Basicity of alcohols

The greater basicity of alcohols over olefins is responsible for the fact that dehydration can be performed by weaker acidic sites than are necessary for olefin isomerization. There are, however, also other factors, such as participation of neighboring groups, which may influence the rate of dehydration of alcohols. 

Secondary alkyl halides will mainly undergo elimination when treated with alcoholates, particularly if the alcoholate is sterically demanding and if the reaction is conducted at high temperatures [60], Because of the high basicity of alcoholates, even primary alkyl halides can undergo dehydrohalogenation on treatment with alcoholates (Scheme 6.16). 

In this section, we study the acidity and basicity of alcohols, their dehydration to alkenes, their conversion to haloalkanes, and their oxidation to aldehydes, ketones, or carboxylic acids. 

Particularly risky will be titration procedures in which the bases being compared are themselves serving as solvent. From this standpoint an often-quoted comparison (322) of the basicities of alcohols by means of titrating a complex chelate indicator with water in the alcohol as solvent should be regarded with considerable reserve. 

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