title: Competition between nucleophilic substitution of halogen (SN Ar) versus substitution of hydrogen (SN ArH)-a mass spectrometry and computational study.
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.
authors.affiliation: Institute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw (Poland).
authors.forename: Kacper
authors.initials: K
authors.lastname: Błaziak
authors.forename: Mieczysław
authors.initials: M
authors.lastname: Mąkosza
authors.forename: Witold
authors.initials: W
authors.lastname: Danikiewicz
keywords: aromatic nucleophilic substitution; density functional calculations; mass spectrometry; substitution of hydrogen