Upon distillation of the fresh shoots of the Aleppo pine (Pinus halepensis, Mill., Pinus maritima, Mill.) collected in southern France, E. Belloni1) obtained 0,681 p. c, and upon distillation of the dried shoots 0,517 p. c. of a light greenish oil with an aromatic taste and characteristic pine needle odor. It possessed the following constants:
B. Oil from dried shoots: d15o0,8963; aD - 20° 15'; [a]D15o - 22,355°; A.V. 5,43; E.V. 8,27 = 2,92 p. c. ester (computed as C10H17O-CO-Ch3); free alcohol 11,9 p. c; combined alcohol 2,28 p. c; total, alcohol 14,18 p. c.
The oils are insoluble in 80 p. c. alcohol, soluble in 10 vols, of 90 p. c. alcohol. They are miscible with alcohol of 95 p. c. strength and stronger.
Upon fractionation from a Ladenburg flask the oils yielded the following results: Oil A: between 155 and 170° 58 p. c. (aD - 27°50'), between 170 and 190° 20 p. c. (aD - 31°40'), residue 20 p. c. Oil B: between 155 and 170° 42 p. c. (aD - 26°42'), between 170 and 190° 20 p. c. (aD - 29° 34'), residue 37 p. c.
The oil contains no aldehydes. The free acid found in the oil distilled from the dry shoots consisted principally of caprylic acid (about 1,396 p. c). The esters are principally those of the lower fatty acids, presumably acetic acid, propionic acid, caprylic acid and lauric acid. The bulk of the oil consists of /-a-pinene with the following properties: b. p. 155 to 157°; d15o0,8618; [a]D15 o - 29°30' (m. p. of nitrosochloride 103°, of nitrolpiperide 118°). Phellandrene and sylvestrene could not be identified in fraction 170 to 190° but limonene or dipentene probably is present. Of the alcoholic components Belloni2) identified /-borneol, m. p. 205°, by means of the phthalic acid anhydride method.
1) Sull' essenza di gemme di Pinus maritima, Mill. Milano 1905. Annuario della Soc. chim. di Milano 11 (1905), fascic. 6; Chem. Zentralbl. 1906, 1. 360.
2) Boll. Chim. Farm. 46 (1906), 185; Chem. Zentralbl. 1906, I. 1552.
In the Algerian needle oil of the Aleppo pine E. Grimal1) demonstrated the presence of phenyl ethyl alcohol, which previously had been observed only in the oils of neroli and rose. He saponified fraction 120 to 135° (10 mm.), shook out the saponified liquid with ether and fractionated the ethereal residue. Fraction 95 to 98° (8 mm.) was treated with phthalic acid anhydride and the resulting ester was saponified. A very aromatic liquid resulted which distilled between 218 and 220 under ordinary pressure and was characterized by the following constants: d15o 1,0187; aD + 0°; nD18o 1,52673. The alcohol was further characterized by elementary analysis, by its behavior during oxidation, and by its phenylurethane.