cui催化1 2二氯乙炔与亚磷酸酯加成反应word格式论文.docxVIP

摘要烯基膦酸酯类(烯基膦)化合物由于其特殊的化学结构，一直被广泛地关注。其结构 的特殊性在于 P 原子直接连接在 C-C 双键上，成为有机合成反应中有用的中间体。例 如，烯基膦化合物可作为生成多聚膦化合物的前体，还可以作为亲二烯体发生环加成 反应，生成含有 P-C 键的多元环化物。由于 P 原子和 C-C 双键的同时存在，烯基膦酸 酯类(烯基膦)化合物在配位化学中得到了大量的应用。近年来，在均相催化中也将烯基 膦化合物作为配体。基于烯基膦酸酯类(烯基膦)化合物在化学各个领域中的广泛用途，本论文重点研究 了简便温和的合成乙烯基亚膦酸酯类化合物的新方法。合成了 8 个乙烯基亚膦酸酯类化合物和 7 个亚磷酸酯类化合物。1报道了以 1,2-二氯乙炔，亚膦酸酯为原料，在 CuI 催化下合成了 8 个二氯乙烯基亚 磷酸酯。产物结构经 IR，1H NMR，13C NMR，31P NMR 和元素分析等进行了表 征。2利用醇，三氯化磷为原料，以氯仿作溶剂，合成了一系列亚磷酸酯。产物经 IR 进 行了结构表征。3利用 1,2-二氯乙炔和二苯基氧膦发生加成反应合成(Z)-(1,2-二氯乙烯基)二苯基氧 膦。并用 X-衍射确认(Z)-(1,2-二氯乙烯基)二苯基氧膦的单晶结构。4对实验结果进行了讨论，考察了不同的原料配比、温度、反应时间等因素对实验结 果的影响。关键词: 乙烯基亚膦酸酯 CuI 催化 二氯乙炔AbstractAlkenylphosphonates were attracted great attention because of their special structures. Hence, these phosphorus derivatives contain a carbon-carbon double bond which directly linked to the phosphorus atom, so they have been used as intermediates in organic synthesis. For example, they were used as precursors of polyphosphines or dendrimers. Alkenyl-phosphonates were also used as dienophiles to generate heterocycle compounds which contain P-C bond in cycloaddition reactions. They are attracted great attention in coordination chemistry due to the presence of both the phosphorus atom and the carbon-carbon double bond. Recently, alkenylphosphonates were also used as ligand for homogeneous catalysis.A new mild and convenient method in the synthesis of vinylphosphonates has been researched because of numerous applications of alkenylphosphines in various fields of chemistry. Hence, eight new compounds of vinylphosphonates and seven phosphite esters have been reported in the paper.Eight novel Dichlorovinylphosphonates were synthesized by reactions of one pot with dichloroacetylene and phosphite esters in presence of CuI. The product structures were characterized by IR, 1H NMR, 13C NMR, 31P NMR and elemental analyses.A serious of phosphite esters were synthesized by the reaction of phosphorus trichloridewith alcohol in the benzene. The product structures were charac