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

• Polyoxometalate (Bu4N)4[γ-PW10O38V2(μ-O)(μ-OH)] catalyzes oxidation of pseudocumene and 2-methylnaphthalene with H2O2.
• Pseudocumene is converted to 2,4,5-trimethylphenol with unusually high regioselectivity.
• 2,3,5-Trimethyl-1,4-benzoquinone becomes the main product under excess of H2O2.
• 2-Methylnaphthalene gives predominantly 6-methyl-1,4-naphthoquinone.

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.

The divanadium-substituted phosphotungstate (Bu4N)4[γ-PW10O38V2(μ-O)(μ-OH)] catalyzes aromatic oxidation of pseudocumene and 2-methylnaphthalene with H2O2 demonstrating unusual regioselectivity.Figure optionsDownload as PowerPoint slide