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Photochemical Smiles rearrangement and Meisenheimer complex formation catalyzed by hydroxide ion via electron hole
Gene G Wubbels1, Nobutoshi Ota, Michelle L Crosier
1Department of Chemistry, University of Nebraska at Kearney, Kearney, Nebraska 68849, USA. wubbelsg@unk.edu
Abstract:
[reactions: see text] 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.
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