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

HRID 2211010Notes

Reaction equation

HRID 2211010 reaction equation
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

Participants

7

Reactant 4

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

Product 1

HCID 152904654-(1-Benzylthio-1-methylethyl)-3-methoxycarbonyl-2-methylene-4-butanolideYield 38.2%

Reagents, catalysts & solvents 2

HCID 23994ZincCatalystHCID 8028TetrahydrofuranSolvent3×

Procedure

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.

Workup

  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

Sources & evidence

ORD record
ord-062d59d83d6c49d89a47c45720f4aab9
Source dataset
uspto-grants-1995_10
Patent number
US05461158

Reaction notes

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