Synthesis Of Functionalized 1,5-benzazepines (Dinitrogen,Oxygen-nitrogen) By Multicomponent Tandem Reactions

1,5-benzodiazepines and 1,5-benzoxazepines are very important class of nitrogencontaining heterocyclic compounds with high physiological activity and pharmacological activity,with anti-anxiety,antidepressant,anticonvulsant,anti-inflammatory,sedation and hypnotic effects.Its important pharmacological value has been extended to the treatment of diseases such as cancer,schizophrenia and cardiovascular diseases.Apart from being biologically active,1,5-benzodiazepines and 1,5-benzoxazepines also find applications as dyes for acrylic fibres in photography.Furthermore,they are key synthons for the synthesis of various fused ring compounds.Therefore,the development of efficient and green synthetic strategies for the synthesis of 1,5-benzodiazepines and 1,5-benzoxazepines remains the research direction of contemporary organic synthesis chemistry.Our group has been working on the green synthesis of 1,5-benzoazepine compounds in the early stage.In view of this,several novel multi-component/tandem pot synthesis methods of 1,5-benzodiazepines and 1,5-benzoxazepines with different structures have been developed in this thesis.To a certain extent,these methods have realized the green synthesis of1,5-benzodiazepines and 1,5-benzoxazepines,and also promoted the development of the current synthesis methodology in a sense.The main work of this thesis is as follows:1.The multicomponent/tandem one-pot synthesis methods were used to efficiently synthesize 26 unreported 3-benzoyl-1,5-benzodiazepines through a magnetic nano-loaded catalyst?Fe₃O₄@SiO₂-CeCl₃?prepared in the early stage of the laboratory?yield 71-90%?.In this method,acyl,ester and carboxyl groups were introduced into the heptacyclic skeleton of1,5-benzodiazepine under mild reaction conditions.Moreover,the plausible reaction mechanism has been proposed.2.A one-pot four-component green synthesis method containing multi-functional1,5-benzodiazepine compounds was developed.These reactions were achieved by reacting?substituted?acetophenone N,N-dimethylformamide dimethyl acetal,?substituted?1,2-phenylenediamine with 2,3-dicarbonyl compounds in EtOH via a magnetic nano-loaded catalyst?Fe₃O₄@SiO₂-CeCl₃?prepared in the pre-laboratory.High efficiency synthesis of 40novel compounds containing acyl,ester,alkyl,aryl and other functional groups substituted by1,5-benzodiazepines.Moreover,the plausible reaction mechanism has been proposed.3.A novel synthesis method of 1,5-benzodiazepine was developed based on the synthesis of mannich-four components in one pot.These reactions were achieved by reacting1,3-dicarbonyl compounds,polyformaldehyde,dimethylamine hydrochloride,?substituted?1,2-phenylenediamine in mixed solvent?water and ethanol?via a magnetic nano-loaded catalyst?Fe₃O₄@SiO₂-Mandelic acid?prepared in the pre-laboratory.A novel 1,5-benzodiazepine compound with the structure of enylamine was synthesized in one pot.Moreover,the plausible reaction mechanism has been proposed.4.A simple and efficient protocol has been developed for the synthesis of 30 novel1,5-benzoxazepine fused tricyclic or tetracyclic via three-component reactions.These reactions were achieved by reacting?substituted?o-aminophenol,?-cyclodione?cyclohexadione,cyclopentadione?,aromatic aldehyde and ethyl glyoxalate in acetonitrile via a magnetic nano-loaded catalyst?Fe₃O₄@SiO₂-LaCl₃?prepared in the pre-laboratory.A novel1,5-benzodiazepine compound was synthesized in one pot.Moreover,the plausible reaction mechanism has been proposed.