Quantification of the nucleophilic reactivity of nicotine

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Byrne, Peter A.
Kobayashi, Shinjiro
Breugst, Martin
Laub, Hans
Mayr, Herbert
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Rate and equilibrium constants of the reactions of nicotine and structurally related compounds with benzhydrylium ions have been determined UV-Vis spectroscopically using stopped-flow and laser-flash techniques. The pyridine nitrogen of nicotine was identified as the site of thermodynamically and kinetically controlled attack. Quantum chemical calculations showed that the introduction of a pyrid-3-yl moiety into the 2-position of N-methylpyrrolidine (to give nicotine) reduces the Lewis basicity of the pyrrolidine ring by 24kJmol(-1), whereas the analogous introduction of a phenyl ring decreases this quantity by only 11kJmol(-1).
Equilibrium constants , Nucleophilicity , Lewis basicity , Kinetics , N‐heterocycles , Scales , Carbocations , Electrophilicity
Byrne, P. A., Kobayashi, S., Breugst, M., Laub, H. and Mayr, H. (2016) 'Quantification of the nucleophilic reactivity of nicotine', Journal of Physical Organic Chemistry, 29(12), pp. 759-767. doi: 10.1002/poc.3580
© 2016 John Wiley & Sons, Ltd. This is the peer reviewed version of the following article: Byrne, P. A., Kobayashi, S., Breugst, M., Laub, H., and Mayr, H. (2016) Quantification of the nucleophilic reactivity of nicotine. J. Phys. Org. Chem., 29: 759-767, which has been published in final form at https://doi.org/10.1002/poc.3580. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.