2,2,3,3,4,4,5,5,6,6-decafluorocyclohexan-1-one

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

Procedure: A 500 ml, 3-necked round bottom flask equipped with an overhead stirrer, an addition funnel, and a condenser was charged with anhydrous cesium fluoride (27.4 g, 0.18 mole), anhydrous diethylene glycol dimethyl ether (258 g, hereinafter diglyme), and dimethyl sulfate (22.7 g, 0.18 mole). Perfluorocyclohexanone (50 g, 0.18 mole) was then added dropwise to the resulting stirred mixture, and stirring was continued for 18 hours after the addition. Water (approximately 200 ml) was added to the resulting mixture, and the lower fluorochemical phase of the mixture was separated from the upper phase and washed once with saturated aqueous sodium chloride solution. Since the fluorochemical phase still contained about 12% diglyme, water was added to it, and the resulting product was azeotropically distilled to yield 32.8 g of c-C6F11OCH3 (b.p.=100° C.), which was free of diglyme. The product identity was confirmed by IR, GCMS, and 1H and 19F NMR. A 500 ml, 3-necked round bottom flask equipped with an overhead stirrer, an addition funnel, and a condenser stirring after the addition the lower fluorochemical phase of the mixture was separated from the upper phase washed once with saturated aqueous sodium chloride solution Since the fluorochemical phase still contained about 12% diglyme, water was added to it the resulting product was azeotropically distilled to yield 32.8 g of c-C6F11OCH3 (b.p.=100° C.), which

Conditions: temp:-10.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of 30 g of perfluorocyclohexanone and 31.7 g of trichloroacetic acid was stirred in a pre-dried reaction vessel containing 113 mL of hexamethylphosphoramide. This mixture was cooled to −10° C. in a dry ice/acetone bath. Slight gas evolution was noted before and during the ketone addition. The stirred milky white reaction mixture was maintained at about 0° C. for an hour and then allowed to warm to 23° C. and stirring was continued 17 hours. The clear yellow solution was quenched with 150 mL of 10% HCl and then transferred to a separatory funnel with 400 mL of ethyl ether. This organic phase was washed with 4×500 mL of dilute HCl and then 300 mL of saturated NaCl solution. The solvent was removed by evaporation. The residue (33.7 g) contained 40.8% product by GC, confirmed by fluorine NMR. This carbinol can be converted to the corresponding acrylate by methods previously described (cf. Example 24). The stirred milky white reaction mixture was maintained at about 0° C. for an hour to warm to 23° C. The clear yellow solution was quenched with 150 mL of 10% HCl transferred to a separatory funnel with 400 mL of ethyl ether This organic phase was washed with 4×500 mL of dilute HCl The solvent was removed by evaporation

Conditions: temp:-10.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of 30 g of perfluorocyclohexanone and 31.7 g of trichloroacetic acid was stirred in a pre-dried reaction vessel containing 113 mL of hexamethylphosphoramide. This mixture was cooled to −10° C. in a dry ice/acetone bath. Slight gas evolution was noted before and during the ketone addition. The stirred milky white reaction mixture was maintained at about 0° C. for an hour and then allowed to warm to 23° C. and stirring was continued 17 hours. The clear yellow solution was quenched with 150 mL of 10% HCl and then transferred to a separatory funnel with 400 mL of ethyl ether. This organic phase was washed with 4×500 mL of dilute HCl and then 300 mL of saturated NaCl solution. The solvent was removed by evaporation. The residue (33.7 g) contained 40.8% product by GC, confirmed by fluorine NMR. This carbinol can be converted to the corresponding acrylate by methods previously described (cf. Example 24). The stirred milky white reaction mixture was maintained at about 0° C. for an hour to warm to 23° C. The clear yellow solution was quenched with 150 mL of 10% HCl transferred to a separatory funnel with 400 mL of ethyl ether This organic phase was washed with 4×500 mL of dilute HCl The solvent was removed by evaporation

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Under a N2 atmosphere 29.5 g of 1,3,5-trichloro-2,4,6-trifluorobenzene (Oakwood Products, Inc.) were dissolved in 150 mL dry ethyl ether. The solution was cooled to −78° C. in an acetone/dry-ice bath, then treated with 62.7 mL n-butyllithium (2 M solution in hexanes) over a two-hour period. Stirring was continued for 3 hours at −78° C. Via syringe, 34.8 g perfluorocyclohexanone were added, and the mixture was stirred at room temperature for 16 hours. The reaction was quenched with dilute HCl and extracted with ethyl ether, and the extracts were dried (using MgSO4) and rotary evaporated. Vacuum distillation (118-120° C., 80-110 Pa) gave 37.3 g 1-(3,5-dichloro-2,4,6-trifluorophenyl) perfluorocyclohexanol (62% yield) as a colorless liquid. the mixture was stirred at room temperature for 16 hours The reaction was quenched with dilute HCl extracted with ethyl ether the extracts were dried (using MgSO4) and rotary evaporated Vacuum distillation (118-120° C., 80-110 Pa)

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Under a N2 atmosphere 29.5 g of 1,3,5-trichloro-2,4,6-trifluorobenzene (Oakwood Products, Inc.) were dissolved in 150 mL dry ethyl ether. The solution was cooled to −78° C. in an acetone/dry-ice bath, then treated with 62.7 mL n-butyllithium (2 M solution in hexanes) over a two-hour period. Stirring was continued for 3 hours at −78° C. Via syringe, 34.8 g perfluorocyclohexanone were added, and the mixture was stirred at room temperature for 16 hours. The reaction was quenched with dilute HCl and extracted with ethyl ether, and the extracts were dried (using MgSO4) and rotary evaporated. Vacuum distillation (118-120° C., 80-110 Pa) gave 37.3 g 1-(3,5-dichloro-2,4,6-trifluorophenyl) perfluorocyclohexanol (62% yield) as a colorless liquid. the mixture was stirred at room temperature for 16 hours The reaction was quenched with dilute HCl extracted with ethyl ether the extracts were dried (using MgSO4) and rotary evaporated Vacuum distillation (118-120° C., 80-110 Pa)

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

Procedure: A 500 ml, 3-necked round bottom flask equipped with an overhead stirrer, an addition funnel, and a condenser was charged with anhydrous cesium fluoride (27.4 g, 0.18 mole), anhydrous diethylene glycol dimethyl ether (258 g, hereinafter diglyme), and dimethyl sulfate (22.7 g, 0.18 mole). Perfluorocyclohexanone (50 g, 0.18 mole) was then added dropwise to the resulting stirred mixture, and stirring was continued for 18 hours after the addition. Water (approximately 200 ml) was added to the resulting mixture, and the lower fluorochemical phase of the mixture was separated from the upper phase and washed once with saturated aqueous sodium chloride solution. Since the fluorochemical phase still contained about 12% diglyme, water was added to it, and the resulting product was azeotropically distilled to yield 32.8 g of c-C6F11OCH3 (b.p.=100° C.), which was free of diglyme. The product identity was confirmed by IR, GCMS, and 1H and 19F NMR. A 500 ml, 3-necked round bottom flask equipped with an overhead stirrer, an addition funnel, and a condenser stirring after the addition the lower fluorochemical phase of the mixture was separated from the upper phase washed once with saturated aqueous sodium chloride solution Since the fluorochemical phase still contained about 12% diglyme, water was added to it the resulting product was azeotropically distilled to yield 32.8 g of c-C6F11OCH3 (b.p.=100° C.), which

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

Procedure: A 500 ml, 3-necked round bottom flask equipped with an overhead stirrer, an addition funnel, and a condenser was charged with anhydrous cesium fluoride (27.4 g, 0.18 mole), anhydrous diethylene glycol dimethyl ether (258 g, hereinafter diglyme), and dimethyl sulfate (22.7 g, 0.18 mole). Perfluorocyclohexanone (50 g, 0.18 mole) was then added dropwise to the resulting stirred mixture, and stirring was continued for 18 hours after the addition. Water (approximately 200 ml) was added to the resulting mixture, and the lower fluorochemical phase of the mixture was separated from the upper phase and washed once with saturated aqueous sodium chloride solution. Since the fluorochemical phase still contained about 12% diglyme, water was added to it, and the resulting product was azeotropically distilled to yield 32.8 g of c-C6F11OCH3 (b.p.=100° C.), which was free of diglyme. The product identity was confirmed by IR, GCMS, and 1H and 19F NMR. A 500 ml, 3-necked round bottom flask equipped with an overhead stirrer, an addition funnel, and a condenser stirring after the addition the lower fluorochemical phase of the mixture was separated from the upper phase washed once with saturated aqueous sodium chloride solution Since the fluorochemical phase still contained about 12% diglyme, water was added to it the resulting product was azeotropically distilled to yield 32.8 g of c-C6F11OCH3 (b.p.=100° C.), which

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

Procedure: A 500 ml, 3-necked round bottom flask equipped with an overhead stirrer, an addition funnel, and a condenser was charged with anhydrous cesium fluoride (27.4 g, 0.18 mole), anhydrous diethylene glycol dimethyl ether (258 g, hereinafter diglyme), and dimethyl sulfate (22.7 g, 0.18 mole). Perfluorocyclohexanone (50 g, 0.18 mole) was then added dropwise to the resulting stirred mixture, and stirring was continued for 18 hours after the addition. Water (approximately 200 ml) was added to the resulting mixture, and the lower fluorochemical phase of the mixture was separated from the upper phase and washed once with saturated aqueous sodium chloride solution. Since the fluorochemical phase still contained about 12% diglyme, water was added to it, and the resulting product was azeotropically distilled to yield 32.8 g of c-C6F11OCH3 (b.p.=100° C.), which was free of diglyme. The product identity was confirmed by IR, GCMS, and 1H and 19F NMR. A 500 ml, 3-necked round bottom flask equipped with an overhead stirrer, an addition funnel, and a condenser stirring after the addition the lower fluorochemical phase of the mixture was separated from the upper phase washed once with saturated aqueous sodium chloride solution Since the fluorochemical phase still contained about 12% diglyme, water was added to it the resulting product was azeotropically distilled to yield 32.8 g of c-C6F11OCH3 (b.p.=100° C.), which

Conditions: temp:-10.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of 30 g of perfluorocyclohexanone and 31.7 g of trichloroacetic acid was stirred in a pre-dried reaction vessel containing 113 mL of hexamethylphosphoramide. This mixture was cooled to -10° C. in a dry ice/acetone bath. Slight gas evolution was noted before and during the ketone addition. The stirred milky white reaction mixture was maintained at about 0° C. for an hour and then allowed to warm to 23° C. and stirring was continued 17 hours. The clear yellow solution was quenched with 150 mL of 10% HCl and then transferred to a separatory funnel with 400 mL of ethyl ether. This organic phase was washed with 4×500 mL of dilute HCl and then 300 mL of saturated NaCl solution. The solvent was removed by evaporation. The residue (33.7 g) contained 40.8% product by GC, confirmed by fluorine NMR. This carbinol can be converted to the corresponding acrylate by methods previously described (cf. Example 24). The stirred milky white reaction mixture was maintained at about 0° C. for an hour to warm to 23° C. The clear yellow solution was quenched with 150 mL of 10% HCl transferred to a separatory funnel with 400 mL of ethyl ether This organic phase was washed with 4×500 mL of dilute HCl The solvent was removed by evaporation

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Under a N2 atmosphere 29.5 g of 1,3,5-trichloro-2,4,6-trifluorobenzene (Oakwood Products, Inc.) were dissolved in 150 mL dry ethyl ether. The solution was cooled to -78° C. in an acetone/dry-ice bath, then treated with 62.7 mL n-butyllithium (2 M solution in hexanes) over a two-hour period. Stirring was continued for 3 hours at -78° C. Via syringe, 34.8 g perfluorocyclohexanone were added, and the mixture was stirred at room temperature for 16 hours. The reaction was quenched with dilute HCl and extracted with ethyl ether, and the extracts were dried (using MgSO4) and rotary evaporated. Vacuum distillation (118-120° C., 80-110 Pa) gave 37.3 g 1-(3,5-dichloro-2,4,6-trifluorophenyl) perfluorocyclohexanol (62% yield) as a colorless liquid. the mixture was stirred at room temperature for 16 hours The reaction was quenched with dilute HCl extracted with ethyl ether the extracts were dried (using MgSO4) and rotary evaporated Vacuum distillation (118-120° C., 80-110 Pa)

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Under a N2 atmosphere 29.5 g of 1,3,5-trichloro-2,4,6-trifluorobenzene (Oakwood Products, Inc.) were dissolved in 150 mL dry ethyl ether. The solution was cooled to -78° C. in an acetone/dry-ice bath, then treated with 62.7 mL n-butyllithium (2 M solution in hexanes) over a two-hour period. Stirring was continued for 3 hours at -78° C. Via syringe, 34.8 g perfluorocyclohexanone were added, and the mixture was stirred at room temperature for 16 hours. The reaction was quenched with dilute HCl and extracted with ethyl ether, and the extracts were dried (using MgSO4) and rotary evaporated. Vacuum distillation (118-120° C., 80-110 Pa) gave 37.3 g 1-(3,5-dichloro-2,4,6-trifluorophenyl) perfluorocyclohexanol (62% yield) as a colorless liquid. the mixture was stirred at room temperature for 16 hours The reaction was quenched with dilute HCl extracted with ethyl ether the extracts were dried (using MgSO4) and rotary evaporated Vacuum distillation (118-120° C., 80-110 Pa)

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

Procedure: A 500 ml, 3-necked round bottom flask equipped with an overhead stirrer, an addition funnel, and a condenser was charged with anhydrous cesium fluoride (27.4 g, 0.18 mole), anhydrous diethylene glycol dimethyl ether (258 g, hereinafter diglyme), and dimethyl sulfate (22.7 g, 0.18 mole). Perfluorocyclohexanone (50 g, 0.18 mole) was then added dropwise to the resulting stirred mixture, and stirring was continued for 18 hours after the addition. Water (approximately 200 ml) was added to the resulting mixture, and the lower fluorochemical phase of the mixture was separated from the upper phase and washed once with saturated aqueous sodium chloride solution. Since the fluorochemical phase still contained about 12% diglyme, water was added to it, and the resulting product was azeotropically distilled to yield 32.8 g of c-C6F11OCH3 (b.p.=100° C.), which was free of diglyme. The product identity was confirmed by IR, GCMS, and 1H and 19F NMR. A 500 ml, 3-necked round bottom flask equipped with an overhead stirrer, an addition funnel, and a condenser stirring after the addition the lower fluorochemical phase of the mixture was separated from the upper phase washed once with saturated aqueous sodium chloride solution Since the fluorochemical phase still contained about 12% diglyme, water was added to it the resulting product was azeotropically distilled to yield 32.8 g of c-C6F11OCH3 (b.p.=100° C.), which