Methanol-Incorporated Photoaddition of<i>N</i>-Methyl-9,10-phenanthrenedicarboximide to Alkenes. Addition at Carbonyl and Phenanthrene-Ring Carbon Atoms
作者:Yasuo Kubo、Mikako Nanba、Etsuko Hayashi、Takeo Araki
DOI:10.1246/bcsj.62.3972
日期:1989.12
Irradiation of acetonitrile–methanol (2:1 v/v) solutions of N-methyl-9,10-phenanthrenedicarboximide (3) with alkenes 5a–g gave methanol-incorporated adducts (9c–f) at a carbonyl carbon atom in 3, those (10c,f) at a phenanthrene-ring carbon atom, and a methanol-adduct 11g to alkene 5g, together with products 4, 6b,e–g, 7b,e–g, and 8e,f obtained by the photoreactions in benzene. The concentration effect of
用烯烃 5a-g 照射 N-甲基-9,10-菲二甲酰亚胺 (3) 的乙腈-甲醇 (2:1 v/v) 溶液,在 3 中的羰基碳原子上产生掺入甲醇的加合物(9c-f)那些在菲环碳原子上的 (10c,f) 和 11g 的甲醇加合物到 5g 烯烃,以及通过光反应获得的产物 4、6b、e-g、7b、e-g 和 8e,f苯。烯烃 5e,f 对产物 6e,f, 7e,f, 8e,f, 9e,f 和 10f 产率的浓度影响表明,9e,f 和 10f 均来自相对短命的单线激发态 3 . 与从烯烃 5a-d,g 到 3 的单线激发态的电子转移 (ΔGet) 相关的自由能变化值和荧光猝灭速率常数支持掺入甲醇的光化学电子转移机制。