1-Bromo-4-nitrobenzene → Trimethyl((4-nitrophenyl)ethynyl)silane

HRID 885778Notes

Reaction equation

HRID 885778 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[CH:4][CH:3]=1.[CH3:11][Si:12]([C:15]#[CH:16])([CH3:14])[CH3:13]>C(NC(C)C)(C)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>[CH3:11][Si:12]([C:15]#[C:16][C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[CH:4][CH:3]=1)([CH3:14])[CH3:13]

Participants

6

Reactant 2

HCID 114661-Bromo-4-nitrobenzeneHCID 66111Trimethylsilylacetylene

Product 1

HCID 4296099Trimethyl((4-nitrophenyl)ethynyl)silaneYield 70%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 7912DiisopropylamineSolvent

Procedure

A mixture of p-bromonitrobenzene (2.02 g, 10 mmol), bis(triphenylphosphine)palladium(II) chloride (0.2 g, 0.3 mmol), and copper(I) iodide (0.05 g, 0.3 mmol) in 40 ml of N,N-diisopropylamine was degassed by freeze/pump/thaw technique (three times). Trimethylsilylacetylene (1.2 g, 12 mmol) was added and the mixture was refluxed for 12 hours. After removal of amine by rotary evaporation, the residue was dissolved in CH2Cl2 and washed with water. The organic layer was dried (Na2SO4), filtered, and rotary evaporated. The residue was purified by column chromatography (EtOAc/hexanes, 1:10) to afford 4-(trimethylsilylethynyl)nitrobenzene (1.53 g, 70%). (Procedure adapted from Takahashi, S; Kuroyama, Y; Sonogashira, K; Hagihara, N. Synthesis, 1980, 627.)

Workup

  1. customwas degassed by freeze/pump/thaw technique (three times)
  2. temperaturethe mixture was refluxed for 12 hours
  3. customAfter removal of amine
  4. customby rotary evaporation
  5. dissolutionthe residue was dissolved in CH2Cl2
  6. washwashed with water
  7. dry with materialThe organic layer was dried (Na2SO4)
  8. filtrationfiltered
  9. customThe residue was purified by column chromatography (EtOAc/hexanes, 1:10)

Sources & evidence

ORD record
ord-7b7536f64eb745a2b48045eebde20384
Source dataset
uspto-grants-2012_08
Patent number
US08242307B1

Reaction notes

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