Dimethylformamide → 2,4-dibromo-6-fluorobenzaldehyde

HRID 896995Notes

Reaction equation

HRID 896995 reaction equation
C(NC(C)C)(C)C.C([Li])CCC.[Br:13][C:14]1[CH:15]=[C:16]([F:21])[CH:17]=[C:18]([Br:20])[CH:19]=1.CN(C)[CH:24]=[O:25]>C1COCC1>[Br:13][C:14]1[CH:19]=[C:18]([Br:20])[CH:17]=[C:16]([F:21])[C:15]=1[CH:24]=[O:25]

Participants

6

Reactant 4

HCID 6228DimethylformamideHCID 7912DiisopropylamineHCID 1370031,3-Dibromo-5-fluorobenzeneHCID 178418339Butyllithium

Product 1

HCID 27739672,4-dibromo-6-fluorobenzaldehyde

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Conditions

Temperature
-78 °C

Procedure

In a flame-dried 250 mL round-bottomed flask equipped with an addition funnel and magnetic stirrer, a mixture of diisopropylamine (4.82 mL, 34.66 mmol) in 100 mL of anhydrous THF was cooled to −78° C. and treated with 2.5N n-butyllithium (13.86 mL, 34.66 mmol) in THF, dropwise. After stirring for 10 minutes a mixture of 3,5-dibromo-1-fluorobenzene (8.0 g, 31.51 mmol) in 16 mL of THF was added dropwise and stirring was continued for an additional 30 minutes. At this point, N,N-dimethylformamide (DMF) (2.68 mL, 34.66 mmol) was added dropwise and stirring continued another 10 minutes at −78° C. The reaction was quenched with saturated aqueous ammonium chloride and the solvent removed on a rotary evaporator. The residue was dissolved in ether, washed with saturated brine and dried over calcium sulfate, filtered and concentrated to an oil, 7.36 g. Purification by flash chromatography using ethyl acetate-hexanes (1:99) gave the title product as a white solid.

Workup

  1. customIn a flame-dried 250 mL round-bottomed flask equipped with an addition funnel and magnetic stirrer
  2. additionwas added dropwise
  3. stirringstirring
  4. waitwas continued for an additional 30 minutes
  5. stirringstirring
  6. waitcontinued another 10 minutes at −78° C
  7. customThe reaction was quenched with saturated aqueous ammonium chloride
  8. customthe solvent removed on a rotary evaporator
  9. dissolutionThe residue was dissolved in ether
  10. washwashed with saturated brine
  11. dry with materialdried over calcium sulfate
  12. filtrationfiltered
  13. concentrationconcentrated to an oil, 7.36 g
  14. customPurification by flash chromatography

Sources & evidence

ORD record
ord-cecf2f5f95d44224b152c799003d4db3
Source dataset
uspto-grants-2005_07
Patent number
US06921760B2

Reaction notes

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