Studies on Tertiary Amine Oxides. LXXVII. The Pseudo-Gomberg Reaction of 4-and 2-Aminopyridine 1-Oxides

Abstract

The 1-oxido-4-pyridyl radical generated by the reaction of 4-aminopyridine 1-oxide with amyl nitrite reacted smoothly with aromatic hydrocarbons, including five-membered heterocycles, i.e. thiophene, furan and pyrrole, to give the arylated products when acetic acid was used as the solvent. The relative rates of reaction with the 1-oxido-4-pyridyl radical indicated that this radical is electrophilic, and this finding was supported by a comparison of molecular orbital energy levels. 2-Aminopyridine 1-oxide also undergoes a similar reaction.