1,3-Difluoro-2-methoxy-4-nitrobenzene → 2,6-Difluoro-3-nitrophenol

HRID 243218Notes

Reaction equation

HRID 243218 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[C:4]([F:11])[C:3]=1[O:12]C>Br.CC(O)=O.C1(C)C=CC=CC=1>[F:11][C:4]1[C:5]([N+:8]([O-:10])=[O:9])=[CH:6][CH:7]=[C:2]([F:1])[C:3]=1[OH:12]

Participants

5

Reactant 1

HCID 681577701,3-Difluoro-2-methoxy-4-nitrobenzene

Product 1

HCID 537967812,6-Difluoro-3-nitrophenol

Reagents, catalysts & solvents 3

HCID 176Acetic AcidSolventHCID 260Hydrogen BromideSolventHCID 1140TolueneSolvent

Procedure

A solution of 1,3-difluoro-2-methoxy-4-nitrobenzene (0.50 g, 2.644 mmol) in 33% HBr in AcOH (4 mL) was heated at 100° C. for 1 h using microwave irradiation. The cooled reaction mixture was diluted with toluene and concentrated in vacuo. The resulting residue was partitioned between aqueous NaHCO3 and EtOAc. The aqueous phase was acidified with 1M HCl and extracted twice with DCM. The combined DCM extracts were washed with water, dried (Na2SO4) and concentrated in vacuo affording the title compound as a buff solid (0.29 g, 63%). 1H NMR (CDCl3, 300 MHz): 7.70 (1H, ddd, J=9.5, 7.8, 5.4 Hz), 7.06 (1H, ddd, J=9.4, 9.0, 2.2 Hz), 5.61 (1H, bs)

Workup

  1. custommicrowave irradiation
  2. customThe cooled reaction mixture
  3. concentrationconcentrated in vacuo
  4. customThe resulting residue was partitioned between aqueous NaHCO3 and EtOAc
  5. extractionextracted twice with DCM
  6. washThe combined DCM extracts were washed with water
  7. dry with materialdried (Na2SO4)
  8. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-01b08e7178e64423bbd50f21c446c827
Source dataset
uspto-grants-2014_02
Patent number
US08653089B2

Reaction notes

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