Tributylvinyltin → 3-Bromo-2-ethenylpyridine

HRID 860711ノート

反応式

HRID 860711 の反応式
Br[C:2]1[C:7]([Br:8])=[CH:6][CH:5]=[CH:4][N:3]=1.[CH2:9]([Sn](CCCC)(CCCC)C=C)[CH2:10]CC.[Li+].[Cl-]>CN(C=O)C.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[Br:8][C:7]1[C:2]([CH:9]=[CH2:10])=[N:3][CH:4]=[CH:5][CH:6]=1

参加物

6

反応物 3

HCID 81998TributylvinyltinHCID 433294Lithium ChlorideHCID 8171022,3-Dibromopyridine

生成物 1

HCID 565907893-Bromo-2-ethenylpyridine収率 53.4%

試薬・触媒・溶媒 2

HCID 178418476HCID 178418476、化合物触媒HCID 6228Dimethylformamide溶媒

反応条件

温度
100 °C

実験手順

A solution of 2,3-dibromopyridine (2.0 g, 8.44 mmol) in DMF (10 mL) was treated with tributyl(vinyl)tin (2.94 g, 9.29 mmol), LiCl (1.07 g, 25.32 mmol), and PdCl2(PPh3)2 (0.296 g, 0.422 mmol). The reaction mixture was heated at 100° C. for 18 hours. The mixture was extracted with hexanes (3×50 mL). The combined hexane layers were extracted with 1N HCl. The aqueous layer was neutralized with 1N NaOH, extracted with hexanes, and the extracts were dried (MgSO4), filtered, and concentrated to provide the desired product as a yellowish oil (0.83 g, 53% yield). MS m/z 184(MH+); 1H NMR (300 MHz, CD3OD) δ 5.53 (dd, J=10.80, 2.01 Hz, 1H), 6.33 (dd, J=16.83, 1.83 Hz, 1H), 7.08–7.26 (m, 2H), 7.96 (dd, J=8.05, 1.46 Hz, 1H), 8.44 (dd, J=4.76, 1.46 Hz, 1H); 13C NMR (300 MHz, CD3OD) δ 121.9, 122.4, 125.7, 134.9, 142.8, 149.5, 154.5.

後処理

  1. extractionThe mixture was extracted with hexanes (3×50 mL)
  2. extractionThe combined hexane layers were extracted with 1N HCl
  3. extractionextracted with hexanes
  4. dry with materialthe extracts were dried (MgSO4)
  5. filtrationfiltered
  6. concentrationconcentrated

出典と根拠

ORDレコード
ord-e91475039af94f64ae5591a9845e553f
出典データセット
uspto-grants-2006_12
特許番号
US07153848B2

反応ノート

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