N-bromobutanimide → 2-[(5-Bromo-2-chloro-3-fluorophenyl)oxy]-4-(bromomethyl)-1-chloro-3-fluorobenzene

HRID 1874912Notes

Reaction equation

HRID 1874912 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([F:19])[C:5]([Cl:18])=[C:6]([O:8][C:9]2[C:14]([F:15])=[C:13]([CH3:16])[CH:12]=[CH:11][C:10]=2[Cl:17])[CH:7]=1.C1C(=O)N([Br:27])C(=O)C1>C(Cl)(Cl)(Cl)Cl.CC(N=NC(C#N)(C)C)(C#N)C>[Br:1][C:2]1[CH:3]=[C:4]([F:19])[C:5]([Cl:18])=[C:6]([O:8][C:9]2[C:14]([F:15])=[C:13]([CH2:16][Br:27])[CH:12]=[CH:11][C:10]=2[Cl:17])[CH:7]=1

Participants

5

Reactant 2

HCID 67184N-bromobutanimideHCID 684864972-[(5-Bromo-2-chloro-3-fluorophenyl)oxy]-1-chloro-3-fluoro-4-methylbenzene

Product 1

HCID 866448922-[(5-Bromo-2-chloro-3-fluorophenyl)oxy]-4-(bromomethyl)-1-chloro-3-fluorobenzeneYield 62.4%

Reagents, catalysts & solvents 2

HCID 6547AzobisisobutyronitrileCatalystHCID 5943Carbon TetrachlorideSolvent

Procedure

2-[(5-bromo-2-chloro-3-fluorophenyl)oxy]-1-chloro-3-fluoro-4-methylbenzene (13.25 g, 36.0 mmol) and NBS (6.41 g, 36.0 mmol) were combined in carbon tetrachloride (150 mL) with a catalytic amount of AIBN (0.296 g, 1.800 mmol) and stirred at reflux for 16 h. The reaction mixture was washed with water, dried over MgSO4, filtered and concentrated to dryness. The residue was purified by chromatography on 330 g silica gel eluted with 0 to 10% Et2O in hexanes to give the desired product, 2-[(5-bromo-2-chloro-3-fluorophenyl)oxy]-4-(bromomethyl)-1-chloro-3-fluorobenzene (10.04 g, 22.47 mmol, 62.4% yield), as a white solid. 1H NMR (400 MHz, DMSO-d6) δ ppm 7.53-7.67 (m, 3H), 6.78 (s, 1H), 4.75 (s, 2H).

Workup

  1. temperatureat reflux for 16 h
  2. washThe reaction mixture was washed with water
  3. dry with materialdried over MgSO4
  4. filtrationfiltered
  5. concentrationconcentrated to dryness
  6. customThe residue was purified by chromatography on 330 g silica gel
  7. washeluted with 0 to 10% Et2O in hexanes

Sources & evidence

ORD record
ord-ca351a5edb2b4d23aa0aa46920519ffa
Source dataset
uspto-grants-2012_11
Patent number
US08304419B2

Reaction notes

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