Difluoroalkylamines from high temperature vapor phase reactions of nitrogen trifluoride with alkanes, ethers and benzene

At temperatures around 400 °C, nitrogen trifluoride (NF3) readily reacts with alkanes and benzene as well as ethers. In all cases, products were N,N-difluoroamines. This is in contrast to difluoroamination of benzylic substrates where the initial N,N-difluoroamines underwent eliminations or rearrangements and were not isolated. Cyclic and acyclic alkanes generated N,N-difluoroaminoalkanes. Benzene substituted on the ring to form N,N-difluoroaniline. Ethers reacted to generate α-N,N-difluoroamino ethers. Little direct fluorination was observed.

Graphical abstract.Figure optionsDownload full-size imageDownload as PowerPoint slideHighlights► Nitrogen trifluoride reacts with alkanes and cycloalkanes at 400 °C to generate N,N-difluoroaminoalkanes. ► Nitrogen trifluoride reacts with ethers and cyclic ethers at 400 °C to generate α-N,N-difluoroaminoalkanes. ► Nitrogen trifluoride reacts with benzene at 400 °C to generate α-N,N-difluoroaniline and fluorobenzene.