Photochemical Smiles Rearrangement and Meisenheimer Complex Formation Catalyzed by Hydroxide Ion via Electron Hole Transfer Catalysis

Photochemical para-to-nitro Smiles rearrangement and para-to-nitro Meisenheimer complex formation occurs for nitrophenoxyethylamines with high concentrations of hydroxide ion in aqueous solution. Both photoreactions show first-order dependence on hydroxide ion concentration, but the mechanism involv...

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Bibliographic Details
Published in:Organic letters 2005-10, Vol.7 (21), p.4741-4744
Main Authors: Wubbels, Gene G, Ota, Nobutoshi, Crosier, Michelle L
Format: Article
Language:English
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Summary:Photochemical para-to-nitro Smiles rearrangement and para-to-nitro Meisenheimer complex formation occurs for nitrophenoxyethylamines with high concentrations of hydroxide ion in aqueous solution. Both photoreactions show first-order dependence on hydroxide ion concentration, but the mechanism involving hydroxide ion does not involve acid−base catalysis. The reactions take place from the triplet excited states of the nitrophenyl ethers. Analysis of quantum yields and kinetics is consistent with an electron hole transfer catalysis mechanism.
ISSN:1523-7060
1523-7052
DOI:10.1021/ol051941p