氯甲酸异丙烯酯溶剂解的详细分析
Detailed Analysis for the Solvolysis of Isopropenyl Chloroformate.
作者信息
D'Souza Malcolm John, Shuman Kevin Edward, Omondi Arnold Ochieng, Kevill Dennis Neil
机构信息
Department of Chemistry, Wesley College, Dover, DE, 19901, USA.
出版信息
Eur J Chem. 2011 Jun;2(2):130-135. doi: 10.5155/eurjchem.2.2.130-135.405.
Abstract
The specific rates of solvolysis (including those obtained from the literature) of isopropenyl chloroformate (1) are analyzed using the extended Grunwald-Winstein equation, involving the N(T) scale of solvent nucleophilicity (S-methyldibenzothiophenium ion) combined with a Y(Cl) scale based on 1-adamantyl chloride solvolysis. A similarity model approach, using phenyl chloroformate solvolyses for comparison, indicated a dominant bimolecular carbonyl-addition mechanism for the solvolyses of 1 in all solvents except 97% 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP). An extensive evaluation of the outcomes acquired through the application of the extended Grunwald-Winstein equation resulted in the proposal of an addition-elimination mechanism dominating in most of the solvents, but in 97-70% HFIP, and 97% 2,2,2-trifluoroethanol (TFE), it is proposed that a superimposed unimolecular (S(N)1) type ionization is making a significant contribution.
摘要
使用扩展的格鲁纳德-温斯坦方程分析了氯甲酸异丙烯酯（1）的溶剂解特定速率（包括从文献中获得的速率），该方程涉及溶剂亲核性的N(T)标度（S-甲基二苯并噻吩鎓离子）以及基于1-金刚烷基氯溶剂解的Y(Cl)标度。采用相似模型方法，以氯甲酸苯酯的溶剂解作为比较，结果表明，在除97% 1,1,1,3,3,3-六氟-2-丙醇（HFIP）之外的所有溶剂中，1的溶剂解主要通过双分子羰基加成机理进行。通过应用扩展的格鲁纳德-温斯坦方程对所得结果进行广泛评估后，提出了在大多数溶剂中占主导地位的加成-消除机理，但在97%-70%的HFIP以及97%的2,2,2-三氟乙醇（TFE）中，推测叠加的单分子（S(N)1）型电离起了重要作用。
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