|
1. |
Proceedings of the Chemical Society, Vol. 13, No. 175 |
|
Proceedings of the Chemical Society, London,
Volume 13,
Issue 175,
1897,
Page 41-56
Preview
|
PDF (1087KB)
|
|
摘要:
Issued 21311897. PROCEEDINGS OF THE CHEIYIICAL SOCIETY. EDITED BY THE SECRETARIES. _-No. 1'75. Session 1896-7. February 18th, 1897. Mr. A. G. Vernon Harcourt, President, in the Chair. Mr. E. Haynes Jeffers mas formally admitted a Fellow of the Society. Certificates were read for the first time in favour of Messrs. Herbert William Leyland Barlow, M.A., M.B., Holly Bank, Urmston, Man-Chester ; Frederick Filmer de Morgan, A.ndely Lodge, Caeran Park, Newport, Monmouthshire ; Louis Charles Deverell, Onslow House, Worthing ; William James George Lasseter, B.A., 10, Stanley Road, Oxford ; Harry Edward William Phillips, B.A., 47,-Chalfont Road, Oxford ; William Herbert Waite, B.A., Park Road, Halifax ; Charles Thomas Foster Watts, 7, Cambrian Crescent, Chester ; John Welsh, 1ZA,Seller Street, Chester.The certificate of the following candidate, recommended by the Council under Bye-law I (3), was also read :-Frederic Hewlett Burton-Brown, Simla, India. It was announced that the following changes in the Officers and Council were proposed by the Council :-As President-Professor James Dewar, M.A., LL.D., F.R.S., vice Mr. A. G. Vernon Harcourt, M.A., D.C.L., LL.D., F.R.S. As Viee-Pvesidents-Professor W. Ramsay, Ph.D., F.R.S., and Professor J. Emerson Reynolds, M.A., F.R.S., vice Professor James Dewar, M.A., LL.D., F.R.S., and Mr. Horace T. Brown, F.R.S. As Ordinury New,-beys ofCounciZ-Messrs. C. T.Heycock, M.A., F.R.S. ;Rudolph Messel, Ph.D. ; Tom Kirke Rose, D.Sc. ; and Alexander Scott, M.A., D.Sc., vice Messrs.Bernard Dyer, D.Sc. ; G. Harris Morris, Ph.D. ; W. A. Shenstone ;and T. Stevenson, M.D. It was also announced that the Council had awarded the Longstaff Medal to Professor William Ramsay, F.R.S., for the discovery of helium, and his share in the investigation of argon. Messrs. H. Brereton Baker, F. D. Chattaway, and John Shields were appointed to audit the Society’s accounts. Of the following Papers, those marked * were read. “18. The formation of dithonic acid in the oxidation of sulphurous acid by potassium permanganate.” By T, S, Dymond and F. Hughes. When a solution of sulphurous acid is titrated with a solution of potassium permanganate, decolorisation of the permanganate ceases when only 89 per cent. of the quantity required to oxidise the sulphurous acid to sulphuric acid has been used.This is due to the formation of dithionic acid in addition to sulphuric acid. The proportion of dithionic acid produced is constant, and is not influenced by either the dilution or the temperature, or the acidity of the solution. Its production, therefore, appears to be an essential part of the reaction, and to be due to the weak oxidising action of the permanganate in a final stage of its reduction. The sulphuric and dithionic acids produced are in the pro- portion required by the supposition that manganese heptoxide is first reduced to the red oxide with production of sulphuric acid, and further reduced to the monoxide with production of dithionic acid, When, how- ever, sulphurous acid is treated with the red oxide, sulphuric acid is the only product.DIWUSSION. The PRESIDENTsaid that he had worked, a number of years ago, upon the reaction between solutions of potassium permanganate and sulphurous acid, before sodium thiosulphate had come into use for estimating iodine. In making determinations without excluding air from the water, he had found that the quantity of permanganate used was far less than the amount necessary for the complete oxidation of the sulphurous acid. He found that the sulphurous acid was oxidised by the atmospheric oxygen dissolved in the water, and so progressively as the water gradually dissolved the oxygen in the air lying over it. As the result of a number of experiments, he proved that the diminu- tion in the quantity of permanganate required increased with the dilution of the sulphurous acid, and also that if the water was boiled until air-free the quantity of permanganate used was larger, but he had not obtained such constant results as Messrs.Dymond and Hughes. He had tried the experiment of adding a small quantity of manganous sulphate to the dilute solution, and had found that this salt also was 43 able to determine the oxidation of sulphurous acid by atmospheric oxygen. He thought the authors' experiments extremely interesting in showing the constant production of dithionic acid. DR. SCOTTthought it would be worth while to try the effect of manganic sulphate in oxidising sulphurous acid.DUNSTANPROFESSOR suggested that it would be interesting to determine whether the formation of dithionic acid occurred at the positive electrode during the electrolysis of a solution of sulphurous acid, since it seemed possible that the dithionic acid might be formed by the oxidation of sulphurous acid in much the same way as per- sulphuric acid was formed by the oxidation of sulphuric acid. He understood that in the remarkable action of manganous sulphafe des- cribed by the President this salt undergoes no change. "19. On the production of pyridine derivatives from ethylic-P-amido- crotonate." By J. Norman Collie, Ph.D., F.R.S. Amongst compounds from which pyridine derivatives can be obtained, ethylic acetoacetate stands out prominently.The author has already called attention to the fact that, when ethylic /3-amido- crotonate is distilled, various pyddine compounds are formed. When the hFdrochloride of ethylic P-amido-crotonate is heated to a tempera-ture of about 120°, it at once condenses according to the equation 2C6H1,N02HC1= ClOHl3NO3+ NH,Cl + C,H,OH + HC1. This com-pound, C10H,$?03, is the ethylic ether of an oxylutidine : it melts at 138-139'. If in its production the hydrochloride of ethylic P-amido- crotonate be heated with one molecular quantity of ethylic P-amido- crotonate, C6H,,N02HC1 +C6H,,N02=CloHI,NO3+NH,C1+ C,H,oH, an isomeric ether is obtained, m. p. 166-167'. The acids obtained from these two ethers melt respectively at 300-304° and 190-191°, and both acids decompose at their melting point, lose carbon dioxide, and give pseudolutidostyril.NH NH \\/ /\CH,*C CO COOC,H,*CH2C CO II I II I COOC,H,-C CH HC CH \c/ \f I I CH3 CH3Ether, m. p. 139". Ether, m. p. 167". Acid, m. p. 3009 Acid, m. p. 190". A. B. Ether A, when boiled with soda, only hydrolyses with consider-able difficulty. It does not react with acetyl chloride, hydroxylamine, 44 or nitrous acids ; strong sulphuric acid dissolves it on warming, but the substance is precipitated unchanged when the mixture is poured into water. With bromine, a mono-substituted derivative is produced, C,oH,,NO,Br, m. p. 158-1 59". With phosphorus penta- chloride, a chloro-lutidine derivative results, CloH,,NO,CI, which is an oil, b.p. 288-290". After prolonged treatment with tin and hydrochloric acid, the chlorine is removed and replaced by hydrogen, and an a-y-dimethyl-/3-ethylic carboxylate of pyridine, b. p. 246-248", is obtained. The acid obtained by the hydrolysis of ether A is very insoluble in water, but can best be recrystallised from that solvent; various attempts were made to convert this acid into the isomeric acid obtained from ether B, but without result, Ether B, which is isomeric with ether A, is hydrolysed at once when added to soda solution and warmed. It gives a compound with phenyl- hydrazine, and when boiled with strong hydrochloric acid is decomposed ; it is much less stable than ether A. With bromine, it gives a di-substituted product at once, CloH,,N0,Br2.This compound, when treated with soda, gires the sodium salt of a dibromo-acid, which acid melts at 22'7-228" with complete decomposi- tion. Ether B gives on hydrolysis an acid, m. p. 19O-19lo, which can easily be crystallised from hot water; when melted it decomposes quantitatively into carbon dioxide and pseudolutidostyril in exactly the same manner as the isomeric acid, m. p. 300--304". Pseudolutido-styril, C,H,(CH,),NO, which is a dimethylpyridine derivative, was first obtained by Hantzsch (Ber., 1884, 17,2904) by the action of heat on a trimethylpyridine derivative. It was found on heating pseudolutido- styril with 7hc dust, that although some dimethylpyridine (lutidine) was formed, the chief product of the reaction was a trimethylpyridine (collidine). Pseudolutidostyril, when acted on by phosphoriis pentachloride, gives a-y-dimethyl-&-chloropyridine,b. p.21 2-21 4O, and this compound when passed over heated zinc dust yields dimethylpyridine alone. DISCUSSION. DR.FORSTERdrew attention to the apparent similarity between the reactions of the pyridine derivatives described by Dr. Collie and certain of the nitrogen derivatives of camphor when Tiemann's formula was employed. DR.KIPPINGwas of opinion that there was no essential difference between Tiemann's formula for camphor and that proposed by Bredt. He thought that the possibility of the occurrence of tautomerism or stereoisomerism in the compounds described by Dr.Collie should be kept in view. DR. COLLIE, in reply, said he had not gone completely into the details of the various reactions be had made use of in preparing these substances, and he thought that when the full paper was read it would be seen that the substances were actually different in constitution, and not merely tautomeric or stereoisomeric. “20. C6 Sodamide and some of its Substitution derivatives.” By A. W. Titherley, M.Sc., Ph.D. Sodamide in its reactions with organic haloid compounds invariably gives rise to complex decompositions without appreciable replacement of the halogen by NH,. The hydrogen of the sodamide, and not the sodium, reacts, giving hydrochloric acid, which with the amide yields ammonia, whilst the group NaN =remains more or less intact, being found afterwards as sodium cyanide and sodium cyanamide.Charring invariably occurs, even when the reaction is conducted with care. Sodamide on treatment with organic substances possessing a weak acid tendency, such as oximes and hydrazines, readily reacts, giving ammonia and sodium derivatives. In benzene solution these are obtained usually as fine crystalline precipitates, which may some-times be crystallised from boiling benzene. Sodium acetoxime, sodium hydrazobenzene, sodi-urn phenylhg drazine, and others have been thus obtained. A series of substitution derivatives of sodamide formed by the re- placement of one or both hydrogen atoms in NaNH, have also been prepared by the interaction of sodamide with (1) Aromatic amines ; (2) Amides, according to the general equations :-(a) NaNH, + R*NH, =NaNH-R + NH, ; (b)NaNH, + R-CONH, = NaNH* CO *R +NH,.In the former case, the reaction is conducted with the substances in the free state in an atmosphere of coal gas, and in the latter, in benzene solution. Potassium ethylamide, KNHC,H,, is formed by the careful action of ethylamine gas upon gently heated potassium. On heating, it readily decomposes into potassium cyanide, charcoal, and hydrogen. Sodium phenylamide, NaNH* C6H,, sodium diphenylamide, NaN(C,H,),, sodium p-tolylamide, sodium /3-naphthylamide, &c., are all very readily pre- pared by the above general reaction. They form white, greenish- yellow, or brown, amorphous solids with conchoidal fracture, or light yellowish powders, which are blackened and decomposed quickly in the air, darkening especially when moistened with benzene.When sodamide reacts with organic amides (best in boiling benzene 46 solution) ammonia is rapidly evolved, and the substituted sodamides are obtained as fine, white, crystalline solids, those of larger molecular weight being appreciably soluble in benzene. Sodium formamide, NaNH. CO *H,sodium acetamide, NaNH* COCH,, sodium propionamide, and sodium benzamide have been thus prepared -the latter apparently identical with the compound obtained by Curtius from the action of sodium upon benzamide by long-continued boiling in xylol solution. The latter class of substituted sodamides are soluble without decom- position in alcohol, and their solutions, on treatment with alcoholic silver nitrate, throw down bright orange-red precipitates of the silver compounds, which are very unstable.From the colour of these silver derivatives, and the difficulty with which they and the sodium com- pounds appear to react with alkyl iodides, &c., the author concludes that the silver and sodium atoms, respectively, are directly attached to nitrogen, and that therefore the above derivatives are to be repre- sented as possessing the ordinary amide and not the imido-hydroxy formula ; the amides themselves are most probably tautomeric sub- stances. W.‘(Rubidamide.” By A. W. Titherley, M.Sc.,Ph.D. Metallic rubidium behaves like the other alkali metals towards ammonia, displacing one atom of hydrogen and forming rubidamide RbNH,.Though not so energetic as in the case of lithium, the action is very rapid and commences in the cold. On heating in a silver boat to between 200-300°, oily drops of the amide quickly form and flow to a liquid in which the metal floats and partly dissolves to a deep blue solution, at once decolorised and converted into rubidamide by the action of ammonia. Rubidamide crystallises in plates melting at 285-287”, higher than sodamide and potassamide, but lower than lithamide. At 400°, it distils undecomposed in a current of ammonia. With water, it is violently decomposed, giving ammonia and rubidium hydrate. Alcohol also decomposes it and its behaviour with organic substances is very similar to that of sodamide or potassamide.“2%. 6‘ On the spectrographic analysis of some commercial samples of metals, of chemical preparations, and of minerals from Stassfurt potash beds.” By W. N. Hartley, F.R.S., and Hugh Ramage. In continuation oftthe work already published (Roy. 1896,Xoc. P~oc., 60,393, and PYOC.,1897, 13, ll), samples were examined of steel made at Middlesbrough from the blast furnace metal smelted from Cleveland clay ironstone, and rolled into rails; of alumina and ‘red mud’ separated from bauxite at the British Aluminium Co.’s Works at Lame, and of the aluminium prepared from the alumina at Foyers and of various commercial alums. It is shown that of the constituents of the blast furnace metal, the alkali metals, calcium, copper, silver, gallium, manganese, and lead are present also in the steel, but the chromium and nickel have been removed.Of the constituents of bauxite, traces of sodium, potassium, calcium, copper, silver, gallium, iron, manganese, and lead are found in the metallic aluminium. These elements are also present in larger quantities in the ‘red mud ’ and in addition nickel and chromium are present. The AZzcms.-Examined directly, by heating 0.5 gram of the dried sample in the oxyhydrogen flame, sodium, potassium, rubidium, calcium, and thallium are found as common constituents, and copper, gallium, iron, and nickel as occasional constituents. More interesting results were obtained by examining the precipitates produced by potassium ferrocyanide in solutions, containing 50 grams of the alum, strongly acidified with hydrochloric acid.These precipitates con-tained the elements sodium, potassium, rubidium, cslesium, copper, silver, calcium, gallium, thallium, nickel, manganese, besides iron, which was also present in the acid radical. The rubidium, ciesium, gallium, and thallium lines are strong in some of the spectra, and the results indicate that these elements a.re almost wholly precipitated by this process. A sample of (‘aluminoferric ” from Messrs. Spence and Sons, Manchester, contained all the elements found in the alums, but in much larger quantities, Of these elements, the pyrites furnishes the thallium and also a trace of indium found in a bye-product of the manufacture of alum, whilst the other elements were traced to the aluminous minerah, bauxite and shale.The shale was richer in alkalis and gallium than the bauxite, but a sample of French bauxite was richer in silver and lithium than either Irish bauxite or shale. Samples of Stassfurt minerals were examined in the course of the investigation, and were found to yield spectra containing no lines of rubidium, cslesium, gallium, or thallium. These salts gave only weak lines of a few elements besides the lines of the principal elements composing them. It is pointed out in the paper that the elements found by their spectra actually exist in the specimens, as there is no possibility of them being accidentally introduced, and furthermore, substances have been examined which have given no trace even of such widely distributed elements as potassium and calcium and in which the D lines are very weak.The systematic examination of railway metal by such an analytical 48 method as is here employed might lead to results of practical impor- tance. The method reveals the presence of small quantities of metals such as copper, silver, gallium and lead, which have not been ccnsidered in dealing with commercial irons, and the influences of which upon the physical properties of t,hese have not been studied. DISCUSSION. DR.RIDEALsuggested that the calcium present ip aluminium and its compounds might be derived from the vessels employed in the manufac- ture as well as from the bauxite.He thought it probable that calcium might be present as metal in commercial specimens of aluminium. 23. Dissociation pressure of alkylammonium hydrosulphides.” By James Walker, D.Sc.,Ph.D., and John S. Lumsden, B.Sc.,Ph.D. The dissociation pressures of ammonium, ethylammonium, and di- methylammonium hydrosulphides have been determined, as well as t,he dissociation pressures of mixtures of these substances in pairs. The values obtained for the mixtures fell in every case considerably below the values calculated from the dissociation pressures of the components by the law of mass action. The ratios of the dissociation pressures of these substances, whether simple or mixed, are independent of the temperature, a fact which proves t,heir heats of dissociation to bo equal. 24.Supposed condensation of benzil with ethyl alcohol. A correc-tion.” By Francis Robert Japp, P.R.S. The author finds that the compound, described by him in a paper published jointly with Miss Owens (Trans., 1885,47, go), as formed by the condensation of benzil with ethyl alcohol, is in reality identical with Japp and Miller’s anhydracetonedibenzil, C31H2404(m. p. 194-1 95O), and that its formation was due to the presence of acetone in the ‘‘ methylated spirit ” (alcohol denatured ” with 10 per cent. of crude wood-spirit), which was used instead of duty-paid alcohol, in the pre- paration of the compound. The formula, C30H2404,ascribed to the condensation compound requires analytical figures differing only very slightly from those required by anhydracetonedibenzil.At the time the paper was published, the authors believed the com- pound to be identical with Limpricht and Schwanert’s etliyldibertxoih, C,,H2,0,, which Jena stated that he had prepared by the action of alco- holic potash on benzil-the reaction employed by the authors. On the strength of this belief, they proposed to alter Limpricht and Schwanert’s 49 formula to C,,H,,O,, and they further cast doubt on the existence of an acetyl derivative which these investigators had prepared. The author regrets the publication of these perfectly baseless criti- cisms on Limpricht and Schwanert’s work. The author is indebted to Professor Alexander Smith for privately informing him that he had not succeeded in preparing the compound from benzil and alcohol, and thus calling his attention to the matter. 25.“The viscosity of mixtures of miscible liquids.” By T, E. Thorpe, F.R.S.,and J. W. Rodger. The authors having measured the viscosity of a large number of liquids, mostly carbon compounds and of very different types, at various temperatures up to the boiling points under a standard atmosphere (Phil.Trans.?1894, 185A, 379 ; 1897, 189A), have made observations on mixtures of chemically indifferent and miscible liquids, with the view of throwing light on the relation of the viscosity of a mixture to the viscosity of its constituents. A sufficiently comprehensive study of this question would afford answers to many questions of interest.Thus it would settle whether viscosity was related to the number of mole- cules per unit volume or per unit surface, and would indicate, therefore, how viscosity observations, and indeed all observations which depend upon surface effects, should be treated. It would also indicate whether, in the case of a mixture of a simple and a complex liquid, the values of the viscosity gave any indication of the decomposition of molecular aggregates, and how such decomposition was related to dilution and temperature. On the present occasion, the authors communicate the results of a series of measurements made at different temperatures on mixtures of carbon tetrachloride and benzene, methyl iodide and carbon disulphide, and ether and chloroform, the last pair of which they studied on ac-count of the relatively considerable evolution of heat which accompanies their admixture.The methods of observation and of reduction were the same as those previously employed, and the apparatus was identical with that already described (Zoc. cit.). In no case could the density of themixture be calculated by the ordinary admixture rule. Carbon tetrachloride and benzene contract on mixing, as already found by F. D. Brown (Trans., 1881, 39, 207); whereas methyl iodide and carbon disulphide expand. Ether and chloroform contract considerably. As regards viscosity, the observations afford additional evidence of the fact indicated by Wijkander and supported by Linebarger, that the viscosity of a mixture of miscible and chemically indifferent liquids is rarely, if ever, under all conditions, a linear function of the com- 50 position.It seldom happens that a liquid in n mixture preserves the particular viscosity it possesses in the unmixed condition. To judge from the instances hitherto studied, the viscosity of the mixture is, as a rule, uniformly lower than the value calculated on the assumption that each constituent exercises an influence proportional to its amount, although many examples are known to the contrary. No simple rela- tion can as yet be traced between the viscosity of a mixture and that of its constituents. In the case of a mixture of ether and chloroform, the viscosity at low temperatures is gyenterr. than the admixture rule would indicate, but as the temperature is raised, or as the mixture giving the maximum contraction is diluted, the viscosity eventually becomes less than the calculated value, when the general course of the curve showing the relation of viscosity to composition resembles that of such mixtures as carbon tetrachloride and benzene, or of methyl iodide and carbon disulphide.The phenomena in the case of a mixture of ether and chloroform would seem, to begin with, to be analogous to those of a mixture of ethyl alcohol and water, but the condition which determines the contraction and the maximum viscosity, whether it be a feeble chemical combination or a molecular aggregation of a purely physical character, is destroyed by heat or dilution.26. ‘‘ Magnesium nitride as a reagent.” By H. Lloyd Snape, D.Sc., Ph.D. The object of the experiments detailed in this paper was to investi- gate whether magnesium nitride could be utilised to introduce nitrogen in the place of oxygen, chlorine, and other negative elements which combine with magnesium. The author investigated the behaviour of magnesium nitride towards chloroform, carbon trichloride, and benzal- dehyde respectively, in the hope that the reactions represented by the following equations would occur :-(1) 2CHC13+ Mg,N, = SMgCI, + 2HCN ; (2) C,Cl, + Mg,N, = 3MgC1, + C,N, ; (3) 3C,H,*CO H + Mg3N2= 3Mg0 + (C,H,*CH),N,. The substances to be treated with magnesium nitride were sometimes passed in the form of vapour over the latter compound, and sometimes directly mixed with it, the mixture being heated in a sealed tube.In no case was the desired nitrogenous compound obtained. The chloroform was not attacked at temperatures at which hydrocyanic acid could exist without decomposition, but at higher temperatures an energetic reaction took place, and the observed resu1t.s were consonant with the reaction 2CHC1, + Mg,N, = 3MgC1, + C, + N, + H,. Carbon trichloride and benzaldehyde were likewise unaffected at temperatures below those at which the anticipated products could be formed. On 51 heating with benzaldehyde to about 240°, a crystalline product, identi- cal with that described by Laurent as amarone, was obtained.Both were subsequently discovered to be identical with the substance named tetraphenylazine by Japp and Burton. (See also the following paper.) 27. ‘‘The identity of Laurent’s amarone with tetraphenylazine.” By H. Lloyd Snape, D.Sc., Ph,D., and Arthur Brooke, Ph.D. Arnarone being required to compare with the substance obtained, as described in the preceding paper, by the action of magnesium nitride upon benzaldehyde, the authors repeated Laurent’s experiments. It was necessary, in the first instance, to prepare benzoylazotide. This, it was found, could be more readily prepared than by the methods pre- viously given, by the action of ammonium cyanide upon benzaldehyde. Laurent had stated that benzhydramide was produced by the long con- tinued action of ammonium cyanide upon benzaldehyde, but this was probably due to his having employed an excess of the former reagent, The formula given by Laurent to benzhydramide would accord with its formation by treating benzoylazotide with benzaldehyde, C,H,*CO*H+ C‘,,H,,N2=C,,H,,N,O*. The authors propose to try whether such a reaction can actually be carried out.The vapours of ammonium cyanide were conducted into a mixture of benzaldehyde and alcohol. Crude benzoylazotide slowly separated out, and was washed with alcohol and recrystallised from benzene. The crystals softened at 198O, and com- pletely melted, with attendant decomposition, at 202’. They were readily soluble in benzene and chloroform ;difficultly soluble in alcohol and carbon disulphide, scarcely at all soluble in ether, and insoluble in water.An estimation of nitrogen established their identity with the benzoylazotide previously obtained by other methods. To prepare amarone, benzoylazotide was next subjected to dry dis- tillation under a pressure of 21 mm. The residue left, after hydro- cyanic acid and other comparatively volatile vapours had been removed, mas crystallised from alcohol containing a small quanity of hydrochloric acid, and washed with some more of the same solution to extract any residual lophine. The crystals which were left melted at 243 to 244O, dissolved in concentrated sulphuric acid giving the characteristic red solution, and behaved towards other solvents precisely in the same manner as the crystalline substance previously prepared from magnesium nitride and benzaldehyde.By analysis, it was found that the empirical formula of amarone was C,,HI,N, not C,,H,,N, as had been stated by Laurent. The amarone which he obtained was evidently not pure, its melting point being only 233’, or about 10’ lower than that of the purified material. 52 Moreover, a comparison of the properties of pure amarone showed it to be identical with the substance named by Japp and Burton tetra- phenylazine, C28H20N,. The authors were kindly supplied by Professor Japp with some of the latter compound, prepared by him from benzoin, for the purpose of instituting this comparison. It was thus established that amarone, as described by Laurent, was actually tetra- phenylazine.It seems probable to the authors that the substance obtained by Curtius and Blumer having ‘the same empirical formula, C,,H,,,N, to which they have not assigned a structural formula, will likewise prove to be tetraphenylazine. The properties of this compound, so far as they have been described, agree with this supposition. 28. “Studies on the interaction of highly purified gases in presence of catalytic agents. Part I.” By Wm. French, M.A. In absence of light, spongy platinum does not appear to bring about combination between oxygen and hydrogen if they have been previously carefully dried ;and, so far, experiments seem to show that, after the gases have been in contact with the platinum, added moisturedoes not cause an explosion.29. ‘‘Contributions to the knowledge of the P-ketonic acids. Part 111.” By S. Ruhemann, Ph.D., M.A. The author arrives at the conclusion, from the further study of the action of ethylic chlorofumarate and ethylic a-chlorocrotonate on ethereal salts of P-ketonic acids, that the substances described before (Trans., 1896,69, 530, 1383) are to be regarded as ketone-compounds, and he gives the corrections necessitated by the change of view con-cerning the constitution of the various products there recorded. He further shows that the substance formed from ethylic chlorofumarate and ethylic acetomethylacetate is to be looked upon as ethylic aceto- allylenedicarboxylate, CH,. CO-C (COOC,H,) :C:CH-COOC,H, Aniline acts on this ethereal salt with formation of an anile-compound which crystallises in yellow plates (m.p. 180’). Ethylic benzoylacetate and ethylicacetonedicarboxylate form, with ethylic a-chlorocrotonate, compounds which are to be represented by the formulae C,H,*C(OH) :7*COOC2H, COOC,H,*CH,*CO* yH*COOC,H, and CH,*CH :C*COOC,H, CH,-CH:C*OOC,H, Ethylic bonzoylbutylene-Ethylic malonylbutylenetricarboxy-dicarboxylate. late. 53 The latter substance, under the influence of ammonia, yields two iso- meric diamides of the ethereal salt, having the formula Cl~H16N205, besides a diamide of the corresponding acid. 30. '' Contributions to the knowledge of the P-ketonic acids Part IV." By S. Ruhemann, Ph.D., M.A., and A.S. Hemmy, B.A., M.Sc. Ethylic acetosuccinate was found to give a colour reaction with ferric chloride, in opposition to the statement of Conrad (Anncclen, 1877, 188, 218). The authors give an account of various substances formed from this ethereal salt under the influence of ammonia and of phenylbydra-zine. In the latter case, ethylic methylphenylpyrazolone acetate is formed, which, on hydrolysis, yields the corresponding acid. The bromo- derivative of ethylic acetoeuccinate was prepared, and on distillation in a vacuum gave ethylic carbotetrinate (cf. Moscheles and Cornelius, Ber., 1888, 21, 2603). Ethylic benzoylsuccinate, obtained according to Perkin's directions (Trans., 1885, 47, 272), was found to distil without decomposition at 192-193' at 10 mm., and to be decomposed by ammonia with forma- tion of succinamide.31. '' Oxidation of phenylstyrenyloxytriazole." By George Young,Ph.D. The oxidation by alkaline potassium permanganate of phenylstyrenyl- oxytriazole, C,H5*CH:CH(C6H,)*C2~3*OH,yields phenyloxytriazole car- boxylic acid, C,H,* C,N,(OH)CO,H. This acid, immediately on liberation, loses carbon dioxide and forms phenyloxytriazole, C6H5*7*N>COH. HC :N The following derivatives of the carboxylic acid have been prepared. Ethylic phenylethoxytriazole carboxylate, Ph*C,N,(OEt)CO,Et, white needles, m. p. 82-83', Amide, CGH,*C,N,(OC2H,)CONH,, white needles, m. p. 149-150'. Silver salt, C,H,* C,N,(OC,H,)CO,Ag + 2H,O. Z'henylethoxytriazole carboxylic acid, when liberated, loses carbon dioxide and forms phenylethoxytriazole, C,H,* C,N3H* OC,H,, needles, m.p. 60'. This compound has also been formed by the action of ethyl iodide on the silver derivative of phenyloxytriazole. 32. "Apih and apigenin." (Preliminary notice). By A. G. Perkin. Apiin, a constituent of parsley (Apiumpetroselinum), was lirst isolated by Braconnot (Amn., 1843, 48,349), and subsequently examined by Plantn and Wallace (Ann., 1850, 74, 262), who found it consisted of a glucoside. Gerichten (Be?..,1876, 9, ll24), in a more detailed investi- gation, assigned it the formula C27H32016,and considered its decom-position by dilute acids to be most probably represented by the equation C27H3,016+H,O =Cl5H10O,+ 2C6H1206,which is based upon the yield of apigenin thus obtained.He described no derivatives of apigenin, but states that by the action of alkali there is produced phloroglucol and an acid, which by prolonged treatment, is decom- posed with formation of protocatechuic acid, p-hydroxybenzoic acid, formic and oxalic acids, Having suspected, from a description of its properties, that apigenin was a yellow colouring matter, and this having been proved to be the case, the present investigation was instituted. It is wished to reserve the further study of the reactions of this interesting substance. The glucoside apiin is somewhat difficult to fully decompose by dilute acids, the apigenin produced after 3 hours' digestion with hydro- chloric acid of sp. gr. 1.04yielding C =64.3;H = 3.90 ;after 10 hours, C = 65.81, 65.74 ;H= 3.45, 4.01 ; and only when so treated for 25 hours are numbers obtained indicating the formula C,,H,oO,, evidently the correct one.Calc., C =66.66 ; H =3.70 ; Found, C =66.34, 66.37 ;H =3.87, 3.81. Apigenin contains no methoxy-groups, and does not combine with mineral acids; it, however, forms a sulphonic acid not yet thoroughly examined. Dibromapigenin crystallises in almost colourless needles, melting above 290O. Cl,H,0,Br2 requires C=42.05 ;H = 1.87 ; Found, C =42.09 ;H = 2.23 ;and a tribenzoyl compound, C,,H70,(C7H,0),, needles, m. p. 2 10-2 12O has also been obtained. Calc., C = 74 23 ; H = 3.78. Found, C= 74.41 ; H = 4-17. Apigenin reacts with diazobenzene, forming C,,H,0,(C6H,N,),, orange-red needles, m.p. 290-2992'. Calc., C=67.78; H=3*74; N = 11.71. Found, C=67*22;H=3-75 ;N= 11.54,11*56;which yields a monacetyl derivative C,,H705(C,H3~)(C6H,~2),;orange-red leaflets, m. p. 259--260". Calc., C =66.92 ; 11:=3.84. Found, C =66.66 ; H =4.05. Experiments on the further acetylisation of this substance are in progress. By treatment with strong alkali, there is obtained from apigenin, phloroglucol, an acid, m. p. 208-209O, probably p-hydroxybenzoic acid, a trace of acetic acid, and a substance crystallising in colourless needles, m. p. lo?'", which bears some resemblance to p-hydroxyacetophenone. Fuming nitric acid decomposes apigenin, the principal product being an acid; yellow needles, m. p. 244-245'. The dyeing properties of apigenin will be described in the full communi- cation. The investigation of these substances will be continued, and the study of the ethylation and methylation of apigenin is also in progress.55 33. ‘‘ Note on the constitution of the so-called nitrogen iodide.’ ” By J. W. Mallet, F.R.S. Mr. Chattaway concludes his paper by saying that ‘‘ at present the formula NH,I, seems best to accord with the reactions of the compound as a whole, and best to group all the known facts regarding it.” Reference to a short paper by my sometime student, Mr. W. H. Seamon, published in the Chemical News, 1881, 44, 188, will show that a very different substance-liquid, and non-ex plosive-gives results on analysis agreeing well with this formula.It was obtained by the action of dry, gaseous ammonia on solid iodine, and appears to be identical with the substance prepared in a different way by Guthrie, of which brief mention is made by Mr. Chattaway in a footnote. I cannot agree with him that in the explosive compound the ratio of N:I is always 1:2. Some analytical results of my own (published in the paper on this subject in the American, Chemical Jou~wal,1879, 1, 4) were quite incompatible with this ratio, and agreed nearly with the ratio 1 :3. In view of the fact that the preparation which gave these results had been freely washed with alcohol and afterwards with ether, I cannot think it probable that any considerable formation and retention of iodoform raised the proportion of iodine.In any discussion of the composition of the explosive substance in question, some attention ought surely to be given to the probable analogy with nitrogen trichloride, for which Gattermann seems to have fairly well established the formula. CERTIFICATE OF CANDIDATE FOR ELECTION AT THE NEXT BALLOT. The Certificate of the following Candidate is recommended by the Council under Bye-law I. (3). Burton-Brown, Frederic Hewlett, C/o Surgeon-General, Government of India, Simla. Surgeon-Captain, Indian Medical Service, M.A. Oxford. At present engaged in the study of the Indian Materia Medica. Late Demy (Natural Science), Magdalen College, Oxford ; 1st Class, Honour School Natural Science, Oxford, 1886. Late Professor of Materia Medica, University of the Punjab.Author of “A Note on the Chemistry of Milk with reference to Hammersten’s Investigations on 56 Cagein,” published in the Pvoceedings of Physiological Society, 1886. Worked in 1883-4 in Laboratory of the late Professor C. Fr. W. Krukenberg, of Jena. The results of investigations undertaken for the professor were published in his Die vergleichende Physiologie;these ref erred to the spectra of certain organic compounds. Wyndham R. Dunstan. At the next Meeting, on Thursday, March 4th, there will be a ballot for the election of Fellows, and the following Papers will be received. The authors of those marked with an asterisk have announced their intention of Veing present. * (‘Some hydrocarbons from American petroleum.I. Normal and Iso-pentane.” By Sydney Young, D.Sc., F.R.S., and G. L. Thomas, B.Sc. * ‘‘The vapour pressures, specific volumes and critical constants of normal pentane ;with a note on the critical point.” By Sydney Young, D.Sc., F.R.S. * ‘‘On the freezing-point curves of alloys containing zinc.” By c‘. T. Heycock, F.R.S., and F. H. Neville.* “The oxides of cobalt and the cobaltites.” By A. H. McConnell and E. S. Hanes. PASTEUR MEMORIAL LECTURE. The Pasteur Memorial Lecture will be delivered by Professor‘Percy Frankland, Ph.D., F.R.S., at an extra meeting of the Society on Thursday, March 25th, at 8 p.m. ANNIVERSARY MEETING. The Anniversary Meeting will be held on Wednesday, March 31st, nt 3 o’clock in the afternoon. ANNIVERSARY DINNER. It has been arranged that the Fellows of the Society and their friends shall dine together at the Criterion Restaurant on Wednesday, March 31st, at 7 p.m. The Secretaries will be gkad to yeceive early notz3cationfrom those TeZlows who intend to be pesent. RICKARD CLAT AND SONS, LIMITED, LONDON AND BGKGAY.
ISSN:0369-8718
DOI:10.1039/PL8971300041
出版商:RSC
年代:1897
数据来源: RSC
|
|