反応 #46674

反応方程式

Di-t-butyl carbonate

4-(4-pyridyl)-2-butanone oxime

lithium aluminum hydride

sodium hydroxide

→

compound

収率 32.0%

4-(3-Aminobutyl)pyridine

収率 32.0%

溶媒

Chloroform

Ethyl acetate

ether

ether

反応条件

後処理

1. 1
   温度cooling
2. 2
   workup.STIRRINGthe whole was stirred at room temperature overnight
3. 3
   温度Further, the mixture was refluxed for two days
4. 4
   workup.STIRRINGstirred under ice-
5. 5
   温度cooling
6. 6
   ろ過the resulting insoluble matter was filtered out with Celite
7. 7
   その他After separation, chloroform in the organic layer
8. 8
   その他was evaporated under reduced pressure
9. 9
   workup.ADDITIONwas added
10. 10
    workup.STIRRINGthe whole was stirred at room temperature
11. 11
    workup.STIRRINGThe whole was stirred overnight
12. 12
    抽出extracted with chloroform (50 ml)
13. 13
    乾燥The organic layer was dried over anhydrous magnesium sulfate
14. 14
    濃縮concentrated under reduced pressure
15. 15
    その他The residue was purified by silica gel column chromatography
16. 16
    workup.ADDITIONA 4 N solution of hydrogen chloride in ethyl acetate (3 ml) and ethanol (1 ml) were added to the residue
17. 17
    workup.STIRRINGthe whole was stirred at room temperature
18. 18
    濃縮the reaction mixture was concentrated under reduced pressure, chloroform (5 ml), methanol (5 ml) and triethylamine (1 ml)
19. 19
    workup.ADDITIONwere added to the residue
20. 20
    濃縮the whole was concentrated under reduced pressure
21. 21
    その他the residue was purified by basic silica gel column chromatography

実験手順

Next, anhydrous ether (19 ml) was added to lithium aluminum hydride (257 mg, 6.77 mmol) under a nitrogen atmosphere, and the mixture was stirred under ice-cooling. A solution of 4-(4-pyridyl)-2-butanone oxime (556 mg, 3.38 mmol) in ether (15 ml) was added dropwise to the mixture over seven minutes, and the whole was stirred at room temperature overnight. Further, the mixture was refluxed for two days and then stirred under ice-cooling. Ethyl acetate was slowly added to the reaction mixture, and then a 1 N aqueous sodium hydroxide solution (slowly at first, total: 20 ml) was added thereto. Chloroform (80 ml) was added thereto, and the resulting insoluble matter was filtered out with Celite. After separation, chloroform in the organic layer was evaporated under reduced pressure. The residue was combined with the aqueous layer, tetrahydrofuran (20 ml) was added thereto, and the whole was stirred at room temperature. Di-t-butyl carbonate (1.48 g, 6.78 mmol) was added thereto. The whole was stirred overnight and extracted with chloroform (50 ml). The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel column chromatography. A 4 N solution of hydrogen chloride in ethyl acetate (3 ml) and ethanol (1 ml) were added to the residue, and the whole was stirred at room temperature. After three hours, the reaction mixture was concentrated under reduced pressure, chloroform (5 ml), methanol (5 ml) and triethylamine (1 ml) were added to the residue, the whole was concentrated under reduced pressure, and the residue was purified by basic silica gel column chromatography to give the target compound (161 mg, 32%) as a brown oily matter.

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