OXIRANYLCARBINYL RADICALS FROM ALLYLOXYL RADICAL CYCLIZATION - CHARACTERIZATION AND KINETIC INFORMATION VIA ESR SPECTROSCOPY

An ESR spin-trapping technique has been used for the detection of oxir anylcarbinyl radicals as discrete reaction intermediates, formed via c yclization of allyloxyl radicals. The latter were obtained by photolys is of the corresponding nitrites, which were generated directly via an exchange reaction between the appropriate allylic alcohols and tert-b utyl nitrite (which also acts as the spin-trap). Experiments have also been conducted with the spin-trap 2,4,6-tribromonitrosobenzene, which has allowed a study to be made of the competition between ring closur e and p-scission of a variety of allyloxyl species.