Nitromethane → 5-(2-Nitroethenyl)-1,3-benzodioxole

HRID 1955140Notes

Reaction equation

HRID 1955140 reaction equation
[CH:1]1[C:6]([CH:7]=O)=[CH:5][C:4]2[O:9][CH2:10][O:11][C:3]=2[CH:2]=1.C([O-])(=O)C.[NH4+].[N+:17]([CH3:20])([O-:19])=[O:18]>C(O)(=O)C>[N+:17]([CH:20]=[CH:7][C:6]1[CH:1]=[CH:2][C:3]2[O:11][CH2:10][O:9][C:4]=2[CH:5]=1)([O-:19])=[O:18]

Participants

5

Reactant 3

HCID 6375NitromethaneHCID 8438PiperonalHCID 517165Ammonium Acetate

Product 1

HCID 949455-(2-Nitroethenyl)-1,3-benzodioxoleYield 80%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Conditions

Temperature
70 °C

Procedure

To piperonal (15.55 kg, 103.5 mol) under mechanical stirring and under nitrogen was added ammonium acetate (13.4 kg, 173.8 mol), acetic acid (45.2 kg), and nitromethane (18.4 kg, 301.4 mol) sequentially. The mixture was warmed to 70° C. After about 30 minutes, the yellow product began to crystallize. The reaction temperature was raised to 80° C. and stirred for about 10 hours until minimal piperonal remains. The somewhat thick reaction mixture was cooled to 10° C. and filtered. The precipitate was washed with acetic acid (2×8 kg) and then water (2×90 kg). The product was dried under a nitrogen purge and then in a vacuum oven at 50° C. for 2 days to afford 15.94 kg (80%) of the title compound as a bright yellow solid.

Workup

  1. customto crystallize
  2. temperatureThe reaction temperature was raised to 80° C.
  3. temperatureThe somewhat thick reaction mixture was cooled to 10° C.
  4. filtrationfiltered
  5. washThe precipitate was washed with acetic acid (2×8 kg)
  6. customThe product was dried under a nitrogen
  7. custompurge

Sources & evidence

ORD record
ord-e18b1ee6a5c1459fb4321e6c0a582f1a
Source dataset
uspto-grants-2000_09
Patent number
US06124341

Reaction notes

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