Nitric Acid → 1-Bromo-4-fluoro-2-methyl-5-nitrobenzene

HRID 715092Notes

Reaction equation

HRID 715092 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([F:8])=[CH:4][C:3]=1[CH3:9].[N+:10]([O-])([OH:12])=[O:11]>S(=O)(=O)(O)O>[Br:1][C:2]1[CH:7]=[C:6]([N+:10]([O-:12])=[O:11])[C:5]([F:8])=[CH:4][C:3]=1[CH3:9]

Participants

4

Reactant 2

HCID 944Nitric AcidHCID 967432-Bromo-5-fluorotoluene

Product 1

HCID 100369831-Bromo-4-fluoro-2-methyl-5-nitrobenzeneYield 104.8%

Reagents, catalysts & solvents 1

HCID 1118Sulfuric AcidSolvent

Procedure

Combine 1-bromo-4-fluoro-2-methylbenzene (30.0 g, 159 mmol) in concentrated sulfuric acid (100 mL), cool to about −5° C., and treat drop wise with nitric acid (11.00 mL, 174 mmol) over 20 minutes. Allow reaction mixture to warm to RT and stir for 30 min. Pour onto crushed ice with stirring and partition with tert-butyl methyl ether (MTBE) (200 mL). Separate the aqueous layer and extract with MTBE (2×50 mL). Combine organic layers, dry and concentrate under reduced pressure to provide 1-bromo-4-fluoro-2-methyl-5-nitrobenzene as an orange-colored viscous oil (39.0 g).

Workup

  1. customAllow reaction mixture
  2. additionPour
  3. customonto crushed ice
  4. stirringwith stirring
  5. custompartition with tert-butyl methyl ether (MTBE) (200 mL)
  6. customSeparate the aqueous layer
  7. extractionextract with MTBE (2×50 mL)
  8. customCombine organic layers, dry
  9. concentrationconcentrate under reduced pressure

Sources & evidence

ORD record
ord-dc782d8cc49045abb6e8f72992bfd651
Source dataset
uspto-grants-2015_11
Patent number
US09187474B2

Reaction notes

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