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

HRID 1822319ノート

反応式

HRID 1822319 の反応式
[CH3:1][O:2][C:3](=[O:14])[CH2:4][CH2:5][C:6]1[CH:11]=[CH:10][C:9]([OH:12])=[CH:8][C:7]=1[CH3:13].[Br:15][C:16]1[CH:21]=[CH:20][CH:19]=[C:18](Br)[C:17]=1[CH3:23].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:14])[CH2:4][CH2:5][C:6]1[CH:11]=[CH:10][C:9]([O:12][C:18]2[CH:19]=[CH:20][CH:21]=[C:16]([Br:15])[C:17]=2[CH3:23])=[CH:8][C:7]=1[CH3:13]

参加物

7

反応物 4

HCID 10796Cesium carbonateHCID 346812,6-DibromotolueneHCID 707002,2,6,6-Tetramethyl-3,5-heptanedioneHCID 13551833Methyl 3-(4-Hydroxy-2-methylphenyl)propanoate

生成物 1

HCID 578941383-[4-(3-Bromo-2-methyl-phenoxy)-2-methyl-phenyl]-propionic acid methyl ester収率 78%

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-hydroxy-2-methyl-phenyl)-propionic acid methyl ester (2.0 g, 10.3 mmol), 2,6-dibromotoluene (7.72 g, 30.9 mmol), cesium carbonate (4.03 g, 12.4 mmol), and 2,2,6,6-tetramethyl-3,5-heptanedione (0.47 g, 2.55 mmol) in 1-methyl-2-pyrrolidinone (20 mL) is purged with N2, and then copper (I) chloride (0.51 g, 5.15 mmol) is added. The reaction is heated to 120° C. for 17 hours under N2, and then cooled and quenched with 1 N HCl (50 mL). The mixture is diluted with water and extracted with Et2O. 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 2.92 g (78%) of the title compound. Rf=0.35 (4/1 hexanes/EtOAc). 1H NMR (400 MHz, CDCl3); MS (ES+) m/z mass calculated for C18H19O3Br 362, found 363 and 365 (M+1 and M+3, 100%).

後処理

  1. customis purged with N2
  2. temperaturecooled
  3. customquenched with 1 N HCl (50 mL)
  4. additionThe mixture is diluted with water
  5. extractionextracted with Et2O
  6. dry with materialThe organic layer is dried (Na2SO4)
  7. customthe solvent is removed in vacuo
  8. customto afford crude product that
  9. customis absorbed on silica gel
  10. custompurified by flash chromatography

出典と根拠

ORDレコード
ord-36beed97a8224dca8cab09bf075cf82d
出典データセット
uspto-grants-2009_10
特許番号
US07608639B2

反応ノート

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