高压、温度和溶剂对噻吩酮与环戊二烯Diels-Alder环加成反应的影响

IF 1.5 4区 化学 Q4 CHEMISTRY, PHYSICAL
Dmitry A. Kornilov, Aliya A. Kornilova, Alexey A. Shulyatiev, Oleg V. Anikin, Akhat G. Mustafin
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引用次数: 0

摘要

获得了高静水压力、温度和溶剂对硫代二苯甲酮与环戊二烯的Diels–Alder反应速率的影响数据。已经测定了几种溶剂中的活化焓、熵、体积和反应体积。硫代二苯甲酮与环戊二烯的Diels–Alder反应的活化熵和体积接近具有C=C和N=N键的亲二烯类化合物的Diels-Alder反应相应的活化参数。硫代二苯甲酮-环戊二烯反应的速率没有随着溶剂极性的增加而增加,这也是其他Diels–Alder反应的特征。硫代二苯甲酮与环戊二烯的反应的特征是活化体积与反应体积的“异常”比率∆V≠/∆Vr-n>;这可以通过与加合物分子相比过渡态分子对溶剂的空间阻碍较小来解释。比较了许多具有C=C、C=S和N=N键的亲二烯烃的活性,并确定了决定它们在Diels-Alder反应中反应性的因素。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
High pressure, temperature, and solvent effect on the Diels–Alder cycloaddition reaction between thiobenzophenone and cyclopentadiene

The data on high hydrostatic pressure, temperature, and solvent influence on the Diels–Alder reaction rate of thiobenzophenone with cyclopentadiene have been obtained. Activation enthalpies, entropies, volumes, and reaction volumes in several solvents have been determined. The activation entropies and volumes of the Diels–Alder reaction of thiobenzophenone with cyclopentadiene are close to the corresponding activation parameters of Diels–Alder reactions involving dienophiles with C=C and N=N bonds. The rate of thiobenzophenone-cyclopentadiene reaction did not increase with increasing solvent polarity, which is also characteristic of other Diels–Alder reactions. The reaction of thiobenzophenone with cyclopentadiene is characterized by an “anomalous” ratio of the activation volume to the reaction volume ∆V/∆Vr-n > 1. This can be explained by the less steric hindrances of transition-state molecules toward the solvent, compared with adduct molecules. The activities of a number of dienophiles with C=C, C=S, and N=N bonds have been compared, and the factors determining their reactivity in Diels–Alder reactions have been established.

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来源期刊
CiteScore
3.30
自引率
6.70%
发文量
74
审稿时长
3 months
期刊介绍: As the leading archival journal devoted exclusively to chemical kinetics, the International Journal of Chemical Kinetics publishes original research in gas phase, condensed phase, and polymer reaction kinetics, as well as biochemical and surface kinetics. The Journal seeks to be the primary archive for careful experimental measurements of reaction kinetics, in both simple and complex systems. The Journal also presents new developments in applied theoretical kinetics and publishes large kinetic models, and the algorithms and estimates used in these models. These include methods for handling the large reaction networks important in biochemistry, catalysis, and free radical chemistry. In addition, the Journal explores such topics as the quantitative relationships between molecular structure and chemical reactivity, organic/inorganic chemistry and reaction mechanisms, and the reactive chemistry at interfaces.
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