Cesium carbonate → trans-2-(6-Chloro-2-oxo-2H-1-benzopyran-4-yloxymethyl)-cyclopropanecarboxylic acid methyl ester

HRID 495148ノート

反応式

HRID 495148 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].C([O-])([O-])=O.[Cs+].[Cs+].[CH3:20][O:21][C:22]([C@@H:24]1[CH2:26][C@H:25]1[CH2:27]OS(C)(=O)=O)=[O:23].S([O-])(=O)(=O)C>CN(C=O)C>[CH3:20][O:21][C:22]([C@@H:24]1[CH2:26][C@H:25]1[CH2:27][O:13][C:5]1[C:4]2[CH:3]=[C:2]([Cl:1])[CH:11]=[CH:10][C:9]=2[O:8][C:7](=[O:12])[CH:6]=1)=[O:23]

参加物

6

反応物 4

HCID 10796Cesium carbonateHCID 85257MethanesulfonateHCID 546863486-Chloro-4-hydroxycoumarinHCID 86591119trans-2-Methanesulfonyloxymethyl-cyclopropanecarboxylic acid methyl ester

生成物 1

HCID 86596928trans-2-(6-Chloro-2-oxo-2H-1-benzopyran-4-yloxymethyl)-cyclopropanecarboxylic acid methyl ester収率 62.4%

試薬・触媒・溶媒 1

HCID 6228Dimethylformamide溶媒

反応条件

温度
100 °C

実験手順

6-chloro-4-hydroxycoumarin (5.09 mmol, 1.0 g) is dissolved in 80 mL of DMF, and Cs2CO3 (7.63 mmol, 2.49 g), and trans-2-methanesulfonyloxymethyl-cyclopropanecarboxylic acid methyl ester (6.14 mmol, 1.28 g) are added. The reaction is heated to 100° C. for 5 hrs, a further 0.2 eq of the mesylate is added, and heating is continued for an additional 2 hrs. After cooling to ambient temperature, the DMF is removed in vacuo. The residue is dissolved in EtOAc and is washed with H2O. The organic layer is dried over MgSO4, is filtered, and the EtOAc is removed under reduced pressure to afford a yellow solid which is chromatographed on SiO2 (35 g) using DCM as the eluent to afford the title compound as a white solid (0.98 g, 62%). 1H NMR (DMSO-d6, 300 MHz) δ 7.75 (2H, m), 7.45 (1H, d), 5.97 (1H, s), 4.22 (2H, m), 3.65 (3H, s), 1.90 (2H, m), 1.19 (2H, m); MS (ESI, Pos.) calcd for C15H13ClO5 m/z [M+H]=309.0, found 309.0.

後処理

  1. temperatureheating
  2. temperatureAfter cooling to ambient temperature
  3. customthe DMF is removed in vacuo
  4. dissolutionThe residue is dissolved in EtOAc
  5. washis washed with H2O
  6. dry with materialThe organic layer is dried over MgSO4
  7. filtrationis filtered
  8. customthe EtOAc is removed under reduced pressure
  9. customto afford a yellow solid which
  10. customis chromatographed on SiO2 (35 g)

出典と根拠

ORDレコード
ord-6a233736ab9448f782b3c9e78c4ea288
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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