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7578950 
Journal Article 
Reactivity of heterocyclic ketones towards chlorination by chloramine-T - A kinetic study 
Selvaraj, K; Venkateswaran, V; Ramarajan, K; Ikramudden, TM 
2001 
Indian Journal of Chemistry. Section B
ISSN: 0376-4699
EISSN: 0975-0983 
40 
101-107 
The kinetics of oxidation of some piperidin-4-ones, oxan-4-ones and thian-4-one-1,1-dioxides by sodium N-chloro-p-toluenesulphonamide (CAT) in the presence of perchloric acid in aqueous acetic acid have been investigated. The reaction is found to be first order each in [oxidant] and in [substrate] at constant acid concentration and ionic strength. Both [H3O-] and [Cl-] catalyse the reaction and while the order with respect to acid is two, that with respect to [Cl-] is fractional. Increase in ionic strength and addition of p-toluenesulphonamide, one of the reaction products, have no influence on the rate. The effect of changing the dielectric constant of the medium on the reaction rate has also been studied. Activation parameters have been evaluated. A mechanism consistent with the experimental data is proposed. The differences in reactivity towards chlorination and the effect of hetero atom on the reaction rate are rationalised.