Acetoacetic Acid → HCID 53772019, compound

HRID 1380090Notes

Reaction equation

HRID 1380090 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:14].C(O)(=O)C.N1CCCCC1>C1C=CC=CC=1.O>[Cl:1][C:2]1[C:9]([Cl:10])=[CH:8][CH:7]=[CH:6][C:3]=1[CH:4]=[C:12]([C:13]([CH3:15])=[O:14])[C:11]([OH:17])=[O:16]

Participants

7

Reactant 4

HCID 96Acetoacetic AcidHCID 176Acetic AcidHCID 8082PiperidineHCID 357452,3-Dichlorobenzaldehyde

Product 1

HCID 53772019HCID 53772019, compound

Reagents, catalysts & solvents 2

HCID 241BenzeneSolventHCID 962WaterSolvent

Procedure

A mixture of 2,3-dichlorobenzaldehyde (0.88 g), 3-nitrooxy-2,2-bis(nitrooxymethyl)propyl ester of acetoacetic acid (1.78 g), acetic acid (50 mg), and piperidine (50 mg) in benzene (10 ml) was refluxed for 1.75 hours, during which time water formed was removed azeotropically. The resulting mixture was cooled, washed successively with water, an aqueous sodium bicarbonate and water, dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give 3-nitrooxy-2,2,-bis(nitrooxymethyl)propyl ester of 2-(2,3-dichlorobenzylidene)acetoacetic acid. Ethyl 3-aminocrotonate was mixed with the product obtained above. The resulting mixture was stirred for 1.5 hours at 80° to 90° C., and then cooled. The mixture in ethyl acetate was washed with an aqueous sodium chloride. The ethyl acetate layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue obtained was subjected to column chromatography and eluted with a mixture of ethyl acetate and toluene (1:12 by volume). The fractions containing the desired compound were collected and evaporated under reduced pressure to give yellowish powders. The powders were recrystallized from ethanol to give yellowish crystals of 3-nitrooxy-2,2-bis(nitrooxymethyl)propyl ester of 4-(2,3-dichlorophenyl)-5-ethoxycarbonyl-2,6-dimethyl-1,4-dihydropyridine-3-carboxylic acid (1.39 g), mp 135° to 137° C.

Workup

  1. customformed
  2. customwas removed azeotropically
  3. temperatureThe resulting mixture was cooled
  4. washwashed successively with water
  5. dry with materialan aqueous sodium bicarbonate and water, dried over anhydrous magnesium sulfate
  6. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-1af76b6bcf0c4d258fb2042fa1855837
Source dataset
uspto-grants-1986_04
Patent number
US04579859

Reaction notes

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