Nitric Acid → 2-Chloro-6-nitro-1H-benzimidazole
Reaction equation
[N+:1]([O-:4])(O)=[O:2].[Cl:5][C:6]1[NH:7][C:8]2[CH:14]=[CH:13][CH:12]=[CH:11][C:9]=2[N:10]=1>>[Cl:5][C:6]1[NH:7][C:8]2[CH:14]=[C:13]([N+:1]([O-:4])=[O:2])[CH:12]=[CH:11][C:9]=2[N:10]=1Participants
Procedure
To 21 0 mL of fuming HNO3, 2-chlorobenzimidazole (13.42 g, 87.95 mmole) was added portionwise over a period of 10 min with stirring and ice-H2O cooling. After the addition, the cooling bath was removed and stirring was continued at room temperature overnight. This reaction mixture was cooled to ~ 0° C., poured into 300 mL of ice, and neutralized carefully with conc. NH4OH to ~ pH 8. The resulting suspension was filtered. The yellowish solid product was washed with portions of H2O and air-dried. The filtrate and washings were combined and extracted with EtOAc (200 mL×2). The EtOAc solution was washed with sat. NaCl solution (200 mL×2), dried (Na2SO4), and evaporated to give 1.3 g of a yellowish solid. The solid was combined with the major part of the product and was recrystallized from MeOH to give 16.34 g (5 crops, 94%) of 19 as yellowish crystals. mp 235°-237° C. MS (El) m/e 196.9984 (100%, M+ =196.9992). 1H NMR (DMSO-d6) d 14.06 (br. s, 1, 1-NH), 8.41 (s, 1, 4-H), 8.14 (dd,. 1, 6-H, J6-4 =2.0 Hz, J6-7 =9.0 Hz), 7.71 (d, 1, 7-H).
Workup
- additionAfter the addition
- customthe cooling bath was removed
- stirringstirring
- temperatureThis reaction mixture was cooled to ~ 0° C.
- additionpoured into 300 mL of ice
- filtrationThe resulting suspension was filtered
- washThe yellowish solid product was washed with portions of H2O
- customair-dried
- extractionextracted with EtOAc (200 mL×2)
- washThe EtOAc solution was washed with sat. NaCl solution (200 mL×2)
- dry with materialdried (Na2SO4)
- customevaporated
Sources & evidence
- ORD record
- ord-9df60af615d4455dbd244a05f748efb4
- Source dataset
- uspto-grants-1997_08
- Patent number
- US05654283
Reaction notes
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