PHILIPPINE TERPENES AND ESSENTIAL OILS, III. 109 



There was no action on the carbonyl group. It is well-known that 

 very many reactions carried out according to the Grignard method give 

 yields which are not by any means quantitative. The secondary products 

 which will throw so much light on the mechanism of this reaction have, 

 as a general rule, been utterly neglected. It is exceedingly probable that 

 these reactions take place in many different directions, depending upon 

 the conditions and upon the reacting masses, as is shown by my work 

 in the terpene series. 



PHELLANDBENE. 

 PHELLANBEENE HYDROCHLORIDE. 



The united terpenes of series Calaoag B-3 were distilled over sodium in vacuo; 

 boiling point, 64°.5 to 65° at 15 millimeters (62° to 62°.5 at 10 millimeters) ; 



specific gravity, ^=0.8349; N?2! = 1.4657; A52!=77°.8. An equal volume of 



dry ligroin was added and the terpene was then saturated with dry hydrogen chlo- 

 ride. After removing the liquid, the residual oil Avas distilled at 1 millimeter 



OOO OAO 



pressure; boiling point, 80° to 83°; specific gravity, ?r^=0.960; N_-=1.4770; 

 chlorine found, 20.2 per cent; chlorine calculated, 20.3 per cent. 



The odor of this hydrochloride is much like that of the corresponding 

 limonene derivative. Phellandrene hydrochloride did not react com- 

 pletely with magnesium in the presence of ether ; therefore, phellandrene 

 hydrobromide was prepared. This compound can not be distilled in 

 vacuo without decomposition and in fact it slowly decomposes with 

 evolution of hydrobromic acid even at the ordinary temperature. Phel- 

 landrene hydrochloride begins to split off hydrochloric acid at about 85°, 

 and must be distilled below that temperature. 



PHELLANDRENE HYDROBROMIDE. 



a phellandrene, boiling point at 9 millimeters 62° to 63° ; specific gravity, 

 ' —=0.8364; Ni— = 1.4673, was mixed with an equal volume of dry petroleum ether 

 and saturated with dry hydrogen bromide. After removing the petroleum ether the 



or\o 



crude hydrobromide had the following properties: Specific gravity, ^i-i- =1.1302; 



,30° ^° 



N = 1.5018; bromine found, 37.6 per cent: calculated, 36.8 per cent. 70 grams 



of this hydrobromide were subjected to the Grignard reaction with 10 grams of 

 magnesium and 200 cubic centimeters of absolute ether, and after the reaction 

 was complete, 40 grams of benzaldehyde were added. A yellow-white solid 

 separated. The reaction mixture was separated into ether soluble and ether in- 

 soluble substances, and each portion was separately decomposed with ice and dilute 

 sulphuric acid. 



82592 — —2 



