Selective Oxygenation of 4,4‘-Dimethylbiphenyl with Molecular Oxygen, Catalyzed by 9-Phenyl-10-methylacridinium Ion via Photoinduced Electron Transfer

Photooxygenation of 4,4'-dimethybiphenyl with oxygen occurs efficiently in the presence of 9-phenyl-10-methylacridinium perchlorate (AcrPh(+)ClO(4)(-)) under visible light irradiation in O(2)-saturated chloroform (CHCl(3)) to yield 4-(4'-methylphenyl)benzaldehyde as a main oxygenated product. Prolonged photoirradiation afforded the further oxygenated product, 4,4'-diformylbiphenyl. The reactive radical intermediates involved in the photocatalytic cycle have successfully been detected by laser flash photolysis and electron spin resonance (ESR) measurements. The photocatalytic mechanism for the oxygenation of 4,4'-dimethybiphenyl via photoinduced electron transfer from 4,4'-dimethybiphenyl to the singlet excited state of AcrPh(+) is clarified based on the dependence of quantum yields on concentrations of substrates and the detected radical intermediates.