Triphenylphosphine → 2-((Trimethylsilyl)ethynyl)nicotinonitrile

HRID 883902Notes

Reaction equation

HRID 883902 reaction equation
[CH:1]1[CH:6]=[N:5][C:4](Cl)=[C:3]([C:8]#[N:9])[CH:2]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[CH3:29][Si:30]([C:33]#[CH:34])([CH3:32])[CH3:31]>C(N(CC)CC)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[CH3:29][Si:30]([CH3:32])([CH3:31])[C:33]#[C:34][C:4]1[N:5]=[CH:6][CH:1]=[CH:2][C:3]=1[C:8]#[N:9]

Participants

6

Reactant 3

HCID 11776TriphenylphosphineHCID 66111TrimethylsilylacetyleneHCID 810792-Chloronicotinonitrile

Product 1

HCID 134111132-((Trimethylsilyl)ethynyl)nicotinonitrileYield 75%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 8471TriethylamineSolvent

Procedure

In a suitably sized pressure vessel, commercially available 2-chloro-nictinonitrile (1.5 g, 10.8 mmol) was combined with triphenylphosphine (0.228 g, 8 mole %) and palladium (II) acetate (0.083 g, 3.5 mol %) in triethylamine (20 mL). Nitrogen was bubbled through the resulting suspension at room temperature for five minutes then trimethylsilylacetylene (8.5 mL, 60.1 mmol) was added, the vessel sealed and immersed in an 80° C. oil bath. After 18.5 h the pressure tube was cooled to room temperature and the contents were filtered. The filtrate was concentrated under vacuum and the crude product purified by flash chromatography on silica gel eluting with EtOAc/hexanes to give the title compound (1.62 g, 75%) as a tan solid.

Workup

  1. customNitrogen was bubbled through the resulting suspension at room temperature for five minutes
  2. customthe vessel sealed
  3. customimmersed in an 80° C.
  4. filtrationthe contents were filtered
  5. concentrationThe filtrate was concentrated under vacuum
  6. customthe crude product purified by flash chromatography on silica gel eluting with EtOAc/hexanes

Sources & evidence

ORD record
ord-7185a3d099154f9dbf55437c00752c77
Source dataset
uspto-grants-2012_08
Patent number
US08236950B2

Reaction notes

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