Hydrochloric Acid → N-benzyl-4-(1-benzylthio-1-methylethyl)-3-methoxycarbonyl-2-methylene-4-butanelactam

HRID 2211012Notes

Reaction equation

HRID 2211012 reaction equation
Cl.[CH2:2]([S:9][C:10]([CH3:21])([CH3:20])[CH:11]=[N:12][CH2:13][C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1)[C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1.Br[CH2:23]/[C:24](=[CH:29]\[C:30]([O:32][CH3:33])=[O:31])/[C:25](OC)=[O:26].[Cl-].[NH4+]>C1COCC1.[Zn]>[CH2:13]([N:12]1[CH:11]([C:10]([S:9][CH2:2][C:3]2[CH:4]=[CH:5][CH:6]=[CH:7][CH:8]=2)([CH3:21])[CH3:20])[CH:29]([C:30]([O:32][CH3:33])=[O:31])[C:24](=[CH2:23])[C:25]1=[O:26])[C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 25517Ammonium ChlorideHCID 10466666Dimethyl bromomethylfumarateHCID 19378136N-(2-benzylthio-2-methylpropylidene)benzylamine

Product 1

HCID 19378132N-benzyl-4-(1-benzylthio-1-methylethyl)-3-methoxycarbonyl-2-methylene-4-butanelactam

Reagents, catalysts & solvents 2

HCID 23994ZincCatalystHCID 8028TetrahydrofuranSolvent3×

Procedure

To a stirred suspension of zinc dust (0.68 g) activated with hydrochloric acid in THF (15 ml), N-(2-benzylthio-2-methylpropylidene)benzylamine (1.42 g) dissolved in THF (15 ml) and dimethyl 2-bromomethylfumarate (1.28 g) dissolved in THF are added dropwise while refluxing under nitrogen atmosphere. The mixture is stirred for additional 1.5 hours under refluxing. To the mixture saturated aqueous ammonium chloride solution is added. After cooling, the mixture is filtered by celite. A reaction product is extracted with ethyl acetate from the filtrate. The organic layer is washed with 1N hydrochloric acid, water and then saturated sodium chloride solution. The organic layer is dried over anhydrous magnesium sulfate and concentrated in vacuo. The oily residue is purified by silica gel column chromatography to give the titled compound.

Workup

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

Sources & evidence

ORD record
ord-7b8d3fc654a84b82af15815be24efb71
Source dataset
uspto-grants-1995_10
Patent number
US05461158

Reaction notes

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