Phenylacetylene → 1-Fluoro-5-methoxy-2-nitro-4-(2-phenylethynyl)benzene

HRID 578788Notes

Reaction equation

HRID 578788 reaction equation
Br[C:2]1[CH:7]=[C:6]([N+:8]([O-:10])=[O:9])[C:5]([F:11])=[CH:4][C:3]=1[O:12][CH3:13].[C:14]1([C:20]#[CH:21])[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1>C(NC(C)C)(C)C.C(OCC)(=O)C.[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Cu]I>[F:11][C:5]1[C:6]([N+:8]([O-:10])=[O:9])=[CH:7][C:2]([C:21]#[C:20][C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)=[C:3]([O:12][CH3:13])[CH:4]=1

Participants

7

Reactant 2

HCID 10821PhenylacetyleneHCID 68996065HCID 68996065, compound

Product 1

HCID 689959411-Fluoro-5-methoxy-2-nitro-4-(2-phenylethynyl)benzeneYield 101.2%

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 11979704Tetrakis(triphenylphosphine)palladiumCatalystHCID 7912DiisopropylamineSolventHCID 8857Ethyl AcetateSolvent

Procedure

A mixture of 2-bromo-5-fluoro-4-nitroanisole (0.46 g), phenylacetylene (67 mg), tetrakis(triphenylphosphine) -palladium(0) (38 mg) and copper (I) iodide (13 mg) in N,N-diisopropylamine (5 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=10/1−5/1) to give 5-fluoro-4-nitro-2-phenylethynylanisole (0.18 g). This material was dissolved in ethyl acetate (5 mL). To the solution was added 10% palladium-carbon powder (0.45 g), and the mixture was stirred at room temperature under a hydrogen atmosphere for 3 hours. 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=10/1−4/1) to give the title compound (87 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=10/1−5/1)

Sources & evidence

ORD record
ord-412419cdc32249eaa8dc39f5a712a74b
Source dataset
uspto-grants-2015_05
Patent number
US09040693B2

Reaction notes

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