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Proceedings of the Chemical Society, Vol. 28, No. 408 |
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Proceedings of the Chemical Society, London,
Volume 28,
Issue 408,
1912,
Page 323-334
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[Issued 30/ 12/12 CHEMICAL SOCIETY. VOl. 28 No. 408 Thursday, December 19th, 1912, at 8.30 p.m., Professor PERCYF FRANKLAND,LL.D., F.R.S., President, in the Chair. Messrs. Ridsdale Ellis, E. L. Lomax, C. E. Sladden, John W. Patterson, and E. A. Cooper were formally admitted Fellows of the Society. Certificates were read for the first time in favour of Messrs.: John Hugh Christie, B.Sc., c/o Dr. Bean, Cross Gates, Leeds. Roland Doumin, 76, Tannsfield Road, Sydenham, S.E. Albert Edward Garrett, B.Sc., Yaverland, Clarence Road, St. Albans. Douglas Henville, 67, Glencoe Street, Newington, Hull. Thomas James Eirkland, B.Sc., Hereward Hall, Ely. William Norman Rae, B.A., Royal College, Colombo, Ceylon. Hermann Horace Roskin, B.Sc., 11, Newlands Road, Middles- brough.William Slessor Simpson, M.A., B.Sc.,Dynamite Factory, Somer- set West, S. Africa. Of the following papers, those marked ic. were read: *321. (‘Aqualitative attempt to harmonise the relation between temperature and rotation for light of all’ refrangibilities of certain active substances, both in the homogeneous state and in solution.” By Thomas Stewart Patterson. Evidence was adduced to show that the temperature-rotation curve for an active substance is probably irregularly periodic, and that in comparing the rotation values for different substances of a similar class account should be taken of something corresponding with phase and something corresponding with amplitude. The influ- ence of a solvent appears to be to shift the temperature-rotation curve as a whole towards a lower or higher temperature with corre- sponding difference in amplitude.The maximum rotation occurs at slightly different temperatures for light of different refrangibili- ties, and this accounts for the phenomenon of anomalous rotation- dispersion. The influence of solvents on anomalous rotation-disper- sioa appears to be just the same as on the temperature of maximum rotation. The recognition of the variation of the temperature of maximum rotation appears to bring into one general scheme all the diverse phenomena of optical activity. DISCUSSION. The PRESIDENTsaid that in all the six cases in which he himself had found a maximum rotation * the latter occurred at a tempera- ture below the melting point of the substance.He suggested that the maximum in such cases might be associated with the complex condition of the liquid in the supercooled state in which two or more different kinds of molecules might be present. Some of the maxima recorded by Dr. Patterson appeared to him to have been obtained at temperatures so high that some decomposition might be feared, but he presumed that the author had taken the possi- bility of a spurious maximum being thus obtained into considera- tion. In reply to the President, Dr. PATTERSONstated that the maxima observed in the temperature-rotation curves was not due in any way to decomposition of the substances on heating. In cooling from a high temperature the rotation was observed to rise and then diminish again.* Ethyl dibenzoyltartrate, ethyl and methyl di-o-toluoyltartmtes, methyl di-o- chloro-, di-o-bromo-, and di-o-iodo-tartrates. 325 “322. It The photography of absorption spectra.” By Thomas Ralph Merton. The photographic methods generally used for the observation of absorption spectra are not suitable for quantitative investiga- tions owing to the complicated conditions which govern the density of a photographic plate. A photographic method has been found for the determination of extinction curves which is free from these objections. *323. The constitution of ortho-diazoimines, Part 11. The p-tolylnaphthatriazoles.” By Gilbert T. Morgan and Frances Mary GCore Micklethwait.In continuation of earlier experiments (PToc., 1910, 26, 151), attempts have been made to prepare the third homeride, having the general formula a~-C’,,H,:N,*C,H,(p). 2 :4-Dinitro-l-p-tolyl-a-naphthylamine(yellow needlM, m. p. 196-198O) obtained by boiling l-chlore2 :4-dinitronaphthalene and ptoluidine in xylene solution, yielded on complete reduction the somewhat oxidisable base l-p-tolyl-1:2 :4-triamimmphthalene (colourless needles, m. p. 177O). The action of nitrous acid on this triamlne is remarkable, as it leads to the elimination of ptoluidine, in the form of ptoluenediazonium chloride, and to the production of 2-amino-l : 4-naphthaquinoneimid0, a compound hitherto obtained by the action of ferric chloride on 2 :4-diamino-a-naphthol.The partial reduction of 2 :4-dinitro-l-p-tolyl-a-naphthylamineis under investigation. “324. Co-ordination compounds of vanadium. Part I. The acyl-acetonates ” By Gilbert T. Morgan and Henry Webster Moss, Vanadium terbenaoylacetonute, dark chocolate-brown leafleb, m. p. 218-220°, was obtained by the interaction of anhydrous vanadium trichloride, benzoylacetone, and alcoholic sodium ethoxide; it is insoluble in water, and dissolves freely in chloroform or benzene. In the moist condition it oxidism to the emerald-green vanadium oxgbisbenzoylacetonate (vanadyl bisb ensoylacetonate), 326 which is more readily prepared by dissolving freshly precipitated vanadyl hydroxide in an alcoholic solution of benzoylacetone. Vanadium oxybisacetylmethylacetorLate (vanadyl bisacetylmethyl- acetonate), sage-green, itcicular prisms, results from the interaction of vanadyl hydroxide and alcoholic acetylmethylacetone.The ultra-violet absorption spectra of the vanadium teracyl-acetonates and vanadium oxybisacylacetonates in alcoholic solution differ from those of vanadium trichloride and vanadyl dichloride in showing persistent absorption bands like the bands exhibited by the acylacetones themselves, whereas the two chlorides indicate only general absorption in dilute solutions. 325. ‘‘ Dlbenzyl-and diphenyl-silicolsand -silicones.” By Geoffrey Naxtin. The author, by means of a tabular comparison between the com- pounds recently described by Kipping (Trans., 1912, 101, 2108 et sq.) and the same on@ previously described by himself (Ber., 1912, 45, 403), controverted Kipping’s statement (Zoc. cit.) that an erroneous account has been given of these compounds.The author pointed out that he had not described any “isomeric ” diphenylsilicols in his paper (Zoc. cit.), as asserted by Kipping, and stated that Kipping had merely ‘‘ rediscovered ” the two modifica- tions of diphenylsilicol described by him ten months previously (Zoc. cit.). The author maintained the correctness of his conclusion that one modification can pass into the other, and vice versa. He pointed out that Kipping himself records the passage of one modi- fication into the other, and actually states that it is a result “which appears to be fully established ” (Zoc.cit., p. 2124). 326. Optically active glycols de ived from the phenyl-lactic acids. cs Part I.” By Alex. McKenzie and Geoffrey Martin. The authors have prepared and examined a number of glycols derived from esters of P-hydroxy-8-phenylpropionicacid and a-hydroxy-B-phenylpropionicacid respectively by the application of Grignard reagents. 327 327. ‘‘Diphenylene. Part 11.’’ By James Johnston Dobbie, John Jacob Fox,and Arthur Josiah Hoffmeister Gauge. Certain derivatives of diphenylene, C6H4:C6H,(Trans.,1911, 99, 683), have been prepaxed. A dibromodiphenylene melting at 171O was obtained by the action of bromine on the hydrocarbon, but at the same time a considerable amount of 2 :2’-dibromodiphanyl was formed.Nitration with a mixture of concentrated sulphuric acid and nitric acid (D 1.5) resulted in the farmation of a tetranitro& phenylene melting at 223O. When diphenylene was heated with diluted nitric acid under pressure, there were formed : (1) a dinitrodiphenylene melting at 2040, (2) diphemylene oxide, (3) 3-nktrophthalic acrid. In preparing the derivatives of diphenylene, a large proportion of the parent substance was invariably converted into waxy and resinous substances. Atteanpta to prepare diphenylene by other method8 than that originally employed were deacribed. Dry distillation of silver diphenate led to the formation of the laetone of 2-hydroxydiphenyl-2/-carboxyliz acid, 76H4’Qtr,C, H,*O but no diphenylene was formed. Finely-divided sodium reacted rapidly with 2 :2’-dibromodipbnyl, forming diphenylene and other substa3lces, of which one agreed in composition with the formula C,,H,Br,, and melted at 3069.328. ‘‘ A new method for the estimation of hypochlorites.” By Herbert Waldiig Williams. Hypochlorites can be titrated with a N/ 10-solution of hydrazine sulphate, the end point being determined by starch-iodide paper. The action appears to be: N2H4+ 2MOCl= N2+ 2H20+2MC1. It is necessary to keep the mixture alkaline throughout, sodium hydrogen carbonate being added if required. Comparison titra- tions made with N/ 10-arsenic trioxide and N/ 10-hydrazine sulphate showed very close agreement. The author finds that, contrary to the statement of Browne and Shetterly, neither ammonia nor azoimide is formed.328 329. bb Ethylation in the flavone group.” By Arthur horge Perkin. Although, except in the case of myricetin, fully ethylated deriv- atives of flavohe colouring matters containing an fiydroxyl adjacent to the carbonyl group have not hitherto been prepared by means of ethyl iodide and alkali, no difficulty exists in producing such compounds if an excess of the reagents is employed. Adopting the procedure found serviceable with myricetin (Trans., 1911, 99, 1725), luteolin (5 grams) gave l~teolin tetraethyl ether, C,,H,O,*(OEt), (Found, Et =28-67), colourless needles, m. p. 153-155O (4 grams), whereas from apigenin (5 grams), ap-genin triethyl ether, C15H702*(OEt)3 (Found, Et=24-58), prismatic needles, m.p. 189-191O (4 grams), was prepared. Quercetin from rutin (10 grams) yielded quercetin pentaethyl ether, CI,H,02(0Et),,colourlew, pkmrttic needles, m. p. 116--118O (11 pams) (Foiiild, Et =32.86 ;C =67-70; H =6-78), and when hydrolysed with alco- holic potassium hydroxide gave protocatechuic acid diethyl ether, and the hydroxyfisetol triethyl ether, C14H2005, m. p. 96-97O (Found, C= 62.79 ;H =7-39)> previously obtained (Zoc. cit.) from myricetin hexaethyl ether. The low melting point of the quercetin pentaethyl ether suggests that this compound may prove to be dimorphous. In a similar way quercetagetin and gossypetin give fully ethylated derivat’ives, which will be described in a later communicd tion, and there is evidence that other analogous ketonic compouuds behave similarly under this treatment. 330.46 The synthesis of some new dimethyltetrahydroquiinolines.” By Arthur James Ewins and Harold King. The synthesis of 4 :8-dimethyl-1 :2 :3 :4-tetrahydroqumoline and of the corresponding 4 :7- and 4 :6-dimethyl bases from the 0-, m-, and ptoluidides of acetoacetic acid has been carried out in order to compare their properties with those of a base, a-cytisolidine, a degradation product of the alkaloid cytisine (Freund, Ber., 1904, 37,16). The abovementioned toluidides have not hitherto been isolated. They were prepared by heating mixtures of the toluidine and ethyl acetoacetate, in molecular proportions, to boiling for one to one and *half minutes.On cooling, the nearly pure toluidides separate out in good yield. On treatment with sulphuric acid at looo for fifteen minutes they yield carbostyrils, and the latter, by reduction with sodium in alcoholic solution, the dimethyltetrahydroquinolines. 329 331. The constitution of cytisine, the alkaloid of Cytisns laburnum 46 Part I, The synthesis of a-cytisolidine and of P-cytisolidine.” By Arthur James Ewins. By the action of hydriodic acid and phosphorus on cytisine, C,,H,,0N2, at a temperature of 225-230°, Freund (Ber., 1904, 37, 16) obtained among other products a feebly basic, crystalline solid, cytisoline, C,,H,,ON (m. p. 198O), and a strongly basic oil, P-cytisolidine, to which he gave the formula C,,H,,N. Cytkoline, on reduction with sodium in alcoholic solution, gave a strongly basic oil of the composition C,,H15N, which was termed a-cytisolidine on account of its supposed isomerism with 8-cytisolidine.The constitutions of these two bases have now been established by their synthesis. a-Cptisolidine is identical with 6 :8-dimethyl-1:2 :3 :4-tetrahydroquinoline (C,,H,,N), and P-cytisolidine with the corresponding 6 :8-dimethylquinoline (CT1,H,,N). The formula assigned to P-cytisolidine by Freund is thus inaccurate. The relationship of the bases obtained by Freund must therefore be as follows: Cytisoline, C,,H,,ON . . ... . .., . . (?)-Hydroxy-6:8-dimethylquinoline.8-Cytisolidine, C,,H,,N.. . . .. ... 6 :8-Dimethylquinoline.a-Cytisolidine, C,,H,,N .........6 : 8-Dimethyl-1 :2 :3 :4tetrahydroquinoline. The. constitution of cytisine, from which cytisoline is formed merely by the eliwiuatioo of the eleuieuts ot ammonia, rewaitts undetermined. 332. Some reactions of the sulphoxylic acids.” By Percy May and Samuel Smiles. Barnett and Leete (Proc., 1911, 27, 120) have shown that when thiobenzanilide is oxidised with hydrogen dioxide the correspond- ing thionyl derivative (I) is formed. When it is considered that C,H,*WH g*C6H, C,H,*N :?*C,H, so SH (1.) (11.1 thiobenzanilide and other thioamides exhibit in many of their reactions the structure of an imino-mercaptan (for example, II), it seems probable that the oxide in question would behave in a similar manner according to the isomeric formula represented by (111).The suspicion is confirmed by the fact that thiobenzanilide C,H,-N :y=C,H, SOH (111.) 330 oxide yields a sodium salt, for there can be no doubt that in this substance the metal is attached to the thionyl group. It is there- fore evident that under certain conditions thiobenzanilide oxide may be regarded as a sulphoxylic acid, and at the time when this investigation was planned only one other substance of this class, namely, formaldehyde sulphoxylate, had been isolated. The tem- porary existence of these. substances in certain reactions has been frequently postulated with varying degrees of certainty, and oppor- tunity has now been taken to test the accuracy of certain assump- tions concerning their reactivities.Fromm and his collaborators (Bey., 1908, 41, 3397; 1909, 42, 3816) have advanced the view that in alkaline solution the sulphoxylic acids are unstable, and tend to undergo simultaneous reduction and oxidation, mercaptans and various products of oxidation being formed. This is fully confirmed by the behaviour of thiobenzanilide oxide in alkaline solution, The sodium salt may be obtained by rapidly cooling a warm solution of the substance in 10 per cent. aqueous sodium hydroxide; it forms very pale yellow needles, which are soluble in cold water, but sparingly so in the cold alkaline medium. The salt is not stable, and if the aqueous solution is warmed it is completely decomposed, yielding benzanilide and thiobenzanilide.It is clear that the latter is formed by reduction of the oxide, and independent experi- ment shows that the former product is obtained when the oxide is treated with dkaline oxidising agents. In explaining the reactions of disulphides with concentrated sulphuric acid, it has also been postulated (Prescott and Smiles, Trans., 1911, 99, 642) that the sulphoxylic acids are capable of condensing in that medium with an aromatic nucleus yielding sulphides, for example : R=SOH+HAr =R*S*Ar+H,O. Support is given to this assumption by the fact that thiobenz- anilide oxide is almost quantitatively transformed by warm sulphuric acid into the phenylbenzothiazole, which has been previ- ously obtained (for example, Ber., 1886, 19,1068) in other ways: C6 H5/-'>C*C,H,HO-S = C6H4<!>C*C6H5 + H20.Among other reactions of this oxide mention may be made of that which takes place with dry hydrogen chloride in presence of a dehydrating agent ;sulphur is eliminated, and the iminochloride of benzanilide is formed as expressed by the following equation : The further investigation has been abandoned owing to the recent discovery (Ber., 1912, 45, 2965) of other sulphoxylic acids of less intricate structure. 333. ‘‘The conde~isation of a-keto-P-anilino-a-phenylethaneand its homologues with carbongl chloride, phenylcarbixide. and phenylthiocarbimide ” By Hamilton XcCombie and Harold Archibald Scarborough. McCombie ancl Parkes (Trans., 1912, 101, 1991) have shown that carbonyl chloride and a-ketcH3-anilino-a@-diphenylethane can be condensed to give 3 :4:5-triphenyl-2 :3-dihydro-2-oxazolone.This synthesis has now been extended to a-keto-fl-anilino-a-phenylethane, which with carbonyl chloride gives 3 :5-diphenyl-2 :3-dihydro-2-oxazolone (I). This reaction has been applied also to compounds in which aniline has been replaced by 0-, m-,and p-toluidine ancl Bnaphthylamine. These oxazoloiies are stable compounds, and their basicity is so slight that no picrates or hydrochlorides could be isolated. Brazier and McCombie (Trans., 1912, 101, 2352) acted on a-keto- 6-anilino-a@-diphenylethane with phenylcarbimide, and obtained 1 :3 :4:5-tetraphenyl-2 :3-dihydro-2-glyoxalone. This reaction has now been extended to a-keto-P-anilino-a-phenylethane,which gives with phenylcarbimide, 1:3 :4-triphenyl-2 :3-dihydro-2-glyoxalone (11).The reaction occurs in two stages; the two compounds are heated together on a water-bath until a white mass is obtained, which on treatment with alcoholic hydrogen chloride yields the glyoxalone ;the corresponding 0-,m-, and p-toluidine and P-naph- thylamine compounds have been obtained : (1.1 (11.1 (111.) The glyoxalones yield salts with picric acid, but not with hydro- chloric acid. These picrates consist of one molecule of the base combined with one molecule of the acid. Phenylcarbimide has been replaced by phenylthiocarbimide yield- ing 1:3 :4-triphenyl-2 :3-dihydre2-glyoxalthione (111). 334. ‘‘ Note on the nitration of p-hydroxyacetophenone.” By Frank Geo.Pope. Gattermann (Ber., 1892, 25, 3523) obtained S-nitro-p-hydroxy- acetophenone in small yield (11 per cent.) by the condensation of o-nitroanisole with acetyl chloride in the presence of aluminium chloride. It crystallises in yellow needles melting at 130*5O. The posit’ion of the nitro-group was determined by oxidising the methyl ether with dilute nitric acid to 3-nitroanisic acid, which had already been obtained by Salkowski. Since the hydroxy-ketone is merely a psubstituted phenol, there appeared to be no reason why nitration should not be directly attempted, and the following experiment was consequently carried out. 3.5 Grams of the finely-powdered hydroxy-ketone were added in small quantities at a time to a well-cooled mixture of 20 C.C.of nitric acid (D 1.42) and 20 C.C. of concentrated sulphuric acid, with constant stirring. After half an hour the mixture was poured on to crushed ice, and the faintly yellow precipitate was collected, well washed, a.nd dried. The aniount of solid matter so obtained was 3.5 grams, and in the crude state melted at 128-130°. This repre- sents a 75 per cent. yield of nitrohydroxyacetophenone. The nitro-compound was then crystallised from boiling water, seprating in slender, yellow needles, melting at 135O. (Found, N =7.92. C,H,O,N requires N=7.73 per cent.) Hence the nitro-compound is 3-nitro-p-hydroxyacetophenone,and further proof is given by the fact that on methylation and subse- quent oxidation with dilute nitric acid, 3-nitroanisic acid is obtained.The acid prepared in this manner melts sharply at 19O-19lo, whereas Salkowski gives 186-187O. The methyl ether which was also obtained simultaneously by Gattermann is readily prepared by methylating p-hydroxyaceto- phenone in alkaline solution with methyl sulphate, and then nitrat- ing the methyl ether in the manner described above. On oxidation with dilute nitric acid it also yields 3-nitroanisic acid (m. p. 19O-19lo), a mixed specimen of the acid as obtained by the two different methods also giving the same melting point. 335. Bromoxylenols obtained from dimethyldihgdroresorcin. (Pre-liminary note.)’ By Arthur William Crossley and Sydney Smith. In 1903 Crossley and Le Sueur (Trans., 1903, 83,110) described experiments on the action of phosphorus haloids on dimethyldi-hydroresorcin, and showed that both with phosphorus pentachloride and especially phosphorus pentabromide, the resulting substances readily undergo transformation into aromatic derivatives, giving in the latter case bromoxylenols. There were described a mono-brornosylenol melting at 83.5-84O and a dibromoxylenol melting at 96-5O.Both these substances gave on treatment with bromine a tribromoxylenol melting at. 183O, which, it was suggested, might 333 be identical with tribromo-o-3-xylenol melting at 184O. A second tribromoxylenol was encountered, melting at 177O. Further work has shown that the reactions are very complicated and susceptible to the slightest variation in experimental condi- tions.Although by no means complete, it is considered desirable to place on record a brief summary of the definite results so far obtained, as the present authors are unable to continue the work conjointly. (1) The monobromoxylenol, m. p. 84O, and the dibromoxylenol, m. p. 96'5O, have been proved to be derivatives of 0-3-xylenol; and although the position of the bromine atom in the former has not yet been decided, the latter has been proved by synthesis to be 4 :5-dibromo-o-3-zylenol. The synthetic formation is indicated by the following formulze : Me Me Xe (2) 4 :5-Dibromo-o-3-xyleno1 has also been obtained by the action of heat or of alcoholic potassium hydroxide on 2 :4:5-tribromo-l : 1-dimethyl-A*-cyclohexen-3-one (tribromoketodimethyltetrahydroben-zene) (ibid., p.124), its formation by loss of hydrogen bromide neoessitat.ing the wandering of a methyl group from carbon atom 1 to carbon atom 2: CMe, CXe H,C/\CHBr --+ HCd\CNe . BrCI\/'ICO BrCI\)C*OH CBr CBr (3) There has been isolated from the action of phosphorus pent,a- bromide on dimethyldihydroresorcin a monobromoxylenol melting at 103O. Although the constitution of this substance has not been proved by synthesis, it would appear to be a derivative of o-4-xyleno1, because on further treatment with bromine it gives a tribromoxylenol, and from this an acetyl derivative, the melting points of which are not lowered on admixture respectively with tribromo-o-4-xylenol and its acetyl derivative. In this rearrangement, therefore, a methyl group has again 334 wandered into anortho-position but from carbon atom 1 to carbon atom 6, instead of carbon atou 2: CMe, CRle /\ -+ MeC(/\ * i)C*OH The work is being continued, and it is hoped shortly to communi-cate more detailed accounts of these transformations and of the nature of the resulting products, for which purpose the synthesis of a number of bromoxylenols is being carried out. 336." Non-aromatio dirtz6aium salts. (Prelhimry note,) 'I By @iIbert T.Xargaa and Joseph Rsilly. The authors have investigated the degree of diazotisability of the following partly aromatic and non-aromatic amines : 4-aminoanti-pyrine, 6-amino-2 :4-dimethylpyrimidine, 4-amino-3 :5-dimethylpyra-zole, 4 -amino -1 : 3 : 5 -trimethylpyrazole, 2-amino-6-oxypurine (guanine), and aminomethyltriazole.When 4-aminoantipyrine hydrochloride is diazotised with ethyl nitrite in alcoholic solution without excess of mineral acid an uncrystallisable, resinous product is obtained on concentrating the solution. With excesB of acid a crystalline diazonium hydrochloride is produced, which after prolonged drying in a vacuum over potass- ium hydroxide corresponds with the formula 2C11H110N4Cl,HCl. The platinichloride, (C,,H,10N,)2PtC1,, the aurichloride, (C11H110N4)AuC14, and the very explosive diclwomate, (C11H110N4)2Cr207,have the normal composition. Although possessing a chemical constitution closely allied to the Aromatic amines, 6-amino-2 :4-dimethylpyrimidine is not diazotisable under the ordinary experimental conditions, and prolonged treat- ment with nitrous acid leads to the formation of the corresponding 6-hydroxy-2 :4-dimethylpyrimidine.4-Amino-3 :5-dimethylpyrazole gives rise to diazonium salts as stable as those of 4-aminoantipyrine, and these substances are being investigated, together with those of 4-amino-1:3 :5-pyrazole. 2-Amino-6-oxypurine does not diazotise under conditions which readily give rise to diazonium salts in the case of aminomethyl-triazole. The next Ordinary Scientific Meeting will be held cm Thursday, January 23rd,1913, at 8.30 p.m. R. CLAY AND SONS, LTD., BRUNSWICK ST.,STAMFORD ST., S.E., AND BUNGAY, SUFFOLK
ISSN:0369-8718
DOI:10.1039/PL9122800323
出版商:RSC
年代:1912
数据来源: RSC
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