1,4-二氢吡嗪的合成及光化学性质的研究

发布时间：2018-06-01 09:46

本文选题：1 + 4-二氢吡嗪　；参考：《北京工业大学》2014年博士论文

【摘要】：1,4-二氢吡嗪是一类具有8π电子体系的反芳香性化合物，在医药和生物制剂等方面有着重要的应用。在综述了1,4-二氢吡嗪合成方法和吡嗪光化学性质的基础上，确定以1,4-二氢吡嗪的合成和光化学性质研究为本论文的主要内容。对1,4-二氢吡嗪合成方法进行研究，探讨影响1,4-二氢吡嗪合成的相关因素，以得到一系列目标化合物。通过对1,4-二氢吡嗪光稳定性和光化学反应的研究，确定1,4-二氢吡嗪的光化学反应的类型及产物结构。对1,4-二氢吡嗪合成方法和光化学性质的研究，为其在医药和生物制剂等方面更广泛的应用提供实验基础，也可为其光氧化反应和光环合反应研究提供理论和实验基础。 1,4-二氢吡嗪的合成研究是对N,N’-二酰基-1,4-二氢吡嗪和N,N’-二芳基-1,4-二氢吡嗪的合成方法进行研究，通过探讨反应因素（反应物、溶剂和催化剂等）对合成得率的影响，以及微波辅助合成技术对合成方法的改进，以得到目标化合物的高效合成方法。在N,N’-二芳基-1,4-二氢吡嗪的合成新方法研究中，建立以N,N’-二芳基-1,4-二氮杂丁二烯为原料的方法。一种合成方法是吡嗪环的修饰，探索以1,4-二氮杂丁二烯为起始原料，先合成吡嗪环，再对其结构修饰以合成1,4-二氢吡嗪的方法；另一种合成方法是吡嗪环的构建，根据Hetero-Diels-Alder反应原理，通过对1,4-二氮杂丁二烯与亲双烯体反应的研究，以合成1,4-二氢吡嗪。通过探讨1,4-二氢吡嗪的合成反应机理，阐明1,4-二氢吡嗪形成过程和其关键影响因素，为1,4-二氢吡嗪合成工艺的优化和放大奠定基础。在1,4-二氢吡嗪的光化学性质研究中，对所合成的N,N’-二酰基-1,4-二氢吡嗪和N,N’-二芳基-1,4-二氢吡嗪的光谱特征、光稳定性和光化学反应进行研究，，以确定其光化学反应的机理和在有机合成中的应用。采用紫外-可见光谱法，研究其吸收光谱特征与结构之间的关系；通过对1,4-二氢吡嗪溶液光稳定性的研究，确定其光化学反应研究的光波范围。在选定的光波照射下，采用液相光化学反应和固相光化学反应两种方式研究1,4-二氢吡嗪的光化学反应。在液相光化学反应研究中，探讨溶剂、浓度、光敏剂等因素对光化学反应的影响，分离并鉴定光化学反应产物；采用自旋捕获电子共振技术，研究1,4-二氢吡嗪的液相光化学反应机理，进一步阐明光化学反应产物的生成机制。1,4-二氢吡嗪固相光化学反应主要研究的是固相模板引导的[2+2]光环合反应。采用热台显微法筛选光环合反应模板，采用混合溶剂挥发法制备1,4-二氢吡嗪和光环合反应模板的共晶体，通过对共晶体光照，以得到1,4-二氢吡嗪的[2+2]光环合反应产物。根据共晶体的X-单晶衍射数据，探讨固相模板引导的1,4-二氢吡嗪[2+2]光环合反应机理，为2,5,8,11-四氮杂四星烷的合成提供理论基础。在1,4-二氢吡嗪的合成及光化学性质研究中，共分离出43个未见文献报道的化合物，其中有27个是1,4-二氢吡嗪和相关反应产物、12个光氧化产物和4个[2+2]光环合反应产物。所合成的化合物的均得到1H NMR、13C NMR、HRMS和X-单晶衍射的结构确认。1,4-二氢吡嗪的液相光氧化反应和固相模板引导的[2+2]光环合反应合成四星烷的研究均未见文献报道，此研究结果可为1,4-二氢吡嗪的更广泛应用提供理论和实验基础。
[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.
【学位授予单位】：北京工业大学
【学位级别】：博士
【学位授予年份】：2014
【分类号】：O626;R914.5

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