Copper Catalyzes The Synthesis Of N-aryl Amides And Carbazole Derivatives

Nitrogenous organic compounds play an extremely important role in human production and the development of a variety of organisms. They widely exist in many kinds of natural products, medicine and chemical products. Inaddition, some of the nitrogenous organic compound material is indispensable to life.Amide compounds and carbazole derivatives are two typical nitrogenous organic compounds, which widely exist in bioactive molecules, organic functional materials and drugs.The development of effective methods to construct the C-N bonds has become a hot topic in organic chemistry. Recently the copper-catalyzed C-N coupling reaction has attracted much interest of chemists. To develop more efficient, lower cost, simpler synthetic method for the amide compounds and carbazole derivatives shows important significance in organic synthesis.Previous studies on the synthesis of N-arylamides from arylboric acids and nitriles mainly contain two methods. One of the methods using the more expensive and dangerous XeF2 as the oxidant, another methods can only be carried out under the co-action of four material:Cu(OTf)2, MesI(OAc)2, BF3·Et20, TMSOTf. In the past, the palladium catalyst was used for the synthesis of carbazols with dibromobiphenyl and aromatic amine, but its price is relatively expensive. Base on those results, after sufficient survery of the literature and numerous attempts, we designed a new approach to N-arylamides and carbazole derivatives.The thesis mainly focused on the following three parts:In the first chapter, we firstly described four different pathways to construct C-N bond, then briefly introduce the synthesis of amide compounds, and finally introduced several common methods of the construction of carbazole derivatives.In the second chapter, an improved method for the synthesis of N-arylamides by the copper-catalyzed reaction of arylboronic acids with nitriles was described in details. We performed the reaction of phenylboronic acid reaction with benzonitrile as templates. Based on the examination of the reaction parameters, we found the optimized reaction conditions for the reaction is that CuBr2 as catalyst,t-BuOK as base, t-BuOH as solvent. On this base, the scope of amidation reaction was expanded by a variety of substituted arylboronic acids and nitriles.23 kinds of N-arylamides were synthesized by the developed method. The advantage of this method was as follows:simple experimental operation, good functional group tolerance and short reaction time. All products are consistent with the expected structure through the characterization of ~1HNMR.In the third chapter, an efficient synthesis of carbazoles via copper-catalyzed double N-arylation of primary amines with 2,2'-dihalobiphenyls is described. We performed the raction between 2,2'-dibromobiphenyls reaction with aniline as a template reaction to screene the reaction parameters. Based on the optimal reaction conditions, the reaction scope was expanded by several aromatic amines and three kinds of 2,2'-dibromobiphenyls.33 kinds of carbazole derivatives were obtained with the developed method. All products are consistent with the expected structure by the characterization of the ~1HNMR.