13358-22-0Relevant academic research and scientific papers
Solvent effect on the volume of activation and volume of the Diels-Alder reaction
Kiselev, Vladimir D.,Konovalov, Alexandr I.,Asano, Tsutomu,Kashaeva, Elena A.,Iskhakova, Gulnara G.,Shihab, Mahdi S.,Medvedeva, Margarita D.
, p. 636 - 643 (2001)
Volumes of activation, ΔV, and reaction, ΔV, partial molar volumes, V, and enthalpies of solution, ΔsolH, were determined for tetracyanoethylene, cyclopentadiene, 1,3-butadiene, trans, trans-1,4-diphenyl-1,3-butadiene and their Diels
Why can the activation volume of the cycloadduct decomposition in isopolar retro-diels-alder reactions be negative?
Kiselev, Vladimir D.
experimental part, p. 117 - 125 (2011/05/19)
Rate constants of the Diels-Alder cycloaddition reaction of anthracene with tetracyanoethylene, enthalpy of solution of reactants and adduct, enthalpy of the reaction in solution, enthalpy and entropy of activation of the forward and retro-Diels-Alder reactions were determined in 14 solvents. Temperature and pressure effects on the rate of the decomposition of the adduct formed from 9-chloroanthracene and tetracyanoethylene were studied. Since the electrostriction effect can be excluded from the consideration of the isopolar Diels-Alder reaction, negative values of the activation volume in the retro-Diels-Alder reactions can be caused by the different possibilities of penetration of the solvent molecules to large steric branched structures of the transition states and adducts.
KINETIC AND THERMOCHEMICAL INVESTIGATION OF THE FORWARD AND REVERSE DIELS-ALDER REACTIONS OF TETRACYANOETHYLENE WITH ANTHRACENE AND 9,10-DIMETHYLANTHRACENE IN CERTAIN SOLVENTS
Kiselev, V. D.,Malkov, V. B.,Konovalov, A. I.
, p. 191 - 200 (2007/10/02)
The Diels-Alder reaction of tetracyanoethylene with anthracene and 9,10-dimethylanthracene was studied in the forward and reverse directions in a series of solvents.The rate constants, enthalpies and entropies of activation, enthalpies of solution of the reagents and adducts, and enthalpies of the reaction were determined.The changes in the enthalpy of solvation of the reagents, the products, and the transition state for the forward and reverse processes were calculated from the obtained data.The equality of the enthalpies of the reaction obtained from the thermochemical (ΔHr) and kinetic (ΔH1-ΔH-1) measurements suggests that the energies of intermolecular stabilization in the transition state for the forward and reverse Diels-Alder reactions are equal.The indentical changes in the enthalpy of solvation of the transition state for the forward and reverse reactions are consistent with its equilibrium solvation.
THE EFFECT OF THE STABILIZATION AND LOCALIZATION ENERGY ON THE REACTIVITY OF THE REAGENTS IN THE DIELS-ALDER REACTION
Konovalov, A. I.,Kiselev, V. D.
, p. 1018 - 1028 (2007/10/02)
The effect of the stabilization and localization energy on the reactivity of the addends in the Diels-Alder reaction was examined.The enthalpies of stabilization were calculated from data on the ionization potentials and electron affinities, and the chang
(Carbomethoxy)maleic Anhydride, a Highly Reactive New Dienophile and Comonomer
Hall, H. K.,Nogues, P.,Rhoades, J. W.,Sentman, R. C.,Detar, M.
, p. 1451 - 1455 (2007/10/02)
(Carbomethoxy)maleic anhydride (CMA), is an extremely reactive dienophile in cycloadditions with butadiene, isoprene, and chloroprene.The second-order rate constants prove it to be more reactive than tetracyanoethylene.Diels-Alder reaction with anthracene gives the normal addition product.With cyclopentadiene, the endo adduct is obtained and with furan the exo adduct.With p-metoxystyrene, anethole, and diphenylethylene, the 2:1 Wagner-Jauregg-type adducts are obtained, while with styrene both Wagner-Jauregg and Diels-Alder ene adduct are formed.Copolymers form in certain conditions.With isobutyl and phenyl vinyl ether, an inverse-lectron-demand Diels-Alder reaction with CMA yields 2-isobutoxy- or 2-phenoxy-6-methoxy-3,4-dihydro-2H-pyran-3,4-dicarboxylic anhydride.These labile dihydropyrans revert to copolymers.
Reaktivity of Substituted 1,3-Butadienes in Diels-Alder-Reactions
Ruecker, Christa,Lang, Dietrich,Sauer, Juergen,Friege, Henning,Sustmann, Reiner
, p. 1663 - 1690 (2007/10/02)
Kinetic data for the reaction of substituted 1,3-dienes with tetracyanoethylene (TCNE) and other dienophiles are interpreted in terms of the FMO-model.While the expectations are fulfilled qualitatively, the kinetic data cannot be correlated quantitatively.This shows that in Diels-Alder reactions besides HOMO-LUMO separation other factors play an important role, for instance the 1,4-distance in the diene and the conformational equilibrium cisoid transoid of the diene.The kinetic data are in accord with a one-step mechanism of the cycloaddition reaction.
