Trimethylsilylacetylene → HCID 13741615, compound

HRID 1644718Notes

Reaction equation

HRID 1644718 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([S:8]([CH3:11])(=[O:10])=[O:9])=[CH:4][CH:3]=1.[CH3:12][Si:13]([C:16]#[CH:17])([CH3:15])[CH3:14]>[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>[CH3:11][S:8]([C:5]1[CH:6]=[CH:7][C:2]([C:17]#[C:16][Si:13]([CH3:15])([CH3:14])[CH3:12])=[CH:3][CH:4]=1)(=[O:10])=[O:9]

Participants

5

Reactant 2

HCID 66111TrimethylsilylacetyleneHCID 770141-Bromo-4-(methylsulphonyl)benzene

Product 1

HCID 13741615HCID 13741615, compoundYield 100%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalyst

Procedure

Bromo-4-methanesulfonyl benzene (50.78 g, 213 mmol) was placed in a 3-necked round bottomed flask and purged with argon. Copper(I) iodide (2.05 g, 10.6 mmol) and bis(triphenylphosphine)palladium(II) chloride (PdCl2(PPh3)2) (7.55 g, 10.6 mmol) were added while purging with argon, followed by the addition of triethylamine (200 mL) and anhydrous dichloromethane (200 mL). (Trimethylsilyl)acetylene (61 mL, 425 mmol) was added and the reaction mixture was stirred at room temperature over 72 hours. The mixture was concentrated, then partitioned between ethyl acetate and water. The combined organic layers were washed with 1 N hydrochloric acid, water, and brine, dried over magnesium sulfate, filtered, and concentrated to afford crude (4-methanesulfonyl-phenylethynyl)-trimethyl-silane (54 g, 213 mmol), which was used in the next step without further purification. MS (ESI+) cald. for C12H16O2SSi [(M+H)+] 252, obsd. 253.

Workup

  1. custompurged with argon
  2. customwhile purging with argon
  3. additionfollowed by the addition of triethylamine (200 mL) and anhydrous dichloromethane (200 mL)
  4. concentrationThe mixture was concentrated
  5. custompartitioned between ethyl acetate and water
  6. washThe combined organic layers were washed with 1 N hydrochloric acid, water, and brine
  7. dry with materialdried over magnesium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated

Sources & evidence

ORD record
ord-08d61c025d164cb2af77474b59017db7
Source dataset
uspto-grants-2012_02
Patent number
US08124629B2

Reaction notes

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