3,3,3-Triethoxyprop-1-yne → Ethyl 3-(2-bromo-5-chlorophenyl)propiolate

HRID 2078231Notes

Reaction equation

HRID 2078231 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([Cl:8])=[CH:4][C:3]=1I.[CH2:10]([O:12][C:13](OCC)([O:16]CC)[C:14]#[CH:15])[CH3:11]>C(#N)C.CCOC(C)=O.[Cu]I.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>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([Cl:8])=[CH:4][C:3]=1[C:15]#[C:14][C:13]([O:12][CH2:10][CH3:11])=[O:16]

Participants

7

Reactant 2

HCID 109209723,3,3-Triethoxyprop-1-yneHCID 510000721-Bromo-4-chloro-2-iodobenzene

Product 1

HCID 67099338Ethyl 3-(2-bromo-5-chlorophenyl)propiolateYield 55.2%

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 6342AcetonitrileSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
23 °C

Procedure

A suspension of 1-bromo-4-chloro-2-iodobenzene (5.4 g, 17.0 mmol), 3,3,3-triethoxyprop-1-yne (4.4 g, 25.6 mmol), copper(I) iodide (976 mg, 5.1 mmol), and trans-dichlorobis(triphenylphosphine)palladium(II) (1.19 g, 1.7 mmol) in ACN (60 mL) was degassed and backfilled with argon. The resulting mixture was treated with TEA (22.0 mL, 157.9 mmol). The reaction flask was capped with a septum and stirred at 23° C. After 90 minutes, the reaction was diluted with EtOAc (300 mL) and washed with water (150 mL). The aqueous layer was extracted with EtOAc (300 mL). The combined organic layers were washed with brine (100 mL), dried over MgSO4, concentrated in vacuo, dissolved in EtOH (50 mL) and water (5 mL) and then treated with p-toluenesulfonic acid monohydrate (5 mg). After stirring at 23° C. for 60 minutes, the solution was concentrated, dissolved in diethyl ether (300 mL) and washed with saturated NaHCO3 solution (100 mL), water (100 mL) and brine (100 mL), dried over MgSO4, and concentrated in vacuo affording 2.7 g of ethyl 3-(2-bromo-5-chlorophenyl)propiolate.

Workup

  1. customwas degassed
  2. customThe reaction flask was capped with a septum
  3. washwashed with water (150 mL)
  4. extractionThe aqueous layer was extracted with EtOAc (300 mL)
  5. washThe combined organic layers were washed with brine (100 mL)
  6. dry with materialdried over MgSO4
  7. concentrationconcentrated in vacuo
  8. dissolutiondissolved in EtOH (50 mL)
  9. additionwater (5 mL) and then treated with p-toluenesulfonic acid monohydrate (5 mg)
  10. stirringAfter stirring at 23° C. for 60 minutes
  11. concentrationthe solution was concentrated
  12. dissolutiondissolved in diethyl ether (300 mL)
  13. washwashed with saturated NaHCO3 solution (100 mL), water (100 mL) and brine (100 mL)
  14. dry with materialdried over MgSO4
  15. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-da7623e434804c49abe95a71d2a579b7
Source dataset
uspto-grants-2011_04
Patent number
US07928139B2

Reaction notes

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