Open AccessTHEORETICAL STUDY OF THE INTERACTION OF 1,2-Ethanedithiol With 1,3-Dichloropropene in the Hydrazrazine Hydrate System
Author(s) -
E. A. Chirkina
Publication year - 2018
Publication title -
vestnik angarskogo gosudarstvennogo tehničeskogo universiteta
Language(s) - English
Resource type - Journals
ISSN - 2686-777X
DOI - 10.36629/2686-777x-2018-1-12-114-120
Subject(s) - chemistry , nucleophile , reagent , hydrate , medicinal chemistry , ring (chemistry) , sulfur , chlorine , nucleophilic substitution , hydrazine (antidepressant) , atom (system on chip) , double bond , hypervalent molecule , carbon atom , chlorine atom , organic chemistry , catalysis , chromatography , computer science , embedded system
According to the results of quantum chemical studies in the framework of the electron
density functional theory, the B3LYP / 6-311 ++ G (d, p) method proposed a theoretical mechanism
for the interaction of 1,3-dichloropropene with 1,2-ethanedithiol in the hydrazine-hydrateKOH system. It was shown that the reaction proceeds sequentially in several stages, including the nucleophilic
substitution of the chlorine atom of the sp3 hybridized carbon atom to the sulfur atom with the formation of the mono-substitution product, which undergoes prototropic allyl rearrangement, providing
the double bond to the atom sulfur. Next, the dithiolan ring closes due to the nucleophilic attack of the
sulfide anion of the second thiol group of the reagent on the carbon atom, which is in the γ position
relative to the second chlorine atom. The resulting vinyldithiolan is isomerized to a more stable
ethylidene-dithiolan as a result of prototropic allyl rearrangement