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Side-chain alkylation of 2,6-lutidine to 2,6-divinylpyridine over basic zeolites

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Abstract

Synthesis of 2,6-divinylpyridine (2,6-DVP) and 2-methyl-6-vinylpyridine (2M6VP) was achieved for the first time by side-chain alkylation of 2,6-lutidine using formaldehyde (37 wt/v) as alkylating agent in heterogeneous conditions at atmospheric pressure, and at a reaction temperature of 300 °C over alkali and alkaline metal ion modified zeolites. A mixture of 2,6-divinylpyridine and 2-methyl,6-vinylpyridine were formed by the alkylation of the 2,6-lutidine over Li, Na, K, Rb, Cs, Mg, Ca, Sr and Ba metal ion modified zeolites. The catalytic activity of 2,6-lutidine was studied over various potassium metal ion modified zeolite molecular sieves like ZSM-5 (30), X, Y, mordenite and MCM-41. Alkali modified ZSM-5 (30) catalyst was found more active in side-chain alkylation of 2,6-lutidine when compared to other zeolites. Among all these catalysts studied K modified ZSM-5 (30) gave best conversion of 2,6-lutidine and selectivity to 2-methyl,6-vinylpyridine. K-ZSM-5 (30) catalyst was employed to study the reaction parameters like reaction temperature, weight hourly space velocity, molar ratio, and time on stream for 2,6-lutidine. The effect of potassium metal ion content and precursors of potassium ion on catalytic activity in side-chain alkylation of 2,6-lutidine was studied. The bifunctional catalyst is required containing medium or weak acidic centers and basic centers in the side-chain alkylation, which is understood through proposed mechanism. The selectivities of 2,6-DVP were 45.2, 40.0, and 30.7% at 73.4, 66.0 and 60.5% conversion at 300 °C from 2,6-lutidine and formaldehyde over K-ZSM-5 (30), Rb-ZSM-5 (30) and Cs-K-ZSM-5 (30), respectively.

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Acknowledgments

Author G.M. is thankful to CSIR for Senior Research Fellowship and also thankful to Dr. M. Ramakrishna Prasad and Dr. K.V.V. Krishna Mohan for help.

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Authors and Affiliations

  1. Catalysis Group, Indian Institute of Chemical Technology, Hyderabad, 500 007, India

    G. Madhavi, S. J. Kulkarni & K. V. Raghavan

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  1. G. Madhavi
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  2. S. J. Kulkarni
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  3. K. V. Raghavan
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Correspondence to S. J. Kulkarni.

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Madhavi, G., Kulkarni, S.J. & Raghavan, K.V. Side-chain alkylation of 2,6-lutidine to 2,6-divinylpyridine over basic zeolites. J Porous Mater 14, 379–385 (2007). https://doi.org/10.1007/s10934-006-9030-1

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  • DOI: https://doi.org/10.1007/s10934-006-9030-1

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