Methyl 4-aminobenzoate → Diethyl (4-methoxycarbonylphenyl)aminomalonate

HRID 1635555Notes

Reaction equation

HRID 1635555 reaction equation
[NH2:1][C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[CH:4][CH:3]=1.Br[CH:13]([C:19]([O:21][CH2:22][CH3:23])=[O:20])[C:14]([O:16][CH2:17][CH3:18])=[O:15]>C1C=CC=CC=1>[CH3:9][O:8][C:6]([C:5]1[CH:4]=[CH:3][C:2]([NH:1][CH:13]([C:14]([O:16][CH2:17][CH3:18])=[O:15])[C:19]([O:21][CH2:22][CH3:23])=[O:20])=[CH:11][CH:10]=1)=[O:7]

Participants

4

Reactant 2

HCID 12082Methyl 4-aminobenzoateHCID 69637Diethyl bromomalonate

Product 1

HCID 10638604Diethyl (4-methoxycarbonylphenyl)aminomalonateYield 85.6%

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent

Procedure

A mixture of methyl 4-aminobenzoate (3.1 g, 20.5 mmol) and diethyl bromomalonate (2.45 g, 10.2 mmol) in a round bottom flask was placed in an oven at 115° C. for 16 h. The reaction mixture, which had turned into a solid cake, was suspended in 20 mL of benzene and filtered. The filtrate was diluted with 50 mL of benzene and the organic layer was washed with 2 N hydrochloric acid (3×10 mL), water (10 mL), dried (Na2SO4) and evaporated to give an oily material which solidified upon standing. The crude was recrystallized from ether/hexane to give 2.7 g (85%) of diethyl (4-methoxycarbonylphenyl)aminomalonate, mp 66-69° C. (ether/hexane).

Workup

  1. filtrationfiltered
  2. additionThe filtrate was diluted with 50 mL of benzene
  3. washthe organic layer was washed with 2 N hydrochloric acid (3×10 mL), water (10 mL)
  4. dry with materialdried (Na2SO4)
  5. customevaporated
  6. customto give an oily material which
  7. customThe crude was recrystallized from ether/hexane

Sources & evidence

ORD record
ord-a648fd3968fd4afb8a1f4ed66d9ad528
Source dataset
uspto-grants-2003_01
Patent number
US06509359B1

Reaction notes

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