Ammonium Chloride → 3-Amino-4-phenyl-6-bromophthalimide

HRID 20997Notes

Reaction equation

HRID 20997 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]1(B(O)O)[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1.[Cl-].[NH4+].C(Cl)(Cl)Cl.CO>C1COCC1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.S1C=CC=C1C([O-])=O.[Cu+]>[NH2:1][C:2]1[C:12]([C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=2)=[CH:11][C:10]([Br:14])=[C:4]2[C:5]([NH:7][C:8](=[O:9])[C:3]=12)=[O:6].[NH2:1][C:2]1[C:12]([C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=2)=[CH:11][C:10]([C:2]2[CH:12]=[CH:11][CH:10]=[CH:4][CH:3]=2)=[C:4]2[C:5]([NH:7][C:8](=[O:9])[C:3]=12)=[O:6]

Participants

9

Reactant 4

HCID 25517Ammonium ChlorideHCID 66827Phenylboronic AcidHCID 21584188Chloroform methanolHCID 684887173-Amino-4-iodo-6-bromophthalimide

Product 2

HCID 684911853-Amino-4,6-diphenylphthalimideYield 11%HCID 684918043-Amino-4-phenyl-6-bromophthalimideYield 66%

Reagents, catalysts & solvents 3

HCID 11194830Cuprous 2-thiophenecarboxylateCatalystHCID 178418397HCID 178418397, compoundCatalystHCID 8028TetrahydrofuranSolvent

Procedure

3-Amino-4-iodo-6-bromophthalimide (80.0 mg, 0.218 mmol) was dissolved in THF (5.6 mL), and the solution was added with phenylboronic acid (80 mg, 0.65 mmol), tetrakis(triphenylphosphine)palladium (20 mg, 0.017 mmol) and copper(I) thiophene-2-carboxylate (125 mg, 0.65 mmol), followed by stirring at room temperature for 14 hours under argon atmosphere. The reaction mixture was added with saturated aqueous ammonium chloride solution and extracted with ethyl acetate. The organic layer was washed with saturated aqueous sodium hydrogencarbonate solution and saturated brine and dried over anhydrous sodium sulfate. The solvent was evaporated under reduced pressure. The residue was purified by slurry using isopropylether, then by preparative thin-layer chromatography (chloroform/methanol=60/1) to obtain 3-amino-4-phenyl-6-bromophthalimide (46 mg, yield 66%) and 3-amino-4,6-diphenylphthalimide (7.6 mg, yield 11%).

Workup

  1. extractionextracted with ethyl acetate
  2. washThe organic layer was washed with saturated aqueous sodium hydrogencarbonate solution and saturated brine
  3. dry with materialdried over anhydrous sodium sulfate
  4. customThe solvent was evaporated under reduced pressure
  5. customThe residue was purified by slurry

Sources & evidence

ORD record
ord-a7a633f7302e4533ab7835672ef5448a
Source dataset
uspto-grants-2010_06
Patent number
US07745641B2

Reaction notes

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