Nitric Acid → 5-Fluoro-2-methyl-1,3-dinitrobenzene

HRID 1901248Notes

Reaction equation

HRID 1901248 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][C:5]([CH3:8])=[C:4]([N+:9]([O-:11])=[O:10])[CH:3]=1.[N+:12]([O-])([OH:14])=[O:13]>S(=O)(=O)(O)O>[N+:12]([C:6]1[CH:7]=[C:2]([F:1])[CH:3]=[C:4]([N+:9]([O-:11])=[O:10])[C:5]=1[CH3:8])([O-:14])=[O:13]

Participants

4

Reactant 2

HCID 944Nitric AcidHCID 679654-Fluoro-2-nitrotoluene

Product 1

HCID 184653725-Fluoro-2-methyl-1,3-dinitrobenzene

Reagents, catalysts & solvents 1

HCID 1118Sulfuric AcidSolvent2×

Procedure

Fuming sulfuric acid (180 mL) is added dropwise to 4-fluoro-2-nitrotoluene (50.21 g) under an argon atmosphere. The internal temperature of the mixture is maintained at 0°-5° C. using an ice/sodium chloride bath. A preformed (ice bath) mixture of fuming nitric acid (30 mL) and fuming sulfuric acid (90 mL) is added dropwise to the previous solution over three hours. The reaction is then allowed to warm to room temperature. After stirring at room temperature for two hours, the mixture is poured slowly into ice and the products are extracted with methylene chloride (4×500 mL). The combined extracts are dried over magnesium sulfate, filtered and rotary evaporated. The crude mixture is filtered through a short pad of silica gel, using 10% ethyl acetate/hexane as solvent, then recrystallized from ethyl acetate/hexane to afford 2,6-dinitro-4-fluorotoluene as a pale yellow solid.

Workup

  1. temperatureThe internal temperature of the mixture is maintained at 0°-5° C.
  2. additionis added dropwise to the previous solution over three hours
  3. additionthe mixture is poured slowly into ice
  4. extractionthe products are extracted with methylene chloride (4×500 mL)
  5. dry with materialThe combined extracts are dried over magnesium sulfate
  6. filtrationfiltered
  7. filtrationThe crude mixture is filtered through a short pad of silica gel
  8. customrecrystallized from ethyl acetate/hexane

Sources & evidence

ORD record
ord-165e92f329d347ffaa821227c6764860
Source dataset
uspto-grants-1996_11
Patent number
US05576437

Reaction notes

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