1,1,2,3,3-pentafluoro-3-fluorosulfonyloxyprop-1-ene

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

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

Procedure: A solution of 53.9 g (0.2 mole) of methyltriethylammonium-3-cyanotetrafluoropropionate prepared as in Part A in 300 ml of diglyme was stirred at -10° to -5° while 46.0 g (0.20 mole) of perfluoroallyl fluorosulfate was rapidly added. The mixture was then stirred at -10° to -5° for 1 hr., and then at -5° to 0° for 4 hr. Removal of volatiles at 35° (5 mm, 6.7×10-1 kPa) through a liquid N2 trap and fractionation gave 10.0 g (29%) of 3-cyanotetrafluoropropionyl fluoride, bp 19°-20°. IR (gas phase): 2265 (CN), 1888 (COF), and 1300-1100 cm-1 (CF) with traces of CO2, SO2F2 and SiF4 present. NMR (CCl4 ; 0°); 19F 25.8 (t of t, JFF 10.1, 5.0 Hz, 1F, COF), -106.7 (d of t, JFF 5.0, 4.6 Hz, 2F, CF2CN), and -118.5 ppm (d of t, JFF 10.1, 4.6 Hz, 2F, CF2C=O). was rapidly added , and then at -5° to 0° for 4 hr Removal of volatiles at 35° (5 mm, 6.7×10-1 kPa) through a liquid N2 trap

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

Procedure: A suspension of 35.9 g (0.617 mol) of flame-dried KF in 750 ml of diglyme was stirred at 0° while 140.0 g (0.617 mol) of 3-bromotetrafluoropropionyl fluoride from part B was added. The mixture was stirred at 0°-5° for another 30 min and then was treated with 141.9 g (0.617 mol) of perfluoroallyl fluorosulfate. The reaction mixture was stirred for 4 h at 0°-5° and then poured into 3 liters of water. The resulting lower layer was washed with 500 ml of water, dried over CaSO4, and distilled to give 132.5 g (57%) of perfluoro(7-bromo4-oxa-1-heptene), bp 96°-99°, trace impurity only by GC. A sample from a similar synthesis was analyzed. IR (CCl4): 5.59μ (CF=CF2). NMR (CCl4): 19F -64.4 (t of m, JFF 9.9 Hz, 2 F, CFBr), -71.9 (d of d of t of d, JFF 24.9, 13.8, ~13, 7.3 Hz, 2F, OCF2C=), -82.8 (t of t of m, JFF ~13, 9.9 Hz, 2F, CF2O), -92.0 (d of d of t of t, JFF 52.0, 39.3, 7.3 Hz, 1F, cis-CF2CF=CFF), -105.3 (d of d of t, JFF 117.7, 52.0, 24.9 Hz, 1F, trans-CF2CF=CFF), -121.9 (m, 2F, CF2), and -190.6 ppm (d of d of t of t, JFF 117.7, 39.3, 13.8, 1.6 Hz, 1F, CF2CF=). was added The reaction mixture was stirred for 4 h at 0°-5° The resulting lower layer was washed with 500 ml of water dried over CaSO4 distilled

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

Procedure: However, in reality, it can be prepared by reacting tetrafluoroethane-β-sultone, KF and CF2═CFCF2OSO2F without isolating FOCCF2SO2F as the intermediate. Specifically, for example, in the presence of a solvent such as tetraglyme, KF and tetrafluoroethane-β-sultone are reacted under cooling, and CF2═CFCF2OSO2F is dropwise added thereto and reacted, whereby CF2═CFCF2OCF2CF2SO2F can be obtained. However, in reality, it can be prepared without isolating FOCCF2SO2F as the intermediate under cooling reacted

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

Procedure: However, in reality, it can be prepared by reacting tetrafluoroethane-β-sultone, KF and CF2═CFCF2OSO2F without isolating FOCCF2SO2F as the intermediate. Specifically, for example, in the presence of a solvent such as tetraglyme, KF and tetrafluoroethane-β-sultone are reacted under cooling, and CF2═CFCF2OSO2F is dropwise added thereto and reacted, whereby CF2═CFCF2OCF2CF2SO2F can be obtained. However, in reality, it can be prepared without isolating FOCCF2SO2F as the intermediate under cooling reacted

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

Procedure: A solution of 53.9 g (0.2 mole) of methyltriethylammonium-3-cyanotetrafluoropropionate prepared as in Part A in 300 ml of diglyme was stirred at -10° to -5° while 46.0 g (0.20 mole) of perfluoroallyl fluorosulfate was rapidly added. The mixture was then stirred at -10° to -5° for 1 hr., and then at -5° to 0° for 4 hr. Removal of volatiles at 35° (5 mm, 6.7×10-1 kPa) through a liquid N2 trap and fractionation gave 10.0 g (29%) of 3-cyanotetrafluoropropionyl fluoride, bp 19°-20°. IR (gas phase): 2265 (CN), 1888 (COF), and 1300-1100 cm-1 (CF) with traces of CO2, SO2F2 and SiF4 present. NMR (CCl4 ; 0°); 19F 25.8 (t of t, JFF 10.1, 5.0 Hz, 1F, COF), -106.7 (d of t, JFF 5.0, 4.6 Hz, 2F, CF2CN), and -118.5 ppm (d of t, JFF 10.1, 4.6 Hz, 2F, CF2C=O). was rapidly added , and then at -5° to 0° for 4 hr Removal of volatiles at 35° (5 mm, 6.7×10-1 kPa) through a liquid N2 trap

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

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

Procedure: A 300-mL four-neck flask provided with a Dimroth condenser, a dropping funnel, and a thermometer was charged with triethylamine hydrochloride (97 g, 703 mmol) and 50 mL of diglyme, and the mixture was stirred by a magnetic stirrer. The Dimroth condenser was cooled using a −20° C. refrigerant, and the reaction flask was cooled to 0° C. in an ice bath. With the dropping funnel, perfluoroallyl fluorosulfate (135 g, 586 mmol) was dropped over about one hour in such a manner that the temperature in the flask was maintained at 10° C. or lower. After the dropping, the mixture was stirred for one hour. The Dimroth condenser was replaced by a Liebig distillation apparatus. The flask was allowed to reach room temperature (25° C.), and the resulting product (having a boiling point of 12° C.) was distilled. An amount of 100 mL of water was added to the flask to terminate the reaction. As a result, 90.7 g of the target perfluoroallyl chloride (purity: 99 GC %) was obtained as a distilled component (yield: 93%). The distillation residue was determined by NMR analysis to include carboxylic acids and ammonium fluorosulfate which were probably generated from hydrolysis of unreacted perfluoroallyl fluorosulfate in terminating the reaction, and an excess amount of triethylamine hydrochloride. A 300-mL four-neck flask provided with a Dimroth condenser, a dropping funnel The Dimroth condenser was cooled using a −20° C. was maintained at 10° C. After the dropping, the mixture was stirred for one hour The Dimroth condenser was replaced by a Liebig distillation apparatus to reach room temperature (25° C.) was distilled An amount of 100 mL of water was added to the flask to terminate the reaction

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

Procedure: A 300-mL four-neck flask provided with a Dimroth condenser, a dropping funnel, and a thermometer was charged with triethylamine hydrochloride (97 g, 703 mmol) and 50 mL of diglyme, and the mixture was stirred by a magnetic stirrer. The Dimroth condenser was cooled using a −20° C. refrigerant, and the reaction flask was cooled to 0° C. in an ice bath. With the dropping funnel, perfluoroallyl fluorosulfate (135 g, 586 mmol) was dropped over about one hour in such a manner that the temperature in the flask was maintained at 10° C. or lower. After the dropping, the mixture was stirred for one hour. The Dimroth condenser was replaced by a Liebig distillation apparatus. The flask was allowed to reach room temperature (25° C.), and the resulting product (having a boiling point of 12° C.) was distilled. An amount of 100 mL of water was added to the flask to terminate the reaction. As a result, 90.7 g of the target perfluoroallyl chloride (purity: 99 GC %) was obtained as a distilled component (yield: 93%). The distillation residue was determined by NMR analysis to include carboxylic acids and ammonium fluorosulfate which were probably generated from hydrolysis of unreacted perfluoroallyl fluorosulfate in terminating the reaction, and an excess amount of triethylamine hydrochloride. A 300-mL four-neck flask provided with a Dimroth condenser, a dropping funnel The Dimroth condenser was cooled using a −20° C. was maintained at 10° C. After the dropping, the mixture was stirred for one hour The Dimroth condenser was replaced by a Liebig distillation apparatus to reach room temperature (25° C.) was distilled An amount of 100 mL of water was added to the flask to terminate the reaction

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

Procedure: A 300-mL four-neck flask provided with a Dimroth condenser, a dropping funnel, and a thermometer was charged with triethylamine hydrochloride (97 g, 703 mmol) and 50 mL of diglyme, and the mixture was stirred by a magnetic stirrer. The Dimroth condenser was cooled using a −20° C. refrigerant, and the reaction flask was cooled to 0° C. in an ice bath. With the dropping funnel, perfluoroallyl fluorosulfate (135 g, 586 mmol) was dropped over about one hour in such a manner that the temperature in the flask was maintained at 10° C. or lower. After the dropping, the mixture was stirred for one hour. The Dimroth condenser was replaced by a Liebig distillation apparatus. The flask was allowed to reach room temperature (25° C.), and the resulting product (having a boiling point of 12° C.) was distilled. An amount of 100 mL of water was added to the flask to terminate the reaction. As a result, 90.7 g of the target perfluoroallyl chloride (purity: 99 GC %) was obtained as a distilled component (yield: 93%). The distillation residue was determined by NMR analysis to include carboxylic acids and ammonium fluorosulfate which were probably generated from hydrolysis of unreacted perfluoroallyl fluorosulfate in terminating the reaction, and an excess amount of triethylamine hydrochloride. A 300-mL four-neck flask provided with a Dimroth condenser, a dropping funnel The Dimroth condenser was cooled using a −20° C. was maintained at 10° C. After the dropping, the mixture was stirred for one hour The Dimroth condenser was replaced by a Liebig distillation apparatus to reach room temperature (25° C.) was distilled An amount of 100 mL of water was added to the flask to terminate the reaction