Synthesis, electrochemical properties, and antioxidant activity of sterically hindered catechols with 1,3,4-oxadiazole, 1,2,4-triazole, thiazole or pyridine fragments

IF 2.2 4区化学 Q2 CHEMISTRY, ORGANIC

Beilstein Journal of Organic Chemistry Pub Date : 2024-09-19 DOI:10.3762/bjoc.20.202

Daria A. Burmistrova, Andrey Galustyan, Nadezhda P. Pomortseva, Kristina D. Pashaeva, Maxim V. Arsenyev, Oleg P. Demidov, Mikhail A. Kiskin, Andrey I. Poddel’sky, Nadezhda T. Berberova, Ivan V. Smolyaninov

{"title":"Synthesis, electrochemical properties, and antioxidant activity of sterically hindered catechols with 1,3,4-oxadiazole, 1,2,4-triazole, thiazole or pyridine fragments","authors":"Daria A. Burmistrova, Andrey Galustyan, Nadezhda P. Pomortseva, Kristina D. Pashaeva, Maxim V. Arsenyev, Oleg P. Demidov, Mikhail A. Kiskin, Andrey I. Poddel’sky, Nadezhda T. Berberova, Ivan V. Smolyaninov","doi":"10.3762/bjoc.20.202","DOIUrl":null,"url":null,"abstract":"Abstract\nA series of new RS−, RS−CH2− and R2N−CH2-functionalized сatechols with heterocyclic fragments such as 1,3,4-oxadiazole, 1,2,4-triazole, thiazole, or pyridine were synthesized by the reaction of 3,5-di-tert-butyl-o-benzoquinone or 3,5-di-tert-butyl-6-methoxymethylcatechol with different heterocyclic thiols. The S-functionalized catechols were prepared by the Michael reaction from 3,5-di-tert-butyl-o-benzoquinone and the corresponding thiols. The starting reagents such as substituted 1,3,4-oxadiazole-2-thiols and 4H-triazole-3-thiols are characterized by thiol–thione tautomerism, therefore their reactions with 3,5-di-tert-butyl-6-methoxymethylcatechol can proceed at the sulfur or nitrogen atom. In the case of mercapto-derivatives of thiazole or pyridine, this process leads to the formation of the corresponding thioethers with a methylene linker. At the same time, thiolated 1,3,4-oxadiazole or 1,2,4-triazole undergo alkylation at the nitrogen atom in the reaction with 3,5-di-tert-butyl-6-methoxymethylcatechol to form the corresponding thiones. The yield of reaction products ranges from 42 to 80%. The crystal structures of catechols with 3-nitropyridine or 1,3,4-oxadiazole-2(3H)-thione moieties were established by single-crystal X-ray analysis. The possibility of forming intra- and intermolecular hydrogen bonds has been established for these compounds. The electrochemical behavior of the studied compounds is influenced by several factors: the nature of the heterocycle and its substituents, the presence of a sulfur atom in the catechol ring, or a thione group in the heterocyclic core. The radical scavenging activity and antioxidant properties were determined using the reaction with synthetic radicals, the cupric reducing antioxidant capacity assay, the inhibition process of superoxide radical anion formation by xanthine oxidase, and the process of lipid peroxidation of rat liver (Wistar) homogenates in vitro.\n<img src='https://www.beilstein-journals.org/bjoc/content/figures/1860-5397-20-202-graphical-abstract.png?max-width=550' border='0'/>\nBeilstein J. Org. Chem. 2024, 20, 2378–2391. doi:10.3762/bjoc.20.202","PeriodicalId":8756,"journal":{"name":"Beilstein Journal of Organic Chemistry","volume":"4 1","pages":""},"PeriodicalIF":2.2000,"publicationDate":"2024-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Beilstein Journal of Organic Chemistry","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.3762/bjoc.20.202","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, ORGANIC","Score":null,"Total":0}

引用次数: 0

Abstract

A series of new RS−, RS−CH₂− and R₂N−CH₂-functionalized сatechols with heterocyclic fragments such as 1,3,4-oxadiazole, 1,2,4-triazole, thiazole, or pyridine were synthesized by the reaction of 3,5-di-tert-butyl-o-benzoquinone or 3,5-di-tert-butyl-6-methoxymethylcatechol with different heterocyclic thiols. The S-functionalized catechols were prepared by the Michael reaction from 3,5-di-tert-butyl-o-benzoquinone and the corresponding thiols. The starting reagents such as substituted 1,3,4-oxadiazole-2-thiols and 4H-triazole-3-thiols are characterized by thiol–thione tautomerism, therefore their reactions with 3,5-di-tert-butyl-6-methoxymethylcatechol can proceed at the sulfur or nitrogen atom. In the case of mercapto-derivatives of thiazole or pyridine, this process leads to the formation of the corresponding thioethers with a methylene linker. At the same time, thiolated 1,3,4-oxadiazole or 1,2,4-triazole undergo alkylation at the nitrogen atom in the reaction with 3,5-di-tert-butyl-6-methoxymethylcatechol to form the corresponding thiones. The yield of reaction products ranges from 42 to 80%. The crystal structures of catechols with 3-nitropyridine or 1,3,4-oxadiazole-2(3H)-thione moieties were established by single-crystal X-ray analysis. The possibility of forming intra- and intermolecular hydrogen bonds has been established for these compounds. The electrochemical behavior of the studied compounds is influenced by several factors: the nature of the heterocycle and its substituents, the presence of a sulfur atom in the catechol ring, or a thione group in the heterocyclic core. The radical scavenging activity and antioxidant properties were determined using the reaction with synthetic radicals, the cupric reducing antioxidant capacity assay, the inhibition process of superoxide radical anion formation by xanthine oxidase, and the process of lipid peroxidation of rat liver (Wistar) homogenates in vitro.

Abstract Image

Beilstein J. Org. Chem. 2024, 20, 2378–2391. doi:10.3762/bjoc.20.202

查看原文本刊更多论文

具有 1,3,4-恶二唑、1,2,4-三唑、噻唑或吡啶片段的立体受阻儿茶酚的合成、电化学特性和抗氧化活性

摘要一系列新的RS−、RS−CH2−和R2N−CH2官能化с；通过 3,5-二叔丁基邻苯醌或 3,5-二叔丁基-6-甲氧基甲基邻苯二酚与不同杂环硫醇的反应，合成了具有 1,3,4-噁二唑、1,2,4-三唑、噻唑或吡啶等杂环片段的邻苯二酚。S 官能化邻苯二酚是由 3,5-二叔丁基邻苯醌和相应的硫醇通过迈克尔反应制备的。起始试剂（如取代的 1,3,4-噁二唑-2-硫醇和 4H-三唑-3-硫醇）具有硫醇–硫酮同分异构的特点，因此它们与 3,5-二叔丁基-6-甲氧基甲基邻苯二酚的反应可以在硫原子或氮原子上进行。就噻唑或吡啶的巯基衍生物而言，这一过程会导致形成带有亚甲基连接体的相应硫醚。与此同时，硫醇化的 1,3,4-恶二唑或 1,2,4-三唑在与 3,5-二叔丁基-6-甲氧基甲基邻苯二酚反应时，氮原子会发生烷基化反应，形成相应的硫酮。反应产物的产率为 42% 至 80%。通过单晶 X 射线分析，确定了含有 3-硝基吡啶或 1,3,4-噁二唑-2(3H)-硫酮分子的儿茶酚的晶体结构。确定了这些化合物形成分子内和分子间氢键的可能性。所研究化合物的电化学行为受几个因素的影响：杂环及其取代基的性质、儿茶酚环中是否存在硫原子或杂环核心中是否存在硫酮基团。利用与合成自由基的反应、铜还原抗氧化能力测定、黄嘌呤氧化酶对超氧自由基阴离子形成的抑制过程以及大鼠肝脏（Wistar）匀浆体外脂质过氧化过程，测定了这些化合物的自由基清除活性和抗氧化特性。Chem.2024, 20, 2378–2391. doi:10.3762/bjoc.20.202

本文章由计算机程序翻译，如有差异，请以英文原文为准。

求助全文

约1分钟内获得全文求助全文

来源期刊

Beilstein Journal of Organic Chemistry 化学-有机化学

CiteScore

4.90

自引率

3.70%

发文量

167

审稿时长

1.4 months

期刊介绍： The Beilstein Journal of Organic Chemistry is an international, peer-reviewed, Open Access journal. It provides a unique platform for rapid publication without any charges (free for author and reader) – Platinum Open Access. The content is freely accessible 365 days a year to any user worldwide. Articles are available online immediately upon publication and are publicly archived in all major repositories. In addition, it provides a platform for publishing thematic issues (theme-based collections of articles) on topical issues in organic chemistry. The journal publishes high quality research and reviews in all areas of organic chemistry, including organic synthesis, organic reactions, natural product chemistry, structural investigations, supramolecular chemistry and chemical biology.