Ethyl Acetate → 2-[N-(4-acetoxy-2-chlorobenzyl)acetamido]-6-bromo-3-nitropyridine

HRID 2181019Notes

Reaction equation

HRID 2181019 reaction equation
[C:1]([NH:4][C:5]1[C:10]([N+:11]([O-:13])=[O:12])=[CH:9][CH:8]=[C:7]([Br:14])[N:6]=1)(=[O:3])[CH3:2].[H-].[Na+].[C:17]([O:20][C:21]1[CH:28]=[CH:27][C:24]([CH2:25]Br)=[C:23]([Cl:29])[CH:22]=1)(=[O:19])[CH3:18].C(OCC)(=O)C>CN(C)C=O.O>[C:17]([O:20][C:21]1[CH:28]=[CH:27][C:24]([CH2:25][N:4]([C:5]2[C:10]([N+:11]([O-:13])=[O:12])=[CH:9][CH:8]=[C:7]([Br:14])[N:6]=2)[C:1](=[O:3])[CH3:2])=[C:23]([Cl:29])[CH:22]=1)(=[O:19])[CH3:18]

Participants

7

Reactant 4

HCID 8857Ethyl AcetateHCID 24758Sodium hydrideHCID 223878242-Acetamido-6-bromo-3-nitropyridineHCID 223879114-Acetoxy-2-chlorobenzylbromide

Product 1

HCID 224851742-[N-(4-acetoxy-2-chlorobenzyl)acetamido]-6-bromo-3-nitropyridineYield 74.1%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent

Procedure

To a solution of 2-acetamido-6-bromo-3-nitropyridine (203 mg) in N,N-dimethylformamide (2.34 ml) was added sodium hydride (60%, 34.3 mg) under ice-cooling, and the mixture was stirred for 1 hr. 4-Acetoxy-2-chlorobenzylbromide (288 mg) was added, and the mixture was stirred for 30 min under ice-cooling and at room temperature for 1 hr. Ethyl acetate (350 ml) and water (700 ml) were added to the reaction mixture under ice-cooling, and the mixture was partitioned. The organic layer was washed with water and saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, filtered and concentrated. The residue was purified by flash silica gel column chromatography and eluted with hexane/ethyl acetate=4/1-3/1. The eluate was concentrated under reduced pressure to give 2-[N-(4-acetoxy-2-chlorobenzyl)acetamido]-6-bromo-3-nitropyridine as an oil (256 mg).

Workup

  1. temperaturecooling
  2. stirringthe mixture was stirred for 30 min under ice-
  3. temperaturecooling
  4. customthe mixture was partitioned
  5. washThe organic layer was washed with water and saturated aqueous sodium chloride solution
  6. dry with materialdried over anhydrous magnesium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customThe residue was purified by flash silica gel column chromatography
  10. washeluted with hexane/ethyl acetate=4/1-3/1
  11. concentrationThe eluate was concentrated under reduced pressure

Sources & evidence

ORD record
ord-24ec935df42c48c5aacc064c54d03538
Source dataset
uspto-grants-2005_05
Patent number
US06890934B2

Reaction notes

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