THE PRODUCTS OF THE REACTION OF THIIRANIUM IONS WITH COMPETING NUCLEOPHILES

The reaction of the stable thiiranium ion, prepared by the reaction of trifluoromethanesulfonic acid and methyl-3-(4-chloropheny1thio) propene with tetraethylammonium chloride in either 3.5 or 36% v/v methanol/dichloromethane with urea as a buffer, forms 2-methoxy-2-methyl-I-propyl 4-chlorophenyl sulfide, 2-chloro-2-methyl-1-propyl 4-chlorophenyl sulfide, and 1-chloro-2-methyl-2-propyl 4-chlorophenyl sulfide as products. While these same products are formed by the addition of 4-chlorobenzenesulfenyl chloride to methylpropene in the same solvents, their proportions differ. This is one of the rare examples in which there is a difference in the product composition of thiiranium ions formed in different ways and allowed to react under identical conditions. One possible explanation for this difference may be that the two thiiranium ions form products by different paths involving different kinds of ion pairs. Copyright © 2014 - Canadian Science Publishing.