Transformation of 2,2-Di(3-nitro-4-chlorophenyl)-1,1,1-trichloroethane in the Alkali–Amide Solvent Medium

E. A. Guzov; Гузов Е. А.; M. B. Kuzhin; Кужин М. Б.; M. P. Baranova; Баранова М. П.; V. N. Kazin; Казин В. Н.

Transformation of 2,2-Di(3-nitro-4-chlorophenyl)-1,1,1-trichloroethane in the Alkali–Amide Solvent Medium

Autores: Guzov E.¹, Kuzhin M.¹, Baranova M.¹, Kazin V.¹
Afiliações:
1. P. G. Demidov Yaroslavl State University
Edição: Volume 94, Nº 2 (2024)
Páginas: 185-193
Seção: Articles
URL: https://journals.rcsi.science/0044-460X/article/view/260282
ID: 260282

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Resumo

A quantum chemical analysis of the transformation pathways of 2,2-di(3-nitro-4-chlorophenyl)-1,1,1-trichloroethane in NaOH–DMF, involving competing reagents, was performed. For each reaction, spatial structures were modeled and the energy parameters of the pre-reaction, activated and post-reaction complexes were calculated. As a result of the analysis of the thermodynamic parameters of the reactions, the most energetically favorable scheme for the transformation of 2,2-di(3-nitro-4-chlorophenyl)-1,1,1-trichloroethane into 2,2-di(3-nitro-4-N,N-dimethylaminophenyl)-1,1-dichloroethene was proposed. The mechanisms of the occurring reactions were established.

Palavras-chave

2,2-di(3-nitro-4-chlorophenyl)-1,1,1-trichloroethane, alkaline hydrolysis of DMF, anionic complex, density functional method, mechanisms of dehydrochlorination and nucleophilic substitution reactions

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Sobre autores

E. Guzov

P. G. Demidov Yaroslavl State University

Email: kaz@uniyar.ac.ru
Rússia, Yaroslavl, 150003

M. Kuzhin

P. G. Demidov Yaroslavl State University

Email: kaz@uniyar.ac.ru
Rússia, Yaroslavl, 150003

M. Baranova

P. G. Demidov Yaroslavl State University

Email: kaz@uniyar.ac.ru
Rússia, Yaroslavl, 150003

V. Kazin

P. G. Demidov Yaroslavl State University

Autor responsável pela correspondência
Email: kaz@uniyar.ac.ru
Rússia, Yaroslavl, 150003

Bibliografia

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2. Fig. 1. Energy profile and dynamics of changes in the interatomic distance (H6–C1, C2–Cl4) of the reaction of dehydrochlorination of 2,2-di(3-nitro-4-chlorophenyl)-1,1,1-trichloroethane with dimethylaminomethanediol carbanion (O-attack). Spatial structures of the pre-reaction (1), activated (2) and post-reaction complexes (3). The charge on the atoms according to Mulliken (A. E.) is given in italics.

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3. Fig. 2. Energy profile and dynamics of changes in the interatomic distance (C1–N3, C1–Cl2) of the nucleophilic substitution reaction of the chlorine atom in the interaction of 2,2-di(3-nitro-4-chlorophenyl)-1,1,1-trichloroethane with carbanion N,N- dimethylaminomethanediol (N-attack). Spatial structures of the pre-reaction (1), activated (2) and post- reaction complexes (3). The charge on the atoms according to Mulliken (A. E.) is given in italics.