【作者】 凌冈；

【导师】 陆世维；

【作者基本信息】 中国科学院研究生院（大连化学物理研究所） ， 有机化学， 2003， 博士

【摘要】 采用CO/Se催化体系，可将硝基苯类与苯胺类化合物一步氧化还原羰基化成脲。它可代替以往的利用光气来给化合物引进一个羰基的方法，具有原子经济反应的高选择性和对环境的友好性，从而越来越受到人们的关注，已成为C₁化学中羰基合成领域的一个重要的研究热点。 本文旨在深入研究和拓宽这一新催化反应的适用范围，考察各种含氮化合物的硒催化羰基化反应，探索含氮杂环的非对称脲的合成规律，试图研究开发替代光气法而直接利用一氧化碳通过羰基化简单、高效地制取一系列有用的羰基化反应产物。以廉价易得的硒粉作催化剂，CO作羰基化剂，通过调节助催化剂，进而研究了邻硝基苯酚、取代的氨基吡啶、取代氨基嘧啶的羰基化反应；考察了在硒、一氧化碳体系中，在强碱（1，8-二氮双环[5，4，0]-十一烷-7-烯）的助催化下，芳甲酰胺和芳硝基的还原取代反应；对激素类农药的重要品种——双氧威、蚊蝇醚的工艺改进进行了探索。 研究了硒催化分子内硝基和酚羟基的环化羰基化反应。以往的文献报道由于酚羟基的活性差，硒不可以催化硝基和酚羟基的羰基化反应。本文首次研究了硝基和酚羟基一步羰基化合成苯并噁唑啉酮，硝基预先不必还原成氨基。对影响反应的多种因素进行了讨论，提供了一种新的制备苯并噁唑啉酮类化合物的合成途径，最高收率为80％；对分子内硝基和醇羟基的环化反应亦进行了研究，在强碱（1，8-二氮双环[5，4，0]-十一烷-7-烯）的催化下，目的产物——苯并噁嗪酮的收率达87％。 以各种取代的氨基吡啶为共试剂，与多种芳香硝基化合物进行硒催化的羰基化反应时，发现吡啶环上氨基的对位如为吸电子基时，可降低氨基的反应活性。对多种取代的氨基吡啶进行了考察。合成了一系列的取代的吡啶基苯基脲类化合物。n摘要 以取代的氨基喀咤为共试剂，与多种芳香族硝基化合物进行了硒催化的碳基化反应，产率最高可达90%左右。考察了氨基位于喀睫的不同位置时对反应收率的影响，同时对反应条件如温度、压力、催化剂量、碱性助催化剂的种类、溶剂的种类进行了全面的考察。 研究了在硒、一氧化碳体系中，在强碱（1，8一二氮双环〔5，4，们一十一烷一7一烯）的催化下，芳甲酞胺和芳硝基的还原取代反应，生成新的芳甲酞胺化合物。对这一反应产生的原因加以阐明，讨论了可能的反应机理。 对保幼激素类杀虫剂双氧威、蚊蝇醚这两个农药品种进行了开发。对合成苯醚醇类化合物的相转移催化剂进行了研究，用廉价的PEG成功地代替了四正丁基嗅化钱催化此类反应;特别是对双氧威的重要中间体—氯乙基氨基甲酸乙酷的开发采用了硒催化一氧化碳拨基化的方法，阐明了此合成方法的技术可行性和应用开发前景。更多还原

【Abstract】 One-pot oxidative-reductive carbonylation of nitrobenzenes with anilines can lead to formation of ureas with CO/Se as a catalytic system. Such a method can replace traditional reaction with phosgene as the carbonylation reagent, involving the toxic reagent and drastic reaction conditions, the new herein studied method is environmentally benignancy and has atom economical selectivity. Recently, it has attracted more and more attention and become one of the challenging and attractive subjects in the field of C1 chemistry.The purpose of this theme is to study the score and limitation of this new catalytic reaction, and synthetic methodology of ureas of N-heterocyclic ring contained, to carry out a simple and effective catalytic synthetic method through the carbonylation with CO and cheap selenium to give out a series of useful fine chemicals. Through adjusting the co-catalysts, further more, the reductive substitution reaction of aromatic acylamide and nitrobenzenes in the system of carbon monoxide catalyzed by selenium with l,8-diazabicyclo[5, 4, 0]undec-7-ene (DBU) was also discussed; The carbonylation of substituted aminopyrimidine and aminopyridine derivatives as co-reagent with substituted nitrobenzenes and thecarbonylation of o-nitrophenol were studied; The technology of hormonelike pesticides-Fenoxycarb and Pyripoxyfen was researched.The cyclic carbonylation of o-nitrophenol and carbon monoxide catalyzed by selenium with l,8-diazabicyclo[5, 4, 0]undec-7-ene and triethylamine as co-catalysts were carried out. All kinds of elements to influence such reaction were investigated, a new method to synthesize the derivatives of benzoxazolinone was proposed and the highest yield of such reaction at the present conditions reached to 80%; At the same reaction conditions, the yield of benzoxazinone through the cyclic carbonylation of 2-nitrobenzyl alcohol and carbon monoxide catalyzed by selenium with l,8-diazabicyclo[5, 4, 0]undec-7-ene and triethylamine as co-catalysts were got to 87%.The electron withdrawing group on the contraposition of amino can greatly influence the yieds of the carbonylation of substituted aminopyridine derivatives as co-reagents with substituted nitrobenzenes. A series of pyridinylureas were synthesized.The highest yield of the selenium-catalyzed carbonylation of substituted nitrobenzenes with substituted aminopyrimidines as co-reagents reached 90% or so. The influence of the position of amino associated with pyrimidine on the reaction yields was discussed. At the same time, the effects of the reaction conditions, including temperature, pressure of CO, catalyst amount, the sorts of bases as co-catalyst and the sorts of solvents were investigated also.The reductive substitution reaction of aromatic acylamide and nitrobenzenes in the system of carbon monoxide catalyzed by selenium with l,8-diazabicyclo[5, 4, 0]undec-7-ene (DBU) and triethylamine as co-catalysts was also discussed and plausible mechanism was postulated.The technology of hormonelike pesticides-Fenoxycarb and Pyripoxyfen was empoldered. The phase transfer catalysis reaction to synthesize l-aryloxy-2-propanols was investigated, the precious phase transfer catalyst-tetrabutylammonium bromide can be replaced by cheap PEG in thisreaction; Above all, the intermediate of Fenoxycarb -2-chloroethylcarbamicacid ethyl ester can be synthesized by carbonylation of chloroethylamine and alcohol with CO catalyzed by selenium.更多还原