反应详情

To a suspension of 507 g of the crude (foam) methiodide of 2-(p-biphenylyl)-5-dimethylamino-3-pentyn-2-ol obtained by step (b) above, in 4 liters of dry tetrahydrofuran, is added dropwise over a period of one hour, with cooling (to keep at room temperature), 478 g of a solution of sodium dihydrobis (2-methoxyethoxy) aluminate 70% w/w in benzene in 800 ml of dry tetrahydrofuran. The resulting mixture is then stirred at room temperature for 2 hours. The mixture is then cooled to 10° and dropwise there is added 3 liters of 2N sodium hydroxide, with stirring and cooling to 10° to 20°. 10 liters of diethyl ether are then added, in one portion, to the mixture. Solids present (inorganic salts) are removed by filtration on Celite. The filtrate is then extracted twice with 5 liter portions of water, the water washes then being washed three times with 5 liters of diethyl ether each time. The combined ether phases are washed once with 3 liters of aqueous saturated brine solution. The combined organic phases are dried over sodium sulfate, filtered, and the filtrate evaporated by rotary evaporation at 40° to obtain the crude product as an oil. The oil is taken up in 7 liters pentane (heated) and then the resulting pentane solution chilled until a precipitate forms. The precipitate is collected by filtration and washed with pentane. The precipitate is crystallized from pentane five times, then dried in a vacuum oven at room temperature for 12 hours to yield the title product, m.p. 65°-66°.

1. additionis added dropwise over a period of one hour
2. temperatureThe mixture is then cooled to 10°
3. stirringwith stirring
4. temperaturecooling to 10° to 20°
5. customSolids present (inorganic salts) are removed by filtration on Celite
6. extractionThe filtrate is then extracted twice with 5 liter portions of water
7. washthe water washes then being washed three times with 5 liters of diethyl ether each time
8. washThe combined ether phases are washed once with 3 liters of aqueous saturated brine solution
9. dry with materialThe combined organic phases are dried over sodium sulfate
10. filtrationfiltered
11. customthe filtrate evaporated by rotary evaporation at 40°
12. customto obtain the crude product as an oil
13. filtrationThe precipitate is collected by filtration
14. washwashed with pentane
15. customThe precipitate is crystallized from pentane five times
16. customdried in a vacuum oven at room temperature for 12 hours