Ammonium formate → ethyl 3-(6-amino-1H-benzimidazol-1-yl)-3-phenylpropanoate

HRID 1676018Notes

Reaction equation

HRID 1676018 reaction equation
[CH2:1]([O:3][C:4](=[O:25])[CH:5]=[C:6]([N:13]1[C:17]2[CH:18]=[CH:19][C:20]([N+:22]([O-])=O)=[CH:21][C:16]=2[N:15]=[CH:14]1)[C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1)[CH3:2].[CH2:26]([O:28][C:29](=[O:50])[CH:30]=[C:31]([N:38]1[C:42]2[CH:43]=[C:44]([N+:47]([O-])=O)[CH:45]=[CH:46][C:41]=2[N:40]=[CH:39]1)[C:32]1[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=1)[CH3:27].C([O-])=O.[NH4+]>C(O)C.O.[Pd]>[NH2:47][C:44]1[CH:45]=[CH:46][C:41]2[N:40]=[CH:39][N:38]([CH:31]([C:32]3[CH:33]=[CH:34][CH:35]=[CH:36][CH:37]=3)[CH2:30][C:29]([O:28][CH2:26][CH3:27])=[O:50])[C:42]=2[CH:43]=1.[NH2:22][C:20]1[CH:19]=[CH:18][C:17]2[N:13]([CH:6]([C:7]3[CH:8]=[CH:9][CH:10]=[CH:11][CH:12]=3)[CH2:5][C:4]([O:3][CH2:1][CH3:2])=[O:25])[CH:14]=[N:15][C:16]=2[CH:21]=1

Participants

8

Reactant 3

HCID 2723923Ammonium formateHCID 67352746Ethyl-3-(5-nitro-1h-benzimidazol-1-yl)-3-phenyl-2-propenoateHCID 67353774Ethyl-3-(6-nitro-1h-benzimidazol-1-yl)-3-phenyl-2-propenoate

Product 2

HCID 67351765ethyl 3-(6-amino-1H-benzimidazol-1-yl)-3-phenylpropanoateHCID 67351926ethyl 3-(5-amino-1H-benzimidazol-1-yl)-3-phenylpropanoate

Reagents, catalysts & solvents 3

HCID 23938PalladiumCatalystHCID 702EthanolSolventHCID 962WaterSolvent

Procedure

To a mixture of ethyl-3-(5-nitro-1H-benzimidazol-1-yl)-3-phenyl-2-propenoate and ethyl-3-(6-nitro-1H-benzimidazol-1-yl)-3-phenyl-2-propenoate (5.34 g, 15.8 mmol) in a mixture of ethanol and water (10:1, 66 mL) was added palladium on carbon (801 mg, 10% w/w Pd) and ammonium formate (6.0 g, 95 mmol). The suspension was heated to reflux, and was stirred at this temperature for 1.5 hours. The reaction mixture was allowed to cool to room temperature, then filtered through Celite®, and the filter pad washed several times with ethanol. The combined filtrates were evaporated in vacuo, and the residue was purified by flash column chromatography on silica gel, eluting with a mixture of dichloromethane and methanol (99:1) to give, in order of elution, ethyl 3-(6-amino-1H-benzimidazol-1-yl)-3-phenylpropanoate, [LCMS (Method A, Mobile Phase I) RT=3.33 min, MH+ 310] and ethyl 3-(5-amino-1H-benzimidazol-1-yl)-3-phenylpropanoate (1.96 g), [LCMS (Method A, Mobile Phase I) RT=3.35 min, MH+ 310].

Workup

  1. temperatureThe suspension was heated
  2. temperatureto reflux
  3. filtrationfiltered through Celite®
  4. washthe filter pad washed several times with ethanol
  5. customThe combined filtrates were evaporated in vacuo
  6. customthe residue was purified by flash column chromatography on silica gel
  7. washeluting with a mixture of dichloromethane and methanol (99:1)

Sources & evidence

ORD record
ord-311afd4a87b14749aa867a06227778b2
Source dataset
uspto-grants-2011_08
Patent number
US08003806B2

Reaction notes

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