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

HRID 1490152Notes

Reaction equation

HRID 1490152 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-bromo-4-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 (3x). The combined extracts were washed with brine (2x), 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) δ 3.24 (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 (3x)
  3. washThe combined extracts were washed with brine (2x)
  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-ba04a7f7604d49028b3a258a72bb74e9
Source dataset
uspto-grants-1997_10
Patent number
US05681842

Reaction notes

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