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Oxygenation and chlorination of aromatic hydrocarbons with hydrochloric acid photosensitized by 9-mesityl-10-methylacridinium under visible light irradiation

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Abstract

Efficient photocatalytic oxygenation of toluene occurs under visible light irradiation of 9-mesityl-10-methylacridinium (Acr+–Mes) in oxygen-saturated acetonitrile containing toluene and aqueous hydrochloric acid with a xenon lamp for 15 h. The oxygenated products, benzoic acid (70 %) and benzaldehyde (30 %), were formed after the photoirradiation. The photocatalytic reaction is initiated by intramolecular photoinduced electron transfer from the mesitylene moiety to the singlet excited state of the Acr+ moiety of Acr+–Mes, which affords the electron-transfer state, Acr•–Mes•+. The Mes•+ moiety can oxidize chloride ion (Cl−) by electron transfer to produce chlorine radical (Cl•), whereas the Acr• moiety can reduce O2 to O •−2 . The Cl• radical produced abstracts a hydrogen from toluene to afford benzyl radical in competition with the bimolecular radical coupling of Cl•. The benzyl radical reacts with O2 rapidly to afford the peroxyl radical, leading to the oxygenated product, benzaldehyde. Benzaldehyde is readily further photooxygenated to yield benzoic acid with Acr•–Mes•+. In the case of an aromatic compound with electron-donating substituents, 1,3,5-trimethoxybenzene, photocatalytic chlorination occurred efficiently under the same photoirradiation conditions to yield a monochloro-substituted compound, 2,4,6-trimethoxychlorobenzene.

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Acknowledgments

This work was supported by a Grant-in-Aid (Nos. 20108010 and 23750014), a Global COE program from the Ministry of Education, Culture, Sports, Science and Technology, Japan and KOSEF/MEST through WCU project (R31-2008-000-10010-0), Korea.

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Authors and Affiliations

  1. Department of Material and Life Science, Graduate School of Engineering, Osaka University and ALCA (JST), Suita, Osaka, 565-0871, Japan

    Kei Ohkubo, Kentaro Mizushima & Shunichi Fukuzumi

  2. Department of Bioinspired Science, Ewha Womans University, Seoul, 120-750, Korea

    Shunichi Fukuzumi

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  1. Kei Ohkubo
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  2. Kentaro Mizushima
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  3. Shunichi Fukuzumi
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Correspondence to Kei Ohkubo or Shunichi Fukuzumi.

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Ohkubo, K., Mizushima, K. & Fukuzumi, S. Oxygenation and chlorination of aromatic hydrocarbons with hydrochloric acid photosensitized by 9-mesityl-10-methylacridinium under visible light irradiation. Res Chem Intermed 39, 205–220 (2013). https://doi.org/10.1007/s11164-012-0643-5

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