Nitric Acid → 5-Fluoro-2-methyl-3-nitrobenzoic acid

HRID 1809466Notes

Reaction equation

HRID 1809466 reaction equation
[F:1][C:2]1[CH:3]=[CH:4][C:5]([CH3:11])=[C:6]([CH:10]=1)[C:7]([OH:9])=[O:8].[N+:12]([O-])([OH:14])=[O:13]>OS(O)(=O)=O>[F:1][C:2]1[CH:3]=[C:4]([N+:12]([O-:14])=[O:13])[C:5]([CH3:11])=[C:6]([CH:10]=1)[C:7]([OH:9])=[O:8]

Participants

4

Reactant 2

HCID 944Nitric AcidHCID 1821145-Fluoro-2-methylbenzoic acid

Product 1

HCID 179850235-Fluoro-2-methyl-3-nitrobenzoic acid

Reagents, catalysts & solvents 1

HCID 1118Sulfuric AcidSolvent2×

Conditions

Temperature
0 °C

Procedure

A solution of 5-fluoro-2-methylbenzoic acid (from Matrix Scientific) in H2SO4 conc. (0.83 M) was cooled down to −10° C. Then, a mixture of fuming HNO3 conc. (2 eq.) and H2SO4 conc. (4 eq.) was added dropwise. After complete addition, the mixture was stirred at 0° C. for 1 h. The reaction mixture was poured onto ice/water and stirred for 10 min and then extracted with EtOAc. The combined organic layers were washed with brine, dried (Na2SO4) and solvent was removed in vacuo yielding the title compound as a yellow solid that was used without further purification in the next step. 1H NMR (300 MHz, DMSO-d6, 300 K) δ 13.86 (1H, bs), 8.09 (1H, dd, J=8.0 and 2.6 Hz), 7.90 (1H, dd, J=8.7 and 2.4 Hz), 2.50 (3H, s).

Workup

  1. additionwas added dropwise
  2. additionAfter complete addition
  3. additionThe reaction mixture was poured onto ice/water
  4. stirringstirred for 10 min
  5. extractionextracted with EtOAc
  6. washThe combined organic layers were washed with brine
  7. dry with materialdried (Na2SO4) and solvent
  8. customwas removed in vacuo

Sources & evidence

ORD record
ord-86ed5c56c035473ab3818538673207b5
Source dataset
uspto-grants-2013_01
Patent number
US08362030B2

Reaction notes

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