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Reaction Method Study On Copper-catalyzed Oxidative Phosphorylamidation Of Diaryl Methane

Posted on:2019-08-01Degree:MasterType:Thesis
Country:ChinaCandidate:P LiFull Text:PDF
GTID:2371330545950499Subject:Organic Chemistry
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Nitrogen compounds are widely found in nature and play an increasingly prominent role in the fields of medicine,pesticides and flame retardants.At the same time,Organic phosphorus chemistry is closely related to human life and has important applications in medicine,agriculture and biological engineering.The unique structure of phosphonamide and phosphonamide,as well as specific drug and material properties,has also attracted extensive attention.The substrates of amines,amides,sulfonamides and sulfoxide have already realized the construction of C?sp3?-N bond.Meet the requirements of environmental friendliness and atomic economy.In this paper,the phosphorylation of diaryl methane was studied,and the new C?sp3?-N bond was constructed by copper catalysis with phosphonamide and diarylmethane as raw materials.The author explore a method of high efficiency,high universality,simple operation and high yield of diarylmethane phosphamide.In this paper,the following research work is carried out on the phosphamide of benzyl C-H bond:This paper briefly introduces the application of nitrogen compounds in biomedicine.The recent progress in the construction of C?sp3?-N bond has been introduced from three aspects:metal catalyzed C?sp3?-H bond amination,Metal-free catalyzed C?sp3?-H bond amination and photocatalytic C?sp3?-H bond amination.According to a large number of literature surveys and the work of our senior teacher,we finally established the research direction and content of this thesis.This paper introduces the synthesis of substrates.The author uses diphenyl phosphonoyl chloride as the raw material to take the nucleophilic substitution reaction with the ammonia.diphenyl phosphamide was synthesized by high yield.Phenyl phosphoryl dichloride reacts with an equivalent alcohol reaction and then react with ammonia under the condition of nitrogen protection.a series of Alkyl phenyl phosphamide were obtained.The optimal reaction conditions for phosphonamidation of two phenyl methane were investigated by using phosphonamide compound and two phenylmethane as template reaction.the optimum reaction conditions were obtained by optimizing the catalysts,oxidants,solvents and temperatures.In this reaction system,the construction of phosphoramide and diphenylmethane C?sp3?-N bond was realized,and a series of target compounds were synthesized with good yield.The competition reaction between toluene,ethylbenzene,diphenyl methane and phosphoramide was designed,and the reaction activity of different benzyl C-H bonds in the reaction system was compared.By referring to the relevant literature and combining the analysis of the experimental results,the author puts forward the reaction mechanism and makes a reasonable explanation to the mechanism of the reaction.The advantages of the two aryl methanyl phosphonylation amination reaction include high economy,simple reaction operation,less by-products and easy separation and purification.At the same time,the reaction conditions are widely applicable to different substrates and have universal tolerance to common functional groups.All the target compounds synthesized in this paper were identified by IR?1H NMR?13C NMR?31P NMR?EI and HRMS.
Keywords/Search Tags:Diarylmethane, Phosphamide, Amination, C(sp~3)-H Bond, C(sp~3)-N Bond
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