钯催化的酰胺羰基化反应合成草铵膦  

Synthesis of Glufosinate by Palladium-catalyzed Amidocarbonylation Reaction

作　　者：詹意 杜晓华[1] 徐振元[1] ZHAN Yi;DU Xiao-hua;XU Zhen-yuan(Catalytic Hydrogenation Research Center, Zhejiang Key Laboratory of Green Pesticides and Cleaner Production Technology, Zhejiang University of Technology, Hangzhou 310014, China)

机构地区：[1]浙江工业大学催化加氢研究中心浙江省绿色农药清洁生产技术研究重点实验室,杭州310014

出　　处：《农药》2018年第6期406-408,共3页Agrochemicals

摘　　要：[目的]研究采用钯催化的酰胺羰基化反应制备草铵膦。[方法]以(3,3-二乙酰氧基)丙基甲基次膦酸异丁酯为初始原料,经酸解得到3-甲基异丁氧基膦酰基丙醛,然后经过钯催化的酰胺羰基化反应得到2-乙酰氨-4-甲基(异丁氧基)膦丁酸,最后经水解、氨化制得草铵膦,并对反应条件进行优化。[结果]3-甲基异丁氧基膦酰基丙醛的收率达到80%,草铵膦的收率可达50%。[结论]钯催化的酰胺羰基化反应为合成草铵膦提供了新的方法,避免了传统工艺中氰化物的使用,减少了三废。[Aims] A new synthetic method for glufosinate by palladium-catalyzed amide carbonylation reaction was studied. [Methods] With isobutyl 3,3-diacetoxy-propylmethylphosphinate as starting material, isobutyl3-oxo-propylmethylphosphinate was obtained by acid hydrolysis and then subjected to palladium-catalyzed amidocarbonylation reaction. The reaction yielded 2-acetylamino-4-methyl（isobutoxy） phosphonobutanoicacid, which was hydrolyzed and aminated to obtain glufosinate. The reaction conditions were optimized. [Results] The yield of isobutyl 3-oxo-propylmethylphosphinate was 80%, and the yield of glufosinate was up to 50%. [Conclusions] Palladiumcatalyzed amidocarbonylation reaction provides a new method for synthesis of glufosinate, avoiding the use of cyanide in traditional processes and reducing wastes.

关 键 词：草铵膦 酰胺羰基化 3-甲基异丁氧基膦酰基丙醛 合成 

分 类 号：TQ460.3[化学工程—制药化工]