Nitric Acid → HCID 19012214, compound

HRID 1729443Notes

Reaction equation

HRID 1729443 reaction equation
[NH2:1][C:2]1[CH:7]=[C:6]([C:8]([F:11])([F:10])[F:9])[CH:5]=[C:4]([NH2:12])[N:3]=1.[N+:13]([O-])([OH:15])=[O:14].[NH4+].[OH-]>OS(O)(=O)=O>[NH2:12][C:4]1[C:5]([N+:13]([O-:15])=[O:14])=[C:6]([C:8]([F:9])([F:11])[F:10])[CH:7]=[C:2]([NH2:1])[N:3]=1

Participants

5

Reactant 3

HCID 944Nitric AcidHCID 14923Ammonium HydroxideHCID 218962064-(Trifluoromethyl)pyridine-2,6-diamine

Product 1

HCID 19012214HCID 19012214, compound

Reagents, catalysts & solvents 1

HCID 1118Sulfuric AcidSolvent

Procedure

To a mixture of 2,6-diamino-4-trifluoromethylpyridine (173 mg) in H2SO4 (3 mL) at 0° C. was added HNO3 (0.048 mL, d=1.40). The stirred mixture was sequentially warmed to RT, aged 1.5 hours, poured onto 50 g ice, neutralized with NH4OH, extracted with EtOAc, filtered through 20 g SiO2 (washed with EtOAc until yellow color eluted), and concentrated to give 70 mg of 2,6-diamino-3-nitro-4-trifluoromethylpyridine as a yellow solid. A 1:1THF/MeOH solution of the nitro compound (65 mg) was hydrogenated (1 atm H2, Ra-Ni, 16 hours at RT), filtered, concentrated, and converted to the title compound by the method outlined in Example 21. FAB MS (M+ +1)=465; 1H NMR (300 MHz, CD3OD) δ 7.61 (t, 2H, J=7.5 Hz), 7.54-7.48 (m, 2H), 7.13-7.04 (AB q, 4H), 6.74 (s, 1H), 5.41 (s, 2H), 2.79 (q, 2H, J=7.5 Hz), 1.16 (t, 3H, J=7.5 Hz).

Workup

  1. extractionextracted with EtOAc
  2. filtrationfiltered through 20 g SiO2 (washed with EtOAc until yellow color eluted)
  3. concentrationconcentrated

Sources & evidence

ORD record
ord-02172ef871dd4490a1c25dcb8d286006
Source dataset
uspto-grants-1994_07
Patent number
US05332744

Reaction notes

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