﻿14 CLOVER. 



that this terpene is considerably lower than phellandrene in refractive 

 power and specific gravity. As with the oil of Sample VII, it was 

 not found possible to obtain any solid derivatives except phellandrene 

 nitrite. 



The high-boiling oil from this sample was redistilled. On the second frac- 

 tionation it showed so small a portion of constant-boiling product that it was 

 totally discarded. 



Sample XI. — This sample was small in amount and to obtain enough 

 terpene oil to work with, the latter was completely removed at a temper- 

 ature of 200°. The oil was not purified in vacuo but was redistilled twice 

 at ordinary pressure, passing over the second time mostly from 173° to 



on 



178°, a 'j)= — 50°. 7. This is the only case in which the lrevo-rotatory 



oil has been obtained from a sample of elcml. The oil gave a precipitate 

 of phellandrene nitrite, but the yield was not large. In cold, glacial acetic 

 acid a tetrabromide was separated but a much better yield was obtained in 

 amyl alcohol and ether. When recrystallized twice from alcohol, it 

 showed a melting point of 104° to 105°. The tetrabromide of lsevo- 

 limonene in chloroform at 9° and at a concentration of 12.85 per 

 cent gives [a]p= — 73.45 as determined by YVallach and Conrady. 12 

 The amount of pure bromide at hand was not large enough for an accurate 

 estimation, but it was found to be lsevo-rotatory and to about the degree 

 just mentioned. A small portion of it was carefully weighed out and 

 mixed with exactly the same amount of pure dextro-limonene tetra- 

 bromide. The mixture was dissolved in a small amount of acetic ester 

 and alcohol was then added. On cooling, pure dipentene tetrabromide 

 crystallized out. Melting point 124°. The oil, therefore contains lasvo- 

 limonene and phellandrene, the latter being probably dextro-rotatory. 

 That the laevo-limonene was not formed by the action of heat upon the 

 phellandrene will be seen from experiments given under phellandrene. 



Sample XII was taken from a medium-sized tree which contained no 

 fruit. The resin was quite soft. The purified terpene oil obtained from 

 this sample showed a boiling point of 176° to 176°. 7 at ordinary pressure, 

 a ^=+100°. 3 (XII, A, purified). It is evidently pure dextro-limo- 

 nene. Other data concerning the oil will be inserted under the heading of 

 limonene. 



• The high-boiling oil from this sample, which had been removed at 240°, was 

 fractionated twice, and the greater part of it was obtained as a product which 

 boiled completely from 167° to 170° at 35 millimeters (XII.B, purified). Sp. gr., 



^?= 0.8677; a ??= +71.6°. It was light greenish-yellow in color and not so 



viscous as those oils having a specific gravity around 0.95. It was the only 

 optically active, high-boiling oil isolated from a sample of Manila elemi. 



™Ann. Chcm. (Liebig) (1889), 252, 145. 



