Mechanisms of front-side substitutions. The transition states for the SNi decomposition of methyl and ethyl chlorosulfite in the gas phase and in solution - Research portal of Justus Liebig University Giessen:

Journal article

Mechanisms of front-side substitutions. The transition states for the SNi decomposition of methyl and ethyl chlorosulfite in the gas phase and in solution

Authors list: Schreiner, PR; Schleyer, PV; Hill, RK

Publication year: 1994

Pages: 1849-1854

Journal: The Journal of Organic Chemistry

Volume number: 59

Issue number: 7

ISSN: 0022-3263

DOI Link: https://doi.org/10.1021/jo00086a041

Publisher: American Chemical Society

Abstract:
We examined the front (S(N)i)- and back (S(N)2)-side substitutions of methyl and ethyl chlorosulfite in isolated and in simulated solution conditions using ab initio MO methods. All methyl chlorosulfite structures were optimized up to the MP2(fc)/6-31+G* level, but the changes are small with increased sophistication of the computational method. Consequently, we optimized ethyl chlorosulfite structures at HF/6-31G* and computed single point energies at MP2(fc)/G-31+G*//HF/6-31G*. Solution effects were simulated by means of single point energies on the HF/6-31G* optimized geometries using the self consistent reaction field (SCRF) model. Dielectric constants epsilon of hexane, carbon tetrachloride, sulfur dioxide, methanol, and water were employed. While the front-side substitution of methyl chlorosulfite is favored in the gas phase and in nonpolar solvents, back-side attack is preferred in polar solvents due to a more favorable stabilization of the back-side transition state. The S(N)i mode is preferred for ethyl chlorosulfite, in the gas phase and in all solvents; the cationic center is stabilized more by hyperconjugation than by solvent interaction.

Authors/Editors

- Uni.-Prof. Dr. Peter Richard Schreiner, PhD

Citation Styles

Harvard Citation style: Schreiner, P., Schleyer, P. and Hill, R. (1994) Mechanisms of front-side substitutions. The transition states for the SNi decomposition of methyl and ethyl chlorosulfite in the gas phase and in solution, The Journal of Organic Chemistry, 59(7), pp. 1849-1854. https://doi.org/10.1021/jo00086a041

APA Citation style: Schreiner, P., Schleyer, P., & Hill, R. (1994). Mechanisms of front-side substitutions. The transition states for the SNi decomposition of methyl and ethyl chlorosulfite in the gas phase and in solution. The Journal of Organic Chemistry. 59(7), 1849-1854. https://doi.org/10.1021/jo00086a041