2,3-Dichloropropene → N-(2-chloroprop-2-enyl)-N-(2-hydroxy-2-phenylethyl)-4-nitrobenzenesulfonamide

HRID 1437039Notes

Reaction equation

[OH:1][CH:2]([C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1)[CH2:3][NH:4][S:5]([C:8]1[CH:13]=[CH:12][C:11]([N+:14]([O-:16])=[O:15])=[CH:10][CH:9]=1)(=[O:7])=[O:6].[H-].[Na+].[Cl:25][C:26]([CH2:28]Cl)=[CH2:27]>CN(C=O)C>[Cl:25][C:26](=[CH2:27])[CH2:28][N:4]([CH2:3][CH:2]([OH:1])[C:17]1[CH:18]=[CH:19][CH:20]=[CH:21][CH:22]=1)[S:5]([C:8]1[CH:9]=[CH:10][C:11]([N+:14]([O-:16])=[O:15])=[CH:12][CH:13]=1)(=[O:7])=[O:6]

Participants

Conditions

Temperature: -10 °C

Procedure

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.

Workup

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

Sources & evidence

ORD record: ord-3339641e1fb6412889e2202cffe698ab
Source dataset: uspto-grants-2009_11
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07622468B2

Reaction notes

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