Nitric Acid → 1-(6-Nitro-1,3-benzodioxol-5-yl)ethan-1-one

HRID 747816Notes

Reaction equation

HRID 747816 reaction equation
[CH3:1][C:2]([C:4]1[CH:9]=[CH:8][C:7]2[O:10][CH2:11][O:12][C:6]=2[CH:5]=1)=[O:3].[N+:13]([O-])([OH:15])=[O:14].CCOC(C)=O>C(O)(=O)C.CCCCCC>[CH3:1][C:2]([C:4]1[C:9]([N+:13]([O-:15])=[O:14])=[CH:8][C:7]2[O:10][CH2:11][O:12][C:6]=2[CH:5]=1)=[O:3]

Participants

6

Reactant 3

HCID 944Nitric AcidHCID 8857Ethyl AcetateHCID 76622Acetopiperone

Product 1

HCID 920221-(6-Nitro-1,3-benzodioxol-5-yl)ethan-1-one

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 8058HexaneSolvent

Procedure

A solution of 50 g (0.305 mole) 3,4-methylenedioxy-acetophenone (Aldrich) in 200 mL glacial acetic acid was added dropwise over 30 minutes to 700 mL of cold (2-4° C.) 70% HNO3 with stirring (NOTE: the reaction will overheat without external cooling from an ice bath, which can be dangerous and lead to side products). At temperatures below 0° C., however, the reaction can be sluggish. A temperature of 3-5° C. seems to be optimal). The mixture was left stirring for another 60 minutes at 3-5° C., and then allowed to approach ambient temperature. Analysis by TLC (25% EtOAc in hexane) indicated complete conversion of the starting material within 1-2 hr. When the reaction was complete, the mixture was poured into ˜3 liters of crushed ice, and the resulting yellow solid was filtered off, washed with water and then suction-dried. Yield ˜53 g (84%), used without further purification.

Workup

  1. customthe reaction
  2. temperaturewithout external cooling from an ice bath
  3. customAt temperatures below 0° C., however, the reaction
  4. customA temperature of 3-5° C.
  5. waitThe mixture was left
  6. stirringstirring for another 60 minutes at 3-5° C.
  7. customto approach ambient temperature
  8. customwithin 1-2 hr
  9. filtrationthe resulting yellow solid was filtered off
  10. washwashed with water
  11. customsuction-dried
  12. customYield ˜53 g (84%), used without further purification

Sources & evidence

ORD record
ord-15d52751961d4e6da688d93a246004e1
Source dataset
uspto-grants-2008_07
Patent number
US07399584B2

Reaction notes

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