Trimethylsilylacetylene → Trimethyl((2-nitrophenyl)ethynyl)silane

HRID 1424551Notes

Reaction equation

HRID 1424551 reaction equation
I[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[N+:8]([O-:10])=[O:9].[CH3:11][Si:12]([C:15]#[CH:16])([CH3:14])[CH3:13]>CCN(CC)CC.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>[CH3:11][Si:12]([CH3:14])([CH3:13])[C:15]#[C:16][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[N+:8]([O-:10])=[O:9]

Participants

6

Reactant 2

HCID 66111TrimethylsilylacetyleneHCID 69115o-Iodonitrobenzene

Product 1

HCID 11333470Trimethyl((2-nitrophenyl)ethynyl)silaneYield 76%

Reagents, catalysts & solvents 3

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

Procedure

A mixture of 2-iodonitrobenzene (2.0 g, 8.0 mmol), bis(triphenylphosphine)palladium(II) chloride (0.30 g, 0.40 mmol) and copper(I) iodide (0.080 g, 0.40 mmol) in 25 mL of Et3N was degassed by freeze/pump/thaw technique (three times). Trimethylsilylacetylene (1.0 g, 10 mmol) was added and the mixture was stirred for 18 hours. The reaction mixture was filtered through a celite pad and the pad was rinsed with CH2Cl2. The filtrate was washed with sat. NH4Cl (aq.) and brine and the organic layer was dried (Na2SO4), filtered, and concentrated. The residue was purified by column chromatography (Hexane, then EtOAc;Hexane=1:60, 1:30) to afford trimethyl((2-nitrophenyl)ethynyl)silane (1.33 g, 76%): 1H-NMR (300 MHz, CDCl3) δ 8.02 (dd, J=8.1, 1,2 Hz, 1H), 7.66 (dd, J=7.5, 1.5 Hz, 1H), 7.56 (ddd, J=7.2, 7.2, 1.2 Hz, 1H), 7.45 (ddd, J=8.1, 8.1, 1.5 Hz, 1H) , 0.28 (s, 9H).

Workup

  1. customwas degassed by freeze/pump/thaw technique (three times)
  2. filtrationThe reaction mixture was filtered through a celite pad
  3. washthe pad was rinsed with CH2Cl2
  4. washThe filtrate was washed with sat. NH4Cl (aq.) and brine
  5. dry with materialthe organic layer was dried (Na2SO4)
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customThe residue was purified by column chromatography (Hexane

Sources & evidence

ORD record
ord-cf4612c4378e4ec2930d3e890d52626a
Source dataset
uspto-grants-2015_01
Patent number
US08927728B2

Reaction notes

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