稳定同位素标记甲基毒死蜱-D6的合成研究  

Synthesis of Stable Isotope Labelled Methyl Chlorpyrifos-D6

作　　者：涂亚辉 邓晓军[3] 钟佳琪 赵超敏[3] 罗勇 潘洁 徐仲杰 TU Yahui;DENG Xiaojun;ZHONG Jiaqi;ZHAO Chaomin;LUO Yong;PAN Jie;XU Zhongjie(Shanghai Research Institute of Chemical Industry CO.,LTD.,Shanghai 200062,China;National Isotope Engineering Technology Research Center-Shanghai Sub-Center,Shanghai 200062,China;Technology Center for Animal Plant and Food Inspection and Quarantine,Shanghai Entry-Exit Inspection and Quarantine Bureau,Shanghai 200135,China)

机构地区：[1]上海化工研究院有限公司,上海200062 [2]国家同位素工程技术研究中心上海分中心,上海200062 [3]上海出入境检验检疫局动植物与食品检验检疫技术中心,上海200135

出　　处：《同位素》2020年第3期173-179,共7页Journal of Isotopes

基　　金：“食品安全关键技术研发”重点专项(2017YFC1601300);上海市中央引导地方科技发展专项资金项目(YDZX20173100004528)。

摘　　要：甲基毒死蜱是农业生产上常用的有机磷农药之一,在农药残留检测中引起广泛关注。本文以三氯硫磷为起始原料和价廉易得的甲醇-D4作为稳定同位素标记源,经过两步亲核取代反应合成重要的同位素标记中间体O,O-二甲基硫代磷酰氯-D6。在两相反应体系中,利用相转移催化剂催化同位素标记中间体:O,O-二甲基硫代磷酰氯-D6与3,5,6-三氯吡啶-2-醇合成稳定同位素标记甲基毒死蜱-D6,可作为农药残留检测用的内标试剂。优化反应原料摩尔比、溶剂等实验条件。该合成路线安全可靠,操作简单,对设备无特殊要求,适合实验室规模合成。产品经1H NMR、GC、GC-MS结构表征确定为甲基毒死蜱-D6。以消耗的甲醇-D4计算,甲基毒死蜱-D6的总收率为44.2%,纯度为98.3%,丰度99.0atom%D。With the rapid development of society and the gradual improvement of living standards,the problem of pesticide residue in food safety detection had aroused widespread concern.Among them,organophosphorus pesticide residues in food such as vegetables and fruits frequently occurred.Among them,methyl chlorpyrifos is one of the organophosphorus pesticides commonly used in agricultural production,which is causing widespread concern in pesticide residue detection.The purpose of this paper is to synthesize a stable isotope labelled methyl chlorpyrifos-D6 as an internal standard reagent for accurate detection of pesticide residues.Using trichlorosulfate as the starting material and the cheap and easily available methanol-D4 as a stable isotope labelling source,an important isotopically labelled dimethyl chloroth-iophosphate-D6 was synthesized by a two-step nucleophilic substitution reaction as an intermediate.The isotopically labelled dimethyl chloroth-iophosphate-D6 and 3,5,6-trichloropyridin-2-ol were used in the two-phase composite system to synthesize the stable isotope-labeled methyl chlorpyrifos-D6 by phase transfer catalyst.The methyl chlorpyrifos-D6 could be used as an internal standard reagent for pesticide residue detection.A better synthetic route was obtained by optimizing the experimental conditions such as the molar ratio of the reaction raw materials and the solvent.This synthetic route was safe,reliable,easy to operate,and had no special requirements for equipment,which was suitable for the laboratory scale.The product was identified by 1H NMR,GC and GC-MS.The yield of methyl chlorpyrifos-D6 with a purity of 98.3%and an isotope abundance of 99.0atom%D was 44.2%based on the consumed methanol-D4.

关 键 词：稳定同位素标记 O O-二甲基硫代磷酰氯-D6 甲基毒死蜱-D6 内标试剂 

分 类 号：TL99[核科学技术—核技术及应用] TQ453.22[化学工程—农药化工]