2-Nitropropane → 1,1-Dimethyl-2-hydroxy-2-(3,4-methylenedioxyphenyl)nitroethane

HRID 616256Notes

Reaction equation

HRID 616256 reaction equation
[Na].[N+:2]([CH:5]([CH3:7])[CH3:6])([O-:4])=[O:3].[CH:8]1[C:13]([CH:14]=[O:15])=[CH:12][C:11]2[O:16][CH2:17][O:18][C:10]=2[CH:9]=1.S(=O)(=O)(O)O.S(=O)(=O)(O)[O-].[Na+]>CO.O>[CH3:6][C:5]([N+:2]([O-:4])=[O:3])([CH3:7])[CH:14]([OH:15])[C:13]1[CH:8]=[CH:9][C:10]2[O:18][CH2:17][O:16][C:11]=2[CH:12]=1

Participants

8

Reactant 5

HCID 3982-NitropropaneHCID 1118Sulfuric AcidHCID 8438PiperonalHCID 516919Sodium BisulfateHCID 5360545Sodium

Product 1

HCID 234548521,1-Dimethyl-2-hydroxy-2-(3,4-methylenedioxyphenyl)nitroethaneYield 34.9%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 962WaterSolvent2×

Procedure

A solution of 55.2 g (2.4 g atom) of sodium in 2.62 liters of methanol cooled to 25° C was added to 684 g (689.5 ml; 7.68 moles) of 2-nitropropane after which 360.4 g (2.4 moles) of piperonal were added. The solution was stirred at room temperature for 18 hours, cooled in an ice bath and acidified with 2.4 liters of 1N sulphuric acid. The resulting mixture was diluted with 5 liters of water, and an oil which precipitated was syphoned off and added to a rapidly stirred solution of 187.4 g (1.8 moles) of sodium bisulphate in 1.2 liters of water. The mixture was stirred for 15 minutes, after which the solid formed was separated and washed three times with ether. The organic layer was separated off, washed with brine, dried and concentrated to an oil which was crystallised from a mixture of 250 ml of toluene and 850 ml of hexane to give 1,1-dimethyl-2-hydroxy-2-(3,4-methylenedioxyphenyl)nitroethane m.p. 88°-91° (Yield 200.4 g). The mother liquor from the crystallisation was diluted with a further liter of hexane to give a further crop of the product, m.p. 88°-91° (49.9 g; total yield 250.3 g, 43.6%).

Workup

  1. additionwere added
  2. temperaturecooled in an ice bath
  3. customan oil which precipitated
  4. stirringThe mixture was stirred for 15 minutes
  5. customafter which the solid formed
  6. customwas separated
  7. washwashed three times with ether
  8. customThe organic layer was separated off
  9. washwashed with brine
  10. customdried
  11. concentrationconcentrated to an oil which
  12. customwas crystallised from a mixture of 250 ml of toluene and 850 ml of hexane

Sources & evidence

ORD record
ord-c4f24c1d9edf40989a62a2b56d7cb7b6
Source dataset
uspto-grants-1978_02
Patent number
US04073798

Reaction notes

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