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Proceedings of the Chemical Society, Vol. 25, No. 354 |
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Proceedings of the Chemical Society, London,
Volume 25,
Issue 354,
1909,
Page 81-100
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摘要:
Zssued 2613109 PROCEEDINGS OF THE CHEMICAL SOCIETY. Pol. 26 No.354. Thursday, March 18th, 1909, at 8.30 p.m., Sir WILLIAMRAYSAY? K.C.B., F.R.S., President, in the Chair. Messrs. F. P. Dunn, J. T. Furnell, J. H. Jeffery, P. May, A, ii. Robertson, and W. 0. Wootton were formally admitted Fellows of the Society. Certificates were read for the first time in favour of Messrs. : Albert Riley Blackburn, B.Sc., Marshville, Derby Road, Widnes, Lancs. Walter Campbell, Albert House, Westcliff-on-Sea, Daniel Little Couch, 9, Charlmont Road, Tooting, S.W. Edward Gordon Couzens, B.Sc., 47, Allfarthing Lane, Wandamorth. Francis Clifford Dyche-Teague, B.Sc., 8, Mount Road, Hendon, N.W. Charles James Grist, Apsley House, Banstead, Surrey. Leonard Angelo Levy, B.A., B.Sc., 60, Priory Road, West Rampstead, N.W.Robert Miiller, Royal College of Science, South Kensington, S.W. Frederick Leigh Okell, c/o Straits Trading Co., Singapore. John Webster, 44,Holmewood Gardens, Brixton Hill, S.W. A Certificate has been authorised by the Council for presentation to ballot under Bye-law 1(3) in favour of Mr.: Henry Ernest John Bletcher, Winnipeg, Manitoba. The PRESIDENTannounced that those Fellows desirous of supporting the International Memorial to the late Marcelin Berthelot should forward their subscriptions to M. H. Bocquillon-Limousin, 2BisRue Blanche, Paris. Of the following papers, those marked * were read : "76. '(Liquid and solid radium emanation.'' By Robert Whytlaw Gray and Sir William Ramsay, K.C.B.In the course of some recent work on radium emanation, the authors have prepared this gas in a state of fair purity, and it appeared worth while trying to liquefy it by pressure. It was therefore introduced into a very fine-bore capillary tube of 0.08 mm. diameter, fitted in a com-pression apparatus of the kind used by Ramsay and Young, and com- pressed to a smaller volume. When sufficiently small, there was seen at the conical point of the tube a minute column of liquid, easily visible under low microscopic power. By altering the volume, more or leas liquid could be condensed. In short, by transmitted light all the usual phenomena of condensing and evaporating a liquid were observed. The liquid is colourless, and indistinguishable from water, or from, say, liquefied argon or xenon.If,however, the illumination from behind be extinguished, and the tube be viewed by its own illumina-tion, even in broad daylight, the liquid is visible as a greenish or bluish-green phosphorescent layer, not very luminous, but more luminous than the gaseous layer. Its vapour pressures were measured at -12.8O and 16.2O (atmospheric temperatures), and 47' (boiling point of carbon disulphide). But the gas was not quite pure; pressure rose during condensation. All0 wing approximately for this, Ramsay and Young's rule was made use of to calculate the vapour-pressure curve. The pressures and temperatures are as follows : P. T. 1 P. P. 100 mm. -74.5" 1000 mm. -43.1" YY200 -66.1 .-31 '0 '9500 -53.6 -12.8 760 -48'5 10,000 ,' +1.5'9 These vapour pressures must be taken as only approximate.The density of the liquid could be estimated, too, with rough approximation, as about 7, assuming that of the gaseous emanation to be 100 times that of gaseous hydrogen; it is considerably higher than that of xenon, namely, 3.52. This liquid, as remarked, is only feebly phosphorescent. But if cooled by touching the tube with cotton-wool moistened with liquid (melting point of ice), 0' sulphur dioxide), of(boiling point 10" 83 air, it turns brilliant; the colour changes to a bright steel-blue, and it blazes with light. Continued application of liquid air changes the colour, first to white, then to yellow, and finally to orange. Through the microscope it looks like a brilliant little arc light.On removing the liquid air, the reverse change occurs; the orange light becomes yellow, then white, and then blue; and there seems to be some sort of disturbance in the tube, as if crystals of a solid were disintegrating ; then appears the faintly phosphorescing liquid, and if the volume be large enough, the still more faintly phosphorescing gas. Trans-mitted light shows merely a colourless liquid, as before. These changes can be reproduced again and again; they were exhibited to several persons in the laboratory. There is no doubt that the substance which is brilliantly luminous is a solid. In Nabre (1909, 79, 457), Professor Rutherford describes experi- ments in which he obtained such I‘ a brilliant point of phosphorescent light ” ; and he measured the temperature at which the ‘‘ initial con- densation of the emanation ” occurred at atmospheric pressure ; he found it to be -65O.Inthe light of the above experiments, it is difficult to say what he was observing; probably, the solidifying point of the emanation, although he speaks of having seen ‘‘ small drops of liquid emanation on the walls of the capillary.’’ “77. gb Optically active Substances which contain no asymmetric atom.” (Prelimhaq note.) By William Henry Perkin,William Jackson Pope, and Otto Wallach. The possible existence of optically active substances which contain no asymmetric atom in the molecule was foreseen many years ago by van’t Hoff, but the attempts hitherto made to obtain such com-pounds have been unsuccessful.All the constitxhional formula at present assigned to substances which exhibit optical activity in the liquid state indicate the presence of one or more asymmetric atoms in the molecule. Some time ago Perkin and Pope (Trans., 1908, 93, 1082) synthesised 1-methylcycZohexylidene-4-aceticacid, and pointed out that, on the basis of the tetrahedral environment of the carbon atom in methane, this substance possesses an enantio-morphous molecular configuration, and should hence exist in optically active forms. The constitutional formula, however, comprises no atom which can be described as asymmetric, no matter which definition of an asymmetric atom be adopted.The authors have now succeeded in separating from the synthetic and optically inactive acid a pure optically active modification of 1-methylcyclohexylidene-4-aceticacid by the method described below. To a hot aqueous solution of two molecular proportions of externally compensated sodium 1-methylcyclohexylidene-4-acetateis added a hot aqueous solution of very slightly less than one molecular proportion of brucine hydrochloride ;during admixture alcohol is added in just sufficient quantity to prevent the solution becoming turbid owing to separation of an oily salt. On cooling and scratching with a glass rod, rather less than one-half of the acid separates as crystalline brucine laevo-l-met]&ylcyclohexylidene-4-~cstccte, C,~H,,O,N,,O,H1,0,, 2H20, whilst most of the dextro-component of the acid remains in solw tion as sodium salt.After crystallisation from dilute alcohol to remove adherent mother liquor, the pure salt is obtained in colourless needles melting at 97'; it shows the specific rotatory power [a], -58.1' in a 0.8 per cent. alcoholic solution. lsvo-l-Methylcyclohexy~~dsrae-4-aceticacid is obtained from the brucine salt by addition of hydrochloric acid to its hot aqueous solution ; after crystallisation from light petroleum'the optically active acid melts at 52*5*, and shows the specific rotatory power [a]=-81' in alcoholic solution. On treatment with fuming hydrobromic acid it yields the potentially inactive 4-bromo- 1-methylcyclohexyl-4-acetic acid, CH cH2*cH2>CBr*CH,*C02H,G>C<CH,*CH, which mehs at 78O.DISCUSSION. Dr. TUTTOKasked whether Prof. Pope had been able to measure the crystals, and if so, whether he had found$hem to belong, as usual in cases of optical activity, to one of the eleven enantiomorphous classes which exhibit lower symmetry than the maximum symmetry of their system. Dr. MCKENZIEreferred to the work of Marckwald and Meth in this connexion. Reference was also made to the fact that the configurations assigned to the active inosites represent these compounds as not possessing an asymmetric atom. Replying to Dr. Tutton, Prof. Pope stated that attempts were being made to examine derivatives of the active acid goniometrically in order to ascertain whether Pasteur's law holds in connection with the crystalline form of substances which owe their optical activity to the new kind of asymmetry now discovered.In reply to Prof. Armstrong, it was observed that although the molecule contains no asymmetric atom, an asymmetric system forms part of the molecular configuration, and that the optical activity arises from the enantiomorphism thus introduced. In connexion with Dr. McKeuzie’s remarks, Prof. Pope observed that no doubt can now exist that the acid described by Marckwald as 1-methylcycZohexylidene-4-aceticacid is really 1-methylcycZohexene-4-aceticacid, the molecule of which contains an asymmetric carbon atom. The configuration assigned to inosite certainly contained asymmetric carbon atoms.‘78. “The constituents of the rhizome of Apocynum androsaemi-folium.” By Charles Watson Moore. The material employed in this investigation was the rhizome of Apocynum androsaenaifolium, LinnB. An alcoholic extract of the rhizome, when distilled in a current of steam, yielded small amounts of an essential oil and acetovanillone. The non-volatile constituents of the rhizome, as obtained after treating the alcoholic extract with steam, consisted of a brown resin (A) insoluble in either hot or cold water; a brown resin (B) soluble in the hot aqueous liquid, but which was slowly depoeited on standing ;and material which remained dissolved in the cold aqueous liquid. The brown resin (A) yielded small quantities of ipuranol, C,H3,0,(0H), (m.p. 285-290°), and acetovanillone ;palmitic, stearic, oleic, and linolic acids, and n large quantity of unsaponifiable material. From the latter, two new alcohols, nndrosterol, C,,H,,*OH (m. p. 208-2 lo’), and Aomo-mdvosterol, C,7H,3*OH(m. p. 192’), were obtained, whilst the presence of a third alcohol was proved by the isolation of its brornoacetyl derivative (m. p. 265-268”). Androsterol yields an acetyl derivative (m. p. 212-214O) and a rnonobromoacetyl derivative (m. p. 228-230’). AcetyZAomoandrosterol melts at 236’. The brown resin (B) yielded a further small quantity of acetovanillone. The portion of the alcoholic extract of the rhizome which was soluble in cold water, and from which the abovedescribed resins had been removed, contained large amounts of sugar and tannin.It yielded a quantity of aceto-vanillone (m. p. 115), which was also present in the form of its glucoside, androsin, CH,*CO*C,H,(O-CH,) * 0-C,H,,0,,2H20 (m. p . 2lS-220°), and a new substance, apocynummm, C,sH,,06,2H,0 (m. p. 170-175”), which possesses an intensely bitter taste, is highly toxic, and represents the chief active constituent of the rhizome. 86 “79. The action of phosphorus pentachloride on the methglene ethers of catechol derivatives. Part IV. Derivatives of di-hydroxyphenyl-acetic, -glycollic, and -glyoxylic acids.” By George Barger and Arthur James Ewins. Starting from ethyl 3 :4-methylenedioxymandelate, which is more readily obtained from piperonalcyanohydrin than the corresponding acid (previously obtained by Lorenz, Ber., 1881, 14, 793), the authors have prepared a number of methplene ethers and cyclic carbonates related to 3 :4-dihydroxymandelic acid, C,H,(OH),*CH(0H)*C02H, and to 3 :4-dihydroxyphenylglyoxylic acid, C6H3(OH),*CO*CO,H, and also these acids themselves. 3 :4-Dihydroxymandelic acid and its derivatives are very soluble in water, quite unlike epinephrine (adrenaline), which also contains the complex C,H,(OH),*CH(OH)*.Dihydroxymandelic acid is much less htable than the corresponding keto-acid. “80. “Studies in the azine series. Part I. The constitution of safranine.” By John Theodore Hewitt, Sidney Herbert Newman, and Thomas Field Winmill. Phenosafranine has the composition of a salt (chloride) of phenyl-phenazonium.According to Bernthsen the two amino-groups are symmetrically situated, whilst Witt supposed that one was in the phenyl group, only one being attached to the phenazine nucleus. The question was apparently decided in favour of Bernthsen’s formula by Karner and Schraube, who obtained identical dialkylsafranines by the oxidation of (a)one molecule of as-dialkyl-p-phenylenecliaminewith two molecules of aniline, and (b) one molecule each of p-phenylenediamine, aniline, and its dialkyl derivative. More recently P. Barbier and P. Sisley (Ann. Chirn. Phys., 1908, [viii], 13, 96) have stated that phenosafranine, as prepared by oxidising p-phenylenediamine with aniline, consists essentially of the asymmetric compound mixed with small amounts of an isomeride having the structure given by Bernthsen.The present authors find that the hydroxyaposafranone obtained from safranine is identical with that prepared by Jaubert’s method from nitrosophenol and rn-hydroxydiphenylamine (Ber., 1895, 28, 273), since the acetyl derivatives prepared from both specimens melt at 271O (uncorr.) whether alone or mixed (Fischer and Hepp give 265-268’ : Ber., 1897, 30, 401). The synthesis of an asymmetric phenosafranine by oxidation of aniline with 2 :4’-diaminodiphenylamine described by Barbier and Sisley (Zoc. cit., p. 102) could not be realised, any safranine obtained by them probably owing its origin to admixed 4 :4’-diaminodiphenyl-amine, since potassium dichromate converts 2 :4’-diaminodiphenpl-amine into aminophenazine whether aniline be present or not.The experiments recorded are only compatible with the symmetrical (Bernthsen’s) formula for phenosafranine. “81. ‘-The condensation of amides with esters of acetylenic acide.” By Siegfried Ruhemann. Ruhemann and Nerriman (Trans., 1905, 87, 1383) have shown that acetylacetone condenses with phenylpropiolyl chloride to a yellow furfuran derivative (I); this readily changes into its red isomeride (11),which, with bases, forms blue salts, and with hot sodium carbonate yields a colourless acid (111) isomeric with (I)and (11). These changes mere represented thus : CHPh:y-CO>cAc -~ fi(OH)*CO yPh:y*CO,H>CAC ---0-CMe CPh-CMe CMe:CAc (1.) (11.1 (111.) The correctness of these formuh follows from the fact that ethyl phenylpropiolate condenses with sodiobenzamide to a coloured compound, CIGHl,O,N(dark red needles, m.p. 184O), which, with alkalis, forms blue salts; the substance which is to be regarded g(OH)’cO>N or co*c(oH)>N, shows in as dip~~enyklik~topyrk~ne, CPh=CPhCPh--CPh I its properties and structure a striking resemblance both to the compound (11) and the similarly const,ituted substances (see Ruhemann and Merriman, Zoc. cit.) and to isatin. On boiling with potassium hydroxide, it decomposes quantitatively into ammonia, oxalic acid, and deoxybenzoin. DISCUSSIOX. Dr.HEWITTfully agreed with Dr. Ruhemann that in the compounds he described the sodium probably attached itself to an oxygen atom.He ventured to suggest this might be equally well expressed by a rearrangement of the conjugate double linkings as by the formation of a. bridged ring. *82. Studies in asymmetric synthesis. Part VII. The influence of the d-amyl group.” By Alex. McKenzie and Hermann August Xtlller. The action of magnesium organic compounds on cl-amyl pyruvate and d-amyl benzoylformate respectively has been examined. The asymmetric synthesis of &-lactic acid by the reduction of d-amyl pyruvate was described. It appears that the more optically active is the directing asymmetric agent the more pronounced is the asymmetric synthesis. Attempts to substitute gallic acid for 3-nitrophthalic acid in order to effect the separation of cZ-amyl alcohol from fuse1 oil were not successful.”83. LL Contributions to the chemistry of cholesterol and coprosterol.” By Charles Dorge. The author has investigated the action of ozone on the following cholesterol derivatives : cholestenone, the acid C27H,404,/3-cholestanol, coprosterol, $-coprosterol, and the ketones corresponding with these and a-chole&anol. All of these with the exception of a-cholestanol, which is indifferent,react with ozone, and the determination of the ozone numbers of these eompounds confirms generally the view of Nolinari (Ber., 1908, 41, 2782) that a second double linking is present in the cholesterol molecule. For this there is no other chemical evidence, and the addition of the second molecule of ozone has now been shown to take place with considerable difficulty, so that this may not be a case of simple addition, hut of a development of some grouping in the molecule under the influence of ozone with subsequent addition.Reasons were given for. ascribing to the compound previously obtained by the action of phenylhydrazine on coprostanone (Tram., 1908, 93,1627) a constitution of the carbazole type. A crystalline nitrosite was prepared and analysed. 84. ‘‘Iodine dioxide.” By Matthew Xoncrieff Pattison Hnir. Reference was made to the work of Millon, in 1844, and of Rammerer, in 1861,on an oxide of iodine said to be composed of iodine and oxygen united in the ratio of I :20, none of which work satis- factorily proved the existence of the compound.The compound 10,, or P,O,, has been prepared by the dehydration and partial deoxidation of iodic acid by heating that acid with concentrated sulphuric acid. Two methods of analysing iodine dioxide were described. It was shown that the interactions of this oxide and oxalic acid, in the presence of sulphuric acid, at looo, and with boiling water, are severally represented by the equations : (1) I,o, +4C2H20,=I, +4H204-8C0, and (3) 5120, +4H,O =8HI0, +I,. Iodine dioxide is a pale yellow, crystalline solid of specific gravity 49;it is decomposed at about 130' into iodine and oxygen. The molecular weight of the compound has not been determined. The reactions of the oxide with acids and with various reagents were described ;in most of these interactions, iodine pentoxide and iodine are produced.Iodine dioxide is slightly soluble in cold concentrated sulphuric acid ; 100C.C. of the acid dissolve 1.54 grams of the oxide at 15' to 20'. Inasmuch as iodine dioxide forms a compound with sulphur trioxide having the composition I,O,,3SO3, the oxide has dightly basic properties. This compound is not decomposed by heating to loo', but begins to give off iodine, oxygen, and sulphur trioxide at about 120'. Incidentally, it was shown that iodic anhydride and sulphur trioxide combine, when heated together at looo, to form a compound which has the composition I,0,,2503. The slightly basic characters of the two oxides of iodine emphasise the connexions between iodine and manganese.85. ''A polarlmetric method of identifying chitin." By James Colquhoun Irvine. A solution of chitin in concentrated hydrochloric acid is slowly transformed into glucosamine hydrochloride at the ordinary temperature. The change is greatly accelerated by keeping the solution at 45O,being then complete in eight to ten hours. Under these conditions, the hydrolysis is quantitative, no humic compounds or other colouring matters are produced, and thus the reaction may be followed polarimetrically. As chitin is hvorotatory, the conversion into glucosamine hydrochloride is accompanied by a characteristic ''inversion," the average result (calculated on the initial concentration) being : [a]'? -14.1' -+ [a12 +56.0°.The results obtained showed great uniformity, n'nd thus the method can be applied as a test for chitin, which is capable of positively identifying 0.1 gram of the substance. The constancy of rotatory power observed with specimens of chitin 90 prepared from widely different sources affords strong evidence that the substance is a definite compound of uniform composition and structure. As '' spongin " and '' keratin " did not show any optical inversion during hydrolysis, it seems doubtful if these substances are in any way related to chitin. The different formulae suggested for the latter compound have been examined in their relationship to the polarimetric results, the best agreement being given by the expression (C30H50019N4)n,in which aminoglucose and acetylaminoglucose residues are present in the proportion of one to three.86. ''The conversion. of d-a-rnethylisoserine into d-a-methylglyceric acid." By Francis William Kay. In the course of investigating the action of nitrosyl bromide on the P-amino-acids, it was found that a-methyliaoserine (P-amino-a-hydroxy -isobutyric acid) was converted into P-bromo-a-methyl-lactic acid (P-bromo-a-hy droxyiuobutyric acid), which melts at 102-1 03" (uncorr.), and has already been described by Melikoff (AnnaZen, 1886, 234, 213) : NH,*CH;CMe(OH)*COzH 2%CH,Br*CMe( OH)*CO,H. d-a-Methylkoserine by a similar treatment yields d-P-bromo-a-methyZ-Zactic acid, which crystallises from benzene in needles, m. p. 114' funcorr.), and has [a]? + 7-40°in approximately 10 per cent.aqueous solution. The action of the theoretical amount of alcoholic potassium hydroxide (2 mols.) converts the above bromo-acid into potassium d-a-metiaylglycidate, pCH,Br*CMe(OH)*C0,H -+ O<CMe.2 CO,K. This salt crystallises in silvery leaflets, and has [a]: -11.57". When potassium d-a-methylglycidate is heated with water to ZOO', it undergoes hydroxylation and is transformed into potosskwn d-a-methytglycercde: pO<CM 2e*C0,K -+ OH*CH,*CMe(OH)*CO,K The aqueous solution of this salt has a specitic rotation of -4°000. 87. The action of steam on iron." (Preliminary note.)By John Albert Newton Friend. The author has studied the action of steam on iron at temperaturerr ranging from looo to a red heat.It is found that pure, carbon 91 dioxide-free steam has no action on pure iron until those tempera- tures are reached at which the steam begins to dissociate, when a black oxide (presumably Fe,O,) is produced. The conclusion is drawn that the usual statement that steam is decomposed by red-hot iron is not true. The reaction really takes place in two stages, involving (i) the dissociation of the steam, and (ii) combination of the iron with the dissociated oxygen. 88. 6G The constitution of sulphurous, sulphuric, carbonic, and formic acids." By John Albert Newton Friend. In a recent communication, Miss Smedley (Traias., 1909, 95, 231) has discussed the constitution of the carboxyl group, and incidentally suggests that carbonic, sulphurous, and sulphuric acids may be represented by the schemes : n fi HO-C-OH HO-S-OH HO--S--OH 9 '.\., I* '\\..I 0'/ and \/\/ .'0 00 The instability of the first two acids is attributed to the symmetrical arrangement of the third atom of oxygen between two hydroxyl groups. Tbe present author considers, however, that such an explanation is not. sufficient, Arguing along similar lines it would be expected that an acid containing a fourth atom of oxygen between three hydroxyl groups would be too unstable to exist, but orthophosphoric acid, PO(OH),, is comparatively very stable. Evidence has already been adduced (Friend, Trans.,1908, 93, 266) to show that the molecules of sulphur di- and tri-oxides are most probably correctly repregented by the schemes : and -o=s //O j 9 UO where the thick lines represent the free valencies, and the thin,jthe latent valencies.Since the latent valencies of the third oxygen atom in the trioxide are unsaturated, the latter readily combines with water to form a stable hydrate, which then undergoes more or less complete rearrangement to sulphuric acid until equilibrium is attained : Since the hydrate is exceedingly stable, there is little tendency for 92 the reactions to proceed from right to left ; heme the stability of the sulphuric acid. With sulphur dioxide, however, the case is different. The latent valencies of the two oxygen atoms mutually saturate each other, and there is little tendency for a hydrate to form; hence equilibrium is obtsined according to the following schemes : SO,+H,O SO0\O:H, O=S, /O-H/Iu,/ 0-H when only a small quantity of the hydrate is present, and the relative concentration of the sulphurous acid can therefore never be great.This would account for the instability of the acid, and the fact that its solution exhibits all the properties of the dioxide. It might appear at &st sight that, since sulphur dioxide is unsaturated, a hydrate of the tYPe H,O-r =SO, might be formed. This is, however, not possible, as the free valencies of the sulphur are positive, whereas one of the latent valencies of the oxygen is positive and the other negative (Friend, Zoc. cit.). Carbon dioxide and carbonic acid may be represented by the schemes : ,O-H 0-H’ and a similar explanation for the instability of the acid holds.In formic acid a carboxylic group is present, and the latent valencies of the two oxygen atoms mutually satisfy each other, thus : H--C---O-H That carbon monoxide does not dissolve in water to form formic acid is explained by the fact that the free and latent valencies of the oxygen atom saturate the four free valencies of the carbon atom, a saturation which is rendered possible bF the amphoteric nature of the latter (Friend, Zoc. cit.); hence it is not until some vigorous method is adopted for breaking this connexion, as, for example, the action of the gas on heated potassium hydroxide, that formic acid can be prepared. 89. “The formation and reactions of imino-compounds.Part IX. The formation of derivatives of cyclopentane from a8-dicyano-derivatives of butane.” By Stanley Robert Best and Jocelyn Field Thorpe. When ethylene dibromide reacts with dry ethyl sodiocyanoacetate (compare this vol., p. 17) in benzene solution, ethyl a$dicyanoadipate 93 (I) is formed, and this compound is readily transformed into ethyl carbonate and ethyl 2-imino-3-cyanocyclopentane-l-carbox:yZate(11),from which 1-imino-2-cyanocyclopentnne(HI)can be easily obtained. vH,*CH(CN)*CO,Et YH,--CH(CN) >C:NHCH,*CH(CN)*CO,Et, CH,*CH( C0,Et) (1.1 (11.) i. (111.) These imino-compounds are hydrolysed by cold miaeral acids, yielding ethyl 5-cyanocyclopentan-l-one-2-carboxylat~(IV) and 2-cyano-cyclopentan-1 -one (V) respectively, whilst further treatment with acids yields, in both cases, cyclopentanone (VI).YH,---CH(CN) FH,*CH(CN) $?H,*CH,>coCH,*CH( C0,Et) CH,-CH, >c* CH,*CH, (IV.) (V.1 (~71.) Themethylation of ethyl 5-cyanocyclopentan- 1-one-2-carboxylate (JV) leads to the formation of ethyl 5-cyano-5-msthylcyclopentan-1-OM-2-carboxylate (VII) and ethyl 5-cyano-2 :5-dimethylcyc1openta~-1-om-2-carheylate (VIII); the first-named compound, on hydrolysis, is trans-formed into 2-cyano-2-rnethylcyclopentan-1-one(IX), which is identical with the compound prepared by the methylation of 2-cyanocydo-pentan-1-one (V). $?H,-CMe(CN) $lH,-CMe(CX) ?H,*CNe(CN)>co@H,-CH(CO,Et) CH,-CNe(CO,Et) CH,-cJ3, (VII.) (VIII.) (IX.) The ethylation of ethyl 5-cyanocyclopentan-1-one-2-earboxylate(11) yields a mixture consisting of four parts of the 0-ethyl derivative and one part of the C-ethyl derivative.The cyclopentane ring in these compounds is stable towards acid hydrolysing agents, and therefore S-r/zetl~?/lcyclopent~~-1-oILe (X), 3 :5-dimathylcyclo~entaiL-1-one (XI),aid 2-ethylcyclopentan-1-one(XII) can be readily obtained from the compounds mentioned above. ?He-CHXe yH,*CHMe CH2-CHE5C0CH,-CH, CH,.CHiClle >” CH,-CH, (S.) (XI.) (XII.) The ring is, however, readily broken by the action of alkalis, the final product in every case being either adipic acid or an alkyl derivative. Probably the most remarkable instance of the instability of the cyclopentane ring under these conditions is afforded by the sodium 94 derivative of $-cyanocyclopenton-1-one(XIII), which dissolves in water, forming the sodium salt of 6-cyanovaleric acid (XIV), from which adipic acid (XV) can be obtained on further hydrolysis.$Xf2*CNa(C”)>Co YH,*CH,.CN ~H,-CH,*CO,H CH,- CH, CH2*CH,*C02Na CH2*CH2*C0,H (XIII.) (SIV.) (57’.) 90. The preparation of methyl 1 : 1-dimethylcydopentan-3:4-dione-2:5-dicarboxylate.” By Jocelyn Field Thorpe. Methyl 1 : 1-dimethylcyclopentan-3 : 4 -dione-2 : 5-dicarboxylate, CMez*CH(Co2 )>CO, was first prepared and identified by Dieckmann bH(C0, )--CO (Ber., lS99, 32,1934), the method used for its preparation being the interaction of ethyl oxalate and methyl PP-dimethylglutarate in the presence of sodium ethoxide.Dieckmann prepared this substance with the expressed object (Zoc. cit., p. 1935) of ultimately obtaining from it by reduction and by methylation and rednction acids of the same formulae as those proposed by Bredt for camphoric acid and apocamphoric acid, but he remarks (Zoc. cit., p. 1933) that the yield of the dimethyl salt is exceedingly small. Dieckmann was evidently unable to overcome the initial difficulties occasioned by this poor yield, as the syntheses proposed by him mere ultimately accomplished by Komppa (Bei-., 1901, 34, 2472 ; 1903, 36, 4332). In the first of these papers (Bey., 1901, 34, 2473), Komppa stated that be had succeeded in obtaining an ‘I almost quantitative yield ” of methyl-l : 1-dimethylcycZopentan-3 : 4-dione-2 :5-dicarboxylate from ethyl oxnlate and methyl PP-dimethylglutarate.He omitted to mention, however, either in his paper on apocamphoric acid or on camphoric acid, the conditions under which this increased yield could be obtained. During the past two years the author has made numerous experi- ments with the object of reproducing the conditions employed by Komppa, because it was desired to prepare a quantity of this methyl salt for the purposes of another investigation, but in no one of these experiments has the yield exceeded 10 per cent. of the theory. In view of this difficulty, and of the fact that private communica- tions with Professor Komppa have been unsuccessful in obtaining the details of this important preparation, the author suggests that, as eight years have now elapsed since the publication of Komppa’s paper on apocamphoric acid, and six years since he published his preliminary paper on the synthesis of camphoric acid, publication of the full experimental details is highly desirable.91. Condensations of cyanohydrins. Part I. Condensation pro dnc ts from anisald e hydecyano h ydrin and cinnamalde h yde-cyanohydrin.” By Hamilton McCombie and Ethel Parry. Minovici (Ber., 1899, 32, 2206) described the action of dehydrating agents on anisaldehydecyanohy drin as resulting in the production of a compound melting at 146O, to which he assigned the formula CH3*O*C,H4~CH(CN)*CO*C6H,*O*CH,.This substance has now been shown bo be 2 :5-di-p-methosydiphenyloxazole,7=a(c6H,*o&) cH:c(C6H,*OMe)>o, which was originally described by Minovici himself (Ber., 1896, 29, ZlOO), and its formation in this reaction is due to the presence of unchanged aldehyde in the cyanohydrin.When pure anisaldehydecyanohydrin is subjected to the action of gaseous hydrogen chloride, two substances are formed, namely :(1) a compound melting at 156O, the constitution of which is to be more fully investigated, and (2) 3-hto-2 :5-cli-p-methoxydipheny2-3:4-clihydro-1:4-diazine, N<CH.C,C .oMe)>NH (compare Japp and Knox, C(C,H,* OMe) CO 6-4-Trans., 1905, 87, 701). Cinnamaldehydecyanohydrin, on being subjected to the action of gaseous hydrogen chloride, yields 3-keto-2 :5-distyi-yl-3:4-dihyde.0-1 :4-diaxine.92. Labile isomerism among the acylsalicylamide, acylhydroxy- amine, and phenylbenzometoxazine groups.” By Arthur Walsh Titherley and William Longton Hioks. In order to throw fresh light on the mechanism underlying the wandering of acyl groups in derivatives of salicylamide and aromatic 0-hydroxyamines, the behaviour of phenylbenzometoxazone with phosphorus pentachloride has been studied ;and evidence has been obtained that the resulting 2 :4-dichlorophenylbenzometoxazine under the influence of phosphoryl chloride exhi bits tautomeric behaviour owing to wandering of chlorine atoms, thus : CCl:N*POCl, C6H4<O* CCl ,Ph (B.1 A bright yellow, crystalline substance is obtained which is decomposed by water, yielding benzoylsalicylonitrile, but by 98 per cent.sulphuric acid yielding AT-benzoylsalic ylamide . As the same yellow solid is produced by the action of phosphorus pentachloride on benzoylsalicylonitrile, it must be regarded either as a mixture of A and B, or one of these in a labile form. In the production of the yell0 w substance from phenylbenzo-metoxitzone, various by-products are obtained, among which the double compound of phosphoryl chloride and 4-chlorophenylbonzometoxazine,cc1:yC,H,<O--,HPh, appears to be present. Benzylidene chloride is also produced in considerable quantity together with chloro-phosphorus derivatives of salicylonitrile. 93. The alkyl compounds of platinum.” By William Jackson Pope and Stanley John Peachey.The authors have continued the investigation of the salts derived from trimethylplatinic hydroxide, (CH,),Pt*OH, concerning which they have already published a preliminary note (Proc., 1907, 23, 86). 94. Note on the preparation of trimethylcyc2ohexenone(isophorone)6‘ from ethyl malonate and chlorodimethylcyclohexenone.” By Arthur William Crossley and Charles Gilling. In a recent communication (Trans.,1909,95,20) it has been shown that when the sodium compound of ethyl malonate acts on 5-chloro-1 :1-dimethyl-A*-cycZohexen-3-one,the condensation product does not consist of the substance having formda I,as might have been expected, but of ethyl 1 : 1-dimethyl-A4-cycZohexen-3-one-5-acetate(11). The formation of this latter compound necessitates the elimination of a carbethoxy-group, and it has now been proved that the reaction affords another instance of the production of ethyl carbonate during such condensations : CH(CO,Et), + EtOH (1.1 CH,*CO,Et + CO(OEt), (11.) (compare Thorpe, Tram., 1905, 87, 1681; also PTOC.,1909, 25, 17; Leuchs and Geserick, Be?.., 1908, 41, 4171).Twenty-four grams of chlorodimethylcyclohexenone were treated with ethyl malonate as already described (Zoc. cit., p. 23). The steam 97 distillate was extracted with ether, the ethereal solution dried, evaporated, and the residual 28 grams of liquid fractionally distilled, using a colonna. After three distillations, 7-6grams of a liquid with an ethereal odour were obtained, boiling constantly at 126O, and giving the following numbers on analysis : 0.1927 gave 0.3575 CO, and 0.1471 H,O.C = 50.59 ; H = 8-48. C,H,oO, requires C = 50.84 ; H = 8-47 per cent. These data prove the substance to be ethyl carbonate. 95. ‘‘Asimple gas-drying apparatus for use with a mechanical exhaust pump.” By George Stanley Walpole. It is found convenient in chemical laboratories to use a mechanical exhaust pump for many purposes, especially in conjunction with GASES_--___--i’r.j .4PWL*TU s I 1 /-== distillation apparatus. To maintain the pump in such a condition that at any moment it is capable of working at its maximum efficiency, it must be kept dry by use of either a steam-jacket or else. an eflicient drying apparatus interposed between it and the still.98 The accompanying drawing represents a form of desiccator which has been in use continuously for some months under somewhat severe conditions. The gases from the still pass directly down the tower A. If the tap E be closed and P open, they pass through the concentrated sulphuric acid in the reservoir B. This is the arrangement when t,he still is being exhausted at the commencement of [distillation or when only a moderate vacuum is required. If the tap P is closed and E opened, the gases pass up the tower, meeting a slow stream of sulphuric acid running over the glass beads and regulated by tap C. In this arrangement a short circuit is thus established which eliminates the hydrostatic pressure of the sulphuric acid in the bottle B, and there is no resistance offered to the gases passing to the pump.It is advisable to leave all taps turned off when the apparatus is not in me. The acid from B can be run out periodically, and if suitable, used again. 96. Some esters of antimony trioxide.” By John Francis MaoKey. Lang, MacKey, and Gortner (Trans.,19OS, 93, 1364) described a new method for the esterification of arsenious oxide with the aliphatic alcohols and with phenol and its homologues, and expressed the opinion that similar esters might be obtained from antimony trioxide and the same alcohols and phenols. In the present work attempts have been made to form these esters by treating a mixture of antimony trioxide and the alcohol or phenol in the following ways : (1) heating under a reflux condenser; (2) heating with Soxhlet attachment and anhydrous copper sulphate ; (3) heating in sealed tubes at 150’; (4) heating with metallic calcium; (5) treating with anhydrous oopper sulphate in the cold.By the second method, yields of from 3 per cent. in the case of ethyl antimonite to 15 per cent. in the case of isobutyl antimonite, and of 40 per cent. in the case of phenyl antimonite to 48 per cent. in the case of m-tolyl antimonite, were obtained. By heating with metallic calcium a yield of 60 per cent. was obtained with phenyl antimonite. The following esters were isolated in quantity : msthyl, ethyl, propyE, isobutyl, amyl, isoamyl, phewpl 0-, m and p-tolyl antimonites.The aliphatic esters are all liquids, which decompose on heating at atmospheric pressure into antimony trioxide and the alcohol from which they were prepared, whilst phenyl, o-tolyl, and p-tolyl antimonites are solids melting at 13O, 16O, and 14O respectively. The boiling points of these esters, under 30 mm. pressure, are as follows : methyl, 65’; ethyl, 115-120°; propyl, 143’; isobutyl, 144O; 99 amyl, 170° ; isoamyl, 163O ; phenyl, 250' ; 0-tolyl, 352' ; nz-tolyl, 300° ; and p-tolyl, 345'. They are soluble in absolute alcohol, ether, chloroform, or benzene, but decompose immediately on the addition of water into antimony trioxide and the alcohol from which they were prepared. Accurate methods of analysis have been worked out for both the esters of the aliphatic alcohols and the esters of phenol and its homologues.On analysis these esters were found to correspond with the general formula R,SbO,. ADDITIONS TO THE LIBRARY. THE FOLLOWING BOOKS HAVE BEEN PRESENTED TO THE LIBRARY BY Mr. EDWARD DAVIES. Boyle, Robert. Opera varia, quorum posthac exstat catalogus. Cum indicibus necessariis, multisque figuris aeneis. Geneve 1680. 12 parts. (2 copies, 7 wanting portrait.) Experi mentorum novoi-urn physico -mechanicor urn continuatio secunda, etc. pp. viii + 132. ill. Genevae 1682. (2 copies.) --Apparatus ad historiam naturalem sanguinis humsni, ac spiritus precipue ejusdem liquoris. pp. viii + 47. Geneve 1686. -Observationes de Salvedine Maris.pp. 23. Genevae 1686. Tentamen porologicum sive ad porositatem corporum tum animslium, tum solidorurn detegendam. pp. vi + 46. Genevze 1686. De specificorum rernediorum cum corpusculnri philosophia concordia, etc. pp. viii + 64. Genevae 1687. Tractatus de ipsa natura, etc. pp. xvi + 111. Genevae 168s. Origo formarurn et qualitaturn juxta philosophiam corpus-cularem, etc. pp. xxxii+ 147. Geneva 1688. -Noctiluca aeria sive nova qiiaedam phEnomena in substantie factitie sive artificialis, Sponte Lucidae, procluctione observata, etc. pp. 108. Genevae 1693. Summa veneratio Dao nb humano intellectu debita, etc. pp. 43. Geneve 1693. Medicina hydrostatics, sive hydrostntica materiae medic* applicata, etc. pp. xii + 70. Colonize Allobrogum 1693.De amore seraphic0 seu de quibusdam ad Dei amorern stimulis pp. viii+59. Genevae 1693. -Experimenta nec non observationee circa variarum particu-larium qualitatum originem, sive productionem mechanicam : Quibus accesserunt tract,atua quo irnperfecta chyrnistarum doctrina de 100 qualitatibus detegitur, & quaedam in hypothesin de alcali 8: acido animadversiones. pp. xvi + 144. Genewe 1694. -Exercitationes circa utilitatem philosophia naturalis experi- mentalis, etc. pp. xvi + 602. Geneva 1694. Novorum experimentorum physico-mechanicorum continuatio prima, etc. pp. xii + 133. ill. Geneva 1694. -Experimenta et nota? circa producibilitatem chymicorum pxincipiorum : Qua sunt totidem partes appendicis ad Scepticum Chymicum.pp. xii + 92. Genevae 1694. Examen dialogi physici doinini T. Hobbs, de natura aeris, etc. pp. viii+67. Geneva? 1695. Tractatus varii continentes nova experimenta circa relationem inter flammam & aerem et circa explosiones, etc. pp. iv+ 120. Genevze 1696. Generalia capita pro historia naturali regionum majorum vel minorum, etc. pp. iv + 39. GenevE 1696. Excellentia theologie cum naturali philosophia, etc. pp. viii + 87. Genevs 1696. At the next Ordinary Meeting on Thursday, April lst, 1909, at 5.30 p.m., the following papers will be communicated : ‘(The affinity values of certain alkaloids.” By V. H. Veley. I‘ The preparation and properties of the N-tribromo-substituted hydrazines usually styled the dinzoperbromides.” By F. D, Chattaway.‘‘ The coloured salts a,nd derivatives of the thiovioluric acid group.” Preliminary note. By P. C. C. Isherwood. “Nitrosoacetylamino-derivatives of the benzene and diphenyl series.” By J. C. Cain.‘‘Observations on phycoerythrin, the pigment of the red algae.” By E. K. Hanson. -__ -R. (’LAY i~nSOTS. LTD., BREAD sr. HILL, E.c., AND BUNGAY, SUL*FOLK.
ISSN:0369-8718
DOI:10.1039/PL9092500081
出版商:RSC
年代:1909
数据来源: RSC
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