Selective oxidation of pseudocumene and 2-methylnaphthalene with aqueous hydrogen peroxide catalyzed by γ-Keggin divanadium-substituted polyoxotungstate

Article abstract of DOI:10.1016/j.jorganchem.2015.04.020

The catalytic performance of a γ-Keggin divanadium-substituted phosphotungstate, (Bu₄N)₄[γ-PW₁₀O₃₈V₂(μ-O)(μ-OH)], has been evaluated in the selective oxidation of 1,2,4-trimethylbenzene (pseudocumene, PC) and 2-methylnaphthalene with the green oxidant, 35% aqueous hydrogen peroxide. Under conditions of H₂O₂ deficiency ([PC]/[H₂O₂] = 17-22), PC oxidation proceeded with unusually high chemo- and regioselectivity, producing exclusively 2,4,5-trimethylphenol (2,4,5-TMP) and 2,3,5-TMP in a molar ratio of 7.3/1 and a yield of 73% based on the oxidant. Isomeric 2,3,6-trimethylphenol was found in trace amounts. Under conditions of H₂O₂ excess ([H₂O₂]/[PC] = 8), 2,3,5-trimethyl-1,4-benzoquinone (TMBQ, vitamin E key intermediate) formed with 41% selectivity at 41% substrate conversion. Atypical regioselectivity was also found in the oxidation of 2-methylnaphthalene which gave predominantly 6-methyl-1,4-naphthoquinone (6-MNQ) rather than isomeric 2-MNQ. The ratio between the isomers could be altered by varying the catalyst and oxidant amounts.