Acetamidomalonic acid diethyl ester → 1-Acetyl-4-(4-chloro-2-nitrophenyl)-2,3-dihydro-1H-pyrrole-2,2-dicarboxylic acid diethyl ester

HRID 1390834Notes

Reaction equation

HRID 1390834 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([C:8](=[CH2:11])[CH:9]=O)=[C:4]([N+:12]([O-:14])=[O:13])[CH:3]=1.[C:15]([NH:18][CH:19]([C:25]([O:27][CH2:28][CH3:29])=[O:26])[C:20]([O:22][CH2:23][CH3:24])=[O:21])(=[O:17])[CH3:16].C[O-].[Na+].O.C1(C)C=CC(S(O)(=O)=O)=CC=1>O.C1C=CC=CC=1>[CH2:23]([O:22][C:20]([C:19]1([C:25]([O:27][CH2:28][CH3:29])=[O:26])[CH2:9][C:8]([C:5]2[CH:6]=[CH:7][C:2]([Cl:1])=[CH:3][C:4]=2[N+:12]([O-:14])=[O:13])=[CH:11][N:18]1[C:15](=[O:17])[CH3:16])=[O:21])[CH3:24]

Participants

7

Reactant 4

HCID 14041Acetamidomalonic acid diethyl esterHCID 521998p-Toluenesulfonic acid monohydrateHCID 10942334Sodium MethoxideHCID 128784952-(4-Chloro-2-nitrophenyl) acrolein

Product 1

HCID 128784981-Acetyl-4-(4-chloro-2-nitrophenyl)-2,3-dihydro-1H-pyrrole-2,2-dicarboxylic acid diethyl ester

Reagents, catalysts & solvents 2

HCID 241BenzeneSolvent2×HCID 962WaterSolvent

Procedure

A solution of 143.0 g (0.676 mol) of 2-(4-chloro-2-nitrophenyl) acrolein in 600 ml. of benzene was added over 1.5 hour to a stirred suspension of 148.5 g (0.684 mol) of diethyl acetamidomalonate and 0.80 g of sodium methoxide in 600 ml. of benzene. The Michael addition was complete after 30 minutes. 3.8 g of p-toluenesulfonic acid monohydrate was added and the mixture was heated at reflux for 40 minutes with constant removal of the water formed. The reaction mixture was washed with saturated sodium bicarbonate and brine. After drying with anhydrous NaSO4, the orange solution was concentrated to yield 278.5 g, m.p. 90-95°. Crystallization from ethanol (500 ml) gave 264.6 g (95%) of deep yellow crystals, m.p. 96-98°. A sample was recrystallized again from ethanol: m.p. 96.5-98°.

Workup

  1. additionThe Michael addition
  2. temperaturethe mixture was heated
  3. customformed
  4. washThe reaction mixture was washed with saturated sodium bicarbonate and brine
  5. dry with materialAfter drying with anhydrous NaSO4
  6. concentrationthe orange solution was concentrated
  7. customto yield 278.5 g, m.p. 90-95°
  8. customCrystallization from ethanol (500 ml)
  9. customgave 264.6 g (95%) of deep yellow crystals, m.p. 96-98°
  10. customA sample was recrystallized again from ethanol

Sources & evidence

ORD record
ord-d48f26a4454d4eef87c1ce6c3b0c5b47
Source dataset
uspto-grants-1979_02
Patent number
US04140697

Reaction notes

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