反应详情

温度

60 °C

350 mg (8 mmol) of sodium hydride (as a 55% w/w dispersion in mineral oil) were added to a solution of 1.426 g (4 mmol) of 3'-O-[(1,1-dimethylethyl)dimethylsilyl]thymidine [Can. J. Chem., 56, 2768 (1978)] in 8 ml of tetrahydrofuran under an atmosphere of argon, and the resulting mixture was stirred at 60° C. for 2 hours and then allowed to cool to room temperature. A solution of 988 mg (4 mmol) of benzyl bromide in 2 ml of tetrahydrofuran was then added dropwise to the mixture, followed by 300 mg (2 mmol) of sodium iodide. The reaction mixture was then stirred at room temperature for 17 hours, after which it was freed from the solvent by distillation under reduced pressure. The concentrate was dissolved in 50 ml of ethyl acetate, and the resulting solution was washed twice each time with 50 ml of a saturated aqueous solution of sodium chloride. It was then dried over anhydrous magnesium sulfate and the solvent was distilled off under reduced pressure. The residue was dissolved in 4 ml of tetrahydrofuran, and 4 ml of a 1M tetrahydrofuran solution of tetrabutylammonium fluoride were added to the solution. The resulting mixture was then stirred at room temperature for 2 hours. At the end of this time, the solvent was removed by distillation under reduced pressure, and the residue was dissolved in 50 ml of ethyl acetate. The resulting solution was washed twice, each time with 50 ml of a saturated aqueous solution of sodium chloride. The mixture was dried over anhydrous magnesium sulfate, and then the solvent was removed by distillation under reduced pressure. The residue was purified by column chromatography through 60 g of silica gel (230-400 mesh) using a gradient elution method, with methylene chloride containing from 1 to 2.5% by volume methanol as the eluent, to give 377.7 mg (yield 23%) of the title compound.

1. temperatureto cool to room temperature
2. stirringThe reaction mixture was then stirred at room temperature for 17 hours
3. distillationafter which it was freed from the solvent by distillation under reduced pressure
4. dissolutionThe concentrate was dissolved in 50 ml of ethyl acetate
5. washthe resulting solution was washed twice each time with 50 ml of a saturated aqueous solution of sodium chloride
6. dry with materialIt was then dried over anhydrous magnesium sulfate
7. distillationthe solvent was distilled off under reduced pressure
8. dissolutionThe residue was dissolved in 4 ml of tetrahydrofuran
9. addition4 ml of a 1M tetrahydrofuran solution of tetrabutylammonium fluoride were added to the solution
10. stirringThe resulting mixture was then stirred at room temperature for 2 hours
11. customAt the end of this time, the solvent was removed by distillation under reduced pressure
12. dissolutionthe residue was dissolved in 50 ml of ethyl acetate
13. washThe resulting solution was washed twice
14. dry with materialThe mixture was dried over anhydrous magnesium sulfate
15. customthe solvent was removed by distillation under reduced pressure
16. customThe residue was purified by column chromatography through 60 g of silica gel (230-400 mesh)
17. washa gradient elution method