35469-61-5Relevant articles and documents
Substitution of the nitro group with Grignard reagents: Facile arylation and alkenylation of pyridine N-oxides
Zhang, Fang,Zhang, Song,Duan, Xin-Fang
, p. 5618 - 5620 (2013/01/15)
The unprecedented substitution of a nitro group with aryl or alkenyl groups of Grignard reagents affords 2-aryl or alkenylpyridine N-oxides in modest to high yields with high chemoselectivity. This protocol allows a simple and clean synthesis of various 2
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.
