Water → 5-Fluoro-3-nitro-2-vinylpyridine

HRID 473423

反応式

HRID 473423 の反応式
Br[C:2]1[C:7]([N+:8]([O-:10])=[O:9])=[CH:6][C:5]([F:11])=[CH:4][N:3]=1.[CH2:12]([Sn](CCCC)(CCCC)C=C)[CH2:13]CC.O>O1CCOCC1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.Cl[Pd]Cl>[F:11][C:5]1[CH:6]=[C:7]([N+:8]([O-:10])=[O:9])[C:2]([CH:12]=[CH2:13])=[N:3][CH:4]=1

参加物

6

反応物 3

HCID 962WaterHCID 81998TributylvinyltinHCID 207912432-Bromo-5-fluoro-3-nitropyridine

生成物 1

HCID 583186385-Fluoro-3-nitro-2-vinylpyridine

試薬・触媒・溶媒 2

HCID 6102075Dichlorobis(triphenylphosphine)palladium触媒HCID 312751,4-Dioxane溶媒

反応条件

温度
110 °C

実験手順

To a solution of 2-bromo-5-fluoro-3-nitropyridine (20 g, 90.50 mmol) in 1, 4 dioxane (270 mL) was added tributyl vinyl tin (34.54 g, 108.60 mmol). The reaction mixture was degassed using nitrogen for 30 min. Bis-(triphenylphosphin)-palladium(II)-chloride (3.17 g, 4.5 mmol) was added to the reaction mixture. Reaction mass was stirred at 110° C. for 16 h. The reaction mixture was cooled to 25° C. Water was added to the reaction mass and extracted with EtOAc. Organic layer was washed with brine and dried over Na2SO4. The organic layer was concentrated in vacuo and purified by column chromatography on silica gel using 0-2% EtOAc in hexane to give 5-fluoro-3-nitro-2-vinylpyridine: 1H NMR (400 MHz, DMSO-d6): δ 5.742 (dd, 1H, J=2 Hz, 10.8 Hz), 6.45 (dd, 1H, J=2 Hz, J=16.8 Hz), 7.11-7.17 (m, 1H), 8.489-8.516 (m, 1H), 8.959 (d, 1H, J=2.4 Hz).

後処理

  1. customThe reaction mixture was degassed
  2. customfor 30 min
  3. customReaction mass
  4. temperatureThe reaction mixture was cooled to 25° C
  5. extractionextracted with EtOAc
  6. washOrganic layer was washed with brine
  7. dry with materialdried over Na2SO4
  8. concentrationThe organic layer was concentrated in vacuo
  9. custompurified by column chromatography on silica gel using 0-2% EtOAc in hexane

出典と根拠

ORDレコード
ord-251d108115194ba7a6729f7cd7b6c1b3
出典データセット
uspto-grants-2014_01
特許番号
US08633313B2

関連ノート

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