Steric and electronic substitution effects on the thermal oxidation of 5-carboethoxy-2-oxo-1,2,3,4-tetrahydropyridines

Various 4-aryl substituted 5-carboethoxy-2-oxo-1,2,3,4-tetrahydropyridines were oxidized to their corresponding 4-aryl-5-carboethoxy-2-oxo-1,2-dihydropyridines by potassium peroxydisulfate in aqueous acetonitrile under thermal conditions. The products were obtained in good to excellent yields. Based on the proposed mechanism, the removal of the hydrogen from the C4-atom of the heterocyclic ring by the hydroxyl radical formed in situ is occurred in the rate determining step, which is influenced by the steric and electronic effects of the substituted aryl group attached to this atom and also the stability of the radical intermediate involved in the oxidation reaction. The experimental results were supported by the computational studies.