4-Nitrobenzaldehyde → HCID 23004114, compound

HRID 382691Notes

Reaction equation

HRID 382691 reaction equation
[C:1]1([C:7](=O)[CH2:8][C:9]([O:11]CCC#N)=[O:10])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[N+:17]([C:20]1[CH:27]=[CH:26][C:23]([CH:24]=O)=[CH:22][CH:21]=1)([O-:19])=[O:18].[NH2:28]/[C:29](/[CH3:35])=[CH:30]\[C:31]([O:33][CH3:34])=[O:32]>C(O)(C)C>[CH3:34][O:33][C:31]([C:30]1[CH:24]([C:23]2[CH:26]=[CH:27][C:20]([N+:17]([O-:19])=[O:18])=[CH:21][CH:22]=2)[C:8]([C:9]([OH:11])=[O:10])=[C:7]([C:1]2[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=2)[NH:28][C:29]=1[CH3:35])=[O:32]

Participants

5

Reactant 3

HCID 5414-NitrobenzaldehydeHCID 643918Methyl 3-aminocrotonateHCID 23004134HCID 23004134, compound

Product 1

HCID 23004114HCID 23004114, compoundYield 55.1%

Reagents, catalysts & solvents 1

HCID 3776IsopropanolSolvent

Procedure

A solution of 5.0 g of 2-cyanoethyl 3-phenyl-3-oxopropionate (23.1 mmol), 6.98 g of 4-nitrobenzaldehyde (46.2 mmol), and 5.32 g of methyl 3-aminocrotonate (46.2 mmol) in 100 mL of isopropanol were heated at reflux temperature for 2 days, cooled, and the solvent was removed in vacuo. This residue was dissolved in 50 mL of warm dioxane and 1.21 g of NaOH in 25 mL of water was added to the reaction mixture. The resulting maroon solution was stirred for 3 hrs. The solvent was removed in vacuo. The residue was partitioned between water (100 mL) and ethyl acetate (50 mL), separated, and washed with ethyl acetate (3×50 mL). The aqueous extract was acidified with concentrated HCl (pH 2-3), the precipitated solids were filtered, and washed with water (2×20 mL). The crude product was recrystallized from acetone-water mixture to give 5.02 g (55%) of yellow amorphous solid: mp 190-191° C.; Anal. Calcd for C21H18N2O4: C, 63.96; H, 4.60; N, 7.10. Found: C, 63.86; H, 4.59; N, 7.04.

Workup

  1. temperatureat reflux temperature for 2 days
  2. temperaturecooled
  3. customthe solvent was removed in vacuo
  4. dissolutionThis residue was dissolved in 50 mL of warm dioxane
  5. addition1.21 g of NaOH in 25 mL of water was added to the reaction mixture
  6. customThe solvent was removed in vacuo
  7. customThe residue was partitioned between water (100 mL) and ethyl acetate (50 mL)
  8. customseparated
  9. washwashed with ethyl acetate (3×50 mL)
  10. extractionThe aqueous extract
  11. filtrationthe precipitated solids were filtered
  12. washwashed with water (2×20 mL)
  13. customThe crude product was recrystallized from acetone-water mixture

Sources & evidence

ORD record
ord-c67612d6eb83466abdd992e85c6bbd96
Source dataset
uspto-grants-2001_10
Patent number
US06310076B1

Reaction notes

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