Photocatalytic oxidation of several primary aliphatic amines on irradiated TiO2 powders suspended in anhydrous acetonitrile led to good yields of the corresponding symmetrical N-alkylidene amines. Mechanistic electrochemical investigation of the reaction revealed intermediate formation of an immonium cation in an ECE route. This species is generated via electrooxidation of an α-amino radical formed by deprotonation of the primary oxidation product, an aminium cation radical. The influence of the metal oxide surface on radical cation reactivity is discussed. © 1986.
Fox, M. A., & Younathan, J. N. (1986). Radical cation intermediates in the formation of schiff bases on irradiated semiconductor powders. Tetrahedron, 42(22), 6285–6291. https://doi.org/10.1016/S0040-4020(01)88091-1