Ruthenium(III)-catalyzed oxidation of substituted ethanols by sodium N-bromo-p-toluenesulfonamide in hydrochloric acid medium

Abstract

The kinetics of oxidation of substituted alcohols, RCH2CH2OH (R = H-, OEt-, OMe-, NH2-, Cl- and Br-) by sodium N-bromo-p-toluenesulfonamide or bromamine-T (BAT), catalyzed by ruthenium(III) chloride in the presence of HCl, has been studied at 303K. The reaction rate shows first order dependence each on [BAT], [alcohol] and [RuIII]. The reaction rate is inversely dependent on [H+]. Addition of halide ions and the reduction product, p-toluenesulfonamide has no significant effect on the rate. Composite activation parameters ΔH‡, ΔS‡ and ΔG‡ were computed by studying the reaction at different temperatures (298–313K). The rate decreased in D2O medium and the solvent isotope effect k′(H2O)|k′(D2O) = 1.63 and 1.68 for EtOH and BrCH2CH2OH respectively. Proton inventory studies have been made in H2O–D2O mixtures for both alcohols. The conjugate acid, TsNHBr, is assumed to be the reactive species. The rates do not correlate satisfactorily with Taft substituent constants. The protonation constant (25.3) of monobromamine-T has been evaluated. From enthalpy-entropy relationships and Exner correlations, the isokinetic temperature (β) was found to be 368 K, which is much higher than the experimental temperature, indicating that enthalpy factors control the rate. The proposed reaction mechanisms and the derived rate laws are consistant with the observed kinetic data. The rate of oxidation of alcohols RCH2CH2OH follows the order: H > Br > OEt > OMe > Cl > NH2.