Hydrochloric Acid → N-benzyl-4-(1-benzylthio-1-methylethyl)-2-ethylidene-4-butanelactam

HRID 2211013Notes

Reaction equation

HRID 2211013 reaction equation
Cl.Br[CH2:3]/[C:4](=[CH:9]\[CH3:10])/[C:5](OC)=[O:6].[CH2:11]([S:18][C:19]([CH3:30])([CH3:29])[CH:20]=[N:21][CH2:22][C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1)[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1.[Cl-].[NH4+]>C1COCC1.[Zn]>[CH2:22]([N:21]1[CH:20]([C:19]([S:18][CH2:11][C:12]2[CH:13]=[CH:14][CH:15]=[CH:16][CH:17]=2)([CH3:30])[CH3:29])[CH2:3][C:4](=[CH:9][CH3:10])[C:5]1=[O:6])[C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 25517Ammonium ChlorideHCID 11019705Methyl 2-bromomethylcrotonateHCID 19378136N-(2-benzylthio-2-methylpropylidene)benzylamine

Product 1

HCID 53674808N-benzyl-4-(1-benzylthio-1-methylethyl)-2-ethylidene-4-butanelactamYield 19%

Reagents, catalysts & solvents 2

HCID 23994ZincCatalystHCID 8028TetrahydrofuranSolvent3×

Procedure

To a stirred suspension of zinc dust (0.53 g) activated with hydrochloric acid in THF (20 ml), methyl 2-bromomethylcrotonate (1.50 g) dissolved in THF (10 ml) and N-(2-benzylthio-2-methylpropylidene)benzylamine (2.00 g) dissolved in THF (10 ml) were added dropwise in the order named at about 30° C. under nitrogen atmosphere and ultrasonic irradiation. The mixture was stirred overnight at room temperature. To the mixture saturated aqueous ammonium chloride solution was added. The mixture was filtered by celite. A reaction product was extracted with ethyl acetate from the filtrate. The organic layer was washed with IN 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 1.03 g (40%) of the titled compound No.7-1 and 0.48 g (19%) of the titled compound No.7-2.

Workup

  1. additionwere added dropwise in the order
  2. customnamed at about 30° C. under nitrogen atmosphere
  3. customultrasonic irradiation
  4. filtrationThe mixture was filtered by celite
  5. extractionA reaction product was extracted with ethyl acetate from the filtrate
  6. washThe organic layer was washed with IN hydrochloric acid, water
  7. dry with materialThe organic layer was dried over anhydrous magnesium sulfate
  8. concentrationconcentrated in vacuo
  9. customThe oily residue was purified by silica gel column chromatography

Sources & evidence

ORD record
ord-e03ea93b583047caa0a9dd1057e4706b
Source dataset
uspto-grants-1995_10
Patent number
US05461158

Reaction notes

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