Methanol → Methyl 5-(2,4-dichlorophenyl)-4-imidazol-2-yl-5-oxo-2-phenylthiopentanoate

HRID 1823528

反応式

HRID 1823528 の反応式
CC(C)([O-])C.[Cl:6][C:7]1[CH:12]=[C:11]([Cl:13])[CH:10]=[CH:9][C:8]=1[C:14](=[O:21])[CH2:15][C:16]1[NH:17][CH:18]=[CH:19][N:20]=1.[C:22]1([C:28](=[CH2:33])[C:29]([O:31][CH3:32])=[S:30])[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1.CO>C(O)(C)(C)C.ClCCl>[Cl:6][C:7]1[CH:12]=[C:11]([Cl:13])[CH:10]=[CH:9][C:8]=1[C:14](=[O:21])[CH:15]([C:16]1[NH:20][CH:19]=[CH:18][N:17]=1)[CH2:33][CH:28]([C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1)[C:29]([O:31][CH3:32])=[S:30]

参加物

7

反応物 4

HCID 887Methanol2 回HCID 45749132-Methylpropan-2-olateHCID 221427181-(2,4-dichlorophenyl)-2-(1H-imidazol-2-yl)ethanoneHCID 86586215Methyl 2-phenylthioprop-2-enoate2 回

生成物 1

HCID 54447738Methyl 5-(2,4-dichlorophenyl)-4-imidazol-2-yl-5-oxo-2-phenylthiopentanoate収率 71%

試薬・触媒・溶媒 2

HCID 6344Dichloromethane溶媒2 回HCID 6386tert-Butanol溶媒

実験手順

A solution (1 M) of tert-butoxide in tert-butanol (54.9 ml) was added to a stirred solution of 1-(2,4-dichlorophenyl)-2-imidazol-2-ylethan-1-one (0.11 M) and methyl 2-phenylthioprop-2-enoate (0.14 M) dissolved in dichloromethane (300 ml) and methanol (200 ml) at room temperature. The reaction, which developed a dark color, was typically stirred overnight (ca. 16 h) under argon. The reaction was monitored by TLC using 5% methanol in dichloromethane as the solvent system. Additional methyl 2-phenylthioprop-2-enoate was added as needed to consume all of the starting 1-(2,4-dichlorophenyl)-2-imidazol-2-ylethan-1-one. The reaction was quenched by the addition of sat. aq. NH4Cl (˜100 ml). The mixture was transferred to a separatory funnel and diluted with ethyl acetate (300 ml). The aqueous layer was removed and the organic layer was washed with sat. aq. NH4Cl (3×100 ml), brine (100 ml), and dried with Na2SO4. After filtration and evaporation, the residue was purified by flash chromatography over silica gel. The column was eluted starting with 100% dichloromethane to remove the non-polar methyl 2-phenylthioprop-2-enoate. The product was eluted with 3% methanol in dichloromethane. After drying overnight in vacuo, methyl 5-(2,4-dichlorophenyl)-4-imidazol-2-yl-5-oxo-2-phenylthiopentanoate as a deep red glass was obtained in 71% yield. A further 10% yield of product could be obtained by resubmitting side product contaminated fractions to a second purification by flash chromatography.

後処理

  1. customat room temperature
  2. customThe reaction, which
  3. custom(ca. 16 h)
  4. customto consume all of the starting 1-(2,4-dichlorophenyl)-2-imidazol-2-ylethan-1-one
  5. customThe reaction was quenched by the addition of sat. aq. NH4Cl (˜100 ml)
  6. customThe mixture was transferred to a separatory funnel
  7. additiondiluted with ethyl acetate (300 ml)
  8. customThe aqueous layer was removed
  9. washthe organic layer was washed with sat. aq. NH4Cl (3×100 ml), brine (100 ml)
  10. dry with materialdried with Na2SO4
  11. filtrationAfter filtration and evaporation
  12. customthe residue was purified by flash chromatography over silica gel
  13. washThe column was eluted
  14. customto remove the non-polar methyl 2-phenylthioprop-2-enoate
  15. washThe product was eluted with 3% methanol in dichloromethane
  16. customAfter drying overnight in vacuo

出典と根拠

ORDレコード
ord-69a4d11c72be4f7d8a7be6eeb87f3a93
出典データセット
uspto-grants-2006_05
特許番号
US07037918B2

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