Pyridine → Toluene-4-sulfonic acid 6-chloro-2-oxo-2H-1-benzopyran-4-yl ester

HRID 495149ノート

反応式

HRID 495149 の反応式
[Cl:1][C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][CH:11]=1)[O:8][C:7](=[O:12])[CH:6]=[C:5]2[OH:13].N1C=CC=CC=1.[C:20]1([CH3:30])[CH:25]=[CH:24][C:23]([S:26](Cl)(=[O:28])=[O:27])=[CH:22][CH:21]=1>C(Cl)Cl>[Cl:1][C:2]1[CH:11]=[CH:10][C:9]2[O:8][C:7](=[O:12])[CH:6]=[C:5]([O:13][S:26]([C:23]3[CH:24]=[CH:25][C:20]([CH3:30])=[CH:21][CH:22]=3)(=[O:28])=[O:27])[C:4]=2[CH:3]=1

参加物

5

反応物 3

HCID 1049PyridineHCID 73974-Toluenesulfonyl chlorideHCID 546863486-Chloro-4-hydroxycoumarin

生成物 1

HCID 46179801Toluene-4-sulfonic acid 6-chloro-2-oxo-2H-1-benzopyran-4-yl ester収率 90%

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒

実験手順

6-Chloro-4-hydroxycoumarin (25.4 mmol, 5.0 g) is suspended in DCM (50 mL) and pyridine (63.3 mmol, 5.1 mL) is added. The mixture is cooled in an ice bath and p-toluenesulfonyl chloride (26.8 mmol, 5.1 g) is added. The ice bath is removed and the compound slowly dissolves and a solid is deposited (pyridine HCl). After 1 hr the mixture is transferred to a separatory funnel, HCl (2 M) is added, and a solid is formed. The organic layer is removed and the solid-containing aqueous layer is filtered to remove the precipitate. The filtrate is washed with DCM and the combined organic layers are washed with H2O, NaHCO3 (sat.), H2O, and brine. The extract is then dried over MgSO4 and is evaporated. The residue is triturated with Et2O to give the title compound (8.0 g, 90%) as a cream solid. 1H NMR (CDCl3, 400 MHz) δ 7.91 (2H, d, J=8 Hz), 7.54 (1H, d, J=2 Hz), 7.51 (1H, dd, J=2, 9 Hz), 7.42 (2H, d, J=8 Hz), 7.26 (1H, d, J=9 Hz), 6.38 (1H, s), 2.49 (3H, s); LCMS (MeCN—H2O, Luna 3μC18(2) 30×4.6 mm; MS (ESI, Pos.) calcd for C16H11ClO5S m/z [M+H]=351 found [no mass ion detected].

後処理

  1. temperatureThe mixture is cooled in an ice bath
  2. customThe ice bath is removed
  3. dissolutionthe compound slowly dissolves
  4. additionHCl (2 M) is added
  5. customa solid is formed
  6. customThe organic layer is removed
  7. filtrationthe solid-containing aqueous layer is filtered
  8. customto remove the precipitate
  9. washThe filtrate is washed with DCM
  10. washthe combined organic layers are washed with H2O, NaHCO3 (sat.), H2O, and brine
  11. dry with materialThe extract is then dried over MgSO4
  12. customis evaporated
  13. customThe residue is triturated with Et2O

出典と根拠

ORDレコード
ord-119b9690803a4d869af22da53c819932
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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