Quantification of the nucleophilic reactivity of nicotine
J.Phys.Org.Chem. 2016, 29, 759-767
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 24 kJ mol−1, whereas the analogous introduction of a phenyl ring decreases this quantity by only 11 kJ mol−1. Copyright © 2016 John Wiley & Sons, Ltd.