Effect of Medium on the Kinetics of Stereoselective Synthesis of a Highly Functionalized Cyclopropanesame

IF 1.4 Q3 CHEMISTRY, MULTIDISCIPLINARY

Physical Chemistry Research Pub Date : 2020-03-01 DOI:10.22036/PCR.2019.176786.1607

F. Mahmoudi, M. Shahraki, Sayeydmosatfa Habibi-khorassani

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Abstract

The effect of different media on the kinetics and mechanism of formation of diethyl (1S, 2S)-3, 3-dibenzoylcyclopropane-1, 2-dicarboxylate was investigated. The reaction was accelerated with changing the medium from non-ionic to ionic. Among the selected ionic salts, NaCl was the best salt to increase the reaction rate of the titled synthesis about 2.5-fold (kobs = 1.295 M-1.min-1 against kobs = 3.105 M-1.min-1). The incremental effect of ionic salts was found to be in this order: NaCl > NaBr > KBr > KCl. Isokinetic plots for the reaction in the presence of different salts were obtained and a linear relationship which indicated an identical mechanism for all reactions, was found. Moreover, the effect of cationic, nonionic, and anionic surfactants on the reaction rate was evaluated. Substantial reduction on the reaction rate and change in the mechanism was observed with the addition of an anionic surfactant such as sodium dodecyl sulfate. The values of activation parameters were also estimated (ΔH‡ = 80.1 ± 0.6 kJ.mol-1, ΔS‡ = 23.9 ± 2.0 J.mol-1.K-1, and ΔG‡ = 72.9 ± 1.1 kJ.mol-1) and the positive value of ΔH‡ confirmed the endothermic process and entropy value referred to an associative mechanism.

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介质对高功能化环丙烷立体选择性合成动力学的影响

研究了不同介质对(1S, 2S)- 3,3 -二苯甲酰环丙烷- 1,2 -二羧酸二乙酯生成动力学和机理的影响。将介质由非离子型变为离子型，加速了反应。在所选择的离子盐中，NaCl的效果最好，可使反应速率提高2.5倍(kobs = 1.295 M-1)。min-1对kobs = 3.105 m -1 min-1)。离子盐的增量效应依次为:NaCl > NaBr > KBr > KCl。得到了不同盐存在下反应的等速图，发现了表明所有反应具有相同机理的线性关系。考察了阳离子、非离子和阴离子表面活性剂对反应速率的影响。在阴离子表面活性剂如十二烷基硫酸钠的加入下，反应速率明显降低，反应机理发生了变化。对激活参数值也进行了估计(ΔH‡= 80.1±0.6 kJ)。mol-1， ΔS‡= 23.9±2.0 J.mol-1。K-1， ΔG‡= 72.9±1.1 kJ.mol-1)， ΔH‡的正值证实了吸热过程和熵值的关联机制。

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来源期刊

Physical Chemistry Research CHEMISTRY, MULTIDISCIPLINARY-

CiteScore

2.70

自引率

8.30%

发文量

期刊介绍： The motivation for this new journal is the tremendous increasing of useful articles in the field of Physical Chemistry and the related subjects in recent years, and the need of communication between Physical Chemists, Physicists and Biophysicists. We attempt to establish this fruitful communication and quick publication. High quality original papers in English dealing with experimental, theoretical and applied research related to physics and chemistry are welcomed. This journal accepts your report for publication as a regular article, review, and Letter. Review articles discussing specific areas of physical chemistry of current chemical or physical importance are also published. Subjects of Interest: Thermodynamics, Statistical Mechanics, Statistical Thermodynamics, Molecular Spectroscopy, Quantum Chemistry, Computational Chemistry, Physical Chemistry of Life Sciences, Surface Chemistry, Catalysis, Physical Chemistry of Electrochemistry, Kinetics, Nanochemistry and Nanophysics, Liquid Crystals, Ionic Liquid, Photochemistry, Experimental article of Physical chemistry. Mathematical Chemistry.