New hydrazinecarbothioamides 5a-d bearing 5H-dibenzo[a,d]an-nulene moiety were synthesized using classical procedures. 1H-NMR analysis indicated the existence of two conformational isomers, a major axial (about 75%) and a minor equatorial one (25%) which are interconvertible by middle ring inversion. Cyclization of 5a-d compounds in NaOH solution produced the corresponding 1,2,4-triazoles-3(4H)-thiol 6a-d compounds which proved to be pure axial isomers. All the new compounds were extensively characterized by elemental analysis, IR-, UV-, 1H-NMR and 13C-NMR spectroscopy and biological investigated using phytobiological tests