反应详情

A stirred solution of compound 94 (9.00 g, 21.8 mmol) in phosphorus oxychloride (50 mL) was heated at 100° C. for 20 min. After cooling to room temperature, the solvent was evaporated under vacuum. The residue was poured into crushed ice (100 g). A 10% aqueous sodium hydrogenocarbonate solution (100 mL) and dichloromethane (100 mL) were added successively at 0° C. The mixture was stirred until the brown oil was totally dissolved. The solution was decanted and the aqueous layer was then extracted with dichloromethane (3×200 mL). The organic layers were combined, dried on magnesium sulfate, filtered and evaporated under reduced pressure. The residue was chromatographed (Al2O3, AcOEt/cyclohexane, 9/1, v/v) to give compound 95 (7.12 g, 16.5 mmol) as a yellow solid. Yield 76%; Rf (Al2O3, AcOEt/cyclohexane, 9/1, v/v) 0.34; mp 76-78° C.: IR (KBr) ν 1329, 1477, 1558, 1636, 2798, 2966, 3300 cm−1; 1H NMR (400 MHz, CDCl3) δ 1.01 (t, 6H, J=7.1 Hz), 2.58 (q, 4H, J=7.1 Hz), 2.70 (t, 2H, J=5.8 Hz), 3.55 (q, 2H, J=5.8 Hz), 7.39 (se, 1H), 7.73 (d, 1H, J=8.8 Hz), 7.96 (dd, 1H, J=1.8, 8.8 Hz), 8.55 (d, 1H, J=1.8 Hz), 8.93 (s, 1H); MS m/z 433 (M+2, 2), 431 (M+, 6), 417 (3), 415 (8), 317 (6), 315 (20), 289 (2), 287 (6), 189 (6), 161 (9), 128 (5), 99 (6), 86 (100), 72 (6), 56 (13).

1. customthe solvent was evaporated under vacuum
2. additionThe residue was poured
3. custominto crushed ice (100 g)
4. additionA 10% aqueous sodium hydrogenocarbonate solution (100 mL) and dichloromethane (100 mL) were added successively at 0° C
5. dissolutionwas totally dissolved
6. customThe solution was decanted
7. extractionthe aqueous layer was then extracted with dichloromethane (3×200 mL)
8. customdried on magnesium sulfate
9. filtrationfiltered
10. customevaporated under reduced pressure
11. customThe residue was chromatographed (Al2O3, AcOEt/cyclohexane, 9/1