3,3-Dimethyl-1-butyne → HCID 57804186, compound

HRID 2102930Notes

Reaction equation

HRID 2102930 reaction equation
Br[C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[C:4]([Cl:12])[CH:3]=1.[CH3:13][C:14]([CH3:18])([CH3:17])[C:15]#[CH:16]>CCN(CC)CC.CN(C=O)C.[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>[Cl:12][C:4]1[CH:3]=[C:2]([C:16]#[C:15][C:14]([CH3:18])([CH3:17])[CH3:13])[CH:11]=[CH:10][C:5]=1[C:6]([O:8][CH3:9])=[O:7]

Participants

7

Reactant 2

HCID 135123,3-Dimethyl-1-butyneHCID 22058730Methyl 4-Bromo-2-chlorobenzoate

Product 1

HCID 57804186HCID 57804186, compoundYield 82.3%

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 6228DimethylformamideSolventHCID 8471TriethylamineSolvent

Conditions

Temperature
100 °C

Procedure

A mixture of methyl 4-bromo-2-chlorobenzoate (400 mg, 0.0016 mol), copper(I) iodide (30 mg, 0.00016 mol), 3,3-dimethyl-1-butyne (0.29 mL, 0.0024 mol) and bis(triphenylphosphine)palladium(II) chloride (110 mg, 0.00016 mol) in Et3N (5 mL) and DMF (2 mL) was heated at 100° C. in a 50 mL sealed reaction vessel for 32 hours. After cooling, the mixture was filtered through Celite® and the filter cake was washed repeatedly with ethyl acetate. The organic phase was washed with brine, dried (Na2SO4), and concentrated under vacuum. The residue was purified by column chromatography on silica gel to give the product (330 mg, 82%) as a light yellow oil.

Workup

  1. customsealed
  2. customreaction vessel for 32 hours
  3. temperatureAfter cooling
  4. filtrationthe mixture was filtered through Celite®
  5. washthe filter cake was washed repeatedly with ethyl acetate
  6. washThe organic phase was washed with brine
  7. dry with materialdried (Na2SO4)
  8. concentrationconcentrated under vacuum
  9. customThe residue was purified by column chromatography on silica gel

Sources & evidence

ORD record
ord-f135c3d011094209a76b8da0543447eb
Source dataset
uspto-grants-2009_08
Patent number
US07576099B2

Reaction notes

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