N-bromobutanimide → 3-{[3-(Bromomethyl)-6-chloro-2-fluorophenyl]oxy}-2,5-dichlorobenzonitrile

HRID 1874894Notes

Reaction equation

HRID 1874894 reaction equation
[Cl:1][C:2]1[C:9]([O:10][C:11]2[C:16]([Cl:17])=[CH:15][CH:14]=[C:13]([CH3:18])[C:12]=2[F:19])=[CH:8][C:7]([Cl:20])=[CH:6][C:3]=1[C:4]#[N:5].C1C(=O)N([Br:28])C(=O)C1>C(Cl)(Cl)(Cl)Cl.CC(N=NC(C#N)(C)C)(C#N)C>[Br:28][CH2:18][C:13]1[C:12]([F:19])=[C:11]([O:10][C:9]2[C:2]([Cl:1])=[C:3]([CH:6]=[C:7]([Cl:20])[CH:8]=2)[C:4]#[N:5])[C:16]([Cl:17])=[CH:15][CH:14]=1

Participants

5

Reactant 2

HCID 67184N-bromobutanimideHCID 684840922,5-Dichloro-3-[(6-chloro-2-fluoro-3-methylphenyl)oxy]benzonitrile

Product 1

HCID 684833023-{[3-(Bromomethyl)-6-chloro-2-fluorophenyl]oxy}-2,5-dichlorobenzonitrileYield 51.7%

Reagents, catalysts & solvents 2

HCID 6547AzobisisobutyronitrileCatalystHCID 5943Carbon TetrachlorideSolvent

Procedure

2,5-dichloro-3-[(6-chloro-2-fluoro-3-methylphenyl)oxy]benzonitrile (1.01 g, 3.06 mmol) and NBS (0.544 g, 3.06 mmol) were combined in carbon tetrachloride (30 mL) with a catalytic amount of AIBN (0.025 g, 0.153 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 80 g silica gel eluted with 0 to 10% Et2O in hexanes to give the 3-{[3-(bromomethyl)-6-chloro-2-fluorophenyl]oxy}-2,5-dichlorobenzonitrile (0.647 g, 1.580 mmol, 51.7% yield) as a white solid. 1H NMR (400 MHz, DMSO-d6) δ ppm 8.03 (d, J=2.20 Hz, 1H), 7.53-7.64 (m, 2H), 7.29 (d, J=1.92 Hz, 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 80 g silica gel
  7. washeluted with 0 to 10% Et2O in hexanes

Sources & evidence

ORD record
ord-c27139b022f34236a04ed3260cae1311
Source dataset
uspto-grants-2012_11
Patent number
US08304419B2

Reaction notes

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