2-Butyn-1-ol → 4,5-Dichloro-6-(2-butynyloxy)pyrimidine

HRID 1760002Notes

Reaction equation

HRID 1760002 reaction equation
[H-].[Na+].[CH2:3]([OH:7])[C:4]#[C:5][CH3:6].[Cl:8][C:9]1[C:14]([Cl:15])=[C:13](Cl)[N:12]=[CH:11][N:10]=1.[Cl-].[NH4+]>O1CCCC1>[Cl:8][C:9]1[C:14]([Cl:15])=[C:13]([O:7][CH2:3][C:4]#[C:5][CH3:6])[N:12]=[CH:11][N:10]=1

Participants

6

Reactant 4

HCID 129912-Butyn-1-olHCID 24758Sodium hydrideHCID 25517Ammonium ChlorideHCID 2490074,5,6-Trichloropyrimidine

Product 1

HCID 225997514,5-Dichloro-6-(2-butynyloxy)pyrimidineYield 94.2%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Procedure

In 18 ml of tetrahydrofuran was suspended 0.56 g of sodium hydride (60% in oil), to which 2 ml of a tetrahydrofuran solution containing 0.8 g of 2-butyn-1-ol was slowly added dropwise with stirring at room temperature. The mixture was stirred at room temperature for 20 minutes and then cooled to 0° C., to which 3 ml of a tetrahydrofuran solution containing 2 g of 4,5,6-trichloropyrimidine was slowly added dropwise, followed by further stirring at 0° C. for 2 hours. The reaction mixture was then poured into a saturated aqueous ammonium chloride solution and extracted three times with ethyl acetate. The organic layers were combined, washed with brine, dried over anhydrous magnesium sulfate, and then concentrated. The residue was subjected to silica gel column chromatography to give 2.23 g of 4,5-dichloro-6-(2-butynyloxy)pyrimidine.

Workup

  1. additionwas slowly added dropwise
  2. stirringThe mixture was stirred at room temperature for 20 minutes
  3. additionwas slowly added dropwise
  4. stirringby further stirring at 0° C. for 2 hours
  5. extractionextracted three times with ethyl acetate
  6. washwashed with brine
  7. dry with materialdried over anhydrous magnesium sulfate
  8. concentrationconcentrated

Sources & evidence

ORD record
ord-946a80190605409c941cc83abf641a7c
Source dataset
uspto-grants-2005_01
Patent number
US06838463B2

Reaction notes

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