Hexane → 2-(Methylsulfanyl)-4-[(trimethylsilyl)ethynyl]pyrimidine

HRID 1269036Notes

Reaction equation

HRID 1269036 reaction equation
I[C:2]1[CH:7]=[CH:6][N:5]=[C:4]([S:8][CH3:9])[N:3]=1.C(N(CC)CC)C.[CH3:17][Si:18]([C:21]#[CH:22])([CH3:20])[CH3:19].CCCCCC>O1CCCC1.[Cu]I>[CH3:9][S:8][C:4]1[N:3]=[C:2]([C:22]#[C:21][Si:18]([CH3:20])([CH3:19])[CH3:17])[CH:7]=[CH:6][N:5]=1

Participants

7

Reactant 4

HCID 8058HexaneHCID 8471TriethylamineHCID 66111Trimethylsilylacetylene2×HCID 38589014-Iodo-2-(methylthio)pyrimidine

Product 1

HCID 184466162-(Methylsulfanyl)-4-[(trimethylsilyl)ethynyl]pyrimidineYield 99%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 8028TetrahydrofuranSolvent

Procedure

4-Iodo-2-(methylsulfanyl)pyrimidine (2.0 g, 8.1 mmol) was dissolved in anhydrous tetrahydrofuran (50 mL). To this solution was added triethylamine (1.4 mL, 10.1 mmol), copper (I) iodide (80 mg, 0.4 mmol) and dichlorobis(triphenylphosphine) palladium (II) (140 mg, 0.24 mmol). (Trimethylsilyl)acetylene (1.4 mL, 10.1 mmol) was added dropwise to the resulting solution. After the addition of (trimethylsilyl)acetylene was complete the reaction was stirred at room temperature for 2 hours. Hexane was added to the reaction mixture and the mixture was filtered to remove precipitates. The solution was concentrated to give a syrup, that was purified by silica gel chromatography (1:1 ethyl acetate:hexane) to give 1.76 g (99%) of 2-(methylsulfanyl)-4-[(trimethylsilyl)ethynyl]pyrimidine. 2-(Methylsulfanyl)-4-[(trimethylsilyl)ethynyl]pyrimidine (1.76 g, 8.0 mmol) was dissolved in methanol (60 mL). To this solution was added potassium fluoride (467 mg, 8.0 mmol) and the resulting mixture stirred at room temperature for 5 minutes. The solution was concentrated and ethyl acetate and water were added. The phases were separated and the aqueous phase extracted with additional ethyl acetate. The organics were combined, dried over magnesium sulfate, filtered and concentrated to give 1.0 g (83%) of 4-ethynyl-2-(methylsulfanyl)pyrimidine as a white solid. 1H NMR (CDCl3): δ 8.51 (d, 1H), 7.06 (d, 1H), 3.34 (s, 1H), 2.56 (s, 3H); MS m/z 151 (M+1).

Workup

  1. filtrationthe mixture was filtered
  2. customto remove
  3. customprecipitates
  4. concentrationThe solution was concentrated
  5. customto give a syrup, that
  6. customwas purified by silica gel chromatography (1:1 ethyl acetate:hexane)

Sources & evidence

ORD record
ord-adcf4855163b4d1d8c99ef4dcc95af2b
Source dataset
uspto-grants-2007_04
Patent number
US07199120B2

Reaction notes

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