Acetic Acid → HCID 53770526, compound

HRID 1649402Notes

Reaction equation

HRID 1649402 reaction equation
[CH3:1][C:2]1[CH:9]=[C:8]([CH3:10])[CH:7]=[C:6]([CH3:11])[C:3]=1[CH:4]=O.[CH2:12]([O:14][C:15](=[O:21])[CH2:16][C:17]([CH2:19][Cl:20])=[O:18])[CH3:13].N1CCCCC1.C(O)(=O)C>C1C=CC=CC=1.C(OCC)(=O)C.O>[CH2:12]([O:14][C:15](=[O:21])[C:16](=[CH:4][C:3]1[C:2]([CH3:1])=[CH:9][C:8]([CH3:10])=[CH:7][C:6]=1[CH3:11])[C:17](=[O:18])[CH2:19][Cl:20])[CH3:13]

Participants

8

Reactant 4

HCID 176Acetic AcidHCID 8082PiperidineHCID 102542,4,6-TrimethylbenzaldehydeHCID 69484Ethyl 4-chloroacetoacetate

Product 1

HCID 53770526HCID 53770526, compoundYield 39%

Reagents, catalysts & solvents 3

HCID 241BenzeneSolventHCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Procedure

90 g of 2,4,6-trimethylbenzaldehyde, 150 g of 4-chloroacetoacetic acid ethyl ester, 2.6 ml of piperidine and 7 ml of glacial acetic acid were dissolved in 60 ml of benzene and the solution was boiled for 6 hours using a water separator. 200 ml of ethyl acetate were added to the cooled solution, the solution was extracted in each case once with saturated sodium bicarbonate solution, water and 1 M citric acid solution and the extract was dried over magnesium sulphate and evaporated. The crude product was subjected to incipient distillation under a high vacuum in order to free it from excess 4-chloroacetoacetic acid ethyl ester. After chromatography of the product on Silica gel 60 (Merck, 70-230 mesh), 21 g of the E-isomer could be crystallized with isopropanol and 3:1 Z/E mixture remained as the mother liquor in the form of an oil. Total yield: 39%. E-isomer: melting point 85°.

Workup

  1. extractionthe solution was extracted in each case once with saturated sodium bicarbonate solution, water and 1 M citric acid solution
  2. dry with materialthe extract was dried over magnesium sulphate
  3. customevaporated
  4. distillationThe crude product was subjected to incipient distillation under a high vacuum in order
  5. customAfter chromatography of the product on Silica gel 60 (Merck, 70-230 mesh), 21 g of the E-isomer could be crystallized with isopropanol and 3:1 Z/E mixture

Sources & evidence

ORD record
ord-052a5b9879bd4b049e3c9f20ebad22fc
Source dataset
uspto-grants-1983_11
Patent number
US04416880

Reaction notes

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