本文選題：超分子催化 + 三組分反應(yīng)�。� 參考：《昆明理工大學(xué)》2016年碩士論文

【摘要】：超分子催化是最接近于天然酶的化學(xué)反應(yīng)形式。主要是通過主體大分子與客體小分子間的相互作用來實(shí)現(xiàn)。環(huán)糊精作為第二代超分子主體,不僅可以用于分子識(shí)別和自組裝,而且其可作為超分子催化劑催化化學(xué)反應(yīng)。p-環(huán)糊精由于價(jià)廉易得而獲得最多關(guān)注,但存在水溶性較差的缺點(diǎn)。而且由于其官能團(tuán)單一,導(dǎo)致其催化性能和范圍受到較大限制。對(duì)p-環(huán)糊精進(jìn)行結(jié)構(gòu)修飾是一種有效的改造手段,而使用氨基對(duì)其進(jìn)行修飾,可望將超分子催化與胺催化相結(jié)合,從而有效增強(qiáng)其在有機(jī)合成中的應(yīng)用。本論文一共設(shè)計(jì)并合成了6種不同長度氨基鏈修飾的p-環(huán)糊精催化劑(ACDs, a0-5),將其用于催化多組分反應(yīng)。一方面,通過觀察此類催化劑在反應(yīng)中的催化效果,獲取催化劑結(jié)構(gòu)與反應(yīng)效果之間的構(gòu)效關(guān)系；另一方面,利用核磁共振、質(zhì)譜和光譜滴定等手段研究其反應(yīng)機(jī)理,為進(jìn)一步的研究提供一定的理論基礎(chǔ)。本論文完成的主要工作如下：一、合成了4種氨基側(cè)鏈修飾的β-環(huán)糊精(a0-3),將其用于催化合成一系列四酮類化合物。該實(shí)驗(yàn)的主要內(nèi)容包括：1、以苯甲醛和5,5-二甲基-1,3-環(huán)己二酮為底物進(jìn)行催化劑篩選及反應(yīng)條件優(yōu)化。2、對(duì)反應(yīng)底物進(jìn)行篩選,底物涉及芳香醛、脂肪醛、醛類似物、二酮及其類似物。3、通過核磁(1H-NMR和2D-NMR), HR-MS和Job's曲線等手段對(duì)催化機(jī)理進(jìn)行研究。4、通過催化劑循環(huán)使用次數(shù)及回收實(shí)驗(yàn)對(duì)催化劑效能進(jìn)行評(píng)估。本文一共合成了30種四酮產(chǎn)物(產(chǎn)率58-97%),我們發(fā)現(xiàn),隨著氨基側(cè)鏈的延長,催化效率越高。該方法綠色、高效、操作簡單、適合的底物范圍廣泛。最重要的是催化劑在循環(huán)使用8次后,催化效率依然保持在90%以上。而且催化劑回收方法簡單、綠色環(huán)保。二、本論文又合成了另外兩種氨基側(cè)鏈修飾的p-環(huán)糊精(a4-5),將一整系列的ACDs用于催化2-氨基-4H-苯并吡喃類化合物的合成。實(shí)驗(yàn)內(nèi)容主要包括：1、以苯甲醛、丙二腈、間苯二酚為底物進(jìn)行催化劑的篩選及反應(yīng)條件優(yōu)化。2、對(duì)底物進(jìn)行篩選,不僅設(shè)計(jì)合成簡單的2-氨基-4H-苯并吡喃類化合物,而且還設(shè)計(jì)合成了復(fù)雜的螺環(huán)化合物。3、通過核磁(1H-NMR和2D-NMR), HR-MS等手段對(duì)催化機(jī)理進(jìn)行研究。實(shí)驗(yàn)中一共設(shè)計(jì)合成了32種化合物(10種新化合物),通過對(duì)催化劑的篩選我們發(fā)現(xiàn),只有一定長度的氨基側(cè)鏈能夠使反應(yīng)高效生成目標(biāo)產(chǎn)物,首次發(fā)現(xiàn)該類催化劑能影響三組分反應(yīng)產(chǎn)物的化學(xué)選擇性。本文設(shè)計(jì)合成了一系列氨基修飾的β-環(huán)糊精催化劑,并對(duì)其在三組分反應(yīng)中的催化作用進(jìn)行研究。首次揭示這種胺類環(huán)糊精在多組分反應(yīng)中產(chǎn)生化學(xué)選擇性的深層次機(jī)理,可以為此類超分子主體/有機(jī)催化劑共同構(gòu)建的超分子催化體系的設(shè)計(jì)提供新思路。
[Abstract]:Supramolecular catalysis is the closest form of chemical reaction to natural enzymes. It is mainly realized by the interaction between host macromolecule and guest small molecule. As the second generation supramolecular host, cyclodextrin not only can be used for molecular recognition and self-assembly, but also can be used as a supramolecular catalyst to catalyze the chemical reaction. Because of its single functional group, its catalytic performance and range are limited greatly. The modification of p-cyclodextrin structure is an effective means of modification, but it is expected to combine supramolecular catalysis with amine catalysis to effectively enhance its application in organic synthesis. In this paper, six kinds of p-cyclodextrin catalysts (ACD _ s, a0-5) modified with different lengths of amino chains were designed and synthesized, which were used to catalyze multicomponent reactions. On the one hand, the structure-activity relationship between the structure of the catalyst and the reaction effect was obtained by observing the catalytic effect of the catalyst in the reaction; on the other hand, the reaction mechanism was studied by means of nuclear magnetic resonance, mass spectrometry and spectral titration. To provide a theoretical basis for further research. The main work of this thesis is as follows: firstly, four kinds of 尾 -cyclodextrin modified 尾 -cyclodextrin (尾 -cyclodextrin) (尾 -cyclodextrin) were synthesized and used to catalyze the synthesis of a series of tetraketones. The main contents of the experiment include: 1, using benzaldehyde and 5-dimethyl-1-dimethyl-3-cyclohexanedione as the substrates to screen the catalyst and optimize the reaction conditions. The substrate includes aromatic aldehydes, aliphatic aldehydes and aldehydes analogues. The catalytic mechanism was studied by NMR, 2D-NMR-NMR, HR-MS and Job's curves. The catalytic efficiency was evaluated by the recycle times of the catalyst and the recovery experiment. A total of 30 tetraketones were synthesized in this paper. We found that the higher the catalytic efficiency is with the prolongation of the amino side chain. The method is green, efficient, easy to operate and suitable for a wide range of substrates. The most important thing is that the catalytic efficiency remains above 90% after 8 cycles. And the catalyst recovery method is simple, green environmental protection. Secondly, two other amino side chain modified pcyclodextrin 4-5N were synthesized in this paper. A series of ACDs was used to catalyze the synthesis of 2-amino-4H-benzopyran compounds. The main contents of the experiment include: 1, screening of catalysts with benzaldehyde, malonitrile and resorcinol as substrates, optimization of reaction conditions, screening of substrates, design and synthesis of simple 2-amino-4H-benzopyran compounds. The complex snail compound. 3 was designed and synthesized, and the catalytic mechanism was studied by NMR, 2D-NMRO, HR-MS and so on. A total of 32 compounds and 10 new compounds were designed and synthesized in the experiment. By screening the catalyst, we found that only a certain length of amino side chain could efficiently produce the target product. It was found for the first time that this kind of catalyst could affect the chemical selectivity of the reaction products. A series of amino-modified 尾 -cyclodextrin catalysts were designed and synthesized in this paper. It is the first time to reveal the deep mechanism of the chemical selectivity of this amine cyclodextrin in multicomponent reactions, which can provide a new idea for the design of supramolecular catalytic system constructed by the supramolecular host / organic catalyst.
【學(xué)位授予單位】：昆明理工大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2016
【分類號(hào)】：O621.251

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1 任玉峰;氨基修飾的β-環(huán)糊精催化三組分反應(yīng)的研究[D];昆明理工大學(xué);2016年

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本文編號(hào)：1822716