THEORETICAL STUDY OF THE INTERACTION OF 1,2-ETHANEDITHIOL WITH 1,3-DICHLOROPROPENE IN THE HYDRAZRAZINE HYDRATE SYSTEM
Rubrics: CHEMISTRY AND CHEMICAL TECHNOLOGY
Authors:
Type:
Article
Pages:
from 114
to 120
Status:
Published
Received:
05.12.2018
Accepted:
18.12.2018
Published:
18.12.2018
Language:
Russian
Keywords:
1,3-dichloropropene, 1,2-ethanedithiol, allyl regrouping, reaction mechanism, nucleophilic addition, electron density functional theory, B3LYP, reaction energy profile.
Abstract (English):
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
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
Keywords:
1,3-dichloropropene, 1,2-ethanedithiol, allyl regrouping, reaction mechanism, nucleophilic addition, electron density functional theory, B3LYP, reaction energy profile.
1,3-dichloropropene, 1,2-ethanedithiol, allyl regrouping, reaction mechanism, nucleophilic addition, electron density functional theory, B3LYP, reaction energy profile.
