| Abstract | Radicals of the types mentioned in the title have been generated and the kinetics and products of their decay have been examined. N-Alkoxy-N-alkylamino, ROṄR′, and N-alkoxyamino, ROṄH, radicals decay with second-order kinetics at about 10% of the diffusion-controlled rate. N-Alkoxyanilino radicals, ROṄC6H5, are much more persistent, they decay with first-order kinetics and exist in equilibrium with their dimers, ΔH ∼ 13.5 kcal/mol. N-Alkoxyaminos yield alcohols as the only organic products of decay, and N-ethoxyanilino yields only ethanol and trans-azobenzene. N-Alkoxy-N-alkylamino radicals generally yielded complex mixtures of products. However, N-benzyloxy-N-benzylamino gave approximately equimolar amounts of O-benzylbenzaldoxime, benzyl alcohol, benzaldehyde, and ω,ω′-azotoluene. The first of these products must arise by disproportionate. It is proposed that the other three products are formed via a Russell-type six-center concerted decomposition of an N-N coupled product. This type of decay appears to be confined to N-benzyloxy-N-alkylamino radicals, presumably because the benzylic hydrogens are activated by the adjacent phenyl group. |
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