4-Nitroaniline → 4-[(4-nitrophenyl)amino]-4-oxobutanoic acid

HRID 991404Notes

Reaction equation

HRID 991404 reaction equation
[N+:1]([C:4]1[CH:10]=[CH:9][C:7]([NH2:8])=[CH:6][CH:5]=1)([O-:3])=[O:2].[C:11]1(=[O:17])[O:16][C:14](=[O:15])[CH2:13][CH2:12]1>C(OCC)(=O)C.N1C(C)=CC=CC=1C>[N+:1]([C:4]1[CH:10]=[CH:9][C:7]([NH:8][C:11](=[O:17])[CH2:12][CH2:13][C:14]([OH:16])=[O:15])=[CH:6][CH:5]=1)([O-:3])=[O:2]

Participants

5

Reactant 2

HCID 74754-Nitroaniline2×HCID 7922Succinic anhydride2×

Product 1

HCID 27699804-[(4-nitrophenyl)amino]-4-oxobutanoic acid

Reagents, catalysts & solvents 2

HCID 79372,6-LutidineCatalystHCID 8857Ethyl AcetateSolvent

Procedure

p-Nitroaniline (PNA) (0.1 g, 0.724 mmol) and succinic anhydride (SA) (0.29 g, 2.898 mmol) were dissolved in ethyl acetate (EtOAc) (4 mL). Slight warming was required to dissolve both PNA and SA. The reaction was started by adding 2 drops of 2,6-lutidine. The reaction was held at a temperature of 70° C. overnight (19 hrs). The reaction vessel was placed in the refrigerator and the cold EtOAc was decanted from the solid reaction products. The reaction products were then rinsed with cold EtOAc (1 mL). The crude product, p-nitrosuccinanilic acid, was obtained by removing some reaction co-products using thin layer chromatography (TLC). The solid reaction products were dissolved in N,N-dimethylformamide (DMF) and spotted on Kieselgel 60 F254 HPTLC plates containing a concentration zone (EM Science No. 13728). The plates were developed using solvent system chloroform (CHCl3):EtOAc:methanol (MeOH):formic acid, 86:10:4:1%. The desired product remained at the origin. The origin band was scraped and eluted with DMF. The DMF was removed with a stream of argon gas. The sample was dissolved in 30% MeOH/H2O and made slightly basic using a solution of sodium hydroxide (4 N). The product was collected from HPLC using a 15 cm×4.6 mm, 5 μm, Supelcosil LC-ABZ column with a solvent system of 30% MeOH at a flow rate of 1 mL/min., at 254 nm; sodium p-nitrosuccinanilate (C10H9N2NaO5) in a yield of 59%. Accurate mass measurement was observed by Fast Atom Bombardment on the double sodium ion at 283.0326 (calculated for C10H9N2Na2O5+, 283.03069 (Δ1.91 ppm)).

Workup

  1. temperatureSlight warming
  2. customwas held at a temperature of 70° C. overnight (19 hrs)
  3. customthe cold EtOAc was decanted from the solid reaction products
  4. washThe reaction products were then rinsed with cold EtOAc (1 mL)

Sources & evidence

ORD record
ord-bbb272a958594f94ac7d77f9cb071143
Source dataset
uspto-grants-2002_10
Patent number
US06465194B2

Reaction notes

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