Sodium hydride → Methanesulfonamide, N-(2-bromo-4-nitrophenyl)-

HRID 1955825Notes

Reaction equation

HRID 1955825 reaction equation
[Br:1][C:2]1[CH:8]=[C:7]([N+:9]([O-:11])=[O:10])[CH:6]=[CH:5][C:3]=1[NH2:4].[H-].[Na+].[CH3:14][S:15](Cl)(=[O:17])=[O:16]>CN(C=O)C>[N+:9]([C:7]1[CH:6]=[CH:5][C:3]([NH:4][S:15]([CH3:14])(=[O:17])=[O:16])=[C:2]([Br:1])[CH:8]=1)([O-:11])=[O:10]

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 25840Benzenamine, 2-bromo-4-nitro-HCID 31297Methanesulfonyl chloride

Product 1

HCID 6452493Methanesulfonamide, N-(2-bromo-4-nitrophenyl)-

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

Commercially available 2-bromo4-nitroaniline (10.0 g, 46.07 mmol) was dissolved in DMF (250 mL) and NaH (60% in oil dispersion; 3.7 g, 92.15 mmol) added portion wise at 0° C. After 15 minutes, methanesulfonyl chloride (10.7 mL, 138.23 mmol) was added and the reaction was stirred overnight at ambient temperature. The reaction was quenched with 1M citric acid (100 mL) and extracted with ethyl acetate (3×). The combined extracts were washed with brine (2×), dried (MgSO4), filtered and concentrated in vacuo to yield a red oil that was purified by flash chromatography (silica gel; 20% EtOAc/Hexane) to afford the title compound as a yellow solid which was recrystallyzed from ether/hexanes. mp 148°-151° C; 1H NMR (300 MHz, DMSO-d6) δ3.24 (s, 3H), 7.70 (d; J=9 Hz; 1H), 8.23 (dd; J=9, 3 Hz; 1H), 8.49 (d; J=3 Hz; 1H), 9.85 (br. s., 1H). MS (DCI-NH3) m/z 312 (M+NH4)+.

Workup

  1. customThe reaction was quenched with 1M citric acid (100 mL)
  2. extractionextracted with ethyl acetate (3×)
  3. washThe combined extracts were washed with brine (2×)
  4. dry with materialdried (MgSO4)
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customto yield a red oil that
  8. customwas purified by flash chromatography (silica gel; 20% EtOAc/Hexane)

Sources & evidence

ORD record
ord-cd1af645953c4710811a97fe723fc413
Source dataset
uspto-grants-1998_07
Patent number
US05776984

Reaction notes

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