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Proceedings of the Chemical Society, Vol. 20, No. 284 |
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Proceedings of the Chemical Society, London,
Volume 20,
Issue 284,
1904,
Page 173-212
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摘要:
Issued 12111/04 PROCEEDINGS OF THE CHEMICAL SOCIETY. VOl. 20. No. 284. The following are abstracts of papers received during the vacation and published or passed for publication in the Trunsuctione. 137. “The action of chromyl chloride on stilbene, styrene, and phenanthrene.” By George Gerald Henderson and Thomas Gray, Each of the hydrocarbons, stilbene, styrene, and pbenanthrene, when treated with chromyl chloride in carbon disulphide solution, yields a solid, brown additive compound. These solids are decomposed by water, and oxidation products of the hydrocarbons are liberated. Stilbene is oxidised to bend, and, with partial decomposition, to benzophenone and benzaldehyde. Styrene yields benzaldehyde as the chief product, together with a trace of phenylacetaldehyde and a small amount of a chlorinated compound, The sole product obtained from phenanthrene was phenanthraquinone.138. “The stereoisomeric tetramethyl methylglucosides and tetra-methyl glucose.’y By Thomas Purdie and James Colquhoun Irvine. The pentamethyl glucose (m. p. 42-43’) obtained from tetramethyl- glucose, either by the silver oxide method of alkylation or by the action of methyl alcohol containing hydrogen chloride (Tmns., 1903, 83, 1035), proves to be tetra;met~yE~-met~yZgZulcoside; the stereo-isomeric liquid a-glucoside is produced simultaneously, but in much 174 smaller proportion. The P-glucosido is chnractorised by its laevo-rotatory power, its more rapid hydrolysis by hydrochloric acid, and its msceptibility to the hydrolytic action of emulsin.In aqueous solution, tetramethyl glucose, like glucose itself, exhibits phenomena of multirotation. The a-form (m. p. 88-89'; [alto+ 100*8') is obtained by repeated crystallisation of the crude aldose from petroleum; the p-form (Tanret's y-form), or at least a mixture con-taining a large excess of it ([a]:" 73-1'), is produced by heating the a-form above its melting point. The modification, which is stable in solution ([a]:" 83*3'), is apparently a mixture of the two dynamic isomerides, In the solid state, the P-isomeride reverts to the a-form. Multirot.ation was also observed in benzene and carbon tetra-chloride, and therefore neither ionisntion nor the formation of hydrates or compounds of the acetd classis essential for the occurrence of this phenomenon.139, ' The alkylation of galactose." By James Colquhoun Irvine and Adam Cameron. The silver oxide method of alkylation, when applied to a-methyl- galactoside, gives rise to tetramethyl a-methglgalactoside, a colourless, refractive liquid (b. p. 136-137'/11 mm., [a]g" of tbe pure Iiqiiid is + 105*'7",and in aqueous solution [a]:" is + 143.4'). Hydrolysis with hot dilute hydrochloric acid leads to the production of tetramethyl galactose, a colourless, refractive syrup (b. p. 172'/13 mm.). After distillation, the alkylated sugar displays multirotation, not only in water, but also in n!cohol and benzene, the permsneut values for these three solvents being + 109*5O, 62*6O, 90.0' respectively. In other respects, also, the behaviour of the compound supports the view that it has an oxidic structure.When the substance is either heated with metbyl alcohol and hydrochloric acid or treated with silver oxide and methyl iodide, the stereoisomeric tetramethyl a-and P-methylgalactosides are produced, the latter method giving a large excess of the P-compound, whilst the former yields a greater proportion of the a-isomeride. The crystalline p-form (m. p. 44-45') is much more readily hydrolysed than its isomeride, either by dilute acids or by emulsin. 140. "A method for the rapid ultimate analysis of certain organic compounds," By John Norman Collie. The method consists in burning the substance in a known volume of oxygen, noticing any change in the volume of the gas, and then, by absorbing the carbon dioxide produced, data sufficient for the calcula- tion of the percentage amounts of carbon and hydrogen are obtained.Only those substances can be estimated which are not appreciably volatile in a vacuum, and which contain only carbon and hydrogen or carbon, hydrogen, and oxygen. The time required for an analysis is only about an hour ; the amount of substance used can be reduced to nearly one-tenth of that ordinarily employed, and as the measure- meuts depend on volumes of gases the method is very accurate. 141. “The comparative nitrifying power of soils.” By Sydney Francis Ashby. The method devised for comparing quantitatively the power of cultivated soils to convert their ammonia into nitrites and nitrates has justified itself by :-(1) ‘Yielding samples giving reasonably similar nitrifying power from different parts of the same field.(2) Causing equal seedings from the same sample to show similar nitrifying power. (3) Minimising loss of nitroget by volatilisation of ammonia and denitrification during incubation. (4) Limiting the incubation period to about 30 days. (5) Showing a nitrifying power of the soils tested which corre- sponds with their fertility as gauged from manuring and crop produc- tion, 142. ‘‘ The action of organic bases on olefinic ketonic compounds.” By Siegfried Ruhemann and Edwin Roy Watson. Benzylideneacetylacetone readily unites with sn-toluidine, p-tolu-idiue, ni-chloroitniline, pchloroaniline, P-naphthylamine, and piperidine, but it does not combiue with o-toluidine, a-naphthylamine, or tetra-11ydroquinolino.Piperidinobenzylacetylacetone, C,H,*CH( NC,H,,)*CH(CO*CH3)2, is stable in a dry atmosphere, but in the presence of moisture it gradu-ally decomposes with the formation of benzylidenebisacetylacetone, benzaldehyde, and piperidine. The production of benzylidenebisacotylacetone and similar com-pounds from benznldehyde and ketonic compounds is therefore pre-ceded by the formation of additive compounds of piperidine with ole6nic ketonic compounds. This view is supported by the fact that benzyl- ideneacetylacetone, which combines with piperidine, also condenses with acetylacetone in the presence of the base to form benzylidenebis-acetylacetone, whilst no such reaction takes place if tetrahydroquin-oline, which does not form an additive compound with the olefinic ketone, is used instead of piperidine.176 With phe’nylhydrazine, dibenzylideneacetone forms the phenyl-hydrazone, (C,H,CH:CH),C:N*NH.C,H,,and not an additive com-pound ;with ammonia, it yields a mixture of substances from which has been isolated the compound having the formula C,,H,,N,. Benzylideneacatophenone dibromide, when condensed with ammonis, yields aminobenzylideneacetophenone, C,H,*C( NH2):CH*CO*C,H5, it therefore follows that the corresponding compound obtained by Wieland (Bey,, 1894, 27, 1150) from ammonia and p-nitrobenzylidene- acetophenone dibromide is also unimolecular.143. ‘‘Halides of the acridines and naphthacridines.” By Alfred Senier and Percy Corlett Austin. The halogens combine directly with the acridines, forming a series of well-defined, crystalline compounds, which are sparingly soluble in organic media, and are obtained by mixing the reagents either alone or in a suitable solvent. The products, which have characteristic colours, are unstable, especially in presence of water. The fluorescence, when in solution, which is so marked a character of acridines generally, and which depends on the presence of the acridine “ fluorophore,” is absent, except in three instances. That these compounds are not substitution derivatives follows from their instability, the small number of halogen atoms which they contain, and the fact that no acridone is formed when they are treated with water or alkalis.They are therefore additive compounds, namely, halides. Moreover, the addition takes place in the acridine ring, for, were it otherwise, monadic atoms would be added only in pairs, which, however, is not the case, and a higher number would combine owing to the disruption of the centric benzene linkings. Adopting this view, two formulae are possible for the dihalides. The first, which is of the type of the dihydrides or diliydroacridines (Bernthsen and Bender, Ber., 1883, 18, lSOS), is suggested for the non-fluorescent dihalides, and the second, corresponding with the acridinium salts, alkylhalides, and alkylhydroxides, is employed for the dihalides which exhibit fluorescence.In accordance with the foregoing hypothesis, the tetrahalides should have formulz of the former non- fluorescent type, and acridine tetrabromide, the only tetrahalide described, was found to be non-fluorescent. Those compounds which contain one halogen atom combined with one and three molecular proportions of base respectively are regarded as being products intermediate between the bases and the dihalides, in the one case, and the dihalides and tetrahalides in the other, and to these products dimolecular formulz are assigned. 177 144. ‘‘Reactions involving the addition of hydrogen cyanide to carbon compounds. Part 11. Cyanohydrins regarded as complexacids,” By Arthur Lapworth.Under certain conditions, an aqueous solution of potassium cyanide readily dissolves benzaldehyde and camphorquinone. From the re-sulting liquids, cryst ltlline additive products having approximately the compositions CPH60,KCN,2~H,0and C,,H,,0,,KCN,3H20 have been isolated. These substances behave as salts of the corresponding cyanohydrins, which are probably much feebler acids than hydrocyanic acid itself. 145. ‘(Reactions involving the addition of hydrogen cyanide to carbon compounds, Part 111. Action of potassium cyanide on mesityl oxide,” By Arthur Lapworth. It was shown that when mesityl oxide is heated with potassium cyanide dissolved in dilute alcohol, hydrogen cyanide is first assumed at the ethylenic carbon linking, and that the potassium hydroxide which is simultaneously produced converts the product into meaitonic acid ;more prolonged heating results in the formation of mesitylic acid, which necessitates the addition of a second molecule of hydrogen cyanide in this case to the cirbonyl group, and the subsequent hydro- lysis of the product.146. ‘I 6-Aminocoumarin.” By Gilbert Thomas Morgan and Frances Mary Gore Micklethwait. 6-Aminocoumarin, although resembling the naphthylamines in con- taining two unsaturated rings, nevertheless behaves towards diazonium salts like a para-substituted benzenoid amine, giving rise to stable diazoamino-derivativep. This base and its mono- and di-alkylated compounds and the cor- responding hydrazine and diazocyanide are all coloured substances, whereas the salts of these bases, the acyl derivatives of the primary and secondary aruines, the nitrosoarnines of the monoalkyl derivatives, the diazonium salts of the parent base and its quaternary bromides and iodides are colourless.178 147. ‘‘ Studies in asymmetric synthesis. I, Reduction of menthylbenzoylformate. 11. Action of magnesium alkyl haloids on menthyl benzoylformate.:’ By Alexander McKenzie. When I-menthyl dl-mandelate is hydrolysed by an amount of potassium hydroxide insufficient for complete hydrolysis, an optically active mandelic acid is invariably obtained from the potassium salt thus formed. The mixture of eaters remaining after this partial hydrolysis, when completely hydrolysed, yields mandelic acid which is either optically active or inactive, according to the experimental con-ditions.In the complete hydrolysis, by potassium hydroxide, of a mixture of E-menthyl d-mandelate and I-menthyl I-mandelate con-taining an excess of either of those esters, racemisation phenomena are observed. On reducing menthyl benzoylformate to menthyl mandelate and hydrolysing the latter, the mandelic acid obtained was inactive. But it does not follow from this result that equal amounts of I-menthyl d-mandelate and I-menthyl I-mandelate wera present in the product obtained by the reduction of menthyl benzoylformate, since, even if unequal amounts had been present, the mandelic acid obtained might still have been inactive owing to the racemising effect of the hydro- lysing alkali.Further investigation showed that a slight excess of I-menthyl I-mandelate was present in the reduction product, which, however, on hydrolysis, yielded r-mandelic acid. When menthyl benzoylformate, PhCO*C02*CloH19, is acted on by magnesium methyl iodide and the magnesium addition compound then decomposed by water and dilute acid, a new asymmetric carbon atom is produced. In this instance, no racemising effects are ob- served on Lydrolysing the product with alkali, since an optically active potassium salt is present in solution after the complete removal of the I-menthol, and this salt yields an optically active phenylmethylglycollic acid, CMePh(OH)*CO,H. An optically active phenylethylglycollic acid was also obtained in a similar manner.That the optical activity exhibited by phenylmethylglycollic and phenylethylglycollic acids, prepared by Grignard’s reaction, was actually due to their asymmetric synthesis was shown by preparing diphenylglycoliic (benzilic) acid from menthyl benzoylformate and magnesium phenyl bromide. In this case, where a new asymmetric carbon atom was not produced, the resulting acid was inactive, 179 148, The relation of position isomerism to optical activity. 11. The rotation of the menthyl esters of the isomeric chlorobromo- benzoic acids.” By Julius Berend Cohen and Henry Stanley Raper. The authors have extended the research of Briggs and Cohen on the relation of position isomerism to the rotations of the menthyl esters of the six dichlorobenzoic acids (Trans.,1903, 83, 1213) by preparing and examining the menthyl esters of the ten isomeric chlorobromo- benzoic acids.The molecular rotations of these esters agree in n very satisfactory way with those of the dichlorobenzoic esters. The greatest effect in decreasing the rotation is produced when the halogen enters the ortho-position with respect to the ester group; the least when both halogens are in the meta-position. The mean order of magnitude, beginning with the ester of lowest rotation, is as follows : 2:6; 2:3; 2:5; 2:4; 3:4; 3:5; phenyl, which is precisely the order of rotation of the dichloro-esters. When the chlorine is nearer to the ester group than the bromine, a greater depression in the rotation is produced than by the reverse arrangement.Moreover, when the chlorine occupies the ortho-position to the ester group, the rotation is lower than that of the correspondiDg dichloro-ester. The general effect of bromine is to influence the rotation less than the chlorine-a result which seems to follow from the effect of the monohalogen esters. The great contrast afforded by the two symmetrical compounds of both series, namely, the 3 :5-and 2 :6-esters, is not a little remarkable, and these isomerides may be regarded as the first and last terms of a series in which the 2 :6-compounds have a high melting point and low rotation, whilst the 3 :5-isomerides have a low melting-point, low density, and high rotation.149. “The relation of position isomerism to optical activity. 111. The rotation of the menthyl esters of the isomeric iodobenzoic acids.” By Julius Berend Cohen and Henry Stanley Raper. In a former communication (Cohen and Briggs, Bans., 1903, 83, 1216), the rotations of the menthyl esters of the three monochloro- benzoic acids were given and compared with the constants obtained for the monobromobenzoic esters by Tschugaeff. The authors have now determined the constants for the menthyl esters of the three iodobenzoic acids, 180 50. “The chlorination of the trichlorotoluenes in presence of th e aluminium-mercury couple. The constitution of the tetrachloro- toluenes. Part V.” By Julius Berend Cohen and Henry Drysdale Dakin.In previous papers (Part III., Trans., 1901, 79, 1111 ;Part IV., Trans., 1902, 81, 1325), the authors have traced the progressive chlorination of toluene as far as the formation of the trichlorotoluenes. The products formed on introducing a fourth chlorine atom into each of the six trichloro toluenes have now been investigated. On chlorinating 3 :4 :5-trichlorotoluene at Oo, the chlorine enters the side-chain instead of the nucleus, Although there appears to be no general law determining the position of the fourth entrant chlorine atom, yet there exists a remarkable agreement between the positions taken by the entrant chlorine atoms and nitro-groups when the first two chlorine atoms have been intro- duced into either benzene or toluene.Whatever the ultimate ex-planation may be, it is clear that after the first two chlorine atoms have been introduced into benzene and toluene the special rules which usually govern substitution are wholly or in part set aside in favour of a more general law which includes both the substituent chlorine atom and also the nitro-group. 151. “The chemical dynamics of the reactions between sodium thio-sulphate and organic halogen compounds. Part I. Alkyl haloids. ” By Arthur Slator. The reactions between sodium thiosulphate and methyl, ethyl, and ethylene haloids have been investigated in dilute solution and shown to be in most cases bimolecular, thus : CR,I +S,O,”= CR,S,O,’ +1’. Water was used as a solvent whenever possible, but in a few cases a mixture of this liquid and alcohol had to be employed. The rate of reaction is approximately trebled for a rise of loo.The velocity-coefficients may be used to compare the reactivities of these haloids. With two of the compounds (C,H,ICl, C2H,BrC1), the velocity of the reaction with excess of thiosulphate is independent of this excess and the reaction is therefore unimolecular. To explain this result, it is suggested that tho haloids are capable of existing in two tautomeric forms, and that the measurable reaction represents the change of one form into the other. 152. “Note on methyl fluoride.” By John Norman Collie, Methyl fluoride under 2 mm. pressure, when contained in a vacuum tube having aluminium electrodes and subjected to the spark from an 181 induction coil, gives a bluish-green colour.The spectrum, however, rapidly changes, and the characteristic lines of hydrogen make their appearance. When sparked under the ordinary pressure, the gas is almost immediately decomposed in the following manner : 4CH,F = 4C+4H2+2H2F2. In glass tubes, a secondary change occurs; the silicon fluoride formed by the action of the hydrogen fluoride on the glass is reduced by the hydragen, and silicon is deposited : SiF,+ 2H, =2H2F2+ Si. 153. ‘‘Acetylenic ketones.” By Edwin Roy Watson. The action of various bases on bromobenzglideneacetophenone, C,H,*CBr:CH*CO*C6HS, has been investigated in the hope that a molecule of hydrogen bromide might thereby be eliminated from this compound (compare Ruhemann and Watson, Trans.,1904, 85, 457).The action of solid powdered potash gives rise to phenylacetylene, potassium benzoate, and potassium bromide. The action of alcoholic ammonia gives rise to aminobenzylidene- acetophenone, CGH,-C(NH2):CH*COeC6H5,and by the action of piper-idine two compounds, dipipcridinobenzylacetophenone and piperidino- benzylideneacetophenone, are produced. Strong bases replace the bromine atom in bromobenzy lideneacetophenone by an amino-or substituted amino-group. Phenylpropiolyl chloride reacts readily with anisole to produce the expected acetylenic ketone, methoxybenzoylphenylacetylene. On substituting benzene for anisole the simple reaction no longer occurs, but several substances are produced, including a hydrocarbm having the empirical formula C14H12.Methoxybenzoylphenylacetylene and piperidine yield piperidino-methoxybenzoylstyrene, C,H,*C(NC,H,,):CHoCO*C,H4*O*CH3,whilst the action of hydroxylamine gives rise to 1-phenyl-3-methosyphenyl-isooxazole. Benzoylphenylacetylene yields the phenylhydrazone, C,H,*CSC=C(:N=NH*C,H,)*C,H,, and the anilinobenzoylstyrene, C,H,~C(~H~C,H,):CH*CO°C6H5,when treated with phenylhydrazine and aniline respectively. 154. ‘‘Note on bergamot oil and other oils of the citrus series.” ByHerbert Edward Burgess and Theodore Henry Page. Acetic acid, octylene, pinerie, campheno, and limene have been identified as constituents of a specimea of pure oil of bergamot. The pungency of the first fractions of this oil on distillation is accounted 182 for by the acetic acid, which was also found in smaller quantities in lemon oil and is probably present in the other oils of this series.The octylene found in lemon oil was identical with that in bergamot oil, for both gave butyric acid on oxidation with potassium per-manganate. It is probably a normal constituent of the citrus oils. A second phenylurethane isolated from the terpineol fraction of distilled oil of limes melts at 132", is more soluble than that obtained from ordinary terpineol, crystallises in tufts of needles, and gives on hydrolysis an oil with an intense odour ol distilled oil of limes. 155. "The resolution of externally compensated dihydro-a-methyl- indole." By William Jackson Pope and George Clarke, jun, On crystallising externally compensated dihydro-a-methylindole with d-bromocamphorsulphonic acid, I-di h ydro-a-methy lindole d-bromo-camphorsulphonate, C9H,1N,Cl,H1,Br0*S03H,first separates, and on purification crystallises in needles (m.p. 179.5-180.5' ;[MID+278' in aqueous solution). With caustic soda, it yields I-dihydro-a-methyl- indole, which is obtained as a colourless oil (b. p. 228-229'; [a]D-13.61' in a 1 dcm. tube). The base is dextrorotatory in ethyl alcohol and benzene solutions, but laevorotatory in ethereal solution. A more sparingly soluble dihydro-a-methylindole d-bromocamphor- sulphonate (m. p. 124-125') accompanies the above salt, but, although it has the low molecular rotatory power of [MID+ 242.6' in aqueous solution, corresponding with the presence of a basic ion of [MID -30°, this salt yields inactive base and inactive benzoyl and acetyl deriva- tives.On adding caustic soda to the final mother liquors obtained during the resolution, impure d-dih ydro-a-methylindole separates, but was not obtained free from the lmo-isomeride; its benzoyl and acetyl derivatives were, however, prepared in a state of purity, and have properties corresponding with those of their optical antipodes, 156. "The vapour pressures of sulphuric acid solutions and the mole- cular condition of sulphuric acid in concentrated solution." By Bryce Chudleigh Burt. The vapour pressures of sulphuric acid solutions of various concen- trations (from 25 to 95 per cent. H,SO,) have been determined by an ebullioscopic method.The values so obtained lie on smooth curves when plotted against temperature and concentration. The molecular weight has been calculttted from Raoult's corrected formula : 183 where m--molecular weight of solute ; M= molecular weight of solvent in the gaseous state; g= weight of solute ; G =weight of solvent ;p =vapour pressure of pure solvent ;p' =vapour pressure of solution, The values for m obtained vary over very wide limits, increasing with rise of temperature and decreasing with increase in concentration. The different values do not lie on smooth curves when plotted against temperature and concentration. These abnormalities can only be explained by supposing that com- bination occurs between the solvent and solute with the formation of complex molecules, the formation of such complexes being favoured by an increase in concentration but not by a rise in temperature, 157, ''Reactions involving the addition of hydrogen cyanide to carbon compounds.Part IV. Addition of hydrogen cyanide to benzylideneacetophenone." By Archie Cecil Osborn Hann and Arthur Lapworth. The addition of hydrogen cyanide to benzylideneacetophenone takes place only in presence of a considerable quantity of potassium cyanide, and the failure of Rupe and Schneide (Bey., 1895, 28,957) to bring about the addition process is thus explained. When the solution is but feebly alkaline, the product is P-benzoyl-a-phcnylpropionitrile, CHPh(CN)*CH,*COPh, but in presence of alkali the latter condenses with unaltered benzylideneacetophenone 60 yield the compouiid C,,H,,ON, which Rupe and Schneide obtained in small quantities.The oxime, CHPh(C0,H) CH,*CPh:N*OH, when warmed with sulphuric acid, undergoes the Beckmann change, yielding phengl-succinic acid and aniline, by which reaction the constitution of the ketonic acid is established. By means of the quinine salt, P-benzoyl-a-phenylpropionicacid was resolved into its optical isomerides ; the Zcevo-acid, melting at 176-178' in 6 per cent. ethyl acetate solution, had [a],-157.57', whilst the dextro-acid had [a],+ 157.3O. 158. '' The bromination of silver cyanate." By George Dean. Silver cyanate, when treated with an equivalent weight of bromine in a sealed tube, yielded a yellow product, AgCNOBr.The substance, which did not darken on exposure to light, gave off bromine when heated above 70". At 300-400", the bromine evolved from the sub- stance was accompanied by a thick sublimate of cyanogen bromide. The substance dissociated under 10-20 mm. pressure. Water acts on the compound, yielding silver bromide, cyan uric acid, carbon dioxide, and nitrogen; hydrochloric acid gives rise to a mixture of silver chloride and bromide, whilst cyanogen chloride, bromine, and oxygen are eliminated. The compound oxidises alcohol to acetaldehyde. When the cyanate was brominated at a lower temperature, much more halogen was absorbed ; the product, however, was readily decomposed a current of air, leaving the lens brominated compound.159. ‘‘The decomposition of chloral hydrate by sodium hydroxide and ’ by certain salts.” Emil Alphonse Werner. It is shown that the quantity of chloral hydrate decomposed by sodium hydroxide is a function OF the temperature, for one molecular propor-tion of this alkali is capable of decomposing from one to four molecular proportions of the hydrate with production of chloroform, sodium formate, and free formic acid. Sodium acetate and similar salts are also capable of decomposing the hydrate with the production of formic acid. Water and dilute acids do not decompose chloral hydrate in this manner. Two alternative theories are put forward to explain the decomposition.Firstly, it is assumed that a sodium derivative, CCl,*CH(QNa)*OH, formed on adding the alkali or salt, is immediately decomposed into chloroform and sodium formate, The decomposition of relatively large proportions of the hydrate by sodium hydroxide is easily explained in this way. Secondly, the production of “nascent ” carbon monoxide, ;::-.C:O, as distinct from CiO, is suggested, this hypothetical substance then uniting with water to give formic acid. 160. “ Contributions to the history of glyoxylic acid.” By Heinrich Debus. Two views still prevail with regard to the formula of glyoxylic acid : some chemists represent its composition by the formula C,H20,,H,0, whilst others prefer the expression C2H,0,. The author, after discussing the arguments in favour of each formula, comes to the conclusion that the formula C,H,O,,H,O is more in harmony with the properties of glyoxylic acid than the other.Some basic salts of glyoxylic acid are described which readily de- compose into the corresponding glgcollates and oxalates. 161. ‘‘The colouring matters of the stilbene group. I.” By Arthur George Green. The colouring matters of the stilbene class cannot have the simple structure assigned to them either by 0.Fischer and Hepp or by Bender 185 and Schultz. Apart from the general improbability that substances so constituted would have dyeing properties, the following facts indi- cate that they have a more complex structure :-( 1) Colouring matters can be obtained from p-nitr otoluenesulphonic acid by condensation with alkalis under suitable conditions, which, although having the general characteristics of Curcurnine S or Direct Yellow, contain aldehydic groups in addition to the stilbene group.(2) Stilbene dyes of mixed type can be obtained by condensing dinitrostilbenedisulphonic acid with aromatic amines under the influ- ence of alkalis. (3) Curcuinine or Direct Yellow does not give rise on oxidation to dinitrostilbenedisulphonicacid, but furnishes a yellow dye of greener shade which is very similar to the first product of the alkaline reduc- tion of dinitrostilbenedisulphonic acid. The author has endeavoured to elucidate the constitution of the crimson-red compound which invariably precedes the formation of the stilbene colouring matter and is evidently the first phase of the condensation.The fact that this substance, on oxidation with hypochlorite, gives dinitrostil benedisulphonic acid (Green and Wahl, Ber., 1897, 30, 3097) and is again regenerated from this acid on reduction, supported by a study of its phenyl ester and the analogous chloro-compound (compare next abstract), leads to the view that the crimson-red intermediate compound is a nitroso-stil bene or stilbene nitrolic acid having a quinonoid structure in alkaline solution. 162, “The colouring matters of the stilbene group. 11,” By Arthur George Green, Fred Scholefield, and Fred Marsden, In order to elucidate the constitution of the crimson-red compound obtained on heating p-nitrotol uenesulphonic acid with caustic alkalis, and which forms the first phase of the stilbene condensation, the authors have investigated the behaviour of the corresponding phenyl ester, CGH,(CH3)(80,C6H,)( N0,)[1 :2 : 41, and cnloro-compound, C,H,(CH3)Cl(N0,)[l : 2 :41.The first of these compounds, in alco- holic solution, gives, on adding caustic soda, an intense bright blue coloration even in the cold ;the second gives a reddish-violet coloration at 20-30°. It being found impracticable to isolate these coloured substances on account of their extreme instability, their behaviour on oxidation was studied. They are rapidly decolorieed both by sodium hypochlorite and by air, and give riss to derivatives of dinitrostilbene.From the phenyl ester, a mixture of the trans-and cis-phenyl dinitrostilbenedi- sulphonates was produced. The same two compounds were also obtained from Green and Wahl’s dinitrostilbenedisulphonic acid by conversion 186 into the sulphonic chloride and treatment with sodium phenoxide. This fact serves to confirm the constitution assigned above, and also shows that the dinitrostilbenedisulphonic acid, and probably also the crimson- red intermcdiate compound and the stilbene colouring matters generally, must consist of mixtures of trans-and cis-isomeridse. The reddish-violet intermediate compound from o-chloro-pnitro-toluene, on oxidation with air or sodium hypochlorite, yielded a mixture of trans-and cis-dichlorodinitrostil benes ;the yield of the two isomerides being nearly theoretical, the formation of a third substance is excluded and a simple connection between the coloured intermediate compound and the respective dinitrostilbene derivative is indicated.This is further supported by the fact that these dinitrostilbene derivatives are readily reconverted by alkaline reducing agente, such as phenglbydr-azine and caustic soda, into the blue and reddish-violet compounds from which they are obtained. The authors are thus led to assign to the latter the structure of nitrosostilbenes or stilbene nitrolic acids. 163. ‘‘Researches on chromorganic acids : the behaviour of chromic hydroxide towards oxalic acid and certain other organic acids,” By Emil Alphonse Werner, An aqueous solution of oxalic acid, when saturated with chromic hydroxide, yields a deep purplish-red liquid, which, on evaporation, leaves a dark green residue, appearing almost black by reflected light.This compound hils the propcrties of a true chromoxah acid, H5Cr4(C20,),(0H),,4H20, and yields an ammonium salt, (NH4),Cr4(C204)6(0EC)53 Whilst thoroughly washed chromic hydroxide is readily dissolved by oxalic acid in the proportion required by the formula Crz(C204)3,this is not the case with other related organic acids. Under similar conditions, malonic acid dissolves approximately 50 per cent. of the calculated amount, whereas, with succinic acid, the interaction is inappreciable. A chromomalonic acid, having the formula H5Cr4(C3H204),(0H),,6H20, analogous to the chromoxalic acid, mas obtained, and also a chromo- malonate, K2Cr2(C3H20,),,1OH,O, forming dark purplish-red crystals, the analogue of Croft’s red chromoxalate.The proportion of chromic hydroxide dissolved by malic, tartaric, tricarballylic, citric, glycollic, and lactic acids under the conditions described is relatively small, varying from a minimum of 12 per cent. (malic acid) to D maximum of 27 per cent. (lactic acid). In all these cases, chromorganic acids are produced, having, in general, properties resembling those of chromoxalic acid. With tartaric acid, a saline chromium tartrate, Crz(C,H40,)3, is also formed. When the red salt, K,Cr2(C,04)4,10H20, is boiled in aqueous solution with 2 mols. of 187 potassium oxalate, the blue chromoxalate, XeCr,(C204)6,6H20, is produced; a similar result is brought about by other salts, such as potassium acetate, malonate, or succinate, and so far no chromium compound containing two different acid groups has been obtained.A well-defined potassium boro-oxalate, K2(Bo),(C20,),,3H,C), which is readily obtained by boiling solutions of potassium metaborate and oxalic acid or boric acid and potassium hydrogen oxalate is described. A similar compound is not formed with malonic or succinic acid. 164. “The effect of colloidal platinum on mixtures of Caro’s per- sulphuric acid with hydrogen peroxide.” By Thomas Slater Price and John Albert Newton Friend. Although solutions of hydrogen peroxide and Caro’s acid have no appreciable action on each other, the addition of colloidal platinum causes interaction, oxygen being evolved, according to the equation H2S0,+H,O, =H2S04+H20+ O,, or H2S,09+ 2H20, =2H,S04+H,O +20,.The rate of evolution of oxygen gives a measure of the velocity of the reaction ;titration methods cannot be used, since there are no accurate methods of estimating hydrogen peroxide and Cclro’s acid in the presence of each other. It was found that, as long as the platinum was not precipitated out of the solution, the velocity constants, whether of the second or the third order (corresponding with the above equations), continually increased. This increase is considered to be due to two causes : (1) the gradual increase in the reactivity of the platinum during the reaction; (2) the independent and concurrent decomposition of the hydrogen peroxide and Caro’s acid respectively. In some cases, the velocity curve was a straight line.The effect of varying the concentration of the platinum was also studied, but no definite connection between concentration and velocity could be traced, except that a diminution in velocity was associated with a decrease in concentration of the platinum. In alkaline solutions, the results obtained were indefinite, since inter- action takes place in the absence of platinum and the velocity seems to depend on the rate of stirring. 165. “ The acylation of amides.” By Arthur Walsh Titherley. The conversion of a primary into a secondary amide and a secondary into a tertiary amide cannot, in general, be effected by treatment with acyl chlorides and anhydrides, but by first replacing the hydrogen of the -CO*NH, or -CO*NH*CO-group by sodium ;the resulting sodium acylamide reacts usually with considerable energy with acyl chlorides or, preferably, anhydridw, yielding acylated derivatives.Sodium benzamide and benzoic anhydride, for example, yield sodium di benz- amide and benzoate. At the same time, a tertiary amide (tribenzamide) is formed owing to the interaction of a portion of the sodium dibenz- amide and benzoic anhydride, Although the action is normal in the aromatic and aliphatic series respectively, abnormal results are obtained on attempting to apply the method to the synthesis of mixed aliphatic aromatic secondary amides.Thus, neither sodium acetamide and benzoic anhydride nor sodium benzamide and acetic anhydride yield the expected acetylbeoz- amide in appreciable quantity, the main product of either of these condensations being sodium dibenzamide. Cyclic anhydrides appear to behave normally. Thus, succinic anhydride and sodium benzarnide give rise to benxoylsuccinamic acid (needles, m. p. 180') and s-dibe~~zoyZsuccinu~~de(m. p. 21 1"). A further application of sodium acylamides for the purpose of acylation is based on their condensation with esters (Z'runs., 1902, 81, 1520), but the condensation is abnormal with esters and sodium acyl- amides which contain the groups -CH,*CO,Et and -CH,*CO*NHNa respectively. Methyl oxalate yields the disodium derivative of di-benzoyloxamide, but benzoyloxalimide, which was also anticipated, is not produced.s-D~benxoy~oxccm~de(m. p. 227') is readily soluble in sodium hydr- oxide, but the solution readily undergoes hydrolysis, forming benz- amide and sodium oxalate. Echyl succinate and sodium benzamide readily react, but do not yield either ethyl benzoyl succinamate, dibenzoylsuccinamide, or benzoylsuccinimide ; the chief products are sodium succinimide and ethyl benzoate. A very convenient process for acylating amides direct consists in treating directly with the acyl chloride the amide dissolved in pyridine (compare Freundler, Compt. rend., 1902, 136, 1553 ; 1903, 137, 712-714). The method is limited in the same sense as the sodium acylamide anhydride method, since in this case also aromrttic acyl radicles tend to displace aliphatic groups ; hence it is impossible to prepare acebylbenzamide from benzoyl chloride and a pyridine solution of acetamide.That the method may be applied to the acylation of secondary as well as primary amides is shown by the fact that dibenzamide when subjected to this process yields 50 per cent. of tribenzamide. Benxoylsuccinimide (m. p. 129-130") is readily obtained by the action of benzoyl chloride on a pyridine solution of succinirnide. 189 166. '' The composition of beryl.'' By James Holms Pollok, The irregular results obtained on the analysis of compounds of glucina, prepared from various samples of the oxide, suggested that there was something in the composition of the beryl that had so far been overlooked.The glucina employed was extracted from Limoges beryl during a previous research, and was known to give too high an equivalent, although analysis failed to indicate the presence of aluminium or any other base. This glucina was fractionated by crystallisation of the sulphate, by solution in ammonium carbonate, and by precipitstion from hydrofluoric acid solution by potassium hydrogen fluoride. The glucina was recovered from the various fractions, converted into anhydrous chloride, and the various specimens of this salt snalysed. In certain fractions, a progressive rise in the equivalent of the base was observed, giving figures ranging from 4.77 to 8.1'7.Samples of glucinum chloride were then fractionated by distillation, the most volatile and least volatile portions being analysed separately. Three samples of the most volatile portions yielded equivalents of 9.08, 10.81, and 11-29, Other fractions obtained by collecting the chloride that was first formed, apart from that which distilled over later, gave, on analysis, equivalents o€ 12-30, 14.80, and 18-74, Only a small quantity of the chloride with the highest equivalent was obtained; the most careful analysis failed to detect in it the presence of aluminium, iron, or any other element, the sample having the chemical properties OF glucinum only. A spectroscopic examination of the various specimens with high equivalents showed that certain lines, only faintly visible in ordinary samples of glucina, became steadily stronger as the equivalent increased, and the known lines of glucinum became somewhat fainter.These results indicate that beryl contains a new element having in the main the chemical properties of glucinum, but a much higher equiva- lent ;its chloride is moro volatile and more readily formed than that of glucinum, and the oxide is not so readily precipitated from a hydro-fluoric acid solution by potassium hydrogen fluoride. 190 Thursday, November 3rd, 1904. Prof. W. A, TILDEN, D.Sc., F.R.S,, President, in the Chair. Messrs. C. R. Beck, J. H, Johnston, R. Lessing, J. Marsh, and H, 5. Shelton were formally admitted Pellows of the Society.Certificates were read for the first time in favour of Messrs. Walter Henry Bentley, B.A., 18, Oaten Hill, Canterbury. John Wyclif Black, 20, Mardale Crescent, Edinburgh. Thomas Story Busher, B. A., Queen’s College, OxEord. Lawrence Caldecott, 47, Woburn Place, Russell Square, W.C. Robert John Caldwell, B.Sc., A.C.G.T., 49, Merritt Road, Crofton Park, S.E. Peter Skinner Clark, M.B., Ch.M., Cape Town, Cape Colony, South Africa. Frederick Clarkson-Harold, 10, Fee’s Terrace, Long ford, Ireland. Robert Cornthwaite, Agricultural Laboratory, Halifax. William Crabb, B.Sc., The Grammar School, Penistone, Yorks. James Edward Cunningham, A.R.C.S., 21, Blenheim Gardens, Willesden Green, N.W. Harold Deane, B.Sc., 34, Drakefield Road, Upper Tooting, S.W.Francis Dickinson, 26, O’Connell Avenue, Berkeley Road, Dublin. Edward Evans, 33, Ranelagh Road, Westminster, S.W. Thomas Wallace Fagan, B. A,, Harper Adams Agricultural College, Newport, Salop. John Kerr Forrest, Hawsleigh, Balaclava Road, St. Kilda, N.S.W. Thomas Reginald Hodgson, The Sycamores, Poulton-le-Fylde, Lancs. George William Thomas Horrod, 294, Brixton Hill, S.W. John Kenneth Harold Inglis, M.A., B.Sc., University College, W.C. Thomas Campbell James, B. A,, B.Sc., 4, Belmont Terrace, Llanelly. Walter Hichmond James, 49, Wednesfield Road, Wolverhampton. John Richard Johnson, Apothecaries’ Hall, E.C. Horace Francis Jones, 3, Kerry Crescent, Calne, Wilts. William App Jones, A.B., A.M., Ph.D., 123, 18th Street, New York.Alfred Francis Joseph, A.R.C.S., 95, Marylands Road, Maida Vale,W. James Stanley Lauder, c/o B. Harvey, Qu’Appelle, N.W.T., Assa., Canada. Arthur Garfield Levy, B.Sc., A.I.C., c/o B. Blount, Esq., 76, York Street, S.W. James Patrick Longstaff,B.Sc,, 19, Fettea Row, Edinburgh. Arthur Thomas McDougall, B.A., 3, Albion Road, College Park, S.E. Harold Joseph Clarke Mathews, Massey’s Brewery, Ltd., Burnley, Lancs. 191 Ernest Westby Millnr, A.R.C.S., Windsor, Monkstomn, Co. Dublin. Marie Jean Louis Ernest Rouillard, B.Sc., Malvern, Natal. Percy Edwin Spielmann, A.R.C.S., 21, Cadogan Gardens, S.W Harry Stanley, B.Sc., The Park, Southend Village, Catford, S.E. Thomas Sutcliffe, 19, Rhodes Street, Halifax, YorkP.Paul John Thibault, Howell, N.S.W. DougIas Frank Tmiss, M.Sc., 89, Wood Lane, Harborne, Birmingham. Herbert Wood Watson, B.Sc., 111, Brudenell RoAd, Hyde Park, Leeds. William Henry Willcox, M.D., B.Sc., F.I.C., St. Mary's Hospita1,W. Frank John Wyeth, M.A., 14, Preston Drove, Brighton. The PRESIDENT,in announcing the lamented death of Professor Lobry de Bruyn, which occurred in July, after a short illness, reminded the Society that the deceased was one of the Honorary Foreign Mern-bers elected recently. A letter of sympathy and condolence had been immediately sent in the name of the Society to the widow, and it was hoped that an obituary notice would shortly appear in the Journal. Of the following papers, those marked * were read : "167."Studies on the dynamic isomerism of a-and @-crotonic acids. Part I." By Robert Selbg Morrell and Edward Kenneth Hanson. To show the change in the melting point with variation in the com- position of a mixture of a-and p-crotonic acids at temperatures below the melting point of the less fusible component (a-crotonic acid), weighed quantities of the a-acid were added to a known weight of the P-acid, and the freezing point of the mixture observed. It wi~sfound that; the freezing point of the ,!?-crotonic acid fell from 14.96' to a minimum -lalo,of and then rose to 43.9' on gradunl addition of the a-acid until the mixture contaihed 30.8per cent. of the @-acid. To complete the melting point curve, the lowering of the freezing point of a-crotonic acid by the P-isomeride was observed, and it was found that the curve was a continuous one from 16' through -3' (eutectic point) to 71.9". There is no compound of a-and p-crotonic acids between these temper- atures. The investigation on the composition of the two acids at tempera-tures between 100' and 168' showed that p-crotonic acid changed on heating into the a-modification, and the composition of the mixture was found by cooling the fused mass rapidly and determining its freez-ing point.From the observed values of the freezing points for known mixtures of the two acids, the composition of the mixture was fixed 192 without having recourse to estimation by chemical methods. At 168', the curve showing the transformation of the P-acid into the a-acid met the similar curve for the a-acid changing into the @acid ,the composition at this point was '76 and 24 per cent.of the a-and /3-acids respectively. The boiling point under the ordinary pressure of a mixture of a-and p-crotonic acids is 168-174' (compare Michael, J.pr. Chem., 1892, [ii], 46, 146). These preliminary experiments furnish no evidence as to the exist- ence of a compound of a-and p-crotonic acids between 100' and 168'. *168. The constitution of nitrogen iodide." By Oswald Silberrad. The empirical formuh of nitrogen iodide has been established by Chattaway (Amer. Chern. J., 1900, 23, 363, 369, and 1901, 24, 138, 159, 318, 330, 342) as N,H,I,, but the analytical results obtained by earlier workers showed great variations, chiefly due to unsuitable methods of preparation, insufficient precautions agaiust the decomposing action of light, aud faulty methods of analqsis.In view of the methods of preparation and properties of the compound, the formula N2H,T3 admits of two possible constitutions : NH,:KI, and NHI,:NH,T. Chattawap'a work does not differentiate between these two formula?, and the earlier investigations offer no further proof as to the constitution. On the one hand, the liberation of ammonia by the action of acids supports the former configuration, whilst the formation of di-iodomethylamine by the action of methyl iodide appears to render the latter formula probable. No direct derivatives of nitrogen iodide have so far been pre-pared in a pure state, the metallic compounds investigated have been incorrectly formulated owing to impurities in the products, and the only organic derivatives of nitrogen iodide hitherto obtained are those prepared by Stahlschmidt (Poggendorf's Ann., 1863,119,421) by the action of methyl iodide.These substances are so indirectly related to nitrogen iodide that they afford no definite proof as to its constitution. In order to obtain substitution products closely related to nitrogen iodide, the action of zinc ethyl has been studied, and in this way it has been found possible to obtain direct proofs as to the constitution of the iodide. Zinc ethyl reacts slowly with nitrogen iodide, producing volatile paraffins together with a white, amorphous compound, insoluble in ether, from which ammonia and triethylamine are obtained on treat-ment with dilute acid and subsequent distillation with aqueous 193 caustic potash.From this it is evident that the constitution of nitro-gen iodide is represented by the formula NH3:N13, and that the action of zinc ethyl proceeds according to the equation : This formula for the iodide is also supported by many of the observations of earlier investigators. DISCUSSION. Dr. CHATTAWAYrecalled the fact that in conjunction with Dr. Orton (Amer. Chem. JournuZ, 1901, 24, 342) he had shown thst the formula H3N:N13 alone could explain the actions which take place when nitrogen iodide is slowly decomposed by a stream of water.In such a progressive decomposition, this molecule is broken up and the ammonia mashed away, while NI, mixed with iodine remains in the solid residue, If the ratio N : 31 could have been obtained, the formula would have been established beyond question, but, owing to the accumulation of iodine, a possibility of experimental error was introduced, and the ratio 1.1 8N :31 was the nearest approach to this on which they felt able to rely confidently ; this ratio, however, excludes all formulE except the one they put forward. Although he regarded this formula as un-doubtedly correct, neverthelcss Dr. Silberrad's evidence was not quite conclusive. He drew attention to the small yield of triethylamine, and suggested that under the experimental conditions much of the base mould be found in combination with ethyl iodide as tetra-ethylammonium iodide.It seemed unlikely that nitrogen iodide could be properly dried in quantity by washing with alcohol and afterwards with ether, especially as the compound so very readily interacted with alcohol with the production of ethyl iodide, aldehyde, and ammonia. The triethylamine obtained under these conditions might have been formed by the interaction of ethyl iodide and the liberated ammonia, He hoped to be able shortly to publish the results obtained by the study of the interaction of nitrogen iodide and the magnesium alkyl compounds, particularly the benzyl derivatives. Mr. SMART,in replying on behalf of Dr. Silberrad, who was absent, stated that, although ammonia was produced in quantitative yield by the interaction of nitrogen iodide and zinc ethyl, yet the proportion of triethylamine obtained in these experiments was so small that it could not be detected until the experimental conditions had been care- fully worked out, and even then large quantities of the iodide had to be treated in order that the base might be isolated and identified.The personal risk involved in treating a kilogram of nitrogen iodide under ether with zinc ethyl wzts very small in comparison with the 194 danger incurred in dropping the dry iodide into an ethereal solution of zinc ethyl. He believed that a pure metallic derivative of the nitrogen iodide had actually been obtained, and that a paper on this subject would shortly be communicated to the Society.“169. ‘‘The available plant food in soils.” By Herbert Ingle. The results of the author’s investigation of the available plant food in soils lead to the following conclusions : (1) That extraction with a 1 per cent. solution of citric acid for 7 days renders a soil much less fertile, especially at first, but that chemical changes in such soil, during the growth of the plants, gradu- ally render it again capable of supplying plant food. (2) That beans are able to extract a larger portion of the potash and phosphoric acid present in the soil than barley. This was especi- ally 80 in the case where extracted soil was used. (3) That Dyer’s method (Trccna., 1894, 65, 115) of determining 6‘ available )’plant food in soils is of considerable value in estimating their relative fertility, but that another factor must be considered, namely, the rate at which the “a~ailable” plant food is renewed, especially if the soils exist under different climatic conditions.Whilst this is probably the same or nearly so for soils under similar climatic conditions, it may be, and probably is, very different in tropical or sub-tropical soils to what it is in those of temperate climates. DISCUSSION. Dr. DYERsaid that he had seen photographs of Mr. Ingle’s pot culture experiments, and these certainly seemed to confirm the view that the phosphoric acid and potash soluble in 1 per cent. citric acid solution corresponded with the quantity of those constituents imme- diately available as plant food.But the most interesting part of BIr. Ingle’s work on the subject was that showing the recuperative power of soils even after they had been artificially denuded of imme-diately available mineral food. 170. The basic properties of oxygen : compounds of the ethers with nitric acid.)’ By Julius Berend Cohen and John Gatecliff. In view of recently published results on the additive compounds of the ethers, the following observations which were made early in the year may be of interest. In extracting with ordinary ether the pro- ducts of the nitric acid oxidation of substituted toluenes, it wits 195 frequently observed that, after dehydrating and removing the ether on the water-bath, a small quantity of yellow liquid remained which had a characteristic odour quite unlike that of ether.If this liquid were more strongly heated, or even left for a time, it decomposed with a succession of little explosions and the evolution of nitrous fumes, The liquid is produced by the action of nitric acid on ether and behaves qualitatively like a mixture of these two substances. When added to strong sulphuric acid, nitric oxide is evolved, this result being also obtained by adding strong nitric acid to a mixture of strong sulphuric acid and ether. The liquid behaves like nitric acid to phenol, benzene, and aniline. In order to ascertain whether it had a definite composi- tion the following experiments were made. Definite volumes of the purified ether and dilute nitric acid (IHNO, : 2H20) were shaken up in a separating funnel, the lower layer was removed, and the ethereal layer dehydrated for 24 hours over anhydrous sodium sul- phate.The excess of ether was then removed by distillation until the thermometer registered 50°, when the process wits stopped, for if the temperature rises above this point decomposition occurs and brown fumes are evolved. Air was now blown into the pale yellow residue contained in a beaker until the odour of ether had almost disappeared. As in this state the liquid decomposes rapidly at the ordinary temperature and slowly even at Oo, quantities of one to two grams were rapidly weighed and made up with water to 100 C.C. A measured volume was then titrated with standard caustic soda, usiog methyl-orange as indicator, The following results were obtained with purified methylated ether, ethyl ether, and propyl ether.Ether employed. Percentage of nitric Volumes of ethcr and dilute acid in the product. nitric acid takeu. Methylated ether ... 45-2 50 C.C. HNO, ; 50 C.C. ether ... 44.4% 50 ,, 50$9 99 9, 1, 99... 44.4 25 9) 50 7, Ethyl ether ......... 47.3 50 9, 5087 Y9 ......... 475 50 ># 509, 99 Y9 Propyl ether ......... 33.8 50 7, 50 7,3) 99 ......... 35.9 50 9, 50 7,9, * The ether in this case was not distilled, but evaporated at the ordinary temper- ature under 20 mm. pressure. The calculated amounts of nitric acid corresponding with the formulae (C2H5)20,HN03and (C,H7),0,HN0, are 46 and 38.2 per cent, respectively.The agreement in the case of ethyl ether is quite satisfactory. The compound with propyl ether is evidently less stable at the ordinary temperature, the a5nity for nitric acid appearing to diminish with increasing molecular weight. Amy1 ether and dilute 196 nitric acid have no interaction at the ordinary temperature, and this is also the case with dimethylquinol, the only aromatic ether investigated. 171. “The condensation of formaldehyde with acetone. A pre-liminary note.” By Emil Alphonse Werner. When acetone is mixed with a 40 per cent. solution of formaldehyde, no interaction takes place until a small amount of alkali is added ;if the liquids are mixed in the undiluted form, the addition of a small amount of caustic potash causes after a few moments a very violent reaction, the liquid boils, and an orange-red, resinous condensation pro- duct separates.When the substances are mixed in 10 per cent. aqueous solution, the reaction proceeds much more slowly, tho liquid gradually assumes a dark yellow colour, showing a green fluorescence ; after one hour, the condensation product commences to separate as a bright orange-yellow powder, and at the end of 24 hours the reaction is complete. During the change, the alkalinity of the liquid diminishes considerably. The condensation product, when thoroughly mashed and dried, forms an orange-yellow, amorphous, satiny powder with a peculiar odour. It has the empirical formula C,H,O : analysis gave C=68*97 and 69.58, H=7*46 and 7.54 per cent., whilst the calculated percentages are C =69.56, H =7.24.The compound is freely soluble in alcohol, acetone, or glacial acetic acid, and is precipitated unchanged by water; it dissolves sparingly in benzene, chloroform, or ether. The same substance is produced whether the acetone or the formaldehyde be used in excess. It might have been expected that a compound having the composition C,H60, that is, a polymeride of CH:CH*CO*CH,(C =68.56, H =8*56), would have been formed ;this, however, does not appear to be the case. With bromine in glacial acetic acid solution, it behaves as a saturated compound, hydrogen bromide is evolved, and a mono-brominated deriva- tive formed, which separates on diluting with water as a dark brown powder.The addition of hydrochloric acid to the alkaline filtrate from the original experiment produces a yellow precipitate having the same composition as the orange-yellow condensation product. 172. “The union of hydrogen and chlorine. Rate of decay of the activity of gaseous chlorine.” By Joseph William Mellor. The rate at which active chlorine returns to the ordinary condition follows the exponential law x= xoe-at, where x denotes activity at time 197 t, and a and xo are constants (abeing 2.2 approximately). This is true wben the activity is induced either by the electric discharge or by exposure to light. 173. “Note on the influence of certain salts and organic sub-stances on the oxidation of guaiacum.” By Miss Edith Gertrude Willcock.The author has investigated the influence of various salts on the oxidation of guaiacum with hydrogen peroxide by determining the time necessary to produce a standard blue tint when the conditions were so adjusted that the concentration of guaiacum, peroxide, and salt, and the temperature were the same throughout the series. It mas found that the oxidation was accelerated by the chlorides of ammonium, lithium, potassium, barium, iron, and aluminium, the bromides of sodium and potassium, potassium iodide, sodium fluoride, and potassium nitrite ; whereas the nitrates of ammonium, potassium, and barium, and the sulphates of sodium, potassium, and magnesium had no appreciable influence.These results show (1) that the influence of the s tlt is determined by the nature of the anion, and (2) that the halogen salts as a group accelerate the oxidation. OF the salts examined, those of the halogens alone showed a true accelerating action, for although potassium nitrite certainly accelerates the oxidation of guaiacum by hydrogen peroxide, yet as it will itself oxidise this resin in the absence of the peroxide ibs influence is not comparable with that of the salts which have no independent oxidis- ing action ;this remark also applies to ferric chloride. A comparison of the salts of the halogens among themselves showed that the iodides have the greatest accelerating action, the effect of the others diminishing in the following order ; namely, bromides, chlor- ides, and fluorides.The position of the iodides in the list may be connected with the oxidising action of hydrogen peroxide on these salts. Salts such as aluminium chloride and sodium fluoride, which form acid solutions, have a relatively feeble accelerating power. Ordinary ‘‘ pure ” aluminium chloride readily oxidises guaiacum even in the absence of peroxide, but a specially purified sample of the salt had no independent oxidising actiou whatever, and it increased the rate of oxidation by hydrogen peroxide only very slightly. The activity of commercial aluminium chloride is probably due to the pre- sence of ferric chloride. The acids of the acetic series have no accelerating action, but the metallic salts of the lower members of the series have a slight 198 influence, due probably to the fact that they are hydroljsed by water into free acid and base.Carbohydrates and proteids have no action. Formaldehyde is commonly described as oxidising guaiacum, but this effect is probably due to impurities. The commercial product is an active oxidiser, turning guaiacum blue even in the absence of hydrogen peroxide, but pure formaldehyde, freshly prepared by the distillation of paraf ormaldehyde, has no action whatever. Commercial glycerol readily oxidises guaiacum, turning the resin blue immediately, but in this case also the action seems to be due to impurities, for when freshly distilled under diminished pressure in the dark it has no effect by itself, although, like methyl and ethyl alcohols and ethylene glycol, it assists the accelerating action of the metallic haloids at the ordinary temperature (15-25’).These sub- stances, however, at 50-70” all exert a retarding influence, and this may be due to some absorption of the available oxygen by the alcohol. The carbohydrates dextrose, l;evulose, sucrose, maltose, dextrin, starch, glycogen, arid mastic decrease the accelerating action of the salts, and the proteid globulin has the same action. The action of carbohydrates and protsids (globulins) in diminishing the accelerating power of salts is probably due to the fact that the organic substance, being itself oxidisable, absorbs a part of the oxygen which is liberated, and also to its influence on the degree of dis-sociation of the salt (compare Walker and Hambly, Ti-arts., 1897, 71, 61).The effect of sucrose on the electrical conductivity of sodium chloride has been measured by Mr. Hardy, who found that the pre- sence of 16 per cent. of this sugar in a normal solution of the salt diminished the electrical conductivity by 23 per cent. (compare J. Yhysiot?,, 1903, 29, 26). The accelerating action of the alcohols is adequately explained by their influence on the solubility of the guaiacum. When an alcoholic solution of the resin is added to water, precipitation occurs, but on the addition of more of the alcohol the precipitate redissolves. This was found to be the case with all the alcohols examined except mannitol, and this substance alone failed to accelerate the oxidation of the guaiacum.174. d‘ Note on the influence of potassium persulphate on the estima-tion of hydrogen peroxide.” By John Albert Newton Friend. It was shown in a recent communication (Trans., 1904, 85, 59’7 that in ordinary circumstances a correct estimate of hydrogen per- 199 oxide is not obtained by titration with potassium permanganate. The author now shows that for every molecule of peroxide not accounted for a molecule of peraulphate disappears. This observa- tion suggests that the reaction H202+K,S208=K2S0,+H2S04+0, probably takes place, this change being catalytically accelerated by some oxide of manganese formed during titration.175. “The influence of sunlight on the dissolution of gold in aqueous potassium cyanide.” By William Arthur Caldecott. The fact that the formation of potassium thiocyanate in aqueous solution, under the conditions indicated by the equation PbS + KCy + 0=PbO +KCNS, is accelerated by bright sunlight was noted some years ago by Bette1 and Feldtmann (Proc. Chem. Metallurg. SOC. 8. Africa, 1896, 1, 267). In a paper published last year (J.Chem. Metccllurg. SOC.S. Africa, 1903, 4, 51) by E. H. Johnvon and the author, the analogy between potassium aurocyanide and potassium thiocyanate with regard to their formation and reduction was dis- cussed, The following experiments were carried out with the view of ascer- taining whether sunlight accelerated the formation of potassium auro- cyanide, as well as that of potassium thiozyanate.A strip of gold foil weighing 832.5 milligrams and having a total superficial area of 852 sq. mm. was immersed in a 0.5 per cent. potass- ium cyanide solution, contained in a clear glass litre bottle at about 19’. In another similar glass vessel, coated with three layers of black varnish, was placed a corresponding amount of the potassium cyanide solution and a strip of gold foil weighing 900 milligrams, but with a superficial area equal to that of the other strip. The two bottles were then exposed to direct sunlight for about 54 hours daily during five days, the loss of weight of the gold foil strips was noted, the maximum temperatures of the solutions being recorded daily.The results were as follows : The clear bottle. The blackened bottle. Gold dissolved in Gold dissolved in milligrams. Temp. milligrams. Temp. 1st day ........... 25.5 3 6O 20.0 40’ 2nd day ............ 21.0 34 17.0 38 3rd day ............ 28.0 34 20.0 38 4th day ............ 27.0 37 17.0 40 5th day ............ 32.0 39 19.0 43 Daily average ...... 26.7 36 18.6 39.8 200 This table shows that the rate of dissolution of the gold in the clear glass bottle was 43 per cent. greater than that in the blnckened vessel, although the temperature of the solution was on an average 3.8' lower t>han in the former case. The lately published researches of Berthelot (Compt. rend., 1904, 139, 169) indicate that the aborption of oxygen by aqueous pot msium cyanide is accelerated by sunlight.The greater rapidity with which gold dissolves in potassium cyanide solution in bright sunlight may hence be considered as being due to the liberation of more nascent cyanogen, in proportion to the additional oxygen absorbed, with the consequent increased formation of aurous cyanide. 176. ('The fractional hydrolysis of amygdalinic acid. isoAmgg-dalin." By Henry Drysdale Dakin. As amygdalinic acid, prepared by the action of hot baryta solution on amygddin, gives racemic mandelic acid on mrnplete hydrolysis with acids, it is therefore probably a partially racemic substance, and may be considered as being the maltoside of inactive mandelic acid. On fractional hydrolysis, it was found that the mandelic acid set free in the earlier stages of the reaction was strongly dextro- rotatory, whilst that liberated at a later stage was Iwvorotatory.By repeated crpstallisation of the magnesium salts and of the free acids derived from the products of hydrolysis, it was found possible to isolate both cptically active varieties of mandelic acid in a pure state. Starting from amygdalin, which on hydrolysis gives I-mandelic acid almost exclusively, it is thus possible to prepare both cl-and I-mandelic acids without employing any additional opticnlly active substance. The production of an isomeric partially racemic amygdalin, as the result of the limited action of bnryta solution on amygdalin, was sug-gested by J.W. Walker (Trans., 1903, 83, 472), but efforts to isolate the substance were unsuccessful. The substance has now been obtained in crystalline form, and its main properties have been investigated ; it is very much more soluble in water and alcohol, has a much lower melting point and a higher specific rotation than ordinary amygdalin. The close relationship between the two substances is shown by the fact that both are similarly attacked by the enzyme?, emulsin and maltase. The new substance gives aruygdalinic acid and ammonia on treatment with alkali, whilst with concentrated acids it yields mandelic acid, glucose, and ammonia. The mandelic acid set free on complete hydro- lysis with hydrochloric acid is distinctly dextrorotatory, whereas that derived from ordinary amygdalin is kevorotatory.The suggested cause of this surprising result is that the two forms of which iso- 201 amygdalin, as a partially racemic substance, may be asmmed to be composed are hydrolysed at unequal rates, and that the form which is least readily hydrolysed undergoes progressive racemisation. 177. '' The effect of anhydrides on organo-magnesium bromides. Part I. The action of phthalic anhydride on magnesium a-naphthyl bromide." By Samuel Shrowder Pickles and Charles Weizmann. Although Grignard's reaction has been ext#ensively used for the production of hydrocarbons, alcohols, and acids from ketones and esters, the effect of this reaction on anhydrides does not seem to have been studied. With the object of discovering another method for the preparation of certain quinones and their derivatives, the magnesium reaction was tried with magnesium a-naphthJ 1 bromide and phthalic anhydride.The course of the reaction may be expressed as follows : (1) Formation of additive compound : co /C( C,,H,)*OMgGrC6H*<cO>0 + C,o'l[,'MgBr = c~H~<--co--->o* (3) Further action of water : the product of the reaction being a keto-acid, in this case, a-naphthoyl- o-benzoic acid. Such acids, on treatment with strong sulphuric acid, pass aImost at once into quinones, the foregoing acid, for example, yielding naphth- anthraquinone. Subsequent experiments have shown ttat the above reaction is capable of general application. Thus, using phthalic anhydride and bromobenzene, the authors have obtained benzoyl-o-benzoic acid and anthraquinone, and with phthalic anhydride and /3-bromonaphthalene they have obtained P-naphthoyl-o-benzoic acid and naphthacene-quinone. Experiments are now being carried out in the aliphatic series with succinic anhydride and various fatty bromides.202 178. (‘The combustion of ethylene.” By William Arthur Bone and Richard Vernon Wheeler. The combustion of ethylene appears to be essenti:zlly a process of hydroxylation, that is, oxygen initially enters the hydrocarbon and is distributed between the carbon and hydrogen, giving rise to hydroxyl- ated molecules, which sooner or later, according to the rapidity of the process, undergo thermal decompositions into simpler products.The stages in the combustion are represented by the following scheme : CO+H, CO+H,O CO,+H,O The more salient features of the experiments may be summarised as follows : (1) There is no preferential combustion of either carbon or hydro-gen when ethyIene interacts with a quantity of oxygen insufficient to burn it completely to steam and oxides of carbon. The separation of carbon or hydrogen, when it does occur, is to be entirely ascribed to secondary thermal decompositions. (2) Formaldehyde is the most prominent intermediate oxidation product, and at low temperatures its formation is probably preceded by that of a less oxygenated product. (3) The formation of aldehydes precedes that of steam and oxides of carbon. (4) The stage in the combustion process at which secondary decom- positions set in is determined entirely by the temperature conditions.Below the ignition point, such changes do not come into play to any appreciable extent until the stage corresponding with the formation of formic acid is reached. The greater part of this substance theii decomposes into carbon monoxide and steam, whilst the remainder is further oxidised to carbonic acid, which in turn breaks down into carbon dioxide and steam. Above the ignition point, the formaldehyde produced rapidly decomposes into carbon monoxide and hydrogen. (5) There is no Separation of carbon or liberation of acetylene, even in the explosive combustion of ethylene, except when the oxygen present is insufficient to burn the hydrocarbon to formaldehyde.In such circumstances, the excess of ethylene is thermally decomposed, yielding carbon, hydrogen, methane, and traces of acetylene. Some evidence was obtained under suitable conditions of the transformation of the initial product, CH,:CH*OH, into the isomeric acetaldehyde, which is then independently oxidised to carbon monoxide, water, and formaldehyde,as proved in a previous paper. 203 The authors have not yet decided whether at low temperatures the oxygen is conveyed to the hydrocarbon directly or indirectly, but at high temperatures, as, for example, in the explosion wave, it is believed -that there is a direct passage from to H*!?oH as the result H*C*H H*C*OH’ of collisions between single molecules of ethylene and oxygen.179. 6c The decomposition of methylcarbamide.” By Charles Edward Fawsitt. This investigation has been conducted on similar lines to that on carbamide (Zeit.physikal. Chem., 1902, 41, 601), and it is found that the mechanism of the decomposition is precisely similar in the two cases, so that the theory put forward to explain the decomposition of carbamide is also applicable in the present instance. The decomposition of methylcarbamide by acids is due to a trans-formation of the methylcarbamide into methylamine cyanate, which is subsequently decomposed by the acid. The initial transforma- tion is a reaction of the first order, and the velocity coefficient at 99’ is almost exactly one-half that of carbamide. In these experiments it is only the free methylcarbamide which represents the active con- centration of substance decomposing at any instant, A direct hydro- lysis is brought about only very slightly even by very concentrated alkali, and the reaction with pure water is very much slower than is the case with carbamide.180. Position isomerism and optical activity ; the methyl and ethyl esters of di-o-, -m-, and -p-nitrobenzoyltartaric acids.” By Percy Faraday Frankland and John Harger. The authors describe the preparation and properties of the six esters in question, which were obtained by the action of the three isomeric nitrobenzoyl chlorides on methyl and ethyl tartrates respectively. The rotation of each was determined in the fused state, and over a wide range of temperature, in some cases from 15’ to 180’.All these com- pounds, like the corresponding dibenzoyl- and di toluyl-tartrates, are strongly laevorotatory. The p-and mnitrobenzoyl groups were found to exercise a very great rotatory effect, the molecular rotations of the diethyl di-p- and di-m-nitrobenzoyltartratesand of the dimethyl di-p- nitrobenzoyltartrate being considerably in excess of those exhibited by the corresponding dibenzoyl- and ditoluyl-tartrates. The dimethyl di-m-nitrobenzoyltartrate, on the other hand, exhibited a molecular 204 rotation which, although considerably greater than that of dimethyl dibenzoyltartrate, was almost identical with that oE dimethyl di-m- toluyltartrate.The o-nitrobenzoyl group behaved in an a1together exceptional manner, its relative rotatory influence being entirely dependent on the temperature. Thus it ha;, been previously shown by one of the authors (P. Frankland and Wharton, Trans., 1896, 69, 1591) that the rotatory effect of the o-toluyl group is inferior to that of the benzoyl group, and it would have been anticipated, therefore, that the o-nitro- benzoyl radicle should exert a still smaller effect ;this was actually found to be the case above 130°,but with fall af temperature its rotatory effect so rapidly increases that at 15O the latter proved to ba even greater than that of the p-nitrobenxoyl group. This abnormal behaviour of the o-nitrobenzoyl group, which was only fully studied in the case of the ethyl compound, was thus limited to the superfused state, the melting point of diethyl di-o-nitrabenzoyltartratebeing 143’.This melting point, again, is exceptional in being considerably higher than that of the meta-(95.8”) and that of the para- (126.5’) com-pounds respectively. The rotation of all these compounds is very sensitive to temperature, diminishing in every case as the latter rises, much the largest tem- perature-coefficient being possessed by the ortho-compound. 181. “The action of nitrogen sulphide on organic substances. Part II.” By Francis Ernest Francis and Oliver Charles Minty Davis. The action of nitrogen sulphide on anisaldehyde gives rise to tri- pmethoxycyenidine and anisamidine sulphate, which are isolated by taking advantage of their solubilities in benzene and water respec-tively.An insoluble derivative of anisamidioe, containing sulphur, is also produced which is very stable towards alkalis but yields anisoylanisamidine on treatment with strong acids. 182. “Reduction products &di thylanhydracetonebenzil, and condensation products of benzaldehydes with ketones.” By Francis Robert Japp and William Maitland. When up-dimethylanhydracetonebenzilis boiled for a few minutes with fuming hydriodic acid, it is reduced to a cyclopentenone deriva-tive (m.p. 122.): 205 This compound is identical with that which Vorlander and Wilcke (Ber., 1898, 31, 1887) obtained by the action of hydrogen chloride on dimethyldiphenyltetrahydro-y-pyrone,but which they erroneously regard as dibenzylidenediethylketone.By further reduction with hydriodic acid, it yields the corresponding cyclopentanone derivative. The authors have prepared various alkyl derivatives of tetra-hydro- y-pyrone by the usual method of condensing benzaldehyde with aliphatic ketones, and have studied their reactions, especially with the view of obtaining cyclopentenone derivatives. 183. '' Interaction of sodium phenylglycidate with phenylhydr- azine." By Francis Robert Japp and William Maitland. When sodium phenylglycidate is heated with phenplhydrazine in alcoholic solution at looo, 4-hydroxy-1:5-diphenyl-3-pyrccxolidons (m.p. 173.5') is obtained in the form of its sodium salt: + CGH5mNH-NH2= C,H;y --"">CO + H20.C,H; CH*CH(OH) heat or of dehydrating agents, hydroxydiphenyl- pyrazolidone is converted into 1:5-diphenyl-3-pyrazolone, C6H,'r'NH C6H;C :CH>'O (m.p.252O), previously obtained by Know (Bey., 1887, 20, 1107) by distilling cinnamoylphenylhydrazine. 184. a-Benzoyl-P-trimethacetylstyrene."By Francis Robert Japp and William Maitland. The authors have obtained a-benzoyl-,8-trimethacetylstyrene, C6H5*7=7H C,H;CO CO*C(CH,), (m. p. 115'), by the action of potassium hydroxide on a mixture of benzil and methyl tert.-butyl ketone. In its reactions, it closely resembles up-dibenzoyls tyrene (Japp and Klingemann, Trans., 1890, 57, 662), except that, on heating, it is converted into a mixture of 206 (m.p. 150') andtwo isomeric wotolactonss, (CH,),C*C8H*VC6H5)2CO \/ 185. '(Olefinic ketonic compounds." By Siegfried Ruhemann. Rabe (Ber., 1902, 35,3947) stated that the additive compound of aniline and ethyl benzylideneacetoacetate melted at 78' instead of at 105' (erroneously printed as 103') as found by Ruhemann and Watson (Trans.,1904, 85,1170). On re-examination, it was found that the melting point could be raised to 106-107°, which closely agreed with that given by Francis (Bey., 1903, 36, 937) for the substance he obtained by combining benzylideneaniline with ethyl acetoacetate. The author also examined the action of potassium cyanide on benzylideneacetylacetone and ethyl benzylideneacetoacetate respect- ively, and found that in the first case cyanobenzylacetylncetone, C6H5*CH(CN)*CH(CO*CH,),(m.p. 127-128'), and, in the other, ethyl cyanobenzylacetoacetate,C6H,~CH(CN)*CH(CO*CH3)*C02*C,H5, are produced, On hydrolysis with caustic potash, the former nitrile furnishes phenylacetopropionic acid, C,H,*CH( CO,H)*CH,*CO*CH,, whilst ethyl cyanobenzylacetoacetate yields a mixture of phenylaceto-propionic and phenylauccinic acids. Under the influence of concen-trated sulphuric acid, cyanobenzylacetylacetone is transformed into phenyldiacetopropionic acid, C,H,*CH(CO,€I)CH(CO*CH,), (m. p. 149-150') ;ethyl cyanobenzylacetoacetate, on the other hand, furnishes the dihydropyrone derivative, NH--C(CH3)>C*C0,*C,H5.ICO*CH(C6H,) The mode of formation and the properties of cinnamylideneacetyl-acetone, C,H;CH:CH*CH:C(CO*CH,), (m.p. 103-104'), are also described. This di-olefinic ketone, on exposure to light, undergoes a change similar to that occurring in the case of cinnamylidenemalonic acid (Liebermann, Ber., 1895, 28,1440 ;Riiber, Ber., 1902, 35,2411), and yields a colourless substance (m. p. 158-159') which has double the molecular weight of cinnamylideneacetylacetone. These two com- pounds are still under examination. 207 186. ':Aa-Oleic acid." By Henry Rondel Le Sueur. In a former communication (Trans., 1904, 85, 827), tbe author stated that he was engaged in the preparation of an isomeride of oleic acid containing the double linking between the a-and P-carbon atoms, and, although the work is not complete, the appearance of a paper by G.Ponzio (Gaxzetta, 1904, 34, ii, 77; Chem. Centr., 1904, ii, 691) on the same subject necessitates the publication of the results so far obtained. Aa-Oleic acid, C,,H,,*CH:CH*CO,H, obtained by the action of alcoholic potash on u bromostearic acid, crystallises from light petro- leum in long, flat needles melting at 5s-59'; its ethyl ester melts at 25-26". The acid, on oxidation with potassium permanganate, yields ap-di/Lydi.oxystearic acid melting at 126q which on further oxidation yields palmitic acid, thereby proving the position of the double linking. 187. "Action of magnesium alkyl halides on derivatives of camphor." By Hartin Onslow Forster. The action of magnesium alkyl halides on derivahives of camphor is not always normal, and several interesting changes have been observed. The compound, C,,H,,O,, from camphorquinone and magnesium methiodide is a volatile, colourless compound, dissolving readily in organic media and very sparingly in water, from which it crystallises in minute, transparent prisms and needles melting at 132'.A 2 per cent. solution in absolute alcohol is optically inactive. The compound, C,,H,,O,N, from isonitrosocamphor and magnesium methiodide is soluble in acids and alkalis, forming colourless solu-tions; it separates from boiling water as a crystalline powder and melts at 180'. The compound, C,,H,,O,N, from nitrocamphor and magnesium methiodide is insoluble in sodium carbonate solution, but dissolves in aqueous sodium hydroxide ; it crystallises from petroleum in lustrous leaflets melting at 83". The cornpound from hydroxymethylenecamphor and magnesium methiodide is a colourless, fragrant oil which boils at 234O/765 mm., has sp.gr. 0.9639, and [a],,170.8'. It is insoluble in aqueous sodium hydroxide, and gives no coloration with ethereal ferric chloride, 208 188. ‘‘ Sulphonchloroalkylamides.” By Frederick Daniel Chattaway. In the course of an investigation of nitrogen halogen derivatives of the sulphonamides, a number of compounds yielded by various methyl, ethyl, and benzyl derivatives of the sulphonamides have been obtained. All the sulphonalkylamides are readily converted by a solution of hypochlorous acid into the corresponding chloroamides, RSO,*NHR’+ HOCl =RSO,*NClR’ + H,O.Those containing methyl and ethyl groups are comparatively stable, whereas those in which benzyl occurs undergo spontaneous decomposition afker a few hours ; even when kept in dry air, chlorine and hydrogen chloride are liber- ated, while a pungent odour, resembling that of benzaldehyde, becomes apparent. When rapidly heated, they all decompose with evolution of gas, but without explosion. Like the sulphondichloroamides, they are very reactive, and promise to be of considerable value in the syn- thesis of secondary amines containing different a1 kyl groups. The following compounds are typical examples of a long series of these substances which has been prepared. Bsnzenesulphonchloro-methylamide, C,H,*SO,*NCl-CH,, colourless, short rhombs, m.p. 81’ ; benzenesulphonchloroethylamide, C,H,*SO,*NCI*C,H,, colourless plates, m. 1’.52’; benzenesulphonchlorobenzylamide,C6H,*sO2*NC1*CH,=C~~,, colourless, slender prisms, m. p. 109’ ;p-toluenesulphonchloromethyl-amide, CH,~C6H,~S02~~C~~CH3,colourless prisms, m. p. 82’ ; m-nitro-benzenesulphonchloromethylamide, NO,*C,H,*SO,*NCl*CH,, pale yellow, four-sided plates, m. p. 136’ ;a-naphthalenesulphonchloromethyl-amide, CloH7*S0,*NCl*CH,, colourless, six-sided prisms, m. p. 78”; a-naphthalenesulphonchlorobenzylamide, C,,K~*SO,*NCl*CH,*C,H,, very pale yellow prisms, m. p. 94’ ; /3-naphthalenesulphonchloromethyl-amide, colourless prisms, m. p. 9lo; P-naphthalenesulphonchloro-propylamide, C,,H7*SO2*NCl*C3Hp, colourless plates, m.p. 86’. RESEARCH FUND. A Meeting of the Research Fund Committee will be held in December next. Applications for grants, to be made on forms which can be obtained from the Assistant Secretary, must be received on or before Monday, December 5th, 1904. 209 At the next ordinary meeting, on Wednesday, November 16tb, 1904, at 5,30 p.m., the following papers will be communicated : 4‘ The isomerism of the amidines of the naphthalene series.” By R. Meldola and J. H. Lane. ‘‘Theory of the production of mercurous nitrite and of its conversion into various mercury nitrates.” By P. C. Rsy.‘‘Amidechloroiodides.” By G. D. Lander. “ A new synthesis of isocaprolactone and some derivatives.” By D.T. Jones and G. Tattersall. “The influence of substitution in the nucleus on the rate of oxida-tion of the side-chain. Part 11. Oxidation of the halogen derivatives of toluene.” By J. B. Cohen and J. Miller. “The halogen derivatives of naphthacenequinone.” By S. 5. Pickles and C. Weizmann. Constitution of pyrazolidone derivatives.” By B. Prentice. ADDITIONS Y.0THE LIBRARY. I. Donations. Arnold, Carl. Compendium of chemistry, including general, in- organic, and organic chemistry. Translated by John A. Mstndel. pp. 627. New York 1904. From the Publishers. Beadle, Clayton. Chapters on papermaking. Vol. I. pp. 151. London 1903. From the Author. Behring, E. VOD. The suppression of tuberculosis, together with observations concerning phthisiogenesis in man and animals, and suggestions concerning the hygiene of cow stables and the production of milk for infant feeding, with special reference to tuberculosis.Translated by Charles Eolduan, pp. vi +85. New York 1904. From the Publishers. Benedicks, Carl. Recherches physiques et physico-chimiques sur Pacier ail carbone. pp. 219. ill. Uppsala 1904. From the Author. Getman, Frederick H. Laboratory exercises in physical chemistry. pp. viii + 241. New York 1904. From the Publishers. Girard, Charles. A.nalyse des matihres alimentaires, et recherche de leurs falsifications. pp. 871. ill. Paris 1904. From the Publisher Graebe, Carl. Graebe-Peier, Cassel, 20th September, 1903. pp. 138. ill. Genf 1903. From Dr, R. H.Aders Plimmer. 210 Hollernaq A. P. A laboratory manual of organic chemistry for beginners. An appendix to the author's text-book of orgAnic chemistry. Translated by A. Jamigson Walker. pp. 78. New York 1904. From the Publishers. Jones, Cbapman. The science and practice of photogritphy. Fourth edition. pp. 569. ill. London 1904. From the Author. Jouet, H. Index to the literature of thorium, 1817-1902. Smith-aonian Miscellaneous Collections. Vol. xliv. Washington 1904. From the Smithsonian Institution. Ky6to Imperial University. 3Xemoirs of the College of Science and Engineering. Vol. I, No. 1. 1903. From the University. Langworthy, C. F., and Austen, Peter 1'. The occurrence of aluminium in vegetable products, animal products, and natural waters.A contribution to the bibliography of the subject. pp. 168. New York 1904. From the Publishers. Leach, Albert E. Food inspection and analysis. For the use of public analysts, health officers, sanitary chemists, and food economists. pp. xiv+787. ill. New York 1904. From the Publishers. Lippmann, Edmund 0. von. Die Chemie der Zuckerarten. 3rd edition of Die Zuckerccrten zlnd ihre De&vnte. 2 vols. pp. 2003. Braunschweig 1904. From the Publishers. Liversidge, A. Tables for qualitative chemical analysis. pp. 126. London 1904. From the Author. Manchester, Rivers Department. Annual Report, year ending March 30th, 1904. pp. 44. From the Corporation. Morse, Irving H. Calculations used in cane-sugar factories.A practical system of chemical control for Louisiana sugar-houses and other cane-producing countries. pp. viii + 75. New York 1904. From the Publishers. Riggs, Louis Warner. Elementary manual for the chemical Iabora- tory. pp. 138. New York 1904. From the Publishers. Royal Society of London. Record. Second edition, 1901. pp. 427. From the Society. Schmidt, G. C. Die Kathodenstrahlen. pp. 120. ill. Braun-schweig 1904. From tlie Publishers. Stoddart, F. Wallis. On the best method of sewage disposal for small communities. pp. 32. ill. Bristol 1904. From the Author. Sutton, Francis. Systematic handbook of volumetric analysis. Ninth edition. pp. xii+617. ill. London 1904. From the Author. Treadwell, F. P. Analytical chemistry. Volume 11.Quantitative analysis. Translated by William T. Hall. pp. 654. ill. New York 1904. From the Publishers. United States, Philippine Commission. -Report of the Superinteud- 211 ent of Government Laboratories in the Philippine Islands, for the year ended September lst, 1903. pp. 278. ill. 1004. From the Commission. University of California. Report of work of the Agricultural Experiment Station of the University of California. 1901 -1903. pp. 222. ill. From the University. Wachter, Wilhelm. Das Feuer in der Natur, im Kultus und Mythua, im Volkerleben. pp. 166. Leipzig 1904. From the Publisher. Wallace, Robert.. Argentine shows and live stock. pp. 154. ill. Edinburgh 1904. From the Author. Wassermsm, A. Immune sera : haemolgsins, cytotoxins, and pre- cipitins. Authorised translation by Charles Belduan.pp. 77. ill. New York 1904. From the Publishers. West Indies, Imperial Department of Agriculture. Sugar-cane experiments in the Leeward Islands. Part I. Experiments with vai ieties of sugar-cane, with appendices on the chemical selection of sugar-citne. Pnrt IT. Manurial experiments. pp. 68, 115. Barbados 1904. From the Dzpartment. Bischof, Carl. Die feuerfesten Tone, Deren Vorkommen, Zusam- menst. tzung, Untersuchung, Behandlung und Andwendung. Mit Beriicksichtigung der feuerfesten Materialien uberhaupt. Dritte Auflage von Hermann Kaul. pp. viii+446. ill. Leipzig 1904. Borehers, W. Die Beziehungen z wischen Aquivalentvolumen und Atomgewicht. Ein Beitrag zur Festigung und Vervollstiindigung des periodischen Systems der Elemente.pp. 17. Halle 1904. Collin, Eugene, et Perrot, Em, Les rksidus industriels de la fabrica- tion des huiles et essences utilishs par l’agriculture comme aliments et comme engrais. pp. 299. ill. Paris 1904. Eder, J. M., and Valenta, E. Beitrage zur Photochemie und Spectralanalyse. pp. 868. ill. Wien 1904. Hammsrsten, Olof. Lehrbuch der physiologischen Chemie. Fiinfte Aufiage. pp. 7 15. Wiesbaden 1904. Hime, Henry W. L. Gunpowder and ammunition, their origin and progress. pp. 256. London 1904. Jahrbucl der :Radioaktivitat und Elektronik. Herausgegeben von Johannes Stark. Band I, 1904. Kekul6, August. Uber die Konstitution un? die Metamorphosen der chemischen Verbindungen und uber die chemische Natur des Kohlenstoffs.Untersuchungen uber aromatische Verbindungen. .Herausgegeben von A. Ladenburg. (Ostwald's KZccssiker, No. 145.) Leipzig 1004. Kepler, Johannes. Dioptrik oder Schilderung der Folqen, die sich aus der unlangst gemachten Erfinduog der Fernrohre fur das Sehen und die sichtbaren Gegenstande ergeben, 16 11. Herausgegeben von Ferdinand Plehn. (Ostwald's Klassiker, No. 144.) Leipzig 1904. Konig, J. Chemie der menschlichen Nahrnngs- und Genussmittel. Band 11. Die menschlichen Nahrungs- und Gmussmitt el, ihre Herstel- lung, Zusammensetzung und Beschaffenheit, nebst einem Abriss uber die Ernahrungslehre. Vierte Adage. pp. xxv + 1557. ill. Berlin 1904. Lassar-Cohn. Allgemeine Gesicht spunkte fiir organisch-cbemisches Arbeiten.pp. 79. Hamburg 1904. Moller, Joh. Die elektrochemische Reduktion der Nitroderivate organischer Verbindungen in experimenteller und theoretischer Beziehung. pp. 113 + vii. Halle 1904. Ostwald, Wilhelm, Abhandlungen und Vortriige, 1887-1903. pp. x + 468. Leipzig 1904. Sturm, C. Abhandlung iiber die Auflosung der numerischen Gleichungen, 1835. Herausgegeben von Alfred Loewy. (Ostwald's Kkcssiker, No. 143.) Leipzig 1904. Walden, P. Wilhelm Ostwitld. Werner, A. Lehrbuch der pp. 120. ill. Stereochemie. Leipzig 1904. pp. xvi + 474. ill. Jena 1904. III. Pamphlets. Bigelow, W. D. Foods and food control. I. Legislation during the year ended July 1, 1903. (U.S. Dept. of Agric. Bureau of Chemistry Bulletin, No. 83, Part I.) 1904. British Guiana. Report by Professor Harrison on the results of experimerits with varieties of canes carried on on sugar plant ations in the colony.pp. 8. Demerara, 1904. Cain, John Cannell. The constitution of the ammonium compounds. (From the Mem. Manchester Phil. Soc., 48, 1904.) Cape of Good Hope. Report of the Senior Analyst for the year 1903. pp. 72. 1904. Davis, Charles B. Steely malt in modern brewing and the filter press. (From the Z'vansactions of the American Brewing Institute, 2, 1904.) R. CLAY ANDSONS, LTD., BREAD 31'. HIIL, E.C., AND BUNOAY, SUFFOLK.
ISSN:0369-8718
DOI:10.1039/PL9042000173
出版商:RSC
年代:1904
数据来源: RSC
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