Methyl Acrylate → Ethyl (2E)-3-(5-formyl-2-pyridinyl)-2-propenoate

HRID 43356

反応式

HRID 43356 の反応式
Br[C:2]1[CH:7]=[CH:6][C:5]([CH:8]=[O:9])=[CH:4][N:3]=1.[C:10]([O:14][CH3:15])(=[O:13])[CH:11]=[CH2:12].[C:16]1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.C([O-])(=O)C.[Na+]>CN(C=O)C.[CH2-]C=C.[CH2-]C=C.Cl[Pd+].Cl[Pd+]>[CH:8]([C:5]1[CH:6]=[CH:7][C:2](/[CH:12]=[CH:11]/[C:10]([O:14][CH2:15][CH3:16])=[O:13])=[N:3][CH:4]=1)=[O:9]

参加物

7

反応物 4

HCID 7294Methyl AcrylateHCID 80271Tri-o-tolylphosphineHCID 517045Sodium AcetateHCID 117692346-Bromo-3-pyridinecarboxaldehyde

生成物 1

HCID 86628160Ethyl (2E)-3-(5-formyl-2-pyridinyl)-2-propenoate収率 93.7%

試薬・触媒・溶媒 2

HCID 61538Palladium, di-mu-chlorobis(eta3-2-propenyl)di-触媒HCID 6228Dimethylformamide溶媒

反応条件

温度
170 °C

実験手順

A mixture of 2-bromo-5-formylpyridine (500 mg, 2.6 mmol), methyl acrylate (0.6 ml, 6.5 mmol), tri-(o-tolyl)phosphine (80 mg, 0.26 mmol), allyl palladium (II) chloride dimer (47 mg, 0.13 mmol) and sodium acetate (1.08 g, 8 mmol) in DMF (10 ml) was heated at 170° C. in a microwave reactor for 0.75 h. The reaction mixture was filtered through Celite® then diluted with DCM and water. The organic phase was dried, concentrated in vacuo and purified by chromatography to give the title compound as a white solid (50 mg). δH (CDCl3, 250 MHz) 10.14 (1H, s), 9.09 (1H, d), 8.19 (1H, dd), 7.72 (1H, d), 7.57 (1H, d), 7.08 (1H, d), 3.85 (3H, s). MS (ES): MH+ 192.

後処理

  1. filtrationThe reaction mixture was filtered through Celite®
  2. additionthen diluted with DCM and water
  3. customThe organic phase was dried
  4. concentrationconcentrated in vacuo
  5. custompurified by chromatography

出典と根拠

ORDレコード
ord-c0809180160c4ca9954d8ce9512a8b6f
出典データセット
uspto-grants-2013_09
特許番号
US08536182B2

関連ノート

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