Correlation of the rates of solvolysis of n-octyl fluoroformate and a comparison with n-octyl chloroformate solvolysis
Correlation of the rates of solvolysis of n-octyl fluoroformate and a comparison with n-octyl chloroformate solvolysis
复制标题
DOI：
10.1039/b109169g
复制
发表时间：
2002-01-01
期刊：
影响因子：
--
通讯作者：
D'Souza, MJ
中科院分区：
文献类型：
--
作者：
Kevill, DN;D'Souza, MJ
在 24.2 摄氏度下，在 28 种纯溶剂和二元溶剂中测量了氟甲酸正辛酯的具体溶剂分解速率。对于已知 N-T（溶剂亲核性）和 Y-Cl（溶剂电离能力）值的 23 种溶剂，使用两项 Grunwald-Winstein 方程的相关性会导致对 1.80 +/- 0.13（l 值）和 0.79 +/- 0.06（m 值）两个尺度变化的敏感性。对于七种溶剂，对氯甲酸正辛酯溶剂分解进行了平行研究，并且在大多数情况下，F：Cl比速率比高于统一值，与决定速率的缔合-解离（加成-消除）途径的缔合步骤一致。
The specific rates of solvolysis of n-octyl fluoroformate have been measured at 24.2 degreesC in 28 pure and binary solvents. For the 23 solvents for which both N-T (solvent nucleophilicity) and Y-Cl (solvent ionizing power) values are known, a correlation using the two-term Grunwald-Winstein equation leads to sensitivities towards changes in the two scales of 1.80 +/- 0.13 (l value) and 0.79 +/- 0.06 (m value), respectively. For seven solvents, a parallel study was made of n-octyl chloroformate solvolysis and F : Cl specific rate ratios were, in most instances, above unity, consistent with the association step of an association-dissociation (addition-elimination) pathway being rate-determining.