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

HRID 340286Notes

Reaction equation

HRID 340286 reaction equation
Br[C:2]1[CH:12]=[CH:11][C:5]([C:6]([O:8][CH2:9][CH3:10])=[O:7])=[CH:4][C:3]=1[CH3:13].[CH2:14]([Si:16]([CH2:21][CH3:22])([CH2:19][CH3:20])[C:17]#[CH:18])[CH3:15].C(N(CC)CC)C>CN(C=O)C.C(OCC)(=O)C.[OH-].[NH4+].[Cu]I>[CH3:13][C:3]1[CH:4]=[C:5]([CH:11]=[CH:12][C:2]=1[C:15]#[C:14][Si:16]([CH2:21][CH3:22])([CH2:19][CH3:20])[CH2:17][CH3:18])[C:6]([O:8][CH2:9][CH3:10])=[O:7]

Participants

8

Reactant 3

HCID 8471TriethylamineHCID 637947(Triethylsilyl)acetyleneHCID 21729626Ethyl 4-bromo-3-methylbenzoate

Product 1

HCID 66874679Ethyl 3-methyl-4-((triethylsilyl)ethynyl)benzoate

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolventHCID 14923Ammonium HydroxideSolvent

Procedure

A solution of ethyl 4-bromo-3-methylbenzoate (from the previous step) (1.0 eq.), triethyl(ethynyl)silane (1.1 eq.), trans-dichlororbis(triphenylphosphine)palladium (II) (10 mol %), copper (I) iodide (20 mol %), and triethylamine (5.0 eq.) in DMF (0.3 M) was stirred at 60° C. overnight. After cooling to ambient temperature, the reaction mixture was diluted with ethyl acetate and 10% aqueous ammonium hydroxide. The two phases were separated, and the aqueous layer was extracted twice with ethyl acetate. The combined organic layers were washed with brine, dried over anhydrous MgSO4, and concentrated en vacuo. The crude material was purified by flash chromatography on a COMBIFLASH® system (ISCO) using 0-5% ethyl acetate in hexane to give ethyl 3-methyl-4-((triethylsilyl)ethynyl)benzoate as a yellow oil.

Workup

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

Sources & evidence

ORD record
ord-e7d1da00bdf544eb8d3d21076df84a62
Source dataset
uspto-grants-2014_11
Patent number
US08895577B2

Reaction notes

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