本文選題：路易斯堿 + 活化環(huán)丙烷　； 參考：《東北師范大學(xué)》2016年碩士論文

【摘要】：活化的環(huán)丙烷和環(huán)氧乙烷在現(xiàn)代化學(xué)中,受到了許多學(xué)者的關(guān)注�；罨沫h(huán)丙烷及環(huán)氧乙烷能在路易斯酸或布朗斯特酸作用下發(fā)生開環(huán)反應(yīng)；開環(huán)后的中間體可在親核試劑的作用下發(fā)生環(huán)合或環(huán)加成反應(yīng)。環(huán)合所得到的化合物基本骨架廣泛存在于天然產(chǎn)物中,有重要的意義。有機(jī)催化是現(xiàn)代合成化學(xué)中較受關(guān)注的研究領(lǐng)域,近幾年有機(jī)胺的催化較為常見,有機(jī)胺是一類擁有N原子和孤電子對(duì)的有機(jī)化合物,也是常見的有機(jī)合成中間體,它可與某些有機(jī)物生成較穩(wěn)定的大分子化合物,增加分子的復(fù)雜程度。本文也對(duì)有機(jī)胺的催化做了探究。本文主要研究了活化環(huán)丙烷和環(huán)氧乙烷,在路易斯堿作用下的開環(huán)及開環(huán)中間體在有機(jī)合成中的應(yīng)用。第一部分首先研究了1-乙�；�-1-酰胺基環(huán)丙烷及其衍生物在不同的路易斯堿作用下開環(huán)原位生成穩(wěn)定的兩性離子中間體,該中間體在適當(dāng)?shù)臈l件下容易被分離,可實(shí)現(xiàn)克級(jí)制備。并通過一鍋煮法可使中間體與親電試劑發(fā)生親核反應(yīng),形成具有生物活性的含季碳中心的五元內(nèi)酰胺化合物。在實(shí)驗(yàn)過程中,若將氫氧化鈉的用量增加為2.5倍量,時(shí)間延長(zhǎng)至12小時(shí),產(chǎn)物會(huì)變成脫羰基的產(chǎn)物。在此基礎(chǔ)上我們還研究了1-乙�；�-1-苯甲�；h(huán)丙烷及其衍生物的開環(huán)反應(yīng),發(fā)現(xiàn)反應(yīng)機(jī)理是先生成兩性離子中間體,伴隨著時(shí)間延長(zhǎng),溫度增加,中間體會(huì)進(jìn)一步生成2,3-二氫呋喃產(chǎn)物。與此同時(shí)1,1-二酯基環(huán)丙烷化合物在有機(jī)堿的作用下也可以開環(huán),生成帶有羧酸根的內(nèi)鹽。本文也對(duì)反應(yīng)機(jī)理進(jìn)行了推測(cè)。第二部分主要研究有機(jī)胺對(duì)活化環(huán)氧乙烷的開環(huán)反應(yīng)。有機(jī)堿(如DABCO)的加入使得環(huán)氧乙烷的C-O鍵斷裂,經(jīng)過分子內(nèi)氧環(huán)合形成新的三元含氧雜環(huán)中間體,隨后發(fā)生�；w移,脫去有機(jī)堿形成多取代順式烯酯化合物。烯酯既可以作為烯基、羰基的來源,也可以合成某些高分子聚合物。本文合成烯酯的方法具有原子利用率高,環(huán)境污染小,產(chǎn)率高,操作簡(jiǎn)便等優(yōu)點(diǎn)。在實(shí)驗(yàn)中對(duì)產(chǎn)物的結(jié)構(gòu)進(jìn)行了核磁共振氫譜、核磁共振碳譜、質(zhì)譜以及一些化合物X-ray單晶衍射的表征。
[Abstract]:Active cyclopropane and ethylene oxide have attracted much attention in modern chemistry. The active cyclopropane and ethylene oxide can undergo ring opening reaction under the action of Lewis acid or Brownst acid, and the intermediate after ring opening can take place cyclization or cycloaddition reaction under the action of nucleophilic reagent. The basic framework of the compounds obtained by cyclization exists widely in natural products, which is of great significance. Organic catalysis is an important research field in modern synthetic chemistry. In recent years, the catalysis of organic amines is more common. Organic amines are a class of organic compounds with N atoms and lone electron pairs, and are also common intermediates in organic synthesis. It can form more stable macromolecular compounds with some organic compounds, increasing the molecular complexity. The catalysis of organic amines is also discussed in this paper. In this paper, the applications of active cyclopropane and ethylene oxide, ring opening and ring opening intermediates under the action of Lewis base in organic synthesis were studied. In the first part, we studied the formation of stable amphoteric ion intermediates from 1-acetyl-1-amino-cyclopropane and its derivatives in situ under different Lewis bases. The intermediates are easily separated under suitable conditions. It can be prepared in gram level. The nucleophilic reaction between the intermediate and the electrophilic reagent can be carried out by one-pot cooking method to form a quaternary lactam compound with biological activity containing the quaternary carbon center. During the experiment, if the amount of sodium hydroxide was increased to 2.5 times and the time was prolonged to 12 hours, the product would become the product of decarbonylation. On this basis, we also studied the ring-opening reaction of 1-acetyl-1-benzoyl cyclopropane and its derivatives. The intermediate will further produce 2o 3-dihydrofuran products. At the same time, 1-diester cyclopropane compounds can also open rings under the action of organic bases to form internal salts with carboxylic acids. The reaction mechanism is also speculated. In the second part, the ring opening reaction of organic amine on activated ethylene oxide was studied. The addition of organic base (such as DABCO) breaks the C-O bond of ethylene oxide and forms a new ternary oxygen-containing heterocyclic intermediate through intramolecular oxygen cyclization. Then acyl group migration occurs and the organic base is removed to form polysubstituted cis-alkyl compounds. Alkenyl esters can be used as sources of alkenyl and carbonyl groups, and some polymers can also be synthesized. In this paper, the method of synthesizing alkenyl ester has the advantages of high atomic utilization ratio, low environmental pollution, high yield and easy operation. The structure of the product was characterized by nuclear magnetic resonance (NMR), nuclear magnetic resonance (NMR) carbon spectroscopy (NMR), mass spectrometry (MS) and X-ray single crystal diffraction.
【學(xué)位授予單位】：東北師范大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2016
【分類號(hào)】：O621.25

【參考文獻(xiàn)】

相關(guān)博士學(xué)位論文 前1條

1 王兵;苯乙烯環(huán)氧化催化劑制備與環(huán)氧苯乙烷生產(chǎn)過程優(yōu)化研究[D];大連理工大學(xué);2015年

相關(guān)碩士學(xué)位論文 前2條

1 王尚文;路易斯堿催化丙交酯聚合及端羥基聚丙交酯的二異氰酸酯擴(kuò)鏈反應(yīng)研究[D];北京化工大學(xué);2013年

2 董春明;官能團(tuán)化環(huán)丙烷的合成和應(yīng)用研究[D];吉林大學(xué);2013年

，

本文編號(hào)：1775466