ON THE TRIGGERING OF FREE-RADICAL REACTIVITY OF DIMETHYLDIOXIRANE

Performing the reaction in the presence of CCl3Br, and/or in inert gas atmosphere, dramatically changes the reaction kinetics, rate-law and product distribution of adamantane oxyfunctionalization by dimethyldio xirane (la). The kinetics of decomposition of the dioxirane is also ma rkedly influenced by the addition of CCl3Br and by depletion of O-2 ga s. ?he data suggest that these conditions can trigger dioxirane radica l reactions; these are widely different from the straightforward, high ly selective concerted O-insertion into C-H bonds which would take pla ce in the absence of CCl3Br and of conditions inducing radical reactiv ity.