磷酸三乙酯 → Ethyl 1-ethyl-5-fluoro-6,7-dimethoxy-4-oxo-1,4-dihydroquinoline-3-carboxylate

HRID 525935笔记

反应方程式

HRID 525935 反应方程式
[F:1][C:2]1[C:11]([O:12][CH3:13])=[C:10]([O:14][CH3:15])[CH:9]=[C:8]2[C:3]=1[C:4](=[O:21])[C:5]([C:16]([O:18][CH2:19][CH3:20])=[O:17])=[CH:6][NH:7]2.F[C:23]1C=C2C(C(=O)C(C(OCC)=O)=CN2)=C(OC)[C:24]=1OC.C(=O)([O-])[O-].[K+].[K+].P(OCC)(OCC)(OCC)=O>O>[CH2:23]([N:7]1[C:8]2[C:3](=[C:2]([F:1])[C:11]([O:12][CH3:13])=[C:10]([O:14][CH3:15])[CH:9]=2)[C:4](=[O:21])[C:5]([C:16]([O:18][CH2:19][CH3:20])=[O:17])=[CH:6]1)[CH3:24]

参与物

6

反应物 4

HCID 6535磷酸三乙酯HCID 11430碳酸钾HCID 86732801Ethyl 7-fluoro-5,6-dimethoxy-4-oxo-1,4-dihydroquinoline-3-carboxylateHCID 86732802Ethyl 5-fluoro-6,7-dimethoxy-4-oxo-1,4-dihydroquinoline-3-carboxylate

产物 1

HCID 86732803Ethyl 1-ethyl-5-fluoro-6,7-dimethoxy-4-oxo-1,4-dihydroquinoline-3-carboxylate收率 57.6%

试剂、催化剂与溶剂 1

HCID 962聚[6-[4-(4-氰基苯基)苯氧基]己基甲基丙烯酸酯]溶剂

反应条件

温度
120 °C

实验过程

A mixture of ethyl 5-fluoro-6,7-dimethoxy-4-oxo-1,4-dihydroquinoline-3-carboxylate and ethyl 7-fluoro-5,6-dimethoxy-4-oxo-1,4-dihydroquinoline-3-carboxylate (103 g, 349 mmol), and potassium carbonate (72.3 g, 523 mmol) in triethyl phosphate (297 ml, 1744 mmol) was stirred at 120° C. for 8 h. LCMS indicated completion of the reaction. The reaction mixture was cooled down to rt and diluted with water, extracted with DCM, dried over sodium sulfate and concentrated in vacuo. The crude material was recrystallized in EtOH, the precipitate was collected by filtration and washed by cold EtOH and dried in air. Another recrystallization afforded pure ethyl 1-ethyl-5-fluoro-6,7-dimethoxy-4-oxo-1,4-dihydroquinoline-3-carboxylate (65 g, 201 mmol, 57.6% yield) as a brown solid. LCMS: (M+H)+: 324.1.

后处理

  1. customcompletion of the reaction
  2. temperatureThe reaction mixture was cooled down to rt
  3. extractionextracted with DCM
  4. dry with materialdried over sodium sulfate
  5. concentrationconcentrated in vacuo
  6. customThe crude material was recrystallized in EtOH
  7. filtrationthe precipitate was collected by filtration
  8. washwashed by cold EtOH
  9. customdried in air
  10. customAnother recrystallization

来源与证据

ORD记录
ord-a0e1ef3c75644de480d9b9e5db872a98
来源数据集
uspto-grants-2016_05
专利号
US09340556B2

反应笔记

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