On the chichibabin amination of quinoline and some nitroquinolines

Quinoline is aminated into 2-aminoquinoline (55-60%) when treated with potassium amide/liquid ammonia/potassium permanganate at ?65°. When the amination is carried out by allowing the solution of quinoline in potassium amide/liquid ammonia to raise from ?60° to + 15° before addition of potassium permanganate, the main product is 4-aminoquinoline. Using as reagent liquid ammonia/potassium permanganate (thus without the presence of potassium amide) 3-nitroquinoline is exclusively aminated at ?40° into 4-amino-3-nitroquinoline. Using the same conditions, from 4-nitroquinoline 3-amino-4-nitroquinoline is obtained. The mechanism of these amination reactions is discussed.