The reaction of 2,6-dichloro-4-phenylquinoline (I) with refluxing hydrazine hydrate gives 6-chloro-2-hydrazino-4-phenylquinoline (II), which is cyclocondensed with triethyl orthoacetate (A) in refluxing xylene yielding 7-chloro-1-methyl-5-phenyl-s-triazolo[4,3-a]quinoline (III). The oxidation of (III) to 5-chloro-2-(3-methyl-4H-1,2,4-triazol-4-yl)benzophenone (V) can be performed with sodium periodate and ruthenium dioxide in acetone-water, or first with ozone in CH2Cl2 giving 4-(2-benzoyl-4-chlorophenyl)-5-methyl-4H-1,2,4-triazol-3-carboxaldehyde (IV), which is then oxidized to (V) with silver oxide in methanol. The condensation of (V) with formaldehyde in xylene at 125 C affords 5-chloro-2-(3-(hydroxymethyl)-5-methyl-4H-1,2,4-triazol-4-yl)benzophenon (VI), which by reaction with PBr3 in chloroform is converted into 5-chloro-2-(3-bromoethyl-5-methyl-4H-1,2,4-triazol-4-yl)benzophenon (VII). Finally, this product is cyclized with ammonia in THF - methanol.
The reaction of 7-chloro-5-phenyl-1,3-dihydro-3H-1,4-benzodiazepine-2-thione (VIII) with acetylhydrazine (B) in refluxing anhydrous ethanol gives 7-chloro-5-phenyl-2-(2-acetylhydrazino)-1,3-dihydro-3H-1,4-benzodiazepine (IX), which is cyclized by heating at 250 C.
The reaction of 7-chloro-5-phenyl-2-hydrazino-1,3-dihydro-3H-1,4-benzodiazepine (X) with refluxing acetaldehyde (C) gives 7-chloro-5-phenyl-2-ethylydenhydrazino-1,3-dihydro-3H-1,4-benzodiazepine (XI), which is cyclized by refluxing in chloroform (10.5 h) or by heating at 160-72 C (10 min).