반응 #414565

반응 방정식

piperidine

ethanol

Hydroxylamine hydrochloride

formaldehyde

sodium methoxide methanol

sodium methoxide

3-quinuclidinone hydrochloride

sodium hydroxide

ethanol

→

voluminous white needles

수율 17.0%

2-(1-Piperidinylmethyl)-1-azabicyclo[2.2.2]octan-3-one oxime

수율 17.0%

용매

—

petroleum ether

water

water

반응 조건

후처리

1. 1
   온도Separately, a cooled
2. 2
   workup.STIRRINGthe mixture was stirred at room temperature for 15 minutes
3. 3
   온도refluxed for 45 minutes
4. 4
   온도cooled
5. 5
   기타The organic layer was separated
6. 6
   추출the aqueous solution was extracted with petroleum ether (100 ml)
7. 7
   건조The combined organic layers were dried (MgSO4)
8. 8
   농축concentrated in vacuo
9. 9
   workup.DISSOLUTIONdissolved in methanol (100 ml)
10. 10
    workup.STIRRINGthe mixture was stirred for 18 hours
11. 11
    기타the methanol was removed in vacuo
12. 12
    여과The suspension was filtered
13. 13
    기타the solid was collected
14. 14
    기타dried
15. 15
    추출extracted with methylene chloride (3×100 ml)
16. 16
    건조the combined extracts were dried (Na2SO4)
17. 17
    농축concentrated in vacuo
18. 18
    기타triturated from ether
19. 19
    기타The combined solids were recrystallized from 2-propanol

실험 절차

A slurry of 3-quinuclidinone hydrochloride (16.2 g, 100 mmoles) in ethanol (16.5 ml) and water (7 ml) was treated with sodium hydroxide (4.0 g, 100 mmoles) and stirred for 15 minutes. Separately, a cooled (0° C.) mixture of piperidine (15 ml, 150 mmoles), water (15 ml), and ethanol (10 ml) was treated with 37% aqueous formaldehyde (11.5 ml, 150 mmoles), and the mixture was stirred at room temperature for 15 minutes. The mixtures were combined, refluxed for 45 minutes, cooled, and diluted with petroleum ether (250 ml). The organic layer was separated and the aqueous solution was extracted with petroleum ether (100 ml). The combined organic layers were dried (MgSO4), concentrated in vacuo, and dissolved in methanol (100 ml). Hydroxylamine hydrochloride (7.7 g, 110 mmoles) was added, followed by 25% sodium methoxide/methanol (2.16 g, 10 mmoles), and the mixture was stirred for 18 hours. Additional 25% sodium methoxide (21.6 g, 100 mmoles) was added, and the methanol was removed in vacuo and replaced with water (100 ml). The suspension was filtered, and the solid was collected and dried. The filtrate was saturated with sodium chloride, extracted with methylene chloride (3×100 ml), and the combined extracts were dried (Na2SO4), concentrated in vacuo, and triturated from ether. The combined solids were recrystallized from 2-propanol to yield 4.1 g (17%) of voluminous white needles, mp 196°-198° C. (dec).

출처