本文選題：1 + 4-二氫吡嗪��； 參考：《北京工業(yè)大學(xué)》2014年博士論文

【摘要】：1,4-二氫吡嗪是一類具有8π電子體系的反芳香性化合物，在醫(yī)藥和生物制劑等方面有著重要的應(yīng)用。在綜述了1,4-二氫吡嗪合成方法和吡嗪光化學(xué)性質(zhì)的基礎(chǔ)上，確定以1,4-二氫吡嗪的合成和光化學(xué)性質(zhì)研究為本論文的主要內(nèi)容。對(duì)1,4-二氫吡嗪合成方法進(jìn)行研究，探討影響1,4-二氫吡嗪合成的相關(guān)因素，以得到一系列目標(biāo)化合物。通過(guò)對(duì)1,4-二氫吡嗪光穩(wěn)定性和光化學(xué)反應(yīng)的研究，確定1,4-二氫吡嗪的光化學(xué)反應(yīng)的類型及產(chǎn)物結(jié)構(gòu)。對(duì)1,4-二氫吡嗪合成方法和光化學(xué)性質(zhì)的研究，為其在醫(yī)藥和生物制劑等方面更廣泛的應(yīng)用提供實(shí)驗(yàn)基礎(chǔ)，也可為其光氧化反應(yīng)和光環(huán)合反應(yīng)研究提供理論和實(shí)驗(yàn)基礎(chǔ)。 1,4-二氫吡嗪的合成研究是對(duì)N,N’-二酰基-1,4-二氫吡嗪和N,N’-二芳基-1,4-二氫吡嗪的合成方法進(jìn)行研究，通過(guò)探討反應(yīng)因素（反應(yīng)物、溶劑和催化劑等）對(duì)合成得率的影響，以及微波輔助合成技術(shù)對(duì)合成方法的改進(jìn)，以得到目標(biāo)化合物的高效合成方法。在N,N’-二芳基-1,4-二氫吡嗪的合成新方法研究中，建立以N,N’-二芳基-1,4-二氮雜丁二烯為原料的方法。一種合成方法是吡嗪環(huán)的修飾，探索以1,4-二氮雜丁二烯為起始原料，先合成吡嗪環(huán)，再對(duì)其結(jié)構(gòu)修飾以合成1,4-二氫吡嗪的方法；另一種合成方法是吡嗪環(huán)的構(gòu)建，根據(jù)Hetero-Diels-Alder反應(yīng)原理，通過(guò)對(duì)1,4-二氮雜丁二烯與親雙烯體反應(yīng)的研究，以合成1,4-二氫吡嗪。通過(guò)探討1,4-二氫吡嗪的合成反應(yīng)機(jī)理，闡明1,4-二氫吡嗪形成過(guò)程和其關(guān)鍵影響因素，為1,4-二氫吡嗪合成工藝的優(yōu)化和放大奠定基礎(chǔ)。 在1,4-二氫吡嗪的光化學(xué)性質(zhì)研究中，對(duì)所合成的N,N’-二�；�-1,4-二氫吡嗪和N,N’-二芳基-1,4-二氫吡嗪的光譜特征、光穩(wěn)定性和光化學(xué)反應(yīng)進(jìn)行研究，，以確定其光化學(xué)反應(yīng)的機(jī)理和在有機(jī)合成中的應(yīng)用。采用紫外-可見光譜法，研究其吸收光譜特征與結(jié)構(gòu)之間的關(guān)系；通過(guò)對(duì)1,4-二氫吡嗪溶液光穩(wěn)定性的研究，確定其光化學(xué)反應(yīng)研究的光波范圍。在選定的光波照射下，采用液相光化學(xué)反應(yīng)和固相光化學(xué)反應(yīng)兩種方式研究1,4-二氫吡嗪的光化學(xué)反應(yīng)。在液相光化學(xué)反應(yīng)研究中，探討溶劑、濃度、光敏劑等因素對(duì)光化學(xué)反應(yīng)的影響，分離并鑒定光化學(xué)反應(yīng)產(chǎn)物；采用自旋捕獲電子共振技術(shù)，研究1,4-二氫吡嗪的液相光化學(xué)反應(yīng)機(jī)理，進(jìn)一步闡明光化學(xué)反應(yīng)產(chǎn)物的生成機(jī)制。1,4-二氫吡嗪固相光化學(xué)反應(yīng)主要研究的是固相模板引導(dǎo)的[2+2]光環(huán)合反應(yīng)。采用熱臺(tái)顯微法篩選光環(huán)合反應(yīng)模板，采用混合溶劑揮發(fā)法制備1,4-二氫吡嗪和光環(huán)合反應(yīng)模板的共晶體，通過(guò)對(duì)共晶體光照，以得到1,4-二氫吡嗪的[2+2]光環(huán)合反應(yīng)產(chǎn)物。根據(jù)共晶體的X-單晶衍射數(shù)據(jù)，探討固相模板引導(dǎo)的1,4-二氫吡嗪[2+2]光環(huán)合反應(yīng)機(jī)理，為2,5,8,11-四氮雜四星烷的合成提供理論基礎(chǔ)。 在1,4-二氫吡嗪的合成及光化學(xué)性質(zhì)研究中，共分離出43個(gè)未見文獻(xiàn)報(bào)道的化合物，其中有27個(gè)是1,4-二氫吡嗪和相關(guān)反應(yīng)產(chǎn)物、12個(gè)光氧化產(chǎn)物和4個(gè)[2+2]光環(huán)合反應(yīng)產(chǎn)物。所合成的化合物的均得到1H NMR、13C NMR、HRMS和X-單晶衍射的結(jié)構(gòu)確認(rèn)。1,4-二氫吡嗪的液相光氧化反應(yīng)和固相模板引導(dǎo)的[2+2]光環(huán)合反應(yīng)合成四星烷的研究均未見文獻(xiàn)報(bào)道，此研究結(jié)果可為1,4-二氫吡嗪的更廣泛應(yīng)用提供理論和實(shí)驗(yàn)基礎(chǔ)。
[Abstract]:1,4- two hydropyrazine is an anti aromatic compound with 8 pi electron systems. It has important applications in medicine and biological agents. On the basis of the synthesis method of 1,4- two hydropyrazine and the photochemical properties of pyrazine, the synthesis and photochemical properties of 1,4- two hydropyrazine are determined as the main content of this paper. 1,4- two The synthesis method of pyrazine was studied and the related factors affecting the synthesis of 1,4- two pyrazine were investigated to obtain a series of target compounds. Through the study of the photostability and photochemical reaction of 1,4- two pyrazine, the type and structure of the photochemical reaction of 1,4- two hydropyrazine was determined. The synthesis and photochemical properties of 1,4- two pyrazine were made. The study provides an experimental basis for its wider application in medicine and biologics, and provides a theoretical and experimental basis for its photooxidation reaction and the study of the photosynthetic reaction.
The synthesis of 1,4- two hydropyrazine is a study of the synthesis of N, N '- two acyl -1,4- two hydropyrazine and N, N' - two aryl -1,4- two hydropyrazine. The effect of reaction factors (reactants, solvents and catalysts, etc.) on the synthesis rate and the improvement of synthesis methods by microwave assisted synthesis to obtain target compounds High efficiency synthesis method. In the study of the synthesis of N, N '- two aryl -1,4- two pyrazine, a method was established with N, N' - two aryl -1,4- two azobutadiene as raw material. A synthesis method was the modification of pyrazine ring, which was used as the starting material of 1,4- two azotadiene, first as a pyrazine ring, and then modified to synthesize the 1,4- two hydropyrazine. The other synthesis method is the construction of pyrazine ring. According to the principle of Hetero-Diels-Alder reaction, the reaction of 1,4- two azotadiene with bienes is studied to synthesize 1,4- two pyrazine. By discussing the synthesis reaction mechanism of 1,4- two hydropyrazine, the formation process of 1,4- two hydropyrazine and its key influencing factors are clarified, which are 1,4- Two the optimization and amplification of the hydropyrazine synthesis process lay the foundation.
In the photochemical properties of 1,4- two pyrazine, the spectral characteristics, photostability and photochemical reaction of the synthesized N, N '- two acyl -1,4- two hydropyrazine and N, N' - two aryl -1,4- two hydropyrazine were studied in order to determine the mechanism of the photochemical reaction and the application in organic synthesis. The relationship between the spectral characteristics and the structure; through the study of the photostability of the 1,4- two hydropyrazine solution, the light wave range of the photochemical reaction was determined. The photochemical reaction of 1,4- two hydropyrazine was studied by liquid photochemical reaction and solid photochemical reaction under the selected light wave. The liquid photochemical reaction was used in the liquid phase photochemical reaction. In the study, the effects of solvents, concentration, photosensitizer and other factors on the photochemical reaction were investigated, and the photochemical reaction products were separated and identified. The mechanism of the liquid phase photochemical reaction of 1,4- two hydropyrazine was studied by the spin capture electron resonance technique, and the mechanism of the formation mechanism of the photochemical reaction product was further elucidated by.1,4- two hydropyrazine solid phase photochemical reaction. The [2+2] photoperiod reaction guided by solid phase template is studied. The eutectic of the 1,4- two hydropyrazine and the photoperiazine reaction template is prepared by the hot stage microscopy, and the co crystal of the 1,4- two hydropyrazine and the photoperiazine reaction template is prepared by the mixed solvent evaporation method. The [2+2] photoperiod reaction products of the 1,4- two hydropyrazine are obtained by the photolation of the eutectic. Diffraction data were used to investigate the mechanism of solid phase template directed 1,4- two hydropyrazine [2+2] ring reaction, providing a theoretical basis for the synthesis of 2,5,8,11- four azacarane.
In the study of the synthesis and photochemical properties of 1,4- two pyrazine, 43 compounds have not been reported, including 27 1,4- two hydropyrazine and related reaction products, 12 photooxidation products and 4 [2+2] photosynthetic reaction products. The synthesized compounds have been confirmed by the structure of 1H NMR, 13C NMR, HRMS and X- single crystal diffraction. The results of the liquid phase photooxidation of 4- two hydropyrazine and the synthesis of [2+2] by solid phase template guided synthesis of tetrametane have not been reported. The results can provide theoretical and experimental basis for the wider application of 1,4- two pyrazine.
【學(xué)位授予單位】：北京工業(yè)大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2014
【分類號(hào)】：O626;R914.5

【參考文獻(xiàn)】

相關(guān)期刊論文 前1條

1 黃乃聚;尤晨;章道道;;環(huán)糊精在有機(jī)合成中的應(yīng)用[J];有機(jī)化學(xué);1987年06期

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