Triethylamine → HCID 90092497, compound

HRID 1774560Notes

Reaction equation

HRID 1774560 reaction equation
[S:1]1[CH:5]=[CH:4][CH:3]=[C:2]1[C:6](Cl)=[O:7].C(N(CC)CC)C.[C:16]([O:24][CH2:25][C:26]#[CH:27])(=[O:23])[C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1>O1CCOCC1.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>[C:16]([O:24][CH2:25][C:26]#[C:27][C:6](=[O:7])[C:2]1[S:1][CH:5]=[CH:4][CH:3]=1)(=[O:23])[C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1

Participants

7

Reactant 3

HCID 8471TriethylamineHCID 789282-Thiophenecarbonyl chlorideHCID 336291Prop-2-yn-1-yl benzoate

Product 1

HCID 90092497HCID 90092497, compoundYield 39.4%

Reagents, catalysts & solvents 3

HCID 83717Copper iodideCatalystHCID 178418476HCID 178418476, compoundCatalystHCID 312751,4-DioxaneSolvent

Procedure

A solution of 2-thiophenecarbonyl chloride (549 mg, 3.75 mmol) in anhydrous dioxane (15 mL) was bubbled with argon for 10 minutes. Triethylamine (1.31 mL, 9.36 mmol) was added and the bubbling was maintained for 5 minutes. Bis(triphenylphosphine)palladium(II) dichloride (88 mg, 0.12 mmol), copper iodide (48 mg, 0.25 mmol) and propargyl benzoate (0.45 mL, 3.12 mmol) were added, and the reaction mixture was stirred for 1 hour at room temperature, under argon atmosphere. The solution was filtered and water (20 mL) was added to the filtrate. Layers were separated, and the aqueous layer was extracted with dichloromethane (2×20 mL). The combined organic layers were washed with a saturated solution of sodium hydrogenocarbonate (20 mL), dried over sodium sulfate and concentrated in vacuo. The residue was purified by flash chromatography on silica gel (cyclohexane/ethyl acetate 100/0 to 95/5) to provide 4-oxo-4-(thiophen-2-yl)but-2-yn-1-yl benzoate (3a) (333 mg, 1.23 mmol, 39%).

Workup

  1. temperaturethe bubbling was maintained for 5 minutes
  2. filtrationThe solution was filtered
  3. additionwater (20 mL) was added to the filtrate
  4. customLayers were separated
  5. extractionthe aqueous layer was extracted with dichloromethane (2×20 mL)
  6. washThe combined organic layers were washed with a saturated solution of sodium hydrogenocarbonate (20 mL)
  7. dry with materialdried over sodium sulfate
  8. concentrationconcentrated in vacuo
  9. customThe residue was purified by flash chromatography on silica gel (cyclohexane/ethyl acetate 100/0 to 95/5)

Sources & evidence

ORD record
ord-da048b8f0ba84da6a57ab2eb827cda2f
Source dataset
uspto-grants-2016_02
Patent number
US09260395B2

Reaction notes

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