【摘要】：自由基反應(yīng)是一類重要的反應(yīng)類型。由于自由基活潑,反應(yīng)性強,能夠快速反應(yīng)生成穩(wěn)定分子等諸多優(yōu)點,一個世紀(jì)以來備受化學(xué)研究者的關(guān)注。各種自由基反應(yīng)方法相繼報道,并普遍用于化學(xué)合成、醫(yī)藥和農(nóng)藥等領(lǐng)域。但就可持續(xù)發(fā)展而言,研究新型自由基反應(yīng)仍然具有重要意義。本文的研究內(nèi)容包含以下兩部分:(1)FeCl_2催化條件下實現(xiàn)了烯基環(huán)丙烷類底物的三氟甲基化反應(yīng),考察了23種不同類型的底物,以最高可達(dá)到96%的收率獲得了含三氟甲基的二氫萘衍生物。該方法具有反應(yīng)條件溫和、催化劑廉價易得、反應(yīng)時間短等優(yōu)點。隨后我們將三氟甲基化產(chǎn)物進(jìn)行還原和脫羧衍生化轉(zhuǎn)化。最后為驗證可能的反應(yīng)機理,設(shè)計對照實驗,證明該反應(yīng)可能是自由基反應(yīng)。(2)非金屬催化的條件下實現(xiàn)了烯基環(huán)丙烷類底物的疊氮化反應(yīng),考察了20種不同類型的底物,以最高可達(dá)到88%的收率獲得了含疊氮基的二氫萘衍生物,該方法反應(yīng)條件溫和、反應(yīng)原料廉價易得、反應(yīng)時間短等優(yōu)點。最重要的是該反應(yīng)無需金屬催化劑。隨后進(jìn)行疊氮化產(chǎn)物的衍生化實驗,分別進(jìn)行與炔烴的點擊反應(yīng)和還原氨化反應(yīng)。最后設(shè)計對照實驗,對反應(yīng)機理進(jìn)行研究,表明該反應(yīng)可能是自由基反應(yīng)
[Abstract]:Free radical reaction is an important type of reaction. Because of the active free radicals, strong reactivity, rapid reaction to produce stable molecules and many other advantages, it has attracted the attention of chemical researchers for a century. Various free radical reaction methods have been reported and widely used in chemical synthesis, medicine and pesticides. However, as far as sustainable development is concerned, it is still of great significance to study new free radical reactions. The main contents of this paper are as follows: (1) trifluoromethylation of allyl cyclopropane substrates was carried out under the condition of FeCl_2, and 23 different substrates were investigated. The derivative of dihydronaphthalene containing trifluoromethyl was obtained in 96% yield. The method has the advantages of mild reaction conditions, cheap catalyst and short reaction time. The trifluoromethylation products were then reduced and decarboxylated. Finally, in order to verify the possible reaction mechanism, a controlled experiment was designed to prove that the reaction may be a free radical reaction. (2) the azide reaction of allyl cyclopropane substrates was realized under the condition of non-metal catalysis, and 20 different substrates were investigated. The dihydronaphthalene derivatives containing azide group were obtained in a yield of up to 88%. The reaction conditions were mild, the raw materials were cheap and easy to obtain, and the reaction time was short. The most important thing is that the reaction does not require a metal catalyst. Then the azide products were derivatized and the click-down reaction and reductive ammoniation reaction with alkynes were carried out respectively. Finally, a controlled experiment was designed to study the reaction mechanism, which indicates that the reaction may be a free radical reaction.
【學(xué)位授予單位】：上海師范大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O621.251
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本文編號：2181636