Cesium carbonate → 1-Bromo-4-(2,4-difluorophenoxy)-2-fluoro-5-nitrobenzene

HRID 633522Notes

Reaction equation

HRID 633522 reaction equation
[Br:1][C:2]1[CH:7]=[C:6]([N+:8]([O-:10])=[O:9])[C:5]([F:11])=[CH:4][C:3]=1[F:12].C(=O)([O-])[O-].[Cs+].[Cs+].[F:19][C:20]1[CH:25]=[C:24]([F:26])[CH:23]=[CH:22][C:21]=1[OH:27]>CS(C)=O>[Br:1][C:2]1[CH:7]=[C:6]([N+:8]([O-:10])=[O:9])[C:5]([F:11])=[CH:4][C:3]=1[O:27][C:21]1[CH:22]=[CH:23][C:24]([F:26])=[CH:25][C:20]=1[F:19].[Br:1][C:2]1[CH:7]=[C:6]([N+:8]([O-:10])=[O:9])[C:5]([O:27][C:21]2[CH:22]=[CH:23][C:24]([F:26])=[CH:25][C:20]=2[F:19])=[CH:4][C:3]=1[F:12]

Participants

6

Reactant 3

HCID 10796Cesium carbonateHCID 1230512,4-DifluorophenolHCID 2230781-Bromo-2,4-difluoro-5-nitrobenzene

Product 2

HCID 904159951-Bromo-4-(2,4-difluorophenoxy)-2-fluoro-5-nitrobenzeneHCID 904186191-Bromo-2-(2,4-difluorophenoxy)-4-fluoro-5-nitrobenzene

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent

Procedure

A mixture of 1-bromo-2,4-difluoro-5-nitrobenzene (0.5 g, 2.10 mmol) and cesium carbonate (0.685 g, 2.10 mmol) in DMSO (10.50 mL) was treated dropwise with 2,4-difluorophenol (0.273 g, 2.10 mmol), stirred for 60 minutes at ambient temperature and partitioned between ethyl acetate and water, adjusting the pH to 6 with 1 M HCl. The organic layer was washed with water, saturated aqueous sodium chloride, dried (MgSO4), filtered, and concentrated. Purification by chromatography (silica gel, 0-30% ethyl acetate in heptanes) afforded the title compound and 1-bromo-4-(2,4-difluorophenoxy)-2-fluoro-5-nitrobenzene as an inseparable mixture (0.59 g, 81%).

Workup

  1. custompartitioned between ethyl acetate and water
  2. washThe organic layer was washed with water, saturated aqueous sodium chloride
  3. dry with materialdried (MgSO4)
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customPurification by chromatography (silica gel, 0-30% ethyl acetate in heptanes)

Sources & evidence

ORD record
ord-5e93caf2891d47e6b8f113ebe17841b7
Source dataset
uspto-grants-2016_04
Patent number
US09321764B2

Reaction notes

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