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Direct ring‐open mechanism of pyridine formation by replacement of one carbon in benzene with one nitrogen atom
Author(s) -
Lu Haoyun,
Qian Mengqi,
Wang Qiang,
Yang Yanhui
Publication year - 2020
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.4061
Subject(s) - chemistry , benzene , dissociation (chemistry) , isomerization , pyridine , photochemistry , reaction mechanism , ring (chemistry) , heteroatom , catalysis , medicinal chemistry , organic chemistry
It is hardly replaced one carbon in benzene with other heteroatom by direct breaking of the particularly strong C=C bond in benzene not only due to the high dissociation energy of benzene ring but also due to more limit to the C–H activation. Direct ring‐open of benzene has been mainly limited to the high dissociation energy. In our former research, we have found an ion‐molecule reaction via simple replacement of one carbon in benzene with nitrogen atom. But the reaction mechanism still remains unresolved. Herein, we demonstrate the direct ring‐open mechanism in benzene through theoretical study of potential energy surface, in which benzene attacked by H 2 NO 2 + ion with the formation of pyridine. Reaction mechanisms have been confirmed that ring‐open in benzene involves two steps that include attacking reaction and isomerization process. It is found that H 2 NO 2 + ion trend to attack benzene with dissociation of H 2 O firstly. The isomerization process happens is most favorable in the evolution potential energy surface of the isomer C 6 H 5 N(H)O + . It has been verified of the theory, which is consistent with the experiment. The mechanism derived from this study may provide guidance for promoting the reaction yield and selectivity of aromatics ring‐open reaction.