Theoretical Study on the Reaction Mechanism for Diels-Alder Cycloaddition of C50(D5h) with 1,3-Butadiene and 2,3-Disubstituted 1,3-Butadienes

Chem. J. Chinese Universities ›› 2009, Vol. 30 ›› Issue (11(1)): 16.

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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

Abstract

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

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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[J]. Chem. J. Chinese Universities, 2009, 30(11(1)): 16.

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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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