21945-42-6Relevant articles and documents
Kinetics of reductive N-O bond fragmentation: The role of a conical intersection
Lorance, Edward D.,Kramer, Wolfgang H.,Gould, Ian R.
, p. 15225 - 15238 (2007/10/03)
N-alkoxyheterocycles can act as powerful one-electron acceptors in photochemical electrontransfer reactions. One-electron reduction of these species results in formation of a radical that undergoes N-O bond fragmentation to form an alkoxy radical and a neutral heterocycle. The kinetics of this N-O bond fragmentation reaction have been determined for a series of radicals with varying substituents and extents of delocalization. Rate constants varying over 7 orders of magnitude are obtained. A reaction potential energy surface is described that involves avoidance of a conical intersection. A molecular basis for the variation of the reaction rate constant with radical structure is given in terms of the relationship between the energies of the important molecular orbitals and the reaction potential energy surface. Ab initio and density functional electronic structure calculations provide support for the proposed reaction energy surface.
Facile synthesis of 1,2-diaryl- and triarylethenes with supported fluoride bases
Hellwinkel,Goke,Karle
, p. 973 - 978 (2007/10/02)
Differently substituted arenecarbaldehydes, mainly benzaldehydes, can be very efficiently condensed with a wide variety of methylbenzenes having an electron-withdrawing group in the para-position, as well as with fluorenes, xanthene, cyclopentadienes and indenes by using a standardized KF- or CsF-Al2O3 base system in dimethylformamide.
