D'Souza Malcolm J, Wirick Jeremy, Deol Jasbir, Kevill Dennis N
Department of Chemistry, Wesley College, 120 N. State Street, Dover, DE 19901-3875.
Department of Chemistry and Biochemistry, Northern Illinois University, DeKalb, IL 60115-2862, USA.
Trends Org Chem. 2018;19:1-11.
The experimentally measured rates of solvolysis of 2-chloroethoxycarbonyl chloride (2-chloroethyl chloroformate, , 2-chloroethoxycarbonyl -toluenesufonate , and phenoxycarbonyl -toluenesulfonate () were followed at 25.0 °C in various pure and binary aqueous-organic solvents with varying degrees of polarity. An analysis of the rate constants for , and , was carried out using the two-term extended Grunwald-Winstein equation and comparisons are made to the previously published results for ethyl and phenyl chloroformate esters. The / rate ratios and the Grunwald-Winstein ratios indicate the probability of a dominant bimolecular carbonyl-addition pathway in the more nucleophilic solvents. Nevertheless in and , in the strongly hydrogen-bonding 70% and 50% HFIP mixtures, a side-by-side ionization mechanism is favored.
在25.0℃下，于各种具有不同极性程度的纯溶剂和二元水-有机溶剂中，跟踪测量了2-氯乙氧基羰基氯（2-氯乙基氯甲酸酯）、2-氯乙氧基羰基对甲苯磺酸酯和苯氧基羰基对甲苯磺酸酯的溶剂解实验速率。使用二项扩展的格鲁恩瓦尔德-温斯坦方程对、和的速率常数进行了分析，并与先前发表的氯甲酸乙酯和苯酯的结果进行了比较。/速率比和格鲁恩瓦尔德-温斯坦比表明在亲核性更强的溶剂中存在占主导的双分子羰基加成途径的可能性。然而，在和中，在强氢键作用的70%和50%六氟异丙醇混合物中，并行电离机制更受青睐。
