The Effect of Temperature and Solvent upon the Addition of 4-Chlorobenzenesulfenyl Chloride to cis- and trans-1-Phenylpropene

The effect of temperature upon the product composition of the addition of 4-chlorobenzenesulfenyl chloride to cis- and trans-1-phenylpropene in 1,1,2,2-tetrachloroethane has been studied. The kinetically controlled product in both cases is the adduct with Markownikoff orientation while the thermodynamically controlled product is the one with the anti-Markownikoff orientation. Kinetic and thermodynamic parameters have been determined for the isomerization of the threo as well as the erythro adducts. The effect of different solvents on the product composition has been studied at 25°. The regioselectivity towards Markownikoff product parallels the increasing acidity and anion solvating ability of the solvent.