本文選題：無金屬催化 + α　； 參考：《鄭州大學(xué)》2017年碩士論文

【摘要】：1,4-二羰基化合物普遍存在于自然界中,在農(nóng)業(yè)、醫(yī)藥、化工等領(lǐng)域是一種十分有價(jià)值的化合物。特別的是,1,4-二羰基是合成五元雜環(huán)類化合物的重要結(jié)構(gòu)單元,如呋喃、噻吩、吡咯和環(huán)戊烯酮等。本論文主要探究了α,α-二芳基烯丙醇和苯甲醛在無金屬催化條件下經(jīng)過氧化重排反應(yīng)得到1,4-二羰基化合物,研究結(jié)果如下:1.本文以α,α-二芳基烯丙醇為底物,TBPB(過氧化苯甲酸叔丁酯)為綠色的氧化劑,以便宜易得的苯甲醛作為酰基化試劑,甲苯為反應(yīng)溶劑,在120o C下反應(yīng)24小時(shí),得到1,4-二羰基化合物,產(chǎn)率高達(dá)94%。該課題的新穎之處在于無需底物的修飾、沒有強(qiáng)酸強(qiáng)堿的參與,具有操作簡(jiǎn)單、高效、環(huán)境友好等優(yōu)點(diǎn),并且沒有多余的副產(chǎn)物,原子經(jīng)濟(jì)效應(yīng)突出。（？）2.為了闡明反應(yīng)機(jī)理,設(shè)計(jì)了對(duì)比試驗(yàn),結(jié)果顯示:α,α-二芳基烯丙醇和苯甲醛在不加入TBPB的標(biāo)準(zhǔn)條件下反應(yīng)時(shí),沒有檢測(cè)到相應(yīng)目標(biāo)產(chǎn)物的存在,說明TBPB對(duì)反應(yīng)的順利進(jìn)行起著關(guān)鍵性作用。并在標(biāo)準(zhǔn)條件下,向反應(yīng)體系中加入2 equiv的自由基捕捉劑TEMPO(2,2,6,6-四甲基哌啶-氮氧化物),沒有得到目標(biāo)產(chǎn)物,說明在該反應(yīng)機(jī)理中可能存在自由基歷程。根據(jù)對(duì)比實(shí)驗(yàn)和已發(fā)表的相關(guān)文獻(xiàn)的參考,推測(cè)了可能的反應(yīng)機(jī)理:（?）
[Abstract]:1) 4-dicarbonyl compounds are widely found in nature and are valuable compounds in agriculture, medicine, chemical industry and so on. In particular, the 4-dicarbonyl group is an important structural unit for the synthesis of quaternary heterocyclic compounds, such as furan, thiophene, pyrrole and cyclopentenone. In this paper, we studied the oxidation rearrangement of 偽, 偽 -diarylallyl alcohol and benzaldehyde under the condition of non-metal catalysis to obtain 1o 4-dicarbonyl compound. The results are as follows: 1: 1. Using 偽, 偽 -diarylallyl alcohol as substrate, TBPBas as green oxidant, cheap benzaldehyde as acylation reagent, toluene as reaction solvent, and reaction at 120o C for 24 hours, a 1-dimethyl-4-dicarbonyl compound was obtained. The yield is as high as 94. The novelty of this subject lies in the fact that there is no substrate modification, no strong acid and strong base, simple operation, high efficiency, environmental friendliness, and no superfluous by-products, so the atomic economic effect is obvious. In order to elucidate the reaction mechanism, a comparative experiment was designed. The results showed that when 偽, 偽 -diarylallyl alcohol and benzaldehyde reacted without TBPB, the corresponding target products were not detected. It is concluded that TBPB plays a key role in the smooth progress of the reaction. Under the standard conditions, the free radical trapping agent of 2 equiv was added to the reaction system, and the target product was not obtained, indicating the existence of free radical mechanism in the reaction mechanism. According to the comparative experiments and the references of the published literatures, the possible reaction mechanism is deduced.
【學(xué)位授予單位】：鄭州大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O621.25

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