N~1~,N~4~-Bis(4-nitrophenyl)benzene-1,4-dicarboximidic acid → n,n'-bis(4-aminophenyl)terephthalamide

HRID 1981054Notes

Reaction equation

HRID 1981054 reaction equation
[N+:1]([C:4]1[CH:9]=[CH:8][C:7]([NH:10][C:11](=[O:30])[C:12]2[CH:29]=[CH:28][C:15]([C:16]([NH:18][C:19]3[CH:24]=[CH:23][C:22]([N+:25]([O-])=O)=[CH:21][CH:20]=3)=[O:17])=[CH:14][CH:13]=2)=[CH:6][CH:5]=1)([O-])=O.[H][H]>[Ni].CC(N(C)C)=O>[NH2:25][C:22]1[CH:21]=[CH:20][C:19]([NH:18][C:16](=[O:17])[C:15]2[CH:28]=[CH:29][C:12]([C:11]([NH:10][C:7]3[CH:8]=[CH:9][C:4]([NH2:1])=[CH:5][CH:6]=3)=[O:30])=[CH:13][CH:14]=2)=[CH:24][CH:23]=1

Participants

5

Reactant 2

HCID 252808N~1~,N~4~-Bis(4-nitrophenyl)benzene-1,4-dicarboximidic acidHCID 178418361HCID 178418361, compound3×

Product 1

HCID 244300n,n'-bis(4-aminophenyl)terephthalamide

Reagents, catalysts & solvents 2

HCID 935NickelCatalystHCID 31374DimethylacetamideSolvent

Conditions

Temperature
100 °C

Procedure

Into a 300 ml. pressure-vessel of stainless steel equipped with a magnetic stirrer, a thermometer, and a hydrogen inlet tube, were placed 145 ml. of dimethylacetamide, 18 grs. of N,N'-bis(4-nitrophenyl)terephthalamide prepared in Procedure (b-ii) above, and 2 grs. of Raney nickel. While stirring the contents of the vessel, the temperature was slowly raised to 100° C. Hydrogen gas of about 600 psi was introduced to the bottom of the vessel via the hydrogen inlet tube. The above hydrogen pressure and reaction temperature were maintained for about 5 to 6 hours, so that the hydrogenation reaction could be completed. The reaction product was filtered at 100° C. to separate the Raney nickel catalyst therefrom, and cooled down to 5° C. The resulting yellowish precipitate was collected by filtration and recrystallized from the dimethylacetamide solvent to afford the titled compound in the form of beautiful needle-shaped pale yellow crystals. Yield: 15.32 grs. (97.7% of theoretical value); m.p.: 300° C. (dec.). The IR spectrum showed carbonyl absorption at 1,660 cm-1, and an amide stretch at 3,300 cm-1 (asym); 3,325 cm-1 (sym). For the NMR analysis of the compound, deuterated dimethylsulfoxide solvent was used. The chemical shift of each portion in the NMR spectra was found to be as follows:

Workup

  1. temperaturewere maintained for about 5 to 6 hours, so that the hydrogenation reaction
  2. filtrationThe reaction product was filtered at 100° C.
  3. customto separate the Raney nickel catalyst
  4. temperaturecooled down to 5° C
  5. filtrationThe resulting yellowish precipitate was collected by filtration
  6. customrecrystallized from the dimethylacetamide solvent

Sources & evidence

ORD record
ord-fca388bc037d424facd7b7d0d897c619
Source dataset
uspto-grants-1985_04
Patent number
US04511709

Reaction notes

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