Benzyl chloroformate → HCID 12146494, compound

HRID 1836950Notes

Reaction equation

HRID 1836950 reaction equation
[H-].[Na+].Cl.Cl.[NH2:5][C@@H:6]1[CH:11]2[CH2:12][CH2:13][N:8]([CH2:9][CH2:10]2)[CH2:7]1.[C:14](Cl)([O:16][CH2:17][C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1)=[O:15]>[Cl-].[Na+].O>[CH2:17]([O:16][C:14](=[O:15])[NH:5][C@@H:6]1[CH:11]2[CH2:12][CH2:13][N:8]([CH2:9][CH2:10]2)[CH2:7]1)[C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1

Participants

5

Reactant 3

HCID 10387Benzyl chloroformateHCID 24758Sodium hydrideHCID 12494972(R)-(+)-3-Aminoquinuclidine Dihydrochloride

Product 1

HCID 12146494HCID 12146494, compound

Reagents, catalysts & solvents 1

HCID 57417360Sodium chloride; waterSolvent

Procedure

Sodium hydride (dispersion 55%) 0.33 g (7.5 mmol) is washed with petrolether and the solvent is removed by separation (decantation). Then, the sodium hydride is carefully suspended in dimethylformamide (12.5 ml). To this suspension (R)-(+)-3-aminoquinuclidine dihydrochloride 0.50 g (2.5 mmol) is added. The initially exothermic reaction is then stirred at room temperature for one hour and then carbobenzoxy chloride 0.39 ml (2.75 mmol) is added to the reaction mixture within 15 minutes. The again initially exothermic reaction is stirred at room temperature for 90 minutes, then the mixture is poured into 10% brine (NaCl/water solution) and then four-times extracted with toluene. The combined organic phases are dried and evaporated. The crude oily residue is dissolved in dioxane (5 ml) and 0.31 ml of a 4 M hydrochloric acid is added. The mixture is then stirred at room temperature till the product precipitates. The crystals are filtered, washed with dioxane and ether and dried to give the title product. Mp=228-229° C. Optical rotation +6.3° (c=0.5, water).

Workup

  1. customthe solvent is removed by separation (decantation)
  2. customThe initially exothermic reaction
  3. customThe again initially exothermic reaction
  4. stirringis stirred at room temperature for 90 minutes
  5. extractionfour-times extracted with toluene
  6. customThe combined organic phases are dried
  7. customevaporated
  8. dissolutionThe crude oily residue is dissolved in dioxane (5 ml)
  9. addition0.31 ml of a 4 M hydrochloric acid is added
  10. stirringThe mixture is then stirred at room temperature till the product
  11. customprecipitates
  12. filtrationThe crystals are filtered
  13. washwashed with dioxane and ether
  14. customdried

Sources & evidence

ORD record
ord-964956c2072543d79fbbc21aa36eb0ae
Source dataset
uspto-grants-2004_08
Patent number
US06780861B2

Reaction notes

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