Water → 4-bromo-1-(3-chloro-2-methylbenzyl)-2-methyl-6-nitro-1H-benzo[d]imidazole

HRID 1622442Notes

Reaction equation

HRID 1622442 reaction equation
[Br:1][C:2]1[C:10]2[N:9]=[C:8]([CH3:11])[NH:7][C:6]=2[CH:5]=[C:4]([N+:12]([O-:14])=[O:13])[CH:3]=1.Br[CH2:16][C:17]1[CH:22]=[CH:21][CH:20]=[C:19]([Cl:23])[C:18]=1[CH3:24].C(=O)([O-])[O-].[Cs+].[Cs+].O>CN(C=O)C>[Br:1][C:2]1[C:10]2[N:9]=[C:8]([CH3:11])[N:7]([CH2:16][C:17]3[CH:22]=[CH:21][CH:20]=[C:19]([Cl:23])[C:18]=3[CH3:24])[C:6]=2[CH:5]=[C:4]([N+:12]([O-:14])=[O:13])[CH:3]=1

Participants

6

Reactant 4

HCID 962WaterHCID 10796Cesium carbonateHCID 105130911-(Bromomethyl)-3-chloro-2-methylbenzeneHCID 866878134-bromo-2-methyl-6-nitro-1H-benzo[d]imidazole

Product 1

HCID 866878144-bromo-1-(3-chloro-2-methylbenzyl)-2-methyl-6-nitro-1H-benzo[d]imidazoleYield 98.2%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
80 °C

Procedure

A mixture of 4-bromo-2-methyl-6-nitro-1H-benzo[d]imidazole (67 g, 258 mmol), 1-(bromomethyl)-3-chloro-2-methylbenzene (68 g, 309 mmol), prepared as described in example 1, step b, and cesium carbonate (126 g, 387 mmol) in DMF (800 mL) was stirred at 80° C. for 2 h. After cooled to room temperature, the mixture was poured into 1.5 L of water. The resulting precipitate was filtered, washed with water (300 mL), ether (100 mL) and dried in vacuo to give the crude product (100 g, 98%) as a brown solid; LC/MS: MS (ES+) m/e 394 [M+H]+; 1H NMR (300 MHz, DMSO-d6) δ ppm 2.48 (s, 3H), 2.54 (s, 3H), 5.73 (s, 2H), 6.06 (d, J=7.8 Hz, 1H), 7.06 (t, J=7.8 Hz, 1H), 7.38 (d, J=7.8 Hz, 1H), 8.30 (d, J=1.8 Hz, 1H), 8.60 (d, J=1.8 Hz, 1H).

Workup

  1. customprepared
  2. temperatureAfter cooled to room temperature
  3. filtrationThe resulting precipitate was filtered
  4. washwashed with water (300 mL), ether (100 mL)
  5. customdried in vacuo

Sources & evidence

ORD record
ord-0798c16d6e07479c8befb6ec1992e96b
Source dataset
uspto-grants-2014_07
Patent number
US08778937B2

Reaction notes

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