当前位置: X-MOL 学术Int. J. Chem. Kinet. › 论文详情
Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)
Estimation of reaction kinetics for aromatic and heterocycles nitration in mixed acids through computational chemistry approach
International Journal of Chemical Kinetics ( IF 1.5 ) Pub Date : 2020-10-30 , DOI: 10.1002/kin.21445
Pandurang M. Jadhav 1, 2, 3 , Raj K. Pandey 3 , Amol A. Kulkarni 1, 2
Affiliation  

Nitration of aromatic compounds and heterocycles in mixed acid environment is one of the regularly performed large‐scale reactions in the chemical industry. Although the reaction mechanism of nitration of aromatics in mixed acid is well established, the development of a methodology for the evaluation of kinetics of exothermic aromatic nitrations in a simplified and accurate way is necessary. Here we evaluate the applicability of a kinetic evaluation methodology based on Hammett's acidity function, acidity function, and empirical activity coefficient for the nitration reaction. The contributions from the functional groups on the aromatic ring and quantitative structure‐activity relationships technique are considered for these evaluations. Natural bond orbital and magnetic index nucleus independent chemical shift analyses were carried out to obtain the substitution constants. The rate constant and activation energy values were evaluated at various temperatures and sulfuric acid strengths. The results were validated by comparing with the experimental data from the literature for several molecules. The effect of various functional groups (viz carbonyl, carboxyl, methyl, and amine) substituted on the benzene ring was also evaluated. For a few identified substrates, the data were used for estimation of residence time needed for complete conversion in continuous stirred tank reactor and in a plug flow reactor to quantify the effect of substitution constant and strength of sulfuric acid. The approach will help select a suitable reactor.

中文翻译:

通过计算化学方法估算混合酸中芳族和杂环硝化反应的动力学

混合酸环境下的芳香族化合物和杂环的硝化反应是化学工业中经常进行的大规模反应之一。尽管已经很好地确定了混合酸中芳香族化合物硝化反应的反应机理,但仍需要开发一种以简化且准确的方式评估放热芳香族硝化动力学的方法。在这里,我们基于哈米特的酸度函数,酸度函数和硝化反应的经验活性系数,评估了动力学评估方法的适用性。这些评估考虑了芳香环上官能团的贡献和定量构效关系技术。进行了自然键轨道和磁指数核独立的化学位移分析,以获得取代常数。在各种温度和硫酸强度下评估速率常数和活化能值。通过与文献中几种分子的实验数据进行比较,验证了结果。还评估了在苯环上取代的各种官能团(即羰基,羧基,甲基和胺)的作用。对于一些已鉴定的底物,将数据用于估算在连续搅拌釜反应器和活塞流反应器中完成转化所需的停留时间,以量化取代常数和硫酸强度的影响。该方法将有助于选择合适的反应堆。在各种温度和硫酸强度下评估速率常数和活化能值。通过与文献中几种分子的实验数据进行比较,验证了结果。还评估了在苯环上取代的各种官能团(即羰基,羧基,甲基和胺)的作用。对于一些已鉴定的底物,将数据用于估算在连续搅拌釜反应器和活塞流反应器中完全转化所需的停留时间,以量化取代常数和硫酸强度的影响。该方法将有助于选择合适的反应堆。在各种温度和硫酸强度下评估速率常数和活化能值。通过与文献中几种分子的实验数据进行比较,验证了结果。还评估了在苯环上取代的各种官能团(即羰基,羧基,甲基和胺)的作用。对于一些已鉴定的底物,将数据用于估算在连续搅拌釜反应器和活塞流反应器中完全转化所需的停留时间,以量化取代常数和硫酸强度的影响。该方法将有助于选择合适的反应堆。通过与文献中几种分子的实验数据进行比较,验证了结果。还评估了在苯环上取代的各种官能团(即羰基,羧基,甲基和胺)的作用。对于一些已鉴定的底物,将数据用于估算在连续搅拌釜反应器和活塞流反应器中完全转化所需的停留时间,以量化取代常数和硫酸强度的影响。该方法将有助于选择合适的反应堆。通过与文献中几种分子的实验数据进行比较,验证了结果。还评估了在苯环上取代的各种官能团(即羰基,羧基,甲基和胺)的作用。对于一些已鉴定的底物,将数据用于估算在连续搅拌釜反应器和活塞流反应器中完成转化所需的停留时间,以量化取代常数和硫酸强度的影响。该方法将有助于选择合适的反应堆。该数据用于估计在连续搅拌釜反应器和活塞流反应器中完全转化所需的停留时间,以量化取代常数和硫酸强度的影响。该方法将有助于选择合适的反应堆。该数据用于估计在连续搅拌釜反应器和活塞流反应器中完全转化所需的停留时间,以量化取代常数和硫酸强度的影响。该方法将有助于选择合适的反应堆。
更新日期:2020-10-30
down
wechat
bug