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

HRID 525794ノート

反応式

HRID 525794 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.C([Li])CCC.Cl[C:17]([O:19][CH3:20])=[O:18].CO>C1COCC1.ClCCl.CCCCCC.C(OCC)C>[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

8

反応物 4

HCID 887MethanolHCID 6586Methyl chloroformateHCID 112752517-Chlorothieno[3,2-b]pyridineHCID 178418339Butyllithium

生成物 1

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

試薬・触媒・溶媒 3

HCID 6344Dichloromethane溶媒HCID 8028Tetrahydrofuran溶媒HCID 21584099Diethylether hexane溶媒

実験手順

7-chlorothieno[3,2-b]pyridine (19.7 g, 0.116 mol) was taken up in THF (400 mL) and cooled to approximately −70 C. The n-butyllithium (1.6M, 80 mL, 0.128 mol) was added dropwise with stirring under an atmosphere of nitrogen. The solution was stirred at −70 C for 1 hour at which time neat methyl chloroformate was added via dropwise addition. The reaction mixture gradually warmed to room temperature and was stirred for over the weekend. The reaction mixture was treated with 25 mL of methanol and then concentrated to dryness leaving a maroon residue. The crude solid was taken up in dichloromethane and passed through a silica gel column eluting with 1:1 hexane/ethyl acetate. Fractions containing the product were combined and concentrated to give a red solid. Trituration with 9:1 hexane/diethyl ether afforded methyl 7-chlorothieno[3,2-b]pyridine-2-carboxylate as a pink solid after filtration. Yield: 14.5 g (55%); MS [M+H]+ 227.9; 1HNMR (CDCl3) δ: 8.7 (d, 1H), 8.3 (s, 1H), 7.4 (d, 1H) ppm.

後処理

  1. temperaturecooled to approximately −70 C
  2. additionwas added via dropwise addition
  3. stirringwas stirred for over the weekend
  4. concentrationconcentrated to dryness
  5. customleaving a maroon residue
  6. washeluting with 1:1 hexane/ethyl acetate
  7. additionFractions containing the product
  8. concentrationconcentrated
  9. customto give a red solid

出典と根拠

ORDレコード
ord-490aefdf1bd7416cb353719fc94ba182
出典データセット
uspto-grants-2016_05
特許番号
US09340555B2

反応ノート

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