非贵金属促进实现杂环类化合物的膦酸化

发布时间：2018-02-20 23:28

本文关键词： 杂环化合物亚磷酸三乙酯 C-P键构筑　出处：《南昌大学》2016年硕士论文　论文类型：学位论文

【摘要】：芳基膦酸酯和杂环膦酸酯类化合物在药物化学、有机磷农药、P配体化学及材料化学、有机合成等方面有着举足轻重的地位。近年来,针对有机磷化学领域的研究开展十分迅速。有机磷化合物在许多方面都显示出它的重要性,渐渐的成为了一门独立的化学分支。例如一些含氮的膦酸酯类化合物在农作物上有着很大的作用,已经在除草剂,除菌剂上得到了广泛的应用。然而,尽管有机膦酸酯类化合物在许多方面的应用逐年增加,但仍存在许多的缺陷,如制作成本昂贵,后处理困难并影响环境等。近几年来针对通过经济高效,绿色环保的方法合成膦酸酯类化合物,已经吸引了科学家们的广泛注意。所以,本课题组报道了多种合成杂环芳基膦酸酯的新颖方法。在I_2/air的反应体系中首次高效的合成了苯并VA唑的双膦酸酯化合物。以I_2作为促进剂,苯并VA唑和亚磷酸三乙酯为底物,在乙腈溶剂中可绿色速高效的实现C=N双键的加成构建了C-P和N-P键,同时对阿布佐夫反应进行了一个延伸和拓展。I_2促进苯并VA唑单膦酸酯化合物的合成。在当量的I_2为促进剂及过硫酸钾为氧化剂的条件下,苯并VA唑衍生物与亚磷酸三乙酯在乙腈为溶剂的作用下实现了2位C_(sp2)-H键的功能化构建了一个C-P键得到了苯并VA唑膦酸酯类化合物。该反应的特点是避免了使用过渡金属,同时对大部分底物都能得到良好的产率。通过CuCl_2催化高选择性的合成3位香豆素膦酸酯产物。以CuCl_2作为催化剂,K_2S_2O_8为氧化剂,亚磷酸三乙酯与香豆素衍生物为底物的体系,在乙腈中高效高选择性的合成了3-膦酸酯香豆素的衍生物,该体系的适用性比较好,对大部分类似的化合物都能达到预期的产率。
[Abstract]:Aryl phosphonic acid esters and heterocyclic phosphonate compounds in medicinal chemistry, organophosphorus pesticides, chemical materials and chemical P ligand, plays an important role in organic synthesis. In recent years, the research in the field of organic phosphorus chemistry is developing very rapidly. Organophosphorus compounds in many aspects shows its importance gradually. As an independent branch of Chemistry. For example, some nitrogen-containing phosphonate compounds has great effect on crops, has been in the herbicide, bactericide has been widely used. However, despite the use of organic phosphonic acid ester compounds in many areas has increased year by year, but there are still many defects, such as the production cost is expensive, postprocessing difficulties and the influence to the environment. In the last few years through economic efficient and green method synthesis of phosphonic acid ester compounds, has attracted a wide range of scientists note Italy. So, the research group reported a novel method for synthesis of a variety of heterocyclic aryl phosphonates. In the reaction system of I_2/air for the first time in the efficient synthesis of benzo bisphosphonate compounds with VA. Using I_2 as promoter, VA and benzo triazole three ethyl phosphite as substrates in acetonitrile solvent C=N double green efficient speed bonus to construct the C-P and N-P keys at the same time on the Abu Geoff reaction conducted an extension and expansion of.I_2 promote the synthesis of benzo VA oxazole single phosphonate compounds. The equivalent I_2 promoter and conditions of potassium persulfate as oxidant, benzo VA quinazoline derivatives and sub phosphoric acid ethyl ester three achieved in acetonitrile as solvent under the action of 2 C_ (SP2) function of -H key to build a C-P key VA benzo triazole phosphonate compounds are obtained. The reaction is to avoid the use of transition metal, while most of the substrate can be obtained Good yield. The catalytic synthesis of CuCl_2 with high selectivity of 3 coumarin phosphonate compounds. Using CuCl_2 as catalyst, K_2S_2O_8 as oxidant, three ethyl phosphite and coumarin derivatives as substrate in acetonitrile system, highly selective and efficient synthesis of 3- phosphonate coumarin derivatives, the applicability of the system well, the most similar compounds can achieve the desired yield.

【学位授予单位】：南昌大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O627.51

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