Acetic Anhydride → HCID 13469470, compound

HRID 1164605Notes

Reaction equation

HRID 1164605 reaction equation
[CH3:1][C:2]1[NH:3][C:4]([CH:23]=O)=[C:5]([C:18]([O:20][CH2:21][CH3:22])=[O:19])[CH:6]([C:13]2[O:14][CH:15]=[CH:16][CH:17]=2)[C:7]=1[C:8]([O:10][CH2:11][CH3:12])=[O:9].Cl.[NH2:26]O.C([O-])(=O)C.[Na+].C(OC(=O)C)(=O)C>C(O)(=O)C>[CH3:1][C:2]1[NH:3][C:4]([C:23]#[N:26])=[C:5]([C:18]([O:20][CH2:21][CH3:22])=[O:19])[CH:6]([C:13]2[O:14][CH:15]=[CH:16][CH:17]=2)[C:7]=1[C:8]([O:10][CH2:11][CH3:12])=[O:9]

Participants

6

Reactant 4

HCID 7918Acetic AnhydrideHCID 443297Hydroxyamine hydrochlorideHCID 517045Sodium AcetateHCID 13469467HCID 13469467, compound

Product 1

HCID 13469470HCID 13469470, compoundYield 51.6%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

A mixture of diethyl 2-methyl-4-(2-furyl)-6-formyl-1,4-dihydropyridine-3,5-dicarboxylate (1.6 g), hydroxylamine hydrochloride (383.6 mg) and sodium acetate (787.6 mg) in acetic acid (14 ml) was stirred for 30 minutes at room temperature. To the mixture, acetic anhydride (1 ml) was added and stirred for 1.5 hours at room temperature and further stirred for an hour under reflux. After removal of the acetic acid from the reaction mixture, water was added to the residue and the mixture was extracted with ethyl acetate. The extract was washed with saturated sodium bicarbonate solution and water and dried, and then the solvent was distilled off under reduced pressure. The resultant brown oil (1.8 g) was purified by column chromatography on silica gel by an eluent (a mixture of 15 parts of chloroform and one part of ethyl acetate by volume). The concentrate (920 mg) of the fraction of the eluate which showed one spot on thin-layer chromatography and the concentrate of one (450 mg) which showed plural spots respectively gave crystals (totally 875 mg) and these were recrystallized from a mixture of diethyl ether and n-hexane to give pure crystals (818 mg) of diethyl 2-methyl-4-(2-furyl)-6-cyano-1,4-dihydropyridine-3,5-dicarboxylate, m.p. 139° to 141° C.

Workup

  1. stirringstirred for 1.5 hours at room temperature
  2. stirringfurther stirred for an hour
  3. temperatureunder reflux
  4. customAfter removal of the acetic acid from the reaction mixture, water
  5. additionwas added to the residue
  6. extractionthe mixture was extracted with ethyl acetate
  7. washThe extract was washed with saturated sodium bicarbonate solution and water
  8. customdried
  9. distillationthe solvent was distilled off under reduced pressure
  10. customThe resultant brown oil (1.8 g) was purified by column chromatography on silica gel by an eluent (
  11. additiona mixture of 15 parts of chloroform and one part of ethyl acetate by volume)
  12. concentrationThe concentrate (920 mg) of the fraction of the eluate which
  13. concentrationthe concentrate of one (450 mg) which
  14. customthese were recrystallized from a mixture of diethyl ether and n-hexane

Sources & evidence

ORD record
ord-4ffd1da70825432f9380b3cbdff1c147
Source dataset
uspto-grants-1983_01
Patent number
US04370334

Reaction notes

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