Study On Cross-Coupling And Hydrocyanation Reaction Of Trifluoromethylated Acylhydrazones

Trifluoromethylated compounds have been widely used in the fields of medicine,pesticides and materials.At present,the introduction of trifluoromethyl group into organic molecules can be mainly classified to the following two methods:trifluoromethylation reagent method and trifluoromethyl building block method.In the second method,uses CF₃-containing small organic molecules are mainly used as the building block,followed by chemical transformations to build CF₃-containing organic compounds.Among many trifluoromethyl building blocks,trifluoromethylated acylhydrazones can be used in trifluoromethylation reaction because of its low cost,easy availability and stable properties.In this paper,we based on a brief review of the research progress in free radical addition of imine carbon-nitrogen double bond,we use trifluoromethylated acylhydrazones as a trifluoromethyl building block with diaryloxyphosphines and cyclic ethers to explore the cross-coupling reaction.In addition,we study on the hydrocyanation reaction of trifluoromethylated acylhydrazones.The thesis mainly consists of the following three parts:Chapter one:Research Progress in Free Radical Addition Reaction of Imine In this chapter,the radical addition reactions of free-radical donors to the carbon and nitrogen ends of carbon-nitrogen double bonds of imine compounds were mainly reviewed,respectively.Chapter two:Study on the Cross-Coupling Reaction of Trifluoromethylated Acylhydrazones with Diaryloxyphosphines.In this chapter,the cross-coupling reaction of trifluoromethylated acylhydrazones with diaryloxyphosphines mediated by benzoyl peroxide and copper acetate was explored and a series of functional trifluoromethylated acylhydrazone phosphine oxides were obtained.We constructed a C-P bond on the carbon atom of carbon nitrogen double bond in trifluoromethylated acylhydrazone molecules for the first time,which provides a simple and efficient strategy for the synthesis of functional trifluoromethylated acylhydrazones with potential biological activity.Chapter three:Study on the Cross-Coupling Reaction of Trifluoromethylated Acylhydrazones with Cyclic Ether under the Visible Light.In this chapter,we explored the synthesis of multifunctional trifluoromethylated acylhydrazone cyclic ether compounds through the cross-coupling reaction of trifluoromethylated acylhydrazones and cyclic ethers under the visible light.The method has simple steps and little environmental pollution,as a new method for green and economic synthesis of multifunctional trifluoromethyl acylhydrazone compounds.Chapter four:Study on the Hydrocyanation Reaction of Trifluoromethylated Acylhydrazones.The Lewis acid catalyzed 1,2-addition reaction of trifluoromethylated acylhydrazones with trimethylsilyl cyanide was investigated,and a series of cyanohydrazide compounds containing trifluoromethyl group were afforded in high yield.The method could be easily operated in mild reaction conditions,which provides an efficient method for the synthesis of trifluoromethylated hydrazides with structural diversity.