Synthesis Of Triarylacrylonitriles And 1,2-bis(phenylthio)ethenes Directly Using Calcium Carbide As A Solid Acetylene Source

Calcium carbide is a stable and inexpensive solid that is used as raw materials for the production of acetylene gas by hydrolysis in the chemical industry.Traditiona l ly,when it is used as a raw material for the preparation of organic compounds,the calcium carbide must be converted into acetylene first,and then acetylene is used to participate in the reactions.Acetylene,however,is a gas.Its flammable and explosive characteristics make it difficult to store and transport,the conditions required to participate in the reaction are severe,and the operation difficulty is relatively large.Encouragingly,recent studies have shown that carbide can be used directly as a sustainable,easy processing and low-cost raw material,and is an efficient acetylene source in situ chemical conversion.This means that a variety of important organic compounds can be prepared directly using carbide,which not only simplifies the traditional process of preparing acetylene,but also reduces the experimental reaction conditions.Therefore,as the main source of acetylene gas,solid carbide is a safer and cheaper alternative to acetylene gas to produce acetylene derived chemicals.Triarylacrylonitrile plays an important role in organic synthesis.They are starting materials for many intermediates with biologically activity.For example,resverat ro l synthesized by them can inhibit certain tumours(breast and prostate cancer).At the same time,it also has a very wide applications in the material chemistry.At present,it is mainly synthesized by the reaction of benzophenone and phenylacetonitrile,but this process is complicated,cumbersome and low yield.Bis(phenylthio)ethenes is an important class of unsaturated organosulf ur compounds,which have Z-and E-isomers.Their Z-isomer is beneficial to the formation of coordination compounds.However,(Z)-1,2-bis(phenylthio)ethenes is mainly synthesized by the reaction of 1,2-dichloroethene or 1,1-dichloroethene with disulfide,but the substrate(dichloroethene)is difficult to obtain,the source is not commercial available,the security is low and it is difficult to control.This dissertation focuses on the synthesis of a series of triaryl acrylonitriles using calcium carbide as a solid source of alkyne,potassium ferrocyanide as a green cyanide source and various iodoaromatic hydrocarbons as substrates;and the synthesis of(Z)-1,2-diarylthioethylenes using calcium carbide as a solid source of alkynes to react with diphenyl disulfide.This paper is mainly divideded into three chapters: Chapter ?: The research progress of calcium carbide in organic synthesis and material chemistry,and the synthesis and application of triarylacrylonitrile and(Z)-1,2-diarylthioethylene are reviewed.Chapter ?: A series of triarylacrylonitriles were synthesized by using calcium carbide as a solid alkyne source,potassium ferrocyanide as a green cyanide source and different substituted iodobenzenes as substrates by one-pot multi-component procedure.This method first combines the inexpensive and easy-to-get calcium carbide with the environmently friendly cyanide reagent potassium ferrocyanide in one organic reaction,effectively avoids the use of highly toxic cyanating source and flammable and explosive acetylene gas.In addition,the range of reaction substrates is extensive and the posttreatment is simple.The products,triarylacrylonitriles,have the potential applicatio n in medicine and material chemistry.Chapter ?: A series of(Z)-1,2-diarylthioethylenes were synthesized by reacting solid calcium carbide with diaryldisulfides.This method provides a new approach for the preparation of unsaturated alkene sulfides.This method is a green,environmenta l ly friendly and transition metal-free.And high yield,low cost,simple operation,easy posttreatment and high stereoselectivity are the advantages of the protocol.