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

HRID 1747462Notes

Reaction equation

HRID 1747462 reaction equation
[CH3:1][O:2][C:3](=[O:12])[C:4]1[CH:9]=[C:8]([Cl:10])[CH:7]=[CH:6][C:5]=1[OH:11].[N+:13]([O-])([OH:15])=[O:14]>S(=O)(=O)(O)O>[CH3:1][O:2][C:3](=[O:12])[C:4]1[CH:9]=[C:8]([Cl:10])[CH:7]=[C:6]([N+:13]([O-:15])=[O:14])[C:5]=1[OH:11]

Participants

4

Reactant 2

HCID 944Nitric Acid2×HCID 77684Benzoic acid, 5-chloro-2-hydroxy-, methyl ester

Product 1

HCID 235651Methyl 5-chloro-2-hydroxy-3-nitrobenzoateYield 89%

Reagents, catalysts & solvents 1

HCID 1118Sulfuric AcidSolvent2×

Conditions

Temperature
0 °C

Procedure

Methyl-5-Chloro-2-hydroxylbenzoate (30 g, 160 mmol) is suspended in sulfuric acid (140 mL) and cooled to 0° C. in an ice bath. Nitric acid (13 mL) in sulfuric acid (30 mL) is added drop wise to the suspension over 30 minutes while maintaining the reaction temperature at 0° C. The reaction is warmed to room temperature and stirred for 4 hours. An additional 6 mL of nitric acid is added drop wise to the reaction over 30 minutes and the reaction is heated to 45° C. for 16 hours. The reaction is poured onto crushed ice, and the resulting yellow precipitate collected and washed with copious amount of water and dried in vacuo to give the title compound (33 g 142 mmol, 89%). LCMS (ESMS): m/z 232.7 (M+H+).

Workup

  1. temperaturewhile maintaining the reaction temperature at 0° C
  2. temperatureThe reaction is warmed to room temperature
  3. customwise to the reaction over 30 minutes
  4. temperaturethe reaction is heated to 45° C. for 16 hours
  5. additionThe reaction is poured
  6. customonto crushed ice
  7. customthe resulting yellow precipitate collected
  8. washwashed with copious amount of water
  9. customdried in vacuo

Sources & evidence

ORD record
ord-d6fc059d26ac4c30a490eee9e9913950
Source dataset
uspto-grants-2015_10
Patent number
US09150556B2

Reaction notes

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