77. "Optically Active Substances which contain no Asymmetric Atom." (Preliminary 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 compounds have been unsuccessful. All the constitutional 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. In Nature (1909, lxxix., 457), Prof. Rutherford describes | goniometrically in order to ascertain whether Pasteur's experiments in which he obtained such "a brilliant point law holds in connection with the crystalline form of subof phosphorescent light"; and he measured the tem- stances which owe their optical activity to the new kind of perature at which the "initial condensation of the emana- asymmetry now discovered. In reply to Prof. Armstrong, tion" occurred at atmospheric pressure; he found it to be it was observed that, although the molecule contains no -65°. In the light of the above experiments, it is difficult asymmetric atom, an asymmetric system forms part of the to say what he was observing; probably, the solidifying-molecular configuration, and that the optical activity arises point of the emanation, although he speaks of having seen from the enantiomorphism thus introduced. In connection "small drops of liquid emanation on the walls of the with Dr. McKenzie's remarks, Prof. Pope observed that no capillary." doubt can now exist that the acid described by Marckwald as 1-methylcyclohexylidene-4-acetic acid is really 1-methylcyclohexene-4-acetic acid, 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 androsæmifolium." By CHARLES WATSON MOORE. The material employed in this investigation was the An rhizome of Apocynum androsæmifolium, Linné. 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 deposited on standing; and material which remained dissolved in the cold aqueous liquid. The brown resin (A) yielded small quantities of ipuranol, C23H38O2(OH)2 (m p. 285—290°), and acetovanillone; palmitic, stearic, oleic, and linolic acids, and a large quantity of unsaponifiable material. From the latter, two new alcohols, androsterol, C30H49'OH (m. p. 208-210°) and homoandrosterol, C27H43'ÕH (m. p. 1929), were obtained, whilst the presence of a third alcohol was proved by the isolation of its bromoacetyl derivative (m. p. 212–214°), and a monobromoacetyl derivative (m. p. 228-230°). Acetylhomoandrosterol melts at 236°. The brown resin (B) yielded a further small quantity of aceto CH Some time ago Perkin and Pope (Trans., 1908, xciii., 1082) synthesised 1-methylcyclohexylidene-4-acetic acid, CH2 CH2>C:CH CHC CH2 CH2 CO,H and pointed out that, on the basis of the tetrahedral environment of the carbon atom in methane, this substance possesses an enantiomorphous 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-methylcyclohexyl-(m. p. 265-268°). Androsterol yields an acetyl derivative idene-4-acetic acid by the method described below. To a hot aqueous solution of two molecular proportions of externally compensated sodium 1-methylcyclohexylidene4-acetate is 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 any oily salt. On cooling and scratching with a glass rod, rather less than one-half of the acid separates as crystalline brucine lævo-1-methylcyclohexylidene-4-acetate, C23H2604N2, C9H14O2,2H2O, whilst most of the dextro-component of the acid remains in solution 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. vanillone. It The portion of the alcoholic extract of the rhizome which was soluble in cold water, and from which the above described resins had been removed, contained large amounts of sugar and tannin. yielded a quantity of acetovanillone (m. p. 115°), which was also present in the form of its glucoside, androsin, CH3 CO C6H3(O CH3) O C6H1105,2H2O (m. p. 218– 220°), and a new substance, apocynamarin, C28H3606,2H2O (m. p. 170-175°), which possesses an intensely bitter taste, is highly toxic, and represents the chief active constituent of the rhizome. *79. "The Action of Phosphorus Pentachloride on the Methylene Ethers of Catechol Derivatives. Part IV. Derivatives of Dihydroxyphenyl-acetic, glycollic, and Lævo-1-Methylcyclohexylidene-4-acetic acid is obtained-glyoxylic Acids.” By GEORGE BARGER and Arthur from the brucine salt by addition of hydrochloric acid to its DISCUSSION. Dr. TUTTON asked whether Prof. Pope had been able to measure the crystals, and if so, whether he had found them 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. MCKENZIE referred to the work of Marckwald and Meth in this connection. 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 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, xiv., 793), the authors have prepared a number of methylene ethers and cyclic carbonates related to 34-dihydroxymandelic acid, C6H3(OH)2 CH(OH) CO2H, and to 3: 4-dihydroxyphenylglyoxylic acid, C6H3(OH)2 CO CO2H, 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 C6H3(OH)2 CH(OH).. Dihydroxymandelic acid is much less stable 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) phenylphenazonium. According to Bernthsen the two amino-groups are symmetrically situated, whilst Witt of 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 Körner and Schraube, who obtained identical dialkylsafranines by the oxidation of (a) one molecule of asdialkyl-p-phenylenediamine with 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. Chim. Phys., 1908, [8], xiii., 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 m-hydroxydi: phenylamine (Ber., 1895, xxviii., 273), since the acetyl derivatives prepared from both specimens melt at 2710 (uncorr.) whether alone or mixed (Fischer and Hepp give 265-268°, Ber., 1897, xxx., 401). The synthesis of an asymmetric phenosafranine by oxidation of aniline with 2: 4'-diaminodiphenylamine described by Barbier and Sisley (loc. cit., p. 102) could not be realised, any safranine obtained by them probably owing its origin to admixed 4: 4'-diaminodiphenylamine, since potassium dichromate converts 2: 4'-diaminodiphenylamine 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 Acids." By SIEGFRied Ruhemann. Ruhemann and Merriman (Trans., 1905, lxxxvii., 1383) have shown that acetylacetone condenses with phenylpropiolyl chloride to a yellow furfuran derivative (I.); this readily changes into its red isomeride (II.), which, with bases, forms blue salts, and with hot sodium carbonate yields a colourless acid (III.) isomeric with (I.) and (II.). These changes were represented thus :CHPh:C-CO O CMe (I.). : C(OH) CO CACI CAC | 167 pyruvate and d-amyl benzoylformate respectively has been examined. The asymmetric synthesis of d-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 d-amyl alcohol from fusel oil were not successful. *83. "Contributions to the Chemistry of Cholesterol and Coprosterol." By CHARLES DORÉE. The author has investigated the action of ozone on the following cholesterol derivatives :-Cholestenone, the acid C27H4404, 3-cholestanol, coprosterol, -coprosterol, and the ketones corresponding with these, and a-cholestanol. All of these with the exception of a-cholestanol, which is indifferent, react with ozone, and the determination of the ozone numbers of these compounds confirms generally the view of Molinari (Ber., 1908, xli., 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, but 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 (Trans., 1908, xciii., 1627) a constitution of the carbazole type. A crystalline nitrosite was prepared and analysed. (To be continued). CORRESPONDENCE. MATHEMATICALLY HARMONISING THE ELEMENTS-A CORRECTION. To the Editor of the Chemical News. SIR,-In arriving at the weights of carbon and neon (CHEMICAL NEWS, xcix., 148), I indicated reduced values, as the line intersecting C, O, and Ne is a curve, whereas the values should have been increased. Please note therefore that carbon should read 12.00+ instead of 11999+, and neon 20.00+ instead of 19.999+. The small amounts involved are, of course, indeterminable, but the curve which intersects oxygen exactly shows whether they are increments or decrements, and I have taken this way o indicating it. That the true weight of carbon is above 12 rather than below it, is very probable judging from the determinations that have been made.-I am, &c., 7, Doughty Street, London, W.C., March 29, 1909. F. H. LORING. RE VALENCY AND ENERGY. To lhe Editor of the Chemical News. SIR,-In Dr. Friend's recently published volume entitled "The Theory of Valency" I have noticed the following passage (p. 164): "Le Bas has found that valency may be connected with the amount of energy in the molecule, and illustrates this view with the aid of the heats of combustion of the hydrocarbons. It is pointed out that the molecular heats of combustion of the hydrocarbons are proportional to their valency numbers." May I be allowed to call the attention of the author, and of readers of this book in general, to the following facts: 1. In reply to my first criticism of his views, Mr. Le Bas tacitly admitted that the molecular heats of combustion of the hydrocarbons are not, in general, proportional to their valency numbers, since in the case of unsaturated hydrocarbons, constants (depending on the unsaturated links) were to be added to the heats calculated from the valency numbers (see CHEMICAL NEWS, xcvi., 58). 2. That a further criticism of Mr. Le Bas's hypothesis (CHEMICAL News, xcvi., 136), in which I went fully into the question, did not receive a reply. This may, I presume, be taken as implying that Mr. Le Bas admits the validity of my criticism.—I am, &c., H. STANLEY REDGROVE. The Polytechnic, Regent Street W. CHEMICAL NOTICES FROM yields carbon monoxide and diphenylacetic acid when 5>CH-COOH. COO \o/ Similarly phenyltolylacetic ether gives phenyltolylglycidic acid when saponified, and the glycidic acid yields phenyltolylacetic acid on heating. Apparently the aldehyde is not formed owing to the presence of the two atoms of tertiary carbon in the neighbourhood of the CO group of the generating ketones. Halogen Derivatives of y-Oxycrotonic Acid.— MM. Lespieau and Viguier.-Bromine with y-oxytetrolic acid yields an acid alcohol, CH2OH-CBr=CBr-CO2H, and a lactone, CH2-CBr=CBr-CO. The lactone beO FOREIGN longs to the maleic series, while the acid which is relatively stable towards heat and does not readily give lactone (except under the influence of reagents which frequently cause the transformation of a substance into a stereo Comptes Rendus Hebdomadaires des Séances de l'Académie des Sciences. Vol. cxlviii., No. 7, February 15, 1909. Melting - point of Platinum. C. Féry and C. Chéveneau. Various investigators who have determined the melting-point of platinum have obtained results which differ by as much as 4.6 per cent. These differences appear to be due to the gaseous medium in which the fusion is performed. The authors' determinations also give a difference of 30 to 40° (17 to 2.3 per cent), which does not appear to be caused by a variation in the emissive power of platinum. Thermal Phenomena accompanying the Action of Water on Aluminium Powder.-E. Kohn-Abrest and J. Carvallo.-When water acts on aluminium powder in the exothermic interval the grains of aluminium are attacked, yielding hydrated oxides of aluminium. Calorimetric measurement shows that the reaction sets free 8100 cals. for 4.82 grms. of pure aluminium, which would be about 90,000 cals. for a molecule of aluminium (Al2). From the results of chemical analysis, the reducing power towards ferric sulphate, the amount of hydrogen set free when the powder is attacked by hydrochloric acid, the proportion of combined water, and the amount of oxygen fixed by the aluminium, it may be concluded that other oxides exist in the powder besides that of aluminium. isomer) belongs apparently to the fumaric series. It is quite easy to fix iodine by y-tetrolic acid when the acid CH2OH-CI = CI-CO2H is formed. to on MISCELLANEOUS. Royal Institution.-The following are the lecture arrangements at the Royal Institution after Easter :Prof. F. W. Mott, two lectures on "The Brain in Relation Right-handedness and Speech"; Prof. Svante Arrhenius, two lectures on 66 Cosmogonical Questions " (the Tyndall Lectures); Prof. J. Garstang, two lectures on "The Hittites-(1) Monuments of Egypt and Asia Minor, (2) Recent Discoveries in Asia Minor and Northern Syria"; Dr. F. Gowland Hopkins, two lectures on " Biological Chemistry"; Mr. James Paterson, three lectures on "Aspects of Applied Aesthetics-(1) How a Fine Art New, (3) Art and Ethics"; Mr. J. G. Millais, three lecInstinct may be best Developed, (2) Landscape Old and tures on Newfoundland; Prof. W. E. Dalby, two lectures Mr. R. T. Günther, two lectures on the Earth Movements A Modern Railway Problem-Steam v. Electricity"; Raleigh, two lectures on "(1) Edmund Burke, (2) Burke's Prose"; Dr. W. H. R. Rivers, two lectures on "The Secret Societies of Banks' Islands"; and Dr. F. F. Blackman, two lectures on "The Vitality of Seeds and Plants(1) A Vindication of the Vitality of Plants, (2) the Life and Death of Seeds." The Friday Evening Meetings will be resumed on April 23, when Mr. Alexander Siemens will deliver a Discourse on "Tantalum and its Industrial Applications." Succeeding Discourses will probably be given by Dr. Edmund Gosse, Major Ronald Ross, Prof. G. E. Hale, Hon. Ivor Guest, Dr. J. Emerson Reynolds, Prof. J. A. Fleming, Prof. Sir James Dewar, and other gentlemen. of the Italian Coast and their Effects"; Prof. Walter Catalytic Oxidation of Hypophosphorous Acid by Copper.-J. Bougault.-When sodium hypophosphite is treated with an excess of copper sulphate a brownish yellow precipitate is obtained; this appears to be a cuprous salt, probably the hypophosphite. It is gradually reduced to copper. In presence of an excess of hypophosphite a brown precipitate of the hydride is formed. On heating on the water-bath hydrogen is evolved, and a reddish precipitate is formed on the surface of the liquid. The hypophosphite is converted partially into phosphate and phosphite. The reaction slackens and finally stops before all the hypophosphite has been transformed. If the liquid is decanted and more hypophosphite is added hydrogen is again evolved. This operation can be repeated and a large quantity of hydrogen obtained with a small quantity of copper. Prob- MONDAY, 5th.-Royal Society of Arts, 8. (Cantor Lecture). ably the water is decomposed in presence of the catalyser, hydrogen being evolved while the oxygen oxidises the hypophosphite. Exception to the General Method of Preparing Aldehydes by means of Glycidic Acids.-René Pointet. -According to Darzens the glycidic acids liberated by a mineral acid from the products of the saponification of B-glycidic ethers with concentrated soda may be decomposed by heating into carbon dioxide and aldehyde R R>C−CH–COOH=CO+r>CH–CHO. With diphenylacetic aldehyde and its homologues this method gives very poor results. Diphenylglycidic acid MEETINGS FOR THE WEEK. "Steam Turbines," by G. Gerald Stoney. TUESDAY, 6th.-Royal Society of Arts, 4:30. "Ceylon, its Industries for Sewage Effluents," by S. Rideal and W. T. Burgess. "Determination of the Oxygen Absorbed by Sewage and Effluents by a Modification of Kubel's Method," by W. Carter. "Note on Enkabang and Teglam Fats and Katio Oil from Sarawak," by C. J. Brooks. "Composition of Milk," by H. D. Richmond. NO CLOCCING OF TUBES. NO LEAKY JOINTS. Generation can be stopped Instantly by simply turning NOTHING TO GET OUT OF ORDER. 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