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Kinetics and thermochemistry of the [2π+2σ+2σ]‐cycloaddition of quadricyclane with 2,3‐dicyano‐1,4‐benzoquinone
Author(s) -
Kornilov Dmitry A.,
Anikin Oleg V.,
Kolesnikova Anastasia O.,
Bermeshev Maxim V.,
Gubaidullin Aidar T.,
Kiselev Vladimir D.
Publication year - 2019
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.21264
Subject(s) - cycloaddition , chemistry , quadricyclane , thermochemistry , enthalpy , benzoquinone , kinetics , photochemistry , double bond , adduct , medicinal chemistry , computational chemistry , organic chemistry , catalysis , thermodynamics , isomerization , physics , quantum mechanics
Two‐stage [2π+2σ+2σ]‐cycloaddition of quadricyclane ( 2 ) with 2,3‐dicyano‐1,4‐benzoquinone ( 1 ) with a huge difference in the activity of two reaction centers has been studied. In the first stage (kinetic control), the cycloaddition of 2 takes place on the activated С 2 =С 3 bond of 1 to form the monoadduct 3 , and in the second stage the cycloaddition of 2 on the С 5 =С 6 bond of the monoadduct 3 occurs by 6 orders of magnitude lower with the formation of bisadduct 4 . The structures of adducts 3 and 4 have been proved by NMR data and the X‐Ray method, respectively. The kinetics of the first and second stages, the enthalpy of dissolution of 1 in the π‐donor solvents, and the enthalpy of the reaction 1+2→3 have been measured.