5-Bromo-1-methyl-1H-benzo[d]imidazole

To a solution of 4-bromo-N’-methylbenzene-1, 2-diamine (1.7 g, 8 mmol) in triethyl orthoformate (10 mL) was added PTSA•H20 (152 mg, 0.8 mmol). The mixture was stirred at 85 °C for 2 h, poured into H20 (50 mL) and extracted with EA (40 mL x 2). The organic layers were dried over anhydrous Na2SO4, filtered, concentrated in vacuo, and purified by silica gel column chromatography (PE/EA = 50/1 to 10/1) to afford 5-bromo-1-methyl-1H-benzo[djimidazole (1.5 g, 89 percent) as a yellow solid. LC-MS mlz: 211.1 [M+Hf’. tR= 1.90 mm.To a mixture of 5-bromo-N’-methylbenzene-1, 2-diamine (2.0 g, 10.0 mmol) in 15 mL of trimethoxymethane was added p-TsOH.H20 (0.172 g, 0.02 mmol) at RT and the mixture was stirred at 105 °C for 1 h, cooled and concentrated in vacuo. The residue was purified by column chromatography on silica gel (20.0 g, PE/EA: 10/1-5/1) to afford 6-bromo-1-methyl-1H-benzo[djimidazole as a yellow solid (1.6 g, 76 percent). LC-MS mlz: 213.0 [M+Hf’. Purity (214 nm): 99percent; tR = 1.57 minA mixture of 5-bromo-l-methyl-li7-benzo[7]imidazole (302.3 mg, 1.432 mmol), diphenylmethanimine (341.5 mg, 1.885 mmol), t-BuONa (271.1 mg, 2.821 mmol), BINAP (89.7 mg, 0.144 mmol) and Pd2(dba)3 (130.6 mg, 0.1426 mmol) in l, 4-dioxane (10 mL) was heated to 100 C and stirred overnight under N2 atmosphere and then concentrated in vacuo. The residue was diluted with water (40 mL) and the resulting mixture was extracted with a mixed solvent of DCM/MeOH (10/1 (v/v), 50 mL x 3). The combined organic layers were dried over anhydrous Na2S04, filtered and concentrated in vacuo to give the crude product as a brown solid (0.446 g), which was used directly in the next step without further purification.MS (ESI, pos.ion) m/z: 312.4 [M+H]+.5-Bromo-1-methyl-1H-benzo[d]imidazole (302.3 mg, 1.432 mmol), Benzophenone imine (341.5 mg, 1.885 mmol), t-BuONa (271.1 mg, 2.821 mmol), BINAP (89.7mg, 0.144mmol)And Pd2(dba)3 (130.6 mg, 0.1426 mmol) was dissolved in 1, 4-bicyclohexane (10 mL).The reaction mixture is at 100 C, Stir in the nitrogen atmosphere overnight.After the reaction was completed, it was concentrated under reduced pressure.The residue was diluted with water (40 mL).The resulting mixture was extracted with a mixed solvent of DCM and MeOH (10/1 (v/v), 50mL×3).The combined organic phases were dried with EtOAc EtOAc m.The crude product was used in the next step without further purification.

Molecular Weight:211.06
XLogP3:2.1
Hydrogen Bond Acceptor Count:1
Exact Mass:209.97926
Monoisotopic Mass:209.97926
Topological Polar Surface Area:17.8
Heavy Atom Count:11
Complexity:151
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes