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Proceedings of the Chemical Society, Vol. 16, No. 226 |
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Proceedings of the Chemical Society, London,
Volume 16,
Issue 226,
1900,
Page 143-162
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摘要:
Issued 2 9/6/1900 PROCEEDINGS OF THE CHEMICAL SOCIETY. EDITED BY THE SECRETARIES. VOl. 16. No. 226. June Zlst, 1900. Professor THORPE, C.B., F.R.S., President, in the Chair. A ballot for the election of Fellows was held, and the following were subsequently declared duly elected :-Messrs. James Ashton ; George E. Battle, B.A.; Charles Barjen Brooke, jun, ; Angel0 Cantin ; Ernest Owen Courtman ; Richard H. C. Gompertz, B Sc. ; John Henry Gough; Henry Bertie Gritton ; Percy John Hinks; Tajiro Ichiokn ; John B. Leathes, M.A., M.B. ; Alexander Ernest McKenzie ; Hugh JlcNnir ; Sidney Scrivener Napper ; David Herbert Patrick; IT. C. Nanjunda Row, B.A., 3T.B. ; 31. Goolab Roy ; Oswald Silberrad, Ph.D. ; Timothy A. Sniiddy ; Herbert Procter Smith ;George Edward Tomlins ;John Traquair.Of the following papers, those marked * were read :-“89. “Researches on morphine. I.” By S. B. Schryver and I?. H. Lees. The authors have found that the alcoholic hydroxyl group in mor-phine is readily replaceable, and they have prepared the compounds described below. Chloi.omoqhide, C,7H,,0,NCI, prepared by the action of phosphorus trichloride on dry morphine. It melts at 190’ with decomposition, and dissolves readily in chloroform and in methyl alcohol. The hydyochloyide, C17H,,0,NCl,HCI, and hydi-obq*omide, C17Hls0,NCl,HBr, have also been prepared. On treatment with acetic anhydride, the nzonoacetyl derivative, C17H170(0C,H,0)NCI, is obtained melting at 178-179O. 144 B?*omomo~phide,C17H,,02NBr,melting with decomposition at 170°, has a very bitter taste and dissolves readily in chloroform and benzene.Its hydrochloride and hydrobromide crystallise with one molecule of water. Bromomorphide can also be prephred by the action of concen-trated hydrobromic acid on morphine. By treating chloromorphide with tin and hydrochloric acid, desoxy-ntorphine hydrochloride, 2(C17Hl,0,NHC1),3H20, is obtained as glisten- ing needles. The salt is lzevorotatory ;[.]: = -140.3". It was found that on heating chloro- and bromo-morphide and their hydrochlorides with water, decomposition took place, bromomorphide giving the hydrobromide of a base isomeric with morphine ; for this new base the authors propose the name isonzoqvhine. Isomorphine and its derivatives are more powerfully lzvorotatory than morphine and its corresponding derivatives.The salts of isomorphine are much more readily soluble than those of morphine. Isomorphine melts at 246-247", is readily soluble in methyl alcohol, but only very sparingly so in ether, chloroform, or benzene. Recrystallised from hot water, it is obtained as glistening needles. In methyl alcohol, {a]: = -164.3'. For the hydrochZorid6, Cl7HlSO,N,HC1, [a]:: = -150' ; for the I~ydrobromida,C17H,90,N,HBr,H,0, [a]: = -127.2' for the anhydrous salt. The ntet?tiociide, C,7H,90,N,CH,I, melts with vigorous decomposition at 279"; in aqueous solution, [a]: = -91.5". Morphine methiodide also melts at 279", but for it [.ID = -72.9". l3y treatment of isomorphine methiodide in aqueous solution with bilver sulphate and barium hydroxide, a very alkaline solution of the hydroxide is obtained, which, dried in a vacuum, sets first to a de-liquescent mass of fern-like crystals, and on further dehydration in a vacuum yields a solid which can readily be powdered, This substance dissolved in methyl alcohol does not react in the cold with methyl iodide, but does so readily on warming, giving a methiodide extremely soluble in water and in methyl alcohol, but only slightly so in ethyl alcohol.For it [a]? = -96.4'. This compound is not identical with codeine methiodide. The determinations recorded in the following table mere made with the free bases dissolved in methyl alcohol, and the salts (anhydrous) in water : I Free base. Hydrochloride.Hydrobromide. I I I--__-__-Morphine .... . ...,........... -130.9" [a]z6= -111.5" 1 [a];O= -100.4 Chloromorphicie ......... ..... [a]:'= -375.2 [a];l= -313.7 [a];= -268.6 Bromomorphide ,. . , , ... . .. . . . . f66.6 I +41'1 [u]i5= +39'5 Chloromorphide, bromomorphide, desoxymorphine and isomorphine 145 are all devoid of narcotic action. The significance of these facts and the relationship between morphine and isomorphine were also discussed. *90. '' On the oxime of mesoxamide and some allied compounds." By Martha Annie Whiteley, B.Sc. The compound formed by the action of nitrosyl chloride on malon-amide (Tilden and Forster, Tvanns., 1895, 67,490) appears to be the iso-nitroso-derivative, NH,OC*C(NOH)*CONH,.It dissolves readily in water, has an acid reaction, and melts with decomposition at 187'. It forms alkaline salts which are bright yellow in colour and are easily soluble in water. Its most characteristic reaction is the production of an intense purple coloration when neutralised with an alkali and a solu-tion of ferrous sulphate added. This is due to the formation of a double potassium ferrous salt, KFe(C3H4N30&, which crystallises from concentrated solutions in minute prisms having the lustre of bronze. The acetyl derivative of the oxime resembles the original substance in appearance, and melts with decomposit,ion at 190'. The ethyl ether is crystalline, and melts at 150-151". The oxime can be prepared by the action of nitrous acid on the aqueous solution of malonamide, and by the action of hydroxylamine on dibromomalonamide. By the action of nitrous acid on the oxime, a crystalline, sparingly soluble compound is obtained, which melts with decomposition at about 215'. It contains the proportion of nitrogen corresponding to a pseudo-nitro1 of the formula CONH,* C<No * CONK,.It does not respond NO2 to Liebermann's test, nor does it react as an oxime. By the continued action of nitrous acid, oxalic acid was the only solid product obtained. The oxime is reduced by hydriodic acid to aminomnlonamide, CONH,. CHNH,. CONH,, the hydriodideof which crystallises in prisms. The oxime of pyruvamide, CH,*C(NOH)*CONH,, prepared by the action of ammonia on the oxime of ethyl pyruvate, melts at 176-177" and closely resembles the oxime of mesoxamide, but the alkaline solu- tions exhibit no decided yellow colour, whilst the colour produced by the addition of ferrous sulphate to the alkaline solution is reddish-brown.In attempting to prepare the oxime of pyruvamide by the joint action of ammonia and hydroxylamine on ethyl pyruvate, the chief product ob- tained was the oximidohydroxainic acid, CH,. C:NOH* C<zgH, which is readily soluble, melts with decomposition at 143', and is distin-guished, not only by the cherry-red colour which is produced by the addition of ferric chloride, but by the production of an intense reddish- 146 brown liquid and subsequent precipitate on the addition of ferrous sulphate to the alkaline solution.Succinamide submitted to the action of nitrosyl chloride or of nitrous acid is attacked but slowly, yielding succinic acid, but no oxime or other derivative. Attempts to prepare Piutti's p-oxime of the half acid ethylsuccinic ester mere not successful ;this was apparently due to the spontaneous conversion of the ,@compound into Ebert's a-isomeride. Cramer (Bey., lS91, 24, 1204) represents the P-compound as the stable, and the a-as the labile isomeride. "91, On dimethyldiacetylacetone, tetramethylpyrone, and orcinol derivatives from diacetylacetone." By J. N. Collie, F.R.S., and B,D. Steele, M.Sc. That dimethylpyrone is capable of acting as a basic substance, forming salts with acids has already been clearly shown (Collie, Trans., 1899, 75, 710). This work has been continued and the basic properties of tetrnmethylpyrone have been investigated.The sodium salt of dimethylpyrone reacts with methyl iodide, giving dimethyldiacetylacetone, m. p. S7', C7H,C?,Na2 +2CH31= C,H,O,( CH,), +2NaI. When warmed with hydrocnforic acid this compound loses water and is converted into tetrarnethyZpy~one, C7H,03(CH,), =C7H,0,(CH,I, +H,O. Tetramethylpyrone melts at 92O. It crystallises from water as a monohydrate, m. p. 63-64'. It forms a hydrochloride and a platinichloride, but appears to be less basic than dimethylpyrone. From the residues after separation of the dimethyldiacetylacetone, two other substances have been ieolated, (1) trimethylpyrone, C,H,,O,, m.p. 7S0, which forms a platinichloride ; and (2) a derivative of orcinol, C9H1202,m. p. 150', possibly trimethyl- 1:2 :4-dihydroxy-3:5-benzene. This orcinol derivative resembles mesorcinol in a very remarkable manner, but it is difficult to see how mesorcinol, which is 1:3 :5-trimethyl-2 :4-dihydroxybenzene, could be produced from dimethyl-diacetylacetone. A second orcinol derivative, C,H,,O,, was obtained by treating the crude product of the action of methyl iodide on disodiumdiacetyl-acetone with hydrochloric acid. It melts at 105' and in all its reactions resembles the compound melting at 150'. Dimethylpyrone unites with sodium ethoxide to form a compound, C,H,O,NaOEt, which on treatment with acids yields ethyldiacetyl-acetone, C7H903Et.This latter substance is very unstable, and easily decomposes into alcohol and dimethylpyrone when heated with acids. "92. '' Dehydracetic acid." By J. N. Collie, F.R.S. Since the publication of a paper on dehydracetic acid (Collie and Le Sueur, Trans.,1894, 65,254), several reactions and the properties of various compounds of the acid have been investigated, all of which agree with the formula put forward by the author some years ago, namely, that dehydracetic acid is the lactone of tetracetic acid. The production of dehydracetic acid from triacetic lactone has been accom- plished, as indicated by the following equation, C6H603+(CH,CO),O =C,H,O, + CH,CO,H. Although neither acetyl chloride nor acetic anhydride react with triacetic lactone alone, if the lactone be boiled with acetic anhydride and a little sulphuric acid or sodium acetate, dehydracetic acid is formed. The action of ammonia on the isomeric acid C,H,O, (obtained by Feist from the dichloride of dehydracetic acid) has been investigated,and an acid, C,H,NO,, has been obtained identical with that previously isolated from the products of the action of heat on ethyl P-amidocrotonate.The production of dehydracetic acid from several of its dried salts has been studied. The dried sodium and silver salts treated with hydrogen chloride, and the dried lead salt with hydrogen sulphide, give dehydracetic acid. The conductivity of a very pure sample of dehydracetic acid has been determined by Prof.J. Walker, who finds it to be 0*0001. "93. '' The decomposition of hydroxyamidosulphates by copper sulphate." By E. Divers and T. Haga. When a hydroxyamidosulphate is heated in solution with copper sulphate it is entirely decomposed. This takes place in such a manner as to throw much light on the nature of the obscure decompositions of these salts, as well as of the hydroximidosulphates and hydroxylamine salts when impure. No change is observed in the copper sulphate during the change it brings about, but of its alternate reduction and oxidation evidence is given, if, instead of the sulphate, cupric chloride be employed, as this is reduced to cuprous chloride, The principal change caused by the copper sulphate may be repre-sented by the equation 2Cu(H2NS0,), =Cu(H,NSO,), +Cu(H,NSO,),, the latter salt being represented by the actual products CU(H~NSO~)~= N,O +H20+H,SO, + CuSO,.Another change always takes place at the same time, being less marked when the temperature is low, and more so when the temperature is high. For example, a hydroximidosul phate resists the action of the copper sulphate until the temperature of the solution is over 1OOO, when it hydrolyses to hydroxyamidosulphate, 28 per cent. of which decomposes so that all its sulphur becomes dioxide, its hydrogen water, and its nitrogen nitrous oxide. If one-third of the hydroxyamidosulphate decomposed thus, the reaction would be expressed by the equation, 3Cu(H,NSO,), = 2N,O + 4H20+2S0, + 2CuS0, + Cu(H,NSO,),.Hydroxyamidosulphate decomposing under theinfluence of copper sulphate may give as little as 34 per cent. of its sulphur as dioxide. In all cases, the quantity of sulphur appearing as sulphate approximately equals that as amidosulphate. The pro-duction of any free nitrogen is still doubtful; it could only be formed when the sulphur as sulphate exceeded in amount that existing as amidosulphate. *94. “The degradation of glycollic aldehyde.” By H. J. H. Fenton. As glycollic aldehyde is now obtainable in a pure state (Tkccns., 1895, 67, 774), experiments are being carried on with a view of studying its relationships and properties. The author showed that by means of Wohl’s reaction formaldehyde may readily be obtained from glycollic aldehyde.Glycollic aldoxime is obtained as a syrup from the interaction of the aldehyde and hydroxylamine in alcoholic rsolu- tion, but it has not been obtained quite pure. When this syrup is mixed with acetic anhydride and sodium acetate, a violent reaction takes place, and the acetyl derivative of glycollic nitrile (b. p. 177’) is formed. Thisisidentical with that obtained by Henry (Conzpt.rend., 1890, 110,759-760) from formaldehyde and hydrogen cyanide. When this acetyl derivative is acted upon by the calculated quantity of ammoniacal solution of silver oxide, silver cyanide separates in a crystalline state, and a product is obtained which, with dilute sulphuric acid, yields abundance of formaldehyde. 95. 66Noteson the chemistry of chlorophyll.” By Leon Marchlewski, Ph.D., and C.A. Schunck. The authors first discussed the absorption spectrum of unaltered chlorophyll, and conclude (1) that this spectrum is characterised by three bands between the lines B and F and three between F and K, ; (2) that the bands exhibited by crude leaf extracts are caiised by one chemical compound, chlorophyll, and not by several substances ; (3) that no solution which does not exhibit this spectrum can be said to contain chlorophyll, no mat’ter how it may have been prepared. Unaltered chlorophyll, by the action of hydrochloric acid, ought to give both phylloxanthin and phyllocya,nin, the latter most certainly. The authors contend that Hartley’s “blue chlorophyll” is not un- 149 altered chlorophyll, but a derivative closely allied to alkachlorophyll, since its spectrum is quite different from that of unaltered chlorophyll and gives with acids phyllotannin or its derivatives, but neither phylloxanthin nor phyllocyanin.As to the several L‘ chlorophylls,” the authors corroborated the results of Hartley and Eorby’s experiments, which tend to show the existence of a colouring matter besides chlorophyll proper and the members of the xanthophyll group. They show, however, that Hart- ley’s “yellow chlorophyll ” is a mixture of this additional colouring matter with members of the xanthophyll group, and that by removing the latter its colour is green ;the name “yellow chlorophyll ” is there- fore unsuitable. Crude leaf extracts therefore contain two green colouring matters, chlorophyll proper and another which is present only in small quantity ;this exhibits a red fluorescence and is character-ised by an absorption band in the red which is more refrangible than that of true chlorophyll.The authors described a method by which chlorophyll could be obtained almost free from this green colouring matter, and from the members of the xanthophyll group. The action of bromine on phylloporphyriri and hEmatoporphyrin is very similar, and this is considered by the authors as an additional proof of the close relationship of these substances. 96. “A new series of pentamethylene derivatives, I.” By W. H. Perkin, jun,, Jocelyn F. Thorpe, and C. Walker. When ethyl aa’-dibrom-PP-dimethylglutarate, C0,Et *CHBr*C(CH,),*CHBr*CO,Et, is treated with an alcoholic solution of potash, it is converted quantita- y(OC,H,)CO,H ,which separates tively into ethoxycaroniccccid, (CH,),C<CH, CO,H from benzene in long needles melting at 136’; the ccniiydyide, made by distilling the acid, boils at 160-165’ (50 mm.), and on boiling with water is reconverted into the acid.When warmed with concentrated sulphuric acid, or when heated with hydrobromic acid in a sealed tube, the acid is converted into the anhydride of asym-dimethylsuccinic acid, (CH,),F---CO>(),CH,*COL which melts at 39’, and on boiling with water yields asym-dimethyl- succinic acid melting at 139”. When ethyl di bromdimethylglutarate is condensed in alcohol solu- tion with an equimolecular proportion of ethyl sodiomalonate, a 60 per cent.yield of an ester of the probable formula 150 is produced; it is a thick liquid which boils at 234' (20 mm.), and on hydrolysis with alcoholic potash is converted into the tribasic acid, Y(CO,H)*CH,*C0,H (CH3)2C<CH. CO,H ,a colourless substance which separates Y from water in small needles and melts at 176' with evolution of aqueous vapour. When ethyl dibromdimethylglutarate is condensed with 2 equivalents of ethyl sodiomalonate in the presence of excess of sodium ethoxide, a yellow sodium compound of the formula Q(CO,Et)* y(Na)* CO,Et (~HJ~C<C(CO,Et)*CO is produced to the extent of 60 per cent,. of the theoretical amount ; it is a remarkably stable substance, giving in alcoholic solution a deep red coloration with ferric chloride, and on hydrolysis in the cold with methyl alcoholic potash is converted into Q(CO,Et)*$lK*CO,Etthe yellow potassium compound, (CH3)2C<C,C0,K>.co , this when acidified, gives the corresponding acid ester, F1(CO2Et)*FH*CO2Et (CH3)2c<cp02H )-co 9 which crystallises from dilute alcohol in large prisms and melts at 755 On distilling this acid ester under diminished pressure, carbon dioxide is eliminated, and the ester, (CH,),C< Q(CO,Et)* vH*CO,Et CH-GO passes over at 201' (30 mm.) as a thick oil which gives an intense violet colour with ferric chloride, and on hydrolysis with potash is con- stance crystallising from concentrated hydrochloric acid in large prisms and melting at 179'; it gives a red coloration with ferric chloride.When the sodium compound mentioned above is treated with an equal weight of potash dissolved in ethyl alcohol, it passes into solution, and on boiling deposits a potassium salt, of the probable constitution, ?(CO,K)-QK*CO,K ; this, on being acidified, yields a mix-(CH3)2C<C( CO,K)*CO ture of two isomeric acids, which can be separated by recrystallisation from dilute hydrochloric acid. The more soluble acid is identical with the acid mentioned above melting at 179', the less soluble acid crystal-lises from dilute hydrochloric acid in needles melting at 154-1 55';with evolution of carbon dioxide ;it gives an intense violet colour with ferric chloride; the first acid is called the a-,the second the P-modification.Both modifications, the 6-on heating above its melting point, the a-on heating with water in a sealed tube at 200°, are quantitatively convert ctl into the acid, (CH,),C<CII~(CO,H)*FH,co , which crystallises 151 from water in fern-like needles melting at 180' and subliming when heated, in long, silky needles ;the sernicarbaxone melts and decomposes at 225', and the hydrazone at 217'. On reducing the ketonic acid melting at 180' with sodium amalgam it behaves in a remarkable manner, the ketoce group remaining intact and the trimethylene linkage being reduced, forming the acid, CH*(CO,H)*FH2 (UH3)2<CH -co , which separates from water in microscopic needles melting at 103' ;the sernicarbaxone decomposes at 215'.When the yellow sodium compound mentioned above is treated in alcoholic solution with methyl iodide it is converted into the ester ~(C0,Et)*~(CH3)C0,Et (CH3)~~~C(Co2Et)*co , a colourless oil boiling at 219' (20 mm.) and gLving no coloration with ferric chloride. On hydrolysis with methyl alcoholic potash, this ester is converted into a potassium salt which when acidified gives the acid y(C0,H)*S(CH3)*C0,H (CH3)2C <CH- co , a colourless substance crystal-lising from benzene in lustrous plates melting at 146', this, when heated in aqueous solution at 200°, gives the acid, ~(co,H)*QH(cH,) (CH,),C<CH-co ,which separates from water in glisten- ing plates and melts at 134'; the semicaybaxone decomposes at 230'.If the potassium salt just mentioned be not separated, but the heating continued, it passes into solution with the formation of an acid characterised by being practically insoluble in dry ether, and which differs from the acid melting at 146' in containing 1 mol. of water of constitution. It separates slowly from water in large prisms melting at 237O, and when distilled under ordinary pressure passes over at about 270' as an oil which solidifies on cooling. This on boiling with water is converted into an isomeric acid which separates from water in needles melting at 18O-1Slo, with formation of the anhydride. The reactions of these compounds seem to indicate that they are stereoisomeric furfurane derivatives having the formula C(CO,H)*C(CH,)CO,K >o (CH3)2C<dH CH(0H) The investigation of these compounds, which are closely allied to several derivatives of the camphor and terpene series, is in progress, and experiments are being carried out in order to study the behaviour of other glutaric acids under the conditions indicated above.97. LL Experiments on the synthesis of camphoric acid. 111. The action of sodium and methyl iodide on ethyl dimethylbutanetri- carboxylate.” By W. H. Perkin, jun., and Jocelyn Field Thorpe. When ethyl dimethylbutanetricarboxylate (Trans., 1899, 75, goo), dissolved in toluene, is treated with sodium and then with methyl iodide, a considerable yield of an ester is obtained which boils at 168-170’ (18 mm.), and on analysis gives numbers agreeing with the formula C14H2205, The method of formation of this substance clearly indicates that it must have one of the two following constitutional formulte : C(CH,), C(CH3),/\ /\CO,Et*$lH y(CH,)CO,Et 7H27HC0,Et CH,*CO CO--C( CH,)CO,Et’ I.11. If the ester has the constitution represented by formula I, it must be closely allied to, and will probably be easily converted into, an acid C(CH3),/\having the constitutional formula CO,H*YH ?(CH,)*CO,H, assigned CH,. CH, by Bredt to camphoric acid. On reduction by means of sodium amalgam, bhis ester is converted quantitatively into a syrupy hydroxy-acid, which on long standing shows signs of crystallising. The analysis of this acid and its silver salt shows that it has the formula C,,H1GO,; it is therefore isomeric with camphanic acid.The authors are contincling the investigation of these substances. 98. LL The oxyphenoxy- and phenylenoxy-acetic acids.” By W. Carter and W. Trevor Lawrence. The phenylenoxyacetic acids, CGH,(OCH2C0,1’I),, are obtained ac-cording to either of the following equations : 1. C,H,(ONa), +2CH2BrC0,Et =C,H4(0CH2CU,Et), +2NaBr. 2. C,H4(ONa)2 + 2CH,ClCO,Na =C,H,(OCH,CO,Na), +3NaC1. The condensation according to the first equation is not complete in the cases of resorcinol and hydroquinol, and a certain amount of acid ester, C,H,(OH)(OCH,CO,Et), corresponding to the oxyphenoxyacetic acids is formed, and may be separated from the neutral ester by potash solution.On pouring the esters into alcoholic potash the potassium salts of the acids are precipitated as microcrystalline powders, which when acidified yield the free acids, The amides are obtained from the esters by shaking with aqueous ammonia, the aniline salts result on boiling the acids with a benzene solution of aniline, and the anilides are obtained by heating the acids to 190' with aniline. Pyrocatechol derivatives. Ethyl pyrocatecholdiacetute, C,H,(OCH,CO,Et),, boils at 230-232' (30 mm.). Pyrocatecholdiacetic cccid, C6H,(OCH,C'0,H),, needles from water, m. p. 178'. Aniline scclt, m. p. 250'. Bcwizcm scclt, 2(C,,H,06Ba),H20. Pys~ocutecholdiucetanilide,C,H,(OCH,CONHPh),, m. p. 196". P~?.ocutecho~c~iucetu~zic~e,C,H4(OCH,CO~H,)2, m.p. 203'. Ethyl yyrocatecho~naonoacet ute. C,H,(OH) (OC'H,CO,Et), b. p. 155' (30 mm.). P~rocatecholmolzoacetic mid, C6H4(OH)( OCH,CO,H), prisms from water, m. p. 152'. A~zkyds~opyrocutechoZmonocccetic O*CH acid, C,H,<~.~~', prisms from ligroin, m. p. 57'. Pgrocatechol-monoacetunilide, C,H,(OH)(OCH,CONHPh), m. p. 161'. [Compare Moureu, Bull., 1899, [iii], 21, 1071. Resorcinol derivatives. Ethyl resorcindiacetate, C,H,(OCH2C02Et),, m. p. 42' (B. 40°), b. p. 228' (32 mm.). Reso~cindiacetic acid, C,H,(QCH,CO,H),, m. p. 195'. The silver, copper, and iron salts are amorphous, the calcium and barium salts crystalline. Aniline scclt, m. p. 137'. Resorcindiucet-anilicle, C,H,(OCH,CONHPh),, m. p. 169' (B. ca. 182').Ivaidoestes-, [C,H,( OCH,CO,Et)OCH,CO] ,N H, m. p. 43'. liesorcindiacetamide, C6H4(QCH2CONH2),, m. p. 167". 2 : 4 : 6-Trinitro~eso~cindiucetic acid, C,H(NO,),(OCH,UO,H),, is formed by boiling resorciadiacetic acid with nitric acid, m. p. 174', converted by potash at 140' into styphnic acid. Resorcinrnonocccetic cccid, 3 (C,H,O,),H,O, m. p. 158', anhydrous needles from toluene, m. p. 160' (B. 158'). Resorcinmono-acetnnilicle, m. p. 125'. Hydroquinol derivatives. Ethyl I~~droguinol~icccetute, G',H,(OCH,CO,Et),, needles from ligroin, m. p. 72'. Hydroquinoldiacetic acid, C,H,(OCH,CO,H),, prisms in-duble in all solvents tried except acetic acid, m. p. 251' (B. ca. 246"). Hydroquinoldiacetanilide, C,H,(OCH,CONHPh),, m. p. 210'. The ammonium salt crystallises in needles from water, the silver and copper salts are amorphous, and the calcium and barium salts crystalline.Hydvoquinolmonoacetic acid, 3( C,H,O,),H,O, prisms from water, anhydrous needles from toluene, m. p. 152'. Aniline salt, m. p 119'. Hydroqwinolmonoacetanilide,C,H,(OH)(OCH2CONHPh), m. p. 101'. The melting points in brackets, and indicated by B, refer to a 154 private communication from Prof, C. A. Bischoff, who is engaged in the investigation of many of these substances, in pursuance of his ''Studies on Condensations," and to whom we therefore relinquish their further study. 99. '(The condensation of ethyl a-bromoisobutyrate with ethyl malonates and ethyl cyanacetates : a-methyl a'-isobutylglutaric acid." By W.Trevor Lawrence, B.A.,Ph.D. The author showed that the following general reactions hold good : I. CNaRX( C0,Et) +CBr(CH,),CO,Et =CRX( CO,Et)*C(CH,),(CO,Et) +NaBr, when the sodium compound is in suspension, 11. CNaRX(CO,Et,) +CBr(CH,),(CO,Et) = CRX(CO,E;t)*CH,*CH(CH,)(CO,Et)+NaBr, when the sodium compound is in solution, where R=H or an alkyl group ; X=(CN) or (C0,Et). The behaviour of ethyl bromoisobutyrate is probably influenced by the degree of ionisation of the sodium compound. The author suggests that the hydrobromic acid liberated from the bromoisobutyric ester combines with (the enolic form of) ethyl sodio- malonate or -cyanacetate to form a hypothetical addition compound, for /ONaexample, CN*CHR*C-Br , which condenses with the unsaturated \OC,H, ester with separation of sodium bromide.The following substances were isolated and investigated in the course of this research :--I. In the condensation of ethyl sodioisobutylmalonate with ethyl a-bromoisobutyritte, or ethyl a-methacrylate in alcoholic solution. Ethgl a-methyl-a'-isobutyllwopccnetricarboxylade, CH(CH,)CO,Et* CH,* C(C,H,)(CO,Et),, b. p. 1S5' (18 mm.), converted by hydrolysis with alcoholic potash in to t fie potassium salt of a-methyl-a'-isobutylpopanetricarboxylicacid. This acid melts at 167-168" (with evolution of carbon dioxide and formation of cis- and trans-metlhylisobutylglutaric acids). The cis-and tram-methylisobutylglutaric acids, CH(CH,)(CO,H)*CH,*CH( C,H9)C0,H, are best separated by crystallisation from boiling ligroin (b.p. 110-1200). cis-Acid, m. p., 121'. Anhydride, a liquid, b. p. 196' (50 mm.). Anilic acid, C',,B,,03N, m. p. 164'. trans-Acid, m. p. 86-87'. Anhydride, a liquid, b. p. 178' (22 mm.). Anilic acid, m. p. 196'. The tyans-acid may be converted into the cis-modificat ion by heating 155 with hydrochloric acid in a sealed tube, or into the cis-anhydride by distillation or by heating with acetic anhydride to 220'. 11. In the condensation of ethyl sodioisobutylcyanacetate, b.p. 165" (50 mm.), with ethyl bromoisobutyrate or ethyl a-methacrylate in alcoholic solution : in the condensation of ethyl sodiocyanacetate with ethyl methacrylate and subsequent addition of is0butyl bromide. EthyI a-methyl-a'-isobutyl-a'-cyccnoglutayate, CH(CHJC0,Et *CH,*C(C,H,)(CN)(CO,Et), b.p. 196O (25 mm.), on hydrolysis with alcoholic potash, is converted into the potassium salt of a substance, C,,H,,O,N, which melts at 164O, with evolution of carbon dioxide. This substance is possibly a mixture of methylisobutylcyanoglutaric acid with the monocarboxylic acid of methylisobutylglutarimide, as on distillation (295O, 760 mm.) the imide (m. p. 78O) of the cis-acid (insoluble in sodium carbonate) and the nitrile of the ts*ans-acid are obtained. It is converted by hydrochloric acid into a mixture of tram-glutaric acid and cis-glutarimide. The complete hydrolysis of the nitrile or imide is effected by 50 per cent. sulphuric acid. 111. In the condensation of ethyl bromoisobutyrate with ethyl sodio- isobutyl-malonate or -cyanacetate in benzene solution : in the con-densation of ethyl bromoisobutyrate with ethyl sodiocyanacetate in alcoholic solution with subsequent addition of isobutyl bromide.Ethyl aa-dimethyl-a'-isobutyl-a' cyansuccinate, b. p. 180' (20 mm.), CO,Et*C(CH,),* CH(C,H,)(CN)(CO,Et), when hydrolysed with alcoholic potash and then acidified, gives a pasty mass of cyano-acid-on com-plete hydrolysis with 50 per cent. sulphuric acid it gives aa-dimethyl-a'-isobutylsuccinic cccid, CO,H*C(CH,),*CH( C,H,)CO,H, prisms from water, m. p. 141O. Experiments on the oxidation of methylisobutylglutaric acid (the study of which was the original object of this research) with potass- ium permanganate either at 60' or in the cold, showed that the greater part of the acid could be recovered unchanged, the oxidation products consistingof oxalic acid, isobutylmalonic acid, a fatty acid (isobutylacetic acid ?), two liquid acids, of which one appeared to be a hydroxy-acid, C10H1805,and the other an unsaturated acid, ClOHl6O4,and a crystal- line acid, m.p. SOo, of the same composition. These acids were obtained in very small quantities and their com- plete separation was both difficult and probably unsuccessful. 156 100. '(Xethylisoamylsuccinic acid. 11.'' By W. Trevor Lawrence, B.A.,Ph.D. The anil of trans-a-methyl-a'-isoamylsuccinic acid melts at 11So, and that of the cis-acid at 116'. The partial conversion of the cis- into the trccns-modification may be brought about by heating with hydrochloric acid, and the reverse change by heat'ing the twins-acid with acetic anhydride at 210'.The cis-anhydride is converted by phosphorus pentabromide, bromine, and alcohol into ethyl a-bromomethylisoamylsuccinate (b. p. 155', 20 mm.), C14H2504Br,which, when poured into hot alcoholic potash forms the potassium salt of isoamylcitraconic acid, C02H*C(CH,) :C(C',H,,)*CO,H. Oxidation of methylisoamylsuccinic acid by means of potassium permanganate gave results similar to those obtained by the oxidation of the isomeric methylisobutylglutalric acid (compare preceding abstract) ; only a small portion of the acid mas oxidised by the per- manganate, giving oxalic acid, a liqnid acid having the formula C10H1604,and a lactonic acid having the same formula and melting at 103'.Correction.-Isoczmylsuccinic acid melts at 83-84', not 76' as previously stated (PYoc.,1899, 15, 163). 101.(' The estimation of furfural." By William Cormack. The process proposed by the author is based on the oxidation of fwfural to pyromucic acid by means of an arnrnoniacal solution of silver oxide, according to the equation C,H40, + Ag,O = C,H,03 + 2Ag. The action takes place quantitatively when the solutions are warmed. A known volume of a decinormal silver oxide solution, somewhat in excess of that required for the oxidation of the furfural, is added to the furfural solution, the reduced silver is filtered off through asbestos, and the silver remaining in the filtrate estimated by means of deci-normal ammonium thiocyanate.The method is applicable to furfural solutions such as those derived from fibres by distillation with hydrochloric acid, the furfural being distilled over with steam from the solution after neutralisation with a1kaline carbonate, and subsequent slight acidification with oxalic acid. 102. (( The constitution of hydrogen cyanide.'' By John Wade. When potassium cyanide is heated with alkyl potassium sulphates at: st lower temperature than in the preparation of nitriles, the isomeric isocyanide is often the principal product. The author also 157 has found that practically all the isocyanides can be converted into nitriles by the action of heat.The formation of nitriles in the above interaction is thus accounted for, and one of the arguments in favour of the nitrilic constitution of hydrogen cyanide disappears. Isocyanides form crystalline products with aldehydes, probably homologous with the aldehyde cyanhydrins, for which the formula R*?H’?:NH is suggested, as the ordinary formula does not account -0-for their anomalous behaviour with alkalis. Compounds have in this way been obtained from acetaldehyde and benzaldehyde in conjunction with methyl-, ethyl- and phenyl-isocyanides. Isocyanides also form crystalline products with alkyl iodides in presence of alcohol. This interaction accounts for the non-appearance of isocyanides, and probably for the formation of nitriles, when potass- ium cyanide is heated with alkyl iodides in presence of alcohol.Corn-pounds of this class have been obtained from m‘ethyl-, ethyl-, propyl-, isopropyl-, butyl-, isoamyl-, and phenyl-isocyanides in conjunction with methyl, ethyl, propyl, isopropyl, isobutyl, and isoamyl iodides. n-Propyl isocyanide, and n-but92 isocyanicle do not appear to have been prepared before. They are formed by interaction of the alkyl iodides with silver cyanide, and boil respectively at 97-99O and 118-120O (uncorr.). 103. 6‘ Inhibiting effect of etherification on substitution in phenols,’’ By Henry E. Armstrong and Edward W. Lewis, The inhibiting effect on substitution produced by introducing methyl, ethyl or benzyl in place of the hydroxylic hydrogen in phenolpsra- sulphonic acid has already been referred to (Armstrong, P7*0c., 1899, 15,177).At the last meeting of the British Association, it was pointed out that “ benzoyl appears to exercise a very remarkable inhibitive effect, as preliminary experiments show that benzoylated phenol- parasulphonic acid remains unattacked by bromine under conditions which involve the conversion of the unbenzoylated acid into tribromo- phenol.” This observation has since been confirmed, and the ex-periments have been extended in order to determine the effect of radicles generally. Besides benzoyl, pheny lsulphonyl, Ph*SO,*, benzyl- sulphonyl, Ph*CH,*SO,*,and the radicle of Reychler’s cnmphorsulphonic acid, C,, HI,O*SC),*, afford complete protection against bromine.PicryI, C,H,(NO,),*, also appears to behave like benzoyl, but owing to the instability of picrylphenolparasulphonate in aqueous solution it is difficult to determine the exact nature of the change effected by bromine. Acetyl, on the other hand, exercises an effect similar to that produced by methyl and ethyl ; and the complex radicle phenacyl, Ph*CO*CH,*,derived from acetophenone, acts much in the same way as acetyl. Difficulty has been experienced in determining the influence of the isomeric radicle phenacetyl, Ph*CH,*CO*, owing to the in-stability of the ether produced by it; apparently, it also resembles acetyl. In order to ascertain whether a determining influence is exercised by hydrogen in association with the carbon atom which becomes attached to the phenolic oxygen, tertiary butyl was introduced into phenolparasulphonate.The effect produced by this radicle seems to be altogether different from that of either methyl or ethyl, because on treating the sulphonate with one molecular proportion of bromine, only rnonobromosulphonate is obtained, the sulphonic radicle remaining intact, but it is displaced by a second molecular proportion of bromine; the methyl and ethyl derivatives are, to a large extent, directly converted into the parabromophenol ethers. In view of this observation it will be necessary to examine other alkyl derivatives. 104. ‘(Bromination of oxYazo-compounds.” By Henry E. Armstrong and Percy C.C. Isherwood. The observations recently made by Hewitt and Aston and by Auwers unquestionably prove that the compound formed by the inter- action of phenol and a diazobenzene salt, behaves, in the main, as benzeneazophenol, and there is no doubt that the isodynamic hydrazone comes prominently into evidence only in the presence of acids; it is clear, however, that the equilibrium is easily disturbed in either direc- tion, and that in such a case the constitution cccn onlp be finally in- ferred from physical rather than chemical properties.The authors must confess to having been too much influenced by the extraordinary difference in the behaviour of this compound towards excess of bromine as compared with that of its ethylated derivative, but apparently it is not necessary to infer from this that the two are structurally different, as the principle developed by one of them in discussing the laws which govern substitution in benzenoid compounds suffice to afford an explanation of the dissimilarity.The conversion of benzeneazophenol into benzeneazodibromophenol and its resolution by excess of bromine into diazobenzene and tri-bromophenol are comparable with the conversion of phenolpara-sulphonic acid, first into the dibromosulphonate, and then into tribromophenol and sulphuric acid. Ethylation exercises an inhibiting influence such as is referred to in the previous abstract, benzeneazophenetol being converted by bromine in presence of sodium acetate only into benzeneazomonobromophenetol. This compound is also formed when a solution of the phenetol in glacial acetic acid is brominated, but at the same time a “hydro-bromide perbromide” is formed which is readily deprived of its bromine by reducing agents.In a previous note (PYoc., 1899, 15, 243), the mistake was made of inferring from observations made with this latter compound that benzeneazo-orthobromophenetol is an easily reducible substance. As the separation of the azo-group from Hewitt and Aston’s benzeneazodiorthobromophenol by bromine is effected even in presence of sodium acetate, it cannot be argued that the scission is consequent on the formation of the hydrazone, and the stability of benzeneazo-phenetol must therefore be ascribed to the change produced by dis- placing the hydroxylic hydrogen, The extreme readiness with which the compound assumes the hydrazone form is manifest from the fact that if the sodium acetate be omitted and two molecular proportions of bromine are used, the substance being merely dissolved in acetic acid, benzeneazodiorthobromophenol is mainly resolved into bromo- diazobenzene and tribromophenol. Benzoylated benzeneazophenol, like benzoylated phenolparasulphonic acid, is unaffected by b rornine.Clearly, it mill be desirable to study further oxy-as well as amido-azo-compounds from the points of view indicated in the preceding abstract. 105. Meta-sulphonation of aniline.” By Henry E. Arrnstrong and W,Berry, It has been pointed out by one of the authors that, “in order to produce meta-derivatives from amines, it is necessary to paralyse, as far as possible, the ordinary ortho-para-orien tating influence of the amino-group and to give opportunity for the attack to take place in the nucleus” (Proc., 1899, 15, 177 ; compare B.8. Repoist, 1899, 685, $ 11). In the case of aniline, sulphuric acid alone appears to be capable of exercising the necessary protective influence, because if the sulphate be dissolved in a large excess of chlorosulphonic acid, the mixture may be heated to 30-40’ without any appreciable amount of hydrogen chloride being evolved. Under these conditions, the chlorosulphonic acid is not a sufficiently powerful sulphonating agent to produce even the sulphamate. Consequently, if aniline sulphate be added to a sufficiently strong fuming sulphuric acid, it is in part converted into the meta- sulphonic acid, the nucleus apparently being directly attacked.It is therefore possible to convert aniline into either para-or ortho-or meta-sulphonic acid at will. 160 106. .6i Phenylacetylchloramine and analogous compounds.” By Henry E. Armstrong. The author calls attention to the discrepancies in the descriptions given of the properties of phenylacetylchloramine, and discusses the manner in which it undergoes isomeric change. 107. Benzglanilinesulphonic acids.” By Ida Smedley. These acids have been prepared in order to compare their behaviour with that of the corresponding methyl and ethyl derivatives studied by Miss Evans (Proc., 1895, 11,235 ; 1896, 12,234).Anilineparasulphonic acid is readily benzylated by digesting an aqueous solution of its sodium salt with benzyl chloride and alkali, the mono-or di-benzyl derivative being formed according to the proportions used. The meta-acid is dibenzylated with extreme readiness. In their behaviour with bromine, the dibenzylated closely resemble the dimethylated acids. It may therefore be assumed that benzyl does not promote the displacement of the sulphonic group as it does when introduced into phenolparasulphonic acid in place of the hydroxylic hydrogen, but it undoubtedly has an influence different from that exercised by either methyl or ethyl. Thus it is characteristic of dimethyl- and diethyl-sulphanilic acids that, when acted on by bromine, each is converted into an ortho-brominated acid capable of combining with bromine to form a comparatively stable perbromide.The dibenzyl acid yields a similar monobrominated acid, but this does not form a perbromide; it is, however, very easily deprived of its benzyl by the further action of bromine. 108. Benzeneorthodisnlphonic acid.” By Henry E. Armstrong and S. S. Napper, The authors have prepared benzeneorthodisulp honic acid by applying Leuckart’s xanthate method (J.pr. Chena., 1890, 41, 179) to para- bromanilineorthosulphonic acid, A series of compounds has thus been obtained corresponding with those prepared by Miss Walter (Proc., 1895, 11, 141) from sulphanilic acid. Potassium parabromophenylxanthateorthosulphonate is easily soluble in water, from which it crystallises with 10 molecules of water. When hydrolysed by means of sulphuric acid or alcoholic potash, it yields the corresponding thiophenolsulphonic acid, C6H,Br(SH).S0,H, or its potassium salt, the thiophenetolsulphonate, C6H,Er(SEt)*S0,K, being also formed when it is hydrolysed by aqueous potash, and when it is decomposed by heating at about 200”.161 Bromobenzene-3 : 4-disulphonic acid is conveniently prepared by directly oxidising the xanthate with potassium permanganate. Its sulphochloride crystallises in monosymmetric prisms melting at 58O. The amide crystallises in brilliant anorthic prisms; the anilide in monosymmetric plates melting at 182'. It is converted into benz-eneorthodisulphonic acid by boiling its aqueous solution with soda and zinc dust.Sodium benzeneorthodisulphonate is very soluble in water, from which it crystallises in long, transparent prisms. The barium salt is sparingly soluble even in hot water, and crystallises in glistening plates. Unlike 1:2-naphthalene-1:2-orthodisulphonicacid, but like toluene-3 :4-disulphonic acid, benzeneorthodisulphonic acid is converted into the corresponding chloride by phosphorus pentachloride. This crystallises in magnificent monosymmetric prisms melting at 143'. The corresponding amide and anilide also crystallise in monosym- metric prisms, the former melting at 252O, the latter at 241'. A comparison of the acid with phthalic acid is being made. 109. "An isomeride of furfurine." By J.P,Millington, B.Bc,, and H. Hibbert, B.Sc. By the application of the method of Japp and Moir (Truns., 1900, 77, 637) for the preparation of isoamarine from amarine the authors have succeeded in preparing an isomeride of furfurine. It crystallises from water in needles melting sharply at 143O(furfurine melts at 116O) and on analysis was found to correspond with the formula C1,Hl2N,O,. A platinichloride and silver derivative have been obtained of which the f ormulze are (C,,H,,N,O,),H,PtCI and C,,H,,N,O,Ag respectively. 110. The mono- and di-acetyl and phenacetyl diethyl tartrates. By J. McCrae andT. S.Patterson. The preparation of monoacet yl, diacetyl, monophenacetyl, and di- phenacetyl diethyl tartrates mas described. Considerable difficulty was experienced in the purification, and different methods had to be adopted in each case.The specific rotation of these substances has been determined at various temperatures with the following results :-Monoacetyl diethyl tartrate ............ [a]: = 1-9.30' y,,Diacetyl ,.........." [alp= +6.30° Alonophenacetyl ,, ,, ............ [a]2p = +30.38' Diphenacetyl ,, ,, ............ [u]: = + 17'92O A cornpaxison is instituted, on the one hand, between the series of 162 monoacidyl tartrates, where it is shown that the phenacetyl radicle exerts a much greater influence than that exerted by the acetyl radicle, and, on the other hand, between the members of the series of diacidyl tartrates where the acetyl and phenacetyl radicles behave similarly but very differently from the toluyl radicles.The regularity of the influence exerted by the successive introduc- tion of two acidyl groups is noticed. The first acidyl group increases the rotation of the diethyl tartrate, but the second acidyl group diminishes the rotation of the monoacidyl compound. NILSON MEMORIAL LEG TURE. The Nilson Memorial Lecture will be delivered by Professor Otto Pettersson, of Stockholm, on the evening of Thursday, July 5th, 1900. The Chair will be taken at S.30. LIBRARY. The Library will be closed €or stock-taking during the first fortnight of August. Fellows are requested to return all Library books in their possession before July 28th.
ISSN:0369-8718
DOI:10.1039/PL9001600143
出版商:RSC
年代:1900
数据来源: RSC
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