Triethylamine → Methyl 3-methyl-4-((triethylsilyl)ethynyl)benzoate

HRID 340329Notes

Reaction equation

HRID 340329 reaction equation
Br[C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[CH:4][C:3]=1[CH3:12].[CH2:13]([Si:15]([CH2:20][CH3:21])([CH2:18][CH3:19])[C:16]#[CH:17])[CH3:14].C(N(CC)CC)C>CN(C=O)C.C(OCC)(=O)C.O.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.[Cu](I)I>[CH3:12][C:3]1[CH:4]=[C:5]([CH:10]=[CH:11][C:2]=1[C:14]#[C:13][Si:15]([CH2:20][CH3:21])([CH2:18][CH3:19])[CH2:16][CH3:17])[C:6]([O:8][CH3:9])=[O:7]

Participants

9

Reactant 3

HCID 8471TriethylamineHCID 637947(Triethylsilyl)acetyleneHCID 3294148Methyl 4-bromo-3-methylbenzoate

Product 1

HCID 66875322Methyl 3-methyl-4-((triethylsilyl)ethynyl)benzoate

Reagents, catalysts & solvents 5

HCID 83717Copper iodideCatalystHCID 178418476HCID 178418476, compoundCatalystHCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Procedure

A solution of methyl 4-bromo-3-methylbenzoate (1.0 eq.), triethyl(ethynyl)silane (1.0 eq.), bis(triphenyl-phosphine)palladium chloride (10 mol %), copper iodide (10 mol %), and triethylamine (5.0 eq.) in DMF (0.04 M) was stirred at 60° C. for 4 hours. After cooling to ambient temperature, the reaction mixture was diluted with ethyl acetate and water. The two phases were separated. The organic layer was washed twice with water, dried over anhydrous MgSO4, and concentrated en vacuo. The crude material was purified by flash chromatography on a COMBIFLASH® system (ISCO) using 0-50% ethyl acetate in hexane to give methyl 3-methyl-4-((triethylsilyl)ethynyl)benzoate as a white solid.

Workup

  1. customThe two phases were separated
  2. washThe organic layer was washed twice with water
  3. dry with materialdried over anhydrous MgSO4
  4. concentrationconcentrated en vacuo
  5. customThe crude material was purified by flash chromatography on a COMBIFLASH® system (ISCO)

Sources & evidence

ORD record
ord-31dd3471896c4e18b9f91e9a1e992d5e
Source dataset
uspto-grants-2014_11
Patent number
US08895577B2

Reaction notes

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