﻿16 CLOVER. 



rotation was just one-half of this number. The oil had the characteristic 

 odor of phellandrene and gave a heavy precipitate of the nitrite. A por- 

 tion distilled at ordinary pressure boiled completely from 172° to 173°. 5. 

 This product has the highest rotation of any sample of phellandrene 

 obtained. 



The purified, high-boiling oil boiled from 168°. 5 to 172° at 37 millimeters 

 on the third distillation, and it constituted most of the unpurified product. 



Sp. gr. 3 4 °= 0.9461; a ^= — 0.8°; n^ = 1.4944 (XVLB, purified). 



Sample XVII. — The purified terpene oil boiled almost completely from 

 86° to 87°. 5 at 48.5 millimeters and therefore, accordingly, a little higher 

 than phellandrene should distill (XYII,A purified). In contained much 

 phellandrene but the rotation as well as the boiling point indicated that 



so so 



some other substance was present, a D = 4-73°. 5; n-£>= 1.4693. A por- 

 tion of it distilled from 173° to 174°. 5 at ordinary pressure. No crystal- 

 line bromide could be obtained in acetic acid, nor in ether and amyl alcohol. 

 No limonene could be detected by tests with ethyl nitrite in acetic acid 

 or in ligroin. In preparing phellandrene nitrite, no crystals of terpinene 

 nitrite appeared in the mother-liquor on standing. The crude phellan- 

 drene nitrite was dissolved in a small amount of chloroform, filtered and 

 precipitated with ether. Melting point, 114° to 117°. On recrystallizing 

 from acetic ester without warming, it melted at 119°. 5 to 121°. On re- 

 crystallizing it melted at 120° to 121°. The crude nitrite obtained con- 

 stituted about 50 per cent of the weight of the original oil. The rotation 

 of the nitrite melting at 119°. 5 to 121° was approximately that found by 

 Wallach for pure a-phellandrene a-nitrite obtained from several sources, 

 so that it appears that the low rotation of this sample of phellandrene 

 and the variation observed in the rotation of the other samples obtained, 

 are not to be explained by assuming the presence of varying amounts of 

 laevo-phellandrene. It will be brought out later that the second sub- 

 stance in this oil is lasvo-limonene. The high-boiling oil from this sample 

 was redistilled 3 times and a product obtained boiling within 3°. On 

 standing, this oil soon separated an unusually large amount of crystals, 

 identical with those previously observed. 



Sample XVIII. — The purified terpene oil boiled completely from 

 88°. 7 to 90°.4 at 54.5 millimeters pressure. It was found to be phellan- 

 drene and judging from the boiling point was almost, if not quite, pure, 

 (XVIII,A, purified). The rotation, however, is somewhat lower than 



Of) 



that of some of the phellandrene oils, a j^= -[-113°. 5. On standing 



for a couple of months the sample contained a small quantity of the 

 familiar crystals. 



