New Green Chemistry Reaction Of C-Se Bond Formation And The Synthesis Of Building-blocks Of New Molecular Shuttle

It has been researched on the reaction of terminal acetylenes with diaryl diselenides catalyzed by cesium hydroxide. We discover that at low temperature, two selenium atoms of diaryl diselenides transform into products and the reaction give almost quantitative alkynyl selenides with oxygen as oxidant; at room temperature under N2, the reaction give (Z)-l,2-bis(arylseleno)alkenes.Trimethylsilylacetylene differ from l-alkyl(aryl)-yne since its hydrogen proton and trimethylsilyl group can react with base. It has been researched on the reaction of trimethylsilylacetylene with diphenyl diselenide catalyzed by cesium hydroxide. The results show that solvent, temperature and with oxygen as oxidant have great impact on products. In THF at -20 C under air, two selenium atoms of diphenyl diselenide transform into products and the reaction give l,2-bis(phenylseleno) acetylene as main product; but the reaction give tri(phenylseleno)ethene as main product at RT. In DMF at RT under N2, the reaction give (Z)-1,2- bis(phenylseleno)ethene.The mechanism of all the reactions have been discussed. All the compounds have been characterized by 1HNMR,13CNMR and MS. The research discover the green chemistry reaction of C-Se bond formation. It afford a new pathway for the synthesis of two classes of organoselenium reagents of alkynyl selenide and vinylic selenide.Molecular shuttle is the front research field in organic chemistry. It has not been reported on ion-shaped molecular shuttle which control movement based on coordination and inner-salt shaped molecular shuttle. Two new types of molecular shuttle have been designed. The first one is that which is able to control the movement of the bead by the coordination with metal ion by incorporating 2,2' -bipyridine unit into its dumbbell-shaped component. The second one is inner-salt shaped molecular shuttle. Dumbbell-shaped compounds for building the first one and 3-aryloxy-1,2-epipropan as basic building-blocks for building second one have been synthesized. Their synthesis methods have been discussed and the properties of all kinds of intermediates has been researched. The structures of all compounds have been characterized by 1HNMR and 13CNMR.