Hydrochloric Acid → 3',4'-Methylenedioxymandelic acid

HRID 1654558Notes

Reaction equation

HRID 1654558 reaction equation
[Cl-].[Li+].[OH-:3].[K+].[CH:5]1[C:10]([CH:11]=[O:12])=[CH:9][C:8]2[O:13][CH2:14][O:15][C:7]=2[CH:6]=1.C(Br)(Br)Br.Cl.[O:21]1[CH2:26]COCC1>[Cl-].C([N+](CCCCCCCC)(CCCCCCCC)C)CCCCCCC>[CH2:14]1[O:15][C:7]2[CH:6]=[CH:5][C:10]([CH:11]([OH:12])[C:26]([OH:21])=[O:3])=[CH:9][C:8]=2[O:13]1

Participants

8

Reactant 6

HCID 313Hydrochloric AcidHCID 5558BromoformHCID 8438PiperonalHCID 14797Potassium HydroxideHCID 312751,4-DioxaneHCID 433294Lithium Chloride

Product 1

HCID 1196183',4'-Methylenedioxymandelic acidYield 57%

Reagents, catalysts & solvents 1

HCID 21218Trioctylmethylammonium chlorideCatalyst

Procedure

42.4g (1 mol) of lithium chloride and 140.3 g (2.5 mol) of potassium hydroxide were dissolved in 500 ml of ice water, and then, 10 g of a 90% trioctylmethylammonium chloride aqueous solution was added thereto. A solution prepared by dissolving 75 g (0.5 mol) of piperonal and bromoform (containing 13 v/v % ethanol, about 0.63 mol) in 500 ml of dioxane was dropwise added to the solution at a temperature of at most 5° C., and then, the mixture was stirred at the same temperature for 24 hours. The reaction mixture was adjusted to pH 1.5 with 130 ml of 6N hydrochloric acid and extracted with 500 ml of ethyl acetate. 500 ml of water was added to the organic layer, adjusted to pH 8.0 with potassium carbonate powder, and the aqueous layer was separated. 130 ml of 6N hydrochloric acid was added to the aqueous layer to adjust pH 1.5 and then extracted with 500 ml of ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and then concentrated under reduced pressure. A crystalline residue was collected by filtration, washed with methylene chloride and diethyl ether and dried under reduced pressure to obtain 55.5 g (yield: 57%) of the above identified compound as the slightly yellow powder.

Workup

  1. customA solution prepared
  2. additionwas dropwise added to the solution at a temperature of at most 5° C.
  3. extractionextracted with 500 ml of ethyl acetate
  4. addition500 ml of water was added to the organic layer
  5. customthe aqueous layer was separated
  6. addition130 ml of 6N hydrochloric acid was added to the aqueous layer
  7. extractionextracted with 500 ml of ethyl acetate
  8. dry with materialThe organic layer was dried over anhydrous magnesium sulfate
  9. concentrationconcentrated under reduced pressure
  10. filtrationA crystalline residue was collected by filtration
  11. washwashed with methylene chloride and diethyl ether
  12. customdried under reduced pressure
  13. customto obtain 55.5 g (yield: 57%) of the

Sources & evidence

ORD record
ord-5536ffedc8794cf0a7d2eab93aafdc5a
Source dataset
uspto-grants-1995_04
Patent number
US05407930

Reaction notes

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