The Rates and Products of Addition of 4-Chlorobenzenesulfenyl Chloride to a Series of Side Chain Methyl Substituted Styrenes

Abstract

The rates of addition and the product compositions have been determined for the addition of 4-chlorobenzenesulfenyl chloride to a series of seven side chain methyl substituted styrenes in 1,1,2,2-tetrachloroethane at 25°. Unlike the addition to the corresponding series of methylated ethylenes, the effect of the methyl groups is not cumulative. The effect of the methyl groups depends upon whether or not the β-methyl group is cis to the phenyl. When it is cis, the rate of addition is decreased compared to styrene and substitution of additional methyl groups has only a small effect on the rate of addition. In compounds lacking a cis-β-methyl group the rate of addition more closely resembles that for addition to the methylated ethylenes. Steric hindrance between the cis-methyl and phenyl groups is believed to be the cause of this difference in behavior between the ethylene and styrene series.