On the Essential Oil contained in the Alcohol of Madder.

The Chemical Gazette 329, 1.7.1856

By F. Jeanjean.

For several years an alcohol has been obtained in the South of France in considerable quantities, by the fermentation of the saccharine matters contained in the root of the madder. The alcohol thus obtained always possesses a very disagreeable and characteristic odour, and the author has examined it to ascertain the nature of the foreign bodies contained in it.

The products obtained by him formed a liquid of less density than water, and aſter some time deposited crystalline lamellae. When distilled, it furnished liquid products up to 446°F., but afterwards a solid white matter was deposited in the neck of the retort. If the distillation be arrested at this point, the belly of the retort becomes filled with crystals presenting the appearance of the fronds of ferns.

From the indications of the thermometer immersed in the boiling liquid, the author suspected the presence of propionic and butyric alcohols in the first products of the distillation; the stoppage of the thermometer at 266°F. indicated the probable presence of amylic alcohol, and the products boiling at this temperature being in larger quantity than the preceding, he was enabled to analyse them, when he found them to agree in composition with amylic alcohol.

The solid matter passing at 446°F., when pressed between paper, washed in a large quantity of water, and purified by repeated crystallization from aether, forms a white powder, of a peppery odour, which however resembles that of ordinary camphor. Its analysis gave—

	I.	II.
C	77.7	77.82
H	12.2	11.9
O	10.1	10.28

corresponding with C₂₀ H₁₈ O₂, the formula of Bornean camphor.

This substance possesses a hot burning taste, and when sublimed forms small hexagonal prisms. It gives rise to the gyratory movements of camphor when thrown upon water; it is but slightly soluble in water, but very soluble in ordinary acetic acid, and in alcohol and aether, from which it is thrown down by water. Distilled over chloride of zinc or anhydrous phosphoric acid, it gives origin to a hydrocarbon, the odour of which resembles at once those of the essential oils of citron and bergamotte. Lastly, it is converted into ordinary camphor by the action of boiling nitric acid, as was observed by M. Pelouze to be the case with the camphor obtained from Dryobalanops camphora.

The crystals which are deposited naturally in the crude material possessing all the properties of those obtained by distillation, the author concluded that their formation was due to the hydration of a pre-existent hydrocarbon. To isolate this, he took the liquid which passed above 284° F. in the first distallation, digeted it over potash and chloride of calcium, and distilled it several times to free it from the camphor which it had carried over; it formed a liquid boiling at 320°F., with an odour like that of the essence of madder. Its analysis gave-
C 88.23
H 11.81
and the density of its vapour being 4.85, its formula is C₂₀ H₁₆, cor responding with 4 vols. of vapour. This hydrocarbon therefore corresponds with that of Bornean camphor, and like it will be isomerous with turpentine.

The quantity of the hydrocarbon was insufficient for the determination of its behaviour towards polarized light. The camphor deviated the plane of polarization to the left. A solution of 20 grms. of camphor in 100 cub. centims. of alcohol giving a deviation of 12 degrees, the author concludes from Biot's formula that the rota tory power of this camphor for a length of 100 millims. is
[a]=–34.5.

- Comptes Rendus, May 5, 1856, p. 857.