Organic peroxides. Part 12. The preparation and properties of some triazinyl peroxides

Abstract

The triazinyl peroxides (A; X = Y = OOBu^t; X = OMe, Y = OOBu^t; X = Y = OMe; X = NEt₂, Y = OOBu^t; X = Y = NEt₂) and (B) have been prepared from the reaction between the appropriate peroxidic nucleophile and chlorotriazine. The structures of the peroxides are confirmed by their ¹³C n.m.r. spectra, and by the recovery of t-butyl hydroperoxide when the peroxides (A; X = Y = OOBu^t; X = OMe, Y = OOBu^t) were hydrolysed. [graphic omitted]. These peroxides are thermally stable up to ca. 90 °C. Photolysis of the peroxides (A) gives the radical Bu^tO· and XYC₃N₃O·. The e.s.r. spectra of the triazinoxyl radicals could not be observed, but the adducts XYC₃N₃OCH₂CH₂· and XYC₃N₃OP(OMe)₃, which they form with ethylene and with trimethyl phosphite, respectively, were detected. It is suggested that these properties imply that the radicals have a σ-O rather than a π-delocalised structure.