Process Improvements for the Preparation of Insecticide Clothianidin

作者：Wang, Qin; Wu, Yi; Wang, Kunyan; Sun, Yanxue; Zhu, Hongjun^*; Yu, Juan; Xu, Chaohang

来源：Asian Journal of Chemistry, 2014, 26(10): 2815-2819.

DOI：10.14233/ajchem.2014.15801

• Insecticide
• Clothianidin
• Mannich reaction
• Optimization

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 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 %.

• 出版日期2014-5
• 单位南京工业大学