Abstract—3-Iodo-l-azaazulenes were easily ethynylated by Sonogashira-Hagihara reaction to give 3-ethynyl-l-azaazulenes. Cyclization of 2-amino-3-ethynyl-1-azaazulene was achieved by heating in the presence of copper (II) acetate or copper (II) trifluoromethanesulfonate, and l, 9-diaza-l#-cyclopent [û] azulene derivatives were obtained. Reaction of 2-chloro-lazaazulene with lithium phenylacetylide gave 3-chloro-l-(2-chloro-l- ...