Isomerization of 1,1,2,3,3-pentafluoro-1,5-hexadiene upon reaction with fluoride ions. First example of sequential anionotropic and prototropic allylic rearrangements
Upon heating in DMF medium with KF and 18-crown-6 1,1,2,2,3-pentafluoro-1,5-hexadiene (1) is converted to 4,5,6,6,6-pentafluoro-1,3-hexadiene and 1,1,1,2,3-pentafluoro-2,4-hexadiene. Reaction of (1) with KHF2 results in the formation of its HF addition product, namely, 4,4,5,6,6,6-hexafluoro-1-hexene. We assume that the driving force in the isomerization of (1) is the formation of conjugated products, involving both the fluorinated and nonfluorinated portions of the molecules, preferably with the minimum number of fluorine atoms attached to the double bond.
Keywordsnonconjugated polyfluorinated dienes allylic rearrangement nucleophilic isomerization hydrosilylation hydrofluorination
Unable to display preview. Download preview PDF.
- 1.B. E. Smart, The Chemistry of Functional Groups. Suppl. D. (S. Patai, Z. Rapaport, eds.), Chap. XIV, Wiley, Chichester (1983).Google Scholar
- 2.(Patent) Application 57-85329 (Japan) (1982); RZhKhim 10N18 (1983).Google Scholar
- 3.I. P. Kolenko, A. V. Podol'skii, M. I. Kachalkova, M. I. Kodess, F. M. Mukhametshin, and A. V. Tiunov, Izv. Akad. Nauk, Ser. Khim., No. 8, 1885 (1984).Google Scholar
- 4.W. Brunskill, W. T. Flowers, R. Gregory, and R. N. Haszeldine, Chem. Commun., No. 21, 1444 (1970).Google Scholar