Producción CyT
21ST ISFC&ISOFT´15 - Homolytic Aromatic Substitution of Aniline Derivatives with Perfluoroalkyl Groups. Cesium-mediated Radical Initiation
Congreso
Fecha:
2015Editorial y Lugar de Edición:
SOCIEDAD INTERMACIONAL DEL FLUORResumen *
The radical homolytic aromatic substitution reactio(HAS) is well documented and has been notoriously employed to accomplish perfluoroalkyl group substitutions on many (hetero)aromatic nuclei.We have employed this reaction in the past to effect the fotoinduced HAS on activated aromatic compounds to synthesize perfluoroalky-substituted aromatics bearing electron-donating groups, in the absence of formal leaving groups, and in water or aqueous organic solvent mixtures [1]. Also, the HAS reaction of (hetero)arenes with perfluoroalkyl groups has been attempeted successfully in the presence of radical initiators such as tert-butylhydroperoxide [2]. The photoinduced HAS reactions of aminoaromatic compounds lack in efficiency due to the presence of the radical cation of the amines, that induce oligomerization.and reduce perfluoroakyl group substitution yields. In this work, we present a thermal radical HAS reaction of aniline derivatives with perfluoroalkyl moieties in the presence of cesium carbonate in 1,4-dioxane as solvent, rendering perfluoroalkyl-substituted aniline derivatives in good-to-excellent yields.Although the mechanism of the radical initiation of this reaction is still under investigation, we shall present some evidence based on Linear Free Energy Relationships, and cast some light into the reaction intermediates. Información suministrada por el agente en SIGEVAPalabras Clave
PERFLUOROALKYLATIONRADICAL FLUORINATION