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

HRID 2057507Notes

Reaction equation

HRID 2057507 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 the 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
  17. dry with materialthe methanol and dried at 60° C. in vacuo for 12 hours

Sources & evidence

ORD record
ord-544596a8e4a440f8afe94c3a0529be5e
Source dataset
uspto-grants-1980_07
Patent number
US04211705

Reaction notes

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