Trimethylsilylacetylene → HCID 59404985, compound

HRID 1892209Notes

Reaction equation

HRID 1892209 reaction equation
Br[C:2]1[CH:3]=[C:4]([N+:9]([O-:11])=[O:10])[C:5]([CH3:8])=[N:6][CH:7]=1.[CH3:12][Si:13]([C:16]#[CH:17])([CH3:15])[CH3:14]>C(N(CC)CC)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>[CH3:8][C:5]1[C:4]([N+:9]([O-:11])=[O:10])=[CH:3][C:2]([C:17]#[C:16][Si:13]([CH3:15])([CH3:14])[CH3:12])=[CH:7][N:6]=1

Participants

6

Reactant 2

HCID 66111TrimethylsilylacetyleneHCID 250672665-Bromo-2-methyl-3-nitropyridine

Product 1

HCID 59404985HCID 59404985, compoundYield 91.1%

Reagents, catalysts & solvents 3

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

Conditions

Temperature
80 °C

Procedure

To a solution of 5-bromo-2-methyl-3-nitropyridine (9.38 g, 43.2 mmol) and (trimethylsilyl)acetylene (9.16 mL, 64.8 mmol) in triethylamine (300 mL) were added bis(triphenylphosphine)palladium(II) chloride (3.34 g, 4.75 mmol) and copper(I) iodide (1.64 g, 8.64 mmol). The reaction mixture was allowed to stir for 4 h at 80° C. and then cooled to rt and filtered through Celite®. The filter pad was washed with EtOAc and the filtrate was washed with saturated aqueous NaHCO3 (500 mL) then brine (500 mL). The organic solution was dried over Mg2SO4, filtered and concentrated. The residue was purified by column chromatography to give 2-methyl-3-nitro-5-[(trimethylsilyl)ethynyl]pyridine (9.22 g, 91%). LCMS (FAL): Rt=11.04 min, m/z=235.1 (M+H).

Workup

  1. temperaturecooled to rt
  2. filtrationfiltered through Celite®
  3. washThe filter pad was washed with EtOAc
  4. washthe filtrate was washed with saturated aqueous NaHCO3 (500 mL)
  5. dry with materialThe organic solution was dried over Mg2SO4
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customThe residue was purified by column chromatography

Sources & evidence

ORD record
ord-96dba331347f46d8abb7640f227849d6
Source dataset
uspto-grants-2013_08
Patent number
US08507667B2

Reaction notes

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