Catalytic synthesis of heterocyclic compounds with a cineole moiety based on α-pinene

IF 4.7 2区 化学 Q2 CHEMISTRY, PHYSICAL
Alexander Yu. Sidorenko , Tatiana V. Khalimonyuk , Yulia M. Kurban , Irina V. Ilyina , Nikolai S. Li-Zhulanov , Oksana S. Patrusheva , Atte Aho , Ivo Heinmaa , Konstantin P. Volcho , Nariman F. Salakhutdinov , Dmitry Yu. Murzin , Vladimir E. Agabekov
{"title":"Catalytic synthesis of heterocyclic compounds with a cineole moiety based on α-pinene","authors":"Alexander Yu. Sidorenko ,&nbsp;Tatiana V. Khalimonyuk ,&nbsp;Yulia M. Kurban ,&nbsp;Irina V. Ilyina ,&nbsp;Nikolai S. Li-Zhulanov ,&nbsp;Oksana S. Patrusheva ,&nbsp;Atte Aho ,&nbsp;Ivo Heinmaa ,&nbsp;Konstantin P. Volcho ,&nbsp;Nariman F. Salakhutdinov ,&nbsp;Dmitry Yu. Murzin ,&nbsp;Vladimir E. Agabekov","doi":"10.1016/j.apcata.2024.120070","DOIUrl":null,"url":null,"abstract":"<div><div>Cineole is a natural compound that is used in traditional medicine and pharmaceuticals. This work describes for the first time the selective catalytic synthesis of heterocyclic compounds with a cineole fragment by condensation of 8-hydroxy-6-hydroxymethyllimonene (α-pinene based platform molecules) with thiophene-2-carbaldehyde. Acid-modified halloysite nanotubes and commercial montmorillonites K-10 and K-30 were used as heterogeneous catalysts and compared with the traditional ones. The materials were characterized by SEM, EDX, N<sub>2</sub> adsorption-desorption, MAS NMR, and FTIR with pyridine methods. Selectivity to the product with the 1,8-cineole moiety increased slightly with increasing solids acidity, reaching 77 % on K-10, which was the same as in the presence of BF<sub>3</sub>·Et<sub>2</sub>O. Over strong Brønsted acid (Amberlyst-15), mainly intramolecular cyclization of the diol occurred. Formation of the product with the 1,4-cineole fragment was more pronounced at high initial reagents concentrations, or when water was added, since it is formed through another intermediate containing two hydroxy groups. The reaction mechanism and pathways are discussed using both experimental data and DFT calculations. The use of a catalytic system based on resistant to leaching montmorillonite K-10 in methylene chloride allowed generation of the products with a 1,8-cineole moiety with selectivity up to 96 % depending on the aldehyde.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"691 ","pages":"Article 120070"},"PeriodicalIF":4.7000,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Applied Catalysis A: General","FirstCategoryId":"1","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0926860X24005155","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0

Abstract

Cineole is a natural compound that is used in traditional medicine and pharmaceuticals. This work describes for the first time the selective catalytic synthesis of heterocyclic compounds with a cineole fragment by condensation of 8-hydroxy-6-hydroxymethyllimonene (α-pinene based platform molecules) with thiophene-2-carbaldehyde. Acid-modified halloysite nanotubes and commercial montmorillonites K-10 and K-30 were used as heterogeneous catalysts and compared with the traditional ones. The materials were characterized by SEM, EDX, N2 adsorption-desorption, MAS NMR, and FTIR with pyridine methods. Selectivity to the product with the 1,8-cineole moiety increased slightly with increasing solids acidity, reaching 77 % on K-10, which was the same as in the presence of BF3·Et2O. Over strong Brønsted acid (Amberlyst-15), mainly intramolecular cyclization of the diol occurred. Formation of the product with the 1,4-cineole fragment was more pronounced at high initial reagents concentrations, or when water was added, since it is formed through another intermediate containing two hydroxy groups. The reaction mechanism and pathways are discussed using both experimental data and DFT calculations. The use of a catalytic system based on resistant to leaching montmorillonite K-10 in methylene chloride allowed generation of the products with a 1,8-cineole moiety with selectivity up to 96 % depending on the aldehyde.
基于α-蒎烯的桉叶油脑杂环化合物的催化合成
桉树脑是一种天然化合物,用于传统医学和药物。这项工作首次描述了8-羟基-6-羟甲基柠檬烯(α-蒎烯基平台分子)与噻吩-2-乙醛缩合的桉树脑片段选择性催化合成杂环化合物。以酸改性高岭土纳米管和商品蒙脱土K-10和K-30为催化剂,并与传统催化剂进行了比较。采用SEM、EDX、N2吸附-脱附、MAS NMR、FTIR等方法对材料进行了表征。随着固体酸度的增加,对1,8-桉树脑部分产物的选择性略有增加,在K-10上达到77 %,与BF3·Et2O存在时相同。在强Brønsted酸(Amberlyst-15)上,二醇主要发生分子内环化。在高初始试剂浓度下,或在加水时,产物与1,4-桉树脑片段的形成更为明显,因为它是通过另一种含有两个羟基的中间体形成的。利用实验数据和DFT计算对反应机理和途径进行了讨论。使用基于抗浸出蒙脱土K-10在二氯甲烷中的催化系统,可以产生具有1,8-桉树脑片段的产品,根据醛的不同,选择性高达96% %。
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
Applied Catalysis A: General
Applied Catalysis A: General 化学-环境科学
CiteScore
9.00
自引率
5.50%
发文量
415
审稿时长
24 days
期刊介绍: Applied Catalysis A: General publishes original papers on all aspects of catalysis of basic and practical interest to chemical scientists in both industrial and academic fields, with an emphasis onnew understanding of catalysts and catalytic reactions, new catalytic materials, new techniques, and new processes, especially those that have potential practical implications. Papers that report results of a thorough study or optimization of systems or processes that are well understood, widely studied, or minor variations of known ones are discouraged. Authors should include statements in a separate section "Justification for Publication" of how the manuscript fits the scope of the journal in the cover letter to the editors. Submissions without such justification will be rejected without review.
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
确定
请完成安全验证×
copy
已复制链接
快去分享给好友吧!
我知道了
右上角分享
点击右上角分享
0
联系我们:info@booksci.cn Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。 Copyright © 2023 布克学术 All rights reserved.
京ICP备2023020795号-1
ghs 京公网安备 11010802042870号
Book学术文献互助
Book学术文献互助群
群 号:481959085
Book学术官方微信