Dimethylformamide → 2-Bromo-3-fluoro-6-nitroaniline

HRID 1056097Notes

Reaction equation

HRID 1056097 reaction equation
[Br:1][C:2]1[C:7](F)=[C:6]([N+:9]([O-:11])=[O:10])[CH:5]=[CH:4][C:3]=1[F:12].C(=O)([O-])[O-].[NH4+].[NH4+].C[N:20](C=O)C.CCN(CC)CC>O>[Br:1][C:2]1[C:3]([F:12])=[CH:4][CH:5]=[C:6]([N+:9]([O-:11])=[O:10])[C:7]=1[NH2:20]

Participants

6

Reactant 4

HCID 6228DimethylformamideHCID 8471TriethylamineHCID 517111Ammonium CarbonateHCID 137327452-Bromo-1,3-difluoro-4-nitrobenzene

Product 1

HCID 194297802-Bromo-3-fluoro-6-nitroanilineYield 97%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

Prepared according to WO 2010/046388. 2-Bromo-1,3-difluoro-4-nitrobenzene (600a) (27.15 g, 114 mmol) was treated with ammonium carbonate (Sigma Aldrich, 10.96 g, 114 mmol) and DMF (200 mL) followed by Et3N (47.7 mL, 342 mmol) and stirred at RT for 48 h. The mixture was treated with water and extracted with DCM (300 mL). The DCM layer was washed with water (3×200 mL) and brine (3×200 mL), dried over MgSO4, filtered and concentrated affording crude 2-bromo-3-fluoro-6-nitroaniline (25.99 g, 111 mmol, 97% yield) as a bright yellow amorphous solid. 1H NMR (400 MHz, CDCl3) δ ppm 8.22 (1H, dd, J=9.6, 5.9 Hz), 6.81 (2H, br. s.), 6.56 (2H, dd, J=9.6, 7.2 Hz). 19F NMR (376 MHz, CDCl3) δ ppm −90.92 (1F, s). m/z (ESI, +ve ion) 234.9/236.9 (M+H)+.

Workup

  1. customPrepared
  2. extractionextracted with DCM (300 mL)
  3. washThe DCM layer was washed with water (3×200 mL) and brine (3×200 mL)
  4. dry with materialdried over MgSO4
  5. filtrationfiltered
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-3c5dabb38be2424597224e6292c334db
Source dataset
uspto-grants-2016_07
Patent number
US09394297B2

Reaction notes

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