PHOTOLYSIS OF FORMAMIDES AND ACETAMIDES STUDIED BY ELECTRON SPIN RESONANCE

The primary free-radical producing step in the photolysis of formamide is shown to be the formation of H atoms and CONH2 radicals. Photolysis of acetamide produces CH3 and CONH2. Substitution of a methyl group on the nitrogen atom in these compounds does not change the primary step in that C-H and C-C bond scission is observed for N-methylformamide and N-methylacetamide, respectively. The free radicals produced at –196° were identified from their esr absorption spectra. The use of deuterium-labeled samples and generation of free radicals by OH radical attack on the parent molecules were used to help identify the free radicals produced in the photochemical decompositions. © 1969, American Chemical Society. All rights reserved.