42749-62-2Relevant academic research and scientific papers
Isomerization of triphenylmethoxyl: The wieland free-radical rearrangement revisited a century later
DiLabio, Gino A.,Ingold,Lin, Shuqiong,Litwinienko, Grzegorz,Mozenson, Olga,Mulder, Peter,Tidwell, Thomas T.
supporting information; body text, p. 5982 - 5985 (2010/10/02)
(Figure Presented) Old wisdom teaches a new lesson : The rate constant for the isomerization of thermally generated triphenylmethoxyl to Ph 2(PhO)C has been determined both experimentally and by DFT calculations (see scheme), and the results vindicated Wieland's 1911 observations and conclusions-in contrast to photochemically based findings.
Neophyl-like Rearrangement of Alkoxy Radicals: Direct Detection of a Bridged Intermediate by Time-Resolved Absorption Spectroscopy
Falvey, Daniel E.,Khambatta, Binaifer S.,Schuster, Gary B.
, p. 1056 - 1059 (2007/10/02)
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 spirooctadiene-type radical.
