During the N-benzoylation reaction for the synthesis of N-substituted aminopyrimidines, an undesired N,N-diacylation reaction took place. The extension of this N-acylation reaction to a series of several 2-aminopyrimidines, aminopyrazines and highly deactivated anilines produced analogous results. The possible mechanism responsible for that behavior is investigated and an advantageous alternative procedure for the clean formation of the desired amides is suggested.