本文關(guān)鍵詞：基于二氧化碳與端炔的羧化反應(yīng)構(gòu)建含氮稠雜環(huán)　出處：《南開大學(xué)》2016年碩士論文　論文類型：學(xué)位論文

  更多相關(guān)文章： 二氧化碳 羧化反應(yīng) 銅基離子液體 雜環(huán) 異吲哚酮并異VA唑類稠環(huán) 一鍋兩步 合成方法 綠色化學(xué) 環(huán)化反應(yīng)

【摘要】：二氧化碳是溫室氣體的主要成分,同時也是分布最廣、儲量豐富的碳一資源。作為一種廉價易得、安全的可再生碳一合成子,二氧化碳資源化利用的有效途徑之一就是將其轉(zhuǎn)化為具有高附加值的精細化工產(chǎn)品。目前,工業(yè)生產(chǎn)所消耗的二氧化碳已經(jīng)取得一定的規(guī)模,但由于二氧化碳分子熱力學(xué)穩(wěn)定性和動力學(xué)惰性的限制,化學(xué)利用二氧化碳的量還遠遠不能與化石原料的消耗量相比。除此之外,二氧化碳資源化利用產(chǎn)品結(jié)構(gòu)不夠豐富,其中90%以上是用于生產(chǎn)尿素、無機碳酸鹽、碳酸酯、聚碳酸酯和水楊酸等,僅有小部分二氧化碳用于其它高附加值化學(xué)品的制備。從有機合成的角度來看,拓展二氧化碳應(yīng)用范圍,提高二氧化碳應(yīng)用規(guī)模的有效策略分為兩方面,一是通過調(diào)控金屬、配體等設(shè)計更高效的催化劑或采用高能態(tài)的原料,降低二氧化碳的轉(zhuǎn)化能壘,從而實現(xiàn)溫和條件下二氧化碳的化學(xué)轉(zhuǎn)化;二是設(shè)計更為綠色、實用的反應(yīng)路徑,提高反應(yīng)的選擇性和步驟經(jīng)濟性,從而有效地將二氧化碳“固定”在有機分子中。實現(xiàn)溫和條件(低壓)下二氧化碳的轉(zhuǎn)化可以降低能耗、減少設(shè)備消耗,有利于實驗室基礎(chǔ)研究結(jié)果快速應(yīng)用于工業(yè)生產(chǎn)。炔酸酯是一類缺電子炔烴,常常作為邁克爾加成反應(yīng)的受體廣泛應(yīng)用于構(gòu)筑雜環(huán)化合物。我們課題組在金屬催化二氧化碳的化學(xué)轉(zhuǎn)化方面積累了大量經(jīng)驗,在此基礎(chǔ)上,我們開展了常壓二氧化碳化學(xué)利用的研究:1)炔酸酯在雜環(huán)化合物合成中的應(yīng)用非常廣泛。從商品化的末端炔烴出發(fā),以二氧化碳作為碳一合成子通過C(sp)-H鍵直接羧化的方法制備炔酸酯是最具優(yōu)勢的合成路線。使用新型的銅基離子液體[Cu(Im12)2][CuBr2]為催化劑,高效實現(xiàn)了末端炔烴的羧化酯化反應(yīng)。催化劑合成簡單,且不需要使用額外的配體,在室溫、常壓二氧化碳下就可實現(xiàn)端炔羧化反應(yīng)。底物適用面較廣,帶有吸電子取代基和給電子取代基的底物均能以高收率(70~96%)轉(zhuǎn)化為相應(yīng)炔酸酯產(chǎn)物。通過13C NMR檢測到了銅催化劑對底物炔烴的活化,催化劑中包含的長烷基鏈取代的咪唑配體使催化劑具有更高的溶解性、疏水性和穩(wěn)定性,增強了中心銅原子的電子云密度,使得反應(yīng)可以在溫和條件下高效進行。2)異吲哚酮并異VA唑類稠環(huán)化合物廣泛存在于天然產(chǎn)物和藥物活性成分中,吲哚酮結(jié)構(gòu)具有良好的抗菌、抗炎活性,而異VA唑類衍生物也是一類具有良好殺蟲、抗菌、抗炎生物活性的雜環(huán)有機化合物。我們使用CuCl/PPh3催化端炔與二氧化碳的羧化反應(yīng)制備炔酸酯,隨后向反應(yīng)體系中直接加入N-羥基鄰苯二甲酰亞胺(NHPI),通過一鍋兩步法成功地實現(xiàn)異吲哚酮并異VA唑類稠環(huán)化合物的合成(收率65~96%)。該體系的優(yōu)點在于以羧化反應(yīng)促進環(huán)化反應(yīng),無需分離中間產(chǎn)物炔酸酯,三苯基膦即作為羧化反應(yīng)的配體,同時也用作催化劑促進第二步的環(huán)化反應(yīng)。經(jīng)過羧化酯化環(huán)化反應(yīng),同時構(gòu)建了兩個C-C鍵和兩個C-O鍵,將二氧化碳分子拓展到藥物分子中的合成中。3)作為由二氧化碳制備的高附加值產(chǎn)品,炔酸酯的應(yīng)用也是二氧化碳資源化利用的更進一步體現(xiàn)。我們以炔酸酯和NHPI為原料,使用廉價易得的NaOAc·3H2O為催化劑,合成具有潛在生物活性的異吲哚酮并異VA唑類稠環(huán)化合物。該方法只需10 mol%的催化劑用量便可實現(xiàn)該[3+2]環(huán)化反應(yīng)高效進行。另外,通過設(shè)計控制實驗,認為NHPI鹽作為真正的催化中心,促進該反應(yīng)以類似oxa-Michael-aldol的反應(yīng)機理進行。
[Abstract]:Carbon dioxide is the main component of greenhouse gases, but also the most widely distributed and abundant carbon resources. As a kind of cheap, renewable carbon synthon safety, one of the effective ways of resource utilization of carbon dioxide is converted into high value-added fine chemical products. At present, the consumption of industrial production carbon dioxide has a certain scale, but because the carbon dioxide molecular thermodynamic stability and kinetic inertia constraints, compared to chemical consumption by the amount of carbon dioxide is far from fossil raw materials. In addition, CO2 utilization structure of the product is not rich, of which more than 90% is used in the production of urea, inorganic carbonate, carbonate, polycarbonate salicylic acid and etc., only a small part of the carbon dioxide used for other high value-added chemicals. The preparation of organic synthesis from the angle of extension. The application scope of exhibition of carbon dioxide, improve carbon dioxide effective strategy application scale is divided into two aspects, one is through the regulation of metal catalyst, ligand to design more efficient use of raw materials or energy state, reduce carbon dioxide conversion barrier, so as to realize the two chemical oxygen carbon conversion under mild conditions; the two is to design more green. The utility of the reaction path, improve the reaction selectivity and the steps of economy, thus effectively carbon dioxide will be "fixed" in organic molecules. Mild conditions (low pressure) conversion of carbon dioxide can reduce energy consumption, reduce equipment consumption, is conducive to the laboratory study results rapidly applied in industrial production. Propargyl ester is a kind of electron deficient alkyne, often as the Michael addition reaction of receptor is widely applied to the construction of heterocyclic compounds. The chemical area in metal catalyzed carbon dioxide into our research group Tired of a lot of experience, on this basis, we carried out research on atmospheric chemistry of carbon dioxide by: 1) propargyl ester is widely used in the synthesis of heterocyclic compounds. Terminal alkynes from commercialization of carbon to carbon dioxide as a synthesis by C (SP) for direct carboxylation of -H bond with method of preparing alkyne ester is the most advantage of the synthetic route. The use of copper based ionic liquid type [Cu (Im12) 2][CuBr2] as catalyst, the efficient implementation of carboxyl esterification reaction of terminal alkynes. The catalyst synthesis is simple, and does not need to use additional ligands, at room temperature, atmospheric CO2 can achieve the alkyne carboxylation reaction substrates. Wide, with electron withdrawing substituents and electron donating substituents are substrates with high yield (70~96%) into the corresponding Alkynoates products. Through the 13C NMR detected the activation of copper catalyst to substrate catalyst containing alkynes. Long alkyl chain substituted imidazole ligand of the catalyst has higher solubility, hydrophobicity and stability, enhance the electron density of central copper atom, the reaction can be efficiently.2 under mild conditions) isoindolones and ISO VA azole fused ring compounds exist widely in natural products and active pharmaceutical ingredients in indole, ketone structure has good antibacterial, anti-inflammatory activity, different VA azole derivatives are a kind of good insecticidal, antibacterial, anti-inflammatory and biological activity of heterocyclic organic compounds. We use CuCl/PPh3 and carbon dioxide catalyzed alkyne carboxylation reaction preparation of propargyl ester, then directly added to the reaction system of N- hydroxy two methyl benzene imide (NHPI), the two step is achieved successfully by one pot synthesis isoindolones and ISO VA azole fused ring compounds (yield 65~96%). The advantages of this system is to promote the cyclization reaction to carboxylation reaction, no The need to separate the intermediate product of propargyl ester, three phenyl phosphine ligands as carboxylation reaction, but also used as a catalyst to promote cyclization reaction in second steps. After carboxylation esterification cyclization, and constructed two C-C bonds and two C-O bonds, will be extended to the synthesis of.3 in carbon dioxide molecules in drug molecules) as a high value-added products from carbon dioxide preparation, further reflect the Alkynoates application is carbon dioxide utilization. We use Alkynoates and NHPI as raw materials, the use of cheap NaOAc 3H2O as catalyst, synthesis of isoindolone potential biological activity and different VA azole fused ring compounds. This method only needs a catalyst dosage of 10 mol% can achieve the [3+2] cyclization reaction efficiently. In addition, through the design of control experiment, NHPI salt as the catalytic center of the real, to promote the reaction to oxa-Michael-aldol like reaction The mechanism is carried out.

【學(xué)位授予單位】：南開大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2016
【分類號】：X701;O626

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