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Abstracts of the Proceedings of the Chemical Society, Vol. 3, No. 32 |
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Proceedings of the Chemical Society, London,
Volume 3,
Issue 32,
1887,
Page 7-17
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摘要:
ABSTRACTS OF THE PROCEEDINGS OB THE CHEMICAL SOCIETY. No.32. Session 1886-87. February 3rd, 1887. Dr. Hugo Muller, F.R.S., President,, in the Chair. Certificates were read for the first time in favour of Messrs. Cecil Howard Cribb, 38, Soh0 Square ; Joseph Frank Geisler, Mer- cantile Exchange Buildings, Hudson and Harrison Streets, New Pork; Thomas Albert Hedley, 41, St. Jean Baptiste Street, Mon- treal ; Joseph William O'Connor, 28, Aberaeron Place, N.W. ; Gerald Tattersal Moody, 229, Rye Hill, S.E. The following were elected Fellows of the Society :-Messrs. William Henry Coates, Thomas Cooksey, Arthur Henry Downes, M.D., Hamilton Emmons, George Arthur Goyder, E. Hori, Hubert McKeow, J. F. McArthur, Dai-id Henry Nagel, Thomas Burden Reay, Charles E.Sohn, Junr., Lionel W. Stansell, James Pim Strangman, D. A. Sutherland, Jokichi Takamink. The following papers were read :-5. " The Absorption of GaseB by Carbon.'' By Charles J. Baker. A series of experiments are described in which carbon in the form of animal charcoal, previously heated in vucuo, was saturated with oxygen, both dry and moist, at a low temperature ; the carbon thus treated, enclosed in a vacuous tube, was then heated for some time at loo", and finally the absorbed gas was extracted and analy sed. Using moist oxygen, it was found that no gas was given off at 12" from the carbon which had been exposed for one hour at -15" in such an atmosphere; on heating the carbon thus treated at 100" during seven days, snd then exhausting at this temperature, it;gave 8 about seven times its volume of gas consisting of carbon dioxide.No carbon dioxide was produced on digesting carbon and water vapour for a similar period and then exhausting. Using dry oxygen and proceeding similarly, no gas was given off from the charcoal at 100" ; however, on raising the temperature to about, 450", gas was expelled, consisting mainly of carbon monoxide mixed with carbon dioxide. Dried carbon was then charged with dried carbon dioxide, and the gas was extracted by heating at about 450" as before ; it consisted of carbon monoxide and dioxide, the propor- tion of the former being less the more carehlly the carbon was dried. The author, therefore, coiicludes that the more carefully moisture is excluded, the less does the carbon burn in the carbm dioxide which it absorbs; and further that carbon is burned directly to cai-bon monoxide by absorbed oxygen.DISCUSSION. Mr. F. J. M. PAGEasked whether the author had ascertained if the same carbon coiild be used repeatedly ; that is to say, m7as it possible to burn away the whole of the carbon, or was the action confiued to the surface. Professor ODLTNG,who had communicated the paper, said this had not been ascertained ; he thought, however, it was probable that the carbon would become less and less absorptive, but that the action would continue in proportion as absorption took place. 6. " An Explanation of the Laws which govern Substitution in the case of Benzenoid Compounds." By Henry E.Armstrong. Certain mono-derivatives of benzene, especially those containing a hydrocarbon radicle, one of the halogens, hydroxyl or amidogen yield a mixture of the para-and ortho-di-derivatives in proportions which vary both according to the nature of the compound dealt with and of the reagent, and the conditions under which the change is effected; and if produced at all, the meta-derivative is formed in but a small proportion. If, however, the radicle present in the mono- derivative be NO,, COH, COZH, S03H,the meta-di-derivative appears invariably to be the chief product. Hitherto no explanation of this difference in the behaviour of the two series of mono-derivatives has even been suggested. In seeking to arrive at an explanation it is necessary to form a, clear conception of the manner in which " substitution " is etfected.The author is of opinion that in the first instance an additive compound is formed ; and he points out that KekulB has long since 9 insisted in the plainest terms on this interpretation of those cases of change which are commonly spoken of as “double decompositions.” He is inclined to believe that the tendency of negative to attract and combine with negative elementss-to which he has of late frequently directed attention-is the effective cause ; and that the additive Corn- pound is formed from those mono-derivatives which obey the ‘(para-ortho law ” by the fixation of the reacting molecule upon the carbon- atom which carries the radicle : separation of water or halogen hydride ensuing thereon, the radicle of the reacting molecule assumes the place either of an ortho- or of a para-hydrogen atom.It is easy to understand the formation of the ortho-di-derivative, as the hydrogen- atom displaced is associated with a carbon-atom contiguous to that to which the reacting molecule attaches itself. The formation of the para-compound is attributed by the author to the tendency towards symmetry, EO frequently evidenced in cases of isomeric change and in other ways by benzenoid compounds ; and not to the existence of any direct connexion between carbon-atoms relatively in the para-position. The formation of metn-derivatives is believed by the author to result, from the addition of the reacting molecule not to the carbon-atom of the benzene-ring but to the radide which in the mono-derivative is attached to one of the carbon-atoms of the ring; he is, however, of opinion that in order to explain why the additive compound thus constituted yields a meta-di-derivative, it; will be necessary to obtain further information regarding the “ dynamics ” of such changes.DISCUSSION. Professor ODLIR’Gobserved that any attempt to solve the problem of the action of the commonly employed reagents, chlorine or bromine, nitric acid and sulphuric acid on one set of phenic mono-derivatives to produce under ordinary conditions mainly para-di-derivatives, and on another set of phenic mono-derivatives to produce mainly meta-di- derivatives, was entitled to a thoughtful and grateful consideration.But in his opinion a distinction should be drawn between the abstract cause of the result-as when Professor Armstrong attributed the habitual preferential formation of para-derivatives to the existence of a tendency to the formation of symmetric compounds, and the mechanism leading to the result-as when he represented the forma- tion of ortho-derivatives as being an nlmosf necessary consequence of the particular process by which he cmceived the substitution to be effected. The former suggestion did not appear to help the matter forward very much ; but the latter suggestion was at any rate in the nature of a real explanation :though, for himself, he was not prepared to admit the general principle that the previous combination af 10 reagents was an invariable and determining condition of their reaction.Under exposure to bright daylight, a mixture of equal volumes of chlorine and marsh-gas, for instance, reacted even with violence; and, in his opinion, while the evidence as to the fact of their previous combination was of the smallest, the evidence as to the previous combination being the determining condition of the reaction was none at all. Admitting, however, that in the case of phenic reactions a previous combination took place in the particular manner BO ingeniously conceived by Professor Armstrong as favouring the production of ortho-compounds, the general question, exemplified in the special case of the nitro-bromo-derivatives, for instance, why, starting from the mono-bromo-derivative we should get mainly a para-di-derivative instead of an ortho-di-derivative, and why, starting from the mono-nitro-derivative we should get malinly a meta-di-derivative rather than either a para- or an ortho-di-derivative, still remained a problem, and one of very great interest, towards the solution of which Professor Armstrong had, at any rate, made a serious advance.It was clear that the nature of the product depended a good deal on the conditions of, and mode6 of effecting, the reaction. He might here eaythat having regard to the usual rpodes of experi-menting, he was accustomed to point out that where the pre-existing radicle was one of the typical radicles formulatted as C1, OH, NH,, and CH,, respectively, or some.closely related radicle, the tendency was to the formation of 1-4 di-derivatives ; and that where the pre-existing radicle was one of the acidic radicles formulated as NOz, S03H,and C02H,or some allied radicle, the tendency was to the production of 1--3 di-derivatives. Having regard to the want of absolute con-cordance even in the writings of the present day, and to the extreme confusion in the writings of the last twenty years, as to the attribu- tion of the prefixes para-, ortho- and meta-, he preferred to speak of t'he different sets of compounds as 1-4, and 1-2 and 1-3 deriva-tives respectively. At the same time the expression of the primary 1, in each case, was for the most part superfluous, and might be omitted with advantage; only, to avoid confusing the other numerals with multiples, it was preferable to denote them by means of the small Roman or italic figures used by doctors when writing their prescrip- tions, instead of by the usual Arabic figures.Thus while speaking of the two liquid dibromobenaenes, or as he preferred to call them dibromo-phenoenes, as one- two, and one-three dibromophenoene re- spectively, he was accustomed to write and formulate them as ij-di- bromo-phenoene or ij-C6H4Br,, and iij-dibromo-phenoene or iij-C6H4Br, respectively, the so printed names and €ormule being much shorter and clearer than those usually employed. These expressions, more- 11 over, stand in direct relation to the facts that ij-dibromo-phenoene gives origin to two tribromo-derivatives, and that iij-dibromo-phenoene gives origin to three tribromo-derivatives.As regards the expression of the 1-4 or crystalline dibromo-phenoene, he was accustomed to write and formulate it as jv-dibromo-phenoene, or jv-C,H,Br, ; but it might be very well expressed as j-dibromo-phenoene or j-C,H,Br,, which would associate it with the fact of its giving origin to oGe tribromo-phenoene only. Mr. GROVESreferred to the absorption of chlorine in large quantity by chloroform and carbon tetrachloride, and thought that facts such a8 these ought to be taken into account. He did not think that the tendency to form symmetrical di-derivatives was so universal as suggested by the author : the formation of resorcinol from benzene- pumdisulphonic acid was a case in point.Dr. W. H. PERKIN,Jun., thought that the production from hydrazo-benzene, not only of benzidine but also of an isomer, was evidence against Dr, Armstrong’s view as to the manner in which para-compounds were formed. Dr. ARMSTRONG,replying to Professor Odling’s objection that tho para-derivative was the chief product, and not the ortho- as should be the case according to his (Dr. Armstrong’s) explanation of the manner in which substitution was effected, said tha,t this was by no means always the case : in a recent investigation of the chlorotoluenes, for example, it had been shown that about twice as much ortho- as para-dichlorotoluene was formed.The proportions in which para- and ortho-derivatives were formed, appeared, however, to vary greatly, and to depend very much on the conditions obtaining at the time of change. He was of opinion that the ’behaviour of the paraffins afforded the strongest evidence in support of his view that addition preceded substitution : the affinity of the ca>rbon-atoms being all but satisfied, especially in the lowest terms, substitution was effected but slowly in consequence of the small extent to which the chlorine was able to combine with the paraffin; and it was most important to observe that when chlorine had once become introduced, the intro- duction of other atoms could be effected more and niore readily-the chlorine already introduced rendering the molecule more ready to combine with chlorine.Mr. Groves’s reference to the solubility of chlorine in chloroform and carbon tetrachloride was most apposite. The behaviour of hydrazobenzene appeared to him to be perfectly in harmony with his views, the isomer formed together with benzidine being the ortho-compound. Cases such as were referred to by Mr. Groves mere probably not simple isomeric changes, but involved the successive occurrence of several distinct changes. 12 7. " Some Derivatives of Tetramethylene." By G. H. Calman and Di-. W. H. Perkin, Jun. On heating calcium tetramethyIenemonocarboxylat,e with lime, a gas and an oil are produced, two-thirds of the former consisting of ethylene, and the remaining third being a mixture of hydrogen, methane and carbonic oxide.The oil contains two new ketones, ditetramethylene ketone- CH2{ gg}CHaCO-CH { :?} CHz. B. p. 204-205" ; and methyltetramethylene ketone or acetyl-tetramethylene-:::}{CH,*CO*CH CH,. R.p. 137-138". Tetramethylene aldehyde has also been prepared by heating calciuni tetramethylenemonocarboxylate with calcium formate ; it boils at 115-117'. 8. "Derivatives of Yentamethylene." By Dr. W. H. Perkin, Jun. The sodium-derivative of ethyl malonate is converted by the action of trimethylene bromide into ethylic tetramethylenedicarboxylate and ethylic pentane-wz w,-tetracarboxylate, (C00Et)2*CH*CHz*CH,*CH,-CH(COOEt)2. On hydrolysis this latter yields the tetracerboxylic acid, On heating this acid to 200" it is converted into a-pimelic acid and carbonic anhydride. If ethylic pentanetetracarboxylate be treated with sodic ethylate, a disodium compound, (C0OEt),CNa*CHz*C HZ*CH,*CNa- (C 00Et)2, is formed.By treating this disodium-derivative with bromine, ethylic pentamethylenetetrncarboxylate,(C00Et)zC*CH,*CH,*CH,*C(COOEt),, I I is obtained. On hydrolysis this salt yields the tetracarboxylic acid, which on heating to 200" loses 2 molecules of carbonic anhydride, being con- verted into pentamethylenedicarboxylic acid-7I /CH-COOHCH, a crystalline body melting at 160". Ethylic pentamethylenedicarboxylate is a disagreeably smelling oil, boiling at 249-25'2". Pentamethylenedicarboxylic anhydride me1 ts at 64-67".DISCUSSION. Dr. A. K. MILLERasked : Had Dr. Perkin made any attempts to prepare hexamethylene rings T Reactions which would furnish cornpounds so constituted might easily be suggested ; and their pro- duction would afford considerable support to the arguments adduced in favour of the view tha,t those now described were tetra- and penta- methylene ring-compounds. Dr. ARMSTRONGremarked on the peculiarly interesting and valuable cha,racter of Dr. Perkin's work on polymethylene-d erivatives. In his paper on tetramethylene cornpounds Dr. Perkin had most clearly established the difference between what he called tetramethylene compounds and the known isomeric allyl-derivatives which it was conceivable might be formed in reactions such as were described; but it did iiot follow from this that the bodies in question were tetramethylene compounds : we were admittedly dealing with bodies of a novel type, and it was therefore necessary to be very cautious in applying knowledge gained by study of their physical properties, as we were unacquainted with the properties of any comparable series of compounds.Great differences were to be noted between maleic and fumaric acids, and between citra-, ita- and mesaconic acids, which could not at present be satisfactorily explained in terms of our conventional symbols ; and it WRS conceivable that open-chain compounds might exist having properties vei-y different from those of the known allyl-derivatives.Dr. PERKIN,Senr., said that in their physical properties the corn-pounds discovered by his son were altogether peculiar : they behaved nearly as saturated bodies, and therefore the only way at present of representing them was to employ closed-chain formula. The maleic compounds behaved as unsaturated bodies, and the fumaric com-pounds were still further removed from saturated compounds. The properties of the tetrametbylene compounds were in no sense akin to those of the maleic-fumaric, or citra-ita-mesacocic series. Dr. PERKIN,Junr., said that in the paper referred to he had only sought to prove that allylacetic and allylmalonic acids were different from what he had termed tetramethylene-mono- and di-carboxylic acids; the latter might have some quite different formula to those which he had proposed, but they could not be regarded as parallel compounds to the fumaric or itaconic acids.Dr. ARMSTRONGadded that it must not be forgotten that tri-methylene, CH2*CH2*CH2, although unsaturated, behaves practically as a sat'urated compound. 14 9. The Decomposition of Potassium Chlorate and Perchlorate by Heat." By Percy F. Frankland, Ph.D., B.Sc., A.R.S.M., and John Dingwall. The authors have reinvestigated the paints in the decomposition of' these bodies which were raised by Teed (Proceedings,Nos. 12 and 16, 1885-86). In the first series of experiments, potassium chlorate was partlially decomposed by heating in a tube over a naked flame. The results are summarised in the following table :-On KClO, actually decomposed.I ProportionPercentage of oxygen evolvccl on weight of KC10, takeu. Percentage KCl of oxygen formed evolved. (per cent.). 1 formed. I---No. 1. 2.66 ................ 6 -30 22 -48 71 -22 20 -87 No. 2. 5.19 ............... 6 -27 22 '43 '71-30 20 *s4 No. 3. 6.47 ................ '7 -09 23-68 69 93 22.32 -----I_-I Equation-10KC1037 6KC104 + 4KC1+ 302requires .............. 7*83 24* 34 67-83 24 -00 SKClO, =5KC104+3KCl+ 202 requires .................. 6 53 22 -81 70 -66 21 -33 2KC103= KC104 +KC1+02 reqiiires .................. 13.05 30.42 56 '53 32-00 On KC10, aotually decomposed. I I I1 PyoportionPerceatage of oxygen evolved of oxygenon weight of KC103 t,aken.Percentage uc1 KC1O, evolved toof oxygen formed formeu evolved. per cent.). (per cent.) 7' *57 partsof RC1I formed. I--I I No. 1. 6-89 ............... 8-14 1 25.44 1 66'42 1 23 -88 Na. 2. 6.78 ................ 8.76 26.03 65.21 25.10 No. 3. (KC10, mixed with powdered glass) 14'30 ...... 15'34 I 33-55 I 51.11 I 39.10 15 In further experiments the potassium chlorate was decomposed at a temperature below that at which potassium perchlorate suffers change, by heating it in the vapour of boiling sulphur (p. 14). It appears, therefore, that when potassium chlornte is partially decomposed by heat, the decomposition may be expressed by equa-tions of the type 8KC103 = 202 + KC104 + 3KC1, and that the more complete the decomposition the more does it approximate to that indicated by the eqnation 2KClO3 = KC104 + KC1 + 02.The authors have fully established the formation of potassium chlorate in the first stages of the decomposition of potassium per- chlorate. This reaction is of interest as forming an exception to Berthelot's law of maximum work, the well-known formation of potassium perchlorate from potassium chlorate being a reversible change. In a first series of experiments with perchlorate, the potassium chlorate was determined by means of the zinc-copper couple method. Finding, however, that the couple had a very slight action on per- chlorates, a second series of experiments were made, in which tho chlorate formed was determined by evaporation with chlorhydric acid; the results entirely substantiate those of the first series, and are as follows :-~~ On KC104 decomposed.Percentage of oxygen evolved on weight of I(C104 taken. Oxygenevolved KC1 .formed (per cent.). (per cent.). I formed, No. 1. 6'34 ................ 36-54 38 *70 24.76 70 '41 No. 2. 7'80.. .............. 36'63 38 -79 24.58 70'42 No. 3. 84 '05 ................ 43'60 49 *21 7.19 66 '06 The equation- 7KC10,-2KC103+5KC1+110, requires .................. 36 -29 38'44 25 *27 70-40 10. " The Action of Chlorine on Methyl Thiocyanate." By Dr. J. William James, University College, Cardiff. The author describes the result of the action of chlorine on methyl thioeyanate, a reaction first studied by Cahours, a3ndafterwards by Riehe.On passing dry chlorine into methyl thiocyanate at the ordinary temperature to complete saturation, the reaction being completed in sunlight, methyl thiocyanate is decomposed into cyawuric chloride, tkiocarbon,yl chloride (CSCl,), and the tetmcidoride, CSCI,. The latter is identical with the perchlormet hyl mercaptan of Ratlike, obtained by the action of chlorine on carbon disulphicle in presence of iodine. The chief reaction which takes place is : SCH,SCN + 11C1, = C,N,CI, + 2CSCld + CSC1, + 9HC1. Cahours studied the reactions in a qualitative manner only ; and Riche did not show the presence of either thiocarbonyl chloride or tetrachloride, and moreover, obtained a body of the formula C,SCl,, which, as is shown, must have been a mixture of CSCI, and C,N,CI,.The author has further established that when chlorine is passed into thiocarbonyl chloride it is completely absorbed, forming thio- carbonyl tetrachloride ; and that by the prolonged action of t8he gas this latter substance is decomposed into carbon tetrachloride and sulphur dichloride. The well-known fact that carbon disulphide is converted by chlorine into these two bodies seems therefore to be the result of a series of reactions, viz.: (1) CS, + 2C12 = CSCL + SC1,; (2) CSICI, + c1, = CSCl,; (3) csc1, + c1, = CCl, + sc1,. 17 Norwegian North Sea Expedition. XVI. Zoology. Mollusca. 11: by H. Priele : Christiania, 1886 : from the Editorial Committee. Proceedings and Transactions of the Royal Society of Canada : vol.iii, for the year 1885: Montreal, 1886 : from the Society. Progress of a Century; or, the Age of Iron and Steam: by E. Lawrence : London, 1886 : from the Author. A Catalogue of Scientific Periodicals (1865-1882) : by H. Carring-ton Bolton : Washington, 1835 : from the Smithsonian Institution. Index to the Literature of Explosives. Part I : by C. E. Munroe: Baltimore, 1886: from the Author. Der Chilisalpeter, seine Bedentung und Anwendung als Dunge- mittel : von A. Stutzer : Berlin, 1886 : from Mr. Warington. 11. By Purchase. Lehrbuch der Angewendeten Optik : von C. Gauge : Braunschweig, 1886. Bus Pharmazeutischer Vorzeit in Bild und Wort : von H. Peters : Berlin, 1886. Die Analyse der Milch : von E.Pfeiffer : Wiesbaden, 1886. Mohr’s Lehrbnch der Chemisch-analytischeii Titrirmethode : Nen bearbeitet : von A. Classen : 8 Auf: Braunschweig, 1886. Vierteljahreschrift der Chemie der Nahriings- und Genussmittel. I Heft, 1and 2 (continued) : Berlin, 1886. Zeitschrift fur Biologie : vols. i-oii. The Gas Engineer’s Chemical Manual: by J. Alfred Wanklyn: London, 1886. At the next meeting, on February 17th, the following papers will be read:- “The Influence of Temperature on the Heat of Dissolution of Salts.” By S. U. Pickering. “ Studies on the Laws of Substitution in the Naphthalene Series.” Part 111. By Dr. Armstrong and W. P. Wynne. HARRISON ANY SONS, PXIXTEXS IN ORYINARY TO HER MAJESTY, ST.MARTIN’B LANK.
ISSN:0369-8718
DOI:10.1039/PL8870300007
出版商:RSC
年代:1887
数据来源: RSC
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