本文選題：鐵 + 伯醇��； 參考：《吉林大學(xué)》2014年碩士論文

【摘要】：在有機(jī)合成中，為了合成結(jié)構(gòu)較為復(fù)雜的化合物，碳碳鍵的構(gòu)成是最基本的，也是極為重要的。構(gòu)成碳碳鍵的方法之一就是烷基化反應(yīng)，而以往所用的烷基化試劑，如烷基磺酸酯、烷基鹵化物等，烷基化反應(yīng)后副產(chǎn)物較多，不符合環(huán)保性，原子利用率也較低。為此，人們開始探索活化醇作烷基化試劑，特別是活化伯醇作烷基化試劑的新型烷基化反應(yīng)。 但是，現(xiàn)在以活化伯醇作烷基化試劑的烷基化反應(yīng)仍存在許多不足和缺點(diǎn)：1)現(xiàn)有方法絕大多數(shù)以稀有的貴重金屬Pd、Ru、Rh、Ir等作為催化劑，這顯然與當(dāng)今社會(huì)所大力提倡的可持續(xù)發(fā)展戰(zhàn)略不符；2)大多數(shù)催化劑并非市售品，而需要特制，因而不利于該方法的進(jìn)一步推廣與應(yīng)用；3)許多方法尚需依賴復(fù)雜的含N或P配體，或者需要另行添加氫授（受）體，才能得以實(shí)現(xiàn)，不僅降低反應(yīng)的原子利用率，，同時(shí)也增加了反應(yīng)后處理的難度；4)相當(dāng)多的方法還需化學(xué)計(jì)量堿的參與，對(duì)環(huán)境造成了較大影響。而活化伯醇作烷基化試劑仲醇β位直接氧化性烷基化的研究非常少，僅有兩種催化劑分別為貴重金屬Pd和Ag，而且Pd做催化劑時(shí)，反應(yīng)中需加入大量的氫受體1-decene，還使用了化學(xué)劑量的堿；另外一種Ag類催化劑，并非市售，還需要復(fù)雜的高溫活化以及氫化后方能使用。因此，在該方面對(duì)新型催化劑尤其是廉價(jià)的金屬催化劑的迫切需求已經(jīng)成為化學(xué)家所面臨的一大問(wèn)題。 實(shí)驗(yàn)室曾首次將鐵類催化劑用于活化伯醇為烷基化試劑的仲醇β位直接烷基化反應(yīng)。該催化體系具有許多優(yōu)點(diǎn)：1)首次應(yīng)用廉價(jià)的鐵類催化劑，且為市售；2)在催化劑量堿的作用下；3)不添加任何配體以及氫受體等，克服了以往該類烷基化反應(yīng)的不足與缺點(diǎn)。本實(shí)驗(yàn)在實(shí)驗(yàn)室前期工作基礎(chǔ)上，對(duì)鐵類催化劑——乙酰丙酮亞鐵，在活化伯醇作烷基化試劑的仲醇β位直接氧化性烷基化反應(yīng)中的應(yīng)用進(jìn)行了深入地研究；并在研究過(guò)程發(fā)現(xiàn)了該催化劑在活化伯醇作烷基化試劑的仲醇β位直接烷基化反應(yīng)中也頗具應(yīng)用潛力。這些工作為此類烷基化反應(yīng)提供了新的催化系統(tǒng)，為貴重的過(guò)渡金屬催化劑找到了新的廉價(jià)替代品。這些研究也讓我們對(duì)鐵類催化劑有了進(jìn)一步的認(rèn)識(shí)與理解。 我們首先在實(shí)驗(yàn)室前期研究基礎(chǔ)上，將乙酰丙酮亞鐵應(yīng)用于活化伯醇作烷基化試劑的仲醇β位直接氧化性烷基化反應(yīng)中，篩選出了以1-苯基乙醇與苯甲醇為底物的模型反應(yīng)的最佳條件。然后對(duì)該催化系統(tǒng)的底物適用性進(jìn)行了深入研究，得到了九種高級(jí)酮式產(chǎn)物，產(chǎn)率可達(dá)良好到優(yōu)秀。本研究是首次將鐵類催化劑應(yīng)用于活化伯醇作烷基化試劑的仲醇β位直接氧化性烷基化反應(yīng)中，同時(shí)也是首次開發(fā)出了可用于該類反應(yīng)的廉價(jià)金屬催化劑，為此類反應(yīng)以往的貴金屬催化系統(tǒng)找到了優(yōu)良的替代品。 在實(shí)驗(yàn)中，我們還發(fā)現(xiàn)在活化伯醇作烷基化試劑的該仲醇β位直接氧化性烷基化反應(yīng)條件的基礎(chǔ)上，僅需增加溶劑用量，主要產(chǎn)物即可由高級(jí)酮式產(chǎn)物逐漸轉(zhuǎn)變?yōu)槠渌鶎?duì)應(yīng)的高級(jí)醇式產(chǎn)物。并且我們還欣喜地發(fā)現(xiàn)，該催化系統(tǒng)與前述仲醇β位直接氧化性烷基化反應(yīng)一樣，也可以在空氣氛圍下進(jìn)行。在此基礎(chǔ)上，本人對(duì)其底物適用性進(jìn)行了初步研究，并獲得了可喜的階段性成果。本研究工作，再次向人們展示了廉價(jià)金屬，尤其是鐵類催化劑，在活化醇類化合物作烷基化試劑的有機(jī)反應(yīng)應(yīng)用中，具有廣闊的應(yīng)用前景與開發(fā)潛力。 本研究工作所探討的活化伯醇作烷基化試劑的兩個(gè)反應(yīng)，均為單步反應(yīng)，采用廉價(jià)易得金屬催化劑——乙酰丙酮亞鐵，使用催化劑量的堿，不需加任何氫授（受）體與配體，反應(yīng)可在空氣下進(jìn)行。該研究極大地降低了反應(yīng)成本與反應(yīng)難度，原子利用率高，對(duì)環(huán)境的影響小，更加符合綠色化學(xué)和可持續(xù)發(fā)展戰(zhàn)略的要求。通過(guò)本實(shí)驗(yàn)的研究進(jìn)一步加深了我們對(duì)鐵類催化劑的認(rèn)識(shí)，也進(jìn)一步地?cái)U(kuò)展了有機(jī)合成反應(yīng)中鐵類催化劑的應(yīng)用。
[Abstract]:In organic synthesis, in order to synthesize complex compounds, the composition of carbon and carbon bonds is the most basic and extremely important. One of the methods to form carbon carbon bonds is alkylation, and alkylation reagents used in the past, such as alkyl sulfonate and alkyl halides, have more by-products and are not environmentally friendly. Therefore, people began to explore the new alkylation reaction of activated alcohols as alkylation reagents, especially activated primary alcohols as alkylation reagents.
However, there are still many shortcomings and shortcomings in alkylation reagents with activated alkyl alcohols as alkylation reagents: 1) most of the existing methods use rare precious metals as Pd, Ru, Rh, Ir as catalysts. This is obviously inconsistent with the sustainable development strategy advocated by today's society; 2) most of the catalysts are not marketable, but need special. It is unfavorable to further popularization and application of this method; 3) many methods still need to rely on complex N or P ligands, or the need to add hydrogen (acceptor) body to be realized, not only to reduce the atomic utilization of the reaction, but also to increase the difficulty of the reaction after the reaction. (4) a considerable number of methods also require the participation of the stoichiometric base. There is a great influence on the environment. But the study of activated primary alcohol as an alkyl reagent is very rare. Only two kinds of catalysts are precious metals Pd and Ag, and when Pd is used as catalyst, a large amount of hydrogen receptor 1-decene is added to the reaction, and the chemical dose of alkali is also used; the other kind of Ag catalyst, It is not sold in the market, but also requires complex high temperature activation and the use of hydrogen in the rear. Therefore, the urgent need for new catalysts, especially cheap metal catalysts, has become a major problem for chemists.
The laboratory has used the iron catalyst for the first time to activate primary alcohols as alkylation reagents for secondary alkylation of secondary alcohols. The catalytic system has many advantages: 1) the first use of cheap iron catalysts, and the market for sale; 2) not adding any ligands and hydrogen receptors under the action of the catalyst; 3) to overcome the previous alkane On the basis of early laboratory work, the application of the iron catalyst, acetyl acetone, in the direct oxidative alkylation of secondary alcohols of activated primary alcohols as alkylation reagents, was deeply studied, and the catalyst was alkylated in activated primary alcohol. The reagents also have potential applications in the direct alkylation of secondary alcohols, which provide new catalytic systems for such alkylation, and have found new cheap alternatives for the valuable transition metal catalysts. These studies have also given us a further understanding and understanding of the iron catalysts.
On the basis of preliminary laboratory studies, the optimum conditions for the model reaction with 1- phenyl ethanol and benzyl alcohol as substrates were screened in the direct oxidation alkylation of secondary alcohols from activated primary alcohols to alkyl alcohol as alkylation reagents. Then the substrate suitability of the system was deeply studied. Nine kinds of advanced ketones are obtained. The yield is good to excellent. This study is the first time to use the iron catalyst in the alkylation of activated beta alcohol as an alkyl agent for the alkylation of secondary alcohols. It is also the first time to develop a cheap metal catalyst for this kind of reaction. The chemical system has found a good substitute.
In the experiment, we also found that on the basis of the direct oxidative alkylation of the secondary alcohols of activated primary alcohol as an alkylation agent, only the amount of solvent was needed, and the main product was gradually transformed from the advanced ketone product to its corresponding high alcohol product. On the basis of this, I have made a preliminary study on the applicability of the substrate and obtained the gratifying stage results. In this study, the cheap metals, especially the iron catalysts, were shown to the alkylation of activated alcohols. The organic reactions of the agents have broad application prospects and development potential.
The two reactions of activated primary alcohols as alkylation reagents are a single step reaction, using a cheap and readily available metal catalyst, acetyl acetone, and the use of a catalyst amount of alkali, without the addition of any hydrogen (acceptor) body and ligand, and the reaction can be carried out in the air. This study greatly reduced the reaction cost and difficulty of reaction. The high efficiency of atomic utilization and less influence on the environment is more in line with the requirements of the strategy of green chemistry and sustainable development. Through this study, we have further deepened our understanding of the iron catalyst and further expanded the application of the iron catalyst in the organic synthesis reaction.
【學(xué)位授予單位】：吉林大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2014
【分類號(hào)】：R914

【共引文獻(xiàn)】

相關(guān)會(huì)議論文 前1條

1 楊健;劉昕;孟大利;陳紅艷;宗智慧;馮亭亭;王小禹;李杰;孫凱;;廉價(jià)金屬活化醇類化合物做烷基化試劑的有機(jī)合成反應(yīng)研究[A];中國(guó)化學(xué)會(huì)第十屆全國(guó)有機(jī)合成化學(xué)學(xué)術(shù)研討會(huì)會(huì)議論文集[C];2012年

相關(guān)碩士學(xué)位論文 前1條

1 晏鳳霞;釕催化伯醇參與C-C，C-O鍵的形成研究[D];江南大學(xué);2013年

本文編號(hào)：2022935