Trimethylsilylacetylene → 3,4-Dimethoxy-5-((trimethylsilyl)ethynyl)benzoic acid

HRID 638934Notes

Reaction equation

HRID 638934 reaction equation
I[C:2]1[CH:3]=[C:4]([CH:8]=[C:9]([O:13][CH3:14])[C:10]=1[O:11][CH3:12])[C:5]([OH:7])=[O:6].[CH3:15][Si:16]([C:19]#[CH:20])([CH3:18])[CH3:17]>CCN(CC)CC.C1C=CC=CC=1.[Cu]I.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH3:14][O:13][C:9]1[CH:8]=[C:4]([CH:3]=[C:2]([C:20]#[C:19][Si:16]([CH3:18])([CH3:17])[CH3:15])[C:10]=1[O:11][CH3:12])[C:5]([OH:7])=[O:6]

Participants

7

Reactant 2

HCID 66111TrimethylsilylacetyleneHCID 2304593-Iodo-4,5-dimethoxybenzoic acid

Product 1

HCID 686851233,4-Dimethoxy-5-((trimethylsilyl)ethynyl)benzoic acidYield 100.6%

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418397HCID 178418397, compoundCatalystHCID 241BenzeneSolventHCID 8471TriethylamineSolvent

Procedure

To a stirred solution of 3-iodo-4,5-dimethoxybenzoic acid (6.16 g, 20.0 mmol) in a mixture of Et3N (40 mL) and benzene (40 mL) at room temperature, was added CuI (380 mg, 2 mmol), Pd(PPh3)4 (462 mg, 0.4 mmol) and (trimethylsilyl)acetylene (3.4 mL, 24 mmol). After stirring for 3 days at room temperature, the solvent was removed in vacuo, the residue was diluted with 1 N HCl aqueous solution (300 mL) and then extracted with EtOAc (3×100 mL). The combined organic layer was washed with brine (300 mL), dried over Na2SO4 and concentrated in vacuo to give 3,4-dimethoxy-5-(trimethylsilanylethynyl)benzoic acid (5.6 g). The product was used without further purification.

Workup

  1. customthe solvent was removed in vacuo
  2. additionthe residue was diluted with 1 N HCl aqueous solution (300 mL)
  3. extractionextracted with EtOAc (3×100 mL)
  4. washThe combined organic layer was washed with brine (300 mL)
  5. dry with materialdried over Na2SO4
  6. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-e5a1440fae174ca295e66496290d471d
Source dataset
uspto-grants-2010_04
Patent number
US07691843B2

Reaction notes

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