Artículo
Nudelman, N.S.; Mancini, P.M.E.; Martinez, R.D.; Vottero, L.R. "Solvents effects on aromatic nucleophilic substitutions. Part 5. Kinetics of the reactions of 1-fluoro-2,4-dinitrobenzene with piperidine in aprotic solvents" (1987) Journal of the Chemical Society, Perkin Transactions 2(8):951-954
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Abstract:
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.
Registro:
| Documento: | Artículo |
| Título: | Solvents effects on aromatic nucleophilic substitutions. Part 5. Kinetics of the reactions of 1-fluoro-2,4-dinitrobenzene with piperidine in aprotic solvents |
| Autor: | Nudelman, N.S.; Mancini, P.M.E.; Martinez, R.D.; Vottero, L.R. |
| Filiación: | Departamento de Química Orgánica, Universidad de Buenos Aires, Ciudad Universitaria, 1428 Buenos Aires, Argentina Inst. de Investigaciones de Productos Naturales, Análisis y Síntesis Orgánica, IPNAYS (CONICET-UNL-FIQ), 3000 Santa Fe, Argentina |
| Año: | 1987 |
| Número: | 8 |
| Página de inicio: | 951 |
| Página de fin: | 954 |
| Título revista: | Journal of the Chemical Society, Perkin Transactions 2 |
| ISSN: | 1472779X |
| Registro: | https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_1472779X_v_n8_p951_Nudelman |
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Citas:
---------- APA ----------
Nudelman, N.S., Mancini, P.M.E., Martinez, R.D. & Vottero, L.R. (1987) . Solvents effects on aromatic nucleophilic substitutions. Part 5. Kinetics of the reactions of 1-fluoro-2,4-dinitrobenzene with piperidine in aprotic solvents. Journal of the Chemical Society, Perkin Transactions 2(8), 951-954.Recuperado de https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_1472779X_v_n8_p951_Nudelman [ ]
---------- CHICAGO ----------
Nudelman, N.S., Mancini, P.M.E., Martinez, R.D., Vottero, L.R. "Solvents effects on aromatic nucleophilic substitutions. Part 5. Kinetics of the reactions of 1-fluoro-2,4-dinitrobenzene with piperidine in aprotic solvents" . Journal of the Chemical Society, Perkin Transactions 2, no. 8 (1987) : 951-954.Recuperado de https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_1472779X_v_n8_p951_Nudelman [ ]
---------- MLA ----------
Nudelman, N.S., Mancini, P.M.E., Martinez, R.D., Vottero, L.R. "Solvents effects on aromatic nucleophilic substitutions. Part 5. Kinetics of the reactions of 1-fluoro-2,4-dinitrobenzene with piperidine in aprotic solvents" . Journal of the Chemical Society, Perkin Transactions 2, no. 8, 1987, pp. 951-954.Recuperado de https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_1472779X_v_n8_p951_Nudelman [ ]
---------- VANCOUVER ----------
Nudelman, N.S., Mancini, P.M.E., Martinez, R.D., Vottero, L.R. Solvents effects on aromatic nucleophilic substitutions. Part 5. Kinetics of the reactions of 1-fluoro-2,4-dinitrobenzene with piperidine in aprotic solvents. 1987(8):951-954.Available from: https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_1472779X_v_n8_p951_Nudelman [ ]
