Ammonium Chloride → HCID 66803709, compound

HRID 551613Notes

Reaction equation

HRID 551613 reaction equation
[C:1]([O:5][C:6](=[O:19])[CH2:7][C@@:8]1([CH2:15][N+:16]([O-])=O)[CH2:14][C@@H:13]2[C@H:9]1[CH:10]=[CH:11][CH2:12]2)([CH3:4])([CH3:3])[CH3:2].[Cl-].[NH4+]>C(O)C.O.[Fe]>[C:1]([O:5][C:6](=[O:19])[CH2:7][C@@:8]1([CH2:15][NH2:16])[CH2:14][C@@H:13]2[C@H:9]1[CH:10]=[CH:11][CH2:12]2)([CH3:2])([CH3:4])[CH3:3]

Participants

6

Reactant 2

HCID 25517Ammonium Chloride2×HCID 90790353HCID 90790353, compound

Product 1

HCID 66803709HCID 66803709, compound

Reagents, catalysts & solvents 3

HCID 23925IronCatalyst3×HCID 702EthanolSolvent2×HCID 962WaterSolvent2×

Procedure

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%).

Workup

  1. temperatureunder heating to reflux
  2. temperatureto cool
  3. additiondiluted with saturated saline
  4. filtrationa saturated aqueous solution of sodium bicarbonate, and ethyl acetate, and filtered through Celite
  5. customto remove insoluble matter
  6. customThe filtrate was separated into organic and aqueous layers
  7. washThe organic layer was washed with saturated saline
  8. dry with materialdried over anhydrous magnesium sulfate
  9. distillationThen, the solvent was distilled off under reduced pressure
  10. customto obtain
  11. additiona mixture of the compound of interest
  12. stirringthe mixture was stirred for 9 hours
  13. temperatureunder heating
  14. additionwas further added
  15. temperatureto cool
  16. additiondiluted with saturated saline
  17. filtrationa saturated aqueous solution of sodium bicarbonate, and ethyl acetate, and filtered through Celite
  18. customto remove insoluble matter
  19. customThe filtrate was separated into organic and aqueous layers
  20. washThe organic layer was washed with saturated saline
  21. dry with materialdried over anhydrous magnesium sulfate
  22. distillationThen, the solvent was distilled off under reduced pressure
  23. customto obtain the compound of interest as a pale yellow oil substance (17.53 g, 95%)

Sources & evidence

ORD record
ord-36323f55e8404badae235019ed942a32
Source dataset
uspto-grants-2011_05
Patent number
US07947738B2

Reaction notes

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