反应详情

To 350 ml of liquid ammonia was added 0.06 g of ferric nitrate. When the ferric nitrate dissolved, 1.0 g of sodium was added. The mixture was stirred until a black precipitate formed. To the mixture was then added 3.25 g of sodium. The solution was stirred until the mixture turned gray after which acetylene was bubbled through the reaction for 2 hrs. To the mixture was then added 25 g (0.177 mol) of N-acetyl-4-piperidone in 100 ml of dry THF. The mixture was subsequently stirred for 3 hrs. during which time acetylene was bubbled through. The reaction was then quenched by addition of 10 g (0.187 mol) of ammonium chloride. The ammonia was allowed to evaporate overnight. To the mixture was then added 75 ml of saturated ammonium nitrate and 40 ml of 25% ammonium hydroxide. The mixture was then extracted twice with chloroform, dried over potassium carbonate, filtered and the solvent evaporated to provide a white solid. The solid was washed with anhydrous ether and dried. The crude yield of 1-acetyl-4-ethynyl-4-piperidinol was 17.9 g (0.107 mol, 60.6%). Recrystallization from ethyl acetate provided analytically pure material, m.p. 132°-134° C. The material appeared pure by TLC (silica; 2% methanol/chloroform), Rf =0.2; (silica; 10% methanol/dichloromethane), Rf =0.4, IR (chloroform), 1H-NMR (CDCl3) and MS (MH+ =168) are consistent with the assigned structure.

1. customformed
2. stirringThe solution was stirred until the mixture
3. customwas bubbled through the reaction for 2 hrs
4. stirringThe mixture was subsequently stirred for 3 hrs
5. customduring which time acetylene was bubbled through
6. customto evaporate overnight
7. additionTo the mixture was then added 75 ml of saturated ammonium nitrate and 40 ml of 25% ammonium hydroxide
8. extractionThe mixture was then extracted twice with chloroform
9. dry with materialdried over potassium carbonate
10. filtrationfiltered
11. customthe solvent evaporated
12. customto provide a white solid
13. washThe solid was washed with anhydrous ether
14. customdried
15. customRecrystallization from ethyl acetate
16. customprovided analytically pure material, m.p. 132°-134° C