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Reaction of hypochlorous acid with imidazole: Formation of 2‐chloro‐ and 2‐oxoimidazoles
Author(s) -
Je. R.,
Kushwaha P. S.,
Mishra P. C.
Publication year - 2007
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.20768
Subject(s) - hypochlorous acid , imidazole , chemistry , density functional theory , polarizable continuum model , computational chemistry , polarizability , transition state , reaction coordinate , ring (chemistry) , aqueous solution , stereochemistry , organic chemistry , molecule , catalysis , solvation
Reaction of hypochlorous acid (HOCl) with imidazole (Im) taken as a model for the 5‐membered ring of guanine, leading to the products 2‐chloro‐ and 2‐oxo‐imidazoles was investigated at the B3LYP/6‐31+G* and B3LYP/AUG‐cc‐pVDZ levels of density functional theory. For all cases, single point energy calculations were performed at the MP2/AUG‐cc‐pVDZ level of theory using the geometries optimised at the B3LYP/AUG‐cc‐pVDZ level. Intrinsic reaction coordinate calculations were performed to ensure genuineness of all the calculated transition states. Effect of aqueous media was investigated by solvating all the species involved in the reactions using the polarizable continuum model. It is found that 2‐chloroimidazole (2‐ClIm) can be formed following three different reaction schemes while 2‐oxoimidazole (2‐oxoIm) can be formed following two different reaction schemes. The calculated barrier energies show that formation of 2‐oxoIm would be less favored than that of 2‐ClIm, which explains the experimental observations on relative yields of 8‐chlorodeoxyguanosine and 8‐oxodeoxyguanosine. © 2007 Wiley Periodicals, Inc. J Comput Chem 2008