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.