Synthesis And Applications Of Macrocyclic Tetraamides Metal Complexes

The macrocyclic polyamides are excellent organic ligands with unique structure.They have strong tendency to bind with transition metal ions,therefore to form metal complexes.Macrocyclic polyamido metal complexes have various properties and are widely used in the fields of chemistry,biology and medicine.Thus,it has profound significance to further explore the synthesis and expand the application of thses metal complexes.Starting from 3,4-diaminopyridine,2-aminoisobutyric acid,phthalic anhydride,hydrazine hydrate,oxalyl chloride,dimethyl malonic acid,and anhydrous metal chlorides etc,4 metal complexes and 9 macrocyclic polyamido ligands were synthesized.The influence of the reaction condition such as temperature,time,solvent,mode of feeding and rate of feeding etc was studied and optimized.All the products and intermediates were characterized with NMR,MS and IR.In a amiderization of mono BOC protected 3,4-diaminopyridine with acyl chloride,a in situ HOBT activated ester method gave better outcome than that reacted directly with acyl chloride.The reaction could further raised the yield from 22%with anhydrous tetrahydrofuran up to about 53%with anhydrous methylene chloride.It was found that the BOC deprotection could proceed much more mildly and efficiently under ultrasound.The yield is 96%.The research on a 13-membered macrocyclic tetraamido Fe complex for the degradation of a dye using H2O2 as the oxidant revealed that this showed high activity under broad range of pH.In a dye degradation model reaction,the rate of TOC and COD removal were 41.09%? 42.05%respectively.The preliminary research of a 13-membered macrocyclic tetraamido Cu complex showed that the benzyl alcohol could be oxidized to beazaldehyde selectively with the Cu complex/TEMPO/O2.The conversion and selectivity were 79%and 73.42 respectively.