The reaction of 2,4-dinitrofluorobenzene with aniline, cyclohexylamine, and 1,2-diaminocyclohexanes in aprotic solvents. A new approach to the 'dimer mechanism'

The reaction of 2,4-dinitrofluorobenzene (DNF) with aniline in toluene and in chloroform at 35°C shows a third-order kinetic dependence on [amine]. In hydrogen-bond acceptor (HBA) solvents, an important rate increase, and a second-order dependence on [amine], are observed. Finally, the reaction show...

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Publicado: 1990
Acceso en línea:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_1472779X_v_n7_p1073_Nudelman
http://hdl.handle.net/20.500.12110/paper_1472779X_v_n7_p1073_Nudelman
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Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires
id paper:paper_1472779X_v_n7_p1073_Nudelman
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spelling paper:paper_1472779X_v_n7_p1073_Nudelman2023-06-08T16:17:29Z The reaction of 2,4-dinitrofluorobenzene with aniline, cyclohexylamine, and 1,2-diaminocyclohexanes in aprotic solvents. A new approach to the 'dimer mechanism' The reaction of 2,4-dinitrofluorobenzene (DNF) with aniline in toluene and in chloroform at 35°C shows a third-order kinetic dependence on [amine]. In hydrogen-bond acceptor (HBA) solvents, an important rate increase, and a second-order dependence on [amine], are observed. Finally, the reaction shows a second-order dependence on non-nucleophilic tertiary amines. All these results are fully consistent with the previously proposed 'dimer nucleophile mechanism.' Another approach towards confirming the mechanism was designed: a system where an 'intramolecular dimer nucleophile' is possible. The reactions of DNF with cyclohexylamine, and with cis-and trans-1,2-diaminocyclohexane, were studied in toluene, and also in toluene-methanol mixtures in some cases. The kinetic order observed, as well as the enhanced reactivity of the cis isomer and the solvent effects are new evidence in favour of the 'dimer nucleophile' mechanism. The results cannot be explained by other, alternative mechanisms. 1990 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_1472779X_v_n7_p1073_Nudelman http://hdl.handle.net/20.500.12110/paper_1472779X_v_n7_p1073_Nudelman
institution Universidad de Buenos Aires
institution_str I-28
repository_str R-134
collection Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
description The reaction of 2,4-dinitrofluorobenzene (DNF) with aniline in toluene and in chloroform at 35°C shows a third-order kinetic dependence on [amine]. In hydrogen-bond acceptor (HBA) solvents, an important rate increase, and a second-order dependence on [amine], are observed. Finally, the reaction shows a second-order dependence on non-nucleophilic tertiary amines. All these results are fully consistent with the previously proposed 'dimer nucleophile mechanism.' Another approach towards confirming the mechanism was designed: a system where an 'intramolecular dimer nucleophile' is possible. The reactions of DNF with cyclohexylamine, and with cis-and trans-1,2-diaminocyclohexane, were studied in toluene, and also in toluene-methanol mixtures in some cases. The kinetic order observed, as well as the enhanced reactivity of the cis isomer and the solvent effects are new evidence in favour of the 'dimer nucleophile' mechanism. The results cannot be explained by other, alternative mechanisms.
title The reaction of 2,4-dinitrofluorobenzene with aniline, cyclohexylamine, and 1,2-diaminocyclohexanes in aprotic solvents. A new approach to the 'dimer mechanism'
spellingShingle The reaction of 2,4-dinitrofluorobenzene with aniline, cyclohexylamine, and 1,2-diaminocyclohexanes in aprotic solvents. A new approach to the 'dimer mechanism'
title_short The reaction of 2,4-dinitrofluorobenzene with aniline, cyclohexylamine, and 1,2-diaminocyclohexanes in aprotic solvents. A new approach to the 'dimer mechanism'
title_full The reaction of 2,4-dinitrofluorobenzene with aniline, cyclohexylamine, and 1,2-diaminocyclohexanes in aprotic solvents. A new approach to the 'dimer mechanism'
title_fullStr The reaction of 2,4-dinitrofluorobenzene with aniline, cyclohexylamine, and 1,2-diaminocyclohexanes in aprotic solvents. A new approach to the 'dimer mechanism'
title_full_unstemmed The reaction of 2,4-dinitrofluorobenzene with aniline, cyclohexylamine, and 1,2-diaminocyclohexanes in aprotic solvents. A new approach to the 'dimer mechanism'
title_sort reaction of 2,4-dinitrofluorobenzene with aniline, cyclohexylamine, and 1,2-diaminocyclohexanes in aprotic solvents. a new approach to the 'dimer mechanism'
publishDate 1990
url https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_1472779X_v_n7_p1073_Nudelman
http://hdl.handle.net/20.500.12110/paper_1472779X_v_n7_p1073_Nudelman
_version_ 1768544054619930624

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