• V S Srinivasan

      Articles written in Journal of Chemical Sciences

    • Nucleophilic substitution at a benzylic carbon by an ambident nucleophile—A linear free energy relationship

      K Madhavan V S Srinivasan N Venkatasubramanian

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      The kinetics of reaction between benzyl chloride and phenol (or substituted phenols) in the presence of sodium hydroxide have been investigated. A differential application of the effect of substituents on the reaction rate to distinguish between a rate-limiting oxygen or carbon attack has been attempted. Considerable scatter in the Hammett plot for the latter attack points to an essentially O-alkylation. The rate constants correlate well with pKa values of the different phenols. The influence of salt and solvent on the reaction rate suggests this reaction to be an ion-dipole one.

    • Micellar catalysed chlorination of acetophenone by chloramine-T

      V Raghunathan P S Raghavan K Vaidyanathan V S Srinivasan

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      The chlorination of acetophenone by chloramine-T cat has been catalysed by anionic micelle, sodium lauryl sulphate (NaLS). Though the order in cat is one, the order in acetophenone is fractional at lower concentration and becomes zero at higher concentration in the presence and absence of NaLS. This is probably due to the change in rate-determining step. At lower acetophenone concentration, the decomposition of enol-chlorinating species complex is rate-determining whereas at higher concentration, the formation of chlorinating species is rate determining. The graph ofk2 versus detergent concentration is sigmoidal and the positive co-operativityversus log[D] graph is 1.11, indicating possible interaction between micelle and substrate.

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