Photoalkylation of 10-Alkylacridinium Ion via a Charge-Shift Type of Photoinduced Electron Transfer Controlled by Solvent Polarity
作者:Shunichi Fukuzumi、Kei Ohkubo、Tomoyoshi Suenobu、Kouta Kato、Mamoru Fujitsuka、Osamu Ito
DOI:10.1021/ja004311l
日期:2001.9.1
(DeAcrH+) in a nonpolar solvent (benzene) is found to be as efficient as those of 10-methylacridinium cation (MeAcrH+) and DeAcrH+ in a polar solvent (acetonitrile). Irradiation of the absorption bands of MeAcrH+ in acetonitrile solution containing tetraalkyltin compounds (R(4)Sn) results in the efficient and selective reduction of MeAcrH+ to yield the 10-methyl-9-alkyl-9,10-dihydroacridine (AcrHR)
发现在非极性溶剂(苯)中,从各种电子供体到 10-癸吖啶鎓阳离子 (DeAcrH+) 的单线激发态的光致电子转移反应与 10-甲基吖啶鎓阳离子 (MeAcrH+ ) 和 DeAcrH+ 在极性溶剂(乙腈)中。在含有四烷基锡化合物 (R(4)Sn) 的乙腈溶液中,对 MeAcrH+ 的吸收带进行辐照会导致 MeAcrH+ 的有效和选择性还原,从而产生 10-甲基-9-烷基-9,10-二氢吖啶 (AcrHR)。当 MeAcrH+ 被可溶于苯的 DeAcrH+ 取代时,在苯中会发生相同类型的反应。使用 4-叔丁基-1-苄基-1,4-二氢烟酰胺 (Bu(t)BNAH) 代替 R(4)Sn,R'AcrH+(R' = Me 和 De)的光烷基化也在乙腈和苯中进行, 产生 MeAcrHBu(t)。量子产率测定、电子供体对 R'AcrH+ 的荧光猝灭以及通过激光闪光光解实验直接检测反应中间体表明,R'AcrH+