Ammonium Hydroxide → 4-Amino-2-fluoro-5-nitrobenzonitrile

HRID 1858010Notes

Reaction equation

HRID 1858010 reaction equation
[F:1][C:2]1[CH:9]=[C:8](F)[C:7]([N+:11]([O-:13])=[O:12])=[CH:6][C:3]=1[C:4]#[N:5].[OH-].[NH4+:15]>C(O)C>[NH2:15][C:8]1[C:7]([N+:11]([O-:13])=[O:12])=[CH:6][C:3]([C:4]#[N:5])=[C:2]([F:1])[CH:9]=1

Participants

4

Reactant 2

HCID 14923Ammonium HydroxideHCID 118197152,4-Difluoro-5-nitrobenzonitrile

Product 1

HCID 104197934-Amino-2-fluoro-5-nitrobenzonitrile

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

A mixture comprising 2,4-difluoro-5-nitrobenzonitrile (9.03 g, 0.049 mol) and ethanol (10-15 mL) was stirred at ambient temperature while concentrated ammonium hydroxide (40 mL) was slowly added to give a precipitate. The precipitate was isolated by filtration and lyophilized to give 4-amino-2-fluoro-5-nitrobenzonitrile (7.84 g, 0.043 mol) as an off-white solid; PB-CI/MS: 182=(MH+); 1H-NMR (300 Mhz, DMSO-d6): 6.856(d, 1H), 8.22(bs, 2H), 8.577(d, 1H). A mixture of 4-amino-2-fluoro-5-nitrobenzonitrile (3 g, 0.017 mol), PtO2 (≈300 mg) and methanol (20 mL)was hydrogenated (1 atm) for approximately 12 hours, filtered over celite and concentrated to dryness to provide 4,5-diamino-2-fluorobenzonitrile (2.5 g, 0.017 mol) as a brown solid PB-CI/MS: 152=(MH+); 1H-NMR (300 Mhz, DMSO-d6): 4.7(bs, 2H), 5.863(bs, 2H), 6.375(d, 1H), 6.56(d, 1H).

Workup

  1. additionwas slowly added
  2. customto give a precipitate
  3. customThe precipitate was isolated by filtration

Sources & evidence

ORD record
ord-d861ca2fa468475dbbae5297081b5754
Source dataset
uspto-grants-2000_11
Patent number
US06150379

Reaction notes

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