Acetic Acid → 3-(3-Chloropropoxy)-4-methoxy-6-nitrobenzoic acid

HRID 384812Notes

Reaction equation

HRID 384812 reaction equation
[Cl:1][CH2:2][CH2:3][CH2:4][O:5][C:6]1[CH:7]=[C:8]([CH:12]=[CH:13][C:14]=1[O:15][CH3:16])[C:9]([OH:11])=[O:10].[N:17]([O-:19])=[O:18].[Na+].C(O)(=O)C.[N+]([O-])(O)=O>O>[CH3:16][O:15][C:14]1[C:6]([O:5][CH2:4][CH2:3][CH2:2][Cl:1])=[CH:7][C:8]([C:9]([OH:11])=[O:10])=[C:12]([N+:17]([O-:19])=[O:18])[CH:13]=1

Participants

6

Reactant 4

HCID 176Acetic AcidHCID 944Nitric AcidHCID 230330123-(3-Chloropropoxy)-4-methoxybenzoic acidHCID 23668193Sodium Nitrite

Product 1

HCID 230330043-(3-Chloropropoxy)-4-methoxy-6-nitrobenzoic acidYield 927.7%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
40 °C

Procedure

In a 50 mL volume glass flask equipped with a stirrer, a thermometer and a dropping funnel were placed 9.57 g (38.7 mmol) of 3-(3-chloropropoxy)-4-methoxybenzoic acid (purity: 99%) obtained in Reference Example III-13, 0.27 g (3.87 mmol) of sodium nitrite, and 12.5 mL of acetic acid. The resulting mixture was heated to 40° C. under stirring. To the reaction mixture was dropwise added slowly 16.2 g (154.8 mmol) of nitric acid (60 wt. %), and the mixture was heated at the same temperature for 5 hours. After the reaction was complete, 20 mL of water was added to the reaction mixture, and the aqueous mixture was cooled to 20° C., precipitating a crystalline product. The crystalline product was collected by filtration, washed successively with 30 mL of water and 30 mL of n-heptane, and dried under reduced pressure, to give 10.4 g (isolated yield: 92.0%, purity: 99% in terms of area percentage determined by high performance liquid chromatography) of 4-methoxy-5-(3-chloropropoxy)-2-nitrobenzoic acid as a white crystalline product. 4-Methoxy-5-(3-chloropropoxy)-2-nitrobenzoic acid had the following characteristics.

Workup

  1. customIn a 50 mL volume glass flask equipped with a stirrer
  2. temperaturethe mixture was heated at the same temperature for 5 hours
  3. temperaturethe aqueous mixture was cooled to 20° C.
  4. customprecipitating a crystalline product
  5. filtrationThe crystalline product was collected by filtration
  6. washwashed successively with 30 mL of water and 30 mL of n-heptane
  7. customdried under reduced pressure

Sources & evidence

ORD record
ord-a3c3e951220e4cc4a7cf976c9a7e5d25
Source dataset
uspto-grants-2013_02
Patent number
US08367824B2

Reaction notes

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