反应详情

温度

0 °C

H2O2 (70%, 0.49 mL, ca. 9.7 mmol) was added dropwise to a stirred solution of TFAA (1.4 mL, 9.7 mmol) in DCM (10 mL) at 0° C. The solution was stirred at 0° C. for 5 min, warmed to 20° C. for 10 min, then cooled to 0° C. and added to a stirred solution of 1-oxide 102 (320 mg, 1.0 mmol) and TFA (0.38 mL, 4.9 mmol) in DCM (20 mL) at 0° C. The solution was stirred at 20° C. for 4 h, diluted with dilute aqueous NH3 solution (10 mL) and extracted with CHCl3 (4×30 mL). The combined organic fraction was dried and the solvent evaporated. The residue was purified by chromatography, eluting with a gradient (0-5%) of MeOH/DCM, to give 1,4-dioxide 104 (148 mg, 44%) as a red solid: mp (MeOH/DCM) 119-121° C.; 1H NMR δ 8.27 (s, 1H, H-9), 8.23 (s, 1H, H-5), 3.45 (br t, J=4.5 Hz, 4H, 2×CH2O), 3.21-3.33 (m, 4H, 2×CH2), 2.68-2.81 (m, 3H, H-7, CH2), 2.48 (t, J=6.5 Hz, 2H, CH2N), 2.37 (br t, J=4.5 Hz, 4H, 2×CH2N), 2.06-2.13 (m, 2H, CH2), 1.20 (d, J=6.4 Hz, 3H, CH3); 13C NMR δ 155.2, 154.7, 150.2, 139.1, 133.8, 115.9, 113.9, 67.0 (2), 58.0, 53.5 (2), 41.4, 40.8, 35.0, 28.8, 21.8, 20.1. Anal. calcd for C18H24N4O3.¼CH3OH: C, 62.2; H, 7.2; N, 15.9. Found: C, 62.3; H, 7.0; N, 16.0%.

1. temperaturewarmed to 20° C. for 10 min
2. temperaturecooled to 0° C.
3. stirringThe solution was stirred at 20° C. for 4 h
4. extractionextracted with CHCl3 (4×30 mL)
5. customThe combined organic fraction was dried
6. customthe solvent evaporated
7. customThe residue was purified by chromatography
8. washeluting with a gradient (0-5%) of MeOH/DCM