Potassium Carbonate → HCID 15013402, compound

HRID 413653Notes

Reaction equation

HRID 413653 reaction equation
I[C:2]1[CH:9]=[CH:8][C:5]([C:6]#[N:7])=[CH:4][CH:3]=1.[C:10]([O:14][CH2:15][CH3:16])(=[O:13])[C:11]#[CH:12].C(=O)([O-])[O-].[K+].[K+]>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.[Cu]I.C1COCC1>[C:6]([C:5]1[CH:8]=[CH:9][C:2]([C:12]#[C:11][C:10]([O:14][CH2:15][CH3:16])=[O:13])=[CH:3][CH:4]=1)#[N:7]

Participants

7

Reactant 3

HCID 11430Potassium CarbonateHCID 12182Ethyl propiolateHCID 764674-Iodobenzonitrile

Product 1

HCID 15013402HCID 15013402, compoundYield 45%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 8028TetrahydrofuranSolvent

Procedure

3.65 g of p-iodobenzonitrile, 6.25 g of ethyl propiolate, 220 mg of dichlorobis(triphenylphosphine)palladium, 120 mg CuI, and 4.42 g potassium carbonate were combined in a round-bottom flask along with 50 mL freshly distilled THF. This mixture was refluxed while magnetically stirring for 4 hrs. THF was then removed in vacuo. The reaction mixture was extracted with CH2Cl2 (2×150 mL). The combined organic layers were washed with H2O (2×100 mL) and brine (1×100 mL), dried over MgSO4, and concentrated to give a brown/black oily solid as a crude product. Purification by automated flash chromatography (silica gel, ethyl acetate/hexanes) gave the intermediate product ethyl (4-cyano)phenylpropiolate as a white solid in 45% yield. This intermediate product was analyzed by 1HNMR (CDCl3) δ1.36 (t, 3 H, J=7.2 Hz), 4.31 (q, 2 H, J=7.2 Hz), 7.67 (s, 4 H).

Workup

  1. temperatureThis mixture was refluxed
  2. customTHF was then removed in vacuo
  3. extractionThe reaction mixture was extracted with CH2Cl2 (2×150 mL)
  4. washThe combined organic layers were washed with H2O (2×100 mL) and brine (1×100 mL)
  5. dry with materialdried over MgSO4
  6. concentrationconcentrated
  7. customto give a brown/black oily solid as a crude product
  8. customPurification by automated flash chromatography (silica gel, ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-bdc19b6652ce4216a3b515e131ee4fc8
Source dataset
uspto-grants-2003_05
Patent number
US06569600B2

Reaction notes

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