13358-22-0Relevant articles and documents
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
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.
(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.
