Nitric Acid → 1-Bromo-2-methyl-3,4-dinitrobenzene

HRID 1518117Notes

Reaction equation

HRID 1518117 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([N+:8]([O-:10])=[O:9])[C:3]=1[CH3:11].[N+:12]([O-])([OH:14])=[O:13]>OS(O)(=O)=O>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([N+:12]([O-:14])=[O:13])=[C:4]([N+:8]([O-:10])=[O:9])[C:3]=1[CH3:11]

Participants

4

Reactant 2

HCID 944Nitric AcidHCID 1235372-Bromo-6-nitrotoluene

Product 1

HCID 158896331-Bromo-2-methyl-3,4-dinitrobenzeneYield 67%

Reagents, catalysts & solvents 1

HCID 1118Sulfuric AcidSolvent

Procedure

The title compound was prepared by an adaptation of the procedure described by Mundla, S. R. (Tetrahedron Lett. 2000, 41, 4277-4279). 2-Bromo-6-nitrotoluene (1.09 g, 5.05 mmol) was placed in a 50 mL round-bottom flask equipped with a magnetic stir bar. Conc. H2SO4 (10 mL) was added, and the solid was allowed to dissolve. The reaction was cooled in an ice bath, and fuming nitric acid (1.5 eq., 0.340 mL, 7.57 mmol) was added dropwise via syringe at a rate such that the temperature of the mixture remained below 10° C. After completion of the addition, the reaction was allowed to warm to RT and stir for 2 h. The reaction mixture was poured into crushed ice, and the precipitate was isolated by filtration. The solid was washed with water (30 mL) and allowed to air dry. The crude product was purified by column chromatography using a 40-g SiO2 pre-packed column eluting with EtOAc/hexanes, 0:1 to 1:4, v/v over 30 min, yielding 879 mg (67%) of the title compound. 1H-NMR (400 MHz, CDCl3) δ: 7.97 (d, J=8.8 Hz, 1H), 7.91 (d, J=8.8 Hz, 1H), 2.45 (s, 3H).

Workup

  1. customThe title compound was prepared by an adaptation of the procedure
  2. customequipped with a magnetic stir bar
  3. dissolutionto dissolve
  4. temperatureThe reaction was cooled in an ice bath
  5. customremained below 10° C
  6. additionAfter completion of the addition
  7. additionThe reaction mixture was poured
  8. custominto crushed ice
  9. customthe precipitate was isolated by filtration
  10. washThe solid was washed with water (30 mL)
  11. customto air dry
  12. customThe crude product was purified by column chromatography
  13. washeluting with EtOAc/hexanes, 0:1 to 1:4, v/v over 30 min

Sources & evidence

ORD record
ord-3e30c79fb16d4529b37557d6f3108460
Source dataset
uspto-grants-2012_07
Patent number
US08232409B2

Reaction notes

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