【摘要】：聯(lián)烯是一類高活性的有機(jī)分子,它作為一種重要有機(jī)合成砌塊在現(xiàn)代有機(jī)合成中具有高度的應(yīng)用價(jià)值。聯(lián)烯的親核加成反應(yīng)是一類極其重要的有機(jī)反應(yīng),但由于聯(lián)烯反應(yīng)位點(diǎn)眾多,在親核加成時(shí)需要控制位點(diǎn)才能得到選擇性好的產(chǎn)物。在聯(lián)烯端位引入官能團(tuán)能有效改變其電子云分布,當(dāng)聯(lián)烯與吸電子官能團(tuán)相連時(shí),就能使中間碳電子云密度降低,更傾向于發(fā)生各種親核加成反應(yīng)。本論文是基于環(huán)丙基聯(lián)烯酮具有多個(gè)反應(yīng)位點(diǎn),利用不同類型的親核試劑與其反應(yīng),高度區(qū)域和立體選擇性地構(gòu)建各種復(fù)雜分子。論文主要內(nèi)容包括以下幾個(gè)方面:第一部分研究了以亞磺酸鈉衍生物作為親核試劑對(duì)環(huán)丙基聯(lián)烯酮的親核加成。我們發(fā)現(xiàn)在不同的溶劑可以控制生成不同位點(diǎn)的加成產(chǎn)物,在MeOH中得到β-磺�；a(chǎn)物,在DMSO中得到γ-磺�；a(chǎn)物,兩種類型磺�；a(chǎn)率很高,而且立體選擇性也很好,同時(shí)該反應(yīng)的機(jī)理也被詳細(xì)研究。接著我們對(duì)β-加成產(chǎn)進(jìn)行碘環(huán)化得到四取代呋喃產(chǎn)物,同時(shí)也開發(fā)了一鍋法從環(huán)丙基聯(lián)烯酮與苯亞磺酸鈉反應(yīng)完后直接碘環(huán)化得到四取代呋喃產(chǎn)物,及對(duì)生成的碘代四取代呋喃產(chǎn)物轉(zhuǎn)化研究。第二部分研究了以亞硝酸鈉作為親核試劑與環(huán)丙基聯(lián)烯酮反應(yīng),同樣在不同溶劑下分別得到了β,γ-二硝化,γ-硝化及分子內(nèi)氧化生成肟的產(chǎn)物。在CH3CN作溶劑下生成β,γ-二硝化產(chǎn)物;在DMSO作溶劑下γ-硝化產(chǎn)物被得到;在CH3OH溶劑中,β,γ-二硝化產(chǎn)物能發(fā)生分子內(nèi)氧化反應(yīng)生成肟的產(chǎn)物。
[Abstract]:Diene is a class of highly active organic molecules. As an important organic synthetic block, it has high application value in modern organic synthesis. The nucleophilic addition reaction of diene is a very important organic reaction, but because there are many sites in the reaction, it is necessary to control the site in order to obtain the selective product. The introduction of functional groups to the terminal of bienes can effectively change the distribution of electron clouds. When they are connected with the electron functional groups, the density of intermediate carbon electron clouds can be reduced, and they tend to occur various nucleophilic addition reactions. Based on the multiple reaction sites of cyclopropyldienone, various complex molecules were constructed by using different nucleophilic reagents in high region and stereoselectivity. The main contents of this paper are as follows: in the first part, the nucleophilic addition of cyclopropylenone with sodium sulfonate derivatives as nucleophilic reagent was studied. We found that the addition products at different sites can be controlled in different solvents, 尾 -sulfonylation products can be obtained in MeOH and 緯 -sulfonylation products can be obtained in DMSO, the yields of two types of sulfonylation are very high, and the stereoselectivity is very good. At the same time, the mechanism of the reaction has also been studied in detail. Then we cyclized the 尾 -adduct to get tetrasubstituted furan products. At the same time, we also developed a one-pot method to obtain tetrasubstituted furan products from cyclization of cyclopropylenone with sodium benzenesulfonate by direct iodine cyclization. And study on the transformation of the product of tetra-substituted furan. In the second part, the products of 尾, 緯 -dinitrification, 緯 -nitration and intramolecular oxidation to form oxime were obtained by reaction of sodium nitrite with cyclopropyldienone in different solvents. 尾, 緯 -dinitrification products were obtained in CH3CN solvent; 緯 -nitration products were obtained in DMSO solvent; in CH3OH solvent, 尾, 緯 -dinitrification products could undergo intramolecular oxidation to produce oxime.
【學(xué)位授予單位】：浙江理工大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O621.256.7

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