Nitrogen → HCID 14508126, compound

HRID 486418Notes

Reaction equation

HRID 486418 reaction equation
N#N.[CH3:3]C[O-].[Na+].[CH2:7]([O:9][C:10](=[O:19])[CH:11]([C:16](=[O:18])[CH3:17])[CH2:12][C:13]([CH3:15])=[CH2:14])[CH3:8].[I-]>C(O)C>[CH2:7]([O:9][C:10](=[O:19])[C:11]([C:16](=[O:18])[CH3:17])([CH3:3])[CH2:12][C:13]([CH3:15])=[CH2:14])[CH3:8]

Participants

6

Reactant 4

HCID 947Nitrogen2×HCID 30165Iodide IonHCID 97705Ethyl 2-acetyl-4-methylpent-4-enoateHCID 2723922Sodium ethoxide

Product 1

HCID 14508126HCID 14508126, compound

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Conditions

Temperature
15 °C

Procedure

A 2000 ml flask, equipped with mechanical stirring, a condenser and N2 atmosphere, is charged with 24.3 g of N2 and 400 ml of ethanol to prepare sodium ethylate. After cooling to 15° C., the ethyl-2-acetyl-4-methyl-4-pentenoate (161.4 g) is added to the solution over 30 min while maintaining the temperature at 15° C.-20° C. To this is then added, all at once, 15 g of iodide. The exothermic reaction is controlled with an ice bath to keep the temperature at 30° C. for about 90 min. Stirring is continued over 2 hrs and 30 min at 20° C., and the mixture is then taken to reflux for 4 hrs. The reaction mixture is left at rest for 56 hrs, and then the NaI precipitate is filtered. Toluene (700 ml) is added and the mixture filtered again. Toluene/ethanol azeotrope (700 ml) (rotavapor. 74° C./6× 104Pa) is distilled and 250 ml of the distillate is added to the residue. After cooling to 5° C., a new filtration is carried out. The filtrate is evaporated (74° C./2.7×104Pa). Raw product is purified on a Vigreux column, and then in a glass bolos column topped by a total reflux head, to yield ethyl-2-acetyl-2,4-dimethyl-4-pentenoate.

Workup

  1. temperaturewhile maintaining the temperature at 15° C.-20° C
  2. additionTo this is then added
  3. customThe exothermic reaction
  4. customis controlled with an ice bath
  5. customat 30° C.
  6. customfor about 90 min
  7. temperatureto reflux for 4 hrs
  8. waitThe reaction mixture is left at rest for 56 hrs
  9. filtrationthe NaI precipitate is filtered
  10. additionToluene (700 ml) is added
  11. filtrationthe mixture filtered again
  12. custom(700 ml) (rotavapor. 74° C./6× 104Pa)
  13. distillationis distilled
  14. addition250 ml of the distillate is added to the residue
  15. temperatureAfter cooling to 5° C.
  16. filtrationa new filtration
  17. customThe filtrate is evaporated (74° C./2.7×104Pa)
  18. customRaw product is purified on a Vigreux column

Sources & evidence

ORD record
ord-15db06836fee44cd85bd0f58bb718ac5
Source dataset
uspto-grants-1994_03
Patent number
US05292719

Reaction notes

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