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Abstracts of the Proceedings of the Chemical Society, Vol. 2, No. 30 |
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Proceedings of the Chemical Society, London,
Volume 2,
Issue 30,
1886,
Page 263-269
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摘要:
ABSTRACTS OF THE PROCEEDINGS OF THE CHEMICAL SOCIETY. No. 30. Session 1886-87. December 16th, 1886. Dr. Hugo Muller, F.R.S.,President, in the Chair. Messrs. A. Percy Hoskins and M. Hunter were formally admitted Fellows of the Society. Certificates were read for the first time in favour of Messrs. William Henry Coates, Hedon House, 11, Archway Road, Highgate, N. ; Thomas Cooksey, B.Sc., 284, Pentonville Road, N. ; Hamilton Emmons, Mount Vernon Lodge, Leamington, U.S.A. ; Herbert McKeon, 123, Lansdowne Place, Brighton ; J. F. McArthur, Belgrave Crescent, Eccles ; David Henry Nayel, 21, Tay Street, Dundee; Joseph de Carle Smith, Junr., Norwich; Lionel W. Stansell, 16, Hardy Street, Maidstone ; D. A. Sutherland, Burntisland Oil Works, Burntisland, N.B.The following were duly elected Fellows of the Society :-Messrs. Horace Edward Brothers ; Francis J.H. Coutts ; Tamemasa Haga ; Henry John Hardy ; Michitada Kawakita ; Walter Leach ; Stephen James Pentecost ; Henry Joshua Phillips ; P. Yeshwant Sheshadri ; Tetsukichi Shimidzu ; Joseph Stapleton ; William Phillips Thompson ; Hikorokuro Yoshida. The following papers were read :-116. (‘Researches on the Constitution of ‘Azo- and Diazo-deriva- tives.’ I. Diazoamido-compounds.” By R. Meldola, F.R.S., and F. W. Streatfeild. In this paper the authors give the results of the application of the method described by them in a former communication (Trans., 1886, 624)to determine the constitution of the diazoamido-compounds. The compound described in the previous paper, paradinitrodiazoamido.benzene, has the symmetrical formula, N02*CsHaoN2*NH*CsH4*N0,, (1) (4) (4) (1)and is consequently nnsuitedfor the settlement of the question of intramolecular migration of the Nz-group. An unsymmetrical com- pound has therefore been prepared from paranitraniline and diazo- tised metanitraniline : it forms yellow needles melting at 211",and furnishes on decomposition with chlorhydric acid a mixture of meta-and paranitranilines, and of meta- and paranitrochlorobenzenes. Its ethyl-derivatke, prepared by the authors' method, melts at 148"' and gives on decomposition with chlorhydric acid a mixture of ethyl-met%- and ethylparanitraniline, and of the two corresponding nitro-chlorobenzenes.A method of identifying a mixture of meta- and paradiamines depending upon the colour reaction on oxidation (" indamine " formation) is described in the paper. In order to throw some light upon the reaction which takes place when these compounds are decomposed by being heated with chlorhydric acid, experiments have been made by heating diazonitrobenzene chlorides with chlorhydric acid in the presence of similar and dissimilar nitranilines, but the products were found to be identical in all cases with those of the corresponding diazoamido-compounds, so that it appears probable that these latter compounds are actually formed in the first instance. Metadinitrodiazoamidobenzene (Griess, Liebig's Annalew, 121,272) has been prepared by the action of 1mol.propor-tion of NaNO, upon two of metanitraniline dissolved in chlorhydric acid ; it forms straw-coloured needles melting at 194", and decom- poses when heated with strong chlorhydric acid into metanitrochloro- benzene and metanitraniline. The ethyl-derivative forms opaque whitish-yellow needles melting at 119"; it is decomposed by chlor- hydric acid into ethylmetanitraniline and metanitrochlorobenzene. The formula of these compounds are N02*G6Hq*N2*NH*CsH4*NOzand (1) (3) (3) (1) with the question of the identity of mixed diazoamido-compounds. In accordance with the results obtained by Griess (Bey., 1874, 1619) and other observers, it has been proved that the compound obtained by the action of diazotised paranitraniline upou metailitraniline is identical with the above-mentioned compound formed by the action of diazotised metanitraniline upon paranitraniline.The two com- pounds have the same melting point (211°), and give the same products on decomposition by chlorhydric acid ; the same holds good with respect to their ethyl-derivatives (m. p. 148'). From these facts it follows that in the formation of this compound isomeric change must take place in one or the other mode of preparation, and in 265 order to throw light upon this question, the authors have prepared for comparison the ethyl-derivatives resulting from the action of the diazotised nitranilines upon the ethylnitranilines. Thus by combining diazotised metanitraniline with ethylparanitraniline, a compound of C2H5)*C6H4*N02the formula N02*C6&*N2*N( is obtained.This is iso-(1) (8) (4) (1) meric with the ethyl-derivative (m. p. 148") above described ; it melts at 174-175", and is decomposed by chlorhydric acid into metanitro- chlorobenzene and ethylparanitraniline. On the other hand, by the action of diazotised paranitraniline upon ethylme tanitraniline, the the product is apparently an amidoazo- compound forming orange- yellow needles melting at 187". From diazotised paranitraniline and of m. p. 192", described in a previous paper (Trans., 1886, 630), is obtained. In a similar manner, diazotised metanitraniline acts upon ethylmetanitraniline with the formation of the dinzoethylamido-com- pound of m. p. 119", described in the present paper, The further applicability of the authors' method has been tested by preparing benzyl-derivatives of the foregoing dinitrodiazoamido-com- pounds.N02-CsH4*N,*N( *C6H4*N0,C7H1) crystallises from benzene in (1) (4) (4) (1)small yellow needles melting at 190" ; the corresponding modification 1:3-3 : 1 melts at 142", and the benzyl-derivative of the unsym- metrical dinitrodiaxoamido-compound melts at 180". The decomposi- tion products of the benzyl-derivatives are analogous to those of the corresponding ethyl-derivatives. Summarising their results, the authors point out that the evidence obtained in the course of the present investigation shows a distinct tendency of the N2-gronp to migrate to the para-position with respect to the other substituents : thus when metanitraniline is diazotised and combined with paranitr- aniline, the resulting compound has been proved to have the constitu- on first consideration, NO2*C6H,*N,.NH.C6II,.NO,.This migration is (1) (3) (4) (1)possibly effected through the formation of an intermediate additive compound as suggested by Victor Meyer (Ber., 1881, 2447), but the authors propose to submit this point to further investigation.DISCUSSION. Mr. FRISWELLasked did Professor Meldola invai-iably use the sealed tube method: might not a less violent method be employed ? He thought that probably what had been said of the easy decomposability sf some of the amido-azo-compounds referred to might be extended to all such bodies.Professor MELDOLA in reply, said that it was not always necessary to heat in a tube: mere boiling sufficed in many cases. 117. “The Influence of Silicon on the Properties of Iron and Steel.” Part I. By Thomas Turner, Assoc. R.S.M. After referring to the work of previous observers in this direction, including Bessemer, Gautier, Mrazek, Pourcel, Riley, Snelus, and others, the author gives an account of experimsnts undertaken to determine the influence of silicon on the purest form of iron obtain- able in considerable quantities. For these experiments metal was taken from the basic Bessemer vessel, at the end of the blow, and before any addition of manganese had been made. This metal had the following composition : C = 0.03, Mi = 0.0098, S = 0,039, Mn = 0~06,P = 0.04.It was mixed in a red-hot clay crucible with varying small quantities of silicon pig, containing 10.3 per cent. of silicon, the product being afterwards examined. The most important results are given in the following table :-Si per cent. by analysis. Limit of elasticity.Tons per sq. in. Breaking load. Tons per sq. in. Ratio limik to break. Extension per cent. on 10 inches. Reduction of area per cent. Relative hardness. 0 ‘0098 0 -02 13 -01 13 -08 21 *so 19 -95 0 ‘597 0 *656 27 *7 17 *ti ’77-@ 40.3 18 16 0 *035 0.039 15 -69 16 ‘42 23 ‘0’7 23-28 0 -680 0 $‘04 16 -3 18’2 31 -8 37 -7 17 17 0.08 16’72 23.77 0 ‘704 24 -2 44.9 20 0.117 18 -00 28 -05 0 -642 15 -6 26 *8 21 0 -13 18’37 25 *68 0 -715 18 *8 41.9 20 0 -027 17 95 21 95 0.861 26 -0 67 -4 15 Other specimens were prepared to which more silicon was added, but these broke in pieces in attempting to roll them.The last specimen in the above list is not comparable with the others, as in this case the silicon existed in the opidised condition, and the material more closely resembled the original metal in its behaviour. The author draws the following conclusions from his experiments. That the addition of silicon, in the form of silicon pig, to the purest iron obtainable in commerce tends to distinctly reduce its suitability for being rolled. With only a few hundreths per cent. of silicon, the metal remains quiet in the mould. Red shortness appears to increase 267 with the amount of silicon, though the welding properties appear to be quite unaffected ; the metal was tough when cold, with all propor- tions of silicon.The limit of elasticihy and tensile strength increase with addition of silicon, but the extension and the reduction of area are seriously diminished. The relative hardness is but slightly affected, and appears to be connected with the tenacity of the material. With 0.4 of silicon and 0.21 of carbon a steel was obtained which was difficult to work hot, but could be hardened, and was very tough when cold. The author points out that these results would be con- siderably modified by the presence of larger quantities of carbon and manganese, such as are met with in practice. DISCUSSION.In reply to a question by Dr. P. Frankland, Mr. TURNERsaid that the high qualities of the sample which he had stated contained oxidised silicon (silica), were due not to the presence of this body, but to the absence of silicon. The PRESIDENTasked if Mr. Turner could give any explanation of the boiling over, which he had referred to as occurring when the silicon-iron mas added. Mr. TURNERsaid that the matter had been somewhat fully dis- cussed elsewhere, and it was generally believed to be due to the evolution of gas which the iron had been able to retain in con-sequence of its containing silicon. 118. “The Distribution of Nitrifying Organisms in the Soil.” By R. Warington, F.R.S. The result of 69 experiments with clay or loamy soil from various depths shows that the nitrifying agent is present almost without exception down to 3 feet from the surface ; samples from below this depth did not always exhibit the power of causing nitrification, and none of the samples of soil taken 8 feet from the surface produced nitrification. The nitrifying organism present in the subsoil is apparently in a feeble condition, nitrification starting much later in solutions seeded with subsoil than in those seeded with surface soil.Reasons are given for believing that in agriculture, nitrification is practically confined to the surface soil. The nitrogenous matter present in the subsoil is, however, nitrifiable if exposed to favourable conditions. DISCUSSION. Dr.PERCY remarked that it appeared desirable to use FRANKLAND it nutritive material more constant in composition than urine in 268 experiments on nitrification. He objected to the term “nitrifying organisms :” Heraeus, in Berlin, having recently proved that there were a considerable number of organisms capable of inducing nitrifica- tion. Mr. WARINGTONsaid that, however unfit urine might be for a certain class of experiments, as the object he had in view was to ascertain if nitrifying organisms were present, he maintained that it was suEcient t,o have an easily nitrifiable solution. The President had asked-were nitrifying organisms present in essentially siliceous soils? He had no experience except with Rothamspd soils, but he should say that they were if such soils were found to contain nitrates ; moreover, Miintz had shown that if the organisms once became established in a bed, whatever its nature, it became more or less capable of effecting nitrification in suitable liquids passed through it.119. “Isomeric Change in the Phenol Series. The Action of Bromine on the Dibromonitrophenols.” By A. R. Ling. The author’s experiments have been conducted with the view of, if possible, obtaining some explanation of the isomeric change of dibromortho- into dibromoparanitrophen ol by the action of bromine first observed by Armstrong (Clzem. Xoc. J.,1875, 520). As products of the action of bromine on dibromorthonitrophenol he has obtained tetrabromoquinone, which is the chief product, together with bromo-and dibromoparcmitrophenol and orthobromodinitrophenol ; dibromo-paranitrophenol and bromine yielding bromo~aranitrophenol, ortho- bromodinitrophenol and te trabromoquinone.It would seem that the formation of the bromanil involves the partial debromination of the dibromonitrophenol, the resulting bromorthonitrophenol then undergoing isomeric change : the bromo- paranitrophenol thus produced is in part converted into bromodinitro- phenol by the nitric acid resulting from the nitroxyl displaced in the formation of bromanil, and in part into dibromoparanitrophenol. DISCUSSION. Mr. GROVESasked if the author had tested his bromine for iodine ; minute traces of this latter often had a most material influence : thus Dribromophenol was readily converted into bromainil by means of bromine containing a little iodine, but not by pure bromine; and not a few other similar cases might be mentioned. 120.“Some Azines.” By Francis R. Japp, F.R.S,, and Cosmo Innes Burton, B.Sc. The authors have endeavoured to ascertain whether ditolane- 269 azotide, C2eH20Nz,and diphenant hrylene-avotide, C2sH16N,(Trans., 1886, 826 and 843), belong to the class of the ketines or to that of the axines, They find that no ditolane-aeotide is formed wheQ beazil-monohydroxim is treated with tin and hydrochloric aoid, con.. trwy to what might be expeoted to OGCUP if the azotide were a ketine, They further show that there is ;t close analogy between diphen= anthrylene-azotide and Witt’s a-p-naphthaaine (Bey,, 19, 2794), and they have succeeded in synthesising the latter compound by heating p-naphthaquinane with ammonium acetate-a reaction which exaotly corresponds with that in which diphenanthrylene-azotide is obtained from phenanthraquinone (Trans., 1886, 829, foot-note) , These analogies, together with the fact that ditolane-azotide may be trans- formed into diphenanthrylene-azotide (Trans., 1886, 843), lead them to regard these compounds as azines : c*c C*N* C6H5 C,H,*C*N*C*CtjH4II I II I II I II IC,jH5*CqN.C*CaH5 CJ&*C*N*C*CsH4 SALE OP THE {‘ ABSTRACTS OF PROCEEDINGS.” The “Abstracts of Proceedings” are purchasable at a price of seven shillings and sixpence per annum, post free.Intending sub-scribers are requested to apply to Mr. VANVOORST,Paternoster Row, London. NOTICE TO AUTHORS OF PAPERS. To facilitate the preparation of the abstract accounts of the Pro-ceedings at the meetings of the Society, all authors are requested to furnish abstracts of their communications, and to send their papers so that they may be in the hands of the Secretaries, if possible, on the Monday before the day of meeting. HARRISON AND SONS, PRINTERS IN ORDINARY TO HER MAJESTY, ST. MARTIN’S LANE.
ISSN:0369-8718
DOI:10.1039/PL8860200263
出版商:RSC
年代:1886
数据来源: RSC
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