Ethylene Glycol → 1,4-Dioxaspiro[4.5]decan-8-ylmethanol

HRID 1605105Notes

Reaction equation

HRID 1605105 reaction equation
CCO[C:4]([CH:6]1[CH2:12][CH2:11][C:9](=[O:10])[CH2:8][CH2:7]1)=[O:5].[CH2:13](O)[CH2:14][OH:15].C1(C)C=CC(S(O)(=O)=O)=CC=1.O>C1C=CC=CC=1>[CH2:13]1[O:10][C:9]2([CH2:8][CH2:7][CH:6]([CH2:4][OH:5])[CH2:12][CH2:11]2)[O:15][CH2:14]1

Participants

6

Reactant 4

HCID 174Ethylene GlycolHCID 962WaterHCID 6101p-Toluenesulfonic acidHCID 317638Ethyl 4-oxocyclohexanecarboxylate

Product 1

HCID 100808381,4-Dioxaspiro[4.5]decan-8-ylmethanol

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent

Procedure

Ethyl cyclohexanone-4-carboxylate (335 g.), 550 ml. ethylene glycol and 21 g. of p-toluenesulfonic acid in 5.5 liters of benzene were heated at reflux with stirring for 24 hours while water was separated by means of a water trap. The mixture was cooled and poured into 4 liters of ice water. The benzene layer was separated, washed with 1 liter of 5% sodium bicarbonate, 1 liter of water and 1 liter of saturated sodium chloride solution, dried and evaporated to dryness to give, after distillation, 245.6 g. of ethyl cyclohexanone-4-carboxylate ethylene ketal; b.p. 95-99.5°C. (0.07 mm.); N25D 1.4620. A solution of 35 g. of the ketal-ester in 50 ml. of dry tetrahydrofuran was added dropwise to 5.7 g. of lithium aluminum hydride in 250 ml. of dry tetrahydrofuran, and the mixture was heated at reflux for 5 hours and cooled to room temperature. A saturated sodium chloride solution (11.4 ml.) was added dropwise and heating at reflux was continued for one hour. The mixture was cooled and filtered, and the filtrate was dried and evaporated to dryness to give 26.9 g. of 4-hydroxymethylcyclohexanone ethylene ketal as a clear, colorless oil which was used without further purification.

Workup

  1. temperatureat reflux
  2. customwas separated by means of a water trap
  3. temperatureThe mixture was cooled
  4. additionpoured into 4 liters of ice water
  5. customThe benzene layer was separated
  6. washwashed with 1 liter of 5% sodium bicarbonate, 1 liter of water and 1 liter of saturated sodium chloride solution
  7. customdried
  8. customevaporated to dryness
  9. customto give
  10. distillationafter distillation, 245.6 g
  11. additionof dry tetrahydrofuran was added dropwise to 5.7 g
  12. temperatureof dry tetrahydrofuran, and the mixture was heated
  13. temperatureat reflux for 5 hours
  14. additionA saturated sodium chloride solution (11.4 ml.) was added dropwise
  15. temperatureheating
  16. temperatureat reflux
  17. temperatureThe mixture was cooled
  18. filtrationfiltered
  19. customthe filtrate was dried
  20. customevaporated to dryness
  21. customto give 26.9 g
  22. customof 4-hydroxymethylcyclohexanone ethylene ketal as a clear, colorless oil which was used without further purification

Sources & evidence

ORD record
ord-71f4f55b35804ad4aed11ff60a5a44a9
Source dataset
uspto-grants-1976_04
Patent number
US03948939

Reaction notes

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