Triethylamine → 2-Bromo-4-chloro-1-[2-(trimethylsilyl)ethynyl]benzene

HRID 56636Notes

Reaction equation

HRID 56636 reaction equation
C(N(CC)CC)C.[Br:8][C:9]1[CH:14]=[C:13]([Cl:15])[CH:12]=[CH:11][C:10]=1I.[C:17]([Si:19]([CH3:22])([CH3:21])[CH3:20])#[CH:18]>C1COCC1.C(OCC)(=O)C.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>[Br:8][C:9]1[CH:14]=[C:13]([Cl:15])[CH:12]=[CH:11][C:10]=1[C:18]#[C:17][Si:19]([CH3:22])([CH3:21])[CH3:20]

Participants

8

Reactant 3

HCID 8471TriethylamineHCID 66111TrimethylsilylacetyleneHCID 137413262-Bromo-4-chloro-1-iodobenzene

Product 1

HCID 1020785952-Bromo-4-chloro-1-[2-(trimethylsilyl)ethynyl]benzene

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

Under argon, 2.89 ml (20.7 mmol, 5.0 eq.) of triethylamine, 2.99 g (4.1 mmol) of 2-bromo-4-chloro-1-iodobenzene and 489 mg (4.97 mmol, 1.2 eq.) of ethynyl(trimethyl)silane were added successively to a solution of 73 mg (0.10 mmol, 0.025 eq.) of bis(triphenylphosphine)palladium(II) chloride and 20 mg (0.10 mmol, 0.025 eq.) copper(I) iodide in 27 ml of THF, and the mixture was stirred at RT overnight. The reaction mixture was then diluted with ethyl acetate and filtered through Celite, and the filtrate was concentrated under reduced pressure. After addition of ethyl acetate/water and phase separation, the organic phase was concentrated under reduced pressure. The crude product was purified by flash chromatography (silica gel 60, mobile phase: cyclohexane/ethyl acetate mixtures). Yield: 3.21 g (quant.)

Workup

  1. filtrationfiltered through Celite
  2. concentrationthe filtrate was concentrated under reduced pressure
  3. additionAfter addition of ethyl acetate/water and phase separation
  4. concentrationthe organic phase was concentrated under reduced pressure
  5. customThe crude product was purified by flash chromatography (silica gel 60, mobile phase: cyclohexane/ethyl acetate mixtures)

Sources & evidence

ORD record
ord-ab0362d6ec0a4e289da25ab56c96eca7
Source dataset
uspto-grants-2016_09
Patent number
US09434690B2

Reaction notes

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