Substituent Effect of the Benzene Ring on Thermal Rearrangement of the Substituted Benzyl Group from exo-S to N(3) in (rac)2-Substituted Benzylthio-4-methoxycarbonyl-Δ^2-1,3-thiazolines

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The substituent effect of the benzene ring in the catalytic thermal rearrangement of the substituted benzyl group from exo-S to N(3) in compounds 1a-o was investigated. The reactivity order of the rearrnagement with various substituents was as follows; (high)p-OMe≫ p-Me>H, p-F, p-Cl, p-Br≫ p-CN, p-NO_2,p-CO_2Me (low). A crossover experiment employing compounds 1k and 2d (Exp. 2 in Chart 3) or compounds 1d and 2k (Exp. 3 in Chart 3) furnished interesting and informative results. Detailed comparison of these results with those of the ordinary experiments (Exp. 1 and Exp. 4 in Chart 3) provided support for a reaction mechanism involving benzylic cation formation of substituted benzyl bromides as the key step in the catalytic thermal rearrangement.
1988-02-25