Efficient transesterification of ethyl acetoacetate with higher alcohols without catalysts

Tetrahedron Letters

Volumn 49, Issue 10, 2008, Pages 1645-1647

  Koval, L I ^a   Dzyuba, V I ^a   Ilnitska, O L ^a   Pekhnyo, V I ^a  

^a INSTITUTE OF GENERAL AND INORGANIC CHEMISTRY   (Ukraine)

Author keywords

Ketoesters; Alcohols; Molecular sieves; Transesterification

Indexed keywords

2 METHYL 2 BUTANOL; ACETOACETIC ACID; ACETOACETIC ACID ETHYL ESTER; ALCOHOL; UNCLASSIFIED DRUG;

ARTICLE; CATALYST; CHEMICAL STRUCTURE; KINETICS; REACTION TIME; SYNTHESIS; TRANSESTERIFICATION;

EID: 38949207877     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.tetlet.2008.01.018     Document Type: Article

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21. General procedure for the transesterification: freshly distilled (or sublimated) dry alcohol (1 equiv) and ethyl acetoacetate (1 equiv) were refluxed (Table 1) in dry toluene under an inert-gas atmosphere in a system provided with Soxhlet extractor body (filled with molecular sieves) to remove the ethanol formed. Toluene was chosen as a solvent since it forms an azeotropic mixture with an ethanol content of 70%, owing to which the effectiveness of ethanol removal increases (unlike benzene, in which the reaction does not go to completion under the same conditions). The inert atmosphere was produced by passing argon through a capillary; gas bubbles created boiling centers on the one hand and prevented superfluous resinification of the reaction medium on the other hand. The extent of the reaction was checked by TLC. The solvent was removed using a rotary evaporator. The residues were distilled in vacuo to yield the products. All products were analyzed by bp, NMR, IR, GC and HPLC, and the spectra were consistent with the structures of the desired products.
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