Acetone → (1S*,5S*)-3,4-dichloro-5-ethoxymethyl-8-oxabicyclo[3.2.1]octa-3,6-dien-2-one

HRID 341657Notes

Reaction equation

HRID 341657 reaction equation
[Cl:1][C:2]1[C@:3]2([CH2:13][O:14][CH2:15][CH3:16])[O:12][C@H:6]([C:7](Cl)(Cl)[C:8]=1[Cl:9])[CH:5]=[CH:4]2.CC(C)=[O:19].C(=O)(O)[O-].[Na+]>[N+]([O-])([O-])=O.[Ag+].O>[Cl:9][C:8]1[C:7](=[O:19])[C@H:6]2[O:12][C@@:3]([CH2:13][O:14][CH2:15][CH3:16])([C:2]=1[Cl:1])[CH:4]=[CH:5]2

Participants

6

Reactant 3

HCID 180AcetoneHCID 516892Sodium BicarbonateHCID 68731449(1S*,5S*)-2,3,4,4-tetrachloro-1-ethoxymethyl-8-oxabicyclo[3.2.1]octa-2,6-diene

Product 1

HCID 68732000(1S*,5S*)-3,4-dichloro-5-ethoxymethyl-8-oxabicyclo[3.2.1]octa-3,6-dien-2-one

Reagents, catalysts & solvents 2

HCID 24470Silver NitrateCatalystHCID 962WaterSolvent

Conditions

Temperature
65 °C

Procedure

Silver nitrate (26 g, 0.154 mol) is added to a stirred mixture of (1S*,5S*)-2,3,4,4-tetrachloro-1-ethoxymethyl-8-oxabicyclo[3.2.1]octa-2,6-diene (23.5 g, 0.077 mol), acetone (450 ml) and water (450 ml) and the mixture is heated at 65° C. for 16 hours. The reaction mixture is cooled to room temperature, and a saturated solution of aqueous sodium bicarbonate is added to adjust the pH to 7-8. The mixture is filtered through a plug of diatomaceous earth, and the filtrate is concentrated under reduced pressure to remove most of the acetone. The aqueous mixture is extracted with ethyl acetate (3×250 ml) and the organic extracts are combined, dried over anhydrous sodium sulfate, filtered and the filtrate is evaporated. The residue is purified by column chromatography on silica gel to give (1S*,5S*)-3,4-dichloro-5-ethoxymethyl-8-oxabicyclo[3.2.1]octa-3,6-dien-2-one (6 g) as a yellow oil.

Workup

  1. temperatureThe reaction mixture is cooled to room temperature
  2. filtrationThe mixture is filtered through a plug of diatomaceous earth
  3. concentrationthe filtrate is concentrated under reduced pressure
  4. customto remove most of the acetone
  5. extractionThe aqueous mixture is extracted with ethyl acetate (3×250 ml)
  6. dry with materialdried over anhydrous sodium sulfate
  7. filtrationfiltered
  8. customthe filtrate is evaporated
  9. customThe residue is purified by column chromatography on silica gel

Sources & evidence

ORD record
ord-363bcfa19bd24f8f9c382c4b871a0b58
Source dataset
uspto-grants-2014_11
Patent number
US08895761B2

Reaction notes

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