Ammonium fluoride → 3-Amino-4-(thiophen-2-yl)-6-bromophthalimide

HRID 21001Notes

Reaction equation

HRID 21001 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([Sn](CCCC)(CCCC)[C:20]1[S:21][CH:22]=[CH:23][CH:24]=1)CCC.[F-].[NH4+]>C1COCC1.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[NH2:1][C:2]1[C:12]([C:20]2[S:21][CH:22]=[CH:23][CH:24]=2)=[CH:11][C:10]([Br:14])=[C:4]2[C:5]([NH:7][C:8](=[O:9])[C:3]=12)=[O:6]

Participants

6

Reactant 3

HCID 25516Ammonium fluorideHCID 27793732-(Tri-n-butylstannyl)thiopheneHCID 684887173-Amino-4-iodo-6-bromophthalimide

Product 1

HCID 684893823-Amino-4-(thiophen-2-yl)-6-bromophthalimideYield 87.3%

Reagents, catalysts & solvents 2

HCID 178418476HCID 178418476, compoundCatalystHCID 8028TetrahydrofuranSolvent

Procedure

3-Amino-4-iodo-6-bromophthalimide (100 mg, 0.273 mmol) was dissolved in THF (5 mL), and the solution was added with 2-(tributylstannyl)thiophene (0.173 mL, 0.546 mmol) and bis(triphenylphosphine)dichloropalladium (15 mg, 0.022 mmol), followed by stirring under reflux for 12.5 hours under argon atmosphere. The reaction mixture was added with 10% aqueous ammonium fluoride solution, extracted with ethyl acetate. The organic layer was washed with saturated brine and dried over sodium sulfate. The solvent was evaporated under reduced pressure. The residue was purified by slurry using hexane, then purified by preparative thin-layer chromatography (chloroform/acetonitrile=30/1) to obtain 3-amino-4-(thiophen-2-yl)-6-bromophthalimide (77 mg, yield 87%).

Workup

  1. temperatureunder reflux for 12.5 hours under argon atmosphere
  2. extractionextracted with ethyl acetate
  3. washThe organic layer was washed with saturated brine
  4. dry with materialdried over sodium sulfate
  5. customThe solvent was evaporated under reduced pressure
  6. customThe residue was purified by slurry
  7. custompurified by preparative thin-layer chromatography (chloroform/acetonitrile=30/1)

Sources & evidence

ORD record
ord-bd1d487b26d04c6bb41832b318163851
Source dataset
uspto-grants-2010_06
Patent number
US07745641B2

Reaction notes

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