Triethylamine → (4-Fluorophenylethynyl)trimethylsilane

HRID 1797048Notes

Reaction equation

HRID 1797048 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][C:5](I)=[CH:4][CH:3]=1.C(N(CC)CC)C.[CH3:16][Si:17]([C:20]#[CH:21])([CH3:19])[CH3:18]>O1CCCC1.[Cu]I.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[F:1][C:2]1[CH:7]=[CH:6][C:5]([C:21]#[C:20][Si:17]([CH3:19])([CH3:18])[CH3:16])=[CH:4][CH:3]=1

Participants

7

Reactant 3

HCID 8471TriethylamineHCID 96054-FluoroiodobenzeneHCID 66111Trimethylsilylacetylene2×

Product 1

HCID 5102724(4-Fluorophenylethynyl)trimethylsilane

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
23 °C

Procedure

4-Fluoroiodobenzene (112 mL, 0.97 mol) and triethylamine (176 mL, 1.26 mol) are dissolved in dry tetrahydrofuran (1.2 L) and nitrogen gas was bubbled through the solution for about 20 min. Copper (I) iodide (1.08 g, 5.7 mmol) and bis(triphenyphosphine)palladium dichloride (2.15 g, 3 mmol) are added and then trimethylsilylacetylene (178 mL, 1.3 mol) was added dropwise over about 40 min with the temperature being maintained at about 23° C. A large amount of precipitate forms (presumably Et3NHCl) which necessitates mechanical stirring. Following complete addition of the trimethylsilylacetylene the mixture was allowed to stir at room temperature for about 18 hours. The mixture was filtered and the solid washed with cyclohexane. The combined filtrates are concentrated under reduce pressure to give a brown oil. Application of this oil to a pad of silica gel followed by elution with cyclohexane gave a yellow solution. Removal of the solvent gave the title compound as a yellow oil; 182.8 g (95%).

Workup

  1. customnitrogen gas was bubbled through the solution for about 20 min
  2. filtrationThe mixture was filtered
  3. washthe solid washed with cyclohexane
  4. concentrationThe combined filtrates are concentrated
  5. customto give a brown oil
  6. washApplication of this oil to a pad of silica gel followed by elution with cyclohexane
  7. customgave a yellow solution
  8. customRemoval of the solvent

Sources & evidence

ORD record
ord-fc1f715bef1b4085a8b402a6c5fb3437
Source dataset
uspto-grants-2006_04
Patent number
US07034030B2

Reaction notes

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