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

HRID 599336Notes

Reaction equation

HRID 599336 reaction equation
[N+:1]([O-:4])(O)=[O:2].[Cl:5][C:6]1[CH:11]=[C:10]([F:12])[CH:9]=[CH:8][C:7]=1[NH2:13].CCOC(C)=O>OS(O)(=O)=O>[Cl:5][C:6]1[CH:11]=[C:10]([F:12])[C:9]([N+:1]([O-:4])=[O:2])=[CH:8][C:7]=1[NH2:13]

Participants

5

Reactant 3

HCID 944Nitric AcidHCID 8857Ethyl AcetateHCID 75013Benzenamine, 2-chloro-4-fluoro-

Product 1

HCID 202345022-Chloro-4-fluoro-5-nitroanilineYield 32%

Reagents, catalysts & solvents 1

HCID 1118Sulfuric AcidSolvent

Procedure

Concentrated nitric acid (8.8 g, 91 mmol) was added drop wise over 30 min to a stirred solution of 2-chloro-4-fluoro-phenylamine (12 g, 82.3 mmol) in conc H2SO4 acid (100 mL) at −10° C. The mixture was stirred at that temperature for 10 min. Then the reaction mixture was poured into cooled EtOAc, and ice water was added. The organic layer was separated and washed with brine and saturated NaHCO3 solution, dried (MgSO4) and concentrated in vacuo. Recrystallization (ethyl ether) provided 2-chloro-4-fluoro-5-nitroaniline (5.0 g, 32% yield). 1H NMR (400 MHz, DMSO-d6): δ7.59 (d, J=11.2 Hz, 1 H), 7.48 (d, J=7.2 Hz, 1 H), 5.84 (s, 2 H).

Workup

  1. additionThen the reaction mixture was poured
  2. additionwas added
  3. customThe organic layer was separated
  4. washwashed with brine and saturated NaHCO3 solution
  5. dry with materialdried (MgSO4)
  6. concentrationconcentrated in vacuo
  7. customRecrystallization (ethyl ether)

Sources & evidence

ORD record
ord-2e20d31727ec45bcaa16b7dd1af2a573
Source dataset
uspto-grants-2011_03
Patent number
US07897762B2

Reaction notes

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