Trimethylsilylacetylene → 2-Chloro-4-(2-(trimethylsilyl)ethynyl)pyridine

HRID 19782Notes

Reaction equation

HRID 19782 reaction equation
Br[C:2]1[CH:7]=[CH:6][N:5]=[C:4]([Cl:8])[CH:3]=1.[CH3:9][Si:10]([C:13]#[CH:14])([CH3:12])[CH3:11]>C(N(CC)CC)C.[Cu]I.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.Cl[Pd]Cl>[Cl:8][C:4]1[CH:3]=[C:2]([C:14]#[C:13][Si:10]([CH3:12])([CH3:11])[CH3:9])[CH:7]=[CH:6][N:5]=1

Participants

6

Reactant 2

HCID 66111TrimethylsilylacetyleneHCID 38477704-Bromo-2-chloropyridine

Product 1

HCID 219853912-Chloro-4-(2-(trimethylsilyl)ethynyl)pyridineYield 91%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 6102075Dichlorobis(triphenylphosphine)palladiumCatalystHCID 8471TriethylamineSolvent

Procedure

A mixture of 2.5 g of 4-bromo-2-chloropyridine (12.6 mmol), 2.2 ml of (trimethylsilyl)acetylene (15.1 mmol), 153 mg of copper(I)iodide (0.79 mmol) and 287 mg of bis(triphenylphosphine)palladium(II)chloride (0.41 mmol) in triethylamine (15 ml) was stirred at RT for 1 h. The triethylamine was then removed in vacuo, water was added and the mixture was extracted with diethylether. The combined organic extracts were then washed with water and brine, dried (Na2SO4), filtered and concentrated in vacuo to give a residue which was purified by column chromatography (heptane/EtOAc 100:0 to 98:2) to give 2-chloro-4-trimethylsilanylethynyl-pyridine (2.394 g, 91%) as a light yellow liquid. MS (ISP) 210.1 (M+H)+.

Workup

  1. customThe triethylamine was then removed in vacuo, water
  2. additionwas added
  3. extractionthe mixture was extracted with diethylether
  4. washThe combined organic extracts were then washed with water and brine
  5. dry with materialdried (Na2SO4)
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. customto give a residue which
  9. customwas purified by column chromatography (heptane/EtOAc 100:0 to 98:2)

Sources & evidence

ORD record
ord-42fbcf0d962848b08f31746a54c93e2b
Source dataset
uspto-grants-2010_06
Patent number
US07745477B2

Reaction notes

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