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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Autor principal: Nudelman, N.S
Formato: Capítulo de libro
Lenguaje:Inglés
Publicado: 1989
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100 1 |a Nudelman, N.S. 
245 1 4 |a The ‘dimer mechanism’ in aromatic nucleophilic substitution by amines in aprotic solvents 
260 |c 1989 
270 1 0 |m Nudelman, N.S.; Depto. Química Orgánica, Facultad de Ciencias Exactas y Naturales Universidad de Buenos Aires, P. 3, Cdad. Universitaria, Buenos Aires, 1428, Argentina 
506 |2 openaire  |e Política editorial 
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504 |a Nudelman, N.S., Palleros, D., (1983) J. Org. Chem., 48, p. 1607 
504 |a Nudelman, N.S., Cerdeira, S., (1983), p. 695. , J. Chem. Soc. Perkin Trans. 2; Becker, G., Bernasconi, C.F., Zollinger, H., (1966) Helv. Chim. Acta, 49, p. 10 
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504 |a Bernasconi, C.F., Zollinger, H., (1966) Helvetica Chimica Acta, 49, p. 2570 
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520 3 |a 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.  |l eng 
593 |a Depto. Química Orgánica, Facultad de Ciencias Exactas y Naturales Universidad de Buenos Aires, P. 3, Cdad. Universitaria, Buenos Aires, 1428, Argentina 
773 0 |d 1989  |g v. 2  |h pp. 1-14  |k n. 1  |p J Phys Org Chem  |x 08943230  |w (AR-BaUEN)CENRE-576  |t Journal of Physical Organic Chemistry 
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