Theoretical Study on the Thermal Isomerization from 1,2-Butadiene to 2-Butyne

Abstract

Abstract: Ab initio UHF/631G^** method was employed to study the reaction mechanisms of the thermal isomerization from 1,2-butadiene to 2-butyne, which involves two reaction pathways. The geometries of the reactant, the intermediates, the transition states and the product for the reaction are optimized by Berry technique. Each transition states was further confirmed by having one and only one imaginary vibrational frequency. In addition, the zero point energies were calculated for correcting the energies of stationary points. As an important intermediate, 1-methylcyclopropene play a significant part in the isomerization. The calculated activation energy of the pathway proceeding in multisteps via 1-methylcycloproene etc is 28683 kJ/mol, which is in good agreement with arrhenius value of 26460 kJ/mol. The results indicate that the thermal rearrangement of 1,2-butadiene to 2-butyne via 1-methyl-cyclopropene is more energetically favourable than that via two-step hydrogen-shift process.

Key words: Isomerization, Transition state, Ab initio method

CLC Number:

O643

TrendMD:

LEI Ming, QIAN Ying, WANG Yan, FENG Wen-Lin . Theoretical Study on the Thermal Isomerization from 1,2-Butadiene to 2-Butyne[J]. Chem. J. Chinese Universities, 1998, 19(4): 586.

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Theoretical Study on the Thermal Isomerization from 1,2-Butadiene to 2-Butyne

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