Abstract The reactions of polyfluorochalcones with o-aminothiophenol in methanol in the presence of HCl afford polyfluorine-substituted 2, 3-dihydrobenzo [b][1, 5] thiazepines. In some cases, the cyclization is accompanied by fluorine substitution in the perfluorophenyl ring. Probably, the formation of thiazepines proceeds through the Michael thia-adduct. The Zn salt of o-aminothiophenol reacts with chalcones in DMF exclusively via fluorine ...