4-bromo-3,3,4,4-tetrafluorobutan-1-ol

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

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

Conditions: temp:55.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 4-Bromo-3,3,4,4-tetrafluoro-1-butanol (19.92 g, 88.54 mmol) was added to a slurry of NaHCO3 (22.31 g, 265.6 mmol) and Na2S2O4 (46.25 g, 265.6 mmol) in 60 mL of acetonitrile and 88 mL of water. The mixture was heated at about 55° C. for two days in a wax bath without stirring due to the large amount of solids present. 19F NMR spectra showed almost no conversion to product. The temperature was then increased to about 80° C. As the temperature increased, sufficient of the inorganic salts (NaHCO3 and Na2S2O4) dissolved to allow for stirring of the mixture. Additional sodium dithionite (17 g) and sodium bicarbonate (15 g) were added. NMR spectra showed that further reaction had occurred. The reaction mixture was allowed to cool to ambient temperature and additional water (100 mL) and acetonitrile (100 mL) were added so that all the solid material dissolved. NMR spectra were taken of each layer. The aqueous layer contains sulfinate and perhaps a small amount of sulfonate, but no starting bromide, while the acetonitrile layer shows a considerable amount of starting material. The layers were separated. The aqueous layer was set aside, and additional sodium dithionite (30 g) and sodium carbonate (38 g) were added to the acetonitrile layer (200 mL) along with about 100 mL of water. The reaction mixture was heated at about 85° C. overnight. The solution was cooled, filtered, combined with the previously separated aqueous layer, and the volatiles were removed on a rotary evaporator. The resulting crunchy solid was washed with about 200 mL of ether and dried under vacuum. The temperature was then increased to about 80° C dissolved for stirring of the mixture NMR spectra showed that further reaction to cool to ambient temperature dissolved The layers were separated additional sodium dithionite (30 g) and sodium carbonate (38 g) were added to the acetonitrile layer (200 mL) along with about 100 mL of water The reaction mixture was heated at about 85° C. overnight The solution was cooled filtered the volatiles were removed on a rotary evaporator The resulting crunchy solid was washed with about 200 mL of ether dried under vacuum

Conditions: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 1 L reactor was charged with 100.0 g (0.44 mole/1.0 equivalent) of 4-bromo-3,3,4,4-tetrafluorobutan-1-ol, 300 g of acetonitrile, 250 g of water, 108.2 g (0.62 mole/1.4 equivalent) of sodium dithionite and 53.4 g (0.52 mole/1.2 equivalents) of triethylamine, followed by 4 hours of stirring at 60° C. Upon confirming the termination of the reaction, the reaction liquid underwent cooling and 100 mL of 1N HCl was added thereto, followed by stirring. Subsequently, an organic layer was separated, and then the organic layer was subjected to distillation of the solvent, thereby obtaining 264 g of a target triethylammonium 1,1,2,2-tetrafluoro-4-hydroxy-butane-1-sulfinate. It exhibited a purity of 46% and a yield of 88% at this time. the termination of the reaction the reaction liquid underwent cooling by stirring Subsequently, an organic layer was separated the organic layer was subjected to distillation of the solvent

Conditions: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 1 L reactor was charged with 100.0 g (0.44 mole/1.0 equivalent) of 4-bromo-3,3,4,4-tetrafluorobutan-1-ol, 300 g of acetonitrile, 250 g of water, 108.2 g (0.62 mole/1.4 equivalent) of sodium dithionite and 53.4 g (0.52 mole/1.2 equivalents) of triethylamine, followed by 4 hours of stirring at 60° C. Upon confirming the termination of the reaction, the reaction liquid underwent cooling and 100 mL of 1N HCl was added thereto, followed by stirring. Subsequently, an organic layer was separated, and then the organic layer was subjected to distillation of the solvent, thereby obtaining 264 g of a target triethylammonium 1,1,2,2-tetrafluoro-4-hydroxy-butane-1-sulfinate. It exhibited a purity of 46% and a yield of 88% at this time. the termination of the reaction the reaction liquid underwent cooling by stirring Subsequently, an organic layer was separated the organic layer was subjected to distillation of the solvent

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

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

Procedure: A 2 litter reactor was charged with 151 g (0.67 mol) of 4-bromo-3,3,4,4-tetrafluorobutan-1-ol, 600 ml of acetonitrile, 600 ml of water, 112 g (1.33 mol/2.0 equivalent)) of sodium hydrogencarbonate, and 235 g (1.35 mol/2.0 equivalent) of sodium dithionite in a nitrogen stream. The mixture was stirred at room temperature for 12 hours. The reaction solution was extracted four times with 500 ml of acetonitrile. The solvent was evaporated from the resulting organic layer to obtain 120 g of the target sodium 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sulfinate. The purity of the product was 80% and the yield was 77%. The reaction solution was extracted four times with 500 ml of acetonitrile The solvent was evaporated from the resulting organic layer

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

Procedure: A 2 litter reactor was charged with 151 g (0.67 mol) of 4-bromo-3,3,4,4-tetrafluorobutan-1-ol, 600 ml of acetonitrile, 600 ml of water, 112 g (1.33 mol/2.0 equivalent)) of sodium hydrogencarbonate, and 235 g (1.35 mol/2.0 equivalent) of sodium dithionite in a nitrogen stream. The mixture was stirred at room temperature for 12 hours. The reaction solution was extracted four times with 500 ml of acetonitrile. The solvent was evaporated from the resulting organic layer to obtain 120 g of the target sodium 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sulfinate. The purity of the product was 80% and the yield was 77%. The reaction solution was extracted four times with 500 ml of acetonitrile The solvent was evaporated from the resulting organic layer

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

Procedure: Also, the sulfonic acid salt of formula (1) can be synthesized by starting with 4-bromo-3,3,4,4-tetrafluoro-1-butene which is readily available in the industry, effecting hydroboration with a borane such as 9-borabicyclo[3.3.1]-nonane (9-BBN) in a solvent such as n-hexane or tetrahydrofuran by a standard technique, treating the product with an oxidizing agent such as aqueous hydrogen peroxide in the presence of a base such as sodium hydroxide to form 4-bromo-3,3,4,4-tetrafluorobutanol, and esterifying it with carboxylic halide in the presence of a base such as triethylamine.

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

Procedure: Also, the sulfonic acid salt of formula (1) can be synthesized by starting with 4-bromo-3,3,4,4-tetrafluoro-1-butene which is readily available in the industry, effecting hydroboration with a borane such as 9-borabicyclo[3.3.1]-nonane (9-BBN) in a solvent such as n-hexane or tetrahydrofuran by a standard technique, treating the product with an oxidizing agent such as aqueous hydrogen peroxide in the presence of a base such as sodium hydroxide to form 4-bromo-3,3,4,4-tetrafluoro-1-butanol, followed by conversion into a sulfinic acid form and subsequently into a sulfonic acid form.

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

Procedure: Also, the sulfonic acid salt of formula (1) can be synthesized by starting with 4-bromo-3,3,4,4-tetrafluoro-1-butene which is readily available in the industry, effecting hydroboration with a borane such as 9-borabicyclo[3.3.1]nonane (9-BBN) in a solvent such as n-hexane or tetrahydrofuran by a standard technique, treating the product with an oxidizing agent such as aqueous hydrogen peroxide in the presence of a base such as sodium hydroxide to form 4-bromo-3,3,4,4-tetrafluoro-1-butanol, followed by conversion into a sulfonic acid form and subsequently into a sulfonic acid form.

Conditions: temp:55.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 4-Bromo-3,3,4,4-tetrafluoro-1-butanol (19.92 g, 88.54 mmol) was added to a slurry of NaHCO3 (22.31 g, 265.6 mmol) and Na2S2O4 (46.25 g, 265.6 mmol) in 60 mL of acetonitrile and 88 mL of water. The mixture was heated at about 55° C. for two days in a wax bath without stirring due to the large amount of solids present. 19F NMR spectra showed almost no conversion to product. The temperature was then increased to about 80° C. As the temperature increased, sufficient of the inorganic salts (NaHCO3 and Na2S2O4) dissolved to allow for stirring of the mixture. Additional sodium dithionite (17 g) and sodium bicarbonate (15 g) were added. NMR spectra showed that further reaction had occurred. The reaction mixture was allowed to cool to ambient temperature and additional water (100 mL) and acetonitrile (100 mL) were added so that all the solid material dissolved. NMR spectra were taken of each layer. The aqueous layer contains sulfinate and perhaps a small amount of sulfonate, but no starting bromide, while the acetonitrile layer shows a considerable amount of starting material. The layers were separated. The aqueous layer was set aside, and additional sodium dithionite (30 g) and sodium carbonate (38 g) were added to the acetonitrile layer (200 mL) along with about 100 mL of water. The reaction mixture was heated at about 85° C. overnight. The solution was cooled, filtered, combined with the previously separated aqueous layer, and the volatiles were removed on a rotary evaporator. The resulting crunchy solid was washed with about 200 mL of ether and dried under vacuum. The temperature was then increased to about 80° C dissolved for stirring of the mixture NMR spectra showed that further reaction to cool to ambient temperature dissolved The layers were separated additional sodium dithionite (30 g) and sodium carbonate (38 g) were added to the acetonitrile layer (200 mL) along with about 100 mL of water The reaction mixture was heated at about 85° C. overnight The solution was cooled filtered the volatiles were removed on a rotary evaporator The resulting crunchy solid was washed with about 200 mL of ether dried under vacuum