Nucleophilic Attack at Heterocyclic Nitrogen: Unusual Reactivity of the Benzotriazole Heterocyclic Ring

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.