物理化学学报 >> 2013, Vol. 29 >> Issue (03): 508-515.doi: 10.3866/PKU.WHXB201212071

理论与计算化学 上一篇    下一篇

用密度泛函活性理论和Hammett常数预测单双取代苯酚的酸性

刘良红1, 张鹏飞2, 黄莺1   

  1. 1 湖南中医药大学药学院, 长沙 410208;
    2 中南大学湘雅医院卫生部肿瘤蛋白质组学重点实验室, 长沙 410008
  • 收稿日期:2012-10-11 修回日期:2012-12-07 发布日期:2013-02-25
  • 通讯作者: 张鹏飞, 黄莺 E-mail:zhangpf690421@csu.edu.cn; xiangyi_huang@yahoo.com.cn
  • 基金资助:

    黄莺受湖南省自然科学基金项目(11JJ5065), 湖南省大学生研究型创新型项目(Xiang Jiao Tong [2011] 272)和湖南中医药大学“十二五”校级重点学科药物分析学项目资助; 张鹏飞受国家重大新药创制项目(2012ZX09303013-06), 国家自然科学基金项目(81272609)和湖南省卫生厅科研基金项目(B2010-004)资助; 刘良红受湖南中医药大学研究生科研创新项目(2012cx07)资助

Molecular Acidity of Singly and Doubly Substituted Phenols: Predictions from Density Functional Reactivity Theory and Hammett Constants

LIU Liang-Hong1, ZHANG Peng-Fei2, HUANG Ying1   

  1. 1 School of Pharmacy, Hunan University of Chinese Medicine Changsha Hunan 410208, P. R. China;
    2 Key Laboratory of Cancer Proteomics of Chinese Ministry of Health, Xiangya Hospital, Central South University, 87 Xiangya Road, Changsha, Hunan 410008, P. R. China
  • Received:2012-10-11 Revised:2012-12-07 Published:2013-02-25
  • Supported by:

    HUANG Ying was supported by the Natural Science Foundation of Hunan Province, China (11JJ5065), Hunan College Student Research Study, Innovative Experiments, China (Xiang Jiao Tong [2011] 272), and “Twelfth Five-Year” Key Discipline of Hunan University of Chinese Medicine- Pharmaceutical Analysis Science, China; ZHANG Peng-Fei was supported by the Funds from the Major New Drug Discovery Science and Technology, China (2012ZX09303013-06), National Natural Science Foundation of China (81272609), and Public Health Department of Hunan Scientific Research Foundation, China (B2010-004); LIU Liang-Hong was supported by the 2012 Innovation Program of Hunan University of Chinese Medicine for Postgraduate Students, China (2012cx07).

摘要:

用从头算和密度泛函理论准确预测分子的酸碱性仍然是一个悬而未决的理论和计算难题. 近年来运用密度泛函活性理论(DFRT)发展的分子静电势和价自然原子轨道等概念为该问题的解决提供了一个简单而有效的途径. 最近我们还提出用Hammett常数预测分子酸碱性, 并发现对苯甲酸衍生物其预测精度与DFRT方法一致. 本文将这两个新方法运用于苯酚衍生物体系以验证其普适性, 一共计算了83个体系. 发现二者均可以得到较好的预测精度, 且DFRT方法比Hammett常数结果稍好. 对进一步从局部和整体角度理解分子性质的起源以及这些性质的决定因素提供了有益启示. 该文同时还验证了Hammett常数求和规则的普适性.

关键词: 分子酸性, 密度泛函活性理论, Hammett常数, 分子静电势, 自然原子轨道, 苯酚

Abstract:

Accurate prediction of molecular acidity with ab initio and density functional theory approaches is of great interest, but remains a challenging task. Density functional reactivity theory (DFRT) with quantum descriptors, such as molecular electrostatic potential and valence natural atomic orbital energies, has recently been developed and used for this purpose. Our previous study of substituted benzoic acids revealed a novel approach to quantitatively predict molecular acidity using the Hammett constant, which gave the same prediction accuracy as that of DFRT. In this work, we applied these two approaches to singly and doubly substituted phenol systems, a total of 83 molecules, confirming their effectiveness and robustness. High accuracy was obtained using both approaches, with the DFRT approach achieving slightly higher accuracy than the Hammett approach in general. These results shed further light on the molecular features governing physiochemical properties such as acidity and basicity, both locally on the atomic level and globally on the functional group or molecular level. Our present results confirm the validity of the sum rule of Hammett constants for doubly and multiply substituted compounds.

Key words: Molecular acidity, Density functional reactivity theory, Hammett constant, Molecular electrostatic potential, Natural atomic orbital, Phenol

MSC2000: 

  • O641