Analytical solution to the Curtin-Hammett/Winstein-Holness kinetic system

Seeman, Jeffrey I.; Farone, William A.

doi:10.1021/jo00404a002

Cited by 36 publications

(24 citation statements)

References 7 publications

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“…Unfortunately, an analytical solution is not possible for the more complicated Equation (2) . Consequently, the determination of reaction‐rate constants is extremely complicated, if not impossible, for some sets of Equation (2) systems, even when the experiments are conducted under pseudo‐first‐order conditions, just as David England and Werner Hentschel discovered to their certain dismay as described by Huisgen…”

Section: Introductionsupporting

confidence: 90%

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Rolf Huisgen's Classic Studies of Cyclic Triene Diels–Alder Reactions Elaborated by Modern Computational Analysis

2020

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Rolf Huisgen explored the Diels–Alder reactions of 1,3,5‐cycloheptatriene (CHT) and cyclooctatetraene (COT) with the dienophiles maleic anhydride and 4‐phenyl‐1,2,4‐triazoline‐3,5‐dione (PTAD) to determine the kinetics and mechanisms of various electrocyclizations and Diels–Alder reactions. These reactions have been examined with density functional theory. Modern computational chemistry has provided information not previously available by experiment. Transition states for all the reactions have been identified, and their Gibbs energies are used to explain the experimental reactivities. Zwitterionic intermediates were not found in the [4+2] cycloadditions of both CHT or COT with PTAD and are thus not involved in these reactions. [2+2+2] cycloadditions, as an alternative path to the Diels–Alder products, are highly disfavored. Rapid double nitrogen inversion was found for the cycloaddition products with PTAD.

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Section: Introductionsupporting

confidence: 90%

“…For all relative values of k ij in Equation (3) systems, an analytical solution was determined by Seeman and William A. Farone, and a general equation at reaction completion was provided by Nicolai Zefirov . Unfortunately, an analytical solution is not possible for the more complicated Equation (2) .…”

Section: Introductionmentioning

confidence: 99%

Rolf Huisgen's Classic Studies of Cyclic Triene Diels–Alder Reactions Elaborated by Modern Computational Analysis

2020

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“…Hammett en los años cincuenta, con la idea de proporcionar un tratamiento para diferenciar la distribución de una población conformacional en el estado basal (en equilibrio) de un sistema conformacionalmente móvil con la proporción del producto final de una reacción en donde participan ambos confórmeros (Gold, 1983). Es decir, si en una reacción química se obtiene un producto (A 1 ) a partir de un isómero conformacional (A 2 ) y otro diferente (A 4 ) a partir del otro confórmero (A 3 ) (suponiendo que estos dos isómeros se interconvierten rápidamente en relación con la velocidad de formación de los productos y que los productos no se interconvierten), la composición de los productos no depende prácticamente de las proporciones relativas de los isómeros conformacionales en el sustrato, sino de la diferencia en las energías libres de Gibbs (∆G ≠ ) de los estados de transición respectivos, figura 3 (Seeman, 1978). De acuerdo con la figura 3, la proporción de los productos se da por la ecuación.…”

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La relación entre la conformación y la reactividad

Morales

Gordillo²

2018

Educación Química

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<span>Este artículo está dirigido a los estudiantes de licenciatura y posgrado en Química. Su contenido podría ser usado como material de apoyo para los profesores de Química Orgánica de nivel superior interesados en enseñar mecanismos de reacción y teoría. Los dos ejemplos que se presentan en el manuscrito son representativos del campo de aplicación del denominado principio de Curtin-Hammett</span>

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“…qftzitrog(~tz It is interesting to calculate the second n-bond energy of nitrogen by using data from s t~~d i e s of thermal decomposition of several azo conipounds. This is done using the sequence of reactions he mechanism of nitrogen formation is assumed to be A completc solution of this nlechanisnl has been rcportetl by Seeman and Farone (15). If equilibriuni is maintained between the two isomers.…”

Section: Rate Of Decotrlj>ositio~z Ofthe Trvo Isomersmentioning

confidence: 99%

The thermal decomposition of azobenzene

Barton¹,

Hodgett²,

Skirving³

et al. 1983

Can. J. Chem.

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The rate of nitrogen formation during the thermal decomposition of azobenzene in static and stirred-flow systems was measured over the temperature range of 368.9 °C to 437.4 °C. The first order rate constant was found to be given by the expression[Formula: see text]A consideration of the equilibrium constant between cis-azobenzene and trans-azobenzenc, and the rate of attainment of equilibrium, leads to the conclusion that a small concentration of cis-azobenzene is always present, at equilibrium with the trans isomer. Since the cis isomer is likely to be more reactive than the trans isomer the rate constant cannot be ascribed to the trans isomer alone. No effect of variation of surface-to-volume ratio could be detected. Some preliminary experiments in which toluene and ethylene were employed as additives indicated that these did not affect the rate of formation of nitrogen. Nevertheless, because of a certain amount of scatter in the results, a small effect could not be excluded. There were at least nine products, in addition to nitrogen.

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Analytical solution to the Curtin-Hammett/Winstein-Holness kinetic system

Cited by 36 publications

References 7 publications

Rolf Huisgen's Classic Studies of Cyclic Triene Diels–Alder Reactions Elaborated by Modern Computational Analysis

Rolf Huisgen's Classic Studies of Cyclic Triene Diels–Alder Reactions Elaborated by Modern Computational Analysis

La relación entre la conformación y la reactividad

The thermal decomposition of azobenzene

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