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

Oxygenation and chlorination of aromatic hydrocarbons with hydrochloric acid photosensitized by... 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. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Research on Chemical Intermediates Springer Journals

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

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Publisher
Springer Journals
Copyright
Copyright © 2012 by Springer Science+Business Media B.V.
Subject
Chemistry; Catalysis; Physical Chemistry; Inorganic Chemistry
ISSN
0922-6168
eISSN
1568-5675
D.O.I.
10.1007/s11164-012-0643-5
Publisher site
See Article on Publisher Site

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.

Journal

Research on Chemical IntermediatesSpringer Journals

Published: Jun 21, 2012

References

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