Quantum Chemistry Studies on Mechanism of Gas Phase Photochemical Chlorination of 2-Chloropyridine

Abstract

Abstract: The gas phase reaction mechanism of the photochemical chlorination of 2-chloropyridine was theoretically studied by using DFT B3LYP/3-21G~* method.The activation energy leading to 2,3-dichloropyridine,2,4-dichloropyridine,2,5-dichloropyridine and 2,6-dichloropyridine were also calculated respectively.The calculated results consistently show that the energy of transition state and the activation energy for the formation of 2,6-dichloropyridine were the lowest among the four reaction pathways.Therefore,the main product should be 2,6-dichloropyridine.The IRC result showed that the breaking of C—H and the forming of C—Cl were concerted but not synchronous.The structure of the transition state was near to 2,6-dichloropyridine,which showed that it was a late transition state.During the whole reaction processing,the Cl· acted as a nucleophilic specie,donating the electron.Therefore,S_N2 mechanism was speculated for the reaction of Cl· with 2-chloropyridine.

Key words: 2-Chloropyridine, Photochemical chlorination, Transition state, DFT

CLC Number:

O626
O641

TrendMD:

HAO Jin-Ku, HUA Fang, YANG En-Cui, CAO Ying-Yu, YANG Kun, ZHAO Yan . Quantum Chemistry Studies on Mechanism of Gas Phase Photochemical Chlorination of 2-Chloropyridine[J]. Chem. J. Chinese Universities, 2005, 26(10): 1896.

References

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