Nitric Acid → Methyl 3-acetylamino-6-bromo-2-nitrobenzoate

HRID 215805Notes

Reaction equation

HRID 215805 reaction equation
S(=O)(=O)(O)O.[C:6]([NH:9][C:10]1[CH:11]=[CH:12][C:13]([Br:20])=[C:14]([CH:19]=1)[C:15]([O:17][CH3:18])=[O:16])(=[O:8])[CH3:7].[N+:21]([O-])([OH:23])=[O:22]>O>[C:6]([NH:9][C:10]1[C:19]([N+:21]([O-:23])=[O:22])=[C:14]([C:13]([Br:20])=[CH:12][CH:11]=1)[C:15]([O:17][CH3:18])=[O:16])(=[O:8])[CH3:7]

Participants

5

Reactant 3

HCID 944Nitric AcidHCID 1118Sulfuric AcidHCID 58891822Methyl 5-acetamido-2-bromobenzoate

Product 1

HCID 11151255Methyl 3-acetylamino-6-bromo-2-nitrobenzoateYield 62%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

To conc. sulfuric acid (150 mL), methyl 5-acetylamino-2-bromobenzoate (Reference Compound No. 1-(2), 18.5 g, 68.1 mmol) was added portionwise at 0° C., and conc. nitric acid (150 mL) was added dropwise thereto over 1 hour. The reaction mixture was stirred for 30 minutes, poured into iced water (1 L), and then the whole was extracted with ethyl acetate (500 mL, twice). The organic layer was washed with water (1 L, twice), saturated aqueous sodium hydrogen carbonate solution (1 L), and saturated brine (1 L) successively, dried over anhydrous magnesium sulfate, and then the solvent was removed under reduced pressure. The obtained residue was purified by silica gel column chromatography (hexane-ethyl acetate) to give the titled reference compound (13.4 g) as a yellow solid. (Yield 62%)

Workup

  1. addition1-(2), 18.5 g, 68.1 mmol) was added portionwise at 0° C.
  2. extractionthe whole was extracted with ethyl acetate (500 mL
  3. washThe organic layer was washed with water (1 L
  4. dry with materialtwice), saturated aqueous sodium hydrogen carbonate solution (1 L), and saturated brine (1 L) successively, dried over anhydrous magnesium sulfate
  5. customthe solvent was removed under reduced pressure
  6. customThe obtained residue was purified by silica gel column chromatography (hexane-ethyl acetate)

Sources & evidence

ORD record
ord-50602020d33742b5a22a19f282244236
Source dataset
uspto-grants-2012_06
Patent number
US08193187B2

Reaction notes

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