Extended Grunwald-Winstein analysis - LFER used to gauge solvent effects in p-nitrophenyl chloroformate solvolysis.
Extended Grunwald-Winstein analysis - LFER used to gauge solvent effects in p-nitrophenyl chloroformate solvolysis.
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DOI：
10.3390/ijms9112231
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发表时间：
2008-11
影响因子：
5.6
通讯作者：
Kevill DN
中科院分区：
文献类型：
--
作者：
D'Souza MJ;Shuman KE;Carter SE;Kevill DN
使用扩展的（两项）Grunwald-Winstein方程分析了氯甲酸对硝基苯酯（1）在25 °C下的溶剂分解比速率。对于39种溶剂，得到的溶剂亲核性（l）和溶剂电离能力（m）的灵敏度（l = 1.68±0.06和m = 0.46±0.04）与以前对氯甲酸苯酯（2）和氯甲酸对甲氧基苯酯（3）观察到的结果相似。将新的动力学数据在几个含氟代醇的混合物的意见，合理化的反应是敏感的取代基效应和反应机制，涉及的添加（协会）步骤的添加-消除（协会-解离）途径的速率决定。还将1、2和3的l/m比与先前公布的氯甲酸苄酯（4）和氯甲酸对硝基苄酯（5）的l/m比进行比较。
Specific rates of solvolysis at 25 °C for p-nitrophenyl chloroformate (1) are analyzed using the extended (two-term) Grunwald-Winstein equation. For 39 solvents, the sensitivities (l = 1.68±0.06 and m = 0.46±0.04) towards changes in solvent nucleophilicity (l) and solvent ionizing power (m) obtained, are similar to those previously observed for phenyl chloroformate (2) and p-methoxyphenyl chloroformate (3). The observations incorporating new kinetic data in several fluoroalcohol-containing mixtures, are rationalized in terms of the reaction being sensitive to substituent effects and the mechanism of reaction involving the addition (association) step of an addition-elimination (association-dissociation) pathway being rate-determining. The l/m ratios obtained for 1, 2, and 3, are also compared to the previously published l/m ratios for benzyl chloroformate (4) and p-nitrobenzyl chloroformate (5).
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影响因子：
3.6
作者：
Bentley, TW;Harris, HC;Szajda, SR
通讯作者：
Szajda, SR
影响因子：
5.6
作者：
Kevill, Dennis N.;Koyoshi, Fumie;D'Souza, Malcolm J.
通讯作者：
D'Souza, Malcolm J.
影响因子：
3.6
作者：
Kevill, DN;Abduljaber, MH
通讯作者：
Abduljaber, MH
DOI：
10.1039/b109169g
发表时间：
2002-01-01
期刊：
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2
影响因子：
--
作者：
Kevill, DN;D'Souza, MJ
通讯作者：
D'Souza, MJ
DOI：
10.1039/a701140g
发表时间：
1997-09-01
期刊：
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2
影响因子：
--
作者：
Kevill, DN;DSouza, MJ
通讯作者：
DSouza, MJ