Reactions of 5-(1,4-benzodioxan-2-yl)-1,3,4-oxadiazole-2-thiol with N-substituted chloroacetamides gave a series of the corresponding derivatives at the sulfur atom. Addition reactions of 5-(1,4-benzodioxan-2-yl)-1,3,4-oxadiazole-2-thiol to the C=C double bond of acrylonitrile, acrylamide, and ethyl acrylate, as well as Mannich condensation with morpholine and piperidine, were studied. The synthesized compounds were evaluated for their antibacterial activity.