Solvents effects on aromatic nucleophilic substitutions. Part 5. Kinetics of the reactions of 1-fluoro-2,4-dinitrobenzene with piperidine in aprotic solvents
The kinetics of the reaction between 1-fluoro-2,4-dinitrobenzene and piperidine were studied in toluene, benzene, dioxane, trichloroethane, tetrahydrofuran, chlorobenzene, ethyl acetate, chloroform, dichloromethane, acetone, acetonitrile, and nitromethane. The second-order rate coefficient is almost...
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| Otros Autores: | , , |
| Formato: | Capítulo de libro |
| Lenguaje: | Inglés |
| Publicado: |
1987
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| Acceso en línea: | Registro en Scopus Handle Registro en la Biblioteca Digital |
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| Sumario: | The kinetics of the reaction between 1-fluoro-2,4-dinitrobenzene and piperidine were studied in toluene, benzene, dioxane, trichloroethane, tetrahydrofuran, chlorobenzene, ethyl acetate, chloroform, dichloromethane, acetone, acetonitrile, and nitromethane. The second-order rate coefficient is almost insensitive to the amine concentration in chloroform, acetonitrile, and nitromethane; for the other solvents this value of k3/k2 is greater than 102, indicating neat base catalysis. The trend in k3/k2 does not follow the solvent basicity order; the solvents insensitive to base catalysis are those which exhibit hydrogen-bond donor (HBD) properties. These results are interpreted as an indication that in this reaction the detachment of the nucleofuge is the rate-limiting step in most of the aprotic solvents studied; those solvents which are H B D assist the departure of fluoride, and the formation of the intermediate is the rate-determining step. This conclusion was confirmed by kF/k Cl determinations. A simple linear energy solvation correlation was found between the parameter ET(30) and kA obtained at [B] < 10-2M. For higher amine contents increasing deviations were found. |
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| ISSN: | 1472779X |