4-甲硫基苯基二正丙基磷酸酯的合成  

Synthesis of 4-(methylthio)phenyl Di-n-propyl Phosphate

作　　者：施介华[1] 严巍[1] 王桂林[1] 王纪康[1] 

机构地区：[1]浙江工业大学药学院绿色合成技术国家重点实验室培育基地,浙江杭州310032

出　　处：《高校化学工程学报》2005年第6期798-802,共5页Journal of Chemical Engineering of Chinese Universities

摘　　要：以正丙醇、三氯化磷、4-甲硫基苯酚等为原料,合成有机磷杀虫、杀菌剂丙虫磷以及中间体二正丙基亚磷酸酯等。通过正交优化试验,考察了温度、时间和物料配比对二正丙基亚磷酸酯的合成收率的影响。确定了二正丙基亚磷酸酯的合成工艺条件。在此工艺条件下,二正丙基亚磷酸酯的平均合成收率达89.4%。在二正丙基亚磷酸酯的合成基础上,探索了二正丙基磷酰氯的合成工艺条件,在所选择的合成条件下,二正丙基亚磷酸酯氯化制备二正丙基磷酰氯的收率达92%以上。同时,较系统地考察了高选择性有机磷杀虫、杀菌剂丙虫磷的合成的工艺条件如反应温度、反应时间、缚酸剂种类以及缚酸剂的用量。在通过正交优化试验获取的较适宜的合成工艺条件下,丙虫磷的合成收率达90%以上(以4-甲硫基苯酚投料计)。二正丙基亚磷酸酯和丙虫磷的结构用IR和1H-NMR表征。An organ phosphorous pesticide, 4-（methylthio）phenyl di-n-propyl phosphate （propaphos）, and intermediates, di-n-propyl phosphite and di-n-propyl chlorphosphate, were synthesized by using n-propanol, phosphorus trichloride, 4-（methylthio）phenol, etc. as starting materials. Based on orthogonal test, the factors influencing the synthesis of di-n-propyl phosphite, such as reaction temperature, reaction time and molar ratio of reactant, were investigated. The experiment results show that the mean yield of 89.4% can be obtained under following optimal reaction conditions： molar ratio of n-propanol to phosphorus trichloride 3：1, reaction temperature 70℃, and reaction time 1.5 h. The reaction conditcons for di-n-propyl chlorophosphate preparation were studied. Under the selected reaction conditions, the yield of di-n-propyl chlorophosphate prepared with di-n-propyl phosphite could reach above 92%. Meanwhile, the reaction conditions for synthesis of propaphos, such as reaction temperature, reaction time, molar ratio of reactant were investigated, and the optimal one were found as the following： molar ratio of4-（methylthio）phenol, phosphite and sodium hydroxide 1：1.4：2.3, reaction temperature 70℃, reaction time 2 h. Under these conditions, the yield of propaphos could reach above 90%. The structure of di-n-propyl phosphite and propaphos prepared were identified by IR and ^1H-NMR spectra.

关 键 词：4-甲硫基苯基二正丙基磷酸酯 二正丙基亚磷酸酯 二正丙基磷酰氯 4-甲硫基苯酚 丙虫磷 杀虫剂 合成 

分 类 号：TQ453.22[化学工程—农药化工]