1,2,4-Triazin-3-ylthio-, 1,2,4-triazepin-3-ylthio-, 1,2,4-triazol-3-ylthio-, and 1,2,4,3-triazaphosphol-5-ylthio-1,5-benzodiazepines 4-20 were prepared via the reaction of 2-oxo-4-phenyl-2,3-dihydro-1H-1,5-benzodiazepin-3-ylhydrazonothiocarbamate (2) with halocompounds, dicarbonyl compounds, enaminones, 4-chlorobenzaldehyde, 4-chlorobenzylidenemalononitriles, N,N-dimethylformamide dimethylacetal, carbon disulfide, and 2,4-bis(4-methoxyphenyl)-1,3,2,4-dithiadiphosphetane-2,4-disulfide (Lawesson's reagent).