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Conversion of Dextrorotatory Terpene from Russian Turpentine by means of Hydratation and Dehydratation. By F. FLAWITZKY (Ber., 20, 1956-1965).-The dextrorotatory terpene employed was prepared from steam-distilled Russian turpentine by fractional distillation and treatment with dry potash; it was then warmed with sodium. It boils at 155.5-156.5° (corr.), sp. gr. = 0·8764 at 0° and 0.8600 at 20° (water at 4° 1). Coefficient of expansion between 0° and 20° = 0·00095. At 20° (with 100 mm.) [a]D= + 27·5. [a]D= Molecular refraction

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+ 27.5 0.8600

= + 32.0°.

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=71-24. The terpene was treated with twice its weight of a mixture of 3 parts 90 per cent. alcohol and 1 part sulphuric acid of sp. gr. = 1.64. After six days, the solution was separated from the unchanged terpene, decomposed by water (kept cool with ice), and the portion which separated washed first with water, then with alkali. The product, when dried over potash, showed rotation (with 100 mm.) [α]D = 35.6°; that is 81° more than in the case of the original terpene. The product precipitated from the solution dissolved in alcoholic sulphuric acid only to the extent of one half; when steam distilled, it gave three distillates having different rotatory powers. A substance boiling at 213-7° to 217-7° was obtained. [x]D = +44-5 at 19.5° (with 100 mm.). Analysis showed it to be a hydrate, C10H16, H2O. It forms a thick liquid, insoluble in water, miscible with alcoholic sulphuric acid, and has a peculiar odour and a bitter burning taste. Sp. gr. = 0·9335 at 0° and 0.9189 at 19.5°.

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Coefficient of expansion = 0.00081. [a]D=+484. Molecular refractive power 77.28. A table is given showing the similarity between the dextro- and lævo-terpene hydrates. When the hydrate is saturated with hydrogen chloride, the hydrochloride C10H16(HCl), is formed; this crystallises from alcohol in tabular crystals melting at 49.5°.

The fraction of the substance of the rotatory power [a] = + 35·6°, which boiled below 210°, gave [a]D = + 40·0°. When purified by repeated distillation over sodium, it boiled at 173-176°, and crystals separate on cooling it to -25°. After being again distilled, it was pure. [a] = 491 at 15°. Sp. gr. = 0.8627 at 6° and 0.8480 at 20°. Coefficient of expansion = 0·00089. [a]D=+57·6. It differs, therefore, distinctly from the original terpene, but resembles lævoisoterpene, and is, therefore, described as dextro-isoterpene.

The new dextro-isoterpene resembles the dextro-isoterpene from oil of lemon in its molecular refraction and other physical properties. When the new isoterpene is saturated with hydrogen chloride, it becomes heated, but no crystalline hydrochloride separates. The dihydrochloride, C10H16(HCI), is obtained by saturating the solution of the terpene in glacial acetic acid with hydrochloric acid, and adding water; it separates from alcohol in crystals melting at 49°.

N. H. M. Action of Glacial Acetic Acid on Lævogyrate Camphene. By J. LAFONT (Compt. rend., 104, 1717-1719).-Lævogyrate camphene, obtained by the action of alcoholic potassium acetate at 150°

on

terebenthene hydrochloride, was heated with 15 parts of glacial acetic acid in sealed tubes at 100° for about 60 hours. The product was then distilled in a vacuum, and the portion boiling above 100° was again treated in the same way, this process being repeated six times. The final product was washed with water and fractionated in a vacuum. The fraction boiling at 155-158° under normal pressure consists of non-combined camphene, the rotatory power of which has diminished to [a]D = 19° 53'. It yields a hydrochloride with a rotatory power [a]D Ꭰ = + 9° 32'. The fraction boiling at 125-127° under a pressure of 35 mm. consists of a dextrogyrate acetate, which is liquid at the ordinary tempe. rature, but becomes pasty at -50°; sp. gr. at 0° 1.002; rotatory power [a]p = 19° 41'. If heated with alcoholic potash in sealed tubes, it yields borneol, which when purified by sublimation melts at 211°. Its rotatory power is [a]D = +14° 51'; when treated with nitric acid, it yields a camphor which melts at 175°, and has a rotatory power [a] 20° 2′.

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The action of acetic acid on lævogyrate camphene yields only one acetate, which is dextrogyrate, and when this is treated with alcoholic potash it yields potassium acetate and camphenol only.

C. H. B.

Black Pepper Oil. By L. A. EBERHARDT (Arch. Pharm. [3], 25, 515-519). The oil had a specific gravity of 0-87352 at 15°, and showed a greenish colour, due neither to chlorophyll nor to copper. At 22°, the oil had a lævorotatory power of 3.2° in a column 100 mm. long. On rectification, a very small quantity passed over at 160°. Fractions obtained at 170°, 176°, and 180° were colourless; 190° faint

VOL. LII.

3 t

green; 250° green; 310° brown-green. Above 310°, a brown tenacious residue was obtained in which phenol could not be detected.

The 170° fraction, when rectified under reduced pressure, gave a terpene boiling at 164-165°, and showed a left-handed rotation of 7.6° in 100 mm.; it gave numbers agreeing with the formula C10H16, and a vapour-density of 480° by Hofmann's method. The composition of the other fractions was much the same as this. The terpene hydrate was obtained by Tilden's method (this Journ., 1878, 247). The tetrabromide was also obtained in well-crystallised forms. The oil consists of a lavorotatory terpene and isomeric compounds of higher boiling points. J. T.

B-Chloronitro-camphor. By P. CAZENEUVE (Bull. Soc. Chim., 47, 926-927).-The B-chloronitro-camphor previously described (Abstr., 1884, 1041) is more readily soluble in alcohol than the a-compound, and may, therefore, be separated from its isomeride by washing the mixture with 80 per cent. alcohol. On spontaneous evaporation, the solution obtained deposits microscopic crystals which may be purified by repeated recrystallisation from 93 per cent. alcohol. Thus obtained it is a soft camphor-like substance, crystallising in microscopic arborescent forms; it softens at 91°, and melts at 98; it is dextrorotatory, an examination of its alcoholic solution showing it to have the rotatory power [a]; = + 10·5°. The chlorine in this compound is much less stable than in its isomeride, as alkalis decompose it at the normal temperature, metallic chlorides and nitro-camphors being formed. Sodium ethoxide also attacks it, sodium chloride, and what appears to be an ethyl ether of a nitrocamphor, being formed. A copper-zinc couple also decomposes it, nitro-camphor being produced. The a-compound yields the same reactions, but only on prolonged boiling; the nitro-camphors formed are, however, the same in each case.

A. P.

Strophanthus and Strophanthin. By A. W. GERRARD (Pharm. J. Trans. [3], 17, 923; comp. this vol., p. 991).-Boiling alcohol completely removes both oil and extract from Strophanthus seed at one operation; the oil can then be easily poured from the extract, and adhering traces washed away with a little ether. The author was, like Elborne, unable to obtain any alkaloïd from the hairs of Strophantus seeds.

Strophanthin was prepared by dissolving the alcoholic extract, filtering, adding tannic acid in excess, and then collecting the precipitate, which after washing was mixed with basic lead acetate. The mixture was then dried, exhausted with warm alcohol, and filtered. Traces of lead were removed by hydrogen sulphide, and on evaporation strophanthin was obtained as a scaly residue, which was finally purified by solution in water and treatment with animal charcoal.

Strophanthin has well-marked glucosidal characters. The author was unable to obtain strophanthin in crystals as described by Fraser. R. R. Cubebin. By E. SCHÄR (Arch. Pharm. [3], 25, 531-539).Cubeb powder when extracted with ether yields a compound which

closely resembles aconitine and digitalin in its reactions, and also shows some resemblance to veratrine and morphine. This is probably cubebin, a non-nitrogenous, indifferent substance occurring crystallised in cubebs. Comparing cubebin and veratrine, the sulphuric acid test is most characteristic when the substances are dissolved in chloroform. On contact with concentrated sulphuric acid, cubebin gives at once an intense purple-red colour at the surface of contact, whilst veratrine passes through orange-yellow, yellowish-red, and blood-red to purple-red; also a characteristic fluorescence appears in the latter case. Cubebin, unlike veratrine, gives no purple-cherry-red colour with concentrated hydrochloric acid, neither do cane-sugar and slightly diluted sulphuric acid give the very characteristic colour reaction of veratrine. Sulphuric acid containing 10 to 15 per cent. of water gives with cubebin after a longer or shorter time, according to the strength of the acid and the temperature, the beautiful red tint described by Grandeau as produced by digitalin with concentrated sulphuric acid. A little bromine added to the cubebin mixture produces sooner or later the strong bluered coloration which has been considered as characteristic of digitalin. These two substances can be distinguished by their reactions with phosphomolybdic acid and with hydrochloric acid. The reactions of cubebin and aconitine are also compared and but slight differences were observed. The author hopes to investigate further. J. T.

Pterocarpin and Homopterocarpin from Sandal Wood. By CAZENEUVE and HUGOUNENQ (Compt. rend., 104, 1722-1725).— Powdered sandal wood is mixed with an equal weight of calcium hydroxide, moistened with water, dried on a sand-bath, and extracted with ether. The colouring matter and resins unite with the lime and form compounds insoluble in ether. The yellow ethereal solution is distilled to dryness, the residue dissolved in alcohol of 93°, and afterwards recrystallised from alcohol and finally from ether. product is a mixture of pterocarpin and homopterocarpin, and these can be separated by means of carbon bisulphide, which dissolves the homopterocarpin. 1 kilo. of sandal wood yields about 5 grams of homopterocarpin and 1 gram of pterocarpin.

The

Pterocarpin, C10H3O3, forms white lamellar crystals insoluble in water and in cold alcohol, but somewhat more soluble in the hot liquid, slightly soluble in ether, from which it crystallises in lamellæ, insoluble in carbon bisulphide in the cold but slightly soluble on heating; readily soluble in chloroform, from which it crystallises in large monoclinic prisms with lævohemihedral faces. When dissolved in chloroform, it has a lævorotatory power [a]; = 211. When heated, it becomes pasty above 145°, and melts at 152° with slight decomposition. It has a neutral reaction, is insoluble in acids and in concentrated potash solution even when boiled, gives a green coloration with concentrated nitric acid, and is decomposed by fused potash with development of an odour of coumarin.

Homopterocarpin, C12H12O3, has the same general properties as pterocarpin. It crystallises well in needles which are soluble in ether, chloroform, benzene, and carbon bisulphide. It is strongly lævogyrate, and when dissolved in chloroform has a rotatory power

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[x]; 199°. It softens at 70°, begins to melt at 82°, and is completely fused at 86°; solidification takes place very slowly. Concentrated potash solution has no action even at 200°, but with fused potash it yields carbonic anhydride and phloroglucol, and an odour of coumarin is perceptible. When homopterocarpin is heated with twice its weight of concentrated hydrochloric acid at 120° for ten hours, it yields a red-brown, lustrous product which seems to be resorcinol ether, OH CH, O.C.H, OH. The supernatant acid has a yellow colour, and when the acid is expelled and the liquid mixed with ammonia a very fluorescent substance is obtained. Methyl chloride is also formed in this reaction. This result indicates that homopterocarpin contains the resorcinol-group with one or several methylgroups. In its stability and general properties, it resembles the internal anhydrides of the benzene series, especially coumarin.

The compound now described as homopterocarpin was formerly called pterocarpin (Bull. Soc. Chim., 1874).

C. H. B.

Bitter Principle of Calamus Root. By A. GEUTHER (Annalen, 240, 92-110).-The author has repeated the experiments of Thoms (Abstr., 1886, 895), and obtained the following results: (1) the acorin prepared by Thoms' method contains nitrogen; it is a mixture of ethereal oil, acid, and bitter principle. No sugar is formed when it is boiled with dilute alkali. (2) Thoms' acoretin is not a product of acorin but forms the bitter principle contained in that substance. Acoretin is not reduced by nascent hydrogen but remains unaltered. When calamus root is steam distilled, a distillate containing methyl alcohol is obtained. N. H. M.

Chlorophyll. By E. SCHUNCK (Proc. Roy. Soc., 42, 184-188).-The author prepares compounds of phyllocyanin and carbonic anhydride. Carbonic anhydride passed through alcoholic phyllocyanin in the presence of ferrous hydrate gave no result. With copper oxide, a slight action took place. With zinc oxide, the colour of the phyllocyanin changes to bluish-green, exhibiting absorption-bands similar to those of phyllocyanin zinc acetate. On adding acid, it is decomposed into phyllocyanin and carbonic anhydride. The absorption-bands and general properties of phyllocyanin zinc-compounds resemble those of chlorophyll. In order to determine their relative stability, compounds of phyllocyanin with zinc, ferrous, and cupric acetates together with uncombined phyllocyanin and chlorophyll were exposed to air and daylight. The cupric compound was very stable, whilst the zinccompound decomposed almost as easily as chlorophyll itself, the ferrous compound holding a position between the zinc-compound and uncombined phyllocyanin. On boiling phyllocyanin with aqueous potash and zinc-dust, and acidifying with acetic acid, a precipitate is obtained which dissolves in ether, giving absorption-bands similar to those of phyllocyanin zinc acetate, but moved further away from the red. Compounds having characteristic absorption-bands are also obtained by the action of hydrochloric acid and tin on phyllocyanin.

H. K. T.

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