火炸药学报2025，Vol.48Issue(12)：1103-1109,7.DOI:10.14077/j.issn.1007-7812.202507009
苦基氯合成副产物1,2-二氯-3,5-二硝基苯的反应机理
Reaction Mechanism of 1,2-Dichloro-3,5-dinitrobenzene as a By-product in the Synthesis of Picryl Chloride
摘要
Abstract
To investigate the reaction mechanism of 1,2-dichloro-3,5-dinitrobenzene as a by-product during the nitration process,the effects of key process parameters such as introduction time of hydrogen chloride,volume ratio of mixed acid(fu-ming sulfuric acid/fuming nitric acid),dosage of 1-chloro-2,4-dinitrobenzene and nitration temperature on the mass concentra-tion of by-product were explored.High performance liquid chromatography(HPLC)was used to monitor the changes in the concentration.The results show that the mass concentration of by-products is the highest when the introduction time of hydro-gen chloride is 3 h,the mixed acid volume ratio is 5∶1,the addition of raw material is 1.0g,and the nitration temperature is controlled at 130℃.As the concentration of fuming nitric acid decreases in the later stage of the nitration reaction,the excess fuming sulfuric acid reacts with chloride ions in the raw material.In the strong acid system,this reaction leads to the generation of Cl·free radicals via homolysis,or the formation of Cl+equivalent species through combination with H+.These active species(Cl·or Cl+)then participate in electrophilic substitution,promoting the formation of the by-product of 1,2-dichloro-3,5-dinitrobenzene.By extending the nitrification time,controlling the volume ratio of mixed acid and nitrification tempera-ture,and avoiding the introducing of hydrogen chloride,the formation of by-products can be effectively inhibited and the purity of picryl chlorine can reach 95％or higher.关键词
有机化学/苦基氯/1,2-二氯-3,5-二硝基苯/硝化/耐热炸药/LLM-126Key words
organic chemistry/picryl chloride/1,2-dichloro-3,5-dinitrobenzene/nitration/heat-resistant explosive/LLM-126分类
军事科技引用本文复制引用
崔杨瑞,张紫薇,翟连杰,陆明,许元刚..苦基氯合成副产物1,2-二氯-3,5-二硝基苯的反应机理[J].火炸药学报,2025,48(12):1103-1109,7.基金项目
国家自然科学基金(No.22105102,No.22135003) （No.22105102,No.22135003）
中国科协青年人才托举工程(No.YESS20210074) （No.YESS20210074）
