On The Free Radical Addition Reaction Of Sulfonylhydrazide With Alkene And Alkyne Under The Action Of Different Oxidants

Selenium,as a necessary trace mineral element in the human body,has its existence in people’s daily life,medical treatment and medicine and so on.In organic compounds,selenium can be introduced,transformed and removed in a variety of simple ways,which makes the reaction of selenium very important.Among them,vinyl sulfone selenides are synthetic intermediates with extensive research value and broad biological activities.Although there are many synthetic methods of vinyl selenide,this paper introduces a novel and diastereoselective synthetic method of vinyl sulfone selenide.However,this paper introduces a new and diastereoselective synthesis method of vinyl sulfone selenides,and a method for the catalytic synthesis of carbonyl sulfone compounds with small molecular organic compounds.In this thesis,the three-component reaction of selenium dioxide,sulfonyl hydrazide compounds and alkynes to prepare polyfunctional substituted alkenyl sulfone selenides was firstly studied.The selectivity of the reaction is controlled by controlling the reaction conditions,so that a compound with different structures can be produced as the main product under two different conditions.In this experiment,the reaction of selenium dioxide,p-toluenesulfonyl hydrazide and phenylacetylene was selected as the template reaction,and the effects of various factors such as solvent,reaction temperature,reaction time and material ratio were investigated by the single-factor control variable optimization method.Influenced and obtained the optimal reaction conditions with the trans product 4ad as the main product:Condition A: 1.0 m L of 1,4-dioxane was used as the solvent,the temperature was 70 °C,the material ratio of phenylacetylene,p-toluenesulfonyl hydrazide and selenium dioxide was2:2.6:2,and under this condition The overall yield of the two isomers 4ad and 5ad can reach98% with a selectivity of 8:1.The optimal reaction conditions for the cis product 5ad as the main product are:Condition B: 1.0 m L/0.5 m L of 1,4-dioxane/water mixed solution was used as solvent,the temperature was 70 °C,and the material ratio of phenylacetylene,p-toluenesulfonyl hydrazide and selenium dioxide was 2:2: 0.5,and under this condition,the total yield of the two isomers 4ad and 5ad can reach 99%,and the selectivity can reach 1:8.Under two different optimal conditions,the generality of substrates was studied for different hydrocarbyl sulfonyl hydrazides and hydrocarbyl alkynes,respectively.Among them,there are 17 kinds of alkylsulfonylhydrazide substrates and 14 kinds of terminal alkynes.Under the condition of A,a total of 27 different trans-alkenylselenyl products were obtained,and the highest total yield of cis-trans isomers could reach 98%,and the selectivity could reach 20:1.Under the condition of B,a total of 20 different cis-alkenylselenyl products were obtained,and the highest total yield of cis-trans isomers could reach 99%,and the selection could reach 1:20.There are four kinds of intramolecular alkynes,all of which can obtain cis-alkenyl selenium products under the condition A,the highest yield reaches 80%,and the selectivity reaches 1:20.Under the condition of B,only the intermediate can be obtained,and the corresponding alkenylselenyl product cannot be obtained by further reaction.A possible reaction mechanism is then proposed and discussed through controlled experiments to capture reaction intermediates.Then,the existing synthesis methods of carbonyl sulfone compounds were studied.In this thesis,p-toluenesulfonyl hydrazide and styrene were used as reaction templates to react with the induction of free radical initiators.It’s using air oxygen to generate carbonyl sulfone compounds by oxidative bifunctionalization.The reaction conditions were screened by the single-factor controlled variable method.The factors such as the promoter,solvent,reaction temperature and material ratio of free radical initiators were investigated respectively.The optimal conditions were obtained: 0.05 mmol of 1,3,5-m-methyltriazine alkane was used as the promoter agent,1.5 m L of 1,4-dioxane was used as solvent,the temperature was 70 °C,the material ratio was 1:0.5.Its yield reached 92% under this reaction conditions.Under the optimal conditions,the substrate broadness study was carried out,among which 12 kinds of alkenes,14 kinds of aromatic sulfonyl hydrazides were obtained,and 19 kinds of carbonyl sulfones were obtained.A possible reaction mechanism is then proposed and discussed through controlled experiments to capture reaction intermediates.