Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Kinetics and Mechanism of Oxidation of Styryl Biphenyl and Styryl Fluorenyl Ketones by Pyridinium Chlorochromate

  • Published : 1999.12.20
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Abstract

The kinetics of oxidation of substituted styryl 4-biphenyl ketones and of substituted styryl 2-fluorenyl ketones by pyridinium chlorochromate (PCC) have been studied in 90% acetic acid- 10% water (v/v) containing perchloric acid and NaClO₄ at $10^0,\;20^0,\;30^0$ and 40℃. The reactions are first order in styryl ketones and PCC. The second order rate constants are well correlated only with σ$^+$ constants implying development of positive charge adjacent to benzene ring in the transition state. The effects of varying [HClO₄] and the percentage of acetic acid on the reactions have also been analysed. A mechanism involving nucleophilic attack of PCC leading to an unsymmetric intermediate from which epoxides are formed is proposed.

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References

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