Ammonia → 6-Methyl-2,4-bis(2,2,2-trifluoroethoxy)pyridin-3-amine

HRID 1354255Notes

Reaction equation

HRID 1354255 reaction equation
[F:1][C:2]([F:22])([F:21])[CH2:3][O:4][C:5]1[C:10]([N+:11]([O-])=O)=[C:9]([O:14][CH2:15][C:16]([F:19])([F:18])[F:17])[CH:8]=[C:7]([CH3:20])[N:6]=1.S(S([O-])=O)([O-])=O.[Na+].[Na+].S(=O)(=O)(O)O.N>C(O)(C)C.O>[NH2:11][C:10]1[C:5]([O:4][CH2:3][C:2]([F:22])([F:1])[F:21])=[N:6][C:7]([CH3:20])=[CH:8][C:9]=1[O:14][CH2:15][C:16]([F:18])([F:19])[F:17]

Participants

7

Reactant 4

HCID 222AmmoniaHCID 1118Sulfuric AcidHCID 24489Sodium Dithionite3×HCID 230924206-Methyl-3-nitro-2,4-bis(2,2,2-trifluoroethoxy)pyridine

Product 1

HCID 230924336-Methyl-2,4-bis(2,2,2-trifluoroethoxy)pyridin-3-amineYield 80.3%

Reagents, catalysts & solvents 2

HCID 962WaterSolvent4×HCID 3776IsopropanolSolvent

Conditions

Temperature
80 °C

Procedure

2,4-Bis(2,2,2-trifluoroethoxy)-6-methyl-3-nitropyridine (45.00 g, 134.7 mmol) was dissolved in isopropanol (300 mL), and a solution of sodium dithionite (78.00 g, 448.0 mmol) in water (300 mL) was added thereto under stirring at 80° C. Fifteen minutes after starting of the reaction, a solution of sodium dithionite (16.50 g, 94.8 mmol) in water (51 mL) was added to the reaction mixture. Further, 25 minutes after starting of the reaction, a solution of sodium dithionite (11.10 g, 63.8 mmol) in water (51 mL) was added to the reaction mixture and then stirred for ten minutes. After completion of reaction, 4 mol/L aqueous sulfuric acid (201 mL) was added to the reaction mixture, followed by stirring for 30 minutes at 90° C. After the reaction mixture was allowed to cool, 28% aqueous ammonia (360 mL) was added thereto under cooling with ice, followed by stirring for 30 minutes. The reaction mixture was diluted with water and then extracted with chloroform. The organic layer was washed with saturated brine and then dried over sodium sulfate anhydrate, followed by concentration under reduced pressure. The thus-obtained crystals were recrystallized from hexane, to thereby yield 3-amino-2,4-bis(2,2,2-trifluoroethoxy)-6-methylpyridine (32.91 g, yield 80%) as pale yellow needles.

Workup

  1. customFifteen minutes after starting of the reaction
  2. customFurther, 25 minutes after starting of the reaction
  3. stirringstirred for ten minutes
  4. additionwas added to the reaction mixture
  5. stirringby stirring for 30 minutes at 90° C
  6. temperatureto cool
  7. temperatureunder cooling with ice
  8. stirringby stirring for 30 minutes
  9. extractionextracted with chloroform
  10. washThe organic layer was washed with saturated brine
  11. dry with materialdried over sodium sulfate anhydrate
  12. concentrationfollowed by concentration under reduced pressure
  13. customThe thus-obtained crystals were recrystallized from hexane

Sources & evidence

ORD record
ord-8daba8bd7102438ba3e369eedb7b588e
Source dataset
uspto-grants-2007_05
Patent number
US07223764B2

Reaction notes

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