Studies On The Synthesis Of Three Kinds Of Fully-substituted1,2,3-Triazole In Using Of Coopper(Ⅰ) Catalysts And Inorganic Base

Researches show that1,4,5-trisubstituted-1,2,3-triazoles are playing a more and more important rolein drug research and development, the synthesis of new material and the establishing of lead compoundsbase and biological dimmers. The synthesis of fully-substituted1,2,3-triazoles is becoming an importantway to research the structure activity relationship and improve the biological activity of structure-activitydrugs containing triazoles.CuAAC (copper-catalyzed azide-alkyne cycloadditions) reaction is proposed recently that using a Cu(I)effective catalytic between organic azides and terminal alkynes to get1,4,5-trisubstituted-1,2,3-triazolesthrough1,3-dipolar cycloaddition reaction. The reaction has the following advantages:(1) it's a mildreaction, and not sensitive to oxygen or water;(2) the raw material and additive using in reaction are easilyto obtain;(3) the solvent used in the reaction are usually easy to remove;(4) the coproducts may be gettedrarely, that is to say the products could be separated easily;(5) the products are stable.As the methods of using copper(I) catalyst to synthesis1,4,5-trisubstituted-1,2,3-triazoles(fully-substituted1,2,3-triazoles) are still very scarce now, and most of these compounds synthesismethods need to use precious metals and triarylphosphine ligands through coupling reaction or C-Hactivation reaction——that not only obey the atom economy principle, and also needs high temperature andother harsh reaction conditions usually.In this case, using CuAAC reaction to get1,4,5-trisubstituted-1,2,3-triazoles with structure diversityeffectively is becoming a more and more meaningful work in the researching of synthetic methodology.We are interested in the synthesis and the application of fully-substituted1,2,3-trizaoles, and we havedone some research as followed：Firstly, we have reviewed mainly the development of fully-substituted1,2,3-trizaoles in the last few years, and divided the synthesis methods into three categories tointroduce.Secondly we have found the CuBr/inorganic base reaction system first, that is to use organicazides and terminal alkynes as the substrate, and get5,5'-bis (1,2,3-triazole) effectively. The reactionconditions was optimized, and the range of this mothed was expanded. Experimental results show that the price of the raw material in the reaction system is very inexpensive, the reaction conditions are very mildand the yields are good, what's more, the substrate structure diversity is satisfied well.The next, we have found when the temperature of this system raised in the system of synthesizing5,5'-bis(1,2,3-triazole), the products5-alkynyl-1,2,3-triazoles became the main products instead of5,5'-bis(1,2,3-triazole). And we have made use of1-benzyl-4-phenyl-5-(phenylethynyl)-1H-1,2,3-triazoleas the intermediate, to develop the application of5-alkynyl-1,2,3-triazoles through importing carbonyl,ester, carboxyl, iminazole and quinoxaline ect to get diversified structure of5-substituted-1,2,3-triazoles.At last, we have expanded the CuBr/inorganic base system to the synthesis of carbon ring compounds,and develop a new convenient method to get seven, eight, nine, ten and twelve-membered ring molecularby building the intramolecular sp2carbon-carbon bond under the function in copper catalysts.