TEMPO‐Mediated Electrocatalytic Oxidation of Cyclohexanol to Cyclohexanone

ABSTRACT Cyclohexanol is a key intermediate in the production of cyclohexanone, a ketone widely used in the chemical industry, especially in the manufacture of nylon and other polymers. In this work, we propose an alternative route based on the indirect electrooxidation of cyclohexanol in an organic medium, using 2,2,6,6‐tetramethylpiperidine‐1‐oxyl (TEMPO) and different organic bases as the redox mediator. Cyclic voltammetry and in situ FTIR were used to elucidate the reaction mechanism and confirm the product identity, while controlled‐potential electrolysis assessed the synthetic performance. The results indicate that electrooxidation occurs efficiently at 0.26 V (vs. Fc/Fc + ) in the presence of 1,1,3,3‐tetramethylguanidine (TMG), which showed superior alcohol transformation. Chronoamperometry revealed current decay after 120 min, associated with substrate consumption. In situ FTIR and FTIR‐ATR confirmed selective cyclohexanone formation with a characteristic band at 1709 cm −1 . After 4 h of electrolysis, conversion reached approximately 94 ± 6% with a Faradaic efficiency of 83 ± 5%.