Acetoacetic Acid → 5-Methoxycarbonyl-6-dimethoxymethyl-2-methyl-4-(3-nitrophenyl)-1,4-dihydropyridine-3-carboxylic acid

HRID 1380094Notes

Reaction equation

HRID 1380094 reaction equation
[N+:1]([C:4]1[CH:5]=[C:6]([CH:9]=[CH:10][CH:11]=1)[CH:7]=O)([O-:3])=[O:2].[C:12]([OH:18])(=[O:17])[CH2:13][C:14]([CH3:16])=O.[NH2:19]/[C:20](/[CH:26]([O:29][CH3:30])[O:27][CH3:28])=[CH:21]\[C:22]([O:24][CH3:25])=[O:23]>C(O)(C)(C)C>[CH3:25][O:24][C:22]([C:21]1[CH:7]([C:6]2[CH:9]=[CH:10][CH:11]=[C:4]([N+:1]([O-:3])=[O:2])[CH:5]=2)[C:13]([C:12]([OH:18])=[O:17])=[C:14]([CH3:16])[NH:19][C:20]=1[CH:26]([O:29][CH3:30])[O:27][CH3:28])=[O:23]

Participants

5

Reactant 3

HCID 96Acetoacetic AcidHCID 74493-NitrobenzaldehydeHCID 14025164Methyl 3-amino-4,4-dimethoxycrotonate

Product 1

HCID 202420645-Methoxycarbonyl-6-dimethoxymethyl-2-methyl-4-(3-nitrophenyl)-1,4-dihydropyridine-3-carboxylic acidYield 109.7%

Reagents, catalysts & solvents 1

HCID 6386tert-ButanolSolvent

Procedure

A solution of 3-nitrobenzaldehyde (3.02 g), 3-nitrooxy-2,2-bis(nitrooxymethyl)propyl ester of acetoacetic acid (7.10 g) and methyl 3-amino-4,4-dimethoxycrotonate (3.50 g) dissolved in tert-butyl alcohol (12 ml) was refluxed for 15 hours. The resulting mixture was cooled and concentrated under reduced pressure. The residue obtained was subjected to column chromatography on silica gel (200 g) and eluted with a mixture of toluene and ethyl acetate (10:1 by volume). The fractions containing the desired compound were collected and evaporated under reduced pressure to give a viscous oil of 3-nitrooxy-2,2-bis(nitrooxymethyl)propyl ester of 5-methoxycarbonyl-6-dimethoxymethyl-2-methyl-4-(3-nitrophenyl)-1,4-dihydropyridine-3-carboxylic acid (8.60 g).

Workup

  1. temperaturewas refluxed for 15 hours
  2. temperatureThe resulting mixture was cooled
  3. concentrationconcentrated under reduced pressure
  4. customThe residue obtained
  5. washeluted with a mixture of toluene and ethyl acetate (10:1 by volume)
  6. additionThe fractions containing the desired compound
  7. customwere collected
  8. customevaporated under reduced pressure

Sources & evidence

ORD record
ord-8c071ecbf5334962b40f98a25b4be9b2
Source dataset
uspto-grants-1986_04
Patent number
US04579859

Reaction notes

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