Water → 4-(4-Methylpent-1-ynyl)-2-(methylthio)pyrimidine

HRID 859968Notes

Reaction equation

HRID 859968 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][CH:18]([CH3:22])[CH2:19][C:20]#[CH:21].O>O1CCCC1.[Cu]I.CCOCC>[CH3:17][CH:18]([CH3:22])[CH2:19][C:20]#[C:21][C:2]1[CH:7]=[CH:6][N:5]=[C:4]([S:8][CH3:9])[N:3]=1

Participants

8

Reactant 4

HCID 962WaterHCID 8471TriethylamineHCID 1389484-Methyl-1-pentyneHCID 38589014-Iodo-2-(methylthio)pyrimidine

Product 1

HCID 694392334-(4-Methylpent-1-ynyl)-2-(methylthio)pyrimidineYield 92%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a cold (0° C.) solution of 4-iodo-2-(methylthio)pyrimidine (4.73 g, 21.2 mmol) in tetrahydrofuran (70 mL) was added copper (I) iodide (404 mg, 2.12 mmol), dichlorobistriphenylphosphine palladium (II) (744 mg, 1.06 mmol), and triethylamine (8.8 mL, 63.8 mmol). 4-Methyl-pentyne (5.0 mL, 42.5 mmol) was added dropwise to the reaction mixture and the resultant solution was stirred at 0° C. for 30 minutes and then at room temperature for 72 hours. Water and ether were added and the layers separated. The organic layer was washed with brine. The aqueous layer was extracted with ether and the combined organics were dried over magnesium sulfate. Filtration and concentration followed flash chromatography on silica gel (4:1 hexane-ether) provided 4-(4-methylpent-1-ynyl)-2-(methylthio)pyrimidine (4.0 g, 92%) as a clear oil. 1H NMR (CDCl3) δ 8.44 (d, 1H), 6.96 (d, 1H), 2.56 (s, 3H), 2.35 (d, 2H), 1.97 (M, 1H), 1.05 (d, 6H); MS m/z 207 (M+1).

Workup

  1. customthe layers separated
  2. washThe organic layer was washed with brine
  3. extractionThe aqueous layer was extracted with ether
  4. dry with materialthe combined organics were dried over magnesium sulfate
  5. filtrationFiltration and concentration

Sources & evidence

ORD record
ord-6238d71f8fc74ffd8aaeae14e976e49b
Source dataset
uspto-grants-2006_12
Patent number
US07153863B2

Reaction notes

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