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

HRID 127493ノート

反応式

HRID 127493 の反応式
[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]

参加物

7

反応物 4

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

生成物 1

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

試薬・触媒・溶媒 2

HCID 241Benzene溶媒2 回HCID 962Water溶媒

実験手順

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°.

後処理

  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

出典と根拠

ORDレコード
ord-dff1ad9b473e474881f1f1d242c7a345
出典データセット
uspto-grants-1981_03
特許番号
US04256641

反応ノート

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