Methanol → HCID 54103468, compound

HRID 544721Notes

Reaction equation

HRID 544721 reaction equation
C([O:4][C:5]1[CH:10]=[CH:9][C:8]([CH3:11])=[CH:7][C:6]=1[CH:12]([CH3:15])[CH:13]=C)(=O)C.I([O-])(=O)(=O)=[O:17].[Na+].S(=O)(=O)(O)O.[CH3:27][OH:28]>O1CCOCC1.O.[Os](=O)(=O)(=O)=O.[O-2].[O-2].[O-2].[Cr+6]>[CH3:27][O:28][C:13](=[O:17])[CH:12]([C:6]1[CH:7]=[C:8]([CH3:11])[CH:9]=[CH:10][C:5]=1[OH:4])[CH3:15]

Participants

9

Reactant 4

HCID 887MethanolHCID 1118Sulfuric AcidHCID 23667635Sodium periodateHCID 54330111HCID 54330111, compound

Product 1

HCID 54103468HCID 54103468, compound

Reagents, catalysts & solvents 4

HCID 30318Osmium TetroxideCatalystHCID 10219390chromium (VI) trioxideCatalystHCID 962WaterSolvent3×HCID 312751,4-DioxaneSolvent

Procedure

A mixture of 20.4 g (0.1 mole) of 4-methyl-2-(1-methyl-2-propenyl)-phenyl acetate and 100 mg (0.4 mmole) of osmium tetroxide in 300 ml of dioxane and 100 ml of water is stirred at room temperature for 30 minutes, then, in the course of 30 minutes, 42.8 g (0.2 mole) of sodium periodate are added in portions and the mixture is subsequently stirred for one hour. The resulting precipitate is filtered off and then washed with dioxane/water (1:1). The aqueous-organic phase is concentrated in vacuo to approximately one third and extracted with methylene chloride. The oily crude product obtained after drying and after removal of the methylene chloride is taken up in 100 ml of acetone and oxidised by adding dropwise in the course of half an hour a solution of 7.2 g (72 mmoles) of chromium trioxide and 6.2 ml of concentrated sulphuric acid in 40 ml of water. Subsequently, 3 ml of methanol and 200 ml of water are added, the acetone is removed in vacuo, the aqueous phase is extracted with ether and the ther solution is extracted three times with 10% sodium hydroxide solution. The aqueous alkaline solution is left to stand at room temperature for 3 hours, then adjusted to pH 3 with concentrated hydrochloric acid and extracted with ether. The oil obtained after drying and after removal of the ether is stirred for 2 hours with 300 ml of saturated methanolic hydrochloric acid. Subsequently, the methanol is removed in vacuo and the residue is partitioned between ether and dilute sodium bicarbonate solution. The crude product obtained after drying and concentrating by evaporation the organic phase is chromatographed over silica gel with methylene chloride. Subsequent recrystallisation of the pure fractions from methylene chloride/petroleum ether yields 2-(2-hydroxy-5-methylphenyl)-propionic acid methyl ester having a melting point of 104°-106°.

Workup

  1. stirringthe mixture is subsequently stirred for one hour
  2. filtrationThe resulting precipitate is filtered off
  3. washwashed with dioxane/water (1:1)
  4. concentrationThe aqueous-organic phase is concentrated in vacuo to approximately one third
  5. extractionextracted with methylene chloride
  6. customThe oily crude product obtained
  7. customafter drying
  8. customafter removal of the methylene chloride
  9. customthe acetone is removed in vacuo
  10. extractionthe aqueous phase is extracted with ether
  11. extractionthe ther solution is extracted three times with 10% sodium hydroxide solution
  12. waitThe aqueous alkaline solution is left
  13. waitto stand at room temperature for 3 hours
  14. extractionextracted with ether
  15. customThe oil obtained
  16. customafter drying
  17. customafter removal of the ether
  18. stirringis stirred for 2 hours with 300 ml of saturated methanolic hydrochloric acid
  19. customSubsequently, the methanol is removed in vacuo
  20. customthe residue is partitioned between ether and dilute sodium bicarbonate solution
  21. customThe crude product obtained
  22. customafter drying
  23. concentrationconcentrating by evaporation the organic phase
  24. customis chromatographed over silica gel with methylene chloride
  25. customSubsequent recrystallisation of the pure fractions from methylene chloride/petroleum ether

Sources & evidence

ORD record
ord-699a9af70131407597a6bcc35b69c484
Source dataset
uspto-grants-1984_05
Patent number
US04451462

Reaction notes

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