Acetic Acid → 1,3-Benzenedicarboxylic acid, 5-(2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl)-

HRID 2163442Notes

Reaction equation

HRID 2163442 reaction equation
[N+:1]([C:4]1[CH:5]=[C:6]([C:13]([OH:15])=[O:14])[CH:7]=[C:8]([CH:12]=1)[C:9]([OH:11])=[O:10])([O-])=O.C(O)(=O)C.[C:20]1(=O)[O:25][C:23](=[O:24])[CH:22]=[CH:21]1>[OH-].[Na+].[Pd].O1CCOCC1>[C:20]1(=[O:25])[N:1]([C:4]2[CH:5]=[C:6]([C:13]([OH:15])=[O:14])[CH:7]=[C:8]([CH:12]=2)[C:9]([OH:11])=[O:10])[C:23](=[O:24])[CH:22]=[CH:21]1

Participants

7

Reactant 3

HCID 176Acetic Acid2×HCID 7923Maleic AnhydrideHCID 120695-Nitroisophthalic acid

Product 1

HCID 107538771,3-Benzenedicarboxylic acid, 5-(2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl)-

Reagents, catalysts & solvents 3

HCID 23938PalladiumCatalystHCID 14798Sodium HydroxideSolventHCID 312751,4-DioxaneSolvent

Procedure

211.2 g (1.0 mol) of 5-nitroisophthalic acid are dissolved in 1,590 g of aqueous sodium hydroxide (90.0 g of sodium hydroxide in 1,500 ml of water) and the solution is rendered neutral with 15 ml of anhydrous acetic acid and hydrogenated in the presence of 10 g of a palladium-on-charcoal catalyst (5% by weight of Pd). The catalyst is filtered off and a solution of 118.0 g (1.2 mols) of maleic anhydride in 150 ml of dioxane is added to the filtrate in the course of 2 hours, whilst stirring vigorously. A white suspension is formed and is stirred overnight at 20°-25° C., 250 ml of acetic acid are then added and the mixture is stirred for a further 2 hours. The amide-acid which has precipitated is filtered off, washed with water and methanol and dried at 30° C. in vacuo for 24 hours. The reaction product (315 g) is then heated, in 2,500 ml of acetic anhydride, whilst stirring, to 80°-85° C. for 30 minutes. About 1.8 liters of liquid (acetic acid + acetic anhydride) are distilled off under a waterpump vacuum. The residual suspension is poured onto 2,000 g of ice and the mixture is stirred overnight. The reaction product which has precipitated is filtered off, washed with water and methanol and dried at 60° C. in vacuo for 12 hours. 210 g of white, crystalline 5-maleimidylisophthalic acid are obtained; melting point > 300° C. (= 80% of theory, based on the nitroisophthalic acid).

Workup

  1. filtrationThe catalyst is filtered off
  2. customA white suspension is formed
  3. stirringis stirred overnight at 20°-25° C.
  4. stirringthe mixture is stirred for a further 2 hours
  5. customThe amide-acid which has precipitated
  6. filtrationis filtered off
  7. washwashed with water and methanol
  8. customdried at 30° C. in vacuo for 24 hours
  9. temperatureThe reaction product (315 g) is then heated, in 2,500 ml of acetic anhydride
  10. stirringwhilst stirring, to 80°-85° C. for 30 minutes
  11. distillationAbout 1.8 liters of liquid (acetic acid + acetic anhydride) are distilled off under a waterpump vacuum
  12. additionThe residual suspension is poured onto 2,000 g of ice
  13. stirringthe mixture is stirred overnight
  14. customThe reaction product which has precipitated
  15. filtrationis filtered off
  16. washwashed with water and methanol
  17. customdried at 60° C. in vacuo for 12 hours

Sources & evidence

ORD record
ord-f394b0100283476ea5fcf11e44ff0dda
Source dataset
uspto-grants-1979_01
Patent number
US04134895

Reaction notes

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