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Proceedings of the Chemical Society, Vol. 25, No. 352 |
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Proceedings of the Chemical Society, London,
Volume 25,
Issue 352,
1909,
Page 53-64
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摘要:
54 Reginald Cyril Herbert Cooke, 17, St. Edmund’s Terrace, Regent’s Park, N.W. Henry Jermain Maude Creighton, 3l.A ., Halifax, Nova Scotia, Canada. Philip Henry Crewe, Glencairn, Woods Moor, Stockport. John Frederick Haws, Parkfield Villa, Newton-by-Frankby, Cheshire. Reginald Vernon Hickinbotham, 144, West Street, Maritzburg, Natal. Arthur Edwin Tate, B.Sc., Gladstone House, Salter Row, Pontef ract. Francis Lawry Usher, B.Sc., 18, Clifton Park, Bristol. The selection by the Council of Professor F. S. Kipping, F.K.S., as Longstaff Medallist for 1909 was announced, the presentation to be made at the Annual General Meeting. It was stated that the following changes in the Officers and Council were proposed by the Council : President to retire: Sir William Ramsay, K.C.B.The-Presidents to retire: Dr. R. Messel and Prof. W. H. Perkin. Ordinary Members of Council to retive: Dr. H. A. D. Jowett, Dr. F. E.Matthews, Dr. W. J. Sell, Dr. J. Wade. As President: Prof, Harold B. Dixon. As Vice-Presidentswho have filled the ofice of President : Prof. H. E. Armstrong, Prof. A. Crum Brown, Sir William Crookes, Sir James Dewar, Dr. A. G. Vernon Harconrt, Prof. It. Meldola, Dr. H. Miiller, Prof. W. Odling, Sir William RamBay, Prof. J. Emerson Reynolds, Sir Henry E. Roscoe, Dr. W. J. Russell, Prof. T. E. Thorpe, and Prof. W. A. Tilden. As Treasurer :Dr. Alexander Scott. As Hon. Secretnr&s: Dr. M. 0. Forster and Prof. Arthur W. Crossley. A8 Foreign, Secretavy :Dr. Horace T. Brown.As Vice-Presidents:Prof. J. Campbell Brown, Prof. J. N. Collie, Dr. J. J. Dobbie, Prof. F. S. Kipping, Sir A. Pedler, Prof. James Walker. As New Ordinar9 Members of Council: Prof. W. A. Bone, Mr. C. E. Groves, Dr. G. T, Morgan, Dr. A. E. H. Tutton. Dr. Arthur Harden, Dr. V. H. Veley, and Dr. J. A. Voelcker were elected Auditors to Audit the Society’s Accounts. 55 A ballot for. the election of Fellows was held, and the following were subsequently declared elected : George Henry Joseph Adlam, B. ,4. John Hrgh Jeffery. Hubert Rrunskill. Henry Huinphreys Jones. Arthur Clayton, B. Sc. Horace Keeble. Herbert Edwin Cocksedge, B. A., K.Sc. Joseph Leedham. Alfred Bertram Coles, M.A. John Essoa McGillvray, M.A. John Charles Jesser Coope.William George Martin, B. Sc. Frederick Percy Dunn, B. SC. Percy May. Frederick Ferraboschi. Wi1:iam Norton Morley, B.Sc. John Thomas Fox. Frederick Hubert Painter, B. SC. Arthur Gordon Francis, B. Sc. Joseph Allen Pickard, B. SC. John Thomas Furnell. Frank George Pope. Ross Aiken Gortner, M.A., B.Sc. Colston James Regan. John Wilberforce Green. liobert Robinson, M. Sc. Alfred George Cooper Gwyer, B.Sc. , Herbert Rogers. Ph. D. Philip John Sageman. Robert Main Harland. J. H. Charles Schulten, Ph.D. Walter Norman Haworth, M.Sc. David Segaller. Eric Hayward. James Thomas Stevenson. Frank Higson. Reginald Wells Varley. James Henry Hoseason. Guy Ransom Warwick, B. A. Ralph Hough. Percy Charles Henry West. Xobert Ernest Jackson.Thomas Jabez Wild. Of the following papers, those marked * were read : *45. (( A study of some asymmetric compounds.” By Frederic Stanley Kipping. When a dl-acid is treated with a d-base, the product is a mixture of the dAdB- and ZAdB-salts, and when a a?-acid is combined with a dl-base, the ,components of the product are dAdB and dAZB. If therefore A and B represent a particular acid and a particular base respectively, and dl-Amay be resolved with the aid of d-B, it might be inferred that dl-B could also be resolved with the aid of d-A. The dAdB-component is common to both original products, and as ZAdB and dAZB are enantiomorphously related and have the same solubility in any given optically inactive solvent, the observed difference in solubility between dAdB and lAdB should also be effective in the case of dAdB and dAZB.Now dl-sulphobenzylethylpropylsilicyloxide may be resolved with d-(or with E)methylhydrindamine (Trans., 1908, 93,457) ; experiments showed, however, that dl-methylhydrindamine could not be resolved with the aid of d-sulphobenzylethylpropylsilicyl oxide under similar conditions. dl-Methylhydrindamine may be resolved by fractionally crystal-lising its d-hydrogen tartrate from water (Tattersall, Trans., 1904, 85, 169); it is now shown that dl-tartaric acid may be resolved with d-methylhydrindamine under similar conditions, and that both the dAdB-and the ZAdB-components may be isolated in one series of crjstallisations. dl-Hydrindamine cannot be resolved by fractionally crystallising its d-rnandelate from water ;dl-mandeiic acid, however, is very easily resolved by fractionally crystallising from water its salt with &(or with I-)hydrindamine.These results seem to show that partly racemic molecules exist in solution. DISCUSSIOK. Nr. A. E. DUNSTANagreed with Prof. Kipping that the physico- chemical evidence for the existence of racemic compounds in solution was slight, owing to the dissociation of these substances, but he pointed out that the results published by Clerk Ranken and Taylor, Stewart, Dunst'an and Thole, all indicated that undoubtedly there was a small difference between the physical properties of the racemic and the active compound when dissolved. Noreover, these diff ereuces were consistent and increased with the concentration.*46. '' The decomposition and sublimation of ammonium nitrite." By Prafulla ChanQa Ray. When an aqueous solution of ammonium nitrite is heated in a vacuum at about 37-40', only a very small portion of the salt decomposes according to the equation : NH,NO, =2H,O +N, ; the main bulk of the salt crystallising out. If the temperature is then gradually raised to 70°, slow decomposition continually proceeds according to the above equation, but the major portion sublimes un- changed. When this sublimate is heated by means of a naked flame, the gaseous products are nitrogen and nitric oxide, the latter often amounting to as much as 6 per cent. DISCUSSION. Dr. DIVERSremarked on thy interest attached to the crystallisation of ammonium nitrite from its aqueous solution and of the sublimation of a salt hitherto supposed to be too unstable for these operations to be poasible. The generation of much nitric oxide when the sublimed salt was vaporised and further heated seemed to indicate the occurrence of a decomposition tending to that production of hydrazine which Professor Ray had looked for : 2NH,NO, =N,H, +2B,O +ZNO, the elements of the hydrazine appearing as ammonia and nitrogen.57 Dr. VELEYconcurred with the author that ammonium nitrite in solution is best prepared by the decomposition of silver nitrite and ammonium chloride. It was a most interesting point that such a solution could be evaporated in a vacuum without decomposition, and that the ammonium nitrite could not only be crystallised out, but even purified by sublimation. The observation tvas :remarkable that if the conditions were such that the solid salt decomposed, then nitric oxide in a small proportion was formed in addition to nitrogen.Blanchard (Zeitsch. phgsikaZ. Chem., 1902, 41, 681; and ibid., 1905, 51, 117) had shown that when an aqueous solution containing potential ammonium nitrite is heated under atmospheric pressure, nitric oxide is formed in about the same proportion as that found by the author, but on reduction of pressure the proportion is reduced to nil. It would thus appear that the solid salt and aqueous solutions give the same result, although under reverse conditions.*47. The estimation of hydroxyl derivatives in mixtures of organic compounds.” By Harold Hibbert. Hibbert and Sudborough’s method (Trans., 1904, 85, 033) for the estimation of hydroxyl groups in carbon compounds can be applied with equal success to mixtures of hydroxyl derivatives with other organic compounds, for example, ketones, esters, nitriles, etc. It is necessary to take rather more of the Grignard reagent than is sufficient to combine with both substances. In this way the author has been able to estimate a-naphthol in presence of various ketones, ethyl benzoate, methyl hydrogen succinate, and acetonitrile, as well as chloral in a mixture of this with acetone. *48. 6‘ A simple method for determining the chemical affinity* of orgrmio substances.” By Harold Hibbert.The author bas shomu (preceding paper) that hydroxyl deriv-atives can be estimated in presence of ketones if excess of the Grignard reagent is employed. If now a quantity of the latter is taken, insufficient to combine with both, it is obvious that a partition * The author suggests using the term aflnergy (compounded from a$in-ity and en crgy ; German equivalent = affinergie) as a substitute for Michael’s chemicnl potcnlial (Annaletr, 1908,363,21) in order to avoid confusion with the physical conception of potential (as in electrical potential), with which it lias nothing in coLlllllOll, 58 of the reagent between the two substances mill take place, and the amount of methane evolved will depend on their relative masses and reaction velocities, assuming, of course, that all the products (apart from the methme) remain in solution. The latter condition is fulfilled by working in phenetole solution. By taking the same hydroxyl compound, mixing it with equimolecular quantities of various ketones, and using the same (insufficient) amount of magnesium methyl iodide solution, it is thus possibIe to measure the relative reaction velocities of the ketones towards the reagent, since these are indirectly proportional to the amounts of methane evolved.The method serves in this way as a means for determining the chemical affinity of organic compounds. The relative affinities (using a-naphthol) of the following ketones have already been determined : dimethyl, methyl ethyl, and diethyl ketone ; aceto- and benzo-phenone.DISCUSSIOK. Dr. LAPWORTHasked if the author had fully considered his assumption that velocity of reaction in non-reversible changes might be taken as a measure of affinity. Scientists were agreed that changes could only occur spontaneously when a diminution in potential thereby resulted, but at present this principle, whilst often serving to indicate the direction of change in it chemical system, was difficult to develop for irreversible changes, and the determination of affinity seemed hardly satisfactory except in such cases where equili- brium conditions could be ascertained. Dr. SENTERsaid that in his opinion the reactivity of a chemical system could best be expressed, with van’t Hoff, by means of the equation : Reaction Velocity =Driving Force/Resistance.The driving force was the ‘6 chemical affinity ” and depended on the free energy of the system, which could be calculated, in a perfectly definite way, from equilibrium measurements. The reaction velocity might be enormously affected by slight changes in the medium or by catalysts, neither of which could, in general, modify to any great extent the free energy (or the chemical affinity). The fact that the free energy and the reaction velocity are affected so differently by reagents allowed to some extent of their investigation separately, and there-fore this method of regarding the matter seemed to possess distinct ndvantages.The PRESIDENTremarked that it is essential to distinguish between an energy and one of the factors of an energy : 59 just as Heat Energy =Temperature x Entropy, and as Electric Energy =Electric potential x Electric quantity, so Chemical Energy =Chemical Affinity x Chemical quantity. Now as chemical quantity is proportional to electric quantity (as is proved by Faraday’s law), it follows that chemical and electric affinity must also be proportional. Therefore, by determining electric potential, chemical affinity is measured. The word ‘‘affinergy ” appears to be confusing, inasmuch as it combines the conception of a factor of an energy with the energy itself. *49. ‘(Chlorine generated by potassium permanganate : its preparation and purity.” By Edgar Wedekind and Samuel Judd Lewis.The method of preparing chlorine by dropping concentrated hydro -chloric acid on crystals of pot.tssium pxm mgatnate, which was suggested by Graebe (Bey., 1902, 35,43), is stated to yield the gas free from oxides of chlorine, but no experimental proof of this is given by that author. The purity of the gas has now, however, been ascertained by the following experiments : (1) On passing the gas through sulphuric acid no reddish coloration is produced, showing the absence of chlorine peroxi.de. (The formation of chlorine monoxide is improbable, as this would be at once decomposed by the hydrochloric acid.) (2) 2-11 Grams of tin were heated to dull redness in a stremn of the gas; the residue weighed only 0.7 milligram.(3) The gas is com- pletely absorbed by mercury. (4)A definite volume of the gas was absorbed by a solution of 15 grains of potassium iodide in water, and the iodine liberated was titrated with sodium thiosulphate solution, of which 168.70 C.C. (mean of four determinations) were required, whereas in a corresponding experiment with chlorine, generated from pure manganese dioxide and hydrochloric acid (and assumed to be free from oxides of chlorine, carbon dioxide, etc.), 168.67 C.C. of thio-sulphate solution (mean of six determinations) were used. DISCUSSION. Dr. SCOTTpointed out that, as potassium permanganate often con-tains small quantities of chlorate, chlorine prepared by its means is peculiarly liable to be contaminated with traces of chlorine oxides.The only safe test for t,he presence of these is to absorb the gas in a neutral solution of potassiiim iodide, and then decolorise it 60 exactly by means of sodium thiosuiphate; if, on adding to the colour- less solution pure dilute hydrochloric acid, no iodine is liberated, then the chlorine may be regarded as quite free from its oxides, but any iodine liberated is exactly equivalent to the combined oxygen, since, in neutral solution, it goes to form iodate in accordance with t’he following equations : 3C1,O + 7KI =31, +KIO, + 6KC1 3C1, =31, 3C1,O + 12KI +6HC1= 61, + 3H,O + 12ICCI 3(0)=31, and 6010, + 1OK1=31, + IKIO, +6KCl 3C1, =31, 6C10, + 30KI + 24HC1= 151, + 12H,O + SOKC1 60, =121,.Neither of the authors’ assumptions : (a)that hypochlorous anhy- dride must be absent, because of the presence of a large excess of hydrochloric acid, or (b)that, chlorine peroxide could not be present, as the sulphuric acid by which the gas was dried did not acquire a reddish colour, was justified. What their experiments did prove wag that the gas thus prepared was of the same order of purity as that from hydrochloric acid and manganese dioxide. 50. “The isolation of the aromatic sulphinic aoide.” By John Thomas. The aromatic sulphinic acids are characterised, as a class, by forming ferric salts which are insoluble in water and fairly concentrated mineral acids; this property cm be usefdly applied in the separation of these acids from the solutions in which they are produced.The ferric salts of benzenesulphinic, a-and p-toluonesulphinic, and a-and /3-naphthalenesulphinic acids have been prepared arid characterised, arid simple methods indicated for converting them into the corre-sponding sulphinic acids, sulphonyl chlorides, and sulphonamides. 51. LL Analytical investigation of zirconium metal.” By Edgar Wedekind and Samuel Judd Lewis. Jn view of zirconium having not yet been obtained in a pure condition, and of the lack of analytical data regarding the composition of the specimens obtained by various workers, the authors have worked out methods of analysis which make it possible to determine the pro- portions of the most common impurities. The zirconium existing in the free state is separated as the tetrachloride from that in combina- tion with oxygen by burning tho substance in pure chlorine; in this way the proportion of oxygen is determined directly. Nitrogen is 61 estimated by a method similar to that of Kjeldahl ;carbon by com-bustion of the metal in oxygen at very low pressure, and subsequent absorption of the carbon dioxide produced.52. (‘The action of ethylene dibromide on monomethylaniline.” By John Gunning Moore Dunlop and Humphrey Owen Jones. By the interaction of two gram-molecules of monomethylaniline with one gram-molecule of ethylene di bromide, di phenylpiperazine (m. p. 163’) is formed by a reaction represented by the equation : 4NHXePh +2C2H,Br2=PhN<~~,:~~>NPh,ZHBr+ 2NAXe2Ph,.E€Br.When four gram-molecules of monomethylaniline are used instead of two in this interaction, diphenyldimethylethylenediamine, NMePh*CH,*CH2*NMePh, melting at 4T0,is produced. 53. (‘Salicylidene-m-toluidine, a new phototropic compound ; salicylideneamines : salicylamides.” By Alfred Senier and Frederick George Shepheard. In continuation of previous work on acridine synthesis, a series of new salicylideneamines and salicylamides have been prepared. Among these, saZicyEidene-m-toZ~uidinehas special interest, as it exhibits photo- tropy (Marckwald, Zeitsch. physikal. Chenz., 1899, 30, 140). On crystallisation from its solutions, the crystals are pale yellow, but when exposed to sunlight the colour changes quickly to deep orange, and this colour change is reversed, although more slowly, when the crystals are placed in the dark.This reversible reaction is due to light waves of high refrangibility; it does not take place in solution, and the sensibility of the compound remains unimpaired after at least a month’s time. KO evidence could be obtained of triboluminescence or phosphorescence. Salicylidene-m-toluidine behaves in this respect like the anhydrous chloride of quinoquinoline and P-tetrachloro-a-ketonaphthalene studied by Marckwald. It is similar also to the fulgenic acid compounds investigated by Stobbe (Annalen, 1908, 359, 1). Probably phototropy in this instance, as is supposed to be the case in others, depends on the existence of two stereo- or other isomerides formed respectively under the influence of short or long waves of light.54. “The action of ethyl carbamate on esters of organic acids and mustard oils.” By Siegfried Ruhemann and John Gillies Priestley. Ethyl phenylpropiolate does not form an additive product with ethyl sodiocarbamate, but condenses with it to yield ethyl pheityl-popioZyZcarbamute, C,H,CiC*CO*NH*CO,Et. This reaction has been applied to the preparation of acyl derivatives of ethyl carbamate from esters of fatty and fatty-aromatic acids. In this way, also, ethyl formylcarbamate, CHO*NH*CO,Et, has been obtained, which is readily hydrolysed by mineral acids, even in the cold. The esters of benzenecarboxylic acids form either only very small quantities of the acyl derivatives of ethyl carbamate, as with ethyl benzoate, or no trace of the acyl carbarnate, as with ethyl o-phthalnte. Phenylthiocarbimide reacts with ethyl sodiocarbamate to form carboxyethylphenylthiocarbimide, NH(CO,Et)*CS*NH:C,H, (see Doran, Ikuns., 1896, 69, 326), and a yellow compound having the H.cs.rformula C6H5mN -yo, which is anhydro- dipheny Id ithiobiuret-C6H,*N:C -S cwboxyZic acid.-1t-forms colourless sodium and potassium salts, and is readily decomposed by alkalis. Allylthiocarbimide yields with ethyl sodiocarbemate a substance, CDH110NSS2,with similar properties to those of the former compound. 55. (‘The hydrolysis of amggdalin by emulsin. Part 111. Synthesis of d-benzaldehydecyanohydrin.” By Samuel James Manson Auld.The assumption generally made that benzaldehydecyanohydrin must be formed as an intermediate product of the decomposition of amygdalin by emulain is objected to, and evidence has been brought forward showing that an asymmetric synthesis of d-benzsldehyde-cyanohydrin takes place under the influence of emulsin, and that its formation in this manner proceeds more rapidly than its formation during the hydrolysis of amygdalin by emulsin. Emulsin can also induce the formation of an optically active hydroxybenzaldehyde- cyanohydrin from hydroxybonzaldehyde and hydrocyanic acid. 63 ADDITIONS TO THE LIBRARY. I. Donatiom. Fischer, Emil. Untersuchungen uber Kohlenhydrate und Fermente (1884-1908).pp. viii+ 912. Berlin 1909. (Recd. 21/1/09.) From the Author. Guttmann, Oscar. The manufacture of explosives. Twenty years' progress. Four Cantor Lectures delivered at the Royal Society of Arts in November and December, 1908. pp. viii + 84. ill. London 1909. (Becd. 17/2/09.) From the Publishers : Messrs. Whittaker & Co. fiordon Memorial College, Khartoum, Third report, of the Wellcome Research Laboratories. pp. 477. ill. London 190s. (Recd. 15/2/09.) From the Director. Supplement to the third report, Review of some of the recent advances in tropical medicine. By Andrew Balfour and R.G. Archibald. pp. 251. London 1908. (Recd. 15/2/09.) From the Director, Johnson, Charles Morris. Rapid methods for the chemical analysis of special steels, steel-making alloys, and graphite.pp. vi + 22 1. New Uork 1909. (Red. 12/2/09.) From the Publishers : Messrs. John Wiley & Sons. Linnean Society of London. The Darwin-Wallace Celebration held on Thursday, 1st July, 1908. pp. viii+ 134. ill. London 1908. (Recd. 15/2/09 .) From the Society. Senter, George. Outlines of physical chemistry. pp. xvii + 369, ill. London 1909. (Recd. 26/1/09.) From the Publishers : Nessrs. Methuen & Co. Stewart, Alfred Walter. Recent advances in organic chemistry. pp. xv + 296. London 1908. (Recd. 25/1/09.) From the Author. Symons, Brerrzton. Genesis of metallic ores and of the rocks which enclose them. pp. xxxiii + 494. ill. London 1908. (Recd. 19/1/09.} From the Author. Woburn Experimental Fruit Farm.Tenth report. By the Duke of Bedford and Spelizcer U. Pickering. pp. iv+50. London 1909. (Recd. 26/1/09.) From the Authors. 64 ANNIVERSARY DINNER. It has been arranged that the Fellows of the Society and their friends shall dine together at the Whitehall Rooms, Hotel Metropole, at 6.30 for 7 o’clock, on Thursday, March 25th, 1909 (the day fixed for the Annual General Meeting). The price of the tickets will be One Guinea each, including wine. All applications for tickets must be received not later than Thursday, March 18th next. Tickets will be forwarded to Fellows on receipt of a remittance for the number required, made payable to ‘‘ Mr. S. E. Carr ” and addressed to the Assistant Secretary, Chemical Society, Burlington House, W.At the next Ordinary Scientific Meeting, on Thursday, March 4th, 1909, there mill be a ballot for the election of an Honorary and Foreign Member, and the following papers will be communicated : ‘I The action’of anhydrosiilphuric acid on triphenylsilicol.” ByG. Martin and F. S. Kipping. “ The ignition temperatures of gases.” By H. B. Dixon and H. F, Coward. ‘‘Diazohydroxylarnino-compoundsand the influence of substituting groups on the stability of their molecules.” By N. L. Gebhard and H. B. Thompson. “Tetraketopiperazine. Part 11.” By A. T. de Moulpied and. A. Rule. (‘The alkaloids of Senecio Zatifulius,” By H. E. Watt. ‘(The miscibility of the pyridine bases with water and the .influence of a critical-solution point on the shape of the melting-point curve.” By 0. Flnschner. 6‘ An interpretation of the Hantzsch-Werner hypothesis.” By M. 0. Forster and F. P. Dunn. ‘‘The triazo-group. Part IX. Transformation of cinnamoylazo-imide into cinnamenylcarbimide (cinnamenyl isocyanate).” By M. 0. Forster. (( The preparation of dichlorocarbamide.” By F. D. Chattaway. The interaction of rnethylenediamines or methyleneanilines and carbimides or thiocarbimides ;thiotetrahydroquinazolines,methylene-carbamides, dicarbanilidomethylenediamines and their hom~log~e~.’~ By A. Senier and F. G. Shepheard. 54. CLAY ANI) SOhS, LTD., BHhAD hT. HILL, E.C., AND BUNOAY, YUYEVLU.
ISSN:0369-8718
DOI:10.1039/PL9092500053
出版商:RSC
年代:1909
数据来源: RSC
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