Citation: LIU Liang-Hong, ZHANG Peng-Fei, HUANG Ying. Molecular Acidity of Singly and Doubly Substituted Phenols: Predictions from Density Functional Reactivity Theory and Hammett Constants[J]. Acta Physico-Chimica Sinica doi: 10.3866/PKU.WHXB201212071 shu

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

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 Date: 11 October 2012
Available Online: 7 December 2012
Fund Project: 黄莺受湖南省自然科学基金项目(11JJ5065) (11JJ5065) 湖南省大学生研究型创新型项目(Xiang Jiao Tong [2011] 272) (Xiang Jiao Tong [2011] 272) 张鹏飞受国家重大新药创制项目(2012ZX09303013-06) (2012ZX09303013-06) 国家自然科学基金项目(81272609) (81272609)湖南省卫生厅科研基金项目(B2010-004)资助 (B2010-004) 刘良红受湖南中医药大学研究生科研创新项目(2012cx07)资助 (2012cx07)

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 verning 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.
- Molecular acidity,
- Density functional reactivity theory,
- Hammett constant,
- Molecular electrostatic potential,
- Natural atomic orbital,
- Phenol
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