在叔胺立体效应和溶剂极性之间找到适当的平衡,以提高环氧氯丙烷乙酰分解的区域选择性和动力学性能

IF 1.9 4区 化学 Q2 CHEMISTRY, ORGANIC
Kseniia Yutilova, Anastasiia Tkach, Vladislav Tarasenko, Elena Shved
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引用次数: 0

摘要

在 "乙酸-环氧氯丙烷-四氢呋喃(硝基苯)-三烷基胺 "反应系列中,通过动力学方法和傅立叶变换红外光谱法研究了导致形成区域异构体氯醇酯的不对称环氧乙烷开环反应。研究了溶剂极性和叔胺结构对区域选择性和反应速率的影响。研究选择了碱性相当但亲核性和空间结构不同的叔胺作为催化剂。研究表明,在不同极性的溶剂中,初始反应体系的组分既可以氢键复合物的形式存在,也可以单个物质的形式存在。研究还确定了在不同极性溶剂中酸和胺的反应顺序。建立了反应速率与胺的亲核性和结构参数以及溶剂极性之间的相关性。用 1H NMR 光谱法研究了反应的区域选择性,使用的是区域异构反应产物的比率。结果表明,叔胺的结构和溶剂的极性有效地控制了环氧氯丙烷催化乙酰分解的区域选择性和速率。详细介绍了反应的区域流动方案。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Finding the right balance between tertiary amine steric effect and solvent polarity for the regioselectivity and kinetics of epichlorohydrin acetolysis

Finding the right balance between tertiary amine steric effect and solvent polarity for the regioselectivity and kinetics of epichlorohydrin acetolysis

Finding the right balance between tertiary amine steric effect and solvent polarity for the regioselectivity and kinetics of epichlorohydrin acetolysis

The asymmetric oxirane ring-opening reaction leading to the formation of regioisomeric chlorohydrin esters was studied in the reaction series “acetic acid–epichlorohydrin–tetrahydrofuran (nitrobenzene)–trialkylamine” by kinetic methods and FT-IR spectroscopy. The effect of solvent polarity and the structure of tertiary amines on the regioselectivity and reaction rate were studied. Tertiary amines with comparable basicity but different nucleophilicity and spatial structure were chosen as catalysts. It was shown that in solvents of different polarity, the components of the initial reaction system are present both as hydrogen-bonded complexes and as individual substances. The reaction orders with respect to acid and amine in solvents of different polarity were established. Correlations between the reaction rate and the parameters of nucleophilicity and structure of amines as well as the polarity of the solvent were established. The regioselectivity of the reaction was studied by 1H NMR spectroscopy using the ratio of regioisomeric reaction products. It was shown that the regioselectivity and rate of catalytic acetolysis of epichlorohydrin are effectively controlled by the structure of tertiary amines and the polarity of the solvent. The scheme of reaction regio-flows was detailed.

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来源期刊
CiteScore
3.60
自引率
11.10%
发文量
161
审稿时长
2.3 months
期刊介绍: The Journal of Physical Organic Chemistry is the foremost international journal devoted to the relationship between molecular structure and chemical reactivity in organic systems. It publishes Research Articles, Reviews and Mini Reviews based on research striving to understand the principles governing chemical structures in relation to activity and transformation with physical and mathematical rigor, using results derived from experimental and computational methods. Physical Organic Chemistry is a central and fundamental field with multiple applications in fields such as molecular recognition, supramolecular chemistry, catalysis, photochemistry, biological and material sciences, nanotechnology and surface science.
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