Methyl 2,4-Dihydroxybenzoate → HCID 3316729, compound

HRID 1377667Notes

Reaction equation

HRID 1377667 reaction equation
[CH3:1][O:2][C:3](=[O:12])[C:4]1[CH:9]=[CH:8][C:7]([OH:10])=[CH:6][C:5]=1[OH:11].[H-].[Na+].[C:15]([O:19][C:20]([NH:22][CH2:23][CH2:24][CH2:25]Br)=[O:21])([CH3:18])([CH3:17])[CH3:16]>CN(C=O)C>[CH3:1][O:2][C:3](=[O:12])[C:4]1[CH:9]=[CH:8][C:7]([O:10][CH2:25][CH2:24][CH2:23][NH:22][C:20]([O:19][C:15]([CH3:16])([CH3:18])[CH3:17])=[O:21])=[CH:6][C:5]=1[OH:11]

Participants

5

Reactant 3

HCID 16523Methyl 2,4-DihydroxybenzoateHCID 24758Sodium hydrideHCID 4460490tert-butyl N-(3-bromopropyl)carbamate

Product 1

HCID 3316729HCID 3316729, compoundYield 51%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a 0° C. stirred solution of 2,4-dihydroxybenzoic acid methyl ester (5 g, 30 mmol) in dry DMF (100 mL) was added sodium hydride (1.2 g of a 60% suspension in mineral oil, 30 mmol). After 1 h, the solution was warmed to ambient temperature and stirred for 1 h. To the solution was added N-t-butyloxycarbonyl-3-bromopropylamine (10.6 g, 45 mmol). The reaction was stirred at ambient temperature for 24 and the solvent was removed under reduced pressure. The residue was dissolved in EtOAc (250 mL) and washed with water (2×200 mL) and brine (100 mL). The EtOAc layer was dried (MgSO4), filtered, and the solvent was removed under reduced pressure. The residue was purified by pressurized silica gel column chromatography using 1:4 EtOAc:hexanes as eluant. The product-containing fractions were pooled and the solvent was removed under reduced pressure. The resulting oil crystallized from ether to give 4-(3-(t-butyloxycarbonylamino)propyloxy)-2-hydroxybenzoic acid methyl ester (51% yield).

Workup

  1. stirringThe reaction was stirred at ambient temperature for 24
  2. customthe solvent was removed under reduced pressure
  3. dissolutionThe residue was dissolved in EtOAc (250 mL)
  4. washwashed with water (2×200 mL) and brine (100 mL)
  5. dry with materialThe EtOAc layer was dried (MgSO4)
  6. filtrationfiltered
  7. customthe solvent was removed under reduced pressure
  8. customThe residue was purified by pressurized silica gel column chromatography
  9. customthe solvent was removed under reduced pressure
  10. customThe resulting oil crystallized from ether

Sources & evidence

ORD record
ord-66d66bba0703410a896c655e219f3e21
Source dataset
uspto-grants-1997_09
Patent number
US05665719

Reaction notes

Loading…