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Kinetic and mechanistic studies on the reactions of peroxynitrite with estrone and phenols

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Abstract

Reaction of peroxynitrite with estrone, a female sex hormone, was carried out in tetrahydrofuran (THF)/H2O (8: 2) basic solutions. The major products are the corresponding o-quinone, nitroestrone and 2,2′-biphenol. The reaction of phenols with peroxynitrite under the same conditions leads also to the formation of quinones, nitrophenols and biphenols. The major mechanistic pathways take place via a one-electron oxidation of the phenolic group leading to the formation of a phenoxyl radical intermediate which is further oxidized by peroxynitrite (or by intermediates generated from peroxynitrite) to give the final products. A Hammett correlation of the rate constants for the oxidation of meta substituted phenols support a radical mechanism. The kinetic isotope factors rule out the involvement of a C-H bond cleavage in the rate-determining step. A multistep mechanism showing major intermediates involved in the reaction and the final products has been proposed.

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Authors and Affiliations

  1. Department of Applied Chemical Sciences, Jordan University of Science and Technology, Irbid, 22110, Jordan

    A. M. Al-Ajlouni, K. Q. Shawakfeh & R. Rajal

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  1. A. M. Al-Ajlouni
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  2. K. Q. Shawakfeh
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  3. R. Rajal
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Correspondence to A. M. Al-Ajlouni.

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Published in Russian in Kinetika i Kataliz, 2009, Vol. 50, No. 1, pp. 96–105.

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Al-Ajlouni, A.M., Shawakfeh, K.Q. & Rajal, R. Kinetic and mechanistic studies on the reactions of peroxynitrite with estrone and phenols. Kinet Catal 50, 88–96 (2009). https://doi.org/10.1134/S0023158409010121

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