Selective oxidation of pseudocumene and 2-methylnaphthalene with aqueous hydrogen peroxide catalyzed by γ-Keggin divanadium-substituted polyoxotungstate
| Autor: | Vasiliy Yu. Evtushok, Olga V. Zalomaeva, Gennadii M. Maksimov, Oxana A. Kholdeeva |
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| Rok vydání: | 2015 |
| Předmět: |
Aqueous solution
Organic Chemistry Substrate (chemistry) Regioselectivity Homogeneous catalysis Biochemistry Medicinal chemistry Catalysis Inorganic Chemistry chemistry.chemical_compound chemistry Yield (chemistry) Materials Chemistry Organic chemistry Physical and Theoretical Chemistry Hydrogen peroxide Selectivity |
| Zdroj: | Journal of Organometallic Chemistry. 793:210-216 |
| ISSN: | 0022-328X |
| DOI: | 10.1016/j.jorganchem.2015.04.020 |
| Popis: | 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. |
| Databáze: | OpenAIRE |
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