反应详情

A solution of sodium nitrite (20. g, 0.28 mol) in water (100 mL) was slowly added to a solution of 2-methoxy-pyridin-3-ylamine (36 g, 0.25 mol) in hydrochloric acid (20% aqueous solution, 60 mL) at 0° C. After stirring for 10 minutes, a cooled (0° C.) solution of acrolein (25 mL, 0.37 mol) in acetone (25 mL) containing calcium oxide (5 g, 0.09 mol) was slowly added to the reaction mixture. This was then followed by a solution of cuprous chloride (2.5 g, 0.025 mol) in acetone (25 mL) containing hydrochloric acid (20% aqueous solution, 5 mL). The mixture was stirred at 0 to 30° C. for 3 hours, and then extracted three times with dichloromethane (150 mL). The combined organic layers were washed with a saturated aqueous solution of sodium bicarbonate, a saturated aqueous solution of sodium chloride, dried over sodium sulfate, filtered, and evaporated to dryness to give a black viscous oil. The crude product was passed through a short silica column to give a crude product, which was used directly in the next step.

1. additionwas slowly added to the reaction mixture
2. stirringThe mixture was stirred at 0 to 30° C. for 3 hours
3. extractionextracted three times with dichloromethane (150 mL)
4. washThe combined organic layers were washed with a saturated aqueous solution of sodium bicarbonate
5. dry with materiala saturated aqueous solution of sodium chloride, dried over sodium sulfate
6. filtrationfiltered
7. customevaporated to dryness
8. customto give a black viscous oil