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Proceedings of the Chemical Society, Vol. 28, No. 398 |
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Proceedings of the Chemical Society, London,
Volume 28,
Issue 398,
1912,
Page 45-59
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摘要:
[Issued 15/3/12 PROCEEDINGS OF THE CHEMICAL SOCIETY. VOl. 28. No.398. Thursday, March 7th, 1912, at 8.30 p.m., Professor J. NORMAN COLLIE,Ph.D., F.R.S.,Vice-president, in the Chair. Messrs. H. J. Backer, John C. Withers, George A. Stokes, Row-land H. Ellis, B. C. Smith, and Thomas A. Brunjes were formally admitted Fellows of the Society. Certificates were read for the first time in favour of Messrs. : Daniel Arkell, B.Sc., Oratory School, Birmingham. Evelyn Ashley Cooper, B.Sc., Arborfield, Woodcote Valley Road, Purley, Surrey. Frederick Charles Eastick, B.A., The Drive, South Woodford. John Burke Farlie, jun., 54, Wellington Road, Old Charlton, S.E. Oliver Richard Howells, B.Sc., Bracondale School, Norwich. James O’Mara, B.A., Dunlica, College Raad, Dulwich, S.E.John Rennie, Maisonette, Rufford Park, Yeadon, Leeds. Arthur Thompson, Bryn Teg, Chetwynd Road, Wolverhampton. A ballot for the election of Honorary and Foreign Members was held, and the following were subsequently declared duly elected : Prof. Philippe A. Guye (Geneva). Dr. Thomas Burr Osborne (Newhaven, Conn.). Prof. Paul Wa.lden (Riga). Prof. Richard Willstiitter (Zurich). 46 The names of the Fellows recommended by the Council for election as Officers and as Ordinary Members of Council for the year 1912 to 1913 were read from the Chair. Of the following papers, those marked * were read: *57. 66 Isomeric change of halogen-substituted diacylanilides into acylaminoketones.” By Andrea Angel. The isomeric change of diacylanilides into derivatives of 0-amino-benzophenone, which has been shown to occur (Trans., 1904, 85, 386) under the! influence of heat and a catalyst when an alkyl group is present in the para-positioa with respect to the nitrogen atom, has been found to take place in a similar manner jf negative para-substituents such as chlorine or bromine are present in the acylated aniline.Dib enzoyl-p-chloroaniline and dib enzoyl-p-b romoaniline undergo rearrangement into 5 -chloro -o -0 enzoylaminob enzophenone and 5-bromo-o-benzoylaminob ensophenone respectively, thus : These are pale yellow, crystalline substances, melting at 108O and 122O respectively, which are with some difficulty hydrolysed to the corresponding aminohalogenbenzophencmes. 5-Bromo-o-aminob enzophenone (m.p. 111O) resembles the chloro- compound (loc. cit., p. 344) very closely. It crystdlises from dilute alcohol in bright yellow needles, and is somewhat volatile in steam. It is a weak base, forming crystalline salts with acids, which, however, are so readily hydrolysed that they turn yellow in moist air. *38. “Studies in the camphane series. Part XXXII. Stereo-isomeric modifications of isonitroso-epicamphor, the third and fourth monoximes of camphorquinone.” By Martin Onslow Forster and Hans Spinner. Although aryliminederivatives of camphor, when heated with hydroxylamine hydrochloride and sodium acetate, yield either ordinary isonitrosocamphor or the dioxime of camphorquinone (Trans., 1909, 95, 942), there are produced from phenylimino-camphor in presence of alkali two isomeric oximes.The a-oxime, H-<$XN*C H‘ ’* CNOH ’, crystallises from alcohol in massive, transparent, 47 sulphur-yellow prisms, melting at 112O, and has [a]=335-4O. The P-oxime separates less readily from alcohol, but does not dissolve so freely as the isomeride in benzene, chloroform, or petroleum; it crystallises in very pale brown needles melting at 172O, and has [a], 304.4O. This modification is transformed into the isomeride when heated above the melting point. COisoNitroso-efpzcamphor, CsH14(&NOII' as obtained by hydro- lysing the a-oxime of phenyliminocamphor with dilute hydrochloric acid, melts at 137O, and has [aID -179'4O.If the fused substance is heated further, it becomes semi-solid owing to transformation into a more stable isomeride, which is conveniently produced by boiling an aqueous solution of the unstable one; this form of isonitroseepicamphor crystallises from water in long, lustrous, flat needles, melting at 170°, and has [a],,-2O0*lo. The two substances differ markedly as regards their solubility in petroleum, and they form distinct benzoyl derivatives ; both develop with alkali hydroxide the yellow coloration characteristic of isonitroso-ketones, and the diluted solution yields with ferrous sulphate a bluish-violet precipitate resembling that given by isonitrosocamphor. Phenyl. hydrazine leads to an oxime of camphorquinonephenylhydrazone, whilst hydroxylamine gives rise to a dioxime of camphorquinone.Hence it seems clear that the new isonitroso-ketones have to epicamphor (Lankshear and Perltin, Proc., 1911, 27, 166) the rela- tionship borne by the two modifications of isonitrosocamphor towards camphor itself. The production of isonitros+epicamphor in two forms therefore completes the series of oximes theoretically obtainable from cam-phorquinone; four dioximes and four monoximes are now known. +39. ('The synthesis of glyoxaline derivatives allied to pilocarpine." By Frank Lee Pyman. The Zactone of a(/3-hydroxyethyl-)j3-g~yoxaZine-4(or5)-propionic ucid (I),which has certain constitutional features in common with pilocarpine (11),has been prepared by hydrolysing ethyl 4(or 5)-gZy-oxalinemet hyl- y-phenoxy ethylmarlonate, a product obtained by the act ion of 4(or 5)-chloromethylglyoxaline on ethyl y-phenoxyethyl- malonate : yH,*$!H*CH,*$*NH C,H,*$!H*QH°CH2*g-NMe CH, CO C ON'>CH CO CH, CH-N WH \/ \/0 0 (1.1 (11.) 48 Neither this base nor an A--methyl derivative has any pronounced physiological action.a-4(or 5)-Glyoxalinemethyl-8-et hylsuccinic acid (111), a compound C,H,*FH-C;H*CH,*~* 11 CO,H CO,H CH*N'CH (111.) containing the skeleton of pilocarpine, has been prepared by con- densing 4(or 5)-chloromethylglyoxaline with ethyl a-cyano-8-ethyl- succinate, and hydrolysing the resulting ethyl &$(or 5)-glyoxaZim-metl"Lyl-a-qanflo-fl-ethgZsuccinate. Its ethyl ester proved to be physiologically inactive.The preparation of 4(or 5)-&oxaline-formaldehyde, C,H,N,*CHO, was also mentioned, and a description given of the free base, 4(or 5)-Baminoethylglyoxaline. "40. '(Calcium nitrate. Part I. The two-component system, calcium nitrate, water. Part 11. The three-component system, calcium nitrate, nitric acid, water at 25O." By Henry Bassett, jtln., and Hugh Stott Taylor. The solubility of calcium nitrate in water has been studied between the temperatures of -28'7O (the cryohydric temperature) and 151O (the boiling point of the saturated solution). There are only three hydrates of calcium nitrate, namely, Ca(N03),,4H,0, Ca(NO3),,3H,O, and Ca(N0,),,2H20, each of which is stable in contact with its saturated solution over a definite range of tem-perature.The tetra- and tri-hydrates have true melting points. The solubility of calcium nitrate increases rapidly with rise of temperature throughout the range of existence of the several hydrates, but at 51O, where the anhydrous Ca(NO,), becomes the stable solid phase, the solubility reaches a value which hardly changes with further rise of temperature. The addition of nitric acid lowers the solubility of calcium nitrate, and at the same time promotes dehydration. Solubility determina- tims have been made at 25O between the limits of nitric acid concentration of 0 and 98 per cent. In contact with pure water and dilute nitric acid solutions, Ca(N03),,4H,0 is the stable solid phase, whilst the anhydrous Ca(NO,), is alone stable in presence of the most concentrated acid solutions. Between these two extremes, however, there are well marked intermediate regions, where the stable solid phases are Ca(N0,),,3H20 and Ca(NO,),,ZH,O respec-tively.49 41. ‘‘ The chemistry of the glutaconic acids. Part 111. Glutaconic acid and its P-alkyl derivatives.” By Norman Bland and Jocelyn Field Thorpe. Glutaconic acid, /3-methylglutaconic acid, and /3-phenylglutaconic acid readily yield hydroxy-anhydrides of the formuls (I),(11),and (111)respectively : These compounds are monobasic acids, and give intense colora- tions with ferric chloride. Glutaconic acid behaves towards aniline in the same manner as it,s a-mono-substituted derivatives, and the eis-semianilide prepared from the hydroxy-anhydride and aniline (IV) passes into the trans-semianilide (V) when heated : dH,*CO*NHPh CH,*CO*NHPh UV.) (V.) The hydroxy-anhydrides from the &substituted acids yield, on the other hand, semianilides (VI), which pass into hydroxy-anils (VII)when heated : CH*CO,H (VII.) The hydroxy-anils behave on titration as monobasic acids, but their salts are stable, and do not regenerate the salts of the semi- anilide when heated. It is evident that the attachment of an alkyl group to the &carbon atom of glutaconic acid confers increased stability on those forms of the derivatives of the acids which have the mobile hydrogen outside the three-carbon system. 42. ‘(Asymmetric quinquevalent nitrogen compounds of simple molecular constitution.” By William Jackson Pope and John Read.In 1891 LeBel described the preparation of methylethylpropyliso-butylammonium salts, and the manner in which, by the action of 50 Penicillium glaucum on a solution of the corresponding chloride, he obtained a solution which exhibited it small rotatory power; from this observation LeBel concluded that he had succeeded in obtaining optical activity which could be associated with the presence of an asymmetric quinquevalent nitrogen atom. In 1899 Marckwald prepared salts of the above-named base by the interaction of methylpropylisobutylamine and ethyl iodide, and, since he obtained no optical activity by the action of the organism as described by LeBel, concluded that the latter author’s observa- tions were not correct.In a reply to Marckwald, LeBel attributed the failure to confirm his observations to the production of a different quaternary ammonium iodide by Marckwald’s process and his own, which consisted in causing ethylpropylisobutylamine to combine with methyl iodide. The authors have prepared ethylpropylisobutylamine in a state of purity, and have found that it combines with methyl iodide, yielding a quaternary ammonium iodide identical with that obtained by the alternative method used by Marckwald. They find that the behaviouq of ethylpropylisobutylamine towards methyl iodide is quit? unlike that described by LeBel. It is consequently concluded that LeBel did not succeed in preparing methylethylpropylisobutylammonium iodide, and that he did not obtain a substance of which the optical activity could be associated with the presence of an asymmetric quinquevalent nitrogen atom.43. ‘(The interaction of phosphorus and potassium hydroxide solution.” By Manindra Nath Banerjee. An explanation was given, by means of a series of equations, of the mechaiiism of the reaction between phosphorus and potassium hydroxide solution. 44. “The triazo-group. Part XX. Azoimides of the propane series ” By Martin Onslow Forster and John Charles Withers. By methods, the principles of which are familiar, y-triuzopToppZ-amine was prepared along with P-triacopropylamine, which it greatly exceeds in stability, resembling B-triazoethylamine.ay-Bistriazo-isqropgl alcohol and up-bistriazopropyl alcohol were described, together with the respective bistriazocibloropropnes; from the former of these ay-bistriazopropplene has been obtained. 51 ‘a45. Viscosity and association. Part 11. The viscosity of geometrical isomerides.’’ By Ferdinand Bernard Thole. The author has determined the viscoaity of a large number of geometrical isomerides, typical members of the ethylenic compounds, the oximes and the phenylhydrazones being examined. From the results certain general rules have been drawn, by help of which it has been possible to confirm the formuls for the camphorquinonephenylhydrazones suggested by Forster and Zimmerli (Trans., 1911, 99, 478), and to assign formulae to the acetaldehydephenylhydrazones described by Lockemann and Liesche (Annalen, 1905, 34, 214).46. 4c The chemistry of the glutaconic acids. A correction.” By Jocelyn Field Thorpe. In Part I of this series (Trans.,1911,99,2188) the work previously recorded on the alkylation of esters of the type of ethyl glutaconate was summarised, and it was concluded that under certain conditions the hydrogen atom of the complex X-CH: could be displaced by sodium through the agency of alcoholic sodium ethoxide. This conclusion was based on the formation of aby-trimethyl- glutaconic acid (IV) from the ester (111),which was obtained from the ester (11) by the action of sodium ethoxide and methyl iodide; the structure of the last-named substance being evident owing to its formation from the potassium compound (I)and methyl iodide : CO,Et*CK(CN)*CMe:CH*CO,Et-+CO,Et*CMe(CN)*CMe:CH*COEt (I.(11.) -+CO,Et*CMe( CN)* CMe:CRle* C0,Et (111.) -+ CO,H*CHMe*CMe:CMe-CO,H (IV.1 In the original paper (Trans., 1905, 87, 1674) two possible struc- tures for this potassium compound were considered, namely, (V) and (VI), and of these formula (V) was regarded as the more probable because of the strongly negative character of the hydrogen atom displaced. It is, however, evident, in view of the presence of the mobile hydrogen atom which has since been demonstrated, that there is still another possibility, which is represented by formula (VII) : CN Me CN Me CN Me CE-G:I I CH*C0,Et CH--b:I CK*CO,Et C=C*CHK*CO,EtI I .CO,Et I (!!O,Et 60,Eti (V.) VI.) (VII.) 52 In a recent communication (Trans., 1912, 101, 249) it was shown that the esters of substituted glutaconic acids containing the mobile hydrogen atom react with sodium ethoxide so as to retain this hydrogen, and it is therefore evident that if this statement is true the potassium compound must have the formula (VII), because in order to form a compound o'f formula (V) the ester would have to part with its mobile hydrogen atom. Fortunately, it is a very simple matter to prove that the potassium compound has the structure represented by formula (VII), because, when the metal is displaced by benzyl, an ester (VIII) is produced, which is hydrolysed with remarkable ease by alkali hydroxide, yielding cyanoacetic acid and benzylacetone (IX) : CN Me CH,Fh CN Me CH,Ph I I I IC==C--CH*CO,Et --+ CH, + &O--bEI,.I C0,Et (VIII.) It is proposed to give the full experimental details of this curious reaction in a subsequent communication, but it may be stated here that the benzylated ester (VIII) exists in two well-defined modi- fications, one giving a coloration with Eerric chloride and dissolving in alkali, the other giving no coloration and being insoluble in alkali. It is the soluble ester only which undergoes disruption in the above manner. There is, then, no reason to assume that the formation of a6y-trimethylglutaconic acid involves the displacement of the hydrogen atom of the complex X*CH: by sodium, because the course of the reaction can now be represented in the following way : CO,E t*C(CN):CMe*CHK*CO,Et-+ C0,Et C(CN):CMe*CHMe C0,Et -+ CO,Et*CNa(CN).CMe:CMe*CO,Et-+ C0,Et*CMe(CN~*C1Sle:CMe*C02Et That is to say, the introduction of the sodium atom in the second operation, involving it5 it does the displacement of the mobile hydrogen atom, causes the metal to take up the most negative position in the system (compare Truns., 1912, 101, 249).The following experimental corrections are therefore necessary : Trans., 1905, 87, 1694, Zine 21 from top: The formuta of the potassium compound should be C?O,Et*C(CN):CMe*CHK*CO,Et. Ibid., 1695, Eine 4 from top: The name of the ester should be ethyl y-cyano-a8-dirnethylglutaconate,and the formula C0,Et-C(CN) :CMe*C!HMe*CO,Et or CO,Et*C(CN)*CMe(H)*CMe*CO,Et.Ibid., 1708, line 18 from top: The name of the ester should be ethyl y-cyano-&methyl-u-ethylglutaconate, and the formula @O,Et.C(CN);CMe- CHE t*CO,E t or CO,EtA3(CN>*CMe(H)*C’Et.CO2Et. 47. “The catalytic action of copper at 300” on some alcohols of the terpene group.” By George Ballingall Neave. The Sabatier-Senderens test for distinguishing between primary, secondary, and tertiary alcohols (BUZZ.SOC.chim., 1905, [iii], 53, 263) has been extended to some alcohols of the terpene group. E-Borneo1 was converted into 2-camphor, fenchyl alcohol into fenchone, and menthol into menthone, aJ1 three behaving as secondary alcohols. The following, which are regarded as tertiary alcohols, yielded unsaturated hydrocarbons : terpineol and terpin gave dipentene ;isoborneol gave camphene.Sobrerol, which contains both a secondary and a tertiary alcoholic group, was converted into pinol. 48. “ Preparation of the nitrites of the primary, secondary, and tertiary amines, Part 11.” By Pailchiinan Neogi. Coniinium nitrite has been isolated, in fairly good yield, from a mixture of the hydrochloride of the base and the alkali nitrites. 49. “Trialkylammonium nitrites and nitrites of the bases of the pyridine and quinoline series. Part 111.’’ By Pailchiinan Neogi. Coniinium nitrite, colourless fibrous crystals, sublimes unchanged when heated in a vacuum, and then decomposes with the formation of nitrosoconiine.Coniine methonitrit e forms a viscous, reddish- yellow liquid. Pipe:l’idine etlconitrite crystallises in colourless plates. Pyridine ethonitrit e is a colourless liquid. 50. “The glucoside and oil of Caesalpina bonducella.” By Kshitibhushan Bhaduri. The seeds of Caesalpina. boducella yield an alkaloid, for which bhe author suggests the name natin. The oil has D27 0.9132, iodine value 96.1, and saponification value 292.8. 51. (( Constituents of Vernonia anthelmintica. Part I.” By Kshitibhushan Bhaduri. The seeds of Vernonia anthelmintica contain a glucoside, to which the name slmmerajin, is assigned. The oil has D25 0.9731, iodine value 91.7, and saponification value 305.7. 54 52. Substituted isothiohydantoins.” 1c By Augustur Edward Dixon and John Taylor.Substituted thioureas (or thiocarbamides), including one, or two, hydrocarbon radicles, when treated with ethyl chloroacebate, produce the corresponding isothiohydantoins. If, however, the thiourea ccntains an acyl substituent, interaction does not occur. On the other hand, chloroacetyl chloride readily attacks thioureas containing an acyl radicle, but not with elimination of two hydrogen atoms; instead, the acyl radicle is expelled (yielding an acid chloride), and the residue, joining with the glycolyl group, forms a non-acylated isothiohydantoin ;thus, for example : PhN:C<tzAc +CICH,*COCi =AcCl +PhN:C<N H*(? + HCI. S-CH, A trisubstituted thiourea, including purely hydrocarbon radicles, X, Y, Z, unites directly with chloroacetyl chloride.In this case, the linking, *S*CH,-CO*,characteristic of the isothiohydantoins, is not produced, but -S*CO*CH, instead, the resultant compound behaving as the hydrochloride of a base, XYN*C(NZ)*8*CO-CH2C1, N-~iphenylisothwkydantoiii,Ph,N*C<N’?O is formed when a-CH.,’L chloroacetyl chloride acts on n-benzoyl-v-diphenylthiourea, n-acetyl-v-diphenylthiourea, or v-diphenylthiourea ; it crystallises from alcohol in brilliant, white prisms, meIting at 198O (corr.). The phenylisothiohydantn obtained from aa-acetylphenyl-thiocarbamide and chloroacetyl chloride is the same as that from the ah-isomeride ;this is attributed to a preliminary transformation of the former variety into the latter during the course of thO interaction.53. (c The conversion of d-glucosamine into d-glucose.” (Pre-liminary note.) By James Colquhoun Irvine and Alexander Hynd. The scheme suggested in a previous paper (Trans., 1911, 99, 250) for the conversion of d-glucosamine into d-glucose has now been successfully completed, and, pendiug publication of the detailed results, the authors consider it advisable to outline the reactions in a preliminary note, in view of the fact that other workers have been engaged on the same subject (J. Amer. Chem. Soc., 1911, 33, 766). Glucosamine hydrochloride has been converted, as already described (loc. cit.), into methylglucosamine hydrochloride. As this compound is here shown to be definitely related to glucose it may now be termed anhmmethylglucoside hydrochloride.Like other 55 derivatives of glucosamine, it reacts abnormally with nitrous acid, and although ammonia is evolved when the compound is heated a-ith alkali hydroxides, the reaction seems to be complex, and does not yield methylglucoside. Recourse was therefore had to the silver oxide method of methylation which resulted in the formation of a, methyl! aminomethylglucoside (m. p. 89-90°; [u]: -14'9O in methyl alcohol) as the first definite product. Further methylation gave dimethyl aminomcthylylucoside as a colourless syrup, from which the substituted amino-group was expelled by heating with barium hydroxide. The product, on exhaustive methylation, was converted into tetramethyl methylglucoside, which was identified by analysis, boiling point, and specific rotation. The removal of the methyl groups was effected in two stages.On hydrolysis with dilute acid, tetramethyl glucose was obtained, and its identity confirmed by analysis, melting pbint (85--86O), and by the specific rotation in water ([U]~+ 82.1O). To complete the series of reactions, the alkylated sugar was reduced to the parent hexose by heating with a 40 per cent. solution of hydrogen iodide at 94O. &Glucose, showing the permanent specific rotation [a]: +52.407 was thus obtained in good yield. The conversion of glucosamine into glucose is thus possible through the following reactions : d-Glucosamine hydrochloride +bromotriacetylglucosamine hydro-bromide -+ triacetyl srninomethylglucoside hydrobromide --+amino-methylglucoaide hydrochloride --+methyl rr,minomethylglucoside -+ dimethyl aminomethylglucoside -+ tetramethyl methylglucoside -+ tetramethyl glucose -+ d-glucose.In the course of the work, the salts of aminornethylglucoside were re-examined so as to secure accurate comparison with those described by Fischer (Ber., 1911, 44, 132). The specific rotations for the hydrochloride and hydrobromide in aqueous solution are now found to be -24'22O and -20'23O respectively, and are thus identical with those found by Fischer. The decomposition points are, however, 190° and 181°7 values which are uniformly 25O lower than those quoted by Fischer. It seems possible that in Fischer's aminomethylglucoside the amino-group is attached to the carbon atom in either the B-or €-position to the glucosidic group.This assumption would explain the isomerism of the aminomethylgluco- sides, and is also in agreement with the production from triacetyl bromomethylglucoside of an anhydroglucose capable of forming anhydrophenylglucosazone (Fischer, Ber., 1912, 45, 456). The examination of aminoglucosides prepared from glucosamine is being continued. 56 54. “The chemistry of the glutaconic acids. Part IV. The structure of the glutaconic acids.” By Jocelyn Field Thorpe. The experimental evidence recorded in the previous parts of this series was reviewed, and the conclusion was drawn that the stable forms of the derivatives of glutaconic acid have a structure similar to that of glutaconic acid itself, in which the tautomeric hydrogen atom is within the three-carbon system and static on the B-carbon atom of this system.The labile acids are those first formed by the hydration of the hydroxyanhydrides, and are in reality the y-alkyl derivatives of glutaconic acid. The two forms of a-methylglutaconic acid may therefore be represented in this way: I1Me*F*CO,H hIe C---co Me*G*CO,H yH2 CH >o YHICH*CO,H CH C(OH) CH,*CO,H Normal form. Hydroxy-auhydride. Labile acid. The initial momentum acquired by the hydrogen atom at the .moment of its introduction by the hydration of the hydroxy-anhydride carries it, if unchecked, into the three-carbon system ;if, however, this “spring” is restrained by alkali or casein, the hydrogen is brought to rest within the crtrbonyl system.It was also shown that the esters of the glutaconic acids may be of four distinct types, which may be either tautomeric, desmoi tropic, or structurally different. Examples of all four types have been isolated and identified. 55. Epicamphor @-camphor).” (Preliminary note.) By Julius Bredt and William Henry Perkin, jun. Epicamphor (I),the isomeride the ordinary camphor (11),has CH,*yH-cOI IYMe2C‘H,*CMe-CH, (1.) (11.1 been obtained by two processes, namely, (i) in small quantities, from camphanecarboxylic acid by bromination, hydrolysis, and subse-quent oxidation of the resulting crude hydroxycamphanecarboxylic acid (Lankshear and Perkin, Proc., 1911, 27, 166), and (ii) from bornylenecarhoxylic acid by conversion into the azide, and then into aminobornylene, which, on hydrolysis with hydrochloric acid, yields epicamphor in a yield of 80 per cent.of that theoretically possible (Bredt and Hilbing, Clmn. Zeit., 1911, 35,765). A new and convenient process for the preparation of epicamphor has now been worked out, and is briefly as follows: 57 Methyl bornylenecarboxylate is converted by the action of hydroxylamine hydrochloride and sodium methoxide into bornylene-hydroxamic acid, C,,H,,*C!(OH) :NOOH, which melts at 136O, and yields an acetyl derivative melting at 112O. When this hydroxamic acid is heated, it undergoes a remarkable decomposition, yielding epicamphor and ammonia,, and the sodium salt of the hydroxamic acid is decomposed by toluene-psulphonyl chloride with the forma- tion of a syrupy substance, from which epicamphor may be obtained in a yield of 60 per cent.of that theoretically possible by treatment with hydrochloric acid and distillation in a current of steam. Epicamphor melts at 184--185O, and is lavorotatory, having [a]D -58.24O; it yields an oxime (m. p. 103O) and a semicarbazone (m. p. 238O). Bromoep'camphor, CIOH150Br, obtained by heating epicamphor with bromine in looo, melts at 134O, and has [a], -69.3O. Epib orneol, C,,H,,*OH, is produced when epicamphor is reduced with sodium and alcohol; it melts at 182--183O, and yields a urethane melting at S2O; it is perhaps a mixture of epiborneol and epiisobolrneol.When epicamphor is treated with sodamide and isoamyl nitrite, it is converted into a mixture of two isonitroso-derivatives, C,,H,,O:N*OH, which may be separated by crystallisation from light petroleum. The more sparingly soluble a-isonitroso-epicam- phor melts at 170°, and has [u]~-201.9; P-isonitroso-epicamphor melts at 140°, and has [a], -184'3O, and when it is heated above its melting point it is converted into the a-isomeride. Both the a-and B-isomerides yield camphorquinone on treatment with formaldehyde and hydrochloric acid, and are converted by concen- trated sulphuric acid into the imide of camphoric acid (m. p. 244O). dminoep'camphor, C,,H,,0*NH2,, is readily obtained when 8-iso-nitrosoepicamphor is reduced in alkaline solution by zinc dust.It separates from light petroleum as a satiny, crystalline mas, melts at 168-170°, and has approximately La],, + 30.15O. Experiments on the reduction of aisonitrosoepicamphor are in progress. Epicamyhorcarboxylic acid, C,,H,,0*C02H, is produced when sodium or sodamide acts on epicamphor in the presence of carbon dioxide. It melts at 122O, gives a green coloration when ferric chloride is added ta its alcoholic solution, and is decomposed, on heating, into epicamphor and carbon dioxide. Bromoepicuinphorcurbozylic acid melts at 148-150°, and is decomposed at this temperature with the formation of the same bromoepicamphor (m. p. 134O) as is obtained by the direct brominaticm of epicamphor (see above).The investigation of epicamphor is being continued in various directions. 58 ADDITIONS TO THE LIBRARY. I. Donations. Abderhalden, Emil. [Editor.] Handbuch der biochemiechen Arbeitsmethoden. Vol. V. ii. Wien 1912. M. 34-. (Reference.) From the Publishers : Messrs. Urban & Schwarzenberg. Bigelow, 8.Lawrence. Theoretical and physical chemistry. New York 1912. pp. xiiif544. ill. $3 net. (Recd. 19/3/12.) From the Author. The Chemical World. A monthly journal of chemistry and chemical engineering. Vol. I, No. I, etc. Londou 1912. ill. Annual subscription 6/-, post free. (Reference.) From the Publishers: Messrs. J. & A. Churchill. Dyson,8.S., and Clarkson, X.8. Cbemic*al works. Their design, erection, and eqnipment.London 1912. pp. xii + 207. ill. 21/-net. (Red 2/3/12.) From the Publishers : Messrs. Scott, Greenwood & Son. Institute of Chemistry of Qreat Britain and Ireland. A list of official chemical appointments compiled, . . . by Richard B. Pilcher, 4th edition. London 1912. pp. 246. 2/-net. (Recd. 22/2/12.) From the Institute. MacDonald, George William. Historical papers on modern explosives. With an introduction by Sir Andrew Noble. London 1912. pp. xi + 192. 7/6 net. (Recd. 20/2/ 12.) From the Author. XKacEwan, Peter. Pharmaceuticd Formulas . . . collected chiefly from The Chemist and Druggist and The Chemists' and Druggists' Diaries. 8th edition. London 1911. pp. xvi + 1040. lo/-. (Recd. 17/2/ 12.) From the Author.Nisbet, Harry. Theory of sizing. Manchester 1912. pp. xi + 75. ill. 2/6 net. (Recd. 10/2/12.) From the Publiehers : Messrs. Emmott & Go., Ltd. 11. By Purchase. Beckurts, H., and Liining, 0. Die Methoden der Massarialyse. Part 11. Braunschweig 1912. pp. ix+483 to 842. 111. M. 10.-(Recd. 22/2/12.) Treadwell, Pi*e&erick Pearson. Analytical chemistry. Voluule I. Qualitative analysis, Authorised translation from the Get man by William 2". Hall. 2nd edition. New York 191 1. pp. xi +469. ill. 17/-net. (Recd. 23/2/12.) 59 ANNUAL GENERAL MEETING. The Annual General Meeting will be held on Thursday, March 28th, 1912, at 4.30 p.m., when the President will deliver his address, entitled, “ Some Stereochemical Problems.” VAN’T HOFF MEMORIAL.Subscriptions to the Van’t Hoff Memorial Fund should be sent to the Treasurer of the Society (Dr. Alexander Scott, F.R.S.).The sum already promised and received amounts to 244 14s. Od. The next Ordinary Scientiiic Meeting of the Society will be held OA Thursday, March 21st, 1912, at 8.30 p.m., when the following papers will be communicated : “ isoErucic acid.” By A. K. Macbeth and A. W. Stewart. ‘‘ Yarahydroxystilbene and its derivatives.” By J. T. Hewitt, W. Lewcock, and F. G. Pope. “The chemistry of the glutaconic acids. Part V. The esters of substituted glutaconic acids.” By N. Bland and J. F. Thorpe.‘‘Syntheses of 3-hydroxy-(1)-thionaphthen.” By A. M. Hutchison and S. Smiles. R. CLAY AND SONS, LTD., BRUXBRIclt Sl‘.,STAMFORD ST., S.E., AND BUNGAY, SUFFOLK.
ISSN:0369-8718
DOI:10.1039/PL9122800045
出版商:RSC
年代:1912
数据来源: RSC
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