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Nucleophilicities of the Anions of Arylacetonitriles and Arylpropionitriles in Dimethyl Sulfoxide

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journal contribution
posted on 02.01.2009 by Oliver Kaumanns, Roland Appel, Tadeusz Lemek, Florian Seeliger, Herbert Mayr
The rates of the reactions of the colored para-substituted phenylacetonitrile anions 1ac and the phenylpropionitrile anions 2ac with Michael acceptors (3au) were determined by UV−vis spectroscopy in DMSO at 20 °C. The reactions follow second-order kinetics, and the corresponding rate constants k2 obey the linear-free-energy relationship log k2(20 °C) = s(N + E), from which the nucleophile-specific parameters N and s of the carbanions 1ac and 2ac have been derived. With nucleophilicity parameters from 19 < N < 29, they are among the most reactive nucleophiles which we have so far parametrized. In DMSO, the nucleophilicity of the tert-butoxide anion is comparable to that of the p-cyanophenylacetonitrile anion 1b.