Study On The Construction Of Nitrogen And Sulfur Heterocycles Using Aromatic Amines And Aliphatic Amines As Materials

Thiazine and thiazole compounds,as a class of organosulfur compounds containing sulfur-nitrogen bonds,have been drawn much interest in diverse fields due to their vital applications in the field of organic synthesis,photoliable therapy,materials chemistry,and food science,particularly in the area of pharmaceuticals and industrial manufacturing.Therefore,in this paper,the five-membered and six-membered sulfur nitrogen heterocyclic compounds are constructed via the activation of the aromatic ketone C（sp³）-H bonds under metal-free and additive-free conditions.And with the participation of molecular oxygen,the C-C single bond was further oxidized to successfully synthesize cis-[1,4]thiazine compounds with C=C double bonds.In addition,lacunary polyoxometalate foams have been prepared for efficient aerobic oxidative coupling of S-H bonds with N-H bonds.The specific work is as follows:1.A controlled strategy for selective synthesis of 2-acylbenzothiazoles and bibenzo[b][1,4]thiazines from aryl methyl ketones and disulfanediyldianilines was realized using I₂/DMSO or I₂/Me CN systems,respectively.The desired products were synthesized in only 15 minutes with moderate to excellent yields（50-90%）under microwave-assisted,metal-free conditions.To gain insight into mechanism of this reaction,the control experiments were designed.All the products were characterized by ¹H NMR,¹³C NMR,and HRMS.2.Twelve examples of（Z）-dibenzo[1,4]thiazine compounds has been successfully synthesized with the participation of molecular oxygen and the assistance of microwave.（Z）-dibenzo[1,4]thiazine were obtained through a one one-step reaction of disulfanediyldianilines and aryl methyl ketones with I₂/DMSO systems.All the products were characterized by ¹H NMR,¹³C NMR,and HRMS.3.Four transmition-metal substituted LPOMs（TM-LPOMs）have been shaped on the commercial carboxymethylcellulose（CMC）by a facile freeze-drying strategy,forming the TM-LPOMs-based CMC foam materials,TM-LPOMs@CMC-F（TM=Cu,Co,Mn,Ni;F=20%,40%,60%,80%）.These foam materials were characterized by IR,PXRD,UV,SEM,et al.Cu-LPOMs@CMC can serve as powerful heterogeneous aerobic oxidative coupling catalysts for coupling of thiols and amines to construct S-N bonds of sulfenamides in up to 96%yield.Moreover,the catalyst was recycled and reused up to three runs without any significant loss of its catalytic activity.