1,1,1,2,3,3-hexafluoro-2-(1,1,2,2,3,3,3-heptafluoropropoxy)-3-(1,2,2-trifluoroethenoxy)propane

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

Procedure: In a dry box, tetrahydrofuran (THF, 1000 mL) and dimethyl 5-hydroxyisophthalate (42.00 g, 0.20 mol) were added to an oven dry round bottom reaction flask equipped with a stirrer and an addition funnel; then potassium t-butoxide (6.16 g, 0.055 mol) was added. 1,1,1,2,2,3,3-Heptafluoro-3-(1,1,1,2,3,3-hexafluoro-3-(1,2,2trifluorovinyloxy)propan-2-yloxy)propane (216 g, 0.50 mol) was then added via the addition funnel forming a reaction. The reaction was allowed to stir at room temperature. After 24 hours the reaction was terminated via the addition of 80 mL of 10% HCl. The reaction was concentrated at reduced pressure, diluted with dichloromethane, washed with 10% HCl (2×100 mL) and then with water (2×100 mL) forming an organic phase and a crude product. The organic phase was dried over anhydrous sodium sulfate and concentrated at reduced pressure. The crude product was purified by column chromatography to give 86.07 g (67.32%) yield of dimethyl 5-(1,1,2-trifluoro-2-(1,1,2,3,3,3-hexafluoro-2-(perfluoropropoxy)propoxy)ethoxy)isophthalate. dry round bottom reaction flask equipped with a stirrer and an addition funnel forming a reaction After 24 hours the reaction was terminated via the addition of 80 mL of 10% HCl The reaction was concentrated at reduced pressure diluted with dichloromethane washed with 10% HCl (2×100 mL) with water (2×100 mL) forming an organic phase The organic phase was dried over anhydrous sodium sulfate concentrated at reduced pressure The crude product was purified by column chromatography

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

Procedure: In a dry box, tetrahydrofuran (THF, 1000 mL) and dimethyl 5-hydroxyisophthalate (42.00 g, 0.20 mol) were added to an oven dry round bottom reaction flask equipped with a stirrer and an addition funnel; then potassium t-butoxide (6.16 g, 0.055 mol) was added. 1,1,1,2,2,3,3-Heptafluoro-3-(1,1,1,2,3,3-hexafluoro-3-(1,2,2trifluorovinyloxy)propan-2-yloxy)propane (216 g, 0.50 mol) was then added via the addition funnel forming a reaction. The reaction was allowed to stir at room temperature. After 24 hours the reaction was terminated via the addition of 80 mL of 10% HCl. The reaction was concentrated at reduced pressure, diluted with dichloromethane, washed with 10% HCl (2×100 mL) and then with water (2×100 mL) forming an organic phase and a crude product. The organic phase was dried over anhydrous sodium sulfate and concentrated at reduced pressure. The crude product was purified by column chromatography to give 86.07 g (67.32%) yield of dimethyl 5-(1,1,2-trifluoro-2-(1,1,2,3,3,3-hexafluoro-2-(perfluoropropoxy)propoxy)ethoxy)isophthalate. dry round bottom reaction flask equipped with a stirrer and an addition funnel forming a reaction After 24 hours the reaction was terminated via the addition of 80 mL of 10% HCl The reaction was concentrated at reduced pressure diluted with dichloromethane washed with 10% HCl (2×100 mL) with water (2×100 mL) forming an organic phase The organic phase was dried over anhydrous sodium sulfate concentrated at reduced pressure The crude product was purified by column chromatography

Conditions: temp:85.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A clean, dry, 600 mL, stainless steel, Parr pressure reactor was charged with spray-dried potassium fluoride (10.0 grams, 0.17 mole), anhydrous diglyme (129 grams), and Adogen™ 464 phase transfer catalyst (2.2 grams). The reactor was sealed, cooled with a dry ice-acetone bath, evacuated, and charged with perfluoropropionyl fluoride (70.0 grams, 0.42 mole) and C3F7OCF(CF3)CF2OCF═CF2 (170 grams, 0.39 mole). The reactor was heated to 85° C., held for 16 hours with agitation, and cooled to room temperature. The resulting intermediate ketone-containing reaction mixture (0.39 mole based on starting vinyl ether) was used without further purification and was combined with an additional amount of anhydrous diglyme (1000 grams), potassium fluoride (35.7 grams, 0.62 mole), catalyst (28 grams, 56 percent solution in diglyme), and diethyl sulfate (121.2 grams, 0.79 mole) in a 3 L flask. With stirring, the flask was heated to 52° C. for 16 hours. At the end of this time, potassium hydroxide (52 grams, dissolved in 300 g water) was added, and the resulting mixture was heated to 65° C. and then distilled azeotropically using a Dean Stark trap, from which the resulting lower fluorochemical phase was separated during the distillation. The resulting product was distilled (b.p.=189-191° C.) to a purity of 92 percent. Product structure was confirmed by IR and GCMS. A clean, dry The reactor was sealed cooled with a dry ice-acetone bath evacuated cooled to room temperature was used without further purification the flask was heated to 52° C. for 16 hours the resulting mixture was heated to 65° C. distilled azeotropically from which the resulting lower fluorochemical phase was separated during the distillation The resulting product was distilled (b.p.=189-191° C.) to a purity of 92 percent

Conditions: temp:85.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A clean, dry, 600 mL, stainless steel, Parr pressure reactor was charged with spray-dried potassium fluoride (10.0 grams, 0.17 mole), anhydrous diglyme (129 grams), and Adogen™ 464 phase transfer catalyst (2.2 grams). The reactor was sealed, cooled with a dry ice-acetone bath, evacuated, and charged with perfluoropropionyl fluoride (70.0 grams, 0.42 mole) and C3F7OCF(CF3)CF2OCF═CF2 (170 grams, 0.39 mole). The reactor was heated to 85° C., held for 16 hours with agitation, and cooled to room temperature. The resulting intermediate ketone-containing reaction mixture (0.39 mole based on starting vinyl ether) was used without further purification and was combined with an additional amount of anhydrous diglyme (1000 grams), potassium fluoride (35.7 grams, 0.62 mole), catalyst (28 grams, 56 percent solution in diglyme), and diethyl sulfate (121.2 grams, 0.79 mole) in a 3 L flask. With stirring, the flask was heated to 52° C. for 16 hours. At the end of this time, potassium hydroxide (52 grams, dissolved in 300 g water) was added, and the resulting mixture was heated to 65° C. and then distilled azeotropically using a Dean Stark trap, from which the resulting lower fluorochemical phase was separated during the distillation. The resulting product was distilled (b.p.=189-191° C.) to a purity of 92 percent. Product structure was confirmed by IR and GCMS. A clean, dry The reactor was sealed cooled with a dry ice-acetone bath evacuated cooled to room temperature was used without further purification the flask was heated to 52° C. for 16 hours the resulting mixture was heated to 65° C. distilled azeotropically from which the resulting lower fluorochemical phase was separated during the distillation The resulting product was distilled (b.p.=189-191° C.) to a purity of 92 percent

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

Procedure: Conversion of CF3CF2CF2OCF(CF3)CF2OCF═CF2 to CF3CF2CF2OCF(CF3)CF2OCF2COOCH3 (bp 91-92° C. at 133 mbar) was carried out as described in U.S. Pat. No. 4,987,254. The ester was reacted with aqueous ammonia and methanol was removed by distillation resulting in CF3CF2CF2OCF(CF3)CF2OCF2COONH4. All structures were confirmed by F-NMR spectra. Due to an isomer content in the vinyl ether, an isomer with the structure CF3CF2CF2OCF2CF(CF3)OCF2COOX (X═CH3, NH4) was found. was removed by distillation resulting in CF3CF2CF2OCF(CF3)CF2OCF2COONH4

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

Procedure: Conversion of CF3CF2CF2OCF(CF3)CF2OCF═CF2 to CF3CF2CF2OCF(CF3)CF2OCF2COOCH3 (bp 91-92° C. at 133 mbar) was carried out as described in U.S. Pat. No. 4,987,254. The ester was reacted with aqueous ammonia and methanol was removed by distillation resulting in CF3CF2CF2OCF(CF3)CF2OCF2COONH4. All structures were confirmed by F-NMR spectra. Due to an isomer content in the vinyl ether, an isomer with the structure CF3CF2CF2OCF2CF(CF3)OCF2COOX (X═CH3, NH4) was found. was removed by distillation resulting in CF3CF2CF2OCF(CF3)CF2OCF2COONH4

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

Procedure: Conversion of CF3CF2CF2OCF(CF3)CF2OCF═CF2 to CF3CF2CF2OCF(CF3)CF2OCF2COOCH3 (bp 91-92° C. at 133 mbar) was carried out as described in U.S. Pat. No. 4,987,254. The ester was reacted with aqueous ammonia and methanol was removed by distillation resulting in CF3CF2CF2OCF(CF3)CF2OCF2COONH4. All structures were confirmed by F-NMR spectra. Due to an isomer content in the vinyl ether, an isomer with the structure CF3CF2CF2OCF2CF(CF3)OCF2COOX (X═CH3, NH4) was found. was removed by distillation resulting in CF3CF2CF2OCF(CF3)CF2OCF2COONH4

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

Procedure: In the dry box, THF (50 mL) and 4-vinylphenol (5.00 g of a 10% solution in propylene glycol) were added to an oven dry RB flask equipped with a stirrer, Potassium carbonate (0.35 g, 0.0025 mol) was then added. 1,1,1,2,2,3,3-Heptafluoro-3-(1,1,1,2,3,3-hexafluoro-3-(1,2,2-trifluorovinyloxy)propan-2-yloxy)propane (2.70 g, 0.00625 mol) was then added via the addition funnel and the reaction allowed to stir at room temperature. The reaction mixture was heated to a gentle reflux under nitrogen overnight. An aliquot was withdrawn and concentrated under vacuum and analyzed via proton NMR which showed the complete conversion to be 1-(1,1,2-trifluoro-2-(1,1,2,3,3,3-hexafluoro-2-(perfluoropropoxy)propoxy)ethoxy)-4-vinylbenzene. The cooled reaction mixture was then concentrated at reduced pressure taken up in methylene chloride washed with water (˜25 mL) separated, then dried over anhydrous sodium sulfate. The separated organic phase was then concentrated at reduced pressure and then column chromatograph on silica gel obtaining 1.15 g (about 50.0%) of the theoretical yield) of product. dry RB flask equipped with a stirrer The reaction mixture was heated to a gentle reflux under nitrogen overnight An aliquot was withdrawn concentrated under vacuum The cooled reaction mixture was then concentrated at reduced pressure washed with water (˜25 mL) separated dried over anhydrous sodium sulfate The separated organic phase was then concentrated at reduced pressure column chromatograph on silica gel obtaining 1.15 g (about 50.0%) of the theoretical yield) of product

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

Procedure: In the dry box, THF (500 mL) and methyl 4-hydroxybenzoate (26.6 g, 0.175 mol) were added to an oven dry RB flask equipped with a stirrer, Potassium carbonate (12.00 g, 0.087 mol) was then added. 1,1,1,2,2,3,3-Heptafluoro-3-(1,1,1,2,3,3-hexafluoro-3-(1,2,2-trifluorovinyloxy)propan-2-yloxy)propane (94.5 g, 0.219 mol) was then added via the addition funnel and the reaction allowed to stir at room temperature. The reaction mixture was heated to a gentle reflux, oil temperature about 80° C., under nitrogen overnight. An aliquot was withdrawn and concentrated under vacuum and analyzed via proton NMR that showed the complete conversion to the desired material. The cooled reaction mixture was then filtered through silica gel and then concentrated at reduced pressure, resulting in 101.52 g (99.33%) yield of the desired material. dry RB flask equipped with a stirrer The reaction mixture was heated to a gentle reflux, oil temperature about 80° C., under nitrogen overnight An aliquot was withdrawn concentrated under vacuum The cooled reaction mixture was then filtered through silica gel concentrated at reduced pressure

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

Procedure: In the dry box, tetrahydrofuran (25 mL) and 4-hydroxybenzaldehyde (0.61 g, 0.005 mol) were added to a round bottom flask equipped with a stirrer. Potassium carbonate (0.175 g, 0.00126 mol) was then added to the flask. 1,1,1,2,2,3,3-Heptafluoro-3-(1,1,1,2,3,3-hexafluoro-3-(1,2,2-trifluorovinyloxy)propan-2-yloxy)propane (3.24 g, 0.0075 mol) was then added via the addition funnel and the reaction was placed in an oil bath and heated to a gentle reflux for two hours. The content was analyzed by proton NMR and shown to be 1-ethynyl-3-(1,1,2-trifluoro-2-(1,1,2,3,3,3-hexafluoro-2-(perfluoropropoxy)propoxy)ethoxy)benzene. equipped with a stirrer the reaction was placed in an oil bath heated to a gentle reflux for two hours

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

Procedure: In the dry box, tetrahydrofuran (25 mL) and 4-hydroxybenzaldehyde (0.61 g, 0.005 mol) were added to a round bottom flask equipped with a stirrer. Potassium carbonate (0.175 g, 0.00126 mol) was then added to the flask. 1,1,1,2,2,3,3-Heptafluoro-3-(1,1,1,2,3,3-hexafluoro-3-(1,2,2-trifluorovinyloxy)propan-2-yloxy)propane (3.24 g, 0.0075 mol) was then added via the addition funnel and the reaction was placed in an oil bath and heated to a gentle reflux for two hours. The content was analyzed by proton NMR and shown to be 1-ethynyl-3-(1,1,2-trifluoro-2-(1,1,2,3,3,3-hexafluoro-2-(perfluoropropoxy)propoxy)ethoxy)benzene. equipped with a stirrer the reaction was placed in an oil bath heated to a gentle reflux for two hours

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

Procedure: Conversion of CF3CF2CF2OCF(CF3)CF2OCF═CF2 to CF3CF2CF2OCF(CF3)CF2OCF2COOCH3 (bp 91-92° C. at 133 mbar) was carried out as described in U.S. Pat. No. 4,987,254. The ester was reacted with aqueous ammonia and methanol was removed by distillation resulting in CF3CF2CF2OCF(CF3)CF2OCF2COONH4. All structures were confirmed by F-NMR spectra. Due to an isomer content in the vinyl ether, an isomer with the structure CF3CF2CF2OCF2CF(CF3)OCF2COOX(X═CH3, NH4) was found. was removed by distillation resulting in CF3CF2CF2OCF(CF3)CF2OCF2COONH4