Transesterification over various zeolites under liquid-phase conditions |
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Authors: | M. Sasidharan R. Kumar |
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Affiliation: | a Laboratory for Membrane Chemistry, Tohoku AIST, 4-2-1 Nigatake, Miyagino-ku 983-8551, Sendai, Japan b Catalysis Division, National Chemical Laboratory, Pune 411 008, India |
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Abstract: | Transesterification of β-keto esters with a variety of alcohols to the corresponding β-keto esters has been carried out efficiently over aluminosilicates simply by refluxing in toluene under liquid-phase conditions. Aliphatic β-keto esters exhibit the higher reactivity than the aromatic and/or cyclic β-keto esters, whereas other esters such as -keto esters, ,β-unsaturated esters, normal esters, and -halo esters fail to undergo the transesterification. The reaction proceeds smoothly with primary alcohols than the tertiary-, cyclic-, and allylic alcohols. The large-pore zeolites such as Y, mordenite, and β show higher activity than the medium-pore ZSM-5 and the partial removal of framework aluminum from the large-pore zeolites by dealumination increases their activity. The aluminum containing mesoporous MCM-41 shows poor activity. Among the different solvents used toluene leads to the highest activity and the optimum catalyst concentration found was ca. 20 wt.% of the substrate. The activity increases with increasing reaction temperature. The reaction pathway consists of formation of acyl ketene intermediate by the interaction of β-keto esters with Brønsted acid sites of the catalyst, followed by nucleophilic attack of the alcohol at the electrophilic center and successive elimination of the proton to give the product. |
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Keywords: | Transesterification β-keto esters Zeolites Dealumination Liquid-phase |
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