1-Bromo-3-chlorobenzene → HCID 67068489, compound

HRID 536112Notes

Reaction equation

HRID 536112 reaction equation
[CH2:1]([O:3][C:4]([C:6]1[NH:7][CH:8]=[CH:9][C:10]=1[NH2:11])=[O:5])[CH3:2].Br[C:13]1[CH:14]=[C:15]([Cl:19])[CH:16]=[CH:17][CH:18]=1.C1C=CC(P(C2C(C3C(P(C4C=CC=CC=4)C4C=CC=CC=4)=CC=C4C=3C=CC=C4)=C3C(C=CC=C3)=CC=2)C2C=CC=CC=2)=CC=1.C(=O)([O-])[O-].[Cs+].[Cs+]>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C(O)C>[Cl:19][C:15]1[CH:14]=[C:13]([NH:11][C:10]2[CH:9]=[CH:8][NH:7][C:6]=2[C:4]([O:3][CH2:1][CH3:2])=[O:5])[CH:18]=[CH:17][CH:16]=1

Participants

7

Reactant 4

HCID 79281-Bromo-3-chlorobenzene2×HCID 10796Cesium carbonateHCID 634876Binap, (A+-)-HCID 2773439Ethyl 3-amino-1H-pyrrole-2-carboxylate

Product 1

HCID 67068489HCID 67068489, compoundYield 15.1%

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalyst3×HCID 702EthanolSolvent

Conditions

Temperature
100 °C

Procedure

A mixture of 3-amino-1H-pyrrole-2-carboxylic acid ethyl ester (0.20 g, 1.3 mmol), 3-bromochlorobenzene (0.30 g, 1.6 mmol), Pd2(dba)3 (0.048 g, 0.052 mmol), rac-BINAP (0.048 g, 0.078 mmol) and cesium carbonate (0.59 g, 1.8 mmol) was heated at 100° C. in a sealed microwave vial under nitrogen atmosphere overnight. Additional Pd2(dba)3 (0.10 g, 0.11 mmol) and R,S-BINAP (0.11 g, 0.18 mmol) were added and the reaction was continued stirring at 100° C. overnight. Additional 3-bromochlorobenzene (0.15 g), Pd2(dba)3 (0.098 g) and R,S-BINAP (0.098 g) were added and the reaction was continued stirring at 100° C. for three more days. The reaction mixture was poured into ethanol and the resulting solution was filtered. The filtrate was evaporated in vacuo and the residue was purified by flash column chromatography (heptane/ethyl acetate gradient; 0 to 30% ethyl acetate), obtaining 0.052 g (15%) of the title compound.

Workup

  1. stirringthe reaction was continued stirring at 100° C. for three more days
  2. filtrationthe resulting solution was filtered
  3. customThe filtrate was evaporated in vacuo
  4. customthe residue was purified by flash column chromatography (heptane/ethyl acetate gradient; 0 to 30% ethyl acetate)

Sources & evidence

ORD record
ord-d24ba42fa80e4d1584c31bb5a8e59455
Source dataset
uspto-grants-2014_10
Patent number
US08859568B2

Reaction notes

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