金属铋配合物催化的Biginelli反应研究

发布时间：2018-04-28 16:49

本文选题：Biginelli反应 + 3　；参考：《江苏科技大学》2016年硕士论文

【摘要】：Biginelli反应是将醛、脲/硫脲和β-二羰基化合物合成3,4-二氢嘧啶-2(1H)-酮/硫酮(DHPMs)的反应。DHMPs具有广泛的生物活性,可作为抗癌药、降压药、钙拮抗剂、细胞有丝分裂驱动蛋白Eg5阻止剂、α1a-肾上腺素拮抗物、抗炎剂和抗病毒剂等。DHPMs的结构单元也是一种重要的药物骨架,一些具有抗HIV病毒活性的生物碱就具有这种结构单元。本文以BiCl3、6-羟基嘌呤为原料,合成一种新的金属铋配合物,并对其在Biginelli反应中的应用进行了重点研究:第一,通过挥发法合成了两种金属铋配合物(C_4H_(12)N_2)_2[BiCl6]Cl·H_2O和(C_5H_6N_4O)(C_5H_5N_4O)_3(C_5H_4N_4O)[Bi_2Cl_(11)]Cl_2,经过表征后确定单晶结构。第二,将(C_5H_6N_4O)(C_5H_5N_4O)_3(C_5H_4N_4O)[Bi_2Cl_(11)]Cl_2应用于Biginelli反应合成3,4-二氢嘧啶-2(1H)-酮类化合物,在加热回流的乙醇中催化反应,催化剂可回收使用。通过一系列单因素实验对催化剂、溶剂等条件进行了考察,确定了最优反应条件,合成了一系列的3,4-二氢嘧啶-2(1H)-酮类化合物,并通过MS、1H NMR等方法对合成的化合物进行了表征。第三,将(C_5H_6N_4O)(C_5H_5N_4O)_3(C_5H_4N_4O)[Bi_2Cl_(11)]Cl_2应用于Biginelli反应合成3,4-二氢嘧啶-2(1H)-硫酮类化合物,在加热回流的乙醇中与三氟甲磺酸共同催化反应。在3,4-二氢嘧啶-2(1H)-酮类化合物合成条件的基础上进一步优化了反应条件,添加三氟甲磺酸作为助催化剂,合成了一系列的3,4-二氢嘧啶-2(1H)-酮类化合物,并通过MS、1H NMR等方法对合成的化合物进行了表征。
[Abstract]:Biginelli reaction is the synthesis of 3n4-dihydropyrimidine-2Hoxanone / thione DHPMs from aldehyde, urea / thiourea and 尾 -dicarbonyl compounds. DHMPs have a wide range of biological activities and can be used as anticancer drugs, antihypertensive drugs, calcium antagonists. The structural units of cell mitogen Eg5 blockers, 伪 1a- adrenaline antagonists, anti-inflammatory agents and antiviral agents are also important drug skeletons, and some alkaloids with antiviral activity have this kind of structural units. In this paper, a new metal bismuth complex was synthesized from BiCl _ 3 and 6-hydroxypurine, and its application in Biginelli reaction was studied. Through volatilization, two kinds of metal and bismuth complexes, C5H / S / C _ 4H _ S / C _ 4H _ S / C _ 5H _ 5S _ 4N _ 4O) have been synthesized. [BiCl6] Cl _ H _ S _ 2O _ 2 [BiCl6] Cl _ H _ S _ 2O and C _ 5H _ 6N _ 4O _ O _ T _ 2S _ 5C _ 5H _ 5N _ 4O _ O _ T _ (C _ 5H _ 5N _ 4O _ O) have been synthesized. Second, take the C5HS / C _ 5H _ 5N _ 4O _ s _ _ _ Cl_2 _ _ _ / _ _ _, _ _ _ The catalyst and solvent were investigated by a series of single factor experiments, and the optimum reaction conditions were determined. A series of 3H 4- dihydropyrimidine-2o-1H ~ (-1) H ~ (-1) ketones were synthesized, and the synthesized compounds were characterized by MS ~ (1H) H NMR. Third, Cl_2 will be used in the Biginelli reaction for the synthesis of 3H-dihydropyrimidine -2H1-thione compounds, and for the catalytic reaction with trifluoromethylsulfonic acid in heated refluxed ethanol, and will be used for the synthesis of C5H4N4OOC _ 5H _ 5N _ 4O _ s _ _ _ On the basis of the synthesis conditions of 3O4-dihydropyrimidine -2H ~ (-1) H ~ (-1) H ~ (-1) -ketone, a series of 3 ~ (4) -dihydropyrimidine ~ (21) H ~ (-1) H ~ (-1) -ketone compounds were synthesized by adding trifluoromethyl sulfonic acid as a co-catalyst. The synthesized compounds were characterized by MS 1 H NMR.
【学位授予单位】：江苏科技大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O641.4;O621.251

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