Quantification of the nucleophilic reactivity of nicotine†. (31st May 2016)

• Record Type: Journal Article
• Authors: Byrne, Peter A.; Kobayashi, Shinjiro; Breugst, Martin; Laub, Hans; Mayr, Herbert
• Other Names: Herges Rainer guestEditor.
• Is Part Of: Journal of physical organic chemistry. Volume 29:Number 12(2016)
• Page Start: 759
• Page End: 767
• Publication Date: 2016-05-31
• Subjects: equilibrium constants -- nucleophilicity -- Lewis basicity -- kinetics -- N‐Heterocycles; Chemistry, Physical organic -- Periodicals; 547.1
• DOI: 10.1002/poc.3580
• Languages: English
• ISSNs: 0894-3230

Abstract

Abstract : 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. Abstract : The pyridine ring in nicotine reduces the nucleophilicity and Lewis basicity of the pyrrolidine nitrogen to such an extent that benzhydrylium ions react selectively at the pyridine nitrogen of nicotine.