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

HRID 861933Notes

Reaction equation

HRID 861933 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/exane 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/exane

Sources & evidence

ORD record
ord-b5d2debb08114d4bbd5323b062d82f54
Source dataset
uspto-grants-1998_02
Patent number
US05716966

Reaction notes

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