Study On The Reaction Of Ketone With Acetonitrile Under The Synergistic Activation Of CaC₂ And CsF

CaC2 is an ionic compound.C=C2-ions have many unique properties and deserve further study,such as strong Lewis basicity,strong reducibility,strong dehydration,and nucleophilicity.However,the strong lattice structure and insolubility of CaC2 in organic solvents limit its application in organic synthesis.Therefore,it is of great significance to study the new uses of calcium carbide in producing some high value added chemicals by utilizing its intrinsic properties reasonably.In addition to be used as acetylene source,CaC2 can also be used as a strong alkaline activator for some base-catalyzed reactions,especially the reactions involving trace amounts of water such as ketone condensation.The reaction can be promoted by calcium carbide due to its instant removal for the water byproduct.Therefore,the thesis will study the application of CaC2 as an alkaline activator and dehydrating agent for the synthesis of high value-added chemicals.Firstly,the condensation reaction of acetonitrile with acetone or cyclohexanone under the synergistic activation of CaC2 and CsF was studied to prepare the corresponding acrylonitriles.In this process,the effects of calcium carbide and barium fluoride,as well as the reaction temperature,time and the amount of barium fluoride on the reaction were investigated.By analyzing the liquid phase products,the reaction mechanism of acetone or cyclohexanone with acetonitrile was proposed.The reaction of butanone and cyclohexanone with acetonitrile under the optimum conditions of acetone and cyclohexanone was studied.Secondly,2-cyclopentylenecyclopentanone was prepared for the first time by rapid condensation of cyclopentanone under the synergistic activation of CaCi and CsF.We explored the role of CaC2 and CsF,as well as the effects of temperature,time,and amount of CsF on the reaction.The condensation reaction mechanism of cyclopentanone was proposed by analyzing the liquid phase product.Finally,the reaction rules of ketones with acetonitrile were summarized according to the reaction results.