Methyl [[(methoxycarbonyl)amino](methylthio)methylene]carbamate → Methyl (1-methyl-5-(4-aminophenoxy)-benzimidazol-2-yl)carbamate

HRID 1294060Notes

Reaction equation

HRID 1294060 reaction equation
[CH3:1][NH:2][C:3]1[CH:8]=[CH:7][C:6]([O:9][C:10]2[CH:15]=[CH:14][C:13]([N+:16]([O-])=O)=[CH:12][CH:11]=2)=[CH:5][C:4]=1[N+:19]([O-])=O.[CH3:22][O:23][C:24]([NH:26][C:27](=NC(OC)=O)SC)=[O:25]>CO.[Pd]>[CH3:1][N:2]1[C:3]2[CH:8]=[CH:7][C:6]([O:9][C:10]3[CH:15]=[CH:14][C:13]([NH2:16])=[CH:12][CH:11]=3)=[CH:5][C:4]=2[N:19]=[C:27]1[NH:26][C:24](=[O:25])[O:23][CH3:22]

Participants

5

Reactant 2

HCID 98708Methyl [[(methoxycarbonyl)amino](methylthio)methylene]carbamateHCID 17755333N-Methyl-4-(4-nitrophenoxy)-2-nitroaniline2×

Product 1

HCID 17755417Methyl (1-methyl-5-(4-aminophenoxy)-benzimidazol-2-yl)carbamateYield 12.3%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 887MethanolSolvent

Procedure

To a mixture of N-methyl-4-(4-nitrophenoxy)-2-nitroaniline (Intermediate 8B -2.10 g, 2.27 mmol) in MeOH (100 mL) was added 5% Pd—C (catalytic amount) and stirred at room temperature under H2 atmosphere. After 7 hrs, the catalyst was removed by filtration then the solvent was evaporated off. The residual mixture was dissolved into MeOH (50 mL) and added 1,3-bis(methoxycarbonyl)-2-methyl-2-thiopseudourea (3.0 g, 14.5 mmol). The mixture was refluxed overnight. The solvent was removed by evaporation and sequence purification on SiO2 column chromatography gave title compound (87.3 mg, 4%): MS m/e 313 (M+1).

Workup

  1. customthe catalyst was removed by filtration
  2. customthe solvent was evaporated off
  3. dissolutionThe residual mixture was dissolved into MeOH (50 mL)
  4. temperatureThe mixture was refluxed overnight
  5. customThe solvent was removed by evaporation and sequence purification on SiO2 column chromatography

Sources & evidence

ORD record
ord-a226441c0c6e4a14bc2bb4b2c4e62e57
Source dataset
uspto-grants-2007_07
Patent number
US07238813B2

Reaction notes

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