Synthesis And Construction Study Of Tetraazamacrocycle Compounds

Macrocyclic polyamine compound is a type of unique and excellent ligand for coordinating metal ions. It both can complex metal ions, and may surpass a molecule with the organic positive charge ammonium ion or the organic negative ion bringing negative charge along to complexing action happened, also may come into being supermolecular according to host-guest complexing formation. Macrocyclic polyamine metal complexes as enzyme models are widely used in chemical biology, medicine and gene therapy.1,4,7,10-tetraazacyclododecane (cyclen) and its derivatives have been used in chemistry, biology, medicine and many other fields due to their coordination properties. Synthesis of cyclen and its derivatives is rather difficult. A comprehensive review on the methods of preparing cyclen was made. The ligand was synthesized by adopting two different synthetic routes, and these two synthetic methods were summarized. First referring to the improved synthetic method of Richman-Aktkins, the target molecule was obtained successfully from triethylenetetramine and ethylene glycol; second by the synthetic methods of amide acetals, cyclen was synthesized by DMF-DMA and TETA through three-step procedure.The ramification 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) macrocyclic cyclen is one of the most investigated compound which can chelate metallic ion. In this article we had synthesized the ramification DOTA by improved synthetic methods. Another N-the same substituted of cyclen, the compound 11 and 12 have been designed and prepared. Compound 12 was determined by X-ray single crystal diffraction. The crystals are Orthorhombic with space group Pbcn, a = 17.3174(15) A, b = 12.9891(11) A, c = 19.3379(17) A,α=β=γ= 90°, V = 4349.8(7) A³, Z = 4, D_c = 1.302 mg/m³, F(000) = 1804,μ= 1.001 mm^-1, R1 = 0.0426, wR₂ = 0.0795. The results show that C-H…πinteraction exists in the construction of the compound.The single-arm and double-arm of cyclen 19 and 20 have been synthesized. The structures of these compounds were consistent with the date obtained from ¹H NMR et al, and Compound 19 was characterized by X-ray single crystal diffraction. The crystals are monoclinic with space group C2/c, a = 24.145(6) A, b = 16.013(4) A, c = 16.632(4) A,α=γ= 90°,β= 120.360(3)°, V = 5.5486(6) nm³, Z = 8, Dc = 1.146 g/cm³, F(000) = 2056,μ= 0.082 mm-1, R₁ = 0.0853, wR₂ = 0.2331 (I>2σ(I)).In this dissertation, new macrocyclic polyamine compounds have been designed and synthesized. The synthetic methods and effect factors of the compounds have been systematically studied, and the synthetic methods of them have been discussed in detail. Four new pendant-armed benzene-containing cyclen derivatives were synthesized,and characterized by IR, MS, 1HNMR and X-ray single crystal diffraction. A total of two crystal structures of these compounds were determined by X-ray single crystal diffraction, and were first reported. A series of convenient and efficient reactions have been developed and a series of useful and creative results have been obtained.