Trimethylsilylacetylene → HCID 86715741, compound

HRID 930442Notes

Reaction equation

HRID 930442 reaction equation
[C:1]([Si:3]([CH3:6])([CH3:5])[CH3:4])#[CH:2].Br[C:8]1[C:9]([C:15]#[N:16])=[N:10][CH:11]=[C:12]([Cl:14])[CH:13]=1>[Cu]I.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Pd].CN(C=O)C>[Cl:14][C:12]1[CH:13]=[C:8]([C:2]#[C:1][Si:3]([CH3:6])([CH3:5])[CH3:4])[C:9]([C:15]#[N:16])=[N:10][CH:11]=1

Participants

6

Reactant 2

HCID 66111TrimethylsilylacetyleneHCID 225912463-Bromo-5-chloropyridine-2-carbonitrile

Product 1

HCID 86715741HCID 86715741, compoundYield 39.9%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 11979704Tetrakis(triphenylphosphine)palladiumCatalystHCID 6228DimethylformamideSolvent

Procedure

A pressure vessel was charged with TEA (7.65 mL, 55.2 mmol), ethynyltrimethylsilane (2.32 mL, 16.6 mmol), copper (I) iodide (0.263 g, 1.380 mmol), palladium (0) tetrakis(triphenylphosphine) (0.558 g, 0.483 mmol), 3-bromo-5-chloropicolinonitrile (3.0 g, 13.8 mmol), and DMF (50 ml). The vessel was flushed with argon, sealed, stirred at ambient temperature for 15 minutes, and then heated at 50° C. for 4 hours. The solution was diluted with water and extracted with EtOAc. The combined organic layers were concentrated, and the residue was purified by silica-gel chromatography, eluting 0-50% ethyl acetate in hexane, to afford the title compound (1.3 g, 5.5 mmol). MS m/z=235 (M+H).

Workup

  1. customThe vessel was flushed with argon
  2. customsealed
  3. temperatureheated at 50° C. for 4 hours
  4. additionThe solution was diluted with water
  5. extractionextracted with EtOAc
  6. concentrationThe combined organic layers were concentrated
  7. customthe residue was purified by silica-gel chromatography
  8. washeluting 0-50% ethyl acetate in hexane

Sources & evidence

ORD record
ord-ee8e413be8cc4fa0903bedf1b50b9c48
Source dataset
uspto-grants-2016_03
Patent number
US09296734B2

Reaction notes

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