摘要
合成了6个含多供电子基的苯胺类化合物,为合成更稳定的芳基五唑提供了原料。合成过程中,以CMC稳定的纳米铁颗粒为还原剂,以[DMFH]H2PO4为催化剂,还原芳香族硝基化合物,改进了铁粉还原产生大量废水、铁泥的缺点,使反应更加绿色环保;此外,还原以对氨基苯磺酸制得的偶氮化合物,合成得到所需的苯胺类化合物。并通过量子化学方法计算了芳基五唑衍生物分解所需的能量壁垒,以此为依据,比较了苯环上供电子基的数量及不同位置对芳基五唑化合物稳定性的影响。苯环上间、对位的供电子基有利于芳基五唑的稳定,供电子基在对位时对稳定性的影响要强于间位,邻位的供电子基增大了空间位阻,不利于芳基五唑的稳定。
To obtain the suitable intermediates for stable arylpentazoles, six anilines with multi-electron- donating groups were synthesized. These anilines are reduced from aromatic nitro compounds by using CMC stabilized iron nanoparticles as reductant and [ DMFH ] H2PO4 as catalyst. This novel method eliminated the disadvantages of producing wastewater and iron mud and made the reaction more environmental. In addition, these anilines are reduced from azo compounds which were prepared from p- aminobenzene sulfonic acid. Energy barriers for the decomposition of the arylpentazoles were also calculated based on density functional theory. Based on the energy barriers, we found two main factors which affected the stability of arylpentazoles： the number of electron-donating groups and different positions of electron-donating groups on the benzene ring. The results show that 1 ） more electron- donating groups usually make the arylpentazoles more stable; 2 ） both para-substituted and meta- substituted electron-donor groups can significantly improve the stability, and the effect of the previous one is especially better than the latter one. Due to steric factor, the stability of all ortho-substituted arylpentazoles decreases.
出处
《精细化工》
EI
CAS
CSCD
北大核心
2014年第12期1531-1536,共6页
Fine Chemicals
基金
部预研项目(批准号:03010101)~~
关键词
多供电子基
芳基五唑
还原
密度泛函
能量壁垒
精细化工中间体
multi-electron-donating groups
arylpentazoles
reduction
DFT
energy barrier
finechemical intermediates
