4-Nitrobenzaldehyde → 5(4H)-Oxazolone, 2-methyl-4-[(4-nitrophenyl)methylene]-

HRID 526026Notes

Reaction equation

HRID 526026 reaction equation
[N+:1]([C:4]1[CH:11]=[CH:10][C:7]([CH:8]=O)=[CH:6][CH:5]=1)([O-:3])=[O:2].[C:12]([NH:15][CH2:16][C:17]([OH:19])=[O:18])(=O)[CH3:13].C([O-])(=O)C.[Na+].C(OC(=O)C)(=O)C>>[CH3:13][C:12]1[O:19][C:17](=[O:18])[C:16](=[CH:8][C:7]2[CH:10]=[CH:11][C:4]([N+:1]([O-:3])=[O:2])=[CH:5][CH:6]=2)[N:15]=1

Participants

5

Reactant 4

HCID 5414-NitrobenzaldehydeHCID 7918Acetic AnhydrideHCID 10972AcetylglycineHCID 517045Sodium Acetate

Product 1

HCID 3644985(4H)-Oxazolone, 2-methyl-4-[(4-nitrophenyl)methylene]-Yield 66.5%

Conditions

Temperature
120 °C

Procedure

4-Nitrobenzaldehyde (53.7 g, 0.356 mol), N-acetylglycine (49.9 g, 0.427 mol) and sodium acetate (37.9 g, 0.463 mol) were mixed with acetic anhydride (168 g, 1.78 mol) and the resulting mixture heated with stirring to 120° C. for 6 hrs, giving a dark suspension. The mixture was then cooled to RT overnight, resulting in the formation of a precipitated solid. The reaction mixture was poured into ice-water (150 g) and the resulting suspended solid was collected by filtration. The crude solid product was washed with acetone (100 ml) then recrystallized from hot acetone (650 ml) to give a crystalline solid that was washed with 50% aqueous ethanol, then dried in vacuo to give 2-methyl-4-(4-nitrobenzylidene)oxazol-5(4H)-one (55.0 g, 66%) as pale yellow needles. The crystallisation mother liquors and washes were combined and evaporated to give a solid residue that was recrystallized from acetone to give a second crop of 2-methyl-4-(4-nitrobenzylidene)oxazol-5(4H)-one (8 g, 10%). The combined yield of 2-methyl-4-(4-nitrobenzylidene)oxazol-5(4H)-one was 63 g (76%)

Workup

  1. temperaturethe resulting mixture heated
  2. customgiving a dark suspension
  3. temperatureThe mixture was then cooled to RT overnight
  4. customresulting in the formation of a precipitated solid
  5. filtrationwas collected by filtration
  6. washThe crude solid product was washed with acetone (100 ml)
  7. customthen recrystallized from hot acetone (650 ml)
  8. customto give a crystalline solid
  9. washthat was washed with 50% aqueous ethanol
  10. customdried in vacuo

Sources & evidence

ORD record
ord-7789251c69634c018337f509d5c9cc84
Source dataset
uspto-grants-2016_05
Patent number
US09345680B2

Reaction notes

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