Theoretical Study of Photochemical Chlorination of Pyridine in Gas Phase──Transition States of Addition Mechanism and IRC Analysis

Abstract

Abstract: The addition mechanism of pyridine reacting with chlorine radical was studied theoretically bysemi-empirical method PM3.The results show that there exist two transition states on each reaction pathof obtaining 2-chloropyridine, 3-chloropyridineopyr and 4-chloropyridine.The energies of chief transitionstate and activation barrier for leading to 2-chloridine are the lowest among the three reaction paths, whichare -110293.6 and 139.2 kJ/mol respectively, so 2-chloropyridine is obtained priorly.On getting 2-chloropyridine, from the variation of bond length, bond order and net charge, we can concludde that theformation of C－Cl is concerted with the breaking of conjugated double bond, and the break of C-Hisconcerted with the reconformation of conjugated double bond Both inductive and resonance effects can in-fluence the net charge of chlorine atom.

Key words: Pyridine, Photochemical chlorination, Reaction mechanism, Transition state, IRC, PM3

CLC Number:

O742

TrendMD:

HAD Jin-Ku, YANG En-Cui, WANG Wan-De, ZHAO Xiao-Jun, CAO Ying-Yu, HAN Xiao-Yan . Theoretical Study of Photochemical Chlorination of Pyridine in Gas Phase──Transition States of Addition Mechanism and IRC Analysis[J]. Chem. J. Chinese Universities, 2002, 23(5): 828.

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Theoretical Study of Photochemical Chlorination of Pyridine in Gas Phase──Transition States of Addition Mechanism and IRC Analysis

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