4-Bromotoluene → HCID 67136338, compound

HRID 230934Notes

Reaction equation

HRID 230934 reaction equation
[C:1]([C:3]1[C:4]2[C:11]([O:12][CH3:13])=[CH:10][CH:9]=[CH:8][C:5]=2[S:6][CH:7]=1)#[CH:2].Br[C:15]1[CH:20]=[CH:19][C:18]([CH3:21])=[CH:17][CH:16]=1>C(N(CC)CC)C.C(OCC)C.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.[Cu]I>[CH3:13][O:12][C:11]1[C:4]2[C:3]([C:1]#[C:2][C:15]3[CH:20]=[CH:19][C:18]([CH3:21])=[CH:17][CH:16]=3)=[CH:7][S:6][C:5]=2[CH:8]=[CH:9][CH:10]=1

Participants

7

Reactant 2

HCID 78054-BromotolueneHCID 23103561HCID 23103561, compound

Product 1

HCID 67136338HCID 67136338, compound

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418397HCID 178418397, compoundCatalystHCID 3283Diethyl EtherSolventHCID 8471TriethylamineSolvent

Procedure

3-Ethynyl-4-methoxybenzo[b]thiophene (0.15 g) was dissolved in triethylamine (10 mL). To the solution were added 4-bromotoluene (0.11 mL), tetrakis(triphenylphosphine)palladium (0) (92 mg) and copper (I) iodide (30 mg), and the mixture was heated for ref lux under an argon atmosphere for 10 hours. The reaction mixture was diluted with diethyl ether, and the insoluble material was removed by filtration. The filtrate was concentrated under reduced pressure, and the residue was purified by column chromatography on silica gel (eluent: n-hexane-n-hexane/ethyl acetate=50/1) to give 4-methoxy-3-[2-(4-methylphenyl)ethynyl]benzo[b]thiophene (27 mg). This material was dissolved in ethanol (1.5 mL). To the solution was added 10% palladium-carbon powder (10 mg), and the mixture was stirred at room temperature under a hydrogen atmosphere overnight. The insoluble material was removed by filtration, and the filtrate was concentrated under reduced pressure to give 4-methoxy-3-[2-(4-methylphenyl)ethyl]-benzo[b]thiophene (27 mg). This material was dissolved in dichloromethane (1.5 mL). To the solution was added boron tribromide (0.011 mL) at −78° C., and the mixture was stirred at the same temperature for 1 hour. Then the mixture was stirred under ice-cooling for 1 hour. The reaction mixture poured into water, and the resulting mixture was extracted with ethyl acetate. The extract was washed with a saturated aqueous sodium hydrogen carbonate solution and brine, and dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure, and the residue was purified by column chromatography on silica gel (eluent: n-hexane/ethyl acetate=15/1) to give the title compound (10 mg).

Workup

  1. temperaturethe mixture was heated for ref lux under an argon atmosphere for 10 hours
  2. customthe insoluble material was removed by filtration
  3. concentrationThe filtrate was concentrated under reduced pressure
  4. customthe residue was purified by column chromatography on silica gel (eluent: n-hexane-n-hexane/ethyl acetate=50/1)

Sources & evidence

ORD record
ord-6c8ef164e0f24662af4f15b7d4fc8508
Source dataset
uspto-grants-2009_07
Patent number
US07566699B2

Reaction notes

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