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- W1986872252 abstract "The C8H10 hydrocarbons 1, 3, 4, and 6 have been thermolyzed in a static system and the Arrhenius parameters have been obtained. Calorimetric measurements have been carried out to determine the heats of formation. From these data an experimental energy hypersurface is constructed which shows the following remarkable features: 1) The ground-state energy of endo-1 is higher than that of exo-4 by 8 kcal mol−1. 2) The predominant reaction pathway of endo-1 is the formally forbidden [2σ + 2π] cycloaddition to 3, the mechanism of which is discussed. 3) Although the activation energies of the routes 4→6 and 4→3 are the same, the reaction yielding 6 is faster due to a sizeably higher A factor. 4) The tetracycle 3 chooses the microscopic reverse pathway, i.e. its thermolysis proceeds via exo-4 to give the diene 6. Die C8H10-Kohlenwasserstoffe 1, 3, 4 und 6 wurden im statischen System thermolysiert, und die Arrhenius-Parameter wurden gemessen. Die Bildungswärmen wurden kalorimetrisch bestimmt. Aus diesen Daten läßt sich eine experimentelle Energiehyperfläche konstruieren, die folgende Merkmale aufweist: 1) Die Grundzustandsenergie von endo-1 ist um 8 kcal mol−1 höher als die von exo-4. 2) Der wichtigste Reaktionsweg ausgehend von endo-1 ist die formal verbotene [2σ + 2π]-Cycloaddition zu 3, deren Mechanismus diskutiert wird. 3) Obwohl die Aktivierungsenergien der Wege 4→6 und 4→3 gleich sind, verläft die Reaktion zu 6 aufgrund des größeren A-Faktors rascher. 4) Der Tetracyclus 3 thermolysiert gemäß dem Prinzip der mikroskopischen Reversibilität über exo-4 zu dem Dien 6." @default.
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- W1986872252 date "1987-02-01" @default.
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- W1986872252 title "An experimental approach to the C <sub>8</sub> H <sub>10</sub> hypersurface. Kinetic and thermochemical investigations on a formally forbidden ground‐state [2σ + 2π] cycloaddition" @default.
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- W1986872252 doi "https://doi.org/10.1002/cber.19871200209" @default.
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