Azobisisobutyronitrile → HCID 57179453, compound

HRID 635093Notes

Reaction equation

HRID 635093 reaction equation
[CH2:1]([O:3][C:4]([C:6]1(/[C:10](/[CH3:17])=[CH:11]/[C:12]([O:14]CC)=O)[CH2:9][CH2:8][CH2:7]1)=[O:5])[CH3:2].Br[N:19]1[C:23](=O)[CH2:22][CH2:21][C:20]1=O.N(C(C)(C)C#N)=N[C:28](C)([CH3:31])[C:29]#N.[C:38](=O)(O)[O-].[Na+]>C(Cl)(Cl)Cl>[CH2:1]([O:3][C:4]([C:6]1([C:10]2[CH2:17][N:19]([C@H:23]([C:22]3[CH:31]=[CH:28][CH:29]=[CH:20][CH:21]=3)[CH3:38])[C:12](=[O:14])[CH:11]=2)[CH2:7][CH2:8][CH2:9]1)=[O:5])[CH3:2]

Participants

6

Reactant 4

HCID 6547AzobisisobutyronitrileHCID 67184N-bromobutanimideHCID 516892Sodium BicarbonateHCID 21260989HCID 21260989, compound

Product 1

HCID 57179453HCID 57179453, compoundYield 43%

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent

Procedure

(E)-Ethyl 3-(1-ethoxycarbonylcyclobutyl)-2-butenoate (16.91 g, 70 mmol) was dissolved in chloroform (180 ml), and the solution was mixed with N-bromosuccinimide (12.53 g, 70 mmol) and a catalytic amount of azobisisobutyronitrile and heated under reflux for 18 hours. After completing the reaction, the solvent was evaporated, the thus obtained residue was mixed with carbon tetrachloride (100 ml), insoluble material was removed by filtration and then the resulting filtrate was concentrated. The thus obtained residue was dissolved in ethanol (100 ml) and mixed with sodium bicarbonate (11.82 g, 140 mmol). At room temperature, thereto was added dropwise (S)-phenylethylamine (9.87 ml, 77 mmol). After completing the dropwise addition, the mixture was heated under reflux for 3 hours. After completing the reaction, the solvent was evaporated, and the thus obtained residue was mixed with methylene chloride (300 ml). After removing insoluble material by filtration, the solvent was evaporated and the resulting-residue was subjected to silica gel column chromatography and eluted with an eluant of n-hexane:ethyl acetate=1:1, to thereby obtain 19.57 g (43%) of the title compound in an oily form.

Workup

  1. temperatureunder reflux for 18 hours
  2. customthe reaction
  3. customthe solvent was evaporated
  4. additionthe thus obtained residue was mixed with carbon tetrachloride (100 ml), insoluble material
  5. customwas removed by filtration
  6. concentrationthe resulting filtrate was concentrated
  7. dissolutionThe thus obtained residue was dissolved in ethanol (100 ml)
  8. additionthe dropwise addition
  9. temperaturethe mixture was heated
  10. temperatureunder reflux for 3 hours
  11. customthe reaction
  12. customthe solvent was evaporated
  13. additionthe thus obtained residue was mixed with methylene chloride (300 ml)
  14. customAfter removing insoluble material
  15. filtrationby filtration
  16. customthe solvent was evaporated
  17. washeluted with an eluant of n-hexane

Sources & evidence

ORD record
ord-5bac177201d446468bd4fe3c61a706cb
Source dataset
uspto-grants-2001_02
Patent number
US06184388B2

Reaction notes

Loading…