Iodobenzene → HCID 68997712, compound

HRID 578787Notes

Reaction equation

HRID 578787 reaction equation
[C:1]([O:5][C:6]([NH:8][C:9]1[CH:14]=[C:13]([C:15]#[CH:16])[CH:12]=[CH:11][C:10]=1[F:17])=[O:7])([CH3:4])([CH3:3])[CH3:2].I[C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1>C(NC(C)C)(C)C.C(OCC)(=O)C.[Cu]I>[C:1]([O:5][C:6]([NH:8][C:9]1[CH:14]=[C:13]([C:15]#[C:16][C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=2)[CH:12]=[CH:11][C:10]=1[F:17])=[O:7])([CH3:4])([CH3:3])[CH3:2]

Participants

6

Reactant 2

HCID 11575IodobenzeneHCID 58022178HCID 58022178, compound

Product 1

HCID 68997712HCID 68997712, compoundYield 96.2%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 7912DiisopropylamineSolventHCID 8857Ethyl AcetateSolvent

Procedure

A mixture of 1-(tert-butoxycarbonylamino)-5-ethynyl -2-fluorobenzene (0.11 g), iodobenzene (0.1 g), tetrakis -(triphenylphosphine)palladium(0) (16 mg) and copper (I) iodide (5 mg) in N,N-diisopropylamine (2 mL) was stirred at room temperature overnight. The reaction mixture was diluted with ethyl acetate. The insoluble material was removed by filtration, and the filtrate was concentrated under reduced pressure. The residue was purified by column chromatography on silica gel (eluent: n-hexane/ethyl acetate=10/1) to give 1-(tert -butoxycarbonylamino)-2-fluoro-5-phenylethynylbenzene (0.14 g). This material was dissolved in ethyl acetate (3 mL). To the solution was added 10% palladium-carbon powder (50 mg), and the mixture was stirred at room temperature under a hydrogen atmosphere for 2 hours. The insoluble material was removed by filtration, and the filtrate was concentrated under reduced pressure to give 1-(tert-butoxycarbonylamino)-2-fluoro -5-(2-phenylethyl)benzene (0.11 g). To this material was added hydrochloric acid (4 mol/L ethyl acetate solution, 3 mL), and the mixture was stirred at room temperature for 1 hour. The reaction mixture was poured into a saturated aqueous sodium hydrogen carbonate solution, and the resulting mixture was extracted with ethyl acetate. The extract was dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The residue was purified by column chromatography on silica gel (eluent: n-hexane/ethyl acetate =8/1 -5/1) to give the title compound (53 mg).

Workup

  1. customThe insoluble material was removed by filtration
  2. concentrationthe filtrate was concentrated under reduced pressure
  3. customThe residue was purified by column chromatography on silica gel (eluent: n-hexane/ethyl acetate=10/1)

Sources & evidence

ORD record
ord-7db41d83a0c348b9aac6ca459f274cc0
Source dataset
uspto-grants-2015_05
Patent number
US09040693B2

Reaction notes

Loading…