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

HRID 1957450노트

반응식

HRID 1957450 반응식
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]

참가 물질

5

반응물 3

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

생성물 1

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

시약·촉매·용매 1

HCID 6386tert-Butanol용매

실험 절차

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. 13C-NMR (75.5 MHz, CDCl3) 14.26, 25.15, 31.21, 33.56, 36.15, 53.21, 60.49, 173.38, 183.52 ppm.

후처리

  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

출처 및 근거

ORD 기록
ord-34703e5228f94cc084b90594efb21117
출처 데이터셋
uspto-grants-1998_07
특허 번호
USRE035865

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