Living Edition
| Editors: Jinbo Hu, Teruo Umemoto

Fluoroolefin-Amine Adduct Deoxofluorination

  • Viacheslav Petrov
Living reference work entry
DOI: https://doi.org/10.1007/978-981-10-1855-8_24-1

Fluoroolefin-amine adducts (FAAs) belong to a broader group of α,α-fluoroalkyl amino reagents (FAR). FAAs are widely used for the conversion of alcohols and acids into the corresponding alkyl or acyl fluorides. Fluoroolefin-amine adducts (FAAs) are one of the oldest group of organic fluorinating agents, which became very popular due to their availability, simple synthesis, and ability to convert alcohols and acids into alkyl and acyl fluorides. The application of the first representative of this group – adduct of chlorotrifluoroethylene and diethylamine (Yarovenko reagent) – as a reagent for conversion of alcohols into alkyl fluorides was reported in 1959 [1].

The chemistry of FAAs and FAR was previously overviewed. Detailed reports can be found in the following articles: synthesis and chemistry of Yarovenko reagent [1], Yarovenko and Ishikawa reagents [2], TFEDMA reagent [3], adducts of amines and 2-H-pentafluoropropene [4], and FAR reagents [5].

The synthesis of FAAs is...

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  1. 1.
    C.M. Sharts, Sheppard, W.A, Org. Reactions 21 (1974), pp. 158–173 and references herein.Google Scholar
  2. 2.
    S. Bohm, “Yarovenko and Ishikawa Reagents” in: Methods of Organic Chemistry (Houben Weyl), ed B. Basner, Hagemann, H., Tatlow J.C. (New York, 2000),v. E10b/1, pp. 99–112 and references herein.Google Scholar
  3. 3.
    C.P. Junk, V.A. Petrov, “1,1,2,2-Tetrafluorethyl-N,N-Dimethylamine” in e-EROS Encyclopedia of Reagents for Organic Synthesis (John Wiley & Sons, Ltd., 2014), pp. 1–2Google Scholar
  4. 4.
    J. Walkowiak, H. Koroniak, “Preparation of α-Fluoro Amino and α-Fluoro Enamino Reagents” in: Efficient Preparation of Fluorine Compounds, ed. H.W. Roesky (J.Wiley & Sons Inc., 2013), Chpt. 58, pp. 379–384.Google Scholar
  5. 5.
    V.A. Petrov, α,α-Fluoroalkyl(alkenyl) amino reagents (FAR) – recent development, Adv. Org. Synth. 2 (2006) 269–290 and references hereinGoogle Scholar
  6. 6.
    N.N. Yarovenko, M.A. Raksha, Fluorination with α-fluorinated amines, Zh. Obshch. Khim. 29 (1959) 2159–2163.Google Scholar
  7. 7.
    D.E. Ayer, (to DuPont) US Pat. 3,153,644 (1964).Google Scholar
  8. 8.
    I.L. Knunyants, L.S. German, B.L. Dyatkin, Addition reactions of perfluoroölefins. VI. Reaction of perfluoroisobutylene and perfluoropropylene with nucleophilic reagents, Izv. Akad. Nauk SSSR, Ser. Khim. (1956) 1353–1360.Google Scholar
  9. 9.
    A. Takaoka, H. Iwakiri, N. Fujiwara, N. Ishikawa, Use of hexafluoropropene and dialkylamine adducts as fluorinating agents for alcohols and carboxylic acids. Synthesis of tetrafluoropropionamidines, tetrafluoroethyl-substituted benzo heterocycles, and fluorocytosine derivatives, Nippon Kagaku Kaishi (1985) 2161–2168.Google Scholar
  10. 10.
    D.C. England, L.R. Melby, M.A. Dietrich, R.V. Lindsey, Jr., Nucleophilic reactions of fluoroölefins, J. Am. Chem. Soc. 82 (1960) 5116–5122.Google Scholar
  11. 11.
    V.A. Petrov, W. Hong, W.C. Petersen, S. Swearingen, 1,1,2,2-Tetrafluoroethyl-N,N-dimethylamine: a new selective fluorinating agent, Fluorinated Bioact. Compd. Agric. Med. Fields, Proc. Conf. (1999) 18/11–18/13.Google Scholar
  12. 12.
    V.A. Petrov, S. Swearingen, W. Hong, W. Chris Petersen, 1,1,2,2-Tetrafluoroethyl-N,N-dimethylamine: a new selective fluorinating agent, J. Fluorine Chem. 109 (2001) 25–31.CrossRefGoogle Scholar
  13. 13.
    F. Aribi, E. Schmitt, A. Panossian, J.-P. Vors, S. Pazenok, F.R. Leroux, A new approach toward the synthesis of 2,4-bis(fluoroalkyl)-substituted quinoline derivatives using fluoroalkyl amino reagent chemistry, Organic Chemistry Frontiers 3 (2016) 1392–1415.CrossRefGoogle Scholar
  14. 14.
    I.G. Maslennikov, K.I. Eremin, Reaction of perfluorinated vinyl ethers with diethylamine, Russ. J. Gen. Chem. 81 (2011) 1741–1742.CrossRefGoogle Scholar
  15. 15.
    H. Koroniak, J. Walkowiak, K. Grys, A. Rajchel, A. Alty, R. Du Boisson, 1,1,3,3,3-Pentafluoropropene secondary amine adducts as new selective fluorinating agents, J. Fluorine Chem. 127 (2006) 1245–1251.CrossRefGoogle Scholar
  16. 16.
    I. Dlouha, J. Kvicala, O. Paleta, Reactivity study of 1,1,2,4,4,5,7,7,8,8,9,9,9-tridecafluoro-5-trifluoromethyl-3,6-dioxanon-1-ene in nucleophilic reactions: fluorination properties of secondary amine adducts, J. Fluorine Chem. 117 (2002) 149–159.CrossRefGoogle Scholar
  17. 17.
    G.G. Furin, L.S. Pressman, L.M. Pokrovsky, A.P. Krysin, K.W. Chi, Reaction of 1,1,2-trifluoro-2-hexafluoro-2′-(heptafluoropropoxy)propoxyethylene with amines or alcohols, J. Fluorine Chem. 106 (2000) 13–24.CrossRefGoogle Scholar
  18. 18.
    G.G. Furin, I.A. Salmanov, V.G. Kiriyanov, Reaction of 1,1,2-trifluoro-2-[hexafluoro-2-(heptafluoropropoxy)propoxy]ethene with some amines, Zh. Prikl. Khim. 72 (1999) 1345–1353.Google Scholar
  19. 19.
    A. Takaoka, H. Iwakiri, N. Ishikawa, Perfluoropropene-dialkylamine reaction products as fluorinating agents, Bull. Chem. Soc. Jpn. 52 (1979) 3377–3380.CrossRefGoogle Scholar
  20. 20.
    A.D. B. Haveaux, M. Rens, A. R. Sidani, J. Toye, and L. Ghosez, α-CHLORO ENAMINES, REACTIVE INTERMEDIATES FOR SYNTHESIS: 1-CHLORO-N,N,2-TRIMETHYLPROPENYLAMINE. Org. Synth. 59 (1979) 26.CrossRefGoogle Scholar
  21. 21.
    A. Colens, Demuylder, M., Téchy, B., Ghosez, L., Nouveau J. Chim., 1 (1977) 369.Google Scholar
  22. 22.
    E.D. Bergmann, Cohen, A., Isr. J. Chem. 3 (1965) 71.CrossRefGoogle Scholar
  23. 23.
    M. Hudlicky, Lejhankova, I., Coll. Czech. Chem. Commun. 31 (1966) 1416.CrossRefGoogle Scholar
  24. 24.
    J. Kopecky, Smejkal, J., Collect. Czech. Chem. Commun. 45 (1980) 2971.CrossRefGoogle Scholar
  25. 25.
    D.E. Ayer, Tetrahedron Lett. (1962) 1065.Google Scholar
  26. 26.
    S. Watanabe, T. Fujita, K. Suga, I. Nasuno, Fluorination of fatty alcohols with 1,1,2,3,3,3-hexafluoropropyldiethylamine, JAOCS, J. Am. Oil Chem. Soc. 60 (1983) 1678–1679.CrossRefGoogle Scholar
  27. 27.
    S. Watanabe, T. Fujita, K. Suga, I. Nasuno, T. Kuramochi, Fluorination of various terpenic alcohols and fatty alcohols with N,N-diethyl-1,1,2,3,3,3-hexafluoropropylamine, Yukagaku 33 (1984) 58–60.Google Scholar
  28. 28.
    S. Watanabe, T. Fujita, Y. Usui, Y. Kimura, T. Kitazume, Fluorination of halo alcohols with 1,1,2,3,3,3-hexafluoropropyldiethylamine, J. Fluorine Chem. 31 (1986) 135–141.CrossRefGoogle Scholar
  29. 29.
    S. Watanabe, T. Fujita, Y. Usui, T. Kitazume, Fluorination of hydroxy esters with N,N-diethyl-1,1,2,3,3,3-hexafluoropropylamine, J. Fluorine Chem. 31 (1986) 247–253.CrossRefGoogle Scholar
  30. 30.
    S. Watanabe, T. Fujita, M. Sakamoto, H. Endo, T. Kitazume, Reactions of nitro alcohols with N,N-diethyl-1,1,2,3,3,3-hexafluoropropylamine, J. Fluorine Chem. 38 (1988) 243–248.CrossRefGoogle Scholar
  31. 31.
    S. Watanabe, T. Fujita, M. Sakamoto, T. Kuramochi, T. Kitazume, Reactions of monoesters of ethylene glycol with N,N-diethyl-1,1,2,3,3,3-hexafluoropropylamine, J. Fluorine Chem. 36 (1987) 361–372.CrossRefGoogle Scholar
  32. 32.
    N.N. Yarovenko, Raksha M.A., Shemanina V.N, Vasilyeva, A.S, J. Gen. Chem USSR, Engl.Transl., 27 (1957).Google Scholar
  33. 33.
    C.P. Junk, V.A. Petrov, (E. I. du Pont de Nemours and Company, USA. 2009).Google Scholar
  34. 34.
    F. Liska, Dedek, V., Cvak, L., Collect. Czech. Chem. Commun. 31 (1966) 1416.CrossRefGoogle Scholar
  35. 35.
    F. Munyemana, A.M. Frisque-Hesbain, A. Devos, L. Ghosez, Synthesis of alkyl halides under neutral conditions, Tetrahedron Lett. 30 (1989) 3077–3080.CrossRefGoogle Scholar
  36. 36.
    P. Kirsch, in: Modern Fluoroorganic Chemistry, (Wiley-VCH, 2009).Google Scholar
  37. 37.
    J. Leroy, Herbert, E., Wakselman, C., Maximum optical; rotation of 2 F-octane?, J. Org. Chem. 44 (1979) 3406.CrossRefGoogle Scholar
  38. 38.
    V. Dedek, Liska, F., Chem. Commun. (Cambridge) 32 (1967) 4297.Google Scholar
  39. 39.
    F. Liska, Dedek, V., Cvak, L., Collect. Czech. Chem. Commun. 40 (1975) 1441.CrossRefGoogle Scholar
  40. 40.
    J. Kopecky, Smejkal, J., J. Chem. Ind. (1969) 271.Google Scholar
  41. 41.
    K. Ogu, Akazome, M., Ogura K., Propargyl alcohols, J. Fluorine Chem. 125 (2004) 429–438.CrossRefGoogle Scholar
  42. 42.
    M.A. K. Ogu, K. Ogura,, Allylic alcohols Ishikawa, Tetraherdron Lett. (1998) 305–308.Google Scholar
  43. 43.
    J. Walkowiak, M. Tomas-Szwaczyk, G. Haufe, H. Koroniak, Synthesis of α-trifluoromethylated amides by Eschenmoser-Claisen-type rearrangement of allylic alcohols, J. Fluorine Chem. 143 (2012) 189–197.CrossRefGoogle Scholar
  44. 44.
    D. O’Hagan, J. Fluorine Chem. 43 (1989) 371.CrossRefGoogle Scholar
  45. 45.
    N. Lui, S. Pazenok, (Bayer CropScience AG, Germany). WO 2008049531, 2008.Google Scholar
  46. 46.
    L.M. Grieco, G.A. Halliday, C.P. Junk, S.R. Lustig, W.J. Marshall, V.A. Petrov, Reactions of 1,1,2,2-tetrafluoroethyl-N,N-dimethylamine with linear and cyclic 1,3-diketones, J. Fluorine Chem. 132 (2011) 1198–1206.CrossRefGoogle Scholar
  47. 47.
    D.G. Cox, L.G. Sprague, D.J. Burton, The facile preparation of hydrofluoric acid-free polyfluorinated acyl fluorides, J. Fluorine Chem. 23 (1983) 383–388.CrossRefGoogle Scholar

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© Springer Nature Singapore Pte Ltd. 2018

Authors and Affiliations

  1. 1.FluoroproductsChemours Co.WilmingtonUSA