HETEROARYLAMINATION AND HETEROARYLSULFIDATION OF 2-CHLORO-1-AZAAZULENES

Heteroarylamination and heteroarylsulfidation of 2-chloro-1-azaazulenes (1) were investigated. Palladium catalyzed coupling of 2-amino-1-azaazulenes (2) with I underwent to give bis(1-azaazulen-2-yl)amine derivatives in good yields, but the reaction of 2-mercapto-1-azaazulenes (4) with I did not give good results in the same conditions. The reaction of 4 with I under basic conditions gave bis(1-azaazulen-2-yl) sulfide derivatives in good yields. Heteroarylamino-substitution was proceeded on the reaction of 4-amino-3-mercapto-4H-1,2,4-triazoles (6) with I in BuOH under reflux, whereas heteroarylsulfido-substitution was proceeded on the reaction of 6 with I in the presence of NaH in dioxane.