Nucleophilic epoxide ring opening in the system "epichlorohydrin–carboxylic acids–tetrabutylammonium iodide–solvent (e=15.1–28.7)"

Q4 Chemistry

Voprosy Khimii i Khimicheskoi Tekhnologii Pub Date : 2023-05-01 DOI:10.32434/0321-4095-2023-147-2-4-159-167

K. Yutilova, E. Bakhalova, E. Shved, А.V. Kravchuk, L. S. Lisova

{"title":"Nucleophilic epoxide ring opening in the system \"epichlorohydrin–carboxylic acids–tetrabutylammonium iodide–solvent (e=15.1–28.7)\"","authors":"K. Yutilova, E. Bakhalova, E. Shved, А.V. Kravchuk, L. S. Lisova","doi":"10.32434/0321-4095-2023-147-2-4-159-167","DOIUrl":null,"url":null,"abstract":"The mechanism of the oxirane ring opening by carboxylic acids with different volume of substituents in the system \"epichlorohydrin(ЕCH)–RCOOH–tetrabutylammonium iodide–solvent (=15.1–28.7)\" was studied in the excess of ECH at the temperatures of 40–800C by methods of chemical kinetics and correlation analysis. The effects of solvent polarity (ECH and its mixtures with THF and nitrobenzene), temperature, and spatial structure (topological steric effect index TSEI) of carboxylic acids on the proceeding of the reaction were investigated. The structure of the reaction products was determined by gas chromatography–mass and 1H NMR spectroscopy. It was found that the reaction accelerates with a decrease in the solvent polarity, an increase in temperature and steric effect in the structure of the reagent. It was shown that the tetraalkylammonium carboxylate (R'4N+–OOCR) which formed in situ causes the final product formation in the rate-determining step of the reaction mechanism.","PeriodicalId":23684,"journal":{"name":"Voprosy Khimii i Khimicheskoi Tekhnologii","volume":"509 1","pages":""},"PeriodicalIF":0.0000,"publicationDate":"2023-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Voprosy Khimii i Khimicheskoi Tekhnologii","FirstCategoryId":"1085","ListUrlMain":"https://doi.org/10.32434/0321-4095-2023-147-2-4-159-167","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q4","JCRName":"Chemistry","Score":null,"Total":0}

引用次数: 0

Abstract

The mechanism of the oxirane ring opening by carboxylic acids with different volume of substituents in the system "epichlorohydrin(ЕCH)–RCOOH–tetrabutylammonium iodide–solvent (=15.1–28.7)" was studied in the excess of ECH at the temperatures of 40–800C by methods of chemical kinetics and correlation analysis. The effects of solvent polarity (ECH and its mixtures with THF and nitrobenzene), temperature, and spatial structure (topological steric effect index TSEI) of carboxylic acids on the proceeding of the reaction were investigated. The structure of the reaction products was determined by gas chromatography–mass and 1H NMR spectroscopy. It was found that the reaction accelerates with a decrease in the solvent polarity, an increase in temperature and steric effect in the structure of the reagent. It was shown that the tetraalkylammonium carboxylate (R'4N+–OOCR) which formed in situ causes the final product formation in the rate-determining step of the reaction mechanism.

查看原文本刊更多论文

“环氧氯丙烷-羧酸-四丁基碘化铵-溶剂(e= 15.1-28.7)”体系中的亲核环氧化合物开环

采用化学动力学和相关分析的方法，在40 ~ 800℃的过量ECH条件下，研究了不同取代基体积的羧酸在“环氧氯丙烷(ЕCH) - rcooh -四丁基碘化铵-溶剂(15.1 ~ 28.7)”体系中开环的机理。考察了溶剂极性(ECH及其与四氢呋喃和硝基苯的混合物)、温度和羧酸的空间结构(拓扑立体效应指数TSEI)对反应进行的影响。采用气相色谱-质谱法和1H NMR谱法测定了反应产物的结构。结果表明，溶剂极性的降低、温度的升高和试剂结构的位阻效应会使反应加速。结果表明，原位生成的四烷基羧酸铵(R'4N+ -OOCR)在反应机理的速率决定步骤中导致最终产物的生成。

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

Voprosy Khimii i Khimicheskoi Tekhnologii Chemical Engineering-Chemical Engineering (all)

CiteScore

0.90

自引率

0.00%

发文量

期刊介绍： Voprosy Khimii i Khimicheskoi Tekhnologii (Issues of Chemistry and Chemical Technology) is published bimonthly by the Ukrainian State University of Chemical Technology and accepts Ukrainian- or English language high-quality original articles and reviews concerning various fields of research in chemistry and chemical engineering. Our unusual title “Voprosy khimii i khimicheskoi tekhnologii” originates from the transliterated initial Russian title “Issues of Chemistry and Chemical Technology“. The fact of the matter is that Voprosy khimii i khimicheskoi tekhnologii was founded in 1965 as a scientific journal mainly for Russian-reading and Russian-speaking readership when «the Iron Curtain» existed. Since 1991, after Ukraine declared its independence, our Journal began to publish the articles in Ukrainian and English. Multilingualism is our established tradition. We remember and cherish our traditions, but we follow the latest trends in modern science. Papers that are multidisciplinary or address new or emerging areas of chemistry and chemical engineering are particularly encouraged. Thus, the scope is dynamic. It includes but is not limited to the traditional areas of general, inorganic, organic, analytical, physical chemistry and electrochemistry, as well as all conventional areas of chemical engineering (chemistry of high molecular compounds, technology of inorganic and organic substances, processing of combustible minerals, chemical technology of silicates, processes and apparatus of chemical productions, etc.). The Journal publishes papers dealing with newer interdisciplinary areas such as materials science, nano-science, catalysis, computational and theoretical chemistry, surface phenomenon and colloidal systems, environmental chemistry, green chemistry.