Tetrahydrofuran → Ethyl 4-ethynylbenzoate

HRID 963009Notes

Reaction equation

HRID 963009 reaction equation
I[C:2]1[CH:12]=[CH:11][C:5]([C:6]([O:8][CH2:9][CH3:10])=[O:7])=[CH:4][CH:3]=1.C[Si]([C:17]#[CH:18])(C)C.[F-].C([N+](CCCC)(CCCC)CCCC)CCC.C1COCC1>C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.Cl[Pd]Cl.[Cu]I.C(N(CC)CC)C>[C:17]([C:2]1[CH:12]=[CH:11][C:5]([C:6]([O:8][CH2:9][CH3:10])=[O:7])=[CH:4][CH:3]=1)#[CH:18]

Participants

8

Reactant 4

HCID 8028TetrahydrofuranHCID 66111TrimethylsilylacetyleneHCID 142891Ethyl 4-iodobenzoateHCID 2724141Tetrabutylammonium Fluoride

Product 1

HCID 15540683Ethyl 4-ethynylbenzoate

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 6102075Dichlorobis(triphenylphosphine)palladiumCatalystHCID 8471TriethylamineSolvent

Procedure

A solution of ethyl 4-iodobenzoate (6.9 g, 25 mmol), (trimethylsilyl)acetylene (7.1 mL, 50 mmol) and triethylamine (200 mL) was purged with argon for 10 minutes, and then treated with bis(triphenylphosphine)palladium (II) chloride (175 mg, 0.25 mmol) and copper (I) iodide (48 mg, 0.25 mmol). The suspension was stirred at room temperature for 3 hours and concentrated under the vacuum of a water aspirator. The residue was dissolved in hexane and washed with 10% aqueous HCl. The layers were separated and the aqueous layer was extracted 2× with hexane. The combined organic fractions were washed with water, and brine. The separated organic layer was treated directly with 1M solution of tetrabutylammonium fluoride and THF (35 mL, 35 mmol). After 30 minutes, the solution was washed with water (2×), and brine, dried (MgSO4) and filtered through silica gel. The solvents were removed under reduced pressure and the residue was purified by silica gel chromatography (98:2, hexane:ethyl acetate) to give the title compound as a yellow oil.

Workup

  1. concentrationconcentrated under the vacuum of a water aspirator
  2. dissolutionThe residue was dissolved in hexane
  3. washwashed with 10% aqueous HCl
  4. customThe layers were separated
  5. extractionthe aqueous layer was extracted 2× with hexane
  6. washThe combined organic fractions were washed with water, and brine
  7. waitAfter 30 minutes
  8. washthe solution was washed with water (2×), and brine
  9. dry with materialdried (MgSO4)
  10. filtrationfiltered through silica gel
  11. customThe solvents were removed under reduced pressure
  12. customthe residue was purified by silica gel chromatography (98:2, hexane:ethyl acetate)

Sources & evidence

ORD record
ord-24b4d2dd43444d8e8b280501867b69b6
Source dataset
uspto-grants-1998_06
Patent number
US05760276

Reaction notes

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