超声连续流合成2-甲基-4,6-嘧啶二酮  

Synthesis of 2-Methyl-1H-pyrimidine-4,6-dione by Ultrasonic Continuous Flow

作　　者：王栋嵘 张圣龙 廉鹏[1] 王锡杰[1] 陈松[1] 王伯周[1] WANG Dong-rong;ZHANG Sheng-long;LIAN Peng;WANG Xi-jie;CHEN Song;WANG Bo-zhou(Xi'an Modern Chemistry Research Institute,Xi'an 710065,China)

机构地区：[1]西安近代化学研究所,陕西西安710065

出　　处：《火炸药学报》2023年第3期214-220,I0008,共8页Chinese Journal of Explosives & Propellants

基　　金：国家自然科学基金(No.22175139)。

摘　　要：为探索超声强化化学反应的可行性,掌握强化工艺规律,选取FOX-7前体2-甲基-4,6-嘧啶二酮(MPO)的合成作为研究对象,设计了MPO连续流合成方法。以盐酸乙脒和丙二酸二乙酯为原料,经连续缩合、酸化合成得到MPO,并利用红外光谱(IR)、质谱(MS)及元素分析等进行了结构表征;探究了超声强化作用下缩合反应的关键影响因素及工艺规律。结果表明,最佳反应条件为停留时间9min,反应温度60℃,超声功率150W,原料摩尔比n(盐酸乙脒)∶n(丙二酸二乙酯)为1∶1.15,反应液浓度1.0mol/L(以盐酸乙脒计);得到MPO收率86.6%,纯度99.7%,反应时间由传统釜式工艺的7.5h缩短至9min,大大提高了反应效率,获得的产品粒径小于100μm,粒径均匀、分散性好,表明该超声反应器连续制备效率高,有大规模的应用前景。In order to explore the feasibility of ultrasonic irradiation enhanced reaction and master the strengthening process characteristics,the synthesis process of FOX-7 precursor 2-methyl-1H-pyrimidine-4,6-dione(MPO)was selected as the study object,and the continuous flow synthetic method of MPO was designed.By using acetamidine hydrochloride and diethyl malonate as raw materials,MPO was obtained by continuous condensation and acidification.The structure was characterized by infrared spectrum(IR),mass spectrometry(MS)and elemental analysis.The key factors and technological rules of condensation reaction under ultrasonic irradiation strengthening were investigated.The results show that the optimal reaction conditions are as follows:residence time of 9min,reaction temperature of 60℃,ultrasonic irradiation power of 150W,raw material molar ratio n(acetamidine hydrochloride)∶n(diethyl malonate)of 1∶1.15,and the concentration of the reaction solution of 1mol/L(calculated by acetamidine hydrochloride).The yield of MPO is 86.6%,and the purity is 99.7%,the reaction time is shortened from 7.5h in the tank reactor to 9min in the ultrasonic reactor,which means the substantial improvement of reaction efficiency.The particle size of the product is less than 100μm with uniform particle size and good dispersion,showing that the ultrasonic reactor has high continuous production efficiency and exhibits a large-scale application prospect.

关 键 词：有机合成 2-甲基-4 6-嘧啶二酮 MPO 超声 连续流 

分 类 号：TJ55[兵器科学与技术—军事化学与烟火技术] O62[理学—有机化学]