The New Synthetic Way Of ?-aminoamide And The Application Of Two Kinds Of Nitrogen And Phosphorus Heterocyclic Ligand Catalysts

This article has three parts.Firstly, the new synthetic way of ?-aminoamide.?-Aminoamide and its derivatives which widely used in drug, dye and electronic materials are important intermediates in organic synthesis. ?-Aminoamide was used as a certain reaction catalyst and catalytic ligands. Because ?-aminoamide has a wide range of applications, the research of their synthesis method is very important,but its synthetic methods is very limited. Generally, there are a lot of methods for synthesis of ?-aminoamide, such as the traditional Ugi reaction, the improving Ugi reaction, ?-amino acrylic hydrolysis, the reaction of ?-amino acide esterification then ammonia, etc., however,these reactions have some shortcomings, for example, there are many steps, harsh reaction conditions. So it's necessary to develop a simple and efficient synthesis of amide.In the modern organic synthesis, organic silicon compound can protect or activat some groups of the reaction substrate by inserting organic silicone group to achieve a pleasant result. In this paper,carbamoylsilane with the silicon and the carbonyl group can be used as a nucleophilic reagent to react with carbon and nitrogen double bond, introduce the ammonia acyl directly, generating ?-aminoamide.In this part of the article, we have synthesized two carbamoylsilanes successfully, N-?methoxymethyl?-N-methyl-?trimethylsilyl?-formamide?1? and N-methyl-N-[?R?-2-benzethyl]benzethylcarbamoylsilane?2?. The reaction between carbamoylsilanes 1 and 2with a series of N-benzenesulfonimides 3-14 that we concerned, 10 kinds of ?-amino secondary amide compounds were synthesized with the former, while 10 kinds of highly stereo-selectivity of ?-amino tertiary amide compounds were synthesized by the later, and the result of the reaction is discussed from the space of the substituent effect, electronic effect and induction effect. Finally, we put forward the possible reaction mechanism.In this part, we put forward two new synthetic methods of?-aminoamide compounds, especially enantioselective synthesis reaction. On the one hand, we provide a new way for the synthesis of amino acids, peptides, proteins, and drug intermediates. On the other hand, this way also filled in some shortages in organic silicon chemistry research of our country, therefore, this study has important application value and scientific significance.Secondly, the Heck reaction of styrene and aryl bromide with nitrogen and phosphorus heterocyclic ligand catalyst.Aryl halide of alkenyl reaction is a kind of very important Heck reaction. Aryl halide can react with many different kinds of olefins compounds, such as acrylic ester, acrylonitrile, acrylamide, alkenyl ether, styrene, etc., in which the reaction of styrene and aryl halide was widely used. In this type of reaction, the different ligands of Pd??? catalyst were used.In the part, we study the influence of the reaction betweenstyrene and a series of aryl bromide with new catalytic system Bdppy/PdCl₂?CH₃CN?₂catalytic, which forms a new coupling reaction of C-C bond. Firstly, the influence of the solvents and substrateis is discussed, the result shows that when the solvent is DMA and the substrate is K₃PO₄, catalyst has a good catalytic activity in the reaction. Under the best condition,we research the coupling reaction of styrene and a series of aryl bromide to find the yield are high which proves Bdppy/PdCl₂?CH₃CN?₂catalytic can catalyze the reaction of styrene and a series of aryl bromide effectively.Thirdly, the polymerization of styrene with nitrogen and phosphorus heterocyclic ligand catalyst.The polystyrene is a kind of thermoplastic resin, which is widely used, generally formed by the polymerization of styrene, the catalysts used in the polymerization reaction we generally divided into three kinds, early transition metal, rare earth metal and late transition metal catalysts. Among the late transition metal catalysts, the nickel catalyst has the wisest application.The third part of this paper mainly studies the new catalyst Bdpm/NiBr₂ catalytic polymerization of styrene caused by methylaluminoxane solution?MAO?.The experimental results show that the catalytic systems of?Bdpm/NiBr₂?/MAO for styrene monomer has higher catalytic activity. After studying the influence of the amount of catalyst(n_Ni), the reaction temperature?T? and the mole ratio of initiator and catalyst(nMAO/n_Ni) in the polymerization reaction, we get the best polymerization conditions: when it is in toluene solution,n_Ni=9x10^-6mol, nMAO/n_Ni=1000, and reacts for 3 h at 70 ?, the conversion?Conv.? of polystyrene reaction is 92.0 %, the number-average molecular weight?Mn? is 25.8x10^-4g/mol and molecular weight distribution?PDI? is 1.23. By ¹H NMR,¹³C NMR analysis method,we explore the structure and properties of polymer.