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Proceedings of the Chemical Society, Vol. 9, No. 129 |
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Proceedings of the Chemical Society, London,
Volume 9,
Issue 129,
1893,
Page 233-242
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摘要:
PROCEEDINGS OF THE CHEMICAL SOCIETY. No.129. Session 1893-94. November 16th, 1893. Dr. Armstrong, President, in the Chair. Messrs. J. H. Coste, R. C. T. Evans and C. A. Mitchell were form-ally admitted Fellows of the SocietJy. Certificates were read for the first time in favour of Messrs. David Anderson, 14,St. Julian’s Road, Kilburn, N.W. ;‘.William Edward Bamber, Spring Lawn, Henton, Bolton ; Williani Rowland Bird, 73, Albion Street, New Swindon, Wilts ; Chuni La1 Bose, 24,Mohendro Bose’s Lane, Calcutta ; John Cannell Cain, Stubbins Villa, Stubbins, near Manchestel. ; F. I). Chattaway, St. Bartholomew’s Hospital, E.C. ; Samuel Henry Davies, Dalton Hall, Manchester ; John Puncan, RI.D., St. Petersburg, ‘Russia; Frank Evershed, Kenley, Surrey ; George Trench, Standard House, Faversham ; Ernest William Gay, 14, St. Julian’s Road, Kilburn, N.W.; Edward Frank Harrison, 17, Bloomsbnry Square, W.C.; Edmond Herbert Hills, Darland House, Chatham ; John Winder Holmes, 28, Crooms Hill, Greenwich ; DaTid Hamilton Jackson, M.A., B.Sc., Royal College of Science, South Kensington ; George F. Gaubert, Ph.D., Anilin Fnbrik, Ludwigshaferi am Eh. ; Robert Leonard Jenks, 68, Victoria Road, Clapham, S.W. ; A. Lapworth, 13, Duchess Itoad, Birmingham ; Godfrey Melland, Victoria Park, Manchester ; J. M. Murray, B.Sc., Highfield, Holmes Chapel, Cheshire ; Richard PauluGz, Colombo ; William Henry Pearson, 5, Rryn Villas, Blaina, Monmouth; J. Holms Pollock, 37, Athole Gardens, Glasgow ; Meredith Young, M.B., C.M., Brighouse, Yorks.The following is the text of a. letter addressed by the President to Professor Mendelhef, the President of thc Russian Chemical Society, St. Petersburg :- (( Learning that the Society over which you preside will celebrate its 25th Anniversary on the 18th of this month, I beg, on behalf of the Chemical Society of London, to tender our most hearty con-gratulations and our good wishes for the future. " Notwithstanding the grave difficulties which your language im- poses, your English colleagues learn from time to time of your labours, the name of your Society and a record of its work regu- larly appearing in our volume of abstracts of chemical papers. We are thus frequently brought face to face with researches of the greatest interest and importance, and the wish that we could enjoy less restricted intercourse with our Russian colleagues is often felt among us. Wc look forward to the time when this wish will be gratified, and trust that it may not, be far distant.'I Our Society is proud to have enrolled your name on its list of foreign members, and to have welcomed you as one of its Faraday4 Lecturers ; and the roll also includes the name of Beilstein, which: however, is no longer the mere name of an individual, but a house-hold word throughout the chemical world, and one which cannot be mentioned without the feeling of gratitude arising in the chemist's mind. There are many other names of Russian chemists indelibly associated in our memories with discoveries of f unda-mental importance .' ' Of the following papers those marked * were read :-"76.'I The normal butylic, heptylic and octylic ethereal salts of active glyceric acid." By Percy Frankland, Ph.D., B,Sc., F.R.S., and John MacGregor, M.A. The authors hare previously described the preparation and pro- perties of the methylic, ethylic, propylic, isopropylic, normal, secondary and isobutylic salts of both inactive and active glyceric acids, and have shown that in ascending the homologous series of ealt's of active glyceric acid the rotatory power increases with thr molecular weight,, but that the rotation of the normal butylic coni- pound is considerably less than this general relationship indicated it should be.In order to ascertain whether the increase in rota-tory power continues indefinitely as the molecular weight increases, they have now prepared and examined the heptylic and octylic salts, and have also again prepared the normal butylic salt, which they had not before obtained in a state of purity. As will be seen from the subsequent table, the results show that the rotatory power does not increase indefinitely as the homologous series is ascended, but that a maximum rotation is reached apparently at the butylic compound in the case of the normal series, the specific 235 rotation of the heptylic being less, and that of the octylic still less than that of the normal butyl compound. Such a maximum rotabion in a homologous series has been pre- dicted by Guye from a Consideration of t,he successive values of the product of asymmetry, but the calculated maximum, as will be seen from the table, falls on the propylic instead of on the butylic compound.In the case of the salts containing secondary radicles, of which, however, only the isopropylic and secondary butylic com-pounds have been examined, the maximum rotation is actually exhibited by the propylic compound as predicted by calculation. I Observed Specific Mol. Mol. Product, Etlicreal sdt. rotation. rotation. deviation. of asym-metyy.[.ID. [MI,. [SlD. (P x 10”. I-------------I Metliylic .. . .. . . 1‘2798 -13.2’ -4 -80’ -5.76 -27 -9 288 -8 Ethylic .... . . . , 1-1981 -21 *7 -9 -18 -12 ‘30 -52 ‘8 344 -8 Yropy lic .. . .. .. 1*144Y -29 *4 -12.94 -19 .l5 -$4 *Y 358 2 Isopropylic. .. .. 1-1303 -26 ’5 -11-82 -17 -49 -67 -8 358 -2 Butylic (norm.), 1-1034 -29’0 -13-19 -21 -37 -77 -0 346 -8 Isobntylic . . , . . 1*lo51 -31 -2 -14 -23 -23 -0.5 -86 -9 346 -8 Butylic (sec.) . . . 1-1052 -23 -2 -10 *58 -17.14 -61 -7 346 -8 Hepty lic . . , . . . . 1-0390 -23 ’3 -11 *30 -23 -05 -68 *3 268 -7 Octjlic . . ,. .... 1-0263 -20 *8 -10 -22 -22 -28 -ti2 *6 241 -8 “7. ‘‘ The ethereal salts of diacetylglyceric acid in relation to the con- nection between optical activity and chemical constitution.” ByPercy Frankland, Ph.D., B.Sc:, F.R.S., and John MacGregor, M.A. The methylic, ethylic, propylic, isopropylic and isobutylic salts of active diacetylglyceric acid were prepared by heating ths corre- sponding salts of active glyceric acid with an excess of acetyl chloride, and then fractionally distilling in 2;aczio.These compounds are colourless, almost inodorous liquids, volntilising without de- composition even under ordinary atmospheric pressure at between 200” and 300”. Tlle special interest attaching to them consists in the circumstance that, both in the methylic and ethylic compounds respectively, two of the groups attached to the asymmetric carbon atom are of equal mass, and, therefore, according to Guye’s theory, these two compounds should be inactive, or nearly so, or at any rate some of the members of this series should exhibit a rotation of opposite sign to that exhibited by the glyccrates.As will be seen from the table, some of these anticipations are realised, the sip througlioot being similar to that of the ethereal salts of glyceric acid, the increase in rotation on ascending the series ot diacetylglycerat,es pracaeding 011 lines almost parallel to those fol-lowed in ascending the glycerate series, the diacetylglycerates only starting from a higher level of rotation, so to speak. The authors consequently again urge the necessity of also taking into considera- tion the qualitative nature of the groups attached to the asymmetric carbon atom, and not8their masses only. Observed Specific Molecular Molecular ProdI1Cts Etheveal Density rotation at i‘otation rotation. deri ation. asy 111 in?try15’ C. in 0f salt. 15”/15”.198.4mm. L-aIIY CWD. viD. (I’ x 10”).tnbe (a),,. ----~ Methglic .... 1 -199s -280 .€it> -120.04 -240 ‘56 -80.0 0 ‘0 EthFlic .. . ... 1 *1574 -37 -46 -16 ‘31 -35 -56 -108.2 0.0 Proiljlic ..... 1 ‘1263 -43 -52 -19 -47 -45 -17 -129 -5 17 ‘44 ‘Isopropylic . . . 3 ‘1193 -39 -YO -17 ‘97 -41.69 -119 -1 17 *4 Isobutylic ,. . . -20 ’48 -50 ‘33 -136 -7 41 *‘3 Mr. L. &I.JOSES observed that inasmuch as the product of dis-symmetry employed presupposes the equality of the distances of the centres of gravity of the combined groups from the central carbon atom, it can only give an approximate indication of wlieiie the maximum “molecular deviations” will be found. Iii the case of the diacetylglycerates, as the salts which have this product = 0 show marked activity, we should expect considerable divergeiicc between the obserryed and predicted maxima.Mr. KODGERdrew special attent’ioii to the fact that the ‘‘ iiioloculai. deviation,” -eniployed by Guje in a rcceut communica- a x d:,1 tioii, was probably the true value of the molecular rotxtory power. a -is evidently the angle of rotation produced bg unit lengtli of sub-stance. is the molecular length or a length which for dif-d-: ferent substances contains the same nuniber of molecules, aiid the “molecular deviation ” is, therefore, proportional to the angle of rotation produced by the same number of molecules or to the rotation per molecule, The dimensions of tlhis quantity nre tliose of ail angle -the physical magnitu de actnally measured--wh ereas the ordinary iiieasure of inolecular rotation -ct X 31 is nil aiiglc uiu1tii)licd by ti SLIP1 tl 237 face.He also pointed out that the effect of temperature on rotatory power had been little studied. Such experiments as had been made indicated, however, that the teniperature change varied with the chemical nature of the substance, and hence that relationships obtained at the same temperature, according to the usual custom, would no longer be the same if the temperature of comparison were altered, For these reasons the significant speculations of Guye could only be subjecte’d to a fair test, when “ molecular deviations ” had been measured at temperatures at which, as regards the property under consideration, the substances were in comparable states.“79.“The oxidation of paxatoluidine.” By Arthur G.Green. The red crystalline substance obtained by Rarsilowsky in 1873 by oxidising paratoluidine with potassium ferrocyanide has been variously considered as a polymeric parazotoluene, as a tritoluylene- diamine and a complex amidoazo-compound. The author has re-examined this remarkable substance. He arrives at the conclusion that the substance is a diparatolylimide represented by the formula 3 C6H(Cb3)(NH2)<NC,H:NC7H derived from amidotoluquinone. This 1 6 conclusion is deduced from the following facts. The base 1ias the empirical composition C7H7N, and its molecular weight corresponds to the formula C21H,,N,. By treatment with chlorhydric acid it is readily decomposed, one paratoluidine residue being split ofl and a second being removed by further treatment of the intermediate product. On reduction, it takes up 2 atoms of hydrogen, affording a stable, colourless leuco-base.This latter is readily reoxidised to the original substance, has very slight basic properties, and is not decom- posed by acids or further reduced by boiling with stannous chloride. The leuco-base condenses readily with benzil forming a coloured azonium compound ; and it yields colourless, non-oxidisnbIe anhydro- compounds with formic and acetic acids, thus showing a11 the cha- racteristics of a mono-substitubed cjrthodiamine. This result, taken in conjunction with the presence of two parattolylimide groups in the original substance, as shown by its decomposition by acids, proves that the leuco-base is a diparatolyltriamidotoluene.Of the three possible formulae for this compound the greatest probability attaches to that in which the two tolylnmido-groups are relatively in the Pam- position. This formula would represent the leuco-base as an amido- derivative of diparatolylparatolylenediamine. The diparatolylpara-tolyleiiediamine was accordingly prepared by heating hydrotolu- quinone with paratoluidine and zinc chloride and submitted to com- parison with the leuco-base. A marked similarity in appearance and properties was observable, entirely in accordance with the view that the latter is the amido-derivative of the former.Moreover, the di- paratolylparatolylenediamine was converted by oxidation into tolu- quinonediparatolyldiamine, and this substance showed a striking similarity in its appearance and in all its properties to Barsilowsky’s base. There could, therefore, be little doubt that the tolylamido- groups in the leuco-base and the tolylimido-groups in the original compound occupy the para-position to each other, and that conse-quently the constitution of the Barsilowsky base is that given above, whilst its leuco-compound must be represented by the formula CsH,(CH,)(NH2)(NHC7H7)[l : 4 :3 : 61. In agreement with this conclusion, the synthesis of Barsilowsky’s base was effected by oxidation of a mixture of orthamidometaparaditolylamine and para- toluidine in acetic acid solution, whilst its lower homologue was pre- pared in a similar manner from orthamidometaparaditolylamine and aniline.“79. “The action of benzoic chloride on urine in presence of alkali. Formation of benzoic derivatives of urochrome.” By J. L. W. Thudichum, M.D.,F.R.C.P. The author has examined the products of the action of benzoic chlor- ide on urine in the presence of alkali. The urine rendered strongly alkaline with soda, and filtered from the precipitated phosphates, is mixed with benzoic chloride in the proportion of 50 C.C. for each litre of urine used. The mixture is kept cool and constantly agitated, care being taken to maintain a strong alkaline reaction. A yellowish-white, semi-solid precipitate separates, which by extrac- tion with alcohol may be separated into three parts: (1) an oily substance soluble in cold alcohol, (2) a solid soluble in hot alcohol, (3j a small quantity of a solid insoluble in boiling alcohol, which was not further examined.The oil and the solid substances are con- sidered to be mixtures of various benzoic derivatives of urochrome, the normal colouring matter of urine, and of alcoholic compounds present in the urine. The mixed solid derivatives of urochrome contain between 58.9 and 63.2 per cent. of carbon, 5 per cent. of hydrogen, and between 3 and 1.5 per cent. of nitrogen, from which the author concludes that they are mixtures of polybenzoic de- rivatives, as he found 12 per cent. of nitrogen in urochrome. The solid benzoic derivatives may be most readily crystallised by dissolving the original precipitate in boiling absolute alcohol, filter- ing the hot liquid and evaporating until crystallisation begins. By fractionally crystallising the resulting mass from hot alcohol, the author separated it into three portions: (1) a crystalline solid not 239 diswlvrd by boiling spirit (" illsoluble ester "), (2) c1-yst:lllillc needles soluble in boiling spirit (" needle ester "), (i3) lamina: re-sembling cholesterol in appearance soluble in cold spirit (" cholestel+oid cster"j. The mother liquor contains for the most part the oily benzoic derivatives of urochrome.By the action of benzoic chloride on an aqueous solution of 111'0-chrome (prepared by the ferric chloride method), solid benzoic de- rivatives were obtained containing 1.77 per cent.of nitrogen. The same result may be secured by precipitating urine wit11 pbospho- tungstic acid, regenerating by means of bai-yta and extracting the residue with alcohol. 'l'he alcoholic solution, when mixed with mercuric chloride, furnishes a precipitate containing the urochrome and other bases. If this precipitate be deconiposed with hydrogen sulpliide, an acid liquid is obtained which, when acted on with benzoic chloride aiid soda, affords a precipitate of the lseiizoic de- rivatives of urochrome. Similarly, if the precipitate obtained by adding phosphotnngstic 01' phosphomolybdic acid to acidified urine be dissolved in soda and the solution be mixed with benzoic chloride, the same derivatires of urochrome are precipitated.B'rom this beliavionr the author concludes that urochrorne is at once am alcohol and a base. The benzoic derivatives of urochrome are hydrolpsed by strong alkali, but the liberated urochrome is, to some extent, decomposed, especially if the liquid be heated. Some, however, iiiay be recovered by acidulating the strong alkaline solution with dilute sulphuric acid and peci 1,itatiiig with phosphotuiigstic acid and decomposing the precipitate mi th barium carbonate in the usual manner. When the derivatives are hj-drolysed by heating with dilute sulphuric acid, iiiuch of the liberat ed urochrome suffers decomposition, produciiig tlie substance called LJ-the author umpittilz, as well as other uro-cliroiiie '' resins " (r~twnelaninand omicholin).Neither urocliiwine 1101' ih black deconiposition product, ur~rnelaiiin, are carbohydrates. 130th coiitaiu nitrogen. 9'11~ " cholesteroid ') benzoic derivative obtained from nriiie furnislied on conibustion results agreeing with tlie forniula CI3Hl2Ob. When hydrolysed with dilute sulphuric acid, it yields about 50 per cent. of beiizoic acid, together with a resinous substance. It con-tttiiied ciiily a truce of nitrogen, aiid is probably the derivative of an alcohol. The author obtained no beiizoic derivative of ;tuy substance in the natuiw of a sugar (cf. Wedenski, Zeit. physiol. Chem., 13,122). 80. ''The combination of hydrocarbons with picric acid and other nitro-compounds." By William A, Tilden and Martin 0.Forster. The authors have instituted a conipvund dc scribed by Lex trait in 1886, which is formed by heating picric acid with pinene. It contains the elements of picric acid and a terpene, but differs from the picrates of other hydrocarbons in forming a peculiar potassium salt, in yielding picramide and borneol when submitted to the action of alcoholic ammonia, and in forming borneol and not simply a hydrocarbon under the influence of aqueous alkalis. The authors have also instituted experiments on the behaviour of other hydrocarbons with nitro-compounds generally, from whioh it appears that, in order that a compound may be formed, at least two nitro-groups must be present in the nitro-derivative concerned.They conclude that the oxygen of the nitro-groups affords the link which, in ordinary cases, binds the hydrocarbon to the nitro-com- pound, while in the case of the pinene derivative the oxygen of the hydroxyl is probably also involved. 81. The formation of pyrrol derivatives from aconitic acid." ByS.Ruhe mann, Ph.D., M.A., and F. E. Allhusen, B.A. The authors find that when the ethereal salt of dibromotricarb-allylic acid (which they prepared by exposure of a mixture of ethylic aconitate and bromine to direct sunlight) and aniline in-teract, besides a compound melting at 87-88', which they regard as ethylic anhydroanilaconitate, an oil is formed which, on heat- ing at 250-260°, yields an isomeride, ethylic phenylpyrrolonedi- carboxylate, melting at 181".82. " The conversion of a-hydrindonoxime into hydrocarbostyril." ByF. Stanley Kipping, Ph.D., D.Sc. The peculiay inti*amolecular change first obseived by Beckrnann in the case of diphenylacetoxime has been carefully studied by V. Neyer, Hantasch and others during the last few years, and it has been shown that a great many open-chain hydroximes may be converted into substituted umides in accordance with the equa- tion RR'CZNOH = R-CO*NH-R'or R.NHaC0.R'. The behaviour of hydyoximes of cycloid ketones, however, has been but little investigated. Camphoroxime has been shown to yield campholenonitrile, CIOHI5N,and not a substituted aniide, as was to be expected from the behnviour of isonitrosocamphor, whicli yields camphorimide (Angelo, Be?.., 26, 59 ; Manasse, ibid., %1), and the only case, in fact, in which the desired change has hitherto been accomplished with the hydroxime of a cycloid ketone of known constitution appears to be that of phenanthra-quinonemonoxime, which, as Wegerhoff has shown (h'er.., 1888, 241 23.55), is readily transformed into cliphenimide, C&,*CO 76H4'c0>NH, the closed chain of 6 carbon atoms being converted CsHa*C0 into a closed chain of 7 atoms by the introduction of an imido- group. These considerations led the author to study the behaviour of hydrindonoxime. On subjecting this to the action of phosphorus pentachloride and water successively, it yielded a small quantity of a crystalline substance melting at 163", represented by the formula C:,H,NO (found C = 73-26; H = 6.32 ; required C = 7347; H = 6.12 per cent.).As far as could be ascertained without direct com- parison, this substance is identical with hydrocarbostyril. This change from C,H,< CHZ-->CH, into C,II,<CH~*QH~C:NOH NH*CO is, to some extent, analogous to the conversion of pyrroline into chloro-or bromo-pyridine, which appears to be ono of t'hc few cases on record of the conversion of a ring with 5into one containing 6 elements, although the reverse operation, namely, the transformation of a ring containing 6 into one containing 5 elements is known, from Zincke's work, to be easily accomplished. The publication of this note is desirable owing to the appearance of a paper by Wallach in the last number of the Amah(277, 154)) in which he describes preliminary experiments on the behaviour of hydroximes of cycloid ketones. 83."The constitution of lapachol and its derivatives. 11. The azines of the lapachol group." By Samuel C. Hooker, The author gives an account of azines of the lapchol group pre-pared from orthotoluylenediamine, and fully discusses the relations existing between lapachol and a-and P-lapachone and the changes occurring in the quinone group in the course of the transformation of these compounds into each other. The constitution of several of the compounds is discussed in relation to their colour. The com- pounds described are methyllnpazine, me thylbromolapazine, methyl- lapeurhodone, methylhydroxylapeurhodone, methyl-a-naphtheurhodol and methylchloronaphtheurhodone.242 ADDlTIONS TO THE LIBRARY. I. Donations. Smit,hsoninn Institution : Miscellaueous Colleclions. 850. A Select Bibliography of Chemistry, 1492-1892, by H. C. Rolton. Washing-ton 1893. From the Institution. Practical Agricultural Chemistry for Elementary Students, hg J. €3. Coleman and F. T. Addyman. London 1893. From the Publishers. Graham-Otto’s Ausfuhrliches Lehrbuch der Chemie. Dritte Auflage. Erater Band. Dritte Abtheiiung. Beziehungen zwischen pliysikal-ischen Eigenschaften nn Chemischer Znsnmmensetznng der K6rpt.r. Heransgegeben von H. Landolt. Kwte Hiilfte. Bmunschweig 189;3, Prom the Editoi-. ParnThlets. The Origin of Melinite and Lyddite, by H.Sprengel. London. A Contribution to the History of the Electric Incandescent Vacuum Lamp, by H. Sprengel. London 1&91. From the Author. RESEARCH FUND. A meeting of the Research Fund Committee will be held in December. Fellows desiring grants are requested to make applicn-tion before December 9th. At the next meeting, on December 7th, there will be a ballot for the election of Fellows, and the following papers will be rend :-“An apparatus for the extraction and estimation of the gases dis- solved in water.” By Dr. Truman. ‘‘The oxides of the elements and the pwiodic law.” By R. &I. Deeley. Correction in certificate of William Fred Mawer (Proc., No. 128, p. 226), for “ JoEiii Watts ” rend “ John Muter.” HARRISON AND SONS,PXINTEBS IN OEDINABY TO HER MAJESTY, ST. MABTIN’S LANE.
ISSN:0369-8718
DOI:10.1039/PL8930900233
出版商:RSC
年代:1893
数据来源: RSC
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