Bromide ion → 2-Acetoxymethyl-5-chloro-4-nitrobenzonitrile

HRID 1739836Notes

Reaction equation

HRID 1739836 reaction equation
[Br-].[C:2]([O-:5])(=[O:4])[CH3:3].[Na+].[Cl:7][C:8]1[C:9]([N+:17]([O-:19])=[O:18])=[CH:10][C:11]([CH3:16])=[C:12]([CH:15]=1)[C:13]#[N:14]>CN(C=O)C.O>[C:2]([O:5][CH2:16][C:11]1[CH:10]=[C:9]([N+:17]([O-:19])=[O:18])[C:8]([Cl:7])=[CH:15][C:12]=1[C:13]#[N:14])(=[O:4])[CH3:3]

Participants

6

Reactant 3

HCID 259Bromide ionHCID 517045Sodium AcetateHCID 102417995-Chloro-2-methyl-4-nitrobenzonitrile

Product 1

HCID 154289162-Acetoxymethyl-5-chloro-4-nitrobenzonitrileYield 47%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent

Conditions

Temperature
0 °C

Procedure

The above partially purified bromide was dissolved in DMF (300 mL) and cooled to 0° C. Sodium acetate (18.0 g, 0.22 mol) was added. The mixture was stirred at 60° C. for 30 min. After cooling, the mixture was diluted with H2O and extracted with EtOAc. The EtOAc extract was washed with H2O (2×), dried over anhydrous MgSO4 and concentrated in vacuo. Chromatography over silica gel and elution with hexanes:EtOAc (9:1) yielded a front fraction containing 5-chloro-4-nitro-2-methylbenzonitrile and dibromide. Further elution with hexanes:EtOAc (2:1) gave the title compound (19.5 g, 47%) as a pale yellow solid.

Workup

  1. temperatureAfter cooling
  2. extractionextracted with EtOAc
  3. extractionThe EtOAc extract
  4. washwas washed with H2O (2×)
  5. dry with materialdried over anhydrous MgSO4
  6. concentrationconcentrated in vacuo
  7. washChromatography over silica gel and elution with hexanes:EtOAc (9:1)
  8. customyielded a front fraction
  9. washFurther elution with hexanes:EtOAc (2:1)

Sources & evidence

ORD record
ord-2c53d19978404f3b88444786a3feb41e
Source dataset
uspto-grants-1999_10
Patent number
US05968958

Reaction notes

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