2-Bromothiophene → 2-[(Trimethylsilyl)ethynyl]thiophene

HRID 1460987Notes

Reaction equation

HRID 1460987 reaction equation
Br[C:2]1[S:3][CH:4]=[CH:5][CH:6]=1.[CH3:7][Si:8]([C:11]#[CH:12])([CH3:10])[CH3:9]>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.[Cu]I.C(N(CC)CC)C>[CH3:7][Si:8]([CH3:10])([CH3:9])[C:11]#[C:12][C:2]1[S:3][CH:4]=[CH:5][CH:6]=1

Participants

6

Reactant 2

HCID 138512-BromothiopheneHCID 66111Trimethylsilylacetylene

Product 1

HCID 5968702-[(Trimethylsilyl)ethynyl]thiopheneYield 82.4%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 8471TriethylamineSolvent

Procedure

Under a nitrogen atmosphere a solution of 12.0 grams (0.074 mole) of 2-bromothiophene, 9.0 grams (0.092 mole) of trimethylsilylacetylene, and 120 ml of triethylamine was stirred, and 0.52 gram (catalyst) of bis(triphenylphosphine)palladium(II) chloride and 0.28 gram (catalyst) of copper(I) iodide were added. Upon completion of addition, the reaction mixture was stirred at ambient temperature during an 18 hour period. After this time the reaction mixture was concentrated under reduced pressure to a residue. The residue was dissolved in diethyl ether, and the solution was washed with two portions of an aqueous 10% ammonium chloride solution, one portion of water, and one portion of an aqueous solution saturated with sodium chloride. The organic layer was dried with sodium sulfate and filtered. The filtrate was concentrated under reduced pressure to a residue. The residue was subjected to column chromatography on silica gel. Elution was accomplished using 10% methylene chloride in hexane. The appropriate fractions were combined and concentrated under reduced pressure yielding 11.0 grams of 2-trimethylsilylethynylthiophene. The nmr spectrum was consistent with the proposed structure.

Workup

  1. additionUpon completion of addition
  2. concentrationAfter this time the reaction mixture was concentrated under reduced pressure to a residue
  3. dissolutionThe residue was dissolved in diethyl ether
  4. washthe solution was washed with two portions of an aqueous 10% ammonium chloride solution, one portion of water, and one portion of an aqueous solution saturated with sodium chloride
  5. dry with materialThe organic layer was dried with sodium sulfate
  6. filtrationfiltered
  7. concentrationThe filtrate was concentrated under reduced pressure to a residue
  8. washElution
  9. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-281d8650bfbd44769e19ea9a37bf7f93
Source dataset
uspto-grants-1991_12
Patent number
US05073564

Reaction notes

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