Acetic Acid → methyl 5-methoxy-4-(3-bromopropoxy)-2-nitrobenzoate

HRID 384783Notes

Reaction equation

HRID 384783 reaction equation
[Br:1][CH2:2][CH2:3][CH2:4][O:5][C:6]1[CH:15]=[CH:14][C:9]([C:10]([O:12][CH3:13])=[O:11])=[CH:8][C:7]=1[O:16][CH3:17].[N:18]([O-:20])=[O:19].[Na+].C(O)(=O)C.[N+]([O-])(O)=O>O>[CH3:17][O:16][C:7]1[C:6]([O:5][CH2:4][CH2:3][CH2:2][Br:1])=[CH:15][C:14]([N+:18]([O-:20])=[O:19])=[C:9]([CH:8]=1)[C:10]([O:12][CH3:13])=[O:11]

Participants

6

Reactant 4

HCID 176Acetic AcidHCID 944Nitric AcidHCID 10935561HCID 10935561, compoundHCID 23668193Sodium Nitrite

Product 1

HCID 11727750methyl 5-methoxy-4-(3-bromopropoxy)-2-nitrobenzoateYield 931.3%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
40 °C

Procedure

In a 100 mL volume glass flask equipped with a stirrer, a thermometer and a dropping funnel were placed 10.2 g (33.0 mmol) of methyl 4-(3-bromopropoxy)-3-methoxybenzoate (purity: 98%) obtained in Example II-16, 0.23 g (3.30 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 13.8 g (132.0 mmol) of nitric acid (60 wt. %), and the mixture was heated at 40-50° C. for 5 hours. After the reaction was complete, 30 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 10.7 g (isolated yield: 92.0%, purity: 99% in terms of area percentage determined by high performance liquid chromatography) of methyl 5-methoxy-4-(3-bromopropoxy)-2-nitrobenzoate as a white crystalline product.

Workup

  1. customIn a 100 mL volume glass flask equipped with a stirrer
  2. temperaturethe mixture was heated at 40-50° C. 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-20a3f340346d45fd8a91d56240b022f7
Source dataset
uspto-grants-2013_02
Patent number
US08367824B2

Reaction notes

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