Selective Oxidation of Cyclohexanone to Adipic Acid Using Molecular Oxygen in the Presence of Alkyl Nitrites and Transition Metals as Catalysts

This paper presents a not previously reported catalytic system consisting of transition metals Co²⁺ and Mn²⁺ and alkyl nitrites R-ONO for the oxidation of cyclohexanone with oxygen to adipic acid. The influence of type and amount of catalyst, temperature, time, and type of raw material on conversion and product composition were determined. In addition, the oxidation of selected cyclic ketones such as cyclopentanone, cyclohexanone, cyclooctanone, cyclododecanone, 2-methylcyclohexanone, 3-methylcyclohexanone, and 4-methylcyclohexanone in acetic acid as solvent was performed. The results showed that R-ONO systems, under established reaction conditions, form NO·radicals, which oxidize to NO₂ under a strong oxidization reaction environment. The Co²⁺/Mn²⁺/NO₂ system was shown to be highly active in the oxidation of cyclic ketones with oxygen.