Toluene-4-sulfonic acid 6-chloro-2-oxo-2H-1-benzopyran-4-yl ester → 4-(6-Chloro-2-oxo-2H-1-benzopyran-4-yl)-butyronitrile

HRID 495150ノート

反応式

HRID 495150 の反応式
[Cl:1][C:2]1[CH:3]=[CH:4][C:5]2[O:10][C:9](=[O:11])[CH:8]=[C:7](OS(C3C=CC(C)=CC=3)(=O)=O)[C:6]=2[CH:23]=1.[Br-].[C:25]([CH2:27][CH2:28][CH2:29][Zn+])#[N:26]>C1COCC1>[Cl:1][C:2]1[CH:3]=[CH:4][C:5]2[O:10][C:9](=[O:11])[CH:8]=[C:7]([CH2:29][CH2:28][CH2:27][C:25]#[N:26])[C:6]=2[CH:23]=1

参加物

4

反応物 2

HCID 46179801Toluene-4-sulfonic acid 6-chloro-2-oxo-2H-1-benzopyran-4-yl esterHCID 178511034HCID 178511034、化合物

生成物 1

HCID 118174844-(6-Chloro-2-oxo-2H-1-benzopyran-4-yl)-butyronitrile収率 73%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒2 回

反応条件

温度
60 °C

実験手順

Toluene-4-sulfonic acid 6-chloro-2-oxo-2H-1-benzopyran-4-yl ester (1.05 g, 3 mmol) is dissolved in THF (30 mL) under nitrogen and [P(o-tolyl)3]2PdCl2 (120 mg, 0.15 mmol) is added 3-cyanopropylzinc bromide (9 mL of a 0.5 M solution in THF, 4.5 mmol) is added and the resulting yellow solution is stirred at 60° C. for 2 hrs. Silica gel is added to the dark red reaction mixture, which is concentrated in vacuo and purified by flash column chromatography eluting with CH2Cl2 and gradually increasing polarity to 1% MeOH—CH2Cl2 to give a residue which is triturated with Et2O to give the title compound (0.54 g, 73%) as a cream solid. 1H NMR (DMSO-d6, 400 MHz) d 7.92 (1H, d, J=2 Hz), 7.68 (1H, dd, J=9, 2 Hz), 7.46 (1H, d, J=9 Hz), 6.47 (1H, s), 2.90 (2H, t, J=7 Hz), 2.63 (2H, t, J=7 Hz), 1.94 (2H, q, J=7 Hz). LCMS (MeCN—H2O, MeCN—H2O, Luna 3 m C18(2) 30×4.6mm; (ESI Pos.) calcd for C13H10ClNO2 m/z [M+H]=248; found [no mass ion detected].

後処理

  1. additionis added
  2. additionSilica gel is added to the dark red reaction mixture, which
  3. concentrationis concentrated in vacuo
  4. custompurified by flash column chromatography
  5. washeluting with CH2Cl2
  6. temperaturegradually increasing polarity to 1% MeOH—CH2Cl2
  7. customto give a residue which
  8. customis triturated with Et2O

出典と根拠

ORDレコード
ord-a75ea56a91f6433281c39ce7cacd9627
出典データセット
uspto-grants-2009_05
特許番号
US07538233B2

反応ノート

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