Trimethylsilylacetylene → 2-Methyl-2-(3-trimethylsilanylethynyl-phenyl)-propionitrile

HRID 656455Notes

Reaction equation

HRID 656455 reaction equation
[C:1]([Si:3]([CH3:6])([CH3:5])[CH3:4])#[CH:2].Br[C:8]1[CH:9]=[C:10]([C:14]([CH3:18])([CH3:17])[C:15]#[N:16])[CH:11]=[CH:12][CH:13]=1>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)C>[CH3:18][C:14]([C:10]1[CH:11]=[CH:12][CH:13]=[C:8]([C:2]#[C:1][Si:3]([CH3:6])([CH3:5])[CH3:4])[CH:9]=1)([CH3:17])[C:15]#[N:16]

Participants

6

Reactant 2

HCID 66111TrimethylsilylacetyleneHCID 105132942-(3-Bromophenyl)-2-methylpropanenitrile

Product 1

HCID 671872992-Methyl-2-(3-trimethylsilanylethynyl-phenyl)-propionitrile

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 6342AcetonitrileSolvent

Procedure

Ethynyltrimethylsilane (4.0 mL, 28.9 mmol) was added to a mixture of ACN (100 mL), TEA (25 mL), 2-(3-bromophenyl)-2-methylpropionitrile (5.0 g, 22.3 mmol), (Ph3P)2PdCl2 (780 mg, 1.11 mol) and copper(I) iodide (130 mg, 0.68 mmol) under nitrogen atmosphere. The reaction mixture was refluxed for 3 hours, cooled to ambient temperature, concentrated to a black residue and filtered through silica gel with 20% ethyl acetate in hexane. The filtrate was concentrated to a red oil and chromatographed on silica gel with 2% ethyl acetate in hexane. Obtained 2-methyl-2-(3-trimethylsilanylethynylphenyl)-propionitrile (4.00 g, 74%) as an orange oil. 1H NMR (DMSO-d6) δ: 0.24 (s, 9H), 1.69 (s, 6H), 7.43 (m, 2H), 7.56 (m, 2H).

Workup

  1. temperatureThe reaction mixture was refluxed for 3 hours
  2. concentrationconcentrated to a black residue
  3. filtrationfiltered through silica gel with 20% ethyl acetate in hexane
  4. concentrationThe filtrate was concentrated to a red oil
  5. customchromatographed on silica gel with 2% ethyl acetate in hexane

Sources & evidence

ORD record
ord-a7344ba588fc444cb9aa7dafa33fc64b
Source dataset
uspto-grants-2011_12
Patent number
US08071762B2

Reaction notes

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