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Product-Rate Correlations for Solvolyses of 2,4-Dimethoxybenzenesulfonyl Chloride
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  • Product-Rate Correlations for Solvolyses of 2,4-Dimethoxybenzenesulfonyl Chloride
  • Product-Rate Correlations for Solvolyses of 2,4-Dimethoxybenzenesulfonyl Chloride
저자명
Kim. Soo Ryeon,Choi. Hojune,Park. Jong Keun,Koo. In Sun,Koh. Han Joong
간행물명
Bulletin of the Korean Chemical Society
권/호정보
2014년|35권 1호|pp.51-56 (6 pages)
발행정보
대한화학회
파일정보
정기간행물|ENG|
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이 논문은 한국과학기술정보연구원과 논문 연계를 통해 무료로 제공되는 원문입니다.
서지반출

기타언어초록

The solvolysis rate constants of 2,4-dimethoxybenzenesulfonyl chloride (1) in 30 different solvents are well correlated with the extended Grunwald-Winstein equation, using the $N_T$ solvent nucleophilicity scale and $Y_{Cl}$ solvent ionizing scale, with sensitivity values of $0.93{pm}0.14$ and $0.65{pm}0.06$ for l and m, respectively. These l and m values can be considered to support a $S_N2$ reaction pathway. The activation enthalpies (${Delta}H^{ eq}$) were 12.4 to $14.6kcal{cdot}mol^{-1}$ and the activation entropies (${Delta}S^{ eq}$) were -15.5 to -$32.3kcal{cdot}mol^{-1}{cdot}K^{-1}$, which is consistent with the proposed bimolecular reaction mechanism. The solvent kinetic isotope effects (SKIE) were 1.74 to 1.86, which is also in accord with the $S_N2$ mechanism and was possibly assisted using a general-base catalysis. The values of product selectivity (S) for solvolyses of 1 in alcohol/water mixtures was 0.57 to 6.5, which is also consistent with the proposed bimolecular reaction mechanism. Third-order rate constants, $k_{ww}$ and $k_{aa}$, were calculated from the rate constants ($k_{obs}$), together with $k_{aw}$ and $k_{wa}$ calculated from the intercept and slope of the plot of 1/S vs. [water]/[alcohol]. The calculated rate constants, $k_{calc}$ ($k_{ww}$, $k_{aw}$, $k_{wa}$ and $k_{aa}$), are in satisfactory agreement with the experimental values, supporting the stoichiometric solvation effect analysis.