Ammonia → 5-(Trifluoromethyl)pyridine-2,3-diamine

HRID 923787Notes

Reaction equation

HRID 923787 reaction equation
Br[C:2]1[C:3]([NH2:12])=[N:4][CH:5]=[C:6]([C:8]([F:11])([F:10])[F:9])[CH:7]=1.C(CC(=O)C)(=O)C.C(=O)([O-])[O-].[Cs+].[Cs+].[NH3:26]>O.[Cu+2].C(CC(=O)C)(=O)C.CN1C(=O)CCC1>[F:9][C:8]([F:11])([F:10])[C:6]1[CH:7]=[C:2]([NH2:26])[C:3]([NH2:12])=[N:4][CH:5]=1

Participants

8

Reactant 4

HCID 222AmmoniaHCID 10796Cesium carbonateHCID 31261AcetylacetoneHCID 130641553-Bromo-5-(trifluoromethyl)pyridin-2-amine

Product 1

HCID 102144255-(Trifluoromethyl)pyridine-2,3-diamine

Reagents, catalysts & solvents 3

HCID 21863952acetylacetone copper(II)CatalystHCID 962WaterSolventHCID 13387N-methyl-2-pyrrolidoneSolvent

Conditions

Temperature
110 °C

Procedure

To an autoclave reactor, 3-bromo-5-trifluoromethyl-pyridine-2-ylamine (40 g), acetylacetone copper(II) (2.2 g), acetylacetone (6.6 g), cesium carbonate (59 g), and NMP (105 ml) were added, and then 28% of aqueous ammonia solution (25 mL) was added under ice-cooling. After the reactor was sealed, the mixture heated to 110° C., and stirred with heating for 12 hours. The mixture was ice-cooled to room temperature, then diluted with water, and extracted with ethyl acetate. The combined organic layer was dried over sodium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to give 15 g 5-trifluoromethyl-pyridine-2,3-diamine (Compound (1F)-22).

Workup

  1. temperaturecooling
  2. customAfter the reactor was sealed
  3. temperaturewith heating for 12 hours
  4. temperaturecooled to room temperature
  5. extractionextracted with ethyl acetate
  6. dry with materialThe combined organic layer was dried over sodium sulfate
  7. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-c845f950bbc84a73b69e9660240a44ec
Source dataset
uspto-grants-2016_03
Patent number
US09278983B2

Reaction notes

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