Nucleophilicities of the Anions of Arylacetonitriles and Arylpropionitriles in Dimethyl Sulfoxide

The Journal of Organic Chemistry, 2009, 74 (1), 75-81 (pdf) published on 26.11.2008
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The rates of the reactions of the colored para-substituted phenylacetonitrile anions 1a-c and the phenylpropionitrile anions 2a-c with Michael acceptors (3a-u) 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 1a-c and 2a-c 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.
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