Cyanuric chloride → 4-Bromo-2,5-difluorobenzonitrile

HRID 516549Notes

Reaction equation

HRID 516549 reaction equation
N1C(Cl)=NC(Cl)=NC=1Cl.[Br:10][C:11]1[C:19]([F:20])=[CH:18][C:14](/[CH:15]=[N:16]/O)=[C:13]([F:21])[CH:12]=1>CN(C=O)C.O>[Br:10][C:11]1[C:19]([F:20])=[CH:18][C:14]([C:15]#[N:16])=[C:13]([F:21])[CH:12]=1

Participants

5

Reactant 2

HCID 7954Cyanuric chloride2×HCID 90310471(NE)-N-[(4-bromo-2,5-difluorophenyl)methylidene]hydroxylamine

Product 1

HCID 149849124-Bromo-2,5-difluorobenzonitrileYield 68%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent2×

Procedure

A solution of cyanuric chloride (3.12 g, 16.94 mmol) and dry DMF (8.5 mL) was stirred for 30 min or until the formation of white solid. Disappearance of cyanuric chloride was confirmed by TLC. (E)-4-bromo-2,5-difluorobenzaldehyde oxime (4.0 g, 16.94 mmol) in DMF (26 mL) was added dropwise to the suspension and stirred for 1 h. The reaction mixture was diluted with water and extracted with hexanes. The organic extract was washed with water, washed with saturated brine solution, dried (Na2SO4), filtered, and evaporated to dryness under reduced pressure. The crude product was purified by flash chromatography (SiO2, eluting with 2-20% ethyl acetate in hexanes) to provide the title compound as a white solid (2.5 g, 68%): 1H NMR (400 MHz, CDCl3) δ 7.40 (dd, J=5.36, 7.10 Hz, 1H), 7.52 (dd, J=5.40, 7.66 Hz, 1H); EIMS m/z 218.

Workup

  1. extractionextracted with hexanes
  2. extractionThe organic extract
  3. washwas washed with water
  4. washwashed with saturated brine solution
  5. dry with materialdried (Na2SO4)
  6. filtrationfiltered
  7. customevaporated to dryness under reduced pressure
  8. customThe crude product was purified by flash chromatography (SiO2, eluting with 2-20% ethyl acetate in hexanes)

Sources & evidence

ORD record
ord-1e1a92b39dc64c6a9286b85c2c873bce
Source dataset
uspto-grants-2015_08
Patent number
US09113629B2

Reaction notes

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