QUANTUM-CHEMICAL STUDY OF THE REACTION MECHANISM 1,2-ETHEDITIOL WITH 1,3-DICHLOROBUTEN-2
Rubrics: CHEMISTRY AND CHEMICAL TECHNOLOGY
Authors:
2.
, Russian Federation
Type:
Article
Pages:
from 104
to 105
Status:
Published
Received:
05.04.2019
Accepted:
14.01.2023
Published:
15.04.2019
Language:
Russian
Keywords:
1,2-ethanedithiol, 1,3-dichlorobutene-2, reaction mechanism, nucleophilic substitution, theory of the electron density functional, B3LYP, potential energy surface.
Abstract (English):
According to the results of a quantum chemical study in the framework of the electron density functional theory using the В3LYP / 6-311++ G (d, p) method, a theoretical mechanism of the reaction of 1,3-dichlorobutene-2 with 1,2-ethanedithiol in the hydrazine hydrate-KOH system has been proposed. It is shown that this interaction proceeds sequentially in several stages, including nucleophilic substitution of the chlorine atom located on the sp3 hybridized carbon atom by the sulfur atom (SN2 mechanism) with the formation of a monosubstitution product, which under the action of alkali undergoes dehydrochlorination by the bimolecular mechanism E2, to form acetylene intermediate. The obtained acetylene derivative closes into the final dithian cycle as a result of the intramolecular nucleophilic attack of the free thiolate group on the -carbon atom of the acetylene fragment.
According to the results of a quantum chemical study in the framework of the electron density functional theory using the В3LYP / 6-311++ G (d, p) method, a theoretical mechanism of the reaction of 1,3-dichlorobutene-2 with 1,2-ethanedithiol in the hydrazine hydrate-KOH system has been proposed. It is shown that this interaction proceeds sequentially in several stages, including nucleophilic substitution of the chlorine atom located on the sp3 hybridized carbon atom by the sulfur atom (SN2 mechanism) with the formation of a monosubstitution product, which under the action of alkali undergoes dehydrochlorination by the bimolecular mechanism E2, to form acetylene intermediate. The obtained acetylene derivative closes into the final dithian cycle as a result of the intramolecular nucleophilic attack of the free thiolate group on the -carbon atom of the acetylene fragment.
Keywords:
1,2-ethanedithiol, 1,3-dichlorobutene-2, reaction mechanism, nucleophilic substitution, theory of the electron density functional, B3LYP, potential energy surface.
1,2-ethanedithiol, 1,3-dichlorobutene-2, reaction mechanism, nucleophilic substitution, theory of the electron density functional, B3LYP, potential energy surface.
