Lithium Chloride → 4-Trichloromethyl-6,6-dimethyl-2-oxo-3-oxabicyclo[3.1.0]hexane

HRID 370567Notes

Reaction equation

HRID 370567 reaction equation
[Cl:1][C:2]([Cl:17])([Cl:16])[CH:3]1[CH:8]2[C:6](C(OC)=O)([C:7]2([CH3:10])[CH3:9])[C:5](=[O:15])[O:4]1.[Cl-].[Li+]>CN(C)P(=O)(N(C)C)N(C)C.CCOCC>[Cl:17][C:2]([Cl:1])([Cl:16])[CH:3]1[CH:8]2[CH:6]([C:7]2([CH3:10])[CH3:9])[C:5](=[O:15])[O:4]1

Participants

5

Reactant 2

HCID 433294Lithium ChlorideHCID 12525246Methyl 4-trichloromethyl-6,6-dimethyl-2-oxo-3-oxabicyclo[3.1.0]hexane-1-carboxylate

Product 1

HCID 125252184-Trichloromethyl-6,6-dimethyl-2-oxo-3-oxabicyclo[3.1.0]hexaneYield 28%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 12679HexamethylphosphoramideSolvent

Procedure

To a solution of methyl 4-trichloromethyl-6,6-dimethyl-2-oxo-3-oxabicyclo[3.1.0]hexane-1-carboxylate (1.52 g, 0.005 mole) in 10 ml of hexamethylphosphoric triamide was added lithium chloride (0.42 g, 0.010 mole). After heating at 75° for two hours, the cooled reaction mixture was diluted with ether. The ethereal solution was washed with water, dried over magnesium sulfate, and the ether was removed by evaporation, yielding a residue which was purified by column chromatography on silica gel using 9/1 n-hexane/ethylacetate as the eluent to give 4-trichloromethyl-6,6-dimethyl-2-oxo-3-oxabicyclo[3.1.0]hexane (0.34 g, 28% yield) as an oil.

Workup

  1. temperatureAfter heating at 75° for two hours
  2. customthe cooled reaction mixture
  3. washThe ethereal solution was washed with water
  4. dry with materialdried over magnesium sulfate
  5. customthe ether was removed by evaporation
  6. customyielding a residue which
  7. customwas purified by column chromatography on silica gel using 9/1 n-hexane/ethylacetate as the eluent

Sources & evidence

ORD record
ord-ca7708caf82b4d1087b62986e1b9dd7e
Source dataset
uspto-grants-1985_07
Patent number
US04526987

Reaction notes

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