Chloroform → Ethyl 4,5,7-trichloro-8-methoxyquinoline-3-carboxylate

HRID 623416ノート

反応式

HRID 623416 の反応式
[CH2:1]([O:3][C:4]([C:6]1[CH:7]=[N:8][C:9]2[C:14]([C:15]=1[Cl:16])=[CH:13][CH:12]=C[C:10]=2[O:17][CH3:18])=[O:5])[CH3:2].S(Cl)([Cl:22])(=O)=O.[CH:24]([Cl:27])(Cl)Cl>>[CH2:1]([O:3][C:4]([C:6]1[CH:7]=[N:8][C:9]2[C:14]([C:15]=1[Cl:16])=[C:13]([Cl:22])[CH:12]=[C:24]([Cl:27])[C:10]=2[O:17][CH3:18])=[O:5])[CH3:2]

参加物

4

反応物 3

HCID 6212Chloroform2 回HCID 24648Sulfuryl chloride2 回HCID 3045573-Quinolinecarboxylic acid, 4-chloro-8-methoxy-, ethyl ester

生成物 1

HCID 57939336Ethyl 4,5,7-trichloro-8-methoxyquinoline-3-carboxylate収率 29%

反応条件

温度
65 °C

実験手順

To a stirred solution of 4-chloro-8-methoxy-quinoline-3-carboxylic acid ethyl ester (1.00 g, 3.76 mmol) in chloroform (50 mL) was added, dropwise over 1 h, a solution of sulfuryl chloride (15 mL) in chloroform (15 mL) whilst maintaining the temperature at 25-30° C. The solution was then heated at 60-70° C. for 48 h. During this time, further sulfuryl chloride (2 mL) was added at regular intervals (2, 24 and 30 h). The solution was allowed to cool to RT and added to ice-aqueous ammonia, adjusting the pH to 8. The mixture was then extracted with dichloromethane (20 mL×3), the extracts combined and concentrated. Column chromatography (silica gel, dichloromethane/methanol (100:1)) gave the title compound 26 as a cream solid (0.36 g, 29%). 1H-NMR (CDCl3, 400 MHz): δ 9.04 (s, 1H), 7.78 (s, 1H), 4.51 (q, J=7.1, 2 H), 4.14 (s, 3H), 1.46 (t, J=7.1, 3 H).

後処理

  1. temperatureto cool to RT
  2. additionadded to ice-aqueous ammonia
  3. extractionThe mixture was then extracted with dichloromethane (20 mL×3)
  4. concentrationconcentrated

出典と根拠

ORDレコード
ord-2681281dee0f4661a296868bacfedb0d
出典データセット
uspto-grants-2016_04
特許番号
US09302993B2

反応ノート

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