Electrophilic additions to alkenes. Part VII. The addition of 2,4-dinitrobenzenesulphenyl chloride to aliphatic alkenes

Abstract

The rates of addition of 2,4-dinitrobenzenesulphenyl chloride to aliphatic alkenes in acetic acid at 25·0 °C are correlated by the equation, log k/k₀=ρ*Σσ*+δΣE_s, where log k₀=–1·28, ρ*=–2·84, and δ= 0·664. Rates for trans-alkenes were excluded from this correlation as with similar studies involving chlorination and bromination. 2,4-Dinitrobenzenesulphenyl chloride is less selective in its addition reactions than chlorine or bromine and this is attributed to the greater participation by sulphur as a neighbouring group which reduces the effect of electron-releasing groups in the alkene. Steric effects are of relatively greater importance with the sulphenyl halide than with the halogens and this also contributes to the lower selectivity.