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Proceedings of the Chemical Society, Vol. 30, No. 436 |
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Proceedings of the Chemical Society, London,
Volume 30,
Issue 436,
1914,
Page 301-310
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摘要:
PROCEEDINGS OF THE CHEMICAL SOCIETY. Vol. 30 No. 436 Thursday, December 17th, 1914, at 8.30 p.m., Professor W. H. PERKIN,LL.D., F.R.S., President, in the Chair. The PRESIDENTieferred to the loss the Society had sustained through death on November 28th, 1914, of Dr. Johann Wilhelin Hittorf, of Miinster, who was elected an Honorary and Foreign Member on February 6th, 1908. It was announced that, in accordance with a decision of iho Council, after December, 1914, the ‘‘Proceedings ” would appear in a contracted form, and would be issued once a month with the Journal. Messrs. J. D. Robertson, R. R. Baxter, H. M. Spiers, and J. F. Levy were formally admitted Fellows of the Chemical Society. Certificates were read for the first time in favour of Messrs.: Samuel Culloch Bone, 30, Long Lane, Garston, Liverpool. Frederick Alfred Mason, B.A., Ph.D., 21, Queen Square, W.C Albert Parker, M.Sc., The University, Birmingham. Harold Gordon Rule, B.Sc., Ph.D., 2, Roseneath Terrace, Edin- burgh. The following Certificate has been authorised by the Council for presentation t.0 ballot under Bye-law I (3) : James Fraser, 44,Cumballa Hill, Bombay, India. 302 Of the following papers, those marked * were read: “298. ‘‘ isoDibenzoylglucoxylose.” By Frank Tutin. Power aad Salway (T., 1914, 105, 767, 1062) described a new, crystalline!, bitter substance, dibenzoylglucoxylose, which they obtained from the leaves of Daviesia latifolia. The present author now finds that this substance is associated with a small proportion of a more sparingly soluble isomeride.isoDibenzoyZgZucoxyZose, C,,H,O,,, crystallises in small, colourless needles, melts at 173--174O, and possesses a bitter taste. The, occurrence of rutin in Daviesia leaves has been confirmed. *299. ‘‘ Aromatic selenium compounds.” (Preliminary note,)By Frank Lee Pyman, Rather more than a year ago, at the suggestion of Dr. Charles Walker, of Glasgow, attempts were made to form the selenium analogue of arsanilic acid, namely, paminopbenylselenic acid, NH,*C,H,*SeO,H, in order to determine its physiological action. Whilst aniline sulphate and arsenate readily yield sulphanilic and arsanilic acid respectively at an elevated temperature, no such compound could be obtained from aniline selenate.It was found, however, that phenylselenious acid gave on nitration a nitrophenyl-selenious acid, NO,*C,H,*SeO,H (yellow niedles, m. p. 156-157O), in good yield. This gave on reduction successively nitrophenyl diselenide, (NO2*C6H,-Se), (yellow spears, m. p. 83*), and amino-phenyl diselenide, of which the dihydrochloride was obtained in a cryst+alline form, (HCl,NH,*C,H,*Se), (yellow grains, m. p. 291-292O). Aminophsnpl diselenide gave on acetylation acetyl-aminophenyk diselenide, (CH,-CO*NH*C,H4-Se)2 (yellow needles, m. p. 185--186O), which dissolved in concentrated nitric acid form- ing acetylaminophenylselenious acid, CH,-CO*NH*C,H,*SeO,H (colourless needles, m. p. 209O). From the latter compound the salts OI acetylaminophenylselenic acid were obtained on oxidation with potassium permanganate, and the free acid was readily hydrolysed with formation of aminophenylselenic acid, NH2*C,H4*SeOsH,2H,0 (colourless needles, m.p. of the anhydrous salt 229O). Whilst it appears probable that these substances are meta-substituted deriv- atives of aromatic selenium compounds, no direct proof to this end has yet been obtained, but the work will be resumed shortly. In the meantime it is thought desirable to give a preliminary account of the results obtained in view of the fact that aromatic selenium compounds are receiving attention from other workers (compare Lesser and Weiss, Ber., 1912, 45, 1835; 1913, 46, 2640; Morgan and Elliott, this vol., p.248). DIscussION. Professor MORGANstated that the introduction of selenium into the aromatic nucleus through the agency of the diazo-reaction in conjunction with potassium selenocyanate was applicable only in the case of diazonium compounds which did not yield cyclic diazo- derivatives when their solution was rendered alkaline or even feebly acidic. For example, the amino-group of pchloroaniline was readily replaced by selenium, but this reaction did not occur with 4-chloro- 3-nitroaniline, the diazonium salt of which was converted by alkalis or even by aqueous sodium acetate into the comparatively stable diazo-anhydride : I this product resisting completely the attack of selenocyanate. Dr. TUCK suggested that it might be possible to settle which nitrophenylselenious acid had been obtained by nitration, by the preparation of the three isomerides by the action of the nitro- benzenediazonium chlorides on potassium selenocyanide.This reac- tion should give the diselenide which could be converted into the nitrophenylselenious acid by oxidation or into the aminophenyl- selenious acid by the method described by Dr. Pyman. *300.(‘Blue adsorption compounds -of iodine. Part 111. Derivatives of 2-and 4-pyrone.” By George Barger and Walter William Starling. The conditions for the formation of blue additive compounds of iodine with a large number of coumarin, chromone, xanthone, and flavone derivatives were described. These blue substances are sometimes mixed crystals, often amorphous adsorption compounds.The effect of electrolytes on adsorption was discussed, and also the effectof the chemical constitution of the adsorbent. 304 301. “The action of mercuric, cupric and platinic chlorides on organic sulphur compounds.” By Prafulla Chandra RBy . Ethyl and ethylene mercaptans have been found to yield with platdnic chloride chloro-mercaptides of the formula PtCl(XEt),*PtCl(SEt), and C2H,:S2:PtCl*S*C,H,~SH respectively. Thiocarbamide and thioacetamide under the action of platinic chloride at first undergo tautomeric change into the stable thiolic modifications, NH,-C( :NH)*SHand CH,*C( :NH)*SH, respectively, and then react with platinic chloride as in the above typical instances, yielding the chloro-mercaptides : PtCl,[S*C( :NH)*NH,],,HCl and PtCl,[S*C( :NH)*CH,],,H(;”I.Thiosemicarbazide likewise undergoes tautomeric change, and then loses a molecular proportion of ammonia, thus: The reactive thiol group in the product is readily att,acked by platinic chloride, giving the chloro-mercaptide, Tautomerisation on exactly similar lines is also brought about by rnonochloroacetic acid. Similar changes are equally effected by cupric chloride with the formation of the corresponding cwjwic cldoromercaptides; the latter, however, are not basic, and there- fore do not combine with hydrogen chloride. It is found that the behaviour of monochloroacetic acid towards thiocarbamide (T., 1914, 105, 2159) and other potential mercaptans is strictly con-formable to that of platinic chloride.302. ‘‘ Conversion of I-phenylchloroacetic acid into d-diphengl-succinic acid.” By Alex. McHenzie, Harry Dugald Keith Drew, and Gerald Hargrave Martin. The authors have examined the action of certain Grignard reagents on r-and I-phenylchloroacetic acids and on T-phenyl-bromoacetic acid. The following change amongst others has been effected : C,H,*7H*CO2HZ-C,H5*CHC11*C0,H+ d-co2H,cH.C , G5 305 Both the 6-and I-aP-dihydroxy-af@-triphenylethanes can be obtained from I-mandelic acid, thus : (by CI;Hj’iWgBr)I-C,H,*CH(OH)*C‘02H -___ 3 Z-CGH,*CH~(OH)*C(CoH,),.OH I 303. ‘(A method of separating the dihydroxybenzenes.” By Thomas Gray and George Shevas Cruikshanks. Quinol di-p-nitrobenzoate is very sparingly soluble in acetone, whereas the corresponding derivative of resorcinol dissolves rela- tively easily.This property, in conjunction with the sparing solubility of the lead salt of catechul in water, supplies a method for the separation of the three dihydroxybenzenes. The mixed phenols are dissolved in a small quantity of water, an excess of an aqueous solution of lead acetate is added, and the lead salt of catechol collected. The filtrate is acidified with sulphuric acid, extracted with ether, and the phenols are recovered by evaporating the dried ethereal solution. The residual phenols, consisting substantially of resorcinol and quinol, are then con-verted into d-i-p-nitrobenzoates, and the latter are separated by crystallisation from acetone.The phenols may be regenerated from the nitrobenzoates by saponification with alcohoIic potassium hydroxide in an atmosphere of hydrogen or nitrogen, and aubse- quent acidification. Catecho,! di-p-nitrobensoate, C,,H,,O,N,, crystallises from acetone in long, hair-like needles, melting at 164O. On0 gram dissolves in. 450 C.C. of boiling alcohol and in 20 C.C.of boiling acetone. Resorcinol di-p-nitrob el7 zoate forms long, hair-like needles, melt- ing at 182O. One gram dissolves in 1000 C.C. of boiling alcohol and in 45 C.C. of boiling acetone. Quinol di-p-nitrobensoate forms needle-shaped crystals or hexa-gonal plates. melting at 256O. One gram dissolves in 8000 C.C. of boiling alcohol and in 420 C.C. of boiling acetone.304. L6 a-Hydroxy-P-phenylcrotonolactone.” By Norman Hall, James Edward Hynes, and Arthur Lapworth. Wheri an attempt was made to eliminate the oximino-group from a-oximino-B-phenylpropionic acid by heating the latter with form- aldehyde and hydrochloric acid, the product obtained was not the expected phenylpyruvic acid, C,HsOs, but a compound having the formula CI0H8O3,derived from phenylpyruvic acid in the following manner : C9H803+ CH,O =CloHs03+H,O. The new compound is soluble in aqueous sodium carbonate, but is precipitated from the solution by excess of carbon dioxide. It gives an intense green coloration in alcoholic solution with ferric chloride, and, in the same solvent, it instantaneously absorbs at least 0.9 mol. of bromine in the cold.When oxidised with hydrogen peroxide it yields benzoylcarbinol and oxalic acid, whilst on distilla- tion it gives atropic acid and an oil which is probably styrene. The authors consider that the substance is closely related to the compounds known as " oxolactones," but in view of its behaviour towards bromine and the complete absence of any ketonic charac- ters, they feel confident in ascribing to it the enolic structure: As the acyl and alkyl derivatives show no ketonic properties they probably also belong to the ~iyd1.oxycl.otonolactone type in spite of the fact' that they are inert towards bromine in the cold. 305. Preparation of ethyl malonate and ethyl cyanoacetate." 'I By Harold Archibald Scarborough. The following process for the preparation of ethyl malonate gives a much better yield than that usually recommended.In a 1500 C.C. flask chloroacetic acid (100 grams) dissolved in water (ZOO c.c.) is warmed to 50°, neut'ralised with sodium carbon-ate, the solution filtered, and then potassium cyanide (80 grams) is slowly added, the mixture being cooled from time to time so that the reaction does not become violent. After heating on the water-bath for half-an-hour the flask is connected with a condenser and receiver, and the latter with the pump, and heated on the water-bath under diminished rressure until the whole of the water has been removed and the mass is quite dry.* The almost colourless residue is gradually mixed with a cooled solution of alcohol (ZOO c.c.) and sulphuric acid (160 c.c.), and heated on the water-bath for four hours with frequent shaking.Water is then added, the ethyl malonate extracted with ether, the ethereal solution wsll washed with water and sodium carbonate, dried, the ether distilled off, and the ethyl malonate fractionated * This ij much better than the usual method of removing the water by heating finally at !35", which always ciuse3 decomposition and loss. 307 under a pressure of 100 mm., and then under ordinary conditione. The yield of the ester boiling at 196-200° is 104 grams, or 60 per cent. of that theoretically possible. Preparation of Ethyl 6’yanoacetate.-This ester may be readily prepared by a modification of the process recommended by Kolbe and Hugo Miiller (,4nmZen, 1864, 131,348, 350).Ethyl chloro- acetate (100 grams) dissolved in alcohol (100 C.C. of 97 per cent.) is mixed with finely powdered potassium cyanide (55 grams), gradu- ally warmed, and then left until the vigorous reaction has subsided. The mass is then heated to boiling for fifteen minutes, the potassium chloride removed by filtration, and the alcohol removed from the crimson solution by distillation under diminished pressure. The residue is mixed with ether, the ethereal solution filtered, and, after removal of the ether on the water-bath, the crude product is distilled as rapidly as possible under diminished pressure, and then fractionated under ordinary conditions. The yield of ethyl cyano- acetate boiling at 205-208O is about 45 per cent.of that theoreti- cally possible. 306. “Investigations on the dependence of rotatory power on chemical constitution. Part XII. The rotatory powers of some esters of benzoic and of 1-and 2-naphthoic acids with optically active secondary alcohols,” By Joseph Kenyon and Robert Howson Pickard. A description of the properties of some of the benaoates and 1-and 2-naphthoates of d-P-butanol, d-&hexanol, d-B-heptanol, d-P-octanol, 6-0-decanol, d-P-undecanol, d-y-nonanol, and d-benzyl- methylcarbinol was given. The optical rotatory dispersive powers of the benzoates are simple at low temperatures and complex at higher temperatures, as has been found also in the case of the corresponding aliphatic esters.On the other hand, the dispersive powers of the naphthoates are complex at low and also at high temperatures in agreement with the hypothesis previously put forward that the naphthyl radicle and an esterified carboxylic group are each possible centres of a special kind of dynamic isoinerism at low and high temperatures respea tively. 307. “The optical rotatory power of derivatives of succinic acid in aqueous solutions of inorganic salts. Part 11.” By George William Clough. The rotatory powers of methyl hydrogen d-tartrate, sodium hydrogen d-tartrate, methyl Z-malate, and I-malic acid have been 308 measured in aqueous solution and in aqueous sodium chloride at various temperatures. The results of these measurements, together with those recorded in Part I (T., 1914, 105, 49), indicate that sodium and barium haloids in aqueous solution exert a specific effect on the rotatory power of those hydroxy-derivatives of succinic acid which contain a carboxyl or carbalkyloxy-(ester) group, this effect being usually opposite to that caused by dilution.308. 2 :4-Dicblorophenylhgdrazine.” By Frederick Daniel Chattaway and Charles Frederick Byrde Pearce. From the circumstance that 2 :4-dichlorophenylhydrazine, which should be obtainable from perhaps the most easily made chloro- substituted aniline, has never been described, it might be inferred that its preparation offers some difficulty. This, however, is not the case; it is easily obtained by the ordinary method, and is a stable, well-crystallised compound showing the usual behaviour of halogen substituted aromatic hydrazines, and yielding a series of well-crystallised hydrazides and hydrazones.ADDITIONS TO THE LIBRARY. I. Dorcations. Hurst, George H., and Simmons, IVillinrn Eerbert. Textile soaps and oils. A handbook on the preparation, properties, and analysis of the soaps and oils used in textile manufacturing, dyeing, and printing. 2nd edition. London 1914. pp. xi+ 189. ill. 7s. 6d. net. (Recd. 21/11/14.) From the Authors. Watts, Olivev P. Laboratory course in electrochemistry. New York 1914. pp. vi + 150. ill. (Recd. 20/11/14.) 4s. 2d. net. From the Publishers : The McGraw-Hill Book Co. 11. By Purchase. Scudder, Heyward. The electrical conductivity and ionization constants of organic compounds. A bibliography of the periodical literature.London 1914. pp. 568. 12.9. 6d. net. (Recd. 15/12/14.) 309 111. Pamphlets. Auerbach, Friedrich. Studien iiher Formaldehrd. IV. Die Dampfe von Formaldehyd und seineo Polymeren. (From the Arb. K. Gesund., 1914, 47.) Beadle, Clayton, and Stevens, Henry Potter. The production of rubber of uniform colour. (From the Rutber Recueil., 1914.) Beam, Filliam, and Freak, Gilbert A. An improvement in the electrical metbod of determining salt in soil. (From the Cairo Xcientijc Journal, 1914, 8.) Doherty, William iVichusZ. The estimation of carbon dioxide in the air. (From the Report Aztstmlasian Aseoc. Adv. Xci., 1913, 14.) Fourneau, E., and Page, Harold J.Sur l’identitk entre la yohimbiue et 1% qudbrachine. (From the Bull. Sci. pharmacol., 1914, 2 1.) Long, J. I$., and Muhleman, G. V. The mutual action of certain digestive fei ments. (From the Arch. Int. Xed., 1914, 13.) Moir, James. Quinonoid oxidation products of dianisidiue, and their polymerisation. (From the 8, African J.of Sci., 1914.) Pfyl, B., and Turnau, R, hfassanalytische Be.stimmung des Kaseins in dei. Rlilch niittels des Tetraserums. (From the Arb. K. Gesund., 1914, 47.) Shorey, Edrnund C. The preseuce of some benzene derivatives in soil>. (From the J.Agric. Res., 1914, 1.) INFORMAL MEETING). The Rooms of the Society will be opened for an Informal Meet- ing on January 14th, 1915, at 8 p.m., when the President and Council will be glad to receive Fellows.Smoking will be permitted and light refreshments will be provided. Fellows are invited to exhibit apparatus and specimens of interest, and to show experiments; those Fellows wishing to do go are requested to communicate with the Assistant Secretary not later than Monday, January 11th. 310 At the next Ordinary Scientific Meeting on Thursday, January 21st, 1915, at 8.30 p.m., the following papers will be communi- cated : (‘Granidine. Part 11. Copper derivatives.” By H. Krall. “ Guanidine. Part 111. Potassium derivatives.” By H. Krall. (‘Guanidine. Part IV. Silver derivatives and constitution.” By H. Krall. Studies in alcoholysis. Part I. Dilatometric determination of the velocity of alcoholysis in the presence of a large excess of alcohol.” By G.C. Eolhatkar. “The wet oxidation of metals. Part IV. The question of passivity.” By B. Lambert and H. E. Cullis. “The velocit8y of ionisstion at low temperatures.” By A. R. Normand. ERRATUM. PROCEEDINGS,1914. Page 283, line lo*, for (‘Iles, George Cochrane ” rend “Iles, Charles Cochrane,” * From bottom. NOTICE. The Council have decided that the issue of the Proceedings in their present form shall cease with the present number, which completes the thirtieth volume. In future the Proceedings will be issued in an abbreviated form along with the Journal, but will be paged independently so that they may be bound either with the Journal or separately. It has been found necessary to raise the selling price of the Journal (containing the Proceedings), as from the end of 1914, to $3 per annum. PBINTED IN QREAT BRITAIN BY 11. CLAI AND SONS, LTD., BRUNSWICh STREET, STAYFOBD STBEET, S.E., AND BUNQAY, SUBrOLB.
ISSN:0369-8718
DOI:10.1039/PL9143000301
出版商:RSC
年代:1914
数据来源: RSC
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