Role of Added Chloride Ions in Alteration of Reaction Pathway in the Oxidation of Cyclic Ketones by Dichloroisocyanuric Acid— A Kinetic Study

Authors: Y. Lakshman Kumara, R. Venkata Nadh, P. S. Radhakrishnamurtia

Effect of added chloride ions on kinetics and pathway of reaction between cyclic ketones (five to eight membered rings) and dichloroisocyanuric acid (DCICA) was studied in aqueous acetic acid—perchlo ric acid medium. Formation of aliphatic dicarboxylic acids as the end products demonstrates the ring cleav age oxidation. Positive effect of acid and negative effect of dielectric constant on the reaction rate reveals a interaction between positive ion (oxidant in the form of H2OCl+) and dipolar substrate molecule. Zero and first orders by oxidant in absence and presence of added chloride ions illustrates the participation of substrate as enolic form of ketone and protonated ketone, respectively, in the rate determining steps. The observed order of reactivity of cyclic ketones (cyclohexanone > cyclooctanone > cyclopentanone > cycloheptanone) was explained on the bases of ring strain, change of hybridization and conformational considerations. The envisaged plausible mechanism based on order of reactants in presence and absence of added chloride ions was substantiated by the order of Arrhenius parameters.

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[v1] 2019-05-19 05:20:14

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