Hydrochloric Acid → 4-(1-Benzylthio-1-methylethyl)-3-methoxycarbonyl-2-methylene-4-butanolide

HRID 2211010Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 2211010
Cl.[CH2:2]([S:9][C:10]([CH3:14])([CH3:13])[CH:11]=[O:12])[C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1.Br[CH2:16]/[C:17](=[CH:22]\[C:23]([O:25][CH3:26])=[O:24])/[C:18](OC)=[O:19].[Cl-].[NH4+]>C1COCC1.[Zn]>[CH2:2]([S:9][C:10]([CH:11]1[O:12][C:18](=[O:19])[C:17](=[CH2:16])[CH:22]1[C:23]([O:25][CH3:26])=[O:24])([CH3:14])[CH3:13])[C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1

Komponenten

7

Edukt 4

HCID 313Hydrochloric AcidHCID 25517Ammonium ChlorideHCID 10466666Dimethyl bromomethylfumarateHCID 10702996HCID 10702996, Verbindung

Produkt 1

HCID 152904654-(1-Benzylthio-1-methylethyl)-3-methoxycarbonyl-2-methylene-4-butanolideAusbeute 38,2 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 23994ZincKatalysatorHCID 8028TetrahydrofuranLösungsmittel3×

Versuchsvorschrift

To a stirred suspension of zinc dust (0.67 g) activated with hydrochloric acid in THF (15 ml), 2-benzylthio-2-methylpropionaldehyde (1.00 g) dissolved in THF (5 ml) and dimethyl 2-bromomethylfumarate (1.28 g) dissolved in THF (5 ml) were added dropwise in the order named while refluxing under nitrogen atmosphere. The mixture was refluxed for an additional 1.5 hours and saturated aqueous ammonium chloride solution was added to it. After cooling the mixture was filtered by celite. A reaction product was extracted with ethyl acetate from the filtrate. The organic layer was washed with 1N hydrochloric acid, water and then saturated sodium chloride solution. The organic layer was dried over anhydrous magnesium sulfate and concentrated in vacuo. The oily residue was purified by silica gel column chromatography to give 0.63 g (38%) of the titled compound.

Aufarbeitung

  1. additionwere added dropwise in the order
  2. temperaturewhile refluxing under nitrogen atmosphere
  3. temperatureThe mixture was refluxed for an additional 1.5 hours
  4. temperatureAfter cooling the mixture
  5. filtrationwas filtered by celite
  6. extractionA reaction product was extracted with ethyl acetate from the filtrate
  7. washThe organic layer was washed with 1N hydrochloric acid, water
  8. dry with materialThe organic layer was dried over anhydrous magnesium sulfate
  9. concentrationconcentrated in vacuo
  10. customThe oily residue was purified by silica gel column chromatography

Quellen und Nachweise

ORD-Eintrag
ord-062d59d83d6c49d89a47c45720f4aab9
Quelldatensatz
uspto-grants-1995_10
Patentnummer
US05461158

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