"The Liberation of Helium from Minerals by the Action of Heat." By D. ORSON WOOD, B.Sc., A.R.C.Sc. Experiments were made to determine how the volume of helium liberated from radio-active minerals by the action of heat depends on the temperature, and on the time for which that temperature is maintained; in particular with a view to the future use of heat to release all the helium contained in minerals not easily treated by chemical methods. The minerals experimented on were monazite and thorianite-the one comparatively poor and the other very rich in helium. The ground minerals were heated in vacuo in tubes of Jena glass or quartz, by an electric heater consisting of a single coil of nickel wire, to temperatures up to 1200° C., which were measured by a Pt resistance thermometer or a Pt Pt-Rh thermocouple. The gas released was purified by drawing it through KOH and P2O5 tubes and finally by Na-K electrodes. The volume was measured in a modified McLeod gauge (described by Prof. Strutt, Proc., vol. lxxx.) specially constructed for the measurement of volumes over a large range-1 cc. to 1 cmm. Curves are given to show the volume of helium liberated with time at constant temperatures (250-1000° C.), and also the percentage of the total content obtainable after prolonged heating at the different temperatures. The way in which the gas must be supposed to be retained within the mineral to accord with the results obtained is discussed, and it is concluded:-(1) That heat may be used for the complete liberation of the gas if a sufficiently high temperature (about 900° C.) is reached; and (2) that the results are in agreement with the supposition that a small proportion of the gas is diffused through the mineral, and that the remainder is concentrated in very minute cavities within it. "The Chromophil Tissues and the Adrenal Medulla." Prof. SWALE VINCENT. CHEMICAL SOCIETY. Prof. HAROLD B. DIXON, M.A., F.R.S., President, in the Chair. (Concluded from p. 214). *90. "Studies in Fermentation. Part III. The Role of Diffusion in Fermentation by Yeast Cells." By ARTHUR SLATOR and HENRY JULIUS SALOMON SAND. An Facts of a directly experimental nature lead to the belief that during the fermentation of a sugar by yeast, diffusion usually supplies the latter with material so rapidly that convection currents in the solution do not play any part in determining the apparent velocity of the reaction. investigation has now been carried out by means of the apparatus described previously, in order to determine the limiting conditions under which convection currents would begin to become a controlling factor of the rate of the process. These have been deduced from the following formula, which were shown to represent with sufficient accuracy the changes of concentration in a stationary solution in which uniformly distributed yeast cells are operative: -C-Сo-3F/8πER and C1-Co= F/8πKR. In this expression, C represents the concentration of the sugar at any point of the solution not in the immediate vicinity of a yeast cell, C, the concentration on the surface of a cell, Co the concentration at its centre, R its radius, and the diffusion coefficient of the sugar. F is the amount of sugar fermented per cell per unit of time, and was determined by experiment to be approximately 3 x 10-14 g/sec. at 30°. DISCUSSION. Dr. HORACE BROWN fully recognised the importance of knowing the particular conditions under which diffusivity becomes a factor in limiting the specific activity of the yeast cell. The results of an enquiry which he had made some time ago, employing the electrostatic analogy, were in substantial agreement with the conclusions of the authors, but he differed in some important points of detail, and considered that it was unnecessary to make any assumptions as to the particular mode in which absorption of the sugar takes place within the cell. The phenomena of steady diffusion induced by an absorbing sphere in a diffusive field are closely analogous to those presented by an insulated conductor of the same dimensions which has received an electrical charge. In the former case, when the permanent state has been reached, there are produced around the sphere a series of concentric shells of the diffusate which in distribution, although with opposite sign, correspond with the shells of equipotential in the dielectric surrounding the charged sphere. The variations in the gradient of concentration of the diffusate, as measured along the lines of flux, correspond exactly with the variations in the gradient of potential around the charged sphere, measured along the lines of force. In the special case of a spherical yeast cell immersed in a solution of sugar, if the concentration of the diffusate at a remote point is represented by p, and that at the immediate surface of the cell by or, then the gradient of concentration at the surface, on which the rate of absorption depends, will be represented by P-01, being the radius of the cell. If F be taken as the total absorption in unit time, then :— F = 4πr 2 (p − P1) k = 4πr(p—p1)k, 2 being the coefficient of diffusivity of the sugar. F has been experimentally determined, all the problems When actual values in C.G.S. units are substituted, and given by the authors can be solved by simple mathematical treatment, and without the necessity of making any assumptions as to the particular mode in which the sugar is dealt with in the interior of the cell or the amount of resistance introduced by the cell-membrane. His (the speaker's) determinations of the amount of sugar fermented by a single yeast cell in a second of time at a temperature of 17-20° led to a value of F of o'92 X 10-14 grm. The authors of the paper had found 3'0 x 10-14 for a temperature of 30°. Taking into account the temperature-coefficient, which had been previously determined by Dr. Slator, these two results were almost identical. One of the problems presented by the authors was to ascertain the minimal concentration, p, of a sugar solution which would be just sufficient to supply the yeast cell with its requirements by diffusion only. From the above formula, and taking the value of F as 3'0 x 10-14, it follows that : that is to say, the minimal gradient of concentration at the surface of the cell must be 0.85 mgrm. per litre if these conditions are to be fulfilled. If the absorption of the sugar were complete at the exterior surface of the cell, then pi would be zero, and the required minimal concentration of the sugar solution, p, would be 0.85 mgrm. per litre. We know, however, that the metabolism of the sugar takes place within the cell, and therefore that pr must have a positive value, which, however, cannot exceed 0.85 mgrm. per litre if the gradient is to remain constant and p is to be at a minimum. The values p and pr can be evaluated by looking at the problem somewhat differently. Let it be supposed that all the fermentative processes are reversed, the activity of the cell as measured by F remaining the same. The cell will now emit sugar into the surrounding medium, and when p is at a minimum, that is, zero, the concentration pr at the exterior surface of the cell must equal the gradient, that is to say, must be equal to 0.85 mgrm. per litre if the outward flow is maintained at F. This must also represent the minimal surface concentration when the cell is absorbing sugar and p is also at a minimum; hence, under | is also taking place during the titration. As, however, it these latter conditions, p=2p1=170 mgrms. per litre, instead of 1.29 mgrms. as found by the authors. By the same reasoning it could be shown that with maximal stirring a concentration of 0.85 mgrm. per litre ought to be sufficient to supply the cell with its full requirements. In this way it seems possible to avoid all complications introduced by having to take into account internal diffusion, the rate of metabolism and diffusion within the cell being included in the value of p1, which can be evaluated by simple means. Apart from all calculations of this kind, it is evident that diffusion can play but a very small part in limiting the activity of the cell when we consider the very large surface area represented by a relatively small amount of yeast. o'I grm. of pressed yeast, corresponding with about 0.025 grm. of dry substance, contains about 4X 108 cells, representing a surface area of 804 sq. cm. When this yeast is actively fermenting at 30°, this large area is called upon to deal with not more than about 43 mgrms. of sugar per hour. Dr. Slator, in reply, expressed the opinion that it was not possible to calculate these limiting conditions unless diffusion in the yeast cell itself was taken into consideration. *91. " Synthesis of p-Hydroxyphenylethylalkylamines." By GEORGE STANLEY WALPole. The methylamino- and ethylamino-homologues of hydroxyphenylethylamine have been prepared in order that their physiological properties might be examined. The starting point was p-methoxyphenylethylamine, and the series of reactions employed may be represented by the following scheme : MeO C6H4 CH2 CH2 NH2 → MeO-C6H4CH2CH2NHẠC -> MeO C6H4 CH2 CH2 NAc(Alk) →→ 2 HO C6H4 CH2 CH2 NH(Alk). Another series of compounds was prepared similar to the above, but in which the benzenesulphonyl group replaced the acetyl group whenever it occurred. In chemical and physical properties, p-hydroxyphenylethylmethylamine m. p. 130°) and p-hydroxyphenylethylethylamine (m. p. 157-158°) resemble the parent substance, p-hydroxyphenylethylamine, very closely. The hydrochlorides melt at 148.5° and 184-185° respectively. A dibenzoyl derivative, melting at 99, and a platinichloride, melting at 205°, were prepared from the hydrochloride of p-hydroxyphenylethylmethylamine. The platinichloride corresponds exactly with the data given by Blau for the platinichloride prepared from the base obtained by the destructive distillation of surinamine. There is no longer room for doubt, therefore, that the latter substance is, as supposed, methyltyrosine. 92. "The Condensation of Anisaldehyde with Resorcinol." By FRANK GEORGE POPE and HUBERT HOWARD. In continuation of their previous work (Trans., 1910, xcvii., 78), the authors have condensed anisaldehyde with resorcinol, and have prepared 2: 4-dihydroxy-4-methoxybenzhydrol and its derivatives. 10-Hydroxy-7-phenyldihydro-aß-phenonaphthacridine was also described. 93. "The Influence of Persulphates on the Estimation of Hydrogen Peroxide with Permanganate." By JOHN ALBERT NEWTON FRIEND. The author showed a few years ago (Trans., 1904, lxxxv., 547, 1533; 1905, lxxxvii., 738, 1367; and 1906, lxxxix., 1092) that, in ordinary circumstances, a correct estimate of hydrogen peroxide in the presence of potassium persulphate is not obtained by titration with permanganate, for the amount of the latter used always falls short of that required theoretically. It was further shown that for every molecule of peroxide not accounted for by the perman. ganate, a molecule of persulphate disappears. This suggests that the reaction H2O2 + K2S2O8 = K2SO4 + H2SO4 +Õ2 | proceeds with extreme slowness in ordinary circumstances, the author assumed that it is here "catalytically accelerated by some oxide of manganese formed during titration." In a recent communication (Oesterr. Chem. Zeit., 1910, No. 3), Dr. A. Skrabal, whilst acknowledging the correctness of the experimental work, has suggested another interpretation. He says:-"Nach unserer Meinung dürfte die von Friend beobachtete Erscheinung dadurch besser charakterisiert werden, dass man dieselbe in die Klasse der induzierten Reaktionen verweist. Wir nehmen alse an, das die Reaktion 5H2S2O8+2KMnO4+2H2O= = K2SO4 +2MnSO4 + 7H2SO4+502 welche für sich allein nicht oder nur ausserordentlich langsam verläuft, durch die freiwillige und rasche Reaktion zwischen Hydroperoxyd und Permanganat induziert wird.” If, however, such were the case, it is clear that more permanganate would be required in the titrations than theory demands for the decomposition of the peroxide, the excess being measured by the extent to which the reaction between permanganate and persulphate is induced. less permanganate is actually required, such an explanation is seen to be untenable. Since In a private communication, Dr. Skrabal has kindly given the author permission to state that he acknowledges the error, which arose through his consulting abstracts of the author's papers instead of the originals. He prefers, however, to regard the reaction which takes place between the persulphate and peroxide as "induced " rather than as catalytically accelerated by an oxide of manganese. This is merely a question of choice of terms, however, for induction is very frequently merely a special case of catalysis, neither of which is at present understood. 94. "Amido-oximes and Thioamides." By WILLIAM FRASER RUSSELL. The conversion of thioamides into amido-oximes by the action of hydroxylamine is restricted to those thioamides of the type R CS NHR, those of the formula RCS NRR scarcely being acted on by hydroxylamine under the same conditions. The author has prepared a number of thioamides of the second type, and the effect of hydroxylamine on them was described. 95. "Preparation of the Acyl Derivatives of the Aldehydecyanohydrins." Part II. By OLIVER CHARLES MINTY DAVIS. The reaction between acyl chlorides, aldehydes, and aqueous potassium cyanide (Trans., 1909, xcv., 1403) has been further investigated, and found to be quite general for all types of aldehydes. Benzoyl lactonitrile, a- benzoyloxyisohexonitrile, and benzoyloxyoctonitrile have been prepared; they are oils of high boiling-points. With the exception of acetone, it was found impossible to obtain compounds from ketones analogous to the aldehyde-cyanohydrin derivatives. From acetone, benzoyloxyisobutyronitrile, m-nitrobenzoyloxyisobutyronitrile, and carbethoxyisooxybutyronitrile were obtained. The reactions of the acylaldehhyde-cyanohydrins have also been investigated. 96. "Some Derivatives of Tetramethyl Ferrocyanide." By ERNALD GEORGE JUSTINIAN HARTLEY. Dry potassium ferrocyanide reacts readily with methyl sulphate at 80-90° with the formation of potassium methyl sulphate and a substance which could not be obtained pure, but probably has the composition Me, FeC6N6,2MeSO4, 2MeHSO4. This, on further heating or on keeping in a vacuum, gives off methyl sulphate, and is converted into Me, FeC6N6, Me2SO4, H2SO4, a very stable substance soluble in water and methyl alcohol, and crystallising well from the latter solvent. It gives none of the usual reactions for iron or for ferro- or ferri-cyanides, but on 97. "The Molecular Refraction of Thiocyanates and other Salts." By AUGUSTUS EDWARD DIXON and JOHN TAYLOR. From previous observations (Hawthorne, Trans., 1906, Ixxxix., 556; Dixon and Taylor, Ibid., 1908, xciii., 2153), it appears that, as calculated by the formula 4° the mean refraction value of the group SCN in organic combinations is about 23.3 units; it is now shown that the refraction effect of this group in the thiocyanates of sodium, potassium, ammonium, calcium, and aluminium is considerably higher, the mean value being about 26 units. In this respect the SCN group resembles the halogens, which give higher values in metallic salts than in organic combinations. The refraction value of the group C204 was found to be substantially the same in potassium oxalate and in ethyl oxalate, the mean numbers being 21.6 and 21.8 respectively. For SO, in sodium, potassium, and ammonium sulphates, the mean value was 16.89; in various alkyl sulphates, 1753; and in ethyl sulphate, 1891; this was the only case noted in which an acid residue gives a lower value in metallic salts than in esters. Silicon thiocyanate showed in its chemical behaviour no sign of being a thiocarbimide; this agrees with the conclusion of Emerson Reynolds (Trans., 1906, lxxxix., 397). 98. "Estimation of Carbon in Iron and Steel and in Iron Alloys by Direct Combustion." By THOMAS ERNEST HULL. In the process which is often recommended for determining the carbon-content of iron alloys (ferromanganese, ferrosilicon, silicospiegel, &c.), namely, to ignite the drillings with powdered and ignited lead chromate, the author finds that, at the high temperature involved (800-960°), the lead chromate is decomposed into chromic oxide and basic lead chromate, and that the former is not retained in the usual drying apparatus, and consequently is absorbed by the potash in the potash-bulbs, thus leading to a high result in the amount of carbon found. There is no doubt that the decomposition of the lead chromate is solely due to the high temperature employed. The following method for the determination of carbon in iron and steel is found to be both simple and accurate : -The finely-drilled sample is weighed into an asbestos boat (made from strips of moistened asbestos millboard), which has been previously heated to full redness, and into which a layer of recently ignited silver sand has been introduced. The ignition in oxygen is carried out at 900-960°, the residual gases are dried by passing through concentrated sulphuric acid contained in a Mohr's bulb, and the carbon dioxide is absorbed by 30 per cent potassium hydroxide solution in the usual weighed bulbs. In the case of ferromanganese, &c., it is advisable to ignite the finely-powdered sample with zinc oxide. The porcelain or silica-glass tube is always packed loosely with asbestos and copper oxide. 99.2-Methyl-1: 3-benzoxazine-4-one and Related Derivatives." By WILLIAM LONGTON HICKS. Salicylamide and acetaldehyde (paradehyde) condense under the influence of hydrogen chloride at 80° to form CO NH oxazine ring may be ruptured by means of sodium 100. "The Examination of the Atmosphere at various Altitudes for Oxides of Nitrogen and Ozone." BY WALTER HAYHURST and JOHN NORMAN PRING. Methods were devised to carry out accurately a qualitative examination of the atmosphere for the presence of Ozone and oxides of nitrogen at various altitudes. Experiments were made systematically on and above Glossop Moor, in Derbyshire, during three or four months in summer, and were supplemented by a number of tests on sea- and mountain-air at various places in this country. It was found that oxides of nitrogen were always present in quantities which vary largely from time to time, and that the amount of ozone was, in every case, too small to be detected in the experiments conducted at ground level, and at intermediate altitudes (up to 8000 feet). It was shown, in consequence, that the amount of ozone is less than 0.003 mgrm. in the quantity of air dealt with in each experiment (between 1 and 10 cubic metres). Experiments at very high altitudes, ranging up to ten miles, were carried out with the help of free balloons, and in these the presence of small quantities of ozone, averaging about 0.2 mgrm. in o'r to o'3 cubic metre of air, detected; the quantity of oxides of nitrogen was found to be rather less. was 101. "Derivatives of S-Alkylphenazothionium." By EDWARD DE BARRY BARNETT and SAMUEL SMILEs. Whilst thiodiphenylamine and methyl iodide when heated together yield the N-methyl derivative, these reagents in presence of mercuric iodide at the atmospheric temperature furnish the methyl-sulphonium iodide. This substance reacts with silver oxide, yielding S-methylphenazothionium. 102. "Preparation of Substituted Indoles from Benzoin and Secondary Arylamines." By MARION BROCK RICHARDS. Japp and Murray (Trans., 1894, lxv., 889) showed that by heating benzoin with primary arylamines in presence of zinc chloride or of the hydrochloride of the amine, 2:3diphenylindoles could be prepared. The author now finds that, by employing secondary in place of primary arylamines, substituted diphenylindoles may be obtained. Thus by the interaction of benzoin and methylaniline in presence of zinc chloride or of methylaniline hydrochloride, 2: 3-diphenyl-1-methylindole is formed, according to the equation:C6H5 NHMe + COPh·CHPh·OH = NMe. CPh+2H2O. In like manner, by employing other arylamines, corresponding diphenylindoles have been prepared. 103. The "The Interaction of Hydrogen and Chlorine. Nature of Photochemical Inhibition." By DAVID LEONARD CHAPMAN and PATRICK SARSFIELD MACMAHON. The nature of photochemical inhibition was discussed. Experiments on the inhibitive influence of ozone and chlorine dioxide on the interaction of chlorine and hydrogen in light (of which a preliminary account has already appeared) were described in detail. A description was also communicated of experiments which showed that the influence of chlorine monoxide on the rate of combination of hydrogen and chlorine is inappreciable. 104. A New Synthesis of Thioxanthone and its Derivatives." (Preliminary Note). By ERIC GORDON DAVIS and SAMUEL SMILES. o-Carboxybenzenesulphinic acid, which is prepared by reducing the chloride of o-sulphobenzoic acid with sodium 2-methyl-1 : 3-benzoxazine-4-one, C6H4O-CHMe CHMe The sulphite may be condensed with benzene, naphthalene, or their derivatives in presence of dehydrating agents, yielding 222 Action of Phosphorus Pentachloride on Unsaturated Compounds. the corresponding thioxanthones. The preparation of o-carboxybenzenesulphinic acid is troublesome, but it is not necessary directly to prepare the acid in order to obtain the desired thioxanthone. Thus thiosalicylic acid in presence of suitable oxidising agents may be directly condensed with aromatic substances, giving the compounds in question. The yields obtained by the latter method are between 80 and 90 per cent of the theoretical. A more complete investigation of the reaction and its products is now being made. 105. "The Action of Phosphorus Pentachloride on Dibenzamide." By ARTHUR WALSH TITHERLEY and ELIZABETH WORRALL. Dibenzamide in presence of chloroform or ether reacts readily with phosphorus pentachloride, yielding a-chloroN-benzoylbenzimide, C6H5 CCI:NBz, identical with the product of the action of phosphorus pentachloride on a-benzilmonoxime (Beckmann, Annalen, 1897, ccxcvi., 279). a-Chloro- benzoylbenzimide readily undergoes fission above 100° into benzoyl chloride and benzonitrile, and with boiling water, benzoic acid and benzonitrile are formed. On the other hand, by the action of cold water for four or five weeks, or atmospheric moisture at 100° for twenty-four hours, much dibenzamide is produced, together with benzoic acid, and benzonitrile, derived by simultaneous fission. Dibenzamide is also produced in good yield by treatment with cold concentrated sulphuric acid and subsequent dilution with water. 106. "Amphoteric Metallic Hydroxides." (Part k). By JOHN KERFoot Wood. The author has continued his investigations of the basic and acidic characters of various metallic hydroxides (Trans., 1908, xciii., 411). The hydroxides now examined are those of zinc, glucinum, and lead. It is found that lead hydroxide is both the strongest acid and strongest base; glucinum hydroxide is the weakest base, and zinc hydroxide the weakest acid. The order of acidity agrees with that arrived at by Hantzsch by other methods (Zeit. Anorg. Chem., 1902, xxx., 302). The author agrees with Hantzsch in considering the formula of sodium plumbite to be Pb(OH)ONa, but differs in his views as to the formula of the salt present in a solution of sodium zincate. The form of the curve showing the solubility of hydroxide in solutions of sodium hydroxide of varying concentration points to sodium zincate having the formula Zn(ONa)2. Glucinum forms a salt of analogous composition to that of sodium zincate, but there is also some CHEMICAL NEWS, 108. "Contribution to Our Knowledge of Oxonium Com pounds.” (Preliminary Note). By ALFRED ARCHIBALD BooN, KENNETH MCKENZIE, and JOHN FOUNTAIN REID. Aldehydes can be condensed with dimethylpyrone, giving coloured bases, which form intensely coloured oxonium salts with acids. From furaldehyde a canaryyellow base (m. p. 200°) was obtained, and from benzaldehyde, a pale yellow compound (m. p. 169°). The salts are either bright red or bright yellow. The study so far indicates that the colour of the salts depends on the nature of the aldehyde used in condensation, as well as that of the acids employed in their production. The condensation takes place according to the following scheme :— The possibility of applying the known relations between optical rotatory power and constitution to determining the structure of organic compounds was discussed. alternative formulæ R·SO2 SR and R·SO SO R for the An attempt has been made to decide between the compounds known as "disulphoxides." The polarimetric examination of dicamphoryl-B-disulphoxide, methyl- and n-butyl-camphoryl-3-disulphoxides, and sodium camphorzinc-thiosulphonate indicates that whilst compounds containing identical alkyl groups, R, R, exist undoubtedly in the symmetrical form (true disulphoxides), those in which the two groups R, R' are not the same may exist in the thiosulphonic form (when R differs widely in nature or approximates to R'). No evidence of transitional forms mass from R') or in the true disulphoxide form (when R evidence in support of the existence of a compound having the formula GI(OH)ONa. 107. "The Action of Methyl tert.-Butyl Ketone on Ketols." (Part I.). By ALFRED ARCHIBALD BOON. The author has found that methyl tert.-butyl ketone does not condense in the presence of potassium cyanide with furoin; but with benzoin a 7-diketone (C20H2202) was obtained after prolonged action. This compound is almost colourless, soluble in most organic solvents, and melts at 110-111°. It forms a monoxime and a dioxime; the latter decomposes at its melting-point (210°). Only one substance, although two others appear to be formed at the same time, was isolated in the pure state when phenylhydrazine was allowed to act on the y-diketone. This compound, 1-anilino-2-tert.-butyl-4: 5-diphenylpyrrole or 1:3: 4-triphenyl-6-tert-butyldihydropyridazine, melts at 167-168°, and was obtained in very small amount. has, however, been obtained. Additional evidence has been drawn from the behaviour of disulphoxides towards alcoholic hydrogen chloride. Unsaturated Compounds." By REGINald William Lane 110. "The Action of Phosphorus Pentachloride on some CLARKE. Piperonylacrylic acid (3: 4-methylenedioxyphenylacrylic acid) when treated with phosphorus pentachloride at 160°, yields a B-dichloro-3 : 4 - dichloromethylenedioxyphenylpropionyl chloride, CC12<>C6H3 CHCI CHCI-COCI, showing that not only are the hydroxyl group and the two methylene hydrogen atoms replaced by chlorine, but also that the substance unites with chlorine at the ethenoid linking, From this substance aß-dichloro-3: 4-carbonyldioxyphenylpropionic acid,— The pyrrole-red reaction was given by the y-diketone, and from it was obtained 2-tert-butyl-4: 5-diphenylfuran, C20H200, m. p. 68-69° (Trans., 1904, lxxxv., 1497), and the following pyrrole derivatives :-A compound, C20H21N, m. p. 98-99°, and 1-phenyl-2-tert.-butyl-4 5-a-chloro-3: 4-carbonyldioxyphenylacrylic acid,— diphenylpyrrole, m. p. 202-203°. Several attempts were made to prepare a thiophen derivative from the compound C20H22O2, but without success. From the author's experiments it would appear that the tert-butyl group has some direct influence on the formation of the thiophen and furan derivatives. Co<o>C6H3 CHCI CHCI-CO2H, Co<o>C6H3-CH:CCI CO2H, and a-chloro-3: 4-dihydroxyphenylacrylic acid (a-chlorocaffeic acid), C6H3(HO)2 CH:CCI CO2H, have been obtained. In view of this behaviour of piperonylacrylic acid, the action of phosphorus pentachloride on other unsaturated substances has been investigated under similar conditions. Cinnamic acid was found to yield as-dichloro-B-phenylpropionyl chloride, C6H5 CHCI CHCI COCI. cinnamic acid gave aas-trichloro-p-phenylpropionyl chloride, C6H5 CHCI∙CCI2 COCI, from which the corresponding acid and methyl ester were obtained. a-Chloro Phenylpropiolic acid gave a3-dichlorocinnamyl chloride, 2:3-dichloroindenone, and 2: 2:3: 3-tetrachlorohydrindone. Crotonic acid yielded aß-dichlorobutyryl chloride, and cinnamaldehyde gave an aẞyy-tetrachloro-a-phenylpropane, different from that obtained by Charon and Dugoujon (Comptes Rendus, 1903, cxxxvi., 94). 111. "Experiments on the Synthesis of the Terpenes. Part X. (continued) Synthesis of Sylvestrene (d-Carvestrene)." (Preliminary Note). By WILLIAM HENRY PERKIN, jun. In a previous communication (Trans., 1907, xci., 480) the synthesis of dl-1-methyl-A1-cyclohexene-3-carboxylic acid (I.) was described, and it was shown that the ester of this acid, on treatment with magnesium methyl iodide, is converted into dl-dihydrocarvestrenol or A1-m-methyl iodide is converted into dl-dihydrocarvestrenol or A1-mmenthenol-(8) (II.). This tertiary alcohol is readily decomposed by boiling with potassium hydrogen sulphate, with elimination of water and formation of dl-carvestrene (III.). The author has now succeeded in resolving dl-1-methylAl-cyclohexene-3-carboxylic acid by means of brucine, and the d-acid thus obtained distils at 1420/20 mm. and has [a]D +70°. Ethyl d-1-methyl-A1-cyclohexene-3-carboxylate, which distils at 143-144°/100 mm. and has [a] +66°, reacts readily with magnesium methyl iodide, with the formation of d-dihydrocarvestrenol or A1-m-menthenol-(8), which distils at 108-111°/30 mm. and has the constitution represented by II. It is remarkable that this tertiary alcohol is optically inactive, but that it is in reality d-dihydrocarvestrenol is shown by the fact that, when treated with hydrochloric acid, it yields d-carvestrene dihydrochloride. This substance melts sharply at 72°, has [a]p +22'0°, and is identical with sylvestrene dihydrochloride, as was proved by direct comparison with a specimen of this hydrochloride, for which the author is indebted to Prof. Wallach. The latter melted at 72° and had [a] D +22·6°, and when mixed with the synthetical dihydrochloride there was no alteration in melting-point. Since sylvestrene dihydrochloride yields sylvestrene on treatment with aniline, the synthesis of this important terpene is complete, and these experiments prove conclusively that sylvestrene is the dextro-modification of carvestrene, and has the constitution represented by the Formula III. given above. |