Study On Synthesis Of Benzo(2H) Pyran-4-one And Cyanone Derivatives

Benzo?2H?pyran-4-one is a core structure in benzopyrone compounds,also known as4-chromanone.Benzo?2H?pyran-4-one derivatives have antibacterial,anti-inflammatory,anti-oxidant,anti-HIV,anti-cancer and other biological activities.They are also backbone of many biologically active drug molecules and are widely used in pharmaceutical intermediates and the synthesis of biologically active molecules.Ketonitrile compounds exist widely in nature and are often used in medicine,textile and other industries.Aromatic cyano ketone compounds are an important type of structure in cyanide,and they are also important organic synthesis intermediates.In recent years,the synthesis of benzo?2H?pyran-4-one derivatives and ketonitrile derivatives has become a promising research topic.How to synthesize these two types of compounds in a green and efficient manner has also become an important problem for researchers to solve urgently.Firstly,2-allyloxybenzaldehyde derivatives was used as substrates in this article,and explore the feasibility of free-radical ring closure reactions between molecules in the absence of metal catalyst.Then the influence of reaction conditions on the reaction was discussed,and optimal reaction conditions were obtained:TBAB?1.0 eq?is used as additive,K₂S₂O₈?2.0 eq?is used as oxidant,DCE is used as solvent,and react at 100?under N₂ protection for 15 h.A total of 17 benzo?2H?pyran-4-one derivatives were synthesized under optimal reaction conditions,the substrate reacts with aromatic aldehydes with different substituents,and obtains good yields.All products were characterized by MS,NMR,and determined as the target structure.Next,the synthesis of ketonitrile derivatives by Suzuki coupling catalyzed by palladium is discussed in the article.Then the influence of reaction conditions on the reaction was discussed,and optimal reaction conditions were obtained:Pd?OAc?₂?0.03 eq?was used as catalyst,PCy₃?0.07 eq?was used as ligand,K₂CO₃?2.0 eq?was used as base,dioxane was used as solvent,and the reaction was carried out at 70?for 8 h under N₂ protection.A total of 26 derivatives were designed and synthesized under optimal reaction conditions,boric acid with different substituents used as substrates,and obtains good yields.All products were characterized by MS,NMR,and determined as the target structure.Finally,the synthesis of trifluoromethyl ketone derivatives by Suzuki coupling catalyzed by palladium is discussed in the article.Then the influence of reaction conditions on the reaction was discussed,and optimal reaction conditions were obtained:Pd?OAc?₂?0.05 eq?was used as catalyst,PCy₃?0.1 eq?was used as ligand,K₂CO₃?2.0 eq?was used as base,CH₃CN was used as solvent,and the reaction was carried out at 70?for 8 h under N₂protection.A total of 12 derivatives were designed and synthesized,boric acid with different substituents used as substrates,and obtains good yields.All products were characterized by MS,NMR,and determined as the target structure.