Boron trifluoride etherate → 6-bromo-2-(4-tert-butoxycarbonylbenzyl)-1-oxo-4-phenyl-1,2-dihydroisoquinoline-3-carboxylic Acid Methyl Ester

HRID 750175Notes

Reaction equation

HRID 750175 reaction equation
[CH3:1][O:2][C:3]([C:5]1[N:6]([CH2:23][C:24]2[CH:29]=[CH:28][C:27]([C:30]([OH:32])=[O:31])=[CH:26][CH:25]=2)[C:7](=[O:22])[C:8]2[C:13]([C:14]=1[C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1)=[CH:12][C:11]([Br:21])=[CH:10][CH:9]=2)=[O:4].[C:33](OC(=N)C(Cl)(Cl)Cl)([CH3:36])([CH3:35])[CH3:34].B(F)(F)F.CCOCC.C(=O)([O-])[O-].[K+].[K+]>C(Cl)Cl>[CH3:1][O:2][C:3]([C:5]1[N:6]([CH2:23][C:24]2[CH:25]=[CH:26][C:27]([C:30]([O:32][C:33]([CH3:36])([CH3:35])[CH3:34])=[O:31])=[CH:28][CH:29]=2)[C:7](=[O:22])[C:8]2[C:13]([C:14]=1[C:15]1[CH:16]=[CH:17][CH:18]=[CH:19][CH:20]=1)=[CH:12][C:11]([Br:21])=[CH:10][CH:9]=2)=[O:4]

Participants

6

Reactant 4

HCID 8000Boron trifluoride etherateHCID 11430Potassium CarbonateHCID 2734700Tert-butyl 2,2,2-trichloroethanimidateHCID 102890466-bromo-2-(4-carboxybenzyl)-1-oxo-4-phenyl-1,2-dihydroisoquinoline-3-carboxylic Acid Methyl Ester

Product 1

HCID 691566226-bromo-2-(4-tert-butoxycarbonylbenzyl)-1-oxo-4-phenyl-1,2-dihydroisoquinoline-3-carboxylic Acid Methyl EsterYield 77.8%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a solution of 6-bromo-2-(4-carboxybenzyl)-1-oxo-4-phenyl-1,2-dihydroisoquinoline-3-carboxylic acid methyl ester (300 mg) and 2,2,2-trichloroacetoimidate tert-butyl ester (400 mg) in methylene chloride (6 ml) was added dropwise a catalytic amount of boron trifluoride diethyl etherate at room temperature and the mixture was stirred for 1 hr. To the reaction mixture was added 10% aqueous potassium carbonate solution, and the mixture was concentrated under reduced pressure and extracted with ethyl acetate. The organic layer was washed with water and saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by basic silica gel column chromatography (ethyl acetate) and the obtained crystals were washed with methanol to give the title compound (260 mg).

Workup

  1. concentrationthe mixture was concentrated under reduced pressure
  2. extractionextracted with ethyl acetate
  3. washThe organic layer was washed with water and saturated brine
  4. dry with materialdried over anhydrous sodium sulfate
  5. concentrationconcentrated under reduced pressure
  6. customThe residue was purified by basic silica gel column chromatography (ethyl acetate)
  7. washthe obtained crystals were washed with methanol

Sources & evidence

ORD record
ord-0c0c03e16cee4341b0ca2bdbdb98fc2b
Source dataset
uspto-grants-2008_07
Patent number
US07402595B2

Reaction notes

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