Trimethylsilylacetylene → 3-[(Trimethylsilyl)ethynyl]benzonitrile

HRID 606785Notes

Reaction equation

HRID 606785 reaction equation
[CH3:1][Si:2]([C:5]#[CH:6])([CH3:4])[CH3:3].I[C:8]1[CH:9]=[C:10]([CH:13]=[CH:14][CH:15]=1)[C:11]#[N:12]>C(N(CC)CC)C.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>[CH3:1][Si:2]([C:5]#[C:6][C:8]1[CH:9]=[C:10]([CH:13]=[CH:14][CH:15]=1)[C:11]#[N:12])([CH3:4])[CH3:3]

Participants

7

Reactant 2

HCID 66111Trimethylsilylacetylene2×HCID 1443413-Iodobenzonitrile

Product 1

HCID 225703183-[(Trimethylsilyl)ethynyl]benzonitrileYield 83%

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178419050HCID 178419050, compoundCatalystHCID 8471TriethylamineSolventHCID 8857Ethyl AcetateSolvent

Procedure

Add trimethylsilylacetylene (3.4 mL, 24.0 mmol) to a mixture of bis(triphenylphosphine)palladium (II) dichloride (766 mg, 1.1 mmol), copper (I) iodide (418 mg, 2.2 mmol) and 3-iodobenzonitrile (5 g, 21.8 mmol) in triethylamine (20 mL). Upon addition of the trimethylsilylacetylene an exothermic reaction occurs and after about 4 min the reaction mixture solidifies. Cool the reaction mixture for about 15 min, dilute with ethyl acetate (100 mL), filter through fluted filter paper using ethyl acetate and concentrate. Dissolve the residue in ethyl acetate (200 mL) and wash sequentially with an aqueous solution of 0.1 N hydrochloric acid and a saturated aqueous solution of sodium chloride. Dry (sodium sulfate), filter and concentrate. Purify the residue by silica gel chromatography, eluting with 0:100 to 5:95 ethyl acetate:hexanes, to give the title compound as a tan solid (3.6 g, 83%).

Workup

  1. customan exothermic reaction
  2. temperatureCool the reaction mixture for about 15 min
  3. filtrationfilter
  4. filtrationthrough fluted filter paper
  5. concentrationconcentrate
  6. dissolutionDissolve the residue in ethyl acetate (200 mL)
  7. washwash sequentially with an aqueous solution of 0.1 N hydrochloric acid
  8. dry with materialDry (sodium sulfate)
  9. filtrationfilter
  10. concentrationconcentrate
  11. customPurify the residue by silica gel chromatography
  12. washeluting with 0:100 to 5:95 ethyl acetate

Sources & evidence

ORD record
ord-dbc324667dfe48e0abbb4cc35fc4f348
Source dataset
uspto-grants-2011_03
Patent number
US07915424B2

Reaction notes

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