Triethylamine → Methyl 4-trimethylsilylethynylbenzoate

HRID 2405662Notes

Reaction equation

HRID 2405662 reaction equation
[CH3:1][O:2][C:3](=[O:11])[C:4]1[CH:9]=[CH:8][C:7](Br)=[CH:6][CH:5]=1.[CH3:12][Si:13]([C:16]#[CH:17])([CH3:15])[CH3:14].C(N(CC)CC)C>C1COCC1.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.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[CH3:1][O:2][C:3](=[O:11])[C:4]1[CH:9]=[CH:8][C:7]([C:17]#[C:16][Si:13]([CH3:15])([CH3:14])[CH3:12])=[CH:6][CH:5]=1

Participants

7

Reactant 3

HCID 8471TriethylamineHCID 12081Methyl 4-bromobenzoateHCID 66111Trimethylsilylacetylene

Product 1

HCID 640161Methyl 4-trimethylsilylethynylbenzoateYield 93%

Reagents, catalysts & solvents 3

HCID 11776TriphenylphosphineCatalystHCID 178418476HCID 178418476, compoundCatalystHCID 8028TetrahydrofuranSolvent

Procedure

Under argon condition, 4-bromobenzoic acid methyl ester (500 mg, 2.33 mmol), bis(triphenylphosphine)palladium dichloride (Pd(PPh3)2Cl2; 86.1 mg, 0.116 mmol), triphenylphosphine (PPh3; 18.3 mg, 0.0698 mmol), trimethylsilyl acetylene (TMS acetylene; 493 μL, 3.49 mmol), and triethylamine (Et3N; 486 μL, 3.49 mmol) were dissolved in 10 mL of dry THF and the reaction mixture was stirred for 20 minutes at room temperature. To this cuprous iodide (CuI; 8.86 mg, 0.0465 mmol) was again added and the mixture was stirred for 15 hours at room temperature. Upon completion of the reaction, the solvent was removed by distillation under reduced pressure and then 20 mL of n-pentane was added to the residue. The mixture was filtered through celite pad to remove the precipitate. The resulting solution was concentrated by distillation under reduced pressure, and purified by column chromatography to obtain 503 mg (2.16 mmol, 93%) of the desired compound.

Workup

  1. stirringthe mixture was stirred for 15 hours at room temperature
  2. customUpon completion of the reaction
  3. customthe solvent was removed by distillation under reduced pressure
  4. addition20 mL of n-pentane was added to the residue
  5. filtrationThe mixture was filtered through celite pad
  6. customto remove the precipitate
  7. concentrationThe resulting solution was concentrated by distillation under reduced pressure
  8. custompurified by column chromatography

Sources & evidence

ORD record
ord-5f89f14c0bdf4c08ab2dff50ebb34faa
Source dataset
uspto-grants-2014_08
Patent number
US08809012B2

Reaction notes

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