6-broMo-1-Methyl-1H-benzo[d]iMidazol-2(3H)-one

6-Bromo-l-methyl-lH-benzo[d]imidazol-2(3H)-one: tert-Butyl 5- bromo-2-oxo-2, 3-dihydrobenzo[d]imidazole-l-carboxylate (12 g, 38 mmol) (Puwen Zhang, et. al., Bioorganic Medicinal Chemistry Letters 1 1 (2001) 2747-2750 hereby incoporated by reference) and anhydrous disodium carbonate (3.2 niL, 77 mmol) were mixed in 200 mL THF. To this mixture was added dimethyl sulfate (15 mL, 153 mmol). The mixture was stirred at room temperature for 18 hours. The solvent was evaporated. The residue was dissolved in EtOAc and washed with brine and dried over sodium To a solution of2-amino-4-bromobenzenethiol (500 mg, 2.50 mmol)in acetic acid (25mL)was added triphosgene (490 mg, 1.70 mmol). The mixture was heated at reflux for 18 h.After cooling to room temperature, the solution was partially concentrated under reducedpressure, water was added, and the resulting precipitate was removed via filtration, and washedwith aqueous NaOH (1M). The filtrate was acidified with aqueous HCl (2 N)to pH 2, and placed in a refrigerator for 12 h. The resulting precipitate was filtered, washed with water, anddried under reduced pressure to give the title compound (133 mg, 24percent)as a while powder thatrequired no further purification. 1H NMR (400 MHz, DMSO-d6)8 10.97 (s, 1H), 7.33 (d, J = 1.9Hz, 1H), 7.13 (dd, J = 8.2, 1.9 Hz, 1H), 6.91 (d, J = 8.2 Hz, 1H), 3.26 (s, 3H)5-Bromo-N1-methylbenzene-1, 2-diamine (14 g, 69.3 mmol) was dissolved in THF (200 mL), CDI (13.4 g, 83.2 mmol) was added. The mixture was reflux about 2 hours under N5-Bromo-Nl-methylbenzene-l, 2-diamine (14 g, 69.3 mmol) was dissolved in THF (200 mL), CDI (13.4 g, 83.2 mmol) was added, the mixture was reflux about 2 hours under N[00338] 6-Bromo-l-methyl-lH-benzo[d]imidazol-2(3H)-one: tert-Butyl 5- bromo-2-oxo-2, 3-dihydrobenzo[d]imidazole-l-carboxylate (12 g, 38 mmol) (Puwen Zhang, et. al., Bioorganic Medicinal Chemistry Letters 1 1 (2001) 2747-2750 hereby incoporated by reference) and anhydrous disodium carbonate (3.2 niL, 77 mmol) were mixed in 200 mL THF. To this mixture was added dimethyl sulfate (15 mL, 153 mmol). The mixture was stirred at room temperature for 18 hours. The solvent was evaporated. The residue was dissolved in EtOAc and washed with brine and dried over sodium To a solution of2-amino-4-bromobenzenethiol (500 mg, 2.50 mmol)in acetic acid (25mL)was added triphosgene (490 mg, 1.70 mmol). The mixture was heated at reflux for 18 h.After cooling to room temperature, the solution was partially concentrated under reducedpressure, water was added, and the resulting precipitate was removed via filtration, and washedwith aqueous NaOH (1M). The filtrate was acidified with aqueous HCl (2 N)to pH 2, and placed in a refrigerator for 12 h. The resulting precipitate was filtered, washed with water, anddried under reduced pressure to give the title compound (133 mg, 24percent)as a while powder thatrequired no further purification. 1H NMR (400 MHz, DMSO-d6)8 10.97 (s, 1H), 7.33 (d, J = 1.9Hz, 1H), 7.13 (dd, J = 8.2, 1.9 Hz, 1H), 6.91 (d, J = 8.2 Hz, 1H), 3.26 (s, 3H)EXAMPLE 4 6-Bromo-1-methyl-1, 3-dihydro-benzoimidazol-2-one Prepared from 5-bromo-3-methyl-2-oxo-2, 3-dihydro-benzoimidazole-1-carboxylic acid tert-butyl ester in the same fashion as that of White solid: mp 237-238 C.; 1H-NMR (DMSO-d6) delta11.0 (s, 1H), 7.35 (d, 1H, J=1.58 Hz), 7.14 (dd, 1H, J=7.89, 1.58 Hz), 6.92 (d, 1H, J=7.89 Hz), 3.3 (s, 3H); MS (ES) m/z 227([M+H]+, 50%), 229([M+H]+, 50%); Anal. Calc. For C8H7BrN2O: C, 42.32, H, 3.11; N, 12.34 Found: C, 42.35; H, 3.07; N, 11.89.EXAMPLE 4 6-Bromo-1-methyl-1, 3-dihydro-benzoimidazol-2-one Prepared from 5-bromo-3-methyl-2-oxo-2, 3-dihydro-benzoimidazole-1-carboxylic acid tert-butyl ester in the same fashion as that of White solid: mp 237-238 C.; 1H-NMR (DMSO-d6) delta 11.0 (s, 1H), 7.35 (d, 1H, J=1.58 Hz), 7.14 (dd, 1H, J=7.89, 1.58 Hz), 6.92 (d, 1H, J=7.89 Hz), 3.3 (s, 3H); MS (ES) m/z 227([M+H]+, 50%), 229([M+H]+, 50%); Anal. Calc. For C8H7BrN2O: C, 42.32, H, 3.11, N, 12.34. Found: C, 42.35, H, 3.07 N, 11.89.By the method disclosed in the literature (J. Org. Chem., (1995), 60, 1565-1582), tert-butyl 5-bromo-2-oxo-2, 3-dihydro-1H-benzimidazole-1-carboxylate is synthesized, which is further methylated in a similar manner to Reference Example 10 to give tert-butyl 5-bromo-3-methyl-2-oxo-2, 3-dihydro-1H-benzimidazole-1-carboxylate. Subsequently, to a solution of tert-butyl 5-bromo-3-methyl-2-oxo-2, 3-dihydro-1H-benzimidazole-1-carboxylate (1.65 g, 5.04 mmol) in acetic acid (5 mL) is added a 4N solution of hydrochloric acid in 1, 4-dioxane solution (5 mL, 20.0 mmol), and the mixture is stirred at 20-25C for one hour. The reaction solution is concentrated under reduced pressure, and thereto is added toluene. The mixture is evaporated under reduced pressure again to give 6-bromo-1-methyl-1, 3-dihydro-2H-benzimidazol-2-one (1.16 g). Further, the same procedures in Reference Examples 3, 4 are repeated to give (5-bromo-3-methyl-2-oxo-2, 3-dihydro-1H-benzimidazol-1-yl)acetic acid. 1H-NMR (400 MHz, DMSO-d6): delta 3.33 (s, 3H), 4.60 (s, 2H), 7.13 (d, 1H, J=8.3Hz), 7.21 (dd, 1H, J=8.3, 1.9Hz), 7.44 (d, 1H, J=1.8Hz), 13.14 (br, 1H).

Molecular Weight:227.06
XLogP3:1.4
Hydrogen Bond Donor Count:1
Hydrogen Bond Acceptor Count:1
Exact Mass:225.97418
Monoisotopic Mass:225.97418
Topological Polar Surface Area:32.3
Heavy Atom Count:12
Complexity:209
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes