【作者】 黄文明；

【导师】 罗群力；

【作者基本信息】 西南大学 ， 有机化学， 2010， 硕士

【摘要】 巯基化合物是在生物及医药方面有着重要作用的一类有机化合物。它们在人体内的新陈代谢及酶催化过程中起着重要作用。半胱氨酸(Cys)、同型半胱氨酸(Hcys)、谷胱甘肽(GSH)等小分子的巯基化合物含量的高低与人类的某些疾病如艾滋病(AIDS),帕金森综合症(Parkinson’s diseases)以及心血管病有关。因此,发展合适的检测试剂来测定巯基化合物有十分重要的意义。本文设计合成了一系列苯磺酸内酯衍生物、香豆素衍生物以及半花菁类衍生物,用于检测巯基化合物。1.苯磺酸内酯衍生物的合成以廉价易得的糖精钠为原料,经甲基化、格氏反应、环化,合成苄位多取代的甲苯磺酸内酯,再经硝化、还原,得到相应的硝基衍生物和氨基衍生物;以邻甲酰基苯磺酸钠为原料,经环化、还原合成苯磺酸内酯。初步的探索研究结果表明,所得到的系列苯磺酸内酯衍生物常规反应条件与巯基化合物反应非常缓慢,将其作为巯基化合物的检测试剂存在一定困难。2.香豆素衍生物的合成以间苯二酚为原料,经过甲酰化、醚化、碘代、成环、Heck偶联,得到香豆素的丙烯酸甲酯衍生物,但它在常规反应条件与巯基化合物不反应,不能作为巯基检测试剂；以间苯二酚为原料,经环化、甲酰化、醚化、adol反应得到香豆素的adol反应产物,虽能顺利地与巯基化合物反应,但反应前后紫外吸收光谱变化较小,不适于用紫外分光光度法检测硫醇化合物,运用其他分析方法使用该试剂来检测硫醇化合物的分析方法有待建立。3.半花菁化合物的合成以及对巯基化合物的检测通过简单的三步方法合成了六个半花菁类化合物,它们能与乙硫醇迅速反应,反应前后紫外吸收光谱变化显著。为此,初步建立了紫外-可见分光光度法测定巯基化合物的分析方法,该方法在10-5～10-4mol／L的巯基化合物检测浓度范围内存在较好的线性关系。更多还原

【Abstract】 Thiols, which play a crucial role in biology and medicine,and play an important role in metabolic pathways.Low molecular weight thiol-containing compounds such as cysteine (Cys), glutathione (GSH), homocysteine (Hcys), plasma levels of which have been linked to various human diseases such as AIDS, and Parkinson’s diseases, as well as cardiovascular diseases. Therefore, it is of importance to detect thiols using appropriate reagents. In this dissertation, it was described the synthesis of novel hemicyanine dyes compounds, benzenesulfolactones and coumarins and their application in detecting thiols.Part1 Synthesis of benzenesulfolactonesMulti-substituted benzenesulfolactones was synthesized starting from cheap saccharin sodium via methylation, Grignard reaction, cyclization, and further transformed into nitro derivative by nitrification and then amino derivative by reduction. Benzenesulfolactone was sythesized starting from 2-formylbenzenesulfonate via cyclization and then reduction. It was show that by preliminary research, the speed of the obtained benzenesulfolactones reacting with thiols in normal condition is so slow that there are some difficuties to be as detecting thiols’reagents.Part 2 Synthesis of coumarinsMethyl acrylate of coumarins was synthesized starting from resorcinol via formylation, etherification, iodination, cyclization, Heck cross-coupling reaction. It doesn’t react with thiols in normal condition, so this compound cann’t be a reagent for detecting thiols.The adol coupound of coumarins was synthesized starting from resorcinol visa cyclization, formylation, etherification,adol reaction.Although it reacts with thiols,the difference value of UV absorbance before and after reaction is small. Hence, the compound also cann’t be reagent for detecting thiols by UV analysis. Other analycial mothods to detect thiols with this compound will be established in future.Part 3 Synthesis of hemicyanine dyescompounds and their application in detecting thiolsSix hemicyanine dyes compounds were designed and prepared concisely via three steps.They can react with ethanethiol quickly, and the difference value of UV absorbance is significant before and after reaction.Hence, the analycal mothod of detecting thiols by UV-visible pectrophotometer was preliminarily established. A linear calibration curve can be observed in the range of 10-5～10-4mol/L.更多还原