Ethyl propiolate → Ethyl 3-(4-iodophenyl)propiolate

HRID 1057154Notes

Reaction equation

HRID 1057154 reaction equation
I[C:2]1[CH:7]=[CH:6][C:5]([I:8])=[CH:4][CH:3]=1.[C:9]([O:13][CH2:14][CH3:15])(=[O:12])[C:10]#[CH:11]>C(N(CC)CC)C.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.[Cu]I>[I:8][C:5]1[CH:6]=[CH:7][C:2]([C:11]#[C:10][C:9]([O:13][CH2:14][CH3:15])=[O:12])=[CH:3][CH:4]=1

Participants

7

Reactant 2

HCID 12182Ethyl propiolateHCID 12208p-Diiodobenzene

Product 1

HCID 66800188Ethyl 3-(4-iodophenyl)propiolateYield 39.6%

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 8471TriethylamineSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
80 °C

Procedure

To a mixture of 1,4-diiodobenzene (1.0 g, 3.03 mmol), Pd(PPh3)2Cl2 (580 mg, 0.606 mmol) and CuI (115 mg, 0.606 mmol) in triethylamine (20 mL), ethyl propiolate (590 mg, 6.06 mmol) was added under N2. The resulting mixture was stirred at 80° C. for 16 h under N2. The reaction mixture was diluted with EtOAc (50 mL) and filtered. The filtrate was washed with water (3×10 mL), dried over Na2SO4 and concentrated in vacuo. The residue was purified on a silica gel column using 0-10% EtOAc in petroleum ether to afford the title compound (360 mg, 30%). 1H NMR (DMSO-d6, 400 MHz): δ 7.86 (d, 2H), 7.45 (d, 2H), 4.24 (q, 2H), 1.25 (t, 3H).

Workup

  1. additionwas added under N2
  2. filtrationfiltered
  3. washThe filtrate was washed with water (3×10 mL)
  4. dry with materialdried over Na2SO4
  5. concentrationconcentrated in vacuo
  6. customThe residue was purified on a silica gel column

Sources & evidence

ORD record
ord-1ebb9b6abd864606b35eaa3d3c730ed6
Source dataset
uspto-grants-2016_07
Patent number
US09399646B2

Reaction notes

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