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Catalysis in Green Chemistry and Engineering

ISSN Imprimir: 2572-9896
ISSN En Línea: 2572-990X

Catalysis in Green Chemistry and Engineering

DOI: 10.1615/CatalGreenChemEng.2019030025
pages 43-54

GREEN SYNTHESIS OF 2,3-OXYBUTYL MALONONITRILE VIAMICHAEL REACTION OF METHYL VINYL KETONE WITH MALONONITRILE OVER TITANIA AND ZINC LOADED HYDROTALCITE CATALYSTS

Amarsinh L. Jadhav
Department of Chemical Engineering, Institute of Chemical Technology, Nathalal Parekh Marg, Matunga, Mumbai 400019, India
Ganapati D. Yadav
Department of Chemical Engineering, Institute of Chemical Technology, Nathalal Parekh Marg, Matunga, Mumbai 400019, India

SINOPSIS

Hydrotalcites have come of age. A modification of hydrotalcite activated with zinc and titanium was used to synthesize novel materials to catalyze Michael addition reaction of malononitrile with methyl vinyl ketone. The product of this reaction, 2,3-oxybutylmalononitrile, has applications in pharmaceuticals, perfumery, and flavor industries, where it is produced by non-green routes. The effect of mesoporous tubular structure in generation of mild basic sites in modified hydrotalcite-based catalysts is discussed in this article. The reaction is atom economical from a Green Chemistry point of view. Titanium and zinc-based hydrotalcite catalysts were synthesized by using titanium isopropoxide, zinc nitrate, aluminum nitrate, and magnesium nitrate in basic medium by combustion synthesis using different fuels. These modified hydrotalcites were characterized by SEM, EDXS, N2 adsorption, CO2-TPD, NH3-TPD, and XRD techniques. Zinc-modified Al-Mg hydrotalcite using glycine as the fuel was the most selective, active, and reusable catalyst. A Langmuir-Hinshelwood-Hougen-Watson (LHHW) model was used to establish the reaction mechanism and kinetics. All species were weakly adsorbed, leading to the second order power law model. Using a mole ratio of 1:2 of methyl vinyl ketone to malononitrile, with methanol as solvent and 0.01 g/cm3 catalyst loading, the reaction gave 61.9% conversion of methyl vinyl ketone and 94.6% selectivity to 2,3-oxybutyl malononitrile in 3 h at 60°C. The apparent activation energy was 10.12 kcal/mol. The process is green.

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