Electrochemical oxidation of C4-vanillin- and C4-isovanillin-1,4-dihydropyridines in aprotic medium: Reactivity towards free radicals

This work reports the electrochemical oxidation of two new synthetic C4-vanillin and -isovanillin-1,4-dihydropyridines in aprotic medium. Its reactivity with alkylperoxyl radicals ABAP-derived at pH 7.4 is also studied. Voltammetry, coulometry, controlled-potential electrolysis, UV–visible spectroscopy and GC–MS techniques were employed to collect data that permitted us to study its oxidation. Effect of TBA-OH addition on the oxidation was electrochemically and spectroscopically followed. In aprotic medium, the oxidation mechanism involves the formation of the pyridine derivative, which was generated by controlled-potential electrolysis (CPE) at 1270 mV and identified by GC–MS technique as the final product of the electrolysis. Spectroelectrochemical experiments also support the formation of the pyridine derivative from the oxidation of both 1,4-dihydropyridines. Direct reactivity of synthesized compounds towards alkylperoxyl radicals ABAP-derived was determined. Results reveal that the inclusion of vanillin radical or its positional isomer, isovanillin in the 4-position of the dihydropyridine ring produced a significant positive effect on the reactivity towards alkylperoxyl radicals, even compared with commercial dihydropyridine drugs with a well-known antioxidant ability. Scavenging mechanism involves the electron-transfer and the formation of a pyridine derivative, which was identified by GC–MS.