Ethyl Acetate → 2-Methanesulfonyloxy-5-methylbenzoic acid methyl ester

HRID 889236Notes

Reaction equation

HRID 889236 reaction equation
[H-].[Na+].[CH3:3][O:4][C:5](=[O:14])[C:6]1[CH:11]=[C:10]([CH3:12])[CH:9]=[CH:8][C:7]=1[OH:13].[CH3:15][S:16](Cl)(=[O:18])=[O:17].CCOC(C)=O>C1COCC1>[CH3:3][O:4][C:5](=[O:14])[C:6]1[CH:11]=[C:10]([CH3:12])[CH:9]=[CH:8][C:7]=1[O:13][S:16]([CH3:15])(=[O:18])=[O:17]

Participants

6

Reactant 4

HCID 8857Ethyl AcetateHCID 24758Sodium hydrideHCID 31297Methanesulfonyl chlorideHCID 89802Methyl 5-methylsalicylate

Product 1

HCID 866389792-Methanesulfonyloxy-5-methylbenzoic acid methyl ester

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Conditions

Temperature
0 °C

Procedure

To a ice cooled suspension of sodium hydride (60%, 1.3 g, 78.3 mmol) in THF (100 mL) is added a solution of 2-hydroxy-5-methylbenzoic acid methyl ester (10 g, 60 mmol) in THF (20 mL) and it is stirred at 0° C. Then a solution of methanesulfonyl chloride (8.2 g, 72 mmol) in THF (20 mL) is added dropwise. The reaction mixture is stirred at RT for 18 h. Then the reaction mixture is cooled in an ice bath and slowly ice is added to quench the reaction. EtOAc is used to extract. Brine is added to the aqueous phase and re-extracted with EtOAc. The combined organic phase is washed with water, brine, dried over NaSO4 and MgSO4, and concentrated to give the title compound as an oil. It is used directly in the next step.

Workup

  1. stirringThe reaction mixture is stirred at RT for 18 h
  2. temperatureThen the reaction mixture is cooled in an ice bath
  3. additionslowly ice is added
  4. customto quench
  5. customthe reaction
  6. extractionto extract
  7. additionBrine is added to the aqueous phase
  8. extractionre-extracted with EtOAc
  9. washThe combined organic phase is washed with water, brine
  10. dry with materialdried over NaSO4 and MgSO4
  11. concentrationconcentrated

Sources & evidence

ORD record
ord-bfd77a7eb4ed4c36bd2f27f4462f51ec
Source dataset
uspto-grants-2012_08
Patent number
US08252820B2

Reaction notes

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