DFT calculations of the neighboring groups effects on cheletropic reaction of 2,5-Dihydrothiophene sulfone

Z. Javanshir, S. Jameh-bozorghi, Parasto Peyki
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引用次数: 3

Abstract

In this research DFT calculations were used to investigate the neighboring effects on cheletropic reaction of 2,5-Dihydrothiophene sulfone(1). Structural properties and stereoelectronic behavior in the activation energy and enthalpy of cheletropic reaction was performed for 2,5-Dihydrothiophene sulfone where substitutions of CF3; CCl3 and CBr3 that were placed on Sulfolen were investigated by using DFT-B3LYP/6-311+G** level of theory. The Results of calculations using B3LYP, HF and MP2 [basic 6-311+G**] showed that the trend of electronic effects on the cis and trans state is different. Reaction rate and activation energy in cis compounds showed that increasing electronegativity and decreasing the band length reduced the reaction speed. Trend of reaction rate and activation energy in Trans compounds showed that in cheletropic reaction rate and activation energy not only electronic effects but also the Steric effects play a main role. DFT/B3LYP/6-311+G** calculation results also confirm these results. In cis compounds, 2,5- three Floro metyl Sulfolen(2) has the highest activation energy about (12.25 kcal/mol) and the lowest rate of reaction. In trans compounds, Trans-2,5- three chloro metyl Sulfolen(7) has the highest activation energy about (12.99 kcal/mol) and the lowest rate of reaction.
邻基对2,5-二氢噻吩砜亲电反应影响的DFT计算
本研究采用DFT计算研究邻域效应对2,5-二氢噻吩砜(1)的亲电反应的影响。研究了2,5-二氢噻吩砜的结构性质和立体电子行为,其中取代CF3;采用DFT-B3LYP/6-311+G**理论水平研究了CCl3和CBr3在磺胺上的作用。用B3LYP、HF和MP2[碱性6-311+G**]计算的结果表明,电子效应对顺反态的影响趋势不同。顺式化合物的反应速率和活化能表明,电负性越大,能带长度越短,反应速度越慢。反式化合物的反应速率和活化能变化趋势表明,在亲电反应速率和活化能中,除了电子效应外,位阻效应也起主要作用。DFT/B3LYP/6-311+G**的计算结果也证实了这些结果。在顺式化合物中,2,5- 3 Floro - metyl Sulfolen(2)的活化能最高(12.25 kcal/mol),反应速率最低。反式化合物中,反式-2,5-三氯甲基磺胺(7)的活化能最高,为12.99 kcal/mol,反应速率最低。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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