Potassium Carbonate → 4-bromo-1-(3-chloro-2-methylbenzyl)-6-nitro-2-(trifluoromethyl)-1H-benzo[d]imidazole

HRID 1622485Notes

Reaction equation

HRID 1622485 reaction equation
[Br:1][C:2]1[C:10]2[N:9]=[C:8]([C:11]([F:14])([F:13])[F:12])[NH:7][C:6]=2[CH:5]=[C:4]([N+:15]([O-:17])=[O:16])[CH:3]=1.Br[CH2:19][C:20]1[CH:25]=[CH:24][CH:23]=[C:22]([Cl:26])[C:21]=1[CH3:27].C(=O)([O-])[O-].[K+].[K+]>CN(C)C=O>[Br:1][C:2]1[C:10]2[N:9]=[C:8]([C:11]([F:12])([F:13])[F:14])[N:7]([CH2:19][C:20]3[CH:25]=[CH:24][CH:23]=[C:22]([Cl:26])[C:21]=3[CH3:27])[C:6]=2[CH:5]=[C:4]([N+:15]([O-:17])=[O:16])[CH:3]=1

Participants

5

Reactant 3

HCID 11430Potassium CarbonateHCID 23091Benzimidazole, 4-bromo-6-nitro-2-(trifluoromethyl)-HCID 105130911-(Bromomethyl)-3-chloro-2-methylbenzene

Product 1

HCID 866878434-bromo-1-(3-chloro-2-methylbenzyl)-6-nitro-2-(trifluoromethyl)-1H-benzo[d]imidazoleYield 56.2%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
90 °C

Procedure

Charged a 100 mL round bottom flask containing 4-bromo-6-nitro-2-(trifluoromethyl)-1H-benzo[d]imidazole (4.3 g, 13.87 mmol) dissolved in N,N-Dimethylformamide (DMF) (30 mL) with 1-(bromomethyl)-3-chloro-2-methylbenzene (3.81 g, 17.34 mmol) then added potassium carbonate (4.79 g, 34.7 mmol). The resulting reaction suspension was stirred for 6 h at 90° C., then cooled to RT, and filtered to remove potassium carbonate. The resulting filtrate was concentrated to a small volume (˜10 mL), and diluted with water. The aqueous suspension was extracted with chloroform (3×), the organic extracts were combined, washed with brine, dried over Na2SO4, filtered, and finally concentrated in vacuo. The crude solid was slurried in hexane to provide 4-bromo-1-(3-chloro-2-methylbenzyl)-6-nitro-2-(trifluoromethyl)-1H-benzo[d]imidazole (3.5 g, 7.80 mmol, 56.2% yield). The material was carried onto the nitro reduction without further purification. MS (ES+) m/e: 449.0, 450.8 [M+H]+(bromine pattern). 1H NMR (400 MHz, CHLOROFORM-d) δ ppm 8.55 (d, J=2.02 Hz, 1H) 8.08 (d, J=1.77 Hz, 1H) 7.40 (d, J=8.08 Hz, 1H) 7.04 (t, J=7.96 Hz, 1H) 6.23 (d, J=7.83 Hz, 1H) 5.63 (s, 2H) 2.52 (s, 3H)

Workup

  1. additionCharged a 100 mL round bottom flask
  2. customThe resulting reaction suspension
  3. temperaturecooled to RT
  4. filtrationfiltered
  5. customto remove potassium carbonate
  6. concentrationThe resulting filtrate was concentrated to a small volume (˜10 mL)
  7. additiondiluted with water
  8. extractionThe aqueous suspension was extracted with chloroform (3×)
  9. washwashed with brine
  10. dry with materialdried over Na2SO4
  11. filtrationfiltered
  12. concentrationfinally concentrated in vacuo

Sources & evidence

ORD record
ord-733f88a8e215406b9bbea8da2b5ac315
Source dataset
uspto-grants-2014_07
Patent number
US08778937B2

Reaction notes

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