PHILIPPINE TERPEXES A\D ESSENTIAL OILS, III. 105 



substances, as would be expected from bodies of this nature formed 

 according to the reaction of Grignard. I will record but a few of the 

 experiments performed to show the type of reactions. 



LIMONENE HYDROCHLORIDE. 



(1) Limonene from eleini, distilled over sodium with an equal volume of pe- 

 troleum ether, was saturated with dry hj'drochloric acid gas; limonene hydro- 

 chloride with the following properties was obtained on distilling this product in 

 vaetw: 



OAO 



Boiling point at 12 millimeters' pressure, 95° to 07°, specific gravity, ^ 



0.961G; N§5!=1.47.58; a10!=80°.1; yield, 90 per cent. 



Found Calcnlated 



(percent). (percent). 



■ CI 20.2 20.3 



Fifty grams of this limonene hydrochloiide, 10 grams of magnesium, and 100 

 cubic centimeters of absolute ether were allowed to react in an atmosphere of dry 

 hydrogen. When the reaction was over, 4.5 grams ( calculated 4.3 grams of ortho- 

 formic ester) were added."* The resulting reaction was not violent and, therefore, 

 the mixture was heated for two hours on a steam bath, the greater part of the 

 ether escaping through the reflux condenser. The yellowish, solid reaction product 

 was during the next morning treated in the usual manner by placing it upon 

 crushed ice and adding dilute, cold sulphuric acid. There were thus obtained 48 

 grams of an oil (calculated 85 grams). This oil consisted principally of the 



dihydroterpene C,„PI,,, boiling at 171° to 173°; N§5! = 1.4G10. The ortho-formic 



ester had apparently disappeared in the aqueous solution, as alcohol and formic 

 acid were both easily detected therein. 



(2) Limonene hydrochloride 60 grams, absolute ether 150 cubic centimeters, 

 magnesium 10 grams. After the reaction was over, 60 grams of ortho-formic ester 

 were added with very vigorous stirring. The apparatus was arranged to catch any 

 gas which might be evolved during the reaction, but none was obtained. After 

 heating for two hours on a steam bath, the reaction mass was .separated into ether 

 soluble and ether insoluble portions, and each portion was decomposed separately 

 with ice and dilute sulphuric acid. 



Portion soluble in ether. Portion insoluble in ether. 



Alcohol, 23.1 grams. Alcohol, 12.5 grams. 



Formic acid, 8 grams. Formic acid, 7.5 grams. 



Oil, 45 grams, which consisted of 7 grams High boiling oil, 5 grams. This latter 

 "Vorlauf," 31 grams of C,„H,s, and 4 oil boils at 150° to 220° at 10 milli- 

 grams of a high boiling oil. The meters, leaving a tarry residue of 2.3 

 "Vorlauf" contained considerable grams. The 2.5 grams high boiling 

 quantities of ethyl formate and the oil, distilled once gave no reaction 

 high boiling oil gave no reaction with with phenylhydrazine, and dilute 

 plienylhydrazine, even after boiling boiling acids had no effect on it. 

 with dilute acids and was probably 

 principally a diterpene. 



'" Kahlbaum fraetioned several times over small amounts of sodium with which 

 it reacts only slightly; boiling point, 144° to 146° ; N 2^ = 1.3935. 



