Diethyl Ether → 9-Azabicyclo[3.3.1]nonan-3-one--hydrogen chloride (1/1)

HRID 1655274Notes

Reaction equation

HRID 1655274 reaction equation
[Cl:1]C(Cl)(Cl)COC([N:7]1[CH:12]2[CH2:13][CH2:14][CH2:15][CH:8]1[CH2:9][C:10](=[O:16])[CH2:11]2)=O.CCOCC>C(O)(=O)C.[Zn]>[ClH:1].[CH:8]12[NH:7][CH:12]([CH2:13][CH2:14][CH2:15]1)[CH2:11][C:10](=[O:16])[CH2:9]2

Participants

5

Reactant 2

HCID 3283Diethyl EtherHCID 156461169-(2,2,2-Trichlorocarbethoxy)-9-azabicyclo[3.3.1]nonan-3-one

Product 1

HCID 197915239-Azabicyclo[3.3.1]nonan-3-one--hydrogen chloride (1/1)Yield 86%

Reagents, catalysts & solvents 2

HCID 23994ZincCatalystHCID 176Acetic AcidSolvent3×

Conditions

Temperature
65 °C

Procedure

To suspension of zinc (67.2 g, 1.03 g-atom) in glacial acetic acid (40 mL) at 65° C. was slowly added a solution of 9-(2,2,2-trichlorocarbethoxy)-9-azabicyclo[3.3.1]nonan-3-one (80.9 g, 0.26 mol) in glacial acetic acid (120 mL) over 1 hour. An additional 40 mL of glacial acetic acid was used to rinse the addition funnel and the reaction was stirred at 65° C. until no further gas evolution was observed. The reaction was allowed to cool slightly and water (40 mL) was added to dissolve the organic acetate salts. The reaction was filtered and solvent was removed under vacuum. The resultant orange oil was slowly added to concentrated ammonium hydroxide (80 mL) using water (80 mL) to aid in the transfer. An additional 80 mL of concentrated ammonium hdroxide was added, followed by the addition of a solution of 31 g of sodium hydroxide in 155 mL of water. The solution was extracted with methylene chloride (6×300 mL), dried over anhydrous sodium sulfate, filtered, and concentrated to an oil. The oil was dissolved in 200 mL of ether and the solution was slowly added to 1N hydrogen chloride in ether (310 mL) while vigorously stirring to give 38.7 g (86% yield) of a colorless hydrochloride, m.p. 216°-219° C. after trituration with ether and drying. Anal. (C8H14ClNO).

Workup

  1. washto rinse the addition funnel
  2. temperatureto cool slightly
  3. additionwater (40 mL) was added
  4. dissolutionto dissolve the organic acetate salts
  5. filtrationThe reaction was filtered
  6. customsolvent was removed under vacuum
  7. additionThe resultant orange oil was slowly added to concentrated ammonium hydroxide (80 mL)
  8. additionAn additional 80 mL of concentrated ammonium hdroxide was added
  9. additionfollowed by the addition of a solution of 31 g of sodium hydroxide in 155 mL of water
  10. extractionThe solution was extracted with methylene chloride (6×300 mL)
  11. dry with materialdried over anhydrous sodium sulfate
  12. filtrationfiltered
  13. concentrationconcentrated to an oil
  14. dissolutionThe oil was dissolved in 200 mL of ether
  15. additionthe solution was slowly added to 1N hydrogen chloride in ether (310 mL)
  16. stirringwhile vigorously stirring

Sources & evidence

ORD record
ord-176c84b5e7344bfeb0209ac73d7a51ee
Source dataset
uspto-grants-1993_10
Patent number
US05250537

Reaction notes

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