2,2,3,3,4,4,5,5-octafluoropentan-1-ol

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:277.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: The same catalyst was used from Example 4 above. The reactor was cooled to 277° C. The alcohol (CF3CF2CH2OH) flow of 0.49 mL/hr (2.0 sccm, 3.3×10-8 m3 /s), the COCl2 flow of 3.0 sccm (5.0×10-8 m3 /s), the HF flow of 7.0 sccm (1.2×10-7 m3 /s), and an N2 flow of 2 sccm (3.3×10-8 m3 /s) were begun. The gaseous effluent was analyzed by GCMS and found to be 89.3-90.5% CF3CF2CH2F over a 2 hour period with no evidence for catalyst deactivation. over a 2 hour

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a mixture of 2,3,4,5,6-pentafluorobenzoic acid (1 g) and 2,2,3,3,4,4,5,5-octafluoropentanol (1.18 g) in N,N-dimethylformamide (5 ml) was added 62% sodium hydride (0.39 g) at room temperature. The mixture was stirred at the same temperature for 1 hour, and thereto was added a mixture of water and ethyl acetate. The separated organic layer was washed with water and brine, dried over magnesium sulfate, filtered, and evaporated in vacuo. The residue was purified by chromatography on silica gel to give 4-(2,2,3,3,4,4,5,5-octafluoropentyloxy)-2,3,5,6-tetrafluorobenzoic acid (923.0 mg). was added The separated organic layer was washed with water and brine dried over magnesium sulfate filtered evaporated in vacuo The residue was purified by chromatography on silica gel

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a mixture of 2,3,4,5,6-pentafluorobenzoic acid (1 g) and 2,2,3,3,4,4,5,5-octafluoropentanol (1.18 g) in N,N-dimethylformamide (5 ml) was added 62% sodium hydride (0.39 g) at room temperature. The mixture was stirred at the same temperature for 1 hour, and thereto was added a mixture of water and ethyl acetate. The separated organic layer was washed with water and brine, dried over magnesium sulfate, filtered, and evaporated in vacuo. The residue was purified by chromatography on silica gel to give 4-(2,2,3,3,4,4,5,5-octafluoropentyloxy)-2,3,5,6-tetrafluorobenzoic acid (923.0 mg). was added The separated organic layer was washed with water and brine dried over magnesium sulfate filtered evaporated in vacuo The residue was purified by chromatography on silica gel

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 50 g of H(CF2)4CH2OH was dissolved in 100 ml of dimethyl sulfoxide (DMSO). 22.4 g of sodium hydroxide was added with stirring, and then 33 g of allyl chloride was dded slowly at room temperature over 2 hours. Stirring was continued for 5 hours. After filtration of precipitates, the solution was heated on a water bath to remove unreacted allyl chloride. The solution was poured into a large amount of water to separate H(CF2)4CH2OCH2 --CH=CH2. A small quantity of BPO of the order of mg was added to H(CF2)4CH2OCH2 --CH=CH2, and then thiolacetic acid was added with stirring at room temperature over 2 hours. Unreacted thiolacetic acid was removed under reduced pressure. 100 cc of methanol and 10 g of sodium hydroxide were added, and reaction was carried out at 60° C. for 3 hours. After cooling to room temperature, the reaction product was poured into a large amount of water to give crude H(CF2)4CH2OCH2CH2CH2SH. Upon distillation, there was obtained a purified product having bp. 57° C./3 mmHg. The structure of this compound was confirmed by 1H--NMR. Stirring After filtration of precipitates the solution was heated on a water bath to remove unreacted allyl chloride The solution was poured into a large amount of water to separate H(CF2)4CH2OCH2 --CH=CH2 A small quantity of BPO of the order of mg was added to H(CF2)4CH2OCH2 --CH=CH2 thiolacetic acid was added with stirring at room temperature over 2 hours was removed under reduced pressure 100 cc of methanol and 10 g of sodium hydroxide were added reaction was carried out at 60° C. for 3 hours

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 50 g of H(CF2)4CH2OH was dissolved in 100 ml of dimethyl sulfoxide (DMSO). 22.4 g of sodium hydroxide was added with stirring, and then 33 g of allyl chloride was dded slowly at room temperature over 2 hours. Stirring was continued for 5 hours. After filtration of precipitates, the solution was heated on a water bath to remove unreacted allyl chloride. The solution was poured into a large amount of water to separate H(CF2)4CH2OCH2 --CH=CH2. A small quantity of BPO of the order of mg was added to H(CF2)4CH2OCH2 --CH=CH2, and then thiolacetic acid was added with stirring at room temperature over 2 hours. Unreacted thiolacetic acid was removed under reduced pressure. 100 cc of methanol and 10 g of sodium hydroxide were added, and reaction was carried out at 60° C. for 3 hours. After cooling to room temperature, the reaction product was poured into a large amount of water to give crude H(CF2)4CH2OCH2CH2CH2SH. Upon distillation, there was obtained a purified product having bp. 57° C./3 mmHg. The structure of this compound was confirmed by 1H--NMR. Stirring After filtration of precipitates the solution was heated on a water bath to remove unreacted allyl chloride The solution was poured into a large amount of water to separate H(CF2)4CH2OCH2 --CH=CH2 A small quantity of BPO of the order of mg was added to H(CF2)4CH2OCH2 --CH=CH2 thiolacetic acid was added with stirring at room temperature over 2 hours was removed under reduced pressure 100 cc of methanol and 10 g of sodium hydroxide were added reaction was carried out at 60° C. for 3 hours

反応条件: temp:277.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: The same catalyst was used from Example 4 above. The reactor was cooled to 277° C. The alcohol (CF3CF2CH2OH) flow of 0.49 mL/hr (2.0 sccm, 3.3×10-8 m3 /s), the COCl2 flow of 3.0 sccm (5.0×10-8 m3 /s), the HF flow of 7.0 sccm (1.2×10-7 m3 /s), and an N2 flow of 2 sccm (3.3×10-8 m3 /s) were begun. The gaseous effluent was analyzed by GCMS and found to be 89.3-90.5% CF3CF2CH2F over a 2 hour period with no evidence for catalyst deactivation. over a 2 hour

反応条件: temp:277.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: The same catalyst was used from Example 4 above. The reactor was cooled to 277° C. The alcohol (CF3CF2CH2OH) flow of 0.49 mL/hr (2.0 sccm, 3.3×10-8 m3 /s), the COCl2 flow of 3.0 sccm (5.0×10-8 m3 /s), the HF flow of 7.0 sccm (1.2×10-7 m3 /s), and an N2 flow of 2 sccm (3.3×10-8 m3 /s) were begun. The gaseous effluent was analyzed by GCMS and found to be 89.3-90.5% CF3CF2CH2F over a 2 hour period with no evidence for catalyst deactivation. over a 2 hour

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 60 mL of acetic acid, 0.46 g sodium nitrite, TEMPO (0.35 g), CH3CO2Na (6.88 g) and 6.5 g of 2,2,3,3,4,4,5,5-octafluoro-pentan-1-ol were placed in a 100 mL1 glass flask equipped with a balloon containing oxygen, a reflux condenser and a stirrer. The mixture was stirred for 16 hr at 60° C. upon which the mixture was acidified as described in example 17 and extracted with diethyl ether (three times). The combined organic phases were washed with water and dried over magnesium sulfate. The solvent was removed at a rotary evaporator and the residue was distilled to give 3.82 g of acid (20 mmHg, 65° C.). Yield: 55%. equipped with a balloon extracted with diethyl ether (three times) The combined organic phases were washed with water dried over magnesium sulfate The solvent was removed at a rotary evaporator the residue was distilled

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 5.2 ml water, 19 ml MeCN, 0.34 g KBr, TEMPO (0.12 g), and 6 g of 2,2,3,3,4,4,5,5-octafluoro-pentan-1-ol were placed in a 100 mL glass flask equipped with a dropping funnel and stirrer. 45 mL of 15% (wt) aq. NaOCl buffered to pH 8-9 were added via the dropping funnel in 3 portions over two days while stirring at room temperature. Then concentrated sulphuric acid were added to render the reaction mixture acidic. (pH 1-2). The reaction mixture was extracted three times with diethyl ether and the combined organic phases were dried over magnesium sulphate. The solvent was evaporated to give a colorless liquid (8.98 g), which was distilled using a water pump (15 mmHg, 73° C.) to give 5.13 g of the acid. Yield: 80%. 1H NMR (CDCl3): 6.08 (tt, J=52 Hz, J=5.3 Hz, 1H); 8.6 (s, 1H); 19F NMR (CDCl3): −120.6 (t, J=9.2 Hz, 2F); −125.81 (m, 2F); −130.61 (m, 2F); −138.4 (dm, J=52 Hz, 2F). equipped with a dropping funnel and stirrer were added via the dropping funnel in 3 portions over two days The reaction mixture was extracted three times with diethyl ether the combined organic phases were dried over magnesium sulphate The solvent was evaporated

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 5.2 ml water, 19 ml MeCN, 0.34 g KBr, TEMPO (0.12 g), and 6 g of 2,2,3,3,4,4,5,5-octafluoro-pentan-1-ol were placed in a 100 mL glass flask equipped with a dropping funnel and stirrer. 45 mL of 15% (wt) aq. NaOCl buffered to pH 8-9 were added via the dropping funnel in 3 portions over two days while stirring at room temperature. Then concentrated sulphuric acid were added to render the reaction mixture acidic. (pH 1-2). The reaction mixture was extracted three times with diethyl ether and the combined organic phases were dried over magnesium sulphate. The solvent was evaporated to give a colorless liquid (8.98 g), which was distilled using a water pump (15 mmHg, 73° C.) to give 5.13 g of the acid. Yield: 80%. 1H NMR (CDCl3): 6.08 (tt, J=52 Hz, J=5.3 Hz, 1H); 8.6 (s, 1H); 19F NMR (CDCl3): −120.6 (t, J=9.2 Hz, 2F); −125.81 (m, 2F); −130.61 (m, 2F); −138.4 (dm, J=52 Hz, 2F). equipped with a dropping funnel and stirrer were added via the dropping funnel in 3 portions over two days The reaction mixture was extracted three times with diethyl ether the combined organic phases were dried over magnesium sulphate The solvent was evaporated