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

HRID 436857Notes

Reaction equation

HRID 436857 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 twenty-four 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 five hours and cooled to room temperature. A saturated sodium chloride solution (11.4 ml.) was added dropwise and heated 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 five hours
  14. additionA saturated sodium chloride solution (11.4 ml.) was added dropwise
  15. temperatureheated
  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-dc212f48d3c64a858b5beee6bb156eb8
Source dataset
uspto-grants-1977_06
Patent number
US04028382

Reaction notes

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