Diethyl Malonate → Diethyl (3-nitropyridin-2-yl)propanedioate

HRID 1168232ノート

反応式

HRID 1168232 の反応式
[H-].[Na+].[C:3]([O:11][CH2:12][CH3:13])(=[O:10])[CH2:4][C:5]([O:7][CH2:8][CH3:9])=[O:6].Cl[C:15]1[C:20]([N+:21]([O-:23])=[O:22])=[CH:19][CH:18]=[CH:17][N:16]=1.[Cl-].[NH4+]>CS(C)=O>[N+:21]([C:20]1[C:15]([CH:4]([C:5]([O:7][CH2:8][CH3:9])=[O:6])[C:3]([O:11][CH2:12][CH3:13])=[O:10])=[N:16][CH:17]=[CH:18][CH:19]=1)([O-:23])=[O:22]

参加物

6

反応物 4

HCID 7761Diethyl MalonateHCID 24758Sodium hydrideHCID 25517Ammonium ChlorideHCID 796132-Chloro-3-nitropyridine

生成物 1

HCID 13147345Diethyl (3-nitropyridin-2-yl)propanedioate収率 73.8%

試薬・触媒・溶媒 1

HCID 679Dimethyl Sulfoxide溶媒

実験手順

Sodium hydride (60% dispersion in oil, 5.57 g, 0.14 mol) was carefully washed with hexanes under nitrogen before the addition of DMSO (115 mL). Diethyl malonate (22.3 g, 0.14 mol) was added dropwise over 20 min, and the mixture was stirred for an additional 30 min at room temperature. 2-Chloro-3-nitropyridine (10 g, 0.06 mol) was added to the reaction, and the reaction was placed in a pre-heated oil bath set to 100° C. for 15 min. The reaction was cooled to room temperature and poured into aqueous ammonium chloride (saturated solution, 150 mL). The aqueous solution was extracted with EtOAc:hexanes (1:1) four times (200 mL each), and the organic layers were combined. The organics were concentrated to afford a solid that was recrystallized from a minimal amount of EtOAc:hexanes (1:1) to provide the title compound (12.5 g, 70% yield). APCI MS m/z 281 (M−H).

後処理

  1. customthe reaction was placed in a pre-heated oil bath
  2. waitset to 100° C. for 15 min
  3. temperatureThe reaction was cooled to room temperature
  4. extractionThe aqueous solution was extracted with EtOAc:hexanes (1:1) four times (200 mL each)
  5. concentrationThe organics were concentrated
  6. customto afford a solid
  7. customthat was recrystallized from a minimal amount of EtOAc:hexanes (1:1)

出典と根拠

ORDレコード
ord-722c7960c3a04e37869ecea7cbeeb469
出典データセット
uspto-grants-2003_09
特許番号
US06624171B1

反応ノート

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