Indirect electrochemical oxidation of picolines. Ab-initio treatment

الملخص EN

The structures of 2-picoline, 3-picoline and 4-picoline (neutral and intermediate cationic species) have been optimized using 6- 311G* basis set at RHF and UHF levels.

The results of MOcalculations were interpreted in terms of energies and coefficients of their molecular orbitals (HOMO and LUMO), stabilization energy, and dipole moments.

The computed electronic charge density of HOMO was located on CH2 + group of 2- and 3-picoline cationic species, which prevented the formation of aldehyde diacetate.

On the other hand, all charge densities of HOMO in cationic 4-picoline were mainly localized on the ring with no charge density on CH2 + group.

The CH2 + group of 4-picoline cationic species could eventually be easily attacked by acetate to form aldehyde diacetate.

The results of MO calculations confirmed the suggested oxidation mechanism reported.