Diethyl methylmalonate → Diethyl (3-oxo quinuclidin-2-yl)methyl-methylmalonate

HRID 1105662Notes

Reaction equation

HRID 1105662 reaction equation
[O-]CC.[Na+].[Na].[CH3:6][CH:7]([C:13]([O:15][CH2:16][CH3:17])=[O:14])[C:8]([O:10][CH2:11][CH3:12])=[O:9].[CH2:18]=[C:19]1[C:24](=[O:25])[CH:23]2[CH2:26][CH2:27][N:20]1[CH2:21][CH2:22]2>C(O)C.C(O)(=O)C>[O:25]=[C:24]1[CH:23]2[CH2:26][CH2:27][N:20]([CH2:21][CH2:22]2)[CH:19]1[CH2:18][C:7]([CH3:6])([C:8]([O:10][CH2:11][CH3:12])=[O:9])[C:13]([O:15][CH2:16][CH3:17])=[O:14]

Participants

7

Reactant 4

HCID 11857Diethyl methylmalonateHCID 3229732-Methylene-3-quinuclidoneHCID 2723922Sodium ethoxideHCID 5360545Sodium

Product 1

HCID 54084773Diethyl (3-oxo quinuclidin-2-yl)methyl-methylmalonate

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 702EthanolSolvent2×

Procedure

Ethanolic sodium ethoxide, previously prepared from 2.9 g of metallic sodium and 100 ml of ethanol, was added to diethyl methyl-malonate, 50 g, and the mixture was refluxed for 30 min. then cooled to 5°. A solution of 2-methylenequinuclidin-3-one, 39.4 g, in ethanol, 50 ml, was then added dropwise and with stirring. After 16 hrs. at room temperature, the resulting solution was neutralized with acetic acid then subjected to evaporation at reduced pressure. Water, 100 ml was added and the mixture was extracted with chloroform. Evaporation of this solvent gave diethyl (3-oxo quinuclidin-2-yl)-methyl-methylmalonate, 72 g (81%), m.p., 58.4° (from petroleum ether).

Workup

  1. temperaturethe mixture was refluxed for 30 min.
  2. temperaturethen cooled to 5°
  3. customat room temperature
  4. customthen subjected to evaporation at reduced pressure
  5. additionWater, 100 ml was added
  6. extractionthe mixture was extracted with chloroform
  7. customEvaporation of this solvent

Sources & evidence

ORD record
ord-bb1ae86741a34ec0b8f989f63622ce57
Source dataset
uspto-grants-1982_01
Patent number
US04309544

Reaction notes

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