Nitric Acid → 5-Bromo-2,3-dimethylbenzoic acid

HRID 1771702Notes

Reaction equation

HRID 1771702 reaction equation
[CH3:1][C:2]1[C:10]([CH3:11])=[CH:9][CH:8]=[CH:7][C:3]=1[C:4]([OH:6])=[O:5].[N+]([O-])(O)=O.[Br:16]Br>C(O)(=O)C.O.[N+]([O-])([O-])=O.[Ag+]>[Br:16][C:8]1[CH:9]=[C:10]([CH3:11])[C:2]([CH3:1])=[C:3]([CH:7]=1)[C:4]([OH:6])=[O:5]

Participants

7

Reactant 3

HCID 944Nitric AcidHCID 117822,3-Dimethylbenzoic acidHCID 24408Bromine

Product 1

HCID 668959895-Bromo-2,3-dimethylbenzoic acidYield 83.9%

Reagents, catalysts & solvents 3

HCID 24470Silver NitrateCatalystHCID 176Acetic AcidSolventHCID 962WaterSolvent2×

Procedure

To a solution of 2,3-dimethylbenzoic acid (5 g, 33.3 mmol, 1.0 eq) in acetic acid (167 mL) at room temperature was added a solution of conc. nitric acid (25.2 g, 399 mmol, 12 eq), water (15 g, 0.83 mmol, 25 eq) and bromine (5.85 g, 36.6 mmol, 1.1 eq). A solution of silver nitrate (7.35 g, 43 mmol, 1.3 eq) in water (43 mL) was then added dropwise over 30 min. Once addition was completed, the reaction was stirred at room temperature for 1 h, then quenched by addition of water and EtOAc. The aqueous layer was extracted with EtOAc and the combined organic extracts were washed with water and brine, dried (Na2SO4), filtered and evaporated in vacuo to give the title compound as a yellow solid (6.4 g, 83%).

Workup

  1. additionOnce addition
  2. customquenched by addition of water and EtOAc
  3. extractionThe aqueous layer was extracted with EtOAc
  4. washthe combined organic extracts were washed with water and brine
  5. dry with materialdried (Na2SO4)
  6. filtrationfiltered
  7. customevaporated in vacuo

Sources & evidence

ORD record
ord-00b35b8177a041dfb08c39923f514293
Source dataset
uspto-grants-2016_02
Patent number
US09249085B2

Reaction notes

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