摘要:

PROCEEDINGS OF THE CHEMICAL SOCIETY. No. 131. Session 1893-94. December 21st, 1893. Dr. Armstrong, President, in the Chair. Messrs. Frank Comyns, Martin 0. Forster, Henry Garnett and Arthur R. Ling were formally admitted Fellows of the Society. Certificates mere read for the first time in favour of Messrs. Walter Grafton, 11, Grosvenor Road, Upton Park, Essex ; Robert Hamilton, 5, Lake Street, Hunslet, Leeds ; W. Pellew Harvey, Golden, British Columbia ; R. Hornhy, B.A., Long Preston, Leeds ; Walter Jardine, 86,Victoria Place, Perth ; Clifford Walker Lee, the Atacama Mineral Company, Taltac, Chili ; John Peven, Jun., Blair Terrace, Greenock ; A. B. Robertlson, Dungoyne, Bearsden, by Glasgow ; William Lloyd Williams, Erbistock Villa, 10,Miskin Road, Dartford.The following is the text of a reply received by the President to his recent letter of congratulation to the Russian Chemical Society ; the letter is signed by I). Mendeleeff, President, and D. Konowalow, Secretary, of the Society :-‘‘In the name of Russian chemists we tender to you our hearty thanks for the congratulations and the sentiments expressed by you in Tour letter of the 15th November, 1893, in the name of the London Chemical Society. “The possibility, suggested by you, of a closer tie between the eminent London Chemical Society and the young Russian one was received with greatest applause. We hope, as well as you, that the time is not far off when this closer connection will take place. We desire it the more as we expect to gain the more by it.” Of the following papers those marked * were read :-"91." Corydaline. Part 111. Oxidation with potassium permanganate." By James J. Dobbie, M.A., D.Sc., and Alexander Lauder. By the oxidation of corydaline with potassium permanganate an acid is obtained which contains three atoms of carbon less than the alkaloid. This substance, which the authors have named corydal- ink acid, has the formula C,9H,lN0,,. It is easily soluble in hot water, from which it separatec, on cooling, in long, flat, prismatic crystals, containing 3 mols. of water of crystallieation. Corydalinic acid is also soluble in methyl and ethyl alcohol, but is insoluble in ether, chloroform and benzene. When heated, corydalinic acid sublimes mi thout changing, and then condenses in the form of beautifid, silky needles. It melts wifhout decomposing between 175"and 180".Corydalinic acid is teira-basic ; t,he following salts have been pre- pared and analysed: a normal and acid silver salt, C,,HI,NO,,Ag4 md C,,H,,NO,,Ag, ; an acid potassium salt, C19HlgN0,,K, ; a normal and acid barium salt, C,,H,,NO,,Ba, and C,,H,,NO,,Ba; and the normal lead salt, C,,H,7N0,2Pb2. The acid silver salt, when carefully heated, yields a beautiful sublimate of corydalinic acid. The normal silver and barium salts are appreciably soluble in water ; the lead salt is almost insoluble. When treated with fuming iodhydric acid, one molecular proportion of corydalinic acid gives four molecular propwtions of metEigl iodide, showing that the four methoxy-groups which corydaline contains are st.ill present in the acid.The formula of the acid may,' therefore, be written C,,H,N (OCH,),(COOH),. Corydalinic acid is split up into a number of simpler substances by the action of fuming iodhydric acid. Of these, the one which is formed in largest quantity is a non-nitrogenous acid, which crystallises from the iodhydric solution in long, slender, colourless needles. The formula of this acid, which the authors temporarily name corydalic acid, is C,H,,Os. When heated, corydalic acid melts at 200", under-going decomposition. It is a powerful reducing agent: when silver nitrate is added to its aqueous solution, a white precipitate is obtained, which partially dissolves on heating, and is partially reduced, silver separating ; in presence of ammonia, the reduction is instan-taneous, even in the cold, Copper acetate is rapidly reduced to cuprous oxide on heating with an aqueous solution of the acid. Ferric chloride colours sdutions of the acid intense green, the colour changing to violet on the addition of ammonia or sodium carbonate.A phenol is evolved when corjdalic acid is heated with lime. 253 The authcrs experienced great difficulty in obtaining definite salts of corjdulic acid, partly on account of the ease with which gome of them decompose, and partly because of the difficulty of ascertaining the precise conditions under which the acid and normal salts respec- tively can be obtained.A lea2 salt of the formala C,H608Pb2 was prepared, as well as a salt containing IL larger proportion of lead. Corydalic acid appears to be a dihydroxytricarhoxylic derivative of a reduced benzene ring, the hydrogen both of the hydrosyl and carboxyl groups being displaceable by metal, as in the case of other phenolic acids. The mother liquors from corydalic acid contain several substances, including a, nitrogenous compound, which have not yet been investigated. The authors consider it probable that corydalinic acid is a deriva-tive of phenylpgridine, in which three carboxyl- and two methoxy- gi-oups are united to a partially reduced benzene ring and one carboxyl- and two rnethoxy-groups to the pyridine ring. The form-ation of suGh nn acid from corydaline would be most easily accountcd for by the assumption that corydaline is itself a derivative of a, naphthaquinoline.Corydalinic acid would thus be obtained from corydaline in the same manner as phenylpyridiiiedicarboxy!ic acids are obtained by the oxidation of the naphthaquinolines. It is further probable that the three carbon atoms of corydalitie which are split off during oxidation are attached to the benzene ring, and are represenhed by two of the three carboxyl groups present in this portion of the acid. Corydaline is very stable towards potassium hydrate, only a small portion of the alkaloid undergoiug alteration, even when heated at 180" during many hours with a large excess of this ageut. "92. "The properties of a-benzaldoxime and some of its derivatives." By Wyndham R.Dunstan, F.R.S,, and C. M. Luxmoore, B.Sc. The autkors wish to place on record cerbaiii facts they have obserr,>d during the course of an investigation of the isomerism of. th.3 benzaldoximes which is not yet comlileted. Cryst a1lisat ionof a-Benzal doxi?ne.--RIIore tkan ayear agotheyobserw d that sc-benzaldoxime, which had been described by Petraczek, Reck~nanii, Hantzsch and previous observers as a yellowish oil, could be crystallised by cooling, with ice and salt, the colonrless highly-refractive liquid obtained by distilling the yellow oil under iseduced pressure, The substance is best recrystallised from its solution in light petroleunl. The crystals melt at 34'.Bohh the isomeric benzaldoximes arc, therefore, crystalline compounds, the P-oxime melting at 129". As the result of a considerable experience in t,he preparation of the 254 a-compound the authors find the method suggested by Beckmanu, in which the aldehyde is acted on by hydroxylamine, to be pre- ferable to that proposed by Lachowitx (Ber., 22, 28871, namely, the interaction of hydrobenzamid e and hy droxylam ine hydrochloride. Action of kyilrogen chloride on u-EenzaldoxL'nze.-Beckmann has shown that hjdrogen chloride, as well as hydrogen sulphate, converts a-benzaldoxime into theisvmeric /3-benzaldoxime. The authors also find that, when the a-compound or its ethereal solution is charged with dry hydrogen chloride at the ordinary temperature, the hydrochloride of p-benzaldoxime is obtained, separr1,ting from the ethereal solution in pearly crystals which melt at 66-67".This compound is best recrystallised from its solution in chloroform by the cautious addition of light petroleum. When dissolved in water at O", it dissociates into hydrogen chloride and p-benzaldoxime (which may be recovered by means of ether). If, however, the mixture be allowed to stand, especially at the ordinary temperature, the dilute acid quickly trans- forms the /3-oxime into the a-oxime. Dry hydrogen chloride and aqueous hydrogen chloride, under the same conditions, tend, there-fore, to induce isomeric change in opposite directiosis : the dry gas at ordinary temperhtures changing the a-compound into the /?-corn- pound, whilst the aqueous acid, under 'similar circumstances, changes the /3-into the a-compound.Hantzsch did not succeed in producing a hydrocliloride of a-benzaldoxime. The authors have obtained this substance by leading dry hydrogen chloride into an ethereal solution of the a-compound, well cooled below O", amy rise in temperature being avoided. It is thrown down as a pulverulent precipitate melt'ing somewhat indefinitely near 103". When dry it appears to be perfectly stable at the ordinary temperature, but on attenipting to crystallise it from chloroform isomeric change takes place, and the hydrochloride of th.:: p-benzaldoxime is obtained. When acted 011 by dilute aqueous ammonia at O", the a-hydrochloride furnishes the a-oxime.Action of hydrogen bromide and hydrogen iodide.-Neither the hydro- bromide nor the hydriodide of a-benzaldoxime could be isolated. Even at temperatures below 0", when these gaseous bydrides are led into an ethereal solution of the oxime, the hydrobromide and the hydriodide of /3-benzaldoxime are produced. The hydrobromide (C,EI,C H:NOH) melts at 77-78" ; the hydriodide is unstable, decomposing on standing, iodine being liberated. Action of hydrogeib $uoride.-No hydrofluoride of a-henzaldoxime could be obtained. Hydrogen fluoride throws out from an ethereal solution of the oxime, cooled belov O", a salt which proved, on analysis, to be the dsihydr ofluoride of p-benzaldoxime (C,H,(I€KI:NOH~BHF). Action of RZLZ~~L~/W~Cacid.-Bccktnann observed that when benz-aldoxime is dissolved in concentrated sulphuric acid and the solu- tion is poured into water at 0" the isomeric B-benzaldoxime results.The authors find that the isomeric change, as in the similar case of hydrogen chloride, is preceded by the formation of an unstable a-benzaZdoxirne sulpliate, which may be prepared, as an oil, by mixing a-benzaldoxime with an ethereal solution of sulphuric acid cooled to about -15". Dilute aqueous ammonia, acting at 0" regenerates a-benzaldoxinie from this compound. The oily salt very readily undergoes isomeric changc into solid /3-benzaldosime sulphate. On standing, or on vigoi*ously stirring the liquid cooled to O", solidifica-tion occu1-s owing to the formation of P-benzaldoainze sulphate (C,H,CH:NOEC,H,SO,), which furnishes P-benzaldoxime when de- composed at 0" witth dilute aqueoiis ammonia.Crystallisation of Acet2/1-a-be~zalcloxime.--This compound has hitherto been regarded as an oil. It can, however, when pure, be crystallised by vigorously stirring the liquid cooled below 0". The crystals melt between 14"and 16". Both the acetyl-a-benzaldoxime and the acetyl-/3-benzaldoxime are, therefore, crystalline solids. Action of Alkyl HaZoids.-Methyl bromide, and apparently other alkyl haloids, act on a-benzaldoxirne, furnishing crystalline derivatives, which the aut'hors are investigating 893. '' The interaction of acid chlorides and nitrates." By Henry E. Armstrong and A. Lapworth. It was shown by one of the authors in 1873 (C'hem.Xoc. Journ., p. 683) that acetic chloride and nitrates interact, forming acetic oxide, and that a mixture of chlorine and nitric peroxide gases is evolved instead of the compound NO,Cl, which at that time was supposed to be capable of existing: it was suggested that in the case of silver nitrate perhaps the initial change involved the formation of silver acetate, chlorine and nitric peroxide, and that silver chloride and acetic oxide were then formed by the interaction of the silver acetate and acetic chloride. These observations were confirmed- in 1886 by W. C. Williams (Chenz. SOC.Trans., p. 222), in so far as the production of chlorine and nitric peroxide was concerned, but Lacowicz had meanwhile stated (Ber., 1884, 1281; 1885, 2990) that the gaseous products of such interchanges are nitric peroxide and oxygen, a result which was not confirmecl by Williarns.The authors have extended the observations in order to throw further light on the evolution of chlorine in such cases, and with the object of elucidating the function of chlorine in acid chlorides (cf. these Proceedings, 1891,60). By displacing the air from the apparatus by carbon dioxidc, and thcn passing the crolved gases first throngh oil of vitriol and afterwards through alkali coniained in an apparatus such as is used iii dctt:rmiiiiug niti*ogcu, they have satisfied them- selves that only chlorine and nitrogen peroxide are evolved. Quan-titative experiments show that in the case of silver nitrate and acetic chloride half the chlorine is evolved and lialf retained as metallic chloride ; but it would seem tliat cliloridc is only produccd when the chloride used is capable of acting 011 the salt which is formed in the i rii tiad int,craction :thus chlorosulphonic acid, C1S03H, and potassium nitrate afford little or no chloride, the nitrate being converted into acid Lulphate. The results of experiments with a variety of acid chlorides and nitrates appear to justify the conclusion that the inter- action is one involving the mere displacement of the chlorine of the chloride by oxygen from the nitrate; and, in point of fact, nitric anhydride is found to act in the manner to be expected 011 this assumption, at once converting acetic and benzoic chlorides into the corresponding oxides, chlorine and nitric peroxide.As nitric peroxide has no action on silver nitrate, and as nitrxlic chloride has no exist- ence, the formation of nitric anhydride by Dcville’s method must be considered to be a dircct outcome of the interaction of silver nitrate and chlorine : and if silver nitrate be regarded as a compound of the formula Ag,O*N,O,-a view on behalf of which much may be said- it is conceivable that chlorine simply acts on the “ silver oxide radicle,” removing it from combination with the nitric anhydride, and consequently liberating the latter. The results obtained appear generally to support the conclusion that the chlorine in acid chlor- ides is not possessed of the special activity which is commonly attributed to it.“94. “The freezing points of triple alloys.” By C. T. Heycock and F. H. Neville. Continuing their experiments on the freezing points of alloys, the authors find that gold and cadmium, which in previous experiments seemed to combine together to form a compound (AuCd), behave similarly when they are topther dissolved in tin, bismuth, thallium or lead. The interaction of these metals appears, therefore, to be independent of the nature of the solvent. Silver and cadmium, when dissolved together in different metallic solvents, give results rcsembling those obtained with gold and cadmium. Dissolved in tin or lead the maximum freezing point is reached when the ratio of the two metals is 2Ag: Cd, and in thallium the ratio is almost the same.With bismuth, however, the 257 maximum freezing point is reached at the proportion 4Ag: Cd. The existence of metallic compounds having these formule seems to be probable. Aluminium, when dissolved with tin and gold, behaves as if it were composed of molecules of the composition Al,. The maximurtl freezing point of a mixture of aluminium and tin to which gold has been added is identical with that of pure tin, and corresponds with the proportion AlzAu,.,. It appears probable from these results that a st$able, insoluble compound (AuAlJ is produced, the gold corn-pletely removing the aluminium from solution. This compound is apparently idehtical with Roberts-Bus ten's purple alloy of aluminium and gold.*95. " Synthesis of pentamethylenecarboxylic acid, hexamethylenecarb- oxylic acid, hexhydrobenzoic acid and azelaic acid. By E. fiaworth, B.Sc., and W.H. Perkin, Junr., F.R.S. With the object of preparing hexhydrobenzoic acid synthetically by the interaction of pentamethylene dibromide and ethylic sodio- malonate, the authors followed the directions given by Gustavson and Demjanoff (J.pr. Chern., 39,548) for the preparation of the dibrom- ide from the diarnine obtained by reducing trimethylene cyanide ; they obtained from 1500 grams of trimethylene bromide only 90 grams of what was supposed to be pentamethylene bromide, but which, judging from the results obtained with it, chiefly consisted of tetramethylene bromide.The main product of the interaction of this bromide and ethylic sodiomalonate was 1:1-pentamethylenedi-carboxylic acid, C5H8(CO,H),. On distilling this acid, a monocarb- oxylic acid was obtained which was identified by direct comparison with that prepared by Wislicenus and Giirtner from the cycloid ketopentamethylene produced from adipic acid. By distilling the oil from which the pentamethylenedicarboxylic acid had crystallised out, a higher fraction was obtained consisting of hevamethylenecarboxylic acid, which proved to be identical with the hexhydrobenzoic acid prepared by Aschau from benzoic acid. In addition to the two dicarboxylic acids derived from tetra- and penta-niethjlene bromides respectively and a single molecular pro- portion of malonate, a tetracarboxylic acid was also isolated which was derived from 1mol.of pentamethjlene bromide and 2 of malon-ate ; on dist,illation, this acid was resolved into carbon dioxide and a heptanedicarboxylic acid which proved to be identical with azelaic acid prepared by oxidising Chinese wax. 258 By brominating pentamethyleiiecarboxylic acid and then removing hydrogen bromide, a pentamethenylenecarboxylic acid was obtained identical with that prepared by Wislicenus aiid Gartiler. from hydr- ~xypentnmeth~lenecitrboxylicacid. This acid, which is represented by the formula H,C< CH,*fiH CH,C *CO,H’ resembles benzoic acid in appear- aiice, and not only has the same melting point, but also sublimes with great readiness.“86. ‘I The conversion of ortho- into para-, and of para-into ortho-quin-one derivatives. I. The condensation of aldehydes with 8-hydroxy-a-naphthaquinone.” By S. C. Hooker and W. C. Carnell. Attention has been directed in previous communications on lapa- chol derivatives to the formation of anhydrides by the removal of water or of hydrogen chloride or bromide from compounds of the 0 A’\ x(oH.c~.B~)It was found that the majority of theform I II\/\g lapachols gave two isomeric anhydrides, the one an 01-, the other a /3-naphthaquinone derivative, while a few hare afforded but a single anhydride derived from the P-quinone. In order to ascertain whether 0-1 /\/\ I anhydrides of the form I I Ix-are generally produced, the authors have studied the behayiour of compounds sjnthetically pre- pared from aldehydes and p-hydroxy-a-naphthaquinone,such as were first obtained by Zincke and Thalen (Bey., 21, 2203).From soma of these, small quantities of anhydrides were obtained by Schooch. The authors’ experiments show that the conclusions arrived at by Zincke and his pupils tbat these anhydrides were ol-quinone derivatives was incorrect., and that-as was to be anticipated from the results arrived at in the course of the lapachol iaesearch-they are in reality /3-quinone derivatives, the formation of the anhydride also involving the passage of the a-illto the p-quiuone. It would appear probable that the 0 0 /\/\OH OH/\/\ compounds of the form 1 I I 1 I I derived from alcle- \/\.\c<\o/v x bydes nnd hydroxy-a-naphthaquinoue,are convertcd into anhydrides 259 001 I A/ \/\A/,of the form I 1 I lo ,as when brought into contact tvitli \/\./v&\.X orthotoluylenediamine these anhydrides afford only monazines. Tt has been shown that in the lapachol group both the a-and p-anhydrides are readily hydrated, and yield the same hydroxylapachol, a change which, in the case of the /%anhydrides, involves the reconversion of the ortho- into the para-quinone ; tbe synthesised anhydrides behave similarly, but the change is more difficult to demonstrate, 2-s the hydroxy-deriratives very rapidly undergo change in contact even with very dilute caustic soda-an inter-action which is being studied in detail. The compounds dealt with are those derived from berzaldehyde, acetaldehyde, valeralde- hyde and cuminic, salicylic and cinnamic aldehydes : iu all cases the anhydrides obtained were orange or red compounds, yellow being the colour characteristic of the a-anhydride."97. "The synthesis of lapachoLJJ By S. C. Hooker. By heating hydroxynnphthaquinone dissolved in acetic acid together with valeric a.ldehyde and concentrated chlorhydric acid, the author has obtained an isoineride of lapachol crystallising in orange-red needles, which melts at 119-120", and forms violet-coloured salts with atkali metals ; its acetate$ melts at 74". From this compound others have been obtained containing the same number of carbon atorris as lapachol, and identical with substances prepared from lapachol.At the next meeting, on Thursday, January 18th, 1894, at 8 P.M., the following papers will be read :-“ The molecular formulae of some liquids as determined by their moleculzlr surface energy.” By Professor Ramsay, F.R.S., and Miss Emily Aston, B.Sc. “ Contributions to our knowledge of the aconite alkaloids.” VIII. “ On picraconitine.” Ey Professor Dunstan and Mi-. E. F. Harrison. IX. “ The action of heat on aconitine.” By Professor Dunstnn and Mr. F. H. Carr. X. “Further observations on the conversion of nconitine into isaconitine.” By Professor Dunstan and Mr. F. H. Carr. “ The interaction of benzylamine with ethylic chloracetate.” Drs. Mason and Winder. By “ Condensation of benzylamine with benzenoid aldehydes.” Drs. Mason and Winder. By HARRISON AND SONS,PRINTERS IN OBDINABY TO HER MAJESTY, ST.MARTIN’S LANE.

ISSN:0369-8718    

DOI:10.1039/PL8930900251

出版商:RSC    

年代:1893

数据来源: RSC