反应详情

温度

0 °C

6-Hydroxy-pyrimidine-4-carbaldehyde oxime (9.3 g, 67 mmol) was stirred in 37 ml POCl3 under N2 at 40° C. for 30 min, 60° C. for 30 min, and 80° C. for one h. N,N,-Dimethylaniline was added very slowly by syringe, and stirredfor one h at 80° C. After cooling to 0° C., the mixture was poured into a separatory funnel containing 300 g of ice. The mixture was carefully swirled, then extracted with 500 ml t-BuOMe. The organic layer was washed with 1 N HCl (4×100 ml), then several times with NaHCO3, then brine. Acidic and basic aqueous layers were separately back-extracted with t-BuOMe, and the organics again washed with 1 N HCl, saturated aqueous NaHCO3, and brine. The combined organic layers were dried with Na2SO4 and concentrated by rotary evaporator. The residue was filtered through a pad of silica gel, applying in CH2Cl2 and eluting with 10:1 hexanes/t-BuOMe. Fractions were carefully concentrated to obtain 6-chloro-pyrimidine-4-carbonitrile as a (volatile) pale yellow, semi-crystalline solid.

1. customat 80° C
2. additionthe mixture was poured into a separatory funnel
3. extractionextracted with 500 ml t-BuOMe
4. washThe organic layer was washed with 1 N HCl (4×100 ml)
5. extractionAcidic and basic aqueous layers were separately back-extracted with t-BuOMe
6. washthe organics again washed with 1 N HCl, saturated aqueous NaHCO3, and brine
7. dry with materialThe combined organic layers were dried with Na2SO4
8. concentrationconcentrated by rotary evaporator
9. filtrationThe residue was filtered through a pad of silica gel
10. washeluting with 10:1 hexanes/t-BuOMe
11. concentrationFractions were carefully concentrated