Physical Sciences and Mathematics Commons^™

Quantum Chemical Investigations Of Nucleophilic Aromatic Substitution Reactions And Acid Dissociations Of Aliphatic Carboxylic Acids, David Henry Schory

Browse all Theses and Dissertations

Quantum chemical analysis was used to examine nucleophilic aromatic substitution reactions of fluorinated benzophenones, diphenyl sulfones, and triphenylphosphine oxides. Some experimental results for these compounds were contrary to conventional wisdom, which holds that calculated atomic charges for the aromatic sites and ¹³C-NMR and ¹⁹F-NMR chemical shifts should allow prediction of the preferred sites for aromatic substitution. Density functional theory (B3LYP/6-31+G*//RM1) and semi-empirical (RM1) quantum chemical calculations were employed to study the intermediates in the reaction pathways in order to identify the preferred paths for aromatic substitution. In most cases studied para substitution pathways had the lower energy intermediates …