草铵膦的绿色合成工艺

A Green Process for Glufosinate

[目的]草铵膦合成的绿色工艺研究。[方法]以甲基亚磷酸二乙酯为原料,与丙烯醛反应生成1-二乙氧基-3-(乙氧基甲基膦酰基)丙烷,经稀酸水解得到3-(甲基羟基膦酰基)丙醛,再与碳酸氢铵及氢氰酸利用Bucherer-Bergs反应环合,经氧化钙水解,二氧化碳通入反应液去除钙离子得到草铵膦。[结果]水解反应的最佳条件:投料量摩尔比例n(甲基亚磷酸二乙酯)∶n(氧化钙)∶n(水)为1∶2∶35,反应温度140℃,反应时间10 h。[结论]草铵膦的总收率可达70%。该方法合成草铵膦的工艺后处理简单,反应生成的副产品碳酸钙可以焙烧处理后以氧化钙形式套用,同时生成的二氧化碳也可回收循环利用。该工艺避免了废固的产生,可实现草铵膦的绿色生产。

[Aims]This study aims to develop a green process for glufosinate.[Methods]1-Diethoxy-3-(ethoxymethylphosphoryl)propane was obtained by reacting diethoxyl methylphosphine with acrolen,and followed by hydrolysis with dilute sulfuric acid to give 3-[hydroxy(methyl)phosphoryl]propionaldehyde.The Bucherer-Bergs reaction of the aldehyde with ammonium bicarbonate and hydrogen cyanide afforded a hydantoin derivative,ethyl 2-(2,5-dioxoimidazolidin-4-yl)ethyl(methyl)phosphinate,which was hydrolyzed by calcium hydroxide and then introduced carbon dioxide into reaction system for removing calcium cations to give glufosinate.[Results]The optimal molar ratio of hydrolysis reaction is 1∶2∶35(diethoxyl methylphosphine:calcium oxide:water).The optimum reaction temperature is 140℃and the reaction time is 10 h.[Conclusions]The total yield of glufosinate is up to 70%.The process for glufosinate is simple,economic and green,as the by-product calcium carbonate can be process to recycle.The process avoids the generation of waste solids and realizes the green production of glufosinate.