t=? ay 
52 : REPORT OF SCHIMMEL & Co. APRIL 1914.00 
The purest form of hydrochloride, m.p. 68, was again afforded by the fraction 
boiling between 168 and 171°, whereas the hydrochloride isolated from the three 
fractions boiling between 171 and 178° mostly melted as low as 63°, acquired a yellow 
colour when exposed to light, and gradually became somewhat decomposed. In addition 
we obtained considerable proportions of the chloride, which remains liquid in a freezing 
mixture. . 
For the further identification of the /-sylvestrene we warmed 20 gr. hydrochloride 
from fraction 173 to 175°, m.p. 68 and [@])—19,5° with 20 gr. aniline and 5 cc. 
alcohol on wire-netting until aniline hydrochloride was separated out; after which we 
distilled it by steam, adding acetic acid. The J/-sylvestrene regenerated by this 
method (about 10 gr.) possessed the following characters: b. p. 172 to 180°, diso 0,8604, 
Oy — 45°0', np» 1,47838. With acetic anhydride and sulphuric acid, the /-sylvestrene 
gave the familiar intense blue coloration, and also a small last runnings, b. p. 180 
to 185°. After three months the preparation had bécome much resinified. 
As a check-test we diluted with aniline under similar conditions a preparation 
of d-sylvestrene hydrochloride, m. p. 71°. The principal portion of the regenerated 
d-sylvestrene boiled between 178 and 182°; its constants were as follows: disco 0,8659, 
Op +54°17'; nps».0 1,47936. This product also, when treated with acetic anhydride and 
sulphuric acid, gave the blue coloration and was partly resinified after three months’ 
standing. A small last runnings boiling between 182 and 184° was less optically 
active: «) + 41° 43’. 
When the deep-brown coloured liquid chlorides were decomposed with aniline 
we obtained a rather impure sylvestrene (b.p. 170 to 185°; dis0 0,8712; a% — 13° 40’) 
which nevertheless gave the blue coloration with sulphuric acid and acetic anhydride. 
It was a noteworthy circumstance that the fractions of the original oil did not give 
this colour-reaction, although they were certainly rich in sylvestrene. 
The terpene which results from the decomposition of sylvestrene dihydrochloride, 
as Haworth, Perkin and Wallach) have shown, is not a uniform body, but invariably 
consists of a mixture of several hydrocarbons, which can only be partially separated. 
For this reason the properties of the regenerated sylvestrenes also differ. 
Haworth and Perkin’), when resolving a synthetically-prepared J/-sylvestrene 
hydrochloride, m. p. 70 to 72°; sp. rot. @) —21,8°, with diethyl aniline, obtained a 
l-sylvestrene possessing the following characters: b.p. 176 to 178°, digo 0,848, &p — 68,2°, 
Np 1,4761. | 
In order to obtain irrefragable proof that the terpene which occurs in the oil of 
Dacryodes hexandra is in effect I-sylvestrene, we mixed the /-hydrochloride, m. p. 68°, 
obtained from it with an equal quantity of d-sylvestrene hydrochloride, m.p. 71°, and 
crystallised it from methyl alcohol. The result was an inactive carvestrene hydro- 
chloride, melting sharply at 52°. Thus the presence of /-sylvestrene in this oil, 
which was only rendered probable by the investigations of A. More, is now proved 
beyond doubt. 
Elecampane Oil. We have just worked up an excellent parcel of root, rich in 
oil, and we are therefore again able to supply new oil with a full helenine-content. 
We have been able to reduce the price of the newly-distilled oil somewhat. 
1) Liebigs Annalen 399 (1913), 156; Report October 1918, 135. — *%) Journ. chem. Soc. 104 (1913), 2234; 
See p. 132 of the present Report. me ae i 
