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https://doi.org/10.5562/cca2822

Nucleofugalities of Neutral Leaving Groups in 80 % Aqueous Acetonitrile

Sandra Jurić ; University of Zagreb, Faculty of Pharmacy and Biochemistry, Ante Kovačića 1, 10000 Zagreb, Croatia
Toni Portolan ; University of Zagreb, Faculty of Pharmacy and Biochemistry, Ante Kovačića 1, 10000 Zagreb, Croatia
Olga Kronja ; University of Zagreb, Faculty of Pharmacy and Biochemistry, Ante Kovačića 1, 10000 Zagreb, Croatia

Sažetak

Nucleofugalites of tetrahydrothiophene, dimethyl sulfide and differently substituted pyridines in 80 % aqueous acetonitrile have been derived from the S_N1 solvolysis rate constants of the corresponding X,Y-substituted benzhydryl derivatives (1–10). In sol-volysis of sulfonium ions in 80 % aqueous acetonitrile, where acetonitrile is a good cation solvator, the solvation of the reactant ground state is an important rate determining variable since the positive charge is almost entirely located on the leaving group. As a consequence, reaction rates of sulfonium ions are more sensitive to the substrate structure in 80 % aqueous acetonitrile than in pure and aqueous alcohols, which are less efficient as cation solvators. In solvolysis of pyridinium ions the solvation of the reactant ground state is less important, since the positive charge is considerably distributed between the carbon at the reaction center and the leaving group. In such cases the important rate determining variable is solvation of the transition state. Slower reactions of pyridinium sub-strates progress over later, carbocation-like transition states in which the solvation is more important, so those substrates solvolyze slightly faster in aqueous acetonitrile than in methanol (k_80AN > k_M). Faster reactions proceed over earlier TS in which the solvation is diminished, so those substrates solvolyze somewhat faster in methanol than in aqueous acetonitrile (k_80AN < k_M).

This work is licensed under a Creative Commons Attribution 4.0 International License.

Ključne riječi

nucleofugality; reactivity; neutral leaving groups; solvolysis; aprotic solvent

Hrčak ID:

155797

URI

https://hrcak.srce.hr/155797

Datum izdavanja:

20.6.2016.

Posjeta: 1.798 *