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DOI: 10.1039/A705667B (Paper) Reference Section for: J. Chem. Soc., Perkin Trans. 2, 1998, 325-334

Catalysis in aromatic nucleophilic substitution. Part 12.1 Kinetics of the reactions of some 2-phenoxy- and 2-([hair space]p-nitrophenoxy)-3-nitro-5-X-thiophenes with benzylamine and N-benzylmethylamine in benzene

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Giovanni Consiglio, Vincenzo Frenna, Elisabetta Mezzina, Antonio Pizzolato and Domenico Spinelli

Abstract

The rate constants of the title reactions have been measured in benzene at 20 °C. The reactions with benzylamine are not base-catalysed. The second-order kinetic constant for the reactions with N-benzylmethylamine, with the exception of the unsubstituted compound (X = H), increases in a hyperbolical way with increasing nucleophile concentration. A non-linear regression treatment of kinetic data allows the calculation of k1 and k3B/k–1 for each catalysed system. k3B/k–1 is not a monotonic function of the X substituent. This result has been rationalised on the grounds of a specific base–general acid (SB–GA) mechanism for the base catalysis.

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