Abstract
Terpyridines are unique class of functional compounds that is extensively spotlighted in diverse fields like synthesis of supramolecular chemistry, nanomaterials, medicinal chemistry intermediates, drugs and active pharmaceutical ingredients and so on. The key challenges for the production of terpyridine lie in the bulk scale synthesis of intermediates. The expansively used synthon for terpyridine synthesis is 4′-chloro-2,2′:6′,2″-terpyridine and their bulk scale synthesis under the ambient conditions using a Fe3O4@SiO2 magnetic nanomaterial catalyst is investigated in the present work. In the protocol stabilized, ethyl-2-pinacolate and acetone were reacted in the presence of NaH to obtain 1,5-bis(2-pyridinyl) pentane-1,3,5-trione. The enolate of acetone is difficult to generate even with NaH and we used Fe3O4@SiO2 to increase the rate of H2 gas evolution. The triketone is cyclized with CH3COONH4 to obtain 2,6-bis(2-pyridinyl)-4-pyridine. This reaction proceeds quantitatively and the off-white solid was easy to isolate from the reaction medium. The subsequent aromatization was observed with PCl5/POCl3 and acidic silica gel promoted the product yield to reach ~78%. The crux of the present protocol is that it does not involve any column purification and significant yield of 4′-chloro-2,2′:6′,2″-terpyridine can be conveniently attained. The Fe3O4@SiO2 aids in the stabilization of carbonyl on the solid support and abstraction of hydrogen from methyl group of acetone. The 40 nm sized Fe3O4@SiO2 favored the maximum yield attributed to the density of active sites to promote the reactions. Due to high value nature of 4′-chloro-2,2′:6′,2″-terpyridine, the nominal 30% yield improvement achieved at the bulk scale gauges significant at the industrial scale.
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Acknowledgements
We thank Dr. G. C. Reddy, eminent scientist at VMSRF, Bangalore for technical guidance, process chemistry advice and methods to deploy in the chemical reactors. This research is supported by Department of Science and Technology, DST Nanomission, Government of India, under with Grant no. SR/NM/NT-1034/2015.
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Chandrappa, M., Reddy, G.V.S., Fazlur, R. et al. Fe3O4@SiO2 magnetic nanoparticles for bulk scale synthesis of 4′-chloro-2,2′:6′,2″-terpyridine. Chem. Pap. 71, 2445–2453 (2017). https://doi.org/10.1007/s11696-017-0238-0
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DOI: https://doi.org/10.1007/s11696-017-0238-0