AN IMPROVED SYNTHESIS OF ETHYL 6-(BENZIMIDAZOL-2-YL) PYRIDINE-2-CARBOXYLATE AND APPLICATION OF ITS NICKEL COMPLEX TOWARDS ETHYLENE CATALYTIC BEHAVIOR
DOI:
https://doi.org/10.51406/jnset.v11i2.1967Keywords:
benzimidazolylpyridine, nickel complex, co-catalyst, ethylene oligomerizationAbstract
Ethyl 6-(benzimidazol-2-yl)-pyridine-2-carboxylate (EBIPC) was efficiently synthesized by condensation reaction of β-keto ester pyridine carboxylate and o-phenylenediamine. The compound was characterized by elemental analysis and spectroscopic techniques (IR and NMR) to confirm its molecular structure. This new protocol afforded a product with higher yield (65.1%) and reduced number of reaction steps. Upon activation with trimethylaluminum (Me3Al) as the co-catalyst, the nickel complexes exhibited high catalytic activities for ethylene oligomerization (up to 1.26 x 106 g mol-1(Ni) h-1). Various polymerization reaction conditions significantly influenced the catalytic properties of the complexes.
References
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Asma, M., Adewuyi, S., Kuang, X., Amin, B., Sun, W.–H. 2008. An improved synthetic protocol and plausible mechanism in forming acetylpyridines from 2,6-dicarbethoxypyridine. Letters in Organic Chemistry, 5: 296–299.
Barni, E., Savarino, P.J. 1977. 2-(Methylpyridyl or quinolyl)benz-X-azoles. Heterocyclic Chem., 14: 937–940.
Furniss, B.S. Hannaford, A.J., Smith, P.W.G., Tatchell, A.R. 1989. Vogel’s Textbook of Practical Organic Chemistry. England: ELBS/Longman, pp. 786–790.
Dolinsky, M.C.B., Lin, W.O., Dias, M.L. 2006. Ethylene polymerization with nickel complexes containing aminophosphine ligands. Journal of Molecular Catalysis A: Chemical, 258: 267–274.
Hao, P., Zhang, S., Sun, W.–H., Shi, Q., Adewuyi, S., Lu, X. & Li, P. 2007. Synthesis, characterization and ethylene oligomerization studies of nickel complexes bearing 2-benzimidazolylpyridine derivatives. Organometallics, 26: 2439–2446.
Hou, J., Sun, W.-H., Zhang, S., Ma, H., Deng, Y. & Lu, X. 2006. Synthesis and characterization of tridentate nickel complexes bearing P^N^N and P^N^P ligands and their catalytic property in ethylene oligomerization.. Organometallics, 25: 236–244.
Jenkins, J.C., Brookhart, M. 2004. A mechanistic investigation of the polymerization of ethylene catalyzed by neutral Ni (II) complexes derived from bulky anilinotropone ligands. J. Am. Chem. Soc., 126: 5827–5842.
Keim, W. 1990. Nickel: An element with wide application in industrial homogenous catalysis. Angew. Chem. Int. Ed. Engl., 29: 235–244.
Keim, W., Behr, A. , Limbacker, B., Kruger, C. 1983. Novel nickel-oligomerization catalysts with arsenic-oxygen chelate ligands. Angew. Chem. Int. Ed. Engl., 22: 503–504.
Keim, W., Kowaldt, F.H., Goddard, R., Kriige, C. 1978. Novel coordination of (Benzoy1methylene)triphenylphosphorane in a nickel oligomerization catalyst. Angew. Chem. Int. Ed. Engl., 17(6): 466–467.
Mukherjee, S., Patel, B. A., Bhaduri, S. (2009). Selective ethylene oligomerization with nickel oxime complexes. Organometallics, 28(10): 3074–3078.
Nelkenbaum, E., Kapon, M., Eisen, M. S. 2005. Synthesis and molecular structures of neutral nickel complexes: Catalytic activity of (benzamidinato)(acetylacetonato)nickel for the addition polymerization of norbornene, the oligomerization of ethylene, and the dimerization of propylene. Organometallics, 24: 2645–2659.
Rachita, M. J., Huff, R. L., Bennett, J. L., Brookhart, M. 2000. Oligomerization of ethylene to branched alkenes using neutral phosphinosulfonamide nickel (II) complexes. J. Polym. Sci. Part A: Polym. Chem., 38: 4627–4640.
Speiser, F., Braunstein, P. & Saussine, L. 2004. Nickel and iron complexes with oxazoline- or pyridine-phosphonite ligands: synthesis, structure and application for the catalytic oligomerization of ethylene. J. Chem. Soc., Dalton Trans, 1539–1545.
Sun, W.–H., Hao, P., Zhang, S., Shi, Q., Zuo, W. & Tang, X. 2007. 2-(Benzoimidazole)-6-(1-aryliminoethyl)pyridyl complexes of iron (II) and cobalt (II) as highly active catalysts for ethylene oligomerization and polymerization: Synthesis, characterization and their catalytic behaviors. Organometallics, 25: 666–708.
Sun, W.–H., Zhang, S., Jie, S., Zhang, W., Li, Y., Ma, H., Chen, J., Wedeking, K., Fröhlich, R. J. 2006. Synthesis, characterization and ethylene oligomerization studies of nickel complexes bearing 2-imino-1, 10-phenanthrolines. J. Organomet. Chem., 691: 4196–4203.
Sun, W.–H., Zang,W., Gao, T., Tang, X., Chen, L., Li, Y., Jin, X. 2004. Synthesis and characterization of N-(2-pyridyl)benzamide-based nickel complexes and their activity for ethylene oligomerization. J. Organomet. Chem., 689: 917–929.
Wehrmann, P., Zuideveld, M., Thomann, R., Mecking, S. 2006. Copolymerization of ethylene with 1-butene and norbornene to higher molecular weight copolymers in aqueous emulsion. Macromolecules, 35: 5995–6002.
Zaidman, A.V., Kayumoy, R.R., Beloy, G.P., Pervova, I.G., Lipunov, I.N., Kharlampidi, Kh. E. 2010. Ethylene oligomerization in the presence of catalytic systems based on nickel (II) formazanates. Petroleum Chemistry, 50(6): 450–454.
