Trimethylsilylacetylene → Methyl 4-(acetylamino)-2-chloro-5-[(trimethylsilyl)ethynyl]benzoate

HRID 1891016Notes

Reaction equation

HRID 1891016 reaction equation
[CH3:1][O:2][C:3](=[O:16])[C:4]1[CH:9]=[C:8](I)[C:7]([NH:11][C:12](=[O:14])[CH3:13])=[CH:6][C:5]=1[Cl:15].[C:17]([Si:19]([CH3:22])([CH3:21])[CH3:20])#[CH:18]>ClCCl>[CH3:1][O:2][C:3](=[O:16])[C:4]1[CH:9]=[C:8]([C:18]#[C:17][Si:19]([CH3:22])([CH3:21])[CH3:20])[C:7]([NH:11][C:12](=[O:14])[CH3:13])=[CH:6][C:5]=1[Cl:15]

Participants

4

Reactant 2

HCID 66111TrimethylsilylacetyleneHCID 11839202Methyl 4-acetamido-2-chloro-5-iodobenzoate

Product 1

HCID 11839199Methyl 4-(acetylamino)-2-chloro-5-[(trimethylsilyl)ethynyl]benzoateYield 209.5%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

To a stirred solution of 2-Chloro-4-acetamido-5-iodobenzoic acid methyl ester (2.5 g, 2.8 mmol) in dichloromethane (15.0 mL) were cuprous iodide (0.135 g, 0.71 mmol) and dichloro(bistriphenylphosphine)palladium(II) (0.25 g, 0.31 mmol). The mixture was cooled in an ice bath and added ethynyltrimethylsilane (0.825 g, 8.4 mmol). The resulting mixture was stirred under nitrogen at room temperature for 16 h. The mixture was diluted with dichloromethane (15.0 mL), washed with 5% citric acid, followed by water and dried (MgSO4). After the removal of the solvent, mixture was purified by silica gel flash chromatography using 20% ethyl acetate in heptane to afford the title compound as a light brown powder (1.9 g, 86%), m/z=252 (MH+—SiMe3).

Workup

  1. temperatureThe mixture was cooled in an ice bath
  2. washwashed with 5% citric acid
  3. dry with materialdried (MgSO4)
  4. customAfter the removal of the solvent, mixture
  5. customwas purified by silica gel flash chromatography

Sources & evidence

ORD record
ord-6d492b45304741c0a0c002e93bb1c605
Source dataset
uspto-grants-2013_08
Patent number
US08507499B2

Reaction notes

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