Aromatic Substitution

Modern Nucleophilic Aromatic Substitution

Quantum Chemical Studies of Aromatic Substitution Reactions

In this thesis, density functional theory (DFT) is used to investigate the mechanisms and reactivities of electrophilic and nucleophilic aromatic substitution reactions (SEAr and SNAr respectively). For SEAr, the σ-complex intermediate is preceded by one (halogenation) or two (nitration) π-complex intermediates. Whereas the rate-determining transition state (TS) for nitration resembles the seco...

Polycyclic aromatic triptycenes: oxygen substitution cyclization strategies.

The cyclization and planarization of polycyclic aromatic hydrocarbons with concomitant oxygen substitution was achieved through acid catalyzed transetherification and oxygen-radical reactions. The triptycene scaffold enforces proximity of the alcohol and arene reacting partners and confers significant rigidity to the resulting π-system, expanding the tool set of iptycenes for materials applicat...

TRIPHENYLPHOSPHINE CATALYZED AROMATIC ELECTROPHILIC SUBSTITUTION OF 2-HYDROXYACETOPHENONE MEDIATED BY VINYLTRIPHENYLPHOSPHONIUM CATION

Protonation of the highly reactive 1:l intermediate produced in the reaction between triphenylphosphine and dimethyl acetylenedicarboxylate by 2- hydroxyacetophenone leads to vinyltriphenylphosphonium salt, which undergoes aromatic electrophilic substitution reaction with the conjugate base to produce compounds 4,5, and 6 in 1 : 1.2:0.5 ratios

Synthesis of polynitroxides based on nucleophilic aromatic substitution.

The scope and limitations of the synthesis of polynitroxides by nucleophilic substitution of electron-deficient fluorinated aromatic compounds are described. The method provides a facile route to the formation of polynitroxides exhibiting strong electron exchange between nitroxide groups.