(o-Carboxyphenylthio)acetic acid → 3-Chloro-1-benzothiophene-2-carbaldehyde

HRID 1362030

反応式

HRID 1362030 の反応式
O=P(Cl)(Cl)[Cl:3].[C:6]([CH2:9][S:10][C:11]1[CH:19]=[CH:18][CH:17]=[CH:16][C:12]=1[C:13](O)=O)(O)=[O:7].[CH3:20][N+:21]([CH3:24])=[CH:22][Cl:23].[Cl-:25]>CN(C=O)C>[CH3:20][N+:21]([CH3:24])=[CH:22][Cl:23].[Cl-:3].[Cl:25][C:13]1[C:12]2[CH:16]=[CH:17][CH:18]=[CH:19][C:11]=2[S:10][C:9]=1[CH:6]=[O:7]

参加物

6

反応物 3

HCID 8660(o-Carboxyphenylthio)acetic acidHCID 24813Phosphorus oxychlorideHCID 77311Chloro-N,N-dimethylformiminium chloride

生成物 2

HCID 77311Chloro-N,N-dimethylformiminium chlorideHCID 8181213-Chloro-1-benzothiophene-2-carbaldehyde収率 68%

試薬・触媒・溶媒 1

HCID 6228Dimethylformamide溶媒

実験手順

Vilsmeier reagent was prepared via the dropwise addition of POCl3 (7.9 mL, 84 mmol) into ice-cold DMF (14 mL). A solution of 2-carboxymethylsulfanyl-benzoic acid (3.0 g, 14 mmol) in DMF (15 mL) was added dropwise to the Vilsmeier reagent. The resulting mixture was warmed to room temperature and then heated to 80° C. for 3.5 h. The reaction mixture was cooled to ambient temperature. Crushed ice was added until a bright yellow precipitate appeared. The solid was isolated by filtration. Purification by flash column chromatography (silica gel, hexanes/ethyl acetate 3:2) gave the title compound (1.87 g, 68%) as a yellow powder: 1H NMR (300 MHz, CDCl3) δ 10.36 (s, 1H), 8.03 (m, 1H), 7.86 (m, 1H), 7.59-7.53 (m, 2H).

後処理

  1. temperatureheated to 80° C. for 3.5 h
  2. temperatureThe reaction mixture was cooled to ambient temperature
  3. additionCrushed ice was added until a bright yellow precipitate
  4. customThe solid was isolated by filtration
  5. customPurification by flash column chromatography (silica gel, hexanes/ethyl acetate 3:2)

出典と根拠

ORDレコード
ord-c6ebb43eecd24317a3331641aa9a3d91
出典データセット
uspto-grants-2011_02
特許番号
US07879872B2

関連ノート

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