Commercial and scientific notes on essential oils. 49 



The constants of the principal and the aqueous oil (together with those observed 



by Miller 1 ) in 1916) were as follows: — 













Principal oil 





Aqueous oil 



% 



1916 



1919 



1916 





1919 



dno 



0.915 



0.913 



d 25 o 0.939 



0.948 and 0.959 



Acid value . . . 



7.24 



4.27 2 ) 



37.0 





— 



Ester value . . . 



2.2 



5.65 2 ) 



7.6 





17.7 



Sapon. value . . 



9.44 



10.92 2 ) 



44.6 





— 



Ester v. after acet. 



23.5 



17.8 



51.8 





50.9 



These figures show that the water oils contain more free acid, more esters and 

 more free alcohols than the principal oils. The following constituents of the cohobated 

 oil were identified: — A valeric acid (in all probability; silver salt), a large quantity of 

 impure borneol, furfural (aniline acetate reaction), and traces of eugenol (benzoate, 

 m. p. 69 to 70°). 



The main oil was separated by fractionation, first under atmospheric pressure, into 

 10 fractions boiling between 85 and 174°, then under 30 mm. pressure, into 10 more 

 fractions boiling between 75 and 125°. Miller 3 ) had proved formerly the presence in 

 these fractions of following bodies: — valeric, salicylic and butyric acids, aldehydes, 

 pinene, limonene, camphor, borneol, and cineole. In addition to these constituents 

 which, except limonene, were also identified by Kremers, the latter author succeeded 

 in identifying nopinene (nopinic acid, m. p. 126°; nopinone semicarbazone, m. p. 188°). 

 The constants of a saponified fraction of the b. p. 90 to 95° pointed to the presence 

 of thujone (d 25 o 0.929, «— 3.0°, n D25 o 1.4588). The tribromide (Wallach) showed the 

 m. p. 121°; the semicarbazone was readily formed, but was either a mixture of the 

 derivatives of «- and /2-thujone, or of thujone with that of another ketone. 



From 100 g. of a fraction boiling above 140°, Kremers obtained 35.5 g. of a blue 

 oil, containing azulene, b. p. 135 to 136° (1.1 mm.), and 59 g. non-blue oil. With alcoholic 

 picric acid solution, azulene yielded instantly the picric acid addition compound. After 

 removal of the azulene by means of phosphoric acid, the oil was fractionated (pressure, 

 5 to 0.1 mm.) into 8 fractions boiling between 80 and 180°. From the portions boiling 

 between 100 and 115° (0.5 mm.) the author obtained, by distillation with sodium, a 

 fraction with the constants: — b. p. 105 to 110°, d 20O 0.916, a — 13.75° (100 mm. tube), 

 n 1.4990, mol. refr. 65.4, which yielded a benzylamine base, m. p. 172 to 173°, and a 

 hydrate, m. p. 94 to 95°. The presence of caryophyllene, therefore, must be considered 

 as proved. 



As a supplement to Kremers' notes on the work of Miller on milfoil oil, we add 

 the following statements culled from Miller's paper, the copy of which reached us only 

 recently. E. R. Miller 3 ) obtained by steam-distillation partly from the entire (fresh or 

 dried) plant, partly from the flowers or the leaves of Achillea millefolium, L. cultivated 

 near Madison a series of oils, all of which were dark blue. The flowers yielded more 

 blue oil than the leaves. Distillation of the lower two-thirds of the plant is unprofitable. 

 Drying of the plant apparently produces no change in either the quantity or quality of 

 the oil. Apparently, there exist some definite relations between yield on one hand and 

 density and refractive index on the other. As stated above, Miller separated the oil 

 into various fractions and proved the existance of following constituents in the oil: — 

 I- and ^7-pinene (nitrosochloride, m. p. 102 to 103°; nitrolpiperidin, m.p. 119°), Mimonene(?) 



*) Cf. Bull. 785, University of Wisconsin. See also further below on this page. — 2 ) These figures do not agree 

 with Qach other. — *) Bull. Univ. Wisconsin No. 785. 



4 



