Water → HCID 59309820, compound

HRID 1513009Notes

Reaction equation

HRID 1513009 reaction equation
[Cl:1][C:2]1[C:3]([N+:20]([O-])=O)=[CH:4][C:5]([O:9][CH2:10][C:11]2[C:16]([O:17][CH3:18])=[CH:15][CH:14]=[CH:13][C:12]=2[F:19])=[C:6]([OH:8])[CH:7]=1.C(=O)([O-])[O-].[K+].[K+].Br[CH2:30][C:31]([O:33][CH2:34][CH3:35])=[O:32].O>CN(C)C=O>[NH2:20][C:3]1[C:2]([Cl:1])=[CH:7][C:6]([O:8][CH2:30][C:31]([O:33][CH2:34][CH3:35])=[O:32])=[C:5]([O:9][CH2:10][C:11]2[C:16]([O:17][CH3:18])=[CH:15][CH:14]=[CH:13][C:12]=2[F:19])[CH:4]=1

Participants

6

Reactant 4

HCID 962WaterHCID 7748Ethyl bromoacetateHCID 11430Potassium CarbonateHCID 593099095-Chloro-2-(2-fluoro-6-methoxybenzyloxy)-4-nitrophenol

Product 1

HCID 59309820HCID 59309820, compound

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a suspension of 5-chloro-2-(2-fluoro-6-methoxybenzyloxy)-4-nitrophenol (5 g) and potassium carbonate (3.16 g) in N,N-dimethylformamide (15 mL) was added ethyl bromoacetate (2.2 mL), and the mixture was stirred at room temperature for 3 days. The reaction mixture was poured into water, and the resulting mixture was extracted with ethyl acetate. The extract was washed with brine, and dried over anhydrous sodium sulfate. The solvent was removed under reduced pressure, and the residue was dissolved in tetrahydrofuran (75 mL). To the solution were added methanol (75 mL) and nickel(II) bromide (0.17 g). To the mixture was added sodium borohydride (1.73 g) under ice-cooling, and the mixture was stirred at the same temperature for 30 minutes, and then stirred at room temperature for 30 minutes. The reaction mixture was poured into a saturated aqueous sodium hydrogen carbonate solution, and the resulting mixture was extracted with ethyl acetate. The extract was washed with water and brine, and dried over anhydrous sodium sulfate. The solvent was removed under reduced pressure, and the residue was purified by column chromatography on silica gel (eluent: n-hexane/ethyl acetate=3/1−2/1) to give the title compound (4.11 g).

Workup

  1. extractionthe resulting mixture was extracted with ethyl acetate
  2. washThe extract was washed with brine
  3. dry with materialdried over anhydrous sodium sulfate
  4. customThe solvent was removed under reduced pressure
  5. dissolutionthe residue was dissolved in tetrahydrofuran (75 mL)
  6. additionTo the solution were added methanol (75 mL) and nickel(II) bromide (0.17 g)
  7. additionTo the mixture was added sodium borohydride (1.73 g) under ice-
  8. temperaturecooling
  9. stirringthe mixture was stirred at the same temperature for 30 minutes
  10. stirringstirred at room temperature for 30 minutes
  11. additionThe reaction mixture was poured into a saturated aqueous sodium hydrogen carbonate solution
  12. extractionthe resulting mixture was extracted with ethyl acetate
  13. washThe extract was washed with water and brine
  14. dry with materialdried over anhydrous sodium sulfate
  15. customThe solvent was removed under reduced pressure
  16. customthe residue was purified by column chromatography on silica gel (eluent: n-hexane/ethyl acetate=3/1−2/1)

Sources & evidence

ORD record
ord-8b6971009d9c41f3852e4246cd40fd70
Source dataset
uspto-grants-2012_07
Patent number
US08217069B2

Reaction notes

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