Nucleophilic substitution of 3-bromo-4-phenyl-1H-[1,5]benzodiazepin-2-one (1) with thiourea or guanidine
in presence of potassium carbonate afforded 1,5-benzodiazepin-3-ylimidothiocarbamate 2 or 1,5-
benzodiazepin-3-ylguanidine 3, respectively. Pyrimidylthiobenzodiazepines 5–13 were obtained via the
reaction of compound 2 with malononitrile dimer, diethyl malonate, methylenemalononitriles, or a mixture
of an aldehyde and β-keto esters or acetylacetone, catalyzed using ceric ammonium nitrate. Reaction of
compound 2 or 3 with α-halo esters, nitriles, and/or ketones afforded imidazoles 14–20, respectively.