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Hexafluorobutadiene is an organofluorine compound with the formula (CF2=CF)2. A colorless gas, it has attracted attention as an etchant in microelectronics. It is the perfluoroanalogue of butadiene.

Preparation

It can be prepared by coupling of fluorinated C2 precursors. Addition of iodine monochloride to chlorotrifluoroethylene gives iododichlorotrifluoroethane that can be coupled in the presence of mercury to give 1,2,3,4-tetrchlorohexafluorobutane:

2 CF2Cl−CFCl(I) + Hg → CF2Cl−CFCl−CFCl−CF2Cl + HgI2

Zn-induced dechlorination of this tetrachloride gives the desired perfluorinated diene:[1]

CF2Cl−CFCl−CFCl−CF2Cl + 2 Zn → CF2=CF−CF=CF2 + 2 ZnCl2

Reactions

The diene can be rehalogenated, e.g. with bromine upon UV irradiation:[1]

CF2=CF−CF=CF2 + 2 Br2 → CF2Br−CFBr−CFBr−CF2Br

Hexafluorobutadiene dimerizes via a [2+2] process at 150 °C to give perfluorinated divinylcyclobutanes.[2]

In the presence of the strong Lewis acid aluminium chlorofluoride, hexafluorobutadiene isomerizes to hexafluoro-2-butyne:[3]

CF2=CFCF=CF2 → CF3C≡CCF3

See also

References

  1. ^ a b Haszeldine, R. N. (1952). "849. Fluoro-olefins. Part I. The Synthesis of Hexafluorobuta-1:3-diene". Journal of the Chemical Society (Resumed): 4423. doi:10.1039/jr9520004423.
  2. ^ Lemal, David M.; Chen, Xudong (2005). "Fluorinated Cyclobutanes and Their Derivatives". In Zvi Rappoport; Joel F. Liebman (eds.). The Chemistry of Cyclobutanes. PATAI'S Chemistry of Functional Groups. pp. 955–1029. doi:10.1002/0470864028.ch21. ISBN 0470864001.
  3. ^ Petrov, V.A.; Krespan, C.G.; Smart, B.E. (1996). "Electrophilic reactions of fluorocarbons under the action of aluminum chlorofluoride, a potent Lewis acid". Journal of Fluorine Chemistry. 77 (2): 139–142. Bibcode:1996JFluC..77..139P. doi:10.1016/0022-1139(96)03391-x.

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