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

HRID 1380095Notes

Reaction equation

HRID 1380095 reaction equation
[CH3:1][O:2][C:3]([C:5]1[CH:6]([C:20]2[CH:25]=[CH:24][CH:23]=[C:22]([N+:26]([O-:28])=[O:27])[CH:21]=2)[C:7]([C:17]([OH:19])=[O:18])=[C:8]([CH3:16])[NH:9][C:10]=1[CH:11](OC)[O:12]C)=[O:4]>Cl.CC(C)=O.C(OCC)(=O)C>[CH:11]([C:10]1[NH:9][C:8]([CH3:16])=[C:7]([C:17]([OH:19])=[O:18])[CH:6]([C:20]2[CH:25]=[CH:24][CH:23]=[C:22]([N+:26]([O-:28])=[O:27])[CH:21]=2)[C:5]=1[C:3]([O:2][CH3:1])=[O:4])=[O:12]

Participants

5

Reactant 1

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

Product 1

HCID 202420636-Formyl-5-methoxycarbonyl-2-methyl-4-(3-nitrophenyl)-1,4-dihydropyridine-3-carboxylic acidYield 79%

Reagents, catalysts & solvents 3

HCID 180AcetoneSolventHCID 313Hydrochloric AcidSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
20 °C

Procedure

A solution 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 (7.50 g) dissolved in a mixture of 6N hydrochloric acid (22.5 ml) and acetone (90 ml) was stirred for 6.5 hours at 20° C. The resulting mixture was evaporated under reduced pressure. The residue obtained was dissolved in ethyl acetate, and washed successively with water, an aqueous sodium bicarbonate and an aqueous sodium chloride. The ethyl acetate solution was dried over anhydrous magnesium sulfate and evaporated 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 and recrystallized from a mixture of ethyl acetate and diisopropyl ether to give yellow crystals of 3-nitrooxy-2,2-bis(nitrooxymethyl)propyl ester of 6-formyl-5-methoxycarbonyl-2-methyl-4-(3-nitrophenyl)-1,4-dihydropyridine-3-carboxylic acid (5.23 g), mp 125° to 125.5° C.

Workup

  1. customThe resulting mixture was evaporated under reduced pressure
  2. customThe residue obtained
  3. washwashed successively with water
  4. dry with materialThe ethyl acetate solution was dried over anhydrous magnesium sulfate
  5. customevaporated under reduced pressure
  6. customThe residue obtained
  7. washeluted with a mixture of toluene and ethyl acetate (10:1 by volume)
  8. additionThe fractions containing the desired compound
  9. customwere collected
  10. customevaporated under reduced pressure
  11. customrecrystallized from a mixture of ethyl acetate and diisopropyl ether

Sources & evidence

ORD record
ord-60e89a080e4c4052a7fe16f512addce2
Source dataset
uspto-grants-1986_04
Patent number
US04579859

Reaction notes

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