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. 1983 Jun 15;212(3):539–547. doi: 10.1042/bj2120539

Comparative studies on the cumene hydroperoxide- and NADPH-supported N-oxidation of 4-chloroaniline by cytochrome P-450.

P Hlavica, I Golly, J Mietaschk
PMCID: PMC1153127  PMID: 6882382

Abstract

The present study confirms that cytochrome P-450 can act as a catalyst in the cumene hydroperoxide-supported N-oxidation of 4-chloroaniline. Analogous to the NADPH/O2-driven N-oxidation process, product dissociation is likely to limit the overall rate of cytochrome P-450 cycling also in the peroxidatic pathway. The oxy complexes involved in either metabolic route differ with respect to stability, spectral properties and need for thiolate-mediated resonance stabilization. With the organic hydroperoxide, the metabolic profile is shifted from the preponderant production of N-(4-chlorophenyl)hydroxylamine to the formation of 1-chloro-4-nitrobenzene. This finding suggests that the peroxide-sustained N-oxidation mechanism differs in several ways from that functional in the NADPH/O2-dependent oxenoid reaction. Thus one-electron oxidation, triggered by homolytic cleavage of the oxygen donor, is proposed as the mechanism of peroxidatic transformation of 4-chloroaniline.

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Selected References

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