Tokar A. Quantum-chemical investigation of cage amines reactivity, their N-substituted and epoxy derivatives

The objects are mechanisms of cage amines arylphosphorylation and arylsulfonylation reactions as well as intramolecular cyclization of N-substituted aminoderivatives of epoxynorbornane row. The purpose of the work is to investigate of cage amines reactivity and to establish of the quantitative characteristics and regularities for these type reactions. Меthods – the geometrical parameters of compounds and transition state structures of reactions have been calculated at ab initio B3LYP/6-31G(d), BHandHLYP/6-31G(d) and MP2/6-31+G(d) levels of theory. – The results of investigation for aminolysis of diphenylchlorophosphate by methylamine have demonstrated the decisive role of “non-classic” front-side attack of nucleophile in this reaction. The nucleophilic reactivity of Nitrogen atoms in structures of N-substituted endo-5-aminomethyl-exo-2,3-epoxybicyclo[2.2.1]heptane derivatives in epoxide ring-opening reactions have been estimated. The electronic conductivity for «epoxide-acid» molecular systems of N-carbonyl derivatives of endo-5-aminomethyl-exo-2,3-epoxybicyclo[2.2.1]heptane with amido- and carbamoyl- fragments have also been investigated. Area of application – theoretical organic chemistry.