本文選題：肟自由基 + 異VA唑啉　； 參考：《蘭州大學(xué)》2017年碩士論文

【摘要】：自由基串聯(lián)反應(yīng)作為一種合成雜環(huán)化合物的重要策略,近些年來被廣泛的研究和應(yīng)用。在這些自由基串聯(lián)反應(yīng)中,多數(shù)是用碳原子作為中心進(jìn)行反應(yīng)的研究,相比較而言,雜原子自由基為中心的自由基串聯(lián)反應(yīng)研究的較少。而肟自由基作為一種重要的雙雜原子自由基,近來也被應(yīng)用到自由基串聯(lián)反應(yīng)中,為異VA唑啉類和環(huán)狀硝酮類化合物的合成提供了一種高效、便捷的方法。雖然肟自由基參與的串聯(lián)反應(yīng)近幾年一直有化學(xué)家在報道,但是其參與的和內(nèi)烯烴的串聯(lián)反應(yīng)以及和疊氮烯的串聯(lián)反應(yīng)至今無人報道。本論文的主要研究內(nèi)容是通過對肟自由基的結(jié)構(gòu)以及性質(zhì)的研究和認(rèn)識,設(shè)計(jì)了肟自由基參與的連續(xù)串聯(lián)反應(yīng),實(shí)現(xiàn)了官能團(tuán)的異VA唑啉類化合物高效、便捷、有效的合成。本論文分為三個部分:第一章:文獻(xiàn)綜述,簡要介紹了肟自由基的結(jié)構(gòu)和性質(zhì),并對其在有機(jī)化學(xué)反應(yīng)中的應(yīng)用做了簡要綜述。第二章:用內(nèi)烯烴二硫縮烯酮和β,γ-不飽和酮肟作為原料,在無溶劑,非金屬,過氧化苯甲酸特丁酯(TBPB)作為氧化劑的條件下,利用肟自由基參與的串聯(lián)反應(yīng),實(shí)現(xiàn)了分子間的串聯(lián)環(huán)化加成,此反應(yīng)中伴隨著C(sp3)-O和C(sp3)-C(sp2)鍵的形成,同時也實(shí)現(xiàn)了異VA唑啉功能化的二硫縮烯酮化合物高效,便捷的合成。第三章:用疊氮烯和不飽和酮肟作為廉價易得的原料,用醋酸錳(III)二水合物作為氧化劑,乙腈作為溶劑,在氬氣條件下,溫度為30 oC時反應(yīng)4個小時。實(shí)現(xiàn)了肟自由基參與的分子內(nèi)雙鍵的氧烷基化/氮烷基化反應(yīng);與此同時,還實(shí)現(xiàn)了異VA唑啉類衍生物和環(huán)狀硝酮類衍生物的合成。該反應(yīng)具有收率高,適用于各種相應(yīng)的底物,易于操作,條件相對較溫和等特點(diǎn)。
[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, 緯 -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，

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