Grignard reagents attack 1-imidoylbenzotriazoles at the imidoyl carbon atom and also at the benzotriazolyl N-2 and N-3 atoms leading to complex reaction mixtures, the composition of which allowed identification of the main reaction paths. Mechanisms are discussed. Previous examples of nucleophilic attack on pyridine-like nitrogen atoms are reviewed. The 1-imidoylbenzotriazoles were prepared from amides with benzotriazole and phosphoryl chloride. Amides derived from secondary amines give α-(benzotriazol-1-yl) enamines.