Trimethylsilylacetylene → HCID 58368507, compound

HRID 1192511Notes

Reaction equation

HRID 1192511 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-e413d8e931d24d4c9bef3020aa00f91c
Source dataset
uspto-grants-2014_03
Patent number
US08680108B2

Reaction notes

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