Ammonium Chloride → 3-Amino-6-fluoro-2-(pyridin-2-ylamino)benzonitrile

HRID 243063Notes

Reaction equation

HRID 243063 reaction equation
[F:1][C:2]1[C:7]([C:8]#[N:9])=[C:6]([NH:10][C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][N:12]=2)[C:5]([N+:17]([O-])=O)=[CH:4][CH:3]=1.[Cl-].[NH4+]>CO.O.[Fe]>[NH2:17][C:5]1[C:6]([NH:10][C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][N:12]=2)=[C:7]([C:2]([F:1])=[CH:3][CH:4]=1)[C:8]#[N:9]

Participants

6

Reactant 2

HCID 25517Ammonium ChlorideHCID 681580896-Fluoro-3-nitro-2-(pyridin-2-ylamino)benzonitrile

Product 1

HCID 681581043-Amino-6-fluoro-2-(pyridin-2-ylamino)benzonitrileYield 54.3%

Reagents, catalysts & solvents 3

HCID 23925IronCatalystHCID 887MethanolSolventHCID 962WaterSolvent

Procedure

6-Fluoro-3-nitro-2-(pyridin-2-ylamino)benzonitrile (1.3 g, 5.0 mmol), iron powder (1.12 g, 20.1 mmol), and ammonium chloride (1.55 g, 30.2 mmol) in methanol (20 mL) and water (7 mL) were heated at 90° C. for 3 h. The reaction mixture was filtered and the filtrate concentrated in vacuo. The residue was dissolved in water and extracted with EtOAc (3×40 mL). The combined organic extracts were washed with brine, dried (MgSO4) and concentrated in vacuo to yield the title compound as a yellow solid (620 mg, 54%). 1H NMR 400 MHz δ (CDCl3): 9.05 (1H, ddd, J=7.5, 1.1, 0.8 Hz), 9.00-8.89 (1H, m), 7.34 (1H, ddd, J=9.1, 6.2, 1.7 Hz), 7.23-7.19 (1H, m), 6.83 (1H, s), 6.80 (1H, d, J=2.8 Hz), 6.65 (1H, ddd, J=7.6, 6.4, 1.4 Hz), 4.53 (2H, br s).

Workup

  1. filtrationThe reaction mixture was filtered
  2. concentrationthe filtrate concentrated in vacuo
  3. dissolutionThe residue was dissolved in water
  4. extractionextracted with EtOAc (3×40 mL)
  5. washThe combined organic extracts were washed with brine
  6. dry with materialdried (MgSO4)
  7. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-9d5bd1ea93664ab089dc5d985db2951d
Source dataset
uspto-grants-2014_02
Patent number
US08653089B2

Reaction notes

Loading…