Abstract 1-Azacycl [3.2. 2] azines were synthesized from 2-methylthioimidazo [1, 2-a] pyridines, 2a and 2b, by using [2+ 8] cycloaddition reaction with dimethyl acetylenedicarboxylate as the key step. Synthesis of 1-azabenzo-[h] cycl [3.2. 2] azine was also described.