Origin. The needle oils of Pinus silvestris, L. (Ger. Kiefer or Fohre) differ in their properties according to their geographical source. Hence they will be discussed separately according to countries.

German "Kiefernadelol." In an experimental way this oil has been distilled occasionally. Although it is but little inferior to other needle oils, particularly to Latschenkieferol, it has not found application in perfumery and the soap industry. Hence its production is not a regular one. Occasionally it is obtained as a by-product in the production of the extract of the leaves of Pinus silvestris.

Fresh needles distilled by Schimmel & Co. in July yielded 0,55 p. c.2), those distilled in December 0,45 p. c. of oil3).

On another occasion the same firm distilled twigs collected in May and June, at which time the influence which the method of distillation exerted on the product was also ascertained. In one instance the dry material was distilled with steam, in another it was soaked. Of both distillations the fractions obtained during different time intervals were collected separately. These fractions as well as the bulked oils were examined and the bulked oils compared with oils obtained as a unit. The following table reveals the results obtained1).

1) Report of Schimmel & Co. Oct. 1905, 59.

2) Report of Schimmel & Co. October 1896, 62.

3) Bertram and Walbaum, Arch, der Pharm. 231 (1893), 300; M.Troger and A. Beutin, ibidem 242 (1904), 521.

Oil

%

d15°

aD

nD 20°

A.V.

E.V.

E.V.

after acetyl.

Ester

Total bor-neol

1. Dry steam distillation.

a) after 3 hrs. obtained

0,189

0,8721

+5° 36'

1,47568

1,8

6,3

2,2

b) „ 4 addit. hrs. obt.

0,1

0,8797

+3° 45'

1,47917

2,8

2,3

0,8

c) by cohobation obt. .

0,0075

0,8913

+ 1°56'

1,48306

4,1

10,9

3,8

d) a, b and c combined

0,2965

0,8755

+5°

1,47715

2,6

5,6

18,6

1,9

5,2

2. Water and steam distillation.

1.

a) after 3 hrs. obtained

0,173

0,8773

+ 5°31'

1,47811

0,9

6,5

2,3

b) „ 4 addit. hrs. obt.

0,152

0,8882

+5° 50'

1,48180

3,6

5,6

1,9

c) a and b combined .

0,325

0,8824

+5°41'

1,47996

2,4

6,0

2,1

ii.

Total distillate after7 hrs.

0,8822

+3° 10'

1,47899

2,8

9,3

26,0

3,3

7,3

Properties2). Pine needle oil has a specific gravity of 0,865 to 0,886 and an angle of rotation aD + 5 to + 10°. Two Austrian oils have been found to be slightly lsevogyrate (up to - 1°55'). Upon fractional distillation 10 p. c. came over between 160 and 170°, and 46 p.c. between 170 and 185°. With 7 to 10 vol. of 90 p. c. alcohol the oil yields a clear solution. Ester content 1 to 3,5 p. c. (computed as bornyl acetate). Ester content after acetylation 15,1 p.c.8).

Composition. Like the needle oils already mentioned, German pine needle oil contains a-pinene, but unlike that of others it is dextrogyrate2)3) (m. p. of nitrolbenzylamine 122 to 123°). It also contains d-sylvestrene. The dihydrochloride obtained at first melted below 50°, but after repeated crystallization attained the constant melting point of 72°. Hence the presence of dipentene in the oil is also to be assumed, since the melting point of this compound has a decided depressing influence on that of syl-vestrene dihydrochloride.

1) Report of Schimmel & Co. April 1910, 91.

2) Bertram and Walbaum, loc. cit. 300; Report of Schimmel & Co. October 1896, 72.

3) M.Troger and A. Beutin, Arch. der Pharm. 242 (1904), 521.

The saponification liquid of the oil contains acetic acid, which in the oil is combined with an alcohol not yet determined (presumably borneol or terpineol). In the highest fractions cadinene (m. p. of dihydrochloride 118°) has been found.

From the pine sprouts (male and female inflorescences) H. Haensel1) distilled an oil of the following properties: d15o0,8839; aD - 22°; S. V. 19,5; S. V. after acetylation 58; boiling temperature 160 to 210°.

Swedish Pine Needle Oil is distilled in the district Jonko-ping, Sweden, from pine needles by steam. It enters commerce as Schwedisches Fichtennadelol. It is used for hygienic and medicinal purposes: for inhalations with diseases of the lungs, as ingredient for medicinal baths and for inhalations in sick rooms.

Properties. In its general properties and composition, Swedish pine needle oil agrees with the German oil. Sp. gr. 0,872; optical rotation + 10°40'; upon fractionation it yields 44 p. c. between 160 and 170°, and 40 p. c. between 170 and 185°. It contains d-a-pinene (m. p. of nitrolbenzylamine 122 to 123°), d-sylvestrene (m. p. of dihydrochloride, 72°) and small amounts of an ester (3,5 p. c. computed as bornyl acetate), the nature of which has not yet been determined, but which, to judge from the odor, appears to be bornyl acetate2).

English Pine Needle Oil differs from the German and Swedish oils by its laevorotation.

Umney3) has distilled the needles of the Scotch fir (Pinus siIvestris, L.) at different seasons. In June he obtained 0,5 p. c, in December 0,133 p. c. of volatile oil, the sp. gr. of which varied between 0,885 and 0,889, and the angle of rotation between aD - 7,75 and - 19°. The ester content, computed as bornyl acetate, varied between 2,9 and 3,5 p. c. The fractional distillation of the two oils gave the following results:

1) Apotheker Ztg. 20 (1905), 396.

2) Bertram and Walbaum, Arch, der Pharm. 231 (1893), 299.

3) Pharmaceutical Journ. 55 (1895), 161, 542.

Oil distilled

in June

in December

from 157 to 167°.....

8%

13%

„ 167 „ 177° .....

27%

24 %

„ 177 „ 187° .....

20%

9%

„ 187 „ 197° .....

3%

6%

„ 197 „ 240°.....

7%

7%

„ 240 „ 252°.....

6%

4%

29%

37%

Composition. The lowest fraction deviated the ray of polarized light 13° to the left (100 mm. tube) and possessed all of the properties of l-a-pinene. Fraction 171 to 175° was slightly dextrogyrate (+0,75°), behaved like dipentene1), and gave the sylvestrene reaction with glacial acetic acid and sulphuric acid.

Hence it may be assumed that, with the exception of the opposite rotation, English pine needle oil agrees in composition with the German and Swedish oils.