Photochemical Smiles rearrangement and Meisenheimer complex formation catalyzed by hydroxide ion via electron hole transfer catalysis.
[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.
Wubbels
Gene G
GG
Department of Chemistry, University of Nebraska at Kearney, Kearney, Nebraska 68849, USA. wubbelsg@unk.edu
Ota
Nobutoshi
N
Crosier
Michelle L
ML