• R Balakrishnan

      Articles written in Journal of Chemical Sciences

    • Micellar catalysed oxidative cyclisation of 1,3,5-triaryl formazan

      R Balakrishnan P S Raghavan Vangalur S Srinivasan

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      The kinetics of Tl(III) acetate oxidation of 1,3,5-triaryl formazan has been studied in 90% aqueous HOAc, in the presence of added anionic detergent, sodium-lauryl sulphate(NaLS) and cationic detergent, cetyltrimethylammonium bromide (ctab). Both surfactants enhance the reaction rate, indicating that the reactive species involved is possibly neutral. From the substituent influence observed in the micellar phase Hammett correlations have been attempted. Higher negative ϱ values obtained in the presence of ctab, indicate that the transition state is more electron-deficient. The positive co-operativity calculated for the micellar catalysed reactions (3.0) indicates possible hydrophobic interaction between micelle and formazan.

    • Oxidation of benzaldehyde semicarbazone by Tl(III) acetate—a structure reactivity correlation

      R Balakrishnan Vangalur S Srinivasan

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      The kinetics of Tl(III) acetate oxidation of semicarbazones of benzaldehyde and substituted benzaldehydes have been investigated in aqueous (90%) acetic acid. Electron-releasing substituents in the phenyl ring enhance the rate of the reaction, whereas electron-withdrawing substituents retard the rate. The rho value of −1 favours electron-deficient transition state. To account for the major product of the reaction,viz respective benzaldehyde, a suitable scheme involving N-thallated intermediate has been proposed

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