High temperature vapor phase reactions of nitrogen trifluoride with benzylic substrates

At temperatures around 400 °C, nitrogen trifluoride (NF3) readily reacts with benzylic substrates. Products vary with the substrate, but are all the result of difluoroamination at the benzylic position. Toluene and ethylbenzene produce benzonitrile. Cumene produces α-methylstyrene. Diphenylmethane produces benzanilide. Little or no direct fluorination or radical dimerization is observed.

Graphical abstractFigure optionsDownload full-size imageDownload as PowerPoint slideHighlights► At temperatures around 400 °C, nitrogen trifluoride (NF3) reacts with toluene or ethylbenzene to produce benzonitrile. ► NF3 reacts with cumene to produce α-methylstyrene. ► NF3 reacts with diphenylmethane to produce benzanilide. ► Products are the result of difluoroamination at the benzylic position. Little or no direct fluorination or radical dimerization is observed.