4-Methyloxybenzyl chloride → HCID 21391683, compound

HRID 461659Notes

Reaction equation

HRID 461659 reaction equation
[OH:1][CH:2]([C:6]1[CH:11]=[CH:10][C:9]([C:12]([OH:14])=[O:13])=[CH:8][CH:7]=1)[C:3]([OH:5])=[O:4].[CH3:15][O:16][C:17]1[CH:24]=[CH:23][C:20]([CH2:21]Cl)=[CH:19][CH:18]=1>CS(C)=O.C1C=CC=CC=1>[OH:1][CH:2]([C:6]1[CH:11]=[CH:10][C:9]([C:12]([O:14][CH2:21][C:20]2[CH:23]=[CH:24][C:17]([O:16][CH3:15])=[CH:18][CH:19]=2)=[O:13])=[CH:8][CH:7]=1)[C:3]([OH:5])=[O:4]

Participants

5

Reactant 2

HCID 699934-Methyloxybenzyl chlorideHCID 22626649HCID 22626649, compound

Product 1

HCID 21391683HCID 21391683, compound

Reagents, catalysts & solvents 2

HCID 241BenzeneSolventHCID 679Dimethyl SulfoxideSolvent

Procedure

To a suspension of 4.9 g of the dipotassium salt of DL-α-hydroxy-4-carboxyphenylacetic acid (mp 201° ~ 203° C) in 40 ml of dimethylsulfoxide were added 6.2 g p-methoxybenzylchloride and stirred overnight at ambient temperature. 50 ml of ice-water were added to the reaction mixture, adjusted to pH 7.5 and extracted several times with ethyl acetate. The combined ethyl acetate layers were washed with water, dried over anhydrous magnesium sulfate and evaporated in vacuo. The oily residue was dissolved in 60 ml of 50% acetone. To the solution was added a phenolphthalein reagent and then dropwise a 2N-sodium hydroxide solution at 40° ~ 45° C with stirring. The reaction was continued until the red color was maintained for 5 minutes. Then acetone was removed under weakly reduced pressure. The aqueous layer was washed several times with ethyl ether, and then adjusted to pH 2.5 with a 20% hydrochloric acid solution after the addition of ethyl acetate. The aqueous layer was extracted several times with ethyl acetate. The combined organic layers were washed several times with a small amount of an aqueous sodium chloride saturated solution, dried over anhydrous magnesium sulfate. The solvent was removed in vacuo to give an oily residue. The residue was dissolved in benzene and left overnight in an ice-box, yielding crystals of DL-α-hydroxy-4-(p-methoxybenzyloxycarbonyl) phenylacetic acid of 7.4 g (78.5%).

Workup

  1. extractionextracted several times with ethyl acetate
  2. washThe combined ethyl acetate layers were washed with water
  3. dry with materialdried over anhydrous magnesium sulfate
  4. customevaporated in vacuo
  5. dissolutionThe oily residue was dissolved in 60 ml of 50% acetone
  6. additionTo the solution was added a phenolphthalein reagent
  7. stirringdropwise a 2N-sodium hydroxide solution at 40° ~ 45° C with stirring
  8. temperaturewas maintained for 5 minutes
  9. customThen acetone was removed under weakly reduced pressure
  10. washThe aqueous layer was washed several times with ethyl ether
  11. additionafter the addition of ethyl acetate
  12. extractionThe aqueous layer was extracted several times with ethyl acetate
  13. washThe combined organic layers were washed several times with a small amount of an aqueous sodium chloride saturated solution
  14. dry with materialdried over anhydrous magnesium sulfate
  15. customThe solvent was removed in vacuo
  16. customto give an oily residue
  17. waitleft overnight in an ice-box

Sources & evidence

ORD record
ord-3a4e1aeaa8704a62906623a8ab6cfabc
Source dataset
uspto-grants-1977_12
Patent number
US04064122

Reaction notes

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