一种新型四齿1,2-HOPO螯合剂的合成、金属配位研究  

Synthesis and metal-complexation of a new tetradentate derivative as a potential therapeutic chelating agent

作　　者：闫镒腾 金波[1] 彭汝芳[1] 楚士晋[1] 

机构地区：[1]西南科技大学四川省非金属复合与功能材料重点实验室--省部共建国家重点实验室培育基地,四川绵阳621010

出　　处：《安全与环境学报》2017年第4期1476-1483,共8页Journal of Safety and Environment

基　　金：国家自然科学基金项目(51572230)

摘　　要：以6-羟基-2-吡啶羧酸为原料,经5步反应合成得到一种新型四齿β-二酮1,2-羟基吡啶酮衍生物。通过红外、核磁、质谱对其结构进行了表征。采用电位-光谱结合的方法,测定了四齿β-二酮1,2-羟基吡啶酮衍生物与UO2+2、Cu^(2+)、Zn^(2+)和Fe^(3+)的络合能力。结果表明,四齿β-二酮1,2-羟基吡啶酮衍生物对UO2+2和Fe3+有明显的络合能力,有望成为一种新型铀酰离子促排剂(p UO2=15.4)和铁螯合剂(p Fe=21.22)。The article is to present the sysnthesis result of a new sort of tetradentate ligand based on 1-hydroxy-2（ 1H）-pyridinone as a uranyl chelating agent. The target product has been synthesized as a reuslt of 5 steps of the experimental reaction,that is,the hydroxylation,the hydroxyl protection,the amidation,the acyl chloridation and that of deprotection. Beginning with the commercially available 6-hydroxy-picolinic acid,the first step is to synthesize the carboxylate-derivatized 1,2-HOPO,which is followed by the second step,a step on how to protect the hydroxyl of pyridone ring. In the due step,the said 1,2-HOPOBn carboxylic acid can be directly condensed with the ethanolamine so as to work out N-（ hydroxyethyl）-1-benzyloxy-2（ 1H）-pyridinone-6-amide,which has to contain the reactive hydroxyl group and should be prone to be made to react with the malonyl dichloride to form the N,N-bis（ N-（ hydroxyethyl）-1-benzyloxy-2（ 1H）-pyridinone-6-amido） malonate. And,finally,it has to deprotect the benzyl groups again to get the desirable renovated tetradentate chelator through a process of hydrogenation at the presence of Pd/C. And,next,the prepared ligands should be examined and characterized via the1 H NMR spectroscopy,the13 C NMR spectroscopy,the FTIR spectroscopy as well as the mass spectrometry. The final analysis and evaluation results should prove to be well in accord with the structure of the actual products,so as to verify its capacity well qualified as a metal sequestering agent,both with the protonation constant and p M for the oriented uranyl ion,ferric（ III）,copper（ II） and zinc identified and determined in accordance with the standardized potentiometric-spectrophotometric measurements.More exactly speaking,in its neutral form,the ligand should have two dissociable protons,well in accord with the pyridinone hydroxy groups. Whereas the first 2 protonation constants（ lg KH1=9. 22,lg KH2= 9. 07） has to tend to be easily attributed to the hydroxypyridinone hydroxy groups,the other 2

关 键 词：环境工程学 1 2-羟基吡啶酮 铀酰离子 络合 

分 类 号：X503.1[环境科学与工程—环境工程]