Abstract

A mechanism has been proposed for the reaction of 1,3-dichloropropene with dipotassium propane-1,3-bis(dithiolate) in the system hydrazine hydrate–potassium hydroxide on the basis of DFT quantum chemical calculations at the B3LYP/6-311++G(d,p) level of theory. The first stage of this reaction has been found to be nucleophilic substitution of one chlorine atom of 1,3-dichloropropene linked to the sp³-carbon atom by the sulfur atom of propane-1,3-bis(thiolate) to give the corresponding monosubstitution product. Further transformations of the latter could lead to the formation of six-, seven-, and eight-membered sulfur heterocycles, as well as of a linear structure as a result of reaction of the monosubstitution product with the second 1,3-dichloropropene molecule.

中文翻译：

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有机反应机理的量子化学研究：X. 丙烷-1,3-双（硫醇盐）二钾与 1,3-二氯丙烯在水合肼-KOH 系统中的反应

摘要

基于 B3LYP/6-311+ 的 DFT 量子化学计算，提出了 1,3-二氯丙烯与丙烷-1,3-双（二硫醇盐）二钾在水合肼-氢氧化钾体系中反应的机理+G( d , p ) 理论水平。已发现该反应的第一阶段是与sp ³相连的 1,3-二氯丙烯的一个氯原子的亲核取代-碳原子被丙烷-1,3-双（硫醇盐）的硫原子取代，得到相应的单取代产物。后者的进一步转化可能导致六元、七元和八元硫杂环的形成，以及作为单取代产物与第二个 1,3-二氯丙烯分子反应的结果的线性结构。