Polymer modification and synthesis using sulphenyl derivatives. Part 8. Addition of arylsulphenyl chlorides to polyisoprene

Abstract

Toluene-p-sulphenyl chloride reacts smoothly with cis-1,4-polyisoprene (PIP) in various proportions, but the resulting adducts decompose spontaneously via loss of hydrogen chloride. From an examination of model compounds and of the adducts of PIP with other sulphenyl chlorides, it is concluded that decomposition results from the saturation of successive double bonds along the polymer chain. The extent of decomposition indicates a high degree of regioselectivity in the original addition reaction. Some light is shed on the mechanisms of sulphenyl chloride additions to olefins and of the decomposition of aryl ω-halogenoalkyl sulphides.