双氧水/钨酸钠高效催化氧化制备邻二硝基甲苯  

Synthesis of Dinitrotoluene by Highly Efficient Catalytic Oxidation in H2O2/Na2WO4 System

作　　者：张敏[1] 刘红利[1] 刘影 葛忠学[1] 丁可伟[1] 翟连杰[1] 朱勇[1] ZHANG Min;LIU Hong-li;LIU Ying;GE Zhong-xue;DING Ke-wei;ZHAI Lian-jie;ZHU Yong(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：《化学试剂》2020年第12期1509-1514,共6页Chemical Reagents

基　　金：国家自然科学基金资助项目(11904281)。

摘　　要：为提供一种高产率、高纯度的2,3-二硝基甲苯及3,4-二硝基甲苯的合成方法,以双氧水/浓硫酸为氧化体系,钨酸钠为催化剂,2-甲基-6-硝基苯胺、4-甲基-2-硝基苯胺分别为原料,通过催化氧化探索了两种邻二硝基甲苯的合成方法,产率分别为93.5%和92.3%,纯度为98.8%和99.2%。利用红外光谱、核磁共振谱及元素分析对其结构进行了表征,分别考察了不同的氧化体系、反应温度、反应时间、氧化剂用量和催化剂用量等因素对产率和纯度的影响,获得了合成2,3-二硝基甲苯和3,4-二硝基甲苯的最佳工艺条件。并对催化氧化反应机理进行了推测。利用DSC对化合物的热稳定性进行了分析,结果表明:2,3-二硝基甲苯及3,4-二硝基甲苯的熔点分别为63.66、65.16℃,气化起始温度分别为169.5、148.16℃。Synthesis of 2,3-dinitrotoluene and 3,4-dinitrotoluene with high yield and purity were carried by catalytic oxidation in H2O2/H2SO4/Na2WO4 system from 2-methyl-6-nitroaniline and 4-methyl-2-nitroaniline,respectively.The yield of 2,3-dinitrotoluene was 93.5%with the purity of 98.8%,and the yield of 3,4-dinitrotoluene was 92.3%with the purity of 99.2%.The structures were confirmed by FT-IR,1HNMR,13CNMR and elemental analysis.The effects of oxidant system,reaction temperature,reaction time,oxidant dosage and catalyst dosage on the oxidation reaction to prepare dinitrotoluene were investigated,and the optimized synthesis conditions were obtained.The mechanism of catalytic oxidation was speculated.The thermal stabilities of dinitrotoluene were studied by differential scanning calorimetry(DSC).The melting point of 2,3-dinitrotoluene and 3,4-dinitrotoluene were 63.66℃and 65.16℃,respectively.And the gasification starting temperatures were 169.5℃and 148.16℃,respectively.

关 键 词：钨酸钠 过氧化氢 二硝基甲苯 催化氧化 氧化体系 

分 类 号：TJ55[兵器科学与技术—军事化学与烟火技术]