Nitric Acid → Ethyl 4,5-bis(2-methoxyethoxy)-2-nitrobenzoate

HRID 1094536Notes

Reaction equation

HRID 1094536 reaction equation
[CH3:1][O:2][CH2:3][CH2:4][O:5][C:6]1[CH:7]=[C:8]([CH:14]=[CH:15][C:16]=1[O:17][CH2:18][CH2:19][O:20][CH3:21])[C:9]([O:11][CH2:12][CH3:13])=[O:10].S(=O)(=O)(O)O.[N+:27]([O-])([OH:29])=[O:28].[Cl-].[Na+]>C1(C)C=CC=CC=1.C(O)(=O)C>[CH3:21][O:20][CH2:19][CH2:18][O:17][C:16]1[C:6]([O:5][CH2:4][CH2:3][O:2][CH3:1])=[CH:7][C:8]([C:9]([O:11][CH2:12][CH3:13])=[O:10])=[C:14]([N+:27]([O-:29])=[O:28])[CH:15]=1

Participants

7

Reactant 4

HCID 944Nitric AcidHCID 1118Sulfuric AcidHCID 5234Sodium ChlorideHCID 2808992Ethyl 3,4-bis(2-methoxyethoxy)benzoate

Product 1

HCID 11186961Ethyl 4,5-bis(2-methoxyethoxy)-2-nitrobenzoateYield 100%

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 1140TolueneSolvent

Procedure

In a 20 L-volume glass reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, the acetic acid solution containing 2,023 g (6.78 moles) of ethyl 3,4-bis(2-methoxyethoxy)benzoate prepared in the Synthesis Example 1 was placed. To the solution, 318 g (3.18 moles) of concentrated sulfuric acid was gently added while stirring the solution at room temperature. The mixture was heated to 60 to 70° C. To the mixture, 1,857 g (20.34 moles) of 69 wt. % nitric acid was gently added while stirring the mixture. The resulting mixture was allowed to react for 2 hours while maintaining the temperature. After the reaction was complete, the reaction solution was cooled to room temperature. To the reaction solution, 5,200 mL of a 20 wt. % aqueous sodium chloride solution and 5,200 mL of toluene were added. The separated organic layer (toluene layer) was washed twice with 7,800 mL of a 1 mole per L aqueous sodium hydroxide solution, and further washed twice with 7,800 mL of a 20 wt. % aqueous sodium chloride solution. The organic layer was concentrated under reduced pressure to obtain 2,328 g of ethyl 4,5-bis(2-methoxyethoxy)-2-nitrobenzoate as an orange liquid (isolation yield: 100%).

Workup

  1. customIn a 20 L-volume glass reaction vessel
  2. customequipped with a stirrer
  3. customprepared in the Synthesis Example 1
  4. temperatureThe mixture was heated to 60 to 70° C
  5. stirringwhile stirring the mixture
  6. customto react for 2 hours
  7. temperaturewhile maintaining the temperature
  8. temperaturethe reaction solution was cooled to room temperature
  9. washThe separated organic layer (toluene layer) was washed twice with 7,800 mL of a 1 mole per L aqueous sodium hydroxide solution
  10. washfurther washed twice with 7,800 mL of a 20 wt. % aqueous sodium chloride solution
  11. concentrationThe organic layer was concentrated under reduced pressure

Sources & evidence

ORD record
ord-d09bbc392c654dd981e68dd387d89643
Source dataset
uspto-grants-2012_03
Patent number
US08133999B2

Reaction notes

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