Water → (E)-3-amino-4-(2-methoxycarbonylvinyl)-6-bromophthalimide

HRID 21003Notes

Reaction equation

HRID 21003 reaction equation
[NH2:1][C:2]1[C:12](I)=[CH:11][C:10]([Br:14])=[C:4]2[C:5]([NH:7][C:8](=[O:9])[C:3]=12)=[O:6].[C:15]([O:19][CH3:20])(=[O:18])[CH:16]=[CH2:17].C(N(CC)CC)C.O>C(#N)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[NH2:1][C:2]1[C:12](/[CH:17]=[CH:16]/[C:15]([O:19][CH3:20])=[O:18])=[CH:11][C:10]([Br:14])=[C:4]2[C:5]([NH:7][C:8](=[O:9])[C:3]=12)=[O:6]

Participants

7

Reactant 4

HCID 962WaterHCID 7294Methyl Acrylate3×HCID 8471Triethylamine3×HCID 684887173-Amino-4-iodo-6-bromophthalimide

Product 1

HCID 68491786(E)-3-amino-4-(2-methoxycarbonylvinyl)-6-bromophthalimideYield 71%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalyst3×HCID 6342AcetonitrileSolvent

Procedure

3-Amino-4-iodo-6-bromophthalimide (500 mg, 1.36 mmol) was dissolved in acetonitrile (25 mL), and the solution was added with methyl acrylate (0.245 mL, 2.72 mmol), palladium acetate (24 mg, 0.11 mmol) and triethylamine (1.90 mL, 13.6 mmol), followed by stirring under reflux for 5 hours under argon atmosphere. The mixture was added with methyl acrylate (0.122 mL, 1.36 mmol), palladium acetate (24 mg, 0.11 mmol) and triethylamine (1.90 mL, 13.6 mmol) and further stirred for 142 hours. The mixture was added with methyl acrylate (0.245 mL, 2.72 mmol), palladium acetate (24 mg, 0.11 mmol) and triethylamine (0.95 mL, 6.8 mmol) and further stirred for 20 hours. The reaction mixture was added with water, extracted with ethyl acetate. The organic layer was washed with saturated brine and dried over sodium sulfate. The solvent was evaporated under reduced pressure and the residue was purified by slurry using chloroform to obtain (E)-3-amino-4-(2-methoxycarbonylvinyl)-6-bromophthalimide (313 mg, yield 71%).

Workup

  1. temperatureunder reflux for 5 hours under argon atmosphere
  2. stirringfurther stirred for 142 hours
  3. stirringfurther stirred for 20 hours
  4. extractionextracted with ethyl acetate
  5. washThe organic layer was washed with saturated brine
  6. dry with materialdried over sodium sulfate
  7. customThe solvent was evaporated under reduced pressure
  8. customthe residue was purified by slurry

Sources & evidence

ORD record
ord-ae9544d82ea846afb076e374e90907ed
Source dataset
uspto-grants-2010_06
Patent number
US07745641B2

Reaction notes

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