MOFs Catalyzed N-Alkylation Of Aromatic With Alcohols

Nitrogen containing organic compounds is a very important class of compounds which widely exists in nature and plays an very important role in people's life and industrial production. Because of its unique properties, the nitrogenous organic compounds has important application in chemical production, pharmaceutical synthesis and national defense. In recent years, with the development of society, the research of nitrogen containing organic compounds becomes a hotspot in the world and the N-alkylation reaction is one of them. In view of N-alkylation reaction is widely applied in the synthesis of pharmaceuticals, pigments production and Synthesis of organic polymeric materials,more and more researchers of chemistry gradually pay more attention to N-alkylation and to find a method with simple reaction conditions, atom economy and green enviromental protection becomes a research hotspot of chemists.The study of N-alkylation has a long history. More than 100 years ago, Ullman was using aniline as nitrogen source, bromobenzene as N-alkylation reagent and acquired N-alkylation products by cross coupling reaction. Later, on the basis of this reaction people improve catalyst, addition agent, solvent and reaction temperature to increase reaction efficiency and to extend range of substrates. After decades of exploration, people have made great achievements in this method. However, because the halide has a lot of toxicity and its byproduct hydrogen halides have great pollution to the environment; researchers have to explore new N-alkylation reagents. In recent years, with the development of the concept of green chemistry, to explore the reaction conditions of less toxicity or non-toxicity and green environmental protection has become the focus of research workers. Through continuous exploration of reserchers find that alcohol can also be used as a N-alkylation agent. The byproduct is water when uses alcohol as the reagents of N-alkylation. Alcohol is cheap and easy to get and the more important thing is the alcohol is virtually non-toxic. So it can reduce the cost. Therefore, it becomes the focus of scientific researchers. The traditional method to take alcohol as the reagent of N-alkylation is catalyzed by noble metal catalyst. The reaction rate is relatively high, but the cost is also higher and the reaction conditions are higher. In recent years, heterogeneous catalysts can be used in the development of cheap metals, but the catalytic system has poor selectivity. In view of the above problems, in order to save costs and to simplify the reaction conditions, our research group improves the selectivity of the product regard as our concept by using metal organic frameworks(MOFs) and ligand as the catalytic system of acid to catalytic alcohol and amine N-alkylation reaction.This thesis has three parts:Chapter 1: A review of N-alkylation reaction of amines with alcohols. In this paper, for nearly 20 years literatures about using alcohol as the reagents of N-alkylation were collected, classified, summaried. Taking the various metal catalysts in catalytic N-alkylation reaction as the main line, the type, ligand, additive, temperature, solvent reaction conditions of catalyst were analyzed.Chapter 2: Ni(BDC)-MOF catalyzed N-alkylation reaction research of anilines with benzyl alcohols. This chapter mainly two parts.(1) Ni(BDC)-MOF was preparedted and preliminary characterization;(2) the reaction of alcohol catalysis and aromatic amines to generate N,Ndisubstituted product using Ni(BDC)-MOF as catalyst, trifluoroacetic acid(TFA) as additive, 1,2-bis(diphenylphosphine) ethane(dppe) as ligand, toluene solvent catalyzed system. The method with alcohol as N-alkylation reagents is not only green environmental protection but also good selectivity product to the second replacement.Chapter 3: The research to the reaction Cu(BTC)-MOF catalytic aromatic alcohols to aromatic amine N-alkylation. This chapter mainly reports the methord and preliminary characterization to prepare Cu(BTC)-MOF by trimesic acid and Cu(NO3)2·3H2O; the reaction to Cu(BTC)-MOF catalytic alcohol of aromatic amines to generate N,N-disubstituted product. Because the reaction takes cheap copper as catalyst and has higher yield obtained disubstituted product and a higher selectivity. The reaction mechanism is being explored.