N-(4-chloro-3-fluorophenyl)-3-nitropyridin-2-amine → N2-(4-chloro-3-fluorophenyl)pyridine-2,3-diamine

HRID 2272703Notes

Reaction equation

HRID 2272703 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([NH:8][C:9]2[C:14]([N+:15]([O-])=O)=[CH:13][CH:12]=[CH:11][N:10]=2)=[CH:4][C:3]=1[F:18]>[Ni].C(OCC)(=O)C>[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([NH:8][C:9]2[C:14]([NH2:15])=[CH:13][CH:12]=[CH:11][N:10]=2)=[CH:4][C:3]=1[F:18]

Participants

4

Reactant 1

HCID 86730067N-(4-chloro-3-fluorophenyl)-3-nitropyridin-2-amine

Product 1

HCID 61466916N2-(4-chloro-3-fluorophenyl)pyridine-2,3-diamine

Reagents, catalysts & solvents 2

HCID 935NickelCatalystHCID 8857Ethyl AcetateSolvent

Procedure

A mixture of N-(4-chloro-3-fluorophenyl)-3-nitropyridin-2-amine (C11) (5.0 g, 19 mmol) and Raney nickel (3 g) in ethyl acetate (400 mL) was degassed three times with hydrogen. The reaction mixture was then hydrogenated at room temperature for 20 hours. After removal of the catalyst via filtration, the filtrate was concentrated in vacuo. Purification via silica gel chromatography afforded the product as a gray solid. Yield: 3.1 g, 13 mmol, 68%. 1H NMR (400 MHz, CDCl3) δ 7.87 (dd, J=4.9, 1.6 Hz, 1H), 7.38 (dd, J=11.5, 2.5 Hz, 1H), 7.24 (dd, J=8.5, 8.4 Hz, 1H), 7.06 (dd, J=7.6, 1.6 Hz, 1H), 6.92 (ddd, J=8.7, 2.5, 1.0 Hz, 1H), 6.82 (dd, J=7.6, 4.9 Hz, 1H), 6.37 (br s, 1H), 3.38 (br s, 2H).

Workup

  1. customwas degassed three times with hydrogen
  2. customAfter removal of the catalyst
  3. filtrationvia filtration
  4. concentrationthe filtrate was concentrated in vacuo
  5. customPurification via silica gel chromatography

Sources & evidence

ORD record
ord-5aefc373734747c0880bfe4fe039bffc
Source dataset
uspto-grants-2015_09
Patent number
US09120788B2

Reaction notes

Loading…