The Related Coupling Research Of Sodium Arylsulfinate And Aryl Alkyne

Sonogashira coupling reaction plays an important role in the synthesis of many complex drugs, organic molecules and natural products which may be used to prepare the alkynyl and aryl ketone compound and has been very mature after many years of development. However, it is still a hot topic in organic synthesis. Furthermore, The formation of diaryl alkyne can get a very practical significance through the reaction of aryl-sulfonate and aryl alkyne, due to the stability and low cost advantages of aryl-sulfonate.Biaryl, diaryl sulfides, diaryl sulfides and their derivatives formed through couplings of C-C or C-S bond are also the basic structural unit of the materials of many biologically active compounds, natural products, drugs and functional intermediates and have a very wide range of applications in modern synthetic organic chemistry.The main work of this paper is divided into the following three parts:(1) Optimizing the conditions of the standard substrate of phenylacetylene and p-methoxy-iodobenzene including investigating the type of solvent, type and amount of base, the amount of solvent, the amount of catalyst and other respectively factors to obtain the optimal reaction conditions for this reaction: the standard substrate p-methoxy-iodobenzene in an amount of 0.2 mmol, an amount of a palladium catalyst was 0.075 mol%,3.0 equivalents of CH3COONa as the base, the solvent was DMSO in an amount of 1.0 mL, the reaction temperature was 50℃ under the atmosphere of N2 protection,1.5 equivalent of the phenylacetylene, and under those conditions the yield was 93%. Next, including extended iodobenzene, bromobenzene, chlorobenzene and alkynes, the broad-spectrum resistance were examined under the optimal reaction conditions described above and further modifications of reaction; The results showed that the optimal reaction conditions were good adaptability for the electronic effects or spatial effects, it also suggested that the nano-palladium catalyst performed the high catalytic effect.(2) We got the optimal conditions which sodium arylsulfinate can generate different homocoupling products in the different conditions:① As the substrate, the amount of sodium arylsulfinate was 0.2 mmol, the dosage of Pd (OAc)2 was 5 mol%, the amount of the solvent DMF was 0.8 mL, reaction temperature was 110 ℃, the dosage of additive catalyst FeBr3 was 5 mol%. When the reactions were in this optimal conditions 7h, biphenyl yield can reach 99%. ② The amount of sodium arylsulfinate was 0.4 mmol, the dosage of Pd (OAc)2 was 1 mol%, the amount of NMP was 1 mL, reaction temperature was 150 ℃, after 25 h, diphenyl sulfide yield can reach 81%.③ Sodium benzene substrate in an amount was 0.2 mmol, the amount of Fe was 2 equiv., hydrochloric acid of 12mol/L in an amount was 4.0 equiv., the amount of the solvent DMF was 1 mL, the reaction temperature was 130 ℃, after 7 h, the yield of diphenyl disulfide can reach 93%. Next, under optimal conditions, examining the extended sodium arylsulfinate can get the good yield.(3) Conducting a preliminary screening conditions of oxidative coupling reaction of sodium arylsulfinate and phenylacetylene, we successfully get the ideal product.