Rates and Alkyl Group Size in Solvolysis of Alkyl Derivatives

Article abstract of DOI:10.1021/jo00367a001

The logarithm of solvolysis rate constants in 80percent aqueous ethanol of 1,1-dimethyl-1-alkyl chlorides 1 and 1-phenyl-1-alkyl chlorides 2 decrease monotonically with increasing number of carbon atoms in the alkyl group.The first member of both series deviates from the corresponding correlation lines which have the some slope.In contrast, solvolysis rates in 80percent aqueous ethanol of 1-methyl-1-alkyl tosylates 3 do not depend upon the size of the alkyl group.The results are rationalized in terms of a mechanism that is very similar in reactions of series 1 and 2 but different from that of series 3.