Bromine → 4-Bromo-6-fluoro-3-hydroxy-2-nitrobenzoic acid

HRID 259936Notes

Reaction equation

HRID 259936 reaction equation
[F:1][C:2]1[C:7]([C:8]([OH:10])=[O:9])=[C:6]([N+:11]([O-:13])=[O:12])[C:5]([OH:14])=[CH:4][CH:3]=1.C([O-])(=O)C.[Na+].[Br:20]Br>C(O)(=O)C.O>[Br:20][C:4]1[CH:3]=[C:2]([F:1])[C:7]([C:8]([OH:10])=[O:9])=[C:6]([N+:11]([O-:13])=[O:12])[C:5]=1[OH:14]

Participants

6

Reactant 3

HCID 24408BromineHCID 517045Sodium AcetateHCID 450895826-Fluoro-3-hydroxy-2-nitrobenzoic acid

Product 1

HCID 541626324-Bromo-6-fluoro-3-hydroxy-2-nitrobenzoic acidYield 74.7%

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 962WaterSolvent

Procedure

6-Fluoro-3-hydroxy-2-nitrobenzoic acid (22 mg, 0.11 mmol) was dissolved in acetic acid (2 mL). Sodium acetate (10 mg, 0.12 mmol) and Br2 (10 μL, 0.19 mmol) was added and the reaction mixture was left at room temperature for 14 h. The temperature was raised to 50° and the reaction was continued for another 4 h. Evaporation gave a residue which was dissolved in water, and after adjustment of the pH the aqueous phase was extracted with EtOAc. Washing of the organic phase with water and evaporation gave a crude product which was purified by flash chromatography on SiO2. Eluation with toluene-EtOAc-HOAc afforded the product (23 mg). 1NMR (CD3OD): δ8.0 (d, J=8.7, 1H); MS (EI, 70 eV): m/z (rel. int.) 279/281 (M+, 40/38)

Workup

  1. temperatureThe temperature was raised to 50°
  2. waitthe reaction was continued for another 4 h
  3. customEvaporation
  4. customgave a residue which
  5. extractionafter adjustment of the pH the aqueous phase was extracted with EtOAc
  6. washWashing of the organic phase with water and evaporation
  7. customgave a crude product which
  8. customwas purified by flash chromatography on SiO2

Sources & evidence

ORD record
ord-5249d91b0f18421a8b8c29cc20028613
Source dataset
uspto-grants-1996_06
Patent number
US05523475

Reaction notes

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