2-bromo-2,2-difluoroethanol

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

Procedure: A glass flask equipped with a thermometer, a condenser and a dropping funnel was charged with 271 g (2.24 moles) of pivaloyl chloride, 360 g (2.23 moles) of 2-bromo-2,2-difluoroethanol and 1.5 L of diisopropyl ether, followed by stirring. Then, 318 g (3.14 moles) of triethylamine was added dropwise thereto, in an iced bath. After the termination of the dropping, stirring was conducted for 1 hour at room temperature. Then, the termination of the reaction was confirmed by gas chromatography. With the addition of 300 mL of water, a reaction solution was completely dissolved therein, followed by adding 500 mL of 2N hydrochloric acid thereto. The reaction solution was separated into an organic layer and a water layer, followed by extracting the water layer with 500 ml of diisopropyl ether. Subsequently, the organic layer was rinsed with 500 ml of saturated brine, followed by drying with anhydrous sodium sulfate. Thereafter, a solvent was distilled off, thereby obtaining 485 g (82% yield, 93% purity) of 2-bromo-2,2-difluoroethyl pivalate in the form of a light yellow liquid. A glass flask equipped with a thermometer, a condenser and a dropping funnel After the termination of the dropping, stirring a reaction solution was completely dissolved The reaction solution was separated into an organic layer by extracting the water layer with 500 ml of diisopropyl ether Subsequently, the organic layer was rinsed with 500 ml of saturated brine by drying with anhydrous sodium sulfate Thereafter, a solvent was distilled off

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

Procedure: In tetrahydrofuran, 1-adamantanecarbonyl chloride and 2-bromo-2,2-difluoroethanol were mixed and ice cooled. Triethylamine was added to the mixture. By standard separation operation and solvent distillation, 2-bromo-2,2-difluoroethyl 1-adamantanecarboxylate was obtained. This compound was converted into a sodium sulfinate with sodium dithionite and then oxidized with hydrogen peroxide, yielding the target compound, sodium 2-(1-adamantanecarbonyloxy)-1,1-difluoroethane-sulfonate. ice cooled By standard separation operation and solvent distillation

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

Procedure: In tetrahydrofuran, 1-adamantanecarbonyl chloride and 2-bromo-2,2-difluoroethanol were mixed and ice cooled. Triethylamine was added to the mixture. By standard separation operation and solvent distillation, 2-bromo-2,2-difluoroethyl 1-adamantanecarboxylate was obtained. This compound was converted into a sodium sulfinate with sodium dithionite and then oxidized with hydrogen peroxide, yielding the target compound, sodium 2-(1-adamantanecarbonyloxy)-1,1-difluoroethanesulfonate. ice cooled By standard separation operation and solvent distillation

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

Procedure: Pivalic chloride and 2-bromo-2,2-difluoroethanol were mixed in tetrahydrofuran and ice cooled. Triethylamine was added to the mixture. Subsequent standard separatory operation and solvent distillation gave 2-bromo-2,2-difluoroethyl pivalate. This compound was converted into a sodium sulfinate using sodium dithionite and then oxidized with hydrogen peroxide, yielding the target compound, sodium 2-(pivaloyloxy)-1,1-difluoroethanesulfonate. ice cooled Subsequent standard separatory operation and solvent distillation

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

Procedure: Pivalic chloride and 2-bromo-2,2-difluoroethanol were mixed in tetrahydrofuran and ice cooled. Triethylamine was added to the mixture. Subsequent standard separatory operation and solvent distillation gave 2-bromo-2,2-difluoroethyl pivalate. This compound was converted into a sodium sulfinate using sodium dithionite and then oxidized with hydrogen peroxide, yielding the target compound, sodium 2-(pivaloyloxy)-1,1-difluoroethanesulfonate. ice cooled Subsequent standard separatory operation and solvent distillation

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

Procedure: One exemplary compound may be synthesized by reacting 2-bromo-2,2-difluoroethanol with pivalic chloride or anhydride to form 2-bromo-2,2-difluoroethyl pivalate, converting the bromo group into sodium sulfinate using a sulfur compound such as sodium dithionite, and converting sulfinic acid into sulfonic acid using an oxidizing agent such as hydrogen peroxide. This is followed by cation exchange with a triarylsulfonium halide or the like. The pivalic ester is then subjected to alkaline hydrolysis. Through reaction with (meth)acrylic anhydride, the alcohol resulting from hydrolysis is converted into a (meth)acrylic derivative, yielding the end compound. One exemplary compound may be synthesized

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

Procedure: These recurring units may be synthesized, for example, by the following method. One exemplary compound may be synthesized by reacting 2-bromo-2,2-difluoroethanol with pivalic chloride or anhydride to form 2-bromo-2,2-difluoroethyl pivalate, converting the bromo group into sodium sulfinate using a sulfur compound such as sodium dithionite, and converting sulfinic acid into sulfonic acid using an oxidizing agent such as hydrogen peroxide. This is followed by cation exchange with a triarylsulfonium halide or the like. The pivalic ester is then subjected to alkaline hydrolysis. Through reaction with (meth)acrylic anhydride, the alcohol resulting from hydrolysis is converted into a (meth)acrylic derivative, yielding the end compound. One exemplary compound may be synthesized

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

Procedure: These recurring units may be synthesized, for example, by the following method. One exemplary compound may be synthesized by reacting 2-bromo-2,2-difluoroethanol with pivalic chloride or anhydride to form 2-bromo-2,2-difluoroethyl pivalate, converting the bromo group into sodium sulfinate using a sulfur compound such as sodium dithionite, and converting sulfinic acid into sulfonic acid using an oxidizing agent such as hydrogen peroxide. This is followed by cation exchange with a triarylsulfonium halide or the like. The pivalic ester is then subjected to alkaline hydrolysis. Through reaction with (meth)acrylic anhydride, the alcohol resulting from hydrolysis is converted into a (meth)acrylic derivative, yielding the end compound. One exemplary compound may be synthesized

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

Procedure: A glass flask equipped with a thermometer, a condenser and a dropping funnel was charged with 271 g (2.24 moles) of pivaloyl chloride, 360 g (2.23 moles) of 2-bromo-2,2-difluoroethanol and 1.5 L of diisopropyl ether, followed by stirring. Then, 318 g (3.14 moles) of triethylamine was added dropwise thereto, in an iced bath. After the termination of the dropping, stirring was conducted for 1 hour at room temperature. Then, the termination of the reaction was confirmed by gas chromatography. With the addition of 300 mL of water, a reaction solution was completely dissolved therein, followed by adding 500 mL of 2N hydrochloric acid thereto. The reaction solution was separated into an organic layer and a water layer, followed by extracting the water layer with 500 ml of diisopropyl ether. Subsequently, the organic layer was rinsed with 500 ml of saturated brine, followed by drying with anhydrous sodium sulfate. Thereafter, a solvent was distilled off, thereby obtaining 485 g (82% yield, 93% purity) of 2-bromo-2,2-difluoroethyl pivalate in the form of a light yellow liquid. A glass flask equipped with a thermometer, a condenser and a dropping funnel After the termination of the dropping, stirring a reaction solution was completely dissolved The reaction solution was separated into an organic layer by extracting the water layer with 500 ml of diisopropyl ether Subsequently, the organic layer was rinsed with 500 ml of saturated brine by drying with anhydrous sodium sulfate Thereafter, a solvent was distilled off

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

Procedure: A glass flask equipped with a thermometer, a condenser and a dropping funnel was charged with 271 g (2.24 moles) of pivaloyl chloride, 360 g (2.23 moles) of 2-bromo-2,2-difluoroethanol and 1.5 L of diisopropyl ether, followed by stirring. Then, 318 g (3.14 moles) of triethylamine was added dropwise thereto, in an iced bath. After the termination of the dropping, stirring was conducted for 1 hour at room temperature. Then, the termination of the reaction was confirmed by gas chromatography. With the addition of 300 mL of water, a reaction solution was completely dissolved therein, followed by adding 500 mL of 2N hydrochloric acid thereto. The reaction solution was separated into an organic layer and a water layer, followed by extracting the water layer with 500 ml of diisopropyl ether. Subsequently, the organic layer was rinsed with 500 ml of saturated brine, followed by drying with anhydrous sodium sulfate. Thereafter, a solvent was distilled off, thereby obtaining 485 g (82% yield, 93% purity) of 2-bromo-2,2-difluoroethyl pivalate in the form of a light yellow liquid. A glass flask equipped with a thermometer, a condenser and a dropping funnel After the termination of the dropping, stirring a reaction solution was completely dissolved The reaction solution was separated into an organic layer by extracting the water layer with 500 ml of diisopropyl ether Subsequently, the organic layer was rinsed with 500 ml of saturated brine by drying with anhydrous sodium sulfate Thereafter, a solvent was distilled off

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

Procedure: Pivalic acid chloride and 2-bromo-2,2-difluoroethanol were mixed in tetrahydrofuran and ice cooled. Triethylamine was added to the mixture. By standard separation operation and solvent distillation, 2-bromo-2,2-difluoroethyl pivalate was obtained. This compound was converted into a sodium sulfinate with sodium dithionite and then oxidized with hydrogen peroxide, yielding the target compound, sodium 2-(pivaloyloxy)-1,1-difluoroethanesulfonate. ice cooled By standard separation operation and solvent distillation

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

Procedure: 1-adamantanecarbonyl chloride and 2-bromo-2,2-difluoroethanol were mixed in tetrahydrofuran, and ice-cooled. Triethylamine was added into the mixture, and then a typical liquid separating operation and a distillation removal of solvent were conducted, to obtain 1-adamantanecarboxylic acid=2-bromo-2,2-difluoroethyl. Next, conversion into sodium sulfinate by sodium dithionite and oxidation by hydrogen peroxide were conducted for the mixture, to obtain intended sodium 2-(1-adamantanecarbonyloxy)-1,1-difluoroethanesulfonate. ice-cooled a typical liquid separating operation a distillation removal of solvent