Neophyl-like Rearrangement of Alkoxy Radicals: Direct Detection of a Bridged Intermediate by Time-Resolved Absorption Spectroscopy

Article abstract of DOI:10.1021/j100366a006

The neophyl-like rearrangment of alkoxy radicals was examinde by means of picosecond time scale absorption spectroscopy.The triphenylmethoxy radical (Ph3CO^.) rearranges to form the α-phenoxydiphenylmethyl radical (Ph2COPh^.) with a rate constant greater than 5 x 10¹⁰ s^-.The rearrangment of 1,1-diphenylethoxy radical (PhCH3CO^.) was also examined.In acetonitrile solution, an intermediate is formed in less than 17 ps and then decays with a lifetime of 312 ns.It is proposed that this intermediate is a brigded spiro<2.6>octadiene-type radical.