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

HRID 894284Notes

Reaction equation

HRID 894284 reaction equation
[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

Participants

5

Reactant 1

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

Product 1

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

Reagents, catalysts & solvents 3

HCID 45052134Bis(pentane-2,4-dione-kappa~2~O~2~,O~4~)copperCatalyst2×HCID 3283Diethyl EtherSolventHCID 312751,4-DioxaneSolvent2×

Procedure

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 1N 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 eluent, to give (±)-4-trichloromethyl-6,6-dimethyl-2-oxo-3-oxabicyclo[3.1.0]hexane (0.55 g, 53% yield).

Workup

  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 1N 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 eluent

Sources & evidence

ORD record
ord-b1ce49b1e0cf40d2841076c6a4321f27
Source dataset
uspto-grants-1981_08
Patent number
US04283341

Reaction notes

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