【作者】 杨鹏；

【导师】 王治永；

【作者基本信息】 重庆大学 ， 工程硕士（化学工程领域）（专业学位）， 2017， 硕士

【摘要】 吡唑作为最常见的杂环结构之一,广泛存在于多种具有显著生物活性的天然产物和药物分子之中,在医药、农业方面有着重要的应用。吡唑衍生物还被广泛应用于材料化学、食品工业和液晶材料等领域。此外,取代的吡唑衍生物作为配体,也被成功的应用到过渡金属催化的偶联反应中。因此发展全新高效、绿色的策略合成吡唑衍生物是非常必要的。本文基于原位生成的腈亚胺作为关键中间体,发展了两种高区域选择性合成多取代吡唑的方法,详细内容如下:(1)研究了碘化亚铜催化的α-氯代腙和末端炔的串联环化反应,采用一锅法方便有效的合成结构多样性的1,3,5-三取代-1-H-吡唑类化合物,该反应通过末端炔对原位生成的腈亚胺的亲核加成得到α,β-炔基腙,随后在碘化亚铜作用下发生分子内亲电环化得到吡唑衍生物。(2)发展了α-氯代腙与环丙-2-烯-1,1-二腈衍生物的1,3-偶极环加成反应,在碱促进下,快速有效的合成了四取代的吡唑衍生物,该方法具有操作简单,反应条件温和等特点。更多还原

【Abstract】 Pyrazole,one of the most common heterocyclic structures,is widely found in natural products and drug molecules with significant biological activity,and has important applications in drug and agriculture.Moreover,some pyrazoles are used in polymer chemistry and food industry,while some have liquid crystal properties.Substituted pyrazoles have also been applied as ligands for transition metal-catalyzed reactions.It is highly desirable for the development of a direct method for the synthesis of pyrazole derivatives.This thesis is based on in situ formation of nitrile imine as a key intermediate,two methods of regioselectivity synthesis of substituted pyrazole were developed,the content is as follows:Firstly,we described copper(I)iodide catalyzed tandem reaction of α-chlorohydrazone and acetylene,using a pot method to facilitate the effective synthesis 1,3,5-trisubstitute-1H-pyrazoles,this reaction obtain the α,β-alkynylhydrazone by the nucleophilic addition of the acetylene to the in situ formed nitrile imine,and in the role of copper under the action of molecular electrophilic cyclization reaction to Synthesis pyrazoles.Secondly,we have developed a efficient method for the synthesis of fully substituted pyrazoles with α-chlorohydrazone and cycloprop-2-ene-1,1-dicarbonitrile via a 1,3-dipolar cycloaddition reaction,this method has the characteristics of simple operation,mild reaction condition etc.更多还原