%0 Journal Article %A Kaumanns, Oliver %A Appel, Roland %A Lemek, Tadeusz %A Seeliger, Florian %A Mayr, Herbert %D 2009 %T Nucleophilicities of the Anions of Arylacetonitriles and Arylpropionitriles in Dimethyl Sulfoxide %U https://acs.figshare.com/articles/journal_contribution/Nucleophilicities_of_the_Anions_of_Arylacetonitriles_and_Arylpropionitriles_in_Dimethyl_Sulfoxide/2888422 %R 10.1021/jo802241x.s001 %2 https://ndownloader.figshare.com/files/4586437 %K Dimethyl Sulfoxide %K nucleophilicity parameters %K carbanions 1 %K phenylpropionitrile anions 2 %K rate constants k 2 %K reactive nucleophiles %K UV %K DMSO %X 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. %I ACS Publications