肟自由基参与的串联反应的研究

发布时间：2018-05-05 18:02

  本文选题：肟自由基 + 异VA唑啉　； 参考：《兰州大学》2017年硕士论文

【摘要】：自由基串联反应作为一种合成杂环化合物的重要策略,近些年来被广泛的研究和应用。在这些自由基串联反应中,多数是用碳原子作为中心进行反应的研究,相比较而言,杂原子自由基为中心的自由基串联反应研究的较少。而肟自由基作为一种重要的双杂原子自由基,近来也被应用到自由基串联反应中,为异VA唑啉类和环状硝酮类化合物的合成提供了一种高效、便捷的方法。虽然肟自由基参与的串联反应近几年一直有化学家在报道,但是其参与的和内烯烃的串联反应以及和叠氮烯的串联反应至今无人报道。本论文的主要研究内容是通过对肟自由基的结构以及性质的研究和认识,设计了肟自由基参与的连续串联反应,实现了官能团的异VA唑啉类化合物高效、便捷、有效的合成。本论文分为三个部分:第一章:文献综述,简要介绍了肟自由基的结构和性质,并对其在有机化学反应中的应用做了简要综述。第二章:用内烯烃二硫缩烯酮和β,γ-不饱和酮肟作为原料,在无溶剂,非金属,过氧化苯甲酸特丁酯(TBPB)作为氧化剂的条件下,利用肟自由基参与的串联反应,实现了分子间的串联环化加成,此反应中伴随着C(sp3)-O和C(sp3)-C(sp2)键的形成,同时也实现了异VA唑啉功能化的二硫缩烯酮化合物高效,便捷的合成。第三章:用叠氮烯和不饱和酮肟作为廉价易得的原料,用醋酸锰(III)二水合物作为氧化剂,乙腈作为溶剂,在氩气条件下,温度为30 oC时反应4个小时。实现了肟自由基参与的分子内双键的氧烷基化/氮烷基化反应;与此同时,还实现了异VA唑啉类衍生物和环状硝酮类衍生物的合成。该反应具有收率高,适用于各种相应的底物,易于操作,条件相对较温和等特点。
[Abstract]:As an important strategy for the synthesis of heterocyclic compounds, free radical series reaction has been widely studied and applied in recent years. In the series reaction of these free radicals, most of the reactions were carried out with carbon atom as the center, compared with that of the heteratomic radical, the studies on the series reaction of heteratomic free radical were less. Oxime radical, as an important diheteratomic radical, has recently been used in the series reaction of free radical, which provides an efficient and convenient method for the synthesis of iso-VA azoline and cyclic nitrone compounds. Although the series reactions involving oxime radicals have been reported by chemists in recent years, the series reactions of oxime radicals with endolefins and with azidene have not been reported. The main research content of this thesis is to design the continuous series reaction of oxime radical by studying the structure and properties of oxime radical, and to realize the efficient, convenient and effective synthesis of functional group iso-VA azoline compounds. This paper is divided into three parts: chapter 1: literature review. The structure and properties of oxime radical are briefly introduced, and its application in organic chemical reaction is briefly reviewed. Chapter 2: using endolefins dithioenone and 尾, 纬 -unsaturated ketone oxime as raw materials, under the conditions of solvent free, non-metallic, TBPBO _ 2 as oxidant, the series reaction of oxime radical was used. The series cyclization addition between molecules was realized, which was accompanied by the formation of C(sp3)-O and Cnsp _ 3C _ (P _ (2) bonds, as well as the efficient and convenient synthesis of VAisozoline functionalized dithioketene compounds. In chapter 3, azidene and unsaturated ketone oxime were used as cheap raw materials, manganese acetate II I) dihydrate as oxidant, acetonitrile as solvent, and reaction temperature 30 鈩，

本文编号：1848738