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Influence of Aprotic Solvents on the Transmission of Anomalous Substituent Effects on 13C NMR Chemical Shifts at the Carboxyl Carbon (δco) in Meta-Substituted Benzoic Acids: A Strong Evidence for π-Polarization Mechanism

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Abstract

Anomalous (reverse) substituent-induced 13C nuclear magnetic resonance chemical shifts at the carboxyl carbon (δco) in meta-substituted benzoic acids have been studied for 11 substituents having varying electronic effects in 4 aprotic (nonhydroxylic) solvents of varying polarity by employing different dual substituent parameter models. The regression results for apolar aprotic solvents provide a strong evidence for through space π-polarization mode of transmission of reverse meta-substituent effects on the carboxyl carbon in benzoic acids. The results for dipolar aprotic solvents indicate significant specific solvation of π-polarized forms of the acids. The study showed further that an apolar aprotic solvent has a distinct preference over a dipolar aprotic one for investigating intrinsic substituent effects on chemical shifts in aromatic molecules.

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Acknowledgments

Thanks are due to Banaras Hindu University, Varanasi, for financial assistance to one of the authors (R.S.). We thank Mr. R. C. P Bipin for meticulous recordings of NMR spectra and Mr. Satish Kumar for computer assistance.

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  1. Department of Chemistry, Faculty of Science, Banaras Hindu University, Varanasi, 221 005, India

    Susanta K. Sen Gupta & Ruchi Shrivastava

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  1. Susanta K. Sen Gupta
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  2. Ruchi Shrivastava
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Correspondence to Susanta K. Sen Gupta.

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Sen Gupta, S.K., Shrivastava, R. Influence of Aprotic Solvents on the Transmission of Anomalous Substituent Effects on 13C NMR Chemical Shifts at the Carboxyl Carbon (δco) in Meta-Substituted Benzoic Acids: A Strong Evidence for π-Polarization Mechanism. Appl Magn Reson 42, 321–332 (2012). https://doi.org/10.1007/s00723-011-0276-7

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  • DOI: https://doi.org/10.1007/s00723-011-0276-7

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