AbstractDuring a study on the amination of 4‐phenylpyrimidine in potassium amide/ liquid ammonia it was found that the extent to which theSN(ANRORC) mechanism operates in the amination largely depends upon whether an ammonium salt is used in quenching the reaction. The composition of the σ‐adduct mixture, the structure of the open‐chain intermediates, the inhibition of theSN(ANRORC) mechanism and the course of the amination in apolar solvents have been investigated. In addition, it has been found that, in the amination of 4‐tert‐butylpyrimidine, theSN(ANRORC) mechanism occurs to only a very limi