Synthesis Of Polysubstituted 1,2-Dihydroisoquinoline Imine And ?-Arylamidine Derivatives

Ketenimine plays an important role in participating in the multi-component reaction as an important synthon for the construction of different heterocyclic compounds and has attracted more and more attention The kete nimine intermediate with high activity,selectivity and other characteristics,from its participation in the heterocyclic compounds obtained in the biological,pharmaceutical,materials and other fields can play a very important role.In modern organic che mistry,one of the hottest areas of research is the multi-component reaction involving ketenimine.The aim of this thesis is to investigate the role of N-sulfonyl imine intermediates in the synthesis of different types of complex compounds in multi component reactions.Its main contents and results are as follows:1.Three-component reaction of benzyl 2-acetylene methanesulfonate catalyzed by cuprous bromide,sulfonyl azide and aniline was developed.The reaction can synthesize polysubstituted 1,2-dihydroisoquinolin-3?4H?-imine derivative in series in one step at 60?under N₂ condition.The reaction conditions are mild,the reaction is simple,the product is novel,and the different substituents are expanded to obtain relatively high yield,the yield range of 35%-89%,of which 2-ethynylbenzyl methanesulfonate electron withdrawing yield was better than the electron donor to the best meta-effect,The crystal diffraction structure of product 7a was also measured.2.A one pot method for the three component reactions of copper bromide with copper bromide as the catalyst and with electron withdrawing group of benzene sulfonyl amine and terminal alkyne and sulfonyl azide has been developed.The reaction was obtained by tandem addition to the product o f the amidine intermediate,and then the beta-carbon attacked the carbon-sulfur-bonded carbon,resulting in smiles rearrangement to finally obtain the alpha arylamidine.The Smiles rearrangement finally obtained?-aryl amidine derivatives,which can achieve the C?sp3?-H arylation of the?-position carbon in the molecule.The system works best under N₂ at room temperature,without the involvement of expensive metals Efficient reaction,good atomic economy,high yield,with a good substrate range,The yield range of 38%-95%,of which the best neighbor nitro.All products were characterized by 1H-NMR,GC and MS,The single crystal structure of 4o was obtained.In addition,we propose possible mechanisms.