Allyl bromide → Methyl 4-(allyloxy)-3-iodobenzoate

HRID 2181673Notes

Reaction equation

HRID 2181673 reaction equation
[OH:1][C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[CH:4][C:3]=1[I:12].[H-].[Na+].[CH2:15](Br)[CH:16]=[CH2:17]>CN(C=O)C>[CH2:17]([O:1][C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[CH:4][C:3]=1[I:12])[CH:16]=[CH2:15]

Participants

5

Reactant 3

HCID 7841Allyl bromideHCID 24758Sodium hydrideHCID 11346465Methyl 4-hydroxy-3-iodobenzoate

Product 1

HCID 11186196Methyl 4-(allyloxy)-3-iodobenzoateYield 60%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

Methyl 4-hydroxy-3-iodobenzoate (1.85 g, 6.65 mmol) is dissolved in anhydrous DMF (15 mL) in a dry flask under nitrogen, treated with NaH (60% dispersion in oil, 265 mg, 6.65 mmol) and stirred for 1 h at RT. Allyl bromide (633 μL, 7.32 mmol) is added and the mixture is stirred for 16 h. The mixture is concentrated and the residue is partitioned between EtOAc (25 mL) and H2O (25 mL). The organic layer is washed with a 50% saturated mixture of 1:1 NaC/NaHCO3 (2×10 mL), dried (MgSO4) and concentrated to a yellow oil which solidified to a white solid upon standing (2.12 g). The crude material is chromatographed over 100 g slurry-packed silica gel, eluting with 10% EtOAc/hexane. The appropriate fractions are combined and concentrated to afford 1.27 g (60%) of methyl 4-(allyloxy)-3-iodobenzoate as a colorless oil which solidified on standing. MS for C11H11IO3 (EI) m/z: 318 (M)+.

Workup

  1. stirringthe mixture is stirred for 16 h
  2. concentrationThe mixture is concentrated
  3. customthe residue is partitioned between EtOAc (25 mL) and H2O (25 mL)
  4. washThe organic layer is washed with a 50% saturated mixture of 1:1 NaC/NaHCO3 (2×10 mL)
  5. dry with materialdried (MgSO4)
  6. concentrationconcentrated to a yellow oil which
  7. customThe crude material is chromatographed over 100 g slurry-packed silica gel
  8. washeluting with 10% EtOAc/hexane
  9. concentrationconcentrated

Sources & evidence

ORD record
ord-5874123d145b41b18ad163ef88ad1818
Source dataset
uspto-grants-2005_05
Patent number
US06894042B2

Reaction notes

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