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

HRID 1622477Notes

Reaction equation

HRID 1622477 reaction equation
[Br:1][C:2]1[C:10]2[N:9]=[C:8]([CH:11]([F:13])[F:12])[NH:7][C:6]=2[CH:5]=[C:4]([N+:14]([O-:16])=[O:15])[CH:3]=1.Br[CH2:18][C:19]1[CH:24]=[CH:23][CH:22]=[C:21]([Cl:25])[C:20]=1[CH3:26].C(=O)([O-])[O-].[K+].[K+]>CN(C=O)C>[Br:1][C:2]1[C:10]2[N:9]=[C:8]([CH:11]([F:12])[F:13])[N:7]([CH2:18][C:19]3[CH:24]=[CH:23][CH:22]=[C:21]([Cl:25])[C:20]=3[CH3:26])[C:6]=2[CH:5]=[C:4]([N+:14]([O-:16])=[O:15])[CH:3]=1

Participants

5

Reactant 3

HCID 11430Potassium CarbonateHCID 105130911-(Bromomethyl)-3-chloro-2-methylbenzeneHCID 866878364-bromo-2-(difluoromethyl)-6-nitro-1H-benzo[d]imidazole

Product 1

HCID 866878374-bromo-1-(3-chloro-2-methylbenzyl)-2-(difluoromethyl)-6-nitro-1H-benzo[d]imidazoleYield 107%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a 100 mL round bottomed flask containing DMF (17 mL) was added 4-bromo-2-(difluoromethyl)-6-nitro-1H-benzo[d]imidazole (2.3 g, 7.88 mmol), 1-(bromomethyl)-3-chloro-2-methylbenzene (2.4 g, 10.93 mmol) and potassium carbonate (2.3 g, 16.64 mmol). The resultant suspension was heated to 70° C. and after stirring for 20 minutes LC/MS indicated that almost all starting material had been consumed so the heat was turned off and the reaction was allowed to stir overnight at rt. The next day the mixture was diluted with 75 mL H2O and stirred for 10 minutes resulting in the precipitation of a light brown solid. The solid was isolated by filtration and was washed 3× with H2O and 3× with hexanes to provide 4-bromo-1-(3-chloro-2-methylbenzyl)-2-(difluoromethyl)-6-nitro-1H-benzo[d]imidazole (4.2 g, 8.39 mmol, 107% yield) as light brown solid. The NMR and LC/MS were consistent with desired product and the crude product will be used in subsequent reactions without further purification. LC/MS: MS (ES+) m/e 431.9 [M+H]+; 1H NMR (400 MHz, DMSO-d6) δ ppm 8.76 (d, J=2.02 Hz, 1H), 8.45 (d, J=2.02 Hz, 1H), 7.32-7.68 (m, 2H), 6.99-7.12 (m, 1H), 6.06 (d, J=7.58 Hz, 1H), 5.90 (s, 2H), 2.47 (s, 3H)

Workup

  1. customhad been consumed so the heat
  2. stirringto stir overnight at rt
  3. additionThe next day the mixture was diluted with 75 mL H2O
  4. stirringstirred for 10 minutes
  5. customresulting in the precipitation of a light brown solid
  6. customThe solid was isolated by filtration
  7. washwas washed 3× with H2O and 3× with hexanes

Sources & evidence

ORD record
ord-6c9bc429fc924f7789bba6341a9d15b3
Source dataset
uspto-grants-2014_07
Patent number
US08778937B2

Reaction notes

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