Ethyl bromoacetate → Ethyl 4-(1,1-dimethylethoxycarbonyl)amino-3-methylphenoxyacetate

HRID 1459412Notes

Reaction equation

HRID 1459412 reaction equation
[CH3:1][C:2]([CH3:16])([O:4][C:5]([NH:7][C:8]1[CH:13]=[CH:12][C:11]([OH:14])=[CH:10][C:9]=1[CH3:15])=[O:6])[CH3:3].C([O-])([O-])=O.[Cs+].[Cs+].Br[CH2:24][C:25]([O:27][CH2:28][CH3:29])=[O:26]>CN(C=O)C>[CH3:3][C:2]([CH3:16])([O:4][C:5]([NH:7][C:8]1[CH:13]=[CH:12][C:11]([O:14][CH2:24][C:25]([O:27][CH2:28][CH3:29])=[O:26])=[CH:10][C:9]=1[CH3:15])=[O:6])[CH3:1]

Participants

5

Reactant 3

HCID 7748Ethyl bromoacetateHCID 10796Cesium carbonateHCID 15429162tert-Butyl (4-hydroxy-2-methylphenyl)carbamate

Product 1

HCID 15429168Ethyl 4-(1,1-dimethylethoxycarbonyl)amino-3-methylphenoxyacetateYield 78%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a 200 mL round bottomed flask with a stirring bar, and an argon inlet was added 4-(1,1-dimethylethoxycarbonyl)amino-3-methylphenol (5.00 g, 22.39 mmol), Cs2CO3 (14.59 g, 44.78 mmol), DMF (50 mL), and ethyl bromoacetate (2.61 mL, 23.51 mmol). This mixture was stirred vigorously at ambient temperature for 24 h. The mixture was filtered through a frit and the DMF was removed under high vacuum. The residue was dissolved in EtOAc (300 mL) and washed with H2O (2×) and brine (1×). Drying (MgSO4), filtration, and removal of the solvent in vacuo gave a solid. This material was triturated with 5% Et2 O-hexane, the solid was collected by filtration and dried in vacuo to give 5.40 g (78%) of ethyl 4-(1,1-dimethylethoxycarbonyl)amino-3-methylphenoxyacetate as a white, crystalline solid.

Workup

  1. filtrationThe mixture was filtered through a frit
  2. customthe DMF was removed under high vacuum
  3. dissolutionThe residue was dissolved in EtOAc (300 mL)
  4. washwashed with H2O (2×) and brine (1×)
  5. customDrying
  6. filtration(MgSO4), filtration, and removal of the solvent in vacuo
  7. customgave a solid
  8. customThis material was triturated with 5% Et2 O-hexane
  9. filtrationthe solid was collected by filtration
  10. customdried in vacuo

Sources & evidence

ORD record
ord-da8ae778ede6433caee061d1248faf80
Source dataset
uspto-grants-1998_12
Patent number
US05854245

Reaction notes

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