Nitromethane → Beta-Nitrostyrene

HRID 2269678Notes

Reaction equation

HRID 2269678 reaction equation
CO[C:3]1[CH:4]=[C:5]([CH:8]=[C:9]2OCO[C:10]=12)[CH:6]=O.C([O-])(=O)C.[NH4+].[N+:19]([CH3:22])([O-:21])=[O:20]>C(O)(=O)C>[N+:19]([CH:22]=[CH:6][C:5]1[CH:8]=[CH:9][CH:10]=[CH:3][CH:4]=1)([O-:21])=[O:20]

Participants

5

Reactant 3

HCID 6375NitromethaneHCID 220161,3-Benzodioxole-5-carboxaldehyde, 7-methoxy-HCID 517165Ammonium Acetate

Product 1

HCID 7626Beta-NitrostyreneYield 133.7%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent3×

Procedure

Under N2, 3-Methoxy-4,5-methylenedioxybenzaldehyde (928 g, 97%, w., 5 mol), Acetic acid (2.5 L), followed by ammonium acetate (664 g, 8.5 mol) and HOAc (1 L) were added to a 22-L 4-necked flask equipped with a an overhead stirrer, a thermometer and a refluxing condenser. The mixture was stirred at room temperature for 10 minutes. Nitromethane (1350 mL, 25 mol) and acetic acid (1 L) were subsequently added. The mixture was heated and stirred at 95° C. for 6 hours. The reaction was monitored with HPLC [HPLC conditions: Zorbax Rx-C8 (25 cm×4.6 mm); column temperature 35° C.; gradient elution from 5:95 to 90:10-acetonitrile:water (0.1% phosphoric acid) in 15 minutes; flow-1.5 mL/min.; UV detection at 230 nm. Retention time: 3-Methoxy-4,5-methylenedioxybenzaldehyde-9.7 min.; 4-Methoxy-6(2-nitrovinyl)-1,3-Benzodioxole-11.8 min.]. After the reaction was completed, the mixture was cooled down to room temperature and filtered. The yellow solid was washed with acetic acid (2×500 mL) and water (2×1000 mL) and the product was dried under vacuum for 3 days to give 997 g of product. (yield 89%) 1H NMR(CDCl3/300 MHz) 7.90(d, J=15.0 Hz, 1H), 7.48(d, J=15.0 Hz, 1H), 6.74(m, 2H), 6.08(s, 2H), 3.95(s, 3H) ppm.

Workup

  1. additionwere added to a 22-L 4-necked flask
  2. customequipped with a an overhead stirrer
  3. temperatureThe mixture was heated
  4. stirringstirred at 95° C. for 6 hours
  5. washThe reaction was monitored with HPLC [HPLC conditions: Zorbax Rx-C8 (25 cm×4.6 mm); column temperature 35° C.; gradient elution from 5:95 to 90:10-acetonitrile:water (0.1% phosphoric acid) in 15 minutes; flow-1.5 mL/min.; UV detection at 230 nm. Retention time: 3-Methoxy-4,5-methylenedioxybenzaldehyde-9.7 min.; 4-Methoxy-6(2-nitrovinyl)-1,3-Benzodioxole-11.8 min.]
  6. temperaturethe mixture was cooled down to room temperature
  7. filtrationfiltered
  8. washThe yellow solid was washed with acetic acid (2×500 mL) and water (2×1000 mL)
  9. customthe product was dried under vacuum for 3 days

Sources & evidence

ORD record
ord-33ea17d99dcf4cf89faa64ea8ac89ebf
Source dataset
uspto-grants-2001_12
Patent number
US06329536B1

Reaction notes

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