The Design And Synthesis Of 1-Substituted-1,2,3-Triazole Carboxylic Acid Derivatives And Their Complexes

The 1,2,3-triazole derivatives are important five-membered N-heterocyclic compounds, which are widely used in pesticides, pharmaceuticals, materials and other fields. When the 1,2,3-triazole carboxylic acid derivatives act as organic ligands, they have both advantages of N-heterocyclic compounds and carboxylic acid derivatives. In other words, they have various coordination modes, which made them good ligands. On the basis of some preliminary study on 1,2,3-triazole carboxylic acid derivatives, this paper will continue to do further research. Based on current research, several types of 1,2,3-triazole carboxylic acid derivatives are designed and synthesized. The main contents of this paper are including: 1. the synthesis of ligands3-aminopyridine,3-aminophenol,4-acetamidoaniline, methyl 3-aminobenzoate and methyl 4-aminobenzoate used as raw materials, the corresponding organic azides were obtained after diazotization and azidation. Then following reaction steps include cyclization which react between azides and ethyl acetoacetate containing active methylene and hydrolysis. Finally, six kinds of 1,2,3-triazole carboxylic acid derivatives have been synthesized successfully. They are 1-(3-pyridyl)-5-methyl-1H-1,2,3-triazole-4-carboxylic acid,1-(3-hydroxyphenyl)-5-methyl-1H-1,2,3-triazole-4-carboxylic acid, 1-(4-acetamido-phenyl)-5-methyl-1H-1,2,3-triazole-4-carboxylic acid, 1-(4-amino-phenyl)-5-methyl-1H-1,2,3-triazole-4-methyl formate, 1-(3-carboxy-pheny1)-5-methyl-1H-1,2,3-triazole-4-carboxylic acid, and 1-(4-carboxy-pheny1)-5-methyl-1H-1,2,3-triazole-4-carboxylic acid. According to the number of deprotonated hydrogen, the names of ligands are abbreviated as HL1, HL2, HL3, L4, H2L5、H2L6. Compounds have been characterized by FT-IR, NMR and MS spectrum. Wherein methyl 3-aminobenzoate and methyl 4-aminobenzoate were prepared by 3-aminobenzoic acid,4-aminobenzoic acid reacted with methanol. 2. the synthesis of complexesEleven metal-organic complexes have been constructed under diffusion, solution or hydrothermal method:[Mn(L1)2(H2O)4] (1)、[Zn(L1)2(H2O)4] (2)、[Ni(L1)2(H2O)4] (3)、[Cu(L2)2] (4)、[Co(L2)2(H2O)2]·H2O (5)、[Pb(L2)2] (6)、[Zn(L2)2(H2O)] (7)、 [Cu(L3)2]CH3OH(8)、[Cu(L4)2]·3H2O (9)、[Zn(L5)(H2O)2]n (10)、[Zn(L6)(H2O)2]n (11). Their structures were determined by X-ray diffraction. Parts of complexes have also been characterized by TGA, UV spectrum and fluorescence spectrum.