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Proceedings of the Chemical Society, Vol. 29, No. 409 |
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Proceedings of the Chemical Society, London,
Volume 29,
Issue 409,
1913,
Page 1-20
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[issued 30/1/13 PROCEEDINGS OF THE CHEMICAL SOCIETY. Vol. 29 No.409. Thursday, January 23rd, 1913, at 8.30 p.m., Professor PERCYF ERANKLAND,LL.D., F.R.S., President, iu. the Chair. Messrs. James W. NcBain, &I. Nierenstein, Arthur J. Hale, anc W. Compton Till were formally admitted Fellows of the Society. The PRESIDENTrer'erred to the loss sustained by the Society through death, of : El(ctcd. 1)Led. Brthur Crozier Clande: ... June 18th 1902 January 17th, 1913 John MoArthur ... ... ... I>ect~mberIst, 1887 December 9th, 1912 Artliur Richardson ... ... Juue 18th, 1885 June Ist, 1912 Henry Seward ... ... ... Jarinary 20th, 1S70 April 12th, 1912 Certificates were read for the first time in favour of Messrs.: William Beaih, 152, St.George's Road, Hull. Percy Charles Burr, B.Sc:., Essex Lodge, Ravensbourne Park Catford, S.E. Harold Eeginald Septimus Clotworthy, B.A., B.Sc., 39, Trinitj College, Dublin. John Albert C'ockshutt, M.Sc., Queen's College, Taunton. Tin Kari Giose, B.A., 23/i, Baniatola Street, Hatkhola P.O. Calcutta. George Watson Gray, 8, Inner Temple. Liverpool. 2 Daniel William Lloyd, B.Sc., The Manse, Ormonde Road, Kil- kenny. Walter Cyril Loynes, Eastfield, Comberton Road, Kidderminster. Alexander Killen Macbeth, M.A., B.Sc., 3, Victoria Terrace, Cregagh, Belfast. Henry Stephen Martin, 64, Dyke Road, Brighton. Aylmer Henry Xaude, Great Baddow, Chelmsford. Joseph Horsnell May, 21, Donovan Avenue, Muswell Hill, N.Ernest Joseph Mumford, 67, Hatherley Road, Walthamstow, N.E. John Walter Smith, B.Sc., 48~,Hurstbourne Road, Forest Hill, S.E. Hubert Rogers Wood, c/o Messrs. Fenner, Alder and Co., Ltd., Millwall, E. A Certificate has been authorised by the Council for presentation to ballot under Bye-law I (3) in favour of Mr. Jonathan Parker, c/o The Wattle Extract Co., 42, Anglo-African House, Durban, Natal. Of the following papers, those marked * were read: “1. ‘‘ The constituents of the rhizome and roots of Caulophgllum thalictroides.” By Prederick Be ding Power and Arthur Henry Salway. The material employed for this investigation consisted of the rhizome and roots of the American plant, Cauloyhyllum thalic-troides (Linng), Michaux (Nat. Ord.Berberidaceae). A preliminary test showed the presence of an alkaloid, and a small amount of an enzyme was obtained, which slowly hydrolysed amygdalin. An alcoholic extract of the ground material, when distilled in a current of steam, yielded a small amount of an essential oil. From the alcoholic extract the following definite compounds were isolated : (i) Methylcytisine, C12HI6ON2(m. p. 137O; [a]=-221-6O), the picrate of which melts at 228O; (ii) a crystalline glucoside, caulosapnin, C,4H8,017,4H20 (m. p. 250-255O), which on hydro- lysis is resolved into caulosapogenim, C42H6606(m. p. 315O), and dextrose ; (iii) a new crystalline glucoside, caulophyllosaponin, C66H104017(m. p. 250--260°; [aID +32-3O), which on hydrolysis is resolved into caulophyllosapogenin, C,H,,O, (m.p. 315O), and arabinose; (iv) a phytosterol, C2,R,,0 (m. p. 153O); (v) citrullol, C,,H,,O,(OH>,; (vi) a mixture of fatty acids, consisting of palmitic, stearic, cerotic, oleic, and linolic acids. The alcoholic extract also 3 contained a quantity of sugar, which yielded d-phenylglucosazone (m. p. 210°), and a comparatively small amount of resinous material. Methylcytisine represents the alkaloid first isolated by J. U. Lloyd (Proc. A m.er. Yharm. Assoc., 1893, 41, 115), and designated by him “ caulophylline,” but its composition had not heretofore been known. The glucoside to which the name of mulosuponin has now been given is undoubtedly identical with a glucosidic substance, which was likewise first obtained by Lloyd, and termed “ leontin,” although its formula had not been correctly determined.Its complete characterisation has now been effected. “2. (‘Ionisation and the law of mass action.” By William Robert Bousfield. The author showed that the dilution laws for strong electrolytes formulated by Rudolphi, van’t Hoff, and Kohlrausch (with some others) are all trne in the region of very high dilution, all being equivalent in that region to the simple law: (1 -a)=h-4 x Constant, where h is the total number of molecules of water per mol. of solute. In this region the law for weak electrolytes becomes: (1 -a)=h-* x Constant. The fundamerital difference between weak and strong electrolytes may therefore be thus stated: For weak electrolytes, at great dilution, the active mass of the undissociated fraction is inversely proportional to the mass of the water.For strong electrolytes, at great dilution, the active mass of the undissociated fraction is inversely proport.iona1 to the square root of the mass of the water. The question of the best method of arriving at the true coefficient of ionisation was also considered. DISCUSSION. In reply to Dr. Senter, Mr. EOUSFIELDstated that he thought it was by a special consideration of the active mass of the dissociated fraction of the solute that the formulae would be ultimately brought into conformity with the law of mass action. As to the manner in which the theory of ionic sizes reconciled the series of values for freezing-point depressions, he referred to a former paper (Phil.Trans., 1906, A, 206, 149). 4 *3. “The character and cause of the blue fluorescence which develops in alkaline solutions containing quinol and sulphite on exposure to the air.” By Thomas Cunningham Porter. Moist pbenzoquinone and quinhydrone each react directly with neutral as well as with acid alkali-metal sulphites to form com-pounds which differ according to which of the reagents is in excess. With excess of sulphite remarkably stable compounds such as (NH,HSQ,),C&C,O, are produced. These, in turn, form with alkali- and alkaline-earth-metal hydroxides substances which give brilliantly fluorescent aqueous solutions. The character of this blue fluorescence was described, and it was shown that the fluorescence of “ stale ” quinol and sulphite photo- graphic developers is identical with it, and due to the same cause.*4. “ The form of extinction curves : cobalt nitrate solutions.” By Thomas Ralph Merton. An investigation has been made of the extinction curves of cobalt nitrate solutions, which exhibit a single absorption band in the visible spectrum. It has been found that the curve may be repre- sented within the limits of experimental error by a simple mathe- matical expression. It is suggested that many of the apparently anomalous forms of extinction curves which are found are due to the superposition of some such simple type as the above. 5. (‘The hydrolysis of ethylene glycol diacetate.(Preliminary note.)’’ By Ernest Graham Bainbridge. The author has investigated the action of sodium ethoxide in alcoholic solution on ethylene glycol diacetate at the boiling point of the mixture, and finds that ethyl acetate is produced. A yield of 85 per cent. of ethylene glycol can readily be obtained as follows: A molecular mixture of ethylene glycol diacetate and sodium ethoxide is heated on a steam-bath to remove the ethyl acetate and excess of alcohol, the residue treated with water, and distilled under diminished pressure. The distillate is then fraction- ated, the yield being almost that required by theory. The author is at present engaged in working out the mechanism of the reaction, and in further investigating the action of sodium ethoxide and sodium hydroxide on ethylene glycol diacetate.5 6. "The chemistry of the glutaconic acids. Part VII. The normal and labile forms of ay-dimethylglutaconic acid and their reduction to cib.-ay-dimethylglutaric acid." By Jocelyn Field Thorpe and Arthur Samuel Wood. It has been found possible to isolate the labile modification of ay-dimethylglutaconic acid, which is a crystalline substance melting at 118O. The view expressed in previous parts of this series that both the labile and normal forms of substituted glutaconic acids have a &configuration is supported by the fact that both the labile and normal forms of ay-dimethylglutaconic acid yield cis-ay-dimethylglutaric acid on reduction : -7 Me*CO,H (pz-CM~-CO,H -'3.FKMe*CO,HNormal acid (m. p. 147"). vJ32 Me CO,H /--+ CH xe0CO, K FHCHMe*CO,H Labile acid (m. p.-118"). cis-ay-Dimethylglataric acid (m. p. 128"). The properties of the labile acid were described. 7. "The influence of water on the partial pressure of hydrogen chloride above its alcoholic solutions." By William Jacob Jones, Arthur Lapworth, and Herbert Muschamp Lingford. The authors have determined the partial pressures of hydrogen chloride above its anhydrous alcoholic solution over a range from 0'275iV to 3*19N,and aIso in presence of small quantities of water up to 2.5 gram-molecules per litre. The apparatus used consisted of three saturators of the type devised by Gahl, united by ground- glass joints with mercury seals, and containing in order, anhydrous ethyl alcohol, the hydrogen chloride solution, and water respec-tively.Hydrogen was passed through the apparatus, which was wholly immersed in a thermostat at 25' & 0.05, the use of air having been found to lead to chemical change and inconsistent results; the volume of gas used was determined from the weight of alcohol which passed from the first saturator, whilst the hydrogen chloride expelled from the second solution (which remained practically constant in concentration) was ascertained by titration of the liquid in the third saturator. The results obtained were consistent, and the method appeared 6 to give. satisfactory values, except possibly with very low pressures (0.2 mm.or less), when water was present. A somewhat complicated formula, based on Dolezalek’s expres- sion, serves to express t.he influence of the concentration of hydrogen chloride or water, or both together, over a wide range. 8. ‘‘Quinone-ammonium derivatives. Part 11. Nitro-haloid, di- haloid, and azo-derivatives.” By Raphael Meldola and William Francis Hollely. In continuation of their former paper (T., 1912, 101, 912) the authors described new types of quinone-ammonium derivatives con- taining halogens and azo-groups. The isolation of these compounds had been made possible by the discovery that the nitro-groups in the dinitrotrimethylammonium-benzoquinonedescribed in their last communication could be either partly or completely reduced, the resclting amino- and diamino-compounds being amenable to treat- ment by all the ordinary diazo-methods.The compounds described were of the types: X =halogen. The preparation of the bisazo-compound from &naphthol and the isolation of the first of the quinone-ammonium derivatives contain- ing an asymmetric nitrogen atom was preliminarily indicated by the authors. The relationship between the colour and constitution of the compounds was .further considered, and preference provision- ally given to the ‘(aci ”-form for the nitro-group in the nitro-deriv- atives which are invariably coloured, the corresponding haloid derivatives being colourless : 0 0 \/ Colouretl. The “quinole” structure for the hydrated form (T.7 1912, 101, 918) was considered to have received further support from the experimental results obtained, 7 9.(‘The chemical nature of some radioactive disintegration products.” By Alexander Fleck. It has been found that uranium-X, mesothorium-2, radioactinium, thorium-B and C, actinium-B and C, radium-B, C, and E, have chemical properties identical with those of some already known element. Uranium-X and radioactinium are chemically similar to and non-separable from thorium, mesothorium-2 is non-separable from actinium, thorium-B is non-separable from lead, radium-B and actinium-B are extremely similar to lead and most probably non-separable from it ;thorium-C, radium-C, and actinium-C are very closely allied to bismuth, and probably chemically similar to it. The present view that there is only one product, radium-&’, between radio-lea,d and polonium has been confirmed by the direct measurement of the growth of radium-F from radium-E.Radium-E has chemical properties identical in all respects with those of bismuth. 10. The action of ammonia and alkylamines on reducing sugars.” By James Colquhoun Irvine, Robert Fraser Thomson, and Charles Scott Garrett. The action of ammonia, in methyl-alcoholic solution, on various sugar derivatives has been re-investigated. The reactions were carried out in the cold, and in the absence of a catalyst. From the fact that sucrose, a-methylglucoside, and tetramethyl a-methyl-glucoside were unaffected under these conditions whilst glucono-lactone was converted into gluconnmide, the deduction is made that the formation of the scscalled “imines” of the sugars is due to condensation of tho reducing group with one molecule of ammonia.These imines are thus to be regarded as unstable amino-sugars, and the absence of salt formation is due to the ready hydrolysis of the complexes. According to this view of the structure of these compoiinds, reducing sugars should be capable of condensation with both primary and secondary amines, and it is now shown that glucose reacts with ethylamine, diethylamine, and dimethylamine to give ethylamz‘noylucose, diethylaminoglucose, and dimethylamino-glzi cose respectively. Ethylaminoglucose is crystalline, and shows measurable mutarotation, and the same change was detected in the case of “ glucoseimine.” The action of ammonia on lzvulose gave, in addition to 2:5-di- tetrahydroxybutylpyrazine, a second product, C,H,O,N, which, although inactive, was converted into glucosephenylosazone, dis- playing the normal rotation.The constitution of this product, and the possible cause of the great variation in stability shown by amino-sugars were discussed. 11. I' Th chlorination of iodophenols. Part 11. The chlorination of o-haloid derivatives of p-iodophen01." By George King and Hamilton McCombie. The work described by Brazier and McCombie (T., 1912, 101, 968) on the chlorination of p-iodophenol has now been extended to other p-iodophenols in which one or both of positions 2 and 6 is occupied by another halogen atom.Willgerodt (Ber., 1892, 25, 3495) states that when 2:4:6-tri-iodophenol is chlorinated in chloroform solution only an oily substance results. The authors have confirmed this result, but were able to obtain an iodo-dichloride when either carbon tetrachloride or light petroleum was employed as the solvent. This iodo-dichloride is more stable than the one derived from piodophenol, and differs further frpm the latter compound in that on decom-position chlorine is liberated and tri-ioclophenol is regeneralxd. As both the solvent and the temperature employed in these chlorinations had an influence on the products obtained, a detailed study of these influences was made. In glacial acetic acid at 15O the main products of the reaction were (1) a tetrachloro-compound : and (2) chloroanil.In boiling acetic acid solution a copious yield of chloroanil was obtained. 3 :6-Dibromo-4-iodophenol gave an iodo-dichloride which resembled the compound derived from tri-iodophenol in that on decomposing chlorine is evolved and the original phenol is regenerated. It has been shown by Brazier and McCombie that 2 :6-dichloro-4-iodo-phenol can be converted into an iodo-dichloride which decomposes with evolution of hydrogen chloride and the formation of a further substitution product. Hence the presence of two bromine or two iodine atoms in positions 2 and 6 protects the hydrogen atoms 3 and 5 from attack. 2 :4-Di-iodophenol and 2-bromo-4-iodophenol both yield id+ dichlorides which on decomposing lose hydrogen chloride and give 6-chl01-0-2:4-di-iodophenol and 6-chloro-2-bromo-4-iodophenol respec-tively.While the iodophenols described yield unstable iodo-dichloridee, it has been found in this case, as was noticed in the case of p-iodo-phenol, that the dcyl derivatives yield stable iodo-dichlorides. In the case of all ths polyiodo-compounds which are described it was found that only one of the iodine atoms becomes tervalent. 9 In these cases evidently the hydroxyl and acyl groups destroy the tervalency of the iodine atoms in the same way as the methyl group does in 2 :4-di-iodotoluene (Willgerodt and Simonis, Ber., 1906, 39, 269) and the nitro-group in 3 :5-di-iodonitrobenzene (Willgerodt and Ernst, Ber., 1901, 34, 3406).12. ‘‘ Quercetagetin.” By Arthur George Perkin. Quercetagetin, C,,H1008, the colouring matter of the African marigold (Y’agetes ptula) (P., 1902, 18, 75), when methylated with excess of methyl iodide and alkali gives quercetagetin pentamethpl ether, C,,H,O,(OMe),, pale yellow needles, m. p. 161-162O, and querce tage tin hexamet hyZ ether, Cl5R4O2(OMe),, colourless needles, m. p. 157-158O. Quercetagetin hexuethyl ether, C1,H4O2(0Et),, colourless needles, m. p. 139-141°, by hydrolysis with alcoholic potassium hydroxide gives protocatechuic acid diethyl ether, and a ketone, puercetagetoz t e truethyl ether, HO*C,H(OEt),*CO *CH2*OEt, prismatic needles, m. p. 46--48O, which yields the oxime, C16H2,06N, m.p. 93-950, and with permanganabe an acid (quercetagetinic acid), needles, m. p. 100-102°. The pentahydroxyflavonol consti. tution : OH is assigned to quercetagetin, which is thus isomeric with myricetin (T., 1911, 99, 1721), but the positions of the hydroxyl groups, O:O€I:OH:OH*, in the tetrahydroxybenzene nucleus have not yet been decided. Acetylquercetagetin melts at 209-211°, and not at 203-205° as previously stated. b613. Hydroxyquinol- phthalein anhydride and hy droxy qui nol-benzein.” By Kedar Nath Ghosh and Edwin Roy Watson. From certain theoretical considerations it was argued that gallein, pyrogallol-benzein, and a compound obtained from benz- aldehyde and pyrogallol by condensation with hydrochloric acid (M. Hofmann, Ber., 1893, 26, 1139) should have valuable dyeing properties.It was found that pyrogallol-benzein has dyeing pre perties equally as good as those of gallein, but its good properties have probably been overlooked on accoupt of an unfavourable report (Doebner and Forster, Annulen, 1890, 257, 63). The con-densation of benzaldehyde and pyrogallol gives no dyestuff. H ydmxypuznol-ph thalein anhydride, C2,HI2O,, obtained by con-densing hydroxyquinol and phthalic anhydride, separatee from 10 alcohol in red crystals; it forms a tetra-ncetyb derivative, C20H803(0A~)4,crystallising from benzene in colourless, rhombic form, melting at 267O. It dyes mordanted wool scarlet on alum and tin, violet on chrome, and brownish-black on iron mordants.The shades are not fast. Hydroxy puiizol-benzein, C38H2AOll,was produced by condensing hydroxyquinol aiid benzotrichloride. It is obtained as a dark red, amorphous sdbstance by hydrolysing the pure tetra-acetyb deriv-ative, C38H2,07(0Ac),, which separates from benzene in yellow, needle-shaped crystals, melting at 235O. Hydroxyquinol-benzein dyes exactly the same shade as the corresponding phthalein anhydride, and the dyeings are also not fast. 14. 2 :2’-Ditolyl-5:5’-dicarboxglic acid.” By James Kenner and Ernest Witham. The dinitrite, m. p. 158O, dimethyl ester, m. p. 134O, and diethyl ester, m. p. 76O, of 2 :2/-ditolyl-5 :5/-dicarboxylic acid were prepared by the action of copper powder on the corresponding derivatives of o-iodo-p-toluic acid.Tetramethyl di-vhenyl-2 :5 :2/ :5/-tefracnrboxyZate, m. p. 156O, was obtained in a similar manner from dimethyl iodoterephthalate. The properties of certain of these compounds differed from those observed by Liebermann in compounds to which he attributed the same constitution, and the conclusion was drawn that the latter derivatives were differently constituted. 15. ‘‘The carbonylferrocganides.” By Herbert Ernest Williams. The carbonylf errocyanides exist in the mother liquor resulting from the working up of “cyanogen mud.” They can be recovered by precipitating with ferric salts, boiling the precipitate with lime, precipitating the f errocyanide present as calcium ammonium f erro-cyanide, by converting a portion of the liquor into the ammonium salt, mixing with the bulk, and boiling.The filtrate is boiled with lime to remove the excess of ammonia and the salt allowed to crystallise. The salts of the alkali- and alkaline earth-metals, including lithium and magnesium, are very soluble, and several are deliquescent. The salts of the heavy metals are for the most part insoluble in water ;lead, chromic, stannic, and alumina salts produce no precipitate. The following salts were described : Ammonium salt, (NH,)3Fe(C”),C0,3H,0 ; 11 dimethylaniline salt, (C,H,*NMe~3H3Fe(CN),C0,8H20, sparingly soluble; diethylaniline salt,, (C,H,*NE~),H3Fe(CN),C0,3H20, spar-ingly coluble ; barium salt, Ba3[Fe(CN),C0],,14H20. The calcium salt, Ca3[Fe(CN),COJ2,SH20, is deliquescent and forms double salts, CaKFe(CN),C0,5HB0 and CaNH4Fe(CN),,C0.The cobalt salt, C'O,[F~(CN),CO]~,~~H~O,is reddish-pink, loses 13H20 at looo, and turns blue ;it also forms the salt, Co4K[Fe(CN),C0],,2lH,O. The cadmium salt, Cd,LFe(CN),C0],,7H20, is white, and becomes an-hydrous at looo;the cupric salt, CU,[F~(CN),CO]~,~~H,O, is pale green, and loses 7H20 at looo; when crystallised from ammonia it gives the salt, CU,~F~(CN)~CO]~,~NH,,~H,O,which is olive-green, and also forms the salt, Cu7K,[Fe(C"),CO],,XH20. The lithium salt, Li3Fe(CN),C0,4H,0, is deliquescent, and loses 2H,O at looo. The maynesium salt, i\lIg,[Fe(CN),C0]2,16H20, loses 10H20 at looo; the maitganese salt, Mn3[Fe(CN),CO],,18H20, is white, loses 15H20 at looo, and when oxidised with nitric acid forms a dark brown manganomanganic salt.The niclxl salt, Ni,[l?e(CN),C0]2,1 3H20, is apple-green, loses EH,O at looo, and with ammonia gives the pale blue salt, Ni,[Fe(CN),C0~2,2NH3,4H,0. The zinc salt, Zn3[Fe (CN) 5CO],, 7H,O , is white, loses 4H,O at looo, and gives with ammonia the salt, Zn,[Fe(CN)5C0]2,4NH374H20. 16. ''The so-called disodium derivative of diethgl malonate." By Alexander Killen Macbeth and Alfred Walter Stewart. In the course of an investigation of the absorption spectra of malonic acid derivatives, the results of which will be published shortly, the authors have been led to examine the spectra of solu- tions of diethyl malonate and diethyl methylmalonate in the pres- ence of sodium ethoxide; and as the results do not form part of the main work they are now published.It was for some time assumed that diethyl maIonate was capable of forming both a mono- and a di-sodium derivative. The latter substance would have the coinposition N+C7H,,0, ;but Vorlander (Ber., 1903, 36,268) threw considerable doubt on its existence, as molecular-weight determinations in boiling alcohol (Vorlander and Schilling, ibid., 1899, 32, 1876) showed that it behaved as if it were a mere mixture of the monosodium derivative with sodium ethoxide. Vorlander concluded from an examination of the con- ductivities of solutions of the free ester, the sodium derivative, and sodium ethoxide, that a &rue sodium substitution product was present, and not a mere additive compound of one molecule of ester 12 plus one molecule of sodium ethoxide.To this substance he ascribed the formula CHNa(C0,Et)2, thus representing it as a C-derivative and not an 0-derivative. Considerable doubt is thrown on this conclusion by the later work of Haller and Muller (Compt. rend., 1904, 139,llSO), for by means of the refractometric method they were able to show that malonic derivatives were salts of $-acids having the metallic atom attached to a non-carbon atom. On this assumption, the formula of the monosodium derivative of diethyl malonate would be NaO*C(OEt):CH*C02Et, whilst the disodium derivative would be NaO-C(OEt):C:C(OEt)*ONa. Sub-stances of such structures should differ very considerably from one another, and it seemed possible that some fresh evidence might be obteined from this point of view with regard to the existence of the supposed disodium derivative.Diethyl malonate in the presence of excess of sodium ethoxide shows a band in its spectrum which is not found in that of the free ester. The band has its head at oscillation frequency 3900, and occurs in N/1000-ester solution in the presence of N/lO-sodium ethoxide. This band might be due to the presence of either a moEo-or di-sodium derivative. In order to decide between the two, the spectrum of diethyl methylmalonate in the presence of excess of sodium ethoxide was photographed, and it was found that the band observed in this case was exactly similar to the other, although it occurred at a higher concentration (N/lOO-ester with N/10-sodium ethoxide).Since in diethyl methylmalonate only one displaceable hydrogen atom remains, it seems fair to conclude from the resemblance between the spectra that only one hydrogen atom is displaced by sodium in diethyl malonate; and that even in the presence of excess of sodium ethoxide no disodium derivative is produced. The reason for the difference in the dilutions at which the heads of the two bands appear may be traced, in part at least, to the fact that although the concentration of sodium ethoxide is the same in both cases, in the solution of diethyl malonate there are two hydrogen atoms capable of being displaced for every one such hydrogen atom in the diethyl methylmalonate solution.Hence the amount of sodium derivative formed will be less in the latter case than in the former. This view is stFengthened by the fact that when a series of solu- tions containing sodium ethoxide and diethyl malonate were examined, the penetration of the band was found to diminish as the quantity of ethoxide was decreased, that is, as the number of collisions between ethoxide and ester molecules was lessened. It seems evident that spectroscopic evidence cannot be brought into 13 agreement. with the idea of the existence of a disodium derivative of diethyl malonate. The following figures give the outlines of the various curves. The dashes indicate the region of the bands, and the figures on the left hand represent the logarithms of thicknesses of N J100,OOO-solution.Diethyl Malonate in the Presence of N/ 10-Sodium Ethoxide. Log. thicknesses. Spcctrum transmitted to 1/~. 50 340 40 3.52 30 363 24 366 23 369-414, 428 22 373-400, 430 21 Head of band, 434 20 43 8 Diethyl Methylmalonute in the Presence of N/ 10-Sodium Ethoxide. Log. thicknesses. spectrum transmitted to l/h. 40 344 33 365 32 367-414, 428 31 367-413, 428 30 Head of band, 428 Diethyl Malonate (NJ 100) in the Presence of N/ 1000-Sodium Etlzoxide. Log. thick11esses. Spectrum transmitted to I/h. 49 418 40 444 Diethyl! Malonate (N/ 1000) in the Presence of N J 100-Sodium E thoxid e. Log. thicknesses. 8pectrum transmitted to I/A. 39 363 36 367 -414, 431 34 867-414, 442 33 374-400, 444 32 Head of band, 444 Diethyl Methylmalonate (NJ 100) in the Presen.ce of N J500-Sodium Ethoxid e.Log. thicknesses. Spectrum transmitted to 1/~. 49 367 48 37 1 47 371 46 423 40 442 14 Diethyl iWethyl,malonate (Ni 1000) in the Presence of N/5O-Sodizim Ethoxide. Log. thicknesses. Spectrum transmitted to Ijh. 39 367-413, 427 3s 367-413, 427 37 373-400, 42Y 36 Head ot’band, 428 30 444 17. (‘&-Derivatives of adipic and P-methyladipic acids ; and the preparation of muconic and p-methylmuconic acids.’’ By Henry Stephen and Charles Weizmann. A full description wa;s given of the compounds of which a pre-liminary account has been published (P., 1912, 28, 94), and also of the following : Methyl as-dibromoadipat e, CO,Me*CHBr*CH,*~H,*CHBr*CO,Me, crystallises from alcohol in white needles melting at 75O, and distil- ling at 18Z0/10 mm. The corresponding ethyl ester melts at 65O and distils at 195Oj10 mm.Muconic acid melts a9d decomposes at 298O. The methyl ester melts at 15S0, and distils at 185O/12 mm. The ethyl ester distils at ZOOO/ 12 mm. /3-fMethylmuconic acid, CO,H*CH:C‘Me*CH:CH=CO,H, is a white, crystalline powder melting and decomposing at 235O. The methyl ester distils at 145O/9 mm., and the ethyl ester at 175O/10 mm.; both are colourless liquids. 18. (‘The measurement of tryptic protein hydrolysis by determina-tion of the tyrosine liberated.” By Samuel James Manson Auld and Thomas Duncan Mosscrop.Brown and Millar’s method of following tryptic protein hydro- lysis cannot be carried out in ordinary protein digests without the use of an external indicator, since the bromination of tyrosine is not momenta1 towards the end of the reaction. Starch and iodine cannot be used to detect the end-point, since the solution is acid. A suitable indicator for small quantities of bromine (in the presence of sodium bromide) is methyl-violet, which shows marked colour changes. 19. The interaction of iodine and thiocarbamide.” By Hugh Marshall. In the Transactions for November last there appears a paper by E. A. Werner on “The Interaction of Iodine and Thiocarbamide. The Properties of Formamidine and its Salts,” in which the author 15 refers to work done by me in connexion with the same subject (Yroc.Roy. SOC.Edin., 1902, 24, 233). The statements regarding my work and views are so inaccurate that I can only assume that they have been based on some abstract of my paper, and not on the paper itself; thus, on p. 2169 of Werner’s paper it is stated, in reference to my work and earlier work by McGowan: ‘(Unfortun-ately both these investigators were misled as regards the true nature of the compound formed, which they considered to be an additive compound, ( dithiocarbamide di-iodide,’ (CSN2H,),12, the forma- tion of hydriodic acid and the saline character of the substance having escaped their attention.” As my original paper is not readily accessible to chemists gener- ally, it may be permissible to quote the following passages from it, to show how incorrect the above statement is, so far as it regards my views, and to show that much of what is contained in Werner’s paper had already been made known.On p. 236 (Zoc. cit.): “The nature of such a second reaction is suggested by the saline nature of the compound, and the pheno- mena are explicable on the assumption that in aqueous solution the di-iodide undergoes ionisation, and that the increased ionisation produced by the dilution is the cause of the diminished dissociation. In addition to the first balanced action: [(CSN,H,)& zz 2CSN,H,+I,], we may therefore assume the second one, represented by the equation : (CSN,H,),12 = (CSN,H,),” +2I’. ‘(This assumption that the di-iodide and its analogues are true salts is justified by the readiness with which they undergo double decomposition with other salts, as exemplified by the precipitation of the sparingly soluble dinitrate.Further, the aqueous solution of the di-iodide dissolves free iodine, like solutions of metallic iodides ;it precipitates lead iodide and silver iodide from solutions of lead and silver salts; with mercuric chloride it gives a precipitate of mercuric iodide, soluble in excess of the di-iodide.” On p. 238: “It will be observed that thiourea is to a certain extent analogous to a metal; a molecule of it corresponds to half an atom of a dyad metal. Like a metal, it unites directly with the halogens to form salts. It can ( reduce ’ metallic salts from a higher to a lower stage; thus, Rathke (Bey., 1884, 17, 297) found that it acts upon cupric sulphate to form cuprous sulphate-momentarily- and the sulphate corresponding to the di-iodide : CuSO, + 2CSN,I14= Cu,SO, + (CSN,H,),SO,.The cuprous su1phat.e unites with more thiourea to form a complex compound. Ot,her cupric salts behave in a similar manner. “When thio-urea is added to a concentrated solution of ammonium persulphate there is a considerable evolution of heat, and, on cooling, the above sulphate separates out, whilst ammonium sulphate remains in solution : 2CSN2H4 +(NH4)2S,O8 =(CSN2H&SO4 +(NH~)zSO~, corresponding to such an action as: Zn +(NH,),S208=ZnSO, +(NH4),S0,. “The exact constitution of the class of salts here dealt with does not appear to have been very fully investigated, and in what precedes I have simply adopted the formuh generally employed.Adopting the imide formula for thiourea, the most plausible assumption is that the salts may be represented by the graphic formula : y3,X y3,X H N: C-S-S-C :N H’ The difficulty of satisfactorily investigating this and other points is considerable, owing to the instability of the hydroxide of the corresponding amine base.” In the interval since the publication of my paper I have, in conjunction with Mr. Blackadder, studied these substances further, and the publication of the results has only been delayed in order to allow of completion of certain details. At the Dundee meeting of the British Association I made a short contribution on the subject, especially with regard to analogous compounds containing the group =S=S*S*in place of *S*S*.17 ADDITIONS TO THE LIBRARY. I. Donations. Annals of Philosophy; or, magazine of chemistry, mineralogy, mechanics, natural history, agriculture, and the arts. By Thomas Thomson. 16 vols. London 1813-1820. [VoZs. 1 and 2, second edition.1 -New series. [Edited by Richard Phillips. 12 vols. London 1821-1826. (Reference.) From Mr. J. A. Audley. 11. .By Purchase. Brislee, F. J. An introdyction to the study of fuel. London 1912. pp. xxii+269. ill. 8s. net. (Recd. 12/12/12.) Hofer, Hans von. Das Erdol und seine Verwandten. 3rd edition. Brnunschweig 1912. pp. xvif 35I.M. 12.--. (Recd. 12/12/12.) Hoffmann,M. R. Lexikon der anorgsnischen Verbindungen. Vol. I., etc. Leipzig 1910 +. (Rpferencc.) Kohler, Hippolyt. Die Fabrikation des Russes und der Schwarze. 3rd edition. Braunschweig 1916. pp. viii+229. ill. M. 7.-. (Recd. 12/ 12/ 12.) Landolt, Hans Heinrich, Biirnstein, Richard, and Roth, Walther A. [With others.] Physikalisch-chemische Tabellen. 4th edition. Berlin 1912. pp. xvi + 1313. M. 56. -. (Reference.) 111. Pamphlets. Beam, JViZZiam. The determination of humus, especially in hetlvy clay soils. (From The Cairo Sci. J., 1912, 6.) Bocci, Balduino. La semplificazione degli enzimi col metodo combinato dell’ autolisi e della dialisi. (From the Proc. ve7.b. R. Accad. Fisiocritici, Siena, 19 12.) Bruni, G.Reazioni di doppio scambio in chimica organics. (From the Atti R. Inst. Veneto Sci., 19 11, 70.) Bruni, G., and Amadori, M. Sul calore di formazione delle soluzioni solide, (From the Atti R. Inst. Veneto Sci., 1911, 71,) Bruni, G., and Meneghini, D. Sulla formazione di soluzioni solide fra sali alcalini per diffusione a110 stato cristallino. (From the Atti R. Inst. Veneto Sci., 1911, 71.) Gramout, Amaud de. Sur les spectres stellaires et leur classification. (From the Annuaire bur. Jes Lowjtucies, 1911.) 18 Gramont, Arnaud de. Nouvel appareil a spectres d’btincelles des liquides sans raies d’klectrodes. (From the Compt Rend. Assoc. lirancaise Avance. Sci ,19 10.) --Notice sommaire sur les travaux ecientifiqiies. pp. 36. Paris 1910.(Together with 1G reprints of papers published in journals already in the Library.) Harrison, W. H., and Sivan, M. R.Ramaswami. A contribution to the knowledge of the black cotton sdaof India. (From the Mem. Dept. Ayric. India. Ciiem. Series, 1912, 2.) Inghilleri, G. Azione dell’ anilina sui sali di iiranile. (From the Atti R. Acccsd. Fisiocritici, Siena, 1911). Inghilleri, G., and Gori, G. Sc=alcuni sali complessi delllt chiriolina con i ssli d’uranile. (From the dtti R. Accad. Risiocritici, Simc6, 1909.) Jona, Temistocle. Crioscopia degli estratti di carne. pp. 15. Fossano 191 1. Ricerca di dipeptidi nelle sostanze estrattive dei muscoli. pp. 19. Fossano 1911. Sui cornposti azotati contenuti nell’ estratto di came.pp. 87. Fossano 19 11. Komppa, Gust. Ueber das y-y-dimethylpiperidin. (From the Ann. Acud. Sci. Pennicce, 1911, A, 3.) Luzzatto, R., and Satta, G. Intorno a1 comportamento nell’ organism0 animale del Psrajodanisolo. (From tliv Arch. Farm. spwim., 1912, 13.) Miyake, K. Ueber das Verhalten der Pentosane und Methyl-pentosane der Samen von Glycine hispida uncl von Phaseolus vulgaria wahrend des Keimungsvorganges. (From the J.Coll. Ayric., Tohoku Imp. L‘niv., Sapporo, Japan, 1912, 4.) -An improvement of the method for the determination of Galactan. (From the J. Coll. Ayric., Tohoku Imperid Ur&srsity, 1912.) Ottolenghi, Donato. Ueber die Wirkung der SPuren der Basen rind einiger Salze auf die bakteriziden Sera. (From the Zeitseh. Im-munitutsforsch. exp.5!’fter., 19 12.) Riy, I+*afullcLCiiandra, and Datta, Rasik Lal. On isomeric allyl- amines. (From the J.and Proc., Asicctic SOC.Bsnyal, 1912, N.S. 8) Rothermundt, M., and Dale, J. Experimentelle Studien uber die Wirkungxweise des Atoxyls in vitro und im ‘L’ierk8rper. (From the Zeitsch. Immunitatsforsch. exp. l’herapie, 1912, 12.) Rupp, E.,and Kropat, K. Ueber eine einfttche Bastirnmnng des Gesamtquecksilbers in Hydrargyrum s slicylicum. (From the Apolh. Zeit., 1 9 12,) 19 Schirmer, Wolfgnng. Beitrage zur chemischen Kenntnis der Gummi- und Schleimarten. pp. 67. Strassburg i.E. 1911. Schmidt, Emst. Ueber das Kreatinin. (From the Apoth. Zeit., 1912). Ueber die Darstellung des Glycocyamidins. (From the Zeitech.AZZg. Oesterr. Apothekeruereiws, 1912.) Schottky, Hermann. Ueber die Veranderungen von Blattmetallen beim Erhitzen infolge von Oberflachenkriiften. (From the Nachc. k. Ges. Wiss. Gottingen, 1912.) Tammann, 6. Ueber die Abhangigkeit der Krystallform von der Temperatur und die Rekrystal1isai;ion in Konglomeraten. (From the Nachr. K. Ges. Wiss. Gottingen, 1912.) Tammann, G. Zur Thermodynamik der Gleichgewichte in Einstoff- systemen. (From the Nachr. k. Ges. Wiss. Gottingen, 1911). Valenti, Adriano. Contributo allo studio del comportamento nell’ organismo di alcuni derivati arsenicali organici (salvarsan e cacodilato di sodio. (From the Arch. Farm. sperim., 1912, 11.) Vassiliev, A. M. The origin of the names of the chemical elements. An attempt at a compilation.pp. 40. Kasan 1912. [In Russian.] Venth, Emst. Ueber emulsinartige Enzyme. pp. 53. Strassburg, i.E. 1912.) ANNIVERSARY DINNER. It has been arranged that the Fellows of the Society and their friends shall dine together at the Whitehall Rooms, Hotel Metro- pole, at 7 for 7.30 o’clock, on Friday, March 14th, 1913 (the day fixed for the Annual General Meeting). The Council has decided to invite Fellows to become Stewards for this Dinner, the additional liability of each Steward not to exceed 10s. 6d. The price of the tickets will be One Guinea each, including wine, and half a guinea each, not including wine. All applications for tickets must be received not later than Friday, March 7th, 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 Assist,ant Secretary, Chemical Society, Burlington House, W. 20 At the next Ordinary Scientific Meeting on Thursday, February 6th, 1913, at 8.30 p.m., the following papers will be communicated: “The presence of helium in the gas from the interior of an X-ray bulb.” By Sir William Ramsay. .‘The presence of neon in hydrogen after the passage of the electric discharge through the latter at low pressures.” By J. N. Collie and 11. Patterson. -. Vaubel’s supposed phenyldi-imine.” By 35. 0. Forster and .I.C. Withers. “The mode of combustion of carbon.” By T. F. E. Rhead and R. 17. Wheeler. “The latent heat of vapours.” (Preliminary note.) By M. P. ,%pplebey and D. L. Chapman. ‘ISome derivtLtives of o-xylene.” (Preliminary note.) By J. L. Simonsen. R. CIA1 AND SONS, I,TD. RHUhSRIClK ST., STilrlkOIll) ST., S.E., iND BUVOAT. OLFTOLL.
ISSN:0369-8718
DOI:10.1039/PL9132900001
出版商:RSC
年代:1913
数据来源: RSC
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