonging apparently to the rhombic system; in the plates, the axial plane was parallel to the large face, and the direction of the acute bisectrix was at right angles to the direction of greatest length. The anhydrous substance, when melted on a glass slip be- neath a cover-glass, solidified rapidly, forming radiate or fan-shaped structures split up by linear air-spaces. The function of the third pair of oxygen atoms was not easy to determine, but as the substance gave no oxime, phenylhydrazone, or acetyl derivative, i t was surmised that a lactone ring was present in the molecule.A small quantity of the acid was therefore heated to boiling with a known excess of N/10 sodium hydroxide for half an hour, and, after cooling, the excess of alkali remaining was determined. It was found that no hydrolysis had occurred, the acid remaining dibasic, as before. As the acid had a composition and a melting point identical with those of ‘( /3-hydroxycamphoronic acid,” obtained by Kachler and Spitzer from camphoronic acid, it was thought possible that the two substances might be identical, although ‘ I /3-hydroxycamphoronic acid” is stated to be tribasic. To obtain further evidence on the point., the acid was converted into its ethyl ester by treatment with absolute alcohol and hydrogen chloride. The substance thus obtained crystallised from a mixture of ethyl acetate and light petroleum in thin, six-sided plates melting at 161°, which is exactly the melting point given by Kachler and Spitzer for the ester of their acid. The identification of the acid was com- pleted by preparing ‘ I /3-hydroxycamphoronic acid ” by the method described later.In order to ascertain whether the oxidation of the hydrolytic pro- duct of tribromocamphonolactone had proceeded further than to P-camphoranic acid, the syrupy mother liquors were extracted from the porous plate by hot water, and subjected to distillation in a cur- rent of steam for several hours in order to separate the volatile acids. The aqueous distillate was then carefully neutralised with milk of lime, filtered, and evaporated nearly to drpness.A granular salt separated towards the end of this operation, and was collected and decomposed by hydrochloric acid, the acid being extracted with pure ether in the usual way. The residue obtained on evaporating the It melted sharply at 246’.ACIDS OBTAINED FROM a-DIBROMOCAMPHOR, 25 ethereal solution was again converted into calcium salt, which was collected and decomposed once more. The acid which was thus obtained melted a t 150-151°, formed an anhydride which melted at 36-37O, and was identical with that pre- pared from the trimethylsuccinic acid obtained by fusing a-camphoranic acid with potassium hydroxide. It appears, therefore, that the product obtained from tribromocam- phonolactone by the above process consists mainly of P-camphoranic acid with small quantities of camphoronic acid and trimethylsuccinic acid, and it is remarkable that no a-camphoranic acid could be de- tected, although it is a substance which would probably be isolated easily from such a mixture.&omination of Camphoyonic Acid. The action of bromine on camphoronic acid takes place only under pressure in closed tubes at l4Oo or thereabouts, and bromo-acids are not obtained, as hydrogen bromide is at once eliminated, and a mix- ture of the lactones of a- and P-hydroxycamphoronic acids is formed. Bredt (Amnden, 1898, 299, 158) did not succeed in brominating cam- phoronic acid or any of its derivatives under the ordinary pressure, but found it necessary t o conduct the bromination in closed tubes and to employ the purified anhydro-chloride.The authors have found that, as in so many other cases, the action of bromine on the mixture obtained by treating the acid with phosphorus pentabromide does not lead to satisfactory results, but that if phos- phorus pentachloride is employed, an excellent yield of the mono- brominated compounds can be obtained. The procedure was as follows. Camphoronic acid was converted into the anhydro-acid by heating it in a flask at about 130-140° until water vapour ceased to be evolved. The cooled and powdered product was then carefully mixed with phosphorus pentachloride (1 mol.), heated on the water-bath for half an hour, and allowed to cool. Bromine (14 mols.) was then added, the temperature gradually raised to 100" during about an hour, maintained a t that point for about 6 hours, and the product then poured on to ice and allowed to stand overnight.The granular product thus obtained consisted almost entirely of a mixture of the anhydro-chlorides of a- and /3-bromocamphoronic acids, and these may be converted into the bromo-acids by boiling with nearly anhydrous formic acid. To obtain the a- and /3-camphoranic acids, the mixture of bromo- acids was boiled with water for several hours and the liquid then cooled, and rendered faintly alkaline with baryta water. The barium salt of a-camphoranic acid separated almost at once as a fine, crystalline26 COHEN AND DAKIN: REDUCTION OF TRINITROBENZENE AND powder, and the acid obtained from this was used for the preparation of trimethylsuccinic acid for purposes of identification. The filtrate from the barium a-camphoranate was acidified with hydrochloric acid, extractsd with ether, and the P-camphoranic acid examined. It was found to be identical in every respect with the acid obtained by the former process. A quantity of P-camphoranic acid prepared in this way was crystal- lised from water; the clear crystals were then allowed to dry in the air and at once analysed : 0.2921 gave 0,4612 CO, and 0.1622 H20. C9H,,0,,2H,0 requires C = 42.8 ; H = 6.3 per cent. The equivalent of the acid in the hydrated crystals was determined by titration with N/10 sodium hydroxide, using phenolphthalein as indicator. The number obtained was 130, whilst that required for a dibasic acid of the formula C9H,0,,2H20 is 126. CHEMICAL DEPARTMENT, SCHOOL OF PHARMACY, 17, BLOOMSBURY SQUARE, W.C. C = 43.1 ; H = 6.2.

ISSN:0368-1645    

DOI:10.1039/CT9028100017

出版商:RSC    

年代:1902

数据来源: RSC

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26 COHEN AND DAKIN: REDUCTION OF TRINITROBENZENE AND IV.-Note on the Reduction of Trinitrobenxene and Trinitrotoluene with Hydyogen Sulphide. By JULIUS B. COHEN and HENRY D. DAKIN. THE reduction of the 2 : 4 : 6-trinitrotoluene was originally undertaken with the object of producing an amino-group in the para-position, and by its removal of obtaining eventually 2 : 6-dinitrotoluene, a compound which we required in the study of the chlorination products of toluene. The reduction of trinitrotoluene to 2 : 6-dinitro-4-toluidine by means of ammonium sulphide is described by Tiemann (Bey., 1870, 3, 218) and Beilstein (Bey., 1880, 13, 243), but the yield we obtained was small, and we did not succeed in improving it or in suppressing a quantity of tarry impurity which makes its appearance at the same time.After many unsuccessful attempts to effect reduction with ammonium sulphide and other agents, we tried a methyl alcoholic solution of crystallised ammonium sulphide, passing in hydrogen sulphide a t the same time to displace air and keeping the whole well cooled. We found that the reaction proceeded vigorously even when the quantity of ammonium sulphide present was very far below the theoretical amount. Finally, we simplified the method by adding a few drops of concentrated ammonia to an alcoholic solution of the trinitro-TRINITROTOLUENE WIT€€ HYDROGEN SULPHIDE. 27 compound and saturating with hydrogen sulphide. The product, filtered from sulphur and poured into water, formed a bright yellow, crystalline precipitate, which was not the anticipated dinitrotoluidine, but, as we eventually discovered, 2 : 4-dinitro-6-tolylhydroxylamine, Precisely the same reaction occurs with trinitrobenzene. 2 ; 4-Di~itro-6-tolylhydroxylamine.Twenty grams of finely powdered trinitrotoluene were suspended in about 100 C.C. of absolute alcohol, about 0.5 C.C. of concentrated ammonia was added, and the mixture cooled in ice. Hydrogen sulphide was then passed in with frequent shaking, I n a short time, the colour of the solution deepened and the heavy crystals of trinitrotoluene, which at first settled to the bottom, were soon replaced by a thick, bulky, deep yellow precipitate, which filled the liquid. After about an hour, no further increase in the quantity of precipitate appeared, and the mixture was warmed for a moment on the water-bath and filtered quickly into a flask standing in ice.The precipitate was washed with hot alcohol until the filtrate was colourless. A residue of sulphur remained which weighed 6.3 grams. The alcoholic filtrate deposited, on standing, a mas3 of needle-shaped crystals, which were separated and amounted to 4.7 grams. This fraction contained a small proportion of dinitrotolylhydroxylamine, mixed with some compound of high melting point, and melted indefinitely from 130-160'. The product of high melting point is 2 : 6-dinitro-4-toluidine, for, on boiling 0.6 gram of this fraction for 2 hours with concentrated hydrochloric acid so as to convert the hydroxylamine compound into the insoluble 2 : 4-dinitro-6-toluidineY diluting and filtering, 0.3 gram of orange crys- tals melting at 167-169', which is the melting point of the 2 : 6- dinitro-base, was deposited from the filtrate.The filtrate was poured into water, which precipitated the bulk of the hydroxylarnine compound. It was filtered, washed with water, and carefully dried. The weight was 11.5 grams. It was extracted with successive quantities of benzene, in which it all eventually dis- solved, each portion being kept separate. The last extracts yielded crystals melting sharply at 143-145', which did not change by successive recry stallisations and were therefore regarded as pure. The substance was analysed with the following results :28 REDUCTION OF TRINITROBENZENE WITH HYDI~OGEN SULPHIDE. 0.2377 gave 39.5 C.C. moist nitrogen at 17" and 764 mm.N = 19.45. 0.1595 ,, 27.25 ? > ,, 17" ,, 760mm. N=19*79. C,H,O,N, requires N = 19272 per cent. A xolecular weight determination by the boiling point method gave 0.1 81 gram in 11.43 grams of benzene raised the boiling point by 0*1979 The compound reduces alcoholic silver nitrate, depositing a mirror ; it also reduces Fehling's solution. It readily dissolves in alcohol, but is less soluble in benzene and insoluble in light petroleum. From benzene, it crystallises in rhombohedra. It dissolves in boiling dilute hydrochloric acid unchanged and then crystallises in small, pale yellow needles. On prolonged boiling, it becomes insoluble and changes to a colourless, crystalline compound. The same result is much more rapidly effected by concentrated hydrochloric acid.Half a gram of the hydroxylamine compound, boiled with about ten times its weight of strong hydrochloric acid for half an hour, yielded 0.3 gram of the colourless substance, the following result : Mol. mt., found = 215 ; calculated = 213. 2 ; 4-0initl.o-6-tolzcidine. The colourless compound was crystallised from benzene, from which It was analysed with it separated in needles melting at 212-213Q. the following results : 0.1857 gave 0.2884 CO, and 0,0575 H,O. 0.1475 ,, 2'7.7 C.C. moist nitrogen at 26' and 759 mm. N = 20% 0,220 gram in 8.1 grams of benzene raised the boiling point by 0*160°. C = 42.35 ; H = 3.44. C7H70,N, requires C = 42.6 ; H = 3.5 ; N = 21.3 per cent. Mol. wt., found == 221 j calculated = 197. The substance is insoluble in sodium hydroxide solution or in dilute hydrochloric acid. Neither stannous chloride nor sodium nitrite in acid solution has any action on it.It dissolves unchanged in strong sulphuric acid and is reprecipitated by water. The conversion of p-phenylhydroxylamine into p-aminophenol by mineral acids has been studied by Bamberger (Beg.., 1894, %, 1349), and takes place by intramolecular rearrangement : C,H,*NH*OH + OH*C,H,aNH,. I n the present case, the substance produced is not a phenol, but, The conversion must there- according to analysis, a dinitrot01 uidine. fore be accompanied by the removal of oxygen. CH,. C,H,(NO,),*NH*OH: = CH,*C,H2( NO,),*NH, + 0.THE SYNTHESIS OF ALKYLTRICARBALLYLIC ACIDS. 29 This is precisely what happens, for if the hydroxylamine compound be boiled with hydrochloric acid and indigo solution, the colour is slowly discharged, or with hydrochloric acid and potassium iodide, iodine is liberated.As the amino-compound melts at 212-213', it must be the 2 : 4-di- nitro-6-toluidine,as the only other possible isomeride melts at 166-168O. This substance has not been previously prepared. As we have seen, the hydroxylamine compound acts both as a reducing and an oxidising agent. It is also worthy of remark that, whereas ammonium sulphide converts trinitrotoluene in to 2 : 6-dinitro-4-toluidine, iri which the p-nitro- group is reduced, the action of hydrogen sulphide is to reduce the nitro- group in the ortho-position. 1 ; 3-Dinih.o-5-phenyl~~drox?/Zamine. This substance is prepared from 1 : 3 : 5-trinitrobenzene in exactly the same way as the tolyl derivative, but although the yield is smaller, the product is more readily obtained in a pure state. It forms dark orange crystals melting at 114-1169 Nine grams of trinitrobenzene yielded 4.5 grams of pure hydroxylamine derivative. Dinitrophenylhydroxylamine reduces alcoholic silver nitrate solution, On analysis, the following result was obtained : N=21*53. 0.113 gave 20-8 C.C. moist nitrogen at 15' and 756 mm. On boiling with concentrated hydrochloric acid, the substance a t first passes into solution, but very soon a precipitate appears. The product is then poured into water, boiled up, and allowed to crgstallise. On cooling, dark orange needles separate out, which melt sharply a t 158-159". This is the melting point of 3 : 5-dinitroaniline, with which it is undoubtedly identical, a fact which serves to confirm the nature of the reaction in the case of the tolyl derivative. We propose to con- tinue this investigation. C6H,0,N3 requires N = 21.10 per cent. THE YORKSHIRE COLLEGE.

ISSN:0368-1645    

DOI:10.1039/CT9028100026

出版商:RSC    

年代:1902

数据来源: RSC

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THE SYNTHESIS OF ALKYLTRICARBALLYLIC ACIDS. 29 V.-The Synthesis of Al~~~ltricarballylic Acids. By WILLIAM A. BONE and CHARLES H. G. SPRANKLING. IN a previous communication (Trans., 1899, 75, 839), we described a method for the preparation of ethyl esters of cyanosuccinic acid and its alkyl derivatives ; for some time past, we have been investigating a general method for the synthesis of alkyltricarballylic acids, based30 BONE AND SPRANKLING: THE SYNTHESIS OF on the interaction of the sodium compounds of these othyl cyano- suucinates with the ethyl esters of a-bromo-fatty acids, as indicated by the general equation, CR,. C0,Et CN CR,Br*CO,Et + N E L C < ~ ~ ~ ~ ~ I = ~<~~,,, -I- NaBr, CR2 c02E CR, CO,E t where R indicates hydrogen or any alkyl radicle, A reference to the literature of the subject shows that tricarballylic aoid and its a-alkyl derivatives have been generally obtained by the condensation of the sodium compound of ethyl malonate, or one of its alkyl derivatives, with ethyl fumarate or maleate, and subsequent hydrolysis of the resulting ester, as follows : vNa( C0,E t), CRNa(C0,Et)2 +- CH*Co2Et I I = QH*CO,Et CH*Co2Et CHR*CO,Et Auwers and others (Ber., 1891, 24, 30'7, 288'7) prepared a number of a-alkyltricnrballylic acids from ethyl fumarate, but so far as we know no attempt has been made to see whether dialkyltricarballylic acids can be obtained by any similar method.In 1896, Zelinsky (Bey., 29, 333, 616) showed that three apparently stereoisomeric ay-dimethyltricarballylic acids are obtained when the highest fraction of the oil which results from the interaction of ethyl cyanoacetate (1 mol.), sodium ethoxide (2 mols.), and ethyl a-bromo- propionate (2 mols.) in alcoholic solution is hydrolysed with sulphuric acid.His investigation of the subject was incomplete and he has since abandoned it. Just as we were beginning our experiments, Haller and Blanu (Compt. rend., 1900, 131, 19) synthesised aa-dimethyltricarballylic acid from ethyl cyanosuccinate, but except in this one instance the practicability of preparing tricarballylic acids from ethyl alkylcgano- succinates has not so far been,studied.* As the result of a long and systematic investigation of the matter, we have shown that anyalkyltricarballylic acid in which the alkyl radicle or radicles occupy an a-position with respect to either of the two extreme carboxyl groups may readily be prepared by the method we have indicated.Besides the method just discussed, there is obviously another possible way of passing over from an acid of the succinic to one of the tricarballylic series, namely, by the interaction of an ethyl mono- * Since this paper was written, however, Dr. H. A. D. Jowett has published an account of the preparation of a-ethyltricarballylic acid from ethyl a-cyano-B-eth yl- succinate and ethyl bromoacetate (Trans. 1901, 79, 1346).ALKYLTRICARBALLYLIC ACIDS. 31 bromosuccinate with ethyl sodiocyanoacetate or malonate as represented by the general equation, C02Et*CR2*CRBr*C02Et i- NaCH<co,Et CN - - CO,Et*CR,*CR(CO,Et)*CH(CN)*CO,Et + NaBr, where R represents hydrogen or an alkyl radicle (or radicles).Hitherto, only tricarballylic acid itself has been prepared by this method (Emery, Bey. 1890,23,3759), and we therefore extended our experiments in this direction in order to ascertain whether this second method possesses any advantages over the first, or vioe versa. The results are very decisive on this point, for they indicate that whereas the first (" cyano- succinate ") method is a general one, the second can only be applied in certain cases (owing partly to the circumstance that the bromination of many substituted succinic acids does not proceed regularly, and partly also to the tendency which some ethyl bromosuccinates exhibit to lose hydrogen bromide and form unsaturated compounds). And, further, even when the second method can be applied, the yields of resulting tricarballylic acids are camparatively poor, Incidentally, however, we have accumulated valuable information as to the bromina- tion of alkylsuccinic acids, which will be briefly discussed later.During the course of the experiments, we have added to the know- ledge of the pr'operties of various alkyltricarballylic acids, their anhydro-acids and monomethyl salts, but have not been able con- jointly to finish the scheme of work originally drawn up; the results so far obtained are, however, sufficiently complete in themselves to justify their publication. The investigation of this interestiag and important series of acids will be continued. I. PREPARATION OF ETHYL CYANOTRICARBALLYLATES FROM ETHYL CYANOSUCCINATES.The method adopted may be briefly described as follows : To a solu- tion of 5.75 grams of sodium in alcohol is added one-fourth of a gram- mol. of the ethyl cyanosuccinate ; the sodium compound of the latter, which is at once formed, remains in solution. Rather more than the calculated quantity of the a-bromo-fatty ester is then cautiously added in small portions at a time. The interaction which follows is generally very vigorous, much heat is developed, and sodium bromide separates. The liquid usually becomes neutral after being heated for 30 to 60 minutes on the water-bath, after which it is poured into water and the ethyl cyanotricarballylate extracted with ether in the usual manner. On fractionating the crude oil under diminished pressure (20-35 mm.), a certain amount of it passes over at temperatures below 150"; the32 BONE AND SPRANKTJING: THE SYNTHESIS OF thermometer then rises rapidly to about ZOO', when the ethyl cyano- tricarballylate begins to distil.The following are the particulars concerning the yields, &c., obtained in the various preparations, and the properties of the refractionated ethyl cyanotricarballylates. Ethyl C~anotricarballylcte. The yield of refractionated oil obtained from ethyl cyanosuccinate and ethyl bromoacetate amounted to 75 per cent. of that theoretically possible; under 28 mm. pressure, it boiled a t 206-212'. On being rapidly cooled, the distillate solidified. By dissolving the solid in the minimum quantity of warm glacial acetic acid, then adding hot water until a faint turbidity appeared, and setting the liquid aside to cool slowly, the whole of the substance separated after some hours in prismatic and transparent crystals which melted sharply a t 40-41'.On analysis : 0,2213 gave 0.4421 CO, and 0.1376 H,O. 0.3116 ,, C = 54-48 ; H = 6.90. 13.8 C.C. nitrogen at 18' and 752 mm. N = 5.07. C,,H,,O,N requires C = 54.73 ; H = 6.66 ; N = 4.91 per cent, CH,*CH(CO,Et)*C*CH,*CO,Eb Ethyl a-ilfet h ylcyanotricarbally Zat 6, A CN C0,Et This substance may be prepared by the interaction of either the sodium derivative of ethyl 6-methylcyanosuccinate and et hy 1 bromo- acetate or of the sodium derivative of ethyl cyanosuccinate and ethyl a-bromopropionate. The first named method is much the better of the two, and the yield obtained by it amounted to 70 per cent.of the theoretical. The refractionated oil boiled at 202-204' under 23 mm. pressure, had a density d O o / 4 O = 1.1339, and a refractive index pNa = 1.4461. On analysis : 0.2002 gave 0.4137 CO, and 0,1316 H,O. 0.3102 ,, 12.75 C.C. nitrogen at 15' and 771 mm. N=4.87. C1,H210,N requires C = 56-18 ; H = 7-02 ; N = 4.68 per cent, C=55*86 ; H=7*31. Ethyl ay-Bimeth~ZcyanotricarbuZlylate, CH,* CH(C0,Et) C*CH( CH,) -CO,Et /\ CN C0,Et The yield of refractionated oil obtained from ethyl P-methylcyano- succinate and ethyl a-bromopropionate amounted to 65 per cent, of the theoretical. It boiled at 208-210' under 30 mm. pressure, had aALKYLTRICARBALLYLIC ACIDS. 33 density d Oo/4'=la1215, and a refractive index pNa=1*4484. analysis : On 0.1976 gave 0.4146 CO, and 0.1353 H,O.0,2863 ,, 11.3 C.C. nitrogen a t 16' and 758 mm. N = 4.59. C-57.21 ; H = 7.61. C,,H,,O,N requires C = 57-50 ; H = 7.34 ; N = 4.47 per cent. (CH3),C(C02Et)*C*CH,*C0,Et EthpZ aa-Dimethylcyanotl.iccco.baZZyZate, /\ CN C0,Et This may be prepared either by the method adopted by Haller and Blanc (Zoc. cit.) by the interaction of ethyl sodiocyanosuccinate and ethyl a-bromoisobutyrate, or by the interaction of ethyl PP-dimethylsodio- cyanosuccinate and ethyl bromoacetate. We have tried both methods and find that the second is by far the better one; the yield obtained by it amounts to 55 per cent. of the theoretical, and if after fraction- ating the crude product the portion of lower boiling point be again heated with a small quantity of sodium ethoxids in alcohol, a further quantity of the cyanotricarballylate is formed, bringing the total yield up t o nearly 70 per cent, of the theoretical. The refractionated oil boiled at 202-204' under 17 mm.pressure, had a density d 0°/4" = 1.1353, and a refractive index pNa = 1.4503. On analysis : 0.2006 gave 0,4206 CO, and 0,1341 H,O. C = 57.19 ; H = 7.43. U,,H2,0,N requires C = 57.50 ; H = 7.34 per cent. EthgZ ay-Diisopropg Zc?lanotricarbaZlgZate. This was prepared by the interaction of ethyl P-isopropylsodiocyano- succinate and ethyl a-bromoisovalerate ; the experiment cannot be properly carried out in an open vessel on the water-bath, as the reaction only proceeds very slowly under these conditions. The mixture was accordingly heated in soda-water bottles at 100' under pressure for 10-12 hours ; on fractionating the resulting crude oil under 15 mm.pressure, we obtained from 6 1 grams of ethyl /3-isopropylcyanosuccinate originally taken the following fractions : (a) Below 150 O... 33 grams. (y) 205-215 O... 10 grams. (p) 150-205" ... 37 grams. (6) Above 215O, a few drops only. The fraction (p) contained large quantities of nitrogen and bromine, and evidently consisted of :I mixture of unchanged cyanosuccinato and bromoisovalerate ; the fraction (a) contained no nitrogen to speak cf, but a large qiiantity of bromine, They were accordingly mixed, and after determining the amount of bromine in the mixture, the VOL. LXXXI. D34 BONE AND SYRANKLING: THE SYNTHESIS OF corresponding quantity of sodium ethoxide in alcoholic solution was added to it.The whole was then heated in a soda-water bottle a t 100" for 10 hours, as before, and on fractionating the resulting oil a further 10 grams passed over a t 205-215O under 15 mm. pressure. This was mixed with the fraction y obtained in the first part of the experiment, and the mixed oils were afterwards refractionated under 16 mm. pres- sure ; finally, 17 grams of a nearly colourless oil boiling a t 208-212' were obtained, which represent an 18 per cent. yield. On analysis : 0.2016 gave 0,4672 CO, and 0.1596 H20. 0.3259 C = 63.2 ; H = 8.8. ,, 11.1 C.C. nitrogen a t 5" and 762 mm. N=4.09. C,,H,lOoN requires C = 63.51 ; H = S.65 ; N= 3.90 per cent. The oil was very thick and viscous, it had a density d 0"/4" = 1.075 and refractive index pNa = 1.4595.Hydrolysis of the Oils.-With the exception of ethyl ay-diisopropyl- cyanotricarballylate, all the oils just described can be readily hydro- lysed by boiling them in a reflux apparatus for 10 to 20 hours with strong hydrochloric acid. This method we accordingly adopted. I n no case did any solid acid separate on cooling the liquid after all the oil had dissolved, nor did we find i t feasible to isolate the acids by means of their calcium salts, a plan which answers very well in the case of alkylsuccinic acids. We therefore resorted to the simple ex- pedient of saturating the liquid in each case with ammonium sulphate and then thoroughly extracting it with pure ether. After drying the ethereal solution over anhydrous sodium sulphate and distilling off the solvent, there remained an oily residue which usually solidified in the course of a few hours.This was then either recrystallised from a suitable solvent, or, in cases where it consisted of a mixture of isomeric acids, was submitted to a suitable process for their separation. I n one case, namely, that of act-dimethyltricarballylic acid, the oil which remained after distilling off the ether did not solidify even after stand- ing many days, and tthere was evidence that the hydrolysis had been incomplete; on heating the oil with dilute (10 per cent.) hydrochloric acid under pressure at 190"for a few hours, and afterwards evaporating the liquid in a vacuum over strong sulphuric acid, the pure acid was obtained . 11. TRICARBALLYLIC ACIDS, THEIR ANRYDRO-ACIDS AND MONOMETHYL SALTS. TrricarballyZic Acid.The acid, after being recrystallised from a mixture of glacial acetic acid and chloroform, melted at 157-159". On analysis :AI~KYLTKICARBALLYLIC ACIDS. 35 0.1806 gave 0*2703 CO, and 0.0762 H,O. 0.2164 silver salt gave 0.1407 Ag. C: = 40.81 ; H = 4.69. Ag = 65.02. CGH806 requires C = 40.90 ; H = 4.54 per cent. c,H,OGAg, ,, The dissociation constant of the acid is 0.022, a value practically identical with that given by Walker (0.0224) for tricarballylic acid (Trans., 1892, 61, 707). The calcium salts of this and the other acids of the tricarballylic series described in this paper are readily soluble in cold water, but are almost entirely precipitated when the solution is boiled. When a 25 per cent. solution of calcium chloride is added to a cold solution of the neutral ammonium salt of tricarballylic acid, no separation of the calcium salt occurs ; on boiling the solution, however, a dense, c r p t a l - line precipitate instantly appears which entirely redissolves when the liquid is cooled again.The process of alternately precipitating and then redissolving the calcium salt may be repeated several times, but the precipitate seems very gradually to become less soluble in cold water. The behaviour of these calcium salts may be contrasted with those of the succinic acids which, when once precipitated from a hot solution of the ammonium salts, 20 not redissolve when the liquid is cooled, Acids of the two series may be readily separated by means of their calcium salts. Anhyclro-acid.-The characteristic property which the tricarballylic acids possess of yielding anhydro-acids (generally crystalline) when they are boiled with acetyl chloride, or maintained a t a temperature of 200" or upwards, was first noticed by Emery (Ber., 1891, 24, 596) in the case of tricarballylic acid itself.These anhydro-acids combine the functions of a true anhydride and a monobasic acid, but it has not yet been shown whether in their formation from the tricarballylic acid, the elements of water are eliminated from the ap- or the ay-carboxyl groups, or, in other words, whether, say in the case of tricarballylic acid, the anhydro-acid has the formula I or 11. yH,* UO,H VH,--CO\ 1. $!H-CO CH,*CO Ag = 65-16 per cent. 11. FH*CO,H >O. >o CH,-CO' The best way of preparing these anhydro-acids is to dissolve the tricarballylic acid in warm acetyl chloride, and, after boiling the solu- tion for 2-3 hours in a reflux apparatus, to distil off the solvent and afterwards fractionate the residual liquid under diminished pressure.I n the case of tricarballylic acid, the anhydro-acid passed over between 215" and 225' under 45 mm. pressure; on cooling, it completely solidified, and after recrystallisation from a mixture of chloroform and glacial acetic acid, melted a t 130-131'. 0 236 BONE AND SPRANKLING: THE SYNTHESIS OF 0,1715 gave 0.2830 CO, and 0.0615 H,O. C,H,05 requires C = 45.57 ; H = 3.79 per cent. The following investigation of the monomethyl salts of tricarballylic acid shows that the anhydro-acid has probably the constitution ex- pressed by the formula I. Monomethyl Xdts.-There are two possible isomeric monomethyl salts of tricarballylic acid, and three methods by which they may be prepared, namely, ( d ) by the direct partial esterification of the acid ; ( b ) by the partial hydrolysis of the trimethyl ester, and (c) by the solution of the anhydro-acid in methyl alcohol.We have carefully investigated these methods as follows. (a) Direct EsteriJication of the Acid.-Five grams of the acid were heated for 10 minutes with methyl alcohol containing just sufficient dry hydrogen chloride to effect the esterification of one carboxyl group. The excess of alcohol was then distilled off under reduced pressure. A colourless oil * remained, which entirely dissolved in a cold solution of sodium carbonate, and on being titrated with a standard solution of barium hydroxide proved to have an acidity corresponding t o that of a methyl dihydrogen salt.The silver salt, prepared by adding silver nitrate t o a solution of the oil exactly neutralised with dilute ammonia, was analysed as follows : C = 45.10 ; H = 3.98. 0.1726, on ignition, gave 0.0920 h g . C,HsOGAg2 requires Ag = 53.47 per cent.? There can be no doubt, therefore, that the oil had the composi- tion of a methyl dihydrogen tricarballylate. The next question t o be decided was whether the oil was a single substance or a mixture of the two isomeric monomethyl salts. We according deter- mined its dissociation constant on the supposition that whereas a single monomethyl salt would give a value for the constant K which would remain practically the same for successive dilutions, a mixture of two isomeric monomethyl salts would be indicated by well-marked variations in the value of K on dilution.The results indicated that the oil was a single substance. * None of the methyl dihydrogen salts of tricarballylic acids investigated by 11s are solids, so that it was impossible to purify them by crystallisation ; nor did distillation under reduced pressure serve the purpose ; the evidence of their purity is derived from a study of their dissociation constants. -f Besides analysing the silver salts of the monomethyl dihydrogen tricarballylates described in the paper, we always ascertained the acidity of each by titration with a standard barium hydroxide solution.In each case, practically the calculated amount of the alkali was required. Ag = 53.30.ALKYLTR~CARBALr~Y LIC ACIDS. 37 Dissociation Constcmt. K= 0'0075. (Temp. 25O.) V. P U S 112. K. 7.62 8.2 7 0.0236 0,00748 15.24 11.65 0.0333 0,00753 30.48 16.42 0,0469 0.00756 60.96 23.03 0,0658 0*00761 (b) Purtial Hydrolysis of Trinzethyl Tricarba2Eylate.-It was first of all necessary t o prepare the trimethyl ester from the acid by snturat- ing a solution of it in methyl alcohol with dry hydrogen chloride in the usual manner. The resulting oil was washed with a dilute sodium carbonate solution, and distilled under 48 mm. pressure, when it passed over at 205--208'. It was then quit,e colourless, having a density d Oo/4O= 1.1381, and a refractive index pNa= 1.4398.On analysis : 0.2110 gave 0.3823 CO, and 0.1246 H20. C,H,,O, requires C = 49.50 ; H = 6.42 per cent. Six grams of the oil were added to a quantity of potassium hydr- oxide, dissolved in methyl alcohol, just sufficient to effect the hydrolysis of two methoxy-groups. A drop of a methyl alcoholic solution of phenolphthalein was added, and the liquid allowed to stand at the ordinary temperature in an atmosphere free from carbon dioxide until only the faintest pink tinge remained. Two drops of a methyl alcoholic solution of met.hy1-orange were then added, and dry hydrogen chloride passed into the well-cooled liquid until a pink colour first appeared. The liquid was at once filtered from the potassium chloride which had separated, and the filtrate evaporated in an exhausted desiccator over sulphuric acid.The residual oil was dissolved in a slight excess of sodium carbonate solution, and the liquid extracted with pure ether in order t o remove any trace of unchanged trimethyl ester. Finally, the solution was acidified with hydrochloric acid, and again extracted with pure ether, About 4.6 grams of a colourless oil were thus obtained; the silver salt was prepared and analysed as follows : C -- 49.41 ; H= 6-56. 0.2610 gave on ignition 0,1389 Ag. Its dissociation constant was then determined as follows : Ag = 53.32. CTH,0,Ag2 requires Ag = 53.47 per cent. Dissociution constant. K= 0.00925. (Temp. 2 5 O . ) 2'. P U. 172. K. 11 a47 9.15 0.0320 0.00922 22.94 15.78 0.0457 0.00926 45.88 22.1 2 0.0632 0.00929 91.76 30.94 0.0884 0.0093338 BONE AND SPRANRLING: THE SYNTHESIS OF These numbers show that the oil WBS a single monomethyl di- hydrogen tricarballylate and isomeric with that obtained by the direct esterification of tricarballylic acid.Now it has been shown by V. Meyer, Sudborough, and other workers on the subject of esterifi- cation that a carboxyl attached to a primary carbon atom is much more easily esterified than one attached to a secondary carbon atom; consequently we must regard the monomethyl dihydrogen tricarballylate obtained by the direct esterification of the acid as hhe a-compound, C0,Me*CH,*CH(C0,H)*CH2*C0,H, and therefore the isomeric ester obtained by the partial hydrolysis of $rimethyl tricarballylate must be the P-compound, CO,H*CH,*CH(CO,Me)*CH,*CO,H. ( c ) By Solution of the Anhydro-mid in Methyl Alcohol.-The anhydro- acid was boiled for 45 minutes in a reflux apparatus on a sand-bath with a quantity of pure dry methyl alcohol slightly in excess of that required to effect its conversion into the monomethyl dihydrogen salt.The liquid wits then placed in a vacuum over sulphuric acid in order to get rid of the slight excess of alcohol, and, after some days, the residue was subjected to a further purification by means of sodium carbonate as described under ( b ) . The silver salt of the purified oil mas analysed as follows : 0.1167 gave on ignition 0.0611 Ag. The dissociation constant of the monomethyl salt wnq determined as Ag=52*35. C7H,06Ag2 requires Ag = 52.47 per cent. follows : Dissociation constccnt. K = 0.00945.(Temp. 25O.) u. PV* 112. K. 12.82 9.74 0.0342 0.00945 25.64 16.80 0.0480 0.00944 51.28 23.55 0.0673 0,00946 102.56 32.87 0.0939 0-00949 This shows, therefore, that the monomethyl dihydrogen tricarballyl- ate obiained by dissolving the anhydro-acid in methyl alcohol is the &compound, CO,H*CH,*CB(CO,Me) *CH,°C02H, and such as can only result from an anhydro-acid of the constitution represented by formula I (p. 35). a-Metl~yltricccrbaZZyylic Acids, CH,*CH(C0,H)*CH(C02H)*CH2~~02H. Since this acid contains two asymmetric carbon atoms, it exists in two inactive forms, meso- and racemic. Auwers, von Meyenberg, and Kobner (Ber., 1891, 24, 307, 2887) succeeded in isolating these from the hydrolysed product of the condensation of ethyl fumarateALKYLTRICARBALLYLIC ACIDS.39 (1 mol.) with ethyl sodiomethylmalonate (2 mols). Their acids melted at 134O and 184' respectively, and it was shown that the isomeride of lower melting point is partially converted into the other on being boiled with strong hydrochloric acid. Our experiments showed that when 26 grams of ethyl a-methyl- cyanotricarballylate were hydrolysed with strong hydrochloric acid in the manner described, 16.5 grams of a mixture of isomeric acids were obtained ; this only solidified aEter being kept for some days in ice. The substance, however, still contained a little nitrogen, and it was therefore heated with dilute (10 per cent.) hydrochloric acid in sealed tubes a t 180-200' for 24 hours. The solid which finally remained after evaporating the liquid to dryness melted between 160' and 170".On rapidly extracting this residue with small quantities of cold water, one of the stereoisomeric acids dissolved, and the melting point of the residue gradually rose to 179O and afterwards remained constant. The washings, on evaporation, yielded a residue melting between 136' and 145O, and when this was once again subjected to fractional extrac- tion with cold water, an acid melting a t 134-135' was obtained from the first washings. The acids were analysed and their dissociation constants determined as follows : trans-Acid, m. p. 179". 0.1624 gave 0.2633 CO, and 0.0769 H,O. 0.3007 silver salt gave 0.1897 Ag. C = 44.11 ; H = 5.35. Ag= 63.10. C7H,,0, requires C = 44.21 ; H = 5.26 per cent. C7H70,Ag, ,, Ag = 63.39 per cent. Dissociation Constant.K= 0.0322. (Temp. as0.) V. P V . I?&. K. 20.0 27.46 0.0767 0.0319 40.0 37.42 0.1069 0.0320 80.0 52.14 0.1489 0.0326 160.0 71-10 0.2032 0.0324 cis-Acid, m. p. 134-135'. C7HI0O6 requires C = 44-21 ; H = 5.26 per cent. 0.21 13 gave 0.3425 GO, and 0.1023 H,O. C = 44.09 ; H = 5.38. Dissocichtion Cbmtant. K= 0*0480. (Temp. 25O.) V. Pw 112. K. 20.64 32.83 0.0938 0.0470 41.28 45*89 0.1311 0.0475 82.56 66.52 0.1 900 0.0481 165.12 90.00 0.2583 0,048640 BONE AND SPRANKLING: THE SYNTHESIS OF Anhydvo-acid.*--We have found that each acid on being dissolved in acetyl chloride yields its own liquid anhydro-acid, and that even after being distilled under reduced pressure neither of the anhydro-acids solidifies. Each anhydro-acid, however, with water yielded the acid from which it was originally derived, and on heating the trans-anhydro- acid with acetyl chloride, or acetic anhydride, for several hours, it was completely transformed into the cis-isomeride.Conversion of cis- into trans-Acid.-We are able to confirm Auwers' observation that the cis-acid is partially converted into the trans-iso- meride on being treated with hydrochloric acid under ,pressure at 190-200° and find that equilibrium is established when 80 per cent. is so transformed. The behaviour of the anhydro-acids leaves no doubt as to the con- stitution of the two isomeric acids from which they are derived; the cis-anhydride is the more easily formed from its acid, and is more stable than the trans-isomeride. The two acids, therefore, have the following constitutions : H* C CO,H CO,H*(PH H*?* CO,H H*F*H H*$?*H C0,H CO,H Monomethyl SaZts.-So far we have only studied the monomethyl salts of the &-acid ; on determining the dissociation constants of those prepared by the three methods described in the case of tri- carballylic acid (pp. 36-38), we obtained practically identical numbers as follows : trans-Acid, m. p.179". cis-Acid, m. p. 134-135". Mean values of K at 25". .Direct esterification of acid ........................... 0.00893 Partial hydrolysis of trimethyl ester.. ................ 0.00857 Solution of anhydro-acid in methyl alcohol ......... 0*00888 At this stage of the inquiry we do not feel able to express any decided opinion as to the interpretation of these results, and the matter is receiving further investigation.Monomethyl salt prepared by ay- DimethyZtricabaZZ~Zic Acids, CH,*CH( C0,H) CH( CO,H)*CH(CH,) *CO,H. By the hydrolysis of the oil of higher boiling obtained by the inter- actiou of sodium ethoxide (2 mols.) ethyl cyanoacetate, (1 mol.), and * Auwers did not study these substances.ALRYLTRICARBALLYLIC ACIDS. 41 ethyl a-bromopropionate (2 mols.), Zelinsky (Zoc. cit.) obtained three isomeric acids, C,H,,06, as follows : K for M. p. M. p. acid. acid. anhydro-acid. 203 -204' 0.042 11 1-1 13' 175-1 76 0-054 129-130 (1) (2) (3) 148-149 0.051 117-119 and although his experiments were not quite conclusive, he brought forward evidence in favour of the view that the three acids are stereo- isomeric ay-dimethyltricarbnllylic acids, If this be so, it is the only instance of the synthetical formation of three inactive stereoisomeric forms of a compound, C(abc)*C(ab)*C(abc), corresponding to the three trihydroxyglutaric acids (the one Izevorotatory, to which there is, of course, a corresponding racemic ' acid, and the other two ' meso '- inactive) obtained by Fischer (Ber., 1891, 24, 1842, 2686, 4222) by the oxidation of I-arabinose, xylose, and ribose respectively.The point seemed t o us sufficiently important to warrant further and independent investigation. When ethyl ay-dimethylcyanotricarballylate was hydrolysed by boiling it with excess of strong hydrochloric acid for 12 hours, and the resulting liquid extracted with ether, a solid mass was obtained which melted gradually between 140' and 160O. By boiling it for some time with successive small quantities of hydrochloric acid, part dissolved, leaving finally an insoluble constituent which melted at 206-207O, and was not altered by further treatment with hydrochloric acid.On concentrating the hydrochloric acid solution in a vacuum over sulphuric acid, two sucessive crops of crystals were obtained which melted at 170-188' and 171 -1 73' respectively. This second fraction was twice recrystallised from strong hydrochloric acid and then melted sharply at 174". We were unable to isolate any third acid either from the first crop of crystals melting at 170--188O, or from the hydrochloric acid mother liquors. The two acids melting at 206-207' and 174" were analysed, and their dissociation constants determined, as follows : Briefly stated, our results are as follows.Acid, m. p. 206-207'. 0.1706 gave 0.2951 CO, and 0.0922 H,O. 0,1064 silver salt gave 0.0654 Ag. C,H,,O, requires C = 47.58 ; H = 5.88 per cent. C,H,O,Ag, ,, C = 47.1 9 ; H = 6.01. Ag = 61.49. Ag = 61.70 per cent,.42 BONE AND SPRANKLING: THE SYNTHESIS OF Dissociation constant. K = 0.0445. (Temp. 25O.) 21. F U * m. K. 33.71 40.18 0.1 148 0.0441 67.42 55.81 0.1594 0.0448 134.84 75.93 0.2169 0,0446 269.68 101.70 0.29 1 1 0,0443 Acid, m. p. 174". 0,1926 gave 0.3302 CO, and 0.1038 H,O. 0.1099 silver salt gave 0.0676 Ag. C,H,,O, requires C = 47.58 ; H = 5.88 per cent. C8H,06Ag, ,, C-47-49 ; H=5*99. Ag=61*56. Ag = 61-70 per cent. Dissociatiolz colzstant. K= 0.0545. (Temp. 25O.) V. Pv. m. K. 20.7 35-03 0.1 002 0,0559 41.4 48.67 0.1 38'7 0.0540 82.8 66.72 0.1 906 0.0542 165.6 90.60 0.2588 0,0546 Anhydro-aids.-Each acid dissolved in acetyl chloride, yielding its own solid anhydro-acid ; that obtained from the acid of higher melting point (206-207O) fused at 110-112°, and that from the acid of lower melting point (174') fused a t 130".Mutual Conversion.-(l) The acid melting at 206-207' was heated for 4 hours a t 180° under pressure with acetic anhydride, and from the dark-coloured liquid the acid melting at 174" was recovered by means of its potassium salt. It is clear, therefore, that the nnhydro- acid of the former is a t high temperatures converted into that of the latter. (2) The acid melting at 174" was partially converted into that melt- ing at 206-207" by heating it with strong hydrochloric acid at 210" for several hours.There can be no doubt, therefore, that these two acids are identical with two of the acids obtained by Zelinsky, and, further, that they are stereoisomeric. Zelinsky hydrolysed the oil from which he obtained his three acids with sulphuric acid ; we therefore hydrolysed another portion of the ethyl uy-dimethylcyanotricarballylate by boiling it with 50 per cent. sulphuric acid. The operation was rather a slow one, and was only complete after 2 or 3 days. On cooling the liquid a crop of crystals, A, separated, melting at 190' or thereabouts; on furtherALKYLTRICARBAT~LYLIC ACIDS. 43 concentrating the mother liquor, two more crops of crystals were obtained, namely, R, melting at 170-180°, and C, at temperatures be- low 139'.From fractions A and B, by furtherpurification, were obtained two acids melting a t 204-206' and 174-176', identical in all respects with those obtained in the earlier experiments. Fraction C was sub- mitted to two or three recrystallisations fro= water ; its melting point gradually rose to 143" and then remained constant ; analysis showed that it had the empirical formula C8H,,06. On being treated with acetyl chloride, it yielded an anhydro-acid, C8Hlo05, melting quite sharply a t 116-117", which with water regenerated the original acid. Dissociation constant. K= 0.0572. (Temp. 25'.) 2). P U * m. K. 21.78 36.97 0.1056 0.0573 43.56 57.1 1 0.1 460 0.0573 87.1 2 69.80 0.1994 0.0570 174.24 94.29 0,2693 0.0569 The most curious point about this acid is that on being warmed with strong hydrochloric acid it is very quickly and quantitatively transformed into the acid melting a t 174"; for example, on recrystal- lising a portion of i t from warm hydrochloric acid its melting point rose to 160-164', after a second recrystallisation to 171-173', and after a third to 174'.The question therefore arises : Is this acid melting at 143" a third inactive stereoisomeric form of ay-dimethyltricarballylic acid, or is it merely a molecular mixture of the other two forms? Three facts are in favour of the first view, namely (1) that it yields its o w n anhydro- acid with acetyl chloride ; (2) that its dissociation constant varies very little with successive dilutions, and is higher than the correspond- ing values for the other two acids ; and (3) that treatment with strong hydrochloric acid converts it into the second (174") acid, whereas the acid melting at 206" remains absolutely unchanged when heated with hydrochloric acid under the ordinary pressure.One of the three acids must be the racemic (tvans-) form, the other two must be meso-modifications of uy-dimethyltricarballylic acid which we may distinguish as the cis,- and cis,-acids. Since the an- hydro-acid of the acid melting at 174" is the most stable of the three anhydro-acids at high temperatures, it is probably one of the cis- (meso-) forms ; the other cis-form is, therefore, the acid melting at 143". The someride having the highest melting point must therefore be the trams- or racemic form, as under :44 BONE AND SPRANKLING: THE SYNTHESIS OF p 3 p 3 p 3 H-Q* C0,H H* ?*CO,H H* Q* C0,H H* C*CO,H H*y*CO,H CO,H*y*H CO,H*$'*H H*F*CO,H H 7 C0,H Trans- or iacemic, m.p. 206-207'. cEr, CH3 CH3 cis,- and cis,-Acids (meso). At present we are unable to decide which of the two acids, melting a t 174' and 143' respectively, is the cis,- and which the cis,-form. The further investigation of the subject is in hand, however. au-Dimet~yZtricarbaZZ~Zic Acid, (CH3),C(C02H)*CH(C0,H)*CH,*C0,H. This acid is a very interesting member of the series, inasmuch as it is an oxidation product of pinonic acid (Tiemann and Semmler, Ber., 1895, 28, 1349), also of fenchone (Gardner and Cockburn, Trans., 1898, 63, 710) and camphoceenic acid (Jagelki, Bey., 1899, 32, 1498). The acid we obtained by hydrolysing ethyl aa-dimethylcyanotricarb- allylate melted at 143'.On analysis : 0.21 36 gave 0.3722 CO, and 0.1145 H,O. C = 4751 ; H = 5.96. C,H,,O, requires C = 47.58 ; H = 5.88 per cent. Dissociation constant. K= 0.0318. (Temp. 25O.) V . Pu* 712. h-. 23.67 29-16 0-0833 0.0320 47.34 40.39 0.1 154 0.0318 94.68 54.67 0.1562 0,0315 189.36 75-12 0,2146 0.0309 The anhydro-acid, recrystallised from chloroform, melted at 0,2022 gave 0.1900 CO, and 0.1003 H20. C,H,,O, requires C = 51.61 ; H = 5.3'7 per cent. The trimethyl ester was a thick oil boiling at 170-174' under 33 mm. pressure; it had a density d Oo/4O= 101403 and a refractive index pNa = 1 -441 7. 135-136'. On analysis : C = 51.25 ; H = 5.50. 0.1829 gave 0,3588 CO, and 0,1236 H,O. Monomethyll XaZts.-There are three possibleisomeric monomethyl salts of this acid, namely, (a) (CH,),C(C0,H)*CH(C0,H)*CH2*C0,Me, (6) (CH3),C(C0,H)*CH(C0,Mc)*CH,*C02H, and C=53.5 ; H= 7.51.CllH1806 requires C = 53.7 ; H = 7.32 per cent. (c) (CH,),C(CO,Me)*CH(CO,H)*CH,*CO,H.ALRYLTRICARBALLYLIC ACIDS. 45 We prepared monomethyl salts from the acid, the trimethyl ester, and the anhydro-acid, by the methods already described (pp. 36-38), with the following results : (i) By Direct Esterijication of the Acid.-A colourless oil. 0,1526 of its silver salt gave 0.076 Ag. Ag = 49.79. C1,H1,O,Ag, requires Ag = 50.00 per cent. Dissociation constant. K = 0.01 80. (Temp. as0.) V. PV. 721. K. 31.2 25.34 0.0724 0-0181 62.4 35.10 0.1003 0.0179 124.8 48.52 0.1386 0.0179 249.6 65.92 0.1883 0.01 75 There can be no doubt, therefore, that the oil was a single sub- stance, and from the fact that it was formed by the direct esterification of the acid (which contains only one primary CO,H group), we may conclude that it has the formula (a).(ii) By Partial Hydyolysis of the Trimethyl Ester.-A colourless oil. 0*2038 of i t s silver salt gave 0.1022 Ag. Ag=50*12. Dissociation constant. K = 0,00865, (Temp. 2 5 O . ) V. P V . 71%. K. 8.95 9.63 0.0275 0*00870 17.90 13.51 0.0386 0.00866 3590 18.94 0.0541 0.00863 71.60 26-28 0.0751 0.00859 There can be no doubt that the oil was a single substance and quite different from that obtained by direct esterification of the acid, but we have no means of judging at present which of the two formulae, ( b ) and (c), represents its constitution. (iii) Pbonz the Anhydro-acid.-A colourless oil.0.1286 of its silver salt gave 0.0642 Ag. Ag=4991 per cent. Dissociution constant. K= 0.01 86. (Temp. 2 5 O . ) 2'. PV* 71%. K. 12.52 15.89 0.0454 0.01 89 25.04 23.14 0.0661 0.0186 50.08 31.96 0.0913 0.0183 This monomethyl salt, therefore, is probably the same as that Comparing now the obtained by the direct esterification of the acid.46 BONE AND SPRANKLING: THE SYNTHESIS OF values for K, determined for tricarballylic and aa-dimethyltricarballylic acids and their monomethyl salts, Nonomethyl salt from Acid. Acid. Trimethyl ester. Anhydro-acid. 0.00925 Tricarballylic.. . .. . . . . . .. . . . 0.022 0 *O 09 4 5 aa-Dimethyltricarballylic 0.032 0.0180 0.00865 0.01860 we see that in both cases the monomethyl salt obtained by the direct esterification of the acid is quite different from that obtained by the par- tial hydrolysis of the trimethyl ester ; but that the salt obtained from the anhydro-acid is in the one case identical with that obtained from the trimethyl ester, and, in the other case, with that yielded by direct esterification of the acid.0.0075 a y - Dii so pro py lt riccw b d l y lic Acids. These acids were prepared with the view of determining whether the substitution of two isopropyl groups in ay-positions has an influence upon the dissociation constant of tricarballylic acid at all com- parable with that exerted upon the constant of succinic acid by the symmetrical substitution of two hydrogen atoms by isopropyl groups (compare Trans., 1900, 77, 667). Ethyl ay-diisoi?rol3ylc~c~no~r~c~~,balZyZate is a difficult oil to hydrolyse ; we found it best to perform the operation in two stages, namely, (l), with alcoholic potassium hydroxide, and (2), with 50 per cent.sulphuric acid. Finally, on extracting the acid liquid with ether we obtained from 17 grams of oil 9.8 grams of a solid mixture of stereoisomeric acids. These were difficult to separate, but on dissolving the mixture in water, saturating the solution with hydrogen chloride, and allowing it to stand for some time, we were able to resolve it into fractions of higher and lower melting point, by reason of the greater solubility of the latter. Two pure stereoisomeric acids were finally obtained, melting a t 173' and 156" respectively. Each yielded its own liquid anhydro-acid, but we had not sufficient material to investigate these properly, and it is possible tbat, had we been able to purify them further they would have solidified.The acid of higher melting point was transformed into the anhydro- acid of its isomeride on being boiled for many hours with acetyl chloride. Each acid was analysed, and its dissociation constant determined as follows : Acid, m. p. 173'. 0.2326 gave 0.4707 CO, and 0.1653 H,O. 0.1687 silver salt gave 0.0943 Ag. C,,H,oO, requires C = 55.38 , H = 7.69 per cent, C,,H,70,Ag, ,, C = 55.18 ; H = 7.90. Ag =5640. Ag = 55-90 per cent.ALKYLTRICARBAl~LYLIC ACIDS. 47 Dissociation constant. K = 0,193. (Temp. 25'.) I). m . K. 171.5 151.6 0.4332 0.1 93 343.0 191.5 0,5469 0.192 686.0 233.1 0.6660 0.1 94 1372.0 270.7 0.7731 0.192 Acid, m.p. 156'. 0,1971 gave 0,3982 CO, and 0,1397 H,O. C = 55.09 ; H = 7.8s. 0.2018 silver salt gave 0.1130 Ag. C,,H,,O, requires C = 55-38 ; H= 7.69 per cent. C,,HI7O,Ag, ,, Ag=55*99. Ag = 55.90 per cent. Dissociation constant. K= 0.1625. (Temp. 25O.) V. PV. m. K. 95.9 113.7 0.3241 0.1621 191.8 148.8 0.4250 0.1628 383.6 188.3 0.5380 0.1633 767.2 230.0 0,6570 0.1 640 If we compare these values with those for tricarballylic acid (0.022) and a-isopropyltricarballylic acid (0*0434--Auwers, Zoc. cit.), we see a t once that, in both cases, the introduction of the two isopropyl radicles has had a very marked ' raising ' effect on the dissociation constant, but there is no such enormous difference between the constants of the two isomerides as there is between those of cis- and tmns-s-diisopropyl- succinic acids.The subject of the variation of dissociation constants with molecular constitution in this series of acids presents many interesting features, and will be discussed more fully in a future communication. 111. TRICARBALLYLIC ACIDS FROM ETHYL BROMOSUCCINATES. As already stated, we have studied the preparation of ethyl cyano- tricarballylates by the interaction of ethyl bromosuccinates with the sodium compound of ethyl cyanoacetate, and have been able to carry it out in the following instances. Yricarbullylic Acid, The best method for preparing tolerably pure ethyl bromosuccinate, is to act on succinic anhydride with the calculated quantity of dry amorphous phosphorus and bromine, to form the dibromide of mono- bromosuccinic acid, and afterwards to pour the product into excess of48 BONE AND SPRANKLING: THE SYNTHESIS OF alcohol.I n this way we obtained an 80 per cent. yield of ethyl bromosuccinate boiling a t 140-143' under 29 mm. pressure, On condensing this with the calculated quantity of ethyl sodiocyanoacetate suspended in alcohol, a 70 per cent. yield of ethyl cyanotricarballylate resulted ; when hydrolysed, this yielded tricarballylic acid, melting at 157-159'. On analysis : 0.2023 gave 0.3028 CO, and 0.0854 H,O. C = 40.81 ; H = 4.69. C6H806 requires C = 40.90 ; H = 4.54 per cent. a-MethyZtricarbaZZylic Acid. On brominating 26 grams of monomethylsuccinic acid by the Hell- Volhard-Zelinsky method, pouring the product into alcohol, and extracting the resulting bromo-ester with ether, we obtained 38 grams of an oil which distilled over a t 151-153' under 44 mm.pressure. On analysis : 0.4166 gave 0.2798 AgBr. Br = 29-07. There are two possible isomeric ethyl monobromomethylsuccinates, C,H1,O4Br requires Br = 29.96 per cent. namely, (a) CH,*CBr(C0,Et)*CH2*C0,E t, and If the oil obtained by the method first indicated had the formula (a), then on condensing it with ethyl sodiocyanoacetate we should obtain the cyano-ester of P-methyltricarballylic acid ; on the other hand, if i t had the constitution (p), it would under similar treatment yield the cyano-esters of the a-methyltricarballylic acids, On trying the experiment we obtained a 50 per cent. yield of an ethyl methylcyanotricarballylate (b. p. 235-245' under 30 mm.pressure) which, on hydrolysis with strong hydrochloric acid, yielded the two a-methyltricarballylic acids, melting a t 177-180' and 134' respec- tively, but not a trace of any /3-methyltricarballylic acid. Hence the ethyl monobromomethylsuccinate obtained when methylsuccinic acid is brominated in the manner described has the constitution CH,*CH(CO,Et)* CHBr C0,Et. (p) CH,*CH( COzEtj*CHBr.CO,Et. The two a-methyltricarballylic acids obtained were analysed as Acid, m. p. 177--180'. 0.1921 gave 0.3174 CO, and 0.0953 H,O. 0.3011 silver salt gave 0.1900 Ag. Acid, m. p. 134". 09614 gave 0.4228 GO, and 0.1280 H,O. 0.1991 silver salt gave Oe1255 Ag. C7Hlo06 requires C=44.21 ; H=5-26 per cent. C7H70,Ag, ,, follows : C = 44.0 ;. H = 5.51. A g = 63.10. C=44*11 ; H=5*44.Ag = 63.06. Ag = 63.39 per cent.ALKY LTRICARBALLYLIC ACIDS. 49 aa-Dirnetk?lltricar6aZZyZ~c Acid. Twelve grams of as-dimethylsuccinic acid, on bromination by the Hell-Volhard-Zelinsky method, yielded 20 grams of monobromo-ester boiling at 159-164' under 70 mm. pressure. On analysis : 0,2442 gave 0.1589 AgBr. Br = 27-69. CloHI7O,Br requires Br = 28.47 per cent. On condensing this with the calculated quantity of ethyl sodiocyano- acetate, we obtained a 50 per cent. yield of ethyl aa-dimethylcyanotri- carballylate boiling at 210-220° under 35 mm. pressure. When hydrolysed with strong hydrochloric acid, this yielded aa-dimethyltri- carballylic acid melting at 140-142'. On analysis : 0.2611 gave 0.4554 CO, and 0.1408 H,O. 0.2122 silver salt gave 0.1308 Ag. C,Hl,O, requires C = 47.58 ; H = 5 *88 per cent. C,H,O,Ag, ,, We have also studied the bromination of cis-s-dimethylsuccinic acid by methods similar to those already described. Many workers have investigated the bromination of this and the isomeric trawls-acid under varying conditions and with widely different results. Hell and Roth- berg (Ber., 1889, 22, 66) state that both acids behave normally on bromination, yielding cis-monobromodimethy lsuccinic acid ; Zelinsky and Krnpivin (Ber., 1889, 22, 390), Bischoff and Voit (Bey., 1890, 23, 390), and Auwers and Imhauser (Ber., 1891,24, 2233), on the contrary, assert that neither acid can be brominated under any conditions, and that the substance which results is always the anhydride of pyre cinchonic acid (m. p. 95O), so that if any monobromo-anhydride (or acid) is momentarily produced it must a t once lose hydrogen bromide as follows : C = 47.59 ; H = 5.99. Ag=61%1. Ag = 61.71 per cent, Our own experience shows that when a mixture of cis-s-dimethylsuccinic acid and amorphous phosphorus is treated with the quantity of dry bromine required to form the dibromide of the monobromo-acid, bromina- tion certainly takes place, for on pouring the product into alcohol, and extracting and fractionating the resulting ester, we obtained a very fair yield of a bromo-ester containing 26.86 per cent. of bromine (C10H1,04Br requires Br = 28.47 per cent.). On condensing this bromo-ester with ethyl sodiocyanoacetate, sodium bromide was at once eliminated, but the product obtained was not a cyanotricarballylic ester, and up to the present we have not been VOL. Lxxxr. E50 BONE AND SFRANKLING : able to ascertain what really happened. investigation. The subject is still under I n conclusion, we wish to state that one of us is investigating the preparation and properties of tri- and tetra-methyltricarballylic acids. The cost of the materials required for this investigation has been largely defrayed out of grants from the Research Fund of the Society. THE OWENS COLLEGE, MANCHESTER.

ISSN:0368-1645    

DOI:10.1039/CT9028100029

出版商:RSC    

年代:1902

数据来源: RSC

摘要:

50 BONE AND SFRANKLING : VI.-The Bromination of Trimethylsucciiaic Acid and the Interaction of Ethyl B1.ornotri~~~etlzylsuccinate mad Ethyl Sodiocyanoucetate. By WILLIAM A. BONE and CHARLES H. G. SPRANKLING. IN connection with our investigations on the synthesis of alkyltricarb- allylic acids, me have recently studied the bromination of trimethyl- succinic acid, and the interaction of ethyl bromotrimethylsuccinate and ethyl sodiocyanoacetate. Some years ago, one of us, in conjunction with Professor W. H. Perkin, jun., unsuccessfully attempted the synthesis of i-camphoronic (aup-trimethyltricarballylic) acid by a method involving this reaction, which is expressed by the following equation : ( CH3),C(C02Et)*CBr(CH3)*C02Et + NaCH(CN)*CO,Et = NaBr + (CH3)2C(C02Et)*C(CH,)(C02Et)*CH(CN)*C02Et. As a matter of fact, a crystalline acid melting at 137" and quite different from i-camphoronic acid was finally isolated from the hydro- lytic products of the resulting cyano-ester, but the quantity obtained was too small to allow of a satisfactory investigation of its properties being made, The study of the subject was for the time being aban- doned, partly on account of the difficulty experienced in preparing a sufficient quantity of trimethylsuccinic acid by any method then known, and also because Yerkin and Thorpe succeeded in synthesising i-camphoronic acid by another method in 1897 (Trans., 71, 1169).Since, however, the preparation of large quantities of pure trimethyl- succinic acid is no longer a difficult matter, we decided to reinvestigate the subject, and, if possible, to ascertain the cause of the earlier failure to synthesise camphoronic acid.In 1898, Gustav Komppa (Acta Xoc. Scielzt. Fenn., 24, 1; also Abstr.,THE RROMJNATION OF TRI?~~ETHYJ~SUCCINIC ACID. 5 I 1899, i, 419) tried to prepare bromotrimethylsuccinic acid by the action of phosphorus pentabromide on the corresponding hydroxy-acid. H e was, however, unable to isolate any pure product from the complex mixture of substances obtained, and his experiments indicated that the three methyl groups in hydroxytrimethylsuccinic acid greatly hinder the replacement of hydroxyl by bromine. The results of our experiments may be briefly stated as follows : (1) When trimethylsuccinic acid is heated with the calculated quantity of bromine under pressure a t 1 30°, it is quantitatively converted into the characteristic white crystalline 6romotrimethylsuccinic anhydride melting a t 197-198'; it is not possible to obtain the pure bromotri- methylsuccinic acid by dissolving this anhydride in hot water, since partial decomposition, with loss of hydrogen bromide, occurs during the process.(2) If the bromination of trimethylsuccinic acid be carried out according to the Hell-Trolhard-Zelinsky (phosphorus and bromine) method and the product poured into alcohol, a mixture of bromo- anhydride and ethyl bromotrimethylsuccinate results, from which it is very difficult to obtain the latter substance in a tolerably pure state. (3) Both the bromo-anhydride and ethyl bromotrimethylsuccinate readily lose hydrogen bromide under the influence of an alkali.Ey heating the bromo-anhydride with diethylaniline and subsequently pouring the liquid into a solution of potassium hydroxide, we obtained the potassium salt of methylenedimethylsuccinic acid, C7H,,04. The ethyl ester of this acid very readily combines with hydrogen bromide, forming a bromo-ester, C7H,104Br, which, so far as we have been able t o ascertain, seems to be identical with the ethyl bromotrimethyl- succinate, (CH,),C(CO,Et) CBr( CH,)* CO,Et, prepared directly from trimet hylsuccinic acid. We would point out i n this connection that Vincenzo Paolini (Gccxzetta, 1900, 30, ii, 497)) by acting on ethyl hydroxytrimethyl- succinate with phosphorus pentachloride, has obtained the ethyl ester of an acid, C7H1004, melting a t 153-154'.Since this acid neither absorbed bromine or hydrogen bromide a t the ordinary temperature, nor decolorised cold alkaline permanganate, he concluded that its molecule was not unsaturated, and described it as dimethyltrimethyl- enedicarboxybk acid. The formation of such an acid he explained by supposing that the ethyl chlorotrimethylsuccinate formed in the first instance by the action of phosphorus pentachloride on the ester of the hydroxy-acid at once loses hydrogen chloride, the elimination of which takes place between the chlorine and a hydrogen atom of a methyl group attached t o the other carbon atom, so that 'ring- formation ' occurs thus, E 252 BONE AND SPRANKLING : - 70,Et ~ Y0,Et C02Et CH,*C CH,*$>CH, C0,Et CH,. F* CH, 1 CH3*Y*CH, CH,* $!*OH 1 CH,*Y*CL C0,Et L C0,Et His acid certainly appears to have properties quite different from those of methylenedimethylsuccinic acid, and we are therefore led to the interesting conclusion that the elimination of hydrogen bromide from a bromotrimethylsuccinic derivative and of hydrogen chloride from a chlorotrimethylsuccinic molecule may occur in two entirely different ways.This is a point which certainly deserves further investigation. (4) Ethyl bromotrimethylsiiccinate reacts with ethyl sodiocyano- acetate, yielding the cyano-ester of a tribasic acid, C,H,,O,, melting a t 137-13S0, and isomeric with i-cnmphoronic acid (m. p. 169-17Z0). Tbe formation of such an acid can be explained on the supposition that ethyl bromotrimethylsuccinate loses hydrogen bromide, forming ethyl methylenedimethylsuccinate, which at once condenses with the ethyl cyanoacetate as follows : -+ (CH,),C(CO,Et)*C(CO,Et): CH, + CH2( CN)*CO,E t = (CH,),C(CO,Et) CH( CO,Et)*CH,*CH( CN) *CO,Et.I f this interpretation of the matter be correct, the acid, C,H,,O,, obtained on hydrolysing the product with hydrochloric acid would be aa-dimethyZbuta~e-ap6-tl.icar~oxyZic acid, (CH,),C(CO,H)*CH(CO,H) *CH,* CH,* C0,H ; the results of a ' potash fusion ' of the acid, which yielded acetic and trimethylsuccinic acids, are consistent with this view of its constitution. EXPERIMENTAL. Bromination of TrimthyZauccinic Acid. Tormation of BromotrimethyZ- succinic Anhydride and Eth y Z Bromotrime th y Zsuccinate. (1) HcZl-PoZhal.d-ZeZinsky Method.-We have a t various times carried out experiments in which rather more than the calculated quantity of dry bromine was slowly dropped on a well cooled mixture of trimethyl- succinic acid and the theoretical amount of dry amorphous phosphorus.I n each case, a vigorous reaction ensued accompanied by a strong evolution of hydrogen bromide, which only ceased after the mixture had been heated on the water-bath in a reflux apparatus for 6 or 8 hours. On dropping the resulting brown liquid into an excess of alcohol (well cooled in ice) and afterwards pouring the alcoholic solution into a large excess of water, a beavy brown oil separated, which wasTHh BROMINATION OF TRIMETHYLSUCCINIC ACID. 53 extracted with ether in the usual manner. After washing the ethereal solution with dilute ( 5 per cent,) sodium carbonate solution, then drying it over anhydrous sodium sulphate, and finally distilling off the ether, there remained a heavy reddish-brown oil which appeared to decompose when we tried to distil it under reduced pressure.Analyses showed, however, that samples prepared at different times invariably contained from 30 to 33 per cent. of bromine, or consider- ably more than that required for ethyl bromotrimethylsuccinate, CllHI9O4Br, namely, 27.12 per cent. Brmotrimethylsuccinic Anhydride. -After the oil had stood for some weeks in an exhausted desiccator over sulphuric acid, yellowish crystals began to separate; these were removed from time to time, and after being pressed on a porous plate were recrystallised from hot benzene. When quite pure, they melted sharply at 197-198'.The substance was insoluble in cold water or a cold solution of sodium carbonate, but readily dissolved in a warm solution of potassium hydroxide without, however, any formation of alcohol. It was, therefore, neither an acid nor an ester ; the following analysis showed that it had a com- position corresponding to that of bromotrimeth ylsuccinic anhydride, and a further study of its properties showed it to be this substance." 0.1691 gave 0.2368 CO, and 0.0600 H,O. C = 38.19 ; H = 3.95. 0.2364 ,, 0.2036 AgBr. Br=36.64. C7Hg0,Rr requires C = 38.06 ; H = 4.07 ; Br = 36.20 per cent. Ethyl Bronaotrimethy2succinate.-The crude oil was kept for several months until no further separation of bromoanhydride occurred : on analysing the residual oil, we obtained, for two different preparations, the following numbers : (1) 05202 gave 0-3525 AgBr.(2) 0.2528 ,, 0.1713 AgBr. Br=28*83 ,, It, therefore, still contained 1.7 per cent. more bromine than that Br=28.82 per cent. * Assuming that the dibromide of bromotrimethylsuccinic acid is produced by the action of phosphorus and bromine on trimethylsuccinic acid, the formation of this bromoachydride can only be accounted for on the supposition that when the bromo-dibromide is dropped into alcohol, only part of it is decomposed, yielding ethyl bromotrimethylsuccinate, and that the other part reacts with the alcohol somewhat as follows : (CH,),C*COBr (CH3)2C--CO -k 2C2H5'OH = >O + 2C2H5Br + H20, CH,*hBr'COBr CH,*hBr*CO I + (CH,),y*CO2C2Hb CH,'CBr 'COBr (CH,),C--CO >O f C,H,Br.( CH3),C' COBr or (2) + C,H,'OH = HBr + CH,*bBr 'COBr CH,&Br*CO54 BONE AND SPRANKLING : required for ebhyl bromotrimethylsuccinate, an indication that there remained a fair quantity of the bromo-anhydride in solution (a mix- ture of 81.3 parts of bromo-ester and 18.7 of bromo-anhydride would contain 28.8 per cent. of bromine). With a view to the complete esteri- fication of this bromo-anhydride, the oil was repeatedly heated with an excess of etbyl alcohol containing 5 per cent. of hydrogen chloride ; by this means, the bromine was reduced to 28.0 per cent. As we subsequently found, however, that the bromo-anhydride, when treated with alcohol and hydrogen bromide, forms only the monoethyl salt, it mas evident that the oil now consisted of a mixture of neutral and acid esters.We therefore dissolved i t in pure ether and extracted the solution with a 5 per cent. sodium carbonate solution. On distil- ling off the ether, me found that the residual oil could now be fraction- ated under reduced pressure without undergoing any appreciable decomposition. Under 20 mm., the greater portion of it distilled over between 160" and 170" as a faint yellow oil having a very pungent odour. The following analysis indicated that i t was practically pure ethyl br omotri me t hy lsuccina t e :* 0,2934 gave 0,1846 AgBr. Br =; 26-76. C,,H,,O,Br requires Br = 27.1 2 per cent. (2) Action of Bromine on T&methylsucci.nic Acid at 120-130'.- Bromotrimethylsuccinic anhydride may be most conveniently prepared in quantity by the following method.Five grams of trimethylsuccinic acid are heated with an equal weight of dry bromine in a sealed tube at 120-130O for 6 to 8 hours. The careful regulation of the temperature is important, since below 120" the bromination is not complete, and above 140' the contents of the tube are liable t o char. Great care should be taken in opening such tubes after the heating, for the pressure in them is very great, and since dense clouds of hydrogen bromide are evolved it is advisable to carry out the operation in the open air. A solid with a slight orange colour remains after the pressure has been relieved; sometimes it swells up considerably during the escape of gas, and may occasionally froth over out of the tube, and it is therefore advisable to have a large beaker a t hand in which to receive any that may be so forced out. The solid should be washed with a cold dilute solution of sodium carbonate, dried on a porous plate, and recrystallised from hot benzene.The yield is quantitative. * The preparation of this ester is best carried out by dropping the brominated trimethylsuccinic acid into excess of ice-cold ethyl alcohol containing 5 per cent, of hydrogen bromide, heating the solution for about three hours on the water-bath to convert the bromo-anhydride into the monoethyl salt, and subsequently removing the lat,ter by nieans of a cold 5 per cect. solution of sodium carbonate.THE BROMINATION OF TRIMETHYLSUCCINIC ACID. 55 When pure, the bromo-anhydride melts a t 197-198' ; it is quite in- soluble in cold water or a cold dilute solution of sodium carbonate.We endeavoured to prepare bromotrimet hylsuccinic acid by dissolving the anhydride in warm water and evaporating the solution until, on cooling, crystals appeared. I n this way, colourless needles were Ob- tained which, however, melted indefinitely between 120' and 130°, and contained only 31-1 per cent. of bromine; since the bromo-acid, C7HI1O4Br, requires 33.5 per cent. of bromine, i h was evident that some decomposition had occurred during the solution of the bromo- anhydride, and a subsequent careful examination showed that hydrogen bromide is slowly liberated during the process. Action of AZcohol and Sodium Ethoxide on the B1.onzo-ccnhydride.- On heating the bromo-anhydride with a molecular proportion of sodium ethoxide in ethyl alcohol, the liquid became neutral in about half an hour without, however, any separation of sodium bromide.On passing dry hydrogen chloride into the resulting liquid, sodium chloride separ- ated, and as soon as the whole of the sodium had been thus eliminated the liquid was filtered and the clear filtrate evaporated in a vacuum over sulphuric acid. There finally remained a colourless, semi-solid mass containing 30.3 per cent. of bromine, which exhibited all the pro- perties of an acid ester (ethyl hydrogen bromotrimethylsuccinate, C,H,,O,Br, requires Br = 30.0 per cent.). The same substance was obtained by heating the bromo-anhydride with an excess of ethyl alcohol in sealed tubes a t 160' and afterwards distilling off the excess of alcohol on the water-bath. I n neither of these experiments were we able to detect the formation of any neutral ester, and in each case the product instantly and completely dissolved in a cold solution of sodium carbonate with evolution of carbon dioxide. Our attempts to purify the substance by distillation under reduced pressure were unsuccessful, since decomposition began a t temperatures below the boiling point.We also made several unsuccessful attempts to prepare the silver salt of this acid ester, but as soon as silver nitrate was added to its aqueous solution neutralised with dilute ammonia, a copious yellow precipitate of silver bromide appeared, and we were not more success- ful in experiments in which freshly prepared silver carbonate was added to the aqueous solution.Action of Diethy Zaniliiae on the Bromo-anhydride. Methylenedirnethyl- succinic Acid, C7Hlo0,. As bromotrimethylsuccinic anhydride showed a tendency to lose hydrogen bromide on being boiled with water, we decided to study the action of diethylaniline on i t with the view of preparing the correspond- ing unsaturated acid.56 BONE AND SPRANKLING : Accordingly, a solution of 10 grams of the bromo-anhydride in 15 grams of diethylaniline was heated in a reflux apparatus on a sand- bath for 10 hours, after which it was poured into a hot concentrated solution of potassium hydroxide. After the diethylaniline had been extracted with ether, t.he alkaline liquor was acidified, saturated with ammonium sulphate, and again extracted with ether.I n this way a solid acid was obtained which was purified by dissolving it in excess of sodium carbonate soluti.on, extracting resinous matter with chloroform, then boiling the solution with animal charcoal, finally acidifying and extracting it with pure ether. The pure acid was thus obtained as perfectly white crystals which melted a t 140-141'. On analysis : 0.2063 gave 0.401.0 CO, and 0.1290 H,O. C = 52.9 ; H = 6-51. C7H,,04 requires C = 53-16 ; H = 6.33 per cent. ~ethylenedimethylszcccilzic acid, (CH3)2y*C02H melts a t 140-1 41', is CH2: C* C0,H' fairly soluble in cold water, and, like other succinic acids, gives an in- soluble calcium salt when a solution of its neutral ammonium salt is boiled with calcium chloride solution. Its aqueous solution instantly decolorises alkaline permanganate and rapidly absorbs bromine in the cold.The acid is readilyesterified, and its liquid diethyl ester boils at 173-176' under 755-760 mm. Action of Bromine on the Diethyl Esteq*.-On adding a solution of bromine in chloroform to the diethyl ester, the halogen a t once dis- appeared ; as soon as no more of it was absorbed, the chloroform was distilled off and the residual oil a t once hydrolysed with hydrochloric acid. On cooling, a white crystalline dibromo-acid separated, which after recrystallisation from hydrochloric acid melted at 178 -179'. On analysis : 0,3027 gave 0.3529 AgBr. Br=49*6. C7H,,04Br2 requires Br = 50.0 per cent. Action of Hydrogen By*omide on the Diethyl Estei*.-Ten grams of the diethyl ester were mixed with an aqueous solution of hydrogen bromide (saturated at 0').Milch heat was evolved, the bromide being very quickly absorbed. The product was extracted with ether, and the ethereal solution washed with dilute sodium carbonate solution and after- wards dried over anhydrous sodium sulphate. On distilling off the ether there remained a liquid diethyl ester of a bromo-acid which contained an amount of bromine corresponding to that required for the empirical formula C,,H,,O,Br. Thus : 0.4165 gave 0.2650 AgBr. Br = 27.07. C11H1,04Br requires Br = 27.12 per cent.THE BROMINATION OF TRIMETHYLSUCCINIC ACID. 57 Most probably, therefore, this oil was ethyl bromotrimethylsuccin- ate, (CH3),C(C02C,H,)*C(CH3)Br*C02C2H5, although it is just possible that it was the isomeric ethyl a-methyl-8-bromobutane-py-dicarboxyl- ate, (CH,),C( CO,C,H,)*C)H( C0,C2H,)*CH2Br.On comparing the action of the oil with that of the ethyl bromotrimethylsuccinate obtained by the direct bromination of trimethylsuccinic acid (see p. 54) on ethyl sodiocyanoacetate (see next section), identical products were obtained in the two experiments. We afterwards found that the identity of these products does not necessarily imply the identity of the two bromo-esters in question, so that which of the two foregoing formulae represents the constitution of the oil obtained by the action of hydrogen bromide on diethyl methylenedimethylsuccinate is a point we have not yet definitely established. Interaction of Ethyl Bromotrimet~ylsuccinat~ and Ethyl Xodiocyano- acet 8 t e.(1) To a solution of 1'5 grams of sodium in 20 grams of alcohol were added 7.5 grams of ethyl cyanoacetate and 19 grams of ethyl bromotrimethylsuccinate ; much heat was developed, sodium bromide separated, and the liquid became neutral after being heated for 3 hours on the water-bath. The product was extracted with ether and fractionated under 20 mm. pressure. A fair proportion of it passed over between 130Oand 150°, the temperature then rose rapidly toabove 200°, and about half of the oil distilled between 210'and 215'. This higher fraction was hydrolysed by boiling it with strong hydrochloric acid for 24 hours. On cooling the liquid, no crystals separated, so it was saturated with ammonium sulphate and thoroughly extracted with ether. In this way, a white crystalline acid was isolated which, after recrystallisation from strong hydrochloric acid, melted sharply a t 137-138O.This, it will be observed, is the same melting point as that of the acid obtained by one of us and Professor Perkin some years ago by the same series of reactions. The acid was therefore not i-camphoronic acid (m. p. 169--172O), and, further, all attempts to iso- late any camphoronic acid from the hydrolytic products by means of its characteristic barium salt entirely failed, so me can only conclude that none had been formed. Analysis of our acid, however, indicated that it was tribasic and isomeric with camphoronic acid, C,H1,O,, thus : 0,1364 gave 0.2500 GO, and 0.0813 H,O. 0.1095 silver salt gave 0.0657 Ag. C = 49.87 ; H = 6.62. Ag = 60.0. Ag = 60.10 per cent. C,Hl,O, requires C = 49.53 ; H = 6.42 per cent.C,H110,Ag3 ,,58 THE BROMINATION OF TRIMETHYLSUCCINIC ACID. (2) In another experiment, 11 grams of the bromo-ester obtained by the action of hydrogen bromide on ethyl methylenedimethylsuccinate mere added to the calculated quantity of ethyl sodiocyanoacetate sus- pended in alcohol. Sodium bromide a t once separated and on continu- ing the experiment as described in the preceding paragraph, we finally obtained a cyano-ester boiling a t 230--240° under 40 mm. pressure. This on hydrolysis with hydrochloric acid yieided the same acid, C,H,,O,, melting at 137". Pusion of the Acid, C,H,,O,, with Potassium Hgdroxide. In order to obtain evidence as to the constitution of the acid, 5 grams OF the substance were fused with n paste of 30 grams of potassium hydroxide a t 180-200°. A vigorous decomposition ensued. After being cooled, the fused product was dissolved in water, acidified with dilute sulphuric acid, and the liquid then distilled with steam. The distillate contained a fatty acid, the analysis of whose silver salt showed it was acetic acid. 0.2021 silver salt gave 0.1303 Ag. Ag=64.47. C2H,02Ag requires Ag =-2 64.67 per cent. On extracting the residual liquor with ether, a solid wid melting a t 147" and in other respects i4entical with trimethgleuccinic acid was obtained. (An analysis of the silver salt of this acid was made, but the results have, unfortunately, bertn mislaid ; they agreed well with the calculated numbers for silver trimethylsuccinate.) These results are quite consistent with the view that tbe acid C,H,,O, is aa-dimet~~~lbutane-apS-lricai.boxylic acid, and indeed it is difficult to see what other constitution could be assigned to it. The further investigation of its properties has, for the time being, been stopped on account of lack of material, but will be resumed in the near future. We desire to state that the greater part of the materials required for this research was purchased out of agrant from the Research Fund of the Society. THE OWENS COLLEGE, MANCHESTER.

ISSN:0368-1645    

DOI:10.1039/CT9028100050

出版商:RSC    

年代:1902

数据来源: RSC

摘要:

CONSTITUENTS OF THE ESSENTIAL OIL OF ASARUM CANADENSE. 59 VL-The Constituents of the Esseizticcl Oil qf Asurum Canadense . By FREDERICK B. POWER and FREDERIC! H. LEES. THE aromatic essential oil distilled from the underground portion, rhizome, and rootlets of Asarunz canadense, comtnonly known as Canada Snake-root, was first investigated by one of us a number of years ago (Power, Inaug. Diss., Strassburg, 1880 ; PYOC. Amev. Pharm. ASSOC., 1880,28, 464). I n that investigation, the following substances were isolated. (1) A terpene, C,OHIB, b. p. 163-166'; (2) two fragrant alcohols, differing considerably in their boiling points and also in their odour, but both possessing the same empirical formula, CloHl,O. The alcohol of lower boiling point, 196-199', was termed nsurol, and had an odour which recalled that of coriander, but was also somewhat camphoraceoua, whilst the alcohol of higher boiling point, 222-226', had a rose-like fragrance ; (3) a fraction, possessing but little odour, b.p. 254-257", representing the largest single con- stituent of the oil, which, upon oxidation with chromic acid, afforded an acid of the composition C,H,,O,. This acid mas subsequently showu by Petersen (Beis., 1888, 21, 1062) to be veratric acid and was obtained by him by the oxidation of an analogous substance contained in the oil of Asarurn europaeum, boiling a t about 250", which he proved to be eugenol methyl ether ; (4) a fraction collected a t 275-350°, which contains a deep blue oil of undetermined composition ; (5) a large amount of acetic acid, combined with the above-mentioned alcohols in the form of acetic esters, together with a very small amount of a less soluble, oily acid, which appeared t o consist of, or at least to contain, valeric acid.I n consideration of the advance in knowledge of the constituents of essential oils since the period of the first investigation, and the means which are now available for the more positive identification and classification of these constituents by the preparation of well-defined and mostly crystallisable derivatives, it has seemed desirable again to subject the oil in question to a careful chemical examination. EX P E R I N E N T A L . The oil employed for this research, about 2 kilos. in amount, was distilled by Messrs. Schimmel & Co. of Leipzig. Its density a t 15'/15" was 0.952, and its rotation aD= - 3'24' in a 100 mm.tube. The oil was first shaken with a 5 per cent. solution of sodium carbonate in order to remove the free acids, which were examined in connection with the acids obtained by the subsequent hydrolysis of the60 POWER AND LEES: THE CONSTITUENTS OF THE oil. It was then shaken three times successively with a 5 per cent. solution of sodium hydroxide, and afterwards with water until the washings were neutral. The combined alkaline liquids were shaken twice with ether to remove any adhering oil, then acidified with sulphuric acid, completely extracted with ether, and the ethereal liquid dried with calcium chloride. After distilling off the ether, the residual liquid was distilled in a vacuum.Under 10 mm. pressure, it began to distil at 155O, rising rapidly to 250', and the last portion was observed to solidify in the condenser. When refractionated, there mere obtained : I. A light coloured oil boiling at 172' under 35 mm. pressure. 11. A dark oil which boiled somewhat below 200' under 10 mm. pressure and solidified on cooling. The Phenol, C,H,,O,. The first of the preceding fractions was distilled under the ordinary (762 mm.) pressure and afforded : (1) A light greenish liquid, becoming brown on standing, and boiling below 245'. (2) A light yellow liquid, boiling at 245-260°, which did not solidify a t - 169 (3) A small residue, from which R little crystalline substance separated on cooling. Of these fractions, (I) and (2) were analysed. (1) 0.1402 gave 0.3606 CO, and 0.1008 H,O.C = 70.1 ; H = 8.0. (2) 0.1493 ,, 0.3923 CO, ,, 0,1066 H,O. C=71.*6 ; H=7*9. These two fractions were then subjected to a final fractionation (a;) A few drops only distilled below 220'. ( b ) From 220' the mercury rose rapidly to 2.15". (c) The chief portion distilled between 245' and 255', and was (d) Only a few drops distilled above 255'. Eraction (c) was then analysed. 0.1523 gave 0.3992 CO, and 0.1073 H,O. These results indicate that the phenol contained in asarum oil has the empirical formula C9H,,0,. It is a nearly colourless, oily liquid, having an odour recalling, but more agreeable than, that of creosote. In the process of liberating the phenol from its alkaline solution a somewhat clove-like odour was developed, and this at first led us to suspect that the phenol contained some eugenol.This, however, is under the ordinary pressure, with the following result : fairly constant a t 248-252". C = 71.5 ; H = 7.8. C,H,,O, requires C=71*1 ; H=7*9 per cent.ESSENTIAL OIL OF ASARUM CANADENSE. 61 rendered highly improbable, both on account of the constancy of the analytical results and the characteristic colour reaction which was afforded by all the fractions, but most strikingly by the principal fraction (c). Thus a very small quantity of the phenol, when dissolved in 90 per cent. alcobol, gives, with a trace of very dilute ferric chloride, a beautiful violet colour which only gradua.lly fades, whilst eugenol, under the same conditions, gives a green. If, however, the phenol from asarum oil be dissolved in absolute alcohol, and a trace of a stronger solution of ferric chloride added, it affords a green colour, whilst eugenol, under these conditions, gives a deep blue.The amount of the phenol available did not permit of the formation of any deriva- tives, but as it is not identical with any of the known phenols of the formula indicated, it is evidently a new substance, and we shall endea- vour to determine its constitution by some synthetical experiments. IdeiLtiJication of Palmitic Acid. It was noted that in the first distillation of the phenol, a solid sub- stance separated in the condenser, and that in a subsequent fractiona- tion the higher fraction, designated as I1 (p. 60), solidified on cooling. This was, therefore, brought upon a porous tile, and the substance subsequently dissolved in hot light petroleum, from which, on cooling i t crystallised in colourless, pearly plates.I t s melting point was 60-61", and this remained unchanged on recrystallisation. On analysis, i t was identified as palmitic acid : 0.0874 gave 0.2382 00, and 0.0982 H,O. C: = 74.3 ; H = 12.5. C,,H,,02 requires C = '75.0 ; H = 12.5 per cent. Ident$catim of Finene. X e p a t i m of the Terpene.-The oil, which had been shaken with a dilute solution of sodium hydroxide as previously described, was washed with small, successive portions of water until the washings were neutral, and dried with anhydrous sodium sulphate. It was then distilled under diminished pressure and the portion collected which boiled below 100' under 10 mm.pressure. After several frac- tionations of this portion and drying with potassium carbonate, the lowest fraction, which distilled below 85' under 10-15 mm. pressure, was collected. Its density was 0.8566 at 18'/16', which proved the absence of any olefinic terpene. These liquids were then further fractionated under the ordinary pressure, when the greater portion finally distilled below 165', (a), chiefly at 159-161", and only exceedingly small fractions were collected between 165' and 170" (/I) and from 170-180° (7). These were analysed, with the following results :62 POWER AND LEES: THE CONSTITUENTS OF THE (a) 0.1252 gave 0,4003 CO, and 0.1320 H,O. C = 87.2; H = 11.7. (/I) 0.1526 ,, 0.4873 CO, ,, 0,1606 H,O. C=87.1 ; H = l l * $ . (7) 0.1558 ,, 0.4920 CO, ,, 0.162s H,O.C = 86.1 ; I1 = 11.6. CloHl, requires C = 85.2 ; H = 11 *8 per cent. Ymction below 165' -This fraction, boiling chiefly between 159O and 161°, which is seen to consist of a nearly pure hydrocarbon, amounted to about 2 per cent. of the original oil. Its physical con- stants were as follows : d 16"/16" = 0,8563. a r = + 1'36'. It readily formed a crystallisable nitrosochloride melting sharply at 103-104°. From the latter, the nitrolpiperidide was prepared, which, after re- crystallisation from methyl alcohol, melted sharply a t 118 -1 19'. This fraction thus consisted of pinene, and its low rotation indicates it to be a mixture of the d- and I-forms. Petersen (Ber., 1888, 21, 1059) has previously recognised the terpene existing in the oil of both the European and American species of Asccruma as pinene, in the former as the Lvariety, but identified it only by the formation of an oily monobromide and by its conversion into dipentene.As it was possible that the very small fraction of our oil collected between 170" and 180' might contain dipentene or limonene, it was treated with bromine, but only an uncrysfallisable, oily product was obtained. After being carefully dried, a bromine determination was made of this, with the following result : 0.2915 gave 0.3'762 AgBr. Br = 54.9. C,,H,,Br, requires Br = 54.1 per cent. This result serves to prove the absence of either dipenteno or limonene, both of which form crystallisable tetrabromides, CloHl,Br,. By a careful examination of all the fractions, no terpene other than pinene could be detected in the oil.Hydrolysis of the Oil. For further examination, all the oil boiling above the tergene frac- tion was now hydrolysed by boiling with alcoholic potassium hydr- oxide for about 2 hours in a flask provided with a reflux condenser. After distilling off the greater portion of the alcohol from a water- bath, the liquid was brought into a separating funnel and sufficient water added to effect the separation of the oil. The latter was then drawn off, the aqueous alkaline liquid shaken with successive portions of ether, and the ether extracts mixed with the separated oil. The latter was then mashed several times with water, and these washings added to the aqueous alkaline liquid. The ethereal solution of the oil was quickly dried with calcium chloride, filtered, the ether distilled off, and the residue finally subjected t o fractional distillation, firstESSENTIAL OIL OF ASARUM CANADENSE.63 under diminished pressure, and then in part under the ordinary pres- sure. The following fractions were eventually obtained : 195--203', 203-208", 208-216', 216-222", 222-235", 235--?145',and 245-2660". Identijication of I;inccbool. Pkaction 195-203'.-This was a large fraction which, when re- distilled under the ordinary pressure, passed over mainly a t 199' and almost entirely at 198-202' under 768 mm. pressure. It is a colour- less, fragrant liquid. It was analysed and its physical constants were determined with the following results : 0,1372 gave 0.3910 CO, and 0.1436 H,O. C = 77.7 ; H = 11.6.C,,H,,O requires C = 77.9 ; H = 11.7 per cent. d 15*5°/150=0*S711. aD= + 10'48' in a 100 mm. tube ; La]D= + 12.4". When oxidised with chromic acid, it afforded citral, which was ob- tained as a pale yellow liquid of strong, lemon-like odour, distilling at 110-115° under a pressure of 10-12 mm. The latter, by condensa- tion with pyruvic acid and P-naphthylamine, was converted into the crystalline a-citryl-/?-naphthacinchoninic acid, melting a t 1cj5-19S0. The identity of this fraction with d-ZinaZoob is therefore definitely established. It corresponds to the substance C,,H,,O (b. p. 196-199"), which in the first investigation of the oil was designated asarol. Fraction 203-2085.-Thia fraction was too small for further ex- amination, and evidently consisted simply of a mixture of the preced- ing and the following fractions.Fraction 20S-216°.-This was a small fraction, which distilled mostly between 208' and 212'. It was analysed, and its physical constants were determined, with the following results : 0.1368 gave 0,3866 CO, and 0.1424 H20. C = 77.1 ; H= 11.6. 0.14'72 ,, 0.4154 CO, ,, 0.1524 H,O. C=77.0; H=11*5. C,,H,,O requires C = 77.9 ; H = 11 -7 per cent. d 15~5°/150=0~911; aD= -0'24' in a 100 mm. tube. IdentiJicatiorn of Borneo 2. The liquid had a camphoraceous and also somewhat rose-like odour. When subjected to a temperature of - 10" for an hour, no crystalline substance separated. As this fraction of the oil was relatively small, and as its constituents were evidently contained to some extent in the next higher fraction, the two fractions were mixed.A portion, how- ever, of the higher fraction was reserved for special examination. This mixture of the two fractions was now gently oxidised with Fittig's oxidation mixture (Ber., 1885, 18, 3207) in the following64 POWER AND LEES: THE CONSTITUENTS OF THE proportions: 10 parts of oil, 80 parts of potassium dichromate, and 120 parts of sulphuric acid, the latter diluted with three times its volume of water. The oxidising mixture was added in small amounts a t a time to the oil, which was kept cool by immersion of the containing flask in water, After all the chromic acid solution had been added, the mixture was heated on a water-bath for about 20-30 minntes. It was then distilled from a water-bath under diminished pressure and the camphor which separated in the condenser and dis- tillate was collected by filtration, and dried on a porous tile.A little of the sulnlimed product was found to meIt sharply at 175O. A deter- mination of its specific rotation in 90 per cent. alcohol gave the follow- result : uD = - 1'45' ; I = 0.5 dcm. ; c = 8.684 ; [aID = - 40.3'. For further identification of the camphor, the oxime was prepared, and found to melt at 115-116O. As camphor could not be detected in the fraction of the original oil, its formation by the above method of oxidation is conclusive proof of the presence of 1-bonzeol in the oil. The chromic acid liquor remaining from the distillation of the cam- phor was subsequently shaken out several times with ether, the ethereal solution washed with a little water, dried with calcium chloride, and the ether removed by distillation.The residual light yellow oil, which had a strong odour of acetic acid, was found to be not entirely soluble in cold sodium carbonate solution. It was consequently redissolved in ether and the ethereal solution shaken out several times with a dilute solution of sodium carbonate in order to remove the acids, The ethereal solution was then washed with a little water, dried with calcium chloride, and the ether removed by distillation. The residue was a light yellow oil possessing a coumarin-like odour, and on standing a short time became a crystalline paste. This was drained on a porous tile, when the substance was obtained quite white. After recrystallisa- tion from dry ether it melted at 62O, and was insoluble in sodium carbonate solution.On analysis : 0.1148 gave 0.2731 CO, and 0*0902 H20. C = 64.9 ; H = 8.7. C,,H,,O, requires C = 65.2 ; H = 8.7 per cent. This substance is undoubtedly identical with the ketokactons, C,oH,,O, (m. p. 62-63'), which was isolated as a product of the oxidation of terpineol by chromic acid by Wallach, and has been further studied by him, as also by Tiemann and others (AnnaZen, 1893, 275, 153; 277, 118; Ber., 1895, 28, 1773, 1781). The sodium carbonate solution from which the ethereal solution of the above ketolactone had been separated was acidified with hydrochloric acid, and shaken out several times with ether. TheESSENTIAL OIL OF ASARUM CANADENSE. 65 ethereal solution was washed once with water, dried with calcium chloride, and the ether removed by distillation.The residue was a light yellow syrup, whicb, on standing, deposited a crystalline acid. The syrup was consequently diluted with ether, in which the crys- tals appeared to be sparingly soluble, and from which they were easily separated by filtration. After washing with dry ether, the substance was finally recrystallised from boiling ether. It melted at 173-174" and dissolved with effervescence i n a cold solution of sodium carbonate. 0.1 16s gave 0.2266 CO, and 0.0695 H,O. C7Hl0O4 requires C = 53.2 ; H = 6.3 per cent8. This acid is evidently identical with terebic acid, CTHIo04 (m. p. 175O), which has been found as a direct oxid+tion product of terpineol, as also of the ketolactone, CloH,,O, (Tiemann and Mahla, Ber., 1896, 29, 2621).The syrup from which the terebic acid crystallised was not examined but probably contained terpenylic acid, which always accompanies terebic acid when terpineol or the ketolactone is oxidised with chromic acid mixture. I t is thus shown that the fractions of the oil which served for the identification of borneol also contained a con- siderable amount of terpineol. I n the first investigation of asarum oil, a considerable fraction was collected at 222-226', and as a portion of this was still available it WJS thought of interest to examine i t again. It was therefore oxidised with a chromic acid mixture in the manner just described, and among the products of oxidation there were isolated and identified : camphor (m. p. 175") ; the ketolactone, C,,H,,O, (m, p.62') ; and terebic acid (m. p. 173-114"). It therefore contained borneol and terpineol, and, apparently, a small amount of geraniol, as it had the characteristic rose-like odour. C = 52.9 ; H = 6.6. .Tdentijcation of Teqirzeol. phoraceous and also a somewhat rose-like odour. its physical constants were determined, with the following results : C = 77.5 ; H = 11.4. Praction 216-222°.-This was a small fraction. I t had a cam- I t was analysed and 0.1647 gave 0.4682 CO, and 0.1698 H,O. 0.1633 ,, 0.4610 CO, ,, 0.1680 H,O. C = 77.0 ; H= 11-4. C,,H,,O requires C = 77.9 ; H = 11.7 per cent. d 15-5°/15"-0*9267 ; a,= - S"26' i n a 100 mm. tube. The portion of this fraction which had not been used in connection with t h e preceding one, as described under the latter, was employed for the direct identification of terpineol.I n view of the presence of small amounts of other alcohols, the following method was employed. VOL. LXXXI. F66 POWER ,4ND LEES: THE CONSTITUENTS OF THE The liquid was shaken with a concentrated solution of hydriodic acid (sp. gr. Z*O), when a heavy, dark oil was formed. This was separated from the aqueous layer, and shaken with a dilute solution of sodium bisulphite to remove any free iodine. The oil was then washed with water and allowed to stand, when after a short time crystals began to form, and finally the whole became a crystalline paste. This was spread on a porous tile, when a small quantity of nearly white needles was obtained, which, after recrystallisation from light petro1,eum (b.p. 30-40°), melted a t 80'. This melting point was identical with that of dipentene dihydriodide, C,,,HI8T2, which, for the purpose of comparison, we had also prepared from pure crystallised terpineol, and when the two hydriodides were intimately mixed, the melting point remained unchanged. The formation of t h i s derivative, and of the products of oxidation described in the preceding section, proves conclusively the presence of terpineol in the oil. The optical rotation of the fraction from which it was obtained indicates i t to be the I-form. Identijcation, of Gevanio 1. Fruction 223--3359-This fraction was collected within the above limits, in view of the possible presence of both citronellol and geraniol. It was relatively small in amount, and was analysed, and its physical constants were determined, with the following results : 0.1544 gave 0,4370 CO, and 0,1549 H,O.C = 77.2 ; H = 11.1. 0.1420 ,, 0.3999 CO, ,, 0.1433 H,O. c! = 76.8 ; H= 11.2. C,,,H,,O requires C= 77.9 ; H = 11.7 per cent. I t possessed a camphoraceous and also a fragrant, rose-like odour. Although its high density and rotation indicated that i t contained a considerable amount of terpineol, and its analysis also showed an admixture with some of the next higher fraction, the small amount of liquid precluded its further purification by simple distillation. The odour of this fraction afforded such convincing evidence of the presence of geraniol t h a t Erdmann's method, which depends on the formation of the crystalline geranioldiphenylurethane (m.p. 82O), was resorted to for the identification of the substance (J. pr. Chem., 1897, [ii], 56, 8). The oil was treated with diphenylcarbamic chloride in presence of pyridine, as described by Erdmann ; the syrupy residue left after distilling the product with steam was then purified by extraction with ether, and the ethereal solution emporated after extraztlon with dilute hydrochloric acid. The residual light brown oil was mixed with a little alcohol, when it soon formed a crystalline paste, which was drained on a porous tile. The substance was finally recrystallised d 15*5'/15O = 0.9340 ; uD = - 9'8' in a 100 mm. tube.ESSENTIAL OIL OF ASARUM CANADENSE. 67 from a little alcohol, from which it separated in fine, glistening needles melting sharply at 81-82O. On analysis : 0,1444 gave 0.4163 CO, and 0.1015 H,O.C,,H,70,N requires C = 79.1 ; I€ = 7.7 per cent. The fraction by gentle oxidation with chromic acid afforded a little citral, but although the amount of the latter was too small for con- version into the naphthacinchoninic acid derivative, the evidence was already sufficiently conclusive of the presence of geradol in this fraction of the oil. There was, on the other hand, no indication of the presence of citronellol. It may be noted that in the first investigation of asarum oil by one of us, a fraction was obtained corresponding approximately in boiling point (222-226O) to that just described, and that this, on more energetic oxidation with chromic acid, afforded, besides acetic acid, a small amount of a crystallisable acid.As a specimen of the latter had been preserved, it has been re-examined and shown to be a mixture of terebic and terpenylic acids. Frcbction 235-245O.-This was very small in amount, and was evidently a mixture of the preceding and following fractions ; a little of the crystallised geranioldiphenylurethane mas obtained from it by thc method previously described. C = 78.6 ; H = 7%. Identijcation of Eugenol Methy? Ethes-. flraction 245-260°.-This constitutes the largest fraction of the oil. On redistillation under the ordinary pressure it was easily resolved into a large fraction, which was collected between 250° and 256O, but distilled for the most part between 252O and 254'. It is a colourless, nearly odourless liquid, and was analysed, and its physical constants were determined, with the following results : 0 1648 gave 0.4522 CO, and 0.1238 H,O.C = 74.8 ; H = 8.3. CllH1,O, requires C = 74.2 ; H = 7.9 per cent. d 15'/16"= 1.0239 ; uD= - 2'44' in a 100 mm. tube. I t has been shown by Petersen (Ber., 1888, 21, 1064) that the oil obtained from the allied European species of Asuvum contains a sub- stance of the same composition, boiling at about 250', which on oxidation affords veratric acid, and was Fully identified as eugenol methyl ether. I n the first investigation of the oil of Asarum canadense by one of us, a fraction was collected a t 254-257',which on oxidation with chromic acid afforded a small amount of a crystalline acid, COH1004, and this Petersen has likewise found to be identical with veratric acid, The same specimen of acid, after recrystallisation from water, me now find to soften at 1 7 2 O , and to melt compIet,ely at 177-178".F 268 POWER AND LFES: THE CONSTI'I'UENTS OF THE The confirmation of the identity of this fraction with eugenol methyl ether has now been effected by the preparation of the crystalline bromoeugenol methyl ether dibromide, C,H,Br( OCH,)-C,H,Br,, which melts at 78-79O (Wasserman, Contpt. vend., 1879, 88, 1206). This was accomplished as follows : To the liquid dissolved in dry chloroform, and cooled in a mixture of ice and salt, the requisite quantity of bromine, also dissolved in chloroform, was added, drop by drop, and any slight excess of bromine removed afterwards by shaking the solution with a little sulphurous acid.The chloroform solution was separated, dried, and filtered, and the chloroform removed by rapidly drawing dry air through the solution. The residue was a thick syrup, which, when dissolved in alcohol, deposited a quantity of glistening crystals. These, on recrystallisation from absolute alcohol, separated in glistening, felt-like needles, which melted at 78-79". The optical activity of the fraction is due to admixture with a small amount of a higher fraction, which it is difficult to separate completely by fractional distillation. 8earch for isoEugeno2 Methyl Ethr.-As it has been assumed by Mittmann (A?& Pharm., 1889, 22'7, 543) that the substance con- tained in asarum oil is not eugenol methyl ether but the isomeride, we have thought i t desirable to ascertain the correctness of this opinion. For this purpose, a portion of the original oil which had been deprived of terpene was fractionated under diminished pressure before being subjected to hydrolysis. As eugenol methyl ether boils at 128-130' (10 mm.) and isoeugenol methyl ether at 142' (10 mm.), fractions were first collected at 130-140' and a t 140-155O under a pressure of about 10 mm.Further fractionation mas conducted under 60 mm. pressnre, at which eugenol methyl ether was found to boil a t 16Cj0, and isoeugenol methyl ether a t 179". A large fraction was thus collected at 163-16'7' (60 mm.), and also a fraction at 175-185" (60 mm.). For the differentiation of these two substances recourse was had to bromination, as eugenol methyl ether in the cold yields the bromo bromide, whereas isoeugenol methyl ether under tlie same conditions yields only a dibromide melting a t 99--l0lo (Ber., 1890,23, 11 67).On applying this test to the two fractions, only the cryst illine derivative melting a t 78-79' was obtained, which proves that the original oil does not contain isoeugenol methyl ether. Fraction boiling above 260'. This fraction was distilled under reduced pressure, and after a large number of distillations under 60 mm. pressure the following fractions were obtained : Below 175', 175-2 9 5', 195 -2 1 O', 210 --220°, and 220-2 30'.ESSEKTIAL OIL OF ASARUM CANADENSE. The characters of these fractions are shown in the following table : 69 Boiling point (60 nim.). Below 175" 175-195 195-210 210-220 220-230 Analysis.- C=76*0; H= 9.3 C=78'4 ; H=10.3 C=81*1 ; H=10'5 - Rotation in 100 mm. tube. Solubility in 70 per cent. alcohol. Very freely soluble Very freely soluble Very freely soluble Less freely soluble Turbid Colour. Slight Light yellow Bluish Bluish Greenish The fraction collected below 175" consisted chiefly of eugenol methyl ether. The three subsequent fractions had a n odour resembling that of cedar wood, and when a few drops were dissolved in glacial acetic acid and a drop of concentrated hydrochloric or sulphuric acid added, a n intense reddish-violet colour was produced. The fraction 220-230' was very small in amount, The analysis OF the principal fractions, and particularly their ready solubility in dilute alcohol, proved that they consisted of oxygenated compounds, and did not contain a sesqui- terpene." As the fraction 21C!-220° was the largest, this was again carefully distilled, and the following fairly constant fraction obtained, which was more fully examined.Fq*action 212-217' (60 mm.).-This is a thick, viscid liquid, having R fine blue colour and an odour recalling that of cedar wood. It does not solidify when exposed for some time to a temperature of - IS". It is very freely soluble in '70 per cent, alcohol and affords the same colour reaction as the fraction from which it was obtained. It was analjsed, and its physical constants mere determined, with the followkg results : 0.1069 gave 0.3133 CO, and 0*1009 H,O. A molecular weight determination gave the following result : 0 4184 gram depressed the freezing point of 30.17 grams of phenol by 0.48', whence mol.wt. = 214. This result mould agree very well with a sesquiterpene alcohol of the formula C,,H,,O (mol. wt. = 222), but the analytical figures do not accord with those required for this substance (C = 81.1 ; H = 11.7 per cent.). It is probable, therefore, that the fraction snalyscd still consisted of more than one substance. The statcinent in " The Volatile Oils," by Gildemeister and Hoffniaiin (p. 123) hat " Seiiimler, in 1889, obtained from asartun oil a hydrocarbon, C16H2,, boiling a t about 255" " is an error of translation. It properly refers to the oil of Cccrlij~cz acaulis or Carline thistle (German, Eberwzcrz), which is described on p. 690 of the same work. C = 79.9 ; H = 10 5. d15'/16'=1*0063~ a D = -3'; 2=100mm;C=3'678;[a]~= -Sl.5'.70 POWER AND JJEES: THE CONSTITTJENTS OF THE Treatment with Ph.osp?twic Oxide.-In order to obtain further evidence respecting the character of these bluish fractions, an attempt was made to dehydrate them, The remainder of the fractions 195-210Oand 210-220' (60 mm.), about 5 grams of each, was separately dissolved in dry benzene, phosphoric oxide added, and the liquids boiled for about an hour, when they acquired a deep purple-red colour.After distilling off the benzene, the residues were distilled under diminished pressure, Fraction, 195-210' (60 mm.) afforded a liquid which distilled between 175' and 210' under 60 mm. pressure. It had a bright green colour, a cedar-like odour, and was insoluble in 70 per cent. alcohol.0-106s gave 0.3198 CO, and 0.1000 H,O. C = 81.7; H = 10.4 per cent. Fraction 21 0-220° (60 mm.) afforded a liquid which distilled chiefly It had an olive-green d 15O/15O = 0,975 ; [ a ] D = - 37'. between 200' and 220' under 60 mm. pressure. colour, a cedar-like odour, and mas insoluble in 70 per cent. alcohol. 0.1073 gave 0.3300 CO, and 0.1006 H,O. C = 83.9; H = 10.4 per cent- d 15'/15O =: 0.985 ; [ a ] D = - 35.5'. Both these liquids, when dissolved in glacial acetic acid and treated with a drop of hydrochloric acid, afforded a purplish or red colour. Although the insolubility of these products in alcohol and the increase in the per- centage of carbon by the above treatment was evidence of the forma- tion of a hydrocarbon, the substances themselves were not sufficiently pure to admit of further identification.They mere finally dissolved in dry ether, the solutions saturated with dry hydrogen chloride, and allowed to stand for several days, but from the very dark, oily residues no crystallisable hydrochloride could be obtained. Although several essential oils are known to afford high boiling fractions of a deep blue colour, which have been designated as ccewlein by Gladstone, and as ccxulene by Piesse, no properly charac- terised compound has as yet been isolated from any one oE them. Acids obtained by the Hydrolysis of the Oil. The strongly alkaline, aqueous liquid, separated from the hydrolysed oil and completely extracted with ether, as previously described, was evaporated to a small bulk, then acidified with sulphuric acid and distilled with steam.The first portion of the distillate was slightly turbid, but it soon became clear. The entire acid liquid was then made alkaline with sodium carbonate, and extracted several times with ether. After distilling off the ether there remained a small amount of a dark coloured, highly aromatic oil. This was insolubleESSEKTIAL OIL OF AYARC'M CANADENSE. 71 in a cold solution of sodium hydroxide, but dissolved readily on warming. The alkaline solution of the substance was shaken with ether t o remove any impurity, and then acidified with sulphuric acid, which liberated the original oil. This was again taken up with ether, the ethereal solution washed with a little water, dried, evaporated, and the slightly coloured, oily residue finally placed in a V~CLIOUS desiccator over paraffin to remove the last traces of ether, and then analysed.0,0463 gave 0.1298 CO, and 0 0403 H,O. This substance, to which we assign the provisional formula C,,H,,O,, is evidently a Zactone. Although existing in extremely small amount, so that we have not been able to examine it further, its powerful odour indicates that it must have considerable influence on the odour of the original oil. To it is also possibly due the somewhat clove-like odour which was observed in the isolation of the phenol (p. 60). After the lactone had been separated from the liquid which had been made alkaline with sodium carbonate, this liquid was concentrated, strongly acidified with sulphuric acid, and shaken four times successiveiy with ether.The ethereal solution was washed twice with water, dried, and distilled. On fractionating the residue, nearly all distilled between 110' and 120'. A portion of this was converted into the barium sa,lt, and from the latter the silver salt mas prepared which gave the following figures on analysis : C,H,O,Ag requires Ag = 64.7 per cent. This served to confirm the presence of acetic acid, the previous invest- igation having shown that esters of this acid were present in consider- able amount in the oil. Acids of Higher Boiling Point.-The residue from the distillation of the acetic acid was very small in amount, and was therefore mixed with a larger portion of acids obtained by shaking the original oil with a solution of sodium carbonate, The whole of the acids of higher boiling point, after standing over potash in a vacuous desiccator, was first fractionated under 10 mm., and then under the ordinary pressure, when the following three fractions were obtained.C = 76.1 ; H= 9.7. C,,H,,O, requires C = 76.4 ; H = 9.1 per cent. 0.085 gave on ignition 0.0550 Ag. Ag = 64.7. (1) Below 240'; (2) 240-280'; (3) 280-300'. The last fraction became solid on standing, and from the residue in the flask crystals were separated which, after recrystallisation from hot light petroleum, melted at 57-58O ; these consisted apparently of pal- mitic acid, which had been extracted by means of caustic alkali from the original oil. The first two fractions were redistilled and the follow-72 ESSENTIAT, OIL OF ASARUM CANADENSE. ing fractions collected : A, 140 -200 ; B, 200--230' ; C, 230-270°.D was fraction (3) from the first distillation (b. p. 280--300'). They were yellowish, oily liquids, nearly equal in amount, and were present altogether to the extent of about 2 grams in a kilo. of the original oil. They were first converted into ammonium salts, and then fractionally precipitated by silver nitrate. The various silver salts were spread on porous plates, and then dried at 80' for half-an-hour. On analysis, they gave the following results : A,. B,. Ag= 45.1 ,, 13,. Ag=47*1 ,, C,. Ag=36*7 , C,. Ag=39.5 ,, D,. Ag=34.5 ,, D,. Ag=39*2 ,, Ag = 46.1 per cent. ; A,. Ag = 48.4 per cent. C,H,,O, A g requires Ag = 48.4. CI,H,,O, Ag requires A g = 35- 1 per cent. It is thus seen that these acids of high boiling point constitute a n exceedingly complicated mixture, the amounts of eilver found corre- sponding t o those required for salts of acids ranging from C,H,,O, t o C,,H,,O,. A further separation and identification of them would require a very much larger quantity of material than was available for the purpose, It may also be noted that from the method by which the chief portion of these acids was obtained, it is evident that they exist in the oil in a free state, and not in the form of esters. Xurnmar y. From the results of this investigation, the oil of Asarum canadense 1. A phenol, C,H,,02, 2. 3. d-Linalool, 4. I-Borneol, 5. I-Terpineol, 6. Gersniol, 7. Eugenol methyl ether, 8. 9. A lactone, C14H2002, is seen to contain the followiiig substances : Pinene, apparently a mixture of the d- and I forms, A blue oil, of undetermined composition, consisting of oxygen- ated substances of alcoholic nature, 10. Palmitic acid, 11. Acetic acid, and 12. A mixture of fatty acids intermediate between acetic and palm- itic acids. I n order to ascertain approximately the amounts of the principal constituents, the following determinations were made with the original oil :POWER AND SHEDDEN: DERIVATIVE8 OF GALLIC ACID. 73 1. The eugenol methyl ether was determined by Zeisel's method. 0.1898 gram of oil gave 0.1S46 gram AgI, whence eugenol methyl ether = 36.9 per cent. The amount of esters,calculatedasC,,K,7'C,H,O,, is27.5 per cent. The total amount of alcohols, C,,H,,O, free and as esters, after acetylating the hydrolysed oil, was found to be 34.9 per cent., hence the amount of free alcohols is 13.3 per cent. I n reality, the amount of free alcohols is somewhat larger than this, as i t is known that lin- alool and terpineol cannot be quantitatively acetylated. As about 2 per cent. of pinene was found in the oil, the con- stituents of high boiling point, blue oil, &c , would amount to some- what less than 20 per cent. 2. 3. 4. THE WELLCOME CIIEMICAL RESEARCH LABORATORIES.

ISSN:0368-1645    

DOI:10.1039/CT9028100059

出版商:RSC    

年代:1902

数据来源: RSC

摘要:

POWER AND SHEDDEN: DERIVATIVE8 OF GALLIC ACID. 73 VII I. -Deri.vu tives of Gallic Acid. By FREDERICK B. POWER and FRANK SHEDDEN. IN a paper entitled : (6 The Chemical Character of so-called Iodotannin Compounds” (PiLarm. Journ., 1901, [iv], 13, l47), the authors have recorded the results of an investigation which was undertaken for the purpose of ascertaining the character of the compounds prepared by the direct action of iodine on tannic acid in the presence of water. It was shown that under these conditions no definite compound of either tannic or gallic acid with iodine could be formed, and it therefore seemed of interest to ascertain whether iodine could be introduced into the gallic acid molecule by indirect methods. With this object in view, the following method of procedure was adopted.The well-crystallised ethyl gallate was converted into its triacetyl derivative, which, on nitra- tion, yielded etlhp? diniti.odiacetylgcclkate. This substance, on hydrolysis with sulphuric acid, was converted into ethyl dinit?-oycc~%cte, and from the latter, on reduction, ethyl monoaminogaJZate and ethyl diaminogallate were obtained in the form of hydrochlorides. These hydrochlorides were then separately diazotised, and the resulting solutions boiled with potassium iodide in accordance with the well-known reaction. Although many experiments were made, it was not possible to isolate any product containing iodine. As most of the substances required for the original purpose of this investigation represent new derivatives of gallic acid, the xethod of preparation and their characters are here described.74 POWER AND SHEDDEN: DERIVATIVES OF GALT,IC ACID.EthpZ Di~it?.ocliacel~ZgalZate, C,( N02)2(C2H,02)2(OH)*C0,C2H5. By the direct acetylation of ethyl gallate, the ethyl triacetylgallate was first prepared, which has been described by Schiff (Beilstein's gandbuch, 2, 1922) as a thick yellow oil, which very slowly deposits crystals. No difficulty was experienced, however, in obtaining it in colourless crystals from either acetic acid or alcohol. I t melts at 133". The triacetyl ester was nitrated in the following manner. One hundred grams of the triacetyl ester were added to a cold mixture of 50 C.C. each of nitric acid (sp. gr. 1.42) and sulphuric acid, and 150 C.C. of glacial acetic acid. The mixture, while being kept cool, was allowed t o stand for five hours.The product was poured into a litre of water, the yellow, crystalline precipitate filtered off, and the nitro-compound separated from some unchanged ethyl triacetylgallate by treatment with sodium carbonate, in which it readily dissolved. The acid filtrate from the above-mentioned yellow precipitate mas extracted several times with ether and the ethereal liquid shaken out with carbonate solution. This was mixed with the main sodium carbonate solution obtained as above and the whole acidified with hydrochloric acid. The separated yellow oil soon formed a crystal- line cake, which was collected and recrgstallised from chloroform. It formed lemon-yellow needles which melted a t 165'. 0.1466 gave 0.2260 CO, and 0-0486 H,O. C = 42.0 ; H= 3.7.0.1974 ,, 13.3 C.C. moist nitrogen a t 11' and 744 mm. N = '7.9. C,,H120,,N2 requires C = 41 *9 ; H = 3.2 ; N = 7.5 per cent. The substance is strongly acid, dissolving in sodium carbonate with effervescence and forming a n orange-red solution. It only dissolves slowly in absolute alcohol, and the solution gives a bluish-green color- ation with ferric chloride. The ethyl triacetylgallate was nitrated in another manner with some- what different results. One hundred grams of the substance mere mixed in a flask with 100 C.C. of nitric acid (sp. gr. 1*42), and, after being kept cool for five hours, the mixture was worked up in the manner already described. By this method, the product consisted of a mixture of the dinitro-ester and the dinitrodiacetyl ester.An attempt was made t o form the sodium salt of ethyl dinitro- diacetylgallate by dissolving i t in alcohol and adding one atomic pro- portion of sodium dissolved in a little alcohol. No precipitate mas produced, even after a portion of the alcohol had been evaporated off in a vacuum. On standing for several days, an odour of ethyl acetate mas developed, and small, bright red crystals were deposited, wbich consisted of the sodium salt of ethyl dinitroyallute.POWER AND SHEDDEN: DERIVATIVES OF GALLIC! ACID. '75 Ethp? Dinitl.otriaccetyZgaZZ~te, C,(NO,),( C, H,0,)3*C0,C,H,. This was prepared by the acetylation of the dinitrodiacetyl com- pound, in the formation of which one acetyl group had become elim- inated during the process of nitration.It mas obtained in colourless needles, which gradually become yellow, and melt at 145-146'. C= 43.0 ; H=3*3. 0.1716 gave 0.2704 GO, and 0.0504 H,O. 0.2086 ,, 12.4 C.C. moist nitrogen at 16' and 768 mm. N = 7.0. C,,Hl,01,N2 requires C = 43.5 ; H = 3.4 ; N = 6.8 per cent. The substance was insoluble i n sodium carbonate. Its cold alcoholic solution gave no reaction with ferric chloride, but on boiling, a bluish- green colour was produced. EthgZ Binits*ogaZZate, C,(N0,),(OH),*C02C2H,. This was prepared by boiling the dinitrodiacetyl compound with 50 per cent. sulphuric acid, when it crystallised out on cooling. The ethyl radicle was not eliminated by this procedure. It was obtained in the form of small, yellow scales, of asomewhat deeper colour than the dinitrodiacetyl compound.When placed in the melting point apparatus a t 80-85O it melted, but after drying a t rz gentle heat it fused at 153'. 0.8040 air-dried substance lost 0.0486 H,O a t 100'. H,O = 6.0. It was recrystallised by dissolving the dried substance in absolute ether and adding an equal volume of light petroleum. The crystals, after drying for a few minutes in a water-oven, softened at 1 5 1 O and melted to a clear liquid at 153-154'. C6(N02)2(OH),*C0,C,H,,H20 requires H,O = 5-9 per cent. 0,1432 gave 0.1990 CO, and 0.0382 H,O. C = 37.9 ; H = 3.0. 0.1662 ,, 14.4 C.C. moist nitrogen a t 20' and 759 mm. N = 9.9. C,H,O,N, requires C = 37.5 ; H = 2.7 ; N = 9.7 per cent. The substance dissolves readily in absolute alcohol, and the solution gives an olive-green colour with ferric chloride.It could not be hydrolysed by heating in a sealed tube with hydrochloric acid at 125' for six hours. It was also heated in a sealed tube with 50 per cent. sulphuric acid at 155' for five hours without altering the melting point or other properties. Ethyl gallate, on the other hand, when heated in a sealed tube with 30 per cent. sulphuric acid at 150°, is completely hydrolysed. On boiling with an excess of alcoholic sodium hydroxide, the substance was destroyed. It was treated with strong ammonia in the hope of forming the smide, but only tarry products were obtained,76 POWER AND SHEDDEN: DERlVATIVES OF GALLIC ACID. Reduction of EthgZ Dinibi.ogalZcte.-T~ie crude nitro-compound was reduced by warming with tin and hydrochloric acid.After the reaction was over, the liquid was diluted with water and the tin completely removed by hydrogen sulphide. The clear liquid was distilled in a vacuum, and, when it had become concentrated to a small bulk, white, needle-shaped crystals began to separate out, The distillation was then stopped and the crystalline precipitate filtered off and washed with dilute hydrochloric acid, This substance proved to be the hydrochloride of ethyl monoarninogallate. The yield was about 12 per cent. of the original substance. The filtrate and washings were evaporated to complete dryness in a vacuum. The residue was R crystalline mass, which was purified by dissolving it in hot methyl alcohol and diluting the solution with hot chloroform. A light brown or nearly white, crystalline powder was thus obtained, which consisted of the hydrochloride of ethyl diccrninc- gallate.The yield of the latter was very variable, ranging from about 10 to 25 per cent. of the original substance. The formation of the above monoamino-derivative by reduction was a t first thought to be due to the presence of a mononitro-ester in the material used. This, however, was not the case, inasmuch as a pure ethyl dinitrociiacetylgdlate afforded the same yield of the monoamino- hydrochloride. The conclusion may thus be drawn that the formation of the monoamino-derivative is due to some change in the process of reduction. HpdrocAloride of Ethyl Monoaminogdkate, C,H(NH2)(OH),*C02C,H5,HCl,H20. This substance has the following characters. It is readily soluble in water and the solution remains colourloss.Its alcoholic solution gives a dark green colour with ferric chloride. It melts at 210' with blackening and frothing. When rccrystallised by dissolving i t in hot absolute alcohol and adding chloroform to tbe solution, it still melted a t 210°, and was quite white, showing no tendency to change on keeping. When dissolved in a little water, it could be precipitated by the addition of strong hydrochloric acid, and this reaction, besides the other characters of the substance, distinguishes it from the diamino- gallate. It may be heated in a water-oven without any change in weight. 0.1186 gave 0.1760 CO, and 0.0540 H20. 0.1290 ,, 0.1908 CO, ,, 0.0586 H20. C=40.3; H=5*05. 0.1724 ,, 8.8 C.C. moist nitrogen at 24' and 753 mm.N = 5.65. 0.1950 ,, 0,1058 gram AgC1. C1= 13.4. 0.5504 a t 105' lost 0.0392 H20. C = 40.5 ; H = 5.05. H,O= 7.1. C,H1,O,N,HC1,H,O requires C = 40.4 ; H = 5.2 ; N = 5.2 J C1= 13.3 ; H,O = 6.7 per cent.POWER AND SHEDDEN: DERIVATIVES OF GALLIC ACID. 77 The ethyl monoaminogallate was dissolved in an excess of dilute hydrochloric acid, and t o the ice-cold solution a dilute solution of sodium nitrite was slowly added until there was a permanent excess. The liquid was heated on a water-bath for 20 minutes, and, after cooling, the brown crystals were filtered off. The product was almost insoluble in cold water, but dissolved in boiling water, and on cooling the solution long, orange-yellow needles were deposited. The solution was yellow, and gave deep purplish- brown colour with ferric chloride.The substance melted with sudden decomposition at 182'. When recrystallised from dilute acetic acid, it formed fine, reddish-brown needles melting as before at 182'. 0 2350 at 100' lost 0.0178 H,O. The dried substance was analysed with the following result : 0.1108 gave 0,1938 CO, and 0.0432 H,O. C = 47.7 ; H = 4.3. 0 0924 ,, 10 C.C. moist nitrogen at 24' and 769 mm. N = 12.3. C,H,O,N, requires C = 48.2 ; H = 3.5 ; N = 12.5 per cent. 0.1114 gram dissolved in 15.59 grams of pure phenol depressed the This corresponds to a molecular weight of One gram of the substance was heated with three times its weight of water in a sealed tube a t 220' for four hours, when complete solution was effected. The dark brown liquid was filtered from a small amount of a black residue, saturated with ammonium sulphate, and extracted with ether.The ethe-eal solution, when washed with water, dried with sodium acetate, and evaporated, left a yellowish, oily liquid which became crystalline. The crystals, after washing with a little light petroleum, melted at 1 3 9 O , and were free from nitrogen. Their aqueous solution gave a brown colour with alkalis and a bluish-black one with ferric chloride. After recrystallisiog this from toluene, about 0.2 gram of the substance was obtained, and it then melted at 140' without decomposition. I t was dried in a water-oven and then ana.lysed : H20 =i 7.6. C,H,05N,,H,0 requires H,O = 7.4 per cent. freezing point by 0.263". 201. Mol. wt. of C,H,O,N, = 224. 0.1084 gave 0.2174 CO, and 0.0504 H,O.C,HloO, requires C=54.5 ; H= 5.1 per cent. The substance thus produced was therefore undoubtedly ethyl gallate, the nitrogen having been completely eliminated by heating the diazogallate with water. C = 54.7 ; H = 5.2.78 POWER AND SHEDDEN: DERIVATIVES OF GALLIC ACID. On treating the diazo-compound with stannous chloride in cold hydrochloric acid, considerable effervescence was produced and it became completely dissolved. After removing the tin by hydrogen sulphide, the products of the reaction Ewere found to be ammonium chloride arid ethyl gallate. The production of ethyl gallate from this diazo-compound will serve to explain the formation of the monoamino- ester by the reduction of ethyl dinitrogallate (p. 76). Hydroeldoride of Ethyl Diaminogdlate, C,( NH2)2( OH)3*C0,C,H,, 2HC1.This substance, as obtained in the manner already described, forms a fine, crystalline powder of a light brown colour. By redissolving it in hot absolute alcohol (in which it is somewhat sparingly soluble) and adding ethyl acetate it becomes much lighter in colour, but when kept shows a tendsncy to darken. The alcoholic solution rapidly assumes a pink hue. It is very easily oxidised. It dissolves readily in water, but the solution almost immediately becomes blue, and, on standing, blue flakes are deposited. The blue colour is intensified by the cautious addition of ferric chloride, but is destroyed by adding an excess. If the solution in water be acidified with hydrochloric acid, the blue colour changes to pink (compare Ber., 1887, 20, 335 ; 1893, 26, 2 184).Unlike ethyl monoaminogallate, it cannot be precipitated from its aqueous solution by hydrochloric acid. It melts with decom- position a t 197". 0.1318 gave 0.1738 00, and 0.05'70 H,O. C= 35.9 ; H= 4.8. 0.1330 ,, 0,1746 CO, ,, 0.0538 H,O. C = 35.7 ; H=4*5. 0.2139 ,, 19.6 C.C. moist nitrogen a t 23' and 76.4 mm. N = 10.4. 0.1588 ,, by Carius' method, 0.1530 AgCl. C1= 23.7. C9H,,O,N,,2HC1 requires C = 35.9; H = 4.6; N = 9.3; CI = 23.6 per cent. In order to ascertain the action of nitrous acid on this diamiao-ester, 6.6 grams of the substance were mixed with an excess of dilute hydro- chloric acid. The resulting dark coloured solution was cooled with water and a dilute solution of sodium nitrite gradually added, which caused considerable effervescence and the evolution of some nitrous fumes. This liquid was extracted with ether, but on distillation the latter left only a very slight residue. The remaining liquid was heated on a water-bath, when there was considerable effervescence, and, after this had ceased, a small portion of the liquid, when boiled with potassium hydroxide, evolved ammonia. The remainder was extracted with chloroform, then made alkaline with sodium carbonate and again extracted with chloroform, but in neither case was any definite product obtained. After drying in a vacuum, i t was analysed. THE WELLCOME CHEMICAL RESEARCH LABORATO~~IES.

ISSN:0368-1645    

DOI:10.1039/CT9028100073

出版商:RSC    

年代:1902

数据来源: RSC

摘要:

STEVENS : THIOCARBAMIDE HYDROCHLORIDE. 79 1X.- Thiocarbumide J3y HENRY P. STEVENS, 31. A . , Ph.D. THIOCARBAMIDE hydrochloride is stated by Glutz (Annalen, 1870, 154, 40) to be obtained from thiocarbamide stannochloride by removal of the tin and concentration of the resulting aqueous solution, as a crys- talline substance which could be purified by recrystallisation from alcohol. It was not analysed, nor was its melting point given, and the only evidence brought forward by Glutz to shorn that i t was thiocarb- amide hydrochloride is the fact that with platinic cliloride it gave a double salt, and with silver nitrate a mixed precipitate of silver chloride and the silver compound of thiocarbamide. Reynolds (Annalen, 1869, 150, 232) was unable to prepare the hydro- chloride, whilst Claus (Annalen, 1875, 179, 131) states that, like Reynolds, he had been unable to prepare the hydrochloride directly, but had often obtained the pure salt by Glutz’s method, in spite of which assertion, however, no analysis is given nor is the salt in any way further characterised.It is therefore a matter of doubt whether thiocarbamide hydrochloride has hitherto been isolated in a pure state. On investigating the question, it was found that identical products were obtained by Glutz’s method and by bringing together aqueous solutions of thiocarbamide and hydrochloric acid in the calculated pro- portion. The white, crystalline substance produced on evaporation of the solutions on the water-bath is very soluble in alcohol, and when frac- tionally recrystallised from this solvent, it yields, in addition to some unchanged thiocarbamide, well-formed, prismatic crystals having an ill- defined melting point and containing an amount of chlorine too small for such a compound as CS(NH,),,HCI.Repeated crystallisation from alcohol, instead of purifying the compound, lowered the percentage of chlorine without, a t tho same time, yielding any free thiocarbamide. Eventually the hydrochloride was obtained pure by the folIowing method. Thiocarbamide was dissolved in more than sufficient of the most concentrated, warm, aqueous hydrochloric acid to convert the whole into hydrochloride. On allowing the solution to stand, the hydrochloride separated out in thick, massive crystals. The mother liquor was poured off from the crystals, which were then redissolved by gently warming in the smallest possible quantity of hydrochloric acid, from which, on standing, the greater part again separated.It is difficult to dry the crystals without slight loss of hydrogen chloride; they may, however, be obtained in a pure state by pouring off the mother liquor, washing them rapidly with cold alcohol on the filter pump, and drying them over calcium chloride. On analysis :80 STEVENS : THIOCARBAMIDE HYDROCHLORJDE. I. 0.1212 gave 0.1546 AgCl. C1=31.54. 11. 0.2374 ,, 0°3017 AgCI. C1= 31.42. CH5N,C1S requires C1= 31 -38 per cent. As thiocarbamide in aqueous solution has a neutral reaction with respect to litmus, the whole of the chlorine can be accounted for as hydrochloric acid by titration with decinormal ammonium hydroxide solution.Thus, in analysis 11, the substance was titrated, before pre- cipitation, with silver nitrate and gave C1= 31.46 per cent. The salt, when exposed to air, rapidly effloresces with the loss of some hydrogen chloride, of which about one-half can be removed by prolonged exposure in a vacuum over strong sulphuric acid and potassium hydr- oxide. I t is extremely soluble in water or alcohol. If silver nitrdte be gradually added to a solution of the hydrochloride, the precipitate first formed redissolves immediately in the excess of the hydrochloride solution, and on allowing the clear liquid to stand, fine, needle-shaped crystals separ- ate out which melt at 172" and on oxidation with nitric acid yield silver chloride. They appear t o be identical with the compound BCS(NH,),, AgCl (m.p. 170-171") obtained by Reynolds (Trans., 1892, 61, 252) by dissolving silver chloride in a hot alcoholic solution of t hiocarbamide. Thiocarbamide forms additive compounds with alkyl iodides and bromides on standing in the cold or heating in sealed tubes (Claus, Annalen, 1875, 179, 145 ; Bernthsen and Klinger, Ber., 1878, 11, 492, &c.); but no statement, however, is to be found with regard to its behaviour with the alkyl chlorides. On treating a solution of thio- carbamide in alcohol with ethyl chloride, freed from hydrochloric acid by bubbling through water with calcium carbonate in suspension, no appreciable action took place even on warming the solution. Never- theless, it was possible that ethyl chloride, formed in the solution itself by the action of hydrochloric acid on the alcohol, might prove more reactive, and this was eventually found to be the case.An alcoholic solution of thiocarbamide hydrochloride, prepared by dissolviDg thiocarbamide in about ten times its weight of alcohol in which the necessary amount of hydrogen chloride had been dissolved, was boiled for several days in a reflux apparatus on a water-bath. The solution was evaporated down twice with fresh quantities of alcohol to remove any slight excess of hydrochloric acid. The product, a thick, unpleasant smelling oil, solidified completely on standing and stirring with a glass rod. Like thiocarbamide hydrochloride, it was extremely soluble in water or alcohol, but insoluble in other solvents provided they were dry, and on this account much difficulty was experienced in finding a suitable solvent for its recrystallisation. Eventually the product was dissolved by gently warming and shaking in glacial acetic When heated, it softens gradually and melts below 100".METHOD FOR DETERMINING SMALL QUANTITIES OF CARBONATES.81 acid, a few drops of water or alcohol being added to promote solution. Dry ether, insufficient in amount to cause any permanent precipitation, was then added in small quantities a t a time to the cold solution, and the whole set aside to stand; a crop of crystals formed which was filtered off, and the mother liquor treated with more other. I n this manner, by a process of fractional crystallisation, the new substance was obtained in a state of purity. It is more soluble than thiocarb- amide hydrochloride in the mixture of glacial acetic acid and ether, and separates when pure from the same solvent in long, slender prisms. It melts gradually just below 100'. The aqueous solution of the salt is neutral to litmus, but the whole of the chlorine is precipitated as silver chloride by silver nitrate in dilute nitric acid solution. Chlorine estimations showed that i t is an additive product of thiocarbamide and ethyl chloride, or, from anot,her point of view, that it is ethyl-+-thio- carbamide hydrochloride. C1= 25.02. C,H,N2C1S requires C1= 25 -20 per cent, This hydrochloride behaves similarly t o the hydriodide obtained by direct combination of thiocarbamide and ethyl iodide. It follows, therefore, that thiocarbamide hydrochloride cannot be recrystallised from alcohol, as it reacts with it to give ethyl-$-thiocnrb- amide hydrochloride. 0,2097 gave 0,2122 AgC1. 0.2183 ,, 0,2227 AgCI. C1= 25.22. C H ~ ICAL LABORATORY, ST. THOMAS' HOSPITAb, S.E.

ISSN:0368-1645    

DOI:10.1039/CT9028100079

出版商:RSC    

年代:1902

数据来源: RSC

摘要:

METHOD FOR DETERMINING SMALL QUANTITIES OF CARBONATES. 81 X -A Method for Detem&ing Small Quantities of Carbonates. By ALFRED DANIEL HALL and EDWARD JOHN RUSSELL, THE determination of small quantities of carbonates in material like soil is attended with many difficulties, owing t o the solubility of the carbon dioxide in the acid used for decomposing the carbonate. When the soil contains 2 per cent. or more of carbonates, calculated as calcium carbonate, Scheibler’s apparatus may be used, and the empirical correction for solution of the carbon dioxide (Warington, Chern. News, 1875, 31, 253) will not introduce a greater experimental error than attaches to the natural variation of the sample for analysis. But with small proportions of calcium carbonate, 0.5 per cent. and VOL.LXXXI. G82 HALL AND RUSSELL: A METHOD FOR below, Scheibler’s apparatus becomes unworkable, for all the gas pro- duced remains in the reacting acid. Gravimetric methods, where the carbon dioxide is either weighed directly or by difference, require very refined manipulation when 100 grams of soil have to be attacked by acid and the mixture boiled, &c., to obtain quantities like 0.1 gram of carbon dioxide. Working in a vacuum by ordinary gas analysis methods, the carbon dioxide can be collected and measured, but there are, again, difficulties due to solution which render the process tedious and susceptible of error. The suggestion has often been made that the soil should be treated with a known volume of standard acid, and the amount of calcium carbonate present calculated from the acid neutralised.This process, however, always gives results which are too high, owing to the fact that various humates, silicates, and in some cases ferric oxide, are also attacked by the acid without liberating any acid which affects the indicator. Stutzer and Hartleb (Zeit. angew. Chem., 1899, 12, 448) have pro- posed to distil the soil with a solution of ammonium chloride; the calcium carbonate present forms ammonium carbonate by double de- composition ; this dissociates, and the ammonia is caught by standard acid and titrated. This method is open to all the sources of error indicated above (compare Schutte, Zeit. angew. Chem., 1899, 14, 854 ; Woy, Chem. Centr., 1899, ii, 847 ; and ImmendorB, Zeit. angew. Chem., 1900, 15, 1177).I n searching for a more workable process, the authors have devised the apparatus described below, by means of which the main source of error in determinations of carbon dioxide, its solubility, is eliminated. The process is also reasonably rapid and requires no special skill in manipulation. ( A ) is the reaction bulb, about 60 C.C. in capacity. It is connected from below with tho small funnel (B), carrying the stopcock (a). ( A ) is connected to the rest of the apparatus by a cup joint at ( b ) . (C) is a second bulb, rather smaller than ( A ) (in the apparatus actually used, its capacity was 42.5 c.c.); on the tube connecting (C) to the rest of the apparatus is a stopcock (c). The stopcocks and cup joint must be well ground and lubricated so as to maintain a vacuum.( D ) is a capillary tube 800 mm. long, dipping into a small reservoir of mercury and serving as a manometer; a third stopcock (d) is placed between the manometer and the pump. The bulbs ( A ) and (C) can be enclosed in a water-bath. Before t h e apparatus is fixed on the stand, the capacity of the bulb (C) must be ascertained with accuracy ; this may be done by filling the bulb with mercury and then weighing the mercury when shaken out and collected. The apparatus is figured on p. 83.DETERMINING SMALL QUANTITIES OF CARRONATES. 83 Two to 10 grams of the substance in a finely powdered state are introduced into ( A ) and covered with water, the cup joint is wiped, well lubricated, and ( A ) then joined to the rest of the apparatus. The cup joint is sealed with a little mercury, a little also being poured into the funnel (B), so that the bore of the tap is quitefilled.The stop- cock ( c ) is opened, and connection made to a good pump until approxi- mately a vacuum is established inside the apparatus. Entire freedom from air is not necessary, but when determining very small quantities of carbon dioxide (1 to 5 C.C. from 10 grams of soil), the pressure should be run down until the manometer indicates little more than the P 6- vapour pressure of water within the apparatus. When dealing with larger quantities of gas, for example, 10 to 20 c.c., a mercury pump is not necessary, it is sufficient to use a good water pump or hand air pump that will establish an internal pressure of 50-60 mm. of mercury. The stopcock (d) is closed, the height of the mercury in (D) and the temperature of the water-bath are read ; this reading = R.Stopcock ( c ) is then closed, a well-boiled and cooled mixture of equal volumes of sulphuric acid and water is placed in the funnel (B), and a few C.C. introduced into the reacting bulb. Since it enters from below, the liquid and soil get well stirred up ; the mixture is left For a few minutes G 284 HALL AND RUSSELT,: A METHOD FOR to cool down t o the temperature of the bath, then the apparatus is shaken to expel the carbon dioxide present in excess in the solution, and allowed to stand, with further occasional shaking, until the gauge shows a constant reading. The gas evolved causes an increase of pressure inside the apparatus, and the manometer column is read agnin=R1.Communication is now made with the bulb (C) by opening the stopcock (c), the gas ex- pands again into (C) and the mercury rises again in (D). A little time and shaking cause the gas dissolved in the liquid i n ( A ) t o come into equilibrium with the gas above at the new pressure; the mano- meter column is then read when constant, and = B,. Assuming the temperature, t, of the water-bath has remained constant, and calling d the difference in mm. between R and R,, d' the difference in mm. between R and R,, and C the volume of C.d.d' (d - d')760 the bulb (C), then the volume of gas evolved a t N.T.P. = .* The operation amounts t o finding ac unknown volume of 273 2 m gas in ( A ) by the change in pressure produced when it expands by a known volume.The advantage of the method lies in the fact that the volume of soil, liquid, &c., which may have been introduced into ( A ) is immaterial, and does not appear in the calculation, and especially * The complete proof of the formula given is as follows : Let x = the p. v. of the carbon dioxide evolved at the given temperature. A = the volume of the apparatus excluding (C) and the liquid in ( A ) . C = the volume of (C). P = barometer reading. n = tension of aqueous vapour at the given temperature, k = the volume of carbon dioxide soluble in the liquid in ( A ) a t unit R, R, and R, = the readings as above. pressure, At starting, the apparatus contains some air = ( A +B)(P - R - a). ( C ) is shut off and x of carbon dioxide evolved. Then : z+A(P-R-a) = A ( P - R , - a ) + k ( R - R , ) X = A + k . .. . . . [l] €2-€2, The gas is then allowed to expand into (C), when x + ( A + C ) ( P - R- a ) = ( A + C)(P -3, -n) + k ( R - XJ x. = A + C + k . . . . . . [2] A-8, Combining [I] and [2] x - C+Z - - ~ R-R, R-R,DETERMINING SMALT, QUANTITIES OF CARBONATES. 85 that the effect of the gas remaining dissolved in the liquid in ( A ) is also eliminated. The liquid is saturated by the gas, so that the gas within and without the liquid is in equilibrium. When the volume is increased by opening the stopcock to ( C ) , an amount of gas, propor- tional to the reduction in pressure, escapes from the liquid. I n brief, the gas contained in the liquid of ( A ) obeys the same laws as the gas above the liquid, and the liquid becomes practically only a portion of the gas-filled space of ( A ) .It is necessary to have some solid particles like soil or glass beads in ( A ) , otherwise the liquid becomes, and remains, obstinately super- saturated with carbon dioxide, nor can the excess be shaken out. This tendency to supersaturation forms the chief difficulty in working with the apparatus; the amount of substance taken should be such that the pressure of the carbon dioxide liberated does not exceed 100 or 150 mm., or the time required t o obtain equilibrium becomes very great, and may even amount to 2 or 3 hours. The lower the pressure, or, in other words, the smaller the amount of carbonate present, the easier the determination is t o carry out ; the limit is fixed only by the accuracy with which the gauge can be read. Appended are a few numbers obtained with the apparatus i n the case of pure sodium carbonate and Iceland spar, the bulb ( A ) being half filled with glass beads : Number. Substance taken. 0'000624 gram Na,CO, 0.00125 ,) ,, 0 0025 ,, ,> 0.005 2 , 7 , 0.010 ,) ,> 0.020 ,, 9 , 0.0503 ) ) CaCO, CO, a t N.T.1'. (calc.). 0.13 C.C. 0'26 ,) 0'53 ,, 1.06 ,, 2.11 ,, 4'22 ), 11.26 ,) :O, a t N.T. 1'. (foulid). 0'15 C.C. 0'26 ,, 0'51 ,, 4'38 ,, 1'00 ), 2.00 ), 11'18 ,, The apparatus may be conveniently applied to any reaction involv- ing the measnrement of a gas evolved from a liquid. SOUTH E-4STElt.N AGRICULTURAL COLLEGE, WYE.

ISSN:0368-1645    

DOI:10.1039/CT9028100081

出版商:RSC    

年代:1902

数据来源: RSC