|
1. |
Proceedings of the Chemical Society, Vol. 30, No. 435 |
|
Proceedings of the Chemical Society, London,
Volume 30,
Issue 435,
1914,
Page 289-300
Preview
|
PDF (730KB)
|
|
摘要:
[Ismud 11/12/14 PROCEEDINGS OF THE CHEMICAL SOCIETY. Vol. 30 No. 435 Thursday, December 3rd, 1914, at 8.30 p.m., Professor W. H. PERKIN,LL.D., F.R.S., President, and, subsequently, Dr. M. 0. Forster, F.R.S., in the Chair. The PRESIDENTannounced, with deep regret, that Dr. Cecil Reginald Crymble, of University Cbllege, London, who was elected a Fellow on May 4th, 1911, had been killed in action on November 20th. Mr. J. de Carle Smith was formally admitted a Fellow of the Chemical Society. Certificates were read for the first time in favour of Messrs.: Sidney Albert Brazier, M.Sc., 2, Mansfield Villas, Yardley Wood Road, Mmeley, Birmingham. Neal Brodie, B.Sc., Government Test House, Alipore, India. John Gerald Frederick Druce, Coorribe End, Whitchurch, Reading.Charles Hinde, 936, 8th Avenue West, Vancouver, British Columbia. Ronald MacInnes, 17, Shrewsbury Road, New Southgate, N. Arthur Dawes Robinson, B.A., Bradley Court,, Mitcheldean, Glos. Ramtaran Sen, L.M.S., Bacteriological and Chemical Labora- tory, Shillmg, Assam, India. 290 John Taylo'r, M.Sc. 3, Laurel Villas, Mardyke, Cork. Renry Terrey, B.Sc., University College, Gower Street, W.C. Su-Hian Ting, 130, Latchmere Road, Clapham Common, S.W. Mewrs. J. A. Goodson and H. King were elected Scrutators, and a ballot for the election of Fellows was held. The following were subsequently declared as duly elected : Hugh Logie Allan. Cliarles Cochrane Iles, M. D., D. P. H . Henry Atlas. George von Kaufmann, Junr.William Bacon, B. Sc. George King, M.Sc. Charles Kelway Bamber. Herbert Levinstein, M. Sc., Ph.D. Srish Chandra Banerji. Joseph Frederick Levy. Durgasanker Bhattacharj e. James Lyttle McKee, B.A., Ph.D. Arthur Henry Bowell. Benjamin Stanley Mellor, M. Sc. Alexander John Boyd. Alfred Edgar Newlnnd. John Rradshaw, M .Sc. Henry Cecil Ratcliffe. Frank Brinsley, M.Sc. Joseph Druminond Robertson. James Meikle Brown, B. Sc. Rajkuniar Sen, M.Sc. John Arthur Cresswick. William Kershaw Slater, B. Sc. Harry Cunliffe. Henry Michael Spiers, H.A., B.Sc. Frederick Raiiie Ennos, B. A., B. Sc. Alan West Stewart, D.Sc. James Ferguson. Mark Thonipson. Alexander Fleck, 13. Sc. Olin Freeman Tower, Ph, U. Ernest George, B.A. Hugh Vivian. George Noel Grinling. Arthur Henry Wardle.Thomas Clifton Hnrford. Of the following papers, those marked * were read: "281, "A redetermination of the atomic weight of tin." By Henry Vincent Aird Briscoe. The atomic weight of tin has been redetermined by measurement of the ratio 4Ag : SnC1,. The' stannic chloride was prepared from pure commercial tin and pure chlorine, and was purified by repeated fractional distillation. Its final purification and collection in weighed bulbs was effected by its decantatJon and fractional distillation in a sealed and exhausted apparatus. The amount of silver required to react with the chloride present was ascertaired by a gravi-volumetric method, the end-point being found by nephelometric tests. Precipitation of metastannic acid produced by the hydrolysis of stannic chloride in dilute solution during the analyses was prevented by the addition of oxalic acid or tartaric acid. All the usual precautions were taken.Fifteen concordant analyses of fifteen separate fractions of stannic chloride give for the atomic weight' of tin a mean value approximat- ing closely to 118.10. 291 DISCUSSION. Dr. SCOTTremarked that previous determinations of the atomic weight of tin seemed to centre round one or other of the numbers 118 and 119. The earlier experiments pointed to the lower number, whilst the later very concordant results of Bongartz and Classen (who employed five different ratios) seemed to indicate the higher number as the true value.A thorough revision on modern lines was therefore urgently needed, and he was glad the author had undertaken this work, even although that had resulted in a value between the two whole numbers given, thus removing tin from the list of elements the atomic weight of which closely approximated to a whole number. The obvious method of determining the atomic weight of an element by converting it into an oxide, or a lower oxide into a higher one (or the reverse process), too often gave unsatisfactory results, especially when the element formed a series of oxides. This suggested that perhaps a series of chlorides might be no better, and the higher chloride might be the most unsuitable when the behaviour of the higher chlorides of mercury, antimony, and phos- phorus on vaporisation was recalled.The author depended almost entirely on fractional distillation for the purification of his staniiic chloride. Dr. Scott agreed with the author that the methods, as well as some of the substances, employed by Bongartz and Classeii w0re almost cert-ain to give too high results. In reply to the President, Mr. BRISCOEsta7ted that it was iiot to be supposed that liquid chlorine supplied in steel cylinders was entirely free from impurity, but that such impurity, if present, would be eliminated during the subsequent fractionation of the stannic chloride; in any case, the purity of the chlorine was prob- ably of the same order as that of the tin. Replying to Dr. Scott, the author said that the difficulties attend- ing the fractionation in a vacuum were such that the investigation of the original end-fractions, in which the impurities might have been expected to accumulate, was not undertaken.The possibility that staiinic chloride might dissociate into stannous chloride and chlorine had not been overlooked, but con-sidering that the distillations took place below 30°, and that the chloride was, in most casw, condensed at the temperature of liquid air, it seemed likely that no dissociation occurred, or that if it did occur, the chlorine would be eliminated in the early fractions, With reference to Dr. Senter’s criticism that only one substance, stannic chloride, was analysed, it was pointed out thab tin formed so few compounds suitable for precise manipulation or analysis that the choice of ratios was very limited.292 b4“288. The isomerism of the oximes. Part VI. p-Dimethylamino-benzaldoxime.” By Oscar Lisle Brady and Frederick Percy Dunn. Contrary to expectation it has been found that pdimethylamino- benzaldoxime exists only in the anti-form, all attempts to prepare its isomeride having failed. The diphenylcarbamyl derivative, however, like the diphenylcarbamyl derivatives of other aromatic aldoximes, has the syn-configuration; on the other hand, it is possible ta obtain two carbanilino-derivatives, one of anti- and the other of syn-structure. DIsccssION. In reply to Dr. Forster, Mr. BRADY said that the question of inner-salt formation had been considered, but the authors were of opinion that this would not take place in the presence of the excess of hydrogen chloride in the formation of the hydrochloride.The possibility of salt-formation at the dimethylamino- in prefer- ence to the oximino-group seemed to be unlikely in view of the fact that an identical hydrochloride was obtained by the action of the oxime with hydrogen chloride and by heating the aldehyde to 50° in alcoholic solution with hydroxylamine hydrochloride. *289. (( Organo-derivatives of bismuth. Part 11. The stability of derivatives of quinquevalent bismuth.” By Frederick Challenger and Charles Frederick Allpress. By the action of iodine monochloride or monobromide on tri-p henylbismuthine, iodobenzene and diphenylchlorobismuthtine, BiPh,Cl, or diphenylbromobismutlhm respectively are produced.Diphenylchlorobismuthine (m. p. 184-185O) has also been pre- pared from triphenylbismuthine and bismuth chloride, and by boiling triphenylbismuthine dichloride with benzene. By the action of iodine on triphenylbismuthine, iodobenzene, diphenyliodobismuthine, and a red compound containing more than 50 per cent. of iodine are formed. The latter undergoes decom- position on extraction with hot benzene, yielding bismuth iodide. With cyanogen iodide, triphenylbismuthine gives theoretical yields of iodobenzene and diphemylcyanobismuthzne, BiPh,CN, which melts and decomposes at about 210O. When tri-a-naphthylbismuthine reacts with iodine, a portion is converted into iodonaphthalene and bismuth iodide, whilst some of the bismuthine is recovered unchanged.With iodine monochloride or monobromide at least 75 per cent. of the theoretical yield of iodonaphthalene is obtained, and this 293 is also formed by the action of iodine monochloride on diphenyl-a- naphthylbismuthine. Iodine monochloride and diphenylbromobismuthine interact with the production of iodobenzene and phenylchlorobromobismuthine. DIscusSION. In reply to Dr. Forster, Dr. CHALLENGERstated that the experi- mental difficulties connected with the manipulation of the trialkyl- bismuthinea were considerable, and that in the presence of air these substances could not be prepared by the action of magnesium alkyl haloids on bismuth bromide, owing to oxidation.The same was true of the action of magnesium benzyl chloride and magnesium cyclohexyl bromide. Attempts to prepare diphenylethylbismuthine by the action of magnesium ethyl bromide on diphenylbromobismuthine led to the formation of triethyl- and triphenyl-bismuthines. 290. The reduction of cupric salts by sugars.” By William Cramer. The reduction of cupric salts by sugars in alkaline solution proceeds readily as far as metallic copper. The formation of cuprous oxide, which is usually regarded as the end-point of the reaction, is only an intermediate stage at which the reaction may be stopped by using an excess of the cupric salt. 291. ‘‘ Some properties of solutions of the boric acids in alcohol. A modified boiling-point apparatus.” By James Brierley Firth and James Eckersley Myers.A form of boiling-point apparatus was described by which trust- worthy and steady readings may be obtained. It is found that the additton of small quantities of ortho- and meta-boric acids and boron trioxide to ethyl alcohol causes a lowering of the boiling point. The volatilities of solutions of these thre’e substances in alcohol have been measured, and it is found that the effect on the boiling point is least with the most volatile solute and vice versa. 292. ‘‘ A new method of preparing alkylated sugars.” By Walter Norman Haworth. The methods hitherto available for the alkylation of sugars and the simple carbohydrates generally have involved the application of alkyl iodides and dry silver oxide, which reagents were first 294 employed for the etherification of sugars by Purdie and Irvine (T., 1903, 83,1021).It has now been observed that practically all the methylated sugar derivatives obtained in the St. Andrew's laboratories during the past twelve years can be, prepared conveniently and expedi- tiously by the agency, under carefully chosen conditions, of methyl sulphate and commercial sodium hydroxide. Other sugar deriv- atives, not previously described, have also been prepared by this method. An important fact, which emerges as the result of this investi- gation, is, that methylation of the hydroxyl groups of a sugar-chain proceeds in definite stages, certain groups displaying a tendency to' undergo etherification in preference to others.These partly methylated sugars are well characterised, homogeneous sub- stances, which are formed as intermediate stages of the methylation process. The sub joined list of compounds, which were, described, serves to illustrate this point : Heptamethyl sucrose ..................... b. p. 193"/0.18IIIIII. Octamethyl ,, ............................. b. p. 176"/0'05 IIIIII. Tetramethyl methylglucouitle ................ b. p. 10So/O-l I~III. Trimethyl *..... ........... b. p. 124"/0'1 111111.39 Tetramethyl glucose ............................. m. p. 84". ,, niethylgalactositle ............... b. p. 110"/0.15Irliii. Trimethyl >? ........... b. p. 154"/18mni. Tetramethyl methylmannositle ............. b.p. llOo/O.33 nrni. Trimethyl ,> ............ b. p. 155"/18 nini. Dimethyl saliciu ................................. m. p. 122". Monomethyltartaric acid ........................ 111. p. 1'74". and various inethyl derivatives of mannitol and lactole. These substances have been characterised by their various physical properties, and with this improved means of preparation they are now rendered easily accessible for purposes of synthetic and other work which is in progress. 293. '' The rate of saponification of derivatives of ethyl benzoate." By Hamilton McCombie and Harold Archibald Scarborough. The rate of saponification of derivatives of ethyl benzoate by potassium hydroxide in absolute ethyl alcohol has been studied at 30°.The influence of halogen substituents is to raise the velocity of saponification in comparison with the uneubstituted ester, whilst hydroxyl, an?ino- and methyl groups have a strong retarding effect. The values obtained for bromo-substituted esters are a mean between those for the corresponding chloro- and iodo-derivatives, even in the exceptional case of the para-substit'uted compounds, 295 where the iodo-ester is saponified more rapidly than the chloro-compound. The influence of water on the rate of saponification of ethyl benzoate was also studie’d, and it was found that on increasing the quantity of water, the value of k increased as follows : In absolute alcohol, k =0.00543. In 73.4 per cent. alcohol, k=0*081.In 60-0 per cent. alcohol, k =0.148. 294. ‘‘ Contribution to our knowledge of semicarbazones. Part IV. Action of hydrogen chloride.” By Forsgth James Wilson, Isidor Morris Heilbron and Maggie Millen Jeffs Sutherland. The action of hydrogen chloride on varying types of seini-carbazones and phenylsemicarbazones results in the formation of coloured or colourless salts contlaining I, 18, 2, or 24 molecular proportions of hydrogen chloride; which show different degrees of stability. The monohydrochIorides are more stable than the di hydrochlorides, whilst those containing molecular proportions of hydrogen chloride intermediate between 1, 2, and 3 are extremely unstable and tlend to lose hydrogen chloride, giving stable mono- hydrochlorides.For example, a-piperonylideneacetonesemicarb-azone gives an unstable, vermilion salt containing ZgHCl, which rapidly loses hydrogen chloride until 13 molecular proportions are lost, when a stable, orange salt is obtained. Acetonesemicarbazone gives a colourless salt containing lJHC1, which is very unstable, tending to form a stable salt containing 1HC‘l. Salts were pre-pared from cinnamaldehydesemicarbazone, acetonesemicarbazone, acetophenonesemicarbazone, and benzaldehydesemicarbazone, and also from the corresponding phenylsemicarbazones. 295. ‘(Attempts to resolve metallic salts of amino-acids and other co-ordinated compounds.” (Preliminary note.) By Thomas Vipond Barker. Since the publication of a previous paper on co-ordination, iso- morphism, and valency (T., 1912, 101, 2484), the author has been engaged in attempts to effect certain optical resolutions in the province of co-ordinated compounds.In view of the fact that the anticipated molecular configurations present some novel features of interest, which may have applications in other branches of chem-istry, it is possible that a short notice may be of some value to other workers. Further, the fact that the attempted resolutions have so far been unsuccessful, makes it likely that two or three 296 years may elapse before the author has had time to work through the whole of the material he has in view, which circumstance makes it desirable to issue a preliminary note. One of the most remarkable successes that has attended the appli- cation of Werner’s theory of subsidiary valency is the satisfactory theoretical interpretation it provides for the abnormal character of many complex salts.The violet-blue dour of the copper salts of glycine and of certain other amino-acids is accompanied by an abnormally low electrical conductivity in aqueous solutions ; the latter anomaly is also characteristic of the corresponding salts of tervalent cobalt, and has led Ley to the conclusion that the nitrogen atom of the amino-group is combined to the metal by virtue of a subsidiary valency, whereby a cyclic structure is produced. The graphic formula of copper glycine may therefore be represented .. . thus : N H2*CH2*C0,*Cu*C02*CH2*NH2,which it will be convenient 1 to abbreviate to CCu 3 in which the arrow head denotes the nitrogen attachment.Now if the above formula is spacially contained in a single plane there is obviously no prospect of molecular enantiomorphism, but if, as seems likely, the four points of attachment are tetrahedrally arranged round the copper, the configuration is not identical with its mirror image. Any successful resolution, then, of copper glycine into optically active components would involve the definite proof that Ley’s interpretation is correct, but it would also have the following additional and, in the author’s opinion, more fundamental consequences: (1) Although everyone is forced to admit that Werner’s resolutions prove the subsistence of enantiomorphous con- figurations, there appears to be some reluctance in accepting all the theoretical consequences, or, at any rate, those involved in Werner’s interpretation.In so far as this reluctance is due to the fact that there is in every one of Werner’s cases an unco-ordinated part, the chemical relation and spacial position of which, with regard to the nucleus, are quite vague, there could be no such scepticism in a case like copper glycine, since every part of the formula, except the nitrogen attachment, is precisely settled by the structure theory of organic chemistry, and molecular enantioniorphism would in itself demand this nitrogen attachment. (2) Although enantiomorphous, the molecule would contain no asymmetric atom, for the copper would possess a two-fold axis of symmetry; the whole molecule would really present an instance of Werner’s so-called ‘‘ molecular asymmetry I,”which term is, however, obviously misleading since the molecule is symmetrical.297 It need scarcely be emphasised that the same enantiomorphous features are theoretically realisable in the copper (nickel, palladium, platinum) salts of the homologues of glycine. Moreover, it is possible to foresee additional items of interest : with sarcosine, CH3*NH*CH2*C02H,the nitrogen would be united to four different groups, which, if tetrahedrally arranged, will confer on it asym-metry. Again, with a-alanine there is a theoretical augmentation of the number of isomerides: if a d-and an k-molecule unite with the same copper, internal compensation will be prevented by the tetrahedral arrangement, and there may therefore be two pairs of enantiomorphous configurations, Cudd, Cull, and Cudl, Culd.With regard to the salts of the tervalent metals, it may be men- tionel that Ley actually obtained two ‘‘ stereoisomerides,” one of which he referred to a cis-trans-form of the octahedral structare. This supposition is somewhat unlikely and entirely unnecessary, for two stereoisomerides, each endowed with enantiomorphous possi- bilities, are realisable by the employment of cis-configurations, owing to the fact that the group -.-NH2.CH;CO,-, unlike ethylenediarnine, ...-N H;CH,.C€i;S H -,is in itself unsymmetri- cal. Thus we may have: Enantiomorphous pair of Enantiomorphous pair of symmetrical cobalt glycine.nnsyninietrical cobalt glycine. Very similar features of theoretical interest may again be expected in the class of the metallic dithiocarbamates about which these can scsrcely linger any constitutional obscurities in view of tht! very convincing work of DelBpine. These substances possess considerable crystallising powers, a fact which the author has been able to verify. Finally, there is the very important group of com-pounds, investigated by Tschugaev, which may be represented by fo-rmulze of the types Pt(DH), and ‘;I (’O(L)H)~,in which DH NH3 signifies the following residue of diacetyldioxime, cH3*C--p3,II . ..NOH NO-Although many other cases could be cited, the above enumera- tion would appear to complete the list of substances which may be considered suitable, botmh by reason of their accessibility and crystal- lising power. The author would emphasise the fundamental feature common to all, namely, their neutral character, which has its origin in the perfect saturation of all the valencies, both prin- cipal and subsidiary, within the co-ordination sphere.Although obviously enhancing the theloretical value of any optical resolution, the neutral character of the substances in question introduces con- siderable difficulties in the technique, for the employment of an optically active base or acid is out of the question. There’ only remains the method of spontaneous crystallisation, or, in other words, the chance that the substances may resolve themselves.As already mentioned, no positive success can be recorded up to the present ; certain of the substances, including the stereoisomeric cobalt glycines, have been definitely abandoned. In conclusion, it may be pointed out that the above stereochsmi- cal considerations lead immediately to the theoretical possibility of a novel kind of molecular enantiomorphism amongst organic sub- stances. Thus a compound of the type yp2>C<FQ2 althoughCQ, CY, possessing a symmetrical configuration, is nevertheless enantio-morplious. If the chemist will accept the only precise meaning that can be given to tho term asymmetric atom,” namely, an atom devoid of all symmetry, he will doubtless come to the conclusion that the above type of structure contains no asymmetric atom.296. ‘‘ Synthesis of pinacones. Part XI.” By William Parry. The action of sulphuric acid on some of the unsymmetrical pina- cones described in Part I (T.,1911, 99, 1169) has been studied. (1) 66-Dimethylhexan-y-one, CMe,Et*COEt, obtained when p-methyl-y-ethylpentane-By-diol is heated with dilute sulphuric acid, is a colourless oil with an odour of peppermint, boiling at 148--152O/773 mm. On oxidation with chromic acid mixture it yields (i) carbon dioxide, (ii) acetic acid, (iii) aa-dimethylbutyric acid, CMe,Et.C02H, thus proving its constitution. (2) €€-DimethyZoctcol-6-o/ze, CMe2Pra.COPra, obtained by the action of cold concentrated sulphuric acid on P-methyl-y-propyl-hexane-fly-diol, is a colourless oil with a faint odour of peppermint, and boils at 182--186O/765 mm. The semicarbazoile forms white needles, melting at 145O.The constitution of the pinacolin is proved by its oxidation to (i) acetic and propionic acids by chromic acid mixture, (ii) aa-di- methylvaleric acid, CM@?ra*CO,H, by chromic acid in glacial acetic acid. (3) The pinacone, OH-CM~*C(C,H,l)2*OH, is obtained by the 299 interaction of magnesium isoamyl bromide and ethyl a-hydroxyiso- butyrate; it forms white, waxy needles, melting at 34-35O. By cold concentrated sulphuric acid it is converted into fl[@-tetm-ameth$decan-e-one, C5H1,*@M~*CO~C,H,,,yellow oil, boiling at 132--134O/25 mm., which does not form a semicarbazone.The con- stitution of this pinacolin is proved by its oxidation to (i) isovaleric acid, by chromic acid mixture ; (ii) aa6-trimethylhexoic acid, C,R,,*CM~*CO,H,by chromic. acid in glacial acetic acid. (4) y y-Diphenylbutan-8-one, CMePh,*COMe, is obtained as a yellow oil, b. p. 180°/ 18 mm., when aa-diphenyl-fl-methylpropane-afl-diol is heated with dilute sulphuric acid. It solidifies when seeded with a crystal of the acetophenonepinacolin described by Thoerner and Zincke (Ber., 1878, 11,1989), and then melts at 41°, thus proving the identity of the two pinacolins. Further confima- tion of this identity is afforded by the oxidation of the yellow oil to aa-diphenylpropionic acid, CMePh2*C02H, by chromic acid mixture. 297. ‘(Substitution in aromatic hydroxy-oompounds.Part 11. Acetgl-nitro-substitution.” By Victor John Harding. An Pccount was given of the action of nitric acid on various methoxyaoetophenones. In those cases where the acetyl group occupies a position which, in the parent phenol ether, is active to iiitric acid, it is found that the acetyl group is displaced by the nitro-group. This is termed acetyl-nitro-substitution. The following acetophenones are found to undergo this substitution : (a) 3 :4-di-methoxyacetophenoiie, (b) 4 :5-dimethoxy-o-Idyl methyl ketone, (c) 3 :4 :5-trimethoxyacetophenone: OMe OMe OMe/\I OMef\ \/’Ac (4’ OMe 0Me -+ OMe(\ OMe 300 Where the acetyl group occupies a position which, in the parent, phenol ether, is inactive to nitric acid, it is found that a nitro-ketone is produced.Thus 2 :3 :4-trimethoxyacetophenone on nitra- tion gives 6-nitro-2 :3 :4-trimetho~yacetophenone~and not 4-nitr~ pyrogallol trimethyl ether: OMe (?Me ERRATUM. PROCEEDINGS, 1914. Page 270, line 10, for “Alexander Rule” rend “Alexander Rule and John Smeath Thomas.” At the next Ordinary Scientific Meeting on Thursday, December 17th, 1914, at 8.30 p.m., the following papers will be com-municated : I‘ isoDibenzoylglucoxylose.” By F. Tutin. ‘‘ Platini-, mercuri-, and cupri-chloromercaptides and tauto-merisation of o’rganic thio-compounds as brought about through the agency of mercuric, cupric and platinic chlorides.” By P. C. RBy. PIIIST€J) IN GREAT BRITAIS BT If. CIkY 4KD SONS, LTD., B!?I SSIVICB ST’TFFT, SIA31FORTI STRFFT, S F., AXD BTYQ4Y. SUFFOLK.
ISSN:0369-8718
DOI:10.1039/PL9143000289
出版商:RSC
年代:1914
数据来源: RSC
|
|