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Rearrangements in the cerium(IV) and manganese(III) oxidations of substituted naphthalenes and the nih shift mechanism

Bhatt, Vivekananda M and Pariasamy, Mariappan (1994) Rearrangements in the cerium(IV) and manganese(III) oxidations of substituted naphthalenes and the nih shift mechanism. In: Tetrahedron, 50 (11). pp. 3575-3586.

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Official URL: http://dx.doi.org/10.1016/S0040-4020(01)87034-4

Abstract

Ceric ammonium sulphate oxidation of 1- and 1,4- disubstituted naphthalenes gives 2- and/or 2,3- disubstituted 1,4- naphthoquinones through migration of substituents (D, Br, Ph). Similar rearrangements are also observed in the manganese(III) oxidation and also in the anodic oxidation of these substrates. The results are consistent with the proposal that these oxidations go through the formation of radical cation followed by reaction with H2O and further oxidation of the radical to the carbocationic intermediate on the way to the corresponding 1,4-naphthoquinone. Oxidation of 1,4-diphenylnaphthalene gives 2,3-diphenyl-1,4-naphthoquinone or 4-hydroxy- 2,4- diphenyl - 1(4)R - naphthalenone. The results are in accordance with the conclusion that such rearrangements do not require prior formation of arene oxide intermediates, originally proposed for the NM shift mechanism.

Item Type: Journal Article
Additional Information: Copyright of this article belongs to Elsevier science.
Department/Centre: Division of Chemical Sciences > Organic Chemistry
Date Deposited: 11 Apr 2011 06:41
Last Modified: 11 Apr 2011 06:41
URI: http://eprints.iisc.ernet.in/id/eprint/36783

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