Magnetic Nano-catalysis Catalyzes Green Synthesis Of 1,5-benzoazazepines

1,5-benzoazazepines（diazepines,sulfur nitrogens）are an important class of nitrogen-containing（sulfur）seven-membered heterocyclic compounds,which are used as analgesics,sedatives,anticonvulsants,antidepressants,anxiolytics and hypnotics agents due to their extensive pharmacological and biological activities.Recently,the results of medical research indicated that 1,5-benzoazazepines could be used as antibiotics,anticancer and antiviral（HIV）agents.In addition,they are important intermediates for the preparation of fused ring derivatives.Therefore,research on the synthesis of 1,5-benzoazazepines（dinitrogen,sulfur nitrogen）has become one of the hot topics.In this paper,a green and novel synthetic methods were developed,and a total of 63 novel 1,5-benzoazazepines（dinitrogen,sulfur nitrogen）compounds were synthesized.The specific research work is as follows:1、The ternary magnetic nano-loaded L-proline was used to catalyze the Knoevenagel reaction.Synthesis ofα,β-unsaturated ketone compounds at room temperature under ethanol as solvent.The 2-aryl-4-methyl-1,5-benzothiazepine compounds of the twelve enamine structures and two imine structures were obtained via domono reaction,which have not been reported in literature.The reaction was achieved by reactingα,β-unsaturated and（substituted）anthrathiophene as raw materials in EtOH under room temperature and Lewis acid CeCl₃ as the catalyst.All the structures of target compounds were analyzed and characterized by MS,IR,¹H NMR,¹³C NMR and elemental analysis.Moreover,the possible reaction mechanism was proposed.The self-made catalysts were analyzed and characterized by means of infrared spectroscopy,solid powder diffraction,scanning electron microscope,transmission electron microscopy,energy spectrum,specific area test and magnetic test.The results showed that magnetic nano-supported L-proline catalysts were successfully prepared.The self-made ternary magnetic nano-supported catalyst has high catalytic activity and can be separated by an external magnet.2、The two-component domino reaction for the synthesis of 5 novel 1,5-benzodiazepine compounds with amide structure and special extra-ring double bond substitution.These reactions were achieved by reacting（substituted）1,2-phenylenediamine,1,3-acetonedicarboxylate as raw materials in EtOH under room temperature-reflux and CeCl₃-KI as the catalyst.All the structures of target compounds were analyzed and characterized by MS,IR,¹H NMR,¹³C NMR and elemental analysis.Moreover,the possible reaction mechanism was proposed.3、The three-component domino reaction for the synthesis of 44 novel1,5-benzodiazepine compounds with special out-of-ring double bonds and multiple ester group substituted（Z）configurations,which have not been reported in the literature.These reactions were achieved by reacting（substituted）1,2-phenylenediamine,1,3-acetonedicarboxylate and aldehyde as raw materials in EtOH under room temperature and ternary magnetic nano-supported CeCl₃ as the catalyst.All the structures of target compounds were analyzed and characterized by MS,IR,¹H NMR,¹³C NMR,elemental analysis and X-ray（Vdb）.Moreover,the possible reaction mechanism was proposed.