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Proceedings of the Chemical Society, Vol. 27, No. 393 |
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Proceedings of the Chemical Society, London,
Volume 27,
Issue 393,
1911,
Page 303-322
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摘要:
PROCEEDINGS OF THE CHEMICAL SOCIETY. VOl. 27. No.393. Thursday, December 7th, 1911, at 8.30 p.m., Dr. M. ONSLOW FORSTER,D.Sc., Ph.D.? F.R.S. (Vice-president), in the Chair. Mr. F. Thomas was formally admitted a Fellow of the Society. Certificates were read for the first time in favour of Messrs.: Hilmar Johannes Backer, D.Chem., 4, Upper Bedford Place, W.C. Ernest Arthur Bearder, M.Sc., Mayfield, Wythenshawe Road, Sale. Gibbs Blackstock, B.A., 79, Prince Arthur Avenue, Toronto. Frederic Feruandez Curtis, 20, Bury Street, Bloomsbury, W.C. Rowland Holliday Ellis, Hope Cottage, Brayton Road, Selby. Thomas Sidney Haines, 73, Kennington Avenue, Bristol. William McMillan, 72, Wellington Street, Greenock. Ernest Meyer Myers, c/o The Shelton Iron, Steel, and Coal Co., Ltd.,Stoke-on-T rent.William Johnson Smith Naunton, B.A., B.Sc., 1, New Street, Woodbridge. James Pettigrew Ogilvie, Homedale, Hendon Lane, Finchley, N. William Raitt, Dehra Dun, N.P., India. Walter Morrell Roberts, &I.Sc., The Cedars, Whalley Range, Manchester. 304 Bertram James Smart, B.Sc., Testing Office, Lithgow, N.S.W. Cecil Hamersley Waldron, 28, Hungerf ord Road, Camden Road, N. John Charles Withers, Ph.D., 83, Edgeley Road, Clapham, S.W. A ballot for the election of Fellows was held, and the following were declared subsequently duly elected : Arthur Cecil Bescohg, B.A. Gaston NiliB-Martin. Bertram Alfred I3ull. Thomas Peers Parkes, B.Sc. Joseph Beauchamp Bull. David Henry Peacock, R.A., B.Sc. Eiiwin Johnson Charlton, KSc.R. Venkata Rao, B.A. Barun Chandra Dutt, M.A. Percy James Raymond. Charles Christiau Gardthausen. Joseph Reilly, B.A. John Henry Garner, 13.S~. John Ffrdid Richardson. Arthur Josiah Hoffrneister Gauge. Noel Douglas Ridsdale. Rufus Gaunt, KSc., Ph. D. William Hristow Saville. Sydney Hall, B.SL Lionel Gowing-Scopeu. James Hogan Hill. Bernard Charlie Smith. Cyril Viri cent Hodgson, John Henry Smith. Henry James Hodsman, 14.Sc. George Alfred Stokes. Alexander Frederick Hogg, 111. A. Kapibram Hardevram Vakil, B. A. Sant Ram Khosla. Ernest Vanstone, B.Sc. Harold King, M.Sc. Alexey Mikhailovich Vassiliev. Geoffrey Martin, 81,Sc., Ph. D. Harry James Vipiid, B.A. Robert Mills. George M7ishard, B. A. BhAgavatula Viswa Nath.Ernest Walter Wright. Of the following papers, those marked * were read : *308. Chemical examination of the root of Ipomoea orizabensis.” By Frederick Belding Power and Harold Rogerson. The matierial employed for this investigation consisted of the root of Ipomoea om’zab ensis, Ledanoiis (Nat. Ord. Convolvdaceae), commonly known as ‘(Mexican Scammony Root.” The root contained 14.55 per cent. of resin, 71 per cent. of which was soluble in ether. After purification with animal charcoal, the resin was obtained nearly colourless. It then melted at 125-130°, and had [ajD-23*0°. For a complete examination of the root, 48-76 kilograms of the ground material were extracted with hot alcohol. The resulting extract, when distilled in a current of steam, yielded a small amount of a pale yellow essential oil.From the portion of the extract which was soluble in water the following compounds were isolated : (i) scopoletin, C,,H,O, ; (ii) 3 :4-dihydroxycinuamic acid, C,H,O,, from which the methyl ester (m. p. 158-160O) was prepared. The aqueous liquid con- 305 tained, furthermore, a quantity of sugar, which yielded d-phenyl- glucosazone (m. p. 205--206O), and from a portion of the original alcoholic extract a small amount of sucrose was also obtained. The portion of the alcoholic extract which was insoluble in water consisted of a resin which possased the abovementioned characters. This resin, by successive extraction with various solvents, was resolved into a number of products which were for the most part amorphous, and not entirely glucosidic, but by the further treat- ment of these products many well-defined substances were obtained.It has thus been shown that the resin is exceedingly complex in character, and it follows that the so-called “ jalapin,” which includes all those constituents of the resin which are soluble in ether, cannot be represented by any of the various formulz hitherto assigned to it. *309. The constitution of ergothioneine : a betaine related to histidine.” By George Barger and Arthur James Ewins. Ergothioneine, CSH,,0,N3S, a crystalline base isolated from ergot by Tanret in 1909, has been found to be a betaine of thiolhistidine (a-amino-P-2-thiolglyoxaline-4(or 5)-propionic acid).On boiling with 50 per cent. aqueous potassium hydroxide tri- methylamine is eliminated, and an acid, C6H6O&& (P-2-thiolgly-oxaline4(or 5)-acylic acid), is obtained. On oxidation with dilute nitric acid the latter yields P-glyoxaline-4( or 5)-acrylic acid, from which on reduction P-glyoxaline-4(or 5)-propionic acid is produced. The treatment of ergothioneine with ferric chloride leads to the formation of histidine-betaine. “310. The methane equilibrium.” By John Norman Pring and Dorian Macefield Fairlie. Carbon was heated electrically in hydrogen at definite known temperatures between llOOo and 2000°, and under pressures between 10 and 200 atmospheres. The velocity of the formation of methane was found to increase rapidly with the pressure, and to proceed to a final equilibrium stage.As would follow from the law of maSS action for a true equili- brium, the value of pC?H,/lp,(H,)2 was always found to be constant under different pressures if the temperature were the same, and the same modification of carbon used. With amorphous carbon, temporary equilibrium values were obtained, iri which at all temperatures the amount of methane was greater than that corresponding with the true equilibrium 306 with graphite. The relative difference between the equilibrium values for a.morphous carbon and graphite increases with the tem- perature. It follows from this, by applying Kirchhoff’s law, that the mean specific heat of amorphous carbon is, at all the tempera- tures concerned in this work, higher than that of graphite, and that the diff ereiice increases with the temperature.No appreciable effect was exerted by high pressures on-the yield of acetylene and ethylene, and no other hydrocarbon was formed. Ic31P. I‘ The decomposition of nitric acid by light.” By William Colebrook Reynolds and William Henry Taylor. The authors have investigated the decomposition of nitric acid by light, and find that the reaction is reversible, the products of decomposition slowly recombining more or less completely in the absence of light. The extent of the decomposition and recombina- tion was illustrated by a series of curves. They have proved that pure anhydrous nitric acid decomposes very slowly in the dark, giving the same products of decomposition. DISCUSSION.Dr. VELEYexpressed his satisfaction that the authors had amply confirmed the conclusion drawn from certain elementary experiments by Manley and himself (Phil. Trans., 1908, A, 191, 367) that the vapour of nitric acid rather than the liquid is decomposed by sunlight. The observations of the authors that the reaction, 4HN0, =2H20i-2h’,O, -+-0,, is reversible on alteration of condi-tions, appeared to be of especial interest, and was in accordance wibh results obtained in the study of other reactions in which nitric acid took part. More information might possibly have been obtained from the authors’ results if sunshine records had been given; although it was shown that the actinic effect of the sun was greater in August than in May, a.result to be expected, yet the difference found between the effects in May and March was almost inappreciable, a result contrary to general experience. Professor T. TURNERasked for information as to the method whereby the pressure in the tubes had been estimated, and how the gases were collected and measured. It was also suggested that: by means of a capillary tube closed at the upper end and inserted inside the closed tube, a continuous series of pressure observations might perhaps be taken, instead of only determining the final pressure at the end of the test. 307 Dr. SCOTTasked whether the authors had considered the possi- bility of traces, especially of hydrochloric acid and of iron, acting as catalysts.These and other substances which might act thus might conceivably come from the glass apparatus used. The curves of the pressures obtained with the various proportions of liquid and vapour space were remarkable in the case of a, reversible action. Mr. REYNOLDS,in reply to Dr. Scott, stated that it was possible that traces of iron and chlorine too small to be detected by the ordinary reagents were present in the acid employed through contact with glass. If such traces affected the results, it was, however, curious that the phenomena were so regular when different samples were employed, and that in clear silica tubes rather greater decomposition occurred than in glass; moreover, as only the vapolur waa decomposed, it was unlikely that iron affected the phenomena. "312.('Derivatives of o-xylene. Part I. 3-Nitro-~1-xgleneand 3 :6-dinitro-o-xylene." By Arthur William Crossley and Gertrude Holland Wren. 3-Nitro-o-xylene has been prepared from 3 :4-dinitro-o-xylene by reduction with stannous chloride to 3-nitro-o4-xylidine, and replacement of the amino-group in this substance by a hydrogen atom. A comparison of the properties of 3-nitro-o-xylene obtained in this way with the 3-nitro-o-xylene isolated from the products of the ation of a mixture of nitric and sulphuric acids on o-xylene (Tram., 1909, 95,208) showa that the latter contains some of the isomeric 4-nitro-o-xylene, probably about 7 per cent. 3 :6-Dinitro-o-xylene (compare Trans., 1909, 95, 210) has now been obtained in a pure condition from the products of direct nitration of o-xylene.It crystallises from alcohol in sheaves of needles, melting at 89-90°. "313. '' Derivatives of o-xylene. Part 11. Dinitro-o-xylidines." By Arthur William Crossley and George Francis Morrell. Attempts to prepare 3:6-dinitreo-xylene by conversion of 3:4 :6-trinitro-0-xylene into 3 :6-dinitrc~ol-xylidine and elimina-tion of the amino-group from this substance have been unsuc-cessful. The nitregroup in position 3 is the one attacked by reducing agents. 308 In the course of the experiments five of the six theoretically possible dinitro-o-xylidines have been prepared, and tJheir propertia CH3 CH3 CH3 /\cH, NO;\,)NO, NO,()CH, \/*=2 *H2 M.p.143”. NO2 M.p. 161”. NH2 31. p. 210”. M.p. 172”. &I.p. 143”. (1.1 were demribed. The missing 3 : 6-dinitro-o-4-xylidine(I)is the one which it was desired to prepare for the initial object of this research. DISCUSSION. Dr. MORGANdrew attention to the interesting analogy misting between the interaction of alcoholic ammonia and 3 : 4 : 5-trinitro-o-xylene and 3 : 4: 6-trinitro-o-xylene, whereby the mobile nitro- groups (4-N02 and 3-N02 respectively) were replaced by amhe groups, and the formation of aromatic mines from 1-chlore2 : 4-dinitrobenzene or 1: 2 : 4-trinitrobenzene, in which a mobile chloro- or nitrocradicle is directly replaced by an aminclgroup. This extreme mobility of the chloro- or nitrocradicle was conditioned by the presence of two other nitregroups in ortho-par* or di-orthe positions with respect to the reactive substituent (compare Hepp, Aden, 1882, 215, 363).314. The absorption of the halogens by dry slaked lime.” By William Arthur Reginald Wilks. It wm shown that bromine is absorbed from carbon tetrachloride solution by slaked lime (dried in a vacuum), with the production of an “adsorption compound,” which is brick-red. The colour of bromine bleaching powder” is due to this product. Iodine gives a similar adsorption compound, which is almost black. The concentrations of bromine in the solution (C2)and in the lime (C,) are connected by the formula 3= k, when n is one-c: third. The aidsorption of iodine obeys a similar formala, ~tbaing atill onethird, but the constant k has a value different from that of bromine.309 Adsorption phenomena could not be detected when chlorine was absorbed by dry slaked lime under the same conditions as before, but the results showed that in this case a chemical compound wtt9 formed. 315. “A method of determining carbon and nitrogen in organic compound^.'^ By Edward Percy Frankland. With reference to the author’s method for the simultaneous determination of carbon and nitrogen in organic substances (Tram., 1911, 99, 1783), his attention has been drawn to the fact that similar determinations were made by Klingemann (AnnuZen, 1893, 275, 92), using a gas apparatus for the estimation of nitrogen and carbon dioxide.Whilst aware that Dr. Klingemann had carried out an investigation on the production of nitric oxide during the combustion of nitrogenous substances in a vacuum (Ber., 1889, 22, 3064), the author regrets that he wi~snot previously cognismt of the fact that determinations of carbon in organic compounds had been made by the Frankland-Armstrong process, and that, there- fore, he was unable to make reference to Dr. Klingemann’s second communication on this subject. The author considers that the principal advantage of the process a5 described by him lies in the avoidance of all complicated apparatus for gas analysis, thus rendering the method of more general utility. 316. ‘‘Diphenylcyclopentenone.” By Siegfried Ruhemann and William Johnson S.Naunton. With the view of preparing cyclic triketones with three adjacent ketonic groups similar to triketohydrindene, 3 :4-diphenylcy clo-pentenone (Japp and Lander, Trans., 1897, 71, 131) was treated with p-nitrosodirnethylaniline. This reaction yields two condensa- tion products with two and three dimethylaminoanilegroupe respectively : flPh-$XN*C,H,*NMe, RPh.9:N*C,H,-N M e2 CPh CO and CPh C:N*C,H,*NMe, vC:N-C,H,*NMe, vC:N*C6H,*NMe2 Both compounds on hydrolysis with mineral acids yield 6-dirnethyZaminoanz20-3 :4-diphenylcyclopentene-l:2-dione : 310 which on heating with concentrated hydrochloric acid at 130-140° forms diphenylmaleic anhydride : 5 -Dimethylaminoanilo-3:Cdiphenylcy clopentene-1 :2-dione when treated with bromine gives a yellow bromo-derivative, C,H, 902N2Br, but with an excess of the halogen an unstable perbromide is produced, which on boiling with alcohol decomposes to yield the same yellow mouobromo-derivative along with a scarlet dibromo-compound, C,,H,8~2N2Br,.With fuming nitric acid the substance forms a scarlet dinitro-derivative, C,5H,802Nz(N0,)2;on reduction with zinc dust and acetic acid it furnishes a colourless compound, C25TI,202N,. 5-Dimethylaminoanib3 :4-diphenylcyclopentene-l : 2-dione is deep red or orange, according to whether it separates from concentrated or dilute alcoholic solutions. It forms salts, which, however, readily dissociate with water. It, further, has the remarkable property of being transformed into a colloid on the addition of water to its solutions in absolute alcohol or acetone.This spontaneously liquefies, with separation of crystals in the course of two or three day6. Neither the bromo-nor the nitrederivatives show this phenomenon. 317. (( Electrolytic reduction. Part V. Benzylidene bases.” By Herbert Drake Law. A series of compounds were reduced by the electrolytic metbod in continuation of similar experiments with the aromatic aldehydes. The results agreed closely with those previously obtained. Two classes of compounds were formed, according to the following general equations : R*CH:X +2H =R*CH2*XH. 2R*CH:X +2H= R*CH(XH)*CH(XH)*R. Thus benzylidene-p-toluidine yielded benzyl-p-bluidine, di-p-tolui- dinodibenzyl, and a green resin.The relative quantity of each constituent varied with the conditions of the experiment, but followed the same rules as those previously given in the case of benzaldehyde. The quantities of each substance formed varied very considerably with a change in constitution. The resin formed diminished as the formula of the reduced substance approached the most symmetrical arrangement of the substituted groups. 311 318. “The porosity of iron and its relation to passivity and corrosion.” By John Albert Newton Friend. The author showed that: (1) The surface of iron is slightly porous, so that when the metal is immersed in certain solutions the latter are absorbed to a minute extent. (2) The passivity induced by immersion of iron in alkaline solutions, such as those of sodium and potassium hydroxides, is due to absorption of small quantities of these alkalis within the pores of the metal.(3) There rare thus more kinds of passivity than one. 319. (* Molecular rotatory power in normal homologous series. Part I. Optically active derivatives of the higher aliphatic alcohols and acids.” By Thomas Percy Rilditch. The variation of different types of physical properties in consecu-tive members of an homologous series was discussed, and it was pointed out that whilst the more additive properties increase in arithmetical progression on ascending such a series, certain essen- tially constitutive properties tend in these circumstances to arrive at a constant value.A survey of the existing data on the molecular rotahry powers of optically active homologues shows that here also, although hitherto only the first few members of series of this type have been available, this function nevertheless reaches in many cases an approximately constant figure, characteristic of the opticdly active series concerned ;moreover, those series which do not yield constant values for [MID almost invariably contain strongly unsaturated groups. The author therefore proposes to investigate the homologues of higher molecular weight of some apparently irregular series, in order to determine whether the presence of unsaturation is here a disturbing factor in the lower members. To this end it was necessary in the first place to ensure that, in series the lower members of which rapidly attained constancy of molecular rotatory power, the homologixes of high molecular weight should maintain their “series constant ’I of molecular rotation. Investigation of the I-menthyl esters, and brucine and cinchonine salts of myristic, palmitic, and stearic acids, and of the hydrogen camphorates and camphor-B-sulphonates of cetyl and myricyl alcohols, showed that, within narrow limits, the molecular rotatory powers of the normal aliphatic esters of I-menthol, d-camphoric acid, and d-camphor-P-sulphonic mid, and of the normal aliphatic salts of brucine and cinchonine become numerically constant in each series after the first few members are passed.312 320. 6c Molecular rotatory power in normal homologous series.Part 11. The menthyl esters of the a-bromoaliphatic acids.” By Harold Christopher and Thomas Percy Hilditch. The effect of introducing an unsaturated group in close proximity to the carboxyl residue of a series of optically active normal aliphatic esters has been studied by the authors in connexion with the problem of the disturbing effect of unsaturation referred to in the preceding paper. The a-bromo-derivatives of the aliphatic esters of I-menthol were eaployed in the present investigation on account of the ease with which these compounds may be obtained in the pure condition. It was found that whilst the first two members of the series (menthyl bromoacetate and a-bromopropionate) pmsessed molecular rotatory powers markedly above the normal, the anomaly rapidly declined to a minimum, slightly sub-normal value, thereafter rising very much more gradually to an approximately constant value (in the case of menthyl a-bromomyristate and a-bromopalmitate).The final constant molecular rotations appeared to be a very few degrees in excess of those of the corresponding members of the saturated, non-substituted aliphatic menthyl esters. 321. cc Note on methyl-n-tridecyl- and methyl-n-pentadecyl-carbinols and the corresponding ketones.” By Robert Howson Pickard and Joseph Kenyon. In a recent communication (Trans., 1911, 99, 45) the authors have described the resolution into their optically active components of the members of the series of carbinols from methylethylcarbinol to methyl*-undecylcarbinol.It was intended to continue the aeries so as to .include methyl-n-tridecyl- and methyl-n-pentadecyl- carbinols, but it has been found that the method of bringing about the resolution of the various members of the series fails in the cme of these caibinols, containing fifteen and seventeen carbon atoms respectively. This note contains a short description of the compounds isolated during the course of the experiments, and also shows that the catalytic method with thorium oxide (Senderens, Compt. rend., 1909, 149, 995) can be used for the formation of ketones, even when they contain many carbon atoms. Methyl-n-fridecyl Retone, CH,*CO-C,,H2,.-Myristic acid (300 grams) dissolvsd in glacial acetic acid (2400 grams) was passed at an hourly rahe of 50 C.C.through a Jena-glass tube containing thorium oxide, and heated to 400O. The products of the reaction were condensed, dir-lsolved in ether, and washed with a solution of sodium hydroxide until free from acid. Myristic acid (125 grams) 313 WZLSrecovered from the washings, mixed afresh with glacial acetic acid, and again treated. When the products from the two opera- tions were fractionally distilled, 200 grams of methyl-n-tridecyl ketone were obtained. The residue in the flask when rec-qstallised from ethyl alcohol yielded 30 grams of myristone, which melted at 75-76O. Methyl-n-tricZecyE ketone boils at 184O/20 mm., and on cooling sets to a soft mass of crystals, which melt at 37O.It readily forms the senticarbazone, which crystallises from ethyl alcohol in needles melting at 126.5O. (Found, N=15*0. Calc., N=14*8 per cent.) Methyl-n-tridecykarbinol, CH,*CH(OH)*C13H27,is readily ob-tained when the corresponding ketone is reduced by sodium in 96 per cent. alcoholic solution, little, if any, pinacone being formed. It boils at 181--183O/19 mm., and on cooling sets to a crystalline mass, which melts at 38-39O. The hydrogen prhthdate * crystallises from light petroleum in pearly leaflets, and melts at 61-62O. The brucine salt crystallises from acetone in needles, which, when dried in the air, melt at 80-85O, but after desiccation in a vacuum or after heating at 105O for a few minutes they melt at 172-175O.After two recrystdlisations, on poiarimetric examination : 1.01363, made up to 20 C.C. with ethyl alcohol, gave a -6*25O, whence [a] -61'66O. The strychnine salt crystallises from chloroform and acetone in hair-like needles, melts about 130°, and has; [aID -52'6O when dissolved in chloroform. The hydrogen phthalate obtained from the purest specimen of these saltswas in each case found to be quite inactive when examined in the polarimeter. The hydroyen succimte crystallises from light petroleum in nacreous leaflets, which melt at 60-61O. The brucine salt is a wax, and unsuitable for fractional crystallisation. The corresponding derivatives of heptadecane were obtained by similar methods. Seventy-nine grams of methyl-n-pentadecyl ketone, CH3*CO*Ci,H31, were obtained from 112 grams of palmitic acid.It boils at 197O/ 12 mm., crystallises from ethyl alcohol in pearly leaflets melting at 48O, and can be regenerated unchanged from the semicarbazone, which crystallises from dilute ethyl alcohol in very small needles melting at 125'5O. Mat~tyZ-n-~eittaciecyZcar73inolboils at 230°/ 16 mm., forms inde- finitely shaped crystals, and melts at 46O. The hydrogen phthalate * The purity of each of the acid esters described in this note was ascertained by titration of their alcoholic solutions with a standard solution of sodium hydroxide. 314 Beparates from light petroleum as a mass of needles, which melt at 50-5lc. The hydrogen szcccznate separates from light petroleum in a microcrystalline condition, and meits at 64-65O.The bmcine salts of each of the esters were prepared and recrystallised several times, but no ester could be obtained which exhibited any trace of optical activity. 322. (‘An experimental investigation of the bleaching process.” By Sydney Herbert Higgins. Solutions of the hypochlorites of lithium, sodium, and potassium prepared from bleaching powder solution by precipitation with solutions of the alkali sulphates or carbonates have identical bleach- ing properties; the bleaching efficiencies of these solutions are almmt equal to that of the original bleaching powder solution. Curves showing (1) the evolution of oxygen from hypochlorite solutions and from solutions of sodium peroxide in contact with copper oxide; (2) the rate of bleaching of solutions of hypochlorites and of sodium peroxide, (3) the rate of oxidation of oxalic mi bypotassium permanganate and the rate of liberation of iodine from potassium iodide by acidified sodium peroxide solution (Harcourt and Esson, Phil.Trans., 1866, 156, 193), point to the conclusion that the actions in all these cases are similar, that is, unimolecular. Hypochlorites therefore bleach because of their readiness directly to produce nascent oxygen. Those substances which accelerate the evolution of oxygen from solutions of hypochlorites or of peroxides also assist the evolution of that gas when they are heated along with potassium chlorate; hence it is taken that the main action in the latter caseis a unimolecular one. Chlorine water is a much weaker bleaching agent than solutions of hypochlorites ; therefore the bleaching action of the latter cannot be due to the generation of free chlorine as stated by Taylor (Trans., 1910,97,2541).Chlorine water probably owes its bleaching properties to t.he presence of hypochlorous acid in solution. The proof that the production of chlorine from bleaching powder solution and the stimulation of the bleaching action of that solution have no comexion with one another has led the author to consider the two questions separately. In pursuit of this line of argument he gave further experiments supporting previous conclusions (compare Taylor, this vol., p.243). 323. (‘The direct esteriflcation of saturated and unsaturated acids.” By Ebenezer Rees Thomas and John Joseph Sudborough. The esterification of a number of saturated and unsaturated organic acids has been studied by heating the acid with a large 315 excess of pure ethyl alcohol at looo in sealed tubes for given periods, and titrating the amount of free acid left. The results show that an ab-oleiine linking has a retarding effect, except when the unsaturated acid is a very much s$ronger acid than its saturated analogue, for example, methyl hydrogen maleate, which is some two hundred times as strong an acid as methyl hydrogen succinate. In such a case the olefinic acid is esterified more rapidly than the corresponding sat.urat.ed acid.A &unsaturated acid is usually esterified somewhat more rapidly than its saturated analogue, and a yZ-olefinic linking appears to have but little effect on the rate of esterification. The influence of substituent,s in both saturated and unsaturated acids is marked. 324. “The influence of three- and four-membered carbon rings on the refractive and dispersive power of organic compounds.’’ ByGustaf Jim Ostling. The molecular refraction 2nd dispersion of several derivatives of cydopropane and cyclobutane have been determined and calculated according to the formula : The cyclopropane derivatives were tanacetone and its derivatives, esters of carbonic acids, a new hydrocarbon, namely, 1 :2-dimethyl-cyclopropane, and some others.The cyclobutane compounds were chiefly esters of various acids. It was shown that (1) the three- as well as the four-carbon ring exerts an influence on the molecular refraction. The increment in the case of a three-carbon ring is for Ma+0.67 and for M, + 0.71 ; in the case of a four-carbon ring for Ma+ 0.45 and for 91, + 0.48. (2) A small exaltation is noticeable when the thee-carbon ring is conjugated with a double bond (EZ D= -+ 6.2). (3) The three- and the four-carbon rings have practically no influence on the molecular dispersion. (4)The conjugation of a three-carbon ring and a double bond increases the molecular dispersion about 10 per cent. The magnetic rotatior! for a saturated tricyclic terpene, /3-pinolene, has4 also been determined.hb325. Contributions to our knowledge of semicarbazones.” (Bre-liminary note.) By Isidor Morris Heilbron and Forsyth James Wilson. In the course of some recent experiments the autlmrs observed that m-nitrobenzylicienedeovybellzoill on treatment with semicarb- 316 azide acetate formed two distinct semicarbazones, a colourless and a yellow modification. The addition of sodium hydroxide solution. to an alcoholic solution of either the colourless or the yellow form produced an intense yellow coloration, which was destroyed by acids. As semicarbazones have not as yet been very fully studied, the authors are extending their observations to semicarbazones derived from both saturated and unsaturated ketones and aldehydes. Phenyl styryl ketone gives on direct treatment with semicarbazide acetate two distinct semicarbazones : a colourless form, melting at 168O, which is rapidly precipitated from a dilute alcoholic solution, and a more soluble yellow form obtained by dilution of the mother- liquors.On attempting t30recrystallise this yellow modification from chloroform, the authors found that it passes into a third modification, which crystallises in colourless, silky needles melting at 180O. This semicarbazone in the dry state is unstable, being gradually reconverted on exposure to diffused sunlight into the yellow modification. KO melting point for this yellow form can be obtained, as it passes when heated above 160° into the colourlesa modification melting at 180°.Alcoholic solutions of both colourless semicarbazones give with sodium hydroxide intensely yellow products, which are still under investigation. The absorption spectra of these various semicarbazones are being investigated in the hope of throwing further light on the subject. It has also been found that semicarbazones of both saturated and unsaturated aldehydes and ketones are affected by ultraviolet light, stereoisomerides being apparently produced in some cases, decomposition products in others. Investigations in this direction are also in progress. 326. ‘(Conductivity and dissociation of diacetyltartaric acid.” By Stella Deakin and Albert Cherbury David Rivett. Diacetyltartaric anhydride is hydrated too rapidly for the course of the action to be followed by the conductivity method (compare Rivett and Sidgwick, Trans., 1910, 93,732, 1677).Since some con- nexion appears to exist in such a case between rate of hydration and first dissocia-tion constant of the acid, a determination o’f the latter was desirable, and has been made, giving the value 2.5 x 10-2, a higher figure than is given by the acid corresponding with any anhydride the rate of hydration of which has been measured. The second dissociation constant approsirnates to 0.11 x 317 327. A synthesis of ‘thioindigo.’” (Preliminary note,) By William George Prescott and Samuel Smiles When 0-thiol- or o-dithio-benzoic acid is treated with malonic acid or its ester in the presence of warm concentrated sulphuric acid a vigoroils reaction occurs, and (‘thioindigo ” is formed.From pre- liminary experiments the yield of the latter subst?ance appears to be as high as about 85 per cent. of the theoretical, exclusive of thioindigosulpboiiic acid which is simultaneously produced. Traces of hydroxybenzothiophen were also isolated. There is no doubt %hat the preliminary stage of the interaction depends on the forma- tion of the sulphoxylic acid (Trans., 1911, 99, 640), which then reacts as follows : “ZHcf3R4<~oH + CH,(CO,Et), = C6H,<y>C(C0,Eb)2 +2H,O. Condensation of these thio-acids with ethyl acet,oacetate, substi- tuted malonic acids, and similar substances may also be effected; these interactions are now being more closely invest,igated.$28. Asymmetry in the supposed absence of an asymmetric atom.” ic By James Ernest Xarsh. Everest’s paper (this vol., p. 285) disposes effectively of the claim that a new type of asymmetry exists which is not dependent on the presence of an asymmetric atom in the molecule. At the same time the views of Everest involve him in a difEculty of another kind: in the conversion of the unsaturated acid into its dibromide, the asymmetric carbon atom (1) is represented as losing ik asymmetry, while a new asymmetric carbon atom (7) is created in a different part d the molecule outside the ring: c%+>C<QH2* CH,>C=C<;O,H (1) CH,*CH, (4) (7) CO,H Perkin, Pope, and Wallach, in stating (Proc., 1909,25,83) that the constituticmal formula of the unsaturated acid (( compriw no atom which cam be described as asymmetric, no matter which definition of an asymmetric atom be adopted,” have overlooked the definition given by the author (Phil.Mag., 1888, [v], 26, 426). He there defined an aqmmetric carbon atom m one which, when replaced by ita image, gives a formula different from the original formula. This idea involved the consideration of an atom isolated from the 318 rest of the molecule, and was justified in view of van’t Hoff’s theory (Rix Anntes, etc., 1887, pp. 27 and 28) that the tetrahedron the centre of which is occupied by the carbon atom acquires an asym- metric form owing to: the effect of four different affinities on it; thus the asymmetrically deformed atom can be considered apart from the particular groups to which it is attached.The groups may be four or less, according as the atom is situated in open-chain or in one or more rings. The atom being asymmetric will have il non-supeqmable image. The replacement of the atom by its image was represented in the author’s paper as brought about by an exchange of position of two of the groups attached to the atom. The same inversion may be done by flyping the tetrahedron (that is, by turning it inside out), a process applicable to the stereocentric benzene formulz, and one which affords a simple explanation of the phenomenon called the TValden inversion. In this method of treatment there is no need for a kind of dissection of a formula, as employed by Everest to prove four different groups, a process which must become difficult when there are several asymmetric atoms in the molecule.The views expressed in the author’s paper lead to the conclusion that the methylcyclohexylideneacetic acid has three asymmetric carbon atoms in the molecule (l),(4), and (7), and that all three remain asymmetric in the bromine additive compound. The exchange of position of any two groups or linkings attached to C (1) in either acid gives a formula different from the original one, being, in fact., that of the optical isomeride. The case is the same with C (4) and C (’7). The unsaturated acid is certainly a compound of a novel type, in that with three asymmetric carbon atoms there are only two possible isomerides, and those enantio- morphous.A somewhat similar example of a limited isomerism is that of the trihydroxyglutaric acids, where also with three asymmetric carbon atoms there are only two isomerides which are here optically inactive (without including the active forms which have only two 3symmetric atoms). Perkin and Pope (Trans.,1911, 99, 1510) claim that in the methylcyclohexylideneacetic acid ‘‘the optical activity is due to the enantiomorphous configuration of the molecule as a whole.” This is certainly true, not only of this acid, but of every optically active substance whatever, and the author stated it in the paper already mentioned. The converse has also proved true that unless the molecule as a whole is asymmetric it will be optically inactive, however many asymmetric atoms it may contain.The term “centmasymmetry ” is therefore not only unnecessary, but mislead- ing; and van’t Hoff’s original propositilon with regard to carbon 319 still holds good, that every optically active compound has an asp-metric atom in the molecule, although the presence of asymmet,ric car Son does not II ecessarily involve optical activity. 329. (‘Latent heats of vaporisation of mixed liquids. Part 11.” By Dan Tgrer. In continuation of previous investigations (Trans., 1911, 99, 1633) it was pointed out that a mixture of two liquids has really two latent heats, namely, (1) heat absorbed when 1 gram of the mixture vaporises at constant temperature and pressure from an infinitely large quantity of the mixture of known composition.It is supposed that no change in the composition occurs in this process. (2) Heat absorbed when 1gram of a mixture is completely vaporised at constant temperature. If x is the composition of the liquid in (1) and y the composition of the vapour which leaves it, and if y is also the composition of the 1 gram of liquid in (2), then it can be easily shown that: (LP>s=(W,+H, where Lp and Lc are the two latent heats respectively defined above, and H is the heat developed when 1 gram of the mixture of com-position y is added to an infinitely large quantity of the liquid of cornposition x. Values of Lp for several mixtures have been experi- mentally determined, and also the compositions y of the vapour boiling off from mixtures of known compositions, and from this data values of Lc have been calculated.It was shown that whilst the results for Ly do not appear to bear any simple relation to the compositions of the mixtures, those for Lc follow Trouton’s equation : LCLU15? =constant, where LW is the mean moiecular weight of the mixture and T is the temperature. 330. (‘Influence of double linking on optical activity.” By Percy Faradag Frankland and Hugh Henry O’Sullivan. The authors have compared the relative rotatory effects of the ally1 and ?i,-propyl groups in the following pairs of compounds : In liquid state. [Mly.Meuthoxyacetic allylaniide ............... -192.5” Menthoxyccetic n-propylamide ..........193.7 Ally1 menthoxyacetate ..................... 234.4 n-Propyl menthoxyacetate ............... 234.1 Menthyl allylaminoacetate .............. 160‘5 Menthyl n-propylaminoacetate ......... 158’3 320 The differences in molecular rotation are thus very small; indeed, in the case of the allyl and propyl menthoxyacetates t,he allyl has slightly the higher rotation at low temperatures and the propyl compound at high temperaturw. In the case of the allyl- and propyl-amides of t.artaric and malic acids previously investigated by one of the authors (Trans., 1906, 89, 1854 and 1861), the differences in rotation mere much more pronounced, and in both instances the propyl compound had the higher rotation, thus : In pyridine solution./ . [M]:O‘. [q0”. Tartaric. Jla!ic. Allylamide ............... +251 -72.70 n-Propylamide ......... -t289 -90 3 These greater differences in rotation in the case of the tartaric and malic compounds are probably due to there only being three intervening atoms between the unsaturated and the asymmetric carbon atoms, whilst in the above menthyl compounds there are in all cases five intervening atoms between the unsaturated carbon atom of the allyl and the nearest asymmetric carbon of the menthyl gr*UP* 331. cc The action of aliphatic amines on s-dibrornosuccinic acid. Part I.” By Edward Percy Frankland and Henry Edgar Smith. The authors have prepared the dipropylamino- and dibutylamino- succinic acids, R*NH*(?H*CozH by t.he action of It-propylamineR*NH*CH*CO~K’ and mbutylamine respectively on s-dibromosuccinic acid in alcoholic solution. The reaction appears to proceed in a manner analogous to that described by E.P. Frankland (Trans., 1911, 99, 1775) in the case of benzylamine and s-dibromosuccinic acid. The alkylamino- acids yield copper salts, hydrochlorides, and dinitrosderivatives. 332. “The velocity of the reaction between iodic and sulphurous acids in vaxions media.” By Thomas Stewart Patterson and William Collins Forsgth, The influence of methyl alcuhol, ethyl alcohol, n-propyl alcohol, and of acetone on the velocity of the reaction between iodic acid and sulphurous acid was described. 321 ADDITIONS TO THE LIBRARY. I. Donations. Braccesco, Gioranni.La esyositione di Geber Filosofo . . . , nella quale si dicbiarano molti nobilissimi secreti della Natura. In Vinegia appremo Gabriel Giolito d6 Ferrari 1562. pp. 160. (Reference.) From Dr. J. N. Goldsmith. Dunstan, Albert Ernest, and Thole, Ferdinand Bernard. Textbook of practical chemistry for technical institutes. pp. viii + 335. ill. London 1911. (Recd. 16/11/11.) From the Publishers : Meesrs. Methuen & Co., Ltd. Espagnet, Joanne8 d’. Das Geheime Werck der Hermetischen Phil oeophie, Worinnen die natiirli chen und kunstlichen Geheim nusse der Naterie dee Philosopbischen Steins, wie auch die Art und Weise zu arbeiten richtig und ordendlich offenbahret sind. pp. [xi‘] + 90. [Wanting pp. 37-38, 71-72 and 87-88.] Leipzig 1685.(Reference.) From Dr. J. N. Goldsmith. Royal Society of London. Catalogue of a collection of early printed books in the Library. pp. 120. London 1910. (Recd. 20/11/11.) 11. By Puvchase. Barthel, Chr. Methods used in the examination of milk and dairy products. Translated by T. Goodwin. pp. xi+ 260. ill. London 1910. (Hecd. 20/11/11.) Blount, Bertram, and Bloxam, Arthur George. Chemistry for engineers and manufacturers. 2nd edition. 2 vols. pp. xii + 392, xv +513. ill. London 1911, 1910. (Recd. 17/11/11.) Bottger, WiZhelm. Stand und Wege der analytischen Chemie. (Die cbemische Analyse, Vol. XIII.) Stuttgart 191 1. (Recd. 24/11/11 .) Hober, RudoZf. Pbysikalische Chemie der Zelle und der Gewebe. 3rd edition, pp. xv+ 671. Leipzig 1911.(Recd. 25/11/11.) Rideal, Samuel. Disinfection and the preservation of food. Together with an account of the chemical substances used as anti- septics and preservatives. 3rd edition. pp. xii + 494. ill. London 1903. (Recd. 17/11/11,) Ubbelohde, L., and Goldschmidt, J’. Handbuch der Chemie und Technologie der Ole und Fette. Vol. 111, part 2. pp. xiv+381 to 1195. ill. Leipzig 1911. (Recd. 24/11/11.) 322 At the next Ordinary Scientific Meeting on Thursday, December 2lst, 191 1, at 8.30p.m., the following papers will be communicated: “Investigations on the dependence of rotatory power on chemical constitution. Part 11. The rotations of some secondary alcohols containing the isopropyl group.” By R. H. Pickard and J. Kenyon. (‘The alcohols of the hydroaromatic and terpene series. Part 11. The menthols corresponding with optically inactive menthone.” ByR.H. Yickard and W. 0. Littlebury. “The absorption spectra of quinine, cupreine, 6-methoxyquinoline and 6-hydroxyquinoline.” By J. J. Dobbie and J. J. Fox. R. CLAY AND SONS LTD.. BRUNSWICK ST., STAMFORD ST., S.E., AND BUNGAY, SUFFOLK.
ISSN:0369-8718
DOI:10.1039/PL9112700303
出版商:RSC
年代:1911
数据来源: RSC
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