Iodine → 4-Chloro-2-iodothieno[2,3-B]pyridine-5-carbonitrile

HRID 1178611

反応式

HRID 1178611 の反応式
[Cl:1][C:2]1[C:7]([C:8]#[N:9])=[CH:6][N:5]=[C:4]2[S:10][CH:11]=[CH:12][C:3]=12.C([N-]C(C)C)(C)C.[Li+].CCCCCCC.O1CCCC1.C(C1C=CC=CC=1)C.[I:41]I>O1CCCC1.O.ClCCl>[Cl:1][C:2]1[C:7]([C:8]#[N:9])=[CH:6][N:5]=[C:4]2[S:10][C:11]([I:41])=[CH:12][C:3]=12

参加物

8

反応物 4

HCID 807IodineHCID 2724682Lithium diisopropylamideHCID 114129074-Chlorothieno[2,3-b]pyridine-5-carbonitrileHCID 22742125Tetrahydrofuran heptane ethylbenzol

生成物 1

HCID 100417134-Chloro-2-iodothieno[2,3-B]pyridine-5-carbonitrile収率 50.6%

試薬・触媒・溶媒 3

HCID 962Water溶媒HCID 6344Dichloromethane溶媒HCID 8028Tetrahydrofuran溶媒2 回

実験手順

To a solution of 4-chlorothieno[2,3-b]pyridine-5-carbonitrile (1.2 g, 6.16 mmol) [Khan, M. A.; Guarconi, A. E., J. Heterocyclic Chem., 14, 807 (1977)] in 72 mL of tetrahydrofuran at −78° C. is added dropwise 2.0 M lithium diisopropylamide in heptane/tetrahydrofuran/ethylbenzene (3.7 mL, 7.40 mmol). After stirring for 35 minutes, a solution of iodine (1.9 g, 7.40 mmol) in 8 mL of tetrahydrofuran is added dropwise over 20 minutes. The reaction mixture is stirred at −78° C. for 4 hours, then 85 mL of dichloromethane and 20 mL of water are added. The mixture is allowed to warm to room temperature. The reaction mixture is partitioned between water and dichloromethane. The organic layer is washed with a solution of sodium thiosulfate, dried over magnesium sulfate, filtered and concentrated in vacuo. The residue is purified by flash column chromatography eluting with dichloromethane to provide 1.0 g of 4-chloro-2-iodothieno[2,3-b]pyridine-5-carbonitrile as colorless crystals, mp 181–182° C.; 1H NMR (DMSO-d6) δ 8.00 (s, 1H), 8.88 (s, 1H); MS 320.8 (M+H)+.

後処理

  1. stirringThe reaction mixture is stirred at −78° C. for 4 hours
  2. customThe reaction mixture is partitioned between water and dichloromethane
  3. washThe organic layer is washed with a solution of sodium thiosulfate
  4. dry with materialdried over magnesium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customThe residue is purified by flash column chromatography
  8. washeluting with dichloromethane

出典と根拠

ORDレコード
ord-d601d2acd7984d228fa876d923b493a0
出典データセット
uspto-grants-2007_10
特許番号
US07276519B2

関連ノート

読み込み中…