Polyfluorinated 2,4-diaryl-2,3-dihydro-1H-1,5-benzodiazepines: Synthesis and new rearrangement into polyfluorodihydrobenzimidazo[1,2-a]quinolines

• Published in: Journal of fluorine chemistry Vol. 162; pp. 66 - 70
• Main Authors: Borodina, Elena A., Orlova, Natalia A., Kargapolova, Irina Yu, Gatilov, Yury V.
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 01-06-2014
• Subjects: Alcohols; Fluorine; Intramolecular fluorine substitution; Nuclear magnetic resonance; Polyfluorinated 2,4-diaryl-2,3-dihydrobenzo-1H-1,5-diazepines; Polyfluorinated dihydrobenzimidazo[1,2-a]quinolines; Polyfluorochalcones; Quaternary ammonium salts; Rearrangement; Spectra; Synthesis (chemistry); Triethylamine; X-rays; Polyfluorinated 2,4-diaryl-2,3-dihydrobenzo-1H-1,5-diazepines; Intramolecular fluorine substitution; Polyfluorinated dihydrobenzimidazo[1,2-a]quinolines; Polyfluorochalcones; Rearrangement
• ISSN: 0022-1139; 1873-3328
• DOI: 10.1016/j.jfluchem.2014.03.013

•Polyfluorochalcones with 1,2-diaminobenzene give benzo-1H-1,5-diazepine derivatives.•Polyfluorobenzo-1H-1,5-diazepines transform to tetracyclic benzimidazoquinolines.•The structures are confirmed by X-ray.
Interaction of polyfluorinated chalcones (pentafluorobenzalacetophenone, benzalpentafluoroacetophenone and decafluorochalcone) with 1,2-diaminobenzene in alcohols in the presence of triethylamine or quaternary ammonium salt (TEBAC) has been investigated. In the presence of TEBAC in 2-propanol polyfluorinated 2,4-diaryl-2,3-dihydro-1H-1,5-benzodiazepines are formed. Some of them undergo intramolecular fluorine substitution and unusual rearrangement into a previously unknown polyfluoro-containing tetracyclic compounds—(6aR)-1,2,3,4-tetrafluoro-6a-aryl-6a,7-dihydrobenzimidazo[1,2-a]quinolines, under the reaction conditions as well as in absence of TEBAC. The structures are established on NMR spectra and confirmed by X-ray.