反应详情

温度

-77 °C

A solution of 7.2 ml 2,2,6,6-tetramethylpiperidine (0.034 mol) in 300 ml of dry THF was cooled to -8° C. as 25 ml of 1.6 M butyllithium (0.04 mol) in hexane was added dropwise. The reaction was stirred 20 min then cooled to -77° C. A solution of 2.9 ml of 2-chloropyrazine (0.031 mol) in 5 ml of THF was added to the reaction dropwise. After 15 min, 4.4 g of 3-quinuclidinone (0.0352 mol) in 5 ml of THF was added dropwise and the reaction stirred another 1.5 h. A solution of 8 ml of concentrated HCl and 4 ml of ethanol was added and the cooling was removed. When the temperature reached -5° C., 20 ml of 5 N NaOH was added and the volatile organics were evaporated. The residue was suspended in 50 ml of ice-water and the mixture filtered. The aqueous filtrate was extracted 3× with 50 ml of CHCl3. The extracts were combined with the solid collected from the filtration and the volume of the mixture adjusted to 450 ml with additional CHCl3. The mixture was heated on a steam bath until most of the solid had dissolved. The mixture was dried, filtered, and the solvent evaporated to give a dark brown solid that was recrystallized from isopropanol to give 6.3 g of (7), mp 215°-216° C. NMR ppm (CDCl3) 1.25(1H, m), 1.5 (2H, m), 2.2 (1H, m), 2.65-3.1 (6H, m), 3.6 (1H, bs), 4.05 (1H, d), 8.3 (1H, d), 8.5 (1H, d). Anal. C11H14ClN3O requires C: 55.12; H: 5.89; N: 17.53%. Found C: 55.21; H: 5.99; N: 17.30%.

1. additionwas added dropwise
2. waitAfter 15 min
3. stirringthe reaction stirred another 1.5 h
4. customthe cooling was removed
5. customreached -5° C.
6. addition20 ml of 5 N NaOH was added
7. customthe volatile organics were evaporated
8. filtrationthe mixture filtered
9. extractionThe aqueous filtrate was extracted 3× with 50 ml of CHCl3
10. filtrationcollected from the filtration
11. temperatureThe mixture was heated on a steam bath until most of the solid
12. dissolutionhad dissolved
13. customThe mixture was dried
14. filtrationfiltered
15. customthe solvent evaporated
16. customto give a dark brown solid that
17. customwas recrystallized from isopropanol