The ‘dimer mechanism’ in aromatic nucleophilic substitution by amines in aprotic solvents

The mechanism of aromatic nucleophilic substitutions by amines in protic solvents is well established; on the contrary the mechanism/s of the reactions in aprotic solvents is/are still subject of controversy. The present paper describes several systems for which fourth‐order kinetics (third‐order in...

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Publicado: 1989
Acceso en línea:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_08943230_v2_n1_p1_Nudelman
http://hdl.handle.net/20.500.12110/paper_08943230_v2_n1_p1_Nudelman
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spelling paper:paper_08943230_v2_n1_p1_Nudelman2023-06-08T15:47:48Z The ‘dimer mechanism’ in aromatic nucleophilic substitution by amines in aprotic solvents The mechanism of aromatic nucleophilic substitutions by amines in protic solvents is well established; on the contrary the mechanism/s of the reactions in aprotic solvents is/are still subject of controversy. The present paper describes several systems for which fourth‐order kinetics (third‐order in amine) were observed. A mechanism is proposed to account for this as well as other observation such as: overall negative energies of activation, quadratic dependence of kA with non‐nucleophilic tertiary bases, spectacular effects of hydrogen‐bond donor (HBD) and hydrogen‐bond acceptor (HBA) catalysts, etc. Other alternative mechanisms are also discussed. Copyright © 1989 John Wiley & Sons Ltd. 1989 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_08943230_v2_n1_p1_Nudelman http://hdl.handle.net/20.500.12110/paper_08943230_v2_n1_p1_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 mechanism of aromatic nucleophilic substitutions by amines in protic solvents is well established; on the contrary the mechanism/s of the reactions in aprotic solvents is/are still subject of controversy. The present paper describes several systems for which fourth‐order kinetics (third‐order in amine) were observed. A mechanism is proposed to account for this as well as other observation such as: overall negative energies of activation, quadratic dependence of kA with non‐nucleophilic tertiary bases, spectacular effects of hydrogen‐bond donor (HBD) and hydrogen‐bond acceptor (HBA) catalysts, etc. Other alternative mechanisms are also discussed. Copyright © 1989 John Wiley & Sons Ltd.
title The ‘dimer mechanism’ in aromatic nucleophilic substitution by amines in aprotic solvents
spellingShingle The ‘dimer mechanism’ in aromatic nucleophilic substitution by amines in aprotic solvents
title_short The ‘dimer mechanism’ in aromatic nucleophilic substitution by amines in aprotic solvents
title_full The ‘dimer mechanism’ in aromatic nucleophilic substitution by amines in aprotic solvents
title_fullStr The ‘dimer mechanism’ in aromatic nucleophilic substitution by amines in aprotic solvents
title_full_unstemmed The ‘dimer mechanism’ in aromatic nucleophilic substitution by amines in aprotic solvents
title_sort ‘dimer mechanism’ in aromatic nucleophilic substitution by amines in aprotic solvents
publishDate 1989
url https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_08943230_v2_n1_p1_Nudelman
http://hdl.handle.net/20.500.12110/paper_08943230_v2_n1_p1_Nudelman
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