Trimethylsilylacetylene → HCID 58368507, compound

HRID 515841Notes

Reaction equation

HRID 515841 reaction equation
[CH3:1][Si:2]([C:5]#[CH:6])([CH3:4])[CH3:3].[Cl:7][C:8]1[C:9](I)=[CH:10][C:11]([OH:18])=[C:12]([CH:17]=1)[C:13]([O:15][CH3:16])=[O:14]>C(N(CC)CC)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:7][C:8]1[C:9]([C:6]#[C:5][Si:2]([CH3:4])([CH3:3])[CH3:1])=[CH:10][C:11]([OH:18])=[C:12]([CH:17]=1)[C:13]([O:15][CH3:16])=[O:14]

Participants

6

Reactant 2

HCID 66111TrimethylsilylacetyleneHCID 58368557HCID 58368557, compound

Product 1

HCID 58368507HCID 58368507, compoundYield 95.3%

Reagents, catalysts & solvents 3

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

Conditions

Temperature
20 °C

Procedure

A solution of copper (I) iodide (1.1 g, 5.8 mmol) in triethylamine (32 mL) was degassed with nitrogen, treated with (trimethylsilyl)acetylene (4.5 mL, 32 mmol), degassed with nitrogen, and stirred at 20° C. for 10 minutes. The reaction mixture was treated with bis(triphenylphosphine)palladium(II) chloride (0.56 g, 0.80 mmol), degassed with nitrogen, and stirred at 20° C. for 30 minutes. The reaction mixture was treated with methyl 5-chloro-2-hydroxy-4-iodobenzoate (5.0 g, 16 mmol), degassed with nitrogen, and stirred at 75° C. for 2 hours. The reaction mixture was filtered over celite, washed with ethyl acetate, and concentrated to a crude residue. Purification via flash column chromatography using ethyl acetate in hexanes (0%-20%) gave the desired product (4.31 g, 95%). LCMS for C13H16ClO3Si (M+H)+: m/z=283.1; Found: 282.9.

Workup

  1. customdegassed with nitrogen
  2. customdegassed with nitrogen
  3. stirringstirred at 20° C. for 30 minutes
  4. customdegassed with nitrogen
  5. stirringstirred at 75° C. for 2 hours
  6. filtrationThe reaction mixture was filtered over celite
  7. washwashed with ethyl acetate
  8. concentrationconcentrated to a crude residue
  9. customPurification via flash column chromatography

Sources & evidence

ORD record
ord-722b63a8166d479295464d17fada2f8a
Source dataset
uspto-grants-2015_08
Patent number
US09108984B2

Reaction notes

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