河北大学
硕士学位论文
卡宾衍生物及其环加成反应的研究
姓名：***
申请学位级别：硕士
专业：有机化学
指导教师：李小六；胡文浩
reaction scheme
2011-05
摘要
有机合成化学是合成复杂有机分子的基础，新反应类型、新的反应中间体、以及经典反应在合成中的应用等研究一直是化学领域的热点。近年来，卡宾参与的环加成反应、氮宾的插入反应、氮杂环卡宾催化剂的合成，以及金属催化的C-C偶联反应的应用得到了广泛发展。
卡宾(carbene)又称碳宾、碳烯，是亚甲基-CH2及其取代衍生物的总称。卡宾作为重要的中性活泼中间体，在有机合成中得到广泛的应用。主要用于增长碳链、制备小环烷烃、制取多环化合物。
过渡金属催化的C-C偶联以反应条件温和，产率高等特点在有机合成领域得到了广泛应用。
基于此，我们研究了卡宾、氮宾参与的1,3-偶极环加成反应，合成了金鸡纳碱NHC 类催化剂，噻唑硫脲类，咪唑硫脲类催化剂；过渡金属催化下硝基甲苯与碘代苯的C-C 偶联反应，优化了反应条件，合成了2-氨基二苯甲酮。
具体研究内容如下：
第一部分：以α-重氮羰基化合物与氨基醇为起始原料，制备重氮亚胺类化合物。通过系统研究提出了可能胺解的反应机理。并且将氮杂环卡宾作为配体开发了新型金鸡纳碱NHC类催化剂，噻唑硫脲类和咪唑硫脲类催化剂，研究了催化剂在醛的安息香缩合反应中的应用。
第二部分：研究了过渡金属催化下硝基甲苯和碘代苯的C-C偶联反应制备了2-氨基二苯甲酮。意外发现发生偶联反应的同时还发生了氧化还原反应。
关键词卡宾氮宾氮杂环卡宾偶联反应
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Abstract
Organic synthesis is the basis for synthesis of complex organic molecules, The p-urpose of this passage is to cast some light on new reaction types, new synthetic inte rmediates, and the classic reaction to inspire organic chemists to pay more attention t-o this hot field. In recent years, carbene cycloaddition reaction, insertion by nitrene, N-heterocyclic carbene catalysts, and transition metal catalysis C-C coupling reaction h as been widely applied development.
Carbene is methylene and its substituted derivatives in general. Carbene as a neut -ral active intermediates in organic synthesis has been used widely. Mainly used for g -rowing carbon chain, prepared a small ring hydrocarbons, extraction of polycyclic co-mpounds.
Transition metal-catalyzed C-C coupling reactions with mild conditions, high yield characteristics in the field of organic synthesis have been applied rapidly.
Based on this, we studied the carbene and nitrene participate in the 1,3 - dipolar cycloaddition reaction. We synthesized cinchona alkaloids, thiazole thiourea, imidazole thiourea catalyst; Transition metal-catalysis of nitrobenzene with iosobenzene C-C cou -pling reactions, optimum of reaction conditions, synthesis of 2-aminobenzophenone.
Part I: With α-diazo carbonyl compound and amino alcohols as starting material. Prepared diazo imine compounds and study of reaction mechanism. We have synthesiz ed a new class of NHC cinchona catalyst, thiazole thiourea and imidazole thiourea cat -alyst. in the benzoin condensation reaction of aldehydes in the application.
Part II: The second part focuses on transition metal catalysis of o-nitrobenzene w -ith iodobenzene C-C coupling reactions. We are surprised to find that the coupling re -action occurred and redox reactions. Synthesis of 2-aminobenzophenone.
Keywords carbene nitrene N-heterocyclic carbene cross-coupling reaction
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