Synthesis And Application Of Fused-Ring Triazole-(Sulfonyl)triazene Derivatives And Preliminary Study On The Participation Of Phosphorus Radicals In 1,6-Enyne Cyclization

The first part of the research mainly introduces the synthesis and application of fused-ring triazene derivatives.Triazene derivatives are a class of nitrogen-containing compounds with electronic tunability and optical activity,and are widely used in the detection of metal ions and the synthesis of heterocyclic compounds.At present,triazene mainly exists in three structural forms:linear,cyclic,and?-electron conjugate.Among them,?-electron conjugated triazene has been widely used in organic synthesis,material chemistry and medicine,such as intermediates of different heterocyclic compounds or natural products,light sensitive materials,and DNA alkylating agents for treating cancer.Wait.The existing method for synthesizing?-electron conjugated triazene derivatives is mainly to form a nitrogen heterocyclic carbene under strong base,low temperature or room temperature by coupling a nitrogen heterocyclic carbene precursor and an organic azide compound.Various substituted?-conjugated triazene synthesis can be achieved.Based on our previous research work,we envisage the use of ethylpyrido-triazolium salts and sulfonyl azides to obtain a series of triazenes,which are expected to have the same optical properties and biological activities as azines.Through conditional screening,the optimal conditions were determined as follows:nitrogen protection,fused ring triazolium salt,sulfonyl azide derivative and potassium t-butoxide dissolved in acetone,monitored by TLC,completed after 2 hours,distilled under reduced pressure,The product was isolated by column chromatography.And new?-conjugated triazene were synthesized,the highest yield was 95%.The reaction has the advantages of simple operation,short reaction time and high yield.It was found by UV and fluorescence experiments that the compounds are selective and sensitive to Fe³⁺.In the Fe³⁺concentration change experiment,we found that the compound has a linear correlation in the range of 0-450?M Fe³⁺concentration,and the detection limit is lower than the standard of drinking water.It can be used as a potential fluorescent probe for the environmental water sample Fe³⁺ion.Detection.The second part mainly introduces the preliminary investigation of the series reaction of phosphorus?phosphine?radicals and 1,6-enynes.Benzofuran,benzothiophene and anthracene are important heterocyclic compounds,among which drugs such as benzamromone,raloxifene and pradol are important in clinical application.In addition to having a heterocyclic structure,these drugs generally have different degrees of acylation or substitution at the C₃ and C₂positions.The synthesis of such compounds can be obtained by cyclization of a free radical with a 1,6-enyne such as a trifluoromethyl group,a benzenesulfonyl group,a nitro group or the like.Moreover,different substituent groups change their physicochemical properties or pharmacological activities to some extent,such as introducing a trifluoromethyl group at the C₂ position of the aromatic heterocyclic ring,which can increase the solubility,lipophilicity and metabolic stability of the compound.Phosphorus?phosphine?radicals can be catalyzed by different conditions to be olefin or alkyne?-carbonylphosphorus.Therefore,in this paper,the phosphorus?phosphine?radical and the 1,6-alkenyl are oxidatively phosphatized in series to obtain C₃-acylation.Heterocyclic compound.A preliminary methodological study on the oxygenation cascade reaction involving phosphorus?phosphine?radicals was carried out.We use1-?phenylethynyl?-2-?vinyloxy?benzene as a substrate,diethyl phosphite and diphenylphosphine oxide as a source of phosphorus?phosphine?radicals under metal oxidation and photocatalysis.Conditional screening,the experimental results finally succeeded in the synthesis of phosphorus?phosphine?-substituted C₃-acylated benzofuran ring,but after a series of conditions screening,still failed to break through the reaction limit,the reaction yield was low.We hope to re-engineer the reaction substrate and adjust the reaction conditions in the later stage to gradually solve these problems,and further explore the physical and chemical properties and application value of such compounds.