Nitromethane → 1-Methyl-4-[2-(2-nitrovinyl)-phenyl]-piperazine

HRID 1530857Notes

Reaction equation

HRID 1530857 reaction equation
[CH3:1][N:2]1[CH2:7][CH2:6][N:5]([C:8]2[CH:15]=[CH:14][CH:13]=[CH:12][C:9]=2[CH:10]=O)[CH2:4][CH2:3]1.Cl.CNC.[F-].[K+].[N+:22]([CH3:25])([O-:24])=[O:23]>C1(C)C=CC=CC=1>[CH3:1][N:2]1[CH2:7][CH2:6][N:5]([C:8]2[CH:15]=[CH:14][CH:13]=[CH:12][C:9]=2[CH:10]=[CH:25][N+:22]([O-:24])=[O:23])[CH2:4][CH2:3]1

Participants

6

Reactant 4

HCID 6375NitromethaneHCID 10473Dimethylamine, hydrochlorideHCID 522689Potassium FluorideHCID 27955662-(4-Methylpiperazin-1-yl)benzaldehyde

Product 1

HCID 698579991-Methyl-4-[2-(2-nitrovinyl)-phenyl]-piperazine

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

A mixture of 2-(4-methylpiperazin-1-yl)benzaldehyde (5 grams, 24.5 mmol, prepared according to the method of D. Reinhoudt et al., Synthesis, 1987, 641), dimethylamine hydrochoride (4 grams, 49 mmol), potassium fluoride (0.213 grams, 3.7 mmol) and nitromethane (100 mL) in anhydrous toluene (100 mL) was refluxed under nitrogen using a Dean Stark trap to collect the azeotroped water. After 2 hour the reaction was determined to be completed by thin layer chromatography using triethylamine: methanol: ethyl acetate (5:10:85). The solvents were removed in vacuo and the residue was partitioned between methylene chloride and saturated aqueous sodium carbonate. The organic layer was then washed with saturated sodium chloride, dried and concentrated to a red oil, 5.69 grams. Chromatography using silica gel on a 4×1.75 inch column, eluting with 100% ethyl acetate followed by increasing percentages of methanol, produced 4.03 grams of 1-methyl-4-[2-(2-nitrovinyl)-phenyl]-piperazine as a light orange solid. 1H-nmr (CDCl3, 400 MHz) δ 8.35 (1H, d, J=13.9 Hz), 7.66 (1H, d, J=13.7 Hz), 7.46 (2H, m), 7.10 (2H, m), 2.99 (4H, m), 2.63 (4H, m), 2.38 (3H, s).

Workup

  1. customprepared
  2. temperaturewas refluxed under nitrogen using a Dean Stark trap
  3. customto collect the azeotroped water
  4. customThe solvents were removed in vacuo
  5. customthe residue was partitioned between methylene chloride and saturated aqueous sodium carbonate
  6. washThe organic layer was then washed with saturated sodium chloride
  7. customdried
  8. concentrationconcentrated to a red oil, 5.69 grams
  9. washeluting with 100% ethyl acetate
  10. temperatureby increasing percentages of methanol

Sources & evidence

ORD record
ord-1e78f033fe8a4ec896f3b92844d44740
Source dataset
uspto-grants-2001_03
Patent number
US06197773B1

Reaction notes

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