Ethylene Glycol → 1,4-Dioxaspiro[4.5]decane-7-carboxylic acid

HRID 1654688Notes

Reaction equation

HRID 1654688 reaction equation
[O:1]=[C:2]1[CH2:7][CH2:6][CH2:5][CH:4]([C:8]([O:10]CC)=[O:9])[CH2:3]1.[CH2:13](O)[CH2:14][OH:15].[OH-].[Na+]>C1C=CC=CC=1.C(O)C.O.C1(C)C=CC(S(O)(=O)=O)=CC=1>[O:1]1[C:2]2([CH2:7][CH2:6][CH2:5][CH:4]([C:8]([OH:10])=[O:9])[CH2:3]2)[O:15][CH2:14][CH2:13]1

Participants

8

Reactant 3

HCID 174Ethylene GlycolHCID 14798Sodium HydroxideHCID 118096Ethyl 3-oxocyclohexanecarboxylate

Product 1

HCID 5674921,4-Dioxaspiro[4.5]decane-7-carboxylic acid

Reagents, catalysts & solvents 4

HCID 6101p-Toluenesulfonic acidCatalystHCID 241BenzeneSolventHCID 702EthanolSolventHCID 962WaterSolvent

Procedure

A mixture of ethyl 3-oxocyclohexanecarboxylate (Nallet, J- P., et al, Bull. Soc. Chem. Fr., Part II, No. 3-4, pages 153-156 (1979)) (101.7 g) ethylene glycol (38.9 g) and para-toluenesulfonic acid (5.5 g) in 1000 mL of benzene is refluxed with a Dean-Stark trap for 4 hours. The solution is cooled, washed with 1N sodium hydroxide and brine, dried over magnesium sulfate, and evaporated in vacuo to give 113.1 g of a light oil which is dissolved in 1000 mL of ethanol, treated with sodium hydroxide (25.3 g) in 250 mL of water, and refluxed for 2.5 hours. The mixture is concentrated in vacuo, cooled in an ice bath, and acidified with ice-cold 1N aqueous hydrochloric acid solution to a pH of 2. The title compound is extracted with chloroform (2×500 mL), dried over magnesium sulfate, and concentrated in vacuo. The title compound (99.3 g) is obtained as a yellowish oil, which is determined to be 98% pure by gas chromatography and is carried on without further purification.

Workup

  1. temperatureThe solution is cooled
  2. washwashed with 1N sodium hydroxide and brine
  3. dry with materialdried over magnesium sulfate
  4. customevaporated in vacuo
  5. customto give 113.1 g of a light oil which
  6. temperaturerefluxed for 2.5 hours
  7. concentrationThe mixture is concentrated in vacuo
  8. temperaturecooled in an ice bath
  9. extractionThe title compound is extracted with chloroform (2×500 mL)
  10. dry with materialdried over magnesium sulfate
  11. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-d9b0ff9ab3ab42adbeff21c9c9ac6291
Source dataset
uspto-grants-1995_04
Patent number
US05409931

Reaction notes

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