The Synthesis And Application Of Aza-macrocycloalkanes And Their Derivatives

Aza-macrocycloalkanes and their derivatives are a sort of new ligands with excellent performance. Now, they are widely used in medical treatment, biological medicine, and other realms with bright future. However, over decades, there is barely a laboratory method which could handle with simple operations, facile materials, and high yields.In order to synthesis aza-macrocycloalkanes efficiently and conveniently, this research combined the existing Richman-Atkins Method and its improvements, summarized a route with diethylenetriamine, ethylenediamine, triethylenetetramine and diethanolamine as starting materials, via tosylation, cyclisation, detosylation, methylation and oxidation procedures, synthesized cyclen, TACN and PACP, and their methylated derivatives, oxidized methylated derivatives, and the condensed product of glyoxal and cyclen. Characterized them by melting point, IR, and 1H-NMR. In these compounds, the oxidized methylated derivatives were first synthesized, had not been reported. Compared with literature, cyclisation and detosylation were general and creative ones with higher yields in this route. Meanwhile, several coordination compounds were prepared with those ligands, and three benzo-macrocyclic sulfonamides were synthesized. In the end, two compounds were selected for the preliminary catalytic activity test.