Reaktion #638795

Reaktionsgleichung

ammonium chloride

Tert-butyl[(1R,5S,6S)-6-(nitromethyl)bicyclo[3.2.0]hept-3-en-6-yl]acetate

ammonium chloride

→

Tert-butyl[(1R,5S,6S)-6-(aminomethyl)bicyclo[3.2.0]hept-3-en-6-yl]acetate

Lösungsmittel

water

ethanol

water

ethanol

Reaktionsbedingungen

Aufarbeitung

1. 1
   Temperaturunder heating to reflux
2. 2
   Temperaturto cool
3. 3
   workup.ADDITIONdiluted with saturated saline
4. 4
   Filtrationa saturated aqueous solution of sodium bicarbonate, and ethyl acetate, and filtered through Celite
5. 5
   Sonstigeto remove insoluble matter
6. 6
   SonstigeThe filtrate was separated into organic and aqueous layers
7. 7
   WaschenThe organic layer was washed with saturated saline
8. 8
   Trocknendried over anhydrous magnesium sulfate
9. 9
   workup.DISTILLATIONThen, the solvent was distilled off under reduced pressure
10. 10
    Sonstigeto obtain
11. 11
    workup.ADDITIONa mixture of the compound of interest
12. 12
    workup.STIRRINGthe mixture was stirred for 9 hours
13. 13
    Temperaturunder heating
14. 14
    workup.ADDITIONwas further added
15. 15
    Temperaturto cool
16. 16
    workup.ADDITIONdiluted with saturated saline
17. 17
    Filtrationa saturated aqueous solution of sodium bicarbonate, and ethyl acetate, and filtered through Celite
18. 18
    Sonstigeto remove insoluble matter
19. 19
    SonstigeThe filtrate was separated into organic and aqueous layers
20. 20
    WaschenThe organic layer was washed with saturated saline
21. 21
    Trocknendried over anhydrous magnesium sulfate
22. 22
    workup.DISTILLATIONThen, the solvent was distilled off under reduced pressure
23. 23
    Sonstigeto obtain the compound of interest as a pale yellow oil substance (17.53 g, 95%)

Vorschrift

Tert-butyl[(1R,5S,6S)-6-(nitromethyl)bicyclo[3.2.0]hept-3-en-6-yl]acetate (peak 2, 20.7 g, 77.4 mmol) was dissolved in ethanol (200 mL) and water (100 mL). To the solution, iron powder (34.69 g, 619.5 mmol) and ammonium chloride (2.09 g, 38.72 mmol) were added, and the mixture was stirred for 6.5 hours under heating to reflux. The mixture was allowed to cool, then diluted with saturated saline, a saturated aqueous solution of sodium bicarbonate, and ethyl acetate, and filtered through Celite to remove insoluble matter. The filtrate was separated into organic and aqueous layers. The organic layer was washed with saturated saline and then dried over anhydrous magnesium sulfate. Then, the solvent was distilled off under reduced pressure to obtain a mixture of the compound of interest and the starting material at almost 1:1 ratio (20.18 g, estimated by 1H-NMR). This mixture was dissolved again in ethanol (200 mL) and water (100 mL). To the solution, iron powder (40.36 g, 720.7 mmol) and ammonium chloride (4.18 g, 78.1 mmol) were added, and the mixture was stirred for 9 hours under heating to reflux while iron powder (32.73 g, 584.5 mmol) was further added thereto in three portions. The mixture was allowed to cool, then diluted with saturated saline, a saturated aqueous solution of sodium bicarbonate, and ethyl acetate, and filtered through Celite to remove insoluble matter. The filtrate was separated into organic and aqueous layers. The organic layer was washed with saturated saline and then dried over anhydrous magnesium sulfate. Then, the solvent was distilled off under reduced pressure to obtain the compound of interest as a pale yellow oil substance (17.53 g, 95%).

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