﻿THE TERPENE OILS OF MANILA ELEMI. 17 



Most of the high-boiling oil after 3 fractionations was obtained as a product 

 boiling completely from 168°. 5 to 172° at 37 millimeters. Just as is XVI, B, 



purified, it is yellow in color and of high viscosity. Sp. gr.,'^ =0.9559; a * =-|-2 ; 



30 

 n j. =1.4950. This oil also deposited a good quantity of crystals on standing. 



Sample XIX gave a purified terpene oil boiling from 90° to 91° at 



50 millimeters pressure (XLX,A, purified); a ^=-{-98°; n ^=1.4680. 



It is evidently practically pure limonene, although the rotation is a little 

 lower than usual. From the high-boiling oil of this sample it was 

 found impossible to isolate a considerable portion which would show a 

 narrow range in boiling point. 



Sample XX. — The purified terpene oil from this sample boiled com- 

 pletely from 81°. 7 to 83° at 35.5 millimeters, a g>= +97°. The sub- 

 stance appeared to be practically pure limonene, although the rotation 

 is lower than that of any other sample isolated. It gave no test for 

 phellandrene. 



Sample XXI proved to be especially interesting. It was small in 

 amount and was a fresh, soft resin when collected, although nearly four 

 months elapsed before it was distilled. The terpene oil on the second 

 distillation passed over almost completely within 1°, the boiling point 

 lying between that of phellandrene and limonene. Its rotation was 

 +4°. Because of its rotation and boiling point, it was at first supposed 

 to be terpinene, but no test for terpinene could be obtained. The oil 

 contained no phellandrene according to notes made at the time it was 

 distilled. There can be no doubt on this point, as the phellandrene nitrite 

 would certainly have been noted in the test for terpinene, the tests always 

 being made in essentially the same manner. On long standing, even 

 after having been inoculated with a crystal of terpinene nitrite, no 

 separation of this substance occurred. On the same day that the test for 

 terpinene was made and when it was found that the terpinene nitrite was 

 not being formed, the oil was treated with bromine in cold acetic acid 

 and a crystalline bromide obtained. This was recrystallized from acetic 

 ester. The crystals did not appear to be those of dipentene tetra- 

 bromide, as they melted at about 117° with darkening and effervescence. 

 The substance was recrystallized from alcohol, in which it appeared to be 

 more soluble than dipentene tetrabromide. The crystals were lustrous 

 plates and melted at 116°, with darkening and effervescence. It was 

 noted at the time that these crystals were entirely different from those 

 of dipentene tetrabromide with which I was very familiar and which I 

 rather expected to obtain when the test was made. The substance was 

 certainly the tetrabromide of terpinolene discovered by Wallach 13 in 



13 Awri. Chem. (Licbig) (1SS5), 230, 262; (1887), 239, 23. 

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