Introduction of the aminooxy group on to nitroaromatic and heterocyclic rings : Synthesis and properties of O-(nitroaryl)hydroxylamines

The reaction of halonitrobenzenes with t-butyl N-hydroxycarbamate (2), gave t-butyl N(nitroaryloxy)carbamates (3), which yielded on acidolysis with trifluoroacetic acid, O-(nitroaryl)hydroxylamines (4). Compounds 4 were utilized for the amination of anionic nitrogens and of carbanions. Attempts to apply the method to the synthesis of hydroxylamines substituted on the oxygen by heterocyclic rings (pyridine, pyrimidine, pyrazine, triazine, purine and benzothiazole) yielded only the corresponding hydroxy compounds. However, the formation of a N,O-dipyridylhydroxylamine derivative (22b) indicates that O(5-nitro-2-pyridyl)hydroxylamine (17) existed as a highly reactive intermediate.