Cesium fluoride → 1,1-Dimethylethyl [2-[1-(ethyloxy)ethenyl]-5-fluoro-6-(methyloxy)-3-pyridinyl]carbamate

HRID 15130

반응식

HRID 15130 반응식
Cl[C:2]1[C:7]([NH:8][C:9](=[O:15])[O:10][C:11]([CH3:14])([CH3:13])[CH3:12])=[CH:6][C:5]([F:16])=[C:4]([O:17][CH3:18])[N:3]=1.[F-].[Cs+].C([Sn](CCCC)(CCCC)[C:26]([O:28][CH2:29][CH3:30])=[CH2:27])CCC.[F-].[K+]>O1CCOCC1.[Pd].C(P(C(C)(C)C)C(C)(C)C)(C)(C)C.C(P(C(C)(C)C)C(C)(C)C)(C)(C)C>[CH2:29]([O:28][C:26]([C:2]1[C:7]([NH:8][C:9](=[O:15])[O:10][C:11]([CH3:14])([CH3:13])[CH3:12])=[CH:6][C:5]([F:16])=[C:4]([O:17][CH3:18])[N:3]=1)=[CH2:27])[CH3:30]

참가 물질

7

반응물 4

HCID 25953Cesium fluorideHCID 522689Potassium FluorideHCID 619414Stannane, tributyl(1-ethoxyethenyl)-HCID 71463986tert-Butyl (2-chloro-5-fluoro-6-methoxypyridin-3-yl)carbamate

생성물 1

HCID 866141461,1-Dimethylethyl [2-[1-(ethyloxy)ethenyl]-5-fluoro-6-(methyloxy)-3-pyridinyl]carbamate

시약·촉매·용매 2

HCID 2734558Bis(tri-tert-butylphosphine)palladium(0)촉매HCID 312751,4-Dioxane용매

반응 조건

온도
100 °C

실험 절차

A degassed solution of 1,1-dimethylethyl [2-chloro-5-fluoro-6-(methyloxy)-3-pyridinyl]carbamate (20 g, 72.2 mmol) in 1,4-dioxane (200 ml) was treated with bis(tri-tert-butylphosphine) palladium(0) (1.05 g), caesium fluoride (21.93 g) and tributyl[1-(ethyloxy)ethenyl]stannane (26.9 ml) then heated to 100° C. overnight. The cooled mixture was treated with 10% aqueous potassium fluoride solution. After 0.5 hour stirring, the mixture was filtered through Kieselguhr, washing with 1,4-dioxane. Ethyl acetate and water were added to the filtrate. The phases were separated and the aqueous phase extracted twice with ethyl acetate. The combined organic extracts were dried over magnesium sulphate and evaporated. The residue was rapidly chromatographed eluting with 25-50% dichloromethane in hexane affording the product as a light brown oil (22.2 g, 99%).

후처리

  1. filtrationthe mixture was filtered through Kieselguhr
  2. washwashing with 1,4-dioxane
  3. additionEthyl acetate and water were added to the filtrate
  4. customThe phases were separated
  5. extractionthe aqueous phase extracted twice with ethyl acetate
  6. dry with materialThe combined organic extracts were dried over magnesium sulphate
  7. customevaporated
  8. customThe residue was rapidly chromatographed
  9. washeluting with 25-50% dichloromethane in hexane affording the product as a light brown oil (22.2 g, 99%)

출처 및 근거

ORD 기록
ord-7f2d49d4ac4a426ea06dc7242d782435
출처 데이터셋
uspto-grants-2010_06
특허 번호
US07732460B2

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