﻿28 CLOVER. 



30 

 The product was distilled with steam and the distilled oil showed a „ =-{-38°. 



Phellaiulrene nitrite prepared from this in the usual manner melted at 119° to 

 120°. 5 after the first recrystallization from acetic ester. In chloroform solution 

 at a concentration of 3, the specific rotatory power was found to be about the 

 same as that produced in previous cases by the a-nitrite and therefore there 

 was no evidence that any racemic phellandrene had been formed. 



After what has been brought out concerning the rapid change in rota- 

 tion which the nitrite undergoes in solution, it must be borne in mind 

 that the values obtained for this property of the nitrite are only ap- 

 proximate, but when they are taken for different samples under the same 

 conditions, they are abundantly adequate for purposes of comparison. 



The phellandrene used in the heating experiments (1), (2), and (3) 

 was taken from sample XIV,A, purified, which, as will be brought out 

 later, contained a small amount of kuvo-limonene. The process was 

 therefore repeated with a quantity of XVI,A, purified, which, so far as 

 it was possible to determine, is pure phellandrene. The substance was 

 heated in a sealed tube for forty-eight hours at 210° to 215°. The prod- 

 uct was colorless. The oil after having been distilled with steam still gave 



a slight test for phellandrene and showed a ^ = — 18°. The lsevo-rotation 



of the product appears therefore to be due to a product of isomerization 

 of phellandrene. This oil, when dissolved in cold carbon tetrachloride 

 and heated with bromine, combined at once with less than 2 atoms 

 of the latter and considerable hydrobromic acid was evolved. Further 

 action was much slower. The same result was obtained in glacial acetic 

 acid, although in this case the evolution of hydrobromic acid was not 

 so apparent, as it was probably held in solution by the acetic acid. 



A portion of the same sample of freshly purified phellandrene used 

 in the last experiment was sealed in a nearly filled flask and allowed to 



stand for three months. The original rotation was a p=-fl29 .8. 



On opening the flask it was found to be a ^ =127°. 1, accordingly a 



decrease of about 3°. Phellandrene, therefore, undergoes a slow altera- 

 tion at ordinary temperatures, probably the same which takes place more 

 rapidly at a higher temperature. 



Action of hydrochloric acid. — About 30 grams of phellandrene, taken 

 from the oil, V,A, purified, were heated with metallic sodium for a few 

 minutes, then distilled from the later into a dry fractioning flask 



(a ^=:-|-115.5 ) and mixed with an equal volume of dry carbon 



disulphide. A slow stream of very dry hydrochloric acid was then passed 

 into the liquid, the exit tube having been attached to a tube of calcium 

 chloride. The acid was readily absorbed and the liquid appeared to 

 become heated more quickly than when limonene had been employed 

 under the same conditions. It was kept cool by immersing the flask 



