本文選題：可見光催化　切入點(diǎn)：交叉脫氫偶聯(lián)反應(yīng)　出處：《深圳大學(xué)》2017年碩士論文

【摘要】：光催化反應(yīng)是一種綠色清潔的反應(yīng)途徑,通常以可見光作為能源來誘發(fā)化學(xué)反應(yīng)的進(jìn)行。可見光誘導(dǎo)光氧化還原反應(yīng)策略已經(jīng)被廣泛應(yīng)用于活性有機(jī)小分子的合成中。通過光化學(xué)反應(yīng),化學(xué)家們已經(jīng)實(shí)現(xiàn)了醛酮羰基α位的取代反應(yīng),環(huán)加成反應(yīng),α氨基碳自由基反應(yīng),芳烴及烯烴的三氟甲基化,亞胺陽離子為中間體的反應(yīng)等,成功地構(gòu)建了C-C鍵、C-O鍵、C-P鍵、C-N鍵。本論文介紹了可見光催化在交叉脫氫偶聯(lián)反應(yīng)中的研究進(jìn)展,并圍繞可見光催化劑的負(fù)載做了相關(guān)工作:首先,選擇具有較好透光性和穩(wěn)定性的聚二甲基硅氧烷(PDMS)作為有機(jī)海綿載體;然后利用表面修飾技術(shù)(空氣等離子體)在海綿表面引入親水性的羥基官能團(tuán),并用2-甲基丙烯�；一谆然@(METAC)進(jìn)行自由基聚合修飾;最后,用離子交換的方法在PDMS-MATAC海綿上負(fù)載玫瑰紅(Rose Bengal,RB)染料,從而獲得海綿負(fù)載的可見光催化劑。所獲得的海綿光催化劑通過SEM、EDS等表征手段進(jìn)行定性分析,并通過1H NMR進(jìn)行定量表征,負(fù)載量為0.01mmol/g。催化活性方面,PDMS-RB海綿光催化劑對于四氫異喹啉類衍生物與硝基甲烷、丙酮、重氮乙酸乙酯類反應(yīng)具有普遍的適用性,取得了預(yù)想的催化效果。傳統(tǒng)的二氧化硅、高分子聚合物、金屬有機(jī)框架和石墨烯等固體催化劑載體需要通過過濾、離心方法來實(shí)現(xiàn)催化劑的分離,而PDMS海綿載體光催化劑僅需通過簡易操作,反應(yīng)結(jié)束后直接將海綿夾出反應(yīng)體系就能實(shí)現(xiàn)催化劑與反應(yīng)物的分離。另外,對該催化劑的回收利用進(jìn)行研究,以四氫異喹啉與硝基甲烷為模型反應(yīng),催化劑循環(huán)利用次數(shù)≥15次(收率≥85%),且催化活性沒有明顯降低。為進(jìn)一步驗(yàn)證PDMS-RB海綿光催化劑在工業(yè)應(yīng)用中的可行性,組建一個(gè)連續(xù)流動的反應(yīng)裝置(包含一個(gè)蠕動泵、一段玻璃管和一條燈帶)。在測試以N苯基四氫異喹啉與硝基甲烷為模型的放大量反應(yīng),僅需48 h就取得了88%的柱層析收率,此時(shí)催化劑的用量僅為1.4 mol%。這是一個(gè)很容易構(gòu)建的簡易裝置,任何一個(gè)簡易的有機(jī)化學(xué)實(shí)驗(yàn)室均可搭建這種裝置來做大規(guī)模的合成反應(yīng)。此外,將玫瑰紅光催化劑的催化反應(yīng)類型做了進(jìn)一步的拓展,實(shí)現(xiàn)了N芳基四氫異喹啉類酯與馬來酸酐類衍生物的[3+2]環(huán)加成反應(yīng)。首次將玫瑰紅結(jié)合過渡金屬鹽實(shí)現(xiàn)了叔胺類α位C-H鍵烯基化反應(yīng)。PDMS海綿經(jīng)過共價(jià)鍵修飾,以谷氨酸為Linker,成功將玫瑰紅、脯氨酸連接在PDMS海綿上,制備了疏水性的雙功能催化劑。以芳基四氫異喹啉與丙酮的曼尼烯反應(yīng)為模型,驗(yàn)證了該催化劑以水作為溶劑的催化效果。總之,通過表面改性技術(shù)對PDMS海綿高分子材料進(jìn)行修飾,修飾后的海綿通過離子交換技術(shù)與可見光催化劑玫瑰紅結(jié)合,成功地開發(fā)了一種簡單、高效的有機(jī)海綿光催化劑。在可見光誘導(dǎo)下,對于CDC反應(yīng),海綿光催化劑顯示出優(yōu)良的催化活性。PDMS有機(jī)海綿光催化劑具有:穩(wěn)定性強(qiáng)、易于回收、重復(fù)利用次數(shù)多、反應(yīng)活性高、易放大量實(shí)驗(yàn)等優(yōu)點(diǎn)。結(jié)果表明PDMS海綿是一種很有前途的非均相催化載體。在PDMS海綿上固定其他催化劑的研究(包括多功能催化劑和實(shí)現(xiàn)立體選擇性的交叉脫氫偶聯(lián)反應(yīng))相關(guān)的更有趣的轉(zhuǎn)換實(shí)驗(yàn)正在進(jìn)行中。
[Abstract]:The photocatalytic reaction is a way of green cleaning, usually in the visible light as the energy to induce chemical reactions. The synthesis of visible light induced photo oxidation reduction reaction strategy has been widely used in active organic molecules. Through photochemical reactions, chemists has achieved the substitution reaction of aldehyde and ketone carbonyl alpha bits, cycloaddition, alpha amino carbon free radical reaction, aromatics and olefins three fluoromethylation, iminium cation intermediate reaction, the successful construction of the C-C key, C-O key, C-P key, C-N key. This paper introduces the research progress in visible light catalytic dehydrogenation cross coupling reaction. And around the load of visible light catalyst to do related work: first, with good transparency and stability of two polydimethylsiloxane (PDMS) as organic sponge carrier; then using surface modification technology (air plasma) in the sea The introduction of hydrophilic hydroxyl groups on the surface of cotton, and 2- methacryloyl ethyl three methyl ammonium chloride (METAC) modified by free radical polymerization; finally, using the method of ion exchange in PDMS-MATAC sponge load Rose (Rose Bengal, RB) to obtain dye, visible light catalyst load. The obtained sponge sponge light catalyst by SEM, EDS were characterized by means of qualitative analysis and quantitative characterization of 1H by NMR, the load of 0.01mmol/g. catalytic activity, PDMS-RB sponge photocatalyst for four isoquinoline derivatives and nitro - methane, acetone, ethyl diazoacetate reaction has general applicability, achieved the expected catalytic effect the traditional silica, polymers, metal organic frameworks and graphene solid catalyst carrier by filtration, centrifugation to separate the catalyst, and PDMS sponge The carrier photocatalyst only by simple operation, after the reaction will be directly isolated from sponge clamp reaction system can realize the catalyst and the reactants. In addition, research on the recovery of the catalyst utilization, with four isoquinoline and nitromethane as a model reaction, the catalyst recycling more than 15 times (yield = 85%) and, without loss of catalytic activity. In order to further verify the feasibility of PDMS-RB sponge photocatalyst in industrial application, the formation of a continuous flow reactor (including a peristaltic pump, a glass tube and a lamp). In the test with N four phenyl isoquinoline and nitromethane as a reaction the model, only 48 h made column yield of 88%, the amount of catalyst is 1.4 mol%. which is a simple device, it is easy to construct, any simple organic chemical laboratory can build this Device to do large-scale synthesis. In addition, the red rose type catalytic reaction catalyst was further expanded, [3+2] ring N four aryl hydrogen isoquinoline derivatives and ester of Maleic Anhydride Addition Reaction for the first time. The red roses with transition metal salts to achieve tertiary amine ene C-H key alpha the reaction of.PDMS sponge through covalent modification, such as glutamic acid Linker, successfully rose red, proline connection in PDMS sponge, hydrophobic bifunctional catalysts were prepared. The Manny ene reaction of aryl four isoquinoline with acetone as a model, proved the catalyst with water as solvent catalytic effect in short, through the surface modification technology of modified PDMS foam polymer material, the modified sponge rose by ion exchange technique is combined with visible light catalyst, successfully developed a simple and efficient machine with the sea Cotton. Photocatalyst under visible light induced, for the CDC reaction, sponge photocatalyst showed excellent catalytic activity of.PDMS organic light sponge catalyst: strong stability, easy to recycle, reuse times and high reactivity, easy to put a large number of experiments. The results show the advantages of the PDMS sponge is a very promising heterogeneous catalytic carrier. Research on fixed other catalysts in PDMS sponge (including multifunctional catalyst and cross dehydrogenative coupling for stereoselective conversion) more interesting experiments are underway.

【學(xué)位授予單位】：深圳大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O643.36

【參考文獻(xiàn)】

相關(guān)期刊論文 前2條

1 張艷;馮柏年;;過渡金屬催化的不對稱交叉脫氫偶聯(lián)反應(yīng)研究進(jìn)展[J];有機(jī)化學(xué);2014年12期

2 戴小軍;許孝良;李小年;;可見光催化在有機(jī)合成中的應(yīng)用[J];有機(jī)化學(xué);2013年10期

，

本文編號：1696703