2,5-BIS(TRIFLUOROMETHYL)-3,6-DIOXAUNDECAFLUORONONANOYL FLUORIDE

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

Procedure: A reaction was carried out in the same manner as in Example 1-3, except that the mixture (2.1 g) was changed to a mixture of (CF3)2CFOCOCF(CF3)OCF2CF(CF3)OCF2CF2CF3 and (CF3)2CHOCOCF(CF3)OCF2CF(CF3)OCF2CF2CF3 in a ratio of 8:2 (mass ratio) (hereinafter this mixture will be referred to as the fluorinated ester mixture, 10.0 g), and the NaF powder (0.02 g) was changed to KF powder (0.03 g). After cooling, a liquid sample (7.9 g) and a gas sample (1.9 g) were recovered. They were respectively analyzed by GC-MS, whereby it was confirmed that in the gas sample, the above-identified compound was the main product, and in the liquid sample, FCOCF(CF3)OCF2CF(CF3)OCF2CF2CF3 was the main product. The yield of the above-identified compound as calculated by GC in the same manner as in Example 1-3, was 95.2%. Further, from the liquid sample, FCOCF(CF3)OCF2CF(CF3)OCF2CF2CF3 (5.9 g) was obtained. After cooling a liquid sample (7.9 g) and a gas sample (1.9 g) were recovered

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

Procedure: A reaction was carried out in the same manner as in Example 1-3, except that the mixture (2.1 g) was changed to a mixture of (CF3)2CFOCOCF(CF3)OCF2CF(CF3)OCF2CF2CF3 and (CF3)2CHOCOCF(CF3)OCF2CF(CF3)OCF2CF2CF3 in a ratio of 8:2 (mass ratio) (hereinafter this mixture will be referred to as the fluorinated ester mixture, 10.0 g), and the NaF powder (0.02 g) was changed to KF powder (0.03 g). After cooling, a liquid sample (7.9 g) and a gas sample (1.9 g) were recovered. They were respectively analyzed by GC-MS, whereby it was confirmed that in the gas sample, the above-identified compound was the main product, and in the liquid sample, FCOCF(CF3)OCF2CF(CF3)OCF2CF2CF3 was the main product. The yield of the above-identified compound as calculated by GC in the same manner as in Example 1-3, was 95.2%. Further, from the liquid sample, FCOCF(CF3)OCF2CF(CF3)OCF2CF2CF3 (5.9 g) was obtained. After cooling a liquid sample (7.9 g) and a gas sample (1.9 g) were recovered

Conditions: temp:140.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: FSO2CF2CF2COOCF2CF(CF3)OCF2CF(CF3)OCF2CF2CF3 (3.6 g) obtained in Example 2-5 was charged into a flask together with NaF powder (0.02 g) and heated at 140° C. for 10 hours in an oil bath with vigorous stirring. At the upper portion of the flask, a reflux condenser having the temperature maintained at 20° C. was installed. After cooling, a liquid sample (3.4 g) was recovered. As a result of the analysis by GC-MS, CF3CF2CF2OCF(CF3)CF2OCF(CF3)COF and the title compound were confirmed as the main products. The NMR yield of the title compound was 70.9%, and the yield of CF3CF2CF2OCF(CF3)CF2OCF(CF3)COF was 72.0%. maintained at 20° C. After cooling a liquid sample (3.4 g) was recovered

Conditions: temp:140.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: FSO2CF2CF2COOCF2CF(CF3)OCF2CF(CF3)OCF2CF2CF3 (3.6 g) obtained in Example 2-5 was charged into a flask together with NaF powder (0.02 g) and heated at 140° C. for 10 hours in an oil bath with vigorous stirring. At the upper portion of the flask, a reflux condenser having the temperature maintained at 20° C. was installed. After cooling, a liquid sample (3.4 g) was recovered. As a result of the analysis by GC-MS, CF3CF2CF2OCF(CF3)CF2OCF(CF3)COF and the title compound were confirmed as the main products. The NMR yield of the title compound was 70.9%, and the yield of CF3CF2CF2OCF(CF3)CF2OCF(CF3)COF was 72.0%. maintained at 20° C. After cooling a liquid sample (3.4 g) was recovered

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

Procedure: A reaction was carried out in the same manner as in Example 1-3, except that the mixture (2.1 g) was changed to a mixture of (CF3)2CFOCOCF(CF3)OCF2CF(CF3)OCF2CF2CF3 and (CF3)2CHOCOCF(CF3)OCF2CF(CF3)OCF2CF2CF3 in a ratio of 8:2 (mass ratio) (hereinafter this mixture will be referred to as the fluorinated ester mixture, 10.0 g), and the NaF powder (0.02 g) was changed to KF powder (0.03 g). After cooling, a liquid sample (7.9 g) and a gas sample (1.9 g) were recovered. They were respectively analyzed by GC-MS, whereby it was confirmed that in the gas sample, the above-identified compound was the main product, and in the liquid sample, FCOCF(CF3)OCF2CF(CF3)OCF2CF2CF3 was the main product. The yield of the above-identified compound as calculated by GC in the same manner as in Example 1-3, was 95.2%. Further, from the liquid sample, FCOCF(CF3)OCF2CF(CF3)OCF2CF2CF3 (5.9 g) was obtained. After cooling a liquid sample (7.9 g) and a gas sample (1.9 g) were recovered

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

Procedure: CF3(CF2)2OCF(CF3)CF2OCF(CF3)COF (120.69 g) was loaded into an autoclave and stirred under a nitrogen stream, and HO(CH2)3OCH(CH3)CH2OH (15.1 g) prepared in Example 2-3 was fed over 2 hours, while the temperature in the autoclave was maintained at 30° C. or below. Then, the reaction solution was stirred at room temperature under a nitrogen stream overnight and poured onto saturated aqueous NaHCO3 (500 mL) with ice. was maintained at 30° C. or below stream overnight

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

Procedure: A suspension of 58.1 g (1.0 mol) of flame-dried KF in 1400 ml of dry diglyme was stirred at 25° while 333 g (0.67 mol) of hexafluoropropene oxide trimer was added rapidly. The two-phase system was stirred at 25° for 2 hr, during which time about half of the fluorocarbon layer slowly dissolved. The mixture was stirred at 5°-10° while 230 g (1.0 mol) of 1 was added. The mixture was stirred at 5°-10° for 2.5 hr, then overnight at 25°, and poured into 2 l. of H2O. The aqueous layer was extracted with 100 ml of CFCl2CF2Cl, and the combined organic layers washed with 2 l. of H2O, extracted with 100 ml of conc. H2SO4, clarified with CaSO4, filtered and distilled. Hydrolysis and bubbling were apparent in the water washed. Distillation afforded major fractions of 2 and 3, bp 55°-71° (20 mm) and 140 g of crude CF3CF2CF2OCF(CF3)CF2OCF(CF3)CO2H, bp mainly 101°-104° (20 mm). Redistillation of combined fractions of 2 and 3 gave 80 g of impure 3, bp 81°-86° (80 mm) and 33.0 g (8%) of 2, bp 94°-95° (80 mm). was added rapidly slowly dissolved was added overnight at 25°, and poured into 2 l The aqueous layer was extracted with 100 ml of CFCl2CF2Cl the combined organic layers washed with 2 l of H2O, extracted with 100 ml of conc. H2SO4 filtered distilled Hydrolysis bubbling washed Distillation

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

Procedure: A suspension of 58.1 g (1.0 mol) of flame-dried KF in 1400 ml of dry diglyme was stirred at 25° while 333 g (0.67 mol) of hexafluoropropene oxide trimer was added rapidly. The two-phase system was stirred at 25° for 2 hr, during which time about half of the fluorocarbon layer slowly dissolved. The mixture was stirred at 5°-10° while 230 g (1.0 mol) of 1 was added. The mixture was stirred at 5°-10° for 2.5 hr, then overnight at 25°, and poured into 2 l. of H2O. The aqueous layer was extracted with 100 ml of CFCl2CF2Cl, and the combined organic layers washed with 2 l. of H2O, extracted with 100 ml of conc. H2SO4, clarified with CaSO4, filtered and distilled. Hydrolysis and bubbling were apparent in the water washed. Distillation afforded major fractions of 2 and 3, bp 55°-71° (20 mm) and 140 g of crude CF3CF2CF2OCF(CF3)CF2OCF(CF3)CO2H, bp mainly 101°-104° (20 mm). Redistillation of combined fractions of 2 and 3 gave 80 g of impure 3, bp 81°-86° (80 mm) and 33.0 g (8%) of 2, bp 94°-95° (80 mm). was added rapidly slowly dissolved was added overnight at 25°, and poured into 2 l The aqueous layer was extracted with 100 ml of CFCl2CF2Cl the combined organic layers washed with 2 l of H2O, extracted with 100 ml of conc. H2SO4 filtered distilled Hydrolysis bubbling washed Distillation

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

Procedure: A suspension of 58.1 g (1.0 mol) of flame-dried KF in 1400 ml of dry diglyme was stirred at 25° while 333 g (0.67 mol) of hexafluoropropene oxide trimer was added rapidly. The two-phase system was stirred at 25° for 2 hr, during which time about half of the fluorocarbon layer slowly dissolved. The mixture was stirred at 5°-10° while 230 g (1.0 mol) of 1 was added. The mixture was stirred at 5°-10° for 2.5 hr, then overnight at 25°, and poured into 2 l. of H2O. The aqueous layer was extracted with 100 ml of CFCl2CF2Cl, and the combined organic layers washed with 2 l. of H2O, extracted with 100 ml of conc. H2SO4, clarified with CaSO4, filtered and distilled. Hydrolysis and bubbling were apparent in the water washed. Distillation afforded major fractions of 2 and 3, bp 55°-71° (20 mm) and 140 g of crude CF3CF2CF2OCF(CF3)CF2OCF(CF3)CO2H, bp mainly 101°-104° (20 mm). Redistillation of combined fractions of 2 and 3 gave 80 g of impure 3, bp 81°-86° (80 mm) and 33.0 g (8%) of 2, bp 94°-95° (80 mm). was added rapidly slowly dissolved was added overnight at 25°, and poured into 2 l The aqueous layer was extracted with 100 ml of CFCl2CF2Cl the combined organic layers washed with 2 l of H2O, extracted with 100 ml of conc. H2SO4 filtered distilled Hydrolysis bubbling washed Distillation

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

Procedure: A suspension of 58.1 g (1.0 mol) of flame-dried KF in 1400 ml of dry diglyme was stirred at 25° while 333 g (0.67 mol) of hexafluoropropene oxide trimer was added rapidly. The two-phase system was stirred at 25° for 2 hr, during which time about half of the fluorocarbon layer slowly dissolved. The mixture was stirred at 5°-10° while 230 g (1.0 mol) of 1 was added. The mixture was stirred at 5°-10° for 2.5 hr, then overnight at 25°, and poured into 2 l. of H2O. The aqueous layer was extracted with 100 ml of CFCl2CF2Cl, and the combined organic layers washed with 2 l. of H2O, extracted with 100 ml of conc. H2SO4, clarified with CaSO4, filtered and distilled. Hydrolysis and bubbling were apparent in the water washed. Distillation afforded major fractions of 2 and 3, bp 55°-71° (20 mm) and 140 g of crude CF3CF2CF2OCF(CF3)CF2OCF(CF3)CO2H, bp mainly 101°-104° (20 mm). Redistillation of combined fractions of 2 and 3 gave 80 g of impure 3, bp 81°-86° (80 mm) and 33.0 g (8%) of 2, bp 94°-95° (80 mm). was added rapidly slowly dissolved was added overnight at 25°, and poured into 2 l The aqueous layer was extracted with 100 ml of CFCl2CF2Cl the combined organic layers washed with 2 l of H2O, extracted with 100 ml of conc. H2SO4 filtered distilled Hydrolysis bubbling washed Distillation

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

Procedure: CF3(CF2)2OCF(CF3)CF2OCF(CF3)COF (120.69 g) was loaded into an autoclave and stirred under a nitrogen stream, and HO(CH2)3OCH(CH3)CH2OH (15.1 g) prepared in Example 2-3 was fed over 2 hours, while the temperature in the autoclave was maintained at 30° C. or below. Then, the reaction solution was stirred at room temperature under a nitrogen stream overnight and poured onto saturated aqueous NaHCO3 (500 mL) with ice. was maintained at 30° C. or below stream overnight

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

Procedure: A suspension of 58.1 g (1.0 mol) of flame-dried KF in 1400 ml of dry diglyme was stirred at 25° while 333 g (0.67 mol) of hexafluoropropene oxide trimer was added rapidly. The two-phase system was stirred at 25° for 2 hr, during which time about half of the fluorocarbon layer slowly dissolved. The mixture was stirred at 5°-10° while 230 g (1.0 mol) of 1 was added. The mixture was stirred at 5°-10° for 2.5 hr, then overnight at 25°, and poured into 2 l. of H2O. The aqueous layer was extracted with 100 ml of CFCl2Cl, and the combined organic layers washed with 2 l. of H2O, extracted with 100 ml of conc. H2SO4, clarified with CaSO4, filtered and distilled. Hydrolysis and bubbling were apparent in the water washed. Distillation afforded major fractions of 2 and 3, bp 55°-71° (20 mm) and 140 g of crude CF3CF2CF2OCF(CF3)CF2OCF(CF3)CO2H, bp mainly 101°-104° (20 mm). Redistillation of combined fractions of 2 and 3 gave 80 g of impure 3, bp 81°-86° (80 mm) and 33.0 g (8%) of 2, bp 94°-95° (80 mm). was added rapidly slowly dissolved was added overnight at 25°, and poured into 2 l The aqueous layer was extracted with 100 ml of CFCl2Cl the combined organic layers washed with 2 l of H2O, extracted with 100 ml of conc. H2SO4 filtered distilled Hydrolysis bubbling washed Distillation