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Cyclic and Acyclic N═N Bonds in Reactions with Some Alkenes and Dienes
Author(s) -
Kiselev Vladimir D.,
Kornilov Dmitry A.,
Konovalov Alexander I.
Publication year - 2017
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.21094
Subject(s) - chemistry , cyclooctatetraene , enthalpy , cycloheptatriene , reaction rate , tautomer , diethyl azodicarboxylate , medicinal chemistry , reversible reaction , kinetics , computational chemistry , photochemistry , thermodynamics , organic chemistry , catalysis , molecule , triphenylphosphine , physics , quantum mechanics
The kinetics of the Diels–Alder (DA) reactions of 4‐phenyl‐1,2,4‐triazoline‐3,5‐dione 1 , trans ‐diethyl azodicarboxylate 2 , and tetracyanoethene 3 with 1,3‐cyclohexadiene 4 , cycloheptatriene 5 , 1,3‐cycloheptadiene 6 , cyclooctatetraene 7 , and 1,3‐cyclooctadiene 8 in a range of temperatures and pressures has been studied. Values of the enthalpy, entropy, and volume of activation, as well as the enthalpy and volume of reaction have been obtained. Observed reaction rates of 5+1 and 7+1 have been compared with the known rate of norcaradiene 17 formation in the equilibrium 5 ⇌ 17 , and that of bicyclo[4,2,0]‐octa‐2,4,7‐triene 20 in the equilibrium 7 ⇌ 20 . The kinetic data show that the rate of formation of 17 from 5 is much greater than the loss rate of dienophile 1 in reaction of 5+1 . In contrast, the formation rate of tautomer 20 is less than the loss rate of dienophile 1 in reaction of 7+1 . This reflects that the consecutive reaction of 5 → 17 (+ 1 ) → 15 is possible whereas the consecutive reaction of 7 → 20 (+ 1 ) → 22 does not occur as the only way.