Nitric Acid → Methyl 5-bromo-2-hydroxy-3-nitrobenzoate

HRID 415165Notes

Reaction equation

HRID 415165 reaction equation
[Br:1][C:2]1[CH:3]=[CH:4][C:5]([OH:12])=[C:6]([CH:11]=1)[C:7]([O:9][CH3:10])=[O:8].[N+:13]([O-])([OH:15])=[O:14]>OS(O)(=O)=O>[Br:1][C:2]1[CH:3]=[C:4]([N+:13]([O-:15])=[O:14])[C:5]([OH:12])=[C:6]([CH:11]=1)[C:7]([O:9][CH3:10])=[O:8]

Participants

4

Reactant 2

HCID 944Nitric AcidHCID 77683Methyl 5-bromosalicylate

Product 1

HCID 970238Methyl 5-bromo-2-hydroxy-3-nitrobenzoateYield 85.3%

Reagents, catalysts & solvents 1

HCID 1118Sulfuric AcidSolvent2×

Procedure

To a mixture of methyl 5-bromo-2-hydroxybenzoate (150 g, 0.65 mol) in concentrated H2SO4 (320 mL) below 0° C. was added dropwise a mixture of concentrated HNO3 (69.2 g, 0.71 mol) and concentrated H2SO4 (97 mL) with stirring below 5° C. After the addition, the mixture was stirred at this temperature for 3 hr. The reaction mixture was poured into crash ice and the precipitate was collected, washed with cold water, hot ethanol and dried to give methyl 5-bromo-2-hydroxy-3-nitrobenzoate (153 g, yield 85%). 1H-NMR (400 MHz, CDCl3-d) δ 4.04 (s, 3H), 8.25 (d, J=2.4 Hz, 1H), 8.28 (d, J=2.4 Hz, 1H), 11.92 (s, 1H); LC-MS (ESI) m/z 278 [M+1]+.

Workup

  1. additionwas added dropwise
  2. additionAfter the addition
  3. stirringthe mixture was stirred at this temperature for 3 hr
  4. additionThe reaction mixture was poured into crash ice
  5. customthe precipitate was collected
  6. washwashed with cold water, hot ethanol
  7. customdried

Sources & evidence

ORD record
ord-7ab10bccf63d422481dcb243509d55eb
Source dataset
uspto-grants-2012_01
Patent number
US08088760B2

Reaction notes

Loading…