【摘要】：C-H鍵廣泛存在于自然界中，通過C-H鍵活化構(gòu)建C-X（X=C, N, P, S）鍵。由于不需要通過對C-H鍵進(jìn)行官能團(tuán)化，縮短了有機(jī)合成路線，具有步驟經(jīng)濟(jì)性和原子經(jīng)濟(jì)性。而C-N鍵和C-C鍵是最常見的兩種化學(xué)鍵，通過C-H活化構(gòu)建芳基C-N鍵和芳雜環(huán)C-C鍵具有重要的研究意義。 含有C-N鍵的有機(jī)化合物廣泛存在于自然界，是一類構(gòu)成生命基礎(chǔ)的重要化合物。芳胺作為一種重要的含氮化合物，廣泛存在與具有生物活性的天然產(chǎn)物和藥物分子中，并且是很多化工產(chǎn)品的重要原料和組成部分，對我們的生活有著重要的意義。因此，高效、經(jīng)濟(jì)、環(huán)保的構(gòu)建芳基C-N鍵始終有機(jī)化學(xué)的一個研究熱點。 構(gòu)建芳基C-N鍵的方法有很多，例如銅催化的Ullmann偶聯(lián)反應(yīng)，鈀催化的Buchwald-Hartwig偶聯(lián)反應(yīng)和芳基硼酸參與的Chan-Lam偶聯(lián)反應(yīng)。這些都是構(gòu)建芳基C-N鍵的有效方法，被廣泛的應(yīng)用于實驗合成中。但這些反應(yīng)常常需要先將Ar-H鍵進(jìn)行官能團(tuán)化再和胺發(fā)生偶聯(lián)，無疑增加了合成的工作量，不具步驟經(jīng)濟(jì)性。因此，直接利用芳基C-H鍵和N-H鍵脫氫偶聯(lián)構(gòu)建芳基C-N鍵成為了許多有機(jī)化學(xué)家追求的目標(biāo)。 近年來，氧化脫氫偶聯(lián)反應(yīng)構(gòu)建C-N鍵的研究取得了一定的進(jìn)展。已經(jīng)實現(xiàn)了用機(jī)過氧化物或者無機(jī)鹽作氧化劑的條件下使芳香sp2C-H鍵與N-H鍵直接脫氫偶聯(lián)，這種直接脫氫偶聯(lián)合成苯胺化合物的方法具有突出的步驟經(jīng)濟(jì)性。但同時大量的過氧化物和高價金屬鹽等氧化劑在反應(yīng)中的使用，也帶來一些無法避免的問題，，例如大量副產(chǎn)物產(chǎn)生，導(dǎo)致原子經(jīng)濟(jì)性下降；體系殘留大量氧化劑殘體，造成分離困難；普遍價格較高，造成環(huán)境污染等。而O2替代有機(jī)過氧化物和高價金屬鹽等作氧化劑，不僅可以有效避免上述問題，而且O2廉價、易得、綠色環(huán)保，是一種既具有步驟經(jīng)濟(jì)性，又具有原子經(jīng)濟(jì)性的芳香sp2C-H鍵和胺基N-H鍵偶合構(gòu)建芳基C-N鍵的方法。因此，本文以此為基礎(chǔ)用亞銅催化，O2氣氧化2-苯基吡啶衍生物與乙酰苯胺衍生物脫氫偶聯(lián)建芳基C-N鍵，合成了一些列芳胺化合物。 本文內(nèi)容如下： 1.以2-苯基吡啶及其衍生物與乙酰苯胺及其衍生物作為底物，CuBr作為催化劑，O2氧化脫氫直接構(gòu)建芳基C-N鍵。合成一系列含有吡啶基的芳胺化合物。同時對反應(yīng)溶劑及溶劑量、催化劑及其用量、溫度和時間等因素進(jìn)行了篩選，并推測了反應(yīng)機(jī)理。共合成了19個芳胺化合物，其結(jié)構(gòu)均經(jīng)過了NMR的鑒定。 2.以喹啉衍生物和苯氧乙酸衍生物為底物，AgNO3為催化劑，K2S2O8為氧化劑，水和二氯甲烷為溶劑（體積比為1：1），在三氟乙酸的存在下合成了一系列2-（苯氧甲基）喹啉化合物，并對反應(yīng)條件進(jìn)行了優(yōu)化，分別討論了催化劑、溶劑、氧化劑、溫度、時間對反應(yīng)的影響。共合成了11個目標(biāo)化合物，其結(jié)構(gòu)均經(jīng)過NMR鑒定。
[Abstract]:C-H bond exists widely in nature. C-X (XC, N, P, S) bond is formed by activation of C-H bond. Because the C-H bond does not need to be functionalized, the organic synthesis route is shortened and the step economy and atomic economy are obtained. C-N bond and C-C bond are the two most common chemical bonds. The aryl C-N bond and heterocyclic C-C bond can be synthesized by C-H activation. Organic compounds containing C-N bonds are widely found in nature and are important compounds that form the basis of life. As an important nitrogen-containing compound, aromatic amines are widely found in natural products and drug molecules with biological activity, and are important raw materials and components of many chemical products, which are of great significance to our life. Therefore, efficient, economical and environmentally friendly construction of aryl C-N bond has always been a hot spot in organic chemistry. There are many methods to construct aryl C-N bond, such as copper catalyzed Ullmann coupling reaction, palladium catalyzed Buchwald-Hartwig coupling reaction and aryl boric acid Chan-Lam coupling reaction. These are effective methods for the construction of aryl C-N bonds and are widely used in experimental synthesis. However, these reactions often require the Ar-H bond to be functionalized and then coupled with amine, which no doubt increases the workload of synthesis and is not economical in step. Therefore, the direct dehydrogenation coupling of aryl C-H bond and N-H bond to form aryl C-N bond has become the goal of many organic chemists. In recent years, some progress has been made in the synthesis of C-N bond by oxidative dehydrogenation coupling reaction. Direct dehydrogenation coupling of aromatic sp2C-H bond and N-H bond with mechanical peroxide or inorganic salt as oxidant has been realized. This method of direct dehydrogenation coupling to aniline compound has remarkable step economy. However, at the same time, the use of a large number of oxidants such as peroxide and high-valence metal salts also brings some unavoidable problems, such as the production of a large number of by-products, resulting in the reduction of atomic economy. A large number of oxidant residues in the system make it difficult to separate, and the general price is high, resulting in environmental pollution. The substitution of O2 for organic peroxides and high value metal salts as oxidants can not only effectively avoid the above problems, but also be cheap, easy to obtain, green and environmentally friendly. It is a step economy. The aryl C-N bond was constructed by coupling the aromatic sp2C-H bond and the amino N-H bond with atomic economy. Therefore, some aromatic amines were synthesized on the basis of Cu _ 2O _ 2 gas oxidation of 2-phenylpyridine derivatives with acetaniline derivatives by dehydrogenation of aryl C-N bonds. The content of this paper is as follows: 1. The aryl C-N bond was directly synthesized by oxidative dehydrogenation of O2 with 2-phenylpyridine and its derivatives and acetanilide and CuBr as catalyst. A series of aromatic amines containing pyridyl were synthesized. At the same time, the reaction solvent and solvent amount, catalyst and its dosage, temperature and time were screened, and the reaction mechanism was deduced. Nineteen aromatic amines were synthesized and their structures were all identified by NMR. 2. Using quinoline derivative and phenoxyacetic acid derivative as substrate, AgNO3 as catalyst, K2S2O8 as oxidant, water and dichloromethane as solvent (1:1 by volume), A series of 2- (phenoxymethyl) quinoline compounds were synthesized in the presence of trifluoroacetic acid, and the reaction conditions were optimized. The effects of catalyst, solvent, oxidant, temperature and time on the reaction were discussed. Eleven target compounds were synthesized and their structures were all identified by NMR.
【學(xué)位授予單位】：鄭州大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2014
【分類號】：R914

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相關(guān)期刊論文 前1條

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