反应详情

温度

-78 °C

Anhydrous tetrahydrofuran (10 ml) was added to (4S,5R)-3,4-dimethyl-1-(5,5,6,6,7,7,8,8,8-nonafluorooctanoyl)-5-phenylimidazolidin-2-one (1.20 g, 2.5 mmol) under nitrogen atmosphere, and the resulting mixture was cooled to −78° C. Lithium bis(trimethylsilyl)amide (2.75 ml, 1.0 M in tetrahydrofuran, 2.75 mmol) was added to the mixture, which was then stirred for 1 hour. After addition of 8-bromo-1-octene (714 mg, 3.0 mmol) and HMPA (1.25 ml) at −78° C., the reaction mixture was warmed with stirring up to −50° C. over 2 hours and up to 0° C. over 30 minutes, and then stirred for 12 hours at 0° C. The reaction mixture was quenched with saturated aqueous ammonium chloride at 0° C., and then extracted with a mixed solvent of ethyl acetate and n-hexane (3:7). The organic layer was washed sequentially with saturated aqueous potassium bisulfate, saturated aqueous sodium chloride, saturated aqueous sodium bicarbonate and saturated aqueous sodium chloride, dried over anhydrous magnesium sulfate, and then filtered. The filtrate was concentrated under reduced pressure using an evaporator and the resulting residue was purified by silica gel column chromatography (Kanto Kagaku, silica gel 60 (spherical, neutral), 40–100 μm, eluent: ethyl acetate/n-hexane=1/5 3/7) to give (4S,5R)-3,4-dimethyl-1-[(2R)-2-(3,3,4,4,5,5,6,6,6-nonafluorohexyl)-9-decenoyl]-5-phenylimidazolidin-2-one (1.37 g, Yield 93%).

1. temperaturethe reaction mixture was warmed
2. stirringwith stirring up to −50° C. over 2 hours and up to 0° C. over 30 minutes
3. stirringstirred for 12 hours at 0° C
4. customThe reaction mixture was quenched with saturated aqueous ammonium chloride at 0° C.
5. extractionextracted with a mixed solvent of ethyl acetate and n-hexane (3:7)
6. washThe organic layer was washed sequentially with saturated aqueous potassium bisulfate, saturated aqueous sodium chloride, saturated aqueous sodium bicarbonate and saturated aqueous sodium chloride
7. dry with materialdried over anhydrous magnesium sulfate
8. filtrationfiltered
9. concentrationThe filtrate was concentrated under reduced pressure
10. customan evaporator
11. customthe resulting residue was purified by silica gel column chromatography (Kanto Kagaku, silica gel 60 (spherical, neutral), 40–100 μm, eluent: ethyl acetate/n-hexane=1/5 3/7)