Triethylamine → Methyl 4-trimethylsilylethynylbenzoate

HRID 1180814Notes

Reaction equation

HRID 1180814 reaction equation
Br[C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[CH:4][CH:3]=1.[CH3:12][Si:13]([C:16]#[CH:17])([CH3:15])[CH3:14].C(N(CC)CC)C>C1COCC1.CCOC(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>[CH3:12][Si:13]([C:16]#[C:17][C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[CH:4][CH:3]=1)([CH3:15])[CH3:14]

Participants

7

Reactant 3

HCID 8471TriethylamineHCID 12081Methyl 4-bromobenzoateHCID 66111Trimethylsilylacetylene2×

Product 1

HCID 640161Methyl 4-trimethylsilylethynylbenzoateYield 94.7%

Reagents, catalysts & solvents 3

HCID 178418476HCID 178418476, compoundCatalyst2×HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
0 °C

Procedure

A stirred solution at room temperature of methyl 4-bromobenzoate (8.84 g, 41.11 mmol), Pd(PPh3)2Cl2 (840 mg, 1.20 mmol) and Cul (455 mg, 2.39 mmol) in anhydrous THF (200 ml) was saturated with nitrogen for 15 min. Then, the solution under nitrogen was cooled down at 0° C., and trimethylsilylacetylene (7.2 ml, 50.91 mmol) and triethylamine (22 ml, 157.8 mmol) were added successively. The reaction mixture was allowed to warm up at room temperature. After 2 h, Pd(PPh3)2Cl2 (100 mg) and Cul (80 mg) and trimethylsilylacetylene (0.5 ml) were added again, and the reaction mixture was stirred overnight. Then, the reaction mixture was diluted with AcOEt and successively washed with a saturated aqueous solution of NH4Cl and brine, dried over MgSO4, filtered and concentrated. The crude residue was then purified by flash chromatography on silica gel (AcOEt/hexane:5/95□10/90) to afford the title compound XXXI (9.05 g, 38.95 mmol, 94% yield) as a yellow sticky solid. 1H NMR: (400 MHz, CDCl3) δ (ppm): AB system (δA=7.67, δB=7.22, JAB=8.5 Hz, 4H), 3.63 (s, 3H), 0.00 (s, 9H).

Workup

  1. temperatureto warm up at room temperature
  2. washsuccessively washed with a saturated aqueous solution of NH4Cl and brine
  3. dry with materialdried over MgSO4
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customThe crude residue was then purified by flash chromatography on silica gel (AcOEt/hexane:5/95□10/90)

Sources & evidence

ORD record
ord-eee7f7ff81164d4abef9520dc63e3821
Source dataset
uspto-grants-2007_10
Patent number
US07282608B2

Reaction notes

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