반응 #414566

반응 방정식

Magnesium sulfate

formaldehyde

hydroxylamine hydrochloride

sodium methoxide

sodium methoxide

sodium hydroxide

pyrrolidine

ethanol

quinuclidine-3-one hydrochloride

ethanol

→

fine colorless needles

수율 36.0%

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

수율 36.0%

용매

ether

반응 조건

후처리

1. 1
   workup.STIRRINGthe solution was stirred at 25° C. for 30 minutes
2. 2
   온도the mixture was refluxed for 4 hours
3. 3
   온도cooled
4. 4
   workup.STIRRINGthe mixture was stirred for 15 minutes
5. 5
   여과filtered
6. 6
   농축The filtrate was concentrated in vacuo
7. 7
   workup.DISSOLUTIONdissolved in methanol (100 ml)
8. 8
   여과was filtered
9. 9
   농축The filtrate was concentrated in vacuo to a residue, which
10. 10
    workup.DISSOLUTIONwas dissolved in methylene chloride (150 ml)
11. 11
    여과filtered
12. 12
    농축The filtrate was concentrated in vacuo
13. 13
    기타the residue was triturated from cold ether

실험 절차

A suspension of quinuclidine-3-one hydrochloride (16.2 g, 0.1 mole) in 95% ethanol (25 ml) was treated with 50% sodium hydroxide (8.0 g, 0.1 mole) and stirred until homogeneous. In a separate reactor a cooled (0° C.) solution of pyrrolidine (10.7 g, 0.15 mole) in 95% ethanol (25 ml) was treated dropwise with 37% aqueous formaldehyde (11.5 ml, 0.15 mole), and the solution was stirred at 25° C. for 30 minutes. The two solutions were combined and the mixture was refluxed for 4 hours, cooled, and added to ether (250 ml). Magnesium sulfate was added, and the mixture was stirred for 15 minutes and filtered. The filtrate was concentrated in vacuo, dissolved in methanol (100 ml), and treated with hydroxylamine hydrochloride (7.65 g, 110 mmoles), then with 25% sodium methoxide (2.2 g, 10 mmoles). After 2 hours at room temperature additional 25% sodium methoxide (21.6 g, 100 mmoles) was added and after 15 minutes the solution was filtered. The filtrate was concentrated in vacuo to a residue, which was dissolved in methylene chloride (150 ml) and filtered. The filtrate was concentrated in vacuo, and the residue was triturated from cold ether, then from cold acetonitrile ether to afford 8.09 g (36%) of fine colorless needles, mp 194°-195° C.

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