Photosubstitution of Dicyanobenzenes by Allylic Silanes, Germanes, and Stannanes via Photoinduced Electron Transfer.

摘要: Photoreactions of 1,2- and 1,4-dicyanobenzenes (o- p-DCB) with allylic silanes, germanes, stannanes in acetonitrile were studied under various conditions. In these photoreactions, one cyano groups o- p-DCB was replaced by groups. With trimethyl(3-methyl-2-butenyl)silane, -germane, -stannane, the photosubstitution occurred at both α- γ-positions moiety a constant ratio, regardless kinds metals. 1,3-Dicyanobenzene (m-DCB) less reactive to reaction. The reactivity group 14 organometallic compounds increased order: Si- < Ge- Sn-compounds. photoreactions sensitized aromatic hydrocarbons such as phenanthrene triphenylene, also accelerated adding Mg (ClO4)2 alkylbenzenes. Quantum yields for formation substitution products decreasing oxidation potentials compounds. A key step is reaction radical anions d...