Reaction Method Study On N-arylation Of Diphenylphosphonamide/P-alkoxyphenylphosphonamide

We refer to N-containing organic compounds containing amide bonds as amides in many N-containing organic compounds.Its species is very rich and can be divided into amides,sulfonamides,sulfoxide imines,phosphonamides,etc.Depending on the atomic structure it contains.In the amide molecule,N is sp² hybridized and the amide bond is negatively charged.Therefore,amide is widely used in the synthesis of high molecular polymers,natural products,and drug molecules.Therefore,such compounds as phosphonamides possess some specific drug activity.The study of phosphonamide is very important for the treatment of some diseases.In this paper,phosphonamides were studied for their arylation.Phosphonamides a nd arylboronic acids were used as starting materials.A series of N-arylated phosphonamides were successfully prepared by cross-coupling to form new C-N bonds.In this paper,we studied the synthesis of the phosphonamide N-arylation.The following studies were carried out:?1?We first introduced the the types of amide and its application value and summarizes the use of Cham-Evans-Lam coupling method to construct a new C-N bond.Finally,we introduced a variety of amide arylation method.Thus,the research direction and content of this subject are confirmed.?2?We introduced the synthesis of the substrate:?i?Diphenylphosphinic chloride of simple structure,cheap and easy to getas as a starting material,at room temperature,it with ammonia water direct reaction,diphenylphosphinic acid amide 2aa were been synthesized?ii?A series of phosphonamides 2ab-2am were synthesized efficiently by using phenylphosphonic dichloride as starting material,under the protection of nitrogen,phenylphosphonic dichloride reacted with the alcohol,then reacted with ammonia water.?3?We used alkynl diphenylphosphinamide and methylbenzoic acid as model substrates to optimize the reaction conditions.The optimal reaction conditions were obtained by optimizing the conditions such as additives and their dosage,solvent,alkali,temperature,reaction time,molecular sieve and other conditions were screened.Then,under the optimum conditions,we obtianed a series of N-arylated phosphonamides with various functional groups in high yields through cross-coupling.?4?The author also made some derivatization experiments in the third chapter,under the best reaction conditions,diphenylphosphine and arylborate can also obtain N-arylated products with higher yield.In addition,we are using the N-arylated product by obtained in this experiment as a raw material,reacted with themethylbenzoic acid,the temperature of the product was raised to 120°C to obtain the N,N-diarylated product.By referring to the reaction mechanism proposed by our predecessors and according to the structure of the obtained target compound and the reaction conditions:a possible cross-coupling reaction mechanism was proposed,and the reaction mechanism was reasonably explained.In this paper,all the target compounds synthesized in this paper were confirmed by ¹H NMR,¹³C NMR,³¹P NMR,EI,IR and HRMS.The phosphonamides and arylboronic acids studied in this article are cross-coupled to synthesize N-arylated phosphonamides with the advantages of atomic economy,less by-products,simple operation and easy separation.Moreover,the target compounds are easy to be separated.The system has a wide range of applicability to different substrates and is generally tolerant to common functional groups,providing a new method for the synthesis of 3-hetero isocoumarins.