Correlations of the specific rates of solvolysis of aromatic carbamoyl chlorides, chloroformates, chlorothionoformates, and chlorodithioformates revisited
Correlations of the specific rates of solvolysis of aromatic carbamoyl chlorides, chloroformates, chlorothionoformates, and chlorodithioformates revisited
复制标题
DOI：
10.3390/i8040346
复制
发表时间：
2007-04-01
影响因子：
5.6
通讯作者：
D'Souza, Malcolm J.
中科院分区：
文献类型：
--
作者：
Kevill, Dennis N.;Koyoshi, Fumie;D'Souza, Malcolm J.
确定了氯甲酸苯酯的其他具体溶剂分解速率。这些值与文献值相结合，总共提供了 49 个数据点，这些数据点用于简单和扩展的 Grunwald-Winstein 处理。还汇总了文献值，以允许在比以前更多的溶剂中处理三种 N-芳基-N-甲基氨基甲酰氯、氯硫代甲酸苯酯、氯二硫代甲酸苯酯和 N,N-二苯基氨基甲酰氯。对于最后列出的两个，表明了包含由芳环参数（I）控制的术语的有意义的中等强度的证据。对于氨基甲酰氯的氮上仅具有一个芳环的电离反应，或者对于通过加成-消除（缔合-解离）机制进行的氯甲酸酯或氯硫代甲酸酯的溶剂解，没有发现需要包含该参数的证据。
Additional specific rates of solvolysis are determined for phenyl chloroformate. These values are combined with literature values to give a total of 49 data points, which are used within simple and extended Grunwald-Winstein treatments. Literature values are also brought together to allow treatments in more solvents than previously for three N-aryl-N-methylcarbamoyl chlorides, phenyl chlorothionoformate, phenyl chlorodithioformate, and N,N-diphenylcarbamoyl chloride. For the last two listed, moderately strong evidence for a meaningful inclusion of a term governed by the aromatic ring parameter ( I) was indicated. No evidence was found requiring inclusion of this parameter for ionization reactions with only one aromatic ring on the nitrogen of carbamoyl chlorides or for the solvolyses of the chloroformate or chlorothionoformate proceeding by an addition-elimination (association-dissociation) mechanism.