p-Diiodobenzene → (4-Iodophenylethynyl)trimethylsilane

HRID 2111463Notes

Reaction equation

HRID 2111463 reaction equation
[CH3:1][Si:2]([C:5]#[CH:6])([CH3:4])[CH3:3].[I:7][C:8]1[CH:13]=[CH:12][C:11](I)=[CH:10][CH:9]=1>[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.C1COCC1>[I:7][C:8]1[CH:13]=[CH:12][C:11]([C:6]#[C:5][Si:2]([CH3:4])([CH3:3])[CH3:1])=[CH:10][CH:9]=1

Participants

6

Reactant 2

HCID 12208p-DiiodobenzeneHCID 66111Trimethylsilylacetylene

Product 1

HCID 11808725(4-Iodophenylethynyl)trimethylsilaneYield 130.9%

Reagents, catalysts & solvents 3

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

Conditions

Temperature
40 °C

Procedure

To a mixture of (trimethylsilyl)-acetylene (2.0 mL, 14 mmol) and 1,4-diiodobenzene (9.4 g, 28 mmol) in freshly distilled TEA (40 mL) and THF (20 mL) in a 100 mL Schlenk flask were added CuI (0.19 g, 1.0 mmol) and PdCl2(PPh3)2 (0.30 g, 0.43 mmol) with stirring. The flask was then evacuated and purged with argon (3 times) on a Schlenk line. The mixture was heated at 40° C. (oil bath), sealed and stirred for 4 h. The solvents were removed under reduced pressure. The residue was dissolved in ethyl ether (150 mL), washed with H2O (3×100 mL), dried (MgSO4) and filtered. The solvent removed under reduced pressure. The resulting residue was purified by column chromatography (silica, petroleum ether/ethyl ether, 10:1) to afford 5.5 g (85%) of an off-white solid. mp 57-59° C. (lit.25 56-58° C.); 1H NMR δ 0.33 (s, 9H), 7.18, 7.64 (AA′BB′, J=8.7 Hz, 2×2H); 13C NMR δ 0.24, 94.2, 96.1, 102.6, 123.4, 133.5, 137.8; FAB-MS obsd 299.9821, calcd exact mass 299.9882 (C11H13ISi).

Workup

  1. customThe flask was then evacuated
  2. custompurged with argon (3 times) on a Schlenk line
  3. customsealed
  4. stirringstirred for 4 h
  5. customThe solvents were removed under reduced pressure
  6. dissolutionThe residue was dissolved in ethyl ether (150 mL)
  7. washwashed with H2O (3×100 mL)
  8. dry with materialdried (MgSO4)
  9. filtrationfiltered
  10. customThe solvent removed under reduced pressure
  11. customThe resulting residue was purified by column chromatography (silica, petroleum ether/ethyl ether, 10:1)

Sources & evidence

ORD record
ord-d35771fab93648758710178358861c0c
Source dataset
uspto-grants-2009_04
Patent number
US07518905B2

Reaction notes

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