LEGUMINOS^E 481
per cent,, and Maracaibo oil 2 per cent, of /2-caryophyllene. African
copaiba oil contains only O87 per cent, of this hydrocarbon.
Several investigations have established the presence in African
copaiba balsam oil of considerable proportions of a dextro-rotatory
sesquiterpene, possessing the properties of cadinene, but affording a
laevo-rotatory hydrochloride. Schimmel & Co.^1 have examined the first
runnings of the sample, and submitted 600 grams thereof to careful
fractionation. They obtained the following principal fractions with
more or less constant boiling-points ;—-
- 119° to 120° (10 mm.) ; 246° to 248° (750 mm.) 10 per cent.; on _ 13° 7 ^
248° „ 250° ( „ „ ) 70 „
250° „ 251° ( „ „ ) 10
12-)° ,
130° ,, 125° ( „
, 133°( „„ ) ; 258° „
„„ ) ; 267° „
270° „263°( „
270° ( „
273° ( „„„ ) —
., ) 20 „ „
„ 2 73°( „ ,,; AD _ 6° 52'.. aD + 50°.
The principal fraction (No. 3) had the same boiling-point as cadinene.
The other characters of the " cadinene-fraction " isolated from the oil were:
tf 15 o 0-9261, [a]D + 60° 40', ?ID2O° 1-51112.
Fraction 2 (20 gr., ao - 6° 52') was tested for caryophyllene. With
glacial acetic and sulphuric acids it afforded no caryophyllene alcohol, but
when nitric oxide was passed into the ethereal solution according to
Deussen's method described above they obtained 2
- 33 per cent, of a nitro-
genous body, derived from ^-caryophyllene (melting-point 155° to 156*
from acetone).
Fraction 1 (100 gr., d 15 o 0-9077, [a]D - 13° 21', nD2o° 1-48943) only
afforded the smallest traces of the nitrogenous body from /3-caryophyllene,
and can therefore have contained next to nothing of this sesquiterpene.
Iti yielded neither a solid nitrosochloride nor a nitrosite, but it afforded
30 per cent, of a solid hydrochloride, melting-point 117° to 118° and [<X]D
- 36'38° in a 509 per cent, chloroform solution. These characters, as
well as the fact that no depression in the melting-point was obtained by
admixture with Z-cadinene hydrochloride, showed it to be identical with
this body.
When treated with sodium acetate in a glacial acetic acid solution the
hydrochloride yielded a cadinene possessing the following properties :
boiling-point 273
°
to 275°, dl5 0-9229, [a]D - 116-73°, n^o 1-50651; when
treated with hydrochloric acid gas cadinene hydrochloride, melting-point
118, was again formed.
The liquid chlorides freed by suction from the cadinene hydrochloride
of fraction I were examined for the presence of other chlorides. As they
could not be distilled in vacuo they were boiled with their own weight of
sodium acetate in glacial acetic acid solution, for the purpose of eliminat-
ing the hydrochloric acid, and the resulting oil was fractionated in vacuo.
Of three equal fractions thus obtained—
(a) 111° to 121° (7 mm.), (b) 121° to 130°, (c) 130° to 135°,
(b) and (c) afforded copious proportions of cadinene hydrochloride, melting-
point 117-5° and 118
J
, only fraction (a) failed to yield a solid product.
The liquid chlorides of fraction 1 were practically identical in character
with the solid chloride, and must therefore have consisted in the main of
cadinene hydrochloride.
(^1) Report, April (1914), 48.
VOL. I. 31