Bondarenko V. Physicochemical patterns of processes of electrochemically activated introduction of carbon dioxide into fluorine-containing imines with preparation of fluorine-containing amino acids

The thesis is devoted to study of physicochemical patterns of processes of electrochemical activation and carboxylation of fluorine-containing aromatic imines (benzalaniline derivatives) with preparation of fluorine-containing aminoacids. Possibility of preparation of flourine-containing derivatives of phenylglycine via electrocarboxylation of series of benzalanilines was shown. It was shown, that electrochemical activation of imines leading to formation of radical anions is the key step of such processes. The influence of various factors on processes of electrochemical carboxylation of fluorine-containing imines was studied. It was shown, that introduction of electron-withdrawing substituents, which are in resonance with reactive center (carbon atom of C=N bond) in both aromatic rings of imines lead to decreasing of fluorine-containing aminoacids yields (for aminoacids with substituents in aniline fragment yields decrease in sequence CH3 (54%) > H (47%) > F (46%) > Cl (39%) > > CF3 (30%) > COOEt (27%)). On basis of studing of solvent and supporting electrolyte nature on these processes it was established, that factors which increase strong ion paring between radical anions and supporting electrolyte cations (deareasing of solvent polarity and cation radius), decrease the carboxylation efficiency. The best yields of aminoacids at cathodes with weak imine adsorbtion (GC, brass) and with the absent of simultanious reduction of imines and CO2 (GC, Zn) was obtained. Relationship between aminoacids yields and imines parameters of reduction obtained by cyclic voltammetry was established.