水热法合成3-硝基吡唑的工艺优化
仝志珂1,王明亚1,陈 军2,侯 璐3,丁倩楠1,申帆帆1,潘红霞2,李永祥1,曹端林1

(1.中北大学 化学与化工学院,山西 太原 030051; 2.湖北东方化工有限公司,湖北 襄阳 441400; 3.山西江阳化工有限公司,山西 太原 030051)

有机化学; 熔铸炸药载体; 3-硝基吡唑; 3-NP; 水热法; 热重排; 氮杂环化合物

Process Optimization of the Preparation of 3-Nitropyrazole by Hydrothermal Method
TONG Zhi-ke1, WANG Ming-ya1, CHEN Jun2, HOU Lu3, DING Qian-nan1, SHEN Fan-fan1, PAN Hong-xia2, LI Yong-xiang1, CAO Duan-lin1

(1.School of Chemistry and Chemical Engineering, North University of China, Taiyuan 030051, China; 2.Hubei Dongfang Chemical Co., Ltd, Xiangyang Hubei 441400, China; 3.Shanxi Jiangyang Chemical Co., Ltd., Taiyuan 030051, China)

organic chemistry; melt-cast carrier explosive; 3-nitropyrazole; hydrothermal method; thermal rearrangement; nitrogen heterocyclic compounds

DOI: 10.14077/j.issn.1007-7812.202304016

备注

为解决合成3-硝基吡唑(3-NP)时重排时间长、重排试剂毒性大、N-硝基吡唑(N-NP)易升华等问题,以N-硝基吡唑为原料,采用水热法以二甲苯作为重排溶剂制备了3-NP; 并采用显微镜和红外光谱对其结构进行了表征。对水热法重排反应温度、反应时间、填充度等因素进行了优化。结果表明,该方法较佳反应条件为:反应温度180℃,保温时间3h,填充度为15%,对应理论压力为6.130MPa,此时3-NP得率为100%,产品纯度稳定在99%以上,该工艺所得产物无需进行后处理可直接使用; 重排溶剂二甲苯在水热法中固液体积比(N-NP:二甲苯)为1:3时产品得率较高,大大节约了溶剂成本,重排试剂价格低、易得、毒性小,水热法有望替代传统合成3-NP工艺。
In order to solve the problems of long rearrangement time, high toxicity of rearrangement reagents and easy sublimation of N-nitropyrazole(N-NP)in the synthesis of 3-nitropyrazole(3-NP), N-nitropyrazole was used as raw material to prepare 3-NP by the hydrothermal method using xylene as the rearrangement solvent, and the structures were characterized by microscope and IR spectrum. The reaction temperature, reaction time, filling degree and other factors were optimized. The results show that the optimal reaction conditions are as follows: reaction temperature of 180℃, holding time of 3h, filling degree of 15%, and the yield of 3-NP at corresponding theoretical pressure of 6.130MPa is 100%. The product purity is stabilized above 99%, showing that the product obtained by this process can be directly used without post-treatment. The product yield is high when the solid-to-liquid ratio(N-NP:xylene)is 1:3 in the hydrothermal method. Due to the low consumption, low cost, and low toxicity of rearrangement solvent, the hydrothermal method is expected to replace the traditional synthetic process of 3-NP.
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