Amination of dinitrobenzenes with liquid methylamine/potassium permanganate

Article abstract of DOI:10.1002/recl.19951140104

1,3-Dinitrobenzene (1a) and some simple monosubstituted derivatives (1b-g) were aminated with a liquid methylamine solution of potassium permanganate (LMA/PP) to give the corresponding mono- and bis(methylamino)-substituted compounds (3a-e and 4a). 1,2-Dinitrobenzene (1i) was aminated with LMA/PP to give 2-(methylamino)-1-nitrobenzene (3f) in high yield.The intermediacy of 4-(methylamino) ?-adducts of 1,3-dinitrobenzene (2a), 2-chloro- (2b) and 2-amino-1,3-dinitrobenzene (2c) was established by 1H NMR spectroscopy.Quantum-chemical calculations for the dinitrobenzenes suggest that, in general, the experimentally observed regioselectivity of the methylamination is satisfactorily described by frontier molecular orbital (FMO) interaction of the reagents.