串联反应一锅合成茚酮稠合1,5-苯并二氮杂䓬化合物

One-pot Synthesis of Indanone Fused 1,5-benzodiazepines by Tandem Reaction

以取代的邻苯二胺、1,3-茚满二酮、醛类化合物(苯乙醛,苯丙醛)为原料,无水乙醇为溶剂,对甲苯磺酸为催化剂,应用串联反应一锅合成了8种结构新颖的茚酮稠合1,5-苯并二氮杂䓬化合物.该串联反应经历了两次亲核加成-消除反应过程,形成含烯胺和亚胺结构的活性中间体,再经分子内碳碳偶联环合和质子迁移形成了目标化合物,针对该三组分串联反应提出了合理的反应机制.该方法具有新颖、绿色环保、反应条件温和、底物范围广等诸多优点,为苯并二氮杂䓬化合物的合成提供了高效简便的新思路.

Eight novel indanone fused 1,5-benzodiazepine compounds were synthesized by one-pot tandem reaction using substituted o-phenylenediamine,1,3-indandione,and aldehydes(phenylacetaldehyde,phenylpropanal)as raw materials,absolute ethanol as solvent and p-toluenesulfonic acid as catalyst.Experiments showed that the tandem reaction underwent two nucleophilic addition-elimination reaction processes to form an active intermediate containing both enamine and imine structures,and then the target compound was formed through intramolecular carbon-carbon coupling cyclization and proton transfer.A reasonable reaction mechanism was provided for the three-component tandem reaction.The synthesis method has many advantages,such as novelty,green environmental protection,mild reaction conditions,wide range of substrates,which provides a new efficient and convenient approach for the synthesis of benzodiazepine compounds.