Hydrochloric Acid → Propanoic acid, 2-(4-hydroxyphenoxy)-, ethyl ester

HRID 1904439Notes

Reaction equation

HRID 1904439 reaction equation
S(OOS([O-])(=O)=O)([O-])(=O)=[O:2].[K+].[K+].[C:13]1([OH:19])[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1.Cl.Br[CH:22]([CH3:28])[C:23]([O:25][CH2:26][CH3:27])=[O:24]>O.[OH-].[Na+]>[OH:19][C:13]1[CH:18]=[CH:17][C:16]([O:2][CH:22]([CH3:28])[C:23]([O:25][CH2:26][CH3:27])=[O:24])=[CH:15][CH:14]=1

Participants

7

Reactant 4

HCID 313Hydrochloric Acid2×HCID 996PhenolHCID 24412Potassium PersulfateHCID 79040Ethyl 2-bromopropionate

Product 1

HCID 3017597Propanoic acid, 2-(4-hydroxyphenoxy)-, ethyl ester

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 14798Sodium HydroxideSolvent

Conditions

Temperature
20 °C

Procedure

A solution of potassium persulfate (27 g, 0.1 mole) in water (500 ml) was added slowly to a stirred solution of phenol (9.4 g, 0.1 mole) in aqueous 10% sodium hydroxide (200 ml) which was maintained at or below a temperature of 20° C. throughout the addition. After stirring for a period of 36 hours at room temperature the solution was acidified to pH 4.0 (Congo red) using concentrated hydrochloric acid and the acidic solution was extracted with diethyl ether (2 x 500 ml). The aqueous phase was made alkaline with sodium hydroxide and the water was removed by distillation under reduced pressure to give a solid residue. The residue was acidified and extracted with aqueous 90% ethanol (500 ml). The aqueous ethanolic solution was made strongly basic and then heated under reflux while ethyl 2bromopropionate (18 g, 0.1 mole) was added dropwise. After heating under reflux for a period of 2 hours the hot solution was acidified with concentrated hydrochloric acid and then stirred overnight at room temperature. The solvent was removed by distillation under reduced pressure and the residue was dissolved in ethanol (500 ml). Concentrated sulfuric acid (1 ml) was added to the ethanolic solution and the mixture was heated under reflux for a period of 48 hours. The solvent was removed by distillation under reduced pressure and the residue was partitioned between water and dichloromethane. The organic phase was dried (over anhydrous magnesium sulfate) and the solvent was removed by distillation under reduced pressure to give a dark-coloured oil. The crude product was chromatographed over silica gel (eluent dichloromethane) to give ethyl 2-(4-hydroxyphenoxy)propionate as a colour less oil.

Workup

  1. additionthroughout the addition
  2. extractionthe acidic solution was extracted with diethyl ether (2 x 500 ml)
  3. customthe water was removed by distillation under reduced pressure
  4. customto give a solid residue
  5. extractionextracted with aqueous 90% ethanol (500 ml)
  6. temperatureheated
  7. additionwas added dropwise
  8. temperatureAfter heating
  9. temperatureunder reflux for a period of 2 hours the hot solution
  10. stirringstirred overnight at room temperature
  11. customThe solvent was removed by distillation under reduced pressure
  12. dissolutionthe residue was dissolved in ethanol (500 ml)
  13. additionConcentrated sulfuric acid (1 ml) was added to the ethanolic solution
  14. temperaturethe mixture was heated
  15. temperatureunder reflux for a period of 48 hours
  16. customThe solvent was removed by distillation under reduced pressure
  17. customthe residue was partitioned between water and dichloromethane
  18. dry with materialThe organic phase was dried (over anhydrous magnesium sulfate)
  19. customthe solvent was removed by distillation under reduced pressure
  20. customto give a dark-coloured oil
  21. customThe crude product was chromatographed over silica gel (eluent dichloromethane)

Sources & evidence

ORD record
ord-05667a447ae34ae4947fe02a45839368
Source dataset
uspto-grants-1989_06
Patent number
US04837355

Reaction notes

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