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DFT analysis of the nucleophilicity of substituted pyridines and prediction of new molecules having nucleophilic character stronger than 4-pyrrolidino pyridine

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Abstract

Some commonly used 3-substituted, 4-substituted and 3,4,5-substituted pyridines were examined using DFT to predict the nucleophilicity behavior based on four different methods known in the literature. HOMO-LUMO energy calculations were done using DFT/B3LYP/6-311G + (d,p) level of theory. To establish the most suitable nucleophilicity scale for all the ranges of pyridines covered herein, either Hammett substituent constant (σ) or experimental nucleophilicity values were computed. On the basis of this study, some new 4-substituted pyridines with enhanced nucleophilicity have been proposed. Nucleophilic behaviour of a few predicted molecules was found to be better than that of 4-pyrrolidino pyridine.

Four methods were applied for predicting nucleophilicity of substituted pyridines. Good linear regression coefficient was achieved particularly for 4-substituted pyridines. Based on the outcome of the study, some new molecules having nucleophilic character stronger than 4-pyrrolidino pyridine are predicted.

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Acknowledgements

Financial support from UGC (Grant No. 41-206/2012/ SR) is gratefully acknowledged.

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Authors and Affiliations

  1. Department of Chemistry, Gauhati University, Guwahati, 781 014, Assam, India

    KAUSTAVMONI DEKA & PRODEEP PHUKAN

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  1. KAUSTAVMONI DEKA
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  2. PRODEEP PHUKAN
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Correspondence to PRODEEP PHUKAN.

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Supplementary Information (SI)

Additional information pertaining to leave-one-out correlation and regression analysis by distribution of molecules into training and test sets is available in Supporting Information at www.ias.ac.in/chemsci.

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DEKA, K., PHUKAN, P. DFT analysis of the nucleophilicity of substituted pyridines and prediction of new molecules having nucleophilic character stronger than 4-pyrrolidino pyridine. J Chem Sci 128, 633–647 (2016). https://doi.org/10.1007/s12039-016-1057-5

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  • DOI: https://doi.org/10.1007/s12039-016-1057-5

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