新型烟碱类杀虫剂Imicyafos的合成

Synthetic Process of Novel of Novel Pesticides Imicyafos

[目的]改进合成工艺,缩短合成路线,提高总收率。[方法]以O,O-二乙基硫代磷酰氯为起始原料,在碱的作用下,与溴代正丙烷反应得到O,O-二乙基-S-正丙基磷酸酯,再经五氯化磷或三氯氧磷氯化得到O-乙基-S-正丙基磷酰氯(Ⅰ);单氰胺与原碳酸四甲酯反应生成N-氰基亚胺碳酸二甲酯,然后与N-乙基乙二胺环化生成1-乙基-2-(N-氰基亚胺)咪唑(Ⅱ)。O-乙基-S-正丙基磷酰氯(Ⅰ)在碳酸钠催化下与1-乙基-2-(N-氰基亚胺)咪唑(Ⅱ)反应得到目的产物imicyafos。[结果]经1H NMR光谱鉴定,产品结构与imicyafos一致。[结论]该工艺简单经济,条件温和,适合工业化生产。

[Aims] The study aims to improve and shorten synthetic process and to increase yield. [Methods] O,O- Diethyl phosphorochloridothioate was reacted with 1-bromopropane in the presence of NaOH to give O,O-diethyl S-n-propane phosphorothioate, followed by chlorination with PC15 or POCI to give the intermediate of O-ethyl-S- n-propylphosphorochloride thiolate（I）; dimethyl cyanocarbonimidare was synthesized starting from cyanamide and tetramethyl orthocarbonate, and then was reacted with N-ethyl ethylenediamine in chloroform to give the intermediate of 1-ethyl-2-（N-cyanoimino）imidazolidine. The target product of imicyafos was afforded by reaction of O-ethyl-S-n- propylphosphorochloride thiolate and 1-ethyl-2-（N-cyanoimino）-imidazolidine in DMF. [Results] The product thus obtained is identified with ~H NMR. [Conclusions] This process is simple, mild and economical, which is suitable for industrial scale manufacture.