Formation of aminoxyls by oxidative addition of N-tert-butylhydroxylamine to acceptor olefins

Abstract

The reaction between an acceptor olefin (symbolized as CC and substituted by at least one conjugatively electron-withdrawing group) and N-tert-butylhydroxylamine in the presence of t-BuNO as an oxidant gives an aminoxyl which formally is a spin adduct of HC–C˙ and t-BuNO and in the appropriate cases identical to the aminoxyl formed in the thermal or photochemical reaction between CC and α-phenyl-N-tert-butylnitrone (PBN). The acceptor olefins studied were N-phenylmaleimide, maleimide, N-methylmaleimide, maleic anhydride, diethyl fumarate, diethyl 2,3-(²H₂)fumarate, diethyl maleate, trimethyl ethylenetricarboxylate, 1,4-benzoquinone, fumaronitrile, methyl acrylate, methyl methacrylate and acrylonitrile.