Structure-reactivity relationship in the oxidation of aryl aliphatic ketones by CeIV

Kinetics of oxidation of aryl aliphatic ketones by Ce^IV in presence of HClO₄ in aqueous acetic acid medium has been studied. Reactivity has been found to be that substituents of electron withdrawing nature accelerate the reaction and the reverse is true with electron releasing substituents. A mechanism of radical intermediate is postulated to explain the observed phenomena. The unusual reactivity of the alkoxy derivatives may be traced to a change in the mechanism routed through a carbonium ion centre or alternatively it might be due to the hydrolysis of the alkoxy derivatives leading to the higher reactivity observed.