Synthesis of hydrofluoroethers (HFEs) as alternatives to CFCs

Volume 9, Issue 1, February 2024     |     PP. 13-24      |     PDF (430 K)    |     Pub. Date: September 25, 2018
DOI:    1341 Downloads     3370 Views  

Author(s)

Wei Li, Beijing Institute of Technology, 5 South Zhongguangcun Street, Haidian District, Beijing, 100081, P.R. China; Zhejiang Chemical Industry Research Institute Co., Ltd., Hangzhou 310023, P.R. China.
Zhikai Guo, Zhejiang Chemical Industry Research Institute Co., Ltd., Hangzhou 310023, P.R. China.
Hengdao Quan, Beijing Institute of Technology, 5 South Zhongguangcun Street, Haidian District, Beijing, 100081, P.R. China.

Abstract
A facile synthetic route for the preparation of a series of hydrofluoroethers (HFEs) was developed. This route was based on two key reactions. The first reaction involved the alcoholysis of various fluoroalcohols with p-toluenesulfonyl chloride in a sodium hydroxide solution, while the second involved the Williamson ether syntheses of the desired HFEs from the corresponding tosylates using sodium methoxide in methanol. As a result, a range of HFEs were synthesized using this mild and efficient method.

Keywords
hydrofluoroethers • alcoholysis • Williamson ether synthesis

Cite this paper
Wei Li, Zhikai Guo, Hengdao Quan, Synthesis of hydrofluoroethers (HFEs) as alternatives to CFCs , SCIREA Journal of Chemistry. Volume 9, Issue 1, February 2024 | PP. 13-24.

References

[ 1 ] A. Sekiya, S. Misaki, A continuing search for new refrigerants, Chem. Tech. 26 (1996) 44–48.
[ 2 ] L. Chen, S. Kutsuna, K. Tokuhashi, A. Sekiya, R. Tamai, Y. Hibino, Kinetics and mechanism of (CF3)2CHOCH3 reaction with OH radicals in an environmental reaction chamber, J. Phys. Chem. A. 109 (2005) 4766–4771.
[ 3 ] F.F. Osterstrom, T.J. Wallington, M.P.S. Andersen, O.J. Nielsen, Atmospheric chemistry of (CF3)2CHOCH3, (CF3)2CHOCHO, and CF3C(O)OCH3, J. Phys. Chem. A. 119 (2015) 10540–10552.
[ 4 ] C.G. Krespan, V.N. Malliharijuma, Fluorinated methylethers. U.S. Patent 5382704, Jan. 15, 1995.
[ 5 ] K. Toshikazu, W. Mineo, Process for preparing luoromethyl 1,1,1,3,3,3- hexafluoroisopropylether. W.O. Patent 9730961, Oct. 21, 1997.
[ 6 ] M.T. Baker, J.H. Tinker, Process for the synthesis of hexafluoroisopropyl ethers. U.S. Patent 5705710, Jan. 6, 1998.
[ 7 ] V.A. Grinberg, S.R. Sterlin, L. Penisovich, Electrochemical perfluoroalkoxylation of aromatic compounds, Russ. Chem. Bull. 46 (1997) 1441–1444.
[ 8 ] W.E. Hanford, G.W. Rigby, Polyfluoroorganic ethers and their preparation. U.S. Patent 2409274, Oct. 15, 1946.
[ 9 ] J.D. Watson, L. Jackson, Catalytic preparation of fluoroethers. U.S. Patent 3291844, Dec. 13, 1966.
[ 10 ] W.T. Miller, E.W. Fager, P. H. Griswold, The addition of methyl alcohol to fluoroethylenes, J. Am. Chem. Soc. 70 (1948) 431–432.
[ 11 ] A.L. Henne, M. Nager, Trifluoropropyne. II. The triple bond and the acetylenic hydrogen, J. Am. Chem. Soc. 74 (1952) 650–652.
[ 12 ] X.M. Zhang, Radical substituent effects of alpha-fluorine and alpha-trifluoromethyl groups, J. Org. Chem. 63 (1998) 3590–3594.
[ 13 ] A.L. Henne, M.A. Smook, Fluorinated ethers, J. Am. Chem. Soc. 72 (1950) 4378–4380.
[ 14 ] J.A. Young, P. Tarrant, A new method of preparation of esters of difluoroacetic acid, J. Am. Chem. Soc. 72 (1950) 1860–1861.
[ 15 ] L. Hyunjoo, S.K. Hoon, K. Hongyon, Selective production of difluoromethyl methyl ether from chlorodifluoromethane using alkali metal carbonates, J. Fluorine Chem. 107 (2000) 133–136.
[ 16 ] N. Takada, A. Takashi, A. Sekiya, Preparation and physicochemical properties of F-tert-butyl alkyl ethers, J. Fluorine Chem. 92 (1998) 167–171.
[ 17 ] P.A. Champagne, Y. Benhassine. J. Desroches, J.F. Paquin, Friedel–Crafts reaction of benzyl fluorides: Selective activation of C–F bonds as enabled by hydrogen bonding, Angew. Chem. Int. Ed. 53 (2014) 13835–13839.
[ 18 ] W.C. Feng, Method for synthesis of 1,1,1,3,3,3-hexafluoroisopropyl methyl ether. China Patent 101544547, Sep. 30, 2009.
[ 19 ] S.V. Kovalenko, J. Swinson, Preparation of methyl fluoroalkyl ethers. U.S. Patent 20100312019, Dec. 9, 2010.
[ 20 ] M. Hanack, J. Ullmann, Facile synthesis of trifluoro- and hexafluoroisopropyl halides, J. Org. Chem. 54 (1989) 1432–1435.
[ 21 ] S.C. Miller, Profiling sulfonate ester stability: identification of complementary protecting groups for sulfonates, J. Org. Chem. 75 (2010) 4632–4635.