R. Nakagaki, M. Hiramatsu, Takeshi Watanabe
Jul 1, 1985
Citations
0
Influential Citations
60
Citations
Journal
The Journal of Physical Chemistry
Abstract
The reaction mechanisms of the photo-Fries rearrangement of 1-naphthyl acetate has been studied by means of steady-state photolysis and laser flash photolysis. A radical pair consisting of the 1-naphthoxyl and acetyl radicals is concluded to be a reaction intermediate. The yield of an in-cage product (2-acetyl-1-naphthol) exhibits a positive external magnetic field effect for the ester labeled by magnetically active /sup 13/C, but no effect for the normal /sup 12/C ester. The magnetic field effect observed for the labeled ester is quantitatively or semiquantitatively explained in terms of the radical-pair mechanism by considering hyperfine coupling between magnetically active nuclei (/sup 1/H and /sup 13/C) and an unpaired electron in the acetyl radical. The in-cage product is formed through the singlet radical pair. 26 references, 5 figures, 3 tables.