Reaktion #414565

Reaktionsgleichung

piperidine

ethanol

Hydroxylamine hydrochloride

formaldehyde

sodium methoxide methanol

sodium methoxide

3-quinuclidinone hydrochloride

sodium hydroxide

ethanol

→

voluminous white needles

Ausbeute 17.0%

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

Ausbeute 17.0%

Lösungsmittel

—

petroleum ether

water

water

Reaktionsbedingungen

Aufarbeitung

1. 1
   TemperaturSeparately, a cooled
2. 2
   workup.STIRRINGthe mixture was stirred at room temperature for 15 minutes
3. 3
   Temperaturrefluxed for 45 minutes
4. 4
   Temperaturcooled
5. 5
   SonstigeThe organic layer was separated
6. 6
   Extraktionthe aqueous solution was extracted with petroleum ether (100 ml)
7. 7
   TrocknenThe combined organic layers were dried (MgSO4)
8. 8
   Einengenconcentrated in vacuo
9. 9
   workup.DISSOLUTIONdissolved in methanol (100 ml)
10. 10
    workup.STIRRINGthe mixture was stirred for 18 hours
11. 11
    Sonstigethe methanol was removed in vacuo
12. 12
    FiltrationThe suspension was filtered
13. 13
    Sonstigethe solid was collected
14. 14
    Sonstigedried
15. 15
    Extraktionextracted with methylene chloride (3×100 ml)
16. 16
    Trocknenthe combined extracts were dried (Na2SO4)
17. 17
    Einengenconcentrated in vacuo
18. 18
    Sonstigetriturated from ether
19. 19
    SonstigeThe combined solids were recrystallized from 2-propanol

Vorschrift

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).

Quelle