Cesium carbonate → 3-{4-[3-(4-Chloro-2-phenoxy-phenoxy)-phenoxy]-2-methyl-phenyl}-propionic acid methyl ester

HRID 1822257

反応式

HRID 1822257 の反応式
[CH3:1][O:2][C:3](=[O:21])[CH2:4][CH2:5][C:6]1[CH:11]=[CH:10][C:9]([O:12][C:13]2[CH:18]=[CH:17][CH:16]=[C:15](Br)[CH:14]=2)=[CH:8][C:7]=1[CH3:20].[Cl:22][C:23]1[CH:28]=[CH:27][C:26]([OH:29])=[C:25]([O:30][C:31]2[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=2)[CH:24]=1.C(=O)([O-])[O-].[Cs+].[Cs+].CC(C)(C(=O)CC(=O)C(C)(C)C)C>CN1CCCC1=O.[Cu]Cl>[CH3:1][O:2][C:3](=[O:21])[CH2:4][CH2:5][C:6]1[CH:11]=[CH:10][C:9]([O:12][C:13]2[CH:18]=[CH:17][CH:16]=[C:15]([O:29][C:26]3[CH:27]=[CH:28][C:23]([Cl:22])=[CH:24][C:25]=3[O:30][C:31]3[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=3)[CH:14]=2)=[CH:8][C:7]=1[CH3:20]

参加物

7

反応物 4

HCID 10796Cesium carbonateHCID 707002,2,6,6-Tetramethyl-3,5-heptanedioneHCID 127742954-Chloro-2-phenoxyphenolHCID 578941923-[4-(3-Bromo-phenoxy)-2-methyl-phenyl]-propionic acid methyl ester

生成物 1

HCID 578942213-{4-[3-(4-Chloro-2-phenoxy-phenoxy)-phenoxy]-2-methyl-phenyl}-propionic acid methyl ester収率 33.2%

試薬・触媒・溶媒 2

HCID 62652Cuprous chloride触媒HCID 13387N-methyl-2-pyrrolidone溶媒

反応条件

温度
120 °C

実験手順

A mixture of 3-[4-(3-bromo-phenoxy)-2-methyl-phenyl]-propionic acid methyl ester (0.474 g, 1.36 mmol), 4-chloro-2-phenoxy-phenol (0.30 g, 1.36 mmol), cesium carbonate (0.531 g, 1.63 mmol), copper (I) chloride (0.067 g, 0.677 mmol) and 2,2,6,6-tetramethyl-3,5-heptanedione (0.063 g, 0.342 mmol) in 1-methyl-2-pyrrolidinone (5 mL) is heated to 120° C. for 20 hours under N2. The reaction is cooled and quenched with 1 N HCl (20 mL). The mixture is then diluted with Et2O and extracted with water. The organic layer is dried (Na2SO4), and the solvent is removed in vacuo to afford crude product that is absorbed on silica gel and purified by flash chromatography using 9/1 hexanes/ethyl acetate to afford 0.221 g (33%) of the title compound. Rf=0.29 (4/1 hexanes/EtOAc). 1H NMR (400 MHz, CDCl3); MS (ES+) m/z mass calculated for C29H25O5Cl 488, found 489 and 351 (M+1 and M+3, 100%).

後処理

  1. temperatureThe reaction is cooled
  2. customquenched with 1 N HCl (20 mL)
  3. additionThe mixture is then diluted with Et2O
  4. extractionextracted with water
  5. dry with materialThe organic layer is dried (Na2SO4)
  6. customthe solvent is removed in vacuo
  7. customto afford crude product that
  8. customis absorbed on silica gel
  9. custompurified by flash chromatography

出典と根拠

ORDレコード
ord-4bf89494741449f5a7848209732cd3dc
出典データセット
uspto-grants-2009_10
特許番号
US07608639B2

関連ノート

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