Research Of One-pot Synthesis Of Methylthio Aryl Diynes

Organic compounds, that contain several thiomethyls at the terminal, can assemble nanoparticles to nanoparticle clusters, whose size and shape can be adjusted by the compounds. Our laboratory had designed and synthesized arylethyne thio ethers, which are different in shape,Ï€conjugated and contain several thiomethyls. Those compounds are important for getting some functional molecules that have good assembling effect, especially for getting those that can control the shape and the size of the cluster. Based on the preceding research of our laboratory, this paper synthesized some aryldiynes thio ethers,which areÏ€conjugated and contain several thiomethyls at the terminal.Halogenated aryldiynes methylthio ethers are important material for synthesizing aryldiynes methylthio ethers that have several thiomethyls at the terminal. But there haven't been any satisfactory methods for preparing those compounds so far. Therefore, this paper studied the methodology for preparation of aryldiynes methylthio ethers using methyl thio methyl phenyl sulfone (MP-S) and arylpropargyl aldehydes. Firstly, MP-S was prepared according to the modified Ogura method, and a series of arylpropargyl aldehydes were synthesized from halogenated arenes by Sonogashira reaction and oxidation. Then, the one-pot reaction using MP-S and arylpropargyl aldehydes was discussed, and a series of aryldiynes methylthio ethers were successfully prepared accordingly. The method has following advantages: accessible materials, simple manipulation and good yield.In order to clarify the course of the formation of aryldiynes methylthio ethers, the mechanism of the one pot reaction was studied step by step. After trapping and structure analysis of the intermediates forming at the different steps of the reaction, the mechanism of double elimination was confirmed. The results from X-ray crystallographic analysis indicated that the intermediates with double bond have E configuration.In the last part of the paper, the preparation of V shaped and Y shaped aryldiynes methylthio ethers with several thiomethyls at the terminal were studied using halogenated aryldiynes methylthio ethers synthesized by one-pot reaction. Iodic aryldiynes methylthio ethers reacted with diarylethyne and triarylethyne respectly by Sonogashira reaction afforded successfully V shaped and Y shaped aryldiynes methylthio ethers. The structure of some intermediates and all target compounds synthesized in this paper were characterized by ¹H NMR, ¹³C NMR, MS and IR.