40 mm., and has the distinct odour of hyacinth shown by List's terpilenol. Its rotatory power is [a]D= +67° 30'.

Citrene, when treated with formic acid in the cold during three months, affords some cymene and a compound, C20H32, which boils at 212°. This is a viscous, yellow substance with odour resembling that of copaiba, sp. gr. = 0·9404 at 0°; it does not affect polarised light. Citrene and formic acid give the same products when heated at 100° in a sealed tube during 18 hours. J. T.

Terpinol. By G. BOUCHARDAT and R. VOIRY (Compt. rend., 106, 663-665).—When terpilenol, boiling at 172-176° (Abstr., 1887, 677), is saturated with hydrogen chloride at -25°, the oxygen com-pound, for which the authors propose the name terpane, is converted into the hydrochloride 2C10H1O,HCl, whilst the terpilenic bydrocarbon forms the hydrochloride C10H16,2HCl. If the liquid is not cooled, the terpane is at once converted into the dihydrochloride. When the compound (C10H18O)2,HCl is washed with water at 0°, it is decomposed with development of heat and liberation of terpane. The hydrochloric acid is removed by treatment with dilute alkali, and the terpane is distilled under a pressure of 15 mm. at a temperature not exceeding 80°. The product boils at 78-79° in a vacuum, and is impure, but yields solid terpane if cooled to -50-55°; the formation of crystals being accelerated by the addition of a fragment of the terpane from eucalyptol. This terpane boils at 174°, and its sp. gr. (0·935 at 0°) and melting point (-3° to -1°) are identical with those of terpane from eucalyptol and similar natural products. Its odour recalls that of menthol, &c. Hydrogen chloride converts it into the crystalline hydrochloride, (C10H18O)2HCl, which liquefies in a vacuum or under water with liberation of terpane. In a sealed tube, it decom-poses spontaneously into C10H16,2HCI, C19H190 and water. When treated with an ethereal solution of bromine, terpane yields a granular cinnabar-red product, which is a mixture of a red additive product with colourless substitution-derivatives; this reaction, like that with hydrochloric acid, may be used to separate terpane from terpilenol but requires greater precautions. The terpane thus obtained always retains a small quantity of a hydrobromide of sp. gr. above 0.977, analogous to but more stable than the hydrochloride.

It follows from these reactions that List's terpilenol consists of inactive crystalline terpinol or terpol, C10H16O, boiling at 218°; terpane, CHO, boiling at 175° and crystallising at -1°; and inactive terpilene, C10H16.

Terpane differs from active and inactive terpilenols in that it does not combine with acids or anhydrides to form ethereal salts. This confirms Wallach's observations, and supports his view that terpane is the ether or anhydride of terpene.

C. H. B.

Oxidation of Hydrazocamphenes. By C. TANRET (Compt. rend., 106, 660-662 and 749-751).-If a cold solution of a-hydrazocamphene in 1 per cent. sulphuric acid is gradually mixed with standard potassium permanganate solution until the colour just ceases to be discharged, it yields a blue precipitate of azocamphene,

64

CHAN,Os. This is dissolved in ether, and the solution first washed with water and with dilute soda solution and then evaporated to dryness. Azocamphene thus obtained melts at 153°, and is insoluble in water but very soluble in cold ether, alcohol, and chloroform. Α 50 per cent. ethereal solution gradually deposits a white crystalline powder which is insoluble in cold alcohol or ether but dissolves on heating with formation of a blue solution. The crystals become blue at 80°, and if kept at this temperature for some time regain their solubility in cold alcohol or ether. The white crystals have the same composition as the blue compound, melt at 153°, and are insoluble in cold water but dissolve in their own weight of chloroform, the solution becoming blue. It is evident that azocamphene can exist in two modifications, which the author distinguishes as eyanazocamphene and leucazocamphene. The azocamphene from p-hydrazocamphene exists only in the form of a blue resinous mass. Azocamphene is neutral to litmus and does not give with ferric chloride the violet coloration characteristic of the hydrazocamphenes.

At a temperature somewhat above its melting point, azocamphene decomposes with evolution of oxides of nitrogen. It also decomposes when heated with dilute acids or even with water, yielding hydrazocamphene and an acid,. C2HNO,, which is somewhat resinous and is only slightly soluble in water, but dissolves in ether or chloroform. Its salts with alkalis and alkaline earths are soluble in water; the silver salt is only slightly soluble. Prolonged boiling with water decomposes it with production of a new acid which is insoluble in ether and has a high rotatory power.

Concentrated nitric acid acts very violently on the hydrazoeamphenes, but the diluted acid yields the blue azocamphene, which, however, rapidly disappears. When the reaction has moderated, strong nitric acid is added, and the product is crystallised by concentration and converted into the calcium salt, which is recrystallised and then decomposed by hydrochloric acid. The terebenthic acid, CHO, thus obtained forms small anhydrous rhomboidal prisms, soluble in 8.2 parts of water at 14° and in 23 parts of ether, very soluble in alcohol, but insoluble in chloroform. It is optically inactive, melts at 164°, and at a higher temperature loses water, and then partially decomposes. When small quantities are distilled, a syrupy anhydride, soluble in chloroform, is obtained. When fused with potash, it decomposes above 240° with evolution of hydrogen and production of acetate, oxalate, and formate.

Terebenthic acid is bibasic, and the normal salts of the alkalis and alkaline earths are soluble and non-crystallisable. The acid ammonium salt forms slender needles soluble in eight parts of water. The acid calcium salt is only very slightly soluble and forms microscopic crystals. Neutral solutions of terebenthates give precipitates with solutions of silver, copper, lead, and iron (ferric), but no precipitates with solutions of zinc, cobalt, nickel, manganese, or mercury. The silver salt is granular, the copper salt is a blue green powder. The normal zinc salt is soluble and non-crystallisable; when heated with water at 45°, it decomposes into a soluble acid salt, and a basic salt which is insoluble in the hot liquid but is partially decomposed when the

liquid cools, and yields a solution which, if concentrated, coagulates at 24°, but becomes limpid again when cooled.

Terebenthic acid is obtained from both a- and B-hydrazocamphene. Nitric acid also produces other acids less rich in carbon and not crystallisable.

Monohydrated sulphuric acid has no action on the hydrazocamphenes in the cold, but if the hydrazocamphene is treated at 200° with one-fifth its weight of acid it blackens, swells up, and evolves nitrogen and sulphurous anhydride. When the residue is treated with water and agitated with chloroform, it yields dihydrocamphines, C20H3N2O4, which are also formed, together with an alkaline carbonate and cyanide, when hydrazocamphenes are fused with potash.

Chromic acid converts hydrazocamphenes into neutral brown resinous products, insoluble in water, but soluble in alcohol, ether, and chloroform. C. H. B.

Diterebenthyl. By A. RENARD (Compt. rend., 106, 856—858).— Diterebenthyl was allowed to fall drop by drop into an iron tube heated to incipient redness. Very little carbon was deposited, but some hydrogen, mixed with ethylene and propylene, was given off. The fraction of the product boiling below 70° contained amylene and hexylene, pentane, and hexane. The fraction at 70-78° contains hexine, and that at 100-110° consists chiefly of heptine. The most abundant fraction boils at 150-180°, and contains cymene and terebenthene hydrocarbons. It is evident that when decomposed by heat diterebenthyl yields practically the same product as terebenthene or essence of resin obtained by the distillation of colophony.

Bromine in carbon bisulphide forms the unstable derivative C20H30Br2, which, when heated at 300°, yields diterebenthylene, a colourless, slightly fluorescent, thick oily liquid which boils at 345350°; sp. gr. at 12° = 0·9821; rotatory power for D in a column 1 cm. long = +4°; vapour-density, 93. It does not alter when exposed to air, and is not affected by hydrogen chloride. Bromine yields the compound C20H2Br, as a deep-brown, amorphous mass. Well-cooled fuming nitric acid dissolves the hydrocarbon without evolution of nitrogen oxides, and on adding water the trinitroderivative, C20H25(NO2)3, separates as a bulky, flocculent, yellow precipitate. Cold concentrated sulphuric acid has no action, but the bot acid or, better, the fuming acid, yields a sulphonic acid, CH SO3H, distinguished from diterebenthylsulphonic acid by its greater mobility. C. H. B.

Camphor Bases. By E. BAMBERGER (Ber., 21, 1125–1131).— In a previous paper the author has called attention to the analogy existing between the bases of the camphor-group and B-tetrahydronaphthylamine (this vol., p. 159). This is well shown in the case of bornylamine, which, like ẞ-tetrahydronaphthylamine, has a peculiar piperidine-like odour, is strongly alkaline, and reacts with diazobenzene chloride to yield an oil having properties similar to those of diazoamidotetrahydro-ß-naphthylamine (compare this vol., p. 712), Bornylamine nitrate is not decomposed by prolonged boiling with

water, and noteworthy quantities escape decomposition when a 10 per cent. aqueous solution is heated at 130° for four hours. Finally, just as B-tetrahydronaphthylamine decomposes into naphthalene, ammonia, and hydrogen (loc. cit.), so bornylamine seems to yield ammonia and either camphor or its decomposition products. On these grounds, the author considers that bornylamine is a tetrahydroderivative of an aromatic base, and is probably tetrahydrocarvacrylamine. From this it follows that camphor, which yields bornylamine on treatment with ammonium formate (Leuckart and Bach, Abstr., 1887, 376), a reaction involving, as Leuckart has shown, the displacement of the oxygen present in the carbonyl-group by hydrogen and the amido-group, is a ketotetrahydrocy mene [Pr: 0: Me = 1: 3:47.

Camphylamine, which Leuckart (loc. cit.) regards as a positionisomeride of bornylamine, differs from the latter, since it has the properties of a fatty amine, and yields a hydroxy-derivative in the usual way. The remainder of the paper is devoted to a discussion of the probable formula of the anhydride of camphoroxime.

W. P. W.

Lactucerin. By O. HESSE (Annalen, 244, 268-273).-The melting point of pure a-lactucerol varies. If the temperature is slowly raised it melts at 173°, but if it is rapidly heated it melts at 181°. The diacetate, prepared by boiling a mixture of lactucerol with acetic anhydride crystallises in plates and melts at 198-200°. The monacetate melts 'between 202° and 207°. The dibenzoate is freely soluble in ether, chloroform, and light petroleum. It melts at 156°. W. C. W.

=

Apiole. By J. GINSBERG (Ber., 21, 1192-1194).-When apiole is boiled with alcoholic potash, a compound is obtained, which crystallises in satiny scales, and has the same percentage composition as apiole (compare v. Gerichten, this Journal, 1876, ii, 533). On oxida tion with nitric acid (sp. gr. 1:48), apiole yields oxalic acid and a nitro-compound. This crystallises in lustrous, golden needles, melts at 1162, and on reduction with stannous chloride and alcoholic hydrogen chloride is converted into a base, which crystallises from water in long, yellow needles, melts at 118°, dissolves in mineral acids with a red colour, and gives with ferric chloride a violet coloration rapidly changing to blood-red. The picrate of the base crystallises in small, brown scales; the hydrochloride is an indistinctly crystalline powder, and the acetyl-derivative crystallises in colourless scales, melts at 260°, and is sparingly soluble in cold alcohol and ether.

W. P. W.

Emodin in Nephroma Lusitanica. By E. BACHMANN (Chem. Centr., 1888, 47, from Ber. deut. Bot. Ges., 5, 192-194).—The colouring matter obtained from this lichen behaves towards alkalis like crysophanic acid, but differs from the latter in being readily soluble in alcohol, glacial acetic acid, and amyl alcohol. The colouring matter agrees most closely with emodin, a substance first found in rhubarb, and occurring also in the bark and berries of Rhamnus frangula. J. P. L.

Chlorophyll. By J. WOLLHEIM (Ann. Agronom., 14, 141-143, from Bot. Centr., 32, 310).—The author, who has been studying this substance both spectroscopically and chemically for some time past, gives the following preliminary notice of his results :

The fresh solution in absolute alcohol is fluorescent, whilst the colouring matter in the fresh leaf is not. The absorption-bands are the same in relative intensity, but are narrower, and a little displaced towards the blue end of the spectrum. Fuming hydrochloric and sulphuric acids give non-fluorescent solutions with absorption-bands exactly like those of the fresh leaf. It is therefore evident that the colouring matter is changed by the action of alcohol. On adding water to the acid solutions, or weak acids to the alcoholic solution, a greenish-brown precipitate is obtained, soluble in alcohol, ether, chloroform, and benzene, giving the first two bands like the fresh tincture, the band III more feeble, IV stronger, and in addition a fifth band between = 491 and λ = 509, which has already been observed in the fresh leaf, but which appears to belong to a second absorbing substance. Fresh leaves treated with alkalis give fluorescent solutions with absorption-bands still more displaced towards the blue, and also the band III feebler and IV stronger than in the tincture. When the alkaline solution is gently heated, the bands are restored to their normal intensity, and the fluorescence disappears, but the displacement of the bands persists. When the greenish-brown precipitate (chlorophyllane) is dissolved in pure hydrochloric acid, the green solution (Frémy's phyllocyanin) again gives the spectrum of the fresh tincture. It seems, therefore, that certain atoms combined during the formation of chlorophyllane, and causing the reinforcement of band IV, are removed or substituted under the influence of hydrochloric acid. Water gives with this solution another precipitate (phyllocyanic acid), whose alcoholic solution shows a strong band IV. This suggests the entrance of hydroxyl into the combination. The spectrum of phyllocyanic acid is identical with that of chlorophyllane. The precipitate, redissolved and reprecipitated many times, washed, and taken up by chloroform, may be obtained in crystals; after many crystallisations these contain no iron or mineral matter, and give on analysis numbers corresponding with the formula C2HN3O6. Phyllocyanic acid is a compound with a fatty substance. Its ammoniacal solution being precipitated with lead acetate, the precipitate extracted with alcohol, and the green alcoholic solution decomposed with hydrogen sulphide, the reddish-brown substance is left in the alcoholic solution, which is fluorescent, and gives the spectrum of chlorophyllane: whilst the band V has disappeared, showing that it belonged to the fatty substance precipitated by the lead salt. The fatty substance, whose spectrum coincides with that of xanthophyll, is no other than cholesterin. The red-brown substance thus freed from cholesterin is called by the author phyllorubin, and has the properties of an alcohol. On oxidation it behaves exactly like the bilirubin of the bile, becoming in succession blue, violet, red, and yellow. Oxidised with precaution, it yields an acid, whose copper salt shows the same displacement of absorption-bands towards the blue as alkaline chlorophyll. This copper salt is easily formed, and is the substance that gives the fine