反应详情

温度

-50 °C

A 250 ml, three-necked flask equipped with a magnetic stir bar, a low-temperature thermometer, a condenser filled with dry ice/acetone, and a balloon is charged with dry THF (100 mL). The flask is cooled to approximately −50° C. and tetrafluoroethylene is passed through a tube of silica and then through a needle into the THF until saturation is reached (as judged by inflation of the balloon). The flask is allowed to warm to −5 to −10° C. which causes the balloon to inflate slightly (most of the gas will be trapped by the condenser). To a separate 50 ml. flask is added NaH (100 mg, 4.2 mmol, 80% suspension in oil), and the oil is removed by repeated washing with dry THF under argon. A solution of previously distilled allyl alcohol (3.0 g 52 mmol) in dry THF (2 ml) is slowly added by syringe with stirring and the mixture is allowed to stir for an additional 10 min. This solution is then transferred dropwise by syringe to the three-necked flask with stirring at −5 to −10° C. After approximately 3 hr, the reaction is checked by GC (60° C.) of a small aliquot and, if needed, additional tetrafluoroethylene is bubbled into the solution for about 5 min. The product elutes just after the allyl alcohol. Further additions of tetrafluoroethylene are usually required. The addition reaction usually requires 6 hr. The reaction is then placed under argon, cooled to −60° C. and n-butyllithium (one equivalent in hexane) is added dropwise over 2 hr. from an addition funnel while the temperature is kept constant at −60° C. The mixture is cooled to −78° C., water (2 ml) is added, the cooling bath is removed and the solution is stirred overnight. The solution is basified with aqueous NaOH and the solvent removed in vacuo. The residue is acidified with 1N HCl and extracted three times with ether. The organic layers are combined and extracted with saturated NaHCO3. The aqueous extract is acidified to pH 1 with HCl and extracted three times with ether. The presence of the difluoro acid is confirmed by NMR of a small aliquot.

1. customA 250 ml, three-necked flask equipped with a magnetic stir bar
2. temperatureto warm to −5 to −10° C. which
3. customthe oil is removed
4. washby repeated washing with dry THF under argon
5. stirringto stir for an additional 10 min
6. customThis solution is then transferred dropwise by syringe to the three-necked flask
7. stirringwith stirring at −5 to −10° C
8. customis checked by GC (60° C.) of a small aliquot
9. customadditional tetrafluoroethylene is bubbled into the solution for about 5 min
10. additionThe addition reaction usually requires 6 hr
11. temperaturecooled to −60° C.
12. customfrom an addition funnel while the temperature is kept constant at −60° C
13. temperatureThe mixture is cooled to −78° C.
14. customthe cooling bath is removed
15. stirringthe solution is stirred overnight
16. customthe solvent removed in vacuo
17. extractionextracted three times with ether
18. extractionextracted with saturated NaHCO3
19. extractionThe aqueous extract
20. extractionextracted three times with ether