肼在二甲基亚砜中pKa的预测  

Theoretical Predictions of pKa's of Hydrazines in Dimethyl Sulfoxide Solution

作　　者：陈曼[1] 张潇方[1] 于海珠[1] Chert Man Zhang Xiaofang Yu Haizhu(Department of Chemistry and Center for Atomic Engineering of Energy Materials, Anhui University, Hefei 230601, China)

机构地区：[1]安徽大学化学化工学院,安徽合肥230601

出　　处：《广东化工》2016年第21期15-18,共4页Guangdong Chemical Industry

基　　金：安徽大学高层次人才引进计划J01006021

摘　　要：肼基化合物广泛应用于有机合成及生物医药领域,对于这类分子的酸性标度为相关研究提供了重要数据。文章以22个实验测量的肼基化合物的p Ka为样本,系统研究了不同密度泛函方法对这类分子p Ka值预测的效果。发现使用6-311+G(2df,2p)全电子基组的B3LYP和M06-2X方法能准确预测不同肼的p Ka值,其中M06-2X/6-311+G(2df,2p)由于包含色散校正更适用于复杂的多官能团分子体系。运用这一方法,理论预测了32种常用于生产生活中的肼在二甲基亚砜(DMSO)溶剂中的p Ka值,并归纳了取代基类型影响p Ka值的结构-活性关系。Hydrazmes （with -N-N- bond） have been widely used in organic synthesis, material science and phannaceutical chemistry. The present sludy aims to find out a reliable method to accurateIy predict the pKa＇s of the hydrazines, whose pKa＇s are remain unknown in these days. To achieve this goal, we first put effort in comparing the theoretical pKa＇s and the reported experimental pKa＇s of 22 hydrazines with selected density functional theory, methods, namely the B3 LYP/6-31G （d）, B3LYP/6-311 ＋G （2df, 2p） and M06-2X/6-311 ＋G （2dr. 2p）. The M06-2X/6-311 ＋G （2dt; 2pl method is determined to be the optimal method, and was therefore used lbr predicting pKa values of different hydrazines in the study.

关 键 词：肼 密度泛函理论 PKA值 理论预测 结构.活性关系 

分 类 号：TQ227.3[化学工程—有机化工]