Methanol → Methyl 2-chloro-4-methylpyridine-3-carboxylate

HRID 1959594ノート

反応式

HRID 1959594 の反応式
[Zn](C)C.[CH3:4][O:5][C:6](=[O:15])[C:7]1[C:12](Br)=[CH:11][CH:10]=[N:9][C:8]=1[Cl:14].[CH3:16]O>O1CCOCC1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[CH3:4][O:5][C:6](=[O:15])[C:7]1[C:12]([CH3:16])=[CH:11][CH:10]=[N:9][C:8]=1[Cl:14]

参加物

6

反応物 3

HCID 887MethanolHCID 44190945Methyl 4-bromo-2-chloronicotinateHCID 178477796HCID 178477796、化合物

生成物 1

HCID 17862852Methyl 2-chloro-4-methylpyridine-3-carboxylate

試薬・触媒・溶媒 2

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)触媒HCID 312751,4-Dioxane溶媒

反応条件

温度
70 °C

実験手順

ZnMe2 (2.0 M in toluene, 15.5 mL, 25 mmol) was added to a stirred mixture of 4-bromo-2-chloro-nicotinic acid methyl ester (9.6 g, 38 mmol) and Pd(dppf)Cl2 (0.50 g, 0.61 mmol) in anhydrous dioxane (180 mL). After stirring for 8 h at 70° C., the reaction mixture was cooled to room temperature, MeOH (15 mL) was added and the solvent was removed in vacuo. The residue was partitioned between EA (300 mL) and water (50 mL). Concentrated aqueous HCl was then added until the emulsion became homogeneous. The organic layers were dried over Na2SO4, filtered, and concentrated in vacuo. The residue was purified by flash chromatography on silica gel (elution with hexane/EA 2:1) to give the title compound. MS (m/z): 186.0 [M+H+].

後処理

  1. temperaturethe reaction mixture was cooled to room temperature
  2. customthe solvent was removed in vacuo
  3. customThe residue was partitioned between EA (300 mL) and water (50 mL)
  4. additionConcentrated aqueous HCl was then added until the emulsion
  5. dry with materialThe organic layers were dried over Na2SO4
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. customThe residue was purified by flash chromatography on silica gel (elution with hexane/EA 2:1)

出典と根拠

ORDレコード
ord-9236a5a400ce455e88f05601d277935f
出典データセット
uspto-grants-2013_04
特許番号
US08410134B2

反応ノート

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