4-Nitroaniline → Methyl 2-[(4-nitrophenyl)amino]-3-oxobutanoate

HRID 239902

Reaction equation

HRID 239902 reaction equation
[N+:1]([C:4]1[CH:10]=[CH:9][C:7]([NH2:8])=[CH:6][CH:5]=1)([O-:3])=[O:2].[N+](=[C:13]([C:18](=[O:20])[CH3:19])[C:14]([O:16][CH3:17])=[O:15])=[N-]>C1(C)C=CC=CC=1.CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O.[Rh+2].[Rh+2]>[N+:1]([C:4]1[CH:10]=[CH:9][C:7]([NH:8][CH:13]([C:18](=[O:20])[CH3:19])[C:14]([O:16][CH3:17])=[O:15])=[CH:6][CH:5]=1)([O-:3])=[O:2]

Participants

5

Reactant 2

HCID 74754-NitroanilineHCID 545379602-Diazonio-1-methoxy-3-oxobut-1-en-1-olate

Product 1

HCID 70968068Methyl 2-[(4-nitrophenyl)amino]-3-oxobutanoateYield 98%

Reagents, catalysts & solvents 2

HCID 152122Dirhodium tetraacetateCatalystHCID 1140TolueneSolvent

Conditions

Temperature
120 °C

Procedure

Under an argon atmosphere, to a solution of 4-nitroaniline (3.84 g) in toluene (278 mL) were added methyl 2-diazo-3-oxobutanoate (5.13 g) and rhodium(II) acetate dimer (250 mg), and the mixture was stirred at 120° C. for 1 hr. The solvent was evaporated under reduced pressure, and the residue was purified by silica gel column chromatography [eluent; hexane:ethyl acetate=9:1→hexane:ethyl acetate=7:3 (volume ratio)] to give the title compound (4.63 g, yield 98%) as a yellow solid.

Workup

  1. customThe solvent was evaporated under reduced pressure
  2. customthe residue was purified by silica gel column chromatography [eluent; hexane:ethyl acetate=9:1→hexane:ethyl acetate=7:3 (volume ratio)]

Sources & evidence

ORD record
ord-1cfa878266b04a4fb7715964e4164ab7
Source dataset
uspto-grants-2014_02
Patent number
US08642770B2

Linked notes

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