Sodium Thiosulfate → 8-Ethyl-2-methoxy-1-methoxymethoxynaphthalene

HRID 654670Notes

Reaction equation

HRID 654670 reaction equation
[CH2:1]([C:3]1[CH:4]=[CH:5][CH:6]=[C:7]2[C:12]=1[C:11]([O:13][CH2:14][O:15][CH3:16])=[C:10](C=O)[CH:9]=[CH:8]2)[CH3:2].ClC1C=CC=C([C:26](OO)=[O:27])C=1.S([O-])([O-])(=O)=S.[Na+].[Na+]>ClCCl>[CH2:1]([C:3]1[CH:4]=[CH:5][CH:6]=[C:7]2[C:12]=1[C:11]([O:13][CH2:14][O:15][CH3:16])=[C:10]([O:27][CH3:26])[CH:9]=[CH:8]2)[CH3:2]

Participants

5

Reactant 3

HCID 24477Sodium ThiosulfateHCID 70297m-Chloroperbenzoic acidHCID 102435412-Naphthalenecarboxaldehyde, 8-ethyl-1-(methoxymethoxy)-

Product 1

HCID 101059698-Ethyl-2-methoxy-1-methoxymethoxynaphthaleneYield 74.8%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

220 g of 8-ethyl-1-methoxymethoxy-2-naphthalenecarbaldehyde was dissolved in 1540 ml of dichloromethane, to which 186 g of 80 to 85% m-chloroperbenzoic acid was added portion by portion. The reaction solution generated heat and was gently refluxed. The reaction solution was ice-cooled, to which 200 ml of a saturated sodium thiosulfate aqueous solution was added. The precipitated insoluble matters were removed by filtration and washed with dichloromethane. The filtrate was washed with a saturated sodium hydrogencarbonate aqueous solution and a saturated saline solution and dried with anhydrous magnesium sulfate. After removal of the solvent by distillation, 254 g of the resultant residue was dissolved in 500 ml of methanol, to which 89 g of potassium hydroxide preliminarily dissolved in 200 ml of water was added, followed by refluxing for 20 minutes. The reaction solution was poured into 700 mo of cooled 2N hydrochloric acid and extracted with ethyl acetate. The resultant organic phase was washed with a saturated saline solution and dried with anhydrous magnesium sulfate, from which the solvent was distilled off. 278 g of the resultant residue was dissolved in 600 ml of N,N-dimethylformamide, to which 500 g of anhydrous potassium carbonate and 256 g of methyl iodide were added, followed by agitation at 60° C. for 2 hours. The insoluble matters were filtered off and washed with ethyl acetate. Water was added to the resultant filtrate, which was extracted with ethyl acetate. The resultant organic phase was washed with a saturated saline solution and dried with anhydrous magnesium sulfate. After removal of the solvent by distillation, the resultant residue was purified by silica gel column chromatography to obtain 166 g of the caption compound as a yellow oily substance.

Workup

  1. additionwas added portion by portion
  2. temperatureThe reaction solution generated heat
  3. temperaturewas gently refluxed
  4. additionwas added
  5. customThe precipitated insoluble matters were removed by filtration
  6. washwashed with dichloromethane
  7. washThe filtrate was washed with a saturated sodium hydrogencarbonate aqueous solution
  8. dry with materiala saturated saline solution and dried with anhydrous magnesium sulfate
  9. customAfter removal of the solvent
  10. distillationby distillation, 254 g of the resultant residue
  11. dissolutionwas dissolved in 500 ml of methanol, to which 89 g of potassium hydroxide
  12. dissolutionpreliminarily dissolved in 200 ml of water
  13. additionwas added
  14. temperatureby refluxing for 20 minutes
  15. additionThe reaction solution was poured into 700 mo of cooled 2N hydrochloric acid
  16. extractionextracted with ethyl acetate
  17. washThe resultant organic phase was washed with a saturated saline solution
  18. dry with materialdried with anhydrous magnesium sulfate, from which the solvent
  19. distillationwas distilled off
  20. dissolution278 g of the resultant residue was dissolved in 600 ml of N,N-dimethylformamide, to which 500 g of anhydrous potassium carbonate and 256 g of methyl iodide
  21. additionwere added
  22. filtrationThe insoluble matters were filtered off
  23. washwashed with ethyl acetate
  24. additionWater was added to the resultant filtrate, which
  25. extractionwas extracted with ethyl acetate
  26. washThe resultant organic phase was washed with a saturated saline solution
  27. dry with materialdried with anhydrous magnesium sulfate
  28. customAfter removal of the solvent
  29. distillationby distillation
  30. customthe resultant residue was purified by silica gel column chromatography

Sources & evidence

ORD record
ord-840d5c94966d4d2fbfbb672937dad7d9
Source dataset
uspto-grants-1992_07
Patent number
US05134111

Reaction notes

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