Cesium carbonate → 5-Bromo-3-(5-ethyl-1H-pyrazol-3-ylamino)-1-methylpyridin-2(1H)-one

HRID 407674

反応式

HRID 407674 の反応式
[CH2:1]([C:3]1[NH:7][N:6]=[C:5]([NH2:8])[CH:4]=1)[CH3:2].Br[C:10]1[C:11](=[O:18])[N:12]([CH3:17])[CH:13]=[C:14]([Br:16])[CH:15]=1.C(=O)([O-])[O-].[Cs+].[Cs+].CC1(C)C2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)OC2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=CC1=2>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].O1CCOCC1>[Br:16][C:14]1[CH:15]=[C:10]([NH:8][C:5]2[CH:4]=[C:3]([CH2:1][CH3:2])[NH:7][N:6]=2)[C:11](=[O:18])[N:12]([CH3:17])[CH:13]=1

参加物

7

反応物 4

HCID 10796Cesium carbonateHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 36143503,5-Dibromo-1-methylpyridin-2(1H)-oneHCID 219910953-ethyl-1H-pyrazol-5-amine

生成物 1

HCID 670161795-Bromo-3-(5-ethyl-1H-pyrazol-3-ylamino)-1-methylpyridin-2(1H)-one収率 43%

試薬・触媒・溶媒 2

HCID 9811564Bis(dibenzylideneacetone)palladium触媒HCID 312751,4-Dioxane溶媒

実験手順

A 100-mL single-neck round-bottomed flask equipped with a magnetic stirrer and a reflux condenser was charged with 1,4-dioxane (80 mL), 5-ethyl-1H-pyrazol-3-amine (3.33 g, 30.0 mmol), 3,5-dibromo-1-methylpyridin-2(1H)-one (9.6 g, 36 mmol), and cesium carbonate (19.5 g, 60 mmol). After bubbling nitrogen through the suspension for 10 minutes, Xantphos (1.73 mg, 3.0 mmol) and tris(dibenzylideneacetone)dipalladium(0) (1.36 mg, 1.5 mmol) were added. The system was subjected to three cycles of vacuum/argon flush and heated at reflux for 2 h. It was then filtered immediately. The solid was washed with dioxane (3×30 mL) and the combined filtrate was concentrated under reduced pressure. The residue was purified by silica-gel column chromatography eluting with petroleum ether/ethyl acetate (2:1 to 1:2) to afford 122a (3.8 g, 43%) as a red solid. MS-ESI: [M+H]+ 297.0

後処理

  1. customA 100-mL single-neck round-bottomed flask equipped with a magnetic stirrer and a reflux condenser
  2. customAfter bubbling nitrogen through the suspension for 10 minutes
  3. customflush
  4. temperatureheated
  5. temperatureat reflux for 2 h
  6. filtrationIt was then filtered immediately
  7. washThe solid was washed with dioxane (3×30 mL)
  8. concentrationthe combined filtrate was concentrated under reduced pressure
  9. customThe residue was purified by silica-gel column chromatography
  10. washeluting with petroleum ether/ethyl acetate (2:1 to 1:2)

出典と根拠

ORDレコード
ord-e96e3f51904445afb841d15716e27d1d
出典データセット
uspto-grants-2014_06
特許番号
US08754077B2

関連ノート

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