Nitrogen → 4-(Methylthio)-7-((trimethylsilyl)ethynyl)thieno[3,2-d]pyrimidine

HRID 1465033Notes

Reaction equation

HRID 1465033 reaction equation
Br[C:2]1[C:6]2[N:7]=[CH:8][N:9]=[C:10]([S:11][CH3:12])[C:5]=2[S:4][CH:3]=1.C1(NC2CCCCC2)CCCCC1.[C:26]([Si:28]([CH3:31])([CH3:30])[CH3:29])#[CH:27].N#N>C(#N)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>[CH3:12][S:11][C:10]1[C:5]2[S:4][CH:3]=[C:2]([C:27]#[C:26][Si:28]([CH3:31])([CH3:30])[CH3:29])[C:6]=2[N:7]=[CH:8][N:9]=1

Participants

8

Reactant 4

HCID 947NitrogenHCID 7582DicyclohexylamineHCID 66111TrimethylsilylacetyleneHCID 469284277-Bromo-4-methylsulfanylthieno[3,2-d]pyrimidine

Product 1

HCID 673274394-(Methylthio)-7-((trimethylsilyl)ethynyl)thieno[3,2-d]pyrimidineYield 65.6%

Reagents, catalysts & solvents 3

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

Conditions

Temperature
80 °C

Procedure

7-Bromo-4-(methylthio)thieno[3,2-d]pyrimidine (3 g, 11.49 mmol) was dissolved in acetonitrile (30 mL) and then bis(triphenylphosphine)palladium(II) dichloride (204 mg, 0.29 mmol), CuI (76 mg, 0.40 mmol), dicyclohexylamine (2.5 mL, 12.64 mmol) and ethynyltrimethylsilane (3.2 mL, 22.98 mmol) were added thereto. The reaction mixture was treated with N2 gas for 15 minutes and stirred at 80° C. for 14 hours. The reaction mixture was cooled to room temperature, filtered using Celite and washed with ethyl acetate (50 mL). The filtrate was washed with brine and concentrated by drying with MgSO4. The resulting mixture was purified by silica gel chromatography (ethyl acetate/hexane=1:9˜2:8) to obtain the title compound (2.1 g, 65% yield) as a yellowish solid.

Workup

  1. temperatureThe reaction mixture was cooled to room temperature
  2. filtrationfiltered
  3. washwashed with ethyl acetate (50 mL)
  4. washThe filtrate was washed with brine
  5. concentrationconcentrated
  6. dry with materialby drying with MgSO4
  7. customThe resulting mixture was purified by silica gel chromatography (ethyl acetate/hexane=1:9˜2:8)

Sources & evidence

ORD record
ord-a36e33a791074d14a69a0490b9d346bd
Source dataset
uspto-grants-2015_04
Patent number
US08999973B2

Reaction notes

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