1,2-Dichloroethane → cis-2-[1-Oxo-2-propenyl]cyclobutanecarboxylic acid

HRID 1706048Notes

Reaction equation

HRID 1706048 reaction equation
[Cl-].[Al+3].[Cl-].[Cl-].[CH:5]12[C:12](=[O:13])[O:11][C:9](=[O:10])[CH:6]1[CH2:7][CH2:8]2.Cl[CH2:15][CH2:16]Cl>>[O:10]=[C:9]([C@H:6]1[CH2:7][CH2:8][C@H:5]1[C:12]([OH:11])=[O:13])[CH:15]=[CH2:16]

Participants

4

Reactant 3

HCID 111,2-DichloroethaneHCID 1382613-Oxabicyclo(3.2.0)heptane-2,4-dioneHCID 6451240Aluminum(III) Chloride

Product 1

HCID 54060140cis-2-[1-Oxo-2-propenyl]cyclobutanecarboxylic acid

Procedure

A mixture of aluminum chloride (66.7 g., 0.5 M), 1,2-cyclobutanedicarboxylic anhydride (31.5 g., 0.24 M) and 1,2-dichloroethane (1 liter) in a 2 liter 3-neck flask equipped with a gas inlet tube, a mechanical stirrer and a drying tube is stirred rapidly and ethylene is bubbled in for 4.5 hours. This mixture is poured into 900 ml. 5% hydrochloric acid and ice. The layers are separated and the organic layer is washed with water and taken to dryness in vacuo. The aqueous layer is extracted with ether (300 ml.). The extract is washed with water and combined with material from the original organic layer and taken to dryness. The residue is heated with 150 ml. of 10% potassium carbonate on a steam bath for fifteen minutes. After cooling the mixture is extracted three times with ether. The aqueous portion is acidified and the product (1.5 g.) is extracted into ether. The original ether extracts are combined and extracted with 150 ml. of 10% potassium carbonate solution. This aqueous layer is then acidified with hydrochloric acid and the product cis-2-[1-oxo-2-propenyl]cyclobutanecarboxylic acid (24.3 g.) is extracted into ether. Both samples (25.8 g., 67%) crystallize on standing.

Workup

  1. customequipped with a gas inlet tube, a mechanical stirrer and a drying tube
  2. customethylene is bubbled in for 4.5 hours
  3. additionThis mixture is poured into 900 ml
  4. customThe layers are separated
  5. washthe organic layer is washed with water
  6. extractionThe aqueous layer is extracted with ether (300 ml.)
  7. washThe extract is washed with water
  8. temperatureThe residue is heated with 150 ml
  9. waitof 10% potassium carbonate on a steam bath for fifteen minutes
  10. temperatureAfter cooling the mixture
  11. extractionis extracted three times with ether
  12. extractionthe product (1.5 g.) is extracted into ether
  13. extractionextracted with 150 ml
  14. extractionthe product cis-2-[1-oxo-2-propenyl]cyclobutanecarboxylic acid (24.3 g.) is extracted into ether
  15. customBoth samples (25.8 g., 67%) crystallize

Sources & evidence

ORD record
ord-d4514c52f9e1432bbec031486c28e43c
Source dataset
uspto-grants-1980_06
Patent number
US04206137

Reaction notes

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