Photochemical primary process of photo-Fries rearrangement reaction of 1-naphthyl acetate as studied by MFEprobe

Literature Information

Publication Date 2010-11-03
DOI 10.1039/C0CP00077A
Impact Factor 3.676
Authors

Masao Gohdo, Tadashi Takamasu, Masanobu Wakasa


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Abstract

Photo-Fries rearrangement reactions of 1-naphthyl acetate (NA) in n-hexane and in cyclohexane were studied by the magnetic field effect probe (MFE probe) under magnetic fields (B) of 0 to 7 T. Transient absorptions of the 1-naphthoxyl radical, T–T absorption of NA, and a short-lifetime intermediate (τ = 24 ns) were observed by a nanosecond laser flash photolysis technique. In n-hexane, the yield of escaped 1-naphthoxyl radicals dropped dramatically upon application of a 3 mT field, but then the yield increased with increasing B for 3 mT < B ≤ 7 T. These observed MFEs can be explained by the hyperfine coupling and the Δg mechanisms through the singlet radical pair. The fact that MFEs were observed for the present photo-Fries rearrangement reaction indicates the presence of a singlet radical pair intermediate with a lifetime as long as several tens of nanoseconds.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
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