3,4-difluoro-N-(2-nitrophenyl)aniline → N-(3,4-difluorophenyl)benzene-1,2-diamine

HRID 1818834Notes

Reaction equation

HRID 1818834 reaction equation
[F:1][C:2]1[CH:3]=[C:4]([CH:15]=[CH:16][C:17]=1[F:18])[NH:5][C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][C:7]=1[N+:12]([O-])=O>C(OCC)(=O)C.CO.[Pd]>[F:1][C:2]1[CH:3]=[C:4]([NH:5][C:6]2[C:7]([NH2:12])=[CH:8][CH:9]=[CH:10][CH:11]=2)[CH:15]=[CH:16][C:17]=1[F:18]

Participants

4

Reactant 1

HCID 595607683,4-difluoro-N-(2-nitrophenyl)aniline

Product 1

HCID 29067155N-(3,4-difluorophenyl)benzene-1,2-diamineYield 51%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 21584119Ethylacetate methanolSolvent

Procedure

A solution of 3,4-difluoro-N-(2-nitrophenyl)aniline (22.76 g, 91 mmol) in 50% ethyl acetate/methanol (500 mL) was treat with palladium on carbon 10 w. % loading, matrix activated carbon support (3.07 g). The reaction mixture was placed on the Parr shaker for 3 h at 60 psi. The reaction mixture was filtered through celite and evaporated. The crude reaction product was purified by flash chromatography (SiO2, 3→50% ethyl acetate/heptane) to provided N-(3,4-difluorophenyl)benzene-1,2-diamine (10.17 g, 51%) as a brown solid: HPLC purity 99.9% at 210-370 nm, 9.4 min.; Xterra RP18, 3.5 u, 150×4.6 mm column, 1.2 mL/min, 85/15-5/95 (Ammon. Form. Buff. Ph=3.5/ACN+MeOH) for 10 min, hold 4 min.

Workup

  1. filtrationThe reaction mixture was filtered through celite
  2. customevaporated
  3. customThe crude reaction product
  4. customwas purified by flash chromatography (SiO2, 3→50% ethyl acetate/heptane)

Sources & evidence

ORD record
ord-00d583feb80d4ac7906933d3f37dcbf6
Source dataset
uspto-grants-2009_10
Patent number
US07601722B2

Reaction notes

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