TERPEIVES AND ESSENTIAL OILS, I. 53 



reduction of limonene livdrochloride with sodium and alcohol at a tem- 

 perature not higher than 10°. Semmler's dihydro-limonene had a Ijoiling 

 point of 173° to 174°; specific gravity, 20°=0.829; N"d =1.463; Pol.= 

 +40, while the same hydrocarbon prepared from phellandrene hydro- 

 chloride by reduction with sodium and amyl alcohol has a boiling point 

 of 171° to 172°; specific gravity, 20°=0.839; Nb=1.4601; Po1.=+25. 

 Experiment 2. — The limonene was distilled from orange peel oil and had the 



OAO ono OQO 



following constants: Specifie gravity, ^ = 0.8365 ; A^ = 117.2; N^ = 1.4080; 



30° 30° 30° 



the hydrochloride, specific gravity, -—-=0.9675; N^=— =1.4770; A^=— =06.5°. 



The analysis gave: 



Found 



Calculated for CmHuCI 



(per cent). 



(per cent). 



20.26 



20.3 



CI 



Fifty grams of this substance were now put through the Grignard reaction 

 with 9 grams of magnesium and 150 cubic centimeters of dry ether in the 

 apparatus used for experiment 1, the reaction being started with methyl iodide 

 and iodine. There resulted 38 grams of crude oil (calculated 39.8 grams), con- 

 taining onl}' 0.61 per cent of chlorine, so that 3 per cent of the total hydrochloride 

 used had not been acted upon by the magnesium. This oil was separated into two 

 fractions by careful distillation in vacuo with the following results : 



No. 1 : B. P. 85° to 86° at 40 millimeters, 29.2 grams containing no chlorine. 



No. 2: A residue of 7.3 grams containing chlorine. 



Number 1 possessed the peculiar, etherdike odor of the dihydroterpene and gave 



ono ono ono 



the following constants: Specific gravity, ^ = 0.8258; N^f-=1.4580; A— -=78.2. 



The following was the analysis: 



0.1468 gram substance gave 0.4674 gram CO. and 0.1725 gram H.O. 



Found Calculated for CioHis 



(percent). (percent). 



C 86.81 86.9(5 



H 13.09 13.04 



Twenty-eight grams of the oil Ci„H,s were now diluted with an equal volume of 



carbon bisulphide, drj' hydrogen chloride passed into the mixture to saturation 



and the whole kept in ice and salt for ten hours. The product was purified in 



the usual manner and yielded 23 grams of an oil boiling between 110° and 115° 



at 30 millimeters pressure, 8 grams of residue remaining in the distilling flask. 



30° 30° 



The following were the constants: Specific gravity, —5- =0.931; N— - = 1.4624; 



30° 



A— —=6.8°. The analysis gave: 



Found Calculated for C10H19CI 



(percent). (percent). 



CI 20.4 20.3 



A gram of this oil when treated with sodium ethylate in alcohol, yielded a 

 liquid of very pleasant odor, probably the corresponding ethoxy-derivative. 

 Twenty grams of the chloride so produced were subjected to the Grignard reaction 

 in an atmosphere of hydrogen, 4 grams .of magnesium and 60 cubic centimeters 

 of ether being used, the reaction being inaugurated with a little methyl iodide, 

 it proceeded vigorously. There were obtained 14 grams of a chlorine-free oil 



