Nitric Acid → 2,3,4-Trifluoro-5-nitrobenzoic acid

HRID 992384Notes

Reaction equation

HRID 992384 reaction equation
S(=O)(=O)(O)O.[N+:6]([O-:9])(O)=[O:7].[F:10][C:11]1[C:19]([F:20])=[C:18]([F:21])[CH:17]=[CH:16][C:12]=1[C:13]([OH:15])=[O:14]>O>[N+:6]([C:17]1[C:18]([F:21])=[C:19]([F:20])[C:11]([F:10])=[C:12]([CH:16]=1)[C:13]([OH:15])=[O:14])([O-:9])=[O:7]

Participants

5

Reactant 3

HCID 944Nitric AcidHCID 1118Sulfuric AcidHCID 3029322,3,4-Trifluorobenzoic acid

Product 1

HCID 158712412,3,4-Trifluoro-5-nitrobenzoic acidYield 78%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

To gently stirring concentrated sulfuric acid (50 ml) was added fuming nitric acid (3.4 ml, 0.076 mol). Solid 2,3,4-trifluorobenzoic acid (10.00 g, 0.05565 mol) was added directly in increments. After stirring 45 minutes, the reaction mixture had become an orange homogeneous solution which was then poured over chilled water (400 ml). The resulting aqueous suspension was extracted with diethyl ether (3×200 ml). The combined extracts were dried with anhydrous magnesium sulfate and concentrated in vacuo to yield 12.30 g of a dull, light-yellow solid. Recrystallization from chloroform (50 ml) afforded 9.54 g of the pale yellow microcrystalline product; 78% yield; m.p. ; 1H-NMR (400 MHz; DMSO)δ 14.29 (broad s, 1H), 8.43-8.38 (m, 1H); 13C-NMR (100 MHz; DMSO) δ162.41, 154.24 (dd, JC-F=270.1, 10.7 Hz), 148.35 (dd, JC-F=267.0, 9.2 Hz), 141.23 (dt, JC-F=253.4 Hz), 133.95,1 23.30 (d, JC-F=2.2 Hz), 116.92 (dd, JC-F=18.2, 3.8 Hz); 19F-NMR (376 MHz; DMSO) δ−120.50 to −120.63 (m), −131.133 to −131.27 (m), −153.63 to −153.74 (m).

Workup

  1. additionwas then poured
  2. extractionThe resulting aqueous suspension was extracted with diethyl ether (3×200 ml)
  3. dry with materialThe combined extracts were dried with anhydrous magnesium sulfate
  4. concentrationconcentrated in vacuo
  5. customto yield 12.30 g of a dull, light-yellow solid
  6. customRecrystallization from chloroform (50 ml)

Sources & evidence

ORD record
ord-fa39dea5646243b7bddfadc76cca2222
Source dataset
uspto-grants-2002_10
Patent number
US06469004B1

Reaction notes

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