A Kinetic Study of the Friedel-Crafts Phenylsulfonylation of Alkylbenzenes in Nitrobenzene

Abstract

The reaction of alkylbenzenes with benzenesulfonyl chloride in the presence of aluminum chloride was studied kinetically in nitrobenzene.
The rate constants k₃ were in good agreement with Hammett-type linear free energy relationships, that is, Yukawa-Tsuno equation (log f=ρ(σ+γΔσ_R+), ρ=-4.8, γ=0.6).
Differences in activation energies and activation entropies at the o- and p-positions and the m- and p-positions were -0.27 kcal/mol, -2.1 e.u./mol and 1.2, -1.4 for toluene, -1.2, -2.1 and 0.48, -2.3 for ethylbenzene, -1.9, -9.9 and 0.53, -1.9 for isopropylbenzene and and -, - and 0.1, -3.0 for t-butylbenzene, respectively.