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

HRID 2297212

Reaktionsgleichung

Reaktionsgleichung von HRID 2297212
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]

Komponenten

7

Edukt 4

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

Produkt 1

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

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 6344DichloromethaneLösungsmittel2×HCID 6386tert-ButanolLösungsmittel

Versuchsvorschrift

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.

Aufarbeitung

  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

Quellen und Nachweise

ORD-Eintrag
ord-093e1619b81a48f791b16ca0bcbdce3f
Quelldatensatz
uspto-grants-2002_12
Patentnummer
US06489344B1

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