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Experimental and density functional study on electronic structure and electronic circular dichroism of the phenylpyrazole insecticides enantiomers and the probable chiral catabolites

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Abstract

The stable conformations of three phenylpyrazole insecticides enantiomers and their probable chiral catabolites, marked A, B, C, a, b and c, are identified via Monte Carlo searching with the MMFF94 molecular mechanics force field. The electronic circular dichroism of flufiprole (A) and ethiprole (B) was recorded. Moreover, the DFT method is utilized to optimize for the searched conformers. Then, the electronically excited states involving the first 30 excited states were computed using the time-dependent density functional theory method. The conformations selected to investigate in this article were the most stable conformers, and the UV and ECD spectra were in accord with the experimental values. The delocalized transition between benzene ring and pyrazole groups causes the strong absorptions of the electronic transitions at the UV–visible range. Three bands appear in the ECD spectra, in which the lower-energy ECD band is a delocalized π py → π ph* electronic transition. In addition, the higher and highest energy bands originate from the localized π ph → π ph* electronic transition. The calculated UV and ECD spectra were in good accordance with reported experimental values. Since the ECD spectrum at the B3LYP/6-311++G** level is indistinctively different from that at the B3LYP/6-31+G* level, it is necessary for the diffuse functions to be added to the 6-311++G** basis set, especially considering the solvent effect.

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Acknowledgments

The project was supported by the Natural Science Foundation of China (NSFC) (Nos. 61361002, 21262049), the “Chun Hui” Plan of Chinese Ministry Education (No. Z2011125), the Scientific Research Foundation of Education Department of Yunnan Province (No. 2013FZ121), the Youth Program of Yunnan Province (No. 2014FD054), the General Program of Yunnan Provincial Education Department (No. 2015Y455), the Chemistry of Key Construction Disciplines for Master Degree Program in Yunnan (No. HXZ1303) and the Educational Reform Program of Hong He University (No. JJJG1412).

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Authors and Affiliations

  1. School of Science, Honghe University, Mengzi, 661199, Yunnan, People’s Republic of China

    Gao-Zhang Gou, Bo Zhou, Ling Shi & Wei Liu

  2. College of Chemistry and Chemical Engineering, Yunnan Normal University, Kunming, 650500, People’s Republic of China

    Shao-Ming Chi

  3. College of Pharmaceutical Science and Chemistry, Dali University, Dali, 671000, Yunnan, People’s Republic of China

    Chao-Yong Mang

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  1. Gao-Zhang Gou
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  2. Bo Zhou
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  3. Ling Shi
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  6. Wei Liu
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Correspondence to Gao-Zhang Gou or Wei Liu.

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Published as part of the special collection of articles “Health & Energy from the Sun”.

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Gou, GZ., Zhou, B., Shi, L. et al. Experimental and density functional study on electronic structure and electronic circular dichroism of the phenylpyrazole insecticides enantiomers and the probable chiral catabolites. Theor Chem Acc 135, 137 (2016). https://doi.org/10.1007/s00214-016-1892-y

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