Competition between nucleophilic substitution of halogen (SN Ar) versus substitution of hydrogen (SN ArH)-a mass spectrometry and computational study

Chemistry : a European Journal
Kacper BłaziakWitold Danikiewicz

Abstract

The mechanism of intramolecular gas-phase reactions of N-(2-X-5-nitrophenyl)-N-methylacetamide carbanions (X=H, F, Cl) has been studied using negative ion electrospray mass spectrometry ((-)ESI-MS) technique and modelled computationally. It was proven that all three anions form cyclic σ(H) adducts, which undergo elimination of water. In the case of X=F, formation of the σ(F) adduct, leading to SN Ar reaction, was a competing process. This is the first proof that also in the gas phase formation of σ(H) adduct proceeds faster than σ(X) adduct and only when X=F, rates of these two processes are comparable. The experimental results are in full agreement with quantum chemical calculations.

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Dec 6, 2014·Journal of Mass Spectrometry : JMS·Beata WilenskaWitold Danikiewicz

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Citations

Apr 22, 2015·Journal of the American Society for Mass Spectrometry·Magdalena Zimnicka, Witold Danikiewicz
May 25, 2016·Journal of the American Chemical Society·Kacper BłaziakMieczysław Mąkosza
Feb 15, 2017·The Journal of Organic Chemistry·Joakim H Stenlid, Tore Brinck
Feb 19, 2021·The Journal of Organic Chemistry·Niklas F Eisele, Konrad Koszinowski
Jan 10, 2018·Journal of the American Society for Mass Spectrometry·Barbara Franczuk, Witold Danikiewicz

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