Abstract
The oxidation of aliphatic unsymmetrical ketones-n-propyl methyl ketone and isobutyl methyl ketone and cyclic ketone-cyclohexanone by ceric perchlorate in perchloric acid (≈0·5–2·0 M) was studied in the temperature range 10°–30° C. The kinetics of the reactions were followed by measuring rate of Ce4+ disappearance effecting variations in [Ce4+], [Ketone], [HClO4], ionic strengthμ, temperature, etc., and the reactions were found to be 2nd order—first order each with respect to [Ce4+] and [ketone]. No evidence for complex formation between Ce4+ and ketone was obtained from kinetics or by an independent absorptiometric method. Ce4+ (aq) and enol of the ketones were the active species for oxidation. Correlations between rates of enolisation of ketones and oxidation of the latter by Ce4+ were observed. The rate constants and their thermodynamic data were calculated and discussed. A mechanism based on the concept of oxidation as a process of successive hydroxylation of organic molecules is proposed.
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