From the leaves of the Nepal sassafras or Nepal camphor tree, Cinnamomum glanduliferum, Meissn., a lauraceous tree growing in the southern districts of the Himalaya mountains, R. S. Pearson, of Dehra Dun, obtained a camphor which is identical with the Japanese drug. The crude product sent to Schimmel &Co.3) melted at 175°. Upon recrystallization from dilute alcohol the melting point rose to 176°. The specific angle of rotation of the purified camphor was [a]D + 46,32° (in a 55,55 p.c. solution in 90 p.c. alcohol). In a 43,91 p.c. xylene solution it was [a]D +49,12° and after the solution had stood ten days it dropped to [aD + 48,72°. The oxime melted at 118° and, as was to be expected, showed a reversed optical rotation, it being laevogyrate. Upon boiling the crude product with acetic acid anhydride the presence of alcoholic substances, e.g. borneol, could not be ascertained, hence it consisted of d-camphor only.
The leaves of a tree, the later investigation4) of which proved it to be Cinnamomum glanduliferum, Meissn., and which grew in the Villa Rothschild at Cannes, yielded upon distillation 0,52 p.c. of a volatile oil which was characterized by a decided cardamom odor. d15o058 and 0,9031; aD26° 12'
1 Verslag 's Lands Plantentuin te Buitenzorg 1895, 39.
2) Jaarb. dep. Landb. in Ned.-Indie, Batavia 1910, 49.
3) Report of Schimmel &Co. October 1910, 145.
*) Ibidem April 1905, 83. This reference erroneously quotes Laurus Camphora as the plant from which the oil in question is derived. Comp. also ibidem April 1913, 41.
and - 24°57'; A.V. 0,34 and 0,9; E.V. 8,82 and 18,4; E.V. after acetylation 46,9 and 55,3; soluble in 1 to 1,5 vol. or more of 80 p.c. alcohol.
The first-mentioned oil has been examined as to its constituents. Under a pressure of 4 mm. it boils between 35 and 95°. In the lowest boiling portion the presence of a-pinene was demonstrated (m. p. of nitrolbenzylamine 123°). The presence of camphene is probable, but its definite characterization by means of conversion into isoborneol was not accomplished. Furthermore the oil contained much cineol (m.p. of the iodol compound 112°).
Upon further fractionation in vacuum, of those portions of the oil which had passed over above 76° under 4 mm. pressure, the principal fraction which came over between 85 and 86° (5 mm.; aD - 58°23') and which constituted about 10 p.c. of the original oil, consisted of l-a-terpineol. This alcohol was characterized by its phenylurethane (m.p. 113°), as well as by its nitrosochloride (m.p. 112°). Upon inoculation of the strongly cooled fraction with solid terpineol, prolonged standing in the cold resulted in the separation of crystalline terpineol that melted at 35°. It is noteworthy that this oil contained no camphor, whereas the oil examined by Pearson consisted almost entirely of this substance.
The oil from the wood of this plant has been distilled by S. S. Pickles1). The crude material used consisted of short pieces of the wood deprived of its bark. From the saw dust 2,95 p.c. of oil, computed with reference to the non-comminuted wood, were obtained. Computed with reference to the saw dust itself, the yield was 4,16 p.c. This difference is attributed to the loss of moisture which the wood suffered during the process of comminution. The oil constitutes a light yellow liquid, the odor of which reminds one distinctly of safrol, also of anise: d15/15o1,1033; aD20o - 0°4'; S.V. 2,8; E.V. after acetylation 7,0; soluble in 5 vol. or more of 80 p. c. alcohol and in one-half vol. of 90 p.c. alcohol. Terpenes, acids, alcohols, esters, aldehydes and ketones are either absent, or present in very small quantities only. The bulk of the oil boils between 245 and 280° and contains very much safrol. This has the following properties: m.p. 9°; d15o1,1059; aD + 0. It was characterized by its oxidation to piperonal (m.p. 37°) and by its a-nitrosite (m.p. 130 to 131°). In fraction 152 to 157° (12 mm.) Pickles found myristicin which he converted into dibromomyristicin dibromide (m.p. 129°) and dibromomyristicin (m.p. 52°). In order to convert the allyl group into the propenyl group, the fraction containing myristicin was heated with alcoholic potassa. The fraction was then oxidized with potassium permanganate, resulting in the formation of myristicinic aldehyde (m.p. 130°) and myristicinic acid (m. p. 212,3°), also of trimethyl gallic acid (m.p. 167 to 168°). The formation of trimethyl gallic acid indicates the presence of isoelemecin in the fraction treated with potassium hydroxide. It may, therefore, be assumed that the original oil contains elemicin. The other constituents of the oil are free palmitic acid (m.p. 62,5°), a phenol-like substance and a mixture of esters of low molecular fatty acids.
1) Journ. chem. Soc. 101 (1912), 1433. - Bull. Imp. Inst. 10 (1912), 298.