铜催化非张力酮碳碳键断裂合成哌啶酯的研究

发布时间：2018-04-12 18:22

本文选题：铜催化 + 非张力酮　；参考：《湘潭大学》2017年硕士论文

【摘要】：开发有机化合物转化的新策略一直是有机化学研究的核心内容之一。通过碳碳键断裂,能够对有机化合物碳骨架结构进行重新构建,进而实现复杂化合物或多官能团化合物的高效合成。近年来,与羰基相连碳碳键断裂的研究引起了人们的广泛关注,这是由于羰基化合物,如醛、酮等,广泛存在于自然界中,同时很多羰基化合物都是商业化的、可直接购买获得的试剂,或者可容易地通过化学方法加以合成。因此,发展基于酮类化合物的碳碳键断裂、转化的新方法,无疑将扩展羰基化合物利用的范围。传统的酮类碳碳断裂的研究主要集中在张力环酮体系中。然而,张力酮的合成本身就相当困难复杂。与之相比,非张力酮的获得与合成就容易很多。然而,从能量的角度来说,由于缺乏环张力的驱动,非张力酮碳碳键的断裂具有较大的挑战性。本论文主要开展了铜催化非张力酮碳碳键断裂合成2,2,6,6-四甲基-1-哌啶基酯的研究。本论文的研究包括以下几部分内容:第一部分,以2-四氢萘酮与2,2,6,6-四甲基哌啶氧化物为原料,通过铜催化碳碳键断裂开环合成3-(2-甲酰基-苯基)-丙酸2,2,6,6-四甲基哌啶-1-基酯的反应尝试和条件优化。通过一系列的条件优化(催化剂、配体、溶剂、温度、胺),最终确定该反应的最优条件为催化剂二水氯化铜(10 mol%),配体1,10-菲罗琳(一水)(20mol%),苯胺(10 mol%),溶剂乙腈(2 mL),40°C,空气条件下。第二部分,对反应底物的普适性进行探讨。在最优化条件下,具有不同取代的α-芳基环酮或链酮都能很顺利地转化生成相应的酯。含不同取代基的2,2,6,6-四甲基哌啶氧化物在该反应条件下也能较好的兼容。为了说明所发展反应的实用性,对目标产物3-(2-甲酰基-苯基)-丙酸2,2,6,6-四甲基哌啶-1-基酯进行了一系列的合成衍生。第三部分,对3-(2-甲酰基-苯基)-丙酸2,2,6,6-四甲基哌啶-1-基酯及相应衍生物的结构表征,包括氢谱、碳谱、红外、高分辨质谱等。总之,本文研究发展了一种铜/空气的绿色催化体系,实现了非张力酮碳碳键断裂合成2,2,6,6-四甲基-1-哌啶基酯的新转化。本研究结果丰富了α-芳基环酮或链酮的转化手段,拓展了这类羰基化合物转化、使用的范围。
[Abstract]:The development of new strategies for the conversion of organic compounds has been one of the core contents of organic chemistry research.The carbon skeleton structure of organic compounds can be reconstructed by carbon-carbon bond breakage, and the efficient synthesis of complex compounds or multi-functional compounds can be realized.In recent years, the research of carbon-carbon bond fracture associated with carbonyl group has attracted much attention, because carbonyl compounds, such as aldehydes and ketones, are widely present in nature, and many carbonyl compounds are commercial.The obtained reagents can be purchased directly or can be easily synthesized by chemical methods.Therefore, the development of a new method of carbon-carbon bond breaking and transformation based on ketones will undoubtedly expand the range of utilization of carbonyl compounds.The traditional research of ketone carbon and carbon fracture is mainly concentrated in tension ring ketone system.However, the synthesis of tension ketones itself is quite difficult and complex.In contrast, it is much easier to obtain and synthesize non-tension ketones.However, from the point of view of energy, the fracture of non-tensional keto-carbon bond is challenging due to the lack of ring tension.In this paper, the synthesis of 2 ~ (2 +) ~ (26) -tetramethyl-6-methyl-1-piperidyl ester catalyzed by copper was studied.The research of this thesis includes the following parts: in the first part, 2-tetrahydronaphthalene ketone and 2O2O2O6O6-tetramethylpiperidine oxide are used as raw materials.The reaction experiment and optimization of the reaction conditions for the synthesis of 3-h2formyl-phenyl-propionic acid by copper catalyzed carbon-carbon bond cleavage and ring opening were studied in this paper. The reaction conditions were optimized for the synthesis of 3-trichloro-2-formyl-phenyl-propionate.In the second part, the universality of reactive substrate is discussed.Under the optimal conditions, 伪-aryl cyclic ketones or chain ketones with different substitutions can be transformed into corresponding esters successfully.The reaction conditions also showed that 2O2O2O6O6-tetramethylpiperidine oxide containing different substituents could be compatible with each other.In order to demonstrate the practicability of the developed reaction, a series of synthetic derivatization was carried out for the target product 3-O2-formyl-phenyl-propionic acid, 2-trimethylpiperidine-6-tetramethylpiperidine-1-yl ester.In the third part, the structures of 3-H2formyl-phenyl-propionic acid 2O2O2O6O6-tetramethylpiperidine-1-yl ester and its derivatives are characterized, including hydrogen spectrum, carbon spectrum, infrared spectrum, high resolution mass spectrometry and so on.In conclusion, a copper / air green catalytic system has been developed to realize the new conversion of 2 ~ (2 +) ~ (2 +) ~ (2 +) ~ (2 +) ~ (6) -tetramethyl-1-piperidyl ester by breaking the carbon-carbon bond of non-tensionic ketones.The results of this study enrich the conversion methods of 伪-aryl cyclic ketones or chain ketones and expand the range of conversion and application of these carbonyl compounds.
【学位授予单位】：湘潭大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.251

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