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...
References
C.M. Sharts, Sheppard, W.A, Org. Reactions 21 (1974), pp. 158–173 and references herein.
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.
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. 1–2
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.
V.A. Petrov, α,α-Fluoroalkyl(alkenyl) amino reagents (FAR) – recent development, Adv. Org. Synth. 2 (2006) 269–290 and references herein
N.N. Yarovenko, M.A. Raksha, Fluorination with α-fluorinated amines, Zh. Obshch. Khim. 29 (1959) 2159–2163.
D.E. Ayer, (to DuPont) US Pat. 3,153,644 (1964).
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.
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.
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.
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.
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.
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.
I.G. Maslennikov, K.I. Eremin, Reaction of perfluorinated vinyl ethers with diethylamine, Russ. J. Gen. Chem. 81 (2011) 1741–1742.
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.
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.
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.
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.
A. Takaoka, H. Iwakiri, N. Ishikawa, Perfluoropropene-dialkylamine reaction products as fluorinating agents, Bull. Chem. Soc. Jpn. 52 (1979) 3377–3380.
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.
A. Colens, Demuylder, M., Téchy, B., Ghosez, L., Nouveau J. Chim., 1 (1977) 369.
E.D. Bergmann, Cohen, A., Isr. J. Chem. 3 (1965) 71.
M. Hudlicky, Lejhankova, I., Coll. Czech. Chem. Commun. 31 (1966) 1416.
J. Kopecky, Smejkal, J., Collect. Czech. Chem. Commun. 45 (1980) 2971.
D.E. Ayer, Tetrahedron Lett. (1962) 1065.
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.
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.
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.
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.
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.
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.
N.N. Yarovenko, Raksha M.A., Shemanina V.N, Vasilyeva, A.S, J. Gen. Chem USSR, Engl.Transl., 27 (1957).
C.P. Junk, V.A. Petrov, (E. I. du Pont de Nemours and Company, USA. 2009).
F. Liska, Dedek, V., Cvak, L., Collect. Czech. Chem. Commun. 31 (1966) 1416.
F. Munyemana, A.M. Frisque-Hesbain, A. Devos, L. Ghosez, Synthesis of alkyl halides under neutral conditions, Tetrahedron Lett. 30 (1989) 3077–3080.
P. Kirsch, in: Modern Fluoroorganic Chemistry, (Wiley-VCH, 2009).
J. Leroy, Herbert, E., Wakselman, C., Maximum optical; rotation of 2 F-octane?, J. Org. Chem. 44 (1979) 3406.
V. Dedek, Liska, F., Chem. Commun. (Cambridge) 32 (1967) 4297.
F. Liska, Dedek, V., Cvak, L., Collect. Czech. Chem. Commun. 40 (1975) 1441.
J. Kopecky, Smejkal, J., J. Chem. Ind. (1969) 271.
K. Ogu, Akazome, M., Ogura K., Propargyl alcohols, J. Fluorine Chem. 125 (2004) 429–438.
M.A. K. Ogu, K. Ogura,, Allylic alcohols Ishikawa, Tetraherdron Lett. (1998) 305–308.
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.
D. O’Hagan, J. Fluorine Chem. 43 (1989) 371.
N. Lui, S. Pazenok, (Bayer CropScience AG, Germany). WO 2008049531, 2008.
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.
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.
Author information
Authors and Affiliations
Corresponding author
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2018 Springer Nature Singapore Pte Ltd.
About this entry
Cite this entry
Petrov, V. (2018). Fluoroolefin-Amine Adduct Deoxofluorination. In: Hu, J., Umemoto, T. (eds) Fluorination. Synthetic Organofluorine Chemistry. Springer, Singapore. https://doi.org/10.1007/978-981-10-1855-8_24-1
Download citation
DOI: https://doi.org/10.1007/978-981-10-1855-8_24-1
Received:
Accepted:
Published:
Publisher Name: Springer, Singapore
Print ISBN: 978-981-10-1855-8
Online ISBN: 978-981-10-1855-8
eBook Packages: Springer Reference Chemistry and Mat. ScienceReference Module Physical and Materials ScienceReference Module Chemistry, Materials and Physics