Acetic Acid → HCID 53921987, compound

HRID 1649409Notes

Reaction equation

HRID 1649409 reaction equation
[CH2:1]([O:3][C:4](=[O:10])[CH2:5][C:6]([CH2:8][Cl:9])=[O:7])[CH3:2].[CH3:11][O:12][C:13]1[CH:20]=[C:19]([O:21][CH3:22])[C:18]([O:23][CH3:24])=[CH:17][C:14]=1[CH:15]=O.C(O)(=O)C.N1CCCCC1>C1C=CC=CC=1.C(OCC)(=O)C.O>[CH2:1]([O:3][C:4](=[O:10])[C:5](=[CH:15][C:14]1[CH:17]=[C:18]([O:23][CH3:24])[C:19]([O:21][CH3:22])=[CH:20][C:13]=1[O:12][CH3:11])[C:6](=[O:7])[CH2:8][Cl:9])[CH3:2]

Participants

8

Reactant 4

HCID 176Acetic AcidHCID 8082PiperidineHCID 205252,4,5-TrimethoxybenzaldehydeHCID 69484Ethyl 4-chloroacetoacetate

Product 1

HCID 53921987HCID 53921987, compoundYield 28.6%

Reagents, catalysts & solvents 3

HCID 241BenzeneSolventHCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Procedure

42 g of 4-chloroacetoacetic acid ethyl ester, 50 g of 2,4,5-trimethoxybenzaldehyde, 2.5 ml of glacial acetic acid and 1 ml of piperidine were dissolved in 60 ml of benzene and the solution was boiled for two hours using a water separator. Although conversion was not yet complete, the mixture was worked up. It was diluted with 200 ml of ethyl acetate, extracted in each case three times with saturated sodium bicarbonate solution, water, 1 M citric acid solution and again with water, dried and evaporated. On fractional crystallization of the residue from methanol, first 20 g of pure product, as the E/Z mixture, and then 10.5 g of unreacted aldehyde could be crystallized. In addition to a large amount of product, the mother liquor still contained only a little aldehyde and, after preliminary purification by chromatography on silica gel, could likewise be crystallized. A further 25 g of product were obtained.

Workup

  1. extractionextracted in each case three times with saturated sodium bicarbonate solution, water, 1 M citric acid solution and again with water
  2. customdried
  3. customevaporated
  4. customOn fractional crystallization of the residue from methanol, first 20 g of pure product
  5. customas the E/Z mixture, and then 10.5 g of unreacted aldehyde could be crystallized
  6. additionIn addition to a large amount of product
  7. customafter preliminary purification by chromatography on silica gel
  8. customcould likewise be crystallized

Sources & evidence

ORD record
ord-1b2e38a1bd484e17a56ccfc5605eca94
Source dataset
uspto-grants-1983_11
Patent number
US04416880

Reaction notes

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