反应详情

A solution of 1.1 g. of 3,5-bis(t-butyldimethylsilyloxy)-1-methanesulfonyloxy-2-desoxy-2,2difluororibose, 0.83 g. of 5-fluoro-2,4-bis(trimethylsilyloxy)pyrimidine, and 0.655 g. of trifluoromethanesulfonyloxytrimethylsilane in 20 ml. of methylene chloride was refluxed for approximately 17 hours under nitrogen. The reaction mixture was cooled to room temperature and 3 ml. of methanol was added thereto. The resulting solution was stirred for approximately 30 minutes at room temperature and the precipitated solid was collected by filtration. The filtrate was evaporated to dryness under vacuum at 50° and the residue was dissolved in 15 ml. of methylene chloride saturated with anhydrous hydrogen bromide. The resulting suspension was stirred for approximately 30 minutes and the volatiles were removed in vacuo at 45° . The residue was dissolved in 15 ml. of water and the aqueous solution was extracted one time with 10 ml. of ethyl acetate. The aqueous layer was neutralized with sodium carbonate to a pH of approximately 7 and the solution was evaporated to dryness in vacuo at 50°. The residue was dissolved in about 6 ml. of water and the resulting solution was chromatographed in 2 ml. portions on a Whatman ODS-3 50 cm reverse-phase column using water as the eluent to provide 30 mg. of 1-(5-fluoro-2,4-dioxo-1H,3H-pyrimidin-1-yl)-2-desoxy-2,2-difluorori (CD3OD, 90 MHz) δ 3.63-4.6 (m, 4H), 4.79 (s, 3H), 6.04 (t, J=7 Hz, 1H), 8.07 (d, J=6 Hz, 1H); mass spec. m/e=282 =p.

1. filtrationthe precipitated solid was collected by filtration
2. customThe filtrate was evaporated to dryness under vacuum at 50°
3. dissolutionthe residue was dissolved in 15 ml
4. stirringThe resulting suspension was stirred for approximately 30 minutes
5. customthe volatiles were removed in vacuo at 45°
6. dissolutionThe residue was dissolved in 15 ml
7. extractionof water and the aqueous solution was extracted one time with 10 ml
8. customthe solution was evaporated to dryness in vacuo at 50°
9. dissolutionThe residue was dissolved in about 6 ml
10. customof water and the resulting solution was chromatographed in 2 ml
11. customto provide 30 mg