Sodium hydride → Methyl 3-benzyloxycarbonylmethoxy-5-hydroxybenzoate

HRID 1740315Notes

Reaction equation

HRID 1740315 reaction equation
[OH:1][C:2]1[CH:3]=[C:4]([CH:9]=[C:10]([OH:12])[CH:11]=1)[C:5]([O:7][CH3:8])=[O:6].[H-].[Na+].Br[CH2:16][C:17]([O:19][CH2:20][C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1)=[O:18]>CN(C)C=O>[CH2:20]([O:19][C:17]([CH2:16][O:1][C:2]1[CH:3]=[C:4]([CH:9]=[C:10]([OH:12])[CH:11]=1)[C:5]([O:7][CH3:8])=[O:6])=[O:18])[C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 62576Benzyl bromoacetateHCID 75076Methyl 3,5-Dihydroxybenzoate

Product 1

HCID 21838035Methyl 3-benzyloxycarbonylmethoxy-5-hydroxybenzoate

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
10 °C

Procedure

To a mixture of methyl 3,5-dihydroxybenzoate (20 g) in N,N-dimethylformamide (200 ml) was added sodium hydride (60% in mineral oil, 5.23 g) slowly at 10° C. After stirring at 10° C. for 30 minutes, benzyl bromoacetate (20.7 ml) was added dropwise to the mixture over 10 minutes. The reaction mixture was stirred at room temperature overnight and then evaporated in vacuo. Ethyl acetate (400 ml) and water (100 ml) was added to the residue and the mixture was adjusted to pH 5 with hydrochloric acid. Two layers were separated and the organic layer was washed successively with water and brine, dried over magnesium sulfate and evaporated in vacuo. The residue was purified by column chromatography on silica gel eluting with a mixture of toluene and ethyl acetate (20:1). The fractions containing the desired product were collected and evaporated in vacuo to give methyl 3-benzyloxycarbonylmethoxy-5-hydroxybenzoate (12.92 g).

Workup

  1. stirringThe reaction mixture was stirred at room temperature overnight
  2. customevaporated in vacuo
  3. additionEthyl acetate (400 ml) and water (100 ml) was added to the residue
  4. customTwo layers were separated
  5. washthe organic layer was washed successively with water and brine
  6. dry with materialdried over magnesium sulfate
  7. customevaporated in vacuo
  8. customThe residue was purified by column chromatography on silica gel eluting with a mixture of toluene and ethyl acetate (20:1)
  9. additionThe fractions containing the desired product
  10. customwere collected
  11. customevaporated in vacuo

Sources & evidence

ORD record
ord-64e64928d85849d18d5bb3b9a9f4ce12
Source dataset
uspto-grants-1999_10
Patent number
US05968985

Reaction notes

Loading…