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Proceedings of the Chemical Society, Vol. 26, No. 369 |
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Proceedings of the Chemical Society, London,
Volume 26,
Issue 369,
1910,
Page 65-72
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摘要:
[/suw,ed 30/3/ 10 PROCEEDINGS OF THR CHEMICAL SOCIETY. Vol. 26. No.369. Thursday, March 17th, 1910, at 8.30 p.m., Professor HAROLDB. DIXON,M.A., F.R.S., President, in the Chair. The PRESIDENTreferred to the loss sustained by the Society in the death of Geheimrath Professor Dr. Hans Landolt (elected sn Honorary and Foreign Member in lSSS), and, on the same day, Monday, March 14th, of Professor James Campbell Brown, a Vice-President of the Society. Messrs. A. L. Landau and N. V. Sidgwick were formally admitted Fellows of the Society. Certificates were read for the first time in favour of Messrs. : John Bethwaite, 48, Northumberland Street, Workington. Harry Farrands, M. A., The College, Isleworth. Charles Samuel Garland, 18,Derwent Grove, Dulmich, S.E.Edwin Harrison, 18, Old Swan Lane, Upper Thames Street, E.C. Horace George Mason, B.Sc. , The Grammar School, Kingsbridge, South Devon. Francis Edwin Needs, 7, Effingham Road, St. Andrew's Park, Bristol. Of the following papers, those marked * were read : *74. '' Organic derivatives of silicon. Part XIII. Optically active compounds containing one asymmetric silicon group." By Frederick Challenger and Frederic Stanley Kipping. Experiments on the resolution of dl-dibenzylethylpropylsilicane-monosulphonic acid, CH2Ph*SiEtPr*CH2*C,H,*S0,H(Part XII, l'rmcs 1910,97,142),were described. Several bases were tried without success, but on systematically crystallising the brucine salt, extreme fractions differing in melting point by about 80' were obtained.These two fractions had the same specific rotations. The sparingly soluble one contained an acid which with I-menthylamine, cinchonidine, and strychnine gave compounds identical ic melting point and specific rotation, within the limits of experimental error, with the corre-sponding salts of the dl-acid. Moderately concentrated solutions ol the sodium salt of this resolution product seemed to be optically inactive. In these circumstances additional evidence had to be procured before arriving at a definite conclusion, but in the end it was proved beyond all question that the acid had been resolved into its enantio-morphously related components. The optically pure I-acid, prepared from the spapingly soluble brucine salt, has a specific rotation of about [.ID -0.75" in concentrated alcoholic solutions of its sodium salt.With all optically active bases which were examined, except, of course, with brucine, it gives salts which are almost indistinguishable by melting point or specific rotation determinations from the corresponding derivatives of the dl-acid. These results are very similar to those previously obtained in the case of the active and dl-sul phobenzy le thy1 propylsilicy1 oxides, which contain two asymmetric silicon groups (Kipping, Trans.,1907, 91, 234 ; 1908,93, 465), but in the present instance the enantiornorphous character of the active acid is even more rarely exhibited. *75. The rate of hydration of acetic anhydride." By Albert Cherburg David Rivett and Nevi1 Vincent Sidgwick.The authors have determined the velocity of the above reaction in water at 26O by means of the conductivity. The conductivity and viscosity of solutions of acetic acid from 3Ndownwards were measured, and it was shown that if the ionic velocity is assumed to be propor-tional to the fluidity (the reciprocal of the viscosity), Ostwald's law holds for this acid up to a normality of 0.94, whereas in its simple form it does so only up to 0.05. The velocity of hydration of the anhydride showed that the reaction was a unimolecular one. It is not catalysed by hydrogen ions, and beyond a certain point the constant falls steadily with increasing concentration. 67 “76. “The colour and ionisation of cupric salts. Part 11.” By Nevi1 Vincent Sidgwick and Henry Thomas Tizard.In continuation of previous work (l’rccns., 1908, 93, 187), the authors have redetermined the depth of colour of cupric acetate, pro- pionate, and formate in water, and the influence of acid on it. Excess of acid markedly diminishes the colour in the acetate and propionate, the diminution reaching a limit when about one equivalent of acid has been added ;further addition has no effect. No change is produced with the formste. This points to the existence of hydrolysis, the product of which has in the first two cases a deeper colour than the salt. The fall in (molecular) colour on adding excess of acid is constant, and independent of the dilution. The conductivity and viscosity of solutions of these three salts, (1) neutral, (2) in presence of one equivalent, (3) in presence of two equivalents of the acid, have also been measured.In strong solutions of the acetate or propionate, the second equivalent diminishes the conductivity, owing no doubt to the increase of viscosity. Assuming ionic velocity to be proportional to fluidity, then if po,pr,p2 are the molecular conductivities, and qo, ql, qa the viscosities of the three solutions at any concentration, A! =plyL-(p2v2-plql) is the corrected conductivity of a neutral solution in which no hydrolysis should occur, The difference H=M-p0yo is the change of conductivity duo to the hydrolysis. 11was found to be very nearly constant. It increases slightly with dilution, but much less than X, which appears to indicate the improbable conclusion that the hydrolysis diminishes with increasing dilution.If the only dissociation taking place over the range examined is CuA, GUA.+ A’, and the colour of CuA2 and Cub is constant, and if Mis proportional to the degree of ionisation, then on plotting the colour against M, a straight line should be obtained. As a fact, however, the rise of colour at high concentrations is greater than this. Possible causes of this disagreement were discussed. From the values of M, those of the velocities of the CuA* ion and of K, the dissociation constant of the salt, have been calculated. The agreement in K at not too great dilutions is good, but the ionic velocities are unexpectedly high.*77. “Some new metallic carbonyla.” By the late Ludwig Mond, Heinrich Hirtz, and Matthewman Dalton Cowap. A description was given of a new cobalt carbonyl, Co(CO),, which is obtained by the action of heat on the carbonyl Co(CO),. ilfolyhdenurn carbonyl, NO(CO)~,and a ruthenium cnrbonyl have also been preptred. 68 "78. "Studies of dynamic isomerism. Part X. The relationship between absorption spectra and isomeric change. Absorption spectra of camphorcarboxglic acid and its derivatives." ByThomas Martin Lowry, Cecil Henry Desch, and Herbert William Southgate. Pour types of absorption curve were described : (1) Camphorcarboxylic acid, its sodium salt, esters, amide, and piper- idide give a shallow band at 1/A 3450.This band is also given by the dimethyl derivative, C,H14<A0CMe'co2Me, and is attributed to the carbonyl group. The diethyl derivative is abnormal, and appears to be differently constituted. (2) The halogen derivatives, C,H,,<bOCC1[BrI*COX , give con-tinuous absorption curves, but with a well-marked extension near the point where the bands appear in the spectra of the parent substances. (3) In presence of alkalis the esters and amide give a deep band at 1/X 3450; this is attributed to the formation of an enolic sodium (4) The enolic acyl derivatives, C,H,,<I c*Co*o*R1,d*O*CO*R,give continuous absorption curves. "79. ''Studies of dynamic isomerism. Part XI. The relationship between absorption spectra and isomeric change.Absorption speotra of the acyl derivatives of camphor." By Thomas Martin Lowry and Herbert William Southgate. (1) Oxymethylenecamphor and its methyl and ethyl esters, C:CH-OR ~*Hl,<bO ,give a deep band at 1/X 3800. ,CBr*CHO(2) The bromo-derivative, C,H,4\60 , gives a continuous (3) The sodium salt, CsH14<8:",",y, gives a deep band at 1/X3350. curve with a well-marked extension. The same band is given by aminomethylenecamphor, which is therefore Iformulated as C,H,,<I c*CHo The anhydride gives a band atC*NH,' C*CO*HH*CO*C1/X 3500, arid is probably C,H,,<g ~>C,H1,, whilst the 69 acetyl derivative, which gives a band at 1/X 4000, is perhaps (4)Acetyl-, propionyl-, and butyryl-camphor give a band at l/h 3550; on the addition of sodium hydroxide, a deep band is developed at 1/X 3250.(5) Benzoylcamphor (enolic form) gives R band at l/X 3250; this is moved to l/X 3150 in the sodium salt, and to 1/X 3500 in the acetyl and benzoyl derivatives. 80. “The action of aromatic amines on ethyl malonate.” By Frederick Daniel Chattaway and James Montrose Duncan Olmsted. The statements hitherto made respecting this reaction leave the impression that the esters of malonanilic and malonotoluidic acids are only to be obtained with difficulty, and that they are not formed by the interaction of malonic ester and aromatic amines. The recent work of Chattaway and Mason (Trans., 1910, 97, 339) has shown that the interaction of malonic ester and halogen-substituted anilines follows a perfectly regular course, and that both halogen-substituted ethyl malonanilates and malonanilides are formed. The authors find that unsubstituted aromatic arnines act similarly.When aniline or a toluidine is heated with ethyl malonate, the ester of malonanilic or the corresponding malonotoluidic acid is first formed, this being converted into malonanilide or a malonotolui-dide by the further action of the amine. As the corresponding acids can be obtained in nearly theoretical amounts by hgdrolysing the esters, this is by far the simplest method of preparing them. 81. ‘‘ Synthesis of dipeptides of lauric and wnonoic acids. Products of the condensation of lauric and n-nonoic acids with glycine, Janine, and leucine.” (Preliminary note.) By Arthur Hopwood and Charles Weizmann. During the course of some experiments on the synthesis of substances of possible physiological importance, the authors have prepared the following : a-Bronzo-n-monoyZ chloride, C,H,,Br-COCl, prepared by heating a-hromononoic acid and phosphorus pentachloride, boils at 118-1 ZOO/ 9 mm.a-Bwrno-n-nonoylglycine, C,H,GBr*CO*NH*CH,*CO,H, prepared by the interaction of a-bromononoyl cliloride and glycine in alkaline solution, is crystalline and melbs at 116”. a-Amino-n-nonoyZgZycine, NH,*C,H,,*CO*NH*CH,*CO,H, prepared from a-bromononoylglycine and concentrated aqueous ammonia, melts at 215-216’. A similar series of compounds has been obtained by the condensation of a-bromo-n-nonoyl chloride with alanine and with leucine ; also from n-lauric acid by the interaction of a-bromo-n-lauryl chloride and glycine, alanine, and leucine respectively.82. “The densities and molecular weights of neon and heliun?.” By Herbert Edmeston Watson. A considerable quantity of neon has been prepared in a high state of purity, the separation from helium having been effected by a fractionation from charcoal at the temperature of liquid air. The weight of a normal litre of this gas was found to be 0.9002 gram, this being the mean of eleven determinations, and the error should not exceed 0.0003. The value originally found by Ramsay and Travers was 0.8 91. The density of helium was also measured, the figure 0,1782 being obtained, but as this was the mean of only two determinations with the same sample of gas, it should not be considered correct to more than 1 part in 500.Some experiments were carried out on the rate of diffusion of a mixture of neon and helium through quartz, with the view of effecting a separation by this means. It was found, however, that quartz is slightly permeable to neon, and, moreover, that the rate of diffusion of helium was far smaller than had been expected. An estimate of the amounts of helium and neon in the atmosphere gave the values 1 part by volume in 185,000 and 1 in 65,000 respectively. In conjunction with Mr. F. P. Burt, the author has calculated, according to Berthelot’s method, the molecular weights of these gases, using the figures obtained by Burt for the compressibility of helium values for the densities. The molecular weight of helium is thus found to be 3.994, and of neon, 20.200. 83.6‘ The molecular weights of krypton and xenon.” By Herbert Edmeston Watson. The densities of krypton and xenon were recently determined by Moore (Truns.,1908, 93,2181), but in deducing the molecular weights, no correction was applied for compressibility, although with these gases this correction may amount to a considerable qnantity. and the above I.)Pt.6,1910,Soc.,Paraday(Trans. 0’ atand neon 71 The compressibility has now been calculated from the critical constants by Guye’s method (J.CAim. Phys., 1906, 5, 5), and the figures obtained were compared with those deduced from the com- pressibility measurements of Ramsay and Travers (Proc.Roy. Soc., 1901, 6’7,329). As these were carried out only at pressures exceeding 25 atmospheres, there is natnrally a considerable amount of uncertainty in the results, but, nevertheless, the agreement is as good as can be expected. The results obtained, as well as the corresponding figures for the other inactive gases, are sumrnarised in the following table, L being the weight of a normal litre, and A the compressibility coefficient between 0 and 1 atmosphere : L (grams). A x 106. Mol. wt. Helium ............... 0.1782 0 3.994 Neon .............. 0-9002 105 20’200 Argon ............ 1.7809 -93 39’SSl li ryptoii ............... 3.708 -215 82.92 X enoil.................. 5-851 -690 130’22 84. ‘(Studies in the diphenyl series. Part I. Acetylation of benzidine derivatives.” By John Cannell Cain and Percy May. The authors have studied the acetylation, by means of acetic anhydride in aqueous-alcoholic solution, of several bases of the benzidine series, and have determined the relative proportions of mono- and di-acetyl derivatives formed. The presence of negative groups in all cases diminishes the degree of acetylation, and it was suggested that this influence of negative groups (which of course is well known) may be due to the existence of a double linking between the negative atom or group and the nitrogen atom. Several new mono-and di-acetpl derivatives of substituted benzidines were described.85. ‘(Additive compounds of s-trinitrobenzene with arylamines. Combination as affected by the constitution of the arylamine.” By John Joseph Sudborough and Stanley Hoskings Beard. A description was given of additive compounds prepared from s-trinitrobenzene and a number of aromatic arnines, and the relation- its capacity to form an additive compound, (b) the colour of the additive compound, was discussed. (.) the amine and ofship between the constitution 72 BANQUET TO PAST PRESIDENTS. The Banquet to Past Presidents will be held at the Savoy Hotel, on Thumday, May 26th, 1910. Further particulars will be announced shortly. At the next Ordinary Scientific Meeting on Thursday,April 21st, 1910, at 8.30 p.m., the following papers will be communicated : “ Tetranitroaniline.” By B. Flurscheim and T. Simon, “Experiments on the Walden inversion. Part IV. The inter- conversion of the optically active atrolactinic acids.” By A. McKenzie and G. W. Clough. “Studies in fermentation. Part 111. Tho r61e of diifusion in fermentation by yeast cells.” By A. Slator and H. J. S. Sand. R. CLAY AND SONS, LTD., BREAD ST. HILL, E.C. AND BUNGAY, SUFFOLli.
ISSN:0369-8718
DOI:10.1039/PL9102600065
出版商:RSC
年代:1910
数据来源: RSC
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