Acetic Anhydride → HCID 13388332, compound

HRID 1164604Notes

Reaction equation

HRID 1164604 reaction equation
[CH3:1][C:2]1[NH:3][C:4]([CH:27]=O)=[C:5]([C:22]([O:24][CH2:25][CH3:26])=[O:23])[CH:6]([C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][C:14]=2[N+:19]([O-:21])=[O:20])[C:7]=1[C:8]([O:10][CH2:11][CH3:12])=[O:9].Cl.[NH2:30]O.C([O-])(=O)C.[Na+].C(OC(=O)C)(=O)C>C(O)(=O)C.C(OCC)(=O)C.C1C=CC=CC=1>[CH3:1][C:2]1[NH:3][C:4]([C:27]#[N:30])=[C:5]([C:22]([O:24][CH2:25][CH3:26])=[O:23])[CH:6]([C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][C:14]=2[N+:19]([O-:21])=[O:20])[C:7]=1[C:8]([O:10][CH2:11][CH3:12])=[O:9]

Participants

8

Reactant 4

HCID 7918Acetic AnhydrideHCID 443297Hydroxyamine hydrochlorideHCID 517045Sodium AcetateHCID 13388352Diethyl 2-methyl-4-(2-nitrophenyl)-6-formyl-1,4-dihydropyridine-3,5-dicarboxylate

Product 1

HCID 13388332HCID 13388332, compoundYield 61.1%

Reagents, catalysts & solvents 3

HCID 176Acetic AcidSolventHCID 241BenzeneSolventHCID 8857Ethyl AcetateSolvent

Procedure

A mixture of diethyl 2-methyl-4-(2-nitrophenyl)-6-formyl-1,4-dihydropyridine-3,5-dicarboxylate (2.03 g), hydroxylamine hydrochloride (417 mg), sodium acetate (861.4 mg) in acetic acid (15 ml) was stirred at room temperature for 30 minutes. Acetic anhydride (1 ml) was added to the reaction mixture, and the mixture was stirred at room temperature for 90 minutes and further refluxed for an hour. The acetic acid was distilled off under reduced pressure, and to the resultant residue was added water, and the aqueous mixture was adjusted to pH 7 to 8 with sodium bicarbonate and extracted with diethyl ether. The extract was washed with water, dried over magnesium sulfate and then concentrated under reduced pressure to give an oil. This oil was subjected to column chromatography on silica gel with an eluent [a mixture of 4 parts of benzene and one part of ethyl acetate by volume]. The resultant oily substance (1.7 g) was crystallized by treating with a mixture of diethyl ether and n-hexane. These crystals (1.5 g) were recrystallized from a mixture of diethyl ether and n-hexane to give pure crystals (1.23 g) of diethyl 2-methyl-4-(2-nitrophenyl)-6-cyano-1,4-dihydropyridine-3,5-dicarboxylate, mp 126° to 127.5° C.

Workup

  1. stirringthe mixture was stirred at room temperature for 90 minutes
  2. temperaturefurther refluxed for an hour
  3. distillationThe acetic acid was distilled off under reduced pressure
  4. additionto the resultant residue was added water
  5. extractionextracted with diethyl ether
  6. washThe extract was washed with water
  7. dry with materialdried over magnesium sulfate
  8. concentrationconcentrated under reduced pressure
  9. customto give an oil
  10. customThe resultant oily substance (1.7 g) was crystallized
  11. additionby treating with a mixture of diethyl ether and n-hexane
  12. customThese crystals (1.5 g) were recrystallized from a mixture of diethyl ether and n-hexane

Sources & evidence

ORD record
ord-2f8b1462df4749f3aaa0d75549a3caba
Source dataset
uspto-grants-1983_01
Patent number
US04370334

Reaction notes

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