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Proceedings of the Chemical Society, Vol. 29, No. 411 |
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Proceedings of the Chemical Society, London,
Volume 29,
Issue 411,
1913,
Page 49-64
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[?smed 27/2/13 PROCEEDINGS OF THR CHEMICAL SOCIETY. Vol. 29. No.411. Thursday, February 20th, 13i3, at 8.30 p.m., Professor PERCYF. FRANKLAND,LL.D., F.R.S., President, in the Chair. The PRESIDENTreferred to the loss sustained by the Society through death of: Elected. Died. Otis Coe Johnson ............... Alxrcli sth, 1897 Theodore David Lichtenstein February 21st, 1879 (ieorge Matthey .................. May 3rd, 1870 B. Venkata Rao .................. Decembzr 7th’ 1911 June 6th, 1912 October 23rd, 1912 February, 14th, 1912 1912 Certificates were read for the first time in favour of Messrs. : Horace George Battye, 25, Roman Place, Roundhay, Leeds. Noel G uilbert Stevenson Coppin, KSc., Rydal Mount, Runcom, Cheshire. Harold Davies, 18, Windsor Road, Ilford.Fritz Haber, Post Lichterfelcle, 3, Berlin-Dahlem. Darab Dinsha Kanza, M.A., Indian Institute of Science, Bangalore. Emmanuel I?. Kur, Learansa, Devonshire Road, St. Anne’s-on- Sea. Bhaichand Anupchand Mehta, M.A., Indian Institute of Science, Bangalore. Francis Martin Potter, B.Sc., 6, Stavordale Road, Highbury, N. Arthur Samuel Robinson, B.Sc., King’s School, Pontefract. Reginald William Rusby, Westgate, Greenhill Road, Moseley, Birmingham. 50 Hormusji Kharshedji Sahiar, M.A., Indian Institute of Science, Bangalore. William James Stansfield, 12, Bell Hatt Terrace, Savile Park, Halifax. A Certificate has been authorised by the Council under Bye-law 1(3) in favour of: Ferrand Paget, Bombay Burma Trading Corporation, Ltd., Bangkok, Siam.The following announcements were made : (1) That the following changes in the Officers and Council were proposed by the Council: President to retire.-Prof. Percy F. Frankland. Secretary to retire.-Prof. Arthur W. Crossley. Foreign Secretary to retire.-Dr. Horace T. Brown. Vice-Presidents to retire.-Dr. M. 0. Forster and Prof. A. Liversidge. Ordinary Members of Cmcncil to retire.-Prof. UT.A. Bone, Mr. A. R. Ling, Dr. A. McKenzie, and Dr. J. C. Philip. As President.-Prof. W. H. Perkin. As I;'ice-Presidenztswho have filled the ofice of President.-Prof. H. E. Armstrong, Prof. A. Crum Brown, Sir William Crookes, Sir James Dewar, Prof. H. B. Dixon, Prof. Percy F. Frankland, Dr. A. G. Vernon Harcourt, Prof.R. Meldola, Dr. H. Muller, Prof. W. Odling, Sir William Ramsay, Prof. J. Emerson Reynolds, The Right Hon. Sir Henry E. Roscoe, Sir Edward Thorpe, and Sir William A. Tilden. As Treasurer.-Dr. Alexander Scott. -4s Zon. Secretaries.-Dr. Samuel Smiles and Dr. J. C. Philip. As Foreign Secretary.-Prof. Arthur W. Crossley. As ~ice-Presidents.--Prof. H. B. Baker, Dr. G. T. Beilby, Dr. Horace T. Brown, Prof. E. J. Mills, Prof. G. T. Morgan, and Prof. M7. Jackson Pope. As iYew Ordinary Membei-s of Council.-Dr. G. Barger, Mr. E. J. Bevan, Prof. F. G. Donnan, and Prof. K. J. P. Orton. (2) That Fellows were invited to attend a meeting of the Faraday Society to be held in the rooms of the Chemical Society on Wednesday, March 12th, from 4 to 6 and 8 to 10 p.m., when a discussion on " Colloids and their Viscosity " would take place.Prof. J. Millar Thomson, Dr. Samuel Rideal, and Prof. J. J. Dobbie were elected Auditors to audit the Society's Accounts. A ballot for the election of Fellows was held, and the following were subsequently declared elected : Theodore William Gull Acland. Peter Thomacr Lcitch. Neil Kensington Adam, R.A. Daniel William Lloyd, B.8c. William Bcuth. Walter Cyril Loynes. C‘rellyn Colgrave Bissett, B.Sc. Alexander Iiilleii Macbeth, M.A., B.Sc. Albert Brier, KSc. Henry Stephen Rlartin. Percy Charles Burr, B.Sc. Aylnier Henry Maude. John Hugh Christie, B.Sc. Joseph Horsnell May. Harold Reginald Septimus Clotworthy, Ernest Joseph bfumford.E.A., B.Sc. Paul Murphy. John Albert Cockshutt, M. Sc. Jonathan Harold Kaylor, BI.Sc. Charles George Cutbush. Thomas Joseph Nolan, pui. Sc. Daniel James Davies, B.Sc. Jonathan Parker. Roland Doumiii. CorneIius Theodore Pollard, B. Sc. James Henry Edmondson. William Norman Rae, B.A. Thomas Lenton Elliott. Hcrmann Horace Roskin, B.Sc. Click Richardson Evans, I3.A. William Slessor Simpson, M.A., E.Sc. Albert Edward Garrett, B.Sc. John Walter Ehnith, B.Sc. Tio Kari Gliose, B.A., L. M.S. Harold Victor Taylor. Robert Gilmour, B.Sc.. P1i.D. Percy James Thompson. George Watson Gray. Bertrand Turner, B.Sc. Douglas Henville. Thomas Willoughby Turnill. James Arthur Hewitt, B.Sc. Edward Webb, B. Sc. William Joseph IIolt. Siddons Sidclons Wilson.Alfred Leslie Howells, B.Sc. Hubert Rogers Wood. Thomas James Kirkland, E.Sc. Of the following papers, those marked * were read : “39. “The mode of combustion of carbon.” By Thomas Fred Eric Rhead and Richard Vernon Wheeler. The authors, in continuation of their work on the combustion of carbon, whereby they showed that carbon dioxide and carbon mon-oxide are produced together when carbon is burned, described experiments made to account for t,his simultaneous production of the two oxides. It was shown that carbon, at all temperatures up to 900° and probably above that temperature, has the power of pertinaceously retaining oxygen. This oxygen cannot be removed by exhaustion alone, but only by increasing the temperature of the carbon during exhaustion.When quickly released in this manner, it appears, not as oxygen, but as carbon dioxide and carbon monoxide. The proportions in which it appears in these two oxides when completely removed depends on the temperature at which the carbon has been heated during oxygen-fixation. It.was shown also t.hat no physical explanation alone can account 52 for this ('fixation " of oxygen, but that, in all probability, it is the outcome of a physico-chemical attraction between oxygen and carbon. Physical, inasmuch as it seems hardly possible to assign any definite molecular formula to the complex formed, which indeed exhibits progressive variation in composition ; chemical, in that no isdlstion of the complex can be effected by physical means.Decomposition of the complex by heat produces carbon dioxide and carbon monoxide. At a given temperature of decomposition these oxides make their appearance in a given ratio. Further, when a rapid stream of air at a given temperature is passed over carbon (which has previously been saturated with oxygen at t,hat temperature), carbon dioxide and carbon monoxide appear in the products of combustion in nearly the same ratio as they do in the products of decomposition of the complex at that temperature. It is therefore suggested that the first product of combustion of carbon is a loosely-formed physico-chemical complex, which can be regarded as an unstable compound of carbon and oxygen of an at present unknown formula, C,O,.It is probable that no definite formula can be assigned to this complex. DIscuSSION. Professor SMITHELLS,after commending the previous paper by the same authors for its new observations and as a lucid and trust- worthy account of the history of the controverted question of the combustion of solid carbon, said that he saw no prima facie objec- tion to the doctrine of C,O,. The case of the combustion of solid carbon was essentially different from that of carbon in gaseous compounds. In that case observa- tions on the rate of explosion of cyanogen mixed with different proportions of oxygen, and analysis of the gases in the flame of cyanogen, as well as spectroscopic evidence, pointed to carbon monoxide as the first product. The argument relating to the more likely co-operation of two molecules rather than three, C,N, -+ 0, rather than C,N,+ ZO,, as the first transaction in a molecular system, was not applicable to the case of solid carbon.The molecule of solid carbon, judging from the very high volatilisation tempera- ture of the element, was probably of great atomic complexity, and it could easily be believed that such an atomic complex in the stationary position of the solid state, rained upon by a shower of oxygen molecules, could, at a moderate temperature, result in the production of Cl,O,, where 5 and y might be very high numbers. The complex, of course, at a higher temperature would be resolve2 into the proportions of CO and C'O, conformable to the equilibrium 53 at that temperature of the system: solid carbon, carbon monoxide, carbon dioxide.Professor DONNANasked what period of time the authors waited after pumping off the gases in order to determine the final pressure of carbon monoxide and carbon dioxide in equilibrium with the assumed complex Cr,O,. As the carbon monoxide and dioxide were produced initially in the adsorbed layer or in the solid carbon, the establishment of equilibrium might take some time. Professor BONE,replying on behalf of the authors, said that tbe point raised by Professor Donnan was dealt with in the paper; the authors’ evidence for the formation of the complex C,O, was largely cumulative, and could only be judged by a detailed study of the experimental work as a whole.Speaking personally, he had still an open mind on the subject, although, like Professor Smithells, he had no a priori difficulty in accepting the idea of the primary formation of the said complex. With regard to the President’s remarks about the probable cause of the spontaneous combustion of coal, he thought that it might be attributed to the oxidation of the constituents extractable by pyridine, which decomposed on heating below 700°, yielding chiefly paraffin hydrocarbons and little hydrogen (see Burgess and Wheeler’s papers on “ The Volatile Constituents of Coal ”), and which were probably derived from the resinous matter in the vegetable debris from which the coal originated. “40. The interaction of bromine and the sulphides of /3-naphthol.Part II.” By Thomas Joseph Nolan and Samuel Smiles. The diacetyl derivative of the unstable sulphide was converted into the anhydride by treatment with boiling acetic anhydride and sodium acetate. This anhydride-termed isonaphtha$hioxin-was found to be different from that obtained by dehydrating the stable sulphide. With bramine it yielded a dibromonaphtha-thioxin, which was identical with the product formed by the inter- action of this halogen and the acetyl derivative of the unstable sulphide. Previous experiments (T., 1912, 101, 1420) had shown that with bromine this sulphide yields tfie dibromosulphonium-quinone, and it was concluded that the different result now obtained with the acetyl derivative is due to liberation of acetyl bromide at a preliminary stage of the interaction, the two cases being represented as follows : C20Hl,S(OH)2+ Br, =o:~,o~6:s:c,o~6:o+ 21IBr.C,,H,,S(OAc), + Br, =O:~,,,H6:S:C,,,’E-I,:0+ 2AcBr. Independent experiment proved that in the presence of acetyl 54 bromide and bromine the sulphoniuin-quinone yields the dibromo- naphthathioxin. The diacetyl derivative of the stable sulphide did not react with bromine under the conditions chosen in these experiments. It was also pointed out that the properties of the hydroxyl groups in the unstable sulphide correspond mith those of am unsaturated tertiary alcohol. 41 “The nomenclature of the rhamnose group and of other substances related to the aldohexoses.” By Hugh Harshall.In view of the definite establishment, by E. Fischer and K. Zacb (Ber., 1912, 45, 3761), of the configuration of “rhamnose” and “isorhamnose,” the author suggested the adoption of a systematic nomenclatura for the group, based on that of the aldohexose group, so as to avoid the multiplication of novel names and the use of prefixes “iso,” etc. It was proposed that the name rhamnose should be used for the whole isomeric group, and be prefixed by the stem of the name of the aldose having the same configuration; the individual names would then be :-(d-and I-) mannorhamnose (ordinary rhamnose), glueorhamnose (isorhamnose or isorhodeose), idorhamnose, gulorhanznose, galactorhamnose, talorhamnose, allo-rhamnose, altrorhamnose. It was also suggested that a similar prin- ciple should be applied in the case of other hexose derivatives which would have eight pairs of stereoisomerides; at least, to those con- taining any two different terminal groups out of the following four: CO,H, CHO, CH,-OH, CH,, such as the isomerides of glucuronic acid.42. ‘‘Some green iron cganogen compounds.” By Herbert Ernest Williams. A solution of ammonium ferrocyanide when boiled in contact with the air, forms a dull green deposit, which has the formula Fe,///Fe”(NH,),[Fe//(CN),],,SH,Osimilar potassium compound, ; a Fe2///Fe/’K8[Fe’/(CN),],,6H20, is produced by adding very dilute hydrochloric acid gradually to a boiling solution of potassium ferro- cyanide, and by substituting ammonium chloride solution for the hydrochloric acid t’he compound F~///FeN(NH,),K[Fe(CN),],,3H,O is produced.Somewhat similar compounds of ferrosoferric ferro- cyanides of a dull blue colour were prepared, agreeing with the formulae : Fe2”/Fe,Wa,[Fe(CN),I,,6H2O and Fe,’/’Fe,N(~H,),[Fe(CN),],,8H,0, 55 These compounds can be considered as molecular compounds of the ferric double salts and ferrous ferrocyanides, as in the case of the blue iron cyanogen compounds. Ferric ferrocyanide when boiled with concentrated nitric acid ia converted into the green compound, Fe7’//[Fe//Fe//1(CN),21,,54H20. By boiling ferric potassium ferrocyanide with nitric acid a green compound, Fe,,”~[Fe~~Fe,”’(CN),,],,lOOH,O,is obtained ;this com-pound is also produced by passing chlorine through freshly precipi- tated ferric ferrocyanide.The addition of ferric salts to a solution containing one equiva- lent of ferrocyanide and more than three equivalents of ferricyanide yields a fine dark green precipitate of the composition: Fe2g’~~K3[Fe~~F~~~’(~N),a]9,210H20. When ferrous potassium f errocyanide, obtained by distilling potassium ferrocyanide with dilute acid, is oxidised whilst still boiling with excess of nitric acid, the violet compound, Fe,lllK FFe2 /IF 1112L e (WIal,6Hz0,is produced. Cupric ferrocyanide when boiled with concentrated nihric acid also yields a f errof erricyanide of the composition Cu7[Fe’~Fe~~~(CN),2]2,30H,0. From a consideration of the formation of these green compounds, and particularly of the copper compound, it is probable that they are ferric ferroferricyanides, and not ferrosoferric ferricyanides.43. (‘Catalytic decomposition of hydrogen peroxide.” By Gwen Dyer and Alice Barbara Dale. It has been generally accepted on the authority of Bredig and Miiller von Berneck (Zeitsch. pl~ysikal.Chem., 1900, 31,389) that the cat>alytic decomposition of hydrogen peroxide in aqueous solution proceeds as a unimolecular reaction : H,OZ -+H2O +0. Bredig’s observations seem to have been made with solutions of about 0-0007 gram of hydrogen peroxide per C.C. The present authors find that in a solution containing 0.0025 gram of hydrogen peroxide per C.C. the action appears to be a bimolecular one: 2H,O,-+ 2H20 + 02.Fifty C.C. of the solution were kept at constant temperature of 20°, 2 C.C. of Bredig’s colloidal platinum solution being added as a catalyst. Successive quantities of 5 C.C. were titrated with potassium permanganate at exactly noted intervals, varying from five to ten minutes. 56 Taking C,, C&, C, ... as the volumes of permanganate required after intervals of t,, t, t, .. . minutes, the values of K were calcu- iated in accordance with each of the following equations: c(1). K=-1 .log'=c -1 .log--2, etc., for a reaction of the first t, -t, c, t, -t, c,order. (2). K=-, ----c1-"--c,c, t, -t, .',,c2-C',C', etc., for a reaction of the t,-t, second order. KU). K (2).0.005877 0.001547 0'0043 89 0'001558 0'00 5123 0'001621 0-003980 0,0017930'00 5006 0 001675 0'004592 0-001793 The discrepancy between the successive values of K shown in the first column, and the comparative constancy of the values calcu- lated in the second column, appear to indicate a bimolecular react ion.44. ''The decomposition of hydrogen peroxide by colloidal platinum." By Harold Llewelyn Bassett. Bredig investigated the decomposition of hydrogen peroxide by colloidal platinum, and found the change to be unimolecular (Bredig and Miiller, Zeitsch. physikal. Chem., 1900, 31,258). In subsequent discussions of the mechanism of the decomposition, Senter and Sand accept Bredig's result as to the order of the reaction, and the point seems to have been assumed to be finally settled (Proc.Roy. Soc., 1904, 74, 356, 566). The experiments were repeated by Miss Dyer and Miss Dale (see preceding abstract), but it was noticed that very poor unimolecular constants were usually obtained, and the results often corresponded more closely with a bimolecular change. It appeared of interest to investigate the cause of these apparent anomdies, and it was found that the order of the reaction depends entirely OLI the coiicentration of the hydrogen peroxide. Bredig and others worked with solutions of about 1/50 gram-molecular weight per litre, or even greater dilution than this, and at these dilutions the decomposition certainly is unimolecular. On increas- ing the concentration, however, the reaction slowly becomes bimolecular, and bimolecular constants are obtained at a concen-tration of about li9 gram-molecular weight per litre.After this, increase of concentration does not affect the order of the reaction, 57 but owing to the rapid evolution of oxygen the experimenta1 diffi- culties in obtaining constants become very great. Nernsth suggests that in such cases as these the velocity measured is not that, of the chemical change, but simjly that of the diffusion of the solute to the surface of the particles of colloidal metal. Be assumes that equilibrium is at once set up when this surface is reached. Senter and Sand discuss this hypothesis and the importance of the part played by convection in the liquid. Their results suggest that the hypothesis, if at a.11 true, will have to be considerably modified to acccunt for the observed values for the velocity constants.It is assumed all through these papers that decomposi- tiori of the hydrogen peroxide actually takes place when the molecules come into contact with the surface of the platinum. This would account for the action being unimolecular, but it is difficult to see how a bimolecular change can be explained in this way. A single molecule would break up when it reaqhed the surfaca of the pla.tinum, and this decomposition would have no connexion with that of other molecules. To account for the bimolecular change in stronger solutions it is now suggested that, as the concentration increases, hydrogen peroxide molecules meet in the film of solute surrounding the platinum particles without ever reaching the surface of the platinum, and are decomposed in this surface film by contact with one another, possibly owing to the influence of surface tension. The opportunity for this would clearly be greater in stronger solutions, and with steadily increasing concentration it would gradually become the more important decomposition.Finally, in solutions giving a bimolecular constant, it is practically the only one taking place. Further increase of concentration, whilst increas- ing the amount decomposed, would have no effect on the order of the reaction, in agreement with experiment. The bimolecular decomposition depends on the presence of at least two hydrogen peroxide molecules in a given small space at the same time, and this will clearly depend only on the concentration of the hydrogen peroxide, and will not be affected by the amount of platinum present.This view as to the change in the character of the decomposition with increasa of concentration appears to explain satisfactorily all the experimental facts observed. In carrying out the experiments slightly acid hydrogen peroxide was used, the presence of acid having been shown by Bredig not to affect the course of the decomposition. Solutions of the various strengths were made up and placed in a thermostat at 25O. When 58 the solutions had reached the temperature of the bath, 2 C.C.of colloidal platinum solution were added to 100 C.C.of the hydrogen peroxide solution. These proportions were used in all the experi- ments. Titrations were made on 5 or 10 C.C.of the solution at intervals of five or teii minutes, according to the strength of the hydrogen peroxide. Potassium permanganate was used of strengths to give convenieut titzations in the various cases. An attempt was made to estimate' the hydrogen peroxide by potassium iodide in excess of sulphuric acid, but it was unsuccessful owing to the length of time required to complete the reaction with the hydriodic acid. With the stronger hydrogen peroxide solutions, great difficulty was experienced owing to the rapid evolution of bubbles of oxygen in the pipette, making accurate measurement very difficult. The figures at the heads of the columns below give the strengths of the hydrogen peroxide in gram-molecules per litre. The constants are calculated with ordinary logarithms as their actual magnitudes are not discussed, and as different strengths of permanganate were used, the bimolecular-constant values are not comparable, and are only to be considered as regards their constancy.Unimol eczclar Constants. 0'0034. 0'0141. 0.0208. 0.107. 0.119. 0.145. 0.205. 0 014 0.022 0'021 0'018 0.0043 0.0075 0 0083 0.016 0.024 0'023 0 012 0 0041 0*006Y 0'0066 0.015 0.022 0.020 0.011 0*0040 0.0062 0-0072 0.013 0.019 0'018 0'010 0.0032 0.0057 0-0071 0 015 0,017 0.017 0.008 0-0036 0.0051 0.0053 0.015 0.015 0'015 0.008 0.0035 0-0054 0'006i Bimole cular Constants.0.0034. 0'0141. 0.0208. 0.107. 0.119. 0.146. 0'205. 0*0036 0.002s 0 0027 0*0016 0.0050 0'001E 0'0012 0.0047 0-0042 0.0038 0.0019 0*0049 0'0015 0.0011 0'0048 0'0049 0 0042 0.0022 0-0051 0.0015 0.0013 0'0052 0-0057 0'0048 0'0021 0'0346 0.0015 0.0013 0.0073 0 0061 0.0056 0'0020 0'0046 0'0014 0-0011 0*0090 0.0082 0,0058 0'0023 0.0050 0-0316 0 0012 45. '* The absorption spectra of substances containing labile hydrogen atoms." By Peter Joseph Brannigan, Alexander Killen Macbeth, and Alfred Walter Stewart. An examination of various compounds containing a displaceable hydrogen atom showed that they may be divided into two classes: (a) those which, whilst showing ody general absorption in alcoholic solution, give rise to a banded absorption in presence of alkali; and 59 (b) those which do not conform to this rule, even when the sodium derivative can be isolated.With regard to the first class of compounds it has been found that several derivatives of malonic acid develop bands the penetration of which is dependent on the amount of alkali present in the solution. This confirms Hantzsch’s observations on ethyl acetoacetate. The bands are evidently due to the presence of the sodium derivatives of the various substances, and have nothing to do with the tautomeric changes assumed by Baly and Desch to explain their existence. To explain the differ- ence between the spectra of the enolic form and the sodium salt, Hantzsch’s suggestion of internal complex salt formation may be accepted, or an alternative one based on Gebhard’s views on affinity may bO employed.In either case it seems that if a band is to be produced by the sodium salt the sodium atom must come into the 1:5-or 1:6-position with regard to a carbonyl group, as the sodium derivative of urethane shows no band in its spectrum. A similar explanation can be put forward to account for the presence of the band in the spectrum of ethyl j3-aminocrotonate. 46. ‘‘ Researches on the constitution of physostigmine. Part 11. The synthesis of 3-dimethylaminoacetyl-2-methylindoleand 2-~-dimethylamino-~-hydroxgpropylindole.”By Arthur Henry Salway. The author described the synthesis of two indole derivatives containing an aliphatic sidechain, which is oxygenated, and possesses a tertiary basic nitrogen atom, in combination with the indole nucleus, namely : /\--~~CO-CH,-NM~, f\-F \/\/C*CHs and \/\/C*CH(NMe,) *CH2*CH,*OH.NH NH These substances were prepared for the purpose of comparing their properties with those of eseroline, C13H180N2,which has previously been shown (T., 1912, 101, 988) -to contain, in all probability, an indole complex. As a result of the investigation it is concluded that eseroline is not a simple indole compound containing an open side-chain. 47. Contributions to our knowledge of semicarbazones. Part 11. The semicarbazones of mesityl oxide.” By Forsyth James Wilson and Isidor Morris Heilbron. A semicarbazone of mesityl oxide (a-semicarbazone) melting at 164O has been prepared by Scholtz (Ber., 1896,29, 612), and further 60 investigated by Harries and Kaiser (Ber., 1899, 32, 1338).The authors find that this a-semicarbazone when exposed in chloroform solution to ultraviolet light is partly converted into a stereo-isomeride (&form) melting at 133-134O, the difference between the two forms being due to nitrogen isomerism in the sense of the Hantzsch-Werner hypothesis. The differences between the four semicarbazones of phenyl styryl ketone previously studied by the authors (T.,1912, 101, 1482) is due to nitrogen stereoisomerism combined with carbon stereoisomerism, whilst in the present case carbon stereoisomerism is excluded. The two modifications give practically identical absorption spectra, which are not affected by alkali; also, they undergo no change of colour in light.In order that absorption may bo affected by alkali and phototropy be evident, the authors conclude that carbon and nitrogen stereo-isomerism are both necessary. The a-semicarbazone on distillation yielded a substance melting at 1290, which is probably cyclic in structure (Scholtz, Harries, and Kaiser, Zoc. cit.). The same compound can be obtained by distil- ling the P-semicarbazone, a transformation of the P-into the a-form first taking place. On exposure in chloroform solution to ultraviolet light both modifications are partly converted into one another, an equilibrium between the two forms being established. 48. (‘Oxidation of the nitro-o-xylenes with dilute nitric acid.” By Charles Horne Warner.The two mononitrcw-xylenes are readily oxidised with dilute nitric acid, giving in almost quantitative amount the corresponding nitrophthalic acids (T.,1909, 95, 207). In view of this fact it seemed of interest to investigate the behaviour of this reagent towards the di- and tri-nitro-o-xylenes, especially since some of the nitrophthalic acids which it was hoped to obtain were required for comparison with substances resulting from other reactions. The oxidations do not, however, proceed smoothly ; the nitrophthalic acids are only obtained in small amounts, and the products are not easily isolated in a pure condition. When 3 :5-dinitro-o-xylene (ib id., p. 209) was oxidised with dilute nitric acid in sealed tubes, it yielded a liquid and a solid product..On evaporation, the former gave 3 :5-dinitro-o-phthalic acid (compare Merz and Weith, Ber., 1882, 15, 2708), which could not be completely purified by crystallisation alone, but was obtained, melting at 225O, through its monoethyl ester (Beilstein and Kurbator, dr?naZen, 1880, 202, 227). The acid crystallises from 61 water saturated with hydrogen chloride in long, thin, flattened needles. The diethyl ester, obtained by heating the silver salt in a dry benzene solution of ethyl iodide, separates from alcohol in fine, colourless needles, melting at 73O. The ankydride was prepared by heating the acid with excess of acetyl chloride. It crystallises from a mixture of ethyl acetate and light petroleum (b.p. 40-80°) in stout, colourless needles, melting at 161O. Water very readily reconverts it into the acid, exposure to laboratory air being sufficient to effect this change. From the solid product mentioned above there was isolated 3 :5-dinitro-o-toluic acid melting at 206O (compare Jacobsen and Wierss, Ber., 1883, 16,1959). 3 :4-Dinitro-o-phthalic acid was obtained by the oxidation of the corresponding dinitro-o-xylene with dilute nitric acid. It separates from concentrated hydrochloric acid in small, colourless needles,. melting and evolving gas at 204-205O. The diethyl ester, prepared through the silver salt, crysfallises from alcohol in colourless needles melting at 69O. 3 :4-Dinitro-o-toluic ncid, which is produced in the above reaction, crystallises from a mixture of ethyl acetate and light petroleum (b.p. 40-60°) in stout, colourless needles, melting at 182O. The ðyl ester was prepared from the silver salt of the acid ; it separafies from alcohol in colourless, rectangular plates, melting at, 63O. Both 3 :4 :5-trinitro-and 3 :4 :6-trinitro-o-xylene appear to be. completely decomposed when heated with dilute nitric acid in sealed tubes. 49. ‘‘Phosphonium and ammonium iodidesi.” By Alfred Holt and James Eckersley Myers. Phosphonium iodide vapour decomposes on heating when it is, dry, rendering the purification of this substance by sublimation extremely difficult. The substance appears to be unchanged when sublimed in the presence of traces of water vapour.The behaviour of ammonium iodide under similar conditions was described as a comparison. 50. ‘‘ The phosphoric acids and some phosphates.” By Alfred Holt and James Eckersley Myers. Experiments with two polymeric forms of metaphosphoric acid were described, and it was shown that the hydration of the mono- variety is unimolecular. 62 Experiments with glacial phosphoric acid lead to the belief that its vapour does not have a composition corresponding with the formula HPO,. Examination of the metaphosphates of the alkalis failed to give evidence that they are derived from acids other than mono- and tri -me tap hosp horic acids. 51. (( Optical activity and enantiomorphism of molecular and crystal structure.” By Thomas Vipond Barker and James Ernest Marsh.It was pointed out that no molecular configuration is enantio- rnorphous unless it is devoid of all the following three elements of symmetry-plane, centre, and alternating axis. Enantiomorphism is, however, compatible with the presence of ordinary axes of symmetry, so that an enantiomorphous structure is not necessarily asymmetric, that is, totally devoid of symmetry. The diuxssion of the conditions necessary for optical activity in the liquid and crystalline states leads to the conclusion that the optical activity of crystals of magnesium sulphate, monohydrated sodium dihydrogen phosphate, Schlippe’s salt, sodium uranyl acetate, sodium chlorate, and sodium bromate cannot be referred to a spiral arrangement of the molecules in the crystal edifice!, which arrangement is possible in quartz, cinnabar, and others, but must be due to the same cause as the optical activity in crystals of sucrose, namely, an enantiomorphous configuration of the molecule.Enantioniorphous constitutions developed on lines of co-ordination were proposed for the six substances in question. The inactive character of the solutions was attributed to auto-racemisation. 52. “Some double salts with acetone of crystallisation and the crystallisation of silver iodide, silver bromide, and cuprous iodide.” By James Ernest Marsh and W. C. Rhymes. The iodides of silver, lead, and copper form double salts with the alkali metal iodides, which are readily soluble in acetone.Many of these salts crystdlise well on evaporation of the acetone in dry air. The rubidium silver salt has the composition RbI,2AgI,2C3R,O, the potassium salt KI,2AgI,2C3H,0, and the ammonium salt, which crystallises in a different form, NH,I,2AgI,3C3H,0. These salts lose acetom readily on exposure to air. The potassium salt slowly deliquesces, and ultimately crystals of silver iodide are deposited from the solution thus formed. If lithium iodide and silver iodide in the proportion of LiI to 2AgI are dissolved in acetone and the solution is exposed to the air, no double salt separates, but large, transparent crystals of silver 63 iodide gradually form. Silver bromide has been obtained well crystallised from solution in lithium bromide and acetone.Crystal-line cuprous iodide has also been obtained from solution in lithium iodide and acetone. 53. “The relation between the absorption spectra of acids and their salts.” By Robert Wright. An examination of the absorption spectra in aqueous solutions of a number of acids and their sodium salts seems to justify the following conclusions: (1) There is not of necessity a relation between absorptive power and degree of ionisation, for many feeble acids show the same spectra as their highly, ionised salts. (2) Although change of absorptive power on salt formation may in some cases be due to a difference in the structures of the acid and its salt, still many acids show spectra different from those of their salts, even when such change of structure in the molecule is hardly possible.54. ‘(Synthetical experiments in the group of the isoquinoline alkaloids. Part 111. The constitution of anhydrocotarnine-acetophenone, etc., together with an account of some new condensation products of cotarnine.” By Edward Hope and Robert Robinson. The authors have submitted to a careful examination the con- densation products of cotarnine with acetophenone and ethyl phenylacetate, which were first described by Liebermann and his co-workers (Bey., 1904, 37,Zll), and regarded by them as deriv- atives of A’-methylaminoethylbenzaldehyde. It is now found that these substances are in reality derivatives of tetrahydroisoquinoline, and are therefore constituted analogously to narcotine and hydrastine.New condensation products of a similar nature have been prepared by the condensation of cotarnine with phenylaceto- nitrile, 1-hydrindone, 1:3-diketohydrindene, indene, isatin, fluorene, and 1-me thylindole. 55. “The identification of ipuranol and some allied compounds as phytosterol glucosides.” By Frederick Belding Power and Arthur Henry Salwag. It has previously been recorded in connexion with the description of ipuranol and some allied compounds to which distinctive names and formulze had been assigned, such as citrullol, trifolianol, ipurganol, bryonol, cluytianol, etc., that they yield colour reactions very similar to those given by the phytosterols. The observation 64 has now been made that several of these compounds, when heated under suitable conditions with aqueous hydrogen chloride, undergo hydrolysis, with the formation of a phytosterol and dextrose.The formula originally assigned to ipuranol, namely, CZ3H4,,O4, requires C= 72.6 ;H =10.5, whereas a sitosterol glucoside, C33H5606,requires C=72*3; H=10*2 per cent., and the latter figures are likewise in excellent agreement with the analytical results recorded for ipuranol and some allied compounds. The hydrolysis of ipuranol may there- fore be represented by the following equation : C,3H,,0, + H,O =C,,H4,0 + C6H&& It is concluded that all the conipounds of the type of ipuranol are glucosidic in character, although the phytosterols obtained by their hydrolysis are not in all eases identical.In place of the distinctive names which have previously been assigned to a number of these substances, it is proposed to designate them collectively as phytosterolins. 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 Assistant Secretary, Chemical Society, Burlingtoa House, W. The next Ordinary Scientific Meeting will be held on Thursday, March 6th, 1913, at 8.30 p.m., when the following paper will be communicated : “Quinonoid salts of nitroanilines.” By A. G. Green and F. M. Rowe. R. CLAY AND SONS, LTD., BRUNSWICK ST., STAMFORD 1T., S.E., AND BUNGAP, YUFFOLP.
ISSN:0369-8718
DOI:10.1039/PL9132900049
出版商:RSC
年代:1913
数据来源: RSC
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