Ohkubo Kei, Kobayashi Takaki, Fukuzumi Shunichi
Department of Material and Life Science, Graduate School of Engineering, Osaka University, ALCA, Japan Science and Technology Agency (JST), Suita, Osaka 565-0871, Japan.
Opt Express. 2012 Mar 12;20 Suppl 2:A360-5. doi: 10.1364/OE.20.00A360.
One-pot alkoxylation of benzene with alcohols occurs under photoirradiation of 3-cyano-1-methylquinolinium ion in an oxygen-saturated acetonitrile solution containing benzene and alcohols. The photocatalytic reaction mechanism was clarified by nanosecond laser flash photolysis. The photocataytic alkoxylation of benzene is initiated by photoinduced electron transfer from benzene to the singlet excited state of 3-cyano-1-methylquinolinium ion, followed by the nucleophilic addition of alcohols to benzene radical cation. In the case of photoethoxylation, the optimal product and quantum yields of ethoxybenzene were 20% and 10%, respectively.
在含有苯和醇类的氧气饱和乙腈溶液中，在3-氰基-1-甲基喹啉鎓离子的光照射下，苯与醇类发生一锅法烷氧基化反应。通过纳秒激光闪光光解阐明了光催化反应机理。苯的光催化烷氧基化反应是由苯向3-氰基-1-甲基喹啉鎓离子的单重态激发态的光诱导电子转移引发的，随后醇类亲核加成到苯自由基阳离子上。在光乙氧基化反应中，乙氧基苯的最佳产物产率和量子产率分别为20%和10%。
