Ethyl 4-ethynylbenzoate → HCID 86752692, compound

HRID 963014Notes

Reaction equation

HRID 963014 reaction equation
I/C=C/C1C(=O)CCCC=1C.I/[CH:13]=[CH:14]/[C:15]1[C:16](=[O:23])[CH2:17][CH2:18][C:19]([CH3:22])([CH3:21])[CH:20]=1.[C:24]([C:26]1[CH:36]=[CH:35][C:29]([C:30]([O:32][CH2:33][CH3:34])=[O:31])=[CH:28][CH:27]=1)#[CH:25]>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>[CH3:21][C:19]1([CH3:22])[CH2:18][CH2:17][C:16](=[O:23])[C:15](/[CH:14]=[CH:13]/[C:25]#[C:24][C:26]2[CH:36]=[CH:35][C:29]([C:30]([O:32][CH2:33][CH3:34])=[O:31])=[CH:28][CH:27]=2)=[CH:20]1

Participants

7

Reactant 3

HCID 15540683Ethyl 4-ethynylbenzoateHCID 18414960HCID 18414960, compoundHCID 86752693HCID 86752693, compound

Product 1

HCID 86752692HCID 86752692, compound

Reagents, catalysts & solvents 3

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

Conditions

Temperature
40 °C

Procedure

A solution of (E)-2-(2-iodoethenyl)-3-methyl-2-cyclohexen-1-one (Compound 19, 0.22 g, 0.797 mmol), ethyl 4-ethynylbenzoate (0.167 g, 0.956 mmol) and triethylamine (9.5 mL) was purged with argon for 10 minutes, and then treated with bis(triphenylphosphine)palladium (II) chloride (28 mg, 0.04 mmol) and copper (I) iodide (8 mg, 0.04 mmol). The solution was stirred 40° C. for 3 hours, and concentrated under a water aspirator vacuum. The residue was dissolved in ethyl acetate and washed with saturated aqueous NH4Cl. The layers were separated and the aqueous layer was extracted 2× with ethyl acetate. The combined organic fractions were washed with water, and brine, and dried (MgSO4). The solvents were removed under reduced pressure, and the residue was purified by silica gel chromatography (88:12, hexane:ethyl acetate) to give the title compound as a yellow crystaline solid.

Workup

  1. concentrationconcentrated under a water
  2. dissolutionThe residue was dissolved in ethyl acetate
  3. washwashed with saturated aqueous NH4Cl
  4. customThe layers were separated
  5. extractionthe aqueous layer was extracted 2× with ethyl acetate
  6. washThe combined organic fractions were washed with water, and brine
  7. dry with materialdried (MgSO4)
  8. customThe solvents were removed under reduced pressure
  9. customthe residue was purified by silica gel chromatography (88:12, hexane:ethyl acetate)

Sources & evidence

ORD record
ord-b8bca4819e2e40ae882a70a3645843b3
Source dataset
uspto-grants-1998_06
Patent number
US05760276

Reaction notes

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