Water → Methyl 4-bromo-2-nitrobenzoate

HRID 906603Notes

Reaction equation

HRID 906603 reaction equation
[Br:1][C:2]1[CH:10]=[CH:9][C:5]([C:6]([OH:8])=[O:7])=[C:4]([N+:11]([O-:13])=[O:12])[CH:3]=1.[CH3:14]I.O>CN(C)C=O>[CH3:14][O:7][C:6](=[O:8])[C:5]1[CH:9]=[CH:10][C:2]([Br:1])=[CH:3][C:4]=1[N+:11]([O-:13])=[O:12]

Participants

5

Reactant 3

HCID 962WaterHCID 6328Methyl iodideHCID 37744674-Bromo-2-nitrobenzoic acid

Product 1

HCID 18350461Methyl 4-bromo-2-nitrobenzoateYield 90.6%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
0 °C

Procedure

To solution of 4-bromo-2-nitro-benzoic acid (9 g, 36.58 mmol) in dimethylformamide (36 mL) cooled to 0° C. were added 1,8-diazabicyclo[5.4.0]und-7-ene (28.09 mL, 182.9 mmol) and MeI (11.4 mL, 182.5 mmol). The reaction mixture was stirred at 0° C. for 15 min and at r.t. for 48 h. The mixture was poured into water and extracted with EtOAc (2×). The combined organic phases were washed with water (2×), dried (Na2SO4) and concentrated to dryness. The crude product was purified by flash chromatography (hexanes to EtOAc/hexanes (4:6)) to give 4-bromo-2-nitro-benzoic acid methyl ester (8.62 g, 33.147 mmol, 90%). 1H-NMR (CDCl3, 400 MHz) 8.02 (s, 1H), 7.81 (dd, J=2.3, 10.5 Hz 1H), 7.66 (d, J=8.2 Hz, 1H), 3.92 (s, 3H).

Workup

  1. extractionextracted with EtOAc (2×)
  2. washThe combined organic phases were washed with water (2×)
  3. dry with materialdried (Na2SO4)
  4. concentrationconcentrated to dryness
  5. customThe crude product was purified by flash chromatography (hexanes to EtOAc/hexanes (4:6))

Sources & evidence

ORD record
ord-e0a5b760d57d4e39a9ba8cb32484d8e6
Source dataset
uspto-grants-2011_09
Patent number
US08012988B2

Reaction notes

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