Sulfuric Acid → Methyl 3-bromo-5-nitrobenzoate

HRID 1071959Notes

Reaction equation

HRID 1071959 reaction equation
[N+:1]([C:4]1[CH:5]=[C:6]([CH:11]=[CH:12][CH:13]=1)[C:7]([O:9][CH3:10])=[O:8])([O-:3])=[O:2].S(=O)(=O)(O)O.[Br:19]Br>S(=O)(=O)(O)O.S([O-])([O-])(=O)=O.[Ag+2].CO>[Br:19][C:12]1[CH:11]=[C:6]([CH:5]=[C:4]([N+:1]([O-:3])=[O:2])[CH:13]=1)[C:7]([O:9][CH3:10])=[O:8]

Participants

7

Reactant 3

HCID 1118Sulfuric AcidHCID 24408BromineHCID 69260Methyl 3-nitrobenzoate

Product 1

HCID 239341Methyl 3-bromo-5-nitrobenzoateYield 72%

Reagents, catalysts & solvents 3

HCID 1118Sulfuric AcidCatalystHCID 178418844HCID 178418844, compoundCatalystHCID 887MethanolSolvent

Conditions

Temperature
90 °C

Procedure

A mixture of methyl 3-nitrobenzoate (122 g, 674 mmol), silver sulphate (100 g, 320.7 mmol) and concentrated sulfuric acid (750 mL) was stirred mechanically and heated at 90° C. To this mixture was added bromine (37 mL), dropwise, over 2 h. The reaction was stirred another hour, cooled and filtered. The filtrate was mixed with 2 L water and 1 Kg crushed ice. The solid was filtered and dried to afford a mixture of the desired methyl ester and free acid hydrolysis product. The mixture was taken up into methanol (1 L), treated with 10 drops concentrated sulfuric acid and refluxed for 12 h. The reaction mixture was allowed to cool and the crystals that were deposited were collected and dried in a desiccator to afford 126 g (72% yield) of methyl 3-bromo-5-nitrobenzoate (EX-119A): 1H NMR (300 MHz, CDCl3) δ 8.65 (s, 1 H), 8.44 (s, 1 H), 8.37 (s, 1 H), 3.94 (s, 3H).

Workup

  1. stirringThe reaction was stirred another hour
  2. temperaturecooled
  3. filtrationfiltered
  4. additionThe filtrate was mixed with 2 L water and 1 Kg
  5. customcrushed ice
  6. filtrationThe solid was filtered
  7. customdried
  8. customto afford
  9. temperaturerefluxed for 12 h
  10. temperatureto cool
  11. customthe crystals that were deposited were collected
  12. customdried in a desiccator

Sources & evidence

ORD record
ord-aad666afc1da407fb87b99859c5f9a8a
Source dataset
uspto-grants-2005_06
Patent number
US06908919B2

Reaction notes

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