Triethylamine → 5-[2-(Trimethylsilyl)ethynyl]pyridine-3-carbonitrile

HRID 606783Notes

Reaction equation

HRID 606783 reaction equation
Br[C:2]1[CH:3]=[N:4][CH:5]=[C:6]([CH:9]=1)[C:7]#[N:8].C(N(CC)CC)C.[CH3:17][Si:18]([C:21]#[CH:22])([CH3:20])[CH3:19]>C(OCC)(=O)C.C1(C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)[Pd][P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Cu]I>[CH3:17][Si:18]([C:21]#[C:22][C:2]1[CH:3]=[N:4][CH:5]=[C:6]([CH:9]=1)[C:7]#[N:8])([CH3:20])[CH3:19]

Participants

7

Reactant 3

HCID 8471TriethylamineHCID 66111TrimethylsilylacetyleneHCID 7367935-Bromonicotinonitrile

Product 1

HCID 161156995-[2-(Trimethylsilyl)ethynyl]pyridine-3-carbonitrileYield 109.3%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178419050HCID 178419050, compoundCatalystHCID 8857Ethyl AcetateSolvent

Procedure

Combine 5-bromonicotinonitrile (10.0 g, 53.0 mmol), bis(triphenylphosphine)palladium (II) dichloride (1.86 g, 2.65 mmol), copper (I) iodide (1.04 g, 5.46 mmol) and triethylamine (50 mL, 359 mmol) in a sealed tube under nitrogen and treat with (trimethylsilyl)acetylene (8.00 mL, 56.75 mmol). Stir the resultant black reaction mixture at 70° C. for 1.7 h and cool to room temperature. Dilute the reaction mixture with ethyl acetate and wash with a saturated aqueous solution of sodium chloride. Dry (sodium sulfate), filter and concentrate. Dissolve the residue in dichloromethane and filter through a pad of diatomaceous earth/silica gel. Wash with 80:20 dichloromethane:ethyl acetate. Concentrate the filtrate to give 11.6 g of the title compound as a brownish-tan solid. This material contains minor impurities, which do not have an adverse effect on subsequent chemistry (see PREPARATION 4). The crude material is purified by silica gel chromatography, eluting with 95:5 to 85:15 hexanes:ethyl acetate to give the title compound.

Workup

  1. customblack reaction mixture at 70° C. for 1.7 h
  2. washwash with a saturated aqueous solution of sodium chloride
  3. dry with materialDry (sodium sulfate)
  4. filtrationfilter
  5. concentrationconcentrate
  6. dissolutionDissolve the residue in dichloromethane
  7. filtrationfilter through a pad of diatomaceous earth/silica gel
  8. washWash with 80:20 dichloromethane
  9. concentrationConcentrate the filtrate

Sources & evidence

ORD record
ord-ec7aa1888d354008ba7344fdc23f2607
Source dataset
uspto-grants-2011_03
Patent number
US07915424B2

Reaction notes

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