Acetoacetic Acid → H-152/81

HRID 1380089Notes

Reaction equation

HRID 1380089 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](/[CH3:25])=[CH:20]\[C:21]([O:23][CH3:24])=[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][CH3:24])=[O:22])=[C:19]([CH3:25])[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 643918Methyl 3-aminocrotonate

Product 1

HCID 2794058H-152/81Yield 78%

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 methyl 3-amino-crotonate (0.46 g) in tert-butyl alcohol (3 ml) was refluxed for 4.5 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 a mixture of chloroform and methanol (100:1 by volume). The fractions containing the desired compound were collected and evaporated under reduced pressure. The residue obtained was recrystallized from a mixture of diethyl ether and diisopropyl ether to give 3-nitrooxy-2,2-bis(nitrooxymethyl)propyl ester of 4-(2,3-dichlorophenyl)-5-methoxycarbonyl-2,6-dimethyl-1,4-dihydropyridine-3-carboxylic acid (1.11 g), mp 115° to 117.5° C.

Workup

  1. concentrationconcentrated under reduced pressure
  2. customThe residue obtained
  3. washeluted with a mixture of chloroform and methanol (100:1 by volume)
  4. additionThe fractions containing the desired compound
  5. customwere collected
  6. customevaporated under reduced pressure
  7. customThe residue obtained
  8. customwas recrystallized from a mixture of diethyl ether and diisopropyl ether

Sources & evidence

ORD record
ord-ddba936e8dbf4d18af998d53a21239d4
Source dataset
uspto-grants-1986_04
Patent number
US04579859

Reaction notes

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