Nitric Acid → 4-Chloro-2-fluoro-5-nitroaniline

HRID 380783Notes

Reaction equation

HRID 380783 reaction equation
[Cl:1][C:2]1[CH:8]=[CH:7][C:5]([NH2:6])=[C:4]([F:9])[CH:3]=1.[N+:10]([O-])([OH:12])=[O:11]>S(=O)(=O)(O)O>[Cl:1][C:2]1[C:8]([N+:10]([O-:12])=[O:11])=[CH:7][C:5]([NH2:6])=[C:4]([F:9])[CH:3]=1

Participants

4

Reactant 2

HCID 944Nitric AcidHCID 938984-Chloro-2-fluoroaniline

Product 1

HCID 137530614-Chloro-2-fluoro-5-nitroanilineYield 86%

Reagents, catalysts & solvents 1

HCID 1118Sulfuric AcidSolvent

Conditions

Temperature
-15 °C

Procedure

A solution of 4-chloro-2-fluoroaniline (10.0 g, 69 mmol) in concentrated sulfuric acid is cooled to −20° C., treated dropwise with 90% nitric acid (5.0 mL, 107 mmol) over ten minutes, stirred at −15° C. for 90 minutes, and poured onto ice. The resultant aqueous mixture is extracted with diethyl ether, neutralized with 50% sodium hydroxide solution, and extracted again with diethyl ether. The organic extracts are combined, washed sequentially with dilute sodium hydroxide solution and brine, dried over anhydrous magnesium sulfate, and concentrated in vacuo to give the title product as a brown solid (11.3 g, 86% yield, mp 82-83.5° C.) which is identified by 1H, 19F and 13C NMR spectral analyses.

Workup

  1. additionpoured onto ice
  2. extractionThe resultant aqueous mixture is extracted with diethyl ether
  3. extractionextracted again with diethyl ether
  4. washwashed sequentially with dilute sodium hydroxide solution and brine
  5. dry with materialdried over anhydrous magnesium sulfate
  6. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-8d429f62a4324041bd713cb6b79054ab
Source dataset
uspto-grants-2001_10
Patent number
US06303783B1

Reaction notes

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