Bi-complex Catalyzes 1,6-conjugation Addition Of Para-quinone Methides

1,6-Conjugated addition reaction is an organic reaction that can increase the carbon chain,and para-quinone methylates?p-QMs?are one of the most ideal substrates for this type of reaction due to their unique molecular structure.Asymmetric diarylmethane derivatives are the core skeleton of many biologically active molecules,such as diarylmethyl sulfide derivatives showing potential antitumor and antimalarial activities;asymmetric triarylmethane derivatives are a good structural motif is widely used in drugs,functional materials and organic synthesis.In this paper,using p-QMs as the parent structural unit and different nucleophiles,such as thiol,?-keto acid and 2-naphthol can achieve 1,6-conjugated addition reaction under the catalytic conditions of recyclable bismuth catalyst,synthesis asymmetric diaryl and triarylmethane derivatives.The specific content is as follows:First,in this paper,(C₄H₁₂N₂)₂[BiCl₆]Cl?H₂O catalyst was prepared by volatilization method with metal bismuth chloride and anhydrous piperazine.Its structure has been verified by X-ray single crystal diffraction.Second,using(C₄H₁₂N₂)₂[BiCl₆]Cl?H₂O as a catalyst to catalyze the 1,6-conjugated addition reaction of p-QMs and thiophenol derivatives.Reaction in methylene chloride solvent at room temperature,screening the optimal reaction conditions in terms of catalyst,solvent,batching ratio,etc.By single factor method,conducting catalyst recyclable recycling experiment,synthesizing a series of sulfur-containing asymmetric diarylmethane derivative compounds which structure is characterized by IR,MS,¹H NMR,¹³C NMR and other methods.Third,using(C₄H₁₂N₂)₂[BiCl₆]Cl?H₂O as a catalyst,under mild conditions,achieving1,6-conjugated addition reaction of p-QMs and?-keto acid derivatives to synthesize asymmetric diarylmethane derivatives.The reaction is carried out under optimal conditions,and the experimental operation is simple and convenient.The experimental reaction mechanism is explored through a controlled experiment,the sequence of addition and decarboxylation is proved,the catalyst can be recycled,and a series of asymmetric diaryls are synthesized methane derivative,and its structure was characterized by IR,MS,¹H NMR,¹³C NMR and other methods.Fourth,using(C₄H₁₂N₂)₂[BiCl₆]Cl?H₂O as a catalyst,the 1,6-conjugated addition reaction of p-QMs and 2-naphthol was used to synthesize an asymmetric triarylmethane derivative.Reaction at room temperature in methylene chloride solvent,single factor method was used to screen the optimal reaction conditions in terms of catalyst,solvent,batch ratio,etc.,catalyst recyclability experiment was carried out,and a series of asymmetric triarylmethane derivatives were synthesized.The structure of the compound was characterized by IR,MS,¹H NMR,¹³C NMR and other methods.