本文選題：重氮化合物 + 烯胺酮　； 參考：《江蘇師范大學(xué)》2017年碩士論文

【摘要】：重氮化合物在有機(jī)合成中是一類高活性的合成子,在金屬或非金屬催化下,原位脫去氮?dú)?轉(zhuǎn)化為高活性的金屬卡賓或卡賓中間體,能夠與適當(dāng)?shù)挠H核試劑作用,生成一些重要的功能有機(jī)分子。它不僅能夠參與含氮化合物的合成,也能夠進(jìn)行去重氮化串聯(lián)反應(yīng),實(shí)現(xiàn)官能團(tuán)的轉(zhuǎn)化。因此,在近幾年來(lái)的研究中,成為有機(jī)合成化學(xué)領(lǐng)域的研究焦點(diǎn)之一。本文以α-重氮芳酮為關(guān)鍵底物,用其與不同的反應(yīng)試劑進(jìn)行反應(yīng),通過(guò)去重氮化官能團(tuán)轉(zhuǎn)化,合成結(jié)構(gòu)多樣的含氮氧的有機(jī)小分子,最大限度地使起始原料轉(zhuǎn)化為目標(biāo)分子,避免了反應(yīng)中間體的分離,充分體現(xiàn)了此類反應(yīng)的原子經(jīng)濟(jì)性、合成高效性和環(huán)境友好性。本論文由以下四部分組成:第一部分介紹了重氮化合物的性質(zhì)特征及其進(jìn)行去重氮化構(gòu)建C-X鍵的方法。詳細(xì)地描述了近幾年來(lái)化學(xué)工作者對(duì)此底物展開的一系列研究,包括不同金屬催化下卡賓插入的交叉偶聯(lián)反應(yīng)和自由基反應(yīng),為本文提供了選題依據(jù),意義,創(chuàng)新點(diǎn)和研究方法。第二部分發(fā)展了芳甲酰重氮和芳乙炔,芳胺三組分原料在銠/銅的協(xié)同催化下的偶聯(lián)反應(yīng),合成了具有高立體選擇性的(Z)-N-芳基烯胺酮。該反應(yīng)過(guò)程涉及銠卡賓的原位形成與轉(zhuǎn)金屬化、插入遷移和親核加成等過(guò)程,構(gòu)建了C-N和C-C鍵。該反應(yīng)具有優(yōu)秀的(Z)-選擇性,這是分子內(nèi)的氫鍵造成的。第三部分發(fā)展了一類新型的自由基誘導(dǎo)的三組分反應(yīng)。該反應(yīng)以簡(jiǎn)單易得的原料N,N-二甲基苯胺、N-羥基鄰苯二甲酰亞胺與ɑ-重氮芳酮為原料,在醋酸碘苯為自由基引發(fā)劑,在室溫下進(jìn)行自由基引發(fā)的去重氮化的三組分反應(yīng),合成未見文獻(xiàn)報(bào)道的α-氨基氧基-β-氨基酮,即異吲哚1,3-二酮衍生物。通過(guò)實(shí)施控制實(shí)驗(yàn)證實(shí)此轉(zhuǎn)化過(guò)程涉及自由基機(jī)理。該反應(yīng)在無(wú)金屬催化條件下進(jìn)行,一步實(shí)現(xiàn)C-C和C-O鍵的構(gòu)建,同時(shí)完成了C(sp3)-H的官能團(tuán)化。第四部分介紹α-重氮芳酮在醋酸碘苯介導(dǎo)下與兩分子的N-羥基鄰苯二甲酰亞胺反應(yīng),在室溫下進(jìn)行自由基引發(fā)的去重氮化的三組分反應(yīng),合成了一系列結(jié)構(gòu)多樣的雙異吲哚1,3-二酮衍生物。用N-羥基丁二酰亞胺拓展上述反應(yīng),發(fā)現(xiàn)此反應(yīng)底物也能適用于目前的自由基引發(fā)的串聯(lián)反應(yīng),提供了一系列的雙吡咯烷2,5-二酮衍生物�？刂茖�(shí)驗(yàn)證實(shí)該反應(yīng)過(guò)程同樣也涉及自由基歷程。所有合成的產(chǎn)物結(jié)構(gòu)均經(jīng)核磁共振譜、紅外光譜以及高分辨質(zhì)譜等表征,部分產(chǎn)物結(jié)構(gòu)經(jīng)單晶X-衍射進(jìn)一步確證。
[Abstract]:In organic synthesis, diazo compounds are a kind of highly active synthesizers, which, under the catalysis of metal or non-metal, remove nitrogen in situ and convert to highly active metal carbene or carbene intermediates, which can interact with appropriate nucleophilic reagents. Some important functional organic molecules are produced. It can not only take part in the synthesis of nitrogen-containing compounds, but also can carry out the series reaction of dediazotization to realize the conversion of functional groups. Therefore, in recent years, the research has become one of the focuses in the field of organic synthesis chemistry. In this paper, 偽 -diazo aromatic ketones were used as the key substrates to react with different reaction reagents. By the deazotization of functional groups, small organic molecules containing nitrogen and oxygen with various structures were synthesized to maximize the conversion of starting materials into target molecules. The separation of reaction intermediates is avoided, and the atom economy, synthesis efficiency and environmental friendliness of such reactions are fully demonstrated. This paper is composed of four parts: the first part introduces the properties of diazo compounds and the method of deazotization to construct C-X bond. This paper describes in detail a series of studies on this substrate carried out by chemical workers in recent years, including the cross-coupling reaction and free radical reaction of carbene insertion catalyzed by different metals, which provides the basis and significance for this paper. Innovation and research methods. In the second part, the coupling reaction of aryl diazo and aryl acetylene and aromatic amines was developed under the synergistic catalysis of rhodium and copper, and the high stereoselectivity of azo-N-aryl enamine was synthesized. The reaction involves in situ formation and transformation of rhodium carbene, insertion migration and nucleophilic addition. C-N and C-C bonds were constructed. This reaction has excellent selectivity, which is caused by intramolecular hydrogen bonding. In the third part, a new type of free radical-induced three-component reaction is developed. In this reaction, three components of diazotization initiated by free radical at room temperature were carried out by using simple and easy raw materials, N- N- dimethylaniline-N-hydroxy phthalimide and diazo-aromatic ketone as raw materials and iodobenzene acetate as free radical initiator. The synthesis of 偽-aminoxy-尾-amino ketone, I. e., isoindoline 1 and 3-dione derivatives, has not been reported in the literature. The mechanism of free radical involved in the conversion process was confirmed by the control experiment. The reaction was carried out under the condition of no metal catalysis, C-C and C-O bonds were constructed in one step, and the functionalization of C(sp3)-H was completed at the same time. In the fourth part, the reaction of 偽 -diazo aryl ketone with N-hydroxyphthalimide is introduced, which is mediated by iodobenzene acetate, and three components of diazotization initiated by free radical are carried out at room temperature. A series of diisoindole 1-3-diketone derivatives with various structures were synthesized. N- hydroxysuccinimide was used to expand the above reactions. It was found that the substrate could also be used in the series reactions initiated by free radicals and a series of derivatives of dipyrrolidine 2o 5-dione were provided. The control experiment confirmed that the reaction process also involved the free radical process. The structures of all the synthesized products were characterized by NMR, IR and high resolution mass spectrometry, and some of the structures were further confirmed by single crystal X-ray diffraction.
【學(xué)位授予單位】：江蘇師范大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O621.3

【相似文獻(xiàn)】

相關(guān)期刊論文 前10條

1 金關(guān)泰;Б.А.波采依考希茨;;談?wù)劮枷阕逯氐衔锏慕Y(jié)構(gòu)問(wèn)題[J];化學(xué)通報(bào);1960年02期

2 穆寶菡;;一種新的高速重氮感光劑——2,5-二乙氧基-4-(4＇-甲苯基硫代)苯重氮氯化鋅復(fù)鹽的合成[J];化學(xué)通報(bào);1980年07期

3 ;染料增感重氮化合物的光解作用[J];感光材料;1978年03期

4 朱楚斌;許新華;章文迪;;重氮化合物屬性對(duì)曬圖紙性能的影響[J];天津造紙;1992年03期

5 袁翰青;;重氮化合物的發(fā)明人——格里斯[J];化學(xué)教育;1982年02期

6 董祥林;微泡法感光材料[J];感光材料;1975年04期

7 蔣媛;巧烤PS版[J];印刷技術(shù);1998年09期

8 嚴(yán)國(guó)兵;匡春香;彭程;王劍波;;鈀催化重氮化合物反應(yīng)的研究進(jìn)展[J];有機(jī)化學(xué);2009年06期

9 王雪良;周，

本文編號(hào)：1889593