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Perfluorocarbenes Produced by Thermal Cracking. Barriers to Generation and Rearrangement.

Christopher J. Cramer1, Marc A. Hillmyer

  • 1Department of Chemistry and Supercomputer Institute, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455-0431.

The Journal of Organic Chemistry
|October 25, 2001
PubMed
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This study explores generating perfluoroalkylcarbenes from oxiranes. While requiring higher energy than difluorocarbene generation, these carbenes offer stable intermediates for reactions with unsaturated polymers.

Area of Science:

  • Organic Chemistry
  • Computational Chemistry

Background:

  • Difluorocarbene generation is a known technology.
  • Perfluoroalkylcarbenes are valuable synthetic intermediates.

Purpose of the Study:

  • To investigate thermal cracking of substituted oxiranes for perfluoroalkylcarbene generation.
  • To compare carbene generation barriers with difluorocarbene.
  • To assess carbene stability and potential rearrangement pathways.

Main Methods:

  • Ab initio density functional theory calculations.
  • Analysis of reaction barriers and transition states.
  • Investigation of unimolecular rearrangement pathways for perfluorocarbenes.

Main Results:

  • Barriers for fluoro(perfluoroalkyl)carbene generation are higher than for difluorocarbene.

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  • Carbene stability is linked to singlet carbene stability.
  • Perfluorocarbene rearrangements follow specific energy trends: 1,2-alkyl shifts < 1,2-fluorine shifts < 1,3-fluorine shifts.
  • Extrusion of SiF(4) from perfluorosilylalkanes is a viable alternative method.

    • Conclusions:

    • Thermal oxirane cracking is a feasible, though energy-intensive, route to perfluoroalkylcarbenes.
    • Generated carbenes exhibit good stability for reactions with olefins.
    • Alternative methods like SiF(4) extrusion offer advantages when thermal conditions are limiting.