AbstractThe reaction of 3‐aminopyrazole with imidate esters such as ethyl acetimidate, gaveN‐(pyrazol‐3‐yl)acetamidine (1) rather than the isomeric 2‐acetamidoyl‐3‐aminopyrazole. Ring closure of 1 with orthoesters such as ethyl propionimidate, afforded unsymmetrically substituted 2.4‐dialkylpyrazolo[1,5‐a]‐1,3,5‐triazines such as 4‐ethyl‐2‐methylpyrazolo[1,5‐a]‐1,3,5‐triazine (3). The structure of 1 was confirmed by several alternate syntheses. The unique feature of this two‐step synthetic approach to the synthesis of pyrazolo[1,5‐a]‐1,3,5‐triazines is that it is a convenient method of preparing fused triazines based on available pyrazoles rather