Acetoacetic Acid → HCID 22923935, compound

HRID 1380091Notes

Reaction equation

HRID 1380091 reaction equation
[Cl:1][C:2]1[C:9]([Cl:10])=[CH:8][CH:7]=[CH:6][C:3]=1[CH:4]=O.[C:11]([OH:17])(=[O:16])[CH2:12][C:13]([CH3:15])=O.[NH2:18]/[C:19](/[CH3:27])=[CH:20]\[C:21]([O:23][CH:24]([CH3:26])[CH3:25])=[O:22]>C(O)(C)(C)C>[Cl:1][C:2]1[C:9]([Cl:10])=[CH:8][CH:7]=[CH:6][C:3]=1[CH:4]1[C:20]([C:21]([O:23][CH:24]([CH3:26])[CH3:25])=[O:22])=[C:19]([CH3:27])[NH:18][C:13]([CH3:15])=[C:12]1[C:11]([OH:17])=[O:16]

Participants

5

Reactant 3

HCID 96Acetoacetic AcidHCID 357452,3-DichlorobenzaldehydeHCID 111372742-Butenoic acid, 3-amino-, 1-methylethyl ester

Product 1

HCID 22923935HCID 22923935, compoundYield 88.9%

Reagents, catalysts & solvents 1

HCID 6386tert-ButanolSolvent

Conditions

Temperature
25 °C

Procedure

A solution of 2,3-dichlorobenzaldehyde (0.70 g), 3-nitrooxy-2,2-bis(nitrooxymethyl)propyl ester of acetoacetic acid (1.42 g) and isopropyl 3-aminocrotonate (0.57 g) in tert-butyl alcohol (3 ml) was refluxed for 5.5 hours. The resulting mixture was cooled to 25° C., and then concentrated under reduced pressure. The residue obtained was subjected to column chromatography on silica gel (60 g) and eluted with chloroform. The fractions containing the desired compound were collected and evaporated under reduced pressure to give white powders. The powders were recrystallized from a mixture of diethyl ether and diisopropyl ether to give white crystals of 3-nitrooxy-2,2-bis(nitrooxymethyl)propyl ester of 4-(2,3-dichlorophenyl)-5-isopropoxycarbonyl-2,6-dimethyl-1,4-dihydropyridine-3-carboxylic acid (1.36 g), mp 155° to 156.5° C.

Workup

  1. concentrationconcentrated under reduced pressure
  2. customThe residue obtained
  3. washeluted with chloroform
  4. additionThe fractions containing the desired compound
  5. customwere collected
  6. customevaporated under reduced pressure
  7. customto give white powders
  8. customThe powders were recrystallized from a mixture of diethyl ether and diisopropyl ether

Sources & evidence

ORD record
ord-68a33aa177554789b2087c554f837934
Source dataset
uspto-grants-1986_04
Patent number
US04579859

Reaction notes

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