Trimethylsilylacetylene → Methyl 2-chloro-5-((trimethylsilyl)ethynyl)benzoate

HRID 456871Notes

Reaction equation

HRID 456871 reaction equation
[CH3:1][O:2][C:3](=[O:12])[C:4]1[CH:9]=[C:8](I)[CH:7]=[CH:6][C:5]=1[Cl:11].[CH3:13][Si:14]([C:17]#[CH:18])([CH3:16])[CH3:15]>C(N(CC)CC)C.Cl[Pd-2](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.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[CH3:1][O:2][C:3](=[O:12])[C:4]1[CH:9]=[C:8]([C:18]#[C:17][Si:14]([CH3:16])([CH3:15])[CH3:13])[CH:7]=[CH:6][C:5]=1[Cl:11]

Participants

7

Reactant 2

HCID 66111TrimethylsilylacetyleneHCID 35563912Methyl 2-chloro-5-iodobenzoate

Product 1

HCID 57422929Methyl 2-chloro-5-((trimethylsilyl)ethynyl)benzoateYield 98.1%

Reagents, catalysts & solvents 4

HCID 11776TriphenylphosphineCatalystHCID 83717Copper iodideCatalystHCID 178418903HCID 178418903, compoundCatalystHCID 8471TriethylamineSolvent

Procedure

A mixture of 2-chloro-5-iodo-benzoic acid methyl ester (3.5 g, 12 mmol), dichlorobis(triphenylphosphino)palladium(II) (0.04 g, 0.06 mmol), triphenylphosphine (0.06 g, 0.24 mmol), copper iodide (0.05 g, 0.24 mmol), (trimethylsilyl)acetylene (1.9 g, 19.2 mmol) in triethylamine (40 mL) was heated at reflux for 12 h. The mixture was concentrated in vacuo, diluted with ethyl acetate (150 mL) and washed sequentially with 10% aqueous citric acid, water, and brine. The organic solution was dried, filtered and concentrated in vacuo to afford the title compound (3.14 g).

Workup

  1. temperaturewas heated
  2. temperatureat reflux for 12 h
  3. concentrationThe mixture was concentrated in vacuo
  4. additiondiluted with ethyl acetate (150 mL)
  5. washwashed sequentially with 10% aqueous citric acid, water, and brine
  6. customThe organic solution was dried
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-35f1d8e447844d7bb99c7c89a2e4d1d5
Source dataset
uspto-grants-2007_03
Patent number
US07186742B2

Reaction notes

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