Transient Intermediates in the PHoto-Fries Isomerization of Phenyl Acetate via Spontaneous Raman Spectroscopy

Article abstract of DOI:10.1021/ja00371a004

Nanosecond-time-resolved 416- and 395-nm Raman spectroscopy is used to observe intermediate species in the solution-phase unimolecular isomerization and fragmentation of phenyl acetate.In aqueous solvent both fundamental and overtone vibrations are observed, while in CH3OH, CCl4, and ethylene dlycol only overtones are investigated.The time evolution and solvent dependence of the spectra allow resolution of three species: phenoxy radical and (apparently) 6- and 4-acetylcyclohexadienones.These data support a caged radical photo-Fries mechanism; however, the relative yields do not correlate with bulk viscosity.