Nitric Acid → 1,5-Difluoro-3-methoxy-2-nitrobenzene

HRID 254320Notes

Reaction equation

HRID 254320 reaction equation
[F:1][C:2]1[CH:3]=[C:4]([O:9][CH3:10])[CH:5]=[C:6]([F:8])[CH:7]=1.[N+:11]([O-])([OH:13])=[O:12].O.C(OCC)(=O)C>ClCCl>[F:1][C:2]1[CH:7]=[C:6]([F:8])[CH:5]=[C:4]([O:9][CH3:10])[C:3]=1[N+:11]([O-:13])=[O:12]

Participants

6

Reactant 4

HCID 944Nitric AcidHCID 962WaterHCID 8857Ethyl AcetateHCID 27245183,5-Difluoroanisole

Product 1

HCID 103301291,5-Difluoro-3-methoxy-2-nitrobenzeneYield 72%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of 3,5-difluoroanisole (30 g, 208 mmol) in 260 mL dichloromethane was added HNO3 (>90% fuming, 60 mL) dropwise at 0° C. The resulting solution was stirred at 0° C. for 3 hours, then washed water. The aqueous phase was extracted with dichloromethane. The organic phase was washed with brine, dried over magnesium sulfate and condensed on a rotavap. The residue was recrystallized in hexane and ethyl acetate to provide 28.5 g (72% yield) of 1,5-difluoro-3-methoxy-2-nitrobenzene as an off-white powder. 1H NMR (400 MHz, DMSO) δ ppm 7.20 (m, 2H), 3.91 (s, 3H).

Workup

  1. extractionThe aqueous phase was extracted with dichloromethane
  2. washThe organic phase was washed with brine
  3. dry with materialdried over magnesium sulfate and condensed on a rotavap
  4. customThe residue was recrystallized in hexane

Sources & evidence

ORD record
ord-61f6444c4c2c4fdd8432415429340b72
Source dataset
uspto-grants-2011_01
Patent number
US07875618B2

Reaction notes

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