Nitric Acid → 4,5-Difluoro-2-nitrophenol

HRID 660830Notes

Reaction equation

HRID 660830 reaction equation
[F:1][C:2]1[CH:3]=[C:4]([OH:9])[CH:5]=[CH:6][C:7]=1[F:8].[N+:10]([O-])([OH:12])=[O:11].S([O-])([O-])(=O)=O.[Mg+2]>ClCCl.S([O-])([O-])(=O)=O.[Ni+].[NH4+]>[F:8][C:7]1[C:2]([F:1])=[CH:3][C:4]([OH:9])=[C:5]([N+:10]([O-:12])=[O:11])[CH:6]=1

Participants

6

Reactant 3

HCID 944Nitric AcidHCID 24083Sulfuric acid magnesium salt (1:1)HCID 759273,4-Difluorophenol

Product 1

HCID 27741824,5-Difluoro-2-nitrophenol

Reagents, catalysts & solvents 2

HCID 171000000CID 171000000CatalystHCID 6344DichloromethaneSolvent

Procedure

To a solution of 3,4-difluorophenol (1.56 g, 7.69 mmol) in dichloromethane (10 mL) under a blanket of nitrogen is added ammonium nickel sulfate (2.0 g, 5.07 mmol), with vigorous stirring, followed by the addition of nitric acid (69%, 0.770 mL, 7.69 mmol). The resulting heterogeneous mixture is then stirred at RT for 5-10 min; at this point a bright orange solution was observed along with a mild exothermic gaseous emission. (LC/MS indicated the formation of one single product.) Anhydrous magnesium sulfate (˜1 g) is then added to the reaction mixture, which is stirred and filtered to afford an orange solution. Removal of dichloromethane under reduced pressure affords an orange solid residue. (low melting solid, sublimed upon storage) 1H NMR (400 MHz, δ, CDCl3): 10.61 (s, 1H), 8.01 (m, 1H), 7.00 (m, 1H).

Workup

  1. stirringis stirred
  2. filtrationfiltered
  3. customto afford an orange solution
  4. customRemoval of dichloromethane under reduced pressure
  5. customaffords an orange solid residue

Sources & evidence

ORD record
ord-24b30ef56a0044b098d313b005ea4b25
Source dataset
uspto-grants-2011_12
Patent number
US08084448B2

Reaction notes

Loading…