Azobisisobutyronitrile → HCID 57179453, compound

HRID 635114Notes

Reaction equation

HRID 635114 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.C(OCC)(=O)C.CCCCCC>[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

8

Reactant 4

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

Product 1

HCID 57179453HCID 57179453, compoundYield 43%

Reagents, catalysts & solvents 3

HCID 6212ChloroformSolventHCID 8058HexaneSolventHCID 8857Ethyl AcetateSolvent

Procedure

(E)-Ethyl 3-(1-ethoxycarbonylcyclobutyl)-2-butenoate (16.91 g, 70 mmol) was dissolved in chloroform (180 ml) and N-bromosuccinimide (12.53 g, 70 minol) and a catalytic amount of azobisisobutyronitrile were added thereto. The thus obtained mixture was heated under ref lux for 18 hours. After completing of the reaction, the solvent was evaporated and carbon tetrachloride (100 ml) was added to the residue. Then, insoluble matter was filtered off and the filtrate was concentrated. The residue was dissolved in ethanol (100 ml) and sodium hydrogencarbonate (11.82 g, 140 mmol) was added thereto. Next, (S)-phenylethylamine (9.87 ml, 77 mmiol) was added dropwise thereinto at room temperature. After completing the addition, the resultant mixture was heated under reflux for 3 hours. After completing the reaction, the solvent was evaporated and methylene chloride (300 ml) was added to the residue. The insoluble matter was filtered off and the solvent was evaporated. The residue thus obtained was subjected to silica gel column chromatography (eluent: n-hexane:ethyl acetate=1:1) to obtain 19.57 g (43% of the title compound as an oily substance.

Workup

  1. temperatureThe thus obtained mixture was heated under ref lux for 18 hours
  2. customAfter completing of the reaction
  3. customthe solvent was evaporated
  4. additioncarbon tetrachloride (100 ml) was added to the residue
  5. filtrationThen, insoluble matter was filtered off
  6. concentrationthe filtrate was concentrated
  7. dissolutionThe residue was dissolved in ethanol (100 ml)
  8. customat room temperature
  9. additionthe addition
  10. temperatureunder reflux for 3 hours
  11. customthe reaction
  12. customthe solvent was evaporated
  13. additionmethylene chloride (300 ml) was added to the residue
  14. filtrationThe insoluble matter was filtered off
  15. customthe solvent was evaporated
  16. customThe residue thus obtained

Sources & evidence

ORD record
ord-dd2377c5c26747c299e859d2d830a19a
Source dataset
uspto-grants-2001_02
Patent number
US06184388B2

Reaction notes

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