5,5,6,6,7,7,8,8,8-nonafluorooctan-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:0.00; pressure:0.00; stir:

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

Procedure: A solution of diethyl azodicarboxylate (3.5 g, 20 mmol) in dry diethyl ether (20 cm3) was added dropwise into a stirred solution of 5,5,6,6,7,7,8,8,8-nonafluorooctan-1-ol (Preparation 2A, 5.8 g, 20 mmol), 4-bromophenol (3.5 g, 20 mmol) and triphenylphosphine (5.3 g, 20 mmol) in dry diethyl ether (50 cm3) at room temperature.

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

Procedure: A solution of diethyl azodicarboxylate (3.5 g, 20 mmol) in dry diethyl ether (20 cm3) was added dropwise into a stirred solution of 5,5,6,6,7,7,8,8,8-nonafluorooctan-1-ol (Preparation 2A, 5.8 g, 20 mmol), 4-bromophenol (3.5 g, 20 mmol) and triphenylphosphine (5.3 g, 20 mmol) in dry diethyl ether (50 cm3) at room temperature.

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

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

Procedure: To a mixture of 12.50 g of 4-(nonafluorobutyl)-1-butanol and 150 mL of 48 weight percent hydrobromic acid was slowly added 15 mL of concentrated sulfuric acid. The reaction mixture was heated at 100° C. for 18 hr, and then poured into 500 mL of water. The mixture was extracted with hexanes, and the combined organic phases were washed with saturated aqueous sodium bicarbonate and dried over anhydrous magnesium sulfate. Filtration and concentration afforded 12.50 g of crude 1-bromo-4-(nonafluorobutyl)butane as a light amber liquid, which was used without further purification. The mixture was extracted with hexanes the combined organic phases were washed with saturated aqueous sodium bicarbonate dried over anhydrous magnesium sulfate Filtration and concentration

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

Procedure: To a mixture of 12.50 g of 4-(nonafluorobutyl)-1-butanol and 150 mL of 48 weight percent hydrobromic acid was slowly added 15 mL of concentrated sulfuric acid. The reaction mixture was heated at 100° C. for 18 hr, and then poured into 500 mL of water. The mixture was extracted with hexanes, and the combined organic phases were washed with saturated aqueous sodium bicarbonate and dried over anhydrous magnesium sulfate. Filtration and concentration afforded 12.50 g of crude 1-bromo-4-(nonafluorobutyl)butane as a light amber liquid, which was used without further purification. The mixture was extracted with hexanes the combined organic phases were washed with saturated aqueous sodium bicarbonate dried over anhydrous magnesium sulfate Filtration and concentration

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

Procedure: A solution of 5,5,6,6,7,7,8,8,8-nonafluorooctan-1-ol (7.8 g, 26.70 mmol) in dichloromethane (150 ml) was cooled to 0° C. Triethylamine (9.29 ml, 66.75 mmol) and methanesulfonyl chloride (2.48 ml, 32.04 mmol) were added dropwise to the solution, followed by stirring for 1 hour. After the reaction was completed, water was added to the reaction mixture, which was then extracted twice with dichloromethane. The combined organic layers were washed with water and saturated aqueous sodium chloride, and then dried over anhydrous magnesium sulfate. After distilling off the solvent, the residue was purified by silica gel column chromatography (eluent: ethyl acetate/hexane=1/4) to give 1-methanesulfonyloxy-5,5,6,6,7,7,8,8,8-nonafluorooctane (8.5 g, Yield 86%). was then extracted twice with dichloromethane The combined organic layers were washed with water and saturated aqueous sodium chloride dried over anhydrous magnesium sulfate After distilling off the solvent the residue was purified by silica gel column chromatography (eluent: ethyl acetate/hexane=1/4)

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

Procedure: A solution of potassium hydroxide (53.59 g, 955.09 mmol) in water (200 ml) was added to a solution of diethyl 2-(3,3,4,4,5,5,6,6,6-nonafluorohexyl)malonate (19.4 g, 47.75 mmol) in ethanol (400 ml), followed by stirring for 6 hours at 60° C. After the reaction was completed, the reaction mixture was adjusted to pH 5 at room temperature by slowly adding 1N hydrochloric acid dropwise, and then extracted twice with ethyl acetate. The combined organic layers were washed with saturated aqueous sodium chloride and dried over anhydrous magnesium sulfate. After distilling off the solvent, the residue was stirred in dimethyl sulfoxide for 18 hours at 170° C. After the reaction was completed, water was added to the reaction mixture, which was then extracted three times with ethyl acetate. The combined organic layers were washed with water and saturated aqueous sodium chloride, and then dried over anhydrous magnesium sulfate. After distilling off the solvent, anhydrous tetrahydrofuran (200 ml) was added to the residue and the resulting mixture was cooled to −30° C. Borane-methyl sulfide complex (10M in THF, 8.5 ml, 85 mmol) was slowly added dropwise to this mixture, followed by stirring for 3 hours at room temperature. After treatment with methanol at 0° C., water was added to the reaction mixture, which was then extracted twice with ethyl acetate. The combined organic layers were washed with water and saturated aqueous sodium chloride, and then dried over anhydrous magnesium sulfate. After distilling off the solvent, the residue was purified by silica gel column chromatography (eluent: ethyl acetate/hexane=1/20) to give 5,5,6,6,7,7,8,8,8-nonafluorooctan-1-ol (9.4 g, Yield 60%). was adjusted to pH 5 at room temperature extracted twice with ethyl acetate The combined organic layers were washed with saturated aqueous sodium chloride dried over anhydrous magnesium sulfate After distilling off the solvent the residue was stirred in dimethyl sulfoxide for 18 hours at 170° C water was added to the reaction mixture, which was then extracted three times with ethyl acetate The combined organic layers were washed with water and saturated aqueous sodium chloride dried over anhydrous magnesium sulfate After distilling off the solvent, anhydrous tetrahydrofuran (200 ml) was added to the residue the resulting mixture was cooled to −30° C by stirring for 3 hours at room temperature was then extracted twice with ethyl acetate The combined organic layers were washed with water and saturated aqueous sodium chloride dried over anhydrous magnesium sulfate After distilling off the solvent the residue was purified by silica gel column chromatography (eluent: ethyl acetate/hexane=1/20)

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

Procedure: A solution of diethyl azodicarboxylate (3.5 g, 20 mmol) in dry diethyl ether (20 cm3) was added dropwise into a stirred solution of 5,5,6,6,7,7,8,8,8-nonafluorooctan-1-ol (Preparation 2A, 5.8 g, 20 mmol), 4-bromophenol (3.5 g, 20 mmol) and triphenylphosphine (5.3 g, 20 mmol) in dry diethyl ether (50 cm3) at room temperature.