separable by crystallisation from chloroform. The corresponding methyl ethers melt at 107° (4-nitro-), 83° (6-nitro-; phenylhydrazone, m. p. 154°), and 102° (2-nitro-), respectively. From the nitration product of m-methoxybenzaldehyde (prepared from 50 g. of hydroxybenzaldehyde, 60 c.c. of 25% sodium hydroxide, 200 c.c. of water, and 55 g. of methyl sulphate) only the 2-nitro-compound can be isolated in pure condition. with 4-Nitro-3-hydroxybenzaldehyde condenses arylsulphonylacetonitriles to give a-arylsulphonyl B-4-nitro-3-hydroxyphenylacrylonitriles, (NO2)(OH)CH3 CH.C(CN) SO2Ar, a-benzoyl derivatives. In this way, benzoyl-o-nitroa-benzaldoxime, m. p. 112°, benzoyl-p-nitro-a-benzaldoxime, m. p. 196°, benzoyl-3: 4-methylenedioxy-abenzaldoxime, m. p. 168°, benzoyl-o-methoxy-a-benzaldoxime, m. p. 96°, and benzoyl-p-dimethylaminoa-benzaldoxime, m. p. 138°, were prepared. The action of keten on x-aldoximes yields the acetyl-a-aldoxime (e.g., acetyl-3: 4-methylenedioxy-a-benzaldoxime, m. p. 105°), and on the B-aldoximes the acetyl-3-aldoxime. By Hantzsch's method, acetyl-o-nitro-B-benzaldoxime, m. p. 73°, was prepared, but in other cases the derivatives were contaminated with unchanged oxime. Phenylcarbimide reacts with 3:4-methylenedioxywhere Ar is phenyl (m. p. 155-156°), p-tolyl (m. p. <-benzaldoxime to give a mixture of carbanilino184°), p-chlorophenyl (m. p. 170°), p-bromophenyl (m. p. 3: 4-methylenedioxy-a-benzaldoxime, m. p. 182-183°), o-anisyl (m. p. 187°; acetate, m. p. 156 (decomp.), and the B-isomeride, m. p. 84° (decomp.), 157°), p-phenetyl (m. p. 188°), or B-naphthyl (m. p. the B-compound being more readily prepared from the 174°). 6-Nitro-3-hydroxybenzaldehyde condenses B-aldoxime. In a similar manner, carbanilino-oless easily, giving a-p-toluenesulphonyl-3-(6-nitro- methoxy-a-benzaldoxime, m. p. 107° (decomp.), was 3-hydroxyphenyl)acrylonitrile, m. p. 115-116°, and obtained. Diphenylcarbamyl chloride with o-meth the corresponding p-chlorobenzenesulphonyl (oily; oxybenzaldoxime causes inversion to diphenylacetate, m. p. 130-131°) and o-anisolesulphonyl (oily; carbamyl-o-methoxy-3-benzaldoxime, m. p. 124° acetate, m. p. 142–143°) derivatives. Similarly, the (decomp.), and ethyl chloroformate forms with 4-nitro-3-methoxybenzaldehyde reacts readily, whilst a-cinnamaldoxime carbethoxy-a-cinnamaldoxime, m. p. the 6-nitro ether gives much difficulty. a-p-Toluene- 64°; with the B-oxime, the nitrile is formed. sulphonyl-3-(4-nitro-3-methoxyphenyl)acrylonitrile,m.p. a-Naphthylcarbimide with a-cinnamaldoxime yields 188°, and the corresponding p-chlorobenzenesulphonyl (m. p. 206°) and p-bromobenzenesulphonyl derivatives are described. From the 6-nitro-ether and p-chlorobenzenesulphonylacetonitrile a small amount of a substance, m. p. 117–118°, was obtained. Reduction of the sodium hydrogen sulphite compound of 6-nitro-3-methoxybenzaldehyde with hot ferrous sulphate and sodium carbonate solution gives 6-amino-3-methoxybenzaldehyde (phenylhydrazone, m. p. 179-180°), isolated as hydrochloride from an ethereal solution. The amino-aldehyde condenses with p-chlorobenzenesulphonylacetonitrile to form 2-amino6-methoxy-3-p-chlorobenzenesulphonylquinoline, m. p. 181-182° (described in error as a 2-methylquinoline derivative in the original), and with p-toluenesulphonylacetonitrile to give a base, m. p. 164°. 2-Nitro-3-methoxybenzaldehyde reacts with arylsulphonylacetonitriles, forming a-arylsulphonylB-(2-nitro-3-hydroxyphenyl)acrylonitriles; the p-toluenesulphonyl (m. p. 209°), p-chlorobenzenesulphonyl (m. p. 202°), p-bromobenzenesulphonyl (m. p. 215°), and o-anisolesulphonyl (m. p. 193°) compounds are obtained much more easily than their 6-nitroisomerides. Similarly, 2-amino-3-methoxybenzaldehyde (see preceding abstract) reacts readily than the 6-amino-aldehyde, forming 2-amino8-methoxy-3-arylsulphonylquinolines, MeO-C2H2<CH:C•SO2Ar 6 more N=C•NH2 where Ar is phenyl (m. p. 243-244°), p-chlorophenyl (m. p. 266°), p-bromophenyl (m. p. 281°), p-tolyl (m. p. 256-257°), o-anisyl (m. p. 260°), or p-phenetyl (m. p. 272-273°). C. HOLLINS. Isomerism of the oximes. XXIII. Acyl derivatives. O. L. BRADY and G. P. McHUGH (J.C.S., 1925, 127, 2414-2427; cf. A., 1925, i, 674). The action of benzoyl chloride, not only on a-aldoximes, but also on B-aldoximes, invariably yields the 104° a-naphthylcarbamyl-a-cinnamaldoxime, m. p. 152°, and with B-cinnamaldoxime yields a-naphthylcarbamyl-ẞ-cinnamaldoxime, which exists in yellow amorphous and colourless crystalline modifications, both m. p. 125° (decomp.). B. W. ANDERSON. Isomerism of the oximes. XXIV. 4-Meth oxy-3-methyl-, 3-nitro-4-methyl-, and some 52°, B. W. ANDERSON. p. stereoisomerides (having identical m. p.), of which the yellow form is the less stable. The stability of the yellow form decreases, and the resistance of the molecule to fission by alkaline reagents increases, with increasing mol. wt. Similar properties are observed in the isomerides of the ethyl and n-propyl homologues of 3-methoxy-4-hydroxystyryl methyl ketone. The existence of two distinct isomerides of 3:4methylenedioxystyryl methyl ketone and of 3-methoxy-4-hydroxystyryl methyl ketone has been established by solubility measurements. B. W. ANDERSON. Isomerisation of ay-diphenylallyl alcohol to phenyl ẞ-phenylethyl ketone. H. ÑомURA (Bull. Soc. chim., 1925, [iv], 37, 1245-1247).—ay-Diphenylallyl alcohol, m. p. 56.5-57° (acetate, b. p. 211°/9 mm.), obtained by the action of magnesium phenyl bromide on cinnamaldehyde (cf. Kohler, A., 1904, i, 595), is converted by sodium ethoxide or alcoholic potassium hydroxide almost quantitatively into phenyl 3-phenylethyl ketone, m. p. 72° (oxime, m. p. 84.5-85°; cf. Schneidewind, A., 1888, 704; Perkin, J.C.S., 1891, 59, 1007). R. BRIGHTMAN. Phenyl α-acenaphthyl ketone [3-benzoylacenaphthene] and phenyl-a-acenaphthylmethane [3-benzylacenaphthene]. K. DZIEWOŃSKI and M. RYCHLIK (Ber., 1925, 58, [B], 2239–2249).— 3-Benzoylacenaphthene (annexed formula), m. P: 100-101° (cf. Perrier, A., 1904, i, 804; CH2 CH2 Graebe and Haas, A., 1903, i, 409), is Bz conveniently prepared in 60-70% yield by the action of aluminium chloride on a solution of benzoyl chloride and acenaphthene in carbon disulphide at 15-20° and separation of the benzoyl compound from unchanged material by fractional distillation with superheated steam. It is reduced by zinc dust and potassium hydroxide or by sodium amalgam to phenyl-a acenaphthylcarbinol, m. p. 113-114°, which is transformed by sodium and boiling ethyl alcohol into 3-benzylacenaphthene, m. p. 110-111°, identical with the product obtained previously (Dziewoński and Dotta, A., 1904, i, 390) from benzyl chloride and acenaphthene in the presence of molten zinc chloride and considered erroneously to be 2-benzylacenaphthene. The incorrectness of the previous conclusion is further established by the oxidation of the benzyl or benzoyl compound to the same 4-benzoylnaphthalic anhydride, m. p. 200-201°. The 3-benzoyland 3-benzyl-naphthalic acids (Dziewoński and Wechsler, A., 1904, i, 803) and the tribenzyldecacyclene and dibenzyldinaphthylenethiophen (Dziewoński and Dotta, A., 1904, i, 803) are therefore all to be regarded as 4- instead of 3-derivatives. 4-Benzoylnaphthalic anhydride is converted by hydroxylamine in hot dilute aqueous alkaline solution into the d-oxime, m. p. 254-255° (decomp.) [cf. Dziewoński and Dotta, loc. cit.), which is transformed by a boiling mixture of glacial acetic acid and acetic anhydride into the B-oxime, m. p. 199-200° (cf. Graebe and Haas, loc. cit.); the reverse transformation is effected in more dilute acetic acid solution. The oximes appear to be stereoisomeric. 4-Benzyl Bz C naphthalic anhydride may be prepared by reduction of 4-benzoylnaphthalic anhydride with activated zinc dust and sodium hydroxide solution. 4-Benzoylnaphthalic acid is converted by potassium hydroxide at 180° into naphthalic and benzoic acids. 3-Benzoylacenaphthenequinone, m. p. 199-200°, obtained by oxidation of 3-benzoylacenaphthene in boiling glacial acetic acid solution with sodium dichromate, yields an amorphous trioxime, decomp. 94-96°. 3-Benzoylacenaphthene is converted by sulphur at 200-210°into a mixture of Bz dibenzoyldinaphthylenethiophen (I), m. p. 213–215°, and tribenzoyldecacyclene [tribenzoyltrinaphthylenebenzene], m. p. 335–336°. Nitration of 3-benzoylacenaphthene leads to the formation of (?) 4-nitro-3-benzoylaceraphthene, m. p. 169-171°, in which the nitro-group is certainly present in the a-position of the naphthalene nucleus. 5-Nitro-4-benzoyl naphthalic anhydride, m. p. 273°, and the corresponding imide, m. p. 302-304° (decomp.), are also described. H. WREN. 8118 (I.) C. Ketens in the Friedel Crafts reaction. DE W. HURD (J. Amer. Chem. Soc., 1925, 47, 2777 2780).-Keten reacts with anisole, in presence of one equivalent of aluminium chloride, in carbon disulphide solution, with formation of o- and p-methoxyyields similarly acetophenone and products of higher acetophenones, together with higher ketones. Benzene b. p. Keten is practically inert towards acetophenone in presence of one or two equivalents of aluminium chloride. Naphthalene reacts similarly ketones, and a dark, resinous solid, m. p. 110-160°. with keten at 0°, affording a- and B-naphthyl methyl reaction is carried out at the b. p. of the solvent. a- and B-Dinaphthyls are also produced when the Keten forms an additive product with aluminium chloride when passed into a suspension of the latter in carbon disulphide. The additive product forms a white powder at -10°, and reacts readily with benzene and anisole, with evolution of hydrogen chloride. F. G. WILLSON. Affinity of the group, C(OH) C(:N-OH), for copper. Relationship between atomic grouping and specific affinity. F. FEIGL, G. SICHER, and O. SINGER (Ber., 1925, 58, [B], 2294-2303).—The ability of x-benzoinoxime to yield an insoluble copper salt (I) and its permanence Ph-Ctowards ammonia have been reported ON (I) previously (Feigl, A., 1923, ii, 880). Further investigation has shown that the ability to yield green copper Ph.C -Cu C.Ph salts insoluble in water but decom posed by acids is a general property of acyloins. Variation of the radicals R and R', in the compounds CHR(OH)·CR'(:N⚫OH), has no influence in this respect, but affects the behaviour of the copper salts towards ammonia. Insolubility in ammonia or inability to add ammonia is observed only with those compounds in which the groups R and R' co-ordinat ively saturate the copper atom. This ability is possessed by all aryl groups and it is a matter of indifference whether the acyloins are symmetrical or unsymmetrical. Substituents in the benzene nucleus are without influence; a phenyl group may be replaced by the co-ordinatively unsaturated aminogroup. Only those aliphatic acyloins in which the carbon chain contains more than three atoms have a similar influence. This must be ascribed to the existence of an affinity field in aliphatic residues, and not merely to the effect of the size of the groups, since the copper compounds of phenylbenzoinoxime, CPh2(OH) CPh(:N OH), and benzylbenzoinoxime, in which heavy groups are present, are soluble in ammonia, owing, probably, to the mutual saturation of the residual affinities of the two aromatic residues attached to the same carbon atom. magnesium alkyl halides on phenylglycollamide or on phenylglycollonitrile, obtained by the action of sodium cyanide on the sodium hydrogen sulphite compound of benzaldehyde; with the nitrile secondary alcohols of the type CHPHR.OH are always formed as by-products and lower yields result. Phenylacetylcarbinol is obtained in not more than 15% yield (cf. A., 1923, i, 789); phenylpropionylcarbinol (x-hydroxyphenylmethyl ethyl ketone), m. p. 32-33°, b. p. 124-128°/11 mm., 40% yield from the amide (semicarbazone, m. p. 89-90°; oxime, m. p. 97°); phenylbutyrylcarbinol (a-hydroxyphenylmethyl propyl ketone), b. p. 159-162°/28 mm., d 1.064 (semicarbazone, m. p. 157-158°; oxime, oil); phenylisoThe copper salts are prepared by treating an butyrylcarbinol (x-hydroxyphenylmethyl isopropyl alcoholic solution of the oxime with aqueous or ketone), m. p. 44-45°, distils at 160-170°/35 mm., alcoholic copper acetate solution. The amorphous 28-30% yield, from the amide (semicarbazone, m. p. precipitates are purified from co-precipitated, basic 158-159°; oxime, liquid); a-hydroxyphenylmethyl copper salts by digestion with dilute acetic acid, n-butyl ketone, a yellow oil, d 1-045, distilling at 145whilst excess of the oxime can be removed by alcohol. 160°/13 mm., 20% yield, from the amide (semiThe copper salts of the following compounds are carbazone, m. p. 152-153°; oxime, m. p. 95-96°); described: lævuloseoxime, acetoloxime, acetoinoxime, a-hydroxyphenylmethyl isobutyl ketone, orange-yellow, propioinoxime, n-butyroinoxime, n-valeroinoxime, b. p. 155-157°/38 mm., d 1.048, 17% yield (semin-hexoinoxime, n-heptoinoxime, diphenylacetoin- carbazone, m. p. 123°; oxime, m. p. 99-100°), and oxime, benzoinoxime, furoinoxime, anisoinoxime, a-hydroxyphenylmethyl benzyl ketone, m. p. 115-116°, cuminoinoxime, piperonyloinoxime, a-hydroxyphenyl- 30% yield (semicarbazone, m. p. 189-190°). The acetamideoxime, benzfuroinoxime, benzanisoinoxime, last-named differs from the remaining ketols in being cuminanisoinoxime, p-dimethylaminobenzoinoxime, non-volatile in steam. Reactions between solutions of benzoin and of aromatic aldehydes in pyridine and metallic copper. H. MOHLER (Helv. Chim. Acta, 1925, 8, 740-757). The dissolution of copper in pyridine solutions of benzoin has been traced to a reaction of benzoic acid with copper. The deep blue compound which results consists of copper benzoate with pyridine of crystallisation. The mean rate of dissolution of the metal has been determined at constant temperature. Parallel experiments were carried out by passing in a current of air or nitrogen and by using benzil, benzoic acid, and benzilic acid. The dissolution of copper in pyridine solutions of benzoin is a heterogeneous double reaction with at least two induction phenomena. The oxidation of benzoin to benzoic acid by oxygen is bound up with the presence of copper, and pyridine plays a definite part in the whole reaction. The benzoic acid will react with copper only in the presence of oxygen or a reducible substance. The combination of copper, pyridine, and oxygen is therefore a very strong oxidising system. The rate of dissolution of copper in dilute pyridine solutions of the following aldehydes has been measured: benzaldehyde, anisaldehyde, p-tolualdehyde, p-dimethylaminobenzaldehyde, p-nitrobenzaldehyde, cinnamaldehyde. Not only the rates of oxidation of the aldehyde, but also the rates of dissolution of copper depend on the chemical constitution of the respective aldehydes. R. A. MORTON. Ketone-alcohols of the general formula, CHPh(OH) CO-R. M. TIFFENEAU and (MLLE.) J. LEVY (Bull. Soc. chim., 1925, [iv], 37, 1247-1251) Ketone-alcohols have been obtained by the action of R. BRIGHTMAN. Co-ordinated compounds of the alkali metals. II. N. V. SIDGWICK and F. M. BREWER (J.C.S., 1925, 127, 2379-2387; cf. Sidgwick and Plant, A., 1925, i, 298). The sodium or potassium derivatives exist in a non-polar form, in which the metal exhibits of ethyl acetoacetate and some similar compounds 2-covalency, forming part of a chelate ring; these are soluble in benzene and have a definite m. p. Many metallic derivatives which are insoluble in benzene alone dissolve readily in presence of the parent substance or some similar compound, the metal being here 4-covalent and forming a bichelate compound. The sodium derivative of benzoylacetone behaves as a salt, but readily takes up 2 mols. of water from 96% alcohol, the hydrate containing 4-covalent sodium, and being soluble in hydrocarbons. Several similar compounds, and some containing lithium and potassium, have been prepared. Sodium and potassium derivatives of salicylaldehyde combine with excess of the aldehyde, forming bichelate additive compounds, and the same aldehyde forms similar compounds with sodium and potassium o-nitrophenoxides. Whereas lithium atoms are limited to a covalency of four, 6-covalent metallic atoms are found in additive com pounds of the disodium and dipotassium salts of quinizarin with 4 mols. of salicylaldehyde. B. W. ANDERSON. Perylene and its derivatives. XI. A. ZINKE, R. SPRINGER, and A. SCHMID (Ber., 1925, 58, [B], 2386-2391; cf. A., 1925, i, 1436, and previous abstracts).-4: 10-Dichloro- or 4: 10-dibromo-perylene is converted by concentrated sulphuric acid at 165-170° into hydrogen halide and 4: 10-perylenequinone, which could be isolated only as the additive compound (C20H10O2)2,H2O. It is transformed by distillation with zinc dust and zinc chloride into perylene. Reduction with sodium hyposulphite in alkaline solution followed by treatment with the appropriate aroyl chloride affords the dibenzoyl, m. p. 324°, and di-p-bromobenzoyl, m. p. 359-361°, derivatives of 4: 10-perylenequinol; the mol. wts. of these compounds are established by Rast's method, using perylene as solvent. H. WREN. 20 p. Olefinic terpene ketones from the volatile oil of flowering Tagetes glandulifera. I. T. G. H. JONES and F. B. SMITH (J.C.S., 1925, 127, 25302539). The volatile oil of T. glandulifera contains, in addition to ocimene (30%) and d-limonene (3%), 5-10% and 50-60%, respectively, of two new terpenes. These are yn-dimethyl-Aa-octen-e-one, b. p. 185°, d5 0.8354, n 1-4295, [x] +1.5° (semicarbazone, m. p. 92.5°; oxime, b. p. 222°), and n-methyl-y-methylene-▲-octen-e-one, "tagetone," b. 210°, dis 0.8803, n 1-4895 (oxime, b. p. 126°/25 mm.). yn-Dimethyl-Aa-octen-e-one on reduction yields yn-dimethyloctan-e-one, b. p. 188° (semicarbazone, m. p. 91.5°; oxime, b. p. 225°), and on oxidation gives B-isovaleryl-a-methylpropionic acid, m. p. 25° (semicarbazone, m. p. 165°), with some isovaleric and formic acids. Reduction of tagetone in ether by sodium gives a substance, C10H180, b. p. 197°, d155 0-8524, n 1-4490, and a pinacol, C20H3402, b. p. 183°/4 mm., d155 0-9258, n 1-4820, containing four double linkings. Oxidation of tagetone yields isovaleric and oxalic acids. B. W. ANDERSON. Occurrence of sylvestrene. B. S. RAO and J. L. SIMONSEN (J.C.S., 1925, 127, 2494-2499). The oils from Pinus sylvestris and P. pumilio contain no sylvestrene; treatment of the oil with hydrogen chloride yields sylvestrene dihydrochloride, but this is formed from the A3-carene present. It is improbable that sylvestrene occurs in nature. B. W. ANDERSON. Action of metals on dipentene dihydrohalide. Preparation of a synthetic diterpene. K. C. ROBERTS (J.C.S., 1925, 127, 2451). When alcoholic solutions of cis- and trans-dipentene dihydrobromide and of trans-dipentene dihydrochloride were shaken with finely divided silver or copper, loss of hydrogen halide took place, with production of dipentene, which polymerised to a diterpene, C2H32, b. p. 173-183°/ 13 mm., n 1.5170, do 0-9361, iodine value, 103. B. W. ANDERSON. Constitution of pulegone, tertiary alkylpulegols, and pulegenes. V. GRIGNARD and J. SAVARD (Compt. rend., 1925, 181, 589-592; cf. Grignard, A., 1901, i, 681; Rupe, A., 1908, i, 556; Auwers and Eisenlohr, A., 1910, ii, 368).—Treatment with ozone demonstrates the presence in pulegone of two isomerides, ß-pulegone, i.e., 1-methyl-4-A4(8) isopropylidenecyclohexan-3-one, and 15-18% of a-pulegone, i.e., 1-methyl-4-A3-isopropylidenecyclohexan-3-one. Treatment with organo-magnesium compounds yields the isomeric tertiary alkylpulegols present in the same relative proportions. When these alcohols are treated with dehydrating agents (e.g., acetic anhydride, phosphorus trichloride), however, different proportions of the isomeric unsaturated hydrocarbons are obtained, the reaction products containing the following proportions of a-isomeride: methylpulegene, 68%; n-propylpulegene, 24%; n-butylpulegene, 50%; isopropylpulegene, 43%. x-Methylpulegene on treatment with ozone yields y-methyl-e-ketoheptoic acid (Rupe, loc. cit.), and must therefore have the structure, 1:3-dimethyl4-48-isopropylidene-3-cyclohexene (I). B-n-Propylpulegene when treated with ozone gives a-methylglutaric acid and is therefore 1-methyl-3-n-propyl CMe:CH2 CMe2 4-A48-isopropylidene-A2-cyclohexene (II). It is suggested that the homologous compounds have analogous formulæ, but the absence of the exaltation of molecular refraction to be anticipated from the system of conjugated unsaturated linkings is remarkable. L. F. HEWITT. Borneol in spruce turpentine. A. S. WHEELER and C. R. HARRIS (J. Amer. Chem. Soc., 1925, 47, 2836-2838).-See B., 1925, 1012. Camphor oils. III. Action of oxalic acid on terpin hydrate. K. ONO (Mem. Coll. Sci. Kyōtō, 1925, 9, [A], 75-79; cf. Aschan, A., 1919, i, 336).-Terpin hydrate, heated on an oil-bath for 5 hrs. with twice its volume of 0.5% oxalic acid solution, gave good yields of a-terpineol and some B-terpineol. B. W. ANDERSON. Camphor oils. IV. Reaction of Japanese acid clay to terpin hydrate and terpineol. K. ONO (Mem. Coll. Sci. Kyōtō, 1925, 9, [a], 153–159). Both terpineol and terpin hydrate when treated with Japanese acid clay yield principally p-cymene and p-menthane, probably undergoing dehydration before decomposing into these products. B. W. ANDERSON. SCHAERER (Helv. Chim. Acta, 1925, 8, 853-865).— Esters of camphylcarbinol. H. RUPE and M. Since the reduction of hydroxymethylenecamphor to camphylcarbinol introduces a new asymmetric carbon atom, this substance should occur in two stereoisomeric forms. No evidence of the existence of these stereoisomerides is found with camphylcarbinol or with the majority of its esters, but the isobutyrate has been isolated in two forms. Camphylcarbinol has [x] +62-22°, and its formate [ +18-13°. A series of esters has been prepared by the action of the respective acid chlorides on the carbinol in presence of pyridine, and distilled in a high vacuum: propionate, b. p. 63°, m. p. 28-36° indef., d20 1-042, [a] +55-37°, and in 10% benzene solution +16-15°; isobutyrate, b. p. 61°, da 1-0217, [a] +56-16°, which deposited crystals, m. p. 31.5— 33, having [a in 10% benzene solution +23-48°, whilst the liquid portion had the corresponding value +36-85°; n-butyrate, b. p. 73°, do 1·0254, [a] +53-45° (+33-35° in benzene); n-valerate, b. p. 82°, d 1.0140, [a] +49-18° (+29-57° in benzene); hexahydrobenzoate, b. p. 95°, d 1·0507, [x] +49-49° (+32-16° in benzene); phenylacetate, b. p. 120°, d 1.0902, [x] +40·94° (+26-59° in benzene); B-phenylpropionate, b. p. 141°, de 1·0791, [x] +38.56° (+27-43° in benzene); cinnamate, b. p. 145°, do 1.1004, [a] +46-06° (+21.82° in benzene); crotonate, b. p. 79°, da 1·0506, [a] +56·52° (+34-30° in benzene); sorbate, b. p. 99°, da 1-0433, [a] +54-55° (+33-86° in benzene). Optical rotatory powers are tabulated in all cases for four different wave-lengths: the value [a]/[a] is remarkably constant throughout 2.36 with 591.5, 2,2 0.09271, these figures being almost identical with those for the hydroxymethylenecamphor derivatives. The curves relating 1/[a] to 22 for the propionate and isobutyrate are not quite straight lines, a fact which is taken to confirm the indications of the presence of the expected stereoisomerides. G. M. BENNETT. Cymarin and strophanthin. A. WINDAUS, G. REVEREY, and A. SCHWIEGER (Ber., 1925, 58, [B], 1509-1514; cf. Windaus and Hermanns, A., 1915, i, 703, 704; Jacobs and co-workers, A., 1923, i, 123; 1924, i, 65, 867, 1331).-Strophanthidin resembles cholesterol in that it contains a tetracyclic system. It is an unsaturated hydroxylactone similar to the genins of the Digitalis glucosides, from which it differs by the presence of the ketonic group in addition to three hydroxy-groups. Further, it has one carbon atom less than the Digitalis genins, so that the fundamental substance of strophanthidin, C2H6O3, appears to be the next lower homologue of hexahydrodigitaligenin. The methylsemiacetal of dianhydrostrophanthidin (cf. A., 1924, i, 867) is hydrogenated in glacial acetic acid suspension in the presence of platinum, pretreated with hydrogen, to hexahydrodianhydrostrophanthidin, C23H3O4, m. p. 208°, whereas, if the metal has been treated previously with oxygen, octahydrodianhydrostrophanthidin, C2H3604, m. p. p. 265-266° (monoacetyl derivative, m. p. 185°), is obtained. The octahydro-compound is converted by cautious oxidation with chromic acid into the hexahydro-derivative. The latter compound is transformed by amalgamated zinc and hydrochloric acid into deoxyoctahydrodianhydrostrophanthidin, C2H36O3, m. p. 224°. H. WREN. of Strophanthin. VIII. Carbonyl group strophanthin. W. A. JACOBS and A. M. COLLINS (J. Biol. Chem., 1925, 65, 491–505; cf. A., 1925, i, 566, 1082, and earlier abstracts).-Oxidation with chromic acid in acetic acid solution of dianhydrostrophanthidin yielded a dilactone, C23H2604, m. p. 253-254°, [a]-178° in chloroform, together with a small amount of a lactonic acid, C2H28052 m. p. 268°, [a] -100° in 95% alcohol. This acid was also obtained by the oxidation of dianhydrostrophanthidin with potassium permanganate in acetone solution, in which case none of the dilactone was formed. This result is taken to show that dianhydrostrophanthidin exists as an equilibrated mixture of an oxidic and an aldehydic form, the a former of which is oxidised specifically by chromic acid and the latter by potassium permanganate. The above dilactone, on hydrolysis, gave a dibasic acid, C23H3006, m. p. 249–251°. The lactone, with hydrogen and palladium, gave a tetrahydro-derivative, C23H3004, m. p. 275—277°, [a] +3.0° in chloroform; hydrolysis of this compound by boiling for 2 hrs. with 0-05N-sodium hydroxide opened one lactone ring, giving a lactonic acid, m. p. 225-230°; for complete hydrolysis, boiling for 5 hrs. with 2N/3-sodium hydroxide was required. The tetrahydrodilactone still contained a double linking. With some difficulty two more hydrogen atoms were introduced to form a hexahydrodilactone, C23H3204, m. p. 265-267°, [a] +14° in chloroform; this substance did not reduce Tollens' reagent; its second lactone group showed a resistance to hydrolysis similar to that observed with the tetrahydro-derivative. The lactonic acid obtained previously (A., 1923, i, 65) by the oxidation of strophanthidin with potassium permanganate in acetone solution is now given the formula C23H3207, it being assumed to be formed by the oxidation of the aldehydic form of strophanthidin as indicated above; on treatment with concentrated hydrochloric acid, it gave a dilactone, C23H30O6, m. p. 235-236°, [a] +100° in methyl alcohol; dihydrostrophanthidin under similar conditions yielded an analogous lactonic acid, C2H3407, platelets with 2H2O, effervescing at 132—133°, [a]B +47° in methyl alcohol, and this in turn a dilactone, C2H2O6, m. p. 232-234°, [a] +84° in methyl alcohol; the latter substance did not reduce Tollens' reagent; both these dilactones showed a resistance to the hydrolysis of the second lactone group similar to that observed with the anhydro-derivatives described above. Oxidation with chromic acid of the dilactone, C23H3006, yielded a ketodilactone, CH2806, m. p. 285°, [a] +93° in pyridine, which in turn gave an oxime, m. p. above 285°. The same ketodilactone was obtained by a similar oxidation of pseudostrophanthidin (A., 1925, i, 566), which is not oxidised by potassium permanganate in acetone; pseudostrophanthidin is therefore to be regarded as a stable oxidic form of the hydroxyaldehyde, strophanthidin. C. R. HARINGTON. MeO 23 Tannins and related substances. XXI, Molecular rearrangement of catechin derivatives. K. FREUDENBERG, G. CARRARA, and E. COHN (Annalen, 1925, 446, 87-95; cf. A., 1925, i, 1165).-trans-Epicatechin tetramethyl ether (I) on dehydration OMe yields an anhydroCOMe epicatechin tetramethyl ether (II). The wandering of the dimethoxyphenyl group during the dehydration has been proved by the synthesis of the hydrogenation product of (II). MeO CH2 CHCH⚫OH (I.) OMe MeO CH OMe (II.) MeŎ CH2 By the condensation of 3: 4-dimethoxyphenylacetonitrile with phloroglucinol trimethyl ether is |