3-Chlorobenzenesulphonyl chloride → Ethyl 2-bromo-4-{[(3-chlorophenyl)sulfonyl]amino}-6-methylthieno[2,3-b]pyridine-5-carboxylate

HRID 573592ノート

反応式

HRID 573592 の反応式
[NH2:1][C:2]1[C:7]([C:8]([O:10][CH2:11][CH3:12])=[O:9])=[C:6]([CH3:13])[N:5]=[C:4]2[S:14][C:15]([Br:17])=[CH:16][C:3]=12.CC(C)([O-])C.[Na+].[Cl:24][C:25]1[CH:26]=[C:27]([S:31](Cl)(=[O:33])=[O:32])[CH:28]=[CH:29][CH:30]=1>C1COCC1.CN(C=O)C.O>[Br:17][C:15]1[S:14][C:4]2=[N:5][C:6]([CH3:13])=[C:7]([C:8]([O:10][CH2:11][CH3:12])=[O:9])[C:2]([NH:1][S:31]([C:27]3[CH:28]=[CH:29][CH:30]=[C:25]([Cl:24])[CH:26]=3)(=[O:33])=[O:32])=[C:3]2[CH:16]=1

参加物

7

反応物 3

HCID 179093-Chlorobenzenesulphonyl chlorideHCID 23676156Sodium t-butoxideHCID 68323734Ethyl 4-amino-2-bromo-6-methylthieno[2,3-b]pyridine-5-carboxylate

生成物 1

HCID 68323811Ethyl 2-bromo-4-{[(3-chlorophenyl)sulfonyl]amino}-6-methylthieno[2,3-b]pyridine-5-carboxylate収率 69.5%

試薬・触媒・溶媒 3

HCID 962Water溶媒HCID 6228Dimethylformamide溶媒HCID 8028Tetrahydrofuran溶媒

実験手順

Alternatively, to a stirred solution of ethyl 4-amino-2-bromo-6-methylthieno[2,3-b]pyridine-5-carboxylate (Description 66) (3.76 g, 11.93 mmol) in THF (60 mL) and DMF (30 mL) was added sodium tert-butoxide (2.87 g, 29.8 mmol) and 3-chlorobenzenesulfonyl chloride (3.36 mL, 23.86 mmol). The reaction mixture was stirred at RT under nitrogen for ca. 30 min and was then diluted with water (ca. 30 mL) and concentrated in vacuo. The residue was purified by chromatography on silica, eluting with a gradient of 0-50% ethyl acetate/DCM, to afford the title compound (4.06 g). Alternatively, to a stirred solution of ethyl 4-amino-2-bromo-6-methylthieno[2,3-b]pyridine-5-carboxylate (Description 66) (7 g, 22.21 mmol) in THF (100 mL) and DMF (50 mL) was added sodium tert-butoxide (5.34 g, 55.5 mmol) and 3-chlorobenzenesulfonyl chloride (6.25 mL, 44.4 mmol). The reaction mixture was then stirred at RT under nitrogen for ca. 30 min. The reaction mixture was quenched with saturated NH4Cl solution (ca. 200 mL) and extracted with DCM (ca. 80 mL×5). The combined organics were dried and concentrated in vacuo. The residue was purified by chromatography on silica, eluting with a gradient of 0-50% ethyl acetate in DCM, to afford material (8.24 g). 200 mg of the material was re-purified with a gradient of 0-30% ethyl acetate in DCM, to afford the title compound (115 mg).

後処理

  1. concentrationconcentrated in vacuo
  2. customThe residue was purified by chromatography on silica
  3. washeluting with a gradient of 0-50% ethyl acetate/DCM

出典と根拠

ORDレコード
ord-0d3f860b90d34afb8b292e4c782b42c0
出典データセット
uspto-grants-2015_05
特許番号
US09029545B2

反応ノート

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