Acetic Acid → Ethyl 2-(2-methoxycarbonylbenzyliden)-4,4-diethoxyacetoacetate

HRID 1164632Notes

Reaction equation

HRID 1164632 reaction equation
[CH:1]([C:3]1[CH:12]=[CH:11][CH:10]=[CH:9][C:4]=1[C:5]([O:7][CH3:8])=[O:6])=O.[CH2:13]([O:15][CH:16]([O:25][CH2:26][CH3:27])[C:17](=[O:24])[CH2:18][C:19]([O:21][CH2:22][CH3:23])=[O:20])[CH3:14].C(O)(=O)C.N1CCCCC1>C1C=CC=CC=1>[CH3:8][O:7][C:5]([C:4]1[CH:9]=[CH:10][CH:11]=[CH:12][C:3]=1[CH:1]=[C:18]([C:17]([CH:16]([O:15][CH2:13][CH3:14])[O:25][CH2:26][CH3:27])=[O:24])[C:19]([O:21][CH2:22][CH3:23])=[O:20])=[O:6]

Participants

6

Reactant 4

HCID 176Acetic AcidHCID 8082PiperidineHCID 243003Methyl 2-formylbenzoateHCID 11138577Ethyl 4,4-diethoxy-3-oxobutanoate

Product 1

HCID 54462958Ethyl 2-(2-methoxycarbonylbenzyliden)-4,4-diethoxyacetoacetateYield 116.3%

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent2×

Procedure

To a mixture of methyl 2-formylbenzoate (4.92 g), ethyl 4,4-diethoxyacetoacetate (7.2 g) and acetic acid (0.36 g) in benzene (15 ml) was added portionwise each one third portion of a solution of piperidine (306 mg) in benzene (5 ml) for each 20 minutes' interval, and the mixture was heated to reflux for 3 hours under removing off azeotropically the resulting water. After cooling, the reaction mixture was diluted with additional benzene (25 ml), washed three times with water and successively with diluted aqueous sodium bicarbonate solution, water and saturated aqueous sodium chloride solution and dried over magnesium sulfate. The solvent was distilled off under reduced pressure to give reddish oil (12.7 g) of crude ethyl 2-(2-methoxycarbonylbenzyliden)-4,4-diethoxyacetoacetate which was used in the following reaction without any further purification.

Workup

  1. temperaturethe mixture was heated
  2. temperatureto reflux for 3 hours
  3. customunder removing off azeotropically the resulting water
  4. temperatureAfter cooling
  5. additionthe reaction mixture was diluted with additional benzene (25 ml)
  6. washwashed three times with water
  7. dry with materialsuccessively with diluted aqueous sodium bicarbonate solution, water and saturated aqueous sodium chloride solution and dried over magnesium sulfate
  8. distillationThe solvent was distilled off under reduced pressure

Sources & evidence

ORD record
ord-42a6d8f22a044207803dbeea8e05f9da
Source dataset
uspto-grants-1983_01
Patent number
US04370334

Reaction notes

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