论文部分内容阅读
[目的]研究不采用剧毒氰化物原料的非Strecker法合成草铵膦铵盐的工艺路线。[方法]以廉价易得的三氯化磷和亚磷酸三乙酯为原料制备氯代亚膦酸二乙酯,经格氏反应得到甲基亚膦酸二乙酯;甲基亚膦酸二乙酯与二溴乙烷在自制催化剂催化下反应得到甲基(2-溴乙基)膦酸乙酯;然后与乙酰氨基丙二酸二乙酯负离子在甲苯中反应,经盐酸酸化,氨水铵化得到草铵膦铵盐。[结果]以三氯化磷计,甲基亚膦酸二乙酯收率为57.6%;以甲基亚膦酸二乙酯计草铵膦铵盐收率为25.8%;制备的草铵膦铵盐各性能指标与文献相符。[结论]以三氯化磷、亚磷酸三乙酯为原料制备氯代亚膦酸二乙酯,经格氏反应得甲基亚膦酸二乙酯是一条原材料成本较低、收率较高、易于工业化的合成路线;甲基亚磷酸二乙酯与二溴乙烷反应制备甲基(2-溴乙基)膦酸乙酯的反应可通过优化催化剂的设计提高过程收率;草铵膦的收率略低于目前以氰化物为原料的Strecker法。
[Objective] The research aimed to study the technological route of non-Strecker synthesis of glufosinate ammonium without using highly toxic cyanide raw materials. [Method] The diethyl chlorophosphinate was prepared by cheap and readily available phosphorus trichloride and triethyl phosphite as raw materials, and the methylphosphonite diethyl ester was obtained by Grignard reaction. Ethyl (2-bromoethyl) phosphonate is obtained by the reaction of ethyl ester and dibromoethane under the catalysis of self-made catalyst. Then, the product is reacted with diethyl acetamidomalonate anion in toluene, acidified with hydrochloric acid, The glufosinate ammonium salt is obtained. [Result] The yield of diethyl methylphosphonite was 57.6% with phosphorus trichloride and the yield of glufosinate ammonium was 25.8% with diethyl methylphosphonite. The prepared glufosinate Ammonium salt performance indicators in line with the literature. [Conclusion] Diethyl chlorophosphite was prepared by using phosphorus trichloride and triethyl phosphite as raw materials. Diethyl methylphosphonite produced by Grignard reaction was a raw material with low cost and high yield , Easy-to-industrial synthetic route; the reaction of diethyl methylphosphite with dibromoethane to produce ethyl (2-bromoethyl) phosphonate can improve the yield of the process by optimizing the design of the catalyst; glufosinate The yield is slightly lower than the current cyanide-based Strecker method.