反应详情

温度

55 °C

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.

1. temperatureThe temperature was then increased to about 80° C
2. dissolutiondissolved
3. stirringfor stirring of the mixture
4. customNMR spectra showed that further reaction
5. temperatureto cool to ambient temperature
6. dissolutiondissolved
7. customThe layers were separated
8. additionadditional sodium dithionite (30 g) and sodium carbonate (38 g) were added to the acetonitrile layer (200 mL) along with about 100 mL of water
9. temperatureThe reaction mixture was heated at about 85° C. overnight
10. temperatureThe solution was cooled
11. filtrationfiltered
12. customthe volatiles were removed on a rotary evaporator
13. washThe resulting crunchy solid was washed with about 200 mL of ether
14. customdried under vacuum