Ryan and Dillon — On Higher Tertiary Alcohols. 239 



Hence the latter compound should be more difficult to form ; and the 

 reaction between the alcohol and acetic acid should give rise to a larger pro- 

 portion of unsaturated hydrocarbons. This is in accordance with the facts. 



We have already seen that the tertiary alcohols form unsaturated hydro- 

 carbons under conditions where esters might be expected, and Wolkoff and 

 Bougaieff' have found that the lower members of the series split off water 

 when heated in a sealed tube to 240-250° C, in presence of a trace of hydriodic 

 acid or methyl iodide. It might therefore be surmised that the formation of 

 unsaturated hydrocarbons would take place easily when the higher tertiary 

 alcohols are heated with potash-lime. We have found, however, that below 

 250° C. no such change occurs ; but when the temperature was raised to 300° C, 

 the production of unsaturated bodies but no evolution of hydrogen was 

 observed. 



In considering the anomalous behaviour of beeswax towards potash-lime 

 in the light of these facts, we must bear in mind that the formation of 

 unsaturated hydrocarbons from tertiary alcohols might take place more 

 readily when these bodies are in the form of esters than when they are in the 

 free state. If, therefore, the so-called hydrocarbons obtained by the action of 

 potash-lime on beeswax should prove to contain appreciable quantities of 

 oxygen, it might be inferred that tertiary alcohols were present ; but if oxygen 

 was found to be absent, the hydrocarbons might still be due to the decompo- 

 sition of such alcohols under the conditions of the experiment. 



Experimental Part. 



PreiMration of Esters. Methyl Palmitate. — 20 grammes of Palmitic 

 acid and 100 c.c. of methyl alcohol were warmed in a beaker on the water- 

 bath until the alcohol had begun to boil. Concentrated sulphuric acid was 

 added slowly drop by drop from a pipette. When three or four c.c. of acid had 

 been added, oily drops began to appear in the liquid and these collected to 

 form a layer on the surface of the alcohol. When 10 c.c. of the acid 

 had been added the beaker was replaced on the water-bath for a few minutes. 

 It was then cooled ; the solid cake of ester was separated from the liquid 

 layer, and dissolved in ether. The ether solution was washed with water, 

 then with dilute sodium bicarbonate, and finally again with water. It was 

 then dried over sodium sulphate and the ether was evaporated off. The yield 

 of ester was 20 grammes. 



Methyl palmitate is a white wax-like solid, which crystallizes in needles, 



' Journ. Russ. Chem. Soc, 1885, p. 276. 



