Cyclopropylacetylene → HCID 57804096, compound

HRID 2102915Notes

Reaction equation

HRID 2102915 reaction equation
Br[C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8]C)=[O:7])=[C:4]([CH3:12])[CH:3]=1.[C:13]([CH:15]1[CH2:17][CH2:16]1)#[CH:14]>C(N(CC)CC)C.[Cu](I)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>[CH:15]1([C:13]#[C:14][C:2]2[CH:11]=[CH:10][C:5]([C:6]([OH:8])=[O:7])=[C:4]([CH3:12])[CH:3]=2)[CH2:17][CH2:16]1

Participants

6

Reactant 2

HCID 138823CyclopropylacetyleneHCID 22031226Methyl 4-bromo-2-methylbenzoate

Product 1

HCID 57804096HCID 57804096, compoundYield 71.5%

Reagents, catalysts & solvents 3

HCID 83717Copper iodideCatalystHCID 178418476HCID 178418476, compoundCatalystHCID 8471TriethylamineSolvent

Conditions

Temperature
80 °C

Procedure

Methyl 4-Bromo-2-methylbenzoate (1.0 g, 4.4 mmol) was dissolved in triethylamine (5 mL). To the mixture was added copper iodide (43 mg, 5 mol %), followed by PdCl2(PPh3)2 (157 mg, 5 mol %) and ethynylcyclopropane (1.43 ml, 12 mmol). The mixture was heated in a sealed pressure tube at 80° C. for 3 hours. After completion of the reaction, the triethylamine was evaporated and the residue was dissolved in EtOAc and filtered through Celite®. The organic layer was washed with water, brine, and dried (Na2SO4), then filtered and concentrated under vacuum. The residue was purified by column chromatography on sililca gel using EtOAc-hexane (0-100% gradient) as eluent to give the desired product (630 mg). The product was dissolved in 10 mL of MeOH and 10 mL of 2N LiOH and the mixture was refluxed overnight. The MeOH was evaporated and the basic layer was washed with EtOAC, acidified, and re-extracted with EtOAC. The organic layer was washed with brine, dried (Na2SO4), filtered and concentrated under vacuum to give the desired product as a beige solid (461 mg). m/z 201 (M+1).

Workup

  1. customAfter completion of the reaction
  2. customthe triethylamine was evaporated
  3. dissolutionthe residue was dissolved in EtOAc
  4. filtrationfiltered through Celite®
  5. washThe organic layer was washed with water, brine
  6. dry with materialdried (Na2SO4)
  7. filtrationfiltered
  8. concentrationconcentrated under vacuum
  9. customThe residue was purified by column chromatography on sililca gel

Sources & evidence

ORD record
ord-b5e27706ce004925b9df39ebb6fca80f
Source dataset
uspto-grants-2009_08
Patent number
US07576099B2

Reaction notes

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