Electrochemical behaviour of 1-benzyl-3-carbamoylpyridinium chloride,a NAD+ model compound

In aqueous media, 1-benzyl-3-carbamoylpyridinium ion undergoes an initially reversible one-electron reduction to produce a free radical, which irreversibly dimerises to a 4,4′-linked diastereoisomeric pair. At more negative potential, the free radical undergoes a further one-electron reduction to a mixture of 1,6- and 1,4-dihydropyridine derivatives. At sufficiently positive potential the dimers can be oxidised back to pyridinium cation. The dimeric products are strongly adsorbed on the electrode surface, also at potential values where 2e products are formed, and this is a preparative drawback for the dimers and the dihydropyridines. Such problems can be overcome by the addition of benzene and of surface-active substances respectively. A detailed mechanism of the electrochemical reduction of 1-benzyl-3-carbamoylpridinium ion is proposed.