摘要:

J O U R N A L H. E. AEMSTRONQ, Ph.D., F.R.S. C. GRAHAM, D.Sc. DAVID HOWARD. F. R. JAPP, M.A., Ph.D. HERBERT MCLEOD, F.R.S. R. MELDOLB. OF HUGO MULLER, Ph.D., F.R.S. F. J. 35. PAGE, B.Sc. W. H. PERPIN, Ph.D., F.R.S. R. T. PLIMPTON, Ph.D. W. J. RUSSELL, Ph.D., F.R.S. J. MILIAR THOMSON. THE CHEMICAL SOCIETY. 6;bitar : C. E. GROVES, F.R.S. %ub-&bitrrr : A. J. GREENAWAY. Vol. XLVII. 1885. TRANSACTIONS. LONDON: J. V A N VOORST, 1, PATERNOSTER ROW. 1885.LOWDON : HARPISON AND SONS, PBIKTEES IF ORDINARY TO IIER MAJESTY, ST. MARTIN’B LAKE.C O N T E N T S . PAPERS READ BEFORE THE CHEMICAL SOCIETY, PAQE 1.-Contributions t o our Knowledge of Acetoacetic Ether. By J. WILLIAM JAMES, Ph.D., F.C.S., University College of 11.-On Additive and Condensation Compounds of Diketones By FRANCIS R.JAPP, M.A., Ph.D., and N. 111.-On some New Paraffins, By KHAN BAHADUR BOMANJI 1V.-On a New Method of Determining the Vapour-pressures of Solids and Liquids, and on the Vapour-pressure of Acetic Acid. By WILLIAM RAMSAY, Ph.D., and SYDNEY YOUNG, D.Sc. . . 42 V.-On the Application of Iron Sulphate in Agriculture, and its Value as a Plant-food. By DR. A. B. GRIFflfTHS, Lecturer on Chemistry and Physics, Technical College, Nanchester, &c. V1.-Action of the Halogens on the Salts of Trimethylsulphine. By LEONARD DOBBIN, Ph.D., and ORME MASSON, M.A., D.Sc., Chemical Laboratory of the University of Edinburgh . 56 VI1.-On the Decomposition of Silver Fulminate by Hydro- chloric Acid. By EDWARDIVERS, &I.D!, and MICHITADA KAWAKITA, M.E. . . (2) VII1.-On the Constitution of Fulminates.By EDWARD DIVERS, M.D., with Note by Dr. ARMSTRONG. . . 77 1X.-Notes on the Chemical Alterations in Green Fodder during its Conversion into Ensilage. By CLIFFORD RICHARDSON, Assistant Chemist U.S. Department of Agriculture . . 81 X.-On Condensation Compounds of Bend with Ethyl Alco- hol. By FRANCIS R. JAPP, M.A., Ph.D., and Miss MARY E. XI.--Note on the Solubility of Certain Salts in Fused Sodium Nitrate. By F. B~CKELL GUTHRIE, Demonstrator of XI1.-Kote on the Heats of Dissolution of the Sulphates of By SPENCER UMFREVILLE PLCKER- South Wales, Cardiff . . I H. J. MILLER, Ph.D. . . 11 SORABJI, Ph.D., C.E., &c. . . 37 with Ketones. 46 OWENS, B.S. (Cincinnati) . . 90 Chemistry, Queen’s College, Cork . . . 94 Potassium and Lithium.ING, M.A. Oxon., Chemical Lecturer at Eedford College . 98i v CONTENTS. PAQB XII1.-Calorimetric Determinations of Magnesium Sulphate. By SPENCER UMFREVILLE PICKERING, M.A. Oxon., Lecturer on Chemistry at Bedford College . By ADOLF STAUB, Ph.D., and WATSON SMITH, Lecturer in Technological Chemistry in the Owens College, Manchester . . 104 By T. E. THORPE, F.R.S., Professor of Chemistry in the Yorkshire College, Leeds . . 108 XV1.-Note on the Constitution of Propylene Chlorhydrin. By Dr. H. FORSTER MORLEP and ARTHUR G. GREEN, Tufnell Scholar at University College . . 132 XVI1.-Action c;f Zinc Ethide on the Benzoate of Propylene Chlorhydrin. By Dr. H. FORSTER MORLEY, M.A., and ARTHUR G. GREEN, Tufnell Scholar a t University College . 134 111. Some Experi- ments on Strychnine. By W.A. SHENSTONE, Lecturer on. Chemistry in Clifton College . . . . 139 X1X.-On the Physiological Action of Brucine and Bromo- strychnine. By T. LAUDER BRUNTON, M.D., F,R.S. . . 143 XX.-Crystal.lography of Bromostrychnine. By H. A. &hERS, M.A. . C . . C . . 144 XXL-Formation of Pg ridine Derivat,ives from Malic Acid. By H. v. BCHMANN and W. WELSH . . 145 XXI1.-On Ni trobenzalmabnic Acids. By CHARLES M. STUART, XXII1.-On Chemical Changes in their Relation to Micro- XX1V.-Toughened Filter-papers. By F:. E. H. FRANCIS, XXV.-A Quick Method for the Estimation of Phosphoric Acid XYV1.-The Oxides of Nitrogen. By W. RAMSAY and J. TUDOR Communication from the Laboratory of Uni- XXVI1.-Note on Methylene Chloriodide. By J. SAKURAI, Pro- XXVII1,-The Illuminating Power of Methane. By LEWIS T.WRIGHT, Assoc. M.I. C.E. . . 200 XX1X.-Conversion of Pelouze’s Nifrosulphates into Hypo- nitrites and Snlphites. By EDWARD DIVERS and TAMEJJASA HAGA . . . 203 XXX.-The Constitution of some Non-saturated Oxygenous Salts, and the Reaction of Phosphorus Oxychloride with Sulphites and Nitrites. By EDWARD DIVERS, M.D. . . 205 100 X1V.-On certain Derivatives of Isodiuaphthyl. XV.-On the,Atomic Weight of Titanium. XVII1.-The Alkalo‘ids of Nux Vomica. M.A., FelIow of St. John’s CoIlege, Cambridge . . 155 organisms. By E. FRANKLAND, D.C.L., M.D., LL.D., F.R.S. 159 Government Chemist, British Guiana . . . 183 in Feertilisers, By J. S. WELLS . . 185 CUNDALL. versity College, Bristol , . 187 fessor of Chemisti-y, University of Tokio, Japan .. 198CONTENTS. V PAQE XXX1.-The Illuminating Power of Hydrocarbons. By PERCY F. FRANKLAND, Ph.D., B.Sc., Associate of the Royal School of Mines . . 235 XXXI1.-Benzoylacetic Acid and some of its Derivatives. Part 11. By W. H. PERKIN, Jun., Ph.D., Privatdocent at the University of Munich . . 240 XXXII1.-Benzoylacetic Acid and some of its Decivatives. Part 111. By W. H. PERKIN, Jun., Ph.D., Privatdocent at the University of Munich . . 262 XXX1V.-Presence of Choline in Hops. By PETER GRIESS, Ph.D., F.R.S., and G. H. HARROW, Ph.D. . . 298 Annual General MeeCing . . . . 300 XXXV.-Combustion in Dried Gases. By H. BRERETON BAKER, B.A., Brackenbury Scholar of Balliol College, Oxford . 349 XXXV1.-The Ortho-Vantidates of Sodium and thair Analogues. By HARRY BAKER, Berkeley Fellow in the Owens College, Manchester .. . 353 XXXVK-The Formation of Hyponitrites from Nitric Oxide. By EDWARD DIVERS and TAMEMASA HAG& . . 361 XXXVIIL-The Existence of Barium and Lead Nitrososulphates. By EDWARD DIVERS and TAMEMASA HAGA . . 364 XXX1X.-Preparation of Ethylene Chlorothiocyanate and P-Chlorethylsulphonic Acid. By J. WILLIAM JBMES, Uni- versity College, Cardiff . . 365 XL.-Derivatives of Taurine. Part I. By J. WILLIAM JAMES, Ph.D., F.C.S., University College of South Wales, Cardiff 367 XL1.-A Crystalline Tricupric Sulphate. By W. A. SHENSTONE 375 XLI1.-Crystallography of CuSOa,2CuH20z. (Supplement to XLII1.-A Modified Bunsen Burner. By W. A. SHENSTONE . 378 XL1V.-On some Points in the Composition of Soils; with Results Illustrating the Sources of t8he Fertility of Mani- toba PrsLirie Soils.By Sir J. B. LAWES, Bart., LL.D., F.ItZIS.: and J. H. GTLBERT, Ph.D., LLD., F.R.S., V.P.C.S. . . 380 XLV.-The Chlorination of Phloroglucol. By CHARLES S. S. WEBSTER . . . 423 XLV1.-On the Unit adopted for the Atomic Weights. By LOTHAR MEYER and KARL SEUBERT . . 426 XLVI1.-The Atomic Weight of Silver and Prout’s Hypothesis. XLVII1.-A New and Simple Method for the Quaiititative Separation of Tellurium from Selenium. By EDWARD DIVERS, M.D., and MASACHIKA SHIMOS~, M.E., Imperial XLI.) By H. A. MIERS, M A . . . 377 By LOTHAR MEYER and KARL SECBERT . . 434 Japanese College of Engineering, Thkio . . 439vi CONTEK T S. XLTX-Reactions of Selenious Acid with Hydrogen Sulphide, and of Sulphurous Acid with Hydrogen Selenide.By EDWARD DIVERS, M.D., and TETSUKICHI SHIMIDZU, M.E., Imperial Japanese College of Engineering, T6kio . L.-Researches on the Action of the Copper-zinc Couple on Organic Bodies. Part X. On Bromide of Benzyl. By -J. H. GLADSTONE, Ph.D., F.R.S., and ALFREP TRIBE, F.C.S., Lecturer on Metallurgy to the Medical School of the National Dental Hospital . LL-On the Existence of Nitrous Anhydride in the Gaseous State. By G. LUNGE . . LIT.-On the Reaction between Nitric Oxide and @xygen under varying Conditions. By G. LUNGE . LIT1.-Detection and Estimation of Iodine. By ERNEST H. COOK, B.Sc. (Lond.), A.R.C.S., Bristol Trade and Mining School . L1V.-The Selective Slteration of the Constituents of Cast Iron. By THOMAS TURNER, Assoc. R.S.M., Demonstrator of Chemistry, Mason College .By V. H. VELEY, M.A., F.I.C., of the Laboratory, Christ Church, Oxford . LV1.-On the Sulphides of Titanium. By T. E. THORPE, F.R.S. LV1T.-Colorimetric Method for Determining Small Quantities of Iron. By ANDREW THOMSON, M.A., B.Sc., Student in the Chemical Laboratory of University College, Dundee . . LVII1.-On the Constlitntion of the Halo'id Derivatives of Naphthalene. (Fourth Notice.) By RAPHAEL MELDOLB, Professor of Chemistry in the Finsbury Technical College ; City and Guilds of London Institute . L1X.-On the Non-crystallisable Products of the Action of Diastase upon Starch. By HORACE T. BROWN and G. H. MORRIS, Ph.D. . LX.-The Decomposition of Carbonic Acid Gas by the Electric Spark. By HAROLD B. DIXON, MA., The I h k e of Bed- ford's Lecturer on Chemistry a t Bnlliol College, and HUBERT F.LOWE, B.A., late Brakenbury Scholar of Balliol LX1.-The Influence of Silicon on the Properties of Cast Iron. By THOMAS TURNER, Assoc. R.S.M. (Demonstrator of Che- mistry, Mason College) . LXII. --R rominated Derivatives of Diphenyl, Tolyl benzene, and Ditolyl. By THOMAS CARNELLEY, D.Sc., and ANDREW THOMSON, M.A., B.Sc., University College, Dundee LXII1.-On the Cause of the Decrepitations in Samples of so- called Explosive Pyrites. By B. BLOUNT . LV.-On some Sulphur Compounds of Calcium. College, Oxford . . . . . PAG, 4 1 448 457 465 471 474 478 491 493 497 527 5 71 577 586 593CONTESTS. vii PAGE LXIV.-The Specific Action of a Mixture of Sulphuric and Acids upon Zinc in the Production of Hydroxyamine. By EDWARD DIVERS, M.D., and TETSUKICHI SHIMIDZU, M.E., Imperial Japanese College of Engineering, Tokio LXV.-On the Behaviour of Stannous Chloride towards Nitric Oxide, and towards Nitric Acid.By EDWARD DIVERS and TAMEMASA HAGA . LXV1.-On the Constitution and Reactions of Liquid Nitric Peroxide. By EDWARD DIVERS, M.D., and TETSUKICHI LXV1I.-On the Action of Pyrosulphuric Acid upon Certain Metals. By EDWARD DIVERS, M.D., and TETSUKICHI LXVII1.---A Method for Obtaining Constant Temperatures. By Professor WILLIAM RANSAY, Ph.D., and SYDNEY YOUNG, D.Sc., Lecturer and Demonstrator of Chemistry, University College, Bristol . LX1X.-Researches on Secondary and Tertiary Azo-Compounds. No. 111. By RAPHAEL MELDOLA, Professor of Chemistry in the Finsbury Technical College, City and Guilds of London lnstitute .LXX.-Note on the Spontaneous Polymerisation of Volatile Hydrocarbons at the Ordinary Atmospheric Temperature. By Sir HENRY E. ROSCOE, F.R.S. LXXL-On the Non-existence of Gaseous Nitrous Anhydride. By WILLIAM RAMSAY, Ph.D., and J. TUDOR CUNDALL . LXXI1.-On some Derivatives of Anthraquinone. By A. G. PERKIN and W. H. PERKIN, jun., Ph.D. LXXII1.-Researches on the Relation between the Molecular Structure of Carbon Conipounds and their Absorption Spectra. (Part VII.) By W. N. HARTLEY, F.R.S., Pro- fessor of Chemistry, Royal College of Science, Dublin . LXX1V.-On the Action of Gypsum in Promoting NitrXcation. By 1%. WABINGTON . LXXV,-Contributions toward the History of Formyl and Thio- f ormyl Compounds derived from Aniline and Homologous Bases.By ALFRED SENIER, M.D. . LXXV1.-Action of Phenyl Cyanate on Polyhydric and certain Monohydric Alcohols and Phenols. By H. LLOYD SNAPE, B.Sc. . LXXVI1.-Chemical Examination of the Constituents of Cam- phor Oil. Communication from the Chemical Society of Tokio by HIKOROKURO YOSHIDA, Chemist to the Imperial . SHIMIDZU, M.E. . . . SHIMIDZU, M.E. . . . . . Geological Survey . . . 597 623 630 636 640 657 669 672 679 685 758 762 7 70 779... vlll CON TENTS. LXXVIIL-On the Synthetical Formation of Closed Carbon- chains. By W. H. PEEKIN, Jun., Ph.D., Privatdocent at the University of Munich . . LXX1X.-Action of Sodic Alcohdates on Ethereal Fumarates and Maleates. By T. PURDIE, Ph.D., B.Sc., Assoc. R.S.M., Professor of Chemistry in the University of St. Andrews . LXXX.-Contributions to the Chemistry of the Cerite Metals. 111. By B. BRAUNER, Ph.D., F.C.S., late Berkeley Fellow of the Owens College, Adjunct and Privatdocent in the LXXX1.--.A New Method of Preparing Aromatic Hydro- carbons. By RICHARD ANSCH~~TZ . LXXXI1.-On the Decomposition of Aromatic Ethereal Salts of Fumaric Acid. By RICHARD ANSCH~~TZ and QUIRIN WIRTZ . LXXXII1.-The Influence of Silicon on the Properties of Cast Iron. Part 11. By THOMAS TURNER, Assoc. R.S.M. (De- monstrator of Chemistry, Mason College) . LXXXlV.--On the Relation of Diazo benzeneanilide to Amido- azobenzene. By R. J. FRISWELL and A. G. GREEN . LXXXV.-On an apparently New Hydrocarbon from Distilled Japanese Petroleum. By EDWARD D~VERS and TEIKICHI NAKAMURA, Imperial College of Engineering, Tbkio, Japan . Bohemian University, Prague . . . PAGB 801 855 8 79 898 899 902 91 7 924

ISSN:0368-1645    

DOI:10.1039/CT88547FP001

出版商:RSC    

年代:1885

数据来源: RSC

摘要:

JAPP AND MILLER: KETONES AND DIKETONES. 11 11.-On Additive and Condensation Compouncls of Diketones with Ketones. By FRANCIS R. JAPP, M.A., Ph.D., and N. H. J. MILLER, Ph.D. Iutroduction. IN a former communication by Japp and Streatfeild (this Journal, 1882, Trans., 270), it was shown that phenanthraquinone, acetone, and ammonia react according to the equation- and that, when the compoiind thus obtained is treated with aqueous acids, it takes up water and parts with ammonia, yielding a compound of the formula Cl,H,,O,; this contains the elements of acetone and phenanthraquinone, and may, in fact, be obtained in small quantity by heating these two subst,ances together. It may therefore receive, the name acetonephenanthraquinone. Owing to the ease with which, on heating, it was decomposed into acetone and phenanthraquinone, a12 JAPP AKD MlLLER ON COMPOUNDS OF constitutional formula was assigned to it, in which the union of the two molecules of the generating compounds was represented as taking place by means of the oxygen-atoms.A further study of the reactions of this compound has now shown that it possesses the constitution- C~HT,. C (OH) .CH2. CO.CH3 * I I c6& co Thus when reduced with zinc-dust in acetic acid solution, it yields ;I compound of the formula CI,H,,O :- C~H1403 + H, = C17H120 + 20H2. As the carbon residues of the acetone and phenanthraquinone molecules do not part company during this reaction, it is highly im- probable that they could have heen united merely through the medium of the oxygen-atoms. The chief argument, however, in favour of the constitutional formula above given is to be found in the analogy to several similar compounds to be described in the present communication.Owing to the greater ease with which these compounds can be obtained, their reactions have been more thoroughly studied. The above formula, is also in keeping wit'h the analogy to the additive compound of orthonitrobenzaldehyde with acetone- NO,. CeH*.CH( OH). CHz.CO. CH3, since obtained by Raeyer and Drewsen (Ber. 15, 2858). appears to be- The most probable formula for acetonephenanthraqninoiiimide CsH,. C ( OH). C H,. C 0. CH, C6H4. C (NH) I I That the imido-group attaches itself to the phenanthraquinone resi- due, and not to the acetone residue, is rendered probable by the results which we have obtained by acting with potash solution on a mixture of phenanthraquinone and acetone.In this case no imidogen can replace the oxygen of one carbonyl-group of the phennnthra- quinone : under the influence of the potash, therefore, both carbonyl- groups take part in the reaction, and an additive compound of one molecule of phenanthraquinone with two molecules of acetone is obtained. To this compound we assign the formula- * This formula was first suggested by Dr. Armstrong during the discussion which followed the reading of the above-mentioned paper, but was rejected a t the time by the authors of the paper.DIKETONES WITH KETOSES. 13 C,H*.C( OH). C H2. CO.CH3 C6H,.C(OH>.CH,.CO.C& I I Diacetonephenanthraquinone. Under other conditions, we obtain an additive compound of 2 mols.of phenanthraquinone with 1 mol. of acetone. We also describe con- densation compounds obtained from the above additive compounds by the elimination of the elements of water. I n order to extend the application of these reactions, we have studied the action of potash on mixtures of benzil with acetone and with acetophenone respectively, and have obtained the compounds- C6H5. C(OH).CH,. CO .CH3 CtjH5.C(OEC).CH,.CO.C6Hj C6H5. CO and I C6H5. CO I Acetonebenzil. Acetophenonebeuzil. The compound obtained from acetonebenzil by the abstracbion of water has considerable theoretical interest. Whereas acetophenone- benzil parts with its hydroxjl-group along with a hydrogen-atom from the contiguous methylene-group to yield an unsaturated compound of the formula- C6H5.C : CH.CO.CsHj I C6H5.C0 Y Dehy drace tophenonebenzil.in the case of acetonebenzil the hydroxyLgroup appears to be elimi- nated along with a hydrogen-atom from the methyl-group, so as to form a closed chain componnd of the formula- CsH,. C < : :;> C 0. I C6H,.b0 Dehydracetonebenzil. The evidence in favour of these views will be given in detail in the present paper. 1. PHENANTHRAQUINONE AND ACETONE. a. Action of a Small Quantity of Potash on a Mixture of Phenanthra- quinone and Acetone. 50 grams of very finely powdered phenanthraquinone were intro- duced into it small flask along with 43 grams of pure acetone* ( L e . , in * Many of the reactions deacribed in this paper yield no trace of the desirecl14 JhPP AND MILLER ON COMPOUNDS OF the proportion of 1 mol.of the quinone to 3 mols. of acetone) and 2 C.C. of a strong solution of potash (sp. gr. 1.27) were then added. On shaking the flask, a reaction took place attended with considerable rise of temperature : the phenanthraquinone dissolved, and the liquid became dark-coloured. After standing over night, the whole had solidified to a yellowish-brown mass. This was broken up, then triturated with ether until completely disintegrated, poured upon a, filter, and washed with ether until the liquid ran through only slightly coloured. The treatment of the filtrate will be described later on. The crude substance was thus obtained as a yellowish powder. The first ethereal washings from the above process were almost black, and, as it seemed therefore that the strong potash had exer- cised a prejudicial influence, experiments were made to ascertain whether, by employing a more dilute solution of potash, a purer product could not be obtained.It was found that, under these con- ditions, far less heat was evolved, the solution retained its pale colour, and the quinone, without dissolving, was transformed into an almost white powder. These favourable appearances were, however, entirely deceptive. The white powder, on treatment with solvents, proved to be merely phenanthraquinone superficially coated with the new compound. In order that a complete transformation of the quinone may take place, there must be complete solution, and this, as far as our experiments go, is best effected as above by the use of strong potash, and at the expense of a portion of t’he material.The yellowish powder was dissolved in boiling acetone, in which it is sparingly soluble. From the acetone solution, it was deposited, by spontaneous evaporation,* in well-formed short oblique prisms, which, after recrystsllising two or three times, were quite colourless. The new substance is sparingly soluble in the ordinary organic solvents. Glacial acetic acid and amyl alcohol dissolve it most readily, but by boiling with these solvents it is speedily decomposed. Acetone and benzene were found to be the most suitable solvents. products unless pure acetone is employed, and for this purpose a purification by means of the bisulphite compound is necessary. I n the case of one of these reac- tions, which with acetone from the bisulphite compound gave excellent results, we attempted to employ a sample of acetone which had been repeatedly fractioned with a Le Bel-Henninger apparatus, and showed a constant boiling point ; but hardly any of the compound was obtained.We may remark that various bought specimens of acetone, ostensibly prepared “ from the bisulphite compound,” utterly failed to stand the test of these reaction?, and yielded only resinous products from which nothing definite could be extracted. * In a short preliminary notice of this reaction, forwarded to Berlin in English, and published in the Berichte (16, 282), the words of the English manuscript ‘‘ by spontaneous evaporation ” were transformed by the Berlin translator into ’‘ unter freiwilliger Erwarmung ” (“ with spontaneous rise of temperature ”) .DIKETONES WITH KETONES.15 The melting point cannot safely be employed as a criterion of purity. When heated, the compound turns yellow between 150" and 160", and melts a t 187", a t the same time giving off acetone. The substance which remains behind is impure phenanthraquinone. Analysis gave numbers agreeing with the formula C,,H,oOI :- Substance. CO,. OH,. I ...... 0.1594 0,4321 0.0930 I1 ...... 0.1550 0.4212 0.0908 I11 ...... 0.1713 0.4637 0.09 78 Calculated for Pound. -7 C,OH2004. r-.-A-- rh-- 7 I. 11. 111. C20 .... 240 74.07 73.93 74.11 73.82 H2, .... 20 6.18 6.47 6.50 6-34 0 4 .... 64 19.75 324 100.00 - - - - - Analyses I and I1 were made with one preparation; in I11 a The compound has been formed according to the equation- second preparation was employed. C,aH@, + 2C3HtiO = CmHmOa, Phenanthmquinone.Acetone. Diacetone- phenanthraquinone. and we assign to it the constitution expressed by the formula already given on p. 13. In accordance with the system of nomenclature adopted by us for these compounds, it would receive the name diacetonephenant hraquinone. Action of Acetic Anhydride on Diacetonephenanthrapuinone.-A few grams of the compound were boiled with acetic anhydride. No more anhydride than is sufficient for solution ought to be employed, and the boiling should be discontinued as soon as everything has dissolved, otherwise only a red resin is obtaiiied. On cooling the liquid-an operation which ought to be performed rapidly-white crystals were deposited ; these were washed with ether and recrys- tallised from boiling benzene.The new substance was thus obtained in colourless pointed prisms, melting a t 179-181". A further quantity of less pure substance can be separated from the acetic anhydride mother-liquor by shaking it with water; but if alcohol is employed to destroy the. excess of anhydride, nothing but the red resin is obtained. The colourless compound gave the following results on analysis :-16 JAPP AND MILLER ON COMPOUNDS OF Substance. cop OH,. I ........ 0.1478 0.4232 0.01340 11.. ...... 0-1174 0.3365 0.0628 These numbers lead t o the formula C20H,803 :- Calculated for FDund. CWH1803. r-L 7 C,, ...... 240 78.43 78.13 78-18 HIS ...... 18 5.88 6.31 5-94 0,. ....... 48 15.69 306 100.00 r--,---7 I.11. - - -- -- Different preparations were used in these analyses. The compound is therefore formed from diacetonephenanthra- quinone by the elimination of a molecule of water, and may be named deh y d rodiace ton eph enan t h r a p iizone : - C20Hm04 - OH, = C20H1803. Dehydrodiacetone- phenaiithraqui none. There are various ways in which a molecule of water might be removed from a compound of the constitution of diacetonephenan- thraquinone: our experiments do not enable us to decide between these. We could not succeed in preparing an additive compound with bromine. Taking into consideration the fact that monacetonephenanthra- quinone does not part with water when treated with acetic anhydride, it seems the most probable view that in the foregoing case the dehydration takes place between two hydroxyl-groups.Regarding diacetonephenanthraquinone as a glycol, the compound obtained by dehydration would thus be an analogue of ethylenic oxide :- CGH4.C -CHz.CO.CH, CGH,. C-CHZ. C 0. CH, I I>O Formation of Monacetonephena~ntlwaquinone. - The dark-colonred ethereal washings obtained in the preparation of diacetonephenan- thraqninone were decolorised by shaking with freshly ignited animal charcoal. On spontaneous evaporation, the solution deposited colourless crystals of monacetonephenanthraquinone, recognisable by its melting point (goo), and its characteristic crystalline form.DIKETONES WITH KETONES. 17 b. Action of an Excess of Potash on a Misture of Phenanthrapuinoiae and Acetone. If an excess of the potash solution (sp.gr. 1.27) is employed in this reaction, the yield of diacetonephenanthraquinone is not so good, and the ethereal washings contain a new substmce. The quantity of the latter was small; but sufficient was obtained for a,nalysis. It was crystallised several times from boiling benzene until a constant melting point was obtained. It is deposited from the benzene solution in groups of small colourless needles, which under the microscope appear as long pointed prisms. It is moderately soluble in hot benzene or alcohol; almost insoluble in these liquids in the cold. Ether dissolves it rather readily. It melts a t 195" without evolving gas. Analysis gave figures leading to the formula C1,HI2O2 :- Substance. cop OHZ. I ........ 0.1310 0.3946 0.0591 Calculated for * C17H,202* Found. C, ,........ 204 82-25 82.1 5 HI2 ...... 12 4-85 5.01 0, ........ 32 12.90 248 100.00 - -- - The compound is a condensation-product of phenanthraquinone and acetone, and we therefore propose to name it dehydracetonephenccntkra- pinone :- CiaHsOz + CJ&O = CiJizO, + OH2. Phenanthraquinone. Acetone. Deh ydracetone- phenanthraquinone. It is probably formed from monacetonephenantbraqninone by elimi- nation of a molecule of water. The corresponding transformation in the case of monacetonebenzil is described later on. The difficulty of obtaining this substance in any quantity precluded a study of its reactions. Its constitution, however, is probably analogous to that of the corresponding condensation-product of benzil and acetone ( q . ~ .) . c. Acetonephennnthraguinone. I n order to study the reactions of this compound, a quantity of it was prepared from acetonephenanthraquinonimide by a method mentioned by Japp and Streatfeild (Trans., 1882, 273), but not VOL. XLVTI. C18 JAPP AND MILLER ON COMPOUNDS OF further worked out by them. This method consists in the decompo- sition of the latter compound with an aqueous solution of oxalic acid. The following mode of applying the reaction was found to give satis- factory results: 50 grams of phenanthraquinone were shaken in a flask with 60 grams of acetone and 40 C.C. of strong aqueous ammonia, and the acetonephenanthraquinonimide thus formed was filtered off and washed with ether as described in the above-mentioned paper. Without getting rid of the adhering ether, the crude compound was suspended in water, and the r e d t i n g thick cream poured, with constant stirring, into a solution of 90 grams of crystallised oxalic acid in 800 grams of water (temperature about.25'). Almost every- thing dissolved ; but in a short time the liquid became turbid, and the separation of minute needles of acetonephenanthraquinone commenced. After standing for two days, the compound was separated by filtration, and thoroughly washed with cold water in order to remove any oxalic acid. It was then dried by exposure to the air, and dissolved in ether. By spontaneous evaporation of the ethereal solution, the compound was obtained in large lustrous prismatic crystals. The last ethereal mother-liquors, which are rather dark, may be decolo- rised by shaking with freshly ignited animal charcoal.From 50 grams of phenanthraqixinone, 37 grams of a pure product were obtained. A c t i o n of Nascent H y d r o g e n o n Acetonephenanthraquinone.-A quantity of the above compound was dissolved i n cold glacial acetic acid, and zinc-dust was added in small quantities from time to time, keeping the flask in cold water. After a few days, the whole was poured into water to precipitate the substance and dissolve zinc acetate. The substance was then collected along with the excess of zinc-dust, dried at ordinary temperatures, and extracted from tlie zinc-dust with ether, in which it, is very soluble. The impure substance, remaining after evaporation of the ether, was crystallised from hot alcohol, which removed a quantity of very soluble red gum.It was deposited from the alcoholic solution in long slender needles, which, on recrystallisation from the same solvent, melted constantly at 121". The compound is soluble in almost all proportions in ether and chloroform, readily soluble in boiling alcohol, almost insoluble in cold alcohol. It sublimes without decomposition in feathery crystals. The yield of substance is small. Analysis gave the following results :- Substance. cop OH,. I.. ...... 0.0986 0.3168 0.04aa I1 ........ 0*1130 0.3601 0.0545 These numbers lead to the formula C1,HI20.DIRETONES WITH KETOXES. 1 9 Calculated for Found. 7 C1iH120. (--A- * 1. 11. C1, ...... 204 87-93 87.62 87.68 H,, ...... 12 5.17 5.49 5.40 0 ........ 16 6.90 232 100.00 - - - - These analyses were made with different preparations of sub- stance.I n the formation of this compound, 1 mol. of acetonephenanthra- quinone takes up 1 mol. of hydrogen and parts with 'L mols. of water :- C,7Hi,O, + H2 = c17H120 + 20Hz. When bromine is added to a solution of the substance in chloro- form, the colour of the bromine instantly disappears, and a bromine- derivative-probably additive-separates in slender needles. The quantity obtained was not sufficient for analysis, and the prepara- tion of a larger quantity would have involved the sacrifice of mom phenanthraquinone than we could conveniently spare. Action of Dilute Potash o n Monctcetonephe?zanthrapuino?ze in Alcoholic Solution.-A few drops of dilute aqueous potash were added to a cold alcoholic solution of monacetonephenanthraquinone.The liquid a t once assumed a yellow colour, and minute crystals adhering to the sides of the vessel soon began to form. The separation of crystals was complete in about 24 hours, when the liquid was poured off, and the crystals, which welre yellow, were washed with alcohol, dried, and recrystallised from boiling benzene until they were colourless. Thus obtained, the substance forms minute rhomboidal crystals which, when heated, turn yellow at 150-160", and melt at 190", evolving gas and leaving an orange-coloured residue of phenanthra- quinone. It is very sparingly soluble in all the usual solvents, and is deposit'ed from its benzene solution only after long standing. Analysis gave figures agreeing with the formula C31H2205 :- Substance.co,. OH,. I.. ...... 0-1344 0.3858 0.0617 11. 0.1054 0.3020 0 * 0 45 6 C31H.2205. r-A- 1 F - 7 I. 11. CB1 ...... 372 78.48 78.28 78.14 H2, ...... 22 4-63 4.80 4.80 0 5 . . ...... 80 16.89 I - ....... Calculated for Found. -- - 474 100*00 c 220 JAPP AND MILLER ON COMPOUNDS OF The formation of this compound may be expressed thus :- 2G,Hi*O3 = CSiHzzO, + CsHsO. Monacetonephenanthra- Acetonediphen- Acetone. quinone. anthraquinone. It thus contains the elements of 1 mol. of acetone with 2 mols. of phenanthraquinone, and may receive the name ncetonediphenanthra- quinone. Judging from analogy, it most probably possesses the con- stitution- CsH,. C (OH). CH,. CO .CH,.C( OH). C6H4 CO--CsHr C,H,.CO I I . 1 1 There are thus three distinct, compounds containing the elements of phenanthraquinone and acetone in different proportions :- Phenanithra- Resulting Acetone.quinone. compound. 1 mol. + 1 mol. = C1,H1403 (Acetonephenanthra- qninone) . quinone) . quinone) . - - C20H200a (Diacetonephenanthra- C31H2205 (Ace tonedip henanthra- 2 7 9 + 1 97 1 >, + 2 ,> - - Action of Strong Potash on a Solution of Acetonephenanthraquinone in Acetone.-On adding an excess of strong potash (sp. gr. 1.27) to a cold concentrated solution of acetonephenanthraquinone in acetone, the liquid became dark, and considerable heat was liberated. On cooling, the liquid layer floating on the surface of the potash solidified, and on washing the substance with ether and recrystallising it from acetone, the characteristic crystals of diacetonephenanthraquinone were obtained, melting at 187".The following reaction had there- fore occurred :- C17H1403 + C3H6O = CZOHZOO4. Acetone- Acetone. Dittcetone- phenanthraquinone. phenanthraquinone. Action of Amines on Acetonephenanthraquinone.-It had already been shown (Zoc. cit.) that by the action of ammonia on acetone- phenanthraquinone, one oxygen-atom of this compound could be replaced by imidogen. We, therefore, determined to study the action of amines. The reaction was allowed to take place in the cold in ethereal solution. With ethylamine, nothing b u t a green gummy mass was obtained which turned blue when treated with hydrochloric acid. With diethy lamine, crystals were gradually deposited from the21 DIKETONES WITH KETONES. ethereal solution. These proved to be acetonediphenanthraquinone ; so that the action of diethylamine was identical with that of potash.With aniline, the substance yielded nothing but a green, gummy mass. 2. BENZIL AXD ACETONE. By the action of an aqueous solution Qf potash on a mixture of benzil and acetone, three distiuct products may be obtained according to the conditions of the experiment. a. By acting with a small quantity of potash on benzil dissolved in an excess of acetone, the additive compo,und acetonebenxi,? is formed :- a. Cl4HlO02 + CsH60 = C17H1603. Acetonebeazil. b. By employing an excess of potash under conditions otherwise the same as the foregoing, a condensation-product of 1, mol. of benzil with 1 mol. of acetone is obtained :- c. By acting with a small quantity of potash on acetone mixed with an excess of b e n d , a condensation-product of 2 mols.of benzil with 1 mol. of acetone is formed :- a. Action of a small Quantity of Potash o n a Mizture of Benxil with Zxcess of Acetone. 50 grams of finely powdered b e n d are introduced into a flask along with 30 grams of acetone," and $ C.C. of strong potash (sp. gr. 1.27) is added. The flask is then corked, after which the whole is shaken until the benzil has entirely dissolved, about an hour being required for this operation. The liquid at the same time assumes a reddish colour. If, after standing for two or three days there is no sign of crystallisation, a drop of the liquid should be removed, allowed to solidify by exposure to the air, and the crystalline sub- stance thus obtained added to the contents of the flask.The whole is again allowed to stand as long as the separation of crystals con- * The employment of an acetone purified by means of the bisulphite compound is i n this reaction indispensable-not merely for obtaining a good yield of the com- pound, but in order to obtain any of the compound a t all (see note, p. 13).22 JAPP AND MILLER ON COMPOUNDS OF tinues, a process which is generally complete in about a week. Be- fore pouring off the still liquid portion from the crystals, it is ad- vantageous, especially in warm weather, to allow the flask to remain for some time in a refrigerator. On the other hand, the aid of the refrigerator must not be called in before the reaction is complete, otherwise a separation of unaltered benzil will occur.The crystals, after draining from the mother-liquor, should be washed with a small quantity of ether (which must be free from alcohol, since alcoholic potash has a specific action on the substance), then dis- solved in ether, and the solution allowed to evaporate spontaneously. I n this way the new compound is obtained in large colourless square prisms, frequently a quarter of an inch in thickness, with flattened ends and corners generally cut off. It is deposited from a hot alcoholic solution, on cooling, in small lustrous crystals. It is readily soluble in ether and in hot alcohol; but only moderately in cold alcohol. It melts a t 78". The powdered substance, after drying over sulphuric acid, is electric. A further quantity of the substance can be obtained from the oily mother-liquors, but it was found more advantageous to treat these with an excess of strong potash, and in this way to obtain the condensation-compound dehydracetonebenzil, C1,Hl4O2 (vide i n f i n ) , which, from its sparing solubility, can more readily be purified.Analysis of the substance gave figures leading to the formula CIjHieO3 :- Substance. GO,. OH,. I ........ 0.1190 0.3306 0,0644 11. ....... "0-1 305 0.3634 0.0718 CalcuIated for Found. c ,7 H 160 3' 7- 7 rL-- -3 I. 11. C,, .... 204 76-11 75.76 75.91 Hi, .... 16 5.97 6*@1 6.11 0, ...... 48 17.92 268 100.00 - - - -- The substance is therefore an additive compound of benzil a i d acetone in equal molecular proportion (see Equation a, p. 21). It, would receive the name acetonebenziZ.(For the constitutional formula of this compound see p. 17.) Dilute potash cannot be employed with advantage in the preparation of this compound. The react<ion requires a longer time than with coiicentrated potash, and there is the additional drawback that a larger quantity of uncrystallisable oily substance is formed. A c t i o n of Heat o n AcetonebenziL-A weighed quantity of substanceDIKETONES WITH KETONES. 23 was introduced into a tubulated flask, which was connected with another similar flask, the latter to act as receiver. The flask with the substance was heated in a sulphuric acid bath, and the receiver was cooled with ice. A little below 200°, a few drops of liquid distilled over, and a t 200" the liquefied substance in the flask boiled slowly, whilst a colourless liquid collected in the receiver.The heating was continued until nothing further distilled over. The dark-coloured residue, which solidified on cooling, was weighed; and the distillate was also weighed. The solution, on cooling, deposited characteristic, yellow, needle-shaped crystals of benzil, melt- ing at 94". The distillate had the odour of acetone, and on redistillation it boiled between 56" and 58". Mixed with hydrogen sodium sulphite, it became hot, and, on cooling, the liquid deposited crystals of the acetone double compound. The residue was dissolved in hot alcohol. The following are the quantitative results :- Weight of substance .............. 6.38 grams. ,? residue (benzil) ........ 5.25 ,, Loss.. .......................... 0.03 ,, 9 , distillate (acetone) ......1.10 ?, Supposing the decomposition to have taken place according to the equation- C,,H,ba = C,,H& + C3Hs0, Acetonebenzil. Benzil. Acetone. the weight of b e n d obtained from the above weight of substance ought t o have been 5 grams, and that of the acetone 1.38 grams. For an experirnent of this kind, the above may be regarded as a sufficiently close approximation. The decomposition is therefore analogous to that which acetom- phenanthraquinone undergoes under the influence of heat (Trans., 1882, 274). Oxidation of AcetoneberzziL-The study of the oxidation of this com- pound was undertaken, less with a view of throwing light on its constitution than of comparing its behaviour towards oxidising ngent,s with that of the condensation-product dehydracetonebenzil (4.v.).By oxidation with a mixture of potassium dichromate and dilute sulphuric acid, hhe products obbained were benzoic and acetic acids. The formation of acetic acid is of importance in conneckion with the fact that the condensation-product yields no trace of acetic acid on oxidation. We also attempted, by oxidising with chromic anhydride in acetic24 JAPP AND MILLER ON COMPOUNDS OF acid solution, to obtain some intermediate product, but without success. Action of Ammonia on, Acetonebend.-20 grams of the cornpound were dissolved in ether, and the solution was saturated with dry ammonia. A separation of crystals cominenced during the process, and, on standing, the quantity of crystalline substance increased. The liquid was poured off, the cryst,als washed with ether, and recrystal- lised from boiling alcohol, from which the compound was deposited in groups of small, colourless plates, melting a t 176".In melting, i t turns red and evolves gas. The crystals also assume a faint pink colour by long exposure to the air. With hydrochloric acid and with oxalic acid, they yield a red gum. Analysis gave results agreeing with the formula CI~H~~NO, :- Substance. cop OH,. I.. ...... 0.1316 0,3662 0.07134 11.. ...... 0-1468 0.4096 0.0880 111.. ...... G.1228 0.3438 0.0730 IV. 0.1104 gram burnt with cupric oxide in a vacuum gave 5.40 C.C. V. 0.0886 gram gave 4.00 C.C. moist nitrogen at 14", and under moist, nitrogen a t 14', and under 756 mm. pressure. 759 mm. pressure. Calculated for Found.m C',;H17N02. r-- 7Jc-- -7 I. 11. C , 7 . . .. 204 76.40 75-89 76.09 76.35 - - HIT.. .. 1 7 6.37 6.61 6.66 6.60 - - N . . . 14 5.24 0, . 5 . . 32 11.99 u 5.72 5.30 - -- - - -- - - - -- 267 '100.00 Different preparations were employed in these analyses. The following equation expresses the formation of this compound :- C,,H,,O, + NH, = C,,H,,NO, + OH,. Acetonebenzil. Acetonebenzilimide. This formation of acetonebenzilim,ide, as we propose to name the compound, corresponds with that of acetonephenanthraquinoiiimide (Trans., 1882, 274), from acetonephennnthraquinone and ammonia. Action of Hydroxylanzine 07% Acetonebenzi1.-An attempt to prepare a hydroxylamine-derivative by heating the compound in alcoholic solu- tion with hydroxylamine hydrochloride failed.The s o l u t i o n instantly became red on warming, and nothing but red resin was obtained. AsDIKETONES WITH KETONES. 25 this was probably due to the action of the hydrochloric acid liberated in the reaction, the experiment was repeated, employing free hydroxyl- amine. For this purpose a quantity of acetonebenzil was dissolved in alcohol, and to this liquid a concentrated aqueous solution of two molecuIar proportions of hydroxylamine hydrochloride mixed with a slight excess of sodic carbonate, was added. After standing for two days, a consideramble quantity of a white crjstalline substance had separated. An excess of water was added in order to precipitate the organic mbstance and dissolve the inorganic salts. By recrystallisa- tion from boiling alcohol, the new compound was obtained in small colourless crystals, melting at 146".It is also moderately soluble in boiling benzene, but only sparingly soluble in ether. Hydrochloric acid converts it into a red resin. Analysis gave figures agreeing with the formula C17H,,N0, :- Substance. cop OH,. I .... ,. .. 0.1371 0.3612 0.0756 11.. .. .. .. 0.1114 0.2930 0.0616 111. 0.1070 gram burnt witb cupric oxide in a vacuum gave 4.7 C.C. moist nitrogen at 17*7", apd under 763.5 mm. pressure. Calculated for Found. A C17H,, N 03. r- 7 r - F I. 11. 111. C1, .. .. 204 72.08 71.85 71.73 - Hi,.. .. 17 6.01 6.12 6.14 - N .. .. 14 4.95 - 0, .... 48 16.96 -. - - -- 5.10 -- - 283 100.00 Only one molecule of hydroxylamine has therefore taken part) in the condensation, and the formation of the compound is expressed by the equation- C17Hi603 + PJH,(OH) = C ~ ~ H I ~ N O ~ + OH2.All attempts to induce the compound thus obtained to react with a second molecule of hydroxylnmine failed, although acetonebenzil must be assumed to contain two carbonyl-groups. This negative result is: however, in harmony with the investigations, since published, of Ceresole (Bey., 17, 812), who shows that di-carbonyl compounds do not react with two molecules of hydroxylamine, unless the carbonyl- groups are directly united. A c t i o n of Potash on a Xolution of Acetonebend in Acetone.-A small quantity of the compound was dissolved in acetone, and an excess of strong potash (sp. gr. 1.27) added. After standing for a day, the26 JAPP AND MILLER ON COMPOUNDS OF solution, which had become very dark, was poured into water.The substance which separated was dried and then recrystallised from boiling benzene. It was thus obtained in yellow crystals, melting a t 147" , and proved to he dehydracetonebenzil, a condensation-product of benzil with acetone described later on. The reaction had therefore taken place according to the equation- C17H1603 - OH2 = C1'IHIi027 Deli ydracetonebenzil. and no diacetone compound had been formed as in the case of the corresponding phenanthraquinone reaction. Action of Dilute Alcoholic Potash on Acetoizebenzi1.-Prom 4 to 5 grams of the compound were dissolved in sufficient alcohol to keep the substance in solution in the cold, 5 drops of concentrated alcoholic potash were added, and the whole was allowed to stand in a corked flask.The solution assumed a light-red colour, and colourless lustrous crystals were gradually deposited on the sides of the flask. These were washed with alcohol and then recrystnllised from benzene until the constant melting point 194-195" was obtained. Analysis led to the formula C31H2401 :- Substance. cop OH,. 0.1462 0.4522 0.0692 Calculated for C 3 1 ~ 2 . 1 0 4 . rL- 7 Found. CSl ........ 372 80.87 80.62 H,, ........ 24 5.21 5.19 O I . . ........ 64 13.92 460 100.00 - - -- The compound is identical with one described later on (dehydracetone- dibenzil) obtained by the action of potash on a mixture of acetone with excess of benzil (see also Equation c, p. 21). The reaction in which it is formed in the present case differs from the reaction of alcoholic potash with acetonephenanthraquinone (p.20), inasmuch as with the quinone compound there was elimination of acetone only, whereas in the present case both acetone and water are eliminated :- 2Ci7H1,Oa = c31Euo1 + CaHc,O + OH,. Acetonebenzil. Dehydracetone- Acetone. di hcnzil. The action of various other reagents-phosphoric chloride, acetic anhydride, nascent hydrogen-was tried, but without yielding any definite result.DIKETONES WITH KETONES. 27 b. Action of an Excess of strong Potash on a Mizture of B e n d with aw Ezcess of Acetone. 100 grams of pure acetone, 150 grams of finely powdered benzil, and 1 C.C. of potash solution (sp. gr. 1.27) were introduced into a flask, and shaken until all the benzil had dissolved; after which 20-:?0 C.C.of the potash solution were added, and the whole, after thoroughly shaking, was allowed to stand for a day. A t the end of this time, the layer of acetone and benzil floating on the surface of the excess of potash had solidified. The potash was poured off, and the contents of the flask were shaken with hot water, which melted the crude product and removed the remains of the potash. The product, which solidified on cooling, mas graund in a mortar, extracted in a flask with a, small quantity of ether, and then washed on a filter with ether until the filtrate passed through only slightly coloured. I n this way, the dark-colonred impurities were for the most part removed. The yellowish-grey powder thus obtained was crystallised from hot alcohol or benzene until the constant melting point 147" was obtained.The alcoholic solution deposits the cornpound in large, canary-yellowx prisms; from benzene it separates in tufts of needles of the same colour. Animal charcoal had no effect in removing this colour, nor could the above melting point be altered by recrystallisation. The appear- ance of the compound was perfectly homogeneous, and we had no reason to suspect the presence of an impurity, especially as analysis gave figures agreeing well with those required for a condensation- product of 1 mol. benzil with 1 mol. of acetone, formed with elimina- tion of 1 mol. of water. I n an experiment, however, to be described later, in which the substance was oxidised with chromic anhydride in acetic acid solution, there was obtained, along with a new acid, a colourless neutral substance, which was deposited from benzene in forms indistinguishable from those of the above yellow compound, but melting a t 149".On analysis this colourless compound gave figures agreeing with the formula deduced f o r the yellow compound. The oxidation had therefore removed from the supposed yellow com- pound a coloured impurity, and had at the same time slightly raised the melting point. In order to dispel any doubt as to the identity of the white and yellow compounds, a mixture of the two was dissolved in benzene. Crystals of a p a l e r yellow colour were deposited, not a mixture of white and yellow crystals. The following are the analytical results, which lead to the formula C17H1102 :- See, however, following paragraph.28 JAPP AND MILLER ON COMPOUNDS OF Substance.coz. OHz. I ...... 0.1176 0.3502 0-0614 I1 ...... 0.1234 0.3679 0.0638 I11 ....... 0.1330 0.3978 0.0686 IV ...... 0.1348 0.4034 0.0700 Calculated for Found. C17H1402. r- 7 Cl,.. .... 204 81.60 81.21 81-31 81.57 81.61 Hid.. .... 14 5.60 5.80 5.74 5.74 5-77 0, ...... 32 12.80 250 100*00 I. 11. 111. IV. rL- 7 - - - - -- -- Analyses I and I1 were made with the yellow substance ; I11 and The formation of the compound is expressed by the equation- I V with the colourless substance. In all probability acetonebenzil is formed as an intermediate product. The conversion of acetonebenzil into this compound has been already described (p. 25). As the new compound is derived from acetonebenzil by the removal of a molecule of water, we propose to name it dehydracetwdenzil.It is worthy of note that this con- version cannot be effected by means of acetic anhydride. As regards the constitution of dehydracetonebenzil, apparently the most natural supposition would be to regard it as an analogue of Claisen and Ponder's benzalacetone, C~H,F,.CH CH.CO.CH3, (Annulen,, 223, 138), obtained by the condensation of benzaldehyde wit'h acetone under the influence of dilute caustic soda. According to this view, it would be a benzoyl-derivative of benzalacetone and would possess the formula- The behaviour of this compound with bromine and with oxidising agents is, however, quite incompatible with this view. Its beha- vinur with oxidising agents can best be accounted for by the supposi- tion that it is a closed-chain compound of the forrnula-DIKETONES WITH KETONES. 29 C6H,.C0 Deh ydracetonebenzil.(See also p. 13.j Action of Bromine o n Dehydracetonebenzil.*-lO grams of the compound were dissolved in su5cient chloroform to keep the whole in solution in the cold, and a solution of bromine in chloroform was gradually added. The colour of the bromine did not disappear. After standing for some time, fumes of hydrobromic acid were given off, and a crystalline substance was deposited. Both the chloroform and the bromine had been carefully dried before using. The crystalline substance was washed with chloroform and recrystallised from hot glacial acetic acid, from which it was depo- sited on cooling in slender colourless needles, melting a t 172” with blackening and decomposition.It is only sparingly soluble in alcohol. Two bromine determinations (method of Carius) gave figures pointing to a monobromo-substitution compound :- Substance. AgBr. I ........ 0.2872 0.1627 I1 ........ 0.2538 0.1458 Found. Calculated for f------ 7 C1,H,3Br02. I. 11. Br in 100 parts .......... 24.21 24.10 24.U In order t o make perfectly sure that this monobrominated com- pound had not been obtained from a dibromide by decomposition during recrystallisa,tion, a fresh quantity of the substance was pre- pared, washed thoroughly with cold chloroform, dried a t ordinary temperatures, and then analysed. This preparation gave 26.2 per cent. of bromine, showing it to be merely an impure monobromo- compound. A compound of formula (I) ought, judging from the analogy of benzalacetone and the other compounds prepared by Claisen, to yield a dibromide.That dehydracetonebenzil has not this formula is rendered still more probable by the fact that dehydracetophenone- benxil ( q . ~ . ) , in which the substitution of phenyl for methyl appears to have prevented the formation of a closed chain, and which has a constitution corresponding with formula (l), readily forms an additive compound with bromine. * For all reactions here dcscribed, the yellow compound was employed.30 JAPP AND MILLER ON COMPOUXDS OF Oxidation of D~hlldmcetonebenzil.--20 grams of the yellow com- pound were dissolved in glacial acetic acid, and an equal weight of chromic acid-also dissolved in acetic acid-was gradually added. The mixture, which became slightly warm, was finally boiled with a reflux condenser in order to finish the reaction. It was then poured into water, which occasioned a separation of organic substance.The whole was extracted with ether, and the ethereal solution was shaken with a solution of sodium carbonate in order to remove acids. On evaporating the ether, some unattacked dehydracetonebenzil was obtained, but in a colourless condition. The sodium carbonate solution was acidified with hydrochloric acid and extracted with ether. On distilling off the ether, an acetic acid solution of a new orgarh acid remained behind, and, by allowing the acetic acid to evaporate in a desiccator over lime, the new acid was obtained in almost colourless crystals, whilst any benzoic acid that had been formed remained in the mother-liquor.The acid was recrystallised from boiling benzene until it showed a constant melting point. Thus purified, it forms tufts of colourless needles, melting at 152'. It is readily soluble in boiling benzene, but separates almost entirely on cooling. Boiling water dissoIves it sparingly. Analysis gave the following results :- Substance. ( 2 0 2 . OH,. I.. ...... 0.1331 0.3682 0.0672 11.. ...... 0,1276 0.3530 0.0642 These numbers lead to the formula C16&03 :- Calculated for Found. C16H1403* rd- 7 TL-- I. II. C,6 .... 192 7 5 - 2 75.44 75.44 H 1 4 .... 14 3-51 5.61 5-59 O3 ..... 48 18.90 254 100.00 - - - -- A siZver s d t was prepared by precipitating a solution of the ammon- The dry salt It gave the following figures on combustion :- ium salt with silver nitrate.is electric. It forms a white powder. Substance. cop OH2 4 5 0.1418 0.2752 0.0466 0,0424DIKETONES WITH KETONES. 31 Calculated for C16H1303Ag* w- Found. C I S . . a . 192 53.18 52-92 Hi3 ...... 13 3-60 3.6 4 Ag ....... 108 29.92 29.90 O3 ........ 48 13-30 361 100.00 - - -- The barium salt was obtained by boiling the acid with barium car- bonate, and allowing the solution t o evaporate over sulphuric acid. Like all the soluble salts of this acid which we examined, its difference of solubility in hot and cold solutions is very slight. It was obtained in rosettes of flat prisms of the formula (c16H1303),Ba,20H,. It parts with its water of crystallisation at 100". 0.3064 gram of air-dried salt lost at 100" 0.0160 gram, and the resulting 0.2904 gram anhydrous salt gave 0.1042 gram barium sul ph ate.Calculated for (C16H1303),Ba,20H2. Found. OH, in 100 parts ....... 5.30 5.22 Ba in 100 parts ........ 21.30 21.09 Calculated for (C16H1303)2Ba* Found. The acid is formed from dehydracetonebenzil according to the equatian- Ci,Hi,O, + 3 0 = Ci6H1403 + COz. Supposing dehydracetonebenzil to possess the constitution repre- sented by formula (l), the oxidation of such acompound to an acid of the formula ClsH140, would be very difficult t o account for. It would be necessary to assume that the methyl-group at the end of the chain is oxidised away, the carbonyl-group converted into carboxyl, and that then the two unsaturated carbon-atoms, under conditions which generally lead to the separation of such atoms, take up, in presence of a powerful oxidising agent, hydrogen and become saturated.On the other hand, by adopting formula (2) for dehydracetone- bend, the formation of the acid can be explained. In the first place by a separation of the carbonyl from one of the methylene-groups in the closed chain, and by conversion of carboxyl-groups, an acid of the formula ............... COO H C6H5*7 < c H,. c o OH C6&.CO these separated groups into3-2 JAPP AND MILLER ON COMPOUNDS O F would be obtained. It is well known that ketonic acids vary greatly in stability according to the class to which they belong. Those ketonic acids are stable in which carboxyl and carbonyl are directly united, as in pyruvic acid, or in which carboxyl and carbonyl are attached to different carbon- atoms, as in lawulic (/%acetylpropionic) acid ; those are unstable, in which carboxyl and carbonyl are attached to the same carbon-atom, as in the case of acetoacetic acid: such acids readily part with carbonic anhydride, yielding a ketone.An acid of the above formula would unite in itself the properties of two of the above classes; it would be unstable as regards the carboxyl-group attached to the same carbon-atom as the benzoyl-group ; and it would be stable as regards the ohher carboxyl-group. Under the conditions of the oxidation experiment, this acid would part with carbonic anhydride from the first of these carboxyl-groups (as indicated in the formula), yielding the monobasic acid :- C6Hs.CH.CH2.COOH This acid is a bibasic ketonic acid.I C6H5. C O which would thus be P-benzoylhy drocinnamic acid. Although we regard the above as the most probable of the various constitutional formula that might be suggested for the acid, we must call attention to the fact that the only reactions which we have tried in confirmation of this coiistitution have yielded negative results. Thus, by the action of nascent hydrogen we hoped to obtain a lactone ; but after subjecting the acid for some days to the action of sodium-amalgam, nearly the whole of the original substance was recovered unchanged, and only a trace of an indifferent oil was formed, which, however, did not appear to be a lactone, as it did not dissolve in caustic alkalis on heating." We further hoped, by the action of hydroxylamine, to prove the ketonic character of the acid; but no action took place with hydroxylamine hydrochloride in aqueous alcoholic solution a t 100".The various other constitutions that might be suggested for this acid-thus that it is an acid of the glycidic type, or that it is an unsaturated acid containing an alcoholic hydroxyl-group-are still less in keeping with its reactions and mode of formation, The chief obstacle to a thorough study of this acid is the di&culty of obtaining it in any considerable quantity, the yield being very small. As a dehydracetonebenzil of formula (1) ought to yield acetic acid on oxidation, it seemed of importance to show that this acid was not * Of course this insolubility in caustic alkalis does not absolutely prove that the oil was not a lactone.DIKETONES WITH KETONES.33 formed, especially as acetonebenzil readily yields acetic acid. A quantity of dehydracetonebenzil was therefore boiled with a mixture of dilute sulphuric acid and potassium dichromate, until all action had ceased. The liquid was then distilled until about a third had passed over; the distillate was filtered from benzoic acid, neutralised with sodium carbonate, and evaporated to dryness. Not the slightest trace of acetic acid could be obtained from this residue. Another portion of dehydracetonebenzil was oxidised with a 5 per cent. permanganate solution in the cold. The filtrate from the man- ganese dioxide, when acidified and extracted with ether, yielded as chief product benzoic acid, along with a small quantity of benzoylforniic acid, identified by means of the characteristic thiophene reaction.We satisfied ourselves that p-benzoylhydrocinnamic acid does not give this reaction. The action of the following reagents upon dehydracetonebenzil WRS also tried, but without definite result :-acetic anhydride, alcoholic ammonia, potash (fusion) , hydriodic acid and amorphous phosphorus, zinc-dust a t higher temperatures, zinc-dust with acetic acid. c. Action of a Xmall Quantity of Potash on a 2Cli'zture of Acetone with Excess of Bend. 50 grams of finely powdered benzil were introduced into a flask with 20 grams of pure acetone and 4 C.C. of potash solution (sp. gr. 1.27). The flask was shaken until all the benzil had dissolved, this process requiring about an hour. After standing for a day, the con- tents of the flask, which were almost solid, were shaken with ether.A small quantity of acetonebenzil went into solution and a sparingly soluble white crystalline powder remained, which, after washing with ether, was recrystallised from benzene until the constant melting point 194-195" was obtained. Besides acetonebenzil, the ethereal washings contained an uncrystsl- lisable gum, which, however, by shaking with more potash, could be converted into the sparingly soluble crystalline compound. Analysis gave results agreeing with the formula C31H,a0, :- Substance. CO,. OH,. I.. ...... 0.1194 0.3520 0.0550 11. ....... 0.14'20 0.4182 0.0666 111.. ...... 0.1656 0.4874 0.0790 VOL. XLVII. D34 JAPP AND MILLER ON COMPOUNDS OF Calculated for Found.C3lH2.104 * I----- 7 r--L-- I. IT. 111. C,, .. .. 372 80.8; 80.40 80.32 80.27 H,, .. .. 24 5.21 5.30 5-21 5-30 0 4 .... 64 13.92 - - - -- -- 460 100.00 The compound is identical with that obtained by the action of dilute alcoholic potash on acetonebenzil (p. 26). I t s forniation in the present case occurs by the abstraction of 1 mol. of water from 2 mols. of benzil and 1 mol. of acetone. It woixld therefore receive the name dehydra~etonedibenzi1:- 2CiaH1002 + CJLO = CsiH2aOa + OH,. Dehydracetonedibenzil is almost insoluble in cold benzene and alcohol; even boiling alcohol dissolves it but sparingly. The best solvent is boiling benzene, from which it is deposited, after some time, in well-formed colourless crystals. From the alcoholic solution, it separates with 1 mol.of alcohol of crystallisation, which is retained at loo", but given off at 120". When the crystals containing alcohol of crystallisation are heated in a capillary tube they melt at 158- 160". yesult :- Alcohol of cry stallisation was 0.2410 gram air-dried substance, tion, lost a t 120" 0.0222 gram. determined with the following containing alcohol of crys tall isa- Calculated for ~31H'3404,C2H60. Found. C,H,O in 100 parts . . . . . . . . 9.09 9.21 3. BENZ~L AXD ACETOPHENONE. a. A c t i o n of Potash iu the Cold on a Mixture of B e n z i l a n d Acetopherzone. Equal molecular proportions of acetophenone and finely powdered benzil were shaken in a flask with an excess of strong potash (sp. gr. 1.27) and allowed to stand. At first the potash solution remained in suspension, but after a few days it separated, whilst the organic substance formed a solid cake on the surface. This cake was ground with water, thoroughly washed, and, after drying, shaken with ether.The greater part dissolved, leaving a yellow powder, which proved to be dehydracetophenonebenzil, a compound to be described later. On spontaneous evaporation, the ethereal solution deposited large colourless oblique prisms, and the mother-DIKETONES WITH KETONES. 33 liquor from these crystals yielded a further quantity of the same substance, contaminated however with unchanged benzil. By crystal- lisation from alcohol, the colourless substance was obtained pure in flat oblique prisms, melting at 102'. It is readily soluble in ether and in boiling alcohol, sparingly soluble in alcohol in the cold. When heated above its melting point, it gives off acetophenone, Rhich may be recognised by its odour.Analysis gave numbers agreeing with the formula C,,H,,O, :- Substance. co:. OH:. I . . ...... 0.1426 0.4 170 0.0724 11.. . . . . . . 0.1498 6.43378 0.07G6 The formation of this compound is expressed by the equation- Ci,Hio02 + CJ&O = CyZHir303, and it would receive the name aceto~~1~e~zoizelieri;iZ. Its constitotional, formula would be- C6H5.C (0 H).CH2.Co.C,H, I CsH,. c 0 b. Action of Potash, aided by Heat, 011 a Mixtiire of Betwil a h c J Acetophenone. The ingredients were mixed as in the preceding expei*iment; but heat was applied until the whole of the benzil had fused, after which the flask was allowed to stand for some hours at a tein- psratnre sufficiently high to prevent solidification.On allowing the flask to cool, the layer of organic substance floating on the surface of +he potash solidified. The solid cake was treated as in the former experiment. This time, the ethereal extract contained only a small quantity of a reddish oil and a trace of maltmered benzil. No aceto- phenonebenzil was formed on this occasion. The portion undissolved by the ether was recrystallised from hot alcohol, until it exhibited the constant melting point 129". It crystszllises in tufts of flat pointfed yellowish needles, which are very sparingly soluble in ethey and in cold alcohol, but dissolve readily in boiling alcohol. u 236 JAPP AND MILLER: DIRETONES AND KETONES. The analytical figures agreed with the formula C,,H,,O, :- Subatance. con.OH,. I.. . . . . . . 0.1582 0.4900 0.0748 11.. 0.1996 0.4010 0.0628 . . . . . . Calculated for Found. C25)3[1602. 7<-7 rd- -7 I. 11. C2.2 . . . . 264 84.61 84.47 84-38 Hlti . . . . 16 5.13 5-25 5.38 02.. .... 32 10.26 ' - - -- - 312 100.00 This compound is formed by the condensation of a molecule of benzil with a molecule of acetophenone :- It may therefore receive the name dehydracetophenonsbenxil. Acticn of Bromine on DehydracetophenonebenzX--The compound was dissolved in cold chloroform, avoiding an excess of the solvent, and one molecular proportion of bromine was added. On standing, the colonr due to the bromine gradually became much fainter, without however entirely disappearing, and a bromine-derivative was deposited in large crystals. There was no evolution of hydrobromic acid. The crystals were of a reddish colour, and, when exposed to the air, gave off a faint odour of bromine, even after standing for some days, at the same time becoming opaque. As it was found impossible to re- crys tallise this substance without decomposition, the freshly prepared crystals were washed with chloroform, exposed for a short time to the air, powdered, the powder dried for two hours over sulphuric acid, and in this condition analysed. A bromine estimation (Carius) gave figures which were somewhat too high for a tetmbromide-an entirely unexpected result. 0.1864 gram of substance gave 0,2278 gram of silver bromide. Calculated f o r CT4Hl6O2Br4. Pound. Br in 100 parts.. ...... 50.63 52.00 Heated in a capillary tube the substance becomes dark at about rO , turns pale again at aboiit 80", and melts between 110" and 115". The bromine was in a state of very unstable combination. A por- tion of the substance which had been allowed t o remain for some weeks in a desiccator over lime, had parted with nearly the whole f - 0SORABJI ON SOME NEW PARAFFINS. 37 of its bromine, and was found, after recrystallisation from alcohol, to have been reconverted into dehydracetophenonebenzil. We are unable satisfactorily to explain the formation of a tetra- bromide. A dehydracetoph enonebenzil of the formula- C,H,.C CH.CO.C,&, C,H,.CO ought to yield a dibromide, and it is conceivable that this dibromide might form a molecular compound with a second molecule of bromine, similar to the molecular compounds of acetic acid with bromine a i d hydrobromic acid. In any case, the action is nnomaIous and deserves further study. For the present, however, we regard this reaction as sufficient evidence of the unsaturated character of dehydracetophenone- benzil, and the foregoing is the only probable constitutional formula which would represent it as an unsaturated compound. The fusing points of dehydracetonebenzil and dehydracetophenone- benzil also render it probable that these compounds do not belong to one and the same category. Whereas acetophenonebenzil, a com- pound which may be regarded as derived from acetonebenzil by the substitution of phenyl for methyl, fuses higher than acetonebenzil, clehydracetophenonebenzil fuses 20" lower than dehydracetonebenzil. The high melting point of the latter compound is probably due to the fact that it is, as assumed in this paper, a closed-chain compouiid. Norrnnl School of Xcience, So 11 th Kensing ton.

ISSN:0368-1645    

DOI:10.1039/CT8854700011

出版商:RSC    

年代:1885

数据来源: RSC

摘要:

SORABJI ON SOME NEW PARAFFINS. 37 By KHAN BAHADUR BOMANJI SORABJI, Ph.D., C.E., &c. AT present, comparatively little is known of the higher members of the paraffin series; the difficulty of separating them froiu one another rendering it impossible t o isolate them from their natural sources, such as petroleum, ozokerit, &c, The solid paraffin obtained from such sources can be partly separated into its constihents by means of fractional crystallisation, but the fractions thus prepared ere still far from being homogeneous and pure compounds. In order to study these higher paraffins, therefore, it is necessary t o prepare them synthetically. Several syntheses of this kind hare35 SORABJI ON SOME NEW PARAFFINS. lately been made by Krafft (Abstr., 1882, 1271 and l272), but many gaps in the series of paraffins still remain, and the present communica- ticn gives the results of an endeavour to prepare some of the missing members of the series.The method which appeared most likely to yield satisfactory results was that of Wiirtz, which consists in treating the iodide of an alcohol radicle with sodium, according to the equation- But in these reactions more or less of the paraffin containing the same number of carbon-afoms as the alcohol radical is almost always produced, according to the equation- 2CwH2,1+J + Na2 = 2NaI + ClrHzn + CnH2% + 2 . As my especial aim was the preparation of dicetyl, CS2HG6, and the paraffin cetane, C,,H,,, which would probably be produced as a bye- product, had not been prepared from cetyl iodide, it appeared of interest first to make and examine this body so as to minimise, as far as possible, the after difficulty of the purification of the dicetyl.I. Cetane from C'etyl Iodide. This paraffin was obtained from the iodide by the reduction of the latter by concentrated hydriodic acid in the presence of phosphorus, and also by the digestion of the iodide with zinc and hydrochloric aci d , Cetyl iodide was mixed with four times its weight of pure alcohol, and introduced into a flask containing a considerable quantity of granulated zinc, the flask being connected with a i-eflux condenser. Fuming hydrochloric acid was then slowly added, causing a t once a precipitation of a heavy oil (cetyl iodide). After four or five days' digestion, the oil rose to the top of the liquid, but as it still contained much iodine it was resubjected to the same treatment for a, week.Water was then added, and the oil which separated was washed repeatedly with concentrated sulphuric acid containing nitric acid, with water, with caustic soda, and with water until it no longer con- tained a trace of iodine. It was then dried over solid potash and distilled. Cetane, thus obtained, boils constantly at 278', and when cooled, solidifies to a crystalline mass which melts a t 18-20'. A combustion yielded the results- Calculated. rL-- 7 Found. CI6 . . . . . . 192 84.96 per cent. 84.76 €Id4 . . . . . . . 34 15.04 ,, 15 29SORABJI ON SOME NEW PARAFFINS. 39 Two vapour-densities made with V. and C. Meyer's apparatus yielded 7.9 and 7.85 respectively, theory requiring 7.84.Zincke's dioctyl (An~zalen, 152, 16) from primary octyl iodide melted a t 21", and the same body obtained from mercury octyl by Eichler (Bey., 12, I882) had a melting point of 14". Cetane resembled Zincke's dioctyl in all other respects, and its low melting point, as well as that of Eichler's compound, is probably due to the presence of a trace of im- purity. Cetane is miscible in all proportions with alcobol and ether: and as cetene is also very soluble in these reagents, the purification of dicetyl from these bye-products did not seem to offer any difficulty. 11. Dicetyl f r o m CetyZ Iodide. Cetyl iodide dissolved in six times its weight of ether was intro- duced into a flask connected with a reflux condenser. Finely cut sodium was then added, and the whole allowed to stand for some time a t the ordinary temperahre.Action set in rapidly, the metal became coated with sodium iodide, and iridescent flakes were deposited in the liquid. The reaction was completed by heating the mixture for 10 hours on the water-bath. On cooling, no trace of cetyl iodide could be detected, but the whole liquid became filled with beautiful glistening scales. In order to remove excess of sodium, alcohol was added, and after the evolution of hydrogen had ceased, the precipitated sodium iodide was dissolved by the addition of water. The whole was then thrown on a filter and the residual crystalline mass dried, and extracted with boiling absolute alcohol, in which it is almost insoluble. Dicetyl is also nearly insoluble in ether, but dissolves readily in boiling glacial acetic acid, crystallising out again almost entirely on cooling. When recrystallised twice from acetic acid, it melts at 70" and distils undecomposed, but at a temperature lying far above t'he range of the mercury thermometer.On cooling, the distillate solidifies to beautiful pearly scales. Dicetyl is neither dissolved nor blackened when treated with concentrated sul- phuric acid at 150". Combustions yielded the following results :- 11. 0.1470 ,, ,, 0.4592 ,, 0.1956 ,, I. 0.1655 gram subs. gave 0.5138 gram COzand 0.2197 gram H,O. These yield t'he numbers- Calculated. Pound. rA-- 7 w - - - - - I C32 = 384 = 85.33 85.18 85.19 H 6 6 = 66 = 14.67 14.84 14.7840 SORABJI ON SOME NEW PARAFFINS. Vapour-densities conducted by means of V.and C . Meyer's ap- paratus gave tlhe numbers:- I. 0*2:354 gram substance gave 12.56 C.C. air a t 18" and 743.9 mm. 11. 0.2332 gram substance gave 13.10 C.C. air a t 23" and 746.1 mm. 111. 0.0929 gram substance gave 5.20 C.C. a i r a t 23" and 746.1 mm. pressure. pressure. pressure. The results when calculated out give- Found. v-- 7 Calculated. I. 11. 111. C32H66.. . . . . 15.5 16.1 15.64 15.70 The mother-liquors from the crude dicetyl yielded, on evaporation, a very slighh crystalline residue, which proved to be almost entirely dicetyl. It is thus clear that hardly any bye-products are formed in this reaction. 111. Ethyl-cetyl from E t h y l and Cetyl Iodides. This compound was obtained by allowing sodium, cut in thin flakes, to act on a mixture of ethyl and cetyl iodides dissolved in ether.The reaction was slower than when cetyl iodide alone was used. A good deal of dicetyl was formed, but( the ethoric liquid contained a second body, which, on evaporat'ion of the ether, remained as a colourless oil. After purification with sulphuric acid, &c., as before, this oil was dried with solid potash a8nd distilled, when it passed over a t 312-313", and the distillate solidified when cooled with ice. This substance was undoubtedly ethyl-cetyl, but the quantity obtained was too small for a combustion or vapour-density determination. It is also doubtful whether it was quite pure, so that the above boiling point must only be looked upon as approximate. IV. Dihepty l fiom Heptyl Iodide. Although heptyl alcohol can be prepared without great difficulty from oenanthaldehyde, and the iodide is very easily obtainable from the alcohol, on attempt appears yet to have been made to synthesise the normal paraffin of the formula, ClaHw from this iodide.It was thought that the synthesis of normal diheptyl might prove of some interest. The heptyl alcohol employed was prepared from oenanthaldeh yde in part by Cross's method (Chenz. Xoc. J., 1877, 32, 124), as modifiedSORABJI ON SOME NEW PARAFFINS. 41 by Jourdan (AnnaZen, 200, l02), in part by Krafft's method for the reduction of aldehydes of high molecular weight (Abstr., 1883, 1075). According t o the tirst-named process, a solution of the aldehyde in glacial acetic acid is reduced by means of sodium-amalgam ; accord- ing to the second, a similar solution is employed, but zinc-dust takes the place ol sodium-amalgam.A better yield of alcohol and a smaller admixture of bye-products was obtained by the first than by the second process. The heptyl alcohol boiled at 175*5", and gave satis- factory numbers on analysis. It was converted into the iodide by saturating i t with gaseous hydriodic acid (Moslinger, AnnaZen, 185, 55). The conversion of the iodide into the paraffin was effected in a manner precisely similar to that employed in the case of dicetyl. The reaction was completed a t the ordinary temperature in about three days. Diheptyl, prepared in this way, is a colourless mobile oil having a slight odour. It boils without decomposition at 245" under 750 mm. pressure. When cooled by means of ice, it solidified to a lamellar. crystalline mass, which began to melt again at Go, and was completely liquid at 10.5". The pure iodide boiled at 201". Analpis yielded the following results :- 0-1880 gram substance gave 0.5831 gram CO, and 0.2616 gram H20. Calculated. r--L-- 7 Found. Cia.. . . . . . 168 84.80 per cent. 84.58 H30 .... .. 30 15.20 ,, 15.47 Vapour-density determinations gave the numbers- I. 0.0602 gram substance gave 7.40 cm. air at 21" and 747.2 mm. 11. 0.0429 gram substance gave 5.35 cm. air at 23" and 746.1 mm. pressure. pressure. These numbers when calculated out give 7.06 and 7.04 respectively, whilst theory requires for the formula CIdHso, 6.82. In conclusion, I have to express my thanks to Professor Johannes Wislicenus, at whose suggestion and in whose laboratory this work was carried out, both for the interest he has taken in my work, and for the valuable advice he has given me during its progress.

ISSN:0368-1645    

DOI:10.1039/CT8854700037

出版商:RSC    

年代:1885

数据来源: RSC

摘要:

42 IV.- On a New Method of Determining the Tapour-pressures of Solids aid Liquids, and on the Vapour-pressure of Acetic Acid. By WILLIAM R.AMSAY, Ph.D., and SYDNEY YOUNG, D.Sc. I N determining the vapour-pressure of acetic acid, Regnault (MLmoires de I'dcadeinie, 1862, 26, 51-60) found at 0" numbers varying between 3.23 mm. and 4.9 mm., whilst Landolt (Annulen, Suppl. v1, 157) gave 7.6 mm. ; at lo", Regnault gave numbers differing as much as 6.3 and 8.2 mm., and at that temperature Landolt found 12.1 mm. ; at 1.5" the difference is still more striking, €or the pressure given by €henu (Annales de Chimie [3], 18, 226j is 7 mm., by Regnault 8.7 to 10.4 mm., and by Landolt 15.1 ; while at 14", Wullner (Pogy. Ann., 103, 529) observed a pressure of 15.7 mm. No one has attempted to account for these discrepancies, except Regnault, who supposed his variations t o be due to the presence of acetone when the vapour-pres- sure was high, and of water when low.In the course of an investigation '' On the Temperature of Volatili- sation of Solids (Trans. Roy. SOC., Part I, 18%, p. 37), a method of ascertaining the vapour-pressure of liquids, differing essentially from the one usually employed, was devised, of which the following i3 a description :- A is a vertical tube, closed at the top by an accurately fitting india- rubber cork perforated with two holes, through one of whichRAMYAY AND YOUNG ON VAPOUR-PRESSURES, ETC. 43 thermometer passes, the bulb of which is completely covered with cotton-wool, adhering closely when moist. Through the other hole is inserted a short narrow glass tube, drawn out to a point a t its lower end, and slightly curved so that the point touches the thermometer.To the other end of this tube is connected by india-rubber tubing a small reservoir, B ; the passage of liquid from B is controlled by means of a screw-clip. It is thus possible to allow liquid to enter the apparatus, trickling down the thermometer and soaking the cotton- wool. A t C a tube, 15 nim. in diameter, is sealed on to the vertical tube. The tube .C communicates with the condenser E ; near the poiut of junction an exit-tube, F, leads to a Sprengel pump. On one side of the exit-tube, a narrow tube, D, is sealed. This narrow tube is for the purpose of admitting air into the apparatus, and is closed by a short piece of india-rubber tubing and a screw-clip.The tube A may be heated either by hot water or paraffin, or it may be jacketed with a wider tube, as shown in the figure, and exposed to the vapour of any desired liquid. The condenser, E, may be cooled with a freezing mixture, especia,lly if the liquid is volatile. The actual experiment is performed by exhausting the apparatus as perfectly as possible with a Sprengel’s pump, to which a gauge is attached ; by unscrewing the screw-clip, liquid enters the apparatus, trickles down the thermometei-, and thoroughly moistens the cotton- wool. When a sufficient quantity has entered, the screw-clip is closed. The tube is then heated, and the temperature 2nd pressure noted as soon as they have become consbant. A little air is admitt,ed by means of the clip a t D, and the pressure and temperature again read off.When the supply of liquid on the cotton-wool has become exhausted, more of the liquid is admitted. This process is repeated until a snfficient number of observations have been taken. The results may he checked by beginning a t a high pressure, and gradually ex- hausting the apparatus with the pump, reading whenever convenient. We think that this process has advantages over the usual one, inasmuch as the temperature of the whole apparatus has not to be kept constant, and the pressure can be regulated as desired, and a great number of observations taken ; moreover, the extreme difficulty of introducing a liquid free from air into a barometer tube is avoided. We are induced to think that the presence of air and moisture is the cause of most of the discrepancies in the results obtained by different observers.This method is equally applicable to the determination of the vapour- pressure of solids, by substituting a cork perforated with one hole instead of two, and coating the thermometer with the solid, by dipping it repeatedly into the melted substance. The only precaution required is to avoid dipping the bulb E so deeply into the freezing-mixture as44 RAMSAY AND YOUNG: NEW METHOD OF DETERMINING to block the exit-tube by condensation of the solid. Results proving the accuracy of this process have already been communicated in the paper previously referred to. The results obtained by this process of determining vaponr-pressures agreed closely, in the case of water, with Regnnult's results.We are therefore confident that the following numbers for acetic acid closely approximate to the truth. Moreover, as will be pointed out in a, sub- sequent paper, the curve for acetic acid given by this process is abso- Vapour-pressure of Acetic Acid. Solid. Temp. - 5.68" - 0.60 + 1.85 2 -86 5 *32 6.30 6.41 6 -68 7 -09 7 *20 8 *40 8.50 8 -72 9 *16 10 *40 11 *39 11-70 12 -10 12 *20 12.60 13.30 13 -96 14 *30 14 -58 14.85 15 -15 15.40 15.60 15 .SO 16 -09 16.20 16.32 16 * 4 i Pres. --- 1 ' 3 mm. 1 *95 2 -35 2 '80 3 *30 3.70 3 -75 3 *85 4 *oo 4 -05 4.25 4.35 4 -60 4 -70 5.30 5 -75 6 -15 6 *05 6 *05 6 -65 6 -75 7.30 7 *20 7 -95 8 -00 8.40 8.75 8.55 8 -85 8.95 9 '10 9 *15 9 *45 Liquid. Temp. 2 '72" 4 -20 4.70 6.30 7 *06 7 '13 8 '54 8 *58 9 -70 10 *60 10.70 12 '30 13 *70 14 *20 14 *39 14 *72 14.90 15 '50 15 *60 15 -70 16 -75 17 *OO 18 *60 19'20 20 '10 20 *go 21.40 21 * 68 22 -05 22.40 23 'OC! 23 -40 25.60 27 *20 27 *30 31 *30 32-70 36 .l o --- Pres. --- 4 *OO mm. 4 -25 4.75 5.00 5 *25 5 - 4 4 5.95 5 .Y5 6 -20 6-50 6 '75 7.30 8 *10 8.30 8.45 8 '50 8.55 9 '10 9 *15 9 -35 10 *45 9-75 11 *10 11 -05 12 '00 12 -45 12 *65 12 *85 13 -05 12 *go 13 *65 13 -80 15 *95 16 -80 17 *45 21 *80 2z -90 28.30 Liquid. Temp. 36 -9' 40 '1 43 *8 48 '2 48 -5 49 '2 49 -65 50 *5 53-5 57 -4 59 -6 61 -8 68 '5 69 '1 71 -6 73 -2 76 -4 78 -8 79 -8 81 -65 83.4 83 -9 84 -6 87 -5 91 -4 94 -5 97 - 4 98 *6 100-6 103 -3 105 *45 107 -45 110 *4 112 -4 113 -4 114 *1 117.15 --- Pres. 28 *9 mm. 34 '3 41 -7 51 -3 51.*7 53 *7 55 -6 58'1 66 -7 78 -7 87.6 96 *3 127 * 5 131 '9 146.3 156 - 2 177 *3 194 -4 19Y -5 215 -2 228.0 236-3 242 *1 267 -8 307 *Y 344 -3 376 - 4 396 *3 425 *2 460 -3 501 '8 540 -0 587 *1 623 *8 642 -6 657 -5 717 -9THE VAPOUR-PRESSURES OF SOLIDS AND LIQUIDS. 45 lntely coincident with that obtained by the usual process, when air and moisture were rigorously excluded, and when an absolutely pure specimen was employed. These results, which are here arranged in order, mere obtained in eight different series, f o r each one of which the acetic acid was fractionated from a large stock. From the numbers, the following results were obtained by graphic interpolation; it may be interesting to compare them with results obtained by Regnaidt, by Landolt, and by Wiilluer.1 Rarnsar and Young. I Tcnip. P. (solid). 00.. ,. i 2.02 10. .. .. 5.19 20. . . . . 30.. . . . 40. . . . . 50. . . . . , 60.. . . . 70. . . . . , 80 . . . . . I 90.. . . . ' - - - - - - - - 100.. . . . - 110 .....I - P. (liquid). 3 -50 6 .34 11 -80 19 -90 34 *o 56 '2 88 -3 137 *1 202 '0 292 '8 416.5 582 -6 Regnault. Pres. 3.23- 4.89 6.30- 8.20 11 '58-13 '65 ~~ Landolt. Pres. - 7 . 6 12.1 18 *9 29 *1 44.1 66 .O 97 -4 142 -0 204 - 3 290 -6 408 -5 - Wiillner. Pres. 19 .o 30 -5 45 * 5 72 *o 107 -3 155'2 232 -9 346 *7 473 .o - Results are also given by Bineau: a t 15', 7.70 rnm. ; at 22", 14.5 mm.; at 32', 23 mm. ; and by Naumann (Annulen, 155, 325) at 7S0, 185 mm. I n conclusion, it may be pointed out that the correct boiling point of a liquid a t atmospheric pressure is best determined by wrapping cotton-wool, or if the liquid at>tacks that substance, a,sbestos, round the bulb of the thermometer. By this plan, even though the vapour limy be superheated, yet the liquid in contact with the thermometer bulb must be a t the true boiling poiiit, since it has a free surface of evaporation. It is to be hoped that future experimenters will adopt this method, for little confidence is to be placed in the results obtained in t,he usual way.

ISSN:0368-1645    

DOI:10.1039/CT8854700042

出版商:RSC    

年代:1885

数据来源: RSC

摘要:

46 V.-On t h e AppZicatiorL of &-on SiilplintP i n Agricultiwe, and its V ~ Z L L ! as a PLtrLt-Jlbod. By DR. A. B. GRIFFITHS, Lecturer on Chemistry and Physics, Technical College, Manchester, &c. IN tliis paper, details are given of some of my most recent work on the use of ferrous sulphate as a manure. This year, I have grown legumii~ous, root, and cereal crops with and without an iron manure. The experimental plots of land were (as in the experiments last year) in the vicinity of Bromsgrove, Worcestershire. The soil consists chiefly of clay and loam derived from the Lias, or the upper members of the New Red Sandstone formations, and in a former paper, “Expei.imenta1 Investigations on the Value of Iron Sulphate as a Manure f o r Certain Crops,” (this Journal, Trans., 1884, p.71), analyses of this soil are given. This year, six plots of well-drained land were chosen all about the same area. On plots Nos. I and 11, the experiments performed last year on a leguminous crop (beans) were repeated. Plot No. I was manured with crystallised ferrous sulphate of commerce (the quantity applied being 4 cwt. to the acre). Plot No. I1 was left in its normal condition. As in former experiments, the same number of bean seeds were planted on the same day, on each plot of land. At the end of the season the yield of each plot of land was as follows :- TABLE I. ~~ Plot of land (manured with FeSO,). Plot, of land (normal). Total weight of crop (grain + straw) .. .. .. .. .. .. 1 6215 lbs. 1 5325 lbs. I 4793 Ibs. (2.) Weight whcm dry. 4105 lbs. The crop of beans (Vicia faha) grown by the aid of the iron manure ~iclded 44 bushels of grain, whilst the crop grown without the iron manure yielded only 28 bushels, so again there is a marked difference iu the weight of the produce of the two plots of land.Last year (loc. cit.), the iron manure gave an increase of 21 bushels of beans, and now there is an increase of 16 bushels.GRIFFITHS ON THE APPLICATION OF IRQN SULPHATE. ETC . 47 TABLE II.-Awlyses of Ashes of E n t i r e Plants . 4 -910 17 -965 18 -021 5 *999 8 -002 1 -734 40 *831 1 *162 1.376 100 000 ..... Iron oxide. Fe.03.. .............. Potash. K20 .................... Soda. Na. 0 .................... Lime. CaO .................... Magnesia. MgO ................ Silica. SiO. ....................Phosphoric oxide. P,O. .......... Sulphuric oxide. SO, ............ Sodium chloride ................ 1 *002 20 -984 18 ‘213 7 e125 8 -839 2 *836 37 *814 1 -396 1.790 99 -999 .-. Plants grown with iron manure . W i t h iron manure . Plants grown without iron manure . Without iron manure . ...-...... .... I... ~~~~ TABLE 111.-Analyses ?[ Ashes of Pods ~ niitus the Seeds . Iron ocide.Fe20. ................ Potash. K,O .................... Soda. Na. 0 .................... Lime. CaO .................... Magnesia. MgO ................ Silica. SiO. .................... Phosphoric oxide. P.O. .......... Sulphuric oxide. SO. ............ Chlorine ...................... 1 Grown with iron 1 manure . 2 -094 40 999 2 -986 7 ‘001 7 *142 0 *552 36.235 2 *582 0 -407 Grown without iron manure . 0 *924 42 *332 3 -715 6 -548 7 ‘231 0 -525 34 *400 3 -442 0 -883 I loo *Ooo 1 99.998 TABLE TV.-Analyses of Aslies of the Seeds ........ Iron oxide, Fe203 .............. Potash, K20 .................... Soda, Na, 0 .................... Lime, CaO .................... Magnesia, MgO ................ Silica, SiOz .................... Phosphoric oxide, P.O. .......... Sulphuric oxide, SO3 ............ Chlorine ........ , ..... , ....... 0 -575 42 *502 1 -362 4 *783 7 -111 0 ‘800 38 -799 2 a546 1 *511 0 ‘574 42 *498 1 -365 4 -779 7 *124 0 *810 38 ‘800 2 *531 1 *519 99.989 1 100-00048 GRIFFITHS ON THE APPLICATION OF 1883. 4 -221 1 .063 3.158 41 -902 37 *941 3-961 With iron Without manure. iron manure. The analyses were performed in duplicate.From the tables (pp. 46, 47)’ it will be seen that the crop of beans was greatly increased by manuring the land with iron sulphate ; in fact as much as 1422 lbs. when gathered, and 1220 lbs. when dry, also with an increase of 16 bushels of grain. Comparing them with the results obtained last year, the analyses of the ashes of the various parts of the plant agree very remarkably. Last year an increase of 1573 !bs. was obtained with the iron manure when the crop was gathered, and 13951bs. when dry, and an increase of 21 bushels of grain over the crops grown without the iron manure. From last year’s analyses and in those given in the present paper, it will be seen that the percentage of ferric oxide in the ashes of the various parts of the plant is much larger when the plants have been grown with ferrous sulphate than without it ; and also that the phosphoric oxide in the ash increases as the ferric oxide increases.I n Table IV, which is theresult of the analyses of the ashes of the seeds, it is plain that there is no difference whether the crop is grown with or with- out an iron manure. Thus confirming for a second time on a large scale that the ash of the seed or embryo of a plant is very constant in its composition whatever manure is appiied to the land. The next two tables illustrate the percentage of Ir’e,O, and P,O, in the ashes of the two seasons’ crops. 1884. ?Fithout Difference. manure. iron manure. ___-------___,--_______ 4.910 1 ‘008 3 ‘908 40.831 37.814 3 -017 I With iron Fe,O,. P,O, . 1883. With iron 1 Without manure.iron manure. Difference* 0.911 1.110 1.821 Fe,O3. 2.021 1884. With iron Without manure. iron manure. -- ---- 2.094 0.924 1-170 36.235 34.400 1-835 TABLE VI.-Fods minus Seeds.IRON SULPHATE IN BGRICULTL’RE. 49 From the above, i t is evident that there is an increase of about 3 per cent. of ferric oxide and phosphoric oxide in the ashes of the entire plant, when grown iu a soil containing an iron manure ; and an increase of about 1 per cent. of ferric oxide, and nearly 2 per cent. of phosphoric oxide in the ashes of the pods. I am fully convinced that the proposition I advocated nearly two years ago (Chem. News, 47, 27), that a “fairly large proportion of soluble irorL in a soil i s favourable to the growth of plants deaeloping n large amoicnt of clilorophyll,” is a proved fact; and this has been con- firmed by all my subsequent researches, and by the recent determina- tiom of chlorophyll which Dr.W. J. Russell has performed on plants grown with and without an iron manure. I shall refer again t o Dr. Russell’s experiments in the latter part of this paper. Cereal Crops. The next crop to be considered is the cereal. As in the experi- ments with beans, these wheat crops were grown on well-drained land and under like conditions as to sunshine and rainfall. Of two plots each of the same area, one was manured with iron sulphate (+ cwt. to the acre) and the other was left in a normal condition. At the end of the season, the yield of each plot was as follows :- TABLE VII. Plot of land manured with FeS04. Plot of land (normal).Total weight of crop (grain + straw) ,. ,. .. .. .. .. 5021 lbs. 1 4301 lbs. I 5030 lbs. 1 4360 Ibs. The crop of wheat grown by the aid of the iron manure yielded 28 bushels of grain, whilst the crop grown without the aid of the iron manure yielded 27 bushels of grain. From these investigations, an iron manure does not appear t o be of so great a value as a plant-food in the case of the cereal as in the leguminous crop; for the yield is much the same whether an iron manure is used or not. But there is one well ascertained fact in favour of the use of ferrous sulphate for wheat crops, and that is, t h e plants VOL. XLVII. E50 GRIFFITHS ON THE APPLICATION OF Grown with iron manure. were healthier and completely resisted the attack of the wheat mildew (“rust ”) : whilst the other crop not manured with iron was attacked to a certain extent; and this may account for the increase of 1 bushel of grain over the crop grown on the normal plot of land.As in the experiments with the leguminous crop, analyses (in duplicate) of the ashes of the various parts of the plants of each plot of land were made with the following results :- Grown without iron manure. TABLE VIIL-Analyses of Ashes of E’ntire Plant. - 2 *ooo 12 ‘561 2 ’4q10 3 -710 5 -334 64 -724 4.524 4 ‘222 0 ”514 99.999 ------ Iron oxide, Fe,O, ............... Potash, K20,. .................. Hoda, Na,O .................... Lime, Ca.0 .................... Magnesia, MgO ................ Silica., SiO, .................... Pho.sphoric oxide, P,O, .......... Sulpliuric oxide, SO, ............Chlorine ...................... I-----I---- ------ 2’521 12 ‘024 2.135 3 *634 5 -412 64 -846 4 *424 4 *511 0 -493 100 ‘ GOO TABLE 1X.-Analyses of Ashes of Seeds. ~~ ~ I Grown with iron manure . I Grown without iron manure. Iron oxide, Fe,O, ............... Sods, Na,O .................... Lime, CaO ..................... Magnesia, MgO ................ Silica, SiO, .................... Phosphoric oxide, P,05 .......... Sulphuric oxide, SO, ............ Chlorine ..................... Potash, K,O ................... 1.142 31.024 2 ’504 10.503 3 *676 1 *937 46 .d%d 1,300 0 *cis2 100~000 ---- 1 *124 32.392 2 *497 10 *668 1 964 45.269 1 *294 1.007 3.784 99.999 The Zeaves of the wheat gave 3.814 per cent. of ferric oxide when the crop had been grown with iron, and only 1.642 per cent.when not so treated. The ash analyses in the case of the entire wheat plant show that there is an increase of about per cent. of ferric oxide in the plants manured with iron; but this is all that can be said, and the phos- phoric oxide is increased by nearly 1 per cent.IRON SULPIIATE IN AGRICULTURE. Plot of land manured with FeSO,. -__---__ 51 ------- Ivon ox7..de, Fe20, .............. Potash, K20.. .................. Soda, Na,O .................... Lime, CaO .................... Silica, SiO, .................... Phosphoric oside, P20, .......... Sulphuric oxide, SO2 ............ Magnesia, M go ................ Chlorine.. ..................... Root Crops. A8 before, two plots of land were chosen; one was manured with iron sulphabe (4 cwt.to the acre) and the other was left normal. On these two plots of land, turnips were grown ; the yield of each plot was as follows :- TABLE X. -. Total weight of crop (root + leaves) ............ 50,104 lbs. Plot of land normal. ----__.- Weight; when gathered. 44,216 lbs. The plot of land manured with ferrous sulphate gave 164 tons, whilst the plot of land in its normal state gave only 13 tons of turnip roots. It is evident that there is a great increase in the produce by manuring the land with iron sulphate. The next two tables give the analyses of the ashes of this root- crop. TABLE XI.-Analyses of Ashes of Turnip Roots. Grown with iron manure. --- 1 '210 43 *a43 3 *862 12 968 1 .goo 0 *816 1'7 -910 5.010 3 '487 Grown without iron manure.---- 0.321 50 *124 3 -621 13 '024 2 .ooo 1.215 16 412 G .954 6 328 The analyses in XI and XI1 (which were done in duplicate) show that there is an increase of nearly four times the amouut of frrric oxide in the turnip roots grown with the iron manure over those grown without it ; and in the turnip leaves there is more than three times the per- E 2GR'IFFITHS ON THE APPLICATION OF Grown with iron manure. -_- ----- ------ Grain ........................ 4 -920 Straw ........................ 2 *188 centage of ferric oxide in the ashes of the crop grown with iron as compared with that grown without iron. Grown without iron manure. -- 4,869 1.198 TABLE XI.-Analyses of Ash of Turnip Leaves. Grain ........................ Chaff'. ......................... Straw.......................... ----- ----- ------- ] ~ o n ozide, Fe20, .............. Potash, K20 ................... Sods, Na,O .................... Limz, CaO ................... Silica, SiO, .................... Phosphoric oxide, P20, .......... Chlorine.. ..................... Magnesia, MgO ................ Sulphuric oxide, SO3 ............ 1 899 0 *820 0 -674 3.393 --- Grown with iron manure. 3 -202 26.124 6.210 34.452 2 *541 1 -462 6 *943 13 *910 5 -154 99 -998 Grown without iron manure. -_I_-- 0 *986 27 -921 7.024 35 *G20 4.199 2 .I34 4.218 11 *999 5.898 99 *999 Nitrogen in the Crops. The next set of three tables gives my determinations of the per- centage of n i t r o g e n i n each crop. TABLE XIII.--ni'itrogen in Beans (Vicia faba). TABLE XIV.-Nitrogen ii~ Wheat (Trit'icum vulgare). Grown with iron manure.Grown without iron manure. 1.802 0.821 0.363 2.9S6IRON SULPHATE IX AGRICULTURE. 33 Grown with iron manure. TABLE XV.--Nitrogert i n Turnips (Brassica rapa). Grown zoithout iron manure. Root .......................... Leaf .......................... ---______---- I---I---- - 2.189 2 *181 4 280 8.265 6 . 4 9 6.416 ---- __--______--...--I Soluble carbohydrates.. \h'oodyfibre ........ ,. Fat.. ................ I have also estimated the percentage of soluble carbohydrates (soluble in dilute acids), woody fibre (insoluble in dilute acids), and fat. Table XVI details the results. Plants grown withozct iron manure. Beans. 1 2:;. Wheat. Ez:: Turnip. ______ ~ .......... 49 -32 38 *24 66.21 31 *95 6.29 '7.93 33.67 1 2-98 43.69 1 45 1.32 ~ 1.48 0.32 1.65 1 TABLE XVI.Plants grown with iron manure. I-- /--I-- I--I--- ------ Soluble carbohydrates.. 55 -81 I Woody fibre.. ........ 10.21 Fat.. .............. 2.94 I 1.82 0.81 The above table shows that the carbohydrates, woody fibre, and t'at are all more or less increased when the plants have been grown by the aid of ferrous sulphate. The next table gives the determinations by Dr. W. J. Russell of the d u t i v e amounts of c h l o r o p h y l l in samples of t,he leaves from each of my crops. He has kindly determined the relative amounts in equal weights and in eqrial areas of each sample, with the following re- sults :-54 GRIFFITHS ON THE APPLICATION OF TABLE XVIL-Dr. Russell’s Estimation of the Relative Amount Of Chlorophyll in the Leaves.No. of Sample. 1 ........ 2 ........ 1 ........ 2 ........ 1 ........ 2 ........ Leaves. Beans (grown with FeSO,) ........ Beans ( .. withoict FeSO,) ..... Turnip ( .. without FeSO,).. ... Wheat ( .. with .. ).. . . . Turnip (grown with FeSO,) ....... Wheat ( .. without .. ). .... I n equal areas. -- 100 79 59 4Q 115 100 I n equal weights. 100 76 61 39 ’72 81 - The leaves were collected on the same day, and were of the same age in each case. From the above determinations, it is evident that iron nourishes the chlorophyll granules, a proposition I advanced some few years ago. From Dr. Russell’s analyses, it will be seen that in each plant-with the exception of wheat-when the plants have been grown with an iron manure, the chlorophyll in “ equal areas ” and in “ equal weights ” has been greatly increased.And now comes the question, what has increased the chlorophyll ? The iron, because it nourishes the granules, and always is to be found near to the granules themselves in the crystallised condit>ion when sections of the leaves are examined microscopically. (See my paper, Cjienz. SOC. J., Trans., 1883, p. 195.) General Conclusions. My enquiries on this subject have led me to the following con- clusions as to the effect of ferrous sulphate as a plant-food :- I. I n the case of those plants which develop a large amount of chlorophyll, for examples, beans, cabbages, and turnips, an iron manure is most beneficial, considerably increasing the harvest. (See the present paper and Trans., 1884, pp. 71-75 ; Chenz.News, 47, 27 11. An iron manure greatly increases the percentage of soluble carbohydrates, woody fibre, and fat in certain plants, this, of course, being an outcome of the increase in the amount of chlorophyll in the leaf; for the chlorophyll forms starch, which is converted into “ carbohydrates,” cellulose, &c. 111. I have found monoclinic crystals of ferrous sulphate near t o the chlorophyll granules when sections of the leaves are examined under the highest powers of the ~nicroscope, the crystals being tested chemically and proved to be ferrous sulphate. (See Trans., 1883, pp. 125-197 ; also Journal Royal Microscopical Society, 1883, p. 536.) -78.) (See the present paper.)IRON SULPHATE IN AGRICULTURE. 55 IV. That in certain cases the phosphoric oxide in the ashes of plants grown with this new manure increases as the ferric oxide increases.(See present paper ; also Trans., 1884, pp. 71-75 ; Chem. News, 47, 27-28.) V. That ferrous sulphate is a good plant-food, proved by the increase in the harvest as shown above; yet in excess it acts as a poison to plant-life, a solution containing 3 per cent. of FeSOI being fatal to most plants; and when the amount of ferric oaide in the ash of all the plants examined was 10yer cent. the plant previously died. (See Chem. News, 50, 167; Chemiker-Zeitung, 1884, p. 757; and Chem. News, 50, 193,) VI. The sulphur of the ferrous sulphate acts as a, food for the protoplasm of the cell, and the iron for the chlorophyll itself. (See (:hem. News, 49, 237, 265; 50, 32 ; also Chefiaiker-Zeitung, 1884, 1). 863 ; this Journal, Abstr., 1884, p. 848.) VII. The nitrogen in the plants grown with ferrous sulphate is to some extent increased. VIII. Iron sulphate increases the amount of chlorophyll in the leaf. (See Dr. Russell’s estimations in present paper.) IX Iron sulphate acts i n the soil as an antiseptic agent, destroy- ing t o some extent certbin parasitic diseases which attack our crops. (See Ohern. News, 49, 279 ; Abstr., 1884, p. 1070.) X. My experiments have also led me to conclude that the most active rays of white light for root-absorption are between Fraunhofer’s lines D and E. (See present paper.) (See Trans., 1884, pp. 74-75.) In conclusion, I wish to tender my best thanks to Dr. W. J. Russell, F.R.S., for his determinations of the relative amounts of chlorophyll in the plants. I also wish to thank Dr. T. L. Phipson, F.C.S., and my friends Mr. T. P. Wright, Dr. J. Johnstone, M. E. C. (jonrad, F.C.S., of Bordeaux, and Mr. E. L. Rhead (Demonstrator in Chemistry, Technical College, Manchester), for many kind sugges- tions.

ISSN:0368-1645    

DOI:10.1039/CT8854700046

出版商:RSC    

年代:1885

数据来源: RSC

摘要:

VI.-Action of the Halogens o n t h e Salts of Trimethylsul~7LiiLe. By LEOKARD DQBBIN, Ph.D., and ORME MASSON, M.A., D.Sc., Chemical Laboratory of the University OE Edinburgh. I. Action qf Iodine on the Haloid Salts. WHEN dry trimethylsulphine ioaide is shaken up with an ethered solution of iodine, i t becomes converted into a heavy black tarry liquid, which smells strongly of iodine; this is easily soluble in alcohol, and it reappears unchanged when the solution is evaporated. It decomposes slowly when warmed with water, iodine being evolved. It was not found possible to obtain the substance in a state fit for analysis, but there is no doubt that it is of the order of the so-called polyiodides. Jiirgensen ( J . pr. Chenz., 3, 338) obtained a similar compound of triethylsulphine, which gave a crystalline double salt with mercuric iodide.The bromide and the chloride of trimethylsulphine behave in a similar manner ; but, if the tarry product is washed with ether and dissolved in alcohol, large reddish-black crystals arc obtained when the solution is evaporated over sulphuric acid. These crystals smell of iodine and are not stable in the air. I n thtse circumstances, it was not thought worth while to analyse them, but their general resemblance t>o the more stable compounds described below leaves no doubt in our minds that they consist respectively of the bromo-diiodide and the ch loro-&iodide of trimethylsulphine,-Me,SBrI, and Me,SClI,. A compound in all respects similar to, and probably identical with, the second of these, is obtained by acting on trimeth~lsulphine iodide with iodine monochloride.11. Actio?& of Bromine o n the Iodide. When bromine vltpour is poured over dry trimethylsulphine iodide, niuch beat is developed and the colonrless crystals melt to a dark red liquid. The reaction goes more quickly, and, in fact, with violence, if the bromine is added in the liquid state. When addition of bromine produces no further action, the heavy red oil is exposed for. a short time to the air, whereby it loses most of the excess of bromine and becomes solid. The ma,ss is then broken up, shaken two or three times with a little ether, to remove the last traces of bromine, and dissolved in sufficient hot alcohol ; as the solution cools, an abundant crop of brilliant orange-red crystals is deposited. The mother-liquorDOBBIX AND MASSOPU': ACTION O F THE HALOGENS, ETC. 57 gives a further but smaller yield when allowed to evaporate in a vacuum; these crystals are of a somewhat darker shade in colour than the others, although of the same composition.The total yield approaches rery nearly to that indicated by theory. Analysis shows the compound t o be trimethy ZsuZphine dibronziodide, Me,STBr2. The sulphur was estimated by combustion with a .niixture of five parts of potassium carbonate t o one of potassium chlorate,- a method we would recommend for those cases where the sulphur is combined directly with methyl, &c. The halogens were estimated in solutions obtained by decomposing the salt with dilute sulphurous acid: in one, the bromine was determined after removing the iodine with cup& sulphate ; in the other, the total halogen was determined as silver salt.I. 0.2625 gram gave 0.0946 gram GO, and 0.0623 gram H20. 11. 0.2564 ,, 0.0944 gram CO, and 0.0605 gram H,O. 111. 0.2329 ,, 0.1421 gram BaS04. IV. 0.2258 ,, 0.2330 gram AgBr. V. 0.1073 ,, 0.1797 gram mixed AgBr and Ag'l. 1 I Calm- I lated. C, . . . . . , . 9.87 H, , . . . . . . 2.47 s .. .. . ,. 8.79 I . . . . . * . 34.89 Er,. . . . . , . 43.96 Found. l----I-- I--- -- Properties of Trimethylsulphi?Le Dibromiodide.-The orange-red crys- tals are not deliquescent, and are perfectly stable in air. When heated, they melt a t 94-95', with partial decomposition. A brown oily distillate passes over at higher temperatures and, finally, a t about 180', methyl sulphide and iodine vapour.The crystals are somewhat soluble in cold alcohol or ether, and much more so in hot alcohol. The alcoholic solution seems to undergo slight decom- position on long standing. The reaction with water is very characteristic ; for the crystals, when shaken with it, with or with- out the application of heat, quickly melt to a black oil, which resembles the periodide in appearance. On long boiling, it dissolves in the water, iodine beiag evolved. Platinic cldoride, added t o the alcoholic solution, produces a bulky flesh-coloured precipitate.58 DOBBIN AND MASSON: ACTION OF THE HALOGENS This is soluble in hot water, from which it crystallises in the golden cubes and octahedra chai*acteristic of trimethylsiilphine platino- chloride.Estimations of the platinum confirmed its identity. I. 0.237’7 gram of the salt gave 0.0824 gram of platinum. 11. 0.2436 ,, Y, 0.0843 ,, 9 , Found. Calculated for r-A 7 (Me3S) 2PtClo. I. 11. Pt per cent. .. . . . . . . . . . 34.94 34-66 3460 Freshly precipitated silver oxide, when shaken with the alcoholic solution, is converted into halojid salt, the liquid at the same time losing its orange colour and acquiring an alkaline reaction. This is due to the formation of trimethylsulphine hydroxide. On evapora- tion, some crystals of iodoform are obtained. Silver nitrate and silver suZp3hate also decolorise the alcoholic solution, rendering it strongly acid. The corresponding salts of trimethylsulphine are probably pmduced, but the reactions have not been fully investigated.Alco- holic potash, added to the alcoholic solution till the colour is gone, gives a yellow precipitate which increases on the addition of water, and is proved to be iodoform by its smell and general properties. The filtrate from this contains halo’id salts of potassium and tri- methylsulphine. The final action of aqueous potash on the crystals themselves is the same, except that no iodoform is produced; but there seems to be a t first an unstable product formed which impaxts an opalescent green colour to the solution. Ammonia solution a t once converts the crystals of the dibromiodide into a black solid matter which, after carehl washing and drying, has the appearance and properties of iodide of nitrogen, exploding with great violence and extreme readiness.The filtrate contains haloid salts of am- monium and trimethylsulphine. I f the gas be blown from t h e mouth of a bottle of ammonia solution over the orange-red crystals, these at once acquire a dark green colour which, however, the warmth of the hand is sufficient to dispel. But if the crystals be submittfed to a current of dry ammonia, this initial green colour quickly gives place to black, which is in tarn succeeded, in the course of two hours or more, by a uniform light apple-green. These phenomena are due to the formation of a direct addition product of the composi- tion Me3SIBr2,2NH3. It is an amorphous, non-explosive, light-green solid body, stable only in an atmosphere of ammonia. In a current of dry air, it loses ammonia and reverts to the intermediate black condition, the loss being very rapid at first, then slower and slower, Ammonia gas acts quite differently.ON THE SALTS OF TRIMETBYLSULPHINE.59 though it probably becomes complete in the course of time. At a temperature of 75-80' the compound melts, ammonia is rapidly evolved, and the original dibromiodide is left. Mere solution i n alcohol effects a similar decomposition. Water dissolves it with liberation of iodine, which explains the formation of iodide of nitrogen by the action of excess of ammonia solution on the dibromiodide. The composition of this very unstable compound could be deter- mined only synthetically. It was done in the following manner. The powdered dibromiodide was placed in a porcelain boat inside a short glass-stoppered tube, the weight of the tube and boat together being known, as well as that of the substance taken.The tube was then clamped in a horizontal position, and closed with a cork through which passed two tubes-one for outlet and the other, reaching to the far end, for inlet of the ammonia. The gas, dried by passing through U-tubes containing solid potash, wars then allowed to act for a quarter of an hour, at the end of which time it was displaced for a few seconds by dry air, and, the cork having been quickly exchanged for the glass stopper, the tube was weighed. This operation was repeated several times, unt,il the weight became constant. While weighing-though this was done a,s quickly as possible-the light green colour became tarnished with black a't the edges.0.7172 gram of the dibromiodide became 0.7841 gram by absorption of ammonia. Gain per cent. 9.34 9.32 Calculated for Me,SIBr2,2NH3 . . . . Found .. . . .. .. .. .... .. .. .. .. .. 111. Action of Chlorine on t h e Iodide. Chlorine, well washed and dried, is passed into a flask containing dry powdered trirnethylsulphine iodide. This a t once melts, much heat being developed, and a pasty black substance is formed, which quickly changes to a light yellow solid body. If the flask be sur- rounded with cold water, the product will remain of a dark colour, for the reaction is checked a t the first stage ; but it n a y be completed by afterwards substituting warm water for the cold and continuing the passage of the chlorine. The final product consists of trirnethyl- suZphine dicl~loriodide, Me,SICl,.It is readily purified in the same manner as the dibromiodide, and separates from the hot alcoholic solution in an abundant crop of canary-yellow crys t'als, which closely resemble the di bromiodicle in general properties. The mother-liquor, when evaporated in a vacuum, yields a smaller crop of crystals, of a darker shade, but identical composition. On long standing, the alco-60 DOBBIN AND MASSON: ACTION OF THE HALOGENS holic solution undergoes some decomposition, distinctly more than in the case of the dibromiodide. Annlysis.-I. 0.1953 gram of the substance gave 0.0931 gram CO, and 0.0582 gram H,O. 11. 0.1847 gram gave 0.0892 gram CO, and 0.0565 gram H,O. 111. 02321 ,, 0.1959 ,, RaSOp. ~~ -- c,. ......... I .......... c12 ......... 2 .:::: :: :: -- Calculated. 13 *09 13 -05 3-27 1 3.31 11.63 - 46 -18 - 25 -83 1 - 1to.00 I - ------- Found. 11. j 111. I-- --- I - I - Pmperties.-The yellow crystals of the dichloriodide are stable in air a t ordinary temperatures. They melt a t 103-104" with partial decomposition, evolve a, brown oily distillate when further heated, and the vapours of methyl sulphide and iodine above 170". Platinic chloride, added to the alcoholic solution, gives a bulky precipitate, shown to consist of trimethylsulphine platinochloride by its general properties and by the following analyses :- I. 0.1176 gram gave 0.0404 gram of platinum. 11. 0.1621 ,, 0.2458 ,, AgCI. Calculated for ( Me,S),PtmC16. Found. Pt ............ 34.94 (I.) 34.35 C1 ............ 37-71 (TI.) 37.51 With siZver salts and with caustic potash, the dichloriodide acts in a manner precisely similar to the dibromiodide.Ammonia solution de- composes i t with formation of iodide of nitrogen. With perfectly dry amwzoizia gas, it forms the compound Me,SIC1,,2NH3, the varions stages in the reaction being hardly distinguishable from those in the formation of the corresponding dibromiodide derivative. The final product, however, is not so light in colour ; and, when exposed to the atmosphere, it not only loses ammonia but absorbs moisture, and becomes converted into a wet black paste, which is not the case with its analogue. In other respects it resembles it closely. The compo- sition was determined synthetically in the manner already described.ON THE SALTS OF TRIMETHYLSULPHINE. 61 0.2738 gram of the dichloriodide became 0.3067 gram by absorption of ammonia :- Gain per cent.Calculated for Me,SIC1,,2NH3. ....... 12.36 Found.. .......................... 12.@2 IV. Action of Iodine Monochloyide on the Cliloyide. This results, as might be expected, in the formation of trinzethyl- sulphine dichloriodide. The reaction which takes place when the iodine monochloride is poured gradually over the dry chloride closely resembles that produced by t,he act,ion of bromine on the iodide. Much heat is developed, and the salt melts to a black pasty mass. This, however, assumes a light yellow colour and dry consistency when purified by a few washings with ether. The crystals obtained by cooling the hot alcoholic solution are identical in appearance and properties with those of the dichloriodide obtained by the method already described. The yield is large.V. A c t i o n of Iodine Monocldoride on t h e Bromide. This action produces a body which, after washing with ether, separates from hot alcohol in the form of crystals, which are inter- mediate in colour between the light yellow dichloriodide and the orange-red dibromiodide, both of which it otherwise closely resembles. It melts at 87" with partial decomposition, which becomes complete a t 180-190". Combustions of the substance gave the following results, showing that it consists of t i i m e t h y h 1 p h i ? i e chlorobromiodide, ISIeJSIBrC1, I. 0.3071 gram substance gave 0.1314 gram CO, and 0.0832 gram 11. 0.3228 gram substance gave 0.1378 gram GO, arid 0.0894 gram H,O. H,O.Found. Calculated €or +- Me,SIBrCl. I. 11. C ............ 11-27 11.67 11.64 H 2.82 3.01 3.07 . . . . . . . . . . . . VI. Action of Bromine on t h e Bromide. This action resembles that of bromine on the iodide, but the pro- perties OP the products of the two reactions are quite different. Heat is evolved, and the crystals melt to a dark-red heavy liquid, which does not, solidify when washed with ether ; nor can it be crystallised62 DOBBIN AND MASSON: ACTION OF THE HALOGENS from alcohol, as it separates unchanged in appearance when the soh- tion is evaporated. When surrounded with a freezing mixture of snow and salt, it becomes more viscous but does not solidify. It smells OE bromine; and it is slowly decomposed on exposure to the atmosphere, drops of a solution of trimethylsulphine bromide (which is deliquescent) making their appearance on the surface of the liquid after a day or two.It is decomposed much more quicklywhen heated on the water-bath, and tlie bromide is then obtained in the crystalline state. Even when the subst,ance is kept in a desiccator containing sul phuric acid, there is cont'inuous, though slow, loss of bromine. When shaken with water, it is slowly decoaposed and passes into solution. As such a body could not be obtained in a state fit for analysis, it was thought desirable to make some quantitative synthetic expe- riments with perfectly dry materials. The purity of the trimethyl- sulphine bromide was first ascertained by an estimation of its bromine. 0.2260 gram of the salt gave 0.2695 gram AgBr.Calculated. Found. Br ...... .... .... 50.95 50.74 In this and subsequent experiments with the bromide and chloride, which are both extremely deliquescent, special precautions were em- ployed to obtain the salt in a perfectly dry state. It was placed in a small porcelain boat inside a glass tube, the boat and tube, with it ground glass stopper, being previously weighed. The tube was then placed horizontally, without its stopper, in a larger tube surrounded with boiling water, and closed by a doubly perforated cork. The salt being thus kept a t loo", dry air was led Over its surface for from two to three hours. The tube was then quickly stoppered and weighed with its contents. By replacing the glass stopper hy a cork provided with inlet and outlet tubes, it was possible afterwards t o operate on the weighed salt with a stream of chlorine, or of air charged with bromine vapour, and to weigh the product (after clearing the tube out with dry air) without more than a momentary exposure to the atmosphere.0.2441 gram of the dry bromide was exposed for two hours to a perfectly dry current of air charged with bromine vapour. The red oil, which was rapidly formed, continued during that time to increase in volume, in depth of colour, and in mobility. The increase in weight was 1.3'208 gram, which is equivalent to a gain of from t,en to eleven atoms of bromine by one molecule of the bromide ; and there is no reason to suppose that the absorption would have stopped there, Dry air was then passed over the surface of the liquid for several hours, aud weighings were made a t intervals ; after which the tubeON THE SALTS 03' TRIMETHPLSULPHINE. 63 and its contents were left for three days in a desiccator containing solid potash and then again weighed.The following table shows the results of this experiment :- Air passed. -- - 2 hours . . . 4 ,) ... 6 ,, ... 8 ,, ... 9 ,, ... 11 ), ... After 3 d q s orer IiOH Weight. --- 1 *5649 0 *7510 0 -5483 0 -5031 0 *477'/ 0 *4689 0 -4613 } 0.4467 Weight gained. --- 1 -3208 0.5069 0 *3042 0 -2590 0 -2336 0 *2248 0 '2172 0 -2026 Gain per cent. 541 207 124 106 95 92 89 83 Mols. of Br gained by 1 mol. of Me3SBr. 5.30 2'03 1.22 1 0 9 3 0 *go 0 -87 0 -81 Now, the calculated percentage gain, for the formation of Me,SBr,, is 101.9, so that it is obvious that this compound, if formed at all, tends, on the one hand, to absorb a large excess of bromine when in an atmosphere containing it, and, on the other, t o decompose steadily when in air free from bromine.As it is impossible, however, to isclate this or any other definite compound, a11 we can assert is that bromine does combine with trimethylsulpliiiie bromide with develop- ment of heat, and that the analogy of the dibromiodide is in favour of the supposition that the tribromide is formed. VII. Action qf Bromine on the C l b r i J e . This action is precisely similar in character and appearance to tbat of bromine on the bromide. A dark-red oil is rapidly formed, which goes on absorbing bromine as long as it is exposed to air charged with the vapour of that substance, but gives it up again, a t a pro- gressively decreasing rate, in a current of dry air or i n a desiccator containing solid potash.It is unuecessary to give the details of the experiments, as they were similar to the one described in the last paragraph: they afforded no evidence in favour of the existence of the chlorodibromide, Me3SBr2Cl, or of that of any other definite compound.64 DOBBIN AKD MASSON: ACTION OF THE HALOGENS VIII. Actim of Chlorine on t h e Bromide, At the first touch of chlorine, the colourless crystals of trimethyl- sulphine bromide assume an orange tinge ; and then they gradually melt to a clear yellow viscous liquid, in which, at first, solid orange- coloured pieces may be seen floating. The final product smells of chlorine, which it evolves when exposed over solid potash or sub- jected t o a current of dry air.Wa,ter acts on it, causing the liberation of minute bubbles of chlorine. The following quantitative experiment was made. 0.2i46 gram of the dry bromide was subjected to the action of dry chloriue for one hour, at the end of which time it was found to weigh 0.4100 gram. A second hour's chlorination increased this to 0.4169 gram ; and it did not increase further. This i s equivalent to a gain of 51.8 per cent'., or 1.146 molecules of chlorine by one molecule of the bromide, the formation of Me3SBrC12 requiring a percentage gain of 45.2. The product was then allowed to stand for two days over solid potash, after which the weight was found to be 0.3873 gram, which corresponds to a gain of 41.0 per cent., or 0.907 molecule of chlorine by one molecule of the bromide.On further exposure it con- tinued to lose weight, though slowly. The experimental evidence in this case, therefore, decidedly favours the belief that trimethylsulyhine dichlorobromide, MeJSBrC12, is formed, which is what one would expect from the analogy of the dichlor- iodide. No doubt, the very different physical properties of chlorine and bromine may account for the fact that trimethylsulphine bromide (and, as will be seen, chloride) absorbs but a sniaIl excess of the former, though an apparently unlimited excess of the latter. IX. Action of C h l o h e o n the Chloride. I n order to observe this action properly, it is necessary to have both the chlorine and the chloride absolutely dry.If this precaution be taken, the crystals will turn yellow and begin to melt the instant the chlorine touches them. There is no sensible development of heat. Afler a few minutes the whole mass becomes converted into a clear pale yellow liquid, which undergoes no further change of appearance, though i t goes on absorbing chlorine f o r some few minutes longer. This product has some charact,eristic properties. When exposed to the air f o r a very brief period, i t suddenly solidifies; and when once this (apparently physical) change has taken place, the substance is not in the least affected by subsequent exposure to a chlorine current, however prolonged. Thus, in one experiment, the current of chlorine was stopped as soon as the product appeared to be uniformly liquid (five minutes from comniencement), and dry air was thenON THE SALTS OF TRIJLETHYLSULPHIXE.65 weight of chloride teken. passed through to sweep out the tube. This caused the substance to solidify, It was weighed and then again exposed to chlorine €or half an hour; but the weight was found to be unchanged, though the quantity of chlorine taken up mas not nearly so large as in other experiments. I n another case, after nearly the maximum amount had been absorbed (twenty minutes from commencement), some accidental cause produced sudden solidification ; and the rapid escape of dissolved chlorine caused the formation of a number of small crater-like excrescences on the surface. The action of a drop of water on the solid compound is particularly striking, for it causes a violent effervescence of chlorine.At the same time trimethyl- sulphine chloride passes into solution. Absolute alcohol and ether both decompose i t in a similar manner; but the cblorine is, of course, not liberated as such. The chlorinated chloride is decomposed more rapidly in dry air than any of the other compounds already described. The purity of the chloride employed in the experiments tabulated below was tested by means of a chlorine estimation. 0.3100 gram of the salt gave 0.3899 gram of AgCI. Calculated for Me,SCl. Found. C1 .... .. .. .. .. 31.55 31-1 I weight of product. In every experiment, the salt was dried for fi-om two to three hours in the manner already described. In experiment I the tube was swept out wihh a current of dry air before weighing, so that the product assumed the solid state.In the other cases, this was avoided by weighing the tube full of chlorine (with its cork, and tubes closed by caoutchouc caps) ; and the weight to be deducted for this extra chlorine was determined as accurately as possible by prelimi- nary experiments. In experiment IV it was proved that the maximum weight had been gained. per cent. No. of experiment --- I ,. .... 11 ...... 111 .. .... IV .... .. c1 gained by Me,SCl. 0 -2770 0'3110 0 *2377 0.2344 0 -3874 0'5170 0 *4068 0 *4036 39 -85 66.23 71 '14 72 *18 0 -631 1.049 1 a137 1.144 (maximum) Time allowed. -- In order to prove bejond doubt that the reaction consists in the simple addition of chlorine, and that there is no substitution of that VOII.XLVIT. I?66 DOBBIN AND MASSON: ACTION OF THE HALOGENS element for hydrogen, a com'bustion of the product of experiment I was made, the results of which may be compared with those obtained from the unacted-on chloride, I. 0.2634 gram of the unacted-on chloride gave 0.3045 gram CO, and 0.1918 gram H,O. 11. 0.2770 gram of the chloride, after it had been acted on by chlorine, gave 0.3217 gram CO, and 0-2020 gram H,O. Found. r---- 7 I. 11. Calculated Before Aft.er for Me,SCl. chlorination. chlorination. C ............ 32.00 31.72 31.67 H ............ 8.00 8-14 8-10 From these experiments, it seems fair to conclude that trim,ethyZ- sulphine trichloride. Me,SCl,, is formed-a peculiar and unstable com- pound possessed of a limited power of dissolving chlorine when placed in an atmosphere of that gas.X. Action of Halogens o n the Sulphnte. We have not yet fully investigated the reactions of trimethyl- sulphine sulpbate with the halogens; hut we have ascertained by experiments the following fact8. (1.) Iodine does not combine with it in the same way as it does with the haloid salts. (2.) Bromine combines with it to form a red solid body, which resembles the dibromiodide rather tlhan the prodncts obtained by brom ination of the bromide and chloride, but is less stable than the former. (3.) Chlorine acts on it to form a product which close17 resembles the trichloride in its general proporties, and particularly in the rapid effervescence of chlorine which occurs when water is dropped on it, We are pursuing the investigation of these reactions and of those of the halogens with other salts of trimethylsulphine.XI. Summary and Theoretical Considerations. It has been shown that all the haloid salts of trimethylsulphine combine directly wich chlorine, bromine, iodine, and iodine mono- chloride. In no case does there occur a replacement of one halogen by the other. The product of each reaction may be formulated as MesSX, (if we understand X to represent C1, Rr, or I, indiscriminately), this being proved with certainty in some cases, and fairly inferred in those where proof is wanting. In the following table, which shows the ten possible variations of the general formula, a query (?)ON THE SALTS OF TRIMETHYLSULPHINE. 67 indicates that the substance has not been proved by quantitative experiments to have the formula attributed to it.This proof might be obtained in the caees of Nos. I1 and 111; in those of I, WI, and VIII, this is rendered impossible by the readiness with which the compounds dissolve excess of the halogen, a,nd by their unstable na,ture. - NO. I I1 I11 IV V V I TI1 VIII IX X - Me,BT,? .. Me3S12Br ? . Me3S12Cl ? . Me,STBr2 . . Me3SIBrCl. Me,SICl, , . Me,SBr, ?.. Me,SBr,Cl? Me,SHrCl, . Me,SCl,.. Appearance. Black tarry matter.. .... Dark crystals .......... Dark crystals .......... Orange-red crystals .... Orange crystals ........ Yellow crystals ........ Orange-red viscous liquid Orange-red viscous liquid Yellow viscous liquid.. .. Yellow liquid (or solid). . Behaviour in dry air. Perfectly st able.. Perfedy stable. . Stable. ......... Loses Br slowly.. Loses Br slowly.. Loses CI (and Br? Loses Cl.. ...... How produced. Me,SI + I, Me3SBr + I, Me,SCl + I,, or Me,SI + IC1 R.le3~I + Br2 Me,SBr + ICl Me,SI + (312, or Me,SCl + IC1 Me,SBr + Br, Me,SCl + Br, Me,SHr + C1, Me,SCl + C1, I n this list, it will be seen that those compounds are the most stable which contain one iodine-atom ; that those which contain more than one are difficult to purify ou account of peculiarities which seem to characterisc many of the known polyiodides of oiypnic bases ; and that those which contain no iodine tend to break up into their com- ponents, except in an atmosphere of chlorine or bromine, a,s the case may be. As regards the constitution of tlhese compounds, three theories are worthy of consideration.The first would regard them as examples of mere nioleculttr combination, and would write the general formula Me,SX,X,. This, however, is not in accordance with the nature of the decomposition which the crystalline members of the series undergo when heated, nor with the fact that so high a tempera- ture is required to effect it. The second theory is represented by X the formula Me3S-X<X, and assumes that the halogen-atom of the original salt becomes triad. I n support of this may be quoted the general reactions of the dibromiodide and the dichloriodide, and particularly the fact that they combine with two iuolecules of ammonia ; also the ease with which the trichloride breaks up, inasmuch as we should certainly expect the monad group C1, to be very unstable if it exists a t all.But this theory obviously cannot account for the com- bination of trimethylsulphine sulphate with bromine and with chlorine; and this fact must be regarded as affording it strong argument against F 268 DOBBIN AND MASSON: ACTION OF THE HALOGENS, ETC. the theory ; for we have already pointed out the striking similarity between the compounds so formed and some of those derived from the haloid salts. The third theory is capable of general application to all the bodies we have described. It assumes that they are trimethyl-sulphinic salts, Me3S-X, in which the sulphur atom is hexad. /x ‘X The analogy between these bodies and the so-called polyiodides (Weltzien, Ann. Chem. Pliarm., 86, 292; 91, 36 : Tilden, this Journal, 1865, 99: Jorgensen, Ber., 2, 460; J.pr. CYhem., 3, 145, 328) and polybromides (Marquart, J. pr. Chern., 1, 429) of the nitrogeu bases is well marked. Moreover, Tilden (this Journal, 1866, 145) describes a dichloriodide of tetrethylammonium, which he obtained by acting on the chloride with iodine monochloride; and Weltzien (Ann. Cliem. Pharm., 99, 11) also obtained some similar compounds by indirect means. Professor Crum Brown suggested t.0 us, therefore, that we should investigate the hitherto untried action of bromine on the iodide of tetramethylammonium; and we have found that this reaction produces a red crystalline body so closely resembling the dibromiodide of trimethylsulphine as to leave no doubt of its true nature. Moreover, we have found that both bromine and chlorine unite with the sulphate of tetramethylammonium to form compounds which cannot be distinguished by their general properties from those obtained from the corresponding trimethylsulphine salt. We purpose making a complete investigation of the halogen com- pounds of the tetramethylammonium salts ; but what we have already observed, taken together with the work of t,hose chemists whom we have quoted, seems to justify us in saying that there is a large class of substances formed by the union of halogens with the salts of organic bases; and that any theory, to be acceptable, must be appli- cable equally to such examples as the ‘‘ pQlyiodides,” the dibrorniodide of trimethylsulphine, the trichloride of trimethylsulphine, the product resulting from the union of bromine with tetramethylanimonium iodide, and the products obtained by the union of bromine and chlorine with the sulphates of trimethylsulphine and tetramethylammonium. If, therefore, the bodies we have described are trimethylsulphinic salts, containing hexad sulphur, it would seem that nitrogen is capable of becoming heptad. Further evidence is, however, wanted on this point. In conclusion, we desire to express our gratitude t o Professor Crum Brown for having given us the great benefit of his aid and advice in this investigation.

ISSN:0368-1645    

DOI:10.1039/CT8854700056

出版商:RSC    

年代:1885

数据来源: RSC

摘要:

69 VII.-On the Decomposition of Silver Fulmina,te by Hydrochloric Acid. By EDWARD DIVERS, M.D., and MICHITADA KAWAKITA, M.E. THE Society has receired from us a note of the fact that silver fulmi- nate differs from mercury fulminate in yielding much less than the full amount of hydroxyammoninm chloride, and in yielding ammo- nium chloride. The present communication contains the results of our further examination of the action of hydrochloric acid on silver fulminate, and also those of the examination of the action of dilute hydrochloric acid on mercury fulminate, and on fulminurates, in relation to the production of hydroxyammonium chloride, formic acid, and ammonia, and of Steiner's production of oxalic acid from mercui-y fulminate. The silver fulminate was prepared in small quantities at a time, and was dried, with certain precautions, in an oven at or near 100".I n two preparations we determined the silver as chloride, and found 71.79 and 71.76 per cent., in place of 72.00 as calculated. Unlike the mercury salt, silver fulminate is energetically attacked by concentrated hydrochloric acid. As mentioned in our paper on mercury fulminate, it is hardly necessary to use Steiner's precau- tion of working with that salt only when moist; and although the reaction between silver fulminate and the acid is of a kind sugges- tive of danger, we have used it in the dry state without accident. The concentrated acid, as i t comes in contact with the bulky salt', causes i t to shrivel up and decompose with a loud hissing noise and development of heat. If the heating is not checked, the silver chlo- ride produced is a t first stained orange, but rapidly loses this colour, imparting it to the acid mother-liquor. The heating may be pre- vented or reduced, both by taking only a small quantity of the fulmi- nate at a time, and by dropping it into a considerable excess of the acid artificially cooled.The colour of the solution disappears during subsequent evaporation. Resides the colouring matter, there is a t first among the products of the reaction an unstable, colourless substance, which gives an intense wine-red colour with ferric chloride, both in the strongest acid solution or in one t,hat has been neutralised. Long standing in the cold or a few minutes' hating, deprives the solution of the power of changing in colour with ferric chloride.This substance is also formed from mercury fulminate, and, as we have already pointed out in our preliminary note, is probably identical with that met with by Gay- Lussnc and Liebig in their examination of silver fulminate, and70 DIVERS AND KAWAKITA: DECOMPOSITION O F SILVER described by them as a chlorinated acid containing nitrogen, and not precipitable by silver nitrate. Thi8 acid, however, is stated by them to have given the red colour only when the solution had been previously neutralised with alkali. In all cases when silver fulminate is treated with hydrochloric acid, the odour of hydrogen cyanide is perceptible, but more markedly when dilnte acid is taken. Two determinations were made of the amount of hydrogen cyanide produced when concentrated hydro- chloric acid is used ; in one experiment this was found t o be 0.29, and in another 0.38 per cent.The determinations were made with cai*e, but the results are to be taken as only approximately accurate, and as serving to show the smallness of the quantities of hydrogen cyanide produced. The procedure was first to let hydrochloric acid through a tap-funnel iiito a retort containing the dry, weighed fulminate, and connected air-t'ight with two U-tubes in series containing solution of potassium hydroxide, and, next, slowly to aspirate air through the apparatus for some time, the retort being kept warm. The contents of the receivers were then treated with enough silver nitrate to cause a precipitate, and were filtered. Lastly, the silver in solution in the alkaline liquid was determined and taken, in calculating the hydrogen cyanide, as having existed in the solution as silver potassium cyanide.Liebig's vo1umeti.i~ method could not be employed, because of the presence in the solution along with the cyanide of a minute quantity of some substance sharply reducing silver to the metallic state. The process of estimating the hydrogen cyanide indicated, there- fore, the possibility of the simnltaneous generation of a very small quantity of a highly volatile and oxidisable matter. Besides showing this reducing action on silver nitrate, the alkaline solution acquired in some experiments a slight brown colonr during the aspiration. Our endeavours to isolate or identify any such substance, 01% to get uniform indications, were, however? unsuccessful , and we believe now that traces of the contents of the retort must have been carried over mechanically, although unnoticed, by being first thrown up into the head of the retort by the violent action between the acid and the fulminate when they met, and then washed down into the receiver by condensing vapours.The hissing noise of the decomposition of silver fulminate by hydrochloric acid is connected with a not inconsiderable escape of carbonic anhydride. We have collected this escaping gas by decom- posing the fulminate with acid in a tube exhausted of air by the Sprengel pump, and have obtained in this way 4.4 per cent., which is the equivalent of & of the total carbon. This quantity is largely in excess of what can possibly be liberated when the fulminate is dropped suddenly into abundance of acid, and its production is due toFULMINATE BY HYDROCHLORIC ACID.71 the fact that, when working in a vacuum, the acid has to be added to the fulminate, and then meets it in the form of fine streams or jets- a condition of things allowing of great local beating and thus favour- i n g the generation of carbonic anhydride. Working in a retort, filled with air as usual, and adding the whole of the acid to be used suddenly to the fulminate, we have collected the escaping carbonic anhydride in barium hydroxide solution, and thus obtained evidently much less than when working in a vacuum, although as yet we have made no exact measurement of the quantity formed in this way.During the evaporation of the acid solution, a little carbonic anhydride continues to escape from it with the vapour, even after the precaution has been taken to expose it for some time in au open vessel on a water-bath before distilling. In the decomposition of silver fulminate by hydrochloric acid, there is liberated no gas but carbonic anhydride and hydrogen cyanide, neither nitrogen, nitrous oxide, nitric oxide, nor carbon monoxide, The yield of hydroxyammonium chloride depends on the strength of the hydrochloric acid used. In decomposing the fulminate, care was taken to miriimise the spontaneous heating-up of the mixture. The fulminate was added to moderate excess of the fuming acid in some cases, and in others to large excess. The product was warmed, diluted, well shaken to collect together the silver chloride, and filtered.The hydroxyammonium chloride was titrated with iodine solution. The quantities obtained in separate experiments were thus found to be:- 29.8, 29.1, 32.1, 29.8, 28.9, 30.4 37.4, and 31.6 per cent. These results show considerable uniformity, wit,h some exceptions, and represent very nearly two-thirds of the hydroxyammonium chloride equivalent to the whole of the nitrogen, that is, 46.33 per cent., two-thirds of which is 30.9. We have no reason to doubt the accuracy of any of these numbers, and attribute the irregularities observable to variations in the proportions of hydrochloric acid taken, although we are not able now to establish this to have been the case in these particular analyses.But, as we shall show that we can make the yield vary to some extent by varying the conditions of the ex- periment, we do not consider that any special significance is to be attached to the fact that about two-thirds of the nitrogen appears as hydroxyammonium chloride when concentrated acid is used. Uni- form procedure has given us uniform results, and by breaking through this we can make the results vary, and can increase the yield of this salt. For the estimation of formic acid, distillation was necessary before titration could be made, because of the presence of ammonium chlo-72 DIVERS AND KAWAKITA ON THE DECOMPOSITION OF ride. The distillation was finished in a current of air, and the heat so managed as t o leave the hydroxyammonium chloride as far as practicable undecomposed." The formic acid was measured by de- ducting the quantity of alkali equivalent to the hydrochloric acid found by titration with silver nitrate from the alkali required by the total acid, and calculating the difference as formic acid.In the ex- periment which gave us the fifth of the enumerated quantities of hydroxyammonium chloride, that is, 28.9 per cent., we obtained 19.8 per cent. of formic acid. The full quantity of formic acid is 30.67 per cent., and two-thirds of this is 20.44, so that we obtained almost two-thirds of the total formic acid possible, just as we obtained nearly two-thirds of the hydroxyammoninm chloride. We have attempted to estimate the formic acid? by weighing the * We have fewer determinations of formic acid than of hydroxyammonium chlo- ride, because of several failures in measuring it.Some of these were due apparently to the passing over of spray into the receiver in consequence of distilling in small retorts too full, to which practice we were tempted by the difficulty, when the retort was large, of getting over all the formic acid without overheating the hydroxy- ammonium chloride. This source of error was afterwards avoided by the obvious expedient of distilling with the retort not so full. Other failures were experienced through the presence of a very large excess of hydrochloric acid along with the formic acid, auch an excess having been taken in order to keep down by its mass the temperature of the reaction as much as possible, and lessen the production of hydro- gen cyanide.Sodium phosphate added to the contents of the retort, to fix some of the hydrocliloric acid, rendered the distillation difficult and unsatisfactory. After- wards, by taking a much smaller proportion of hydrochloric acid, this cause of failure was removed. It is, besides, dificult to see in what way silver fulminate could be decomposed in which the formic acid would not be equivalent to the hydroxyammonium chloride, unless the liberation of much hydrogen cyanide took place. f I n our paper on n.ercury fulminate we described an experiment in which, by titration of the formic acid from 2.6665 grams of mercury fulminate, and working on thirds, we determined its amount to be 3 per cent. less than the calculated quan- tity--31.3 instead of 32.4-surely a result having no great pretension to close accu- racy, considering that our mercury and hydroxyaminonium chloride determinations were in almost perfee: accordance with theory.As mercury fulminate has been known since the beginning of this century, as it is 60 years since it was examined by Liebig, and as no analysis of this salt had been published in all that time, except the partial one by Liebig, in which he got 56.9 per cent. mercury instead of 70.4, we thought it of interest to use our results for the purpose of showing for the first time the composition of mercury fulminate by analysis. This having been done by us, Dr. Schotten, in abstracting our paper for the Berichte der deutsch. chem. #es., has endeavoured to raise doubts in the minds of his readers as to the accuracy of our results.There was and is no better method of determination open to us; a finding by titration of only 97 per cent. of the calculated amount of formic acid was cer- tainly no refiiiement of accuracy beyond the capability of the method ; and a devia- tion of even double that extent from the truth would still have left our result suffi- cient to prove all we attempted to make it do. In the text of this paper, we gim After all, sufficient determinations for the purpose are given.SILVER FULXINATE BY HYDROCHLORIC ACID. 73 calomel produced by it from mercuric chloride, but not with success. H. Rose lias proved that in the presence of alkali chlorides, the pre- cipitation of mercurous chloride is incomplete, but this fact was no obstacle to us.We had before us a mixture of formic and hydro- chloric acids, and this we proceeded to neutralise with washed pre- cipitated mercuric oxide. To test the method, we operated on lead formate and found if work quite successfully. The lead salt was treated with enough hydrochloric acid to decompose it, and mercuric oxide was then added in excess. Digestion on a water-bath, aided by frequent stirring, and then a second digestion with dilute hydrochloric acid, gave the theoretical quantity of mercurous chloride. In one experiment we got 30.80, in another 30.83 per cent. of formic acid, whilst pure lea,d formate should yield 30.97 per cent. The method has the great recommendation of depending on the weighing a compound more than ten times heavier than the substance estimated.But un- fortunately, as we have said, we found that it would not serve our purpose. The large proportion of hydrochloric acid present proved a fatal obstacle. This acid formed an oxychloride during the long digestion necessary to insure the decomposition of all the formic acid, which it was generally impossible to dissolve out thoroughly from the mercurous chloride by fresh hydrochloric acid, without at the same time deconiposing some of it into metal and mercuric chloride. After many trials we gave up our attempt to use this method. Whatever inay be the yellow or orange matter which is formed when the silver fulminate is allowed to grow hot by its reaction with hydrochloric acid, the following experiments serve to show t h a t it is formed at the expense of that portion of the fulminate which would otherwise become hydroxylamine and formic acid in contact with con- centrated hydrochloric acid.That it is not formed from the other third of the fulminate, or a t least from that third alone, is also to be seen in the fact that, with cooling, only a trace of it is produced, although no portion of this third is gained as formic acid and hydroxy- ammonium chloride. I n two separate portions, in order to moderate the rise in tempera- ture, 2.6330 grams were drenched with fuming hjdrochloric acid, without cooling. The resulting solution, which had a distiiict yellow colour, gave, by direct titration with iodine, hydroxyammonium chloride 27.65 per cent., and by titration with alkali, after distillation, other determinations of formic acid by this method, the degree of accuracy of which may safely be measured approximately by the hydroxyammonium determinations, and as we have suppressed nothing, we offer these to show what the method is capable of.We should add that in all proba,bilit.y the hydroxgammonium is not an exact measure of the formic acid, but measures this and the very small quantity of hydrogen cyanide together.74 DIVERS AND KAWAKITA ON TIE DECOMPOSITION OF formic acid 18.67 per cent. These quantities are about one-twelfth less than two-thirds of the whole. Next, in order to lead to a still greater rise in temperature, 1.9830 grams were treated in one lot in the same way. Much heat was developed, and a t first the silver chloride was very strongly coloured, but soon gave up its colouring matter to the solution. The hydroxyammonium chloride was in this case found to be only 21.55 per cent., or less than half the f u l l quantity.The change in the results obtained by using dilute hydrochloric acid instead of the concentrated, is considerable, and is important as serving t o tone down the contrast between mercury fulminate and silver fulminate. Although the use of the acid in the dilute state seems to favour the production of hydrogen cyanide, both hydroxy- ammonium chloride and formic acid are increased in quantity much above two-thirds. A small quantity of silver fulminate, 0.3175 gram, being put uuder water, concentrated hydrochloric acid solution was added to the extent of about half the volume. The hydroxFammonium chloride obtained in this case was 43.52 per cent., which is not very far short of the full quantity, 46-33 per cent., whilst the yield with undiluted acid was only 30 per cent., as already fully recorded.A modification of the preceding experiment was made by using hot liquids. 0.36975 gram of fulminate was placed in hot water, and hot, diluted hydrochloric acid added. Iu this case, 41.60 per cent. of hydroxyammonium chloride was produced, a lower yield, and illus- trating the injurious effect of heat. Once more, 4.28225 grams of fulminate, in two quantities, were treated with cold water and hydrochloric acid, and the resulting solu- tion, after the usual heating on the water-bath, divided into portions in which both hydroxyammonium chloride and formic acid were deter- mined.We found :- Per cent. 42.15 evaporation ................................ 42.17 with iodine.. ................................ 42.88 28.35 Hydroxyammonium chloride, by direct titration .... 3 7 ,, weighed as residue on Hydroxyammonium chloride, by tit'ration of residue Formic acid, by titration with alkali.. ............ From these results, it appears that about nine-tenths of the silver fulminate had become formic acid and hy droxyammoniu m chloride. When silver fulminate has been treated with concentrated hydro- chloric acid, we always find ammonium chloride present in quantity among the products. I n this respect, silver fulminate is in marked contrast with the mercury salts. But when dilute acid is used, thisSILVER FULMINATE BY HYDROCHLORIC ACID.7 5 difference between the salts is no longer observable. Along with the increasing yield of hydroxyammonium chloride and formic acid that attends dilution of the hydrochloric acid, there goes a lessening of the quantity of ammonium chloride down even to nothing. The results last given show that in the experiment with dilute acid, no ammonium chloride was formed, or practically none, for the difference 0.3 between 42.17 and 41.88 may safely be set down to the presence of water and hydrochloric acid as impurities. Qualitative testing gave only doubtful evidence of any ammonia being present. I n contrast with the result in which dilute hydrochloric acid was employed, may be presented results which were obtained with con- centrated hydrochloric acid :- Hydroxyammonium chloride, by direct Mixed chlorides as residue on evapora- Hydroxyammonium chloride, by titra- I.11. 111. IV. titration. ....................... 29.80 29.08 32.13 30.42 tion .......................... 34.90 35.03 37.39 35.37 tion of residue .................. 27.60 - 30.07 - Ammonium chloride, by difference .... 7.3 - 7.3 - Although among these experiments T I and I V were not followed out, the two numbers given enable the others to be inferred. Ammonia was tested for qualitatively, after destruction of the hgdroxyam- moriium chloride with iodine, and found abundantly. Ammonium chloride 7.3 per cent. IS equivalent to more than a fifth of the total nitrogen of the fulminate. Ammonia, so far, having been determined only by difference in weight between the evaporation-residue and the hydroxyammonium chloride measured by titration, an attempt was made to estimate i t directly.Some silver fulminate having been treated with con- centrated acid in the usual way, a portion of the solution was treated with copper sulphate and potassiiim hydroxide in a closed flask, in order to destroy hydroxylamine. The resulting alkaline solution and precipitate were then distilled for ammonia. B u t the process proved unsatisfactory, inasmilch as free ebullition was impracticable in con- sequence of the mixture bumping; and therefore only part of the liquid could safely be distilled over, so that some ammonia must have been retained by the copper hydroxide. We succeeded, however, in getting in this way three-fourths of the quantity of the ammonia indicated by the indirect method.Instead of making further trials to determine the ammonia directly, we made two chlorine determinations in the evaporated residue of chlorides, as well as hydroxyammonium chloride determi-76 ON THE DECOMPOSITION OF SILVER FULMINATE. nations by iodine titration. We found in one case, as difference between total residue and hydroxyammonium chloride, ammonium chloride 4.92 per cent. of the fulminate, and, as the equivalent of the difference between the total chlorine found and that calculated from ihe hydroxyammonium chloride, 4.33 per cent. ammonium chloride. I n the other case we found, as difference by weight, 7-65, and as difference by the chlorine method, 7.20 per cent. ammonium chloride. These determinations of the chlorine served not only to estimate the ammonia, but also to confirm the view that the oxidisable part of the residue was hydroxyammonium chloride and nothing else. It was in the experiments just detailed that we also determined the hydrogen cyanide, and as the only nitrogenous products we have observed have been hydroxylamine, ammonia, and hydrogen cyanide, the quantities obtained of these three substances should contain all the nitrogen.This they do not quite do, as the following statement shows :- I. 11. Nitrogen as hydroxyammonium.. .. 7-34 6-36 97 ammonia 1.13 1.88 7, hydrogen cyanide 0.15 0.20 9 7 unaccounted f o r . . 0.51 0.89 7 7 silver fulminate 9.33 9.33 ............ .... .... -- - ...... It is tolerably certain that some ammonia escapes, if not duying the evaporation, at least during the drying of the residue in the dish.Menxyy fulnzinnte, when treated with dilute hydrochloric acid, yields no ammonia. By using one measure of concentrated acid to three measures of water, mercury fulminate can be thoroughly decomposed a t the heat of a water-bath. The yield of hydroxy- ammonium chloride is somewhat diminished, and that, of hydrogen cyanide increased. Hydroxyammonium chloride, 43.51 per cent., was thus obtained, the calculated quantlity being 48.94 per cent. There no longer exists, therefore, any difference between the two salts as fulminates, what difference they show being caused by the metallic radicals. The same hydrolysis occurs with both fulminates ; but in the case of the silver salt, in consequence probably of the sharp separation of the silver chloride in the solid state, the decom- position generates heat SO rapidly that the formic acid and hydroxy- ammonium chloride change into carbonic acid and ammonium chloride :- CzAg2N202 + 4HC1 + 40H2 = 2CH302 + 2NH40C1 + 2AgC1 and CH2Oz + NH40C1 = CH203 + NH,Cl.DIVERS ON THE COX3TITUTION OF FULMINATES.77 Hydrochloric Acid aml Fulviinurates. We have only made a special examination of the behaviour of hydrochloric acid with fulminurates, to see whether these salts were capable of generating hydroxyammonium chloride and formic acid. As already known, fulminurates yield some ammonium chloride when heated with aqueous hydrochloric acid. We have experimented with potassium fulminurate and silver f u lminurate, and have obtained neither hydroxyammonium chloride nor formic acid. Hydrochloric acid does not seem to have much action on fulminurates. Non-productiosi, of Oxalic Acid from Fzhainates. We have already published an account of our failure t o find even a trace of oxalic acid among the products of decomposition of mercury fulminate by sulphuric acid, or by aqueous hydrogen sulphide. But as it is stated that Steiner got oxalic acid by decomposing mercury fulminate with hydrogen sulphide, using ether instead of water as a menstruum, and even to have obtained it in crystals (see Watts’s Dictioi~n~y), we have followed his process, using as little ether as practicable, so as to avoid as far as possible the accidental presence of water. We have repeated the experiment, and on evaporating the ethereal solution, after saturating it with hydrogen sulphide, as directed, could find no trace of oxalic acid in the residue, and for our own part we believe t,hat oxalic acid cannot be produced from fulmi- nates by any method yet published.

ISSN:0368-1645    

DOI:10.1039/CT8854700069

出版商:RSC    

年代:1885

数据来源: RSC

摘要:

DIVERS ON THE COX3TITUTION OF FULMINATES. 77 Q1II.-On the Cons titution of Fulminates. By EDWARD DIVERS, M.D. Since I laid before the Society my conclusion as to the probable constitution of the fulminates being different from any previously attributed to it, Kawakita and myself have shown the improbability of Liebig having really obtained silver fulminate without the co- operation of nitric acid with the nitrous acid, and are glad to have had the correctness of our results upheld by Armstrong on theoretical grounds. In accepting also iny criticism of his own formula for the fulminates, Armstrong pointed out a t the same time that in represent- ing the formation of t'he silver fulminate from alcohol and nitrous acid, as I did, I had laid myself open to like criticism. This is true, and it is a relief t o me to know that this change which my formula78 DIVERS ON THE CONSTITUTION OF’ FULMINATES.for fulminates could not legitimately represent can no longer be regarded as possible. I was led by this formula to doubt whether Kekul6’s dibromonitro- acetonitrile could have the constitution expressed by its name, and pointed out that it should probably be represented by the for- mula O:C:N.O.N:C:Br,. 1 have not yet fulfilled my intention of examining this body, but have seen the original commnnication in the Bericlde, 5, 89, by Sell and Biedermann, describing the corresponding iodine compound, and see by it how little further examination is really necessary to show that the carbons of these bodies are not directly joined. These chemists have found that the end-product of hydrogenising the iodine compound by tin and hydro- chloric acid is methglamine, and that the formation of this body is preceded by that of abundance of hydrogen cyanide.This asppears to me conclusive evidence that the carbons are not directly united. Hydrolysis seems highly improbable as a cause of the separation of the carbon-atoms, supposed to be united, because these halojd com- pounds have already been produced by the action of bromine or iodine in presence of water. Armstrong has amended his original formula. He suggclsts it theory of the conversion of alcohol into fulminate, in whicb the alcohol first becomes hydroxyethaldehydrol, and is then acted on half by hydroxylamine and half by nitrous acid. To the latter part of this theory I cannot assent, as I do not believe that these bodies can act without mutiial destruction or destruction of each other’s derivatives.As regards the formula he now proposes for the fulminates, it is unfortunate that this is given in an erroneous form in his note, A correction of i t has since been made in the list of the errata, which I will venture to suggest still requires amending. According to the correction, fulminic acid is HOCNC(NO€I), and this allows of no explanation of tlie conversion of both nitrogens into hydroxylamine, and must therefore, in my opinion, be rejected. I had previously corrected his formula for myself, as originally given, to I 1 and find that Schotten has done the same for the Referate of the Berichte. Even when I assume that this formula really represents Armstrong’s present views, I can hardly agree wit>h him in regarding i t as differing but slightly frotn that which he brought forward in 1875, namely, (N0)HC: C(N0H).For not to insist on the import- ance of tlie difference between an ethylene and an ethane type, I see a, profound difference between them, in that one of the atoms ofDIVERS ON THE COSSTIT UTION OF FULMINATES. 79 oxygen unites carbon to nitrogen in the present formula, whilst i t is only united to nitrogen in the earlier one. In many respect the formula HCNOC(N0H) is as satisfactory as the one proposed by me, HCNONCOH. But I find a strong argument in favour of the latter in the fact that it shows fhe hydroxyl in union with nitrogenised carbon, and na,turally, therefore, as in cyanic acid, markedly basic.I n the other formula, the hydroxyl of a hydroxylamine derivative is represented not only as basic, but as capable even of taking part without difficulty in double decomposi- tions in water, and yielding the various bimetallic fulminates. But so far as I know, the hydroxyl of hydroxylamine has proved itself t o be analogous to “ alcoholic ” hydroxyl in carbon compounds, its hydrogen being replaceable by organic radicals only, and not by metals in pre- sence of water, if a t all. Schramm’s hydroxylamine compounds, con- taining silver or sodium, may or may not be metsloxyl-derivatives. The sodium compound appears unable to exist in water. I have only to add that I see my use of the radical : N.0.N : has the support of Goldschniidt, who, a little before my paper on the fulminates was published, had used it in representing the possible constitution of a dioximido-derivative of phenanthraquinone. m Note on the above by Dr.Armstrong. My chief object in publishing a “ note on the formation and con- stitution of the fulminates” was to call attention to what I believe to be the fact, viz., that the fulminate is not the immediate product of the action of nitrous acid on alcohol in presence of mercury or silver salt ; and to indicate a direction in which, in my opinion, synthetical experiments should be prosecuted. With reference to Dr. Divers’ criticism, although nitrous acid and hydroxylaniine tend to destroy each other, yet I believe it to be both possible and pro- bable that they may be generated Bide by side without mutual destruction, if a third body is present with which one or both may enter into reaction, o r which tends to exercise a protective influence. His own remarkable observations on the action of tin 011 a mixtiire of nitric arid chlorhydric acids may be cited in support of this view.Illy formula was not put forward as a final expression of the pro- perties of the fulminates; as I particularly stated, the formula printed-or rather which should have been printed, * * was not the only one which could be deduced. N.C.OH The two formulae N. c (N.oH)’80 RICHARDSON : CHEMICAL ALTERATIONS IN GREEN which I incline to regard as the most probable are, however, the following :- N.CH 0. C (N. OH). N /C.O* . . \C (N.OH) But while I am of opinion thak these formulae fully take into account both the elimination of the two nitrogen-atoms as hydroxylamine and also the formation of bimetallic fulminates, I do not think we can at present further discuss with advantage the several formulae put forward by Divers and myself; they, however, will doubtless serve to guide us both in investigating the subject, and in obtaining evidence which may ultimately furnish a solution of the problem. I may here point out that although the fulminates have hitherto always been regarded as " dicarbon '' derivatives, on account of their formation from ethyl alcohol, there is no direct evidence before us that such is actually the case, and it is especially noteworthy that Divers has always failed to obtain oxalic acid by hydrolysis of fulminates.

ISSN:0368-1645    

DOI:10.1039/CT8854700077

出版商:RSC    

年代:1885

数据来源: RSC

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80 RICHARDSON : CHEMICAL ALTERATIONS IN GREEN IX.-Notes o n the Chemical Alterations in Greert Fodder during its Conversion into Ensilage. By CLIFFORD RICHARDSON, Assistant Chemist U.S. Department of Agriculture. IN recent numbers of the Journal of the Chemical Society, Professor Edward Kinch and Dr. 0. Kellner have published some observations on the changes which take place in the nitrogenous constituents of fodders. Analyses which I have made during the past two years throw additional light on the subject., and are, although somewhat incom- plete, presented here. Professor Kinch found that 55 per cent. of the total nitrogen pre- sent in the ensilage of grass was of a non-albuminoid nature, whilst in the original grass only 9 per cent. was of this form. In the case of mangel leaves Kellner found that of the total nitrogen present 27.8 per cent. in the original leaves, 45.5 per cent.in the ensilage, and as much as 59.7 per cent. in the ensilage preserved in stoppered jars was non-albuminoid. In the ensilage of maize I have found :-FODDER DURING ITS CONVERSION INTO EXSILAGE. 81 Per cent. of total nitrogen as non-albumino’id. Original stalks. ..................... 21 -2 Ensilage No. 1.. .................... 44.6 Ensilage No. 2 ...................... 49.6 Dried fodder ...................... 15% Ensilage from young maize .......... 53.3 Ensilage from older maize.. .......... 47.1 These results with grass, mangels, and maize show that in the conditions existing in silos a large portion of the albuminoids are converted into non-albumino’id nitrogenous substances, whilst in the ordinary drying of fodder EO such change seems to take place.Kinch and Kellner both found that a portion of the nitrogen of the original plant was lost or did not appear in the analysis. With grass it was 13 per cent.; with mangels 27.8 per cent. in the unpressed ensilage in the jar, and as much as 59.8 per cent. in that in the open silo. The latter high percentage is doubtless due to the carrying away in the expressed juice of much soluble nitrogenous substance, I am in possession of but few quantitative data in regard to maize, but have found that in the samples of ensilage which I have examined there is a comparatively large amount of ammonia combined with the acids produced by fermentation, acetic and lactic, which o€ course is lost in drying the specimens for analysis.In the results, this pro- duces an apparent loss of nitrogen in the ensilage itself: it is at any rate a loss of nitrogen of nutritive value. A quantitative deter- mination of the ammonia salts in one specimen of ensilage (Serial No. 1693) gave the following results :- Weight of ensilage taken ............ 4000.0 Equivalent to dry substance .......... 620.0 Weight of NHICl 8.660 Per cent. of nitrogen from dry substance 0.366 .................... Equivalent to nitrogen. ............... 2.266 Equivalent to alhumino’ids ............ 2.287 That the nitrogen was in the form of ammonia and not a more complex amine was proved by the following analysis :- Weight of ammonia salt taken ...... Weight of platinochloride found .... 0.1000 0.4105 Equivalent to NHaCl ..............0.0990 This ammonia salt, probably acetate, would be lost in the process of drying, and produce a corresponding deficit in the relative pel’- centage of nitrogen in the analysis. In fact, a loss of 2.29 per cent. of nlbuminoids iu the dry substance of an avemge maize stalk, con- VOL. XLVII. G82 RICHARDSON : CHEMlCAL ALTERATIONS IN GREEN taining 7.50 per cent., amounts to a little moi-e than 30 per cent. of the total nitrogenous substance in the plant, and t o about the loss which Kellner found in his experiments with mange1 leaves not under pressure. The remaining non-albuminoiid nitrogen is probably largely of an amide nature, as, like Kellner, I have found very small amounts of peptones.Attempts, however, to separate any amides in a crystal- line condition have resulted in obtaining nothing but a syrupy nitro- genous substance. The loss of nitrogenous substance from ccnversion into ammonium salts and decomposition on drying is relatively compensated for by the large loss of carbohydrates, so that in the analytical figures neither loss is prominent, and they are at first glance deceptive. The control of course lies in an absolute knowledge of the weight lost by the fodder in the silo, or in the relative increase in one of the constituents which is less liable to change, as for instlance the ash. But as Kellner has shown, pressure is very liable to remove the soluble part of the ash in the juice expressed, and thus entire dependence cannot be placed on this element.An interesting experiment was carried or, at the New Jersey Experi- ment Station in 1881, in which the ash served as a basis for calcula- tion without apparently vitiating the results. Ten tons of green fodder “corn” was divided into two lots on September lst, one half being stacked in the field, and the other packed in a silo of the capacity of 12 tons, after being cut in short lengths. At the same time, a camrefully selected sample of the green fodder was prepared for analysis. In November, 1200 lbs. of the dried fodder was run through a cutter, and an average sample prepared for analysis. On the 23rd of December a specimen of the ensilage was selected. The composition of the three substances was as follows :- Green stalks. Dried stalks. Ensilage.Original substance- Water .......... 75.00 39.37 74.50 Bsh ............ 1-58 4-63 1.97 Fat.. ............ 0.22 0.66 0.27 N.-free extract.. .. 15.60 32.85 13.58 Crude fibre ...... 6.35 18.65 7.92 Crude albumin.. .. 1.25 3.84 1.76 100~00 100~00 100.00FODDER DURING ITS CONVERSION INTO Dry substance- Ash ............ 6.32 7.64 Fat ............ 0.88 1.09 N.-free extract.. .. 62-40 54.18 Crude fibre ...... 2-5-40 30.76 Crude albumin.. .. 5.00 6-33 ENSILAGE. 83 7.71 1.06 53-24 31-07 6-92 ~~ 100~00 100*00 1u0.00 As 100 lbs. of the dry matter of the green fodder contained 6.32 lbs. of ash, the amounts of the other constituents corresponding with this weight of ash and therefore with each original 100 lbs. of stalks, were calculated in order to show the absolute loss of each constituent.Green stalks. Dried stalks. Xnsilage. Ash.. .................... 6.32 6.32 6.32 Fat ...................... 0.88 0.90 0.86 N.-free extract ............ 62.40 44.82 49.64 Crude fibre.. .............. 25.40 25.44 25.49 Crude albumin ............ 5-00 5.24 5.67 Total weight of dry matter to 6.32Ibs. of ash .......... 100*00 82.72 81.98 The loss in t>his case is seen t o fall upon the carbohydrates entirely, and to be as great for the dry fodder as f o r the ensilage. There is an apparent slight increase in albuminolds, which can be explained by the fact that the calculation is made as if no ash had been lost by being dissolved or expressed in the two preserved samples. This is remark- able as showing that in this case, quite at variance with other instances, the nitrogen suffered little o r no loss, and that in fact the whole loss fell upon the carbohydrates.This may he due t o the short time during which the maize was in the silo, as all samples which I have examined have not been taken o u t for several months. These results at least show how varied the conditions are and how unsafe it is to generalise from any one experiment. This point is made evident in the analyses appended t o this paper. As to the nature of the fermentation and the proximate principles involved, I have made some observations. In but one sample out of many examined has any trace of Xaccharomyces been found, As a rule the juice expressed from the fresh ensilage is swarming with Bacillus subtilis, together with some species of Bacterium and Micro- coccu,s.No signs of the ordinary lactic or viscous ferment have been observed. The fermentation does not appear therefore to be of an alcoholic nature, or similar to any with which we are well acquainted. Analyses show the presence of an insufficient amount of alcohol, gum, G 284 RICHARDSON : CHEMICAL ALTERATIONS IN GREEN or free acid for any of the usual forms of fermentation, as can be seen from the following determinations. Alcohol was never absent in any of the ensilages experimented on, but in all was present in such small quantities as to be distinguished only by the iodoform test. Lactic acid has always been detected, but never in large quantity. Acetic acid is the chief acid of the ensilage. The relative proportion of the two acids varies largely, the following being a few deter- minations :- Serial No.1003 ........ 1004 ........ 1500 ........ 1501 ........ 1502 ........ 1677 ........ 1693 ........ Per cent. in ensilage of f - - y - - b - Y Lactic acd. Acetic acid. traces 2.12 0.15 1.59 0.52 0.80 0.24 undet. 0.26 1.02 0.13 undet. 0-11 undet. Total as acetic acid. 1840 .............. 2.40 1841 .............. 1.42 The whole amount of acid present was from 1 t o over 2 per cent., the lactic acid not rising above six-tenths of a per cent. The presence of lactic acid was determined by expressing the juice from a specimen of ensilage, distilling off the volatile acetic acid by repeated distillations, and neutralising the residue with zinc carbonate. The crystals of zinc lactate which were obtained on evaporation were crystallised and analysed.They contained :- Analysis. Theory. Water .......... 18.46 18.1 8 ZnO ............ 26-11 27.27 Gum or similar substance is not formed in any large amounts in the silo. Unchanged sugar has been found in the juice expressed from two ensilages, but as a rule it completely disappears. No. 1003 contained 2.40 per cent., No. 1004 1.07, and No. 1541 0.76 per cent. of reducing sugars. The fibre is of course increased in relative amount, but absolutely it is probable that it is but slightly altered. In Table I (pp. S5-S6) analyses of a number of ensilages are presented together with those of a dried fodder and several green stalks atFODDER DURIKG ITS CONVERSION INTO ESSILAGE. 85 0 m e t-* * - i- E- - .- i i c p p T l .- F 10 9 _ _ _ ~ L- - 1' yyl?FFl- IS -#--mL-cI 0 o*o*--# h X - 4 3 L 0 3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . r . . . . . - . . . . . * . . . . . . , . . ' X . . . : : , : :.5 : . . : i2 i g . . : s : s I : ; i 5 .a 0) . : i0) :- 3 ; i : E a " g ; i izga i U'aG? 2 % :*?gW ';d ,% d ,-5 I x .gs 4 B 2 c z i; .. . . . . . . . . . . . . . .- c i m o l m t - ??P"W U a w m t - 0 * m * t - - o t o t - CQr-mU2.m mp9y.F -#m . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . * . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . :: : : : : * . . a . 3 : ; : : a ; ; i 13 : :a :- 2 .Q I -TABLE I cont i?aued.-A?zatyses of Maize Silage and of Maize Foddey. ---PA--- Original substance- Water ...................................................................... Ash .......................................................................... Oil, R.C................................................................. Nitrogen-f. ee extract .................................................. Crude fibre ............................................................ N x 6 2 5 = "albuminoids" ., .................................... Dry substance- Ash .......................................................................... Oil, gLc. ................................................................. Nitrogen-free extract ................................................. Crude fibre .............................................................. N x 6.25 = " albuminoids" ...................................... In the cthcr rxtract- In the nit rogen-free extract- Non-volatiitn free acid ...............................................Sugars, &., sol. in 80 prr crnt. alcohol; sol. in water .. Substances, 601. in 80 per cent. aIeoho1; insol. in watcr .. GUUl, R.C. ................................................................ Nitrogen ................................................................. Non-albnxninoid nit,rogen,. .......................................... Pcr cent. of nitrogen as nun-alburninoid ....................... I n the " albuminoids "- I n the original substance- Acetic acid ............................................................ Lactic acid .............................................................. Juice per cent ......................................................... Sugars .................................................................... Solids ...................................................................... Sililge.1 Silage. 16ii. 1 1693. (Blair.) I (Blair.) I _--_____ 81 67 1'04 1-04 1.09 I 0-79 10.17 8 '47 1'39 1 1.34 100'00 ~ 100-00 4'64 1 3'86 __I-___.__ 5 '68 5 .96 55 '50 25 -30 7 '56 100 .oo - -- 0 .i'2 10'59 2 '90 2.91 1 '21 0 '54 44 '6 I 0 *13 - - I Silage. 1652. (Young.) 82 '61 1 .14 1-01 9 2 1 4 '96 1'04 100.00 Silage. 1653. (Old.) --- 78 *62 1-21 1 '46 11.39 5 -80 1 -52 100 '00 6 '68 6 3 9 5 'oa 5 '84 54 -64 53 '08 8 '67 5 9 7 24 '93 28 .:ia p___--__ 100~00 1 100'00 ____---- o -72 l - 5 '68 6 .8? 63 '26 27.12 7-12 100 .oo ---_ 8 '34 - - 3 '66 - - 3'58 I - , - 1-14 0 *54 5 i '1 Dried fodder. 1654. 27 -25 2 .I2 2 3 3 50 -02 1 2 '7.5 5.33 100'00 - --.-- 1-18 0 '18 15 '6 Green fodder.It;"<. St ,lkq for 1677 and 1693. 85 'SF 1 ' X i 0.58 7 .2i 2.48 1 9 0 I00 '00 -- ---- 13.31 3 'il 51 -77 17'67 13 '54 100'00 --- Stalks. Egyptian maize. Y onng anthers just out. -- 81 *90 1 'I1 0 4.1 9 -25 3.04 1.26 100 .oo -_-- 7 *39 2 '89 61 '25 20.15 8 '32 100 *oo -I_---FODDER DURING ITS CONVERSION INTO ENSILAGE. 8'7 various stages of development. From them, much may be learned as to the variations to be expected. The composition of the stalks of green maize is subject to very wide variations, as may be seen by the few analyses quoted. This then is a primary cause of differences in the composition of the ensilage, and, although it is due largely to the period of growth a t which the stalks are cut, yet there are often marked differences in composition in those o f the same stage of development, even in the same field.In a series of analyses of the stalks of Egyptian sugar corn and Lindsay's horse-tooth corn, completed by me, and published in the Beport of the Commissioner of Agriculture for l g 8 l and 1882, these variations are shown, The specimens, the analysis of which are here given, were all from a small plot of carefully selected stalks only a few rods square, and yet, in many instances, they show the largest variations from a regular series. The variations which are found in the composition of the stalks while they are in a condition to be packed in a silo, that is to say, from the appearing of the tops until the grain is well formed, are included within the following limits :- Highest. Lowest.Water in green substance 91.60 79.10 Dry substance.. ........ 20.90 8.40 Ash .................. 9.72 3-54! Oil .................. 3.43 1.68 Crude fibre.. .......... 31.29 21.56 Albuminoids .......... 11.53 1.67 Percentage of nitrogen as non-albumino'id ...... 70.4 18.0 These limits, together with a study of the individual analyses, serve to show the primary cause of the differences in ensilages. As t'o variations produced by other causes, illustrations are found in the samples numbered 1652, 1653, 1677, and 1693. Numbers 1652 and 1653 are analyses of ensilage from young and old stalks. The younger would naturally contain more ash and albuminoYds as it went into the silo, but the nitrogenous substances would be in such a condition, from the greater amount of soluble nitrogen, as to make them more liable to conversion into ammonium salts. This is the case with No.1652. I n it, the ash is higher than in the older speci- men, but the nitrogen is lower from a greater loss. The relative t-lmount of non-albuminold nitrogen is also lower in the younger than in the older sample. I n other respects, they do not differ largely, although one was from stalks on which the ears were well formed, and Carbohydrates .......... 69-40 59.60TABLE 11.-Egyptian Sugar Corn (Maize), plaated A p d 30th, 1881. cx, 'x, ------- D eve lopme 11 t- Height, in feet .................... Diameter, in inches ................ Total weight, in grams.. ............ Weight of stalk.. .................... leaves. .................. .. top ..................... Per cent. of stalk in whole plant.. .... .. ear.. .................... Dry substance- Aih .............................. Criide fat. ........................ Nitrogen-free extract. ............... Crude fibre.. ...................... Crude albumin .................... T o t a l nitrogen .................... Per cent. of nitrogen as non-albumino'id Water. ........................... Ash .............................. Crude f a t . . ..................... Nitrogen-free extract. ............... Crude fibre.. ...................... Crude albumin .................... Non-albumino';d nitrogen. ........... 0 ri gina 1 subs t a n ce- 526. July 5th, top just out. 7.0 1 -2 12442 ' 0 960 .O 216 *O 66 *O 77 *3 - 9 9 2 2 *58 50 -60 27 *01 10 *09 1 *61 0 *99 61 *4 91.60 0 *83 0 *21 4 -25 2 *27 0 -85 540.July l l t h , anthers not out. -- 7 -2 1 '2 1097 * 0 585 -0 468 '0 44.0 53 '3 - 9 *09 1 '80 51 '29 26 '38 11.53 1 '85 1 '27 68 -6 91-30 0 *79 0 .16 4 * d k 5 2.30 1 '01 547. July lltli, anthers out, filling. 8 -5 1-1 1037 *O 5 -42 430 -0 35 -0 52 *1 - 6 -53 1 *68 52 *41 31.29 8.09 1 -29 0.85 65 .9 88 *30 0 9 6 0 -19 6 14 3 -66 0.95 Stalks. 562. J u l s 18th. --- 9 -0 1 -2 1378.0 613 .O 651 *O 26 *O 83 -0 44 -9 5 *60 3.48 60.45 26 -04 4 '43 0 -71 0.31 43 -7 85 *90 0 *79 0 *49 8.53 3 *67 0 -62 576. July 25th, silk out. 9 . 2 1 ' 2 1642 -0 575 0 737 '0 78 *O 252 *O 35 -0 4 -81 2 -7; 61 *53 26 '09 4 *85 0 *78 0 -39 50-0 83 '20 0 -81 0 *46 10 *34 4 -38 0 *81 580. August 1st) our formed.10 -2 1 *6 1722 -0 636 *O 86 2 '0 32 -0 190 0 37 -0 5 -87 2 '35 66 "72 22 -07 2 -99 0 '48 0 *29 60 *5 80 *20 1 *16 0 -47 13 -21 4 '37 0 -59 694. Axgust 8th. 10 *o 1 *2 1068 *O 593.0 300 *O 9 .o 166 .O 55 -5 4 -97 2 el0 67 -37 21 '82 3.74 0 -60 0 -33 55 *o 80 *60 0 -96 0 *41 13.07 4.23 0 -73FODDER DURING ITS CON'VERSION INTO ENSILAGE. 89 the other from stalks on which the ears had made no appearance. In comparison with the ensilages, the dried fodder, No. 1654, from stalks of the same field as the old ensilage, No. 1652, shows several advan- tages. As has been already remarked, its nitrogenous constituents have not suffered so much change, only 15.6 per cent. being in a non- albumindid form as compared with 53.3 and 47.1 per cent. in the ensila'ges. A smaller loss of carbohydrates has left the relative per- centages of fibre, fat, and ash, low; and the evidence points to the fact that the stalks must have dried rapidly and with few changes, furnishing a fodder of much better composition than that analysed in New Jersey.In Nos. 1677 and 1693, we have analyses of two specimens of en- silage taken from the same silo within a few days of each other. One has lost more ash and nitrogen than the other, and this is due probably to greater pressure on the first sample, which had lost expressed juice carrying with it nitrogenous matter and ash. In other respects they are much alike. The variations in composition, which are found among the analyses of ensilage, lie within the following limits :- Water ................ Ash .................. Oil .................. Carbohydrates ........ Fibre ................ Albumino'ids (N x 6.25). . Per cent. of nitrogen as non-albuminoid ...... Dry substance. ......... Ash .................. Oil ................... Carbohydrates ........ Fibre ................ Albumino'ids .......... Or for dry siibstance- Highest. 84.80 2.01 1.80 15-37 7.54 2.77 53.3 15.20 8.87 9-12 61.84 28.58 11.97 Lowest. 70.60 0.9 1 0.79 7.75 2.85 1.04 47.1 29.40 5-68 5-08 48.43 18.76 5.97 By comparison with t.he extremes for green stalks, it is seen that the albuminoids are higher in the dry substance of one of the en- silages, No. 1502, than in the dry substance of any of the stalks. The high figures in the ensilage are probably only relative, due to a great loss of carbohydrates and little change of albuminolds. Exact quavtitative experiments are greatly to be desired, in order that we may have some explanation of the interesting changes which undoubtedly occur. Washington, October, 1884.

ISSN:0368-1645    

DOI:10.1039/CT8854700080

出版商:RSC    

年代:1885

数据来源: RSC

摘要:

90 X.-On Condensation Colnpoutzds of .Benzil with Ethyl Alcohol. By FRANCIS R. JAPP, M.A., Ph.D., and Miss MARY E. OWENS, B.S. (Cincinnati). IN preparing benzilic acid by heating benzil with alcoholic potash, Jena (AnnaZen, 155, 79) observed the formation of a neutral compound, melting at 200", to which he ascribed the formula CIrH,,Oz, regarding it as isomeric with benzoin. He assigned to it the name tolane nlcohoZ. The quantity at his disposal was insufficient for further investigation. Limpricht and Schwanert (Ber., 4, 335) obtained the same com- pound by heating together benzoin and alcoholic potash with access of air. They arrive at the conclusion that it is a derivative of benzoin (al'though they show in the same experiment that benzil is formed under the above conditions by the oxidising action of the air upon the benzo'in), and state their suspicion that the benzil employed by Jeiia must have contained benzo'in.On the strength of their analyses (not published) they arrive at the formula C30H2601, and name the compound ethy Zdib enzozn. We have found that, by the protracted action of very dilute alcoholic potash on benzil in the cold, the above compound is formed in large quantity. The yield, amounting in one experiment to 6 grams from 10 grams of carefully purified benzil, quite precludes the possi- bility of a formation from benzoin present as an impurity. Our analyses lead to the formula, C30H2404, which differs from that of Limpricht and Schwanert by containing two atoms of hydrogen fewer. 'l'he formation of such a compound from benzil and alcohol might be expressed by the equation- 2C~J3~00~ + C2H6O = C30H2JOr + OHg.In order to prepare this compound, 10 grams of caustic potash were dissolved in 2; litres of alcohol, and to the solution thus obtained 200 grams of finely powdered benzil were added. The whole was shaken until the liquid was saturated with benzil, after which it was allowed to stand, shaking from time t o time. The separation of the compound begins at the end of the first or second day, and is practi- cally complete in about a fortnight. It is t'hus obtained as a crystalline pawder, but, when a larger quantity of alcohol is employed, so as to have all the benzil in solution from the commencement, it separates in moderately large lustrous crystals. The crude substance was washed with ether, to remove unaltered benzil, and then recrystallised, first from benzene, and afterwards fromJ A P P AND OWENS: CONDENSATIOS COMPOUKDS OF BENZIL.91 alcohol. The latter solvent deposits the compound in small lustrous crystals. These contain alcohol of crystallisation, which they lose only after long heating at 120". The compound, thus freed from alcohol, melted at 200--201", and yielded on analysis numbers agreeing with the formula C30H2104. We append, for the sake of comparison, the theory for Limpricht and Schwanert's formula C30H2604 :- At 100" they are permanent. Substance. co,. OH2. I. .... 0.1258 0.3694 0.0612 11. .... 0.1448 0.4260 0.0702 Calculated for (Japp and Owens.) C,,H,,O,. C ...... 80-36 H ...... 5.36 0 ...... 14.28 100.00 Calculated for C 3 0 H 2 6 0 4 .Found. (Limpricht and r--h-- 7 Schwanert .) I. 11. 80.00 80.08 80.24 5.78 5.41 5.38 14.22 - - 100~00 The difference in the percentages required by the two formulie is certainly rather small f o r analysis alone to decide between them, but we think that the mode of formation which we have just described renders the first formula the more probable. Purther, if the second formula were correct, the errors of analysis, both for carbon and hydrogen, would be in the wrong direction, whereas with the first formula the errors are in the usual direction. We think that the results obtained by our predecessors are possibly due to their having overlooked the alcohol of crystallisation, or, at all events, to their not having taken into account the difficulty of com- pletely expelling this alcohol.They crystallised the substance from alcohol, but none of them mention the presence of alcohol of crjstal- lisation. Jena appears t o have analysed a compound from which only a portion of the alcohol had been expelled. Thus, the formula C'30H2a01,C2H60 requires C 77.73 and H 6.07 per cent., whilst Jena finds C 78.7 and H 5.8 per cent., o r values intermediate between the foregoing and those required for the formula C3"H2*04. A similar, though smaller, error may have lowered the carbon and raised the hydrogen in Linipricht and Schwanert's analyses. The melting point of the substance analysed would probably afford no intimation of the presence of the alcohol, for we have found that the crystals containing alcohol do not, unless the temperature is rapidly raised in determining the melting point, melt lower than those from which the alcohol has been previously expelled.92 JAPP AND OWENS : CONDENSATION COMPOUNDS A determination of alcohol of crystallisation was made, with the 1.3890 gram of crystallised substance, on heating at 120", lost, following result :- 0.1284 gram.Calculated for C30H2404,C2H60. Found. Alcohol in 100 parts.. .. 9-31 9.24 As the percentage of hydrogen in the compound CWHZ4O4,C2HGO differs from that of a compound of the formula C30H2604,C?H60, we analysed a specimen of the air-dried substance containing alcohol of cry s t allisa ti on :- Substance. cop OHz. 0.1145 0.3256 0.0619 Calculated for C30H2404,C2H60' r-A-- Found. H,, .... 30 6.07 6.01 0, ......80 16.20 494 100.00 C3?. ..... 384 77.773 77-55 - - The formula C30H2604,C2H60, on the other hand, requires C 77.42 and H 6-45 per cent. The value obtained for hydrogen, coupled with that yielded by the compound dried at 120", appears to us to afford strong evidence in farour of the formula with less hydrogen. From a solution in hot benzene, the condensation-product is deposited in minute rhombojIda1 plates generally grouped in rosettes, and containing benzene of cry stallisation. The crystals, when ex- posed to the air, effloresce and become opaque. A portion of the crystallised substance, freed from adhering benzene by pressure between filter-paper and brief exposure to the air, 011 heating at 120", lost 14.96 .per cent. of its weight. The formula C,,H,,04,CsHs requires a loss of 14.83 per cent, Limpricht and Schwanert (Zoc.cit.) state that by heating " ethyldi- benzoi'n " with acetyl chloride, a monacetyl-derivative melting at 145" is obtained. We have been unable to confirm this result. The sub- stance may be heated for an hour with acetyl chloride at 100" without undergoing change. Protracted heating, or a higher temperature, produces resinification. We were equally unable to obtain an acetyl- derivative by boiling the substance with acetic anhydride. We have, however, made an observation which, we think, explains the supposed existence of a monacetyl-derivative. When the condensation-product is recrystallised several times from glacial acetic acid, the meltingOF BENZIL WITH ETHYL ALCOHOL.93 point sinks each time, until a limit is reached, when a substance is obtained melting at about 130". This limit may be reached in a single crystallisation, by boiling the compound for some hours with the acetic acid. The substance thus obtained is not an acetyl-deriva- tive, but a compound of the condensation-product with acetic acid (or possibly with acetyl and hydroxyl). On exposure to the air, and more rapidly on heating, it parts with acetic acid; and its melting point lies anywhere between 130" and 200" (the melting point of the original substance), according to the amount of drying to which it has been subjected. It is possible that Limpricht and Schwanert, if they employed acetic acid as a solvent, may have obtained this molecular compound, and analysed a product from which the acetic acid had been only partially expelled.This would account for t,he melt'ing point found by these investigators ; and the substance in this condition would also give figures agreeing more or less with those required for a monacetyl-derivative, seeing that the composition of such a derivative lies almost intermediate between that of the mole- cular compound and that of the original condensation-product. Calculated for r----------- c ........ 75.59 78.37 80.36 H ........ 5.51 5.31 5.36 0 18.90 16.32 14-28 100~00 100*00 100~00 C 3 C 1 H 2 4 0 4 , C 2 ~ 4 ~ 2 . C30H23(C2HR0)04. CROH240? ........ A specimen of the molecular compound, melting at 133", gave on analysis C 75.48 and H 5.34 per cent. As Limpricht and Schwnnert publish no details of preparation, or analytical figures, in connection with their acetyl compound, we have no means of tesiing the correctness of the above supposition. I n the benzene mother-liquors remaining from the purification of the foregoing condensation-product, we found a second substance, which was deposited in minute yellow crystals melting at 232".A larger quantity of this substance was obtained from the original alcholic potash mother-liquors (after removing the compound C3,,HNO4), by acidifying with hydrochloric acid, distilling off the alcohol to a small bulk, and precipitating the organic substance by the addition of water. This precipitated substance was treated with alcohol, in order t o remove benzoic acid and a soluble resin, and the crystalline residue was dissolved in hot phenol, and reprecipitated with alcohol.By a repetition of this crystallisation from Fhenol, the substance was94 GUTRRIE ON THE SOLUBlLITY OF CERTAIN SALTS obtained as a yellow crystalline powder, melting as above at 232". Analysis gave numbers agreeing with the formula C46H3104 :- Substance. cop. OH,. I . . . . 0.13.54 0.4204 0,0657 I1 .. .. 0.1534 0.4769 0.0742 I11 . . . . 0.1492 0.4640 0.0735 Calculated for Found. C46IW4. r---- 7 r-"- -7 I. 111. 111. C 4 6 . . . . 552 84.92 84.67 84.78 84.81 H,, . . 34 5.23 5.39 5.37 5.47 0 4 . . .. 64 9-85 - - - - -- 650 100.00 These analyses were made with different preparations. The formation of a compound of the above formula from benzil and alcohol may be expressed by the following equation :- 3C,4H,,O, + 2CZHt3O = C$,jH,,O4 + 4OHz. We have also found that dilute alcoholic potash acts slowly on henzo'in i n the cold, and, when air is excluded during the reaction, gradually converts it into a compound crystallising in silky needles, which melt at 250°, and are apparently distiiict from any of the compounds hitherto obtained by the action of potash on benzo'in. An account of this reaction is reserved for a future communication. Normal School of Xcieiice, South Kensington.

ISSN:0368-1645    

DOI:10.1039/CT8854700090

出版商:RSC    

年代:1885

数据来源: RSC