Oleum Sabinae. - Sadebaumol. - Essence de Sabine. Origin. The savin, Juniperus Sabina, L. is a tree-like shrub-) that grows wild in the mountains of Central and Southern Europe and that is occasionally cultivated.
1) Report of Schimmel & Co. October 1911, 105.
2) P. Guigues, Une foret de sabines dans les Hautes-AIpes. Bull. Sciences Pharmacol. 9 (1902), 33.
Production. The oil is obtained by the steam distillation of the leaves and ends of twigs, the Summitates Sabinae. The yield varies, according to the time of collection and the freshness of the material, between 3 and 5 p.c.1). The leaves used for distillation are obtained primarily from the Tirol. In Southern France also oil of savin is distilled, but there the leaves and branches of related species (J. phoenicea and /. thurifera var. gallica) are mostly used 2). Hence the constants of the French oils are different. In consequence it was formerly supposed that they represented true oil of savin adulterated with oil of turpentine.
Properties. Oil of savin is a colorless or yellowish liquid of a disagreeable narcotic odor and a bitter, pungent, camphor-like taste. d15o 0,907 to 0,930; a D + 38 to +62o3); nD20o 1,473 to 1,479; A.V. up to 3; E.V. 107 to 138; E.V. after acetylation 127 to 154. It is soluble in 1/2 and more parts of 90 p.c. alcohol. Of 80 p.c. alcohol 5 to 15 vol. are required, but the solution thus obtained is not always perfectly clear. Upon repeated fractionation, 25 to 30 p.c. are obtained below 175°4).
Composition. Concerning the hydrocarbons of the lower fractions there has been much ambiguity for a long time. The results of an investigation published by Dumas5) in 1835 indicated the presence of pinene or camphene. Dumas had isolated a fraction 155 to 161° that had the composition C10H16. Upon the oxidation of the terpene that boiled at about 161°, Grunling6) obtained terephthalic and terebic acids which indicated pinene. Fromm7) then obtained about 25 p.c. of a terpene fraction below 165°, but he did not succeed in identifying pinene or any other known terpene. Inasmuch as it is important to know in the testing for adulterations whether the oil contains pinene or not, Schimmel & Co.1) refractionated the portion that distilled below 160°. From 25 kg. of oil they thus obtained but 13 g. of a hydrocarbon with the boiling point of pinene. However, a part of this consisted of sabinene. Neither did it give the reactions characteristic for pinene. Thus it was shown that savin oil contains at most traces of pinene and that the investigations by Dumas and Grunling were conducted either upon an oil adulterated with pinene or upon an oil that had been obtained from other species of Juniperus (see above). The proof of the presence of very small amounts of a-pinene was accomplished by J. W. Agnew and R. B. Croad2) who obtained upon the oxidation of fraction 160° with mercuric acetate a mixture of pinol hydrate (m. p. 131°, of dibromide 131 to 132°; m. p. of pinol dibromide 94°) and 8-hydroxycarvotanacetone (m. p. of semicarbazone 1750)3).
1) With regard to the abnormally low yields from fresh and dry twigs see E. F. Ziegelmann, Pharm. Review 23 (1905), 22.
2) E. Perrot and Mongin, A propos de la Sabine et des especes botaniques de Juniperus fournissant la drogue commerciale. Bull. Sciences pharmacol. 9 (1902), 38. The authors demonstrate that the French drug is a mixture of the twigs of Juniperus Sabina, J. phcenicea and /. thurifera var. gallica, of which /. phcenicea constitutes the bulk. Similar conditions prevail in the distillation of French savin.
3) In connection with an English oil Umney and Bennett observed aD +68°.
4) Berl. Berichte 33 (1900), 1192 and 1463.
5) Liebig's Annalen 15 (1835), 159.
6) Beitrage zur Kenntnis der Terpene. Inaug. Diss., Strafiburg 1879, p. 27. - See also Levy, Berl. Berichte 18 (1885), 3206. 7) Berl. Berichte 33 (1900), 1192.
In 1900 Semmler4) discovered in savin oil a new terpene, sabinene C10H16, which boils between 162 and 165°. (See vol. 1, p. 300), and which he oxidized to sabinene glycol (m. p. 54°) and to sabinic acid (m. p. 57°). Whereas until recently only (d-sabinene had been found in savin oil (comp. vol. 1, p. 300), Agnew and Croad found /-sabinene. In fraction 170 to 180° Schimmel & Co.5) proved the presence of a-terpinene (m. p. of nitrosite 156°).
The principal constituent is an alcohol C10H16O which was first isolated by E. Fromm6) and named sabinol by him. It is contained in the oil partly free, partly as ester, the acetate (silver salt7)) predominating. According to Fromm8) the higher boiling acids are a mixture of a liquid, dibasic acid which boils at 255° and which probably has the composition C20H36O5, and a solid acid C14H1608 which boils at about 260° and melts at 181°.
1) Report of Schimmel & Co. April 1908, 97. *) Analyst 37 (1912), 295.
3) Comp. Henderson and Agnew, Journ. chem. Soc. 95 (1908), 289, and Henderson and Eastburn, ibidem 1465. 4) Berl. Berichte 33 (1900), 1463. 5) Report of Schimmel & Co. April 1911, 106. 3) Berl. Berichte 31 (1898), 2025. 4) Report of Schimmel & Co. October 1895, 44. 5) Berl. Berichte 33 (1900), 1210.
Sabinol (see vol. I p. 390) has a specific gravity of 0,950 at 15° and boils between 210 and 213° (b. p. 77 to 78° under 3 mm.)1). When oxidized with permanganate, it yields a-tan-acetogen dicarboxylic acid (m. p. 140°). Sabinol acetate is characterized by its very high optical rotation. A sabinol with aD + 6° yielded an acetate (b. p. 81 to 82° under 3 mm.; d15o0,972) of aD + 7901).
The fraction above 220° contained a substance that combined with bisulphite. It had an odor that reminded of cuminic aldehyde and boiled between 127 and 129° (20 mm). This substance (d16o0,9163; aD + 11°40'), about the composition of which nothing is known, yields a phenyl hydrazone that melts at 40 to 45° and an oxime that melts at 85°2).
In fraction 220 to 237° Schimmel & Co.3) found citronellol (m. p. of the silver salt of the acid phthalate 126 to 127°). In one of the tailings F. Elze4) found geraniol (m. p. of diphenyl-urethane 82°) and dihydrocuminic alcohol (m. p. of naphthyl-urethane 146 to 147°).
In the highest fractions of savin oil Wallach5) ascertained the presence of cadinene.
In the aqueous distillates resulting from cohobation, Schimmel & Co.6) found methyl alcohol, furfurol and diacetyl. In the first fraction of the oil Elze4) found traces of n-decyl aldehyde (m. p. of semicarbazone 102°; m. p. of /7-caprinic acid 31°).
Test. The principal adulterant of savin oil is the oil of Juniperus phcenicea7) (probably also that of /. thurifera var. gallica). As to its properties this oil is like a mixture of savin oil and French turpentine oil.
Like that of French turpentine oil, the presence of added oil of /. phcenicea may be recognized by lowering of the specific gravity, reduction or reversion of the angle of rotation to the left, lowering of the saponification value and diminution of the solubility in alcohol. In both cases the exact proof of their presence is supplied by the isolation and identification of pinene, since, as has already been pointed out, oil of savin contains but traces of this terpene.
1) Elze, Chem. Ztg. 34 (1910), 767.
2) Report of Schimmel & Co. April 1900, 43.
3) Ibidem October 1907, 80.
4) Chem. Ztg. 34 (1910), 767.
3) Liebig's Annalen 238 (1887), 82.
6) Report of Schimmel & Co. October 1900, 62 and April 1903, 73.
7) Umney and Bennett, Pharmaceutical Journ. 75 (1905), 827.