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Proceedings of the Chemical Society, Vol. 26, No. 378 |
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Proceedings of the Chemical Society, London,
Volume 26,
Issue 378,
1910,
Page 321-331
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摘要:
Issued 13/12/ 10 PROCEEDINGS OF THE CHEMICAL SOCIETY. Vol. 26. No. 3'78. Thursday, December lst, 1910, at 8.30 p.m., Professor H~ROLDB. DIXON,M.A., Ph.D., F.R.S., President, in the Chair. Messrs. F. S. Long and Horace Finnemore were formally admitted Fellows of the Society. Certificates were read for the first time in favour of Messrs.: Albert Ashe, Laurie Square, Romford. Morris Cutner, B.Sc., 21, Bairstow Street, Preston. James Edward A. Devlin, Marist Brothers College, Uitenhage, Cape Colony. William Temple Gardner, Bruern, Alexandra Road, Upper Parkstone. Harold James Page, Avondale, Meteor Road, Westcliff -on-Sea. Robert Viner Stanford, M.Sc., Ph.D., Cardiff City M'ental Hos-pital, Whitchurch, Glam. A ballot for the election of Fellows was held, and the following were declared duly elected : Malcolm Percival Applebey.Stewart McGregor Rosmortli, E. Sc. Manindraiiath Banerjee. AndrB Bracher. Fred Wilkinson Barwick. Frederick Hugh Rochfort Brady. Sarat Chandra Bhattacharya, M.A. John C. Briggs. 322 Henry Vincent Bird Briscoe, B.Sc. Dhirendranath Mitra, B.A. John Brown, B.Sc. Harold Moore, B. Sc. Bertram Hayward Buttle. James Eckersley Myers, B.Sc. Frank Anthony Camp. Valliyil Govindan Nair, B.A., B.Sc. Frederick Challenger, B.Sc. Sidney Herbert Newman, B.Sc. Reginald Thomas Colgate. John Hamilton Paterson, M. Sc. Thomas Watts Coslett. Alfred John Pennington. Marshall Perley Cram, A.M., Ph.D. Benjamin Ashwell Posford. David Chalmers Crawford, M.A., B.Sc. Hari Prasad, B.A.Charles Crichton. Frederick Valentine Ramsden. John Hughes Davies, B.Sc., Ph.D. Alfred Oswald Ransome. Arthur Dodd. Thomas John Recs, E.A., B.Sc. James Hugh Duncan. Gangaram Rajendrarao Rele. William Gidley Emmett, B.A. Joseph Ridgway, B. A. Ainslie Jackson Ensor, B.Sc. James Beglar Robinson. John George Finlayson, B.A. Rajendra Nath Sen, M.A., M.Sc. George Alexander Goddon. Frederick Herbert Sharpe. Count Arnaud de Gramont. Percy Lancelot James Smith, M.A. Fred. Holt, R.Sc. William James Pittock Smith. Prince Mahmood Ali Khan, B.A. Jwala Prasad Srivastava, R.Sc. Edmund Knecht, KSc., P1i.D. Claude Vnreille Temperley, R.Sc. William Arthur Knight, M. A. Augustus George Terrey. Bertram Lambort, M.A. Leo Tschngaeff.Alleyne Leechman. Richard Babington Turbutt, €3. A. Kenneth Stewart Low. Joseph Turner. Clement Ward Lowe. John Fleming Culun Brown Vance. David Jackson MacGeorge. Robert Lander Mackenzie Wallis, B. A. Malcolm McNish. Arthur Eernard Williams. Rikti Majima. Herbert Gonlding Williams, B. SC. James Irvine Ornie Masson, M.Sc. William Norman Stewart Wright. Thomas R. Merton, B.Sc. Syed Muhammad Yusuf, B.Sc. Alec Duncan Mitchell, B. Sc. Of the following papers, those marked * were read: *321. The triazo-group. Part XV. Triazoethylene (vinylazo- imide) and the triazoethyl halides.” By Martin Onslow Forster and Sidney Herbert Newman. Tria.zoefhyZene (vinylazoimide), CH2:CHN3, prepared by the action of hot alcoholic potassium hydroxide on triazoethyl bromide or iodide, is a pale yellow liquid, boiling at 26O/760 mm.The dibromide is rapidly decomposed by cold water, yielding bromo-acetaldehyde with hydrazoic and hydrobromic acids. B-Chloro-a-triazoethalze (triazoet73yl chloride), N3*CH,*CH2CI, obtained from triazoethyl iodide by heating it with mercuric chloride, boils at 45O/25 mm., and has D24 1.2855. P-Bromo-a-triuzoethme (triazoethyl bromide), N,*CH2*CH,Br, arising from triazoethyl alcohol and phosphorus tribromide, boils at 49O/ 20 mm., and has Dl9 1-6675. P-Zodo-a-triazoethane (tyiazoethyl iodide), N,*CH,-CH,I, produced when a solution of sodium iodide in dry acetone acts on the foregoing substance, boils at 68O/20 mm., and has D?51.9154. B-T?-iaZoethJ etlw, N,*CH,*CH,*0*CzH5, is the result of heating triazoethyl alcohol with et,hyl iodide and dry silver oxide; it boils at 49O/25 mm., and has D24 0.9744.DISCUSSION. The PRESIDENTasked Dr. Forster whether he had attempted to heat' ths vapour of triazoethylene, and, if so, whether it had exploded. Dr. T. CALLANinquired whether the authors had tried the action of silver azide on triazoethyl iodide with a view to obtaining, by simple replacement of the iodine by the triazo-group, a compound with two triazo-groups in the molecule. Dr. FORSTERstated that the vapour of triazoethylene had not been heated; nor had any attempt been made to effect interaction between triazoethyl iodide and silver azide, because the symmetrical bistriazoethane which should arise could be prepared by a more simple process, and had already been examined."322. c6 The dinitro-derivativesof dimethyl-p-toluidine." By ailbert T. Morgan and Arthur Clayton. Although dimethyl-p-toluidine, when nitrated in concentrated sulphuric acid solution, yields only 2-nitrodimethyl-p-toluidine, yet when the nitration mixture is poured into water so that the fem- peration rises to 40°, the reaction proceeds a stage further, and 2 : 5-dinitrodimetliyl-p-toluidine (m. p. 103-104°) is produced. The position assumed by the second nitro-group in this compound was ascertained in the following manner. 2-Nitrodimet-hyl-p-t oluidine, when reduced and acet ylated, yielded 2-acetyl-4: 4-dimethyl-2 : 4-diaminotoluene, which, on nitration, gave 5-nit ro-2-ucet ylaminodi'methyl-p-toIthidine. On reduction, this nitro- compound furnished 2 -acetyl -2 : 5 -diaminodimethyl-p-tohidine, which, by the agency of the Sandmeyer reaction, gave rise to 5-brorno-2-acetylaminodimeth yl-p-tohidine, the constitution of which has already been determined.The foregoing 2-acetyl-2 : 5-diaminodimethyl-p-toluidine was con- verted into 2 : 5-diacetyldiaminodimethyl-p-toluidine,which can also be prepared by reducing 2 : 5-dinitrodimethyl-p-toluidine and acetylating the resulting 2 : 5-diaminodimet~hyl-ptoluidine,thus 324 demonstrating the position of the second nitro-group in 2: 5-di-nitrodimethyl-p-toluidine. 2 : 6-Diizitrodimethy~-p-to~~~d~~e(m. p. 192O), was prepared by the action of methyl sulphate on 2: 6-di-nitrocptoluidine. DISCUSSION.Dr. FLURSCHEIMmentioned that Crum Brown and Gibson’s rule, which did not profess to explain the directing influences in the benzene nucleus, had also ceased to correspond with facts (compare J. p. Chem., 1902, [ii], 66, 322). He had also proved that the alternate hypothesis advocat,ed by Dr. Morgan-the prevention of orth+par&substitution by the negativity of a substituent-also did not agree with facts (compare J. pr. Chem., 1902, [ii], 66, 329; 1905, [ii], 71, 500). On the other hand, he had himself suggested a solution based on the varying strength of “ single ” bonds (compare Zoc. cit., and J. pr. Chem., 1907, [ii], 76, 197, for directing influence of methyl; also Ber., 1906, 39,2015), and this had been borne out by every observed fact.The sole exception had hitherto been Dr. Morgan’s suggestion (Proc., 1910, 25, 82) that, in dilute acid, a second nitregroup entered 2-nitrodimethyl-p-toluidine and possibly in the 6-position. The experimental decision had been left to him and Mr. Clayton, and their results had vindicated his (the speaker’s) theory. Dr. MORG.4N7 in reply, said that they regarded the nitration phenomenon from a mechanical standpoint, based on the Pope and Barlow theory of the configuration of benzene, whereas Dr. Flurscheim, in looking at the matter rather from the point of view of EekulB’s benzene formula, laid too much stress on the connexion between unsaturation of the substituent radicle and its power of inducing ortho-para-substitution. But although the unsaturated groups, NH,, OH, etc., induced substitution in the orthepara- positions, yet the methyl radicle did the same, and the latter group could not fairly be assumed to possess much residual affinity. On the other hand, he regarded the groups, -NH,*HSO,, -NH,R*HSO,, and -NI%R,*HSO,, present; when aromatic amines were nitrated in concentrated sulphuric acid, as being distinctly unsaturated complexes owing to the presence of double linkings in the sulphate group: Nevertheless, these complexes did not usually induce substitution in ortho-para.-posit3ions, but in meta-positions. Where the latter positions were not assumed, as in the case of m-toluidine, the 325 exceptional orientation could be traced to the influence of other substituents (Noelting and Stoecklin, Ber., 1891, 24, 564) : NO,/\ 1\/INH3*HS04 /? L\jNH3*HS04 CH, /? Main product./\NO2 - +- /JNH,*HSO, \/ INH,*HSO, Produced in least (/NH3*HS0, amount. NO2 In this nitration, the nitro-groups took up the positions t>hey would assume even in the absence of the NH3*HS04radicle, this result indicating that the directive (attractive) influence of the saturated methyl group prevailed over the influence of the sulphate complex, the repulsive effect of which wits observed only in the fact that 6-nitro-m-toluidine was the chief product. *323. “Experiments on the Walden inversion. Part VI. Con-version of the optically active a-hydroxy-a-phenylpropionic acids into a-chloro-a-phenylpropionicacids.” By Alex.McRenzie and George William Clough. The authors find t,hat thionyl chloride and phosphorus pent& chloride behave differently towards I-a-hydroxy-a-phenylpropionic acid, inasmuch as the former gives I-a-chloro-a-phenylpropionic acid, whereas the latter gives d-a-chloro-a-phenylpropionic acid. The action of thionyl chloride and of phosphorus pentachloride on optically active ethyl a-hydrox.y-a-phenylpropionatehas also been examined. 324. ‘‘ The auto-reduction of hydrazines.” By Frederick Daniel Chattaway and Montague Aldridge. Aromatic hydra.zines, when heated, undergo simultaneous oxidation and reduction, whereby an amine, ammonia., nitrogen, and a hydrocarbon are produced, according to the equation: 2R*NH*NH2=RNH2+NH3+N,+RH. The reaction is a general one, and, in the case of unsubstituted primary hydrazines, such as phenylhydrazine, the tolylhydrazines, and the naphthylhydrazines, takes place quantitatively.It pro-ceeds slowly even at the boiling temperature, the rate increasing rapidly as the boiling point of the hydrazine is approached. It. is 326 thus impossible to obtain any hydrazine in a state of purity by distillation. The slow decomposition which hydrazines undergo on keeping, even when air is excluded, is due to this auto-reduction. In the case of hydrazines containing a substituted aromatic residue, although this primary decomposition takes place to a considerable extent, other reactions may also occur on heating, especially at a high temperature, due to the presence of the sub- stituting atoms or groups.325. “The activity of acids as catalysts in relation to the nature of the solvent medium,” By Harry Medforth Dawson. The influence of the nature of the solvent on the rate of the tautomeric change of acetone, in presence of sulphuric acid as a catalyst, has been investigated in alcohol-water mixtures ranging from pure water to anhydrous alcohol. It is found that the velociby of the tautomeric change is nearly independent of the composition of the solvent if this contains less than about seventy volumes per cent. of ethyl alcohol. As the proportion of alcohol is increased, t,he reaction velocity increases, slowly at first, but afterwards more and more rapidly, until in anhydrous alcohol the speed is more than one hundred times as great as it is in aqueous solution.The large changes in velocity are probably due to changes in the catalytic activity of the acid in the different solvents. Although the velocities in alcohol and in water differ to such a very large extent, the concentrations of the positive acid ions in equimolar acid solutions appear to be very nearly equal, and it is supposed that the actual catalyst is represented by free hydrogen ions, which, however, in consequence of their relatively small concentration, play only a subsidiary part in connexion with the electrical conductivity of the solutions.328. “The volume of a solute in solution.” By Dan Tyrer. The volume changes which occur on the dissolution of a solute have been measured, and the specific solution volume of the solute has been calculated by means of the equation: where v is the specific solution volume, or the change in volume caused by the dissolution of 1gram of the solute, d the percentage concentration of the solution, S, the specific volume of t.he solution, and S, that of the pure solvent. The values of Sl and the values of 29, calculated according to the above equation, have been deter- mined for a large number of solutions of various solutes and solvents by means of the dilatometer and pyknometer. Normal organic solutes and solvents have been used to avoid complications through molecular association or dissociation.It has been found that (1) the specific solution volume is, in most cases, constant and quite independent of the concentration, (2) the specific solution volume of the solute varies but slightly from solvent to solvent. The cause of the variations with change of solvent was discussed, and the hypothesis was put forward that through an increase or decrease in the molecular attraction between the molecules of solvent and solute, a contraction or expansion of the solvent occurs, causing a variation in the calculated specific volume of the solute in solution. 327. ‘‘ Theabsorption spectra of Borne derivatives and isomerides of 1:2-diketo-A3-cycZopentene.” By John Edward Purvis.The results of this investigation show that (1) the colour is determined primarily by the monoketonic and diketonic structures ; (2) the absorption in the more refrangible regions of the mono-ketonic compounds is determined by the type of ring in which the ketonic structure occurs; (3) in the diketonic compounds the colour is modified in the direction of the more refrangible regions by the introduction of an oximine or :N*NHPh group, a result analogous to that previously observed in diketopyrrolines ; (4) in the diketonic compounds the absorption of t’he phenyl- hydrazone or of the isophenazine derivative is wholly different from that of the corresponding substances derived from the diketo-pyrrolines; (5) the difference in the isophenazine compound and in ilbluish-coloured sodium derivative of 1: 2-diketo-h3-cycZopentene is explained as the result of changes in the positional valencies of the ring.6‘328. 4-/3-Aminoethylglyoxaline (P-iminaeolylethylamine)and the other active principles of ergot.’’ By George Barger and Henry Eallett Dale. The identification of an ergot base having a very powerful action on the isolated uterus as 4-&aminoethylglyoxaline (,S-iminazolyl- ethylamine) (this vol., p. 128) has been completed by analysis of the dipicrate, and by a comparison of physiological properties. The method of isolation was described in detail. 328 329. ‘(Synthesis of camphoric acid.” By Gustav Komppa. Although Thorpe (Proc., 1909, 25, 94) was able to obtain only a 10 per cent.yield of methyl diketoapocamphorate, three of the author’s assistants have obtained yields varying from 45 to 70.5 per cent. From the methylated ester, which Blanc and Thorpe (Trans., 1910, 97, 836) state to be the 0-methyl ether, the author has now prepared, for the fifth time, r-dehydrocamphoric acid, and from this has obtained r-camphoric acid. The author maintains the constitution previously assigned by him to methyl diketocamphorate, and shows that the methyl group in question must be attached to carbon and not to oxygen, as boiling hydriodic acid (Zeisel) fails to remove it. 330. ‘6Viscositg and association. Part I. Association of the phenols.” By Ferdinand Bernard Thole. The viscosities of a number of phenols and their derivatives have been measured both in the pure state and in solution.From the results, the following conclusions have been drawn : (1) The results obtained by the viscometric method agree very closely with those derived from other physical constants, such as vapour pressure, dielectric constant, molecular surface energy, molecular refractivity, and molecular weight determined cry6 scopically. (2) The viscosity determinations, using 13 x 106 as amol. vol. criterion of association, show that phenols are associated, the ortho- compounds to the least, and the para-compounds to the greatest, extent. The ethers are not associated, but the acetates show slight association. (3) The carbethoxyl, aldehyde, nitro- and halogen groups exert a marked inhibitive influence on association.Alkyl groups exert only a slight influence. Since the degree of inhibition of association appears to be intimately connected with the degree of unsakuration of the substituent, it is suggested that the depression of association is partly due to an attraction between the latent valency of the hydroxylic oxygen and the unsaturated substituent, the consequence being a diminution of the tendency to form complexes through the latent valency of t’he hydroxyl group. The same hypothesis explains the gradual disappearance of the characteristic reactivity of the carbonyl group in the series acetone-ethyl acetate-acetic acid. 329 (4) Solution in even a comparatively non-dissociating solvent, such as amyl acetate, produces considerable disruption of the molecular aggregates.In a dissociating solvent, such as ethyl alcohol, the dissociatdon is practically complete. 331. Compounds produced by the simultaneous action of nitrites‘( and hyposulphites on nickel salts. A method for the detection of nickel in presence of much cobalt.” (Preliminary note.) By Walter Craven Ball. When solutions of sodium or potassium nitrite and nickel nitrate are mixed, and sodium hyposulphite is gradually added, the liquid assumes the colour of a permanganate solution, and needle-shaped, dark purple crystals separate. This substance, of which the formula is possibly Na,NiNS20,,4H20, seems t’o be the sodium salt of a complex acid containing nickel.The potassium salt, similar in colour, but more soluble, may be obtained by a slight modification of the method. Both salts yield purple precipitates with barium and strontium solutions. Similar complex cyanides, of a.n intense reddish-purple colour, may be obtained by treatment of the above substances with pot#assium cyanide, and also by the oxidation of ammoniacal solutions of hydroxylamine, cont,aining a nickel salt and a cyanide. They are soluble in alcohol and other organic solvents, and afford a ready means of detecting nickel in presence of much cobalt. The compounds are all very unstable, and from their method of preparation would appear to be derived from some compound inter- mediate between nitrous acid and hydroxylamine, possibly from dih ydroxylamine.ADDITIONS TO nm LIBRARY. I. Donution. Fenton, Hewy John Horstman. Outlines of chemistry. With practical work. Part I. 2nd edition. pp. xviii+415. Cambridge 1910. (Recd. 5/12/10.) From the Author. 11. By Purc?mse. Buchner, Georg. Die Metallfarbung und deren Ausfiihrung mit besonderer Beriicksichtigung der chemischen Metallfiirbung. 4th edition. pp. xvi+ 397. Berlin 1910. (Recd. 28/11/10.) Koerner, Wilhelm. Ueber die Bestimmung des chemischen Ortes bei den aromatischen Substanzen. Translated and edited by G. Bruni 330 and B. L.Vanzetti. (Oatwvrtld’s Klassihr, No. 174.) Leipzig 1910. (Recd, 1O/ 1 2/10.) Lomonossow, M. W. Physikalisch-chemische Abhandlungen, 1741-1752. Edited by B. N. Mensohutkin and Jlax Speter, (Ostwald’s Klassiker, Xo.178.) Leipzig 1910. (Recd. 10/12/10.) Rechenberg, C. von. Theorie der Gewinnung und Trennung der Aetherischen Oele durch Destillation. pp. xii + 259 to 751. [Supplement to Gildemeister, E., and Hoffman, Pr., ‘‘Die aetherischen Oele.”] Leipzig 1910. (Reed. 2&/11/10.) Woker, Gertiwd. Die Katalyse. Die Rolle der Katnlyse in der analytischen Chernie. I. Allgemeiner Teil. (Die chemische Analyse, Vol. XI and XII.) Stuttgart 1910. (12ecd. 9/12/10.) 111. Pamphlets. Siegrist, H. De la constitution de quelques ddrivds iodds. (From the J. Suisse Cliim. Phnmn., 1910, 48.) Studzinski, J. Ueber die giftigen Eigenschaften des Blutes. (From the Zentr, Phptiol., 1910, 23.) Tassilly, E. L’essence d’ Ylang-Ylang de la RQunion. (From the Bull.Sci. Phccrm., 1910, 17.) Thunberg, Torsten. Studien uber die Beeinflussung des Gas-austausches des uberlebenden Froschmuskels durch verschiedene Stoffe. (From the skand. Arch. Physiol., 1909, 23.) Thunberg, 2’. Ueber katalytische Beschleunigung der Sauerstoff -aufnahme der Muskelsubstanz. (From the Zentr. Physiol., 1910, 23.) Waidner, C. K, and Burgess, G. K. Note on the temperature scale between 100’ and 500’ C. (From the Bull. Bureau ofstandards, 1910, 7.) Walter, E. Ueber die Verwendung des Benzidins fur den Blut- nachweis, im besonderen uber seine Anmendungsweise in der gerichts- arztlichen Praxis. (From the Beut. Med. Foch., 1910.) Walpole, George Stanley. A method of titrating physiological fluids.(From the Proc. PhysioZ. SOC.,1910; J. Physioz., 40.) Wielen, P. Van der. Dosage de la morphine, de la narcotine et de la codeine dans l’opium et dam les preparations gnlhiques de Popium. (From the BUZZ.Sci. Phccrm., 1910, 17.) ERRATUM. PROCEEDINGS,1910. Page Line 268 20 for ‘‘ethyl ” read I‘ othyle.” 331 At the next Ordinary Scientific Meeting on Thursday, Decem-ber 15th, 1910, at 8.30 p.m., the following papers will be communicated : “Studies on enzyme action. Part XV. The comparative in-fluence of monohydric CnHzn+l alcohols and other non-electrolytes on enzymic activity.” By H. E. Armstrong and E. F. Armstrong. ‘‘ Studies on enzyme action. Part XVI. The enzymes of emulsin (11). Prunase.” By H. E. Armstrong, E.F. Armstrong, and E. Horton. “ Studies on enzyme action. Part XVII. The enzymes of emulsin (111). The probable seat of origin of amygdalin.” By H. E. Armstrong, E. F. Armstrong, and E. Horton. “Studies on enzyme action. Part XVIII. Enzymes of the emulsin type (11). The distribution of P-glucases in plants.” By H. E. Armstrong, E. F. Arnistrong, and E. Horton. “ Studies on enzyme action. Part XIX. Enzymes of the emulsin type (111). Linase.” By H. E. Armstrong and J. V. Eyre. “The interaction of alloxan and glycine.” By W. H. Hurtley and W. 0. Wootton. “ Traube’s molecular-volume method applied to binary mixtures of organic substances.” By W. R. G. Atkins. ‘(Investigations on the dependence of rotatory power on chemical constitution. Part I. The rotations of the simplest secondary alcohols of the fatty series. By R. H. Pickard and J. Kenyon. “ Oxycodeine. A new alkaloid from opium.” By J. J. Dobbie and A. Lauder. ‘I Studies in the carbazole series.” By C. Schwalbe and S. Wolff. “ Syntheses with phenol derivatives containing a mobile nitro- group. Part 111. Complex iminazoles, azo-compounds, and azides.” By R. Meldola and H. Kuntzen. “ The chemistry of mesothorium.” By F. Soddy. B. CLAY AND SOBS, LTD., BREAD ST. HILL, E.C., AND BUBGAY? SUFFOLK.
ISSN:0369-8718
DOI:10.1039/PL9102600321
出版商:RSC
年代:1910
数据来源: RSC
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