Electronic Effect of Substituent of Quinones on their Catalytic Performance in Hydrocarbons Oxidation

Quinones with electron-withdrawing F, Cl or Br groups and N-hydroxyphthalimide (NHPI) were used as catalysts in selective oxidation of hydrocarbons with molecular oxygen as oxidant. The catalytic activity in the selective oxidation of ethylbenzene to oxygenation products was in the following order: p-benzoquinone < tetrafluoro-p-benzoquinone ≈ tetrachloro-p-benzoquinone < tetrabromo-p-benzoquinone (p-TBBQ). Moderate electron-withdrawing power of substituent was suitable for quinone abstracting hydrogen from NHPI to generate reactive phthalimido-N-oxyl (PINO). The catalytic activity of p-TBBQ/NHPI, the best catalyst in our study, was also tested in the selective oxidation of alkylarenes, alkenes and alkanes.