Study On Free Radical Sulfonylation Reaction Based On Sulfonyl Hydrazides As Precursor

Organic sulfone is an important intermediate in organic synthesis and has been widely used in pesticide,medicine,material chemistry and other fields.Usually,sulfonyl radicals are involved in the synthesis of sulfonyl compounds,while sulfonyl hydrazine is often used as a source of sulfonyl radicals due to its stable properties,easy preparation,odorless,low toxicity,and only nitrogen and water as by-products.In recent years,sulfonyl hydrazine has been repeatedly reported in the literature,mainly as a source of aryl sulfones and sulfhydryl sulfides involved in the reaction.Among these reactions,sulfonyl hydrazide as the source of sulfone group has been widely reported.Based on the above characteristics,this article explores the use of arylsulfonyl hydrazides as a sulfonyl radical precursor,respectively,with substituted phenylacetylenes and substituted 2-(allyloxy)benzaldehydes compounds sulfonylation reaction to generate alkynyl sulfone compounds and chromanone compounds containing sulfone groups.The thesis includes the following three parts:The first chapter summarizes the studies on the reactions involving sulfonyl hydrazides reported in the literature in recent years.It mainly introduces the reactions involving sulfonyl hydrazide as a source of aryl,sulfone and thiol groups.In the second chapter,arylsulfonyl hydrazides and substituted phenylacetylenes were used as reaction substrates.Under the catalytic-oxidation system composed of NaI/TBHP,arylsulfonyl hydrazides formed sulfonyl radicals,and sulfonyl was carried out with substituted phenylacetylenes chemical reaction,alkynyl sulfone compounds were synthesized in good yield.We screened the reaction conditions and determined the optimal reaction conditions.And under the optimal reaction conditions,the scope of the reaction substrate was extended.The results show that the reaction has good tolerance to arylsulfonyl hydrazide and substituted phenylacetylene,but the aliphatic sulfonyl hydrazide and fat the terminal alkyne cannot obtain the target product.After referring to the relevant literature,we conducted a series of studies on the mechanism of the reaction and proposed a possible reaction mechanism.This reaction has the advantages of atomic economy,environmental friendliness,fewer by-products,and easy operation.The third chapter studied the use of arylsulfonyl hydrazides and substituted 2-(allyloxy)benzaldehydes as the reaction substrate,AgNO3 as the catalyst,K2S2O8 as the oxidant,CH3CN/H2O=(1:1 V/V)as the reaction solvent was reacted at 80? for 24 h to synthesize chromanone derivatives containing sulfone groups.