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Proceedings of the Chemical Society, Vol. 19, No. 263 |
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Proceedings of the Chemical Society, London,
Volume 19,
Issue 263,
1903,
Page 71-80
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摘要:
Iwued 31/3/03 PROCEEDINGS OF THR CHEMICAL SOCIETY. VOl. 19. No. 263. Wednesday, March 1Sth, 1903. Professor J. Emerson Reynolds, Sc.D., F.R.S., President in the Chair. Messrs. J. M. Wadmore, J. Phelps, and F. Soddy were formally admitted Fellows of the Society. Certificates were read for the first time in favour of Messrs. William Lester St. John Alton, Dungarvan, Putmey Heath, S.W. Henry Gough, c/o. Messrs. J.Lovibond & Sons, Ltd., Greenwich, S.E. William Kirkby, Winster House, Thornfield Road, Heaton Moor. John George Collcutt Lock, 17 Berners Street, W. George G. Pond, M.A., Ph.D., State College, Pennsylvania, U.S.A. Robert James Porter, 11, Arlington Street, Hull. Ernest William Sawdon, B.Sc., 2, Esk Terrace, Whitby. Giles Hadden Welsford, 6, The Orchard, Blackheath, S.E.The PRESIDENTstated, in reference to a petition which had been recently presented to the Council, that he had the authority of the Council to communicate to the Society the terms of the petition 72 and of the resolution of the Council with regard to it, The terms of the petition were : "We, the undersigned Fellows of the Chemical Society, being of opinion that the interests of the general body will be promoted by limiting the period of service of the Honorary Secretaries and Foreign Secretary, do hereby request the Council to earnestly consider the desirability of so limiting the tenure of office." The resolution passed by the Council nem. con., which was duly communicated to Mr. C.E. Groves, who represented the petitioners, was "That this Council is of opinion that the tenure of office of the Officersof the Society should not be indefinitely extended, but that it is not desirable to limit the period by assigning a definite term of years to the tenure of each office." Of the following papers those marked * were read :-"45. "Essential oil of hops." By A. C. Chapman. Since the publication of the earlier results of the study of oil of hops (PToc.,1893, 177 ;Trans.,1895, 67,54, and 780), three more samples of oil of undoubted genuineness have been examined. These had ,the following specific gravities and specific rotations ; Sp. gr. 15"/15". Sp. gr. 20"/20". [4]~00*No.5............... 0.8676 0.8645 +0*303 No.6..............0.8639 0.8610 -0.20' No.7............... 0*8403 0.8357 -0.08' The fraction of lowest boiling point, obtained after prolonged frac- tional distillation under reduced pressure, consisted of a hydrocarbon ClOHIS,which had the following properties : sp. gr. 0.8046 at 15'/15O and 0.8020at 2Oo/2O0; b. p. 74-75" (33 mm.) and 166-168' (774 mm.), undergoing at the same time slight polymerisation. It was optically inactive and had a refractive index 1.4645 at 20' and a molecular refraction 46.8, the calculated number for CloHl, (with 3 double linkings) being 46.78. This compound is therefore an aliphatic hydrocarbon, and its properties are almost identical with those of myrcene ;it absorbs oxygen from the atmosphere and readily under- goes polymeric change, becoming converted into a colourless resin.The next fraction (b. p. 120-130°, 46 mm.) was a very small one, and gave on analysis numbers agreeing with the formula C,,H,,O. It had a sp. gr. 0.8571 at 2Oo/2O0, produced a rotation of -0'40' in a 73 100 mm. tube, and evidently consisted of inactive linalool mixed with a small quantity of some active substance. The third small fraction (b. p. 135-150°, 46 mm.) consisted of an ester, and yielded on saponification isononoic acid, C,H,,O,, and linalool, together with a small quantity of geraniol. The highest and largest fractions in all three samples of oil con-sisted of nearly pure humulene. On submitting the oil to the action of boiling chromic acid mixture, it yielded acetic, valeric, succinic, un-symmetrical dimethylsuccinic (m.p. 140°), and isononoic acids, the last of these having been probably derived from the linalyl ester. When dilute nitric acid was employed in the oxidation, oxalic and acetic acids were the chief soluble products of acidic character. Oxidation experiments made with the fractionated constituents of the oil showed that the dimethylsuccinic acid is derived from the humulene, and succinic acid from the myrcene. The essential oil of hops therefore contains the following compounds: myrcene, humulene, linalool, linalyl isononoate, with small quan-tities of a diterpene and probable traces of some ester of geraniol. In all the freshly distilled samples of oil examined, the hydro- carbons myrcene and humulene mere present to the extent of from 80 to 90 per cent.DISCUSSION. Dr. POWERremarked that the results obtained by Mr. Chapman seemed to leave no doubt respecting the identity of the hydrocarbon of low boiling point contained in hop oil with the myrcene of oil of bay. Attention was also called to the fact that, apart from the interest connected with the general properties of myrcene and the occurrence of such an olefinic terpene in nature, it has recently been utilised in a study of the chemical composition of Para rubber, Harries (Ber., 1902, 35, 3259) has shown that when rubber is treated with nitrous acid it yields a series of nitrosites, one of which has the molecular composition (C,,H,,07N3)2,and appears to be identical in overy respect with a nitrosite obtained from a product of the polymer- isation of myrcene termed dimyrcene, C,,,H,,.It is thus rendered probable that myrcene stands in very close relationship to isoprene and caoutchouc. In reply to Professor Tilden, Mr. CHAPMANsaid that he had not obtained any evidence of the existence of pinene in the oil, The slight optical activity was, in all probability, due to the presence of a small quantity of active linalool, but the intermediate fractions were so small, even when working with considerable quantities of the oil, that it was impossible to arrive at a definite conclusion in regard to this point. 74 *46. (‘A compound of dextrose with aluminium hydroxide.” ByA.C. Chapman. The author has obtained a compound of dextrose with aluminium hydroxide by the following process. To a solution of 8 grams of pure anhydrous aluminium chloride in about 1500 C.C. of 90 per cent. alcohol, powdered dextrose was added until it no longer dissolved after allowing the mixture to remain some time in a warm place. The white, gelatinous precipitate immediately produced by adding aqueous ammonia in slight excess to the filtered solution was collected, washed with 90 per cent. alcohol, and dried until of constant weight in an exhausted desiccatcjr over sulphuric acid. It was not found possible by repeated washing to remove the last trace of chlorine, a small quantity invariably remaining, apparently in the form of a basic chloride.By careful treatment it is, however, possible to obtain a preparation which, after drying, will not contain more than 0.2 to 0-5 per cent. of chlorine. Many different preparations of this compound were made with slightly varying proportions of dextrose and aluminium chloride. The analytical results, although fairly concordant, do not correspond with any simple formula : (1) 0.6010 gave 0.376 CO, and 0.276 H,O. C=17*06;H=5*10. (2) 0.4270 ,, 0.275 CO, ,, 0,196 H,O. C=17*56;H=5*08. (3) 0.4135 ,, 0.264 CO, ,, 0.185 H,O. C=17*41; H=4*96. (4) 0.6010 ,, 0.250A1,0, ; Al=22*01. Three other estimations gave A1 = 22.12,22.18,and 22.34. [3C,Hl,0,,5Al,0,,11H,0]requires C = 17.39; H= 4.67; A1= 21.80 per cent. From these results, it appears probable that the white, flocculent precipitate is a compound of 3 mols.of dextrose with 5 mols. of aluminium hydroxide [3C,Hl,0,,5A1,(OH),], and that this compound, when dried in an exhausted desiccator over sulphuric acid, loses approximately 4 molecules of water (compare Zbam., 1889, 65, 576 ; 1891,59,224). This aluminium compound is a white, amorphous substance, insoluble in water and alcohol, but dissolving in dilute acids. It differs from the similar compounds of dextrose with the oxides of iron and chromium in being insoluble in water when freshly precipitated ; with boiling water, it undergoes partial decomposition into aluminium oxide and dextrose. On drying for some hours at looo, the substance lost 12 per cent.of its weight and acquired a pale yellow colour, but did not char appreciably at this temperature; it burned with extreme readiness when heated more strongly, yielding a mixture of the metallic oxide mixed with carbon, the final residue after prolonged ignition consisting of aluminium oxide. "47. Action of phosphorus haloids on dihydroresorcins. Part 11. Dihydroresorcin." By A. W. Crossley and P. Haas. Dihydroresorcin behaves towards phosphorus haloids in a similar way to its dimethyl derivative (Tkmas., 1903, 83, llO), in fact, as if it possessed the following formula :CH2<Crr;.C(oH)>CH.CH -GO 5-ChZwo-3-keto-A4-tetruhydrobenzene, CH -COCH2<cH~.c-,l>CH, obtained by the action of phosphorus trichloride on dihydroresorcin, is a colourless, highly refractive liquid boiling at 104' (24 mm.) ;it gives a semicarbuzide melting at 190° and on oxidation is converted into glutaric acid.The corresponding brorno-derivative boils at 132.5-1 33O (52 Em.). Phosphorus pentachloride gave rise to 3 :5-dichloro-A2"%&ihydro-benzene, CH2<~~~~$X3H,a colourless, refractive liquid boiling at S8-90° (29 mm). On treatment with excess of phosphoruspentachloride or with bromine, it was converted into m-dichlorobenzene, and on reduc-tion with sodium in moist ethereal solution, yielded a mixture of di- and tetra-hydrobenzenes. This mixture of hydrocarbons readily absorbed two atoms of bromine, and the resulting liquid deposited crystals of dibromodihydro6enZene,C,H,Br,, which separated from light petroleum in transparent, hexagonal prisms melting at 104*5O,and decomposing at 1'70" with evolution of hydrogen bromide.*48. The constitution of cotarnine." By J. J. Dobbie, A. Lauder, and C. K. Tinkler. Although previous investigators are in agreement as to the possible existence of the carbinol form of cotarnine, the question as to whether this constitution or one expressed by an open chain formula should be assigned to solid cotarnine has hitherto remained unsettled. A satisfactory answer has now been furnished by the study of the absorp- tion spectra of this substance and its derivatives. Solid cotarnine begins to undergo a constitutional change as soon as it comes into contact with water or alcohol, but is not altered either by ether or chloroform, and the spectra of the ethereal and chloroform solutions, which may therefore be regarded as the true spectra of cotarnine, 76 agree perfectly with one another and also with those of hydrocotarnine and its salts; moreover, they are identical with those of the cyanide and ethoxyhydrocotarnine, these substances having been regarded as derivatives of the carbinol form.The spectra of dilute aqueous or alcoholic solutions of cotarnine and those given by a solution of cotarnine hydrochloride from which the chlorine has been removed by means of silver oxide are almost iden- tical with the spectra of cotarnine hydrochloride, which, on the other hand, differ widely from the spectra of cotarnine in ether.Cotarnine and all its derivatives hitherto examined spectroscopically conform to one or other of these two forms of spectra. (i) The spectra of cotarnine in aqueous or alcoholic solution and of cotarnine salts show a large amount Gf general absorption with two well-marked absorption bands, one of which is close to the visible region, (ii) The spectra of cotarnine in ether or chloroform, hydrocotarnine, ethoxy- cotarnine, and cotarnine cyanide show less general absorption than the former, and have a band much further removed from the visible region, The substances in the first class are yellow, those in the second are colourless; the latter can all be represented as having a carbinol constitution. When cotarnine is dissolved in anhydrous alcohol, it changes from the carbinol to the quaternary ammonium hydroxide form, CH(OH)*TMe --f.II <CH=rMe-OH CSW,< CH,-CH, CH,*CH, ’ the rearrangement being promoted either by increasing the mass of the alcohol present or by heating. The transformation is effected much more rapidly by methyl than by ethyl alcohol. A colourless solution of cotarnine in alcohol cannot be obtained, but, since this isomeric change proceeds slowly, it is possible in ethyl alcohol, by photographing the freshly prepared solution immediately, and again after successive intervals of time, to trace the transforma- tion through all its phases. The rate of progress of the change may even be determined by comparing photographs of the alcoholic solution with those of the spectra of mixtures of the solutions of the hydro- chloride (ammonium form) and the cyanide (carbinol form) in known proportions.Potassium, sodium, and barium hydroxides, and even ammonia, promote the reverse change to that effected by alcohol. When cotarnine hydrochloride in solution is decomposed by sodium hydroxide, the cotarnine changes at once to the carbinol form, but if an aqueous solution of cotarnine is treated with successively larger quantities of this alkali, the reverse change is gradual, and, as in the case of the opposite change induced by alcohol can be distinctly traced through its various phases, These results explain several of the peculiarities observed by Hantzsch and Kalb (Ber., 1899, 32, 3109) in their experiments on the conductivity of cotarnine.Preliminary experiments indicated that similar results are given by hydrastinine. DISCUSSION. Mr. BALY said that an interesting comparison could be drawn between these absorption spectra of cotarnine compounds and those obtained by Hartley and Dobbie with derivatives of o-oxycarbanil. In the latter case, the lactam esters correspond to the derivatives from the ammonium hydroxide form of cotarnine and the lactim esters to the derivatives from the carbinol form. The absorption spectra of the lactim esters of o-oxycarbanil and of the ammonium hydroxide form of cotarnine both have more general absorption with the absorption band nearer to the visible region than in the case of the spectra of the lactim esters of o-oxycarbanil and the carbinol form of cotarnine.This contrast appears to be the opposite of that observed in the keto- and enolic forms of carbon compounds. Dr. ORTONasked whether the addition of a small quantity of alcohol to the ethereal solution of cotarnine, in which the alkaloid was present in the carbinol (or pseudo-ammonium) form, effected a complete conversion of the carbinol into the true ammonium base; or was, on the other hand, a point of equilibrium reached which was only displaced by addition of a further quantity of alcohol? As the presence of small quantities of bases such as piperidine has such a marked influence on similar isomeric changes, preventing the change of a non-basic into a basic substance and facilitating the reverse process, it would be of interest to know whether any similar observations on the transformation of cotarnine under the influence of alcohol had been made.In reply to Mr. Baly, Professor DOBBIEstated that no such general relation between the absorption spectra of lactams and lactims, as seemed to be implied in the question, had been established. With reference to Dr. Orton’s question, he stated that the amount of change produced by sodium hydroxide in an aqueous solution of cotarnine was found to be proportional to the quantity of caustic alkali added, when the solution was examined immediately after the addition of this reagent. The effect of time on the alkaline solution had not yet been fully investigated.“49. 6LDecompositionof mercurous nitrite by heat.” By P. C. RSy and J. N.Sen. When mercurous nitrite was decomposed by heat in a tube con-nected with a Sprengel pump, nitric oxide escaped mixed with very little nitrogen peroxide, crystals of mercurous nitrate were pro-jected across the upper and cooler part of the tube, just over the decomposing salt, a very little metallic mercury and its basic nitrate were deposited at the sides, whilst a small quantity of amorphous, orange-coloured mercuric oxide was left in the place of the decomposed nitrite. Except when the greater portion of the nitrate which had formed at first had been decomposed by heating more strongly, the average amount of nitric oxide produced corresponded with only 3.3 out of the 5.7 per cent.of nitrogen contained in the nitrite. The production of mercurous nitrate was evidently due to inter- action between nitrogen peroxide and mercury vapour, nitric oxide being the other product. In decomposing, the mercurous nitrite behaves partly as if it had a non-oxylic constitution in yielding mercury and nitrogen peroxide, and partly as if it had an oxylic constitution in giving rise to mercuric oxide and nitric oxide. DISCUSSION. Dr. DIVERSsaid that the authors’ observation of the conversion into crystals of mercurous nitrate of the nitric peroxide and mercury vapour coming from the mercurous nitrite was very interesting and recalled the production of crystals of mercurous chloride from a mixture of mercury vapour, air, and hydrochloric acid, which occurred in the manufacture of that substance in the old Japanese way.It also strikingly confirmed, as the authors had pointed out, the accuracy of the account of the decomposition of silver nitrite, given by Shimidzu and himself years ago. He considered the authors to be mistaken as to the origin of the small quantity of mercuric oxide, which was always produced. That this formed just where the mercurous nitrite had lain was not that the nitrite bad directly decomposed into mercuric and nitric oxides, but that, by the use of a small flame as applied, this spot was the only part of the tube sufficiently hot to bring about the well-known decomposition into this oxide of the mercurous nitrate which was forming out of the gas and vapour, equally and as much here as in the upper and cooler part of the tube.79 50. “The action of nitrogen tetroxide on pyridine,” By J. F. Spencer. In attempting to nitrate pyridine, the author studied the action of nitrogen tetroxide on this base, and although nitropyridine was not isolated an isomeride was produced. The nitrogen tetroxide, which was prepared by the direct combination of nitric oxide and oxygen, mas employed either in the gaseous form or as a liquid at low tempera- tures; but these variations of the experimental conditions did not materially affect the course of the reaction, which gave rise to the same product whether the base was treated alone or in the presence of various solvents.The first product is an unstable, white, crystalline compound which mas ihown by analysis to be an additive compound of pyridine and nitrogen tetroxide. The further action of the latter reagent led to the production of a solid, black substance, which, when treated with water, entirely dissolved, yielding a brownish-red solution ;this solu- tion, on further dilution, gave a yellow, amorphous deposit (i) amount- ing to about 4 per cent. of the pyridine taken. The filtrates, when rendered alkaline, furnished 70 per cent, of unaltered pyridine, but no other basic substance. If, however, the alkaline solution was acidified, it gave a purplish-brown precipitate (ii), the composition of which was not determined. (i) The yellow product, which is insoluble in all the ordinary organic solvents except pyridine, dissolves in mineral acids or aqueous alkalis forming deep red solutions ; when rapidly heated, it decomposes explosively at 234’; on distillation with zinc dust, it yields pyridine : 0.1986 gave 0.3530 GO, and 0.0568 H,O.C =48.66 ;H= 3-19. 0.0691 ,, 13.44 C.C. moistnitrogenat 13’ and764.6 mm. N=22*77. C5H,02N2 requires C =48-38 ;H =3-22 ;N =22.58 per cent. These resuIts were confirmed by many additional analyses. The hydrochloric acid solution of this substance yielded a platinichloride containing 13.53 per cent. Pt. Calculating the molecular weight of the polymeride from thisresult, the value 521 is obtained; this corre- sponds with the molecular formula (C5H402N2),,which has a molecular weight 496.All attempts to depolymerise this substance failed ; mild reducing agents had no action, although tin and hydrochloric acid reduced it to a basic compound, the platinichloride of which contained 31 -49 per cent. Pt, whilst (C5NH4*NH,),H,PtC16 requires 32.6 per cent. Pt. (ii) The purple substance somewhat resembles the yellow compound, but is evidently more complex. 80 The unsatisfactory yields and the highly complex nature of the products have rendered it impossible to pursue this investigation. ADDITIONS TO THE LIBRARY. I. Donations. Reynolds, Osborne. The sub-mechanics of tho universe. Published for the Royal Society of London. Cambridge 1903. From the Author. Weinberg, Boris.L’enseignement pratique de la physique dans 206 lnboratoires de l’Europe, de l’Amerique, et de 1’Australie. Odessa 1902. From the Author. Henri, Victor. Lois ghdrales de l’action des diastases. Paris 1903. From the Author. Plimmer, Robert Henry Aders. The chemical changes and pro- ducts resulting from fermentations. London 1903. From the Publishers. Nilson, Lars Fredrik, and Jolin, Severin. Minnesfesten ofver Berzelius den ‘7 Oktober 1898. Beskrifning p%uppdrag af kungl. vetenskaps akademien. Stockholm [1901]. From the Academy. Clowes, Frank, and Coleman, Joseph Bernard. Quantitative chemical analysis, adapted for use in the laboratories of colleges and schools. 6th ed. ill. London 1903. From the Publishers. At the next ordinary meeting, on Thursday, April 2nd, 1903, at 8 pm.,the following papers will be communicated : (I On the absorption spectra of nitric acid in various states of con-centration.” By W. N. Hartley. I( The dioximes of camphorquinone and other derivatives of isonitroso- camphor.” By M. 0. Forster. (6 Salts of a mercaptoid isomeric form of thioallophanic acid, and a new synthesis of iminocarbaminethioalkyls.” By A. E. Dixon. ‘6 Discoloured rain.” By E. G. Clayton. (6 Derivatives of o-aminobenzophenone and p-aminobenzophenone.” By F. D. Chattaway. 6‘ Reversibility of enzyme or ferment action.” By A. C. Hill. P.. CLAY AXD SOXS, LTD., BitEAD ST. HILL, E.C., AND RONGAY, SUFFOLK.
ISSN:0369-8718
DOI:10.1039/PL9031900071
出版商:RSC
年代:1903
数据来源: RSC
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