Study On The Synthesis Of ?-Enaminonitrile And Its Derivatives And Allyl Palladium Catalyst

?-enaminonitrile is a designable building block,which can be used to synthesize pyrimidine,pyridine,pyrrole,pyrazole,imidazole,isothiazole and pyrrolinone and other heterocyclic compounds.4-aminopyrimidine and 4-amidinopyrimidine are more important components of natural products,agricultural chemicals and biological genetic materials.It is of great significance to synthesize?-enaminonitrile,4-aminopyrimidine and4-amidinopyrimidine with simple methods and mild conditions for studying the synthesis of nitrogen-containing heterocyclic molecules.In the first part of this paper,the synthesis methods of?-enaminonitrilein the literature are described from the perspectives of amide,amine,isocyanide and nitrile,and then the construction methods of its derivatives 4-aminopyrimidine and 4-amidinopyrimidine are introduced.In addition,the preparation method and characteristics of?-allylic divalent palladium halide,which is a kind of organic reaction catalyst,are also introduced.The methods are difficult to operate and have high cost.It can be used as a cushion for one-step synthesis of?-allylic divalent palladium bromide without reducing agent under mild conditions.In the second part of this paper,the main content is to synthesize?-endiaminonitrile,4-aminopyrimidine and 4-amidine pyrimidine under controlled temperature.Through simple temperature control,under the action of Li HMDS base,this part mainly introduces the reaction of self condensation of aliphatic nitriles to?-enaminonitrile,the reaction of synthesis of?-enaminonitrile by aliphatic nitriles and aromatic or heterocyclic nitriles,the reaction of synthesis of?-enaminonitrile by aliphatic nitriles and N,N?-diisopropylcarbodiimide?DIC?,the reactions of synthesis of 4-aminopyrimidine by aliphatic nitriles and aromatic nitriles,the reactions of synthesis of 4-aminopyrimidine by?-enaminonitrile and aromatic or heterocyclic nitriles,the reactions of synthesis of 4-amidinopyrimidine by 4-aminopyrimidine and aromatic or heterocyclic nitriles.101 related compounds were synthesized by these six reactions.The compounds were characterized by ¹H NMR?¹³C NMR?mass spectrometry?X-ray single crystal diffraction.Among the 101compounds,the reaction rules were explored from the aspects of electronic effect,space effect,substituent position and intermolecular hydrogen bonding,which proved the flexibility and diversity of the reaction of nitriles.The discussion of cis–trans isomerization of?-enaminonitriles was concluded based on the results of condensation of various nitriles.The success of amplified gram reaction proved that it had the prospect of industrial production.A new reaction mechanism was proposed based on the reaction conditions of temperature and substrate amount,the mechanism studies demonstrated the possible transfer pathways of electrons and hydrogen protons.In the third part of the thesis,in the chapter of one-step synthesis of allyl palladium complexes,a new method of one-step synthesis of allyl palladium halides with phosphine ligands is introduced.The former method needs to use reducing agent,which can be divided into two steps.One step is to synthesize allyl palladium halide,which is a phosphine ligand,under nitrogen or in air,from palladium acetate,phosphine ligand and allyl halide.The highest yield can be over 85%.It is found that these compounds have the function of catalytic coupling reaction,and can be used as catalysts for olefin C-C bond coupling,azacyclocarbazole cyclization,alkyne oxidation to ketone and other reactions.6 related compounds were synthesized by this method.These palladium catalysts have the characteristics of simple reaction and wide application.