Hydrochloric Acid → 7-Hydroxyspiro[2.5]oct-6-en-5-one

HRID 1747705Notes

Reaction equation

HRID 1747705 reaction equation
[Na].C[C:3](C)([C:7]([O-:9])=O)[C:4]([O-])=[O:5].[C:11]1(=[CH:15]C(=O)C)[CH2:14][CH2:13][CH2:12]1.[OH-].[K+].Cl>O.CO>[OH:9][C:7]1[CH2:12][C:11]2([CH2:13][CH2:14]2)[CH2:15][C:4](=[O:5])[CH:3]=1

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 14797Potassium HydroxideHCID 5360545SodiumHCID 6946994DimethylmalonatHCID 122657211-Cyclobutylidenepropan-2-one

Product 1

HCID 863322587-Hydroxyspiro[2.5]oct-6-en-5-one

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 962WaterSolvent

Conditions

Temperature
35 °C

Procedure

5.75 g Sodium added in portions to 240 ml of methanol and the solution is heated to reflux for 1 hour. 28.4 ml Dimethylmalonate are added and the mixture is heated to reflux for another 10 minutes. The mixture is cooled to 35° C., 350 g 1-cyclobutylidenepropan-2-one (7% in 1,2-dichlorobenzene) are added and the mixture is refluxed for 1 hour. After recooling to room temperature a solution of 28.0 g potassium hydroxide in 130 ml water are added and the mixture is refluxed for 1 hour. The mixture is cooled to room temperature, the pH is adjusted to 1.5 by careful addition of half saturated hydrochloric acid and it is refluxed for 1 hour. The mixture is cooled to room temperature and the aqueous phase is extracted with ethyl acetate. The combined organic phases are dried over sodium sulfate, concentrated in vacuo and the residue is purified by chromatography on silica gel (petroleum ether/ethyl acetate 50:50).

Workup

  1. temperaturethe solution is heated
  2. temperatureto reflux for 1 hour
  3. temperaturethe mixture is heated
  4. temperatureto reflux for another 10 minutes
  5. temperaturethe mixture is refluxed for 1 hour
  6. customAfter recooling to room temperature
  7. additionare added
  8. temperaturethe mixture is refluxed for 1 hour
  9. temperatureThe mixture is cooled to room temperature
  10. temperatureis refluxed for 1 hour
  11. temperatureThe mixture is cooled to room temperature
  12. extractionthe aqueous phase is extracted with ethyl acetate
  13. dry with materialThe combined organic phases are dried over sodium sulfate
  14. concentrationconcentrated in vacuo
  15. customthe residue is purified by chromatography on silica gel (petroleum ether/ethyl acetate 50:50)

Sources & evidence

ORD record
ord-24945bf0602e4587aeb21435c1b7dfa4
Source dataset
uspto-grants-2015_10
Patent number
US09150583B2

Reaction notes

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