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Proceedings of the Chemical Society, Vol. 19, No. 270 |
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Proceedings of the Chemical Society, London,
Volume 19,
Issue 270,
1903,
Page 199-234
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摘要:
Issued 14/ 11/03 PROCEEDINGS OF THE CHEMICAL SOCIETY. VOl. 19. No.270. Extraordinary General Meeting, July 2nd, 1903. Professor TILDEN, F.R.S., President, in the chair. The PRESIDENTstated that this meeting had been summoned to con-sider the following changes in the Bye-laws which had been proposed at one meeting of the Council, and considered and approved at a subsequent meeting. It was proposed by the Treasurer, Dr. H. T. BROWN,and seconded by Professor THOBPE, (‘That Bye-law I., page 13, lines 3 and 4,be altered by deleting the words “ one year.” The Bye-law at present reads :-<c . . . .; and he shall “be entitled, so long as his annual subscription be not one “year in arrear, to one copy of the annual publications of the “Society.. . . .” And that the Circulars in the Appendix be altered as follows :-In Appendix, No. 2, ‘I Letter notifying the Election of a Member,” 5th and 6th lines, p. 26, delete the words “the Assistant 4‘Secretary.” After the words before admission,* ” add the words “Payment should be made direct to the Society’s Bankers ( ) either by Cheque or Post Office Order crossed a/c ‘Chemical Society.’ Your remittance should be accompanied by the enclosed Form with your Name and Address filled in.” 200 In No. 3, ‘‘Annual Circular Letter of Treasurer,” delete from ‘I If paid ” to end of circular, and substitute the same words as added in No. 2. In No. 4,‘‘Annual Circular Letter of the Treasurer to Fellows who are two years in arrear of their Subscriptions,” delete from ‘I Payments should be made ” to end of circular, and substitute the same words as added in No, 2.The motion having been submitted to the meeting was declared by .the President to have been carried unanimously. The following are abstracts of papers received during the vacation, and published or passed for publication in the Transactions. 112. The composition of so-called elzeomargaric acid.” By T. Kametaka. Maquenne having recently shown that the composition of Cloez’s elaeomargaric acid is more closely expressed by C,,H,,O, than by the formula C,7H,,0, adopted by Cloez, the author adduces evidence from his own work on the oil of Elceoeocca vernicia to show that the true formula for the acid is ClsH3,O2.This proof depends on the formation of the bromine additive product, C,,H,,O,Br,, and on the result of the oxidation of the asid by permanganate, the product con- sisting of sativic acid, ClsH32(OH)402,and a small amount of another hydroxy-acid, apparently dihydroxystearic acid. Titrations with standard caustic alkali and baryta solutions give, as a mean result, 280.5 for the molecular weight of el~eomargaric acid, whilst C1sH3202 requires 280. 113. Phosphoric amidines.” By R. M. Caven. Phenyl-p-tolylphosphoric amidine, C6H5NH*PO:N*C6H,CH,, which is formed as a by-product in preparing anilino-p-toluidinophosphoryl chloride (Fmns., 1902, 81,1369), is identical with a compound obtained in the preparation of ptoluidinoanilinophosphoryl chloride, and which should accordingly have the formula C,H,( CH,)-NH*PO:N*C,H,.This identity is not to be attributed to the mobility of a hydrogen atom (compare von Pecbmann, Ber., 1895, 28,869 and 2362), but to the fact that the disubstituted phosphoryl chloride, in whichever way pre-pared, is one and the same substance, and that the derived amidine, whether a single substance or a mixture, results from the withdrawal of hydrogen chloride by the action of the substituting base. Diphenylphosphoric amidine, C6H5NH*PO:NCeH5, and di-ptolyl-phosphoric amidine were prepared from dianilino- and di-p-tolnidino- phosphoryl chloride8 respectively. The formation of such amidines from the diarylaminophosphoryl chlorides by the elimination of hydrogen chloride is facilitated by the agency of basic oxides such as those of silver, mercury, and magnesium.114. 6‘ The mechanism of combustion.” By H. E. Armstrong. Assumicg that chemical interchange and electrolysis are inter- changeable equivalent terms, the author regards oxidation as an indirect process, inasmuch as the oxygen used is only indirectly in- corporated with the oxidised matter ;the oxidation takes place in a circuit composed of the oxidisable substance, conducting water and oxygen, the last of these acting as the depolariser. The results obtained by Bone and -Wheeler are discussed in the light of this hypothesis. It is contended that in the case of methane, for example, oxygen is introduced atom by atom and that a substance such as carbon monoxide is a secondary product, not a direct product of oxidation nor of preferential oxidation of the carbon.115. The constituents of the volatile oil of the bark of Cinnamomum pedntinervium of Fiji.” By E. Goulding. The bark of Cinnamomum pedatinerviuna, a tree indigenous to Fiji, on distillation with steam, yields nearly 1 per cent. of a volatile oil which is almost colourless when first distilled, but gradually assumes a Fellowish-brown colour. This oil has a sweet, aromatic odour, a pungent, spicy taste, sp. gr. 0.964 at 15O/15’, [a]. -4.96’ and nD 1,4963. Its chief constituents are : (i) a teypene; ClOHI6, which has a sp. gr. 0.8659 at 15’/15O, [aID -17.72”, and yields an uncrystal- lisable dibronaide, C,,H,,Br, ; (ii) linalool ; (iii) safrole ; (iv) eugenol ; and probably (v) eugenol methyl ether.The quantitative composition of the oil is approximately as follows: terpene, 15-20 per cent.; alcohols, 30 per cent, ;esters, 1.5 per cent. ;safrole, 40-50 per cent.; eugenol, 1 per cent. ;and 3 per cent. of eugenol methyl ether (2). 116. Condensation of phenols with esters of unsaturated acids. Part VIII.” By S. Ruhemann. The compounds formed from a-naphthol and ethyl chlorofumarate must be formulated as derivatives of a-naphthaketocoumaran (compare 202 Trans., 1902, 81, 419), because although guaiacol reacts with ethyl chlorofumarate to yield only ethylguaiacoloxyfumarate,yet its isomeride, the monomethyl ether of resorcinol, condenses with the ester to furnish ethyl em-methoxyphenoxyfumarate and an orange-coloured keto-coumaran derivative, which is called dimethoxybisbenxaronyl.The latter derivative has properties similar to those recorded for bis-naphtharonyl ;both compounds are reduced to colourless ketocoumaran derivatives by zinc dust and acetic acid, these reduction products being readily oxidised and converted in to red substances. Ethyl phenylpropiolate, when condensed with the monomethyl ether of resorcinol, yields ethyl m-methoxy-P-phenoxycinnamate, the free acid of which loses carbon dioxide on heating and furnishes m-methoxy- phenoxystyrene. Tho diethyl ether of phloroglucinol reacts with ethyl chlorofumarate to form ethyl diethoxyphenoxyfumarate, and with ethyl phenyl- proyiolate to yield ethyl diethoxyphenoxycinnamate. 117."Action of phosphorus trichloride on the aromatic ethers of glycerol. Part 11." By D. B. Boyd. The study of the action of phosphorus trichloride on glycerol diary1 ethers has been extended (Trans., 1901, 79, 1221), and the following substances have been prepared : s-glycerol di-o-tolyl ether (P-hydroxy-ay-di-o-tolyloxypropane)boiling at 226' under 13 mm. pressure and melting at 36-37'' ; the corresponding meta-compound boiling at 232' (1 3 mm.) ;bisdi-o-toEyloxyisopropy1 phosphite and its para-isomeride, which melt at 118-1 19' and 81-82' respectively ; di-o- and di-m-tolyloxyisopropylphosphorousacids melting respectively at 88-49' and 85-87', and certain of their metallic salts.118. '' Attempts to prepare isomeric quaternary salts." By M. Barrowcliff and I?. S. Kipping. In view of the probable existence of isomeric salts of the type R1>NR,R,R, (Trans., 1903, 83,873), the authors have investigated Rl some compounds of this class, including certain salts of the ethyl- propylpiperidinium base already studied by Miss C. de Brereton Evans (Trans.,1897, 71,522) ; but although in all cases one of the radicles consisted of an optically active group, no indication whatever of the existence of isomerides has been observed. Eth?jlp~.opyZpiperidirLizLmd-bromocam~iLorsuEyAonate, C,H,oNEtPr*SO,*CloHl,BrO, crystallises in needles melting at 211"; it is very readily soluble in 203 water and chloroform, sparingly so in ethyl acethte, and insoluble in ether and light petroleum Benzylmet~ylpi~ridiniumd-bi-ornocamphor-suZphonate, C,Hl,NMeBz*S0,*C10H14Br0,melts at 160' when anhydrous and generally resembles the preceding compound.Ethyl-piperidine d-bromocamp~or~phonate, C',H,,NEt,C,,H,,BrO *SO,H, crystallises in needles melting at 158'. These three salts, when repeatedly crystallised fractionally from various solvents under different conditions, did not yield dissimilar fractions. Molecular weight determinations made with ethylpropyl- piperidinium iodide seem to show that whereas in aqueous solution the salt is ionically dissociated in a normal manner, yet in chloroform solution it is associated, possibly Forming trimolecular complexes.119. Some salts of d-and I-a-phenylethylamines." By A. E. Hunter and I?. S. Kipping. The authors have investigated several salts of the d-and Z-com- ponents of dl-phenylethylamine in the hope of obtaining isomerides corresponding with those derived from hydrindamine, but without success. When the d-bromocamphorsulphonateof the dl-base is fractionally crystallised from water, it affords a salt which separates in prisms melting at 206-207', and having in aqueous solution a molecular rotation identical with that of the d-homo-acid, namely, [MID+ 271' ; this salt, however, is not partially racemic, as might be inferred from its optical propertieq but is the compound of the Lbase; the salt of the d-base was not isolated. Although the ion of the Lbase appears to be devoid of optical activity, the free base is distinctly laworotatory in aqueous alcoholic solution, its specific rotation being about [a], -25' ;this behaviour is similar to that of the d-and l-hydrindamines. The benxoyl derivative, prepared from I-a-phenylethylamine by the Schotten-Baumann method, melts at 120°, is optically inactive, and seems to be identical with that of the dl-base.1-a-Phenylethylamine d-ch~oroca~nphorsu~phonatemelts at about 198' and has in aqueous solution a molecular rotation practically identical with that of the d-chloro-acid, namely, [MI, + 1869 1-a- PhenyZethyZccmirze d-cawiphorsulphonate melts at 149-1 50° and is practically indistinguishable by polarimetric examination from the corresponding salt of the dl-base, both substances having a molecular rotation approximating very closely to that of the acid ; apparently the salt of the dl-base is not a definite partially racemic substance.120. 6L P-Bromocinnamic acids.” By J. J. Sudborough and K. J. Thompson. Small amounts of P-bromoallocinnamic acid (m. p. 159--160°) are obtained by the action of alkalis on cinnamic acid dibromide, but are not produced when the ethyl ester is used instead of the free acid di bromide. In aqueous solution, the products of the combination of hydrogen bromide and phenylpropiolic acids consist en tirelg of P-bromo- and /3-bromoccZZo-cinnamic acids ;the relative amounts of the two isomerides being but slightly affected by light, temperature, or concentration of the solvent.The nature of the combination is materially affected by the medium in which the hydrogen bromide is dissolved; when acetic acid is used, more of the P-bromo-acid and less of the P-bromoollo-acid are obtained than when saturated aqueous solutions are employed. With benzene and carbon disulphide, the chief product is a-bromo-cinnamic acid. Similar results have been met with in the combination of ethyl phenylpropiolate and hydrogen bromide. Under the influence of alkalis, P-bromocinnamic acid and its esters lose hydrogen bromide much more readily than the P-bromoccZEo-acid and its esters. Attempts have been made to prepare Michael’s isocinnamic acid in order to determine whether either the allo-.or the iso-acid could be resolved into optically active constituents by the aid of active bases. The experiments made on the reduction of the /3-bromoccZlo-acid indicate that the product, which consists of allocinnamic acid with a trace of ordinary cinnamic acid, does not contain the iso-acid. 121. ‘6 Bapour pressure of aqueous ammonia solutfon. Part 11.” By E. P. Perman. The partial pressures of the ammonia and water-vapour evolved by an aqueous ammonia solution have been found by aspirating a known volume of air through the solution and estimating the amounts of ammonia and water withdrawn. The experiments were made at temperatures ranging from 0’ to 60°, and the concentration of the solutions employed varied from 0 to 22.5 per cent.of ammonia. It was found that the sum of the partial pressures was equal to the total pressure determined by the statical method, and also that the relationship between the partial pressures and the concentration of the solution is that deduced by Duhem and others for binary mixtures of liquids. 2G5 122. (( Isomeric aminoamidines of the naphthalene series. (Fourth communication on anhydro-bases.)” By R. Meldola, J. V. Eyre, and J. H. Lane. The authors have succeeded in isolating the free base, ethenyltri- aminonaphthalene, obtained by the reduction of dinitro-a-aceto-naphthalide by tin and hydrochloric acid. The compound is character-ised by its tondency to form complex hydrates containing 9$, 3& or 1fr mols. of water. The acetate, C,,H,,N,,C2H,0,,H,0, oxdate, C,,Hl,N,,C2H204,2H20, and mercurichloride, C,,H,,N3,HC1,HgC1,,1 HH,O, have been prepared.The N-ethyl derivative of the acetyl derivative having the formula c16Hl$)N3,&H20has been obtained, and characterised by the forma- tion of its picrate, C,6HltON3,C6H2(N02)30H,H20,and aurichloride, C16H,,0N3,HAuCI,, 2H20. By eliminating the NH, group in the ethenyltriaminonaphthalene by the diazo-method, an ethenyldiaminonaphthalene (methylnaphth-imidazole) has been obtained, which differs from the only compound of this formula at present known (Prager, Ber., 1885, 18,2161). The isomerism of the aminoamidines has thus been proved to extend to the parent compounds, so that the cause of the isomerism is to be sought in the structure of the amidine ring.The following salts and derivatives have been prepared : hydrochloride, C12H,oN,,HCI,H,0, chromate, C,,H,,N2,H2Cr0,,2H20, and picrate. The base itself has the formula C,,H,,N,,H,O, and the water could not be expelled without decomposing the compound. The amidine ring apparently breaks down by the action of benzoyl chloride in presence of alkali with the formation of dibenzoyl-o-naphthylene-diarnine. The N-methyl derivative, an oily base, has a crystalline picrate C13H,,N,,C,H2(NO,),OH. The crystalline N-ethyl derivative, C14H14N2 is anhydrous and yields the following crystalline salts : chi.omate, and @crate, C,,H14~,,C6H,(N02),0H,H,0C14H14N2,H,Cr04, ; its aurichloride contains 2H,O and, when heated in the water-oven, becomes converted into the monohydrate.The platinichloride also yields hydratescontaining 4, 2, and 1 mols. of water. The N-ethyl derivative of the known ethenyldiaminonaphthalene (compare Otto Fischer, Ber., 1901,34,935) prepared for comparison nith its isomeride, is found to be resinous, but the chromccte, picrate, platinichloride, and aurichloride are well charac terised. The ethenyltriaminonaphthalene, obtained by the reduction of dinitro-a-acetonaphthalide by iron and hydrochloric acid (Markfeldt’s base) yields a crystalline oxalats with 4H20 and a mercurichloride, 206 C,,Hl1N3,2HC1,HgCI,,5H2O.Its benzoyl derivative has now been prepared by the Schotten-Baumann method (cornpare Trant3., 1900, 7’7, 1165).Ethenyltriaminonaphthalene (Meldola and Streatfeild’s base) is converted into its isomeride (Markfeldt’s) by further reduction with iron and hydrochloric acid, but reduction with sodium amalgam in the presence of acetic acid does not bring about this transformation. Reduction of dinitro-a-acetonaphthalide with zinc and hydrochloric acid gives the original (M. and S.) base. 123. Polythiosulphonic acids of p-diamines.” By A. G. areen and A.G.Perkin. The series of polythiosulphonic acids of p-diamines formerly prepared by one of the authors in collaboration with A. Meyenberg (compare Eng. Pat. Specifications, Nos. 21832, 98 ; 22460, 98 ; 22847, 98 ; 5039, 99 ; 18658, gy ; and 4792, O0) are well-crystallised compounds which, when oxidised together with primary amines and diamines, give rise to a series of black colouring matters possessing the characteristic properties of (‘sulphide ” colours.The present communication deals with the further characterisation of these polythiosulphonic acids, especially of the di-and tetra-thiosulphonic acids of p-phenylenediamine, C,H,(NH,),( S-SO,H), and C, (NH2),(S S03H)4, which are obtained by the oxidation of p-phenylenediamine in the presence of sodium thio- sulphate, using 2 or 4 molecular proportions of the latter with a corresponding quantity of the oxidising agent. Owing to the presence of the S203Hgroups in ortho-positions with respect to the amino-radicles, the p-phenylenediaminedithiosulphonic acid exhi bits several characteristic condensations.Thus, with nitrous Nacid it gives a stable bisdiazosulphide, C,H,(<h ; with organic anhydrides or with aldehydes, it gives anhydro-compounds. On boiling the di- or tetra-thiosulphonic acid with aqueous acids, sulphurous and sulphuric acids are eliminated, and yellow or red salts of sulphide bases are obtained. These bases, which appear to have the constitution C,H,(NR,),<: and :> C6(NH2)2<i9 are of dark colour, insoluble in water and other solvents, but dissolving in an aqueous solution of sodium sulphide, in which respect they resemble the ‘‘ sulphide ” colours ; they are reconverted into the respective polythio- sulphonic acids by prolonged treatment with sulphurous acid in the presence of air. When treated with zinc dust, the dithiosulphonic acid is reduced to the disulphydride C,H,(NH,),(SH),.207 124. ‘&The rotation of the menthyl esters of the isomeric chloro- benzoic acids.” By J. B. Cohen and S. H. C. Briggs. The authors have prepared the menthyl esters of the mono-and di-chlorobenzoic acids, and have compared their specific and molecular rotations. The following represenh the order of optical activity, beginning with the least active : 2 : 6 ;2 :3 ;ortho; 2 :5 ;2 :4 ; 3 :4; 3 :5 ; unsubstituted ; meta ; para. These results lead to the following conclusions : (1) the greatest effect (decrease) in the rotation of the unsubstituted menthyl ester is produced when the halogen enters the ortho-position with respect to the carboxyl group; the least, when the halogen is in the meta- and para-positions, which, singly, slightly increase the rotation, (2) The monohalogen derivatives accord with the rule laid down by Frankland and Wharton (Trans.,1896, 69, 1320, 1583), and confirmed by Guye and Babel (Abstr., 1899, ii, 719) and Tschugaeff (Abstr., 1903, ii, 2), and follow the order : ortho, unsubstituted, meta, para.(3) Two halogens attached to adjoining carbon atoms (2: 3 and 3 : 4) produce a greater effect than either singly. It might be expected that the rotations of the 2 : 3-and 2 : 5-estera would be approximately the same, inasmuch as the chlorine atoms in both isomerides occupy the ortho- and meta-positions with respect to the carboxyl group, but in reality the rotation of the 2 :3-ester is much lower, and that of the 2 :5-isorneride slightly higher than the value obtained for the ortho-compound.The low rotation of the 3 :4-and 3 :5-esters does not support the theory of the lever-arm (Frankland and Wharton, Zoc. cit.). 125. “The reaction between phosphorus and oxygen. Part I.” By E. J. Russell. A small quantity of water is necessary for the oxidation of phos- phorus, and the reaction proceeds most rapidly when that amount is present which is left after drying with sulphuric acid. In the presence of much water vapour, action is considerably retarded. The formation of ozone and hydrogen peroxide requires the presence of excess of water; these bodies are not direct products of the reaction between phosphorus and oxygen, Moderately dried phosphorus and oxygen react under all the pres- sures employed, and the phenomen:i of false equilibrium are not seen.The reaction may be divided into two stages : in the first, oxidation is slow and accompanied by a very feeble glow, the action being 208 apparently unimolecular ; the oxide formed is still under investigation. The second stage begins when the pressure falls below about 500 mm. ; oxidation is continuously accelerated until all the oxygen is absorbed. The luminosity is very marked, and phosphorus pentoxide is formed. No simple expression could be found connecting the velocity of oxida-tion with the pressure of oxygen. When an inert gas, such as nitrogen, is present, the phenomena are substantially the same, but the acceleration of the second period ceases after a time and a retardation sets in.This variation is, how- ever, explained on a purely mechanical hypothesis. When phosphorus oxidises in moist oxygen, the reaction differs from that taking place in dry oxygen in the following respects : (a). It does not begin until the pressure of oxygen is less than about 500 mm. ; when it does take place it is slower, and is much retarded during the earlier part of the reaction. The retardation is explained as being due to a protective film formed by the water on the phosphorus. (b). Ozone and hydrogen peroxide are produced, and, in presence of nitrogen, these substances are accompanied by ammonium nitrite and nitrate.None of the theories at present held completely accounts for these observations. If smaller quantities of water are present (4or 5 mm. pressure in- stead of 16 or 20 mm.), the velocity curve does not differ greatly from that obtained in the absence of water. And the difference observed when the higher quantity of water is present can readily be explained as being due to the protective layer of this liquid. There is no reason to suppose that the primary reaction between the phosphorus and oxygen differs in the two cases. 126. ''Action of hydrogen peroxide on carbohydrates in the presence of ferrous sulphate. IV." By R. S. Morrell and J. M.Crofts. The substances formed by adding hydrogen peroxide solutions of arabinose and rhamnose in the presence of ferrous sulphate yielded osazones with phenylhydrazine acetate, and it was therefore considered that arahinose and rhamnose had been oxidised to the corresponding osones (Trans., 1899, '75, 786, and 1900,77,1219).Aqueous solutions of these two osones have been found to react at the ordinary tempera- ture with p-bromophenylhydrazine, giving rise to osazones. The action of larger quantities of hydrogen peroxide on glucose and fructose has been investigated, and the metallic salts of glyoxylic, glycollic, and trihydroxybutyric acids have been obtained, The formation of gl ycok acid from glucose is peculiar, and is not easily accounted for on the assumption that the sugar molecule is transformed into an osone before a disruption of the carbon chain takes place. 2c9 127.‘(Ethyl benzylideneanilineacetoacetate.” By R. S. Morrell and A. E. Bellars. The authors find that the action of benzylidenenniline on ethyl acetoacetate gives rise to ethyl benzylideneanilineacetoacetate, which melts between 78O and 80’ after recrystallisation from benzene and carbon tetrachloride. The addition of piperidine or minute quantities of sodium ethoxide does not cause any change in the melting point of the recrystallised addition product (compare Schiff, Ber., 1898, 31, 207 ;Rabe, ibid., 1902, 35, 3950 ; Francis, ibid., 1902, 35, 3949): but the solvents used in the recrystallisation must be pwe, otherwise it is impossible to obt,ain the ethyl benzylideneanilineacetoacetate with a constant melting point.The addition of small quantities of sodium ethoxide to a mixture of benzylideneaniline and ethyl acetoacetate causes the formation of a mixture of &-and &-forms of ethyl benzylidenediacetoacetate (Rabe, AnnoZen, 1900, 3 13, 176). The molecular weight of the ethyl benzylideneanilineacetoacetate in benzene or carbon tetrachloride solution decreases as the solution becomes more dilute, and also on heating or when it is kept for some time. 128. ‘6 Studies on enzyme action. I. The correlation of the stereo- isomeric U-and P-glucosides with the corresponding glncosea. ” By E. F. Armstrong. The stereoisomeric a-and P-alkyl glucoses have been converted, by means of enzymes, into the corresponding glucosides.It is thus shown that glucose has a lactonic structure, and consists, in solution, of a mixture of two stereoisomeric lactones. The changes in rotatory power which dissolved glucose undergoes involves the passage of one or other form of the lactone into a mixture of the two. 129. ‘6 A dynamioal study of the Friedel-Crafts reaction.” By B. D. Steele. In order to determine, if possiblo, the mechanism of the Friedel-Crafts reaction, the synthesis of phenyl tolyl ketone from toluene and benzoyl chloride in presence of aluminium or ferric chloride, and that of phenyltolylmethane from toluene and benzyl chloride in presence of the same condensing agents have been studied dynamically. The course of the reaction in each case was followed by passing a rapid 210 current of hydrogen through the reaction mixture, and titrating the hydrochloric acid thus carried over, The following conclusions have been deduced : (I) In the synthesis of a ketone from a hydrocarbon and an acid chloride in the presence of aluminium chloride, the explanation sug- gested by Perrier (Bey., 1900, 33,815) and by Boeseken (Rec.tTav. chim., 1900, 19,19; 1901, 20, 102) seems to be quite justifiable, providing that the aluminium chloride is not present in excess. (2) In the presence of an excess of the condensing agents, the reaction, instead of being unimolecular, becomes bimolecular, and is best explained by assuming that the reagents are two intermediate compounds, each containing aluminium chloride.(3) In the presence of ferric chloride, the reaction is also bimolecular, and is best explained on the foregoing assumption. (4) The synthesis of phenyltolylmethane from toluene and benzyl chloride, in the presence of either aluminium or ferric chloride, is a unimolecular reaction, due to the interaction of the toluene and a compound of the organic and metallic chlorides. Thursday, November 5th, 1903. Professor W. A. TILDEN,D.Sc., F.R.S., President, in the Chair. Messrs C, N. Bennett, G. Barger, H. Cough, W. Mann, C. D. Bibby, and S. H. Woodhouse were formally admitted Fellows of the Society. Certificates were read for the first time in favour of Messrs : Robert Duncombe Abell, Ph. D., D.Sc., Sandbach, Cheshire. Percy Appleyard, Albany, Western Australia.Edward F. Armstong, Ph.D., 55, Granville Park, Lewisham, S.E. Herbert Henry Ashdown, 3, Genesta Road, Plumstead. Herbert Moore Attwell, Limpley Stoke, Bath. William C. Badcock, B. A., The Grammar School, Crediton, Devon. Harold J. Bailey, 40, The Avenue, Pontypridd, South Wales. Thomas Vipond Barker, Exeter College, Oxford. Charles Marsh Beadnell, H.M.S. Barracouta, Capetown. William Beam, M.A., M.D., Pension Sima,Cairo, Egypt. Harold Goodenough Bayly, ‘‘ Moa tside,” Bedford. Henry James Wheeler Bliss, Balliol College, Oxford. 211 Nicholas John Blumaa, 10, Amersham Road, New Cross, S.E. Paul Briihl, Engineering College, Sibpur, near Citlcutta. Erasmus Robert Bug& 327, Grove Green Road, Leytonstone. William Clacher, Bryant wood, Auckland Road, Ilford.William Thomas Daeks, High Street, Shanklin, I.W. Henry Russell Ellis, 177, Warwick Road, W. Charles E. Fawsitt, Ph.D., B.Sc., 9, Foremount Terrace, Glasgow. John A. N Friend, M.Sc., 2, Francis Road, Watford, Herts. Ernest A. Gardiner, B.A., Bretherton, near Preston, Lancs. Frank B. Gatehouse, 56, Windmill Street, Gravosend, Kent. Frank B. Grundy, Red L9dge, King’s Road, Richmond, S.W. John T. Hall, West View, Stanwell, Staines. Harold M. Heasman, 1, Cdisle Road, Finsbury Park, N. Arthur V. Hendrickson, Gas Works, Lower Sydenham, S.E. John G. Howarth, “ Dmes Dyke,” Capstone Road, Bournemouth. Herbert Hymans, 13, Trinity Square, E.C. Edward Charles Ibbotson, 3, Ashgate Road, Sheffield. William H.Jackson, 73, Church Street, West Hartlepool. Thomas Oliver Kent, 89, Loughboro’ Park, Brixton, S.W. John J. Kielty, 71, Cairo Road, Walthamstow. Harley F. Knight, 64, Amhurst Park, Stamford Hill, N. John Laing, Everlie, Skelmorlie, N.B. Francis E. E. Lamplough, B. A., Trinity College, Cambridge. Harold Duff Leadbetter, 95, Cape1 Road, Forest Gate, E. Gervnise Le BAS,B.Sc., Baymont House, St. Aubins, Jersey. David B. Macdonald, 18, Kim berley Road, Leicester. Frederick W. McMahon, 61, Brockley Rise, Forest Hill, S.E. Ernest W. Mann, Willow Avenue, Edgbaston, Birmingham. GJrdon W. Monier-Williams, B A., The Lsmmas, Esher, Surrey. Urban 0. S. Nairne, 7, Hawthorne Terrace, Barking, Essex. James Victor Nevin, Bristol Dispensary, Bristol. Henry George Pike, Downton, Salisbury, Wilts.George Horace G. Plymen, 2, Melton Road, Leicester. William Branch Pollard, B.A., 68, Finnart Street, Greenock, N.B. Stiles W. G. Rich, Stanley Street, South Brisbme, Queensland. Harold E. Richardson, B.A., B.Sc., 63, Lansdowne RDad, Ilford. William David Rogers, 36, Grange Road, Smethwick. George Senter, Ph.D., B.Sc., 37, Rmalds Road, Highbury, N. Arthur Slator, Ph.D., M.Sc., The Priory, Burton-on-Trent. William V. Smith, B.A., 7, Grove Road, Ipswich Road, Norwich. A. W. Stewart, B.Sc., 18, Annfield Terrace, Partick Hill, Glasgow. Arthur Tighe, 20, Marlborough Place, St. John’s Wood, N.W. Arnold Turner, 316, Entwisle Road, Rochdale. William E. S. Turner, B.Sc., 52, Cheshire Road, Smethwick.212 Miles Walker-Pole, Braamfontein, Johannesburg. Carl F. R. Weiss, Ph.D., M.A., Victoria Park, Manchester. Fred Wright, Terry Street, Balmain, N.S.W. Certificates in favour of the following were authorised by the Council for presentation for ballot under Bye-law I. (3) : Thein Kin, Rangoon, Burma. Mata Prasad, Benares, India. P. W. Robertson’, Wellington, New Zealand. The PRESIDENTannounced that the Council had decided that a supplementary number of the Transactions should be issued on December 31st, and that after that date the Journal would be issued on the last day of each month instead of the first day of the month as hitherto, the first number for 1904 being issued on January 31st. The PRESIDENTthen reminded the Society of the announcement he had been permitted to make at the meeting on May 20th in reference to the bust of Dalton which was now before them, and read the following letter from Professor Thorpe.GOVERNMENTLABORATORY, LONDON,W,C. October, 1903. DEARMR.PRESIDENT, Although the walls of the Society’s apartments are adorned with busts, medallions and other mementoes of eminent chemists, there is among them no memorial of one of the most illustrious of all chemists-John Dalton. As a fellow-townsman of Dalton, may I be permitted, in grateful remembrance of the fact that my early education was promoted by a studentship founded in his memory and associated with his name, to laupply, in some small measure, the lack of such a memorial, and to ask that the CounciI will do me the honour to accept the bronze bust which accompanies this letter ‘1 As you are aware, this month one hundred years ago SBW the promulgation of Dalton’s great generalisation.There is, therefore, I venture to hope, a special fitness in preferring my request at this particular time. The bronze is the work of Miss Levick, who is already favourably known to the Society by her reproduction of the bust of Davy in their possession. Of the artistic merits of her present work others must be the judge, but I may be permitted here to express my indebtedness to 213 her for the skill and conscientious care with which she has striven to make a faithful and adequate presentment of the grand old philosopher.She has been greatly assisted by the kindness and co-operation of many friends to whom my acknowledgments are due. Practically all the available material has been placed at her disposal- the copy of the well-known Chantrey bust in the possession of the Literary and Philosophical Society of Manchester ; the Ciwdwell bust belonging to Owens College ; a beautiful but little known steel engraving by Stephenson, given to me by my friend Dr. Blackley ; the portrait in the possession of the Royal Society; the precious daguerreotype formerly in the possession of Daltou’s friend and pupil the late Mr. John Dale, and now the property of the Society; together with a number of other drawings and engravings. I am gratified to know that those who are competent to form an opinion have expressed the conviction that Miss Levick has made admirable iise of her ample material, and that she has succeeded not; only in reproducing the lineaments of the great chemist, but in infusing into them a conception of the simplicity, dignity and! grandeur of his character.I am, Dear Mr. President, Faithfully yours, T.E.THORPE. The Council had that afternoon passed a resolution tendering to- Dr. Thorpe an expression o€ most cordial thanks for his generous and interesting gift. Of the following papers, those marked were read : *130. “The reduction of hydrazoic acid.” By W.T. Cooke. Apart from Peratoner and Oddo’s observation (Gazzettcc, 1895, 25, 2) that ammonia is formed at the cathode when hydrazoic acid is electrolysed, the behsviour of hydrazoic acid when subjected to reducing agents does not appear to have been studied, Considering the acid as a cyclic compound having the formula NH<& the first step in its reduction should lead to the formation of the NHhydride, NH<kH, but the existence of this hypothetical compound seems doubtful in view of the ease with which nitrogen hydrides pass into ammonia.On the other hand, boron, which has even less affinity 214 for hydrogen than nitrogen, forms the corresponding hydride, B3H3 (Ramsay and Hatfield, Proc., 1901,17, 152), so that N,H, may possibly exist as a gas with feebly basic properties. Further reduction would, however, result in a breaking up of the ring, with the formation of ammonia, and possibly hydrazine, as an intermediate product.These substances were actually obtained when the following reducing agents were tried : sodium amalgam, zinc and either hydrochloric or sulphuric acid, sodium polysulphide, and ferrous hydroxide. Ammonia was the chief product, and the hydrazine, which was generally present in small quantities, was obtained in appreciable amount only in those experiments where it was removed from solution in the form of an insoluble compound during the reaction. It may, however, be formed at first in accordance with the equation NH*N,+ 3H2=NH,+N2H,, and then at once reduced, for trial reduction experiments, in which hydrazine sulphate was used instead of hydr-azoic acid, showed that some ammonia was formed.The hydrazoic acid was made by the method devised by Wislicenus (Bey., 1892, 25, 2084), and was employed in approximately decinormal solution. The products of reduction were separated from the mixture by dis- tillation from an alkaline solution, the distilling flask being provided with a ''Kjeldahl" bulb ;in most cases, the distillates, when acidi- fied with hydrochloric acid and concentrated, showed a slight reducing action towards ammoniacal silver nitrate, Fehling's solution, &c. ; the residues in the distilling flasks also produced the same effect, This result might be anticipated since hydrazine hydrate is less volatile in steam than ammonia. The latter substance was recognised by its odour, alkalinity, reaction with Nessler's reagent, and the analyses of its platinichloride.In reducing with sodium amalgam, the solid reagent was slowly added to separate quantities each consisting of 50 to 100 C.C. of acid, so as to maintain a slight effervescence. After about a week, the liquid was decanted from the mercury and distilled. Reduction proceeded more quickly in acid solution, but the hydrazoic acid was easily lost. The addition of sodiurn amalgam to freshly precipitated silver hydrazoato, which had been carefully washed until free from acid, and suspended in water, caused the separation of silver, which partly went into solution in the colloidal condition, giving the liquid a dark brown colour. The hydrazoic acid readily attacked zinc, and when the effervescence had subsided, sulphuric, or occasionally hydrochloric, acid was gradually added in small quantities.In the case of sulphuric acid, a granular deposit of the double salt, (N,H4)2~K2S04,ZnS04(Bey., 1893, 26, 410), was formed on allowing the reaction to continue for at least a week. 215 A solution of this salt, which is fairly soluble in hot water, easily reduces an acid solution of gold chloride. The precipitate of cadmium sulphide obtained on mixing solutions of cadmium hydrazoate and sodium polysulphide was collected after a few days, when the filtrate was found to contain a small quantity of ammonia. An alkaline solution of sodium hydrazonte was used in the case of ferrous hydroxide, and the reduction was carried on at the boiling temperature in a current of hydrogen, the ammonia evolved being collected in dilute acid.The mixture in the flask was distilled while still alkaline, and again when acidified with sulphuric acid, the latter operation being performed in order to recover the unused hydrazoic acid. Similar experiments were also made on the reduction of hydr-aaine sulphate with zinc or sodium amalgam; in both instances, a small amount of ammonia was formed. In the case of zinc and sulphuric acid, the formation of an appreciable amount of hydrogen sulphide was noticed at the beginning of the reduction. These results show that it is possible by the use of reducing agents to split the hydrazoic ring, and that there is certainly no tendency for the ring to become saturated by the addition of two atoms of hydrogen. "131.Preliminary note on the viscosity of liquid mixtures." By A. E. Dunstan and W. H. C. Jemmett. Three typical liquid mixtures have been used in this research, namely: (1) ethyl acetate and benzene; (2) benzene and ethyl alcohol; (3) ethyl alcohol and water. The apparatus used was of Ostwald's pattern; the viscometer was immersed in a bath, which was kept at 25' by means of a thermostat, and was stirred by a current of carbon dioxide. In the first mixture, which consisted of a pair of non-associative unimolecular IiquidP, the viscosity was an additive property, and an almost straight line curve was obtained having a slight concavity, Neither liquid has much effect on the other; the concavity probably indicates slight association.A similar result mas also obtained in the case of a mixture of benzene and carbon disulphide. In the second mixture, where only the alcohol was associative, a minimum point was reached when about 6 per cent. of alcohol was present ; the remaining part of the curve was normal. This minimum point is probably due to further association of alcohol molecules. It has been shown in freezing point determinations that alcohol in benzene gives abnormally high results, and Piokering has recognised a 216 break in the freezing point curve corresponding with 6 per cent. of alcohol. In the third case, both liquids are associative, and as the percentage of either constituent increased, there was a strongly marked rise of viscosity, which culminated in a maximum point, corresponding with 55.83 per cent.of :alcohol. At this point, the proportion of alcohol and water is very approximately 2 mols. water to 1 mol. alcohol. I. Traube (Be., 1886, 19,871) indicates maxima of a similar nature fcr this mixture at about 46-50 per cent. alcohol. Pickering has shown that in the freezing point curve of alcohol in water there is a break at 53 per cent. (Trans., 1893, 63,1012). In the case of the third mixt~ure, each substance possibly dissociates the associated molecules of the otber, thus giving rise to an increased number of active particles. Jones and Murray (Amer. Chent. J., 1903,30,193) have shown that such dissociation is the case for several associative bodies.This would explain the gradually increasing viscosity up to the maximum point corresponding with 2H,0-C2H,0H. The work is being extended to other liquid mixtures. *132. “A contribution to the study of the reactions of hydrogen peroxide.” By J. McLachlan. When solutions of hydrogen peroxide and potassium bichromate are mixed and boiled with sulphuric acid, the volume of oxygen evolved is not equal to twice the available oxygen of the bpdrogen peroxide. The available oxygen in the peroxide solution was estimated by iodometry, the object being to find the available oxygen in 0.56 C.C. of the sample of the peroxide, as this 6gure represents the volume of 0.0008 gram of oxygen.It is essential that the solution of the per- oxide should be dilute, and the sulphuric acid solution should not be stronger than 1 in 5. When stronger solutions of sulphuric acid are added to a ‘solution of potassium iodide, a considerable quantity of iodine is set free before the peroxide solution is added. The proximate cause of the ready production of iodine when stronger solutions of sulphuric acid are added to a solution of pure potassium iodide is believed to be dissolved oxygen, If, in such a solution con- taining some starch paste, the blue colour is destroyed by a drop or two OF a centinormal sodium thiosulphate solution, the coloration re- appears after a definite number of minutes. This regeneration of the blue colour, after its destruction by the thiosulphate solution, will go on for weeks, perhaps €or months or even years, until either the potassium iodide or the sulphuric acid has been used up.With hydro- chloric acid, the blue colour is reproduced in about one-seventh of the 217 time required for its reappearance when the equivalent amount OF sulphuric acid is employed, and hydriodic acid is almost as active. Tartaric acid is about as active as sulphuric acid, phosphoric acid not not quite so active, oxalic acid still less so, whilst with boric acid the time required for the development of the blue colour is about four days. The estimation of the available oxygen in a solution of peroxide of hydrogen by an acidified solution of potassium permanganate has been ‘found to be utterly untrustworthy.Estimations have been made of the available oxygen of manganese dioxide (1) in its original state, (2) after being boiled with a solii-tion of hydrogen peroxide, (3) after being boiled with a solution of hydrogen peroxide and sulphuric acid, the process employed being the oxalic acid method, in which a known weight of manganese dioxide, mixed with a known volume of a normal solution of oxalic acid, and excess of sulphuric acid (1 in 3) is heated until the whole of the dioxide is decomposed, and the excess of oxalic acid then estimated by a standard solution of potassium permanganate. The hydrogen per- oxide solution should be added only after the manganese dioxide and sulphuric acid are thoroughly mixed.The results indicate that (1) the manganese dioxide is not decom- posed by the hydrogen peroxide in accordance with the equation Mn02+H202=MnO+H20+0,, as in reality only a portion of the oxygen is evolved, (2) the presence of sulphuric acid is absolutely essential, for without it the foregoing reaction does not occur. DISCUSSION. Dr. DIVERSsaid that his own experience, as well as that of others, was that a mixture of puye potassium iodide and pure sulphuric acid if sufficiently dilute would remain colourless in the dark for hours in the presence of starch, even when exposed in an open vessel. In contact with the air, such a likely impurity as a very minute quantity of nitrous acid, although too small to cause an immediate effect, acted slowly as a carrier of oxygen and produced an intense coloration. Dr.MCLACHLAN,in reply, said that every effort was made to secure pure potassium iodide. Moreover, the action of traces of iodate or nitrous acid would not be an adequate explanation of the phenomena, unless such substances were normal constituents of the atmosphere as distinct from the air of a chemical laboratory. 218 *133. (6 The constitution of certain silicates.” By C. Simmonds. Silicates of lead, copper, iron, cobalt, and nickel are reduced when heated to redness in hydrogen, and as a rule a silicate containing x atoms of lead or copper yields x atoms of osygen. A few naturally occurring ferruginous silicates behave exceptionally under these con-ditions, some giving up only a portion of the corresponding oxygen, whilst others yield none.The reduced silicates are black powders which, except in the case of lead orthosilicate, do not appear to contain any notable amount of the reduced element in the metallic state. The formuh usually adopted do not furnish a simple interpreta- tion of the results obtained on reduction. In lead metasilicate, 0O:Si<o>Pb, for example, the two oxygen atoms connected with the metal are represented as occupying precisely similar positions in the molecule, and there is no apparent reason why only one should be removed by hydrogen. The formula of such a silicate ought, however, to indicate that at least one atom of oxygen (the displaceable one) is attached to each atom of lead, and also that this labile oxygen is linked to the metal in a manner differing from the mode of attachment of any other oxygen atom.The configuration which satisfies the prescribed conditions most 0-Tbcompletely is that having the grouping >Si< 0.0 The following conclusions have been deduced : (a)The silicon atoms are in direct combination with one another, and not joined by means of oxygen. (b) To the chain of silicon atoms thus formed the oxygen corresponding with (SiO,), is attached, giving rise to a mode of grouping denoted by the formula (c) The oxygen valencies still unappropriated are those by which the basic oxides (PbO, CuO, &c.) become attached to the silica complex, (d) The conception of silicate structure to which these deductions lead is that of a chain, either closed or open, of the following type : 219 0-R-Si< Isi<oO-O .10' -Si< 0-0 0-K" The two free silicon valencies would presumably unite, the silicate thus acquiring a closed chain or ring structure. Or they may possibly be connected by another molecular group-Al,O,, for instance-also giving rise to a ring. They might also conceivably be attached to any univalent atoms or groups, thus forming an open chain. Whether the above type of structure is the rule or the exception is at present uncertain, but that some diversity exists is shown by the behaviour of those ferruginous silicates (for example, staurolite, augite, and epidote) which are not reduced by hydrogen at a red heat.Possibly, a1though not necessarily, these differences may be due to the occurrence of an entirely different kind of structure. The natural silicates which have, so far, been found to undergo practically complete reduction (in the sense already explained) are dioptase, chrysocolla, garnieri te, connarite, chloropal, glauconite, cronstedtite, and thuringite. Ilvaite and stilpnomelane show consider- able, but not complete, reduction, this action being much less marked in the case of hypersthene. ~rscussro~. Mr. C. E. GROVESasked the author whether he had treated the reduced lead silicate with pure mercury and some acid, such as acetic acid, which did not act either on lead or mercury in order to ascertain whether the lead present in this reduced residue was in the metallic state.If it were not, and the author's formula for lead metasilicate, 0.P b for instance, (t)<o.b )%, be accepted, the reduced product must be a remarkable lead-silicon compound having the formula Si<O>Pb0 >..(1Mr. SIMBIONDS,in reply, said that he had experimented with mercury, but not with acetic acid, when testing the reduced silicate residues for metallic lead, and he hoped to deal with the matter more fully at some future date. The composition oE these residues, however, was a question quite distinct from the one discussed in the paper. 220 “134. ‘(The constitution of chrysophanic acid and of emodin.” ByH. A. D.Jowett and C. E. Potter. The authors discussed the evidence bearing on the positions of the substituting groups in the formulze for chrysophanic acid and emodin. They concluded that chrysophanic acid must be represented as 5 : 8-di-hydroxy-1-methylanthraquinone,as previously suggested by Hesse, and emodin as 2 : 5 : 8-or 3 :5 : 8-trihydroxy-1-methylanthraquinone. Emodin, on fusion with caustic alkali or on oxidation with perman- ganate, yielded no definite product. By the action of sodium and methyl iodide on emodin, only the mononzethyl ether, C,,H,,O, (m. p. 200’), mas formed; its dicccetyl com-pound melts at 157’. This emodin methyl ether appeared to differ from the naturally occurring product obtained by Perkin (T~CL’IZS.,1894, 65, 932).Attempts to synthesise the foregoing di- and tri-hydroxy- methylanthraquinones by the condensation of hydroxysalicylic acid with substituted 0-and nz-toluic acids, and also of 1-methylphtlialic anhydride with quinol, were unsuccessful. By the condensation of two molecules of hydroxy-p-toluic acid (CH, :OH = 1:2), three isomeric dihydroxydimethylanthraquinones were produced. 3 :5-Dilqdroxy-2 :6-dimethyla~~thrc~puinone,C1,HI2O4, which formed yellow leaflets not melting below 300°, yielded a diucetyl compound (m. p. 215’) and a vzonomethyl ether (m. p. 214-215’); the latter formed a monoctcetyl compound (m. p. 195-196’). 1 :5-Dihydroxy-2 :6-dinzethylanthi.ccquinone formed red needles (m. p. 224-225*), did not yield a methyl ether, and was insoluble in dilute ammonia.3 : 7-Bihydroxy-2 : 6-dinzethyZan~hruqiiinone formed orange-yellow needles (m. p. 232’) and readily dissolved in dilute ammonia to a red solution. 135. Conductivity of substances dissolved in certain liquefied gases. Preliminary notice.” By B. D. Steele and D. McIntosh. The authors have studied the behzviour of salt solutions in hydrogen chloride, bromide, iodide, sulphide, and pho sphide. In view of the known dissociation of salts when dissolved in hydro-gen fluoride, water, or liquefied ammonia gas, it was anticipated that the foregoing solvents mould all behave as ionising media. This anticipation has, however, been only partially realised. In hydrogen chloride solutior,, sodium chloride, potassium iodide, ferric chloride, and wdter do not conduct at all; potassium per- 221 mitaganate, sodium acetate, ammonium oxalate, and ammonium chloride diminish the resistance only very slightly, whilst potassium cyanide and several haloid salts of the amines yield highly conducting solutions. Trichloroacetic acid, sodium chloride, and water do not conduct in hydrogen bromide solution ; potassium iodide and potassium bromide conduct very slightly, whereas ammonium acetate, potassium cyanide, diethylammonium chloride, and tetramethylammonium chloride conduct well.Potassium cyanide, potassium iodide, phosphonium iodide, and water do not diminish the resistance of hydrogen iodide solution, whilst the haloid salts of the amines reduce it considerably.In hydrogen sulphide solution, hydrochloric acid, sulphuric acid, sodium chloride, and sodium sulphide do not conduct, ammonium chloride conducts only slightly, but ammonjum sulphide and the salts of the amines greatly diminish the resistance of the solvent. Phosphonium iodide, potassium iodide, sodium acetate, ammonium acetate, potassium cyanide, and the salts of the amines do not appre- ciably reduce the resistance of hydrogen phosphide. The salts of some of the ammonium bases greatly reduce the re-sistance of the first four solvents but do not diminish that of liquefied phosphine, and no salt has yet been found which will reduce to any appreciable extent the resistance of this solvent. It is at present impossible to state whether the cases of non-conduction are due to the insolubility of the salts or to solution unaccompanied by ionisation, but systematic quantitative experiments are being made on the foregoing solvents.136. ‘‘The behaviour of metallic oxides towards fused boric anhydride.” BY C. H. Burgess and A. Holt, jun. The authors have investigated the action of fused boric anhydride on many metallic oxides, and find that only a limited number dissolve. Lithium, sodium, potassium, cssium, and rubidium, as carbonates, readily dissolve in boric anhydride in all proportions up to saturation, giving clear glasses, and thallium behaves in the same way. With a very large amount of alkali, however, the glass becomes opaque. Calcium, strontium, barium, zinc, cadmium, magnesium, manganese, lead, and bismuth oxides are insoluble in small quantities, but, on gradually increasing the amount, dissolve to clear glasses; with a further addition of oxide, the mass again becomes opaque except in tbe cases of lead and bismuth, which yield pale yellow, very fusible glasses. 222 The oxide of mercury appears to be soluble, and those of antimony and arsenic slightly so.The oxides of aluminium, beryllium, zircon- ium, tin, cerium, thorium, niobium, and silicon are all quite insoluble. The oxides which colour the borax bead, namely, those of chromium, copper, molybdenum, uranium, iron, nickel, and cobalt, are all insoluble in the fused anhydride, the manganese oxides in this respect behaving exceptionally.The last series of oxides can, however, be dissolved in boric anhydride containing lithium, potassium, cesium, rubidium, and thallium, and the clear glasses obtained with large amounts of the coloured oxides were similar to the borax beads although the colours were sometimes modified, 137. Note on some reactions of vanadium tetrachloride.” By B. D. Steeie. In a series of experiments undertaken with the object of ascertaining whether vanadium tetrachloride might not find useful application as a chlorinating and condensing agent, it was found that on adding this reagent to benzene, a small quantity of a dark mauve solid was pre-cipitated, the yield of this substance was much increased by boiling the mixture, and 13 grams of dried solid were obtained from 25 grams of benzene and 15 grams of vanadium tetrachloride.Analyses showed that the atomic ratio of chlorine to vanadium varied from 3.08 to 2.73, whilst that between carbon and hydrogen was found to be one. The substance rapidly decreased in weight at the ordinary tempera- ture, aud rt freshly prepared sample, when heated at looo, evolved benzene and diminished by 50 per cent., the calculated percentage loss in weight for the compound VCl,(C,H,), being 49.7. In the above reaction, the vanadium tetrachloride was reduced to trichloride, and the liberated chlorine atom attacked the benzene molecule, evolving hydrogen chloride and giving rise to chlorobenzene or some other more highly chlorinated substitution products of benzene.Vanadium tetrachloride failed entirely to bring about chlorination in the case of nitrobenzene, but was used successfully in chlorinating benzene. When a rapid current of chlorine was passed into a mixture of 4.5 grauis of the chloride and 100 grams of benzene, hydrochloric acid mas copiously evolved, and sufficient heat was developed to raise the temperature of the solution nearly to its boiling point. On fraction-ating the product after removal of the vanadium compounds, a con-siderable quantity of substance boiling between 128’ and 132’ was obtained, which was identified as chlorobenzene. Crystals of hexa- 223 chlorobenzene melting at 155O were isolated from the small residue left in the distilling flask. Vanadium tetrachloride has no value as a condensing agent for use in the laboratory.Acetyl chloride and benzene, when condensed in its presence, gave only a very small yield of acetophenone, and other experiments in this direction led to equally unfavourable results. It was found that when the mauve compound, VCI,(C,H,)2,reacted with ether, heat was developed and a blue solution was produced which, on evaporation over sulphuric acid in a desiccator, yielded fine, blue, tabular crystals ;these could only be kept in the presence of an excess of ether and in a dry atmosphere. Satisfactory analyses of this compound could not be made on account of its instability. 138. 6‘ Studies on comparative cryoscopy. Part I. The fatty acids and their derivatives in phenol solution.” By P.W. Robertson. The rate of association of a given compound in any solvent is termed the “ assoce,” and the constant has been determined for the fatty acids and their derivatives in phenol solution. The assoce of the normal fatty acids alternately rises and falls as the series is ascended. If the even members are considered, this cooffi- cient reaches a minimum at hexoic acid and tlien rises rapidly. It is shown that the subsequent rise is probably due to a different kind of association, inasmuch as it is caused by the hydrocarbon portion of the molecule. The assoce is influenced both by the nature and by the position of a substituting group, and, generally, halogens, alkyl radicles of low molecular weight, and phenyl an? benzyl groiips have the same influ- ence. In all cases, when these radicles are introduced into the a-posi-tion with respect to the carboxyl group the assoce is reduced, but in the other non-contiguous positions they have little or no effect.Dicarboxylic acids associate more rapidly than the acids from which they are derived, but here again replacement of the a-hjdrogen atoms causes a reduction in the rate of association. a-Hydroxyl radicles increase the assoce, but substituted amino-groups tend to change its sign. It is noteworthy that the di- and tri-carboxylic acids and the a-amino-acids are exceedingly insoluble in phenol. The rates of association of the substituted acetic acids are intimately connected with their velocities of etherification.224 139. '( Vapour pressures of sulphuric acid solutions, Preliminary note.'' By B. C. Burt. Regnault's determinations of the vapour pressure of sulphuric acid solutions were carried out for concentrations varying from 24 to 84 per cent. at temperatures ranging from 5' to 30'. The vapour pres- sures are now being determined through wider limits of temperature and concentrat>ion by means of a modified form of the apparatus described by Innes (Tmlzs., 1902, 81, 683). The sulphuric acid solutions are heated in a large Jena glass Beck- mann tube, having a stout platinum wire sealed through the bottom, Regular ebullition is ensured by the use of small glass beads, and the tube is kept at a constant temperature by a copper jacket con-taining a suitable liquid boiling under a known pressure.The experimental tube is connected to a large reservoir, the pres- sure of which is kept constant by means of the regulator described by Innes. By suitably adjusting the pressure, which is observed to 0.1 mm. by a mercury manometer, the sulphuric acid can be boiled at any required temperature, this being read off by special normal Jena glass mercury thermometers (Goetze). The appended results indicate the accuracy of the method : Concentration of acid Vapour pressure in percentages. Temperature. in mm. 54-70 131' 637.1 54.70 131 637.2 62.07 131 497.9 62-07 131 497.7 62-07 131 497.7 72.88 132 200.2 72.88 132 200.3 79.57 132.5 70.2 79.57 132.5 70.2 Series B.Concentration of acid Vapour pressure iu percentages. Temperature. in mm. 72-88 157' 421.6 72-88 157 421.5 79.57 157 182-4 79.57 157 182.2 Chlorobenzene waq used as the boiling liquid in series A, and bromobenzene in series B. 225 140. LL Additive compounds of s-trinitrobenzene and alkylated arylamines.” By H. Hibbert and J. J. Sudborough. Mono-and di-alkylated naphthylamines form definite additive com- pounds with s-trinitrobenzene which closely resemble the similar products obtained from a-and P-naphthylamines and the same trinitro- compound. They are stable, red or purplish-black, crystalline sub- stances, and may be crystallised from all the ordinary solvents, including glacial acetic acid, without being resolved into their com- ponents, but are readily decomposed by hot dilute mineral acids.Molecular weight determinations in dilute benzene solution indicate that the dissolved compounds are almost completely resolved into their components. Most of the monoalkylated derivatives, like the compounds from a-and P-naphthylamines, may be acetylated, whereas the additive compounds from the tertiary bases may be boiled with acetic anhydride for hours without undergoing change. A benzoyl derivative has been obtained by the action of benzoyl chloride and alkali hydroxides on a-naphthylamine trinitrobenzene ; it melts at 131-132’ and is identical with the compound formed by the union of benzo-a-naphthalide and s-trinitrobenzene. Ethyl-a-naphthglamine s-trinityobenxene melts at 153*5--154’, and the corresponding diethyl compound at 95-95.5’.DimetiLyl-a-naplit~yZ-amiiw s-trinitrobenzene melts at 105-106’, and ethyl-P-naphthylamine s-trinitrobenzene at 106’, ethylaceto-P-na~~thalides-trinitrobenxene and diethyl-P-nap?&thyZamines-trinityobenxenc melt at 77-78’ and 116O respectively. Mono-and di-alkylated anilines also combine with s-trinitrobenzene, but the products are extremely unstable, and when crystallised from any of the ordinary solvents, or when exposed to the air at the ordinary temperature, are readily decomposed into their components. 141. ‘‘ Interaction between chloric and hydriodic acids.” By 3. McCrae. The action of chloric acid on bydriodic acid is known to take place according to the equation 6H*+ C10,’ + 61’= 31, + CI’+ 3H,O, and its velocity has been studied by the compensation method by Bray (J.Physical Chem., 1903,7,92). Some experiments on this subject had been carried out prior to the publication of Bray’s work, but as they only confirmed these results, the work has been discontinued. The method at first adopted was to mix definite volumes of standard soliltions of potassium chlorate and potassium iodide and add a known 226 volume of N sulphuric acid, so that the concentrations were accurately known. When no acid is added, iodine is not separated, even after 12 months, when the solution is allowed to remain at the ordinary temperature and exposed to daylight. The velocity of the reaction is dependent on the concentration of hydrogen ions, and the reaction is an extremely suitable one for demonstrating the velocity of reaction.If 10 C.C. of 0.2 N potassium chlorate solution, 60 C.C. of 0.2 N potassium iodide solution, and 15 C.C. of N sulphuric acid are mixed, the solution remains almost colourless for a few minutes ;a little of the mixture may then be warmed to show that the velocity is accelerated by rise of temperature. In the course of some hours, the intensity of the coloration incretses perceptibly, but it is only after six or seven weeks that the maximum reaction has taken place at the ordinary tempera- ture, After definite intervals of time, portions of the solution were titrated with N/100 sodium thiosulphste solution, and the velocity of reaction calculated in the ordinary way.During the course of some experiments with excess of potassium chlorate, it was observed$hat the concentration of the iodine in solution rose to a maximum and then diminished; at the same time, much iodine had volatilised on to the cork of the flask containing the solution. The same experiment was then made in a glass-stoppered bottle. The maximum intensity of coloration in this case was apparently reached in about six weeks, and som after iodine began to crystallise out. After about 11 or 12 weeks, the solution was quite colourless, and some very well-developed crystals of iodine were found in the bottle. About two months after the solution had become colourless, the iodine crystals had completely disappeared As there was still the chance of leakage, the same experiment mas carried out in a sealed tube.Five C.C. of N/5 potassium iodine solution, 45 C.C. of N/5 potassium chlorate solution, and 15 C.C. of N sulphuric acid were sealed in a wide glass tube, which was then freely exposed to the light. So far as could be judged by the eye, the maximum intensity of coloration was reached in about 24 days, and on the 27th day, crystals of iodine began to separate. The colourof the solution than began todiminish in intensity, and after about 50 days the colour disappeared completely and the quantity of iodine separated was considerable. The iodine then began to dissolve slowly, and after about five months (from the beginning of the experiment) the whole of the iodine passed completely into solution without imparting any colour to the solution; during the period in which this dissolution was taking place, it was frequently noticed that in proximity with each iodine crystal, a yellow solution wag formed, as if the iodine were being dissolved per Be.These results suggest that the reaction proceeds further than is 227 denoted by the above equation, and they do not suggest in any way that a definite equilibrium is established. Saturated solutions of potassium chlorate were sealed in tubes (1) with a small amount of iodine, and (2j with a large excess of iodine. In both cases, the iodine dissolved and the solution became yellow ; the intensity of coloration appeared to. increase progressively to a maximum after several days, and after four months there is no perceptible evidence of any diminution of the coloration.The fact that the colour only slowly developed shows that it is not due simply to physical dissolution of the iodine in the potassium chlorate solution, but suggests that a chemical reaction has taken place whereby potassium iodide or iodine ions have been formed, which then cause the iodine to pass into solution. As no acid was used in these cases, it is at present not possible to see what bearing the results have OD the previous case, where the reaction takes place in presence of acid. 142. 3 :5-Dichloro-l : 1:2-trirneth~1-A~:4-dihydrobenzene. A cor-rection.” By A.W.Crossley.Some time ago (Trans., 1901, 79, 144), the author described a substance obtained by the action of phosphorus pentachloride on trimethyldihydroresorcin as 3 :5-dichloro-1 :1:Z-trimethyl-A* :4-dihydrobenzene (A2:6-dichloro-3 :4 :4-trimethyl&ihydrobenzene), On further examination, this compound has been shown to be an aromatic substance and is in reality a dichlorotrimeb~ylbenzsna. At tbe time the work was done, it was not known that phosphorus haloids acted on dihydroreeorcins to give aromatic derivatives; the fact has only since been established (T+ans.,1902, 81,1536; 1903, 83,116, 502), moreover as the formula? of these two substances differ only by two hydrogen atoms, analysis is not of much help in deciding between them.Dichlorotrimethyldihydrobenzeneis produced during the action of phosphorus pentachloride on trimethyldihydroresorcin(Zoc. cit.), and is contained in the liquid boiling at 120-125O under 31 mm. pressure. The chemical properties of both these substances mill be described in detail on a future occasion. 228 143. “The estimation of hydroxylamine.” By H. 0. Jones and F. W. Carpenter. The methods hitherto described for the estimation of hydroxylamine were found to be very untrustworthy in the presence of substances such as neutral metallic salts, although these compounds would not be expected to affect the reactions involved. The following process has been devised, which is free from these objections and is simple and accurate.Ten to 20 C.C. of the hydroxylamine solution (which should not contain more than 0.5 per cent. of the base) are added to a hot solution of copper potassium carbonate or copper potassium tartrate, which is well stirred during the addition. The mixture is raised to the boiling point, the cuprous oxide at once collected in a Gooch crucible, washed with hot water, and dissolved in ferric sulphate solution in an atmosphere of carbon dioxide, the ferrous salt produced being titrated with potassium permanganate solution as recommended by Wood and Berry (Proc. Carnb. PhiE. Xoc., 1903, 12, ii, 97). Four mols. of the permanganate correspond with 10 mols. of hydroxyl-amine. The foregoing reactions are not affected by the presence of foreign substances provided that these do not reduce the copper solutions, and the method may be applied to mixtures containing sodium, potassium, ammonia, cobalt, nickel, and zinc salts, carbon dioxide, alcohol, acetic acid, and ketoximes.144. “A study of the isomerism and optical activity of quinque-valent nitrogen compounds.” By H. 0. Jones. An attempt has been made to prepare isomerides of quaternary ammonium compounds of the type N*RR”R,”‘X. The existence of theFe isomerides is theoretically possible on any configuration of the nitrogen atom, since it has been proved conclusively by the work of Pope and his colleagues that the configuration of radicles about a quinquevalent nitrogen atom is a stable one giving rise to optical activity. Taking Bischoff’s “ pyramidal ” configuration, which affords the best explanation of the facts at present known, two isomerides are to be expected, one of which should be capable of existing in optically active forms.Seven compounds of the desired type have been produced (with one exception in two different ways) and their properties studied, but no evidence of isomerism was obtained. The compounds have been cx- amined for optical activi by by the fractional crystallisation of the d-cam- 229 phorsulphonate and the d-bromocamphorsulphonatefrom non-hydroxylic solvents ;in no case was any resolution effected, so that the compound produced in all cases has a planisymmetric configuration. The absence of isomerism is discussed in the light of Kipping’s results on the isomerism of compounds of the type NRH,X, in which R and X both contain an asymmetric carbon atom.Optical activity due to an asymmetric nitrogen atom is to be expected in a-and P-substituted pyridinium compounds and in certain tetrahydroquinolinium derivatives. Several of these compounds have been examined by the method already mentioned, but for some un-known reason no resolution could be effected. d-PhenyZbenxylmethylet?qZammonizcm d-camphorsulphonate melts at 181’ and the corresponding d-iodide at I 46-1 47” ; the platinicldoride of d-phenylmethylethylallylammonium d-bromocamphorsulphonate melts at 159-160’. 145. The influence of various substituents on the optical activity‘6 of tsrtramide.” By P.F.Frankland and A. Slator. This paper forms a part of the systematic investigation being made by one of the authors on the connection between the rotation and chemical constitution of optically active molecules. The preparation and properties of seventeen derivatives of tartramide are described, the series including the methyl, ethyl, and benzyl amides, the anilide toluidides (0-,m-, and p),and a-and P-naphthylamides ;the anil and p-toluil; the hydrazide and phenylhydrazide ; the hydrazones of benzaldehyde, furfuraldehyde, and acetophenone ; as well as the 0-toluidide of diace tyl tartaric acid. In order to avoid errors arising from the possible racemisation of the t,artaric acid, the compounds have, in nearly all cases, been pre- pared by the direct interaction of acid and base, as well as by acting with the base on an ethereal salt of the acid; but, although the latter reaction could generally be made to take place at a lower temperature than the former, no substantial difference in the optical activity of the products was discoverable.All the compounds were, like tartramide itself, dextrorotatory. The molecular rotation is considerably increased by the introduction of the methyl, ethyl, and benzyl groups, whilst a much greater augmentation is effected by the introduction of the aromatic radicles, the highost rotation being obtained in the case of the P-naphthylamide. The two imides-tartranil and tartaric p-toluil-have much lower rotations than the corresponding diamides-tartrsnilide and tartaric p-toluidide-notwithstanding the cyclic groupings present in the former 230 compounds.Similarly, low rotations have, however, also been found by Walden for malanil and malic P-naphthimide. The molecular rotation of tartaric hydrazide is very slightly greater than that of tartramide, whilst that of the phenylhydrazide is much less than that of either ; but, on the other hand, the hydrazones have very high rotations, a circumstance which is very probably due to the double linking which they contain, this grouping, whether between two atoms of carbon 01' between carbon and nitrogen, being known to exert a powerful influence on the rotation. 146. '(The influence of cyclic radicles on optical activity : tartaric ar-and ac-tetrahydro-P-naphthylamides,furfurylamide, and piperidide." By P.F. Frankland and E. Ormerod. The authors describe the preparation and properties of the above compounds. As anticipated, the ar-tetrahydro-P-naphthylamidehas a molecular rotation, [MI:' + 840°, of the same order as those of the ordinary aromatic amides of tartaric acid, whilst the rotation of the ac-tetrahydro-p-naphthylamide,[M]y + 340°, is very much lower, being of the same order as those of the fatty amides : methylamide, [MI? + 278O, and ethylamide, + 279". It has been shown by P. Frankland and F. W. Aston (Trans.,1901, 79, 514) that the rotatory influence of the pyromucyl radicle is very similar to that of the benzoyl and toluyl groups, from which is to be inferred that the furfuran and benzene rings resemble each other in rotatory effect.It would be expected, therefore, that the furfuryl- amide should have a molecular rotation of the same order as that of the benzylamide ;as a matter of fact, they were found to be practically identical, thus : [M Tartaric dibenzylamide ..................... + 300° ,, difurfurylamide .................. + 300-307° Tartaric dipiperidide was found to be practically inactive. 147. ''The rotatory power* of maldiamide, maldi-n-propylamide, and maldibenzylamide." By J. McCrae. Mccldi-n-propylamide and maldibenxylamide were prepared by heating diethyl I-malate with n-propylamine and benzylamine respective1 y. The propylamide melts at 125.5" and the benzylamide at 155.5".The specific rotations are : in acetic acid (c= 4.7 to 5), maldiamide, -45.2"; maldi-n-propylarnide, -47" ; maldibenzylamide, -20.2O ;in 231 pyridine, maldiamide (c =2), -57.7’ ;maldi-rt-propylamide, -419’; maldibenzylamide, -32.4’. By comparing these results with those obtained by Guye and Babel and by Walden for the corresponding anilide and toluidides, it is seen that the effect produced on the rotatory power by the introduction of benzyl groups into maldiamide is similar to that caused by introduc- ing fatty alkyl groups, but is different from that brought about by replacing hydrogen of the amino-groups by aryl radicles. 148. (( Further experiments with phosphorus sesquisulphide.” By E. G. Clayton. In a previous communication (Proc., 1902, 129), it was shown that commercial phosphorus sesquisulphide of good quality had been found to give no reaction with Mitscherlich‘s test.With the object of studying under what conditions, oxidation, or a similar change, is promoted, and whether, by keeping, this compound acquires the property of yielding R luminous vapour when distilled with dilute sulphuric acid, the author has exposed specimens, which had pre-viously given negative results, for various periods under clifferent conditions, the products being then subjected to Mitscherlich’s test. Atmosphere in which the phos-phorus sesqni- sulphide was exposed. Capacity and nature of vessel. Time of in months. exposure Qnantities taken of phosphoruisesqui-sulphideand 10 percent.acid. Observation. Dry air. rightly corked, wide -mouthed bottle, about 90c.c.capacity. 6 grms. C.C. 10 50 Negative result. cence at any stapof the experi-ment, or in any portion of the NO phosphores- apparatus. lir mixed with acetic acid and jell-jar, 4 litres’ capacity. 6 20 100 Result as above. water-vapour. jomewhatair. damF ,oosely stop-pered, wide-mouthed bot-tle, 300 C.C. capacity. 6 20 100 When 35 C.C. had distilled, a faint luminosity ap-peared on coolir~gin the upper coils of the spiral con- denser and in tlie flask. 232 Atmosphere in which the phos- phorus sesqui- sulphide was exposed. Air saturated witl moisture. * kir saturated witl water-vapour. * htmosphere min.gled with am. monia, carbon di. oxide, and water. vapour. lir impregnatedwith hydrochloric acid. Lir over sulphuric acid. [The acid became brown and diluted in the course of the experiment, the air being evident- ly moist.] ltniosphere im-pregnated with nitrogen oxides. Capacity and nature of vessel. Xass shadc, 2 litres’ capacity !ell-jar, 4 litres capacity. tell-jar, 4 litres capacity. llass shade, 21 li tres’ capacity. ilass ~hade~3.75 litres’ capaci ty. lass shade, 21 litres’ capacity. Time of exposurein months. Quantitie taken of 3hosphq.rusesqui-sulphideand 10 pe cent. acid grms. C.C. 5 32 10 50 20 100 20 100 20 100 10 50 Observation. 3trong phosphor-escence in flask, connecting tube, and coils of con-denser.On cool-ing, a vertical stream of lumin-ous vapour de-scended into the flask. Smilar reaction, but less marked. Cxcessively faint phosphorescencein upper coils, none in flask. lfter 30 c.e. had distilled, phos-phorescence ap-peared in uppercoils and connect-ing tube, none in flask. ’owards the end of the experi-ment, a feeble glow appeared,visible iu the up- per coils of t,he condenser only. Sefore 5 C.C. had distilled over, a very strong ph o sphorescenceappeared on cool-ing, and a verti-cal stream of Iight descended into the flask, the in-terior of which became luminous for several min- utes. * In these cases, a garlic odour was perceptible when the glass vessels were removed.233 Quantities Atmosphere in taken of which the phos- Capacity and Time of ihoephorusphorus sequi- nature of exposure sesqui-Observation. sulphide was in sulphide exposed. vessel. months. tnd 10 per:ent. acid. Tams C.C. 10 iir of average Beaker, 300 C.C. 20 100 When 30 C.C. had humidity. capacity. distilled, a dis-tinct but slightluminosity was visible in the up-per coils and con- necting tube, al-though not in the flask. 11 iir of average :lass shade, 21 20 100 kfter 40 C.C. had humidity. litres’ capacity. passed over, traces of phos-phorescence were noticed in tube and coils, but none in flask. -Experiments 9, 10, and 11 were made at a !ater date than the rest, consequently with a sample of sesquisulphide which had already been kept in the laboratory for a longer period.The last two experiments were made with the view of investigating the influence, if any, of the size of the vessel, but the results were not markedly different. The temperature of the laboratory, of course, fluctuated considerably, but similar variations were experienced by samples exposed for the same periods. From the results of these experiments, in which the author was assisted by Mr. G. N. Bacon, it is evident that good commercial phosphorus sesquisulphide undergoes little change if preserved in air of average dryness in nearly filled, well-closed vessels, but that the progress of the oxidation is appreciable in a damp atmo- sphere or in imperfectly closed vessels ; this action takes place par- ticularly rapidly in air saturated with moisture, and perhaps to the greatest extent in the presence of acid vapours, especially such as nitrogen peroxide.Comparative experiments were made with yellow phosphorus, from which a luminous vapour passed over almost as soon as distillation began. With phosphorus sesquisulphide, on the other hand, the phosphorescence in most cases was seen only after the pressure had been diminished by the removal of the lamp, and after a considerable 234 proportion of the liquid had distilled over. The author’s experiments confirm J. Mai and F. Schaffer’s observation (Bey., 1903, 36,870 ; also J. Soc. Chem. Ind., 1903, 22, 511) that the glow differs from that of yellow phosphorus.RESEARCH FUND. A Meeting of the Research Fund Committee mill be held in December. Applications for grants, to be made on forms which can be obtained from the Assistant Secretary, must be received on or before December 7th. At the next ordinary meeting, on Wednesday, November 18th, 1903, at 5.30 p.m., the following papers will be communicated :-‘‘Constitution of ethyl cyanoacetate. Condensation of ethyl cyanoacetate with its enolic form.” By P. Remfrey, and J. F. Thorpe. ‘I The action of water and dilute caustic soda solutions on crystalline and amorphous arsenic.” By W. T.Cooke. The union of carbon monoxide and oxygen and the drying of gases by cooling.” By A. F. Girvan. I‘ Note on a double chloride of molybdenum and potassium.” By G. G. Henderson. &‘ SimplXcation of Zeisel’s method for the determination of methoxy-and ethoxy-groups.” By W. H. Perkin. ‘‘The action of benzamidine on olefine 6-diketones.” By S. Ruhemann. R. CLAY AND SONS, LTD., BREAD BT. HILL, E.C., AND BUBQAY, BUFFOLK.
ISSN:0369-8718
DOI:10.1039/PL9031900199
出版商:RSC
年代:1903
数据来源: RSC
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