反应详情

1-Methyl-3-piperidinol (3.5 g., 0.03 mole) and a small piece of sodium (~0.05 g.) were refluxed in 150 ml. of n-heptane for about 1 hour in a flask equipped with a small distilling head. Methyl α-ethynyl-α-phenylglycolate (4.0 g., 0.02 mole) was then added intermittently over a one hour period with the temperature of the reaction mixture maintained at 90°. The reaction mixture was heated at 90°-95° for three hours during which time very little methanol was collected. The reaction mixture was subsequently refluxed for 11 hours and the azeotrope collected periodically. During this time sodium methoxide (0.075 g.) was added and 50 ml. of fresh n-heptane was added as an equal volume of distillate was collected simultaneously. These operations were carried out twice. Heating was stopped and a total of 0.3 ml. (38% of theory) of methanol was obtained. As the reaction mixture cooled, an oil settled out. The n-heptane was decanted and the residue was washed with ice water (3×10 ml.). Ether and ice were added to the oil and the mixture worked up as described in Example 12, to yield 1.9 g. (35%) of the product as a yellow oil. Crystallization was effected by dissolving the material in ether, adding 30°-60° petroleum ether to produce turbidity and refrigerating the solution for several days. The product melted at 92°-95° after recrystallization from hexane.

1. temperaturemaintained at 90°
2. customwas collected
3. temperatureThe reaction mixture was subsequently refluxed for 11 hours
4. customthe azeotrope collected periodically
5. additionDuring this time sodium methoxide (0.075 g.) was added
6. additionof fresh n-heptane was added as an equal volume of distillate
7. customwas collected simultaneously
8. temperatureHeating
9. custom(38% of theory) of methanol was obtained
10. temperatureAs the reaction mixture cooled
11. customThe n-heptane was decanted
12. washthe residue was washed with ice water (3×10 ml.)
13. additionEther and ice were added to the oil
14. customto yield 1.9 g
15. customCrystallization
16. dissolutionby dissolving the material in ether
17. additionadding 30°-60° petroleum ether
18. customto produce turbidity
19. customfor several days
20. customThe product melted at 92°-95° after recrystallization from hexane