2,2,3,4,4,4-hexafluorobutan-1-ol

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

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

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

Conditions: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: First, 9.1 g (50 mmol) of 2,2,3,4,4,4-hexafluorobutan-1-ol was dissolved in 40 ml of water, to which 14.7 g (50 mmol) of potassium dichromate and 17 ml of concentrated sulfuric acid, and the mixture was heated at 100° C. for 3 hours. After cooling, the reaction mixture was extracted with diethyl ether. The organic layer was dried over anhydrous magnesium sulfate and then concentrated under reduced pressure to give 9.0 g of 2,2,3,4,4,4-hexafluorobutyric acid. After cooling the reaction mixture was extracted with diethyl ether The organic layer was dried over anhydrous magnesium sulfate concentrated under reduced pressure

Conditions: temp:45.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Hexafluorobutanol, CF3CFHCF2CH2OH (65.3 g, 0.34 mol), prepared essentially as described in Example 2) was combined with potassium carbonate (9.9 g, 0.072 mol) and 133 g of acetonitrile in a 600 mL Parr reactor. The temperature of the reactor was raised to 45° C. and CF3OCF═CF2 (65.6 g, 0.39 mol) added as a gas over about two hours. The resulting reaction mixture was stirred for about 18 hours at 45° C. The reactor was cooled and the contents of the reactor filtered to remove the potassium carbonate. The resulting product-containing filtrate was distilled using a concentric tube column, with the product cut boiling at 115-119° C. The product structure was confirmed by GCMS. The resulting reaction mixture The reactor was cooled the contents of the reactor filtered to remove the potassium carbonate The resulting product-containing filtrate was distilled

Conditions: temp:45.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Hexafluorobutanol, CF3CFHCF2CH2OH (65.3 g, 0.34 mol), prepared essentially as described in Example 2) was combined with potassium carbonate (9.9 g, 0.072 mol) and 133 g of acetonitrile in a 600 mL Parr reactor. The temperature of the reactor was raised to 45° C. and CF3OCF═CF2 (65.6 g, 0.39 mol) added as a gas over about two hours. The resulting reaction mixture was stirred for about 18 hours at 45° C. The reactor was cooled and the contents of the reactor filtered to remove the potassium carbonate. The resulting product-containing filtrate was distilled using a concentric tube column, with the product cut boiling at 115-119° C. The product structure was confirmed by GCMS. The resulting reaction mixture The reactor was cooled the contents of the reactor filtered to remove the potassium carbonate The resulting product-containing filtrate was distilled

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

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

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

Procedure: 2,2,3,4,4,4-hexafluorobutan-1-ol (202 g, 1.1 mol, obtained from Sinochem Corp., Beijing, China), 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonyl fluoride (332 g, 1.1 mol, obtained from 3M Company of Saint Paul, Minn.) and water (300 g) were combined in a 3-L, 3-necked round bottom flask. The flask was equipped with a magnetic stirrer, cold water condenser, thermocouple and a 250-mL addition funnel. Aqueous potassium hydroxide (149.3 g, 45 weight percent, 1.22 equivalents) was added dropwise via an addition funnel at such a rate that the temperature did not exceed 35° C. Once the addition of the base was complete the mixture was stirred for 16 hours at room temperature. The precipitated salts were then filtered from the mixture and the lower liquid fluorochemical product phase was separated from the upper aqueous phase. Unreacted 2,2,3,4,4,4-hexafluorobutan-1-ol and 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonyl fluoride were removed by atmospheric distillation. The flask was equipped with a magnetic stirrer, cold water condenser thermocouple and a 250-mL addition funnel did not exceed 35° C Once the addition of the base The precipitated salts were then filtered from the mixture the lower liquid fluorochemical product phase was separated from the upper aqueous phase were removed by atmospheric distillation

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

Procedure: 2,2,3,4,4,4-hexafluorobutan-1-ol (202 grams, 1.1 moles, Sinochem Corp.), 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonyl fluoride (332 grams, 1.1 moles, 3M Company) and water (300 g) were combined in a 3-liter, 3-necked round bottom flask. The flask was equipped with a magnetic stirrer, cold water condenser, thermocouple, and addition funnel. Aqueous potassium hydroxide, 45 percent (149.3 grams, 1.22 moles, Aldrich Chemical Co.) was added dropwise via an addition funnel at such a rate that the temperature did not exceed 35° C. Once the addition of the base was complete the mixture was stirred for 16 hours at room temperature. Precipitated salts were then filtered from the mixture and the lower liquid fluorochemical product phase was separated from the upper aqueous phase. Unreacted 2,2,3,4,4,4-hexafluorobutan-1-ol and 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonyl fluoride were removed by atmospheric distillation. Approximately 400 grams of 2,2,3,4,4,4-hexafluorobutyl 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate were recovered at a purity of 98.9 percent as measured by gas chromatographic analysis. The flask was equipped with a magnetic stirrer, cold water condenser thermocouple, and addition funnel did not exceed 35° C Once the addition of the base Precipitated salts were then filtered from the mixture the lower liquid fluorochemical product phase was separated from the upper aqueous phase were removed by atmospheric distillation Approximately 400 grams of 2,2,3,4,4,4-hexafluorobutyl 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate were recovered at a purity of 98.9 percent

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

Procedure: Example 3 was prepared by combining 2,2,3,4,4,4-hexafluorobutan-1-ol (184 g, 1.012 moles, Lancaster Synthesis Ltd., Ward Hill, Mass.), triethylamine (102 g, 1.008 moles) and methyl-t-butyl ether (350 mL) in a 1-L round bottom flask that was maintained at a temperature between 5° C. and 15° C. with a carbon dioxide/water bath. To the stirred mix, ethylchloroformate (100 g, 0.92 moles) was added from a jacketed addition funnel that was maintained between 5° C. and 15° C. The ethylchloroformate was added over a period of 4 h. Once addition was complete, the reaction mixture was stirred for an additional 16 h and was allowed to warm to room temperature. Then 100 mL of distilled water was added to the reaction mixture. The organic phase was collected. The water phase was extracted twice with 100 mL portions of methyl-t-butyl ether and all of the organic phases were combined. The organic phase was washed with a 100 mL portion of distilled water and a 100 mL portion of 1N HCl. The ether was removed by rotary evaporation. The remaining sample was purified by fractional distillation, using a concentric tube column. The product was analyzed by GC/MS. Example 3 was prepared was maintained at a temperature between 5° C. and 15° C. with a carbon dioxide/water bath To the stirred mix was maintained between 5° C. and 15° C Once addition The organic phase was collected The water phase was extracted twice with 100 mL portions of methyl-t-butyl ether The organic phase was washed with a 100 mL portion of distilled water The ether was removed by rotary evaporation The remaining sample was purified by fractional distillation

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

Procedure: The process of claim 2 comprising (a) reacting at reflux about 1 mole of 2,2,3,4,4,4-hexafluorobutanol and about 1 mole of 11-bromoundecanoic acid to obtain 2,2,3,4,4,4-hexafluorobutyl 11-bromoundecylate and then (b) reacting about 1 mole of 2,2,3,4,4,4-hexafluorobutyl 11-bromoundecylate with about 1 mole pyridine to obtain 2,2,3,4,4,4-hexafluorobutyl 11-pyridylundecylate bromide.