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

HRID 1959594노트

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HRID 1959594 반응식
[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]

참가 물질

6

반응물 3

HCID 887MethanolHCID 44190945Methyl 4-bromo-2-chloronicotinateHCID 178477796HCID 178477796, 화합물

생성물 1

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

시약·촉매·용매 2

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

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온도
70 °C

실험 절차

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+].

후처리

  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)

출처 및 근거

ORD 기록
ord-9236a5a400ce455e88f05601d277935f
출처 데이터셋
uspto-grants-2013_04
특허 번호
US08410134B2

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