| Autor: |
D'Souza MJ; Department of Chemistry, Wesley College, 120 N. State Street, Dover, DE 19901, USA., Knapp JA; Department of Chemistry, Wesley College, 120 N. State Street, Dover, DE 19901, USA., Fernandez-Bueno GA; Department of Chemistry, Wesley College, 120 N. State Street, Dover, DE 19901, USA., Kevill DN; Department of Chemistry and Biochemistry, Northern Illinois University, DeKalb, IL 60115, USA. |
| Abstrakt: |
The specific rates of solvolysis of 2-butyn-1-yl-chloroformate (1) and 2-methoxyphenyl chloroformate (2) are studied at 25.0 °C in a series of binary aqueousorganic mixtures. The rates of reaction obtained are then analyzed using the extended Grunwald-Winstein (G-W) equation and the results are compared to previously published G-W analyses for phenyl chloroformate (3), propargyl chloroformate (4), p-methoxyphenyl choroformate (5), and p-nitrophenyl chloroformate (6). For 1, the results indicate that dual side-by-side addition-elimination and ionization pathways are occurring in some highly ionizing solvents due to the presence of the electron-donating γ-methyl group. For 2, the analyses indicate that the dominant mechanism is a bimolecular one where the formation of a tetrahedral intermediate is rate-determining. |
