CALIBRATION OF VERY FAST ALKYL RADICAL CLOCK REARRANGEMENTS USING NITROXIDES

The nitroxide radical, Tempo, has been shown to combine with alkyl radicals to form hydroxylamines with a rate constant of ca. 109 M-1 s-1 at room temperature and this reaction has been used to measure the rate of some very fast alkyl radical rearrangements. These calibrated “clock” reactions have then been used to investigate the “hydroxyl rebound” reaction in the cytochrome P-450 induced hydroxylation of alkanes. © 1990 De Gruyter