三种砜吡草唑主要代谢物的合成  

Synthesis of Three Major Metabolites of Pyroxasulfone

作　　者：李志洋 尹迪 张宇飞 柳红霞 钟玉君 彭雨晴 周昊 谢练武[1] 赵东江 LI Zhiyang;YIN Di;ZHANG Yufei;LIU Hongxia;ZHONG Yujun;PENG Yuqing;ZHOU Hao;XIE Lianwu;ZHAO Dongjiang(Faculty of Science,Central South University of Forestry and Technology,Changsha 410004,China;Changsha Jiaqiao Biotechnology Co.,Ltd.,Changsha 410000,China)

机构地区：[1]中南林业科技大学理学院,湖南长沙410004 [2]长沙嘉桥生物科技有限公司,湖南长沙410000

出　　处：《合成化学》2024年第9期833-839,共7页Chinese Journal of Synthetic Chemistry

摘　　要：为了满足除草剂代谢物毒理试验的需求,本研究设计并优化了砜吡草唑的3个主要代谢物M1、M3和M4的合成路径。通过全新的合成路径,以1-甲基-3-三氟甲基-4-氯甲基-5-二氟甲氧基-1-H-吡唑为起始原料,经过一系列反应步骤,成功合成了M1和M3。以2-甲基-2-丙烯酸和溴肟为原料,经过一系列反应后成功合成M4。通过核磁共振氢谱、液相质谱和高效液相色谱等方法对代谢物的结构和纯度进行了确定。经过优化合成工艺,M1、M3和M4的产率分别达到了76.9%、82.5%和70.1%。合成的代谢物纯度可达97%以上。本研究首次从合成路线的角度出发,成功设计并制备了这3种砜吡草唑代谢物,为农药登记和农残质检等领域提供了重要的研究基础。In order to meet the needs of toxicological tests for the metabolites of the herbicide Pyroxasulfone,the present study designed and optimized the synthetic pathways of the three main metabolites of Pyroxasulfone,M1,M3 and M4.Through a novel synthetic pathway,M1,M3 were successfully synthesized from 4-(chloroMethyl)-5-(difluoroMethoxy)-1-Methyl-3-(trifluoroMethyl)-1 H-pyrazole after a series of reaction steps.M4 was successfully synthesized from Methacrylic acid and 1,1-Dibromoformaldoxime after a number of reactions.The structure and purity of the metabolites were investigated by NMR-hydrogen spectroscopy(NMR-hydrogen spectrometry),liquid mass spectrometry(LMMS),and high-performance liquid chromatography(HPLC).The structure and purity of the metabolites were determined.After optimizing the synthesis process,the yields of M1,M3 and M4 reached 76.9%,82.5%and 70.1%,respectively.The purity of the synthesized metabolites could reach more than 97%.In the present study,these three Pyroxasulfone metabolites were successfully designed and prepared from the perspective of synthetic routes for the first time,which provides an important research basis for the fields of pesticide registration and quality control of pesticide residues.

关 键 词：砜吡草唑 代谢物 合成路径 工艺优化 毒理试验 农药登记 

分 类 号：O621.3[理学—有机化学]