Abstract
Photolysis of phenyl phenylacetate and its derivatives in homogeneous solutions results in photo-Fries rearrangement products, phenols and diphenylethane as well as phenyl benzyl ethers. Photolysis of these esters adsorbed on silica surface leads only to the formation of or/tho-hydroxyphenones and phenyl benzyl ethers. This observation demonstrates that silica surfaces suppress diffusion and rotation of the photogenerated radicals. Application of a weak external magnetic field upon photolysis of these esters adsorbed on silica surface results in no change in the product distribution, suggesting that the photochemical reaction of these esters originates from the excited singlet state. The rate of the formation of the ortho rearrangement product from the geminate radical pairs adsorbed on silica surfaces is estimated to be 2.0 x 108 s-1.
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Tung, C.H., Wang, X.H., Ying, Y.M. et al. Effects of silica surface and external magnetic field on photochemical reaction of phenyl esters. Res. Chem. Intermed. 21, 613–620 (1995). https://doi.org/10.1163/156856795X00459
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DOI: https://doi.org/10.1163/156856795X00459