Direct C-S Bond Formation For The Construction Of Aryl Sulfone Compounds

Aryl sulfone compounds are an important class of organic compounds containing a sulfone skeleton structure.Such compounds have a wide range of biological activities and potential medicinal values.Therefore,the development of green and efficient methods for constructing such compounds has received extensive attention from synthetic chemists.There are many methods for C-S bond construction,and there are many sulfonylation reagents.At present,the sulfur sources for the synthesis of organic sulfone compounds are mainly organic sulfur reagents,but organic sulfur reagents have their own shortcomings and defects more or less.Mercaptan(thiophenol)is a common source of sulfur,but its smell is unpleasant and toxic,and its liquid or vapor can cause a series of health problems.Sulfonyl chloride as a sulfur source participates in the reaction and often produces harmful by-products and is difficult to handle.The chemical properties of sulfonyl hydrazide are relatively unstable,and may release sulfinate or sulfinic acid under alkaline,water or heating conditions.From the perspective of green chemistry,it is more urgent to find non-toxic alternative sulfonylation reagents.Compared with other sulfur reagents,sodium sulfinates as sulfonylation reagents have many advantages such as odorless,cheap and easy to obtain,stable properties and easy to operate.The sodium sulfinic acid salt has various reactivity.Depending on the reaction conditions,it can be used as a nucleophile or electrophile,and can also generate radicals to participate in the reaction.In view of this,the use of cheap and easily available sodium sulfinate as a sulfur source to synthesize sulfone-containing compounds has attracted more and more attention from organic chemists.Therefore,in order to obtain step economy,we plan to use sodium sulfinate as sulfonylation reagents to directly react with phenolic compounds to construct sulfone-substituted phenolic compounds.In this thesis,phenolic compounds are used as raw materials,high-valent iodine reagents as oxidants to oxidize phenol derivatives in situ to obtain intermediate quinone compounds,sodium sulfinate as sulfonylation reagent,and the Michael addition reaction occurs in a one-pot method,obtaining phenolic compounds substituted with sulfone groups.The reaction substrate has a wide range,tolerating a variety of aryl and alkyl functional groups,and the reaction can achieve good to excellent yields.The reaction can be scaled-up on a gram scale,and there is no yield loss compared with small-scale reactions.At the same time,the gram-scale reaction can obtain pure products without column chromatography using simple filtration and solvent washing methods,which increases the value of this reaction in practical applications.The corresponding target compounds obtained were all subjected to NMR,HR-MS and FT-IR structural analysis,as well as the melting point and other physical and chemical properties of the test and characterization,and a plausible mechanism was proposed.