Neighboring Group and Substituent Effects in Organosulfur Compounds



Thioether groups participate in nucleophilic substitution reactions at adjacent carbon atoms, in the addition of alkane and arenesulfenyl halides onto olefinic double bonds, and in elimination reactions which lead to olefins and which proceed via intermediate episulfonium ions. Studies of alkylthioacrylic acid derivatives, which are readily synthetized because of the neighboring group effect, show that the presence of thioether groups in the α-position of acrylic acid systems leads to particularly high reactivity in “head-to-head” dimerizations.