反应详情

温度

-10 °C

N-(2-hydroxy-2-phenylethyl)-4-nitrobenzenesulfonamide (1-2), 10.0 g, 31 mmol) was placed in a flame-dried 500 mL round bottom flask and dissolved in anhydrous DMF (100 mL). The resulting solution was cooled to −10° C. and treated with NaH (0.9 g, 37 mmol). The resulting bright orange suspension was stirred 30 min at −10° C. 2,3-dichloropropene (3.9 mL, 40 mmol) was added neat dropwise and the reaction immediately turned dark brown. N-Tetrabutylammonium iodide (100 mg, catalytic) was added and the reaction was removed from the ice/acetone bath and warmed to 25° C. The reaction was stirred overnight prior to, quenching with 5% NH4Cl (200 mL) and extraction with EtOAc (3×100 mL). The combined organic layers were washed with H2O (3×100 mL) and NaCl (sat. aq.) prior to drying with MgSO4 and filtration. Concentration under reduced pressure produced an amber oil that was purified by flash column chromatography (SiO2, 0-60% EtOAc/hexanes gradient over 30 min) to yield N-(2-chloroprop-2-enyl)-N-(2-hydroxy-2-phenylethyl)-4-nitrobenzenesulfonamide (1-3) as a light orange oil. 1H NMR (300 MHz, CDCl3) δ 8.31 (d, J=8.8 Hz, 2H), 8.02 (d, J=8.8 Hz, 2H), 7.34 (m, 5H), 5.36 (s, 2H), 5.01 (dd, J=8.0, 4.0 Hz, 1H), 4.25 (d, J=16.2 Hz, 1H), 4.10 (d, J=16.2 Hz, 1H), 3.42 (m, 2H), 2.80 (br s, 1H); MS 379.3 found 379.8 (M−H2O) required.

1. customthe reaction immediately turned dark brown
2. customthe reaction was removed from the ice/acetone bath
3. temperaturewarmed to 25° C
4. stirringThe reaction was stirred overnight
5. customto, quenching with 5% NH4Cl (200 mL) and extraction with EtOAc (3×100 mL)
6. washThe combined organic layers were washed with H2O (3×100 mL) and NaCl (sat. aq.)
7. dry with materialto drying with MgSO4 and filtration
8. concentrationConcentration under reduced pressure
9. customproduced an amber oil that
10. customwas purified by flash column chromatography (SiO2, 0-60% EtOAc/hexanes gradient over 30 min)