Quantification of the nucleophilic reactivity of nicotine

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• 作者：Peter A. Byrne ; Shinjiro Kobayashi ; Martin Breugst ; Hans Laub and Herbert Mayr
• 刊名：Journal of Physical Organic Chemistry
• 出版年：2016
• 出版时间：December 2016
• 年：2016
• 卷：29
• 期：12
• 页码：759-767
• 全文大小：2210K
• ISSN：1099-1395

文摘

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