Electrophilic additions to alkenes. Part II. Kinetics of the reaction of 2,4-dinitrobenzenesulphenyl bromide with cyclohexene in carbon tetrachloride solution

Abstract

The reaction between 2,4-dinitrobenzenesulphenyl bromide and cyclohexene in carbon tetrachloride solution appears to be essentially homogeneous, and polar. Kinetically it is complex, like many electrophilic additions in relatively non-polar solvents, the reaction being first-order in cyclohexene, and above first-order in sulphenyl bromide. The rate equation, Initial rate =k₂°[B][ArSBr]+k₃[B][ArSBr]²+k₄[B][ArSBr]³ where B = cyclohexene, is proposed, and the complexity of this equation attributed to solvation assistance in the transition state by molecules of sulphenyl bromide.