The Study Of Coupling Reaction Promoted By Samarium Reagent-DMF Under The Catalysis Of Copper

This article is divided into four chapters altogether,we make a brief description of the reactions promoted by samarium reagents, samarium diiodide and samarium triiodide in the first chapter.And next we make a brief introduction of copper reagent and DMF related with the first chapter.We can see the coupling reactiongs of α-halogenated aromatic ketone in the system of Sm I₃/CuI/DMF in the second chapter. In the third chapter, we make a exploration of the reaction of phenylacetylene and benzoyl chloride.The fourth chapter introduce the experimental procedure of the two reaction systems and precursors material.The first chapter we briefly recounted some of the literature related to this thesis. Due to the main work of our laboratory is to study the response of samarium reagents, samarium diiodide and samarium triiodide,so we make a introduction of samarium reagents, samarium diiodide and samarium triiodide one by one in literature review.The second chapter we make a detailed report of the first reaction system we have done.We have discovered a new application of samarium triiodide in the role of Cu I.We found a novel and effective method of α-halogenated aromatic ketone synthesis α-hydroxy-1,4-doketone. Through a lot of confirmatory experiments and consulting a large number of relevant literature,we foung that DMSO could provide the hydroxyl in the reaction as the source of oxygen.We also discover that DMF do not play the role of reaction solvent,it can provide oxygen or other functional groups.Finally, through the analysis of the experimental results we confirm that the hydroxyl come form DMF, this is the charm of our reaction.In addition, we have got other two homocoupling products, and the two products are 1,4-diketones and 1,2,3-tri（4-toloyl） cyclopropane. The synthesis of1,2,3-tri（4-toloyl） cyclopropane is critical to our whole experiment.It makes the reaction mechanism of the experiment more clear and makes our experiment more persuasive.Of course, in order to determine the reaction mechanism, we also made a product of hydroxyl dehydration, and it makes our job more convincing. The appearance of 1,4-diketones can highlight the innovation of our products, and meanwhile it also let us know the importance of DMF.In the third chapter, we found that phenylacetylene and benzoyl chloride can produce trans-1,2,4-triphenyl-1,4-dicarbonyl-2-butene in the system of Sm/DMF. The reaction further expand the properities of samarium in DMF, and we have a new understanding of terminal alkynes.We also got another product which produced by benzoyl chloride react with itself in the system of Sm/DMF in room temperature, and other two products which benzoyl chloride react with itself appeared under heating.In order to make the result of the reaction more persuasive, we have done a experiment of phenylacetylene and 4-methyl benzoyl chloride. We further determine the structure of the product through NMR of trans-1,2,4-tri（4-methylphenyl）-1,4-dicarbonyl-2-butene.The fourth chapter mainly includes the reaction apparatus we used in the experiment, the experiment steps we have done, the steps of the experiment some verification experiments and training steps we get the single crystal.