2,2-difluoro-2-fluorosulfonylacetyl fluoride

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 100 ml flask was charged with CH2Cl2 (24 ml) under nitrogen stream and stirred for 10 min at 0° C. and then 2-(fluorosulfonyl)difluoroacetyl fluoride (6.60 g, 37.6 mmol, 1.5 eq.) was added. After 20 minutes, the CH2Cl2 (12 ml) solution of 4-vinyl aniline (2.86 g, 24.4 mmol, 1.0 eq.) and pyridine (1.93 g, 24.4 mmol, 1.0 eq.) was added dropwise to the mixture over 10 minutes. The mixture was allowed to warm to RT and was stirred for 4 hours at RT. 1N HCl was added to the final reaction mixture and the lower layer was separated and washed with 1N HCl and brine. The solution was dried over MgSO4, filtrated and then CH2Cl2 was removed by an evaporator. The target compound was obtained as a white solid (6.57 g) in 96% yield. 1H NMR (400 MHz, CDCl3); delta=5.28 (d, J=10.9 Hz, 1H), 5.74 (d, J=17.6 Hz, 1H), 6.68 (dd, J=10.9, 17.6 Hz, 1H), 7.43 (d, J=8.6 Hz, 2H), 7.53 (d, J=8.7 Hz, 2H), 8.04 (brs, 1H). 19F-NMR (376 MHz, CDCl3, C6F6 as standard) delta=41.27 (t, J=4.6 Hz, 1F), −105.26 (d, J=4.2 Hz, 2F). After 20 minutes to warm to RT was stirred for 4 hours at RT reaction mixture the lower layer was separated washed with 1N HCl and brine The solution was dried over MgSO4 filtrated CH2Cl2 was removed by an evaporator

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 500 ml flask was charged with CH2Cl2 (80 ml) under nitrogen stream and stirred for 10 min at 0° C. and then 2-(fluorosulfonyl)difluoroacetyl fluoride (29.9 g, 166.0 mmol, 1.5 equivalent (eq.)) was added. After 25 minutes, a CH2Cl2 (160 ml) solution of 2-aminoethyl methacrylate hydrochloride (18.4 g, 111.0 mmol, 1.0 eq.) and pyridine (17.5 g, 221.0 mmol, 2.0 eq.) was added drop wise to the mixture over 50 minutes. The mixture was allowed to warm to room temperature (RT) and stirred for 3 hours at RT. 1N HCl was added to the final reaction mixture and the lower layer was separated and washed with 1N HCl and Brine. The solution was dried over anhydrous MgSO4, filtrated and then CH2Cl2 was removed by an evaporator. The crude product was purified by recrystallization (hexane/CHCl3). The target compound was obtained as a white solid (20.4 g) in 64% yield. 1H-NMR (400 MHz, CDCl3); delta=1.93 (dd, J=1.1, 1.2 Hz, 3H), 3.73 (td, J=5.4, 5.2 Hz, 2H), 4.35 (dd, J=5.1, 5.0 Hz, 2H), 5.63 (dq, J=1.4, 1.5 Hz, 1H), 6.12-6.14 (m, 1H), 7.09 (brs, 1H). 19F-NMR (376 MHz, CDCl3, C6F6 as standard); delta=40.68 (t, J=5.1 Hz, 1F), −105.91 (d, J=4.8 Hz, 2F). After 25 minutes to warm to room temperature (RT) stirred for 3 hours at RT reaction mixture the lower layer was separated washed with 1N HCl and Brine The solution was dried over anhydrous MgSO4 filtrated CH2Cl2 was removed by an evaporator The crude product was purified by recrystallization (hexane/CHCl3)

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 500 ml flask was charged with CH2Cl2 (80 ml) under nitrogen stream and stirred for 10 min at 0° C. and then 2-(fluorosulfonyl)difluoroacetyl fluoride (29.9 g, 166.0 mmol, 1.5 equivalent (eq.)) was added. After 25 minutes, a CH2Cl2 (160 ml) solution of 2-aminoethyl methacrylate hydrochloride (18.4 g, 111.0 mmol, 1.0 eq.) and pyridine (17.5 g, 221.0 mmol, 2.0 eq.) was added drop wise to the mixture over 50 minutes. The mixture was allowed to warm to room temperature (RT) and stirred for 3 hours at RT. 1N HCl was added to the final reaction mixture and the lower layer was separated and washed with 1N HCl and Brine. The solution was dried over anhydrous MgSO4, filtrated and then CH2Cl2 was removed by an evaporator. The crude product was purified by recrystallization (hexane/CHCl3). The target compound was obtained as a white solid (20.4 g) in 64% yield. 1H-NMR (400 MHz, CDCl3); delta=1.93 (dd, J=1.1, 1.2 Hz, 3H), 3.73 (td, J=5.4, 5.2 Hz, 2H), 4.35 (dd, J=5.1, 5.0 Hz, 2H), 5.63 (dq, J=1.4, 1.5 Hz, 1H), 6.12-6.14 (m, 1H), 7.09 (brs, 1H). 19F-NMR (376 MHz, CDCl3, C6F6 as standard); delta=40.68 (t, J=5.1 Hz, 1F), −105.91 (d, J=4.8 Hz, 2F). After 25 minutes to warm to room temperature (RT) stirred for 3 hours at RT reaction mixture the lower layer was separated washed with 1N HCl and Brine The solution was dried over anhydrous MgSO4 filtrated CH2Cl2 was removed by an evaporator The crude product was purified by recrystallization (hexane/CHCl3)

Conditions: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 5.8 g potassium fluoride, 60 ml acetonitrile and 12 ml fluorosulfonyl difluoroacetyl fluoride was heated at 80° C. for one hour. The resulting mixture was placed in a stainless steel autoclave and heated at 50° C. for one hour and 80° C. for one hour with 16 g of bromine and 30 g of tetrafluoroethylene. The reaction mixture was poured into a solution of sodium bisulfite, 50 ml 1,1,2-trichloro-1,2,2-trifluoroethane was added and the mixture was distilled to give a distillate boiling up to 100° C. which contained two layers. The organic layer was separated and distilled to give FSO2CF2CF2OCF2CF2Br, b.p. 106°, confirmed by infrared, nuclear magnetic resonance and mass spectroscopy. was added the mixture was distilled to give a distillate boiling up to 100° C. The organic layer was separated distilled

Conditions: temp:20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: CH2═C(CF2OSO2F)2 is added gradually to FSO2CF2CF2OK, which is prepared from freshly dried KF (3.9 g, 0.067 mole) and FSO2CF2COF (12 g, 0.067 mole) in dry diglyme (30 ml). The resulting mixture is stirred 3 hours at 20° C. The reaction mixture is poured into water. The organic layer is washed with aqueous sodium bicarbonate, then water, and then dried over MgSO4. Distillation gives CH2═C(CF3)CF2OSO2F (0.5 g) and CH2═C(CF2OCF2CF2SO2F)2 (9 g, 58% yield, b.pt. 95-96° C. at 15 mm Hg). The organic layer is washed with aqueous sodium bicarbonate water, and then dried over MgSO4 Distillation

Conditions: temp:20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: CH2═C(CF2OSO2F)2 is added gradually to FSO2CF2CF2OK, which is prepared from freshly dried KF (3.9 g, 0.067 mole) and FSO2CF2COF (12 g, 0.067 mole) in dry diglyme (30 ml). The resulting mixture is stirred 3 hours at 20° C. The reaction mixture is poured into water. The organic layer is washed with aqueous sodium bicarbonate, then water, and then dried over MgSO4. Distillation gives CH2═C(CF3)CF2OSO2F (0.5 g) and CH2═C(CF2OCF2CF2SO2F)2 (9 g, 58% yield, b.pt. 95-96° C. at 15 mm Hg). The organic layer is washed with aqueous sodium bicarbonate water, and then dried over MgSO4 Distillation

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 100 ml flask was charged with CH2Cl2 (24 ml) under nitrogen stream and stirred for 10 min at 0° C. and then 2-(fluorosulfonyl)difluoroacetyl fluoride (6.60 g, 37.6 mmol, 1.5 eq.) was added. After 20 minutes, the CH2Cl2 (12 ml) solution of 4-vinyl aniline (2.86 g, 24.4 mmol, 1.0 eq.) and pyridine (1.93 g, 24.4 mmol, 1.0 eq.) was added dropwise to the mixture over 10 minutes. The mixture was allowed to warm to RT and was stirred for 4 hours at RT. 1N HCl was added to the final reaction mixture and the lower layer was separated and washed with 1N HCl and brine. The solution was dried over MgSO4, filtrated and then CH2Cl2 was removed by an evaporator. The target compound was obtained as a white solid (6.57 g) in 96% yield. 1H NMR (400 MHz, CDCl3); delta=5.28 (d, J=10.9 Hz, 1H), 5.74 (d, J=17.6 Hz, 1H), 6.68 (dd, J=10.9, 17.6 Hz, 1H), 7.43 (d, J=8.6 Hz, 2H), 7.53 (d, J=8.7 Hz, 2H), 8.04 (brs, 1H). 19F-NMR (376 MHz, CDCl3, C6F6 as standard) delta=41.27 (t, J=4.6 Hz, 1F), −105.26 (d, J=4.2 Hz, 2F). After 20 minutes to warm to RT was stirred for 4 hours at RT reaction mixture the lower layer was separated washed with 1N HCl and brine The solution was dried over MgSO4 filtrated CH2Cl2 was removed by an evaporator

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 500 ml flask was charged with CH2Cl2 (80 ml) under nitrogen stream and stirred for 10 min at 0° C. and then 2-(fluorosulfonyl)difluoroacetyl fluoride (29.9 g, 166.0 mmol, 1.5 equivalent (eq.)) was added. After 25 minutes, a CH2Cl2 (160 ml) solution of 2-aminoethyl methacrylate hydrochloride (18.4 g, 111.0 mmol, 1.0 eq.) and pyridine (17.5 g, 221.0 mmol, 2.0 eq.) was added drop wise to the mixture over 50 minutes. The mixture was allowed to warm to room temperature (RT) and stirred for 3 hours at RT. 1N HCl was added to the final reaction mixture and the lower layer was separated and washed with 1N HCl and Brine. The solution was dried over anhydrous MgSO4, filtrated and then CH2Cl2 was removed by an evaporator. The crude product was purified by recrystallization (hexane/CHCl3). The target compound was obtained as a white solid (20.4 g) in 64% yield. 1H-NMR (400 MHz, CDCl3); delta=1.93 (dd, J=1.1, 1.2 Hz, 3H), 3.73 (td, J=5.4, 5.2 Hz, 2H), 4.35 (dd, J=5.1, 5.0 Hz, 2H), 5.63 (dq, J=1.4, 1.5 Hz, 1H), 6.12-6.14 (m, 1H), 7.09 (brs, 1H). 19F-NMR (376 MHz, CDCl3, C6F6 as standard); delta=40.68 (t, J=5.1 Hz, 1F), −105.91 (d, J=4.8 Hz, 2F). After 25 minutes to warm to room temperature (RT) stirred for 3 hours at RT reaction mixture the lower layer was separated washed with 1N HCl and Brine The solution was dried over anhydrous MgSO4 filtrated CH2Cl2 was removed by an evaporator The crude product was purified by recrystallization (hexane/CHCl3)

Conditions: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 5.8 g potassium fluoride, 60 ml acetonitrile and 12 ml fluorosulfonyl difluoroacetyl fluoride was heated at 80° C. for one hour. The resulting mixture was placed in a stainless steel autoclave and heated at 50° C. for one hour and 80° C. for one hour with 16 g of bromine and 30 g of tetrafluoroethylene. The reaction mixture was poured into a solution of sodium bisulfite, 50 ml 1,1,2-trichloro-1,2,2-trifluoroethane was added and the mixture was distilled to give a distillate boiling up to 100° C. which contained two layers. The organic layer was separated and distilled to give FSO2CF2CF2OCF2CF2Br, b.p. 106°, confirmed by infrared, nuclear magnetic resonance and mass spectroscopy. was added the mixture was distilled to give a distillate boiling up to 100° C. The organic layer was separated distilled

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A round-bottom flask is charged with 50 ml of CFC-113 and 2.0 g of sodium percarbonate (13 mmoles or 19 mmoles of H2O2 equivalent). After chilling the contents of the flask to 0° C., 2.83 ml of FSO2CF2(C═O)F (25 mmoles) is added and the resulting slurry is stirred magnetically for 3 hours. The reaction mixture is filtered through a pad of Drierite® on glass wool, washing through with fresh CFC-113, an operation assumed to remove any unreacted percarbonate and any free H2O2. The filtrate, now measuring 52 ml in volume, is found to be 0.10 M in peroxide for a 42% yield based on starting FSO2CF2(C═O)F. The reaction mixture is filtered through a pad of Drierite® on glass wool washing through with fresh CFC-113 to remove any unreacted percarbonate

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A round-bottom flask is charged with 50 ml of CFC-113 and 2.0 g of sodium percarbonate (13 mmoles or 19 mmoles of H2O2 equivalent). After chilling the contents of the flask to 0° C., 2.83 ml of FSO2CF2(C═O)F (25 mmoles) is added and the resulting slurry is stirred magnetically for 3 hours. The reaction mixture is filtered through a pad of Drierite® on glass wool, washing through with fresh CFC-113, an operation assumed to remove any unreacted percarbonate and any free H2O2. The filtrate, now measuring 52 ml in volume, is found to be 0.10 M in peroxide for a 42% yield based on starting FSO2CF2(C═O)F. The reaction mixture is filtered through a pad of Drierite® on glass wool washing through with fresh CFC-113 to remove any unreacted percarbonate

Conditions: temp:20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: CH2═C(CF2OSO2F)2 is added gradually to FSO2CF2CF2OK, which is prepared from freshly dried KF (3.9 g, 0.067 mole) and FSO2CF2COF (12 g, 0.067 mole) in dry diglyme (30 ml). The resulting mixture is stirred 3 hours at 20° C. The reaction mixture is poured into water. The organic layer is washed with aqueous sodium bicarbonate, then water, and then dried over MgSO4. Distillation gives CH2═C(CF3)CF2OSO2F (0.5 g) and CH2═C(CF2OCF2CF2SO2F)2 (9 g, 58% yield, b.pt. 95-96° C. at 15 mm Hg). The organic layer is washed with aqueous sodium bicarbonate water, and then dried over MgSO4 Distillation