STUDIES ON β-METHYL-1-AND 3-PHENYL ALLYL CHLORIDES

Article abstract of DOI:10.1016/S0040-4020(01)99326-3

The hydrolysis of β-methyl-1-and 3-phenylallyl chlorides (1a and 1b) have been investigated in aqueosus dioxan and the proposed mechanism compared with those reported for the corresponding 1- and 3-phenylallyl chlorides (2a and 2b).Hydrolysis of 1a and 1b proceeds via the same mechanism as 2a and 2b, respectively, with different behavior by the first intermediate.The first intermediate of 1a rearranges to the corresponding conjugated compound through a transition state rather than an intermediate.Theoretical calculations on the carbonium ions of 1 and 2 using a semiempirical MINDO/3 molecular orbital method show that the charge densities on carbon atoms of 1 are nearly the same as those of 2.The main difference is in the bond angle C¹-C⁸-C⁹.