Skraup-like cyclization of polyfluoro-2-naphthylamines: Vicarious electrophilic substitution of fluorine

Treatment of polyfluoro-2-naphthylamines with glycerol in H2SO4 or CF3SO3H at 150–160 °C gives respective polyfluorobenzo[f]quinolines. The reaction is suggested to proceed via intramolecular vicarious electrophilic substitution of fluorine at the α-position of polyfluorinated naphthalene core.

Graphical abstractPolyfluoro-2-naphthylamines with glycerol in H2SO4 or CF3SO3H at 150–160 °C give polyfluorobenzo[f]quinolines via intramolecular vicarious electrophilic fluorine substitution.Figure optionsDownload full-size imageDownload as PowerPoint slideHighlights► Skraup-like heterocyclization of polyfluoro-2-naphthylamines via fluorine replacement. ► Synthesis of benzo[f]quinolines polyfluorinated on carbocyclic moiety. ► Vicarious electrophilic substitution of fluorine. ► Rationalization of octafluoronaphthalene methyldefluorination by CH3F–SbF5 couple.