Methyl 4-(2-bromoacetyl)benzoate → Ethyl 2-amino-5-(4-(methoxycarbonyl)phenyl)-1H-pyrrole-3-carboxylate

HRID 590621Notes

Reaction equation

HRID 590621 reaction equation
Cl.[NH2:2][C:3](=[NH:10])[CH2:4][C:5]([O:7][CH2:8][CH3:9])=[O:6].Br[CH2:12][C:13]([C:15]1[CH:24]=[CH:23][C:18]([C:19]([O:21][CH3:22])=[O:20])=[CH:17][CH:16]=1)=O>C(O)C>[NH2:10][C:3]1[NH:2][C:13]([C:15]2[CH:24]=[CH:23][C:18]([C:19]([O:21][CH3:22])=[O:20])=[CH:17][CH:16]=2)=[CH:12][C:4]=1[C:5]([O:7][CH2:8][CH3:9])=[O:6]

Participants

4

Reactant 2

HCID 13612771Methyl 4-(2-bromoacetyl)benzoateHCID 15555354Ethyl 2-carbamimidoylacetate hydrochloride

Product 1

HCID 59756752Ethyl 2-amino-5-(4-(methoxycarbonyl)phenyl)-1H-pyrrole-3-carboxylateYield 56.7%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

Na metal (1.96 g, 85.3 mmol) was added portion wise to ethanol (210 mL) and stirred for 30 minutes to get clear solution. To this was added ethyl 3-amino-3-imino-propanoate hydrochloride (CAS: 57508-48-2, 14.25 g, 85.6 mmol) and stirred at room temperature for additional 30 minutes. Finally, methyl 4-(2-bromoacetyl)benzoate (11 g, 42.8 mmol) was added to the reaction mixture and stirred for 16-20 h at room temperature. After completion of the reaction (as indicated by TLC and LCMS), reaction mixture was filtered through celite and the residue was washed with MeOH (50 mL×2). The combined filtrate was concentrated under reduced pressure and the residue was purified using silica gel column chromatography (40% EtOAc in hexane) to provide XI-7-I (7 g, 56.7% yield). LCMS; m/z: 289.1 (M+1)+.

Workup

  1. customto get clear solution
  2. stirringstirred at room temperature for additional 30 minutes
  3. stirringstirred for 16-20 h at room temperature
  4. customAfter completion of the reaction (as indicated by TLC and LCMS), reaction mixture
  5. filtrationwas filtered through celite
  6. washthe residue was washed with MeOH (50 mL×2)
  7. concentrationThe combined filtrate was concentrated under reduced pressure
  8. customthe residue was purified
  9. customto provide XI-7-I (7 g, 56.7% yield)

Sources & evidence

ORD record
ord-89ecfa7f74bc4c589c8c4cb72aefc0a7
Source dataset
uspto-grants-2016_01
Patent number
US09233983B2

Reaction notes

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