Bromine → HCID 86657965, compound

HRID 2366764Notes

Reaction equation

HRID 2366764 reaction equation
[S-:1][C:2]#[N:3].[K+].[NH2:5][C:6]1[CH:7]=[CH:8][C:9]([N:12]([CH3:26])[C:13]2[CH:14]=[C:15]([NH:19][C:20](=[O:25])[C:21]([F:24])([F:23])[F:22])[CH:16]=[CH:17][CH:18]=2)=[N:10][CH:11]=1.BrBr>C(O)(=O)C>[NH2:3][C:2]1[S:1][C:11]2[C:6]([N:5]=1)=[CH:7][CH:8]=[C:9]([N:12]([CH3:26])[C:13]1[CH:14]=[C:15]([NH:19][C:20](=[O:25])[C:21]([F:24])([F:22])[F:23])[CH:16]=[CH:17][CH:18]=1)[N:10]=2

Participants

5

Reactant 3

HCID 24408BromineHCID 516872Potassium thiocyanateHCID 86657966HCID 86657966, compound

Product 1

HCID 86657965HCID 86657965, compoundYield 20.3%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent3×

Procedure

To a solution of potassium thiocyanate (4.31 g, 44.4 mmol) in acetic acid (15 ml) was added a solution of N-[3-[(5-aminopyridin-2-yl)(methyl)amino]phenyl]-2,2,2-trifluoroacetamide (3.46 g, 11.1 mmol) in acetic acid (10 mL), and the mixture was stirred at room temperature for 20 min. To this solution was added dropwise a solution of bromine (1.95 g, 12.2 mmol) in acetic acid (10 mL), and the mixture was stirred at room temperature for 16 hr. The reaction mixture was filtered through celite, and the filtrate was concentrated under reduced pressure. The residue was dissolved in ethyl acetate (140 mL)/tetrahydrofuran (70 mL), and washed with aqueous sodium hydrogen carbonate solution (70 mL) and saturated brine (50 mL). The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (hexane/ethyl acetate=80/20→0/100) to give the title compound (829 mg, 20%) as a violet powder.

Workup

  1. stirringthe mixture was stirred at room temperature for 16 hr
  2. filtrationThe reaction mixture was filtered through celite
  3. concentrationthe filtrate was concentrated under reduced pressure
  4. dissolutionThe residue was dissolved in ethyl acetate (140 mL)/tetrahydrofuran (70 mL)
  5. washwashed with aqueous sodium hydrogen carbonate solution (70 mL) and saturated brine (50 mL)
  6. dry with materialThe organic layer was dried over anhydrous sodium sulfate
  7. concentrationconcentrated under reduced pressure
  8. customthe residue was purified by silica gel column chromatography (hexane/ethyl acetate=80/20→0/100)

Sources & evidence

ORD record
ord-95088d7ef300409f81f1884e8b4807fe
Source dataset
uspto-grants-2014_04
Patent number
US08697874B2

Reaction notes

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