四(三苯基膦)钯是一种重要的有机反应催化剂,市场需求较大.但是目前报道的合成方法中该产品收率不高,废液里残留钯较多,致使生产成本较高.因此,开发一种新合成方法具有重要意义.本文采用温和加热反应及低温处理的方法(处理反应的过程不需要氮气保护),以二氯化钯和三苯基膦为反应原料,二甲亚砜为溶剂,水合肼为还原剂,加热至90℃反应合成四(三苯基膦)钯.通过1 H NMR对其结构进行表征,且测试的熔点和钯含量与标准品一致.采用平行对比实验,通过优化原料、溶剂、反应和纯化方法等,研究影响产物品质的因素,得到最佳工艺条件:氯化钯的钯含量≥59.80％,三苯基膦与氯化钯当量比为4.50,二甲亚砜与三苯基膦体积比为3.00,在90℃下缓慢滴加水合肼,10 ℃下处理反应液,所得产品收率＞98.00％.该方法能满足生产高品质产品的要求.
A New Synthesis Method of Tetrakis(triphenylphosphine)Palladium
Tetrakis(triphenylphosphine)palladium is an important catalyst for organic reactions,which has a large market requirement.The synthesis method has low yield and high production cost due to the large amount of residual palladium in spent liquor at present.Therefore,it is of great significance to develop a new synthesis method.In this article,using the method of mild heating reaction and low temperature treatment(the treatment process does not require nitrogen protection),the tetrakis(triphe-nylphosphine)palladium was synthesized by improved method via heating at 90℃ with palladium chlo-ride and triphenylphosphine in dimethyl sulfoxide followed by addition of hydrazine hydrate as the re-ducing agent.The structure was characterized by 1H NMR,and the melting point and palladium con-tent tested were consistent with the standard.Carrying out parallel experiments,the influencing factors including starting materials,solvent,reaction and purification were investigated in details.When the palladium content of palladium dichloride was more than 59.80％,the equivalent ratio of tripheny-lphosphine to palladium dichloride was 4.50,and the volume ratio of dimethyl sulfoxide to tripheny-lphosphine was 3.00,hydrazine hydrate was slowly added at 90℃ and then the reaction mixture was treated at 10 ℃,the high-quality tetrakis(triphenylphosphine)palladium was synthesized with more than 98.00％total yield.The method can meet the requirement of producing high quality products.
万方数据
维普
