%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://acs.figshare.com/ndownloader/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 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.
%I ACS Publications