Synthesis of perfluoroalkyl trifluoromethanesulfonates from perfluoroalkyl halides. Substitutive electrophilic dehalogenation with chlorine(I) and bromine(I) trifluoromethanesulfonates

Abstract

The reactions of chlorine(I) and bromine(I) trifluoromethanesulfonates with a variety of perfluoroalkyl halides are reported. The reactions form Bra, Cla, or BrCl and the corresponding trifluoromethanesulfonate derivatives of the alkyls in good yields. Twelve new esters are reported and characterized. An Sni-type mechanism for the reactions is proposed with complete retention of configuration by the alkyl on substitution. 24-111 to 22 CCIF3 (3.5), SO3 Cl (5.0) C2F5Br (5.0) 15 -40 to -5 CF3S03C2F5 (2.9), C2F6 (0.5) BrCl (5.9) Cl (6.5) C3F7Br (6.5) 36 -40 to 22 CF3S03C3F7 (4.2), C3F8 (0.6) BrCl (5.7) Cl (4.6) CC12F2 (5.1) 15 -78 to 22 CF3S03CF2C1 (4.2), Cl2 (4.5) 0(5.1) CBr2F2 (5.4) 1 -111 CF3S03CF2Br (0.8), COF2 (4.0), (CF3S02)20 (2.0), BrCl Cl (3.3) CBr2F2 (4.5) 1 -160* ^CF3SG3CF2Br (2.0), COF2 (1.2), (CF3S02)2G (0.6), BrCl Cl(5.0) CCI3F (7.0) 15 -78 to 22 CF3S03CFC12 (4.4), (CF3S02)2G (0.2) Br (3.9) CF3Br (5.0) 15 -111 to -10 CF3S03CF3 (2.9), Br2 (3.9) Br (2.0) CFCb (5.0) 15 -78 to 22 CF3S03CFC12 (1.0), BrCl Cl (4.4) CC12F2 (2.0) 15 -60 to 22 (CF3S03)2CF2 (0.1), CF3S03CF2C1 (1.0), COF2 (0.8), (CF3S02)20 (0.8), Cl2 0(1.2) CBr2F2 (2.5) 11 -150 to -130» COF2 (1.9), (CF3S02)20 (1.5), BrCl Cl (6.1) CC13F (3.0) 15 -85 to -40 CF3S03CC12F (2.2), (CF3SG2) O (0.7), COC1F, Cl2 Br (5.0) CBr2F2 (2.4) 24 -111 to -60 (CF3S03)2CF2 (0.7), CF3S03CF2Br (0.7), (CF3S02)2G (0.35), Br2 (4.5), COF2 (0.9), CF3S03CF3 (0.4) Br (4.1) CC12F2 (2.0) 15 -111 to-50 (CF3S03)2CF2 (0.12), CF3S03CF2C1 (0.6), (CF3SG2)20 (0.6), COF2 (1.), cf3so3cf3 (0.7), BrCl (2.2) Cl (3.5) (CF2Br)2 (1.6) 15 -88 to -30 (CF3S03CF2)2 (0.52), CF3S03CF2CF2Br (0.99), C2F5Br (0.1), BrCl (3.6) 0(5.6) (CF2Br)2 (2.7) 15 -111 to 22* CF3SG3CF2CF2Br (1.0), CF3S03CF2C1(2.9), C2F5Br (1.5), BrCl-Cl2 (5.4) Cl (6.0) (CF2Br)2 (3.0) 1 -111 to-88CF3S03CF2CF2Br (1.7), CF3S03CF3 (0.8), C2F5Br (0.4), BrCl (3.2) Cl (6.9) CBr3F (2.3) 15 -111* CF3S03C(0)F (1.6), (CF3S02)20 (1.8), BrCl (1.6), COBrF Cl (6.9) CC13F (2.3) 24

A novel fluorine‐containing graft copolymer bearing perfluorocyclobutyl aryl ether‐based backbone and poly(methyl methacrylate) side chains

“…Benzoyl peroxide (BPO, Alfa Aesar, 97%) was purified by dissolving in acetone and precipitating in water followed by drying in vacuo at room temperature for 1 day. BrCF 2 CF 2 Br was prepared by condensing equimolar amounts of bromine and tetrafluoroethylene at −195 °C followed by warming up to 22 °C 74. 4‐Methoxytrifluorovinyloxybenzene23 and diheptyl‐2,2′‐bipyridine (dHbpy)75 were prepared according to previous literatures.…”

Perfluorocyclobutyl-based methacrylate monomers: Synthesis and radical polymerization

“…Granular zinc was activated by washing in 0.1 N HCl followed by drying at 140 8C in vacuo for 10 h. 1,2-Dibromotetrafluoroethane was prepared by condensing equimolar amounts of Br 2 and tetrafluoroethylene at À195 8C followed by warming up to 22 8C [23]. All solvents were purified by standard methods prior to use.…”

Advances in the Development of Trifluoromethoxylation Reagents

“…1)). Some other known methods for preparation of TFMT 36 are collected in Scheme 24 [102][103][104][105][106][107][108]. Most of these approaches were based on in situ formation and decomposition of triflic anhydride using dangerously reactive reagents under rather forcing reaction conditions requiring specialized equipment.…”

“…• C[101][102][103][104][105][106][107][108]. sidered as relatively "convenient" for commercial preparation of TFMT.…”