Nitric Acid → 4-Bromo-5-fluoro-2-nitrophenol

HRID 1668351Notes

Reaction equation

HRID 1668351 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([OH:8])=[CH:4][C:3]=1[F:9].OS(O)(=O)=O.[N+:15]([O-])([OH:17])=[O:16].O>C(Cl)Cl>[Br:1][C:2]1[C:3]([F:9])=[CH:4][C:5]([OH:8])=[C:6]([N+:15]([O-:17])=[O:16])[CH:7]=1

Participants

6

Reactant 4

HCID 944Nitric AcidHCID 962WaterHCID 1118Sulfuric AcidHCID 27791534-Bromo-3-fluorophenol

Product 1

HCID 547590604-Bromo-5-fluoro-2-nitrophenolYield 45%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of 4-bromo-3-fluorophenol (89 g, 465.9 mmol) in a mixture of CH2Cl2 (940 mL) and H2SO4 (52.1 mL, 978 mmol) at 0° C., HNO3 (65%) (32.9 ml, 468 mmol) was added dropwise (the mixture turned from colourless to black). The resulting mixture was stirred at 0 ° C. for 1 h and then poured into water. The organic layer was washed with brine, dried (Na2SO4) and the solvent was evaporated under reduced pressure to afford the crude compound which was purified by flash chromatography (SiO2, heptane/toluene 1:3) to give 4-bromo-5-fluoro-2-nitrophenol (49.5 g, 45%). 1H-NMR (400 MHz, CDCl3) 6.95 (d, J=9.0, 1H), 8.38 (d, J=6.2, 1H), 10.69 (s, 1H).

Workup

  1. washThe organic layer was washed with brine
  2. dry with materialdried (Na2SO4)
  3. customthe solvent was evaporated under reduced pressure
  4. customto afford the crude compound which
  5. customwas purified by flash chromatography (SiO2, heptane/toluene 1:3)

Sources & evidence

ORD record
ord-9394bc198e574378a55663025bd0bab3
Source dataset
uspto-grants-2011_08
Patent number
US07989442B2

Reaction notes

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