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Process Improvements for the Preparation of Insecticide Clothianidin
Corresponding Author(s) : Hongjun Zhu
Asian Journal of Chemistry,
Vol. 26 No. 10 (2014): Vol 26 Issue 10
Abstract
This article describes the process improvements for the preparation of the insecticide clothianidin 1. (Z)-1-Methyl-N-nitro-5-propyl-1,3,5-triazinan-2-imine (9) which was obtained by Mannich reaction of (Z)-1-methyl-2-nitroguanidine (5) n-Propylamine and 37 % aqueous formaldehyde solution in 97 % yield. Intermediate 9 was electrophilic substituted with 2-chloro-5-(chloromethyl)thiazole (4) in the presence of acid-binding agent to give (E)-1-[(2-chlorothiazol-5-yl)methyl]-3-methyl-N-nitro-5-propyl-1,3,5-triazinan-2-imine (10) in 90 % yield. The target compound 1 was given by the hydrolyzation of 10 in 88 % yield. The optimized conditions for the preparation of clothianidin were obtained via screening the reaction temperature, reaction time, acid-binding and solvents in three steps. The overall yield of clothianidin 1 was up to 77 %.
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- K.A. Ford, A.G. Gulevich, T.L. Swenson and J.E. Casida, J. Agric. Food Chem., 59, 4860 (2011); doi:10.1021/jf200485k.
- D. Bai, S.C.R. Lummis, W. Leicht, H. Breer and D.B. Sattelle, Pestic. Sci., 33, 197 (1991); doi:10.1002/ps.2780330208.
- M. Liu and J. Casida, Pestic. Biochem. Physiol., 46, 40 (1993); doi:10.1006/pest.1993.1034.
- K. Nishimura, Y. Kanda, A. Okazawa and T. Ueno, Pestic. Biochem. Physiol., 50, 51 (1994); doi:10.1006/pest.1994.1057.
- K. Mori, T. Okumoto, N. Kawahara and Y. Ozoe, Pest Manag. Sci., 58, 190 (2002); doi:10.1002/ps.437.
- E.D. Gundelfinger and R. Schulz, in eds.: F. Clementi, D. Fomasari and C. Gotti, Insect Nicotinic Acetylcholine Receptors: Genes, Structure, Physiological and Pharmacological Properties, in Neuronal Nicotinic Receptors, Experimental Pharmacology, Springer-Verlag, Berlin, Heidelberg (2000).
- K. Matsuda, S.D. Buckingham, D. Kleier, J.J. Rauh, M. Grauso and D.B. Sattelle, Trends Pharmacol. Sci., 22, 573 (2001); doi:10.1016/S0165-6147(00)01820-4.
- M. Tomizawa and J.E. Casida, Pest Manag. Sci., 57, 914 (2001); doi:10.1002/ps.349.
- K. Nanjo, A. Kariya, S. Segami and A. Kariya, US Patent 5166164 (1991).
- P. Faiensch and L. Gsell, IE Patent 903318 (1990).
- U. Hideki, H. Noriko and M. Isao, EP Patent 0446913 (1991).
- S. Kozo, T. Shinichi and M. Koichi, EP Patent 0383091 (1990).
- S. Kozo, T. Shinichi and M. Koichi, EP Patent 0375907 (1990).
- P. Maienfisch, H. Huerlimann and J. Haettenschwiler, Tetrahedron Lett., 41, 7187 (2000); doi:10.1016/S0040-4039(00)01225-9.
References
K.A. Ford, A.G. Gulevich, T.L. Swenson and J.E. Casida, J. Agric. Food Chem., 59, 4860 (2011); doi:10.1021/jf200485k.
D. Bai, S.C.R. Lummis, W. Leicht, H. Breer and D.B. Sattelle, Pestic. Sci., 33, 197 (1991); doi:10.1002/ps.2780330208.
M. Liu and J. Casida, Pestic. Biochem. Physiol., 46, 40 (1993); doi:10.1006/pest.1993.1034.
K. Nishimura, Y. Kanda, A. Okazawa and T. Ueno, Pestic. Biochem. Physiol., 50, 51 (1994); doi:10.1006/pest.1994.1057.
K. Mori, T. Okumoto, N. Kawahara and Y. Ozoe, Pest Manag. Sci., 58, 190 (2002); doi:10.1002/ps.437.
E.D. Gundelfinger and R. Schulz, in eds.: F. Clementi, D. Fomasari and C. Gotti, Insect Nicotinic Acetylcholine Receptors: Genes, Structure, Physiological and Pharmacological Properties, in Neuronal Nicotinic Receptors, Experimental Pharmacology, Springer-Verlag, Berlin, Heidelberg (2000).
K. Matsuda, S.D. Buckingham, D. Kleier, J.J. Rauh, M. Grauso and D.B. Sattelle, Trends Pharmacol. Sci., 22, 573 (2001); doi:10.1016/S0165-6147(00)01820-4.
M. Tomizawa and J.E. Casida, Pest Manag. Sci., 57, 914 (2001); doi:10.1002/ps.349.
K. Nanjo, A. Kariya, S. Segami and A. Kariya, US Patent 5166164 (1991).
P. Faiensch and L. Gsell, IE Patent 903318 (1990).
U. Hideki, H. Noriko and M. Isao, EP Patent 0446913 (1991).
S. Kozo, T. Shinichi and M. Koichi, EP Patent 0383091 (1990).
S. Kozo, T. Shinichi and M. Koichi, EP Patent 0375907 (1990).
P. Maienfisch, H. Huerlimann and J. Haettenschwiler, Tetrahedron Lett., 41, 7187 (2000); doi:10.1016/S0040-4039(00)01225-9.