Ethyl bromoacetate → HCID 54009082, compound

HRID 1459431Notes

Reaction equation

HRID 1459431 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[Cl: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[Cl:15])=[O:6])[CH3:1]

Participants

5

Reactant 3

HCID 7748Ethyl bromoacetateHCID 10796Cesium carbonateHCID 54121498tert-butyl 2-chloro-4-hydroxyphenylcarbamate

Product 1

HCID 54009082HCID 54009082, compound

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a 50 mL round bottomed flask with a stirring bar and an argon inlet was added 4-(1,1-dimethylethoxycarbonyl)amino-3-chlorophenol (0.831 g, 3.41 mmol) and DMF (16 mL). This mixture was cooled in an ice bath then Cs2CO3 (0.552 g, 1.69 mmol) and ethyl bromoacetate (0.37 mL, 3.34 mmol) were added. The resulting mixture was stirred for 6 h, during which time the cooling bath was allowed to expire. The mixture was filtered through a frit and the DMF was removed in vacuo. The residue was dissolved in EtOAc and washed with water (12×) and brine. Drying (MgSO4), filtration and removal of the solvent in vacuo gave an oil which was purified by silica gel chromatography (EtOAc-hexane) to give ethyl 4-(1,1-dimethylethoxycarbonyl)amino-3-chlorophenoxyacetate (34-4) as an oil. 1H NMR (CDCl3): δ 1.30 (m, 3H), 1.53 (s, 9H), 4.27 (m, 2H), 4.57 (s, 2H), 6.78 (br s, 1H), 6.83 (dd, J=2.8, 8.8 Hz, 1H), 6.96 (d, J=2.8 Hz, 1H), 8.02 (br d, J=8.8 Hz, 1H).

Workup

  1. temperatureThis mixture was cooled in an ice bath
  2. filtrationThe mixture was filtered through a frit
  3. customthe DMF was removed in vacuo
  4. dissolutionThe residue was dissolved in EtOAc
  5. washwashed with water (12×) and brine
  6. customDrying
  7. filtration(MgSO4), filtration and removal of the solvent in vacuo
  8. customgave an oil which
  9. customwas purified by silica gel chromatography (EtOAc-hexane)

Sources & evidence

ORD record
ord-baf0e726181640249fe238620a232b49
Source dataset
uspto-grants-1998_12
Patent number
US05854245

Reaction notes

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