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Proceedings of the Chemical Society, Vol. 27, No. 394 |
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Proceedings of the Chemical Society, London,
Volume 27,
Issue 394,
1911,
Page 323-330
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摘要:
[Issued 30/12/11 PROCEEDINGS OF THE CHEMICAL SOCIETY. VOl. 27. No. 394. Thursday, December 21st, 1911, at 8.30 p.ni., Professor PERCYF. FRANKLAND,LL.D., F.R.S.,President, in the Chair. Messrs. Hugh Marshall and C. H. K. Gonville were formally admitted Fellows of the Society. Certificates were read for bhe first tinis in favour of Messrs.: Bred Barrow, KSc., Ph.D., Birkbeck College, Bream’s Buildings, E.C. David Brownlie, B.Sc., 41, Corporation Street, Blanchester. Thomas Alfred Brunjes, 49, St. Donatts Road, New Cross, S.E. Sidney Waterfield Bunker, B.Sc., 30, York Street., Twickenham. Tom Peach Colclough, M.Sc., 47, Vicar Lane, Woodhouse, Sheffield. Cornelius Durham Garbutt, 2, Hartington Road, Garstmi, Liverpool. Jyotish Chandra Ghmh, 105, M.C. Ghosh’s Lane, Howrah, India. Richard Ernest Gibbins, Clytha, Quinton Road, Ccventry. Rupert William Pope, B.Sc., 10, Malpas Road, Brockley, S.E. Howard Vincent Potter, Rosemount, Pollard Road, Whetstone, N. 324 Alfred Reginald Roberts, c/o Canada Cement Co., Shallow Lake, Ontario. Richard Smith, 6, Essex Road, Gorton, Manchester. John Kerfoot Wood, D.Sc., 7, Airlie Terrace, Dundee. A certificate has been authorissd by the Council for presentation to ballot under Bye-Law I (3) in favour of John Duncan, Victoria Street, Waterloo, Sydney, N .S.W. The PRESIDENTannounced that the Longstaff Medal (1912) had been awarded to Dr. H. Brereton Baker, F.R.S.; the actual pre- sentation would be made at the Annual General Meeting of the S0ciet.y in March, 1912.Of the following papers, those marked * were read: “333. “Investigations on the dependence of rotatory power on chemical constitution. Part 11. The rotations of some secondary alcohols containing the isopropyl group.” By Robert Howson Pickard and Joseph Kenyon. The authors have continued their investigations (Trans., 1911, 99, 45), and six alcohols of ths general formula CHMe,-CH (OH)=R, where R =methyl, ethyl, m-propyl, n-amyl, n-hexyl, or n-octyl, were described. Thespecific rotations at ZOO of the dextrorotatory forms of these alcohols are : ~ethylisopropylc~~binol,[a], +4.8O ; ethylisopropyl-carbinol, [a], +15.1O; ~o~liso).ropylcnrbinol, [a]= +21.2O; n -urnyli50propylcarbinol, [a], +22*7O; n-~~exylisopropylcarbinol, [uj, +21*5O, and n-octylisopropylcarbinol, [a], +18’5O. *334.‘(The alcohols of the hydroaromatic and terpene series. Part 11. The menthols corresponding with optically inactive menthone.” By Robert Howson Pickard and William Oswald Littlebury. The authors described an investigation of the relationship existing between the menthols produced by the reduction of one of the two optically inactive stereoisomerides, which have the formula CH --COCHMe<CHi* CH2>CHPra. The following diagram ahows the results obtained : 325 Thymol, by reduction. I I IManthone isoMenthone (semicarbazone, (semicarbazone, in. p. 158"), m. p. 217").by reduction. I I IMenthol, m. p. 34" neoMentho1, m.p. 51" (hydrogen phthalate, ni. p. 130"), (hydrogen phthalate, ni. p. 177'), on resolution. on resolution. 1_____~ I 1 1 I I''Natural "2-menthol, 12-Menthol, d-neoMenth ol Z-neoMen tho1 m.p. 43', [.ID -49". m. p. W, [aID+49". (oil), [a]=+20". (oil), [a],-20". I-Menthone, d-Menthone, [a]=-28". [.ID +28". d-neoMentho1 was found in some residues, which were kindly presented to the authors by Messrs. Schimmel &Co., who obtained the same after working up large quantities of Japanese peppermint oil for Z-menthol. "335. LL The absorption spectra of quinine, cupreine, I-methoxy- quinoline, and 6-hydroxyquinoline." By James Johnston Dobbie and John Jacob Fox. In a paper dealing with the absorption spectra of cinchonine, quinine, and their isomerides (Trans., 1911, 99, l254), it was shown that the absorption spectra of cinchonine and quinoline are practi- cally identical, the reduced half of the cinchonine molecule having little effect on the spectrum.The absorption spectra of quinine and cupreine have now been compared with those of 6-methoxy- quinoline and 6-hydroxyquinoline, with similar results. The four spectra resemble one another very closely. They exhibit three bands each, the principal band having its head at about 1/~3050,and the two others at about 1/~3500and 1/A3750 respec-tively. The chief difference between the spectra of quinine and cupreine on the one hand, and those of rnethoxyquinoline and hydroxyquinoline on the other, lies in the somewhat greater absorp- tion exhibited by the alkaloids. The hydrochlorides of quinine and 6-methoxyquinoline also yield absorption spectra which are nearly identical.The given by N/ 100-solutions of quinine sulphate and methoxyquinoline sulphate (both fluorewent solutiom) differ only in the greater general absorption of the former. 326 ‘I*336. Amino-derivatives of arylsulphonanilides and arylsulphon- P-naphthalides.” By Gilbert T. Morgan and Frances M. G. Wicklethw ait . ‘The toluene-~-sulplionyl derivatives od the m-and p-nitroanilines are readily methylated with methyl halides in alcoholic soda or potash, aiid the correspon cling as-tol?~ei/e-p-siiZ~hoi~?/lrnethyl-rn(anc1 p)-p?~eiiy7~1/eciinminPs are produced by the reduction of these toluene-p-sulphonylmethylnitroanilines. The diazonium salts of the new bases furnish azocolmrs dying on wool or silk by coupling with various naplitholsulplionic acids.Toluene-psulphon-j3-naphthalide yields on nitration, not only toluene-p-sulphonyl-1-nitro-P-naphthylamine,but also toliaene-p-sd-ylLonyl-l :6-dinit~.o-P-iictpkth?/lnmine. The former of these nitro-derivatives is readily methylat~ed, the latter only with some difficulty. The arnines produced by reducing these nitxo-compounds and their alkyl derivatives were described, t’ogether with a similar series of cornpou11 cls cieiiv e’d from P-napfithy1miitie-6-sulphoiii c acid. 337. ‘‘The action of nascent hydrogen on nitric acid.” By Manindra Nath Banerjee and Satish Chandra Banerjee.Veley, in explaining the action of nitric acid 011 metals (Proc. Roy. Soc., 1890, 46, 216; 1893, 52, 27; I’hiE. Trans., 1891, A, 312; J. Sor. Chc7~.177d., 1391, 10, 204), states that the action is due to nitrous acid and to it’s mass present in the solution. He believes that the action is started with inera traces of nitrous acid, always present in the original acit1. He is not in faxour of the nascent hydrogen theory advanced by certain chemists. The authors find that nascent hydrogen has rapid actioii on nitric acid, first decom- posing it (acting catalytically), and then reducing it to the lower oxides of nitrogen, and liiially to ammonia. This arguiiieiit has been further extended to explain tlie action of nitric acid on metals, in which the authors have attempted to prove Ghat it is the nascent hydrogen, and not nitrous acid, that is responsible €or the formatioil of various reduction products.The reaction is found to depend entirely on the capacity of metals to decompose water, and the authors confirin the views of Montenmrtini as to the relation of the action of nitric acid oil metals to that of metals on water (liberating hydrogen), namely, that thoso metals which decompoee w;i.t,er at a high temperature give wit,li nitric acid, nitrogen peroxide, trioxide, arid dioxide; whilst those that decompose water at a low temperature give, in addition to tlie above, nitrous oxide, nitrogen, arid anirrionia;and, lastly, thosr decomposing water at the ordinary ternperature aIs0 evolve hydrogen.327 Nascent hydrogen was obtained from platinum-black which had occluded the gas. The experiments showing the interaction between nitric acid and the platinum-black on the one hand, and the absorp- tion of the products by suitable reagents on the other, were con- ducted in a suitably arranged apparatus. The interaction of the nascent hydrogen and nitric acid results in the ready decomposition of the acid and formation of various reduction products, the free oxygen being wholly coiiverted into water, 338. ‘‘Studies in the camphane series. Part XXXI. Condensation of camphorquinone with nitroniethane, ethyl cyanoacetate, and phenylacetonitrile.” By Xartin Onslow Forster and John Charles Withers. Nitromethy,?enecamphor, C,H,,<hOC:CH.Noz, prepared from cam-phorquinone and wdionitromethane in alcohol, melts at 77O, and is immediately resolved into its factors by warm aquwus alkali; under certain conditions it is accompanied by .nitromethyZhydroxycampTLor, C*Hl,<&)C(oH)*CH2.No2, which melts at 104O, and also gives cam- phorquinone with hot alkali hydroxide.Ethyl campho?.~Zidenec?/nno-c(cef nte (ethyl met hylrnecamphorcyano cnrboqlate), C,B,*<Cl$XC( CN)*CO,*C,H, ¶ produced by the influenre of sodium etlioxide (0.05 mol.) on an alcoholic mixture of camphorquinone and ethyl cyanoacetate, forms lustrous, sulphur-yellow prisins, melting at 97O. The corresponding mid, CiSH,60JN,melts at 141--143O, and the rnrtltyl ester, C,, HI70,N,at S1O.1)hY n yf cyu 110 m cthyI e?iecamphor, obtained from camphorquillone and phenylacetonitrilel with a small proportion of sodium etlioxide, crystallises in massive, yellow prisms, melting at 166O. When ethyl camphorylidenecyanoacetate is treated with hydrogen peroxide, hydrolysis of the cyano-group takes place simultaneously with oxidation. The resulting ctrrtide-ester, Cl,H2,0,N, melts at 209O, and is accompanied by the nmide-acid, C,,H,70,N,H,0, melting at 205O. Both substances, on complete hydrolysis, yield the dibssic acid, C,3H1G07,which melts at 231O. 328 339. ‘‘Solutions of halogen double salts in water and ether.” By James Ernest Marsh. The capability of the halogen double salts to give homogeneous solutions in a mixture of ether and water is limited, on the one hand, by the too great solubility of the salt in one of the solvents, and cin the other by the too slight solubility of the salt in both solvents.Sodium, potassium, rubidium, and barium mercuri-iodides give with ether and water homogeneous solutions, which on warming separate into three layers ;the lithium and ammonium salts are very soluble in ether with a little water, and leave the excess of water undissolved; the msium salt is only sparingly soluble, and has but little effect on a mixture of ether and watetr. Of the bromides, ammonium mercuribromide, and of the chlorides, lithium mercuri- chloride are the only inorganic salts of this sort which have been found to give homogeneous solutions, separating 011 warming into three layers.Potassium mercurichloride resembles cmium mercnri- iodide, and has but little action. Sofar as they have been examined, the sslts of primary ainines resemble the salts of ammonium, whilst tetrainethylammonium rnercuri-iodide resembles the czesium salt, and has even less action. 340. ‘‘ The relation between the absorption spectra of metallic ions and their valency.” By Cecil Reginald Crgmble. The absorption spectra of the aqueous solution of mom than thirty metals have becn examined. It has been found that the metals of constant valeiicy give solutions which are non-absorptive provided that a salt is employed, the acidic radicle of which is itself diactinic. On the other hand, the metals which vary in valency yield absorptive solutions.A conriexion has also been shown to exist between the absorptive properties of solution of metals and the chemical and physical properties of the rnetsls. 341. “The solubility of electrolytes in aqueous solutions. Part 11. Solubility of oxalic acid in other acids.” By James Irvine Orme Masson. In extension of previous work, which dealt with salts in acid solution (Trans., 1911, 99, 1132), measurements have been made of the solubility at 30° of oxalic axeid in solutions of nitric and of hydrochloric acids. In both cases the solubility falls to a minimum as the concentra- 329 tion of solvent acid rises, after which it increases. In nitric acid solutions this increase is terminated by conversion of the solid oxalic acid into the anhydrous: compound, the solubility of which then falls to a second minimum.The concentration of nitric acid at the transition point is about that of “ constant boiling point ” acid. The solubility curves of the dihydrate in both acids are conic in form, and in this respect resemble certain other solubility curves. The assumption of constant molecular volume in solution, which was found to be valid in the earlier cases studied, holds also in these iustances. Supplementary determinations were made with P-naphthalene-sulphonic acid in hydrochloric acid solution. The curve obtained resembles those for the salt-acid examples. 342. The determination of sulphur in petroleum.” By James McConnell Sanders.The llahler or Hempel calorimetric bomb method for estimating the total sulphur in petroleums, although trustworthy, is somewhat lengthy, since the gaseous combuskion products must be absorbed, and when samples poor in sulphur are under treatment, several combustions must be made. The Parr calorimeter is not available for petroleums on account of the small amount of sample which can be treated. ‘The author described a method by which a large sample may be concentrated by treatment with fuming nitric acid and potassium bromidel, the product being absorbed by magnesium oxide, which enables it to be readily removed from the concentrating dish, and burnt in the Parr apparatus with sodium peroxide. Several samples may he treated simultaneously, the final combustion taking about forty-five seconds.Test analyses were given, comparing results with the MahIer horrib method. For samples poor in sulphur a modified lamp method was described, in which a larger sample is completely burnt, thus avoiding the errors in the usual method owing to the sulphur being given off in an irregular manner. Some Mexican and Texan kerosenes contain loosely combined sulphur, which decomposes when heated or when in contact with some metals, such as copper; since samples have been known to blister, and even perforate, a copper lamp, the testing of commercial kerosenes for such unstable sulphur was recommended. The author described a qualitative and quantitative method for the purpose. For the manipulation of the small precipitates of barium sulphate obtained in these operations, the author described a rapid suction- 330 filter method, in which the amount of filter-paper is reduced to a minimum, and the weighing conducted in a very light dish.For the simultaneous treatment of several precipitates a special arrangement of the apparatus was described. ADDITIONS TO THE LIBRARY. 11. By Purchase. Nernst, Walter. Theoretical chemistry from the standpoint of Avogadro’s rule and thermodynamics. Revised in accordance with the sixth German edition by Henry Thomas Tizard. pp. xix+S10. London 1911. (Recd. 16/12/11.) Schidrowitz, Phaip. Rubber. pp. xv + 303. ill. London 191 1. (Becd. 20/12/ 1 1 .) Weimam, P. P. von. Grundziige der Disperaoidchemie. pp. viii+ 127. ill. Dresden 1911. (Red 16/12/11.) The nelxt Ordinary Scientific Meeting will be held on Thursday, January 18th, 1912, at 8.30 p.m. R. CLAY AND SONS, LTD., BRUNSWICK ST., STAMFORD ST., S.E., AND BUNOAY, SUFFOLK.
ISSN:0369-8718
DOI:10.1039/PL9112700323
出版商:RSC
年代:1911
数据来源: RSC
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