Potassium Hydroxide → 4-(Methoxycarbonyl)bicyclo[2.2.2]octane-1-carboxylic acid

HRID 2280739Notes

Reaction equation

HRID 2280739 reaction equation
[C:1]12([C:13]([O:15]C)=[O:14])[CH2:8][CH2:7][C:4]([C:9]([O:11][CH3:12])=[O:10])([CH2:5][CH2:6]1)[CH2:3][CH2:2]2.[OH-].[K+]>CO.O>[CH3:12][O:11][C:9]([C:4]12[CH2:7][CH2:8][C:1]([C:13]([OH:15])=[O:14])([CH2:6][CH2:5]1)[CH2:2][CH2:3]2)=[O:10]

Participants

5

Reactant 2

HCID 14797Potassium HydroxideHCID 2802857dimethyl bicyclo[2.2.2]octane-1,4-dicarboxylate

Product 1

HCID 110420624-(Methoxycarbonyl)bicyclo[2.2.2]octane-1-carboxylic acidYield 56%

Reagents, catalysts & solvents 2

HCID 887MethanolSolvent2×HCID 962WaterSolvent

Procedure

A solution of dimethyl bicyclo[2.2.2]octane-1,4-dicarboxylate (58.0 g, 0.25 mol) in methanol (600 mL) was heated under reflux. To this solution was added a solution of potassium hydroxide (9.8 g, 0.175 mol) in methanol (100 mL) and water (12 mL) over 30 minutes. The reaction mixture was refluxed for 24 h. The solvent was then removed and the residue was diluted with water. The aqueous solution was extracted with ethyl acetate (2×200 mL) to recover starting material (22.0 g), and the aqueous layer was acidified to pH 3 by addition of hydrochloric acid. A precipitate was formed and extracted with ethyl acetate (3×300 mL). The combined extracted were washed with brine, dried over sodium sulfate and concentrated to give the titled product (30.0 g, 0.14 mol, 55% yield). 1H NMR (400 MHz, CDCl3) δ ppm 3.65 (s, 3H), 1.81 (s. 12H); MS (EST) m/z 211.3 [M+H]−.

Workup

  1. temperatureunder reflux
  2. temperatureThe reaction mixture was refluxed for 24 h
  3. customThe solvent was then removed
  4. additionthe residue was diluted with water
  5. extractionThe aqueous solution was extracted with ethyl acetate (2×200 mL)
  6. customto recover
  7. additionthe aqueous layer was acidified to pH 3 by addition of hydrochloric acid
  8. customA precipitate was formed
  9. extractionextracted with ethyl acetate (3×300 mL)
  10. extractionThe combined extracted
  11. washwere washed with brine
  12. dry with materialdried over sodium sulfate
  13. concentrationconcentrated

Sources & evidence

ORD record
ord-1ce9aa7208d040af8d293f0d21d51e47
Source dataset
uspto-grants-2015_09
Patent number
US09139534B2

Reaction notes

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