Methyl chloroformate → Methyl 7-chlorothieno[3,2-B]pyridine-2-carboxylate

HRID 500762ノート

反応式

HRID 500762 の反応式
[Cl:1][C:2]1[CH:7]=[CH:6][N:5]=[C:4]2[CH:8]=[CH:9][S:10][C:3]=12.[Li]CCCC.Cl[C:17]([O:19][CH3:20])=[O:18]>C1COCC1>[Cl:1][C:2]1[CH:7]=[CH:6][N:5]=[C:4]2[CH:8]=[C:9]([C:17]([O:19][CH3:20])=[O:18])[S:10][C:3]=12

参加物

5

反応物 3

HCID 6586Methyl chloroformateHCID 112752517-Chlorothieno[3,2-b]pyridineHCID 178418339Butyllithium

生成物 1

HCID 59424429Methyl 7-chlorothieno[3,2-B]pyridine-2-carboxylate収率 46%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

実験手順

To a stirred solution of 2 (7.0 g, 41.3 mmol) in anhydrous THF (100 mL) at −78° C. under a nitrogen atmosphere was added n-BuLi (24.7 mL, 2.5 M in hexanes, 61.8 mmol). After 1 hour, methyl chloroforrnate (9.6 ml, 124 mmol) was added and the reaction mixture was stirred for an extra hour at the same temperature, quenched with excess methanol and allowed to warm to room temperature. The solvent was then evaporated and the residue was purified by flash chromatography using hexane —AcOEt (70:30) as an eluent. The product from the column was re-crystallized from ethyl acetate to afford title compound 37 (4.3g, 46% yield) as a white solid. 1H NMR (400 MHz, DMSO-d6) δ(ppm): 8.75 (dd, J=0.8 and 4.8 Hz, 1H), 8.26 (d, J=0.8 Hz, 1H), 7.74 (dd, J=0.8 and 5.2 Hz, 1H), 3.93 (s, 3H).

後処理

  1. customquenched with excess methanol
  2. customThe solvent was then evaporated
  3. customthe residue was purified by flash chromatography
  4. customThe product from the column was re-crystallized from ethyl acetate

出典と根拠

ORDレコード
ord-207df06b9c724173a6c5db3cd65710d7
出典データセット
uspto-grants-2010_08
特許番号
US07772247B2

反応ノート

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