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

HRID 15130

反応式

HRID 15130 の反応式
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]

参加物

7

反応物 4

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

生成物 1

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

試薬・触媒・溶媒 2

HCID 2734558Bis(tri-tert-butylphosphine)palladium(0)触媒HCID 312751,4-Dioxane溶媒

反応条件

温度
100 °C

実験手順

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%).

後処理

  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%)

出典と根拠

ORDレコード
ord-7f2d49d4ac4a426ea06dc7242d782435
出典データセット
uspto-grants-2010_06
特許番号
US07732460B2

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