Methyl vinyl ketone → (3E)-4-[6-(benzyloxy)pyridin-3-yl]but-3-en-2-one

HRID 384479ノート

反応式

HRID 384479 の反応式
[CH2:1]([O:8][C:9]1[CH:14]=[CH:13][C:12](Br)=[CH:11][N:10]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[CH3:16][C:17](=[O:20])[CH:18]=[CH2:19].C(N(CC)CC)C.C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C>CN(C=O)C.[Pd].[Pd].C(=CC(C=CC1C=CC=CC=1)=O)C1C=CC=CC=1.C(=CC(C=CC1C=CC=CC=1)=O)C1C=CC=CC=1.C(=CC(C=CC1C=CC=CC=1)=O)C1C=CC=CC=1>[CH2:1]([O:8][C:9]1[N:10]=[CH:11][C:12](/[CH:19]=[CH:18]/[C:17](=[O:20])[CH3:16])=[CH:13][CH:14]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

参加物

7

反応物 4

HCID 6570Methyl vinyl ketoneHCID 8471TriethylamineHCID 80271Tri-o-tolylphosphineHCID 111081912-Benzyloxy-5-bromopyridine

生成物 1

HCID 59527049(3E)-4-[6-(benzyloxy)pyridin-3-yl]but-3-en-2-one収率 38.2%

試薬・触媒・溶媒 2

HCID 9832798Tris(dibenzylideneacetone) dipalladium触媒HCID 6228Dimethylformamide溶媒

反応条件

温度
100 °C

実験手順

To a solution of 2-(benzyloxy)-5-bromopyridine (600 mg) in DMF (12 mL) were added 3-buten-2-one (400 mg), tris(dibenzylidene acetone) dipalladium(0) (74 mg), triethylamine (460 mg), and tris(o-tolyl)phosphine (70 mg) at room temperature under nitrogen flow, and the mixture was stirred at 100° C. for 24 hours. The reaction liquid was allowed to cool, and insolubles were filtered through Celite. Water was added to the filtrate, followed by three times extractions with ethyl acetate. The organic layer was washed sequentially with water and saturated brine, and then dried over anhydrous magnesium sulfate. The solvent was evaporated under reduced pressure, and then the residue was purified by silica gel column chromatography (eluent: hexane/ethyl acetate=9/1-3/2) to obtain (3E)-4-[6-(benzyloxy)pyridin-3-yl]but-3-en-2-one (220 mg).

後処理

  1. customThe reaction liquid
  2. temperatureto cool
  3. filtrationinsolubles were filtered through Celite
  4. additionWater was added to the filtrate
  5. extractionfollowed by three times extractions with ethyl acetate
  6. washThe organic layer was washed sequentially with water and saturated brine
  7. dry with materialdried over anhydrous magnesium sulfate
  8. customThe solvent was evaporated under reduced pressure
  9. customthe residue was purified by silica gel column chromatography (eluent: hexane/ethyl acetate=9/1-3/2)

出典と根拠

ORDレコード
ord-a7d9c3a42b1e4405a47656ffc0a80660
出典データセット
uspto-grants-2013_02
特許番号
US08367702B2

反応ノート

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