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Proceedings of the Chemical Society, Vol. 17, No. 234 |
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Proceedings of the Chemical Society, London,
Volume 17,
Issue 234,
1901,
Page 43-52
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摘要:
OF THE CHEMICAL SOCIETY. EDITED BY THE SECREYARZES. ___--VOl. 17. No. 234. ___-__ March 7th, 1901. Dr. PENKIN,F.R.S., Vice-president, in the Chair. Messrs. T. H. Page and James Moir were formally admitted Fellows of the Society. The following certificates were read for the first time :-Ernest Clark, 9, Polygon Avenue, Stockport Road, Mnnchester ; Thomas Kennedy Cockburn, 26, Elm Street, Whiteinch, Glasgotv ;Eustace Coddington, 131, St. James’ Road, Upper Tooting, London, S.W. ; Hugh Edward Ellis, 18, Belmont Road, Aberdeen ; John Vargas Eyre, 26, Bridge Road West, Battersea Park, S.W. ;Francis Robert Henley, Watford, Rugby; Charles Edward Kenneth &lees, 33, St. Saviour’s Road, Croydon ;Arthur Peacock, Smithies Bridge House, Heckmondwike, Yorks.;William Hammond Robinson, The Limes, Painswick Road, Cheltenham ; Henry Ewing Smith, 22, City Road, London, E.C.; William Henry Taylor, 19, Shafton Road, Victoria Park Road, W.E. Of the following papers, those marked * were read : “29. LL Nomenclature of the acid esters of unsymmetrical dicarb-oxylic acids.” By J. J. Sudborough. After mentioning the systems adopted by Briihl, Wegscheider, and Anschiitz, the author suggeste6 the following nomenclature. Of the two isomeric monoalkyl esters of an umymmetrical dibasic acid, that ester be termed the a-compound which has the higher esteri- 44 Gcation constant, and the other with the lower constant the p-com- pound. The advantages of this system are : (1) similarly constituted esters receive similar names; (2) in the case of many of the simpler acids, the substituent which produces the want of symmetry is in the a-position to the alkylated carboxylic group; (3) ease with which the two esters may be identified.*30. (( Additive compounds of a-and P-naphthylamine with trinitro- benzene derivatives," By J. J. Sudborough. The red needles which were obtained when a-naphthylamine tri- nitrobenzoate was boiled with alcohol (Trans., 1899, 75, 588) are an additive compound of trinitrobenzene with a-naphthylamine. A number of other similar compounds have been obtained ; all are red or reddish-purple in colour, are remarkably stable, may be crystal- lised from glacial acetic acid, and are only slowly decomposed by cold dilute hydrochloric acid ; they are also stable when exposed to the air, and in these properties differ from the additive compounds of trinitrobenzene, with aniline, toluidine, &c., described by Hepp (Anncclen, 1882, 215, 344).The following are the compounds which have been prepared: trinitvo-a-napJtth,ylamine trinitrohenxene, m. p. 2 14' ; P-napJ~tJ~ylamine benzene, m. p. 162' ; a-napl~thylarnine trinitrotoluene, m. p. 141*5', the P-isonzeride, m. p. 113.5' ; a-naphthylcmine pierartaide, m. p. 203O, and the P-isomeyide, m. p. 161.5' ; a-nctplhtlhylanzine ethyltrinitrobenxoate, m. p. 135O, and the p isomeride, rn. p. 126'; a-ncqvhthylamine ethylpicrate, m. p. 79.5' ;and a-rtcbphthylamine nzethylpicrate, m. p. 75". With the object of determining the constitution of these com-pounds, the action of acetic anhydride and of alcoholic potash on them has been studied ;it was thought probable that these reagents might indicate the presence of a hydroxyl group.a-Naphthylamine trinitrobenzene and acetic anhydride warmed for a few minutes yield a monoacetyl derivative, which crystallises from benzene in sulphur-yellow needles melting at 140.5'. The com- pound has the acetyl group attached to nitrogen, as the same sub-stance may be obtained by the direct union of trinitrobenzene and a-acetnaphthalide, and as it yields a-acetnaphthalide on treatment with methyl alcoholic potash. Several similar acetyl derivatives have been prepared. A methyl alcoholic solution of potassium hydroxide decomposes the red compounds, yielding the potassium dei ivative of trinitrobenzene de- scribed by Lobry de Bruyn.45 ”31. Acetylation of arylamines.” By J. J. Sudborough. According to Ulffers and von Janson (Ber.,1894,27,93), acid ortho- substituents retard the introduction of an acetyl group into a primary arylamine, but at the same time facilitate the introduction of a second acetyl group. Quantitative experiments have been made by boiling aniline, o-toluidine, p-toluidine, pseudocumidine, a-and P-naphthylamines with acetic anhydride for an hour and determining the percentage of the arylamine converted into mono-or di-acetyl compounds. The results indicate that a methyl or phenylene group in an ortho-position facilitates diacetylation.All o-substituents, whether of a positive or negative character, thus appear to have the property of accelerating the formation of diacetyl derivatives of primary arylamines. The following new compounds were described : DicccetyZ-~seudocuniid-ine, C,H,Me,.NAc, [Me, : N = 1:2 :4 :51, well developed, transparent prisms melting at 69-5”;cEiacetyl-a-nc~plr,thyZc~mine,C,,H7NAc,, colour-less, hard prisms melting at 130’ ; diacetyl-P-nc~~ht7yZa~tine,colourless plates melting at 66.5’ ; and diacetyl-2 :6-dibrornaniline, large prisms melting at looo. Most of these diacetyl derivatives crystallise re-markably well, and are readily soluble in the ordinary organic solvents. “32. “Formation of amides from aldehydes.” By R.H. Pickard and W. Carter. When an aldehyde is oxidised with ammonium persulphate in the presence of lime, a 30-40 per cent. yield of the amide of the corre- sponding acid is obtained. The greater portion of the remainder OF the aldehyde can be recovered unchanged, and by further oxidation the yield of amide can be increased to 70 per cent. of the weight. of aldehyde taken. Substituted amides can be obtained by using potassium persulphate and an amine. *33. “A method of isolating maltose when mixed with glucose,” By A. C. Hill, M.A. This method is, essentially, one of removal of the glucose by ferment- ation with Saccharomyces Ma~xiccnus,a yeast observed by Hansen in IS88 as not fermenting maltose. It includes also certain details of procedure, which have been found to facilitate, even if they are not necessary to, an easy crystallisation of the maltose after the fermentation is over, and reduce to a minimum such adventitious impurities as the bye-products of fermentation and the oxidation products of the sugars.A pure culture of the yeast, which has been grown in a glucose broth, is washed repeatedly with sterilised tap water, making use of a centrifuge, and is then added to a sterilised solution of the sugars which it is desired to ferment. The solution, which may be in an ordinary flask closed by a cotton wool plug, should not contain much more than 10 per cent. of sugar and should be made up in part with sterilised tap water. The fermentation is conducted at 25-29' and proceeds slowly in the absence of proteid and without any notable multiplication of the yeast cells.When the evolution of carbon dioxide has nearly ceased, the flask is heated for a minute or so at 100Oin the autoclave, and then its contents are freed from celIs by filtration through a porous funnel. Alcohol is added to the solution to one-third of its volume and the lvhole evaporated down in a current of carbon dioxide to a thick syrup under diminished pressure ; if necessary, inore alcohol is added during the evaporation so that the temperature does not rise above 60". The rest of the process resembles that usually employed in the recrystallisation of maltose from 80 to 85 per cent. ethyl alcohol and results in the separation of the maltose quite white at the first crys- tallisation. *34."The vapour pressure of aqueous ammonia solution." ByE,P. Perman, D.Sc. The vapour pressure of aqueous ammonia solutions of concentrations varying from nothing to 35 per cent. has been found by a statical method; the temperatures ranged from 0" to 60". The curves show- ing the variation of pressure with concentration at various tempera- tures are found to be approximately represented by the equation ~(100-c)=ccc+ bc2; a and b are constants, c is the concentration of the ammonia in the solution. The equation may be put in the form p(100 -c) =c.k, when k =a +bc and is the reciprocal of the solubility coefficient. The variation of pressure with temperature (the concentration remaining constant) is expressed with fair accuracy by the equation 1og.p =a +Pt +ytz, a, p, and y being constants, of which y is always negative. The constant p is found to have the same value as the corresponding constant found in the expression 1og.b=a' +P't for the vnte oj' escape of Rmmonia from aqueous solution (Z'mns., 1898, 73, 511).47 “35. “The influence of sodium sulphate on the vapour pressure of aqueous ammonia solution.” By E. P. Perman, D.Sc. The author has determined the vapour pressures of ammonia solu- tions containing sodium sulphate in solution at temperatures varying from 26’ to 47’ and has compared them with corresponding solu-tions of ammonia without sodium sulphate. The curves show no break at 33”, nor do they diverge more than those for ammonia solut.iou.Hence it seems probable that the sodium sulphate does not exist as a hydrate in solution. 36. ‘‘Formation of aromatic compounds from ethyi ghtaconate and its derivatives. The reduction of trimesic acid and the con-version of tetrahydrotrimesic acid into tetrshydroisophthalic acid.” By W.T.Lawrence and W. H. Perkin, jun, In experimenting with the sodium compound of ethyl sodio-dicarb- oxyglutaconate, (CO,Et),CNa.CH:C(CO,Et),, the authors have found that this cornpound, when heated with alcohol at 150°, is decomposed with formation of a large yield of ethyl ti-imesnte, C0,Et /\ CO,Et! \/‘C0,Et ’ and further, that methyl sodiodicarboxyglutaconate under the same conditions is converted into inetlizyl trimesccte.When the sodium compound of ethyl glutaconate, CO2Et*CHNa*CH:CH*C0,Et,is heated with alcohol at 150°, it is also decomposed, but in a different manner, and the product on hydrolysis yields hydi.ox?/iso~)?~t?iaZicmid. This acid was identified by analysis; and by conversion into the met,hyl ester (M.p. 94‘) and into the ethyl ester (m. p. 52’), and it is thus identical with the hydroxyisophthalic acid, OHi/jCO,H 9 \/CO,H which Kupferberg (-7.prakt. Chem., 1877, [ii], 16, 428) obtained by heating sodium salicylate in a current of carbon dioxide. When ethyl methylglutaconate, CO,Et*CHMe*CH:CH*CO,Et, is heated with sodium ethylate and alcohol at 140°, it yields a solid ester melting at 96’ which, on hydrolysis, is converted into an acid 48 very sparingly soluble in water and melting at 216'; these substances are at present under investigation.The authors have also found that when the sodium compound of ethyl malonate is digested with ethyl trichloroacetate there is formed, besides the sodium compound of ethyl dicarboxyglutaconate (Ruhemann, Zw., 1896, 29, lOl7), an ester which on hydrolysis and elimination of carbon dioxide, yield3 aconitic acid. This ester, which is the normd product of the reac-tion, therefore must have the formula (CO,Et),CH*C(CO,Et):C(CO,Et),. When trimeeic acid, dissolved in sodium carbonate, is treated with sodium amalgam, it is readily reduced with formation of a mixture of acids, which are evidently stereoisonleric modifications of tetrahydro-trimesic acid, CO,H CO,€€\)CO,H One of these acids has been isdated in a pure condition, it melts at about 210" and is very sparingly soluble in dry ether.When digested with acetic anhydride it yields a resinous double anhydride of trimesic acid and acetic acid, which on distillation loses carbon dioxide, with formation of tlie anhydride of tetrahydroisophthalic acid. On treatment with potash this anhydride yields tetrahydroisophthalic acid as a colourless crystalline substance sparingly soluble in water and melting at 244"; from its method of formation it must have the formula, CO,H/y\/CO,H ' and is the first tetrahydroisophthalic acid which has so far been pre- pared. The authors are continuing their investigation on the action of sodium ethylate on the derivatives of glutaconic acid and other similarly constituted acids.37. '' Optical activity of certain ethers and esters." By P. A. Guye. The author has confirmed the results of Tachugaeff's observations, quoted by McCrae and Patterson (Trans., 1900, 77, 1096) that thc: optical rotation of compounds containing the phenacetyl group resem- bles more closely that of compounds containing the acetyl or the chloroacetyl group, than that of compounds containing tlie toluyl group, although the mass of the phenacetyl group is more nearly that of the toluyl group than of either of the other groups named. The examination of a number of compounds of amyl (phenyl-amyl oxide* benzyl-amyl oxide, and various amyl esters) has led the author to an analogous conclusion.It is, however, only one case of a more general conclusion already drawn by him, namely, that when substitutions of chains or groups of elements are effected in an asymmetric carbon compound, sufficiently far from the asymmetric carbon atom, the optical rotation is only slightly affected. 38. LL Halogen-substituted thiosinamines.” By A. E,Dixon, M.D, From the researches of Gabriel and others, as well as from his own previous work, the author thought it not unlikely that the ‘chlorallyl- thiourea ’ of Henry (Ber., 5, 18S), obtained from P-chloroallylthio- carbimide and ammonia, might really be the hydrochloride of a ring-CH,: ?--S compound, CH,-N>C*NH,; to test this, he has prepared the thiocarbimide, and examined a number of its compounds with bases.Contrary to anticipation, the addition products so obtained are not closed chain saline derivatives ; no formation of haloid acid occurs, but the constituents unite directly, yielding the corresponding halogen- substituted thiocarbamides. P-C‘hloroccll?/lthiocar~i~ide,CH,:CCl*CH,*NCX, is a colourless, highly refracting oil boiling at about 182’ ; it is slightly soluble in water, has a very pungent odour, and readily blisters the skin. With ammonia it yields Henry’s P-chloroallylthiourea ;prisms, melt- ing at 93.5-94.5O (corr.) ; Henry gives 90-91O. This substance is moderately soluble in water, and easily so in alcohol; the latter solution, if moderately dilute, gives no precipitate with silver nitrate, but is freely desulphurised by warming with alkaline lead tar-trate.CLloroallylthiourea undergoes no isomeric change if boiled in aqueous solution ; when fused with rnonochloracetic acid, ib yields the hydrochloride of p-chI oroaZ lyIthiohydantoin, S-CH,CH2:CCl*CH,*NH-C<N, b0 ,white prisms, which begin to decom- pose at about 170°, and lose the combined acid on recrystallisation froni water. The free thiohydantoin is deposited from water in leaves, and from alcohol in prisms, both forms meltiug at 149O; when hydro- lysed by boiling with dilute alkali, thioglycollic acid is produced. ab-ChZorouZZylphenyltlLiocarbamide, CH,: CC1*CH2*NH.CS*NHC,H,, prepared from the tbiocarbimide and aniline, is deposited from benz- ene in plates, 111.p. 91-92”. When desulphurised by silver nitrate it gives rise to the corresponding ab-cl~loi.oaZZ~l~?~e~~yZccLrbu~~i~~~as slender prisms, m. p. 151-152’. ab-ChZorocclZyZortTiotoZyZthioccwbeinzide separates from weak alcohol in prisms, m. p. S4--85’. ab-Cl~ZoroaZZyZbe.rzxyitT~iocnr6cinaitlecrystallises from a mixture of benzene and light petroleum in very brilliant prisms, m. p. 69”. Unlike the preceding thiocnrbamides, it is not desulphurised when boiled with alkalino lead tartrate. Piperidine yields c~Zo?.oaZl?lZ1~.il,e~idyZtl~ioure ti ansparentl quad- c in rangular plates, in. p. 146-5-147.5”. n-CIAZoroaZ ZyI-v -belizxyZpTieliz?/ItILiou?*ect, c‘, H,Cl K:C(SH) * NBzP h , is deposited from light petroleum in needles, 111.p. 77-78”. /3 Cliloroallyltl-liocnrbimide, disolveti in chloroform, absorbs broini ne, yielding P-cl~loi.o-py-clibronao~~rolJ?/lt~~ioca,~~~i~~ai~e, CH,Br-CClBr*CH,*NCS, a dense, yellowish liquid, volatile in a current of steam; it unites spontaneously with aniline, forming the hydrobromide of a ring com- pound, C,H,GrCl<~~C.NH.C,,W,. The hydrobromide occurred as a sandy powder, LLI. 1’. 112-113°; when treated with cold alkali, hydrogen bromide was removed, but the base could not be obtained in R state fit for analysis. With benzylamine an oily hydrobromide was produced ; from this potash withdraws a molecule of hydrogen bromide, leaving the free base, C3H,Br2<~~C.N.H*CHL.CGf13,which crystallises in prisms, m.p. 107-10S0, and dissolves in hydrobromic acid to re-form the oily hydrobromide. 39. “A form of tautomerism occurring amongst the thiocyanates of electro-negative radicles.” By A. E. Dixon, M.D. Some years ago (T~mzs.,1897, 71, 640; see also 1899, 75, 3-89}, the author remarked that the so-called ‘‘phosphorus trithiocyanate,” P(SCN),, appeared to possess thiocarbimidic as well as thiocyanic properties, and subseqnent investigation tends to show that this power to function in both capacities is also manifested by the pro-ducts obtainable from metallic thiocyanates and the chlorides of a number of electro-negative mineral elements and compound radicles. The chiorides, dissolved in suitable anhydrous solvents, were caused to interact with excess of lead or other metallic thiocyanate, if possible, until the chlorine WRS completely eliminated as metallic chloride ;the solid residue was then filtered off, and the filtrate treated with a base such as aniline.Precipitates were thus obtained, which gave the clesulphurisation tests with lead and silver sdt3, characteristic of thio- carbamides, and were usaally hydrolysecl by contact with water so as to afford the substituted thiourea corresponding to the ba se used. 51 Unfortunately, no efficient method has yet been found for purifying these precipitates, which are rarely free from more or less contamina- tion with basic thiocyanate. ‘‘Phosphorus trithiocyanate,” P(SCN),, gave with- aniline a yellow solid insoluble in cold water, bnt decomposed when boiled with water into phenylthiourea ard an acid of phosphorus ;this substance is probably phosphorus triphenyltrithiourea, P(NH*CS*NH*C,H,),.With o-tolu- idine a yellow powder melting between 81” and 83O was obtained ;it appears to be the corresponding tolyl derivative nearly piire. Both these compounds are very freely soluble in alcohol and acetone, but nearly insoluble in benzene, chloroform, and light petroleum. ‘‘ Phosphoryl trithiocyxnate,” PO(SCN),, obtained in solution by boiling phosphorus oxychloride in dry ciimene with lead thiocyanate, gave with silver and lead salts the usual thiocarbimidic reactions and united spontaneously with aniline, o-toluidine and dry ammonia.The aniline compound was a pale yellow powder melting at aboilt 111-1 12”, freely soluble in alcohol, ethyl acetate, acetone, glacial acetic acid, and nitrobenzene ; insoluble, or nearly so, in chloroform, ether, carbon disulphide, benzene and light petrolcum, It w~tsnearly insoluble in cold water, but dissolved gradually on boiling; the solution contained phosphoric and thiocyanic acids, and on cooling, gave a crystalline deposit of phenylthiourea. The latter appears to be formed by hydrolysis of phosphoryltriphenyltrithiocarbamide : PO(NH*CS*NH*C,H,), + 3H,O = H,PO, + SCSN,H,*C,H,. O~*t?~otoZuidinegave a tenacious oil, hardening presently to a resin-like solid ; its properties resembled those of the phenylic homologue but the substance could not be obtained in a pure condition.Dry ammonia gas yielded a pale yellow granular solid, melting, im- perfectly, below GOO, readily soluble in water, and containing a very appreciable quantity of ammonium thiocyanate. The solution in cold water gave with excess of ammonia, followed by magnesia mixture, scarcely any precipitate. But this solution, if previously boiled and allobved to cool, then reacted freely with the above test; consequently it is inferred that the phosphoric acid does not exist ready formed in the solution, but originates through the hydrolysis of the phosphoryl- trithiourea, PO( CSN,H,),. The ‘‘thionyl thiocyanate ” of McMurtry (Ymns., 1889, 55, 48) differs in physical and chemical characters from all the known electro- negative thiocyanates ;it is suggested that this compound, of which the thiocyanic properties are very feebly marked, mhiist it gives decided thiocxrbimidic reactions, is probably a polymeric form, [SO(NCS),lj,.Carbonyl chloride, in toluene, reacted with lead thiocyanate on standing ; the dissolved sulphuretted product (which was freely de- 52 sulphurised by lead and silver salts) combined at once with aniline, yielding in small quantity a substance melting at about 174’ and possessing the characters of a thiocarbamide. ANNIVERSARY DINNER. It has been arranged that the Fellows of the Society and their friends shall dine together at the Whitehall Rooms, Hotel Metropole, on Wednesday, March 27th, at half-past six for seven o’clock.The price of the tickets is one guinea each including wine. Fellows are par ti~~iIai*lyrequested to give the Secretaries earlv notice of their intention to be prpsent. Tickets will be forwarded to Fellows on receipt of n remittance for the number of tickets required, addressed to the Assistant Secretary, Chemical Society, Burlington House, W. ANNUAL GENERAL MEETING. The Annual General Meeting of the Society for the Election of Officers and other business will be held on Thursday, March 28tb, at three o’clock in the afternoon. At the next meeting, on Thursday, March 21st, the folIowing papers will be communicated : “Researches on morphine, Part 11.” By S. B. Schryver and F. H. Lees. “The constitution of pilocarpine. Part 11.” By H. A. D. Jowett. “Note on the latent heats of evaporation of liquids.” By H. Crompton. (‘Action of dry silver oxide and ethyl iodide on benzoylacetio ester, desoxybenzoin, and benzyl cyanide.” By 9.D. Lander. ‘‘Alkylation of acylarylamines.” By G. D. Lander. RtCJThRD CLAY AND SOXS, LIMITED, LONDON AND I3UXGAT.
ISSN:0369-8718
DOI:10.1039/PL9011700043
出版商:RSC
年代:1901
数据来源: RSC
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