芳基化合物和醌類(lèi)衍生物的選擇性碳?xì)浠罨芯?/H1>
發(fā)布時(shí)間：2018-03-29 06:46
本文選題：碳?xì)浠罨?/strong> 切入點(diǎn)：過(guò)渡金屬催化 出處：《江南大學(xué)》2017年碩士論文
【摘要】：過(guò)渡金屬催化的碳?xì)浠罨墙┠暧袡C(jī)合成界的重要研究領(lǐng)域。醌類(lèi)化合物及其衍生物具有多樣的潛在藥用價(jià)值,因而研究它們的合成方法具有重要的意義。本文主要研究過(guò)渡金屬催化的含氮基團(tuán)導(dǎo)向的芳基化合物的選擇性碳?xì)浠罨王?lèi)衍生物的碳?xì)浠罨�。這些研究可以在一定程度上推動(dòng)導(dǎo)向的芳基化合物的選擇性碳?xì)浠罨难芯窟M(jìn)展,同時(shí)也為一些以芳基醌類(lèi)及含硫芳基醌類(lèi)衍生物為中間體的藥物合成提供新思路。主要內(nèi)容如下:1、銠催化的酰胺導(dǎo)向的選擇性碳?xì)浠罨┗磻?yīng)的研究發(fā)展了以[Cp*RhCl_2]_2為催化劑,以碳酸銀為氧化劑的二芳基酰胺的選擇性碳?xì)浠罨磻?yīng)。該方法加入三氟甲烷磺酸銀來(lái)輔助催化劑催化,可以選擇性生成酰胺N-芳環(huán)一側(cè)的產(chǎn)物;而不加時(shí)則生成C-芳環(huán)一側(cè)的環(huán)化產(chǎn)物。本文報(bào)道的酰胺的烯基化反應(yīng)具有很好的化學(xué)和區(qū)域選擇性以及官能團(tuán)耐受性。機(jī)理探索實(shí)驗(yàn)證明非配陰離子在該反應(yīng)中起了一個(gè)關(guān)鍵作用,并提出了可能的反應(yīng)機(jī)理。2、銠催化的酰胺導(dǎo)向的選擇性碳?xì)浠罨０坊磻?yīng)的研究發(fā)展了一種全新的使用過(guò)渡金屬銠催化酰胺與異氰酸酯選擇性碳?xì)浠罨０坊磻?yīng)合成不對(duì)稱(chēng)酰胺的方法。此類(lèi)反應(yīng)條件簡(jiǎn)單,同時(shí)有著良好到優(yōu)秀的產(chǎn)率。反應(yīng)對(duì)各種異氰酸烷基酯都適用,甚至異氰酸芳基酯也能參與反應(yīng)。該方法提供了一種高效且實(shí)用的不對(duì)稱(chēng)雙酰胺的合成方法。3、銠催化的三唑?qū)虻倪x擇性碳?xì)浠罨┗磻?yīng)的研究設(shè)計(jì)了一種吡啶基苯并三唑類(lèi)化合物來(lái)研究與丙烯酸酯類(lèi)化合物的選擇性碳?xì)浠罨悸?lián)反應(yīng)。反應(yīng)以[Cp*RhCl_2]_2為催化劑,醋酸銅為氧化劑,六氟銻酸銀為添加劑展開(kāi),結(jié)果發(fā)現(xiàn)碳?xì)浠罨軌蜻x擇性的發(fā)生在吡啶環(huán)上,說(shuō)明在這一類(lèi)化合物中三唑基的導(dǎo)向能力要大于吡啶基。此外,我們發(fā)現(xiàn)各種帶供電子基團(tuán)或者吸電子基團(tuán)的苯基苯并三唑類(lèi)化合物均可以得到良好到優(yōu)秀收率的產(chǎn)物。此外,我們也對(duì)該反應(yīng)做了一系列的機(jī)理探索實(shí)驗(yàn)。4、銅催化的苯醌與苯磺酰氯類(lèi)化合物偶聯(lián)生成含硫芳基醌類(lèi)衍生物的研究首次采用苯磺酰氯作為偶聯(lián)試劑,在廉價(jià)的CuI催化和還原劑三苯基磷的幫助下與苯醌偶聯(lián)選擇性地生成含硫芳基醌類(lèi)衍生物,而無(wú)其他磺�；�(lèi)衍生物生成。各種單取代和雙取代的苯磺酰氯都能以中等到良好的產(chǎn)率得到目標(biāo)產(chǎn)物。這為含硫芳基醌類(lèi)衍生物的合成提供了一種新選擇。5、鈀催化的萘醌、鹵代苯酚及鹵代烷烴三組分交叉偶聯(lián)為芳基醌類(lèi)衍生物的研究拓展了一種醋酸鈀催化的合成芳基醌類(lèi)衍生物的方法,采用碘代苯酚及鹵代烷烴與萘醌三組分一鍋法交叉偶聯(lián)來(lái)合成。其中,鹵代烷烴既是反應(yīng)物又是溶劑。與前人的合成方法相比,該方法具有操作簡(jiǎn)單、條件溫和、綠色經(jīng)濟(jì)等突出優(yōu)點(diǎn)。
[Abstract]:Hydrocarbon activation catalyzed by transition metals is an important research field in the field of organic synthesis in recent years. Quinones and their derivatives have a variety of potential medicinal value. In this paper, the selective hydrocarbon activation of nitrogen-oriented aryl compounds catalyzed by transition metals and the hydrocarbon activation of quinone derivatives are studied. Promote to some extent the research progress of selective hydrocarbon activation of oriented aryl compounds, It also provides a new idea for the synthesis of aryl quinones and sulfur-containing aryl quinones derivatives as intermediates. The main contents are as follows: 1, Rhodium catalyzed amide-oriented selective hydrocarbon activation alkylation reaction developed with [Cp*RhCl_2] 2 as catalyst, The selective hydrocarbon activation reaction of diaryl amides with silver carbonate as oxidant. Silver trifluoromethane sulfonic acid was added to assist the catalyst to selectively produce the product of N-aromatic ring of amide. The alkenylation reaction of amides reported in this paper has good chemical and regioselectivity and functional group tolerance. The mechanism exploration experiments have proved that non-ligand anions are present in this reaction. Played a key role, The possible reaction mechanism. 2. Rhodium catalyzed amide-oriented selective hydrocarbon activation amidation reaction has developed a novel transition metal rhodium catalyzed amide and isocyanate selective hydrocarbon activated amide. A method for the synthesis of asymmetric amides by chemical reactions. The conditions for such reactions are simple, At the same time have good to excellent yield. The reaction is applicable to all kinds of isocyanate alkyl ester, Even aryl isocyanate can take part in the reaction. This method provides an efficient and practical method for the synthesis of asymmetric bisamides. Rhodium catalyzed triazole-oriented selective hydrocarbon activation alkylation reaction has been designed. The selective hydrocarbon activation coupling reaction of acrylates with pyridyl benzo triazole compounds was studied. [Cp*RhCl_2] 2 was used as catalyst. Copper acetate is used as oxidant and silver hexafluoroantimonate as additive. The results show that hydrocarbon activation can selectively occur on pyridine ring, indicating that the guiding ability of triazole group in this kind of compounds is greater than that of pyridine group. It has been found that all kinds of phenyl benzo triazole compounds with or without electron groups can be obtained in good yields. We have also done a series of experiments on the mechanism of this reaction. 4. The coupling of benzoquinone catalyzed by copper with benzenesulfonyl chloride derivatives to form sulfur-containing aryl quinone derivatives was studied for the first time using benzenesulfonyl chloride as coupling reagent. Aryl quinone derivatives containing sulfur were selectively synthesized by coupling with benzoquinone with the help of cheap CuI catalysis and triphenyl phosphorus reductant. However, no other sulfonyl quinone derivatives were formed. All kinds of monosubstituted and disubstituted benzenesulfonyl chloride could obtain the target product in medium to good yield. This provides a new choice for the synthesis of sulfur-containing aryl quinone derivatives. 5, palladium catalyzed naphthoquinone, Studies on Cross-Coupling of three components of Halogenated Phenol and Halogenated hydrocarbons to aryl Quinone Derivatives A method for Synthesis of aromatic Quinone Derivatives catalyzed by Palladium Acetate was extended. The method of cross-coupling of iodophenol and halogenated hydrocarbon with naphthoquinone in one pot is used. Halogenated hydrocarbons are both reactants and solvents. Compared with the previous synthesis method, this method is simple in operation and mild in conditions. Green economy and other outstanding advantages.
【學(xué)位授予單位】：江南大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類(lèi)號(hào)】：O621.251
【參考文獻(xiàn)】
相關(guān)期刊論文 前1條
1 韋自娟,李云政;醌類(lèi)衍生物全反式合成方法研究進(jìn)展[J];化學(xué)研究;2004年01期
，
本文編號(hào)：1680036
本文鏈接：http://sikaile.net/kejilunwen/huaxue/1680036.html
本文選題：碳?xì)浠罨?/strong> 切入點(diǎn)：過(guò)渡金屬催化 出處：《江南大學(xué)》2017年碩士論文
【摘要】：過(guò)渡金屬催化的碳?xì)浠罨墙┠暧袡C(jī)合成界的重要研究領(lǐng)域。醌類(lèi)化合物及其衍生物具有多樣的潛在藥用價(jià)值,因而研究它們的合成方法具有重要的意義。本文主要研究過(guò)渡金屬催化的含氮基團(tuán)導(dǎo)向的芳基化合物的選擇性碳?xì)浠罨王?lèi)衍生物的碳?xì)浠罨�。這些研究可以在一定程度上推動(dòng)導(dǎo)向的芳基化合物的選擇性碳?xì)浠罨难芯窟M(jìn)展,同時(shí)也為一些以芳基醌類(lèi)及含硫芳基醌類(lèi)衍生物為中間體的藥物合成提供新思路。主要內(nèi)容如下:1、銠催化的酰胺導(dǎo)向的選擇性碳?xì)浠罨┗磻?yīng)的研究發(fā)展了以[Cp*RhCl_2]_2為催化劑,以碳酸銀為氧化劑的二芳基酰胺的選擇性碳?xì)浠罨磻?yīng)。該方法加入三氟甲烷磺酸銀來(lái)輔助催化劑催化,可以選擇性生成酰胺N-芳環(huán)一側(cè)的產(chǎn)物;而不加時(shí)則生成C-芳環(huán)一側(cè)的環(huán)化產(chǎn)物。本文報(bào)道的酰胺的烯基化反應(yīng)具有很好的化學(xué)和區(qū)域選擇性以及官能團(tuán)耐受性。機(jī)理探索實(shí)驗(yàn)證明非配陰離子在該反應(yīng)中起了一個(gè)關(guān)鍵作用,并提出了可能的反應(yīng)機(jī)理。2、銠催化的酰胺導(dǎo)向的選擇性碳?xì)浠罨０坊磻?yīng)的研究發(fā)展了一種全新的使用過(guò)渡金屬銠催化酰胺與異氰酸酯選擇性碳?xì)浠罨０坊磻?yīng)合成不對(duì)稱(chēng)酰胺的方法。此類(lèi)反應(yīng)條件簡(jiǎn)單,同時(shí)有著良好到優(yōu)秀的產(chǎn)率。反應(yīng)對(duì)各種異氰酸烷基酯都適用,甚至異氰酸芳基酯也能參與反應(yīng)。該方法提供了一種高效且實(shí)用的不對(duì)稱(chēng)雙酰胺的合成方法。3、銠催化的三唑?qū)虻倪x擇性碳?xì)浠罨┗磻?yīng)的研究設(shè)計(jì)了一種吡啶基苯并三唑類(lèi)化合物來(lái)研究與丙烯酸酯類(lèi)化合物的選擇性碳?xì)浠罨悸?lián)反應(yīng)。反應(yīng)以[Cp*RhCl_2]_2為催化劑,醋酸銅為氧化劑,六氟銻酸銀為添加劑展開(kāi),結(jié)果發(fā)現(xiàn)碳?xì)浠罨軌蜻x擇性的發(fā)生在吡啶環(huán)上,說(shuō)明在這一類(lèi)化合物中三唑基的導(dǎo)向能力要大于吡啶基。此外,我們發(fā)現(xiàn)各種帶供電子基團(tuán)或者吸電子基團(tuán)的苯基苯并三唑類(lèi)化合物均可以得到良好到優(yōu)秀收率的產(chǎn)物。此外,我們也對(duì)該反應(yīng)做了一系列的機(jī)理探索實(shí)驗(yàn)。4、銅催化的苯醌與苯磺酰氯類(lèi)化合物偶聯(lián)生成含硫芳基醌類(lèi)衍生物的研究首次采用苯磺酰氯作為偶聯(lián)試劑,在廉價(jià)的CuI催化和還原劑三苯基磷的幫助下與苯醌偶聯(lián)選擇性地生成含硫芳基醌類(lèi)衍生物,而無(wú)其他磺�；�(lèi)衍生物生成。各種單取代和雙取代的苯磺酰氯都能以中等到良好的產(chǎn)率得到目標(biāo)產(chǎn)物。這為含硫芳基醌類(lèi)衍生物的合成提供了一種新選擇。5、鈀催化的萘醌、鹵代苯酚及鹵代烷烴三組分交叉偶聯(lián)為芳基醌類(lèi)衍生物的研究拓展了一種醋酸鈀催化的合成芳基醌類(lèi)衍生物的方法,采用碘代苯酚及鹵代烷烴與萘醌三組分一鍋法交叉偶聯(lián)來(lái)合成。其中,鹵代烷烴既是反應(yīng)物又是溶劑。與前人的合成方法相比,該方法具有操作簡(jiǎn)單、條件溫和、綠色經(jīng)濟(jì)等突出優(yōu)點(diǎn)。
[Abstract]:Hydrocarbon activation catalyzed by transition metals is an important research field in the field of organic synthesis in recent years. Quinones and their derivatives have a variety of potential medicinal value. In this paper, the selective hydrocarbon activation of nitrogen-oriented aryl compounds catalyzed by transition metals and the hydrocarbon activation of quinone derivatives are studied. Promote to some extent the research progress of selective hydrocarbon activation of oriented aryl compounds, It also provides a new idea for the synthesis of aryl quinones and sulfur-containing aryl quinones derivatives as intermediates. The main contents are as follows: 1, Rhodium catalyzed amide-oriented selective hydrocarbon activation alkylation reaction developed with [Cp*RhCl_2] 2 as catalyst, The selective hydrocarbon activation reaction of diaryl amides with silver carbonate as oxidant. Silver trifluoromethane sulfonic acid was added to assist the catalyst to selectively produce the product of N-aromatic ring of amide. The alkenylation reaction of amides reported in this paper has good chemical and regioselectivity and functional group tolerance. The mechanism exploration experiments have proved that non-ligand anions are present in this reaction. Played a key role, The possible reaction mechanism. 2. Rhodium catalyzed amide-oriented selective hydrocarbon activation amidation reaction has developed a novel transition metal rhodium catalyzed amide and isocyanate selective hydrocarbon activated amide. A method for the synthesis of asymmetric amides by chemical reactions. The conditions for such reactions are simple, At the same time have good to excellent yield. The reaction is applicable to all kinds of isocyanate alkyl ester, Even aryl isocyanate can take part in the reaction. This method provides an efficient and practical method for the synthesis of asymmetric bisamides. Rhodium catalyzed triazole-oriented selective hydrocarbon activation alkylation reaction has been designed. The selective hydrocarbon activation coupling reaction of acrylates with pyridyl benzo triazole compounds was studied. [Cp*RhCl_2] 2 was used as catalyst. Copper acetate is used as oxidant and silver hexafluoroantimonate as additive. The results show that hydrocarbon activation can selectively occur on pyridine ring, indicating that the guiding ability of triazole group in this kind of compounds is greater than that of pyridine group. It has been found that all kinds of phenyl benzo triazole compounds with or without electron groups can be obtained in good yields. We have also done a series of experiments on the mechanism of this reaction. 4. The coupling of benzoquinone catalyzed by copper with benzenesulfonyl chloride derivatives to form sulfur-containing aryl quinone derivatives was studied for the first time using benzenesulfonyl chloride as coupling reagent. Aryl quinone derivatives containing sulfur were selectively synthesized by coupling with benzoquinone with the help of cheap CuI catalysis and triphenyl phosphorus reductant. However, no other sulfonyl quinone derivatives were formed. All kinds of monosubstituted and disubstituted benzenesulfonyl chloride could obtain the target product in medium to good yield. This provides a new choice for the synthesis of sulfur-containing aryl quinone derivatives. 5, palladium catalyzed naphthoquinone, Studies on Cross-Coupling of three components of Halogenated Phenol and Halogenated hydrocarbons to aryl Quinone Derivatives A method for Synthesis of aromatic Quinone Derivatives catalyzed by Palladium Acetate was extended. The method of cross-coupling of iodophenol and halogenated hydrocarbon with naphthoquinone in one pot is used. Halogenated hydrocarbons are both reactants and solvents. Compared with the previous synthesis method, this method is simple in operation and mild in conditions. Green economy and other outstanding advantages.
【學(xué)位授予單位】：江南大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類(lèi)號(hào)】：O621.251
【參考文獻(xiàn)】
相關(guān)期刊論文 前1條
1 韋自娟,李云政;醌類(lèi)衍生物全反式合成方法研究進(jìn)展[J];化學(xué)研究;2004年01期
，本文編號(hào)：1680036
本文鏈接：http://sikaile.net/kejilunwen/huaxue/1680036.html
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