4-Nitrobenzaldehyde → HCID 23004102, compound

HRID 396629Notes

Reaction equation

HRID 396629 reaction equation
O=[C:2]([CH2:11][CH2:12][CH3:13])[CH2:3][C:4]([O:6]CCC#N)=[O:5].[NH2:14]/[C:15](/[CH3:21])=[CH:16]\[C:17]([O:19][CH3:20])=[O:18].[N+:22]([C:25]1[CH:32]=[CH:31][C:28]([CH:29]=O)=[CH:27][CH:26]=1)([O-:24])=[O:23]>C(O)(C)C>[CH3:20][O:19][C:17]([C:16]1[CH:29]([C:28]2[CH:31]=[CH:32][C:25]([N+:22]([O-:24])=[O:23])=[CH:26][CH:27]=2)[C:3]([C:4]([OH:6])=[O:5])=[C:2]([CH2:11][CH2:12][CH3:13])[NH:14][C:15]=1[CH3:21])=[O:18]

Participants

5

Reactant 3

HCID 5414-NitrobenzaldehydeHCID 643918Methyl 3-aminocrotonateHCID 23004047HCID 23004047, compound

Product 1

HCID 23004102HCID 23004102, compound

Reagents, catalysts & solvents 1

HCID 3776IsopropanolSolvent

Procedure

A mixture of 2-cyanoethyl 3-oxohexanoate (11.9 mmol), methyl 3-aminocrotonate (11.9 mmol), and 4-nitrobenzaldehyde in 25 mL of isopropanol were heated at reflux temperature for 16 h, cooled, and the solvent was removed under reduced pressure. The residue was dissolved in 15 mL of dioxane (slightly warmed with a heat gun to dissolve the product) and 626 mg of NaOH in 15 mL of water was added to the reaction mixture. After 0.5 hrs, the maroon solution was concentrated to a small volume under reduced pressure, partitioned between 50 mL of water and 50 mL of ethyl acetate, separated, and the aqueous solution was washed with 2×20 mL of ethyl acetate. The aqueous extract was acidified with concentrated HCl (pH=2), and the precipitated oil was extracted with ethyl acetate (2×40 mL). The combined organic extracts were dried (MgSO4), and the solvent was removed in vacuo to give the desired product as a foamy yellow solid. The acid was used in the next step without further purification.

Workup

  1. temperaturewere heated
  2. temperatureat reflux temperature for 16 h
  3. temperaturecooled
  4. customthe solvent was removed under reduced pressure
  5. dissolutionThe residue was dissolved in 15 mL of dioxane (
  6. temperatureslightly warmed with a heat gun
  7. dissolutionto dissolve the product) and 626 mg of NaOH in 15 mL of water
  8. additionwas added to the reaction mixture
  9. concentrationthe maroon solution was concentrated to a small volume under reduced pressure
  10. custompartitioned between 50 mL of water and 50 mL of ethyl acetate
  11. customseparated
  12. washthe aqueous solution was washed with 2×20 mL of ethyl acetate
  13. extractionThe aqueous extract
  14. extractionthe precipitated oil was extracted with ethyl acetate (2×40 mL)
  15. dry with materialThe combined organic extracts were dried (MgSO4)
  16. customthe solvent was removed in vacuo

Sources & evidence

ORD record
ord-6c2ea5e0b2784c899db3be6187c84897
Source dataset
uspto-grants-2003_08
Patent number
US06608086B2

Reaction notes

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