forming ethenyltriphenol, HO C2H12CH2 CH·(C,H,OH)2, and other products. If less than 3 mols. of phenol are taken, an insoluble resin is formed. The crude product is dissolved in alkali, reprecipitated by hydrochloric acid, and distilled in a current of steam to remove the excess of phenol. These three operations must be repeated several times. Ethenyltriphenol yields a triacetate soluble in ether, alcohol, chloroform, acetone, benzene, aniline, phenol, and acetic acid. The acetic acid solution is oxidised by ferric chloride, yielding isorosolic acid, C20H16O3, a dark, carmine-red, amorphous powder. Isorosolic acid yields a sulphonic acid. From an acetic acid solution of isorosolic acid, chromic acid throws down an amorphous insoluble compound containing chromium.

W. C. W.

By

Action of Dichlorether on the Dihydroxybenzenes. J. WISLICENUS and M. SIEGFRIED (Annalen, 243, 171–192).—Ethenyltriresorcinol, C2H3[CH3(OH)2], is formed by the action of dichlorether (14 grams) on 33 grams of resorcinol dissolved in 300 grams of benzene. It is a pale-red, amorphous powder soluble in water, alkalis, alcohol, acetone, and in strong acetic acid. It is precipitated by hydrochloric acid from alkaline solutions, and after the precipitate has been dried in a vacuum, it is sparingly soluble in water, alcohol, and acetic acid. A monacetic derivative is obtained by the action of glacial acetic acid at 85°. It is insoluble in the ordinary solvents, and is converted into an insoluble hexacetate by the action of acetic anhydride at 200°. By the action of acetic anhydride on ethenyltriresorcinol at 170°, an amorphous hexacetate is obtained which is soluble in acetone, chloroform, benzene, and acetic acid. A chocolatecoloured, amorphous substance is formed by boiling ethenyltriresorcinol with glacial acetic acid and ferric chloride. When freshly prepared, it is soluble in alcohol, acetone, and acetic acid. It also dissolves in alkalis, yielding a cherry-red solution. It yields a pentacetate, C20H11(AC),Og When bromine acts on ethenyltriresorcinol, two hydrogen-atoms are eliminated and six are substituted by bromine, yielding C20HBrOe, a substance soluble in alcohol, ether, acetone, chloroform and acetic acid.

10

Ethenyltricatechol is obtained as an amorphous compound by the action of dichlorether on a mixture of pyrocatechol and benzene. It is soluble in alcohol, acetone, acetic acid, and alkalis. It yields a hexacetate. On oxidation with ferric chloride, it loses two atoms of hydrogen, but the product could not be obtained in a pure state, although its pentacetate, C20H(Ac)sO6, was prepared. Bromine converts ethenyltricatechol into the hexabromide, C20H1Bг5O6, from which the pentacetate, C20HВгAсãО, was obtained.

11

Ethenyltriquinol is prepared by the action of dichlorether on a solution of quinol in warm ethyl acetate. It is an amorphous substance, soluble in alcohol, acetone, acetic acid, and in alkalis. The hexacetate is soluble in acetone, chloroform, and acetic acid. Ethenyltriquinol yields a green colouring matter, C20H16O6, when it is treated with ferric chloride; a bromide, CH,Br2Oε, can also be prepared. When an excess of dichlorether acts on a solution of quinol in ethyl acetate,

a resin and a soluble compound are formed. The latter resembles ethenyltriquinol, but has the composition C16H13CIO1.

W. C. W. Action of Sulphur on the Salts of Aromatic Hydroxy-compounds. By M. LANGE (Ber., 21, 260-264).-When B-naphthol is dissolved in aqueous soda and boiled with an excess of sulphur, the latter dissolves and dihydroxydinaphthyl disulphide, S.(CHOH)2, is formed. This crystallises in white, opaque needles. melts at 210° (uncorr.) and is insoluble in water, sparingly soluble in ethyl alcohol, readily soluble in acetic acid, benzene, amyl alcohol, alkalis, and alkaline sulphides. From the mother-liquors, a second compound of like composition can be separated, which crystallises in long, yellow needles, melts at 168-170°, is more soluble in all solvents than dihydroxydinaphthyl disulphide, and is also distinguished from it by its greater acidity. Both compounds yield ẞ-naphthol on distillation and when heated with alkalis or ammonia at 150°. Dihydroxydinaphthyl disulphide is alone formed when ẞ-naphthol is heated with sulphur and lead oxide at 180-200°.

Resorcinol, when treated in like manner, yields a compound, CHOS2, provisionally termed thioresorcinol. It is a yellow powder, which carbonises before fusion, and is almost insoluble in the ordinary solvents, but readily soluble in alkalis, alkaline carbonates, and alkaline sulphides. W. P. W.

Action of Fuming Sulphuric Acid on a-Naphthylamine Hydrochloride. By R. MAUZELIUS (Ber., 20, 3401-3404).-The sulphonic acid prepared by Witt (Abstr., 1886, 554), by the action of fuming sulphuric acid on a-naphthylamine hydrochloride, is shown to be a-amidonaphthalenesulphonic acid. The acid was prepared exactly as described by Witt (loc. cit.), and was purified by means of the calcium salt. The different results obtained by Witt appear to be due to the presence of some impurity. N. H. M.

a-Naphthaldehyde. By E. BAMBERGER and W. LODTER (Ber., 21, 256-260).—When equimolecular proportions of a-naphthabenzylamine hydrochloride and sodium nitrite are dissolved in water, the nitrite of the base, CH, CH2 NH2,HNO2, is obtained; this crystallises from water, in which it is sparingly soluble, in long, slender prisms, and melts and suddenly decomposes at 148.5°.

2

x-Naphthabenzyl alcohol, CH, CH, OH, is prepared by diazotising the amine. It crystallises in long, lustrous needles, melts at 59-60°, boils at 301° (corr.) under 715 mm. pressure, and is readily soluble in alcohol and ether, less soluble in hot water. On oxidation with potassium dichromate and sulphuric acid, it is converted into a-naphthaldehyde, CH, CHO. This is a thick, pale-yellow oil of slightly aromatic odour, which boils at 291 6° (corr.) without decomposition and gives the characteristic aldehyde reactions; the phenylhydrazide crystallises in lustrous, bright-yellow scales and melts at 185°. On treatment with nitric acid (sp. gr. = 1:47) at 5-0°, a mixture of nitraldehydes is obtained, one of which crystallises in lustrous, paleyellow needles, melts at 136°, is very sparingly soluble in cold alcohol,

and does not give a colour reaction with acetone and aqueous soda. a-Naphthaldehyde could not be obtained by distilling calcium. a-naphthoate with calcium formate. W. P. W.

:

1: 4' Bromonaphthalenesulphonic Acid. By R. MAUZELIUS (Ber., 20, 3404-3407).-1: 4' Bromonaphthalenesulphonic acid. (Darmstädter and Wichelhaus, Annalen, 152, 303) is prepared by adding 1 4' diazonaphthalenesulphonic acid to warm, strong hydrobromic acid; the solution is neutralised with potassium carbonate, the potassium salt recrystallised from hot water, dried and rubbed with phosphorus pentachloride; the product is then treated with water, extracted with ether, and crystallised from glacial acetic acid. The chloride is heated with water at 130°. The impure acid melts at 126°. The barium salt (with 2 mols. H2O) is sparingly soluble; the silver salt crystallises in pale-yellow lustrous scales. The chloride crystallises in well-formed crystals melting at 94°. The amide forms. yellowish needles melting at 232-233°. The ethyl salt crystallises well, dissolves readily in alcohol, chloroform, and ether, &c., and melts at 51° (compare also Jolin, Verhand. d. schwed. Akad. d. Wissens., 1877, No. 7). N. H. M.

Reduction of the Thiamides of Aromatic Acids. By E. BAMBERGER and W. LODTER (Ber., 21, 51–56).—When an aromatic thiamide is reduced with zinc and hydrochloric acid, a benzylamine base is not the only product, a hydrocarbon is obtained at the same time in quantities of about 1 to 2 per cent. of the thiamide employed.

Symmetrical di-a-naphthylethane, CH7 CH2 CH2 CH7, is formed in the reduction of a-naphthothiamide in alcoholic solution; on evaporation, an oily resinous mass is obtained; this is treated with soda, and the oil which separates is distilled. As soon as the naphthobenzylamine has passed over, the thermometer rises rapidly above 360° and a thick yellow oil distils, and in a short time solidifies. The dinaphthylethane thus obtained, after purification and crystallisation from alcoholic benzene, forms shining, hexagonal plates which are readily soluble in benzene and chloroform, less so in ether, and sparingly soluble in alcohol with a green fluorescence. The crystals are greenish-yellow, and melt at 160° to a yellow oil with moss-green fluorescence.

Symmetrical di-B-naphthylethane is obtained by extracting with benzene the resinous product formed in the reduction of B-naphthothiamide. It crystallises from benzene and chloroform in shining silver-white, plates melting at 253°, is only sparingly soluble in ordinary solvents, most readily in chloroform and benzene, and less so in boiling alcohol and ether; the solutions have a blue-violet fluorescence.

The resinous product formed in the reduction of benzothiamide contains stilbene, which can be isolated by boiling with alcoholic potash and then distilling with steam. F. S. K.

Action of Dichlorether on Naphthol. By J. WISLICENUS and G. ZWANZIGER (Annalen, 243, 165–171).-Ethenyltri-a-naphthol is formed by the action of dichlorether on a-naphthol. The crude product is purified by solution in alkalis and reprecipitation by acetic acid. It

is an amorphous, white powder, soluble in acetic acid, alcohol, ether, acetone, and in dilute alkalis. It forms a crystalline triacetyl-derivative, C2H2Ac3O. When ethenyltri-a-naphthol is oxidised by ferric chloride, it is converted into a brownish-red colouring matter of the composition CH2O3. The action of dichlorether on ẞ-naphthol is not analogous to its action on a-naphthol. The product, C22H1CIO, crystallises in plates melting at 174°. It resists the action of boiling potash and is not attacked by acetic anhydride. W. C. W.

and molecular refraction

n2

--

Terpenes and their Derivatives. By J. W. BRÜHL (Ber., 21, 145-179). A comparative study of the chemical and physical properties of the terpenes. A table containing the boiling point, rotation, density d, refractive index for the C line n, specific refraction n2 - 1 no - 1 P (P being the molecular (n2 + 2)d' 2 d weight), of a number of the best known terpenes, has been compiled from the data of different observers. The terpenes are thus divided into eight groups, similar to those given by Wallach (Abstr., 1887, 965), phellandrene and terpinene coming under the heading laurene, and menthene and sesquiterpene forming an extra group. These groups are:

1. Citrene (limonene), boiling point 172-179°, the differences probably due to impurities in the specimens examined. Dextrorotatory. Sp. gr. 0.846. Refractive index 1:47. Specific refraction Absorbs 2 mols. HCl, the resulting product being identical with the similar product from dipentene, and giving the latter and not citrene when the hydrogen chloride is removed by means of aniline. From this, and the formation of a tetrabromide melting at 104°, the presence of two unsaturated or double bonds is probable, as also from the molecular refraction which agrees closely with that calculated for such an unsaturated compound.

2. Dipentene. Differs from the above only in being optically inactive and yielding a tetrabromide melting at 124°.

3. Isopentene. Dextrorotatory, differs only slightly from the two former in physical properties.

4 Sylvestrene. Has probably never been prepared in a state of purity, and does not appear to differ in any marked degree from the foregoing.

5. Pinene. Boiling point 155-160°. Sp. gr. 0.859. Refractive index 1-463. Specific refraction 0-320. The molecular refraction is that of a compound containing one double bond. This agrees with the chemical evidence, as pinene combines with 2 mols. of bromine and 1 mol. HCl.

6. Laurene and Menthene.-Boiling point 173-175°. tatory. Resembles pinene in other respects.

Lævoro

7. Camphene.-Solid, melting at 47°; boils at 156-157°. The hydrogen chloride derivative is very unstable and is decomposed by water at ordinary temperatures; it is therefore probable that this is only a molecular compound, camphene containing no double bond, a view supported by its optical properties.

8. Sesquiterpene, C1H2.-Found in volatile oils associated with the

VOL. LIV.

2 c

terpenes. Boiling point 250-260°. Rotation differs for different varieties. From its optical and chemical properties appears to contain two double bonds.

The author regards the terpenes as derivatives of paracymene. Formulæ similar to those of Wallach (loc. cit.) are proposed for citrene, dipentene, pinene, and phellandrene, and a discussion of the various possible formulæ for the other terpenes is entered into.

H. C. Specific Rotation of Dextrocamphoric Acid and its Salts. By W. HARTMANN (Ber., 21, 221-230).-The specific rotation of dextrocamphoric acid and its salts in solution is represented generally by [a] = a + bp or A + Bq, p being the percentage of active substance, q that of the solvent, a the specific rotation for greatest dilution, A that for greatest concentration. The rotation of the free acid in acetic acid, acetone and alcohol varies with the nature of the solvent. The anhydride is optically inactive. The constants in the above equations were determined for solutions of the lithium, magnesium, ammonium, calcium, sodium, potassium and barium salts. By the aid of these constants, the specific rotation of the acid in the salts was calculated, which is more than double that of the free acid, and is nearly equal for all salts for the same dilution. The molecular rotation M = [a]P/100, where P is the molecular weight, was also calculated for solutions of the above salts for p = 0, 5, 10, 15, and 20. It is found that the molecular rotation is very nearly the same for all salts at the same concentration. Hence also the specific rotation increases with the molecular weight. H. C.

Alantic Acid and Alantole. By MARPMANN (Arch. Pharm. [3], 25, 826-827; from Bresl. ärztl. Zeit., 5, 1887).-On distilling the root of Inula helenium with water, a distillate is obtained containing helenin, C2H6O2, alantic anhydride, C1sH20O2, and alantole, C20HO.

Alantic acid crystallised from alcohol, melts at 91°, and sublimes with loss of the elements of water, becoming alantic anhydride; both compounds are insoluble in water, soluble in alcohol, and with alkalis form salts soluble in water. Alantole is an aromatic liquid which boils at 200°, is lævorotatory, and has ozonising properties somewhat similar to those of the turpentine oils. Helenin, alantic acid, and alantole are antiseptics. J. T.

=

Oxidation of 1-Quinolinesulphonic Acid. By H. ZÜRCHER (Ber., 21, 180-182).-Amidosulphobenzoic acid, [COOH: NH,: SO,H 1:2:3], is formed in small quantity when 1-quinolinesulphonic acid is oxidised to quinolinic acid by Fischer and Renouf's method (Abstr., 1884, 1049). The yield amounts to about 5 grams from 90 grams of quinoline. W. P. W.

Reactions of the Opium Alkaloïds. By P. C. PLUGGE (Arch. Pharm. [3], 25, 793-811).-With potassium chromate, solutions of narcotine salts, both cold and warm, give a precipitate of free narcotine. Papaverine in the cold gives a mixture of chromate and free alkaloïd : but with heat free papaverine only. Narceïne in cold saturated