Hydrogen Peroxide → 1-(3-Ethoxy-3-oxopropyl)cyclopentane-1-carboxylic acid

HRID 861694

Reaction equation

HRID 861694 reaction equation
C([C:4]1([CH2:11][CH2:12][C:13]([O:15][CH2:16][CH3:17])=[O:14])[CH2:9][CH2:8][CH2:7][CH2:6][C:5]1=[O:10])(=O)C.OO.S(=O)(=O)(O)[OH:21]>C(O)(C)(C)C>[CH2:16]([O:15][C:13]([CH2:12][CH2:11][C:4]1([C:5]([OH:10])=[O:21])[CH2:9][CH2:8][CH2:7][CH2:6]1)=[O:14])[CH3:17]

Participants

5

Reactant 3

HCID 784Hydrogen PeroxideHCID 1118Sulfuric AcidHCID 190674842-Acetyl-2-[2-(ethoxycarbonyl)ethyl]cyclohexanone

Product 1

HCID 110530121-(3-Ethoxy-3-oxopropyl)cyclopentane-1-carboxylic acid

Reagents, catalysts & solvents 1

HCID 6386tert-ButanolSolvent

Procedure

To a solution of 2-acetyl-2-[2-(ethoxycarbonyl)-ethyl]-cyclohexanone (see Preparation 4) (40 g, 0.16 mol) in tert-butanol (85 ml) was added, dropwise, a 30% aqueous solution of hydrogen peroxide (21.7 ml, 0.19 mol) and concentrated sulfuric acid (0.25 ml, 98% w/w) at room temperature. The mixture was further stirred for 24 hours, partitioned between dichloromethane (100 ml) and distilled water (100 ml) and the layers separated. The dichloromethane layer was washed with 5% aqueous sodium sulphite solution, dried over magnesium sulphate, filtered and concentrated under reduced pressure to give a yellow oil, (34.35 g). Purification of this material by chromatography on silica by eluting with ethyl acetate/hexane (1:2 changing to 1:1), followed by neat ethyl acetate in the latter stages, gave, after combination and evaporation of appropriate fractions, the title compound as a yellow oil, (22.96 g, 67%). RF. 0.28 (silica, ethyl acetate/hexane, 1:1). 1H-NMR (300 MHz, CDCl3):=1.31 (t, 3H), 1.47-1.62 (m, 2H), 1.62-1.82 (m, 4H), 1.92-2.08 (m, 2H), 2.10-2.27 (m, 2H), 2.32-2.46 (m, 2H), 4.19 (q, 2H) ppm. 13 C-NMR (75.5 MHz, CDCl3):=14.26, 25.15, 31.21, 33.56, 36.15, 53.21, 60.49, 173.38, 183.52 ppm.

Workup

  1. customat room temperature
  2. custompartitioned between dichloromethane (100 ml)
  3. distillationdistilled water (100 ml)
  4. customthe layers separated
  5. washThe dichloromethane layer was washed with 5% aqueous sodium sulphite solution
  6. dry with materialdried over magnesium sulphate
  7. filtrationfiltered
  8. concentrationconcentrated under reduced pressure
  9. customto give a yellow oil, (34.35 g)
  10. customPurification of this material by chromatography on silica
  11. washby eluting with ethyl acetate/hexane (1:2 changing to 1:1)
  12. customgave
  13. customafter combination and evaporation of appropriate fractions

Sources & evidence

ORD record
ord-e26c1345351e49c1a25761b246c8403e
Source dataset
uspto-grants-1998_02
Patent number
US05714628

Linked notes

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