Allyl bromide → HCID 22168670, compound

HRID 1715110Notes

Reaction equation

HRID 1715110 reaction equation
[F:1][C:2]1[CH:10]=[CH:9][C:5]([C:6]([OH:8])=[O:7])=[CH:4][C:3]=1[N+:11]([O-:13])=[O:12].C(=O)([O-])[O-].[K+].[K+].[CH2:20](Br)[CH:21]=[CH2:22]>CN(C=O)C>[CH2:22]([O:7][C:6](=[O:8])[C:5]1[CH:9]=[CH:10][C:2]([F:1])=[C:3]([N+:11]([O-:13])=[O:12])[CH:4]=1)[CH:21]=[CH2:20]

Participants

5

Reactant 3

HCID 7841Allyl bromideHCID 11430Potassium CarbonateHCID 679874-Fluoro-3-nitrobenzoic acid

Product 1

HCID 22168670HCID 22168670, compoundYield 83.1%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a mechanically stirred solution of 4-fluoro-3-nitro-benzoic acid (113.0 g, 0.61 mol, 1.0 equiv) in DMF (770 ml) was added portionwise potassium carbonate (168.7 g, 1.22 mol, 2.0 equiv). Allyl bromide (110.8 g, 0.92 mol, 1.5 equiv) was added to the reaction mixture and stirring continued at rt overnight. The reaction mixture was filtered, the filtrate poured into water (4 L), kept for 2 h and then extracted with ethyl acetate (3×1 L). The organic layer was washed with water, dried over Na2SO4 and concentrated by evaporation under reduced pressure. The residue was purified with silica column chromatography eluting with a gradient of hexane/ethyl acetate (100:0→98:2) to obtain 114.1 g (83%) of the title compound. 1H NMR (400 MHz, DMSO): δ 4.86 (d, J=5.4 Hz, 2H), 5.30 (d, J=10.6 Hz, 1H), 5.43 (d, J=17.2, 1H), 6.01-6.10 (m, 1H), 7.73-7.78 (m, 1H), 8.34-8.37 (m, 1H), 8.60 (d, J=7.2 Hz, 1H).

Workup

  1. filtrationThe reaction mixture was filtered
  2. additionthe filtrate poured into water (4 L)
  3. waitkept for 2 h
  4. extractionextracted with ethyl acetate (3×1 L)
  5. washThe organic layer was washed with water
  6. dry with materialdried over Na2SO4
  7. concentrationconcentrated by evaporation under reduced pressure
  8. customThe residue was purified with silica column chromatography
  9. washeluting with a gradient of hexane/ethyl acetate (100:0→98:2)

Sources & evidence

ORD record
ord-c9b654953e8c402f9eea26b146949949
Source dataset
uspto-grants-2010_09
Patent number
US07799806B2

Reaction notes

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