Hydrogen Peroxide → t-Butyl 3-(1-carboxycyclopentyl)propanoate

HRID 374336Notes

Reaction equation

HRID 374336 reaction equation
C([C:4]1([CH2:11][CH2:12][C:13]([O:15][C:16]([CH3:19])([CH3:18])[CH3:17])=[O:14])[CH2:9][CH2:8][CH2:7][CH2:6][C:5]1=[O:10])(=O)C.[OH:20]O>S(=O)(=O)(O)O.C1(C)C=CC=CC=1>[C:16]([O:15][C:13]([CH2:12][CH2:11][C:4]1([C:5]([OH:10])=[O:20])[CH2:9][CH2:8][CH2:7][CH2:6]1)=[O:14])([CH3:17])([CH3:18])[CH3:19]

Participants

5

Reactant 2

HCID 784Hydrogen Peroxide2×HCID 109892762-Acetyl-2-[2-(tert-butoxycarbonyl)ethyl]cyclohexanone

Product 1

HCID 11010130t-Butyl 3-(1-carboxycyclopentyl)propanoate

Reagents, catalysts & solvents 2

HCID 1118Sulfuric AcidCatalystHCID 1140TolueneSolvent

Procedure

To a solution of 2-acetyl-2-[2-(tert-butoxycarbonyl)ethyl]-cyclohexanone (see Preparations 1 and 2) (2.0 g, 7.45 mmol) and concentrated sulphuric acid (98% w/w, one drop) in toluene (6.0 ml) was added, dropwise, a 30% aqueous solution of hydrogen peroxide (1.05 ml, 9.31 mmol) at room temperature. The mixture was stirred for 68 hours at room temperature, treated with a further quantity of a 30% aqueous solution of hydrogen peroxide (0.4 ml, 3.72 mmol) and stirred for a further 16 hours at room temperature. The mixture was partitioned between toluene (25 ml) and 5% aqueous sodium sulphite solution and the layers separated. The toluene layer was washed with dilute aqueous ammonia solution (25 ml of 0.880 ammonia in 200 ml of distilled water, 4×25 ml). The combined aqueous extracts were washed with toluene (25 ml), acidified to pH 2-3 with 5.0N aqueous hydrochloric acid solution and extracted with toluene (3×25 ml). The combined toluene extracts were dried over magnesium sulphate, filtered and concentrated under reduced pressure to give an oil, (1.11 g, 61%). The crude product was crystallized from pentane (7.5 ml/g) to give the title compound as a colorless solid. Rf. 0.28 (silica, hexane/ethyl acetate 2:1).

Workup

  1. customat room temperature
  2. stirringstirred for a further 16 hours at room temperature
  3. customThe mixture was partitioned between toluene (25 ml) and 5% aqueous sodium sulphite solution
  4. customthe layers separated
  5. washThe toluene layer was washed with dilute aqueous ammonia solution (25 ml of 0.880 ammonia in 200 ml of distilled water, 4×25 ml)
  6. washThe combined aqueous extracts were washed with toluene (25 ml)
  7. extractionextracted with toluene (3×25 ml)
  8. dry with materialThe combined toluene extracts were dried over magnesium sulphate
  9. filtrationfiltered
  10. concentrationconcentrated under reduced pressure
  11. customto give an oil, (1.11 g, 61%)
  12. customThe crude product was crystallized from pentane (7.5 ml/g)

Sources & evidence

ORD record
ord-67064fd875344a36a6431184d7d69978
Source dataset
uspto-grants-1992_11
Patent number
US05166406

Reaction notes

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