Elimination and addition reactions. Part 37. A comparative study of electronic, steric, and solvent effects upon reactivity in additions of benzenesulphenyl chloride to alkenes

Abstract

Rates of additions of benzenesulphenyl chloride to 35 alkenes in several solvents have been measured, and the products of the reactions have in most cases been identified. Results for arylalkenes broadly confirm previous work, but the responses to solvent change are not uniform throughout. The reactivity of bridged cycloalkenes is substantially greater than that of cycloalkenes, but that of cyclo-pentadiene dimer is anomalously small. For allylic substrates, the correlation of electron density at the double bond with reactivity is shown by a rectilinear relationship between log k and σ_I. Allyl iodide and allyl alcohol are anomalously more reactive than this correlation would predict; this is accounted for by solvation and by internal solvation effects respectively.