Study On Palladium-catalyze D N-alkylation Reaction Of Amines With Alcohols

As we know, nitrogen-containing organic compounds are important class of organic compounds. With the intensive development of industry and economy, nitrogen-containing organic compounds show more demands and wide applications in chemicals, pharmaceuticals, pesticides and intermediates of organic synthesis. They are gradually becoming the research focus of chemists. For the synthesis of these compounds, N-alkylation reaction is the parimary method because of its simple operation and high conversion rate.As early as one hundred years ago, Ullmann used cross-coupling reaction to synthesize N-phenylaniline with aninline and bromobenzene. In subsequent years, chemists improved this reaction from catalysts, additives and proportion of materials. However, it caused environmental pollution problems because of its acidic byproduct hydrogen bromide. With the rise of green chemistry, alcohols were used as green alkylating reagents due to the only by-product of water. In recent years, N-alkylation reaction by using alcohols as alkylating reagents is paid more and more attention and becomes one of hot topics in organic synthesis. This conversion always needs a noble metal compound or complex as a catalyst. It also suffers long reaction time, high temperature and low selectivity of the products. In order to solve these problems, we use simple palladium compounds as catalyst and an ionic liquid as additive to explore the reaction in the thesis.This thesis has four parts:Chapter 1: A review of N-alkylation reaction of amines with alcohols. In this chapter literatures about N-alkylation reaction with alcohols as alkylating agent in recent years are reviewed in detail. The catalytic system is discussed by dividing into homogeneous and heterogeneous system. The effects of additives, solvent, temperature and the use of carrier on this reaction were also analyzed.Chapter 2: Palladium chloride catalyzed N-alkylation of anilines with benzyl alcohols. Using palladium chloride as the catalyst and an ionic liquid as the promoter, the catalytic N,N-dibenzylation reaction of anilines with benzyl alcohols is smoothly performed in toluene at reflux temperature. The effect of substituents on substrates is examined implemented.Chapter 3: Magnetic nano ferrite catalyzed N-alkylation of aromatic amines with benzyl alcohols. Nano ferrites were prepared by simple, shape and particle size-controlled self propagating combustion and characterized by SEM. Then they were used as catalysts for green N-alkylation of aromatic amines with benzyl alcohols. After screening, Pd-Cu ferrite showed excellent conversion and high selectivity in this transformation with toluene as solvent under reflux temperature. 1-Butyl-3- methylimidazolium hexafluorophosphate is also used as an efficient promoter. The method shows high atom efficiency, s imple operation and easy recovering of the magnetic catalyst, which is in accordance with standard of green chemistry.Chapter 4: Nano Pd-Cu ferrite catalyzed N-alkylation of aniline with aliphatic alcohols. N-alkylation of aniline with ethanol was successfully performed by using nano Pd-Cu ferrite as catalyst and mono-substituted product N-ethylaniline was obtained with high yield. The deep investigations are under going.