Nitric Acid → 3-Bromo-6-fluoro-2-methyl-benzoic acid

HRID 1771719Notes

Reaction equation

HRID 1771719 reaction equation
[F:1][C:2]1[CH:10]=[CH:9][CH:8]=[C:7]([CH3:11])[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[C:7]([CH3:11])=[C:3]([C:2]([F:1])=[CH:10][CH:9]=1)[C:4]([OH:6])=[O:5]

Participants

7

Reactant 3

HCID 944Nitric AcidHCID 24408BromineHCID 134781322-Fluoro-6-methylbenzoic acid

Product 1

HCID 847957933-Bromo-6-fluoro-2-methyl-benzoic acidYield 90%

Reagents, catalysts & solvents 3

HCID 24470Silver NitrateCatalystHCID 176Acetic AcidSolventHCID 962WaterSolvent3×

Procedure

To a stirred solution of 2-fluoro-6-methyl-benzoic acid (1 g, 6.4 mmol, 1.0 eq) in acetic acid (32 mL) was added nitric acid (3.27 mL), water (3 mL) and bromine (0.36 mL). A solution of silver nitrate (1.43 g, 8.4 mmol 1.3 eq) in water (10 mL) was then added dropwise over a period of 15 min. After the addition was completed, stirring was continued a further 1.5 h at room temperature. The reaction was diluted with water and extracted with EtOAc. The combined organic extracts were washed with brine, dried (Na2SO4), filtered and evaporated in vacuo to afford a crude product, which was triturated with hexane to give the title compound as a yellow solid (1.35 g, 90%).

Workup

  1. additionAfter the addition
  2. extractionextracted with EtOAc
  3. washThe combined organic extracts were washed with brine
  4. dry with materialdried (Na2SO4)
  5. filtrationfiltered
  6. customevaporated in vacuo
  7. customto afford a crude product, which
  8. customwas triturated with hexane

Sources & evidence

ORD record
ord-7698ae3601d346bb80bf550732807ea8
Source dataset
uspto-grants-2016_02
Patent number
US09249085B2

Reaction notes

Loading…