C50(D5h)与1,3-丁二烯及2,3-二取代的1,3-丁二烯的Diels-Alder环加成反应机理的理论研究

高等学校化学学报 ›› 2009, Vol. 30 ›› Issue (11(1)): 16.

C₅₀(D_5h)与1,3-丁二烯及2,3-二取代的1,3-丁二烯的Diels-Alder环加成反应机理的理论研究

许秀芳, 尚贞锋, 李瑞芳, 赵学庄

南开大学化学系, 天津 300071

收稿日期:2009-07-28 出版日期:2009-11-30 发布日期:2009-11-30
通讯作者: 许秀芳, 女, 博士, 主要从事富勒烯理论研究. E-mail: xxfang@nankai.edu.cn

Theoretical Study on the Reaction Mechanism for Diels-Alder Cycloaddition of C₅₀(D_5h) with 1,3-Butadiene and 2,3-Disubstituted 1,3-Butadienes

XU Xiu-Fang*, SHANG Zhen-Feng, LI Rui-Fang, ZHAO Xue-Zhuang

Department of Chemistry, Nankai University, Tianjin 300071, China

Received:2009-07-28 Online:2009-11-30 Published:2009-11-30
Contact: XU Xiu-Fang. E-mail: xxfang@nankai.edu.cn

摘要/Abstract

摘要：

用半经验的AM1方法研究了C₅₀(D_5h) 与1,3-丁二烯及7种2,3-二取代的1,3-丁二烯(取代基为F, Cl, Br, I, CH₃, OH和NO₂)的Diels-Alder环加成反应机理. 优化了各环加成反应的反应物、过渡态及产物进行构型, 进行了频率分析, 计算了各反应的活化能和热效应. 计算结果表明, (1) 各反应均经历了协同反应历程, 各反应体系到达过渡态时, 两条正在形成的C—C键在0.2293~0.2527 nm之间. (2) C₅₀(D_5h)与1,3-丁二烯Diels-Alder环加成反应的活化能较低(为15.90 kJ/mol), 且整个反应放出的热量较高(为402.50 kJ/mol), 无论从动力学角度还是从热力学角度该反应都很容易发生, 预计常温下就易进行. C₅₀(D_5h)比C₆₀和C₇₀的反应活性要高得多. (3) 当在1,3-丁二烯的2, 3位取代不同基团后, 不同种类的取代基对C₅₀(D_5h)与1,3-丁二烯的Diels-Alder环加成反应的活化能影响不同: 弱吸电子基或弱给电子基对上述环加成反应的活化能影响不大, 而强给电子基或强吸电子基则明显改变了上述反应的活化能, 强给电子基明显降低活化能, 强吸电子基明显升高活化能. (4) C₅₀(D_5h)与一系列丁二烯环加成反应的逆反应活化能都很高, 在416.51~425.93 kJ/mol范围, 说明形成的环加成衍生物很稳定, 不易分解.

关键词: Diels-Alder环加成反应; 机理; 过渡态; 活化能

Abstract:

The reaction mechanism for Diels-Alder cycloaddition of C₅₀(D_5h) with 1,3-butadiene and 2,3-disubstituted 1,3-butadienes has been investigated using the semiempirical AM1 method. The calculated results show that: (1) All the Diels-Alder cycloaddition reactions take place via a concerted process. The length of the forming C—C bonds in transition states is in the range of 0.2293—0.2527 nm. (2) The activation energy(15.90 kJ/mol) for the cycloaddition of C₅₀(D_5h) with 1,3-butadiene is low. Moreover, this reaction is high exothermic of 402.50 kJ/mol. Therefore, it is predicted that not only kinetically but also thermodynamically the cycloaddition of C₅₀(D_5h) with 1,3-butadiene is easy to take place at room temperature. The C₅₀(D_5h) is more reactive than C₆₀ and C₇₀. (3) Different substituted groups on 1,3-butadiene have different effect on the reaction activation energy of the cycloaddition of C₅₀(D_5h) with substituted 1,3-butadiene. Weak electron-withdrawing or weak electron-donating groups have small effect on the reaction activation energy. While strong electron-withdrawing or strong electron-donating groups have outstanding effect on the reaction activation energy: Strong electron-donating groups obviously lower and strong electron-withdrawing group dramatically increase the reaction activation energy, respectively. (4) All the reverse reaction activation energies for the Diels-Alder cycloaddition of C₅₀(D_5h) with 1,3-butadiene and the substituted 1,3-butadienes are very high and in a range of 416.51—425.93 kJ/mol, indicating that the product of the Diels-Alder cycloadditions is very stable kinetically.

Key words: Diels-Alder cycloaddition; Reaction mechanism; Transition state; Activation energy

TrendMD:

许秀芳, 尚贞锋, 李瑞芳, 赵学庄. C₅₀(D_5h)与1,3-丁二烯及2,3-二取代的1,3-丁二烯的Diels-Alder环加成反应机理的理论研究. 高等学校化学学报, 2009, 30(11(1)): 16.

XU Xiu-Fang*, SHANG Zhen-Feng, LI Rui-Fang, ZHAO Xue-Zhuang.

Theoretical Study on the Reaction Mechanism for Diels-Alder Cycloaddition of C₅₀(D_5h) with 1,3-Butadiene and 2,3-Disubstituted 1,3-Butadienes. Chem. J. Chinese Universities, 2009, 30(11(1)): 16.

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C₅₀(D_5h)与1,3-丁二烯及2,3-二取代的1,3-丁二烯的Diels-Alder环加成反应机理的理论研究

Theoretical Study on the Reaction Mechanism for Diels-Alder Cycloaddition of C₅₀(D_5h) with 1,3-Butadiene and 2,3-Disubstituted 1,3-Butadienes

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