反应详情

To a stirred solution of thymidine (24.22 g, 0.1 mol), N-hydroxyphthalimide (21.75 g, 0.13 mol), triphenylphosphine (34 g, 0.13 mol) in dry DMF (400 ml) was added diisopropylazodicarboxylate (30 ml, 0.15 mol) over a period of 3 h at 0° C. After complete addition the reaction mixture was warmed up to room temperature and stirred for 12 h. The solution was concentrated under vacuum (0.1 mm, <40° C.) to furnish an orange-red residue. The residual gum was washed several times with Et2O and washing were discarded. The semi-solid residue was suspended in EtOH (500 ml) and heated (90° C.) to dissolve the product. On cooling 30.98 g (80%) of 5'-O-phthalimidothymidine was collected in 3-crops as white crystalline material, mp 233°-235° C. (decomp.); 1H NMR (DMSO-d6) δ11.29 (s, 1, NH), 7.85 (m, 4, ARH), 7.58 (s, 1, C6H), 6.20 (t, 1, H1', J1',2' =7.8 Hz, J1',2" =6.5 Hz), 5.48 (d, 1, OH3'), 4.36 (m, 3, H4',5',5"), 4.08 (m, 1, H3'), 2.09-2.13 (m, 2, H2',2"), and 1.79 (s, 3, CH3). Anal. Calcd. for C18H17O7N3.0.7 H2O: C, 54.05; H, 4.64; N, 10.51. Found: C, 53.81; H, 4.25; N, 10.39.

1. additionAfter complete addition the reaction mixture
2. concentrationThe solution was concentrated under vacuum (0.1 mm, <40° C.)
3. customto furnish an orange-red residue
4. washThe residual gum was washed several times with Et2O
5. washwashing
6. temperatureheated (90° C.)
7. dissolutionto dissolve the product
8. temperatureOn cooling 30.98 g (80%) of 5'-O-phthalimidothymidine
9. customwas collected in 3-crops as white crystalline material, mp 233°-235° C. (decomp.)