318 IV. WAXES, HIGHER ALCOHOLS, ETC. 



and 2-butanone. On the other hand, the alcohols are largely insoluble in 

 the highly polar solvents, nitroethane and acetonitrile, with the result that 

 over a wide range they form two immiscible solutions. The solubilities of 

 the Cio to Ci8 alcohols in diethyl ether, acetone, and 95% ethyl alcohol at 

 widely varying temperatures are listed in Table 3. 



As in the case of the corresponding aliphatic acids, the solubility of the 

 alcohols is progressively reduced as the chain length is increased. As would 

 be expected, solubility in all cases increases with a rise in temperature, so 

 that at 20° and higher the 1-decanol is infinitely soluble in the three sol- 

 vents reported in Table 3. At 30°C., infinite solubility also obtains for 

 1-dodecanol, and at 40 °C. the same is true for 1-tetradecanol. As in the 

 case of the fatty acids, the relative effectiveness of different solvents for a 

 given alcohol varies with the temperature. Furthermore, the proportions 

 of the alcohols which dissolve in the several solvents at a fixed temperature 

 vary with the particular alcohol. Thus, in order to state the best solvent 

 under a given condition, one must consider both the alcohol to be dissolved 

 and the temperature of the solution. 



(d) Chemical Reactions of Alcohols. The reaction which is considered 

 most characteristic of alcohols is esterification. Such an interaction occurs 

 readilj'' not only with organic acids but also with inorganic acids. The 

 subject of esterification has been considered in Chapter II. 



On oxidation, primary alcohols are changed first to aldehydes and then 

 to the fatty acid derivatives. When the alcohols are subjected to hydro- 

 genation at 350 °C. under 200 atmospheres pressure with nickel as a catalyst, 

 they become reduced to the corresponding saturated hydrocarbon. 



Two different products may originate on thermal decomposition of 

 alcohols. Thus they may lose hydrogen to yield an aldehyde: 



RCHjOH ►RC-H + Hj 



When the reaction conditions are varied, the product on dehydration will 

 be an olefin: 



RCHjCHzOH ►RCH:CH2 + H2O 



The alcohols are converted to the saturated hydrocarbons having one less 

 carbon when they are subjected to hydrogenolysis by passing them over re- 

 duced nickel catalysts at 250 °C. under a pressure of 100 to 200 atmospheres 

 of hydrogen.^^ Thus, Boeseken and van Senden^^ have reported the jjro- 

 duction of hexane after hydrogenolysis is applied to 1-heptanol. 



«6 B. Wojcik and H. Adkins, /. Am. Chem. Soc, 55, 1293-1294 (19;^:?). 

 " J. Bueseken and G. H. van Senden, Rec. trav. chim., 32, 23-38 (1913), 



