摘要:

J O U R N A L OF THE CHEMICAL SOCIETY. H. E. ARMSTRONG, Ph.D., F.R.S. A. DUPRB, Ph.D.,’F.R.S. C. GRAHAM, D.Sc. F. R. JAPP, M.A., Ph.D. HERBERT MCLEOD, F.R.S. HUGO MULLER, Ph.D., F.R.8. W. H. PERKIN, Ph.D., F.R.S. W. J. RUSSELL, Ph.D., F.R.S. E. SCHUNCP, Ph.D., F.R.S. J. MILLAR THOMSON. mitar : HENRY WATTS, B.A., F.R.S.# %jnb-&;biim : C. E. GROVES, F.R.S. ~~ Vol. XLIII. 1883. TRAXSACTIONS. LONDON: J. V A N VOORST, 1, PATERNOSTER ROW. 1883.LONDON : HAIlRTSON ANT) SONS, PRJPTEllS J S ORT/TNARY TO IIXTl MAJESTY, 8T. XARTiiY'Y LARE.C 0 N T E N T S . PAPERS READ BEFORE THE CHEMICAL SOCIETY. PAQ E 1.-On the Constitution of some Bromine-derivatives of Naph- 11.-On the Constitution of Lophine. (Second Notice.) By FRANCIS R. JAPP, M.A., Ph.D., Assistant Professor of Chemistry in the Normal School of Science, South Ken- 111.--Contributions from the Jodrell Laboratory.I. Contribu- tions to the Chemistry of Lignification. By C. F. CXOSS and E. J. BEVAN. By C. F. CROSS and E. J. BEVAN. 3. The Analysis of Certain Plant Fibres. By C. S. WEBSTER . . 18 1V.-On a Condensation-product of Phenanthraquinone with Ethylic Aceto-acetate. By FRANCIS R. JAPP, M.A., Ph.D., Assistant Professor of Chemistry in the Normal School of Science, South Kensington, and FREDERICK W. STREATFEILD V.-Note on the Preparation of Diphenylene Ketone Oxide. V1.-On Certain Brominated Carbon Compounds obtained in the Manufacture of Bromine. By S. DYSON, Student in the Laboratory of the Porkshire College, Leeds . . . 36 VI1.-On Ethylene Chlorobromide and some Compounds ob- tained from it.By J. WILLIAM JAMES, Ph.D. (Jena), F.C.S., Demonstrator and Lecturer in the Mining School, Bristol . VII1.-On the Condensation-products of (Enanthaldehyde IX.-Condensation-products of CEnanthaldehyde (Part 11). By W. H. PE~KIN, JUNR., Ph.D. . . 67 X. - On the Condensation-products of Isobutaldehyde obtained by Means of Alcoholic Potash. By W. HI. PERKIN, JUNR., Ph.D. 90 XI.-The Alkalo'ids of Nux Vomica. No. 11. On Brucine. By W. A. SHENSTOWE, Professor of Chemistry at Clifton XU.-The Behaviour of the Nitrogen of Coal during Destructive thalene. (Third Notice.) By RAPHAEL MELDOLA . . 1 sington . . 9 2. On the Oxidation of Cellulose. 2 i By W. H. PEEKIN, Ph.D., P.R.S. . . 35 37 (Part I). By W. H. PERKIN, JCJNR., Ph.D. . . 45 College, Bristol .. 101i V CONTENTS. PA0 E Distillation ; with some Observations on the Estimation of Nitrogen in Coal and Coke. By WILLIAM FOSTER, M.A., Lecturer on Chemistry at the Middlesex Hospital . . 105 XII1.-Preliminary Note on some Diazo-derivatives of Nitro- XIV.-Researches on the Induline Group. (Part I.) By XV.-On a New Method o€ Estimating the Halogens in Volatile By RICHARD T. PLLMPL'ON, Ph.D., and XV1.-A Modified Liebig's Condenser. By W. A. SHENSTONE, XVI1.-On Some Fluorine Compounds of Uranium. By ARTHUR SMITHELLS, B.Sc. (Dalton Scholar in the Laboratory of The Owens College) . . 125 XVII1.-On the Volume Alteration attending the Mixture of Salt Solutions. ByW. W. J. NICOL, M.A., B.Sc., F.R.S.E., Lecturer on Chemistry, Mason College, Birmingham . . 135 X1X.-Two New Aluminous Mineral Species, Evigtokite and Liskeardite.By WALTER FLIGHT, D.Sc., F.G.S., of the Department of Mineralogy, British Museum, South Ken- sington . . 140 XX.-On the Absorption of Weak Reagents by Cotton, Silk, and Wool. By EDMUND J. MILLS, D.Sc., B.R.S., and JOKICHI TAKAMINE, of the Imperial College of Engineering, Tokio, Japan . . . , 142 By RICHARD COWPER, A.R. S.M., Demonstrator in the Laboratory of the Royal Naval College . 153 XXI1.-Some Notes on Hydrated Ferric Oxide and its Beha- viour with Hydrogen Sulphide. By LEWIS T. WRIGHT 1.56 XXII1.-Note on Derivatives of Fluorene, C,,Hzo. By W. R. HODGKINSON and F. E. MATTHEWS . . 163 XX1V.-On a-Ethylvalerolactone, a-Ethyl p-Methylvalerolac- tone, and on a Remarkable Decomposition of &Ethyl- aceto-succinic Ether. By SYDNEY YOUNG, B.Sc., Strassburg XXV.-On the Constitution of Molecula,r Compounds. The Molecular Weight of Basic Ferric Sulphate.By SPENCER UMFREVILLE PICKERING, B. A. Oxon, Lecturer in Chemistry at Bedford College . . 182 XXV1.-The Phenates of Amido-bases. By R. S. DALE, B.A., and C. SCHORLEMMER, F.R.S. . . 185 XXV1I.-On some Derivatives of Diphenylene Ketone Oxide. benzyl Cyanide. By W. H. PERKIN, Ph.D., F.R.S. , . 111 Owo N. WITT, Ph.D., F.C.S., and EDWARD G. P. THOMAS Organic Compounds. E. E. GRAVES . . 119 . 112 Professor of Chemistry at Clifton College . . 123 XX1.-On the Action of Chlorine on Certain Metals. University . . 172 By A. G . PERK~N . . . 187CONTEKTS. v PAGE XXVII1.-C hemico-Microscopical Researches on the Cell-con- tents of certain Plants. By A.B. GRIFFITHS, F.C.S., Member of the Liverpool Association of Science and Arts, Medallist in Chemistry and Botany, &c. XX1X.-On Condensations of Compounds which contain the Dicarbonyl-group with Aldehydes and Ammonia. By FRANCIS R. JAPP, M.A., Ph.D., Assistant Professor of Chemistry in the Normal School of Science, South Ken- sington . XXX.-On some Condensation-prodncts of Aldehydes with Acetoacetic Ether and with Substituted Acetoacetic Ethers. By F. E. MATTHEWS . By Sir J. B. LAWES, Bart., LL.D., F.R.S., J. H. GILBERT, Ph.D., F.R.S., and R. WARINGTON . . XXX1.-Contribution to the Chemistry of “ Fairy Rings.” Anniversary Meeting . . . . XXXI1,-On the Estimation of Hydrogen Siilphide and Car- bonic Anhydride in Coal-gas.XXXII1.-Contribution to the Chemistry of the Cerite Metals. By BOHNSLAV BRAUNER, Ph.D., F.C.S., Berkeley Fellow of the Owens College . XXX1V.-Some Compounds of Antimouy and Bismuth contain- ing two Halogens. By R. W. ATKINSON, B.Sc. (Lond.), F.I.C. . XXXV.-crystallographic Examination of the Crystals of Antimonio-potassic Chlorobromide. By R. H. SOLLY, Esq., Cambridge . XXXV1.-On the Gases evolved during the Conversion of Grass into Hay. By PERCY F. FRANKLAND, Ph.D., B.Sc., Demonstrator of Practical Chemistry in the Normal School of Science, South Kensington, and F. JORDAN, F.C.S.. XXXVI1.-Note on an Apparatus for Fractional Distillation under Reduced Pressures. By L. T. THORXE, Ph.D. . XXXVII1.-Notes on the Condition in which Carbon exists in Steel. By SIR FREDERICK ABEL, C.B., F.R.S., and W.H. DEERING, F.C.S. . XXX1X.-On the Spectrum of Beryllium, with Observations relative to the Position of that Metal among the Elements. By W. N. HARTLEY, Royal College of Science, Dublin. . By EDWARD DIVERS, M.D., Principal, and M. SHIMOS~, Student of the Imperial Japanese College of Engineering . X L1.-On Tellurium Sulphoxide. By EDWARD DIVERS and By LEWIS T. WRIGHT . XL.-On a New Oxide of Tellurium. $1. SHl&JOSfi . 195 19 7 200 208 224 267 278 289 293 294 301 303 316 319 323Vi CONTENTS. PAQ E XLI1.-On a New Reaction of Tellurium Compounds. By EDWARD DIVERS and M. SHIMOS~ . . 329 XLII1.-Contributions to the Chemistry of Tartaric and Citric Acid. By the late BEAUMONT J. GROSJEAN, Chemist to Sir J. B. Lawes’ Citric and Tartaric Acid Factory, &fillwall: compiled from the Author’s Manuscripts by R.Warington . XL 1V.-Note on a Basic Ammonio-copper Sulphate. By SPENCER UMFREVILLE PICKEMNG, B.A., Oxon, Chemical Lecturer at Bedford College . . . . . 336 XLV.-Note on the Action of Sulphuric Acid (sp. gr. 1.84) upon Potassium Iodide. By HERBERT JACKSON, King’s XLV1.-Laboratory Notes. By J. H. GLADSTONE, Ph.D , P.R.S., and ALFRED TRIBE, P.C.S., Lecturer on Chemistry in Dulwich College . . . . . 341 XLVIL-The Action of Nitrous Anhydride on Glycerol. By ORME MASSON, M.A., B.Sc., Edinburgh University . . 348 XLVII1.-On the Preparation of t,he Pentathionates. By S. SHAW, Student in the Laboratories of the Owens College , 351 XL1X.-Note on Pentathioriic Acid in connection with the fore- L.-Note on the Action of Allylic Iodide upon Phenol in the By PERCY F.FRANK- By By Professor P. T. By F.I.C., Christ Church Laboratory, 331 College, London . . . 339 goingpaper. By WATSON SMITH . . 355 LAND, Ph.D., B.Sc., andT. TURNER, F.C.S. . 357 presence of Zinc or Aluminium-foil. L1.-On a Bye-product of the Manufacture of Aurin. LI1.-On Samarium and its Compounds. LII1.-The Rate of Decomposition of Ammonium Nitrate. ALEXANDRE CLAPAR~DE and WATSON SX~TH . . 358 CLEVE, Hon. Xember of the Chemical Society . . 362 V. H. VELEY, MA., Oxford . . 370 L1V.-On Evaporation in Vacno. By HERBERT MCLEOD . . 384 LV.-On the Specific Gravity of Paraffin, Solid, Fused, and in Solution. By GEORGE BEILBY . . 388 LV1.-On Homologous Spectra. By TV. N. HARTLEY, F.R.S.E., Professor of Chemistry, Royal College of Science, Dublin .390 LVI1.-Thioxalic Ether. By H. FORSTER MOELEY, D.Sc., and W. JOHNSTON SAINT . . 400 LVII1.-On the Condensation-products formed by Benzoic Aldehyde with Malonic and Isosuccinic Acids. By CHARLES LIX.-A Contribution to the History of the Constitution of Bleaching Powder. By L. TRANT O’SHEA, Assistant Lec- turer and Demonstrator in Chemistry in Firth College, Sheffielcl . . 410 M. STUART, B.A. . . . . . 403CONTENTS. vii LX.-Researches on Secondary and Tertiary Azo-Compounds. No. I. By RAPHAEL MELDOLA . LX1.-On the Production of Hydroxylamine from Nitric Acid. By EDWARD DIVERS, M.D., Principal of the Imperiad Japanese College of Engineering . LXI1.-On some Compounds of Phenols with Amido-bases. By GIBSON DYSON, Dalton Scholar of Owens College . LXII1.-Chemistry of Lacquer (Urushi). Part I. Communi- cation from the Chemical Society of Tokio. By HTKORO- KURO YOSHIDA . Proceedings at t>he Meetings of the Chemical Society, Session Donations to the Library, 1882-83 Index . 1882-83 . . PAGE 425 4.43 466 4 72 487 494 591CONTENTS. vii LX.-Researches on Secondary and Tertiary Azo-Compounds. No. I. By RAPHAEL MELDOLA . LX1.-On the Production of Hydroxylamine from Nitric Acid. By EDWARD DIVERS, M.D., Principal of the Imperiad Japanese College of Engineering . LXI1.-On some Compounds of Phenols with Amido-bases. By GIBSON DYSON, Dalton Scholar of Owens College . LXII1.-Chemistry of Lacquer (Urushi). Part I. Communi- cation from the Chemical Society of Tokio. By HTKORO- KURO YOSHIDA . Proceedings at t>he Meetings of the Chemical Society, Session Donations to the Library, 1882-83 Index . 1882-83 . . PAGE 425 4.43 466 4 72 487 494 591

ISSN:0368-1645    

DOI:10.1039/CT88343FP001

出版商:RSC    

年代:1883

数据来源: RSC

摘要:

JAPP ON THE CONSTITUTION OF LOPHINE. 9 II.-OrL the Constitution of Lophhe. (Second Notice.) By FRANCIS R. JAW, M.A., Ph.D., Assistant Professor of Chemistry in the Normal School of Science, Sodh Kensington. IN No. 11 of the Berichte, 1882, p. 1403 (see also this Journal, 1882, Abstracts, p. 1063) Radziszewski communicahes a new synthesis of lophine by the interact,ion of benzil, benzaldehyde, and ammonia. This reaction corresponds with the synthesis of para-hydroxylophine from benzil, parahydroxybenzaldehyde, and ammonia, described by Japp and Robinson (Bar., 1882, p. 1268; this Journal, 188%, p. 326). I n discussing his synthesis, JAadziszemski comes to the conclusion that lophine has the formula- C,H,-C=N I \CH-GH$? C,&-c=N’ and rejects the forrnda- C,H,-C-NH 11 \C-c,H,, C6H5-C-N--d proposed by Mr.Robinson and myself. I n the latter formula, lophine is represented as belonging to the class of the anhydro-bases described by Hiibner. I shall, therefore, in the present paper, refer to this formula as the “ anhydro-base formula ” of lophine. This formula was based chiefly upon certain analogies drawn from10 JAPP ON THE COXSTITUTION OF LOPHINE. the reactions of phenaiithraquinone with aldehydes and ammonia. I will now endeavour to show that these analogies are well foiinded, in- asmuch as benzil really yields with aldehydes and ammonia the same classes of compounds as phenanthraquinone, though not always under the same conditions ; further, that the anhydro-base formula explains the known reactions of lophine more consistently than that of Ftadzis- zewski ; and lastly, I shall describe an experiment which, though not abrolutely conclusive, affords a strong presumption in favour of the anhydro-base formula.I n order that what follows may bemore readily understood, I will re-state here the two fundamental reactions of phenanthraquinone with aldehydes and ammonia :- C6Ha-cO C6H4-G-0 1. I I + R‘-CHO + NH3 = I 11 b - R ’ + 20H2. C,H4--CO C6H4-C--N’ C,H,-CO CGH, C-NH c6H4- c 0 c6H,-c-N--y 11. I I + R’-CHO + 2NH3= I 11 \C-R’+ 30H2. The first reaction occurs with non-hydroxylsted, the second with hydroxylated aldehydes of the benzene series. This explains s u 6 - ciently why we resortecE to the indirect method of employing a hydr- oxyaldehyde, and thus preparing first a hydroxylophine, instead o€, like Radziszewski, acting upon b e n d with benzaldehyd e in presence of ammonia, and thus preparing lophine directly ; for, following the analogy of the phenanthraquinone reactions, we must have expected in the latter case to obtain the conipound- by a reaction corresponding wibh that expressed in equation I.* I n fact, previously to the publication of Radziszewski’s paper, we had tried the reaction which he describes.Wc hoped t o obtain the above oxygenated compound, and were surprised to find that the reaction yielded lophine. We conducted the experiment under conditions somewhat different from those adhered to by Radziszewski : instead of saturating an alcoholic solution of benzil and benzaldehyde with ammonia a t a temperature of 40-50°, we heated molecular propor- tions of benzil and benzaldehyde with aqueous ammonia under pres- sure-on one occasion a t lOO”, on the second a t 150”.I n the first * We were the more justified in this expectation, inasmuch as chrysoquinone- also a double ketone-yields, with benzsldehgde and ammonia, benzenylamido- chrjsole.JAPP ON THE CONSTITUTION OF LOPIIINE. 11 case the yield of lophilie was 4G per cent. of the theory; in the second 93 per cent. I have repeated Radziszewski’s experiment, and had no difficulty in obtaining lophine, but cannot confirm his statement as to the almost theoretical yield. On the contrary, the yield was in my hands but small. With regard to the above oxygenated compound which I hoped to obtain from benzil, benzaldehyde, and ammonia, it is in the highest degree probable that this compound has been known for a very long time, without, however, its true nature being recognised.(The ex- istence of this compound has, as I shall endeavour to show presently, a distinct bearing upon the question of the constitution of lophine.) Zinin (Annulen, 34, 190), by adding aqueoas ammonia to a warm alcoholic solution of benzil, obtained a compound to which he assigned the formula C42H30N302, and to which the name azobestzii! was after- wards given. Halving this formula, we arrive a t C21H15N0, the formula of the compound sought for. Zinin draws attention to the simultaneous production of ethylic benzoate in the reaction, and re- marks that the formation of azobeiizil is accounted for by this fact, without, however, explaining more precisely in what way this is the case.The formation from benzil and ammonia of a compound of Zinin’s formula corresponds to a reduction, and Zinin probably only meant that this reduction was accounted for by the simultaneous oxidation of a portion of the benzil to benaoic acid. Zinin’s reaction may, I think, be interpreted in the following man- ncr:-In the first place, a portion of the benzil is decomposed in presence of alcohol and ammonia, with formation of ethylic benzoate and benzaldehyde :- The benzaldehyde then reacts with a second molecule of benzil and one molecule of ammonia, yielding azobenzi.1:- CGHS-CO CsH5-C-0 CGHS-CO c6H5-c-x’ I + C,H,-CHO + NHS = 11, b-C6H5 + 20H2, Azobenml. the reaction taking place according to equation I of the phenanthra- quinone series.In order as far as possible to test the correctness of this supposi- tion, and to ascertain the nature of this compound, a quantity of it was prepared by Zinin’s method. Aqueous ammonia was added to a warm alcoholic solution of b e n d till a precipitate was produced ; this12 JAPP ON THE CONSTITUTION OF LOPHINE. was then left in contact with the liquid a t a temperature of about 70" for ten hours. Instead, however, of crystallising the subskance from dcohol, it was found advantageous to extract the whihe crystalliue powder, which formed the product of the reaction, with boiling light petroleum, in which the azobenzil readily dissolved, but the other sub- stances present were practically insoluble. The solution on cooling deposits the pure compound in groups of fine colourless prisms.By crystallisation from boiling alcohol, it was obtained in the very lustrous long thin needles described by Zinin. The fusing point, which is not given by Zinin, was found at 115". The substance boils above the range of the mercurial thermometer. A small quantity was boiled for some time in a test-tube without suffering the slightest decomposition-a behaviour which scarcely points to a compound containing 42 atoms of carbon in its molecule. Concentrated hydro- chloric acid converts it into a gummy hydrochloride. Heated under pressure with the acid to 250", it yields benzoic acid, ammonium chloride, and a resinous mass. Analysis confirmed Ziniu's results :- Substance. cos. OH,. I ........ 0.1157 0.3607 0.0547 11.0.1572 gram burnt with copper oxide in a vacuum gave 6-6 C.C. moist nitrogen at 22" and under 754 mm. pressure. Calculated Found. for C2,H,,N0. w - 7 7-- 1 I. 11. C,, .......... 252 84.85 85.02 5.25 - HI,. ......... 1-5 5.05 N .......... 14 4 71 - 4-71 0 .......... 16 5.39 297 1 O O W - - - -- --- The vaponr-densiky of the substance was determined by Victor Meyer's air-displacement method, heating in a lead-bath, with the following result :- 0.0881 gram displaced 7.3 C.C. air measured moist a t 19", and under 75 7.5 mm. pressure. Calculated for C,,H,,NO. Found. Vapour-density (air = 1) ...... 10% 10.23 The substance, therefore, possesses the formula and molecular weight here assigned to it, and the above may be regarded as the most probable account of the mechanism of the reaction in which it is formed .JAPP ON THE CONSTITUTION O F LOPIJIKE.13 If, on the other hand, in the reaction of benzil with ammonia, the benzaldehyde which is formed by the decomposition of 1 mol. of benzil were to react, together with two molecules of ammonia, upon a second molecule of benzil, lophine would be formed, the reaction taking place according to equation I1 of the phenanbhraquinone series. In fact, Radziszewski has shown that lophine is obtained in small quantity by the act,ion of ammonia upon bemil. What I wish to point out is that in these cases-just as in the corresponding reactions between the methyl ether of salicylaldehyde, phenanthraquinone, and ammonia-we have the two reactions I and I1 taking place simultaneously with the formation of two compounds- one containing 1 atom, the other 2 atoms of nitrogen.Now there is only one at all probable mode of formulating the com- pounds containing 1 atom of nitrogen, consistently with their forma- tion from 1 mol. of double ketone, 1 of aldehyde, and 1 of ammonia. We must assume in them the existence of the complex of atoms- -4-0 -C-N II >c- This is also in accordance with their decompositions. Thus benzenyl- amidophenanthrole and azobenzil, when heated with concentrated hydrochloric acid, are split up into benzoic acid and ammonia, whilst the phenanthrene and stilbene portions of the molecule are resinised under the conditions of the experiment. We have therefore to assume that during the formation of the com- pounds containing 1 atom of nitrogen, an intramolecular re-arrange- ment occurs: the two carbon-atoms of the double ketone-group, -CO-CO-, become united by double bonds. This corresponds with what occurs when a quinone of the ortho-series-also a double ketone-is converted by the achion of reducing agents into a quinol.* * With phenanthraquinone, three cases of this intramolecular re.arrangement, occurring under the influence of reducing (or liy drogenating) agents, or of substances equhalent in their action to reducing agents, are known : the conversion of phenan- thraquinone into phenanthraquinol by the direct addition of two atoms of hydrogen ; the conversion of phenanthraquinone into the monethylic ether of phenanthraquinol, by the successive action of zinc-ethyl and water, the reduction in this case consisting in the indirect addition of the equivalent of two atonis of hydrogen in the shape of ono atom of hydrogen and one ethyl-group ; and lastly, tlie action of aldehydes, together with ammonia, upon phenanthraquinone. The formation of the double compound of phenanthraquinone with hydrogen sodium sulphite might perhaps be added to this list.Since in all such reactions the above-mentioned re-arrangement orccrs in the carbon linkings of the closed lateral chain, no reactions in whicli phenomena of reduction are involved can be emplojed in determining the consti- tution of phenanthraquinone. Practically, all the arguments in favour of Graebe's formula for phenanthraquinone ha-Fe been drawn from some such aource. I hope14 JAPP ON THE CONSTITUTIOK OF LOPHIKE.I n the present case the reducing agent is an aldehyde, and, when the aldehyde has done its work, we have no longer an aldehyde-residue, but an acid-residue in the molecule of the new compound. The occurrence of this re-arrangement has been proved for three double ketones-phenanthraquinone, chrysoquinone, and benzil. As regards the compounds containing 2 atoms of nitrogen in the molecule, it seems to me that the simplest way of formulating these is to assume in them the existence of the complex of atoms- -C-NH -C-N-- I1 y- This is what I have done in the work on phenanthraquinone and in the paper on lophine published in conjunction with Mr. Robinson. I take for granted an intramolecular re-arrangement, such as oceurs in the formation of the oxygenated compound.Radziszewski, on the other hand, assumes in the latter class of compounds the existence of the complex- --C=N. I )CH- -C=N Here the assumption of an intramoleculaz re-arrrangement is dis- pensed with, and this is so far a point in favour of Radziszewski’s formula. This mode of formulating these compounds did not escape me ; but I rejected it for the reasons above given. It seemed to me a more probable assumption that in two reactions of the same class- both condensations of double ketones with aldehydes and ammonia, both of the class of condensations in the ortha-aeries (employing the term “ ortho ” in an extended sense)-occurring simult,aneously in the same operakion, an intra-molecular re-arrangement which must occur in the one and which is conditioned by the reducing action of the aldehyde, should also occur in the other, the same condition being again present.Up to this point I have described the grounds of analogy which led me to prefer the anhydro-base formula for lophine to that of Eadzis- zcwski. I t now remains to regard the two formula3 from the point of view of the reactions of lophine. Radziszewski finds a confirmation of his formula i n the fact that lophine, when fused with potassium hydrate, yields benzgl alcohol and benzoic acid ; and he ascribes the formation of these substances to the action of the alkali upon benzaldehyde furnished by the decomposition shortly to be able to lay before the Society an account of some reactions which are not open to the above objection, and which appear to me to decide in favour of Fi tti g ’ s formula.JAPP ON THE CONSTITUTION OF LOPHINE.13 of the lophine. I cannot find that this reaction decides either way. A compound of the anhydro-base formula would split up under the influence of the alkali into henzoic acid, ammonia, and the hypo- thetical compound- C6H5-C (OH) CsH5-C (OH) I1 a cornpound which csrresponds with 2 mols. of benzaldehyde, and would be decomposed by the alkali with formation of the benzoic acid and benzyl alcohol obtained by Radziszewski. By carefnl oxidation, lophine yields benzamide and dibenzamide, according to the equation: CZ1Hl6N2 4- OHz + 0, = C6H5.C0.NHTI, + NH(C6H5.CO), (Fischer and Troschke). If we adopt the anhydro- base formula, this reaction is readily accounted for.It is only neces- sary to assume that, as is usual i n the oxidation of unsaturated compounds, the separation of the parts of the molecule occurs a t the points where the atorne are connected by double boiids:- 0 .C,H,-C--NH O II . >C-C,H,. CGH5--C I? --N ,/ 0 H, It, is diEcult to gee i n what way Radziszewski’s formula can acaount for this reaction. One point in which the anhydro-base formula appeared to satisfy all requirements was .the way in which it accounted for the formation of compounds containing alcohol.radic1es ; for example : Kuhn’s am- monium-compound, diethyl-lophinium iodide, C,,H,,( CzH,),N,I (cf. this Journal, Trans., 1882, 329), a compound corresponding with Hubner’s diethylanhydrobenzdiamidobeiieene iodide, C,,H, ( CzE&N21. In Radziszewski’s lophine formula there is no peplaceable hydrogen- atom attached to nitrogen, so that the formation of this cornpound of Kuhn’s cannot be aeconnted for.Radziseewski perceives this diffi- culty, but I think that he underrates it. He says that the fact that lophine, although containing no hydrogen directly attached t o nitro- gen, yields compounds, with alcohol-radides “ cannot surprise any one who has studied Hof mann’s beautiful researches on the exhaustive action of methyl iodide upon conine and piperidine.” The cases are, however, scarcely comparable. Dimethylconine and dimethyl- piperidine were obtained by the destructive distillation of the corre- sponding ammonium-hjdroxides--a process very diff ereat from that16 JAPP ON THE CONSTITUTION OF LOPHINE.employed in preparing diethyl-lophinium iodide, which Kuhn obtained by heating lophine with ethyl iodide a t 100". The following simple reaction appeared calculated to decide between the two formula. Rarlziszewski's formula contains, as already pointed out, a benzaldehyde-residue (benzylidene) ; the anhydro-base formula contains a benzoic acid-residue (benzenyl). Fischer and Troschke have shown that lophine may be heated with hydriodic acid and amorphous phosphorus to 220" withoiit change. It seemed to me that if it were possible, by the action of the acid at a still higher temperature, to split up the lophine, a compound of Radziszewski's formula ouzht to yield benzaldehyde, which would tben be reduced to toluene ; whilst, a compound of the mhydro-base formula would yield benzoic acid, which would not undergo further change.As benzoic acid could not, in presence of a powerful reducing agent like hydriodic acid, he fnrnished either by the dibenzyl-residue of Radziszewski's formula, or by the stilbene-residue of the anhydro-base formula, the formation of benzoic acid under these circumstances might be taken as deciding in favour of the latter formula. As a fact, I find that lophine when heated with hydriodic acid and amorphons phosphorus to x temperature a little over 300°, splits up, yielding benzoic acid. As the pressure with strong hydriodic acid proved unmanageable, a mixture of one volume of the strongest hydriodic acid with four volumes of fuming hydrochloric acid was employed instead. That a sufficiency of the reducing agent had been employed, was evident from the fact that, on cooling, the upper part of the tnbes contained crystals of phosphonium iodide.The pressure on opening, in spite of the dilution with hydrochloric acid, was very great. The main portion of the lophine was recovered unchanged, the difficultly soluble lophine salt fusing together and thus escaping further action. Had the above reaction occiirred at a lower temperatnre, I should have regarded it as absolutely conclusive against Radziszewski's for- mula. As i t is, I think the probability that the benzoic acid can have been formed from anything else than a beilzoic acid residue very slight. It is to be borne in mind that, as the temperature rises and the danger of bye-reactions increases, the power of the reducing agent also increases.Further, the temperature, though high, is a t least 100" lower than that at which lophine boils without decomposition. According to a determination made by means of a Geissler high-tem- perature mercurial thermometer registering to 450" (with internal pressure to prevent tihe boiling of the mercury), lophine boils a t 415" (uncorr.). Of course the indications of such an instrument areonly approximate. * * Rsdziszewski also makes some highly ingenious suggestions concerning the con- No resinous products are formed.JAPP ON THE CONSTITUTION OF LOPHINE. 17 In fulfilment of the promise made in the former communication on the above subject, I have studied the action of other aldehydes, toge- ther with ammonia, upon benzil. Parahydroxybenzaldehyde yields, Ftitution of glyoxaline, which he regards as “ lophine, in which the three phenyl- groups are replaced by three hydrogen-atoms.” He considers that when glyoxrtline is formed by the action of ammonia upon glyoxal, a portion of the glyoxal first takes up the elements of water, yielding formic acid (the production of which in the reaction has been observed by Ljubavin’l and formaldehyde ; and that this last sub- stance then reacts with glyoxal and ammonia to form glyoxaline, a reaction which would correspond with that in which lophine is formed from benzaldehyde, benzil, and ammonia.I do not at present propose to go into this subject further than to point out that if, while accepting the above analogy, we formulaic glyoxaline on the basis of the anhydro-formula of lophine, thus :- CH-NH It \CH CH-’J!i=H we arrive a t a formula which, I consider, accounts better for the reactions of this compound than any of the formulce which have aa yet been proposed for it.The only fact connected with glyoxaline which this formula does not readily explain, is the identity of methylglyoxaline with oxalmethyline. Addendum-Since the above was written, Radziszewski has published a second paper (Bey., 15, 2706), in which he describes the synthesis of Wallach’s pamxal- methyline by the interaction of glyoxal, acetaldehyde, and ammonia- here again employing a reaction belonging to the class of condensations discovered by me. He does not appear to have expected to obtain paraoxalmethyline, but only some homologue of glyoxaline. B e formulates paraoxalmethyline on the type of his lophine formula.I intend discussing this reaction more fully elsewhere, but in the meantime desire to take this opportunity of putting on record the following formula?, which are founded upon the glyoxaline formula given above :- CH--N (CH,) II \CH CH-NR Oxalmethyline (identical with methylgiyoxaline), CH-N (CZH,) I1 \C-CH3 CH-NN Oxalethy line. CH-NH II \C-CH, CH-NH Paraoxalme thyline. These formultle, which furnish a consistent account of the reaotions of Wallach’E oxalines, were constructed by me in August last, at which time I suggested to Dr. F. E. Matthews, who was then working with me, that he should attempt the synthesis of pareoxalmethyline from glyoxd, acetaldehyde, and ammonia. I thus predicted the result now obtained by Radziszewski. I wish, however, expressly to state that this train of tliought wa.s mainly suggested by the above speculations of Radziszewski on the formation of glyoxaline. But, a t the same time, I do not think that it would have been possible for Radziszewski, holding the views which he does concerning the constitution of glyoxaline, to predict the formation of paraoxal- methyline in the above reaction. VOL. XLIII. C18 CROSS AND BEVAN: CHEMISTRY OF LIGNIFICATION. as already described, parahydroxylophine. With salicylaldehyde R different reaction occurs : 2 mols. of aldehyde, together with 2 of ammonia, react with 1 of benzil, yielding a compound totally dis- tinct in its properties from parahydroxylophine ; thus :- C 1 3 1 0 0 2 + 2C7H602 + 2NH3 = C-pJlJY204 + 20H2. Benzil. Salicyl- New compound. aldehyde. Furfuraldehyde acts in a similar manner. results of the investigation of this new class of compounds. I hope to be able to lay before the Society, at an early date, the

ISSN:0368-1645    

DOI:10.1039/CT8834300009

出版商:RSC    

年代:1883

数据来源: RSC

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18 CROSS AND BEVAN: CHEMISTRY OF LIGNIFICATION. 111. -CONTRIBUTIONS FROM THE JODRELL LABORA- TORY. 1 .-Contributions to the Chemistry of Lign@catiolz. By C. F. CROSS and E. J. BEVAN. FOLLOWING the views advanced by physiologists on the chemical phenomena of lignification, we were led to forsake the incrustation theory, as not adequately expressing the facts established concerning the origin, properties, and decompositions of the lignified substance, and to adopt, as a working hypothesis, the alternative view of lignose, or bastose, as we ventured to call the jute-fibre substance, viz., that it is a chemical whole in the sense of presenting a true combination rather than a mixture of cellulose with its non-cellulose constituents. Subsequent observations have further justified this course.By means of fractional solution in the ammonia-copper reagent, we uniformly obtained an amorphous modification of the fibre substance, exhibiting properties similar to the original as regards its behaviour both to chlorine and t o acids. In one particular, however, a, difference is observed, in that the freshly precipitated amorphous modification gives only a slight reac- tion with aniline snlphate, and after a second solution and precipit,a- tion no coloration is obtained. That this reaction, supposed to be essentially characteristic of lignose, is in reality due to some product of change (probably of oxidation) is further shown by the fact that this property of giving a yellow colour with aniline salts is entirely lost after the substance has been boiled in a solution of sodium sul- phite, the other properties remaining unaltered. We find moreover that a yellow reaction with aniline salts is characteristic of a numberCROSS AND BEVAN : CHEMISTRY OF LIGNIFICATION.19 of aromatic aldehydes. If, for instance, oil of cinnamon be shaken with a solution of the sulphate, the whole solidifies to a mass of bright yellow needles. Lignose we think, therefore, is to be con- sidered apart from this property. We have previously shown that jute is resolved in various ways, according to the methods or conditions brought to bear upon it, the cellulose for instance appearing either as cellulose or in the form of acids of the pectic class. So also the non-cellulose appears either as an astringent substance, or in the form of the chlorinated derivative pre- viously described.In reference to the latter arid its evident connection with the aromatic series, Dr. Amstrong directed our attention to the researches of Stenhouse and Groves on the chlorination of pyrogallol as probably bearing on the subject. We prepared mairogallol accord- ing to their method (Ckein. Soc. J., 1875), and found that both it and the amorphous substances which constitute the chief portion of the product give, when treated with sodium sulphite solution, a colour- reaction exactly resembling that which is characteristic of the freshly prepared lignose derivative. A close connection of these plant-con- stituents with the trihydric phenols, which can be seen to be suggested on grounds which are independent of this observation, we venture to think is thereby fairly established.Following up this subject, we endeavoured to prepare a more highly chlorinated derivative of bastose. The derivative obtained by the action of chlorine gas upon bastose in presence of moisture is an amorphous yellow body, which, only when freshly prepared, gives the colour-reaction with sodium snlphite. Although this indicates the occurrence of molecular change during the process of purifying the body for analysis, and although its amorphous character places it in that much abused category of substances to which the ordinary criteria of purity are inapplicable, the numbers obtained in the analy- sis of preparations various in origin and differently prepared, were constant, and agreed with those requil.ed by the formula n(C,9H,,CI,0,).In justification of the adoption of this formula we would state first that it was our only guide in investigating the constitution of lignified fibres, and secondly, that substances which go to build up living tissues are of very necessity colloids, and their immediate derivatives also; but because colloiids they are none the less definite, and at all events the method of ultimate analysis must be applied to their inves- tigation until it is shown to be nugatory. The chlorinated compounds experimented npon mere obtained, the one from jute and the other from the fibre of Musa paradisiaca, it monocotyledonous plant. The purified fibres were exposed in the damp state to an atmosphere of chlorine gas, and the reaction being complete, the products were severally dissolved away by means of c 220 CROSS AND BEVAN : CHEMISTRY OF LIGNIFICATION. alcohol, precipitated with water, washed and dried first in a vacuum, and lastly at 100".These were then separately dissolved in glacial acetic acid, and further chlorinated after the manner described by Stenhouse and Groves. The products were separated by pouring the acetic solution into water, whereby they were precipitated in the form of a yellowish-white substance resembling wax. After washing and drying, first in a vacuum, and lastly at loo", they mere analysed, with the following results :- (a). From jute. (b.) From Musa. (a.) 0.4087 gme 0.5550 AgCl. (6.) 0.4892 ,, 0.6689 AgCl + 0*0060 Ag. 0.1234 ,, 0.1788 COz and 0.0435 H,O. 01790 ,) 0.2611 COz and 00564 H,O.(..J ( b . ) Cdc. CBH44C111016. C .......... 39.52 39-77 40.0 H . . ........ 3.92 3.50 3.8 C1 ........ 33.50 34.20 34.0 The products are therefore identical: It is impossible to account for their derivation from the original tetrachlorobastin (which we may represent by the formula C38H3~Cl,01,) by a symmetrical equation. At present we cannot do more than record the results as they stand. Starting indeed with a highly complex molecule, such as both bas- tose and the lower chlorobastin certainly are, and in view of the further complicating action of chlorine upon the trihydric phenols and their derivatives, which has been established by the work previously cited, we have no reason to expect a resolution into simpler molecules by means of this reaction.It would appear that only in the absence of oxidising conditions can this be effected, and it is from this point of view that we are following up the resolution of bstose, lignose, and the chlorobastins by means of the sulphites under extreme conditions of temperature and pressure. Note on, the Constitution of Eignwe. We would record two recent observations which bear upon the question of the mode of union of the constituents of lignose. (1.) Dry chlorine has no action upon this substance, whereas the presence of moisture determines instant combination, with evolution of heat. (2.) The furfural-yielding constituent survives exposure to chlorine, the chlorinated jute fibre giving an abundant yield of this aldehyde by distilling with hydrochloric acid.CROSS AND BEVAN : CHEMISTRY OF LIGNIFICATIOK. 2 1 In conclusion, we wish to express to Sir Joseph Hooker and Professor Thiselton Dyer our recognition of the privilege of occupy- ing the Jodrell Laboratory for tbe purpose of carrying out these researches, and our sincere thanks for their personal kindness to u s during our stay.ADDENDA. (1.) Note on the Xacchulmic C o ~ z t l z h . . Sestini has recently published (Gazsebta, 1882, 292 ; Chem. SOC. J., 1882, 1.182) the results of an investigation of the action of the halogens upon the sacchulmic compounds, and we wish to call atten-. tion to the similarity of the products obtained by him t o those which we have obtained from various substances of vegetable origin. For instance, the chloroxysacchulmide, C22H16C11012, described by him is closely similar to the derivative obtaiued by chlorinating the black substance formed by the action of H2S04 at 60-70” upon the carbo- hydrates, one preparation of which we analysed and found to be CmHl&l,Olo (Chem.8 o c . J., 40, 1122) : these two derivatives are in their properties identical. The resinous matter obtained from the alkaline liquors from Esparto boilers yield a series of chloro-deriva- tives similar in composition and properties to the above; and generally the products of degradation of the carbohydrates, natural and artificial, yield chlorine substitution-products having similau characteristics. Should the presence of an aromatic group in bhese, compounds, of which there appears to be some evidence (Jdresb., 1871, 741; 1872, 771), be established, Sestini’s results will &row additional light upon some of the difficult proble~ms snggesbed by the changes which the carbohydrates undergo in plant tissues.(2). Since reading this paper we have found that+ Dr. Miiller has preceded us in the observation that the reactian of aniline sulphate with lignified fibres, formerly supposed to be characteristic of lignose, is in reality due to some pi*oduct of its change; this he succeeded in removing by means of oxidising agents, such as Schulze’s solution, and dilute solution of chromic acid. We do not appear to have been singular Ih overlooking this obser- vation of Dr. Miiller’s, and we are glad to be able 60 reproduce itl, and add the confirmation afforded by the observations in this paper.* “ Pflanzenfaser,” foot-note to p. 11.2.-On the Oxidation of Cellulose. By C. F. Caoss and E. J. BEVAN. ON boiling cellulose with nitric acid (60 per cent.) it is slowly con- verted into oxalic acid. This decomposition may, however, by carefnl observation, be seen to take place in three stages. In the first place, the cellulose is thoroughly disintegrated, the change doubtless re- sulting in the formation of hydrocellulose (Girard, Bey., 9, 65). Oxidation of this into oxalic acid Ithen ensues. A portion of the iiiass, however, yields but slowly to the action of the nitric acid, in consequenw, as we find, of its conversion into an oxidised derivative, t o which we have provisionally given the name oxycellzt'lose. The quantity of oxycellulose produced appears to be about 30 per cent.of the cellulose acted upon. When thrown upon a filter and washed with hot water, the removal of the acid is attended with gelntinisation of the mass. In this state it is entirely soluble in dilute alkalis, and is precipitated 'from such solutions unchanged and in a form resem- bling peotic acid, on the addition of acids, as also of alcohol, saline solutions, or even strong solutions of the caustic alkalis. Observa- tions of the oornposition of these precipitates showed thah oxycellulose does not form compounds with bases, or at least only of a very weak order, the substance thrown down by alcohol or saline solutions re- taining only traces of inorganic matter. Specimens of oxycellulose obtained from various sources and purified in different ways were anslysed, after drying at 110", with the following results :- (a.) Prepared from cotton, dissolved in NsOH, precipitated with (b.) Prepared from jute, dissolved in NaOH, precipitated by HC1, ( c .) Prepared from jute, dissolved in NaOH, precipitated by HCl, (d.) 'Prepared from pith of AraEia papyrifera, analysed directly after BaC12, and washed. and washed. and washed. washing. a. 0.1756 gram gave 0.2779 COa and 0.0840 H20. J. 0.1329 ,, 0.2121 ,, 0,0642 ,, c. 0.1018 ,, 0.1617 ,, 0.0504 ,, d. 0.1388 ,, 0.2200 ,, 0.0689 ,, Calc. for a. 6. C. d. C , S ~ 2 6 0 , 6 . C .. .. . . . . 43.16 43.52 43.32 43.28 4340 * H . . .. .. . . 5.20 5-36 5.50 5.51 5-22 0 .. .. .. .. 51.64 31.12 51-18 51.26 5138 * Allowing for ash.WEBSTER: ANALYSIS OF CERTAIN PLANT FIBRES.23 Oxycellulose dissolves in concentrated sulphuric acid with a pink colour; the dissolved body, when isolated, is found to be dextro- rotatory, and otherwise similar in properties to ordinary dextrin. The freshly-prepared oxycellulose is not coloured by iodine or by Schulze’s solution, but the horny mass to which it dries is coloured deep blue by the latter. These facts, together with the formation of the “nitro”- body about to be described, establish the cellulosic character of OX-J- cellulose. The “ nitro”-body was prepared in the following way :- The gelatinous oxycellulose was washed with strong nitric acid until free from water, and was then diffused through a mixture of equal volumes of strong sulphuric and nitric acids, in which it quickly dis- solved. The solution, after standing for about an hour, was poured in a fine stream into a large volume of water, by which the “ nitro”- body was precipitated as a white flocculent mass.The product, after drying at 110”, was analysed according to Eder’s method (Ber., 13, l69), with the following result :--X 0.2342 gram gave 25.20 C.C. NO at 770 mm. and 19.4” C. Calc. for C18H,0163 (NO,) Percentage of N. 6.48 6-63 Our object in studying this resolution is to contribute to the solution of the problem of the constitution of cellulose. The decompositions of cellulose, including the above, go to show that it is made up of it, nucleus which exhibits considerable stability, and side groups which oasily yield to oxidation, and whose removal appears to cause only a subsidiary change in the composition or properties of the original.We have commenced the study of the oxidation of cellulose, in pre- sence of alkali, by means of permanganate ; and in addition to pro- ducts of low molecular weight, we have obtained a body exhibiting the characteristic properties of metapectic acid, a result which is in confirmation of the above hypothesis.? 3. The Analysis of Certailz Plant Fibres. By C. S. WEBSTER. AT the instance of Messrs. Cross and Bevan, I undertook the exten- sion of the results obtained by them in the investigation of the jute fibre to a series of the more commonly occurring plant fibres, and the main results of this work are embodied in the following table :- f We think it worthy of record that in a second determination by this method, tvith a larger quantity of substance (0.801 gram), when about 80 per cent.of the total NO had been expelled, the flask containing the boiling ferrous sulphate solu- tion was shattered, with a violent explosion. t Comp. H. Muller, “ Pflanzenfaser,” p. 15,-- 1. Yield of cellulose (C1 method) 2. Character of isolated cellulose 3. Loss in boiling 1 p. e. HKO (5 4. Ditto (60 minutes) . . , . . . . . , , 5. Ash.. .. .. .. .. .. . . . . .. .. .. .. 6. Aggregate elementary com- 7. Lignified or otherwise.. . . , . , , minutes) position , . . . . . , . . . , . , , { Pibro-vasoular bundles of monocotyledonous Agave Ameri- cana. 81 -2 Fibres free. 9.9 14 *6 1 *o 45.9 6 '1 Ligni- fied. Yucca $OriOE&. I 80 ' 8 Fibres free. 14 *6 16 -5 1 *3 - - Ligni- fied, plants, __I knanasst sativa (pine P-pple) * -~ 76.3 Fibres a ggluti- nated.9-6 19 10 1.0 42 -5 5 *6 Ligni- fled. Musa P?radi- smca nilla). c Ma- ~~~ 62 -8 Fibres aggluti- nated. 18 *6 31 -7 1 -6 42 -6 5 . 6 Ligni- fied. Phor- miuni tenax (New Zealand flax). 86 -3 Fibres partia.1ly agglu t i- nated. 5'8 9.9 0 . 9 44 *4 5 *9 Ligni- fled. Boeh- meria P U P 83 -8 Fibres partially aggluti- na! ed. 15 *6 24 '1 3 *7 41 -a 6.0 Not ligiiifled Bast fibres of dicotyledonous plants, Urtica hetero- phylla gherry nettle). 95 30 Fibres free. (Nil. _I 2 -6 7'3 1 -0 42 *9 5 . 9 Not lignified - Crota- laria juncea (Sunn). -- 76 *9 Fibres free. 5 -3 10 -7 0 9 9 - - Ligni- fied. Kibiscua strictus. 63 9 0 Fibres partially aggluti- nated. 13 -7 25 ' 5 2 *o - - Ligni- fied.Linum usitatis- simum (0ax). 82 -0 Fibres free. 7 '8 16 -6 1.7 43 -7 5 -9 Not lignified The specimens of fibres were obt,ained from the Museum a t Kew Gardens. Whole length samples were tvken ; purified by boiling in glacial acetic acid and afterwards in alcohol j dried at 100". 4 8 u1 Y M Cor- .=P chorus % capsu- laris (jute). K r: 75-0 0 Fibres free. Q M -- f2 r/l 2 17.2 z 18.6 q 1'1 47 -1 5.9 2 Ligni- fied. 2 3 - M PWEBSTER : ANALYSIS OF CERTAIN PLANT FIBRES. 25 The reactions of these fibres, which also form an. essential feature in the diagnosis of their constitutions, are detailed below :- Ammonio-coypey Reagent.-These fibres without exception dissolve, more or less rapidly, in contact with metallic copper and strong am- monia. The conflicting impressions which prevail on this point are doubtless referable to the employment of this reagent in its several forms, and to the widely different activities of these.Nitric Acid (in presence of sulphnric acid). The substance of all the above fibres is converted by the action of the usual nitrating mixture into so-called nitro-derivatives, allied to the pyroxylins. In the case of the lignified fibres, the reaction is accompanied by the development of a mahogany-red colour, which on washing gives place to the bright orange of the nitro-derivative in question. Xu@huric Acid (cone.).-The fibres of Boehmeria and Urtica dis- solve to colourless solutions, the solutions of the others are more or less dark coloured. Chlorine Gas.-Chlorine substitution-derivatives are obtained from the fibre substance of the above fibres, with the exception of the Boehmeria, Urtica, and Gnum, the derivatives giving in all cases the characteristic colour-reaction with sodium sulphite.Aniline XuZp3hate.-The solution of this substance, as also of the soluble aniline colours, is a valuable aid in diagnosing the fibres in regard to the distribution of the lignification, and also of encrusting substances. Xeither the Boehmeria, Urtica, nor Linum gives any reaction ; the Ananassa is coloured a uniform faint greenish-yellow ; the Yucca and Agave a pale gold ; Hibiscus bright yellow and streaky 5 CrotaZaria a pale yellow and streaky; and Musa a bright gold, also streaky. Aniline CoZours.-As is well known, the dyeing properties of the fibres vary with the lignification, and this appearing to be correlated with the development of phenols, we may hope to be able to arrive at a more correct understanding of this phenomenon.In dyeing these fibres with a neutral solution of the so-called alkali blue, the effects appear to follow an inverse course, the Boeh- maria showing the deepest colour, the lignified fibres being much paler. This fact is probably referable to the presence of " pectous " substances in the former, and the reaction may prove to be of general use in indicating the presence of acids or acid-forming substances in the plant tissues. In conclusion, I would note the grounds upon which the several determinations included in this method of diagnosis are based : (1.) The yield of cellulose is of sufficiently obvious value, and an observation of its characteristics (2) is the qualitative supplement.c 326 WEBSTER : ANALYSIS OF CERTAIN PLANT FIBRES. The most important differences shown by the various celluloses are in relation to the solvent action of the alkalis upon them, and the degree of this action is usually shown by the condition of the cellulose fibres after washing and drying. The products of the action are in the first instance gelatinous, and those fibres which undergo degradation thereby, show an agglutination of the cellulose fibrils on drying. (3.) The loss of weight sustained by boiling with an alkaline solution of arbitrary strength has been observed in two stages for the purpose of separating its more purely solvent action (continued for five minutes) from what may be termed its degrading action (con- tinued one hour subsequently). These observations throw a certain light on the nature and order of stability of the bodies of which the fibre is composed ; and attention will be drawn to this point in regard to the distinctive character of the jute fibre.(5.) A high percentage of ash-constituents is usually, in plant structures, associated with the presence of gummy or pectic substames ; and the relatively small distribution of the lattler throughout the wood and bast of plants accords with their low percentage of inorganic constituents. It is to be noted that the Boehrneria fibre stands con- spicuously high in regard to its ash, and the presence of pectous substances thus indicated is confirmed by the large loss in weight sustained in the boiling alkaline solution.(6.) Cellulose structures which differ from pure cellulose may be regarded as containing, in addition, ( a ) bodies of the pectic group; ( b ) substances connected with the trihydric phenols ; (c) substances containing furfura1,-the union of these with cellulose being probably such as is known as combination by residues, i.e., to form with the cellulose residue a chemical whole. The groups of compounds under (a) ( b ) and ( c ) differ from one another and from cellulose in respect of elementary composition, and its determination is a certain measure of the quantitative relations of these groups to one another. It may be remarked, that ( b ) and (c) are in all cases yet observed co-incidental, and agree also in respect of high carbon percentage : consequently as factors in the mean carbon percentage of a fibre they cannot as yet be separated. (7.) The chemical evidence of lignification is the formation of sub- stitution-derivatives on exposure to the action of chlorine gas, and the proof of the formation of these is afforded by their characteristic colour-reaction with solutions of the neutral sulphites. To sum up these results and bring out more clearly the distinctive character of the jute fibre, I may recapitulate its more striking points of differentiation from the other fibres included in this investigation. (1.) High carbon percentage. (2.) Power of resisting the continued action of boiling alkaline solutions, from which, together with the re-A CONDENSATION-PRODUCT OF PHENANTHRAQUIXONE, ETC. 27 snlts of an examination of the substances dissolved, it is to be inferred that the pure fibre contains no constituents of the pectic group. (3.) Such uniformity in composition and properties as to permit us to regard it as a chemical whole. (4.) Its comparative simple microscopic features. Some of these characteristics are represented amongst the other fibres, but are never united as in the case of jute, which is therefore to be preferred as a simple type of lignification ; and over biological?!/ complicated structures, such as wood, its superiority is still more manifest.

ISSN:0368-1645    

DOI:10.1039/CT8834300018

出版商:RSC    

年代:1883

数据来源: RSC

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A CONDENSATION-PRODUCT OF PHENANTHRAQUIXONE, ETC. 27 1V.-Om a Condensntion-prod71ct of Phenanthraquinone with Ethylic Aceto-acetate. By FRANCIS R. JAPP, M.A., Ph.D., Assistant Professor of Chemistry in the Normal School of Science, South Kensington, and FECXDK. W. S TREATFEIL D. IN a former communication (this Journal, Trans., 1882, 270) we described the acetonquinimide of phenanthrene, CI,HI5NO2, obtained by the interaction of phenanthraquinone, acetone, and ammonia. In endeavouring to extend this reaction t o other ketones, we substituted ethylic aceto-acetate for acetone. No reaction took place at ordinary temperatures, but on heating phenanthraquinone, ethylic aceto-acetate, and concentrated aqueous ammonia for a short time under pressure at loo", a dark-coloured mass was obtained, from which, by an appro- priate process of purification, a compound was isolated, crystallising in needles, and fusing at 184.5-185-5'.(A description of this process of purification is sup~&uous, as a much better method of preparing the substance is given further on.) The compound did not contain nitrogen. On analysis it yielded figures agreeing with the formula CmHicOa :- Substance. cop. OH,. I .. .. 0.1488 04085 0.0682 I1 .. .. 0.1740 0.4783 0.0790 111 .... 0.14234 0.4079 0-0669 Calculated Bound. for C2,H,,04. r----- v 7- I. 11. 111. Mean. C2,.. .. 240 75.00 74-87 74.96 74.96 7493 HI, .. 16 500 5.09 5-04 3-00 5.06 0, .. .. 64 20-00 - - - (20.01) 320 100.00 100~00 -- - -28 JAPP AND STREATFEILD : A CONDENSATION-PRODUOT OF’ A compound of this formula would be formed from one molecule of phenanthraquinone and one of ethylic aceto-acetate, by the elimina- tion of one molecule of water.C14H802 + c6Hioo3 = C20H,604 + OH,. Phenanthra- Ethylic New quinone. aceto-acetate. compound. The reactions of this compound show that in its formation one atom of oxygen from the quinone is eliminated along with two atoms of hydrogen from the ethylic aceto-acetate, the two resulting dyad groups then uniting by means of the free affinities. From the fact that no such condensation occurs when ethylic diethaceto-acetate is substituted for ethylic aceto-acetate, we may conclude with a high degree of pro- bability that the two hydrogen-atoms thus eliminated are furnished by the methylene group in aceto-acetic acid. The compound would thus possess the formula- c6HI-c0 and might be termed e t h y l i c phenanthroxylene-aceto-acetate.* The reaction is analogous to the condensations of aldehydes with cthylic aceto-acetate described by Claisen ( B e y ., 14, 345), in which, however, gaseous hydrochloric acid was employed as a dehydrating agent. The dehydrating action of aqueous ammonia has not, so far as we are aware, been previously observed. It resembles, however, the dehydrating action of aqueous caustic potash upon acetone described hy Heintz (Annulen, 196, 118). Condensations between aldehydes and ketones have also been effected by means of dilute caustic soda (Schmidt, Ber., 14, 1459; Claisen, ibid., 14, 2468). The foregoing analogy led us to examine whether a caustic alkali could not be substituted for ammonia in the above reaction.Not only did this prove to be the case, but the yield by the new method was fully twice as great as when ammonia was employed ; whilst, owing to the almost total absence of resinous bye-products, the process of puri- fication was materially shortened. After several trials the following mode of conducting the experi- mknt was adopted, as yielding the best result :-lo0 grams of phenan- thraqninone, ground to an impalpable powder (this is essential, as larger particles escape conversion), are introdnced into a flask with * The dyad radical (C,,H,)” is phenanthrylene; the dyad radical (C14HSO)‘’ may be etyled phenanthroxylene.PHENANTHRAQUINONE WITH ETHYLIC ACETO-ACETATE. 2 9 90 grams (an excess) of ethylic aceto-acetate ; 150 C.C. of dilute potash (1 part of solid caustic potash to 6 of water) are now added, and the mixture is gently warmed, agitating all the time.The reaction takes place quickly with considerable rise of temperature, and the orange colour of the yuinone disappears, giving place to the light grey of the crude condensation-product. The product is boiled with water, washed with alcohol, and crjstallised from boiling benzene till the fusing point remains constant. From 100 grams of quinone over 100 grams of a product, once crystallised from benzene and practically pure, were obtained. Gaseous hydrochloric acid does not effect the condensation of phenaa- thraquinone with ethylic aceto-acetate. Properties.-Ethylic phenanthroxylene-aceto-acetate is deposited from its hot benzene solution in tufts of fine white silky needles.It fuses with blackening and evolution of gas at 184.5-185.5'. It is soluble also in alcohol and in glacial acetic acid. On oxidation with a chromic mixture it yields phenanthraquinone. Hot caustic potash decomposes it, yielding a purple or a green solu- tion, according to the concentration of the potash. Dilute potash appears to saponify it slowly in the cold. These reactions have yet to be studied. With bromine in acetic acid solution it appears to form, after long standing, an addition-product. This product, which is much less soluble in acetic acid than the original compound, is slowly deposited from the solution. By recry stallisation from hot glacial acetic acid it was obtained in flat yellow needles.The fusing point could not be determined, as the substance, without previously fusing, became quite black at about 150". A bromine determination gave figures agreeing with the formula C,HI6O,Br2 (Br calculated, 33.33 ; found, 33.84 per cent.). Of course analysis is incompetent to decide between this formula and the formula of a substitution compound C,,H,,04Br2 ; but judging from the analogy of the compounds discovered by Claisen, the probability is greatly in favour of the first formula. The usual method of deciding this question by determining the quantity of bromine requisite for the formation of the compound is scarcely applicable in the present case, owing to the extreme slowness with which the com- pound is formed. In the case of the condensation-product of chloral with ethylic aceto-acetate, Matthews (Dissertation, Bonn, 1882, p.28) observed a similar sluggishness in the way in which this compound combined with bromine. Action of Hydi-iodic Acid upon Eth y lic Phenanthroxy lene-aceto-acetate, -A quantity of the above compound was mixed with amorphous phos- phorus in a flask, and an excess of fuming hydriodic acid was added. A reaction took place, accompanied by a rise of temperature, and the30 JAPP AND STREATFEILD : A CONDEKSATION-PRODUCT OF substance fused to a black pitchy mass. This product, which became semi-solid on cooling, was washed successively with water, with cold alcohol, and with small quantities of ether. The brownish substance which now remained was dissolved in boiling alcohol, and the solution filtered from unchanged amorphous phosphorus.The alcoholic solu- tion deposited on cooling a granular substance, which by repeated crystallisation was obtained in star-shaped aggregations of a pink colour. This colour is due to am impurity, and is best got rid of by dissolving the crystals in boiling light petroleum. On allowing the petroleum solution partially to cool, the colouring matter separates out first on the sides of the Vessel, and the solution, when poured off at the proper moment, deposits almost colourless crystals. A final crystallisation from benzene removes the last traces of colour. The pure substance fused at 124'. We found that the pink-coloured subtance oould be bleached by exposing it in solution to the action of daylight.The above somewhat complicahed process of purification so dimi- nished the quantity of mbstance,, that from 60 grams of ethylic phenanthroxylene-aceto-acetate only 4 grams of the pure reduction- product were obtained. A ~ a l p i s of different prepara- tions yielded numbers corresponding with the formula C20H1603 :- The compound contained no iodine. Substance. (302. OH2. I .... 0-1334 0,3849 0-0658 I1 .. .. Q-2020 0.5836 0-0955 111 .... 0.1429 0.4126 0.0701 Calculated Fwnd . for C20H1603. r-& 7 I. 11. 111. Mean. C20.. .. 240 78.95 7868 78.79 78.75 78.74 (la.... 48 15-79 -c - - (1 5-8 7) 304 100*00 100~00 Hie 16 5.26 5.48 525 5.45 5.39 -- - The hydriodic acid had therefore removed one atom of oxygen from the compound C2,&,0,. This process may be most readily explained by supposing that the acetyl-group of the ketonic acid is first reduced to the group CHS-CH(OH)-, which then parts with water, and is converted into the vinyl-group CH2zCH-.This hypothetical inter- mediate compound would be a derivative of @-hydroxybutyric acid, and the ease with which this acid parts with the elements of water, and is converted into crotonic acid is well known. According to this view the reduction-compound would possess the constitution-PHENANTHRAQUINONE WITH ETHYLIC ACETO-ACETATE. 3 I and to this compound the name ethylic a-pheiaanthrozylene-isocrotollnte might be given. That it is not the oxygen-atom of the phenanthroxylene-group which is removed during the reduction, is very clearly shown by the behaviour of the reduction-product towards caustic alkalis (vide infya) .The same reduction-compound is obtained when the condensation- product is treated in acetic acid solution with zinc-dust : but the yield by this method does not appear to be so good as when hydriodic acid is employed. The reduction-compound forms with bromine in acetic acid solution a compound-probably additive-which has not been examined. On oxidation with 8 chromic mixture the reduction-compound yields phenanthraquinone. On heating between watch-glasses it yields a snblimate of a new compound, in the form of white needles, fusing at 213", the examina- tion of which is described later. A portion of the substance remains as a charred mass. By beating ethylic phenanthroxylene-aceto-acetate with fuming h ydriodic acid and amorphous phosphorus to 200", a second reducticn- conipound was obtained, in the shape of an acid.Mineral acids pre- cipitated it from the solutions of its salts as an amorphous substance, insoluble in all the ordinary organic solvents. Neither the acid nor its salts could be obtained in a crystallised condition, so the further investigation of this substance was abandoned. Behaviour of Ethylic Phe~ccnthrox~lene-isoci*oto.nate towards Caustic A ZkaZis.-Solutions of alkaline carbonates are without action upon this compound, but dilute caustic potash dissolves it readily on gently warming. On adding hydrochloric acid to an alkaline solution thus prepared, a new organic acid was precipitated. This acid was almost insoluble in alcohol and other organic solvents of low boiling point, hut boiling phenol dissolved i t readily, and on carefully diluting the hot solution with alcohol, the acid separated in fine colourless needles, which, after washing with alcohol and drying, fused at 295".This fusing point was not altered by a second crystallisation from phenol. The results of analysis agreed with the formula CI,Hl1O4 :- Substance. coo. OH?. I ........ 0.1144 0,3078 0.0486 11.. .. .. .. 0.1282 0.3446 0-054232 JAPP AND STREATFEILD: A CONDENSATION-PRODUCT OF Calculated for C1&1404. r-A-_ CIR.. ...... 216 73-47 Hla ...... 14 4.76 0 4 . . ...... 64 21.7'7 - --- 294 100*00 The caustic alkali had therefore phcnanthroxylene isocrotonate, but Found. r-- 7 I. 11. Mean. 73.37 73.27 73.32 4.72 4.70 4.71 I 21.97 - 100~00 not merely saponified the ethylic had at the same time effected the addition of the elements of a molecule of water to the acid thus pro- duced :- c20&03 4- OH2 = C,,Hl,O, + C2H60.... (Saponification), C&1203 + OH2 = C18HldO+. ............ (Addition of water). and New acid. An examination of the salts of this acid disclosed the remarkable fact that the acid was dibasic, assuming, as is unavoidable from the mode of formation of the compound m d from its reactions, that the molecular formula is that given above, and not half this formula. Silver SaZt.-This was obtained as a white crystalline insoluble pre- cipitate by adding silver nitrate to a neutral solution of the ammonium salt. It yielded the following numbers on combustion :- Substance. coz. OH,.Ag- 0,1727 0.2687 0.0381 0.0733 Calculated for C18H1204Ag2. (---A-- 7 Found. Cis.. ...... 216 42.52 42-43 Hi,.. ...... 12 2.37 2.45 Agz ...... 216 42.52 42-44 0 4 ........ 64? 12.59 (12.68) - 508 100~00 100~00 Barium Salt.-This salt was prepared by precipitating the ammonium salt with barium chloride. It formed a white, insoluble, crystalline powder. Determinations of barium and water of cry stallisation gave numbers agreeing with the formula C,8H120dBa,20H2-Ba (in crystal- lised salt) : Found, 29.39; calculated, 29-46 per cent. OH, (not entirely expelled below 220°, at which temperature the salt becomes slightly dark-coloured) : Found, 8.33 ; calculated, 7.74 per cent. A slight decomposition had therefore probably taken place. At 180" only 1 mol. of water of crystallisation is expelled.The acid may therefore be formulated C16H12(COOH)2. It does not,PHENANTHRAQUINONE WITH ETHTLIC ACETO-ACETATE. 33 like the two compounds already described, yield phenanthraquinone on oxidation. We repeated the oxidation under varying conditions, but on no occasion was a trace of the easily recognisable quicone formed. This negative result is of importance, as it renders it probable that in the formation of the dibasic acid the closed lateral chain of the phe- nanthrene-group is severed. An inspection of the formula of ethylic phenanthroxylene-isocrotonate shows that it is in fact not possible to obtain from this substance by saponification and simultaneous addition of the elements of water a dibasic acid without thus severing the closed chain.The quantity of substance at our disposal was insuffi- cient to allow of our studying the oxidation-products of the acid. Heated between watch-glasses, the acid yielded a, sublimate of colourless needles fusing at 213", identical with the sublimate obtained from ethylic phenanthroxglene-isocrotonate. A portion of the sub- stance was charred in the process; but the yield of sublimate was better than in the former case. A quantity of this sublimate was therefore prepared from the acid. It was purified by crystallisation from boiling alcohol, in which it dissolves readily, separating out almost entirely on cooling. It was thus obtained in fine colourless silky needles, fusing, as above, at 213". Analysis gave results agree- ing with the formula ClaHloO :- Substance.co,. OH,. 0.06 72 0.2134 0.0326 c,4. . . . HIO. . . . 0 .... We were not ascertain that it sodium sulphite. Calculated for C,,H,,O. r--L 7 Found. .. . . 168 86.60 86.60 .... 10 5.15 5.39 .... 16 8.25 (8.01) 194 100~00 100*00 - able to examine this substance further, except to is insoluble both in caustic alkalis and in hydrogen The small quantity at our disposal sufficed only for a single analysis, and the preparation of the substance in any quantity would be a work of very great labour. To judge from the ease with which the substance sublimes, the above simple formula, is probably also its molecular formula. Constitution of the Dibasic Acid.-There are two ways in which a compound of the formula of ethylic phenanthroxylene-isocrot,onate may by the action of caustic alkali be converted into a dibasic acid.The simplest explanation of the phenomenon consists in supposing that, along with the saponification of the COOC2H5 group, the carbonyl-group of phenanthroxylene is separated from the other carbon-atom of the closed lateral chain ; potassoxyl then attaches34 A CONDENSATION-PRODUCT OF PHENANTHRAQUINONE, ETC. itself to the vacant affinity of the carbonyl, converting it into COOK, whilst t,he remaining hydrogen-atom from the potassium hydroxide satisfies the vacant affinity of the other carbon-atom of the severed lateral chain. The acid would thus possess the constitution repre- sented by the formula- CHxCH, I C,H4-CH=C--COOH. I C6H4-COOH The second mode of regarding the reaction is to suppose that an intramolecular migration takes place similar to that in which phenan- thraquinone is converted by the action of caustic potash into di- phenyleneglycolic acid, a reaction in which the phenanthraquinone takes up the elements of A molecule of water, whilst one of its carbon$-groups is converted into carboxyl.On this assumption the dibasic acid would be a derivative of diphenylene-methane, We think, however, that this last view is to be rejected. The fact that both ethylic phenanthroxylene-isocrotonate and the dibasic acid yield under the influence of heat the same compound, CI4HloO, points to an analogous constitution of the two compounds, a condition which is not fulfilled byrepresenting the one as a derivative of phenanthrene and the other as a derivative of diphenylenemethane, Rejecting therefore this view, there remains for our acceptance the formula above given. A possible constitution for a componnd C14HloO, derived both from ethylic phenanthroxylene-isocrotonate and from the dibasic acid, would be- CCHk-CHz CsH,--CO I I - Such a compound would stand in the same relation to phenanthra- quinone in which deoxybenzoh stands to benzil. An investigation of the reactions of this compound would doubtless have been desirable, and would possibly have thrown light upon the constitution of the compounds from which it is derived. We have already alluded to the difficulties which would attend such an investigation. The chief value of the facts here described lies in their bearing upon the constitution of phenanthraquinone. The formation of such a componnd as ethylic phenanthroxylene-aceto-acetate from ethylic sceto-acetate and phenanthraquinone, furnishes a very strong argu- ment in favoiir of Fittig’s formula for phenanthraquinone as against that of Graebe. The investigakion will be continued.

ISSN:0368-1645    

DOI:10.1039/CT8834300027

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年代:1883

数据来源: RSC

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35 V.--Note on the Preparation of Diphenylene Eetone Oxide. By W. H. PERKIN, Ph.D., F.R.S. WHILST making experiments with the hope of preparing the anhydride of salicylic acid, I ,0, a quantity of salicylic acid was heated with acetic anhydride. o n boiling the mixture, Che acid dissolved, acetic acid and the excess of acetic anhydride used distilling off. A viscid liquid then remained in the retort, solidifying on cooling to a glass-like mass, undoubtedly consisting chiefly of salicylide. On submitting this to distillation, a considerable quantity of an oily product came over, solidifying in the neck of the retort to a crystalline mass. This on being washed with alcohol, and purified two. or three times by crgstal- lisation from that solvent, was obtained in the form of fine pale-yellow needles.I. 0.1450 gram of substance gave 0.4222 of CO, and 0.0571 of OH,. C6H4, co- On analysis this substance gave the following numbers :- 11. 0.1488 7 9 ,> These give percentages agreeing Theory. Carbon . . . . . . 79.59 Hydrogen . . 4.08 0.4335 ,, 0.0559 >, with the formula C13HB02. Experiments. r--- 7 I. 11. 79.41 79.45 4.37 4.1 7 It fuses at 173.5" C. This substance is evidently the same as that obtained by Nerz and Weith (Re?.., 14, 287) by the oxidation of methylene-diphenyl oxide, also by R. Richter ( J . pr. Cheuz., N.F., 23, 349) by distilling basic potassium salicylate with phosphorus oxy chloride. This latter process, however, yields it, so far as I have experimented with it, in only com- paratively small quantities, whereas by the method above described, from 30 to 40 per cent. of the iheoretical quantity is obtained. Its formation fEom salicylide may be represented thus :- 0.co CsH4* { c ~ . o } C6H, = C6H4-CO-C,H4 + CO,. This substance being now obtainable with comparative ease by the above process, my son, Mr. A. G. Perkin, has commenced the study of its derivatives, and of the secondary bodies which are also obtained in its preparation from salicylic acid. VOL. x m r . D

ISSN:0368-1645    

DOI:10.1039/CT8834300035

出版商:RSC    

年代:1883

数据来源: RSC

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36 VL- On certain Brorniiiated Carbon Cornpo~~ids obtained in the .Manu- facture of Bromine. By S. DPSON, Student in the Laboratory of the Yorkshire College, Leeds. THESE compounds were contained in a liquor obtained as a bye-product, at the works of the North British Chemical Company. Mr. Stanford, after making some experiments upon it, forwarded a sample to Dr. Thorpe, who requested me to complete its investigation. Mr. Stanford's experiments led him to believe that the liquid consisted mainly of bromoform. The presence of this compound was not improbable, sinca Hermann, many years ago, had shown (Ann. Chenz. Phariiz., 95, 211) that a similar liquor, from the bromine obtained from the Schonebeck brine, consisted principally of bromoform, the formation of which he explains by the action of free bromine upon the organic matter contained in the mother-liquor from the brine.The liquid received from Mr. Stanford was dried by calcium chlo- ride and submitted partly to fractional distillation, and partly to frac- tional freezing, with the view of isolating these broniinnted compounds. Le Bel-Henninger tubes were used, in order to effect as complete a separation of the different fractions as powible. The liquid distilled almost entirely between 8.2' and 172", some crystals of carbon tetra- bromide being observed in the residue left in the flask. The main portion of the distillate consisted of bromoform, a tolerably constant boiling point being obtained at 148-150". The fractions next in amount boiled at 121-123" and 123-125". These were analysed, and proved t o consist of chlorobromoform.The analysis was conducted in the usual way by ignition with quicklime, and precipitation of the calcium chloride and bromide from a nitric acid solution with silver nitrate. 0.4015 of the liquid gave 0.7074 AgBr, 0.2916 AgCI, and 0.0052 as AgBr = 0.009044 AgBr. o'oo7y reduced Ag = { 0.0027 as AgCl = 0.003584 AgCl. Total AgBr = 0.7164 = 75.97 per cent. Br. Total AgCl = 0.2952 = 18.20 per cent. C1. CHBr2C1 requires 76.7'6 per cent. Br and 17.02 per cent. C1. Two determinations of vapour- den si ty gave- I. 11. 106.2 105.5. Theory requires 104.2.JAMES ON ETHYLENE CHLOROBROMIDE, ETC. 37 The specific gravity at 20" was 2.417. According to Jacobsen and Neumeister (Ber., 1882, 599), the discoverers of chlorobromoform, this body boils a t 123-125", and has a specific gravity at 15" of 2.4450. The existence of carbon tetrabromide as a bye-product in the manu- facture of bromine has already been signalised by Mr. J. C. Hamilton, a former student in this laboratory (Chem. Xoc. J., Jan., 1881). The existence of the recently discovered chlorobromoform as a bye-product in this manufacture has, however, been hitherto unnoticed.

ISSN:0368-1645    

DOI:10.1039/CT8834300036

出版商:RSC    

年代:1883

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JAMES ON ETHYLEBE CHLOROBROMIDE, ETC. 37 VI1.-.On Ethylene Chlorobromide and some Coiripouiids obtuitied from it. By J. WILLIAM JAYEB, Ph.D. (Jena), F.C.S., Demonstrator and Lecturer in the Mining School, Bristol. Pwpamtion. of Ethylene Chlo~obromide. (Maxwell Simpson's Method.) SHORTLY after I had succeeded in obtaining the ethylene chlorothio- cyanate from the ethylene chlorobromide prepared by Lossner's method (this Journal, December, 1879), Maxwell Simpson proposed a melhod f o r the preparation of the latter compound, which, with some little modification, I have found to work remarkably well and easily, as much as 70 per cent. of pure chlorobromide bailing a t 107-109" being obtained. As this method has only been abstracted into the vayious chemical journals from the Proceedings of the Royal Society of London, and since by the discovery that it is possible to replace the bromine only in C2HIC1Br by a compound negative radical, a new interest has been given to the mixed haloid derivatives of the C,H2, series, I venture to describe it a t length:-Dr.Simpson says : " 500 grains of bromine (rather over 32 grams) are dissolved (?) in 4 fluid ounces of a mixture of equal volumes of strong hydrochloric acid" and water. The soIution is introduced into a flask with a long neck and surrounded with ice. Washed chlorine is then passed into it, with repeated agitation, till it ceases to be absorbed. In this way not a trace of bromine is lost, and no solid hydrates are formed cluring the passage of the gaA. On passing oltrfiant gas into the solution, * Both in the original paper and in the Abstracts hypochlorous acid is giren, which IT as B printer's error in the first place.D 238 JAMES ON ETHYLENE CHLOROBROMIDE which should be repeatedly agitated and surrounded with cold water, I obtained a large quantity of an oily liquid which I separated from tho acid solution, washed with dilute potash, and distilled. Almost the entire quantity passed over between 106" and l l O o , most between 108" and 110"." When first using this method, wishing to obtain a large quantity of chlorobromide, I weighed out 500 grams of bromine and followed the above directions. When the operation was completed a quantity of an oil wa3 obtained which, after washing and drying, boiled a t 109- 112", a large portion, however, boiling a t 112-115".The percentage of pure and impure oil obtained was scarcely over 50, while only a few grams distilled a t 106-108", the boiling point of the ethylene chlorobromide obtained by Lossner's method (see this Jwrnal, 1879, Trans., 806). The portion which distilled a t 109--112" was acted upon with potas- sium thiocyanate, as described in my former paper, when only small quantities of ethylene chlorothiocyanate were obtained, the dithio- cyanate, C,H,(SCN),, being chiefly formed. The oil boiling a t 112- 115" produced no chlorothiocyanate, or at the most mere traces, which, owing to the large quantity of dithiocyanate, I was unable to separate. I n spite of the above facts, I was unwilling to believe that this chlorobromide, although boiling 4" or so higher than that previously used, should have so marked an influence upon the formation of the compound in question ; but a number of trials with absolute alcohol satisfied me that such was really the case, since a portion of the chloro- bromide obtained by Simpson's method (b.p. 107-108") formed the chlorothiocyanate in quite as large quandty as by Lossner's. This last experiment convinced me that no isomeric compound was pro- duced, but that probably the chlorobromide of higher boiling point contained an admixture of ethylene dibromide. The numbers ob- tained by combustion, although not differing very widely from those calculated for pure C,H,ClBr, plainly indicated that such was the case, the percentage of carbon and hydrogen being too low. I n order t o substantiate this supposition, 200 grams of ethylene dibromide were acted upon with IPSS thau the theoretical quantity of antimony pentachloride, viz., 130 grams (calc.159), when the chloro- bromide obtained boiled for the most part at 109-111", and this pro- duced comparatively small quantities of the chlorothiocyanate. It occurred to me that the teniperature of passing in the chloriiie may have an influence upon the final result, both as regards the boil- ing point and percentage of oil obtained. With a view to confirming this, 200 grams of bromine were placed in a flask, and 24 fluid ounces of hydrochloric acid and water in equal volumes added ; the flask wasASD SOXE COMPOUNDS OBTAIXED FROM IT. 39 surrounded with ice in small pieces, and left a t rest for half an hour before chlorine was passed in.The temperature inside the flask was just under 2". On completion of the process 140 grams C2HiC1Br, boiling a t 107-log", were obtained. Other experiments gave evcn better yields, but on an average not more than 65--70 per cent. of pure substance can be relied on. The percentage of ethylene chlorothiocyanate produced from this com- pound was quite equal to that given by the chlorobromide of the pentachloride of antimony method, although that substance boils a t a slightly lower temperature. It is advisable to let the delivery-tube dip beneath the bromine; if this be so, the chlorine is taken up much more rapidly. The ahove results show clearly that the temperature a t which the chlorine is passed into the bromine is of paramount importance in obtaining, not only a good yield of chlorobromide, but a compound suitable for further use, although in the latter instance the strength of the alcohol is of equal or perhaps greater importance.This temperature should be as near 0" as possible. The small quantities of bromine used by Simpson left no room f o r the error which I have pointed out, the mixture being quickly oooled to the required temperature. Preparation of Ethyleae Chlorothiocyanate. From a large number of experiments, I have found the following method to give the best yield ; and although it has in part appeared in this Journal, it is perhaps advisable to recapitulate to some extent. After digesting the chlorobromide, boiling a t 107-109", with potas- sium thiocyanate and absolute alcohol, and removing as much of the latter as possible by distillation on the water-bath, the remaining oil was filtered from the separated ethylene dithiocyanate into a small flask, now again distilled until the thermometer showed 120", left to cool, and then placed in a freezing mixture, by which means nearly the whole of the dithiocyanate crystallised out.It is now only necessary to decant or filter off the oil and distil it in a retort, which should not be filled to more than one-tenth of its capacity, the distillation being conducted Yapidly. In this way most of the chlorothiocyanate passes over before the decomposition sets in. When the thermometer indicates 170" or thereabouts, the liquid in the retort will have become dark-brown. A t this point the receirer should be changed, and all oil coming over between 170" and 210" may be taken as pure enough for the further investigation of its pro- perties.The thermometer rises rapidly to ZOO", and nearly the whole of the liquid distils between 200" and 205". The receiver should be removed before 210", as at that temperature a sudden decomposition40 JdhlES ON ETHYLENE CHLOROBROXIDE takes place with much frothing, pungent vapours being evolved which cause violent sneezing and lacrimation. The distressing effect exerted by the products of the above decom- position upon the nose and eyes made it desirable t o prevent, as far as possible, the occurrence of this decomposition. The distillation was accordingly conducted slowly by constantly removing the Bunsen ; this, however, only made matters worse, as the decomposition set in before scarcely half the oil had passed over ; neither did distilling in a vacuum obviate it.Ethylene chlorothiocyanate dissolves in hot water from which i t separates unaltered on cooling. Concentrated sulphuric acid dissolves it, and on warming it becomes decomposed with evolution of sul- phurous anhydride. It is soluble also in hydrochloric acid, but suffers no alteration on warming. On digesting i t with an alcoholic solution of potassium thiocyanate, ethylene dithiocyanate, CzH,( SCN)Z, is produced. This compound has a burning taste, and blisters the skin; sp. gr. 1.98 a t 15" C. For other properties, see this Journal, December, 1879. Action of Sodium Sulpliite upon Ethy leihe Clilorothioc~nnnte.SO,H C,H,< scN . Formation of Elh~lene-tliioc~anoszi~ho?zio Acid, The sodium salt of this new acid may be obtained, mixed with more or less sodium chloride and sulphate, by digesting the chlorothiocyan- ate of ethylene with normal sodium sulphite upon the sand-bath ; but a far more advantageous method is the following, although I have failed to separate the salt from the above-named impurities :- 20 grams of C&CI(SCN) were placed in a stoppered cylinder with 20 grams of crystallised normal sodium sulphite, the aqueous solution of the latter being not too concentrated. In a few moments the liquid turned pink, changing to carmine in less than an hour. The cylinder was now exposed to the direct rays of the sun, and frequently shaken. ru the course of a day or so all the oil was taken up, a brown amorphous substance having formed.The liquid, which had become dark brown, was shaken up with animal charcoal, and the filtrate, which was now almost colourless, was evaporated to dryness, with addition of a little dilute hydrochloric acid. The residue was dissolvetl in water, and a portion of the sodium chloride and sulphate removed by crystallisation. One of the many samples I have made was analysed, and the results obtained tend to show that the sodium salt of a new acid was present in the solid to the extsnt of about 60 per cent.AKD SOME C0MPOUYI)S OBTAINED FROM IT. 41 The following equation expresses its formation :- The mixture of salts contained 24.35 per cent. NaCI, and 16.00 The sum of these impurities being subtracted, two nitrogen Cl.C?H,.SCN + Na,SO, = NaSO,.C,H,.SCN + NaCI.Na2SC),. estimations gave 7.84 and 7.48 per cent., while the formula- requires 7.40 per cent. Concentrated nitric acid had a violent action upon it ; an acid salt of ethylene- disulphonic acid being probably prodoced, SOaNa.C,H,.SO,H. The facility with which chlorethylsulphonic acid may be produced from ethylene chlorothiocyanate by oxidation with fuming nitric acid, has led me to prepare a few of its salts and the chloride. S0,Na.C2Hd. SCN, The mixture of salts was exceedingly deliquescent. Halts of ~ - C l ~ l o ~ e f h ~ l x i ~ l p h o l L i r , Acid. The name P-chlorethylsulphonic acid is chosen in order to bring out the analogy between this acid and /3-chlorpropionic acid, as shown by the following formulse :- CHzC1 CH,C1 CHLCO (0 H) I C: HISO,(OH) I /3-Clilorpropionic acid.,%Chlorethylsulphonic mid. Potassium salt, C,H,C1S03K.-A solution of potassium sulphate mas added t o one of chlorethylsulphonate of barium until no further yre- cipitate formed. The filtrate, after concentration, yielded fine needles, which contained no water of crystallisation. It is insoluble in absolute alcohol and ether. StvoutiunL salt (C,H,ClSO,),Si. + 2OR,, may readily be prepared by acting upon an aqueous solution of the acid with excess of strontium carbonate suspended in wafer. The filtrate, on evaporation, yielded acicular crystals which contained 2 mols. of water. An analysis gave the following numbers :- I. 0.1896 gram of the crystallised salt, dried between blotting- 11.0.2842 gram, after heating to redness and treating with sulphuric paper, lost 0.017 gram a t 100". acid, gave 0.1252 gram SrSOd = 0.05969 Sr. Calculated. Found. Sr , . . . . . 2B20 .... 8-76 ,, 8.96 ,, 21.29 per cent. 21.00 per cent. Zinc salt (C2H,CISOJ2Zn + 60H2.-l'his salt was obtained by42 JBXES ON ETHYLENE CHLOROBROMIDE adding an aqueous solution of the sulphate to the barium salt of the acid. It crystallises in lamina:, and is insoluble in absolute alcohol and ether, but dissolves in weak alcohol. That it crystallises with 6 mols. of water, is proved by the following analysis :- 0.094 gram of air-dried salt, lost by heating to 100" 0.022 gram of water = 23.40 per cent. H20 : calculated for 6H,O 23.47 per cent. Copper salt (C2H4ClS03),Cu + 40Hz.-This salt, prepared by adding R solution of copper sulphate to the barium salt, may be obtained in fine square blue tablets of the triclinic system, by slow evaporation of its solution.After powdering and pressing between filter-paper, the salt was analysed, and the results show that it crystallises with 4 mols. of water, two of which it loses a t loo", becoming lighter in colour ; the remainder a t 120-125", when it is white. Heated above 125' it undergoes slight decomposition. I. 0.338 gram salt lost 0.032 gram a t loo", and on heating to l25', the total loss was 0.0575 gram. 11. 0.30 15 gram lost 0.0880 gram a t loo", and a t 125" 0.048 gram. Calculated. Found. At 100". At 125'. (C?H,CISOq)zCu + 4HzO. 2HzO 8-53 p. C. ; (1) 9.46 16 86 (11) 9.28 16.08 4HgO 17.06 p.O. . . . . . . . . . . , . . . . . , 1 This salt may be obtained crystallised in lamina: of a light blue colour from concentrated solutions. It is iiisoluble in alcohol and ether, but dissolves without difficulty in water, which solution may be boiled without decomposing. ,8- Cli lorethylsulphonic chloride, CzHJ31SOzC1.-This substance was obtained from the potassium salt by the action of phosphorus penta- chloride. It boils 200-205". Action of dry Ammonia upon a n ethereal so7ution qf the Chloride.- An oily liquid is formed, containing nitrogen and sulphur, but no chlorine ; the composition of which has not yet been determined. As the above reaction did not appear to yield any amide, it seemed interesting to study the preparation of the amide of another sulphonic acid, since, so far as I have been able to ascertain, no amides of these acids have been obtained, with the exception of the aromatic com- pounds.Pwpwation, of the Amicle of Ethylszclplionic Acid, CZH5SO2XH2.-- The acid obtained by oxidation of ethyl thiocyanate with red fuming nitric acid, was neutralised mith potassium carbonate, and its potas- salt treated with phosphorus pentachloride. 60 grams of the ethyl-AND SONE COMPOUNDS OBTAINED FROM IT. 43 sulphonic chloride thus obtained were dissolved in anhydrous etther, and ammonia was passed in to saturation. On the ethereal solution evaporating, long, glittering, prismatic crystals, began to separate. These were removed and dried in a vacuum. An estimation of the carbon and hydrogen gave this result :- Calculated for C,H,SO,NH,. Found.C . . . . . . . . 22.01 per cent. H . . . . .. . . 6.42 ,, 7.46 ,, 22.70 per cent'. These numbers not agreeing with the calculated as well as could be wished, the substance was recrgstallised from ether, and tt nitrogen determination showed that it was nom in a state of purity. 0.4080 gram on combustion with CuO, PbCrOl, and Cu, gave 48 C.C. of nitrogen at a temperature of 26" O., and 754 mm. pressure. Calculated. Pound. N , . . . . . . . 12.84 per cent. 12.86 per cent. Absolute alcohol was substituted for the ether in the preparation OE this amide, but the ammonium salt of ethylsulphonic acid was produced. The amide of ethylsnlphonic acid is soluble in water, alcohol, and ether. From its solution in either of these solvents it may easily be obtained in the crystalline form, which is usually that of fiue silky needles.By slow evaporation, however, of its ethereal solution, it may be obtained in well-defined prisms. It does not combine with h-ydrochloric acid or platinic chloride. It melts a t 58" (uncorr.) to a clear colourless liquid, and when heated on platinium foil suffers decomposition. Action of Normal Xodium Sulphite on Ethylene Uibromicle, Some years ago Strecker (Ann. Chem. Phnrm., 148, go), in his iuvestigation of the action of normal sodium sulphite upon various organic compounds containing chlorine, bromine, and iodine, studied its reaction with ethylene dibromide, and obtained the sodium salt of ethylene disulphonic acid, which was apparently the only organic Ealt produced in the reaction.My experiments have, however, shown that isethionate of sodium is also produced, although in very small quantity. When ethylene dibromide or chlorobromide is boiled with an aqne- ous solution of sodium sulphite, the odonr of sulphurous anhydride is distinctly perceptible in a few minutes. On continuing the digestion44 JSMES ON ETHYLENE CHLOROBROJIIDE, ETC. until SO, ceased to be evolved, the liquid was poured off from the remaining oil, evaporated to dryness, and the residue boiled with strong alcohol. On cooling, lamina separated, which analysis has shown to consist chiefly of sodium isethionate, mixed with a little sodium bromide. C2H,Br, + NapSO, + OH, = OH.C2H4.S03Na + NaBr + HBr, the evolution of sulphurous anhydride being of course due to the decomposition of a portion of the sodium sulphite by the hydrobromic acid.Bromine was dis- tinctly found in the salt. The reaction may be thus formulated :- One sample gave these numbers on analysis. Found. I Cdculated for C2H,0HS03Na. I. 11. 111. ' - - C.. ...... 16.21 14.19 H ...... 3.37 2.58 S.. ...... 21.62 - 19.15 19.02 - - The following is a summary of the principal results described in the foregoing pages :- 1. I n preparing ethylene chlorobromide by passing the gas into a solution of chloride of bromine (ClBr), it) is necessary, in order to obtain a pure product and good percentage, that the chlorine he passed into the bromine a t a temperature of about 0" ; otherwise a substance is formed boiling some 3" or 4" higher than pure C&ClBr, which is useless for the advantageous preparation of ethylene chloro- thiocyanate, 2. If ari aqueous solution of neutral sodium sulphite and ethylene chlorothiocyanate be brought together i n direct sunlight, the sodium SO H salt of a new acid, viz., ethylene-thiocyanosulphonic acid, C2HH'<sCb , appears to be produced. 3. By passing ammonia gas into an ethereal solution of chlorethyl- sulphonic chloride, no amide is formed ; with ethyl-sulphonic chloride, however, the corresponding amide is easily obtained. 4. By the action of neutral sodium sulphite in aqueous solution upon ethylene dibromide or chlorobromide, isethionate of sodium is apparently produced, with evolution of sulphurous anhydride, i n addition to the well-known ethylene-disulphonate of sodium obtained by Strecker.

ISSN:0368-1645    

DOI:10.1039/CT8834300037

出版商:RSC    

年代:1883

数据来源: RSC

摘要:

45 VIIL-On the Condeizsatiorr-p1.oducts of Q?naiztlialdeizyde (Part I>. By W. H. PERKIN, JUNR., Ph.D. AXONG the many researches on the condensation of the aldehydes, i t may be well t o mention a few on account of their special bearing on this investigation. Urech (Rer., 13, 483, 590, and 12, 190) found that by the action of dry potassium carbonate on isobutaldehyde, a polymeride of that body is formed, to which he gives the formula (C4H80)3. On distillation, it decomposes into isobutaldehyde, C12H2202, and other condensation- products, a t the same time losing water. Demtschenko (Rer., 6, 1176) obtained from isobutaldehyde by the action of sulphuric acid a polymeride which has also the formula (C,H,O), arid which he mmes pwaisobutaldehyde. This body is, however, not decomposed on distillation.Borodin (Ber., 6, 982) found that by the action of caustic alkali on isovaleraldehyde at 0", a polymerised modification of that body is formed, which decomposes on distillation, with separation of water, into CIqH1,0, and another condensation-product, C20HJ803, both of which are oils. This last body is decomposed bp heating with alkalis into isovaleric acid, isopentylnlcohol, and isovaleraldehyde, which bodies are also formed by heating isovaleraldehyde alone to 240°, or with zinc-turnings to 180". If i~ovalera~ldehyde is allowed to stand for some time with soda, a hydrate of the formula C2,,Hi205 = (CloH2002)2H,0 is formed, which on distillation is deconiposed into isovaleraldehyde and the conden- sation-products ClaH180 and C20H3803.By the action of sodium on isovaleraldehyde, Borodin (Juhresb., 1864, 338 ; Rer., 5, 481) obtained the condensation-products CloH180 and C,,H,,03, polyiaovnleraldehyde, and the alcohol ClOH2?O. This last body gives on oxidation isocapraldehyde, tlie acid ClOH,,O2, an oil which boils a t 250-290°, and to which Borodiii ascribes the formula (C,,H,,O),, also isovaleric acid and isopentyl- aIcohol. Grenier (Jmliresb., 1866, 465) obtained the same body, CloH180, by the action of sodium on ethylisovalerate. Gass and Hell found that dry potassium cai*bonate has, st the ordi- nary temperature, the same action on isovaleraldehyde as caustic potash, but that if the aldehyde is boiled with potassium carbonate, the bodies CloHl,O, C15H2802, and C2,,H,,0s, are formed. This last46 PERKIN ON THE CONDENSATION-PRODUCTS body on distillation decomposes with separation of water, and gives the aldehyde CloH1,O.Of the researches on the condensation-products of oenanthaldehyde, those of Borodin, Bruylants, Tilley, Fittig, and Schiff may be cited. Borodin found (Bey., 5, 431 ) that by the action of caustic alkalis on cenanthaldehy de a t ordinary temperatures, two polymeric modifica- tions are formed. They both give off water on distillat'ion, with formation of CIaH2,O and C,,H,,O,. By heating cenanthaldehyde at 240°, the same bodies are formed. Bruylants (Bey., 8, 415) obtained by the action of potassium car- bonate on cenanthaldehyde, a polymeric modification, which he puri- fied by washing with water and repeatedly crystallising. It melts a t 5 1-52'. Like the polymerides of isobutyl and isovaleryl aldehydes, it decomposes with separation of water on distillation, condensation- products being formed ; one of these boils at 160-170", and appears t o be an aldehyde.Eittig (Annalen, 117, 76) found that if cenanthaldehyde is left in contact with quicklime, heptoic acid, heptyl alcohol, and the hydro- carbons C7HII, C8H16, C9H,,, and amanthacetone, CI3H&, are formed. Tilley (Jahwsb., 1, 566) obtained, by warming cenanthaldehyde with caustic potash to 120", an oil, CldH280, which boiled at 220". By the action both of fused caustic potash and also of aqueous potash on cenanthaldeliyde, he found that heptoic acid is formed. I n the latter case, an oil was separated from the potassium salt, by distilling in steam, mid was then found to have the boiling point 220°, and on analysis numbers were obtained which seemed to show it to be the same body, CllH280, mentioned above.By oxidstion with nitric acid it gives heptoic acid, and by the action of potash heptoic acid is also produced, and a tarry body, hydrogen being evolved at the same time. Schiff found that by saturating an alcoholic solution of cenanth- aldehyde with hydrochloric acid gas, a body of the formula One is a solid and the other an oil. C1(C,Hl*)OC*H, is formed, which on distillation is completely decomposed into CliH260 and other bodies. Rieth and Beilstein (Jahresb., 16, 478) obtained the same body, ClaH,60, by the action of zinc-ethyl on cenan thaldehyde. As in many cases in the above-mentioned researches the formula: only, and not the properties of the bodies obtained, are described, I undertook, at the suggestion of Professor Wislicenus, the following research, in order, if possible, to obtain some clue t o the constitution of the bodies formed by the condensation of the aldehydes, and more especially of those derived from cenanthaldehyde. The cenanthaldehyde used in the following experimeiits was obtainedOF CENANTHALDEHYDE.47 from Rahlbaum, in Berlin. It boiled between 150" and 160". Pure ceiianthaidehyde was found to boil a t 153-154" (thermometer in vapour), and has the specific gravity at 15" = 0.8231 at 30 = 0.8128 at 35 = 0.8099 compared with water a t the same temperatures. Action of Potash ON CEnanthaldehyde. The action of potash on this aldehyde is extremely violent.If oennnthaldehyde is mixed with a concentrated solution of potash in alcohol, the rise of temperature, chiefly owing to condensation, is so great as often to cause the alcohol to boil. The products of this reac- tion consist mainly of potassium heptonte and high condensation-pro- ducts which, owing to their high boiling points, could not be isolated and examined. However, after many experiments, it was found that if a very dilute solution of alcoholic potash is used, the reaction is less complicated, the following method of procedure giving the best results :- 3 grarns of potash were dissolved in about 200 grams of absolute alcohol, and then 200 grams of cenanthaldehyde slowly added, care being taken that the temperature did not rise above 30°, otherwise the reaction was found to go too far, large quantities of high-boiling bodies being produced. The condensation of the cenanthaldehyde takes place very rapidly, and is probably finished in half an hour.At the end of about 24 hours not a trace remains unchanged. I n order to isolate the products of the reaction, the alcohol was first distilled off and then water added, or the product was directly diluted with much water. In either case it was found necessary to shake up the product with ether to perfectly separate the oil from the alkaline solution. The ethereal solution was well washed, first with dilute hydrochloric acid, and then with water, and finally dried over calcium chloride. The following is the examination of the aqueous alkaline solutions from a number of these operations. They were first treated two o r three times with ether t o remove traces of oil, saturated with carbonic anhydride to convert any caustic alkali present into carbonate, and evaporated to dryness on a water-bath.The product was then further dried and several times extracted with absolute alcohol. After the alcohol had been distilled off from these extracts, the saline residue was dissolved in water, acidified with hydrochloric aciil, and the acids thus liberated separated with ether, the ethereal solu-48 PERKIN ON THE CONDENSATION-PRODUCTS tion was then fractioned. cg;reater part of the product came over between 180" and 230". small quantity, however, referred to further on, was left in the retort.. mostly between 220-225", and was, doubtless, heptoic acid.on analysis the following numbers :- After the ether had been distilled off, the A The portion boiling between 180-230", on fractioning, came over It gave 0.2389 substance gave 0.2372 OH, and 0.5659 GOz. Found. Theory, C,HI,COOH. C . . . . G4.60 per cent. H . . . . 11.03 ,, 10.77 ,, 64.61 per cent. The small residne left in the retort was distilled in vacuo, and then fractioned under a pressure of 200 mm., when it came over without, tlhe least decomposition. The best fraction which could be obtained boiled, at this pressure, between 270-290", and gave the following numbers on analysis. These agree fairly well with the calculated percentages for an acid of the formula C,,H,,O, :- 0.1405 substance gave 0.1445 OH, and 0.3811 CO,.Found. Theory, Cl,H,,02 = C,3H25COOH. C . . . . 73.97 per cent. H . . . . 11.42 ,, 11-50 ,, 74-33 per cent. The yield of this acid is perhaps improved by adding hydrochloric acid and extracting the acids directly from the crude potash-salt, instead of saturating with carbonic anhydride, extracting with alco- hol, &c., as long boiling seems to decompose the potassium salt. The properties and salts of this acid are described further on, under the heading " Actioii of Potash on the Aldehyde CldH260." The following is the examination of the ethereal solution of the oily condensation-products. After the ether had been distilled off the remaining oil was carefully fractioned in a stream of carbonic anhydride.* The thermometer rose rapidly to 260", between which temperature and 300" by far the largest quantity of the product dis- tilled over as an almost colourless oil, leaving a black residue in the retort which is referred to further on.This distillate was then re- peatedly fractioned, the greatest care being t,aken to prevent the product from coming in contact with the air. An oil at last was obtained boiling between 277" and 279'. On analysis it gave the following numbers :- f It is very important to bear in mind t,hat, owing to the rapid absorptioii of oxygen from the air by these products, all operations with them must be conducted in an atmosphere of carbonic anhjdride.OF CENANTHALDEHYDE. 49 I . . 0.1796 gram substance gave 0.1979 OH, and 0.5301 CO,. I1 . . 0*1s99 ,, I , 0.1812 ,, 0.4676 ,, 111 .. 0.1890 ,, ,, 0.2146 ,, 0.5539 ,, Found. r---- 7 I. 11. 11. Theory, C14H260. C . . . . 80.49 79.74 79.92 per cent. 80-00 per cent. H . . . . 12-24! 1239 12.61 ,, 12.38 ,, These combustions were made from three different preparations. This body has therefore the composition ClaH260, and is apparently the same substance as that obtained by Borodin, Schiff and Rieth, and Beilstein. It is a colourless oil, having a faint smell and a burning taste. It does not solidify a t -20". I t s specific gravity is- at 15" = 0,8494 at 30 = 0.8416 at 35 = 0.8392 compared with water a t the same temperatures. It absorbs oxygen yery rapidly, so much so, that when placed in a tube full of air, over mercury, in a short time nothing but nitrogen is left in it. This oil reduces a solution of Ag20 in ammonia very easily.It is an aldehyde, and combines, though very slowly, with hydrogen sodium sulphite, so that, only after keeping the two in contact for months, with frequent agitation, a definite body was obtained ; it then had the form of silky crystals slightly soluble in water ; it is apparently decomposed by a solution of sodinm carbonate. This compound was filtered from the excess of hydrogen sodium sulphite, pressed between filter-paper, and in order to insure its freedom from inorganic matter, two or three times wetted with water and again pressed. It was then thoroughly dried, and washed with ether to remove any uncombined oil. When pure it is a beautiful silky-looking crys- talline substrance. A sodium determination gave the following numbers : - 0.4622 gram substance gave 0.1105 gram Na,SO, = 7-74 per cent.The formula Cl4Hz6O,NaHSO3 requires 7.32 per cent. This aldehyde is soluble in ether, alcohol, carbon disulphide, and glacial acetic acid, in 50 per cent. acetic acid it is only sparingly soluble. It is evidently formed by the elimination of tohe elements of water from 2 mols. of cenanthaldehyde, according to the equation- Na. 2C,H,3CO€I = C1sH2,COH + OH,.50 PERKIN ON THE COXDENSATION-PRODUCTS The condensation-products boiling above 300°, which were left in the retort after distilling off the aldehyde, Cl4HZ60, just described, were very thick ; they were first distilled in a vacuum, and then fractioned under a pressure of 350 mm. The principal portion came over between 32@-3,50", above that temperature, however, there remained a considerable quantity in the retort, which could not be purified.The product boiling between 320-350" was very carefully fractioned under the same pressure, till at last the principal quantity was obtained, boiling between 330-3340'. It is a thick light yellow oil, and has a disagreeable smell and burning taste. It does not solidify at -20". It mixes in all proportions with the usual solvents, and reduces ammoniacal silver solution. The amlyses gave the following numbers :- I . . 0.2298 gram substance gave 0.2645 OH, and 0.7064 CO. I1 . . 0.1864 7, ,, 0.2130 ,, 0.5723 ,, IV . . 0.237 ,, ,, 0.2663 ,, 0.7229 ,, I11 .. 0.2076 ,, ,7 0.2377 ,, 0.6433 ,, Found. Calculated for II.III.Iv7 I. C2sH5,O. C . . 83.83 83.73 83.72 84.00 per cent.83.58 per cent. H .. 12-78 12.69 12.60 12.60 ,, 12.43 ,, Nos. 1: and IV were from the first experiment, Nos. I1 and 111 from The a.bove results show that the body has the one made later on. formula CBH,,O. Its specific gravity is- a t 15" = 0.%331 at 30 = 0.8751 at 35 = 0.8723 compared with water at the same temperatures. elimination of 3 mols. of water, according to the equation- It is apparently formed from 4 mols. of oenanthaldehyde by the 4C,H140 = Cz,H,,O + 3OHz. The intermediate body, containing CZ1, and standing between this body and the aldehyde previously described, could not be obtained pure ; it appears to be formed but only in very small quantities. The principal products of the action of potash on oenanthaldehyde, so far as they have been studied, are, therefore, heptoic acid, the acid CllH2602, and the aldehydes C J L O , and CZ8H5,O.Action of Zim Chloride o n GTnantlinldehyde. These experiments were tried in the hope of getting a body corre- sponding to crotonic aldehyde, by the removal of t'he elements of waterOF (ENANTHALDEHYDE. 51 from cenanthaldehyde. The action of zinc chloride on dry oenanth- aldehyde is very violent. If the two are warmed together, two layers are quickly formed ; the lower one being a solution of zinc chloride, and the upper one a dark brown oil, from which nothing definite could be obtained, as it decomposed on distillation. After numerous trials it was found that by modifying the process in the following way, the reaction was less complicated : cenanthaldehyde was shaken up with water until it was thoroughly saturated, separated from the excess of water, and warmed on a water-bath with a very small quantity of zinc chloride.In about 15 hours the action was finished. The product was then dissolved in a small quantity of ether, washed with water, dried, and fractioned. After the removal of the ether, it was distilled first i 7 t vacuo, as a quantity of high-boiling products were present. It was then further fractioned at the ordinary pressure. As soon as the unchanged oenanthaldehyde had distilled over, the thermometer rose rapidly to 260", between which temperature and 300" the principal portion distilled over. The residue was not distilled over ; it contained probably the same high-boiling condensation-products as those obtained by the action of potash on oenanthaldehyde. The product boiling at 260-300", on being fractioned, passed over principally at 276-280", and judging from its boiling point was apparently the aldehyde CIaH2,O.This was proved to be the case by the determination of its specific gravity and analysis :- I . . 0.1598 gram substance gave 0.1790 OHz and 0.4659 CO,. I1 . . 0.1527 ,, ,, 0.1710 ,, 0.4479 ,, Found. rL- 7 I. 11. Theory, C14H260. c . . 79.54 19.97 per cent. 80.00 per cent. H .. 12-44! 12.44 ,, 12.38 ?, The zinc chloride acts therefore ax a dehydrating agent on amanth- aldehyde, as in the case of ordinary aldehyde- 2C7H140 = CJXZO + OH,. The yield of this aldehyde is about 30 per cent., whereas by the potash reaction it ranges from 70 to 83 per cent.of the theoretical quantity. Actioii of Acetic Anhydride o n the Aldehyde, C,,H,,O. This experiment was tried in the hope of getting a diacetate from this body, as in the case of most aldehydes, according t o the equation- and of thus obtaining another proof of its being an aldehyde. VOL. XLIII. E52 PERKIN ON THE CONDENSATION-PRODUCTS A mixture of this aldehyde and acetic anhydride was first boiled for three days in a flask connected with a reversed condenser ; as it was found, however, that little or no reaction had taken place, it was then transferred to a sealed tube, and heated to about 180" for three days. On distilling the product, and after the unchanged anhydride apd acetic acid had distilled off, the thermometer rose rapidly to about 270°, when a small quantity of the unchanged aldehyde came over.The distillation was continued till the thermometer had reached 300°, and then the thick black residue was distilled under a pressure of 350 mm., when by far the largest quantity came over between 300-350". This portion was carefully fractioned under the same pressure. After repeating this operation two or three times, the principal por- tion distilledover between 330-340", as a viscid light yellow oil. On heating this with alcoholic potash it turned dark brown, but no trace of acetic acid could be afterwards found combined with the alkali. The oil left after this treatment decomposed on distillation. It appeared therefore that the body was not an acetate. On analysis it gave the following numbers :- I.0.2353 gram substance gave 0.2600 OH, and 0.7242 COz. 11. 0.1975 ,, ?7 0.2219 ,, 0.6069 ,, Found. r---z I. Theory, Cz8H,o0. c . . 83-94 b3.81 per cent. 83.58 per cent. H .. 12.28 12-48 ,, 12.43 ,, This substance has therefore the composition CzaH500, and is doubt- less identical with the one produced by the action of potash on mnanth- aldehyde, as it possesses practically the same boiling point and specific gravity, and in fact resembles it in every respect. It appears there- fore that the acetic anhydride acts as a dehydrating agent, extracting water from 2 mols. of CIaHZGO, being itself converted into acetic acid, according to the equation- 2ClJ€zGO + (CH,.CO),O = C,,H,oO + 2(CHs.COOH). In order, if possible, to get some idea of the constitution of this body, C2,H500, and of the nature of the groups contained in it, it was €used with excess of caustic potash in a silver crucible.In a short time the whole mass turned quite black and began to froth up and fume. After about five hours' heating it was allowed to cool, dissolved in water, and the oily matter removed with ether. The alkaline solution was then acidulated with hydrochloric acid, and the oily acid which sepa- rated taken up with ether. On distillation this acid boiled betweenOF CESANTHALDEHYDE. 53 190" and 230°, and smelt like heptoic acid. potassium salt and then into a silver salt. It was converted into a This salt gave the following numbers on analysis :- 0.3307 gram substance gave 0.1572 gram Ag = 4'7.53 per cent. = 48-43 per cent. : { :$.jig = 45.57percent. Calculated for It appeared therefore to be a mixture of hexoate and heptoate of silver.I n order t o see whether acetic acid, or any low-boiling acid soluble in water, had been formed, the original aqueous solution, which had been treated with ether, was distilled in steam. The distillate, however, was only very feebly acid, which was probably due to traces of heptoic acid. It appears, therefore, that only hexoic and heptoic acids are formed by the action of fused potash on C2,H5,O, and that, therefore, probably only hexyl and heptyl-groups are contained in it, which, it will be seen, is borne out by the oxidation-products of the body C14H2,0, described further on. It was attempted to distil in vacuo the oil which was separated from the potash salt, but it decomposed, and as only a few drops came over below 350°, it could not be examined.Action of Nascent Hydrogen on the Aldehyde Cl4H2,O. As the body C,,H,,O has the properties of an aldehyde, and at the same time is an unsaturated one, it was thought that it would be interesting to submit it to the action of nascent hydrogen. This was done in two ways-(I) in acetic acid solution; (11) in ethereal solution. I. The aldehyde was dissolved in glacial acetic acid, and excess of sodium-amalgam slowly added, care being taken t o keep the solutioii cool, in order t o prevent, as far as possible, further condensation of the body C1,H?,O. Owing to the addition of considerable quantities of the amalgam, the sodium acetate formed rendered the liquid thick and unmanageable.It was found advisable therefore to precipitate the oil by means of water, wash, dry, &c., dissolve it again in acetic acid, and continue the treatment as before. When a considerable excess of amalgam had been used, the whole was diluted with water, and the oil taken up with ether. The ethereal solution, after being well washed in order to remove as much acetic acid as possible, wag dried and fractioned. After the ether had distilled off, the principal quantity came over between 270-300", and by repeated frac- tioning gave as the chief product a colourless oil boiling between 282-290". An analysis of this substance gave the following numbers :- E 254 PERRIN ON THE CONDENSATION-PRODUCTS 0.1906 gram substance gave 0.2199 OH, and 0,5527 GOz. Found. Theory for C,,Ha60.C . . . . . . 79.08 per cent. H.. .. .. 12.83 ,, 13.21 ,, '79.25 per cent. These numbers agree fairly well with those required by the for- mula c14&,&, which represents the aldehyde as having taken on H,. As will be seen further on this product is an alcohol. 11. The treatment of the aldehyde in ethereal solution with nascent hydrogen was conducted in the following way :- 100 grams C14Hz,0 were dissolved in 400 grams ether, and the mixture poured upon water contained in a large flask, connected with a reversed condenser ; small pieces of sodium were then very slowly added. The reaction was a t first very violent, but became more con- trollable as the water got saturated with sodium hydrate. Before each addition of sodium, the mixture was well shaken, in order to dissolve out the sodium hydrate formed from the ethereal solution, which would otherwise cause the further condensation of the aldehyde C,,H,,O.The operation took about seven days, 50 grams of sodium being used. The ethereal solution was well washed, first with dilute hydrochloric acid, then with water, and afterwards dried over calcium chloride, and fractioned. The principal part distilled over between 260-310°, but a con- siderable residue was left behind, which is referred to further on. In order to separate the new alcohol which is contained in this distillate from any unchanged aldehyde, it was found best to heat the fraction 260-310" with acetic anhydride in a sealed tube a t 180" for three clays. By this means the aldehyde is condensed to Cz6H5,,0, and the boiling point thereby considerably raised, whilst the new alcohol is at the same time converted into an acetate, which boils at about the same temperature as the alcohol itself, and is therefore very easy to obtain moderately pure by fractional distillation. On distillation the largest portion o f the product came over between 280-295", and this on repeated fractioning gave as the principal product an oil boiling between 285-290".This oil, which is the acetate derived from the new alcohol, is a Eolourless, highly refractive liquid, having a, pleasant smell. Its specific gravity is- at 15" = 0.8680, at 30 = 0.8597, a t 35 = 0.8568, compared with water a t the same temperatures. On analysis it gave the following numbers :- .OF (ENANTHALDEHYDE.55 I. 0.2367 gram substance gave 0.2600 OH, and 0.6583 GO,. 11. 0.2130 ,, ,, 0.2298 ,, 0.5919 ,, Found. r-.-7 Theory I. 11. for C,,HB7OC2H3O. c ...... 75.85 75.78 75.59 per cent. H ...... 12.20 11-98 11.81 ,, This acetate is readily decomposed by potash. A determination of the acetic acid produced by its saponification gave the following results :- 2.3442 grams substance saponified with dilute alcoholic potash gave 0.9256 gram potassium acetate = 24.16 per cent. C26O2. Calculated for C14H2,0C2H30 = 23.62 per cent. To obtain the alcohol, the acetate was warmed with alcoholic potash, and completely saponified. Water was then added, and the alcohol taken up with ether. The ethereal solution after being dried was fractioned. When the ether had passed over, the thermometer rose rapidly, the largest quantity of the alcohol coming over between 278" and 290" as a colourless oil.On repeatedly fractioning this, it was obtained nearly pure, and boiling between 280-283'. It gave the following numbers on analysis, which agree satisfactorily with the formula C14H280 :- I. 0.1723 gram substance gave 0.2021 OH, and 0.4999 GO2. 11. 0.1950 ,, ,, 0.2354 ,, 0.5693 ,, Found r-- 'I Calculated I. 11. for C,,H2,0. C ...... 79.12 78.93 per cent. 79.25 per cent. H ...... 13.03 13.41 ,, 13-21 ,, This alcohol is a colourless oil, having but little odour. It does not solidify at a temperature of -20°, and is not oxidised in contact with the air. It does not combine with acid sodium sulphite, nor reduce ammoniacal silver solution. The specific gravity of this alcohol is- at 15" = 0.8520, at 30 = 0.8444, at 35 = 0.8418, compared with water at the same temperatures.Its formation from the aldehyde may be represented thus :- CIsH2,COH + Hz = CIsH2,CHzOH. The oily residue boiling above 300" left in the retort (produced by the action of nascent hydrogen on ClaH,,O in ethereal solution) was56 PERKIN ON THE CONDENSATION-PRODUCTS distilled in a vacuum, and then fractioned under a pressure of 300 mm. At first, almost all the product came over between 310-350", but after repeated fractioning the principal part boiled between 330-340". It gave the following numbers on analysis :- 0.1424 gram substance gave 0.1634 OH, and 0.4370 CO,. Found. Theory for C28H5,0. C ........ 83.69 per cent. 83.58 per cent.H ........ 12.741 ,, 12.43 ,, These numbers agree with the formula for the body C2sH5,0, which is no doubt produced from the aldehyde C,4H2,0, by the condensing action of the sodium hydrate formed in the operation. Nascent hydrogen appears therefore to have no action on this body. Action. of Nascent Hydrogen on th.e Alcohol C,,H,O. In order t o see whether it was possible to obtain a saturated alcohol of the formula (31,,H,,O by the continued action of nascent hydrogen on the unsaturated alcohol CI4H2,O, the following experiments were made :- The alcohol was dissolved in ether, and treated with water and a large excess of sodium (in the same way as in the preparation of the alcohol itself). A t the end of seven days the ethereal solution was separated from the water, and treated again with nascent hydrogen, using a 50 per cent.solution of acetic acid instead of ordinary water; the ethereal solution was then separated, well washed, dried, and after the ether had been distilled off, the oil fractioned. At first the greater part came over between 260" and 290°, but after fractioning two or three times, and last of all collecting between every 5", the largest fraction obtained boiled between 270-275". On analysis this gave the following numbers :- 0.1612 gram substance gave 0.2028 OH2 and 0.4669 GO,. Found. Theory for C,,H,O. C ........ 78.99 per cent. 78.50 per cent. H ........ 13.98 ,, 14.02 ,, It appears therefore that the saturated alcohol, C14H300, is pro- duced by the action of nascent hydrogen on C14H280, though with difficulty, this unsaturated alcohol, as might be expected, being very slowly acted on by nascent hydrogen.This saturated alcohol obtained was not quite free from the unsaturated one, for on dissolving it in carbon bisulphide, cooling t o -lo", and titrating with bromine, it tookOF 03NANTHALDEIiYDE. 57 up a small quantity without evolution of hydrobromic acid. formation of this alcohol is expressed according to the equation- The C13H25CH2OH + H2 = C13H27CH20H. A further description of this alcohol will be found in Part I1 of this investigation under the heading '' Action of Nascent Hydrogen on the Aldehyde C14H280.'' In order to obtain an acetate of this alcohol, it was heated in a sealed tube with an excess of acetic anhydride for some time to 180- 200".On fractioning the product, almost all distilled over between 260--290", and after repeating this operation two or three times, the principal portion obtained boiled at 275-280". I t gave the following results on analysis, agreeing with those required by the formula ClaH,,O.C2HsO :- 0.1320 gram substance gave 0.1501 gram OH2 and 0.3643 GOz. Calculat,ed 75.00 per cent. Found. for CI,H,90C,H30. C . . . . . . . . 75-97 per cent. H ........ 12.63 ,, 12.50 ,, Oxidatiotl. of C 13H25C OH. In order if possible to obtain some definite clue as to the constitution of this aldehyde, several experiments were made with different oxi- dising agents. (1 .) OaidatioiL with, Chromic Acid. 50 grams of ClbH260 were dissolved in glacial acetic acid, and heated with twice its weight of chromic acid dissolved in glacial acetic acid.The reaction was very violent, and the oxidising mixture had t o be added very slowly, the product being well cooled after each addition. Every time the solution of chromic acid was run in, the liquid frothed up, carbonic anhydride being given off in large quantities. As soon as all the chromic acid solution had been added, the product was heated on a water-bath for two hours, to ensure theoxidation being as complete as possible. A considerable quantity of water was then added, and the whole shaken up with ether three or four times. It was afterwards found best to distil off the volatile products from the green liquid by means of steam, and then to treat the distillate with ether, The ethereal solution was separated, washed several times with water, in order to remove as much acetic acid as possible, and the acids contained in it were separated from any neutral bodies formed in the reaction, by treatment with a dilute solution of potash.The potash58 PERKJN ON THE CONDENSATIOS-PRODUCTS solution was then separated from the ethereal, acidulated with hydro- chloric acid, and the acids thus liberated taken up with ether. The ebhereal solution was well washed, dried, and fractioned. After the ether had distillfid off, almost all the remaining products came over between 190-230", but all attempts to get substances with a constant boiling point were in vain. The whole was therefore made into a potas- sium compound by dissolring it in a solution of potassium carbonate and evaporating it to dryness.The saline product was then repeatedly extracted with absolute alcohol, to free it from potassium carbonate, and the solution evaporated to dryness. After repeating this purifica- tion with alcohol, the salt was dissolved in water, and a silver aalt prepared from it by precipitation with nitrate of silver. The salt thus obtained, after being well washed and dried, was analysed, but no good results were obtained, the numbers always coming between those calculated for heptoate and hexoate of silver. Several attempts were made to crystallise the salt from water and alcohol, but without success. As it appeared possible that both acids might be present, the oxida- tion was again repeated, with 100 grams aldehyde, as the yield of acid is very small, most of the aldehyde being oxidised to carbonic anhy- dride.The acids obtained in this operation were then fractioned with great care, and separated principally into two quantities, boiling at 203-2Oi" and 219-228°. Each of these was separately converted into potassium salts, dried, and purified as before with absolute alcohol, and after repeating the purification, dissolved in water. In order to obtain silver salts as pure as possible, each product was fractionally precipitated with silver nitrate into five quantities. Silver determi- nations were then made with the 10 fractions, and these showed with- out douht that the acids found consist of a mixture of hexoic and heptoic acids. The fractions which gave the best silver determinations were com- pletely analysed.Of those prepared from the potassium salt of the acid (b. p. 203--2;07"), fraction 111 gave the best results ; and from the potassium salt of the acid (b. p. 218-228") fraction 11. No. I11 (203-2011") gave the following results on analysis :- I. 0.2098 substance gave 0.2463 GO2, 0.0924 OH2, 0.1019 Ag. 11. 0.2016 ,, ,, 0.2366 ,, 0.0900 ,, 0.0978 ,, Found. r'--"-- Calculated I. I 7 for C5HllCOOAg. 32.28 per cent. C . . . . . . 32.17 Ag .. . . 48.57 48.51 ,, 48.43 ,, 32.01 per cent. H . . . . . . 4.89 4.96 ,, 4.93 ,, There can therefore be no doubt it consisted of hexoate of silver.OF CENANTHALDEHYDE. 59 No. I1 (218-228") fraction gave on analysis the following I. 0.2200 substance gave 0.1102 OHz, 0.2855 COz, and 0.1008 Aq. numbers :- 11. 0.2163 ,, ,, 0.1057 ,, 0.2796 ,, 0.0991 ,, Found.yL- -7 Calculated I. 11. for C6H13COOAg. C . . . . . . 35.38 35.25 per cent. 35.44 per cent. H . . . . . . 5.56 5-43 ,, 5.48 ,, Ag . . . . 45.81 45-82 ,, 45.57 ,, It was therefore without doubt heptoate of silver. The aldehyde C13H?,COH splits up therefore on oxidation into car- bonic anhydride, and heptoic and hexoic acids, according to the equation- ClaH26O + 0, = C6HlsCOOH + C5HiiCOOH + COz. The ethereal solution of the neutral oils from these oxidation experi- ments was then repeatedly fractioned, but no constant boiling point could be obtained. The oil began to boil at 250", but mostly distilled above 360". I hope at some future time to be able to study this subject in a more exhaustive way. (2.) Oxidation by the Air. As it seemed probable that by gentle oxidation, such as direct absorption of oxygen from the air, the acid of the formula C,4&02 would be formed, identical with that obtained by the action of potash, both on mnanthaldehyde and C laH,60, the following experiments were made:-First, a considerable quantity of the aldehyde was exposed to the air in flat dishes for three weeks.In order to hasten the oxidation, the product was gently heated by placing the dishes on a water-bath, and well stirred every day. In a few days it became very thick and slightly yellow, and appeared inclined to become solid on the surface. A second experiment was made by saturating filter- paper with the oil, and then hanging it up in the air for a week to oxidise. The oil was then extracted by digesting with ether.In both cases the oil was afterwards dissolved in ether, and the acids formed separated from the unchanged or neutral oils by shaking with dilute potash-solution. The potash-solutions were treated with ether two or three times, to ensure their freedom from oil, and after being carefully nentralised with sulphuric acid, evaporated to dryness. The whole mass was then extracted several times with absolute alcohol, and again evaporated to dryness. The organic potassium salts were acidulated60 PERKIN ON THE CONDENSATION-PRODUCTS with dilute hydrochloric acid, and treated with ether, the ethereal solution then separated, well washed, dried, and the ether distilled off. The quantity of acid left was very small, and smelt strongly of heptoic acid.It was carefully fractioned, when by far the largest quantity distilled over between 200-230". There was only a very small quantity of a high-boiling acid left behind, which was most probably the acid C14H2602, but it could not be obtained pure enough for analysis. The fraction 200-230" was made into the potassiu~ compound in the usual way, and then precipitated with nitrate of silver ; the silver salt gave the following numbers on analysis :- 0.2219 gram substance gave 0.1072 OH,, 0.2756 GO, 0.1030 Ag. Pound. Calculated { $aAg, { $aA,. C . . . . 33.87 per cent. 32.28 per cent. 35.44 per cent. H . . . . 3-37 ,, 4.93 ,, 5.48 ,, It was therefore undoubtedly a mixture of hexoate and heptoate of silver. The acid C14H2602 may probably have been first formed, but being very unstable rapidly oxidisedunder the influence of the air and potash into heptoic and hexoic acids.The ethereal solution of the neutral oils, which was separated from the acids by shaking with potash, was examined. The oils it contained began to boil at 250°, but the principal part passed over above 300". Several of the fractions were analysed, but; no definite results were obtained ; there appeared, however, to be no unchanged substance left. (3.) Oxidation wifh X i h e r Oxide. As it seemed possible that the acid ClaHZ6O2 might perhaps be obtained in larger quantities by the oxidation of the aldehyde C14H260 with a gentle oxidisillg agent, such as silver oxide, several experiments were made in this direction. The following method was tried :-About 20 grams of ClaHz60 were shaken up with freshly precipitated silver oxide and water in a flask connected with a reversed condenser.The oil quickly adheres to the oxide of silver, and falls to the bottom of the flask, when the greater qua,ntity of the water can be poured off. The mixture was then heated to boiling in a bath of a concentrated solu- tion of carbonate of soda for about 24 hours ; at the end of this time all the silver was reduced. Dilute hydrochloric acid was then added, to decompose any silver salts formed, and the whoIe well shaken up with ether several times, to extract the oil from the precipitated silver. The acid products were separated from the ethereal solution of the oil as before by shaking with dilute potash. The potash-solution was aciduhted with dilute hydrochloric acid, treated with ether, andOF aNARTHALDEHYDE.61 the ethereal solution separated, dried, and fractioned. As soon as the ether had distilled off, nearly all the residue boiled between 190-230". The residue, consisting of high-boiling acid, was again so small that it was found impossible to purify it. The fraction 190-230" was turned into the potash compounds, and then precipitated with nitrate of silver ; a silver determination of the silver salt thus made gave the following result :- 0.2320 gram substance gave 0.1087 LBg = 46-85 per cent. Calculated for C6H&OOAg = 45.57 ; C5H,,COOAg = 48-43. It was therefore as before a mixture of hexoic and heptoic acids. The unoxidised oil gave also the same curious results as those obtained when the ot,her oxidising agents were used.(4.) Action of Potash on the Aldehyde CI4H2,O. As the body C14H260 is an aldehyde, it was thought that it would be interesting t o see what the further action of potash on it would be, more especially as it appeared probable that by this means some clue might be obtained to the constitution of the higher condensation- products of oenanthaldehyde. Alcoholic potash acts very readily on this aldehyde, when it is gently heated with it, the whole becoming black, a considerable quantity of a potash salt being at the same time formed, but the oils in this case are very uninviting, and difficult to purify. If the potassium salts are to be examined, it is best to act on the aldehyde with moderately strong alcoholic potash, and to warm the mixture.In examining the oils, however, the following method was found to give the best results :-200 grams of the aldehyde were dissolved in 500 grams alcohol, and 20 grams of a concentrated solu- tion of potassium hydrate in alcohol added in small quantities every day for about six weeks, the whole being well shaken after each addition. By this means the condensation and other changes take place slowly, and there are also less tarry products formed. The mixture, after standing for another two weeks, was diluted with water, and the oil taken up with ether. The aqueous potash-solution was then acidulated with dilute hydrochloric acid, and the liberated acids which it contained removed with ether. The ethereal solution was dried and fractioned. The greater part distilled over between 210-230" ; there was a small residue left.The fraction 210-230" was made into potash salt, and then into a silver salt. A silver estimation gave the following result :- 0.7520 gram substance gave 0.3433 gram Ag = 45.65 per cent. Calculated for C6H&O0 Ag = 45.57 per cent. It was therefore without doubt heptoate of silver. The residue,62 PERKIN ON THE CONDENSATION-PRODiJCTS which boiled above 230", was transferred to a small retort, and two or three times very carefully fractioned under a pressure of 250 mm. The largest fraction obtained, boiled between 275-280". The quantity was, however, very small-about 2 grams. An analysis of it gave the following results :- 0.1469 gram substance gave 0.1520 gram OH2 and 0,3969 CO,.Found. Calculated C,,H2,02. C . . . . . . . . 74-24, per cent. H .... .. .. 11.49 ), 11.50 ,, 74.33 per cent. This body has therefore the formula ClaH2,02, and is without doubt the same acid as that which was obtained by the action of alcoholic potash on cenanthaldehyde. It is a light yellow oil, possessing but little odour, and does not solidify in a freezing mixture. It dissolves without much difficulty in dilute ammonia. On standing over sul- phuric acid, the ammonia salt quickly deposib an oil which is pro- bably the amide of the acid. A solution of the ammoiiia salt was pre- pared by dissolving the acid in dilute a,mmonia, nearly neutralising with dilute nitric acid, and then allowing thg salt to stand for a short time over sulphuric acid. It was then filtered through a wet filter- paper, and the following salts prepared :- The silver salt is precipitated on adding silver nitrate as a white flocculent precipitate, which is instantly decomposed on boiling with water.The barium saZt, precipitated by adding barium chloride, is a, white amorphous precipitate, insoluble in water, but apparently slightly soluble in alcohol. The calcium salt resembles in every respect the barium salt. The copper snlf is precipitated on adding sulphate of copper, as a beautiful emerald-green precipitate, which is insoluble in water and becomes black on boiling. Unfortunately, the amount of acid procured has been so small that it has not been found possible to prepare enough of its salts for analysis. The potassium salt is difficult t o prepare, a soap being formed on treating the acid with a solution of potassium carbonate.The ethereal solution containing the condensed aldehyde and other neutral bodies was next washed, dried over calcium chloride, and fractioned. After the ether had been slowly distilled off, about 3 grams of oil came over between 100" and 200"; the thermometer then rose rapidly to 250°, between which temperature and 300" a considerable quantity of product distilled over. By far the largest quantity remained behind in the retort above 300", and was reserved for distil- lation in a vacuum. The fraction 100-200" was fractioned, andOF ENANTHALDEHYDE. 63 mostly came over between 170-180". lowing results :- On analysis it gave the fol- 0.1145 gram substance gave 0.1394 gram OH2 and 0.3050 CO,.Calculated Found. fol* CBHlsCH2OH. C ........ 72.64 per cent. 72.41 per cent. H ........ 13.52 ,, 13-79 ,, It was therefore heptyl alcohol. It is formed in very small quantity, only about 1 gram boiling between 170-180" being obtained. The fraction 250-300" was then heated in a sealed tube with excess of acetic anhydride at 180" for three days, in order to modify any un- changed aldehyde. On fractioning, from 5-10 grams distilled over below 300". In order to be certain that none of the aldehyde Cl4H2,O WRS present, this fraction was again heated with acetic anhydride t o 200" for two days, and refractioned. The principal quantity distilled over between 270-295", and after further fractioning, gave from 2-3 grams of an oil which boiled between 280-290".Two analyses of these gave the following results :- I. 0.1210 gram substance gave 0.1293 OH, and 0.3386 CO,. 11. 0.1114 ,, ,, 0.1164 ,, 0.3124 ,, Found. Theory for C,,H2,OC2R,O. 75.59 per cent. 11.' I. C ...... 76-31 76.48 per cent. H ...... 11.87 11-61 ,, 11.81 ,, These numbers agree fairly with the formula C14H270.C2H30, which is that of the acetate of the alcohol C14H280 ; but owing to the small- ness of the quantity, it was found impossible to get i t in a purer con- dition. In order, if possible, to confirm this result by preparing the alcohol, the alcoholic potash reaction was tried again, 150 grams of the aldehyde C,,H,,O being used, the mixture being warmed for two days. The oil was then fractioned as before, and the fraction 250-300" treated with acetic anhydride.The acetate was then saponified with alcoholic potash, and the resulting alcohol repeatedly fractioned. In this way a considerable quantity was obtained boiling between 280- 290°, and gave the following result on analysis :- 0.1088 gram substance gave 0.1304 gram OH, and 0.3176 CO,. Found. Theory for C14H250. C ........ 79.61 per cent. 79.25 per cent. H ........ 13.31 ,, 13-21 ,, It is therefore evident that this alcohol is formed in this reaction,64 PERKIN ON THE COXDENSATION-PRODUCTS although in but small quantities. The residue of the original con- densed product which boiled above 300" was, without doubt, the principal product of the reaction, and as it was very black, it was first distilled under reduced precssure. A considerable quantity came over between 280-360" under 250 mm.pressure. This was several times fractioned under 350 mm. pressure ; the principal quantity obtained boiled between 335-340". It was a light yellow oil, which distilled without the least decomposition in a vacuum. On analysis it gave the following numbers :- 0.1235 gram substance gave 0.1374 OH2 and 0,3770 CO,. Found. Theory for C,,R5,O. C . . . . . . . . 83.25 per cent. H .. .. .. .. 12.36 ,, 12-43 ,, It was therefore the compound CzeHN0 previously described. 83.58 per cent. The products of the action of alcoholic potash on Cl4H2,O are therefore : CZ8H5,0, CJLeO, C6H13CH20H, and the acids C6H13COOH and The body CzsHsO0 is evidently produced by the condensat,ion of two molecules of the aldehyde C,4H260-in exactly the same way as the aldehyde C14Ez60 itself is formed from oenanthaldehyde-according to the equation- 2Cl4HZ6O = C2,H6,0 + OH2.C14H2602. Heptoic acid and heptyl alcohol are probably formed according to the equation- The formation of the acid c&602 and the alcohol C14HZgO may also be represented thus : 2C14H33O + KOH = C14Hz5OOK + c,4H2,o. I n these two last equations the potash evidently exerts an oxidising as well as a reducing action, analogous to the action of the same agent on the aromatic aldehydes, as for example in the case of benzaldehyde, which is converted by it into potassic benzoate and benzyl alcohol :- 2CGH5COH + KOH = C6HbCOOK + C,H,CH,OH. In order to more thoroughly examine these secondary reactions, it would be necessary to work with very large quantities of the aldehyde c14H26°.Theopetica 1 Remarks. As the body C,4H260 on oxidation splits up into heptoic andOF CEKANTHALDEHYDE. 65 hexoic acids, and is an aldehyde, it can only have the following con- stitution :- CH,.CH,.CH,.CH,.CH,. CHz.CH It CH3. CH,. CHp CH2. CH2. C. COH. It may be called hexyl-pentyl-acryl aldehyde, and is formed from two molecules of cenanthaldehyde, according to the equation- CH3.CH2.CH,.CHz.CH2.CH2.CH '0 . CH3. CH,.CH,. CHa.CH,.C.COH /H2 = CH,.CH,.CHz.CH,.CH2.CH2.CH II + OH2. CH3. CH2. CH2. C H, . CHZ. C . C 0 H I n order to show it was unsaturated as indicated by the equation, 51.25 grams of the aldehyde C,,H,,O were dissolved in bisulphide of carbon cooled down t o -lo", and titrated with dry bromine. It took up 39.10 grams bromine (traces of hydrobromic acid only being produced) = 76.32 per cent. ; calculated quantity for ClaH2,0 + Br2 is = 76.66 per cent. In this case there is no doubt that a, body of the following formula is formed :- C H3. CH2. CH,. C H,. C H2. CH2. CHBr CH3.CH2.CH2. CH,.CH2. CBr.COH It is, however, impossible to isolate this product; for as soon as the solution in carbon bisulphide attains a temperature of 30°, hydro- bromic acid begins to come off, and the whole turns black. The oxidation of the aldehyde ClkHz60 takes place apparently according to the following equation :- CH,. CH,.CH,.CH2.CH2.CHz.CH + 0, - II C H,. C H,. C H,. CH,. CH,. C . C OH + c02. C H3. CHZ. C H,. CH . ZCH,. CH,. C 0 0 H + CH3. CHZ. CH,. CH2. CH2. GO OH As the body C,,H,,O is produced by the action of potash or acetic anhydride on C,4H260 with separation of water, it follows that it must be formed from two molecules of C,aH&. By melting with potash, it gives only the two acids: heptoic and hexoic acids. The following formula will therefore represent its constitution :-66 PERKIN ON THE CONDENSATION-PRODUCTS CH,.CH,.CH,.CH,. CHz.CH2.CH It CH3. CH2. CH,. CH,. CH2. C . CH II CH3.CH2.CH,.CH2.CH2.C . CH II CH,. CH2. C H2. CH,. CH2. C. C OH. Its formation from two molecules of C14H2,0 would then take place according to the equation :- CH3,CH2.CH2.CH,.CH,.CH,.CH II .......... CH3. CH2.CH2. CHS.CH2.C.CH iO i :;/iH 2; I CH,. C H,. C H,. CH,. C H,. C . C H-""' If the constitution given for the aldehyde C14H2,0 be correct, the unsaturated alcohol C14H280, which is formed from it by the action of nascent hydrogen, may be represented thus- CH3. CH2. CH2.CHZ.CH2. CH2.CH It CHS.GH2.CH2. CH2.CH2.C. CHZOH, and the saturated alcohol, being formed by the action of nascent hydrogen on the unsaturated alcohol, will therefore have the following constitution :- CH3.CH2.CH,.CH2.CH2. CH2.CH2 I CH3. CH2.CH2.CH2.CH2. CH.CH20H, and is tberefore p-heptyl-heptyl alcohol, or heptyl-pentyl-ethyl alcohol. And finally the acid Cl4HZ6o2 will have the constitution CH3.CH2.CH2.CHD CH,.CH,.CH II C HS. C Hz. CH2. C H2. C H2. C . Q 0 OE, and is therefore hexyl-pentyl-acrylic acid.

ISSN:0368-1645    

DOI:10.1039/CT8834300045

出版商:RSC    

年代:1883

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OF CENAXTHALDEHTDE. 67 IX.-Condensatioiz-~rodzLcts of Ghair thaldehyde (Part 11). By W. H. PERKIN, JuN., Ph.D. Action of Nascent Hydrogen o n GYnanthaldeh yde. Ir; the prepailation of hepbyl alcohol by the action of nascent hydrogen on cenanthaldehyde, there is always a considerable quantity of a high- boiling bye-product formed, which often amounts to 20 per cent. of the cenanthaldehyde used. This remains in the rehort, on distilling off the heptyl alcohol, as a thick brown oil, which, however, does not seem to have been investigated. As it was probable that these oils were simply condensation-products, produced by the dehydrating action of the agents used, and possibly acted on by the nascent hydrogen ; it was thought that they might yield interesting results upon examination. The inquiry was divided into two parts: (l), action of nascent hydrogen on mnanthaldehyde in acid solution ; (2), in ethereal solution.(1.) Aation, of Nascent Hydrogen on Q3'nalztlzaldehyde ilz Acetic Acid Solut&on. The operations were conducted in the same manner as described in Part r, in the section on the action of nascent hydrogen in acid solution on the aldehyde CI1H,,O. It is practically the same as that employed by C. F. Cross (Jour. Ckern. Xoc., 32, 123) for the pre- paration of heptyl alcohol. 200 grams of cenanthaldehyde were used in each operation, and about twice as much sodium amalgam as theoretically required for the formation of heptyl alcohol. At the end of the reaction water was added, and the oil, after being washed, was boiled with a dilute solution of potash, in order t o decom- pose acetates, which are always formed.It was then washed, dried, and distilled under reduced pressure (350 mm.), until the temperature reached 300". The residue was not examined. The distillate was fractioned under ordinary pressure. The principal quantity, consisting of heptyl alcohol and a small quantity of unchanged cenanthaldehyde, came over below 200" ; the thermometer then rose rapidly to 240", between which temperature and 300" a large amount of product distilled over. This last quantity was repeatedly rectified, when three fractions were obtained, boiling between 2$0-275", 275-280", and 280-283", all of about the same size. The analyses of these gave numbers which always came between those calculated for the alde- VOL.XLIII. F68 PERKIN ON THE CONDENSATION-PRODUCTS hyde CliH2,0, and the alcohol Cl1HZBO, so that it appeared very pro- bable that both were present. In order to separate them the fractions between 265-285" were heated in sealed tubes with excess of acet'ic anhydride at 180-200' for four days, and then distilled. After the acetic acid and excess of anhydride had passed over, a considerable quantity of oil was 'obtained boiling between 270-300". There was, however, a dark brown residue left, which would seem to show that, as was anticipated, some aldehyde, such as CliHz6O, was previously present, and had been condensed by the action of the acetic anhydride. The oil distilling between 270-300" was then repeatedly fractio-d, and at last gave a product which boiled pretty steadily between 280- 285".It was a colourless, highly refracting oil, possessing an agree- able odour. The analysis gave the following numbers :- I. 0.1860 gram substance gave 001992 gram OH, and 0.5170 gram 11. 0.2167 gram Substance gave 0.2302 gram OH2 and 0.6030 gram GO,. c 0 2 . Found. r--& 7 C d d d i ~ d C16H3002 = I. 11, CidI32; 0 C, H,O . C.. . . . . 75-81 75989 per cent. 75053 per cent. H .. . . 11.90 11-80 ,, 11-81 ,, This was therefore the acetate derived from the alcohol C14H,0. As this substance, from its composition, should be an unsaturated body, it was dissolved in carbon disulphide, cooled down to -loo, and titrated with bromine. The colour of the bromine disappeared instantaneously without evolution of hydrobromic acid, A quantitative experiment gave the following numbers :- 2.2355 grams substance took up, without evolution of hydrobromic Calculated for C,,H,O, + Br2 = 62.9 per cent.Attempts were made to isolate the bromine addition-product, biit the body decomposes on distilling off the carbon disulphide, giving off hydrobromic acid. On distilling off the alcohol and adding water to the residue, the alcohol ClrHzsO separates as an oil. This was taken up with ether, and the ehhereal solution distilled. After a few fractional distillations the principal quantity came over as a colourless oil boiling at 280-283". Analysis gave the following result :- acid, 1.3477 gram bromine = 60.3 per cent. This acetate was saponified by boiling with alcoholic potash. 0.1494 gram substance gave 0.1777 OH, and 0.4340 CO2.OF CENANTHALDEHYDE.69 Found. Calculated CisH2,CH20H. C ...... 79.33 per cent. 79.25 per cent. H.. .... 1322 ,, 13.21 ,, There can be no doubt that this alcohol and the acetate from which it was separated are the same bodies as those described in Part I, p. 55, as the properties of the two so closely agree. The formation of this alcohol from oenanthaldehyde is probably due to the dehydrating action of the glacial acetic acid and sodium acetate, formed in the reaction, first producing the aldehyde C14H260, a part of which is then acted on by nascent hydrogen, yielding this product. It is practi- cally impossible to separate the aldehyde C&t&O from the alcohol Cl4HT,,0 by fractiocal distillation, but the treatment with acetic anhydride forms an easy way of separating them, as shown in Part I.The products of the action of nascent hydrogen in acid solution, as far as they have been examined, are therefore, heptyl alcohol, pro- bably the aldehyde CllHZ60, and the alcohol C1,H2,O. (2.) Actiorb of Nascent Hbdrogen 018 G%nnSthalclehyde i n Ethereal Solution. This operation was conducted in the same way as that described in Part I, p. 54, where the treatment of an ethereal solution of the aldehyde, C14H260, is described. 450 grams of oenanthaldehyde dis- solved i n about l& to 2 litres of ether, and from 200 to 210 grams of sodium, were used in each experiment, which required from four to five days for completion. The ethereal was separated from the aqueous solution, well washed, first with dilute hydrochloric acid and then with water, and dried over calcium chloride.The examination of the aqueous solution showed that it contained an oily acid boiling between 221-225" ; it gave the following numbers on analysis :- 0.2714 gram substance gave 0.2631 gram OH, and 0.6400 gram c 0,. Found. Calculated for C6HI3COOH. C ...... 64.31 per cent. 64.61 per cent. H ...... 10.77 ,, 10.77 ,, It was therefore heptoic acid. The ethereal solution, containing the neutral oils, wa,s next examined. After the ether had been distilled off, the oil was frac- tioned in a stream of carbonic anhydride. It began to boil a t 150", between which temperature and 'LOO" a considerable quantity disiilled over, consisting of a mixture of heptyl F 270 PEKKTN ON THE CONDENSATION-PRODUCTS ___- C .... .. .. K . . .. .. .. alcohol and unchanged cenanthaldehyde. The thermometer then rose rapidly to 250", a large quantity coming over between 250-300". The residue was reserved f o r distillation in vucuo, and is referred to further on. The portion boiling between 250-300' was several times carefully fractioned in a stream of carbonic anhydride, as the oils oxidise in the air. It was found that when cooled down t o 0" all the fractions from 255-280" deposited crystals, some becoming almost solid. I n order t o obtain this solid product in a pure state, the various fractions were cooled down to -20' in a mixture of ice and hydrochlorie acid, and the oil then filtered off from the crystals as quickly as possible, by means of it Faeuum pump.They were then quickly pressed between filter-payer a t as low a temperature as possible, and further purified by crystallisation from ether, in which they are very soluble ; on allowing the solution to evaporate spontaneously, large transparent crystals, wit>h a beautiful lustre, were deposited. These were filtered off from the ethereal solution, and placed over sul- phuric acid in an atmosphere of CO, for some t h e . The following analyses were made from several preparations :- I. 11. 1x1. VI. ---- -------- '79.56 78.96 '78'86 12.9'7 13.14 13.03 I. 0.1693 gram substance gave 0.197'7 OH, and 0.4939 CO,. 11. 0.2333 ,, 7 ) ,, 0.2760 ,, 0,6755 ,, 111. 0-2426 ,, 7 7 ,, 0.2846 ,,. 0.7015 ,, IV. 0.1343 ,? ,, 0.1818 ,, 0.4474 ,, V. 0.1565. ,, , I ,, 0.1872 ,, 0.4543 ,, VI.0.1985 ,, 1 , ,, 0.2355 ,, 0.5741 , l VII. 0.1308 ,, M ,, 0.1561 ), 0-3795 ,, VIII. 0.1467 ,, ,, ,, 0.1770 ,, 0.4251 ,, 1 VII. 1 VIII. 1 Mean. Found. Theory Cl,H,,O. C .. .. .. .. 1 79-13 I H... ..... 13-26 13-19 ,, 1 79 -09 per cent. Pound. '79 -25 per cent. 13.21 ,,OF (ENANTHALDEHYDE. 71 This substance therefore has the formula C,,H,,O. It is a beautiful body, crystallising in plates which melt at 29.5". It boils without the least decomposition a t 266-268". It is easily soluble in carbon di- sulphide, ether, alcohol, petroleuu et.her, and chloroform. The so!ution in carbon disulphide, if cooled down to -lo", does not take up bro- mine, it therefore appears to be a saturated body. It combines very slowly with hydrogen sodium snlphite, so that, after standing for six months with a concentrated solution of the latter body, it had not quite ceasccl depositing crystals.The amount of the compound obtained was unfortunately too small for analysis. This body also reduces an ammoniacal silver solution, and oxidises, when left in contact with t'he air, b u t only very slowly when in the solid state. From these properties it appears to be an aldehyde. Heated with acetic anhydride for four days in a sealed tube a t 180", it did not form an acetate. Acetic anhydride appears to act on it very slowly, as on fractioning the product there was only a ver.y small residue left in the retoat above 280'. The specific gravity of this aldehyde i n the fused state is- a t 30' = 0.8274 a t 35 = 0.8258 compared with water a t t,he same temperakures.oenanthaldehyde may be expressed by the following equation :- Its formation from 2C7HIAO + H2 = C,,H,,O + OH,. The residue left in the retort above 310°, after distillins off the aldehyde just described, was very thick and black, and was therefore first distilled i r b Z'UCZIO, and then fractioned under a pressure of 300 mm. By the first distillation a considerable quantity of an almost colourless oil distilled over between 310-350". On repeatedly f ractioning under the same pressure, two principal products were obtained, boiling between 315-320" and 320-325", of which the first was the larger. Analyses of these gave the following results :-- I. (320-325") 0.2466 gram substance gave 0.2882 OH, and 11. (315--320") 0.1782 gram substance gave 0.2084 OH, ant1 111.(315-320") 0.1480 gram substance gave 0.1734 OH, atid IV. (315-320") 0.2159 gram substance gave 0.2540 CO, and 0.7347 co,. 0.5332 COP 0.4432 COZ. 0.6466 COz.72 PERKIN ON THE CONDENSATION-PRODUCTS Found. r------"---I- I. 11. 111. I V F Theory CilH4,,0. CI . . . . 81.8 81.60 81.67 61-66 per cent. 81.82 per cent. H . . . . 12.99 12-99 13.02 13.07 ,, 12-99 ,, This body has therefore the formula C2,H4,0. It is a slightly yellow, very thick oil, which does not solidify a t -10". It reduces ammoniacal silver solution, but, does not appear to combine with hy- drogen sodium sulphite. Heated with potash it becomes thick aid black, a small quantity of a potash salt being formed. Boiling with dilute snlphuric acid also decomposes it. In order to see if it were unsaturated, it was dissolved in carbon disulphide, cooled down to -10, and titrated with bromine.The colour of the bromine dis- appeared instantly. A quantitative experiment gave the following result :- 20.65 grams dissolved in carbon disulphide, took up 10.8 grams bromine without the evolution of hydrobromic acid = 52.3 per cent . Calculated for C,,H,,O 4- Br, = 51.9 per cent. It appears therefore to be an unsaturated body. Its formation from cenanthaldehyde may be represented by the following equation :-- 3CTHIdO + H, = C,,H,,O + 20Hz. I t s specific gravity was found to be :- at 15" = 0.8744 a t 30 = 0.8665 at 35 = 0.8637 compared with water a t the same temperatures. The yield of this body is from 5 to 10 per cent. of the mnanthaldehyde used.The residue in the retort, boiling above 359" in vacuo, became solid on cooling. On extracting with ether a white solid body remained behind, which dissolved on boiling with water. On cooling, needles of calcium heptoate crystallised out. A calcium estimation gave 13.44 Ca. Calculated for ( CBH,3C00)2Ca = 13.43 per cent. Ca. The presence of this salt is probably due to the fact that the crude oil was in the first place dried over calcium chloride, which is a little soluble in the oil, and that, at the high temperature employed in the following distillations, it was converted into calcic heptoate. The products of the action of nascent hydrogen in alkaline solution on cenanthaldehyde, as far as they have been examined, are therefore:- Heptyl alcohol : heptoic acid : the solid aldehyde C14H280 : and the body C21Hd"O.OF CENAMTHALDEHYDE.73 Oxidation of the Aldehyde C,,H,O. In order to obtain some idea as to the constitutiion of this aldehyde, Cl4H,,O, and of the nature of the groups contained in it, several oxi- dation experiments were made, much in the same way as in the case of the aldehyde ClaHzsO, described in Part I. The aldehyde C&& was dissolved in glacial acetic acid, and one and a-half times its weight of chromic acid dissolved in glacial acetic acid slowly added, the product being well cooled after each addition. The action is very energetic, large quantities of carbonic anhydride being given off. AS soon as all the chromic acid had been added, the product was heated for two hours 011 a water-bath to complete the oxidation.The pro- duct was treated as in the analogous experiments in Part I. The acids obtained came over between 190" and 230°, and the liquid thus obtained was separated by further distillation into two fractioiis boiling between 195-210° and 210-230". Each of these was con- verted into a potassium compound and then fractionally precipitated with nitrate of silver into five fractions. Silver estimations were made in each of these precipitates. The results showed clearly that a mixture of hexoate and heptoate of silver was present. The silver salts which gave the best results were fully analysed, and gave the following numbers. Of that from tlie potassium salt of the acid (195-210"), fractions IV and V were analysed, with the following results :- I.0.220'21 gram substance gave 0*1000 OH,, 0.2649 CO,, and 11. 0.2479 gram substance gave 0.1121 OH,, 0.2939 C 0 2 , and 111. 0.2267 gram substance gave 0.1040 OH,, 0.2742 COz, and 0.1052 Ag. 0.1202 Ag. 0.1083 Ag. Found. I. 11. - 111. Theory for { $aig. r- C . . . . 32.81 32.33 32.97 per cent. 32.28 per cent. H . . . . 5-05 5.02 5.10 ,, 4.93 ,, Ag . . 47.77 48.48 47.77 ,, 48.43 ,, It was, therefore, without doubt, hexoate of silver. I1 and I11 were analysed with the following results :- Of that from the potassium salt of the acid 218-230" fractions I. 0.2435 gram substance gave 0.1215 OH2, 0.3174 CO,, and 0.1112 Ag.74 PERRIN ON THE CONDENSATION-PRODUCTS 11. 0.1533 gram substance gave 0.0759 OH,, 0.1975 C02, and ITI. 0.2368 gram substance gave 0.1145 OH,, 0.3039 GOL, and 0.0702 Ag.0.1084 Ag. Found. I. 11. 111. 7 Theory for { :gig. r--d--- C . . . . 35.55 35-13 35.00 per cent. 35-44! per cent. H . , . . 5-56 5-50 5-37 ,, 5-48 ,, Ag . . 4-5-66 45.79 45.77 ,, 45.57 ,, It was, therefore, heptoate of silver. The products of the oxidation of the aldehyde CIIH280, by means of chromic acid and acetic acid, are therefore carbonic anhydride, and heptoic and hexoic acids, according to the equation- Oxidation with silver oxide was next tried. This experiment was made in the same way as with the aldehyde C,,H2,0, Part I. The acids obtained were carefully fractioned. By f a r the largest fraction obtained boiled between 19.5- 230" ; thew was, however, a small quantity of a dark-brown resicluo left, which was reserved for distillation in v m m .The distillate 195-230" was converted into a potassium and then into a barium compound. This dried a t 120--130" gave on analysis the following results :- I. 0.1666 gram substance gave 0.1013 RaS04 = 35.79 per cent. Ba. 11. 0.1290 ,, ,, 0.0785 ,, = 35.78 ,, 9 , hexoate of barium . . . . . . . . . . 37.33 Calculated for heptoate of barium . . . . . . . 34.70 per cent. 9 , ,, ,, This barium compound was therefore a mixtnre of barium hexoate and heptoute, the two acids being formed as in the case of the oxida- tion by means of chromic acid. The dark-brown residue remaining in the retort above 230" was first distilled under a pressure of 300°, when most of it came over a t about 230". This was then carefully fractioned a t the ordinary pressure.After a small quantity of heptoic acid had passed over, the thermometer rose rapidly to 300°, almost all the product (about 18 grams) distilling between 300-310". On analysis it gave the following numbers :- I. 0.0967 gram substance gave 0.1029 OH2 and 0.2623 CO,. 11. 0.1341 ,, ,, 0,1428 ,, 0.3680 ,,OF (ENANTHALDEHYDE. 75 Found. 7 Theory rd-- for C14H2S02. I. 11. C . . . . . . 73-97 7359 per cent. 73.60 per cent. H . . , . . . 11-82 11-83 ,, 12.28 ,, This acid, therefore, has the formula C1,H,,O2. It is an almost colourless oil, which distils at the ordinary pressure, apparently with- out the least decomposition. The yield from the aldehyde CI,H2,0 is very small, so that it was found impossible to prepare salts pure enough for analysis. This acid dissolves in ammonia, but the ammonium salt, on st'and- ing, quickly deposits an oil which may possibly be the amide of the acid.It is formed by shaking the a,cid with very dilute potash.; on evaporating, how- ever, it appears to decompose. The formation of this acid from the aldehyde may be expressed thus :- The potash salt is a, soap, and difficult to obtain pure. By cooling to - 10" it becomes very thick, but was not obtained in a, sclid condition. As it seemed possible that the acid just described might be obtained in larger quantity from the aldehyde by employing an alkaline solu- tion of potassium permnnganate, the following experiment was made. About 20 grams of CIIH,,O were mixed with rather more than the calculated quantity of permanganate dissolved in dilute soda, and from time to time the mixture was well shaken up.The oxidation took place rapidly xt first, but afterwards pyoceeded very slowly. At the end of a week alcohol mas added, and the soda solution sepn- rated from the precipitated hydrate of manganese by filtering through glass wool. The acids which had been formed were then liberateti with hydrochloric acid, taken up with ether, and fractioned. How- ever, almost all the acids came over between 200--236", and only a trace of an acid with a high boiling point was present,; this, however, appeared to boil a t the same temperature as that obtained by the oxi- dation with silver oxide. The fraction boiling between 200--230° was converted into potash salts, purified as usual with absolute alcohol, and the silver salts precipitated with nitrate of silver.Analysis gave the following result :- 0.3208 gram substance gave 0.1475 OH3, 0*:!896 CO,, and 0.1567 Ag. Theory for Theory for Pound. C,H,,COOAg. C6 H,,COOAg. C . . . . 33.12 per cent. 32.28 per cent. 35.44 per cent. H . . . . 5-11 ,, 4.93 ,, 5.48 ,, Ag . . 48.84 ,, 48.43 ,, 45.57 ,,76 PERKIK ON THE CONDENSATION-PRODUCTS It was therefore a mixture of hexoate and heptoate of silver. Tho products of the oxidation of C14H2,0 are therefore carbonic anhydride, heptoic and hexoic acids, and ClsH,,COOE. Several attempts were made to purify the neutral oils which were obtained in these experiments by fractional distillation, but although several anaylses were made of different fractions, no good results could be obtained.They begin to boil a t 250°, but by far the greater part boil above 360". Action, of Nascent Hydrogen on the Aldehyde CJl,,O. The crystalline body, ClaH2,O, being an aldehyde, it was thought interesting to try the action of nascent liydrogen on it, in.order, if possible, to get the corresponding alcohol ClrH,O. This would have the same formula as that previously obtained by the action of nascent hydrogen on the alcohol C'JiT,O (Part I, p. 56). The experiment W ~ S made in the following way: The aldehyde was first dissolved in glacial acetic acid, and zinc turnings added, the whole being warmed on a water-bath. It was found advantageous to cover the surface of the zinc with copper, by dipping it in a solution of sulphate of copper, the action being thus very much accelerated, Prom time to time small quantities of water were added ; the mixture was heated a t last nearly to boiling.Water was then added in excess, and after nearly neutralising the acetic acid with potash, the oil was separated and well washed. On distilling, there stiil appeared to be a consider- able quantity of unchanged aldehyde present, t.he product was, there- fore, again treated with nascent hydrogen. This time, however, the sil was dissolved in ether and treated with water and sodium in exactly the same way as was employed in the reduction of amanth- aldehyde, as it was found to give better results. than zinc and acetic acid. After a considerable excess of sodium had been added, the oil was extracted from the aqueous solution with etrher, then dried and fractioned.After t'he ether had been distilled off, the principal quantity of the product came over between 260-2Y0°, only a small residue remaining behind in the retort. This distillate was then several times carefully fractioned, the largest part obtained boiling bet ween 270-275". On analysis it gave the Pollowing numbers :- 0.1500 gram substance gave 0.1881 OH, and 0.4304 CO,. C . . . . . . . . 78.25 per cent. H . . . . . . .. 13.93 ,, 14.08 ,, Found. Theory for CI4HN0. 78.50 per cent. I t therefore has the formula ClrH300.OF (ENANTHALDEHY DE. 77 It is a colourless oil, having but little odour. Cooled down to - 10' it solidifies to a waxy mass, which melts again at the ordinary temperature, When dissolved in carbon disulphide, and cooled down to - lo", it does not take up bromine. Its specific gravity is It does not oxidise in contact with the air.It is soluble in most of the ordinary solvents. at 15' = 0.8368 at 30 = 0*83Gl at 35 = 0.8279 compared with water at the same temperatures, It is, without doubt, the same alcohol as that previously obtained by the action of nascent hydrogen on the unsaturated alcohol CI4H2,0, as it has the same boil- ing point. To further establish this, however, the a.cetate was pre- pared by heating it in a sealed tube with excess of acetic anhydride at lS0" for two days. On the first distillation almost all the oily product distilled over between 270--385", very little residue being left in the retort. On repeating the fractioning, the principal portion came over between 275-280*.0.1165 gram substance gave 0.1310 OH, and 0.3210 CO,. On analysis it gavd the following numbers :- Found. Theory for C,4H~,0C,€T~0. C . . . . . . . . 75.14 per cent. H .. .. .. . . 12.49 ,, 12.50 ,, 75.00 per cent. The numbers agree therefore with those required for the formula In order to prove that this body is an acetate, a determination of the acetic acid, formed by its saponification, was made, which gave tlie following numbers :- 3.5293 grains substance gave 1.3065 grams potassium acetate = The formula Cl$H290.C2H30 requires This acetate is a beautiful colourless oil, possessing an aromatic It boils a t the same temperature as that described in Part I Cooled to - 10" it When warmed with alcoholic potash it is ver,y l t s Cl,Ei,,O.C,H,O, 22.67 per cent.C2Hi,0a. 23.43 per cent. odonr. (275-280"). does not solidify. easily decomposed into potassic acetate and the alcohol ClaHNO. specific gravity is It refracts light very strongly. a t 15" = 0.8559 a t 30 = 0.8476 at 35 = 0.8448 compared with water at the same temperatures.78 PERKIN ON THE CONDENSATION-PRODUCTS It is therefore seen that both the aldehyde C,,H,,COH, and the alco- hol Cl&.TOH, when treated with nascent hydrogen, yield the same body, viz., the alcohol C14H290H. Tli eore't ical Eernnds. As the aldehyde C,aH2s0 splits up on oxidation and carbonic acids, according to the equation- into heptoic, hexoic, CO, + OH2, it must have the following constitution :--- CHI,.CH,.CH?.CH,.C B,.CH.COH. This shows that it is a saturated body. It is isomeric with the alcohol CllHzJO described in Part J, obtained by the action of nascent hydrogen on the aldehyde C1,H2,O.'-CH, This aldehyde Cl,H2,0 contains the group I , whereas the -CH.COH -CH alcohol contains the group 11 -C.CHzOH The production of thiq aldehyde is somewhat difficult .to understand, it is not formed by the action of nascent) hydrogen on the alde- hyde C,aH?,O. It would seem to be probably formed by the action of the nascent hydrogen a t the moment of the condensation of the cenanthaldehyde. A f,urther attempt, to tobtain it from the aldehyde C l J L O was made by dissolving the latter in -ether, cooling in a frAezing mixture, and then adding bromine. As soon as this was no longer decolorised, water WRS added and then sodium, till A small quantity of the ethereal solution taken out was found no longer to contain bromine.The ether was then distilled OK and the residual oil fractioned. A considerable quantity came over between 270-280", which on combustion gave numbers agreeing fairly well with the formuh C14H300 ; it was therefore apparently the same alcohol as that obtainetl by the action of nascent hydrogen on %he aldehyde and alcohol CldH280. On heating with acetic anhydride in a sealed tube, it also gave an acetate. It is quite possible that some of the aldehyde C14H,s0 was formed in this experiment, but could not be separated from the alcohol C,aH,oO. The aldehyde Cl,H,,O is isomeric with myristic aldehyde, which F. Krafft (Ber., 13, 1415) obtained by the d r y distil-OF mNANTHALDEHPDE. 79 Lation of a mixture of barium myristate, barium formate, and lime.It, melts a t 52*5", or 23" higher than my product. The constitution of the acid C14H,,0z obtained by the oxidation of the aldehyde C,,H,,O, is represented thus :- C H,. CHZ. C Hz. CH,. C Hz. C H,. C Hz CH,.CH,.CH,.CH,.CH,.CH.COOH. It is therefore, heptylpentylacetic acid. It also appears to be formed by the action of alcoholic potash on the aldehyde C,,H,,O in the same way as the corresponding acrylic acid CICHz6O2 is obtained from the aldehyde CldH260. In the oxidation of the aldehyde C,aH,80, i t is probable thah this acid is first formed, and then on account of its easy oxidisability is qui'ckly converted into hexoic and heptoic acids. This acid is isomeric with myristic acid, which Krafft (Ber., 12, 1669) obtained by saponsying nutmeg oil.He describes it as a solid body melting a t 53.8", but gives no payticulars as to its constitution. The body having the formula CzlHCoO, which is formed by the union of 3 mois. of cenanbhaldehyde, according to the following equation :- has probably the following constitution :- 31=,H,,O + H, = C2,H,,O + 2HZ0, CH,.~H,.CH,.C.IE,.CHz.CH, CHI II CH3.CH,.CH,.CH,.CH,.C.CH2 I CH,. CH2.CH,.CH,.CH,.CH.COH. This is borne out by the fact that when dissolved in carbon disul- phide and cooled down to -lO", it takes up 2 atoms of bromine, showing that it is unsaturated. The constitution of the alcohol C11H[30@, obtained by the action of nascent hydrogen on the aldehyde ClrHzeO, and the alcohol isomeric with itr, has already been referred to in Part I.It is isomeric with myristic alcohol, which is contained in spermaceti, together with cetyl alcohol and other bodies. Poly merisa tio n of @?a an t Jr a I&lzyde. Bruylants (Bey., 8, 415) has shown that by the action of dry potassium carbonate on oenanthaldehyde a solid polymeride of this body is produced, and i t was thought that it would be of interest to make some experiments wi.th this compound, with a view, if possible, of getting some clue as to its molecular weight, and also of comparing i t with aldol. Borodin mentions that these two bodies appear to be closely related, both of them losing water on distillation, aldol giving80 PERKIN ON THE CONDENSATION-PRODTTCTS crotonic aldehyde ; while the polymeride of mnan thaldehyde gives the bodies C1,H2,O and C28H5103, oenanthaldehyde being also apparently regenerated.The latter reaction seems, however, to be more compli- cated than that with aldol, and the formation of the body C29H5i0J would appear to indicate that the polymeride contained more than twice C7H,,0. The polymeride was prepared as follows by the method used by Bruylants :- 100 grams of ananthaldehyde were mixed with about 20 grams of dry potassinm carbonate, and allowed to stand a t ordinary tempera- tures, the formation of the polymeride generally reqniring about four days. It is, however, hastened by gently warming and shaking the mixture from time to time a t about 40-45"; the polymerisation is then generally complete in 5-6 hours, the aldehyde becoming quite solid. In order to ensure tlhe polymerisation of all the mnanthaldehyde the mass was melted at GO', shaken up with a small quantity of fresh potassium carbonate, and left to crystallise.The product was carefully melted, and well washed with warm water, taking cai*e that the temperature was not above 70". As soon as all the carbonate was dissolved out the water waB separated as much as possible, and the oil left to crystalhe over sulphuric acid. It was then placed in a vessel with a capillary tube at the bottom end connected with a vacuum pump. On working this, the oil was gradually drawn off, leaving the nearly pure polymeride as a white waxy crystalline mass I n order to free it perfectly from oil, i t was pressed between 6lter- paper, moistened with ether, and again pressed. Obtained in this manner, it melted at 52-53', which corresponds with the melting point found by Bruylants. The oil which was drawn off from the crystals on standing for some time at O", deposits a further quantity of this body in crystals-generally as long needles. By repeating this cooling process, most of the product is eventually obtained in a solid state, only a very small quantityof oil remaining.The polymeride of mnanthaldehyde is very easily soluble in alcohol, ether, chloroform, carbon disulphide, petroleum, ether, &c., but it could not be crys- tallised from these solvents. It reduces an ammoniacal solution of oxide of silver very readily. If bromine be added to a solution of this body i n carbon disulphide and cooled in a freezing mixture, it is not decolorised.This generally requires about two days. It was analysed, and gave the following numbers :- 0.2255 gram substance gave 0.2500 OX2 and 0.6079 C02. Found. Theory for (C?H,,O),. C . . . . . . . . 73.53 per cent. H .. .. .. .. 12.32 ,, 12-28 ,, 73.68 per cent.OF CENANTHALDEHYDE. 81 As already stated, it melts at 52-53', and decomposes on heating above 113". The decomposition seems to begin a t that temperature, water being given off, and collecting a t the top of the vessel in which it is heated, as a cloud. In order to examine the decomposition-pro- ducts of this body, 50 grams were distilled in a stream of carbonic anhydride, The substance first melts, and a t about 120' froths up a little. Between 120" and 200" a good deal came over, the thermometer then rose rapidly to 270°, and between this and 300' the amount which distilled over was considerable.A small residue remained behind, which was reserved for distillation in a vacuum. It was noticed that when the substance was quickly distilled, the residue was very small, whereas if the decomposition is allowed to take place slowly, the amount of residue is increased. The oil boiling between 120-200" was then several times carefully fractioned in a current of carbonic anhydride, nearly all of it at last coming over between 152-154", and smelling stronglp of cenanthaldehyde. Shaken up with a solution of hydrogen sodium sulphite it combined directly, and on analysis gave the following numbers :- 0.0929 gram substance gave 0.0988 OH, and 0.2507 CO,. C ........73.59per cent. 73.68 per cent. H ........ 11.81 ,, 12-28 ,, Found. Calculated for C,H,,COH. It wag therefore cenanthaldehyde. The fraction 270-290" was then several times fractioned in an atmofiphere of carbonic anhydride. Almost all came over at last between 275-280', and gave the follow- ing numbers on analysis :- 0.2414 gram substance gave 0.2700 OH, and 0.7063 CO,. Found. Calculated for CI4Hg60. C ........ 79.79 percent. 80.00 per cent. H ........ 12.43 ,, 12.38 ,, It was therefore the aldehyde CIaHz6O, and mas undoubtedly identical with that obtained from cenanthaldehyde by the action of alcoholic potash, and described in Part I. Its specific gravity was practically the same, viz., 0.8504 at 15", as compared with 0.8494. Dissolved in carbon disnlphide it combines with bromine without evolution of hydrobromic acid, and does not solidify a t -15".It may be mentioned that by the decomposition of the polymeride of cenanthaldehyde by distillation, cenanthaldehyde and the body C,,H,,O are easily obtained in a pure state, as the decomposition takes place nearly quantitatively, only a very small residue being formed, The two bodies are very easily separated by fractional distillation,82 PERKIK ON THE CONDENSATION-PRODUCTS mnanthaldehyde boiling a t 154", and the aldehyde Cl4H2,0 at 179'. The residues boiling above 290" (collected from a series of experi- ments) were first distilled in a vacuum, and then fractioned under a pressure of 250 mm. A t the first distillation nearly all came over bettween 310-350" as a light yellow oil.This fraction was then several times carehlly fractioned under the same pressure, when most of it boiled at 330-340", and gave the followirig numbers on analysis :- I. 0.1211 gram substarice gave 0.1349 OH, and 0.3427 GOz. 11. 0.1324 ,, ,, 0.1474 ,, 0.3737 ,, Found. rL- 7 Theory I. 11. for C2,HT,,03. C . . . . . . 77-18 76.98 per cent. 76.71 per cent. H . . . . . . 12.37 12-37 ,,. 12.33 ,, This body seems therefore to have the composition Cz8H5,03. It is an oil of a slightly yellow colour and disagreeable smell, which does riot solidify when cooled down to - 10". When dissolved in carbon disulphide and cooled down to - lo", it takes up bromine without evolution of hydrobromic acid. Quantitative exgerirnents were made with a view of determining the degree of unsatnration of the body, and gave numbers which agreed fairly well with those calculated for the formda C,,H,,03Br,; but on titration with bromine, after a certain point is reached, the oil becomes slightly brown, and this makes it difficult t o ascertain accurately when the bromine ceases to be taken up.It is apparently formed by removal of the elements of water from 4 mols. of cenantihaldehyde. Thus :- 4C,H,,O = Cz8H,,03 + OH,. On heating it with strong alcoholic potash it becomes brown, apparently being converted i iito higher condensation-products. A small quantity of potash com- pound was formed ak the same time, which appeared to be potassium heptoate. Boiling with dilute sulphuric acid also decomposes this oil. The polymeride of cenanthaldehyde splits up, therefore, on distil- lation into water, cenanthaldehyde, the aldehyde CliH260, and the body Cz8H5403.These results therefore agree with those obtained by Borodin. I n order, if possible, t o get some idea as t o the molecular weight of this polymeric modification of cenanthaldehyde, it wa3 thought that by carefully distilling known quantities and then weighing the decom- position-products, i.e., the cenanthol C14H,,0 and the residue, some This body reducea ammoniacal silver solution.OF ~NANTHALDEHYDE. 83 relation might be found which would point to a probable formula. The following results were obtained from three experiments made with the pure substance :- I. 8.9 grams polymeride gave on distillation 4.5 grams crude cenanthaldehyde and water, 3.7 grams C14H2,0, and 0.6 gram residue (= C2aH5403).11. 33.3 grams polymeride gave 16.3 grams cenanthaldehyde and water, 14.1 grams C14H2,0, and 1.3 gram residue boiling above 285". 111. 33.2 grams polymeride gave 16.7 grams oenanthddehyde and water, 14.3 grams Cl4HH,,O, and 0.9 gram residue. The residue was all that boiled above 285", and possibly still con- tained small quantities of Cl4H2,O. These three experiments were purposely made from three different preparations. The last one was made from crystals which had separated out from the oil (obtained by filtering the crude polymeride), on standing for some weeks at 0". The water can be calculated on the supposition that for every mole- cule of ClaH2,0 that is 'formed, one molecule of water is separated, which then gives the following results for cenanthaldehyde and water : - I.Water calculated = 0.3 gram, therefore mnanthaldehyde = 11. Water calculated = 1.2 gram, therefore cenanthaldehyde = 111. Water calculated = 1.2 gram, therefore cenanthaldehyde = 4.2 grams. 15.1 grams. 15.5 grams. Calculated into percentages, the polymeride gives on distillation :- I. 11. 111. CEhnthaldehyde ...... 4!7.19 45.34 46.68 C14H,,0 .............. 41.58 42.34 43.07 Water.. .............. 3.37 3.60 3.61 Residue .............. 6.74 3.93 2-71 These numbers show that equal weights of cenanthaldehyde and ClaH2,0 (+ water) are formed by the destructive distillation of the polymeride, i.e., two molecules of oenanthaldehyde and one of C14H2~0, probably according to the equation :- (C7H140)a = 2C7Hl4O + ClaK60 + 0% molecules of mnanthaldehyde, and has the following constitution :- It appears therefore likely that the polymeride is formed from four POL.XLIII, G84 PERKIN ON THE CONDENSATION-PRODUCTS CH3.CH,.CH2.CH,.CH,. CH,.CH(OH) CH3.CH,.CH,.CH,.CH2.CH.CET(OH) CH3.CH,. CH,.CH,.CH,.CH. CH(0H) CH,.CH,.CH,.C~z.CHa.CH.COH. That it is a saturated body is proved by the fact, that this substance when dissolved in bisnlphide of carbon, does not take up bromine without evolution of hydrobromic mid, and, if it is an aldehyde, this must also be the case from its formula. The different groups in this formula are linked together much in the same way as those in aldol, which splits up into water and crotonic aldehyde according to the equation :- CH3 CH3 p i = 11 + OH, COH COH CH;oH. CH CHiH CH .. ............... It is also very easy to understand the splitting up of the polgmeride of mnanthaldehyde, in a similar way, into water, the aldehyde C,,H2,0, and two molecules of mnanthaldehyde ; thus :- CH3 CH2 CH, CH, CH, CH, CHO (3-33 CH, hH, CH, CH, H.CH CHO- CH3 CH, CH, CH, CHz H . ~ H CH3 CH, CH3 CH, 6Ha - CH2 CEC, CH, CH, COH CHZ - . CH, .................................... CH;OHi-C'HI . , , . ............. COH CH3 CH, kH, CH, + . + CHZ CH, COH + HOH CH3 CH, CH3 CH, CH2 CH, CH, CH, CH, CH, CH, CH=C COH The amount of the body CZ8H5,O3 formed is dependent, as before mentioned, on the rapidity of the distillation. In Experiment I, for example, the polymeride was slowly distilled, and 6.74 per cent. of residue was obtained; whereas in Experiment I11 the retort was heated with an open flame and the distillation conducted very rapidly when only 2.71 per cent.of residue was obtained. The amount ob- tained has rarely reached more than 10 per cent. The formation of this substance from the polymeride of mnanthaldehyde is in itself inOF CENANTHALDEHYDE. 85 favour of this latter substance being built up from fbur molecules of cenanthaldehyde, as the formation of the former is then very easy of explanation ; thus :- C~,H~,OI = C,SH~*O, + OH,. It would be difficult to understand how such a body could be pro- duced by the simple distillation of a mixture of cmanthaldehyde and the aldehyde CIPH2,0. Jts constitution may probably be represented thus :- C H3. C H2. C H2. C Hz. C Hz . C Hz .C H (0 H) CH3.CH2.CHz.CH2.CF€z.CH. CH(0H) CH,.CH,.CH,.CH,.CH,. CH.CH It CH3. CH2. C Hz. CHz. CHz. C. COH. This shows it to be an unsaturated body, which is borne out by its combining directly with bromine. By the action of solid potash a t ordinary temperatures on mnanthaldehyde, Bbrodin states that he obtained two different polymerides ; the one solid and the other liquid. I n order to see if this were the case when potassium carbonate was used, the oil which was filtered off from the solid polymerides was allowed to stand at 0" till it deposited no more crystals, and then completely filtered off. Only a small quantity of oil was obtained, having the appearance of glycerol, and smelling strongly of cenanthaldeh yde, whereas the solid product has very little smell.It was then left for some time over sulphuric acid. On heating, the oil began to decompose a t l d O " , giving off water; at a temperature of 130-140" the decomposition was rery rapid. I n order to see whether it were a different pols- meride or only the solid one mixed with a little impurity which pre- vented its crystallising, two quantitative experiments were made and the distillation-products weighed as before. They gave the following results :- I. 21.6 grams of the oil gave 10.3 grams crude cenanthaldehyde and water, 8.1 grams C,,H,,O, and 2.4 grams residue. 11. 12.2 grams gave 5.7 grams mnanthaldehyde and water, 4.6 grams C14H,,0, and 1.0 gram residue. If the water be calculated as before, the following amounts of cenanthaldehyde and water are obtained :- I.Water calculated = 0.7 gram. Gnanthaldehyde = 9.6 grams. ? ? = 5.5 ,, 11. 7 9 -" 0.4 gram. Calculated into percentages these give the following numbers, as the relative amounts of cenanthaldehyde and C14H2,0 formed :- G 286 PEREIN ON THE CONDENSATION-PRODUCTS CEiianthaldehyde ........ 44.44 4347 per cent. Water ................. 3.24 3.28 ,, C14H260 ................ 37.50 37.70 ,, Residue ................ 11.11 8.19 ,, These two experiments were made from two different preparations. From these results, it appears that the oil is most probably only a mixture of the solid polymeride and a little unchanged cenanthal- dehyde. By the action of potassium carbonate on cenanthaldehyde, it seems therefore that only one polymeride is formed, which is solid and melts at 52-53’.By boiling cenanthaldehyde with potassium car- bonate, the same condensation-products are produced as by the distil- lation of the polymeride, together with potassium heptoate. It is probable that the polymeric modification of isobutaldehyde, which Urech (Ber., 12, 190; 13, 483 and 590) obtained by the action of potassium carbonate on that aldehyde at ordinary temperatures, is derived from at least four molecules of isobutaldehyde. Urech considers that it has the constitution (C4H80), and describes it as a very thick oil, which can be distilled in steam. When distilled, alone, however, it decomposes into water, isobutaldehyde and con- densation-products. From these he isolated a body, C12H2,02 = Demtschenko (Bey., 6, 1176) also obtained st polymeride by the action of sulphuric acid on isobutaldehyde, which has the formula (C,H,O),, and which he called “ paraisobutaldehyde.” It distils without decomposition, and he was thus able to determine its mole- cular weight by taking its vapour-density; this agreed with the formula (C,H,O)3.It therefore appears that the polymeride obtained by Urech is quite st different body, possibly containing at least The same remark applies to the polymeride obtained by Borodin (Ber., 6, 982) from isovalersldehyde, which, on distillation, splits up into water, isovaleraldehyde, Cl0Hl8O, and C20H3802, and the hydrate of which is produced by the action of soda solutions on this alde- hyde at ordinary temperatures. This latter body has the formula By distillation, this hydrate also splits up into water, isovaleralde- 3CdHSc) - OH,.4( CaE30). (C~oHmQ&JLO = (C5H100)4H20. hyde, CIDHl80, and c20Hdb. Action of Nascent Hydrogen on Polyrnerised Q3nar~thaldeh;de. This experiment was made in the hope of obtaining from the poly- merised mnanthaldehyde, a glycol of the formula C28TS5804, by the reduction of the COH-group to CH20H, and of thus confirming the supposition that it is derived from 4 mols. of oenanthaldehyde.OF (ENANTHALDEHPDE. 81 Thirty grams of the polymeride were dissolved in ether, and then treated with 50 per cent. acetic acid, and a large excess of sodium in a flask connected with a reversed condenser. The sodium was added very slowly, and now and then it little acetic acid was poured in, to insure the contents having an acid reaction, as it appeared probable that the polymeride would be easily decomposed by caustic alkali.At the end of the reaction the ethereal solution was well washed t o remove sodium acetate and acetic acid, dried, and the ether distilled off. The residual oil mas then carefully fractioned. Thefirst fraction obtained was from 100--210", and weighed about 5 grams ; the ther- mometer then rose rapidly to 260", and between this and 300" about 5 grams more came over. The greater part, however, boiled above 310", and was left behind in the retort. The product which came over between 100-210" was then repeatedly fractioned, when at last most, of it came over between 174-176", and gave the following numbers on analysis :- 0.1535 gram substance gave 0-1857 OHz and 0.4121 CO,.Found. Calculated C,H,,CH?OH. C .......... 73.22 per cent. 72.441 per cent. H.. ........ 13.44 ,, 13.79 ,, I t is therefore undoubtedly hephyl dcohol. On shaking it with acid sodium sulphite, a small quantity of a compound was formed, indi- cating that a trace of cenanthaldehyde was also present. This mould account for the hydrogen being low and the carbon high in the above analysis. The oil boiling between 250-310" was then repeatedly fractior,ed ; a product mas thus obtained boiling at 297-300". Thequantity was, however, very small, so that it was very difficult to obtain pure. It gave on analysis the following numbers :- ' I. 0.2363 gram substance gave 0.3133 OH, and 0.7268 CO,. 11. 0.1746 7, ,, 0.2133 ,, 0.4936 ,, Found. I. Theory C21H440P. 76.83 per cent. rII.' C...... 77.34 77-10 per cent- H .... 13-58 13.57 ,, 13.41 ,, This substance therefore appears t o have the formula C21H1402. Its formation, together with that of heptyl alcohol by the action of nascent! hydrogen on the polyrneride of cenanthaldehyde, may be repre- sented thus :-88 PERKIK ON THE CONDENSATION-PRODUCTS This reaction can be better understood if the equation is written out as follows ; thus :- + H2 9H3 CIIP CH, ~ W Q $. CH, CH2 CH3 CH2 CH2 OH, CH2 CHP CIT, CH3 CW2 CH2 CH? CH2 CH20H CHf CII, CH2 . . CH(OH). CH CH, &I2 CH CH~OH. + OH2 This substance is a yellowish oil, which does not solidify a t - 20". If dissolved in carbon disulphide and cooled down to - lo", it does not appear to take up bromine. I n order to confirm its molecular weight several attempts were made to debermine its vapour-density, but as it decomposes a few degrees above its boiling point, no useful results were obtained.I hope to have another cpportunity of more thoroughly studying this interesting reaction, and more especially of examining the pro- ducts boiling above 310", which, as yet, I have not been able to obtain pure. Action of Alcoholic Potash o n Acetic Aldehyde. d few experiments were made on the action of very dilate alcoholic potash on ordinary aldehyde, in order to see if i t were possible to obtain as good a yield of crotonic aldehyde by this reaction, as of the corresponding aldehyde, ClaHzsO, from mnanttlialdehyde, more especi- ally as the preparation of the former by the zinc chloride reaction is unsatisfactory, the yield being very small.The aldehyde employed in these experiments was the so-called " concentrated solution " from Kahlbaum, which is a mixture of water, aldehyde, and a trace of a(lcoho1. The aldehyde was mixed with a little alcohol, and then treated every day with small quantities of alcoholic potash, cooling the mixture well after each addition. After standing for some time, a considerable quantity of metaldehyde separated out in large crystals, which were filtered off. From the solution an oil was obtained, which, after washing with a solution of calcium chloride and drying, was fractioned. At first a consider- able quantity of unchanged aldehyde came over, then from 90-135"OF CEXANTHALDEHPDE. 89 a large fraction was obtained; above 130" a dark brown residue was left, which probably contained aldol, as on further heating it decom- posed, giving off water and a small quantity of an oil smelling very like crotonic aldehyde. The product boiling between 90-135" was carefully fractioned in carbonic anhydride.Two fractions were obtained between 100-110" and 115-130". The latter was by far the larger. On repeatedly fractioning the first of these, nearly all of it boiled between 102-1@6", and gave the following numbers on analysis :- 0-2093 gram substance gave 0.1636 OH2 and 0.5229 COz. Found. Calculated CH3.CH= CH.COH. c1 ........ 68-14 per cent. 68.57 per cent. H.. ...... 8-68 ,, 8.57 ,, It was therefore crotouic aldehyde. On standing for some few days in the air, it deposited crystals of crotonic acid, melting at 70", whereas the pure acid melts at 72". The second fraction, on being redistilled, eventually boiled mostly between 123-l%", and gave the following result on analysis :- 0.1264 gram substance gave 0.1014 OHz and 0-2509 COO. Found. Calculated (CH,COH), C ........ 5413 per cent. 34-54 per cent. H . . ...... 8.91 ,, 9.09 ,, It was therefore paraldehyde. The yield of crotonic aldehyde was unfortunately small, but it appears probable that, by modifying the conditions, it might be improved, and this process found to be the easiest method of preparing it. Paraldehyde was the chief product of the reaction. Finally, I append a table of the substances obtained from cenanth- aldehyde, with their boiling points and specific gravities.90 PERKIN ON THE CONDENSATION-PRODUCTS OF - 0~8744 0 -8831 Name of substance. - 0.8665 0 -8751 CEnanthaldehyde ...... C,4H260 = {CoH C13H% . . C,,H,jCOH ........... C13HSCH20H . n 6 s . a C13H2jCHbOC2H30 ..... C,,HgCH,OH ......... C13H27CH2OC2H30. .... Cl,H,,COOH.. ........ C,,H&OOH. ......... C21H400 .............. C28H,,0 .............. CiBHBIOI ............. C28H,60, ............. C21H-14402. ............. Boiling point. 153-154" 277-279' 266-268" 280-283" 270-275" 285-290" 2 75-280' 275-285' 300-310" 310-315" 330-340° (m.p.-29'57 (at 250 mm.) (at 300 mm.) (at 200 mm.) (at 200 mm.) melts at 52-53' 3 30-340" 297-300" Specific gravity compared with water at the same temperature. -- -- 15" I 300 0 * 8231 0 *a494 - 0 -8520 0 *8368 0 t8680 0 *8559 - 0 -8128 0 -8416 0 '8274 0 -8444 0 -8301 0 '8597 0 -8476 - 35O. --- 0 -8099 0 -8392 0 .a258 0.8418 0 %?70 0 *8568 0 -8448 - 0 '8637 0 * 8723 - - - I cannot conclude this paper without expressing my sincere thanks to Prof. Wislicenus, in whose laboratory this research was.carried out, for his kind help and advice during its progress.

ISSN:0368-1645    

DOI:10.1039/CT8834300067

出版商:RSC    

年代:1883

数据来源: RSC

摘要:

90 PERKIN ON THE CONDENSATION-PRODUCTS OF X.-On the Conde7isa~ion-prod~l.cfs of Isobutaldeh yde obtained by Means of Alcoholic Potash. By W. H. PERKIN, Jnn., Ph.D. Condensation-products of Isobutaldehyde. A SHORT time ago there appeared in the Berichte (15, 2363) an abstract of a preliminary notice by Fossek (Monatsh. f. Chern. 3, 622 ; C. J., Abstr., 1882, l274), on the action of an aqueous solution of caustic potash on isobutaldehyde. As I have for some time been working on the condensation-products of isobutaldehyde produced by means of alcoholic potash, in continuation of a research on the condelisation of ananthaldehyde, on which I have been engaged for the last two years, I am compelled to publish my results, although not quite completed,ISOBUTALDEHYUE OBThIhTED BY ALCOHOLIC POTASH.91 especially as they a4re quite different from those obtained by Fossek, alcoholic potash seeming to bring about a series of reactions differing from those obtained by the action of aqueous potash. The method employed f o r preparing the isobutaldeliyde was the following :- 100 grams isobutjlalcohol and 200 grams water were put into a large flask connected with a condenser, warmed up to about SO", and a, concentrated solution of bichromate of potash, mixed with an equal volume of sulphuric acid slowly run in, the contents of the flask being well shaken after each addition, to facilitate the escape of the aldehyde as soon as formed. This concentrated bichromate solution was added, until the oily layer of isobutyl alcohol disappeared from the surface of the mixture in the flask, and the whole was then boiled to drive off any aldehyde still remaining in the liquid.The oily part of the distillate was separated from water, dried as qiiiclily as possible with calcium chloride, and fractioned. The portion which distilled over below 100" was collected apart, and carefully fractioned by using a tube 3 feet high, to facilitate the separation of the aldehyde from the other products. By this means the aldehyde is easily obtained pure, boiling from 60-62". The quantity was from 50-60 per cent. of the theoretical. The condensation witch alcoholic potash was first tried in the follow- i n g way :-50 grams of isobutaldehyde were dissolved in 100 grams absolute alcobol, and then a solution of 2 grams potash in 20 grams alcohol slowly added, the temperature not being allowed t o rise above 30".The mixture after cooling was then mixed with a second. 2 grams potash in alcohol, and after standing for 12 hours, warmed up t o 50" for about 10 minutes. It is important not to warm too long, as other- wise the condensation is apt to go too far, and only high boiling con- densation-products to be produced. The liquid was left to cool, and the saline products separated from the condensed oils, by adding much water and taking the oil up with ether. If the alcohol be first dis- tilled off, the excess of potassium hydrate and saline matter act further on the aldehyde producing higher condensation-products. The aqueous saline solution from several experiments was first examined ; it was thoroughly freed from oily products with ether, concentrated, and acidulated with hydrochloric acid.This caused the separation of some acids, which were extracted wit,h ether. The ethereal solution was washed, dried over chloride of calcium, and distilled. After the ether had distilled off, the principal part of the product came over between 145-180". A considerable quantity afterwards passed over between 180" and 260", leaving a thick tarry residue in the retort ; the portion boiling at 145-180" consisted essentially of iso- butyric acid. It was, however, purified, and converted into its silver salt, A silver determination gam the followiug numbers :-92 PERKIN ON THE CONDENSATION-PRODUCTS OF 0.3846 gram subst'ance gave 0.2142 gram Ag = 55.69 per cent.Calculated for gg>CH.COOAg = 55.38 ,, The fraction boiling between 180-260" was then several times care- fully fractioned, when the largest part obtained boiled at 245-255". This gave on analysis the following numbers :- I. 0.1565 gram substance gave 0.1479 gram OH2 and 0.3839 gram 11. 0.1676 gram substance gave 0.1575 gram OHz and 0,4111 gram CQ,. coz. Found. r d 7 I. 11. Theory C,,H2203. C . . . . .. 66.90 66.89 per cent. 67-29 per cent. H . . . . 10.50 10.44 ,, 10% ,, These numbers therefore agree with those required by the formula C12H2203. The body is therefore an isomeride of octrlacetoacetic acid ; this acid is probably formed by the action of potasb on the aldehyde C12H2202 (which will be found described further on) according to the equation- 2C12HpiOz + KOH = CizH2103K + C12H2402. This acid dissolves somewhat readily in dilute potash, but after standing for some time the potassium salt separates out as a gummy layer on the surface of the liquid.Attempts were also made to prepare the potassium salt by dissolving the acid in dilute alcoholic potash, passing CO,, and filtering off the precipitated potassium carbonate, but in this case the potassium salt was left behind, on evaporating off the alcohol, as an uninviting soap. The acid itself is a light brown oil, having but little odour ; it dissolves in ammonia, and precipitates silver from a solution of silver oxide in ammonia. It distils apparently without decomposition, cooled to -10". By the action of aqueous potash on isobutaldehyde, Fossek obtains an acid to which he assigns the formula CsH160,; this requires It does not solidify.It melts a t 75-80', and is therefore evidently = 60.00 per cent. = 10.00 per cent. quite different from the one described above. The ethereal solution of the condensed oils was well washed. It was dried with chloride of calcium, and fractioned in a stream of car- bonic anhydride. The fraction below 100" contained besides ether a con- siderable quantity of the unchanged aldehyde. That from 100-140" was very small, but between 140-180" a considerable quantity of a colourless oil was obtained, smelling strongly of camphor. The residue'ISOBUTALDEHPDE OBTAINED BY ALCOHOLIC POTASH. 93 in the retort was very small. The oil boiling between 140-180° was fractioned as rapidly as possible, when nearly the whole came over between 70-100", and only a small quantity distilled over between 145-160".There was also a considerable quantity of a high boiling product, which had been produced during the distillation, left behind. This last fraction was once more rapidly fractioned, when the prin- cipal part distilled between 154-157". On analysis it gave the follow- ing numbers :- I. 0.1156 gram substance gave 0,1170 gram OH, and 0.3070 gram 11. 0.1195 gram substance gave 0.1198 gram OH, and 0.3168 gram co,. co,. Found. 7--- 7 I. 11. Theory Cl2Hz2O2. C . . . . . . 72.52 72.30 per cent. 72.73 per cent. H . . ,. 11.24 11-1.4 ,, 11-11 ,, This body appears to have the formula C12H2202, and is probably formed by the separation of a molecule of water from three molecules of isobutaldehyde, thus :- It is a colourless oil, having a powerful ethereal smell and burning taste.It reduces an ammonincal silver solution readily, and combines slowly with acid sulphite of sodium, forming an amorphous-looking mass, very slightly soluble in water, which under the microscope is seen to consist of small crystals displaying colours in polarised light. On the addition of an acid or of sodium carbonate this compound is decomposed, an oil separating ont. It does not solidify when cooled down to -10". I f dissolved in carbon disulphide, and the solution cooled in a freezing mixture, it takes up bromine. It is easily decom- posed by potash, apparently forming a considerable quantity of potassium isobutyrate. This oil is probably the same body as that which Urech obtained (Ber., 13, 590) by distilling the polymerised modification of isobutaldehyde produced by the action of potassium carbonate.He describes it as a colourless oil, possessing an ethereal smell, and boiling a t 154". He also notices that on distilling it decom- poses, leaving a high-boiling residue in the retort. A vapour-density which he made agreed fairly well with tlie formula CBH,,O, but on analysis numbers were obtained which agreed with the formula C12H2&2. As the substance decomposes on pro- longed heating, a vapour-density has probably but little value. Fossek, by the action of sodium acetate on aqueous Dotash, obtained an94 PERKIN ON THE CONDENSATION-PRODUCTS OF aldehyde C,H,,O, boiling at 149-151", which, however, seems to be different from the one described above, as it appears to dist.il without decomposition.It requires 76.19 per cent. of carbon, whereas the siibstance examined by me contained 72.5. By the action of ZnC1, or PC1, on isobutaldehyde, Bossek obtains polymerides derived from 3 mols. of isobutaldehyde. Actiow of Nascent Hydrogen. on the Aldehyde C12H2202. This experiment was tried in order, if possible, to obtain an a.lcohol from the aldehyde CI2Hz2O2, and by this means to obtain some further clue as to its constitution. About 50 grams of the aldehyde were dis- solved in 200 grams of ether, mixed with a small quantity of water, placed in a large flask connected with a reversed condenser, and sodium was added at inbervals and in small pieces, the mixture being kept as cool as possible, and shaken up from time to time to.dissolve out any sodic hydrate suspended in the ether. The ethereal solution was then washed, dried, and fractioned. After the ether had distilled off, most of the oil came over between 260-280", leaving however a small residue in the retort. This oil was slowly fractioned in a Wurtz flask, with a neck ambout 8 inches long, wheu the principal portion came over between 270-275" as a colourless oil, possessing a very strong odour. I. 0.1038 gram substance gave 0,1219 gram OHs and 0.2721 gram 11. 0.1160 gram substance gave 0.1341 gram 0E2 and 0.3039 gram On analysis it gave the following numbers :- c 0 2 . c 0 2 . Fonnd. r - 7 I. 11. Theory C1,H2602. C . . . . . . 71.49 71.21 per cent. 71.28 per cent. H .. .. 13.05 12-85 ,, 12.87 ,, It appears therefore that an alcohol of the formula CI,H2,0z, which is isomeric with ethyl propyl pinacone, had been formed, according to the equation- This body does not solidify at -loo, neither does it combine with acid sodium sulphite. On distillation if, appears to decompose slightly, forming lower and higher fractions. This makes i t difficult to obtain i t in the pure state. I n order, if possible, to obtain an acetate from this body, it was treated with an excess of acetic anhydride a t 180" for four hours, and then fractioned. After the anhydride and acetic acid hadISOBUTALDEHYDE OBTAINED BY ALCOHOLlC POTASH. 95 been slowly distilled off, nearly all the residue boiled between 175- 190". This, on carefully refractioning, gave quantities of distillate of about the same size, boiling at 180-185" and 185-190". Analysis of these gave the following numbers :- 1.(180-185") 0.1298 gram substance gave 0.1245 gram OH, and IT. (185-19G") 0.1336 gram substance gave 0.1311 gram OH, and 0.3211 gram COz. 0.3305 gram COz. Found. Theory. c16H3004 = C12H?402(C2H30)2 6 7.1 3 per cent. 11: I. C.. . . . . 67.46 67.46 per cent. H . . . . 10.66 10.90 ,, 10.48 ,, These numbers indicate that both specimens consisted of a diaceta,te This substance would be produced accord- of the formula C16HN04. ing to the equation :- CH CO C12H2602 + ((7a:co>O)' = C12H2402(cZH3~)2 + 2CH3COOH* A Dumas vapour-density determination was made of this body, and gave 6.289. The molecular weight should therefore be 6,289 x 28.92 =181*87, whereas the theoretical molecular weight for CZ4HazO, = 286, so that apparently in this case, as with the body CI2Hz2O2, decom- position takes place on prolonged heating of the vrtpour.This acebate is a very strong-smelling body, reminding one of peppermint. These result,s must only be looked upon as preliminary, as owing to the very small quantity of the aldehyde C12H2202, at my command, if has been, up t'o the present, impossible to confirm them. In order to study the higher condensation- products the isobut- aldehyde was treated in the same manner as in the previous experi- ment, twice as much potash, however, being employed, and the tem- perature of the reactions allowed to rise to 45". At the conclusion of the operation the mixture was heated on the water-bath to near its boiling point for ten minutes; it was then diluted with water, and the neutral oils were taken up with ether, separated, and treated as before. On distillation a small quantity of oil came over under 200°, which contained, besides the aldehyde C12H2202, a small quantity of a body boiling between 190-200"; this gave on analpsis, numbers approximately agreeing with the formula C,,H3,03 ; the quantity was, however, too small to further examine.After this the thermometer rose rapidly t o 215", and between this and 235" about 20 grams of oil distilled over, leaving in the retort a residue which was reserved for further examination (see p. 99).96 PERKIN ON THE CONDENSATION-PRODUCTS OF On repeatedly distJilling this oil in an atmosphere of carbonic anhy- dride, in a long-necked Wurtz flask, eventually two principal fractions were obtained, boiling between 223-224" and 224-225" ; these gave on analysis the following numbers :- I.0.1307 gram substance gave 0.1363 gram OH, and 0.3381 CO,. II. 0.1778 ,, ,, 0.1833 ,, ,, 0.4576 ,, Found. f---h- 7 Theory I. 11. for C2,,H304. C . . . . . . 70.55 70.19 per cent. 70.17 per cent. H .. . . . . 11.58 11-43 ,, 11-11 ,, This body appears therefore to have the formula C2,H3,0a. Its €or- mation is easily understood, thus :-- 5ClH80 = C,H,,OI + HZO. It is an almost colourless oil, which smells strongly of camphor. When it was left in contact with hydrogen sodium sulphite for two or three weeks, with constant agitation, long transparent needles were formed ; it is therefore apparently an aIdehyde. It does not solidify in a freezing mixture, but becomes extremely viscid. It reduces arnmoniacal silver solution, but does not quickly absorb oxygen from the air.When heated for some hours with 50 per cent. sulphuric acid, i t first becomes black, giving off a considerable quantity of CO,, and a t last it becomes nearly solid. Ether removes an oil from this product which principally distils between 200-240". There was, however, also a low-boiling body present, which I hope to investigate further. This aldehyde, C20H3804, is perhaps the same body as that which Urech obtained (Bey., 13, 593) by distillation of the polymeride of isobutaldehyde produced by the action of potassium carbonate. His product was an intensely yellow oil, boiling between 230-240", and gave, on analysis, C = 71.50 per cent., H = 11.80 per cent.; con- sidering the wideness of the range of boiling point, these agree fairly with the numbers which I obtained.He also determined the vapour- density by Hofmann's method, and found it equal to 6-80, which gives a molecular weight = 196.70 as against 342, calculated for C2,H3,04, SO that it appears that this body decomposes on the prolonged heating of its vapour. In order to confirm these results, two vapour-density determinations were made, the first by the Dumas method, the second by the Victor Meyer method. The vapour-deiisit'y obtained by the Dumas method was 6.64, which agrees fairly with the one found by Urech. The one made by the Victor Meyer niethod gave 5-77.The molecular weight was therefore 28.92 x 5-77 = 167.ISOBUTALDEHYDE OBTAINED BY ALCOHOLIC POTASH. 97 This vapour-density was taken in a lead-bath, so that the body was probably fully decomposed, as this result is about half of the calculated density. It is worth noticing that during the determination by means of the Dumas method, most of the substance distilled off when the bath was up to 2M"; but it was not till the bath had gone up to '252" that all was vaporised. This seems to be a clear indication of its decomposing, as the substance used boiled between 223-224". Ey the action of aqueous potash on isobutaldehyde, Fossek obtained a body boiling at 222-2233 and fusing a t 15.5", to which he gave the formula C8H&,. This formula requires C = 65.75 per cent., H = 12.33 per cent., and a molecular weiglit = 146.There is no doubt it is a different body from the one described above. Action of Acetic Anhydride 0% C20H3801. As it seemed possible that the aldehyde C,oH380a might, by the action of acetic anhydride, form some acetyl compound which would throw light on its constitation, the following experiments were made:-A quantity of this substance was first sealed up in a tube with a slight excess of acetic anhydride (for a monoaeetate), and slowly heated till the temperature reached ISO", and then allowed to cool down. On fractioning the product as soon as the metic anhy- dride and acetic acid had distilled off, nearly all came over between 235-250". This was several times carefully fractioned, when at last the largest quantity was obtained boiling a t 240-242'.On analysis it gave the following results :- I. 0.1345 gram substance gave 0.1263 gram OH, and 0.337.5 CO,. 11. 0.1549 ,, ,, 0.1452 ,, ,, 0.3905 ,, Found. r-- 7 Theoq- I. 11. for Cz2H4,,O5. C . . . . . . 68.43 68.75 per cent. 68.75 per cent. H . . . . , . 10.43 10.42 ,, 10.42 ,, These numbers agree with those required for a monoacetate, produced according to the following equation :- This body is an almost colourless oil, having only a w r y faint smell. It does not solidify in a freezing mixture. Treated with potash it turns black, appearing to saponify very easily. In order to see if acetic anhydride had any further action on this body, it was heated in a sealed tube with excess of acetic anhydride to 200-220" for five98 PERKIN ON THE CONDENSATION-PRODUCTS OF hours, and then refractioned.Nearly all of the oil came over bet ween 240" and 255". This when refractioned two or three times gave, as the principal part, an oil boiling constantly from 248-252", and yielding on analysis the following numbers :- I. 0.1344 gram substance gave 0.1189 OH, and 0.3217 CO,. 11. 0.1372 ,, ,, 0,1235 ,, 0.3389 ,, Found. Theory 67.63 per cent. I. for C24B.,206. r---72 C . . . . . . 67.31 H . . . 3.. 9.83 10.00 ,, 9.86 ,, 67.37 per cent. This body may therefore be regarded as a diacetate derived from CzoHm04, and produced from the monoacetate, according to the equation :- This diacetate resembles the monoacetate in most respects; i t is an almost colourless oil, has very little smell, and does not solidify in a freezing mixture.It distils without the least decomposition. In order to prove that this was really a diacetate, it was quantitatively saponified, and the acetic acid formed was determined. As there was not sufficient of the fraction 248-252", a fraction boiling a t 246-254" was taken, and gave the following results :- 4.1428 gram substance was saponified with alcoholic potash, water added, and the oil ext'racted with ether. The potash-solution was cancentrated, acidulated with sulphuric acid, and distilled into baryta- water, and afterwards the excess of baryta was separated with carbonic anhydride. The weight of barium salt obtained, after evapdration, was 3.1862 grams. As the salt did not look pure, it was thought that it probably contained a small quantity of barium isobutyrate.A barium determination was therefore made which gave 52.74 per cent. This therefore apparently con- sisted of- Theory for Ba (C,H30,)2 = 53.72. Barium acetate . . . . . . 89.86 per cent. = 2.863 grams. Barium isobutyrate.. . . 10.14 ,, = 0.3231 gram. Theory requires that from 4.1428 grams of the diacetate, 2.4800 grams of barium acetate should be formed, which agrees as well as could be expected with the quantity found. There is, therefore, no doubt that it was a diacetate. The dark-brown ethereal solution, which was separated from the potassium acetate, was well washed, dried, and fractioned. After the ether was distilled off, the thermometer rose rapidly to 200", the greater quantity coming over between 215" andISOBUTALDEHYDE OBTAIKED BY ALCOHOLIC POTASH.99 240". A considerable quantity of a black tar was left behind in the retort, which was not further examined. The presence of this, as well as the apparent formation of isobutyric acid, showe that, besides saponifying, the potash had also exercised a further action on the product. The fraction 215-240" was then redistilled, when the principal portion passed over at 217-223", and gave on analysis the following result :- I. 0.1435 gram substance gave 0.1568 OH, and 0.3629 GO,. 11. 0*12-34 ,, ,, 0,1370 ,, 0.3165 ,, Found. r-&- 7 Theory I. 11. for CLOH4204. C ...... 68.97 68.83 per cent. 69-37 per cent. H ...... 12.14 12.14 ,, 12.14 ,, This body has therefore the formula CzoHdZ04, or 4H more than the body C2,H,,0,, which should have been reproduced by the saponifi- cation.This new product is an almost colourless oil, having a 1wculiar odoiir, which does not resemble that of the aldehyde Cz,H,O,. The first of the above combustions is from a fraction boiling between 217-219", and the second from a fraction (219-223"). It therefore appears that by the saponification of the diacetate, the body CzoH,,O1, probably first produced, is further acted on by the reducing and oxidising action of the potash, part being oxidised and part forming tllc body C2,HdZO,. The residue of the condensed isobutaldehyde left in the retort and Loiliiig above 235" was distilled under, a pressure of 100 mm. A considerable quantity came over between 185" and 200"; the next large fraction was between 220-235O.The distillation was discon- tinued when the temperature had reached 280", and decomposition set in. The portion boiling a t 185- 200" was then fractioned under the ordinary pressure, when it nearly all distilled over between 245" and 260". This was then collected between every 5"; the principal product thus obtained boiled at 250- 255". No solid bodies were obtained. On analysis it gave the following results :- I. 0.1234 gram substance gave 0.1231 OH, and 0.3328 CO,. 11. 0.13'70 ,, 9 , 0.13'74 ,, 0.3666 ,, Found. Theory - 1 r : I. for C24,H,,04. C ...... 73.55 72.97 per cent. 72.72 per cent. H ...... 11-08 11.14 ,, 11.11 ,, VOL. XLIII. i r100 PERKlK ON THE CONl3ESShTIOX-PRODUCTS, ETC. It thus appears to have the formula CB4H1404, and is probably pro- duced according to the equation- 6C4H80 = C,,H,,O, + 20H,.It is a stable body, and requires long boiling with dilute sulphuric acid to decompose it. Owing to the small quantity produced in the action of potash on isobutaldehyde, it could only be very little examined. It is an almost colourless oil, and distils at ordinary pressures without decomposition. I t does not seem to combine with acid sulphite of soda. On heating with strong alcoholic. potash, i t turns black and is decomposed, forming a considerable quantity of a potassium salt. Two vapour-density determinations were made which gave 12-61 and 13.21. The calculated density for C,4H4401 = 13.69. From these determinations, it appears evident that this body is much more stable tban the lower condensation-products, as the figures obtained, althougb not agreeing well with the calculated ones, yet go to show that the body is produced by the condensation of six mole- cules~of isobutald ehyde, the next lower one, C2,,HB04, having a calcu- lated density = 11.82.The fraction obtained between 220-235" under a pressure of 100 mm. was then carefully distilled under the same pressure, After repeating this operat,ion several times, a considerable quantity was obtained, boiling constantly at 227-229", which gave on analysis the following numbers :- I. 0.1281 gram substance gave 0.1305 OR, and 0.3630 CO,. 11. 0.1420 ,, ,, 0.1480 ,, 0.4038 ,, Found. r - 7 Theory I. 11. for C,H,,O,. C . . . . . . 77.28 77.55 per cent. 77.77 per cent. H . . . . . . 11.32 11.11 ,, 11-11 y, This body appears therefore to have the formula C28H4803. The formation may be expressed by assuming that four molecules of water are removed from seven molecules of isobutaldehyde zccording to the equation :- 7CkH80 = C,H,,O, + 4OHz. This body is a very thick yellowish oil, having a very faint smell. It distils in a vacuum without decomposition, but at ordinary pressures it appears to split up into lower and higher boiling bodies, a tarry residue being left behind in the retort. This decomposition was also seen when two vapour-density determinations were attempted. By the Victor Meyer process in a lead-bath, they gave 10.42 and 10.77.SHEKSTONE : THE ALRBL0Il)S OF KUX VOMICA. 101 The calculated density for C,H,,O, is 14.94. The still higher-boiling. condensation-products mould be very difficult t o obtain pure, and were not analysed. There appeared, however, t o be a definite body boiling at about 250", under a pressure of 100 mm. A table is appended of the bodies obtained and their boiling points, ClzHy202 .......... C,6H3003 (3) ...... C,2,,€13, 0, .......... C,rH,,O, .......... C,sH4e03 . . . . . . . . . C12H3602 .......... ClZHZ&OZ(GH$O)Z . . C,ZOH,?Oa .......... C1,H,,O, .......... 154-157" 7 223-2.25" 25 0 - 2 5 5 " 227-2229' (100 nim. pressure) 170-175" 1%--190" 240-242" 248-252 O 190 -200" I ) Condensation-products. Alcohol (and acetate) produced by the action of nascent hydrogen on C,,H,O2. Acetates produced by the action of acetic anhydride on C,H,04. i { Prodnced by saponify- c ing C:oH3604 (C,H,O),. 2 17-223' Acid produced by t'lie action of potash on isobu taldehy de. 245-2.55"

ISSN:0368-1645    

DOI:10.1039/CT8834300090

出版商:RSC    

年代:1883

数据来源: RSC