Applications Of Perylene-based Compounds On Energy Transfer And Electron Transfer Photocatalysis

Visible light catalysis,which uses photocatalyst as a carrier to convert light energy into chemical energy to drive chemical reactions,is a research hotspot in green chemistry in recent years.Different from expensive and polluting metal photocatalysts,organic photocatalysts are cheap and easy to obtain,green and environmentally friendly,and have better photochemical properties.In this thesis,perylene-based compounds were used as photocatalysts to achieve important photocatalytic energy transfer and electron transfer reactions,and a series of drug intermediates with important biological activities were synthesized,which laid the foundation for the application of perylene photocatalysts in drug synthesis reactions.In the first part,perylene compounds were used as photosensitizers to achieve the photocatalytic energy transfer reaction and complete the two types of reactions of olefin configuration isomerization and aryl esterification.The optimal conditions for olefin configuration isomerization and aryl esterification were obtained by screening the reaction catalyst,bases,light source,atmosphere and other conditions,and a wide range of substrates was carried out according to the types and positions of functional groups.The olefin configuration isomerization reaction had good functional group compatibility.Both symmetrically substituted and asymmetrically substituted diaryl ethenes could efficiently perform isomerization reactions with good yields and high Z/E ratios.The above substituents included electron-donating groups and electron-withdrawing groups such as methyl,methoxy,halogen,and trifluoromethyl.Also,cinnamic amides and substrates with alkyl groups attached to the double bond could also efficiently achieve the transformation of the double bond configuration.Kinetic experiments showed that as the reaction progresses,E-configuration olefins were gradually converted to Z-configuration olefins,and reached a light-stable state in24 hours.At the same time,the substrates for aryl esterification reactions,including aryl bromides and carboxylic acids,have also been expanded.When electron-withdrawing groups such as cyano,ester,and carbonyl were attached to the para and ortho positions of the aryl bromide,the reaction could proceed smoothly with a high yield,and the pyridine esters,which are active intermediates,could also be achieved with high efficiency.The types of carboxylic acids have also been expanded.Both aromatic acids and aliphatic acids with different substituents could be cross-coupled with aryl bromides with better activities.The fluorescence quenching experiment was used to further verify the reaction mechanism,which confirmed the energy transfer process from the perylene photosensitizer to the nickel complex.This laid the foundation for more in-depth energy transfer research and expansion of the application of perylene compounds in drug synthesis.In the second part,using perylene compounds as photocatalysts,the photocatalytic electron transfer reaction was studied,and the aryl sulfonylation reaction catalyzed by organic photocatalysts was brought out.We explored the reactivity of the reaction under different nickel salts,ligands,bases,and light sources,obtained the optimal conditions for the reaction,and expanded the scope of the substrate aryl bromide.When electron-withdrawing groups,such as cyano,ester,and carbonyl,were attached to the benzene ring of the aryl bromide at the para and ortho positions,the reaction could proceed with a better conversion rate.Heterocyclic compounds such as bromopyridine rings could also react in good yield.In short,we used perylene-based compounds as photosensitizers,and through the study of their photophysical and electrochemical properties,we applied them to energy transfer and electron transfer reactions,and achieved the configurational isomerization of olefins,the synthesis of aryl esters and the synthesis of aryl sulfonyl compounds.The application of perylene photosensitizers in drug synthesis reactions is of great significance for the development of green and efficient drug synthesis methods.