A new azathiacrown ether 4,5:14,15-dibenzo-3,16-dioxo-21-thio-7,12-diazabicyclo [16.2.1] heneicosa-1(20),18-diene (2) and its five derivatives have been synthesized by using thiophene, salicylaldehyde, diamine, bromoacetic acid, acrylonitrile and allyl chloride as starting materials. The structures of these compounds were characterized by elemental analysis, III, H-1 NMR and MS spectra.