Preparation Of Ternary Magnetic Nano-supported Catalyst And Application In Synthesis Of Benzodiazepine

Magnetic nano-supported catalyst is a novel catalyst with several advantages of strong thermal stability,recyclability,high recycling rate andeconomic,environmental protection,etc.Magnetic nano-supported catalyst is a great candidate for the development of clean energy and environmental protection.Therefore,more and more researchers are trying to develop a new kind magnetic nano-supported catalyst and applyinginto organic chemistry synthesis.Benzodiazepine and their derivatives are very important class of nitrogencontaining heterocyclic compounds with high physiological activity and pharmacological activity.The development of these compounds has potential drug applications,and they have been widely used as anticonvulsants,anxiolytics,analgesics,sedatives,antidepressants,hypnotics and anti-inflammatory drugs.Our group has been working on designing and synthesizing 1,5-benzodiazepine compounds,and aimed to develop novel and green synthetic methods,such as one-step multi-component synthesis,tandem reaction synthesis,and supported catalytic synthesis.In this thesis,seven nano-magnetic supported catalysts were successfully prepared.After series characterization analysis,these catalysts were applied to catalytic synthesis of a series of 3-arylcarbonyl-1,5-benzodiazepine compounds,and a special rearrangement reaction was found.The main work was summary as the following three aspects:1?A class compound of 2-phenyl-3-?3-oxobutenyl?-benzoxazoles were synthesized successfully using 2-aminophenol,aromatic aldehyde and 3-butyn-2-one for the first time.All the structures of target compounds were characterized by ¹H NMR,¹³C NMR,IR,MS,elemental analysis and X-ray??c?.According to the mechanism of intermediate that formed by the reaction,it was found that the intermediate was formed by a special rearrangement reaction.Then,the theory of the rearrangement mechanism was verified by density functional theory?DFT?method at B3LYP/6-31G?d,p?level from both molecular energy and atomic charge in Gaussian03 package.2?Seven new ternary magnetic nano-loaded solid acid catalysts were preparedby the dipping method and the chemical method such as the silane coupling agent.The synthetic nano-scale magnetic Fe₃O₄ was used as core and silica was used as the magnetic matrix protection material and loaded solid acid?p-toluenesulfonic acid,cerium chloride,copper chloride,nickel chloride,mandelic acid,silicotungstic acid?on its surface.Then,the ternary magnetic nano-supported with solid acid catalyst were demonstrated via solid powder diffraction,scanning electron microscopy,energy spectrum,transmission electron microscopy,specific area test and magnetic test.3?Based on the synthesized ternary magnetic nano-supported with solid acid catalyst,twelve 3-arylformyl-1,5-benzodiazepine compounds were successfully prepared which have not been reported yet.These compounds were synthesized using substitutedorunsubstitutedo-phenylenediamine,acetophenone,N,N-dimethylformamide dimethyl acetal and cinnamaldehyde?trans-2-hexenal,cyclohexylformaldehyde?in the green solvent EtOH at room temperature under the presence of Fe₃O₄@SiO₂-TsOH.All the structures of target compounds were characterized by ¹H NMR,¹³C NMR,IR,MS and elemental analysis.In addition,the possible reaction mechanism was proposed.The synthesized-catalyst spresented advantages of high catalytic efficiency and recyclability.