Trichloroacetyl chloride → HCID 23565412, compound

HRID 1059287Notes

Reaction equation

HRID 1059287 reaction equation
[C:1]([O:5][C:6]([N:8]1[CH2:15][CH:14]2[C:16](=[CH2:17])[CH:10]([CH2:11][CH2:12][CH2:13]2)[CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].Cl[C:19](Cl)(Cl)[C:20](Cl)=[O:21].C(=O)([O-])O.[Na+]>CCOCC.C(COC)OC.[Cl-].[NH4+].CO.[Zn].[Cu].[Zn]>[C:1]([O:5][C:6]([N:8]1[CH2:9][CH:10]2[C:16]3([CH2:19][C:20](=[O:21])[CH2:17]3)[CH:14]([CH2:13][CH2:12][CH2:11]2)[CH2:15]1)=[O:7])([CH3:4])([CH3:3])[CH3:2]

Participants

10

Reactant 3

HCID 6420Trichloroacetyl chlorideHCID 516892Sodium BicarbonateHCID 18670433HCID 18670433, compound

Product 1

HCID 23565412HCID 23565412, compound

Reagents, catalysts & solvents 6

HCID 23994ZincCatalystHCID 10290809Zinc copper coupleCatalystHCID 887MethanolSolventHCID 3283Diethyl EtherSolventHCID 80711,2-DimethoxyethaneSolventHCID 25517Ammonium ChlorideSolvent

Procedure

To 3.7 g of zinc/copper alloy was added a solution of 1.4 g of 3-(tert-butoxycarbonyl)-9-methylene-3-azabicyclo[3.3.1]-nonane in dry ether (30 ml). Subsequently, a solution of 2.6 ml of trichloroacetyl chloride in dry dimethoxyethane (50 ml) was dropped thereinto and the resulting mixture was reacted at room temperature for 3 hours. Then a saturated aqueous solution of sodium hydrogencarbonate was added to the reaction mixture while maintaining the mixture at 0° C. or below. After filtering off the zinc/copper alloy, the filtrate was extracted with ethyl acetate, washed with a saturated aqueous solution of sodium chloride and dried over anhydrous magnesium sulfate. After concentrating under reduced pressure, the residue was purified by silica gel column chromatography (eluted with ethyl acetate/n-hexane) to thereby give 1.5 g of a yellow oily substance. This product was dissolved in 40 ml of a saturated solution of ammonium chloride in methanol. After adding 1.7 g of zinc, the resulting mixture was reacted at room temperature for 24 hours. After filtering off the zinc, water was added to the residue. Next, it was extracted with ethyl acetate, washed with a saturated aqueous solution of sodium chloride and dried over anhydrous magnesium sulfate. After concentrating, the residue was purified by silica gel column chromatography (eluted with ethyl acetate/n-hexane) to thereby give 0.8 g of the title compound as a colorless oily substance.

Workup

  1. customthe resulting mixture was reacted at room temperature for 3 hours
  2. temperaturewhile maintaining the mixture at 0° C. or below
  3. filtrationAfter filtering off the zinc/copper alloy
  4. extractionthe filtrate was extracted with ethyl acetate
  5. washwashed with a saturated aqueous solution of sodium chloride
  6. dry with materialdried over anhydrous magnesium sulfate
  7. concentrationAfter concentrating under reduced pressure
  8. customthe residue was purified by silica gel column chromatography (eluted with ethyl acetate/n-hexane)
  9. customto thereby give 1.5 g of a yellow oily substance
  10. customthe resulting mixture was reacted at room temperature for 24 hours
  11. filtrationAfter filtering off the zinc, water
  12. additionwas added to the residue
  13. extractionNext, it was extracted with ethyl acetate
  14. washwashed with a saturated aqueous solution of sodium chloride
  15. dry with materialdried over anhydrous magnesium sulfate
  16. concentrationAfter concentrating
  17. customthe residue was purified by silica gel column chromatography (eluted with ethyl acetate/n-hexane)

Sources & evidence

ORD record
ord-b9dcfc8a0608434991248f4f996520ba
Source dataset
uspto-grants-2003_02
Patent number
US06518423B1

Reaction notes

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