3-Methyl-1-trichloromethyl-2-butenyl diazoacetate → 4-Trichloromethyl-6,6-dimethyl-2-oxo-3-oxabicyclo[3.1.0]hexane

HRID 127033

반응식

HRID 127033 반응식
[N+](=[CH:3][C:4]([O:6][CH:7]([C:12]([Cl:15])([Cl:14])[Cl:13])[CH:8]=[C:9]([CH3:11])[CH3:10])=[O:5])=[N-]>O1CCOCC1.CCOCC.CC(CC(C)=O)=O.CC(CC(C)=O)=O.[Cu]>[Cl:13][C:12]([Cl:15])([Cl:14])[CH:7]1[CH:8]2[CH:3]([C:9]2([CH3:11])[CH3:10])[C:4](=[O:5])[O:6]1

참가 물질

5

반응물 1

HCID 542243633-Methyl-1-trichloromethyl-2-butenyl diazoacetate

생성물 1

HCID 125252184-Trichloromethyl-6,6-dimethyl-2-oxo-3-oxabicyclo[3.1.0]hexane수율 56.5%

시약·촉매·용매 3

HCID 45052134Bis(pentane-2,4-dione-kappa~2~O~2~,O~4~)copper촉매2회HCID 3283Diethyl Ether용매HCID 312751,4-Dioxane용매2회

실험 절차

To a refluxing solution of cupric acetylacetonate (0.07 g, 0.27 mole) in 70 ml of dioxane was added drop-dropwise over a 31/2 hour period, under an argon atmosphere, a solution of (±)-3-methyl-1-trichloromethyl-2-butenyl diazoacetate (1.09 g, 0.004 moles) and cupric acetylacetonate (0.007 g, 0.027 mmole) in 10 ml of dioxane. The reaction mixture was then heated under reflux for one hour and evaporated to dryness, yielding a residue which was dissolved in ether. The ethereal solution was washed successively with two portions of aqueous 1 N hydrochloric acid, two portions of aqueous sodium bicarbonate, and twice with saturated aqueous sodium chloride. After drying the solution over magnesium sulfate, the ether was evaporated to afford a pale yellow oil, which was purified by column chromatography on a silica gel column using a 9/1 mixture of n-hexane/ethyl acetate as the eluant, to give (±)-4-trichloromethyl-6,6-dimethyl-2-oxo-3-oxabicyclo[3.1.0]hexane (0.55 g, 53% yield).

후처리

  1. temperatureThe reaction mixture was then heated
  2. temperatureunder reflux for one hour
  3. customevaporated to dryness
  4. customyielding a residue which
  5. washThe ethereal solution was washed successively with two portions of aqueous 1 N hydrochloric acid, two portions of aqueous sodium bicarbonate
  6. dry with materialAfter drying the solution over magnesium sulfate
  7. customthe ether was evaporated
  8. customto afford a pale yellow oil, which
  9. customwas purified by column chromatography on a silica gel column
  10. additiona 9/1 mixture of n-hexane/ethyl acetate as the eluant

출처 및 근거

ORD 기록
ord-a24e740ee3754eeca22a32f79503d176
출처 데이터셋
uspto-grants-1981_03
특허 번호
US04254282

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