Trimethylsilylacetylene → 5-[(Trimethylsilyl)ethynyl]pyrimidine

HRID 505965Notes

Reaction equation

HRID 505965 reaction equation
Br[C:2]1[CH:3]=[N:4][CH:5]=[N:6][CH:7]=1.[CH3:8][Si:9]([C:12]#[CH:13])([CH3:11])[CH3:10]>C1(C)C=CC=CC=1.C(NC(C)C)(C)C.C(OCC)(=O)C.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[Pd].[Cu]I>[CH3:8][Si:9]([C:12]#[C:13][C:2]1[CH:3]=[N:4][CH:5]=[N:6][CH:7]=1)([CH3:11])[CH3:10]

Participants

8

Reactant 2

HCID 66111TrimethylsilylacetyleneHCID 783445-Bromopyrimidine

Product 1

HCID 153496695-[(Trimethylsilyl)ethynyl]pyrimidineYield 85%

Reagents, catalysts & solvents 5

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 11979704Tetrakis(triphenylphosphine)palladiumCatalystHCID 1140TolueneSolventHCID 7912DiisopropylamineSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
60 °C

Procedure

Tetrakis(triphenylphosphine)palladium(O) (727 mg, 0.6 mmol) was added to a stirred, degassed suspension of 5-bromopyrimidine (5.0 g, 31.4 mmol) and copper(I)iodide (120 mg, 0.6 mmol) in toluene and diisopropylamine (1:1, 200 ml) under nitrogen. The reaction mixture was heated to 60° C., trimethylsilylacetylene (4.89 ml, 34.6 mmol) was added and the reaction mixture was stirred for 3 hours at 60° C. The reaction mixture was allowed to cool to room temperature, diluted with ethyl acetate (200 ml) and washed with saturated aqueous ammonium chloride solution (3×100 ml). The organic layer was separated, dried over MgSO4 and concentrated in vacuo. The crude product was purified by flash column chromatography (5% ethyl acetate/heptane) to give 5-trimethylsilanylethynyl-pyrimidine as a pale brown solid, 4.71 g (85% yield). LC at 215 nm; Rt 2.07: 88%, m/z (ES+): 177 (M+H).

Workup

  1. customdegassed
  2. temperatureto cool to room temperature
  3. washwashed with saturated aqueous ammonium chloride solution (3×100 ml)
  4. customThe organic layer was separated
  5. dry with materialdried over MgSO4
  6. concentrationconcentrated in vacuo
  7. customThe crude product was purified by flash column chromatography (5% ethyl acetate/heptane)

Sources & evidence

ORD record
ord-ed51dcd02f0d49728475eac21d451aa2
Source dataset
uspto-grants-2010_08
Patent number
US07781593B2

Reaction notes

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