3,5-Dinitrobenzoyl chloride → [(1R)-1-[(2R)-2-(2,4-Difluorophenyl)-2-oxiranyl]ethyl]3,5-dinitrobenzoate

HRID 279157

Reaction equation

HRID 279157 reaction equation
[F:1][C:2]1[CH:7]=[C:6]([F:8])[CH:5]=[CH:4][C:3]=1[C:9]1([C@H:12]([OH:14])[CH3:13])[CH2:11][O:10]1.[N+:15]([C:18]1[CH:19]=[C:20]([CH:24]=[C:25]([N+:27]([O-:29])=[O:28])[CH:26]=1)[C:21](Cl)=[O:22])([O-:17])=[O:16]>C(Cl)Cl.CN(C)C>[N+:15]([C:18]1[CH:19]=[C:20]([CH:24]=[C:25]([N+:27]([O-:29])=[O:28])[CH:26]=1)[C:21]([O:14][C@@H:12]([C@@:9]1([C:3]2[CH:4]=[CH:5][C:6]([F:8])=[CH:7][C:2]=2[F:1])[CH2:11][O:10]1)[CH3:13])=[O:22])([O-:17])=[O:16]

Participants

5

Reactant 2

HCID 74323,5-Dinitrobenzoyl chlorideHCID 15130436(1R)-1-[2-(2,4-difluorophenyl)-2-oxiranyl]ethanol

Product 1

HCID 10691998[(1R)-1-[(2R)-2-(2,4-Difluorophenyl)-2-oxiranyl]ethyl]3,5-dinitrobenzoateYield 46.3%

Reagents, catalysts & solvents 2

HCID 1146TrimethylamineSolventHCID 6344DichloromethaneSolvent

Procedure

(1R)-1-[2-(2,4-Difluorophenyl)-2-oxiranyl]ethanol (31.5 g) and 3,5-dinitrobenzoyl chloride (40 g) were dissolved in methylene chloride (500 ml), to which trimethylamine (24.1 ml) was added dropwise at ice-bath temperature. After the mixture was stirred at room temperature for 3.5 hours, it was washed with water (150 ml) and 5% sodium bicarbonate aqueous solution successively, dried over magnesium sulfate and concentrated under reduced pressure. The precipitated crystals were filtrated and washed with methylene chloride. The mother liquor and the washings were combined and distilled off under reduced pressure. Ethyl acetate (25 ml) and methanol (300 ml) were added to the residue, and the mixture was cooled in an ice bath. The precipitated crystals were collected by filtration and recrystallized from a mixture of ethyl acetate (25 ml) and methanol (250 ml) to give [(1R)-1-[(2R)-2-(2,4-difluorophenyl)-2-oxiranyl]ethyl] 3,5-dinitrobenzoate (28.7 g) as colorless needles.

Workup

  1. additionwas added dropwise at ice-bath temperature
  2. washit was washed with water (150 ml) and 5% sodium bicarbonate aqueous solution successively
  3. dry with materialdried over magnesium sulfate
  4. concentrationconcentrated under reduced pressure
  5. filtrationThe precipitated crystals were filtrated
  6. washwashed with methylene chloride
  7. distillationdistilled off under reduced pressure
  8. additionEthyl acetate (25 ml) and methanol (300 ml) were added to the residue
  9. temperaturethe mixture was cooled in an ice bath
  10. filtrationThe precipitated crystals were collected by filtration
  11. customrecrystallized from a mixture of ethyl acetate (25 ml) and methanol (250 ml)

Sources & evidence

ORD record
ord-80f214634efa4594864ccfbb47b83c3a
Source dataset
uspto-grants-2002_03
Patent number
US06362206B1

Linked notes

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