Study On The Reaction Of 3-methyleneoxindole With In Suit Formation Of ?-acyl Diazonium Compounds

Spirooxindoles are of great importance in synthetic methods,pharmacochemistry and natural product chemistry.These core structures exist in many natural alkaloids,medicinal value molecules and biological activity molecules,as a result,they have been widespread concern.3-methylene oxindole is a common building block for the synthesis of spirocyclic oxindole by 1,3-dipolar cycloaddition,Michael-type reaction,Diels-Alder reaction,Mannich reaction and other domino reaction.In this dissertation,we could selective construct two different structures by using 3-methylene oxindole and the in situ generated a-acyl diazo compound as the substrates through in the reaction conditions.We achieved the synthesis of spiro dihydropyrazole oxindole compounds and oxindol allyl compounds,respectively.In addition,we discussed the relevant reaction mechanism.The main contents of the paper include the following two parts:In the first chapter,we reviewed the progress of the synthesis of spiro-oxindole derivatives with 3-methylene oxindole as substrate and the application of spiro-hydroxyindole compounds in medicine and so on.In the second chapter,based on our previous study of domino reactions,we studied the reaction of p-toluenesulfonyl hydrazide,monohydrated aryl ketone and 3-methylene oxindole as substrates in the condition of DBU as base,and oxindole pyrazolines were obtained.Through a series of control experiments and the revelation supporting literature,we propose a possible reaction mechanism via in situ generateda-acyl diazo/1,3-dipolar cycloaddition during the reaction process.When we use NaOH as the base and raise the reaction temperature,the allyl-oxindole products were obtained.Through the exploration of the reaction mechanism,we propose the reaction may involve a novel denitrification ring-opening process.