Bulletin of the Korean chemical society | |
Correlation of the Rates on Solvolysis of 2,2,2-Trichloroethyl Chloroformate Using the Extended Grunwald-Winstein Equation | |
Han Joong Koh1  Suk Jin Kang1  | |
关键词: 2; 2; 2-Trichloroethyl chloroformate; Extended grunwald-winstein equation; SN2 Mechanism; Solvent kinetic isotope effect; | |
DOI : | |
学科分类:化学(综合) | |
来源: Korean Chemical Society | |
【 摘 要 】
The solvolysis rate constants of 2,2,2-trichloroethyl chloroformate (Cl3CCH2OCOCl, 3) in 30 different solvents are well correlated with the extended Grunwald-Winstein equation, using the NT solvent nucleophilicity scale and the YCl solvent ionizing scale, with sensitivity values of 1.28 ± 0.06 and 0.46 ± 0.03 for l and m, respectively. The activation enthalpies (ΔH≠) are 10.1 to 12.8 kcal·mol−1 and the activation entropies (ΔS≠) are −27.8 to −36.8 cal·mol−1·K−1, which is consistent with the proposed bimolecular reaction mechanism. The kinetic solvent isotope effect (kMeOH/kMeOD) of 2.39 is also in accord with SN2 mechanism probably assisted by general-base catalysis.
【 授权许可】
Unknown
【 预 览 】
Files | Size | Format | View |
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RO201912010243816ZK.pdf | 515KB | download |